JP2016207041A - Transparent Conductive Laminate and Method for Producing the Same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transparent conducive laminate having high flexibility, transparency and conductivity.SOLUTION: A transparent conductive laminate is prepared by sequentially combining a base material layer containing at least one transparent resin selected from the group consisting of polyester, polycarbonate, polyimide, a polysulfonic resin and polyarylketone, a functional layer containing a cyclic olefin resin containing an olefin unit having an alkyl group having 2 to 10 carbon atoms in the side chain, and a transparent conductive layer. The transparent conductive layer may contain a metal oxide. The transparent conductive laminate further contains an anchor coat layer containing a chlorine-containing resin, and the anchor coat layer may be interposed between the functional layer and the base material layer. The transparent conductive laminate may have the total light transmittance of 80% or more, and a haze of 2% or less. A surface resistance value of the transparent conductive layer may be 50-200 Ω/square.SELECTED DRAWING: None

Description

  The present invention relates to a transparent conductive laminate that can be used for a display device (such as a touch panel display) having a patterned transparent conductive layer, and a method for producing the same.

  In recent years, with the advancement of electronic displays as man-machine interfaces, interactive input systems have become widespread. Among them, devices that integrate a touch panel (coordinate input device) with a display are ATMs (automated teller machines), merchandise management, Widely used in outworkers (diplomatic, sales), information display, entertainment equipment. Lightweight and thin displays such as liquid crystal displays can be made keyboard-less, and their features are alive, so the number of cases where touch panels are used in mobile devices is increasing. The touch panel can be classified into an optical method, an ultrasonic method, a capacitance method, a resistance film method, and the like according to a position detection method. Among these methods, the electrostatic capacitance method is a method for detecting a position by using a change in electrostatic capacitance. However, in recent years, the electrostatic capacitance method adopts an ITO grid method because of its excellent functionality. Capacitive touch panels are in the spotlight as they are used in mobile devices such as smartphones, mobile phones, electronic paper, tablet personal computers (PCs), pen tablets, and game machines. In the ITO grid method, a patterned ITO (indium oxide-tin oxide composite oxide) film is formed on a transparent substrate, but the transparent substrate is usually excellent in transparency and heat resistance. Glass substrates are widely used. However, since glass substrates are easily broken and cannot be produced on a roll-to-roll basis, the use of plastic substrates is also being considered.

  On the other hand, polyester substrates such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) are widely used as transparent plastic substrates because they are inexpensive and excellent in transparency. However, since the polyester substrate has low heat resistance, it is difficult to make the ITO film highly dense (crystallized), and it is difficult to form a conductive film having high transparency and low resistance. Furthermore, since the refractive index of the ITO film is higher than that of the polyester base material, a phenomenon that the pattern by the ITO film is visually recognized (so-called “pattern appearance” or “bone appearance” phenomenon) is likely to occur.

  On the other hand, these characteristics are balanced by interposing an optical adjustment layer between the polyester substrate and the ITO film. However, low resistance required for a capacitive touch panel having a relatively large screen has not been realized in recent tablet PCs and the like. In addition, although the polyimide film is also examined as a transparent plastic base material with high heat resistance, the adhesiveness with respect to a conductive layer is low, and it is easy to absorb water.

On the other hand, utilization of cyclic polyolefin as a transparent base material excellent in transparency and heat resistance is also being studied. JP-A-2011-43628 (Patent Document 1), the copolymerization ratio of norbornene and ethylene 80: 20~90: 10, MVR (melt volume rate) of 0.8 to 2.0 ^3/10 min And a substrate (retardation film) having a retardation of 100 to 150 nm made of an addition (co) polymer of a cyclic olefin having a glass transition temperature of 170 to 200 ° C., and an ITO transparent conductive film formed on at least one surface of the substrate, There is disclosed a capacitive touch panel including In this document, after forming a transparent conductive film while maintaining the temperature of the substrate at -10 to 150 ° C., a transparent conductive film having a resistance value of 100 to 1000 Ω / □ is formed by heat treatment at 140 to 180 ° C. In the examples, after forming an ITO transparent conductive film by sputtering at 90 ° C., a method of heat-treating at 165 ° C. and a method of forming an ITO transparent conductive film by sputtering at 150 ° C., 236 to 256 Ω / □ A transparent conductive laminate for a touch panel having a resistance value of is prepared.

  However, even a substrate formed of such an addition polymer of a cyclic olefin does not have sufficient heat resistance and cannot achieve the low resistance required for tablet PCs.

JP 2011-43628 A (Claims, Examples)

  Accordingly, an object of the present invention is to provide a transparent conductive laminate having high flexibility, transparency and conductivity and a method for producing the same.

  Another object of the present invention is to provide a transparent conductive laminate that can be manufactured by a roll-to-roll method, is not only high in productivity, but can be bent, and can realize a flexible device, and a method for manufacturing the same. is there.

  In order to achieve the above object, the inventors of the present invention are flexible by combining a functional layer containing a cyclic olefin resin containing an olefin unit having an alkyl group having 2 to 10 carbon atoms in the side chain and a transparent conductive layer. The present invention was completed by finding that the transparency and conductivity can be improved while maintaining the properties.

  That is, the transparent conductive laminate of the present invention has a base material layer containing at least one transparent resin selected from the group consisting of polyester, polycarbonate, polyimide, polysulfone-based resin, and polyaryl ketone, and has carbon atoms in the side chain. A functional layer including a cyclic olefin-based resin including an olefin unit having 2 to 10 alkyl groups and a transparent conductive layer are sequentially (in this order) included. The cyclic olefin-based resin may include a chain olefin unit having an alkyl group having 2 to 10 carbon atoms and / or a cyclic olefin unit having an alkyl group having 2 to 10 carbon atoms as a repeating unit, It may be a copolymer containing a cyclic olefin unit (A) having no alkyl group having 2 to 10 carbon atoms and a chain or cyclic olefin unit (B) having an alkyl group having 2 to 10 carbon atoms. . The chain or cyclic olefin unit (B) may be an ethylene or norbornene unit having a linear alkyl group having 4 to 8 carbon atoms. The ratio (molar ratio) between the cyclic olefin unit (A) and the chain or cyclic olefin unit (B) may be about the former / the latter = 50/50 to 99/1. About 210-350 degreeC may be sufficient as the glass transition temperature of the said cyclic olefin resin. The aluminum content of the functional layer may be 50 ppm or less. The transparent conductive layer may contain a metal oxide.

  The transparent conductive laminate of the present invention further comprises a base material layer containing at least one transparent resin selected from the group consisting of polyester, polycarbonate, polyimide, polysulfone resin and polyaryl ketone, The functional layer may be interposed between the transparent conductive layer. The transparent conductive laminate including such a base material layer may further include an anchor coat layer containing a chlorine-containing resin, and the anchor coat layer may be interposed between the functional layer and the base material layer.

  The transparent conductive laminate of the present invention may have a total light transmittance of 80% or more and a haze of 2% or less. The surface resistance value of the transparent conductive layer may be 50 to 200Ω / □. The transparent conductive laminate of the present invention may have a mandrel diameter of 4 mm or less in a bending resistance test according to JIS K5600-5-1.

  In this invention, it is a manufacturing method of the said transparent conductive laminated body including the transparent conductive layer formation process which forms the transparent conductive layer containing a metal oxide on the said functional layer, Comprising: In the said transparent conductive layer formation process, Also included is a production method in which a transparent conductive layer is formed by sputtering at a temperature of 180 ° C. or higher, or after being sputtered and heated at a temperature of 180 ° C. or higher to form a transparent conductive layer. The production method of the present invention may further include a functional layer forming step of forming a functional layer on the base material layer by coating.

  In the present invention, a base layer containing at least one transparent resin selected from the group consisting of polyester, polycarbonate, polyimide, polysulfone resin and polyaryl ketone, and an olefin having an alkyl group having 2 to 10 carbon atoms in the side chain Since the functional layer containing the cyclic olefin-based resin containing the unit and the transparent conductive layer are sequentially combined, transparency and conductivity can be improved while maintaining flexibility. Therefore, it can be manufactured by a roll-to-roll method, and not only can productivity be improved, but also bending and flexible devices can be realized.

[Transparent conductive laminate]
(Functional layer)
The transparent conductive laminate of the present invention includes a functional layer containing a cyclic olefin-based resin containing an olefin unit having an alkyl group having 2 to 10 carbon atoms in the side chain. This functional layer is suitable for optical applications because it has high heat resistance, excellent handleability, and high transparency. In particular, when the transparent conductive layer is formed of a metal oxide layer of an ITO film, crystallization of the metal oxide layer can be promoted, and the conductivity of the transparent conductive layer can be improved.

The cyclic olefin resin only needs to contain an olefin unit having an alkyl group having 2 to 10 carbon atoms (for example, a C _3-10 alkyl group) in the side chain, and the C _2-10 alkyl group is a cyclic olefin resin. Even if the heat generated by increasing the glass transition temperature of the cyclic olefin-based resin is increased because the energy generated by deformation can be converted into thermal energy by being present as a side chain with a high degree of freedom relative to the main chain. , Can retain elasticity and toughness. In particular, in an α-olefin, when the carbon number of the terminal alkyl group is 3 or more, it becomes liquid at room temperature. However, even in the present invention, when the carbon number of the side chain alkyl group is 3 or more, the above-described effects are exhibited. . On the other hand, if the carbon number exceeds 10, the glass transition temperature is too low.

As the C _2-10 alkyl group, for example, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, Examples thereof include linear or branched alkyl groups such as octyl group, 2-ethylhexyl group, nonyl group and decanyl group. These C _2-10 alkyl groups can be used alone or in combination of two or more. Of these, a linear C _3-10 alkyl group (for example, a linear chain such as an n-butyl group, an n-hexyl group, and an n-octyl group) is preferable because of its excellent balance between heat resistance, elasticity, and toughness. C _4-9 alkyl group), more preferably a linear C _4-8 alkyl group (particularly a linear C _5-7 alkyl group such as an n-hexyl group).

As such a cyclic olefin resin, the cyclic olefin resin as a repeating unit is a cyclic olefin having a chain olefin unit having a C _2-10 alkyl group and / or a C _2-10 alkyl group as a repeating unit. The chain may contain a unit (particularly an ethylene or norbornene unit having a linear alkyl group having 4 to 8 carbon atoms), and may be a homopolymer. and Jo olefin units and / or the cyclic olefin unit is preferably a copolymer with other copolymerizable units, a cyclic olefin units having no C _2-10 alkyl group (a), C _2-10 alkyl group A copolymer containing a linear or cyclic olefin unit (B) having

  The polymerization component (monomer) for forming the cyclic olefin unit (A) is a polymerizable cyclic olefin having an ethylenic double bond in the ring, and includes a monocyclic olefin, a bicyclic olefin, and a tricyclic ring. It can be classified into the above polycyclic olefins.

Examples of monocyclic olefins include cyclic C _4-12 cycloolefins such as cyclobutene, cyclopentene, cycloheptene, and cyclooctene.

  Examples of the bicyclic olefin include 2-norbornene; norbornenes having a methyl group such as 5-methyl-2-norbornene and 5,5-dimethyl-2-norbornene; alkenyl groups such as 5-ethylidene-2-norbornene Norbornenes having an alkoxycarbonyl group such as 5-methoxycarbonyl-2-norbornene and 5-methyl-5-methoxycarbonyl-2-norbornene; norbornene having a cyano group such as 5-cyano-2-norbornene Examples: Norbornenes having an aryl group such as 5-phenyl-2-norbornene and 5-phenyl-5-methyl-2-norbornene; Octaline; Octaline having a methyl group such as 6-methyl-octahydronaphthalene .

  Examples of the polycyclic olefin include dicyclopentadiene; 2,3-dihydrodicyclopentadiene, methanooctahydrofluorene, dimethanooctahydronaphthalene, dimethanocyclopentadienonaphthalene, methanooctahydrocyclopentadienaphthalene, and the like. Derivatives having substituents such as 6-methyl-octahydronaphthalene; adducts of cyclopentadiene and tetrahydroindene; 3-pentamers of cyclopentadiene and the like.

These cyclic olefins can be used alone or in combination of two or more. Of these cyclic olefins, bicyclic olefins are preferred because they have a good balance between peelability and flexibility. The proportion of bicyclic olefins (particularly norbornenes) is 10 mol% or more with respect to the total cyclic olefins having no C _2-10 alkyl group (cyclic olefins for forming cyclic olefin units (A)). For example, it is 30 mol% or more, preferably 50 mol% or more, more preferably 80 mol% or more (particularly 90 mol% or more), and may be a bicyclic olefin alone (100 mol%). In particular, when the ratio of the tricyclic or higher polycyclic olefin is increased, it becomes difficult to use for production in a roll-to-roll system.

Exemplary bicyclic olefins, e.g., C _2-10 alkyl which may norbornene have a substituent group other than group (2-norbornene), have a substituent other than C _2-10 alkyl group An example is octalin (octahydronaphthalene). Examples of the substituent include a methyl group, an alkenyl group, an aryl group, a hydroxyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, an acyl group, a cyano group, an amide group, and a halogen atom. These substituents may be used alone or in combination of two or more. Of these substituents, a nonpolar group such as a methyl group is preferable because it does not impair the peelability. Among these bicyclic olefins, norbornenes such as norbornene and norbornene having a methyl group (particularly norbornene) are particularly preferable.

The polymerization component (monomer) for forming the chain or cyclic olefin unit (B) can form a C _2-10 alkyl group as a side chain with respect to the main chain of the cyclic olefin resin, and ethylene. a polymerizable olefins having sex double bond, to form a cyclic olefin units having linear olefins, C _2-10 alkyl group to form a linear olefin units having C _2-10 alkyl group Can be classified as cyclic olefins. The chain olefin unit may be a chain olefin unit generated by ring-opening of a cyclic olefin, but a unit having a chain olefin as a polymerization component is preferable from the viewpoint of easily controlling the ratio of both units.

Examples of the chain olefin include 1-butene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-nonene, 1-decene, 1 Examples include α-chain C _4-12 olefins such as -undecene and 1-dodecene. These chain olefins can be used alone or in combination of two or more. Among these chain olefins, α-chain C _5-12 olefins (for example, α-chain C _6-11 olefins) are preferable, and in terms of excellent balance of various properties such as polymer productivity, Preferred are α-chain C _6-10 olefins (particularly α-chain C _7-9 olefins such as 1-octene).

The cyclic olefin may be a cyclic olefin in which a C _2-10 alkyl group is substituted on the cyclic olefin skeleton exemplified in the paragraph of the cyclic olefin unit (A). As the cyclic olefin skeleton, a bicyclic olefin (particularly norbornene) is preferable. Preferred cyclic olefins having a C _2-10 alkyl group include, for example, 5-ethyl-2-norbornene, 5-propyl-2-norbornene, 5-butyl-2-norbornene, 5-pentyl-2-norbornene, 5- Examples thereof include linear or branched C _2-10 alkyl norbornene such as hexyl-2-norbornene, 5-octyl-2-norbornene, and 5-decyl-2-norbornene. These cyclic olefins can be used alone or in combination of two or more. Among these cyclic olefin, preferably linear _C is _3-10 alkyl norbornene, still preferably linear _C such as linear _{C 4-9} alkyl norbornene (particularly 5-hexyl-2-norbornene _{4- 8} alkyl norbornene).

  The ratio (molar ratio) between the cyclic olefin unit (A) and the chain or cyclic olefin unit (B) is, for example, the former / the latter = 50/50 to 99/1, preferably 60/40 to 95/5, Preferably it is about 70 / 30-90 / 10 (especially 75 / 25-90 / 10). When the ratio of the cyclic olefin unit (A) is too small, the heat resistance is lowered, and when it is too much, the toughness is easily lowered.

The cyclic olefin resin may contain other copolymerizable units in addition to the cyclic olefin unit (A) and the chain or cyclic olefin unit (B). Examples of polymerization components (monomers) for forming other copolymerizable units include α-chain C _2-3 olefins (ethylene, propylene, etc.), vinyl ester monomers (eg, vinyl acetate). , Vinyl propionate, etc.), diene monomers (eg, butadiene, isoprene, etc.), (meth) acrylic monomers [eg, (meth) acrylic acid, or derivatives thereof ((meth) acrylic esters, etc.) ) Etc.]. These polymerization components can be used alone or in combination of two or more. Of these, α-chain C _2-3 olefins such as ethylene and propylene are widely used. The ratio of the other copolymerizable unit is, for example, 10 mol% or less, preferably 5 mol% or less, more preferably 1%, based on the total of the cyclic olefin unit (A) and the chain or cyclic olefin unit (B). It is less than mol%.

  The number average molecular weight of the cyclic olefin-based resin is, for example, 10,000 to 300,000, preferably 20,000 to 250,000, and more preferably 30,000 to 200,000 (particularly 50,000 to 150,000) in terms of polystyrene in gel permeation chromatography (GPC). If the molecular weight is too small, the film-forming property is liable to be lowered, and if it is too large, the viscosity is increased, so that the handleability is liable to be lowered.

  The glass transition temperature (Tg) of the cyclic olefin-based resin can be selected from a range of about 210 to 350 ° C., and is, for example, 210 to 340 ° C., preferably 220 to 330 ° C. (for example, from the point of balance between heat resistance and mechanical properties) 220-310 ° C), more preferably about 230-300 ° C (especially 260-290 ° C). If the glass transition temperature is too low, the heat resistance is lowered and the treatment at high temperature tends to be difficult, and if it is too high, the production becomes difficult. In the present specification, the glass transition temperature can be measured using a differential scanning calorimeter (DSC).

  There is no particular limitation on the polymerization method of the cyclic olefin-based resin, and a conventional method such as addition polymerization using a Ziegler-type catalyst or addition polymerization using a metallocene-based catalyst can be used. Specific polymerization methods include, for example, JP-A No. 2004-107442, JP-A No. 2007-119660, JP-A No. 2008-255341, Macromolecules, 43, 4527 (2010), Polyhedron, 24, 1269 (2005). ), J. Appl. Polym. Sci, 128 (1), 216 (2013), Polymer Journal, 43, 331 (2011). Moreover, the catalyst used for superposition | polymerization can utilize the catalyst etc. which were synthesize | combined by the method as described in these literature.

  The ratio of the catalyst is, for example, 0.0001 to 0.05 parts by weight, preferably 0.0005 to 0.01 parts by weight, and more preferably 0.001 to 0.005 parts by weight with respect to 100 parts by weight of the cyclic olefin monomer. About 01 parts by mass.

Further, a conventional promoter may be used for the polymerization of the cyclic olefin resin. As the promoter, an aluminoxane compound that is a partial hydrolyzate of alkylaluminum (raw material) such as trimethylaluminum is usually used. Examples of the aluminoxane compound include C _1-6 alkylaluminoxanes such as methyl isobutylaluminoxane and methylaluminoxane, and poly C _1-6 alkylaluminoxanes such as polymethylaluminoxane. These aluminoxane compounds can be used alone or in combination of two or more.

  The proportion of the cocatalyst is not particularly limited as long as it is a proportion capable of exhibiting sufficient catalytic activity, and can be selected according to the catalytic activity. When an aluminoxane compound is used, the proportion of aluminum atoms per catalyst molecule is usually from an equivalent amount to 10,000 times the amount, preferably 10 to 5,000 times the amount, more preferably about 50 to 2,000 times the amount. is there.

  The functional layer may further contain a conventional additive. Examples of conventional additives include fillers, antistatic agents, stabilizers (antioxidants, heat stabilizers, light stabilizers, etc.), flame retardants, viscosity modifiers, thickeners, lubricants, antifoaming agents, etc. May be included. In addition, organic or inorganic particles (particularly, anti-blocking agents such as zeolite) may be included as long as the surface smoothness is not impaired.

  The ratio of the cyclic olefin-based resin in the functional layer is, for example, 80% by mass or more, preferably 90% by mass or more, more preferably 95% by mass or more (for example, 95 to 100% by mass) with respect to the entire functional layer. Also good.

  In particular, in the present invention, it is preferable that the content (content) of the metal component (especially aluminum) mixed in the production process of the cyclic olefin resin is small, and the content of the metal component (particularly aluminum) may be 100 ppm or less. For example, it may be about 50 ppm or less (for example, 0.001 to 50 ppm), preferably about 10 ppm or less (for example, 0.05 to 10 ppm), and more preferably about 5 ppm or less (for example, 0.1 to 5 ppm). When there is too much content of a metal component (especially aluminum), there exists a possibility that the high crystallization and transparency of a functional layer may be reduced. As a method of reducing the metal content in the functional layer (cyclic olefin resin), the amount of the catalyst and the cocatalyst is reduced, and the reaction solution after the polymerization is treated by a known method such as acid treatment or alkali treatment. Can be used.

  The average thickness of the functional layer is, for example, about 0.1 to 300 μm, preferably about 0.2 to 100 μm, and more preferably about 0.3 to 50 μm. When the functional layer is used alone as a base material without using the base material layer, the average thickness of the functional layer is, for example, about 10 to 200 μm, preferably about 50 to 150 μm.

  In particular, when the functional layer is a coating film, it may be thin, and the average thickness of the functional layer is, for example, 0.1 to 3 μm, preferably 0.15 to 2 μm, more preferably 0.2 to 1 μm (particularly It may be about 0.25 to 0.5 μm. If the functional layer is thin, it is easy to handle, suitable for a roll-to-roll method, etc., and economically improved. In the case of a coating film, the average thickness can be calculated based on the coating amount (solid content weight per unit area) and density of the functional layer.

(Transparent conductive layer)
The conductive laminate of the present invention further includes a transparent conductive layer, and this transparent conductive layer is usually laminated on one surface of the functional layer. The transparent conductive layer is not particularly limited as long as a conventional transparent conductive layer used for a transparent electrode or the like can be used, is transparent, and has conductivity, and is formed of a conductive polymer. Although it may be a conductive layer or the like, a transparent conductive layer formed of a conductive inorganic compound is preferable from the viewpoint that the effect of the above-described functionality that is formed at a high temperature and excellent in heat resistance can be remarkably exhibited.

The electrically conductive inorganic compound, for example, metal oxides [e.g., _(such as _{InO 2, In 2 O 3,} In 2 O 3 -SnO 2 composite oxide (ITO)) indium oxide, tin oxide _(SnO 2, SnO ₂ —Sb ₂ O ₅ composite oxide, fluorine-doped tin oxide (FTO), etc.), zinc oxide (ZnO, ZnO—Al ₂ O ₃ composite oxide, etc.)], metal (eg, gold, silver, platinum, palladium), etc. Is mentioned. These conductive inorganic compounds can be used alone or in combination of two or more. Of these conductive inorganic compounds, metal oxides are preferable from the viewpoint of transparency and conductivity, and indium oxide such as ITO is widely used.

In the In ₂ O ₃ —SnO ₂ composite oxide (ITO), the ratio of tin oxide (SnO ₂ ) may be 5% by mass or more, for example, 5 to 20% by mass, preferably Is 6 to 15% by mass, more preferably 7 to 12% by mass. In the present invention, a highly crystalline transparent conductive film can be obtained using ITO having a tin oxide ratio of about 10% by mass.

  The transparent conductive layer formed of a conductive inorganic compound can be formed by a conventional method, for example, sputtering, vapor deposition, chemical vapor deposition, etc. (usually sputtering). Such a transparent conductive layer may be, for example, the transparent conductive layer described in JP-A-2009-76544, JP-A-4165173, and JP-A-2004-14984. Among these methods, a transparent conductive layer formed by sputtering is preferable because it is easy to form a uniform thin film and is also effective in maintaining high conductivity by the functional layer under vacuum conditions. .

  The surface resistance value of the transparent conductive layer (particularly a transparent conductive layer formed of a metal oxide such as ITO) can realize a low resistance even though the functional layer is a plastic layer, for example, 200Ω / □ or less (for example, 50 to 200Ω / □), preferably 60 to 150Ω / □, and more preferably about 70 to 120Ω / □.

  The transparent conductive layer can be selected depending on the application. For example, in the case of a touch panel, the transparent conductive layer is usually formed in a planar shape in the analog method and in a stripe shape in the digital method. As a method for forming the transparent conductive layer into a planar shape or a stripe shape, for example, after forming the transparent conductive layer on the entire surface of the functional layer, it is patterned into a planar shape, a stripe shape, or a lattice shape (diamond or rhombus shape) by etching. And a method of forming a pattern in advance. The transparent conductive laminate of the present invention is preferably a patterned transparent conductive layer because the transparent conductive layer can be formed thin to suppress the phenomenon of pattern appearance in a display device (particularly a capacitive touch panel).

  The average thickness of the transparent conductive layer is not particularly limited as long as the transparency is not impaired, and can be selected from a range of about 1 to 1000 nm. From the viewpoint of excellent transparency, for example, 5 to 100 nm, preferably 10 to 80 nm, and more preferably. May be about 15 to 50 nm (particularly 20 to 40 nm). In the present invention, by laminating a transparent conductive layer on a functional layer, a thin and highly crystalline transparent conductive layer can be formed even if it is formed of a metal oxide, so that both transparency and conductivity can be achieved. .

(Base material layer)
The conductive laminate of the present invention further includes a base material layer, and the functional layer is interposed between the base material layer and the transparent conductive layer. By combining a base material layer with the functional layer, the functional layer can be formed on the base material layer by coating, so that a thin and uniform functional layer can be easily formed.

The base material layer is a material that does not impair transparency and flexibility, and from the viewpoint of excellent heat resistance, polyester (poly C _2-4 alkylene arylate resin such as PET and PEN, polyarylate resin, etc.), Polycarbonate (such as bisphenol A type polycarbonate), polyimide [thermosetting polyimide (such as pyromellitic acid-based polyimide, bismaleimide-based polyimide, nadic acid-based polyimide, acetylene-terminated polyimide), thermoplastic polyimide, polyetherimide, polyamideimide, etc. ], Polysulfone resins (polysulfone, polyethersulfone, etc.), polyaryl ethers (polyetherketone, polyetheretherketone, etc.) are preferably used.

These transparent resins can be used alone or in combination of two or more. Of these transparent resins, polyester resins, polyimides, and the like are widely used, and poly C _2-4 alkylene naphthalate resins such as polyethylene naphthalate are particularly preferable from the viewpoint of excellent balance of heat resistance, transparency, and economy. .

  The base material layer may be formed of a stretched film from the viewpoint of imparting retardation and improving film strength. The stretching may be uniaxial stretching, but biaxial stretching is preferred from the viewpoint that the film strength can be improved. The stretching ratio may be, for example, 1.2 times or more (for example, 1.2 to 6 times), preferably 1.5 to 5 times, and more preferably about 2 to 4 times in the longitudinal and transverse directions. It is. If the draw ratio is too low, the film strength tends to be insufficient.

  The average thickness of a base material layer is 5-300 micrometers, for example, Preferably it is 10-200 micrometers, More preferably, it is about 30-100 micrometers.

  The base material layer may also contain a conventional additive exemplified in the section of the functional layer. The ratio of the transparent resin in the substrate layer is, for example, 80% by mass or more, preferably 90% by mass or more, more preferably 95% by mass or more (for example, 95 to 100% by mass) with respect to the entire substrate layer. Also good.

(Underlayer)
In the conductive laminate of the present invention, a conventional underlayer may be formed between the transparent conductive layer and the functional layer in order to improve the adhesion to the functional layer and the conductivity of the transparent conductive layer. As the underlayer, a conventional underlayer can be used depending on the type of the transparent conductive layer. When the transparent conductive layer is formed of a metal oxide such as indium oxide, the base layer may be a layer containing silicon oxide (SiO ₂ ). The average thickness of the underlayer is not particularly limited as long as the transparency is not impaired, and may be, for example, 3 to 100 nm, preferably 5 to 50 nm, and more preferably about 10 to 30 nm.

[Anchor coat layer]
An anchor coat layer may be further interposed between the base material layer and the functional layer in order to improve the adhesion between the two layers. The anchor coat layer may be a conventional adhesive layer, but preferably contains a chlorine-containing resin from the viewpoint that the adhesion of the functional layer containing the cyclic olefin resin to the base material layer can be improved.

  The chlorine-containing resin may be a chlorinated resin such as chlorinated polyethylene or chlorinated polypropylene, but is usually a polymer having a chlorine-containing monomer as a polymerization component. Examples of the chlorine-containing monomer include a vinyl chloride monomer and a vinylidene chloride monomer. These chlorine-containing monomers can be used alone or in combination of two or more. Of these, vinylidene chloride monomer is preferred from the viewpoint of adhesion to the base film.

  The chlorine-containing resin may contain other copolymerizable units other than the chlorine-containing monomer. Examples of the polymerization component for forming other copolymerizable units include a copolymerizable monomer of a cyclic olefin resin exemplified in the section of the functional layer. The copolymerizable monomers can be used alone or in combination of two or more. Among the copolymerizable monomers, vinyl acetate, (meth) acrylic acid, (meth) acrylic acid alkyl ester, (meth) acrylic acid hydroxyalkyl ester, glycidyl (meth) acrylate, (meth) acrylonitrile, etc. are widely used. The

  The proportion of the other copolymerizable units (copolymerizable monomer) may be such that the properties of the chlorine-containing resin are not impaired, and is generally 0.1 to 50% by mass (for example, 0.3 to 25% by mass), preferably 0.5 to 20% by mass, and more preferably about 1 to 15% by mass (for example, 3 to 10% by mass).

  Examples of the chlorine-containing resin include a vinyl chloride polymer [a vinyl chloride monomer homopolymer (polyvinyl chloride), a vinyl chloride copolymer (vinyl chloride-vinyl acetate copolymer, vinyl chloride- (meth) acrylic). Acid ester copolymer, etc.)], vinylidene chloride polymer [vinylidene chloride homopolymer (polyvinylidene chloride), vinylidene chloride copolymer (vinylidene chloride-vinyl chloride copolymer, vinylidene chloride-vinyl acetate copolymer) Polymer, vinylidene chloride- (meth) acrylic acid copolymer, vinylidene chloride- (meth) acrylic acid ester copolymer, vinylidene chloride- (meth) acrylonitrile copolymer, etc.)] and the like. These chlorine-containing resins can be used alone or in combination of two or more.

  Among these chlorine-containing resins, vinylidene chloride polymers (particularly, vinylidene chloride copolymers such as vinylidene chloride-vinyl chloride copolymers) are used because the adhesion between the functional layer and the base material layer can be improved. preferable. In the vinylidene chloride-vinyl chloride copolymer, the ratio (molar ratio) between the vinylidene chloride unit and the vinyl chloride unit is, for example, the former / the latter = 99/1 to 5/95, preferably 97/3 to 10/90, More preferably, it is about 95/5 to 50/50. The vinylidene chloride polymer may not contain an emulsifier, a surfactant and the like contained in the aqueous emulsion.

  The number average molecular weight of the chlorine-containing resin is, for example, 10,000 to 500,000, preferably 20,000 to 250,000, more preferably 25,000 to 100 in terms of polystyrene in gel permeation chromatography (GPC). It may be about 1,000.

  The anchor coat layer may further contain an adhesive component as necessary in order to improve the adhesion between the functional layer and the base material layer. Examples of the adhesive component include polyolefin resin (modified polyethylene such as polyethylene graft copolymer), acrylic resin, polyamide resin, polyester resin (such as thermoplastic copolymer polyester), reactive adhesive component [isocyanate compound, Imino group-containing polymer (polyethyleneimine and the like)] and the like. These adhesive components can be used alone or in combination of two or more.

  Of these adhesive components, reactive adhesive components are preferred, and isocyanate compounds are particularly preferred.

  The isocyanate compound may be a prepolymer or an oligomer having a terminal isocyanate group, but is usually a polyisocyanate such as an aliphatic isocyanate, an alicyclic isocyanate, an aromatic isocyanate, or a derivative thereof. Also good.

  Examples of the aliphatic isocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), and the like. Examples of the alicyclic isocyanate include 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, isophorone diisocyanate (IPDI), and hydrogenated tolylene diisocyanate. (Hydrogenated TDI), hydrogenated xylylene diisocyanate (hydrogenated XDI), hydrogenated diphenylmethane-4,4′-diisocyanate (hydrogenated MDI), and the like. Examples of the aromatic isocyanate include tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), diphenylmethane-4,4'-diisocyanate (MDI), and the like.

  Examples of the isocyanate derivative include, for example, the above-mentioned isocyanate multimer [dimer (uretdione group-containing isocyanate), trimer (isocyanurate ring-containing isocyanate), pentamer, heptamer, etc.], Examples include modified products (such as allophanate-modified isocyanate, burette-modified isocyanate, urea-modified isocyanate, and carbodiimide-modified isocyanate), adducts of polyhydric alcohols and the above isocyanates, and the like.

  Of these isocyanate compounds, aromatic isocyanates such as TDI, MDI, XDI and TMXDI and derivatives thereof are preferred.

  The proportion of the adhesive component may be about 0.1 to 30 parts by mass, preferably 0.5 to 20 parts by mass, and more preferably about 1 to 10 parts by mass with respect to 100 parts by mass of the chlorine-containing resin.

  The anchor coat layer may also contain a conventional additive exemplified in the section of the functional layer. The total ratio of the chlorine-containing resin and the adhesive component in the anchor coat layer is, for example, 80% by mass or more, preferably 90% by mass or more, more preferably 95% by mass or more (for example, 95 to 100% by mass) with respect to the entire anchor coat layer. %).

  The average thickness of the anchor coat layer may be, for example, about 0.01 to 80 μm, preferably 0.05 to 50 μm, and more preferably about 0.1 to 20 μm (particularly 0.2 to 10 μm).

(Characteristics of transparent conductive laminate)
As described above, the transparent conductive laminate of the present invention not only exhibits high conductivity in the transparent conductive layer, but also has excellent transparency, and the total light transmittance may be 80% or more. For example, it is 80 to 99%, preferably 82 to 95%, more preferably about 84 to 92% (especially 85 to 90%). In the present invention, the total light transmittance can be measured in accordance with the JIS K7361-1 method, and can be measured in detail by the method described in Examples described later.

  The transparent conductive laminate of the present invention has a low light scattering property, and haze may be 5% or less (for example, 0.1 to 5%), for example, 2% or less (for example, 0.2 to 2%), Preferably it is 0.3-1.5%, More preferably, it is about 0.4-1% (especially 0.5-0.8%). In the present invention, the haze can be measured according to JIS K7136 method, and can be measured in detail by the method described in the examples described later.

  The transparent conductive laminate of the present invention not only has excellent conductivity and optical properties (transparency), but also has excellent flexibility and bending resistance, and the mandrel diameter in the bending resistance test is 4 mm or less. It may be. In the present invention, the bending resistance test can be measured according to JIS K5600-5-1, and can be measured in detail by the method described in the examples described later.

  The conductive laminate of the present invention further includes other optical layers such as a hard coat layer, an antiglare layer, an anti-Newton ring layer, a light scattering layer, an antireflection layer, a low refractive index layer, a high refractive index layer, a phase difference. Layers and the like may be included.

[Method for producing transparent conductive laminate]
(Transparent conductive layer forming process)
The conductive laminate of the present invention is obtained by a production method including a transparent conductive layer forming step of forming a transparent conductive layer on a functional layer. The formation method of a transparent conductive layer is not specifically limited, According to the kind of transparent conductive layer, it can form using a conventional film forming (film formation) method. When the conductive layer is formed of a conductive inorganic compound, the film forming method may be, for example, physical vapor deposition (PVD) [for example, vacuum deposition, flash deposition, electron beam deposition, ion beam deposition, , Ion plating method (for example, HCD method, electron beam RF method, arc discharge method, etc.), sputtering method (for example, direct current discharge method, radio frequency (RF) discharge method, magnetron method, etc.), molecular beam epitaxy method, laser ablation Etc.], chemical vapor deposition (CVD) [for example, thermal CVD, plasma CVD, MOCVD (metal organic chemical vapor deposition), photo CVD, etc.], ion beam mixing, ion implantation, etc. It can be illustrated. Among these deposition methods, physical vapor phase methods such as vacuum deposition, ion plating, and sputtering, and chemical vapor phase are widely used, and uniform and thin films can be formed. Sputtering is particularly preferred from the standpoint of remarkably developing.

  In the sputtering method, the film forming temperature is, for example, about 60 to 300 ° C, preferably about 80 to 250 ° C, and more preferably about 100 to 200 ° C. Furthermore, in the present invention, since the functional layer is excellent in heat resistance, sputtering at a high temperature is possible, and the sputtering temperature may be 180 ° C. or higher, for example, 180 to 300 ° C., preferably 185 to 250 ° C., more preferably. 190-220 degreeC may be sufficient. In the present invention, since sputtering at a high temperature is possible, when the transparent conductive layer is formed of a metal oxide such as ITO, crystallization of the transparent conductive layer can be promoted, and a dense and low resistance transparent conductive layer is formed. Can be formed.

  In the transparent conductive layer forming step, heat treatment may be performed after sputtering. In particular, when the transparent conductive layer is formed of a metal oxide such as ITO, crystallization of the metal oxide can be promoted by heat treatment. The heat treatment is effective when sputtering is performed at a relatively low temperature. 180 degreeC or more may be sufficient as the temperature of heat processing, for example, 180-300 degreeC, Preferably it is 185-250 degreeC, More preferably, it is about 190-220 degreeC. If the heat treatment temperature is too low, crystallization is not promoted and the conductivity of the transparent conductive layer may be reduced.

  Sputtering and heat treatment may be performed under vacuum or in the presence of an inert gas (such as argon gas) and / or an active gas (such as oxygen gas). Usually, in the sputtering process for forming a transparent conductive layer with a metal oxide, a pre-vacuum process in which pressure is reduced to a high vacuum region, and further, an inert gas is introduced to a vacuum region where glow discharge is generated by applying a voltage. A transparent conductive layer is formed through a sputtering process in which the active gas is turned into plasma and the target is sputtered, and a reactive gas is introduced instead of the inert gas necessary for sputtering to form an oxide film. . Therefore, in order to form a dense transparent conductive layer, it is necessary to suppress the generation of volatile components (moisture, monomer, etc.) from the base material in the vacuum process in the preliminary vacuum process or the sputtering process. In this invention, since generation | occurrence | production of the volatile matter from a functional layer is suppressed, it can be estimated that a precise | minute transparent conductive layer can be formed.

(Underlayer forming process)
When forming the underlayer, the underlayer may be formed on the functional layer by the same method as the transparent conductive layer forming step as a pre-process of the transparent conductive layer forming step.

(Functional layer formation process)
Furthermore, in the said manufacturing method, the functional layer formation process which forms a functional layer is further included as a pre-process of a transparent conductive layer formation process. The method for forming the functional layer is not particularly limited and may be a molding method such as extrusion molding. However, the functional layer is formed on the base material layer by coating from the viewpoint that a uniform and thin functional layer can be easily formed. A functional layer forming step is preferable.

  In the functional layer forming step by coating, a method of drying after coating (or casting) a solution containing the cyclic olefin-based resin on the base material layer is preferable. As the coating method, conventional methods such as roll coater, air knife coater, blade coater, rod coater, reverse coater, bar coater, comma coater, die coater, gravure coater, screen coater method, spray method, spinner method and the like can be mentioned. It is done. Of these methods, the blade coater method, the bar coater method, the gravure coater method and the like are widely used.

  The solvent is not particularly limited as long as the cyclic olefin resin can be dissolved, and a nonpolar solvent can be usually used. Examples of such nonpolar solvents include aliphatic hydrocarbons such as hexane, alicyclic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as toluene and xylene, and aromatic oils such as solvent naphtha. Can be used. These solvents may be used alone or in combination of two or more. Of these, aromatic hydrocarbons such as toluene and aromatic oils such as solvent naphtha are preferred.

  The solid content concentration in the solution is, for example, about 0.1 to 50% by weight, preferably about 0.3 to 30% by weight, and more preferably about 0.5 to 20% by weight (particularly 0.8 to 15% by weight). .

  Drying may be natural drying, or the solvent may be evaporated by heating and drying. 50 degreeC or more may be sufficient as drying temperature, for example, 50-350 degreeC, Preferably it is 60-300 degreeC, More preferably, it is about 80-270 degreeC.

(Anchor coat layer formation process)
When the transparent conductive laminate of the present invention further includes an anchor coat layer, an anchor coat layer forming step of forming the anchor coat layer is further included as a pre-step of the functional layer forming step. The anchor coat layer forming step is also not particularly limited, and may be a molding method such as extrusion molding. However, from the viewpoint that a uniform and thin anchor coat layer can be easily formed, the anchor coat layer is coated on the base material layer by coating. An anchor coat layer forming step of forming is preferable. In this case, the functional layer is formed not on the base material layer but on the anchor coat layer.

  In the anchor coat layer forming step by coating, a method of drying after coating (or casting) a solution containing a chlorine-containing resin on the base material layer is preferable. As the coating method, the same coating method as in the functional layer forming step can be used.

  The solvent is not particularly limited as long as it can dissolve the chlorine-containing resin. For example, in addition to the nonpolar solvent exemplified in the functional layer forming step, a polar solvent can also be used. Examples of polar solvents that can be used include dialkyl ketones such as acetone and methyl ethyl ketone, and ethers such as tetrahydrofuran and dioquinsan. These solvents can be used alone or in combination of two or more. Among these, the combination of a nonpolar solvent and a polar solvent is preferable, and the mass ratio of both is a nonpolar solvent / polar solvent = 1 / 99-50 / 50 (especially 10 / 90-30 / 70) grade. In particular, the nonpolar solvent may be an aromatic hydrocarbon (such as toluene). In addition, the polar solvent may be a combination of dialkyl ketones (such as methyl ethyl ketone) and cyclic ethers (such as tetrahydrofuran), and the mass ratio of the two is dialkyl ketones / cyclic ethers = 1/99 to 50 / It is about 50 (especially 10 / 90-40 / 60).

  The solid concentration in the solution is, for example, about 0.1 to 50% by weight, preferably about 0.3 to 20% by weight, more preferably about 0.5 to 10% by weight (particularly about 0.8 to 5% by weight). .

  Drying may be natural drying, or the solvent may be evaporated by heating and drying. 50 degreeC or more may be sufficient as drying temperature, for example, 50-200 degreeC, Preferably it is 80-180 degreeC, More preferably, it is about 100-150 degreeC.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. The characteristics of the transparent conductive laminates obtained in Examples and Comparative Examples were evaluated by the following methods.

[Glass-transition temperature]
Using a differential scanning calorimeter (“DSC6200” manufactured by SII Nanotechnology Co., Ltd.), the measurement was performed at a temperature rising rate of 10 ° C./min in a nitrogen stream according to JIS K7121.

[Composition ratio of cyclic olefin resin (A) / (B)]
The ratio (molar ratio) between the cyclic olefin unit (A) and the chain or cyclic olefin unit (B) was measured by ¹³ C-NMR.

[Surface resistance value]
About each transparent conductive laminated body, the surface resistance value was measured by the four-terminal method using the surface resistance meter ("Loresta GP MCP-T610 type | mold" by Mitsubishi Analytech Co., Ltd.).

[Total light transmittance]
About each transparent conductive laminated body, based on JISK7361-1, using a D65 fluorescent lamp as a light source, using a haze meter ("NDH-5000W" by Nippon Denshoku Industries Co., Ltd.), total light transmittance Was measured.

[Haze]
About each transparent conductive laminated body, based on JISK7136 method, D65 fluorescent lamp was used as a light source, and the haze was measured using the haze meter (Nippon Denshoku Industries Co., Ltd. "NDH-5000W").

[Flexibility]
Each transparent conductive laminate was cut into 1 × 10 cm squares to prepare sample pieces, and the bending resistance was determined based on the following method. That is, based on the cylindrical mandrel method (JIS K5600-5-1), a sample piece is wound around a plurality of mandrels having different diameters, and whether or not a crack is generated in the wound portion is visually observed. It was evaluated with.

○: No crack is generated in a mandrel having a diameter of 4 mm or less. ×: A crack is generated in a mandrel having a diameter of 4 mm or less.

[X-ray diffraction (XRD)]
About the transparent conductive film of the comparative example 1 and Examples 1-2, the XRD pattern was analyzed using the fully automatic horizontal multi-purpose X-ray-diffraction apparatus (Rigaku Co., Ltd. "SmartLab").

[Production of copolymer]
(Examples 1-4)
Each monomer shown in Table 1 and the catalyst and promoter shown in Table 2 were added to the dried glass reactor. The catalyst and the cocatalyst were each added to the reactor in a state dissolved in toluene. At the polymerization temperature and polymerization time shown in Table 3, the inside of the reactor was stirred and polymerization was continued, and then 1 part by mass of 2-propanol was added to terminate the reaction. Next, after adding concentrated hydrochloric acid shown in Table 3 to the obtained polymerization reaction liquid at room temperature and stirring for 30 minutes, 1/3 amount of ion-exchanged water of the solution amount (volume) was added, and further stirred for 10 minutes. The resulting mixture of the polymerization reaction solution and the aqueous layer was transferred to a separatory funnel, and the aqueous layer was separated and discarded. Next, the same amount of ion exchange water as above was added to the separatory funnel containing the polymerization reaction solution to wash the polymerization reaction solution, and then the aqueous layer was separated. After washing the polymerization reaction solution with ion-exchanged water several times to neutralize the aqueous layer, after pouring the polymerization reaction solution into a large amount of methanol to completely precipitate the polymer, filtering and washing Each copolymer was obtained by drying under reduced pressure at 60 ° C. or more for 1 day or more. The weight of the obtained copolymer was measured (“Yield” in Table 3). The ratio of the obtained copolymer to the amount of catalyst used was calculated (“g (copolymer) / g (catalyst)” in Table 3).

  The types of catalyst and cocatalyst used are as follows.

Catalyst A: [(t-BuNSiMe ₂ Flu) TiMe ₂ ]
Cocatalyst A: 6.5% by mass (as Al atom content) MMAO-3A toluene solution ([(CH ₃ ) _0.7 (iso-C ₄ H ₉ ) _0.3 AlO] n represented by methyl (A solution of isobutylaluminoxane, manufactured by Tosoh Finechem Co., Ltd., containing 6 mol% of trimethylaluminum based on the total amount of Al)
Cocatalyst B: 9.0% by mass (as Al atom content) TMAO-211 toluene solution (methylaluminoxane solution, manufactured by Tosoh Finechem Co., Ltd.), containing 26 mol% trimethylaluminum with respect to the total Al amount )

  The value of “part” in Tables 1 and 2 is a value (part by mass) with respect to 100 parts by mass of 2-norbornene. Moreover, about the promoter A and the promoter B of Table 2, the value of "part" is a value (mass part) as a toluene solution.

  Further, Table 4 shows the number average molecular weight, glass transition temperature (Tg), composition ratio (A) / (B) (molar ratio), and Al content of each copolymer.

[Preparation of transparent film]
20 parts by mass of each copolymer of Examples 1 to 4 and 80 parts by mass of toluene were placed in a sealed container, and each copolymer was dissolved over 24 hours with slow stirring. The obtained solution was pressure filtered through a 10 μm mesh, and then allowed to stand for 24 hours to remove bubbles in the solution. Next, each solution (solution temperature 20 ° C.) was cast on the surface of a PET base material (trade name “T-60”, manufactured by Toray Industries, Inc.) using a bar coater. After casting, the PET substrate was sealed and allowed to stand for 1 minute in order to make the surface uniform (leveling). After leveling, the PET substrate was dried at 60 ° C. for 5 minutes by a hot air dryer, and then the film was peeled from the PET substrate. Next, this film was fixed to a stainless steel frame and dried at 210 ° C. for 30 minutes in a state where the pressure was reduced by a vacuum dryer, to obtain a transparent film (film thickness 100 μm).

(Comparative Example 1)
A 2-norbornene / ethylene copolymer film ("TOPAS (registered trademark) 6017S-04" manufactured by TOPAS Advanced Polymers, GmbH) was used.

(Comparative Example 2)
Instead of the transparent film, a glass plate (1 mm thick, 10 cm square soda lime glass plate) was used.

(Comparative Example 3)
A biaxially stretched polyethylene naphthalate film (“Teonex Q65HA” thickness 50 μm, manufactured by Teijin DuPont Films Ltd.) was used.

[Formation of transparent conductive layer]
On each transparent film (cut to 10 cm square) obtained in Examples 1 to 4, the transparent film of Comparative Example 1 or 3 (cut to 10 cm square), or the glass plate of Comparative Example 2, the flow rate of argon gas was 150 sccm. Then, the flow rate of oxygen gas is 6 sccm, the film forming temperature is 195 ° C., the first layer of silicon oxide layer is 20 nm, the second layer of indium tin oxide layer (tin oxide content 10%) is laminated by 25 nm sputtering. Thus, a transparent conductive laminate was obtained.

  In addition, the transparent film obtained in Comparative Example 1 was melted, and a transparent conductive laminate could not be obtained. On the other hand, a transparent conductive film could be obtained without melting other transparent films. Various characteristic values of each transparent conductive laminate are shown in Table 4.

  In addition, when XRD was measured about the transparent conductive film of the comparative example 1 and Examples 1-2, all were able to observe the diffraction peak resulting from the crystal component of an indium tin oxide.

(Example 5)
(Preparation of coating solution for the first layer)
Toluene, methyl ethyl ketone, and tetrahydrofuran (toluene: methyl ethyl ketone: tetrahydrofuran (parts by mass) = 1.5: 1.5: 7) were mixed and stirred to prepare a uniform solvent (solvent). In this solvent, 100 parts by mass of vinylidene chloride polymer (“PVDC Resin R204” manufactured by Asahi Kasei Chemicals Corporation) and 3 parts by mass of tolylene diisocyanate (TDI) are dissolved, and the coating solution P having a solid content concentration of 3% by mass is dissolved. Got.

(Preparation of coating solution for the second layer)
The copolymer obtained in Example 1 was stirred and dissolved in toluene to obtain a coating liquid C having a solid content concentration of 5% by mass.

(Manufacture of laminated film)
A biaxially stretched polyethylene naphthalate film (“Teonex Q65HA” manufactured by Teijin DuPont Films Co., Ltd., thickness 50 μm) is used as a plastic substrate, and coating solution P is coated by the Mayer bar coating method at a temperature of 130 ° C. for 1 minute. Dry to form the first layer. Further, the coating liquid C was coated on the first layer by the Mayer bar coating method, and dried at a temperature of 100 ° C. for 1 minute to form a second layer to obtain a transparent laminated film. The thickness of the first layer was 0.15 μm, and the thickness of the second layer was 0.35 μm.

(Example 6)
A transparent laminated film was produced according to Example 5 except that the copolymer obtained in Example 2 was used.

(Example 7)
A transparent laminated film was produced according to Example 5 except that the copolymer obtained in Example 3 was used.

(Example 8)
A transparent laminated film was produced according to Example 5 except that the copolymer obtained in Example 4 was used.

(Comparative Example 4)
As a plastic substrate, a biaxially stretched polyethylene naphthalate film (“Teonex Q65HA” manufactured by Teijin DuPont Films Co., Ltd., thickness 50 μm) was used, and aliphatic urethane acrylate (“ADEKA Co., Ltd.“ HC-500-60 ”was used on one side thereof. )) Was coated by the Mayer bar coating method, dried at a temperature of 100 ° C. for 1 minute, and irradiated with ultraviolet rays (100 mJ / cm ² ) to obtain a transparent laminated film. The thickness of the aliphatic urethane acrylate was 1.5 μm.

[Formation of transparent conductive layer]
On each transparent laminated film (cut to 10 cm square) obtained in Examples 5 to 8 and Comparative Example 4, the flow rate of argon gas is 150 sccm, the flow rate of oxygen gas is 6 sccm, and the film forming temperature is 100 ° C., which is the first layer. A silicon oxide layer was laminated by 20 nm, and an indium tin oxide layer (content of tin oxide 10%) as a second layer was laminated by 25 nm sputtering. Further, heat treatment was performed at 200 ° C. for 60 minutes. The surface resistance value was measured before and after the heat treatment. Various characteristics of the obtained transparent conductive laminate are shown in Table 5.

  In the transparent conductive laminates obtained in Examples 5 to 8, the indium tin oxide layer was crystallized more than the transparent conductive laminate obtained in Comparative Example 4, and the surface resistance value was low.

  The transparent conductive laminate of the present invention can be used in various optical display devices that use a transparent conductive layer in a pattern, such as a personal computer, a television, a mobile phone (smartphone), electronic paper, a game machine, a mobile device, It can be used for a touch panel used in combination with a display device (a liquid crystal display device, a plasma display device, an organic or inorganic EL display device, etc.) in a display unit of an electric / electronic or precision instrument such as a clock or a calculator. In particular, because of excellent visibility, it is useful for the upper electrode plate on the viewing side of a projected capacitive touch panel employing an ITO grid method.

Claims (14)

  A base material layer containing at least one transparent resin selected from the group consisting of polyester, polycarbonate, polyimide, polysulfone resin and polyaryl ketone, and an olefin unit having an alkyl group having 2 to 10 carbon atoms in the side chain A transparent conductive laminate comprising a functional layer containing a cyclic olefin-based resin and a transparent conductive layer sequentially.   The transparent electroconductivity of Claim 1 in which cyclic olefin resin contains the cyclic olefin unit which has a chain olefin unit which has a C2-C10 alkyl group, and / or a C2-C10 alkyl group as a repeating unit. Laminated body.   The cyclic olefin-based resin has, as repeating units, a cyclic olefin unit (A) having no alkyl group having 2 to 10 carbon atoms, a chain or cyclic olefin unit (B) having an alkyl group having 2 to 10 carbon atoms, and The transparent conductive laminate according to claim 1, which is a copolymer containing   The transparent conductive laminate according to claim 3, wherein the chain or cyclic olefin unit (B) is an ethylene or norbornene unit having a linear alkyl group having 4 to 8 carbon atoms.   The transparent conductive laminate according to claim 3 or 4, wherein the ratio (molar ratio) between the cyclic olefin unit (A) and the chain or cyclic olefin unit (B) is the former / the latter = 50/50 to 99/1. .   The glass transition temperature of cyclic olefin resin is 210-350 degreeC, The transparent conductive laminated body in any one of Claims 1-5.   The transparent conductive laminate according to any one of claims 1 to 6, wherein the functional layer has an aluminum content of 50 ppm or less.   The transparent conductive laminate according to claim 1, wherein the transparent conductive layer contains a metal oxide.   The transparent conductive laminate according to claim 1, further comprising an anchor coat layer containing a chlorine-containing resin, wherein the anchor coat layer is interposed between the functional layer and the base material layer.   The transparent conductive laminate according to claim 1, having a total light transmittance of 80% or more and a haze of 2% or less.   The transparent conductive laminate according to claim 1, wherein the transparent conductive layer has a surface resistance value of 50 to 200Ω / □.   The transparent conductive laminate according to any one of claims 1 to 11, wherein the mandrel has a diameter of 4 mm or less in a bending resistance test according to JIS K5600-5-1.   It is a manufacturing method of the transparent conductive laminated body including the transparent conductive layer formation process which forms the transparent conductive layer containing a metal oxide on the functional layer in any one of Claims 1-7, Comprising: The said transparent conductive layer In the layer forming step, a transparent conductive layer is formed by sputtering at a temperature of 180 ° C. or higher, or after the sputtering, a transparent conductive layer is formed by heating at a temperature of 180 ° C. or higher.   The manufacturing method of Claim 13 which further includes the functional layer formation process which forms a functional layer by coating on a base material layer.