JPWO2015151489A1 - Composition for forming transparent conductive layer - Google Patents

Abstract

(A) conductive nanofiber; (B) (B-1) a silane compound having an amino group and an alkoxy group, and (B-2) a tetraalkoxysilane compound, (B-3) an amino group, an epoxy group and an isocyanate group A silane having one or more alkoxy groups selected from (B-4) a silane compound having an epoxy group and an alkoxy group, and (B-5) a blocked isocyanatosilane compound having an alkoxy group. Hydrolytic condensate of compound; (C) organic polymer fine particles and / or inorganic fine particles; (D) curing catalyst; (E) a composition for forming a transparent conductive layer comprising a dispersion medium.

Description

  The present invention relates to a composition for forming a transparent conductive layer, a transparent conductive layer obtained from the composition, and a method for producing the transparent conductive layer.

The transparent conductive film is a transparent electrode such as a liquid crystal display (LCD), plasma display panel (PDP), organic electroluminescence (OLED), solar cell (PV) and touch panel (TP), antistatic (ESD) film and electromagnetic wave shielding ( It is used in various fields such as EMI) film and requires low surface resistance, high light transmittance, and high reliability.
Conventionally, ITO (indium tin oxide) has been used for the transparent conductive film used for these transparent electrodes.

However, indium used in ITO has problems of supply insecurity and price increase. Moreover, since the sputtering method which requires a high vacuum is used for ITO film formation, a manufacturing apparatus becomes large-scale and manufacturing time and cost are large. Furthermore, the ITO film is easily broken due to cracks caused by physical stress such as bending. Since high heat is generated during the sputtering of the ITO film, the polymer of the flexible substrate is damaged, so that it is difficult to apply to a substrate with flexibility.
Therefore, the search of the conductive layer material which replaces ITO which solved these problems is actively advanced.

Among conductive layer materials replacing ITO, materials that can be applied and formed without sputtering are attracting attention. For example, (i) poly (3,4-ethylenedioxythiophene) / poly (4-styrenesulfonic acid) Polymer conductive materials such as (PEDOT: PSS) (Patent Document 1); (ii) Conductive materials containing metal nanowires (Patent Document 2 and Non-Patent Document 1); (iii) Random network with silver fine particles Conductive material having structure (Patent Document 3); (iv) Conductive material containing nanostructured conductive component such as conductive material containing carbon nanotubes (Patent Document 4); (v) Metal fine wiring A conductive material (Patent Document 5) made of a fine mesh using a material has been reported.
However, (i) has low light transmittance, and the conductive material is an organic molecule, so that the environmental resistance is poor, and (iii) has a complicated process because a transparent conductive film is prepared using self-organization. iv) has the disadvantage that the carbon nanotube has a black color and low light transmittance due to the carbon nanotubes, and (v) has the disadvantages that conventional processes cannot be used due to the use of photographic technology.

  The conductive material containing the metal nanowire (ii) has been reported as a conductive layer formed on a substrate. Patent Document 6 includes a bond represented by -M1-O-M1- (M1 = Si, Ti, Zr, Al) in a conductive layer, but requires an intermediate layer between the substrate and the substrate. There was a problem in adhesion. Patent Document 7 uses a sol-gel cured product obtained by hydrolysis and polycondensation of an alkoxide compound in a conductive layer as a matrix, but surface treatment of the substrate is necessary to improve adhesion to the substrate. Met. In Patent Document 8, a composition for forming a conductive layer contains a water-soluble polymer and a compound that thermally crosslinks with a —OH group of the water-soluble polymer or an alkoxysilyl group-containing compound and water as essential components. When it is contained, bubbles are likely to be generated during coating, and water tends to remain during drying. In Patent Document 9, the matrix resin forming the transparent conductive layer contains metal nanowires and translucent fine particles, but the adhesion to the substrate is unknown. Moreover, the particle diameter of the translucent fine particles was large, and the transparency and surface resistance were insufficient.

JP 2004-59666 A JP 2009-505358 A JP 2008-78441 A JP 2007-112133 A JP 2007-270353 A JP 2012-238579 A JP 2013-137882 A JP 2013-16455 A JP 2011-29099 A

Shin-Hsiang Lai, Chun-Yao Ou, “SID 08 DIGEST”, 2008, P1200-1202.

  The objective of this invention is providing the composition for transparent conductive layer formation which can form a transparent conductive layer with favorable durability and adhesiveness with a board | substrate.

According to the present invention, the following composition for forming a transparent conductive layer and the like are provided.
1. The composition for transparent conductive layer formation containing the following component (A)-(E).
(A) Conductive nanofiber (B) Hydrolysis condensate of a silane compound having one or more alkoxy groups selected from the following (B-1) and the following (B-2) to (B-5) B-1) Silane compound having amino group and alkoxy group (B-2) tetraalkoxysilane compound,
(B-3) Organoalkoxysilane compound containing no amino group, epoxy group and isocyanate group (B-4) Silane compound having epoxy group and alkoxy group (B-5) Blocked isocyanatosilane compound having alkoxy group ( C) Organic polymer fine particles and / or inorganic fine particles (D) Curing catalyst (E) Dispersion medium 2. The composition for forming a transparent conductive layer according to 1, wherein the hydrolysis-condensation product of the silane compound having an alkoxy group includes the (B-1) to (B-5).
3. 3. The composition for forming a transparent conductive layer according to 1 or 2, which satisfies D / L <0.010, where D is an average particle diameter of the inorganic fine particles and L is an average length of the conductive nanofibers.
4). The composition for forming a transparent conductive layer according to any one of 1 to 3, which satisfies D / L <0.010, where D is an average particle diameter of the organic polymer fine particles and L is an average length of the conductive nanofibers. object.
5. The composition for forming a transparent conductive layer according to any one of 1 to 4, wherein the inorganic fine particles are colloidal silica.
6). The composition for forming a transparent conductive layer according to any one of 1 to 5, wherein the conductive nanofiber has an average diameter of 0.5 nm to 100 nm and an average length of 1 μm to 100 μm.
7). The composition for forming a transparent conductive layer according to any one of 1 to 6, wherein the conductive nanofibers have an average diameter of 1 nm to 100 nm and an average length of 1 μm to 100 μm.
8). The composition for forming a transparent conductive layer according to any one of 1 to 7, wherein the conductive nanofibers have an average diameter of 5 nm to 50 nm and an average length of 3 μm to 50 μm.
9. The composition for forming a transparent conductive layer according to any one of 1 to 8, wherein the conductive nanofiber is a silver nanowire or a carbon nanotube.
10. The composition for forming a transparent conductive layer according to any one of 1 to 9, wherein the conductive nanofiber is a silver nanowire.
11. 11. The transparent conductive layer forming composition according to 10, wherein the silver nanowire has an average diameter of 5 nm to 50 nm and an average length of 5 μm to 30 μm.
12 The transparent conductive layer forming composition according to any one of 1 to 11, wherein the transparent conductive layer obtained from the transparent conductive layer forming composition can be patterned.
13. The transparent conductive layer forming composition as described in any one of 1 to 11, which can be patterned with either an acid or a base.
The transparent conductive layer obtained from the composition for transparent conductive layer formation in any one of 14.1-11.
15. 15. The transparent conductive layer according to 14, which can be patterned.
16. 16. The transparent conductive layer according to 15, which can be patterned with either an acid or a base.
The board | substrate with a transparent conductive layer which has a transparent conductive layer obtained by apply | coating the composition for transparent conductive layer formation in any one of 17.1-13 to a base material.
18. 18. The substrate with a transparent conductive layer according to 17, wherein the transparent conductive layer contains silver nanowires, and the content of the silver nanowires is 5 wt% or more and 98 wt% or less.
19. The substrate with a transparent conductive layer according to 17 or 18, wherein the transparent conductive layer has a total light transmittance of 85 to 100%, a haze of 3.0% or less, and a surface resistance of 5 to 500 Ω / □.
The manufacturing method of the board | substrate with a transparent conductive layer which has a transparent conductive layer which apply | coats the composition for transparent conductive layer formation in any one of 20.1-13 directly to a board | substrate.
The touch panel using the board | substrate with a transparent conductive layer in any one of 21.17-19.
Electrical equipment using the board | substrate with a transparent conductive layer in any one of 22.17-19.
A vehicle using the transparent conductive layer or the substrate with the transparent conductive layer according to any one of 23.14 to 19.

  ADVANTAGE OF THE INVENTION According to this invention, the composition for transparent conductive layer formation which can form a transparent conductive layer with favorable durability and adhesiveness with a board | substrate can be provided.

[Composition for forming transparent conductive layer]
The composition for forming a transparent conductive layer of the present invention comprises the following components (A)-(E):
(A) Conductive nanofiber (B) Hydrolysis condensate of a silane compound having one or more alkoxy groups selected from the following (B-1) and the following (B-2) to (B-5) B-1) Silane compound having amino group and alkoxy group (B-2) tetraalkoxysilane compound,
(B-3) Organoalkoxysilane compound containing no amino group, epoxy group and isocyanate group (B-4) Silane compound having epoxy group and alkoxy group (B-5) Blocked isocyanatosilane compound having alkoxy group ( C) Organic polymer fine particles and / or inorganic fine particles (D) Curing catalyst (E) Dispersion medium

The composition for forming a transparent conductive layer of the present invention contains components (A)-(E) and is a composition excellent in coatability. Since the obtained transparent conductive layer has good adhesion to the substrate, the transparent conductive layer forming composition of the present invention can be directly applied to the substrate to form the transparent conductive layer.
The obtained transparent conductive layer has uniformly dispersed conductive nanofibers, can exhibit both excellent transparency and conductivity, and is excellent in durability.
Hereinafter, each component will be described.

(A) Conductive nanofiber The conductive nanofiber as the component (A) includes metal nanowires and carbon nanotubes. The conductive nanofibers form a network in the coating film obtained from the composition and impart conductivity to the coating film.

  The metal constituting the metal nanowire that is a conductive nanofiber is any selected from the group consisting of gold, silver, platinum, copper, nickel, iron, cobalt, zinc, ruthenium, rhodium, palladium, cadmium, osmium, and iridium. Or an alloy composed of two or more selected from the group. A metal nanowire may be used individually by 1 type, and may be used in combination of 2 or more type. From the viewpoint of obtaining high total light transmittance and high conductivity, the metal nanowire is preferably a gold nanowire, a silver nanowire, or a copper nanowire, and more preferably a silver nanowire.

As the shape of the metal nanowire, for example, a columnar shape, a rectangular parallelepiped shape, a columnar shape having a polygonal cross section, and the like, the column shape or the cross section is a pentagonal shape in applications where high transparency is required. What is the above polygon is preferable.
The cross-sectional shape of the metal nanowire can be detected by applying a metal nanowire dispersion on the substrate and observing the cross-section with a transmission electron microscope (TEM).

The average diameter of the metal nanowire is preferably 100 nm or less, more preferably 50 nm or less, and further preferably 30 nm or less. In order to ensure durability, the average diameter of the metal nanowires is preferably 5 nm or more.
The average length of the metal nanowires is preferably 1 μm to 100 μm, more preferably 3 μm to 50 μm, and even more preferably 5 μm to 30 μm. If the average length of the metal nanowire is too long, there is a concern that aggregates may be produced during the production of the metal nanowire. If the average length is too short, sufficient conductivity may not be obtained.

The average diameter and average length of the metal nanowire can be measured by observing a TEM image or an optical microscope image using a transmission electron microscope (TEM) and an optical microscope.
For example, using an optical microscope, 300 metal nanowires are observed, and the average length of the metal nanowires can be obtained from the average value.
In addition, the average diameter when the short-axis direction cross section of metal nanowire is not circular makes the average value the average value of the length of the longest part by the measurement of a short-axis direction. Also. When the metal nanowire is bent, a circle having the arc as an arc is taken into consideration, and an average value of values calculated from the radius and the curvature is set as an average length.
In order to make the conductive layer transparent, metal nanowires having an average diameter of 50 nm or less and an average length of 5 μm or more are preferable.

The aspect ratio of the metal nanowire is not particularly limited as long as it is 10 or more, and can be appropriately selected according to the purpose, but is preferably 50 to 1,000,000, more preferably 100 to 1,000,000. .
The aspect ratio generally means the ratio between the long side and the short side of the fibrous material (ratio of average length / average diameter), and is calculated from the values of the average length and average diameter measured by the above method. it can.

Carbon nanotubes, which are conductive nanofibers, are carbon-based fiber materials that have a shape in which a graphitic carbon atomic surface (graphene sheet) with a thickness of several atomic layers is wound into a cylindrical shape. Nanotubes (SWNT) and multi-walled nanotubes (MWNT) are roughly classified. In addition, single-walled carbon nanotubes are classified into a chiral type, a zigzag type, and an armchair type depending on the difference in the structure of the graphene sheet, and various types are known.
Any type of carbon nanotube can be used in the present invention as long as it is referred to as such a carbon nanotube. A mixture of these various carbon nanotubes may be used.

The carbon nanotubes are preferably single-walled nanotubes having a large aspect ratio, that is, thin and long. For example, an aspect ratio of 10 ² or more, and preferably 10 ³ or more carbon nanotubes.
The length of the carbon nanotube is usually 1 μm or more, preferably 5 μm or more, more preferably 10 μm or more, and the upper limit of the length is not particularly limited, but is, for example, about 10 mm. As the outer diameter, extremely minute carbon nanotubes on the order of nm are known. The carbon nanotubes are preferably surface-treated with an organic compound. Specifically, it is preferable to improve dispersibility using a surfactant.

(B) Hydrolysis condensate of a silane compound having an alkoxy group As a hydrolysis condensate of a silane compound having an alkoxy group, a hydrolysis condensate of a silane compound (B-1) is further included, and (B-2) to (B-2) to (B) A hydrolyzed condensate of one or more silane compounds selected from B-5).
(B-1) Silane compound having amino group and alkoxy group (B-2) Tetraalkoxysilane compound,
(B-3) Organoalkoxysilane compound containing no amino group, epoxy group and isocyanate group (B-4) Silane compound having epoxy group and alkoxy group (B-5) Blocked isocyanatosilane compound having alkoxy group

The composition for forming a transparent conductive layer of the present invention comprises a hydrolysis condensate of one or more silane compounds selected from (B-1) and (B-2) to (B-5) as the component (B). When included, it may further contain one or more silane compounds selected from (B-6) and (B-7).
(B-6) Silane compound having a double bond between carbons (B-7) Silane compound having a mercapto group and an alkoxy group

The components (B-1) to (B-5) may be hydrolysis condensates, and the components (B-6) to (B-7) may be hydrolysis condensates. The hydrolysis condensate may be a hydrolysis condensate of a single compound of components (B-1) to (B-7), or any of the components (B-1) to (B-7). It may be a hydrolysis condensate of a mixture of two or more.
In the present invention, a silane compound containing an alkoxy group is an alkoxysilane compound and / or a partial condensate thereof, and a partial condensate of an alkoxysilane compound is a part of the alkoxysilane compound condensed and siloxane in the molecule. A polyalkoxysilane compound or a polyorganoalkoxysilane compound formed by forming a bond (Si—O bond).
The hydrolyzed condensate of the silane compound containing an alkoxy group may include a silane compound containing the alkoxy group before hydrolytic condensation in addition to the hydrolyzed condensate of the silane compound containing an alkoxy group.

  The hydrolysis condensate of the silane compound having an alkoxy group preferably contains all of (B-1) to (B-5).

(B-1) Silane Compound Having Amino Group and Alkoxy Group A silane compound having an amino group and an alkoxy group is an alkoxysilane compound that does not contain an epoxy group and an isocyanate group. Moreover, the partial condensate (amino group containing polyorganoalkoxysilane compound) can also be used. These compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

An amino group-containing organoalkoxysilane compound and a partial condensate thereof, which are silane compounds having an amino group and an alkoxy group, can be represented by, for example, the following formula (3).
R ⁴ _b Si (OR ⁵ ) _4-b (3)
[Wherein, R ⁴ represents an alkyl group having 1 to ⁴ carbon atoms; a phenyl group; or an amino group (—NH ₂ group), an aminoalkyl group [— (CH ₂ ) _x —NH ₂ group (where x is 1 to An integer of 3)]), an alkylamino group [-NHR group (where R is an alkyl group having 1 to 3 carbon atoms)], and an alkyl group having 1 to 3 carbon atoms substituted with one or more groups selected from And at least one of R ⁴ is an alkyl group having 1 to 3 carbon atoms substituted with any one of an amino group, an aminoalkyl group and an alkylamino group. R ⁵ is an alkyl group having 1 to 4 carbon atoms, and b is 1 or 2. If R ⁴ is plural, R ⁴ may be the same or different, the plurality of OR ⁵ may be the same or different. ]
In the above formula (3), the alkyl group having 1 to 3 carbon atoms and the alkyl group having 1 to 4 carbon atoms are the same as those in formula (1) or (2) described later. R ⁴ is preferably an alkyl group having 1 to ⁴ carbon atoms or an alkyl group having 1 to 3 carbon atoms substituted with an amino group. R ⁵ is preferably an alkyl group having 1 to 4 carbon atoms. Preferably b is 1.

Specific examples of the amino group-containing organoalkoxysilane compound represented by the formula (3) include N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane and N- (2-aminoethyl) -3-aminopropyl. Trimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-amino Examples include propyltriethoxysilane, N-methylaminopropyltrimethoxysilane, and N-methylaminopropyltriethoxysilane.
Examples of the amino group-containing polyorganoalkoxysilane compound include “KBP-90” manufactured by Shin-Etsu Silicone Co., Ltd.

(B-2) Tetraalkoxysilane Compound As the tetraalkoxysilane compound, a tetraalkoxysilane compound or a partial condensate (polyalkoxysilane compound) bonded by a siloxane bond (Si—O bond) can be used. These compounds may be used individually by 1 type, and may be used in combination of 2 or more type.
The tetraalkoxysilane compound and the partial condensate thereof can be represented, for example, by the following formula (1), and a compound represented by the following formula (6) is particularly preferable.
Si (OR ¹ ) ₄ (1)
[Wherein, R ¹ represents an alkyl group having 1 to 4 carbon atoms or an alkoxyalkyl group having 1 to 4 carbon atoms. A plurality of R ¹ may be the same or different. ]

［式中、Ｒ^１は、上記と同じであり、ｎは１〜１５の整数である。］

[Wherein, R ¹ is the same as above, and n is an integer of 1 to 15.] ]

In formulas (1) and (6), examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and various butyl groups, and R ¹ the OR ¹ is an alkoxyalkyl group having 1 to 4 carbon atoms, for example, 2-methoxyethoxy group, and 3-methoxypropoxy group.
Examples of the tetraalkoxysilane compound include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, and tetraisobutoxysilane.
Examples of the polyalkoxysilane compound include “M silicate 51”, “silicate 40”, and “silicate 45” manufactured by Tama Chemical Industry Co., Ltd., and “methyl silicate 51”, “methyl silicate 53A”, and “ethyl silicate 40” manufactured by Colcoat Co., Ltd. "Ethyl silicate 48" etc. are mentioned.

(B-3) Organoalkoxysilane compound containing no amino group, epoxy group or isocyanate group As the organoalkoxysilane compound, an organoalkoxysilane compound or a partial condensate thereof can be used. The organoalkoxysilane compound does not contain an amino group, an epoxy group, or an isocyanate group.
These compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

As the organoalkoxysilane compound, the organoalkoxysilane compound and the partial condensate thereof are preferably bifunctional alkoxysilane and trifunctional alkoxysilane, and can be represented by, for example, the following formula (2). The compounds represented are preferred.
R ² _a Si (OR ³ ) _4-a (2)
[Wherein, R ² represents an alkyl group having 1 to 10 carbon atoms, a fluorinated alkyl group or phenyl group having 1 to 10 carbon atoms, and R ³ represents an alkyl group having 1 to 4 carbon atoms or an alkoxyalkyl having 1 to 4 carbon atoms. And a is 1 or 2. When R ² are a plurality, the plurality of R ² may be the same or different, a plurality of OR ³ may be the same or different. ]

［式中、Ｒ^２及びＲ^３は上記と同じであり、ｍは１〜１５の整数である。］

[Wherein R ² and R ³ are the same as above, and m is an integer of 1 to 15.] ]

In the formulas (2) and (7), the alkyl group having 1 to 10 carbon atoms may be linear or branched, for example, methyl group, ethyl group, n-propyl group, isopropyl group Various butyl groups, various hexyl groups, various octyl groups, various decyl groups, and the like. Examples of the fluorinated alkyl group include a trifluoroethyl group and a trifluoropropyl group. Moreover, as a C1-C3 alkyl group, a methyl group, an ethyl group, n-propyl group, and an isopropyl group are mentioned. The alkyl group or alkoxyalkyl group having 1 to 4 carbon atoms is as described in the formula (1). Preferably ^{R 2} is an alkyl group having 1 to 4 carbon atoms. R ³ is preferably an alkyl group having 1 to 4 carbon atoms. Preferably a is 1.

  Among the organoalkoxysilane compounds represented by formula (2), trifunctional alkoxysilanes include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, and methyl-tris (2-methoxyethoxy). ) Silane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltributoxysilane, ethyl-tris (2-methoxyethoxy) silane, hexyltrimethoxysilane, hexyltriethoxysilane, hexyltripropoxysilane, hexyl Fluorinated amines such as tributoxysilane, decyltrimethoxysilane, decyltriethoxysilane, decyltripropoxysilane, decyltributoxysilane, trifluoropropyltrimethoxysilane, etc. Kill (trialkoxy) silane, phenyl trimethoxy silane, and phenyl triethoxy silane and the like. Moreover, methyldimethoxy (ethoxy) silane, ethyl diethoxy (methoxy) silane, etc. which contain two types of alkoxy groups are also mentioned.

Examples of the bifunctional alkoxysilane include dimethyldimethoxysilane, dimethyldiethoxysilane, bis (2-methoxyethoxy) dimethylsilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and the like.
Specific examples of the polyorganoalkoxysilane compound include “MTMS-A” manufactured by Tama Chemical Industry Co., Ltd., “SS-101” manufactured by Colcoat Co., Ltd., “AZ-6101” “SR2402” manufactured by Toray Dow Corning Co., Ltd. "AY42-163" and the like.

(B-4) Silane compound having an epoxy group and an alkoxy group The silane compound having an epoxy group and an alkoxy group is a silane compound having an epoxy group and an alkoxy group, and does not include an amino group and an isocyanate group. is there. Moreover, the partial condensate (epoxy group containing polyorganoalkoxysilane compound) can also be used. These compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

An epoxy group-containing organoalkoxysilane compound and a partial condensate thereof, which are silane compounds having an epoxy group and an alkoxy group, can be represented by, for example, the following formula (4).
R ⁶ _c Si (OR ⁷ ) _4-c (4)
[Wherein R ⁶ is an alkyl group having 1 to 4 carbon atoms; a phenyl group; or a glycidoxy group or a 3,4-epoxycyclohexyl group substituted with one or more groups selected from 1 to 6 carbon atoms (preferably Is an alkyl group having 1 to 4 carbon atoms, and at least one of R ⁶ has 1 to 6 carbon atoms (preferably 1 to 4 carbon atoms) substituted with a glycidoxy group or a 3,4-epoxycyclohexyl group. It is an alkyl group. R ⁷ is an alkyl group having 1 to 4 carbon atoms, and c is 1 or 2. If R ⁶ is plural, R ⁶ may be the same or different, a plurality of OR ⁷ may be the same or different. ]

In the above formula (4), the alkyl group having 1 to 4 carbon atoms is as described in the above formula (1), and the alkyl group having 1 to 6 carbon atoms has 1 to 10 carbon atoms in the above formula (2). Among these alkyl groups, those having 1 to 6 carbon atoms. R ⁶ preferably has 1 to ⁶ carbon atoms (preferably 1 to 4 carbon atoms) substituted with one or more groups selected from an alkyl group having 1 to 4 carbon atoms, a glycidoxy group, and a 3,4-epoxycyclohexyl group. And more preferably an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4 carbon atoms) substituted with an alkyl group having 1 to 4 carbon atoms or a glycidoxy group. R ⁷ is preferably an alkyl group having 1 to 4 carbon atoms. Preferably c is 2.

  Specific examples of the epoxy group-containing organoalkoxysilane compound represented by the formula (4) include 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltrimethoxysilane. , 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, and the like.

(B-5) Blocked isocyanate silane compound having an alkoxy group A blocked isocyanate silane compound having an alkoxy group (generally also referred to as a blocked isocyanate silane compound or a blocked isocyanate silane compound) includes an alkoxy group and An alkoxysilane compound containing a blocked isocyanate group but not containing an amino group or an epoxy group. Moreover, the partial condensate (blocked isocyanate group containing polyorganoalkoxysilane compound) can also be used. These compounds may be used individually by 1 type, and may be used in combination of 2 or more type.
The blocked isocyanatosilane compound is an isocyanatosilane compound in which an isocyanate group is protected by a blocking agent such as oxime to be inactive, and is deblocked by heating to activate (regenerate) the isocyanate group (general) Also referred to as an isocyanate silane compound).

The blocked isocyanate group-containing organoalkoxysilane compound and its partial condensate, which are blocked isocyanate silane compounds having an alkoxy group, can be represented, for example, by the following formula (5).
R ⁸ _d Si (OR ⁹ ) _4-d (5)
[Wherein R ⁸ is an alkyl group having 1 to 4 carbon atoms; a phenyl group; or an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4 carbon atoms) substituted with a blocked isocyanate group, and R ⁸ At least one is an alkyl group having 1 to 6 carbon atoms (preferably having 1 to 4 carbon atoms) substituted with a blocked isocyanate group. R ⁹ is an alkyl group having 1 to 4 carbon atoms, and d is 1 or 2. If R ⁸ is plural, R ⁸ may be the same or different, a plurality of OR ⁹ may be the same or different. ]
In the above formula (5), the alkyl group having 1 to 4 carbon atoms and the alkyl group having 1 to 6 carbon atoms are as described in the above formula (1) or (4). Preferably, R ⁸ is an alkyl group having 1 to 4 carbon atoms (preferably having 1 to 4 carbon atoms) substituted with an alkyl group having 1 to 4 carbon atoms or a blocked isocyanate group. R ⁹ is preferably an alkyl group having 1 to 4 carbon atoms. Preferably d is 1.

  Specific examples of the blocked isocyanate group-containing organoalkoxysilane compound represented by the formula (5) include 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, What protected the isocyanate group in compounds, such as 3-isocyanatopropyl methyl diethoxysilane and 3-isocyanatopropyl ethyl diethoxysilane, with the blocking agent is mentioned. Among these, 3-blocked isocyanatopropyltriethoxysilane can be mentioned as a preferable compound.

  Examples of the blocking agent for isocyanate groups include oxime compounds such as acetooxime, 2-butanone oxime, cyclohexanone oxime, methyl isobutyl ketoxime, lactams such as ε-caprolactam, alkylphenols such as monoalkylphenol (cresol, nonylphenol, etc.), Active methylene compounds such as 3,5-xylenol, dialkylphenols such as di-t-butylphenol, trialkylphenols such as trimethylphenol, malonic acid diesters such as diethyl malonate, acetoacetates such as acetylacetone and ethyl acetoacetate , Alcohols such as methanol, ethanol, n-butanol, hydroxyl group-containing ethers such as methyl cellosolve and butyl cellosolve, hydroxyl groups such as ethyl lactate and amyl lactate Esters, mercaptans such as butyl mercaptan and hexyl mercaptan, acid amides such as acetanilide and dimer acid amide, imidazoles such as imidazole and 2-ethylimidazole, pyrazoles such as 3,5-dimethylpyrazole, 1,2 Triazoles such as 1,4-triazole, and acid imides such as succinimide and phthalic imide can be used. In order to control the dissociation temperature of the blocking agent, a catalyst such as dibutyltin dilaurate may be used in combination.

(B-6) Silane compound having a carbon-carbon double bond (B-6) The component is a silane compound containing a group having a carbon-carbon double bond such as a vinyl group, an acryl group, or a methacryl group, preferably Contains an alkoxy group. Moreover, an amino group, an epoxy group, and an isocyanate group are not included.
In addition, the “carbon-carbon double bond” of the component (B-6) does not include an aromatic double bond. In this specification, the aromatic double bond is a double bond in a cyclic conjugated compound having 4n + 2 (n is an integer of 0 or more) π electrons.

When the composition of the present invention includes (B-6) a silane compound having a carbon-carbon double bond, photocuring (UV curing) and electron beam curing (EB curing) are possible in addition to thermal curing.
As the silane compound having a carbon-carbon double bond, a partial condensate thereof (polyorganoalkoxysilane compound containing a group having a carbon-carbon double bond) can also be used. These compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

A silane compound having a carbon-carbon double bond and a partial condensate thereof can be represented, for example, by the following formula (20).
R ²⁰ _e Si (OR ²¹ ) _4-e (20)
[Wherein, R ²⁰ represents an alkyl group having 1 to 4 carbon atoms; vinyl group; or 1 to 6 carbon atoms substituted with a substituent having one or more groups selected from vinyl group, acrylic group and methacryl group. (Preferably having 1 to 4 carbon atoms) an alkyl group, and at least one of R ²⁰ is a carbon number substituted with a substituent having one or more groups selected from a vinyl group, an acrylic group and a methacryl group. It is a 1-6 (preferably C1-C4) alkyl group. R ²¹ is an alkyl group having 1 to 4 carbon atoms, and e is 1 or 2. If R ²⁰ there are a plurality, the plurality of R ²⁰ may be the same or different, a plurality of OR ²¹ may be the same or different. ]

In the formula (20), the alkyl group having 1 to 6 carbon atoms and the alkyl group having 1 to 4 carbon atoms are as described in the formula (1) or (4). Preferably, R ²⁰ has 1 to 6 carbon atoms (preferably 1 to 4 carbon atoms) substituted with one or more groups selected from an alkyl group having 1 to 4 carbon atoms, or a vinyl group, an acrylic group and a methacryl group. ) Alkyl group. Preferably, e is 1.

  The alkyl group having 1 to 6 carbon atoms (preferably 1 to 4 carbon atoms) substituted with a substituent having one or more groups selected from a vinyl group, an acryl group, and a methacryl group is preferably a vinyl group, It is a C1-C6 (preferably C1-C4) alkyl group substituted by 1 or more groups chosen from a vinyloxy group, an acryl group, an acryloxy group, a methacryl group, and a methacryloxy group, More preferably , An alkyl group having 1 to 6 carbon atoms (preferably 1 to 4 carbon atoms) substituted with one or more groups selected from an acrylic group, an acryloxy group, a methacryl group and a methacryloxy group.

  Specific examples of the compound represented by the formula (20) include 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxypropylmethyldiethoxysilane. An acrylic silane compound (acrylic group-containing silane compound) such as 3-methacryloxypropyltriethoxysilane, and a vinyl group-containing silane compound such as vinyltrimethoxysilane and vinyltriethoxysilane.

(B-7) A silane compound having a mercapto group and an alkoxy group A silane compound having a mercapto group and an alkoxy group is a silane compound containing a group having a thiol group (IUPAC; also known as a hydroxyl group, a mercapto group, or a sulfhydryl group). Including an alkoxy group. Moreover, an amino group, an epoxy group, and an isocyanate group are not included. Moreover, the silane compound containing the group which has a triazine thiol group may be sufficient.
Specific examples of the component (B-7) include 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-mercaptopropyltriethoxysilane. Examples of the alkoxy oligomer include X-41-1805, X-41-1818, and X-41-1810 manufactured by Shin-Etsu Chemical Co., Ltd. Furthermore, as a triazine thiol group containing silicone alkoxy oligomer, X-24-9451, X-249452, X-24-9453, X-249454 by Shin-Etsu Chemical Co., Ltd. are mentioned.

(C) Organic polymer fine particles and / or inorganic fine particles The composition for forming a transparent conductive layer of the present invention contains organic polymer fine particles and / or inorganic fine particles. That is, the composition of the present invention may contain either organic polymer fine particles or inorganic fine particles, and may contain both organic polymer fine particles and inorganic fine particles.

Examples of the organic polymer fine particles include those obtained by polymerizing an ethylenically unsaturated compound (acrylic acid, methacrylic acid and derivatives thereof, styrene, vinyl acetate, etc.).
From the viewpoint of manufacturability, dispersibility in the composition, coating property of the composition, transparency of the coating film, and the like, the organic polymer fine particles preferably have an average particle diameter in the range of 1 to 200 nm. What is in the range of 100 nm is more preferable. The average particle size of the organic polymer fine particles can be measured by a dynamic light scattering method. Moreover, when it cannot measure by the dynamic light scattering method, you may measure by the X-ray small angle scattering method.
In the dynamic light scattering method, for example, a solution obtained by diluting organic polymer fine particles 100 times with ion-exchanged water is measured using a dynamic light scattering particle size distribution measuring device (Beckman Coulter Co., Ltd., Coulter Counter N5). The average particle size is obtained by unimodal analysis (monodisperse mode analysis). This is repeated 5 times, and the average value of the average particle diameter for 5 times can be made the average particle diameter of the organic polymer.

  When the average particle diameter of the organic polymer fine particles is D and the average length of the conductive nanofibers is L, it is preferable that D / L <0.010, more preferably D / L <0.0050. is there.

  In the present invention, the organic polymer fine particles are preferably used in a form dispersed in a dispersion medium. Examples of the dispersion medium include water, methanol, ethanol, propanol, 1-methoxy-2-propanol, and the like. Preferred examples include alcohols and cellosolves such as methyl cellosolve. By using such a dispersion medium, the dispersibility of the organic polymer fine particles is improved, and sedimentation can be prevented. More preferably, the dispersion medium is water. When the dispersion medium is water, it can also be used for the hydrolysis and condensation reaction of the silane compound in the formation of the matrix containing Si-O bonds derived from the components (B-1) to (B-5) described above.

There is no restriction | limiting in particular in the manufacturing method of organic polymer fine particle, A conventionally well-known method, for example, an emulsion polymerization method, a fine suspension polymerization method, etc. are employable.
In the emulsion polymerization method, the above monomer is emulsified into fine droplets using an ethylenically unsaturated monomer, an aqueous dispersion medium, an emulsifier composed of an anionic or nonionic surfactant and a water-soluble polymerization initiator. In this method, polymerization is carried out in a surfactant micelle layer surrounding the mixture to obtain a dispersion of fine organic polymer particles.
On the other hand, the fine suspension polymerization solution is first premixed in an aqueous medium by adding the monomer, oil-soluble polymerization initiator, emulsifier and other additives as necessary, and homogenized by a homogenizer, Adjust the particle size of the oil droplets. Next, the homogenized liquid is sent to a polymerization vessel and a polymerization reaction is performed to obtain a dispersion of organic polymer fine particles.
In any of the above methods, the polymerization temperature is about 30 to 80 ° C.

Examples of the water-soluble polymerization initiator used for emulsion polymerization include water-soluble peroxides such as potassium persulfate, ammonium persulfate, and hydrogen peroxide, these initiators or cumene hydroperoxide, t-butyl hydroperoxide, and the like. Redox initiators that combine hydroperoxides with reducing agents such as acidic sodium sulfite, ammonium sulfite, and ascorbic acid, water-soluble azo compounds such as 2,2′-azobis (2-methylpropionamidine) dihydrochloride, etc. Can be mentioned.
On the other hand, examples of oil-soluble polymerization initiators used for fine suspension polymerization include oil-soluble organic peroxides such as diacyl peroxides, ketone peroxides, peroxyesters, peroxydicarbonates, and the like. Examples include azo compounds such as' -azobisisobutyronitrile and 2,2'-azobis (2,4-dimethylvaleronitrile).

Specific examples of the organic polymer fine particles include emulsion-based polymer ultraviolet absorbers ULS-700, ULS-1700, ULS-383MA, ULS-1383MA, ULS-383MG, ULS-385MG, and ULS manufactured by Yushi Co., Ltd. -1383MG, ULS-1385MG, ULS-635MH, etc., Nissin Chemical Industry Co., Ltd. Vinibrand 700, 701, 711, Nippon Zeon Co., Ltd. Nipol series, etc. are mentioned.
The organic polymer fine particles may be used alone or in combination of two or more.

Examples of the inorganic fine particles include metal fine particles such as silver and copper, and metal oxide fine particles such as colloidal silica, titanium oxide, cerium oxide, zirconium oxide, ITO, and ATO (antimony trioxide).
The inorganic fine particles are preferably colloidal silica. Colloidal silica is also called colloidal silica or colloidal silicic acid. In water, it refers to a colloidal suspension of silicon oxide having Si—OH groups on its surface by hydration, and is formed when hydrochloric acid is added to an aqueous solution of sodium silicate. Recently, new preparation methods have been developed one after another, including those dispersed in non-aqueous solutions and fine powders made by the gas phase method, and hollow types with particle sizes from several nanometers. It is various up to several μm.

The average particle diameter of the inorganic fine particles is preferably about 1 to 200 nm. The composition of the particles is indefinite, and some particles are polymerized by forming siloxane bonds (—Si—O—, —Si—O—Si—). The particle surface is porous and is generally negatively charged in water.
The average particle diameter is assumed to be true particles, for example, after drying, firing, and pulverizing inorganic fine particles, using a BET specific surface area measuring device (Monosorb MS-17) to obtain a BET specific surface area by a nitrogen adsorption method. It can be measured by converting to the particle size of time. When the average particle system cannot be measured due to the BET specific surface area, it may be measured by the X-ray small angle scattering method.

  When the average particle diameter of the inorganic fine particles is D and the average length of the conductive nanofibers is L, it is preferably D / L <0.010, more preferably D / L <0.0050.

Commercial products of colloidal silica include “ultra-high-purity colloidal silica” Quartron PL series (product names: PL-1, PL-3, PL-7) manufactured by Fuso Chemical Industry, Nissan “high-purity organosol”, Nissan “Colloidal silica (product names: Snowtex 20, Snowtex 30, Snowtex 40, Snowtex O, Snowtex O-40, Snowtex C, Snowtex N, Snowtex S, Snowtex 20L, Snow Tex OL etc.) and “organosilica sol (product names: methanol silica sol, MA-ST-MS, MA-ST-L, IPA-ST, IPA-ST-MS, IPA-ST-L, IPA-ST-ZL, IPA) -ST-UP, EG-ST, NPC-ST-30, MEK-ST, MEK-ST MS, MIBK-ST, XBA-ST, PMA-ST, DMAC-ST, PGM-ST, etc.) "can be mentioned.
(C) As a component, colloidal silica may be used individually by 1 type, and may be used in combination of 2 or more type.

(D) Curing catalyst The curing catalyst is a catalyst that hydrolyzes and condenses (cures) the above-mentioned silane compounds (B-1) to (B-7), and includes, for example, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, nitrous acid. Inorganic acids such as nitric acid, perchloric acid and sulfamic acid, organic acids such as formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, citric acid, tartaric acid, succinic acid, maleic acid, glutamic acid, lactic acid and p-toluenesulfonic acid Can be mentioned.

Lithium hydroxide, sodium hydroxide, potassium hydroxide, n-hexylamine, dimethylamine, tributylamine, diazabicycloundecene, ethanolamine acetate, dimethylaniline formate, tetraethylammonium benzoate, sodium acetate, potassium acetate Organic metal salts such as sodium propionate, sodium glutamate, potassium propionate, sodium formate, potassium formate, benzoyltrimethylammonium acetate, tetramethylammonium acetate, tin octylate, tetraisopropyl titanate, tetrabutyl titanate, aluminum triisobutoxide , aluminum triisopropoxide, aluminum _{acetylacetonate,} SnCl _4, TiCl 4, etc. Lewis acids ZnCl ₄ and the like can be mentioned, et al That.

Among these curing catalysts, an organic acid can be preferably used because it can be highly dispersed even if the blending amount of (C) is increased and the transparency of the resulting film can be improved. In particular, an organic carboxylic acid, preferably acetic acid, can be preferably used.
(D) As a component, the said curing catalyst may be used individually by 1 type, and may be used in combination of 2 or more type.

(E) Dispersion medium The composition of the present invention is used in a state where conductive nanofibers, inorganic fine particles, organic fine particles and the like are dispersed in a dispersion medium. The dispersion medium is not particularly limited as long as it can uniformly mix and disperse conductive nanofibers. For example, in addition to water, organic substances such as alcohols, aromatic hydrocarbons, ethers, and esters can be used. A system dispersion medium can be mentioned. Among these organic dispersion media, specific examples of alcohols include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, t-butyl alcohol, n-hexyl alcohol, n- Octyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether, 1-methoxy-2-propanol (propylene glycol monomethyl ether), propylene monomethyl ether acetate, diacetone Alcohol, methyl cellosolve, ethyl cellosolve, propyl cellosolve, butyl cellosolve, benzyl alcohol And the like can be given.

Specific examples of other dispersion media include tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, xylene, dichloroethane, toluene, methyl acetate, ethyl acetate, ethoxyethyl acetate, and the like.
Among these dispersion media, water and alcohols are preferable from the viewpoint of performance as a dispersion medium.
(E) As a component, the said dispersion medium may be used individually by 1 type, and may be used in combination of 2 or more type.

(Optional additive)
In addition to the above components, the composition of the present invention may appropriately contain various known additive components used in conventional compositions as necessary.
Examples of the additive component that can be contained as required include a dispersion stabilizer, a leveling agent, a flexibility imparting agent, a lubricity imparting agent, an antioxidant, an antisulfurizing agent, a metal corrosion inhibitor, and an antiseptic. , Bluing agents, antifoaming agents (antifoaming agents), light stabilizers, weathering agents, colorants, viscosity modifiers, fine particle dispersants (antisettling agents), fine particle surface activity modifiers, etc. Can be mentioned.

<Leveling agent>
A leveling agent can be added to the composition in order to improve the smoothness of the resulting coating film and the flowability during coating. Examples of these additives include silicone leveling agents and fluorine leveling agents. , Acrylic leveling agents, vinyl leveling agents, and leveling agents in which fluorine and acrylic are combined. All work on the surface of the coating and reduce the surface tension. Each has its own characteristics and can be used according to the purpose. The ability to lower the surface tension is strong in silicone and fluorine systems, but acrylic and vinyl systems are advantageous in that wetting defects are less likely to occur when recoating.

  As a specific example of the silicone leveling agent, a copolymer of polyoxyalkylene and polydimethylsiloxane can be used. Commercially available silicone leveling agents include FZ-2118, FZ-77, FZ-2161, etc. manufactured by Toray Dow Corning Co., Ltd., KP321, KP323, KP324, KP326, KP340, KP341, etc. manufactured by Shin-Etsu Chemical Co., Ltd. -Performance Materials Japan GK TSF4440, TSF4441, TSF4445, TSF4450, TSF4446, TSF4452, TSF4453, TSF4460, BYK-300, BYK-302, BYK-306, BYK-307, BYK, etc. -320, BYK-325, BYK-330, BYK-331, BYK-333, BYK-337, BYK-341, BYK-344, BYK-345, BYK-346, BY -348, may be mentioned BYK-377, BYK-378, BYK-UV3500, BYK-3510, BYK-3570 and the like polyether-modified silicone oil (polyoxyalkylene-modified silicone oil) and the like.

  Moreover, when heat resistance of 150 degreeC or more is required, the aralkyl modified silicone oil which has polyester modification and a benzene ring is suitable. As a commercially available product of polyester-modified silicone oil, BYK-310, BYK-315, BYK-370 manufactured by BYK Japan Japan Co., Ltd., as a commercially available product of aralkyl-modified silicone oil having a benzene ring, BYK manufactured by BYK Japan Japan Co., Ltd. -322, BYK-323, and the like.

As the fluorine leveling agent, a copolymer of polyoxyalkylene and fluorocarbon can be used.
Examples of commercially available fluorine leveling agents include MEGAFAC series manufactured by DIC Corporation, FC series manufactured by Sumitomo 3M Corporation, and the like.
Examples of commercially available acrylic leveling agents include BYK-350, BYK-352, BYK-354, BYK-355, BYK358N, BYK-361N, BYK-380N, BYK-382, BYK-392 manufactured by BYK-Chemie Japan. And BYK-340 into which fluorine is introduced.

By blending such a leveling agent, the finished appearance of the coating film is improved, and it can be uniformly applied as a thin film. The amount of the leveling agent used is preferably 0.01 to 10% by mass, more preferably 0.02 to 5% by mass, based on the total amount of the composition.
As a method of blending the leveling agent, it may be blended when preparing the composition, or may be blended into the composition immediately before forming the coating film, and further, preparation of the composition and formation of the coating film. You may mix | blend in both the last steps.

<Flexibility imparting agent>
In order to improve the flexibility of the resulting coating film, the composition may contain a flexibility imparting agent as a stress relaxation agent.
As the flexibility imparting agent, for example, a silicone resin or the like can be used.
Examples of commercially available silicone resin, Wacker Co. Resin MK series, for example, a polymer comprising _{Belsil PMS MK (CH 3 SiO 3} /2 of the repeating units (units T), up to 1 wt% _(CH 3) containing ₂ SiO _2/2 units (units D) but also the) or, Si-OH end groups comprises units T and 2% by weight of dimethyl units D of Shin-Etsu Chemical Co., Ltd. KR-242A (98 wt% things), KR-251 (those containing Si-OH end groups comprises units T and 12 wt% of dimethyl units D of 88 wt%) consists of units T of KR-220L (formula _CH 3 _SiO 3/2, And those containing Si-OH (silanol) end groups).

(Content of each component in the composition for forming a transparent conductive layer)
Although content of each component in a composition can be selected suitably, it is preferable to select so that content of each component may become the range shown below, for example.
(E) Except the dispersion medium of a component, each component content with respect to the total amount of (A), (B) [(B-1)-(B-7)], (C) and (D) is mass%. It expresses by. The component (C) preferably used as the dispersion state is calculated using only the solid content, and the dispersion medium included in each component is included in the component (E).

  (A) Content of a component is 5 mass% or more and 98 mass%, for example, Preferably it is 10-75 mass%. If the amount is less than 5% by mass, the conductivity may not be exhibited. If the amount is more than 98% by mass, the adhesion to the substrate may be reduced.

(B-1) Content of a component is about 0.1-30 mass% normally, Preferably it is 1-20 mass%.
(B-2) Content of a component is about 0.01-40 mass% normally, Preferably it is 1-20 mass%.
(B-3) Content of a component is about 0.1-40 mass% normally, Preferably it is 1-30 mass%.
(B-4) Content of a component is about 0.1-30 mass% normally, Preferably it is 1-20 mass%.
The content of the component (B-5) is usually about 0.1 to 50% by mass, preferably 1 to 40% by mass.
The content of the component (B-6) is usually about 0 to 50% by mass, preferably 0.1 to 40% by mass.
The content of the component (B-7) is usually about 0 to 50% by mass, preferably 0.1 to 40% by mass.

The content of the organic polymer fine particles as component (C) is usually about 0 to 50% by mass, preferably 0.1 to 20% by mass.
(C) Content of the inorganic fine particle which is a component is about 0-70 mass% normally, Preferably it is 1-50 mass%.
(D) Content of a component is about 0.001-30 mass% normally, Preferably it is 0.001-20 mass%.
The content of the component (E) is usually about 5 to 100000 parts by weight, preferably 100 to 50000 parts by weight with respect to the total parts by weight of the components (A), (B), (C) and (D). is there.

  In addition, although there is no restriction | limiting in particular as a compounding molar ratio of (B-1) component and (B-5) component, Preferably it is 1: 1-1: 5, More preferably, it is 1: 2-1: 4. is there. If the blending molar ratio of the component (B-1) and the component (B-5) is within the above range, the durability of the resulting coating film is further improved.

The composition for forming a transparent conductive layer of the present invention is substantially only (A), (B), (C), (D) and (E), or (A), (B), (C), ( It may consist only of D) and (E).
Examples of the other components include the optional addition components described above.
Here, “substantially” means that 95% by weight to 100% by weight (preferably 98% by weight to 100% by weight) of the composition for forming a transparent conductive layer is (A), (B), (C). , (D) and (E).
The composition for forming a transparent conductive layer used in the present invention contains inevitable impurities in addition to (A), (B), (C), (D) and (E) as long as the effects of the present invention are not impaired. Also good.

[Method for Preparing Composition for Forming Conductive Layer]
The composition for forming a conductive layer of the present invention is a reaction solution obtained by bringing the components (B-2), (B-3) and (B-4) into contact with the components (C) to (E). (B-5) is added and reacted, and then (B-1) component is added and reacted to prepare a composition, and (A) component is added to the composition to produce. preferable.
Moreover, the reaction product obtained by heating the mixture containing (B-2), (B-3) component and (B-4) component, and (C)-(E) component is added to (B-5) It is more preferable to add and react the component (B-1) and then react the component (B-1) to prepare a composition and add the component (A) to the composition.
Specifically, a first component containing at least (B-2), (B-3) component and (B-4) component, (C) component organic polymer fine particles, (D) and (E) component. A mixed liquid is prepared, and then the inorganic fine particle dispersion liquid composed of the component (C) and the component (E) is mixed to prepare a second mixed liquid, and the component (B-5) is further added to add the third mixed liquid. Prepare. (B-1) component is added to this 3rd liquid mixture, and a composition is prepared. It is more preferable to produce the composition by adding a conductive nanofiber dispersion comprising the components (A) and (E).

Thus, it is preferable to prepare each component separately because the liquid storage stability (such as not gelation) of the composition is improved.
In particular, this effect is more exhibited when the amount of water in the liquid increases due to an increase in the amount of component (C) added. For example, after mixing (B-2), (B-3), (B-4), (C) component organic polymer fine particles, (D) and (E) component, (C) component Add inorganic fine particles. Next, the component (B-5) is mixed, and the component (B-1) is further added to prepare the composition.
In addition, (E) component can dilute a composition by adding, after preparing a composition.

  It is known that the liquid storage stability of a mixed material such as the above composition is liable to affect the liquid pH (for example, “Application of the sol-gel method to nanotechnology / supervision: Sakuo Sakuo” MC Publishing). In the preparation of the composition, the acidic component is mixed as the component (D), and the basic component is mixed as the inorganic fine particles as the component (B-1) and the component (C), so the liquid pH changes depending on the mixing order. As the liquid pH value, for example, the liquid pH value evaluated with a portable pH meter (trade name: Checker 1) manufactured by a calibration pH standard solution, the above first mixed liquid and second mixed liquid are It is preferable that pH ≦ 6, the third mixed solution, and the final mixed solution have pH ≦ 7. In particular, when the liquid pH exceeds 8 when the third mixed liquid, that is, the component (B-1) is mixed, the liquid stability may be lowered. The liquid is preferably kept in an acidic state from the start of preparation of the composition to the end of preparation. That is, it is preferable to prepare the composition by a procedure in which such conditions are maintained.

In addition, the first mixed solution, the second mixed solution, and the third mixed solution are preferably subjected to heat treatment after mixing the respective components. The temperature is preferably 30 ° C to 130 ° C, more preferably 50 ° C to 90 ° C, and the heat treatment time is preferably 30 minutes to 24 hours, more preferably 1 hour to 8 hours. The mixing and heating means is not particularly limited as long as it can uniformly mix and heat.
By heating in this way, the condensation reaction of the components (B-1), (B-2), (B-3), (B-4) and (B-5) in the liquid proceeds and durability is improved. improves. Reactions of the components (B-1), (B-2), (B-3), (B-4), and (B-5) can be analyzed by solution Si-NMR, thereby achieving a suitable structure. Can design. The reaction is often extremely slow at less than 30 ° C. or less than 30 minutes, and when it exceeds 130 ° C. or more than 24 hours, (B-1), (B-2), (B-3), (B -4) and (B-5) reaction is too advanced, the liquid may gel or become highly viscous, and may not be applied.

  (B-1) It is preferable to heat-process the composition after mixing a component. In the case of mixing at room temperature, it is easily affected by the stirring efficiency, and due to this, when the degree of dispersion of the component (B-1) is low, the transparency of the coating (total light transmittance decrease, haze increase) is increased. May fall. The temperature is preferably 30 ° C to 130 ° C, more preferably 50 ° C to 90 ° C, and the time is preferably 5 minutes to 10 hours, more preferably 15 minutes to 6 hours. The mixing and heating means is not particularly limited as long as it can uniformly mix and heat. If the temperature is less than 30 ° C. or less than 5 minutes, the effect of the heat treatment is often poor, and if it exceeds 130 ° C. or more than 10 hours, the liquid may gel or become highly viscous and cannot be applied.

[Transparent conductive layer]
A coating film is formed by apply | coating the composition for transparent conductive layer formation of this invention on a board | substrate. For example, it is applied by a known method such as a spin coater, spray, dipping, curtain flow, bar coater, die coater, blade coater, gravure coater or roll coating.
The thickness of the coating film is preferably adjusted to 10 to 500 nm, more preferably 30 to 200 nm.
Thereafter, the transparent conductive layer is obtained by heating and drying at appropriate drying conditions, usually room temperature to 190 ° C., preferably 80 to 140 ° C. for about 1 minute to 24 hours, preferably 2 to 60 minutes.

  Moreover, when the composition of this invention contains the silane compound ((B-6) component) which has a carbon-carbon double bond, photocuring (UV hardening) and electron beam hardening (EB hardening) are possible.

  In the transparent conductive layer obtained from the composition of the present invention, conductive nanofibers (component (A)) organic polymer fine particles and inorganic fine particles (component (C)) are dispersed in the film.

  Examples of the resin that can be used for the substrate include polyethylene, polypropylene, cycloolefin resins (eg, “ARTON” manufactured by JSR Corporation, “ZEONOR” “ZEONEX” manufactured by Nippon Zeon Corporation), and polyolefins such as polymethylpentene. Resins, polyethylene resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, cellulose resins such as diacetylcellulose, triacetylcellulose, acetylcellulose butyrate, polystyrene, syndiotactic polystyrene, acrylonitrile butadiene styrene Styrenic resin such as resin (ABS resin), imide resin such as polyimide, polyetherimide and polyamideimide, polyamide resin such as nylon, polyether , Ketone resins such as polyetheretherketone, sulfone resins such as polysulfone and polyethersulfone, vinyl chloride resins such as polyvinyl chloride and polyvinylidene chloride, acrylic resins such as polymethyl methacrylate, polycarbonate resins , Polyphenylene sulfide, polyacetal, modified polyphenylene ether, polyvinyl alcohol, epoxy resin, fluorine resin, plastic lens resin polymethyl methacrylate, alicyclic polyolefin, acrylonitrile styrene copolymer, methacryl styrene copolymer, alicyclic acryl, di Examples include glycol diallyl carbonate, diallyl phthalate, polyurethane, polythiourethane, episulfide, etc., and polymer alloys and polymers in which a plurality of the above polymers are mixed It may be a blend. Further, a laminated structure in which a plurality of the above resins are laminated may be used. Among the above resins, polyester resins (particularly polyethylene terephthalate), polyolefin resins and polycarbonate resins are preferable.

The substrate made of these resins may be transparent or translucent, may be colored, or may be uncolored, and may be appropriately selected according to the use. It is excellent in transparency and preferably has no color.
The substrate is not limited to a resin substrate, and may be a glass substrate, a metal substrate, a metal oxide substrate, a ceramic substrate, or the like. For example, a substrate made of a composite material such as resin and glass may be used.
There is no restriction | limiting in particular in the thickness of a board | substrate, Although it selects suitably according to a condition, Usually, it is about 5 micrometers-30 mm, Preferably it is 15 micrometers-10 mm.

The composition of the present invention can form a coating film on a substrate with good adhesion, but in order to further improve the adhesion property, at least the surface of the substrate on which the coating film is formed is optionally oxidized. Surface treatment can be performed by a method, an unevenness method, or the like. Examples of the oxidation method include corona discharge treatment, plasma treatment such as low pressure plasma method and atmospheric pressure plasma method, chromic acid treatment (wet), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, electron beam treatment, and intro treatment. In addition, examples of the roughening method include a sand blast method and a solvent treatment method. These surface treatment methods are appropriately selected according to the type of the substrate, but in general, the corona discharge treatment method is preferably used from the viewpoints of effects and operability. Further, a surface treatment with a silane coupling agent or a primer layer can be provided. However, since it is not necessary to provide a primer layer in the present invention, the structure can be simplified.
Moreover, you may provide a protective layer, a metal layer, and a metal oxide layer on the transparent conductive layer formed on the board | substrate. A metal layer, a metal oxide layer, a resin layer, or the like may be provided between the substrate and the transparent conductive layer.

The total light transmittance of the transparent conductive layer obtained from the composition of the present invention is preferably 85 to 100%, more preferably 90 to 100%.
The haze of the transparent conductive layer obtained from the composition of the present invention is preferably 3.0% or less, more preferably 2.0% or less.
The surface resistance of the transparent conductive layer obtained from the composition of the present invention is preferably 5 to 500 Ω / □, more preferably 5 to 200 Ω / □.
These physical properties can be confirmed by known methods. For example, the total light transmittance and haze can be confirmed by a haze meter, and the surface resistance can be confirmed by a four-probe measurement method or a four-terminal measurement method using a low resistance meter.

[Patterning of transparent conductive layer]
The transparent conductive layer obtained from the composition of the present invention may be patterned. For patterning, a known wet etching process such as photolithography or a laser etching process can be applied as it is. It is also possible to print the pattern directly by screen printing, flexographic printing, ink jet printing or the like. Although a patterning process is not specifically limited, When conductive nanofibers to be used are metal nanowires, such as a silver nanowire, wet etching and laser etching can be used suitably. Laser etching is preferred when the conductive nanofibers are carbon fibers such as carbon nanotubes.

[Pattern method by wet etching]
The patterning method by wet etching includes general photolithography using a photoresist and a photomask, a method of printing and applying an etchant in accordance with a pattern for forming a non-conductive region, and a method of applying an etchant through a non-corrosive mask and so on. Among these, photolithography can be suitably used in terms of reproducibility and accuracy. Also, a dry film that transfers a photosensitive film can be used instead of the photoresist.
When photolithography is used, a resist solution is applied on the formed transparent conductive layer to form a resist layer. Next, the resist layer is patterned by irradiating the resist layer with ultraviolet rays using a photomask and then developing the resist layer. Next, the transparent conductive layer not covered with the resist layer is removed by etching, and the remaining resist portion is peeled off to obtain a patterned transparent conductive layer.

  Since the transparent conductive layer of the present invention has good etchant permeability, it can effectively etch conductive nanofibers such as silver nanowires contained therein.

  As the etchant, an acidic agent that dissolves the conductive nanofibers or cuts and shortens the nanofibers can be used. When the conductive nanofiber is a metal nanowire such as a silver nanowire, for example, an inorganic acid such as hydrobromic acid, nitric acid, sulfuric acid, phosphoric acid, or hydrochloric acid, or an organic acid such as acetic acid, oxalic acid, or methanesulfonic acid is used. be able to. Moreover, the mixed acid containing these in combination can also be used. In particular, hydrobromic acid and nitric acid are preferable.

  An agent that oxidizes and dissolves metal can also be used. When the conductive nanofibers are metal nanowires such as silver nanowires, for example, iron nitrate (III) solution (ferric nitrate solution), iron chloride (III) solution (ferric chloride solution), copper chloride (II) An aqueous solution of a metal compound such as a liquid (cupric chloride liquid), a hydrogen peroxide solution, a mixture thereof, or the like can be used. In order to control the reaction, it may be used by mixing with acid or alkali. For example, a mixed aqueous solution of copper (II) chloride and hydrochloric acid, a mixed solution of hydrogen peroxide water and ammonia water, and the like can be suitably used.

  Alkaline etchants can also be used. When the conductive nanofiber is a metal nanowire such as a silver nanowire, examples thereof include an aqueous sodium hydroxide solution and an aqueous potassium hydroxide solution.

  Commercially available etchants include SEA-NW01, SEA-NW02, SEA-1, SEA-2, SEA-4, SEA-5, ITO-02, ITO-06N, ITO-07N, ITO-101N, Cu-01, Cu -02, Cu-03 (manufactured by Kanto Chemical Co., Inc.), GNW203, GNW300, GNW410 (manufactured by Hayashi Pure Chemical Industries, Ltd., Pure Etch series) can be used.

These chemicals may be used directly in the stock solution or diluted with a solvent such as water. You may add and use an additive. The etching processing temperature and processing time are not particularly limited, but are preferably set according to the type of the etchant and the thickness of the transparent conductive layer. In the optimum state, the optical characteristics such as haze and total light transmittance are the same as those before the treatment, and the surface resistance of the etched region is 10 ⁴ Ω / □ or more. If the treatment is insufficient, the insulating properties are insufficient, and if the treatment is excessive, damage to the substrate or the like may occur and optical characteristics may be deteriorated. In addition, by appropriately controlling the processing temperature and processing time, it is possible to perform partial etching in which conductive nanofibers such as silver nanowires are not completely dissolved but are cut into short fibers to form non-conductive regions. . Thereby, the difference of the reflectance and light scattering of a conduction | electrical_connection part and a non-conduction part can be made small, and the visibility of a pattern can be made low.

[Patterning method by laser etching]
Laser etching can be suitably used as a dry etching method for patterning the transparent conductive layer. In this case, the conductive layer is made non-conductive by evaporating and removing the conductive layer with the condensed laser light. Compared with patterning by wet etching that requires a series of steps of resist coating, mask exposure, development, etching, resist stripping, and cleaning, a highly accurate pattern can be obtained with simple equipment and a short process. When laser etching is applied to the present invention, removability by laser irradiation is good, damage to the base substrate can be suppressed, and etching can be performed efficiently.
Examples of the laser light source include pulsed laser light such as YAG and YVO ₄ and continuous wave laser light such as a carbon dioxide gas laser. In particular, a pulsed laser beam having a wavelength of 1064 nm such as YAG or YVO ₄ or a second harmonic thereof having a wavelength of 532 nm is preferable.

  The transparent conductive layer obtained from the composition of the present invention and the substrate with a transparent conductive layer comprising a transparent conductive layer are a touch panel, a liquid crystal display, an organic EL display, an organic EL illumination, a solar cell, a light control film, a light control glass, and a transparent It is suitably used for electric devices such as heaters and vehicles such as automobiles and trains. Moreover, the said touch panel is used suitably for a display apparatus.

[Composition]
Production Example 1
A composition having the composition shown in Table 1 was prepared.
In addition, the components described under the trade names in Table 1 are specifically as follows:
ULS-1385MG organic polymer fine particles, manufactured by Yushi Kogyo Co., Ltd. (water dispersion / solid content concentration of 30% by mass), average particle size of 55-75 nm (measured by the dynamic light scattering method described above))
MTMS-A: polyorganoalkoxysilane which is a partial condensate of methyltrimethoxylane, manufactured by Tama Chemical Industry Co., Ltd. M silicate 51: polyalkoxysilane which is a partial condensate (average 3 to 5 mer) of tetramethoxysilane, IPA-ST-L manufactured by Tama Chemical Co., Ltd .: colloidal silica, manufactured by Nissan Chemical Industries, Ltd. (isopropanol dispersion, colloidal silica concentration 30% by mass, average particle size 40-50 nm (measurement using the aforementioned BET specific surface area measuring device Measured by the method))

  A sample tube with a volume of 50 ml was charged with 0.80 g of organic polymer fine particles: ULS-1385MG (component (C) + component (E)) and stirred at 500 rpm while 1-methoxy-2-propanol (component (E) was added. ) 4.25 g, water (component (E)) 0.50 g, acetic acid (component (D)) 0.50 g, M silicate 51 (component (B-2)) 0.40 g, MTMS-A ((B-3 ) Component) 1.10 g, dimethoxy-3-glycidoxypropylmethylsilane (component (B-4)) 0.55 g, 20 mass% p-toluenesulfonic acid methanol liquid (component (D) + component (E)) In the order of 0.05 g, each was dropped over 1 minute. Subsequently, after stirring for 60 minutes at room temperature and 500 rpm, the mixture was allowed to stand for one day, which was designated as solution A.

A sample tube with a volume of 20 ml was charged with 1.10 g of 3-isocyanatopropyltriethoxysilane and 0.35 g of 2-butanone oxime (isocyanate group blocking agent), stirred at room temperature at 500 rpm for 10 minutes, and then allowed to stand for one day. This was designated as solution C. The blocking of the isocyanate group was confirmed by the disappearance of the isocyanate group signal by ¹³ C-NMR. The total amount of 3-isocyanatopropyltriethoxysilane and 2-butanone oxime was taken as the amount of the blocked isocyanatosilane compound: (B-5) component.

Into a 200 ml three-necked flask equipped with a condenser, put A solution and a stirrer and stir at 500 rpm while applying IPA-ST-L (component (C) + component (E)) 6.50 g as solution B over 5 minutes. The solution was added dropwise and stirred at room temperature for 60 minutes. Then, it heated at 600 rpm and 80 degreeC under nitrogen stream for 3 hours. Then, C liquid was added, and it stirred at 80 degreeC on the same conditions for 4 hours, Then, it left still at room temperature overnight.
Furthermore, 0.40 g of 3-aminopropyltrimethoxysilane ((B-1) component) was added dropwise thereto as a D solution over 2 minutes. After stirring at room temperature for 10 minutes, the mixture was further heated at 700 rpm and 80 ° C. for 3 hours under a nitrogen stream.

Production Example 2-5
A composition was prepared in the same manner as in Production Example 1 except that the components and amounts shown in Table 1 were used.

[Preparation of silver nanowire dispersion]
Silver nanowire dispersion liquid A was prepared by dispersing silver nanowires having an average diameter of 25 nm and an average length of 20 μm in isopropyl alcohol so that the solid content concentration was 0.5 mass%.
Similarly, silver nanowire dispersion BF shown in Table 2 was prepared.

Example 1
A transparent conductive layer forming composition is prepared by adding 93.90 g of isopropyl alcohol (IPA) to 1.65 g of the composition prepared in Production Example 1, adding 95.50 g of the prepared silver nanowire dispersion A, and stirring at room temperature. Was prepared. The obtained composition for forming a transparent conductive layer has the composition shown in Table 3-1.
In Tables 3-1 to 3-6, the numerical value (%) in parentheses indicates mass% when the total mass of the components (A) to (D) is 100%. Moreover, the numerical value (part) of (E) component shows the mass part with respect to 100 mass parts of total amounts of (A)-(D) component.

  The obtained composition for forming a transparent conductive layer was applied to a glass substrate with a spin coater at 1500 rpm and dried at 100 ° C. for 30 minutes to form a transparent conductive layer on the glass substrate. The following evaluation was performed about the obtained transparent conductive layer. The results are shown in Table 4-1.

(1) Film thickness measurement When the base material was a glass substrate, the film thickness of the transparent conductive layer was measured using a stylus-type film thickness meter, and the average value of five points was taken as the film thickness.
When the substrate was a resin substrate, the film thickness of the transparent conductive layer was measured using AFM, and the average of the minimum value and the maximum value of the distance from the substrate was taken as the film thickness.

(2) Total light transmittance Using a laminate composed of a base material and a transparent conductive layer based on ASTM D1003 using a haze meter (NDH5000, manufactured by Nippon Denshoku Industries Co., Ltd.), the transparent conductive layer based on the base material. The total light transmittance was measured.

(3) Haze Using a haze meter (Nippon Denshoku Industries Co., Ltd., NDH5000), based on ASTM D1003, using a laminate composed of a base material and a transparent conductive layer, the haze value of the transparent conductive layer is determined based on the base material. It was measured.

(4) Surface resistance measurement The surface resistance of the transparent conductive layer was measured by a four-probe measurement method based on JIS K 7194 using a low resistivity meter (Loresta-GP MCP-T-610, manufactured by Mitsubishi Chemical).

(5) Adhesive evaluation A commercially available cellophane tape (Nichiban CT-24 (width: 24 mm)) was applied on the transparent conductive layer and adhered well with a finger pad, and then the cellophane tape was peeled off. The surface resistance of the transparent conductive layer after the cellophane tape was peeled off was measured, and those using silver nanowires were rated as “◯” for those with less than 500Ω / □, and “×” for those with 500Ω / □ or more, and used carbon nanotubes. The thing of less than 3000 ohm / square was made into "(circle)", and 3000 ohm / square or more was made into "x".

(6) Durability In a small environmental tester (Espec Corp., SH-221), a laminate composed of a base material and a transparent conductive layer was exposed under conditions of 60 ° C., 90% RH and 500 hours, and a durability test was conducted. Carried out. The above-mentioned total light transmittance, haze, surface resistance and adhesion were evaluated again for the laminate after the durability test.
Regarding the total light transmittance, the difference between before and after the durability test was less than 10%, “◯”, 10-20% “Δ”, and 20% or more “X”.
Regarding the haze, the difference between before and after the durability test was evaluated as “◯”, 3-5% as “Δ”, and 5% or more as “X”.
Regarding the surface resistance, those using silver nanowires with a surface resistance of less than 500Ω / □ are “O”, those with 500Ω / □ or more are “X”, and those using carbon nanotubes are 3000Ω / Those with less than □ were marked with “◯” and those with 3000Ω / □ or more were marked with “x”.
For adhesion, the adhesion of the transparent conductive layer after the test is evaluated, and the surface resistance after the adhesion evaluation is "O" for silver nanowires less than 500Ω / □, 500Ω / □ or more Is “×”, and those using carbon nanotubes are “◯” when the carbon nanotube is less than 3000Ω / □, and “×” when the carbon nanotube is 3000Ω / □ or more.

Example 2-27
A transparent conductive layer was formed and evaluated in the same manner as in Example 1 except that a composition for forming a transparent conductive layer having the composition shown in Tables 3-1 to 3-6 was prepared. The results are shown in Tables 4-1, 4-2 and Table 5.
Example 2-27 is specifically as follows.

Examples 2 and 3
A transparent conductive layer forming composition was prepared in the same manner as in Example 1 except that the composition prepared in Production Example 2 or 3 was used.

Example 4-7
Except having changed the addition amount of the silver nanowire dispersion liquid A (Ag-NW-25 by Seashell Technologies) used in Example 3 into the amount described in Table 3-1 and 3-2, it carried out similarly to Example 3. A composition for forming a transparent conductive layer was prepared.

Examples 8-12
A transparent conductive layer forming composition was prepared in the same manner as in Example 3, except that the silver nanowire dispersion BF shown in Table 2 was used instead of the silver nanowire dispersion A used in Example 4.

Examples 13 and 14
The composition for forming a transparent conductive layer prepared in Example 3 was subjected to easy adhesion PET film (Toyobo Cosmo Shine A4300, 100 μm) or PC sheet (SABIC Innovative Plastics Lexan film 8010, 100 μm) using bar # 3 with a bar coater. A transparent conductive layer was formed in the same manner as in Example 3 except that the coating was applied to the above.

Examples 15 and 16
A bar formed with a transparent conductive layer in the same manner as in Example 13 except that the bar used for applying the composition for forming a transparent conductive layer in Example 13 was changed to bar # 5 or # 7. By using 7, a thicker coating film than in Example 13 can be obtained.

Example 17
To 1.69 g of the composition prepared in Production Example 3, 0.12 g of 3-methacryloxypropyltrimethoxysilane was further added dropwise and stirred at room temperature for 2 hours, and 112.28 g of silver nanowire dispersion A was further added to the room temperature. The composition for transparent conductive layer formation was prepared by stirring by.
The obtained composition for forming a transparent conductive layer was applied to an easy-adhesion PET film (Cosmo Shine A4300, Toyobo Co., Ltd., 100 μm) using a bar coater using bar # 3, and heat-dried at 100 ° C. for 5 minutes. ultraviolet so that the cm ² was cured by irradiation.

Examples 18 and 19
Example 17 except that instead of the easy-adhesion PET film of Example 17 (Toyobo Cosmo Shine A4300), it was changed to an easy-adhesion PET film (Toray Lumirror U46, 100 μm) or (Toray Lumirror U48, 100 μm), respectively. In the same manner, a transparent conductive layer was formed.

Examples 20 and 21
Example 13 except that 1.91 g or 19.11 g of a triazine thiol group-containing silicone alkoxy oligomer methanol solution (X-249452 manufactured by Shin-Etsu Chemical Co., Ltd.) was added to the composition for forming a transparent conductive layer of Example 13, respectively. In the same manner as above, a composition for forming a transparent conductive layer was prepared.

Examples 22 and 23
2.86 g or 28.65 g of a triazine thiol group-containing silicone alkoxy oligomer methanol solution was further added to the composition for forming a transparent conductive layer of Example 8, respectively, and the base material was made of an easily-adhesive PET film (Toyobo Cosmo Shine). A4300) and a composition for forming a transparent conductive layer was prepared in the same manner as in Example 8 except that bar # 3 was used to coat with a bar coat, and a transparent conductive layer was formed.

Examples 24 and 25
In Example 13, a carbon nanotube dispersion (SWCNT Water solution Gen 2.2 manufactured by KH Chemicals; diameter 1.0 to 1.4 nm, length 5 to 50 μm (catalog value)) was used instead of the silver nanowire dispersion. Transparent conductive layer forming compositions having the compositions shown in Tables 3-5 and 3-6 were prepared.
In Example 24, the obtained composition for forming a transparent conductive layer was applied in the same manner as in Example 13, and further dried at 60 ° C. for 5 minutes and then at 100 ° C. for 5 minutes to form a transparent conductive layer.
In Example 25, the transparent conductive layer obtained in Example 24 was immersed in concentrated nitric acid heated to 60 ° C. for 10 minutes, washed with ion-exchanged water, and dried at 100 ° C. for 5 minutes. Formed.

Examples 26 and 27
A transparent conductive layer forming composition was prepared in the same manner as in Example 15 except that the silver nanowire dispersion A was added to the composition prepared in Production Example 4 or Production Example 5 in the amount shown in Table 3-6. A layer was formed.

Comparative Example 1
The silver nanowire dispersion liquid A was applied to a glass substrate at a spin coater of 1500 rpm, and dried at 100 ° C. for 30 minutes to form a transparent conductive layer. Evaluation similar to Example 1 was performed about the obtained transparent conductive layer. The results are shown in Table 6.

Comparative Example 2
Silver nanowire dispersion liquid A was applied to an easy-adhesion PET film (Toyobo Cosmo Shine A4300, 100 μm) with a bar coater using bar # 3 and dried at 100 ° C. for 30 minutes to form a transparent conductive layer. Evaluation similar to Example 1 was performed about the obtained transparent conductive layer. The results are shown in Table 6.

Comparative Example 3
A silver nanowire dispersion A was further added to a composition in which M silicate 51, acetic acid, p-toluenesulfonic acid methanol solution, and IPA were mixed at room temperature, and a composition for forming a transparent conductive layer was prepared by stirring at room temperature. The obtained composition was applied to an easy-adhesion PET film (Toyobo Cosmo Shine A4300, 100 μm) with a bar coater using Bar # 3 and dried at 100 ° C. for 30 minutes to form a transparent conductive layer. Evaluation similar to Example 1 was performed about the obtained transparent conductive layer. The results are shown in Table 6.

Comparative Example 4
IPA was added to a commercially available silicate coating solution (manufactured by Colcoat, product name: Colcoat PX), and then the silver nanowire dispersion A was added and stirred at room temperature to prepare a composition for forming a transparent conductive layer. The obtained composition was applied to an easy-adhesion PET film (Toyobo Cosmo Shine A4300, 100 μm) with a bar coater using Bar # 3 and dried at 100 ° C. for 30 minutes to form a transparent conductive layer. Evaluation similar to Example 1 was performed about the obtained transparent conductive layer. The results are shown in Table 6.

Comparative Example 5
After adding 1-methoxy-2-propanol to a commercially available silicate coating liquid containing inorganic fine particles (UVHC3000 manufactured by Momentive Performance Materials), a silver nanowire dispersion liquid A is added and stirred at room temperature to form a transparent conductive layer forming composition Was prepared. The obtained composition was applied to an easy-adhesion PET film (Cosmo Shine A4300, 100 μm manufactured by Toyobo Co., Ltd.) using a bar coater using bar # 3 and dried at room temperature for 2 minutes and at 85 ° C. for 5 minutes. It hardened | cured by irradiating an ultraviolet-ray so that it might become 1000 mJ / cm < ² >, and formed the transparent conductive layer. Evaluation similar to Example 1 was performed about the obtained transparent conductive layer. The results are shown in Table 6.

Comparative Example 6
In the composition for forming a transparent conductive layer of Example 1, a composition was prepared in the same manner as in Example 1 except that the silver nanowire dispersion A was not added, and a coating layer was formed on the glass substrate. Evaluation similar to Example 1 was performed about the obtained coating-film layer. The results are shown in Table 6.

Comparative Example 7
A coating layer was formed on a glass substrate in the same manner as in Comparative Example 6 except that the composition of Comparative Example 6 was applied to an easy-adhesion PET film (Toyobo Cosmo Shine A4300, 100 μm) using a bar coater using Bar # 3. The same evaluation as in Example 1 was performed on the obtained coating layer. The results are shown in Table 6.

On the transparent conductive layer produced in Example 1, a photoresist (OFPR-800LB manufactured by Tokyo Ohka Kogyo Co., Ltd.) was applied by spin coating, and pre-baked at 115 ° C. for 2 minutes to form a thin film. Next, the substrate having this thin film was exposed to g-line with an exposure apparatus in which a mask was set, developed in a pattern by dipping in a developing solution, rinsed with pure water, and post-baked at 140 ° C. for 2 minutes. . Thereafter, it was immersed in an etchant (SEA-NW01 manufactured by Kanto Chemical Co., Ltd.) at 25 ° C. for 2 minutes, washed with pure water, immersed in a resist stripping solution (acetone) at room temperature for 10 minutes, and dried to obtain a pattern-shaped transparent conductive film.
It was confirmed that a predetermined pattern can be formed by the etching. The portion remaining by etching did not show a change in surface resistance, but the portion removed by etching had a surface resistance of> 10 ⁷ Ω / □ (over 10 ⁷ Ω / □).

Although several embodiments and / or examples of the present invention have been described in detail above, those skilled in the art will appreciate that these exemplary embodiments and / or embodiments are substantially without departing from the novel teachings and advantages of the present invention. It is easy to make many changes to the embodiment. Accordingly, many of these modifications are within the scope of the present invention.
All the contents of the Japanese application specification that is the basis of the priority of Paris in this application are incorporated herein.

Claims (23)

The composition for transparent conductive layer formation containing the following component (A)-(E).
(A) Conductive nanofiber (B) Hydrolysis condensate of a silane compound having one or more alkoxy groups selected from the following (B-1) and the following (B-2) to (B-5) B-1) Silane compound having amino group and alkoxy group (B-2) tetraalkoxysilane compound,
(B-3) Organoalkoxysilane compound containing no amino group, epoxy group and isocyanate group (B-4) Silane compound having epoxy group and alkoxy group (B-5) Blocked isocyanatosilane compound having alkoxy group ( C) Organic polymer fine particles and / or inorganic fine particles (D) Curing catalyst (E) Dispersion medium   The composition for forming a transparent conductive layer according to claim 1, wherein the hydrolysis condensate of the silane compound having an alkoxy group contains the (B-1) to (B-5).   The composition for forming a transparent conductive layer according to claim 1 or 2, wherein D / L <0.010 is satisfied, where D is an average particle diameter of the inorganic fine particles and L is an average length of the conductive nanofibers.   The transparent conductive layer formation according to any one of claims 1 to 3, wherein D / L <0.010 is satisfied, where D is an average particle diameter of the organic polymer fine particles and L is an average length of the conductive nanofibers. Composition.   The composition for forming a transparent conductive layer according to claim 1, wherein the inorganic fine particles are colloidal silica.   The composition for forming a transparent conductive layer according to claim 1, wherein the conductive nanofiber has an average diameter of 0.5 nm to 100 nm and an average length of 1 μm to 100 μm.   The composition for forming a transparent conductive layer according to claim 1, wherein the conductive nanofibers have an average diameter of 1 nm to 100 nm and an average length of 1 μm to 100 μm.   The composition for forming a transparent conductive layer according to claim 1, wherein the conductive nanofiber has an average diameter of 5 nm to 50 nm and an average length of 3 μm to 50 μm.   The composition for forming a transparent conductive layer according to claim 1, wherein the conductive nanofiber is a silver nanowire or a carbon nanotube.   The composition for forming a transparent conductive layer according to claim 1, wherein the conductive nanofiber is a silver nanowire.   11. The composition for forming a transparent conductive layer according to claim 10, wherein the silver nanowire has an average diameter of 5 nm to 50 nm and an average length of 5 μm to 30 μm.   The transparent conductive layer-forming composition according to claim 1, wherein the transparent conductive layer obtained from the transparent conductive layer-forming composition can be patterned.   The composition for forming a transparent conductive layer according to claim 12, wherein patterning is possible with either an acid or a base.   The transparent conductive layer obtained from the composition for transparent conductive layer formation in any one of Claims 1-11.   The transparent conductive layer according to claim 14, which can be patterned.   The transparent conductive layer according to claim 15, which can be patterned with either an acid or a base.   The board | substrate with a transparent conductive layer which has a transparent conductive layer obtained by apply | coating the composition for transparent conductive layer formation in any one of Claims 1-13 to a base material.   The substrate with a transparent conductive layer according to claim 17, wherein the transparent conductive layer contains silver nanowires, and the content of the silver nanowires is 5 wt% or more and 98 wt% or less.   19. The substrate with a transparent conductive layer according to claim 17, wherein the transparent conductive layer has a total light transmittance of 85 to 100%, a haze of 3.0% or less, and a surface resistance of 5 to 500Ω / □. .   The manufacturing method of the board | substrate with a transparent conductive layer which has a transparent conductive layer which apply | coats the composition for transparent conductive layer formation in any one of Claims 1-13 directly to a board | substrate.   The touch panel using the board | substrate with a transparent conductive layer in any one of Claims 17-19.   An electric device using the substrate with a transparent conductive layer according to claim 17.   The vehicle using the transparent conductive layer in any one of Claims 14-19, or a board | substrate with a transparent conductive layer.