KR20230101808A - conductive optical stack - Google Patents

Abstract

A conductive optical laminate in which deterioration of the metal nanowires is prevented while having a transparent conductive layer including a polarizer and metal nanowires is provided.
The conductive optical laminate of the present invention includes a polarizer, a block layer, and a transparent conductive layer in this order, and the block layer is a resin layer. In one embodiment, the block layer contains an acrylic resin and an epoxy resin. In one embodiment, the conductive optical laminate has a plurality of layers of the block layer.

Description

conductive optical stack

The present invention relates to a conductive optical laminate.

Conventionally, a conductive film in which a metal oxide layer such as an indium/tin composite oxide layer (ITO layer) is formed on a resin film is widely used as a conductive film used for electrodes of a touch sensor or the like. However, the conductive film on which the metal oxide layer is formed has a problem of insufficient flexibility. As a conductive film with excellent flexibility, a conductive film provided with a transparent conductive layer made of metal nanowires or metal meshes using silver, copper, or the like has been proposed.

Japanese Patent Publication No. 2009-505358

A conductive film is used in combination with an image display panel in many cases, and in that case, it may be arrange|positioned and used near a polarizer. In such a case, the component contained in the polarizer (particularly, the iodine component) has an effect, and the metal nanowires in the transparent conductive layer of the conductive film are deteriorated, causing a problem that the conductivity of the conductive film is lowered.

The present invention has been made to solve the above problems, and an object of the present invention is a conductive optical laminate in which deterioration of the metal nanowires is prevented while providing a transparent conductive layer including a polarizer and a metal nanowire or a metal mesh. is to provide

The conductive optical laminate of the present invention includes a polarizer, a block layer, and a transparent conductive layer in this order, the block layer is a resin layer, and the transparent conductive layer contains metal nanowires or metal mesh.

In one embodiment, the said block layer contains an acrylic resin and an epoxy resin.

In one embodiment, the said acrylic resin contains the structural unit derived from an acrylic monomer, and the structural unit derived from the monomer (a) represented by following formula (1).

[Formula 1]

(Wherein, X is a group consisting of a vinyl group, a (meth)acrylic group, a styryl group, a (meth)acrylamide group, a vinylether group, an epoxy group, an oxetane group, a hydroxyl group, an amino group, an aldehyde group, and a carboxyl group represents a functional group containing at least one reactive group selected from, and R ¹ and R ² are each independently a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, an aryl group which may have a substituent, or a substituent; It represents an optional heterocyclic group, and R ¹ and R ² may be linked to each other to form a ring.)

In one embodiment, in the said acrylic resin, the content rate of the structural unit derived from the said monomer (a) is more than 0 weight part and less than 50 weight part with respect to 100 weight part of the acrylic resin.

In one embodiment, the total thickness of the said block layer is 0.1 micrometer - 16 micrometers.

In one embodiment, the conductive optical laminate has a plurality of layers of the block layer.

In one embodiment, the conductive optical laminate further includes a substrate, and the transparent conductive layer is disposed on the substrate.

In one embodiment, the conductive optical laminate further includes a protective layer disposed between the block layer and the transparent conductive layer to protect the transparent conductive layer.

In one embodiment, the metal constituting the metal nanowire is at least one metal selected from the group consisting of gold, platinum, silver, copper, aluminum, rhodium, and nickel.

In one embodiment, the metal constituting the metal mesh is at least one metal selected from the group consisting of gold, platinum, silver, copper, aluminum, rhodium, and nickel.

In one embodiment, the metal nanowire is made of a material obtained by plating at least one metal selected from the group consisting of gold, platinum, silver, copper, aluminum, rhodium, and nickel.

In one embodiment, the metal mesh is made of a material obtained by plating at least one metal selected from the group consisting of gold, platinum, silver, copper, aluminum, rhodium, and nickel.

According to the present invention, it is possible to provide a conductive optical laminate in which deterioration of the metal nanowires is prevented while having a transparent conductive layer including a polarizer and metal nanowires.

1 is a schematic cross-sectional view of a conductive optical laminate according to one embodiment of the present invention.
2(a) to (e) are schematic cross-sectional views of a conductive optical laminate according to another embodiment of the present invention.

A. Overall configuration of the conductive optical laminate

1 is a schematic cross-sectional view of a conductive optical laminate according to one embodiment of the present invention. The conductive optical laminate 100 includes a polarizer 10, a block layer 20, and a transparent conductive layer 30 in this order. The transparent conductive layer 30 contains metal nanowires or metal mesh (not shown). Preferably, the conductive optical laminate may further include a substrate 40 . The transparent conductive layer 30 may be disposed on the substrate 40 .

2(a) to (e) are schematic cross-sectional views of a conductive optical laminate according to another embodiment of the present invention.

As shown in FIGS. 2(a), 2(c), and 2(e), the conductive optical laminates 200, 400, and 600 are protective layers arranged so as to protect the transparent conductive layer 30 You may have (31). The protective layer 31 may be disposed between the block layer 20 and the transparent conductive layer 30 . It is preferable that the protective layer 31 is disposed directly on the transparent conductive layer 30 (that is, without intervening other layers).

As shown in FIGS. 1 and 2(a) to (e), in the conductive optical laminate, each layer (eg, a polarizer, a block layer, a transparent conductive layer, other layers that may be arbitrarily arranged, etc. ), an arbitrary appropriate pressure-sensitive adhesive layer or adhesive layer may be disposed (in the illustrated example, the pressure-sensitive adhesive layer 50).

The block layer 20 may be arranged in a plurality of layers (for example, two layers). As shown in FIGS. 2(d) and (e), in one embodiment, the block layer 20 may be arranged in two layers with the pressure-sensitive adhesive layer 50 (or adhesive layer) interposed therebetween. . By forming a plurality of block layers, the effect of preventing deterioration of the metal nanowire becomes remarkable. The configuration (composition, thickness, etc.) of the multi-layered block layer may be the same or different, respectively. Moreover, you may provide the 2nd block layer on the opposite side to the block layer of a polarizer (not shown). The block layer and the second block layer may have the same configuration or different configurations, respectively.

Although not shown, the conductive optical laminate may further include any appropriate other layer. For example, the conductive optical laminate may have a polarizer protective film arranged on at least one side of the polarizer. In one embodiment, only one side of the polarizer is protected by the polarizer protective film. In one embodiment, a block layer (and/or a 2nd block layer) exhibits the function which protects a polarizer, and is arrange|positioned as a substitute for a polarizer protective film.

In the present invention, as exemplified above, by forming a block layer between the polarizer and the transparent conductive layer, it is possible to prevent a component in the polarizer (typically, an iodine component) from affecting the transparent conductive layer. there is. As a result, deterioration of the metal nanowires in the transparent conductive layer is prevented, and a conductive optical laminate having excellent conductivity and excellent durability can be provided.

B. Polarizer

As the polarizer, any suitable polarizer is used. For example, a dichroic substance such as iodine or a dichroic dye is adsorbed to a hydrophilic polymer film such as a polyvinyl alcohol-based film, a partially formalized polyvinyl alcohol-based film, or an ethylene-vinyl acetate copolymer-based partially saponified film to obtain a single axis Polyene type oriented films, such as what stretched, the dehydration process material of polyvinyl alcohol, and the dehydrochlorination process material of polyvinyl chloride, etc. are mentioned. Among these, a polarizer obtained by adsorbing a dichroic substance such as iodine to a polyvinyl alcohol-based film and uniaxially stretching the polarizer has a high polarization dichroic ratio and is particularly preferable. The thickness of the polarizer is preferably from 0.5 μm to 80 μm.

A polarizer obtained by adsorbing iodine to a polyvinyl alcohol-based film and stretching it uniaxially is typically produced by immersing polyvinyl alcohol in an aqueous solution of iodine, dyeing it, and stretching it 3 to 7 times the original length. Stretching may be performed after dyeing, stretching may be performed while dyeing, or dyeing may be performed after stretching. In addition to stretching and dyeing, for example, swelling, crosslinking, conditioning, water washing, and drying are performed to produce the fabric.

In one embodiment, iodine content of a polarizer is 2 weight% - 25 weight% (preferably 10 weight% - 25 weight%, More preferably, 15 weight% - 25 weight%). In this specification, "iodine content" means the quantity of all the iodine contained in a polarizer (PVA system resin film). More specifically, in the polarizer, iodine exists in the form of iodine ions (I ^- ), iodine molecules (I ₂ ), polyiodine ions (I ₃ ^- , I ₅ ^- ), etc., iodine in this specification The content means the amount of iodine including all of these forms. The iodine content can be calculated, for example, by a calibration curve method of fluorescence X-ray analysis. Moreover, polyiodine ion exists in the state which formed the PVA- iodine complex in a polarizer. By forming such a complex, absorption dichroism can be expressed in the wavelength range of visible light. Specifically, a complex of PVA and tri-iodide ions (PVA·I ₃ ^- ) has an absorption peak around 470 nm, and a complex of PVA and 5 iodide ions (PVA·I ₅ ^- ) has an absorption peak around 600 nm have a peak As a result, polyiodine ions can absorb light in a wide range of visible light depending on their form. On the other hand, iodine ions (I ^- ) have an absorption peak around 230 nm and are not substantially involved in absorption of visible light. Therefore, the polyiodine ion present in a complex state with PVA may be mainly involved in the absorption performance of the polarizer.

The single transmittance of the polarizer is, for example, 30% or more. In addition, the theoretical upper limit of single transmittance is 50%, and the practical upper limit is 46%. In addition, the single transmittance (Ts) is a Y value obtained by measuring with a 2-degree field of view (C light source) of JIS Z 8701 and correcting the visibility, for example, a spectrophotometer with an integrating sphere (manufactured by Nippon Spectroscopy Co., Ltd., product name: V7100). ) can be measured using

The degree of polarization of the polarizer is, for example, 99.0% or more, preferably 99.5% or more, more preferably 99.9% or more.

In one embodiment, a protective film is arrange|positioned on at least one surface of the said light polarizer. When the conductive optical laminate has a polarizer with a protective film, a block layer may be disposed between the polarizer with a protective film and the transparent conductive layer. Arbitrary suitable films are used as said protective film. As a specific example of the material used as the main component of such a film, transparent resins, such as cellulose-type resins, such as triacetyl cellulose (TAC), etc. are mentioned.

C. block layer

Typically, the block layer is a resin layer. In one embodiment, a block layer contains acrylic resin and/or epoxy resin. The content ratio of the acrylic resin to the epoxy resin (acrylic resin:epoxy resin) is preferably 95:5 to 60:40 or 40:60 to 1:99 by weight; more preferably 95:5 to 80:20 or 20:80 to 5:95; More preferably, it is 90:10 to 70:30, or 30:70 to 10:90. Within such a range, it is possible to form a block layer with excellent adhesion to adjacent layers and excellent transparency.

Preferably, the said acrylic resin contains the structural unit derived from an acrylic monomer, and the structural unit derived from the monomer (a) represented by following formula (1). In this specification, an acrylic resin containing a structural unit derived from an acrylic monomer and a structural unit derived from a monomer represented by the following formula (1) may be referred to as "acrylic resin (A)". In addition, the monomer (a) represented by the following formula (1) may be simply referred to as "monomer (a)". By forming a block layer by using the acrylic resin (A) containing structural units derived from the monomer (a) in combination with an epoxy resin, the movement of the polarizer component is prevented, and a conductive optical laminate having remarkably excellent durability can be obtained.

[Formula 2]

(Wherein, X is a group consisting of a vinyl group, a (meth)acrylic group, a styryl group, a (meth)acrylamide group, a vinylether group, an epoxy group, an oxetane group, a hydroxyl group, an amino group, an aldehyde group, and a carboxyl group represents a functional group containing at least one reactive group selected from, and R ¹ and R ² are each independently a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, an aryl group which may have a substituent, or a substituent; represents an optional heterocyclic group, and R ¹ and R ² may be connected to each other to form a ring).

Examples of the aliphatic hydrocarbon group include a linear or branched alkyl group of 1 to 20 carbon atoms which may have a substituent, a cyclic alkyl group of 3 to 20 carbon atoms which may have a substituent, and an alkenyl group of 2 to 20 carbon atoms. As said aryl group, the C6-C20 phenyl group which may have a substituent, the C10-C20 naphthyl group which may have a substituent, etc. are mentioned. As a heterocyclic group, a 5-membered ring group or a 6-membered ring group containing at least 1 hetero atom which may have a substituent is mentioned. In addition, R ¹ and R ² may be linked to each other to form a ring. R ¹ and R ² are preferably a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.

In one embodiment, the reactive group included in the functional group represented by the above X is preferably a (meth)acrylic group and/or a (meth)acrylamide group. By having these reactive groups, the adhesiveness of a polarizer and a block layer can be improved.

In one embodiment, it is preferable that the functional group represented by said X is a functional group represented by the following formula.

[Formula 3]

(Wherein, Z is a group consisting of a vinyl group, a (meth)acrylic group, a styryl group, a (meth)acrylamide group, a vinylether group, an epoxy group, an oxetane group, a hydroxyl group, an amino group, an aldehyde group, and a carboxyl group represents a functional group containing at least one reactive group selected from, and Y represents a phenylene group or an alkylene group).

As a monomer represented by General formula (1), the following compounds can be specifically used.

[Formula 4]

In the acrylic resin (A), the content ratio of the structural unit derived from the monomer (a) is preferably more than 0 parts by weight and less than 50 parts by weight, more preferably, with respect to 100 parts by weight of the acrylic resin (A). It is 0.01 part by weight or more and less than 50 parts by weight, more preferably 0.05 part by weight to 20 parts by weight, still more preferably 0.1 part by weight to 10 parts by weight. Within such a range, a conductive optical laminate having excellent durability can be obtained.

In the acrylic resin (A), the content ratio of the structural unit derived from the acrylic monomer is preferably more than 50 parts by weight with respect to 100 parts by weight of the acrylic resin (A).

Any appropriate acrylic monomer can be used as the acrylic monomer. For example, the (meth)acrylic acid ester type monomer which has a linear or branched structure, and the (meth)acrylic acid ester type monomer which has a cyclic structure are mentioned. In this specification, a (meth)acryl refers to an acryl and/or methacryl.

Examples of the (meth)acrylic acid ester monomer having a linear or branched structure include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and (meth)acrylate. ) n-butyl acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, methyl 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and the like. Preferably, methyl (meth)acrylate is used. The (meth)acrylic acid ester monomer may be used alone or in combination of two or more.

Examples of the (meth)acrylic acid ester monomer having a cyclic structure include cyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, Dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, biphenyl (meth)acrylate, o-biphenyloxyethyl (meth)acrylate, o- Biphenyloxyethoxyethyl (meth)acrylate, m-biphenyloxyethyl acrylate, p-biphenyloxyethyl (meth)acrylate, o-biphenyloxy-2-hydroxypropyl (meth)acrylate, p-biphenyloxy-2-hydroxypropyl (meth)acrylate, m-biphenyloxy-2-hydroxypropyl (meth)acrylate, N-(meth)acryloyloxyethyl-o-biphenyl = Carbamate, N-(meth)acryloyloxyethyl-p-biphenyl=carbamate, N-(meth)acryloyloxyethyl-m-biphenyl=carbamate, o-phenylphenolglycy Biphenyl group-containing monomers, such as dil ether acrylate, terphenyl (meth)acrylate, o-terphenyloxyethyl (meth)acrylate, etc. are mentioned. Preferably, 1-adamantyl (meth)acrylate and dicyclopentanyl (meth)acrylate are used. By using these monomers, a polymer having a high glass transition temperature is obtained. These monomers may be used alone or in combination of two or more. In addition, in this specification, (meth)acryloyl means an acryloyl group and/or a methacryloyl group.

Moreover, you may use the silsesquioxane compound which has a (meth)acryloyl group instead of the said (meth)acrylic acid ester type monomer. By using a silsesquioxane compound, an acrylic polymer with a high glass transition temperature is obtained. Silsesquioxane compounds are known to have skeletons such as various skeleton structures, for example, cage-like structures, ladder-like structures, and random structures. A silsesquioxane compound may have only 1 type of these structures, and may have 2 or more types. A silsesquioxane compound may use only 1 type, and may use it in combination of 2 or more type.

As a silsesquioxane compound which has a (meth)acryloyl group, MAC grade and AC grade of the SQ series of Toa Synthetic Industries Co., Ltd. can be used, for example. MAC grade is a silsesquioxane compound containing a methacryloyl group, and specifically, MAC-SQ TM-100, MAC-SQ SI-20, MAC-SQ HDM etc. are mentioned. AC grade is a silsesquioxane compound containing an acryloyl group, and specifically, AC-SQ TA-100, AC-SQ SI-20, etc. are mentioned.

The acrylic resin (A) is preferably obtained by solution polymerization of monomer components such as an acrylic monomer and monomer (a). Arbitrary suitable solvents can be used as a solvent used by solution polymerization. For example, water; Alcohol, such as methyl alcohol, ethyl alcohol, and isopropyl alcohol; aromatic or aliphatic hydrocarbons such as benzene, toluene, xylene, cyclohexane, and n-hexane; Ester compounds, such as ethyl acetate; Ketone compounds, such as acetone and methyl ethyl ketone; and cyclic ether compounds such as tetrahydrofuran and dioxane. These solvents may be used alone or in combination of two or more. Moreover, you may use together an organic solvent and water. The polymerization reaction can be carried out at any suitable temperature and time. For example, the polymerization reaction can be carried out in the range of 50°C to 100°C, preferably 60°C to 80°C. Moreover, the reaction time is, for example, 1 hour to 8 hours, preferably 3 hours to 5 hours.

Arbitrary suitable epoxy-type resins can be used as said epoxy-type resin. As the epoxy resin, an epoxy resin having an aromatic ring is preferably used. By using an epoxy-based resin having an aromatic ring, a block layer having more excellent adhesion to a polarizer can be formed. As an epoxy resin which has an aromatic ring, For example, Bisphenol-type epoxy-type resin, such as bisphenol-A epoxy-type resin, bisphenol F-type epoxy-type resin, and bisphenol S-type epoxy-type resin; novolak-type epoxy resins such as phenol novolac epoxy resin, cresol novolac epoxy resin, and hydroxybenzaldehyde phenol novolac epoxy resin; Polyfunctional epoxy resins such as glycidyl ether of tetrahydroxyphenylmethane, glycidyl ether of tetrahydroxybenzophenone, epoxidized polyvinylphenol, naphthol type epoxy resin, naphthalene type epoxy resin, biphenyl Type epoxy resin etc. are mentioned. Preferably, bisphenol A type epoxy resins, biphenyl type epoxy resins, and bisphenol F type epoxy resins are used. By using these epoxy resins, it is possible to form a block layer capable of favorably preventing the movement of the iodine component. Epoxy-type resin may use only 1 type, and may use it in combination of 2 or more type.

The weight average molecular weight (Mw) of the epoxy resin is preferably 20,000 or more, more preferably 30,000 or more, still more preferably 37,000 or more. When the weight average molecular weight of the epoxy-based resin is within the above range, a block layer capable of preferably preventing the movement of the iodine component can be formed. A weight average molecular weight can be measured by GPC, for example.

The monolayer thickness of the block layer is preferably 0.1 μm to 8 μm, more preferably 0.2 μm to 3 μm, still more preferably 0.4 μm to 1 μm. As described above, when a block layer containing an acrylic resin and an epoxy resin is formed, a block layer capable of preferably blocking the movement of the iodine component can be formed even though it is thin.

The total thickness of the block layer is preferably 0.1 μm to 16 μm, more preferably 0.1 μm to 8 μm, still more preferably 0.2 μm to 6 μm, still more preferably 0.2 μm to 3 μm , More preferably, they are 0.2 μm to 2 μm, and particularly preferably 0.4 μm to 1 μm. The total thickness of the block layer corresponds to the thickness of a single layer when the block layer is a single layer, and corresponds to the total thickness of the thicknesses of each layer when the block layer is a plurality of layers.

The elastic modulus of the cross section of the block layer is preferably 4 GPa to 8 GPa, more preferably 5 GPa to 6 GPa. If it is such a range, cracks are hard to generate|occur|produce, and a block layer which can function effectively also as a polarizer protective film can be formed. In this specification, the modulus of elasticity of the cross section of the block layer can be measured under the following conditions using a nanoindenter (eg, manufactured by Hysitron Inc., product name: Triboindenter).

Used indenter: Berkovich (triangular pyramid type)

Measurement method: single indentation measurement

Measurement temperature: 23 ℃

Indentation depth setting: 50 nm

The water vapor transmission rate of the block layer is preferably 10 g/m 2 24 h to 2000 g/m 2 24 h, more preferably 100 g/m 2 24 h to 1800 g/m 2 24 h, still more preferably is 150 g/m 2 24 h to 1500 g/m 2 24 h. When the moisture permeability is within the above range, a block layer that can function effectively also as a polarizer protective film can be formed. In addition, the water vapor transmission rate can be determined based on the water vapor transmission rate test (cup method) of JIS Z 0208.

D. Transparent Conductive Layer

As described above, the transparent conductive layer includes metal nanowires or metal meshes. In one embodiment, the transparent conductive layer further includes a polymer matrix. In this embodiment, metal nanowires or metal meshes exist in the polymer matrix. In the conductive layer composed of the polymer matrix, the metal nanowires or metal meshes are protected by the polymer matrix. As a result, corrosion of the metal nanowires or the metal mesh is prevented, and an optical laminate having more excellent durability can be obtained.

The single-layer thickness of the transparent conductive layer is preferably 50 nm to 150 nm, more preferably 55 nm to 140 nm, even more preferably 60 nm to 130 nm, particularly preferably 65 nm to 120 nm am.

The surface resistance value of the transparent conductive layer is preferably 0.01 Ω/□ to 1000 Ω/□, more preferably 0.1 Ω/□ to 500 Ω/□, and particularly preferably 0.1 Ω/□ to 300 Ω. /□, most preferably 0.1 Ω/□ to 100 Ω/□.

In one embodiment, the transparent conductive layer is patterned. As the patterning method, any suitable method may be employed depending on the shape of the transparent conductive layer. The shape of the pattern of the transparent conductive layer may be any suitable shape depending on the purpose. For example, it is described in Japanese Patent Publication No. 2011-511357, Japanese Patent Application Publication No. 2010-164938, Japanese Patent Application Publication No. 2008-310550, Japanese Patent Publication No. 2003-511799, Japanese Patent Application Publication No. 2010-541109. patterns can be heard. After the transparent conductive layer is formed on the substrate, it can be patterned using any suitable method depending on 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, still more preferably 95% or more.

(Conductive layer containing metal nanowires)

The metal nanowire refers to a conductive material made of metal, needle-shaped or filiform in shape, and having a nanometer size in diameter. The metal nanowire may be linear or curved. When a transparent conductive layer made of metal nanowires is used, the metal nanowires form a mesh, so that a good electrical conduction path can be formed even with a small amount of metal nanowires, and a conductive optical laminate having low electrical resistance can be obtained.

The ratio of the thickness d to the length L (aspect ratio: L/d) of the metal nanowire is preferably 10 to 100,000, more preferably 50 to 100,000, and particularly preferably 100 to 10,000. In this way, when a metal nanowire having a large aspect ratio is used, the metal nanowires cross well, and high conductivity can be developed with a small amount of the metal nanowire. As a result, a transparent conductive layer having high light transmittance can be obtained. In the present specification, "thickness of metal nanowire" means the diameter when the cross section of the metal nanowire is circular, and when it is elliptical, it means its short diameter, and when it is polygonal, it means the longest diagonal it means. The thickness and length of the metal nanowire can be confirmed with a scanning electron microscope or a 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 60 nm. If it is such a range, a transparent conductive layer with high light transmittance can be formed.

The length of the metal nanowire is preferably 1 μm to 1000 μm, more preferably 1 μm to 500 μm, and particularly preferably 1 μm to 100 μm. Within such a range, a conductive optical laminate having high conductivity can be obtained.

As the metal constituting the metal nanowire, any appropriate metal may be used as long as it is a highly conductive metal. Examples of the metal constituting the metal nanowire include one or more metals selected from the group consisting of gold, platinum, silver, copper, aluminum, rhodium, and nickel. Moreover, you may use the material which plated these metals (for example, gold plating process). The metal nanowire is preferably composed of one or more metals selected from the group consisting of gold, platinum, silver, and copper.

As a method for producing the metal nanowire, any suitable method may be employed. For example, a method of reducing silver nitrate in a solution, a method of applying a voltage or current applied from the tip of a probe to the surface of a precursor, extracting metal nanowires from the tip of the probe, and continuously forming the metal nanowires. there is. In the method of reducing silver nitrate in a solution, silver nanowires can be synthesized by reducing a liquid phase of a silver salt such as silver nitrate in the presence of a polyol such as ethylene glycol and polyvinylpyrrolidone. Silver nanowires of uniform size are, for example, Xia, Y. et al., Chem. Mater. (2002), 14, 4736-4745, Xia, Y. et al., Nano letters (2003) 3 (7), mass production is possible according to the method described in 955-960.

The content ratio of the metal nanowires in the transparent conductive layer is preferably from 30% by weight to 100% by weight, more preferably from 30% by weight to 90% by weight, with respect to the total weight of the transparent conductive layer. Preferably they are 45 weight% - 80 weight%. Within such a range, a transparent conductive layer excellent in conductivity and light transmittance can be obtained.

The density of the metal nanowire 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 . Within such a range, a conductive layer excellent in conductivity and light transmittance can be obtained.

(Transparent Conductive Layer Containing Metal Mesh)

The transparent conductive layer containing a metal mesh is formed by forming thin metal wires in a lattice pattern on the base material. As the metal constituting the metal mesh, any appropriate metal can be used as long as it is a highly conductive metal. Examples of the metal constituting the metal mesh include at least one metal selected from the group consisting of gold, platinum, silver, copper, aluminum, rhodium, and nickel. Moreover, you may use the material which plated these metals (for example, gold plating process). The metal mesh is preferably composed of at least one metal selected from the group consisting of gold, platinum, silver, and copper.

(polymer matrix)

As the polymer constituting the polymer matrix, any suitable polymer may be used. Examples of the polymer include acrylic polymers; polyester polymers such as polyethylene terephthalate; aromatic polymers such as polystyrene, polyvinyltoluene, polyvinylxylene, polyimide, polyamide, and polyamideimide; Polyurethane-type polymer; Epoxy-type polymer; Polyolefin type polymer; Acrylonitrile-butadiene-styrene copolymer (ABS); cellulose; silicone-based polymers; polyvinyl chloride; polyacetate; polynorbornene; synthetic rubber; A fluorine-type polymer etc. are mentioned. Preferably, pentaerythritol triacrylate (PETA), neopentyl glycol diacrylate (NPGDA), dipentaerythritol hexaacrylate (DPHA), dipentaerythritol pentaacrylate (DPPA), trimethylolpropane tri A curable resin (preferably an ultraviolet curable resin) composed of a polyfunctional acrylate such as acrylate (TMPTA) is used.

E. protective layer

As described above, the conductive optical laminate may have a protective layer disposed to protect the transparent conductive layer.

As a material for forming the protective layer, any appropriate resin composition may be used. Examples of the resin contained in the resin composition include thermosetting resins, photocurable resins (ultraviolet curable resins and visible light curable resins), electron beam curable resins, and the like, and from the viewpoint of workability, ultraviolet curable resins are preferable. A resin composition containing a thermosetting resin is constituted by, for example, an epoxy resin, an unsaturated polyester resin, a phenol resin or a polyurethane resin, and a curing agent added as needed. The resin composition containing photocurable resin or electron beam curable resin is, for example, polymerizable monomers such as monofunctional acrylate and polyfunctional acrylate; Or polymerizable prepolymers, such as polyester acrylate, epoxy acrylate, and polyurethane acrylate; and a photoinitiator added as needed.

The protective layer may be made of conductive resin. Examples of the conductive resin include poly(3,4-ethylenedioxythiophene) (PEDOT), polyaniline, polythiophene, and polydiacetylene.

The protective layer may be made of an inorganic material. Examples of the inorganic material include silica, mullite, alumina, SiC, MgO-Al ₂ O ₃ -SiO ₂ , Al ₂ O ₃ -SiO ₂ , MgO-Al ₂ O ₃ -SiO ₂ -Li ₂ O, and the like. can be heard

The thickness of the protective layer is, for example, 1 μm to 100 μm, more preferably 2 μm to 50 μm, still more preferably 3 μm to 20 μm.

F. Description

The base material is typically made of any suitable resin. Examples of the resin constituting the substrate include cycloolefin-based resins, polyimide-based resins, polyvinylidene chloride-based resins, polyvinyl chloride-based resins, polyethylene terephthalate-based resins, and polyethylene naphthalate-based resins. can Preferably, a cycloolefin based resin is used. A conductive optical laminate having excellent flexibility can be obtained by using a substrate composed of a cycloolefin-based resin.

As the cycloolefin-based resin, for example, polynorbornene may be preferably used. Polynorbornene refers to a (co)polymer obtained by using a norbornene-based monomer having a norbornene ring as part or all of a starting material (monomer). As the polynorbornene, various products are commercially available. Specific examples include "Zeonex" and "Zeonoa" manufactured by Zeon, Japan, "Arton" manufactured by JSR, "Topas" manufactured by Ticona, and "APEL" manufactured by Mitsui Chemicals. can be heard

The glass transition temperature of the resin constituting the substrate is preferably 50°C to 200°C, more preferably 60°C to 180°C, still more preferably 70°C to 160°C. Deterioration at the time of forming a transparent conductive layer can be prevented as long as it is a base material which has a glass transition temperature in this range.

The thickness of the substrate is preferably 8 μm to 500 μm, more preferably 10 μm to 250 μm, still more preferably 10 μm to 150 μm, and particularly preferably 15 μm to 100 μm.

The total light transmittance of the substrate is preferably 80% or more, more preferably 85% or more, and particularly preferably 90% or more. Within such a range, a conductive optical laminate suitable for use as a conductive optical laminate provided in a touch panel or the like can be obtained.

The base material may further include any appropriate additives as needed. Specific examples of additives include plasticizers, heat stabilizers, light stabilizers, lubricants, antioxidants, ultraviolet absorbers, flame retardants, colorants, antistatic agents, compatibilizers, crosslinking agents, and thickeners. The type and amount of additives used may be appropriately set depending on the purpose.

If necessary, you may perform various surface treatments with respect to the said base material. As for the surface treatment, any suitable method is employed depending on the purpose. Examples include low-pressure plasma treatment, ultraviolet irradiation treatment, corona treatment, flame treatment, and acid or alkali treatment. In one embodiment, the surface of the transparent substrate is subjected to surface treatment to make the surface of the transparent substrate hydrophilic. When the base material is made hydrophilic, processability at the time of coating the composition for forming a transparent conductive layer prepared with an aqueous solvent is excellent. In addition, a conductive optical laminate having excellent adhesion between the substrate and the transparent conductive layer can be obtained.

G. Adhesive layer, adhesive layer

As described above, in the conductive optical laminate, any suitable pressure-sensitive adhesive layer or adhesive layer is disposed between each layer (for example, a polarizer, a block layer, a transparent conductive layer, and other layers that may be arbitrarily disposed). it may be

Examples of the adhesive constituting the pressure-sensitive adhesive layer include acrylic adhesives, rubber-based adhesives, vinylalkyl ether-based adhesives, silicone-based adhesives, polyester-based adhesives, polyamide-based adhesives, urethane-based adhesives, fluorine-based adhesives, epoxy-based adhesives, polyether system adhesives are exemplified. An adhesive may be used independently and may be used in combination of 2 or more type. In terms of transparency, processability, durability and the like, an acrylic pressure-sensitive adhesive is preferably used.

The thickness of the pressure-sensitive adhesive layer is typically 5 µm to 300 µm, preferably 10 µm to 150 µm, and more preferably 15 µm to 100 µm.

As the adhesive constituting the adhesive layer, any suitable type of adhesive may be employed. Specific examples include water-based adhesives, solvent-type adhesives, emulsion-based adhesives, non-solvent-type adhesives, active energy ray curable adhesives, and thermosetting adhesives. Examples of active energy ray curable adhesives include electron beam curable adhesives, ultraviolet curable adhesives, and visible ray curable adhesives. Water-based adhesives and active energy ray curable adhesives can be preferably used. Specific examples of the water-based adhesive include isocyanate-based adhesives, polyvinyl alcohol-based adhesives, gelatin-based adhesives, vinyl-based latex-based adhesives, water-based polyurethanes, and water-based polyesters. Specific examples of the active energy ray curable adhesive include (meth)acrylate-based adhesives. Examples of the curable component in the (meth)acrylate-based adhesive include a compound having a (meth)acryloyl group and a compound having a vinyl group. Moreover, the compound which has an epoxy group or an oxetanyl group can also be used as a cationic polymerization hardening type adhesive agent. The compound having an epoxy group is not particularly limited as long as it has at least two epoxy groups in the molecule, and various commonly known curable epoxy compounds can be used. As a preferred epoxy compound, a compound having at least two epoxy groups in a molecule and at least one aromatic ring (aromatic epoxy compound), or a compound having at least two epoxy groups in a molecule, at least one of which constitutes an alicyclic ring; Compounds (alicyclic epoxy compounds) formed between two carbon atoms that do.

The thickness of the adhesive layer is typically 0.01 µm to 7 µm, preferably 0.01 µm to 5 µm.

H. Manufacturing Method of Conductive Optical Laminate

The conductive optical laminate can be manufactured by any suitable method. In one embodiment, a conductive optical laminate can be obtained by bonding a laminate containing a polarizer (hereinafter also referred to as a polarizing plate) and a laminate containing a transparent conductive layer (hereinafter also referred to as a conductive film). . The block layer 20 may be disposed on a polarizing plate (FIG. 1, FIG. 2(a)), or may be disposed on a conductive film (FIG. 2(b), FIG. 2(c)), of the polarizing plate and the conductive film You may arrange|position on both sides (FIG. 2(d), FIG. 2(e)). A polarizing plate and a conductive film can be bonded together via the said adhesive layer or adhesive bond layer.

The block layer can be formed by any suitable method. For example, it can form by coating the composition for block layer formation to a predetermined|prescribed layer (for example, a polarizer, a transparent conductive layer, and a protective layer).

The composition for forming a block layer contains resin constituting the block layer (for example, acrylic resin, epoxy resin, etc.), and further contains any appropriate other component as necessary. As other components, a solvent and an additive are mentioned, for example. As the solvent, a solvent that can be used when solution-polymerizing the resin constituting the block layer may be used, or other solvents may be used. Examples of other solvents include ethyl acetate, toluene, methyl ethyl ketone, and cyclopentanone. These solvents may be used alone or in combination of two or more.

As the coating method of the composition for forming the block layer, various methods such as bar coater coating, air knife coating, gravure coating, gravure reverse coating, reverse roll coating, lip coating, die coating, dip coating, offset printing, flexographic printing, screen printing, etc. method can be employed.

(Manufacture of conductive film)

In one embodiment, the transparent conductive layer in the conductive film applies, for example, a composition for forming a conductive layer containing metal nanowires to a substrate (or a laminate of the substrate and other layers), , After that, the coating layer can be dried and formed.

The composition for forming the conductive layer may include any appropriate solvent in addition to the metal nanowires. The composition for forming a conductive layer can be prepared as a dispersion of metal nanowires. Examples of the solvent include water, alcohol solvents, ketone solvents, ether solvents, hydrocarbon solvents, and aromatic solvents. From the viewpoint of reducing the environmental load, it is preferable to use water. The composition for forming the conductive layer may further contain any suitable additive depending on the purpose. Examples of the additive include a corrosion inhibitor that prevents corrosion of metal nanowires and a surfactant that prevents aggregation of metal nanowires. The type, number and amount of additives used may be appropriately set depending on the purpose.

When the transparent conductive layer includes a polymer matrix, the polymer matrix is coated with a composition for forming a conductive layer as described above, dried, and then coated with a polymer solution (polymer composition, monomer composition) on a layer composed of metal nanowires. ), and then drying or curing the applied layer of the polymer solution. Moreover, you may form a transparent conductive layer using the composition for conductive layer formation containing the polymer which comprises a polymer matrix.

The dispersion concentration of the metal nanowire in the composition for forming a conductive layer is preferably 0.1% by weight to 1% by weight. Within such a range, a transparent conductive layer excellent in conductivity and light transmittance can be formed.

As a method of applying the composition for forming a conductive layer, any appropriate method may be employed. Examples of the coating method include spray coating, bar coating, roll coating, die coating, inkjet coating, screen coating, dip coating, relief printing, intaglio printing, and gravure printing. As a method for drying the applied layer, any suitable drying method (for example, natural drying, blowing drying, heat drying) can be employed. For example, in the case of heat drying, the drying temperature is typically 50°C to 200°C, preferably 80°C to 150°C. Drying time is typically 1 to 10 minutes.

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

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

A transparent conductive layer containing a metal mesh can be formed by any suitable method. For the transparent conductive layer, for example, a photosensitive composition containing silver salt (composition for forming a conductive layer) is applied onto the transparent film, and then exposure and development are performed to form fine metal wires in a predetermined pattern. can be obtained by forming In addition, the conductive layer can also be obtained by printing a paste containing metal fine particles in a predetermined pattern. The details of such a conductive layer and its formation method are described, for example in Unexamined-Japanese-Patent No. 2012-18634, and the description is used here as a reference. Moreover, as another example of the conductive layer comprised from a metal mesh, and its formation method, the conductive layer and its formation method of Unexamined-Japanese-Patent No. 2003-331654 are mentioned.

When the conductive optical layered body (substantially, a transparent conductive film) has a protective layer, the protective layer is, for example, after forming the transparent conductive layer as described above, and further, the material for forming the protective layer (eg For example, a predetermined resin) or a precursor of a material for forming a protective layer (eg, a monomer constituting the resin) is applied, followed by drying and, if necessary, curing can form. As the application method, the above method can be employed. As the drying method, any suitable drying method (for example, natural drying, blow drying, heat drying) can be employed. For example, in the case of heat drying, the drying temperature is typically 100°C to 200°C, and the drying time is typically 1 to 10 minutes. The curing treatment may be performed under any appropriate conditions depending on the resin constituting the protective layer.

The composition for forming the protective layer may include a solvent. Examples of the solvent contained in the composition for forming a protective layer include alcohol solvents, ketone solvents, tetrahydrofuran, hydrocarbon solvents, and aromatic solvents. Preferably, the solvent is volatile. The boiling point of the solvent is preferably 200°C or lower, more preferably 150°C or lower, still more preferably 100°C or lower.

The composition for forming the protective layer may further contain any appropriate additives depending on the purpose. As an additive, a crosslinking agent, a polymerization initiator, a stabilizer, surfactant, corrosion inhibitor etc. are mentioned, for example.

Example

Hereinafter, the present invention will be specifically described by examples, but the present invention is not limited to these examples at all.

[Production Example 1] Production of polarizer with protective film

As the substrate, a long, amorphous isophthalic acid copolymerized polyethylene terephthalate (IPA copolymerized PET) film (thickness: 100 µm) with a water absorption of 0.75% and a Tg of 75°C was used. Corona treatment was performed on one side of the substrate, and polyvinyl alcohol (polymerization degree 4200, saponification degree 99.2 mol%) and acetoacetyl-modified PVA (polymerization degree 1200, acetoacetyl denaturation degree 4.6%, saponification degree 99.0 mol) were applied to the corona-treated surface. % or more, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name: Gosepimer Z200) at a ratio of 9:1, applied and dried at 25°C to form a PVA-based resin layer having a thickness of 13 μm to prepare a laminate did

The obtained layered product was uniaxially stretched at the free end 2.4 times in the longitudinal direction (longitudinal direction) between rolls having different circumferential speeds in a 130°C oven (air assisted stretching).

Next, the laminate was immersed in an insolubilization bath (boric acid aqueous solution obtained by blending 4 parts by weight of boric acid with respect to 100 parts by weight of water) at a liquid temperature of 40°C for 30 seconds (insolubilization treatment).

Next, the layered product is immersed in a 30°C dyeing solution (an aqueous solution containing 7.0 parts by weight of potassium iodide and 1.0 part by weight of solid iodine added to 100 parts by weight of water) so that the transmittance of the obtained polarizer is 42% or more, and dyeing (staining treatment).

Next, it was immersed in a crosslinking bath (boric acid aqueous solution obtained by blending 3 parts by weight of potassium iodide and 5 parts by weight of boric acid with respect to 100 parts by weight of water) at a solution temperature of 40°C for 35 seconds (crosslinking treatment).

After that, the laminate was immersed in an aqueous solution of boric acid at a liquid temperature of 70°C (boric acid concentration: 4.0% by weight), and uniaxial stretching was performed between rolls having different circumferential speeds so that the total draw ratio was 5.5 times in the machine direction (longitudinal direction). (underwater stretching).

Then, the laminate was immersed in a washing bath (an aqueous solution obtained by blending 4 parts by weight of potassium iodide with respect to 100 parts by weight of water) at a liquid temperature of 20°C for 3 seconds (washing treatment).

Then, it was made to dry in a 60 degreeC oven for 60 second, and the laminated body which has a 5 micrometer-thick PVA system resin layer (polarizer) was obtained.

On the polarizer-side surface of the obtained laminate, an ultraviolet curing adhesive was applied so that the thickness after curing was 1 μm, and the coated surface was corona-treated with (meth)acrylic resin film A (thickness 40 μm) having a lactone ring structure. The surfaces were bonded together and the UV curable adhesive was cured. Then, the PET film was peeled from the layered product to obtain a polarizer A with protective film (protective film (40 μm)/adhesive layer (1 μm)/polarizer (5 μm)).

In addition, as the ultraviolet curable adhesive, 40 parts by weight of N-hydroxyethyl acrylamide (HEAA), 60 parts by weight of acryloylmorpholine (ACMO), and a photoinitiator (manufactured by BASF, trade name: IRGACURE 819) 3 What was prepared by mixing parts by weight was used.

[Production Example 2] Production of laminate A (polarizer/block layer/pressure-sensitive adhesive layer with protective film)

(Manufacture of polarizer A with protective film)

It carried out similarly to manufacture example 1, and manufactured the polarizer A with a protective film.

(formation of block layer)

97.0 parts by weight of methyl methacrylate (MMA, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name: methyl methacrylate monomer), 3.0 parts by weight of the monomer represented by the formula (1e), polymerization initiator (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name: 2 0.2 parts by weight of 2'-azobis (isobutyronitrile)) was dissolved in 200 parts by weight of toluene. Then, polymerization reaction was performed for 5 hours, heating at 70 degreeC in nitrogen atmosphere, and the polymer (A) (solid content concentration: 33 weight%) was obtained. The weight average molecular weight of the obtained polymer (A) was 85,000.

10 parts by weight of the polymer (A) and 90 parts by weight of an epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name "JER 1256B40") were mixed to prepare a composition for forming a block layer. The obtained composition for forming a block layer is coated on the polarizer surface of the polarizer A with a protective film so that the thickness after drying is 0.4 μm to form a block layer, and the polarizer A with a protective film (protective film / adhesive layer / polarizer) / block A layered product a composed of layers was obtained.

(formation of adhesive layer)

A monomer mixture containing 99 parts by weight of butyl acrylate and 1 part by weight of 4-hydroxybutyl acrylate was injected into a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet pipe, and a condenser. In addition, based on 100 parts by weight of the monomer mixture (solid content), 0.1 part by weight of 2,2'-azobisisobutyronitrile as a polymerization initiator was injected together with ethyl acetate, and nitrogen gas was introduced while gently stirring to replace nitrogen After that, a polymerization reaction was carried out for 7 hours while maintaining the liquid temperature in the flask at around 60°C. Then, ethyl acetate was added to the obtained reaction liquid to adjust the solid content concentration to 30%. In this way, a solution of an acrylic polymer (base polymer) having a weight average molecular weight of 1.4 million was prepared.

Based on 100 parts by weight of the solid content of the acrylic polymer solution, 0.095 parts by weight of trimethylolpropanexylylenediisocyanate (manufactured by Mitsui Chemicals, trade name: Takenate D110N) as a crosslinking agent and 0.3 parts by weight of dibenzoyl peroxide, as a silane coupling agent 0.2 parts by weight of ganosilane (manufactured by Soken Chemical Co., Ltd., trade name: A100) and 0.2 parts by weight of a thiol group-containing silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X41-1810), and an antioxidant (manufactured by BASF, trade name: Irganox1010) 0.3 part by weight was blended to obtain an acrylic pressure-sensitive adhesive (solution).

The obtained acrylic pressure-sensitive adhesive composition was uniformly coated with a fountain coater on the surface of a polyethylene terephthalate film (separator) treated with a silicone-based release agent, and then dried for 2 minutes in an air circulation constant temperature oven at 155°C to form a thickness of 20 An adhesive layer of ㎛ was formed.

This pressure-sensitive adhesive layer was transferred to the surface of the block layer of layered product a to obtain layered product A (polarizer A/block layer/pressure-sensitive adhesive layer with protective film).

[Production Example 3] Production of layered product B (polarizer A/adhesive layer with protective film)

(Manufacture of polarizer A with protective film)

It carried out similarly to manufacture example 1, and manufactured the polarizer A with a protective film.

(formation of adhesive layer)

In the same manner as in Production Example 2, an adhesive layer having a thickness of 20 μm was formed on the surface of the separator.

This adhesive layer was transferred to the polarizer surface of polarizer A with a protective film, and laminated body B (polarizer A/adhesive layer with a protective film) was obtained.

[Production Example 4] Production of transparent conductive film I (substrate/transparent conductive layer)

(Preparation of composition for forming conductive layer)

Chem. Mater. Silver nanowires were synthesized based on the method described in 2002, 14, 4736-4745.

In pure water, 0.2% by weight of the silver nanowires obtained above and 0.1% by weight of dodecyl-pentaethylene glycol were dispersed to obtain a composition for forming a transparent conductive layer.

(Preparation of transparent conductive film I)

As a substrate, a PET film (manufactured by Mitsubishi Resins, trade name "S100") was used. While conveying this base material using a conveyance roll, the composition for forming a transparent conductive layer was applied onto the base material using a bar coater (manufactured by Daiichi Science Co., Ltd., product name "Bar Coater No. 12") to obtain a wet thickness of 18 A coating layer of μm was formed. After that, it was dried at 120°C for 1 minute to form a transparent conductive layer to obtain a transparent conductive film I (substrate/transparent conductive layer) comprising a substrate and a transparent conductive layer. As a result of measuring the resistance of the obtained film, it was 50 Ω.

[Production Example 5] Production of transparent conductive film II (substrate/transparent conductive layer/protective layer)

In the same manner as in Production Example 4, transparent conductive film I (substrate/transparent conductive layer) was produced.

A diluted solution (ethyl acetate; 1 wt%) of an ultraviolet curable resin (manufactured by Daicel Allnex, trade name "KRM 9495") was applied to the transparent conductive layer surface of the transparent conductive film I so that the wet film thickness was 1 μm. After drying at 100°C for 1 minute and irradiating with 200 mJ of ultraviolet rays, a protective layer having a dry film thickness of 100 nm was formed to obtain transparent conductive film II (substrate/transparent conductive layer/protective layer).

[Production Example 6] Production of transparent conductive film III (substrate/transparent conductive layer/block layer)

In the same manner as in Production Example 4, transparent conductive film I (substrate/transparent conductive layer) was produced.

(formation of block layer)

97.0 parts by weight of methyl methacrylate (MMA, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name: methyl methacrylate monomer), 3.0 parts by weight of the monomer represented by the formula (1e), polymerization initiator (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name: 2 0.2 parts by weight of 2'-azobis (isobutyronitrile)) was dissolved in 200 parts by weight of toluene. Then, polymerization reaction was performed for 5 hours, heating at 70 degreeC in nitrogen atmosphere, and the polymer (A) (solid content concentration: 33 weight%) was obtained. The weight average molecular weight of the obtained polymer (A) was 85,000.

10 parts by weight of the polymer (A) and 90 parts by weight of an epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name "JER 1256B40") were mixed to prepare a composition for forming a block layer. The obtained composition for forming a block layer was coated on the surface of the transparent conductive layer of the transparent conductive film I to a thickness of 0.4 μm after drying to form a block layer, and the transparent conductive film III (substrate/transparent conductive layer/block layer) was formed. got it

[Production Example 7] Production of transparent conductive film IV (substrate/transparent conductive layer/protective layer/block layer)

In the same manner as in Production Example 5, a transparent conductive film II (substrate/transparent conductive layer/protective layer) was prepared.

(formation of block layer)

97.0 parts by weight of methyl methacrylate (MMA, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name: methyl methacrylate monomer), 3.0 parts by weight of the monomer represented by the formula (1e), polymerization initiator (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name: 2 0.2 parts by weight of 2'-azobis (isobutyronitrile)) was dissolved in 200 parts by weight of toluene. Then, polymerization reaction was performed for 5 hours, heating at 70 degreeC in nitrogen atmosphere, and the polymer (A) (solid content concentration: 33 weight%) was obtained. The weight average molecular weight of the obtained polymer (A) was 85,000.

10 parts by weight of the polymer (A) and 90 parts by weight of an epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name "JER 1256B40") were mixed to prepare a composition for forming a block layer. The obtained composition for forming a block layer was coated on the surface of the protective layer of the transparent conductive film II to a thickness of 0.4 μm after drying to form a block layer, and the transparent conductive film IV (substrate/transparent conductive layer/protective layer/block layer ) was obtained.

[Example 1]

Laminate A (polarizer with protective film A/block layer/pressure-sensitive adhesive layer) obtained in Production Example 2 and transparent conductive film I (base material/transparent conductive layer) obtained in Production Example 4 are brought into contact with the pressure-sensitive adhesive layer and the transparent conductive layer. and laminated to obtain a conductive optical laminate (polarizer A/block layer/adhesive layer/transparent conductive layer/base material with protective film).

[Example 2]

Laminate A (polarizer with protective film A/block layer/pressure-sensitive adhesive layer) obtained in Production Example 2 and transparent conductive film II (substrate/transparent conductive layer/protective layer) obtained in Production Example 5, the pressure-sensitive adhesive layer and the protective layer It laminated|stacked so that it might contact, and obtained the electroconductive optical laminate (polarizer A/block layer/adhesive layer/protective layer/transparent conductive layer/substrate with a protective film).

[Example 3]

Laminate B (polarizer with protective film A/pressure-sensitive adhesive layer) obtained in Production Example 3 and transparent conductive film III (substrate/transparent conductive layer/block layer) obtained in Production Example 6 were brought into contact with the pressure-sensitive adhesive layer and the block layer, It laminated and obtained the conductive optical laminate (polarizer A with protective film/adhesive layer/block layer/transparent conductive layer/substrate).

[Example 4]

Laminate B (polarizer with protective film A/pressure-sensitive adhesive layer) obtained in Production Example 3 and transparent conductive film IV (substrate/transparent conductive layer/protective layer/block layer) obtained in Production Example 7, the pressure-sensitive adhesive layer and the block layer are It laminated|stacked so that it might contact, and obtained the electroconductive optical laminated body (polarizer A with a protective film/adhesive layer/block layer/protective layer/transparent conductive layer/substrate).

[Example 5]

Laminate A (polarizer with protective film A/block layer/pressure-sensitive adhesive layer) obtained in Production Example 2 and transparent conductive film III (base material/transparent conductive layer/block layer) obtained in Production Example 6, the pressure-sensitive adhesive layer and the block layer It laminated|stacked so that it might contact, and obtained the electroconductive optical laminate (polarizer A/block layer/adhesive layer/block layer/transparent conductive layer/substrate with a protective film).

[Example 6]

Laminate A (polarizer with protective film A/block layer/pressure-sensitive adhesive layer) obtained in Production Example 2 and transparent conductive film IV (substrate/transparent conductive layer/protective layer/block layer) obtained in Production Example 7 were mixed with an adhesive layer It laminated|stacked so that the block layer might contact, and obtained the electroconductive optical laminate (polarizer A with a protective film/block layer/adhesive layer/block layer/protective layer/transparent conductive layer/substrate).

[Example 7]

It carried out similarly to manufacture example 1, and obtained polarizer A with a protective film (protective film/adhesive layer/polarizer). On the surface of the polarizer A with the protective film on the polarizer side, an ultraviolet curable adhesive was applied to a thickness of 1 μm after curing, and a corona of (meth)acrylic resin film A (40 μm in thickness) having a lactone ring structure on the coated surface The treated surfaces were bonded together, the ultraviolet curable adhesive was cured, and polarizer B with a protective film provided with a block layer (protective film/adhesive layer/polarizer/adhesive layer/block layer (protective film)) was obtained.

This polarizer B with protective film (protective film/adhesive layer/polarizer/adhesive layer/block layer (protective film)) and the transparent conductive film I (substrate/transparent conductive layer) obtained in Production Example 4 were mixed with the adhesive layer and the transparent conductive film. The layers were laminated in contact to obtain a conductive optical laminate (polarizer B with protective film (protective film/adhesive layer/polarizer/adhesive layer/block layer (protective film))/adhesive layer/transparent conductive layer/substrate).

[Comparative Example 1]

Laminate B (polarizer with protective film A/pressure-sensitive adhesive layer) obtained in Production Example 3 and transparent conductive film I (substrate/transparent conductive layer) obtained in Production Example 4 were laminated so that the pressure-sensitive adhesive layer and the transparent conductive layer were brought into contact, , A conductive optical laminate (polarizer A with protective film/adhesive layer/transparent conductive layer/substrate) was obtained.

[Comparative Example 2]

Laminate B (polarizer with protective film A/pressure-sensitive adhesive layer) obtained in Production Example 3 and transparent conductive film II (substrate/transparent conductive layer/protective layer) obtained in Production Example 5 were brought into contact with the pressure-sensitive adhesive layer and the protective layer, It laminated|stacked and obtained the electroconductive optical laminate (polarizer A with a protective film / adhesive layer / protective layer / transparent conductive layer / base material).

＜Evaluation＞

The conductive optical laminates obtained in Examples and Comparative Examples were cut out to a size of 50 mm × 50 mm, and bonded to alkali-free glass through an acrylic pressure-sensitive adhesive to obtain evaluation samples. The conductive optical layered body was arranged so that the base material was on the alkali-free glass side and the polarizer with a protective film was on the outside.

Next, the initial resistance value of the transparent conductive layer was measured using "Model EC-80" manufactured by Napson. In addition, the resistance value of the transparent conductive layer was measured after the evaluation sample was stored for 500 hours in an environment of a temperature of 65°C/humidity of 90% and then returned to room temperature.

Moreover, after separately storing the evaluation sample in an environment of a temperature of 85°C/humidity of 85% for 50 hours and then returning to room temperature, the resistance value of the transparent conductive layer was measured.

The degree of deterioration of the metal nanowire was evaluated from the resistivity change calculated by the resistance value after storage/resistance value before storage (initial resistance value). A result is shown in Table 1. In addition, when the resistance value was ∞ (that is, when it exceeded the measurable range), it was marked as "measurable impossible".

As can be seen from Table 1, according to the conductive optical laminate of the present invention, deterioration of metal nanowires in the transparent conductive layer is prevented by forming a block layer between the polarizer and the transparent conductive layer. Such an effect becomes remarkable by appropriately adjusting the composition of the block layer (Examples 1 to 6), and resistance change under more severe conditions (85°C/85%) can also be suppressed.

10: polarizer
20: block layer
30: transparent conductive layer
40: base
100, 200, 300, 400, 500, 600: conductive optical laminate

Claims (12)

A polarizer, a block layer, and a transparent conductive layer are provided in this order,
The block layer is a resin layer,
A conductive optical laminate in which the transparent conductive layer includes a metal nanowire or a metal mesh. According to claim 1,
The conductive optical laminate wherein the block layer contains an acrylic resin and/or an epoxy resin. According to claim 2,
A conductive optical laminate in which the acrylic resin contains a structural unit derived from an acrylic monomer and a structural unit derived from a monomer (a) represented by the following formula (1):

(Wherein, X is a group consisting of a vinyl group, a (meth)acrylic group, a styryl group, a (meth)acrylamide group, a vinylether group, an epoxy group, an oxetane group, a hydroxyl group, an amino group, an aldehyde group, and a carboxyl group represents a functional group containing at least one reactive group selected from, and R ¹ and R ² are each independently a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, an aryl group which may have a substituent, or a substituent; It represents an optional heterocyclic group, and R ¹ and R ² may be linked to each other to form a ring.) According to claim 3,
In the acrylic resin, the content ratio of the structural unit derived from the monomer (a) is more than 0 parts by weight and less than 50 parts by weight with respect to 100 parts by weight of the acrylic resin. According to any one of claims 1 to 4,
The conductive optical laminate wherein the block layer has a total thickness of 0.1 μm to 16 μm. According to any one of claims 1 to 5,
A conductive optical laminate having a plurality of layers of the block layer. According to any one of claims 1 to 6,
Provide additional equipment,
A conductive optical laminate wherein the transparent conductive layer is disposed on the substrate. According to any one of claims 1 to 7,
The conductive optical laminate further comprising a protective layer disposed between the block layer and the transparent conductive layer to protect the transparent conductive layer. According to any one of claims 1 to 8,
The conductive optical laminate according to claim 1 , wherein the metal constituting the metal nanowire is at least one metal selected from the group consisting of gold, platinum, silver, copper, aluminum, rhodium, and nickel. According to any one of claims 1 to 8,
The conductive optical laminate according to claim 1 , wherein the metal constituting the metal mesh is at least one metal selected from the group consisting of gold, platinum, silver, copper, aluminum, rhodium, and nickel. According to any one of claims 1 to 8,
The conductive optical laminate according to claim 1 , wherein the metal nanowires are made of a material obtained by plating at least one metal selected from the group consisting of gold, platinum, silver, copper, aluminum, rhodium, and nickel. According to any one of claims 1 to 8,
The conductive optical laminate according to claim 1 , wherein the metal mesh is made of a material obtained by plating at least one metal selected from the group consisting of gold, platinum, silver, copper, aluminum, rhodium, and nickel.

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