JP2012169072A - Laminate for forming conductive film, method of forming conductive film, conductive film, conductive element, touch panel and integrated solar cell - Google Patents

Abstract

A laminate for forming a conductive film that is excellent in transparency even after patterning by development and has both conductivity and film strength, a method for producing the same, a conductive film excellent in durability and conductivity using the laminate, A touch panel display using the conductive film and an integrated solar cell are provided.
A photosensitive layer including a conductive fiber having a minor axis diameter of 150 nm or less, a polymer, a compound having an ethylenically unsaturated double bond, and a photopolymerization initiator is provided on the substrate, and the photosensitive layer includes the photosensitive layer. The laminated body for electrically conductive film formation with which the mass P of the polymer contained, the mass M of the compound which has an ethylenically unsaturated double bond, and the mass C of an electroconductive fiber satisfy | fill the following relationship. 2.0 ≦ P / C ≦ 10.0, 0.3 ≦ M / C ≦ 1.5
[Selection figure] None

Description

  The present invention relates to a laminate for forming a conductive film, a method for forming a conductive film using the laminate, a conductive film obtained by the formation method, a conductive element, a touch panel including the conductive film, and an integrated solar cell. About.

  In recent years, a transparent conductive film using metal nanowires produced by a polyol method has been proposed (see, for example, Patent Document 1). This transparent conductive film is a two-layer coating of a conductive layer formed by applying a silver nanowire aqueous dispersion and a photosensitive layer formed by applying a photosensitive composition containing a photosensitive compound and a photopolymerization initiator. It is a patterned conductive film obtained by performing, and then removing the uncured portion by pattern exposure and developing solution. However, since this transparent conductive film has a two-layer structure in which a silver nanowire dispersion liquid is applied and then a photosensitive composition is applied, the coating process must be repeated, and the upper part of the conductive layer. In addition, since the non-conductive pattern forming layer is located, the surface conductivity is liable to be impaired. Furthermore, this method has a problem that it is difficult to form a conductive pattern of a transfer system. In other words, when pattern formation is performed by transferring the conductive layer formed on the temporary support having transferability to another substrate surface, there is a concern that transfer failure may occur due to insufficient adhesion of the conductive layer. Alternatively, since the photosensitive layer needs to be transferred onto the conductive layer, there is a problem that the material structure becomes complicated.

  For this reason, a conductive film for pattern formation that has a single layer structure, excellent surface conductivity, and can be suitably applied to a transfer method is also desired. However, in the case of forming a conductive film material having pattern formability, in general, the conductivity depends on the content and dispersion state of the conductive material, and the film strength is a binder polymer or a dispersion medium of the conductive material. Since it depends on the content of the polymerizable compound, it is difficult to make both compatible, and at present, sufficient performance has not been obtained.

US Application Publication No. 2007/0074316

An object of the present invention is to solve the above-described problems and achieve the following objects. That is, an object of the present invention is for forming a conductive film capable of forming a patterned conductive film, which has a good pattern formability, maintains a high level of conductivity and film strength, and is useful for a transfer method. An object of the present invention is to provide a laminate, a conductive element, a conductive film formation method using the conductive film formation laminate, and a conductive film excellent in conductivity and film strength obtained by the formation method.
A further object of the present invention is to provide a touch panel excellent in responsiveness and durability using the conductive film, and an integrated solar cell excellent in power generation efficiency and durability.

As a result of investigations, the inventors can solve the above problems by controlling the content ratio of the polymer and the conductive fiber as the photosensitive material, the compound having an ethylenically unsaturated double bond and the conductive fiber. The present invention has been completed.
That is, the means for solving the above-described problems are as follows.
<1> On a base material, a conductive fiber having a minor axis diameter of 150 nm or less (hereinafter, simply referred to as “conductive fiber”), a polymer, a compound having an ethylenically unsaturated double bond (hereinafter, “polymerizable compound” as appropriate) And a photosensitive layer containing a photopolymerization initiator, and contained in the photosensitive layer, the mass P of the polymer, the mass M of the compound having an ethylenically unsaturated double bond, and the conductivity It is the laminated body for electrically conductive film formation in which the mass C of a conductive fiber satisfy | fills the following relationship.
2.0 ≦ P / C ≦ 10.0
0.3 ≦ M / C ≦ 1.5

<2> The conductive film-forming laminate according to <1>, wherein the photosensitive layer has a thickness of 0.01 to 0.3 μm.
<3> The total mass B of the dispersion medium, which is a component other than the conductive fibers contained in the photosensitive layer, and the mass C of the conductive fibers satisfy the following relationship <1> or <2> The laminated body for electrically conductive film formation of description.
2.5 ≦ B / C ≦ 15.0
<4> The conductive film-forming laminate according to any one of <1> to <3>, wherein the conductive fiber is a metal nanowire.
<5> The laminate for forming a conductive film according to <4>, wherein the metal nanowire is made of silver or 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 polymer has an average acid value of 50 mgKOH / g or more and 200 mgKOH / g or less.
<7> The conductive material according to any one of <1> to <6>, wherein the compound having an ethylenically unsaturated double bond is a monomer or an oligomer having a plurality of ethylenically unsaturated double bonds in the molecule. Laminate for film formation.
<8> A conductive fiber having a minor axis diameter of 150 nm or less, a polymer, a compound having an ethylenically unsaturated double bond, and a photopolymerization initiator, a polymer mass P, an ethylenically unsaturated double bond on a substrate. In the laminated body formation process which forms the photosensitive layer which the mass M of the compound which has, and the mass C of electroconductive fiber contain in the quantity which satisfy | fills the relationship of following formula (1) and Formula (2), and the obtained laminated body An exposure step of exposing at least a part of the photosensitive layer.
2.0 ≦ P / C ≦ 10.0 Formula (1)
0.3 ≦ M / C ≦ 1.5 Formula (2)

<9> The laminate-forming step includes a conductive fiber having a minor axis diameter of 150 nm or less, a polymer, a compound having an ethylenically unsaturated double bond, and a photopolymerization initiator, a polymer mass P, an ethylenically unsaturated double The process of apply | coating the coating liquid composition for photosensitive layer formation which the mass M of the compound which has a coupling | bonding, and the mass C of an electroconductive fiber satisfy | fill the relationship of following formula (1) and Formula (2) on a base material. Or a conductive fiber having a minor axis diameter of 150 nm or less, a polymer, a compound having an ethylenically unsaturated double bond, and a photopolymerization initiator, a polymer mass P, a compound having an ethylenically unsaturated double bond The photosensitive layer in the laminate for forming a conductive film having the photosensitive layer including the mass M and the mass C of the conductive fiber satisfying the relationship of the following formulas (1) and (2) is provided on the substrate. The process according to <8>, which is a transfer process Conductive film forming method.
<10> The method for forming a conductive film according to claim 9, further comprising a solvent application step of applying a solvent to the photosensitive layer and reducing a dispersion medium contained in the exposed photosensitive layer after the exposure step.
<11> The method for forming a conductive film according to <9> or <10>, further including a development step of removing a non-exposed portion by applying a solvent to the exposed photosensitive layer after the exposure step.
<12> The film thickness of the photosensitive layer in the exposed region in the conductive film-forming laminate after the solvent application step is smaller than the film thickness of the photosensitive layer before the solvent application step <10> or <11>. The method for forming a conductive film according to 11>.
<13> The method for forming a conductive film according to any one of <8> to <12>, wherein the solvent is a solvent selected from water and an alkaline solution.

<14> A conductive film obtained by the conductive film forming method according to any one of <8> to <13>.
<15> The conductive film according to <14>, wherein the sheet resistance is 0.1 to 10,000 Ω / □.
<16> The conductive film according to <14> or <15>, which has a light transmittance of 70% or more.
<17> A compound containing a conductive fiber having a minor axis diameter of 150 nm or less, a polymer, a compound having an ethylenically unsaturated double bond, and a photopolymerization initiator, and having a mass P of the polymer and the ethylenically unsaturated double bond. The conductive element in which the mass M of the conductive fiber and the mass C of the conductive fiber satisfy the following relationship.
2.0 ≦ P / C ≦ 10.0
0.3 ≦ M / C ≦ 1.5
<18> A touch panel comprising the conductive film according to any one of <14> to <16>.
<19> An integrated solar cell comprising the conductive film according to any one of <14> to <16>.
In addition, the conductive element in the present invention includes a material that satisfies the above-mentioned specific relationship, and its use is arbitrary. When forming a layer made of a conductive element, even if it has a base material, It may not have, and may be patterned or may not be patterned.

According to the present invention, using the conductive film forming laminate, the conductive element, and the conductive film forming laminate capable of forming a patterned conductive film in which conductivity and film strength are maintained at high levels. A conductive film excellent in conductivity and film strength obtained by the conductive film forming method and the forming method can be provided.
In addition, according to the present invention, it is possible to provide a touch panel excellent in responsiveness and durability using the conductive film of the present invention, and an integrated solar cell excellent in power generation efficiency and durability.

FIG. 1 is a schematic view showing an example of the conductive layer transfer material of the present invention. 2A to 2C are explanatory views for explaining a transfer method using the conductive layer transfer material of the present invention. FIG. 3 is a schematic cross-sectional view showing an example of a touch panel. 4A to 4D are process diagrams illustrating an example of a method for manufacturing a cell of a CIGS thin film solar battery.

Hereinafter, the conductive composition of the present invention will be described in detail.
Hereinafter, although described based on typical embodiment of this invention, unless it exceeds the main point of this invention, this invention is not limited to described embodiment.
In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

In this specification, the term “light” is used as a concept including not only visible light but also electron beams such as ultraviolet rays, X-rays, and gamma rays.
In this specification, “(meth) acrylic acid” is used to indicate either or both of acrylic acid and methacrylic acid, and “(meth) acrylate” is used to indicate either or both of acrylate and methacrylate. There is.
In addition, unless otherwise specified, the content is expressed in terms of mass, and unless otherwise specified, mass% represents a ratio to the total amount of the composition, and “solid content” is a component excluding the solvent in the composition. Represents.

<< Laminated body for forming conductive film >>
The laminate for forming a conductive film of the present invention comprises, on a substrate, (a) a conductive fiber having a minor axis diameter of 150 nm or less, (b) a polymer, (c) a compound having an ethylenically unsaturated double bond (polymerizability). Compound) and (d) a photosensitive layer containing a photopolymerization initiator, and (b) the mass P of the polymer contained in the photosensitive layer, (c) the mass M of the polymerizable compound, and (A) The mass C of the conductive fiber satisfies the relationship of the following formulas (1) and (2).
2.0 ≦ P / C ≦ 10.0 Formula (1)
0.3 ≦ M / C ≦ 1.5 Formula (2)
At this time, when the photosensitive layer contains a polymer having an ethylenic double bond, its mass depends on the average molecular weight and acid value, and when the weight average molecular weight is 3000 or more and the acid value is 5 mgKOH / g or more, the mass of the polymer When the weight average molecular weight is less than 3000, or when the weight average molecular weight is 3000 or more and the acid value is less than 5 mgKOH / g, it is included in the mass of the polymerizable compound.

Formula (1) shows P / C, ie, the ratio of the content of (b) polymer to the content of (a) conductive fiber, and P / C is 2.0 or more and 10.0 or less. However, it is preferably 3.0 or more and 8.0 or less. If P / C is less than 2.0, the film strength may decrease. If it exceeds 10.0, an increase in haze value may be observed due to too much polymer. In some cases, the conductive fibers are eluted, causing problems such as loss of conductivity and missing patterns.
Formula (2) represents M / C, that is, the ratio of the content of the polymerizable compound (c) to the content of (a) conductive fibers, and M / C is 0.3 or more and 1.5 or less. And preferably 0.5 or more and 1.2 or less. If M / C is less than 0.3, there is a risk that the conductive fibers will be eluted during development, and the conductivity may be lowered. It becomes difficult to obtain the effect of improving conductivity by elution, and there is a possibility that practically sufficient conductivity cannot be obtained. Further, when M / C exceeds 1.5, there is a possibility that a problem of elution failure (pattern omission failure) easily occurs during development of the conductive layer in the unexposed portion.
In addition, the (b) polymer in this invention contains all the polymers used for photosensitive layer formation, for example, the polymer etc. which are used as a polymer dispersing agent of a binder polymer and conductive fiber are included.

Moreover, it is important to satisfy both the above formulas (1) and (2), and it is difficult to obtain the excellent effect of the present invention even if any of the conditions is out of the range. The ratio M / P of the content M of the polymerizable compound (c) to the content P of the polymer (b) contained in the same composition in relation to the above formulas (1) and (2) is: It is preferably 0.03 or more and 1.0 or less, and more preferably 0.06 or more and 0.4 or less.
Although the effect of obtaining the effect of the present invention is not clear by setting the content of the polymer (b) and the polymerizable compound (c) within the range defined by the present invention, it is considered as follows.
By coating or transferring the coating liquid composition for forming the photosensitive layer on the substrate by making the content of the polymer (b) with respect to the polymerizable compound (c) in the photosensitive layer excessive, pattern exposure is performed. In the development, the unexposed part (uncured part) of the photosensitive layer is removed, and the excess (b) polymer that is not immobilized in the cured area of the polymerizable compound (c) from the cured part. Are removed at the same time. As a result, conductive fibers are present at high density in the high-strength film obtained by curing the polymerizable compound (c), and it is considered that both conductivity and film strength are achieved. As a method for increasing the density of the conductive fibers, it is considered that the method of reducing the amount of the polymer added in advance (b) when forming the photosensitive layer is generally considered. Compared with the method of reducing in advance, the relationship between conductivity and film strength is surprisingly the method of (b) setting a larger amount of polymer and removing more (b) polymer during development. Has been found to improve. The reason for this is not clear, but removing more polymer after adding more polymer creates a bias in the placement of the conductive fibers in the conductive film and increases the probability of contact between the conductive fibers. At the same time, it is considered that the polymer (b) that protects the conductive fibers is more easily arranged on the outer side, and the conductivity and the film strength are improved. This effect is obtained by setting the content of the polymer (b) and the polymerizable compound (c) within the range defined by the present invention. At this time, the (c) polymerizability with respect to the content P of the polymer (b) A preferable range of the ratio M / P of the content M of the compound is 0.03 or more and 1.0 or less, and a more preferable range is 0.06 or more and 0.4 or less. This ratio is higher than that of a general photocurable patterning material. Is a low region.
In addition, the removal of the polymer (b) contained in the photosensitive layer in the cured region in the development step is to measure the film thickness of the photosensitive layer in the exposure region before and after the development step (1) or (2), This can be confirmed by the decrease in film thickness. The film thickness of the photosensitive layer after development is preferably in the range of 2 to 70, more preferably in the range of 5 to 40, where 100 is the film thickness before development. In addition, when the conductive fiber is a thermally stable material such as a metal and the dispersion medium that is a component other than the conductive fiber is an organic substance, the conductive fiber and the dispersion medium can be measured by thermogravimetry (TG). By measuring the ratio before and after the development step, the reduction rate of the dispersion medium in the development step can be obtained. The amount of the dispersion medium after development is preferably in the range of 2 to 70, more preferably in the range of 5 to 40, where 100 is the amount of dispersion medium before development.

Moreover, in the photosensitive layer which concerns on this invention, the total mass B of the dispersion medium which is components other than the said conductive fiber contained in a photosensitive layer, and the mass C of the said conductive fiber are following formula (3). ) Is preferably satisfied.
2.5 ≦ B / C ≦ 15.0 Formula (3)
Here, the total mass of the dispersion medium refers to the total content of components other than (a) conductive fibers contained in the photosensitive layer. Examples of components other than (a) conductive fibers include the (b) polymer, (c) polymerizable compound, (d) a photopolymerization initiator, and other additives that are optionally added. At this time, the total mass of the dispersion medium is the total mass of the photosensitive layer after drying, and the mass of the solvent is not included in the total mass of the dispersion medium.
B / C is preferably 2.5 or more, and from the viewpoint that both the film strength and the conductivity are good, the upper limit thereof is preferably 15.0 or less, more preferably Is in the range of 3.0 to 8.0.

Next, the structure of the laminated body for electrically conductive film formation of this invention and each component used there are demonstrated.
Although the laminated body for electrically conductive film formation of this invention requires providing a photosensitive layer on the base-material surface, you may have another layer as needed. First, the photosensitive layer will be described.
(1) Photosensitive layer The photosensitive layer according to the present invention contains at least (a) conductive fibers, (b) a polymer, (c) a polymerizable compound, and (d) a photopolymerization initiator. As long as the effects of the present invention are not impaired, other components may be included depending on the purpose.

<(A) Conductive fiber with short axis diameter of 150 nm or less>
The photosensitive layer of the present invention contains conductive fibers having a minor axis diameter of 150 nm or less. The conductive fiber may take any form of a solid structure, a porous structure, and a hollow structure, but preferably has a solid structure or a hollow structure. In the present invention, a solid structure fiber may be referred to as a wire, and a hollow structure fiber as a tube.
The conductive material forming the fibers is preferably at least one of metal and carbon. For example, metal oxides such as ITO, zinc oxide, and tin oxide, metallic carbon, simple metal elements, and multiple metals Examples thereof include a core-shell structure composed of elements and an alloy composed of a plurality of metals. Moreover, after making into fiber form, you may surface-treat, for example, the metal fiber etc. which were plated can be used. The conductive fiber in the present invention preferably has a length (major axis) of 1 μm or less from the viewpoint that aggregates are not easily formed when the conductive film is transparent.

(Metal nanowires)
From the viewpoint of easily forming a transparent conductive film, it is preferable to use metal nanowires as the conductive fibers. The metal nanowire in the present invention is, for example, metal fine particles having an aspect ratio (average major axis length / average minor axis length) of 30 or more, and the average minor axis length is 1 nm to 150 nm, An average major axis length of 1 μm to 100 μm is preferable.

  The average minor axis length (average diameter) of the metal nanowire is preferably 100 nm or less, and more preferably 30 nm or less. If the average minor axis length is too small, the oxidation resistance deteriorates and the durability may deteriorate, so the average minor axis length is preferably 5 nm or more. If the average minor axis length exceeds 150 nm, it is not preferable because there is a possibility that optical properties are deteriorated due to decrease in conductivity or light scattering.

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 of the metal nanowire is too long, there is a concern that aggregates are produced during the production of the metal nanowire, and if the average major axis length is too short, sufficient conductivity may not be obtained.
Here, the average minor axis length (average diameter) and the average major axis length of the metal nanowires are, for example, to observe a TEM image or an optical microscope image using a transmission electron microscope (TEM) and an optical microscope. In the present invention, the average minor axis length (average diameter) and the average major axis length of the metal nanowires are measured with a transmission electron microscope (TEM; manufactured by JEOL Ltd., JEM-2000FX). Using 300 metal nanowires, the average axial length of the metal nanowires was determined from the average value. In addition, the short-axis length in case the short-axis direction cross section of the said metal nanowire is not circular made short length the length of the longest location by the measurement of a short-axis direction. Also. When the metal nanowire is bent, a circle with the arc as the arc is taken into consideration, and the value calculated from the radius and the curvature is taken as the major axis length.

In the present invention, metal nanowires having a minor axis length (diameter) of 150 nm or less and a major axis length of 5 μm or more and 500 μm or less are contained in the total conductive fiber by 50% by mass or more in terms of metal amount. Preferably, it is 60 mass% or more, more preferably 75 mass% or more.
The short axis length (diameter) is 150 nm or less, and the ratio of metal nanowires having a length of 5 μm or more and 500 μm or less is contained by 50% by mass or more, so that sufficient conductivity is obtained and voltage concentration is achieved. Is less likely to occur, and a decrease in durability due to this can be suppressed, which is preferable. If the photosensitive layer contains conductive particles other than fibers, the transparency may decrease when plasmon absorption is strong, such being undesirable.

The coefficient of variation of the short axis length (diameter) of the metal nanowire used in the photosensitive layer according to the present invention is preferably 40% or less, more preferably 35% or less, and even more preferably 30% or less.
If the coefficient of variation exceeds 40%, the voltage may be concentrated on a wire having a short axis length (diameter), or the durability may deteriorate.
The coefficient of variation of the short axis length (diameter) of the metal nanowires is measured, for example, by measuring the short axis length (diameter) of 300 nanowires from a transmission electron microscope (TEM) image, and the standard deviation and average value thereof. Can be obtained by calculating.

As the shape of the metal nanowire, for example, a cylindrical shape, a rectangular parallelepiped shape, a columnar shape having a polygonal cross section can be used, but in applications where high transparency is required, the cylindrical shape or the cross section is A polygon that is a pentagon or more and preferably has a cross-sectional shape that does not have an acute angle.
The cross-sectional shape of the metal nanowire can be detected by applying a metal nanowire aqueous dispersion on a substrate and observing the cross-section with a transmission electron microscope (TEM).

There is no restriction | limiting in particular as a metal in the said metal nanowire, Any metal may be used, 2 or more types of metals may be used in combination other than 1 type of metal, and it can also be used as an alloy. . Among these, those formed from metals or metal compounds are preferable, and those formed from metals are more preferable.
The metal is preferably 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), and at least one selected from Groups 2-14 More preferably, at least one metal selected from Group 2, Group 8, Group 9, Group 10, Group 11, Group 12, Group 13, Group 14 is more preferable, It is particularly preferable to include it as a main component.

  Specific examples of the metal include copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, iron, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantalum, titanium, bismuth, and antimony. , Lead, or an alloy thereof. Among these, copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium or alloys thereof are preferable, palladium, copper, silver, gold, platinum, tin and alloys thereof are more preferable, silver Or the alloy containing silver is especially preferable.

(Method for producing metal nanowires)
The metal nanowire is not particularly limited and may be produced by any method. However, the metal nanowire is preferably produced by reducing metal ions in a solvent in which a halogen compound and a dispersant are dissolved as follows. Moreover, after forming metal nanowire, it is preferable to perform a desalting process by a conventional method from a viewpoint of dispersibility and the temporal stability of the photosensitive layer.
Moreover, as a manufacturing method of metal nanowire, Unexamined-Japanese-Patent No. 2009-215594, Unexamined-Japanese-Patent No. 2009-242880, Unexamined-Japanese-Patent No. 2009-299162, Unexamined-Japanese-Patent No. 2010-84173, Unexamined-Japanese-Patent No. 2010-86714 Etc. can be used.

The solvent used for the production of the metal nanowire is preferably a hydrophilic solvent, and examples thereof include water, alcohols, ethers, and ketones. These may be used alone or in combination of two or more. May be used in combination.
Examples of alcohols include methanol, ethanol, propanol, isopropanol, butanol, and ethylene glycol.
Examples of ethers include dioxane and tetrahydrofuran.
Examples of ketones include acetone.
In the case of heating, the heating temperature is preferably 250 ° C. or lower, more preferably 20 ° C. or higher and 200 ° C. or lower, further preferably 30 ° C. or higher and 180 ° C. or lower, and particularly preferably 40 ° C. or higher and 170 ° C. or lower. By setting the temperature to 20 ° C. or higher, the length of the metal nanowires to be formed is in a preferable range in which dispersion stability can be ensured, and by setting the temperature to 250 ° C. or lower, the cross-sectional outer periphery of the metal nanowires has an acute angle. Therefore, it is suitable from the viewpoint of transparency.
If necessary, the temperature may be changed during the grain formation process. Changing the temperature during the process has the effect of controlling nucleation, suppressing renucleation, and improving monodispersity by promoting selective growth. There is.

The heating is preferably performed by adding a reducing agent.
The reducing agent is not particularly limited and can be appropriately selected from those usually used. For example, borohydride metal salt, aluminum hydride salt, alkanolamine, aliphatic amine, heterocyclic amine, Aromatic amines, aralkylamines, alcohols, organic acids, reducing sugars, sugar alcohols, sodium sulfite, hydrazine compounds, dextrin, hydroquinone, hydroxylamine, ethylene glycol, glutathione and the like can be mentioned. Among these, reducing sugars, sugar alcohols as derivatives thereof, and ethylene glycol are particularly preferable.
Among these, reducing sugars, sugar alcohols as derivatives thereof, and ethylene glycol are particularly preferable.
Depending on the reducing agent, there is a compound that functions as a dispersant or a solvent as a function, and can be preferably used in the same manner.

In producing the metal nanowire, it is preferable to add a dispersant and a halogen compound or metal halide fine particles.
The timing of addition of the dispersant and the halogen compound may be before or after the addition of the reducing agent, and may be before or after the addition of metal ions or metal halide fine particles. In order to control nucleation and growth, it is preferable to add the halogen compound in two or more stages.

  The step of adding the dispersant may be added before preparing the particles and may be added in the presence of the dispersed polymer, or may be added for controlling the dispersion state after adjusting the particles. When the addition of the dispersant is divided into two or more steps, the amount needs to be changed depending on the length of the metal wire required. This is thought to be due to the length of the metal wire by controlling the amount of metal particles as a nucleus.

  Examples of the dispersant include amino group-containing compounds, thiol group-containing compounds, sulfide group-containing compounds, amino acids or derivatives thereof, peptide compounds, polysaccharides, polysaccharide-derived natural polymers, synthetic polymers, or these. And polymers such as gels. Among these, various polymer compounds used as a dispersant are compounds included in the polymer (b) described later.

Examples of the polymer suitably used as the dispersant include gelatin, which is a protective colloidal polymer, polyvinyl alcohol (P-3), methylcellulose, hydroxypropyl cellulose, polyalkyleneamine, polyalkylamine partially alkyl ester, polyvinyl Preferred examples include pyrrolidone, a copolymer containing a polyvinylpyrrolidone structure, and a polymer having a hydrophilic group such as polyacrylic acid having an amino group or a thiol group.
The polymer used as the dispersant has a weight average molecular weight (Mw) measured by GPC of preferably 3000 or more and 300,000 or less, more preferably 5000 or more and 100,000 or less.

For the structure of the compound that can be used as the dispersant, for example, the description of “Encyclopedia of Pigments” (edited by Seijiro Ito, published by Asakura Shoin Co., Ltd., 2000) can be referred to.
The shape of the metal nanowire obtained can be changed depending on the type of the dispersant used.

The halogen compound is not particularly limited as long as it is a compound containing bromine, chlorine, or iodine, and can be appropriately selected according to the purpose. For example, sodium bromide, sodium chloride, sodium iodide, potassium iodide Compounds that can be used in combination with alkali halides such as potassium bromide, potassium chloride, potassium iodide and the following dispersion additives are preferred.
Some halogen compounds may function as a dispersion additive, but can be preferably used in the same manner.

  As an alternative to the halogen compound, silver halide fine particles may be used, or both a halogen compound and silver halide fine particles may be used.

Further, a single substance having both functions may be used as the dispersant and the halogen compound. That is, by using a halogen compound having a function as a dispersant, the functions of both the dispersant and the halogen compound are expressed with one compound.
Examples of the halogen compound having a function as a dispersant include HTAB (hexadecyl-trimethylammonium bromide) containing an amino group and a bromide ion, HTAC (hexadecyl-trimethylammonium chloride) containing an amino group and a chloride ion, an amino group, Dodecyltrimethylammonium bromide containing bromide ion or chloride ion, dodecyltrimethylammonium chloride, stearyltrimethylammonium bromide, stearyltrimethylammonium chloride, decyltrimethylammonium bromide, decyltrimethylammonium chloride, dimethyldistearylammonium bromide, dimethyldistearylammonium chloride, Dilauryl dimethyl ammonium bromide, dilauryl dimethyl ammonium Mukurorido, dimethyl dipalmityl ammonium bromide, dimethyl dipalmityl ammonium chloride, and the like.

  In addition, the desalting process after metal nanowire formation can be performed by techniques, such as ultrafiltration, dialysis, gel filtration, decantation, and centrifugation.

The metal nanowire preferably contains as little inorganic ions as possible, such as alkali metal ions, alkaline earth metal ions, and halide ions. The electrical conductivity when the metal nanowire is dispersed in an aqueous dispersion is preferably 1 mS / cm or less, more preferably 0.1 mS / cm or less, and even more preferably 0.05 mS / cm or less.
The viscosity at 20 ° C. when the metal nanowire is dispersed in an aqueous dispersion is preferably 0.5 mPa · s to 100 mPa · s, and more preferably 1 mPa · s to 50 mPa · s.

Examples of preferable conductive fibers other than metal nanowires include metal nanotubes and carbon nanotubes which are hollow fibers.
(Metal nanotube)
There is no restriction | limiting in particular as a material of a metal nanotube, What kind of metal may be sufficient, For example, the material of the above-mentioned metal nanowire etc. can be used.
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 3 nm or more, sufficient oxidation resistance is obtained, and when the thickness is 80 nm or less, the occurrence of light scattering due to the metal nanotubes is suppressed.
The average short axis length of the metal nanotubes is required to be 150 nm or less like the metal nanowires. The preferred minor axis diameter is the same as in metal nanowires. The major axis length is preferably 1 μm to 40 μm, more preferably 3 μm to 35 μm, and still more preferably 5 μm to 30 μm.

  There is no restriction | limiting in particular as a manufacturing method of the said metal nanotube, According to the objective, it can select suitably, For example, the method as described in the US application publication 2005/0056118 grade | etc., Etc. can be used.

(carbon nanotube)
A carbon nanotube (CNT) is a substance in which a graphite-like carbon atomic surface (graphene sheet) is a single-layer or multilayer coaxial tube. Single-walled carbon nanotubes are called single-walled nanotubes (SWNT), multi-walled carbon nanotubes are called multi-walled nanotubes (MWNT), and in particular, 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 of conductive fiber)
The aspect ratio of the conductive fiber that can be used in the present invention is preferably 10 or more. The aspect ratio generally means the ratio between the long side and the short side of the fibrous material (ratio of average major axis length / average minor axis length).
There is no restriction | limiting in particular as a measuring method of an 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.

In the photosensitive layer according to the present invention, in addition to the conductive fibers, other conductive materials such as conductive fine particles can be used in combination as long as the effects of the present invention are not impaired. 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 by volume ratio in the composition for forming a photosensitive layer. 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. This is detected 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 method for measuring the average minor axis length and the average major axis length of the conductive fibers is as described above.

<Binder polymer>
The photosensitive layer according to the present invention may contain a binder polymer. The binder polymer is an embodiment of the polymer (b) that is an essential component of the photosensitive layer according to the present invention. The binder polymer is a linear organic polymer, and is a group that promotes at least one alkali solubility in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain) ( For example, it can be appropriately selected from alkali-soluble resins having a hydrophilic group such as a carboxyl group, a phosphoric acid group, and a sulfonic acid group.
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.

  For production of the binder, for example, a known radical polymerization method can be applied. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an alkali-soluble resin by the radical polymerization method can be easily set by those skilled in the art, and the conditions are determined experimentally. Can be determined.

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.

  In addition to the above, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl described in JP-A-7-140654 Methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer Coalescence, etc.

As specific structural units in the alkali-soluble resin, (meth) acrylic acid and other monomers copolymerizable with the (meth) acrylic acid are suitable.
Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. In these, the hydrogen atom of the alkyl group and aryl group may be substituted with a substituent.
Examples of the alkyl (meth) acrylate or aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and pentyl (meth) acrylate. , Hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) Examples include acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and the like. These may be used individually by 1 type and may use 2 or more types together.

Examples of the vinyl compound include styrene, α-methylstyrene, vinyl toluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, CH ₂ ═CR ^1. R ² , CH ₂ = C (R ¹ ) (COOR ³ ) [wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ² represents an aromatic hydrocarbon ring having 6 to 10 carbon atoms. R ³ represents an alkyl group having 1 to 8 carbon atoms or an aralkyl group having 6 to 12 carbon atoms. ] And the like. These may be used individually by 1 type and may use 2 or more types together.

The weight average molecular weight of the binder 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 by a gel permeation chromatography method (also referred to as GPC method as appropriate in the present specification) and obtained using a standard polystyrene calibration curve.

The content of the binder is preferably 5% by mass to 90% by mass, more preferably 10% by mass to 85% by mass, and more preferably 20% by mass to 80% by mass with respect to the total solid content of the composition constituting the photosensitive layer. More preferred is mass%.
In addition, the sum total of content of the polymer used as the said dispersing agent and binder polymer is equivalent to content of (b) polymer in this invention. For this reason, the content of the polymer (b) is within the range of the preferable content of the binder polymer, and in consideration of the polymer content as the dispersant, (a) the conductive fiber and will be described later. (C) Content ratio with a polymeric compound needs to satisfy | fill the content ratio prescribed | regulated in the said invention, and it can attain coexistence with electroconductivity and durability of the electroconductive film obtained by this.

<(C) Compound having an ethylenically unsaturated double bond>
The photosensitive layer contains (c) an ethylenically unsaturated double bond and (d) a photopolymerization initiator having a function of forming an image by exposure.
A compound having an ethylenically unsaturated group (hereinafter also referred to as “polymerizable compound”) is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and has a terminal ethylenically unsaturated bond. It is selected from compounds having at least one, preferably two or more. Among these, from the viewpoint of improving the film strength, those having 4 or more terminal ethylenically unsaturated bonds in the molecule are preferable, and those having 6 or more are more preferable. These have chemical forms such as monomers, prepolymers, i.e. dimers, trimers and oligomers, or mixtures thereof.

  Examples of the polymerizable compound include monofunctional acrylates and monofunctional methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, polypropylene glycol di (Meth) acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipenta Erythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexane All di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate, trimethylolpropane, glycerin, bisphenol, etc. Polyfunctional alcohols obtained by addition reaction of ethylene oxide or propylene oxide and then (meth) acrylated, in Japanese Patent Publication Nos. 48-41708, 50-6034, 51-37193, etc. Described urethane acrylates; polyester acrylates described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, etc .; ) Such as multifunctional acrylates or methacrylates such as epoxy acrylates which are reaction products of acrylic acid. These may be used individually by 1 type and may use 2 or more types together.

  As the polymerizable compound, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are particularly preferable from the viewpoint of film strength.

(C) The content of the polymerizable compound in the composition for forming a photosensitive layer is preferably 2.6% by mass to 37.5% by mass, and more preferably 5.0% by mass to 20.0% by mass. More preferably.
In addition, it is the range of the said preferable content, and it is required to contain the ratio of content of (a) electroconductive fiber and (b) polymer in the ratio prescribed | regulated to this invention.

<(D) Photopolymerization initiator>
Examples of the photopolymerization initiator used in the photosensitive layer according to the present invention include a photoacid generator and a photoradical generator.
-(1) Photoacid generator-
(1) As a photoacid generator, a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photodecolorant for dyes, a photochromic agent, an actinic ray used for a microresist, or the like Known compounds that generate an acid upon irradiation with radiation and mixtures thereof can be appropriately selected and used.

  (1) The photoacid generator is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, and disulfones. , O-nitrobenzyl sulfonate and the like. 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-
(2) The 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.

  Examples of 1,2-quinonediazidesulfonyl chlorides include benzoquinone-1,2-diazide-4-sulfonyl chloride, naphthoquinone-1,2-diazide-5-sulfonyl chloride, and naphthoquinone-1,2-diazide-4-sulfonyl. And chloride. Among these, naphthoquinone-1,2-diazide-4-sulfonyl chloride is particularly preferable in terms of sensitivity.

  Examples of the hydroxy compound include hydroquinone, resorcinol, pyrogallol, bisphenol A, bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2,3,4-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,4,2 ′, 3′-pentahydroxybenzophenone, 2,3,4,3 ', 4', 5'-hexahydroxybenzophenone, bis (2,3,4-trihydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) propane, 4b, 5,9b, 10-tetrahydro- 1,3,6,8-tetrahydroxy-5,10-dimethylindeno [2,1- ] Indene, tris (4-hydroxyphenyl) methane, tris (4-hydroxyphenyl) ethane, 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl]- Ethylidene] bisphenol, and the like.

  Examples of amino compounds include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, and 4,4′-diaminodiphenyl sulfide. , O-aminophenol, m-aminophenol, p-aminophenol, 3,3′-diamino 4,4′-dihydroxybiphenyl, 4,4′-diamino 3,3′-dihydroxybiphenyl, bis (3-amino-4 -Hydroxyphenyl) propane, bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino3-hydroxyphenyl) sulfone, bis (3-amino-4-hydroxy) Phenyl) hexafluoropropane, bi (4-amino-3-hydroxyphenyl) hexafluoropropane, and the like.

The blending amount of the (1) photoacid generator and the (2) quinonediazide compound is based on the difference in dissolution rate between the exposed portion and the unexposed portion, and the allowable range of sensitivity, with respect to 100 parts by weight of the total amount of the binder. It is preferably 1 part by mass to 100 parts by mass, and more preferably 3 parts by mass to 80 parts by mass.
The (1) photoacid generator and the (2) quinonediazide compound may be used in combination.

  In the present invention, among the (1) photoacid generators, compounds that generate sulfonic acid are preferable, and the following oxime sulfonate compounds are particularly preferable from the viewpoint of high sensitivity.

When a compound having a 1,2-naphthoquinonediazide group is used as the (2) quinonediazide compound, high sensitivity and good developability are obtained.
Among the above (2) quinonediazide compounds, the following compounds, in which D is independently a hydrogen atom or a 1,2-naphthoquinonediazide group, are preferred from the viewpoint of high sensitivity.

  However, in said formula, D represents either a hydrogen atom or the following substituents each independently.

-(3) Photoradical generator-
The conductive composition of the present invention uses, as a photosensitive compound, 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. Can do. The photo radical 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 total solid content of the conductive composition. 1 mass%-20 mass% are still more preferable. In the 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 as described in Unexamined-Japanese-Patent No. 2008-268884 is mentioned. Among these, triazine compounds, acetophenone compounds, acylphosphine (oxide)
Of these compounds, oxime compounds, imidazole compounds, and benzophenone compounds are particularly preferred from the viewpoint of exposure sensitivity.

  Examples of the triazine compound include 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl)- s-triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) mono-s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine 2,4,6-tris (monochloromethyl) -s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2 -Methyl-4,6-bis (trichloromethyl) -s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2 (Α, α, β-trichloroethyl) -4,6-bis (trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) ) -4,6-bis (trichloromethyl) -s-triazine, 2- (3,4-epoxyphenyl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4 , 6-Bis (trichloromethyl) -s-triazine, 2- [1- (p-methoxyphenyl) -2,4-butadienyl] -4,6-bis (trichloromethyl) -s-triazine, 2-styryl- 4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (pi-propyl) Xystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4, 6-bis (trichloromethyl) -s-triazine, 2-phenylthio-4,6-bis (trichloromethyl) -s-triazine, 2-benzylthio-4,6-bis (trichloromethyl) -s-triazine, 4- (O-bromo-pN, N- (diethoxycarbonylamino) -phenyl) -2,6-di (trichloromethyl) -s-triazine, 2,4,6-tris (dibromomethyl) -s-triazine 2,4,6-tris (tribromomethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-methoxy-4,6 -Bis (tribromomethyl) -s-triazine, and the like. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the benzophenone compounds include benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, N, N-diethylaminobenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, and the like. Is mentioned. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the acetophenone compound include 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4. -(4-morpholinyl) phenyl] -1-butanone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl (p-isopropylphenyl) ketone, 1-hydroxy -1- (p-dodecylphenyl) ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 1,1,1-trichloromethyl- (p-butylphenyl) ketone 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butano -1 and the like. Specific examples of commercially available products are Irgacure 369, Irgacure 379, and Irgacure 907 manufactured by Ciba Specialty Chemicals. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the imidazole compound include JP-B-6-29285, US Pat. No. 3,479,185, US Pat. No. 4,311,783, and US Pat. No. 4,622,286. Various compounds described in the literature, specifically 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-bromo) Phenyl)) 4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o, p-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2 '-Bis (o-chlorophenyl) -4,4', 5,5'-tetra (m-methoxyphenyl) biidazole, 2,2'-bis (o, o'-dichlorophenyl) -4,4 ', 5 5'-tetraphenylbi Midazole, 2,2′-bis (o-nitrophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-methylphenyl) -4,4 ′, 5 5'-tetraphenylbiimidazole, 2,2'-bis (o-trifluorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, and the like. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the oxime compound include J.I. C. S. Perkin II (1979) 1653-1660), J. MoI. C. S. Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, Japanese Patent Application Laid-Open No. 2000-66385, Japanese Patent Application Laid-Open No. 2000-80068, Japanese Patent Application Publication No. 2004-534797 Compounds and the like. Specific examples include Irgacure OXE-01 and OXE-02 manufactured by Ciba Specialty Chemicals. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the acylphosphine (oxide) compound include Irgacure 819, Darocur 4265, and Darocur TPO manufactured by Ciba Specialty Chemicals.

  As a photoradical generator, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1- is used from the viewpoint of exposure sensitivity and transparency. Butanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2, 2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, N, N-diethylaminobenzophenone, 1,2-octanedione, 1- [4- (phenylthio)-, 2 -(O-benzoyloxime)] is particularly preferred.

In the conductive composition of the present invention, 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-mercaptobenzimidazole, Heterocycles such as N-phenylmercaptobenzimidazole, 1,3,5-tris (3-mercapbutbutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione -Functional 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 total solid content of the conductive composition, and 0.5% by mass. % To 5% by mass is more preferable.

<(E) Other ingredients>
Examples of the other components include various additives such as a crosslinking agent, a dispersant, a solvent, a surfactant, an antioxidant, an antisulfurizing agent, a metal corrosion inhibitor, a viscosity modifier, and an antiseptic.

(E-1) Crosslinking agent The crosslinking agent is a compound that forms a chemical bond with a free radical or acid and heat to cure the conductive layer, and is at least one selected from, for example, a methylol group, an alkoxymethyl group, and an acyloxymethyl group. Melamine compounds, guanamine compounds, glycoluril compounds, urea compounds, phenol compounds or phenol ether compounds, epoxy compounds, oxetane compounds, thioepoxy compounds, isocyanate compounds, or azides substituted with one group And a compound having an ethylenically unsaturated group containing a methacryloyl group or an acryloyl group. Among these, an epoxy compound, an oxetane compound, and a compound having an ethylenically unsaturated group are particularly preferable in terms of film properties, heat resistance, and solvent resistance.
Moreover, the said oxetane resin can be used individually by 1 type or in mixture with an epoxy resin. In particular, when used in combination with an epoxy resin, the reactivity is high, which is preferable from the viewpoint of improving film properties.
In addition, when using the compound which has an ethylenically unsaturated double bond group as a crosslinking agent, the said crosslinking agent is also included by the said (c) polymeric compound, The content is (c) polymerization in this invention. It should be considered that it is included in the content of the active compound.

  The content of the crosslinking agent is preferably 1 part by weight to 250 parts by weight, and more preferably 3 parts by weight to 200 parts by weight with respect to 100 parts by weight of the total amount of the binder.

(E-2) 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.).
In the case where a polymer dispersant is further added as a dispersant other than that used in the production of the conductive fiber, the polymer dispersant is also included in the polymer (b), and the content thereof Should be considered to be included in the content of the polymer (b) in the present invention.
As content of the said dispersing agent, 0.1 mass part-50 mass parts are preferable with respect to 100 mass parts of said binders, 0.5 mass part-40 mass parts are more preferable, and 1 mass part-30 mass parts are. Particularly preferred.
By setting the content of the dispersant to 0.1 parts by mass or more, the aggregation of conductive fibers in the dispersion is effectively suppressed, and by setting the content to 50 parts by mass or less, a stable liquid film in the coating process Is preferable, and the occurrence of uneven coating is suppressed.

(E-3) Solvent The solvent is not particularly limited and may be appropriately selected depending on the intended purpose. For example, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, 3-methoxy Examples include methyl propionate, ethyl lactate, 3-methoxybutanol, water, 1-methoxy-2-propanol, isopropyl acetate, methyl lactate, N-methylpyrrolidone (NMP), γ-butyrolactone (GBL), propylene carbonate, and the like. . These may be used individually by 1 type and may use 2 or more types together.

(E-4) Metal corrosion inhibitor There is no restriction | limiting in particular as a metal corrosion inhibitor, Although it can select suitably according to the objective, For example, thiols, azoles, etc. are suitable.
By containing a metal corrosion inhibitor, a further excellent rust prevention effect can be exhibited. The metal corrosion inhibitor is added to the composition for forming the photosensitive layer in a state dissolved in a suitable solvent, or in the form of powder, or after preparing a conductive film with a conductive layer coating liquid described later, this is added to the metal corrosion inhibitor It can be applied by soaking in a bath.

In the present invention, as described above, the total mass of the dispersion medium contained in the photosensitive layer, that is, the total content B of components other than the conductive fibers and the mass C of the conductive fibers are expressed by the following formula ( The relationship 3) is preferably satisfied, more preferably 2.5 or more and 15.0 or less, and most preferably 3.0 or more and 8.0 or less.
2.5 ≦ B / C ≦ 15.0 Formula (3)
Although depending on the ratio of the polymer and the polymerizable compound contained in the dispersion medium, the mass ratio (B) of the total content B of components other than the conductive fibers in the photosensitive layer and the content C of the conductive fibers / C) is less than 2.5, the mechanical strength of the conductive layer and the deterioration of the adhesion to the transfer substrate, particularly the pattern quality obtained by patterning using photolithography (faithful reproducibility of the exposure pattern) May cause problems such as deterioration. The mass ratio (B / C) may be large, but even if the mass ratio exceeds 15.0, the performance is not improved. On the contrary, the decrease in conductivity due to the decrease in the number of contact points between the conductive fibers, The upper limit value is preferably 15.0, since the electroconductivity layer may be degraded during development and the optical properties such as pattern loss, haze, and light transmittance may be deteriorated.

  A photosensitive layer is formed by apply | coating the composition for photosensitive layer formation containing the said each component on the base material mentioned later, and drying.

The coating method is not particularly limited and may be appropriately selected depending on the purpose. For example, a roll coating method, a bar coating method, a dip coating method, a spin coating method, a casting method, a die coating method, a blade coating method, a bar coating method, and the like. Examples thereof include a coating method, a gravure coating method, a curtain coating method, a spray coating method, and a doctor coating method.
The film thickness (average thickness) after drying of the photosensitive layer is preferably 0.01 μm to 2 μm, and more preferably 0.03 μm to 1 μm. When the average thickness is 0.01 μm or more, the conductive in-plane distribution is uniform, and when the average thickness is 2 μm or less, good transparency is obtained.

<Base material>
The substrate in the conductive film-forming laminate of the present invention is not particularly limited as long as it has a surface on which the photosensitive layer can be formed, and is not particularly limited as long as it is a substrate on which a patterned conductive film is to be formed. It can be used without. Examples 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. Examples of the synthetic resin sheet include a polyethylene terephthalate (PET) sheet, a polycarbonate sheet, a triacetyl cellulose (TAC) sheet, a polyethersulfone sheet, a polyester sheet, an acrylic resin sheet, a vinyl chloride resin sheet, and an aromatic polyamide resin sheet. , Polyamideimide sheet, polyimide sheet and the like.
In addition, when the photosensitive layer according to the present invention is formed on the surface of the transfer substrate to form a conductive film-forming laminate, the conductive film-forming film excellent in pattern formability can be formed on any substrate or support surface. Since the photosensitive layer can be easily formed by transfer, a conductive film-forming laminate using a transfer substrate is also a preferred embodiment.

<Transfer substrate>
There is no restriction | limiting in particular about the shape, structure, size, etc. of the said transfer base material, According to the objective, it can select suitably, For example, a film form, a sheet form, etc. are mentioned as said shape. Examples of the structure include a single layer structure and a laminated structure. The size can be appropriately selected according to the application.

There is no restriction | limiting in particular as said transfer base material, According to the objective, it can select suitably, For example, a semiconductor substrate which has a transparent glass substrate, a synthetic resin sheet (film), a metal substrate, a ceramic board, a photoelectric conversion element. Etc. 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.
Examples of the transparent glass substrate include white plate glass, blue plate glass, and silica-coated blue plate glass. Further, a thin glass substrate having a thickness of 10 μm to several hundred μm, which has been recently developed, may be used.
Examples of the synthetic resin sheet include a polyethylene terephthalate (PET) sheet, a polycarbonate sheet, a triacetyl cellulose (TAC) sheet, a polyethersulfone sheet, a polyester sheet, an acrylic resin sheet, a vinyl chloride resin sheet, and an aromatic polyamide resin sheet. , Polyamideimide sheet, polyimide sheet and the like.
Examples of the metal substrate include an aluminum plate, a copper plate, a nickel plate, and a stainless plate.

The total visible light transmittance of the transfer substrate is preferably 70% or more, more preferably 85% or more, and still more preferably 90% or more. If the total visible light transmittance is less than 70%, the transmittance may be low and may cause a problem in practical use.
In the present invention, it is also possible to use a transfer substrate that has been colored to the extent that the object of the present invention is not hindered.

There is no restriction | limiting in particular in the average thickness of the said transfer base material, Although it can select suitably according to the objective, 1 micrometer-500 micrometers are preferable, 3 micrometers-400 micrometers are more preferable, and 5 micrometers-300 micrometers are still more preferable.
When the average thickness is within the above range, the handling is good and the flexibility is excellent, so that the transfer uniformity is good.

<Cushion layer>
The laminate for forming a conductive film of the present invention may have a cushion layer for improving transferability between the base material and the photosensitive layer. There is no restriction | limiting in particular about the shape of a cushion layer, a structure, a magnitude | size, etc., It can select suitably according to the objective, For example, as said shape, it can be set as a film | membrane form and a sheet form.
Examples of the structure include a single-layer structure and a laminated structure, and the size and thickness can be appropriately selected according to the application.
The cushion layer is a layer that plays a role of improving transferability with the transfer target, and contains at least a polymer, and further contains other components as necessary.

The polymer used for the cushion layer is not particularly limited as long as it is a thermoplastic resin that softens when heated, and can be appropriately selected according to the purpose. For example, acrylic resin, styrene-acrylic copolymer, polyvinyl alcohol, polyethylene , Ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, polyvinyl chloride gelatin; cellulose nitrate, cellulose triacetate, cellulose diacetate, cellulose acetate butyrate, cellulose acetate propio Cellulose esters such as nitrates; homopolymers or copolymers containing vinylidene chloride, vinyl chloride, styrene, acrylonitrile, vinyl acetate, alkyl (carbon number 1-4) acrylate, vinyl pyrrolidone, etc., soluble polymers Esters, polycarbonates, soluble polyamide. These may be used individually by 1 type and may use 2 or more types together.
The polymer used for the cushion layer is preferably a thermoplastic resin that is softened by heating. The glass transition temperature of the cushion layer is preferably 40 ° C to 150 ° C. If it is lower than 40 ° C., it may be too soft at room temperature to be inferior in handling property, and if it is higher than 150 ° C., the cushion layer may not be softened by the heat laminating method, and the transfer property of the conductive layer may be inferior. Further, the glass transition temperature may be adjusted by adding a plasticizer or the like.

  Examples of the other components include organic polymer materials described in paragraph [0007] and later of JP-A-5-72724, various plasticizers for adjusting the adhesive force with the transfer substrate, supercooling materials, Examples thereof include adhesion improvers, surfactants, mold release agents, thermal polymerization inhibitors, and solvents.

  The cushion layer can be formed by applying and drying a cushion layer-use cloth liquid containing the polymer and, if necessary, the other components on a transfer substrate.

  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 cushion layer can be formed by applying a cushion layer-use cloth liquid containing the polymer and, if necessary, the other components on a base material and drying it.

The average thickness of the cushion layer is preferably 1 μm to 50 μm, more preferably 1 μm to 30 μm, and even more preferably 5 μm to 20 μm. By setting the average thickness within the above range, uniform transferability can be obtained and the curl balance of the transfer material can be improved.
When a cushion layer is further provided between the base material and the photosensitive layer, the total average thickness S of the photosensitive layer and the cushion layer and the average thickness N of the base material satisfy the following formula (4). preferable.
S / N = 0.01-0.7 Formula (4)
The S / N is more preferably in the range of 0.02 to 0.6. When the S / N is 0.01 or more, the transfer uniformity to the transfer medium becomes good, and when it is 0.7 or less, the curl balance is excellent.

FIG. 1 is a schematic cross-sectional view showing an example of a conductive film-forming laminate 10 of the present invention. In the present embodiment, the conductive film-forming laminate is used as a transfer material. The conductive film-forming laminate 10 has a cushion layer 14 and a photosensitive layer 16 in this order on the surface of the transfer substrate 12. In order to protect the photosensitive layer 16, a surface protective film may be provided on the surface of the photosensitive layer 16.
As the protective film, a transparent film having a thickness of about 10 μm such as polypropylene or polyethylene may be used.

<< Conductive element >>
The conductive element of the present invention includes a conductive fiber having a minor axis diameter of 150 nm or less, a polymer, a compound having an ethylenically unsaturated double bond, and a photopolymerization initiator, and the mass P of the polymer, the ethylenically unsaturated double The mass M of the compound having a bond and the mass C of the conductive fiber satisfy the following relationship.
2.0 ≦ P / C ≦ 10.0
0.3 ≦ M / C ≦ 1.5
The conductive element in the present invention includes a material that satisfies the above specific relationship, and its use is not particularly limited.

<< Method for Forming Conductive Film >>
Next, a conductive film forming method using the conductive film forming laminate of the present invention will be described.
The conductive film forming method of the present invention includes a laminate forming step of obtaining the conductive film forming laminate of the present invention, and an exposure step of exposing at least a part of the photosensitive layer in the obtained conductive film forming laminate. Or a step of developing the photosensitive medium after the exposure by reducing the dispersion medium with a solvent (developing step (1)), or after the laminate forming step and the exposing step, Instead of 1), the method includes a step (developing step (2)) of removing a non-exposed portion by applying a solvent to the exposed photosensitive layer.
The manufacturing process of the conductive film forming laminate is as described above.
In addition, when using the laminated body for electrically conductive film formation of this invention as a transfer material, the transfer process which transfers a photosensitive layer on a suitable board | substrate is performed prior to the said exposure process.

The transfer process will be described with reference to the drawings.
2A to 2C are schematic views showing an example of a transfer process using the conductive film-forming laminate 10 of the present invention.
FIG. 2A shows a laminate 10 for forming a conductive film having a cushion layer 14 and a photosensitive layer 16 in this order on the surface of the transfer substrate 12. First, as shown in FIG. 2B, the cushion layer 14 and the photosensitive layer 16 of the conductive film-forming laminate 10 are bonded to a glass substrate 18 as a transfer target by applying pressure and heating using a laminator. . When a protective film is provided on the surface of the photosensitive layer 16 of the conductive film-forming laminate 10, the protective film may be first peeled off and laminated.
Conventionally known laminators and vacuum laminators can be used for bonding, and an auto-cut laminator can also be used in order to increase productivity.

Next, as shown in FIG. 2C, the cushioning layer 14 and the photosensitive layer 16 are transferred to the glass substrate 18 by peeling the transfer base material 12.
The substrate to be transferred can be appropriately selected according to the purpose, and examples thereof 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. As the substrate to be transferred, a substrate subjected to a surface treatment such as chemical treatment such as a silane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, or vacuum deposition may be used as desired.

(Exposure process)
The conductive film forming method of the present invention includes an exposure process in which a photosensitive layer provided on a base material or a photosensitive layer transferred onto a desired substrate from a conductive film forming laminate is subjected to pattern exposure.
The light source used for exposure is appropriately selected according to the use of the conductive film and the required resolution. The exposure light source may be selected in relation to the photopolymerization initiator contained in the photosensitive layer, but in general, ultraviolet rays such as g-line, h-line, i-line, and j-line are preferably used. A blue LED may be used.
The pattern exposure method is not particularly limited, and may be performed by surface exposure using a photomask, or may be performed by scanning exposure using a laser beam or the like. 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.

(Development process)
The development step is a step of reducing the dispersion medium of the photosensitive layer after exposure by applying a solvent (development step (1)) or a step of removing a non-exposed portion by applying a solvent to the photosensitive layer after exposure. (Developing step (2)).
As the solvent, an alkaline solution is preferable.
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.
As a developing solution when developing after the exposure, an alkaline solution is preferable. Examples of the alkali contained in the alkaline solution include tetramethylammonium hydroxide, tetraethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium hydroxide, water Examples include potassium oxide. As the developer, an aqueous solution of these alkalis is preferably used.
More specifically, examples of the developer include organic alkalis such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and 2-hydroxyethyltrimethylammonium hydroxide; inorganics such as sodium carbonate, sodium hydroxide, and potassium hydroxide. Examples of the aqueous solution include alkalis.

  Methanol, ethanol, or a surfactant may be added to the developer for the purpose of reducing development residue and optimizing the pattern shape. As the surfactant, for example, an anionic, cationic or nonionic surfactant can be selected and used. Among these, the addition of nonionic polyoxyethylene alkyl ether is particularly preferable because the resolution becomes high.

There is no restriction | limiting in particular as the provision method by the said alkaline solution, According to the objective, it can select suitably, For example, application | coating, immersion, spraying etc. are mentioned. Specifically, dip development in which a substrate or substrate having a photosensitive layer after exposure in an alkaline solution is immersed, paddle development in which the developer is stirred during immersion, a shower in which the developer is poured using a shower or spray Examples include development and a development method in which the surface of the photosensitive layer is rubbed with a sponge or a fiber lump impregnated with an alkaline solution. Among these, the method of immersing in an alkaline solution 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.

<< conductive film >>
Since the conductive film obtained by the method of the present invention uses a conductive film-forming laminate having a photosensitive layer having a relatively high resolution during patterning, a high-resolution patterned conductive film is formed. Here, the conductive film means, for example, a film (interlayer conductive film) provided to conduct between elements arranged in layers.

  Since the conductive layer of the present invention is a high-resolution patterned conductive film excellent in conductivity and durability, for example, a touch panel, a display electrode, an electromagnetic wave shield, an organic EL display electrode, an inorganic EL display electrode, and an electronic paper It is widely applied to flexible display electrodes, integrated solar cells, liquid crystal display devices, display devices with touch panel functions, and other various devices. Among these, a touch panel, a liquid crystal display device, and a display device with a touch panel function are particularly preferable.

<< Touch panel >>
The touch panel of the present invention is not particularly limited as long as it has the conductive film of the present invention, and can be appropriately selected according to the purpose. For example, a surface capacitive touch panel, a projected capacitive touch panel, a resistor Examples include membrane touch panels. The touch panel includes a so-called touch sensor and a touch pad.
The layer structure of the touch panel sensor electrode part in the touch panel is a bonding method in which two transparent electrodes are bonded, a method in which transparent electrodes are provided on both surfaces of a single substrate, a single-sided jumper or a through-hole method, or a single-area layer method. It is preferable that it is either.

Here, an example of the surface capacitive touch panel will be described with reference to FIG. In FIG. 3, the touch panel 20 is provided with a transparent conductor 22 (corresponding to the conductive layer transferred by the conductive layer transfer material of the present invention) so as to uniformly cover the surface of the transparent substrate 21, and is transparent. An electrode terminal 30 for electrical connection with an external detection circuit (not shown) is formed on the transparent conductor 22 at the end of the substrate 21.
In FIG. 3, reference numeral 22 denotes a transparent conductor serving as a shield electrode, 26 denotes an insulating cover layer, 27 denotes a protective film, 28 denotes an intermediate protective film, and 29 denotes an antiglare film. Indicates.
When an arbitrary point on the transparent conductor 22 is touched with a finger or the like, the transparent conductor 22 is grounded through the human body at the touched point, and changes to a resistance value between each electrode terminal 30 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.

(Display device with display function comprising the touch panel of the present invention)
The touch panel of the present invention can be used for a display device with a display function. The display device is not particularly limited except that it includes a glass substrate or a liquid crystal cell having a conductive film transferred using the conductive film-forming laminate according to the present invention as a transfer material, and is appropriately selected depending on the purpose. be able to.
The display device is preferably a liquid crystal display device, and the liquid crystal display device is the same as the liquid crystal display device of the present invention.
The touch panel function can be appropriately selected from those described above.

  The display device provided with the touch panel of the present invention has a high-strength conductive film having excellent conductivity and transparency, the number of parts is reduced, and the weight and thickness can be reduced. It has viewing angle, high contrast, and high image quality.

<< Integrated solar cell >>
There is no restriction | limiting in particular as an integrated solar cell (henceforth a solar cell device) of this invention, The thing 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, a thin film containing Ge in these, and a tandem structure of these two or more layers is a photoelectric conversion layer Used as For film formation, plasma CVD or the like is used.

[Method for producing transparent conductive layer]
The said transparent conductive layer used for the solar cell of this invention is applicable regarding all the said solar cell devices. The transparent conductive layer may be included in any part of the solar cell device, but is preferably adjacent to the photoelectric conversion layer. Although the following structure is preferable regarding the positional relationship with a photoelectric converting layer, it is not limited to this. Moreover, the structure described below does not describe all the parts that constitute the solar cell device, but describes the range in which the positional relationship of the transparent conductive layer can be understood.
(A) Substrate-transparent conductive film (conductive film of the present invention) -photoelectric conversion layer (B) substrate-transparent conductive film (conductive film of the present invention) -photoelectric conversion layer-transparent conductive film (conductive film of the present invention)
(C) Substrate-electrode-photoelectric conversion layer-transparent conductive film (conductive film of the present invention)
(D) Back electrode-photoelectric conversion layer-transparent conductive film (conductive film of the present invention)

The method for forming the conductive film is as described above, and the photosensitive layer in the conductive film-forming laminate of the present invention is transferred onto a substrate, and then exposed and developed to form a conductive film.
After transferring the photosensitive layer, annealing by heating may be performed. In this case, the heating temperature is preferably 50 ° C. or higher and 300 ° C. or lower, and more preferably 70 ° C. or higher and 200 ° C. or lower.
Moreover, you may use what formed and coated the said photosensitive layer on the board | substrate.

Examples of the substrate used for the solar cell include, but are not limited to, the following.
(1) Quartz glass, alkali-free glass, crystallized transparent glass, Pyrex (registered trademark) glass, glass such as sapphire (2) Acrylic resin such as polycarbonate and polymethyl methacrylate, polyvinyl chloride, vinyl chloride copolymer, etc. Thermoplastic resins such as vinyl chloride resin, polyarylate, polysulfone, polyethersulfone, polyimide, PET, PEN, fluorine resin, phenoxy resin, polyolefin resin, nylon, styrene resin, ABS resin, etc. (3) Epoxy resin, etc. Thermosetting resin

  The surface of the substrate may be subjected to a hydrophilic treatment. Moreover, what coated the hydrophilic polymer on the said substrate surface is preferable. These pretreatments improve the adhesion to the photosensitive layer.

  The hydrophilic treatment is not particularly limited and may be appropriately selected depending on the intended purpose. For example, chemical treatment, mechanical roughening treatment, corona discharge treatment, flame treatment, ultraviolet treatment, glow discharge treatment, active plasma Treatment, laser treatment and the like. It is preferable that the surface tension of the surface is 30 dyne / cm or more by these hydrophilic treatments.

The hydrophilic polymer to be coated on the substrate surface 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 Carboxymethylcellulose, hydroxyethylcellulose, polyvinylpyrrolidone, dextran, and the like.
The layer thickness (when dried) of the hydrophilic polymer layer is preferably 0.001 μm to 100 μm, and more preferably 0.01 μm to 20 μm.
The hydrophilic polymer layer is preferably added with a hardener to increase the film strength.
Furthermore, an undercoat layer may be formed between the substrate and the hydrophilic polymer layer as necessary for the purpose of improving adhesion.

<CIGS solar cells>
The CIGS solar cell will be described in detail below.
[Configuration of photoelectric conversion layer]
CuInSe2 (CIS-based thin film) which is a semiconductor thin film having a chalcopyrite structure, consisting of a group Ib element, a group IIIb element and a VIb group element, or Cu (In, Ga) Se2 (CIGS-based thin film) in which Ga is dissolved. ) In the light absorption layer has high energy conversion efficiency and has the advantage of less deterioration in efficiency due to light irradiation or the like. 4A to 4D are cross-sectional views of devices for explaining a general method for manufacturing a cell of a CIGS thin film solar battery.
As shown in FIG. 4A, first, a Mo (molybdenum) electrode layer 32 to be a plus-side lower electrode is formed on the substrate 31. Next, as shown in FIG. 4B, a light absorption layer 33 made of a CIGS thin film and showing a p-type is formed on the Mo electrode layer 32 by composition control. Next, as shown in FIG. 4C, a buffer layer 34 such as CdS is formed on the light absorption layer 33, and an impurity is doped on the buffer layer 34 to show an n + type, which is the negative side. A translucent electrode layer 3 made of ZnO (zinc oxide) is formed. Next, as shown in FIG. 2D, a scribe process is performed collectively from the translucent electrode layer 35 made of ZnO to the Mo electrode layer 32 using a mechanical scribe device. Thereby, each cell of the thin film solar cell is electrically separated (that is, each cell is individualized).

[Tandem type]
When a plurality of semiconductors having different band gaps are used for each spectrum range, heat loss due to the difference between photon energy and band gap can be reduced, and power generation efficiency can be improved. Such a layer using a plurality of such photoelectric conversion layers is called a tandem type. In the case of a two-layer tandem, for example, the power generation efficiency can be improved by using a combination of 1.1 eV and 1.7 eV.

[Configuration other than photoelectric conversion layer]
As the n-type semiconductor forming a junction with the I-III-VI group compound semiconductor, for example, a II-VI group compound such as CdS, ZnO, ZnS, Zn (O, S, OH) can be used. These compounds are preferable because they can form a bonding interface without recombination of the photoelectric conversion layer and the carrier (see JP-A-2002-343987).

〔substrate〕
Examples of the substrate include glass plates such as soda lime glass; polyimide, polyethylene naphthalate, polyethersulfone, polyethylene terephthalate, and aramid films; metal plates such as stainless steel, titanium, aluminum, and copper. A laminated mica substrate described in JP-A-2005-317728 can be used. Among these, as the element substrate, a film shape or a foil shape is preferable.

[Back electrode]
As the back electrode, for example, a metal such as molybdenum, chromium, or tungsten can be used. These metal materials are preferable because they do not easily mix with other layers even when heat treatment is performed. When using a photovoltaic layer including a semiconductor layer (light absorption layer) made of a group I-III-VI compound semiconductor, it is preferable to use a molybdenum layer. In the back electrode, a recombination center exists at the boundary surface between the light absorption layer CIGS and the back electrode. Therefore, if the connection area between the back electrode and the light absorption layer is larger than necessary for electrical conduction, the power generation efficiency is lowered. In order to reduce the contact area, for example, it is preferable to use a structure in which an insulating layer and a metal are arranged in stripes as an electrode layer (see Japanese Patent Laid-Open No. 9-219530).
Examples of the layer structure include a super straight type and a substrate type. When a photovoltaic layer including a semiconductor layer (light absorption layer) made of an I-III-VI group compound semiconductor is used, it is preferable to use a substrate type structure because of high conversion efficiency.

[Buffer layer]
For example, CdS, ZnS, ZnS (O, OH), ZnMgO, or the like can be used as the buffer layer. For example, when the band gap of the light absorption layer is increased by increasing the GaGS concentration of CIGS, the conduction band becomes too larger than the conduction band of ZnO. Therefore, ZnMgO having a large conduction band energy is preferable for the buffer layer.

[Transparent conductive layer]
After forming the buffer layer, the transparent conductive layer used in the solar cell of the present invention is preferably coated using the metal nanowire-containing aqueous dispersion, but after forming the buffer layer, the ZnO layer is formed. The metal nanowire-containing aqueous dispersion may be applied.
As the method for producing the transparent conductive film, preferably, the conductive film-forming laminate of the present invention is used as a transfer material, a photosensitive layer is formed on a substrate by a transfer method, and then dried. It is done. Annealing by heating may be performed after the formation of the photosensitive layer. In this case, the heating temperature is preferably 50 ° C. or higher and 300 ° C. or lower, and more preferably 70 ° C. or higher and 200 ° C. or lower.

The said transparent conductive film can be used for the transparent electrode of all the solar cells. Further, the present invention can also be applied to a crystalline (single crystal, polycrystalline, etc.) silicon solar battery that does not use a transparent electrode as a current collecting electrode. Crystalline silicon solar cells generally use silver-deposited electric wires or electric wires made of silver paste as current collecting electrodes. However, by applying the transparent conductive layer used in the present invention, high photoelectricity can be obtained. Conversion efficiency is obtained.
In addition, the transparent conductive layer used in the solar cell of the present invention has a high infrared wavelength transmittance and a low sheet resistance. Amorphous silicon solar cells, copper / indium / selenium (so-called CIS), copper / indium / gallium / selenium (so-called CIGS), copper / indium / gallium / selenium / sulfur (so-called CIGSS) It is suitably used for I-III-VI group compound semiconductor solar cells.

Examples of the present invention will be described below, but the present invention is not limited to these examples.
In the following examples, the average diameter (average minor axis length) and average major axis length of metal nanowires were measured as follows.

<Average diameter (average minor axis length) and average major axis length of metal nanowires>
Using a transmission electron microscope (TEM; manufactured by JEOL Ltd., JEM-2000FX), 300 metal nanowires were observed, and the average diameter (average minor axis length) and average length of the metal nanowires from the average value. The shaft length was determined.

[Abbreviations for synthesis examples]
The meanings of the abbreviations of the components used in the following synthesis examples are as follows.
AA: acrylic acid MAA: methacrylic acid MMA: methyl methacrylate CHMA: cyclohexyl methacrylate St: styrene GMA: glycidyl methacrylate DCM: dicyclopentanyl methacrylate BzMA: benzyl methacrylate AIBN: azobisisobutyronitrile PGMEA: propylene glycol monomethyl ether acetate MFG : 1-methoxy-2-propanol THF: tetrahydrofuran

(Synthesis Example 1)
<Synthesis of Binder (A-1)>
AA (9.64 g) and BzMA (35.36 g) are used as monomer components constituting the copolymer, and AIBN (0.5 g) is used as a radical polymerization initiator, and these are used as a solvent PGMEA (55.00 g). ) To obtain a PGMEA solution (solid content concentration: 45% by mass) of binder (A-1). 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 11000, the molecular weight distribution (Mw / Mn) was 1.72, and the acid value was 155 mgKOH / g. .

(Synthesis Example 2)
<Synthesis of binder (A-2)>
7.48 g of MFG (manufactured by Nippon Emulsifier Co., Ltd.) was added in advance to the reaction vessel, the temperature was raised to 90 ° C., and MAA (14.65 g), MMA (0.54 g), CHMA (17.55 g) as monomer components. Then, a mixed solution consisting of AIBN (0.50 g) and MFG (55.2 g) as a radical polymerization initiator was dropped into a 90 ° C. reaction vessel over 2 hours in a nitrogen gas atmosphere. After dripping, it was made to react for 4 hours and the acrylic resin solution was obtained.
Next, 0.15 g of hydroquinone monomethyl ether and 0.34 g of tetraethylammonium bromide were added to the obtained acrylic resin solution, and then 12.26 g of GMA was added dropwise over 2 hours. After dropping, after reacting at 90 ° C. for 4 hours while blowing air, it was prepared by adding PGMEA so that the solid content concentration was 45% by mass, and a solution of the binder (A-2) (solid content concentration: 45% by mass) was obtained.
The molecular weight was measured using gel permeation chromatography (GPC). As a result, the polystyrene-equivalent weight average molecular weight (Mw) was 31,300, the molecular weight distribution (Mw / Mn) was 2.32, and the acid value was 74.5 mgKOH / g.

Binder (A-2)

(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 73 ° C. at 3 ° C./min. Then, the stirring rotation speed was reduced to 200 rpm and heated for 5.5 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 form 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).

  As a result, silver nanowires having an average minor axis length of 17.2 μm, an average major axis length of 34.2 μm, and a coefficient of variation of 17.8% were obtained. Among the obtained silver nanowires, the ratio of silver nanowires having an aspect ratio of 10 or more was 81.8%.

Example 1
<Preparation of substrate A having transferability>
On a 75 μm thick polyethylene terephthalate film temporary support (PET temporary support), a coating solution for a thermoplastic resin layer having the following formulation A1 was applied, dried at 100 ° C. for 2 minutes, and further at 120 ° C. for 1 minute. After drying, a cushion layer made of a thermoplastic resin layer having a dry layer thickness of 16.5 μm was formed. Here, the temperatures “100 ° C.” and “120 ° C.” in the drying conditions are both substrate temperatures. The same applies to the temperature under the following drying conditions.

<Prescription A1 of coating solution for thermoplastic resin layer>
Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (= 55 / 11.7 / 4.5 / 28.8 [molar ratio], weight average molecular weight 90,000) 58.4 parts Styrene / acrylic acid copolymer (= 63/37 [molar ratio], weight average molecular weight 8,000) ... 136 parts · 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane
・ ・ ・ 90.7 parts ・ Surfactant Megafac F-780-F
(Manufactured by Dainippon Ink and Chemicals, Inc.) 5.4 parts, methanol, 111 parts, 1-methoxy-2-propanol, 63.4 parts, methyl ethyl ketone, 534 parts

  Next, on the formed cushion layer, an intermediate layer coating solution consisting of the following formulation B is applied, dried at 80 ° C. for 1 minute, and further dried at 120 ° C. for 1 minute to obtain an intermediate layer having a dry layer thickness of 1.6 μm. Were laminated.

<Prescription B of coating solution for intermediate layer>
Polyvinyl alcohol (PVA-205, saponification rate 88%, manufactured by Kuraray Co., Ltd.)
… 3.22 parts ・ Polyvinylpyrrolidone (PVP K-30, IS
1.49 parts, methanol ... 42.9 parts, distilled water ... 52.4 parts

<< Preparation of conductive layer >>
-Preparation of PGMEA dispersion (Ag-1) of silver nanowires-
1 part by weight of polyvinylpyrrolidone (K-30, manufactured by Tokyo Chemical Industry Co., Ltd.) and 100 parts by weight of n-propanol are added to 100 parts by weight of the aqueous silver nanowire dispersion (1) prepared in Preparation Example 1. Then, it was concentrated with a cross flow filter using a ceramic filter (manufactured by NGK) until the mass reached 10 parts by mass. Next, 100 parts by mass of n-propanol and 100 parts by mass of ion-exchanged water were added, and the operation of concentrating until the mass became 10 parts by mass again was repeated 3 times. Further, 1 part by mass of the binder (A-1) and 10 parts by mass of n-propanol were added. After centrifugation, the supernatant solvent was removed by decantation, PGMEA was added, redispersion was performed, and centrifugation was performed. The operation until redispersion was repeated three times, and finally PGMEA was added to obtain a silver nanowire PGMEA dispersion (Ag-1). The final addition amount of PGMEA was adjusted so that the silver content was 2% by mass of silver. The content of the polymer used as the dispersant was 0.05% by mass.

<Production of photosensitive layer forming composition>
A photocurable composition having the following composition was prepared, and the resulting photocurable composition A was obtained.
[Photocurable composition A]
(B) Polymer: (Binder (A-1) obtained in the above synthesis example,
(Solid content 45% by mass PGMEA solution) 37.55 parts by mass (b) Polymer: (Binder (A-2) obtained in the synthesis example,
(Solid content 45 mass% PGMEA, MFG mixed solution) 37.55 mass parts (c) Polymerizable compound: Dipentaerythritol hexaacrylate
15.02 parts by mass (d) Photopolymerization initiator: 2,4-bis- (trichloromethyl) -6
[4- (N, N-diethoxycarbonylmethylamino) -3-bromophenyl] -s-triazine 1.481 parts by mass Polymerization inhibitor: Phenothiazine 0.116 parts by mass Surfactant: MegaFac F784F (DIC Corporation) Made)
0.152 parts by mass surfactant: Solsperse 20000 (Nippon Lubrizol Corporation)
1.88 parts by mass Solvent (PGMEA) 283.2 parts by mass

  In the photocurable composition A, the ratio M / P between the mass M of the photopolymerizable compound (c) and the mass P of the binder (b) was 0.2. Moreover, the ratio of the mass which the component except the solvent PGMEA and the solvent MFG occupied to the total mass was 20%.

The photosensitive layer forming composition (1) was obtained by stirring and mixing the photocurable composition A, the silver nanowire dispersion (Ag-1), the solvent PGMEA, and the solvent MEK.
Here, the mixing ratio of each component is such that the ratio B / C of the mass B of the dispersion medium, which is a component other than silver, and the mass C of silver, which is a conductive fiber, is 5.0, in the photosensitive layer forming composition. The silver concentration was 0.635% by mass. The solvent was added so that the ratio of the total mass of PGMEA and MFG to the mass of MEK was 1: 1. In photosensitive composition A-1, the value of (a) the ratio P / C of the mass of the polymer (b) to the mass of the conductive fiber and the value of the ratio M / C of the mass of the polymerizable compound bond (c) are as follows: As shown in Table 1 below.

The above-mentioned composition for forming a photosensitive layer (1) was applied to the substrate A having transferability described above and dried to prepare a laminate for forming a conductive film (1) (photosensitive transfer material). Here, the average coated silver amount was 0.038 g / m ² and the average film thickness was 0.14 μm.
The obtained conductive film-forming laminate (photosensitive transfer material) was designated as a laminate (1-A). In the laminate (1-A), the ratio S / N of the average value S of the total layer thickness of the photosensitive layer for forming the conductive film and the cushion layer and the average value N of the thickness of the substrate is 0.22. there were.

<< Evaluation >>
For the obtained conductive film-forming laminate (1-A), an evaluation sample is prepared as shown below, and the conductivity, optical characteristics, film strength, and patterning property (exposure pattern fidelity reproducibility) are evaluated. It was.
<Evaluation sample preparation>
Using the laminate (1-A), a conductive material having a conductive film on a glass substrate is prepared by reducing the following transfer process, exposure process, development process, and post-baking process, and the obtained conductive material is conductive. It was set as material (1-B). The obtained conductive material (1-B) was evaluated for conductivity, transparency, film strength, and film thickness reduction rate by the methods described below.

(Transfer process)
The surface of the non-alkali glass substrate having a thickness of 0.7 μm, which was subjected to the pretreatment described later, and the surface of the photosensitive layer of Sample 1-1 were laminated and laminated so that a PET temporary support / cushion layer / intermediate layer A laminate having a laminated structure of / photosensitive layer / glass substrate was formed.
Next, the temporary support was peeled from the laminate.
Here, the pretreatment of the glass substrate was performed as follows.
First, a glass substrate immersed in a 1% aqueous solution of sodium hydroxide was subjected to ultrasonic irradiation with an ultrasonic cleaner for 30 minutes, then washed with ion exchange water for 60 seconds, and then heat-treated at 200 ° C. for 60 minutes. Thereafter, a silane coupling liquid (N-β (aminoethyl) γ-aminopropyltrimethoxysilane 0.3 mass% aqueous solution, trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) was sprayed for 20 seconds with a shower, and pure water The shower was washed. The substrate was heated at a substrate temperature of 105 ° C. for 2 minutes with a substrate preheating device immediately before lamination.

(Exposure process)
The sample after removal of the temporary support was exposed using an ultra high pressure mercury lamp i-line (365 nm) at an exposure amount of 40 mJ / cm <2>. Here, exposure of the photosensitive layer is performed from the cushion layer side through a mask. The mask is a conductive exposure, optical characteristics, a uniform exposure portion for evaluating film strength, and a stripe pattern for patterning evaluation (line / space = 50 μm / 50 μm).

(Development process / process)
A 1% triethanolamine aqueous solution was applied to the exposed sample to dissolve and remove the thermoplastic resin layer (cushion layer) and the intermediate layer. The shortest removal time that could completely remove these layers was 30 seconds.
Next, sodium carbonate developer (0.06 mol / liter sodium bicarbonate, sodium carbonate of the same concentration, 1% sodium dibutylnaphthalene sulfonate, anionic surfactant, antifoaming agent, stabilizer contained, product Name: T-CD1, manufactured by Fuji Film Co., Ltd.), the photosensitive resin layer was developed by shower development at 20 ° C. for 30 seconds and a cone type nozzle pressure of 0.15 MPa, and dried at room temperature. Next, heat treatment was performed at 100 ° C. for 15 minutes.

<Conductivity (surface resistance)>
The surface resistance of the rectangular solid exposure region of the obtained conductive film was measured using Loresta-GP MCP-T600 manufactured by Mitsubishi Chemical Corporation, and the following ranking was performed.

5: Surface resistance value of less than 30Ω / □, extremely excellent level 4: Surface resistance value of 30Ω / □ or more, less than 45Ω / □, Excellent level 3: Surface resistance value of 45Ω / □ or more, less than 60Ω / □, Tolerable level 2: Surface resistance value 60Ω / □ or more and less than 100Ω / □, a slightly problematic level.
1: Surface resistance value is 100Ω / □ or more, which is a problematic level.

<Optical characteristics (total light transmittance)>
Measure the total light transmittance (%) of the rectangular solid exposure area of the conductive film after obtained and the total light transmittance (%) of the glass before transferring the conductive layer laminate using a haze guard plus manufactured by Gardner. And the transmittance | permeability of the transparent conductive film was converted from the ratio, and the following ranking was performed. The CIE visibility function y under the C light source was measured at a measurement angle of 0 °, and the following ranking was performed.

A: good level when transmittance is 90% or more B: slightly problematic level when transmittance is 85% or more and less than 90%

<Optical properties (haze)>
The haze value of the rectangular solid exposure area | region of the electrically conductive film after obtained was measured using the Gardner company make haze guard plus, and the following ranking was performed.

A: Excellent level with haze value of less than 1.5% B: Good level with haze value of 1.5% or more and less than 2.0%.
C: Slightly problematic level with a haze value of 2.0% or more and less than 2.5%.
D: A problem level with a haze value of 2.0% or more and less than 2.5%.

<Patternability>
The pattern shape after development in the stripe pattern exposure part was observed with a digital microscope (VHX-600, manufactured by Keyence Corporation, magnification 2,000 times), and the following ranking was performed.

A: Good stripe pattern reproducibility (pattern missing and missing defects are not recognized)
B1: Stripe pattern formation failure (pattern chipping is observed)
B2: Stripe pattern formation failure (pattern omission failure is observed)

<Membrane strength>
Japan Pencil Inspection Association Test Pencil Scratch Pencil (Hardness HB and Hardness B) set according to JIS K5600-5-4 with a pencil scratch coating film hardness tester (manufactured by Toyo Seiki Seisakusho Co., Ltd., model NP) After scratching over a length of 10 mm under a load of 500 g, exposure and development were performed under the following conditions, and the scratched portion was observed with a digital microscope (VHX-600, manufactured by Keyence Corporation, magnification 2,000 times). The following ranking was performed. In rank 3 or higher, practically no disconnection of the conductive film is observed, and there is no problem that the conductivity can be ensured.
〔Evaluation criteria〕
5: Scratch marks are not recognized by pencil scratching with a hardness of 2H, and an extremely excellent level.
4: Excellent level at which conductive fibers are scraped by pencil scratching with a hardness of 2H and scratch marks are observed, but conductive fibers remain and the exposure of the substrate surface is not observed.
3: Although the substrate surface exposure is observed by pencil scratching with a hardness of 2H, the conductive fiber remains by pencil scratching with hardness HB, and the substrate surface exposure is not observed.
2: A problem level where the conductive film is scraped with a pencil of hardness HB, and the exposure of the substrate surface is partially observed.
1: A very problematic level in which the conductive film was shaved with a pencil of hardness HB and most of the substrate surface was exposed.

<Thickness change rate>
A cross section of the film thickness of the sample after development was obtained by SEM (scanning surface electron microscope), and the film thickness change rate was obtained by comparison with the film thickness before development.

(Examples 2 to 10, Comparative Examples 1 to 12)
The mixing ratio of the photocurable composition A and the silver nanowire dispersion Ag-1 is changed with respect to the method for producing the laminate (1-A), and the mass B of the dispersion medium and the mass C of the silver as the conductive fiber are changed. The ratio B / C value and the film thickness of the photosensitive layer were changed as shown in Table 1 below to obtain laminates (2-A) to laminates (6-A).
In addition, the photocurable composition A was prepared by a method different from that of the photocurable composition A, except that the blending ratio of the polymer and the monomer was changed and the mass ratio was changed as shown in Table 1. Things B, C, D and E were obtained. Here, the mass ratio of the binder (A-1) and the binder (A-2) as the polymer was always 1: 1.
Using these photocurable compositions, the laminate (1-A) and the mass ratio of the conductive fibers, the mass ratio of the binder, and the thickness of the photosensitive layer to be formed were changed as shown in Table 1. Samples were prepared in the same manner, and laminates (1-B) to (4-B), laminates (1-C) to (4-C), laminates (1-D) to (6-D) And laminates (1-E) to (3-E) were obtained.

  Tables 1 and 2 show the results of evaluating the obtained samples in the same manner as the laminate (1-A). From Table 1, when the ratio of the polymerizable compound and the polymer to the conductive fiber is within the range of the present invention, the film quality, conductivity, transparency, haze, and patterning properties are all irrespective of the film thickness of the photosensitive layer. It can be seen that the desired level is maintained. In Table 2, the value which measured the film thickness change rate about the laminated body (1-A), the laminated body (2-B), the laminated body (5-D), and the laminated body (3-E) was shown. .

  The film thickness after the solvent application step is preferably about 20 to 55 when the value before the application step is 100. By the solvent application step, unnecessary substances in the photosensitive layer are removed, and the conductivity is improved. In addition, since the film | membrane intensity | strength will become weak when there is too much removal amount, about 20 is preferable for a lower limit.

(Example 11)
<Production of integrated solar cell>
-Fabrication of amorphous solar cells (super straight type)-
On the glass substrate, the laminate (1-A) of Example 1 is transferred using a laminator to form a photosensitive layer, which is exposed and developed under the same conditions as in Example 1, whereby a glass substrate is obtained. A transparent conductive film was formed thereon. However, the entire surface was uniformly exposed without using a mask. A p-type film with a film thickness of about 15 nm, an i-type film with a film thickness of about 350 nm, and an n-type amorphous silicon film with a film thickness of about 30 nm are formed thereon by a plasma CVD method. The photoelectric conversion element 101 was produced.

(Example 12)
-Fabrication of CIGS solar cells (substrate type)-
On a soda-lime glass substrate, a molybdenum electrode having a film thickness of about 500 nm by a DC magnetron sputtering method, a Cu (In0.6Ga0.4) Se2 thin film that is a chalcopyrite semiconductor material having a film thickness of about 2.5 μm by a vacuum deposition method, a solution A cadmium sulfide thin film having a thickness of about 50 nm was formed by a deposition method.
On top of that, the laminate (1-A) of Example 1 was transferred using a laminator, and exposed and developed under the same conditions as in Example 1, thereby forming a transparent conductive film on the glass substrate, A photoelectric conversion element 201 was produced.

  Next, conversion efficiency was evaluated as follows in each produced solar cell. The results are shown in Table 3.

<Evaluation of solar cell characteristics (conversion efficiency)>
About each solar cell, efficiency was measured by irradiating simulated sunlight of AM1.5 and 100 mW / cm < ² >.

  From the results in Table 3, it was found that high conversion efficiency can be obtained in any integrated solar cell system by using the conductive film-forming laminate of the present invention for forming a transparent conductive film.

(Example 13)
-Fabrication of touch panel-
Sample 1-1 of Example 1 was transferred onto a glass substrate in the same manner as in Example 1, and then exposed and developed to form a transparent conductive film. Using the resulting transparent conductive film, "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) Issued), “FPD International 2009 Forum T-11 Lecture Textbook”, “Cypress Semiconductor Corporation Application Note AN2292”, and the like.
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 laminate for forming a conductive film of the present invention can be used as it is or as a transfer material, and has excellent patternability by development, and excellent transparency, conductivity and durability (film strength). Transparent conductive film, touch panel, antistatic material for display, electromagnetic wave shield, electrode for organic EL display, electrode for inorganic EL display, electronic paper, electrode for flexible display, antistatic film for flexible display, display element, integrated solar cell It can be suitably used for production.

10 Laminate for forming conductive film (transfer material)
12 Transfer base material (base material)
14 Cushion layer 16 Photosensitive layer 18 Transfer object (glass substrate)
DESCRIPTION OF SYMBOLS 20 Touch panel 21 Transparent substrate 22 Transparent conductor 27 Protective film 28 Intermediate protective film 29 Anti-glare film 30 Electrode terminal 32 Mo electrode layer 33 Light absorption layer 34 Buffer layer 35 Translucent electrode layer

Claims (19)

On the substrate, has a photosensitive fiber containing a conductive fiber having a minor axis diameter of 150 nm or less, a polymer, a compound having an ethylenically unsaturated double bond, and a photopolymerization initiator,
Conductive film-forming laminate in which the mass P of the polymer, the mass M of the compound having an ethylenically unsaturated double bond, and the mass C of the conductive fibers contained in the photosensitive layer satisfy the following relationship: .
2.0 ≦ P / C ≦ 10.0
0.3 ≦ M / C ≦ 1.5   The conductive film-forming laminate according to claim 1, wherein the photosensitive layer has a thickness of 0.01 to 0.3 μm. The electroconductivity of Claim 1 or Claim 2 with which the total mass B of the dispersion medium which is components other than the said electroconductive fiber contained in the said photosensitive layer, and the mass C of the said electroconductive fiber satisfy | fill the following relationship. Laminate for film formation.
2.5 ≦ B / C ≦ 15.0   The laminate for forming a conductive film according to any one of claims 1 to 3, wherein the conductive fiber is a metal nanowire.   The laminate for forming a conductive film according to claim 4, wherein the metal nanowire is made of silver or an alloy of silver and a metal other than silver.   The laminate for forming a conductive film according to any one of claims 1 to 5, wherein the polymer has an average acid value of 50 mgKOH / g or more and 200 mgKOH / g or less.   The conductive film forming device according to any one of claims 1 to 6, wherein the compound having an ethylenically unsaturated double bond is a monomer or an oligomer having a plurality of ethylenically unsaturated double bonds in the molecule. Laminated body. On a base material, a conductive fiber having a minor axis diameter of 150 nm or less, a polymer, a compound having an ethylenically unsaturated double bond, and a photopolymerization initiator, a polymer mass P, a compound having an ethylenically unsaturated double bond, A laminated body forming step of forming a photosensitive layer containing the mass M and the mass C of the conductive fiber in an amount satisfying the relationship of the following formulas (1) and (2);
An exposure step of exposing at least part of the photosensitive layer in the obtained laminate;
A conductive film forming method including:
2.0 ≦ P / C ≦ 10.0 Formula (1)
0.3 ≦ M / C ≦ 1.5 Formula (2) The laminate forming step includes
Conductive fibers having a minor axis diameter of 150 nm or less, a polymer, a compound having an ethylenically unsaturated double bond, and a photopolymerization initiator, a polymer mass P, a mass M of a compound having an ethylenically unsaturated double bond, and Or a step of applying a coating solution composition for forming a photosensitive layer on the substrate, wherein the mass C of the conductive fiber satisfies the relationship of the following formulas (1) and (2):
Conductive fibers having a minor axis diameter of 150 nm or less, a polymer, a compound having an ethylenically unsaturated double bond, and a photopolymerization initiator, a polymer mass P, a mass M of a compound having an ethylenically unsaturated double bond, and The step of transferring the photosensitive layer in the laminate for forming a conductive film having the photosensitive layer containing the conductive fiber in an amount satisfying the relationship of the following formulas (1) and (2) to the substrate.
The conductive film formation method according to claim 8.   The conductive film forming method according to claim 9, further comprising a solvent application step of applying a solvent to the photosensitive layer and reducing a dispersion medium contained in the exposed photosensitive layer after the exposure step.   The conductive film forming method according to claim 9 or 10, further comprising a developing step of removing a non-exposed portion by applying a solvent to the exposed photosensitive layer after the exposure step.   The film thickness of the photosensitive layer in the exposed region in the laminate for forming a conductive film after the solvent application step is smaller than the film thickness of the photosensitive layer before the solvent application step. The electrically conductive film formation method of description.   The conductive film forming method according to claim 8, wherein the solvent is a solvent selected from water and an alkaline solution.   The electrically conductive film obtained by the electrically conductive film formation method of any one of Claims 8-13.   The conductive film according to claim 14, wherein the sheet resistance is 0.1 to 10,000 Ω / □.   The conductive film according to claim 14 or 15, which has a light transmittance of 70% or more. A conductive fiber having a minor axis diameter of 150 nm or less, a polymer, a compound having an ethylenically unsaturated double bond, and a photopolymerization initiator;
A conductive element in which the mass P of the polymer, the mass M of the compound having an ethylenically unsaturated double bond, and the mass C of the conductive fiber satisfy the following relationship.
2.0 ≦ P / C ≦ 10.0
0.3 ≦ M / C ≦ 1.5   The touch panel provided with the electrically conductive film of any one of Claims 14-16.   The integrated solar cell provided with the electrically conductive film of any one of Claims 14-16.