JP6557108B2 - Transparent conductive film and touch panel - Google Patents

Description

  The present invention relates to a transparent conductive film and a touch panel.

  Conventionally, it is known to form a conductive layer on the surface of a base film to obtain a conductive film. It is also known to employ a transparent layer as a base film and a conductive layer to obtain a transparent conductive film.

  As such a conductive layer, an inorganic transparent conductive material such as ITO is often used. However, many of the inorganic transparent conductive materials have a problem that a working environment with a high degree of vacuum is required for production, the production process is complicated, and damage is easily caused by deformation. In order to solve such a problem, a conductive layer containing a polythiophene compound has been proposed (for example, Patent Document 1).

JP 2006-116806 A

  However, the conductive layer proposed in Patent Document 1 requires a certain thickness in order to obtain sufficient conductivity. If the thickness is small, the surface resistance cannot be lowered sufficiently. On the other hand, since the said conductive layer has low transparency, when the thickness is thick, the transparency of the conductive film becomes insufficient. Furthermore, the conductive layer has a problem that it has low adhesion to the film, and is particularly easy to peel when repeatedly peeled.

  An object of the present invention is to provide a transparent conductive film that can be easily produced, has low surface resistance, high transparency, and high adhesion between a base film and a conductive layer.

  A further object of the present invention is to provide a touch panel that can be easily manufactured, has high transparency, and has high durability.

As a result of studying to solve the above-mentioned problems, the present inventor has found that the composition of the conductive layer is specified, and that the above-described problems can be solved when this is combined with a specific base film. Completed the invention.
That is, the present invention is as follows.

[1] A base film containing a alicyclic structure-containing polymer or a hydride of a block copolymer of an aromatic vinyl compound and a conjugated diene compound, or a combination thereof, and a surface of the base film And a conductive layer provided on
A transparent conductive film, wherein the conductive layer includes a polythiophene compound, a polystyrene sulfonic acid compound, a conductivity improver, and a polyamide compound.
[2] The transparent conductive film according to claim 1, wherein the conductivity improver contains a phenol derivative.
[3] The transparent conductive film according to [1] or [2], wherein the conductive layer contains a leveling agent.
[4] A touch panel including the transparent conductive film according to any one of [1] to [3].

  The transparent conductive film of the present invention can be easily manufactured, can be a film having low surface resistance, high transparency, and high adhesion between the base film and the conductive layer. Moreover, the touch panel of this invention can be manufactured easily, can be made into a touch panel with high transparency and high durability.

  Hereinafter, the present invention will be described in detail with reference to embodiments and examples, but the present invention is not limited to the following embodiments and examples, and the claims of the present invention and equivalents thereof. Any change can be made without departing from the scope.

[1. Transparent conductive film: Overview]
The transparent conductive film of this invention is equipped with a base film and the conductive layer provided on the surface.

[2. (Base film)
When the transparent conductive film is used as a constituent element of an on-cell type or mid-cell type touch panel, the material of the base film is preferably a material that is easy to obtain a film having low birefringence. Examples of the polymer constituting such a material include alicyclic structure-containing polymers, hydrides of block copolymers of aromatic vinyl compounds and conjugated diene compounds, and mixtures thereof.

[2.1. Alicyclic structure-containing polymer]
The alicyclic structure-containing polymer is a polymer in which the structural unit of the polymer has an alicyclic structure. The alicyclic structure-containing polymer is, for example, a polymer having an alicyclic structure in the main chain, a polymer having an alicyclic structure in the side chain, a polymer having an alicyclic structure in the main chain and the side chain, In addition, a mixture of any two or more of these may be used. Among these, from the viewpoint of mechanical strength and heat resistance, a polymer having an alicyclic structure in the main chain is preferable.

  Examples of the alicyclic structure include a saturated alicyclic hydrocarbon (cycloalkane) structure and an unsaturated alicyclic hydrocarbon (cycloalkene, cycloalkyne) structure. Among these, from the viewpoint of mechanical strength and heat resistance, a cycloalkane structure and a cycloalkene structure are preferable, and a cycloalkane structure is particularly preferable.

  The number of carbon atoms constituting the alicyclic structure is preferably 4 or more, more preferably 5 or more, preferably 30 or less, more preferably 20 or less, particularly preferably per alicyclic structure. Is 15 or less. When the number of carbon atoms constituting the alicyclic structure is within this range, the mechanical strength, heat resistance and moldability of the base film are highly balanced.

  In the alicyclic structure-containing polymer, the proportion of the structural unit having an alicyclic structure is preferably 55% by weight or more, more preferably 70% by weight or more, and particularly preferably 90% by weight or more. When the ratio of the structural unit having an alicyclic structure in the alicyclic structure-containing polymer is in this range, the transparency and heat resistance of the base film are improved.

  Among the alicyclic structure-containing polymers, preferred are norbornene polymers, monocyclic olefin polymers, cyclic conjugated diene polymers, vinyl alicyclic hydrocarbon polymers, and hydrides thereof. Can be mentioned. Among these, norbornene-based polymers are particularly suitable because of their good transparency and moldability.

  Examples of the norbornene-based polymer include a ring-opening polymer of a monomer having a norbornene structure and a hydride thereof; an addition polymer of a monomer having a norbornene structure and a hydride thereof. Examples of a ring-opening polymer of a monomer having a norbornene structure include a ring-opening homopolymer of one kind of monomer having a norbornene structure and a ring-opening of two or more kinds of monomers having a norbornene structure. Examples thereof include a copolymer and a ring-opening copolymer of a monomer having a norbornene structure and an arbitrary monomer copolymerizable therewith. Furthermore, examples of the addition polymer of a monomer having a norbornene structure include an addition homopolymer of one kind of monomer having a norbornene structure and an addition copolymer of two or more kinds of monomers having a norbornene structure. And addition copolymers of a monomer having a norbornene structure and an arbitrary monomer copolymerizable therewith. Examples of these polymers include polymers disclosed in Japanese Patent Application Laid-Open No. 2002-321302. Among these, a hydride of a ring-opening polymer of a monomer having a norbornene structure is particularly suitable from the viewpoints of transparency, moldability, heat resistance, low hygroscopicity, dimensional stability, lightness, and the like. .

Examples of the monomer having a norbornene structure include bicyclo [2.2.1] hept-2-ene (common name: norbornene), tricyclo [4.3.0.1 ^2,5 ] deca-3,7. -Diene (common name: dicyclopentadiene), 7,8-benzotricyclo [4.3.0.1 ^2,5 ] dec-3-ene (common name: methanotetrahydrofluorene), tetracyclo [4.4. 0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene (common name: tetracyclododecene) and derivatives of these compounds (for example, those having a substituent in the ring). Here, examples of the substituent include an alkyl group, an alkylene group, and a polar group. Moreover, these substituents may be the same or different, and a plurality thereof may be bonded to the ring. One type of monomer having a norbornene structure may be used alone, or two or more types may be used in combination at any ratio.

  Examples of the polar group include heteroatoms and atomic groups having heteroatoms. Examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, and a halogen atom. Specific examples of polar groups include carboxyl groups, carbonyloxycarbonyl groups, epoxy groups, hydroxyl groups, oxy groups, ester groups, silanol groups, silyl groups, amino groups, amide groups, imide groups, nitrile groups, and sulfonic acid groups. Is mentioned.

  Examples of monomers capable of ring-opening copolymerization with monomers having a norbornene structure include monocyclic olefins such as cyclohexene, cycloheptene, and cyclooctene and derivatives thereof; cyclic conjugated dienes such as cyclohexadiene and cycloheptadiene; And derivatives thereof. As the monomer having a norbornene structure and a monomer capable of ring-opening copolymerization, one kind may be used alone, or two or more kinds may be used in combination at any ratio.

  A ring-opening polymer of a monomer having a norbornene structure can be produced, for example, by polymerizing or copolymerizing a monomer in the presence of a ring-opening polymerization catalyst.

  Examples of monomers that can be addition copolymerized with a monomer having a norbornene structure include α-olefins having 2 to 20 carbon atoms such as ethylene, propylene, and 1-butene, and derivatives thereof; cyclobutene, cyclopentene, and cyclohexene. And non-conjugated dienes such as 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, and the like. Among these, α-olefin is preferable and ethylene is more preferable. Moreover, the monomer which can carry out addition copolymerization with the monomer which has a norbornene structure may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

  An addition polymer of a monomer having a norbornene structure can be produced, for example, by polymerizing or copolymerizing a monomer in the presence of an addition polymerization catalyst.

  The hydrogenated product of the above-described ring-opening polymer and addition polymer is, for example, carbon in the presence of a hydrogenation catalyst containing a transition metal such as nickel or palladium in a solution of these ring-opening polymer or addition polymer. -Carbon unsaturated bonds can be produced by hydrogenation, preferably 90% or more.

Among norbornene-based polymers, as structural units, X: bicyclo [3.3.0] octane-2,4-diyl-ethylene structure and Y: tricyclo [4.3.0.1 ^2,5 ] decane- Having a 9,9-diyl-ethylene structure, the amount of these structural units being 90% by weight or more based on the total structural units of the norbornene polymer, and the ratio of X and Y It is preferable that the ratio is 100: 0 to 40:60 by weight ratio of X: Y. By using such a polymer, it is possible to make the substrate film excellent in stability of optical characteristics without long-term dimensional change.

  An alicyclic structure containing polymer may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

  The weight average molecular weight (Mw) of the alicyclic structure-containing polymer is preferably 10,000 or more, more preferably 15,000 or more, particularly preferably 20,000 or more, preferably 100,000 or less, more preferably. Is 80,000 or less, particularly preferably 50,000 or less. When the weight average molecular weight of the alicyclic structure-containing polymer is in such a range, the mechanical strength and molding processability of the base film are highly balanced, which is preferable. Here, the weight average molecular weight is calculated by polyisoprene or polystyrene measured by gel permeation chromatography using cyclohexane as a solvent (however, toluene may be used when the sample does not dissolve in cyclohexane). The weight average molecular weight of

  The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the alicyclic structure-containing polymer is preferably 1 or more, more preferably 1.2 or more, preferably 10 or less, more preferably 4 or less, particularly preferably 3.5 or less.

[2.2. Hydrogenated block copolymer of aromatic vinyl compound and conjugated diene compound]
Examples of hydrides of block copolymers of aromatic vinyl compounds and conjugated diene compounds include hydrides [2] obtained by hydrogenating unsaturated bonds of specific block copolymers [1] described below, and hydrides. An alkoxysilyl group-modified product [3] obtained by modifying [2] with alkoxysilyl is exemplified.

[2.2.1. Block copolymer [1]]
The block copolymer [1] comprises one or more polymer blocks [A] per molecule of the block copolymer [1] and one or more polymer blocks [B] per molecule of the block copolymer [1]. ] Is a block copolymer.

  The polymer block [A] is a polymer block having an aromatic vinyl compound unit as a main component. Here, the aromatic vinyl compound unit refers to a structural unit having a structure formed by polymerizing an aromatic vinyl compound.

  Examples of the aromatic vinyl compound corresponding to the aromatic vinyl compound unit contained in the polymer block [A] include styrene; α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4 -Styrenes having an alkyl group having 1 to 6 carbon atoms as a substituent, such as dimethylstyrene, 2,4-diisopropylstyrene, 4-t-butylstyrene, 5-t-butyl-2-methylstyrene; 4-chloro Styrenes having a halogen atom as a substituent, such as styrene, dichlorostyrene, 4-monofluorostyrene; Styrenes having an alkoxy group having 1 to 6 carbon atoms as a substituent, such as 4-methoxystyrene; 4-phenylstyrene Styrenes having an aryl group as a substituent, such as 1-vinylnaphthalene, 2-vinylnaphthal Vinyl naphthalenes such emissions; and the like. One of these may be used alone, or two or more of these may be used in combination at any ratio. Among these, from the viewpoint of hygroscopicity, aromatic vinyl compounds that do not contain a polar group, such as styrene and styrenes having an alkyl group having 1 to 6 carbon atoms as a substituent, are preferable, and are easy to obtain industrially. Styrene is particularly preferred.

  The content of the aromatic vinyl compound unit in the polymer block [A] is preferably 90% by weight or more, more preferably 95% by weight or more, and particularly preferably 99% by weight or more. By increasing the amount of the aromatic vinyl compound unit in the polymer block [A] as described above, the heat resistance of the base film can be improved.

  The polymer block [A] may contain an arbitrary structural unit in addition to the aromatic vinyl compound unit. The polymer block [A] may contain any structural unit alone or in combination of two or more at any ratio.

  As an arbitrary structural unit that the polymer block [A] may contain, for example, a chain conjugated diene compound unit may be mentioned. Here, the chain conjugated diene compound unit refers to a structural unit having a structure formed by polymerizing a chain conjugated diene compound. Examples of the chain conjugated diene compound corresponding to the chain conjugated diene compound unit include, for example, the same examples as those exemplified as the chain conjugated diene compound corresponding to the chain conjugated diene compound unit included in the polymer block [B]. Is mentioned.

  Moreover, as an arbitrary structural unit which the polymer block [A] can contain, for example, a structural unit having a structure formed by polymerizing an arbitrary unsaturated compound other than an aromatic vinyl compound and a chain conjugated diene compound is used. Can be mentioned. Examples of the optional unsaturated compound include vinyl compounds such as chain vinyl compounds and cyclic vinyl compounds; unsaturated cyclic acid anhydrides; unsaturated imide compounds; These compounds may have a substituent such as a nitrile group, an alkoxycarbonyl group, a hydroxycarbonyl group, or a halogen group. Among these, from the viewpoint of hygroscopicity, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-eicosene, It does not have a polar group such as a chain olefin having 2 to 20 carbon atoms such as 4-methyl-1-pentene and 4,6-dimethyl-1-heptene; a cyclic olefin having 5 to 20 carbon atoms such as vinylcyclohexane; Vinyl compounds are preferred, chain olefins having 2 to 20 carbon atoms are more preferred, and ethylene and propylene are particularly preferred.

  The content of any structural unit in the polymer block [A] is usually 10% by weight or less, preferably 5% by weight or less, more preferably 1% by weight or less.

  The number of polymer blocks [A] in one molecule of block copolymer [1] is preferably 2 or more, preferably 5 or less, more preferably 4 or less, and particularly preferably 3 or less. The plurality of polymer blocks [A] in one molecule may be the same as or different from each other.

  When a plurality of different polymer blocks [A] are present in one molecule of the block copolymer [1], the weight average molecular weight of the polymer block having the maximum weight average molecular weight in the polymer block [A] is expressed as Mw. (A1), and the weight average molecular weight of the polymer block having the smallest weight average molecular weight is Mw (A2). At this time, the ratio “Mw (A1) / Mw (A2)” between Mw (A1) and Mw (A2) is preferably 4.0 or less, more preferably 3.0 or less, and particularly preferably 2.0 or less. It is. Thereby, the dispersion | variation in various physical-property values can be suppressed small.

  The polymer block [B] is a polymer block mainly composed of a chain conjugated diene compound unit. As described above, the chain conjugated diene compound unit refers to a structural unit having a structure formed by polymerizing a chain conjugated diene compound.

  Examples of the chain conjugated diene compound corresponding to the chain conjugated diene compound unit of the polymer block [B] include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1, 3-pentadiene etc. are mentioned. One of these may be used alone, or two or more of these may be used in combination at any ratio. Among these, in terms of hygroscopicity, a chain conjugated diene compound not containing a polar group is preferable, and 1,3-butadiene and isoprene are particularly preferable.

  The content of the chain conjugated diene compound unit in the polymer block [B] is preferably 70% by weight or more, more preferably 80% by weight or more, and particularly preferably 90% by weight or more. By increasing the amount of the chain conjugated diene compound unit in the polymer block [B] as described above, the flexibility of the base film can be improved.

  The polymer block [B] may contain an arbitrary structural unit in addition to the chain conjugated diene compound unit. The polymer block [B] may contain any structural unit alone or in combination of two or more at any ratio.

  As an arbitrary structural unit that can be contained in the polymer block [B], for example, it is formed by polymerizing an aromatic vinyl compound unit and any unsaturated compound other than the aromatic vinyl compound and the chain conjugated diene compound. Examples include structural units having a structure. Examples of the structural unit having a structure formed by polymerizing these aromatic vinyl compound units and any unsaturated compound include those exemplified as those which may be contained in the polymer block [A]. The same example is given.

  The content of any structural unit in the polymer block [B] is preferably 30% by weight or less, more preferably 20% by weight or less, and particularly preferably 10% by weight or less. The flexibility of the base film can be improved by reducing the content of any structural unit in the polymer block [B].

  Block copolymer [1] The number of polymer blocks [B] in one molecule is usually 1 or more, but may be 2 or more. When the number of polymer blocks [B] in the block copolymer [1] is 2 or more, the polymer blocks [B] may be the same as or different from each other.

  When a plurality of different polymer blocks [B] are present in one molecule of the block copolymer [1], the weight average molecular weight of the polymer block having the maximum weight average molecular weight in the polymer block [B] is expressed as Mw. (B1), and the weight average molecular weight of the polymer block having the smallest weight average molecular weight is Mw (B2). At this time, the ratio “Mw (B1) / Mw (B2)” between Mw (B1) and Mw (B2) is preferably 4.0 or less, more preferably 3.0 or less, and particularly preferably 2.0 or less. It is. Thereby, the dispersion | variation in various physical-property values can be suppressed small.

  The form of the block of the block copolymer [1] may be a chain type block or a radial type block. Among these, a chain type block is preferable because of its excellent mechanical strength. When the block copolymer [1] has the form of a chain block, the both ends of the molecular chain of the block copolymer [1] are polymer blocks [A], and the resin constituting the base film Since the stickiness can be suppressed to a desired low value, it is preferable.

  A particularly preferable block form of the block copolymer [1] is that the polymer block [A] is bonded to both ends of the polymer block [B] as represented by [A]-[B]-[A]. A triblock copolymer; [A]-[B]-[A]-[B]-[A], the polymer block [B] is bonded to both ends of the polymer block [A]. And a pentablock copolymer in which the polymer block [A] is bonded to the other end of each of the polymer blocks [B]. In particular, a triblock copolymer of [A]-[B]-[A] is particularly preferable because it can be easily produced and the physical properties can be easily within a desired range.

  In the block copolymer [1], the weight fraction wA of the polymer block [A] in the entire block copolymer [1] and the polymer block [B] in the entire block copolymer [1]. The ratio (wA / wB) to the weight fraction wB falls within a predetermined range. Specifically, the ratio (wA / wB) is usually 20/80 or more, preferably 25/75 or more, more preferably 30/70 or more, particularly preferably 40/60 or more, and usually 60/40. Hereinafter, it is preferably 55/45 or less. By setting the ratio wA / wB to be equal to or higher than the lower limit of the above range, the heat resistance of the base film can be improved or the birefringence can be reduced. Moreover, the softness | flexibility of a base film can be improved by making it into an upper limit or less. Here, the weight fraction wA of the polymer block [A] indicates the weight fraction of the whole polymer block [A], and the weight fraction wB of the polymer block [B] is the whole polymer block [B]. The weight fraction is shown.

The weight average molecular weight (Mw) of the block copolymer [1] is preferably 40,000 or more, more preferably 50,000 or more, particularly preferably 60,000 or more, preferably 200,000 or less. More preferably, it is 150,000 or less, Most preferably, it is 100,000 or less.
The molecular weight distribution (Mw / Mn) of the block copolymer [1] is preferably 3 or less, more preferably 2 or less, particularly preferably 1.5 or less, and preferably 1.0 or more. Here, Mn represents a number average molecular weight.
The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the block copolymer [1] were determined as polystyrene-converted values by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent. It can be measured.

  As a method for producing the block copolymer [1], for example, a monomer mixture (a) containing an aromatic vinyl compound as a main component and a chain conjugated diene compound as a main component are contained by a method such as living anion polymerization. Method of alternately polymerizing the monomer mixture (b); after sequentially polymerizing the monomer mixture (a) containing an aromatic vinyl compound as a main component and the monomer mixture (b) containing a chain conjugated diene compound as a main component And a method of coupling ends of the polymer block [B] with a coupling agent.

  The content of the aromatic vinyl compound in the monomer mixture (a) is usually 90% by weight or more, preferably 95% by weight or more, more preferably 99% by weight or more. The monomer mixture (a) may contain any monomer component other than the aromatic vinyl compound. Examples of the optional monomer component include a chain conjugated diene compound and an arbitrary unsaturated compound. The amount of the optional monomer component is usually 10% by weight or less, preferably 5% by weight or less, more preferably 1% by weight or less based on the monomer mixture (a).

  The content of the chain conjugated diene compound in the monomer mixture (b) is usually 70% by weight or more, preferably 80% by weight or more, more preferably 90% by weight or more. The monomer mixture (b) may contain any monomer component other than the chain conjugated diene compound. Optional monomer components include aromatic vinyl compounds and arbitrary unsaturated compounds. The amount of the optional monomer component is usually 30% by weight or less, preferably 20% by weight or less, more preferably 10% by weight or less, based on the monomer mixture (b).

  As a method for polymerizing the monomer composition to obtain each polymer block, for example, radical polymerization, anion polymerization, cation polymerization, coordination anion polymerization, coordination cation polymerization and the like can be used. From the viewpoint of facilitating the polymerization operation and the hydrogenation reaction in the subsequent step, a method in which radical polymerization, anion polymerization, cation polymerization and the like are performed by living polymerization is preferable, and a method in which living polymerization is performed by living anion polymerization is particularly preferable.

  The polymerization can be carried out in the presence of a polymerization initiator. For example, in living anionic polymerization, as a polymerization initiator, monoorganolithium such as n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, and phenyllithium; dilithiomethane, 1,4-dilithiobutane, 1,4-dilithio A polyfunctional organolithium compound such as 2-ethylcyclohexane; One of these may be used alone, or two or more of these may be used in combination at any ratio.

  The polymerization temperature is preferably 0 ° C. or higher, more preferably 10 ° C. or higher, particularly preferably 20 ° C. or higher, preferably 100 ° C. or lower, more preferably 80 ° C. or lower, particularly preferably 70 ° C. or lower.

As the form of the polymerization reaction, for example, solution polymerization and slurry polymerization can be used. In particular, when solution polymerization is used, reaction heat can be easily removed.
When solution polymerization is performed, an inert solvent in which the polymer obtained in each step can be dissolved can be used as the solvent. Examples of the inert solvent include aliphatic hydrocarbon solvents such as n-butane, n-pentane, isopentane, n-hexane, n-heptane, and isooctane; cyclopentane, cyclohexane, methylcyclopentane, methylcyclohexane, decalin, bicyclo And alicyclic hydrocarbon solvents such as [4.3.0] nonane and tricyclo [4.3.0.1 ^2,5 ] decane; aromatic hydrocarbon solvents such as benzene and toluene; One of these may be used alone, or two or more of these may be used in combination at any ratio. Among these, it is preferable to use an alicyclic hydrocarbon solvent as the solvent because it can be used as it is as an inert solvent for the hydrogenation reaction and the solubility of the block copolymer [1] is good. The amount of the solvent used is preferably 200 to 2000 parts by weight with respect to 100 parts by weight of all the monomers used.

  When each monomer composition contains two or more monomers, a randomizer can be used to prevent a single component chain from becoming long. In particular, when the polymerization reaction is performed by anionic polymerization, it is preferable to use, for example, a Lewis base compound as a randomizer. Examples of Lewis base compounds include ether compounds such as dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, diphenyl ether, ethylene glycol diethyl ether, and ethylene glycol methyl phenyl ether; Tertiary amine compounds; alkali metal alkoxide compounds such as potassium-t-amyl oxide and potassium-t-butyl oxide; phosphine compounds such as triphenylphosphine; One of these may be used alone, or two or more of these may be used in combination at any ratio.

[2.2.2. Hydride [2]]
The hydride [2] is a polymer obtained by hydrogenating the carbon-carbon unsaturated bond of the block copolymer [1]. Here, the unsaturated bond of the block copolymer [1] to be hydrogenated includes aromatic and non-aromatic carbon-carbon unsaturation of the main chain and side chain of the block copolymer [1]. Includes any bond.

The hydrogenation rate is usually 90% or more, preferably 97% or more, and more preferably 97% or more of the carbon-carbon unsaturated bond of the main chain and side chain of the block copolymer [1] and the carbon-carbon unsaturated bond of the aromatic ring. Is 99% or more. The higher the hydrogenation rate, the better the transparency, heat resistance and weather resistance of the base film, and the easier it is to reduce the birefringence of the base film. Here, the hydrogenation rate of the hydride [2] can be obtained by measurement by ¹ H-NMR.

  In particular, the hydrogenation rate of the non-aromatic carbon-carbon unsaturated bond is preferably 95% or more, more preferably 99% or more. By increasing the hydrogenation rate of the non-aromatic carbon-carbon unsaturated bond, the light resistance and oxidation resistance of the base film can be further increased.

  The hydrogenation rate of the aromatic carbon-carbon unsaturated bond is preferably 90% or more, more preferably 93% or more, and particularly preferably 95% or more. Since the glass transition temperature of the polymer block obtained by hydrogenating the polymer block [A] is increased by increasing the hydrogenation rate of the carbon-carbon unsaturated bond of the aromatic ring, the heat resistance of the base film is effective. Can be enhanced. Furthermore, the photoelastic coefficient of the substrate film can be lowered.

The weight average molecular weight (Mw) of the hydride [2] is preferably 40,000 or more, more preferably 50,000 or more, particularly preferably 60,000 or more, preferably 200,000 or less, more preferably 150. 1,000 or less, particularly preferably 100,000 or less. By keeping the weight average molecular weight (Mw) of the hydride [2] in the above range, the mechanical strength and heat resistance of the base film can be improved, and the birefringence of the base film can be easily reduced.
The molecular weight distribution (Mw / Mn) of the hydride [2] is preferably 3 or less, more preferably 2 or less, particularly preferably 1.5 or less, and preferably 1.0 or more. By keeping the molecular weight distribution (Mw / Mn) of the hydride [2] in the above range, the mechanical strength and heat resistance of the base film can be improved, and the birefringence of the base film can be easily reduced. .
The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the hydride [2] can be measured in terms of polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent.

  The hydride [2] described above can be produced by hydrogenating the block copolymer [1]. As the hydrogenation method, a hydrogenation method that can increase the hydrogenation rate and causes little chain-breaking reaction of the block copolymer [1] is preferable. Examples of such a hydrogenation method include the methods described in International Publication No. 2011/096389 and International Publication No. 2012/043708.

  Examples of specific hydrogenation methods include, for example, hydrogenation using a hydrogenation catalyst containing at least one metal selected from the group consisting of nickel, cobalt, iron, rhodium, palladium, platinum, ruthenium, and rhenium. The method of performing is mentioned. A hydrogenation catalyst may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios. As the hydrogenation catalyst, either a heterogeneous catalyst or a homogeneous catalyst can be used. The hydrogenation reaction is preferably performed in an organic solvent.

The heterogeneous catalyst may be used as it is, for example, as a metal or a metal compound, or may be used by being supported on a suitable carrier. Examples of the carrier include activated carbon, silica, alumina, calcium carbonate, titania, magnesia, zirconia, diatomaceous earth, silicon carbide, calcium fluoride, and the like. The supported amount of the catalyst is preferably 0.1% by weight or more, more preferably 1% by weight or more, preferably 60% by weight or less, more preferably 50% by weight or less based on the total amount of the catalyst and the carrier. is there. The specific surface area of the supported catalyst is preferably 100m ² / g~500m ² / g. Further, the average pore diameter of the supported catalyst is preferably 100 mm or more, more preferably 200 mm or more, preferably 1000 mm or less, more preferably 500 mm or less. Here, the specific surface area can be obtained by measuring the nitrogen adsorption amount and using the BET equation. The average pore diameter can be measured by a mercury intrusion method.

  Examples of homogeneous catalysts include catalysts in which nickel, cobalt, or iron compounds and organometallic compounds (eg, organoaluminum compounds, organolithium compounds) are combined; organometallics including rhodium, palladium, platinum, ruthenium, rhenium, etc. Complex catalysts; and the like can be used.

Examples of the nickel, cobalt, or iron compound include acetylacetonate compounds, carboxylates, cyclopentadienyl compounds, and the like of various metals.
Examples of the organoaluminum compound include alkylaluminums such as triethylaluminum and triisobutylaluminum; aluminum halides such as diethylaluminum chloride and ethylaluminum dichloride; alkylaluminum hydrides such as diisobutylaluminum hydride; and the like.

  Examples of organometallic complex catalysts include transition metal complexes such as dihydrido-tetrakis (triphenylphosphine) ruthenium, dihydrido-tetrakis (triphenylphosphine) iron, bis (cyclooctadiene) nickel, and bis (cyclopentadienyl) nickel. Is mentioned.

  The amount of the hydrogenation catalyst used is preferably 0.01 parts by weight or more, more preferably 0.05 parts by weight or more, particularly preferably 0.1 parts by weight or more with respect to 100 parts by weight of the block copolymer [1]. Preferably, it is 100 parts by weight or less, more preferably 50 parts by weight or less, and particularly preferably 30 parts by weight or less.

  The temperature of the hydrogenation reaction is preferably 10 ° C or higher, more preferably 50 ° C or higher, particularly preferably 80 ° C or higher, preferably 250 ° C or lower, more preferably 200 ° C or lower, particularly preferably 180 ° C or lower. . By performing the hydrogenation reaction in such a temperature range, the hydrogenation rate can be increased, and the molecular cleavage of the block copolymer [1] can be reduced.

  The hydrogen pressure during the hydrogenation reaction is preferably 0.1 MPa or more, more preferably 1 MPa or more, particularly preferably 2 MPa or more, preferably 30 MPa or less, more preferably 20 MPa or less, and particularly preferably 10 MPa or less. By performing the hydrogenation reaction at such a hydrogen pressure, the hydrogenation rate can be increased, the molecular chain scission of the block copolymer [1] can be reduced, and the operability is improved.

  The hydride [2] obtained by the above-described method is usually obtained as a reaction liquid containing a hydride [2], a hydrogenation catalyst, and a polymerization catalyst. Therefore, the hydride [2] may be recovered from the reaction solution after removing the hydrogenation catalyst and the polymerization catalyst from the reaction solution by a method such as filtration and centrifugation. As a method for recovering the hydride [2] from the reaction solution, for example, a steam coagulation method in which the solvent is removed from the reaction solution containing the hydride [2] by steam stripping; direct solvent removal to remove the solvent under reduced pressure heating And a solidification method in which the reaction solution is poured into a poor solvent of hydride [2] to precipitate or solidify.

  When the recovered hydride [2] is further subjected to a silylation modification reaction (reaction for introducing an alkoxysilyl group), the form thereof is preferably in the form of a pellet from the viewpoint of ease of handling. For example, the molten hydride [2] may be extruded from a die into strands, cooled, and then cut into pellets by a pelletizer, and used for various moldings. In the case of using a solidification method, for example, the obtained solidified product may be dried and then extruded in a molten state by an extruder and may be formed into pellets in the same manner as described above and used for various moldings.

[2.2.3. Modified alkoxysilyl group [3]]
The alkoxysilyl group-modified product [3] is a polymer obtained by introducing an alkoxysilyl group into the hydride [2] of the block copolymer [1] described above. In this case, the alkoxysilyl group may be directly bonded to the hydride [2] described above, and may be indirectly bonded, for example, via a divalent organic group such as an alkylene group. The alkoxysilyl group-modified product [3] is particularly excellent in adhesion to inorganic materials such as glass and metal. Therefore, the base film is usually excellent in adhesiveness with the inorganic material. Therefore, the base film can maintain a high adhesive force to the inorganic material even after being exposed to a high temperature and high humidity environment for a long time.

The introduction amount of the alkoxysilyl group in the modified alkoxysilyl group [3] is preferably 0.1 parts by weight or more, more preferably 0.1 parts by weight or more with respect to 100 parts by weight of the hydride [2] before introduction of the alkoxysilyl group. 2 parts by weight or more, particularly preferably 0.3 parts by weight or more, preferably 10 parts by weight or less, more preferably 5 parts by weight or less, and particularly preferably 3 parts by weight or less. When the introduction amount of the alkoxysilyl group falls within the above range, it is possible to prevent the degree of cross-linking between the alkoxysilyl groups decomposed with moisture or the like from becoming excessively high, so that the adhesion of the base film to the inorganic material is kept high. be able to.
The amount of alkoxysilyl group introduced can be measured by ¹ H-NMR spectrum. In addition, when the introduction amount of the alkoxysilyl group is measured, if the introduction amount is small, the number of integrations can be increased.

Since the weight average molecular weight (Mw) of the alkoxysilyl group-modified product [3] is small in the amount of alkoxysilyl groups introduced, usually the weight average molecular weight (2) of the hydride [2] before introducing the alkoxysilyl group ( Mw) does not change significantly. However, when the alkoxysilyl group is introduced, the hydride [2] is modified in the presence of a peroxide, so that the hydride [2] undergoes a crosslinking reaction and a cleavage reaction, and the molecular weight distribution changes greatly. Tend to. The weight average molecular weight (Mw) of the alkoxysilyl group-modified product [3] is preferably 40,000 or more, more preferably 50,000 or more, particularly preferably 60,000 or more, and preferably 200,000 or less. Preferably it is 150,000 or less, Most preferably, it is 100,000 or less. The molecular weight distribution (Mw / Mn) of the modified alkoxysilyl group [3] is preferably 3.5 or less, more preferably 2.5 or less, particularly preferably 2.0 or less, preferably 1.0. That's it. When the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the alkoxysilyl group-modified product [3] are within this range, good mechanical strength and tensile elongation of the substrate film can be maintained.
The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the alkoxysilyl group-modified product [3] can be measured as values in terms of polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent. .

  The alkoxysilyl group-modified product [3] can be produced by introducing an alkoxysilyl group into the hydride [2] of the block copolymer [1] described above. Examples of the method for introducing an alkoxysilyl group into the hydride [2] include a method in which the hydride [2] and an ethylenically unsaturated silane compound are reacted in the presence of a peroxide.

  As the ethylenically unsaturated silane compound, those capable of graft polymerization with hydride [2] and capable of introducing an alkoxysilyl group into hydride [2] can be used. Examples of such ethylenically unsaturated silane compounds include: vinyltrimethoxysilane, vinyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane and other alkoxy silanes; allyltrimethoxysilane, allyltriethoxysilane Alkoxysilanes having an allyl group such as p-styryltrimethoxysilane, p-styryltriethoxysilane and the like alkoxysilanes having a p-styryl group; 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane Alkoxysilanes having a 3-methacryloxypropyl group such as 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldiethoxysilane; 3-acryloxypropyl Alkoxysilanes having a 3-acryloxypropyl group such as limethoxysilane and 3-acryloxypropyltriethoxysilane; alkoxysilanes having a 2-norbornen-5-yl group such as 2-norbornene-5-yltrimethoxysilane; Etc. Among these, since the effects of the present invention are more easily obtained, vinyltrimethoxysilane, vinyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, allyltrimethoxysilane, allyltriethoxysilane, p-styryltrimethoxy Silane is preferred. Moreover, an ethylenically unsaturated silane compound may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

  The amount of the ethylenically unsaturated silane compound is preferably 0.1 parts by weight or more, more preferably 0.2 parts by weight or more, particularly 100 parts by weight of the hydride [2] before introducing the alkoxysilyl group. The amount is preferably 0.3 parts by weight or more, preferably 10 parts by weight or less, more preferably 5 parts by weight or less, and particularly preferably 3 parts by weight or less.

  As the peroxide, one that functions as a radical reaction initiator can be used. As such a peroxide, an organic peroxide is usually used. Examples of the organic peroxide include dibenzoyl peroxide, t-butyl peroxyacetate, 2,2-di- (t-butylperoxy) butane, t-butylperoxybenzoate, t-butylcumyl peroxide, Dicumyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxyhexane), di-t-butyl peroxide, 2,5-dimethyl-2,5 -Di (t-butylperoxy) hexane-3, t-butylhydroperoxide, t-butylperoxyisobutyrate, lauroyl peroxide, dipropionyl peroxide, p-menthane hydroperoxide and the like. Among these, those having a 1-minute half-life temperature of 170 ° C. to 190 ° C. are preferable, and specifically, t-butylcumyl peroxide, dicumyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl. -2,5-di (t-butylperoxyhexane), di-t-butylperoxide and the like are preferable. Moreover, a peroxide may be used individually by 1 type and may be used in combination of 2 or more type.

  The amount of the peroxide is preferably 0.01 parts by weight or more, more preferably 0.2 parts by weight or more, particularly preferably 0 parts by weight based on 100 parts by weight of the hydride [2] before introducing the alkoxysilyl group. .3 parts by weight or more, preferably 5 parts by weight or less, more preferably 3 parts by weight or less, and particularly preferably 2 parts by weight or less.

  The method of reacting the hydride [2] of the block copolymer [1] with the ethylenically unsaturated silane compound in the presence of a peroxide can be performed using, for example, a heating kneader and a reactor. As a specific example, a mixture of a hydride [2], an ethylenically unsaturated silane compound and a peroxide is heated and melted at a temperature equal to or higher than the melting temperature of the hydride [2] in a biaxial kneader to obtain a desired value. By kneading for this time, the alkoxysilyl group-modified product [3] can be obtained. The specific temperature during kneading is preferably 180 ° C. or higher, more preferably 190 ° C. or higher, particularly preferably 200 ° C. or higher, preferably 240 ° C. or lower, more preferably 230 ° C. or lower, particularly preferably 220 ° C. or lower. It is. The kneading time is preferably 0.1 minutes or more, more preferably 0.2 minutes or more, particularly preferably 0.3 minutes or more, preferably 15 minutes or less, more preferably 10 minutes or less, particularly preferably. 5 minutes or less. When using a continuous kneading facility such as a twin-screw kneader or a single-screw extruder, kneading and extrusion can be performed continuously with the residence time being in the above range.

  The amount of the alkoxysilyl group-modified product [3] in the resin constituting the base film is preferably 95% by weight or more, more preferably 97% by weight or more, still more preferably 98% by weight or more, and particularly preferably 99% by weight or more. It is. By keeping the amount of the alkoxysilyl group-modified product [3] within the above range, the desired effect of the present invention can be stably exhibited.

[2.3. Optional components other than polymers]
The resin used as the material of the base film can contain any compounding agent in addition to the various polymers listed above. Examples of compounding agents include antioxidants, heat stabilizers, light stabilizers, UV absorbers, antistatic agents, dispersants, chlorine scavengers, flame retardants, crystallization nucleating agents, reinforcing agents, antiblocking agents, antiblocking agents. Examples include clouding agents, mold release agents, pigments, organic or inorganic fillers, neutralizing agents, lubricants, decomposition agents, metal deactivators, antifouling agents, and antibacterial agents. These components may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios. The ratio of the arbitrary compounding agent can be appropriately adjusted within a range in which the ratio of the polymer in the resin is a preferable ratio. The proportion of the polymer in the resin is preferably 50% to 100% by weight, more preferably 70% to 100% by weight, and particularly preferably 90% to 100% by weight. By making the ratio of a polymer into the said range, a base film can acquire sufficient heat resistance and transparency.

[2.4. (Structure and properties of base film)
The base film may be a single layer film composed of a single layer, or may be a multilayer film composed of a plurality of layers. In the case of a multilayer, the materials constituting the plurality of layers may be the same. May be different.

  The thickness in particular of a base film is not restrict | limited, It can adjust suitably to the thickness according to the use of a transparent conductive film. For example, it is preferably 5 μm or more, more preferably 10 μm or more, while preferably 200 μm or less, more preferably 150 μm or less. By making the thickness of the base film equal to or higher than the lower limit of the range, the mechanical strength of the base film can be sufficiently increased, and by making the thickness of the base film equal to or lower than the upper limit of the range, The thickness can be reduced.

  Prior to the formation of the conductive layer, the base film may have a surface treated on the surface. Examples of the surface treatment include corona treatment, plasma treatment, and chemical treatment. Thereby, the binding property of a base film and an electroconductive layer can be improved.

  The base film is a resin film that has a low water absorption rate and a small dimensional change due to humidity change from the viewpoint of dimensional stability when the transparent conductive film of the present invention is used as a conductive component in a display device. It is preferable that Specifically, the water absorption rate of the resin can be preferably 2% or less, more preferably 1% or less. This water absorption can be measured according to ASTM D570.

  The substrate film may be an optically substantially isotropic film having a small in-plane retardation Re, or may be an optically anisotropic film having an in-plane retardation Re. When using a transparent conductive film as a component of an on-cell type or mid-cell type touch panel, the base film is preferably a film having a small birefringence. In this case, the upper limit of the Re value is preferably 20 nm or less, more preferably 10 nm or less, and the lower limit of the Re value is ideally 0 nm.

  The arithmetic surface roughness Ra of the surface of the base film on which the conductive layer is formed is preferably 10 μm or less, more preferably 5 μm or less, and particularly preferably 1 μm or less. By reducing the arithmetic average roughness Ra of the surface of the base film as described above, the thickness of the conductive layer formed on the surface can be made uniform. Therefore, since it can suppress that a thin part generate | occur | produces locally in an electroconductive layer, the increase in resistance by the said thin part can be suppressed. Therefore, for example, when a transparent conductive film is used for the touch panel, it is possible to increase the detection sensitivity of the change in capacitance when the touch panel is used. Although there is no restriction | limiting in particular in the minimum of said arithmetic mean roughness Ra, Usually, it is 1 nm or more. The arithmetic average roughness Ra of the surface of the base film can be measured using a non-contact surface shape measuring machine (for example, NewView series manufactured by ZYGO).

[2.5. Manufacturing method of base film]
The manufacturing method of a base film is not specifically limited, It can manufacture by shape | molding the material described above by arbitrary shaping | molding methods. Examples of the molding method include a melt molding method and a solution casting method. Examples of the melt molding method include a melt extrusion method in which molding is performed by melt extrusion, a press molding method, an inflation molding method, an injection molding method, a blow molding method, and a stretch molding method. Among these methods, the melt extrusion method, the inflation molding method, and the press molding method are preferable from the viewpoint of obtaining a base film having excellent mechanical strength and surface accuracy. Among them, the melt extrusion method is particularly preferable because the amount of the residual solvent can be reduced, and efficient and simple production is possible. In particular, the base film manufactured using the melt extrusion method can reduce the outgas from the base film when performing a film forming method such as a sputtering method for forming the conductive layer. Good film formation of the layer is possible. Suitable molding methods include, for example, methods disclosed in JP-A-3-223328, JP-A-2000-280315, and the like.

  Depending on the use of the transparent conductive film, the base film may be subjected to a stretching treatment after molding. However, when the transparent conductive film is used as a constituent element of an on-cell type or mid-cell type touch panel, the base film preferably has a small birefringence. From the viewpoint that the degree of retardation is small even when stress is applied to the film in the production process of the base film, the material of the base film is the aromatic vinyl compound and the conjugate described above as the polymer. Those containing a hydride of a block copolymer of a diene compound are preferred.

  The manufacturing method of the base film may further include an optional step in addition to the above steps. For example, a step of cutting a long base film into an appropriate shape such as a rectangle may be included.

[3. Conductive layer]
The conductive layer in the transparent conductive film of the present invention contains a polythiophene compound, a polystyrene sulfonic acid compound, a conductivity improver, and a polyamide compound.
In the present application, the polythiophene compound and the polystyrene sulfonic acid compound may be collectively referred to as a “conductive polymer”.

[3.1. Polythiophene compound)
The polythiophene compound is a polymer containing a polymer unit having a structure obtained by polymerizing thiophene or a derivative thereof (hereinafter sometimes referred to as “thiophene unit”). Examples of thiophene derivatives include derivatives having substituents at the 3-position and 4-position of the thiophene ring. A more specific example is ethylenedioxythiophene.

  Examples of the polymerization mode of thiophene or a derivative thereof in the polythiophene compound typically include a mode in which the thiophene ring is bonded to other rings at the 2-position and 5-position of the thiophene ring, and more specifically, ethylenedioxythiophene. However, the 2nd and 5th positions of the thiophene ring may be combined with other rings. In the present application, such polyethylene dioxythiophene may be referred to as “PEDOT”.

  The polythiophene compound may have polymerized units other than thiophene units.

  The molecular weight of the polythiophene compound is not particularly limited, and a molecular weight having a desired conductivity can be selected as appropriate.

[3.2. Polystyrene sulfonic acid compound)
The polystyrene sulfonic acid compound is a polymer containing a polymer unit having a structure obtained by polymerizing styrene sulfonic acid or a derivative thereof (hereinafter sometimes referred to as “styrene sulfonic acid unit”). In the present application, a polymer including a polymer unit having a structure obtained by polymerizing styrene sulfonic acid may be referred to as “PSS”. Further, the combination of PEDOT and PSS may be referred to as “PEDOT / PSS”.

  The polystyrene sulfonic acid compound may have a polymerization unit other than the styrene sulfonic acid unit.

  Without being bound by a specific theory, it is believed that the polythiophene compound and the polystyrene sulfonic acid compound have an electric charge in the conductive layer and form an ion pair, thereby exhibiting conductivity. Specifically, the charge delocalized in the polythiophene compound and the charge of the sulfo group in the polystyrene sulfonic acid compound can form a pair. For example, PEDOT and PSS can form a pair schematically shown in the following formula (X).

The ratio of the conductive polymer in the conductive layer and the ratio of the polythiophene compound and the polystyrene sulfonic acid compound in the conductive polymer can be appropriately adjusted so that desired properties such as conductivity can be obtained.
A commercially available product can be used as PEDOT / PSS. Examples of commercially available products include “Clevios (registered trademark) PH500, PH510, PH1000” manufactured by Heraeus.

[3.3. (Conductivity improver)
The conductivity improver is a component that further reduces the surface resistance of the conductive layer.
The conductivity improver can be appropriately selected according to the purpose. Examples of conductivity improvers include ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, catechol, cyclohexanediol , Cyclohexanedimethanol, glycerin, dimethyl sulfoxide, N-methylformamide, N, N-dimethylformamide, isophorone, propylene carbonate, cyclohexanone, γ-butyrolactone, diethylene glycol monoethyl ether, and phenol derivatives. Among these, ethylene glycol, dimethyl sulfoxide, N-methylformamide, and phenol derivatives are preferably used. Most preferred are phenol derivatives.

Specific examples of the phenol derivative include 2,6-dihydroxymethyl-4-methylphenol (hereinafter sometimes referred to as “26DMPC”), 2,4-dihydroxymethyl-6-methylphenol, bis (2-hydroxy-3 -Hydroxymethyl-5-methylphenyl) methane, bis (4-hydroxy-3-hydroxymethyl-5-methylphenyl) methane, 2,2-bis (4-hydroxy-3,5-dihydroxy-methylphenyl) propane, And bis (3-formyl-4-hydroxyphenyl) methane.
As a conductivity improver, 1 type may be used independently and 2 or more types may be used together in arbitrary ratios.

  Usually, as the conductivity improver, a compound having a lower molecular weight than other components (polythiophene compound, polystyrene sulfonic acid compound, and polyamide compound) is used, which can contribute to improvement of conductivity.

  The proportion of the conductivity improver in the conductive layer is preferably 10% by weight or more, more preferably 20% by weight or more, while preferably 55% by weight or less, more preferably 50% by weight or less. When the ratio of the conductivity improver is within the above range, good conductivity can be obtained.

[3.4. Polyamide compound)
In the transparent conductive film of the present invention, the conductive layer contains a polyamide compound. When the conductive layer contains a polyamide compound, a conductive layer having low surface resistance, high transparency, and high adhesion to the base film can be formed. In particular, it is possible to form a conductive layer having high durability when a peeling load is repeatedly applied.

  As a polyamide compound, what can obtain an appropriate effect from various known polyamides and modified polyamides can be appropriately selected. As the polyamide compound, an aliphatic polyamide or an aliphatic modified polyamide can be preferably used.

  Examples of polyamides include nylons such as 6-nylon, 66-nylon, 610-nylon, 11-nylon, 12-nylon, so-called copolymer nylon obtained by copolymerizing two or more polymerized units of the nylon, and others. Fatty acid polyamides and fatty acid block copolymers (polyether ester amides, polyester amides).

  Examples of modified polyamides include those obtained by chemically modifying polyamides such as those exemplified above. Specifically, a modified end group of polyamide, an amide group in the chain, or both are modified. Examples of such modification modes include amino modification, carboxyl modification, hydroxyl modification, alkylamination modification, and alkoxyalkylation modification. When an arbitrary layer such as a pressure-sensitive adhesive layer is laminated on the conductive layer, it is preferable to use these modified polyamides from the viewpoint of adhesion.

Specific examples of the modified polyamide include the following.
Modified polyamide (a): N-alkoxyalkyl modified part or all of the amide group of nylon or copolymer nylon as exemplified above. Examples of such N-alkoxyalkyl-modified embodiments include N-alkoxymethyl-modified, N-alkoxyethyl-modified, and combinations thereof.
Modified polyamide (b): A product obtained by modifying a part or all of the end groups of an aliphatic polyamide. Examples of such modification modes include amino modification, carboxyl modification, hydroxyl modification, and combinations thereof.
Modified polyamide (c): A product obtained by alkylamination or alkoxyalkylation of a part or all of the amide group of an aliphatic polyamide.

  More specific examples of the modified polyamide (b) include those represented by the following general formula (1).

  In formula (1), X and Y represent any of those shown in Table 1 below.

Here, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ are substituted or unsubstituted. Represents an alkylene group. Moreover, l and m represent a polymerization ratio, and it is preferable that l + m = 100. When l is 2 or more, each R ₁ may be the same or different, and when m is 2 or more, each R ₂ may be the same or different. In addition, between the * and * in the general formula (1), the left unit containing R ₁ and the right unit containing R ₂ may be directly bonded, or bonded with an arbitrary polyamide unit in between. It may be. The terminal amino group concentration is preferably at least 10 meq / kg, more preferably 30 meq / kg or more.
Moreover, when it has an amino group and a carboxyl group at the terminal, these preferable ratios are 1.1-10 by amino group / carboxyl group concentration ratio. As a method for adjusting the terminal group, a known method can be used. For example, there may be mentioned a method in which diamines, monoamines, dicarboxylic acids, and monocarboxylic acids are appropriately selected and added so that a predetermined terminal concentration is obtained during polymerization. When the modified polyamide has a hydroxyl group at the terminal, the terminal hydroxyl group concentration is preferably 5 meq / kg or more, and more preferably 10 meq / kg or more. Examples of the method for introducing a hydroxyl group at the terminal include a method of adding hydroxylamines or epoxies to the reaction system so as to obtain a predetermined terminal concentration after polymerization.

  Specific examples of the modified polyamide (c) include those represented by the following general formula (2).

Here, R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ represent a substituted or unsubstituted alkylene group, and R ₁₉ represents a substituted or unsubstituted alkyl group. p and q represent polymerization ratios, p is 50 or more and 90 or less, and p + q = 100.
As a modification method, a conventionally known method can be used. For example, when a part of the amide group is alkoxyalkylated, nylon 6 or the like is reacted with formaldehyde or alcohol to replace the hydrogen atom of the amide bond with the alkoxyalkyl group. Can be obtained.
Among these, those obtained by amino-modifying some or all of the end groups of the aliphatic polyamide and N-alkoxyalkylated nylon are preferably used.

  The weight average molecular weight of the modified polyamide is generally 5,000 to 500,000, preferably 10,000 to 200,000. By setting the weight average molecular weight to 5,000 or more, the durability of the conductive layer can be improved. By setting the weight average molecular weight to 500,000 or less, solubility in a solvent can be improved, and a good normal conductive composition can be obtained.

Examples of specific products of polyamide compounds include “CM4000” and “CM8000” (above, manufactured by Toray), “F-30”, “MF-30”, and “EF-30T” (above, manufactured by Teikoku Chemical Industry). ), And “FR105” and “FR104” (manufactured by Lead City).
As the polyamide compound, one kind of polyamide compound may be used alone, or two or more kinds may be used in combination at an arbitrary ratio.

  In the conductive composition for forming the conductive layer, since the conductive polymer (PEDOT / PSS or the like) is an organic acid, it can function as a catalyst for promoting the crosslinking reaction of the polyamide compound, particularly methoxymethyl-modified polyamide. Therefore, when the conductive composition contains a polyamide compound, particularly a methoxymethyl-modified polyamide, a highly strong conductive layer can be obtained.

  The proportion of the polyamide compound in the conductive layer is preferably 8% by weight or more, more preferably 10% by weight or more, while preferably 25% by weight or less, more preferably 20% by weight or less. By setting the ratio of the polyamide compound to the lower limit or more, good adhesion between the base film and the conductive layer can be obtained. By setting the ratio of the polyamide compound to the upper limit or less, good conductivity can be obtained.

[3.5. Optional components of conductive layer]
The conductive layer may contain an optional component in addition to the polythiophene compound, the polystyrene sulfonic acid compound, the conductivity improver, and the polyamide compound. For example, the conductive layer can include a leveling agent.

  A leveling agent is an additive that improves the film thickness uniformity and surface smoothness of a conductive layer. A surfactant can be used as the leveling agent. Preferable examples of the surfactant include a fluorine-based surfactant, a glycol-based surfactant having an acetylene group in the molecule, and a combination thereof. By using these, a satisfactory leveling effect can be obtained.

  Examples of fluorosurfactants include commercially available anionic, cationic, amphoteric and nonionic ones. Specific examples of commodities include: Surflon S-111n, Surflon S-113, Surflon S-121, Surflon S-131, Surflon S-132, Surflon S-141, Surflon S-145, Surflon S-381, Surflon S-383, Surflon S-393, Surflon SC-101, Surflon KH-40, Surflon SA-100 (above, manufactured by AGC Sey Chemical Co., Ltd.), Megafuck F-114, Megafuck F-410, Megafuck F-493 , Mega Fuck F-494, Mega Fuck F-443, Mega Fuck F-444, Mega Fuck F-445, Mega Fuck F-470, Mega Fuck F-471, Mega Fuck F-472SF, Mega Fuck F-474, Mega Fuck F-475, Mega Fuck R-30, Me Fuck F-477, Mega Fuck F-478, Mega Fuck F-479, Mega Fuck F-480SF, Mega Fuck F-482, Mega Fuck F-484, Mega Fuck F-484, Mega Fuck F-486, Mega Fuck F -487, Megafuck F-172D, Megafuck F-178K, Megafuck F-178RM, Megafuck ESM-1, Megafuck MCF-350SF, Megafuck BL-20, Megafuck R-61, and Megafuck R- 90 (manufactured by Dainippon Ink & Chemicals, Inc.).

  Specific examples of commercial products of glycol surfactants having an acetylene group in the molecule include Surfinol 104E, Surfinol 104H, Surfinol 104A, Surfinol 104BC, Surfinol 104DPM, Surfinol 104PA, Surfinol 104PG. -50, Surfinol 104S, Surfinol 420, Surfinol 440, Surfinol 465, Surfinol 485, Surfinol SE, Surfinol SE-F, Surfinol 504, Surfinol 61, Surfinol 2502, Surfinol 82, and DYNOL 604 (manufactured by Nissin Chemical Industry Co.)

  As a leveling agent, 1 type may be used independently and 2 or more types may be used together in arbitrary ratios.

  The ratio of the leveling agent in the conductive composition is preferably 50 ppm or more, more preferably 100 ppm or more, while preferably 50000 ppm or less, more preferably 30000 ppm or less. By setting the ratio of the leveling agent to the lower limit or more, a sufficient leveling effect can be obtained and a good conductive layer surface can be obtained. By making the ratio of the leveling agent not more than the above upper limit, it is possible to avoid the deterioration of the surface due to the generation of bubbles and to obtain good conductivity.

[3.6. Method for forming conductive layer]
The method for forming the conductive layer on the surface of the base film is not particularly limited, and any method can be adopted. Usually, the conductive layer is conductive by applying a composition containing the above-described components of the conductive layer (the composition may be referred to as “conductive composition” hereinafter) on the surface of the base film. It is obtained by forming a layer of the composition and drying it.

  The conductive composition may contain a solvent in addition to the components of the conductive layer described above. Examples of solvents include water, organic solvents, and combinations thereof. The solvent is particularly preferably a mixture of water and an organic solvent that is compatible with water. Examples of organic solvents that are compatible with water include methanol, ethanol, 1-propanol, and 2-propanol (isopropyl alcohol, IPA), with 2-propanol being preferred.

  When the solvent is water and a mixture of organic solvents compatible with water, the proportion of the organic solvent in the solvent is preferably 50% by weight or more, more preferably 70% by weight or more, while preferably 95% by weight. Below, more preferably 90% by weight or less. When the ratio of the organic solvent in the solvent is within the above range, all components can be dissolved or dispersed well, and a high-quality conductive layer can be easily obtained.

  The polythiophene compound, polystyrene sulfonic acid compound, conductivity improver, polyamide compound, and other optional components of the conductive layer may be available as a product in a state of being dissolved or dispersed in a solvent. In that case, the solvent of such a commodity can be used as a part or all of the solvent constituting the conductive composition.

  The ratio of the solid content (component which does not volatilize under dry conditions among the components of the conductive composition) in the conductive composition can be appropriately adjusted within a range in which the formation of the conductive layer is easy.

  The proportion of each component in the conductive layer usually matches the proportion of each component in the solid content of the conductive composition. Therefore, the ratio of each component other than the solvent in the conductive composition can be appropriately adjusted so that the ratio of each component in the conductive layer becomes a desired ratio.

  The conductive composition can be applied using a coating apparatus such as a bar coater. Application | coating may be performed with respect to the whole surface of the surface of a base film, and may be performed only to the one part area | region of the surface of a base film.

  The conditions for drying the layer of the conductive composition can be appropriately adjusted so that a desired conductive layer is obtained. A drying temperature can be 70-200 degreeC, for example. The drying time can be, for example, 0.5 minutes to 20 minutes.

  After the conductive layer is formed by the drying process, the conductive layer can be formed into a desired shape as necessary. The molding can be performed by a film removal method such as etching or photolithography.

[3.7. Conductive layer shape etc.)
The thickness of the conductive layer is preferably 50 nm or more, more preferably 80 nm or more, while preferably 1000 nm or less, more preferably 900 nm or less. By setting the thickness of the conductive layer to the above lower limit or more, the conductivity can be improved. By setting the thickness of the conductive layer to the upper limit or less, the total light transmittance can be improved.

  The conductive layer can be usually provided only on one side of the base film, but the present invention is not limited to this, and the conductive layer may be provided on both sides of the base film.

[4. Any layer)
The transparent conductive film of the present invention can include an arbitrary layer in addition to the base film and the conductive layer. For example, a primer layer for improving the peel strength can be provided between the base film and the conductive layer. However, it is preferable that the transparent conductive film of the present invention is not provided with a primer, and a conductive layer is directly formed on a base film formed of the material exemplified above. The transparent conductive film of this aspect can be efficiently manufactured with a small number of steps, and the film thickness of the conductive layer becomes uneven due to the uneven shape generated on the primer surface in the primer forming step, and the conductivity is impaired. This can be avoided. The transparent conductive film of the present invention is excellent in that it has the advantages described above by making the components of the conductive layer the specific ones described above and not having the primer layer. Adhesiveness between the base film and the conductive layer can be obtained. Moreover, the transparent conductive film of this invention can be equipped with an adhesive layer on a conductive layer. The transparent conductive film of the present invention obtains good adhesion between the conductive layer and the pressure-sensitive adhesive layer laminated on the conductive layer by setting the components of the conductive layer as described above. Can do.

[5. Properties of transparent conductive film)
The transparent conductive film preferably has a low surface resistance measured on the surface on the conductive layer side. The surface resistance is preferably 200Ω / □ or less, and more preferably 150Ω / □ or less. The lower limit of the surface resistance is not particularly limited, and is ideally 0Ω / □. The transparent conductive film of the present invention has such a low surface resistance by setting the components of the conductive layer as described above, and has high transparency and good base film and conductive layer. Adhesion can be obtained. The surface resistance can be measured using, for example, Loresta-AP MCP-T400 manufactured by Mitsubishi Chemical Corporation.

  The transparent conductive film preferably has high transparency. Specifically, it is preferable to have a high total light transmittance. The total light transmittance of the transparent conductive film is preferably 83% or more, more preferably 85% or more. The upper limit of the total light transmittance is not particularly limited and is ideally 100%. By making the components of the conductive layer as described above, low surface resistance and good adhesion between the base film and the conductive layer can be obtained while realizing such high total light transmittance. .

  The haze of the transparent conductive film is not particularly limited and can be a value according to the application. When using a transparent conductive film as a component of a touch panel, the haze of the transparent conductive film is usually preferably low, preferably 3% or less, more preferably 1% or less.

  The total light transmittance and haze of the transparent conductive film can be measured according to JIS K7136, for example, using a Nippon Denshoku haze meter NDH-2000.

[6. (Use)
The use of the transparent conductive film of the present invention is arbitrary. As an example of a use, the use as an electroconductive structural element in a display apparatus is mentioned. Examples of the conductive constituent element include an antistatic film and a constituent element for detecting contact on the touch panel.

[7. Touch panel)
The touch panel of the present invention includes the transparent conductive film of the present invention.
In the present invention, the touch panel is an electronic component having a combination of a function for displaying an image and a function for detecting a user operation on the display surface of the image. Examples of the touch panel operation detection system of the present invention include a resistive film system, an electromagnetic induction mode, and a capacitive system, and the present invention can be preferably applied particularly to a capacitive touch panel. The image display method of the touch panel of the present invention is not particularly limited, and any display device method such as a liquid crystal display device or an organic electroluminescence display device can be adopted.

  When the touch panel of the present invention includes a liquid crystal display device, the liquid crystal display device includes a liquid crystal cell including a pair of substrates and a liquid crystal compound sealed therebetween, and the front surface side and the back surface of the liquid crystal cell. It can be set as the apparatus containing a pair of polarizing plate provided in the side. In such an apparatus, the position at which the transparent conductive film of the present invention is provided is not particularly limited, and is located outside the pair of polarizing plates (out-cell), inside the pair of polarizing plates and outside the liquid crystal cell (on-cell). In addition, a desired position such as a position inside the liquid crystal cell (in-cell) can be used.

  The transparent conductive film of the present invention can be a film having low surface resistance, high transparency, and high durability, and a film having low birefringence by appropriately selecting a base film. Therefore, it can be preferably used at the on-cell and in-cell positions. Therefore, the touch panel of the present invention can be preferably configured as a touch panel including an on-cell type or in-cell type operation detection device.

  Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the following examples, and can be implemented with any modifications without departing from the scope of the claims of the present invention and the equivalents thereof. The operations described below were performed in a normal temperature and pressure atmosphere unless otherwise specified.

〔Evaluation method〕
(Cross-cut peel test)
According to JIS K5600, it implemented at 100 square of 1 mm square.

(Repeated cellotape (registered trademark) peel test)
In the transparent conductive films obtained in Examples and Comparative Examples, an adhesive tape (manufactured by Nichiban Co., Ltd., trade name “Cellotape CT405AP-24”) is bonded to the layer on the conductive layer side, and the operation of peeling is repeated. Evaluation was performed according to the evaluation criteria.
Excellent: The conductive layer remains without being peeled even after 10 times of bonding and peeling operations.
Good: A conductive layer peels when the operation of bonding and peeling is performed 5 to 9 times.
Defect: The conductive layer peels when the operations of bonding and peeling are performed 1 to 4 times.

(Adhesive adhesion test)
The conductive layer sides of the two transparent conductive films obtained in Examples and Comparative Examples were bonded together using an adhesive (manufactured by Nitto Denko Corporation, trade name “LUCIACS (registered trademark) CS9621T”). The bonded sample was cut into a 50 mm square and allowed to stand for 500 hours in an environment of a constant temperature and humidity chamber (60 ° C., 90%), and then the adhesion was evaluated according to the following criteria.
Excellent: No peeling of the bonded film is observed.
Good: Peeling within 2 mm from the edge of the bonded film is observed.
Good: Peeling within 5 mm from the edge of the bonded film is observed.
Defect: Peeling exceeding 5 mm is observed from the edge of the bonded film.

(Measurement of total light transmittance and haze)
It measured according to JISK7361 and JISK7136 using Nippon Denshoku Co., Ltd. haze meter NDH-2000.

(Measurement of surface resistance)
It measured using Mitsubishi Chemical Corporation Loresta-AP MCP-T400.

[Example 1]
(1-1. Base film)
An alicyclic structure polymer film (manufactured by Nippon Zeon Co., Ltd., trade name “Zeonor film ZF16-100”, thickness 100 μm) was prepared. This film was subjected to corona treatment at a discharge amount of 150 W / m ² / min in the atmosphere using a corona treatment device manufactured by Kasuga Denki Co., Ltd. to obtain a base film.

(1-2. Conductive composition)
The following components were mixed in the following blending amounts to obtain a conductive composition.
PEDOT / PSS dispersion (trade name “Clevios PH1000”, manufactured by Heraeus, aqueous dispersion with a solid content of 1.1%): 0.45 g
Phenol derivative solution (26DMPC / IPA = 1/99): 0.45 g
Polyamide compound resin solution (partial methoxymethylated 6-nylon, methoxymethylation rate 30%, trade name “FR105”, manufactured by Lead City Corporation, partially methoxymethylated 6-nylon / IPA / water = 1/29/70 Solution): 0.1 g
IPA: 1.0g

(1-3. Production and evaluation of transparent conductive film)
The conductive composition obtained in (1-2) was applied to the surface subjected to the corona treatment of the base film obtained in (1-1) with a # 26 bar coater and dried at 120 ° C. for 5 minutes. Thereby, the conductive layer was formed on the surface of the base film, and a transparent conductive film was obtained.
The obtained transparent conductive film was subjected to a cross-cut peel test, a repeated cello tape peel test, an adhesive adhesion test, a total light transmittance measurement, a haze measurement, and a surface resistance measurement. The results are shown in Table 2.

[Example 2]
A transparent conductive film was obtained and evaluated in the same manner as in Example 1 except that the blending ratio of the components of the conductive composition in (1-2) was changed and was as described below. The results are shown in Table 2.
PEDOT / PSS dispersion (same as used in Example 1): 0.4 g
Phenol derivative solution (same as used in Example 1): 0.4 g
Polyamide compound resin solution (same as used in Example 1): 0.2 g
IPA: 1.0g

Example 3
A transparent conductive film was obtained and evaluated in the same manner as in Example 1 except that the type and blending ratio of the components of the conductive composition in (1-2) were changed and the following was performed. The results are shown in Table 2.
PEDOT / PSS dispersion (same as used in Example 1): 0.4 g
Phenol derivative solution (same as used in Example 1): 0.4 g
Polyamide compound resin solution (partially alkylated polyamide, trade name “AQ nylon A90”, manufactured by Toray Industries, Inc., partially alkylated polyamide / IPA / water = 1/29/70): 0.2 g
IPA: 1.0g

Example 4
A transparent conductive film was obtained and evaluated in the same manner as in Example 1 except that the type and blending ratio of the components of the conductive composition in (1-2) were changed and the following was performed. The results are shown in Table 2.
PEDOT / PSS dispersion (same as used in Example 1): 0.4 g
Phenol derivative solution (same as used in Example 1): 0.4 g
Polyamide compound resin solution (including polymerized units of copolymer nylon, 6-nylon, 66-nylon and 610-nylon, trade name “Amilan CM8000”, manufactured by Toray Industries, Inc., copolymer nylon / IPA / water = 1/29 / 70 solution): 0.2 g
IPA: 1.0g

Example 5
(5-1. Production of resin pellets)
Into a reactor equipped with a stirrer in which the inside was sufficiently purged with nitrogen, 550 parts of dehydrated cyclohexane, 45.0 parts of dehydrated styrene, and 0.475 part of di-n-butyl ether were placed. While stirring the whole volume at 60 ° C., 0.83 part of n-butyllithium (15% cyclohexane solution) was added to initiate polymerization, and the reaction was further continued for 60 minutes while stirring at 60 ° C. When the reaction solution was measured by gas chromatography, the polymerization conversion rate was 99.5% at this point.
Thereafter, 10.0 parts of dehydrated isoprene was added to the reaction solution, and stirring was continued at 60 ° C. for 30 minutes. When the reaction solution was measured by gas chromatography, the polymerization conversion rate was 99% at this point.
Thereafter, 45.0 parts of dehydrated styrene was added to the reaction solution, and the whole volume was stirred at 60 ° C. for 60 minutes. When the reaction solution was measured by gas chromatography, the polymerization conversion rate at this point was almost 100%.
Here, 0.5 part of isopropyl alcohol was added to stop the reaction to obtain a polymer solution containing a block copolymer. The obtained block copolymer had a weight average molecular weight (Mw) of 50,400, a molecular weight distribution (Mw / Mn) of 1.03, and the ratio of the styrene block to the isobutylene block was 90:10.

  Next, the polymer solution was transferred to a pressure resistant reactor equipped with a stirrer, and 4.0 parts of a diatomaceous earth-supported nickel catalyst (“E22U” manufactured by JGC Catalysts & Chemicals, 60% nickel supported) as a hydrogenation catalyst. And 100 parts of dehydrated cyclohexane were added and mixed. The inside of the reactor was replaced with hydrogen gas, and hydrogen was supplied while stirring the solution. A hydrogenation reaction was carried out at a temperature of 170 ° C. and a pressure of 4.5 MPa for 6 hours. The weight average molecular weight (Mw) of the block copolymer hydride obtained by the hydrogenation reaction was 53,000, and the molecular weight distribution (Mw / Mn) was 1.04.

  After completion of the hydrogenation reaction, the reaction solution was filtered to remove the hydrogenation catalyst. Then, pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (“Songnox 1010” manufactured by Koyo Chemical Laboratory Co., Ltd.), which is a phenolic antioxidant, was added to the filtrate. 1.0 part of xylene solution in which 05 parts by weight were dissolved was added and dissolved. Next, the solution is filtered with a Zeta Plus (registered trademark) filter 30H (Cuno, pore size 0.5 μm to 1 μm), and further with another metal fiber filter (Nichidai Corp., pore size 0.4 μm). Sequential filtration removed fine solids. Thereafter, cyclohexane, xylene and other volatile components as solvents were removed from the solution at a temperature of 260 ° C. and a pressure of 0.001 MPa or less using a cylindrical concentration dryer (manufactured by Hitachi, Ltd., Contro). The remaining solid content was extruded as a strand in a molten state from a die directly connected to a concentration dryer, cooled, and then cut with a pelletizer to obtain 95 parts of a pellet containing a block copolymer hydride. The resulting block copolymer hydride had a weight average molecular weight (Mw) of 52,200, a molecular weight distribution (Mw / Mn) of 1.05, and a hydrogenation rate of almost 100%.

(5-2. Production of film)
The pellet obtained in (5-1) was molded by a melt extrusion method to obtain a hydride film (thickness: 100 μm) of a block copolymer of an aromatic vinyl compound and a conjugated diene compound.

(5-3. Production and evaluation of transparent conductive film)
A transparent conductive film was obtained and evaluated in the same manner as in Example 1 except that the following matters were changed. The results are shown in Table 2.
In (1-1), the film obtained in (5-2) was used in place of the alicyclic structure polymer film.
The blending ratio of the components of the conductive composition in (1-2) was changed to the same ratio as the orientation ratio in Example 2.

Example 6
A transparent conductive film was obtained and evaluated in the same manner as in Example 1 except that the type and blending ratio of the components of the conductive composition in (1-2) were changed and the following was performed. The results are shown in Table 2.
PEDOT / PSS dispersion (same as used in Example 1): 0.4 g
Phenol derivative solution (same as used in Example 1): 0.4 g
Polyamide compound resin solution (same as used in Example 1): 0.2 g
Leveling agent (ethylene oxide adduct of 2,4,7,9-tetramethyl-5-decyne-4,7-diol, trade name “Surfinol 440”, manufactured by Nissin Chemical Industry Co., Ltd.): 0.0002 g
IPA: 1.0g

[Comparative Example 1]
A norbornene-based resin film (manufactured by JSR Corporation, trade name “ARTON film”, thickness 100 μm, water absorption rate: 0.17%, photoelastic coefficient 3 × 10 ⁻¹³ cm ² / dyne) was prepared. This film was subjected to corona treatment in the air at an irradiation dose of corona discharge electrons of 100 W / m ² / min to obtain a base film.

A conductive composition (trade name “Orgacon S-300” (manufactured by Japan Agfa Gevaert Co., Ltd.)) is applied to the surface of the base film subjected to corona treatment so that the weight of the aqueous dispersion is 25 g / m ^2. And heated at 120 ° C. for 3 minutes to evaporate water. Thereby, the conductive layer was formed on the surface of the base film, and a transparent conductive film was obtained.
The obtained transparent conductive film was subjected to a cross-cut peel test, a repeated cello tape peel test, an adhesive adhesion test, a total light transmittance measurement, a haze measurement, and a surface resistance measurement. The results are shown in Table 3.

[Comparative Example 2]
A transparent conductive film was obtained and evaluated in the same manner as in Example 1 except that the blending ratio of the components of the conductive composition in (1-2) was changed and was as described below. The results are shown in Table 3.
PEDOT / PSS dispersion (same as used in Example 1): 1.0 g
IPA: 1.0g

[Comparative Example 3]
A transparent conductive film was obtained and evaluated in the same manner as in Example 1 except that the blending ratio of the components of the conductive composition in (1-2) was changed and was as described below. The results are shown in Table 3.
PEDOT / PSS dispersion (same as used in Example 1): 0.5 g
Polyamide compound resin solution (same as used in Example 1): 0.5 g
IPA: 1.0g

* 1 HSIS A hydride of a block copolymer of an aromatic vinyl compound and a conjugated diene compound.
* 2 Polyamide / conductive layer Percentage of polyamide compound in the conductive layer (unit weight%).

  As is apparent from the results of Tables 2 to 3, in the examples in which the conductive layer contains the predetermined component of the present invention, compared with the comparative example, while realizing high total light transmittance, low haze and surface resistance, It can be seen that the peel strength is high and the durability is high against repeated peel loads.

Claims (4)

A base film containing a alicyclic structure-containing polymer, or a hydride of a block copolymer of an aromatic vinyl compound and a conjugated diene compound, or a combination thereof; and provided on the surface of the base film. And a conductive layer
A transparent conductive film, wherein the conductive layer includes a polythiophene compound, a polystyrene sulfonic acid compound, a conductivity improver, and a polyamide compound.   The transparent conductive film of Claim 1 in which the said electroconductivity improver contains a phenol derivative.   The transparent conductive film according to claim 1, wherein the conductive layer contains a leveling agent.   A touch panel provided with the transparent conductive film of any one of Claims 1-3.