JP2013012118A - Conductive laminate and touch panel using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conductive laminate which has a conductive layer containing a polythiophene-based conductive agent and reduces a decrease in conductivity with time, and a touch panel in which the conductive laminate is used.SOLUTION: A conductive laminate 1 has at least one pair of a conductive layer 12 and an adhesive layer 21 in contact with each other over the entire surface or a portion thereof, the conductive layer 12 containing a polythiophene-based conductive agent and the adhesive layer 21 containing an ultraviolet absorber. The conductive laminate 1 is used for obtaining a touch panel or the like.

Description

  The present invention relates to a touch panel used as a position input device, and a conductive laminate suitably used for the touch panel.

  A touch panel is an electronic component that functions as a position input device, is combined with a display device such as a liquid crystal panel, and is widely used in mobile phones, portable game machines, and the like. When the operator points to a specific position of the touch panel with a hand or an input pen based on the screen display, the device senses the information on the specific position and can perform an appropriate operation desired by the operator. Interface.

  In the touch panel, there are, for example, a resistance film type and a capacitance method as a method of detecting the position to be pointed, but the capacitance method has been rapidly expanded mainly in mobile devices such as mobile phones. As a typical detection method of the electrostatic capacity method, there are two methods, namely, a surface type for analog detection and a projection type by an integrated detection method using patterned electrodes. In addition, a number of proposals have been made for the projection type configuration for each method and manufacturer, but as a projection type that has recently increased rapidly, an insulating layer sandwiched between conductive layers and a protective plate for the surface can be used by using glass or a resin plate. Many of them have been given durability. In the future, it is expected that by making these various resin films, the movement to reduce costs and make them flexible will expand.

As the conductive layer that is the key to the touch panel, ITO (indium oxide doped with tin oxide) layer, which is formed by dry methods such as sputtering and vapor deposition, is the most frequently used because it can achieve both conductivity and transparency. ing.
However, when the touch panel structural material is made flexible by using a film as described above, the ITO layer has low flexibility, and thus durability may be significantly reduced.
Therefore, a layer using an organic conductive polymer has been studied as a conductive layer having excellent flexibility, and a polythiophene-based conductive agent is known as an organic conductive polymer (for example, a patent) Reference 1).

JP 2006-28439 A

However, the present inventor has found that the conductivity of a conductive layer using a polythiophene-based conductive agent may decrease over time.
The present invention has been made in view of the above circumstances, and has a conductive layer using a polythiophene-based conductive agent and reduced in the decrease in conductivity over time, and the conductive layer. The issue is to provide a touch panel.

As a result of intensive studies by the present inventors, the polythiophene-based conductive agent has low light resistance, and it has been found that ultraviolet rays are at least one cause of the decrease in conductivity over time, and the present invention has been completed.
The conductive laminate of the present invention has at least one pair of conductive layers and an adhesive layer that are in contact with the whole surface or a part thereof, the conductive layer contains a polythiophene-based conductive agent, and at least one of the adhesive layers includes: It contains an ultraviolet absorber.
The ultraviolet absorber is preferably at least one compound having a maximum absorption wavelength at a wavelength of 350 nm or more and an oily or liquid compound at 23 ° C.
The polythiophene conductive agent is preferably at least one selected from the group consisting of 3-hexylthiophene polymer, 3,4-ethylenedioxythiophene polymer, and derivatives of these polymers.
The conductive laminate of the present invention has a set of the conductive layer and the adhesive layer, further includes an insulating layer, and the conductive layer is in contact with one side of the insulating layer, the conductive layer and the adhesive layer In addition, there may be mentioned a mode in which an insulating layer is further provided, and the conductive layer is in contact with both surfaces of the insulating layer.
When the conductive layer is in contact with both surfaces of the insulating layer, it is preferable that each conductive layer is formed in a pattern having regularity in a uniaxial direction, and the patterns are orthogonal to each other.
The insulating layer is preferably formed to be bendable.
The touch panel of this invention comprises the conductive laminated body of this invention, and the transparent sheet laminated | stacked through the said adhesion layer of this conductive laminated body, It is characterized by the above-mentioned.
The touch panel of the present invention is suitable for a capacitive method.

  ADVANTAGE OF THE INVENTION According to this invention, it can provide the conductive laminated body which has the conductive layer using a polythiophene-type electrically conductive agent, the electrical conductivity fall over time was reduced, and the touch panel using this conductive laminated body.

It is sectional drawing which shows the structure of the electroconductive laminated body of the example of 1st Embodiment. It is sectional drawing explaining a conductive layer formation process. It is sectional drawing explaining the adhesion layer formation process. It is sectional drawing which shows the structure of the electroconductive laminated body of the example of 3rd Embodiment. It is sectional drawing which shows an example of the liquid crystal module which comprises the touch panel of this invention. 1 is a cross-sectional view showing a touch panel (touch panel module) manufactured in Example 1. FIG. 2 is a cross-sectional view showing a conductive laminate produced in Example 1. FIG. 1 is a plan view showing a conductive laminate manufactured in Example 1. FIG.

<Conductive laminate>
The conductive laminate of the present invention has at least one pair of a conductive layer containing a polythiophene-based conductive agent and an adhesive layer, and the conductive layer and the adhesive layer are in contact with each other over the entire surface or part thereof.
Hereinafter, the present invention will be described in detail.

(1) First Embodiment Example FIG. 1 is a cross-sectional view showing a conductive laminate 1 according to a first embodiment of the present invention. The conductive laminate 1 of this example includes an insulating layer 11, A conductive layer 12 formed on one side of the insulating layer 11, an adhesive layer 21 formed on the conductive layer 12, and a first base material 22 for peeling covering the surface of the adhesive layer 21 opposite to the conductive layer 12; Have The conductive laminate 1 includes a pair of conductive layers 12 and an adhesive layer 21 that are in direct contact with each other, and has a configuration in which the conductive layer 12 is in contact with one surface of the insulating layer 11.

In addition, drawings, such as sectional drawing shown below, mainly show a layer structure, and there are places where dimensions and thickness are emphasized as appropriate, and are not shown accurately.
In the example of FIG. 1, the conductive layer 12 and the adhesive layer 21 are in contact with each other, but the conductive laminate of the present invention may be one in which the conductive layer and the adhesive layer are in contact with each other.

[Conductive layer]
The conductive layer 12 may be a uniform layer formed on the insulating layer 11 with a substantially uniform thickness, which is used for, for example, an analog resistive film type touch panel or the like, for example, a projected capacitive touch panel A conductive layer having a regular pattern formed for position detection may be used. The regular pattern may be formed by a method in which the conductive layer 12 is partially provided on the insulating layer 11 in advance by various printing methods or the like, or the coating liquid for forming the conductive layer is uniform. It may be formed by removing a part thereof after application by wet etching using an etching solution or dry etching using a laser beam. Even in the case of a uniform layer, a part of the conductive layer 12 may be patterned in order to form an extraction electrode or the like depending on the configuration of the touch panel.

The conductive layer 12 contains a polythiophene-based conductive agent as a conductive substance.
The polythiophene-based conductive agent is a π-conjugated organic conductive polymer that exhibits conductivity by a main chain in which double bonds and single bonds are alternately arranged. High transparency can be achieved.
As a polythiophene-based conductive agent, a polymer of 3-hexylthiophene (hereinafter sometimes abbreviated as 3HT) (hereinafter sometimes abbreviated as P3HT), a derivative thereof, 3,4-ethylenedioxythiophene (hereinafter referred to as P3HT). EDOT) polymer (hereinafter sometimes abbreviated as PEDOT) and one or more selected from the group consisting of derivatives thereof are preferably used. Derivatives such as self-doped polythiophene having a sulfonic acid group in the main chain and organic solvent-dispersed PEDOT copolymerized with a flexible polymer such as polyethylene glycol can also be used, and each layer of the conductive laminate 1 can be used. The material is suitably selected according to the manufacturing method of the member and the conductive laminate 1, for example, the use conditions when a touch panel is used.

  As will be described in detail later, the conductive layer 12 is a method of applying a coating liquid for forming a conductive layer containing a polythiophene-based conductive agent or printing an ink for forming a conductive layer containing a polythiophene-based conductive agent. Is suitably formed. Therefore, in the preparation of the coating liquid or ink, not only the role of a dopant that enhances conductivity, but also polystyrene sulfonic acid that functions as a dispersant for PEDOT that becomes fine particles in water by polymerization (hereinafter sometimes abbreviated as PSS). An aqueous dispersion obtained by polymerizing EDOT in the presence of PEDOT-PVS (hereinafter sometimes abbreviated as PEDOT-PSS), PEDOT-PVS using polyvinyl sulfonic acid (hereinafter sometimes abbreviated as PVS) instead of PSS, etc. It is also suitable to adopt.

  In addition, a conductive layer is formed by adding a high-boiling solvent such as polyethylene glycol, methylformamide, dimethyl sulfoxide, N-methylpyrrolidone or the like, which has been confirmed to improve conductivity, to these PEDOT or derivatives thereof as a secondary dopant. It can also be used as a coating liquid or ink. In that case, the addition amount of the high boiling point solvent in the coating liquid or ink for forming the conductive layer is preferably 10 to 500 parts by mass, more preferably 100 to 300 parts by mass with respect to 100 parts by mass of the polythiophene-based conductive agent. Part. If the addition amount of the high boiling point solvent is too small, the effect as the secondary dopant cannot be sufficiently obtained, and if the addition amount of the high boiling point solvent is too large, the residual amount of the high boiling point solvent to the dry coating film increases. There is a concern of bleeding (elution) after processing as a conductive laminate.

In addition to the polythiophene-based conductive agent and the above-described dopant used as necessary, the conductive layer 12 usually contains a binder component for improving the film formability.
Examples of the binder component include various resin components, or a mixture of a monomer or oligomer that becomes a polymer and a film forming component such as a polymerization initiator or a crosslinking agent that activates these with light or heat. It is appropriately selected depending on the properties of the conductive agent and the type and configuration of the insulating layer 11.

Examples of the resin component include an acrylic resin, a styrene resin, a polyester resin, an alkyd resin, a urethane resin, an amide resin, and the like, or a modified or copolymer resin thereof, and one or more of them can be used.
Examples of the monomer or oligomer include polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, and the like, and one or more of these can be used. Specifically, as the radical polymerization system, monofunctional ethyl carbitol (meth) acrylate, phenol ethylene oxide modified (meth) acrylate, nonylphenol ethylene oxide modified (meth) acrylate, ethoxydiethylene glycol acrylate, acryloylmorpholine, isobornyl (meta) ) Acrylate, N-vinyl pyrrolidone, bifunctional hexanediol di (meth) acrylate, hexanediol ethylene oxide modified diacrylate, neopentyl glycol polyethylene oxide modified di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tri Propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, bisphenol A ethylene oxide Iodine-modified di (meth) acrylate, polyethylene glycol di (meth) acrylate, tri- or more-functional trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide-modified tri (meth) acrylate, glycerin propoxytri (meth) acrylate, di Examples of cationic polymerization systems such as pentaerythritol hexaacrylate and ditrimethylolpropane tetraacrylate include, but are not limited to, epoxy compounds such as glycidyl ether compounds and alicyclic epoxy compounds, oxetane compounds, and vinyl ether compounds. .
In the above, a polyester-type resin can be utilized suitably.

  As the film-forming component, it is preferable to use a component that imparts solvent resistance to the conductive layer, such as a crosslinking agent or a polyfunctional component. Among the above monomers and oligomers, trifunctional or higher functional monomers and oligomers, and silane coupling Examples thereof include organosilanes such as an agent, and epoxy, isocyanate, and melamine crosslinking agents. Among them, a silane coupling agent having an organic functional group and an alkoxyl group in one molecule has not only a binder component but also, for example, a contact surface of the insulating layer 11 with the conductive layer 12 has a hard coat layer containing a Si component. In the case where the insulating layer 11 is made of a PET film having an easy-adhesion layer on the contact surface with the conductive layer 12, it can contribute to improvement of adhesion with the insulating layer 11, which is preferable. On the other hand, the melamine-based cross-linking agent tends to cause a decrease in transparency of the conductive layer 12, and attention is required for its use.

  The amount of the binder component contained in the conductive layer 12 is desirably suppressed to the minimum amount in order to maximize the conductive performance of the polythiophene-based conductive agent. For example, when patterning of the conductive layer 12 is required according to the touch panel method, it is preferable to use a photo-curable photosensitive binder because the conductive layer 12 can be patterned with a photomask. In addition, when patterning the conductive layer 12 by printing, it is preferable to appropriately adjust the addition amount of the binder component and the molecular weight (which greatly affects the viscosity) in order to adjust the ink viscosity to be suitable for various printing methods.

In addition to these main components, the conductive layer 12 has an antioxidant, a heat stabilizer, an ultraviolet absorber, a metal corrosion inhibitor, a pH adjuster, an organic material, as long as it does not significantly impair the conductive performance of the conductive agent. Additives such as particles, inorganic particles, pigments, dyes, antistatic agents, nucleating agents, and coupling agents, and coating aids such as wetting agents and antifoaming agents may be included as appropriate.
Wetting agents and antifoaming agents are effective in preventing defects in the conductive layer 12, and for example, surfactants such as silicone-based, long-chain alkyl-based, and fluorine-based surfactants are used. Care should be taken because the adhesion durability between the insulating layer 11 and the insulating layer 11 tends to be lowered, and silicone-based and long-chain alkyl-based materials are preferably used.
Moreover, these surface active components may be integrated into the binder resin by copolymerization or the like in addition to being mixed as an additive. By adjusting the contact angle of the conductive layer 12 to 50 degrees or more and 100 degrees or less, more preferably 60 degrees or more and 90 degrees or less by blending these components, it is possible to maintain the adhesion durability between the conductive layer 12 and the insulating layer 11 while maintaining the defect. Since the conductive layer 12 having no surface is obtained, it is preferable.

  The conductive layer 12 may further contain another conductive agent as long as the performance of the polythiophene-based conductive agent that is an essential component as a conductive substance is not impaired. Such a conductive agent is preferably used as long as it does not interfere with coating or printing when added to a coating solution or ink for forming a conductive layer. Examples of such conductive agents include metal compounds such as silver and copper (fine particles, wires, pastes or solubilized salts), metal oxide fine particles such as ITO and ATO, organic conductive polymers such as polyaniline, and conductive properties. A carbon nanotube etc. are mentioned and 1 or more types can be used.

  The content of the conductive agent in the conductive layer 12 (the total amount of the polythiophene-based conductive agent and other conductive agents used as necessary) is preferably as high as possible. However, in view of film forming properties and other qualities, 10 It is -90 mass%, More preferably, it is 30-70 mass%. Further, when the ratio of the polythiophene-based conductive agent in the total conductive agent is preferably 50% by mass or more, the conductive layer 12 having excellent flexibility can be formed.

  The conductive layer 12 is preferably highly transparent for the purpose of use in a touch panel or the like. However, since the polythiophene-based conductive agent is a colored substance, the transparency of the conductive layer 12 depends on the content of the polythiophene-based conductive agent. It is greatly affected. The transparency of the conductive layer 12 is preferably 70% or more, and more preferably 88% or more, as the total light transmittance (JIS K7105) of the conductive film comprising the conductive layer 12 and the insulating layer 11. Except for cases where light diffusivity is intentionally required, the haze (JIS K7105) of the conductive film is preferably 5% or less, more preferably 2% or less.

The thickness of the conductive layer 12 varies greatly depending on the use of the conductive laminate 1 and the composition and properties of the conductive agent, and thus cannot be specified unconditionally. The thickness is 1 μm, more preferably 0.02 to 0.08 μm. When the dry film thickness is 0.01 μm or less, it is difficult to ensure the uniformity of conductivity, and when it is 1 μm or more, the efficiency is lowered and the cost is increased.
The conductivity of the conductive layer 12 is preferably a surface resistance of 10 ⁵ Ω / sq or less, more preferably 10 ³ Ω / sq or less, in order to obtain an electrode plate for a touch panel. The surface resistance can be adjusted by the composition of the conductive agent in the coating liquid or ink for forming the conductive layer, the coating amount, and the like.

  A lead electrode may be formed on the conductive layer 12 in a form that can be connected to the surface or the conductive layer 12 depending on the use situation. As a material for the extraction electrode, a highly conductive silver paste, or a metal material such as aluminum or molybdenum is suitable, but is not limited thereto. Moreover, the formation method can utilize well-known methods, such as printing of a paste etc., and sputtering.

[Adhesive layer]
The adhesive layer 21 contains at least an adhesive and an ultraviolet absorber. When the adhesive layer 21 provided on the conductive layer 12 contains an ultraviolet absorber, it is possible to effectively suppress a decrease in conductivity over time of the polythiophene-based conductive agent contained in the conductive layer 12 due to ultraviolet rays.
The thickness of the pressure-sensitive adhesive layer 21 varies depending on the use environment, the composition of the pressure-sensitive adhesive layer 21 and the like, and cannot be generally defined, but is preferably 5 to 500 μm, more preferably 10 to 300 μm. If it is 5 μm or more, sufficient adhesiveness is easily obtained, while if it is 500 μm or less, the conductive laminate 1 is not easily deformed excessively, and the position detection ability is hindered when it is used as a touch panel. It will never be.

(Adhesive)
As the adhesive, for example, a natural rubber adhesive, a synthetic rubber adhesive, an acrylic adhesive, a urethane adhesive, a silicone adhesive, and the like can be used. Further, the pressure-sensitive adhesive may be any of a solvent system, an emulsion system, and an aqueous system. When used in optical applications, a solvent-based acrylic pressure-sensitive adhesive can be particularly preferably used from the viewpoints of transparency, weather resistance, durability, cost, and the like. Among these, from the viewpoint of adhesive quality, a polymer containing ethylhexyl acrylate or butyl acrylate as at least one monomer unit is particularly preferable as the adhesive.
In addition, as the pressure-sensitive adhesive, those in which an acidic group such as a carboxyl group, a phosphoric acid group, or a sulfonic acid group is bonded to a part of the polymer that is the main component of the pressure-sensitive adhesive can be used.

(UV absorber)
As the ultraviolet absorber, one that effectively absorbs a long wavelength portion (UV-A region) of ultraviolet rays having a large influence which deteriorates the conductivity of the conductive layer 12 is desirable, and specifically, maximum (maximum) absorption. Those having a wavelength of 350 nm or more are preferred. And when using the electroconductive laminated body of this invention in an actual use environment, a thing with little compatibility with an adhesive with little possibility that an optical characteristic will fall by precipitation of the added ultraviolet absorber etc. is preferable. The compatibility is determined by a balance with the properties of the pressure-sensitive adhesive that is the main component of the pressure-sensitive adhesive layer. However, it is more preferable that the ultraviolet absorber itself is oily or liquid at 23 ° C., because the concern about precipitation is reduced.

  Here, being oily or liquid at 23 ° C. means that the compound is fluid only with no diluting solvent. The other characteristics of the ultraviolet absorber may be selected according to the properties of the pressure-sensitive adhesive to be combined, but when combined with a solvent-based pressure-sensitive adhesive suitable for the present invention, the ultraviolet light absorber having a hydrophobic functional group containing a long alkyl chain. Is preferably used because of good compatibility. In addition, it is more preferable that the ultraviolet absorber does not contain a halogen atom because it does not easily yellow even when exposed to light for a long time in an actual use environment.

  The structure of the ultraviolet absorber may be any of benzotriazole, triazine, benzophenone, cyanoacrylate, salicylate, and the like. Specifically, benzotriazole 2- (2-hydroxy-5-t -Butylphenyl) -2H-benzotriazole (manufactured by BASF, trade name TINUVIN PS), 5% 2-methoxy-1-methylethyl acetate 95% benzenepropanoic acid, 3- (2H-benzotriazol-2-yl)- 5- (1,1-dimethylethyl) -4-hydroxy, C7-9 side chain and linear alkyl ester (BASF, trade name TINUVIN 99-2), or its dispersion in water (BASF, trade name) TINUVIN 99-DW), octyl-3- [3-tert-butyl-4-hydroxy -5- (5-Chloro-2H-benzotriazol-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazole- 2-yl) phenyl] propionate (BASF, trade name TINUVIN 109), 2- (2H-benzotriazol-2-yl) -4,6-di-t-pentylphenol (BASF, trade name) TINUVIN 328), 5% 2-methoxy-1-methylethyl acetate 95% benzenepropanoic acid, 3- (2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxy, C7 -9 side chain and linear alkyl ester (trade name TINUVIN 384-2, manufactured by BASF), 2- (2H -Benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (manufactured by BASF, trade name TINUVIN 900), 2- (2H-benzotriazol-2-yl) -6 -(1-Methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol (trade name TINUVIN 928 manufactured by BASF), methyl 3- (3- (2H-benzotriazole) 2-yl) -5-t-butyl-4-hydroxyphenyl) propionate / polyethylene glycol 300 reaction product (trade name TINUVIN 1130, manufactured by BASF) 85% of hydroxyphenyltriazine series 2- (4,6- Bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hydroxypheny , And a reaction product of oxirane [(C10-C16 mainly C12-C13 alkyloxy) methyl] oxirane 15% 1-methoxy-2-propanol (manufactured by BASF, trade name TINUVIN 400), or dispersion in water (BASF) Product name TINUVIN 400-DW), 2- (2,4-dihydroxyphenyl) -4,6-bis- (2,4-dimethylphenyl) -1,3,5-triazine and (2-ethylhexyl) -Reaction product of glycidic acid ester (manufactured by BASF, trade name TINUVIN 405), 2,4-bis "2-hydroxy-4-butoxyphenyl" -6- (2,4-dibutoxyphenyl) -1,3 -5-triazine (trade name TINUVIN 460, manufactured by BASF), trade name TINUVI, manufactured by BASF N 477, or a dispersion in water thereof (trade name: TINUVIN 477-DW, manufactured by BASF), trade name: TINUVIN 479, manufactured by BASF, etc. can be exemplified, but are not limited thereto.

  Of these, octyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazole-2-) having an absorption maximum wavelength of 350 nm or more and an oily or liquid state at 23 ° C. Yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate (TINUVIN 109), TINUVIN 447, TINUVIN 400-DW, TINUVIN 447-DW, TINUVIN 99-DW, and the like can be exemplified as more preferable materials.

  The optimum content of the ultraviolet absorber in the adhesive layer 21 varies depending on the thickness of the adhesive layer 21 and cannot be generally specified. However, if the content is too small, a sufficient ultraviolet absorbing effect cannot be exhibited and it is too much. And the optical properties are deteriorated or stable adhesive properties cannot be obtained, so that it is preferably 1 to 10 parts by mass, more preferably 2 to 6 parts by mass with respect to 100 parts by mass of the adhesive.

(Additive)
It is also preferable to add a light stabilizer typified by a hindered amine compound that can be expected to have a synergistic effect with the ultraviolet absorber to the adhesive layer 12. The mechanism of action of the light stabilizer is different from the mechanism of the above-described ultraviolet absorber, and it is presumed that the radical scavenging effect is the main stabilizing effect, generally focusing on three types of HALS oxidants.
Moreover, in order to provide durability to long-term use to an ultraviolet absorber, it is preferable to add an antioxidant typified by a hindered phenol-based compound. For example, if the polymerization initiator used at the time of polymerization of the pressure sensitive adhesive remains in the pressure sensitive adhesive, it is presumed that radicals generated from the residue change the ultraviolet absorber. It is thought that alteration of the absorbent can be suppressed.
Antioxidants are generally classified into primary antioxidants called radical chain terminators and secondary antioxidants that act as peroxide decomposers. Examples of the primary antioxidant include hindered phenol antioxidants, amine antioxidants, and lactone antioxidants. Examples of secondary antioxidants include phosphorus antioxidants and sulfur antioxidants. One or more of these antioxidants can be used.

  The total content of the antioxidant and the light stabilizer is preferably 0.03 to 1.5 parts by mass, and 0.05 to 1.0 parts by mass with respect to 100 parts by mass of the pressure-sensitive adhesive. More preferred. If the content is not less than the above lower limit value, it is possible to reliably maintain the absorbency of ultraviolet rays when used over a long period of time in a high temperature, low temperature and wet heat environment, and if the content is not more than the above upper limit value, for example, transmission at 380 nm It is possible to further prevent an increase in rate and a decrease in adhesive properties.

Examples of other additives include tackifiers, silane coupling agents, metal corrosion inhibitors, and the like, which are used as necessary. Examples of the tackifier include rosin resins, terpene resins, terpene phenol resins, coumarone indene resins, styrene resins, xylene resins, phenol resins, petroleum resins, and the like.
Examples of the silane coupling agent include mercaptoalkoxysilane compounds (for example, mercapto group-substituted alkoxy oligomers).
As the metal corrosion inhibitor, a type that prevents a corrosion by forming a complex with a metal and forming a film on the metal surface is preferable, and a benzotriazole-based metal corrosion inhibitor is particularly preferable.
Furthermore, examples of the additive include a thickener, a pH adjuster, a binder component, a crosslinking agent, an adhesive fine particle, an antifoaming agent, and an antiseptic / antifungal agent.

[Insulation layer]
The conductive laminate 1 in the example of FIG. 1 includes a sheet-like insulating base material as the insulating layer 11, and a pair of the conductive layer 12 and the adhesive layer so that the above-described conductive layer 12 is in contact with the surface. 21 are stacked. The insulating layer 11 may be composed only of a sheet-like insulating base material made of a glass substrate, a resin film, a resin plate, or the like, or may be provided on the insulating base material and the surface thereof as necessary. It may be comprised from the layer of this. The insulating layer 11 is preferably formed to be bendable from the viewpoint of making the conductive laminate 1 flexible. Further, as the insulating layer 11, for example, a polarizing plate used in a liquid crystal module may be used.

(Insulating substrate)
Resin film constituting the insulating substrate and resin of the resin plate include polyethylene terephthalate, polyethylene naphthalate, polypropylene terephthalate, polybutylene terephthalate, polypropylene naphthalate, polyethylene, polypropylene, cellophane, diacetylcellulose, triacetylcellulose, cycloolefin Polymer, acetylcellulose butyrate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, polystyrene, polycarbonate, polymethylpentene, polysulfone, polyetheretherketone, polyethersulfone, polyetherimide, polyimide , Fluororesin, polyamide, (meth) acrylic resin, copolymer of methyl methacrylate and styrene, etc. These may be a mixture thereof.

  Among them, as an insulating base material, from the viewpoint of transparency, weather resistance, solvent resistance, rigidity, cost, etc., a biaxially stretched film of polyethylene terephthalate, a glass substrate, a cycloolefin polymer, or a polycarbonate with good transparency, etc. From the viewpoint of flexibility, a sheet of polyethylene terephthalate biaxially stretched film, cycloolefin polymer, or polycarbonate having good transparency is preferable. Moreover, it is preferable at the point of a flexibility that the thickness of these insulating base materials is 10-200 micrometers.

Various additives may be contained in the insulating base material. Examples of the additive include antioxidants, heat stabilizers, ultraviolet absorbers, organic particles, inorganic particles, pigments, dyes, antistatic agents, nucleating agents, and coupling agents. Although these additives are used as needed, when using the electroconductive laminate 1 for a touch panel, it is preferable to select an additive that does not impair the transparency of the electroconductive laminate 1.
The surface of the insulating base material may be subjected to surface oxidation treatment such as sand blast treatment or solvent treatment, corona discharge treatment, corona discharge treatment, chromic acid treatment, flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, etc. Good.

(Other layers constituting the insulating layer)
As a layer provided on the surface of the insulating base as necessary, for example, an interference fringe countermeasure layer, an optical adjustment layer such as a diffusion preparation layer to which various diffusing agents are added, and the adhesion with the conductive layer 12, Examples thereof include an anchor layer to which a reactive substance such as isocyanate is added. In addition, for patterning of the conductive layer 12 provided on the insulating base material, a foaming release layer may be provided on the insulating base material that can be peeled only at a location irradiated with the active energy ray.
In addition, when the surface of the insulating base material is exposed, or in order to suppress surface scratches that occur on the insulating base material during the process, the surface is a hard coat containing a resin component as a main component and a hard component. A layer may be provided.

The resin component that is the main component of the hard coat layer is preferably an acrylic polymer that is a polymer of a monomer or oligomer having a polymerizable unsaturated group.
The monomer or oligomer having a polymerizable unsaturated group is preferably a polyfunctional (meth) acrylate, such as dipropylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, or tripropylene. Glycol di (meth) acrylate, polyethylene glycol (mass average molecular weight 600) di (meth) acrylate, propylene oxide modified neopentyl glycol di (meth) acrylate, modified bisphenol A di (meth) acrylate, tricyclodecane dimethanol di (meth) ) Acrylate, polyethylene glycol (mass average molecular weight 400) bifunctional (meth) acrylate such as di (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) ) Acrylate, trimethylolpropane ethoxytri (meth) acrylate, polyether tri (meth) acrylate, trifunctional (meth) acrylate such as glycerol propoxytri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol ethoxytetra ( 4 or more functional groups such as (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, propionic acid-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. (Meth) acrylate is mentioned. One or more kinds of these polyfunctional (meth) acrylates can be used.
In order to make the pencil hardness of the hard coat layer 3H or higher, it is more preferable to select a tetrafunctional or higher (meth) acrylate.
The monomer or oligomer having a polymerizable unsaturated group may be thermosetting or active energy ray curable.

As the hard component, reactive inorganic oxide particles and / or reactive organic particles are used. When reactive inorganic oxide particles and / or reactive organic particles are used, antifouling properties, fingerprint adhesion prevention properties, antistatic properties and the like can be imparted.
The reactive inorganic oxide particles are inorganic oxide particles treated with a coupling agent, and the reactive organic particles are organic particles treated with a coupling agent. By treating the inorganic oxide particles or the organic particles with a coupling agent, the bonding strength with the acrylic polymer that is a resin component can be increased. As a result, surface hardness and scratch resistance can be improved, and dispersibility of inorganic oxide particles and organic particles can be improved.

As the inorganic oxide particles, those having high hardness are preferable, and for example, silicon dioxide particles, titanium dioxide particles, zirconium oxide particles, aluminum oxide particles and the like can be used.
Examples of organic particles that can be used include resin particles such as acrylic resin, polystyrene, polysiloxane, melamine resin, benzoguanamine resin, polytetrafluoroethylene, cellulose acetate, polycarbonate, and polyamide.
Examples of the coupling agent include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-mercaptopropyltrimethoxy. Silane, γ-aminopropyltriethoxysilane, γ-aminopropyltriethoxyaluminum and the like can be mentioned, and one or more can be used.
The processing amount of the coupling agent is preferably 0.1 to 20 parts by mass and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the inorganic oxide particles and / or organic particles.

The hard coat layer may contain a flexible component. When the flexible component is contained, generation of cracks when the conductive laminate is punched can be further prevented.
Here, the flexible component is a (meth) acrylate having a polymerizable unsaturated group having one or more polymerizable unsaturated groups in the molecule. Examples of the (meth) acrylates include tricyclodecanemethylol di (meth) acrylate, ethylene oxide modified di (meth) acrylate of bisphenol F, ethylene oxide modified di (meth) acrylate of bisphenol A, ethylene oxide of isocyanuric acid Modified di (meth) acrylate, polypropylene glycol di (meth) acrylate, bifunctional (meth) acrylate such as polyethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylpropane propylene oxide modified tri (meth) Trifunctional (meth) acrylate such as acrylate, trimethylpropane ethylene oxide modified tri (meth) acrylate, urethane (meth) acrylate, polyester Meth) acrylate, polyether (meth) acrylate. In particular, it is more preferable to select trifunctional (meth) acrylate and urethane (meth) acrylate.
These (meth) acrylates can be used singly or in combination of two or more.

[First substrate for peeling]
As the first base material 22 for peeling provided in the conductive laminate 1 in the example of FIG. 1, those obtained by releasing the surface of various sheets and paper such as paper exemplified above as the insulating base material are suitably used. . For the release treatment, a condensation-type or addition-type silicone release agent, a non-silicone release agent such as an olefin, a long-chain alkyl group-containing polymer, or a fluorine is used. The sheet is preferably a resin film such as polyester or polypropylene or paper from the viewpoint of physical properties and cost.
The first substrate 22 for peeling is peeled from the conductive laminate 1, and for example, a cover glass (transparent sheet) is bonded to the exposed adhesive layer 21, or the polarizing plate surface of the liquid crystal module is bonded. To do.

<Method for producing conductive laminate>
The conductive laminated body 1 of FIG. 1 can be manufactured as follows, for example.
(I) Conductive layer formation process The conductive layer 12 is formed in the single side | surface of the insulating layer 11 which consists of an insulating base material, and the conductive film 10 shown in FIG. 2 is obtained. Here, if necessary, patterning of the conductive layer 12 and formation of the extraction electrode can be performed. In FIG. 2, the same components as those in FIG. 1 are denoted by the same reference numerals, and detailed description thereof is omitted. The other figures shown below are handled in the same manner.
(Ii) Adhesive Layer Forming Step On the other hand, as shown in FIG. 3, a coating liquid for forming the adhesive layer 21 is applied and dried on one surface of the first substrate for peeling (peeling substrate) 22 for adhesion. The layer 21 is formed, and the second substrate 23 for peeling is bonded thereon to obtain the pressure-sensitive adhesive sheet 20.
Note that it is preferable that the peeling force of the peeling first base material 22 and the peeling force of the peeling second base material 23 be different because only one of the peeling bases is easily peeled first.
(Iii) Adhesion step Next, the second substrate 23 for peeling is peeled off from the adhesive sheet 20 of FIG. 3 to expose the adhesive layer 21, and the adhesive layer 21 and the conductive layer 12 of the conductive film 10 of FIG. Is attached to obtain the conductive laminate 1 of FIG.
(Iv) Cutting or punching process The conductive laminate 1 is cut or punched and processed into a desired form.
Note that the cutting or punching process is not limited to the form performed after the sticking process, and may be performed before the sticking process.

For the formation of the conductive layer 12 in the above (i), as described above, a known method such as a method of applying a coating liquid for forming a conductive layer or a method of printing ink for forming a conductive layer can be employed.
Examples of the coating method include a method using a blade coater, an air knife coater, a roll coater, a bar coater, a gravure coater, a micro gravure coater, a rod blade coater, a lip coater, a die coater, a curtain coater, and the like. A microgravure coater is preferably used for forming the conductive layer 12 having a small target coating amount.
Examples of the printing method include screen printing, offset printing, flexographic printing, gravure offset printing, and ink jet printing.

When the patterning of the conductive layer 12 is necessary, the conductive layer 12 may be formed only at a necessary position by, for example, a gravure coater or various printing methods, or after forming a uniform conductive layer in advance, a known wet or dry method is used. Unnecessary portions may be removed by an etching method (such as ablation by laser light).
When wet etching is performed, an etching process may be performed after masking a part of the conductive layer by a photolithography method or a screen printing method using various active energy rays. For this process, Japanese Patent Application Laid-Open No. 2008-091487 may be used. Etching solutions for organic conductive polymers described in JP-A-2008-115310 and the like can be suitably used. Alternatively, the etching process may be carried out without masking by directly printing an etching paste such as an ishipe Higper Etch product manufactured by Merck Ltd. on the removed portion of the conductive layer.

  For the formation of the pressure-sensitive adhesive layer 21 in the above (ii), a method of applying the coating solution for forming the pressure-sensitive adhesive layer with the above-mentioned various coaters is suitable, and among them, it is preferable to use a lip coater or a die coater.

In addition, a known method such as coating or printing is adopted for forming other layers such as an anchor layer provided on the insulating base material as necessary, for example, an anchor layer having a relatively small coating amount. For example, a microgravure coater is preferably used for the formation.
For drying at the time of forming each layer, for example, a heated air dryer or a vacuum dryer is used.

In addition, the coating liquid and ink for forming each layer may contain a solvent for dilution in addition to the active ingredient for the purpose of improving paintability and printability. Examples of the solvent include water, alcohol (methanol, ethanol, isopropanol, n-butyl alcohol, etc.), ketone (acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl butyl ketone, ethyl butyl ketone, cyclohexanone, etc.), ether (for example, , Diethyl ether, methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, etc.), toluene, n-hexane, ethyl acetate, butyl acetate, N-methyl-2-pyrrolidone, etc. 1 or more types can be used.
In order to reduce coating unevenness, it is preferable to use solvents having different evaporation rates. For example, it is preferable that a plurality of solvents are appropriately selected from methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, and propylene glycol monomethyl ether, and these are mixed and used.

In order to increase the durability of each layer, a component that promotes curing may be added to the coating liquid and ink for forming each layer. When using a thermosetting cross-linking agent such as an isocyanate compound or an epoxy compound, use a heating furnace or an infrared lamp, etc. to heat the coating when it is dried or with a muro, etc. The film strength may be improved.
On the other hand, when a known photopolymerization initiator, a photosensitive resin, or the like is added, the coating film strength may be improved by accelerating the high molecular weight or crosslinking reaction of the coating film by irradiation with active energy rays.

Examples of the active energy rays include ultraviolet rays and electron beams. Among them, ultraviolet rays are preferable from the viewpoint of versatility. As the ultraviolet light source, for example, a high pressure mercury lamp, a low pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a carbon arc, a xenon arc, an electrodeless ultraviolet lamp, or the like can be used.
As the electron beam, for example, an electron beam emitted from various electron beam accelerators such as a cockloftwald type, a bandecraft type, a resonant transformation type, an insulating core transformer type, a linear type, a dynamitron type, and a high frequency type can be used.
Curing by irradiation with active energy rays is preferably performed in the presence of an inert gas such as nitrogen in order to avoid curing inhibition by oxygen in the atmosphere, and nitrogen gas can be suitably used from the viewpoint of cost.
In addition, the active energy ray irradiation process may be performed in two stages, a preliminary curing process and a main curing process.

The conductive laminate 1 can be produced, for example, by the following method (a) or method (b), and there is no particular limitation.
(A) On the surface of the conductive layer 12 in the conductive film 10, a coating solution for forming the adhesive layer 21 is directly applied and dried to form the adhesive layer 21, and the peeling first substrate 22 is pasted thereon. To wear.
(B) A coating solution for forming the adhesive layer 21 is applied and dried on one surface of the first substrate 22 for peeling to form the adhesive layer 21, and the conductive layer 10 side of the conductive film 10 is formed thereon. Adhere.

(2) Second Embodiment The conductive laminate 1 of the first embodiment includes a pair of conductive layers 12 and an adhesive layer 21 and has an insulating layer 11 made of an insulating substrate. However, the conductive laminate of the second embodiment is different from the first embodiment in that it includes a peelable substrate instead of the insulating substrate 11. Is different.
Such a conductive laminate can be used in combination with another member on the conductive layer side after peeling of the peelable substrate. As the peelable substrate, those exemplified above as the first substrate for peeling can be suitably used.

(3) Third Embodiment FIG. 4 is a cross-sectional view showing a conductive laminate 1 ′ of a third embodiment. The conductive laminate 1 ′ in this example has a conductive layer 12, an adhesive layer 21, and a first substrate for peeling on the surface opposite to the conductive layer 12 in the insulating layer 11 of the conductive laminate 1 shown in FIG. 1. 22 is sequentially laminated. In this embodiment, the conductive layer 12, the adhesive layer 21, and the first substrate for peeling 22 formed on both sides of the insulating layer 11 are layers having different compositions even if they are layers having the same composition on both sides. There may be.
In the conductive laminate 1 ′ having such a configuration, each conductive layer 12 is formed in a pattern having regularity in a uniaxial direction, and the patterns of the conductive layers 12 are in a positional relationship orthogonal to each other. As will be described below, the conductive laminate 1 ′ is suitably used as a main member of a projected capacitive touch panel.
In addition, when it is the form which has two or more sets of an electroconductive layer and an adhesion layer in this way, at least one layer should just contain an ultraviolet absorber as needed.

<Touch panel>
FIG. 5 is a cross-sectional view illustrating an example of a liquid crystal module including the touch panel 100 of the present invention that is a projected capacitive type. The touch panel 100 includes two sheets from the conductive laminate 1 ′ of FIG. The electroconductive sheet which peeled the 1st base material 22 for peeling is comprised. Each of the conductive layers 12-U and 12-L acting as the upper electrode and the lower electrode on both surfaces of the insulating layer 11 is processed into a pattern having regularity in a uniaxial direction, and 12-U of each conductive layer. , 12-L patterns are arranged to be orthogonal to each other for position detection.

The conductive layer 12-U on the upper electrode side is bonded to the cover member (transparent sheet) 101 made of a transparent material such as glass or film via the adhesive layer 21-U, and the conductive layer 12- on the lower electrode side. For example, an adhesive layer 21-L is laminated on L because it is bonded to the polarizing plate surface of the liquid crystal module 102, for example.
The conductive layers 12-U and 12-L include a lead electrode layer (not shown), and the lead electrode layer and the FPC (flexible wiring board) connector 104 are connected. Further, the FPC connector 104 is fixed by FPC or the like. The touch panel 100 is configured by being connected to the capacitance detection circuit 105.
In addition, since the structure of a touch panel is various for every manufacturer or model, it is not limited to this.

  Thus, for example, by using the conductive laminate 1 ′ in the example of FIG. 4, the projected capacitive touch panel 100 as used in the liquid crystal module of FIG. 5 can be easily manufactured. Such a touch panel 100 has the conductive layers 12-U and 12-L containing the polythiophene-based conductive agent having low light resistance, but the adhesive layer 21 facing these conductive layers 12-U and 12-L. Since -U and 21-L contain an ultraviolet absorber, a decrease in conductivity over time due to ultraviolet rays is reduced.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples. In the examples, “%” indicates mass% unless otherwise specified.

[Example 1]
(Preparation of conductive film)
An aqueous dispersion containing a conductive material (PEDOT-PSS) obtained by polymerizing (3,4-ethylenedioxythiophene) in the presence of polystyrene sulfonic acid, and a polyester resin (manufactured by Toyobo Co., Ltd., Bironal) as a binder component MD1200), a surfactant (manufactured by Shin-Etsu Chemical Co., Ltd., leveling agent KP-110) is mixed at a mass ratio of 1: 1: 1 as a solid content, diluted with methanol, and a solid content concentration of 1%. It was set as the liquid mixture A. This mixture A and a silane coupling agent (Shin-Etsu Silicone Co., Ltd. KBM-403) diluted with a water / methanol = 50/50 mixture to give a 1% solution have a mass ratio of 100: 30. To prepare a coating solution A for forming a conductive layer.
This coating liquid A was applied to the first substrate constituting the insulating layer 11 (“biaxially stretched polyethylene terephthalate film provided with an easy adhesion treatment layer on both sides” (trade name “Cosmo Shine A4300”, manufactured by Toyobo Co., Ltd., thickness 100 μm)) on one side, coated with a bar coater to a dry thickness of about 0.2 μm, and then dried to form a conductive layer 12, surface resistance 287 Ω / sq (JIS-K7194 compliant), total light The electroconductive film 10 of the structure shown in FIG. 2 of the transmittance | permeability (based on JIS-K7105) 88.3% was obtained.
Further, a double-sided conductive film having a conductive layer formed on the other side was also obtained for the touch panel.

(Preparation of adhesive sheet)
<Preparation of coating solution for forming an adhesive layer>
Nitrogen gas was sealed in a reactor equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube, and then ethyl acetate as a solvent was added. Next, in the reactor, 65 parts by mass of butyl acrylate as an acrylic monomer, 35 parts by mass of methyl acrylate, 2 parts of acrylic acid, and 0.1 mass of 2,2′-azoisobutyronitrile as a polymerization initiator. The polymer was polymerized for 8 hours at the reflux temperature of the solvent in a nitrogen gas stream while stirring. After completion of the reaction, toluene was added to obtain an acrylic polymer solution. To 100 parts by mass of this acrylic polymer solid content, 2.0 parts by mass of a hindered amine compound (product name: TINUVIN 144, manufactured by BASF) as a light stabilizer, and a hindered phenol compound (trade name: IRGANOX 1520L) as an antioxidant. 0.08 parts by mass) (manufactured by BASF) was added to obtain an adhesive main agent.
Next, with respect to 100 parts by mass of the pressure-sensitive adhesive main component, 1 part of tolylene diisocyanate (product name: Coronate L, manufactured by Nippon Polyurethane Co., Ltd.), a benzotriazole-based liquid ultraviolet absorption having a maximum absorption wavelength at a wavelength of 353 nm 4.0 parts by mass of an agent (product name: TINUVIN109, manufactured by BASF) was mixed to obtain a coating solution for forming an adhesive layer.

<Production of adhesive sheet>
Using the prepared coating liquid for forming an adhesive layer, two types (adhesive sheet α and adhesive sheet β) of the adhesive sheet 20 having the configuration shown in FIG. 3 were prepared as follows.
Using a bar coater, the adhesive layer-forming coating solution is dried on a 38 μm thick PET release film (product name: 38RL07 (5), manufactured by Oji Specialty Paper Co., Ltd.) as the first substrate 22 for release. The coating amount was 175 g / m ² and dried at 100 ° C. for 5 minutes to form an adhesive layer 21. Next, a 38 μm-thick PET release film (product name: 38RL07 (2), Oji Specialty Paper Co., Ltd.) that has been subjected to a release treatment on the surface of the pressure-sensitive adhesive layer 21 so that the release force is lighter than that of the first substrate 22 for release. (Made by company) as a second substrate 23 for peeling, and then left at room temperature for one week, and a pressure-sensitive adhesive sheet comprising a layer configuration of first substrate 22 for peeling / adhesive layer 21 / second substrate 23 for peeling 20 was produced. This is referred to as an adhesive sheet α.
Also, the first substrate for peeling 22 / the adhesive layer 21 / the second substrate for peeling except that the coating amount of the pressure-sensitive adhesive after drying was applied so as to be 50 g / m ^2. A pressure-sensitive adhesive sheet 20 having a layer structure of 23 was produced. This is referred to as an adhesive sheet β.

(Preparation of conductive laminate)
A conductive laminate 1 ″ shown in FIGS. 7 and 8 was produced as follows.
A lead electrode is formed with silver paste (Dotite FA-401CA, manufactured by Fujikura Kasei Co., Ltd.) at both ends of the conductive layer 12 of the conductive film 10 of FIG. 2 cut into 3 cm × 7 cm so that the distance between the electrodes is 5 cm. Thus, a test piece was produced. Using the pressure-sensitive adhesive sheet β cut out to 3 cm × 5.2 cm, the test piece is a large slide glass S9112 (7.6 cm × 5.2 cm: Matsunami Glass Industrial Co., Ltd.) having a thickness of 1.1 mm to be the second base material 31. The product was bonded so that the cross-sectional configuration of the conductive film portion was as shown in FIG. 7 and the layout viewed from above was as shown in FIG. At this time, the adhesive layer 21 was bonded to the glass instead of the second substrate 23 for peeling, and the conductive layer 12 was bonded to the first substrate 22 for peeling. Next, autoclaving was performed for 30 minutes at 50 ° C. and 0.8 Pa. As shown in FIGS. 7 and 8, the layer structure of insulating layer 11 / conductive layer 12 / adhesive layer 21 / second base material 31 was used. A conductive laminate 1 ″ of Example 1 was obtained. In the figure, reference numeral 32 denotes an extraction electrode layer.

(Production of touch panel)
A dry film for photoresist is laminated on the conductive layer of the above-described double-sided conductive film, a quartz mask is overlaid, and a metal halide lamp (multi-metal lamp M03-L31 for ultraviolet curing, manufactured by Eye Graphics Co., Ltd.) A process of irradiating ultraviolet rays with an irradiation amount of 300 mJ / cm ² on each side was performed on both sides. The pattern of the quartz mask was a pattern shape in which the XY electrode patterns were arranged perpendicularly on both sides of the insulating layer made of the first base so that the position of the quartz mask could be detected. In this case, the amount of ultraviolet rays that passed through the first base material and reached the opposite coated surface by the ultraviolet irradiation was very small, so that the patterning of the opposite surface was not reversed. Subsequently, a part of the conductive layer was removed together with the uncured resist using an organic polymer type conductive layer etching solution, and then the remaining resist film was peeled off to obtain a double-side patterned conductive film.

  A lead electrode wire was formed around the double-sided patterned conductive film using the above-described silver paste, and was connected to an FPC connector. Subsequently, 1 mm-thick optical glass (transparent sheet) 101 is bonded to both surfaces of each patterned conductive layer using two adhesive sheets α, and a touch panel module 100 ′ having a configuration shown in FIG. 6 is produced. did.

(Light resistance evaluation)
1) Evaluation by conductive laminate The resistance between electrodes in a normal temperature and normal humidity (23 ° C., 50 RH%) environment for the test piece which is the conductive laminate 1 ″ shown in FIGS. 7 and 8 obtained in Example 1 The value was measured with an ohmmeter. Next, this test piece was placed in a xenon weather meter so that the glass surface was on the light source side, and exposed for 48 hours at an illuminance of 390 W / m ² , a temperature of 63 ° C., and a humidity of 50% RH. After 48 hours, the sample was returned to a room temperature and humidity environment and conditioned for 4 hours, and then the resistance value was measured. Further, this sample was returned to the xenon weather meter, and the resistance value was measured in the same manner as after 48 hours each time the integrated irradiation time reached 96 hours and 240 hours.
2) Evaluation as a touch panel The touch panel module 100 ′ prepared in Example 1 was similarly irradiated with ultraviolet rays using a xenon weather meter, and then checked for operation in a normal temperature and humidity environment, and evaluated according to the following indicators. did. The evaluation results are shown in Table 1.
(Criteria)
A: Good responsiveness was exhibited as before the test.
B: The detection sensitivity was slightly deteriorated.
C: Detection sensitivity deteriorated.

[Example 2]
Conductivity is the same as in Example 1 except that a triazine-based liquid ultraviolet absorber (product name: TINUVIN477, manufactured by BASF) was used instead of TINUVIN109 as the ultraviolet absorber used in the coating solution for forming the adhesive layer. A laminate 1 ″ and a touch panel module 100 ′ were obtained. And it evaluated similarly to Example 1. FIG. The results are shown in Table 1.

[Comparative Example 1]
As a coating solution for forming an adhesive layer, a solution different from Example 1 was prepared only in that a benzotriazole-based liquid ultraviolet absorber (product name: TINUVIN109, manufactured by BASF) was not blended, thereby forming an adhesive layer. Except for this, a conductive laminate 1 ″ and a touch panel module 100 ′ were obtained in the same manner as in Example 1. And it evaluated similarly to Example 1. FIG. The results are shown in Table 1.

  In Examples 1 and 2, the change in resistance value before and after light irradiation was less than that in Comparative Example 1, and the decrease in conductivity over time was reduced.

1, 1 ′, 1 ″ conductive laminate 11 insulating layers 12, 12-U, 12-L conductive layers 21, 21-U, 21-L adhesive layer 100 100 ′ touch panel

Claims (9)

Having at least one pair of conductive layer and adhesive layer in contact with the whole surface or a part thereof,
The conductive layer contains a polythiophene-based conductive agent,
At least one layer of the pressure-sensitive adhesive layer contains an ultraviolet absorber. The ultraviolet absorber is
2. The conductive laminate according to claim 1, which has a maximum absorption wavelength at a wavelength of 350 nm or more and is at least one of an oily or liquid compound at 23 ° C. 3.   The polythiophene conductive agent is at least one selected from the group consisting of 3-hexylthiophene polymer, 3,4-ethylenedioxythiophene polymer, and derivatives of these polymers. The electroconductive laminated body of Claim 1 or 2. While having a set of the conductive layer and the adhesive layer, further comprising an insulating layer,
The conductive laminate according to any one of claims 1 to 3, wherein the conductive layer is in contact with one surface of the insulating layer. While having two sets of the conductive layer and the adhesive layer, further comprising an insulating layer,
The conductive laminate according to any one of claims 1 to 3, wherein the conductive layer is in contact with both surfaces of the insulating layer.   The conductive laminate according to claim 5, wherein the conductive layers in contact with both surfaces of the insulating layer are each formed in a pattern having regularity in a uniaxial direction, and the patterns are orthogonal to each other.   The conductive laminate according to any one of claims 4 to 6, wherein the insulating layer is formed to be bendable.   A touch panel comprising: the conductive laminate according to any one of claims 1 to 7; and a transparent sheet laminated via the adhesive layer of the conductive laminate.   The touch panel according to claim 8, wherein the touch panel is a capacitive type.

Images