JP2012209232A - Conductive patterning material and touch panel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conductive patterning material having high surface hardness, excellent scratch resistance, good patterning properties, high transparency and conductivity, and low haze ratio and surface resistivity, and to provide a touch panel having the conductive patterning material.SOLUTION: The conductive patterning material includes a conductive layer containing metal nano wires having an average short axis length of 50 nm or less and silica microparticles. The ratio (B/A) of the average grain size B nm of the silica microparticles and the average short axis A nm of the metal nano wires is 0.9-5, the content of the metal nano wires in the conductive layer is 0.01-0.07 g/m, the surface resistivity is 300 Ω/sq. or lower, and the haze ratio is 2% or less.

Description

  The present invention relates to a conductive patterning material and a touch panel using the conductive patterning material.

  Transparent conductive materials are widely used for touch panels, display electrodes, electromagnetic shielding, organic EL display electrodes, inorganic EL display electrodes, electronic paper, flexible display electrodes, integrated solar cells, display elements, and other various devices. It is important as a member in the electric and electronic fields.

In recent years, instead of a transparent conductive material such as indium oxide (ITO) doped with tin, a transparent conductive film having a transparent conductive layer including metal nanowires with high transparency, low surface resistivity, and good conductivity Has been proposed (see, for example, Patent Document 1).
Pattern processing is indispensable when using a transparent conductive material as a transparent electrode of an electronic device. In this pattern formation step, durability is required to obtain high conductivity without damaging the transparent electrode. In addition, when using a transparent conductive material for the touch panel, the touch panel is frequently touched by the hand, rubbed with a cloth, or traced with the pen tip. There is a problem that the surface hardness becomes worse, and it is strongly demanded to increase the surface hardness.
Although attempts have been made to provide a hard coat layer on a transparent conductive film made of a transparent conductive material (see, for example, Patent Document 2), when a hard coat layer is provided, cracks may occur in the manufacturing process, or transparent If the adhesiveness with the conductive film is poor, there is a problem such as low handling.

In order to solve this problem, a conductor in which a glass substrate is coated with a conductive composition containing silica fine particles has been proposed as a conductor coated with a conductive composition with increased hardness (see Patent Document 3).
However, this proposed conductor has a surface resistivity of 10 ⁴ Ω / □ or more, and is likely to cause disconnection due to Joule heat generated during energization, and a voltage drop occurs between the upstream and downstream of the wiring. There is a problem in that the area when used for is limited.

In addition, a conductive composition containing conductive fibers having an average minor axis diameter of 0.1 μm to 50 μm and fine particles such as silica having an average particle diameter of 0.4 μm to 100 μm has been proposed (see Patent Document 4). .
However, since the proposed conductive composition has a large average minor axis diameter of conductive fibers and an average particle diameter of fine particles, scattering due to the conductive fibers occurs, resulting in poor transparency and a high haze ratio. There is a problem.

Moreover, the base material with a transparent conductive film provided with the transparent conductive film containing metal nanowire and particle | grains, such as a silica, is proposed (refer patent documents 5 and 6).
However, this proposed transparent conductive film has a small ratio (B / A) of the average particle diameter (B) of the refractive index control particles to the average minor axis length (A) of the metal nanowires. Such a transparent conductive film has a problem that the surface resistivity and haze ratio are high and the surface hardness cannot be increased.

  Therefore, a conductive patterning material having high surface hardness, excellent scratch resistance, good patternability, high transparency and conductivity, low haze ratio and surface resistivity, and the conductive patterning material At present, the provision of touch panels is required.

JP 2009-215594 A JP 2009-70660 A JP 2005-82768 A JP 2004-224829 A JP 2011-29037 A JP 2011-29099 A

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, the present invention provides a conductive patterning material having high surface hardness, excellent scratch resistance, good patternability, high transparency and conductivity, low haze and surface resistivity, and the conductivity. An object is to provide a touch panel having a patterning material.

In order to solve the above-mentioned problems, the present inventors have made extensive studies and as a result, obtained the following findings. That is, a conductive patterning material having a conductive layer containing metal nanowires having an average minor axis length of 50 nm or less and silica fine particles, the average particle diameter Bnm of the silica fine particles, and the average minor axis length of the metal nanowires is the ratio between Anm (B / a) is, is 0.9 to 5, in the conductive layer, a conductive amount of the metal nanowires is 0.01g ^{/ m 2} ~0.07g ^/ m 2 The patterning material has high surface hardness, excellent scratch resistance, good patternability, high transparency with a surface resistivity of 300 Ω / □ or less and high conductivity, and a low haze ratio of 2% or less. The inventors have found that the surface resistivity is low, and have completed the present invention.

The present invention is based on the above findings by the present inventors, and means for solving the above problems are as follows. That is,
<1> A conductive patterning material having a conductive layer containing metal nanowires having an average minor axis length of 50 nm or less and silica fine particles, the average particle diameter Bnm of the silica fine particles, and the average minor axis of the metal nanowires ratio of the length Anm (B / a) is, is 0.9 to 5, the content of the metal nanowires in the conductive layer is ^{0.01g / m 2 ~0.07g / m 2} , A conductive patterning material having a surface resistivity of 300Ω / □ or less and a haze ratio of 2% or less.
<2> The conductive patterning material according to <1>, wherein the ratio (B / A) is 1.1 or more and 4.5 or less.
<3> The conductive patterning material according to any one of <1> to <2>, wherein the silica fine particles have an average particle size of 60 nm or less.
<4> The conductive patterning material according to any one of <1> to <3>, wherein the lower limit of the average particle size of the silica fine particles is (average minor axis length of metal nanowires −2) nm.
<5> The conductive patterning material according to any one of <1> to <4>, wherein an average thickness of the conductive layer is 0.01 μm to 0.3 μm.
<6> The conductive patterning material according to any one of <1> to <5>, wherein the transmittance of the conductive layer is 80% or more, and the surface resistivity of the conductive layer is 10Ω / □ to 150Ω / □. It is.
<7> A touch panel comprising the conductive patterning material according to any one of <1> to <6>.

  According to the present invention, the conventional problems can be solved, the object can be achieved, the surface hardness is high, the scratch resistance is excellent, the patterning property is good, and the transparency and conductivity are high. It is possible to provide a conductive patterning material having a low haze ratio and surface resistivity, and a touch panel having the conductive patterning material.

FIG. 1 is a schematic sectional view showing an example of a layer structure of the conductive patterning material of the present invention. 2A to 2C are explanatory diagrams for explaining an example of a transfer method using the conductive patterning material of the present invention. FIG. 3 is a schematic cross-sectional view showing an example of the touch panel (surface type capacitance type) of the present invention. FIG. 4 is a schematic cross-sectional view showing another example of the touch panel (surface type capacitance type) of the present invention. FIG. 5 is a schematic cross-sectional view showing an example of the touch panel (projection capacitive type) of the present invention. FIG. 6 is a schematic cross-sectional view showing an example of the touch panel (resistance film type) of the present invention.

(Conductive patterning material)
The conductive patterning material of the present invention preferably has at least a conductive layer containing metal nanowires having an average minor axis length of 50 nm or less and silica fine particles, and further preferably has a transfer substrate and a cushion layer. Depending on the situation, it has other layers such as a photosensitive layer, an antifouling layer, a UV cut layer, and an antireflection layer. Moreover, the protective film may be laminated | stacked on the outermost surface.

There is no restriction | limiting in particular about the shape, structure, size, etc. of the said conductive patterning material, According to the objective, it can select suitably, For example, a film | membrane form, a sheet form, etc. are mentioned as said shape. Examples of the structure include a single layer structure and a laminated structure. The size can be appropriately selected according to the application.
The conductive patterning material is flexible and preferably transparent, and the transparent includes colorless and transparent, colored transparent, translucent, colored translucent and the like.

<Conductive layer>
The conductive layer preferably contains at least metal nanowires with an average minor axis length of 50 nm or less and silica fine particles, and further contains a binder and a photosensitive compound, and further contains other components as necessary. To do.

<< Metal nanowires >>
The metal nanowire is a metal nanowire having an average minor axis length of 50 nm or less. In the present invention, “wire” means a fiber having a solid structure.

-Shape-
The shape of the metal nanowire is not particularly limited as long as it is a solid structure, and can be appropriately selected depending on the purpose. For example, the shape of the columnar shape, a rectangular parallelepiped shape, a column shape having a polygonal section, etc. However, in applications where high transparency is required, a cylindrical shape or a cross-sectional shape with rounded polygonal corners is preferable.
The cross-sectional shape of the metal nanowire can be examined by applying a metal nanowire aqueous dispersion on a substrate and observing the cross-section with a transmission electron microscope (TEM).
The corner of the cross section of the metal nanowire means a peripheral portion of a point that extends each side of the cross section and intersects with a perpendicular drawn from an adjacent side. Further, “each side of the cross section” is a straight line connecting these adjacent corners. In this case, the ratio of the “outer peripheral length of the cross section” to the total length of the “each side of the cross section” was defined as the sharpness. A cross-sectional shape having a sharpness of 75% or less is defined as a cross-sectional shape having rounded corners. The sharpness is preferably 60% or less, and more preferably 50% or less. If the sharpness exceeds 75%, the electrons may be localized at the corners, and plasmon absorption may increase, or the transparency may deteriorate due to yellowing or the like.
There is no restriction | limiting in particular as a lower limit of the said sharpness, Although it can select suitably according to the objective, 10% or more is preferable. If the sharpness is less than 10%, the contact probability between nanowires tends to decrease, or the resistance tends to increase.

−Average minor axis length−
The average minor axis length of the metal nanowire (sometimes referred to as “average minor axis diameter” or “average diameter”) is 50 nm or less, preferably 40 nm or less, more preferably 30 nm or less, and more preferably 25 nm or less. Is particularly preferred. When the average minor axis length exceeds 50 nm, scattering due to metal nanowires occurs, and sufficient transparency cannot be obtained, and the haze ratio may be increased.
Moreover, there is no restriction | limiting in particular as a lower limit of the said average short-axis length, Although it can select suitably according to the objective, 1 nm or more is preferable and 10 nm or more is more preferable. When the lower limit value of the average minor axis length is less than 1 nm, the oxidation resistance may deteriorate and the durability may deteriorate.
Therefore, the average minor axis length of the metal nanowire is preferably 1 nm to 50 nm, more preferably 10 nm to 40 nm, still more preferably 10 nm to 30 nm, and particularly preferably 10 nm to 25 nm.
In the present invention, the average short axis length of the metal nanowire is measured by observing the metal nanowire using a transmission electron microscope (TEM), and measuring at least 300 metal nanowires. It is the value which calculated | required the average value of short-axis length.

−Average major axis length−
The average major axis length of the metal nanowire (hereinafter sometimes referred to as “average length”) is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 2 μm or more, 2 micrometers-40 micrometers are more preferable, 3 micrometers-35 micrometers are still more preferable, and 5 micrometers-30 micrometers are especially preferable.
If the average major axis length is less than 2 μm, it may be difficult to form a dense network, and sufficient conductivity may not be obtained. If the average major axis length exceeds 40 μm, the metal nanowire is too long and manufactured. Sometimes entangled and agglomerates may occur during the manufacturing process.
In the present invention, the average major axis length of the metal nanowires is determined by observing the metal nanowires using a transmission electron microscope (TEM), measuring the major axis length, and measuring the length of at least 300 metal nanowires. It is the value which calculated | required the average value of axial length.
Here, when the metal nanowire is bent, a circle having the arc as an arc is taken into consideration, and a value calculated from the radius and the curvature is taken as the long axis length.

-Material-
There is no restriction | limiting in particular as a material of the said metal nanowire, According to the objective, it can select suitably, For example, the group which consists of a 4th period, a 5th period, and a 6th period of a long periodic table (IUPAC1991) At least one metal selected from the group 2, more preferably at least one metal selected from the group 2 to group 14, the group 2, the group 8, the group 9, the group 10, the group 11, Particularly preferred is at least one metal selected from Group 12, Group 13, and Group 14. Further, it is particularly preferable that these materials are contained as a main component.

-Metal-
Examples of the metal include copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, iron, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantel, titanium, bismuth, antimony, and lead. Or alloys thereof. Among these, the metal is preferably silver or an alloy of silver and another metal in terms of excellent conductivity.
There is no restriction | limiting in particular as another metal in the said alloy, Although it can select suitably according to the objective, Platinum, osmium, palladium, and iridium are preferable. These may be used alone or in combination of two or more.

-Manufacturing method-
The method for producing the metal nanowire is not particularly limited and may be produced by any method. While adding a metal complex solution in a solvent in which a dispersion additive and a halogen compound are dissolved, the metal nanowire is heated. It is preferable to produce by reducing metal ions.
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 The method described in the above can also be used.

--Metal complex--
There is no restriction | limiting in particular as said metal complex, Although it can select suitably according to the objective, A silver complex is especially preferable. Examples of the ligand of the silver complex include CN-, SCN-, SO32-, thiourea, ammonia and the like. For these, see “The Theory of the Photographic Process 4th Edition”, Macmillan Publishing, T .; H. Reference can be made to the description by James. Among these, a silver ammonia complex is particularly preferable.
The metal complex is preferably added after the dispersion additive and the halogen compound. Probably because the wire core can be formed with high probability, there is an effect of increasing the proportion of the metal nanowires having an appropriate diameter and length in the present invention.

-Dispersant additive-
The dispersion additive is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include an amino group-containing compound, a thiol group-containing compound, a sulfide group-containing compound, an amino acid or a derivative thereof, a peptide compound, and a polysaccharide. Synthetic polymers, gels derived from these, and the like. These may be used alone or in combination of two or more.
Among these, the dispersion additive is particularly preferably gelatin, polyvinyl alcohol, methyl cellulose, hydroxypropyl cellulose, polyalkyleneamine, partial alkyl ester of polyacrylic acid, polyvinyl pyrrolidone, or polyvinyl pyrrolidone copolymer.
For the structure that can be used as the dispersion additive, for example, the description of “Encyclopedia of Pigments” (edited by Seijiro Ito, published by Asakura Shoin Co., Ltd., 2000) can be referred to.
Moreover, the shape of the metal nanowire obtained can also be changed with the kind of dispersion additive to be used.

--Halogen compounds--
The halogen compound is not particularly limited and may be appropriately selected depending on the intended purpose. However, a compound containing bromine, chlorine, or iodine is preferable, and examples thereof include sodium bromide, sodium chloride, sodium iodide, and iodide. More preferred are alkali halides such as potassium, potassium bromide, potassium chloride, and potassium iodide, and compounds that can be used in combination with the dispersion additive.
Depending on the type of the halogen compound, there may be one that functions as a dispersion additive, but it can be preferably used as well.

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

  The dispersion additive and the halogen compound may be the same substance, or may be used in combination. Examples of the compound in which the dispersion additive and the halogen compound are used in combination include, for example, HTAB (hexadecyl-trimethylammonium bromide) containing an amino group and a bromide ion, and HTAC (hexadecyl-trimethylammonium chloride) containing an amino group and a chloride ion. , Containing amino group and bromide ion or chloride ion, dodecyltrimethylammonium bromide, dodecyltrimethylammonium chloride, stearyltrimethylammonium bromide, stearyltrimethylammonium chloride, decyltrimethylammonium bromide, decyltrimethylammonium chloride, dimethyldistearylammonium bromide, dimethyl Distearyl ammonium chloride, dilauryl dimethyl ammonium bromide, dilauryl di Chill ammonium chloride, dimethyl dipalmityl ammonium bromide, dimethyl dipalmityl ammonium chloride.

--Solvent--
There is no restriction | limiting in particular as said solvent, Although it can select suitably according to the objective, A hydrophilic solvent is preferable and water, alcohol, ethers, ketones etc. are mentioned, for example. These solvents may be used alone or in combination of two or more.
Examples of the alcohols include methanol, ethanol, propanol, isopropanol, butanol, and ethylene glycol.
Examples of the ethers include dioxane and tetrahydrofuran.
Examples of the ketones include acetone.

There is no restriction | limiting in particular as heating temperature at the time of the said heating, Although it can select suitably according to the objective, 250 degrees C or less is preferable, 20 to 200 degreeC is more preferable, 30 to 180 degreeC is still more preferable, 40 to 170 degreeC is especially preferable. The lower the heating temperature, the lower the nucleation probability and the longer the metal nanowires. If the heating temperature is less than 20 ° C., the metal nanowires are likely to be entangled and the dispersion stability may deteriorate. In addition, when the heating temperature exceeds 250 ° C., the corner of the cross section of the metal nanowire becomes steep, and the transmittance in the evaluation of the coating film may be lowered.
As needed, you may change temperature suitably in the formation process of metal nanowire. By changing the temperature during the formation process of the metal nanowires, it is possible to improve the monodispersity improvement effect by controlling the nucleation of metal nanowires, suppressing renucleation, and promoting selective growth.

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. These may be used alone or in combination of two or more. Among these, the reducing agent is particularly preferably a reducing saccharide, a sugar alcohol as a derivative thereof, or ethylene glycol.

Examples of the borohydride metal salt include sodium borohydride and potassium borohydride.
Examples of the aluminum hydride salt include lithium aluminum hydride, potassium aluminum hydride, cesium aluminum hydride, aluminum beryllium hydride, magnesium aluminum hydride, and calcium aluminum hydride.
Examples of the alkanolamine include diethylaminoethanol, ethanolamine, propanolamine, triethanolamine, dimethylaminopropanol, and the like.
Examples of the aliphatic amine include propylamine, butylamine, dipropyleneamine, ethylenediamine, and triethylenepentamine.
Examples of the heterocyclic amine include piperidine, pyrrolidine, N-methylpyrrolidine, and morpholine.
Examples of the aromatic amine include aniline, N-methylaniline, toluidine, anisidine, and phenetidine.
Examples of the aralkylamine include benzylamine, xylenediamine, and N-methylbenzylamine.
As said alcohol, methanol, ethanol, 2-propanol etc. are mentioned, for example.
Examples of the organic acids include citric acid, malic acid, tartaric acid, citric acid, succinic acid, ascorbic acid, and salts thereof.
Examples of the reducing saccharide include glucose, galactose, mannose, fructose, sucrose, maltose, raffinose, stachyose and the like.
Examples of the sugar alcohols include sorbitol.

  Depending on the kind of the reducing agent, it may function as a dispersion additive or a solvent as a function, and can be preferably used in the same manner.

The step of adding the dispersion additive and the halogen compound in the production of the metal nanowire may be before or after the addition of the reducing agent. Before or after the addition of metal halide fine particles, it may be after addition, but in order to obtain metal nanowires with better monodispersity, it is preferable to add the halogen compound in two or more stages.
When the addition of the dispersion additive is divided into two or more steps, the amount needs to be changed depending on the length of the required metal nanowires. This is considered to be due to the length of the metal nanowires by controlling the amount of metal particles as a nucleus.

  After forming the metal nanowires, it is preferable to further perform a desalting treatment. The desalting treatment is not particularly limited and can be appropriately selected from known methods according to the purpose. Examples thereof include ultrafiltration, dialysis, gel filtration, decantation, and centrifugation. .

-Content-
The content of the metal nanowires having an average minor axis length of 50 nm or less in the conductive layer is 0.01 g / m ^{2 to} 0.07 g / m ² , but 0.02 g / m ^{2 to} 0.05 g / m. ² is preferable, and 0.02 g / m ^{2 to} 0.03 g / m ² is particularly preferable.
When the content of the metal nanowire is less than 0.01 g / m ² , the conductive material that contributes to conductivity may decrease and conductivity may decrease, and at the same time a dense network cannot be formed. Voltage concentration may occur, resulting in a decrease in durability and an increase in surface resistivity. Furthermore, when the component which does not contribute largely to electroconductivity other than metal nanowire is included, since this component has absorption, it is not preferable. In particular, when the component other than the metal nanowire is a metal and the plasmon absorption such as a spherical shape is strong, the transparency may be deteriorated.
Moreover, when content of metal nanowire exceeds 0.07 g / m < ² >, surface hardness cannot be raised but a haze rate may become high and the transmittance | permeability may fall.
On the other hand, when the content of the metal nanowire is within the particularly preferable range, it is advantageous in that the surface hardness, the transmittance, and the conductivity are excellent, and the surface resistivity and the haze ratio are low.
The content of the metal nanowires in the conductive layer is the concentration of the dispersion liquid and the concentration of the metal nanowires contained in the dispersion liquid when the dispersion liquid containing the metal nanowires is disposed on the target substrate. It can be adjusted by changing.
The content of the metal nanowires in the conductive layer can be measured by, for example, a fluorescent X-ray analyzer (ICP emission analyzer).

In the present invention, the conductive layer may contain metal nanowires with an average minor axis length exceeding 50 nm, but the content of metal nanowires with an average minor axis length exceeding 50 nm should be smaller. preferable.
There is no restriction | limiting in particular as content of metal nanowire with an average short axis length of 50 nm or less with respect to metal nanowire total amount, Although it can select suitably according to the objective, 50% or more is preferable and 60% or more is preferable. More preferably, 75% or more is particularly preferable. When the content of metal nanowires having an average minor axis length of 50 nm or less with respect to the total amount of metal nanowires is less than 50%, transparency may deteriorate or haze ratio may increase.

For example, when the metal nanowire is a silver nanowire, the content of the metal nanowire having an average minor axis length of 50 nm or less is obtained by filtering the silver nanowire aqueous dispersion to obtain an average minor axis length of 50 nm or less. The metal nanowires and metal nanowires with an average minor axis length exceeding 50 nm are separated, and the amount of Ag remaining on the filter paper using the fluorescent X-ray analyzer in the same manner as described above, and the amount of Ag permeating the filter paper And can be obtained by measuring each of them.
A metal nanowire having an average minor axis length of 50 nm or less is observed by observing a metal nanowire that has passed through the filter paper with a TEM, observing an average minor axis length of at least 300 metal nanowires, and examining its distribution. Make sure.
The filter paper is preferably one that can selectively transmit metal nanowires having an average minor axis length of 50 nm or less.

<< Silica fine particles >>
The silica fine particle is not particularly limited as long as it satisfies the ratio (B / A) described later, and can be appropriately selected according to the purpose. For example, anhydrous silica such as colloidal silica and vapor phase method silica And hydrous silica. These may be used alone or in combination of two or more.

  There is no restriction | limiting in particular as a shape of the said silica particle, According to the objective, it can select suitably, A spherical form may be sufficient and an indefinite form may be sufficient, but a spherical form is preferable. Moreover, a hollow particle may be sufficient. The silica fine particles may be crystalline or amorphous.

  The silica fine particles are used in plasma discharge treatment or corona discharge treatment in order to stabilize dispersion in a dispersion liquid or a coating liquid such as a coating liquid, or to improve affinity and binding properties with a binder component. Those subjected to such a physical surface treatment, and those subjected to a chemical surface treatment with a surfactant or a coupling agent are preferred, and those subjected to a chemical surface treatment with a coupling agent are more preferred.

There is no restriction | limiting in particular as said coupling agent, Although it can select suitably according to the objective, Alkoxy metal compounds, such as a titanium coupling agent and a silane coupling agent, are preferable. These may be used alone or in combination of two or more.
Among these, the treatment with a silane coupling agent having an acryloyl group or a methacryloyl group is particularly preferable.
The silica fine particles are preferably dispersed in the medium in advance before the surface treatment in order to reduce the load of the surface treatment.

  Among these, the silica fine particles are preferably colloidal silica, and particularly preferably colloidal silica whose surface is hydrophobized with a chemically bonded alcohol or organosilyl group.

The colloidal silica is colloidal silica composed of ultrafine particles of silicic anhydride dispersed in a solvent.
There is no restriction | limiting in particular as said solvent, Although it can select suitably according to the objective, Alcoholic organic solvent is preferable.
There is no restriction | limiting in particular as said alcoholic organic solvent, According to the objective, it can select suitably, For example, methanol, ethanol, propanol, butanol, methyl ethyl ketone, (gamma) butyl lactone, isopropyl alcohol etc. are mentioned. These may be used alone or in combination of two or more.

  The main component of the colloidal silica is silicon dioxide, but it may contain alumina or sodium aluminate as a minor component, and as a stabilizer, sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia, etc. An inorganic base or an organic base such as tetramethylammonium may be contained.

There is no restriction | limiting in particular as a manufacturing method of the said colloidal silica, According to the objective, it can select suitably according to the objective, for example, the method of preparing by a sol-gel method, the method of preparing by a water glass method Etc. Moreover, you may use a commercial item.
Examples of the method for preparing the sol-gel method include Werner Stober et al. , J .; Colloid and Interface Sci. , 26, 62-69 (1968), Ricky D. et al. Badley et al. , Langmuir 6, 792-801 (1990), Journal of Color Material Association, 61 [9] 488-493 (1988), and the like.

  Examples of the colloidal silica include those described in JP-A-53-112732, JP-B-57-009051, JP-B-57-51653, and the like. Further, as disclosed in JP-A-10-268464, colloidal silica having an elongated shape having a thickness of 1 nm to 50 nm and a length of 10 nm to 1,000 nm, JP-A-9-218488 or JP-A-10-111544. It is also possible to use composite particles of colloidal silica and organic polymer described in 1.

When using a commercially available product, the product name is methyl ethyl ketone-dispersed silica sol such as MEK-ST-L (average particle size: 45 nm) (manufactured by Nissan Chemical Industries, Ltd.); MA-ST-M (average particle size: 25 nm) Methanol-dispersed silica sol (manufactured by Nissan Chemical Industries, Ltd.); isopropanol-dispersed silica sol (manufactured by Nissan Chemical Industries, Ltd.) such as IPA-ST-ZL (average particle diameter: 100 nm); Oscar 105 (average particle diameter: 60 nm), etc. And γ-butyllactone-dispersed silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd.).
Among these, when using a commercial item, Oscar 105, MEK-ST-L and MA-ST-M are preferable, MEK-ST-L and MA-ST-M are more preferable, and MA-ST-M is Particularly preferred.

  The particle size of the silica fine particles is not particularly limited and may be appropriately selected depending on the intended purpose. The average particle size is preferably 100 nm or less, and more preferably 60 nm or less. When the average particle diameter of the silica fine particles exceeds 100 nm, the surface hardness cannot be increased, the haze ratio is increased, and the transmittance is decreased. Moreover, the contact between silver nanowires may be inhibited and flatness may be deteriorated. The silica fine particles are preferably monodisperse particles.

Moreover, there is no restriction | limiting in particular as a lower limit of the average particle diameter of the said silica fine particle, Although it can select suitably according to the objective, It is satisfy | filling (the average short axis length-2 of metal nanowire-2) nm. preferable. If the lower limit of the average particle diameter of the silica fine particles is less than (average minor axis length of metal nanowires −2) nm, the surface hardness cannot be increased, and the surface resistivity and haze ratio increase. In other words, the conductivity cannot be increased.
Therefore, the upper limit value and the lower limit value of the average particle diameter of the silica fine particles are a numerical range in which an arbitrary upper limit value and an arbitrary lower limit value are appropriately combined according to the average minor axis length of the metal nanowires. Can be adopted.

  Here, the average particle diameter of the silica fine particles is a value obtained by observing the silica fine particles using a transmission electron microscope (TEM), measuring the particle diameter, and obtaining an average value of the particle diameters of at least 300 silica fine particles. In the present invention, the average particle size of the silica fine particles is the number average particle size.

There is no restriction | limiting in particular as content of the silica particle in the said conductive layer, Although it can select suitably according to the objective, 0.1 mass part-500 mass parts are preferable with respect to 100 mass parts of metal nanowires. 50 parts by mass to 300 parts by mass is more preferable, and 80 parts by mass to 200 parts by mass is particularly preferable. When the content of the silica fine particles is less than 0.1 parts by mass with respect to 100 parts by mass of the metal nanowires, the surface hardness may be remarkably reduced. May be high. On the other hand, when the content of the silica fine particles is within the preferable range, it is advantageous in that the surface hardness can be increased without increasing the surface resistivity or the haze ratio.
The content of the silica fine particles in the conductive layer can be measured using, for example, a fluorescent X-ray analyzer (SEA1100, manufactured by SII).

<Ratio of average particle diameter Bnm of silica fine particles / average minor axis length Anm of metal nanowires (B / A) >>>
In the conductive patterning material, when the average particle diameter of the silica fine particles is Bnm and the average minor axis length of the metal nanowire is Anm, the ratio (B / A) is 0.9 or more and 5 or less. However, 1.1 or more and 4.5 or less are preferred, and 2.5 or more and 4.5 or less are more preferred. If the ratio (B / A) is less than 0.9, the surface hardness cannot be increased, and the surface resistivity and haze ratio may increase. If the ratio exceeds 5, the surface hardness is increased. Cannot be carried out, the haze rate is increased, and the transmittance is decreased.
On the other hand, when the ratio (B / A) is 0.9 or more and 5 or less, it is advantageous in that the surface hardness, the transmittance, and the conductivity are excellent, and the surface resistivity and the haze ratio are low.

<< Binder >>
The binder is an organic high molecular weight polymer, preferably in an alkali-soluble resin having at least one group that promotes alkali solubility in a molecule, preferably in a molecule having an acrylic copolymer as a main chain. Can be appropriately selected.
Examples of the at least one group that promotes alkali solubility include 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 the 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.

The organic polymer is preferably a polymer having a carboxylic acid in the side chain, such as a photosensitive resin having an acidic group.
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 Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, as described in JP-A-59-53836 and JP-A-59-71048. Polymers, partially esterified maleic acid copolymers, etc., acidic cellulose derivatives having a carboxylic acid in the side chain, and polymers having a hydroxyl group with an acid anhydride added are preferred. A polymer having an acryloyl group is 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 organic polymer, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxy described in JP-A-7-140654 Propyl acrylate / polymethyl 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 can also be used.

  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 the (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 ( Examples thereof include (meth) acrylate, dicyclopentenyl (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate. 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 ) (where R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ² represents an aromatic carbon atom having 6 to 10 carbon atoms) Represents a hydrogen ring, and R ³ represents an alkyl group having 1 to 8 carbon atoms or an aralkyl group having 6 to 12 carbon atoms). 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 not particularly limited and may be appropriately selected depending on the intended purpose. ~ 300,000 is more preferable, and 5,000 to 200,000 is particularly preferable.
Here, the weight average molecular weight can be measured by a gel permeation chromatography (GPC) method and determined using a standard polystyrene calibration curve.

  The content of the binder is preferably 25% by mass to 80% by mass, more preferably 30% by mass to 75% by mass, and particularly preferably 40% by mass to 70% by mass with respect to the entire conductive layer. When the content of the binder is within the preferable range, it is advantageous in that both developability and conductivity of the metal nanowire can be achieved.

<< Photosensitive compound >>
The said photosensitive compound means the compound which provides the function which forms an image by exposure, or gives the trigger to it. Specific examples include (1) a compound that generates an acid upon exposure (photoacid generator), (2) a photosensitive quinonediazide compound, and (3) a photoradical generator. These may be used individually by 1 type and may use 2 or more types together. In addition, a sensitizer can be used in combination for sensitivity adjustment.

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

The (1) 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, Examples include disulfone and o-nitrobenzyl sulfonate.
Among these, imide sulfonate, oxime sulfonate, and o-nitrobenzyl sulfonate, which are compounds that generate sulfonic acid, are particularly preferable.

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

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

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

Among these, the photosensitive compound is preferably a compound that generates sulfonic acid among the (1) photoacid generators, and the following oxime sulfonate compounds are particularly preferable from the viewpoint of high sensitivity.

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

-(3) Photoradical generator--
The photoradical generator has a function of directly absorbing light or being photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction to generate a polymerization active radical. 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, and more preferably 1% by mass to the total solid content of the conductive layer. 20% by mass is particularly preferred. When the content of the photo radical generator is within the preferable range, it is advantageous in that 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 etc. which are described in Unexamined-Japanese-Patent No. 2008-268884 are mentioned. Among these, triazine compounds, acetophenone compounds, acylphosphine (oxide) compounds, oxime compounds, imidazole compounds, and benzophenone compounds are particularly preferable from the viewpoint of exposure sensitivity.

  As the photoradical generator, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1 is used from the viewpoints 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 preferred.

The arrangement liquid for arranging the conductive layer may use a photoradical generator and a chain transfer agent in combination in order to improve 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-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione Mercapto compounds having: aliphatic polyfunctional mercapto compounds such as pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane Etc. These may be used individually by 1 type and may use 2 or more types together.
The content of the chain transfer agent is preferably 0.01% by mass to 15% by mass, more preferably 0.1% by mass to 10% by mass, and more preferably 0.5% by mass to the total solid content of the conductive layer. 5% by mass is particularly preferred.

<< Other ingredients >>
The other components in the conductive layer are not particularly limited and can be appropriately selected depending on the purpose. Agents, viscosity modifiers, preservatives, various additives such as solvents, etc.

-Dispersant-
The dispersant is used to prevent and disperse the metal nanowires.
The dispersant is not particularly limited as long as it can disperse the metal nanowires, and can be appropriately selected according to the purpose. For example, a commercially available low molecular pigment dispersant or polymer pigment dispersant is used. In particular, a polymer dispersant having a property of adsorbing to metal nanowires is preferably used. Polyvinylpyrrolidone, BYK series (manufactured by Big Chemie), Solsperse series (manufactured by Nippon Lubrizol, etc.), Ajisper series ( Ajinomoto Co., Inc.).

  As content of the said dispersing agent, 0.1 mass part-50 mass parts are preferable with respect to 100 mass parts of said binders, 0.5 mass part-40 mass parts are more preferable, and 1 mass part-30 mass parts are. Particularly preferred. When the content is less than 0.1 parts by mass, the metal nanowires may aggregate in the dispersion, and when the content exceeds 50 parts by mass, a stable arrangement film (for example, (Coating film) cannot be formed, and unevenness in arrangement may occur.

-Crosslinking agent-
The crosslinking agent is a compound that forms a chemical bond with free radicals or acid and heat to cure the conductive layer, and is substituted with at least one group 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 azide compounds, methacryloyl groups or Examples thereof include compounds having an ethylenically unsaturated group containing an acryloyl group and the like. 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.

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

-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, methyl 3-methoxypropionate, 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.

--- Metal corrosion inhibitor ---
There is no restriction | limiting in particular as said metal corrosion inhibitor, Although it can select suitably according to the objective, For example, thiols, azoles, etc. are suitable.
By containing the metal corrosion inhibitor, a further excellent rust prevention effect can be exhibited. The metal corrosion inhibitor is dissolved in a liquid for disposing the conductive layer, dissolved in a suitable solvent, or added as a powder, or after preparing the conductive layer, the metal corrosion inhibitor is added. It can be applied by soaking in a bath.

  As a mass ratio (X / Y) of the total content X of components other than the metal nanowires in the conductive layer (single content in the case of only one type) and the content Y of the metal nanowires, There is no restriction | limiting in particular, Although it can select suitably according to the objective, 0.1-5 are preferable and 0.5-3 are more preferable. When the mass ratio (X / Y) is less than 0.1, deterioration of optical properties such as conductivity, transmittance and haze ratio due to aggregation of metal nanowires, mechanical strength of the conductive layer, and transfer substrate Problems such as deterioration of adhesion, particularly deterioration of pattern quality (faithful reproducibility of exposure pattern) obtained by patterning using photolithography may occur. In addition, when the mass ratio (X / Y) exceeds 5, there may be a decrease in conductivity due to a decrease in the number of contact points between the metal nanowires, and a deterioration in optical characteristics such as haze ratio and light transmittance. .

<< Method for Disposing Conductive Layer >>
There is no restriction | limiting in particular as a method to arrange | position the said conductive layer, According to the objective, it can select suitably, For example, the apply | coating method, the printing method, the spraying method, the inkjet method etc. are mentioned.
The coating method is not particularly limited and can 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, Examples thereof include a bar coating method, a gravure coating method, a curtain coating method, a spray coating method, and a doctor coating method.
Examples of the printing method include letterpress (letterpress) printing, stencil (screen) printing, lithographic (offset) printing, and intaglio (gravure) printing.

<< Thickness of conductive layer >>
The thickness of the conductive layer is not particularly limited and may be appropriately selected depending on the purpose. However, the average thickness is preferably 0.01 μm to 0.3 μm, more preferably 0.01 μm to 0.15 μm, 0.05 micrometer-0.15 micrometer are still more preferable, and 0.01 micrometer-0.08 micrometer are especially preferable. When the average thickness of the conductive layer is less than 0.01 μm, the in-plane distribution of conductivity may be non-uniform, and when it exceeds 0.3 μm, the transmittance is lowered and the transparency is impaired. There is.
The average thickness of the conductive layer is obtained by changing the amount of the dispersion and the concentration of the metal nanowires contained in the dispersion when the dispersion containing the metal nanowires is disposed on the target substrate. Can be adjusted.
Here, the average thickness of the conductive layer is, for example, observed with a scanning electron microscope (SEM) after the cross section of the conductive patterning material is taken out by microtome cutting, or the conductive patterning material is wrapped with an epoxy resin. After embedding, the section prepared with a microtome can be measured by observing with a transmission electron microscope (TEM).
In addition, the said average thickness means the average value of the thickness measured in arbitrary 10 places or more in the said electroconductive patterning material.

<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. In addition, a thin glass substrate having an average thickness of 10 μm to several hundred μm, which has been recently developed, can also be used.

  Examples of the synthetic resin sheet (film) include a polyethylene terephthalate (PET) sheet, a polycarbonate sheet, a polyethersulfone sheet, a polyester sheet, an acrylic resin sheet, a vinyl chloride resin sheet, an aromatic polyamide resin sheet, a polyamideimide sheet, A polyimide sheet etc. are mentioned.

  Examples of the metal substrate include an aluminum plate, a copper plate, a nickel plate, and a stainless plate.

  Among these, the transfer substrate is preferably a synthetic resin sheet, and particularly preferably a polyethylene terephthalate (PET) sheet. The use of a synthetic resin sheet for the transfer substrate is preferable in that it does not break, is excellent in flexibility, can be thinned, is lightweight, is easy to increase in area, and is low in cost.

There is no restriction | limiting in particular as the total visible light transmittance | permeability of the said transfer base material, Although it can select suitably according to the objective, 80% or more is preferable, 85% or more is more preferable, and 90% or more is especially preferable. If the total visible light transmittance is less than 80%, the transmittance may be low and may cause a problem in practice.
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 as thickness of the said transfer base material, Although it can select suitably according to the objective, 1 micrometers-500 micrometers are preferable at an average thickness, 3 micrometers-400 micrometers are more preferable, and 5 micrometers-300 micrometers are especially preferable. If the average thickness is less than 1 μm, the yield may decrease due to difficulty in handling in the conductive layer disposition process. If the average thickness exceeds 500 μm, the thickness and mass are not suitable for portable applications. May be a problem.
Here, the average thickness of the transfer substrate is, for example, observed with a scanning electron microscope (SEM) after the cross section of the conductive patterning material is taken out by microtome cutting, or the conductive patterning material is made of epoxy resin. After embedding, a section prepared with a microtome can be measured by observing with a transmission electron microscope (TEM).
In addition, the said average thickness means the average value of the thickness measured in arbitrary 10 places or more in the said electroconductive patterning material.

<Cushion layer>
The cushion layer is a layer that can improve the uniformity of transfer to the transfer target.
There is no restriction | limiting in particular about the shape, structure, size, etc. of the said cushion layer, According to the objective, it can select suitably, For example, a film | membrane form, a sheet form, etc. are mentioned as said shape. Examples of the 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 a material which forms the said cushion layer, Although it can select suitably according to the objective, It is preferable to contain a polymer.

The polymer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably a thermoplastic resin that softens when heated, such as acrylic resin, styrene-acrylic copolymer, polyvinyl alcohol, polyethylene, and ethylene. -Vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, gelatin, cellulose nitrate, cellulose triacetate, cellulose diacetate, cellulose acetate butyrate, cellulose acetate propionate, vinyl acetate, Homopolymers or copolymers containing vinylidene chloride, vinyl chloride, polyvinyl chloride, styrene, acrylonitrile, alkyl (C1-4) acrylate, alkyl (C1-4) methacrylate, vinyl pyrrolidone, etc. , Soluble polyesters, polycarbonates, soluble polyamide. These may be used individually by 1 type and may use 2 or more types together.
Among these, the polymer preferably contains methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer and styrene / acrylic acid copolymer.

There is no restriction | limiting in particular as glass transition temperature of the said cushion layer, Although it can select suitably according to the objective, 40 to 150 degreeC is preferable. When the glass transition temperature is less than 40 ° C., it may be too soft at room temperature to be inferior in handling properties. There is. Further, the glass transition temperature may be adjusted by adding a plasticizer or the like.
The glass transition temperature can be measured by a differential thermal analysis (DSC) method described in JIS K7121-1987.

  The cushion layer may contain other components other than the polymer. Examples of the other components include an organic high polymer described in paragraph [0007] and thereafter in JP-A-5-72724. Molecular materials, various plasticizers for adjusting the adhesive force to the transfer substrate, antioxidants, sulfidation agents, metal corrosion inhibitors, viscosity modifiers, preservatives, etc., supercooling substances, adhesion improvers, interfaces Examples include activators, mold release agents, thermal polymerization inhibitors, fillers, and solvents. These may be used alone or in combination of two or more.

  The method for forming the cushion layer is not particularly limited and may be appropriately selected depending on the purpose. For example, a cushioning layer-containing liquid containing the polymer and the other components is prepared. Can be formed on the transfer substrate and dried.

  There is no restriction | limiting in particular as a method of arrange | positioning the said cushion layer, According to the objective, it can select suitably, For example, the apply | coating method, the printing method, the spraying method, the inkjet method etc. are mentioned.

There is no restriction | limiting in particular as thickness of the said cushion layer, Although it can select suitably according to the objective, 1 micrometers-50 micrometers are preferable at an average thickness, 1 micrometer-30 micrometers are more preferable, and 5 micrometers-20 micrometers are especially preferable. If the average thickness is less than 1 μm, the uniformity of transfer to the transfer medium may be low, and if it exceeds 50 μm, the curl balance of the transfer material may be low.
The cushion layer has a thickness ratio of 0.01 to 0.7 (N / M) between the total average thickness N of the conductive layer and the cushion layer and the average thickness M of the transfer base. Preferably, 0.02-0.6 is more preferable. If the ratio (N / M) is less than 0.01, the uniformity of transfer to the transfer medium may be lowered, and if it exceeds 0.7, the curl balance may be lost.
Here, the average thickness of the cushion layer is, for example, observed with a scanning electron microscope (SEM) after the cross section of the conductive patterning material is taken out by microtome cutting, or the conductive patterning material is wrapped with an epoxy resin. After embedding, the section prepared with a microtome can be measured by observing with a transmission electron microscope (TEM).
In addition, the said average thickness means the average value of the thickness measured in arbitrary 10 places or more in the said electroconductive patterning material.

<Photosensitive layer>
In the present invention, when the conductive layer does not contain a photosensitive material (binder, photosensitive compound), it is preferable to have a photosensitive layer between the transfer substrate and the conductive layer or on the conductive layer. .
The photosensitive layer contains at least a binder, and contains a photosensitive compound and, if necessary, other components.
There is no restriction | limiting in particular as said binder and a photosensitive compound, Although it can select suitably according to the objective, For example, the thing similar to the said conductive layer can be used.
There is no restriction | limiting in particular as thickness of the said photosensitive layer, Although it can select suitably according to the objective, 0.01 micrometer-100 micrometers are preferable at an average thickness, and 0.05 micrometer-10 micrometers are more preferable.

<Protective film>
The protective film is peeled off when the conductive patterning material is transferred to a transfer target.
Examples of the protective film include polypropylene film, polyethylene film, silicone paper, paper laminated with polyethylene and polypropylene, polyolefin sheet, and polytetrafluoroethylene sheet. Among these, polyethylene film and polypropylene film are mentioned. Is preferred.

<Characteristic>
<< Surface hardness >>
The surface hardness of the conductive patterning material is not particularly limited and can be appropriately selected according to the purpose, but the harder is preferable in that the operation surface is less likely to be scratched when used for a touch panel or the like. In accordance with JIS K5400, the pencil hardness when a scratch test is performed by applying a load of 1 kg from right above a pencil fixed at an angle of 45 degrees is preferably H or more, more preferably 2H or more, and particularly preferably 3H or more. .

<< Surface resistivity >>
The surface resistivity of the conductive patterning material is 300Ω / □ or less, preferably 10Ω / □ to 150Ω / □, more preferably 10Ω / □ to 70Ω / □, and particularly preferably 10Ω / □ to 65Ω / □. . If the surface resistivity exceeds 300 Ω / □, disconnection due to Joule heat generated during energization is likely to occur, and voltage drop occurs between the upstream and downstream of the wiring, limiting the area when used for a touch panel. May cause problems. The low surface resistivity itself is not harmful, but if it is less than 10 Ω / □, it may be difficult to obtain a conductor having a high light transmittance.
The surface resistivity can be measured using, for example, a surface resistance meter (Loresta-GP MCP-T600; manufactured by Mitsubishi Chemical Corporation).

<< Haze ratio >>
The haze ratio of the conductive patterning material is 2% or less, preferably 1.6% or less, more preferably 1.2% or less, and particularly preferably 1% or less. When the haze ratio exceeds 2%, it becomes opaque, and the visibility may be deteriorated when used for a touch panel or the like.
The haze ratio can be measured using, for example, an integrating sphere light transmittance measuring device (Hazeguard Plus; manufactured by Gardner).

<< Transmittance >>
There is no restriction | limiting in particular as the transmittance | permeability of the said electroconductive patterning material, Although it can select suitably according to the objective, 80% or more is preferable, 85% or more is more preferable, and 90% or more is especially preferable. When the transmittance is less than 80%, the conductive pattern becomes conspicuous when used in an image display medium such as a touch panel, and it is necessary to increase power consumption in order to impair image quality or compensate for luminance reduction. Detrimental effects such as occurrence may occur.
The transmittance can be measured, for example, using an integrating sphere light transmittance measuring device (Hazeguard Plus; manufactured by Gardner).

<< Conductivity >>
The conductivity of the conductive patterning material is the reciprocal of the resistivity, and when comparing by relative value, the conductivity can be compared by comparing the reciprocal of the surface resistivity.
The conductivity of the 100 μm line width of the conductive patterning material of the present invention is preferably a relative value with respect to 100 when the reciprocal of the surface resistivity when no silica fine particles are added is 65 or more, and 75 or more. More preferably, 80 or more is particularly preferable. That the said electrical conductivity is less than 65 means that the patterning property has fallen remarkably.
The surface resistivity can be measured using, for example, a surface resistance meter (Loresta-GP MCP-T600; manufactured by Mitsubishi Chemical Corporation).

Hereinafter, an example of the conductive patterning material of the present invention will be described with reference to the drawings. However, the conductive patterning material of the present invention is not limited thereto.
FIG. 1 is a schematic sectional view showing an example of a layer structure of the conductive patterning material of the present invention.
The conductive patterning material 6 in FIG. 1 has a transfer base 1 and a cushion layer 2 and a conductive layer 3 in this order on one surface of the transfer base 1.
In addition, although illustration is abbreviate | omitted, the conductive layer 3 in the electroconductive patterning material 6 may be patterned, and does not need to be patterned. Examples of the patterning include electrode shapes applied with an existing ITO transparent conductive film. Specifically, a stripe-shaped pattern and a diamond pattern disclosed in WO2005 / 114369 pamphlet, WO2004 / 061808 pamphlet, JP2010-33478A, and JP2010-44453A Etc.

<Patterning process>
There is no restriction | limiting in particular as a method of performing the patterning process using the said electroconductive patterning material, According to the objective, it can select suitably, However, The electroconductive layer in the said electroconductive patterning material of this invention, or a to-be-transferred body is used. The transferred conductive layer of the conductive patterning material of the present invention preferably includes an exposure step (exposure step) and a development step (development step), and further includes other steps as necessary. .

-Exposure process-
The exposure step is a step of exposing the conductive layer of the conductive patterning material of the present invention or the conductive layer of the conductive patterning material of the present invention transferred to a transfer target.
As the exposure method, surface exposure using a photomask may be performed, or scanning exposure using a laser beam may be performed. At this time, refractive exposure using a lens or reflection exposure using a reflecting mirror may be used, and exposure methods such as contact exposure, proximity exposure, reduced projection exposure, and reflection projection exposure may be used.

-Development process-
The developing step is a step in which at least one of the exposed portion and the non-exposed portion in the conductive layer is developed by applying a solvent.
In the developing step, when the photosensitive layer is further provided, either the exposed portion or the non-exposed portion in the photosensitive layer is removed.

There is no restriction | limiting in particular as said solvent, Although it can select suitably according to the objective, An alkaline solution is preferable.
There is no restriction | limiting in particular as an alkali contained in the said alkaline solution, According to the objective, it can select suitably, For example, tetramethylammonium hydroxide, tetraethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, sodium carbonate Sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydroxide, potassium hydroxide and the like. These may be used alone or in combination of two or more.

There is no restriction | limiting in particular as a method to provide the said alkaline solution to the said conductive layer, According to the objective, it can select suitably, For example, application | coating, immersion, spraying etc. are mentioned. Specifically, a method of immersing the conductive patterning material of the present invention in an alkaline solution, a method of pouring the alkaline solution into the conductive patterning material of the present invention using a shower or spray, and the conductive of the present invention. For example, a method of applying a napkin or the like in which an alkaline solution is dipped in a conductive patterning material.
Among these, the method of applying the alkaline solution to the conductive layer is particularly preferably a method of immersing the conductive patterning material of the present invention in an alkaline solution.
There is no restriction | limiting in particular as immersion time of the said alkaline solution, Although it can select suitably according to the objective, 10 second-5 minutes are preferable.

<Transfer method>
Next, a method for transferring the conductive patterning material of the present invention will be described.
First, the conductive layer in the conductive patterning material of the present invention is pressurized and bonded onto the transfer target under heating. Conventionally known laminators and vacuum laminators can be used for bonding, and an auto-cut laminator can also be used in order to further increase productivity. Thereafter, the transfer substrate is peeled off, and the conductive layer is transferred to the transfer target.
There is no restriction | limiting in particular as said to-be-transferred body, According to the objective, it can select suitably, For example, a base material, a liquid crystal cell, etc. are mentioned. Among these, a transparent glass substrate and a liquid crystal cell are particularly preferable.

Hereinafter, an example of the transfer method using the conductive patterning material of the present invention will be described with reference to the drawings. However, the transfer method using the conductive patterning material of the present invention is not limited to this.
Here, FIGS. 2A to 2C are explanatory diagrams for explaining an example of a transfer method using the conductive patterning material of the present invention.
The cushioning layer 2 and the conductive layer 3 of the conductive patterning material 6 having the transfer base 1 shown in FIG. 2A and the cushion layer 2 and the conductive layer 3 in this order on one surface of the transfer base 1. As shown in FIG. 2 (B), the laminate is bonded to a transparent substrate 8 as a transfer target by applying pressure and heating using a laminator. Subsequently, as shown in FIG. 2C, the cushioning layer 2 and the conductive layer 3 are transferred to the transparent substrate 8 by peeling the transfer base material 1.

<Application>
The conductive patterning material of the present invention has high surface hardness, excellent scratch resistance, good patternability, high transparency and conductivity, and low haze and surface resistivity. In addition to the touch panel of the present invention, it is widely applied to display electrodes, electromagnetic shields, organic EL display electrodes, inorganic EL display electrodes, electronic paper, flexible display electrodes, integrated solar cells, display elements, and other various devices. Is done. Among these, it is particularly suitably used for a touch panel and a display device with a touch panel function.

(Touch panel)
The touch panel of the present invention includes at least the conductive patterning material of the present invention, preferably further includes a base material, and further includes other members as necessary.

<Base material>
There is no restriction | limiting in particular about the shape, structure, size, etc. of the said base material, According to the objective, it can select suitably, For example, a film | membrane form, a sheet form, etc. are mentioned as said shape. Examples of the 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 base material, According to the objective, it can select suitably, For example, a transparent substrate, a synthetic resin sheet (film), a metal substrate, a ceramic board, a semiconductor substrate which has a photoelectric conversion element, etc. Is mentioned. If necessary, the base material can be subjected to pretreatment such as chemical treatment such as a silane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition and the like.
The transparent glass substrate, the synthetic resin sheet, and the metal substrate are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include the same transfer substrate as the conductive patterning material. It is done.

There is no restriction | limiting in particular as a method of the said touch panel, According to the objective, it can select suitably, For example, a resistive touch panel, a surface capacitive touch panel, a projection capacitive touch panel, an electromagnetic induction touch panel Ultrasonic surface acoustic wave type touch panel, infrared scanning type touch panel, and the like.
In the present invention, the touch panel includes a so-called touch sensor and a touch pad.

  There is no restriction | limiting in particular as a layer structure of the touch-panel sensor electrode part in the said touch panel, Although it can select suitably according to the objective, The bonding system which bonds the said 2 electroconductive patterning material, 1 sheet | seat base It is preferable that any one of a method in which the conductive patterning material is provided on both surfaces of the material, a single-sided jumper or a through-hole method, or a single-area layer method.

An example of the surface capacitive touch panel will be described with reference to FIG. 3, but the touch panel of the present invention is not limited to this.
In FIG. 3, the touch panel 10 is provided with a conductive patterning material 12 so as to uniformly cover the surface of the transparent substrate 11. Electrode terminals 18 for electrical connection with the circuit are formed.
In FIG. 3, reference numeral 13 denotes a conductive patterning material to be a shield electrode, 14 and 17 denote protective films, 15 denotes an intermediate protective film, and 16 denotes an antiglare film.
When an arbitrary point on the conductive patterning material 12 is touched with a finger or the like, the conductive patterning material 12 is grounded through the human body at the touched point, and a resistance value between each electrode terminal 18 and the ground line is measured. Changes. The change of the resistance value is detected by the external detection circuit, and the coordinates of the touched point are specified.

Another example of the surface capacitive touch panel will be described with reference to FIG.
In FIG. 4, the touch panel 20 insulates the conductive patterning material 22 and the conductive patterning material 23 disposed so as to cover the surface of the transparent substrate 21, and the conductive patterning material 22 and the conductive patterning material 23. The insulating layer 24 includes an insulating cover layer 25 that generates a capacitance between a contact target such as a finger and the conductive patterning material 22 or the conductive patterning material 23, and detects the position of the contact target such as a finger. To do. Depending on the structure, the conductive patterning material 22 and the conductive patterning material 23 may be integrally formed, and the insulating layer 24 or the insulating cover layer 25 may be formed as an air layer.
When the insulating cover layer 25 is touched with a finger or the like, the capacitance value between the finger and the conductive patterning material 22 or the conductive patterning material 23 changes. This change in capacitance value is detected by the external detection circuit, and the coordinates of the touched point are specified.

An example of the projected capacitive touch panel will be described with reference to FIG. 5, but the touch panel of the present invention is not limited to this.
FIG. 5 is a diagram schematically illustrating the touch panel 20 as a projected capacitive touch panel through an arrangement in which the conductive patterning material 22 and the conductive patterning material 23 are viewed from the plane.
The touch panel 20 is provided with a plurality of conductive patterning materials 22 capable of detecting positions in the X-axis direction and a plurality of conductive patterning materials 23 in the Y-axis direction so as to be connectable to external terminals. The conductive patterning material 22 and the conductive patterning material 23 are in contact with a plurality of contact objects such as fingertips, and contact information can be input at multiple points.
When an arbitrary point on the touch panel 20 is touched with a finger, the coordinates in the X-axis direction and the Y-axis direction are specified with high positional accuracy.
In addition, as other structures, such as a transparent substrate and a protective layer, the structure of the surface capacitive touch panel can be appropriately selected and applied. Moreover, although the example of the pattern of the electroconductive patterning material by the some electroconductive patterning material 22 and the some electroconductive patterning material 23 was shown in the touch panel 20, the shape, arrangement | positioning, etc. are not restricted to these. .

An example of the resistive touch panel will be described with reference to FIG. 6, but the touch panel of the present invention is not limited to this.
In FIG. 6, the touch panel 30 includes a conductive patterning material 32 through a transparent substrate 31 on which a conductive patterning material 32 is disposed, a plurality of spacers 36 disposed on the conductive patterning material 32, and an air layer 34. The conductive patterning material 33 that can come into contact with the transparent patterning material 33 and the transparent film 35 disposed on the conductive patterning material 33 are supported.
When the touch panel 30 is touched from the transparent film 35 side, the transparent film 35 is pressed, the pressed conductive patterning material 32 and the conductive patterning material 33 come into contact, and the potential change at this position is not shown. By detecting with an external detection circuit, the coordinates of the touched point are specified.

<Application>
Since the touch panel of the present invention has the conductive patterning material of the present invention, it has high surface hardness, excellent scratch resistance, high transparency and conductivity, and low haze ratio and surface resistivity. It can be suitably used for various electronic devices such as ATMs, vending machines, mobile phones, smart phones, portable information terminals, portable game machines, copying machines, car navigation systems, multimedia stations, and information boards.

  EXAMPLES The present invention will be specifically described below with reference to examples of the present invention, but the present invention is not limited to these examples.

(Preparation Example 1: Preparation of silver nanowire aqueous dispersion 1)
-Preparation of additives-
Additive A, additive G, and additive H were prepared in advance by the method shown below.
[Preparation of Additive A]
After dissolving silver nitrate powder 2.1g in pure water and then adding 1N ammonia water until it became transparent, pure water was added so that the total amount was 200 mL.
[Preparation of additive G]
An additive solution G was prepared by dissolving 1.2 g of glucose powder in 200 mL of pure water.
[Preparation of additive H]
Additive liquid H was prepared by dissolving 0.5 g of HTAB (hexadecyl-trimethylammonium bromide) powder in 87.5 mL of pure water.

-Preparation of silver nanowire aqueous dispersion-
Next, silver nanowire aqueous dispersion 1 was prepared by the method shown below.
410 mL of pure water was placed in a three-necked flask, and 87.5 mL of additive H and 200 mL of additive G were added while stirring at 20 ° C. Next, a total of 200 mL of additive A was added dropwise to this solution at 0.3 mL / min. After the additive A was added dropwise, the mixture was stirred for 10 minutes, and 87.5 mL of the additive H was added all at once. Next, the temperature was raised to an internal temperature of 70 ° C. at 5 ° C./min, and stirring was continued for 5 hours to obtain a silver nanowire ammonia dispersion.
The obtained silver nanowire ammonia dispersion was ultrafiltered and concentrated using an ultrafiltration module (ultrafiltration module SIP1013, fractional molecular weight 6,000; manufactured by Asahi Kasei Corporation). After concentration to 50 mL, 950 mL of pure water was placed in the ultrafiltration module and washed. This washing operation was performed 10 times in total to obtain a silver nanowire aqueous dispersion 1.
It was 22 nm when the average short-axis length of the silver nanowire in this silver nanowire aqueous dispersion 1 was measured with the following method.

<Measurement of average minor axis length of silver nanowire>
The silver nanowires in the silver nanowire aqueous dispersion were observed with a transmission electron microscope (TEM) (JEM-2000FX; manufactured by JEOL Ltd.), the short axis length was measured, and 300 silver nanowires were short. The average value of axial length was calculated | required and this was made into the average short-axis length of silver nanowire.

(Preparation Example 2: Preparation of silver nanowire aqueous dispersion 2)
In Preparation Example 1, when the silver nanowire ammonia dispersion was obtained, the internal temperature was changed to 70 ° C. at 5 ° C./min, except that the temperature was raised to 75 ° C. at 5 ° C./min. A silver nanowire aqueous dispersion 2 was prepared in the same manner as in Preparation Example 1.
It was 30 nm when the average minor-axis length of the silver nanowire in the silver nanowire aqueous dispersion 2 was measured by the method similar to the preparation example 1.

(Preparation Example 3: Preparation of silver nanowire aqueous dispersion 3)
In Preparation Example 1, when obtaining the silver nanowire ammonia dispersion, the internal temperature was changed to 70 ° C. at 5 ° C./min, except that the temperature was raised to 80 ° C. at 5 ° C./min. A silver nanowire aqueous dispersion 3 was prepared in the same manner as in Preparation Example 1.
It was 40 nm when the average minor-axis length of the silver nanowire in the silver nanowire aqueous dispersion 3 was measured by the method similar to the preparation example 1.

(Preparation Example 4: Preparation of silver nanowire aqueous dispersion 4)
In Preparation Example 1, when the silver nanowire ammonia dispersion liquid was obtained, the internal temperature was changed to 70 ° C. at 5 ° C./min, except that the temperature was raised to 85 ° C. at 5 ° C./min. A silver nanowire aqueous dispersion 4 was prepared in the same manner as in Preparation Example 1.
When the average minor axis length of the silver nanowire in the silver nanowire aqueous dispersion 4 was measured by the same method as in Preparation Example 1, it was 50 nm.

(Preparation Example 5: Preparation of silver nanowire aqueous dispersion 5)
In Preparation Example 1, in the preparation of additive H, 0.5 g of HTAB powder was dissolved in 87.5 mL of pure water, and 0.1 g of HTAB powder was dissolved in 87.5 mL of pure water. Except for the above, a silver nanowire aqueous dispersion 5 was prepared in the same manner as in Preparation Example 1.
When the average minor axis length of the silver nanowire in the silver nanowire aqueous dispersion 5 was measured by the same method as in Preparation Example 1, it was 100 nm.

(Synthesis Example 1: Synthesis of Binder (A-1))
As a monomer component constituting the copolymer, 7.79 g of methacrylic acid (MAA) and 37.21 g of benzyl methacrylate (BzMA) are used, and 0.5 g of azobisisobutyronitrile (AIBN) is used as a radical polymerization initiator. The binder component (A) represented by the following structural formula (1) is used by polymerizing the monomer component and the radical polymerization initiator in 55.00 g of propylene glycol monomethyl ether acetate (PGMEA) as a solvent. -1) PGMEA solution (solid content concentration: 45 mass%) was obtained. The polymerization temperature was adjusted to 60 to 100 ° C.
As a result of measuring the molecular weight of the binder (A-1) using a gel permeation chromatography (GPC) method, the weight average molecular weight (Mw) in terms of polystyrene was 30,000, and the molecular weight distribution (Mw / Mn) was 2. .21.

(Example 1: Production of conductive patterning material 1)
<Formation of cushion layer>
On one side of a polyethylene terephthalate (PET) film having an average thickness of 30 μm as a transfer substrate, a cushion layer coating solution having the following composition was applied and dried to form a cushion layer having an average thickness of 10 μm.
[Composition of cushion layer coating solution]
・ Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (* 1) ... 6.0 parts by mass Styrene / acrylic acid copolymer (* 2) ... 14.0 parts by mass 2,2-bis [4- (methacryloxypolyethoxy] phenyl] propane (* 3)
・ ・ ・ 9.0 parts by mass ・ Fluorosurfactant (* 4) ・ ・ ・ 0.5 parts by mass ・ Methanol ・ ・ ・ 10.0 parts by mass ・ Propylene glycol monomethyl ether acetate ・ ・ ・ 5.0 parts by mass Methyl ethyl ketone: 55.5 parts by mass (* 1): Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer [copolymerization composition ratio (molar ratio) = 55/30/10/5, weight Average molecular weight = 100,000, Tg≈70 ° C.]
(* 2): Styrene / acrylic acid copolymer [copolymerization composition ratio (molar ratio) = 65/35, weight average molecular weight = 10,000, Tg≈100 ° C.]
(* 3): BPE-500 (made by Shin-Nakamura Chemical Co., Ltd.)
(* 4): Megafuck F-780-F (Dainippon Ink Chemical Co., Ltd.)

<Preparation of conductive layer>
-Preparation of MFG dispersion 1 of silver nanowires-
Polyvinylpyrrolidone (K-30; manufactured by Wako Pure Chemical Industries, Ltd.) and 1-methoxy-2-propanol (MFG) are added to the silver nanowire aqueous dispersion 1, and after centrifugation, the supernatant is decanted. Water was removed. MFG was then added and redispersed. This centrifugation and redispersion operation was performed three times in total to obtain an MFG dispersion 1 of silver nanowires. In the third redispersion operation, the amount of MFG added was adjusted so that the silver content was 1% by mass in the MFG dispersion.

-Preparation of coating solution for conductive patterning material-
The composition shown below was stirred to prepare a coating solution for the conductive layer.
[Composition of coating solution for conductive layer]
Binder (A-1) of Synthesis Example 1 0.241 parts by mass Dipentaerythritol hexaacrylate (* 5) 0.252 parts by mass 2- (dimethylamino) -2-[(4 -Methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (alkylphenone photopolymerization initiator, * 6)
... 0.0252 parts by mass- 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol (crosslinking agent, * 7) 0.0237 parts by mass-UV reactive fluorine-based surface modifier (* 8).. .0.0003 parts by mass-Propylene glycol monomethyl ether acetate (PGMEA)
... 0.9611 parts by mass, 1-methoxy-2-propanol (MFG) ... 41.7 parts by mass, MFG dispersion 1 of silver nanowires ... 54.1 parts by mass, shown in Table 1 below Silica fine particles 2 (average particle size: 25 nm) 2.705 parts by mass (* 5) KAYARAD DPHA (made by Nippon Kayaku Co., Ltd.)
(* 6) IRGACURE 379 (Ciba Specialty Chemicals Co., Ltd.)
(* 7) EHPE-3150 (manufactured by Daicel Chemical Industries)
(* 8) Megafuck F781F (Dainippon Ink Chemical Co., Ltd.)

-Formation of conductive layer-
On the cushion layer of the PET film on which the cushion layer is formed, the conductive coating solution is applied so that the content of silver nanowires in the conductive layer is 0.03 g / m ² , dried, and the average thickness is 0. A conductive layer having a thickness of 0.08 μm was formed. Thereby, the conductive patterning material 1 of Example 1 was produced.
In addition, content of the silver nanowire in a conductive layer was measured and confirmed with the fluorescent-X-ray-analysis apparatus (SEA1100; product made by SII).
Further, the average thickness of the conductive layer was confirmed by observing and measuring with a scanning electron microscope (SEM) after taking out a cross section of the conductive patterning material by microtome cutting.

(Example 2: Production of conductive patterning material 2)
In Example 1, in place of the silica fine particles 2 in the coating liquid of the conductive patterning material, the conductive patterning material 2 was prepared in the same manner as in Example 1 except that the silica fine particles 3 shown in Table 1 below were used. Produced.

(Example 3: Production of conductive patterning material 3)
In Example 1, in place of the silica fine particles 2 in the coating liquid for the conductive patterning material, the conductive patterning material 3 was prepared in the same manner as in Example 1 except that the silica fine particles 4 shown in Table 1 below were used. Produced.

(Example 4: Production of conductive patterning material 4)
In Example 1, the conductive patterning material 4 was prepared in the same manner as in Example 1 except that the silica fine particles 5 shown in Table 1 below were used instead of the silica fine particles 2 in the coating liquid of the conductive patterning material. Produced.

(Example 5: Production of conductive patterning material 5)
In Example 2, it replaced with the silver nanowire aqueous dispersion 1, and produced the electroconductive patterning material 5 by the method similar to Example 2 except having used the silver nanowire aqueous dispersion 2. FIG.

(Example 6: Production of conductive patterning material 6)
In Example 2, it replaced with the silver nanowire aqueous dispersion 1, and produced the electroconductive patterning material 6 by the method similar to Example 2 except having used the silver nanowire aqueous dispersion 3. FIG.

(Example 7: Production of conductive patterning material 7)
In Example 3, it replaced with the silver nanowire aqueous dispersion 1, and produced the electroconductive patterning material 7 by the method similar to Example 3 except having used the silver nanowire aqueous dispersion 4. FIG.

(Example 8: Production of conductive patterning material 8)
In Example 1, at the time of formation of the conductive layer, the coating liquid of the conductive patterning material was changed to that applied so that the silver nanowire content in the conductive layer was 0.03 g / m ^2. The electroconductive patterning material 8 was produced by the method similar to Example 1 except having apply | coated so that content of might be set to 0.01 g / m < ² >.
In addition, content of the silver nanowire in a conductive layer was confirmed by the same method as Example 1.

(Example 9: Production of conductive patterning material 9)
In Example 1, at the time of formation of the conductive layer, the coating liquid of the conductive patterning material was changed to that applied so that the silver nanowire content in the conductive layer was 0.03 g / m ^2. The electroconductive patterning material 9 was produced by the method similar to Example 1 except having apply | coated so that content of might be set to 0.02 g / m < ² >.
In addition, content of the silver nanowire in a conductive layer was confirmed by the same method as Example 1.

(Example 10: Production of conductive patterning material 10)
In Example 1, at the time of formation of the conductive layer, the coating liquid of the conductive patterning material was changed to that applied so that the silver nanowire content in the conductive layer was 0.03 g / m ^2. The electroconductive patterning material 10 was produced by the method similar to Example 1 except having apply | coated so that content of might be 0.05 g / m < ² >.
In addition, content of the silver nanowire in a conductive layer was confirmed by the same method as Example 1.

(Example 11: Production of conductive patterning material 11)
In Example 1, at the time of formation of the conductive layer, the coating liquid of the conductive patterning material was changed to that applied so that the content of silver nanowire in the conductive layer was 0.03 g / m ^2. The electroconductive patterning material 11 was produced by the method similar to Example 1 except having apply | coated so that content of might be set to 0.07 g / m < ² >.
In addition, content of the silver nanowire in a conductive layer was confirmed by the same method as Example 1.

(Example 12: Production of conductive patterning material 12)
In Example 1, when the conductive layer was formed, the coating liquid of the conductive patterning material was applied so that the average thickness of the conductive layer was 0.08 μm, and the average thickness of the conductive layer was 0.01 μm. A conductive patterning material 12 was produced in the same manner as in Example 1 except that the coating was performed as described above.
The average thickness of the conductive layer was confirmed by the same method as in Example 1.

(Example 13: Production of conductive patterning material 13)
In Example 1, when the conductive layer was formed, the coating liquid of the conductive patterning material was applied so that the average thickness of the conductive layer was 0.08 μm, and the average thickness of the conductive layer was 0.15 μm. A conductive patterning material 13 was produced in the same manner as in Example 1 except that the coating was performed as described above.
The average thickness of the conductive layer was confirmed by the same method as in Example 1.

(Example 14: Production of conductive patterning material 14)
In Example 1, when the conductive layer was formed, the coating liquid of the conductive patterning material was applied so that the average thickness of the conductive layer was 0.08 μm, and the average thickness of the conductive layer was 0.3 μm. A conductive patterning material 14 was produced in the same manner as in Example 1 except that the coating was performed as described above.
The average thickness of the conductive layer was confirmed by the same method as in Example 1.

(Comparative Example 1: Production of conductive patterning material 15)
In Example 1, in place of the silica fine particles 2 in the coating liquid of the conductive patterning material, the conductive patterning material 15 was prepared in the same manner as in Example 1 except that the silica fine particles 6 shown in Table 1 below were used. Produced.

(Comparative Example 2: Production of conductive patterning material 16)
In Example 1, the conductive patterning material 16 was prepared in the same manner as in Example 1 except that the silica fine particles 1 shown in Table 1 below were used instead of the silica fine particles 2 in the coating liquid of the conductive patterning material. Produced.

(Comparative Example 3: Production of conductive patterning material 17)
In Example 1, except that silica fine particles were not added to the coating liquid for the conductive patterning material, the conductive patterning material 17 was prepared in the same manner as in Example 1, and the same method as in Example 1 was used. A patterning process was performed.

(Comparative Example 4: Production of conductive patterning material 18)
In Example 1, at the time of formation of the conductive layer, the coating liquid of the conductive patterning material was changed to that applied so that the silver nanowire content in the conductive layer was 0.03 g / m ^2. The electroconductive patterning material 18 was produced by the method similar to Example 1 except having apply | coated so that content of might become 0.08 g / m < ² >.
In addition, content of the silver nanowire in a conductive layer was confirmed by the same method as Example 1.

(Comparative Example 5: Production of conductive patterning material 19)
In Example 1, at the time of formation of the conductive layer, the coating liquid of the conductive patterning material was changed to that applied so that the silver nanowire content in the conductive layer was 0.03 g / m ^2. The electroconductive patterning material 19 was produced by the method similar to Example 1 except having apply | coated so that content of might be 0.005 g / m < ² >.
In addition, content of the silver nanowire in a conductive layer was confirmed by the same method as Example 1.

(Comparative Example 6: Production of conductive patterning material 20)
In Example 1, instead of the silica fine particles 2 in the coating liquid of the conductive patterning material, the silica fine particles 5 shown in Table 1 below are used, and instead of the silver nanowire aqueous dispersion 1, the silver nanowire aqueous dispersion 5 is used. A conductive patterning material 20 was produced in the same manner as in Example 1 except that was used.

<Patterning process>
About the electroconductive patterning materials 1-20 produced in Examples 1-14 and Comparative Examples 1-6, line and space (henceforth "L / S" may be called hereafter) by a method shown below is 100 micrometers / 100 micrometers. A stripe pattern was prepared.
From the mask on each conductive patterning material, a high pressure mercury lamp i-line (365 nm) was exposed at 100 mJ / cm ² (illuminance 20 mW / cm ² ). Each conductive patterning material after exposure was subjected to shower development for 30 seconds with a developer prepared by the method described below. The shower pressure was 0.04 MPa, and the time until the stripe pattern appeared was 15 seconds. Then, it rinsed with the shower of pure water.
[Preparation of developer]
5 g of sodium bicarbonate and 2.5 g of sodium carbonate were dissolved in 5,000 g of pure water.

<Evaluation>
With respect to the conductive layers of the conductive patterning materials 1 to 20 after the patterning treatment, total light transmittance, surface resistivity, conductivity of 100 μm line width, pencil hardness, and haze ratio were measured by the following methods. The results are shown in Table 2 below.

-Measurement of total light transmittance and haze rate-
The total light transmittance (%) and the haze ratio (%) were measured using an integrating sphere type light transmittance measuring device (Hazeguard Plus; manufactured by Gardner).
In addition, haze rate is 2% or less is an allowable range. The total light transmittance is preferably 80% or more.

-Measurement of surface resistivity-
The surface resistivity (Ω / □) was measured using a surface resistance meter (Loresta-GP MCP-T600; manufactured by Mitsubishi Chemical Corporation).
In addition, the allowable range of the surface resistivity is 300Ω / □ or less.

−100μm line width conductivity−
The conductivity of the 100 μm line width of each conductive patterning material is represented by the reciprocal of the resistivity. Therefore, the relative value with respect to the reference value when the reciprocal of the surface resistivity of Comparative Example 3 to which no silica fine particles are added, obtained by measurement of the surface resistivity, is taken as a reference value, and this reference value is taken as 100. And the conductivity of 100 μm line width was compared.
In addition, the relative value of the electrical conductivity is 65 or more is an allowable range.

-Pencil hardness-
The pencil hardness was measured in accordance with JIS K5400 by applying a 1 kg load from right above the pencil fixed at an angle of 45 degrees and performing a scratch test.
Note that the pencil hardness is within an allowable range of H or higher.

From the results of Examples 1 to 14, it can be seen that the conductive patterning material of the present invention has good patternability, high surface hardness, low haze ratio and surface resistivity, and high transparency and conductivity. It was.
On the other hand, in Comparative Examples 1 to 6, at least one of surface hardness, haze ratio, surface resistivity, transparency, and conductivity was at a level that cannot be used for a touch panel or the like. About Comparative Example 5, since the content of the metal nanowire in the conductive layer was 0.01 g / m ² or less, the conductivity was below the detection limit and could not be measured.

(Example 17)
<Production of touch panel>
Using the conductive patterning material of Example 3, "Latest Touch Panel Technology" (issued July 6, 2009, Techno Times), supervised by Yuji Mitani, "Touch Panel Technology and Development", CM Publishing (2004) (December issue), “FPD International 2009 Forum T-11 Lecture Textbook”, “Cypress Semiconductor Corporation Application Note AN2292”, etc., were used to produce a touch panel.
When the produced touch panel was used, since the surface hardness was high, it was excellent in abrasion resistance and was not easily scratched. In addition, the touch panel has excellent visibility due to its high transparency, and has excellent responsiveness to character input or screen operation with at least one of bare hands, hands wearing gloves, and pointing tools due to improved conductivity. Was able to be produced.

The conductive patterning material of the present invention has high surface hardness, excellent scratch resistance, good patternability, high transparency and conductivity, and low haze and surface resistivity. It is widely applied to display electrodes, electromagnetic wave shields, organic EL display electrodes, inorganic EL display electrodes, electronic paper, flexible display electrodes, integrated solar cells, display elements, and other various devices.
In addition, since the touch panel of the present invention has the conductive patterning material of the present invention, the ATM of a bank, a vending machine, a mobile phone, a smartphone, a portable information terminal, a portable game machine, a copying machine, a car navigation system, a multimedia station It can be suitably used for various electronic devices such as a guide plate.

DESCRIPTION OF SYMBOLS 1 Transfer base material 2 Cushion layer 3 Conductive layer 6 Conductive patterning material 8 Transparent substrate 10 Touch panel 11 Transparent substrate 12 Conductive patterning material 13 Conductive patterning material 14 Protective film 15 Intermediate protective film 16 Antiglare film 17 Protective film 18 Electrode terminal 20 touch panel 21 transparent substrate 22 conductive patterning material 23 conductive patterning material 24 insulating layer 25 insulating cover layer 30 touch panel 31 transparent substrate 32 conductive patterning material 33 conductive patterning material 34 air layer 35 transparent film 36 spacer

Claims (7)

A conductive patterning material having a conductive layer containing metal nanowires having an average minor axis length of 50 nm or less and silica fine particles,
The ratio (B / A) between the average particle diameter Bnm of the silica fine particles and the average minor axis length Anm of the metal nanowires is 0.9 or more and 5 or less,
In the conductive layer, the content of the metal nanowires is ^{0.01g / m 2 ~0.07g / m 2} , and a surface resistivity of 300 [Omega / □ or less, a haze of not more than 2% A conductive patterning material.   The conductive patterning material according to claim 1, wherein the ratio (B / A) is 1.1 or more and 4.5 or less.   The conductive patterning material according to claim 1, wherein the silica fine particles have an average particle size of 60 nm or less.   The conductive patterning material according to any one of claims 1 to 3, wherein the lower limit value of the average particle diameter of the silica fine particles is (average minor axis length of metal nanowires -2) nm.   The conductive patterning material according to claim 1, wherein the conductive layer has an average thickness of 0.01 μm to 0.3 μm.   The conductive patterning material according to claim 1, wherein the transmittance of the conductive layer is 80% or more, and the surface resistivity of the conductive layer is 10Ω / □ to 150Ω / □.   A touch panel comprising the conductive patterning material according to claim 1.