WO2018180961A1

WO2018180961A1 - Transparent conductive laminate and production method therefor

Info

Publication number: WO2018180961A1
Application number: PCT/JP2018/011632
Authority: WO
Inventors: 務原; 豪志武藤
Original assignee: リンテック株式会社
Priority date: 2017-03-31
Filing date: 2018-03-23
Publication date: 2018-10-04
Also published as: TW201840261A

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°C of 3,000-8,000 MPa and an elastic modulus at 70°C of 1,000-7,000 MPa; and a production method for the transparent conductive laminate.

Description

Transparent conductive laminate and method for producing the same

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

In recent years, with the development of printed electronics, the area of electronic devices mainly using organic materials, such as organic thin-film solar cells and organic EL lighting, which are expected to spread in the future, has been increased, and in addition, flexibility has been promoted. Yes. As these electronic devices become larger in area, there is a demand for lower resistance for the transparent conductive layer of the transparent conductive film used for them. In response to this requirement, transparent conductivity is required during device operation (current collection or voltage application). In order to suppress degradation of the performance of electronic devices such as photoelectric conversion efficiency and light emission efficiency, which generally arises from the fact that the layer has a high electrical resistivity, the transparent conductive layer has a resistance value lower than that of the transparent conductive layer as an auxiliary electrode layer A structure provided with a pattern layer of fine metal wires or metal paste is used, and a transparent resin layer may be disposed between the fine wires or between the pattern layers.

With respect to the above, Patent Document 1 discloses a flexibility obtained by applying a coating liquid containing transparent conductive particles and a dispersion medium on a transparent base sheet and laminating a transparent conductive film from the viewpoint of making the electronic device flexible. A transparent conductive sheet is disclosed. Patent Document 2 discloses that the transparent conductive layer is formed of indium-tin oxide (ITO) or the like by a dry film forming method from the viewpoint of demanding high transparency and low resistance. .

Japanese Patent Laying-Open No. 2015-162355 JP 2014-216175 A

However, in patent document 1, although it has flexibility because it uses a transparent substrate sheet, it has a configuration in which conductivity is expressed in a transparent conductive film formed by applying a coating liquid containing transparent conductive particles and a dispersion medium. For this reason, there is no disclosure of a transparent conductive film formed by a dry film formation method. Patent Document 2 discloses that the transparent conductive layer is formed on the surface composed of the auxiliary electrode layer and the transparent resin layer by a dry film forming method, but the present inventors have further studied. As a result, due to the strong stress of the film formed by the dry film formation method in addition to the temperature rise during film formation, irregularities occur on the surface of the transparent conductive layer, resulting in a decrease in optical properties, for example, a large haze value. It came to discover that there is a problem of increasing.

In view of the above problems, an object of the present invention is to provide a transparent conductive laminate having excellent optical characteristics and flexibility at the same time.

As a result of intensive studies to solve the above problems, the present inventors have determined that the elastic modulus of the opening portion of the auxiliary electrode layer or the embedded resin layer provided above the opening portion and the auxiliary electrode layer has a specific value. By controlling to the range, it was found that while having flexibility, an increase in haze of the transparent conductive layer formed by the dry film forming method can be suppressed, and the present invention was completed.
That is, the present invention provides the following (1) to (13).
(1) A transparent conductive laminate comprising at least an embedded resin layer, an auxiliary 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 layer A transparent conductive laminate having 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 laminate according to the above (1), wherein the embedded resin layer has a glass transition temperature of 90 ° C. or higher.
(3) The transparent conductive laminate according to the above (1) or (2), wherein the thickness of the embedded resin layer is 0.1 to 100 μm.
(4) The transparent conductive layer according to any one of the above (1) to (3), wherein the transparent conductive laminate further includes an adhesion layer on a surface of the embedded resin layer opposite to the transparent conductive layer. Laminated body.
(5) The transparent conductive laminate according to (4), wherein the adhesion layer has a glass transition temperature of 40 ° C. or higher.
(6) The transparent conductive laminate according to the above (4) or (5), wherein the adhesion layer has a thickness of 1 to 120 μm.
(7) The transparent conductive laminate according to any one of (4) to (6), wherein the adhesion layer has an elastic modulus at 25 ° C. of 100 to 3000 MPa.
(8) The transparent conductive laminate according to any one of (1) to (7), wherein the transparent conductive laminate further comprises a transparent gas barrier layer on a transparent substrate.
(9) The transparent conductive laminate according to (8), wherein the transparent conductive laminate further comprises an adhesion layer between the embedded resin layer and the transparent gas barrier layer.
(10) The transparent conductive laminate according to (1), wherein the metal oxide is formed by sputtering.
(11) A solar cell element or organic electroluminescence element comprising the transparent conductive laminate according to any one of (1) to (10) above.
(12) On the transparent substrate, at least an embedded resin layer, an auxiliary electrode layer, and a transparent conductive layer are included, the transparent conductive layer is made of a metal oxide, and the elastic modulus at 25 ° C. of the embedded resin layer is 3000. A method for producing a transparent conductive laminate having a modulus of elasticity of 1000 to 7000 MPa at 70 ° C., the step of forming the auxiliary electrode layer, the opening of the auxiliary electrode layer, or an auxiliary The manufacturing method of a transparent conductive laminated body including the process of forming the said embedded resin layer on an electrode layer and an opening part, and the process of forming the said transparent conductive layer.
(13) The method for producing a transparent conductive laminate according to (12), further comprising a step of forming an adhesion layer and / or a step of forming a transparent gas barrier layer.

According to the present invention, it is possible to provide a transparent conductive laminate having excellent optical properties and flexibility at the same time.

It is sectional drawing which shows an example of a structure of the transparent conductive laminated body of this invention. It is sectional drawing which shows another example of a structure of the transparent conductive laminated body of this invention.

[Transparent conductive laminate]
The transparent conductive laminate of the present invention is a transparent conductive laminate comprising at least an embedded resin layer, an auxiliary electrode layer, and a transparent conductive layer on a transparent substrate, and the transparent conductive layer is made of a metal oxide. 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.
By controlling the elastic modulus at 25 ° C. and 70 ° C. of the embedded resin layer within the above range, the temperature rise from the dry film formation method before and after the formation of the transparent conductive layer, the stress of the film formed by the dry film formation method An increase in haze due to irregularities on the surface of the transparent conductive layer caused by the above can be suppressed, and a transparent conductive laminate having excellent optical characteristics while maintaining flexibility is obtained.
In the present invention, a “transparent conductive laminate” and a “transparent conductive laminate” are used separately. The “transparent conductive laminate” means a laminate that does not include a transparent conductive layer in the configuration of the “transparent conductive laminate” of the present invention.
The configuration of the transparent conductive laminate of the present invention will be described with reference to the drawings.

FIG. 1 is a cross-sectional view showing an example of the configuration of the transparent conductive laminate of the present invention. The transparent conductive laminate 1 </ b> A has a configuration in which an embedded resin layer 3, an auxiliary electrode 4, and a transparent conductive layer 5 are laminated on a transparent substrate 2. The auxiliary electrode layer 4 has an opening 9 between adjacent auxiliary electrode layers 4, and the embedded resin layer 3 exists 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 laminate of the present invention. The transparent conductive laminate 1B has a structure in which a transparent gas barrier layer 7, an adhesion layer 8, an embedded resin layer 3, an auxiliary electrode 4 and a transparent conductive layer 5 are laminated on a transparent substrate 2 with a primer layer 6 interposed therebetween. is there. The auxiliary electrode layer 4 has an opening 9 between adjacent auxiliary electrode layers 4, and the embedded resin layer 3 exists on the opening 9 and the auxiliary electrode layer 4.
In the above, the embedded resin layer 3 may exist only in the opening 9.

(Base material)
The transparent substrate used in the present invention is not particularly limited, and may be appropriately selected according to the device to be used. For example, it is not particularly limited as long as it has flexibility and high transmittance in the visible light range. , Flexible glass, resin film and the like. Resin film materials include polyimide, polyamide, polyamideimide, polyphenylene ether, polyetherketone, polyetheretherketone, polyolefin, polyester, polycarbonate, polysulfone, polyethersulfone, polyphenylene sulfide, polyarylate, acrylic resin, cyclohexane Examples include olefin copolymers, cycloolefin polymers, aromatic polymers, polyurethane polymers, and the like.
Among these, examples of the polyester include polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), and polyarylate. Examples of the cycloolefin polymer include norbornene polymers, monocyclic olefin polymers, cyclic conjugated diene polymers, vinyl alicyclic hydrocarbon polymers, and hydrides thereof. For example, as a cycloolefin polymer, industrially, Apel (manufactured by Mitsui Chemicals, ethylene-cycloolefin copolymer), Arton (manufactured by JSR, norbornene copolymer), Zeonore (manufactured by Nippon Zeon Co., Ltd., norbornene copolymer) Polymer) and the like. Among such transparent substrates, from the viewpoint of handling properties, biaxially stretched polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) are particularly preferable. From the viewpoint of optical isotropy, a cycloolefin polymer and a cycloolefin copolymer are particularly preferable. From the viewpoint of heat resistance, polyimide is particularly preferable.
When the transparent conductive laminate of the present invention is used for a display device, it is easy to produce the transparent conductive laminate of the present invention by being excellent in handling properties, and excellent in optical isotropy. Can be used.
The thickness of the transparent substrate is preferably 1 to 1000 μm, more preferably 5 to 250 μm, and still more preferably 10 to 200 μm. If it is this range, the mechanical strength as a base material and transparency can be ensured.

(Auxiliary electrode layer)
The auxiliary electrode layer used for this invention is provided in order to reduce the sheet resistance value of the transparent conductive layer of the transparent conductive laminated body of this invention. Moreover, in order to suppress the fall of the light transmittance of a transparent conductive layer, it patterns and provides an opening part normally.

The material of the auxiliary electrode layer is not particularly limited, but patterning is preferably performed using a method such as photolithography. In this case, the material of the auxiliary electrode layer is gold, silver, copper, aluminum, magnesium, nickel, platinum, single metal such as palladium, palladium, silver-palladium, silver-copper, silver-magnesium, aluminum-silicon, aluminum-silver Binary or ternary aluminum alloys such as aluminum-copper and aluminum-titanium-palladium. Among these materials, silver, copper, aluminum, and an aluminum alloy are preferable from the viewpoint of specific resistance, and copper and aluminum alloy are more preferable from the viewpoint of cost, etching property, and corrosion resistance.

Also, a conductive paste containing a conductive material can be used as a material for the auxiliary electrode layer. The conductive paste is not particularly limited. For example, a conductive paste in which conductive fine particles such as metal fine particles, carbon and ruthenium oxide, and conductive carbon materials such as metal nanowires and carbon nanotubes are dispersed in a solvent is used. In addition, a binder component may be included, and two or more kinds of conductive pastes may be mixed and used. An auxiliary electrode layer is obtained by printing and baking or curing this conductive paste.

The material of the metal fine particles is not particularly limited, and examples thereof include materials composed of the single metals and alloys described above. From the viewpoint of conductivity, silver, copper, aluminum and the like are preferable. From the viewpoint of corrosion resistance and chemical resistance, platinum, rhodium, ruthenium, palladium and the like are preferable, and one or more of these metals may be included. Moreover, you may use the composite fine particle like the copper particle which coat | covered silver on the surface layer from a viewpoint of cost, and the resin particle which coat | covered silver on the surface layer from a softness | flexibility viewpoint. Although metal nanowire material is not specifically limited, Silver nanowire, copper nanowire, nickel nanowire, silicon nanowire etc. are mentioned.
The conductive carbon material is inferior to metal in terms of conductivity, but is low in price and 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-walled carbon nanotubes, conductive multi-walled carbon nanotubes, and graphene powder. Further, ruthenium oxide (RuO ₂ ) fine particles are more expensive than the conductive carbon material, but can be used as an 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 be a multilayer structure in which layers made of the same kind of material are laminated, or a multilayer structure in which layers made of at least two kinds of materials are laminated.
The multilayer structure is more preferably a two-layer structure in which layers of different materials are stacked. As such a multilayer structure, for example, it is preferable to form a silver pattern layer first and then form a copper pattern layer on the silver pattern layer, because the corrosion resistance is improved while maintaining high silver conductivity.
Further, for the purpose of improving optical characteristics, the formed auxiliary electrode layer may be subjected to chemical treatment. For example, a blackening treatment to an auxiliary electrode layer mainly made of copper for the purpose of preventing reflection can be mentioned. By performing the blackening treatment, the contrast can be improved when the transparent conductive laminate of the present invention is used in a display device or a lighting device.

The pattern of the auxiliary electrode layer used in the present invention is not particularly limited, and is a lattice, honeycomb, comb, strip (stripe), linear, curved, wavy (sine curve, etc.), polygonal shape. And the like, a circular mesh shape, an elliptical mesh shape, and an indeterminate shape. Among these, a lattice shape, a honeycomb shape, or a comb shape is preferable.

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

(Embedded resin layer)
The embedded resin layer used in the present invention suppresses the occurrence of unevenness on the surface of the transparent conductive layer of the transparent conductive laminate due to the temperature rise during the formation of the transparent conductive layer and the stress relaxation of the film, and the transferability of the auxiliary electrode layer. Used to improve and develop flexibility.

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. When the elastic modulus at 25 ° C. is less than 3000 MPa, the transferability of the auxiliary electrode layer is inferior, so that a transparent conductive laminate using a transfer process cannot be formed. Flexibility falls that the elastic modulus in 25 degreeC is over 8000 Mpa. Further, if the elastic modulus at 70 ° C. is less than 1000 MPa, unevenness is likely to occur on the surface of the embedded resin layer due to thermal shrinkage derived from thermal history during dry film formation and film stress of the transparent conductive layer, and haze In addition to the rise, the transparent conductive layer is easily cracked. When the elastic modulus at 70 ° C. exceeds 7000 MPa, 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 3300 to 7900 MPa, more preferably 3500 to 7500 MPa, still more preferably 3600 to 7300 MPa.
The elastic modulus at 70 ° C. is preferably 1100 to 6700 MPa, more preferably 1200 to 6500 MPa, and still more preferably 1300 to 6400 MPa. When the elastic modulus at 25 ° C. and the elastic modulus at 70 ° C. are in the above ranges, the transferability of the auxiliary electrode layer is improved, and at the same time, stress relaxation of the transparent conductive layer after film formation can be suppressed, and haze increases. This leads to suppression, and a transparent conductive laminate having excellent optical properties is obtained.

The glass transition temperature of the embedded resin layer is preferably 90 ° C. or higher, more preferably 110 ° C. or higher, and further 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-described range.
The thickness of the embedded resin layer is preferably 0.1 to 100 μm, more preferably 1 to 80 μm, and still more preferably 5 to 60 μm. When the 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 embedded. .

The embedded resin layer used in the present invention is not particularly limited as long as the above-described elastic modulus is within the range of the present invention. However, from the viewpoint of obtaining a high elastic modulus even at high temperatures, the embedded resin layer is made of a transparent resin composition containing inorganic fine particles. It may be. Moreover, it does not need to contain inorganic fine particles. Specifically, when inorganic fine particles are included, the following energy ray-sensitive composition is cured.
The energy beam sensitive composition includes (i) an energy beam curable compound, (ii) inorganic fine particles, and (iii) a photopolymerization initiator. By irradiating the energy ray sensitive composition with energy rays, it can be crosslinked and cured.
The composition contains additives such as an ultraviolet absorber, a light stabilizer, an antioxidant, an infrared absorber, an antistatic agent, a leveling agent, and an antifoaming agent as long as the effects of the present invention are not impaired. be able to.
In the present invention, the term “energy beam” means an electromagnetic wave such as an ultraviolet ray or an electron beam or a charged particle beam having energy quanta.

(I) Energy ray curable compound As the energy ray curable compound, a polyfunctional (meth) acrylate monomer and / or a (meth) acrylate prepolymer is preferable, and a polyfunctional (meth) acrylate monomer is more preferable. .
In the present invention, (meth) acrylate means both acrylate and methacrylate, and the same applies to other similar terms.

Examples of multifunctional (meth) acrylate monomers include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and polyethylene glycol diene. (Meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, ethylene oxide modified di (meth) acrylate phosphoric acid, allylation Cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipenta Lithritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, propionic acid modified dipentaerythritol penta (meth) acrylate, di Examples include pentaerythritol hexa (meth) acrylate and caprolactone-modified dipentaerythritol hexa (meth) acrylate.
In addition, you may use these monomers individually or in combination of 2 or more types.

Examples of (meth) acrylate-based prepolymers include polyester (meth) acrylate-based prepolymers, epoxy (meth) acrylate-based prepolymers, urethane (meth) acrylate-based prepolymers, polyol (meth) acrylate-based prepolymers, and the like. It is done.
The polyester (meth) acrylate-based prepolymer can be obtained, for example, by esterifying a hydroxyl group of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol with (meth) acrylic acid. it can. Or it can obtain by esterifying the hydroxyl group of the terminal of the oligomer obtained by adding an alkylene oxide to polyhydric carboxylic acid with (meth) acrylic acid.
The epoxy acrylate prepolymer can be obtained, for example, by reacting (meth) acrylic acid with an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin and esterifying it.
The urethane acrylate prepolymer can be obtained, for example, by esterifying a polyurethane oligomer having hydroxyl groups at both ends obtained by reaction of polyether polyol or polyester polyol and polyisocyanate with (meth) acrylic acid.
The polyol acrylate prepolymer can be obtained by esterifying the hydroxyl group of the polyether polyol with (meth) acrylic acid.
These prepolymers may be used alone or in combination of two or more, and may be used in combination with the polyfunctional (meth) acrylate monomer.

(Ii) Inorganic fine particles The inorganic fine particles used in the present invention are not particularly limited, but damage the basic characteristics of the transparent conductive laminate, such as a decrease in total light transmittance (increase in haze) of the transparent conductive laminate. The silica fine particles, titanium oxide fine particles, alumina fine particles, and calcium carbonate fine particles are exemplified. Among the inorganic fine particles, (i) from the viewpoint of forming a strong bond with the energy ray curable compound, the surface was modified with an organic compound having a polymerizable unsaturated group capable of reacting with the energy ray curable compound. Silica fine particles are preferred.
Silica fine particles whose surface is modified with an organic compound having a polymerizable unsaturated group are prepared by reacting a silanol group on the surface of the silica fine particle with a polymerizable unsaturated group-containing organic compound having a functional group capable of reacting with the silanol group. Can be obtained.
In the present invention, the organic compound having a polymerizable unsaturated group that modifies the surface of the inorganic fine particles is included as a constituent of (ii) the inorganic fine particles, and the above-mentioned (i) energy ray-curable compound and Are distinguished.

As the polymerizable unsaturated group-containing organic compound having a functional group capable of reacting with the silanol group, for example, a compound represented by the following general formula (1) is preferable.

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

Examples of such organic compounds include (meth) acrylic acid chloride, (meth) acrylic acid 2-isocyanate ethyl, (meth) acrylic acid glycidyl, (meth) acrylic acid 2,3-iminopropyl, (meth) (Meth) acrylic acid and derivatives thereof such as 2-hydroxyethyl acrylate, (meth) acrylic acid, (meth) acryloyloxypropyltrimethoxysilane and the like may be mentioned, and these may be used alone or in combination of two or more.

The content of the inorganic fine particles in the entire volume of the embedded resin layer containing the inorganic fine particles is preferably 20 to 70% by volume, more preferably 30 to 65% by volume, and further preferably 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. As the inorganic fine particles, silica fine particles are preferable.

(Iii) Photopolymerization initiator The energy ray-sensitive composition contains a photopolymerization initiator.
Examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 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-morpholino-propan-1-one, 4- (2-hydroxyethoxy) phenyl-2 (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4′-diethylaminobenzene Nzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2 , 4-diethylthioxanthone, benzyl dimethyl ketal, acetophenone dimethyl ketal, p-dimethylaminobenzoate, and the like. These photopolymerization initiators may be used alone or in combination of two or more. Commercially available products such as Irgacure 127, Irgacure 184, Irgacure 819, Darocur 1173 and the like can be used as appropriate.

Examples of commercially available energy ray-sensitive compositions containing the above (i) energy ray-curable compound, (ii) silica fine particles, and (iii) a photopolymerization initiator include, for example, “Opster Z7530”, “Opster Z7524”, “OPSTAR TU4086” (product name, all manufactured by JSR Corporation), and the like.

Further, in the above, an embedded resin layer may be formed using an energy ray sensitive composition comprising (ii) an energy ray curable compound and (iii) a photopolymerization initiator that does not contain silica fine particles. it can.
(I) From the viewpoint of flexibility, the energy ray curable compound is preferably a urethane acrylate compound. For example, 2 mol or more of hydroxyl group is contained per 1 mol of a compound having 2 or more NCO groups in one molecule. Examples thereof include compounds having one or more (meth) acrylic groups in one molecule, obtained by reacting acrylic monomers. Here, hydroxyl group-containing acrylic monomers include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono Examples include hydroxyl group-containing (meth) acrylates such as (meth) acrylate and cyclohexanedimethanol mono (meth) acrylate.
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 diisocyanate and a polyol compound such as diol.
Examples of the polyisocyanate compound include aliphatic polyisocyanates such as hexamethylene diisocyanate and isophorone diisocyanate, and aromatic polyisocyanates such as tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, and phenylene diisocyanate.
Examples of the polyol compound include glycols such as ethylene glycol, propylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol, and 1,4-cyclohexanedimethanol; trivalent or higher polyols such as glycerin and pentaerythritol; polyethylene glycol, polypropylene Polyether-type diols such as glycol, polytetramethylene glycol, polyhexamethylene glycol; the above diols react with dibasic acids such as phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid, and sebacic acid Polyester-type diols obtained in this manner.
For example, as a commercial product, UV curable urethane acrylate resin (manufactured by Nippon Synthetic Chemical Co., Ltd., UT5746, solid content 80% by mass, ethyl acetate solution) and the like can be mentioned.
Examples of the photopolymerization initiator include compounds that generate radicals when irradiated with light. Examples of such photopolymerization initiators include alkylphenone photopolymerization initiators, acylphosphine oxide photopolymerization initiators, and oxime ester photopolymerization initiators.
Of these, acylphosphine oxide photoreaction initiators are preferred from the viewpoint of easy adjustment of the elastic modulus.
By adjusting the amount of the photopolymerization initiator or the like, an embedded resin layer having a predetermined elastic modulus can be obtained.
The content of the photopolymerization initiator is preferably 0.2 to 5 parts by mass, more preferably 0.5 to 3 parts by mass with respect to 100 parts by mass of the (i) energy beam curable compound. When the content of the photopolymerization initiator is in this range, the weather resistance is good and the curability is sufficient.

The energy ray sensitive composition may contain an ultraviolet absorber as necessary.
Examples of the UV absorber include benzotriazole UV absorbers, hindered amine UV absorbers, benzophenone UV absorbers, and triazine UV absorbers. These ultraviolet absorbers may be used alone or in combination of two or more. Among these, a radical polymerizable ultraviolet absorber having a radical polymerizable double bond in the molecule is preferable.
The content when the ultraviolet absorber is contained is preferably 0.1 with respect to a total of 100 parts by mass of (i) active energy ray-curable compound, (ii) silica fine particles, and (iii) photopolymerization initiator. The amount is 2 to 10 parts by mass, more preferably 0.5 to 7 parts by mass.

The energy ray-sensitive composition may contain a light stabilizer as necessary.
Examples of light stabilizers include hindered amine light stabilizers, benzophenone light stabilizers, and benzotriazole light stabilizers. These light stabilizers may be used alone or in combination of two or more.
The content when the light stabilizer is contained is preferably 0.2 with respect to a total of 100 parts by mass of (i) energy ray-curable compound, (ii) silica fine particles, and (iii) photopolymerization initiator. -10 parts by mass, more preferably 0.5-7 parts by mass.
Moreover, in addition to said each component, a polymerization inhibitor, a viscosity modifier, surfactant, an antifoamer, an organometallic coupling agent, a silane coupling agent etc. can be added as needed.

(Transparent conductive layer)
The transparent conductive layer used in the present invention is made of a metal oxide. Metal oxides include indium-tin oxide (ITO), indium-zinc oxide (IZO), aluminum-zinc oxide (AZO), gallium-zinc oxide (GZO), indium-gallium-zinc oxide ( IGZO), niobium oxide, titanium oxide, tin oxide, and the like. These can be used alone or in combination. 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 5 to 200 nm, more preferably 10 to 100 nm, and further preferably 20 to 50 nm. If it is this range, since the thin film which has a high transmittance | permeability, a low surface resistivity, and the uniformity of in-plane resistance is obtained, it is preferable.
The total light transmittance of the transparent conductive layer is preferably 70% or more, more preferably 80% or more, more preferably 90% or more, as measured in accordance with JIS K7361-1. Is more preferable.
The turbidity of the transparent conductive layer is preferably 10% or less, more preferably 5% or less.
The sheet resistance value of the transparent conductive layer is preferably 1000Ω / □ or less, more preferably 500Ω / □ or less, and still more preferably 100Ω / □ or less.

As a method for forming the transparent conductive layer, a dry film forming method is preferable from the viewpoint of obtaining high transmittance and low sheet resistance. For example, resistance vapor deposition, electron beam deposition, molecular beam epitaxy, ion beam, ion plating, sputtering, etc., physical vapor deposition (hereinafter also referred to as “PVD”), thermal CVD, It is a dry film forming method such as a chemical vapor deposition method (hereinafter also referred to as “CVD”) such as a plasma CVD method, a photo CVD method, an epitaxial CVD method, an atomic layer CVD method, or the like.
A sputtering method is preferable because a low sheet resistance value, high-precision film thickness control, a predetermined composition ratio is easily obtained, and quality stability is high. After the film is formed by the above method, a more excellent sheet resistance value can be obtained by performing a heat treatment within a range that does not affect other laminated bodies as necessary.
The dry film forming method referred to here is generally called a dry process method by treating the surface of a material using a gas phase or a molten state.

(Adhesion layer)
The transparent conductive laminate of the present invention preferably further comprises an adhesion layer on the surface of the embedded resin layer opposite to the transparent conductive layer, and is interposed between the embedded resin layer and a transparent gas barrier layer described later. More preferably, the adhesive layer is included.
As described above, the adhesion layer is used to improve adhesion between the embedded resin layer and the transparent gas barrier layer, for example, and to improve flexibility of the transparent conductive laminate.

The elastic modulus at 25 ° C. of the adhesive layer is preferably 100 to 3000 MPa, more preferably 200 to 2400 MPa, and still more preferably 400 to 2200 MPa. When the elastic modulus of the adhesive layer at 25 ° C. is in the above range, the adhesiveness is improved and the flexibility is further improved by interposing directly between the transparent gas barrier layer and the embedded resin layer.

The glass transition temperature of the adhesion layer is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, and further preferably 60 ° C. or higher. The glass transition temperature of the adhesion layer is lower than the glass transition temperature of the embedded resin layer to be combined, and if it is within this range, the adhesion and flexibility are improved.
The thickness of the adhesion layer is preferably 1 to 120 μm, more preferably 3 to 100 μm, and still more preferably 4 to 80 μm. When the thickness of the embedded resin layer is in the above-described range and the thickness of the adhesion layer is in this range, the flexibility of the transparent conductive laminate is improved.

The adhesion layer used in the present invention is not particularly limited as long as the above-described elastic modulus is within the range of the present invention, and is preferably made of a transparent resin composition in the same manner as the embedded resin layer. For example, an energy beam curable compound, a thermoplastic resin, etc. are mentioned.

Examples of the energy ray curable compound include the same compounds as those used for the embedded resin layer described above.

Examples of the thermoplastic resin include polyolefin resins such as polyethylene, polypropylene, polybutene, (meth) acrylic resins, polyvinyl chloride resins, polystyrene resins, polyvinylidene chloride resins, ethylene-vinyl acetate copolymer ken. , Polyvinyl alcohol, polycarbonate resin, fluorine resin, polyvinyl acetate resin, acetal resin, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyester resin such as polybutylene naphthalate (PBN), nylon 6, polyamide resins such as nylon 66, and the like. Moreover, the said resin may be used individually by 1 type, and may be used in combination of 2 or more type. Among these, polyethylene, polypropylene, polystyrene, polyvinyl chloride, and polyvinylidene chloride are preferable.

Examples of commercially available energy ray curable compounds include UV curable acrylic resins (Toyo Ink, UA-A1, solid content 100% by mass), UV curable acrylic resins (Toa Gosei Co., Ltd., UVX6125, solids). 100% by weight) and the like, and Irgacure 819 (manufactured by BASF) as a photopolymerization initiator. Similar to the above-described embedded resin layer, an adhesive layer having a predetermined elastic modulus can be obtained by adjusting the amount of a 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 with respect to 100 parts by mass of the energy ray curable compound. When the content of the photopolymerization initiator is within this range, curability is sufficient.
Moreover, in addition to each said component, a polymerization inhibitor, a viscosity modifier, surfactant, an antifoamer, an organometallic coupling agent, etc. can be added as needed.

(Transparent gas barrier layer)
The transparent conductive laminate of the present invention preferably further includes a transparent gas barrier layer on the transparent substrate. The transparent gas barrier layer used in the present invention suppresses the permeation of water vapor in the atmosphere that has passed through the transparent substrate 2 in FIG. 2, for example, and as a result, the water vapor of the embedded resin layer 3, the auxiliary electrode layer 4, etc. Has a function to prevent transmission. In the present invention, when a 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 from the surface of the transparent substrate without the transparent gas barrier layer. 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 further preferably It is 5.0 × 10 ⁻⁴ (g · m ⁻² · day ⁻¹ ) or less, and particularly preferably 1.0 × 10 ⁻⁴ (g · m ⁻² · day ⁻¹ ) or less. By keeping the water vapor transmission rate in such a range and maintaining the water vapor transmission rate of other layers such as the auxiliary electrode layer and the embedded resin layer at a predetermined value, for example, the transparent conductive laminate of the present invention An increase in sheet resistance can be suppressed without the transparent conductive layer being deteriorated by moisture. Further, when used as a translucent electrode of an electronic device, it is possible to suppress deterioration over time of the active layer and the like inside the device, leading to a longer life of the device.

As a transparent gas barrier layer, a layer containing a metal oxide; a layer obtained by subjecting a layer containing a polymer compound (hereinafter sometimes referred to as “polymer layer”) to a modification treatment such as ion implantation; Can be mentioned.
As a method for forming the layer containing the metal oxide, the above-described method for forming a transparent conductive layer can be used. Furthermore, after film formation, a lower sheet resistance value can be obtained by performing heat treatment within a range that does not affect other laminated bodies as necessary.
Examples of metal oxide materials include metals such as silicon, aluminum, magnesium, zinc, and tin; inorganic materials such as silicon oxide, silicon monoxide, aluminum oxide, magnesium oxide, zinc oxide, indium oxide, tin oxide, and zinc tin oxide Oxides; inorganic nitrides such as silicon nitride, aluminum nitride and titanium nitride; inorganic carbides; inorganic sulfides; inorganic oxynitrides such as silicon oxynitride; inorganic oxide carbides; inorganic nitride carbides; inorganic oxynitride carbides . These can be used alone or in combination of two or more.
In these, the inorganic vapor deposition film | membrane which uses an inorganic oxide, an inorganic nitride, or a metal as a raw material from a gas-barrier viewpoint is preferable. In addition, a silicon oxynitride layer made of a layer containing metal oxide or a layer containing a polysilazane compound and having oxygen, nitrogen, and silicon as main constituent atoms formed by a modification treatment has interlayer adhesion, From the viewpoint of having gas barrier properties and bending resistance, it is preferably used.
Polymer compounds used for the polymer layer include silicon-containing polymer compounds such as polyorganosiloxane and polysilazane compounds, polyimide, polyamide, polyamideimide, polyphenylene ether, polyether ketone, polyether ether ketone, polyolefin, polyester Etc. These polymer compounds can be used alone or in combination of two or more.
Among these, a silicon-containing polymer compound is preferable as the polymer compound because of its superior gas barrier properties. Examples of silicon-containing polymer compounds include polysilazane compounds, polycarbosilane compounds, polysilane compounds, and polyorganosiloxane compounds. Among these, a polysilazane compound is preferable 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 the polysilazane compound-containing layer to plasma ion implantation treatment, plasma treatment, ultraviolet irradiation treatment, heat treatment, and the like. Examples of ions implanted by the plasma ion implantation process include hydrogen, nitrogen, oxygen, argon, helium, neon, xenon, and krypton.
As a specific processing method of the plasma ion implantation processing, a method of injecting ions present in plasma generated using an external electric field into a polysilazane compound-containing layer, or a gas barrier without using an external electric field. There is a method in which ions existing in plasma generated only by an electric field generated by a negative high voltage pulse applied to a layer made of a layer forming material are implanted into the polysilazane compound-containing layer.
The plasma treatment is a method for modifying a layer containing a silicon-containing polymer by exposing the polysilazane compound-containing layer to plasma. For example, plasma treatment can be performed according to the method described in Japanese Patent Application Laid-Open No. 2012-106421. The ultraviolet irradiation treatment is a method for modifying a layer containing a silicon-containing polymer by irradiating a polysilazane compound-containing layer with ultraviolet rays. For example, the ultraviolet modification treatment can be performed according to the method described in JP2013-226757A.
Among these, the ion implantation treatment is preferable because it can efficiently modify the inside of the polysilazane compound-containing layer without roughening the surface and form a gas barrier layer having more excellent gas barrier properties.

The method for laminating the transparent gas barrier layer is not particularly limited, but the laminating method is preferable because it can be easily produced.

The transparent gas barrier layer may be a single layer or a laminate of two or more layers. Further, when two or more layers are laminated, they may be the same or different.
The film thickness of the transparent gas barrier layer is preferably 20 nm to 50 μm, more preferably 30 nm to 1 μm, still more preferably 40 to 500 nm. When the film thickness of the transparent gas barrier layer is within this range, excellent gas barrier properties and adhesiveness can be obtained, and flexibility and coating strength can be compatible.

(Primer layer)
When forming a transparent gas barrier layer on a transparent substrate, a primer layer may be used to improve the adhesion between the transparent substrate and the transparent gas barrier layer. As the primer layer, for example, an acrylic-based, polyester-based, polyurethane-based, or rubber-based primer layer can be appropriately used. The thickness of the primer layer is usually 0.1 to 10 μm, preferably 0.5 to 5 μm. When the thickness of the primer layer is in the above range, by covering the unevenness of the transparent substrate, defects derived from the transparent substrate are reduced, the gas barrier performance of the transparent gas barrier layer is improved, and the transparent substrate Adhesion between the transparent gas barrier layers is improved, and the surface can be smoothly peeled off from the transfer substrate side in a surface smoothness transfer step of the transfer substrate surface described later.

The haze of the transparent conductive laminate of the present invention is preferably 2.5% or less, more preferably 2.0% or less. Further, the increase rate of haze before and after dry film formation (ratio of haze value after dry film formation to haze value before dry film formation) is preferably 1.40 or less, more preferably 1.25. Hereinafter, it is more preferably 1.10 or less. When the haze value and the rate of increase in haze before and after dry film formation are in this range, a transparent conductive laminate having excellent optical properties can be obtained.

The sheet resistance value on the transparent conductive layer side of the transparent conductive laminate of the present invention is preferably 10Ω / □ or less, more preferably 5Ω / □ or less, and further preferably 1Ω / □ or less. When the sheet resistance value is within this range, a transparent conductive laminate having excellent electrical characteristics can be obtained.

The thickness of the transparent conductive laminate is preferably 10 to 300 μm, more preferably 10 to 200 μm, and still more preferably 20 to 150 μm. If it is this range, when a transparent conductive layer is laminated | stacked on a transparent conductive laminated body and it is set as a transparent conductive laminated body, it can provide a high transmittance | permeability and a low sheet resistance value, having flexibility. .
The total light transmittance (T ₀ ) of the opening of the transparent conductive laminate is preferably 80% to 96%, more preferably 90 to 96%, and still more preferably 92% to 96%.
The total light transmittance (T) of the transparent conductive laminate including the auxiliary electrode layer is preferably 80% to 95%, more preferably 83% to 95%, and still more preferably 85% to 95%. is there.
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 is due to an increase in surface resistivity, etc. If electrical characteristics are not impaired, the closer to 1, the better. 0.93 to 0.99 is preferable, 0.96 to 0.99 is more preferable, and 0.97 to 0.99 is even more preferable. is there.
In addition, when the auxiliary electrode layer is printed in the same pattern, it means that the closer the line width of the auxiliary electrode layer is, the closer it is 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 transferability of the auxiliary electrode layer is excellent. Therefore, it is preferable to apply to a solar cell element or an organic electroluminescence element that requires a large area.

[Method for producing transparent conductive laminate]
The method for producing a transparent conductive laminate of the present invention comprises at least an embedded resin layer, an auxiliary electrode layer, and a transparent conductive layer on a transparent substrate, the transparent conductive layer comprising a metal oxide, A method for producing a transparent conductive laminate, wherein the elastic modulus at 25 ° C. of the resin layer is 3000 to 8000 MPa and the elastic modulus at 70 ° C. is 1000 to 7000 MPa, the step of forming the auxiliary electrode layer, Including a step of forming the embedded resin layer in the opening of the auxiliary electrode layer, or on the auxiliary electrode layer and in the opening, and a step of forming the transparent conductive layer.

(Auxiliary electrode layer forming process)
The auxiliary electrode layer forming step is a step of forming a pattern made of the above-described auxiliary electrode layer material on a transfer substrate described later.
As a method of forming the auxiliary electrode layer, after providing an auxiliary electrode layer on which a pattern is not formed on a transfer substrate, a known physical treatment or chemical treatment mainly using a photolithography method, or a combination thereof. The pattern of the auxiliary electrode layer is formed directly by a method of processing into a predetermined pattern shape, or by a screen printing method, a rotary screen printing method, a screen offset printing method, an inkjet method, an offset printing method, a gravure offset printing method, etc. And the like.
As a method for forming an auxiliary electrode layer on which no pattern is formed, a PVD method (physical vapor deposition method) such as a vacuum deposition method, a sputtering method, an ion plating method, a thermal CVD method, an ALD method (atomic layer deposition method). ) And other dry processes such as CVD (chemical vapor deposition), or various coatings such as dip coating, spin coating, spray coating, gravure coating, die coating, and doctor blade, and electrodeposition. A wet process, a silver salt method, etc. are mentioned, and it is suitably selected according to the material of the auxiliary electrode layer.

(Embedded resin layer forming process)
The embedded resin layer forming step is a step of laminating an embedded resin layer on the opening of the auxiliary electrode layer or on the opening and the auxiliary electrode layer, as one aspect. Another aspect is a step of laminating an embedded resin layer on the adhesion layer or the transparent gas barrier layer.

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 doctor blade method, and a Meyer bar coating method.
Examples of the method of irradiating energy radiation include ultraviolet rays and electron beams. The ultraviolet rays are obtained with a high-pressure mercury lamp, a fusion H lamp, a xenon lamp, etc., and the light quantity is usually 100 to 500 mJ / cm ² , while the electron beam is obtained with an electron beam accelerator or the like, and the irradiation dose is usually 150 to 350 kV. Among these energy rays, ultraviolet rays are particularly preferable. In addition, when using an electron beam, a cured film can be obtained, without adding a photoinitiator.

(Transparent conductive layer forming process)
The transparent conductive layer forming step is a step of forming a transparent conductive layer on the surface side composed of the auxiliary electrode layer and the embedded resin layer. The method for forming the transparent conductive layer is as described above.

(Adhesion layer forming process)
The production of the transparent conductive laminate of the present invention preferably further includes an adhesion layer forming step. An adhesion layer formation process is a process of forming an adhesion layer on an embedding resin layer as one mode. In another embodiment, the adhesion layer is formed on the transparent gas barrier layer.
The method for forming the adhesion layer is the same as the method for forming the embedded resin layer described above.

(Transparent gas barrier layer forming process)
The production of the transparent conductive laminate of the present invention preferably further includes 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 primer layer described above. The method for forming and laminating the transparent gas barrier layer is as described above.

(Transfer substrate forming process)
The production of the transparent conductive laminate of the present invention preferably further includes 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 material is not particularly limited, and examples thereof include polyester films such as polyethylene terephthalate and polyethylene naphthalate, polyolefin films such as polypropylene and polymethylpentene, polycarbonate films, and polyvinyl acetate films. Among them, a polyester film is preferable, and a biaxially stretched polyethylene terephthalate film is particularly preferable. The thickness of the support is preferably 10 to 500 μm, more preferably 20 to 300 μm, still more preferably 30 to 100 μm. If it is this range, since mechanical strength can be ensured, it is preferable.

(Peeling layer)
The release layer used in the present invention may or may not be appropriately provided depending on the support to be used. However, in the case of providing, the layer obtained by curing the silicone resin composition or the ultraviolet curable release composition (hereinafter referred to as “cured”). It is sometimes referred to as a “layer”).

The silicone resin composition is not particularly limited, and examples thereof include an addition reaction type silicone resin composition containing a photosensitizer. The addition reaction type silicone resin composition is obtained by adding a catalyst (for example, a platinum-based catalyst) and a photosensitizer to a main agent composed of an addition reaction type silicone resin and a crosslinking agent, and, if necessary, an addition reaction inhibitor. Further, a release adjusting agent, an adhesion improving agent and the like may be added.

Although it does not restrict | limit especially as an ultraviolet curable peeling composition, A well-known ultraviolet curable peeling composition may be sufficient and a commercial item can be used. Specific examples include a silicone-based, fluorine-based, alkyl pendant-based, and long-chain alkyl-based ultraviolet curable release composition. If necessary, the above-described addition reaction inhibitor, peeling regulator, adhesion improver, and the like may be added. Moreover, it is preferable that the ultraviolet curable releasable composition segregates silicon on the surface.

As a method for forming the cured layer, a coating liquid comprising a silicone resin composition or an ultraviolet curable release composition and the above-described additive component used as desired is applied onto the substrate, for example, gravure coating. It can be applied by the method, bar coating method, spray coating method, spin coating method or the like. At this time, an appropriate organic solvent may be added for the purpose of adjusting the viscosity of the coating solution. There is no restriction | limiting in particular as an organic solvent, A various thing can be used. For example, hydrocarbon compounds such as toluene and hexane, ethyl acetate, methyl ethyl ketone, and mixtures thereof are used.

(Transfer process of transfer substrate surface)
In the production of the transparent conductive laminate of the present invention, it is preferable to further include a transfer step on the transfer substrate surface. The transfer process of the transfer substrate surface is a process of peeling the transfer substrate, and the surface composed of the auxiliary electrode layer and the embedded resin layer.
The peeling method of the surface which consists of a transfer base material, an auxiliary electrode layer, and a transparent resin layer does not have a restriction | limiting in particular, It can carry out by a well-known method. By this transfer process, the surface composed of the auxiliary electrode layer and the embedded resin layer can be made excellent in smoothness, increase in haze, etc. can be suppressed, and as a result, the optical characteristics of the transparent conductive laminate can be improved. It leads to improvement.

(Laminate formation process)
In the production of the transparent conductive laminate of the present invention, a step of laminating different laminates by a laminating method or the like may be included. For example, as one aspect, a laminate comprising a transfer substrate / auxiliary electrode layer and a laminate comprising an embedded resin layer / transparent gas barrier layer / primer layer / transparent substrate are laminated to form a transfer substrate / auxiliary electrode. A laminate comprising a layer / embedded resin layer / transparent gas barrier layer / primer layer / transparent substrate may be used. As another aspect, a laminate comprising a transfer substrate / auxiliary electrode layer / embedded resin layer and a laminate comprising a transparent gas barrier layer / primer layer / transparent substrate are laminated to form a transfer substrate / auxiliary electrode layer. A laminate comprising: / embedded resin layer / transparent gas barrier layer / primer layer / transparent substrate may be used. As still another embodiment, a laminate comprising a transfer substrate / auxiliary electrode layer / embedded resin layer / adhesion layer and a laminate comprising a transparent gas barrier layer / primer layer / transparent substrate are laminated, or a transfer substrate / A laminate comprising an auxiliary electrode layer / embedded resin layer and a laminate comprising an adhesion layer / transparent gas barrier layer / primer layer / transparent substrate are laminated to form a transfer substrate / auxiliary electrode layer / embedded resin layer / It is good also as a laminated body containing the adhesion layer which consists of adhesion layer / transparent gas barrier layer / primer layer / transparent substrate. In either case, the transfer substrate is then peeled off from the transfer substrate / auxiliary electrode interface side to form a transparent conductive laminate, and the surface comprising the auxiliary electrode layer and the embedded resin layer of the transparent conductive laminate By forming a transparent conductive layer thereon, the transparent conductive laminate of the present invention can be produced.

According to this production method, a transparent conductive laminate having excellent optical properties and flexibility can be produced.

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

The following evaluation and measurement were performed on the transparent conductive laminate and the transparent conductive laminate prepared in Examples and Comparative Examples. The results are shown in Table 1, Table 2-1, and Table 2-2.
(A) Modulus of elasticity With respect to the embedded resin layer and the adhesion layer (the embedded resin layer is formed after forming the transparent conductive laminate and the adhesion layer is formed), a dynamic ultra-hardness meter (made by Shimadzu Corporation, trade name “DUH- W201S ") was used to perform a load-unloading test under the following measurement conditions, and the elastic modulus was calculated from the slope of the obtained unloading curve.
The elastic modulus may be measured as described in the examples, or after the transparent conductive laminate was prepared, the transparent conductive laminate was cut obliquely with, for example, a diamond knife, and the measurement location was exposed and then exposed. Measurements may be made so that the indenter of the dynamic ultra-micro hardness tester is in vertical contact with the measurement location, or other layers stacked on the measurement location may be removed by etching, etc. You may measure after exposing.
<Dynamic microhardness meter measurement conditions>
Indenter: Triangular pyramid indenter Angle between ridges 115 °
Test mode: Load-unload mode Test force: 1 mN
Load speed: 0.142 mN / sec
Holding time: 5 sec
Measurement temperature: 25 ° C, 70 ° C
(B) Glass transition temperature Tg
In Examples and Comparative Examples, as described later, a predetermined resin solution is used, an embedded resin layer is formed on a slide glass having a thickness of 1 mm, and a viscoelasticity measuring apparatus (manufactured by Netch Japan Co., Ltd., DMA242 E Artemis) is used. Thus, the storage elastic modulus E ′ of the embedded resin layer was measured in a measurement range of 0 to 200 ° C. in a tensile mode with a measurement frequency of 10 Hz. Further, the loss elastic modulus E ″ was measured, and the measurement temperature giving the peak value of the obtained loss tangent tan δ (= E ″ / E ′) was defined as the glass transition temperature Tg. Similarly, for the adhesion layer, a predetermined coating liquid was used to form an adhesion layer, and the glass transition temperature Tg was calculated.
(C) Haze Haze was measured according to JIS K 7136 using a turbidimeter (manufactured by Nippon Denshoku Industries Co., Ltd., HAZE METER NDH5000).
(D) Sheet resistance value ρ
The sheet resistance value ρ was measured using a non-contact type resistance measuring device (manufactured by Napson Corporation, model: EC-80P).
(E) Water vapor transmission rate (WVTR)
Using a water vapor transmission meter (manufactured by MOCON, device name: AQUATRAN), according to JIS K7129, the water vapor transmission rate of the transparent conductive laminate having a transparent gas barrier layer at 40 ° C. and 90% RH (g · m ⁻² · day ⁻¹ ) was measured.
(F) Transferability If the cured resin layer A and the transfer substrate are not zipped and the auxiliary electrode layer can be transferred to the embedded resin layer side, ○, if zipping occurs or adheres to the transfer substrate It evaluated as x.
In the present invention, zipping is “when the auxiliary electrode layer on the transfer substrate is transferred from the transfer substrate to the embedded resin layer side, the auxiliary electrode layer of the transfer substrate does not peel smoothly, and the sound is crispy. It means a phenomenon that repeats peeling or stopping while standing. When transferring, zipping may occur, and the auxiliary electrode layer may not be peeled off from the transfer substrate, and a portion that is not transferred may occur.
(G) Dry-type film-forming property The haze before and after dry-type film formation was measured when a transparent conductive layer was formed to a thickness of 50 nm on the surface composed of the auxiliary electrode layer and the embedded resin layer by the dry-type film formation method. Then, the dry film-forming property was evaluated. The dry film forming resistance refers to fluctuations in the haze value due to dry film formation.
◯: When haze rise is 10% or less Δ: When haze rise is more than 10% and 50% or less x: When haze rise is more than 50% (h) Flexibility Repeated bending tester (YUASA) Using the Koki Co., Ltd.), the sheet resistance value ρ before and after bending 100 times so that the transparent conductive layer of the transparent conductive laminate is convex so that the bent portion is 50 mmφ is measured, and the following standard The flexibility was evaluated according to the following.
◯: When the change in sheet resistance value is ± 0.5Ω / □ or less Δ: When the change in sheet resistance value is more than ± 0.5Ω / sq ± 1Ω / □ or less ×: Change in sheet resistance value ± In the case of exceeding 1Ω / □ (i) Moisture and heat resistance After storage for 1000 hours in an environment of 60 ° C. and 95% RH and then for 24 hours in an environment of 23 ° C. and 50% RH, adhesion and sheet resistance were evaluated.
The adhesion is selected from a transparent conductive layer according to the thickness of the embedded resin layer and the adhesion layer, and a cross cut with a 1 to 2 mm width is selected in a grid pattern so that the cutting edge reaches the gas barrier layer. Adhesive tape (cello tape (registered trademark) manufactured by Nichiban Co., Ltd.) is pasted on the transparent conductive layer surface that is cross-cut into a grid shape, and in accordance with the cross-cut tape method of JIS K5600-5-6 (cross-cut method) (Registered Trademark) A peel test was performed, and the adhesion of the transparent conductive layer, the embedded resin layer, and the adhesion layer was evaluated according to the following criteria. In addition, about adhesiveness, it determined by the following reference | standard.
○: The classification of evaluation results in Table 1 of JIS K5600-5-6 is 0-2
×: The classification of the evaluation results in Table 1 of JIS K5600-5-6 is 3-5
The sheet resistance value was measured by the same method as the sheet resistance value ρ described above.

Example 1
The following UV curable acrylic resin solution A was applied on a slide glass having a thickness of 1 mm with an applicator, dried at 90 ° C. for 2 minutes, and then release sheet B [polyethylene terephthalate film subjected to silicone release treatment] (SP manufactured by Lintec Corporation, SP -PET 381031, thickness 38 μm), and using a conveyor type UV irradiation device (manufactured by Heraeus, high-pressure mercury lamp), the integrated light is irradiated from the coated surface so that the integrated light amount is 250 mJ / cm ^2. Obtained. The film thickness after curing was 50 μm. The embedded resin layer A was peeled from the release sheet B, 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
A solution obtained by adding 1.5 parts by mass of a photoinitiator (Irgacure 819, manufactured by BASF) to 100 parts by mass of UV curable acrylic resin (manufactured by Nippon Synthetic Chemical Co., Ltd., UT5746, solid content 80% by mass, ethyl acetate solution) .

Embed UV curable acrylic resin composition A on alkali-free glass (Corning, EagleXG, 100 mm square, 0.7 mm thickness) so that the film thickness after curing is 25 μm under the same coating and curing conditions as described above. The resin layer A was formed and haze _Ha0 was measured. The results are shown in Table 1. An ITO layer, which is a transparent conductive layer, was formed by sputtering on the embedded resin layer A thus formed under the following conditions, and haze H _a1 after the film formation was measured.
※ transparent conductive layer deposition conditions Target: ITO (JX Nippon Mining & Metals Co., SnO ₂ -5wt%)
・ Method: DC magnetron sputtering ・ Application method: DC500W
・ Substrate heating: None ・ Carrier gas: Argon (Ar)
・ Film pressure: 0.6Pa

[Preparation of transparent conductive laminate A]
As a metal paste (conductive composition) for printing an auxiliary electrode layer made of a thin silver wire, a silver paste (manufactured by Mitsuboshi Belting Co., Ltd., trade name: low-temperature fired conductive paste MDot (registered trademark)) was used, and the line width was 30 μm, Using a screen plate (printing area 100 mm square) having a honeycomb structure with a pitch of 1200 μm, an auxiliary electrode layer is formed on a transfer substrate by printing with a screen printing machine (manufactured by Micro Tech, model name: MT-320TV). did. After printing, temporary drying was performed at 70 ° C. for 1 minute, followed by baking at 150 ° C. for 10 minutes in a conveyor type hot air / IR baking furnace. The transfer substrate used here was PET A4100 (100 μm thickness) manufactured by Toyobo Co., Ltd., and the untreated surface was used as the electrode printing surface. 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 to the transparent gas barrier layer side surface of the transparent substrate having the transparent gas barrier layer described later with an applicator and dried at 90 ° C. for 2 minutes. Laminating the surface provided with the UV curable acrylic resin composition A and the auxiliary electrode layer surface provided on the transfer substrate described above, transfer substrate / auxiliary electrode layer / embedded resin layer A / gas barrier layer / primer layer / A laminate A of transparent substrates was obtained. The laminated body A is irradiated with a conveyor-type UV irradiator (manufactured by Heraeus, high-pressure mercury lamp) from the transparent substrate side having the transparent gas barrier layer so that the accumulated light amount becomes 250 mJ / cm ^2. The embedded resin layer A was cured (thickness of the embedded resin layer A after curing: 25 μm). Finally, the transfer base material is peeled off from the interface side consisting of the embedded resin layer A and the auxiliary electrode layer, so that the auxiliary electrode layer and the embedded resin layer having openings through the transparent gas barrier layer on the transparent base material. A transparent conductive laminate A in which a composite layer composed of A was laminated was prepared, and the elastic modulus and haze H _b0 of the embedded resin layer A at 25 ° C. and 70 ° C. were measured with a dynamic ultra-small surface hardness meter. .
Next, on the auxiliary electrode layer side, the transparent conductive layer was formed to a thickness of 50 nm in the same manner as the transparent conductive layer formation conditions described above to form a transparent conductive laminate, and the haze H _b1 , sheet resistance value ρ, water vapor transmission rate ( WVTR) was measured.

<Preparation of transparent gas barrier layer>
On the transparent substrate (polyethylene naphthalate, manufactured by Teijin DuPont Films, PENQ65HWA, 100 μm thick), the following primer layer forming solution was applied by the bar coating method, dried at 70 ° C. for 1 minute, and then UV light. UV light irradiation was performed using an irradiation line (Fusion UV Systems JAPAN, high-pressure mercury lamp; integrated light quantity 100 mJ / cm ² , peak intensity 1.466 W, line speed 20 m / min, number of passes twice), and a thickness of 1 μm A primer layer was formed.
On the obtained primer layer, a perhydropolysilazane-containing liquid (manufactured by AZ Electronic Materials, trade name: AZNL110A-20) is applied by spin coating, and the obtained coating film is heated at 120 ° C. for 2 minutes. Thus, a perhydropolysilazane layer having a thickness of 200 nm was formed. Further, argon (Ar) was plasma ion-implanted into the obtained perhydropolysilazane layer under the following conditions to form a perhydropolysilazane layer (hereinafter referred to as “inorganic layer A”) in which plasma ions were implanted.
Next, two silicon oxynitride layers (inorganic layer B) were repeatedly formed on the inorganic layer A in the same manner as the inorganic layer A except that the thickness of the perhydropolysilazane layer was 150 nm, and a transparent gas barrier layer was laminated.
* Primer layer forming solution After dissolving 20 parts by mass of dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: A-DPH) in 100 parts by mass of methyl isobutyl ketone, a photopolymerizable initiator (manufactured by BASF) , Trade name: Irgacure 127) added to 3% by mass with respect to the solid content.
Plasma ion implantation was performed using the following apparatus under the following implantation conditions.
<Plasma ion implantation system>
RF power source: Model number “RF56000”, JEOL high voltage pulse power source: “PV-3-HSHV-0835”, Kurita Manufacturing Co., Ltd. <Plasma ion implantation conditions>
・ Plasma generated gas: Ar
・ Gas flow rate: 100sccm
・ Duty ratio: 0.5%
・ Repetition frequency: 1000Hz
・ Applied voltage: -10kV
-RF power supply: frequency 13.56 MHz, applied power 1000 W
-Chamber internal pressure: 0.2 Pa
・ Pulse width: 5 sec
・ Processing time (ion implantation time): 200 sec
・ Conveying speed: 0.2m / min

(Example 2)
A transparent conductive laminate B was prepared in the same manner as in Example 1 except that the embedded resin layer B was formed using the following UV curable acrylic resin solution B, and embedded using a dynamic ultra-small surface hardness meter. The elastic modulus at 25 ° C. and 70 ° C. of the resin layer B and the haze H _b0 of the transparent conductive laminate B were measured. Next, the transparent conductive layer was laminated to obtain a transparent conductive laminate, and haze H _b1 , sheet resistance value ρ, and water vapor transmission rate (WVTR) were measured. Further, as in Example 1, the glass transition temperature Tg of the embedded resin layer B was measured.
* UV curable acrylic resin solution B
10 parts by weight of UV curable acrylic resin (UA-A1 manufactured by Toyo Ink Co., Ltd.) per 100 parts by weight of UV curable urethane acrylate resin (manufactured by Nippon Synthetic Chemical, UT5746, solid content 80% by mass, ethyl acetate solution) A solution obtained by adding 1.5 parts by mass of a photoinitiator (Irgacure 819, manufactured by BASF).

(Comparative Example 1)
A transparent conductive laminate C was produced in the same manner as in Example 1 except that the embedded resin layer C was formed using the following UV curable acrylic resin solution C. Although the elastic modulus at 25 ° C. and 70 ° C. of the embedded resin layer C was measured, haze H _b0 , haze H _b1, etc. of the transparent conductive laminate C were not measured due to poor transferability. 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
50 parts of UV curable acrylic resin (UA-A1 manufactured by Toyo Ink Co., Ltd.) for 100 parts by mass of UV curable acrylic resin (manufactured by Nippon Synthetic Chemical, UT5746, solid content 80% by mass, ethyl acetate solution), light A solution obtained by adding 1.5 parts by mass of an initiator (Irgacure 819, manufactured by BASF).

(Comparative Example 2)
A transparent conductive laminate D was produced in the same manner as in Example 1 except that the embedded resin layer D was formed using the following UV curable acrylic resin solution D. Although the elastic modulus at 25 ° C. and 70 ° C. of the embedded resin layer D was measured, the haze H _b0 , haze H _b1, etc. of the transparent conductive laminate D were not measured because of poor transferability. 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 comprising a UV curable acrylic resin (UA-A1 manufactured by Toyo Ink Co., Ltd.).

(Example 3)
The following adhesion layer coating liquid A was applied onto a slide glass having a thickness of 1 mm with an applicator, dried at 90 ° C. for 2 minutes, and then release sheet B [polyethylene terephthalate film subjected to silicone release treatment] (SP-PET 381031 manufactured by Lintec Corporation). , And a thickness of 38 μm) was applied and irradiated from the coated surface using a conveyor-type UV irradiation device (manufactured by Heraeus, high-pressure mercury lamp) so that the integrated light amount was 250 mJ / cm ² , thereby obtaining an adhesion layer A. The film thickness after curing was 50 μm. The adhesion layer A was peeled from the release sheet B, 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.
* Adhesion layer coating solution A
A coating solution comprising a UV curable acrylic resin (manufactured by Toyo Ink, UA-A1, solid content: 100% by mass).
A transfer substrate with an auxiliary electrode layer was prepared in the same manner as in Example 1. The UV curable acrylic resin solution A is applied to the auxiliary electrode layer side of the transfer substrate with an applicator and dried at 90 ° C. for 2 minutes, and the transfer substrate / auxiliary electrode layer / embedded resin layer A (uncured) A laminate B was formed.
In addition, an adhesion layer A (UV curable acrylic resin (UA-A1 manufactured by Toyo Ink Co., Ltd.)) was applied with an applicator to the transparent gas barrier layer side of the transparent substrate having the transparent gas barrier layer formed in the same manner as in Example 1. Then, irradiation is performed from the adhesion layer A side by a conveyor type UV irradiator (manufactured by Heraeus, high-pressure mercury lamp) so that the integrated light amount is 250 mJ / cm ^2, and the adhesion layer A / transparent gas barrier layer / primer layer / transparent substrate A laminate C (thickness of the adhesion layer A after curing: 5 μm) was formed.
Here, the elastic modulus at 25 ° C. of the adhesion layer A of the laminate C was measured with a dynamic ultra-small surface hardness meter.
Next, the embedded resin layer A of the laminate B and the adhesion layer A of the laminate C are bonded with a laminator, and integrated from the transparent resin substrate side by a conveyor type UV irradiator (manufactured by Heraeus, high-pressure mercury lamp). Irradiation was performed so that the amount of light was 250 mJ / cm ² to cure the embedded resin layer A in the laminate B (thickness of the embedded resin layer A after curing: 25 μm). Finally, by peeling the transfer substrate from the interface composed of the embedded resin layer A and the auxiliary electrode layer, the auxiliary electrode layer having an opening on the transparent resin substrate via the transparent gas barrier layer and the adhesion layer A A transparent conductive laminate E in which a composite layer composed of the embedded resin layer A is laminated is manufactured, and the elastic modulus at 25 ° C. and 70 ° C. of the embedded resin layer A and haze H are measured by a dynamic ultra-small surface hardness meter. _c0 was measured.
Furthermore, a transparent conductive layer was formed to a thickness of 50 nm in the same manner as in Example 1 to obtain a transparent conductive laminate, and haze H _c1 , sheet resistance value ρ, and water vapor transmission rate (WVTR) were evaluated.

Example 4
A transparent conductive laminate F was produced in the same manner as in Example 1 except that the film thickness of the adhesion layer A was changed to 25 μm, and the haze H _c0 of the transparent conductive laminate F was evaluated. Next, the transparent conductive layer was laminated to obtain a transparent conductive laminate, and haze H _b1 , sheet resistance value ρ, and water vapor transmission rate (WVTR) were measured.

(Example 5)
A transparent conductive laminate G was produced in the same manner as in Example 1 except that the thickness of the adhesion layer A was changed to 50 μm, and the haze H _c0 of the transparent conductive laminate G was evaluated. Next, the transparent conductive layer was laminated to obtain a transparent conductive laminate, and haze H _b1 , sheet resistance value ρ, and water vapor transmission rate (WVTR) were measured.

(Example 6)
A transparent conductive laminate H was produced in the same manner as in Example 1 except that the film thickness of the adhesion layer A was changed to 75 μm, and the haze H _c0 of the transparent conductive laminate H was evaluated. Next, the transparent conductive layer was laminated to obtain a transparent conductive laminate, and haze H _b1 , sheet resistance value ρ, and water vapor transmission rate (WVTR) were measured.

(Example 7)
In Example 3, the embedded resin layer A is changed to an embedded resin layer E made of the following UV curable acrylic resin solution E, and coating is performed with a die coater so that the thickness directly above the transfer substrate is 1 μm (after curing). Then, while drying at 70 ° C. for 30 seconds, the adhesion layer A is changed to the adhesion layer B composed of the following adhesion layer coating liquid B, and coated and cured to a thickness of 10 μm (after curing) with a bar coater, Further, except that the embedded resin layer E and the adhesion layer B were bonded, a transparent conductive laminate I was prepared in the same manner as in Example 3, and the embedded resin layer E 25 was measured with a dynamic ultra-small surface hardness meter. The elastic modulus at ° C. and 70 ° C. and the haze H _c0 of the transparent conductive laminate I were measured. In addition, the elasticity modulus in 25 degreeC of the contact | adherence layer B after hardening before bonding was measured with the dynamic ultra fine surface hardness meter similarly to Example 3.
Next, the transparent conductive layer was laminated to obtain a transparent conductive laminate, and haze H _b1 , sheet resistance value ρ, and water vapor transmission rate (WVTR) were measured.
Further, in the same manner as in Example 1, an embedded resin layer E was produced on a slide glass having a thickness of 1 mm using a UV curable acrylic resin solution E (film thickness after curing; 50 μm), and the glass transition temperature Tg. Was measured. Furthermore, the adhesion layer B was produced on the 1 mm-thick slide glass by the same method as Example 3 using the adhesion layer coating liquid B (film thickness after curing: 50 μm), and the glass transition temperature Tg was measured.
* UV curable acrylic resin solution E
A solution prepared by adding a UV curable acrylic resin containing inorganic fine particles (manufactured by JSR, Opstar Z7530, solid content 73 mass%, methyl ethyl ketone solution) as a diluent solvent to adjust the solid content to 30 wt%.
* Adhesion layer coating solution B
1 part by weight of photoinitiator (BASF, Irgacure 819) and 100 parts by weight of silane coupling agent (Shin-Etsu Chemical Co., Ltd.) with respect to 100 parts by weight of UV curable acrylic resin (Toa Gosei Co., Ltd., UVX6125, solid content 100% by weight) , KBM903) to which 1 part by mass is added.

(Example 8)
A transparent conductive laminate J was prepared in the same manner as in Example 3 except that the thickness of the adhesion layer A after curing was 100 μm, and the haze H _c0 of the transparent conductive laminate J was evaluated. Next, the transparent conductive layer was laminated to obtain a transparent conductive laminate, and haze H _b1 , sheet resistance value ρ, and water vapor transmission rate (WVTR) were measured.

As is apparent from Table 1, it was found that a transparent conductive laminate having excellent optical properties (small haze) and flexibility can be obtained by controlling the elastic modulus of the embedded resin layer. Further, as is clear from Tables 2-1 and 2-2, by laminating an adhesion layer having an elastic modulus lower than that of the embedded resin layer and the embedded resin layer, more flexibility and adhesion can be obtained. It was found that a transparent conductive laminate excellent in the above can be obtained.

The transparent conductive laminate of the present invention has excellent optical properties and flexibility at the same time, and further has a small sheet resistance value, such as flexible solar cell elements and organic electroluminescence elements that require a large area. It can also be used for devices.

1A, 1B: transparent conductive laminate 2: transparent substrate 3: embedded resin layer 4: auxiliary electrode layer 5: transparent conductive layer 6: primer layer 7: transparent gas barrier layer 8: adhesion layer 9: opening

Claims

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