JP6803723B2 - Laminate - Google Patents

Description

The present invention relates to a laminate in which a base material, a conductive layer and a coating layer are laminated in this order.

A laminate in which a conductive layer is provided on a base material is widely used in various fields. For example, a laminated body in which a conductive layer is patterned is used as a circuit board in the field of electronic devices such as communication devices. Further, the laminate provided with the ultrafine wiring or the ultrathin wiring as the patterned conductive layer can further form a touch panel or an optical display by combining with a transparent base material.

On the other hand, in such a laminated body, a coating layer covering the conductive layer is usually provided on the conductive layer. The coating layer is provided, for example, for the purpose of protecting the conductive layer. Then, when the laminate provided with such a coating layer is used, for example, in optical applications, it is required that the change in haze is suppressed even under moist heat conditions.

As a laminated film suitable for forming such a coating layer and having a small change rate of haze after wet heat treatment, a film having coating layers on both sides of a polyester film is bonded to both sides of an adhesive layer. Hard coat layers are provided on both sides of the exposed coating layer, the total light transmittance of the laminated film is 90% or more, and the haze change of the laminated film before and after 100 hours of wet heat treatment in an atmosphere of 85 ° C. and 85% RH. A laminated film having a rate of 1.5% or less is disclosed (see Patent Document 1).

Japanese Unexamined Patent Publication No. 2015-083335

However, when the coating layer is provided on the conductive layer using the laminated film described in Patent Document 1, the laminated film is interposed via an intermediate layer such as an adhesive layer or an adhesive layer in addition to the coating layer forming step. There is a problem that a sticking step of sticking the film on the conductive layer is required separately. Further, after the laminated film is attached, there is a problem that the intermediate layer may adversely affect the conductive layer in terms of performance. Further, it is not clear whether or not the change in haze of the entire laminated structure in which the laminated film is attached to the conductive layer in the laminated body after the wet heat treatment is suppressed.

The present invention has been made in view of the above circumstances, and can be manufactured as a laminate in which a base material, a conductive layer, and a coating layer are laminated in this order without performing a step of attaching the formed coating layer. An object of the present invention is to provide a laminate in which a change in haze of the entire laminate is suppressed even under moist heat conditions.

In order to solve the above problems, the laminate according to the first aspect of the present invention includes a base material, a conductive layer provided on the base material, and a coating layer provided on the conductive layer. The laminate having a first haze H ₀ of 3.0% or less measured from the coating layer side was treated in an atmosphere of a temperature of 85 ° C. and a relative humidity of 85% for 118 hours, and then the coating layer side was used. When the second haze H ₁₁₈ of the laminate was measured, the haze change rate ΔH _{118 of the} laminate calculated by the formula I ₁₁₈ : ΔH ₁₁₈ (%) = (H ₁₁₈ −H ₀ ) / H ₀ × 100. Is 100% or less.

The conductive layer may be directly contacted and laminated on the base material, and the coating layer may be directly contacted and laminated on the conductive layer.

According to the above aspect of the present invention, as a laminate in which the base material, the conductive layer and the coating layer are laminated in this order, the laminate can be manufactured without performing the step of attaching the formed coating layer, and the laminate can be manufactured even under moist heat conditions. A laminate is provided in which changes in the overall haze are suppressed.

It is sectional drawing which shows one Embodiment of the laminated body of this invention schematically. It is sectional drawing which shows typically the other embodiment of the laminated body of this invention. It is sectional drawing for schematically explaining the manufacturing method of the laminated body shown in FIG.

<< Laminated body >>
The laminate according to the embodiment of the present invention is a laminate in which the base material, the conductive layer, and the coating layer are laminated in this order, and the haze H ₀ measured from the coating layer side is 3.0% or less. After treating the laminate in an atmosphere of a temperature of 85 ° C. and a relative humidity of 85% for 118 hours, when the haze H _{118 of the} laminate was measured from the coating layer side, it was calculated by the following formula (I ₁₁₈ ). The haze change rate ΔH ₁₁₈ of the laminated body is 100% or less.
ΔH ₁₁₈ (%) = (H ₁₁₈ −H ₀ ) / H ₀ × 100 ・ ・ ・ ・ (I ₁₁₈ )
In other words, the laminate according to the above embodiment includes a base material, a conductive layer provided on the base material, and a coating layer provided on the conductive layer, and is measured from the coating layer side. The laminated body having a first haze H ₀ of 3.0% or less was treated for 118 hours in an atmosphere of a temperature of 85 ° C. and a relative humidity of 85%, and then the second layer of the laminated body was treated from the coating layer side. When the haze H ₁₁₈ is measured, the haze change rate ΔH _{118 of the} laminate calculated by the formula I ₁₁₈ : ΔH ₁₁₈ (%) = (H ₁₁₈ −H ₀ ) / H ₀ × 100 is 100% or less. ..

The laminate of the present invention has, for example, a haze H ₀ of 3.0% or less in the initial stage before being placed under moist heat conditions, and has excellent optical properties. Further, even when the laminate is placed under moist heat conditions and aged, the laminate of the present invention suppresses the change in haze, for example, the haze change rate ΔH ₁₁₈ becomes 100% or less, and preferable optical characteristics are maintained.
The laminate of the present invention having such optical properties can be produced, for example, by adjusting the materials of the base material, the conductive layer and the coating layer, particularly the material of the coating layer.

As will be described later, in the case of providing a coating layer on the conductive layer at the time of manufacturing the laminate, the laminate of the present invention is cured by directly coating the coating layer composition on the conductive layer forming surface of the base material. It is possible to provide a coating layer by allowing the coating layer to be provided. Therefore, the laminate of the present invention can be manufactured without performing a sticking step of separately forming a coating layer and sticking the preformed coating layer to the conductive layer, and the coating layer sticking step is unnecessary. The manufacturing process can be simplified. Further, in the laminate of the present invention, unlike the case where the sticking step is performed, the coating layer can be formed by coating the composition for the coating layer, so that the coating layer does not go through an intermediate layer such as an adhesive layer or an adhesive layer. , The coating layer can be formed directly on the conductive layer and, if necessary, on the base material, and the structure of the laminated body can be simplified. Further, in the laminated body of the present invention, by not providing such an intermediate layer, it is possible to eliminate the possibility that the intermediate layer adversely affects the conductive layer and the coating layer in terms of quality.

In the present specification, the “haze of the laminated body” means the haze of the entire laminated body measured from the side where the coating layer is provided (outer surface of the coating layer) unless otherwise specified. And, "haze" means a value measured according to JIS K7136 unless otherwise specified, and in this invention, the absolute value of the value measured according to JIS K7136 is adopted.

FIG. 1 is a cross-sectional view schematically showing an embodiment of the laminated body of the present invention.
In the laminate 1 shown in FIG. 1, the base material 11, the conductive layer 12, and the coating layer 13 are laminated in this order. In other words, the laminate 1 is configured by providing the coating layer 13 on the base material 11 and providing the conductive layer 12 between the base material 11 and the coating layer 13. That is, the laminate 1 includes a base material 11, a conductive layer 12 provided on the base material 11, and a coating layer 13 provided on the base material 11 via the conductive layer 12.

The base material 11 is preferably in the form of a film or a sheet.
The conductive layer 12 is linear and is provided in a partial region of one main surface (surface, first main surface) 11a of the base material 11. The line length direction (longitudinal direction) of the conductive layer 12 is a direction orthogonal to the cross section of the conductive layer 12 in FIG. The conductive layer 12 is laminated in direct contact with the surface 11a of the base material 11.
The coating layer 13 covers the entire surface of the base material 11 on which the conductive layer 12 is formed, and includes a region of the surface 11a of the base material 11 where the conductive layer 12 is not provided and the surface 12a of the conductive layer 12. , Are in direct contact with and laminated. The coating layer 13 is preferably in the form of a film or a sheet.

From the coating layer 13 side, that is, one main surface of the coating layer 13 (surface, outer surface of the coating layer 13, first main surface of the coating layer 13) 13a, which is opposite to the direction in which the base material 11 is provided. The haze H ₀ of the laminate 1 in the initial stage (for example, the stage immediately after production) before being placed under moist heat conditions, measured from a position separated in the direction, is 3.0% or less.
Further, the laminate 1 having a haze H ₀ of 3.0% or less is treated (humidified heat treatment) for 118 hours in an atmosphere (humidifying heat treatment) at a temperature of 85 ° C. and a relative humidity of 85%, and then the haze H ₀ is measured. When the haze H ₁₁₈ of the laminated body 1 is measured from the coating layer 13 side as in the measurement, the haze change rate ΔH ₁₁₈ of the laminated body 1 calculated by the above formula (I ₁₁₈ ) is 100% or less. ..
The direction in which the haze of the laminated body 1 is measured is indicated by an arrow A in FIG.

FIG. 2 is a cross-sectional view schematically showing another embodiment of the laminated body of the present invention. In FIG. 2, the same components as those shown in FIG. 1 are designated by the same reference numerals as those in FIG. 1, and detailed description thereof will be omitted. This also applies to figures other than FIG.
In the laminated body 2 shown here, the conductive layer 22 is in the form of a film or a sheet, and is laminated by covering a part or all of the surface 11a of the base material 11, and the cross-sectional shape of the coating layer 23 accordingly. It has the same configuration as the laminated body 1 shown in FIG. 1, except that the above is different. In FIG. 2, reference numeral 22a indicates the surface of the conductive layer 22.

An initial stage (eg,) before placing under moist heat conditions, measured from the coating layer 23 side, that is, from a position separated from the surface 23a of the coating layer 23 (from a position separated in a direction opposite to the direction in which the base material 11 is provided). , The haze H ₀ of the laminate 2 in the stage immediately after production) is 3.0% or less.
Further, the laminate 2 having a haze H ₀ of 3.0% or less is treated (humidified heat treatment) for 118 hours in an atmosphere (humidifying heat treatment) at a temperature of 85 ° C. and a relative humidity of 85%, and then the haze H ₀ is measured. When the haze H ₁₁₈ of the laminated body 2 is measured from the coating layer 23 side as in the measurement, the haze change rate ΔH ₁₁₈ of the laminated body 2 calculated by the above formula (I ₁₁₈ ) is 100% or less. ..
The direction in which the haze of the laminated body 2 is measured is indicated by an arrow A in FIG.

The laminate of the present invention is not limited to the configurations shown in FIGS. 1 and 2, and may be a laminate to which other configurations are added as long as the effects of the present invention are not impaired. A laminated body modified as appropriate may be used.
For example, the shape of the conductive layer when the laminated body is viewed in a plan view so as to look down on the surface of the base material can be arbitrarily set according to the purpose, and the conductive layer is patterned into a shape other than linear. You may. The linearly patterned conductive layer is useful, for example, as wiring.

Further, the laminate of the present invention may have, for example, a structure in which a conductive layer and other layers other than the coating layer are provided on the base material. Examples of the other layer include an intermediate layer provided between the base material and the conductive layer or between the conductive layer and the coating layer. Examples of the intermediate layer include an adhesion layer for improving the adhesion between adjacent layers, an adhesive layer or an adhesive layer for stably fixing adjacent layers, and the like, depending on the purpose. It may be selected as appropriate, and is not particularly limited.

However, the laminate of the present invention preferably does not have the intermediate layer, and is laminated with the conductive layer in direct contact with the base material and the coating layer in direct contact with the conductive layer. When the conductive layer is patterned, a laminated body in which the coating layer is directly contacted and laminated in the region where the conductive layer of the base material is not provided is preferable. Such a laminate can be produced by a simplified process, and the effect of the present invention that the change in haze of the entire laminate is suppressed even under moist heat conditions can be obtained particularly remarkably.

Further, the laminate of the present invention is, for example, a laminate in which some layer is laminated on the other main surface of the base material (the back surface, the surface with reference numeral 11b in FIGS. 1 and 2, and the second main surface). It may be the body. Here, examples of the layer laminated on the back surface of the base material include layers similar to the layer laminated on the front surface of the base material, such as a conductive layer, a coating layer, and an intermediate layer.

For example, in the case of a laminate in which a conductive layer and a coating layer are laminated in this order on the back surface of the base material, the haze of the laminate measured from the side of the coating layer provided on the back surface of the laminate (outer surface of the back surface coating layer) is Similar to the haze of the laminate measured from the side of the coating layer provided on the surface of the base material (outer surface of the surface coating layer), the above-mentioned conditions of the present invention (haze change rate ΔH ₁₁₈ is 100% or less). May be satisfied. That is, the haze H _{0 of the} laminate measured from the coating layer side of the back surface of the base material was 3.0% or less, and this laminate was treated for 118 hours in an atmosphere of a temperature of 85 ° C. and a relative humidity of 85%. Later, when the haze H _{118 of the} laminated body is measured from the coating layer side of the back surface of the base material, even if the haze change rate ΔH _{118 of the} laminated body calculated by the above formula (I ₁₁₈ ) is 100% or less. Good.

In the laminated body in which the conductive layer and the coating layer are laminated in this order on the back surface of the base material, the conductive layer and the coating layer may or may not be provided as in the case of the front surface of the base material. You may.
Further, in the case of a laminate in which the conductive layer and the coating layer are laminated in this order on the back surface of the base material, the haze of the laminate measured from the coating layer side of the back surface is the above-mentioned condition of the present invention (haze change rate ΔH). ₁₁₈ does not have to satisfy 100% or less).
Next, each configuration of the laminated body of the present invention will be described in more detail.

<Base material>
The thickness of the base material is preferably 10 to 5000 μm, more preferably 10 to 3000 μm.

The material of the base material is not particularly limited, but preferred materials include, for example, polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polymethylpentene (PMP), and poly. Acrylic resins such as cycloolefin, polystyrene (PS), polyvinyl acetate (PVAC), polymethylmethacrylate (PMMA), AS resin, ABS resin, polyamide (PA), polyimide, polyamideimide (PAI), polyacetal, polyethylene terephthalate. (PET), Polybutylene terephthalate (PBT), Polytrimethylene terephthalate (PTT), Polyethylene naphthalate (PEN), Polybutylene naphthalate (PBN), Polyphenylensulfide (PPS), Polysulfone (PSF), Polyethersulfone PES), polyetherketone (PEK), polyetheretherketone (PEEK), polycarbonate (PC), polyurethane, polyphenylene ether (PPE), modified polyphenylene ether (m-PPE), polyallylate, epoxy resin, melamine resin, phenol Examples thereof include synthetic resins such as resins and urea resins.
In addition to the above, examples of the material of the base material include ceramics such as glass and silicon, and paper.
Further, as the base material, two or more kinds of materials such as glass epoxy resin and polymer alloy may be used in combination.

The base material may be a base material composed of a single layer, or may be a base material composed of two or more layers. When the base material is composed of a plurality of layers, the plurality of layers may be the same as or different from each other. That is, all layers may be the same, all layers may be different, and only some layers may be the same. When the plurality of layers are different from each other, the combination of the plurality of layers is not particularly limited. Here, when the plurality of layers are different from each other, it means that at least one of the material and the thickness of each layer is different from each other. Further, when a plurality of layers are the same as each other, it means that the material and thickness of each layer are the same. When the base material is composed of a plurality of layers, the total thickness of each layer is the above. The thickness of the base material (10 to 5000 μm) is preferable.

<Conductive layer>
The material of the conductive layer is not particularly limited as long as it is a material having conductivity, but from the viewpoint that a conductive layer having a low resistance value can be easily formed, a single metal such as silver or copper, or an alloy (hereinafter, these are summarized). (Sometimes abbreviated as "metal"), more preferably silver or copper.

The thickness of the conductive layer can be arbitrarily set depending on the intended purpose, but is preferably 3 nm to 40 μm, and more preferably 4 nm to 30 μm. When the thickness of the conductive layer is at least the lower limit value (3 nm), the conductivity can be further improved, and the structure of the conductive layer can be maintained more stably. Further, when the thickness of the conductive layer is not more than the upper limit value (40 μm), the laminated body can be further thinned.

The conductive layer may be a layer composed of a single layer, or may be a layer composed of two or more layers. When the conductive layer is composed of a plurality of layers, the plurality of layers may be the same or different from each other, and can be configured in the same manner as in the case of the base material. For example, in the conductive layer composed of a plurality of layers, the total thickness of each layer may be set to the above-mentioned preferable thickness of the conductive layer.

<Coating layer>
The material of the coating layer may be appropriately selected depending on the intended purpose, and is not particularly limited, but is preferably a material having high transparency.
The coating layer is preferably a layer made of a resin or containing a resin as a main component. In the present specification, the "main component" means a component having a content of 30% by mass or more and less than 100% by mass in the target layer.

Examples of the resin include energy ray-curable resins such as ultraviolet curable resins, thermosetting resins, and cured products of these resins, which are energy ray-curable resins or cured products of energy ray-curable resins. It is preferable to have.
That is, examples of the coating layer include an energy ray-curable resin layer such as an ultraviolet curable resin layer, a thermosetting resin layer, and a cured product of these resin layers.

Among them, more preferable coating layers include, for example, a polyurethane (meth) acrylate-containing layer such as a layer composed of polyurethane (meth) acrylate and a layer containing polyurethane (meth) acrylate as a main component; the polyurethane (meth) acrylate. Examples thereof include a layer composed of a cured product of the containing layer.

The layer containing polyurethane (meth) acrylate as a main component is preferably a layer containing polyurethane (meth) acrylate and (meth) acrylic acid ester.
In the layer containing polyurethane (meth) acrylate and (meth) acrylic acid ester, the ratio of the contents of these components is [polyurethane (meth) acrylate (mass)]: [(meth) acrylic acid ester (mass)]. In terms of mass ratio, it is preferably 30:70 to 90:10, more preferably 35:65 to 85:15, and particularly preferably 38:62 to 82:18.
In the layer containing the polyurethane (meth) acrylate and the (meth) acrylic acid ester, the total content of the polyurethane (meth) acrylate and the (meth) acrylic acid ester is preferably 80% by mass or more, preferably 90% by mass or more. Is more preferable, 95% by mass or more is further preferable, and 98% by mass or more is particularly preferable. On the other hand, the upper limit of the total content is not particularly limited, and can be selected from, for example, 99% by mass, 99.5% by mass, and 100% by mass.

In addition, in this specification, "(meth) acrylic acid" is a concept including both "acrylic acid" and "methacrylic acid". The same applies to terms similar to (meth) acrylic acid, for example, "(meth) acrylate" is a concept that includes both "acrylate" and "methacrylate", and is a "(meth) acryloyl group". Is a concept that includes both an "acryloyl group" and a "methacryloyl group".

The weight average molecular weight of the resin before curing is not particularly limited, but is preferably 500 to 30,000, more preferably 800 to 20,000, and particularly preferably 1,200 to 15,000.

The pencil hardness of the coating layer is preferably any of, for example, 4B, 3B, 2B, B, HB, F, H, 2H and 3H. Such a pencil-hardened coating layer is easy to form and can maintain a stable structure.
In addition, in this specification, "pencil hardness" means a value measured according to JIS K5600-5-4 unless otherwise specified.

The thickness of the coating layer can be arbitrarily set depending on the intended purpose, but is preferably 200 nm to 50 μm, more preferably 500 nm to 40 μm, and particularly preferably 800 nm to 30 μm. When the thickness of the coating layer is at least the lower limit value (200 nm), the coating effect of the conductive layer can be further improved, and the structure of the coating layer can be maintained more stably. Further, when the thickness of the coating layer is not more than the upper limit value (50 μm), it is possible to prevent the coating layer from becoming excessively thick.

The coating layer may be a layer composed of a single layer or a layer composed of a plurality of layers of two or more layers. When the coating layer is composed of a plurality of layers, the plurality of layers may be the same or different from each other, and can be configured in the same manner as in the case of the base material. For example, in the coating layer composed of a plurality of layers, the total thickness of each layer may be set to the above-mentioned preferable thickness of the coating layer.

The laminate was treated for t hours (t is a number of 0 or more) in an atmosphere of a temperature of 85 ° C. and a relative humidity of 85%, and then the haze of the laminate measured from the coating layer side (outer surface of the coating layer) was measured. when the H _t, the haze change rate [Delta] H _t after the processing of the laminate, can be defined by the following formula (I _t). The haze change rate ΔH _t is an index of the stability of the optical characteristics of the laminate under moist heat conditions.
_{ΔH t (%) = (H} t -H 0) / H 0 × 100 ···· (I t)

In the laminate of the present invention, haze H ₀ is 3.0% or less, preferably 2.8% or less, more preferably 2.6% or less, and 2.4% or less. Is particularly preferable. When the haze H ₀ is not more than the upper limit value (3.0%), the laminated body has excellent optical characteristics.
On the other hand, in the laminate of the present invention, the lower limit of haze H ₀ is not particularly limited, and may be, for example, 0.2%, 0.4%, 0.6%, or the like.

In the laminate of the present invention, the haze H _91, which is the haze when the laminate is humidified and heat-treated in an atmosphere of a temperature of 85 ° C. and a relative humidity of 85%, is preferably 3.2% or less. It is more preferably 0% or less, further preferably 2.8% or less, and particularly preferably 2.6% or less. When the haze H ₉₁ is not more than the upper limit value (3.2%), the laminated body becomes superior in optical characteristics.
On the other hand, in the laminate of the present invention, the lower limit of the haze H ₉₁ is not particularly limited, and may be, for example, 0.3%, 0.5%, 0.7%, or the like.

In the laminate of the present invention, the haze H ₁₁₈ , which is the haze when the laminate is humidified and heat-treated in an atmosphere having a temperature of 85 ° C and a relative humidity of 85%, and the laminate have a temperature of 85 ° C and a relative humidity of 85%. The haze H _120, which is the haze when humidified and heat-treated for 120 hours in an atmosphere, is preferably 3.5% or less, more preferably 3.3% or less, and preferably 3.1% or less. It is more preferably 2.9% or less, and particularly preferably 2.9% or less. When the haze H ₁₁₈ and the haze H ₁₂₀ are equal to or less than the upper limit value (3.5%), the laminate becomes superior in optical characteristics.
On the other hand, in the laminate of the present invention, the lower limit values of haze H ₁₁₈ and haze H ₁₂₀ are not particularly limited, and may be, for example, 0.3%, 0.5%, 0.7%, or the like.
The haze H _182, which is the haze when the laminate is humidified and heat-treated for 182 hours in an atmosphere having a temperature of 85 ° C. and a relative humidity of 85%, is also in the same numerical range (3.5% or less) as the haze H _118. Is preferable.

In the laminate of the present invention, the haze H ₂₁₇ , which is the haze when the laminate is humidified and heat-treated in an atmosphere of 85 ° C. and 85% relative humidity, and the atmosphere of the laminate at 85 ° C. and 85% relative humidity. haze H ₂₂₄ is a haze in upon 224 hours humidified heat treatment _under, and the temperature 85 ° C. the laminate haze H ₂₃₀ is a haze in upon 230 hours humidified heat treatment in an atmosphere of a relative humidity of 85% 3. It is preferably 8% or less, more preferably 3.6% or less, further preferably 3.4% or less, and particularly preferably 3.2% or less. When the haze H ₂₁₇ , the haze H ₂₂₄ , and the haze H ₂₃₀ are equal to or less than the upper limit value (3.8%), the laminated body has better optical characteristics.
On the other hand, in the laminate of the present invention, the lower limit values of Haze H ₂₁₇ , Haze H ₂₂₄ , and Haze H ₂₃₀ are not particularly limited, and are, for example, 0.3%, 0.6%, 0.9%, or the like. can do.

In the laminate of the present invention, the haze H _412, which is the haze when _the laminate is humidified and heat-treated in an atmosphere of 85 ° C. and 85% relative humidity _{, and the} laminate has an atmosphere of 85 ° C. and 85% relative humidity. Haze H _428, which is the haze when humidified and heat-treated for 428 hours underneath, Haze H _493, which is the haze when _the laminate is humidified and heat-treated for 493 hours in an atmosphere with a temperature of 85 ° C. and a relative humidity of 85%. Haze H ₅₀₀ , which is the haze when humidified and heat-treated in an atmosphere of a temperature of 85 ° C. and a relative humidity of 85%, and when the laminate is humidified and heat-treated in an atmosphere of a temperature of 85 ° C. and a relative humidity of 85% for 511 hours. When the haze H ₅₁₁ and the laminate are humidified and heat-treated in an atmosphere at a temperature of 85 ° C. and a relative humidity of 85% for 564 hours, the haze H ₅₆₄ is preferably 4.0% or less. It is more preferably 8.8% or less, further preferably 3.6% or less, and particularly preferably 3.4% or less. When the haze H _412, haze H _428, haze H _493, haze H ₅₀₀ , haze H ₅₁₁ , and haze H ₅₆₄ are equal to or less than the upper limit (4.0%), the laminate is considered to be superior in optical properties. Become.
On the other hand, in the laminate of the present invention, the lower limit values of Haze H _412, Haze H _428, Haze H _493, Haze H ₅₀₀ , Haze H ₅₁₁ , and Haze H ₅₆₄ are not particularly limited, and are, for example, 0.5% and 0. It can be either 8.8%, 1.1%, or the like.

In the laminate of the present invention, haze when the laminate is humidified and heat-treated at a temperature of 85 ° C. and a relative humidity of 85% for 740 hours or more (for example, haze H ₇₄₁ which is a haze when humidified and heat-treated for 741 hours). Haze H ₇₇₄ when humidified and heat-treated for 774 hours, Haze H ₇₈₁ which is haze when humidified and heat-treated for 781 hours, Haze H ₈₁₆ which is haze when humidified and heat-treated for 816 hours, 1004 hours humidified and heat-treated. Haze H ₁₀₀₄ , which is the haze when humidified and heat-treated for 1011 hours, Haze H ₁₀₁₁ which is the haze when humidified and heat-treated for 1011 hours, Haze H _1124, which is the haze when humidified and heat-treated for 1124 hours, etc.) It is preferably 4.0% or less, more preferably 3.6% or less, for example, 3.2% or less, 2.8% or less, 2.3% or less, 2. It may be any of 0% or less. When the haze after the above-mentioned humidification and heat treatment for 740 hours or more is not more than the upper limit value (4.0%), the laminated body becomes excellent in optical characteristics.
On the other hand, in the laminate of the present invention, the lower limit of the haze after the above-mentioned humidification and heat treatment for 740 hours or more is not particularly limited, and is, for example, 0.5%, 0.9%, 1.2% or the like. can do.

In the laminate of the present invention, the haze change rate ΔH ₁₁₈ when the laminate is humidified and heat-treated at a temperature of 85 ° C. and a relative humidity of 85% for 118 hours is 100% or less, preferably 90% or less. , 80% or less, more preferably 70% or less, particularly preferably 60% or less, and for example, 50% or less. When the haze change rate ΔH ₁₁₈ is not more than the upper limit value (100%), the laminated body has excellent optical characteristics.
On the other hand, in the laminate of the present invention, the lower limit of the haze change rate ΔH ₁₁₈ is not particularly limited, and may be, for example, 5%, 10%, 15%, or the like.

In the laminate of the present invention, the haze change rate ΔH ₉₁ when the laminate is humidified and heat-treated at a temperature of 85 ° C. and a relative humidity of 85% for 91 hours is preferably 85% or less, preferably 70% or less. More preferably, it is more preferably 55% or less, and particularly preferably 40% or less. When the haze change rate ΔH ₉₁ is not more than the upper limit value (85%), the laminated body becomes superior in optical characteristics.
On the other hand, in the laminated body of the present invention, the lower limit of the haze change rate ΔH ₉₁ is not particularly limited, and may be, for example, 2%, 4%, 6%, or the like.

In the laminate of the present invention, the haze change rate ΔH ₁₂₀ when the laminate is humidified and heat-treated in an atmosphere of 85 ° C. and 85% relative humidity, and the atmosphere of 85 ° C. and 85% relative humidity of the laminate. The haze change rate ΔH ₁₈₂ when humidified and heat-treated for 182 hours underneath is preferably 100% or less, more preferably 90% or less, further preferably 80% or less, and more preferably 70% or less. It is particularly preferable that the temperature is 60% or less, and it can be 50% or less, for example. When the haze change rates ΔH ₁₂₀ and ΔH ₁₈₂ are equal to or less than the upper limit value (100%), the laminated body has excellent optical characteristics.
On the other hand, in the laminated body of the present invention, the lower limit values of the haze change rates ΔH ₁₂₀ and ΔH ₁₈₂ are not particularly limited and may be, for example, 5%, 10%, 15% or the like.

In the laminate of the present invention, the haze change rate ΔH ₂₁₇ when the laminate is humidified and heat-treated in an atmosphere of 85 ° C. and 85% relative humidity, and the laminate is in an atmosphere of 85 ° C. and 85% relative humidity. haze change rate [Delta] h ₂₃₀ is at 110% or less at the time of the 230 hours humidified heat treatment in an atmosphere of temperature of 85 ° C., 85% relative humidity the haze change rate [Delta] h _224, and laminates at the time of in the 224 hours humidified heat treatment It is preferably 95% or less, more preferably 80% or less, particularly preferably 65% or less, and for example, 60% or less, 50% or less, and the like. When the haze change rates ΔH ₂₁₇ , ΔH ₂₂₄ and ΔH ₂₃₀ are not more than the upper limit value (110%), the laminate becomes superior in optical characteristics.
On the other hand, in the laminated body of the present invention, the lower limit values of the haze change rates ΔH ₂₁₇ , ΔH ₂₂₄ and ΔH ₂₃₀ are not particularly limited and may be, for example, 5%, 8%, 13%, 18% or the like. ..

In the laminate of the present invention, the haze change rate ΔH ₄₁₂ when the laminate is humidified and heat-treated in an atmosphere of 85 ° C. and 85% relative humidity, and the laminate is in an atmosphere of 85 ° C. and 85% relative humidity. Haze change rate ΔH ₄₂₈ when humidified and heat-treated for 428 hours, haze change rate ΔH ₄₉₃ when the laminate was humidified and heat-treated for 493 hours in an atmosphere with a temperature of 85 ° C and a relative humidity of 85%, and the temperature of the laminate was 85 ° C. Haze change rate ΔH ₅₀₀ when humidified and heat-treated for 500 hours in an atmosphere with a relative humidity of 85%, and haze change rate ΔH when the laminate was humidified and heat-treated for 511 hours in an atmosphere with a temperature of 85 ° C and relative humidity of 85%. The haze change rate ΔH ₅₆₄ when the ₅₁₁ and the laminate are humidified and heat-treated at a temperature of 85 ° C. and a relative humidity of 85% for 564 hours is preferably 110% or less, more preferably 105% or less. , 100% or less, particularly preferably 95% or less, and for example, 85% or less, 75% or less, 65% or less, or the like. When the haze change rates ΔH ₄₁₂ , ΔH ₄₂₈ , ΔH ₄₉₃ , ΔH ₅₀₀ , ΔH _511, and ΔH ₅₆₄ are equal to or less than the upper limit (110%), the laminate becomes superior in optical characteristics.
On the other hand, in the laminate of the present invention, the lower limit values of the haze change rates ΔH ₄₁₂ , ΔH ₄₂₈ , ΔH ₄₉₃ , ΔH ₅₀₀ , ΔH ₅₁₁ and ΔH ₅₆₄ are not particularly limited, and are, for example, 10%, 15%, 20% and the like. It can be either.

In the laminate of the present invention, the haze change rate when the laminate is humidified and heat-treated at a temperature of 85 ° C. and a relative humidity of 85% for 740 hours or more (for example, the haze change rate when the laminate is humidified and heat-treated for 741 hours ΔH _741). , 774 hours humidification heat treatment haze change rate ΔH ₇₇₄ , 781 hours humidification heat treatment haze change rate ΔH ₇₈₁ , 816 hours humidification heat treatment haze change rate ΔH ₈₁₆ , 1004 hours humidification heat treatment Haze change rate ΔH ₁₀₀₄ , haze change rate ΔH ₁₀₁₁ when humidified and heat-treated for 1011 hours, haze change rate ΔH _1124, etc. when humidified and heat-treated for 1124 hours) is preferably 120% or less, preferably 115% or less. It is more preferable that, for example, it may be 95% or less, 85% or less, 75% or less, 65% or less, or the like. When the haze change rate after the above-mentioned humidification and heat treatment for 740 hours or more is not more than the upper limit value (120%), the laminated body becomes more excellent in optical characteristics.
On the other hand, in the laminate of the present invention, the lower limit of the haze change rate after the above-mentioned humidification and heat treatment for 740 hours or more is not particularly limited, and may be, for example, 15%, 20%, 25% or the like. ..

<< Manufacturing method of laminated body >>
In the laminate of the present invention, for example, a step of forming a conductive layer on a base material (hereinafter, may be abbreviated as “conductive layer forming step”) and a step of forming a coating layer on the conductive layer (hereinafter, referred to as , May be abbreviated as "coating layer forming step").

FIG. 3 is a cross-sectional view for schematically explaining the manufacturing method of the laminated body 1 shown in FIG.
When the laminate 1 shown in FIG. 1 is manufactured, the base material 11 shown in FIG. 3A is used. First, as shown in FIG. 3B, the surface of the base material 11 is formed in the conductive layer forming step. The conductive layer 12 is formed on the 11a.
Next, as shown in FIG. 3C, in the coating layer forming step, the forming surface of the conductive layer 12 on the base material 11 is coated with the coating layer 13. As a result, the coating layer 13 is formed on the surface 12a of the conductive layer 12 and the region of the surface 11a of the base material 11 that does not have the conductive layer 12.
From the above, the laminated body 1 is obtained.
Although the laminated body 1 shown in FIG. 1 has been cited and described here, the laminated body of the present invention other than the laminated body 1 can also be obtained by the same method as this method or by a method in which a part of this method is modified. Can be manufactured.
Hereinafter, each step will be described in more detail.

<Conductive layer forming process>
The conductive layer is composed by, for example, attaching a composition as a raw material for forming the conductive layer (hereinafter, may be abbreviated as “composition for conductive layer”) to a target portion on the base material. It can be formed by forming a material layer and appropriately selecting a solidification treatment such as a drying treatment or a heating (firing) treatment on the composition layer (composition for a conductive layer). The heat treatment may also be performed as a drying treatment.
Further, in the conductive layer, the composition for the conductive layer is adhered to a predetermined region or the entire surface of the base material to form a composition layer, and the composition layer (composition for the conductive layer) is formed by the same method as described above. After forming the conductive layer (the conductive layer before patterning), it can also be formed by patterning the conductive layer so as to have a desired shape by a known method such as etching.

When the material of the conductive layer is metal, a metal or a metal ink composition containing a metal-forming material may be used as the composition for the conductive layer.
The metal forming material in the metal ink composition may be only one kind, two or more kinds, and when there are two or more kinds, the combination and ratio thereof can be arbitrarily adjusted.

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

The material for forming the metal to be blended may be any as long as it has a corresponding metal atom (element) and produces a metal by a structural change such as decomposition. For example, a metal salt, a metal complex, or an organic metal compound (metal-). Compounds having a carbon bond) and the like. The metal salt and the metal complex may be either a metal compound having an organic group or a metal compound having no organic group. Among them, the metal forming material is preferably a metal salt, more preferably a silver salt or a copper salt.
By using a metal forming material, a metal is generated from the material, and a conductive layer containing this metal is formed. In the conductive layer in this case, the ratio of the metal can be sufficiently high enough that the conductive layer can be regarded as apparently composed only of metal, and the ratio of the metal in the conductive layer is preferably 97% by mass or more. It is more preferably 98% by mass or more, and particularly preferably 99% by mass or more. The upper limit of the ratio of the metal in the conductive layer is, for example, 100% by mass, 99.9% by mass, 99.8% by mass, 99.7% by mass, 99.6% by mass, 99.5% by mass, 99. It can be, but is not limited to, 4% by mass, 99.3% by mass, 99.2% by mass, and 99.1% by mass.

The metal ink composition is preferably a liquid composition, and a composition in which the metal forming material is uniformly dispersed is preferable.

Hereinafter, a method for forming the conductive layer when a silver ink composition containing a material for forming metallic silver is used as the metal ink composition will be described, but the same method can be used when the metal type is other than silver. A conductive layer can be formed.
The material for forming metallic silver is a material that is decomposed by heating or the like to form metallic silver.

[Silver carboxylate]
Examples of the material for forming metallic silver include silver carboxylate having a group represented by the formula "-COOAg".
In the present invention, one type of silver carboxylate may be used alone, or two or more types may be used in combination. When two or more kinds are used in combination, the combination and ratio of these silver carboxylates can be adjusted arbitrarily.
The silver carboxylate is not particularly limited as long as it has a group represented by the formula "-COOAg". For example, the number of groups represented by the formula "-COOAg" may be only one or two or more. Further, the position of the group represented by the formula "-COOAg" in silver carboxylate is not particularly limited.

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

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

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

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

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

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

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

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

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

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

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

Y ^{1 in} R is independently a fluorine atom, a chlorine atom, a bromine atom or a hydrogen atom. Then, the general formula ^"R ₁ ^-CY 1 ₂ -", ^"CY _{1 3} -" and ^{"R 6 -C (= O) -CY} 1 2 - " In a plurality of ^{Y 1} are each, also identical to one another It may be different.

^{R 1} in R is an aliphatic hydrocarbon group or a phenyl group 1 to 19 carbon atoms _(C 6 _{H 5} -) a, The aliphatic hydrocarbon group for ^{R 1,} is a 1 to 19 carbon atoms Except for the point, the same group as the aliphatic hydrocarbon group in R can be mentioned.
R ² in R is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and examples thereof include groups similar to the aliphatic hydrocarbon group in R.
R ³ in R is an aliphatic hydrocarbon group having 1 to 16 carbon atoms, and examples thereof include the same groups as the aliphatic hydrocarbon group in R except that the carbon number is 1 to 16.
R ⁴ and R ⁵ in R are aliphatic hydrocarbon groups having 1 to 18 carbon atoms independently. That is, R ⁴ and R ⁵ may be the same or different from each other, and examples thereof include groups similar to the aliphatic hydrocarbon group in R except that the number of carbon atoms is 1 to 18.
R ⁶ in R is an aliphatic hydrocarbon group of 1 to 19 carbon atoms, a group represented by a hydroxyl group or a formula "AgO-" The aliphatic hydrocarbon group for R ^6,. 1 to carbon atoms Examples thereof include the same groups as the aliphatic hydrocarbon group in R except that the number is 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), X ¹ is an independently hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, or a phenyl group in which one or more hydrogen atoms may be substituted with a substituent. A benzyl group (C ₆ H _5- CH _2- ), a cyano group, an N-phthaloyl-3-aminopropyl group, a 2-ethoxyvinyl group (C ₂ H _5- O-CH = CH-), or the general formula "R". It is a group represented by " ⁷ O-", "R ⁷ S-", "R ^7- C (= O)-" or "R ^7- C (= O) -O-".
Examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms in X ¹ include the same group as the aliphatic hydrocarbon group in R.

Examples of the halogen atom in X ¹ include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
Phenyl and benzyl groups in X ¹ may be one or more hydrogen atoms is substituted with a substituent, and preferred examples the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom ), Nitro group (-NO ₂ ) and the like, and the number and position of the substituent are not particularly limited. When the number of substituents is plural, these plurality of substituents may be the same or different from each other.

^{R 7} in X ¹ is an aliphatic having 1 to 10 carbon atoms hydrocarbon group, a thienyl group _{(C 4} H 3 S-), or one or more hydrogen atoms is a phenyl group or optionally substituted with a substituent diphenyl group (biphenyl _{group, C 6 H 5 -C 6 H} 4 -) is. Examples of the aliphatic hydrocarbon group in R ⁷ include groups similar to the aliphatic hydrocarbon group in R except that the number of carbon atoms is 1 to 10. Examples of the substituents of the phenyl group and the diphenyl group in R ⁷ include halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom), and the number and position of the substituents are not particularly limited. When the number of substituents is plural, these plurality of substituents may be the same or different from each other.
When R ⁷ is thienyl or diphenyl group, these adjacent group or atom in X ¹ (oxygen atom, a sulfur atom, a carbonyl group, carbonyloxy group) bonding position to is not particularly limited. For example, the thienyl group may be either a 2-thienyl group or a 3-thienyl group.

In the general formula (1), two X ^1s may be bonded to a carbon atom sandwiched between two carbonyl groups as one group via a double bond, and such a group may be used. For example, a group represented by the formula "= CH-C ₆ H _4- NO ₂ " can be mentioned.

X ^1, among the above, a hydrogen atom, a linear or branched alkyl group, a benzyl group, or formula "R ⁷ -C (= O) -" it is a group represented by preferably , It is preferable that at least one X ¹ is a hydrogen atom.

Silver β-ketocarboxylate (1) is 2-methylacetoacetic acid silver (CH _3- C (= O) -CH (CH ₃ ) -C (= O) -OAg), silver acetoacetic acid (CH _3- C (=)). O) -CH _2- C (= O) -OAg), silver 2-ethylacetoacetic acid (CH _3- C (= O) -CH (CH ₂ CH ₃ ) -C (= O) -OAg), silver propionyl acetate (CH ₃ CH _2- C (= O) -CH _2- C (= O) -OAg), silver isobutyryl acetate ((CH ₃ ) ₂ CH-C (= O) -CH _2- C (= O)- OAg), silver pivaloyl acetate ((CH ₃ ) ₃ C-C (= O) -CH _2- C (= O) -OAg), silver caproyl acetate (CH ₃ (CH ₂ ) ₃ CH _2- C (= O) ) -CH _2- C (= O) -OAg), 2-n-silver butylacetoacetate (CH _3- C (= O) -CH (CH ₂ CH ₂ CH ₂ CH ₃ ) -C (= O) -OAg ), Silver ₂ -benzylacetoacetic acid (CH _3- C (= O) -CH (CH ₂ C ₆ H ₅ ) -C (= O) -OAg), Silver benzoyl acetate (C ₆ H ₅ -C (= O)) ) -CH _2- C (= O) -OAg), silver pivaloylacetoacetate ((CH ₃ ) ₃ C-C (= O) -CH _2- C (= O) -CH _2- C (= O) -OAg ), Silver Isobutyrylacetoacetic Acid ((CH ₃ ) ₂ CH-C (= O) -CH _2- C (= O) -CH _2- C (= O) -OAg), 2-Acetyl Pivaloyl Acetate Silver ((CH ₃ ) ₃ C-C (= O) -CH (-C (= O) -CH ₃ ) -C (= O) -OAg), silver 2-acetylisobutyryl acetate ((CH ₃ )) ₂ CH-C (= O) -CH (-C (= O) -CH ₃ ) -C (= O) -OAg) or silver acetone dicarboxylate (AgO-C (= O) -CH _2- C ( = O) -CH _2- C (= O) -OAg) is preferable.

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

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

In the present invention, one type of silver β-ketocarboxylate (1) may be used alone, or two or more types may be used in combination. When two or more kinds are used in combination, the combination and ratio of these silver β-ketocarboxylates can be adjusted arbitrarily.

(Silver carboxylate (4))
The silver carboxylate (4) is represented by the above 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 in R ⁸ include groups similar to the aliphatic hydrocarbon group in R except that the number of carbon atoms is 1 to 19. However, the aliphatic hydrocarbon group for ^{R 8} is preferably a carbon number of 1 to 15, and more preferably from 1 to 10.

When the aliphatic hydrocarbon group in 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 methylene groups that may be substituted with carbonyl groups are not particularly limited, and all methylene groups may be substituted with carbonyl groups. Here, the "methylene group", alone of formula _- not only a group represented by the formula "-CH 2" _- one alkylene in radicals group represented is continuous plurality in "-CH 2" It shall also include the group represented by the formula "-CH _2- " of.

The silver carboxylate (4) is silver pyruvate (CH _3- C (= O) -C (= O) -OAg), silver acetate (CH _3- C (= O) -OAg), silver butyrate (CH ₃ ). -(CH ₂ ) _2- C (= O) -OAg), silver isobutyrate ((CH ₃ ) ₂ CH-C (= O) -OAg), silver 2-ethylhexanoate (CH _3- (CH ₂ )) ) _3- CH (CH ₂ CH ₃ ) -C (= O) -OAg), silver neodecanoate (CH _3- (CH ₂ ) _5- C (CH ₃ ) _2- C (= O) -OAg), Shu It is preferably silver acid (AgO-C (= O) -C (= O) -OAg) or silver malonate (AgO-C (= O) -CH _2- C (= O) -OAg). 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 the silver carboxylate (HO-C (= O) -C (= O) -OAg which was the group represented by the formula "-COOH". , HO-C (= O) -CH _2- C (= O) -OAg) is also preferable.

Similar to silver β-ketocarboxylate (1), silver carboxylate (4) also contains residual raw materials and impurities in the conductor (metal silver) formed by solidification treatment such as drying treatment and heating (firing) treatment. The concentration can be further reduced. Then, when used in combination with a reducing agent, it decomposes at a lower temperature to form metallic silver.

In the present invention, one type of silver carboxylate (4) may be used alone, or two or more types may be used in combination. When two or more kinds are used in combination, the combination and ratio of these silver carboxylates can be adjusted arbitrarily.

The silver carboxylate is silver 2-methylacetoacetic acid, silver acetoacetic acid, silver 2-ethylacetoacetic acid, silver propionylacetate, silver isobutyryl acetate, silver pivaloylacetate, silver caproylacetate, silver 2-n-butylacetate, 2-benzylacetate. Silver acetate, benzoyl acetoacetic acid, silver pivaloylacetoacetate, silver isobutyryl acetoacetic acid, silver acetonedicarboxylate, silver pyruvate, silver acetate, silver butyrate, silver isobutyrate, silver 2-ethylhexanoate, silver neodecanoate, oxalate It is preferably one or more selected from the group consisting of silver acid and silver malonate.
Among these silver carboxylates, silver 2-methylacetoacetic acid and silver acetoacetic acid are excellent in compatibility with nitrogen-containing compounds (among them, amine compounds) described later, and are particularly suitable for increasing the concentration of silver ink compositions. It is mentioned as silver carboxylate.

In the silver ink composition, the content of silver derived from the metallic silver forming material is preferably 5% by mass or more, and more preferably 10% by mass or more. Within such a range (5% by mass or more), the formed conductor (metal silver) becomes more excellent in quality. The upper limit of the silver content is not particularly limited as long as the effect of the present invention is not impaired, but is preferably 25% by mass in consideration of handleability and the like.
In the present specification, "silver derived from the metal silver forming material" has the same meaning as silver in the metal silver forming material blended at the time of manufacturing the silver ink composition, unless otherwise specified. , Silver that still constitutes the metal silver forming material after compounding, silver in the decomposition product that was produced by the decomposition of the metal silver forming material after compounding, and silver that was produced by the decomposition of the metal silver forming material after compounding. It is a concept that includes all of itself (metal silver).

[Nitrogen-containing compound]
The silver ink composition is preferably a composition in which a nitrogen-containing compound is further blended in addition to the metallic silver forming material, particularly when the metallic silver forming material is the silver carboxylate.
The nitrogen-containing compound is an amine compound having 25 or less carbon atoms (hereinafter, may be abbreviated as "amine compound") and a quaternary ammonium salt having 25 or less carbon atoms (hereinafter, abbreviated as "quaternary ammonium salt"). ), Ammium, an ammonium salt formed by reacting an amine compound with 25 or less carbon atoms with an acid (hereinafter, may be abbreviated as "amine salt derived from an amine compound"), and ammonia as an acid. It is one or more compounds selected from the group consisting of ammonium salts formed by reaction (hereinafter, may be abbreviated as "ammonium-derived ammonium salts"). That is, only one type of nitrogen-containing compound may be blended, or two or more types may be used, and when two or more types are used in combination, the combination and ratio of the nitrogen-containing compounds can be arbitrarily adjusted.

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

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

The alkyl group constituting the monoalkylamine may be linear, branched or cyclic, and examples thereof include groups similar to the alkyl group in R, which are linear or branched having 1 to 19 carbon atoms. It is preferably a chain alkyl group or a cyclic alkyl group having 3 to 7 carbon atoms.
Specific preferred monoalkylamines include, for example, n-butylamine, n-hexylamine, n-octylamine, n-dodecylamine, n-octadecylamine, isobutylamine, sec-butylamine, tert-butylamine, 3 Examples thereof include -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, a 2-naphthyl group and the like, and the number of carbon atoms is preferably 6 to 10.

The heteroaryl group constituting the mono (heteroaryl) amine is a group having a hetero atom as an atom constituting the aromatic ring skeleton, and the hetero atom includes, for example, a nitrogen atom, a sulfur atom, an oxygen atom, and the like. Examples include a boron atom. Further, the number of the heteroatoms constituting the aromatic ring skeleton is not particularly limited, and may be one or two or more. When there are two or more heteroatoms, these heteroatoms may be the same or different from each other. That is, these heteroatoms may all be the same, all may be different, or only partly 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 it is preferably a 3 to 12 member ring.

Examples of the heteroaryl group as a monocyclic group having 1 to 4 nitrogen atoms include a pyrrolyl group, a pyrrolinyl group, an imidazolyl group, a pyrazolyl group, a pyridyl group, a pyrimidyl group, a pyrazinyl group, a pyridadinyl group and a triazolyl group. Examples thereof include a tetrazolyl group, a pyrrolidinyl group, an imidazolidinyl group, a piperidinyl group, a pyrazoridinyl group and a piperazinyl group, and a 3- to 8-membered ring is preferable, and a 5- to 6-membered ring is more preferable.
Examples of the monocyclic group having one oxygen atom in the heteroaryl group include a furanyl group and the like, preferably a 3- to 8-membered ring, and more preferably a 5- to 6-membered ring. ..
Examples of the monocyclic group having one sulfur atom in the heteroaryl group include a thienyl group and the like, and a 3- to 8-membered ring is preferable, and a 5- to 6-membered ring is more preferable. ..
Examples of the monocyclic group having 1 to 2 oxygen atoms and 1 to 3 nitrogen atoms in the heteroaryl group include an oxazolyl group, an isooxazolyl group, an oxadiazolyl group, a morpholinyl group and the like, and 3 to 8 It is preferably a membered ring, more preferably a 5-6 membered ring.
Examples of the monocyclic group having 1 to 2 sulfur atoms and 1 to 3 nitrogen atoms in the heteroaryl group include a thiazolyl group, a thiadiazolyl group, a thiazolidinyl group and the like, and have a 3 to 8 membered ring. It is preferably present, and more preferably a 5- to 6-membered ring.
Examples of the heteroaryl group having 1 to 5 nitrogen atoms as a polycyclic group include an indolyl group, an isoindryl group, an indridinyl group, a benzimidazolyl group, a quinolyl group, an isoquinolyl group, an indazolyl group, and a benzotriazolyl group. , Tetrazolopyridyl group, tetrazolopyridazinyl group, dihydrotriazolopyridazinyl group and the like, preferably a 7 to 12-membered ring, and more preferably a 9 to 10-membered ring.
Examples of the heteroaryl group having a polycyclic group having 1 to 3 sulfur atoms include a dithianaphthalenyl group and a benzothiophenyl group, and a 7 to 12-membered ring is preferable. More preferably, it is a 10-membered ring.
Examples of the polycyclic group having 1 to 2 oxygen atoms and 1 to 3 nitrogen atoms in the heteroaryl group include a benzoxazolyl group, a benzoxaziazolyl group and the like, and 7 to 12 thereof. It is preferably a membered ring, more preferably 9 to 10 membered rings.
Examples of the polycyclic group having 1 to 2 sulfur atoms and 1 to 3 nitrogen atoms in the heteroaryl group include a benzothiazolyl group, a benzothiazolyl group and the like, and have a 7 to 12-membered ring. It is preferably present, and more preferably 9 to 10-membered rings.

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

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

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

The aryl group constituting the diarylamine is the same as the aryl group constituting the monoarylamine, and preferably has 6 to 10 carbon atoms. Further, the two aryl groups in one molecule of diallylamine 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 to 12-membered ring. Also, the two heteroaryl groups in a single molecule of di (heteroaryl) amine may be the same or different from each other.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

In the silver ink composition, the blending amount of the nitrogen-containing compound is preferably 0.3 to 15 mol, more preferably 0.3 to 5 mol, per 1 mol of the blended amount of the metallic silver forming material. preferable. When the compounding amount of the nitrogen-containing compound is in such a range (0.3 to 15 mol per 1 mol of the compounding material of the forming material), the stability of the silver ink composition is further improved, and the conductor (metal) is further improved. The quality of silver) is further improved. Further, the conductor can be formed more stably without heat treatment at a high temperature.

[Reducing agent]
The silver ink composition is preferably a composition in which a reducing agent is further blended in addition to the metal silver forming material. By blending the reducing agent, the silver ink composition can more easily form metallic silver, and for example, a conductor (metallic silver) having sufficient conductivity can be formed even by heat treatment at a low temperature.

The reducing agent is one or more reducing agents selected from the group consisting of oxalic acid, hydrazine and a compound represented by the following general formula (5) (hereinafter, may be abbreviated as "compound (5)"). It is preferably a compound (hereinafter, may be simply abbreviated as "reducing compound").
HC (= O) -R ²¹ ... (5)
(In the formula, R ²¹ is an alkyl group having 20 or less carbon atoms, an alkoxy group or an N, N-dialkylamino group, a hydroxyl group or an amino group.)

(Reducing compound)
The reducing compound, oxalic acid (HOOC-COOH), hydrazine _{(H 2} N-NH 2) and the compound represented by the general formula (5) (Compound (5)) one selected from the group consisting of These are the above compounds. That is, only one type of reducing compound may be blended, or two or more types may be used, and when two or more types are used in combination, the combination and ratio thereof can be arbitrarily adjusted.

The alkyl group having 20 or less carbon atoms in R ²¹ has 1 to 20 carbon atoms and may be linear, branched or cyclic, and is the same as the alkyl group in R in the general formula (1). The group is mentioned.

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

The N, N-dialkylamino group having 20 or less carbon atoms in R ²¹ has 2 to 20 carbon atoms, and the two alkyl groups bonded to the nitrogen atom may be the same or different from each other. Each alkyl group has 1 to 19 carbon atoms. However, the total number of carbon atoms of these two alkyl groups is 2 to 20.
The alkyl group bonded to the nitrogen atom may be linear, branched or cyclic, respectively, and the alkyl in R of the general formula (1) except that the number of carbon atoms is 1 to 19. A group similar to the group can be mentioned.

As the reducing compound, hydrazine may be monohydrate (H ₂ N-NH ₂ · H ₂ O).

Preferred compounds among the reducing compounds include, for example, formic acid (HC (= O) -OH); methyl formate (HC (= O) -OCH ₃ ), ethyl formate (HC (= O)). -OCH ₂ CH ₃ ), butyl formate (HC (= O) -O (CH ₂ ) ₃ CH ₃ ) and other formic acid esters; compound (HC (= O) -CH ₂ CH ₃ ), butanal Aldehydes such as (HC (= O)-(CH ₂ ) ₂ CH ₃ ), hexanal (HC (= O)-(CH ₂ ) ₄ CH ₃ ); formamide (HC (= O)- Formamides such as NH ₂ ), N, N-dimethylformamide (HC (= O) -N (CH ₃ ) ₂ ) (represented by the formula "HC (= O) -N (-)-" Compounds having a group); formic acid and the like.

In the silver ink composition, the blending amount of the reducing agent is preferably 0.04 to 3.5 mol, preferably 0.06 to 2.5 mol, per 1 mol of the blended amount of the metallic silver forming material. Is more preferable. When the compounding amount of the reducing agent is in such a range (0.04 to 3.5 mol per mol of the compounding amount of the forming material), the silver ink composition becomes easier and more stable as a conductor. (Metallic silver) can be formed.

[alcohol]
The silver ink composition may be a composition in which alcohol is further blended in addition to the metal silver forming material.

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

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

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

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

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

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

Preferred acetylene alcohols (2) include, for example, 3,5-dimethyl-1-hexin-3-ol, 3-methyl-1-butyne-3-ol, 3-methyl-1-pentyne-3-ol, 2 Examples thereof include −propyne-1-ol, 4-ethyl-1-octyne-3-ol, 3-ethyl-1-heptin-3-ol and the like.

When acetylene alcohol (2) is used, the blending amount of acetylene alcohol (2) in the silver ink composition is preferably 0.01 to 0.7 mol per 1 mole of the metallic silver forming material. , 0.02 to 0.3 mol, more preferably. When the compounding amount of the acetylene alcohol (2) is in such a range (0.01 to 0.7 mol per 1 mol of the compounding material of the forming material), the stability of the silver ink composition is further improved.

The alcohol may be used alone or in combination of two or more. When two or more kinds are used in combination, their combinations and ratios can be adjusted arbitrarily.

[Other ingredients]
The silver ink composition may be a composition containing other components other than the metallic silver forming material, nitrogen-containing compound, reducing agent and alcohol.
The other components in the silver ink composition can be arbitrarily selected depending on the intended purpose, and are not particularly limited. Preferred components include, for example, a solvent other than alcohol, depending on the type and amount of the compounding components. It can be selected arbitrarily.
As the other components in the silver ink composition, one kind may be used alone, or two or more kinds may be used in combination. When two or more kinds are used in combination, their combinations and ratios can be adjusted arbitrarily.

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

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

The blending amount of the other component in the silver ink composition may be appropriately selected according to the type of the other component.
For example, when the other component 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. However, usually, in the silver ink composition, the ratio of the compounding amount of the solvent to the total amount of the compounding components is preferably 50% by mass or less, more preferably 40% by mass or less, and 30% by mass or less. It is more preferably 25% by mass or less, and for example, it may be either 20% by mass or less and 15% by mass or less. The lower limit of the ratio of the blending amount of the solvent described above can be, for example, 5% by mass, which is an example.
When the other component is a component other than the solvent, the ratio of the compounding amount of the other component to the total amount of the compounding component in the silver ink composition is preferably 10% by mass or less, preferably 5% by mass. More preferably, it is less than%.
The ratio of the blending amount of the other components to the total amount of the blending components is 0 mass, that is, the silver ink composition sufficiently exhibits its effect even if the other components are not blended.

In the silver ink composition, all the compounding components may be dissolved, or some or all the components may be dispersed without being dissolved, but it is preferable that all the compounding components are dissolved. It is preferable that the undissolved components are uniformly dispersed.

[Manufacturing method of silver ink composition]
The silver ink composition is obtained by blending a component other than the metallic silver forming material and the metallic silver forming material. After blending each component, the obtained composition may be used as it is as a silver ink composition, or a composition obtained by continuously performing a known purification operation may be used as a silver ink composition, if necessary. In the present invention, particularly when silver β-ketocarboxylate (1) is used as the material for forming the metallic silver, impurities that inhibit conductivity are not generated when each of the above components is blended, or such Since the amount of impurities produced can be suppressed to an extremely small amount, a conductor (metal silver) having sufficient conductivity can be obtained even if a silver ink composition that has not been refined is used.

When blending each component, all the components may be added and then mixed, some components may be added sequentially and mixed, or all components may be added sequentially and mixed. Good. However, in the present invention, the reducing agent is preferably blended by dropping, and the surface roughness of metallic silver tends to be further reduced by suppressing fluctuations in the dropping rate.
The mixing method is not particularly limited, and a method of rotating and mixing a stirrer or a stirring blade or the like; a method of mixing using a mixer, a three-roll roll, a kneader or a bead mill or the like; It may be appropriately selected from known methods.
In the case of uniformly dispersing the undissolved components in the silver ink composition, for example, it is preferable to apply the method of dispersing using the above-mentioned three rolls, a kneader, a bead mill or the like.

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

Preferred silver ink compositions include, for example, a composition obtained by adding a material for forming metallic silver to a nitrogen-containing compound, then adding a reducing agent, and then adding alcohol. An example of a more preferable composition of the silver ink composition obtained in such an order of addition is a composition in which the first nitrogen-containing compound and the second nitrogen-containing compound are used in combination as the nitrogen-containing compound. ..
By using the silver ink composition obtained in such an order of addition, a fine linear silver layer can be formed more stably.

When the first nitrogen-containing compound and the second nitrogen-containing compound are used in combination, the silver ink composition is the first compounding step of blending the metal silver forming material with the mixture of the first nitrogen-containing compound and the second nitrogen-containing compound. And, in the second compounding step of blending the reducing agent with the compounding (Q1) obtained in the first compounding step, and in the compounding (Q2) obtained in the second compounding step, alcohol and, if necessary, The composition obtained by the production method having the third blending step of blending the other components is preferable.

The blending amount of the metallic silver forming material in the first blending step is preferably the total amount of the metallic silver forming material used in the present production method.
The blending amount of the reducing agent in the second blending step is preferably the total amount of the reducing agent used in the present production method.
The amount of alcohol compounded in the third compounding step is preferably the total amount of alcohol used in the present production method.
The blending amount of the other component in the third blending step is preferably the total amount of the other component used in the present production method.

Further, as a preferable silver ink composition, for example, a solvent other than alcohol is added to the nitrogen-containing compound, then a material for forming metallic silver is added, then a reducing agent is added, and then alcohol is added. Composition can be mentioned.
By using the silver ink composition obtained in such an order of addition, a fine linear silver layer can be formed more stably.
Such a silver ink composition using a solvent other than alcohol has, for example, a step of blending a solvent other than alcohol, and the first nitrogen-containing compound and the second nitrogen-containing compound are used in combination as the nitrogen-containing compound. Can be obtained by the same method as the production method having the above-mentioned first compounding step to third compounding step, except that the above-mentioned is not essential.

[carbon dioxide]
The silver ink composition may be a composition further supplied with carbon dioxide. Such a silver ink composition has a high viscosity, and is used for printing methods that require thickening of ink, such as a flexo printing method, a screen printing method, a gravure printing method, a gravure offset printing method, and a pad printing method. Suitable for application.

Carbon dioxide may be supplied at any time during the production of the silver ink composition.
Then, in the present invention, for example, carbon dioxide is supplied to the first mixture in which the metallic silver forming material and the nitrogen-containing compound are blended to obtain a second mixture, and if necessary, to the second mixture. , It is preferable to blend the reducing agent to produce a silver ink composition. Further, when the alcohol or other components are blended, these can be blended at the time of production of either one or both of the first mixture and the second mixture, and can be arbitrarily selected depending on the purpose.

The first mixture can be produced by the same method as the above-mentioned silver ink composition except that the compounding components are different.

In the first mixture, all the ingredients may be dissolved, or some of the ingredients may be dispersed without being dissolved, but it is preferable that all the ingredients are dissolved, and the first mixture is dissolved. It is preferable that the components that are not used are uniformly dispersed.

The compounding temperature at the time of producing the first mixture is not particularly limited as long as each compounding component is not deteriorated, but is preferably −5 to 30 ° C. The blending time may be appropriately adjusted according to the type of blending component and the temperature at the time of blending, but is preferably 0.5 to 12 hours, for example.

The carbon dioxide (CO ₂ ) supplied to the first mixture may be either gaseous or solid (dry ice), or both gaseous and solid. It is presumed that when carbon dioxide is supplied, this carbon dioxide dissolves in the first mixture and acts on the components in the first mixture, thereby increasing the viscosity of the obtained second mixture.

The carbon dioxide gas may be supplied by various known methods of blowing the gas into the liquid, and a suitable supply method may be appropriately selected. For example, one end (first end) of the pipe is immersed in the first mixture, the other end (second end) of the pipe is connected to a carbon dioxide gas supply source, and carbon dioxide gas is passed through the first mixture through this pipe. There is a method of supplying to. At this time, carbon dioxide gas may be supplied directly from the end of the pipe, but for example, a large number of voids that can serve as gas flow paths are provided, such as a porous member, to diffuse the introduced gas. A gas diffusion member capable of being released as minute bubbles may be connected to the end of the pipe, and carbon dioxide gas may be supplied through the gas diffusion member. Further, carbon dioxide gas may be supplied while stirring the first mixture in the same manner as in the production of the first mixture. By doing so, carbon dioxide can be efficiently supplied.

The amount of carbon dioxide gas supplied may be appropriately adjusted according to the amount of the first mixture to be supplied and the viscosity of the target silver ink composition or the second mixture, and is not particularly limited. For example, in order to obtain about 100 to 1000 g of a silver ink composition 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 more preferably 200 L or more. Although the viscosity of the silver ink composition at 20 to 25 ° C. has been described here, the temperature at which the silver ink composition is used is not limited to 20 to 25 ° C. and can be arbitrarily selected. Further, in the present specification, "viscosity" 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 first mixture, and is preferably 1 mL / min or more. More preferably. The upper limit of the flow rate is not particularly limited, but it is preferably 40 mL / min per 1 g of the mixture in consideration of handleability and the like.
Then, the carbon dioxide gas supply time may be appropriately adjusted in consideration of the required carbon dioxide gas supply amount and the flow rate.

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

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 within an appropriate range while mutually considering their respective values. For example, even if the temperature is set low, (1) the flow rate of carbon dioxide gas is set to be large, (2) the supply time of carbon dioxide gas is set to be long, or this (1) and By performing both (2), carbon dioxide can be efficiently supplied. Further, even if the flow rate of carbon dioxide gas is set to be small, (3) the temperature is raised, (4) the supply time of carbon dioxide gas is set to be long, or (3) and ( By performing both of 4), carbon dioxide can be efficiently supplied. That is, by flexibly combining the values within the above numerical range (5 to 70 ° C.) exemplified as the flow rate of carbon dioxide gas and the temperature at the time of supplying carbon dioxide gas, while considering the supply time of carbon dioxide gas. A silver ink composition of good quality can be efficiently obtained.

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

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

The viscosity of the second mixture may be appropriately adjusted according to the purpose such as the silver ink composition or the handling method of the second mixture, and is not particularly limited. For example, when the silver ink composition is applied to a printing method using a high-viscosity ink such as a screen printing method or a flexographic printing method, the viscosity of the second mixture at 20 to 25 ° C. is 3 Pa · s or more. Is preferable. Although the viscosity of the second mixture at 20 to 25 ° C. has been described here, the temperature at which the second mixture is used is not limited to 20 to 25 ° C. and can be arbitrarily selected.

The second mixture can be further blended with one or more selected from the group consisting of the reducing agent, alcohol and other components, if necessary, to obtain a silver ink composition.
The silver ink composition at this time can be produced by the same method as the above-mentioned silver ink composition that does not use carbon dioxide, except that the compounding components are different. Then, in the obtained silver ink composition, all the compounding components may be dissolved, or some components may be dispersed without being dissolved, but all the compounding components are dissolved. It is preferable that the undissolved components are uniformly dispersed.

The temperature at the time of blending the reducing agent is not particularly limited as long as each blending component is not deteriorated, but is preferably −5 to 60 ° C. Then, the temperature at the time of blending may be appropriately adjusted according to the type and amount of the blending component so that the mixture obtained by blending has a viscosity that can be easily stirred.
The blending time may be appropriately adjusted according to the type of blending component and the temperature at the time of blending, but is preferably 0.5 to 12 hours, for example.

The other components may be blended during the production of either the first mixture or the second mixture, or may be blended during the production of both the first mixture and the second mixture, as described above. Good. That is, in the process of producing the silver ink composition through the first mixture and the second mixture, the ratio of the amount of the other components to the total amount of the components other than carbon dioxide ([other components (mass)] / [ Metallic silver forming material, nitrogen-containing compound, reducing agent, alcohol, and other components (mass)] × 100) is preferably 10% by mass or less, more preferably 5% by mass or less, and 0 The silver ink composition fully exhibits its effect without blending by mass, that is, other components.

The silver ink composition to which carbon dioxide is supplied has a viscosity at 20 to 25 ° C., for example, when the silver ink composition is applied to a printing method using a high viscosity ink such as a screen printing method or a flexographic printing method. It is preferably 1 Pa · s or more.

For example, when the reducing agent is blended, the obtained blend (silver ink composition) tends to generate heat relatively easily. When the temperature at the time of blending the reducing agent is high, this blend is in the same state as during the heat treatment of the silver ink composition described later, and therefore, the reducing agent acts to promote the decomposition of the metallic silver forming material. It is presumed that the formation of metallic silver may be initiated in at least a part of the metallic silver forming material. Such a silver ink composition containing metallic silver may be able to form a conductor by performing post-treatment under milder conditions than the silver ink composition not containing metallic silver at the time of forming the conductor. Further, even when the blending amount of the reducing agent is sufficiently large, the conductor may be formed by performing the post-treatment under the same mild conditions. In this way, by adopting the conditions that promote the decomposition of the metallic silver forming material, the conductor can be post-treated by heat treatment at a lower temperature or by drying at room temperature without heat treatment. May be able to form. Further, such a silver ink composition containing metallic silver can be handled in the same manner as a silver ink composition not containing metallic silver, and the handleability is not particularly inferior.

The viscosity of the second mixture in the present invention is higher than usual due to the supply of carbon dioxide as described above. On the other hand, when the reducing agent is added to the second mixture, depending on the type of the second mixture or the reducing agent, the formation of metallic silver is started in at least a part of the metallic silver forming material as described above, and the metallic silver is formed. May precipitate. Here, when the viscosity of the second mixture is high, the aggregation of the precipitated metallic silver is suppressed, and the dispersibility of the metallic silver in the obtained silver ink composition is improved. A conductor obtained by forming metallic silver by a method described later using such a silver ink composition is obtained by blending a reducing agent with a mixture having a low viscosity, that is, a mixture to which carbon dioxide is not supplied. The conductor has higher conductivity (lower volume resistivity) and smaller surface roughness than the conductor when the silver ink composition is used, and the conductor has more preferable characteristics.

Further, in the present invention, it is also preferable to supply carbon dioxide to the mixture containing the metallic silver forming material, alcohol and nitrogen-containing compound to produce a silver ink composition. In this case, the same method as described above can be adopted as the carbon dioxide supply method.

The silver ink composition can be adhered to the substrate by a known method such as a printing method, a coating method, or a dipping method.
Examples of the printing method include a screen printing method, a flexo printing method, an offset printing method, a dip printing method, an inkjet printing method, a dispenser printing method, a jet dispenser printing method, a gravure printing method, and a gravure offset printing method. The pad printing method and the like can be mentioned.
As the coating method, for example, various coaters such as spin coater, air knife coater, curtain coater, die coater, blade coater, roll coater, gate roll coater, bar coater, rod coater, gravure coater, wire bar and the like are used. The method and the like can be mentioned.

In the conductive layer forming step, the thickness of the conductive layer can be adjusted by adjusting the amount of the silver ink composition adhered to the substrate or the blending amount of the metallic silver forming material in the silver ink composition.

When the silver ink composition is dried, it may be carried out by a known method. For example, it may be carried out under normal pressure, reduced pressure or blowing conditions, and under any of atmospheric conditions and an inert gas atmosphere. You may do it. The drying temperature is not particularly limited, and either heat drying or room temperature drying may be used. A preferred drying method when heat treatment is not required includes, for example, a method of drying in the air at 18 to 30 ° C.

When the silver ink composition is heated (baked), the conditions of the heating (baking) treatment may be appropriately adjusted according to the type of the compounding components of the silver ink composition. Usually, the heating temperature is preferably 60 to 370 ° C, more preferably 70 to 280 ° C. The heating time may be adjusted according to the heating temperature, but is usually preferably 1 minute to 24 hours, more preferably 1 minute to 12 hours. Among the materials for forming metallic silver, the silver carboxylate, particularly silver β-ketocarboxylate (1), is different from the material for forming metallic silver such as silver oxide, and uses a reducing agent known in the art. Even without it, it decomposes at low temperatures. Then, reflecting such a decomposition temperature, the silver ink composition can form metallic silver at an extremely lower temperature than the conventional composition, as described above.

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

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

In the present specification, "humidification" means artificially increasing the humidity unless otherwise specified, and preferably the relative humidity is 5% or more. During the heat treatment, the high treatment temperature makes the humidity in the treatment environment extremely low, so the relative humidity of 5% can be said to be clearly an artificially increased humidity.

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

The heat treatment of the silver ink composition may be performed in two steps. For example, in the first-step heat treatment, the silver ink composition is mainly dried instead of forming metallic silver, and in the second-step heat treatment, metallic silver is formed to the end.
In the first-stage heat treatment, the heating temperature may be appropriately adjusted according to the type of the compounding component of the silver ink composition, but is preferably 60 to 120 ° C, more preferably 70 to 110 ° C. preferable. The heating time may be adjusted according to the heating temperature, but is usually preferably 5 seconds to 12 hours, more preferably 30 seconds to 2 hours.
In the second step of heat treatment, the heating temperature may be appropriately adjusted according to the type of the compounding components of the silver ink composition so that metallic silver is formed well, but it may be 60 to 280 ° C. It is preferably 70 to 260 ° C., more preferably 70 to 260 ° C. The heating time may be adjusted according to the heating temperature, but is usually preferably 1 minute to 12 hours, more preferably 1 minute to 10 hours.
As will be described later, when the silver ink composition is attached to a substrate having low heat resistance and heated (baked), the heating temperature in the first and second stages of heat treatment is less than 130 ° C. It is preferably 125 ° C. or lower, more preferably 120 ° C. or lower.

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

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

When the heat treatment under humidified conditions is adopted, the heat treatment of the silver ink composition is performed in the first stage heat treatment under the non-humidified conditions, instead of forming metallic silver as described above. It is particularly preferable to carry out the drying by a two-step method in which the drying is mainly carried out and the metallic silver is formed to the end as described above under humidifying conditions in the second step of the heat treatment.

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., preferably 70 to 110 ° C. More preferred. The heating time is preferably 5 seconds to 1 hour, more preferably 30 seconds to 30 minutes, and particularly preferably 30 seconds to 15 minutes.
The heating temperature during the heat treatment under the second stage humidifying condition, which is performed after the heat treatment under the first stage non-humidifying condition, is preferably 60 to 140 ° C., preferably 70 to 130 ° C. Is more preferable. The heating time is preferably 1 minute to 2 hours, more preferably 1 minute to 1 hour, and particularly preferably 1 minute to 30 minutes.
As will be described later, when the silver ink composition is attached to a substrate having low heat resistance and heat (baked), it is heat-treated under the first-step non-humidifying condition and the second-step humidifying condition. The heating temperature in the heat treatment in the above is preferably less than 130 ° C., more preferably 125 ° C. or lower, and particularly preferably 120 ° C. or lower.

Up to this point, a method for forming a conductive layer has been described when a silver ink composition containing a metallic silver forming material is used as the metal ink composition. When the conductive layer is formed by using another composition for a conductive layer such as a metal ink composition when the metal type is other than silver, for example, in the production method when the above-mentioned silver ink composition is used. The conductive layer can be formed by applying a method in which a part of the composition is changed according to the type of the composition for the conductive layer.

<Coating layer forming process>
In the coating layer, for example, a composition as a raw material for forming the coating layer (hereinafter, may be abbreviated as “composition for coating layer”) is used as a target portion on the base material on which the conductive layer is formed. A composition layer that coats the conductive layer is formed by adhering to the coating layer, and the composition layer (composition for a coating layer) can be formed by appropriately selecting a solidification treatment such as a drying treatment or a heat treatment. .. When the composition for the coating layer is a curable resin composition, the composition layer may be cured to form a coating layer. Then, the heat treatment may be performed in combination with a drying treatment and a curing treatment.

[Curable resin]
Examples of the coating layer composition include an energy ray-curable resin such as an ultraviolet curable resin or a composition containing a thermosetting resin as the curable resin, and the energy ray-curable resin is blended. The composition is preferred.

In the composition for the coating layer, one type of curable resin may be used alone, or two or more types may be used in combination. When two or more types are used in combination, their combinations and ratios can be arbitrarily selected.

(Energy ray curable resin)
Examples of the energy ray-curable resin include polyurethane (meth) acrylate and the like. That is, examples of the composition for a coating layer containing the energy ray-curable resin include a composition containing a polyurethane (meth) acrylate.

The blending amount of the energy ray-curable resin in the composition for the coating layer may be appropriately selected according to the type of the energy ray-curable resin, and is not particularly limited.
For example, when the energy ray-curable resin is a resin other than polyurethane (meth) acrylate, the ratio of the amount of the energy ray-curable resin to the total amount of the compounding components other than the solvent described later is 70% by mass or more. Is preferable. The upper limit of the ratio is not particularly limited, and can be selected from, for example, 100% by mass, 99% by mass, 98% by mass, and the like.

[(Meta) acrylic acid ester]
When polyurethane (meth) acrylate is blended as the energy ray-curable resin, the coating layer composition may be a composition containing (meth) acrylic acid ester in addition to polyurethane (meth) acrylate.
The (meth) acrylic acid ester may be a known (meth) acrylic acid ester, and may be appropriately selected depending on the intended purpose.
In the composition for the coating layer, one type of (meth) acrylic acid ester may be used alone, or two or more types may be used in combination. When two or more types are used in combination, their combinations and ratios can be arbitrarily selected.

In the coating layer composition not containing the (meth) acrylic acid ester, the ratio of the amount of the polyurethane (meth) acrylate to the total amount of the components other than the solvent described later is preferably 70% by mass or more. , 75% by mass or more, more preferably 80% by mass or more, particularly preferably 85% by mass or more, for example, 90% by mass or more, 95% by mass or more, etc. Good. The upper limit of the ratio is not particularly limited, and can be selected from, for example, 100% by mass, 99% by mass, 98% by mass, and the like.

In the coating layer composition containing the (meth) acrylic acid ester, the ratio of the total amount of the polyurethane (meth) acrylate and the (meth) acrylic acid ester to the total amount of the compounding components other than the solvent described later is 70. It is preferably 90% by mass or more, more preferably 75% by mass or more, further preferably 80% by mass or more, particularly preferably 85% by mass or more, for example, 90% by mass or more, 95% by mass. It may be mass% or more. The upper limit of the ratio is not particularly limited, and can be selected from, for example, 100% by mass, 99% by mass, 98% by mass, and the like.

In the composition for the coating layer containing the (meth) acrylic acid ester, the ratio of the blending amounts of the polyurethane (meth) acrylate and the (meth) acrylic acid ester is [polyurethane (meth) acrylate (mass)]: [(. In terms of the mass ratio of [meth) acrylic acid ester (mass)], it is preferably 30:70 to 90:10, more preferably 35:65 to 85:15, and 38:62 to 82:18. Is particularly preferable.

[Hardener]
When the energy ray-curable resin is blended, the coating layer composition is preferably a composition containing a curing agent in addition to the energy ray-curable resin.
The curing agent may be a known curing agent, and may be appropriately selected depending on the intended purpose.
In the composition for the coating layer, one type of curing agent may be used alone, or two or more types may be used in combination. When two or more types are used in combination, their combinations and ratios can be arbitrarily selected.

In the coating layer composition containing the energy ray-curable resin, the ratio of the amount of the curing agent to the amount of the energy ray-curable resin is preferably 1 to 10% by mass, preferably 2 to 8% by mass. More preferably.

[Additive]
The composition for the coating layer may be a composition containing various known additives in addition to the curable resin, the (meth) acrylic acid ester and the curing agent, as long as the effects of the present invention are not impaired.
In the composition for the coating layer, one type of additive may be used alone, or two or more types may be used in combination. When two or more types are used in combination, their combinations and ratios can be arbitrarily selected.
The blending amount of the additive in the composition for the coating layer may be appropriately selected according to the type of the additive, and is not particularly limited.
Preferred additives include, for example, migration inhibitors and surfactants.

(Migration inhibitor)
The migration inhibitor is a compound that suppresses a change in the formation position of the conductive layer on the substrate (migration of the conductive layer). Migration of the conductive layer is likely to occur between adjacent lines, for example, when the conductive layer is patterned in a line-and-space pattern.

Examples of the migration inhibitor include 1,2,3-benzotriazole, 1- [N, N-bis (2-ethylhexyl) aminomethyl] benzotriazole, 1- [N, N-bis (2-ethylhexyl) amino. Methyl] methylbenzotriazole, 2,2'-[[(methyl-1H-benzotriazole-1-yl) methyl] imino] bisethanol, 5-methyl-1H-benzotriazole, 1,2-bis [3-( 4-Hydroxy-3,5-di-tert-butylphenyl) propionyl] hydrazine and the like can be mentioned.

In the coating layer composition, the ratio of the amount of the migration inhibitor to the amount of the curable resin (total amount of the energy ray-curable resin and the thermosetting resin) is 0.2 to 10% by mass. It is preferably 0.5 to 8% by mass, and more preferably 0.5 to 8% by mass.

(Surfactant)
The surfactant may be a known one, and may be any of an anionic surfactant, a cationic surfactant, an amphoteric surfactant and a nonionic surfactant, and may be appropriately selected depending on the intended purpose.

Among them, the surfactant is preferably a nonionic surfactant.
The nonionic surfactant preferably has a fluorine atom, more preferably has a fluoroalkenyl group, and particularly preferably has a perfluoroalkenyl group.

In the composition for the coating layer, one type of surfactant may be used alone, two or more types may be used in combination, and when two or more types are used in combination, the combination and ratio thereof may be arbitrary. You can choose.

When a surfactant is used, the ratio of the blending amount of the surfactant to the total blending component in the coating layer composition is preferably 0.004 to 1% by mass, preferably 0.008 to 0.5. More preferably, it is by mass%. When the ratio is at least the lower limit value, the effect of using the surfactant can be obtained more remarkably. Further, when the ratio is not more than the upper limit value, excessive use of the surfactant is suppressed.

[solvent]
The composition for the coating layer is preferably a composition containing a solvent in addition to the curable resin (energy ray curable resin or thermosetting resin). Since the composition for the coating layer contains a solvent, the handleability is improved.

The solvent is not particularly limited, and preferred solvents include aromatic hydrocarbons such as toluene, o-xylene, m-xylene, and p-xylene; aliphatic hydrocarbons such as hexane, heptane, and octane; ethanol, and the like. Monovalent alcohols such as 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol (isobutyl alcohol), 2-methyl-2-propanol (tert-butyl alcohol); ethylene glycol ( Polyhydric alcohols including dihydric alcohols such as 1,2-ethanediol), propylene glycol (1,2-propanediol), diethylene glycol (2,2'-oxydiethanol); 2-aminoethanol, 3-amino Amino alcohols (compounds having amino groups and hydroxyl groups) such as -1-propanol and 4-amino-1-butanol; 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol (ethylene glycol monopropyl ether), 1- Methoxy-2-propanol, 2-methoxy-1-propanol, 3-methoxy-1-butanol, 1-methoxy-2-butanol, 1-ethoxy-2-propanol, 3-ethoxy-1-propanol, 2- (1) -Methylethoxy) ethanol, 3-methoxy-3-methylbutanol, 1-butoxy-2-propanol and other alkoxy alcohols (compounds having an alkoxy group and a hydroxyl group); dichloromethane, chloroform and other halogenated hydrocarbons; ethyl acetate, glutaru Esters such as monomethyl acid, dimethyl glutarate; ethers such as diethyl ether, tetrahydrofuran (THF), 1,2-dimethoxyethane (dimethylcellosolve); acetone, methyl ethyl ketone (MEK), cyclohexanone, 2,6-dimethyl-4-heptanone , Ketones such as isophorone; nitriles such as acetonitrile; amides such as N, N-dimethylformamide (DMF), N, N-dimethylacetamide; keto such as 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol) Examples thereof include, but are not limited to, alcohols (compounds having a carbonyl group and a hydroxyl group).

In the present invention, neither alcohol nor ketone shall contain ketoalcohol unless otherwise specified. That is, in the present invention, the alcohol does not contain a carbonyl group (-C (= O)-), the ketone does not contain a hydroxyl group (-OH), and the alcohol and the ketone are different from keto alcohol. Distinguish as a thing.

As the solvent, one type may be used alone, two or more types may be used in combination, and when two or more types are used in combination, the combination and ratio thereof can be arbitrarily selected.

In the composition for the coating layer, the ratio of the compounding amount of the solvent to the total amount of the compounding components is preferably 15 to 95% by mass, more preferably 20 to 90% by mass, and 25 to 85% by mass. Is particularly preferred.

The coating layer composition can be produced, for example, by the same method as in the case of the silver ink composition described above, except that the compounding components are different. However, the temperature at the time of blending is preferably 15 to 50 ° C. The blending time is preferably the time required for the blended components to be uniformly dissolved or dispersed, and is preferably, for example, 10 minutes to 12 hours.

The coating layer composition can be attached to a target portion by a known method such as a printing method, a coating method, or a dipping method, as in the case of a silver ink composition, for example.

In the coating layer forming step, the thickness of the coating layer can be adjusted by adjusting the amount of the coating layer composition to be adhered to the target portion or the blending amount of the curable resin or the like in the coating layer composition. ..

The solidification treatment such as the drying treatment and the heat treatment of the coating layer composition can be performed by the same method as in the case of the silver ink composition.

When the composition for the coating layer is cured, it may be irradiated with energy rays such as ultraviolet rays or heated depending on the type of the curable resin contained therein.
For example, in case of curing by irradiation of energy rays, irradiation of energy rays is preferably 200~1200mJ / cm ^2, more preferably 300~1000mJ / cm ^2.

<Process of forming other layers>
In the case of producing a laminate in which a layer other than the conductive layer and the coating layer is provided on the base material as the laminate of the present invention, the other layers are formed at a predetermined timing in the above production method. Steps may be added as appropriate.

<< Electronic equipment, transparent conductive film >>
The laminate is suitable for forming various electronic devices, transparent conductive films, and the like.
For example, an electronic device can be configured to include the base material as a housing (exterior material) by using the laminated body, and at least a part of the housing (exterior material) is formed by the base material in the laminated body. Except for the points, the configuration can be the same as that of a known electronic device. For example, a flat or curved portion of an exterior material in a communication device such as a mobile phone is used as the base material, a thin wire composed of the metallic silver is formed on the exterior material (base material), and the thin wire is used as a circuit. Therefore, the laminated body can be used as a circuit board. Then, for example, a mobile phone can be configured by combining a voice input unit, a voice output unit, an operation switch, a display unit, and the like in addition to the laminated body. Further, by using the patterned silver layer as an antenna, the laminated body can be used as an antenna structure, and the configuration is the same as that of a known data receiving / transmitting body except that the antenna structure is used. As a result, it can be a new data receiver / transmitter. For example, in the laminated body, a non-contact data receiving / transmitting body can be configured by providing an IC chip electrically connected to a silver layer on a base material to form an antenna portion.

Further, the transparent conductive film can be configured to include the silver layer as ultrafine wiring or ultrathin wiring by using the laminate, and is known to be transparent except that the silver layer is provided as ultrafine wiring or ultrathin wiring. It can have the same configuration as the conductive film. In particular, the laminate is suitable for forming a touch panel, an optical display, or the like.
The line width of the ultrafine wiring is preferably 1 to 20 μm, more preferably 1.3 to 15 μm, and particularly preferably 1.5 to 13 μm.
Further, the cross-sectional shape of the ultrafine wiring is preferably a semi-elliptical shape in which almost half of the region in the minor axis direction of the ellipse is cut off.
On the other hand, the thickness of the ultrathin wiring is preferably 5 nm to 10 μm, more preferably 7 nm to 5 μm, and particularly preferably 10 nm to 1 μm.
The cross-sectional shape of the ultra-thin wiring is the same as the cross-sectional shape of the ultra-fine wiring.
In the transparent conductive film, it is preferable that the silver layer satisfies at least one of such line width and thickness. If the silver layer has such a line width or thickness, it is difficult to visually recognize its presence, and thus it is preferable as a transparent conductive film.

Further, in the laminated body, a silver layer can be formed at a low temperature, and a wide range of materials such as a base material can be selected. Therefore, the degree of freedom in design is dramatically improved, and electronic devices, transparent conductive films, etc. It is also possible to make the structure more rational.
The above-mentioned electronic devices, transparent conductive films, and the like can maintain high performance for a long period of time.

Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to the examples shown below.
Table 1 shows the resin components used in the production of the coating layer composition. It is recommended that all the resin components shown in Table 1 be cured by heating at 80 ° C. for 10 minutes and then irradiating with ultraviolet rays at an irradiation amount of 400 mJ / cm ² . "Pencil hardness" in Table 1 means the pencil hardness of the cured product.
In the following, Example 1 will be referred to as Reference Example 1.

[Example 1]
<Manufacturing of laminate>
(Manufacturing of silver ink composition)
In a beaker, 2-ethylhexylamine (1.26 times the molar amount of 2-methylacetate silver described later) and isobutylamine (0.19 times the molar amount of 2-methylacetate silver acetate described later) are mixed. Then, the mixture was stirred for 1 minute using a mechanical stirrer. 52.9 g of silver 2-methylacetate acetate was added thereto so that the liquid temperature was 40 ° C. or lower, and after the addition was completed, formic acid (0.38 times the molar amount of silver 2-methylacetate acetate) was further added. Was added dropwise over 10 minutes and then stirred for 1.5 hours. Next, 3,5-dimethyl-1-hexin-3-ol (“Surfinol 61” manufactured by Air Products Japan Co., Ltd., hereinafter may be abbreviated as “DMHO”) (for silver 2-methylacetate acetate, 0. A silver ink composition was obtained by adding (035 times by molar amount), mixing, and stirring for another 5 minutes. Table 2 shows the types and ratios of each compounding ingredient. In Table 2, the "nitrogen-containing compound (molar ratio)" refers to the amount of the nitrogen-containing compound (number of moles) per mole of the material for forming metallic silver ([number of moles of nitrogen-containing compound] / [metal]. Number of moles of silver forming material]). Similarly, the "reducing agent (molar ratio)" is also the amount of the reducing agent compounded per mole of the metal silver forming material (the number of moles) ([the number of moles of the reducing agent] / [the mole of the metal silver forming material]. Number]). Similarly, for "alcohol (molar ratio)", the amount of alcohol compounded per mole of the metallic silver forming material (number of moles) ([number of moles of alcohol] / [number of moles of metallic silver forming material]). Means.

(Formation of silver layer)
The silver ink composition obtained above is coated on one main surface (surface, first main surface) of a polycarbonate base material (thickness 2 mm) by a gravure offset printing method to obtain a printing pattern. Formed. The printing pattern was a mesh pattern in which a large number of lines having the same width were arranged at predetermined intervals and formed in two orthogonal directions.
Next, the substrate on which the above-mentioned printing pattern is formed is dried in an oven at 100 ° C. for 10 minutes, and further heated (baked) at 100 ° C. for 10 minutes under a humidifying condition with a relative humidity of 99%. A metal silver line-and-space pattern having a width of 4 μm and a distance between adjacent lines in the same direction of 200 μm formed a metallic silver mesh pattern formed in two orthogonal directions. The thickness of the metallic silver (silver layer) forming this mesh pattern was 0.06 to 0.07 μm.

(Manufacturing of composition for coating layer)
Curing agent (2-hirodoxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one, Ciba Japan, Inc. under the condition of 25 ° C. "IRGACURE 127") manufactured by (IRGACURE 127) was added to cyclohexanone and dissolved to obtain a cyclohexanone solution. The amount of the curing agent added was set to be 5% by mass with respect to the amount of the ultraviolet curable resin (A) described later.
Next, the ultraviolet curable resin (A) was added to the cyclohexanone solution whose temperature was adjusted to 45 ° C., and the mixture was stirred to obtain a coating layer composition (A-1). The amount of the ultraviolet curable resin (A) added at this time was such that the content of the ultraviolet curable resin (A) in the coating layer composition (A-1) was 29.6% by mass.
Table 3 shows the types of each compounding component and the content in the coating layer composition (A-1). In addition, in Table 3, the description of "-" in the column of the compounding component means that the component is not compounded.

(Formation of coating layer, production of laminate)
The coating film composition (A-) obtained above by a spin coating method (2000 rpm for 5 seconds, then 3000 rpm for 10 seconds) on the entire surface of the pattern-forming surface of the base material on which a metallic silver mesh pattern was formed. 1) was applied to form a coating film.
Next, the formed coating film is dried at 100 ° C. for 10 minutes, and then the dried coating film is irradiated with ultraviolet rays at an irradiation amount of 800 mJ / cm ² to cure the ultraviolet curable resin (A). As a result, the entire surface of the pattern-forming surface of the base material, that is, the surface of the metallic silver mesh pattern on the pattern-forming surface and the entire surface of the base material on which the metallic silver mesh pattern is not formed. A coating layer was formed to cover. The maximum thickness of this coating layer was 7 μm.
As described above, a mesh-like silver layer is formed as a conductive layer on the base material, and a coating layer is formed on the silver layer and a region on the base material where the silver layer is not provided. Got

<Evaluation of laminated body>
(Pencil hardness of coating layer)
The pencil hardness of the surface of the coating layer of the laminate obtained above was measured according to JIS K5600-5-4. The results are shown in Table 4.

(Haze H of laminated body and haze change rate ΔH)
The laminate obtained above is continuously humidified and heat-treated in an atmosphere of a temperature of 85 ° C. and a relative humidity of 85%, and the laminate is performed before the start of the treatment and when a predetermined time has elapsed after the start of the treatment. for body, from its coating layer side (covering layer outer surface), according to JIS K7136, it was measured haze _H t (%) using a haze meter (manufactured by Murakami color Research Laboratory). The results are shown in Table 4. Incidentally, the absolute value of all measurements of haze H _t shown in Table 4. Then, the haze _{H 0} of the processing before the start (t = 0), and a haze _{H t} of the process after the start time t (t> 0), the formula _{(I t)} by a haze change rate [Delta] H _t of the laminate (%) Was calculated. The results are shown in Table 5.

<Manufacturing and evaluation of laminate>
[Example 2]
(Manufacturing of composition for coating layer)
Curing agent (2-hirodoxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one, Ciba Japan, Inc. under the condition of 25 ° C. "IRGACURE 127") manufactured by (IRGACURE127) was added to 1-propanol and dissolved to obtain a 1-propanol solution. The amount of the curing agent added was set to be 5% by mass with respect to the amount of the ultraviolet curable resin (B) described later.
Next, the ultraviolet curable resin (B) was added to the 1-propanol solution whose temperature was adjusted to 45 ° C., and the mixture was stirred to obtain a coating layer composition (B-1). The amount of the ultraviolet curable resin (B) added at this time was such that the content of the ultraviolet curable resin (B) in the coating layer composition (B-1) was 29.6% by mass.
Table 3 shows the types of each compounding component and the content in the coating layer composition (B-1).

(Manufacturing and evaluation of laminate)
A laminate was produced and evaluated by the same method as in Example 1 except that the coating layer composition (B-1) obtained above was used. The results are shown in Tables 4 and 5.

[Example 3]
(Manufacturing of composition for coating layer)
Same as in Example 2 except that the content of the ultraviolet curable resin (B) in the coating layer composition was changed to 48.8% by mass instead of 29.6% by mass during the production of the coating layer composition. By the method, a coating layer composition (B-2) was obtained. In addition, with respect to the increase in the content of the ultraviolet curable resin (B), the amount of the curing agent added to 1-propanol was the same as in Example 2 with respect to the amount of the ultraviolet curable resin (B) added. The amount was set to 5% by mass, and the amount added was increased as compared with the case of Example 2.
Table 3 shows the types of each compounding component and the content in the coating layer composition (B-2).

(Manufacturing and evaluation of laminate)
A laminate was produced and evaluated by the same method as in Example 1 except that the coating layer composition (B-2) obtained above was used. The results are shown in Tables 4 and 5.

[Example 4]
(Manufacturing of composition for coating layer)
Same as in Example 2 except that the content of the ultraviolet curable resin (B) in the coating layer composition was 67.6% by mass instead of 29.6% by mass when the coating layer composition was produced. By the method, a coating layer composition (B-3) was obtained. In addition, with respect to the increase in the content of the ultraviolet curable resin (B), the amount of the curing agent added to 1-propanol was the same as in Example 2 with respect to the amount of the ultraviolet curable resin (B) added. The amount was set to 5% by mass, and the amount added was increased as compared with the case of Example 2.
Table 3 shows the types of each compounding component and the content in the coating layer composition (B-3).

(Manufacturing and evaluation of laminate)
A laminate was produced and evaluated by the same method as in Example 1 except that the coating layer composition (B-3) obtained above was used. The results are shown in Tables 4 and 5.

[Example 5]
(Manufacturing of composition for coating layer)
Curing agent (2-hirodoxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one, Ciba Japan, Inc. under the condition of 25 ° C. "IRGACURE 127") manufactured by (IRGACURE127) was added to 1-propanol and dissolved to obtain a 1-propanol solution. The amount of the curing agent added was set to be 5% by mass with respect to the amount of the ultraviolet curable resin (C) described later.
Next, the ultraviolet curable resin (C) was added to the 1-propanol solution whose temperature was adjusted to 45 ° C., and the mixture was stirred to obtain a coating layer composition (C-1). The amount of the ultraviolet curable resin (C) added at this time was such that the content of the ultraviolet curable resin (C) in the coating layer composition (C-1) was 29.6% by mass.
Table 3 shows the types of each compounding component and the content in the coating layer composition (C-1).

(Manufacturing and evaluation of laminate)
A laminate was produced and evaluated by the same method as in Example 1 except that the coating layer composition (C-1) obtained above was used. The results are shown in Tables 4 and 5.

[Example 6]
(Manufacturing of composition for coating layer)
Same as Example 5 except that the content of the ultraviolet curable resin (C) in the coating layer composition was changed to 48.8% by mass instead of 29.6% by mass during the production of the coating layer composition. By the method, a coating layer composition (C-2) was obtained. In addition, with respect to the increase in the content of the ultraviolet curable resin (C), the amount of the curing agent added to 1-propanol was the same as in Example 5 with respect to the amount of the ultraviolet curable resin (C) added. The amount was set to 5% by mass, and the amount added was increased as compared with the case of Example 5.
Table 3 shows the types of each compounding component and the content in the coating layer composition (C-2).

(Manufacturing and evaluation of laminate)
A laminate was produced and evaluated by the same method as in Example 1 except that the coating layer composition (C-2) obtained above was used. The results are shown in Tables 4 and 5.

[Example 7]
(Manufacturing of composition for coating layer)
Same as in Example 5 except that the content of the ultraviolet curable resin (C) in the coating layer composition was 67.6% by mass instead of 29.6% by mass during the production of the coating layer composition. By the method, a coating layer composition (C-3) was obtained. In addition, with respect to the increase in the content of the ultraviolet curable resin (C), the amount of the curing agent added to 1-propanol was the same as in Example 5 with respect to the amount of the ultraviolet curable resin (C) added. The amount was set to 5% by mass, and the amount added was increased as compared with the case of Example 5.
Table 3 shows the types of each compounding component and the content in the coating layer composition (C-3).

(Manufacturing and evaluation of laminate)
A laminate was produced and evaluated by the same method as in Example 1 except that the coating layer composition (C-3) obtained above was used. The results are shown in Tables 4 and 5.

[Example 8]
(Manufacturing of composition for coating layer)
Curing agent (2-hirodoxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one, Ciba Japan, Inc. under the condition of 25 ° C. "IRGACURE 127") manufactured by (IRGACURE127) was added to 1-propanol and dissolved to obtain a 1-propanol solution. The amount of the curing agent added was set to be 5% by mass with respect to the amount of the ultraviolet curable resin (D) described later.
Next, the ultraviolet curable resin (D) was added to the 1-propanol solution whose temperature was adjusted to 45 ° C., and the mixture was stirred to obtain a coating layer composition (D-1). The amount of the ultraviolet curable resin (D) added at this time was such that the content of the ultraviolet curable resin (D) in the coating layer composition (D-1) was 29.6% by mass.
Table 3 shows the types of each compounding component and the content in the coating layer composition (D-1).

(Manufacturing and evaluation of laminate)
A laminate was produced and evaluated by the same method as in Example 1 except that the coating layer composition (D-1) obtained above was used. The results are shown in Tables 4 and 5.

[Example 9]
(Manufacturing of composition for coating layer)
Same as Example 8 except that the content of the ultraviolet curable resin (D) in the coating layer composition was changed to 48.8% by mass instead of 29.6% by mass during the production of the coating layer composition. By the method, a coating layer composition (D-2) was obtained. In addition, with respect to the increase in the content of the ultraviolet curable resin (D), the amount of the curing agent added to 1-propanol was the same as in Example 8 with respect to the amount of the ultraviolet curable resin (D) added. The amount was set to 5% by mass, and the amount added was increased as compared with the case of Example 8.
Table 3 shows the types of each compounding component and the content in the coating layer composition (D-2).

(Manufacturing and evaluation of laminate)
A laminate was produced and evaluated by the same method as in Example 1 except that the coating layer composition (D-2) obtained above was used. The results are shown in Tables 4 and 5.

[Example 10]
(Manufacturing of composition for coating layer)
Same as in Example 8 except that the content of the ultraviolet curable resin (D) in the coating layer composition was 67.6% by mass instead of 29.6% by mass during the production of the coating layer composition. By the method, a coating layer composition (D-3) was obtained. In addition, with respect to the increase in the content of the ultraviolet curable resin (D), the amount of the curing agent added to 1-propanol was the same as in Example 8 with respect to the amount of the ultraviolet curable resin (D) added. The amount was set to 5% by mass, and the amount added was increased as compared with the case of Example 8.
Table 3 shows the types of each compounding component and the content in the coating layer composition (D-3).

(Manufacturing and evaluation of laminate)
A laminate was produced and evaluated by the same method as in Example 1 except that the coating layer composition (D-3) obtained above was used. The results are shown in Tables 4 and 5.

[Example 11]
(Manufacturing of composition for coating layer)
Curing agent (2-hirodoxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one, Ciba Japan, Inc. under the condition of 25 ° C. "IRGACURE 127") manufactured by (IRGACURE127) was added to 1-propanol and dissolved to obtain a 1-propanol solution. The amount of the curing agent added was set to be 5% by mass with respect to the amount of the ultraviolet curable resin (E) described later.
Next, an ultraviolet curable resin (E) was added to the 1-propanol solution whose temperature was adjusted to 45 ° C., and the mixture was stirred to obtain a coating layer composition (E-1). The amount of the ultraviolet curable resin (E) added at this time was such that the content of the ultraviolet curable resin (E) in the coating layer composition (E-1) was 29.6% by mass.
Table 3 shows the types of each compounding component and the content in the coating layer composition (E-1).

(Manufacturing and evaluation of laminate)
A laminate was produced and evaluated by the same method as in Example 1 except that the coating layer composition (E-1) obtained above was used. The results are shown in Tables 4 and 5.

[Example 12]
(Manufacturing of composition for coating layer)
Same as in Example 11 except that the content of the ultraviolet curable resin (E) in the coating layer composition was changed to 48.8% by mass instead of 29.6% by mass during the production of the coating layer composition. By the method, a composition for a coating layer (E-2) was obtained. In addition, with respect to the increase in the content of the ultraviolet curable resin (E), the amount of the curing agent added to 1-propanol was the same as in Example 11 with respect to the amount of the ultraviolet curable resin (E) added. The amount was set to 5% by mass, and the amount added was increased as compared with the case of Example 11.
Table 3 shows the types of each compounding component and the content in the coating layer composition (E-2).

(Manufacturing and evaluation of laminate)
A laminate was produced and evaluated by the same method as in Example 1 except that the coating layer composition (E-2) obtained above was used. The results are shown in Tables 4 and 5.

[Example 13]
(Manufacturing of composition for coating layer)
Hardener (2-hirodoxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one, Ciba Japan, Inc. under the condition of 25 ° C. "IRGACURE 127") was added to 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol) and dissolved to obtain a diacetone alcohol solution. The amount of the curing agent added was set to be 5% by mass with respect to the amount of the ultraviolet curable resin (F) described later.
Next, the ultraviolet curable resin (F) was added to the diacetone alcohol solution whose temperature was adjusted to 45 ° C., and the mixture was stirred to obtain a coating layer composition (F-1). The amount of the ultraviolet curable resin (F) added at this time was such that the content of the ultraviolet curable resin (F) in the coating layer composition (F-1) was 29.6% by mass.
Table 3 shows the types of each compounding component and the content in the coating layer composition (F-1).

(Manufacturing and evaluation of laminate)
A laminate was produced and evaluated by the same method as in Example 1 except that the coating layer composition (F-1) obtained above was used. The results are shown in Tables 4 and 5.

[Example 14]
(Manufacturing of composition for coating layer)
Same as Example 13 except that the content of the ultraviolet curable resin (F) in the coating layer composition was changed to 48.8% by mass instead of 29.6% by mass during the production of the coating layer composition. By the method, a coating layer composition (F-2) was obtained. In addition, with respect to the increase in the content of the ultraviolet curable resin (F), the amount of the curing agent added to diacetone alcohol was the same as in Example 13 with respect to the amount of the ultraviolet curable resin (F) added. The amount was set to 5% by mass, and the amount added was increased as compared with the case of Example 13.
Table 3 shows the types of each compounding component and the content in the coating layer composition (F-2).

(Manufacturing and evaluation of laminate)
A laminate was produced and evaluated by the same method as in Example 1 except that the coating layer composition (F-2) obtained above was used. The results are shown in Tables 4 and 5.

[Example 15]
(Manufacturing of composition for coating layer)
Curing agent (2-hirodoxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one, Ciba Japan, Inc. under the condition of 25 ° C. "IRGACURE 127") and 1,2,3-benzotriazole ("BT-120" manufactured by Johoku Chemical Co., Ltd., hereinafter may be abbreviated as "1,2,3-BT") are 4-hydroxy. It was added to -4-methyl-2-pentanone (diacetone alcohol) and dissolved to obtain a diacetone alcohol solution. The amount of the curing agent added is 5% by mass with respect to the amount of the ultraviolet curable resin (F) described later, and the amount of 1,2,3-BT added is the amount of the ultraviolet curable resin (F) described later. The amount was set to 5% by mass with respect to the amount of F) added.
Next, the ultraviolet curable resin (F) was added to the diacetone alcohol solution whose temperature was adjusted to 45 ° C., and the mixture was stirred to obtain a coating layer composition (F-3). The amount of the ultraviolet curable resin (F) added at this time was such that the content of the ultraviolet curable resin (F) in the coating layer composition (F-3) was 29.1% by mass. 1,2,3-BT are migration inhibitors.
Table 3 shows the types of each compounding component and the content in the coating layer composition (F-3).

(Manufacturing and evaluation of laminate)
A laminate was produced and evaluated by the same method as in Example 1 except that the coating layer composition (F-3) obtained above was used. The results are shown in Tables 4 and 5.

[Example 16]
(Manufacturing of composition for coating layer)
Hardener (2-hirodoxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one, Ciba Japan, Inc. under the condition of 25 ° C. "IRGACURE 127") and 5-methyl-1H-benzotriazole (manufactured by Wako Junyaku Co., Ltd., hereinafter may be abbreviated as "5-MBT") are 4-hydroxy-4-methyl-2-pentanone. It was added to (diacetone alcohol) and dissolved to obtain a diacetone alcohol solution. The amount of the curing agent added is 5% by mass with respect to the amount of the ultraviolet curable resin (F) described later, and the amount of 5-MBT added is the amount of the ultraviolet curable resin (F) described later. The amount was set to be 5% by mass with respect to the amount.
Next, the ultraviolet curable resin (F) was added to the diacetone alcohol solution whose temperature was adjusted to 45 ° C., and the mixture was stirred to obtain a coating layer composition (F-4). The amount of the ultraviolet curable resin (F) added at this time was such that the content of the ultraviolet curable resin (F) in the coating layer composition (F-4) was 29.1% by mass. 5-MBT is a migration inhibitor.
Table 3 shows the types of each compounding component and the content in the coating layer composition (F-4).

(Manufacturing and evaluation of laminate)
A laminate was produced and evaluated by the same method as in Example 1 except that the coating layer composition (F-4) obtained above was used. The results are shown in Tables 4 and 5.

[Comparative Example 1]
(Manufacturing of composition for coating layer)
Curing agent (2-hirodoxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one, Ciba Japan, Inc. under the condition of 25 ° C. "IRGACURE 127") manufactured by (IRGACURE127) was added to 1-propanol and dissolved to obtain a 1-propanol solution. The amount of the curing agent added was set to be 5% by mass with respect to the amount of the ultraviolet curable resin (G) described later.
Next, an ultraviolet curable resin (G) was added to the 1-propanol solution whose temperature was adjusted to 45 ° C., and the mixture was stirred to obtain a coating layer composition (G-1). The amount of the ultraviolet curable resin (G) added at this time was such that the content of the ultraviolet curable resin (G) in the coating layer composition (G-1) was 48.8% by mass.
Table 3 shows the types of each compounding component and the content in the coating layer composition (G-1).

(Manufacturing and evaluation of laminate)
A laminate was produced and evaluated by the same method as in Example 1 except that the coating layer composition (G-1) obtained above was used. The results are shown in Tables 4 and 5.

[Comparative Example 2]
(Manufacturing of composition for coating layer)
Curing agent (2-hirodoxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one, Ciba Japan, Inc. under the condition of 25 ° C. "IRGACURE 127") manufactured by (IRGACURE 127) was added to cyclohexanone and dissolved to obtain a cyclohexanone solution. The amount of the curing agent added was set to be 5% by mass with respect to the amount of the ultraviolet curable resin (G) described later.
Next, an ultraviolet curable resin (G) was added to the cyclohexanone solution whose temperature was adjusted to 45 ° C., and the mixture was stirred to obtain a coating layer composition (G-2). The amount of the ultraviolet curable resin (G) added at this time was such that the content of the ultraviolet curable resin (G) in the coating layer composition (G-2) was 29.6% by mass.
Table 3 shows the types of each compounding component and the content in the coating layer composition (G-2).

(Manufacturing and evaluation of laminate)
A laminate was produced and evaluated by the same method as in Example 1 except that the coating layer composition (G-2) obtained above was used. The results are shown in Tables 4 and 5.

The following shows examples in which a migration inhibitor and a surfactant are used as compounding components of the coating layer composition.
In Examples 17 to 29, the "silver ink composition 2" shown below was used.
The "silver ink composition 2" is a composition showing the same haze as the "silver ink composition" described in the section of Example 1 above.

Table 7 shows the surfactants used in the following examples.
Specific examples of the surfactant include Neos's "Futagent 610FM (nonionic, fluorine-containing group (hydrophilic group / lipophilic group) -containing oligomer)" and Neos's "Futergent 602A (nonionic, lipophilic group) -containing oligomer)". Fluorine group (hydrophilic group / lipophilic group) UV-reactive group-containing oligomer) ”, Neos Co., Ltd.“ Surfactant 650AC (nonionic, fluorine-containing group (hydrophilic group / lipophilic group) UV-reactive group-containing oligomer) , And "Futergent 601AD (nonionic, fluorine-containing group (hydrophilic group / lipophilic group) UV-reactive group-containing oligomer)" manufactured by Neos Co., Ltd. was used.

<Manufacturing and evaluation of laminate>
[Example 17, Example 18]
(Manufacturing of Silver Ink Composition 2)
2-Ethylhexylamine (1.45 times the molar amount of 2-methylacetate silver acetate described later) and n-hexane (1.63 times the molar amount of 2-methylacetate silver acetate described later) in a beaker. Was added in this order, and 52.9 g of silver 2-methylacetate acetate was added to the beaker so that the liquid temperature became 50 ° C. or lower while rotating and stirring the mechanical stirrer.
After the addition of 2-methylacetate silver is completed, formic acid (0.5 times the molar amount of 2-methylacetate silver) is added dropwise in a beaker over 10 minutes while maintaining the same state. Then, after the dropping of formic acid was completed, the mixture was further stirred for 1.5 hours as it was.
Next, the acetylene alcohol (2), 3,5-dimethyl-1-hexin-3-ol (hereinafter, may be abbreviated as "DMHO") (0.032 times by molar amount with respect to silver 2-methylacetate acetate). ) And 4-ethyl-1-octyne-3-ol (hereinafter, may be abbreviated as "EOO") which is acetylene alcohol (2) (0.004 times by molar amount with respect to silver 2-methylacetate acetate). The mixture was added to the beaker, and after the addition was completed, the mixture was further stirred as it was for 5 minutes to obtain a silver ink composition.
As the EOO, one manufactured by Tokyo Chemical Industry Co., Ltd. was used.
Table 6 shows the types and mixing ratios of each compounding ingredient.
In Table 6, the “nitrogen-containing compound (molar ratio)” refers to the amount of the nitrogen-containing compound (number of moles) per mole of the material for forming metallic silver ([number of moles of nitrogen-containing compound] / [metal]. Number of moles of silver forming material]).
Similarly, the "reducing agent (molar ratio)" is also the amount of the reducing agent compounded per mole of the metal silver forming material (the number of moles) ([the number of moles of the reducing agent] / [the mole of the metal silver forming material]. Number]).
Similarly, "acetylene alcohol (2) (molar ratio)" also contains the amount (molar number) of acetylene alcohol (2) per mole of the material for forming metallic silver ([the number of moles of acetylene alcohol (2)]]. / [Number of moles of metallic silver forming material]).
Similarly, the "solvent (molar ratio)" is the amount of the solvent compounded per mole of the metallic silver forming material (the number of moles) ([the number of moles of the solvent] / [the number of moles of the metallic silver forming material]). Means.

(Manufacturing of composition for coating layer)
Curing agent (2-hirodoxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one, Ciba Japan, Inc. under the condition of 25 ° C. "IRGACURE 127") and the above 5-MBT in a mixed solvent of 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol) and ethylene glycol monopropyl ether (diacetone alcohol and ethylene glycol mono in the mixed solvent). The mixture was added to a mixed mass ratio of propyl ether to 3: 7) and dissolved to obtain a diacetone alcohol / ethylene glycol monopropyl ether solution. The amount of the curing agent added is 5% by mass with respect to the amount of the ultraviolet curable resin (F) described later, and the amount of 5-MBT added is the amount of the ultraviolet curable resin (F) described later. The amount was set to be 5% by mass with respect to the amount.
Next, an ultraviolet curable resin (F) was added to the diacetone alcohol / ethylene glycol monopropyl ether solution whose temperature was adjusted to 45 ° C., and the mixture was stirred, and then Futergent 610FM was further added to form a coating layer composition. (F-5) was obtained. The amount of the ultraviolet curable resin (F) added at this time was such that the content of the ultraviolet curable resin (F) in the coating layer composition (F-5) was 20% by mass. The amount of the footagent 610FM added was such that the content of the footagent 610FM in the coating layer composition (F-5) was 0.3% by mass. 5-MBT is a migration inhibitor.
Table 8 shows the types of each compounding component and the content in the coating layer composition (F-5).
In addition, the description of "-" in the column of the compounding component in Table 8 means that the component is not compounded.

(Manufacturing and evaluation of laminate)
The present invention relates to Examples 17 and 18 in the same manner as in Example 1 except that the coating layer composition (F-5) obtained above was used and the silver ink composition 2 was used. The laminate was manufactured and evaluated. The results are shown in Tables 9 and 10.
In Example 17, the laminate was prepared so that the thickness of the coating layer was 10 μm at the maximum.
Further, in Example 18, a laminate was prepared so that the thickness of the coating layer was 5 μm at the maximum.

<Manufacturing and evaluation of laminate>
[Example 19, Example 20]
(Manufacturing of composition for coating layer)
Curing agent (2-hirodoxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one, Ciba Japan, Inc. under the condition of 25 ° C. "IRGACURE 127") and the above 5-MBT in a mixed solvent of 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol) and ethylene glycol monopropyl ether (diacetone alcohol and ethylene glycol mono in the mixed solvent). The mixture was added to a mixed mass ratio of propyl ether to 3: 7) and dissolved to obtain a diacetone alcohol / ethylene glycol monopropyl ether solution. The amount of the curing agent added is 5% by mass with respect to the amount of the ultraviolet curable resin (F) described later, and the amount of 5-MBT added is the amount of the ultraviolet curable resin (F) described later. The amount was set to be 5% by mass with respect to the amount.
Next, an ultraviolet curable resin (F) was added to the diacetone alcohol / ethylene glycol monopropyl ether solution whose temperature was adjusted to 45 ° C., and the mixture was stirred, and then Futagent 602A was further added to form a coating layer composition. (F-6) was obtained. The amount of the ultraviolet curable resin (F) added at this time was such that the content of the ultraviolet curable resin (F) in the coating layer composition (F-6) was 20% by mass. The amount of the footagent 602A added was such that the content of the footagent 602A in the coating layer composition (F-6) was 0.3% by mass. 5-MBT is a migration inhibitor.
Table 8 shows the types of each compounding component and the content in the coating layer composition (F-6).

(Manufacturing and evaluation of laminate)
The present invention relates to Examples 19 and 20 in the same manner as in Example 1 except that the coating layer composition (F-6) obtained above was used and the silver ink composition 2 was used. The laminate was manufactured and evaluated. The results are shown in Tables 9 and 10.
In Example 19, the laminate was prepared so that the thickness of the coating layer was 10 μm at the maximum.
Further, in Example 20, a laminate was prepared so that the thickness of the coating layer was 5 μm at the maximum.

[Example 21]
(Manufacturing of composition for coating layer)
Curing agent (2-hirodoxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one, Ciba Japan, Inc. under the condition of 25 ° C. "IRGACURE 127") and the above 5-MBT in a mixed solvent of 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol) and ethylene glycol monopropyl ether (diacetone alcohol and ethylene glycol mono in the mixed solvent). The mixture was added to a mixed mass ratio of propyl ether to 3: 7) and dissolved to obtain a diacetone alcohol / ethylene glycol monopropyl ether solution. The amount of the curing agent added is 5% by mass with respect to the amount of the ultraviolet curable resin (F) described later, and the amount of 5-MBT added is the amount of the ultraviolet curable resin (F) described later. The amount was set to be 5% by mass with respect to the amount.
Next, an ultraviolet curable resin (F) was added to the diacetone alcohol / ethylene glycol monopropyl ether solution whose temperature was adjusted to 45 ° C., and the mixture was stirred, and then Futagent 602A was further added to form a coating layer composition. (F-7) was obtained. The amount of the ultraviolet curable resin (F) added at this time was such that the content of the ultraviolet curable resin (F) in the coating layer composition (F-7) was 20% by mass. The amount of the footagent 602A added was such that the content of the footagen 602A in the coating layer composition (F-7) was 0.1% by mass. 5-MBT is a migration inhibitor.
Table 8 shows the types of each compounding component and the content in the coating layer composition (F-7).

(Manufacturing and evaluation of laminate)
The laminate according to Example 21 was produced by the same method as in Example 1 except that the coating layer composition (F-7) obtained above was used and the silver ink composition 2 was used. And evaluated. The results are shown in Tables 9 and 10.
In Example 21, the laminate was prepared so that the thickness of the coating layer was 5 μm at the maximum.

[Example 22]
(Manufacturing of composition for coating layer)
Curing agent (2-hirodoxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one, Ciba Japan, Inc. under the condition of 25 ° C. "IRGACURE 127") and the above 5-MBT in a mixed solvent of 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol) and ethylene glycol monopropyl ether (diacetone alcohol and ethylene glycol mono in the mixed solvent). The mixture was added to a mixed mass ratio of propyl ether to 3: 7) and dissolved to obtain a diacetone alcohol / ethylene glycol monopropyl ether solution. The amount of the curing agent added is 5% by mass with respect to the amount of the ultraviolet curable resin (F) described later, and the amount of 5-MBT added is the amount of the ultraviolet curable resin (F) described later. The amount was set to be 5% by mass with respect to the amount.
Next, an ultraviolet curable resin (F) was added to the diacetone alcohol / ethylene glycol monopropyl ether solution whose temperature was adjusted to 45 ° C., and the mixture was stirred, and then Futagent 602A was further added to form a coating layer composition. (F-8) was obtained. The amount of the ultraviolet curable resin (F) added at this time was such that the content of the ultraviolet curable resin (F) in the coating layer composition (F-8) was 20% by mass. The amount of the footagent 602A added was such that the content of the footagen 602A in the coating layer composition (F-8) was 0.05% by mass. 5-MBT is a migration inhibitor.
Table 8 shows the types of each compounding component and the content in the coating layer composition (F-8).

(Manufacturing and evaluation of laminate)
The laminate according to Example 22 was produced by the same method as in Example 1 except that the coating layer composition (F-8) obtained above was used and the silver ink composition 2 was used. And evaluated. The results are shown in Tables 9 and 10.
In Example 22, the laminate was prepared so that the thickness of the coating layer was 5 μm at the maximum.

[Example 23]
(Manufacturing of composition for coating layer)
Curing agent (2-hirodoxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one, Ciba Japan, Inc. under the condition of 25 ° C. "IRGACURE 127") and the above 5-MBT in a mixed solvent of 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol) and ethylene glycol monopropyl ether (diacetone alcohol and ethylene glycol mono in the mixed solvent). The mixture was added to a mixed mass ratio of propyl ether to 3: 7) and dissolved to obtain a diacetone alcohol / ethylene glycol monopropyl ether solution. The amount of the curing agent added is 5% by mass with respect to the amount of the ultraviolet curable resin (F) described later, and the amount of 5-MBT added is the amount of the ultraviolet curable resin (F) described later. The amount was set to be 5% by mass with respect to the amount.
Next, an ultraviolet curable resin (F) was added to the diacetone alcohol / ethylene glycol monopropyl ether solution whose temperature was adjusted to 45 ° C., and the mixture was stirred, and then Futagent 602A was further added to form a coating layer composition. (F-9) was obtained. The amount of the ultraviolet curable resin (F) added at this time was such that the content of the ultraviolet curable resin (F) in the coating layer composition (F-9) was 20% by mass. The amount of the footagent 602A added was such that the content of the footagent 602A in the coating layer composition (F-9) was 0.01% by mass. 5-MBT is a migration inhibitor.
Table 8 shows the types of each compounding component and the content in the coating layer composition (F-9).

(Manufacturing and evaluation of laminate)
The laminate according to Example 23 was produced by the same method as in Example 1 except that the coating layer composition (F-9) obtained above was used and the silver ink composition 2 was used. And evaluated. The results are shown in Tables 9 and 10.
In Example 23, the laminate was prepared so that the thickness of the coating layer was 5 μm at the maximum.

[Example 24, Example 25]
(Manufacturing of composition for coating layer)
Curing agent (2-hirodoxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one, Ciba Japan, Inc. under the condition of 25 ° C. "IRGACURE 127") and the above 5-MBT in a mixed solvent of 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol) and ethylene glycol monopropyl ether (diacetone alcohol and ethylene glycol mono in the mixed solvent). The mixture was added to a mixed mass ratio of propyl ether to 3: 7) and dissolved to obtain a diacetone alcohol / ethylene glycol monopropyl ether solution. The amount of the curing agent added is 5% by mass with respect to the amount of the ultraviolet curable resin (F) described later, and the amount of 5-MBT added is the amount of the ultraviolet curable resin (F) described later. The amount was set to be 5% by mass with respect to the amount.
Next, an ultraviolet curable resin (F) was added to the diacetone alcohol solution whose temperature was adjusted to 45 ° C., and the mixture was stirred to obtain a coating layer composition (F-10). The amount of the ultraviolet curable resin (F) added at this time was such that the content of the ultraviolet curable resin (F) in the coating layer composition (F-10) was 20% by mass. 5-MBT is a migration inhibitor.
Table 8 shows the types of each compounding component and the content in the coating layer composition (F-10).

(Manufacturing and evaluation of laminate)
A laminate was produced and evaluated by the same method as in Example 1 in that the coating layer composition (F-10) obtained above and the silver ink composition 2 were used. The results are shown in Tables 9 and 10.
In Example 24, the laminate was prepared so that the thickness of the coating layer was 10 μm at the maximum.
Further, in Example 25, a laminate was prepared so that the thickness of the coating layer was 5 μm at the maximum.

[Example 26]
(Manufacturing of composition for coating layer)
Curing agent (2-hirodoxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one, Ciba Japan, Inc. under the condition of 25 ° C. "IRGACURE 127") and the above 5-MBT in a mixed solvent of 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol) and ethylene glycol monopropyl ether (diacetone alcohol and ethylene glycol mono in the mixed solvent). The mixture was added to a mixed mass ratio of propyl ether to 3: 7) and dissolved to obtain a diacetone alcohol / ethylene glycol monopropyl ether solution. The amount of the curing agent added is 5% by mass with respect to the amount of the ultraviolet curable resin (F) described later, and the amount of 5-MBT added is the amount of the ultraviolet curable resin (F) described later. The amount was set to be 5% by mass with respect to the amount.
Next, an ultraviolet curable resin (F) was added to the diacetone alcohol / ethylene glycol monopropyl ether solution whose temperature was adjusted to 45 ° C., and the mixture was stirred, and then Futergent 650AC was further added to form a coating layer composition. (F-11) was obtained. The amount of the ultraviolet curable resin (F) added at this time was such that the content of the ultraviolet curable resin (F) in the coating layer composition (F-11) was 20% by mass. The amount of Futergent 650AC added was such that the content of Futergent 650AC in the coating layer composition (F-11) was 0.2% by mass. 5-MBT is a migration inhibitor.
Table 8 shows the types of each compounding component and the content in the coating layer composition (F-11).

(Manufacturing and evaluation of laminate)
The laminate according to Example 26 was produced by the same method as in Example 1 except that the coating layer composition (F-11) obtained above was used and the silver ink composition 2 was used. And evaluated. The results are shown in Tables 9 and 10.
In Example 26, the laminate was prepared so that the thickness of the coating layer was 5 μm at the maximum.

[Example 27]
(Manufacturing of composition for coating layer)
Curing agent (2-hirodoxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one, Ciba Japan, Inc. under the condition of 25 ° C. "IRGACURE 127") and the above 5-MBT in a mixed solvent of 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol) and ethylene glycol monopropyl ether (diacetone alcohol and ethylene glycol mono in the mixed solvent). The mixture was added to a mixed mass ratio of propyl ether to 3: 7) and dissolved to obtain a diacetone alcohol / ethylene glycol monopropyl ether solution. The amount of the curing agent added is 5% by mass with respect to the amount of the ultraviolet curable resin (F) described later, and the amount of 5-MBT added is the amount of the ultraviolet curable resin (F) described later. The amount was set to be 5% by mass with respect to the amount.
Next, an ultraviolet curable resin (F) was added to the diacetone alcohol / ethylene glycol monopropyl ether solution whose temperature was adjusted to 45 ° C., and the mixture was stirred, and then Futergent 650AC was further added to form a coating layer composition. (F-12) was obtained. The amount of the ultraviolet curable resin (F) added at this time was such that the content of the ultraviolet curable resin (F) in the coating layer composition (F-12) was 20% by mass. The amount of Futagent 650AC added was such that the content of Futagent 650AC in the coating layer composition (F-12) was 0.1% by mass. 5-MBT is a migration inhibitor.
Table 8 shows the types of each compounding component and the content in the coating layer composition (F-12).

(Manufacturing and evaluation of laminate)
The laminate according to Example 27 was produced by the same method as in Example 1 except that the coating layer composition (F-12) obtained above was used and the silver ink composition 2 was used. And evaluated. The results are shown in Tables 9 and 10.
In Example 27, the laminate was prepared so that the thickness of the coating layer was 5 μm at the maximum.

[Example 28]
(Manufacturing of composition for coating layer)
Curing agent (2-hirodoxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one, Ciba Japan, Inc. under the condition of 25 ° C. "IRGACURE 127") and the above 5-MBT in a mixed solvent of 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol) and ethylene glycol monopropyl ether (diacetone alcohol and ethylene glycol mono in the mixed solvent). The mixture was added to a mixed mass ratio of propyl ether to 3: 7) and dissolved to obtain a diacetone alcohol / ethylene glycol monopropyl ether solution. The amount of the curing agent added is 5% by mass with respect to the amount of the ultraviolet curable resin (F) described later, and the amount of 5-MBT added is the amount of the ultraviolet curable resin (F) described later. The amount was set to be 5% by mass with respect to the amount.
Next, an ultraviolet curable resin (F) was added to the diacetone alcohol / ethylene glycol monopropyl ether solution whose temperature was adjusted to 45 ° C., and the mixture was stirred, and then Futergent 601AD was further added to form a coating layer composition. (F-13) was obtained. The amount of the ultraviolet curable resin (F) added at this time was such that the content of the ultraviolet curable resin (F) in the coating layer composition (F-13) was 20% by mass. The amount of the footagent 601AD added was such that the content of the footagen 601AD in the coating layer composition (F-13) was 0.2% by mass. 5-MBT is a migration inhibitor.
Table 8 shows the types of each compounding component and the content in the coating layer composition (F-13).

(Manufacturing and evaluation of laminate)
The laminate according to Example 28 was produced by the same method as in Example 1 except that the coating layer composition (F-13) obtained above was used and the silver ink composition 2 was used. And evaluated. The results are shown in Tables 9 and 10.
In Example 28, the laminate was prepared so that the thickness of the coating layer was 5 μm at the maximum.

[Example 29]
(Manufacturing of composition for coating layer)
Curing agent (2-hirodoxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one, Ciba Japan, Inc. under the condition of 25 ° C. "IRGACURE 127") and the above 5-MBT in a mixed solvent of 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol) and ethylene glycol monopropyl ether (diacetone alcohol and ethylene glycol mono in the mixed solvent). The mixture was added to a mixed mass ratio of propyl ether to 3: 7) and dissolved to obtain a diacetone alcohol / ethylene glycol monopropyl ether solution. The amount of the curing agent added is 5% by mass with respect to the amount of the ultraviolet curable resin (F) described later, and the amount of 5-MBT added is the amount of the ultraviolet curable resin (F) described later. The amount was set to be 5% by mass with respect to the amount.
Next, an ultraviolet curable resin (F) was added to the diacetone alcohol / ethylene glycol monopropyl ether solution whose temperature was adjusted to 45 ° C., and the mixture was stirred, and then Futergent 601AD was further added to form a coating layer composition. (F-14) was obtained. The amount of the ultraviolet curable resin (F) added at this time was such that the content of the ultraviolet curable resin (F) in the coating layer composition (F-14) was 20% by mass. The amount of the footagent 601AD added was such that the content of the footagen 601AD in the coating layer composition (F-14) was 0.1% by mass. 5-MBT is a migration inhibitor.
Table 8 shows the types of each compounding component and the content in the coating layer composition (F-14).

(Manufacturing and evaluation of laminate)
The laminate according to Example 29 was produced by the same method as in Example 1 except that the coating layer composition (F-14) obtained above was used and the silver ink composition 2 was used. And evaluated. The results are shown in Tables 9 and 10.
In Example 29, the laminate was prepared so that the thickness of the coating layer was 5 μm at the maximum.

As is clear from the above results, the laminates of Examples 1 to 16 had a small haze H ₀ and had favorable optical characteristics. The laminates of Examples 1 to 16 have a small haze change rate at each stage, for example, the haze change rate ΔH ₁₁₈ (%) is 100% or less, and the laminates are even under moist heat conditions. It was confirmed that the change in the overall haze was suppressed and the favorable optical characteristics were maintained.
As described above, the laminates of Examples 1 to 16 are formed by coating and curing the coating layer composition, and are preferable under moist heat conditions regardless of the presence or absence of additives in the coating layer. It had optical characteristics.
Further, in the laminates of Examples 1 to 16, the coating layer had various pencil hardness depending on the material of the coating layer.

Further, as is clear from the above results, the laminates of Examples 17 to 29 had a small haze H ₀ and had preferable optical characteristics. The laminates of Examples 17 to 29 have a small haze change rate at each stage, for example, the haze change rate ΔH ₁₁₈ (%) is 100% or less, and the laminates are even under moist heat conditions. It was confirmed that the change in the overall haze was suppressed and the favorable optical characteristics were maintained.
As described above, in the laminates of Examples 17 to 29, the coating layer is formed by coating and curing the composition for the coating layer, and the coating layer contains an additive, but under moist heat conditions. However, it had preferable optical characteristics.
That is, when the coating layer composition contains a migration inhibitor, even when the coating layer composition contains a migration inhibitor and a surfactant, excellent optical properties are maintained in the laminate of the present invention. I was able to confirm that.
Further, in the laminates of Examples 17 to 29, the coating layers all had a pencil hardness of H to 3H.

On the other hand, the laminate of Comparative Example 1 had a small haze H ₀ and had favorable optical characteristics at the initial stage, but the haze change rate ΔH ₁₁₈ (%) exceeded 100%, and the heat and humidity were high. Under the conditions, the haze of the entire laminate changed significantly, and the optical characteristics deteriorated significantly.
The laminate of Comparative Example 2 had a large haze H ₀ , was inferior in light transmission, and was already inferior in optical characteristics at the initial stage. Further, although the change in haze of the entire laminate under moist heat conditions was suppressed, the change in haze was larger than that in the case of the laminates of Examples 1 to 16.

The present invention can be used in various electronic devices having a conductive layer on a base material, and is suitable for use in optical applications such as touch panels and optical displays, for example.

1, 2, ... Laminated body 11 ... Base material 11a ... One main surface (surface, first main surface) of the base material
11b ... The other main surface of the base material (back surface, second main surface)
12, 22 ... Conductive layer 12a, 22a ... Conductive layer surface 13, 23 ... Coating layer 13a, 23a ... Coating layer surface

Claims (2)

It is a laminated body
With the base material
The conductive layer provided on the base material and
A coating layer provided on the conductive layer is provided.
The laminate having a first haze H ₀ of 3.0% or less measured from the coating layer side was treated in an atmosphere of a temperature of 85 ° C. and a relative humidity of 85% for 118 hours, and then the coating layer side was used. When measuring the second haze H ₁₁₈ of the laminate,
Equation I ₁₁₈ : The haze change rate ΔH _{118 of the} laminate calculated by ΔH ₁₁₈ (%) = (H ₁₁₈ −H ₀ ) / H ₀ × 100 is 100% or less.
The coating layer has a pencil hardness of any of HB, F, H, 2H and 3H .
The conductive layer is a laminate made of silver or copper . The laminate according to claim 1, wherein the conductive layer is directly contacted and laminated on the base material, and the coating layer is directly contacted and laminated on the conductive layer.

Images