JP5445042B2 - Conductive laminate and touch panel using the same - Google Patents

Description

  The present invention relates to a conductive laminate having a protective layer on a conductive layer. More specifically, the present invention relates to a conductive laminate that improves durability against a point load of a touch panel, that is, improved keystroke durability, and has both good durability and low optical reflectivity on the conductive layer side and good optical characteristics. It is. Furthermore, the present invention relates to a conductive laminate used for electrode members such as liquid crystal displays, organic electroluminescence, electronic paper, and related displays and solar cell modules.

  In recent years, mobile phones and game machines equipped with touch panels have become widespread. Electroconductive members for electrodes are used in touch panels. However, since the input to the touch panel is becoming finer, for example, point input is performed with a member with a small tip such as a pen, so the point load on the conductive member to be used There is an increasing demand for durability against keystrokes, that is, keystroke durability.

As a conductive member used for this touch panel, a conductive laminate in which an inorganic silicon oxide layer is further laminated on a conductive layer provided on a substrate has been proposed (Patent Documents 1 and 4). In addition, a conductive laminate has been proposed in which metal fine particles are used as a conductive layer, and a layer containing a silicone monomer or a silicone oligomer as a binder component together with SiO ₂ as a main component is laminated thereon (Patent Document 2). Furthermore, a conductive laminate (Patent Document 3) in which a plurality of layers containing an inorganic oxide layer and a linear organic polysiloxane that is a silicone polymer are sequentially laminated on the conductive layer, or a conductive layer using a polymer compound as a protective layer A conductive laminate laminated on top has also been proposed (Patent Document 4).

JP-A-11-203447 Japanese Patent No. 3442082 Japanese Patent No. 2847704 JP 2003-115221 A

  However, as in Patent Documents 1 and 4, if the layer on the conductive layer is only an inorganic oxide, there is a problem that the flexibility is poor, and the inorganic oxide layer or the conductive layer is cracked or insulated due to long-term keystrokes. However, even if a low molecular weight substance such as a monomer or oligomer is added as a binder component as in Patent Document 2, the flexibility is not improved, and similarly, cracks and cracks due to long-term keystrokes cannot be avoided. Further, even if a high molecular weight organic polysiloxane is contained as in Patent Document 3, if the structure is a linear structure, the point load force is not dispersed and the keystroke durability is not improved. Furthermore, since a touch panel that also serves as a display needs to display an image brightly, the conductive member to be used must have good transparency and optical characteristics as well as durability against keystroke. Even when a molecular compound is used as a protective layer, transparency and optical properties are insufficient.

  In view of the background of such prior art, the present invention aims to improve the durability against the point load of the touch panel, that is, the keystroke durability, and has good durability and good optical characteristics with low reflectivity on the conductive layer side. It is intended to provide a conductive laminate having both.

In order to solve this problem, the present invention employs the following configuration. That is,
(1) A conductive laminate in which a conductive layer and a protective layer using an inorganic silicon oxide are laminated in this order on at least one surface of the base material from the base material side, and the protection using the inorganic silicon oxide A conductive laminate used for a touch panel comprising a resin composition A containing at least one of the groups described in (i) to (iii) below in the layer;
(I) Silicone graft resin (ii) Silicone resin resin (iii) Modified silicone resin (2) The total content (% by mass) of the resin composition A contained in the protective layer is the total mass of the protective layer. The conductive laminate used for the touch panel according to (1), which is 5% by mass or more and 20% by mass or less,
(3) The touch panel according to claim 1 or 2, wherein the protective layer is formed by bonding the inorganic silicon oxide and any of the resins described in (i) to (iii) in the resin composition A. Conductive laminates used for ,
(4) The minimum value of the reflectance curve on the protective layer side is in the wavelength range of 350 to 550 nm, and the average reflectance on the protective layer side at a wavelength of 380 to 780 nm is 4% or less (1) to (3) A conductive laminate used for the touch panel according to any one of
(5) The conductive laminate used for a touch panel according to any one of (1) to (4), wherein the conductive layer contains a linear structure.
(6) Used for the touch panel according to any one of (1) to (5), wherein the total light transmittance based on JIS K7361-1 (1997) when incident from the protective layer side is 80% or more. conductive laminate is,
( 7 ) A touch panel using the conductive laminate according to ( 6 ),
It is what.
Moreover, the electrically conductive laminated body of this invention is used suitably for a touchscreen use. Furthermore, the conductive laminate of the present invention can also be suitably used for display members such as liquid crystal displays, organic electroluminescence, and electronic paper, and used electrode members such as solar cell modules.

  According to the present invention, at least one surface of the base material is laminated in order of the conductive layer and the specific protective layer from the base material side, thereby improving the durability against the point load of the touch panel, that is, the keystroke durability, and A conductive laminate having both good durability and low optical reflectivity on the conductive layer side and good optical characteristics can be provided.

It is an example of the cross-sectional schematic diagram of the electrically conductive laminated body of this invention. It is an example of the schematic diagram of the silicone graft resin of this invention. It is an example of the schematic diagram of the linear structure observed from the conductive layer side of the conductive laminated body of the present invention. It is an example of the schematic diagram of resin of the graft structure which has a hydrophilic group in the side chain of this invention. It is the schematic diagram which showed an example of the touchscreen which is the one aspect | mode of this invention. Schematic diagram of fluidized bed vertical reactor

The conductive laminate of the present invention is a conductive laminate in which a conductive layer and a protective layer made of an inorganic silicon oxide are laminated in this order from the substrate side, and the following (i) to (i) to the protective layer made of the inorganic silicon oxide: A resin composition A containing at least one kind of the resin described in (iii) is contained.
(I) Silicone graft resin (ii) Silicone resin resin (iii) Modified silicone resin When the resin composition A is contained in the protective layer, the keystroke durability of the touch panel can be improved and good durability can be obtained. It is estimated that the reason why the conductive layer side can have both low reflectance and good optical characteristics is as follows.

  In other words, the inorganic silicon oxide in the protective layer can be given good transparency because of its refractive index, and it has less reflection on the protective layer and the transmittance is improved, and the property change with respect to moisture and heat is small and good. Durability can be obtained, but the bonding mode is three-dimensional bonding, and is poor in flexibility and hard, so that inorganic silicon oxide alone is brittle with respect to point load and easily cracked. On the other hand, (i) the silicone graft resin has a branched structure as described later, and (ii) the silicone resin has a structure in which a linear silicone main chain is partially cross-linked. It is presumed that by including in the layer, the force of the point load is easily dispersed to prevent cracking. In addition, (iii) modified silicone has reactive functional groups in the structure such as molecular chain terminal, molecular chain, branched chain, etc., so that inorganic silicon oxide and modified silicone in the protective layer are bonded to each other. It is presumed that the force of the point load is easy to disperse through the connection and prevents cracking. Furthermore, since all of the resins (i) to (iii) have a silicone skeleton, optical properties are similar to those of inorganic silicon oxides compared to polymer compounds other than the silicone skeleton, and there is less reflection and the transmittance is improved. Therefore, good transparency can be imparted.

The conductive laminate of the present invention is a conductive laminate in which a conductive layer and a protective layer made of an inorganic silicon oxide are laminated in this order from the substrate side, and the following (i) to (i) to the protective layer made of the inorganic silicon oxide: A resin composition containing at least one kind of the resin described in (iii) is contained.
(I) Silicone graft resin (ii) Silicone resin resin (iii) Modified silicone resin When the conductive layer is not provided, it does not exhibit conductivity. Moreover, even if a protective layer is not provided or a protective layer is provided, the protective layer does not contain at least one resin of (i) to (iii) or contains (i) to ( If none of the above iii) corresponds to a resin, even if these conductive laminates are incorporated into a touch panel, the keystroke durability is not improved, and the durability and optical properties are also inferior. Furthermore, when the protective layer is not an inorganic silicon oxide, the durability is inferior.

  In the present invention, the protective layer needs to be made of inorganic silicon oxide. When inorganic silicon oxide is not contained, durability will be inferior. Here, the silicone resin containing the resin corresponding to the above (i) to (iii) is also an inorganic silicon oxide in a broad sense because it has a bond of silicon and oxygen, but the inorganic silicon oxidation in the present invention A thing is an inorganic silicon oxide as illustrated below. Specific examples of the inorganic silicon oxide include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, and methyltrimethoxy. Silane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, n-butyltrimethoxy Silane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-pentyltriethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyltrimethoxysilane, vinyltrimethoxysila , Vinyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) ) -3-Aminopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxy Silane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydro Cypropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyl Triethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Triethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureido Examples include trialkoxysilanes such as propyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, and vinyltriacetoxysilane, and organoalkoxysilanes such as methyltriacetyloxysilane and methyltriphenoxysilane. For example, after hydrolyzing these inorganic silicon oxides with various solvents such as alcohol, water, and acid, and applying a coating solution containing both resins corresponding to (i) to (iii), Although a protective layer can be formed by forming by a polymerization reaction, it is not particularly limited thereto.

In the present invention, the protective layer made of the inorganic silicon oxide needs to contain at least one selected from the group consisting of the resins described in the following (i) to (iii).
(I) Silicone graft resin (ii) Silicone resin resin (iii) Modified silicone resin The protective layer does not contain any of the resins (i) to (iii) or contains (i) to ( If none of the resins of iii) is applicable, even if these conductive laminates are incorporated in the touch panel, the keystroke durability is not improved, and the durability and optical properties are also inferior.

  (I) The silicone graft resin will be described. The silicone graft resin here is also called a silicone block polymerization resin, and its structure is illustrated in FIG. Fig. 2 shows the state in which silicone is bonded as a branch polymer to the side chain site of the main polymer, which is the main chain. The type of the main polymer and silicone, the degree of polymerization, the molecular weight, the end of the molecular chain, the molecular chain, Various states and performance are imparted depending on the functional group in the branched chain and the degree of crosslinking.

  Examples of silicone graft resin backbone polymers include polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polycarbonate resins, polyurethane resins, acrylic resins, methacrylic resins, epoxy resins, polyamide resins, polyimide resins, polyethylene resins, polypropylene resins, and polystyrene resins. , Polyvinyl acetate resin, nylon resin, melamine resin, phenol resin, and the like. These resins may be used alone or in combination of two or more types of copolymers and / or mixtures. In some applications, it may have a partially crosslinked structure.

  Next, (ii) the silicone resin resin will be described. Examples of silicone resins that are organic polysiloxanes include silicone oil, silicone rubber (silicone raw rubber), and silicone resin. Of these, silicone oil is a linear silicone resin, and silicone rubber (silicone raw rubber) is a linear structure. These silicone resins have a high degree of polymerization and both have a linear structure. On the other hand, the silicone resin is an organic polysiloxane containing a trifunctional (T unit) or tetrafunctional (Q unit) siloxane unit in the molecule, and has a linear silicone oil and silicone rubber (silicone raw rubber). Unlike it, it has a cross-linked structure and has a high cross-linking density.

  Next, (iii) the modified silicone resin will be described. Silicone with functions derived from functional groups by introducing various functional groups into the structure such as molecular chain ends, molecular chains, and branched chains of silicone. For example, to avoid bleed out as described later Reactive functional groups that form bonds with other components in the protective layer by heat, ultraviolet rays, catalysts, etc., functional groups compatible with other components in the protective layer, and organic solvents used during processing steps Is introduced. Silicone oil, silicone rubber (silicone raw rubber) with various functional groups introduced is a modified silicone with a linear structure, and (ii) those with various functional groups introduced into the silicone resin resin structure are modified with a crosslinked structure. In the present invention, the silicone resin is not particularly limited as long as it is a modified silicone resin having a linear structure or a modified silicone resin having a crosslinked structure.

  The resin composition A containing at least one selected from the group consisting of the resins described in (i) to (iii) according to the present invention may be contained in the protective layer in any manner, and simply mixed. It may be contained in a state, but for reasons such as further improvement of durability as described above, handleability, productivity, bleed out avoidance from the protective layer, etc., the inorganic silicon oxide in the protective layer and the above It is preferable that any one of the resins described in (i) to (iii) of A in the resin composition is bonded. Therefore, for example, a reactive functional group that forms a bond with the inorganic silicon oxide in the protective layer and any of the resins described in (i) to (iii) by heat, ultraviolet rays, a catalyst, etc. Any of the resins described in (i) to (iii) in the structure such as in a chain or in a branched chain can be suitably used.

  In addition to the reactive functional group, an organic solvent or an inorganic silicon oxide used in the protective layer processing step, or a functional group compatible with the resins described in (i) to (iii) above. Although it can have in a structure, such as a molecular chain terminal, a molecular chain, and a branched chain, it is not limited to these. Examples of these reactive functional groups include isocyanate groups, hydroxyl groups, carboxyl groups, alkoxy groups such as methoxy, ethoxy, and isopropoxy, amino groups, and epoxy groups. Other functional groups include, for example, Linear alkyl groups, branched alkyl groups, cycloalkyl groups, alkenyl groups such as vinyl, allyl, hexenyl, aryl groups such as phenyl, tolyl, xylyl, styryl, naphthyl, biphenyl, aralkyl groups such as benzyl, phenethyl, lactone, Other aromatic groups containing heterocyclic rings such as oxazole and imidazole and ring-opening groups thereof, acetoxy group, acrylic group, methacryl group, acryloxy group, methacryloxy group, oxycarbonyl groups such as allyloxycarbonyl and benzyloxycarbonyl, Sulfur-containing element functional groups such as capto and sulfide, nitrogen-containing element functional groups such as ureido and ketimino, halogen-containing element functional groups such as fluoroalkyl groups, and the like. What is necessary is just to select and use, 2 or more types may be mixed, It does not specifically limit to these.

  (I) Specific examples of the silicone graft resin include reactive silicone graft resins X-22-8004, X-22-8053, X-22-8114, X-22-8195, and X-22-8296. (Shin-Etsu Chemical Co., Ltd.), non-reactive silicone graft resins KP-545, X-24-798A (Shin-Etsu Chemical Co., Ltd.) and the like, and (ii) silicone resin resins and (iii) ) Modified silicone resins include polyester-modified X-24-8300, X-24-8310, X-24-8311, KR5230, KR5235 (manufactured by Shin-Etsu Chemical Co., Ltd.), and linear alkyl-modified X-22-2. 8004, X-22-8053, X-22-8114, X-22-8195, X-22-8296, X-24-798A (manufactured by Shin-Etsu Chemical Co., Ltd.) , Z-6018 (manufactured by Dow Corning Toray), acrylic modified KR9706 (manufactured by Shin-Etsu Chemical Co., Ltd.), alkoxy-modified KR213, KR9218 (manufactured by Shin-Etsu Chemical Co., Ltd.), phenyl-modified KR282, KR271 (manufactured by Shin-Etsu Chemical Co., Ltd.), hydroxyl-modified KR211, KR300, KR311, KR212 (manufactured by Shin-Etsu Chemical Co., Ltd.), epoxy-modified ES1001N, ES1002T, ES1023 (manufactured by Shin-Etsu Chemical Co., Ltd.), alkyd Examples include modified KR5206 (manufactured by Shin-Etsu Chemical Co., Ltd.), straight silicone resins KR242A, KR251, KR500 (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like for silicone rubbers, KR114A, KR165, KR169, KR2038 (Shin-Etsu Chemical). Kogyo Co., Ltd.) In the silicone oil system, amino-modified KF-868, KF-880, X-22-3820W, X-22-3939A, KF-8008, KF-8010, X-22-1660B-3 (manufactured by Shin-Etsu Chemical Co., Ltd.) ), Aralkyl-modified KF-410 (manufactured by Shin-Etsu Chemical Co., Ltd.), long-chain alkyl-modified KF-412, X-22-7322 (manufactured by Shin-Etsu Chemical Co., Ltd.), epoxy-modified KF-1001, X -22-2000, KF-105, X-22-163 series, X-22-173DX, X-22-9002 (manufactured by Shin-Etsu Chemical Co., Ltd.), alicyclic epoxy-modified X-22-2046, KF -102, X-22-169 series (manufactured by Shin-Etsu Chemical Co., Ltd.), hydroxyl-modified X-22-4039, KF-6001, KF-9701, X-22-170D X (manufactured by Shin-Etsu Chemical Co., Ltd.), diol-modified X-22-176F (manufactured by Shin-Etsu Chemical Co., Ltd.), carboxyl-modified X-22-3701E, X-22-162C, X-22-3710 ( Shin-Etsu Chemical Co., Ltd.), methacryl-modified X-22-164 series, X-22-174DX, X-22-2475 (manufactured by Shin-Etsu Chemical Co., Ltd.), higher fatty acid ester-modified KF-910, X -22-715 (manufactured by Shin-Etsu Chemical Co., Ltd.), higher fatty acid amide-modified KF-3935 (manufactured by Shin-Etsu Chemical Co., Ltd.), phenyl-modified KF-50 series (manufactured by Shin-Etsu Chemical Co., Ltd.), amino And methoxy modified KF-862, X-22-9192 (manufactured by Shin-Etsu Chemical Co., Ltd.), polyether modified X-22-6266, KF-353, X-22-6191, KF-6011 Shin-Etsu Chemical Co., Ltd.), phenol-modified X-22-1821 (Shin-Etsu Chemical Co., Ltd.), polyether and long chain alkyl and aralkyl-modified X-22-2516, KF-6004 (Shin-Etsu Chemical Co., Ltd.) Co., Ltd.), polyether and methoxy modified KF-889 (manufactured by Shin-Etsu Chemical Co., Ltd.), epoxy and polyether modified KF-1002, X-22-4741 (manufactured by Shin-Etsu Chemical Co., Ltd.), Examples include epoxy and aralkyl-modified X-22-3000T (manufactured by Shin-Etsu Chemical Co., Ltd.), long-chain alkyl and aralkyl-modified X-22-1877 (manufactured by Shin-Etsu Chemical Co., Ltd.), etc. Depending on the properties to be used, at least one kind may be arbitrarily selected and used, and two or more kinds may be mixed, and the invention is not particularly limited thereto.

  The content of the resin composition A contained in the protective layer according to the present invention depends on the type of resin, the difference in structure / bonding mode, etc., and thus cannot be uniquely limited. There is no particular limitation as long as durability, that is, keystroke durability can be improved, and both good durability and low optical reflectivity on the conductive layer side and good optical properties can be provided, but there is no particular limitation on the total mass of the protective layer. The total content (% by mass) of the resin composition A is preferably 5% by mass or more and 20% by mass or less. When the total content is 5% by mass or more and 20% by mass or less, better durability can be obtained while improving keystroke durability. If the amount is less than 5% by mass, the effect of improving the keying durability may be small. If the amount is more than 20% by mass, the durability may be inferior. The total content is more preferably 10% by mass to 15% by mass.

  In the present invention, the minimum value of the reflectance curve on the protective layer side is preferably in the wavelength range of 350 to 550 nm, and the average reflectance on the protective layer side at a wavelength of 380 to 780 nm is preferably 4% or less. When the minimum value of the reflectance curve on the protective layer side is in the wavelength range of 350 to 550 nm and the average reflectance on the protective layer side at a wavelength of 380 to 780 nm is 4% or less, the transparency is high and the color tone is high. Since it becomes a conductive laminated body which is neutral, it is preferable. The conductive layer reflects and absorbs light due to the physical properties of the conductive component itself. Therefore, as a method in which the minimum value of the reflectance curve on the protective layer side is in the wavelength range of 350 to 550 nm and the average reflectance on the protective layer side at a wavelength of 380 to 780 nm is 4% or less, protection on the conductive layer There is a method of forming a protective layer such that the layer becomes an optical interference film. The average reflectance on the protective layer side at a wavelength of 380 to 780 nm is preferably 3% or less, more preferably 2% or less. When the average reflectance is 4% or less, it becomes easy to obtain a conductive laminate having a high transparency and a neutral color tone, and as a result, the performance of a total light transmittance of 80% or more, which will be described later, when used for touch panel applications, etc. It is preferable because it can be obtained with high productivity. Further, it is preferable because generation of interference fringes due to interference of reflected light between the upper and lower sides through the space 22 on the touch panel shown in FIG. 5 can be suppressed. In addition to the role of optical interference, the protective layer is preferably a protective layer that also serves to improve the scratch resistance of the conductive layer and to prevent the conductive component from falling off.

  In order to lower the average reflectance of the protective layer, the refractive index is preferably lower than the refractive index of the conductive layer, and the difference from the refractive index of the conductive layer is preferably 0.3 or more, more preferably 0.4 or more. It is preferable that If the refractive index of the protective layer is higher than the refractive index of the conductive layer, it is not preferable because the average reflectance becomes higher than that of the conductive layer alone. Further, if the difference in refractive index is 0.3 or more, the control range in which the average reflectance is 4% or less is widened, and the process margin in production is increased, which is preferable.

  The components of the conductive layer according to the present invention are metals such as In, Sn, Au, Al, Cu, Pt, Pd, Ag, and Rh, metal oxides such as indium oxide, tin oxide, and zinc oxide, and composite oxides. Conductive thin films such as certain indium-doped tin oxide (hereinafter abbreviated as ITO), antimony-doped tin oxide (ATO) aluminum-doped zinc oxide, etc. are applied by dry processes such as vacuum deposition, sputtering, CVD, and ion plating. The forming method can be used. These methods are disclosed in Japanese Patent No. 2868686 and Japanese Patent No. 4208454, and these conductive thin films can be laminated on the base material of the present invention. It is preferable to use a linear structure. This is because when a linear structure is used, it is possible to perform lamination by an inexpensive wet coat process, unlike the lamination of conductive thin films using an expensive dry process disclosed as the known method. Examples of the linear structure in the present invention include carbon nanotubes (hereinafter abbreviated as CNT), metal or metal oxide nanowires, metal oxide whiskers and needle-like crystals.

  CNT will be described as an example of the linear structure. In the present invention, the CNT used as a component of the conductive layer may be any of single-walled CNT, double-walled CNT, and multilayered CNTs having three or more layers. Those having a diameter of about 0.3 to 100 nm and a length of about 0.1 to 20 μm are preferably used. In order to increase the transparency of the conductive laminate described later and reduce the surface resistance, single-walled CNTs and double-walled CNTs having a diameter of 10 nm or less and a length of 1 to 10 μm are more preferable. Moreover, it is preferable that impurities such as amorphous carbon and catalytic metal are not contained in the aggregate of CNTs as much as possible. When these impurities are contained, they can be appropriately purified by acid treatment or heat treatment. This CNT is synthesized and manufactured by arc discharge method, laser ablation method, catalytic chemical vapor phase method (method using a catalyst in which a transition metal is supported on a carrier in the chemical vapor phase method), etc. A catalytic chemical vapor phase method that can reduce the generation of impurities such as amorphous carbon is preferable.

  In the present invention, a conductive layer can be formed by applying a CNT dispersion, and when the base resin layer contains a graft structure resin having a hydrophilic group in the side chain together with a urethane acrylate resin. It can be used suitably. In order to obtain a CNT dispersion, it is common to perform a dispersion treatment with a CNT and a solvent using a mixing and dispersing machine or an ultrasonic irradiation device, and it is desirable to add a dispersant.

  The dispersant is not particularly limited as long as CNT can be dispersed, but the adhesion of the conductive layer containing CNT dispersed and coated with the CNT dispersion to the substrate, the hardness of the film, and the scratch resistance are not limited. In this respect, it is preferable to select a synthetic polymer or a natural polymer. Furthermore, a crosslinking agent may be added within a range that impairs dispersibility.

  Synthetic polymers include, for example, polyether diol, polyester diol, polycarbonate diol, polyvinyl alcohol, partially saponified polyvinyl alcohol, acetoacetyl group-modified polyvinyl alcohol, acetal group-modified polyvinyl alcohol, butyral group-modified polyvinyl alcohol, silanol group-modified polyvinyl alcohol, Ethylene-vinyl alcohol copolymer, ethylene-vinyl alcohol-vinyl acetate copolymer resin, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, acrylic resin, epoxy resin, modified epoxy resin, phenoxy resin, modified phenoxy resin, phenoxy Ether resin, phenoxy ester resin, fluorine resin, melamine resin, alkyd resin, phenol resin, polyacryl Bromide, polyacrylic acid, polystyrene sulfonic acid, polyethylene glycol, polyvinylpyrrolidone. Natural polymers include, for example, polysaccharides such as starch, pullulan, dextran, dextrin, guar gum, xanthan gum, amylose, amylopectin, alginic acid, gum arabic, carrageenan, chondroitin sulfate, hyaluronic acid, curdlan, chitin, chitosan, cellulose and the like It can be selected from derivatives. The derivative means a conventionally known compound such as ester or ether. These may be used alone or in combination of two or more. Among these, polysaccharides and derivatives thereof are preferable because of excellent dispersibility of CNTs. Furthermore, cellulose and derivatives thereof are preferable because of high film forming ability. Of these, esters and ether derivatives are preferable, and specifically, carboxymethyl cellulose and salts thereof are preferable.

  It is also possible to adjust the blending ratio between CNT and the dispersant. The compounding ratio of the CNT and the dispersant is preferably a compounding ratio that does not cause problems in adhesion to the substrate, hardness, and scratch resistance. Specifically, the CNT is preferably in the range of 10% by mass to 90% by mass with respect to the entire conductive layer. More preferably, it is the range of 30 mass%-70 mass%. When the CNT is 10% by mass or more, it is easy to obtain the necessary conductivity for the touch panel, and furthermore, it is easy to apply uniformly without being repelled on the surface of the substrate, and thus has a good appearance and quality. A conductive laminate can be supplied with high productivity. When the content is 90% by mass or less, the dispersibility of CNTs in a solvent is improved and is less likely to aggregate, which makes it easy to obtain a good CNT coating layer and good productivity. Further, the coating film is also strong, and it is preferable because scratches hardly occur during the production process and the uniformity of the surface resistance value can be maintained.

  In addition, metal and metal oxide nanowires exemplified as the linear structure are disclosed in JP-T-2009-505358, JP-A-2009-146747, JP-A-2009-70660, and Examples of metal oxide whiskers and fibrous needle-like crystals include, for example, WK200B of DENTOR WK series (manufactured by Otsuka Chemical Co., Ltd.), which is a composite oxide of potassium titanate fiber, tin and antimony oxide. , WK300R and WK500 are commercially available, and these linear structures containing the CNTs can be used alone or in combination of a plurality of them, and, if necessary, other micro-to-nano-sized conductive materials A material may be added, and is not particularly limited thereto.

  In the present invention, in order to form a conductive layer containing the linear structure, an underlayer containing a graft structure resin having a hydrophilic group in the side chain is further provided between the base material and the conductive layer. Also good. In the present invention, the conductive component of the conductive layer and the method of laminating the conductive layer are not uniquely limited, but in particular, depending on the type of the above-described linear structure or other conductive component, a solvent dispersion of the conductive component. In particular, it may be laminated by coating as an aqueous dispersion, in which case an underlayer is provided, and when the underlayer further contains a graft structure resin having a hydrophilic group in the side chain, The surface of the underlayer is modified, and it becomes easy to apply uniformly without repelling the dispersion solution of the conductive component. As a result, a conductive laminate having a good appearance and quality can be supplied with high productivity.

  The graft resin here is also called a block polymerization resin or the like, and its structure is illustrated in FIG. FIG. 4 shows a state in which the branched side chains of the main polymer, which is the main chain, are connected in a branch shape. The type of the main polymer and side chain, the degree of polymerization, the molecular weight, the molecular chain end, in the molecular chain, Various states and performance are imparted depending on the functional group in the branched chain and the degree of crosslinking. In the present invention, the graft resin has a hydrophilic group in the branched branched side chain.

Examples of the hydrophilic group include a hydroxyl group (—OH), a carboxyl group (—COOH), a sulfonic acid group (—SO ₃ H), a phosphoric acid group (H ₂ PO ₄ —), an amino group (—NH ₂ ), and the like. In addition, a part of H ⁺ of these hydrophilic groups may have a counter cation such as Na ⁺ , K ⁺ (for example, —ONa, —COONa, —SO ₃ Na, etc.), These hydrophilic groups may be present alone or in combination of two or more in the branched branch side chain. Also, a copolymer and / or a mixture of two types of graft resins having different hydrophilic groups may be used. You may use, It does not specifically limit to these.

  Examples of the backbone polymer of the graft resin include polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polycarbonate resins, polyurethane resins, acrylic resins, methacrylic resins, epoxy resins, polyamide resins, polyimide resins, polyethylene resins, polypropylene resins, polystyrene resins, Examples of the resin include polyvinyl acetate resin, nylon resin, melamine resin, phenol resin, and fluorine resin. These resins may be used alone or in combination of two or more types of copolymers and / or mixtures. It may also have a partially crosslinked structure depending on the application.

  In addition, the graft resin in the underlayer may be contained in any form, and may be contained simply in a mixed state, for reasons such as handling, productivity, and avoiding bleed out from the underlayer. May be present in combination with other components in the underlayer, and for example, reactive functional groups that form bonds with each resin or component in the underlayer by means of heat, ultraviolet rays, catalysts, etc. Graft resins that have functional groups compatible with other components in the formation layer and organic solvents and water used in the layering process of the underlayer in the molecular chain ends of the backbone polymer, in the molecular chain, etc. are preferably used However, the present invention is not limited to these. Examples of the functional group bonded to the molecular chain terminal and molecular chain of these backbone polymers include linear alkyl groups, branched alkyl groups, cycloalkyl groups, alkenyl groups such as vinyl, allyl, hexenyl, phenyl, tolyl, xylyl, Aryl groups such as styryl, naphthyl and biphenyl, aralkyl groups such as benzyl and phenethyl, other aromatic groups including heterocyclic rings such as lactone, oxazole and imidazole, and ring-opening groups thereof, alkoxy groups such as methoxy, ethoxy and isopropoxy, Acetoxy group, acrylic group, methacryl group, acryloxy group, methacryloxy group, oxycarbonyl group such as allyloxycarbonyl / benzyloxycarbonyl, epoxy group, isocyanate group, hydroxyl group, carboxyl group, sulfo group, phosphoric acid group, amino group, Mel Sulfur-containing elemental functional groups such as pto and sulfide, nitrogen-containing elemental functional groups such as ureido and ketimino, and halogen-containing elemental functional groups such as fluoroalkyl groups. It can be preferably used having a hydrophilic group such as hydroxyl group, carboxyl group, sulfonic acid group, phosphoric acid group, amino group, etc., but at least one type can be selected and used depending on the application and required properties Two or more types may be mixed, and the present invention is not particularly limited thereto. When the base layer contains a component other than the graft resin, the content of the graft resin is uniquely limited because it depends on the type of components of the conductive layer, the solvent of the dispersion solution, and further the processability. If the surface of the underlying layer is sufficiently modified and can be applied uniformly without repelling the dispersion solution of the conductive component, or a conductive laminate having a good appearance and quality can be supplied with high productivity, there is no particular limitation. However, when the content is less than 5% by mass with respect to the entire base layer, the modification effect on the surface of the base resin layer may be too small to obtain a difference as compared with the case where it is not contained.

  Specific examples of the graft structure having a hydrophilic group in the side chain include L-20, L-40M, LH-448 and the like of Chemitry (registered trademark) series (manufactured by Soken Chemical Co., Ltd.). Although it can be used, it is not limited to these.

The conductive laminate of the present invention has a surface resistance value on the side of the conductive layer of 1 × 10 ⁰ Ω / □ or more, regardless of the component of the conductive layer and the linear structure. It is preferably 1 × 10 ⁴ Ω / □ or less, more preferably 1 × 10 ¹ Ω / □ or more and 1.5 × 10 ³ or less. By being in this range, it can be preferably used as a conductive laminate for a touch panel. That is, if it is 1 × 10 ⁰ Ω / □ or more, power consumption can be reduced, and if it is 1 × 10 ⁴ Ω / □ or less, the influence of errors in the coordinate reading of the touch panel can be reduced.

  The conductive laminate according to the present invention is preferably a transparent conductive laminate having a total light transmittance of 80% or more based on JIS K7361-1 (1997) when incident from the conductive layer side. When the conductive laminate of the present invention is incorporated into a touch panel as a transparent conductive laminate, the touch panel not only has durability against point load, that is, keystroke durability and durability, but also exhibits excellent transparency. The display of the display provided in the lower layer of the touch panel using a laminated body can be recognized vividly. Transparency in the present invention means that the total light transmittance based on JIS K7361-1 (1997) when incident from the conductive layer side is 80% or more, preferably 85% or more. Preferably it is 90% or more. As a method for increasing the total light transmittance, for example, in addition to the above-described method of setting the average reflectance at a wavelength of 380 to 780 nm on the transparent protective film side to 4% or less, the total light transmittance of the substrate to be used is And a method of increasing the thickness of the conductive layer. As a method for increasing the total light transmittance of the base material, a method of reducing the thickness of the base material or a method of selecting a base material made of a material having a large total light transmittance can be mentioned.

  As the substrate in the transparent conductive laminate of the present invention, a substrate having a high visible light total light transmittance can be suitably used. Specifically, the total light transmittance based on JIS K7361-1 (1997) is 80. % Or more, more preferably 90% or more of transparency. Specifically, for example, a transparent resin, glass, and the like can be used. The film may be a film that can be wound up with a thickness of 250 μm or less, or may be a substrate that exceeds 250 μm in thickness. From the viewpoint of cost, productivity, handleability, etc., a resin film of 250 μm or less is preferable, particularly preferably 190 μm or less, and more preferably 150 nm or less. Examples of the resin include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyimide, polyphenylene sulfide, aramid, polypropylene, polyethylene, polylactic acid, polyvinyl chloride, polycarbonate, polymethyl methacrylate, and alicyclic acrylic resin. , Cycloolefin resin, triacetyl cellulose, and those obtained by mixing and / or copolymerizing these resins. For example, the resin can be unstretched, uniaxially stretched, or biaxially stretched to form a film. As the glass, ordinary soda glass can be used. Moreover, these several base materials can also be used in combination. For example, a composite substrate such as a substrate in which a resin and glass are combined and a substrate in which two or more kinds of resins are laminated may be used. Furthermore, the base material may be surface-treated as necessary. The surface treatment may be provided with a physical treatment such as glow discharge, corona discharge, plasma treatment, flame treatment, or a resin layer. In the case of a film, a film having an easy adhesion layer may be used. The kind of base material is not limited to the above, and an optimal one can be selected from transparency, durability, flexibility, cost, etc. according to the application.

  The film thickness of the protective layer according to the present invention is to improve the durability against the point load of the touch panel, that is, the keystroke durability, and has a good durability and an average reflectance on the transparent protective film side at a wavelength of 380 to 780 nm. Although it will not specifically limit if it is a film thickness which will be 4% or less, Preferably it is 10 nm-150 nm, More preferably, it is 40 nm-120 nm, More preferably, it is 60-100 nm. When the thickness of the protective film is 10 nm or more, the film strength increases, and the function of protecting the conductive layer such as durability and scratch resistance is improved. On the other hand, when the thickness is 150 nm or less, interference fringes due to light interference are not visually recognized, the transmission color tone becomes neutral, and an increase in the surface resistance value of the conductive layer can be suppressed.

  As a method for forming the protective layer on the conductive layer, an optimum method may be selected depending on the material to be formed. Dry methods such as vacuum deposition, EB deposition, sputtering, casting, spin coating, dip coating, bar coating, spraying General methods such as wet coating methods such as blade coating, slit die coating, gravure coating, reverse coating, screen printing, mold coating, print transfer, and inkjet can be used. Among these, a wet coating method using a microgravure that can form a protective layer uniformly and with high productivity is preferable.

  Various additives can be added to the substrate and / or each layer according to the present invention within a range that does not impair the effects of the present invention. Examples of the additives include organic and / or inorganic fine particles, crosslinking agents, flame retardants, flame retardant aids, heat stabilizers, oxidation stabilizers, leveling agents, slip activators, conductive agents, antistatic agents, and ultraviolet rays. Absorbers, light stabilizers, nucleating agents, dyes, fillers, dispersants, coupling agents, and the like can be used.

  Next, the touch panel of the present invention will be described. FIG. 5 is a schematic cross-sectional view showing an example of a resistive film type touch panel. The resistive touch panel has a configuration in which the upper electrode 15 is fixed on the lower electrode 16 by a frame-like double-sided adhesive tape 21. A base layer 2, a conductive layer 3, and a protective layer 4 are laminated in this order on the base materials 17 and 18 constituting the upper and lower electrodes, and the conductive layers 3 of the upper and lower electrodes sandwich the space 22. Thus, they are formed so as to face each other. Further, the base layer 2 may be provided between the base material 17 or 18 and the conductive layer 3. Dot spacers 20 are provided in the space 22 at regular intervals, thereby holding a gap between the upper and lower conductive layers. The upper surface of the base material 17 is a surface where the pen 24 and the tip of the finger come into contact, and a hard coat layer 19 is provided to prevent scratches. The touch panel is operated by applying a voltage from the power source 23 and pressing the surface of the hard coat layer 19 with the pen 24 or the tip of a finger to apply a load, so that electricity flows from the contacted portion. The touch panel having the above configuration is used, for example, by attaching a lead wire and a drive unit and incorporating it on the front surface of the liquid crystal display.

  Since the resistive film type touch panel shown in FIG. 5 is configured through the space 22, the conductive laminate is deformed by a load when input with a pen or a finger and the conductive laminates are brought into contact with each other. This is a touch panel configuration having the highest effect of using the laminate.

  Hereinafter, the present invention will be specifically described based on examples. However, the present invention is not limited to the following examples. First, an evaluation method in each example and comparative example will be described.

(1) Identification of structure and bonding mode of compound in each layer First, a sample is immersed in a solvent, each layer is peeled and collected, and the solvent after immersion is filtered. If there is filter cake, select a solvent having high solubility in the filter cake and dissolve it again. Next, a separable method is selected from general chromatography represented by silica gel column chromatography, gel permeation chromatography, liquid high-performance chromatography, gas chromatography, etc., and the filtrate and the redissolved filtrate solution are each simply used. Separate and purify into one substance. If separation with other components is difficult, use as is.

Thereafter, each substance is appropriately concentrated and diluted, and nuclear magnetic resonance spectroscopy ( ¹ H-NMR, ¹³ C-NMR, ²⁹ Si-NMR), two-dimensional nuclear magnetic resonance spectroscopy (2D-NMR), infrared spectrophotometry. (IR), Raman spectroscopy, mass spectrometry (Mass), X-ray diffraction (XRD), neutron diffraction (ND), low-energy electron diffraction (LEED), high-energy reflection electron diffraction (RHEED), Atomic absorption spectrometry (AAS), ultraviolet photoelectron spectroscopy (UPS), X-ray photoelectron spectroscopy (XPS), X-ray fluorescence elemental analysis (XRF), inductively coupled plasma emission spectroscopy (ICP-AES), electron beam micro The structure and bonding mode were identified by appropriately selecting and combining methods from an analyzer (EPMA), gel permeation chromatography (GPC), and other elemental analysis.

(2) Content of Resin Corresponding to Resins (i) to (iii) in the Protective Layer Isolation and identification were performed in the same manner as in (1). For each single substance after identification, only the substances corresponding to the resins of (i) to (iii) above are selected, and after concentration and dilution as appropriate, each wavelength is measured using a wavelength dispersive X-ray fluorescence analyzer. The intrinsic X-ray peak intensity of the silicon element for the corresponding substance was measured. After that, after preparing a calibration curve of peak intensity and content rate using a standard substance with the same structure as that of each detected resin, that is, the content rate is known, the content of silicon element in the obtained peak intensity value of the sample The ratio was determined from a calibration curve, and the concentration of each resin, that is, the content ratio was determined from the silicon element content. Five places were measured by the same method, and the average of the five places was defined as “resin content”.

(3) Surface resistance value R ₀
The surface resistance on the conductive layer side was measured at a central portion of a 100 mm × 50 mm sample by a four-probe method using a low resistivity meter Loresta-EP MCP-T360 (manufactured by Mitsubishi Chemical Corporation). An average value was calculated for five samples, and this was defined as a surface resistance value _R0 .

(4) Durability (heat resistance)
After heating the sample of (3) in a thermostatic oven with a safety door (SPHH-201, manufactured by ESPEC Corp.) at 150 ° C. for 1 hour, the same position is restored by the same method as in (3) above. The surface resistance value R was measured to calculate R / R ₀ (R ₀ is the value of the item (3)). Similarly, it implemented about 5 samples, and made the average value of each R / _R0 the rate of increase of a surface resistance value, and used it as the heat resistance index. The determination criteria in the present invention are determined as follows. If the grades are A and B, the grade is acceptable, and the grade A is most preferred.
Class A: R / R ₀ ≦ 1.50
Class B: 1.50 <R / R ₀ ≦ 1.80
Class C: R / R ₀ > 1.80
(5) Durability (moisture and heat resistance)
The sample of (3) is subjected to the same method as in (3) above after 240 hours have passed in a thermostat perfect oven (manufactured by ESPEC Corporation, PH-400) at 60 ° C. and 90% RH. Then, the surface resistance value R at the same position was measured again to calculate R / R ₀ (R ₀ is the value of the item (3)). Similarly, it implemented about 5 samples, and made the average value of each R / _R0 the rate of increase of a surface resistance value, and used it as the heat resistance index. The determination criteria in the present invention are determined as follows. If the grades are A and B, the grade is acceptable, and the grade A is most preferred.
Class A: R / R ₀ ≦ 1.50
Class B: 1.50 <R / R ₀ ≦ 1.80
Class C: R / R ₀ > 1.80
(6) Structure of conductive component The surface of the sample on the conductive layer side is subjected to an acceleration voltage of 3.0 kV using a field emission scanning electron microscope (JSM-6700-F, manufactured by JEOL Ltd.) or atomic force. The images were observed with a microscope (NanoScope III manufactured by Digital Instruments). If the surface could not be observed by surface observation, the components of the conductive layer were separated and purified by one of the methods similar to (1), and a sufficient amount of substances corresponding to the conductive components were collected and collected, and then observed in the same manner.

(7) Total light transmittance Based on JIS K7361-1 (1997) using a turbidimeter (cloudiness meter) NDH2000 (manufactured by Nippon Denshoku Industries Co., Ltd.), total light transmittance in the thickness direction of the conductive laminate. The rate was measured by making light incident from the conductive layer side. An average value was calculated from the values measured for five samples, and this was defined as the total light transmittance.

(8) Keystroke Durability of Touch Panel First, in the touch panel of FIG. 5, a 40 mm long × 40 mm wide touch panel was manufactured using the conductive laminates of the examples and comparative examples of the present invention as the upper electrode 15 and the lower electrode 16, respectively. . Next, a silicone rubber pen 3R (manufactured by Touch Panel Laboratories, Inc.) with a pen tip shape of 3 mm radius in the keystroke section (solenoid type) of the keystroke tester (with touch panel laboratory, drive power supply and oscilloscope) Was set on the touch panel produced so that the pen tip was at the center position of the touch panel (vertical position 20 mm, horizontal position 20 mm). Next, a load of 200 g was applied to the touch panel with an applied voltage of 3 V and an additional resistance of 100 kΩ, and the value of the contact resistance when the conductive layers of the upper electrode 15 and the lower electrode 16 in FIG. Next, after pressing the silicone rubber pen for 1 million times at a load of 250 g and 10 Hz, again, the value of contact resistance when a load of 200 g was applied with an applied voltage of 3 V and an additional resistance of 100 kΩ was read as Re, and Re / Rs was calculated. Similarly, three samples were used, and the average value of each Re / Rs was used as an index of the keystroke durability as an increase rate of the contact resistance value. The determination criteria in the present invention are determined as follows. If the grades are A and B, the grade is acceptable, and the grade A is most preferred.
Class A: Re / Rs ≦ 1.15
Class B: 1.15 <Re / Rs ≦ 1.30
Class C: Re / Rs> 1.30
(9) Refractive index About the coating film formed with the coater on the silicon wafer or quartz glass, the change of the polarization state of the reflected light of a coating film is performed using the high-speed spectrometer M-2000 (made by JA Woollam). Was measured at an incident angle of 60 degrees, 65 degrees, and 70 degrees, and the refractive index at a wavelength of 550 nm was obtained by calculation using analysis software WVASE32.

(10) Film thickness of protective layer The film thickness of the protective film of the produced conductive laminate was accelerated at 3.0 kV using a field emission scanning electron microscope (JSM-6700-F, manufactured by JEOL Ltd.). Three arbitrary magnifications were selected from the observation magnifications of 10,000 to 200,000, and the images were observed at each magnification by appropriately adjusting the contrast of the image. Sample cross-section adjustment was performed using a rotary microtome manufactured by Nippon Microtome Laboratory. From any of the obtained cross-sectional photographs, five arbitrary positions were similarly measured at three arbitrary magnifications (calculated from the magnification), and the values at a total of 15 positions were averaged.

(11) Average reflectance The surface opposite to the surface on which the protective layer is provided is uniformly made of water-resistant sandpaper No. 320 to 400 so that the 60 ° C. gloss (JIS Z 8741 (1997)) is 10 or less. After roughening, a black paint was applied and colored so that the visible light transmittance was 5% or less. With a spectrophotometer (UV-3150) manufactured by Shimadzu Corporation, the absolute reflection spectrum in the wavelength region of 300 nm to 800 nm was measured at 1 nm intervals at an incident angle of 5 degrees from the measurement surface, and the wavelength was measured at 380 nm to 780 nm. Average reflectance was determined.

  The material used for the protective layer of each Example and a comparative example is shown below. Each protective layer was laminated on the conductive layer by the methods of Examples and Comparative Examples.

(1) Protective layer material A (inorganic silicon oxide)
The inorganic silicon oxide in the protective layer according to the present invention was obtained as follows.

  In a 100 mL plastic container, 20 g of ethanol was added, and 40 g of n-butyl silicate was added and stirred for 30 minutes. Thereafter, 10 g of 0.1N hydrochloric acid aqueous solution was added, and the mixture was stirred for 2 hours (hydrolysis reaction) and stored at 4 ° C. The next day, this solution was diluted with an isopropyl alcohol / toluene / n-butanol mixed solution (mixing mass ratio 2/1/1) so that the solid content concentration was 2.0% by mass. The refractive index of the inorganic silicon oxide film obtained by applying this solution to a silicon wafer and drying was 1.44.

(2) Protective layer material B
Non-reactive silicone graft resin (Shin-Etsu Chemical Co., Ltd. X-24-798A, 50% concentration solution, resin corresponding to (i), functional group: methyl group, n-butyl group Unable to bond with components in protective layer )
(3) Protective layer material C
Reactive silicone graft resin (Shin-Etsu Chemical Co., Ltd. X-22-8114 concentration 40% solution, resin corresponding to (i), functional group: hydroxyl group, methyl group, n-butyl group and the components in the protective layer Can be combined)
(4) Protective layer material D
Reactive silicone graft resin (Shin-Etsu Chemical Co., Ltd. X-22-8195 concentration 30% solution, resin corresponding to (i), functional group: carboxyl group, methyl group, n-butyl group Can be combined)
(5) Protective layer material E
Non-reactive straight silicone resin (manufactured by Shin-Etsu Chemical Co., Ltd., KR242A 50% concentration solution, resin corresponding to (ii), functional group: methyl group, unable to bind to components in protective layer)
(6) Protective layer material F
Reactive silicone oil resin (Shin-Etsu Chemical Co., Ltd. X-24-8300 concentration 25% solution, resin corresponding to (iii), functional group: hydroxyl group, methyl group can be combined with components in the protective layer)
(7) Protective layer material G
Non-reactive straight silicone oil resin (Shin-Etsu Chemical Co., Ltd. KF-69 100% concentration solution, silicone resin not corresponding to any of (i) to (iii), functional group: methyl group and components in the protective layer Cannot be combined)
(8) Additive A
Reaction catalyst for curing (CAT-AC manufactured by Shin-Etsu Chemical Co., Ltd.).

  The conductive layer and underlayer in each example and comparative example are shown below. Each conductive layer was laminated | stacked with the following each method on the base material in the Example and the comparative example, or on the base layer provided on the base material.

(1) Conductive layer A “ITO conductive layer”
Using an indium tin oxide target having a composition of In ₂ O ₂ / SnO ₂ = 90/10, an ITO conductive film having a thickness of 250 nm was formed by sputtering under an argon / oxygen mixed gas introduction at a vacuum degree of 10 ⁻⁴ Torr. A functional thin film was provided.

(2) Conductive layer B “CNT conductive layer”
(Catalyst adjustment)
2.459 g of ammonium iron citrate (green) (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 500 mL of methanol (manufactured by Kanto Chemical Co., Inc.). To this solution, 100 g of light magnesia (Iwatani Chemical Industry Co., Ltd.) was added, stirred at room temperature for 60 minutes, dried under reduced pressure with stirring at 40 ° C. to 60 ° C. to remove methanol, and the metal salt was added to the light magnesia powder. Was obtained.

(CNT composition production)
CNTs were synthesized in a fluidized bed vertical reactor shown in the schematic diagram of FIG. The reactor 100 is a cylindrical quartz tube having an inner diameter of 32 mm and a length of 1200 mm. A quartz sintered plate 101 is provided at the center, an inert gas and source gas supply line 104 is provided at the lower part of the quartz tube, and an exhaust gas line 105 and a catalyst charging line 103 are provided at the upper part. In addition, a heater 106 is provided that surrounds the circumference of the reactor so that the reactor can be maintained at an arbitrary temperature. The heater 106 is provided with an inspection port 107 so that the flow state in the apparatus can be confirmed.

  12 g of the catalyst was taken, and the catalyst 108 shown in the “catalyst adjustment” portion was set on the quartz sintered plate 101 through the catalyst charging line 103 from the sealed catalyst supplier 102. Subsequently, supply of argon gas from the source gas supply line 104 was started at 1000 mL / min. After the inside of the reactor was placed in an argon gas atmosphere, the temperature was heated to 850 ° C.

  After reaching 850 ° C., the temperature was maintained, the argon flow rate of the raw material gas supply line 104 was increased to 2000 mL / min, and fluidization of the solid catalyst on the quartz sintered plate was started. After confirming fluidization from the heating furnace inspection port 107, supply of methane to the reactor at 95 mL / min was started. After supplying the mixed gas for 90 minutes, the flow was switched to a flow of only argon gas, and the synthesis was terminated.

  The heating was stopped and the mixture was allowed to stand at room temperature, and after reaching room temperature, the CNT composition containing the catalyst and CNTs was taken out from the reactor.

  23.4 g of the CNT composition with a catalyst shown above was placed in a magnetic dish and heated at 446 ° C. for 2 hours in the atmosphere in a muffle furnace (FP41, manufactured by Yamato Scientific Co., Ltd.) that had been heated to 446 ° C. in advance. And then removed from the muffle furnace. Next, in order to remove the catalyst, the CNT composition was added to a 6N aqueous hydrochloric acid solution and stirred at room temperature for 1 hour. The recovered product obtained by filtration was further added to a 6N aqueous hydrochloric acid solution and stirred at room temperature for 1 hour. After filtering this and washing with water several times, 57.1 mg of the CNT composition from which magnesia and metals have been removed can be obtained by drying the filtrate in an oven at 120 ° C. overnight. By repeating the above operation, 500 mg of a CNT composition from which magnesia and metal were removed was prepared.

  Next, 80 mg of the CNT composition after removing the catalyst by heating in a muffle furnace was added to 27 mL of concentrated nitric acid (1st grade Assay 60-61%, manufactured by Wako Pure Chemical Industries, Ltd.) and stirred for 5 hours in a 130 ° C. oil bath. While heating. After completion of heating and stirring, the nitric acid solution containing CNTs was filtered, washed with distilled water, and 1266.4 mg of a CNT composition was obtained in a wet state containing water.

(CNT dispersion coating liquid)
In a 50 mL container, 10 mg of the above CNT composition (converted at the time of drying), 10 mg of sodium carboxymethyl cellulose (Sigma, 90 kDa, 50-200 cps) as a dispersing agent, weighed to 10 g with distilled water, ultrasonic homogenizer output 20 W, Dispersion treatment was performed for 20 minutes under ice cooling to prepare a CNT coating solution. The obtained liquid was centrifuged at 10,000 G for 15 minutes with a high-speed centrifuge to obtain 9 mL of the supernatant. 5 mL of ethanol was added to 145 mL of the supernatant obtained by repeating this operation a plurality of times, to obtain a CNT dispersion coating solution having a CNT concentration of about 0.1% by mass (a mixing ratio of CNT and dispersant of 1: 1) that can be applied by a coater. The refractive index of the CNT conductive layer obtained by applying this CNT dispersion coating liquid to quartz glass and drying was 1.82.

(Formation of CNT conductive layer)
The CNT-dispersed coating liquid was applied with a micro gravure coater (gravure wire number 150R, gravure rotation ratio 80%) and dried at 100 ° C. for 1 minute to provide a CNT coating film.

(3) Conductive layer C "Silver nanowire conductive layer"
Silver nanowires were obtained by the method disclosed in Example 1 (synthesis of silver nanowires) in JP-T-2009-505358. Next, a silver nanowire-dispersed coating liquid was obtained by the method disclosed in Example 8 (nanowire dispersion) of JP-T-2009-505358. This silver nanowire-dispersed coating solution was applied using a bar coater manufactured by Matsuo Sangyo Co., Ltd. and dried at 120 ° C. for 2 minutes to provide a silver nanowire coating film.

(4) Underlayer 10 g of Chemitry (registered trademark) L-20 (manufactured by Soken Chemical Co., Ltd., graft acrylic having a hydroxyl group (—OH) as a hydrophilic group in the side chain, solid content concentration: 26% by mass solution), 3 g of ethyl acetate was prepared, mixed and stirred to prepare a base layer coating solution. This undercoat layer coating solution was applied using a bar coater count 16 manufactured by Matsuo Sangyo Co., Ltd., and dried by heating at 100 ° C. for 3 minutes to obtain an undercoat layer having a coating thickness after drying of 4.8 μm.

Example 1
KAYANOVA (registered trademark) FOP1740 (Nippon Kayaku Co., Ltd.) manufactured by Nippon Kayaku Co., Ltd. on one side, using a polyethylene terephthalate film having a thickness of 188 μm and Lumirror (registered trademark) U46 (manufactured by Toray Industries, Inc.) as a base material. Microgravure coater (gravure wire number 80R, gravure rotation ratio 100%) with a hard coating agent diluted to a solid content concentration of 40% by mass with a 1: 1 mass ratio of toluene and methyl ethyl ketone (MEK). After coating at 80 ° C. for 1 minute, ultraviolet rays were irradiated at 1.0 J / cm ² and cured to provide a hard coat layer having a thickness of 5 μm.

  Next, “conductive layer A” was laminated on the opposite surface of the base material provided with the hard coat layer.

  Next, 50,000.000 g of “Protective layer material A”, 0.8333 g of “Protective layer material B”, and 540.8333 g of “ethyl acetate / toluene mixed solvent (mixing mass ratio 1/1)” were mixed and stirred, and a protective layer was applied. I made a liquid. This protective layer coating solution is applied on the “conductive layer A” by microgravure coating (gravure wire number 80R, gravure rotation ratio 100%), dried at 125 ° C. for 1 minute to provide a protective layer having a thickness of 60 nm. The conductive laminate of the invention was obtained.

(Example 2)
KAYANOVA (registered trademark) FOP1740 (Nippon Kayaku Co., Ltd.) manufactured by Nippon Kayaku Co., Ltd. on one side, using a polyethylene terephthalate film having a thickness of 188 μm and Lumirror (registered trademark) U46 (manufactured by Toray Industries, Inc.) as a base material. Microgravure coater (gravure wire number 80R, gravure rotation ratio 100%) with a hard coating agent diluted to a solid content concentration of 40% by mass with a 1: 1 mass ratio of toluene and methyl ethyl ketone (MEK). After coating at 80 ° C. for 1 minute, ultraviolet rays were irradiated at 1.0 J / cm ² and cured to provide a hard coat layer having a thickness of 5 μm.

  Next, “conductive layer A” was laminated on the opposite surface of the base material provided with the hard coat layer.

  Next, “Protective layer material A” 500.0000 g, “Protective layer material E” 0.8333 g, “Additive A” 0.0042 g, “Ethyl acetate / toluene mixed solvent (mixing mass ratio 1/1)” 541.2458 g Were mixed and stirred to form a protective layer coating solution. This protective layer coating solution was applied on the “conductive layer A” by microgravure coating (gravure wire number 80R, gravure rotation ratio 100%), heated at 125 ° C. for 1 hour to provide a protective layer having a thickness of 60 nm. The conductive laminate of the invention was obtained.

(Example 3)
KAYANOVA (registered trademark) FOP1740 (Nippon Kayaku Co., Ltd.) manufactured by Nippon Kayaku Co., Ltd. on one side, using a polyethylene terephthalate film having a thickness of 188 μm and Lumirror (registered trademark) U46 (manufactured by Toray Industries, Inc.) as a base material. Microgravure coater (gravure wire number 80R, gravure rotation ratio 100%) with a hard coating agent diluted to a solid content concentration of 40% by mass with a 1: 1 mass ratio of toluene and methyl ethyl ketone (MEK). After coating at 80 ° C. for 1 minute, ultraviolet rays were irradiated at 1.0 J / cm ² and cured to provide a hard coat layer having a thickness of 5 μm.

  Next, “conductive layer A” was laminated on the opposite surface of the base material provided with the hard coat layer.

  Next, 50,000.000 g of “Protective layer material A”, 1.6667 g of “Protective layer material F”, and 540.000 g of “ethyl acetate / toluene mixed solvent (mixing mass ratio 1/1)” were mixed and stirred, and the protective layer was applied. I made a liquid. This protective layer coating solution is applied on the “conductive layer A” by microgravure coating (gravure wire number 80R, gravure rotation ratio 100%), dried at 125 ° C. for 1 minute to provide a protective layer having a thickness of 60 nm. The conductive laminate of the invention was obtained.

Example 4
KAYANOVA (registered trademark) FOP1740 (Nippon Kayaku Co., Ltd.) manufactured by Nippon Kayaku Co., Ltd. on one side, using a polyethylene terephthalate film having a thickness of 188 μm and Lumirror (registered trademark) U46 (manufactured by Toray Industries, Inc.) as a base material. Microgravure coater (gravure wire number 80R, gravure rotation ratio 100%) with a hard coating agent diluted to a solid content concentration of 40% by mass with a 1: 1 mass ratio of toluene and methyl ethyl ketone (MEK). After coating at 80 ° C. for 1 minute, ultraviolet rays were irradiated at 1.0 J / cm ² and cured to provide a hard coat layer having a thickness of 5 μm.

  Next, “conductive layer B” was laminated after laminating “underlayer” on the opposite surface of the base material provided with the hard coat layer.

  Next, 50,000.000 g of “Protective layer material A”, 0.8333 g of “Protective layer material B”, and 540.8333 g of “ethyl acetate / toluene mixed solvent (mixing mass ratio 1/1)” were mixed and stirred, and a protective layer was applied. I made a liquid. This protective layer coating solution is applied on the “conductive layer A” by microgravure coating (gravure wire number 80R, gravure rotation ratio 100%), dried at 125 ° C. for 1 minute to provide a protective layer having a thickness of 60 nm. The conductive laminate of the invention was obtained.

(Example 5)
KAYANOVA (registered trademark) FOP1740 (Nippon Kayaku Co., Ltd.) manufactured by Nippon Kayaku Co., Ltd. on one side, using a polyethylene terephthalate film having a thickness of 188 μm and Lumirror (registered trademark) U46 (manufactured by Toray Industries, Inc.) as a base material. Microgravure coater (gravure wire number 80R, gravure rotation ratio 100%) with a hard coating agent diluted to a solid content concentration of 40% by mass with a 1: 1 mass ratio of toluene and methyl ethyl ketone (MEK). After coating at 80 ° C. for 1 minute, ultraviolet rays were irradiated at 1.0 J / cm ² and cured to provide a hard coat layer having a thickness of 5 μm.

  Next, “conductive layer B” was laminated after laminating “underlayer” on the opposite surface of the base material provided with the hard coat layer.

  Next, “Protective layer material A” 500.0000 g, “Protective layer material E” 0.8333 g, “Additive A” 0.0042 g, “Ethyl acetate / toluene mixed solvent (mixing mass ratio 1/1)” 541.2458 g Were mixed and stirred to form a protective layer coating solution. This protective layer coating solution was applied on the “conductive layer A” by microgravure coating (gravure wire number 80R, gravure rotation ratio 100%), heated at 125 ° C. for 1 hour to provide a protective layer having a thickness of 60 nm. The conductive laminate of the invention was obtained.

(Example 6)
KAYANOVA (registered trademark) FOP1740 (Nippon Kayaku Co., Ltd.) manufactured by Nippon Kayaku Co., Ltd. on one side, using a polyethylene terephthalate film having a thickness of 188 μm and Lumirror (registered trademark) U46 (manufactured by Toray Industries, Inc.) as a base material. Microgravure coater (gravure wire number 80R, gravure rotation ratio 100%) with a hard coating agent diluted to a solid content concentration of 40% by mass with a 1: 1 mass ratio of toluene and methyl ethyl ketone (MEK). After coating at 80 ° C. for 1 minute, ultraviolet rays were irradiated at 1.0 J / cm ² and cured to provide a hard coat layer having a thickness of 5 μm.

  Next, “conductive layer B” was laminated after laminating “underlayer” on the opposite surface of the base material provided with the hard coat layer.

  Next, 50,000.000 g of “Protective layer material A”, 1.6667 g of “Protective layer material F”, and 540.000 g of “ethyl acetate / toluene mixed solvent (mixing mass ratio 1/1)” were mixed and stirred, and the protective layer was applied. I made a liquid. This protective layer coating solution is applied on the “conductive layer A” by microgravure coating (gravure wire number 80R, gravure rotation ratio 100%), dried at 125 ° C. for 1 minute to provide a protective layer having a thickness of 60 nm. The conductive laminate of the invention was obtained.

(Example 7)
KAYANOVA (registered trademark) FOP1740 (Nippon Kayaku Co., Ltd.) manufactured by Nippon Kayaku Co., Ltd. on one side, using a polyethylene terephthalate film having a thickness of 188 μm and Lumirror (registered trademark) U46 (manufactured by Toray Industries, Inc.) as a base material. Microgravure coater (gravure wire number 80R, gravure rotation ratio 100%) with a hard coating agent diluted to a solid content concentration of 40% by mass with a 1: 1 mass ratio of toluene and methyl ethyl ketone (MEK). After coating at 80 ° C. for 1 minute, ultraviolet rays were irradiated at 1.0 J / cm ² and cured to provide a hard coat layer having a thickness of 5 μm.

  Next, “conductive layer C” was laminated after “underlayer” was laminated on the opposite surface of the base material provided with the hard coat layer.

  Next, 50,000.000 g of “Protective layer material A”, 1.6667 g of “Protective layer material F”, and 540.000 g of “ethyl acetate / toluene mixed solvent (mixing mass ratio 1/1)” were mixed and stirred, and the protective layer was applied. I made a liquid. This protective layer coating solution is applied on the “conductive layer A” by microgravure coating (gravure wire number 80R, gravure rotation ratio 100%), dried at 125 ° C. for 1 minute to provide a protective layer having a thickness of 60 nm. The conductive laminate of the invention was obtained.

(Example 8)
Other than the composition of the protective layer coating solution being “Protective layer material A” 500.0000 g, “Protective layer material C” 1.0417 g, “Ethyl acetate / toluene mixed solvent (mixing mass ratio 1/1)” 540.6250 g Was prepared in the same manner as in Example 4 to obtain a conductive laminate of the present invention.

Example 9
Other than the composition of the protective layer coating solution being “Protective layer material A” 500.0000 g, “Protective layer material D” 1.3889 g, “Ethyl acetate / toluene mixed solvent (mixing mass ratio 1/1)” 540.2778 g Was prepared in the same manner as in Example 4 to obtain a conductive laminate of the present invention.

(Example 10)
Other than the composition of the protective layer coating solution being “Protective layer material A” 500.0000 g, “Protective layer material B” 1.1640 g, “Ethyl acetate / toluene mixed solvent (mixing mass ratio 1/1)” 557.0370 g Was prepared in the same manner as in Example 4 to obtain a conductive laminate of the present invention.

(Example 11)
Other than the composition of the protective layer coating solution being “protective layer material A” 500.0000 g, “protective layer material C” 1.4550 g, “ethyl acetate / toluene mixed solvent (mixing mass ratio 1/1)” 556.7460 g Was prepared in the same manner as in Example 4 to obtain a conductive laminate of the present invention.

(Example 12)
The composition of the protective layer coating solution was “protective layer material A” 500.0000 g, “protective layer material E” 1.1640 g, “additive A” 0.0058 g, “ethyl acetate / toluene mixed solvent (mixing mass ratio 1/1) ) "A conductive laminate of the present invention was obtained in the same manner as in Example 5 except that 557.6132 g.

(Example 13)
Other than the composition of the protective layer coating solution being “Protective layer material A” 500.0000 g, “Protective layer material F” 2.3280 g, “Ethyl acetate / toluene mixed solvent (mixing mass ratio 1/1)” 55.8730 g Was prepared in the same manner as in Example 4 to obtain a conductive laminate of the present invention.

(Example 14)
Other than the composition of the protective layer coating solution being “Protective layer material A” 500.0000 g, “Protective layer material C” 2.7778 g, “Ethyl acetate / toluene mixed solvent (mixing mass ratio 1/1)” 608.3333 g Was prepared in the same manner as in Example 4 to obtain a conductive laminate of the present invention.

(Example 15)
Other than the composition of the protective layer coating solution being “Protective layer material A” 500.0000 g, “Protective layer material C” 4.0698 g, “Ethyl acetate / toluene mixed solvent (mixing mass ratio 1/1)” 658.7209 g Was prepared in the same manner as in Example 4 to obtain a conductive laminate of the present invention.

(Example 16)
Other than the composition of the protective layer coating solution being “protective layer material A” 500.0000 g, “protective layer material C” 5.6748 g, “ethyl acetate / toluene mixed solvent (mixing mass ratio 1/1)” 721.3190 g Was prepared in the same manner as in Example 4 to obtain a conductive laminate of the present invention.

(Example 17)
Other than the composition of the protective layer coating solution being “Protective layer material A” 500.0000 g, “Protective layer material C” 6.6456 g, “Ethyl acetate / toluene mixed solvent (mixing mass ratio 1/1)” 759.1772 g Was prepared in the same manner as in Example 4 to obtain a conductive laminate of the present invention.

(Example 18)
Other than the composition of the protective layer coating solution being “protective layer material A” 500.0000 g, “protective layer material C” 6.6456 g, “ethyl acetate / toluene mixed solvent (mixing mass ratio 1/1)” 548.2068 g Was prepared in the same manner as in Example 4 to obtain a conductive laminate of the present invention.

(Example 19)
Other than the composition of the protective layer coating solution being “Protective layer material A” 500.0000 g, “Protective layer material C” 6.6456 g, “Ethyl acetate / toluene mixed solvent (mixing mass ratio 1/1)” 337.2363 g Was prepared in the same manner as in Example 4 to obtain a conductive laminate of the present invention.

(Comparative Example 1)
KAYANOVA (registered trademark) FOP1740 (Nippon Kayaku Co., Ltd., solid content concentration: 82% by mass on one side with a base material of 188 μm thick polyethylene terephthalate film, Lumirror (registered trademark) U46 (manufactured by Toray Industries, Inc.) ) Is coated with a microgravure coater (gravure wire number 80R, gravure rotation ratio 100%) at 80 ° C. with a hard coating agent diluted with toluene and methyl ethyl ketone (MEK) mass ratio of 1: 1 to a solid concentration of 40 mass%. After drying for 1 minute, ultraviolet rays were irradiated at 1.0 J / cm ² and cured to provide a hard coat layer having a thickness of 5 μm.

  Next, a laminate was formed without providing a conductive layer and a protective layer on the opposite surface of the substrate on which the hard coat layer was provided.

(Comparative Example 2)
KAYANOVA (registered trademark) FOP1740 (Nippon Kayaku Co., Ltd., solid content concentration: 82% by mass on one side with a base material of 188 μm thick polyethylene terephthalate film, Lumirror (registered trademark) U46 (manufactured by Toray Industries, Inc.) ) Is coated with a microgravure coater (gravure wire number 80R, gravure rotation ratio 100%) at 80 ° C. with a hard coating agent diluted with toluene and methyl ethyl ketone (MEK) mass ratio of 1: 1 to a solid concentration of 40 mass%. After drying for 1 minute, ultraviolet rays were irradiated at 1.0 J / cm ² and cured to provide a hard coat layer having a thickness of 5 μm.

  Next, only the “conductive layer A” was laminated on the opposite surface of the base material on which the hard coat layer was provided, and a protective layer was not provided to obtain a conductive laminate.

(Comparative Example 3)
KAYANOVA (registered trademark) FOP1740 (Nippon Kayaku Co., Ltd.) manufactured by Nippon Kayaku Co., Ltd. on one side, using a polyethylene terephthalate film having a thickness of 188 μm and Lumirror (registered trademark) U46 (manufactured by Toray Industries, Inc.) as a base material. Microgravure coater (gravure wire number 80R, gravure rotation ratio 100%) with a hard coating agent diluted to a solid content concentration of 40% by mass with a 1: 1 mass ratio of toluene and methyl ethyl ketone (MEK). After coating at 80 ° C. for 1 minute, ultraviolet rays were irradiated at 1.0 J / cm ² and cured to provide a hard coat layer having a thickness of 5 μm.

Next, on the opposite side of the base material on which the hard coat layer was provided, an “underlying layer” was laminated, after which only the “conductive layer B” was laminated, and a protective layer was not provided to obtain a conductive laminate.
(Comparative Example 4)
The protective layer coating solution was prepared in the same manner as in Example 1 except that the composition of the protective layer coating solution was 500.0000 g and “ethyl acetate / toluene mixed solvent (mixed mass ratio 1/1)” was 500.0000 g. A conductive laminate was obtained.
(Comparative Example 5)
The protective layer coating solution was prepared in the same manner as in Example 4 except that the composition of the protective layer coating solution was 500.0000 g and “ethyl acetate / toluene mixed solvent (mixed mass ratio 1/1)” was 500.0000 g. A conductive laminate was obtained.

(Comparative Example 6)
The protective layer coating solution was prepared in the same manner as in Example 7 except that the composition of the protective layer coating solution was 500.0000 g and “ethyl acetate / toluene mixed solvent (mixed mass ratio 1/1)” was 500.0000 g. A conductive laminate was obtained.

(Comparative Example 7)
The protective layer coating solution was prepared in the same manner as in Example 1, except that the composition of the protective layer coating solution was 25.0000 g and “ethyl acetate / toluene mixed solvent (mixed mass ratio 1/1)” was 975.000000 g. A conductive laminate was obtained.

(Comparative Example 8)
A protective layer coating solution was prepared in the same manner as in Example 4 except that the composition of the protective layer material C was 25.0000 g and “ethyl acetate / toluene mixed solvent (mixed mass ratio 1/1)” 975.00000 g. A conductive laminate was obtained.

(Comparative Example 9)
Other than the composition of the protective layer coating solution being “protective layer material A” 500.0000 g, “protective layer material G” 0.4167 g, “ethyl acetate / toluene mixed solvent (mixing mass ratio 1/1)” 541.2500 g Was prepared in the same manner as in Example 4 to obtain a conductive laminate.

(Comparative Example 10)
Other than the composition of the protective layer coating solution being “protective layer material A” 500.0000 g, “protective layer material G” 1.1111 g, “ethyl acetate / toluene mixed solvent (mixing mass ratio 1/1)” 6100000 g Was prepared in the same manner as in Example 4 to obtain a conductive laminate.

  In any of Examples 1 to 19, the keystroke durability of the touch panel could be improved. In particular, when the content of the resin contained is within a specific range and has a bond with a component in the protective layer, durability (heat resistance, heat and humidity resistance) is good as well as keystroke durability.

  When the resin contained in the protective layer together with the inorganic silicon oxide is a resin corresponding to (i) to (iii), the keystroke durability could be improved regardless of the type and shape of the conductive layer (Example) 1-7). In addition, when the resin contained in the protective layer together with the inorganic silicon oxide has a bond with the component in the protective layer (Examples 3, 6-9, 12-19), it does not have a bond. Compared with (Examples 1, 2, 4, 5, 10, 12, Comparative Examples 7 to 10), not only keystroke durability but also durability (heat resistance and moist heat resistance) were improved. It is possible to adjust the keystroke durability, durability (heat resistance, heat and humidity resistance), and surface resistance value by appropriately changing the type of resin, the type of functional group, and the content ratio contained in the protective layer together with the inorganic silicon oxide. (Examples 8 to 17). Furthermore, the optical characteristics could be adjusted by appropriately changing the refractive index and thickness of the protective layer (Examples 16 to 19).

  When the conductive layer is not provided (Comparative Example 1), the touch panel does not operate. When the protective layer was not provided (Comparative Example 2), even when the protective layer was provided, only the inorganic silicon oxide (Comparative Examples 4 to 6) had poor keystroke durability regardless of the type of the conductive layer. When the protective layer does not contain inorganic silicon oxide (Comparative Examples 7 and 8), or the resin contained together with the inorganic silicon oxide is a resin other than (i) to (iii) (Comparative Examples 8 and 9) In addition to the keystroke durability, the durability (heat resistance, heat and humidity resistance) was inferior. Further, when no protective layer was provided, the optical characteristics were poor.

  The present invention relates to a conductive laminate that improves durability against a point load of a touch panel, i.e., keystroke durability, and has both good durability and low optical reflectivity on the conductive layer side and good optical characteristics. is there. Furthermore, the present invention relates to a conductive laminate used for electrode members such as liquid crystal displays, organic electroluminescence, electronic paper, and related displays and solar cell modules.

1: base material 2: base resin layer 3: conductive layer 4: protective layer 5: backbone polymer 6 of main chain: silicone bonded as a branch polymer to a side chain site 7: conductivity observed from a direction perpendicular to the laminated surface Surface 8: Carbon nanotube (an example of a linear structure)
9: Nanowire of metal or metal oxide (an example of a linear structure)
10: Metal oxide whisker or needle-like crystal like fiber (an example of a linear structure)
11: Conductive thin film 12: Main polymer of main chain 13: Branched side chain 14: Hydrophilic group 15: Upper electrode 16: Lower electrode 17: Upper electrode substrate 18: Lower electrode substrate 19: Hard coat layer 20 : Dot spacer 21: Double-sided adhesive tape 22: Space 23: Power supply 24: Pen 100: Reactor 101: Quartz sintered plate 102: Sealed catalyst feeder 103: Catalyst input line 104: Raw material gas supply line 105: Exhaust gas line 106 : Heater 107: Inspection port 108: Catalyst

Claims (7)

A conductive laminate formed by laminating a conductive layer and a protective layer using an inorganic silicon oxide in this order on at least one surface of the base material in the protective layer using the inorganic silicon oxide. The electrically conductive laminated body used for the touchscreen which contains the resin composition A containing at least 1 sort (s) among the group which consists of resin as described in following (i)-(iii).
(I) Silicone graft resin (ii) Silicone resin resin (iii) Modified silicone resin The total content of the resin composition A contained in the protective layer (mass%), the touch panel according to claim 1 to the total mass not more than 5% by weight to 20% by weight is relative to the protective layer The conductive laminate used . 3. The touch panel according to claim 1, wherein in the protective layer, the inorganic silicon oxide is bonded to any one of the resins described in (i) to (iii) in the resin composition A. 4. conductive laminate is. The minimum value of the reflectance curve on the protective layer side is in a wavelength range of 350 to 550 nm, and the average reflectance on the protective layer side at a wavelength of 380 to 780 nm is 4% or less. Conductive laminate used for touch panels . The conductive laminate used for a touch panel according to claim 1, wherein the conductive layer contains a linear structure. The electroconductive laminated body used for the touchscreen in any one of Claims 1-5 whose total light transmittance based on JISK7361-1 (1997) when it injects from the protective layer side is 80% or more. A touch panel using the conductive laminate according to claim 6 .

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