JP5428924B2 - 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 containing a conductive component composed of a linear structure. More specifically, the present invention relates to a conductive laminate capable of miniaturizing a pattern formed by chemical etching when forming an electrode member used for a touch panel or the like. Furthermore, it is related with the electroconductive laminated body used also for electrode members used, such as liquid crystal displays, organic electroluminescence, electronic papers, and related displays and solar cell modules.

  In recent years, mobile phones, game machines, personal computers, and the like equipped with touch panels have become widespread. A conductive member for an electrode is used in the touch panel, but a surface of the conductive layer of the conductive member is formed in a desired pattern for a touch panel that enables complicated operations.

  As a conductive member used for this touch panel, a conductive laminate (Patent Document 1), a base comprising a layer made of a polymer compound having a functional group such as an amino group on a conductive thin film layer provided on a substrate, A conductive laminate (Patent Document 2) in which a layer made of a polymer compound such as a cyano group is laminated on a conductive thin film layer made of a metal thin film or a conductive polymer thin film provided on a material, and further on a substrate A conductive laminate (Patent Document 3) in which a layer made of an epoxy resin is laminated on a conductive layer containing spherical metal fine particles provided, and hydrophilic on the conductive layer containing a needle-like conductive metal oxide provided on a substrate Having a functional group or a skeleton structure composed of a specific element, such as a conductive laminate (Patent Document 4) in which layers made of a polymer compound having a cationic quaternary ammonium base or a sulfone group as a functional functional group are laminated Made of polymer compounds Conductive laminate laminated on each conductive thin film layer has been proposed.

  In addition, a conductive laminate (Patent Document 5) in which a plurality of layers containing a linear organic polysiloxane that is a silicone polymer is further laminated in an order in which a conductive thin film layer and an inorganic oxide layer are laminated in this order from the upper side of the base material. A conductive laminate in which a layer containing a polymerizable compound containing a perfluoroalkyl group is further laminated on the hard coat layer and conductive layer containing spherical metal fine particles in this order from the upper side of the substrate (Patent Document 6), etc. A conductive laminate in which a layer having water repellency and oil repellency is laminated on each conductive thin film layer has been proposed.

  Furthermore, a conductive laminate in which a thin silicon coat layer, that is, a silica layer is laminated on a conductive layer containing carbon nanotubes (hereinafter abbreviated as CNT), which are linear structures provided on a polymer substrate (Patent Document) 7) and a conductive laminate in which a layer whose surface wettability is controlled with an additive such as a polymer compound having a hydrophilic group or a surfactant on the conductive layer is also proposed (Patent Document 4). 8).

  On the other hand, as a pattern forming method of these conductive members, a laser ablation method or a chemical etching method using an etching solution is generally used (Patent Document 9). The laser ablation method irradiates the conductive film with near-infrared (NIR) laser light to remove unnecessary portions, so that highly accurate patterning is possible without requiring a resist, but applicable substrates are limited. In addition, the cost is high and the processing speed is slow, so it is not suitable for processing a large area. On the other hand, in the chemical etching method, for example, an etching medium containing an acid has been proposed (Patent Document 10), and this etching medium is formed on a conductive member in a desired pattern (for example, a straight line having a line width of several tens μm to several mm). The pattern portion to which the etching medium is transferred is removed by transferring it to the pattern etc. by screen printing etc., and the pattern is removed (for example, a linear pattern having a line width of several tens of μm to several mm). This is advantageous because of its small number and low cost.

JP 2003-115221 A JP 2007-276322 A Japanese Patent No. 3442082 JP-A-11-198275 Japanese Patent No. 2847704 JP 2001-243841 A Japanese Patent No. 3665969 JP 2004-294555 A JP 2001-307567 A Special table 2009-503825 gazette

  However, like the protective layer of the laminate described in Patent Documents 1, 2, and 4, the layer laminated on the conductive layer is an amino group, a cyano group, a cationic quaternary ammonium base, a sulfone group, or the like. When the polymer compound having a functional group is used as a component, it is resistant to an etching medium (hereinafter referred to as a removing agent) containing an acid or other base component as described in Patent Document 10. Therefore, the desired pattern cannot be formed, the pattern becomes thick, or the pattern cannot be formed neatly. Moreover, when the specific element is not a functional group but a polymer compound having a skeleton structure itself as in Patent Document 3, the resistance to the removal agent is relatively lower than that of the polymer compound containing the specific element as the functional group. It is easy to obtain, and the remover is applied to a relatively desired pattern by a general method such as screen printing on the layer having water repellency and oil repellency as in Patent Documents 5 and 6, not limited to the polarity of the remover. Although it can be laminated, if the conductive layer is a conductive thin film or the conductive component is a non-linear structure such as a metal fine particle, it can be a thin film that is uniform in-plane to conduct electricity. Since the metal fine particles in the layer are densely contained, it is necessary to lengthen the treatment time or increase the acid or base concentration in order to form a pattern. As a result, the acid or base contained in the removal agent Eroded, Patent Document 1, , Thickening of the pattern is generated in the same manner as 4. Furthermore, even if the conductive component is a CNT that is a linear structure as in Patent Document 7, a case where a silica layer with poor oil repellency is laminated with a thin film that does not impair the conductivity, or Patent Documents 4 and 8 Similarly, when the layers forming the hydrophilic surface are laminated, the problem of pattern thickening cannot be solved.

  In view of the background of such conventional technology, the present invention aims to provide a conductive laminate capable of miniaturizing a pattern formed by chemical etching by improving both the conductive layer and the protective layer.

In order to solve this problem, the present invention employs the following configuration. That is,
(1) A conductive laminate in which a conductive layer including a conductive component composed of a linear structure is laminated on at least one surface of a base material in this order, and a protective layer, the protective layer comprising the following (i) and A conductive laminate satisfying (ii),
(I) About the surface of the protective layer, the contact angle of pure water is 80 ° or more, and the contact angle of oleic acid is 13 ° or more,
(Ii) The protective layer is made of a polymer compound that does not contain any of the S element, P element, metal element, metal ion, and N element constituting the functional group.
(2) the polymer compound has a crosslinked structure;
(3) The linear structure has a network structure in which the linear structures are in contact with each other at at least one contact;
(4) A polyfunctional acrylic polymer in which the linear structure is a silver nanowire and the protective layer does not contain any of an S element, a P element, a metal element, a metal ion, and an N element constituting a functional group A compound or a polyfunctional methacrylic polymer compound,
(5) A polyfunctional acrylic polymer compound in which the linear structure is a carbon nanotube and the protective layer does not contain any of an S element, a P element, a metal element, a metal ion, and an N element constituting a functional group Or a polyfunctional methacrylic polymer compound,
(6) The protective layer contains two or more photoinitiators having different maximum absorption wavelengths of 20 nm or more,
(7) The total light transmittance based on JIS K7361-1 (1997) when entering from the protective layer side is 80% or more,
(8) The conductive laminate according to any one of (1) to (7), which is used for a touch panel,
(9) A touch panel using the conductive laminate according to (8),
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, a fine pattern formed by chemical etching is formed on at least one surface of a base material by laminating a conductive layer containing a conductive component composed of a linear structure in that order and a specific protective layer in this order. It is possible to provide a conductive laminate that can be formed.

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 linear structure observed from the conductive layer side of the conductive laminated body of the present invention. It is the schematic diagram which showed an example of the touchscreen which is the one aspect | mode of this invention. It is an example of the cross-sectional schematic diagram of the linear structure vicinity 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 comprising a conductive component composed of a linear structure is laminated on at least one surface of a base material in this order, and a protective layer. The conductive laminate satisfies the following (i) and (ii).
(I) With respect to the surface of the protective layer, the contact angle of pure water is 80 ° or more, and the contact angle of oleic acid is 13 ° or more. (Ii) The protective layer is composed of S element, P element, metal element, metal ion and functional group. It consists of a polymer compound that does not contain any N element constituting the group.
When the conductive component is a linear structure and the protective layer satisfies the above (i) to (ii), the pattern formed by chemical etching can be miniaturized. Yes.

  In other words, if the conductive component is a linear structure, electricity flows from the linear structure even if there is a sparse part where the linear structure does not exist, so the resistance value of the surface is sufficiently low and there is no problem at a practical level. Can be obtained. On the other hand, the conductive laminate patterned by chemical etching needs to be electrically insulated by removing the conductive component of the patterning portion. This is because if the electrical insulation is insufficient, problems such as short-circuiting occur when used as an electrode member, so even if the pattern to be formed can be miniaturized, it cannot be used as an electrode member. Because. When the conductive component is a linear structure, it is presumed that it is easily removed due to the effects described below and electrical insulation is easily obtained.

  On the other hand, since the removal agent contains components other than the removal component such as a binder and a solvent in addition to the acid or base component that is a component for removing the conductive component, the polarity as the removal agent varies depending on the type. Along with the change in polarity, even if the removal agent is transferred on the surface of a normal conductive laminate by screen printing or the like, the removal agent spreads wet and it is difficult to obtain a desired pattern. The pattern cannot be formed neatly due to the occurrence of a thick straight line) or the non-uniform wetting and spreading of the remover.

Here, for the contact angle that is an indicator of the surface wettability of the protective layer laminated on the conductive layer,
(1) For a component having a polarity close to the aqueous system in the remover by making the contact angle of pure water 80 ° or more,
(2) In addition, for the component showing a polarity close to the organic solvent system (oil system) in the remover by setting the contact angle of oleic acid to 13 ° or more,
(3) Still further, with respect to the removal agent showing an intermediate polarity in which water-based and organic solvent-based (oil-based) components are mixed,
Presuming that wetting and spreading can be suppressed, and the removal agent can be finely and finely transferred and laminated on the conductive laminate for any desired pattern with any polarity removal agent. Yes.

  In addition, even if the remover can be finely and finely transferred and laminated on the conductive laminate as described above, the removal of the acid or base component in the remover can be achieved. When the protective layer is not resistant, the acid or base component easily penetrates into the protective layer, and the protective layer peels off and dissolves together with the conductive layer after the removing agent cleaning step. As a result, the pattern becomes thicker than the portion where the removal agent is transferred and laminated, and the pattern becomes thicker than the desired pattern. Here, when the protective layer is made of a polymer compound that does not contain any of the S element, the P element, the metal element, the metal ion, and the N element constituting the functional group, an acid or a removal component in the remover for the following estimation reason: The penetration rate of the base component can be slowed. As a result, the linear structure, which is a conductive component, can be selectively removed to suppress the peeling / dissolution of the protective layer even after the removal agent cleaning step. Therefore, it is estimated that miniaturization is possible without pattern thickening or non-uniformity. When the protective layer is made of a polymer compound that does not contain any of the S element, P element, metal element, metal ion, and N element constituting the functional group, the penetration rate of the acid or base component that is the removal component in the removal agent The estimation reason that can be delayed is shown below.

The S element, the P element, and the N element may have an electron pair that is not bonded to other elements due to their electron orbital state, or a functional group having an ionic bond with a metal ion (for example, —ONa, —COONa, —SO ₃ Na). Etc.), and metal elements may form coordinate bonds. Electron pairs, ionic bonds, and coordination bonds that do not bind to these other elements easily act with the acid or base component that is the removal component in the removal agent, so that the S element, P element, metal element, metal ion, and functionality By easily cleaving or cleaving the bond with the element to which one of the N elements constituting the group was originally bonded, the acid or base component that is the removal component in the removal agent penetrates into the protective layer. It is estimated that it may be easy to do. Furthermore, since the functional group having an ionic bond tends to impart hydrophilicity, it tends to reduce the contact angle of the pure water, and is unsuitable for making the contact angle of pure water 80 ° or more. Therefore, when using a polymer compound that does not contain any of these S element, P element, metal element, metal ion, and N element constituting the functional group, the penetration rate of the acid or base component that is the removal component in the removal agent As a result, it is possible to suppress the peeling / dissolution of the protective layer even after the cleaning step of the removing agent by selectively removing the linear structure which is a conductive component. It is estimated that miniaturization is possible without any non-uniformity.

  Furthermore, by making the conductive component a linear structure, when the acid or base component, which is a removal component that has penetrated into the protective layer, reaches the linear structure and the linear structure starts to be etched, the acid or base While the acid or base component selectively erodes in the linear direction (long axis direction described later) of the linear structure having low resistance to the component, the rate at which the acid or base component penetrates into the protective layer for the reasons described above. Is much slower than that of the protective layer, and as a result, the conductive component can be selectively removed in the cleaning process to suppress peeling and dissolution of the protective layer. It is estimated that there is no fattening or non-uniformity and miniaturization is possible.

The conductive laminate of the present invention has a conductive layer containing a conductive component composed of a linear structure from the substrate side on at least one surface of the substrate. When the conductive layer is not provided, conductivity is not exhibited.
The conductive component of the conductive layer needs to be a linear structure. When the conductive component is not a linear structure as in the prior art (in the case of a non-linear structure), in order to conduct electricity, it can be a thin film that is uniform in the surface or contains fine metal particles in the conductive layer. Therefore, in order to remove the conductive layer, it is necessary to lengthen the processing time or increase the concentration of the acid or base component in order to form a pattern. As a result, the acid or base component contained in the removal agent is reduced. The protective layer is sufficiently eroded together with the conductive layer, and the protective layer is peeled and dissolved after the removing agent cleaning step, resulting in pattern thickening and non-uniformity, and the pattern cannot be miniaturized. On the contrary, even if the processing time for forming the pattern is not lengthened, or the concentration of the acid or base component is increased to suppress pattern thickening or non-uniformity by an internal method, the electrical insulation of the patterning portion is not affected. It becomes insufficient. When a linear structure is used, the acid or base component is selectively used in the linear direction (long axis direction described later) of the linear structure having low resistance to the acid or base component that is a removal component in the remover. By eroding, the relative proportion of the conductive component removed is larger than that of the protective layer. As a result, the conductive component is selectively removed in the cleaning process, and the protective layer is peeled and dissolved, thereby increasing the pattern thickness. There is no unevenness and miniaturization is possible.

  The linear structure in the present invention is a structure in which the ratio of the length of the short axis to the length of the long axis, that is, the aspect ratio = the length of the long axis / the length of the short axis is greater than 1 (on the other hand, For example, a spherical shape has an aspect ratio = 1). Examples of the linear structure include a fibrous conductor and a needle-like conductor such as a whisker. Although the lengths of the short axis and the long axis differ depending on the type of the linear structure and cannot be uniquely limited, the length of the short axis is smaller than the pattern to be formed and is 1 nm to 1000 nm (1 μm). Preferably, the length of the major axis may be such that the aspect ratio = the length of the major axis / the length of the minor axis is greater than 1 with respect to the length of the minor axis. .1 mm) is preferred.

Examples of the fibrous conductor include a carbon-based fibrous conductor, a metal-based fibrous conductor, and a metal oxide-based fibrous conductor. Examples of carbon-based fibrous conductors include polyacrylonitrile-based carbon fiber, pitch-based carbon fiber, rayon-based carbon fiber, glassy carbon, CNT, carbon nanocoil, carbon nanowire, carbon nanofiber, carbon whisker, graphite fibril, etc. Is mentioned. Metallic fibrous conductors include gold, platinum, silver, nickel, silicon, stainless steel, copper, brass, aluminum, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, manganese, technetium, rhenium, iron, Examples thereof include fibrous or nanowire-like metals and alloys produced from osmium, cobalt, zinc, scandium, boron, gallium, indium, silicon, germanium, tin, magnesium, and the like. As the metal oxide-based fibrous _{conductor, InO 2, InO 2 Sn,} SnO 2, ZnO, SnO 2 -Sb 2 O 4, SnO 2 -V 2 O 5, TiO 2 (Sn / Sb) O 2, SiO ₂ (Sn / Sb) O ₂ , K ₂ O—nTiO ₂ — (Sn / Sb) O ₂ , K ₂ O—nTiO ₂ —C or the like, or a nanowire-like metal oxide And metal oxide composites. These may be subjected to a surface treatment. Furthermore, what coated or vapor-deposited the said metal, the said metal oxide, or CNT on the surface of nonmetallic materials, such as a vegetable fiber, a synthetic fiber, and an inorganic fiber, is also contained in a fibrous conductor.

The acicular conductor such as the whisker is a compound made of a metal, a carbon-based compound, a metal oxide, or the like. The metal belongs to the group IIA, IIIA, IVA, VA, VIA, VIIA, VIII, IB, IIB, IIIB, IVB or VB in the short periodic table of elements. Elements. Specifically, gold, platinum, silver, nickel, stainless steel, copper, brass, aluminum, gallium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, manganese, antimony, palladium, bismuth, technetium, rhenium, Examples thereof include iron, osmium, cobalt, zinc, scandium, boron, gallium, indium, silicon, germanium, tellurium, tin, magnesium, and alloys containing these. Examples of the carbon-based compound include carbon nanohorn, fullerene, and graphene. Examples of the metal oxide include InO ₂ , InO ₂ Sn, SnO ₂ , ZnO, SnO ₂ —Sb ₂ O ₄ , SnO ₂ —V ₂ O ₅ , TiO ₂ (Sn / Sb) O ₂ , SiO ₂ (Sn / Sb). ) O ₂ , K ₂ O—nTiO ₂ — (Sn / Sb) O ₂ , K ₂ O—nTiO ₂ —C, and the like. Among these linear structures, silver nanowires or CNTs can be preferably used from the viewpoints of optical properties such as transparency and electrical conductivity.

  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. 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 does not impair the 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. Furthermore, the coating film is also strong, and it is preferable because scratches are less likely to 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 As the needle-like conductors such as whiskers, for example, WK200B, WK300R, WK500 of DENTOR WK series (manufactured by Otsuka Chemical Co., Ltd.), which is a composite compound of potassium titanate fiber, tin and antimony oxide, TM100 of Dentor TM series (manufactured by Otsuka Chemical Co., Ltd.), which is a composite compound of silicon fiber, tin and antimony oxide, is commercially available, and the above linear structures can be used alone or in combination. In addition, if necessary, other micro-to-nano size conductive materials can be added. Ku, but it is not particularly limited thereto.

  In the present invention, the surface of the protective layer laminated on the conductive layer needs to have a pure water contact angle of 80 ° or more and an oleic acid contact angle of 13 ° or more. When the surface of the protective layer has at least either a pure water contact angle of less than 80 ° or an oleic acid contact angle of less than 13 °, when the removal agent is transferred and laminated on the conductive laminate, The removal agent wets and spreads, so that a desired pattern cannot be obtained, the pattern becomes thick, or the removal agent spreads unevenly and the pattern cannot be formed cleanly. On the other hand, when the surface of the protective layer has a contact angle of pure water of 80 ° or more and a contact angle of oleic acid of 13 ° or more, the surface of the protective layer can suppress wetting and spreading regardless of the polarity of the removing agent. It is possible to form a fine and clean pattern with respect to a desired pattern. Here, the contact angle is a value θ calculated when a droplet is allowed to stand on the protective layer side of the conductive laminate of the present invention installed horizontally by a sessile drop method according to JIS R3257. is there. In the present invention, the droplets are carried out as pure water and oleic acid, and the contact angle of pure water is an indicator of surface wettability with respect to a component having a polarity close to the aqueous system in the remover, and the contact angle of oleic acid is Each is employed as an index of surface wettability for a component having a polarity close to that of an organic solvent (oil) in the remover.

  Since the contact angle of pure water on the protective layer side in the present invention depends on the components constituting the protective layer and the like, it may be 80 ° or more and cannot be uniquely limited. Since a finer and finer pattern can be formed without unevenness, it is preferably 85 ° or more, more preferably 90 ° or more, and more preferably 93 ° or more. The upper limit is not particularly limited, but the removal agent may cause transfer defects such as repellency or stacking faults depending on the type and components of the remover, the method of transferring and stacking on the conductive laminate, and the like. Therefore, it is preferably 100 ° or less. In addition, the contact angle of oleic acid on the protective layer side in the present invention depends on the components constituting the protective layer and the like, and can be unambiguously limited as long as it is 13 ° or more. Therefore, it is preferably 30 ° or more, more preferably 40 ° or more, and more preferably 45 ° or more. The upper limit is not particularly limited, but the removal agent may cause transfer defects such as repellency or stacking faults depending on the type and components of the remover, the method of transferring and stacking on the conductive laminate, and the like. Therefore, it is preferably 70 ° or less. The surface of the protective layer according to the present invention has a pure water contact angle of 80 ° or more and an oleic acid contact angle of 13 ° or more. S element, P element, metal element, metal ion and The protective layer may be made of a composition in which an additive is added together with a polymer compound that does not contain any of the N elements that constitute the functional group, but each contact angle range may be satisfied. Since there is a risk of inhibiting the curing reaction of the molecular compound, among the polymer compounds that do not contain any of the S element, P element, metal element, metal ion, and N element constituting the functional group, the polymer compound itself is each It is preferable to select a material satisfying the contact angle range and to form the protective layer only with the polymer compound. Examples of the additives include low molecular weight compounds / monomers / oligomers containing fluorine element (F element), silicone-based low molecular weight compounds / monomers / oligomer resins, and the like. The element, P element, metal element, metal ion, and N element constituting the functional group may be present in the protective layer in a state of being mixed with a polymer compound that does not include any of the elements, S element, P element, It may have a partial bond with a polymer compound that does not contain any metal element, metal ion, and N element constituting the functional group, and is not particularly limited as long as each contact angle range is satisfied. .

The protective layer in the present invention needs to be made of a polymer compound that does not contain any of the S element, P element, metal element, metal ion, and N element constituting the functional group. The S element, the P element, and the N element may have an electron pair that is not bonded to other elements due to their electron orbital state, or a functional group having an ionic bond with a metal ion (for example, —ONa, —COONa, —SO ₃ Na). Etc.), and metal elements may form coordinate bonds. Electron pairs, ionic bonds, and coordination bonds that do not bind to these other elements easily act with the acid or base component that is the removal component in the removal agent, so that the S element, P element, metal element, metal ion, and functionality Any of the N elements composing the group is easily cleaved / cleavage from the element that was originally bonded, and as a result, the acid or base component, which is the removal component in the removal agent, easily penetrates into the protective layer. As a result, pattern thickening and non-uniformity occur, and miniaturization becomes difficult. Furthermore, since the functional group having an ionic bond tends to impart hydrophilicity, it tends to reduce the contact angle of the pure water, and is unsuitable for making the contact angle of pure water 80 ° or more. On the other hand, when a polymer compound that does not contain any of these S element, P element, metal element, metal ion, and N element constituting the functional group is used, the contact angle of the pure water can be easily increased to 80 ° or more. In addition to being able to remove, the removal rate of the acid or base component that is the removal component in the removal agent can be slowed, and as a result, the linear structure that is the conductive component is selectively removed, thereby cleaning the removal agent. Since peeling and dissolution of the protective layer can be suppressed even after the process, there is no pattern thickening or non-uniformity, and miniaturization is possible. Examples of the component of the protective layer include organic or inorganic polymer compounds.

  Examples of the inorganic polymer compound include inorganic oxides such as silicon oxides such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra- Tetraalkoxysilanes such as n-butoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltri Methoxysilane, i-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-pentyltriethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxy Silane, n- Ctyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane 2-hydroxypropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (meth) acryloxypropyl Trialkoxysilanes such as trimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, vinyltriacetoxysilane, methyltriacetyloxysilane, methyltri A sol-gel coating film formed by hydrolysis / polymerization reaction from an alcohol, water, acid, or the like of an organoalkoxysilane such as phenoxysilane, or a sputter deposition film of silicon oxide can be used.

  Examples of the organic polymer compound include thermoplastic resins, thermosetting resins, and photocurable resins, and are appropriately selected from the viewpoint of visible light permeability, heat resistance of the substrate, glass transition point, film hardness, and the like. can do. Examples of these resins include polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polycarbonate resins, acrylic resins, methacrylic resins, epoxy resins, olefin resins such as polyethylene and polypropylene, polystyrene resins, polyvinyl acetate resins, Phenol resin, resin containing chlorine element (Cl element) such as polyvinyl chloride and polyvinylidene chloride, resin containing fluorine element (F element) (for example, polyester resin, acrylic resin, methacrylic resin, epoxy Resin, resin containing elemental fluorine (F element) in the structure of resin such as olefin resin such as polyethylene and polypropylene, silicone resin (linear silicone resin, silicone resin resin, linear silicone resin) Or silicor Copolymers of resin resins and other resins and copolymers of graft structures, silicones of the above linear silicone resins, copolymers of silicone resin resins, copolymers of other resins and copolymers of graft structures Modified silicone resin in which various functional groups are introduced into the structure such as molecular chain terminal, molecular chain, and branched chain), etc., and at least one type can be arbitrarily selected based on the characteristics and productivity that require them. In addition, two or more of these may be mixed, and although not particularly limited to these, from the viewpoint that each of the contact angles can be easily in a specific range, a fluorine element (F element) is used. In addition to optical properties such as transparency, a polyfunctional acrylic polymer compound or a polyfunctional methacrylic polymer compound is preferable for reasons described later in addition to optical properties such as transparency. It can be preferably used.

  Furthermore, in the present invention, when the polymer compound has a cross-linked structure, the penetration rate of the acid or base component as the removal component in the removal agent is reduced, and the linear structure as the conductive component is reduced. The selective removal is particularly preferable because the protective layer can be prevented from peeling and dissolving even after the cleaning step of the removing agent, the pattern is not thickened or non-uniformized, and further miniaturization is facilitated. The cross-linked structure in the present invention is a state in which the bonds of the components forming the protective layer are three-dimensionally connected. By taking the cross-linked structure, the bonds of the components constituting the protective layer become dense and the free space of the protective layer ( As a result of the reduction in the free volume, it is estimated that the penetration of the acid or base component from the remover into the protective layer can be suppressed. The effect of this crosslinked structure is the same whether it is an organic polymer compound or an inorganic polymer compound, but the inorganic polymer compound has a crosslinked structure compared to the organic polymer compound. The cross-linked structure of an organic polymer compound is most preferred because the protective layer becomes brittle due to a decrease in flexibility and flexibility, and the brittle fracture may easily occur in the handling method during production.

  As a method for forming an organic polymer compound into a crosslinked structure, there are a method in which a polyfunctional monomer or polyfunctional oligomer is cured by heating, or a photocuring method is performed by irradiating an active electron beam such as ultraviolet light, visible light, or electron beam. . In the case of thermosetting, since the thermal energy is the driving force of the curing reaction, if the monomers and oligomers are made more multifunctional, it may be necessary to take measures such as a longer time for reactivity and a longer curing time, In the case of photocuring, it contains a photoinitiator as described later, and the reaction easily proceeds in a chain manner depending on the starting species generated by irradiating the active electron beam thereto, so that the curing time is short, etc. More preferred for reasons. Examples of the polyfunctional monomer or polyfunctional oligomer that forms the polyfunctional acrylic polymer compound or polyfunctional methacrylic polymer compound of the present invention include pentaerythritol triacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, trimethylol. Examples include methylolpropane ethoxytriacrylate, glycerin propoxytriacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, pentaerythritol ethoxytetraacrylate, and ditrimethylolpropane tetraacrylate. Based on the characteristics and productivity that require these. At least one kind may be arbitrarily selected, and two or more kinds thereof may be mixed. Furthermore, isophorone diisocyanate may be used as an additive. May have a mixture of isocyanate-based compounds such as sulfonate (IPDI) have some urethane acrylate skeleton containing N elements into different in skeletal structure and functional groups, it is not particularly limited thereto.

  Here, the photoinitiator absorbs light in the ultraviolet region, light in the visible region, active electron beams such as electron beams, and generates active species such as radical species, cation species, and anion species that are reaction initiation species. It is a substance that initiates the reaction of the polymer compound.

  In the present invention, only one photoinitiator may be used alone from the type of the active electron beam to be used, but more preferably two or more photoinitiators each having a maximum absorption wavelength value of 20 nm or more are different. It is preferable to select and use.

  The reason is as follows. For example, when the starting species is a radical species, the radical species is very reactive, but because of its high reactivity, it reacts with the oxygen in the atmosphere before reacting with the polyfunctional monomer or polyfunctional oligomer. The radical may be deactivated, and the curing reaction may not proceed as expected, and the crosslinked structure of the polymer compound may be insufficient. In order to suppress the oxygen inhibition, it may be necessary to take measures such as substituting with an inert gas such as nitrogen or argon, or using an atmosphere deoxygenated, but such a special atmosphere. Lowering the equipment would be disadvantageous in terms of productivity and cost, such as a large-scale facility. Therefore, if the curing reaction proceeds sufficiently even in the atmosphere and a crosslinked structure can be formed, stable production is possible at a low cost, and as a result, a higher quality conductive laminate can be provided. Here, the inventors have found that the maximum absorption wavelength value of the photoinitiator to be mixed is different by 20 nm or more, so that the curing reaction can proceed sufficiently even in a special atmosphere even in the atmosphere.

  In addition, the maximum absorption wavelength here is a wavelength at the maximum value of the absorption spectrum obtained by ultraviolet-visible spectrophotometry (UV-Vis) when the photoinitiator is dissolved in a soluble solvent. Further, when there are a plurality of maximum values, the following is set as the maximum absorption wavelength. Of the plurality of maximum values existing in the region of 200 to 400 nm in the absorption spectrum obtained with an optical path length of 1 cm, the wavelength at the maximum value with the highest absorbance is defined as the maximum absorption wavelength. Here, if the concentration of the photoinitiator when dissolved in a solvent is too high, the maximum value with the highest absorbance will exceed the detection limit of the device used, as if there is no maximum value with the highest absorbance. Therefore, the concentration of the photoinitiator is appropriately changed and measured in the same manner, and the wavelength at the maximum value having the highest absorbance at each concentration is taken as the maximum absorption wavelength. When the difference in maximum absorption wavelength is less than 20 nm, there is a region where the absorption bands of the mixed photoinitiators overlap, and it is estimated that only an effect equivalent to that of one photoinitiator can be obtained. ing. However, an emitter such as a lamp that emits the active electron beam does not actually emit only a single wavelength but emits various wavelengths, and light having a difference in maximum absorption wavelength of 20 nm or more. By mixing two or more initiators, it is possible to absorb a wider range of wavelengths. As a result, by efficiently capturing and using the emitted active electron beam, a sufficient curing reaction can be achieved even in the atmosphere. Can be advanced. Therefore, when 3 or more types of photoinitiators are contained, it is more effective that the difference between the respective maximum absorption wavelengths is 20 nm or more.

  Usable photoinitiators include, for example, benzophenone series such as benzophenone, hydroxybenzophenone, 4-phenylbenzophenone, benzoin series such as benzyldimethyl ketal, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl- 1-phenylpropan-1-one, 2-methyl 1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) ) -Butaneone-1 and other α-hydroxy ketones and α-amino ketones, isopropylthioxanthone, thioxanthone such as 2-4-diethylthioxanthone, methylphenylglyoxylate, etc. can be used, the maximum absorption wavelength value, absorbance, Viewpoint of color sighting, coloring degree, etc. From these, it can use preferably among these photoinitiators. Examples of commercially available products include Ciba (registered trademark) IRGACURE (registered trademark) 184 (manufactured by Ciba Japan Co., Ltd.) and 2-methyl 1 [4- as 1-hydroxy-cyclohexyl-phenyl-ketone. (Methylthio) phenyl] -2-morpholinopropan-1-one as Ciba (registered trademark) IRGACURE (registered trademark) 907 (manufactured by Ciba Japan KK), 2-benzyl-2-dimethylamino-1- ( Examples of 4-morpholinophenyl) -butanone-1 include Ciba (registered trademark) IRGACURE (registered trademark) 369 (manufactured by Ciba Japan Co., Ltd.).

  In the present invention, the linear structure is preferably present in a network structure in the conductive layer. By having a network structure, the number of conductive paths in the surface direction on the protective layer side increases, the protective layer side of the conductive laminate can be easily adjusted to a low surface resistance value, and the acid or base component in the remover has a network structure. By eroding along the path, the linear structure can be eroded more selectively, suppressing the peeling and dissolution of the protective layer even after the cleaning process of the remover, and without pattern thickening or non-uniformity, Furthermore, since it becomes easy to refine | miniaturize, it is especially preferable. The network structure in the invention is that the linear structures are in contact with each other at least one contact, and the smallest network structure is a case where two linear structures have a certain contact. The contact may be formed by any part of the linear structure, the end parts of the linear structure are in contact with each other, the end and the part other than the end of the linear structure are in contact, or the linear structure Parts other than the ends of the body may be in contact with each other, and may be in contact with each other even if the contact points are joined. The network structure can be observed by a method described later, but is not particularly limited. Furthermore, the linear structure may form an aggregate to form a network structure. Here, the aggregate of the linear structures may be, for example, a state in which the linear structures are not regularly arranged and randomly assembled, and the surface of the linear structures in the long axis direction. It may be in a state where they are gathered in parallel. As an example of a state in which the surfaces in the major axis direction are gathered in parallel, it is publicly known that when the aforementioned CNT is used as a conductive layer, it becomes an aggregate called a bundle, and other linear structures are similarly You may have a similar bundle structure.

  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. A touch panel in which the conductive laminate of the present invention is incorporated as a transparent conductive laminate exhibits excellent transparency, and the display of a display provided on the lower layer of the touch panel using the transparent conductive laminate can be clearly recognized. 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, a method for increasing the total light transmittance of a substrate to be used, a method for reducing the film thickness of the conductive layer, and a protective layer as an optical interference film. And the like.

  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. Specific examples include a transparent resin and glass, and the film can be rolled up with a thickness of 250 μm or less, or a substrate with a thickness of more than 250 μm. That's fine. 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. Among these base materials, from the viewpoint of optical properties such as moldability to the base material, transparency, and productivity, polyester films such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), and mixing with PEN and A copolymerized PET film or polypropylene film can be preferably used.

  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.

  Next, a description will be given of a method of laminating so that the protective layer becomes an optical interference film.

  The conductive layer reflects and absorbs light due to the physical properties of the conductive component itself. Therefore, in order to increase the total light transmittance of the transparent conductive laminate including the conductive layer provided on the substrate, the protective layer is provided so as to be an optical interference film with a transparent material, and the wavelength 380 on the optical interference film side is provided. It is effective to lower the average reflectance at ˜780 nm to 4% or less, preferably 3% or less, more preferably 2% or less. When the average reflectance is 4% or less, a performance with a total light transmittance of 80% or more when used for touch panel applications can be obtained with good productivity.

The conductive laminate of the present invention has a surface resistance value on the conductive layer side of 1 × 10 ⁰ Ω / □ or more and 1 × 10 ⁴ Ω / □ or less regardless of the conductive component of the linear structure. More preferably, it is 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.

  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 them, a slit die coating that can uniformly laminate the protective layer and hardly damage the conductive layer, or a wet coating method using a micro gravure that can form the 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 remover used for the present invention will be described. The removing agent used in the present invention contains an acid or base component. By containing an acid or base component, the linear structure can be selectively removed when applied on the protective layer. The remover used for the present invention is:
It contains at least one member selected from the group consisting of an acid having a boiling point of 80 ° C. or higher, a base having a boiling point of 80 ° C. or higher, or a compound that generates an acid or a base by external energy, a solvent, a resin, and a leveling agent. By including a leveling agent, a high osmotic force is imparted to the conductive layer removing agent, and a fibrous conductive component that has been difficult to remove can be easily removed. The removal agent is applied to at least a part of the protective layer on the conductive layer side, heat-treated at 80 ° C. or higher, and the conductive layer is removed by washing with a liquid, thereby removing the portion where the removal agent is applied. The conductive layer can be selectively removed. By applying the remover to a desired location, a complicated and high-definition pattern including acute angles and curves can be arbitrarily formed. The heat treatment temperature is preferably lower than the boiling point of components other than the solvent in the removing agent, and is preferably 200 ° C. or lower.
The removing agent used in the present invention can also easily remove a conductive layer containing a metal such as CNT, graphene, silver or copper having low reactivity as a conductive component.

  The acid preferably used for the remover is not particularly limited as long as the boiling point is 80 ° C. or higher. Here, in the present invention, the boiling point refers to a value under atmospheric pressure, and is measured according to JIS-K5601-2-3 (1999). 100 degreeC or more is preferable and 200 degreeC or more is more preferable. In the present invention, an acid that does not have a clear boiling point under atmospheric pressure and starts thermal decomposition at 80 ° C. or higher prior to vaporization when the temperature is raised is included in the acid having a boiling point of 80 ° C. or higher. Moreover, the thing whose vapor pressure density in the heat processing temperature at the time of removing a conductive layer is 30 kPa or less is more preferable. For example, monocarboxylic acids such as formic acid, acetic acid and propionic acid, dicarboxylic acids such as oxalic acid, succinic acid, tartaric acid and malonic acid, tricarboxylic acids such as citric acid and tricarballylic acid, alkylsulfonic acids such as methanesulfonic acid, benzene Phenyl sulfonic acid such as sulfonic acid, alkyl benzene sulfonic acid such as toluene sulfonic acid and dodecylbenzene sulfonic acid, sulfonic acid compound such as phenol sulfonic acid, nitrobenzene sulfonic acid, styrene sulfonic acid and polystyrene sulfonic acid, organic acid such as trifluoroacetic acid And a partially fluorinated derivative, and inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid. Two or more of these may be contained.

  Among these, acids having high oxidizing power are preferable, and sulfuric acid or sulfonic acid compounds are more preferable. Since the boiling point of sulfuric acid under atmospheric pressure is 290 ° C., for example, the vapor pressure density of sulfuric acid at 150 ° C. is 1.3 kPa or less, the liquid state is maintained even when heated at this temperature, and the linear structure in the conductive layer Deeply penetrates the body. Furthermore, since sulfuric acid has a high oxidizing power, it reacts easily with the conductive layer even at a low temperature of about 80 to 200 ° C., and can be conducted without affecting the substrate by heat treatment in a shorter time than nitric acid or acetic acid. The layer can be removed. In addition, since the sulfonic acid compound is a solid acid under atmospheric pressure, it does not evaporate. For example, the vapor pressure density at 150 ° C. is 1.3 kPa or less, so it evaporates or sublimes even when heated at this temperature. Since the reaction is efficiently promoted during heating, the conductive layer can be removed by a short heat treatment. Furthermore, since the removal agent containing a solid acid can easily control non-Newtonian fluidity, a linear pattern having a small line width of, for example, a line width of about 30 μm is reduced with respect to various substrates with less variation in line width (swell). It is particularly preferable because a high-definition pattern can be formed.

  The base used for this invention will not be specifically limited if a boiling point is 80 degreeC or more, 100 degreeC or more is preferable and 150 degreeC or more is more preferable. In the present invention, a base that does not have a clear boiling point under atmospheric pressure and starts thermal decomposition at 80 ° C. or higher prior to vaporization when the temperature is raised is included in the base having a boiling point of 80 ° C. or higher. Moreover, the thing whose vapor pressure density in the heat processing temperature at the time of removing an electrically conductive film is 30 kPa or less is more preferable. For example, sodium hydroxide, potassium hydroxide, cesium hydroxide, tetramethylammonium hydroxide, barium hydroxide, guanidine, trimethylsulfonium hydroxide, sodium ethoxide, diazabicycloundecene, hydrazine, phosphazene, proazaphosphatran , Ethanolamine, ethylenediamine, triethylamine, trioctylamine, alkoxysilane having an amino group, and the like. Two or more of these may be contained.

  Examples of the compound that generates acid by external energy that is preferably used for the remover include compounds that generate acid by radiation, ultraviolet irradiation and / or heat. For example, sulfonium compounds such as 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate and trifluoromethanesulfonate, benzophenone compounds such as 4,4-bis (dimethylamine) benzophenone and 4,4-dichlorobenzophenone, and benzoins such as benzoin methyl ether Compounds, phenyl ketone compounds such as 4-benzoyl-4-methyldiphenyl ketone and dibenzyl ketone, acetophenone compounds such as 2,2-diethoxyacetophenone and 2-hydroxy-2-methylpropionphenone, 2,4-diethylthioxanthene Thioxanthene compounds such as -9-one and 2-chlorothioxanthone, anthraquinone compounds such as 2-aminoanthraquinone and 2-ethylanthraquinone, benzanthones Anthrone compounds such as Ron and methyleneanthrone, imidazole compounds such as 2,2-bis (2-chlorophenyl) -4,4,5,5-tetraphenyl-1,2-biimidazole, 2- (3,4-dimethoxy) Cytyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (5-methylfuran-2-yl) vinyl] -4,6-bis (trichloromethyl)- Triazine compounds such as 1,3,5-triazine, benzoyl compounds such as 2-benzoylbenzoic acid and benzoyl peroxide, sulfone compounds such as 2-pyridyltribromomethylsulfone and tribromomethylphenylsulfone, 4-isopropyl-4- Methyldiphenyliodonium tetrakis (pentafluorophenyl) borate, diphenyliodonium trif Iodonium compounds such Oro methanesulfonic acid, tetramethylthiuram disulfide, 9-fluorenone, dibenzosuberone, N- methyl acridone, nifedipine, camphorquinone, and the like carbon tetrabromide. Two or more of these may be contained.

  Examples of the compound that generates a base by external energy used in the present invention include compounds that generate a base by radiation, ultraviolet irradiation and / or heat. For example, bis [(α-methyl) -2,4,6-trinitrobenzyloxycarbonyl] methanediphenylenediamine, N-[(2-nitrophenyl) -1-methylmethoxy] carbonyl-2-propylamine, etc. Examples include amine compounds, benzyl carbamates, benzyl sulfonamides, benzyl quaternary ammonium salts, imines, iminium salts, cobalt amine complexes, and oxime compounds. Two or more of these may be contained.

  In the removing agent used in the present invention, the content of an acid having a boiling point of 80 ° C. or higher, a base having a boiling point of 80 ° C. or higher, or a compound that generates an acid or a base by external energy is 1 to 80% by weight in the component excluding the solvent. Is preferred. Among them, the content of the acid having a boiling point of 80 ° C. or higher is preferably 10 to 70% by weight, and more preferably 20 to 70% by weight in the component excluding the solvent. The content of the base having a boiling point of 80 ° C. or higher is preferably 0.01 to 70% by weight in the component excluding the solvent. Further, the content of the compound that generates an acid by external energy is preferably 0.1 to 70% by weight in the components excluding the solvent. The content of the compound that generates a base by external energy is preferably 1 to 80% by weight in the components excluding the solvent. However, it is not limited to this range, and can be appropriately selected depending on the molecular weight of the compound, the amount of acid or base generated, the material and film thickness of the conductive layer to be removed, the heating temperature and the heating time.

  The removing agent used in the present invention contains a solvent. Specific examples of solvents include acetates such as ethyl acetate and butyl acetate, ketones such as acetone, acetophenone, ethyl methyl ketone, and methyl isobutyl ketone, aromatic hydrocarbons such as toluene, xylene, and benzyl alcohol, methanol, ethanol 1,2-propanediol, terpineol, acetyl terpineol, butyl carbitol, ethyl cellosolve, alcohols such as ethylene glycol, triethylene glycol, tetraethylene glycol, glycerol, ethylene glycol monoalkyl ethers such as triethylene glycol monobutyl ether , Ethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, ethylene glycol monoaryl ethers, polymers Ethylene glycol monoaryl ethers, propylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, ethylene carbonate, propylene carbonate, γ-butyrolactone, solvent naphtha, water, N-methylpyrrolidone, dimethyl Examples thereof include sulfoxide, hexamethylphosphoric triamide, dimethylethyleneurea, N, N′-dimethylpropyleneurea, and tetramethylurea. Two or more of these may be contained.

  In the present invention, the content of the solvent is preferably 1% by weight or more, more preferably 30% by weight or more, and more preferably 50% by weight or more in the removing agent. By setting the content of the solvent to 1% by weight or more, it is possible to improve the fluidity of the removing agent and further improve the coating property. On the other hand, 99.9 weight% or less is preferable and 95 weight% or less is more preferable. By setting the content of the solvent to 99.9% by weight or less, the fluidity during heating can be maintained in an appropriate range, and a desired pattern can be accurately maintained.

  The removing agent of the present invention contains a resin. By including the resin, a remover having non-Newtonian fluidity can be obtained and can be easily applied to the conductive laminate by a known method. Moreover, the fluidity | liquidity of the removal agent at the time of heat processing can be restrict | limited, and the precision of an application position can be improved. Examples of the resin include polystyrene resin, polyacrylic resin, polyamide resin, polyimide resin, polymethacrylic resin, melamine resin, urethane resin, benzoguanamine resin, phenol resin, silicone resin, and fluorine resin. Two or more of these may be contained. Among these, when a hydrophilic resin such as nonionic, anionic, amphoteric or cationic is contained, it can be easily washed with water, a basic aqueous solution or an aqueous solution of an organic solvent described later, Residues can be suppressed and in-plane uniformity can be further improved.

  Specific examples of the hydrophilic resin include polyvinyl pyrrolidone, hydrophilic polyurethane, polyvinyl alcohol, polyethyloxazoline, polyacrylic acid, gelatin, hydroxyalkyl guar, guar gum, locust bean gum, carrageenan, alginic acid, gum arabic, pectin, Xanthan gum, cellulose, ethylcellulose, hydroxypropylcellulose, carboxymethylcellulose, sodium carboxymethylhydroxyethylcellulose, acrylamide copolymer, polyethyleneimine, polyaminesulfonium, polyvinylpyridine, polydialkylaminoethyl methacrylate, polydialkylaminoethyl acrylate, polydialkyl Aminoethyl methacrylamide, polydialkylaminoethyl acrylate De, polyepoxy amine, polyamidoamine, dicyandiamide - formalin condensate, polydimethyl diallyl ammonium chloride, polyamine polyamide epichlorohydrin, polyvinyl amine, compounds such as polyacrylic amine and the like of these modified products thereof.

  Among these, a cationic resin that is hardly denatured even under an acid or high temperature condition and exhibits high solubility in a polar solvent is more preferable. By maintaining high solubility, the conductive layer can be removed in a short time after the heat treatment in the step of removing the conductive layer by washing with a liquid. Examples of the cationic resin include polydialkylaminoethyl methacrylate, polydialkylaminoethyl acrylate, polydialkylaminoethyl methacrylamide, polydialkylaminoethyl acrylamide, polyepoxyamine, polyamidoamine, dicyandiamide-formalin condensate, polydimethyl Diallylammonium chloride, guar hydroxypropyltrimonium chloride, polyamine polyamide epichlorohydrin, polyvinylamine, polyallylamine, polyacrylamine, polyquaternium-4, polyquaternium-6, polyquaternium-7, polyquaternium-9, polyquaternium-10, polyquaternium-11, polyquaternium -16, Polyquaternium-28, Polyquaternium- 2, polyquaternium-37, polyquaternium -39, polyquaternium -51, polyquaternium -52, polyquaternium -44, polyquaternium -46, polyquaternium -55, like compounds and modified products thereof, such as polyquaternium -68. For example, polyquaternium-10 has a trimethylammonium group at the end of the side chain. Under acidic conditions, the trimethylammonium group is cationized and exhibits high solubility due to the action of electrostatic repulsion. Moreover, dehydration polycondensation due to heating hardly occurs, and high solvent solubility is maintained even after heating. Therefore, after the heat treatment, the conductive film can be removed in a short time in the step of removing the conductive layer by washing with a liquid.

  In the removing agent used in the present invention, the content of the resin when the resin is used is preferably 0.01 to 80% by weight in the components excluding the solvent. In order to keep the heating temperature required for removing the conductive layer low and shorten the heating time, it is more preferable that the resin content in the removing agent is as small as possible within the range that maintains the non-Newtonian fluidity. The viscosity of the remover is preferably about 2 to 500 Pa · S (25 ° C.), and a uniform coating film can be easily formed by a screen printing method. The viscosity of the remover can be adjusted by, for example, the contents of the solvent and the resin.

  The removing agent used in the present invention preferably contains a leveling agent. By containing the leveling agent, a high osmotic force is imparted to the removing agent, and even a conductive layer including a fibrous conductor can be easily removed. The leveling agent is preferably a compound having a property of reducing the surface tension of the removing agent to less than 50 mN / m. Specific examples of leveling agents include acrylic compounds such as modified polyacrylates and acrylic resins, vinyl compounds and vinyl resins having double bonds in the molecular skeleton, alkyloxysilyl groups, and / or polysiloxane skeletons. Examples thereof include a silicone compound, a silicone resin, a fluorine compound having a fluorinated alkyl group and / or a fluorinated phenyl group, and a fluorine resin. Depending on the material and polarity of the surface of the protective layer, these can be appropriately selected and used. However, fluorine compounds and fluorine resins having a fluorinated alkyl group and / or a fluorinated phenyl group have a surface tension reducing ability. Since it is strong, it is particularly preferably used. In the present invention, any compound having a property of reducing the surface tension to less than 50 mN / m is classified as a leveling agent even if it is a polymer compound.

  In the remover used in the present invention, the content of the leveling agent is the component excluding the solvent from the balance between the surface active ability such as wettability and leveling property to the conductive laminate and the acid content of the resulting coating film. 0.001-10 weight% is preferable, 0.01-5 weight% is more preferable, 0.05-3 weight% is further more preferable.

  In the present invention, when an acid having a boiling point of 80 ° C. or higher or a compound that generates an acid by external energy is included, it is preferable to further include nitrate or nitrite. The reaction rate between the acid and the conductive component may vary depending on the type, but by including nitrate or nitrite, the acid reacts with nitrate or nitrite during the heat treatment, and nitric acid in the system. Therefore, dissolution of the conductive component can be further promoted. For this reason, the conductive layer can be removed by a short heat treatment. Examples of the nitrate include lithium nitrate, sodium nitrate, potassium nitrate, calcium nitrate, ammonium nitrate, magnesium nitrate, barium nitrate, and hydrates of these nitrates. Examples of the nitrite include sodium nitrite, potassium nitrite, calcium nitrite, silver nitrite, and barium nitrite. Two or more of these may be contained. Among these, in consideration of the reaction rate of nitric acid production, nitrate is preferable, and sodium nitrate or potassium nitrate is more preferable.

  The removal agent used in the present invention is inorganic fine particles such as titanium oxide, alumina and silica, thixotropic agent capable of imparting thixotropic properties, antistatic agent, antifoaming agent, viscosity modifier, light stability, depending on the purpose. Agents, weathering agents, heat resistance agents, antioxidants, rust inhibitors, slip agents, waxes, mold release agents, compatibilizers, dispersants, dispersion stabilizers, rheology control agents, and the like.

  An example is given and demonstrated about the manufacturing method of the removal agent used for this invention. First, the resin is added to the solvent and dissolved with sufficient stirring. Stirring may be performed under heating conditions, and stirring is preferably performed at 50 to 80 ° C. for the purpose of increasing the dissolution rate. Next, an acid having a boiling point of 80 ° C. or higher, a base having a boiling point of 80 ° C. or higher, a compound that generates an acid or a base by external energy, a leveling agent, and, if necessary, the additive are added and stirred. The addition method and the addition order are not particularly limited. Stirring may be performed under heating conditions, and stirring is preferably performed at 50 to 80 ° C. for the purpose of increasing the dissolution rate of the additive.

  An example is given and demonstrated about the method of pattern-forming the conductive laminated body of this invention by the chemical etching using a removal agent. A removing agent is applied to a portion to be removed on the protective layer side of the conductive laminate in the present invention. Since the removing agent used in the present invention has non-Newtonian fluidity, it can be applied using a known method regardless of the type, size, and shape of the conductive laminate. Examples of the coating method include screen printing method, dispenser method, stencil printing method, pad printing method, spray coating, ink jet method, micro gravure printing method, knife coating method, spin coating method, slit coating method, roll coating method, curtain Examples thereof include, but are not limited to, a coating method and a flow coating method. In order to further reduce the etching unevenness of the conductive layer, it is preferable to uniformly apply the removing agent on the protective layer of the conductive laminate.

  The thickness of the applied removal film is appropriately determined depending on the material and thickness of the conductive layer to be removed, the heating temperature and the heating time, and it is preferable that the thickness after drying is 0.1 to 200 μm. More preferably, it is -200 micrometers. By setting the thickness of the removing agent after drying within the above range, a necessary amount of the conductive layer removing component is contained in the coating film, and the conductive layer can be more uniformly removed in the surface. Moreover, since the sagging in the lateral direction can be suppressed during heating, a desired pattern can be obtained without any positional deviation of the coating film boundary line.

  Next, the conductive laminate coated with the removing agent is heat-treated at 80 ° C. or higher. The heat treatment temperature is preferably a temperature lower than the boiling point of components other than the solvent in the removing agent, and preferably 200 ° C. or lower. By conducting the heat treatment in the above temperature range, the conductive layer in the portion where the removing agent is applied is decomposed, dissolved or solubilized. The heat treatment method can be selected according to the purpose and application, and examples thereof include, but are not limited to, a hot plate, a hot air oven, an infrared oven, and microwave irradiation with a frequency of 300 megahertz to 3 terahertz.

  After the heat treatment, the removal agent and the decomposed / dissolved material of the conductive layer are removed by washing with a liquid to obtain a desired conductive pattern. The liquid used in the washing step is preferably one in which the resin contained in the removing agent is dissolved. Specifically, ketones such as acetone, alcohols such as methanol, and organic solvents such as tetrahydrofuran are raised, and the organic Examples include, but are not limited to, an aqueous solution containing a solvent, a basic aqueous solution containing sodium hydroxide, ethanolamine, triethylamine and the like, and pure water. In order to wash without residue in the washing step, the liquid may be heated to 25 to 100 ° C. and used.

  The touch panel of the present invention is one in which the conductive laminate of the present invention is mounted alone or in combination with other members, and examples thereof include a resistive touch panel and a capacitive touch panel. A touch panel on which these conductive laminates of the present invention are mounted is used, for example, by attaching a lead wire and a drive unit and incorporating it on the front surface of a liquid crystal display.

  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) Surface resistance value R ₀
The surface resistance value on the conductive layer side was measured at a central portion of a 100 mm × 50 mm sample by an eddy current method using a non-contact resistivity meter (NC-10 manufactured by Napson Co., Ltd.). An average value was calculated for 5 samples, and this was defined as a surface resistance value R ₀ [Ω / □]. When the surface resistance value was not obtained exceeding the detection limit, it was then measured by the following method.

Using a high resistivity meter (Hiresta-UP MCP-HT450 manufactured by Mitsubishi Chemical Corporation), a ring type probe (URS probe MCP-HTP14 manufactured by Mitsubishi Chemical Corporation) is connected and 100 mm × 100 mm in a double ring system. The central part of the sample was measured. An average value was calculated for 5 samples, and this was defined as a surface resistance value R ₀ [Ω / □].

(2) Structure of the laminate After embedding in the vicinity of the portion of the sample to be observed with ice and freezing, or embedding with a component that has a stronger adhesion than ice, such as epoxy resin, rotary manufactured by Nippon Microtome Laboratory Co., Ltd. Using a microtome, set a diamond knife at a knife tilt angle of 3 ° and cut in a direction perpendicular to the film plane. Next, the film cross section obtained was selected from an observation magnification of 10,000 to 200,000 times at an accelerating voltage of 3.0 kV using a field emission scanning electron microscope (JSM-6700-F manufactured by JEOL Ltd.). Then, the contrast of the image was appropriately adjusted and observed at each magnification.

(3) Discrimination of linear structure (structure of conductive component), network state of linear structure Scanning transmission electron microscope (Hitachi scanning transmission electron microscope HD manufactured by Hitachi High-Technologies Corporation) -2700).

  When observation by the above method is difficult, using a field emission scanning electron microscope (JSM-6700-F, manufactured by JEOL Ltd.) at an accelerating voltage of 3.0 kV, an observation magnification of 10,000 to 200,000 times is arbitrary 3 The magnification was selected, the image contrast was adjusted as appropriate, and the image was observed at each magnification.

  Further, when observation by the above method is difficult, using a color 3D laser microscope (VK-9710 manufactured by Keyence Corporation), an attached standard objective lens 10X (CF IC EPI Plan 10X manufactured by Nikon Corporation), 20X (CF IC EPI Plan 20X manufactured by Nikon Corporation), 50X (CF IC EPI Plan Apo 50X manufactured by Nikon Corporation), and 150X (CF IC EPI Plan Apo 150XA manufactured by Nikon Corporation) at each magnification. The same position on the side was observed on the surface, and image analysis was performed from the image data using an observation application (VK-HV1 manufactured by Keyence Corporation) for confirmation.

  If observation is still difficult, then using an atomic force microscope (Digital Instruments, NanoScope III), the cantilever is a silicon single crystal, the scanning mode is a tapping mode, the measurement environment is a temperature of 25 ° C., and a relative humidity of 65% RH. Observed.

  If it cannot be observed by surface observation, a single substance can be obtained by general chromatography such as silica gel column chromatography, gel permeation chromatography, liquid high-performance chromatography, gas chromatography, etc. and other methods that can be separated and purified. After separating and purifying, and concentrating and diluting appropriately, a sufficient amount of a substance corresponding to the conductive component was collected and collected, and then observed in the same manner to determine the linear structure (structure of the conductive component).

(4) Contact angle of the surface on the protective layer side It was performed by a sessile drop method according to JIS R3257. Conductive layer side (protective layer side) of the conductive laminate of the present invention determined from (1) using a contact angle meter (FACE contact angle meter CA-X type (image processing type) manufactured by Kyowa Interface Science Co., Ltd.) ) Was used as the measurement surface and placed horizontally on the sample stage, and pure water was dropped to obtain the contact angle. The contact angle was determined at a total of 10 locations by the same method, and the average value of the 10 points was defined as the contact angle of pure water in the present invention. Subsequently, oleic acid (manufactured by Nacalai Tesque Co., Ltd.) was dropped into another arbitrary 10 places in the same manner, and the average value of 10 points was used as the contact angle of oleic acid in the present invention.

(5) Identification of elements, structure, and bonding state of compound in protective layer The elements contained in the compound in the protective layer, the structure of the compound (polymer structure, etc.), and the bonding state (crosslinking, etc.) are first described in (1) or The surface on the conductive layer side or the protective layer side of the conductive laminate is determined by the method (2). Then, if necessary, as in the method of (3), general chromatography represented by silica gel column chromatography, gel permeation chromatography, liquid high performance chromatography, gas chromatography, etc. and other separation / purification can be performed. Separation and purification into a single substance by a possible method, and concentration and dilution as appropriate.

Next, for the protective layer, dynamic secondary ion mass spectrometry (Dynamic-SIMS), time-of-flight secondary ion mass spectrometry (TOF-SIMS), other static secondary ion mass spectrometry (Static-SIMS), nuclear Magnetic resonance spectroscopy ( ¹ H-NMR, ¹³ C-NMR, ²⁹ Si-NMR, ¹⁹ F-NMR), two-dimensional nuclear magnetic resonance spectroscopy (2D-NMR), infrared spectrophotometry (IR), Raman spectroscopy Method, mass spectrometry (Mass), X-ray diffraction (XRD), neutron diffraction (ND), low-energy electron diffraction (LEED), fast reflection electron diffraction (RHEED), atomic absorption spectrometry (AAS) , Ultraviolet photoelectron spectroscopy (UPS), Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), X-ray fluorescence elemental analysis (XRF), inductively coupled plasma emission Optical method (ICP-AES), electron microanalysis method (EPMA), charged particle excitation X-ray spectroscopy (PIXE), low energy ion scattering spectroscopy (RBS or LEIS), medium energy ion scattering spectroscopy (MEIS), High energy ion scattering spectroscopy (ISS or HEIS), gel permeation chromatography (GPC), transmission electron microscope-energy dispersive X-ray spectroscopic analysis (TEM-EDX), scanning electron microscope-energy dispersive X-ray spectroscopic analysis (SEM-EDX) ), And other elemental analysis methods were appropriately selected and combined to identify and analyze the elements contained in the protective layer compound, structure, and bonding state.

(6) Evaluation of pattern formed by chemical etching As an evaluation of pattern miniaturization, the following (a) to (c) three indexes were used in the pattern of linear lines described later.
(A) Line width of printed pattern of remover / Line width of remover transferred / laminated on conductive laminate.
-It shows that a fine pattern is transcribe | transferred and laminated | stacked on a conductive laminated body, so that line width is thin, and it shows that line thickness is so large that it is thick.
(B) Line width of the etching pattern. Line width of the etched portion after the removing agent transferred and laminated on the conductive laminate is washed with water.
As in the case of (a) above, the thinner the line width, the smaller the pattern is formed, and the thicker the line, the greater the line thickness.
(C) Line linearity (undulation) at the etching boundary of the etching pattern
The standard deviation (σ) of the line width obtained in (b) above.
-The smaller the standard deviation (σ), the higher the definition and the clearer the pattern.

  First, the conductive layer side (protective layer side) of the conductive laminate described in Examples and Comparative Examples is observed by the same method as described in (1) and (2), and the protective layer is formed on the conductive layer. Was confirmed to be laminated.

  Next, a remover described later is prepared, and the film thickness after drying the remover is 2.4 μm using a sus # 500 mesh at the same position as the observed portion on the conductive laminate described in Examples and Comparative Examples. It was screen printed as follows. The print pattern was a straight line with a line length of 5 cm (i) a line width of 50 μm and (ii) 100 μm. After applying the remover, it was placed in an infrared oven, heat-treated at 130 ° C. for 3 minutes, removed from the oven and allowed to cool to room temperature, to obtain a conductive laminate in which the remover was transferred and laminated in a linear pattern. Next, in each of the linear patterns (i) and (ii) of the conductive laminate in which the remover is transferred and laminated, 0.5 cm, 1 cm, 1.5 cm, 2 cm, and 2.5 cm from one end of the line length. (Line midpoint) 3 cm, 3.5 cm, 4 cm (1 cm from the other end), using a color 3D laser microscope (VK-9710 manufactured by Keyence Co., Ltd.), attached standard objective lens 10X (Nikon Corporation CF IC EPI Plan 10X), 20X (Nikon Corporation CF IC EPI Plan 20X), 50X (Nikon Corporation CF IC EPI Plan Apo 50X), 150X (Nikon Corporation) CF IC EPI Plan Apo 150XA) was arbitrarily changed and observed. Next, the image data of each linear pattern of (i) and (ii) is subjected to image analysis using an observation application (VK-HV1 manufactured by Keyence Co., Ltd.), and the maximum value and the minimum value of the line width at each position (the above eight locations) A value was obtained, and an average value of a total of 16 points was calculated, and this value was taken as the line width of the print pattern of the (a) remover.

  Next, the conductive laminate on which the removing agent was transferred and laminated was washed with pure water at 25 ° C. for 1 minute to remove the attached removing agent and decomposition products. The substrate was drained with compressed air and then dried in an infrared oven at 80 ° C. for 1 minute to obtain a conductive laminate in which the conductive layer was patterned.

  The same position (the eight locations) as the observed portion of the patterned portion of the conductive laminate on which the conductive layer was patterned was similarly observed, and the average value of a total of 16 points was defined as the line width of the (b) etching pattern. Further, the standard deviation (σ) was calculated from a total of 16 points.

(7) Electrical insulation of the patterning portion The conductive laminate produced by patterning the conductive layer prepared in (6) was cut at 1 cm from both ends of the line length of each straight line, and 3 cm separated by an etching line. A conductive laminate of × 10 cm was obtained. And the case where the resistance of 10 MΩ or more is shown by applying a probe of an insulation resistance meter (manufactured by Sanwa Denki Keiki Co., Ltd., EA709DA-1) on the right side and the left side of the etching line is passed, less than 10 MΩ The case where resistance was shown was made unacceptable.

(8) Presence or absence of conductive component remaining in patterning portion The patterning portion of the conductive laminate in which the conductive layer prepared in (6) was patterned was observed by the same method as described in (3).

  The case where the conductive component determined in the above (3) could not be confirmed was determined to pass (no remaining conductive component), and the case where it could be confirmed was rejected (conductive component remained).

(9) Difference in maximum absorption wavelength of photoinitiator The components of the protective layer were separated and purified by any method similar to (3), and only the compounds corresponding to the photoinitiator were extracted from the various components. When it was unclear whether the photoinitiator was applicable or not, a compound that was irradiated with an active electron beam to generate any one of radical species, cation species, and anion species was used as a photoinitiator. Next, the photoinitiator was dissolved in various soluble solvents. Next, this solution is put in a quartz cell, and an absorption spectrum at a wavelength of 200 to 900 nm is measured using an ultraviolet-visible spectrophotometer (UV-Bis Spectrophotometer, model V-660 manufactured by JASCO Corporation), and a maximum absorption wavelength is obtained. Asked.

  In each photoinitiator, the absorption spectrum was measured three times in the same manner to determine the maximum absorption wavelength, and the average value was taken as the maximum absorption wavelength of the photoinitiator, and the difference in the maximum absorption wavelength of each photoinitiator was determined.

  When there are a plurality of maximum values, the following is set as the maximum absorption wavelength. Of the plurality of maximum values existing in the region of 200 to 400 nm in the absorption spectrum obtained with an optical path length of 1 cm, the wavelength at the maximum value with the highest absorbance is defined as the maximum absorption wavelength. Here, if the concentration of the photoinitiator when dissolved in a solvent is too high, the maximum value with the highest absorbance will exceed the detection limit of the device used, as if there is no maximum value with the highest absorbance. Therefore, the concentration of the photoinitiator was appropriately changed and measured in the same manner, and the wavelength at the maximum value having the highest absorbance at each same concentration was taken as the maximum absorption wavelength.

(10) Total light transmittance Based on JIS K7361-1 (1997) using a turbidimeter (cloudiness meter) NDH2000 (manufactured by Nippon Denshoku Industries Co., Ltd.), total light transmission 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.
[Example]
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
・ Linear acrylic resin (Foret GS-1000, manufactured by Soken Chemical Co., Ltd., solid content concentration: 30% by mass)
(An organic polymer compound that does not contain any of the S element, P element, metal element, metal ion, and N element constituting the functional group, and does not have a crosslinked structure.)
(2) Protective layer material B
・ Polyfunctional acrylic resin composition (Soukken Chemical Co., Ltd., Full Cure HC-6, solid content concentration 51% by mass)
(An organic polymer compound that does not contain any of the S element, the P element, the metal element, the metal ion, and the N element constituting the functional group, and forms a crosslinked structure with a photoinitiator.)
(3) Protective layer material C
-Polyfunctional acrylic resin composition (Furucure UAF-1, manufactured by Soken Chemical Co., Ltd., solid content concentration 48.4% by mass)
(S-element, P-element, metal element, metal ion and organic polymer compound not containing N element constituting functional group and having F element (fluorine element), and forming a cross-linked structure with a photoinitiator .)
(4) Protective layer material D
・ Polyfunctional acrylic resin composition (Aurex JU-114 manufactured by China Paint Co., Ltd., solid concentration 70% by mass)
(S element, P element, metal element, metal ion, and N element constituting the functional group are all organic polymer compounds having an alkyl chain, and a crosslinked structure is formed by a photoinitiator.)
(5) Protective layer material E
-Polyfunctional urethane acrylate resin composition (Negami Kogyo Co., Ltd. Art Resin UN-904M, solid content concentration 80% by mass)
(S element, P element, metal element, metal ion and N element constituting the functional group are all organic polymer compounds containing N element in the skeleton structure, and the crosslinked structure is formed by the photoinitiator. Form.)
(6) Protective layer material F
・ Polyfunctional acrylic resin composition (manufactured by Soken Chemical Co., Ltd., Full Cure HCE-022, solid concentration 52.1% by mass)
(An organic polymer compound containing an N element and a metal ion that form a functional group, and a crosslinked structure is formed by a photoinitiator.)
(7) Protective layer material G
・ Linear acrylic resin (polymerized below, solid concentration 100% by mass)
(It is an organic polymer compound containing S element and does not have a crosslinked structure.)
Acrylamide t-Butyl Sulphonic Acid (also known as 2-Acrylamide-2-Methyl Propane Sulphonic Acid, 2-acrylamido-2-methylpropane sulfonic acid) and Methyl Methacrylate (also known as methyl methacrylate, 2-methyl-2-propenoic acid, Copolymerized from the abbreviation MMA).

(8) Protective layer material H
・ Linear acrylic resin (polymerized below, solid concentration 100% by mass)
(It is an organic polymer compound containing S element and metal ion, and does not have a crosslinked structure.)
・ Acrylamide t-Butyl Sulphonic Acid Sodium Sait (also known as 2-Acrylamide-2-Methyl Propane Sulphonic Acid Sodium Sait, 2-Acrylic-2-methylpropanesulfonic acid sodium) and Methyl Methyl Methyl Methyl Methyl Methyl -Copolymerized from methyl propenoate, abbreviation MMA).

(9) Protective layer material I
・ Polyfunctional acrylic resin composition (prepared below, solid concentration 40% by mass)
(It is an organic polymer compound containing P element, and a crosslinked structure is formed by a photoinitiator.)
-A resin composition was obtained in the same manner as in Example 1 of JP-A-2008-222848. This resin composition contains the following (12) additive A.

(10) Protective layer material J
Inorganic silicon oxide (silica) composition (prepared below, solid content concentration 3% by mass)
(An inorganic polymer compound that does not contain any of the S element, the P element, the metal element, the metal ion, and the N element constituting the functional group, and forms a crosslinked structure by heat.)
-Ethanol 20g was put into a 100 mL plastic container, 40 g of n-butyl silicate was added, and it 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 3.0% by mass.

(11) Protective layer material K
・ Polyfunctional acrylic resin composition (manufactured by Soken Chemical Co., Ltd., Full Cure UAF-6, solid content concentration 50.9% by mass)
(An organic polymer compound that does not contain any of the S element, the P element, the metal element, the metal ion, and the N element constituting the functional group, and forms a crosslinked structure with a photoinitiator.)
(12) Additive A
Photopolymerization initiator (Ciba Japan Co., Ltd. Ciba (registered trademark) IRGACURE (registered trademark) 184)
・ Maximum absorption wavelength 240nm
(13) Additive B
Photopolymerization initiator (Ciba Japan Co., Ltd. Ciba (registered trademark) IRGACURE (registered trademark) 907)
・ Maximum absorption wavelength 300nm
(14) Additive C
Photopolymerization initiator (Ciba Japan Co., Ltd. Ciba (registered trademark) IRGACURE (registered trademark) 369)
・ Maximum absorption wavelength: 320 nm
(15) Additive D
Photopolymerization initiator (Ciba Japan Co., Ltd. Ciba (registered trademark) IRGACURE (registered trademark) 651)
・ Maximum absorption wavelength 250nm
(16) Additive E
・ Organic low molecular weight compound containing F element (fluorine element) (Optool ^TM DAC, solid concentration 20% by mass, manufactured by Daikin Industries, Ltd.)
(17) Additive F
・ Silicone compound (Shin-Etsu Chemical Co., Ltd. X-22-8114 40% concentration solution, can be combined with protective layer material J by heat)
The conductive layer in each Example and Comparative Example is shown below. Each conductive layer was laminated | stacked by the following each method on the base material in an Example and a comparative example.

(1) Conductive layer A “Acicular silicon dioxide-based / ATO (antimony-doped tin oxide) composite compound conductive layer”
The protective layer material A (acrylic resin) as a binder component, and a needle-like silicon dioxide-based / ATO (antimony-doped tin oxide) composite compound (Dentor TM100, manufactured by Otsuka Chemical Co., Ltd.), short axis: 700 to 900 nm as a conductive component , Long axis: 15 to 25 μm), and mixed so that the amount of the conductive component relative to the entire solid content is 60% by mass (solid content mixing ratio: binder component / conductive component = 40% by mass / 60% by mass), Ethyl acetate was added to this mixed solution to dilute it so that the concentration of the solid content of the paint was 50% by mass, and the concentration was adjusted to obtain a needle-like silicon dioxide-based / ATO (antimony-doped tin oxide) composite compound-dispersed coating solution. This acicular silicon dioxide-based / ATO (antimony-doped tin oxide) composite compound dispersion coating solution was applied onto a substrate using a slit die coat equipped with a shim (shim thickness: 100 μm) made of sus, and 5 ° C. at 120 ° C. It was dried for a minute and provided with a needle-like silicon dioxide-based / ATO (antimony-doped tin oxide) composite compound coating film.

(2) Conductive layer B "Silver nanowire conductive layer"
Silver nanowires (short axis: 50 to 100 nm, long axis: 20 to 40 μm) were obtained by the method disclosed in Example 1 (synthesis of silver nanowire) of 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. The concentration of the silver nanowire-dispersed coating liquid was adjusted so that the amount of silver nanowires relative to the entire coating liquid was 0.05% by mass. This concentration-adjusted silver nanowire dispersion coating solution is applied onto a substrate using a slit die coat equipped with a shim material (shim thickness 50 μm) and dried at 120 ° C. for 2 minutes to form a silver nanowire coating film. Provided.

(3) Conductive layer C “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 solution was applied onto a substrate with a micro gravure coater (gravure wire number 150R, gravure rotation ratio 80%), dried at 100 ° C. for 1 minute, and a CNT coating (short axis as a CNT aggregate in the CNT coating) : 10-30 nm, long axis: 1-5 μm).

(4) Conductive layer D “Acicular ATO (antimony-doped tin oxide) conductive layer”
The protective layer material A (acrylic resin) as the binder component, and the needle-shaped ATO (antimony-doped tin oxide, manufactured by Ishihara Sangyo Co., Ltd.) as the conductive component, the needle-shaped transparent conductive material FS-10P, the short axis: 10 to 20 nm, Long axis: 0.2 to 2 μm), and mixed so that the amount of the conductive component relative to the entire solid content is 60% by mass (solid content mixing ratio: binder component / conductive component = 40% by mass / 60% by mass), Subsequently, ethyl acetate was added to this mixed solution to dilute the solution so that the solid content concentration was 20% by mass, and the concentration was adjusted to obtain a needle-like ATO (antimony-doped tin oxide) dispersion coating solution. This acicular ATO (antimony-doped tin oxide) dispersion coating solution was applied onto a substrate using a bar coater # 12 manufactured by Matsuo Sangyo Co., Ltd., dried at 120 ° C. for 2 minutes, and then acicular ATO (antimony-doped tin oxide). ) A coating film was provided.

(5) Conductive layer E “Copper nanowire conductive layer”
Copper nanowires (short axis: 10 to 20 nm, long axis: 1 to 100 μm) were obtained by the method disclosed in JP-A No. 2002-266007. Subsequently, the silver nanowire disclosed in Example 8 (nanowire dispersion) of JP 2009-505358 A was changed to the copper nanowire of the present invention, and a copper nanowire dispersion coating liquid was obtained by the same method. . The concentration of the copper nanowire-dispersed coating liquid was adjusted so that the amount of copper nanowires relative to the entire coating liquid was 0.05% by mass. This concentration-adjusted copper nanowire dispersion coating solution is applied onto a substrate using a slit die coat equipped with a shim material (shim thickness 50 μm) and dried at 120 ° C. for 2 minutes to form a copper nanowire coating film. Provided.

(6) Conductive layer F “Silver nanoparticle conductive layer”
Dispersion liquid of silver nanoparticles (short axis, long axis (particle diameter): 9 to 15 nm) by the method disclosed in Examples of JP-A-2001-243841 ((2) Preparation of silver nanocolloid coating solution) Got. Subsequently, the silver nanoparticle dispersion liquid was applied by the method disclosed in [Examples 1 to 8] of JP-A-2001-243841 to obtain a silver nanoparticle coating film.

(7) Conductive layer G "Silver nanowire / silver nanoparticle mixed conductive layer"
To the silver nanoparticle dispersion obtained by the method disclosed in the example of JP-A-2001-243841 ((2) Preparation of silver nanocolloid coating solution), Example 8 of JP-T-2009-505358 ( The silver nanowire dispersion coating liquid obtained by the method disclosed in (Nanowire Dispersion) is mixed so that the mass ratio of silver nanoparticle to silver nanowire is silver nanoparticle / silver nanowire = 8/2. A silver nanowire / silver nanoparticle mixed dispersion was obtained. Next, the silver nanowire / silver nanoparticle mixed dispersion is applied onto the substrate by the method disclosed in [Examples 1 to 8] of JP-A-2001-243841. A mixed coating was obtained.

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

  The remover used in each example and comparative example is shown below. Patterning with the removing agent A is performed in each of the conductive laminates of Examples 1 to 16 and Comparative Examples 1 to 14 described later, and patterning with the removing agent B is performed in Examples 2, 3, 6, 10 to 12, Comparative Example 2, It carried out with each conductive laminate of 3, 5, 9-14.

(1) Remover A (Remover containing acid)
70 g of ethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), 30 g of N, N′-dimethylpropyleneurea (manufactured by Tokyo Chemical Industry Co., Ltd.) and 5 g of sodium nitrate are mixed in a container, and this is mixed with polyquaternium-10. 5 g (manufactured by ISP Japan) and 0.5 g of thixatrol MAX (manufactured by Elementis Japan, polyester amide derivative) as a thixotropic agent were added and stirred for 30 minutes while heating to 60 ° C. in an oil bath.

  Next, after removing the container from the oil bath and allowing to cool to room temperature, 0.5 g of a leveling agent (DIC Corporation, F-555) and p-toluenesulfonic acid monohydrate (Tokyo Chemical Industry Co., Ltd.) , Boiling point under atmospheric pressure: 103-106 ° C.) was added and stirred for 15 minutes. The resulting solution was filtered with a membrane filter (Omnipore membrane PTFE manufactured by Millipore Corporation, nominal 0.45 μm diameter) to obtain remover A.

(2) Remover B (a remover containing a base)
The removal agent B was obtained in the same manner as the removal agent A, except that the acid added to the removal agent was changed to 4 g of basic 2-ethanolamine and no nitrate was added.

Example 1
A “conductive layer A” was laminated on one side of a substrate using a 125 μm thick polyethylene terephthalate film, Lumirror (registered trademark) U46 (manufactured by Toray Industries, Inc.) as a substrate.

  Next, 500 g of “protective layer material A”, 0.75 g of “additive E”, and 1501.25 g of “ethyl acetate” were mixed and stirred to prepare a protective layer coating solution. This protective layer coating solution was applied using a slit die coat having a sus material (shim thickness 50 μm) mounted on the “conductive layer A” and dried at 120 ° C. for 2 minutes to form a protective layer having a thickness of 800 nm. It provided and obtained the electrically conductive laminated body of this invention.

(Example 2)
A “conductive layer B” was laminated on one side of a base material using a polyethylene terephthalate film having a thickness of 125 μm and Lumirror (registered trademark) U46 (manufactured by Toray Industries, Inc.) as a base material.

Next, 150 g of “protective layer material C”, 3.41 g of “additive A”, 6.79 g of “additive B”, and 2600 g of “ethyl acetate” were mixed and stirred to form a protective layer coating solution. made. This protective layer coating solution was applied using a slit die coat in which a shim made of sus (material having a thickness of 50 μm) was mounted on the “conductive layer B”, dried at 120 ° C. for 2 minutes, and then irradiated with 1.2 J ultraviolet rays. / Cm ² irradiation and curing were performed, and a protective layer having a thickness of 310 nm was provided to obtain a conductive laminate of the present invention.

(Example 3)
The composition of the protective layer coating solution was 65 g of “protective layer material B”, 68.5 g of “protective layer material C”, 3.12 g of “additive A”, 6.20 g of “additive B”, and 2378 g of “ethyl acetate”. Except for this, it was produced in the same manner as in Example 2, and a protective layer having a thickness of 310 nm was provided to obtain a conductive laminate of the present invention.

Example 4
The composition of the protective layer coating solution was 78 g of “protective layer material B”, 54.8 g of “protective layer material C”, 3.12 g of “additive A”, 6.20 g of “additive B”, and 2378 g of “ethyl acetate”. Except for this, it was produced in the same manner as in Example 2, and a protective layer having a thickness of 310 nm was provided to obtain a conductive laminate of the present invention.

(Example 5)
The composition of the protective layer coating solution was 119.60 g of “protective layer material B”, 7.58 g of “protective layer material D”, 3.12 g of “additive A”, 6.20 g of “additive B”, 2384 g of “ethyl acetate”. Except for the above, it was prepared in the same manner as in Example 2, and a protective layer having a thickness of 310 nm was provided to obtain a conductive laminate of the present invention.

(Example 6)
The composition of the protective layer coating solution was 117 g of “protective layer material B”, 9.47 g of “protective layer material D”, 3.12 g of “additive A”, 6.20 g of “additive B”, and 2385 g of “ethyl acetate”. Except for this, it was produced in the same manner as in Example 2, and a protective layer having a thickness of 310 nm was provided to obtain a conductive laminate of the present invention.

(Example 7)
The composition of the protective layer coating solution was 104 g of “protective layer material B”, 18.94 g of “protective layer material D”, 3.12 g of “additive A”, 6.20 g of “additive B”, and 2388 g of “ethyl acetate”. Except for this, it was produced in the same manner as in Example 2, and a protective layer having a thickness of 310 nm was provided to obtain a conductive laminate of the present invention.

(Example 8)
The composition of the protective layer coating solution is “Protective layer material B” 123.53 g, “Protective layer material D” 10 g, “Additive A” 3.29 g, “Additive B” 3.27 g, “Additive C” 3. A protective laminate having a thickness of 310 nm was prepared in the same manner as in Example 2 except that 27 g and 2517.65 g of “ethyl acetate” were used to obtain a conductive laminate of the present invention.

Example 9
A conductive laminate of the present invention was obtained in the same manner as in Example 8, except that the additive used was not “Additive C” but “Additive D”, and a protective layer having a thickness of 310 nm was provided.

(Example 10)
A “conductive layer C” was laminated on one side of a substrate using a 125 μm thick polyethylene terephthalate film and Lumirror (registered trademark) U46 (manufactured by Toray Industries, Inc.) as a substrate.

Next, 52.7 g of “protective layer material C”, 1.20 g of “additive A”, 2.38 g of “additive B”, and 2367 g of “ethyl acetate” were mixed and stirred to prepare a protective layer coating solution. This protective layer coating solution was applied on the “conductive layer C” by microgravure coating (gravure wire number 80R, gravure rotation ratio 100%), dried at 120 ° C. for 2 minutes, and then irradiated with ultraviolet rays of 1.2 J / cm ^2. Irradiated and cured, a protective layer having a thickness of 75 nm was provided to obtain a conductive laminate of the present invention.

(Example 11)
The composition of the protective layer coating solution was “protective layer material B” 25 g, “protective layer material C” 26.34 g, “additive A” 1.20 g, “additive B” 2.38 g, “ethyl acetate” 2369 g. Except for this, it was produced in the same manner as in Example 10, and a protective layer having a thickness of 75 nm was provided to obtain a conductive laminate of the present invention.

(Example 12)
The composition of the protective layer coating solution was 45 g of “protective layer material B”, 3.64 g of “protective layer material D”, 1.20 g of “additive A”, 2.38 g of “additive B”, and 2371 g of “ethyl acetate”. Except for this, it was produced in the same manner as in Example 10, and a protective layer having a thickness of 75 nm was provided to obtain a conductive laminate of the present invention.

(Example 13)
A “conductive layer D” was laminated on one side of a substrate using a 125 μm thick polyethylene terephthalate film, Lumirror (registered trademark) U46 (manufactured by Toray Industries, Inc.) as a substrate.

Next, 10.54 g of “Protective layer material C”, 0.24 g of “Additive A”, 0.48 g of “Additive B” and 2414 g of “ethyl acetate” were mixed and stirred to prepare a protective layer coating solution. This protective layer coating solution is applied onto the “conductive layer D” by microgravure coating (gravure wire number 80R, gravure rotation ratio 100%), dried at 120 ° C. for 2 minutes, and then irradiated with ultraviolet rays of 1.2 J / cm ^2. Irradiated and cured, a protective layer having a thickness of 15 nm was provided, and a conductive laminate of the present invention was obtained.

(Example 14)
A conductive layer was prepared in the same manner as in Example 13 except that the conductive layer was “conductive layer E”, and a protective layer having a thickness of 15 nm was provided to obtain a conductive laminate of the present invention.

(Example 15)
A conductive layer was prepared in the same manner as in Example 2 except that the conductive layer was “conductive layer G”, and a protective layer having a thickness of 310 nm was provided to obtain a conductive laminate of the present invention.

(Example 16)
A “conductive layer B” was laminated on one side of a base material using a polyethylene terephthalate film having a thickness of 125 μm and Lumirror (registered trademark) U46 (manufactured by Toray Industries, Inc.) as a base material.

  Next, 2000 g of “protective layer material J”, 24.42 g of “additive F”, and 301.18 g of “ethyl acetate / toluene mixed solvent (mixed mass ratio 1/1)” were prepared as a protective layer coating solution. This protective layer coating solution was applied using a slit die coat having a sus material (shim thickness 50 μm) mounted on the “conductive layer B” and dried at 120 ° C. for 2 minutes to form a 310 nm thick protective layer. It provided and obtained the electrically conductive laminated body of this invention.

(Comparative Example 1)
A 125-μm thick polyethylene terephthalate film, Lumirror (registered trademark) U46 (manufactured by Toray Industries, Inc.) was used as a laminate without providing a conductive layer and a protective layer.

(Comparative Example 2)
A conductive laminate with a 125 μm-thick polyethylene terephthalate film, Lumirror (registered trademark) U46 (manufactured by Toray Industries, Inc.) as a base material, with only “conductive layer B” laminated on one side of the base material and no protective layer provided. It was.

(Comparative Example 3)
A protective layer having a thickness of 310 nm is formed on a conductive layer made of a non-linear structure and made of a spherical conductive component, except that the conductive layer is “conductive layer F”. A conductive laminate was obtained.

(Comparative Example 4)
A protective layer having a thickness of 310 nm is provided on a conductive layer made of a non-linear structure and made of a conductive component of a thin film, except that the conductive layer is “conductive layer H”. A conductive laminate was obtained.

(Comparative Example 5)
The composition of the protective layer coating solution was the same as in Example 2 except that the protective layer material B was 150 g, “Additive A” 3.60 g, “Additive B” 7.15 g, “Ethyl acetate” 2748 g. The protective layer having a thickness of 310 nm was prepared and the conductive laminate of the present invention was obtained.

(Comparative Example 6)
Example 2 except that the composition of the protective layer coating solution was “protective layer material K” 150.3 g, “additive A” 3.60 g, “additive B” 7.15 g, “ethyl acetate” 2747 g It produced similarly and provided the protective layer of thickness 310nm, and obtained the electrically conductive laminated body of this invention.

(Comparative Example 7)
The composition of the protective layer coating solution was 87.5 g of “Protective layer material E”, 3.29 g of “Additive A”, 3.27 g of “Additive B”, 3.27 g of “Additive C”, and 2563 g of “Ethyl acetate”. Except for this, it was prepared in the same manner as in Example 2, and a protective layer having a thickness of 310 nm was provided to obtain a conductive laminate of the present invention.

(Comparative Example 8)
The composition of the protective layer coating solution was “protective layer material D” 100 g, “additive A” 3.29 g, “additive B” 3.27 g, “additive C” 3.27 g, “ethyl acetate” 2551 g. Except for the above, it was produced in the same manner as in Example 2, and a protective layer having a thickness of 310 nm was provided to obtain a conductive laminate of the present invention.

(Comparative Example 9)
Example 2 except that the composition of the protective layer coating solution was “protective layer material F” 146.8 g, “additive A” 3.60 g, “additive B” 7.15 g, “ethyl acetate” 2750 g It produced similarly and provided the protective layer of thickness 310nm, and obtained the electrically conductive laminated body of this invention.

(Comparative Example 10)
The composition of the protective layer coating solution was 123.3 g of “protective layer material C”, 6.63 g of “protective layer material G”, 3.12 g of “additive A”, 6.20 g of “additive B”, 2382 g of “ethyl acetate”. Except for the above, it was prepared in the same manner as in Example 2, and a protective layer having a thickness of 310 nm was provided to obtain a conductive laminate of the present invention.

(Comparative Example 11)
The composition of the protective layer coating solution was 123.3 g of “protective layer material C”, 6.63 g of “protective layer material H”, 3.12 g of “additive A”, 6.20 g of “additive B”, 2382 g of “ethyl acetate”. Except for the above, it was prepared in the same manner as in Example 2, and a protective layer having a thickness of 310 nm was provided to obtain a conductive laminate of the present invention.

(Comparative Example 12)
Example 2 except that the composition of the protective layer coating solution was 123.3 g of “Protective layer material C”, 16.58 g of “Protective layer material I”, 6.2 g of “Additive B”, and 2271 g of “ethyl acetate”. And a protective layer having a thickness of 310 nm was provided to obtain a conductive laminate of the present invention.

(Comparative Example 13)
A “conductive layer B” was laminated on one side of a base material using a polyethylene terephthalate film having a thickness of 125 μm and Lumirror (registered trademark) U46 (manufactured by Toray Industries, Inc.) as a base material.

  Next, by the method disclosed in Example ((2) Preparation of silver nanocolloid coating solution) of JP-A-2001-243841 described in the item (6) Conductive layer F “Silver nanoparticle conductive layer” The obtained silver nanoparticle dispersion was evaporated to dryness to obtain silver nanoparticles.

Next, 130.1 g of “protective layer material B”, 3.32 g of “silver nanoparticles”, 3.12 g of “additive A”, 6.20 g of “additive B”, 2377 g of “ethyl acetate” were mixed and stirred. A protective layer coating solution was prepared. This protective layer coating solution was applied using a slit die coat in which a shim made of sus (material having a thickness of 50 μm) was mounted on the “conductive layer B”, dried at 120 ° C. for 2 minutes, and then irradiated with 1.2 J ultraviolet rays. / Cm ² irradiation and curing were performed, and a protective layer having a thickness of 310 nm was provided to obtain a conductive laminate of the present invention.

(Comparative Example 14)
A protective layer coating solution was prepared in the same manner as in Example 16 except that the composition of the protective layer coating solution was only 2000 g of “protective layer material J”, and a protective layer having a thickness of 310 nm was provided to obtain a conductive laminate of the present invention.

  Even if the components of the protective layer are the same, when the conductive component is a linear structure (Example 2), the line of the printed pattern is compared with the case of the non-linear structure (Comparative Examples 3 and 4). Although there is no difference in the width, the width of the etching line pattern is narrow and the line thickness is suppressed. If the contact angle is not in a specific range even if the protective layer component does not contain a specific element (Comparative Examples 5 to 8, 14), line thickening occurs or the line width has a large standard deviation (σ). Although linearity is bad, after adding an additive (Example 16) or mixing resin (Examples 3-9) instead of individual, a contact angle can be adjusted and line thickness is suppressed. The standard deviation (σ) of the line width can be reduced, and a high-definition and beautiful pattern can be formed while being a thin line. Even if the components of the conductive layer are different, this effect is similarly exhibited if it is a linear structure (Examples 10 to 14). On the other hand, a non-linear structure is included together with the linear structure. In the case (Example 15), the width of the etching line pattern was increased compared to the case (Example 2) in which only the linear structure was formed. Further, when the difference in the maximum absorption wavelength of the photoinitiator contained in the protective layer is in a specific range and the content type of the photoinitiator is large (Example 8), the content type of the photoinitiator is small (implementation) Compared to Example 6) and the case where the difference in maximum absorption wavelength deviates from a specific range (Example 9), the width of the etching line pattern could be further reduced. In addition, depending on the conductive component, the type of protective layer, the average thickness adjustment of the protective layer, etc., the conductivity and optical properties of the conductive laminate can be adjusted, and the properties can be adjusted depending on the usage of the conductive laminate. There are also advantages (Example 1).

  When the conductive layer is not provided, the surface resistance value cannot be measured and the conductive laminate cannot be formed (Comparative Example 1). Further, when a protective layer is not provided (Comparative Example 2) or even if a protective layer is provided, if the composition contains a specific element or ion, even if there is no line thickening at the time of printing, the etching line pattern is lined. In addition to being fattened (Comparative Examples 10 to 13), line thickening may already occur during printing of the remover (Comparative Example 9).

  The present invention relates to a conductive laminate capable of miniaturizing a pattern formed by chemical etching when the conductive laminate is processed and formed into an electrode member used for a touch panel or the like. Furthermore, it is related with the electroconductive laminated body used also for electrode members used, such as liquid crystal displays, organic electroluminescence, electronic papers, and related displays and solar cell modules.

1: Base material 2: Conductive layer 3: Protective layer 4: Conductive surface observed from a direction perpendicular to the laminated surface 5: Single fibrous conductor (an example of a linear structure)
6: Aggregation of fibrous conductors (an example of a linear structure)
7: Nanowire of metal or metal oxide (an example of a linear structure)
8: Needle-like conductor such as whisker (an example of a linear structure)
9: Conductive thin film 10: Contact formed by overlapping fibrous conductors 11: Contact formed by overlapping metal or metal oxide nanowires 12: Contact 13 formed by overlapping needle-like conductors such as whiskers : Conductive layered body 14 in which conductive layer and protective layer are patterned 14: Base material 15 of conductive laminated layer in which conductive layer and protective layer are patterned 15: Patterned conductive layer 16: Patterned protective layer 17: Bonding layer 18 with adhesive or pressure-sensitive adhesive 18: base material on the screen side of the touch panel 19: hard coat layer 20 laminated on the base material on the screen side of the touch panel 20: protective layer surface 21: single linear structure forming an aggregate Body 22: Assembly composed of linear structures 23: Base material 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 (9)

A conductive laminate in which a conductive layer containing a conductive component composed of a linear structure and a protective layer are laminated in this order on at least one surface of the substrate from the substrate side, and the protective layer comprises the following (i) and (ii) A conductive laminate satisfying the requirements.
(I) On the surface of the protective layer, the contact angle of pure water is 80 ° or more, and the contact angle of oleic acid is 13 ° or more.
(Ii) The protective layer is made of a polymer compound that does not contain any of the S element, P element, metal element, metal ion, and N element constituting the functional group. The conductive laminate according to claim 1, wherein the polymer compound has a crosslinked structure. The conductive laminate according to claim 1, wherein the linear structure has a network structure in which the linear structures are in contact with each other at at least one contact. The linear structure is a silver nanowire, and the protective layer does not contain any of an S element, a P element, a metal element, a metal ion, and an N element constituting a functional group. The conductive laminate according to any one of claims 1 to 3, which is a functional methacrylic polymer compound. The linear structure is a carbon nanotube, and the protective layer does not contain any of S element, P element, metal element, metal ion, and N element constituting the functional group. The conductive laminate according to claim 1, which is a methacrylic polymer compound. The conductive laminate according to any one of claims 1 to 5, wherein the protective layer contains two or more photoinitiators having different maximum absorption wavelengths of 20 nm or more. The electroconductive laminated body in any one of Claims 1-6 whose total light transmittance based on JISK7361-1 (1997) when it injects from the protective layer side is 80% or more. The conductive laminate according to claim 1, which is used for a touch panel. A touch panel using the conductive laminate according to claim 8.

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