JP2012022844A - Laminate for conductive film formation and method of manufacturing the same, and method of forming pattern, touch panel and integrated solar battery - Google Patents

Abstract

A conductive film-forming laminate, a conductive film-forming laminate, a pattern-forming method, and a touch panel, which are easily electrically connected to external wiring, have excellent surface conductivity, and have improved scratch resistance. And provision of integrated solar cells.
A conductive film forming layer having a base material, a conductive fiber-containing layer containing at least conductive fibers on the base material, and a soluble protective layer containing at least a water-soluble polymer on the conductive fiber-containing layer. It is a laminate. An embodiment in which the average thickness of the soluble protective layer is 0.1 μm to 5 μm and an embodiment in which the water-soluble polymer is at least one selected from polyvinyl pyrrolidone, polyvinyl alcohol, gelatin, and a cellulose derivative are preferred.
[Selection figure] None

Description

  The present invention relates to a conductive film forming laminate, a method for manufacturing a conductive film forming laminate, a pattern forming method, a touch panel, and an integrated solar cell.

  ITO (Indium Tin Oxide) is widely used as a transparent conductive film, but it is difficult to mass-produce an ITO film at a low cost. For example, an ITO film is formed on a flexible plastic substrate in a large area. It is difficult to supply it in a roll form at low cost. In addition, since the photolithography process for patterning the ITO film requires a complicated process, there is a problem that the cost is increased and the productivity is lowered.

  In order to solve the problem related to the ITO film, it has been proposed to use a conductive material such as silver nanowire (see Patent Documents 1 and 2). According to these proposals, a transparent conductive film can be easily produced by applying and forming a plurality of silver nanowire-containing layers on a transparent substrate by a wet process so as to form a network. In addition, a photosensitive material such as a photoresist is contained in the same layer as the silver nanowire-containing layer or an adjacent layer, and the conductive process is relatively easily performed through an exposure process and a development process, or an exposure process, a development process, and an etching process. It is disclosed that a sex pattern can be obtained.

However, since it is necessary to increase the contact frequency between silver nanowires in order to improve conductivity, if the content of the dispersion medium of the silver nanowire-containing layer is limited, the strength of the formed conductive layer becomes weak, It becomes very easy to be damaged. For this reason, if mass production is performed by applying a large area to a web-shaped transparent substrate and then winding it into a roll, the conductive layer is damaged by contact with the pass roller of the coating machine or the back surface of the substrate, and mass production. There is a problem that it cannot withstand.
In order to solve the above problem, for example, as described in Patent Document 1, it may be possible to protect the conductive layer by providing a protective layer such as a photosensitive layer on the silver nanowire-containing layer, but also after development. Since the protective layer remains, there is a problem that the conductive layer is buried under the protective layer, the surface conductivity is lost, and the electrical connection between the conductive layer and the external wiring becomes insufficient.

  Therefore, a conductive film-forming laminate, a conductive film-forming laminate, and a pattern-forming method, a touch panel, and a touch panel, which are easily electrically connected to external wiring and have excellent surface conductivity and improved scratch resistance. At present, prompt provision of integrated solar cells is desired.

US Patent Application Publication No. 2007/0074316 US Patent Application Publication No. 2008/0292979

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, the present invention provides a conductive film-forming laminate, a conductive film-forming laminate, and a method for forming a pattern, which are easily electrically connected to external wiring, have excellent surface conductivity, and have improved scratch resistance. An object is to provide a method, a touch panel, and an integrated solar cell.

Means for solving the problems are as follows. That is,
<1> It has a base material, a conductive fiber-containing layer containing at least conductive fibers on the base material, and a soluble protective layer containing at least a water-soluble polymer on the conductive fiber-containing layer. It is the laminated body for electrically conductive film formation to perform.
<2> The conductive film-forming laminate according to <1>, wherein the soluble protective layer has an average thickness of 0.1 μm to 5 μm.
<3> The conductive film-forming laminate according to any one of <1> to <2>, wherein the water-soluble polymer is at least one selected from polyvinyl pyrrolidone, polyvinyl alcohol, gelatin, and a cellulose derivative.
<4> The conductive film-forming laminate according to any one of <1> to <3>, wherein the conductive fibers are metal nanowires.
<5> The conductive film-forming laminate according to <4>, wherein the metal nanowire is made of any of silver and an alloy of silver and a metal other than silver.
<6> The conductive film-forming laminate according to any one of <1> to <5>, wherein the conductive fiber-containing layer contains a dispersion medium.
<7> The conductive film-forming laminate according to any one of <1> to <6>, wherein the surface resistance of the conductive fiber-containing layer is 0.1Ω / □ to 10,000Ω / □.
<8> The conductive film-forming laminate according to any one of <1> to <7>, wherein the light transmittance is 70% or more.
<9> The conductive film-forming laminate according to any one of <1> to <8>, wherein a photosensitive layer is provided between the substrate and the conductive fiber-containing layer.
<10> The conductive film-forming laminate according to any one of <1> to <9>, wherein the base material is transparent.
<11> The conductive film-forming laminate according to any one of <1> to <10>, which is wound in a roll shape.
<12> On the base material, a conductive fiber-containing layer forming step of forming a conductive fiber-containing layer by applying a conductive fiber-containing layer composition containing at least conductive fibers;
A soluble protective layer forming step of forming a soluble protective layer by applying a composition for a soluble protective layer containing at least a water-soluble polymer on the conductive fiber-containing layer;
It is a manufacturing method of the laminated body for electrically conductive film formation characterized by including.
<13> The method for producing a laminate for forming a conductive film according to <12>, including a soluble protective layer removing step of removing the soluble protective layer by applying a solvent to the soluble protective layer.
<14> The method for producing a laminate for forming a conductive film according to <13>, wherein the solvent is any one of water and an alkaline solution.
<15> An exposure step of exposing at least the conductive fiber-containing layer in the conductive film-forming laminate according to any one of <1> to <11>,
A removal step of removing at least one of the exposed portion and the non-exposed portion in the conductive fiber-containing layer and the soluble protective layer by applying a solvent;
A pattern forming method comprising:
<16> The pattern forming method according to <15>, wherein the solvent is an alkaline solution.
<17> A touch panel using the conductive film-forming laminate according to any one of <1> to <11>.
<18> An integrated solar cell using the conductive film-forming laminate according to any one of <1> to <11>.

  According to the present invention, the conventional problems can be solved, the electrical connection with the external wiring is easy, the surface conductive property is excellent, and the scratch resistance is improved. A laminate manufacturing method, a pattern formation method, a touch panel, and an integrated solar cell can be provided.

1A to 1C are schematic diagrams illustrating a layer structure of a touch panel. FIG. 2 is a schematic cross-sectional view showing an example of a touch panel. FIG. 3 is a schematic explanatory diagram illustrating another example of the touch panel. FIG. 4 is a schematic plan view showing an example of arrangement of conductors in the touch panel shown in FIG. FIG. 5 is a schematic cross-sectional view showing still another example of the touch panel.

(Laminated body for forming conductive film)
The laminate for forming a conductive film of the present invention comprises a base material, a conductive fiber-containing layer on the base material, and a soluble protective layer on the conductive fiber-containing layer, and further if necessary. It has other layers.
The “conductive film-forming laminate” may or may not exhibit conductivity, and may be referred to as a “conductor” when conductivity is exhibited. In addition, the “conductive fiber-containing layer” may or may not exhibit conductivity, and may be referred to as a “conductive layer” when conductivity is expressed. is there.

<Base material>
There is no restriction | limiting in particular about the shape, structure, size, etc. of the said base material, According to the objective, it can select suitably, For example, a film | membrane form, a sheet form, etc. are mentioned as said shape.
Examples of the substrate include a transparent glass substrate, a synthetic resin sheet (film), a metal substrate, a ceramic plate, and a semiconductor substrate having a photoelectric conversion element. If necessary, the substrate can be subjected to pretreatment such as chemical treatment such as a silane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition and the like.

The total visible light transmittance of the substrate is preferably 70% or more, more preferably 85% or more, and still more preferably 90% or more. In the present invention, a substrate that is colored to the extent that the object of the present invention is not hindered can also be used.
There is no restriction | limiting in particular as thickness of the said base material, Although it can select suitably according to the objective, 1 micrometer-5,000 micrometers are preferable, 3 micrometers-4,000 micrometers are more preferable, 5 micrometers-3,000 micrometers are still more preferable. .
If the thickness is less than 1 μm, the yield may decrease due to difficulty in handling in the coating process, and if it exceeds 5,000 μm, the thickness and mass are problematic in portable applications. Sometimes.

<Conductive fiber-containing layer>
The conductive fiber-containing layer contains at least conductive fibers, a dispersion medium, and further contains other components as necessary.

[Conductive fiber]
The structure of the conductive fiber is preferably a solid structure or a hollow structure.
Here, the solid structure fiber may be referred to as a wire, and the hollow structure fiber may be referred to as a tube.
A conductive fiber having an average minor axis length of 5 nm to 1,000 nm and an average major axis length of 1 μm to 100 μm may be referred to as “nanowire”.
In addition, conductive fibers having an average minor axis length of 1 nm to 1,000 nm and an average major axis length of 0.1 μm to 1,000 μm and having a hollow structure may be referred to as “nanotubes”.
The material of the conductive fiber is only required to have conductivity, and is preferably a metal or carbon. Among these, the conductive fiber is a metal nanowire, a metal nanotube, or a carbon nanotube. It is preferable.

<< Metal nanowires >>
-Material-
As the material of the metal nanowire, for example, at least one metal selected from the group consisting of the fourth period, the fifth period, and the sixth period of the long periodic table (IUPAC 1991) is preferable. More preferred is at least one metal selected from Group 14.

-Metal-
Examples of the metal include copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, iron, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantel, titanium, bismuth, antimony, and lead. Or alloys thereof. Among these, silver and an alloy with silver are particularly preferable in terms of excellent conductivity.
Examples of the metal used in the alloy with silver include platinum, osmium, palladium, and iridium. These may be used alone or in combination of two or more.

-Shape-
As the shape of the metal nanowire, for example, a columnar shape, a rectangular parallelepiped shape, a columnar shape having a polygonal cross section, and the like, a column shape or a cross section can be used in applications where high transparency is required. It is preferable that it is a cross-sectional shape with rounded corners.
The cross-sectional shape of the metal nanowire can be examined by applying a metal nanowire aqueous dispersion on a substrate and observing the cross-section with a transmission electron microscope (TEM).

−Average minor axis length diameter and average major axis length−
The average minor axis length of the metal nanowire (sometimes referred to as “average minor axis diameter” or “average diameter”) is preferably 1 nm to 50 nm, more preferably 10 nm to 40 nm, and even more preferably 15 nm to 35 nm. .
When the average minor axis length is less than 1 nm, the oxidation resistance may be deteriorated and the durability may be deteriorated. When the average minor axis length is more than 50 nm, scattering due to metal nanowires occurs and sufficient transparency is obtained. There are times when you can't.
The average minor axis length of the metal nanowires was observed using 300 transmission metal microscopes (TEM; JEM-2000FX, JEM-2000FX), and the average value of the metal nanowires was determined from the average value. The average minor axis length was determined. In addition, the shortest axis length when the short axis of the metal nanowire is not circular is the shortest axis.

The average major axis length (sometimes referred to as “average length”) of the metal nanowires is preferably 1 μm to 40 μm, more preferably 3 μm to 35 μm, and even more preferably 5 μm to 30 μm.
If the average major axis length is less than 1 μm, it may be difficult to form a dense network and sufficient conductivity may not be obtained. If it exceeds 40 μm, the metal nanowires are too long and manufactured. Sometimes entangled and agglomerates may occur during the manufacturing process.
The average major axis length of the metal nanowire is observed, for example, using a transmission electron microscope (TEM; JEM-2000FX, JEM-2000FX). The average major axis length was determined. In addition, when the said metal nanowire was bent, the circle | round | yen which makes it an arc was considered and the value calculated from the radius and curvature was made into the major axis length.
Examples of the method for producing the metal nanowire include, for example, JP 2009-215594 A, JP 2009-242880 A, JP 2009-299162 A, JP 2010-84173 A, and JP 2010-86714 A. Etc. can be used.

<< Metal Nanotubes >>
-Material-
As the metal nanotube material, the above-described metal nanowire material or the like can be used.
-Shape-
The shape of the metal nanotube may be a single layer or a multilayer, but a single layer is preferable in terms of excellent conductivity and thermal conductivity.
-Average minor axis length, average major axis length, thickness-
The thickness of the metal nanotube (difference between the outer diameter and the inner diameter) is preferably 3 nm to 80 nm, and more preferably 3 nm to 30 nm.
When the thickness is less than 3 nm, the oxidation resistance is deteriorated and the durability may be deteriorated. When the thickness is more than 80 nm, scattering due to the metal nanotube may occur.
The average major axis length of the metal nanotube is preferably 1 μm to 40 μm, more preferably 3 μm to 35 μm, and still more preferably 5 μm to 30 μm.

-Manufacturing method-
As a method for producing the metal nanotube, for example, a method described in US Patent Application Publication No. 2005/0056118 and the like can be used.

<< Carbon nanotube >>
The carbon nanotube (CNT) is a substance in which a graphite-like carbon atomic surface (graphene sheet) is a single-layer or multilayer coaxial tube. The single-walled carbon nanotubes are called single-walled nanotubes (SWNT), the multi-walled carbon nanotubes are called multi-walled nanotubes (MWNT), and the double-walled carbon nanotubes are also called double-walled nanotubes (DWNT). In the conductive fiber used in the present invention, the carbon nanotube may be a single wall or a multilayer, but a single wall is preferable from the viewpoint of excellent conductivity and thermal conductivity.

-Aspect ratio-
The aspect ratio of the conductive fiber is preferably 10 or more. The aspect ratio generally means the ratio between the long side and the short side of a fibrous material (ratio of average major axis length / average minor axis length).
There is no restriction | limiting in particular as a measuring method of the said aspect ratio, According to the objective, it can select suitably, For example, the method etc. which measure with an electron microscope etc. are mentioned.
When measuring the aspect ratio of the conductive fiber with an electron microscope, it is only necessary to confirm whether the aspect ratio of the conductive fiber is 10 or more with one field of view of the electron microscope. In addition, the aspect ratio of the entire conductive fiber can be estimated by measuring the major axis length and the minor axis length of the conductive fiber separately.
In addition, when the said conductive fiber is a tube shape, the outer diameter of this tube is used as a diameter for calculating the said aspect ratio.

The aspect ratio of the conductive fiber is not particularly limited as long as it is 10 or more, and can be appropriately selected according to the purpose, but is preferably 50 to 1,000,000, and 100 to 1,000,000. More preferred.
When the aspect ratio is less than 10, network formation by the conductive fibers may not be performed and sufficient conductivity may not be obtained. When the aspect ratio exceeds 1,000,000, the conductive fibers may be formed or handled thereafter. In this case, since the conductive fibers are entangled and aggregate before film formation, a stable liquid may not be obtained.

-Ratio of conductive fibers having an aspect ratio of 10 or more-
The ratio of the conductive fibers having an aspect ratio of 10 or more is preferably 50% or more, more preferably 60% or more, and particularly preferably 75% or more in volume ratio in the total conductive composition. Hereinafter, the ratio of these conductive fibers may be referred to as “the ratio of conductive fibers”.
If the ratio of the conductive fibers is less than 50%, the conductive material contributing to the conductivity may decrease and the conductivity may decrease. At the same time, a voltage concentration may occur because a dense network cannot be formed. , Durability may be reduced. In addition, particles having a shape other than the conductive fiber are not preferable because they do not greatly contribute to conductivity and have absorption. In particular, in the case of metal, transparency may be deteriorated when plasmon absorption such as a spherical shape is strong.

  Here, the ratio of the conductive fibers is, for example, when the conductive fibers are silver nanowires, the silver nanowire aqueous dispersion is filtered to separate the silver nanowires from the other particles. The ratio of the conductive fibers can be determined by measuring the amount of silver remaining on the filter paper and the amount of silver that has passed through the filter paper using an ICP emission analyzer. By observing the conductive fibers remaining on the filter paper with a TEM, observing the short axis lengths of 300 conductive fibers and examining their distribution, the short axis length is 200 nm or less and the long axis length is It confirms that it is an electroconductive fiber whose length is 1 micrometer or more. Note that the filter paper has a short axis length of 200 nm or less in the TEM image and the longest axis of particles other than conductive fibers having a long axis length of 1 μm or more is measured, and is at least twice the longest axis. And it is preferable to use the thing of the length below the shortest length of the long axis of an electroconductive fiber.

  Here, the average minor axis length and the average major axis length of the conductive fiber can be obtained by observing a TEM image or an optical microscope image using, for example, a transmission electron microscope (TEM) or an optical microscope. In the present invention, the average minor axis length and the average major axis length of the conductive fibers are obtained by observing 300 conductive fibers with a transmission electron microscope (TEM) and obtaining the average value. is there.

<< dispersion medium >>
In the present invention, the dispersion medium means all components other than the conductive fibers of the conductive fiber-containing layer. The mass ratio (A / B) between the total content A of the dispersion medium in the conductive fiber-containing layer (a single content in the case of only one type) and the content B of the conductive fiber is 0.1. It is preferable that it is -5.0, and it is more preferable that it is 0.5-3.0. When the mass ratio (A / B) is less than 0.1, deterioration of optical properties such as conductivity, transmittance and haze due to aggregation of conductive fibers, mechanical strength of the conductive fiber-containing layer, and the substrate Problems such as deterioration of adhesion, particularly deterioration of pattern quality (faithful reproducibility of an exposure pattern) obtained by patterning using photolithography may occur. When the mass ratio (A / B) exceeds 5.0, there may be a decrease in conductivity due to a decrease in the number of contact points between the conductive fibers, and deterioration of optical characteristics such as haze and light transmittance.
Since the dispersion medium may be reduced at least partly by elution or the like in the removal step described later, the total content A of the dispersion medium in the present invention uses the amount of the dispersion medium after the removal step. And By designing to reduce the mass of the dispersion medium in the removal process, the conductivity after the removal process is improved while suppressing aggregation of the conductive fibers before the coating and drying process and improving the mechanical strength of the conductive fiber-containing layer. In the present invention, the mass of the dispersion medium is preferably reduced in the removing step. The ratio (A / A0) of the dispersion medium amount A0 before the removal step and the dispersion medium amount after the removal step is preferably 0.01 or more and less than 1, more preferably 0.1 or more and less than 0.8. preferable. The removal of at least a part of the dispersion medium in the removing step can be preferably performed by adding a water-soluble polymer or an alkali-soluble polymer to the dispersion medium.

  In the present invention, the dispersion medium preferably contains a photosensitive compound that imparts the function of forming an image by exposure to the conductive fiber-containing layer or gives the trigger thereof. Specifically, (1) acid by exposure (2) a photosensitive quinonediazide compound, (3) a photoradical generator, and the like. These may be used individually by 1 type and may use 2 or more types together. Moreover, a sensitizer etc. can also be used together for sensitivity adjustment. In addition to these components, various additives such as polymers, monomers, dispersants, solvents, crosslinking agents, surfactants, antioxidants, antioxidants, metal corrosion inhibitors, viscosity modifiers, preservatives, and the like described below. Etc. These components may be appropriately contained as necessary.

-(1) Photoacid generator-
(1) As the photoacid generator, a photoinitiator for photocationic polymerization, a photoinitiator for radical photopolymerization, a photodecolorant for dyes, a photochromic agent, an actinic ray used for a micro resist, etc. Alternatively, known compounds that generate an acid upon irradiation with radiation or a mixture thereof can be appropriately selected and used.

  Examples of the (1) photoacid generator include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, and o-nitrobenzyl sulfonates. Among these, imide sulfonate, oxime sulfonate, and o-nitrobenzyl sulfonate, which are compounds that generate sulfonic acid, are particularly preferable.

Further, a group capable of generating an acid upon irradiation with actinic rays or radiation, or a compound in which a compound is introduced into the main chain or side chain of the resin, such as US Pat. No. 3,849,137, German Patent No. 3914407. Description, JP-A-63-26653, JP-A-55-164824, JP-A-62-69263, JP-A-63-146038, JP-A-63-163452, JP-A-62-153853 The compounds described in JP-A-63-146029, etc. can be used.
Furthermore, compounds capable of generating an acid by light described in each specification such as US Pat. No. 3,779,778 and European Patent 126,712 can also be used.

-(2) Quinonediazide compound-
The (2) quinonediazide compound can be obtained, for example, by subjecting 1,2-quinonediazidesulfonyl chlorides, hydroxy compounds, amino compounds and the like to a condensation reaction in the presence of a dehydrochlorinating agent.

The blending amount of the (1) photoacid generator and the (2) quinonediazide compound is set to 100 parts by mass of the total amount of polymer to be described later in terms of the difference in dissolution rate between the exposed part and the unexposed part and the allowable range of sensitivity. On the other hand, 1 mass part-100 mass parts are preferable, and 3 mass parts-80 mass parts are more preferable.
The (1) photoacid generator and the (2) quinonediazide compound may be used in combination.

  When a compound having a 1,2-naphthoquinonediazide group is used as the (2) quinonediazide compound, high sensitivity and good developability are obtained.

-(3) Photoradical generator-
The conductive fiber-containing layer can use a photoradical generator having a function of directly absorbing light or photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction to generate a polymerization active radical as a dispersion medium. . The photoradical generator preferably has absorption in a wavelength region of 300 nm to 500 nm.

  The said photoradical generator may be used individually by 1 type, and may use 2 or more types together. The content of the photo radical generator is preferably 0.1% by mass to 50% by mass, more preferably 0.5% by mass to 30% by mass with respect to the entire conductive fiber-containing layer, and 1% by mass. -20 mass% is still more preferable. In this numerical range, good sensitivity and pattern formability can be obtained.

  There is no restriction | limiting in particular as said photoradical generator, According to the objective, it can select suitably, For example, the compound group of Unexamined-Japanese-Patent No. 2008-268884 is mentioned. Among these, triazine compounds, acetophenone compounds, acylphosphine (oxide) compounds, oxime compounds, imidazole compounds, and benzophenone compounds are particularly preferable from the viewpoint of exposure sensitivity.

In the conductive fiber-containing layer, a photo radical generator and a chain transfer agent may be used in combination for improving exposure sensitivity.
Examples of the chain transfer agent include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, Heterocycles such as N-phenylmercaptobenzimidazole, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione Polyfunctional mercapto compounds such as pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane Etc. These may be used individually by 1 type and may use 2 or more types together.
The content of the chain transfer agent is preferably 0.01% by mass to 15% by mass, more preferably 0.1% by mass to 10% by mass with respect to the entire conductive fiber-containing layer, and 0.5% by mass to 5 mass% is still more preferable.

-Polymer-
The polymer is a linear organic high molecular polymer, and at least one group that promotes alkali solubility in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be appropriately selected from alkali-soluble resins having (for example, carboxyl group, phosphoric acid group, sulfonic acid group, etc.).
Among these, those that are soluble in an organic solvent and that can be developed with a weak alkaline aqueous solution are preferable, and those that have an acid-dissociable group and become alkali-soluble when the acid-dissociable group is dissociated by the action of an acid. Particularly preferred.
Here, the acid dissociable group represents a functional group that can dissociate in the presence of an acid.

As the linear organic polymer, a polymer having a carboxylic acid in the side chain is preferable.
Examples of the polymer having a carboxylic acid in the side chain include, for example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-59-53836, A methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partial ester, as described in JP-A-59-71048 A maleic acid copolymer, etc., an acidic cellulose derivative having a carboxylic acid in the side chain, a polymer having a hydroxyl group with an acid anhydride added, and a polymer having a (meth) acryloyl group in the side chain Polymers are also preferred.

Among these, benzyl (meth) acrylate / (meth) acrylic acid copolymers and multi-component copolymers composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are particularly preferable.
Furthermore, a high molecular polymer having a (meth) acryloyl group in the side chain and a multi-component copolymer comprising (meth) acrylic acid / glycidyl (meth) acrylate / other monomers are also useful. The polymer can be used by mixing in an arbitrary amount.

The weight average molecular weight of the polymer is preferably from 1,000 to 500,000, more preferably from 3,000 to 300,000, and even more preferably from 5,000 to 200,000, from the viewpoints of alkali dissolution rate, film physical properties and the like. .
Here, the weight average molecular weight can be determined, for example, by a gel permeation chromatography method and using a standard polystyrene calibration curve.

  The content of the polymer is preferably 5% by mass to 90% by mass, more preferably 10% by mass to 85% by mass, and still more preferably 20% by mass to 80% by mass with respect to the entire conductive fiber-containing layer. . When the content is in the range, both developability and conductivity of the metal nanowire can be achieved.

-Dispersant-
The dispersant is used for preventing and dispersing the conductive fibers. The dispersant is not particularly limited as long as the conductive fibers can be dispersed, and can be appropriately selected according to the purpose. For example, commercially available low molecular pigment dispersants and polymer pigment dispersants can be used. In particular, a polymer dispersant having a property of adsorbing to conductive fibers is preferably used. For example, polyvinylpyrrolidone, BYK series (manufactured by Big Chemie), Solsperse series (manufactured by Nippon Lubrizol, etc.), Ajisper series ( Ajinomoto Co., Inc.).

As content of the said dispersing agent, 0.1 mass part-50 mass parts are preferable with respect to 100 mass parts of said polymers, 0.5 mass part-40 mass parts are more preferable, and 1 mass part-30 mass parts are. Particularly preferred.
When the content is less than 0.1 parts by mass, the conductive fibers may aggregate in the dispersion, and when it exceeds 50 parts by mass, a stable liquid film cannot be formed in the coating process. Application unevenness may occur.

<Soluble protective layer>
The soluble protective layer contains a water-soluble polymer, and further contains other components as necessary.

-Water-soluble polymer-
The water-soluble polymer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, gelatin, gelatin derivatives, casein, agar, starch, polyvinyl alcohol, polyacrylic acid copolymer, carboxyalkyl cellulose, water-soluble Cellulose derivatives such as water-soluble cellulose ether, polyvinylpyrrolidone, dextran, polyalkylene glycol and the like. These may be used individually by 1 type and may use 2 or more types together. Among these, polyvinyl pyrrolidone, polyvinyl alcohol, gelatin, and cellulose derivatives are particularly preferable.
The polyvinyl pyrrolidone may be a copolymer having a polymer unit other than the vinyl pyrrolidone unit. Examples of such a copolymer include a vinyl pyrrolidone / vinyl acetic acid copolymer. The polyvinyl alcohol may be a copolymer having a polymer unit other than the vinyl alcohol unit. Examples of such a copolymer include a vinyl alcohol / vinyl pyrrolidone copolymer.
Examples of the water-soluble cellulose derivative include carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose and the like.
Examples of the polyalkylene glycol include polyethylene glycol and an ethylene glycol / propylene glycol copolymer, and a polyalkylene glycol having a weight average molecular weight of 5,000 to 100,000 is preferable.

  The other components are not particularly limited and may be appropriately selected depending on the intended purpose. For example, fillers, surfactants, antioxidants, sulfurization inhibitors, metal corrosion inhibitors, viscosity modifiers, preservatives And various other additives.

The soluble protective layer can be formed by a method for producing a laminate for forming a conductive film, which will be described later.
The average thickness of the soluble protective layer is preferably 0.1 μm to 5 μm, more preferably 0.2 μm to 2 μm, and still more preferably 0.5 μm to 1 μm. If the average thickness is less than 0.1 μm, it may be difficult to obtain the effect of improving scratch resistance. If the average thickness exceeds 5 μm, it may take time to remove the soluble protective layer, or the soluble protective layer may remain. In addition, since the binder of the protective layer is mixed into the conductive fiber-containing layer and the density of the conductive fiber is decreased, the conductivity is lowered even when sufficient time is taken to remove the soluble protective layer. A phenomenon may be seen.
Here, the average thickness of the soluble protective layer can be measured, for example, by observing the cross section of the protective layer with a scanning electron microscope (SEM).

-Photosensitive layer-
In this invention, when the said conductive fiber content layer does not contain the photosensitive compound as a dispersion medium, it is preferable to have a photosensitive layer between the said base material and the said conductive fiber content layer.
The photosensitive layer contains at least a photosensitive compound, and contains a polymer and, if necessary, other components.
There is no restriction | limiting in particular as said photosensitive compound and polymer, Although it can select suitably according to the objective, For example, the thing similar to the said conductive fiber content layer can be used.
There is no restriction | limiting in particular in the thickness of the said photosensitive layer, Although it can select suitably according to the objective, It is preferable that they are 0.01 micrometer-100 micrometers, and it is more preferable that they are 0.05 micrometer-10 micrometers.

(Method for producing conductive film-forming laminate)
The method for producing a laminate for forming a conductive film of the present invention includes at least a conductive fiber-containing layer forming step and a soluble protective layer forming step, a soluble protective layer removing step, and further including other steps as necessary. Become.

<Conductive fiber-containing layer forming step>
The said conductive fiber content layer formation process is a process of apply | coating the composition for conductive fiber content layers containing a conductive fiber on a base material, and forming a conductive fiber content layer.

  The base material and the conductive fiber can be appropriately selected from those described above.

  The method for applying the conductive fiber-containing layer composition is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a roll coating method, a bar coating method, a dip coating method, a spin coating method, or a casting method. , Die coating method, blade coating method, bar coating method, gravure coating method, curtain coating method, spray coating method, doctor coating method, and the like.

The coating amount of the metal nanowires as (content) is not particularly limited and may be appropriately selected depending on the intended ^purpose, it is preferably ^{0.005g / m 2 ~0.5g / m 2} , 0 more preferably ^{.01g / m 2 ~0.45g / m 2} , 0.015g / m 2 ~0.4g / m 2 is more preferable.
When the coating amount is less than 0.005 g / m ² , there may be a portion where the resistance is locally increased, and the in-plane resistance distribution may be deteriorated, and when it exceeds 0.5 g / m ^2. The haze may deteriorate due to the aggregation of metal nanowires during drying after coating.

There is no restriction | limiting in particular as thickness of the said conductive fiber content layer, According to the objective, it can select suitably, 20 nm-5,000 nm are preferable, 25 nm-4,000 nm are more preferable, 30 nm-3,500 nm are Further preferred.
If the thickness is less than 20 nm, the average minor axis length of the metal nanowires is not changed, and the film strength may be reduced. If the thickness exceeds 5,000 nm, the conductive fiber-containing layer cracks. Cracks, transmittance, and haze may deteriorate.

<Soluble protective layer forming step>
The soluble protective layer forming step is a step of forming a soluble protective layer by applying a composition for a soluble protective layer containing at least a water-soluble polymer on the conductive fiber-containing layer.

As the water-soluble polymer, those similar to the soluble protective layer can be used.
The composition for a soluble protective layer contains at least a water-soluble polymer, and contains a solvent and, if necessary, other components.

  The solvent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include methanol, ethanol, 1-propanol, 2-propanol, acetone, 2-butanone, ethyl acetate, propyl acetate, tetrahydrofuran, acetonitrile, Dioxane, toluene, xylene, cyclohexanone, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, N, N -Dimethylformamide, acetic acid, water and the like. These may be used individually by 1 type and may use 2 or more types together. Among these, those that do not dissolve the conductive fiber-containing layer are preferable, and water is particularly preferable.

There is no restriction | limiting in particular as said "application | coating", According to the objective, it can select suitably, For example, all the general liquid phase film-forming methods, such as the apply | coating method, the printing method, the inkjet method, are mentioned The said apply | coating method There is no restriction | limiting in particular, The same method as the application | coating method of the said composition for conductive fiber content layers is mentioned.
Examples of the printing method include letterpress (letterpress) printing, stencil (screen) printing, lithographic (offset) printing, and intaglio (gravure) printing.

<Soluble protective layer removal step>
The soluble protective layer removing step is a step of removing the soluble protective layer by applying a solvent to the soluble protective layer.
The soluble protective layer removing step is performed at the time of pattern formation of the conductive fiber-containing layer in the method for manufacturing the conductive film-forming laminate, but can also be performed together with pattern formation on the user side.

The solvent is preferably either water or an alkaline solution.
There is no restriction | limiting in particular as said water, According to the objective, it can select suitably, For example, pure water, such as ion-exchange water, ultrafiltration water, reverse osmosis water, distilled water, or ultrapure water etc. are mentioned. .
The alkali contained in the alkaline solution is not particularly limited and may be appropriately selected depending on the intended purpose. For example, tetramethylammonium hydroxide, tetraethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, sodium carbonate, Examples thereof include sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydroxide, potassium hydroxide and the like.

There is no restriction | limiting in particular as the provision method of the said water and an alkaline solution, According to the objective, it can select suitably, For example, application | coating, immersion, spraying etc. are mentioned. Among these, immersion is particularly preferable.
There is no restriction | limiting in particular in the immersion time of the said water and an alkaline solution, Although it can select suitably according to the objective, It is preferable that it is 10 second-5 minutes.

(Pattern formation method)
The pattern forming method of the present invention includes an exposure step and a removal step, and further includes other steps as necessary.

<Exposure process>
The exposure step is a step of exposing at least the conductive fiber-containing layer in the conductive film-forming laminate of the present invention.
As the exposure method, surface exposure using a photomask may be performed, or scanning exposure using a laser beam may be performed. At this time, refractive exposure using a lens or reflection exposure using a reflecting mirror may be used, and exposure methods such as contact exposure, proximity exposure, reduced projection exposure, and reflection projection exposure can be used.

<Removal process>
The removal step is a step of removing at least one of the exposed portion and the non-exposed portion in the conductive fiber-containing layer and the soluble protective layer by applying a solvent.
In the said removal process, when it has a photosensitive layer between the said base material and a conductive fiber content layer, either the exposure part and non-exposed part in the said photosensitive layer, and a soluble protective layer are removed.

As the solvent, an alkaline solution is preferable. As the alkaline solution, the same solution as the manufacturing method of the conductive film forming laminate of the present invention can be used.
There is no restriction | limiting in particular as the provision method of the said alkaline solution, According to the objective, it can select suitably, For example, application | coating, immersion, spraying etc. are mentioned. Among these, immersion is particularly preferable.
There is no restriction | limiting in particular in the immersion time of the said alkaline solution, Although it can select suitably according to the objective, It is preferable that it is 10 seconds-5 minutes.

The surface resistance of the conductive fiber-containing layer in the conductive film-forming laminate of the present invention is preferably 0.1Ω / □ to 10,000Ω / □, and preferably 0.1Ω / □ to 1,000Ω / □. It is more preferable. The low surface resistance itself is not harmful, but if it is less than 0.1 Ω / □, it may be difficult to obtain a conductive film-forming laminate having high light transmittance, and 10,000 Ω / □. Exceeding may cause problems such as disconnection due to Joule heat generated during energization, or voltage drop at the upstream and downstream of the wiring, limiting the area when used for a touch panel.
Here, the surface resistance can be measured using, for example, a surface resistance meter (Loresta-GP MCP-T600, manufactured by Mitsubishi Chemical Corporation).

70% or more is preferable and, as for the light transmittance of the laminated body for electrically conductive film formation of this invention, 80% or more is more preferable. When the light transmittance is less than 70%, the conductive pattern becomes conspicuous when used in an image display medium such as a touch panel, and it is necessary to increase the power consumption in order to reduce the image quality or compensate for the decrease in luminance. Detrimental effects such as occurrence may occur.
Here, the said transmittance | permeability can be measured with a self-recording spectrophotometer (UV2400-PC, Shimadzu Corporation make), for example.

  The laminate for forming a conductive film of the present invention has high permeability and low resistance, improved durability and flexibility, and can be easily patterned. For example, a touch panel, an electrode for display, an electromagnetic wave shield, organic It is widely applied to EL display electrodes, inorganic EL display electrodes, electronic paper, flexible display electrodes, integrated solar cells, display elements, and other various devices. Among these, a touch panel, a display element, and an integrated solar cell are particularly preferable.

<Display element>
A liquid crystal display element as a display element used in the present invention includes an element substrate provided with the conductive film-forming laminate of the present invention patterned on the substrate as described above, and a color filter substrate which is a counter substrate. Are aligned and pressure-bonded and then heat-treated and combined to inject liquid crystal and seal the injection port. At this time, the conductive film forming laminate formed on the color filter is also preferably the conductive film forming laminate of the present invention.
Further, after the liquid crystal is spread on the element substrate, the liquid crystal display element may be manufactured by superimposing the substrates and sealing the liquid crystal so as not to leak.
In addition, there is no restriction | limiting in particular about the liquid crystal used for the said liquid crystal display element, ie, a liquid crystal compound, and a liquid crystal composition, Any liquid crystal compound and liquid crystal composition can be used.

(Touch panel)
The touch panel of the present invention is not particularly limited as long as it has the conductive film-forming laminate of the present invention, and can be appropriately selected according to the purpose. For example, a surface capacitive touch panel, a projection electrostatic Examples include a capacitive touch panel and a resistive touch panel.
In this touch panel, the “conductive film-forming laminate” of the present invention is used as a “transparent conductor”, and the “conductive fiber-containing layer” corresponds to the “conductive layer”.

Here, it is preferable that the touch panel has an antireflection film as described below.
<Antireflection film>
The antireflection film is produced by forming a hard coat layer and an antireflection layer on a transparent support.
Here, FIG. 1A to FIG. 1C are schematic views showing a layer structure of the touch panel.
1A includes a display 101, a touch panel 130, and an antireflection film 120. The touch panel 130 includes a first electrode 105, a transparent substrate 104, a second electrode 103, and a transparent adhesive 102. The antireflection film 120 includes an antireflection layer 109 and a hard coat layer 108.
1B includes a display 101, a touch panel 130, and an antireflection film 120. The touch panel 130 includes a protective resin layer 110, a first electrode 105, a transparent substrate 104, and a second electrode 103. And the transparent adhesive 102, and the antireflection film 120 includes an antireflection layer 109 and a hard coat layer 108.
1C includes a display 101, a touch panel 130, and an antireflection film 120. The touch panel 130 includes a transparent adhesive 106, a first electrode 105, a transparent substrate 104, and a second electrode 103. The antireflection film 120 includes an antireflection layer 109, a hard coat layer 108, and a transparent film 107.

-Transparent support-
Since the transparent support is used on the viewer-side surface of the image display device, the transparent support is required to be a colorless film having high light transmittance and excellent transparency. As such a transparent support, it is preferable to use a plastic film.
Examples of the polymer forming the plastic film include cellulose acylate (for example, cellulose triacetate such as TAC-TD80U, TD80UF, cellulose diacetate, cellulose acetate propionate, and cellulose acetate butyrate manufactured by Fuji Film Co., Ltd.), polyamide, Polycarbonate, polyester (for example, polyethylene terephthalate, polyethylene naphthalate), polystyrene, polyolefin, norbornene resin (Arton: trade name, manufactured by JSR Corporation), amorphous polyolefin (ZEONEX: trade name, manufactured by Nippon Zeon Corporation), ( (Meth) acrylic resin (ACRYPET VRL20A: trade name, manufactured by Mitsubishi Rayon Co., Ltd., JP-A-2004-70296 and JP-A-2006-17146 And the like described in JP-ring structure-containing acrylic resin). Among these, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, polyethylene terephthalate, and polyethylene naphthalate are preferable, and cellulose triacetate is particularly preferable.

-Hard coat layer-
The antireflection film is preferably provided with a hard coat layer in order to impart physical strength of the film. The hard coat layer may be composed of a laminate of two or more layers.

  The refractive index of the hard coat layer is preferably 1.48 to 1.90, more preferably 1.50 to 1.80, from the optical design for obtaining an antireflection film. Preferably, it is 1.52-1.65. Since there is at least one low refractive index layer on the hard coat layer, when the refractive index is too small, the antireflection property is lowered, and when it is too large, the color of the reflected light tends to be strong.

  The thickness of the hard coat layer is preferably 0.5 μm to 50 μm, and preferably 1 μm to 20 μm, from the viewpoint of imparting sufficient durability and impact resistance to the film. More preferably, the thickness is 2 μm to 15 μm, more preferably 3 μm to 10 μm. Further, the strength of the hard coat layer is preferably 2H or more, more preferably 3H or more, and further preferably 4H or more, in a pencil hardness test. Further, the hard coat layer is preferably as the wear amount of the test piece before and after the test is smaller in the Taber test according to JIS K5400.

  The hard coat layer is preferably formed by a crosslinking reaction or a polymerization reaction of an ionizing radiation curable compound. For example, it can be formed by applying a composition containing an ionizing radiation-curable polyfunctional monomer or polyfunctional oligomer on a transparent support and subjecting the polyfunctional monomer or polyfunctional oligomer to a crosslinking reaction or a polymerization reaction. . The functional group of the ionizing radiation curable polyfunctional monomer or polyfunctional oligomer is preferably a light, electron beam, or radiation polymerizable group, and among them, a photopolymerizable functional group is preferable. Examples of the photopolymerizable functional group include unsaturated polymerizable functional groups such as a (meth) acryloyl group, a vinyl group, a styryl group, and an allyl group. Among these, a (meth) acryloyl group is particularly preferable. As specific compounds, monomers described in paragraphs [0087] and [0088] of JP-A-2006-30740 can be used, and curing described in paragraph [0089] of JP-A-2006-30740 can be used. The method can be used. In the case of photopolymerization, the photopolymerization initiator described in paragraphs [0090] to [0093] of JP-A-2006-30740 can be used.

  The hard coat layer contains matte particles having an average particle size of 1.0 μm to 10.0 μm, preferably 1.5 μm to 7.0 μm, such as inorganic compound particles or resin particles, for the purpose of imparting internal scattering properties. May be. As these particles, for example, the particles described in paragraph [0114] of JP-A-2006-30740 can be used.

  For the binder of the hard coat layer, for the purpose of controlling the refractive index of the hard coat layer, a high refractive index monomer or inorganic fine particles having a size that does not cause light scattering (the primary particle diameter is 10 nm to 200 nm), or both are used. Can be added. In addition to the effect of controlling the refractive index, the inorganic fine particles also have an effect of suppressing curing shrinkage due to a crosslinking reaction. As the inorganic fine particles, for example, a compound described as an inorganic filler in paragraph [0120] of JP-A-2006-30740 can be used.

-Antireflection layer-
The antireflection film is a film in which an antireflection layer is formed on the hard coat layer and utilizes optical interference. Therefore, the antireflection layer preferably has a refractive index and an optical thickness described below. The antireflection layer may be a single layer, but when a lower reflectance is required, a plurality of antireflection layers are laminated. In the lamination of the plurality of antireflection layers, optical interference layers having different refractive indexes may be alternately laminated, or two or more optical interference layers having different refractive indexes may be laminated. Specifically, an embodiment in which only a low refractive index layer is provided on the hard coat layer, an embodiment in which a high refractive index layer and a low refractive index layer are provided in this order on the hard coat layer, an intermediate refractive index layer on the hard coat layer, A mode in which a high refractive index layer and a low refractive index layer are provided in this order is commonly used. Note that low, medium, and high in the refractive index layer are expressions of the relative magnitude relationship of the refractive index.
The refractive index of the low refractive index layer is preferably set lower than the refractive index of the hard coat layer. When the refractive index difference between the low refractive index layer and the hard coat layer is too small, the antireflection property is lowered, and when it is too large, the color of the reflected light tends to be strong. The difference in refractive index between the low refractive index layer and the hard coat layer is preferably 0.01 or more and 0.40 or less, more preferably 0.05 or more and 0.30 or less (paragraph [0080] of JP2009-201727A. 〕reference).
The refractive index and thickness of each layer preferably satisfy the following.

  The refractive index of the low refractive index layer is preferably 1.20 to 1.46, more preferably 1.25 to 1.42, and still more preferably 1.30 to 1.38. . The thickness of the low refractive index layer is preferably 50 nm to 150 nm, and more preferably 70 nm to 120 nm.

  In order to construct the low refractive index layer on the high refractive index layer and produce an antireflection film, the refractive index of the high refractive index layer is preferably 1.55 to 2.40, It is more preferably 1.60 to 2.20, further preferably 1.65 to 2.10, and particularly preferably 1.80 to 2.00.

  When an antireflective film is prepared by coating a medium refractive index layer, a high refractive index layer, and a low refractive index layer in order from the support, the refractive index of the high refractive index layer is 1.65 to 2.40. It is preferable that it is preferably 1.70 to 2.20. The refractive index of the middle refractive index layer is adjusted to be a value between the refractive index of the low refractive index layer and the refractive index of the high refractive index layer. The middle refractive index layer preferably has a refractive index of 1.55 to 1.80. In addition, the thickness of the said high refractive index layer and the said medium refractive index layer can be made into the optical thickness according to the range of refractive index.

-Low refractive index layer-
The low refractive index layer is preferably cured after the layer is formed. The haze of the low refractive index layer is preferably 3% or less, more preferably 2% or less, and still more preferably 1% or less.

A preferred composition for forming the low refractive index layer is preferably a composition containing at least one of the following.
(1) A composition containing a fluorine-containing polymer having a crosslinkable or polymerizable functional group (2) A composition comprising as a main component a hydrolysis-condensation product of a fluorine-containing organosilane material (3) Two or more ethylenes And a composition containing a monomer having an unsaturated group and inorganic fine particles having a hollow structure.

(1) Composition containing a fluorinated polymer having a crosslinkable or polymerizable functional group As the composition containing a fluorinated polymer having a crosslinkable or polymerizable functional group, a fluorine-containing monomer and a crosslinkable or Mention may be made of a copolymer of monomers having a polymerizable functional group.
Among the above-mentioned copolymers, as a copolymer having a main chain composed only of carbon atoms and comprising a fluorine-containing vinyl monomer polymer unit and a polymer unit having a (meth) acryloyl group in the side chain, JP-A P-1 to P-40 described in paragraphs [0043] to [0047] of 2004-45462 can be used. Further, as a fluorine-containing polymer into which a silicone component is introduced for improving scratch resistance and slipperiness, a graft polymer having a polymer unit containing a polysiloxane moiety in the side chain and a fluorine atom in the main chain is disclosed in JP The compounds described in Tables 1 and 2 of paragraphs [0074] to [0076] of 2003-222702 can be used, and the main chain contains an ethylenically unsaturated group-containing fluorine containing a structural unit derived from a polysiloxane compound. As the polymer, compounds described in JP-A No. 2003-183322 can be used.

  As described in JP 2000-17028 A, a curing agent having a polymerizable unsaturated group may be used in combination with the polymer. Moreover, combined use with the compound which has a fluorine-containing polyfunctional polymerizable unsaturated group as described in Unexamined-Japanese-Patent No. 2002-145952 is also preferable. Examples of the compound having a polyfunctional polymerizable unsaturated group include the monomer having two or more ethylenically unsaturated groups. Moreover, the hydrolysis-condensation product of the organolane described in Unexamined-Japanese-Patent No. 2004-170901 is also preferable, and the hydrolysis-condensation product of the organosilane containing a (meth) acryloyl group is especially preferable. These compounds are particularly preferred because they have a large combined effect for improving scratch resistance, particularly when a compound having a polymerizable unsaturated group is used in the polymer body.

  When the polymer itself does not have sufficient curability, the necessary curability can be imparted by blending a crosslinkable compound. For example, when the polymer body contains a hydroxyl group, various amino compounds are preferably used as the curing agent. The amino compound used as the crosslinkable compound is, for example, a compound containing one or both of a hydroxyalkylamino group and an alkoxyalkylamino group in total, specifically, for example, a melamine compound, Examples include urea compounds, benzoguanamine compounds, glycoluril compounds, and the like. For curing these compounds, an organic acid or a salt thereof is preferably used.

(2) Hydrolyzed condensate of fluorine-containing organosilane material The composition mainly composed of the hydrolyzed condensate of the fluorine-containing organosilane compound is also preferable because of its low refractive index and high coating surface hardness. A condensate of a tetraalkoxysilane with a hydrolyzable silanol-containing compound at one or both ends with respect to the fluorinated alkyl group is preferred. Specific compositions are described in JP-A Nos. 2002-265866 and 2002-317152.

(3) A composition containing a monomer having two or more ethylenically unsaturated groups and inorganic fine particles having a hollow structure As yet another preferred embodiment, a low refractive index layer comprising low refractive index particles and a binder can be mentioned. . The low refractive index particles may be organic or inorganic, but particles having pores inside are preferable. Specific examples of the hollow particles are described in silica-based particles described in JP-A No. 2002-79616. The particle refractive index is preferably 1.15 to 1.40, more preferably 1.20 to 1.30. Examples of the binder include monomers having two or more ethylenically unsaturated groups described in the section of the hard coat layer.

  It is preferable to add the polymerization initiator described on the page of the antiglare layer to the low refractive index layer. When a radically polymerizable compound is contained, it is preferable to add 1 part by mass to 10 parts by mass with respect to 100 parts by mass of the compound, and it is more preferable to add 1 part by mass to 5 parts by mass.

  In the low refractive index layer, inorganic particles can be used in combination. In order to impart scratch resistance, fine particles having a particle size of 15% to 150%, preferably 30% to 100%, more preferably 45% to 60% of the thickness of the low refractive index layer can be used. .

  For the purpose of imparting antifouling properties, water resistance, chemical resistance, slipping properties and the like, a known polysiloxane-based or fluorine-based antifouling agent, slipping agent, etc. are appropriately added to the low refractive index layer. be able to.

-High refractive index layer / Medium refractive index layer-
As described above, the antireflection film can be provided with a layer having a high refractive index between the low refractive index layer and the hard coat layer to enhance the antireflection property.
The high refractive index layer and the medium refractive index layer are preferably formed from a curable composition containing high refractive inorganic fine particles and a binder. As the high refractive index inorganic fine particles that can be used here, the high refractive index inorganic fine particles that can be contained to increase the refractive index of the hard coat layer can be used.

  The high refractive index layer and the medium refractive index layer are preferably a binder precursor (for example, an ionizing radiation curable polyfunctional monomer described later) necessary for forming a matrix in a dispersion in which inorganic particles are dispersed in a dispersion medium. And a polyfunctional oligomer), a photopolymerization initiator, and the like to form a coating composition for forming a high refractive index layer and a medium refractive index layer, and coating for forming a high refractive index layer and a medium refractive index layer on a transparent support. Preferably, the composition is applied and cured by a crosslinking reaction or a polymerization reaction of an ionizing radiation curable compound (for example, a polyfunctional monomer or polyfunctional oligomer).

Furthermore, it is preferable to cause the binder of the high refractive index layer and the medium refractive index layer to undergo a crosslinking reaction or a polymerization reaction with the dispersant simultaneously with or after the coating of the layer.
The binder of the high refractive index layer and the medium refractive index layer produced in this way is, for example, the above-mentioned preferred dispersant and ionizing radiation curable polyfunctional monomer or polyfunctional oligomer are crosslinked or polymerized to form a binder. The anionic group of the dispersant is incorporated. Furthermore, the binder of the high refractive index layer and the medium refractive index layer has a function in which the anionic group maintains the dispersed state of the inorganic particles, and the crosslinked or polymerized structure imparts film forming ability to the binder and contains inorganic particles. To improve the physical strength, chemical resistance and weather resistance of the high refractive index layer and medium refractive index layer.

The binder of the high refractive index layer is added in an amount of 5% by mass to 80% by mass with respect to the solid content of the coating composition of the layer.
The content of the inorganic particles in the high refractive index layer is preferably 10% by mass to 90% by mass, more preferably 15% by mass to 80% by mass with respect to the mass of the high refractive index layer. It is still more preferable that it is mass%-75 mass%. Two or more kinds of the inorganic particles may be used in combination in the high refractive index layer.
When the low refractive index layer is provided on the high refractive index layer, the refractive index of the high refractive index layer is preferably higher than the refractive index of the transparent support.

The thickness when the high refractive index layer is used as an optical interference layer is preferably 30 nm to 200 nm, more preferably 50 nm to 170 nm, and still more preferably 60 nm to 150 nm.
The haze of the high refractive index layer and the medium refractive index layer is preferably as low as possible. The haze is preferably 5% or less, more preferably 3% or less, and still more preferably 1% or less.

  In the present invention, the preferable integrated reflectance of the antireflection antiglare film provided with the low refractive index layer is preferably 3.0% or less, more preferably 2.0% or less, and 1.5 More preferably, it is 0.3% or less.

  In the present invention, it is preferable to further reduce the surface free energy of the surface of the low refractive index layer from the viewpoint of improving the antifouling property. Specifically, it is preferable to use a fluorine-containing compound or a compound having a polysiloxane structure for the low refractive index layer. Further, an antifouling layer containing the following compound may be provided on the low refractive index layer separately from the low refractive index layer.

  Examples of the additive having a polysiloxane structure include a reactive group-containing polysiloxane {for example, “KF-100T”, “X-22-169AS”, “KF-102”, “X-22-3701IE”, “X-22”. -164B "," X-22-5002 "," X-22-173B "," X-22-174D "," X-22-167B "," X-22-161AS "(product name), Shin-Etsu “AK-5”, “AK-30”, “AK-32” (trade name), manufactured by Toa Gosei Co., Ltd .; “Silaplane FM0725”, “Silaplane FM0721” (trade name) In addition, it is also preferable to add, for example, manufactured by Chisso Corporation. Moreover, the silicone type compound of Table 2 and Table 3 of Unexamined-Japanese-Patent No. 2003-112383 can also be used preferably. These polysiloxanes are preferably added in the range of 0.1% by mass to 10% by mass of the total solid content of the low refractive index layer, and more preferably 1% by mass to 5% by mass.

<< Preparation Method of Antireflection Film >>
The antireflection film can be formed by the following coating method, but is not limited thereto.

−Preparation work for application−
First, a coating solution containing components for forming each layer such as a hard coat layer and an antireflection layer is prepared. Usually, since the coating liquid is mainly an organic solvent system, it is necessary to suppress the water content to 2% by mass or less and to seal it to suppress the volatilization amount of the solvent. The organic solvent to be used is selected according to the material used for each layer. In order to obtain the uniformity of the coating solution, a stirrer or a disperser is appropriately used.
The prepared coating solution is preferably filtered before coating so as not to cause a coating failure. It is preferable to use a filter having a pore size as small as possible within a range in which the components in the coating solution are not removed, and the filtration pressure is appropriately selected at 1.5 MPa or less. The filtered coating solution is preferably ultrasonically dispersed immediately before coating to defoam and retain the dispersion.
The transparent support used in the present invention may be subjected to a heat treatment for correcting the base deformation or a surface treatment for improving the coating property and the adhesiveness with the coating layer before coating. Specific methods for the surface treatment include corona discharge treatment, glow discharge treatment, flame treatment, acid treatment, alkali treatment, and ultraviolet irradiation treatment. In addition, as described in JP-A-7-333433, it is preferable to provide an undercoat layer.

  Furthermore, it is preferable to provide a dust removing step as a pre-application step, and as a dust removing method used therefor, the method described in paragraph [0119] of JP 2010-32795 A can be used. In addition, it is particularly preferable to remove static electricity on the transparent support before performing such a dust removal step from the viewpoint of increasing dust removal efficiency and suppressing dust adhesion. As such a static elimination method, the method described in paragraph [0120] of JP 2010-32795 A can be used. Furthermore, the flatness of the film may be secured and the adhesiveness may be improved by the methods described in paragraphs [0121] and [0123] of JP2010-32795A.

-Application process-
Each layer of the antireflection film can be formed by the following coating method, but is not limited to this method. Dip coating method, air knife coating method, curtain coating method, roller coating method, wire bar coating method, gravure coating method, extrusion coating method (die coating method) (US Pat. No. 2,681,294, WO 05/123274) A known method such as a microgravure coating method is used, and among these, a microgravure coating method and a die coating method are preferable. The microgravure coating method is described in paragraphs [0125] and [0126] of JP 2010-32795 A, and the die coating method is described in paragraphs [0127] and [0128] of JP 2010-32795 A. These methods can also be used in the present invention. It is preferable in terms of productivity to apply at a speed of 20 m / min or more by using a die coating method.

-Drying process-
The antireflection film is preferably applied directly on the transparent support or via another layer and then conveyed by a web to a heated zone to dry the solvent.
Various knowledges can be used as a method for drying the solvent. As specific knowledge, descriptions in JP-A No. 2001-286817, JP-A No. 2001-314798, JP-A No. 2003-126768, JP-A No. 2003-315505, JP-A No. 2004-34002, etc. Technology.

  Regarding the temperature conditions of the drying zone, the respective conditions described in paragraph [0130] of JP 2010-32795 A, and the conditions of the drying air are described in paragraph [0131] of JP 2010-32795 A, respectively. Can be used.

-Curing process-
The antireflection film can pass through a zone for curing each coating film by ionizing radiation and / or heat as a web after the solvent is dried or at a later stage of drying to cure the coating film. The ionizing radiation species in the present invention is not particularly limited, and is appropriately selected from ultraviolet rays, electron beams, near ultraviolet rays, visible light, near infrared rays, infrared rays, X-rays, and the like according to the type of the curable composition forming the film. However, ultraviolet rays and electron beams are preferred, and ultraviolet rays are particularly preferred because they are easy to handle and high energy can be easily obtained.

  As the ultraviolet light source for photopolymerizing the ultraviolet curable compound, for example, the light source described in paragraph [0133] of JP 2010-32795 A can be used. As the electron beam, for example, the electron beam described in paragraph [0134] of JP 2010-32795 A can be used. Moreover, about irradiation conditions, irradiation light quantity, and irradiation time, the conditions as described in Paragraph [0135] and [0138] of Unexamined-Japanese-Patent No. 2010-32795 can be used, for example. Further, the film surface temperature, oxygen concentration, and oxygen concentration control method before and after the irradiation are described in, for example, paragraphs [0136], [0137], [0139] to [0144] of JP 2010-32795 A. Conditions and methods can be used.

-Handling for continuous production-
In order to continuously produce the antireflection film, a step of continuously feeding a roll-shaped transparent support film, a step of applying and drying a coating liquid, a step of curing a coating film, A step of winding the support film is performed.

  The above process may be performed every time each layer is formed, or a plurality of coating units-drying chambers-curing units may be provided (so-called tandem method) to form each layer continuously.

In order to produce the antireflection film, as described above, simultaneously with the microfiltration operation of the coating solution, the coating process in the coating unit and the drying process performed in the drying chamber are performed in a high clean air atmosphere, and It is preferable that dust and dust on the transparent support film are sufficiently removed before application. The air cleanliness of the coating process and the drying process is preferably class 10 (353 particles / m ³ or less of particles having a size of 0.5 μm or more) based on the standard of air cleanliness in the US Federal Standard 209E, class 1 It is more preferable that the particle size is 35.5 particles / m ³ or less (0.5 μm or more). In addition, it is more preferable that the degree of air cleanliness is high also in the feeding and winding parts other than the coating-drying process.

  In order to maintain the sharpness of the image, it is preferable to adjust the transparency of the transmitted image in addition to adjusting the surface shape of the antireflection film as smoothly as possible. The transmitted image definition of the antireflection film of the present invention is preferably 60% or more. The transmitted image clarity is generally an index indicating the degree of blurring of an image reflected through a film, and the larger this value, the clearer and better the image viewed through the film. The transmitted image definition is preferably 70% or more, and more preferably 80% or more.

The antireflection film can be used as a surface film on the viewing side of an image display device. The image display device can be applied to various display devices such as various liquid crystal display devices, plasma displays, organic ELs, touch panels. Depending on the properties of the outermost surface of the image display device using the antireflection film, an adhesive layer may be provided on the side surface of the antireflection film that does not have the transparent support coating layer, or the support surface may be saponified. It can be attached to an image display device.
As a method for saponifying the surface of the transparent support that does not have a coating layer, for example, the techniques described in paragraphs [0149] to [0160] of JP 2010-32795 A can be used.

Here, an example of the surface capacitive touch panel will be described with reference to FIG. In FIG. 2, the touch panel 10 includes a transparent conductor 12 that uniformly covers the surface of the transparent substrate 11, and an external detection circuit (not shown) is formed on the transparent conductor 12 at the end of the transparent substrate 11. The electrode terminal 18 for electrical connection is formed.
In the figure, reference numeral 13 denotes a transparent conductor serving as a shield electrode, reference numerals 14 and 17 denote protective films, reference numeral 15 denotes an intermediate protective film, and reference numeral 16 denotes an antiglare film.
When an arbitrary point on the transparent conductor 12 is touched with a finger, the transparent conductor 12 is grounded through the human body at the touched point, and changes to a resistance value between each electrode terminal 18 and the ground line. Occurs. The change of the resistance value is detected by the external detection circuit, and the coordinates of the touched point are specified.

Another example of the surface capacitive touch panel will be described with reference to FIG. In FIG. 3, the touch panel 20 includes a transparent conductor 22 and a transparent conductor 23 disposed so as to cover the surface of the transparent substrate 21, and an insulating layer 24 that insulates the transparent conductor 22 and the transparent conductor 23. The insulating cover layer 25 that generates capacitance between the contact object such as a finger and the transparent conductor 22 or the transparent conductor 23 detects the position of the contact object such as the finger. Depending on the configuration, the transparent conductors 22 and 23 may be configured integrally, and the insulating layer 24 or the insulating cover layer 25 may be configured as an air layer.
When the insulating cover layer 25 is touched with a finger or the like, the capacitance value between the finger and the transparent conductor 22 or the transparent conductor 23 changes. This change in capacitance value is detected by the external detection circuit, and the coordinates of the touched point are specified.
Further, with reference to FIG. 4, the touch panel 20 as a projection capacitive touch panel will be schematically described through an arrangement in which the transparent conductor 22 and the transparent conductor 23 are viewed from the plane.
The touch panel 20 is provided with a plurality of transparent conductors 22 capable of detecting positions in the X-axis direction and a plurality of transparent conductors 23 in the Y-axis direction so as to be connectable to external terminals. The transparent conductor 22 and the transparent conductor 23 are in contact with a plurality of contact objects such as fingertips, and contact information can be input at multiple points.
When an arbitrary point on the touch panel 20 is touched with a finger, the coordinates in the X-axis direction and the Y-axis direction are specified with high positional accuracy.
In addition, as other structures, such as a transparent substrate and a protective layer, the structure of the said surface type capacitive touch panel can be selected suitably, and can be applied. Moreover, although the example of the pattern of the transparent conductor by the some transparent conductor 22 and the some transparent conductor 23 was shown in the touch panel 20, the shape, arrangement | positioning, etc. are not restricted to these.

An example of the resistive touch panel will be described with reference to FIG. In FIG. 5, the touch panel 30 can contact the transparent conductor 32 via the substrate 31 on which the transparent conductor 32 is disposed, the spacers 36 disposed on the transparent conductor 32, and the air layer 34. A transparent conductor 33 and a transparent film 35 disposed on the transparent conductor 33 are supported.
When the touch panel 30 is touched from the transparent film 35 side, the transparent film 35 is pressed, the pressed transparent conductor 32 and the transparent conductor 33 come into contact with each other, and a potential change at this position is not illustrated. By detecting with a circuit, the coordinates of the touched point are specified.

(Integrated solar cell)
The integrated solar cell of the present invention uses the conductive film-forming laminate of the present invention.
There is no restriction | limiting in particular as said integrated solar cell (henceforth a solar cell device), What is generally used as a solar cell device can be used. For example, a single crystal silicon solar cell device, a polycrystalline silicon solar cell device, an amorphous silicon solar cell device composed of a single junction type or a tandem structure type, gallium arsenide (GaAs), indium phosphorus (InP), etc. III-V compound semiconductor solar cell devices, II-VI compound semiconductor solar cell devices such as cadmium tellurium (CdTe), copper / indium / selenium system (so-called CIS system), copper / indium / gallium / selenium system ( So-called CIGS-based), copper / indium / gallium / selenium / sulfur-based (so-called CIGS-based) I-III-VI group compound semiconductor solar cell devices, dye-sensitized solar cell devices, organic solar cell devices, etc. Can be mentioned. Among these, in the present invention, the solar cell device is an amorphous silicon solar cell device constituted by a tandem structure type or the like, a copper / indium / selenium system (so-called CIS system), copper / indium / gallium / A selenium-based (so-called CIGS-based), copper / indium / gallium / selenium / sulfur-based (so-called CIGS-based) I-III-VI group compound semiconductor solar cell device is preferable.

  In the case of an amorphous silicon solar cell device composed of a tandem structure type or the like, amorphous silicon, a microcrystalline silicon thin film layer, or a thin film containing germanium therein, and further, a tandem structure of these two or more layers as a photoelectric conversion layer Used. For film formation, plasma CVD or the like is used.

  Examples of the present invention will be described below, but the present invention is not limited to these examples. In addition, this Example is an example which uses the "laminated body for electrically conductive film formation" of this invention as a "transparent conductor, and a" conductive fiber content layer "corresponds to a" conductive layer. "

(Synthesis Example 1)
<Synthesis of Binder (A-1)>
7.79 g of methacrylic acid (MAA) and 37.21 g of benzyl methacrylate (BzMA) are used as monomer components constituting the copolymer, and 0.5 g of azobisisobutyronitrile (AIBN) is used as a radical polymerization initiator. And a polymerization reaction in 55.00 g of propylene glycol monomethyl ether acetate (PGMEA) using these as a solvent to obtain a PGMEA solution (solid content concentration: 45% by mass) of the binder (A-1) represented by the following formula: It was. The polymerization temperature was adjusted to 60 to 100 ° C.
As a result of measuring the molecular weight using gel permeation chromatography (GPC), the weight average molecular weight (Mw) in terms of polystyrene was 30,000, and the molecular weight distribution (Mw / Mn) was 2.21.

(Preparation Example 1)
-Preparation of silver nanowire aqueous dispersion-
The following additive solutions A, G, and H were prepared in advance.
[Additive liquid A]
0.51 g of silver nitrate powder was dissolved in 50 mL of pure water. Then, 1N ammonia water was added until it became transparent. And pure water was added so that the whole quantity might be 100 mL.
[Additive liquid G]
An additive solution G was prepared by dissolving 0.5 g of glucose powder in 140 mL of pure water.
[Additive liquid H]
Additive solution H was prepared by dissolving 0.5 g of HTAB (hexadecyl-trimethylammonium bromide) powder in 27.5 mL of pure water.

Next, a silver nanowire aqueous dispersion was prepared as follows.
410 mL of pure water was placed in a three-necked flask, and 82.5 mL of additive solution H and 206 mL of additive solution G were added using a funnel while stirring at 20 ° C. (first stage). To this solution, 206 mL of additive solution A was added at a flow rate of 2.0 mL / min and a stirring rotation speed of 800 rpm (second stage). Ten minutes later, 82.5 mL of additive liquid H was added (third stage). Thereafter, the internal temperature was raised to 75 ° C. at 3 ° C./min. Then, the stirring rotation speed was reduced to 200 rpm and heated for 5 hours.
After cooling the obtained aqueous dispersion, an ultrafiltration module SIP1013 (manufactured by Asahi Kasei Co., Ltd., molecular weight cut off 6,000), a magnet pump, and a stainless steel cup were connected with a silicone tube to obtain an ultrafiltration device. .
The silver nanowire dispersion (aqueous solution) was put into a stainless steel cup, and ultrafiltration was performed by operating a pump. When the filtrate from the module reached 50 mL, 950 mL of distilled water was added to the stainless steel cup for washing. The above washing was repeated until the conductivity reached 50 μS / cm or less, and then concentrated to obtain a silver nanowire aqueous dispersion.
About the obtained silver nanowire of Preparation Example 1, the average minor axis length, the average major axis length, the ratio of silver nanowires having an aspect ratio of 10 or more, and the silver nanowire minor axis length were as follows: The coefficient of variation was measured. The results are shown in Table 1.

<Average minor axis length (average diameter) and average major axis length of silver nanowires>
300 silver nanowires were observed using a transmission electron microscope (TEM; JEM-2000FX, manufactured by JEOL Ltd.), and the average minor axis length and average major axis length of the silver nanowires were determined.

<Coefficient of variation of minor axis length of silver nanowires>
Using a transmission electron microscope (TEM; JEM-2000FX, manufactured by JEOL Ltd.), 300 short axis lengths of the silver nanowires were observed, and the amount of silver transmitted through the filter paper was measured. Of silver nanowires having a major axis length of 5 μm or more was determined as the ratio (%) of silver nanowires having an aspect ratio of 10 or more.
The silver nanowires were separated when determining the ratio of silver nanowires using a membrane filter (Millipore, FALP 02500, pore size 1.0 μm).

Example 1
<Sample No. 101>
-Preparation of MFG dispersion (Ag-1) of silver nanowires-
Polyvinylpyrrolidone (K-30, manufactured by Wako Pure Chemical Industries, Ltd.) and 1-methoxy-2-propanol (MFG) are added to the silver nanowire aqueous dispersion of Preparation Example 1, and after centrifuging, decantation is performed. The water in the supernatant was removed, MFG was added, redispersion was performed, and the operation was repeated three times to obtain an MFG dispersion (Ag-1) of silver nanowires. The final MFG addition amount was adjusted so that the silver content was 1% by mass of silver.

-Preparation of composition for negative conductive layer-
0.241 parts by mass of binder (A-1) of Synthesis Example 1, KAYARAD DPHA (mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, Nippon Kayaku Co., Ltd.) 0.252 parts by mass, IRGACURE 379 (photopolymerization) Initiator, manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.0252 parts by mass, EHPE-3150 (manufactured by Daicel Chemical Co., Ltd.) 0.0237 parts by mass as a crosslinking agent, MegaFuck F781F (produced by DIC Corporation) 0.0003 50 parts by mass, 0.9611 parts by mass of propylene glycol monomethyl ether acetate (PGMEA), 44.3 parts by mass of 1-methoxy-2-propanol (MFG), and 54. MFG dispersion (Ag-1) of the silver nanowires. Add 1 part by mass, stir, negative type A composition for a conductive layer was prepared.

-Formation of conductive layer-
By applying and drying the obtained negative conductive layer composition on a polyethylene terephthalate (PET) film having a thickness of 75 μm subjected to corona discharge treatment so that the amount of coated silver is 0.05 g / m ^2. A conductive layer having a thickness of 0.05 μm was formed. As described above, the sample No. 101 transparent conductors were produced. The obtained sample No. The mass ratio of silver to the dispersion medium in the conductive layer 101 was 1.0.

<Sample No. 102>
Sample No. 101, except that a soluble protective layer having an average thickness of 0.8 μm was formed by applying a composition for soluble protective layer having the following composition on the conductive layer and drying it. In the same manner as in Sample 101, Sample No. 102 transparent conductors were produced. The average thickness of the soluble protective layer is an average value of values measured over a region having a length of 50 μm by cross-sectional observation with a scanning electron microscope (manufactured by Hitachi High-Technologies Corporation, S3400N) (the same applies to the following samples). Measured).
-Preparation of composition for soluble protective layer-
・ Polyvinylpyrrolidone (PVP, Wako Pure Chemical Industries, PVP K-30) ... 10g
・ Ion exchange water ... 90g
・ Polyoxyethylene lauryl ether (surfactant) ... 0.05g
The above composition was mixed and stirred to prepare a soluble protective layer composition.

<Sample No. 103>
Sample No. 101, except that a soluble protective layer having an average thickness of 0.8 μm was formed by applying a composition for soluble protective layer having the following composition on the conductive layer and drying it. In the same manner as in Sample 101, Sample No. 103 transparent conductors were produced.
-Preparation of soluble protective layer composition-
・ Polyvinyl alcohol (PVA, PVA205 (saponification rate = 88%); manufactured by Kuraray Co., Ltd.) ... 10 g
・ Ion exchange water ... 90g
・ Polyoxyethylene lauryl ether (surfactant) ... 0.05g
The above composition was mixed and stirred to prepare a soluble protective layer composition.

<Sample No. 104>
Sample No. 101, except that a soluble protective layer composition having the following composition was applied on the conductive layer and dried to form a soluble protective layer having an average thickness of 0.8 μm. In the same manner as in Sample 101, Sample No. 104 transparent conductors were produced.
-Preparation of soluble protective layer composition-
・ Hydroxyethyl cellulose (HEC, manufactured by Daicel Chemical Industries, Ltd.) ... 10g
・ Ion exchange water ... 90g
The above composition was mixed and stirred to prepare a soluble protective layer composition.

<Sample No. 105>
Sample No. 101, except that a soluble protective layer having an average thickness of 0.8 μm was formed by applying a composition for soluble protective layer having the following composition on the conductive layer and drying it. In the same manner as in Sample 101, Sample No. 105 transparent conductors were produced.
-Preparation of soluble protective layer composition-
・ Gelatin (Nitta Gelatin Co., Ltd., Alkaline Ocein Gelatin) ... 5g
・ Ion exchange water: 95g
・ Polyoxyethylene lauryl ether (surfactant) ... 0.05g
The above composition was mixed and stirred to prepare a soluble protective layer composition.

<Sample No. 106>
Sample No. 101, except that a soluble protective layer having an average thickness of 0.8 μm was formed by applying a composition for soluble protective layer having the following composition on the conductive layer and drying it. In the same manner as in Sample 101, Sample No. 106 transparent conductors were produced.
-Preparation of soluble protective layer composition-
・ Polyvinylpyrrolidone (PVP, Wako Pure Chemical Industries, PVP K-30) ... 10g
・ Propylene glycol monomethyl ether (PGME) ... 90g
・ Polyoxyethylene lauryl ether (surfactant) ... 0.05g
The above composition was mixed and stirred to prepare a soluble protective layer composition.

<Sample No. 107>
Sample No. 102, except that the average thickness of the soluble protective layer was changed to 2.5 μm. In the same manner as in Sample No. 102, Sample No. 107 transparent conductors were produced.

<Sample No. 108>
Sample No. 102, except that the average thickness of the soluble protective layer was changed to 0.1 μm. In the same manner as in Sample No. 102, Sample No. 108 transparent conductors were produced.

<Sample No. 109>
Sample No. 101, except that a soluble protective layer having an average thickness of 0.8 μm was formed by applying a composition for soluble protective layer having the following composition on the conductive layer and drying it. In the same manner as in Sample 101, Sample No. 109 transparent conductors were produced.
-Preparation of composition for soluble protective layer-
-Binder (A-1) of Synthesis Example 1 (MAA / BzMA copolymer) ... 10.0 g
・ Propylene glycol monomethyl ether (PGME) ... 90g
The above composition was mixed and stirred to prepare a water-insoluble soluble protective layer composition.

<Sample No. 110>
Sample No. 101, except that a soluble protective layer having an average thickness of 0.8 μm was formed by applying a composition for soluble protective layer having the following composition on the conductive layer and drying it. In the same manner as in Sample 101, Sample No. 110 transparent conductors were produced.
-Preparation of composition for soluble protective layer-
4.44 parts by mass of binder (A-1) of Synthesis Example 1, KAYARAD DPHA (mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.), 4.65 parts by mass, IRGACURE 379 (photopolymerization) Initiator, manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.46 parts by mass, EHPE-3150 (manufactured by Daicel Chemical Co., Ltd.) 0.44 parts by mass as a crosslinking agent, MegaFuck F781F (produced by DIC Corporation) 0.006 Mass parts and 90.0 parts by mass of propylene glycol monomethyl ether (PGME) were added and stirred to prepare a composition for a soluble protective layer having a negative resist composition.

<Sample No. 111>
Sample No. 101, except that a soluble protective layer having an average thickness of 0.8 μm was formed by applying and drying a composition for a soluble protective layer having the following composition on the conductive layer. In the same manner as in Sample 101, Sample No. 111 transparent conductors were produced.
-Preparation of composition for soluble protective layer-
4.44 parts by mass of binder (A-1) of Synthesis Example 1, KAYARAD DPHA (mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, Nippon Kayaku Co., Ltd.) 0.252 parts by mass, IRGACURE 379 (photopolymerization) Initiator, manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.46 parts by mass, EHPE-3150 (manufactured by Daicel Chemical Co., Ltd.) 0.44 parts by mass as a crosslinking agent, MegaFuck F781F (produced by DIC Corporation) 0.006 Part by mass and 90.0 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) were added and stirred to prepare a negative soluble protective layer composition.

<Sample No. 112>
Sample No. 101, except that a soluble protective layer having an average thickness of 0.8 μm was formed by applying a composition for soluble protective layer having the following composition on the conductive layer and drying it. In the same manner as in Sample 101, Sample No. 112 transparent conductors were produced.
-Preparation of composition for soluble protective layer-
KAYARAD DPHA (mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.) 10.0 parts by mass, IRGACURE 379 (photopolymerization initiator, manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.5 mass And 90.0 parts by mass of methyl ethyl ketone were added and stirred to prepare a composition for a soluble protective layer having a hard coat composition.

  Next, for each of the obtained transparent conductors, scratch resistance, light transmittance, surface resistance, patternability, and the mass ratio of silver and the dispersion medium after the development process were evaluated as follows. The results are shown in Table 1.

<Scratch resistance>
Pencil scratch coating film hardness tester (Toyo Incorporated) in which each of the transparent conductors produced was set according to JIS K5600-5-4 with a pencil for pencil inspection (hardness HB and hardness B) certified by the Japan Paint Inspection Association. After scratching over a length of 10 mm with a load of 500 g using Seiki Seisakusho, model NP, exposure and development were performed under the following conditions, and the scratched portion was digital microscope (VHX-600, manufactured by Keyence Corporation, magnification) 2,000 times) and the following ranking was performed.
〔Evaluation criteria〕
○: Scratches are not recognized.
Δ: Although scratch marks are observed, conductive fibers remain, and exposure of the substrate surface is not observed.
X: Scratches are recognized, the conductive fibers are scraped, and exposure of the substrate surface is observed.

Here, exposure and development were performed under the following conditions.
<Exposure and development conditions>
Each obtained transparent conductor was uniformly exposed at 100 mJ / cm ² (illuminance 20 mW / cm ² ) using a high-pressure mercury lamp i-line (365 nm), and then a potassium hydroxide developer CDK-1 (Fuji Shower development is performed for 30 seconds with 1.0% by weight developer (1 part by weight of CDK-1, 99 parts by weight of pure water, 25 ° C.) of Film Electronics Materials Co., Ltd., and ion exchange After rinsing with water for 20 seconds, it was dried.

<Measurement of light transmittance>
A non-scratched portion of each sample exposed and developed under the above conditions was measured at a measurement angle of 0 ° with respect to the CIE visibility function y under a C light source using a haze guard plus manufactured by Gardner.

<Measurement of surface resistance value>
The surface resistance value (SR) was measured using a surface resistance meter (Loresta-GP MCP-T600, manufactured by Mitsubishi Chemical Corporation) for a portion of each sample that was exposed and developed under the above conditions. Sample No. The ratio (SR / SR101) of the surface resistance value of each sample to the surface resistance value (SR101) after drying of 101 was determined and ranked according to the following criteria.
〔Evaluation criteria〕
○: SR / SR101 <1.5
Δ: 1.5 ≦ SR / SR101 <5.0
×: 5.0 ≦ SR / SR101

<Evaluation of patterning properties>
Adhesion exposure was performed using an optical mask including a stripe pattern (line / space = 30 μm / 30 μm) for evaluating patterning characteristics. The exposure was performed at 100 mJ / cm ² (illuminance 20 mW / cm ² ) using a high-pressure mercury lamp i-line (365 nm). Each sample after the exposure was prepared by adding 1.0% by mass of a potassium hydroxide developer CDK-1 (manufactured by FUJIFILM Electronics Materials) (1 part by mass of CDK-1 and 99 parts by mass of pure water). It was developed with a diluted solution (25 ° C.), further rinsed with ion exchange water (25 ° C.), and then dried. Development was performed by shower development, and the shower pressure was 0.04 MPa in both the development process and the rinsing process. The development time was 30 seconds and 60 seconds, and the rinse time was 15 seconds. The pattern part of the obtained sample was observed with a digital microscope (VHX-600, manufactured by Keyence Corporation, magnification: 2,000 times), and the patterning property was evaluated according to the following criteria.
〔Evaluation criteria〕
○: Development residue in unexposed areas is not recognized and patterning property is good.
(Triangle | delta): Although most unexposed parts have been removed by image development, some image development residues are recognized.
X: Most of the unexposed portions were not removed by development, and patterning was poor.

<Measurement of mass ratio of dispersion medium and silver after development process>
The conductive layer is collected from the sample after exposure and development, and the ratio of the dispersion medium amount after development (A) to the silver mass (B) (A / B) was calculated. Here, exposure and development were performed under the same conditions as in the scratch resistance evaluation. The silver content was measured with an ICP emission spectrometer (ICPS-8000, manufactured by Shimadzu Corporation).

* Impossible to measure: 100,000Ω / □ or more

(Example 2)
-Fabrication of touch panel-
Sample No. Using 102 transparent conductors, “Latest Touch Panel Technology” (issued July 6, 2009, Techno Times Co., Ltd.), supervised by Yuji Mitani, “Technology and Development of Touch Panel”, CM Publishing (December 2004) ), “FPD International 2009 Forum T-11 Lecture Textbook”, “Cypress Semiconductor Corporation Application Note AN2292” and the like, and the touch panel was manufactured. Here, Sample No. No. 102 was used for touch panel production, which was exposed and developed under the same conditions as in the scratch resistance evaluation of Example 1.
When the manufactured touch panel is used, it is excellent in visibility by improving the light transmittance, and for input of characters etc. or screen operation by at least one of bare hands, gloves-fitted hands, pointing tools by improving conductivity It was found that a touch panel with excellent responsiveness can be manufactured. The touch panel includes a so-called touch sensor and a touch pad.

(Example 3)
<Production of integrated solar cell>
-Fabrication of amorphous solar cells (super straight type)-
On the glass substrate, the sample No. A transparent conductor 103 was formed, and exposure and development were performed under the same conditions as in the scratch resistance evaluation of Example 1. A p-type having a thickness of 15 nm was formed on the transparent conductor by plasma CVD, an i-type having a thickness of 350 nm was formed on the p-type, and an n-type amorphous silicon having a thickness of 30 nm was formed on the i-type. A 20-nm-thick gallium-doped zinc oxide layer was formed as a back-surface reflecting electrode on the n-type amorphous silicon, and a 200-nm-thick silver layer was formed on the gallium-doped zinc oxide layer to produce an amorphous solar cell.

Example 4
<Production of integrated solar cell>
-Fabrication of CIGS solar cells (substrate type)-
A molybdenum electrode having a thickness of about 500 nm by a DC magnetron sputtering method on a glass substrate, and Cu (In _0.6 Ga _0.4) which is a chalcopyrite semiconductor material having a thickness of 2.5 μm by a vacuum deposition method on the electrode. ) A cadmium sulfide thin film having a thickness of 50 nm was formed on the Se ₂ thin film and the Cu (In _0.6 Ga _0.4 ) Se ₂ thin film by a solution deposition method. On top of the cadmium sulfide thin film, a sample No. 104 transparent conductors were formed, and exposure and development were performed under the same conditions as in the scratch resistance evaluation of Example 1. The CIGS solar cell was produced by the above.

<Evaluation of solar cell characteristics (conversion efficiency)>
About the produced solar cell of Example 3 and 4, the solar cell characteristic (conversion efficiency) was measured by irradiating the artificial sunlight of AM1.5 and 100 mW / cm < ² >. The results are shown in Table 3.

  Since the laminate for forming a conductive film of the present invention is easily electrically connected to external wiring, has excellent surface conductivity, and has improved scratch resistance, for example, touch panel, antistatic for display, electromagnetic wave shield, etc. It can be widely used for electrodes for organic EL or inorganic EL displays, electronic paper, electrodes for flexible displays, antistatics for flexible displays, solar cells, and other various devices.

10, 20, 30 Touch panel 11, 21, 31 Transparent substrate 12, 13, 22, 23, 32, 33 Transparent conductor 24 Insulating layer 25 Insulating cover layer 14, 17 Protective film 15 Intermediate protective film 16 Antiglare film 18 Electrode terminal 33 spacer 34 air layer 35 transparent film 36 spacer 101 display 102 transparent adhesive 103 second electrode 104 transparent substrate 105 first electrode 106 transparent adhesive 107 transparent film 108 hard coat layer 109 antireflection layer 110 protective resin layer 120 reflection Prevention film 130 Touch panel

Claims (15)

  A conductive film comprising: a base material; a conductive fiber-containing layer containing at least conductive fibers on the base material; and a soluble protective layer containing at least a water-soluble polymer on the conductive fiber-containing layer. Forming laminate.   The laminate for forming a conductive film according to claim 1, wherein the soluble protective layer has an average thickness of 0.1 μm to 5 μm.   The conductive film-forming laminate according to claim 1, wherein the water-soluble polymer is at least one selected from polyvinyl pyrrolidone, polyvinyl alcohol, gelatin, and a cellulose derivative.   The conductive fiber-forming laminate according to any one of claims 1 to 3, wherein the conductive fibers are metal nanowires.   The laminate for forming a conductive film according to claim 4, wherein the metal nanowire is made of any of silver and an alloy of silver and a metal other than silver.   The laminated body for electrically conductive film formation in any one of Claim 1 to 5 in which an electroconductive fiber content layer contains a dispersion medium.   The laminate for forming a conductive film according to any one of claims 1 to 6, wherein the conductive fiber-containing layer has a surface resistance of 0.1Ω / □ to 10,000Ω / □.   The laminate for forming a conductive film according to claim 1, which has a light transmittance of 70% or more. A conductive fiber-containing layer forming step of forming a conductive fiber-containing layer by applying a conductive fiber-containing layer composition containing at least conductive fibers on a substrate;
A soluble protective layer forming step of forming a soluble protective layer by applying a composition for a soluble protective layer containing at least a water-soluble polymer on the conductive fiber-containing layer;
The manufacturing method of the laminated body for electrically conductive film formation characterized by including.   The manufacturing method of the laminated body for electrically conductive film formation of Claim 9 including the soluble protective layer removal process which provides a solvent to a soluble protective layer and removes this soluble protective layer.   The method for producing a laminate for forming a conductive film according to claim 10, wherein the solvent is one of water and an alkaline solution. An exposure step of exposing at least the conductive fiber-containing layer in the laminate for forming a conductive film according to any one of claims 1 to 8,
A removal step of removing at least one of the exposed portion and the non-exposed portion in the conductive fiber-containing layer and the soluble protective layer by applying a solvent;
A pattern forming method comprising:   The pattern forming method according to claim 12, wherein the solvent is an alkaline solution.   A touch panel using the conductive film-forming laminate according to claim 1.   An integrated solar cell comprising the conductive film-forming laminate according to claim 1.