JP7015198B2 - Laminate - Google Patents

Description

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

Laminates in which a conductive layer is provided on a substrate are 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 laminated body 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. When the laminate provided with such a coating layer is used, for example, in an optical application, it is required that the change in haze is suppressed even in a harsh environment.

As a laminated film suitable for forming such a coating layer and having a small change rate of haze, a film having coating layers on both sides of a polyester film is bonded to both sides of an adhesive layer to be exposed. The haze change rate of the laminated film before and after 100 hours of wet heat treatment in an atmosphere of 85 ° C. and 85% RH is 1. A laminated film having a content of 5% or less is disclosed (see Patent Document 1).

Japanese Unexamined Patent Publication No. 2015-0833335

However, when the laminated film described in Patent Document 1 is used to provide a coating layer on the conductive layer, the laminated film is interposed via an intermediate layer such as an adhesive layer or an adhesive layer in addition to the step of forming the coating layer. 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. Further, although this laminated film has a small haze change rate before and after the wet heat treatment under specific conditions, it is not clear whether the haze change is suppressed under other harsh conditions. For example, as a harsh condition other than the moist heat condition, a condition where the temperature changes drastically is typical. On the other hand, it is unclear whether or not the change in haze of the laminated body is suppressed when the thermal shock test is performed on the entire laminated body to which the laminated film described in Patent Document 1 is attached to the conductive layer. be.

The present invention has been made in view of the above circumstances, and can be manufactured as a laminated body in which a base material, a conductive layer, and a coating layer are laminated in this order without performing a step of attaching a already formed coating layer. It is an object of the present invention to provide a laminated body in which a change in haze of the entire laminated body is suppressed even after a thermal shock test.

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. In the laminated body, the first haze H ₀ measured from the coating layer side is 3.0% or less, and the laminated body is stored at a temperature of 80 ° C. for 30 minutes, and then the laminated body is stored. Formula I ₂₀₀ when the second haze H200 of the laminate after ₂₀₀ cycles of the thermal shock test was measured in a thermal shock test, where the test of storage at a temperature of -30 ° C for 30 minutes was defined as one cycle. : The haze change rate ΔH ₂₀₀ of the laminate calculated by ΔH ₂₀₀ (%) = (H ₂₀₀ −H ₀ ) / H ₀ × 100 is 70% or less.

The conductive layer may be directly contacted and laminated with the substrate, and the coating layer may be directly contacted and laminated with the conductive layer.

The coating layer may contain at least one of a surfactant and a migration inhibitor.

The surfactant may be a surfactant having a UV reactive group.

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, it can be manufactured without performing the step of attaching the formed coating layer, and the base material and the conductive layer can be manufactured. By constructing a structure in which the coating layer is directly laminated on the layer, a laminated body capable of suppressing deterioration of haze of the laminated body is provided even after a thermal shock test in a layer structure including a conductive layer.

It is sectional drawing which shows typically the laminated body which concerns on one Embodiment of this invention. It is sectional drawing which shows typically the laminated body which concerns on other embodiment of this invention. It is sectional drawing for schematically explaining the manufacturing method of the laminated body shown in FIG. 1.

<< Laminated body >>
The laminate according to the embodiment 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, and the laminate is the coating layer. A test in which the first haze H ₀ measured from the side is 3.0% or less, the laminate is stored at a temperature of 80 ° C. for 30 minutes, and then the laminate is stored at a temperature of -30 ° C for 30 minutes is defined as one cycle. In the thermal shock test, when the second haze H200 of the laminate after the thermal shock test of ₂₀₀ cycles was measured, the formula I ₂₀₀ : ΔH ₂₀₀ (%) = (H ₂₀₀ −H ₀ ) / H. The haze change rate ΔH ₂₀₀ of the laminated body calculated by ₀ × 100 is 70% or less.
That is, in the laminate according to the present embodiment, a base material, a conductive layer, and a coating layer are provided in this order.

In the initial stage before the thermal shock test, the laminate according to the present embodiment has, for example, the haze H ₀ of 3.0% or less and has excellent optical characteristics.
Further, in the thermal shock test defined as one cycle in which the laminated body is stored at a temperature of 80 ° C. for 30 minutes and then stored at a temperature of −30 ° C. for 30 minutes, this test is also carried out after the thermal shock test of 200 cycles. In the laminated body according to the form, the change in haze is suppressed and preferable optical characteristics are maintained, for example, the haze change rate ΔH ₂₀₀ is 70% or less.
The laminate according to the present embodiment having such optical characteristics can be manufactured, for example, by selecting a material suitable for a base material, a conductive layer and a coating layer, particularly a material for the coating layer.

As will be described later, in the laminate according to the present embodiment, when the coating layer is provided on the conductive layer at the time of manufacturing the laminate, the coating layer composition is directly applied to the conductive layer forming surface of the base material. It is possible to provide a coating layer by curing. Therefore, the laminate according to the present invention can be manufactured without separately forming a coating layer in advance and attaching the preformed coating layer to the conductive layer, and the coating layer attachment step is unnecessary. , The manufacturing process can be simplified. Further, in the laminate according to the present invention, unlike the case where the pasting step is performed, the coating layer can be formed by coating the composition for the coating layer, so that the coating layer is interposed through an intermediate layer such as an adhesive layer or an adhesive layer. Instead, the coating layer can be formed directly on the conductive layer and, if necessary, on the base material, and the configuration of the laminated body can be simplified. Further, in the laminated body according to 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 addition, in this specification, "the haze of the laminated body" means the haze of the whole laminated body measured from the side where the covering layer is provided (the outer surface of the covering layer), unless otherwise specified. The term "haze" means a value measured according to JIS K7136 unless otherwise specified, and in the present invention, an absolute value of a value measured according to JIS K7136 is adopted.

FIG. 1 is a cross-sectional view schematically showing a laminated body according to an embodiment 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, from one main surface (surface, outer surface of the coating layer 13, first main surface of the coating layer 13) 13a of the coating layer 13, the direction opposite to the direction in which the base material 11 is provided. The haze (first haze) H ₀ of the laminate 1 in the initial stage before the thermal shock test (for example, the stage immediately after production) measured from a position separated in the direction is 3.0% or less.
Further, in a thermal shock test defined as one cycle, a test in which a laminate 1 having a haze H ₀ of 3.0% or less is stored at a temperature of 80 ° C. for 30 minutes and then stored at a temperature of −30 ° C. for 30 minutes is defined as one cycle. When the haze (second haze) H ₂₀₀ of the laminated body 1 is measured after the thermal impact test of 200 cycles, the haze change rate ΔH ₂₀₀ of the laminated body 1 calculated by the formula I ₂₀₀ is 70% 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 a laminated body according to another embodiment 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 laminate 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 the regions of the surface 11a of the base material 11, and the cross section of the coating layer 23 is accompanied by the coating. It has the same configuration as the laminated body 1 shown in FIG. 1, except that the shapes are different. In FIG. 2, reference numeral 22a indicates the surface of the conductive layer 22.

The initial stage before the thermal shock test (eg, manufacturing) measured from the coating layer 23 side, that is, from the surface 23a of the coating layer 23 (from a position separated in the direction opposite to the direction in which the base material 11 is provided). The haze H ₀ of the laminated body 2 in the stage immediately after) is 3.0% or less.
Further, in the thermal shock test defined as one cycle, a test in which the laminate 2 having a haze H ₀ of 3.0% or less is stored at a temperature of 80 ° C. for 30 minutes and then stored at a temperature of −30 ° C. for 30 minutes is defined as one cycle. When the haze (second haze) H ₂₀₀ of the laminated body 2 is measured after the thermal impact test of 200 cycles, the haze change rate ΔH ₂₀₀ of the laminated body 2 calculated by the formula I ₂₀₀ is 70% 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 according to 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, and a partial configuration may be used. May be a laminated body in which is appropriately changed.
For example, the shape of the conductive layer when the laminated body is viewed in a plane 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 according to 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 according to the present invention is preferably a laminate that does not have the intermediate layer, has a conductive layer in direct contact with the substrate, and is laminated with a 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 laminated body can be manufactured by a simplified process, and the effect of the present invention that the change in the haze of the entire laminated body is suppressed even after the thermal shock test is particularly remarkable.

Further, in the laminate according to the present invention, for example, 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, the second main surface). It may be a laminated body. Here, examples of the layer laminated on the back surface of the base material include layers similar to the layer laminated on the 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 laminated body 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 ₂₀₀ is 70% or less). May be satisfied. That is, the haze H ₀ of the laminated body measured from the coating layer side of the back surface of the base material is 3.0% or less, and this laminated body is stored at a temperature of 80 ° C. for 30 minutes and then stored at a temperature of −30 ° C. for 30 minutes. In the thermal shock test in which the storage test is defined as one cycle, when the second haze H200 of the laminated body is measured after the thermal shock test of _{200 cycles, the haze change of the laminated body calculated by the above formula I 200 is} calculated. The rate ΔH ₂₀₀ may be 70% or less.

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 in the same manner 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). ₂₀₀ does not have to satisfy 70% 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), Polyethylenenaphthalate (PEN), Polybutylene naphthalate (PBN), Polyphenylensulfide (PPS), Polysulfone (PSF), Polyethersulfone (PET) 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 substrate 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, or 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 the plurality of layers are the same as each other, it means that the material and the thickness of each layer are the same.
When the base material is composed of a plurality of layers, the total thickness of each layer may be set to the above-mentioned preferable thickness of the base material (10 to 5000 μm).

<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, 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. It is more preferably 95% by mass or more, and particularly preferably 98% by mass or more. 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 "acryloyl group" and "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 1200 to 15,000.

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 covering layer may be a layer composed of a single layer, or may be a layer composed of two or more layers. When the coating layer is composed of a plurality of layers, the plurality of layers may be the same as 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.

In a thermal shock test defined as one cycle in which the laminate is stored at a temperature of 80 ° C. for 30 minutes and then stored at a temperature of −30 ° C. for 30 minutes, an X-cycle thermal shock test (X is an integer of 1 or more). When the haze of the laminate measured from the coating layer side (outer surface of the coating layer) is H _x , the haze change rate ΔH _x after the treatment of the laminate is calculated by the following formula (I _x ). Can be defined by. The haze change rate ΔH _x is an index of the stability of the optical characteristics under the condition that the temperature of the laminated body changes drastically.
ΔH _x (%) = (H _x −H ₀ ) / H ₀ × 100 ・ ・ ・ ・ (I _x )

After storing at a temperature of 80 ° C. for 30 minutes, the cooling rate when cooling the laminate is preferably 80 to 130 ° C./min, and 95 to 110 ° C. for storage at a temperature of −30 ° C. for 30 minutes. It is more preferably / min.
When storing at a temperature of 80 ° C. for 30 minutes and then storing at a temperature of −30 ° C. for 30 minutes, it is preferable to start cooling immediately (for example, within 1 minute) after the storage at a temperature of 80 ° C. for 30 minutes is completed.

On the other hand, after the test of one cycle is completed, when the test of the next cycle is performed, the laminate is stored at a temperature of -30 ° C for 30 minutes and then stored at a temperature of 80 ° C for 30 minutes. The temperature rate is preferably 20 to 60 ° C./min, more preferably 30 to 40 ° C./min.
After storing at a temperature of -30 ° C for 30 minutes, when storing at a temperature of 80 ° C for 30 minutes for further testing of the next cycle, immediately after the end of the 30-minute storage at a temperature of -30 ° C (eg, for example). It is preferable to start the temperature rise within 1 minute).

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 laminated body of the present invention, the lower limit of haze _H0 is not particularly limited and may be, for example, 0.1%, 0.2%, 0.4%, 0.6% or the like. ..

In the laminated body of the present invention, the haze H ₁₀₀ , which is the haze of the laminated body after 100 cycles of the thermal shock test, is preferably 3.2% or less, more preferably 3.0% or less. It is more preferably 2.8% or less, and particularly preferably 2.6% or less. When the haze H ₁₀₀ is not more than the upper limit value (3.2%), 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 H ₁₀₀ is not particularly limited and may be, for example, 0.1%, 0.3%, 0.5%, 0.7% or the like. ..

In the laminated body of the present invention, the haze H200, which is the haze of the laminated body after ₂₀₀ cycles of the thermal shock test, is preferably 3.5% or less, more preferably 3.3% or less. It is more preferably 3.1% or less, and particularly preferably 2.9% or less. When the haze H ₂₀₀ is not more than the upper limit value (3.5%), 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 _H200 is not particularly limited and may be, for example, 0.1%, 0.3%, 0.5%, 0.7% or the like. ..

In the laminated body of the present invention, the haze H ₃₀₀ , which is the haze after 300 cycles of the thermal shock test, is preferably 3.8% or less, more preferably 3.6% or less. It is more preferably 4% or less, and particularly preferably 3.2% or less. When the haze H ₃₀₀ is not more than the upper limit value (3.8%), 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 H ₃₀₀ is not particularly limited, and may be, for example, 0.1%, 0.3%, 0.6%, 0.9% or the like. ..

In the laminated body of the present invention, the haze H ₄₀₀ , which is the haze after 400 cycles of the thermal shock test, is preferably 4.0% or less, more preferably 3.8% or less. It is more preferably 6% or less, and particularly preferably 3.4% or less. When the haze H ₄₀₀ is not more than the upper limit value (4.0%), 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 H ₄₀₀ is not particularly limited, and may be, for example, 0.1%, 0.5%, 0.8%, 1.1% or the like. ..

In the laminated body of the present invention, the haze H ₅₀₀ which is the haze when the above thermal shock test is carried out for 500 cycles, the haze H ₇₀₀ which is the haze when the above thermal shock test is carried out for 700 cycles, and the above thermal shock test for 800 cycles. Haze H ₈₀₀ , which is the haze when the thermal shock test is performed, Haze H ₉₀₀ , which is the haze when the thermal shock test is performed for 900 cycles, Haze H ₁₀₀₀ , which is the haze when the thermal shock test is performed for 1000 cycles, and the thermal shock. The haze H ₁₅₀₀ , which is the haze after 1500 cycles of the test, is preferably 4.2% or less, more preferably 4.0% or less, still more preferably 3.6% or less. .. When the haze is not more than the upper limit value (4.2%) when the above-mentioned thermal shock test is performed for 500 cycles or more, the laminated body becomes more excellent in optical characteristics.
On the other hand, in the laminated body of the present invention, the lower limit of the haze when the above-mentioned thermal shock test is performed is not particularly limited, and for example, 0.1%, 0.5%, 0.9%, 1.1%. And so on.

In the laminated body of the present invention, the haze change rate ΔH ₁₀₀ after 100 cycles of the thermal shock test is preferably 50% or less, more preferably 40% or less, and more preferably 35% or less. It is more preferably 30% or less, and particularly preferably 30% or less. When the haze change rate ΔH ₁₀₀ is not more than the upper limit value (50%), the laminate becomes more excellent in optical characteristics.
On the other hand, in the laminated body of the present invention, the lower limit of the haze change rate ΔH ₁₀₀ is not particularly limited, and may be, for example, 0%, 2%, 4%, 6% or the like.

In the laminate of the present invention, the haze change rate ΔH ₂₀₀ after 200 cycles of the thermal shock test is 70% or less, for example, 60% or less, 50% or less, 40% or less, 30% or less, 20%. Below, it can be any of 10% or less. When the haze change rate ΔH ₂₀₀ is not more than the upper limit value (70%), the laminated body has excellent optical characteristics.
On the other hand, in the laminated body of the present invention, the lower limit of the haze change rate ΔH ₂₀₀ is not particularly limited, and may be, for example, 0%, 5%, 10%, 15%, or the like.

In the laminated body of the present invention, the haze change rate ΔH ₃₀₀ after 300 cycles of the thermal shock test is preferably 90% or less, more preferably 80% or less, and more preferably 70% or less. Is more preferable, 60% or less is particularly preferable, 50% or less is most preferable, and for example, 40% or less can be used. When the haze change rate ΔH ₃₀₀ is not more than the upper limit value (90%), the laminated body has excellent optical characteristics.
On the other hand, in the laminated body of the present invention, the lower limit of the haze change rate ΔH ₃₀₀ is not particularly limited and may be, for example, 0%, 5%, 10%, 15% or the like.

In the laminated body of the present invention, the haze change rate ΔH ₄₀₀ when the thermal shock test is carried out for 400 cycles and the haze change rate ΔH ₅₀₀ when the thermal shock test is carried out for 500 cycles are both 95% or less. It is preferably 90% or less, and more preferably 90% or less, for example, 80% or less, 70% or less, 60% or less, 50% or less, or the like. When the haze change rate ΔH ₄₀₀ is not more than the upper limit value (95%), the laminate becomes more excellent in optical characteristics.
On the other hand, in the laminated body of the present invention, the lower limit values of the haze change rate ΔH ₄₀₀ and the haze change rate ΔH ₅₀₀ are not particularly limited, and may be, for example, 0%, 5%, 8%, 13%, 18% or the like. be able to.

In the laminate of the present invention, the haze change rate when the thermal shock test is performed for 700 cycles or more (for example, ΔH ₇₀₀ when the thermal impact test is performed for 700 cycles, and when the thermal shock test is performed for 800 cycles). ΔH ₈₀₀ , ΔH ₉₀₀ when the thermal shock test was performed for 900 cycles, ΔH ₁₀₀₀ when the thermal impact test was performed for 1000 cycles, ΔH ₁₅₀₀ when the thermal impact test was performed for 1500 cycles, etc.) was 120%. It is preferably 110% or less, 100% or less, 90% or less, 80% or less, 70% or less, 60% or less, and the like. When the haze change rate after 700 cycles of the thermal shock test is not more than the upper limit value (120%), the laminated body becomes more excellent in optical characteristics.
On the other hand, in the laminated body of the present invention, the lower limit of the haze change rate when the above thermal shock test is performed for 700 cycles or more is not particularly limited, and for example, 5%, 10%, 15%, 20%, 25% and the like. Can be either.

<< Manufacturing method of laminated body >>
The laminate of the present invention is, 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 "conducting layer"). , May be abbreviated as "coating layer forming step"), and can be manufactured by the manufacturing method having.

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 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 covered 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.
As a result, the laminated body 1 is obtained.
In addition, although the explanation was given here by quoting the laminated body 1 shown in FIG. 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 (hereinafter, may be abbreviated as "composition for a conductive layer") as a raw material for forming the 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 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), the conductive layer 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, may be 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 nanoparticles, and silver nanoparticles, silver nanos, etc. Particularly preferred are wires, copper nanoparticles or copper nanoparticles.
In the present specification, the “nanoparticle” means a particle having a particle size of 1 nm or more and less than 1000 nm, preferably 1 to 100 nm, and the “nanowire” means a particle having a width of 1 nm or more and less than 1000 nm, preferably. It means a wire having a diameter of 1 to 100 nm.

The material for forming the metal to be blended may be any material as long as it has a corresponding metal atom (element) and produces a metal by a structural change such as decomposition. 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 of only 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 a 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 even when the metal type is other than silver. A conductive layer can be formed.
The material for forming metallic silver is a material that decomposes 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 kind of silver carboxylate may be used alone, or two or more kinds may be used in combination. When two or more kinds are used in combination, the combination and ratio of the 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 the following general formula (1), β-ketocarboxylate silver (hereinafter, may be abbreviated as “β-ketocarboxylate silver (1)”) and the following general formula (4). It is preferably one or more selected from the group consisting of silver carboxylate (hereinafter, may be abbreviated as "silver carboxylate (4)").
In this specification, the description of "silver carboxylate" is not limited to "β-ketosilver carboxylate (1)" and "silver carboxylate (4)" unless otherwise specified. Inclusive, it shall mean "silver carboxylate having a group represented by the formula" -COOAg "".

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

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

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

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

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

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

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

Examples of the alkenyl group in R include a 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-) One single bond (C-) between the carbon atoms of the alkyl group in R, such as CH ₃ ), 3-butenyl group (-CH ₂ -CH ₂ -CH = CH ₂ ), cyclohexenyl group, cyclopentenyl group, etc. Examples thereof include a group in which C) is replaced with a double bond (C = C).
As the alkynyl group in R, for example, one single bond (C) between carbon atoms of the alkyl group in R, such as an ethynyl group (-C≡CH) and a propargyl group ( _-CH2 -C≡CH). 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, a bromine atom and the like. Can be mentioned. Further, 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 carbide having 1 to 16 carbon atoms. A hydrogen group, a monovalent group formed by bonding the aliphatic hydrocarbon group to an oxygen atom, a fluorine atom, a chlorine atom, a bromine atom, a hydroxyl group (-OH), a cyano group (-C≡N), and a phenoxy group. (-OC ₆ H ₅ ) and the like can be mentioned, 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.
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 a fluorine atom, a chlorine atom, a bromine atom or a hydrogen atom, respectively. Further, in the general formulas "R ¹ -CY 1 _2- ", "CY ¹ _3- " and "R ⁶ -C (= O) -CY ¹ _2- ", even if ^a plurality of Y ^1s are the same as each other. It may be different.

R ¹ in R is an aliphatic hydrocarbon group or a phenyl group (C _{6 H5-} ) having 1 to 19 carbon atoms, and the aliphatic hydrocarbon group in R ¹ has 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 the same group as the aliphatic hydrocarbon group in R.
R ³ in R is an aliphatic hydrocarbon group having 1 to 16 carbon atoms, and examples thereof include the same groups as the aliphatic hydrocarbon group in R except that the carbon atoms are 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 the same group as 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 having 1 to 19 carbon atoms, a hydroxyl group or a group represented by the formula “AgO-”, and the aliphatic hydrocarbon group in R ⁶ has 1 to 1 carbon atoms. Examples thereof include the same group as the aliphatic hydrocarbon group in R except that the number is 19.

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

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

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

R ⁷ in X ¹ is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, a thienyl group _{( C4H3S-} ), or a phenyl group in which one or more hydrogen atoms may be substituted with a substituent. It is a diphenyl group (biphenyl group, C ₆ H ₅ -C ₆ H _4- ). Examples of the aliphatic hydrocarbon group in R ⁷ include 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 ^R7 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 a thienyl group or ^a diphenyl group, the bonding position with the adjacent group or atom (oxygen atom, sulfur atom, carbonyl group, carbonyloxy group) in X1 is not particularly limited. For example, the thienyl group may be either a 2-thienyl group or a 3-thienyl group.

In the general formula (1), 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.

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

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

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, the silver β-ketocarboxylate (1) is decomposed at a low temperature of preferably 60 to 210 ° C., more preferably 60 to 200 ° C. without using a reducing agent known in the art. 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 the β-ketocarboxylate silver can be arbitrarily adjusted.

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

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

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

Similar to β-ketosilver carboxylate (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 kind of silver carboxylate (4) may be used alone, or two or more kinds may be used in combination. When two or more kinds are used in combination, the combination and ratio of the silver carboxylates can be arbitrarily adjusted.

The silver carboxylate is silver 2-methylacetate, silver acetoacetate, silver 2-ethylacetate, silver propionylacetate, silver isobutyryl acetate, silver pivaloyl acetate, silver caproyl acetate, silver 2-n-butylacetate, 2-benzylacetate. Silver acetate, benzoyl silver acetate, silver pivaloylacetacetate, silver isobutyryl acetoacetate, silver acetonedicarboxylate, silver pyruvate, silver acetate, silver butyrate, silver isobutyrate, silver 2-ethylhexanoate, silver neodecanoate, oxalate It is preferably one or more selected from the group consisting of silver acid acid and silver malonate.
Among these silver carboxylates, silver 2-methylacetoacetic acid and acetoacetic acid have excellent compatibility with nitrogen-containing compounds (among others, 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" is synonymous with 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"). (May be), ammonia, an ammonium salt formed by reacting an amine compound with 25 or less carbon atoms with an acid (hereinafter, may be abbreviated as "ammine salt derived from an amine compound"), and ammonia 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 chain-like or cyclic. Further, the number of nitrogen atoms constituting the amine moiety or the ammonium salt moiety (for example, the nitrogen atom constituting the amino group (-NH ₂ ) of the primary amine) may be one or two or more.

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

The alkyl group constituting the monoalkylamine may be linear, branched or cyclic, and examples 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 examples of the monoalkylamine include, for example, n-butylamine, n-hexylamine, n-octylamine, n-dodecylamine, n-octadecylamine, isobutylamine, sec-butylamine, tert-butylamine, 3 -Aminopentane, 3-methylbutylamine, 2-heptylamine (2-aminoheptane), 2-aminooctane, 2-ethylhexylamine, 1,2-dimethyl-n-propylamine and the like can be mentioned.

Examples of the aryl group constituting the monoarylamine include a phenyl group, a 1-naphthyl group, a 2-naphthyl group and the like, 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, may be all different, or may be partially different.
The heteroaryl group may be either monocyclic or polycyclic, and the number of ring members (the number of atoms constituting the ring skeleton) is not particularly limited, but is preferably 3 to 12 membered rings.

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

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

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

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

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

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

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

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

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

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

Up to this point, the chain amine compound and the quaternary organic ammonium salt have been mainly described, but the amine compound and the quaternary ammonium salt have a ring skeleton structure in which nitrogen atoms constituting the amine moiety or the ammonium salt moiety are present. It may be a heterocyclic compound which is a part of the heterocyclic skeleton structure). That is, the amine compound may be a cyclic amine, and the quaternary ammonium salt may be a cyclic ammonium salt. The ring (ring containing nitrogen atoms constituting the amine moiety or ammonium salt moiety) structure at this time may be either monocyclic or polycyclic, and the number of ring members (the number of atoms constituting the ring skeleton) is particularly limited. However, it may be either an aliphatic ring or an aromatic ring.
If it is a cyclic amine, preferable 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" means a nitrogen atom constituting an amine moiety or an ammonium salt moiety. It is a hydrogen atom other than the hydrogen atom bonded to. The number of substituents at this time is not particularly limited, and may be one, two or more, and all of the hydrogen atoms may be substituted with substituents. When the number of substituents is plural, these plurality of substituents may be the same or different from each other. That is, the plurality of substituents may all be the same, all may be different, or only some of them may be different. Further, the position of the substituent is not particularly limited.

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

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

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

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

The amine compounds include n-propylamine, n-butylamine, n-hexylamine, n-octylamine, n-dodecylamine, n-octadecylamine, isobutylamine, sec-butylamine, tert-butylamine, 3-aminopentane, and the like. 3-Methylbutylamine, 2-Heptylamine, 2-aminooctane, 2-ethylhexylamine, 2-phenylethylamine, ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, N-methyl-n-hexylamine, Diisobutylamine, N-methylbenzylamine, di (2-ethylhexyl) amine, 1,2-dimethyl-n-propylamine, N, N-dimethyl-n-octadecylamine or N, N-dimethylcyclohexylamine. Is preferable.
Among these amine compounds, 2-ethylhexylamine has excellent compatibility with the silver carboxylate, is particularly suitable for increasing the concentration of the silver ink composition, 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. The acid may be an inorganic acid such as hydrochloric acid, sulfuric acid or nitric acid, or an organic acid such as acetic acid, and the type of acid is not particularly limited.
Examples of the ammonium salt derived from the amine compound include n-propylamine hydrochloride, N-methyl-n-hexylamine hydrochloride, N, N-dimethyl-n-octadecylamine hydrochloride and the like. Not limited.

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

In the present 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, a first nitrogen-containing compound having 8 or more carbon atoms and a second nitrogen-containing compound having 7 or less carbon atoms may be used in combination.
When the first nitrogen-containing compound and the second nitrogen-containing compound are used in combination, the ratio of the blending amount of the second nitrogen-containing compound to the blending amount of the first nitrogen-containing compound in the silver ink composition 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 compounding amount of the nitrogen-containing compound is preferably 0.3 to 15 mol, more preferably 0.3 to 12 mol, per 1 mol of the compounding amount of the metallic silver forming material. It is preferably 0.3 to 8 mol, and may be, for example, 1 to 8 mol, 2.5 to 8 mol, and 4 to 8 mol. 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 (metal 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 is one selected from the group consisting of oxalic acid (HOOC-COOH), hydrazine (H2 N _{-NH 2 )} and the compound represented by the general formula (5) (compound (5)). These are the above compounds. That is, the reducing compound to be blended may be only one kind, may be two or more kinds, and when two or more kinds are used in combination, the combination and 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 of 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. Examples are similar to the group.

As the reducing compound, hydrazine may be a monohydrate (H2N _{- NH2} · _H2O ).

Preferred compounds among the reducing compounds include, for example, formic acid (HC (= O) -OH); methyl formate (HC (= O) -OCH ₃ ), ethyl formate (HC (= O)). -Formic acid esters such as OCH ₂ CH ₃ ), butyl formate (HC (= O) -O (CH ₂ ) ₃ CH ₃ ); 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 an ester); formic acid and the like can be mentioned.

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 1 mol of the compounding material 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 further containing alcohol 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 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 the substituents is a plurality, the plurality of substituents may be the same or different from each other.

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

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

When the acetylene alcohol (2) is used, in the silver ink composition, the blending amount of the acetylene alcohol (2) is preferably 0.01 to 0.7 mol per 1 mol of the metallic silver forming material. , 0.02 to 0.5 mol, more preferably 0.02 to 0.3 mol. 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, the nitrogen-containing compound, the reducing agent and the 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, and 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.
In addition, in this specification, "normal temperature" means a temperature which is not particularly cooled or heated, that is, a normal temperature, and examples thereof include a temperature of 15 to 25 ° C.

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

The blending amount of the other components in the silver ink composition may be appropriately selected according to the type of the other components.
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 more preferably 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 above-mentioned solvent 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 blending amount of the other component to the total blending component in the silver ink composition is preferably 10% by mass or less, preferably 5% by mass. % Or less is more preferable.
The ratio of the blending amount of the other components to the total blending component is 0 mass, that is, even if the other components are not blended, the silver ink composition sufficiently exhibits its effect.

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 the 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 β-ketocarboxylate silver (1) is used as the material for forming the metallic silver, impurities that inhibit conductivity are not generated or such when each of the above components is blended. 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 the components may be sequentially added and mixed. good. However, in the present invention, the reducing agent is preferably blended by dropping, and further, by suppressing the fluctuation of the dropping rate, the surface roughness of metallic silver tends to be further reduced.
The mixing method is not particularly limited, and a method of rotating and mixing a stirrer, a stirring blade, or the like; a method of mixing using a mixer, a three-roll, a kneader, a bead mill, or the like; a method of adding ultrasonic waves and the like, etc. It may be appropriately selected from known methods.
In the case of uniformly dispersing the undissolved components in the silver ink composition, 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. The temperature at the time of blending may be appropriately adjusted according to the type and amount of the blending component so that the mixture obtained by blending has a viscosity that makes it easy to stir.
Further, the blending time is not particularly limited as long as each blending component is not deteriorated, but is preferably 10 minutes to 36 hours.

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. As an example of a more preferable composition of the silver ink composition obtained in such an order of addition, as the nitrogen-containing compound, a composition in which the first nitrogen-containing compound and the second nitrogen-containing compound are used in combination 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.

When the first nitrogen-containing compound and the second nitrogen-containing compound are used in combination, the silver ink composition is a first compounding step in which a material for forming metallic silver is blended with a 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 compound (Q1) obtained in the first compounding step, and in the compound (Q2) obtained in the second compounding step, alcohol and, if necessary. The composition obtained by the production method having the third compounding 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 blending amount of alcohol in the third blending 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. The composition is 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. It 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 such as flexographic printing method, screen printing method, gravure printing method, gravure offset printing method, pad printing method, etc., which require thickening of ink. 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 containing the metallic silver forming material and the nitrogen-containing compound to form a second mixture, and if necessary, to the second mixture. , It is preferable to add 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 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 the 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), and may be 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 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 this pipe to the first mixture. A method of supplying the gas to the gas can be mentioned. At this time, carbon dioxide gas may be supplied directly from the end of the pipe, but for example, a large number of voids that can serve as a gas flow path are provided, such as a porous member, to diffuse the introduced gas. A gas diffusion member capable of being discharged as minute bubbles may be connected to the end of the pipe, and carbon dioxide gas may be supplied through the gas diffusion member. Further, carbon dioxide gas may be supplied while stirring the 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 the time of using the silver ink composition 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. It is more preferable to have. The upper limit of the flow rate is not particularly limited, but it is preferably 40 mL / min per 1 g of the mixture in consideration of handleability and the like.
The carbon dioxide gas supply time may be appropriately adjusted in consideration of the required carbon dioxide gas supply amount and the flow rate.

The temperature of the 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 (5 ° C), carbon dioxide can be supplied more efficiently, and when the temperature is at least the upper limit (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 to an appropriate range while considering each value mutually. 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 of (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 can be 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 dry ice (solid carbon dioxide) may be supplied by adding the 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 above-mentioned supply amount of carbon dioxide gas.
During and after the addition of the 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 silver ink composition described above without using carbon dioxide. By doing so, carbon dioxide can be efficiently supplied.
The temperature at the time of stirring may be the same as that at the time of supplying carbon dioxide gas. Further, the stirring time may be appropriately adjusted according to the stirring temperature.

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 the time of using the second mixture 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 form 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 in a dispersed state 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. The temperature at the time of blending may be appropriately adjusted according to the type and amount of the blending component so that the mixture obtained by blending has a viscosity that makes it easy to stir.
The blending time may be appropriately adjusted according to the type of the blending component and the temperature at the time of blending, but is preferably 0.5 to 12 hours, for example.

As described above, 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. good. That is, in the process of producing the silver ink composition through the first mixture and the second mixture, the ratio of the compounding amount of the other components to the total amount of the compounding 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 the addition of mass, i.e., other components.

The silver ink composition supplied with carbon dioxide 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 speculated 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 containing no 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 containing no 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 blended into 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 resistivity, that is, a mixture to which carbon dioxide is not supplied. The conductor has higher conductivity (lower volume resistivity), lower surface roughness, and more preferable characteristics than the conductor when the silver ink composition is used.

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

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 a spin coater, an air knife coater, a curtain coater, a die coater, a blade coater, a roll coater, a gate roll coater, a bar coater, a rod coater, and a gravure coater, a 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, under normal pressure, under reduced pressure, or under blowing conditions, and under either atmospheric conditions or 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. As a preferable drying method when heat treatment is not required, for example, a method of drying in the atmosphere at 18 to 30 ° C. can be mentioned.

When the silver ink composition is heated (baked), the conditions of the heating (baking) treatment may be appropriately adjusted according to the type of the compounding component of the silver ink composition. Usually, the heating temperature is preferably 60 to 370 ° C, more preferably 70 to 280 ° C. The heating time may be adjusted according to the heating temperature, but is usually preferably 1 minute to 24 hours, more preferably 1 minute to 12 hours. Among the materials for forming metallic silver, the silver carboxylate, particularly β-ketosilver carboxylate (1), is different from the material for forming metallic silver such as silver oxide, and a reducing agent known in the art is used. Even without it, it decomposes at low temperature. 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 spraying high heat 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 pressure.

As used herein, "humidification" means artificially increasing the humidity, preferably a relative humidity of 5% or more, unless otherwise specified. 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 may be 100%. Then, the heat treatment under the humidifying condition may be performed by spraying high-pressure steam heated to 100 ° C. or higher. By heat-treating under humidifying conditions in this way, higher-purity metallic silver can be formed in a short time.

The heat treatment of the silver ink composition may be performed in two steps. For example, a method in which the silver ink composition is mainly dried instead of forming metallic silver in the first-step heat treatment, and the metallic silver is formed to the end in the second-step heat treatment can be exemplified.
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 the heat treatment, the heating temperature may be appropriately adjusted according to the type of the compounding component of the silver ink composition so that metallic silver is formed well, but it may be 60 to 280 ° C. It is preferably 70 to 260 ° C., more preferably 70 to 260 ° C. The heating time may be adjusted according to the heating temperature, but is usually preferably 1 minute to 12 hours, more preferably 1 minute to 10 hours.
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, and particularly 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 in 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 step 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 above-mentioned 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-humidification" means that the above-mentioned "humidification" is not performed, that is, the humidity is not artificially increased, and the relative humidity is preferably less than 5%. ..

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

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 55 to 130 ° C, preferably 60 to 125 ° C. More preferred. The heating time under the non-humidifying condition of the first step is preferably 5 seconds to 1 hour, more preferably 30 seconds to 40 minutes, and particularly preferably 30 seconds to 25 minutes. ..
The heating temperature during the heat treatment under the humidifying condition of the second stage, which is performed after the heat treatment under the non-humidifying condition of the first stage, is preferably 60 to 140 ° C., preferably 70 to 130 ° C. Is more preferable. The heating time under the humidifying condition of the second stage 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 heated (baked), the heat treatment under the non-humidifying condition of the first stage and the humidifying condition of the second stage are performed. 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 material for forming metallic silver 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 manufacturing 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.

As a modification of the silver ink composition described above, the silver ink composition 2 is shown below.
The silver ink composition 2 shown below may be used for forming the conductive layer in the present invention.
The silver ink composition 2 is shown in detail below.

<Branched chain saturated aliphatic carboxylic acid having 8 to 10 carbon atoms>
The silver ink composition 2 is composed of a branched chain saturated aliphatic carboxylic acid having 8 to 10 carbon atoms in addition to a material for forming metallic silver (for example, an organic silver compound or silver carboxylate). Since the silver ink composition 2 contains the branched saturated aliphatic carboxylic acid, it is possible to form metallic silver having high gloss even when printing is performed while heating the object to be printed. ..

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

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

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

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

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

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

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

The branched saturated aliphatic carboxylic acid has an appropriate reactivity that suppresses a decrease in the glossiness of metallic silver, and is difficult to volatilize from the silver ink composition 2, while the silver ink composition 2 is solidified. It has an appropriate boiling point that is easily vaporized during treatment, and has particularly suitable properties as it exhibits the effects of the present invention.
For example, the boiling point of the branched chain saturated aliphatic carboxylic acid is preferably 180 to 270 ° C, more preferably 200 to 260 ° C, and particularly preferably 215 to 255 ° C. When the boiling point of the branched saturated aliphatic carboxylic acid is at least the above lower limit, the volatilization of the branched saturated aliphatic carboxylic acid from the silver ink composition 2 is suppressed, and the branched chain saturated aliphatic carboxylic acid is suppressed. The effect of using the acid is more remarkable. Further, when the boiling point of the branched saturated aliphatic carboxylic acid is not more than the above upper limit value, the residual branched chain saturated aliphatic carboxylic acid remains in the metallic silver obtained by the solidification treatment of the silver ink composition 2. Metallic silver having more preferable properties such as being suppressed and having high glossiness, conductivity and the like can be obtained.

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

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

As described above, the silver ink composition 2 contains the branched saturated aliphatic carboxylic acid, so that the silver ink composition 2 has high gloss even when printing is performed while heating the object to be printed. Metallic silver can be formed. The reason is not clear, but it is presumed as follows.
That is, in the silver ink composition 2 printed on the object to be printed, silver ions (Ag ⁺ ) are generated from the material for forming metallic silver. In this case, oxygen is coordinated to the silver ions by heating the object to be printed (Ag ⁺ ... O). Next, silver oxide (Ag ₂ O) is generated from the oxygen-coordinated silver ions by a solidification treatment such as a drying treatment or a heating (baking) treatment of the silver ink composition (I) for forming metallic silver. Here, in the case of a silver ink composition that does not contain a branched saturated aliphatic carboxylic acid, silver oxide produced as a by-product is contained in the metallic silver finally produced by the solidification treatment of the silver ink composition. It is presumed that it will be mixed as an impurity and the glossiness of metallic silver will decrease. On the other hand, in the case of the silver ink composition 2 containing the branched saturated aliphatic carboxylic acid, the branched saturated aliphatic carboxylic acid reacts with silver oxide to have 8 to 10 carbon atoms. A silver salt of a branched saturated aliphatic carboxylic acid (may be abbreviated as "branched chain saturated aliphatic carboxylic acid silver" in the present specification) is produced. This branched chain saturated aliphatic carboxylate silver is the above-mentioned silver carboxylate (4), that is, a material for forming metallic silver, and the silver ink composition 2 is similar to the material for forming metallic silver that has been blended from the beginning. Finally, metallic silver is produced by the solidification process. As described above, by using the silver ink composition 2 of the present invention, the silver oxide generated due to the heating of the object to be printed has the luster of metallic silver due to the action of the branched chain saturated aliphatic carboxylic acid. It is presumed that metallic silver with high gloss can be formed by converting it to metallic silver itself instead of the impurities that cause the decrease.

In the silver ink composition 2, the blending amount of the branched saturated aliphatic carboxylic acid is preferably 0.01 to 1 mol per 1 mol of the silver atom in the metal silver forming material, and is 0. It is more preferably 0.02 to 0.7 mol, and particularly preferably 0.03 to 0.4 mol. When the amount of the branched chain saturated aliphatic carboxylic acid is in such a range, the effect of forming highly glossy metallic silver can be obtained even when printing is performed while heating the object to be printed. It will be higher.

Similar to the branched saturated aliphatic carboxylic acid, the metallic silver having high gloss is also applied to the carboxylic acid other than the branched saturated aliphatic carboxylic acid even when printing is performed while heating the object to be printed. There is something that allows the formation of.
The carboxylic acid other than such a branched chain saturated aliphatic carboxylic acid (sometimes referred to as “other carboxylic acid” in the present specification) may be a monovalent carboxylic acid or a divalent or higher carboxylic acid. It may be a polyvalent carboxylic acid, an aliphatic carboxylic acid, or an aromatic carboxylic acid.

The other carboxylic acid preferably does not contain a group having a reducing power such as a formyl group (-C (= O) -H). The silver ink composition 2 containing another carboxylic acid containing no such group suppresses the formation of insoluble matter derived from the metal silver forming material during storage thereof, and has higher handleability at the time of printing. ..

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

The boiling point of the other carboxylic acid is preferably 150 to 290 ° C, and may be, for example, 155 to 280 ° C, 160 to 270 ° C and 160 to 260 ° C. When the boiling point of the other carboxylic acid is at least the above lower limit, the volatilization of the other carboxylic acid from the silver ink composition 2 is suppressed, and the effect of using the other carboxylic acid is more remarkable. Be done. Further, when the boiling point of the other carboxylic acid is not more than the upper limit value, the residual of the other carboxylic acid in the metallic silver obtained by the solidification treatment of the silver ink composition 2 is suppressed, and the glossiness and the conductivity are suppressed. Metallic silver having more preferable characteristics such as high value can be obtained.

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

In the silver ink composition 2, the blending amount of the other carboxylic acid can be the same as the blending amount of the above-mentioned branched chain saturated aliphatic carboxylic acid.

Similar to the silver ink composition described above, the silver ink composition 2 contains a nitrogen-containing compound, a reducing agent, an alcohol, and other substances in addition to the metallic silver forming material and the branched saturated aliphatic carboxylic acid. A composition containing at least one selected from the group consisting of other components may be used.
In this case, the blending amounts of the nitrogen-containing compound, the reducing agent, the alcohol, and other components in the silver ink composition 2 may be the same as in the case of the silver ink composition described above.

[Manufacturing method of silver ink composition 2]
The silver ink composition 2 described above may be used for forming the conductive layer in the present invention.
The silver ink composition 2 is obtained by blending the metal silver forming material, the branched chain saturated aliphatic carboxylic acid, and, if necessary, other components. After blending each component, the obtained product may be used as it is as the silver ink composition 2, or the silver ink composition 2 may be obtained by continuously performing a known purification operation as needed. In the present invention, particularly when β-ketocarboxylate silver (1) is used as the material for forming the metallic silver, impurities that reduce glossiness and conductivity are not generated or impurities are not generated when each of the above components is blended. The amount of such impurities produced can be suppressed to an extremely small amount. Therefore, even if the silver ink composition 2 that has not been refined is used, metallic silver having sufficient glossiness and conductivity can be obtained.

The blending order of each component is not particularly limited. As an example of a preferable compounding method for each component, there is a method in which the branched chain saturated aliphatic carboxylic acid is compounded last. That is, as an example of a preferable production method of the silver ink composition 2, a production method in which all the components other than the branched-chain saturated aliphatic carboxylic acid are blended and then the branched-chain saturated aliphatic carboxylic acid is finally blended is used. Can be mentioned.

When blending each component, all the components may be added and then mixed, some components may be added sequentially and mixed, or all the components may be sequentially added and mixed. good.
The mixing method is not particularly limited, and a method of rotating and mixing a stirrer, a stirring blade, or the like; a method of mixing using a mixer, a three-roll, a kneader, a bead mill, or the like; a method of adding ultrasonic waves and the like, etc. It may be appropriately selected from known methods.
In the case of uniformly dispersing the undissolved components in the silver ink composition 2, 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. The temperature at the time of blending may be appropriately adjusted according to the type and amount of the blending component so that the mixture obtained by blending has a viscosity that makes it easy to stir.
Further, the blending time is not particularly limited as long as each blending component is not deteriorated, but is preferably 10 minutes to 36 hours.

<Carbon dioxide>
The silver ink composition 2 may be further supplied with carbon dioxide. Such a silver ink composition 2 has a high viscosity, and for example, a printing method that requires thickening of ink, such as a flexographic printing method, a screen printing method, a gravure printing method, a gravure offset printing method, and a pad printing method. It is suitable for the application of.

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

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

The amount of carbon dioxide gas supplied may be appropriately adjusted according to the amount of the object to be supplied, the viscosity of the target silver ink composition 2, and the like, and is not particularly limited. For example, in order to obtain about 100 to 1000 g of a silver ink composition 2 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 2 at 20 to 25 ° C. has been described here, the temperature at the time of using the silver ink composition 2 is not limited to 20 to 25 ° C. and can be arbitrarily selected. Further, in the present specification, the “viscosity” means the one measured by using an ultrasonic vibration viscometer unless otherwise specified.

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

The temperature of the object to be supplied at the time of supplying carbon dioxide gas is preferably 5 to 70 ° C, more preferably 7 to 60 ° C, and particularly preferably 10 to 50 ° C. When the temperature is at least the lower limit value, carbon dioxide can be supplied more efficiently, and when the temperature is at least the upper limit value, a silver ink composition 2 having better quality with less impurities can be 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 to an appropriate range while considering each value mutually. For example, even if the temperature is set low, carbon dioxide gas flow rate is set high, carbon dioxide gas supply time is set long, or both are performed efficiently. Can supply carbon. In addition, even if the flow rate of carbon dioxide gas is set to be low, carbon dioxide can be efficiently achieved by raising the temperature, setting the supply time of carbon dioxide gas to a long time, or both. Can be supplied. That is, by flexibly combining the values in the above numerical range exemplified as the flow rate of carbon dioxide gas and the temperature at the time of supplying carbon dioxide gas while considering the supply time of carbon dioxide gas, silver ink of good quality is obtained. The composition 2 is efficiently obtained.

The carbon dioxide gas is preferably supplied while stirring the object to be supplied. By doing so, the supplied carbon dioxide gas can be more uniformly diffused into the object to be supplied, and carbon dioxide can be supplied more efficiently.
The stirring method at this time may be the same as the case of the mixing method at the time of manufacturing the silver ink composition 2 which does not use carbon dioxide.

Dry ice (solid carbon dioxide) may be supplied by adding dry ice to the object to be supplied. The whole amount of dry ice may be added all at once, or may be divided and added stepwise (continuously with a time zone during which the addition is not performed).
The amount of dry ice used may be adjusted in consideration of the above-mentioned supply amount of carbon dioxide gas.
During and after the addition of the dry ice, it is preferable to stir the object to be supplied, for example, it is preferable to stir in the same manner as in the production of the silver ink composition 2 without using carbon dioxide. By doing so, carbon dioxide can be efficiently supplied.
The temperature at the time of stirring may be the same as that at the time of supplying carbon dioxide gas. Further, the stirring time may be appropriately adjusted according to the stirring temperature.

For example, when the silver ink composition 2 is applied to a printing method using a high-viscosity ink such as a screen printing method and a flexographic printing method, 20 to 25 of the silver ink composition 2 to which carbon dioxide is supplied. The viscosity at ° C. is preferably 1 Pa · s or more.

As described above, in the silver ink composition 2 having a viscosity higher than usual due to the supply of carbon dioxide, metallic silver may be formed from at least a part of the metallic silver forming material, and the metallic silver may be precipitated. .. At this time, when the viscosity of the silver ink composition 2 is high, the aggregation of the precipitated metallic silver is suppressed, and the dispersibility of the metallic silver in the obtained silver ink composition 2 is improved. The metallic silver obtained by forming metallic silver by the method described later using such a silver ink composition 2 has a low resistivity, that is, when a silver ink composition 2 to which carbon dioxide is not supplied is used. It has higher gloss, higher conductivity (lower volume resistivity), lower surface roughness, and more preferable properties than the metallic silver of.

Since the step of forming the conductive layer using the silver ink composition 2 on the substrate is the same as the above-mentioned "silver ink composition", it will be omitted below.

<Coating layer forming process>
The coating layer is, for example, a place where a composition as a raw material for forming the coating layer (hereinafter, may be abbreviated as "composition for a coating layer") is used on a substrate on which a conductive layer is formed. It can be formed by forming a composition layer that coats the conductive layer by adhering to the coating layer, and appropriately selecting and performing a solidification treatment such as a drying treatment or a heat treatment on the composition layer (composition for a coating layer). .. 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, for example, a composition containing an energy ray-curable resin such as an ultraviolet curable resin or a thermosetting resin as the curable resin, and the energy ray-curable resin is blended. The resulting 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, the combination and ratio thereof 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 depending on 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 shall be 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 the polyurethane (meth) acrylate is blended as the energy ray-curable resin, the coating layer composition may be a composition containing a (meth) acrylic acid ester in addition to the 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, the combination and ratio thereof can be arbitrarily selected.

In the composition for a coating layer to which the (meth) acrylic acid ester is not blended, the ratio of the blending amount of the polyurethane (meth) acrylate to the total amount of the blending 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 9% by mass or more, more preferably 75% by mass or more, further preferably 80% by mass or more, and particularly preferably 85% by mass or more, for example, 90% by mass or more, 95. 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 coating layer composition 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.

[Curing agent]
When the composition for the coating layer contains an energy ray-curable resin, a composition containing a curing agent in addition to the energy ray-curable resin is preferable.
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 kind of curing agent may be used alone, or two or more kinds may be used in combination. When two or more types are used in combination, the combination and ratio thereof 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. % Is more preferable.

[Additive]
The composition for a 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, the combination and ratio thereof can be arbitrarily selected.
The blending amount of the additive in the coating layer composition may be appropriately selected depending on 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.

As the migration inhibitor, in addition to the above-mentioned components, a component (adhesion-imparting agent) that improves the adhesion between the resin and the metal can also be used. Examples of such a migration inhibitor include triazine derivatives (compounds having a triazine skeleton). In addition, in this specification, a "derivative" means a compound in which one or more hydrogen atoms of the original compound are substituted with a group other than a hydrogen atom, unless otherwise specified. Here, the "group" includes not only an atomic group formed by bonding a plurality of atoms but also one atom.

In the coating layer composition, the ratio of the blending amount of the migration inhibitor to the blending amount of the curable resin (total blending 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.
Further, among the surfactants, those having a UV-reactive group are preferable, and it is particularly preferable that the nonionic surfactant has a UV-reactive group.
When a nonionic surfactant having a UV-reactive group is used, the effect as a surfactant is obtained, and the deterioration of the haze of the coating layer after the thermal shock test is suppressed.

In the composition for a 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, in the coating layer composition, the ratio of the blending amount of the surfactant to the total blending component 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, 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. Monohydric 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 with 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, etc .; ethers such as diethyl ether, tetrahydrofuran (THF), 1,2-dimethoxyethane (dimethylserosolve); acetone, methyl ethyl ketone (MEK), cyclohexanone, 2,6-dimethyl-4-heptanone. , Isophoron and other ketones; acetonitrile and other nitriles; N, N-dimethylformamide (DMF), N, N-dimethylacetamide and other amides; 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol) and the like keto Examples 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 and the silver ink composition 2 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 is adhered 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 the silver ink composition and the silver ink composition 2, for example. Can be done.

In the coating layer forming step, the thickness of the coating layer can be adjusted by adjusting the amount of the coating 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 and the silver ink composition 2.

When the composition for a 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 the case of curing by irradiation with energy rays, the irradiation amount of energy rays is preferably 200 to 1200 mJ / cm ² , and more preferably 300 to 1000 mJ / cm ² .

<Process of forming other layers>
In the case of producing a laminate in which a conductive layer and other layers other than the coating layer are 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 devices, transparent conductive films >>
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 the base material in the laminated body constitutes at least a part of the housing (exterior material). Except for the points, the configuration may be the same as that of a known electronic device. For example, a flat surface or a curved surface 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. This makes it possible to use 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 laminated body, 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 may be 1 to 200 μm, 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.
It is preferable that the transparent conductive film has a silver layer satisfying 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, the 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 have a more rational structure.
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 by way of 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 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 .

Table 2 shows the surfactants used in the following examples.
Specific examples of the surfactant include "Futergent 610FM (nonionic, fluorine-containing group (hydrophilic group / lipophilic group) -containing oligomer)" manufactured by Neos, and "Futagent 610FM" manufactured by Neos, as shown in Table 2. Surfactant 602A (nonionic, fluorine-containing group (hydrophilic group / lipophilic group) UV-reactive group-containing oligomer) ”was used.

Table 3 shows the migration inhibitors used in the following examples.
Specific examples of the migration inhibitor include 5-MBT: 5-methyl-1H-benzotriazole (manufactured by Wako Junyaku Co., Ltd.) and BT-120: 1,2,3-benzo as shown in Table 3. Triazole (manufactured by Johoku Chemical Co., Ltd.), BT-LX: 1- [N, N-bis (2-ethylhexyl) aminomethyl] benzotriazole (manufactured by Johoku Chemical Co., Ltd.), and TT-LX: 1- [N, N- Bis (2-ethylhexyl) aminomethyl] methylbenzotriazole (manufactured by Johoku Chemical Co., Ltd.) and TT-LYK: 2,2'-[[(methyl-1H-benzotriazole-1-yl) methyl] imino] bisethanol ( Johoku Kagaku Co., Ltd.) and VD-2 (manufactured by Shikoku Kasei Kogyo), which is a triazine derivative, were used.

[Comparative Example 1, Example 1]
<Manufacturing of laminated body>
(Manufacturing of silver ink composition)
In a beaker, 2-ethylhexylamine (1.45 times the molar amount of 2-methylacetate silver acetate described later) and n-hexane (1.63 times the molar amount of 2-methylacetate silver acetate described later), Was added in this order, and 52.9 g of silver 2-methylacetate acetate was added to the beaker so that the liquid temperature was 50 ° C. or lower while rotating and stirring the mechanical stirrer.
After the addition of 2-methylacetate silver is completed, formic acid (0.5 times the amount of 2-methylacetate silver) is added dropwise in a beaker over 10 minutes while maintaining the same state. After the addition of formic acid was completed, the mixture was further stirred as it was for 1.5 hours.
Next, the acetylene alcohol (2), 3,5-dimethyl-1-hexyne-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") (0.004 times by molar with respect to silver 2-methylacetate) which is acetylene alcohol (2). 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 4 shows the types and mixing ratios of each compounding ingredient.
In Table 4, 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 the nitrogen-containing compound] / [metal]. Number of moles of silver forming material]).
Similarly, for the "reducing agent (molar ratio)", the blending amount of the reducing agent (number of moles) per mol of the blending amount of the metallic silver forming material ([number of moles of the reducing agent] / [molar of the metallic silver forming material] Number]).
Similarly, in the case of "acetylene alcohol (2) (molar ratio)", the amount of acetylene alcohol (2) to be blended (number of moles) per mole of the metal silver forming material ([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 mol of the metallic silver forming material (number of moles) ([number of moles of the solvent] / [number of moles of the metallic silver forming material]). Means.

(Formation of silver layer)
The silver ink composition obtained above by the gravure offset printing method on one main surface (surface, first main surface) of a polycarbonate base material (thickness 2 mm, Teijin panlight sheet PC-1151). Was applied to form a print pattern. The print pattern was a mesh pattern in which a large number of lines having the same width were arranged at predetermined intervals in two orthogonal directions.
Next, the substrate on which the above-mentioned printing pattern was formed was (1) blown with hot air at 65 ° C. for 5 minutes, blown with hot air at 120 ° C. for 5 minutes, and then preheated at 100 ° C. for 10 minutes. (2) By heating (baking) at 120 ° C. for 10 minutes under a humidified condition with a relative humidity of 70 to 100%, the width is 4 μm, the distance between adjacent lines in the same direction is 200 μm, and the skew angle is 45 °. Metallic silver line-and-space pattern 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.
Similar to Comparative Example 1 and Example 1, the base material on which the silver layer was formed was used in Examples 2 to 15 described later.

(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. "IRGACURE127") and 5-MBT are mixed with a mixed solvent of 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol) and ethylene glycol monopropyl ether (diacetone alcohol and ethylene glycol monopropyl in the mixed solvent). The mixture was added to and dissolved in a mixed mass ratio of 3: 7) with ether to obtain a diacetone alcohol / ethylene glycol monopropyl ether solution. The amount of the curing agent added is 1% by mass with respect to the amount of the above-mentioned ultraviolet curable resin (A), and the amount of 5-MBT added is the amount of the ultraviolet curable resin (A) added. On the other hand, the amount was set to 1% by mass.
Next, the ultraviolet curable resin (A) 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. (A-1) was obtained. 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 20% by mass. The amount of the footergent 610FM added was such that the content of the footergent 610FM in the coating layer composition (A-1) was 0.3% by mass. 5-MBT is a migration inhibitor.
Table 5 shows the types of each compounding component and the content in the coating layer composition (A-1).
In addition, the description of "-" in the column of the compounding component in Table 5 means that the component is not compounded.

(Formation of coating layer, manufacture of laminate)
EB100 manufactured by Konica Minolta (inkjet head product model number: KM512LH (manufactured by Konica Minolta)): Ink injection amount (droplet amount) at one time: The coating composition (A-1) obtained above was applied by an inkjet printing method using 42 pL) to form a coating film.
Next, the formed coating film is dried at 70 ° 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). Thereby, the entire surface of the pattern forming surface of the base material, that is, the entire surface of the metal silver mesh pattern on the pattern forming surface and the surface of the base material on which the metal silver mesh pattern is not formed. A coating layer was formed to cover the above.
As shown in Table 5, in Comparative Example 1, the coating layer was formed so that the maximum thickness of the coating layer was 10 μm.
Further, as shown in Table 5, in Example 1, the coating layer was formed so that the thickness of the coating layer was 5 μm at the maximum.
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>
(Haze H of laminated body and haze change rate ΔH)
For the laminate obtained above, a thermal shock test in which the laminate is stored at a temperature of 80 ° C. for 30 minutes and then stored at a temperature of -30 ° C for 30 minutes (after the laminate is stored at a temperature of 80 ° C. for 30 minutes, the temperature- A test of storage at 30 ° C. for 30 minutes is defined as one cycle).

At this time, in order to store the laminate at a temperature of 80 ° C. for 30 minutes and then store it at a temperature of −30 ° C. for 30 minutes, the cooling rate when cooling the laminate was set to 103 ° C./min. Further, this cooling was started immediately after the storage of the laminate at a temperature of 80 ° C. for 30 minutes was completed.
On the other hand, after the test of one cycle is completed, when the test of the next cycle is performed, the laminate is stored at a temperature of -30 ° C for 30 minutes and then stored at a temperature of 80 ° C for 30 minutes. The temperature rate was 35 ° C./min. Further, this temperature rise was started immediately after the storage of the laminate at the temperature of −30 ° C. for 30 minutes was completed, except when the haze H _x (%) was measured, which will be described later.

Before the start of the thermal shock test (0 cycle) and at the stage where the thermal shock test of a predetermined cycle is performed (100 to 1500 cycles), the laminated body is subjected to JIS K7136 from the coating layer side (coating layer outer surface). Haze H _x (%) was measured using a haze meter (manufactured by Murakami Color Technology Laboratory). The results are shown in Table 6. The measured values of haze H _x shown in Table 6 are all absolute values. Then, from the haze H ₀ before the start of the thermal shock test (x = 0) and the haze H _x in the x cycle (x> 0) after the start of the thermal shock test, the haze of the laminated body is obtained by the above formula (I _x ). The rate of change ΔH _x (%) was calculated. The results are shown in Table 7.

<Manufacturing and evaluation of laminate>
[Example 2, Example 3]
(Manufacturing of composition for coating layer)
The coating layer composition (A-2) was prepared by the same procedure and composition as in Example 1 except that the footagent 602A was used instead of the footagent 610FM shown in the production of the coating layer composition in Example 1. ) Was obtained. That is, the amount of the footergent 602A added was such that the content of the footergent 602A in the coating layer composition (A-2) was 0.3% by mass.
Table 5 shows the types of each compounding component and the content in the coating layer composition (A-2).

(Formation of coating layer, manufacture of laminate)
The above-mentioned Example 1 was carried out by the same method as the procedure of Example 1 except that the above-mentioned coating layer composition (A-2) was used instead of the coating layer composition (A-1) in Example 1. The entire surface of the pattern-forming surface of the substrate on which the same silver layer as shown in is formed, that is, the surface of the metallic silver mesh pattern on the pattern-forming surface and the metallic silver mesh pattern are not formed. A coating layer was formed to cover the entire surface of the substrate and the entire surface of the substrate.
As shown in Table 5, in Example 2, the coating layer was formed so that the maximum thickness of the coating layer was 10 μm.
Further, as shown in Table 5, in Example 3, the coating layer was formed so that the thickness of the coating layer was 5 μm at the maximum.
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

[Example 4, Example 5, Example 6]
(Manufacturing of composition for coating layer)
In Example 4 according to the same procedure and composition as in Example 2 and Example 3, except that the amount of footagent 602A shown in the production of the coating layer composition in Examples 2 and 3 was changed. The corresponding coating layer composition (A-3), the coating layer composition (A-4) corresponding to Example 5, and the coating layer composition (A-5) corresponding to Example 6 were obtained.
In Example 4, the amount of the footergent 602A added was such that the content of the footergent 602A in the coating layer composition (A-3) was 0.1% by mass.
In Example 5, the amount of the footergent 602A added was such that the content of the footergent 602A in the coating layer composition (A-4) was 0.05% by mass.
In Example 6, the amount of the footergent 602A added was such that the content of the footergent 602A in the coating layer composition (A-5) was 0.01% by mass.
Table 5 shows the types of each compounding component and the contents in the coating layer composition (A-3), the coating layer composition (A-4), and the coating layer composition (A-5).

(Formation of coating layer, manufacture of laminate)
In Example 4, the same method as in the procedure of Example 1 except that the coating layer composition (A-3) was used instead of the coating layer composition (A-1) in Example 1. The entire surface of the pattern forming surface of the base material on which the silver layer similar to that shown in Example 1 is formed, that is, the surface of the metal silver mesh pattern on the pattern forming surface and the metal silver mesh. A coating layer was formed to cover the entire surface of the base material on which the pattern was not formed.
As shown in Table 5, in Example 4, the coating layer was formed so that the maximum thickness of the coating layer was 5 μm.
In Example 5, the same method as in the procedure of Example 1 except that the coating layer composition (A-4) was used instead of the coating layer composition (A-1) in Example 1. The entire surface of the pattern-forming surface of the substrate, that is, the surface of the metallic silver mesh pattern on the pattern-forming surface and the surface of the substrate on which the metallic silver mesh pattern is not formed. A coating layer to be coated was formed.
As shown in Table 5, in Example 5, the coating layer was formed so that the thickness of the coating layer was 5 μm at the maximum.
In Example 6, the same method as in the procedure of Example 1 except that the coating layer composition (A-5) was used instead of the coating layer composition (A-1) in Example 1. The entire surface of the pattern-forming surface of the substrate, that is, the surface of the metallic silver mesh pattern on the pattern-forming surface and the surface of the substrate on which the metallic silver mesh pattern is not formed. A coating layer to be coated was formed.
As shown in Table 5, in Example 6, the coating layer was formed so that the maximum thickness of the coating layer was 5 μm.
As described above, an embodiment in which 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. 4. The laminated body according to Example 5 and Example 6 was obtained.

[Example 7, Example 8]
(Manufacturing of composition for coating layer)
Examples 7 and 8 are supported by the same procedure and composition as in Example 1 except that the surfactant Futergent 610FM shown in the production of the coating layer composition in Example 1 is not added. A composition for a coating layer (A-6) was obtained. That is, the coating layer composition (A-6) is a composition prepared without adding a surfactant.
Table 5 shows the types of each compounding component and the content in the coating layer composition (A-6).

(Formation of coating layer, manufacture of laminate)
In Examples 7 and 8, the procedure of Example 1 was used except that the coating layer composition (A-6) was used instead of the coating layer composition (A-1) in Example 1. The entire surface of the pattern-forming surface of the substrate on which the silver layer similar to that shown in Example 1 was formed, that is, the surface of the metallic silver mesh pattern on the pattern-forming surface, by the same method as in the above. A coating layer was formed to cover the entire surface of the base material on which the metallic silver mesh pattern was not formed.
As shown in Table 5, in Example 7, the coating layer was formed so that the maximum thickness of the coating layer was 10 μm.
As shown in Table 5, in Example 8, the coating layer was formed so that the maximum thickness of the coating layer was 5 μm.
As described above, an embodiment in which 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. 7. A laminate according to Example 8 was obtained.

[Example 9]
(Manufacturing of composition for coating layer)
Hardener (2-hirodoxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropane-1-one, Ciba Japan, Inc. under the condition of 25 ° C. "IRGACURE127") and BT-120 were 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 is 2.5% by mass with respect to the amount of the above-mentioned ultraviolet curable resin (A), and the amount of BT-120 added is the amount of the ultraviolet curable resin (A) added. The amount was set to 2.5% by mass with respect to the amount.
Next, the ultraviolet curable resin (A) 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 (A-7). 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-7) was 50% by mass. BT-120 is a migration inhibitor.
Table 5 shows the types of each compounding component and the content in the coating layer composition (A-7).

(Formation of coating layer, manufacture of laminate)
By the spin coating method (2000 rpm for 5 seconds, then 3000 rpm for 10 seconds), the entire surface of the pattern forming surface of the base material on which the same metallic silver mesh pattern as shown in Example 1 was formed was described above. The obtained coating film composition (A-7) was applied to form a coating film.
Next, the formed coating film is dried at 70 ° 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). Thereby, the entire surface of the pattern forming surface of the base material, that is, the entire surface of the metal silver mesh pattern on the pattern forming surface and the surface of the base material on which the metal silver mesh pattern is not formed. A coating layer was formed to cover the above.
As shown in Table 5, in Example 9, the coating layer was formed so that the maximum thickness of the coating layer was 5 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

[Examples 10 to 15]
(Manufacturing of composition for coating layer)
The composition for the coating layer corresponding to Example 10 was carried out by the same procedure and composition as in Example 9 except that BT-120 shown in the production of the composition for the coating layer in Example 9 was changed to BT-LX. The thing (A-8) was obtained.
In Example 10, the amount of BT-LX added was such that the content of BT-LX in the coating layer composition (A-8) was 2.5% by mass.
The coating layer composition corresponding to Example 11 according to the same procedure as in Example 9 except that BT-120 shown in the production of the coating layer composition in Example 9 was changed to TT-LX. A-9) was obtained.
In Example 11, the amount of TT-LX added was such that the content of TT-LX in the coating layer composition (A-9) was 0.5% by mass.
The BT-120 shown in the production of the coating layer composition in Example 9 is referred to as TT-L.
A coating layer composition (A-10) corresponding to Example 12 was obtained by the same procedure as in Example 9 except that the composition was changed to YK.
In Example 12, the amount of TT-LYK added was such that the content of TT-LYK in the coating layer composition (A-10) was 0.5% by mass.
The coating layer composition corresponding to Example 13 according to the same procedure as in Example 9 except that the BT-120 shown in the production of the coating layer composition in Example 9 was changed to 5-MBT. A-11) was obtained.
In Example 13, the amount of 5-MBT added was such that the content of 5-MBT in the coating layer composition (A-11) was 2.5% by mass.
The coating layer composition corresponding to Example 14 according to the same procedure as in Example 9 except that BT-120 shown in the production of the coating layer composition in Example 9 was changed to VD-2. A-12) was obtained.
In Example 14, the amount of VD-2 added was such that the content of VD-2 in the coating layer composition (A-12) was 2.5% by mass.
The coating layer composition (A-13) corresponding to Example 15 was prepared by the same procedure as in Example 9 except that BT-120 shown in the production of the coating layer composition in Example 9 was not added. Obtained.
That is, the coating layer composition (A-13) according to Example 15 is a composition to which a migration inhibitor is not added.
BT-LX, TT-LX, TT-LYK, 5-MBT, and VD-2 are all migration inhibitors.
Table 5 shows the types of each compounding component and the contents in the coating layer compositions (A-8) to (A-13).

(Formation of coating layer, manufacture of laminate)
In Examples 10 to 15, the above-mentioned coating layer compositions (A-8) to (A-13) were used in place of the coating layer composition (A-7) in Example 9, and other examples were carried out. By the same method as the procedure of Example 9, the entire surface of the pattern forming surface of the substrate on which the same silver layer as that shown in Example 1 is formed, that is, the mesh pattern of metallic silver on the pattern forming surface. A coating layer was formed to cover the entire surface of the base material and the surface of the base material on which the metallic silver mesh pattern was not formed.
As shown in Table 5, in each of Examples 10 to 15, the coating layer was formed so that the maximum thickness of the coating layer was 5 μm.
As described above, an embodiment in which 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. The laminated body according to 7 to 15 was obtained.

<Evaluation of laminated body>
(Haze H of laminated body and haze change rate ΔH)
The laminates according to Examples 2 to 15 obtained above were subjected to a thermal shock test in the same manner as in the procedure described in Example 1.
Further, as in Example 1, the haze H _x (%) was measured using a haze meter (manufactured by Murakami Color Technology Research Institute) at the stage where the thermal shock test of a predetermined cycle was carried out. The results are shown in Table 6. The measured values of haze H _x shown in Table 6 are all absolute values. Then, from the haze H ₀ before the start of the thermal shock test (x = 0) and the haze H _x in the x cycle (x> 0) after the start of the thermal shock test, the haze of the laminated body is obtained by the above formula (I _x ). The rate of change ΔH _x (%) was calculated. The results are shown in Table 7.

As is clear from the above results, the laminates according to Examples 1 to 15 had a small haze _H0 and had favorable optical characteristics. The laminated bodies of Examples 1 to 15 have a small haze change rate at each cycle stage, for example, the haze change rate ΔH ₂₀₀ (%) is 70% or less, and a thermal impact of 200 cycles is achieved. It was confirmed that the change in haze of the entire laminate was suppressed even after the test, and that the preferable optical characteristics were maintained.
As described above, in the laminates of Examples 1 to 15, the coating layer was formed by coating and curing the composition for the coating layer, and even after the thermal shock test regardless of the presence or absence of the additive in the coating layer. It had favorable optical properties.
If the haze is not within 2 to 3%, it looks a little cloudy. Therefore, in optical applications, it is generally preferable that the haze is within 2 to 3%.
According to the laminates according to the examples of Examples 2 to 15, the haze is 2% or less even after the thermal shock test of 700 cycles or more, and the haze change rate is 70% even after the thermal impact test of 800 cycles or more. It was as follows, and had particularly excellent 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.

On the other hand, the laminated body of Comparative Example 1 has a high initial haze H ₀ (%) and a haze change rate ΔH ₂₀₀ (%) exceeding 100%, and the entire laminated body after the thermal impact test. The change in haze was large and the optical characteristics deteriorated.
According to the results of Examples 1 to 15 and Comparative Example 1, when the structure of the surfactant added to the coating layer does not contain a UV reactive group and the film thickness of the coating layer is thick, The laminate haze after the thermal shock test tended to deteriorate.
When the surfactant does not contain a UV reactive group, it is considered that the cause is that the surfactant is difficult to be fixed in the coating layer of the laminate.

In Examples 16 to 23 shown below, an example using "silver ink composition 2" is shown.
[Example 16]
<Manufacturing of silver ink composition 2>
In a beaker, 2-ethylhexylamine (78.18 g, 6.53 times the amount of silver 2-methylacetate acetate described later) and 3,5-dimethyl-1-hexin-3-ol (hereinafter, "DMHO"). (1.17 g, 0.10 times the amount of silver 2-methylacetate) is added and mixed, and the mechanical stirrer is rotated to stir, and the liquid is further added here. 2-Methylacetate silver (20.65 g) was added so that the temperature became 40 ° C. or lower to dissolve each compounding component, and stirring was continued at room temperature for one day.
Next, neodecanoic acid (0.13 times the molar amount with respect to silver 2-methylacetate acetate) was added dropwise to this stirred solution so that the solution temperature was 30 ° C. or lower, and the mixture was stirred to obtain a composition of silver ink. A silver ink composition 2 was obtained.
As DMHO, "Surfinol 61" manufactured by Nisshin Kagaku Co., Ltd. was used, and as neodecanoic acid, "Versatic 10" manufactured by Japan Chemtech Co., Ltd. was used. This also applies to the following Examples and Comparative Examples.

Table 8 shows the types and mixing ratios of each compounding ingredient. In Table 8, 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 the nitrogen-containing compound] / [metal]. Number of moles of silver forming material]). Similarly, for "alcohol (molar ratio)", the amount of alcohol compounded per mol of the metallic silver forming material (number of moles) ([number of moles of alcohol] / [number of moles of metallic silver forming material]). Means. Similarly, in the "molar ratio of branched saturated aliphatic carboxylic acid", the blending amount (number of moles) of the branched saturated aliphatic carboxylic acid per mol of the blending material of the metallic silver forming material ([branched chain saturated]. The number of moles of the aliphatic carboxylic acid] / [the number of moles of the material for forming metallic silver]). Further, the description of "-" in the column of the compounding component / blending amount of the silver ink composition 2 means that the component is not compounded. The same applies to the tables after Table 8 showing the types and mixing ratios of the compounding components.
In this embodiment, the "material for forming metallic silver" is "silver β-ketocarboxylate (1)".

(Formation of silver layer)
The silver ink composition obtained above by the inkjet printing method on one main surface (surface, first main surface) of a polycarbonate base material (thickness 0.18 mm, Teijin panlight sheet PC-2151). The object was painted to form a print pattern. The print pattern was a mesh pattern in which a large number of lines having the same width were arranged at predetermined intervals in two orthogonal directions.
As the inkjet printing method, EB100 manufactured by Konica Minolta (inkjet head product model number: KM512MH (manufactured by Konica Minolta)) was used.
Next, the base material on which the above-mentioned printing pattern is formed is blown with hot air at 120 ° C. for 10 minutes in an oven, so that the line width W to be formed and the distance (space S) between adjacent lines in the same direction are determined. , The values shown in Table 9 below, and the line-and-space pattern of metallic silver having a skew angle of 45 ° formed a mesh pattern of metallic silver formed in two orthogonal directions.
That is, in Example 16, a metallic silver mesh pattern having a line width W of 150 μm and a space of 7950 μm was formed by an inkjet printing method.
The thickness of the metallic silver (silver layer) forming this mesh pattern was 0.02 to 0.07 μm.
Also in Examples 17 to 23 described later, the base material on which the silver layer was formed was used.
In Table 9, in addition to the line width W (μm) and the space S (μm) of Example 16, the line width W (μm) and the space S (μm) of Examples 17 to 23 described later are also shown.

(Manufacturing of composition for coating layer)
In Example 16, the same composition for coating layer (A-3) as in Example 4 was prepared and used for forming the coating layer.
The method for producing the coating layer composition (A-3) will be described in detail below.
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. "IRGACURE127") and 5-MBT are mixed with a mixed solvent of 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol) and ethylene glycol monopropyl ether (diacetone alcohol and ethylene glycol monopropyl in the mixed solvent). The mixture was added to and dissolved in a mixed mass ratio of 3: 7) with ether to obtain a diacetone alcohol / ethylene glycol monopropyl ether solution.
The amount of the curing agent added is 1% by mass with respect to the amount of the above-mentioned ultraviolet curable resin (A), and the amount of 5-MBT added is the amount of the ultraviolet curable resin (A) added. On the other hand, the amount was set to 1% by mass.
Next, the ultraviolet curable resin (A) 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 602A was further added to form a coating layer composition. (A-3) was obtained.
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-3) was 20% by mass.
The amount of the footergent 602A added was such that the content of the footergent 602A in the coating layer composition (A-3) was 0.1% by mass.
5-MBT is a migration inhibitor.
Table 10 shows the types of each compounding component and the content in the coating layer composition (A-3).
In addition, the description of "-" in the column of the compounding component in Table 10 means that the component is not compounded.

(Formation of coating layer, manufacture of laminate)
The coating film composition (A-) obtained above by a spin coating method (600 rpm for 5 seconds, then 800 rpm for 5 seconds) on the entire surface of the pattern-forming surface of the base material on which a metallic silver mesh pattern was formed. 3) was applied to form a coating film.
Next, the formed coating film is dried at 70 ° 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). Thereby, the entire surface of the pattern forming surface of the base material, that is, the entire surface of the metal silver mesh pattern on the pattern forming surface and the surface of the base material on which the metal silver mesh pattern is not formed. A coating layer was formed to cover the above.
Further, as shown in Table 10, in Example 16, the coating layer was formed so that the thickness of the coating layer was 5 μm at the maximum.
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>
(Haze H of laminated body and haze change rate ΔH)
The laminated body according to Example 16 obtained above was subjected to a thermal shock test in the same manner as in the procedure described in Example 1.
That is, with respect to the laminate obtained above, a thermal shock test (after storing the laminate at a temperature of 80 ° C. for 30 minutes, after storing the laminate at a temperature of 80 ° C. for 30 minutes and then storing the laminate at a temperature of −30 ° C. for 30 minutes, A test of storing at a temperature of -30 ° C for 30 minutes is defined as one cycle).

At this time, in order to store the laminate at a temperature of 80 ° C. for 30 minutes and then store it at a temperature of −30 ° C. for 30 minutes, the cooling rate when cooling the laminate was set to 103 ° C./min. Further, this cooling was started immediately after the storage of the laminate at a temperature of 80 ° C. for 30 minutes was completed.
On the other hand, after the test of one cycle is completed, when the test of the next cycle is performed, the laminate is stored at a temperature of -30 ° C for 30 minutes and then stored at a temperature of 80 ° C for 30 minutes. The temperature rate was 35 ° C./min. Further, this temperature rise was started immediately after the storage of the laminate at the temperature of −30 ° C. for 30 minutes was completed, except when the haze H _x (%) was measured, which will be described later.

Before the start of the thermal shock test (0 cycle) and at the stage where the thermal shock test of a predetermined cycle is performed (100 to 400 cycles), the laminated body is subjected to JIS K7136 from the coating layer side (coating layer outer surface). Haze H _x (%) was measured using a haze meter (manufactured by Murakami Color Technology Laboratory). The results are shown in Table 11. The measured values of haze H _x shown in Table 11 are all absolute values. Then, from the haze H ₀ before the start of the thermal shock test (x = 0) and the haze H _x in the x cycle (x> 0) after the start of the thermal shock test, the haze of the laminated body is obtained by the above formula (I _x ). The rate of change ΔH _x (%) was calculated. The results are shown in Table 12.

<Manufacturing and evaluation of laminate>
[Example 17, Example 18, Example 19]
(Formation of silver layer)
Similar to Example 16, the silver layers according to Examples 17 to 19 were used, except that the line width W (μm) and the space S (μm) of the metallic silver mesh pattern were changed to the values shown in Table 9. Formed.
That is, in Example 17, as shown in Table 9, the line width W was set to 150 μm and the space S was set to 3875 μm.
Further, in Example 18, as shown in Table 9, the line width W was set to 150 μm and the space S was set to 4875 μm.
Further, in Example 19, as shown in Table 9, the line width W was set to 150 μm and the space S was set to 9950 μm.

(Manufacturing of composition for coating layer)
As the coating layer compositions of Examples 17 to 19, as shown in Table 10, the same coating layer composition (A-3) as in Example 16 was produced.

(Formation of coating layer, manufacture of laminate)
The covering layer and the laminate according to Examples 17 to 19 were formed by the same method as in Example 16.
As shown in Table 10, in Examples 17 to 19, the coating layer was formed so that the thickness of the coating layer was 5 μm at the maximum.
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

[Example 20, Example 21, Example 22, Example 23]
(Formation of silver layer)
Similar to Example 16, the silver layers according to Examples 20 to 23 were used, except that the line width W (μm) and the space S (μm) of the metallic silver mesh pattern were changed to the values shown in Table 9. Formed.
That is, in Example 20, as shown in Table 9, the line width W was set to 150 μm and the space S was set to 7950 μm.
Further, in Example 21, as shown in Table 9, the line width W was set to 150 μm and the space S was set to 3875 μm.
Further, in Example 22, as shown in Table 9, the line width W was set to 150 μm and the space S was set to 4875 μm.
In addition, in Example 23, as shown in Table 9, the line width W was set to 150 μm and the space S was set to 9950 μm.

(Manufacturing of composition for coating layer)
In Examples 20 to 23, the coating layer composition (A-14) shown below was produced and used for forming the 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. "IRGACURE127") and 5-MBT are mixed with a mixed solvent of 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol) and ethylene glycol monopropyl ether (diacetone alcohol and ethylene glycol monopropyl in the mixed solvent). The mixture was added to and dissolved in a mixed mass ratio of 3: 7) with ether to obtain a diacetone alcohol / ethylene glycol monopropyl ether solution.
The amount of the curing agent added is 2.5% by mass with respect to the amount of the above-mentioned ultraviolet curable resin (A), and the amount of 5-MBT added is the amount of the ultraviolet curable resin (A) added. The amount was set to 2.5% by mass with respect to the amount.
Next, the ultraviolet curable resin (A) was added to the diacetone alcohol / ethylene glycol monopropyl ether solution whose temperature was adjusted to 45 ° C., and the mixture was stirred to obtain a coating layer composition (A-14). rice field.
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-14) was 50% by mass.
5-MBT is a migration inhibitor.
Table 10 shows the types of each compounding component and the content in the coating layer composition (A-14).

(Formation of coating layer, manufacture 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. 14) was applied to form a coating film, and the coating layer and the laminate according to Examples 20 to 23 were formed by the same method as in Example 16.
As shown in Table 10, in Examples 20 to 23, the coating layer was formed so that the thickness of the coating layer was 5 μm at the maximum.
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>
(Haze H of laminated body and haze change rate ΔH)
The laminates according to Examples 17 to 23 obtained above were subjected to a thermal shock test in the same manner as in the procedure described in Example 16.
Further, as in Example 16, the haze H _x (%) was measured using a haze meter (manufactured by Murakami Color Technology Research Institute) at the stage where the thermal shock test of a predetermined cycle was carried out. The results are shown in Table 11. The measured values of haze H _x shown in Table 11 are all absolute values. Then, from the haze H ₀ before the start of the thermal shock test (x = 0) and the haze H _x in the x cycle (x> 0) after the start of the thermal shock test, the haze of the laminated body is obtained by the above formula (I _x ). The rate of change ΔH _x (%) was calculated. The results are shown in Table 12.

As is clear from the above results, the laminates according to Examples 16 to 23 had a small haze _H0 and had favorable optical characteristics. The laminates of Examples 16 to 23 have a small haze change rate at each cycle stage, for example, the haze change rate ΔH ₂₀₀ (%) is 70% or less, and a thermal impact of 200 cycles is achieved. It was confirmed that the change in haze of the entire laminate was suppressed even after the test, and that the preferable optical characteristics were maintained.
As described above, the laminates of Examples 16 to 23 are formed by coating and curing the coating layer of the coating layer composition, and when the silver ink composition 2 is used by the inkjet printing method (silver). Even when the layer was formed by an inkjet printing method), it had favorable optical characteristics even after the thermal shock test regardless of the presence or absence of additives in the coating layer.
If the haze is not within 2 to 3%, it looks a little cloudy. Therefore, in optical applications, it is generally preferable that the haze is within 2 to 3%.
According to the laminates according to the examples of Examples 16 to 23, the haze and the haze change rate in 200 cycles and 400 cycles were very small, and they had excellent optical characteristics.
That is, when the silver layer is formed by the inkjet printing method, the excellent optical properties are maintained in the laminate of the present invention even when the line width and the space are changed and the composition of the coating composition is changed. I was able to confirm that it would be done.

The present invention can be used in various electronic devices having a conductive layer on a substrate, 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 (3)

A laminate comprising a base material, a conductive layer provided on the base material, and a coating layer provided on the conductive layer.
In the laminated body, the first haze H ₀ measured from the coating layer side is 3.0% or less.
A test in which the laminate is stored at a temperature of 80 ° C. for 30 minutes and then the laminate is stored at a temperature of −30 ° C. for 30 minutes is defined as one cycle. In the thermal shock test, after 200 cycles of the thermal shock test. When the second haze _H200 of the laminated body was measured,
Equation I ₂₀₀ : The haze change rate ΔH ₂₀₀ of the laminate calculated by ΔH ₂₀₀ (%) = (H ₂₀₀ −H ₀ ) / H ₀ × 100 is 70% or less .
The material of the conductive layer is silver or copper .
Laminated body. The laminate according to claim 1, wherein the conductive layer is in the form of a mesh. The laminate according to claim 1 or 2 , wherein the conductive layer is laminated in direct contact with the substrate, and the coating layer is laminated in direct contact with the conductive layer.

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