TWI720960B - Transparent conductive film with adhesive layer - Google Patents

Abstract

The present invention provides a transparent conductive film with excellent flexibility and high environmental durability.

The transparent conductive film with an adhesive layer of the present invention sequentially includes a transparent substrate, a transparent conductive layer, and an adhesive layer. The transparent conductive layer includes a metal nanowire or a metal mesh. The adhesive layer is composed of The adhesive composition of the base compound and the adhesive material is formed, and the compounding amount of the compound containing the thiol group is 0.01 part by weight to 1 part by weight relative to 100 parts by weight of the adhesive material in the adhesive composition.

Description

Transparent conductive film with adhesive layer

The present invention relates to a transparent conductive film with an adhesive layer.

Previously, as a transparent conductive film used in the electrodes of touch sensors, etc., a transparent conductive film in which a metal oxide layer such as an indium-tin composite oxide layer (ITO layer) is formed on a transparent resin film is often used . However, the transparent conductive film formed with the metal oxide layer has insufficient flexibility, so it is difficult to be used in applications requiring flexibility such as flexible displays.

In addition, as a transparent conductive film, a transparent conductive film including a metal nanowire or metal mesh using silver, copper, or the like has been proposed. Although such a transparent conductive film is excellent in flexibility, it has insufficient resistance to corrosive gas, and the contact of the corrosive gas causes a large decrease in electrical conductivity and a large decrease in light transmittance.

As a method for preventing corrosion of a transparent conductive film containing a metal nanowire or a metal mesh, a method of protecting a conductive layer containing a metal nanowire or metal mesh by a polymer matrix is known (for example, Patent Document 1). However, in order to use a transparent conductive film as an electrode, conduction must be achieved from the surface of the conductive layer. Therefore, the thickness of the polymer matrix is limited, and the metal nanowire or metal mesh cannot be adequately covered by the polymer matrix, thus preventing corrosion. The effect is still insufficient.

[Prior Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Publication No. 2009-505358

The present invention was completed in order to solve the above-mentioned problems, and its object is to provide a transparent conductive film with excellent flexibility and high environmental durability.

The transparent conductive film with an adhesive layer of the present invention sequentially includes a transparent substrate, a transparent conductive layer, and an adhesive layer. The transparent conductive layer includes a metal nanowire or a metal mesh. The adhesive layer is composed of The adhesive composition of the base compound and the adhesive material is formed. In the adhesive composition, the compounding amount of the compound containing the thiol group is 0.01 weight relative to 100 parts by weight of the adhesive material in the adhesive composition Parts ~ 1 part by weight.

In one embodiment, the above-mentioned compound containing a thiol group is represented by the general formula (1); HS-R...(1)

In formula (1), R is an aliphatic hydrocarbon group or an aromatic hydrocarbon group with a carbon number of 1-30.

In one embodiment, the metal nanowire includes one or more metals selected from the group consisting of gold, platinum, silver, and copper.

In one embodiment, the metal mesh includes one or more metals selected from the group consisting of gold, platinum, silver, and copper.

In one embodiment, the transparent conductive layer further includes a polymer matrix.

In one embodiment, the thickness of the transparent conductive layer is 10 nm to 1000 nm.

In one embodiment, a part of the metal nanowire protrudes from the transparent conductive layer.

According to another aspect of the present invention, an electronic device is provided. The electronic device includes the above-mentioned transparent conductive film with an adhesive layer.

According to the present invention, there is provided a transparent conductive film, which is provided with a conductive layer including a metal nanowire or a metal mesh, and an adhesive layer formed of an adhesive composition containing a compound containing a thiol group, thereby being flexible Excellent and high environmental durability.

10‧‧‧Transparent substrate

20‧‧‧Transparent conductive layer

21‧‧‧Metal Nanowire

22‧‧‧Polymer matrix

30‧‧‧Adhesive layer

100‧‧‧Transparent conductive film with adhesive layer

Fig. 1 is a schematic cross-sectional view of a transparent conductive film with an adhesive layer according to an embodiment of the present invention.

A. The overall structure of the transparent conductive film with the adhesive layer

Fig. 1 is a schematic cross-sectional view of a transparent conductive film with an adhesive layer according to an embodiment of the present invention. The adhesive layer-attached transparent conductive film 100 includes a transparent substrate 10, a transparent conductive layer 20, and an adhesive layer 30 in this order. The transparent conductive layer includes metal nanowires or metal meshes. Furthermore, in FIG. 1, the transparent conductive layer 20 represents an example in which a metal nanowire 21 is included. The adhesive layer 30 is formed of an adhesive composition containing a compound containing a thiol group. Hereinafter, the "transparent conductive film with adhesive layer" is also simply referred to as a transparent conductive film.

In one embodiment, the transparent conductive layer 20 is formed of a polymer matrix 22. In this embodiment, a metal nanowire 21 or a metal mesh is present in the polymer matrix 22.

A part of the metal nanowire 21 may protrude from the transparent conductive layer 20. More specifically, a part of the metal nanowire 21 may protrude from the transparent conductive layer 20 to the adhesive layer 30 side. Furthermore, a part of the metal nanowire 21 may protrude outward from the adhesive layer 30. If the metal nanowire 21 is arranged so as to protrude from the transparent conductive layer 20, a transparent conductive film with good conduction can be obtained. In the present invention, even if a part of the metal nanowire protrudes from the transparent conductive layer, the corrosion of the metal nanowire can be prevented.

Generally speaking, the metal-based transparent conductive film may be exposed to corrosive gases in the atmosphere, which may cause the conductivity of the conductive layer to be greatly reduced, and the light transmittance may be greatly reduced. The transparent conductive film of the present invention is provided with an adhesive layer formed of an adhesive composition containing a compound containing a thiol group, so that the compound containing a thiol group in the adhesive layer (or has a structure derived from the compound) The unit polymer) forms a protective film on the metal surface, so that it can be easily combined with the metal body. In this way, the compound containing the thiol group (or the polymer having the structural unit derived from the compound) functions as an anticorrosive agent, thereby preventing the transparent conductive layer Corrosion of metal nanowires or metal meshes. That is, in the present invention, although metal nanowires or metal meshes are used as the material constituting the transparent conductive layer, the corrosion of the material is also prevented, so a transparent conductive film with excellent flexibility and high environmental durability can be obtained. Furthermore, when the transparent conductive layer is composed of a polymer matrix and an anticorrosive agent is added to the polymer matrix, the anticorrosive agent forms a stable composite on the metal surface and forms a barrier at the interface between the metal and the polymer matrix As a result, the appearance of the transparent conductive layer may deteriorate and hardening may be hindered.

The thickness of the transparent conductive film with the adhesive layer is preferably 10 μm to 500 μm, more preferably 15 μm to 300 μm, and still more preferably 20 μm to 200 μm.

The total light transmittance of the transparent conductive film with the adhesive layer is preferably 80% or more, more preferably 85% or more, and particularly preferably 90% or more.

The surface resistance of the transparent conductive film with the adhesive layer is preferably 0.1Ω/□~1000Ω/□, more preferably 0.5Ω/□~500Ω/□, and particularly preferably 1Ω/□~250Ω/□.

B. Adhesive layer

The adhesive layer is formed of an adhesive composition containing a compound containing a thiol group. In more detail, the adhesive composition includes a compound containing a thiol group as an additive and an adhesive material, and the adhesive layer is formed by drying or polymerizing the adhesive composition. Furthermore, the adhesive material includes the concept of a matrix polymer, and monomers and prepolymers (A) as precursors of the matrix polymer. These matrix polymers, monomers and prepolymers (A) can be mixed and used. In the case of using an adhesive composition containing a monomer and/or prepolymer (A) as a precursor of a matrix polymer, the adhesive composition is polymerized to form an adhesive layer, the adhesive The layer contains a matrix polymer containing the monomer and/or prepolymer (A). The matrix polymer in the adhesive layer may or may not contain structural units derived from the above-mentioned thiol group-containing compound. In other words, the compound containing the thiol group can react with the adhesive material to be taken into the matrix polymer in the adhesive layer, or coexist with the matrix polymer in the adhesive layer. In one embodiment, the above The matrix polymer does not contain structural units derived from the above-mentioned compounds containing thiol groups.

In one embodiment, the above-mentioned compound containing a thiol group is added in a state taken into the prepolymer (B). In this embodiment, the monomer for forming the prepolymer (B) and the compound containing a thiol group are reacted to form the prepolymer (B), and then the prepolymer and the adhesive material are mixed to prepare Adhesive composition.

The compounding amount of the compound containing the thiol group relative to 100 parts by weight of the adhesive material in the adhesive composition is 0.01 part by weight to 1 part by weight, preferably 0.01 part by weight to 0.5 part by weight, more preferably 0.01 part by weight Parts to 0.3 parts by weight, more preferably 0.1 parts by weight to 0.2 parts by weight. If it is in this range, the corrosion of the metal nanowire or metal mesh in the transparent conductive layer is prevented. Furthermore, when the prepolymer (B) having a structural unit derived from a compound containing a thiol group is used as described above, "the compounding amount of the compound containing a thiol group" means in the adhesive composition The amount of the thiol group-containing compound introduced into the prepolymer (B). In addition, the prepolymer (B) is not included in the adhesive material.

As the above-mentioned compound containing a thiol group, for example, a compound represented by the general formula (1) can be cited.

HS-R...(1)

In the formula (1), R is an aliphatic hydrocarbon group or an aromatic hydrocarbon group having a carbon number of 1 to 30, preferably an aliphatic hydrocarbon group or an aromatic hydrocarbon group having a carbon number of 1 to 20. R may be linear or branched. In addition, R may include a double bond and/or a triple bond at any appropriate position. In addition, R may have any suitable substituents. Examples of substituents include SH groups, hydroxyl groups, NH ₂ groups, alkyl ester groups, carboxyl groups, allyl groups, and halogen groups. In addition, R may have a substituent containing elements such as N, S, O, Si, and P.

Specific examples of compounds containing thiol groups include: α-thioglycerol, aminoethanethiol, thioglycolic acid, methyl thioglycolate, ethyl thioglycolate, propyl thioglycolate , Butyl thioglycolate, tertiary butyl thioglycolate, 2-ethylhexyl thioglycolate, octyl thioglycolate, isooctyl thioglycolate, decyl thioglycolate, sulfur Generation B Lauryl alkyd, thioglycolate of ethylene glycol, thioglycolate of neopentyl glycol, thioglycolate of pentaerythritol, etc. Among them, preferred are α-thioglycerol, thioglycolic acid, aminoethanethiol, methyl thioglycolate, ethyl thioglycolate, propyl thioglycolate, butyl thioglycolate, sulfur Tert-butyl thioglycolate, 2-ethylhexyl thioglycolate, octyl thioglycolate, isooctyl thioglycolate. If these compounds containing thiol groups are used, the effect of preventing the corrosion of metal nanowires or metal meshes is obvious.

Examples of monomers contained in the adhesive composition include (meth)acrylic monomers, silicon monomers, urethane monomers, epoxy monomers, and the like. Among them, from the viewpoint of transparency and durability, a (meth)acrylic monomer is preferred. Examples of the matrix polymer or prepolymer contained in the adhesive composition include (meth)acrylic monomers, silicon-based monomers, urethane-based monomers, epoxy-based monomers, etc. The matrix polymer or prepolymer.

Examples of the (meth)acrylic monomers include: methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, (meth)acrylate Base) butyl acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tertiary butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate , Heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, (meth) Isononyl acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, ten (meth)acrylate Trialkyl ester, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, cetyl (meth)acrylate, heptadecyl (meth)acrylate, ( Alkyl (meth)acrylates such as stearyl meth)acrylate, isostearyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, etc. . Among them, alkyl (meth)acrylates having a linear or branched alkyl group having a carbon number of 4 to 18 can be preferably used. The content ratio of the alkyl (meth)acrylate relative to 100 parts by weight of all monomers in the adhesive composition is preferably 60 parts by weight or less Above, more preferably 80 parts by weight or more.

、乙烯基吡

、乙烯基吡咯、乙烯基咪唑、乙烯基

唑、乙烯基嗎啉、N-乙烯基羧醯胺類、苯乙烯、α-甲基苯乙烯、N-乙烯基己內醯胺等乙烯基系單體；丙烯腈、甲基丙烯腈等氰基丙烯酸酯系單體；(甲基)丙烯酸縮水甘油酯等含環氧基丙烯酸系單體；(甲基)丙烯酸聚乙二醇酯、(甲基)丙烯酸聚丙二醇酯、(甲基)丙烯酸甲氧基乙二醇酯、(甲基)丙烯酸甲氧基聚丙二醇酯等二醇系丙烯酸酯單體；(甲基)丙烯酸四氫糠酯、氟(甲基)丙烯酸酯、聚矽氧(甲基)丙烯酸酯或丙烯酸2-甲氧基乙酯等丙烯酸酯系單體等。 The aforementioned adhesive composition may further include other monomers. Examples of other monomers include monomers that can be copolymerized with the above-mentioned alkyl (meth)acrylate. Specific examples of the monomer include, for example, acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and other carboxyl-containing groups. Monomers; anhydride monomers such as maleic anhydride and itaconic anhydride; hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxyl (meth)acrylate Hydroxy-containing monomers such as hexyl ester, hydroxyoctyl (meth)acrylate, hydroxydecyl (meth)acrylate, hydroxylauryl (meth)acrylate, (4-hydroxymethylcyclohexyl)methyl methacrylate, etc.; Styrene sulfonic acid, allyl sulfonic acid, 2-(meth)acrylamide-2-methylpropanesulfonic acid, (meth)acrylamide propanesulfonic acid, (meth)sulfopropyl acrylate, ( Sulfonic acid group-containing monomers such as meth)acryloxynaphthalenesulfonic acid. In addition, examples include: vinyl acetate, vinyl propionate, N-vinylpyrrolidone, methylvinylpyrrolidone, vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperidine

Vinylpyridine

, Vinyl pyrrole, vinyl imidazole, vinyl

Vinyl monomers such as azole, vinylmorpholine, N-vinylcarboxamides, styrene, α-methylstyrene, N-vinylcaprolactam, etc.; cyanogens such as acrylonitrile and methacrylonitrile -Based acrylate monomers; epoxy-containing acrylic monomers such as glycidyl (meth)acrylate; polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, (meth)acrylic acid Glycol acrylate monomers such as methoxy glycol ester and methoxy polypropylene glycol (meth)acrylate; tetrahydrofurfuryl (meth)acrylate, fluoro(meth)acrylate, polysiloxane ( Acrylic monomers such as meth)acrylate or 2-methoxyethyl acrylate.

The prepolymer (B) having a structural unit derived from the above-mentioned thiol group-containing compound can be obtained by reacting the monomer for forming the prepolymer (B) with the thiol group-containing compound. As the monomer for forming the prepolymer (B), the above-mentioned monomers can be used.

In one embodiment, as the monomer for forming the prepolymer (B), a (meth)acrylic monomer having an alicyclic structure of three or more rings is used. If you use one with more than three rings The (meth)acrylic monomer with alicyclic structure can form an adhesive layer with excellent durability and adhesion (especially durability and adhesion at high temperature). Examples of (meth)acrylic monomers having an alicyclic structure with three or more rings include: dicyclopentyl methacrylate, dicyclopentyl acrylate, dicyclopentyloxyethyl methacrylate, acrylic acid Dicyclopentyloxyethyl, tricyclopentyl methacrylate, tricyclopentyl acrylate, 1-adamantyl methacrylate, 1-adamantyl acrylate, 2-methyl-2-methacrylate Adamantyl ester, 2-methyl-2-adamantyl acrylate, 2-ethyl-2-adamantyl methacrylate, 2-ethyl-2-adamantyl acrylate and the like.

In the above-mentioned prepolymer (B), the content ratio of the structural unit derived from the (meth)acrylic monomer having an alicyclic structure of three or more rings relative to 100 parts by weight of the prepolymer (B) is preferably It is 40 parts by weight to 80 parts by weight, more preferably 50 parts by weight to 70 parts by weight.

The weight average molecular weight of the prepolymer (B) is preferably 100 to 50,000, more preferably 1,000 to 10,000. The weight average molecular weight can be measured by GPC (gel permeation chromatography) (solvent: THF (tetrahydrofuran)).

The above-mentioned adhesive composition may further contain any appropriate additives as needed. Examples of the additives include initiators, tackifiers, plasticizers, pigments, dyes, fillers, anti-aging agents, conductive materials, ultraviolet absorbers, light stabilizers, peeling regulators, softeners, and interface Active agent, flame retardant, antioxidant, etc. The type, number, and amount of additives used can be appropriately set according to the purpose.

In one embodiment, the adhesive layer may be formed by coating the adhesive composition on the transparent conductive layer, and then polymerizing the coating layer. In this embodiment, after the monomers in the adhesive composition can be partially polymerized, the adhesive composition is coated on the transparent conductive layer to further polymerize the coating layer. As the polymerization method, any appropriate method can be adopted. Preferably, photopolymerization is used. In addition, the adhesive layer formed by polymerization on another substrate can be transferred to the transparent conductive layer.

In another embodiment, after the monomers in the adhesive composition are polymerized to prepare a coating liquid, the coating liquid is applied on the transparent conductive layer, and dried as necessary to form the adhesive Floor.

In another embodiment, an adhesive composition containing a matrix polymer is coated on the transparent conductive layer, and dried as necessary to form the adhesive layer.

The weight average molecular weight of the matrix polymer in the adhesive layer is preferably 200,000-4,000,000, more preferably 400,000-2,000,000.

When the matrix polymer contains the structural unit derived from the compound containing the thiol group, the content ratio of the structural unit derived from the compound containing the thiol group in the adhesive layer is relative to 100 parts by weight of the matrix polymer, Preferably it is 0.01 part by weight to 1 part by weight, more preferably 0.01 part by weight to 0.5 part by weight, still more preferably 0.01 part by weight to 0.3 part by weight, particularly preferably 0.1 part by weight to 0.2 part by weight. If it is in this range, the corrosion of the metal nanowire or metal mesh in the transparent conductive layer is prevented.

When the matrix polymer does not contain structural units derived from the thiol group-containing compound, that is, when the matrix polymer and the thiol group-containing compound coexist in the adhesive layer, the adhesive layer The content ratio of the compound containing the thiol group to 100 parts by weight of the total solid content in the adhesive layer is preferably 0.01 part by weight to 1 part by weight, more preferably 0.01 part by weight to 0.5 part by weight, and more preferably It is 0.01 parts by weight to 0.3 parts by weight, particularly preferably 0.1 parts by weight to 0.2 parts by weight. If it is in this range, the corrosion of the metal nanowire or metal mesh in the transparent conductive layer is prevented.

The thickness of the adhesive layer is preferably 1 μm to 500 μm, more preferably 2 μm to 300 μm.

C. Transparent conductive layer

The transparent conductive layer includes a metal nanowire or a metal mesh. If a transparent conductive layer containing a metal nanowire or a metal mesh is formed, a transparent conductive film with excellent flexibility and excellent light transmittance can be obtained.

In one embodiment, the transparent conductive layer further includes a polymer matrix. In this embodiment, metal nanowires or metal meshes are present in the polymer matrix. In the transparent conductive layer containing the polymer matrix, the metal nanowire or metal mesh is protected by the polymer matrix. As a result, corrosion of the metal nanowire or metal mesh can be prevented, and a transparent conductive film with more excellent durability can be obtained.

The thickness of the transparent conductive layer is preferably 10 nm to 1000 nm, more preferably 20 nm to 500 nm. Furthermore, when the transparent conductive layer includes a polymer matrix, the thickness of the transparent conductive layer is equivalent to the thickness of the polymer matrix.

In one embodiment, the transparent conductive layer is patterned. As a patterning method, any appropriate method can be adopted according to the shape of the transparent conductive layer. The shape of the pattern of the transparent conductive layer can be any suitable shape according to the application. For example, Japanese Patent Application Publication No. 2011-511357, Japanese Patent Application Publication No. 2010-164938, Japanese Patent Application Publication No. 2008-310550, Japanese Patent Application Publication No. 2003-511799, Japanese Patent Application Publication No. 2010-541109 The pattern recorded in the bulletin. After the transparent conductive layer is formed on the transparent substrate, any appropriate method can be used for patterning according to the shape of the transparent conductive layer.

The total light transmittance of the transparent conductive layer is preferably 85% or more, more preferably 90% or more, and still more preferably 95% or more.

(Including transparent conductive layer of metal nanowire)

Metallic nanowire refers to a conductive material that is made of metal, needle-like or thread-like in shape, and nanometer-sized in diameter. Metal nanowires can be straight or curved. If a transparent conductive layer containing metal nanowires is used, the metal nanowires will become a mesh, so that even a small amount of metal nanowires can form a good conductive path, and a transparent conductive film with low resistance can be obtained . Furthermore, by forming the metal nanowire into a mesh shape, openings can be formed in the gaps of the meshes, and a transparent conductive film with high light transmittance can be obtained.

The ratio of the thickness d to the length L of the metal nanowire (aspect ratio: L/d) is preferably 10~ 100,000, more preferably 50 to 100,000, particularly preferably 100 to 10,000. If such a metal nanowire with a large aspect ratio is used, the metal nanowire can cross well, and a small amount of the metal nanowire can exhibit higher conductivity. As a result, a transparent conductive film with high light transmittance can be obtained. Furthermore, in this specification, the "thickness of the metal nanowire" refers to the diameter when the cross-section of the metal nanowire is round, and when it is elliptical, it refers to the short diameter , When it is a polygon, it means the longest diagonal. The thickness and length of the metal nanowire can be confirmed by scanning electron microscope or transmission electron microscope.

The thickness of the metal nanowire is preferably less than 500 nm, more preferably less than 200 nm, particularly preferably 10 nm to 100 nm, and most preferably 10 nm to 50 nm. If it is in this range, a transparent conductive layer with high light transmittance can be formed.

The length of the metal nanowire is preferably 2.5 μm to 1000 μm, more preferably 10 μm to 500 μm, and particularly preferably 20 μm to 100 μm. If it is such a range, a transparent conductive film with high conductivity can be obtained.

As the metal constituting the above-mentioned metal nanowire, any suitable metal can be used as long as it is a metal with relatively high conductivity. Examples of the metal constituting the metal nanowire include silver, gold, copper, nickel, and the like. In addition, it is also possible to use materials that have been plated (for example, gold-plated) on these metals. The metal nanowire preferably includes one or more metals selected from the group consisting of gold, platinum, silver, and copper.

As the manufacturing method of the above-mentioned metal nanowire, any appropriate method can be adopted. Examples include: reducing silver nitrate in a solution; applying voltage or current from the front end of the probe to the surface of the precursor, and using the front end of the probe to draw a metal nanowire, and continuously form the metal nanowire Methods, etc. In the method of reducing silver nitrate in solution, the liquid phase reduction of silver salt such as silver nitrate can be performed in the presence of polyols such as ethylene glycol and polyvinylpyrrolidone to synthesize silver nanowires. Uniform size silver nanowires, for example, according to Xia, Y. etal., Chem. Mater. (2002), 14, 4736-4745, Xia, Y. etal., Nano letters (2003) 3(7), 955-960, which can realize mass production.

The transparent conductive layer containing the metal nanowire can be formed by coating the dispersion liquid obtained by dispersing the metal nanowire in a solvent on the transparent substrate, and then drying the coating layer.

Examples of the above-mentioned solvent include water, alcohol-based solvents, ketone-based solvents, ether-based solvents, hydrocarbon-based solvents, and aromatic-based solvents. From the viewpoint of reducing the environmental load, it is preferable to use water.

The dispersion concentration of the metal nanowire in the metal nanowire dispersion liquid is preferably 0.1% by weight to 1% by weight. If it is in this range, a transparent conductive layer excellent in conductivity and light transmittance can be formed.

The above-mentioned metal nanowire dispersion may further contain any appropriate additives according to the purpose. Examples of the above-mentioned additives include anticorrosive materials that prevent corrosion of metal nanowires, and surfactants that prevent aggregation of metal nanowires. The type, number, and amount of additives used can be appropriately set according to the purpose.

As the coating method of the above-mentioned metal nanowire dispersion liquid, any appropriate method can be adopted. Examples of coating methods include spray coating, bar coating, roll coating, die coating, inkjet coating, screen coating, dip coating, relief printing, and intaglio. Printing method, gravure printing method, etc. As the drying method of the coating layer, any suitable drying method (for example, natural drying, air blowing drying, heat drying) can be adopted. For example, in the case of heating and drying, the drying temperature is typically 50°C to 200°C, and the drying time is typically 1 to 10 minutes.

The content ratio of the metal nanowire in the transparent conductive layer relative to the total weight of the transparent conductive layer is preferably 30% by weight to 90% by weight, more preferably 45% by weight to 80% by weight. If it is such a range, a transparent conductive film excellent in conductivity and light transmittance can be obtained.

When the metal nanowire is silver nanowire, the density of the transparent conductive layer is preferably 1.3 g/cm ³ to 10.5 g/cm ³ , more preferably 1.5 g/cm ³ to 3.0 g/cm ³ . If it is such a range, a transparent conductive film excellent in conductivity and light transmittance can be obtained.

(Contains transparent conductive layer of metal mesh)

The transparent conductive layer containing the metal mesh is formed by forming thin metal wires on the transparent substrate or resin layer in a grid pattern. As the metal constituting the metal mesh, any suitable metal can be used as long as it is a metal with high conductivity. Examples of the metal constituting the metal mesh include silver, gold, copper, nickel, and the like. In addition, it is also possible to use materials that have been plated (for example, gold-plated) on these metals. The metal mesh preferably contains one or more metals selected from the group consisting of gold, platinum, silver, and copper.

The transparent conductive layer including the metal mesh can be formed by any appropriate method. The transparent conductive layer can be formed by, for example, coating a photosensitive composition (composition for forming a transparent conductive layer) containing a silver salt on the transparent substrate, and then performing exposure treatment and development treatment to form fine metal wires into specific The pattern is obtained. In addition, the transparent conductive layer can also be obtained by printing a paste containing metal fine particles into a specific pattern. The details of such a transparent conductive layer and its formation method are described in, for example, Japanese Patent Laid-Open No. 2012-18634, and this description is incorporated into this specification as a reference. In addition, as another example of the transparent conductive layer including the metal mesh and the method of forming the transparent conductive layer, the transparent conductive layer and the method of forming the transparent conductive layer described in Japanese Patent Laid-Open No. 2003-331654 can be cited.

(Polymer matrix)

烯；合成橡膠；氟系聚合物等。較佳為使用包含如下多官能丙烯酸酯 之硬化型樹脂(較佳為紫外線硬化型樹脂)：季戊四醇三丙烯酸酯(PETA)、新戊二醇二丙烯酸酯(NPGDA)、二季戊四醇六丙烯酸酯(DPHA)、二季戊四醇五丙烯酸酯(DPPA)、三羥甲基丙烷三丙烯酸酯(TMPTA)等。 As the polymer constituting the above-mentioned polymer matrix, any suitable polymer can be used. As the polymer, for example, acrylic polymer; polyester polymer such as polyethylene terephthalate; polystyrene, polyvinyl toluene, polyvinyl xylene, polyimide, poly Aromatic polymers such as amides and polyamides; polyurethane-based polymers; epoxy-based polymers; polyolefin-based polymers; acrylonitrile-butadiene-styrene copolymers ( ABS); cellulose; silicon-based polymer; polyvinyl chloride; polyacetate;

Olefin; synthetic rubber; fluorine-based polymer, etc. It is preferable to use a curable resin containing the following polyfunctional acrylate (preferably an ultraviolet curable resin): pentaerythritol triacrylate (PETA), neopentyl glycol diacrylate (NPGDA), dipentaerythritol hexaacrylate (DPHA) ), dipentaerythritol pentaacrylate (DPPA), trimethylolpropane triacrylate (TMPTA), etc.

Preferably, the above-mentioned polymer matrix does not contain metal corrosion preventing materials. If a transparent conductive layer containing no metal corrosion prevention material is formed, a transparent conductive film with excellent appearance can be obtained.

The above-mentioned polymer matrix can be formed by forming a layer containing metal nanowires or metal mesh on a transparent substrate as described above, coating the layer with a polymer solution, and then drying or hardening the coating layer. Through this operation, a transparent conductive layer with metal nanowires or metal meshes in the polymer matrix is formed.

The polymer solution contains the polymer constituting the polymer matrix, or the polymer precursor (monomer constituting the polymer).

The above-mentioned polymer solution may contain a solvent. Examples of the solvent contained in the polymer solution include alcohol-based solvents, ketone-based solvents, tetrahydrofuran, hydrocarbon-based solvents, and aromatic-based solvents. Preferably, the solvent is volatile. The boiling point of the solvent is preferably 200°C or lower, more preferably 150°C or lower, and still more preferably 100°C or lower.

D. Transparent substrate

The thickness of the above-mentioned transparent substrate is preferably 8 μm to 500 μm, more preferably 10 μm to 250 μm, further preferably 10 μm to 150 μm, and particularly preferably 15 μm to 100 μm.

The total light transmittance of the above-mentioned transparent substrate is preferably 80% or more, more preferably 85% or more, and particularly preferably 90% or more. If it is such a range, a transparent conductive film suitable as a transparent conductive film provided in a touch panel etc. can be obtained.

As the resin constituting the above-mentioned transparent substrate, any appropriate resin can be used as long as the effects of the present invention can be obtained. Examples of resins constituting the transparent substrate include cycloolefin resins, polyimide resins, polyvinylidene chloride resins, polyvinyl chloride resins, polyethylene terephthalate resins, and poly(ethylene terephthalate) resins. Ethylene naphthalate resin, etc. More It is preferably a cycloolefin resin. If cycloolefin resins are used, transparent substrates with high moisture barrier properties can be obtained inexpensively. If a transparent substrate with high moisture barrier properties is used, it can be useful as a transparent conductive film for piezoelectric elements with piezoelectric films with low moisture resistance (such as aliphatic polyester resin films). The transparent conductive film.

烯。聚降

烯係指起始原料(單體)之一部分或全部使用具有降

烯環之降

烯系單體而獲得之(共)聚合物。 As the above-mentioned cycloolefin resin, for example, polyether resin can be preferably used.

Ene. Gather down

Alkene means that part or all of the starting materials (monomers) are used to reduce

Ene ring drop

(Co)polymers obtained from olefinic monomers.

烯，市售有各種製品。作為具體例，可列舉：日本Zeon公司製造之商品名「Zeonex」、「Zeonor」；JSR公司製造之商品名「Arton」；TICONA公司製造之商品名「Topas」；三井化學公司製造之商品名「APEL」。 As above

There are various products on the market. As specific examples, include: the brand names "Zeonex" and "Zeonor" manufactured by Zeon Corporation; the brand names "Arton" manufactured by JSR; the brand names "Topas" manufactured by TICONA; the brand names "Topas" manufactured by Mitsui Chemicals Co., Ltd. APEL".

The glass transition temperature of the resin constituting the transparent substrate is preferably 50°C to 200°C, more preferably 60°C to 180°C, and still more preferably 70°C to 160°C.

If it is a transparent substrate with a glass transition temperature in this range, it can prevent deterioration when forming a transparent conductive layer.

The above-mentioned transparent substrate may further contain any appropriate additives as needed. Specific examples of additives include: plasticizers, heat stabilizers, light stabilizers, lubricants, antioxidants, ultraviolet absorbers, flame retardants, colorants, antistatic agents, phase solvents, crosslinking agents, and enhancers. Adhesive etc. The type and amount of additives used can be appropriately set according to the purpose.

As a method for obtaining the above-mentioned transparent substrate, any suitable molding method can be used, for example, self-compression molding method, transfer molding method, injection molding method, extrusion molding method, blow molding method, powder molding method, FRP (Fiber reinforced plastic, fiber reinforced plastic) molding method and solvent casting method, etc., select the appropriate one. Among these manufacturing methods, it is preferable to use an extrusion molding method or a solvent casting method. The reason is that the smoothness of the obtained transparent substrate can be improved, and good optical uniformity can be obtained. Molding conditions can be based on the resin used The composition or type, etc. are appropriately set.

Various surface treatments may be performed on the above-mentioned transparent substrate as needed. The surface treatment adopts any appropriate method according to the purpose. Examples include low-voltage plasma treatment, ultraviolet irradiation treatment, corona treatment, flame treatment, acid or alkali treatment. In one embodiment, the transparent substrate is subjected to surface treatment to make the surface of the transparent substrate hydrophilic. If the transparent substrate is hydrophilized, the processability when the composition for forming a transparent conductive layer prepared from an aqueous solvent (described below) is applied is excellent. In addition, a transparent conductive film having excellent adhesion between the transparent substrate and the transparent conductive layer can be obtained.

E. Purpose

The aforementioned conductive film can be suitably used for electronic equipment such as image display devices. More specifically, the conductive film can be used as an electrode used in a touch panel, etc.; an electromagnetic wave shield that blocks electromagnetic waves that cause malfunctions of electronic equipment, and the like.

[Example]

Hereinafter, the present invention will be specifically explained through examples, but the present invention is not limited in any way by these examples. The evaluation methods in the examples and comparative examples are as follows.

(1) Surface resistance value

The product name "EC-80" manufactured by NAPSON was used for the measurement. The measurement temperature was set to 23°C.

(2) Total light transmittance, haze

The product name "HR-100" manufactured by Murakami Color Research Institute Co., Ltd. was used for measurement. The measurement temperature was set to 23°C. The average value of the 3 repetitions was set as the measured value.

(3) Heating test

The transparent conductive film is cut to length 5cm×width 4.5cm, and a glass plate is laminated on the transparent conductive film to obtain a laminate, and the obtained laminate is put into a constant temperature device (manufactured by Espec Corporation, product name) at a temperature of 90°C. "PH-3KT") and leave it for 240 hours.

Measure the surface resistance value before and after heating by the method of (1) above, according to the rate of change (After heating/Before heating) The durability of the transparent conductive film was evaluated.

[Example 1]

(Synthesis of silver nanowires and preparation of silver nanowire dispersions)

In a reaction vessel equipped with a stirring device, add 0.5 ml of anhydrous ethylene glycol solution (concentration: 1.5×10 ^-4 mol/L) _{of anhydrous ethylene glycol and PtCl 2 at 160°C. After 4 minutes, add 2.5 ml of anhydrous ethylene glycol solution of AgNO 3} (concentration: 0.12mol/l) and anhydrous polyvinylpyrrolidone (MW: 55000) to the obtained solution for 6 minutes. Ethylene glycol solution (concentration: 0.36mol/l) 5ml. After the dropping, it was heated to 160° C. and reacted for more than 1 hour until AgNO _{3 was} completely reduced to produce silver nanowires. Then, acetone was added to the reaction mixture containing the silver nanowires obtained as described above until the volume of the reaction mixture became 5 times, and then the reaction mixture was centrifuged (2000rpm, 20 minutes) to obtain silver nanowires .

The short diameter of the obtained silver nanowire is 30nm~40nm, the long diameter is 30nm~50nm, and the length is 5μm~50μm.

The silver nanowire (concentration: 0.2% by weight) and pentaethylene glycol lauryl ether (concentration: 0.1% by weight) were dispersed in pure water to prepare a silver nanowire dispersion I.

(Preparation of polymer solution for conductive layer formation)

As a solvent, a mixture of isopropanol (manufactured by Wako Pure Chemical Industries, Ltd.) and diacetone alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) at a weight ratio of 1:1 was used. In this solvent, 1.6% by weight of dipentaerythritol, hexaacrylate (DPHA) (manufactured by Shinnakamura Chemical Co., Ltd., brand name "A-DPH"), and a photoreaction initiator (manufactured by Ciba Japan, product name "Irgacure 907" ") 0.09% by weight, polymer solution I was prepared.

(Production of transparent conductive film)

烯系環烯烴膜(日本Zeon股份有限公司製造，商品名「Zeonor」)作為透明基材。 Use drop

An olefin-based cycloolefin film (manufactured by Zeon Co., Ltd., Japan, trade name "Zeonor") was used as a transparent substrate.

Use a bar coater (product name "Bar Coater No. 10" manufactured by Daiichi Science Co., Ltd.) to coat the above-mentioned silver nanowire dispersion A on the transparent substrate, and in a blower dryer at 120°C Let it dry for 2 minutes. After that, the above-mentioned polymer solution I was coated with a wet (Wet) film thickness of 6 μm through a slit mold, and dried in an air dryer at 120° C. for 2 minutes. Then, set the oxygen concentration of 100ppm by ultraviolet light irradiation means Environment (manufactured by Fusion UV Systems, Inc.) accumulated irradiated illuminance of 210mJ / cm ² of UV-curing the polymer solution I, a transparent conductive layer. The surface resistance value of the laminate including the transparent substrate and the transparent conductive layer is 161Ω/□, the total light transmittance is 91.6%, and the haze is 2.0%.

Furthermore, an adhesive composition I (manufactured by Nitto Denko Corporation, trade name "CS9862U") containing acrylic polymer and α-thioglycerin was coated on the transparent conductive layer. The formulation ratio of α-thioglycerol: relative to acrylic 100 parts by weight of the polymer is 0.01 parts by weight) to form an adhesive layer.

As described above, a transparent conductive film including an adhesive layer of transparent substrate (thickness: 100 μm)/transparent conductive layer (thickness: 0.1 μm)/adhesive layer (thickness: 50 μm) was obtained. The obtained transparent conductive film with an adhesive layer was used for the evaluation of (3) above. The results are shown in Table 1.

[Example 2]

Adhesive composition II (manufactured by Nitto Denko Corporation, trade name "CS9912U"; including acrylic polymer and α-thioglycerin, the blending ratio of α-thioglycerin: 0.15 parts by weight relative to 100 parts by weight of acrylic polymer) ) Except that instead of the adhesive composition I, a transparent conductive film was obtained in the same manner as in Example 1. The obtained transparent conductive film with an adhesive layer was used for the evaluation of (3) above. The results are shown in Table 1.

[Example 3]

(Production of prepolymer (b1))

Put 60 parts by weight of dicyclopentyl methacrylate, 40 parts by weight of methyl methacrylate, 3.5 parts by weight of α-thioglycerol, and 100 parts by weight of toluene as a polymerization solvent into a four-necked flask. , Stir at 70°C for 1 hour. Next, 0.2 parts by weight of 2,2'-azobisisobutyronitrile as a polymerization initiator was put into a four-necked flask and reacted at 70°C for 2 hours, and then reacted at 80°C 2 hour. After that, the reaction liquid was put into a temperature environment of 130°C, and toluene and unreacted monomers were dried and removed to obtain a solid acrylic prepolymer (b1). The weight average molecular weight (Mw) of the acrylic prepolymer (b1) was 5.1×10 ³ . Moreover, in the acrylic prepolymer (b1), the content ratio of the structural unit derived from α-thioglycerol was 0.3 parts by weight with respect to 100 parts by weight of the acrylic prepolymer.

(Preparation of Adhesive Composition III)

As monomers, 40.5 parts by weight of isostearyl acrylate, 40.5 parts by weight of 2-ethylhexyl acrylate, 18 parts by weight of N-vinylpyrrolidone, and 1 part by weight of 4-hydroxybutyl acrylate were used. These monomers (total amount: 100 parts by weight) and 0.1 parts by weight of 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by BASF Corporation, trade name "Irgacure 184") as a starting agent were put into a four-necked flask In a nitrogen environment, exposure to ultraviolet rays is performed to partially perform photopolymerization, thereby obtaining a precursor composition containing an adhesive material (including monomers and partial polymers with a polymerization rate of 10%). Add 5 parts by weight of the above-mentioned acrylic prepolymer (b1) and 0.02 parts by weight of trimethylolpropane triacrylate to the obtained precursor composition (including 100 parts by weight of the adhesive material), and then uniformly mix them and Prepare adhesive composition III. In the adhesive composition III, the compounding amount of the compound containing the thiol group is 0.015 parts by weight relative to 100 parts by weight of the adhesive material.

(Production of transparent conductive film with adhesive layer)

The adhesive composition III was applied to the peeling treatment surface of a polyester film with a thickness of 75 μm after peeling treatment on one side with polysiloxane to a thickness of 100 μm to form a coating layer, and on the coating layer After bonding the peeling surface of a 38μm thick polyester film with one side treated by polysilicone peeling, the intensity of the irradiated surface directly below the lamp from the surface of the 38μm thick polyester film side becomes 5mW/cm ² In this way, ultraviolet light is irradiated by a black light lamp that has adjusted the height of the lamp. Polymerization was performed until 3000 mJ/cm ² was irradiated with a light meter to obtain an adhesive layer with a thickness of 150 μm.

In the same manner as in Example 1, a transparent conductive layer was formed on the transparent substrate. Furthermore, the adhesive layer was transferred on the transparent conductive layer to obtain a transparent adhesive layer including a transparent substrate (thickness: 100 μm)/transparent conductive layer (thickness 0.1 μm)/adhesive layer (thickness: 150 μm) Conductive film. The obtained transparent conductive film with an adhesive layer was used for the evaluation of (3) above. The results are shown in Table 1.

[Example 4]

(Production of prepolymer (b2))

Except having used 3.5 parts by weight of thioglycolic acid instead of 3.5 parts by weight of α-thioglycerin, an acrylic prepolymer (b2) was obtained in the same manner as in Example 3. The weight average molecular weight (Mw) of the acrylic prepolymer (b2) is 5.4×10 ³ . Moreover, in the acrylic prepolymer (b2), the content ratio of the structural unit derived from thioglycolic acid was 0.33 parts by weight with respect to 100 parts by weight of the acrylic prepolymer.

(Preparation of Adhesive Composition IV)

Except having used 5 weight part of acrylic prepolymer (b2) instead of 5 weight part of acrylic prepolymer (b1), it carried out similarly to Example 3, and prepared the adhesive composition IV. In the adhesive composition IV, the compounding amount of the compound containing the thiol group is 0.0165 parts by weight relative to 100 parts by weight of the adhesive material.

(Production of transparent conductive film with adhesive layer)

Except that the adhesive composition IV was used instead of the adhesive composition III, in the same manner as in Example 3, a transparent substrate (thickness: 100 μm)/transparent conductive layer (thickness 0.1 μm)/adhesive layer (thickness: 150 μm) was obtained. ) Transparent conductive film with adhesive layer. The obtained transparent conductive film with an adhesive layer was used for the evaluation of (3) above. The results are shown in Table 1.

[Example 5]

(Production of prepolymer (b3))

Except having used 3.5 parts by weight of aminoethanethiol instead of 3.5 parts by weight of α-thioglycerin, an acrylic prepolymer (b3) was obtained in the same manner as in Example 3. The weight average molecular weight (Mw) of the acrylic prepolymer (b3) is 4.9×10 ³ . Moreover, in the acrylic prepolymer (b3), the content ratio of the structural unit derived from thioglycolic acid was 0.32 parts by weight with respect to 100 parts by weight of the acrylic prepolymer.

(Preparation of Adhesive Composition V)

Except having used 5 weight part of acrylic prepolymer (b3) instead of 5 weight part of acrylic prepolymer (b1), it carried out similarly to Example 3, and prepared the adhesive composition V. In the adhesive composition V, the compounding amount of the compound containing the thiol group is 0.016 parts by weight relative to 100 parts by weight of the adhesive material.

(Production of transparent conductive film with adhesive layer)

Except that the adhesive composition V was used instead of the adhesive composition III, a transparent substrate (thickness: 100 μm)/transparent conductive layer (thickness: 0.1 μm)/adhesive layer (thickness: 150 μm) was obtained in the same manner as in Example 3 ) Transparent conductive film with adhesive layer. The obtained transparent conductive film with an adhesive layer was used for the evaluation of (3) above. The results are shown in Table 1.

[Example 6]

烯系環烯烴膜(日本Zeon股份有限公司製造，商品名「Zeonor」)作為透明基材。 Use drop

An olefin-based cycloolefin film (manufactured by Zeon Co., Ltd., Japan, trade name "Zeonor") was used as a transparent substrate.

烯系環烯烴膜進行電暈處理，使表面親水化。之後，於降

烯系環烯烴膜上，使用銀膏(Toyochem股份有限公司製造，商品名「RA FS 039」)藉由網版印刷法形成金屬網(線寬：8.5μm、間距300μm之格子)，於120℃下燒結10分鐘而形成透明導電層。關於包含透明基材及透明導電層之積層體之表面電阻值為155Ω/□，全光線透過率為98.1%，霧度為7.0%。 On the drop

The olefinic cycloolefin membrane undergoes corona treatment to make the surface hydrophilic. After that, Yu Jiang

On the olefin-based cycloolefin film, a silver paste (manufactured by Toyochem Co., Ltd., trade name "RA FS 039") was used to form a metal mesh (line width: 8.5μm, grid with 300μm pitch) by screen printing, at 120°C It is sintered for 10 minutes to form a transparent conductive layer. The surface resistance value of the laminate including the transparent substrate and the transparent conductive layer is 155Ω/□, the total light transmittance is 98.1%, and the haze is 7.0%.

Furthermore, the adhesive combination used in Example 1 was coated on the above-mentioned transparent conductive layer Compound I, an adhesive composition I containing acrylic polymer and α-thioglycerin (manufactured by Nitto Denko Corporation, trade name "CS9862U", blending ratio of α-thioglycerin: relative to 100 parts by weight of acrylic polymer) 0.01 parts by weight) to form an adhesive layer.

As described above, a transparent conductive film including an adhesive layer of transparent substrate (thickness: 100 μm)/transparent conductive layer (thickness: 0.1 μm)/adhesive layer (thickness: 50 μm) was obtained. The obtained transparent conductive film with an adhesive layer was used for the evaluation of (3) above. The results are shown in Table 1.

[Example 7]

Adhesive composition II (manufactured by Nitto Denko Corporation, trade name "CS9912U"; containing acrylic polymer and α-thioglycerin, the blending ratio of α-thioglycerin: 0.15 parts by weight relative to 100 parts by weight of acrylic polymer) ) Except that instead of the adhesive composition I, a transparent conductive film was obtained in the same manner as in Example 6. The obtained transparent conductive film with an adhesive layer was used for the evaluation of (3) above. The results are shown in Table 1.

[Example 8]

The adhesive composition III was prepared in the same manner as in Example 3, and an adhesive layer was obtained.

In the same manner as in Example 6, a transparent conductive layer was formed on the transparent substrate. Furthermore, the above-mentioned adhesive layer was transferred on the transparent conductive layer to obtain a transparent conductive layer comprising a transparent substrate (thickness: 100 μm)/transparent conductive layer (thickness 0.1 μm)/adhesive layer (thickness: 150 μm).性膜。 The film. The obtained transparent conductive film with an adhesive layer was used for the evaluation of (3) above. The results are shown in Table 1.

[Example 9]

The adhesive composition IV was prepared in the same manner as in Example 4, and an adhesive layer was obtained.

In the same manner as in Example 6, a transparent conductive layer was formed on the transparent substrate. Furthermore, the above-mentioned adhesive layer was transferred on the transparent conductive layer to obtain a transparent conductive layer comprising a transparent substrate (thickness: 100 μm)/transparent conductive layer (thickness 0.1 μm)/adhesive layer (thickness: 150 μm).性膜。 The film. The obtained transparent conductive film with adhesive layer was used for the evaluation of (3) above use. The results are shown in Table 1.

[Example 10]

The adhesive composition V was prepared in the same manner as in Example 5, and an adhesive layer was obtained.

In the same manner as in Example 6, a transparent conductive layer was formed on the transparent substrate. Furthermore, the above-mentioned adhesive layer was transferred on the transparent conductive layer to obtain a transparent conductive layer comprising a transparent substrate (thickness: 100 μm)/transparent conductive layer (thickness 0.1 μm)/adhesive layer (thickness: 150 μm).性膜。 The film. The obtained transparent conductive film with an adhesive layer was used for the evaluation of (3) above. The results are shown in Table 1.

[Comparative Example 1]

Adhesive composition VI (manufactured by Nitto Denko Corporation, trade name "CS9892U"; containing acrylic polymer and not containing thiol group-containing compound) was used instead of adhesive composition I, except that it was the same as Example 1 To obtain a transparent conductive film.

[Comparative Example 2]

Adhesive composition VII (manufactured by Nitto Denko Corporation, trade name "CS9922U"; containing acrylic polymer and not containing thiol group-containing compound) was used instead of adhesive composition I, except that it was the same as Example 1 To obtain a transparent conductive film.

[Comparative Example 3]

(Preparation of Adhesive Composition VIII)

Except having used 0.05 weight part of acrylic prepolymer (b1) instead of 5 weight part of acrylic prepolymer (b1), it carried out similarly to Example 3, and prepared the adhesive composition VIII. In the adhesive composition VIII, the compounding amount of the compound containing the thiol group is 0.00015 parts by weight relative to 100 parts by weight of the adhesive material.

(Production of transparent conductive film with adhesive layer)

Except that the adhesive composition VIII was used instead of the adhesive composition III, in the same manner as in Example 3, a transparent substrate (thickness: 100 μm)/transparent conductive layer (thickness 0.1 μm)/Adhesive layer (thickness: 150μm) of the transparent conductive film attached to the adhesive layer. The obtained transparent conductive film with an adhesive layer was used for the evaluation of (3) above. The results are shown in Table 1.

[Comparative Example 4]

Adhesive composition VI (manufactured by Nitto Denko Corporation, trade name "CS9892U"; containing acrylic polymer and not containing thiol group-containing compound) was used instead of adhesive composition I, except that it was the same as Example 6 To obtain a transparent conductive film.

[Comparative Example 5]

Adhesive composition VII (manufactured by Nitto Denko Corporation, trade name "CS9922U"; containing acrylic polymer and not containing thiol group-containing compound) was used instead of adhesive composition I, except that it was the same as Example 6 To obtain a transparent conductive film.

[Comparative Example 6]

The adhesive composition VIII was prepared in the same manner as in Comparative Example 3, and further an adhesive layer was obtained.

In the same manner as in Example 6, a transparent conductive layer was formed on the transparent substrate. Furthermore, the above-mentioned adhesive layer was transferred on the transparent conductive layer to obtain a transparent conductive layer comprising a transparent substrate (thickness: 100 μm)/transparent conductive layer (thickness 0.1 μm)/adhesive layer (thickness: 150 μm).性膜。 The film. The obtained transparent conductive film with an adhesive layer was used for the evaluation of (3) above. The results are shown in Table 1.

According to Table 1, it can be seen that the change rate of the surface resistance value before and after the heating test of the transparent conductive film with the adhesive layer of the present invention is reduced. Regarding this transparent conductive film, the compound containing the thiol group in the adhesive layer can be used as an anti-corrosion agent to easily bond with the metal body to form a protective film on the metal surface, thereby inhibiting the corrosion of the metal.

10‧‧‧Transparent substrate

20‧‧‧Transparent conductive layer

21‧‧‧Metal Nanowire

22‧‧‧Polymer matrix

30‧‧‧Adhesive layer

100‧‧‧Transparent conductive film with adhesive layer

Claims (7)

An adhesive layer-attached transparent conductive film, which sequentially includes a transparent substrate, a transparent conductive layer and an adhesive layer. The transparent conductive layer includes a metal nanowire or a metal mesh. The adhesive layer is composed of The adhesive composition of the base compound and the adhesive material is formed. In the adhesive composition, the compounding amount of the compound containing the thiol group is 0.01 weight relative to 100 parts by weight of the adhesive material in the adhesive composition Part~1 part by weight, the compound containing thiol group is selected from at least one of the group consisting of α-thioglycerol, aminoethanethiol and thioglycolic acid. The transparent conductive film with an adhesive layer of claim 1, wherein the transparent conductive layer includes the metal nanowire, and the metal nanowire includes one selected from the group consisting of gold, platinum, silver, and copper The above metal. The transparent conductive film with an adhesive layer according to claim 1, wherein the transparent conductive layer includes the metal mesh, and the metal mesh includes one or more metals selected from the group consisting of gold, platinum, silver, and copper. The transparent conductive film with an adhesive layer according to claim 1, wherein the transparent conductive layer further comprises a polymer matrix. According to claim 4, the transparent conductive film with an adhesive layer, wherein the thickness of the transparent conductive layer is 10 nm to 1000 nm. The transparent conductive film with an adhesive layer according to claim 4 or 5, wherein the transparent conductive layer includes the metal nanowire, and a part of the metal nanowire protrudes from the transparent conductive layer. An electronic device comprising the transparent conductive film with an adhesive layer as claimed in claim 1.

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