TW201840261A - Transparent conductive laminate and production method therefor - Google Patents

Abstract

The present invention provides: a transparent conductive laminate that simultaneously exhibits excellent optical properties and flexibility and that has, on a transparent base material, at least an embedded resin layer, an auxiliary electrode layer, and a transparent conductive layer, wherein the transparent conductive layer comprises a metal oxide, and the embedded resin layer has an elastic modulus at 25 DEG C of 3,000-8,000 MPa and an elastic modulus at 70 DEG C of 1,000-7,000 MPa; and a production method for the transparent conductive laminate.

Description

Transparent conductive laminate and method of producing the same

The present invention relates to a transparent conductive laminate and a method of producing the same.

In recent years, due to the development of printed electronics, it is expected to be more flexible in terms of the large area of electronic devices mainly using organic materials, such as organic thin film solar cells or organic EL illumination, which are popular in the future. With the large area of these electronic devices, the transparent conductive layer of the transparent conductive film used for these is also required to have a low resistance. In order to suppress the device operation (collection or voltage application), The transparent conductive layer generally has a high electrical resistivity, and the performance of the electronic device such as photoelectric conversion efficiency or luminous efficiency is lowered. In the transparent conductive layer, a metal thin wire having a lower resistance value than the transparent conductive layer is used as the auxiliary electrode layer. Or the structure of the pattern layer of the metal paste, sometimes a transparent resin layer is provided between the thin lines or the pattern layer.

In the above-mentioned Patent Document 1, a transparent conductive sheet having flexibility is disclosed on the basis of the flexibility of the electronic device, and the coating comprising the transparent conductive particles and the dispersion medium is applied to the transparent substrate sheet. The cloth is liquid and laminated with a transparent conductive film. Further, in Patent Document 2, it is disclosed that the transparent conductive layer is formed by a dry film formation method using indium-tin oxide (ITO) or the like from the viewpoint of requiring high transparency and low resistance. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP-A-2015-162355 (Patent Document 2) JP-A-2014-216175

[Questions to be solved by the invention]

However, in Patent Document 1, although the transparency of the transparent base sheet is used, since the transparent conductive film formed by applying the coating liquid containing the transparent conductive particles and the dispersion medium exhibits conductivity, it is a structure. The transparent conductive film formed by the dry film formation method is not disclosed. Further, in Patent Document 2, a transparent conductive layer is formed on the surface formed by the auxiliary electrode layer and the transparent resin layer by a dry film formation method. However, as a result of further examination by the inventors, it was found that, in addition to film formation, The temperature rise is also caused by the strong stress of the film formed by the dry film formation method, and as a result, irregularities occur on the surface of the transparent conductive layer, and there is a problem that the optical characteristics are lowered, for example, the haze value is greatly increased.

The present invention has been made in view of the above problems, and it is an object of the invention to provide a transparent conductive laminate having both excellent optical characteristics and flexibility. [Means to solve the problem]

As a result of repeating the positive review, the present inventors have found that the elastic modulus of the embedded resin layer provided in the opening portion or the opening portion of the auxiliary electrode layer and the upper portion of the auxiliary electrode layer is controlled within a specific value range. Further, the present invention can be completed by having flexibility and suppressing an increase in turbidity of a transparent conductive layer formed by a dry film formation method. That is, the present invention provides the following (1) to (13). (1) A transparent conductive laminated body comprising at least a transparent conductive laminated body in which a resin layer, a supplementary electrode layer, and a transparent conductive layer are embedded on a transparent substrate, wherein the transparent conductive layer is made of a metal oxide The embedding resin layer has an elastic modulus at 25 ° C of 3000 to 8000 MPa and an elastic modulus at 70 ° C of 1000 to 7000 MPa. (2) The transparent conductive laminated body according to (1) above, wherein the glass transition temperature of the embedded resin layer is 90 °C or higher. (3) The transparent conductive laminate according to (1) or (2) above, wherein the thickness of the embedded resin layer is 0.1 to 100 μm. (4) The transparent conductive laminated body according to any one of (1) to (3), wherein the transparent conductive laminated body further includes an adhesive layer on a surface opposite to the transparent conductive layer embedded in the resin layer. (5) The transparent conductive laminated body according to (4) above, wherein the adhesive layer has a glass transition temperature of 40 ° C or higher. (6) The transparent conductive laminate according to (4) or (5) above, wherein the thickness of the adhesive layer is from 1 to 120 μm. (7) The transparent conductive laminated body according to any one of the above (4), wherein the adhesive layer has an elastic modulus at 25 ° C of 100 to 3000 MPa. (8) The transparent conductive laminated body according to any one of the above (1), wherein the transparent conductive laminated body further includes a transparent gas barrier layer on the transparent substrate. (9) The transparent conductive laminated body according to (8) above, wherein the transparent conductive laminated body further includes an adhesive layer between the embedded resin layer and the transparent gas barrier layer. (10) The transparent conductive laminated body according to (1) above, wherein the metal oxide is formed by sputtering. (11) A solar cell element or an organic electroluminescence device comprising the transparent electroconductive laminate according to any one of the above (1) to (10). (12) A method for producing a transparent conductive laminated body comprising at least a buried resin layer, a supplementary electrode layer, and a transparent conductive layer on a transparent substrate, wherein the transparent conductive layer is made of a metal oxide, and the buried a method for producing a transparent conductive laminated body having an elastic modulus of from 3,000 to 8,000 MPa at 25 ° C and an elastic modulus of from 1,000 to 7,000 MPa at 70 ° C, and comprising: a step of forming the auxiliary electrode layer, The step of forming the buried resin layer on the opening of the auxiliary electrode layer, the step of forming the buried resin layer on the auxiliary electrode layer and the opening, and the step of forming the transparent conductive layer. (13) The method for producing a transparent conductive laminate according to the above (12), which further comprises the step of forming an adhesive layer and/or the step of forming a transparent gas barrier layer. [Effect of the invention]

According to the present invention, it is possible to provide a transparent conductive laminate having both excellent optical characteristics and flexibility.

[Transparent Conductive Laminated Body] The transparent conductive laminated layer of the present invention comprises at least a transparent conductive laminated body in which a resin layer, a supplementary electrode layer, and a transparent conductive layer are embedded on a transparent substrate, and the transparent conductive layer is oxidized by metal The embedded resin layer has an elastic modulus at 25 ° C of 3000 to 8000 MPa and an elastic modulus at 70 ° C of 1000 to 7000 MPa. By controlling the elastic modulus at 25 ° C and 70 ° C of the embedded resin in the above range, it is possible to suppress the temperature rise due to the dry film formation method and the film stress formed by the dry film formation method before and after the formation of the transparent conductive layer. The turbidity due to the unevenness of the surface of the transparent conductive layer generated by the increase is increased, and a transparent conductive laminate which maintains the bendability and is excellent in optical characteristics can be obtained. Further, in the present invention, the "transparent conductive laminated body" and the "transparent conductive laminated body" are used differently. The "transparent conductive laminated body" means a laminated body which does not contain a transparent conductive layer in the "transparent conductive laminated body" of the present invention. The configuration of the transparent conductive laminate of the present invention will be described using a schematic diagram.

Fig. 1 is a cross-sectional view showing an example of a configuration of a transparent conductive laminate of the present invention. The transparent conductive laminated body 1A is formed by laminating the resin layer 3, the auxiliary electrode 4, and the transparent conductive layer 5 on the transparent substrate 2. The auxiliary electrode layer 4 has an opening 9 between the adjacent auxiliary electrode layers 4, and the embedded resin layer 3 is present on the opening 9 and the auxiliary electrode layer 4. Similarly, Fig. 2 is a cross-sectional view showing another example of the configuration of the transparent conductive laminated body of the present invention. The transparent conductive laminated body 1B is formed by interposing the undercoat layer 6 on the transparent substrate 2 with the transparent gas barrier layer 7 , the adhesive layer 8 , the embedded resin layer 3 , the auxiliary electrode 4 , and the transparent conductive layer 5 . The auxiliary electrode layer 4 has an opening 9 between the adjacent auxiliary electrode layers 4, and the embedded resin layer 3 is present on the opening 9 and the auxiliary electrode layer 4. In the above, the buried resin layer 3 may be present only in the opening portion 9.

(Substrate) The transparent substrate to be used in the present invention is not particularly limited, and may be appropriately selected depending on the device to be used, and the like, for example, is flexible and has a high transmittance in the visible light region, and is not particularly limited. Glass, resin film, etc. The material of the resin film is exemplified by polyimine, polyamine, polyamidamine, polyphenylene ether, polyether ketone, polyetheretherketone, polyolefin, polyester, polycarbonate, polyfluorene, poly Ether oxime, polyphenylene sulfide, polyarylate, acrylic resin, cycloolefin oligomer, cycloolefin polymer, aromatic polymer, polyurethane polymer, and the like. Among these, examples of the polyester include polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polyarylate, and the like. Further, examples of the cycloolefin polymer include a norbornene-based polymer, a monocyclic cyclic olefin polymer, a cyclic conjugated diene polymer, a vinyl alicyclic hydrocarbon polymer, and the like. . For example, as a cycloolefin polymer, APEL (manufactured by Mitsui Chemicals Co., Ltd., ethylene-cycloolefin copolymer), ARTON (manufactured by JSR Corporation, norbornene copolymer), and ZEONOR (manufactured by Nippon Zeon Co., Ltd., norbornene) are exemplified. Copolymer) and the like. Among these transparent substrates, polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) which are biaxially stretched are particularly preferable from the viewpoint of handleability. From the viewpoint of optical isotropic properties, a cycloolefin polymer or a cycloolefin oligomer is particularly preferred. From the viewpoint of heat resistance, it is particularly preferred to be a polyimine. Since the transparent conductive laminated body of the present invention is easy to manufacture and excellent in optical isotropic properties, the transparent conductive laminated body of the present invention can be preferably used in a display device. The thickness of the transparent substrate is preferably from 1 to 1000 μm, more preferably from 5 to 250 μm, still more preferably from 10 to 200 μm. If it is this range, the mechanical strength and transparency of a base material can be ensured.

(Substituting electrode layer) The auxiliary electrode layer used in the present invention is provided in order to lower the sheet resistance value of the transparent conductive layer of the transparent conductive laminated body of the present invention. Further, in order to suppress the decrease in the light transmittance of the transparent conductive layer, the opening portion is usually patterned.

The material of the auxiliary electrode layer is not particularly limited, but it is preferably patterned by a method such as photolithography. In this case, the material of the auxiliary electrode layer can be exemplified by a single metal such as gold, silver, copper, aluminum, magnesium, nickel, platinum, palladium, etc., silver-palladium, silver-copper, silver-magnesium, aluminum-niobium, aluminum- A binary to ternary aluminum alloy such as silver, aluminum-copper, aluminum-titanium-palladium or the like. Among these materials, silver, copper, aluminum, and aluminum alloy are preferred from the viewpoint of specific resistance, and copper, aluminum alloy is more preferable from the viewpoint of cost, etching property, and corrosion resistance.

Further, as the material of the auxiliary electrode layer, a conductive paste containing a conductive material can be used. The conductive paste is not particularly limited, and for example, a conductive fine particle such as metal fine particles, carbon or cerium oxide, or a conductive carbon material such as a metal nanowire or a carbon nanotube may be used in a solvent, and may further contain The adhesive component may be used by mixing two or more kinds of conductive pastes. The conductive paste is printed, fired or hardened to obtain a supplementary electrode layer.

The material of the metal fine particles is not particularly limited, and examples thereof include materials made of the above-described single metal and alloy. From the viewpoint of conductivity, silver, copper, aluminum, or the like is preferable. The platinum, ruthenium, osmium, palladium or the like is preferably used in terms of corrosion resistance or chemical resistance, and the metal may be contained in one type or two or more types. Further, from the viewpoint of cost, it is also possible to use copper fine particles coated with silver on the surface layer, or to use composite fine particles such as silver-coated resin particles on the surface layer from the viewpoint of flexibility. The metal nanowire material is not particularly limited, and examples thereof include a silver nanowire, a copper nanowire, a nickel nanowire, and a nanowire. The conductive carbon material is inferior in conductivity to metal, but is inexpensive, and is excellent in corrosion resistance and chemical resistance. The conductive carbon material is not particularly limited, and examples thereof include acetylene black, ketjen black, oil furnace black, conductive single-layer carbon nanotubes, conductive multilayer carbon nanotubes, and graphene powder. Further, although the ruthenium oxide (RuO ₂ ) fine particles are expensive compared with the conductive carbon material, they are used as the auxiliary electrode layer because they are conductive materials having excellent corrosion resistance.

The auxiliary electrode layer may be a single layer or a multilayer structure. The multilayer structure may have a multilayer structure in which a layer of the same material is laminated, or a multilayer structure in which two or more layers are laminated. As a multilayer structure, it is better to have a two-layer structure in which layers are formed of different materials. As such a multilayer structure, for example, a pattern layer in which silver is initially formed, and a pattern layer in which copper is formed thereon can be preferably maintained while maintaining high conductivity of silver and improving corrosion resistance. Further, as a purpose of improving optical characteristics, a chemical treatment may be applied to the formed auxiliary electrode layer. For example, for the purpose of antireflection, for example, a copper-based auxiliary electrode layer is subjected to blackening treatment or the like. By applying the blackening treatment, when the transparent conductive laminated body of the present invention is used for a display device or an illuminating device, the contrast can be improved.

The pattern of the auxiliary electrode layer used in the present invention is not particularly limited, and examples thereof include a lattice shape, a honeycomb shape, a comb shape, a strip shape (strip shape), a linear shape, a curved shape, a wave shape (sinusoidal curve, etc.), and a polygon. Mesh-like, round-shaped mesh, elliptical mesh, irregular shape, etc. Among these, it is preferably a lattice shape, a honeycomb shape, or a comb shape.

The thickness of the auxiliary electrode layer is preferably from 10 nm to 20 μm, more preferably from 100 nm to 15 μm, still more preferably from 1 μm to 10 μm. The aperture ratio of the pattern opening portion (the portion where the auxiliary electrode layer is not formed) of the auxiliary electrode layer is preferably 80% or more and less than 100%, more preferably 85, from the viewpoint of transparency (light transmittance). More than % and less than 99%, and more preferably more than 90% and less than 98%. Further, the aperture ratio is a ratio of the total area of the opening to the area of the entire area in which the pattern of the auxiliary electrode layer including the opening is formed. The line width of the auxiliary electrode layer is preferably from 0.1 to 100 μm, more preferably from 1 to 80 μm, still more preferably from 5 to 60 μm. When the line width is within this range, the aperture ratio is wide, the transmittance is ensured, and a stable low-resistance transparent conductive laminate is obtained, which is preferable.

(Embedded resin layer) The embedded resin layer used in the present invention is for suppressing the occurrence of irregularities on the surface of the transparent conductive layer of the transparent conductive laminate due to temperature rise during film formation of the transparent conductive layer and stress relaxation of the film. It is used to show the improvement in transferability and flexibility of the auxiliary electrode layer.

The elastic modulus at 25 ° C of the embedded resin layer is 3000 to 8000 MPa, and the elastic modulus at 70 ° C is 1000 to 7000 MPa. When the modulus of elasticity at 25 ° C is less than 3000 MPa, the transfer property of the auxiliary electrode layer is poor, so that the transparent conductive layered body using the transfer step cannot be formed. When the modulus at 25 ° C exceeds 8000 MPa, the bendability is lowered. In addition, if the modulus of elasticity at 70 ° C is less than 1000 MPa, the heat shrinkage caused by the heat history of the dry film formation and the film stress of the transparent conductive layer are likely to cause unevenness in the surface of the resin, and the turbidity also increases. It is easy to crack the transparent conductive layer. When the modulus at 70 ° C exceeds 7,000 MPa, the stress relaxation of the transparent conductive layer after film formation cannot be sufficiently suppressed, and the transparent conductive layer may be peeled off. The elastic modulus at 25 ° C is preferably from 3,300 to 7,900 MPa, more preferably from 3,500 to 7,500 MPa, and even more preferably from 3,600 to 7,300 MPa. The elastic modulus at 70 ° C is preferably from 1100 to 6700 MPa, more preferably from 1200 to 6500 MPa, and even more preferably from 1300 to 6400 MPa. When the modulus of elasticity at 25 ° C and the modulus of elasticity at 70 ° C are within the above range, the transfer property of the auxiliary electrode layer is improved, and the stress relaxation of the transparent conductive layer after film formation can be suppressed, and the increase in turbidity can be suppressed. A transparent conductive laminate having excellent optical properties.

The glass transition temperature of the buried resin layer is preferably 90 ° C or higher, more preferably 110 ° C or higher, and still more preferably 130 ° C or higher. When the glass transition temperature of the embedded resin layer is within this range, the elastic modulus at 70 ° C can be maintained within the above range. The thickness of the buried resin layer is preferably from 0.1 to 100 μm, more preferably from 1 to 80 μm, still more preferably from 5 to 60 μm. When the film thickness of the embedded resin layer is within this range and the elastic modulus is within the range of the present invention, stress relaxation of the transparent conductive layer after film formation can be suppressed, and the auxiliary electrode layer can be buried.

The embedding resin layer used in the present invention is not particularly limited as long as the elastic modulus is within the range of the present invention, but may be formed from a transparent resin composition containing inorganic fine particles from the viewpoint of obtaining a high elastic modulus even at a high temperature. Further, inorganic fine particles may not be contained. Specifically, when inorganic fine particles are contained, the following energy ray-sensitive composition can be cured. The energy ray-inducing composition contains (i) an energy ray-curable compound, (ii) inorganic fine particles, and (iii) a photopolymerization initiator. By irradiating the energy ray to the energy ray-inductive composition, it is possible to crosslink and harden. Further, the composition may contain an additive such as an ultraviolet absorber, a light stabilizer, an antioxidant, an infrared absorber, an antistatic agent, a leveling agent, or an antifoaming agent, within a range not impairing the effects of the present invention. In the present invention, the term "energy line" means an electromagnetic wave such as an ultraviolet ray or an electron beam or an energy quantum beam in a charged particle beam.

(i) The energy ray-curable compound is an energy ray-curable compound, preferably a polyfunctional (meth) acrylate monomer and/or a (meth) acrylate prepolymer, and more preferably polyfunctional. (Meth) acrylate monomer. In the present invention, the term "(meth)acrylate" means both acrylate and methacrylate, and other similar terms are also the same.

Examples of the polyfunctional (meth)acrylate monomer are 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and neopentyl glycol. (Meth) acrylate, polyethylene glycol di(meth) acrylate, hydroxypivalic acid neopentyl glycol di(meth) acrylate, dicyclopentyl di(meth) acrylate, caprolactone Modified dicyclopentenyl di(meth) acrylate, ethylene oxide modified di(meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate II (Meth) acrylate, trimethylolpropane tri(meth) acrylate, dipentaerythritol tri(meth) acrylate, propionic acid modified dipentaerythritol tri(meth) acrylate, pentaerythritol tri (methyl) Acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, tris(propylene decyloxy) isocyanurate, propionic acid modified dipentaerythritol penta (meth) acrylate, dipentaerythritol Hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and the like. Further, these monomers may be used singly or in combination of two or more.

The (meth) acrylate type prepolymer is exemplified by, for example, a polyester (meth) acrylate prepolymer, an epoxy (meth) acrylate prepolymer, and a urethane (methyl). An acrylate prepolymer, a polyol (meth) acrylate prepolymer, or the like. The polyester (meth) acrylate type prepolymer can be obtained by (meth) acrylating a hydroxyl group of a polyester oligo having a hydroxyl group at both terminals by condensing a polyvalent carboxylic acid with a polyhydric alcohol, for example. . Alternatively, it can be obtained by (meth)acrylating a terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide to a polyvalent carboxylic acid. The epoxy acrylate-based prepolymer can be obtained, for example, by reacting and esterifying an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or a novolak type epoxy resin with (meth)acrylic acid. The urethane acrylate-based prepolymer can be obtained by reacting a polyether polyol or a polyester polyol with a polyisocyanate to obtain a polyurethane oligopolymer having a hydroxyl group at both terminals. Obtained by acylation. The polyol acrylate-based prepolymer can be obtained by (meth)acrylizing a hydroxyl group of a polyether polyol. Further, these prepolymers may be used singly or in combination of two or more kinds thereof, or may be used in combination with the above-mentioned polyfunctional (meth) acrylate monomer.

(ii) Inorganic fine particles The inorganic fine particles used in the present invention are not particularly limited, and the basic characteristics of the transparent conductive laminated body can be reduced without impairing the total light transmittance (increased turbidity) of the transparent conductive laminated body. The internal selection is exemplified by cerium oxide microparticles, titanium oxide microparticles, alumina microparticles, and calcium carbonate microparticles. Among the inorganic fine particles, cerium oxide surface-modified with an organic compound having a polymerizable unsaturated group reactive with the energy ray-curable compound is preferred from the viewpoint of forming a strong bond with the (i) energy ray-curable compound. Microparticles. The cerium oxide microparticles surface-modified with an organic compound having a polymerizable unsaturated group can be organically obtained by reacting a surface stanol group of cerium oxide microparticles with a polymerizable unsaturated group having a functional group reactive with the stanol group. The compound is obtained by reaction. Further, in the present invention, the organic compound having a polymerizable unsaturated group on the surface of the inorganic fine particles is modified as a component of (ii) inorganic fine particles, and is distinguished from the above (i) energy ray-curable compound.

The organic compound containing a polymerizable unsaturated group having a functional group reactive with the stanol group is preferably a compound represented by the following formula (1).

(wherein R ¹ is a hydrogen atom or a methyl group, and R ² is a halogen atom or a group represented by the following formula).

As such organic compounds, for example, (meth)acrylic acid chloride, 2-isocyanate ethyl (meth)acrylate, glycidyl (meth)acrylate, 2,3-imine (meth)acrylate (meth)acrylic acid and its derivatives such as propyl ester, 2-hydroxyethyl (meth)acrylate, (meth)acrylic acid, (meth)acryloxypropyltrimethoxydecane, etc., may be used alone or Two or more types can be used in combination.

The content of the inorganic fine particles in the entire volume of the embedded resin layer containing the inorganic fine particles is preferably from 20 to 70% by volume, more preferably from 30 to 65% by volume, still more preferably from 30 to 60% by volume. When the content of the inorganic fine particles is within this range, for example, the elastic modulus at 70 ° C of the embedded resin layer can be controlled to a high value. Moreover, heat resistance can be improved. The inorganic fine particles are preferably cerium oxide fine particles.

(iii) Photopolymerization initiator The energy ray-inducing composition contains a photopolymerization initiator. Examples of the photopolymerization initiator are benzoin, benzoin methyl ether, benzoin ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, acetophenone, and dimethyl Aminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1 -Phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholine-propan-1-one, 4- (2-hydroxyethoxy)phenyl-2(hydroxy-2-propyl)one, benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, Dichlorobenzophenone, 2-methyl hydrazine, 2-ethyl hydrazine, 2-tert-butyl fluorene, 2-amino hydrazine, 2-methyl thioxanthone, 2-ethyl thiophene Tons of ketone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyldimethylacetal, acetophenone dimethyl acetal, pair - dimethylamino benzoate or the like. These photopolymerization initiators may be used singly or in combination of two or more. Commercially available Irgacure 127, Irgacure 184, Irgacure 819, Darocure 1173, and the like can be suitably used.

Commercial products including the above-described (i) energy ray-curable compound, (ii) cerium oxide microparticles, and (iii) photopolymerization initiator are exemplified by, for example, "OPSTAR Z7530" and "OPSTAR Z7524". "OPSTAR TU4086" (product name, all manufactured by JSR).

Further, in the above, an energy ray-inductive composition comprising (i) an energy ray-curable compound and (iii) a photopolymerization initiator, which does not contain (ii) cerium oxide microparticles, can be used to form a buried resin layer. The (i) energy ray-curable compound is preferably a urethane acrylate-based compound from the viewpoint of flexibility, and is, for example, a molar reaction of a compound 1 having two or more NCO groups in one molecule. A compound having one or more (meth)acrylic groups in one molecule obtained from a hydroxyl group-containing acrylic monomer having an ear content or more. Here, examples of the hydroxyl group-containing acrylic monomer include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and polyethylene. A hydroxyl group-containing (meth) acrylate such as an alcohol mono(meth)acrylate, a polypropylene glycol mono(meth)acrylate, or a cyclohexanedimethanol mono(meth)acrylate. In addition, the compound having two or more NCO groups in one molecule is preferably an oligomer having a molecular weight of about 500 to 50,000 obtained by reacting a polyisocyanate compound such as a diisocyanate with a polyol compound such as a diol. Examples of the polyisocyanate compound include aliphatic polyisocyanates such as hexamethylene diisocyanate and isophorone diisocyanate, or toluene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, and phenyl diisocyanate. Aromatic polyisocyanate. Examples of the polyol compound include glycols such as ethylene glycol, propylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol, and 1,4-cyclohexanediol; glycerin, pentaerythritol, and the like. Polyols of more than 3 yuan; polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, etc.; the above diols and phthalic acid, isophthalic acid A polyester type diol obtained by reacting a dibasic acid such as dicarboxylic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid or sebacic acid. For example, a commercially available product is a UV-curable urethane acrylate resin (manufactured by Nippon Synthetic Chemical Co., Ltd., UT 5746, a solid content of 80% by mass, an ethyl acetate solution). As the photopolymerization initiator, a compound which generates a radical upon irradiation with light is exemplified. Examples of such a photopolymerization initiator include a phenyl ketene photopolymerization initiator, a fluorenyl phosphine oxide photopolymerization initiator, and an oxime ester copolymerization initiator. Among these, a fluorenylphosphine oxide-based photoreaction initiator is preferred because it is easy to adjust the modulus of elasticity. The embedded resin layer having a specific modulus of elasticity can also be formed by adjusting the amount of the photopolymerization initiator or the like. The content of the photopolymerization initiator is preferably 0.2 to 5 parts by mass, more preferably 0.5 to 3 parts by mass, per 100 parts by mass of the (i) energy ray-curable compound. When the content of the photopolymerization initiator is within this range, the weather resistance is good and the curability is sufficient.

The energy ray-sensitive composition may also contain an ultraviolet absorber as needed. Examples of the ultraviolet absorber include a benzotriazole-based ultraviolet absorber, a hindered amine-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, and a triazine-based ultraviolet absorber. These ultraviolet absorbers can be used alone or in combination of two or more. Among these, a radically polymerizable ultraviolet absorber having a radical polymerizable double bond in the molecule is preferred. The content of the ultraviolet ray absorbing agent is preferably 0.2 to 10% by mass based on 100 parts by mass of the total of (i) the energy ray-curable compound, (ii) cerium oxide fine particles, and (iii) photopolymerization initiator. More preferably 0.5 to 7 parts by mass.

The energy ray-sensitive composition may also contain a light stabilizer as needed. Examples of the photostabilizer include a hindered amine light stabilizer, a benzophenone light stabilizer, a benzotriazole light stabilizer, and the like. These light stabilizers may be used singly or in combination of two or more kinds. The content of the light stabilizer is preferably 0.2 to 10% by mass based on 100 parts by mass of the total of (i) the energy ray-curable compound, (ii) cerium oxide fine particles, and (iii) photopolymerization initiator. More preferably 0.5 to 7 parts by mass. Further, a polymerization inhibitor, a viscosity modifier, a surfactant, an antifoaming agent, an organic metal coupling agent, a decane coupling agent, or the like may be added in addition to the above components as needed.

(Transparent Conductive Layer) The transparent conductive layer used in the present invention is made of a metal oxide. Examples of the metal oxides include indium-tin oxide (ITO), indium-zinc oxide (IZO), aluminum-zinc oxide (AZO), gallium-zinc oxide (GZO), and indium-gallium-zinc oxide ( IGZO), cerium oxide, titanium oxide, tin oxide, etc., may be used singly or in plural. Among these, ITO and IZO are particularly preferable from the viewpoints of transmittance, sheet resistance, and stability. The film thickness of the transparent conductive layer is preferably from 5 to 200 nm, more preferably from 10 to 100 nm, even more preferably from 20 to 50 nm. If it is in this range, a film having high transmittance, low surface resistivity, and uniformity of in-plane resistance can be obtained, which is preferable. Further, the total light transmittance of the transparent conductive layer is preferably 70% or more, more preferably 80% or more, and more preferably 90% or more, measured according to JIS K7361-1. The turbidity of the transparent conductive layer is preferably 10% or less, more preferably 5% or less. The sheet resistance of the transparent conductive layer is preferably 1000 Ω/□ or less, more preferably 500 Ω/□ or less, and still more preferably 100 Ω/□ or less.

As a method of forming the transparent conductive layer, a dry film formation method is preferred from the viewpoint of obtaining high transmittance and low sheet resistance. For example, a physical vapor phase growth method (hereinafter also referred to as "PVD") such as a resistance heating vapor deposition method, an electron beam evaporation method, a molecular beam epitaxy method, an ion beam method, an ion plating method, or a sputtering method, or A dry film formation method such as a chemical vapor deposition method (hereinafter also referred to as "CVD") such as a thermal CVD method, a plasma CVD method, a photo CVD method, an epitaxial CVD method, or an atomic layer CVD method. It is preferable to use a sputtering method because it is easy to obtain a low sheet resistance value, a film thickness control with high precision, a specific composition ratio, and high quality stability. After the film formation by the above method, if necessary, heat treatment is applied in a range which does not affect other laminates, whereby a more excellent sheet resistance value can be obtained. The dry film forming method referred to herein also has a surface treated with a gas phase or a molten state, and is generally referred to as a dry process.

(Adhesive layer) The transparent conductive laminated body of the present invention preferably further comprises an adhesive layer on a surface of the resin layer opposite to the transparent conductive layer, and is more preferably embedded in the resin layer and a transparent gas barrier layer to be described later. The aforementioned adhesive layer is included between them. The adhesive layer is used to increase the adhesion of the embedded resin layer to, for example, the above-described transparent gas barrier layer, and to improve the flexibility of the transparent conductive laminate.

The elastic modulus at 25 ° C of the adhesive layer is preferably from 100 to 3,000 MPa, more preferably from 200 to 2,400 MPa, and even more preferably from 400 to 2,200 MPa. When the elastic modulus of the adhesive layer at 25 ° C is in the above range, the adhesive property is improved and the flexibility is further improved by directly interposing between the transparent gas barrier layer and the like and the embedded resin layer.

The glass transition temperature of the adhesive layer is preferably 40 ° C or higher, more preferably 50 ° C or higher, and still more preferably 60 ° C or higher. When the glass transition temperature of the adhesive layer is lower than the glass transition temperature of the embedded resin layer to be combined, the adhesion and the bendability are improved. The film thickness of the adhesive layer is preferably from 1 to 120 μm, more preferably from 3 to 100 μm, still more preferably from 4 to 80 μm. When the film thickness of the embedded resin is within the above range, and the thickness of the adhesive layer film is within the above range, the flexibility of the transparent conductive laminated body is improved.

The adhesive layer used in the present invention is not particularly limited as long as the elastic modulus is within the range of the present invention, and is preferably a transparent resin composition as in the case of the embedded resin layer. For example, an energy ray hardening type compound, a thermoplastic resin, etc. are mentioned.

The energy ray-curable compound is exemplified by the same as those used for embedding the resin layer.

Examples of the thermoplastic resin include polyolefin resins such as polyethylene, polypropylene, and polybutene, (meth)acrylic resins, polyvinyl chloride resins, polystyrene resins, polyvinylidene chloride resins, and ethylene. - vinyl acetate copolymer saponified product, polyvinyl alcohol, polycarbonate resin, fluorine resin, polyvinyl acetate resin, acetal resin, polyethylene terephthalate (PET), polynaphthalene A polyester resin such as ethylene formate (PEN) or polybutylene naphthalate (PBN), a polyamide resin such as nylon 6, or nylon 66. Further, the above resins may be used alone or in combination of two or more. Among these, polyethylene, polypropylene, polystyrene, polyvinyl chloride, and polyvinylidene chloride are preferable.

Commercially available products of the energy ray-curable compound are, for example, UV-curable acrylic resin (manufactured by Toyo Ink Co., Ltd., UA-A1, solid content: 100% by mass), and UV-curable acrylic resin (manufactured by Toagosei Co., Ltd., UVX6125, solid content) 100% by weight or the like, as a photopolymerization initiator, Irgacure 819 (manufactured by BASF Corporation) or the like is exemplified. Similarly to the above-described buried resin layer, an adhesive layer having a specific modulus of elasticity can be obtained by adjusting the amount of the photopolymerization initiator or the like. The content of the photopolymerization initiator is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 5 parts by mass, per 100 parts by mass of the energy ray-curable compound. When the content of the photopolymerization initiator is within this range, the hardenability is sufficient. Further, a polymerization inhibitor, a viscosity modifier, a surfactant, an antifoaming agent, an organic metal coupling agent or the like may be added in addition to the above components as needed.

(Transparent Gas Barrier Layer) In the transparent conductive laminate of the present invention, it is preferred to further include a transparent gas barrier layer on the transparent substrate. The transparent gas barrier layer used in the present invention has a function of suppressing the permeation of water vapor in the atmosphere passing through the transparent substrate 2 in FIG. 2, and as a result, preventing the water vapor from penetrating into the resin layer 3, the auxiliary electrode layer 4, and the like. In the present invention, when the transparent gas barrier layer is laminated on the transparent substrate, the water vapor transmission rate under high humidity conditions of 40 ° C and 90% RH on the surface side of the transparent substrate without the transparent gas barrier layer is higher. It is preferably 1.0 (g·m ^-2 ·day ^-1 ) or less, more preferably 1.0 × 10 ^-2 (g·m ^-2 ·day ^-1 ) or less, and even more preferably 5.0 × 10 ^-4 (g·m ^-2・day ^-1 ) or less, especially preferably 1.0 × 10 ^-4 (g・m ^-2・day ^-1 ) or less. The transparent conductive laminated body of the present invention can be transparently conductive, for example, by maintaining the water vapor transmission rate in the range of the water vapor transmission rate of the auxiliary electrode layer or the other layer embedded in the resin layer. The layer is not deteriorated by moisture, and the increase in sheet resistance can be suppressed. Further, when used as a translucent electrode of an electronic device, it is possible to suppress deterioration of the active layer or the like inside the devices over time, which is related to the long life of the device.

The transparent gas barrier layer is exemplified by a layer containing a metal oxide, a layer obtained by modifying a layer containing a polymer compound (hereinafter sometimes referred to as a "polymer layer"), and the like, and the like. As a method of forming the above-described layer containing a metal oxide, a method of forming the above-described transparent conductive layer can be used. Further, after the film formation, a lower sheet resistance value is obtained by performing heat treatment in a range not affecting other laminates as needed. As a raw material of the metal oxide, for example, a metal such as lanthanum, aluminum, magnesium, zinc, or tin; inorganic cerium oxide, cerium oxide, aluminum oxide, magnesium oxide, zinc oxide, indium oxide, tin oxide, zinc tin oxide, or the like An oxide; an inorganic nitride such as tantalum nitride, aluminum nitride or titanium nitride; an inorganic carbide; an inorganic sulfide; an inorganic oxynitride such as lanthanum oxynitride; an inorganic oxidized carbide; an inorganic carbide; Inorganic oxynitride carbides, etc. These may be used alone or in combination of two or more. Among these, from the viewpoint of gas barrier properties, an inorganic deposited film containing an inorganic oxide, an inorganic nitride or a metal as a raw material is preferred. Further, from the viewpoint of having interlayer adhesion, gas barrier properties, and folding resistance, it is preferred to use oxygen which is formed by reforming a layer containing a metal oxide or a layer containing a polyazane-based compound. Nitrogen and bismuth are the yttria layers formed by the layers of atoms. The polymer compound used for the polymer layer is exemplified by a fluorene-containing polymer compound such as a polyorganosiloxane or a polyazane compound, a polyimine, a polyamine, a polyamidimide, or a polyphenylene ether. , polyether ketone, polyether ether ketone, polyolefin, polyester, and the like. These polymer compounds may be used alone or in combination of two or more. Among these, a polymer compound is preferably a ruthenium-containing polymer compound based on more excellent gas barrier properties. Examples of the ruthenium containing polymer compound include a polyazane-based compound, a polycarbodecane-based compound, a polydecane-based compound, and a polyorganosiloxane compound. Among these, a polyazane-based compound is preferred from the viewpoint of forming a transparent gas barrier layer having excellent gas barrier properties.

The transparent gas barrier layer can be formed, for example, by subjecting a layer containing a polyazide compound to plasma ion implantation treatment, plasma treatment, ultraviolet irradiation treatment, heat treatment, or the like. Examples of the ions to be implanted by the plasma ion implantation treatment include hydrogen, nitrogen, oxygen, argon, helium, neon, krypton, and xenon. The specific treatment method for the plasma ion implantation treatment is exemplified by a method of injecting ions existing in the generated plasma into the layer containing the polyazide compound using an external electric field, or without using an external electric field, only by A method in which ions existing in a plasma generated by applying a negative high-voltage pulse to a layer formed of a material for forming a gas barrier layer is injected into a layer containing a polyazide compound. The plasma treatment is a method in which a layer containing a polyazide compound is exposed to a plasma to modify a layer containing a ruthenium-containing polymer. For example, the plasma treatment can be carried out in accordance with the method described in JP-A-2012-106421. The ultraviolet irradiation treatment is a method in which a layer containing a polyazide compound is irradiated with ultraviolet rays to modify a layer containing a ruthenium-containing polymer. For example, the ultraviolet modification treatment can be carried out in accordance with the method described in JP-A-2013-226757. In these cases, the ion implantation treatment is preferably carried out by roughening the surface of the layer containing the polyazide-containing compound, and it is possible to form a gas barrier layer which is more excellent in gas barrier properties.

The method of laminating the transparent gas barrier layer is not particularly limited, but is preferably a layering method based on ease of manufacture.

The transparent gas barrier layer may be one layer or two or more layers. When two or more layers are laminated, the same may be the same or different. The thickness of the transparent gas barrier layer is preferably from 20 nm to 50 μm, more preferably from 30 nm to 1 μm, even more preferably from 40 to 500 nm. When the film thickness of the transparent gas barrier layer is within this range, excellent gas barrier properties or adhesive properties are obtained, and both flexibility and film strength can be obtained.

(Undercoat layer) When a transparent gas barrier layer is formed on a transparent substrate, an undercoat layer may be used in order to improve the adhesion between the transparent substrate and the transparent gas barrier layer. As the undercoat layer, for example, an undercoat layer of an acrylic type, a polyester type, a polyurethane type, or a rubber type can be suitably used. The thickness of the undercoat layer is usually from 0.1 to 10 μm, preferably from 0.5 to 5 μm. When the thickness of the undercoat layer is within the above range, the unevenness of the transparent substrate can be covered, and the defects from the transparent substrate can be reduced, and the gas barrier property of the transparent gas barrier layer can be improved, and the transparent substrate and the transparent gas barrier layer can be improved. The adhesive force can be smoothly peeled off from the transfer substrate side in the surface smoothness transfer step of the transfer substrate surface to be described later.

The haze of the transparent electroconductive laminate of the present invention is preferably 2.5% or less, more preferably 2.0% or less. Further, the turbidity increase rate before and after the dry film formation (the ratio of the haze value after the dry film formation to the haze value before the dry film formation) is preferably 1.40 or less, more preferably 1.25 or less, and more preferably 1.10 or less. When the turbidity value and the turbidity increase rate before and after the dry film formation are within this range, a transparent conductive layered body excellent in optical characteristics is obtained.

The sheet resistance value on the side of the transparent conductive layer of the transparent conductive laminated body of the present invention is preferably 10 Ω/□ or less, more preferably 5 Ω/□ or less, and still more preferably 1 Ω/□ or less. When the sheet resistance value is in this range, a transparent conductive laminate having excellent electrical properties is obtained.

The thickness of the transparent conductive laminate is preferably from 10 to 300 μm, more preferably from 10 to 200 μm, still more preferably from 20 to 150 μm. When it is this range, a transparent conductive layer is laminated on the transparent conductive laminated body, and when it is made into a transparent conductive laminated body, it is flexible, and can provide high transmittance and low sheet resistance value. The total light transmittance (T ₀ ) of the opening of the transparent conductive laminated body is preferably from 80% to 96%, more preferably from 90% to 96%, still more preferably from 92% to 96%. The total light transmittance (T) of the transparent conductive laminate including the auxiliary electrode layer is preferably from 80% to 95%, more preferably from 83% to 95%, still more preferably from 85% to 95%. The ratio T/T ₀ of the total light transmittance (T) of the transparent conductive laminate including the auxiliary electrode layer to the total light transmittance (T ₀ ) of the opening of the transparent conductive laminate, if not due to the increase in surface resistivity If the electrical property is damaged, the closer to 1, the better, preferably 0.93 to 0.99, more preferably 0.96 to 0.99, and even more preferably 0.97 to 0.99. Further, when the auxiliary electrode layer is printed in the same pattern, the thinner the line width of the auxiliary electrode layer means that it is closer to 1.

The transparent conductive laminate of the present invention has excellent optical properties and flexibility. Further, the sheet resistance value is small, and the transfer property of the auxiliary electrode layer is excellent. Therefore, it can be suitably applied to a solar cell element or an organic electro-sensor element which must be large in area.

[Manufacturing Method of Transparent Conductive Laminate] The method for producing a transparent conductive laminate according to the present invention is a method of producing a transparent conductive laminated body comprising at least a buried resin layer on a transparent substrate The auxiliary electrode layer and the transparent conductive layer are made of a metal oxide. The embedded resin layer has an elastic modulus at 25 ° C of 3000 to 8000 MPa, and the elastic modulus at 70 ° C is 1000 to 7000 MPa. The method includes the steps of forming the auxiliary electrode layer, forming the step of embedding the resin layer on the opening of the auxiliary electrode layer, forming the buried resin layer on the auxiliary electrode layer and the opening, and forming the transparent conductive layer.

(Assisted electrode layer forming step) The step of forming the auxiliary electrode layer forming step on a transfer substrate to be described later to form a pattern formed by the material of the auxiliary electrode layer. The method of forming the auxiliary electrode layer is exemplified by a conventional physical treatment or chemical treatment mainly by photolithography, or a combination of the auxiliary electrode layer having no pattern formed on the transfer substrate. a method of processing into a specific pattern shape, or directly forming a supplementary electrode by a screen printing method, a rotary screen printing method, a screen printing method, an inkjet method, a soft printing method, a gravure printing method, or the like The method of layer pattern, etc. As a method of forming the auxiliary electrode layer which is not formed, a PVD method (physical vapor phase growth method) such as a vacuum deposition method, a sputtering method, or an ion plating method, or a thermal CVD method or an ALD method (atomic layer) can be exemplified. Dry process such as CVD method (chemical vapor phase growth method) such as vapor deposition method, or dip coating method, spin coating method, spray coating method, gravure coating method, die coating method, blade coating Various wet coating processes such as coating or plating, silver salt method, and the like are appropriately selected depending on the material of the auxiliary electrode layer.

(Embedded Resin Layer Forming Step) The embedded resin layer forming step is a step of embedding a resin layer on the opening of the auxiliary electrode layer or on the opening and the auxiliary electrode layer. As another aspect, the step of embedding the resin layer on the adhesive layer or the transparent gas barrier layer is carried out.

Examples of the method for forming the embedded resin layer include a dip coating method, a spin coating method, a spray coating method, a gravure coating method, a die coating method, a knife coating method, and a Maya coating method. As a method of irradiating energy radiation, for example, an ultraviolet ray or an electron beam or the like is exemplified. The above ultraviolet rays can be obtained by a high pressure mercury lamp, a flash H lamp, a xenon lamp, etc., and the amount of light is usually 100 to 500 mJ/cm ² , and on the other hand, the electron beam is obtained by an electron beam accelerator or the like, and the irradiation amount is usually 150 to 350 kV. Among the energy rays, ultraviolet rays are particularly preferred. Further, when an electron beam is used, a cured film can be obtained without adding a photopolymerization initiator.

(Transparent Conductive Layer Forming Step) The transparent conductive layer forming step is a step of forming a transparent conductive layer on the side of the surface formed by the auxiliary electrode layer and the buried resin layer. The method of forming the transparent conductive layer is as described above.

(Adhesive layer forming step) In the production of the transparent conductive laminated body of the present invention, it is preferred to further include an adhesive layer forming step. The adhesive layer forming step is a step of forming an adhesive layer on the buried resin layer. As another aspect, the step of forming an adhesive layer on the transparent gas barrier layer. The method of forming the adhesive layer is the same as the method of forming the buried resin layer.

(Transparent gas barrier layer forming step) In the production of the transparent conductive laminated body of the present invention, it is preferred to further include a transparent gas barrier layer forming step. The transparent gas barrier layer forming step is a step of forming a transparent gas barrier layer on the transparent substrate via the undercoat layer. The method of forming the transparent gas barrier layer and the lamination method are as described above.

(Transfer Substrate Forming Step) In the production of the transparent electroconductive laminate of the present invention, it is preferred to further include a transfer substrate forming step. The transfer substrate forming step is a step of forming a release layer on the support of the transfer substrate.

(Support) The support is not particularly limited, and examples thereof include a polyester film such as polyethylene terephthalate or polyethylene naphthalate, and a polyolefin such as polypropylene or polymethylpentene. A film, a polycarbonate film, a polyvinyl acetate film or the like, among which a polyester film is preferred, and a biaxially oriented polyethylene terephthalate film is particularly preferred. The thickness of the support is preferably from 10 to 500 μm, more preferably from 20 to 300 μm, even more preferably from 30 to 100 μm. If it is this range, mechanical strength can be ensured, and it is preferable.

(Release layer) The release layer used in the present invention may or may not be provided by the support used, but it is preferably a layer which hardens the polyoxymethylene resin composition or the ultraviolet-curable release composition (hereinafter, It is called "hardened layer".

The composition of the polyanthracene resin is not particularly limited, and examples thereof include an addition reaction type polyfluorene oxide resin composition containing a photosensitizer. The addition reaction type polyoxo resin composition is a catalyst (for example, a platinum-based catalyst) and a photosensitizer added to the main component of the addition reaction type polyoxyxylene resin and a crosslinking agent, as needed. An addition reaction inhibitor, a peeling adjuster, an adhesion enhancer, or the like may also be added.

The ultraviolet curable peeling composition is not particularly limited, and may be a conventional ultraviolet curable peeling composition, and a commercially available product can be used. Specifically, a polyoxymethylene-based, fluorine-based, alkyl side chain system, or long-chain alkyl-based ultraviolet curable exfoliating composition can be exemplified. The addition reaction inhibitor, the peeling adjuster, the adhesion promoter, and the like may be added as needed. Further, it is preferred that the ultraviolet curable exfoliating composition segregates cerium on the surface.

The method for forming the hardened layer may be a coating liquid formed of a polyoxyxylene resin composition or an ultraviolet curable release composition and the above-described additive component, which is used as desired, by, for example, a gravure coating method or a bar coating method. A spray coating method, a spin coating method, or the like is applied to the substrate. At this time, an appropriate organic solvent may be added for the purpose of viscosity adjustment of the coating liquid. The organic solvent is not particularly limited, and various ones can be used. For example, a hydrocarbon compound such as toluene or hexane, a mixture of ethyl acetate, methyl ethyl ketone, and the like can be used.

(Transfer Step of Transfer Substrate Surface) In the production of the transparent electroconductive laminate of the present invention, it is preferred to further include a transfer step of transferring the substrate surface. The transfer step of the transfer substrate surface is a step of peeling off the transfer substrate and the surface formed by the auxiliary electrode layer and the embedded resin layer. The peeling method of the transfer substrate and the surface formed by the auxiliary electrode layer and the transparent resin layer is not particularly limited, and it can be carried out by a conventional method. By the present transfer step, the surface smoothness of the auxiliary electrode layer and the embedded resin layer can be excellent, and the increase in turbidity can be suppressed, and as a result, the optical characteristics of the transparent conductive laminated body can be improved.

(Laminating Step Forming Step) In the production of the transparent conductive laminated body of the present invention, it is also possible to have a step of laminating different laminated bodies by lamination or the like. For example, in one aspect, a laminate formed of a transfer substrate/substrate electrode layer and a laminate formed of a buried resin layer/transparent gas barrier layer/undercoat layer/transparent substrate may be laminated. A laminate of the transfer substrate/substrate electrode layer/embedded resin layer/transparent gas barrier layer/undercoat layer/transparent substrate is formed. In another aspect, a laminate formed of a transfer substrate/substrate electrode layer/embedded resin layer and a laminate formed of a transparent gas barrier layer/undercoat layer/transparent substrate may be laminated. A laminate formed of a transfer substrate/substrate electrode layer/embedded resin layer/transparent gas barrier layer/undercoat layer/transparent substrate. Further, as another aspect, the laminate formed of the transfer substrate/substrate electrode layer/embedded resin layer/adhesive layer and the laminate of the transparent gas barrier layer/undercoat layer/transparent substrate may be used. Laminating or laminating a laminate formed of a transfer substrate/substrate electrode layer/embedded resin layer and an adhesive layer/transparent gas barrier layer/undercoat layer/transparent substrate to form a laminate The transfer substrate/substrate electrode layer/embedded resin layer/adhesive layer/transparent gas barrier layer/undercoat layer/transparent substrate is formed into a laminate including an adhesive layer. In either case, the transfer substrate is peeled off from the interface side of the transfer substrate/substance electrode layer to form a transparent conductive laminate, which is formed by the auxiliary electrode layer and the embedded resin layer of the transparent conductive laminate. The transparent conductive layer of the present invention can be produced by forming a transparent conductive layer on the surface.

According to the production method of the present invention, a transparent conductive laminate having excellent optical characteristics and flexibility can be produced. [Examples]

Next, the invention will be described in more detail by way of examples, but the invention is not limited by the examples.

The transparent conductive laminate and the transparent conductive laminate produced in the examples and the comparative examples were subjected to the following evaluation and measurement. The results are shown in Table 1, Table 2-1, and Table 2-2. (a) Elasticity ratio The embedded resin layer and the adhesive layer (the embedded resin layer is formed after the transparent conductive laminated body is formed, and the adhesive layer is formed after the formation), and a dynamic ultra-fine hardness tester (product name manufactured by Shimadzu Corporation) is used. "DUH-W201S") The load-unloading test was carried out under the following measurement conditions, and the elastic modulus was calculated from the slope of the obtained unloading curve. The elastic modulus can be measured as described in the examples, and after the transparent conductive laminated body is produced, the transparent conductive laminated body can be obliquely cut, for example, with a diamond knife or the like, and the exposed portion is exposed, and the exposed measurement portion is vertically contacted with dynamic ultrafine The measurement is carried out by means of a small hardness tester, and the other layer laminated on the measurement site may be removed by etching or the like, and the measurement site may be exposed and then measured. <Dynamic ultra-micro hardness tester> Pressure: Triangular cone angle 115 ̊ Test mode: Load-unload mode Test force: 1 mN Load speed: 0.142 mN/sec Hold time: 5 sec Measurement temperature: 25 ° C, 70°C (b) Glass transition temperature Tg In the examples and the comparative examples, a buried resin layer was formed on a glass slide having a thickness of 1 mm using a specific resin solution, and a viscoelasticity measuring device (DMAZSCH JAPAN, DMA242 E, DMA242 E) was used. Artemis) measures the storage elastic modulus E' of the embedded resin layer in a measurement range of 0 to 200 ° C in a tensile mode at a frequency of 10 Hz. Further, the loss elastic modulus E" was measured, and the measurement temperature at which the peak value of the obtained loss tangent tan δ (=E"/E') was applied was defined as the glass transition temperature Tg. Similarly, the adhesive layer was formed using a specific coating liquid for the adhesive layer, and the glass transition temperature Tg was calculated. (c) Turbidity turbidity was measured using a turbidimeter (HAZE METER NDH5000, manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K 7136. (d) Sheet resistance value ρ The sheet resistance value ρ was measured using a non-contact resistance measuring instrument (manufactured by NAPSON Corporation, model: EC-80P). (e) Water vapor transmission rate (WVTR) Using a water vapor transmission rate meter (manufactured by MOCON Corporation, device name: AQUATRAN), a transparent conductive layer having a transparent gas barrier layer at 40 ° C and 90% RH was measured in accordance with JIS K 7129. The water vapor transmission rate of the body (g·m ^-2 ·day ^-1 ). (f) The embedded resin layer A after the transfer hardening is not spliced with the transfer substrate, and the auxiliary electrode layer can be transferred to the side of the buried resin layer, and is evaluated as ○, and conjugation or conversion occurs. The printed substrate was then evaluated as x. In the present invention, the term "conjugation" means that when the auxiliary electrode layer on the transfer substrate is transferred from the transfer substrate to the side of the embedded resin layer, the auxiliary electrode layer of the transfer substrate slides without being peeled off, and is repeatedly emitted. The sound of squeaking hinders the peeling." When the transfer is performed, the auxiliary electrode layer is not peeled off from the transfer substrate due to the conjugation, and the untransferred portion is generated. (g) Dry film-forming property measurement The turbidity before and after dry film formation when the transparent conductive layer was formed into a film of 50 μm on the surface formed by the auxiliary electrode layer and the embedded resin layer by the dry film formation method, according to the following criteria The dry film forming resistance was evaluated. The dry film-forming property means a change in the turbidity value due to dry film formation. 〇: When the turbidity rises to 10% or less △: When the turbidity rises by more than 10% and is less than 50% × When the turbidity rises by more than 50% (h) The bending property is repeated using a bending tester (manufactured by YUASA Corporation) The sheet resistance value ρ was measured before the bending of the transparent conductive layer of the transparent conductive laminated body with the convex portion of the transparent conductive layer facing upward by 100 mm, and the bending property was evaluated in accordance with the following criteria. 〇: When the sheet resistance value changes to ±0.5 Ω/□ or less △: When the sheet resistance value changes by more than ±0.5 Ω/□ and ±1 Ω/□ or less ×: When the sheet resistance value changes by more than ±1 Ω/□ (i) Heat and humidity resistance The adhesiveness was stored in a 95% RH environment at 60 ° C for 1000 hours, and then stored in a 23 ° C 50% RH environment for 24 hours, and the adhesion and sheet resistance values were evaluated. The adhesive is formed from a transparent conductive layer, and is selected to be a checkerboard shape of 1 mm to 2 mm wide cross-cut according to the thickness of the embedded resin layer and the adhesive layer, and is implemented by the blade tip reaching the gas barrier layer, and the adhesive tape is applied. (CELLOTAPE (registered trademark) manufactured by NICHIBAN Co., Ltd.) is attached to a transparent conductive layer cut into a checkerboard pattern by a NICHIBAN company, and CELLOTAPE (registered trademark) is carried out according to the checkerboard tape method of JIS K5600-5-6 (Cross Cutting Method). In the peeling test, the adhesion of the transparent conductive layer, the embedded resin layer, and the adhesive layer was evaluated in accordance with the following criteria. Further, regarding the adhesion, the determination is made based on the following criteria. 〇: The evaluation results in Table 1 of JIS K5600-5-6 are classified as 0~2 ×: The evaluation results in Table 1 of JIS K5600-5-6 are classified into 3~5 sheet resistance values and the sheet resistance value ρ is measured in the same manner.

(Example 1) The following UV-curable acrylic resin solution A was applied onto a glass slide having a thickness of 1 mm by an applicator, and dried at 90 ° C for 2 minutes, and then peeled off with a sheet B [polyphosphorus stripping treatment). A polyethylene terephthalate film (manufactured by LINTEK Co., Ltd., SP-PET381031, thickness: 38 μm) was bonded, and a conveyor belt type UV irradiation device (manufactured by HERAEUS Co., Ltd., high pressure mercury lamp) was used to accumulate a light amount of 250 mJ/cm ² . Irradiation was performed from the coated surface to obtain a buried resin layer A. Further, the film thickness after hardening was 50 μm. The embedded resin layer A was peeled off from the release sheet B, and the storage elastic modulus E' and the loss elastic modulus E" were measured, and the glass transition temperature Tg was measured from the obtained loss tangent tan δ. * UV-curable acrylic resin solution A for UV-curable acrylic resin (manufactured by Nippon Synthetic Chemical Co., Ltd., UT 5746, solid content: 80% by mass, ethyl acetate solution) 100 parts by mass of a photoinitiator (manufactured by BASF Corporation, Irgacure 819) was added in an amount of 1.5 parts by mass.

The UV-curable acrylic resin composition A was applied to the same coating/hardening conditions as described above in an alkali-free glass (manufactured by Corning Co., Ltd., EagleXG, 100 mm square, 0.7 mm thick) so as to have a film thickness of 25 μm after curing. The resin layer A was buried, and the turbidity H _{a0 was} measured. The results are shown in Table 1. With respect to the embedded resin layer A thus formed, an ITO layer of a transparent conductive layer was formed by sputtering under the following conditions, and the haze H _a1 after film formation was measured. * Transparent conductive layer film formation conditions and target: ITO (SnO ₂ -5wt%, manufactured by JX Nippon Mining & Metal Co., Ltd.) ・Method: DC magnetron sputtering ・Application method: DC500W ・Substrate heating: None, carrier gas : Argon (Ar) ・ Film formation pressure: 0.6Pa

[Production of Transparent Conductive Laminate A] As a metal paste (conductive composition) for printing a supplementary electrode layer made of a thin silver wire, a silver paste (manufactured by MITSUBOSHI BELTING Co., Ltd., trade name: low-temperature baking conductive paste MDot) is used. (registered trademark)), using a screen having a honeycomb structure with a line width of 30 μm and a pitch of 1200 μm (printing area: 100 mm square), using a screen printing machine (manufactured by MICROTEC, model: MT-320TV), by printing on a transfer A supplementary electrode layer is formed on the substrate. After printing, it was temporarily dried at 70 ° C for 1 minute, and then fired in a conveyor type hot air/IR baking furnace at 150 ° C for 10 minutes. The transfer substrate used here was PET A4100 (100 μm thick) manufactured by Toyobo Co., Ltd., and the untreated surface was the printed surface of the electrode. The obtained electrode had a width of 40 μm and a height of 7 μm. Next, the UV-curable acrylic resin composition A was applied by an applicator on the surface of the transparent gas barrier layer of the transparent substrate having the transparent gas barrier layer described later, and dried at 90 ° C for 2 minutes. The surface of the UV-curable acrylic resin composition A is laminated with the auxiliary electrode layer provided on the transfer substrate to obtain a transfer substrate/substrate electrode layer/buried resin layer A/gas barrier layer/primer layer / laminate A of transparent substrate. The laminate A was irradiated with a cumulative light amount of 250 mJ/cm ² from a transparent substrate side having a transparent gas barrier layer by a conveyor belt type UV irradiation machine (manufactured by HERAEUS Co., Ltd., high pressure mercury lamp) to form a laminate A. The buried resin layer A was hardened (the thickness of the buried resin layer A after hardening: 25 μm). Finally, the transfer substrate is peeled off from the interface side formed by the freely embedded resin layer A and the auxiliary electrode layer, and the transparent gas barrier layer is formed on the transparent substrate, and the auxiliary electrode layer having the opening portion and the buried resin layer are formed. The transparent conductive laminated body A obtained from the composite layer formed by A was measured for the elastic modulus and turbidity H _b0 at 25 ° C and 70 ° C of the embedded resin layer A by a dynamic ultra-fine surface hardness meter. Then, on the side of the auxiliary electrode layer, a transparent conductive layer of 50 nm was formed in the same manner as the film formation condition of the transparent conductive layer, and a transparent conductive laminated body was formed, and the haze H _b1 , the sheet resistance value ρ, and the water vapor transmission rate (WVTR) were measured. ).

(Production of Transparent Gas Barrier Layer) The following undercoat layer was formed by a bar coating method on a transparent substrate (polyethylene naphthalate, manufactured by Teijin DuPont Co., Ltd., PENQ65 HWA, 100 μm thick). After heating and drying at 70 ° C for 1 minute with a solution, a UV light irradiation lamp (a high-pressure mercury lamp manufactured by Fusion UV Systems JAPAN Co., Ltd.; cumulative light amount of 100 mJ/cm ² , peak intensity of 1.466 W, linear velocity of 20 m/min, number of passes 2 times was used. UV irradiation was performed to form an undercoat layer having a thickness of 1 μm. On the obtained undercoat layer, a solution containing perhydropolyazane (manufactured by AZ Electronic Materials Co., Ltd., trade name: AZNL110A-20) was applied by a spin coating method, and the resulting coating film was heated at 120 ° C for 2 minutes to form a coating film. A 200 nm thick perhydropolyazane layer. Further, on the obtained perhydropolyazide layer, plasma is ion-implanted with argon (Ar) to form a perhydrogenated azepine layer by plasma ion implantation (hereinafter referred to as "inorganic layer A". "). Next, on the inorganic layer A, a yttrium oxynitride layer (inorganic layer B) was formed twice as in the inorganic layer A except that the thickness of the perhydropolyazide layer was 150 nm, and a transparent gas barrier layer was laminated. * The solution for forming an undercoat layer, dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: A-DPH), was dissolved in 100 parts by mass of methyl isobutyl ketone, and was 3% by mass for the solid content. In the same manner, a solution obtained by a photopolymerizable initiator (manufactured by BASF Corporation, trade name: Irgacure 127) was added. The plasma ion implantation was carried out under the following conditions using the following apparatus. (plasma ion implantation apparatus) RF power supply: model "RF56000", high voltage pulse power supply manufactured by JEOL Ltd.: "PV-3-HSHV-0835", "plasma ion implantation conditions" manufactured by Iwata Manufacturing Co., Ltd. : Ar ・Gas flow rate: 100sccm ・Duty ratio: 0.5% ・Repetition frequency: 1000Hz ・Applied voltage: -10kV ・RF power supply: Frequency 13.56MHz, applied power 1000W ・In-chamber pressure: 0.2Pa ・Pulse width: 5sec ・Processing Time (ion injection time): 200 sec ・Transportation speed: 0.2 m/min

(Example 2) A transparent conductive laminate B was produced in the same manner as in Example 1 except that the embedded resin layer B was formed using the UV-curable acrylic resin solution B described below, and the embedded ultra-fine surface hardness meter was used to measure the embedding. The elastic modulus of the resin layer B at 25 ° C and 70 ° C and the haze H _{b0 of the} transparent conductive laminate B. Next, a transparent conductive laminated body was formed by laminating a transparent conductive layer, and the haze H _b1 , the sheet resistance value ρ, and the water vapor transmission rate (WVTR) were measured. Further, in the same manner as in Example 1, the glass transition temperature Tg of the embedded resin layer B was measured. * UV-curable acrylic resin solution B UV-curable acrylic resin was added to 100 parts by mass of UV-curable urethane acrylate resin (UT5746, manufactured by Nippon Synthetic Chemical Co., Ltd., solid content: 80% by mass, ethyl acetate solution). (UA-A1, manufactured by Toyo Ink Co., Ltd.) 10 parts by mass of a photoinitiator (manufactured by BASF Corporation, Irgacure 819) 1.5 parts by mass of a solution.

(Comparative Example 1) A transparent conductive laminated body C was produced in the same manner as in Example 1 except that the embedded resin layer C was formed using the UV-curable acrylic resin solution C described below. Although the elastic modulus at 25 ° C and 70 ° C of the embedded resin layer C was measured, the turbidity H _b0 and the haze H _b1 of the transparent conductive laminate C could not be measured due to poor transfer. Further, in the same manner as in Example 1, the glass transition temperature Tg of the embedded resin layer C was measured. * UV-curable acrylic resin solution C UV-curable acrylic resin (manufactured by Toyo Ink Co., Ltd.) was added to 100 parts by mass of UV-curable acrylic resin (UT5746, manufactured by Nippon Synthetic Chemical Co., Ltd., solid content: 80% by mass, ethyl acetate solution). UA-A1) 50 parts, a photoinitiator (manufactured by BASF Corporation, Irgacure 819) 1.5 parts by mass of a solution.

(Comparative Example 2) A transparent conductive laminated body D was produced in the same manner as in Example 1 except that the embedded resin layer D was formed using the UV-curable acrylic resin solution D described below. Although the elastic modulus at 25 ° C and 70 ° C of the embedded resin layer D was measured, the turbidity H _b0 , the haze H _{b1 ,} and the like of the transparent conductive laminate D could not be measured due to poor transfer. Further, in the same manner as in Example 1, the glass transition temperature Tg of the embedded resin layer D was measured. * UV-curable acrylic resin solution D A solution of UV-curable acrylic resin (UA-A1, manufactured by Toyo Ink Co., Ltd.).

(Example 3) On the glass slide having a thickness of 1 mm, the following adhesive layer coating liquid A was applied by an applicator, and dried at 90 ° C for 2 minutes, and then peeled off with a sheet B [poly-oxygen stripping treatment) Ethylene phthalate film (SP-PET381031, thickness: 38 μm) was used for bonding, and a conveyor belt type UV irradiation device (manufactured by HERAEUS Co., Ltd., high pressure mercury lamp) was used to accumulate light amount of 250 mJ/cm ² . The coated surface was irradiated to obtain an adhesive layer A. Further, the film thickness after hardening was 50 μm. The adhesive layer A was peeled off from the peeling sheet B, and the storage elastic modulus E' and the loss elastic modulus E" were measured, and the glass transition temperature Tg was measured from the obtained loss tangent tan δ. * The adhesive layer coating liquid A was made of UV-curable acrylic resin (Toyo Ink) A coating liquid prepared by the company, UA-A1, solid content: 100% by mass. A transfer substrate with a supplementary electrode layer was produced in the same manner as in Example 1. The auxiliary electrode was applied to the transfer substrate by an applicator. The UV-curable acrylic resin solution A was applied to the layer side and dried at 90 ° C for 2 minutes to form a layered body B of the transfer substrate/substrate electrode layer/embedded resin layer A (unhardened). The adhesive layer A (UV-curable acrylic resin (UA-A1) manufactured by Toyo Ink Co., Ltd.), self-adhesive layer, was applied to the transparent gas barrier layer side of the transparent substrate having the transparent gas barrier layer formed thereon by an applicator. The side A was irradiated with a cumulative light amount of 250 mJ/cm ² by a belt type UV irradiation apparatus (manufactured by HERAEUS Co., Ltd., high pressure mercury lamp) to form a laminate of the adhesive layer A/transparent gas barrier layer/undercoat layer/transparent substrate. Body C (thickness of the adhesive layer A after hardening: 5 μm). The elastic modulus of the adhesive layer A of the laminated body C at 25 ° C was measured by a dynamic ultra-small surface hardness tester. Next, the adhesive layer A of the laminated body B embedded in the resin layer A and the laminated body C was laminated by a laminating machine A The laminated resin was irradiated so that the cumulative amount of light was 250 mJ/cm ² from the side of the transparent resin substrate by a conveyor type UV irradiation apparatus (manufactured by HERAEUS Co., Ltd., high pressure mercury lamp), and the resin layer A was embedded in the laminated body B. Hardening (thickness of the resin layer A embedded in the cured layer: 25 μm). Finally, the transfer substrate is peeled off by the interface between the resin layer A and the auxiliary electrode layer, and is formed on the transparent resin substrate to block the transparent gas. The barrier layer and the adhesion layer A are laminated with a transparent conductive laminate E having a composite layer of the auxiliary electrode layer and the embedded resin layer A, and the embedded resin is measured by a dynamic ultra-micro surface hardness meter. The elastic modulus and the turbidity H _{c0 of the} layer A at 25 ° C and 70 ° C. Further, a transparent conductive layer of 50 nm was formed in the same manner as in Example 1 to form a transparent conductive laminated body, and the haze H _c1 and the sheet resistance value ρ were evaluated. Water vapor transmission rate (WVTR).

(Example 4) A transparent conductive laminated body F was produced in the same manner as in Example 1 except that the film thickness of the adhesive layer A was changed to 25 μm, and the haze H _{c0 of the} transparent conductive laminated body F was evaluated. Next, a transparent conductive laminated body was formed by laminating a transparent conductive layer, and the haze H _b1 , the sheet resistance value ρ, and the water vapor transmission rate (WVTR) were measured.

(Example 5) A transparent conductive laminated body G was produced in the same manner as in Example 1 except that the film thickness of the adhesive layer A was changed to 50 μm, and the haze H _{c0 of the} transparent conductive laminated body G was evaluated. Next, a transparent conductive laminated body was formed by laminating a transparent conductive layer, and the haze H _b1 , the sheet resistance value ρ, and the water vapor transmission rate (WVTR) were measured.

(Example 6) A transparent conductive laminated body H was produced in the same manner as in Example 1 except that the film thickness of the adhesive layer A was changed to 75 μm, and the haze H _{c0 of the} transparent conductive laminated body H was evaluated. Next, a transparent conductive laminated body was formed by laminating a transparent conductive layer, and the haze H _b1 , the sheet resistance value ρ, and the water vapor transmission rate (WVTR) were measured.

(Example 7) In Example 3, the embedded resin layer A was changed to the embedded resin layer E formed of the following UV-curable acrylic resin solution E, and the die coater was applied to the transfer substrate. The upper side is coated to a thickness of 1 μm (after hardening), and dried at 70 for 30 seconds. On the other hand, the adhesive layer A is changed to an adhesive layer B formed of the following adhesive layer coating liquid B, to a bar coater. After coating with a thickness of 10 μm (after hardening) and curing, and bonding the resin layer E and the adhesive layer B, the transparent conductive laminated body I was produced in the same manner as in Example 3, by dynamic ultra-fine surface. The modulus of hardness of the resin layer E embedded at 25 ° C and 70 ° C and the haze H _{c0 of the} transparent conductive laminate I were measured by a _durometer . Further, the elastic modulus at 25 ° C of the adhesive layer B after curing before bonding was measured by a dynamic ultra-small surface hardness meter in the same manner as in Example 3. Next, a transparent conductive laminated body was formed by laminating a transparent conductive layer, and the haze H _b1 , the sheet resistance value ρ, and the water vapor transmission rate (WVTR) were measured. Further, in the same manner as in Example 1, a UV-curable acrylic resin solution E was used to form a buried resin layer E (thickness: 50 μm after curing) on a glass slide having a thickness of 1 mm, and the glass transition temperature Tg was measured. Further, in the same manner as in Example 3, an adhesive layer B (cured film thickness: 50 μm) was formed on a glass slide having a thickness of 1 mm using an adhesive layer coating liquid B, and the glass transition temperature Tg was measured. * UV-curable acrylic resin solution E UV-curable acrylic resin (OPSTAR Z7530, solid content 73% by mass, methyl ethyl ketone solution) containing inorganic fine particles was added with methyl ethyl ketone as a dilution solvent. It is a solution after the solid content is 30% by weight. *Adhesive layer coating liquid B To 100 parts by mass of a UV-curable acrylic resin (UVX6125, a solid content of 100% by mass), 1 part by mass of a photoinitiator (Irgacure 819, manufactured by BASF Corporation), 1 A coating liquid of a mass part of a decane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., KBM903).

(Example 8) A transparent conductive laminated body J was produced in the same manner as in Example 3 except that the thickness of the adhesive layer A was 100 μm, and the turbidity H _{c0 of the} transparent conductive laminated body J was evaluated. Next, a transparent conductive laminated body was formed by laminating a transparent conductive layer, and the haze H _b1 , the sheet resistance value ρ, and the water vapor transmission rate (WVTR) were measured.

As is understood from Table 1, it is understood that a transparent conductive laminate having excellent optical characteristics (small haze) and flexibility can be obtained by controlling the elastic modulus of the embedded resin. Further, as is understood from Table 2-1 and Table 2-2, it is understood that the adhesive layer and the embedded resin layer having a lower modulus of elasticity than the embedded resin layer can be used to obtain flexibility and adhesion. A more excellent transparent conductive laminate. [Industrial availability]

Since the transparent conductive laminated body of the present invention has excellent optical characteristics and flexibility at the same time, and has a small sheet resistance value, it is also used in a device such as a flexible solar cell element or an organic electroluminescence device which is required to have a large area. be usable.

1A, 1B‧‧‧Transparent conductive laminate

2‧‧‧Transparent substrate

3‧‧‧ buried in the resin layer

4‧‧‧Assisted electrode layer

5‧‧‧Transparent conductive layer

6‧‧‧Undercoat

7‧‧‧Transparent gas barrier

8‧‧‧Adhesive layer

9‧‧‧ openings

Fig. 1 is a cross-sectional view showing an example of a configuration of a transparent conductive laminate of the present invention. Fig. 2 is a cross-sectional view showing another example of the structure of the transparent electroconductive laminate of the present invention.

Claims (13)

A transparent conductive layered body comprising at least a transparent conductive layered body in which a resin layer, a supplementary electrode layer, and a transparent conductive layer are embedded on a transparent substrate, wherein the transparent conductive layer is made of a metal oxide, and the The embedding resin layer has an elastic modulus at 25 ° C of 3000 to 8000 MPa, and an elastic modulus at 70 ° C of 1000 to 7000 MPa. The transparent conductive laminated body according to claim 1, wherein the glass transition temperature of the embedded resin layer is 90 ° C or higher. The transparent conductive laminated body according to claim 1 or 2, wherein the buried resin layer has a film thickness of 0.1 to 100 μm. The transparent conductive laminated body according to any one of claims 1 to 3, wherein the transparent conductive laminated body further includes an adhesive layer on a surface opposite to the transparent conductive layer embedded in the resin layer. The transparent conductive laminated body according to claim 4, wherein the adhesive layer has a glass transition temperature of 40 ° C or higher. The transparent conductive laminated body according to claim 4 or 5, wherein the adhesive layer has a film thickness of 1 to 120 μm. The transparent conductive laminated body according to any one of claims 4 to 6, wherein the adhesive layer has an elastic modulus at 25 ° C of 100 to 3000 MPa. The transparent conductive laminated body according to any one of claims 1 to 7, wherein the transparent conductive laminated body further comprises a transparent gas barrier layer on the transparent substrate. The transparent conductive laminated body according to claim 8, wherein the transparent conductive laminated body further includes an adhesive layer between the embedded resin layer and the transparent gas barrier layer. The transparent conductive laminated body according to claim 1, wherein the metal oxide is formed by sputtering. A solar cell element or an organic electroluminescence device having the transparent electroconductive laminate according to any one of claims 1 to 10. A method for producing a transparent conductive laminated body comprising at least a buried resin layer, a supplementary electrode layer, and a transparent conductive layer on a transparent substrate, wherein the transparent conductive layer is made of a metal oxide, and the embedded resin a method for producing a transparent conductive laminated body having an elastic modulus of 3,000 to 8,000 MPa at 25 ° C and an elastic modulus of 1000 to 7000 MPa at 70 ° C, and comprising: a step of forming the auxiliary electrode layer, and the auxiliary electrode The step of forming the buried resin layer on the opening of the layer, or the auxiliary electrode layer and the opening, and the step of forming the transparent conductive layer. The method for producing a transparent conductive laminate according to claim 12, further comprising the step of forming an adhesive layer and/or forming a transparent gas barrier layer.