KR20150009950A - Base with transparent conductive film and touch panel - Google Patents

Abstract

Provided is a substrate with a transparent conductive film excellent in adhesion to a transparent conductive film and a transparent substrate using metal nanowires over time. A transparent conductive film (3) obtained by laminating a transparent conductive film (3) containing metal nanowires on a transparent substrate (1) via a primer layer (2) having a surface wet tension of 30 mN / m or more specified by JIS K6768: (4). It is preferable that the primer layer (2) comprises 90% by weight or more of a resin component including a cured product of a curable resin and a thermoplastic resin. The curable resin is preferably an ionizing radiation curable resin, more preferably an ionizing radiation curable organic-inorganic hybrid resin. It is preferable that the ratio of the cured product of the curable resin to the thermoplastic resin in the resin powder is 50 wt% or more and 90 wt% or less and the thermoplastic resin is 10 wt% or more and 50 wt% or less.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a transparent conductive film-

The present invention relates to a substrate having a transparent conductive film which can be used for various flat panel displays, transparent electrodes such as touch panels, an antistatic layer, an electromagnetic wave shielding layer, and the like, and a touch panel using the substrate as an electrode.

A metal oxide film obtained by sputtering a metal oxide such as indium tin oxide (ITO) as a transparent conductive film or a conductive film made of a conductive polymer is widely known.

However, the metal oxide film is vulnerable to physical stress such as bending and is liable to be damaged. Therefore, it is difficult to apply it to a product group on which a physical stress is applied. Further, in order to impart high conductivity, it is necessary to set the processing temperature of the deposition or annealing to a high temperature. Therefore, it is difficult to apply it to a plastic substrate. It is also difficult to adhere to a plastic substrate such as polycarbonate. Therefore, it is difficult to properly form on a plastic substrate.

The conductive film made of the conductive polymer is inferior in transparency and conductivity as compared with the metal oxide film, so that it is difficult to apply the conductive film to permeation applications.

As a solution to the above problem, a transparent conductive film formed from metal nanowires has been proposed (Patent Document 1).

Japanese Patent Publication No. 2009-505358

The transparent conductive film of Patent Document 1 exhibits high conductivity and transparency equal to or higher than that of the metal oxide film due to the mutual contact of metal nanowires in the film, and does not have the above-described drawbacks of the metal oxide film.

However, the transparent conductive film of Patent Document 1 has a problem that the adhesiveness is deteriorated over time even though the initial adhesion with the transparent substrate is good.

In one aspect of the present invention, there is provided a transparent conductive film-attached base material excellent in adhesion with time of a transparent conductive film and a transparent base material using metal nanowires, and a touch panel using the base material as an electrode.

The inventors of the present invention have found that when a primer layer having a wet tensile strength of at least a predetermined value is sandwiched therebetween, adhesion of the transparent conductive film containing metal nanowires to the transparent substrate with time can be increased, and the present invention has been accomplished. Thus, stable and continuous use of electronic devices such as a touch panel can be realized.

The transparent conductive film-attached substrate of the present invention is characterized in that a transparent conductive film containing metal nanowires is laminated on a transparent substrate via a primer layer having a surface wet tensile strength of 30 mN / m or more as defined in JIS K6768: 1999.

The touch panel of the present invention is characterized in that the substrate with a transparent conductive film of the present invention is used for an electrode.

The present invention includes the following aspects.

(1) The primer layer may comprise a resin content including a cured resin of a curable resin. In this case, the content of the resin component may be 90 wt% or more in the primer layer.

(2) An ionizing radiation-curable resin can be used as the curable resin, and an ionizing radiation-curable organic-inorganic hybrid resin can be used as the ionizing radiation curable resin.

(3) The resin component in the primer layer may further include a thermoplastic resin together with the cured resin of the curable resin. In this case, the content of the curing resin in the resin component may be 50 wt% or more and 90 wt% or less, and the thermoplastic resin may be 10 wt% or more and 50 wt% or less.

(4) It is also possible to constitute the primer layer together with the resin component and further include particles. In this case, particles having an average particle diameter of 3 탆 or more and 10 탆 or less can be used. The content of the particles may be 0.02 part by weight or more and 1 part by weight or less based on 100 parts by weight of the resin.

(5) The primer layer may contain low refractive index fine particles having an average particle diameter of 1 nm or more and 200 nm or less.

Since the primer layer having a wet tensile strength of not less than a predetermined value is interposed between the transparent conductive film and the transparent conductive film using the metal nanowire, the initial adhesion of the transparent conductive film and the transparent substrate, It is possible to improve adherence to the surface.

Since the touch panel of the present invention uses the substrate with the transparent conductive film of the present invention for the electrode, stable continuous use can be realized.

1 is a cross-sectional view showing an example of a substrate with a transparent conductive film of the present invention.
Explanation of symbols
One… Transparent substrate, 2 ... Primer layer, 3 ... Transparent conductive film, 4 ... A transparent conductive film-adhered substrate.

First, an example of the substrate with a transparent conductive film of the present invention will be described. As shown in Fig. 1, the transparent conductive film-adhered base material 4 of this embodiment is formed by laminating a transparent conductive film 3 on a transparent base material 1 via a primer layer 2. [

As the transparent substrate 1, a plastic film (e.g., various films such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polyethylene, polypropylene, polystyrene, triacetylcellulose, . Among the plastic films, a polyethylene terephthalate film obtained by stretching, particularly biaxial stretching, is preferable because of its excellent mechanical strength and dimensional stability. The thickness of the transparent substrate 1 varies depending on the application, but is generally about 25 to 500 탆, preferably 50 to 200 탆.

The transparent conductive film 3 comprises at least a metal nanowire. As the metal nanowire, any one can be used, and the means for producing the metal nanowire is not particularly limited. For example, known means such as a liquid phase method and a vapor phase method can be used. As a manufacturing method of the Ag nanowire, a method of manufacturing the Au nanowire is disclosed in Japanese Patent Application Laid-Open No. 2006-233252, a manufacturing method of the Cu nanowire is disclosed in Japanese Patent Application Laid-Open No. 2002-266007, Examples of the method for producing the wire include the method described in Japanese Patent Application Laid-Open No. 2004-149871.

Examples of the metal constituting the metal nanowire include elemental metals, alloys and metal oxides. At least one cross-sectional dimension of the metal nanowire is preferably 200 nm or less from the viewpoint of transparency, and is preferably 10 nm or more from the viewpoint of conductivity. The metal nanowire preferably has an aspect ratio of 10 or more from the viewpoint of conductivity, more preferably 50 or more, and further preferably 100 or more.

The transparent conductive film 3 preferably includes a metal nanowire and a resin component for binding the metal nanowire together. As the resin component, a resin component exemplified in the description of the primer layer (2) to be described later can be used. Among them, a cured product of an ionizing radiation curable resin and a thermosetting resin are preferably used.

The content ratio of the metal nanowires in the total solid content forming the transparent conductive film 3 is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.5% by mass or more, and preferably 90% Or less, more preferably 30 mass% or less, further preferably 10 mass% or less. The refractive index of the transparent conductive film 3 is usually about 1.45 or more and 1.52 or less.

The primer layer 2 is interposed between the transparent substrate 1 and the transparent conductive film 3. [ The primer layer 2 is adjusted to have a surface wet tension (JIS K6768: 1999) of 30 mN / m or more, preferably 32 mN / m or more. The initial adhesion between the transparent substrate 1 and the transparent conductive film 3 is improved by laminating the transparent conductive film 3 with the primer layer 2 having a surface wet tension of 30 mN / Together, we have found that adhesion over time can be increased.

It is preferable that most of the primer layer 2 is made of resin. Specifically, the amount of resin in the primer layer (2) is preferably 90% by weight or more, and more preferably 95% by weight or more. It is difficult to adjust the surface wet tension of the primer layer 2 to 30 mN / m or more while maintaining the film strength of the primer layer 2 at a certain high level. On the contrary, when the primer layer 2 is formed so that the resin amount is 90 wt% or more, the surface wet tension of the primer layer 2 can be easily adjusted.

The resin component in this example includes a cured resin or a thermoplastic resin. The cured product referred to in this example is used in combination with a curable resin as a curing subject, and also includes a curing auxiliary such as a polymerization initiator, a polymerization promoter (ultraviolet ray sensitizer, etc.) and a curing agent necessary for curing the curable resin.

The resin component constituting the primer layer (2) includes at least a cured product of a curable resin. When the primer layer 2 including the cured resin of the curable resin is formed, it is easy to adjust the wet tension of the surface to a predetermined value or more as compared with the case where the primer layer 2 is formed only of the thermoplastic resin without containing it .

Examples of the curable resin include a resin such as a polyester resin, an acrylic resin, an acrylic urethane resin, a urethane resin, an epoxy resin, a polycarbonate resin, a melamine resin, a phenol resin, a silicone resin, an acrylate resin (polyester acrylate resin, (Thermosetting resin, ionizing radiation curable resin) capable of forming a cured product (cured film) by thermal or ionizing radiation, such as a polyurethane acrylate resin, an epoxy acrylate resin, It is also possible to use a resin. Of these, an ionizing radiation curable resin is preferable from the standpoints of improvement in adhesion with time of the transparent base material 1 and the transparent conductive film 3, and furthermore, from the viewpoint of forming a cured product excellent in surface hardness.

As the ionizing radiation curing type resin, those which are crosslinked and cured by irradiation with ionizing radiation (ultraviolet ray or electron beam) are used. As such, a mixture of one kind or a mixture of two or more of a photocationic polymerizable photopolymerizable resin, a photopolymerizable photopolymerizable prepolymer or a photopolymerizable monomer may be used.

Examples of the light-ion polymerizable resin include epoxy resins such as bisphenol-based epoxy resins, novolak-type epoxy resins, alicyclic epoxy resins, and aliphatic epoxy resins, and vinyl ether-based resins.

Examples of the photopolymerizable prepolymer include polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, polyether (Meth) acrylate, and the like.

Examples of the photopolymerizable monomer include styrenic monomers such as styrene and? -Methylstyrene, (meth) acrylates such as methyl (meth) acrylate and butyl (meth) acrylate, Substituted amino alcohol esters of unsaturated acids such as unsaturated carboxylic acid amide, 2- (N, N-diethylamino) ethyl (meth) acrylate and 2- (N, N- Acrylate such as ethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, isocyanuric acid triacrylate (such as tris- (2-hydroxyethyl ) -Isocyanuric acid ester (meth) acrylate), 3-phenoxy-2-propanoyl acrylate and 1,6-bis (3-acryloxy-2-hydroxypropyl) Polyfunctional compounds, and trimethylolpropane trithioglycolate, penta And polythiol compounds having two or more thiol groups in the molecule such as erythritol tetrathioglycolate.

In addition to the above-mentioned photopolymerizable prepolymer or photopolymerizable monomer, when the ionizing radiation curable resin is cured by ultraviolet irradiation, it is preferable to contain a curing auxiliary such as a photopolymerization initiator or an ultraviolet ray sensitizer.

Examples of the photopolymerization initiator include photo radical polymerization initiators such as acetophenone, benzophenone, Michler's ketone, benzoin, benzylmethyl ketal, benzoyl benzoate,? -Acyloxime ester and thioxanthone, onium salts, sulfonic acid esters, And a photocationic polymerization initiator such as an organometallic complex. Examples of ultraviolet sensitizers include n-butylamine, triethylamine, tri-n-butylphosphine and the like.

It is particularly preferable to use an ionizing radiation-curable organic-inorganic hybrid resin from the viewpoint of further increasing the adhesiveness with time of the transparent substrate 1 and the transparent conductive film 3. The term "ionizing radiation-curable organic-inorganic hybrid resin" (hereinafter sometimes abbreviated as "organic-inorganic hybrid resin") refers to a method of mixing an organic material with an inorganic material in a manner that is different from an old composite represented by glass fiber reinforced plastic (FRP) And the dispersed state is at or near the molecular level, and the inorganic component and the organic component react with each other by irradiation with ionizing radiation to form a coating film.

The inorganic component in the organic-inorganic hybrid resin may include a metal oxide such as silica and titania, but silica is preferable.

As the silica, a reactive silica into which a photosensitive group having photopolymerization reactivity is introduced on the surface can be mentioned. For example, a compound having four groups represented by the following formulas (1) and (2), a hydrolyzable silyl group and a polymerizable unsaturated group in the molecule may be hydrolyzed by hydrolysis of a hydrolyzable silyl group to a powdery silica or colloidal silica, Those chemically bonded via a silyloxy group by a reaction can be used.

Wherein X is selected from NH, an oxygen atom and a sulfur atom, Y is selected from an oxygen atom and a sulfur atom, provided that when X is an oxygen atom, Y is a sulfur atom.

Examples of the hydrolyzable silyl group include an alkoxysilyl group, a carboxylate silyl group such as acetoxysilyl, a halogenated silyl group such as a chlorosilyl group, an aminosilyl group, an oximesilyl group, and a hydride silyl group . Examples of the polymerizable unsaturated group include an acryloyloxy group, a methacryloyloxy group, a vinyl group, a propenyl group, a butadienyl group, a styryl group, an ethynyl group, a cinnamoyl group, a maleate group and an acrylamide group.

As the reactive silica, an average particle size of preferably 1 nm or more, preferably 100 nm or less, more preferably 10 nm or less is used. By using the reactive silica having an average particle diameter in a predetermined range, it becomes easy to maintain transparency when the primer layer 2 is used.

The content of the inorganic component in the organic-inorganic hybrid resin is preferably 10% by weight or more, more preferably 20% by weight, preferably 65% by weight or less, and more preferably 40% by weight or less. By making the content of the inorganic component 10 wt% or more, the adhesion between the transparent substrate 1 and the transparent conductive film 3 can be made easy. When the content is 65 wt% or less, the transparency of the primer layer 2 can be easily maintained.

As the organic component in the organic-inorganic hybrid resin, a compound having a polymerizable unsaturated group capable of polymerizing with the inorganic component (preferably reactive silica) (for example, a polyfunctional unsaturated organic compound having two or more polymerizable unsaturated groups in the molecule, Unsaturated organic compounds having a polymerizable unsaturated group, and the like).

Examples of the polyvalent unsaturated organic compound include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, Acrylate, trimethylolpropane tri (meth) acrylate, dicyclopentanyl di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, ditrimethylolpropane tetra (Meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di And dipropylene glycol di (meth) acrylate.

Examples of the monovalent unsaturated organic compound include mono (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, (Meth) acrylate, stearyl (meth) acrylate, allyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl Acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycerol (meth) acrylate, glycidyl (Meth) acrylate, methoxyethyl (meth) acrylate, 2- (2-ethoxyethoxy) ethyl (meth) acrylate, (Meth) acrylate, methoxy tri Acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, 2-methoxypropyl (meth) acrylate, methoxydipropylene glycol (meth) (Meth) acrylate, methoxypolypropylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, and polypropylene glycol (meth) acrylate.

It is preferable that the resin component constituting the primer layer (2) contains a thermoplastic resin in addition to the cured resin of the curable resin. The thermoplastic resin is contained in the resin component constituting the primer layer 2 so that the adhesion of the transparent base material 1 and the transparent conductive film 3 with the lapse of time is obtained by forming the primer layer 2 only with the cured resin of the curable resin It can be made even better than the case.

 Examples of the thermoplastic resin include a cellulose resin, an acetal resin, a vinyl resin, a polyethylene resin, a polystyrene resin, a polypropylene resin, a polyamide resin, a polyimide resin and a fluorine resin. Among them, it is preferable to use a thermoplastic resin having a glass transition temperature of 70 캜 or lower from the viewpoint of improving the adhesion with time of the transparent substrate 1 and the transparent conductive film 3.

When the resin component constituting the primer layer 2 is formed of a cured product of an ionizing radiation curable resin and a thermoplastic resin, the weight ratio of the former and the latter is preferably 50% by weight or more and 90% by weight or less and 10% Preferably 50 wt% or less, more preferably 60 wt% or more and 80 wt% or less, and the latter is 20 wt% or more and 40 wt% or less. With such a weight ratio, the adhesion with time can be easily made good, and the strength of the primer layer 2 can be prevented from lowering more than necessary.

The resin component constituting the primer layer (2) may be composed of a resin having a hydrophilic group, or a mixture of a resin having no hydrophilic group and a resin having a hydrophilic group. Or may be a mixture of particles having a hydrophilic group on the surface thereof. Examples of the hydrophilic group include at least one kind selected from the group consisting of polyalkylene oxide, hydroxyl group, carboxyl group, sulfonyl group, phosphate group, amino group, isocyanate group, glycidyl group, alkoxysilyl group, ammonium salt, . With such a constitution, it becomes easy to adjust the wet tension on the surface of the primer layer to a predetermined value or more.

The primer layer (2) preferably contains particles together with the resin component. By including particles in the primer layer 2, the adhesion of the transparent substrate 1 and the transparent conductive film 3 over time can be improved. Particularly, when the primer layer 2 contains a cured product of the organic-inorganic hybrid resin, since the organic-inorganic hybrid resin exhibits an action of pushing up the particles to the surface of the primer layer 2 at the time of curing, Can be improved.

Examples of the particles include inorganic particles (such as silica, alumina, talc, clay, calcium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, titanium dioxide, zirconium oxide and the like), resin particles (for example, , Nylon resin particles, styrene resin particles, polyethylene resin particles, benzoguanamine resin particles, and urethane resin particles).

The average particle diameter of the particles is preferably 3 占 퐉 or more, more preferably 4 占 퐉 or more, preferably 10 占 퐉 or less, and more preferably 8 占 퐉 or less. By setting the average particle size to 3 m or more, the adhesion of the transparent substrate 1 and the transparent conductive film 3 over time can be improved. When it is 10 mu m or less, deterioration of transparency can be prevented. The average particle diameter in this case is calculated by the Coulter counter method.

The particles having an average particle size of preferably 3 탆 or more and 10 탆 or less are preferably contained in an amount of 0.02 parts by weight or more and 1 part by weight or less based on 100 parts by weight of the resin component in the primer layer 2, And not more than 0.5 parts by weight.

It is preferable to adjust the refractive index of the primer layer 2 so that the difference from the transparent conductive film 3 is within 0.05. By setting the refractive index of the primer layer 2 within this range, it is possible to make the pattern difficult to be conspicuous when the transparent conductive film 3 is etched and patterned.

In order to adjust the refractive index of the primer layer 2 to the above-mentioned range, it is preferable that the primer layer 2 contains low refractive index fine particles. Here, from the viewpoints of prevention of aggregation of particles and transparency, the low refractive index fine particles preferably have an average particle diameter of 1 nm or more and 200 nm or less. The average particle diameter in this case is calculated by dynamic light scattering method.

Examples of the low refractive index fine particles include magnesium fluoride, silsesquioxane, silica, polystyrene, calcium fluoride, and cryolite. Among these low-refractive-index fine particles, those having a hollow structure or a mesoporous structure are preferable because they have a lower refractive index.

It is preferable that such low refractive index fine particles are contained in an amount of not less than 0.5 parts by weight and not more than 700 parts by weight based on 100 parts by weight of the resin content in the primer layer (2).

In addition, it is preferable that the primer layer 2 of the present example does not excessively contain a leveling agent (silicone, fluorine, acrylic, etc.). When the leveling agent is excessively contained in the primer layer 2, it is difficult to adjust the wet tension of the surface to 30 mN / m or more.

The thickness of the primer layer 2 is not particularly limited, and can be adjusted by particles to be used. For example, when the primer layer 2 contains particles having an average particle size of 3 mu m or more and 10 mu m or less, the thickness of the primer layer 2 is usually about 2 mu m or more and 9 mu m or less. When the primer layer 2 contains low refractive index fine particles having an average particle size of 1 nm or more and 200 nm or less, the thickness of the primer layer 2 when the primer layer 2 has no high refractive index layer described later is usually 0.5 占 퐉 or more and 3 占 퐉 or less , And the thickness of the primer layer 2 in the case of having a high refractive index layer described later is usually about 10 nm or more and 100 nm or less.

On the transparent conductive film 3, an overcoat layer for protecting the conductive film 3 may be provided. The overcoat layer may be a resin film formed from various resins or an inorganic film formed from an inorganic material.

A high refractive index layer may be provided between the transparent substrate 1 and the primer layer 3. The refractive index of the high refractive index layer is preferably 0.2 to 0.3 higher than the refractive index of the primer layer 2. By having such a high refractive index layer, when the transparent conductive film 3 is etched and patterned, the pattern can be made less conspicuous.

The high refractive index layer is formed from a binder resin and high refractive index fine particles. As the binder resin, the same resin component as that of the primer layer (2) can be used. From the viewpoints of prevention of agglomeration of particles and transparency, the high refractive index fine particles preferably have an average particle diameter of 1 nm or more and 200 nm or less. The average particle diameter in this case is calculated by dynamic light scattering method.

The high refractive index fine particles preferably have a refractive index of 1.6 or more, and examples thereof include particles of an oxide selected from titanium, aluminum, cerium, yttrium, zirconium, niobium and antimony. The high refractive index fine particles are preferably contained in an amount of 5 parts by weight or more and 300 parts by weight or less based on 100 parts by weight of the binder resin in the high refractive index layer.

The thickness of the high refractive index layer is preferably 10 nm or more and 100 nm or less.

Each layer of the transparent conductive film 3, the primer layer 2 and the high refractive index layer of the present example can be formed by coating, drying and, if necessary, coating the composition (coating liquid) containing the respective components, And then irradiated with radiation to form a coating film.

The surface of the transparent conductive film 3 may be subjected to a pressing treatment. The surface of the transparent conductive film 3 can be subjected to pressure treatment to planarize the transparent conductive film 3 that has been unevenly formed by the metal nanowires protruding from the surface. The pressurizing treatment includes a method of passing the substrate 4 with the transparent conductive film through a heat roll having a smooth outer surface formed thereon, or a method of pressing the pressurized surface with a hot press formed of a smooth surface.

The transparent conductive film-adhered base material 4 of this example can be used for various flat panel displays, transparent electrodes such as touch panels, antistatic layers, electromagnetic wave shielding layers and the like. An application example to the touch panel will be described below.

Examples of the touch panel include a resistive touch panel and a capacitive touch panel.

The resistive touch panel includes an upper electrode having a transparent conductive layer on one surface of a transparent substrate and a lower electrode having a transparent conductive layer on one surface of the transparent substrate and a spacer so as to face the transparent conductive layers of the upper electrode and the lower electrode It is composed of basic configuration that is arranged by mediation.

In such a resistive-type touch panel, the above-mentioned transparent conductive film-adhered base material 4 may be used as the upper electrode or the lower electrode.

Capacitive touch panels can be divided into surface capacitive and projected capacitive.

The surface type is composed of a basic structure having a transparent conductive film and a protective layer on one side of a substrate, and electrodes arranged at four corners.

As the substrate constituting the surface-type capacitive touch panel and the transparent conductive film, the transparent conductive film-adhered substrate 4 described above can be used.

The projection type includes an X-axis trace as a conductive element group formed along a predetermined first direction on a transparent substrate, a Y-axis trace as a conductive element group formed along a second direction intersecting with the X-axis trace, And an insulating layer disposed at least at the intersection of the external connection lines and the connection wiring to the external extraction line.

The touch panel of the present invention is constructed so as to have the transparent conductive film-adhered base material 4 described above on a transparent substrate in such a projection type capacitive touch panel.

Example

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in more detail with reference to embodiments. In the present embodiment, " part " and "% " are by weight unless otherwise indicated.

1. Preparation of Coating Solution for Transparent Conductive Film

As the metal nanowire, a silver nanowire fabricated in accordance with the article "Materials Chemistry and Physics vol.114 p333-338" Preparation of Ag nanorodswith high yield by polyol process "was used. The silver nanowire has an average diameter on the short-axis side of 50 nm and an aspect ratio of about 100.

Next, IPA was used as a dispersion medium to prepare a dispersion in which silver nanowires were dispersed at 3.0%. Next, 28.53 parts of silicone resin (Mitsubishi Chemical Corporation: MS51) was dissolved in 53.82 parts of IPA to prepare mother liquor (mother liquor). Next, 15.0 parts by mass of the dispersion liquid was added to the mother liquor, followed by mixing with 2.65 parts of 0.1 H nitric acid, mixing well and stirring for 1 hour under a constant temperature atmosphere of 25 ° C to prepare a 15% To prepare a coating liquid for a transparent conductive film.

2. Fabrication of substrate with transparent conductive film

[Example 1]

On one side of a transparent polyester film (Cosmo Shine A4350: Toyobo Co., Ltd.) having a thickness of 125 占 퐉, a primer layer coating liquid a of the following formulation was applied, dried and irradiated with ultraviolet rays to form a primer layer having a thickness of 3 占 퐉. The wet tension on the surface of the primer layer was 32 mN / m. Subsequently, the transparent conductive layer coating liquid was applied onto the primer layer and dried to form a transparent conductive film having a thickness of 0.3 占 퐉 to obtain a substrate having a transparent conductive film.

≪ Primer layer coating liquid a &

· Photopolymerizable prepolymer 140 parts

(Ionizing radiation-curable organic-inorganic hybrid resin)

(Desolite 7503: JSR Co., solid content 50%, inorganic content 38%)

· Thermoplastic resin 70 parts

(Acridic A166: DIC Co., solid content 45%, glass transition temperature 49 캜)

Photopolymerization initiator 2.2 parts

(Irgacure 651: Chiba, Japan company)

· 0.25 part of acrylic resin particles

(Average particle diameter: 5.8 mu m, coefficient of variation: 7.8%)

Diluent Solvent 230 parts

[Example 2]

A substrate with a transparent conductive film was obtained in the same manner as in Example 1 except that the addition amount of the acrylic resin particles in the primer layer coating liquid (a) was changed to 0.05 part. The wet tension on the surface of the primer layer was 32 mN / m.

[Example 3]

A substrate with a transparent conductive film was obtained in the same manner as in Example 1 except that the primer layer coating liquid (a) was changed to the following primer layer coating liquid (b). The wet tension on the surface of the primer layer was 33 mN / m.

≪ Primer layer coating liquid (b) >

· Photopolymerizable prepolymer (ionizing radiation curable resin) 17 parts

(Beam set 575: Arakawa Chemical Industries, solid content 100%)

· Photopolymerizable monomer (isocyanuric acid triacrylate) 3 parts

(NK Ester A9300: Shin-Nakamura Chemical Co., solid content 100%)

Photopolymerization initiator (Irgacure 651) 0.4 part

· Thinning solvent 30 parts

[Example 4]

A substrate with a transparent conductive film was obtained in the same manner as in Example 1 except that the primer layer coating liquid (a) was changed to the following primer layer coating liquid (c). The wet tension on the surface of the primer layer was 33 mN / m.

≪ Primer layer coating liquid (c) >

· Photopolymerizable prepolymer (beam set 575) 35 parts

· Thermoplastic resin (Acridic A166) 35 parts

Photopolymerization initiator (Irgacure 651) 1 part

Diluting solvent 120 parts

[Example 5]

A substrate with a transparent conductive film was obtained in the same manner as in Example 1 except that the primer layer coating liquid (a) was changed to the following primer layer coating liquid (d). The wet tension on the surface of the primer layer was 32 mN / m.

≪ Primer layer coating liquid (d) >

· Photopolymerizable prepolymer (DeSolite 7503) 68 parts

Photopolymerization initiator (Irgacure 651) 2 parts

Diluting solvent 72 parts

[Comparative Example 1]

A substrate with a transparent conductive film was obtained in the same manner as in Example 1 except that the primer layer coating liquid (a) was changed to the following primer layer coating liquid (e). The wet tension on the surface of the primer layer was 22.6 mN / m or less.

≪ Primer layer coating liquid (e) >

· Photopolymerizable prepolymer (beam set 575) 10 parts

· Photopolymerizable monomer (polyethylene glycol diacrylate) 5 parts

(Component: polyethylene glycol diacrylate)

(NK Ester A-1000: Shin-Nakamura Chemical Co., solid content 100%)

Silicone leveling agent 0.02 part

(Polyether-modified dimethylpolysiloxane)

(BYK331: VICKEMISA, 100% solids)

Photopolymerization initiator (Irgacure 651) 0.5 part

Diluent 23 parts

[Comparative Example 2]

A substrate with a transparent conductive film was obtained in the same manner as in Example 1 except that the primer layer coating liquid (a) was changed to the following primer layer coating liquid (f). The wet tension on the surface of the primer layer was 22.6 mN / m or less.

≪ Primer layer coating liquid (f) >

Mixture of photopolymerizable prepolymer and leveling agent 15 parts

(Unidick 17-824-9: DIC Co., solid content 80%)

Photopolymerization initiator (Irgacure 651) 0.4 part

· Thinning solvent 30 parts

3. Evaluation of adhesion

Based on the checkerboard tape method in JIS K5400: 1990, the initial adhesion and the adhesion with time were evaluated for the substrate with a transparent conductive film obtained by each example. As a result, it was found that the transparent conductive film was not peeled off at all, "? &Quot;, the peeling of less than 10% The results are shown in Table 1.

With respect to the adhesion with time, evaluation was carried out after leaving the substrate with the transparent conductive film obtained by each example at a temperature of 60 DEG C and 90% RH for 500 hours.

The wettability of the surface of the primer layer with the transparent conductive film of Examples 1 to 5 was 30 mN / m or more, and thus the initial adhesion of the transparent conductive film and the adhesion with time were excellent. In particular, the transparent conductive film-attached substrate of each of Examples 1, 2, and 4 has an ionizing radiation-curable resin (including ionizing radiation-curable organic-inorganic hybrid resin) and a thermoplastic resin in the primer layer The adhesion with time was very excellent. Among them, the transparent conductive film-adhered base materials of Examples 1 and 2 contained, in addition to the ionizing radiation curable organic-inorganic hybrid resin and the thermoplastic resin, particles in an average particle size of 3 to 10 μm in the primer layer The adhesiveness with time elapsed was better.

On the other hand, in the base material with a transparent conductive film of Comparative Examples 1 and 2, the wet tension on the surface of the primer layer was less than 30 mN / m. As a result, the initial adhesion of the transparent conductive film was excellent, but the adhesion with time was not satisfied.

Claims (10)

A transparent conductive film comprising a transparent conductive film containing a metal nanowire laminated on a transparent substrate via a primer layer having a surface wet tension of 30 mN / m or more as defined in JIS K6768: 1999. The method according to claim 1,
Wherein the primer layer comprises a resin component including a cured product of a curable resin. 3. The method of claim 2,
Characterized in that an ionizing radiation curable resin is used as the curable resin. The method of claim 3,
Wherein an ionizing radiation-curable organic-inorganic hybrid resin is used as said ionizing radiation curable resin. 5. The method according to any one of claims 2 to 4,
Wherein the resin component further comprises a thermoplastic resin. 6. The method of claim 5,
Wherein the content of the resin component in the resin component is from 50% by weight to 90% by weight of the cured resin of the curable resin, and from 10% by weight to 50% by weight of the thermoplastic resin. 7. The method according to any one of claims 2 to 6,
Wherein the primer layer further comprises particles having an average particle diameter of 3 占 퐉 or more and 10 占 퐉 or less. 8. The method of claim 7,
Wherein the content of the particles relative to 100 parts by weight of the resin is 0.02 part by weight or more and 1 part by weight or less. 9. The method according to any one of claims 2 to 8,
Wherein the primer layer further comprises low refractive index fine particles having an average particle diameter of 1 nm or more and 200 nm or less. A touch panel comprising the electrode with the transparent conductive film according to any one of claims 1 to 9.

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