JP2020191286A - Conductive member and laminate - Google Patents

Abstract

To provide a conductive member having a metal-including layer and an adhesive layer, capable of preventing migration from occurring.SOLUTION: A conductive member 10 includes: a metal-including layer in which metal particles are dispersed in a resin material; and an adhesive layer 2 on one side of the metal-including layer. The adhesive layer includes ammonia and amine of 10 ng/g or less in total.SELECTED DRAWING: Figure 1

Description

An embodiment of the present disclosure relates to a conductive member having a metal-containing layer in which metal particles are dispersed in a resin material.

In recent years, metal particles have been attracting attention as a conductive material used for a conductive member. The conductive member using the metal particles has, for example, a metal-containing layer in which the metal particles are dispersed in the resin material.

By the way, conventionally, the occurrence of migration of conductive members has been a problem. Migration is a phenomenon in which, when a voltage is applied to a conductive member, metal particles contained in a metal-containing layer move as metal ions, and for example, metal is deposited in an insulating region. When migration occurs, for example, when a conductive member is used as a wiring base material for a touch panel, a problem such as a short circuit occurs.

Japanese Unexamined Patent Publication No. 2014-29671

By the way, when the conductive member is used as the wiring base material of the touch panel, the conductive member, that is, the metal-containing layer is usually bonded to the transparent base material by the adhesive layer. However, in the case of the configuration in which the adhesive layer is arranged on the surface of the metal-containing layer, there is a problem that the occurrence of migration becomes remarkable.

The present disclosure has been made in view of the above problems, and an object of the present disclosure is to provide a conductive member having a metal-containing layer and an adhesive layer and capable of suppressing the occurrence of migration.

One embodiment of the present disclosure comprises a metal-containing layer in which metal particles are dispersed in a resin material and an adhesive layer on one surface of the metal-containing layer, and ammonia and ammonia contained in the adhesive layer. Provided is a conductive member having a total amount of amines of 10 ng / g or less.

In one embodiment of the present disclosure, a conductive member having a release base material on a surface of the adhesive layer opposite to the metal-containing layer is provided.

One embodiment of the present disclosure comprises a conductive member having a metal-containing layer in which metal particles are dispersed in a resin material and an adhesive layer on one surface of the metal-containing layer, and the adhesive layer of the conductive member. Provided is a laminate having a functional layer on the side surface and having a total amount of ammonia and amines contained in the adhesive layer of 10 ng / g or less.

In one embodiment of the present disclosure, even if the structure has an adhesive layer on one surface of the metal-containing layer, it is possible to obtain a conductive member capable of suppressing the occurrence of migration.

It is the schematic sectional drawing which shows an example of the conductive member of this disclosure. It is the schematic sectional drawing which shows the other example of the conductive member of this disclosure. It is the schematic sectional drawing which shows the other example of the conductive member of this disclosure. It is the schematic sectional drawing which shows an example of the laminated body of this disclosure. It is explanatory drawing for demonstrating the evaluation method of the wiring deterioration width.

In the present specification, when a certain structure such as a member or a certain area is "above (or below)" another structure such as another member or another area, unless otherwise specified. This includes not only the case of being directly above (or directly below) the other configuration, but also the case of being above (or below) the other configuration, that is, another configuration in between above (or below) the other configuration. Including the case where the element is included.

Hereinafter, embodiments of the present disclosure will be described with reference to drawings and the like. However, the present disclosure can be implemented in many different embodiments and is not construed as limited to the description of the embodiments exemplified below. Further, in order to clarify the description, the drawings may schematically represent the width, thickness, shape, etc. of each part as compared with the embodiment, but this is merely an example, and the interpretation of the present disclosure is used. It is not limited. Further, in the present specification and each figure, the same elements as those described above with respect to the above-mentioned figures may be designated by the same reference numerals, and detailed description thereof may be omitted as appropriate. Further, for convenience of explanation, the phrase "upper" or "lower" may be used for explanation, but the vertical direction may be reversed.

Hereinafter, the conductive member and the laminate according to one embodiment of the present disclosure will be described.

A. Conductive Member The conductive member of one embodiment of the present disclosure has a metal-containing layer in which metal particles are dispersed in a resin material, and an adhesive layer on one surface of the metal-containing layer. It is a member in which the total amount of ammonia and amines contained in the layer is 10 ng / g or less.

The conductive member of one embodiment of the present disclosure will be described with reference to the drawings.
FIG. 1 is a schematic cross-sectional view showing an example of a conductive member according to one embodiment of the present disclosure. As shown in FIG. 1, the conductive member 10 of the present disclosure has a metal-containing layer 1 in which metal particles are dispersed in a resin material, and an adhesive layer 2 on one surface of the metal-containing layer. Further, in one embodiment of the present disclosure, the total amount of ammonia and amines contained in the adhesive layer is 10 ng / g or less.

According to the conductive member of one embodiment of the present disclosure, even if the structure has an adhesive layer on one surface of the metal-containing layer, the conductive member can suppress the occurrence of migration.
The following can be considered as specific reasons for obtaining such an effect.

Conventionally, the occurrence of migration has been one of the problems in conductive members. Migration is a phenomenon in which, when a voltage is applied to a conductive member, metal particles contained in a metal-containing layer move as metal ions, and for example, metal is deposited in an insulating region. Therefore, when the conductive member is used for the sensor electrode of the touch panel or the like, there is a problem that a problem such as a short circuit occurs due to the occurrence of migration. Therefore, as a result of repeated studies on the occurrence of migration, the present inventors have a problem that the occurrence of migration becomes particularly remarkable in the case of a conductive member having a structure in which an adhesive layer is arranged on the surface of the metal-containing layer. Was newly discovered.

The present inventors have repeatedly studied the reason why migration is remarkable when a conductive member having a structure in which an adhesive layer is arranged on the surface of a metal-containing layer is used. As a result, we obtained a new finding that ammonia and amines contained in the adhesive layer have an effect. Specifically, it is as follows. First, it is considered that ammonia and amines have a lone electron pair and thus react with a silver oxide as shown in the following formula or other silver halide to form a complex. Since the complex is ionized and charged, it is considered that the complex is easily moved by applying a voltage to generate a gradient. For this reason, when the adhesive layer is arranged on the surface of the metal-containing layer, the ammonia and amines contained in the adhesive layer facilitate the movement of metal ions, and the occurrence of migration is remarkable. It is thought that

Therefore, according to one embodiment of the present disclosure, even if the structure has an adhesive layer on one surface of the metal-containing layer, the total amount of ammonia and amines contained in the adhesive layer shall be within a predetermined range. Therefore, it is considered that the above-mentioned reaction can be suppressed and the occurrence of migration can be suppressed. Although the case where the metal particles contained in the metal-containing layer are silver particles has been described here as a specific example, the same can be applied to other metal particles such as copper particles.

Hereinafter, each configuration of the conductive member according to one embodiment of the present disclosure will be described.

1. 1. Adhesive layer The adhesive layer in one embodiment of the present disclosure is a member arranged on one surface of the metal-containing layer. Further, in one embodiment of the present disclosure, the total amount of ammonia and amines contained in the adhesive layer is 10 ng / g or less.

In one embodiment of the present disclosure, the total amount of ammonia and amines contained in the adhesive layer may be 10 ng / g or less, preferably 7 ng / g or less, and particularly 1 ng / g or less. Is preferable. When the total amount of ammonia and amines contained in the adhesive layer is within the above range, the ammonia or amines contained in the adhesive layer react with the metal particles contained in the metal-containing layer to form metal ions. It can be suppressed. Therefore, when a voltage is applied to the conductive member, the metal ions move, and it is possible to suppress the occurrence of problems such as metal precipitation in an insulating region having no conductivity.

The term "amines" as used herein refers to primary amines, secondary amines, tertiary amines and the like, and specific examples thereof include monomethylamine, dimethylamine and triethylamine.

The total amount of ammonia and amines contained in the adhesive layer can be measured by the following method. For example, the adhesive layer is placed in a polypropylene bag, 60 ml of ultrapure water is further added, and the adhesive layer is immersed in ultrapure water in the bag. Next, the bag is sealed with a heat sealer, placed in a water bath bath at 100 ° C., and allowed to stand for 1 hour. As a result, the components contained in the adhesive layer are eluted into the ultrapure water. Finally, by measuring the ion concentration of the obtained eluate using an ion chromatograph ICS-3000, the total amount of ammonia and amines contained in the adhesive layer can be measured.
When a liquid pressure-sensitive adhesive layer-forming composition is used as the pressure-sensitive adhesive layer, a liquid pressure-sensitive adhesive layer-forming composition is applied onto a base material and dried, in the same manner as described above. The total amount of ammonia and amines can be measured.

As the adhesive layer in one embodiment of the present disclosure, a sheet-like one may be used, or a liquid adhesive layer forming composition may be applied and dried. When the adhesive layer is in the form of a sheet, it can be arranged by laminating the sheet-like adhesive layer on one surface of the metal-containing layer. When the adhesive layer is liquid, it can be arranged by applying a liquid material constituting the adhesive layer on one surface of the metal-containing layer and drying it.

The composition for forming an adhesive layer constituting the adhesive layer is not particularly limited as long as it can be used for a conductive member and the total amount of ammonia and amines is 10 ng / g or less. As the adhesive layer forming composition constituting such an adhesive layer, for example, an acrylic adhesive composition, a urethane adhesive composition, a silicone adhesive composition, or the like can be used. Above all, it is preferable to use an acrylic pressure-sensitive adhesive composition. When an acrylic pressure-sensitive adhesive composition is used, excellent adhesive strength, heat resistance and weather resistance can be obtained as compared with the urethane-based pressure-sensitive adhesive composition. Further, it is possible to obtain an excellent adhesive force as compared with the silicone-based adhesive composition, and it is also excellent in terms of cost.

When an acrylic pressure-sensitive adhesive composition is used as the material of the pressure-sensitive adhesive layer, the composition for forming the pressure-sensitive adhesive layer may be a thermosetting pressure-sensitive adhesive composition containing a main agent resin and a curing agent, or may be a thermosetting adhesive composition containing a main agent resin and ionizing radiation polymerization. It may be an electron beam curable pressure-sensitive adhesive composition containing a sex monomer or an oligomer.
Here, "ionizing radiation" means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or cross-linking a molecule, and usually, ultraviolet rays or electron beams are used, but other X-rays, Electromagnetic waves such as γ-rays and charged particle beams such as α-rays and ion rays can also be used.

Examples of the main resin used in the acrylic pressure-sensitive adhesive composition include an acrylic acid ester copolymer obtained by copolymerizing an acrylic acid ester with another monomer. Examples of the acrylic acid ester include ethyl acrylate, -n-butyl acrylate, -2-ethylhexyl acrylate, isooctyl acrylate, hydroxylethyl acrylate, and acrylamide. These can be used alone or in combination of two or more.

As the curing agent used in the acrylic pressure-sensitive adhesive composition, for example, an isocyanate-based curing agent and an epoxy-based curing agent are widely used. Examples of the isocyanate-based curing agent include a polyisocyanate compound, a trimeric of a polyisocyanate compound, a urethane prepolymer having an isocyanate group at the end obtained by reacting the polyisocyanate compound with a polyol compound, and a trimeric of the urethane prepolymer. The body etc. can be mentioned. Examples of the polyisocyanate compound include 2,4-tolylene diisocyanate, 2,5-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, hexamethylene diisocyanate and the like. Examples of epoxy-based curing agents include bisphenol A and epichlorohydrin-type epoxy resins; ethylene glycol glycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, 1,6-hexanediol diglycidyl ether, N, N, N'. , N'-tetraglycidyl-m-xylene diamine and 1,3-bis (N, N'-diglycidyl aminomethyl) cyclohexane. These can be used alone or in combination.

Examples of the ionizing radiation polymerizable monomer or oligomer used in the acrylic pressure-sensitive adhesive composition include oligomers such as photoradical polymerizable, photocationic polymerizable, and photoanionic polymerizable. Among these, photoradical polymerizable monomers or oligomers are preferable.
This is because the curing rate is high and it is possible to select from a wide variety of compounds.

When an ionizing radiation polymerizable monomer or oligomer is used in the acrylic pressure-sensitive adhesive composition, the purpose is to increase the sensitivity of the ionizing radiation polymerizable monomer or oligomer, and to reduce the polymerization curing time by ionizing radiation and the irradiation amount of ionizing radiation. , It is preferable to add a polymerization initiator.

In addition to the materials described above, the pressure-sensitive adhesive layer according to one embodiment of the present disclosure includes a plasticizer, a metal chelating agent, a silane coupling agent, a dispersant, a defoaming agent, a light stabilizer, and ultraviolet absorption, if necessary. Agents, heat stabilizers, antioxidants and the like can be added. As these, known ones can be used without particular limitation, and can be appropriately selected depending on the performance required for the adhesive layer.

The thickness of the adhesive layer can be appropriately adjusted according to the use of the conductive member in one embodiment of the present disclosure. The thickness of the adhesive layer is, for example, preferably 25 μm or more, particularly preferably 50 μm or more, and particularly preferably 100 μm or more.
The thickness of the adhesive layer is, for example, preferably 500 μm or less, particularly preferably 300 μm or less, and particularly preferably 200 μm or less. When the thickness of the adhesive layer is within the above range, a predetermined adhesiveness can be obtained, and flexibility can be imparted to the conductive member.

As a method of forming the adhesive layer in one embodiment of the present disclosure, for example, when the adhesive layer is in the form of a sheet, a method of laminating the sheet-like adhesive layer on one surface of the metal-containing layer can be mentioned. .. On the other hand, when a liquid adhesive layer forming composition is used, a method of applying the liquid adhesive layer forming composition on one surface of the metal-containing layer and drying it can be mentioned. Examples of the coating method used at this time include known methods such as a spin coating method, a roll coating method, a die coating method, a spray coating method, and a bead coating method.

2. 2. Metal-containing layer The metal-containing layer in one embodiment of the present disclosure is a member in which metal particles are dispersed in a resin material.

Here, the term "resin material" is a concept that includes monomers, oligomers, polymers, and the like, unless otherwise specified.

Further, the “particle” means, for example, a particle having an average primary particle diameter of 0.1 nm or more and 100 μm or less and having a fibrous, spherical or scaly shape.
The average primary particle diameter can be obtained by a method of directly measuring the size of the primary particles from an electron micrograph. Specifically, when the "particles" are fibrous, the particle image is measured by a transmission electron micrograph (TEM) (for example, H-7650 manufactured by Hitachi High-Tech), and 100 randomly selected primary particles are selected. The length of the minor axis of the above, that is, the average value of the lengths of the fiber diameters can be used as the average primary particle size. When the "particle" has another shape such as a spherical shape or a scaly shape, the particle image is measured by TEM, and the average value of the length of the longest part of 100 randomly selected primary particles is averaged as the primary grain. It can be a diameter.

In the metal-containing layer according to one embodiment of the present disclosure, for example, as shown in FIG. 1, metal particles are uniformly dispersed throughout the metal-containing layer 1, and the entire area of the metal-containing layer 1 has a predetermined conductivity. Part 1a may be used, or as shown in FIGS. 2A and 2B, metal particles may be unevenly dispersed in the metal-containing layer. Specifically, as shown in FIG. 2A, metal particles are concentrated on the surface layer of the metal-containing layer 1 on the adhesive layer 2 side, and the surface layer of the metal-containing layer 1 on the adhesive layer 2 side has a predetermined conductivity. The conductive portion 1a may be provided, and the surface layer of the metal-containing layer 1 opposite to the adhesive layer 2 may be the non-conductive portion 1b. Further, as shown in FIG. 2B, metal particles are concentrated on the surface layer of the metal-containing layer 1 opposite to the adhesive layer 2, and the surface layer of the metal-containing layer 1 opposite to the adhesive layer 2 is predetermined. It is a conductive portion 1a having conductivity, and the surface layer on the adhesive layer 2 side of the metal-containing layer 1 may be a non-conductive portion 1b.

Here, the "surface layer" refers to a region near the surface of the metal-containing layer. Further, the "conductive portion" refers to a region having conductivity due to metal particles, and the "non-conductive portion" refers to a region other than the conductive portion in the metal-containing layer. In addition, "having conductivity" means, for example, that the surface resistance value is 1 × 10 ⁶ Ω / □ or less.

Since the thickness of the metal-containing layer in one embodiment of the present disclosure can be appropriately adjusted according to the use of the conductive member, the size of the metal particles contained in the metal-containing layer, and the like, the description thereof is omitted here. ..

Hereinafter, the metal-containing layer according to one embodiment of the present disclosure will be described separately for a conductive portion and a non-conductive portion.

(1) Conductive portion As the metal-containing layer in one embodiment of the present disclosure, for example, as shown in FIG. 1, the entire area of the metal-containing layer 1 may be the conductive portion 1a, or FIGS. 2 (a) and 2 (b). ), The surface layer of any one of the metal-containing layers 1 may be the conductive portion 1a.

In one embodiment of the present disclosure, a conductive member having desired conductivity can be obtained by having a predetermined amount or more of metal particles in the conductive portion in the metal-containing layer. The conductivity of the conductive portion can be appropriately adjusted according to the use of the conductive member in one embodiment of the present disclosure. For example, the surface resistance value of the conductive portion is 1000 Ω / □ or less. Of these, it is preferably 500 Ω / □ or less, and particularly preferably 100 Ω / □ or less. When the surface resistance value of the conductive portion in the metal-containing layer is within the above range, a conductive member having desired conductivity can be obtained. Further, in one embodiment of the present disclosure, the surface resistance value of the conductive portion can be 1 × 10 ⁶ Ω / □ or more.

The surface resistance value of the conductive portion can be measured, for example, by bringing the Loresta-AX MCP-T370 (Mitsubishi Chemical Analytec) into contact with the surface of the conductive portion.

In the metal-containing layer according to one embodiment of the present disclosure, metal particles are dispersed in the resin material.
In other words, the metal particles are embedded in the resin material. The content of the metal particles contained in the metal-containing layer in one embodiment of the present disclosure is preferably such that the metal-containing layer can achieve the desired conductivity, for example. Specifically, the amount of metal particles is preferably 20 parts by weight or more, and more preferably 50 parts by weight or more with respect to 100 parts by weight of the resin material. Further, the content of the metal particles contained in the resin material is preferably within the above range, preferably 3000 parts by weight or less, particularly preferably 1000 parts by weight or less, based on 100 parts by weight of the resin material. Therefore, it is possible to obtain a conductive member having sufficient conductivity.

In the conductive portion in one embodiment of the present disclosure, for example, the ratio of the elements of the metal particles is preferably 0.05 at% or more in terms of atomic composition percentage, and particularly preferably 0.10 at% or more. It is preferably 0.15 at% or more. Further, the ratio of the elements of the metal particles is preferably 10 at% or less in terms of atomic composition percentage, particularly preferably 7 at% or less, and particularly preferably 5 at% or less. When the ratio of the elements of the metal particles in the conductive portion is within the above range, a predetermined conductivity can be imparted to the conductive portion.
The ratio of the elements of the metal particles present in the conductive portion can be measured under the following conditions using, for example, X-ray photoelectron spectroscopy.
・ Acceleration voltage: 15kV
・ Emission current: 10mA
・ X-ray source: A1 dual anode ・ Measurement area: 300 × 700 μmφ
・ Measure the depth of 10 nm from the surface ・ n = 3 times average value

The thickness of the conductive portion in one embodiment of the present disclosure can be appropriately adjusted according to the use of the conductive base material, the size of the metal particles contained in the conductive portion, and the like, and is not particularly limited. For example, when the metal particles contained in the conductive portion are fibrous, the thickness of the conductive portion is preferably less than the fiber diameter. Since the fiber diameter of the metal particles will be described later, the description here will be omitted.

(A) Metal particles The metal particles in one embodiment of the present disclosure are materials contained in a conductive portion and dispersed in a resin material.

Examples of the metal particles in one embodiment of the present disclosure include particles made of gold, silver, copper, palladium, platinum and the like. In one embodiment of the present disclosure, silver particles or copper particles are preferable, and silver particles are particularly preferable. This is because the effect of suppressing the occurrence of migration becomes remarkable by using the conductive member in one embodiment of the present disclosure. The metal particles contained in the conductive portion may have one type or two or more types.

Here, "silver" refers to silver or a silver alloy, and "copper" refers to copper or a copper alloy.
Further, the "silver alloy" refers to an alloy containing silver as a main component and containing silver to the extent that migration occurs when used for a conductive member. Specifically, the ratio of the element of silver is the atomic composition percentage. It means that it is 90 at% or more.
Further, the "copper alloy" refers to an alloy containing copper as a main component and containing copper to the extent that migration occurs when used for a conductive member. Specifically, the ratio of the element of copper is the atomic composition percentage. It means that it is 90 at% or more.
The ratio of silver or copper elements in the silver alloy or copper alloy can be measured, for example, by quantifying the elements using X-ray photoelectron spectroscopy.

The shape of the metal particles in one embodiment of the present disclosure is preferably a shape that can be dispersed in the resin material and can form a conductive portion having conductivity. For example, fibrous, spherical and scaly shapes can be mentioned. In one embodiment of the present disclosure, it is preferable to use fibrous metal particles.

Here, "fibrous" means, for example, a shape in which the ratio of the length of the major axis to the length of the minor axis, that is, the aspect ratio (length of the major axis / length of the minor axis) is larger than 10. To say.
Further, the "fibrous metal particles" may be linear or curved, and may have a linear portion or a curved portion as a part thereof. Further, the "fibrous metal particles" also includes, for example, a plurality of fibrous metal particles linked together.

In one embodiment of the present disclosure, when the metal particles are fibrous, for example, the fiber diameter which is the length of the minor axis is 200 nm or less, and the fiber length which is the length of the major axis is preferably 1 μm or more. When the fiber diameter is within the above range, it is possible to suppress an increase in the haze value of the conductive member and a decrease in light transmission.

Further, when the metal particles are fibrous, for example, the fiber diameter is preferably 10 nm or more, and in this case, it is possible to form a conductive portion having sufficient conductivity. Further, when the fiber length is within the above range, it is possible to form a conductive portion having sufficient conductivity.

Further, when the metal particles are fibrous, for example, the fiber length is preferably 500 μm or less, and in this case, it is possible to suppress an increase in haze value and a decrease in light transmission due to the occurrence of aggregation. It is possible.

Considering the above-mentioned matters when the metal particles are fibrous, in one embodiment of the present disclosure, the fiber diameter of the metal particles is preferably 15 nm or more, and preferably 180 nm or less.
Further, the fiber length of the metal particles is preferably 3 μm or more, and more preferably 10 μm or more. Further, the fiber length of the metal particles is preferably 300 μm or less, and more preferably 30 μm or less.

The fiber diameter and fiber length of the metal particles can be increased by 10 to 500,000 times by using an electron microscope such as a scanning electron microscope called SEM, a transmission electron microscope called TEM, and a scanning transmission electron microscope called STEM. The fiber diameter and fiber length of the fibrous metal particles can be obtained as an average value of 10 measured points.

When the metal particles in one embodiment of the present disclosure are silver particles or copper particles and are fibrous, the silver particles and copper particles may be metal fibers such as so-called silver nanowires and copper nanowires, or , Acrylic fiber coated with silver or copper may be a metal-coated synthetic fiber. In one embodiment of the present disclosure, one kind of metal fiber or metal-coated synthetic fiber may be used, or the metal fiber and the metal-coated synthetic fiber may be used in combination.

When the metal particles in one embodiment of the present disclosure are metal fibers, examples of the method for forming the metal particles include a wire drawing method for extending a metal such as silver and copper for a long time, a cutting method, and the like. When the metal particles are metal-coated synthetic fibers, examples of the method for forming the metal particles include a method of coating acrylic fibers with a metal such as silver or copper.

(B) Resin Material The resin material in one embodiment of the present disclosure is a material contained in a conductive portion, and is a material in which the above-mentioned metal particles are dispersed.

The resin material in one embodiment of the present disclosure is preferably a resin material capable of dispersing the above-mentioned metal particles, and is preferably a transparent material, for example. Here, "transparent" means, unless otherwise specified, transparent to such an extent that, for example, when the conductive member according to one embodiment of the present disclosure is used in a touch panel display device or the like, it does not interfere with visibility from the operator. It means that. Therefore, "transparent" includes colorless transparency and colored transparency to the extent that it does not interfere with visibility, and is not defined by a strict transmittance, and is transparent depending on the use of the conductive member in one embodiment of the present disclosure. The degree of sex can be determined.

The resin material in one embodiment of the present disclosure is preferably, for example, an ionizing radiation curable resin that is cured by ionizing radiation. Here, "ionizing radiation" means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or cross-linking a molecule, and usually, ultraviolet rays or electron beams are used, but other X-rays, Electromagnetic waves such as γ-rays and charged particle beams such as α-rays and ion rays can also be used.

Examples of the ionizing radiation curable resin include compounds having one or two or more unsaturated bonds such as compounds having a functional group such as an acrylate-based resin. Examples of the compound having an unsaturated bond of 1 include ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene, methylstyrene, N-vinylpyrrolidone and the like. Examples of the compound having two or more unsaturated bonds include trimethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, and pentaerythritol. Tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentylglycoldi (meth) acrylate, trimethylolpropane tri (meth) ) Acrylic, dimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, tripentaerythritol octa (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, isocyanurate tri (meth) acrylate, isocyanurate di. (Meta) acrylate, polyester tri (meth) acrylate, polyester di (meth) acrylate, bisphenol di (meth) acrylate, diglycerin tetra (meth) acrylate, adamantyldi (meth) acrylate, isobolonyl di (meth) acrylate, dicyclopentane Examples thereof include polyfunctional compounds such as di (meth) acrylate, tricyclodecanedi (meth) acrylate, and trimethylolpropane tetra (meth) acrylate. Of these, pentaerythritol triacrylate (PETA), dipentaerythritol hexaacrylate (DPHA) and pentaerythritol tetraacrylate (PETTA) are preferably used. The above-mentioned "(meth) acrylate" refers to methacrylate and acrylate. Further, in one embodiment of the present disclosure, as the ionizing radiation curable resin, the above-mentioned compound modified with PO, EO or the like can also be used.

In one embodiment of the present disclosure, in addition to the above-mentioned compounds, a relatively low molecular weight polyester resin having an unsaturated double bond, a polyether resin, an acrylic resin, an epoxy resin, a urethane resin, an alkyd resin, and a spiroacetal. Resins, polybutadiene resins, polythiol polyene resins and the like can also be used as ionizing radiation curable resins.

The ionizing radiation curable resin can also be used in combination with the solvent-drying resin. Here, the "solvent-drying resin" refers to a resin such as a thermoplastic resin that forms a film only by drying a solvent added to adjust the solid content at the time of coating. By using the solvent-drying resin in combination, it is possible to effectively suppress the occurrence of film defects and the like on the coated surface of the coating liquid when the conductive portion is formed using the resin material.

The solvent-drying resin is not particularly limited, and a thermoplastic resin can be generally used. Examples of the thermoplastic resin include styrene resin, (meth) acrylic resin, vinyl acetate resin, vinyl ether resin, halogen-containing resin, alicyclic olefin resin, polycarbonate resin, polyester resin, and polyamide resin. , Cellulose derivatives, silicone resins and rubbers or elastomers.

Further, the thermoplastic resin is preferably non-crystalline and soluble in an organic solvent such as a common solvent capable of dissolving a plurality of polymers and curable compounds. In particular, from the viewpoint of transparency and weather resistance, styrene resin, (meth) acrylic resin, alicyclic olefin resin, polyester resin, cellulose derivative (cellulose ester, etc.) and the like are preferable.

Further, the resin material may contain a thermosetting resin. Examples of the thermosetting resin include phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, melamine-urea cocondensation resin, and silicon resin. Examples thereof include polysiloxane resin.

(2) Non-conductive portion In the metal-containing layer in one embodiment of the present disclosure, for example, as shown in FIGS. 2A and 2B, the surface layer of any one of the metal-containing layers 1 is the conductive portion 1a. The other region may be the non-conductive portion 1b.

In one embodiment of the present disclosure, the non-conductive portion is a region made of a resin material and having non-conductive properties.

Here, "having non-conductive" means not having conductivity.

Since the resin material contained in the non-conductive portion in one embodiment of the present disclosure can be the same as the resin material used for the conductive portion described above, the description thereof is omitted here.

Further, the non-conductive portion in one embodiment of the present disclosure may have other materials in addition to the resin material, if necessary. Examples of other materials include migration inhibitors for suppressing migration. When the non-conductive portion has a migration inhibitor, the migration resistance of the conductive substrate according to the first embodiment of the present disclosure can be effectively improved. The migration inhibitor can be, for example, the same as that described in Japanese Patent Application Laid-Open No. 2014-32792, and thus the description thereof is omitted here.

The thickness of the non-conductive portion in the present invention can be appropriately adjusted according to the use of the conductive base material of the present invention, and is not particularly limited. For example, it can be in the range of 50 nm to 3000 nm.

3. 3. Peeling Base Material In one embodiment of the present disclosure, for example, as shown in FIG. 3, the peeling base material 3 may be provided on the surface of the adhesive layer 2 opposite to the metal-containing layer 1. The release base material is a member that is peeled off when the metal-containing layer is attached to a desired member via the adhesive layer. Therefore, when the release base material is provided, the surface of the adhesive layer may be contaminated before the metal-containing layer is attached to the predetermined member via the adhesive layer, or the surface of the adhesive layer may be affected. Problems such as scratches can be suppressed, and a high-quality conductive member can be obtained.

The material of the release base material is preferably a material that can be arranged on the surface of the pressure-sensitive adhesive layer and can be peeled off from the pressure-sensitive adhesive layer. The release base material in one embodiment of the present disclosure may or may not have transparency, but it is particularly preferable that it has transparency. Examples of such a peeling base material include a layer composed of a silicone resin, an organic resin-modified silicone resin, a fluororesin, an aminoalkyd resin, a melamine resin, an acrylic resin, a polyester resin, and the like.

The thickness of the release base material is preferably such that it can be placed on the surface of the adhesive layer and then peeled off from the surface of the adhesive layer. For example, it is preferably 15 μm or more, and more preferably 25 μm or more. The thickness of the release base material is preferably 100 μm or less, and more preferably 50 μm or less. When the thickness of the release base material is within the above range, the release base material arranged on the surface of the adhesive layer can be easily peeled off.

The release base material in one embodiment of the present disclosure preferably has a predetermined release force with respect to the adhesive layer. As a specific peeling force, for example, it is preferably 10 mN / 25 mm or more, and more preferably 25 mN / 25 mm or more. The peeling force of the peeling substrate against the adhesive layer is preferably 1000 mN / 25 mm or less, and more preferably 500 mN / 25 mm or less. When the peeling force of the peeling base material with respect to the pressure-sensitive adhesive layer is within the above range, the peeling base material arranged on the surface of the pressure-sensitive adhesive layer can be easily peeled off.

In one embodiment of the present disclosure, in order to improve the peelability of the peeling base material, the surface of the peeling base material on the adhesive layer side may be subjected to a mold release treatment. A generally known process can be used for the release process.

4. Base material The base material in one embodiment of the present disclosure is a member that is arranged on the surface of the metal-containing layer on the metal-containing layer 1 side and supports the metal-containing layer, for example, as shown in FIG.

The base material in one embodiment of the present disclosure may or may not have transparency, but it is particularly preferable that the substrate has transparency. Here, "transparent" means that, unless otherwise specified, for example, when the conductive member of the present invention is used in a touch panel display device or the like, it is transparent to such an extent that it does not interfere with visibility from the operator. Say. Therefore, "transparent" includes colorless transparency and colored transparency to the extent that it does not interfere with visibility, and is not defined by a strict transmittance, and is transparent depending on the use of the conductive member in one embodiment of the present disclosure. The degree of sex can be determined.

Examples of the material constituting the base material include polyester resin, acetate resin, polyether sulfone resin, polycarbonate resin, polyamide resin, polyimide resin, polyolefin resin, (meth) acrylic resin, and polychloride. Examples thereof include vinyl-based resins, polyvinylidene chloride-based resins, polystyrene-based resins, polyvinyl alcohol-based resins, polyarylate-based resins, and polyphenylene sulfide-based resins. Above all, it is preferable to use a polyester resin, a polycarbonate resin, or a polyolefin resin.

Further, the base material in the present invention may be an amorphous olefin polymer (Cyclo-Olefin-Polymer: COP) film having an alicyclic structure. This is a substrate on which norbornene-based polymers, monocyclic cyclic olefin-based polymers, cyclic conjugated diene-based polymers, vinyl alicyclic hydrocarbon-based polymers, etc. are used. For example, Zeonex manufactured by Nippon Zeon Co., Ltd. Zeonoa (norbornene resin), Sumitomo Bakelite's Sumilite FS-1700, JSR's Arton (modified norbornene resin), Mitsui Chemicals' appel (cyclic olefin copolymer), Ticona's Topas (cyclic) Olefin copolymer), Optrez OZ-1000 series (alicyclic acrylic resin) manufactured by Hitachi Chemical Co., Ltd. and the like. Further, as an alternative base material for triacetyl cellulose, an FV series (low birefringence, low photoelasticity film) manufactured by Asahi Kasei Chemicals Co., Ltd. can also be used.

The thickness of the base material can be appropriately adjusted according to the use of the conductive member in one embodiment of the present disclosure, and is not particularly limited, but is preferably 1 μm or more, and more preferably 20 μm or more. Is preferable, and it is particularly preferable that the thickness is 40 μm or more. The thickness of the base material is preferably 100 μm or less, particularly preferably 80 μm or less, and particularly preferably 60 μm or less. When the thickness of the base material is within the above range, mechanical strength can be imparted to the base material, and desired flexibility can be realized.

5. Other Configurations The conductive member according to one embodiment of the present disclosure may have other configurations, if necessary, in addition to the configurations described above. It should be noted that other configurations can be appropriately selected depending on the use of the conductive member and the like, and thus the description thereof is omitted here.

6. Applications The conductive member in one embodiment of the present disclosure can be used, for example, as a display such as a liquid crystal display (LCD) or a plasma display (PDP), or as a transparent electrode such as a touch panel or a solar cell.

B. Laminated body The laminated body in one embodiment of the present disclosure includes a conductive member having a metal-containing layer in which metal particles are dispersed in a resin material, an adhesive layer on one surface of the metal-containing layer, and a conductive member. It is a member having a functional layer on the surface on the adhesive layer side and having a total amount of ammonia and amines contained in the adhesive layer of 10 ng / g or less.

The laminate of one embodiment of the present disclosure will be described with reference to the drawings.
FIG. 4 is a schematic cross-sectional view showing an example of the laminated body according to one embodiment of the present disclosure. As shown in FIG. 4, the laminated body 20 of the present disclosure has a conductive member 10 and a functional layer 6. Further, the conductive member 10 has a metal-containing layer 1 in which metal particles are dispersed in a resin material and an adhesive layer 2 on one surface of the metal-containing layer, and ammonia contained in the adhesive layer. And the total amount of amines is 10 ng / g or less.

According to the laminate of one embodiment of the present disclosure, even if the conductive member has an adhesive layer on one surface of the metal-containing layer, the laminate can suppress the occurrence of migration. Since the specific effects can be the same as those described in the above-mentioned "A. Conductive member" section, the description here is omitted.

Hereinafter, each configuration of the laminated body according to one embodiment of the present disclosure will be described.

1. 1. Conductive Member The conductive member in one embodiment of the present disclosure is a member having a metal-containing layer in which metal particles are dispersed in a resin material and an adhesive layer on one surface of the metal-containing layer. Further, it is a member in which the total amount of ammonia and amines contained in the adhesive layer is 10 ng / g or less.

The adhesive layer, the metal-containing layer, and other configurations constituting the conductive member can be the same as those described in the above-mentioned "A. Conductive member", and thus the description here is made. Omit.

2. 2. Functional layer The functional layer in one embodiment of the present disclosure is a member arranged on the surface of the conductive member on the adhesive layer side.

The functional layer in one embodiment of the present disclosure is usually a functional member constituting the touch panel display device, and can be appropriately selected as needed. Examples of the functional layer include a color filter, a touch panel, a decorative member, a protective layer, a liquid crystal layer, and the like. Further, the functional layer such as the color filter, the touch panel and the decorative member may or may not have a transparent base material. Further, in one embodiment of the present disclosure, the above-mentioned functional layer may be used as a single layer, or two or more layers may be used in combination.

Since a general functional member can be mentioned as the functional layer used in one embodiment of the present disclosure, the description thereof is omitted here.

(Metal-containing layer forming step)
Silver nanowires (minor axis length: 35 ± 15 nm, major axis length: 15 μm, Blueano (manufactured by SLV-NW-35)) are placed on a substrate (material: PET, thickness: 50 μm) at about 0. Contains 01 wt%, 0.01 wt% tetrakisepoxysiloxane, 0.2 wt% (n-pyrrolidonepropyl) methylsiloxane-dimethylsiloxane copolymer, 39.78% isopropyl alcohol, 30% 1-butanol, and 30% cyclohexane. The metal particle composition was applied by using the die coating method to form a wet coating film (thickness: 10 μm). Then, the coating film formed on the substrate was heated in an oven at 70 ° C. for 1 minute to form a conductive portion.

Next, a resin composition containing 20% of BS-1200W (manufactured by Arakawa Chemical Industry Co., Ltd.), 15% of cyclohexanone, and 65% of methyl ethyl ketone, which is an ultraviolet curable material, was die-coated on the obtained conductive portion. It was applied by the method to form a wet coating film (thickness: 1 μm). Then, it was heated in an oven at 70 ° C. for 1 minute to form a non-conductive portion.

(Adhesive layer placement process)
A commercially available adhesive layer (thickness: 50 μm or 100 μm) was placed on one surface of the obtained metal-containing layer. The amounts of ammonia and amines contained in each adhesive layer are shown in Table 1 below.
The amount of ammonia and amines contained in the adhesive layer was measured by the following method. That is, the adhesive layer was placed in a polypropylene bag, 60 ml of ultrapure water was further added, and the adhesive layer was immersed in ultrapure water in the bag. Next, the bag is sealed with a heat sealer, placed in a water bath bath at 100 ° C., and allowed to stand for 1 hour. As a result, the components contained in the adhesive layer were eluted in ultrapure water. Finally, the ion concentration of the obtained eluate was measured using an ion chromatograph ICS-3000 to measure the amount of ammonia and amines contained in the adhesive layer.
Here, the amounts of monomethylamine (MMA), dimethylamine (DMA), and triethylamine (TMA) were measured as amines.

[Evaluation]
(Resistance increase rate)
The resistance increase rate of the obtained conductive member was evaluated. The evaluation method of the resistance increase rate will be described with reference to the figure.

5 (a) to 5 (d) are explanatory views for explaining the evaluation method of the resistance increase rate. As shown in FIG. 5A, the conductive member 10 is prepared, then the central portion of the surface of the conductive member 10 is masked with a polyethylene terephthalate film, and in this state, APC (Furuya Metal Co., Ltd.) is applied. Sputter film formation (apparatus: E400, manufactured by Canon Anelva Corporation) is performed to form a patterned metal layer 5 on the surface of the conductive member 10 as shown in FIG. 5 (b). Then, as shown in FIG. 5C, the conductive member 10 was patterned by a laser (λ = 1064 nm) to prepare wirings 5a and 5b. The length T of the wirings 5a and 5b was 40 mm, the wiring width w was 3 mm, and the gap G between the wirings was 30 μm.

As shown in FIG. 5D, the resistance increase rate is evaluated by applying a voltage of 6 V to one of the wirings 5b and storing it in that state for a maximum of 100 hours in an environment of 60 ° C. and 95% Rh. The terminals of the resistance measuring instrument were brought into contact with the patterned metal layers at both ends of the wiring 5b, and the resistance value was measured and evaluated before and after the voltage was applied.

(Wiring alteration width)
In the evaluation of the wiring alteration width, as shown in FIG. 5D, a voltage of 6 V was applied to one of the wirings 5b, and in that state, the wiring was stored in an environment of 60 ° C. and 95% Rh for a maximum of 100 hours. The wiring alteration width of the wiring 5b, that is, the amount of decrease in the wiring width of the wiring 5b was evaluated.

From the results in Table 2, in Examples 1 and 2 in which the total amount of ammonia and amines contained in the adhesive layer is 10 ng / g or less, a comparative example in which the total amount of ammonia and amines contained in the adhesive layer is 10 ng / g or more. It was found that the increase in the resistance increase rate could be suppressed as compared with 1 and 2. Further, it was found that in Examples 1 and 2, the wiring deterioration width was smaller than that in Comparative Examples 1 and 2, and the occurrence of migration could be suppressed.

1 ... Metal-containing layer 2 ... Adhesive layer 3 ... Detachable base material 4 ... Base material 5 ... Metal layer, wiring 6 ... Functional layer 10 ... Conductive member

Claims (1)

A metal-containing layer in which metal particles are dispersed in a resin material,
It has an adhesive layer on one surface of the metal-containing layer,
A conductive member in which the total amount of ammonia and amines contained in the adhesive layer is 10 ng / g or less.

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