KR102206686B1 - Laminate, metal mesh and touch panel - Google Patents

Abstract

The present invention is a laminate in which a primer layer (B), a metal layer (C) formed of metal nanoparticles (c) and a metal plating layer (D) are sequentially stacked on a transparent substrate (A), wherein the transparent substrate From the side opposite to the surface on which the primer layer (B), etc. of (A) is formed, a laminate having a lightness (L ^* ) of 55 or less as measured by L ^* a ^* b ^* colorimeter, and a metal mesh and a touch panel using the same to provide. The laminate of the present invention has excellent adhesion between a transparent substrate and a metal plating layer such as copper, and when a mesh-like conductive pattern is formed, the conductive pattern is not easily seen even when viewed from the side opposite to the surface of the conductive pattern. It has excellent transparency.

Description

Laminate, metal mesh and touch panel

The present invention relates to a laminate using a transparent substrate, a metal mesh, and a touch panel.

Capacitive touch panels can be multi-touched and can be used outdoors because they do not malfunction even in sunset light, fallen leaves, and insects, so the use of vending machines, station information panels, and table-type touch panels is increasing.

A capacitive touch panel has a structure in which a specific electrode pattern is formed and a position where a pressure is pressed is specified by detecting a change in a capacitance value between electrodes. One method of this capacitive type is to pattern the electrodes on two sides and convert the weak current at the pressurized position into a voltage with a controller to detect it. Therefore, the conductive film used for a capacitive touch panel is required to have a small surface resistivity and high transparency.

Conventionally, as a transparent conductive film, a film in which an ITO (Indium Tin Oxide) film is formed on the surface has been widely used. Since the ITO film is formed on the surface of the film by a vapor deposition method or a sputtering method, it is a problem that the increase in size is limited in terms of cost. Moreover, since the ITO film has a relatively high volume resistivity, when the display becomes large, there is a limit to the reaction speed, such as a weak current at the pressurized position becoming undetectable.

On the other hand, a polyethylene terephthalate (PET) substrate or a polycarbonate substrate in which a copper layer is formed on one or both sides of the substrate is recently used, and a thin wire with a line width of 5 μm or less is formed by photolithography to achieve both low resistivity and transparency. A transparent conductive film called a metal mesh is proposed (see, for example, Patent Document 1). The PET base material on which this copper layer was formed is a method of forming a copper film by depositing copper on the film, and a copper film can be obtained easily. However, since the temperature at the time of depositing copper is lower than the temperature at the time of depositing ITO, there is a drawback that the penetration of copper into the PET substrate is reduced, and the adhesion between the copper layer and the PET substrate is lowered.

Moreover, as a method of forming a copper layer on the surface of a PET substrate, there is a method of applying an adhesive to the PET substrate and bonding it with a roughened copper foil. In this method, while high adhesion between the PET substrate and the copper foil is obtained, when the roughened copper foil is transferred to the adhesive layer to form a fine wire by photolithography, the PET exposed after the copper is etched. There was a drawback that the transparency of the substrate surface was lowered. Moreover, since there are irregularities in the copper foil, when forming a fine wire having a line width of 5 µm by a photolithography method, there is also a drawback that the fine wire cannot be formed with good precision.

In addition, when a copper layer is formed on the surface of the PET substrate, when viewed from the side opposite to the surface on which the copper layer is formed, even if the copper layer is made of fine wires, it becomes visible due to the color tone of the metallic copper with high brightness. There was a problem in that the image on the display installed with is not well visible.

Japanese Unexamined Patent Publication No. 2013-129183

The problem to be solved by the present invention is that the adhesion between the transparent substrate and the metal plating layer such as copper is very excellent, and when a mesh-like conductive pattern is formed, the conductive pattern is well maintained even when viewed from the side opposite to the surface of the conductive pattern. It is to provide a laminate having excellent transparency because it is not visible, a metal mesh using the same, and a touch panel.

The present inventors, as a result of diligent research in order to solve the above problems, have shown that a primer layer, a metal layer formed of metal nanoparticles, and a metal plating layer are sequentially stacked on a transparent substrate, and the primer of the transparent substrate Laminates in which the lightness (L ^* ) of the value measured by the L ^* a ^* b ^* color system from the opposite side to the side where the layer, etc. is formed is not more than a certain value, has excellent adhesion between the transparent substrate and the metal plating layer, and Thus, even when the conductive pattern is formed, the transparency is excellent, and when the mesh-like conductive pattern is formed, the conductive pattern is not easily visible even when viewed from the side opposite to the surface of the conductive pattern. Completed.

That is, the present invention is a laminate in which a primer layer (B), a metal layer (C) formed of metal nanoparticles (c), and a metal plating layer (D) are sequentially stacked on a transparent substrate (A). From the side opposite to the surface on which the primer layer (B), etc. of the transparent substrate (A) is formed, the lightness (L ^* ) of the value measured by the L ^* a ^* b ^* colorimeter is 55 or less, and It is to provide a used metal mesh and a touch panel.

Compared to the method of forming a copper layer by a conventional vapor deposition method or sputtering method, the laminate of the present invention has very excellent adhesion between the transparent substrate and the metal plating layer, and the transparency of the non-patterned portion after forming the conductive pattern with an etching agent is excellent. great. Further, when a mesh-like conductive pattern is formed using the laminate of the present invention, there is a feature that the mesh-like conductive pattern is difficult to see when viewed from a surface where the conductive pattern is not formed. Therefore, the laminate of the present invention is, for example, a conductive pattern, a conductive film for a touch panel, a metal mesh for a touch panel, an electronic circuit, an organic solar cell, an electronic terminal, an organic EL element, an organic transistor, a flexible printed circuit board, a non-contact It can be suitably used as a wiring member such as RFID for an IC card or an electromagnetic shield. In particular, it is optimal for applications such as touch panels that require transparency.

1 is a cross-sectional view of a laminate of the present invention in which a primer layer, a metal layer, a metal plating layer, and a blackening layer are sequentially formed on one side of a transparent substrate.
Fig. 2 is a cross-sectional view of a laminate of the present invention in which a primer layer, a metal layer, a metal plating layer, and a blackening layer are sequentially formed on one side of a transparent substrate, and a primer layer, a metal layer, and a metal plating layer are formed on the other side.
3 shows a metal layer, a metal plating layer, and a blackening layer of a laminate in which a primer layer, a metal layer, a metal plating layer and a blackening layer are sequentially formed on one side of a transparent substrate, and a primer layer, a metal layer, and a metal plating layer are formed on the other side. It is a top view of a metal mesh of the present invention.
4 is a patterning of a metal layer, a metal plating layer, and a blackening layer of a laminate in which a primer layer, a metal layer, a metal plating layer, and a blackening layer are sequentially formed on one side of a transparent substrate, and a primer layer, a metal layer, and a metal plating layer are formed on the other side. A perspective view of a metal mesh of the present invention.
5 is a metal layer, metal plating layer and blackening of the laminate of the present invention in which a primer layer, a metal layer, a metal plating layer, and a blackening layer are sequentially formed on one side of a transparent substrate, and a primer layer, a metal layer, and a metal plating layer are formed on the other side. It is a cross-sectional view of part A shown in FIG. 3 about the metal mesh of this invention in which the layer was patterned.

The laminate of the present invention is a laminate in which a primer layer (B), a metal layer (C) formed of metal nanoparticles (c) and a metal plating layer (D) are sequentially laminated on a transparent substrate (A), From the side opposite to the surface on which the primer layer (B) or the like of the transparent substrate (A) is formed, the lightness (L ^* ) of the value measured by the L ^* a ^* b ^* colorimeter is 55 or less.

The laminate of the present invention may be a laminate in which a primer layer (B) or the like is sequentially laminated on one side of the transparent substrate (A), and a primer layer (B) or the like is sequentially laminated on both sides of the transparent substrate (A). One laminate may be sufficient.

As the transparent substrate (A), it is preferable that the total light transmittance is 20% or more, more preferably 60% or more, and still more preferably 80% or more.

As a material of the transparent substrate (A), for example, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyimide, cycloolefin polymer, polymethyl methacrylate, polyethylene, polypropylene, polyether ether ketone, poly Vinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyurethane, cellulose nanofibers, glass, quartz, silicone, sapphire, and the like.

In addition, when the laminate of the present invention is used as a metal mesh for a touch panel, as the material of the transparent substrate (A), polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyimide, cycloolefin polymer, polymethyl Methacrylate, polyethylene, polypropylene, and glass are preferred.

As the transparent substrate (A), when the laminate of the present invention is used for applications requiring bendable flexibility, a flexible and flexible transparent substrate is preferable. Specifically, a film or sheet-like transparent substrate is preferable.

When the shape of the transparent substrate (A) is in the form of a film or a sheet, the thickness of the transparent substrate in the form of a film or sheet is usually preferably in the range of 1 to 5,000 µm, more preferably in the range of 1 to 300 µm, The range of 1 to 200 µm is more preferable.

In addition, since the adhesion between the transparent substrate (A) and the primer layer (B) described later can be improved, fine irregularities are formed on the surface of the transparent substrate (A) so as not to lose transparency, and Surface treatment for washing of adhered contamination and introduction of functional groups such as hydroxyl group, carbonyl group, and carboxyl group may be performed. Specifically, plasma discharge treatment such as corona discharge treatment, dry treatment such as ultraviolet treatment, wet treatment using an aqueous solution such as water, acid/alkali, or an organic solvent, etc. may be performed.

The primer layer (B) can be formed by applying a primer to a part or all of the surface of the transparent substrate and removing a solvent such as an aqueous medium or an organic solvent contained in the primer.

As a method of applying the primer to the surface of the transparent substrate, for example, a method such as a gravure method, a coating method, a screen method, a roller method, a rotary method, and a spray method may be mentioned.

The surface of the primer layer (B) is for the purpose of further improving the adhesion with the metal layer (C), for example, a plasma discharge treatment method such as a corona discharge treatment method, a dry treatment method such as an ultraviolet treatment method, water or It is preferable that the surface is treated by a wet treatment method using an acidic or alkaline chemical solution, an organic solvent, or the like.

As a method of removing the solvent contained in the coating layer after applying the primer to the surface of the transparent substrate, for example, a method of drying using a dryer to volatilize the solvent is common. As the drying temperature, it is possible to volatilize the solvent and may be set to a temperature within a range that does not adversely affect the transparent substrate such as thermal deformation.

The film thickness of the primer layer (B) formed using the primer varies depending on the use of the laminate of the present invention, but further improves the adhesion between the transparent substrate (A) and the metal layer (C), In addition, a range in which transparency does not decrease is preferable, and the film thickness of the primer layer is preferably in the range of 10 nm to 30 µm, more preferably in the range of 10 nm to 1 µm, and the range of 10 nm to 500 nm is More preferable.

As the primer resin composition (b) used for formation of the primer layer (B), one containing various resins and solvents can be used.

Examples of the resin include a urethane resin, a vinyl resin, a urethane-vinyl composite resin, an epoxy resin, an imide resin, an amide resin, a melamine resin, a phenol resin, a urea formaldehyde resin, a phenol, etc. as a blocking agent. Isocyanate, polyvinyl alcohol, polyvinylpyrrolidone, etc. are mentioned. Among these resins, it is particularly preferable to use a resin composition containing an aromatic ring from the viewpoint of improving the adhesion between the transparent substrate (A) and the metal layer (C) and not reducing the transparency of the transparent substrate (A). .

As a resin composition containing an aromatic ring, a block isocyanate used by blocking a urethane resin, a vinyl resin, an epoxy resin, an imide resin, a melamine resin, a phenol resin, a phenol, etc. is mentioned. Among them, it is preferable to use a urethane resin and a vinyl resin.

As the urethane resin, it is preferable to have an aromatic ring, and a reaction product of a polyol and a polyisocyanate including an aromatic polyester polyol and a polyol having a hydrophilic group is preferable.

The aromatic ring is a polyol used in the production of the urethane resin, and can be introduced into the urethane resin by using a polyol having an aromatic ring.

Moreover, it is preferable that the said urethane resin has a hydrophilic group because the adhesiveness between the said transparent base material (A) and a metal layer (C) can be improved. Examples of the hydrophilic group include anionic group, cationic group, or nonionic group. Among these, an anionic group or a cationic group is preferable, and an anionic group is more preferable.

Examples of the anionic group include a carboxyl group, a sulfonic acid group, and a carboxylate group, a sulfonate group, etc. in which some or all of them are neutralized with a basic compound or the like. Among these, a carboxyl group and a carboxylate group are preferable from the viewpoint of obtaining a resin having good water dispersibility.

Examples of the basic compound usable for neutralization of the anionic group include organic amines such as ammonia, triethylamine, pyridine, and morpholine; Alkanolamines such as monoethanolamine; And metal base compounds containing sodium, potassium, lithium, calcium, and the like.

Moreover, as said cationic group, a tertiary amino group etc. are mentioned, for example. The tertiary amino group may be partially or entirely neutralized with acetic acid or propionic acid.

Moreover, as said nonionic group, a polyoxyethylene group, a polyoxypropylene group, a polyoxyethylene-polyoxypropylene group, etc. are mentioned, for example.

The content of the hydrophilic groups such as anionic groups and cationic groups in the urethane resin is preferably in the range of 15 to 2,000 mmol/kg from the viewpoint of improving the water dispersion stability of the urethane resin in an aqueous medium.

The hydrophilic group can be introduced into the urethane resin by using a polyol or polyisocyanate having a hydrophilic group in part or all of the polyol or polyisocyanate used in the production of the urethane resin.

As the weight average molecular weight of the urethane resin having a hydrophilic group, from the point of obtaining a primer resin composition (b) capable of forming a film having excellent film forming properties and excellent moist heat resistance, water resistance, and heat resistance. The range of 500,000 is preferable, and the range of 20,000 to 100,000 is more preferable.

As the vinyl resin, a vinyl resin copolymerized with a vinyl monomer having an aromatic ring such as styrene and α-methylstyrene is preferable. When producing the vinyl resin, other various vinyl monomers such as alkyl (meth)acrylate can be copolymerized with the vinyl monomer containing the aromatic ring. Moreover, as a specific example of the said vinyl resin, butadiene-styrene copolymer, acrylic-styrene copolymer, etc. are mentioned.

As the primer resin composition (b), it is preferable to contain 1 to 70 mass% of the resin in the primer, and more preferably to contain 1 to 20 mass%, from the viewpoint of improving coatability.

Moreover, various organic solvents and aqueous media are mentioned as a solvent which can be used for the said primer resin composition (b). Examples of the organic solvent include toluene, ethyl acetate, methyl ethyl ketone, and cyclohexanone, and examples of the aqueous medium include water, an organic solvent miscible with water, and mixtures thereof. have.

Examples of the organic solvent miscible with water include alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, ethyl carbitol, ethyl cellosolve, and butyl cellosolve; Ketone solvents such as acetone and methyl ethyl ketone; Alkylene glycol solvents such as ethylene glycol, diethylene glycol, and propylene glycol; Polyalkylene glycol solvents, such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol; And lactam solvents such as N-methyl-2-pyrrolidone.

Moreover, the said resin may have crosslinkable functional groups, such as an alkoxysilyl group, a silanol group, a hydroxyl group, and an amino group, as needed. The crosslinked structure formed by these crosslinkable functional groups may have already formed a crosslinked structure before the fluid is coated, and after the fluid is coated, for example, a crosslinked structure by heating in a firing step You may form.

The primer resin composition (b) may be appropriately added and used as necessary, as well as a crosslinking agent, a pH adjuster, a film-forming aid, a leveling agent, a thickener, a water repellent, and a defoamer.

Examples of the crosslinking agent include a metal chelate compound, a polyamine compound, an aziridine compound, a metal salt compound, an isocyanate compound, and the like, and a thermal crosslinking agent which reacts at a relatively low temperature of about 25 to 100°C to form a crosslinked structure; A thermal crosslinking agent that reacts at a relatively high temperature of 100°C or higher, such as a melamine compound, an epoxy compound, an oxazoline compound, a carbodiimide compound, and a block isocyanate compound, to form a crosslinked structure; Various photocrosslinking agents can be mentioned.

Although the crosslinking agent is different depending on the type, etc., it is preferable to use in the range of 0.01 to 60 parts by mass based on 100 parts by mass of the total of the resin contained in the primer, since it can form a conductive pattern with excellent adhesion. And, it is more preferable to use it in the range of 0.1-10 mass parts, and it is still more preferable to use it in the range of 0.1-5 mass parts.

In the case of using the crosslinking agent, before forming the metal layer (C) described later, a crosslinked structure may be formed on the primer layer (B), and after forming the metal layer (C) described later, for example, in a firing step, etc. You may form a crosslinked structure in the primer layer (B) by heating.

The metal layer (C) is formed on the primer layer (B), and examples of the metal constituting the metal layer (C) include a transition metal or a compound thereof, and among them, an ionic transition metal is preferable. Examples of the ionic transition metal include copper, silver, gold, nickel, palladium, platinum, and cobalt. Among these ionic transition metals, copper, silver, and gold are preferable from the viewpoint of having a low electrical resistance and obtaining a conductive pattern resistant to corrosion. Further, the metal layer (C) is preferably porous, and in this case, it has voids in the layer.

Moreover, copper, nickel, chromium, cobalt, tin, etc. are mentioned as a metal which comprises the said metal plating layer (D). Among these, copper is preferred from the viewpoint of having a low electrical resistance and obtaining a conductive pattern resistant to corrosion.

In the laminate of the present invention, it is preferable that the metal constituting the metal plating layer (D) is filled in the voids present in the metal layer (C), and near the interface between the transparent substrate (A) and the metal layer (C). It is preferable that the metal constituting the metal plating layer (D) is filled up to the voids in the metal layer (C) present in the metal layer (C) because the adhesion between the metal layer (C) and the metal plating layer (D) is further improved.

In the manufacturing method of the laminate of the present invention, first, a primer layer (B) is formed on the transparent substrate (A), and then, a fluid containing nano-sized metal nanoparticles (c) is applied, A method of forming the metal layer (D) by electrolytic or electroless plating after forming the metal layer (C) by removing the organic solvent or the like contained in the fluid by drying is mentioned. When the metal layer (C) is formed, a fluid containing metal nanoparticles (c) is coated on the primer layer (B) and dried to form a metal layer (C'), and then fired to form the metal layer (C'). It is preferable in that the adhesion with the metal plating layer (D) is improved by removing the organic compound containing the dispersant present in the pores to form the pores and forming the porous metal layer (C).

The shape of the metal nanoparticles (c) used for forming the metal layer (C) is preferably in the form of particles or fibers. In addition, the size of the metal nanoparticles (c) is nano-sized, but specifically, when the shape of the metal nanoparticles (c) is particulate, a fine mesh-like conductive pattern can be formed, and resistance Since the value can be further reduced, the average particle diameter is preferably in the range of 1 to 100 nm, and more preferably in the range of 1 to 50 nm. In addition, the said "average particle diameter" is a volume average value measured by the dynamic light scattering method after diluting the said electroconductive substance with a dispersion good solvent. "Nanotrac UPA-150" manufactured by Microtrac can be used for this measurement.

On the other hand, when the shape of the metal nanoparticles (c) is fibrous, a fine mesh-like conductive pattern can be formed and the resistance value can be further reduced, so the diameter of the fiber is preferably in the range of 5 to 100 nm. And a range of 5 to 50 nm is more preferable. In addition, the length of the fiber is preferably in the range of 0.1 to 100 µm, and more preferably in the range of 0.1 to 30 µm.

The content rate of the metal nanoparticles (c) in the fluid is preferably in the range of 1 to 90 mass%, more preferably in the range of 1 to 60 mass%, and more preferably in the range of 1 to 10 mass%.

As a component to be blended in the fluid, a dispersant or a solvent for dispersing the metal nanoparticles (c) in a solvent, and if necessary, a surfactant, a leveling agent, a viscosity modifier, a film forming aid, an antifoaming agent, a preservative, etc. Can be lifted.

In order to disperse the metal nanoparticles (c) in a solvent, it is preferable to use a dispersant having a low molecular weight or a high molecular weight. Examples of the dispersant include dodecanethiol, 1-octanethiol, triphenylphosphine, dodecylamine, polyethylene glycol, polyvinylpyrrolidone, polyethyleneimine, and polyvinylpyrrolidone; Fatty acids such as myristic acid, octanoic acid, and stearic acid; And polycyclic hydrocarbon compounds having a carboxyl group such as cholic acid, glycylic acid and avintic acid. Among these, a polymer dispersant is preferable in that the adhesion between the metal layer (C) and the metal plating layer (D) described later can be improved by making the metal layer (C) porous. The polymer dispersant is polyethyleneimine , Polyalkyleneimines such as polypropyleneimines, compounds in which polyoxyalkylene is added to the polyalkyleneimines, urethane resins, acrylic resins, compounds containing a phosphoric acid group in the urethane resin or the acrylic resin, and the like. .

As described above, by using a polymer dispersant for the dispersant, compared with the low molecular dispersant, the dispersant in the metal layer (C) is removed to form a porous state, and the pore size can be increased, so that the order of submicron from nano order It is possible to form pores of the size. The metal constituting the metal plating layer (D) described later is easily filled in the voids, and the filled metal becomes an anchor, and the adhesion between the metal layer (C) and the metal plating layer (D) described later can be significantly improved.

The amount of the dispersant required for dispersing the metal nanoparticles (c) is preferably 0.01 to 50 parts by mass, more preferably 0.01 to 10 parts by mass, based on 100 parts by mass of the metal nanoparticles (c).

In addition, in the case of forming the porous metal layer (C) by removing the dispersant by firing for the purpose of further improving the adhesion between the metal layer (C) and the metal plating layer (D) described later, the nano-sized metal powder With respect to 100 parts by mass, 0.1 to 10 parts by mass is preferable, and 0.1 to 5 parts by mass is more preferable.

As the solvent used for the fluid, an aqueous medium or an organic solvent can be used. Examples of the aqueous medium include distilled water, ion-exchanged water, pure water, and ultrapure water. Moreover, as said organic solvent, an alcohol compound, an ether compound, an ester compound, a ketone compound, etc. are mentioned.

As the alcohol, for example, methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, sec-butanol, tert-butanol, heptanol, hexanol, octanol, nonanol, decane Ol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, stearyl alcohol, allyl alcohol, cyclohexanol, terpineol, tapineol, dihydroterpineol, ethylene glycol monomethyl ether , Ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol Monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol monopropyl ether, dipropylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, and the like.

In addition, in addition to the metal powder and solvent, ethylene glycol, diethylene glycol, 1,3-butanediol, isoprene glycol, etc. may be used for the fluid as necessary.

As the surfactant, a general surfactant can be used, for example, di-2-ethylhexylsulfosuccinate, dodecylbenzenesulfonate, alkyldiphenylether disulfonate, alkylnaphthalenesulfonate, hexamethaphosphate And the like.

As the leveling agent, a general leveling agent can be used, and examples thereof include a silicone compound, an acetylenediol compound, and a fluorine compound.

As the viscosity modifier, a general thickener can be used, for example, acrylic polymer or synthetic rubber latex that can be thickened by adjusting it to alkali, urethane resin that can be thickened by associating molecules, hydroxyethylcellulose, carboxymethylcellulose, methylcellulose , Polyvinyl alcohol, water-added castor oil, amide wax, polyethylene oxide, metal soap, dibenzylidene sorbitol, and the like.

As the film-forming aid, general film-forming aids can be used, for example, anionic surfactants (dioctylsulfosuccinate soda salt, etc.), hydrophobic nonionic surfactants (sorbitan monooleate, etc.), polyethers. And modified siloxanes and silicone oils.

As the antifoaming agent, general antifoaming agents can be used, and examples thereof include silicone antifoaming agents, nonionic surfactants, polyethers, higher alcohols, polymeric surfactants, and the like.

As the preservative, general preservatives can be used, for example, isothiazoline preservatives, triazine preservatives, imidazole preservatives, pyridine preservatives, azole preservatives, iodine preservatives, pyrithione preservatives, etc. I can.

The viscosity (value measured using a B-type viscometer at 25°C) of the fluid is preferably in the range of 0.1 to 500,000 mPa·s, and more preferably in the range of 0.5 to 10,000 mPa·s. Further, when the fluid is coated (printed) by a method such as an inkjet printing method or convex plate reverse printing described later, the viscosity is preferably in the range of 5 to 20 mPa·s.

As a method of coating or printing the fluid on the primer layer (B), for example, an inkjet printing method, a reverse printing method, a screen printing method, an offset printing method, a spin coating method, a spray coating method, a bar coating method , A die coating method, a slit coating method, a roll coating method, a dip coating method, a pad printing method, a flexo printing method, and the like.

Among these coating methods, in the case of forming the metal layer (C) patterned in a fine line of about 0.01 to 100 μm, which is required when realizing high density of electronic circuits, etc., it is preferable to use an inkjet printing method or a reverse printing method. Do.

As the inkjet printing method, what is generally called an inkjet printer can be used. Specifically, Konica Minolta EB100, XY100 (manufactured by Konica Minolta IJ Co., Ltd.), Dymatics material printer DMP-3000, Dymatics material printer DMP-2831 (manufactured by Fujifilm Co., Ltd.), and the like.

In addition, as the reverse printing method, a convex plate inversion printing method and a concave plate inversion printing method are known. For example, the fluid is applied to the surface of various blankets, and the non-image part is brought into contact with the protruding plate, and the non-image part is A method of forming the pattern on the surface of the blanket or the like by selectively transferring a corresponding fluid to the surface of the plate, and then transferring the pattern onto the transparent substrate layer (A) (surface) is mentioned. have.

Moreover, about printing of a pattern on a transparent molded article, a pad printing method is known. Ink is mounted on the concave plate, and the ink is uniformly filled in the concave portion by scraping it with a squeegee, and a pad made of silicone rubber or urethane rubber is pressed on the plate on which the ink is mounted, and the pattern is transferred onto the pad, The method of transferring to a transparent molded article is mentioned.

The mass per unit area of the metal layer (C) is preferably in the range of 1 to 30,000 mg/m2, and preferably in the range of 1 to 5,000 mg/m2. The thickness of the metal layer (C) can be adjusted by controlling the treatment time, current density, amount of additives for plating, and the like in the plating treatment step at the time of forming the metal plating layer (C).

When the laminate of the present invention is used as a metal mesh to be described later, the metal layer (C), the metal plating layer (D), and the like are removed by etching to be described later, and a mesh pattern is formed to produce a metal mesh. have. At this time, since the metal layer (C) is easily removed by etching and the transparency of the non-patterned portion (etched portion) can be further improved, the mass per unit area of the metal layer (C) is preferably small, and As an example, the range of 1 to 2,000 mg/m 2 is preferable, and the range of 10 to 1,000 mg/m 2 is more preferable.

The metal plating layer (D) constituting the laminate of the present invention is a highly reliable wiring pattern capable of maintaining good conduction without causing disconnection over a long period of time, for example, when the laminate is used for a conductive pattern or the like It is a layer formed for the purpose of forming.

The metal plating layer (D) is a layer formed on the metal layer (C), but the method of forming it is preferably a method of forming by plating treatment. Examples of this plating treatment include a wet plating method such as an electrolytic plating method and an electroless plating method, a dry plating method such as a sputtering method and a vacuum evaporation method. Further, two or more of these plating methods may be combined to form the metal plating layer (D).

In the electroless plating method, for example, by contacting a metal constituting the metal layer (C) with an electroless plating solution, a metal such as copper contained in the electroless plating solution is deposited to form an electroless plating layer (film ) Is how to form.

Examples of the electroless plating solution include those containing metals such as copper, nickel, chromium, cobalt, and tin, a reducing agent, and a solvent such as an aqueous medium or an organic solvent.

Examples of the reducing agent include dimethylaminoborane, hypophosphorous acid, sodium hypophosphite, dimethylamine borane, hydrazine, formaldehyde, sodium borohydride, phenol, and the like.

Moreover, as the said electroless plating solution, monocarboxylic acid, such as acetic acid and formic acid, as needed; Dicarboxylic acid compounds such as malonic acid, succinic acid, adipic acid, maleic acid and fumaric acid; Hydroxycarboxylic acid compounds such as malic acid, lactic acid, glycolic acid, gluconic acid, and citric acid; Amino acid compounds such as glycine, alanine, iminodiacetic acid, arginine, aspartic acid and glutamic acid; Organic acids such as aminopolycarboxylic acid compounds such as iminodiacetic acid, nitrilotriacetic acid, ethylenediaminediacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, or soluble salts of these organic acids (sodium salt, potassium salt, ammonium salt Etc.), amine compounds such as ethylenediamine, diethylenetriamine, and triethylenetetramine, and the like can be used.

It is preferable to use the said electroless plating solution in the range of 20-98 degreeC.

The electrolytic plating method is, for example, by energizing the metal constituting the metal layer (C) or the surface of the electroless plating layer (film) formed by the electroless treatment in contact with an electrolytic plating solution. Metal such as copper contained in the plating solution is deposited on the surface of the conductive material constituting the metal layer (C) provided on the cathode or the electroless plating layer (film) formed by the electroless treatment, and the electrolytic plating layer (metal film) Is how to form.

Examples of the electrolytic plating solution include those containing sulfides of metals such as copper, nickel, chromium, cobalt, and tin, sulfuric acid, and an aqueous medium. Specifically, those containing copper sulfate, sulfuric acid, and an aqueous medium are mentioned.

It is preferable to use the said electrolytic plating solution in the range of 20-98 degreeC.

In the electrolytic plating treatment method, since a highly toxic substance is not used and workability is good, it is preferable to form a metal plating layer (D) made of copper using an electrolytic plating method.

In addition, as the dry plating process, a sputtering method, a vacuum evaporation method, or the like can be used. In the sputtering method, an inert gas (mainly argon) is introduced in a vacuum, and negative ions are applied to a material forming the metal plating layer (D) to generate glow discharge, and then, the inert gas atoms are ionized, and at high speed. Metal plating layer (D) by violently striking gas ions on the surface of the material for forming the metal plating layer (D), repelling atoms and molecules constituting the material for forming the metal plating layer (D), and vigorously adhering to the surface of the metal layer (C). D) is a method of forming.

As a material for forming the metal plating layer (D) by sputtering, for example, chromium, copper, titanium, silver, platinum, gold, nickel-chromium alloy, stainless steel, copper-zinc alloy, indium tin oxide (ITO) , Silicon dioxide, titanium dioxide, niobium oxide, zinc oxide, and the like.

When plating treatment by the above sputtering method, for example, a magnetron sputtering device or the like can be used.

The thickness of the metal plating layer (D) is preferably in the range of 1 to 50 µm. The thickness of the metal plating layer (D) can be adjusted by controlling the treatment time, current density, amount of additives for plating, and the like in the plating treatment step at the time of forming the metal plating layer (D).

When patterning the metal layer (C) and the metal plating layer (D) of the laminate of the present invention as a metal mesh, the thickness of the metal plating layer (D) is usually preferably in the range of 0.1 to 18 µm, and further etching In order to reduce the subsequent wiring width, the metal plating layer (D) is preferably a thin film, preferably in the range of 0.1 to 5 µm, and more preferably in the range of 0.5 to 3 µm. Further, since the line width of the metal mesh portion can further improve transparency, the range of 0.1 to 10 µm is preferable, and the range of 0.5 to 3 µm is more preferable.

The metal layer (C) and the metal plating layer (D) of the laminate of the present invention are patterned as a metal mesh and used as a touch panel to form the surface on which the metal plating layer (D) or the like of the transparent substrate (A) is formed. In the case of providing the display on the outside (viewing side), in order to improve the visibility of the display, it is preferable to further form a blackening layer (E) on the metal plating layer (D). This is, for example, when the metal plating layer (D) is copper, when a mesh-like wiring is visible due to reflection of external light by copper, by forming a blackening layer (E) on the metal plating layer (D) to make it black. , It is possible to prevent reflection of external light, the mesh-shaped wiring is difficult to see, and the visibility of the display is improved.

In the case of using the laminate of the present invention as a metal mesh, a method for producing a primer resin composition (b) is applied to both sides or one side of the transparent substrate (A), followed by drying to form a primer layer (B). A metal layer (C) is formed by coating and drying a fluid containing metal nanoparticles (c) on the primer layer (B), and using an electrolytic plating method, an electroless plating method, or a combination thereof on the metal layer (C). After the metal plating layer (D) is formed, a method of forming a mesh-like conductive pattern by removing unnecessary portions of the metal layer (C) and the metal plating layer (D) with an etching agent is mentioned. In addition, when the metal plating layer (D) or the like is formed on both sides of the transparent substrate (A) and the metal mesh is used as a touch panel of a display, the visibility of the display is further improved. After forming the blackening layer (E) on the metal plating layer (D) on the surface to be (viewing side), it is preferable to remove unnecessary portions with an etchant to form a mesh-like conductive pattern.

In addition, as a method for producing a metal mesh, a primer resin composition (b) is applied on both sides or one side of the transparent substrate (A), and dried to form a primer layer (B), and metal nanoparticles are formed on the primer layer (B). A metal layer (C) which is a mesh pattern is formed by printing and drying a fluid containing particles (c), and a metal plating layer (D) on the metal layer (C) by an electrolytic plating method, an electroless plating method, or a combination thereof A method of forming a is also mentioned. In addition, when the metal plating layer (D) or the like is formed on both sides of the transparent substrate (A) and the metal mesh is used as a touch panel of a display, the visibility of the display is further improved. It is preferable to form a blackening layer (E) on the said metal plating layer (D) of the surface to become (view side).

In the case of forming a primer layer (B), a metal layer (C), a metal plating layer (D), etc. on both surfaces of the transparent substrate (A), forming a conductive pattern on both surfaces to form a metal mesh, one side as shown in FIG. It is preferable to form a stripe-shaped conductive pattern orthogonal to each other on the surface of and the other surface.

The blackening layer (E) can be formed by a wet method or a dry method.

As the wet method, for example, the method described in Japanese Patent Publication No. 58627916 can be used. Specifically, a method of forming a blackening layer (E) with a blackening treatment liquid consisting of at least one compound selected from the group consisting of palladium, ruthenium, and silver, and a compound containing a halide or a nitrogen atom is mentioned. . In addition, when the metal plating layer (D) is copper, a method of oxidizing the copper surface using hypochlorite, chlorite, etc. to produce black copper oxide, or a method of producing black copper sulfide using an aqueous sulfide solution. By the method, the method of forming the said blackening layer (E) is mentioned.

Moreover, the blackening layer (E) can also be formed by cobalt-copper alloy plating. Further, chromate treatment may be applied thereon as a rust prevention treatment. In addition, the chromate treatment is immersed in a solution containing chromic acid or dichromate as a main component and dried to form a rust preventive film.

Examples of the dry method include a method of forming the blackening layer (E) by a sputtering method or a vapor deposition method. Examples of the compound used in this case include at least one metal compound selected from the group consisting of copper nitride, copper oxide, nickel nitride, and nickel oxide.

As the thickness of the blackening layer (E), the mesh-like wiring is not easily visible, the range of 20 to 500 nm is preferable, and the range of 20 to 100 nm is more preferable.

The laminate of the present invention obtained by the above method can be used as a conductive pattern. In the case of using the laminate of the present invention for a conductive pattern, in order to form the metal layer (C) at a position corresponding to the desired pattern shape to be formed, a fluid containing the metal powder is applied, thereby having a desired pattern. A conductive pattern can be manufactured.

Further, the conductive pattern can be produced by, for example, a photolitho-etching method such as a subtractive method and a semi-additive method, or a method of plating on a printed pattern of the metal layer (C).

The subtractive method is a metal plating layer (D) (in the case where a blackening layer (E) is formed, a blackening layer (E)) constituting the laminate of the present invention prepared in advance, corresponding to a desired pattern shape. A method of forming a desired pattern by forming an etching resist layer of a shape and then dissolving and removing the metal layer (C), the metal plating layer (D), etc. of the portion from which the resist has been removed by a subsequent development treatment with a chemical solution to be. As the chemical liquid, a chemical liquid containing copper chloride, iron chloride, or the like can be used.

In the semi-additive method, the primer layer (B) and the metal layer (C) are formed on both sides or one side of the transparent substrate (A), and the surface of the metal layer (C) has a shape corresponding to a desired pattern. After forming a plating resist layer and then forming a metal plating layer (D) by an electrolytic plating method, an electroless plating method, or a combination thereof, the plating resist layer and the metal layer (C) in contact therewith are dissolved and removed with a chemical solution or the like. And, it is a method of forming a desired pattern by forming the blackening layer (E) as necessary on the formed metal plating layer (D).

In addition, the method of plating on the printing pattern of the metal layer (C) is, on the primer layer (B) formed on both sides or one side of the transparent substrate (A), by an inkjet method, a reverse printing method, etc. The pattern of C) is printed, and the metal plating layer (D) is formed on the surface of the metal layer (C) by an electrolytic plating method, an electroless plating method, or a combination thereof, and the blackening layer (E) is formed thereon as necessary. It is a method of forming a desired pattern by forming.

The laminate of the present invention obtained by the above method has excellent adhesion between the transparent substrate and the metal plating layer compared to the conventional method of forming a copper layer by a vapor deposition method or sputtering method, and the ratio after forming a conductive pattern with an etching agent. The transparency of the pattern part is excellent. Further, when a mesh-like conductive pattern is formed using the laminate of the present invention, there is a feature that the mesh-like conductive pattern is difficult to see when viewed from a surface where the conductive pattern is not formed. Therefore, the laminate of the present invention is, for example, a conductive pattern, a conductive film for a touch panel, a metal mesh for a touch panel, an electronic circuit, an organic solar cell, an electronic terminal, an organic EL element, an organic transistor, a flexible printed circuit board, a non-contact It can be suitably used as a wiring member such as RFID for an IC card or an electromagnetic shield. In particular, it is optimal for applications such as touch panels that require transparency.

Example

Hereinafter, the present invention will be described in detail by examples.

[Preparation of resin composition (R-1)]

830 parts by mass of terephthalic acid, 830 parts by mass of isophthalic acid, 685 parts by mass of 1,6-hexanediol, 604 parts by mass of neopentyl glycol, and dibutyl while introducing nitrogen gas in a reaction vessel equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer. 0.5 parts by mass of tin oxide was poured, and polycondensation reaction was performed at 180 to 230°C for 15 hours until the acid value became 1 or less to obtain a polyester polyol having a hydroxyl value of 55.9 and an acid value of 0.2.

1000 parts by mass of the polyester polyol was dehydrated at 100° C. under reduced pressure, cooled to 80° C., 883 parts by mass of methyl ethyl ketone was added, sufficiently stirred and dissolved, 80 parts by mass of 2,2-dimethylolpropionic acid was added, and then 244 parts by mass of isophorone diisocyanate was added and reacted at 70°C for 8 hours.

After completion of the reaction, the mixture was cooled to 40°C, neutralized by adding 60 parts by mass of triethylamine, and then mixed with 4700 parts by mass of water to obtain a transparent reaction product.

Methyl ethyl ketone was removed from the reaction product under reduced pressure at 40 to 60°C, and then water was mixed to obtain a resin composition (R-1) having a nonvolatile content of 10% by mass and a weight average molecular weight of 50000.

[Preparation of resin composition (R-2)]

To a heat-resistant polymerization apparatus equipped with a stirrer, 90 parts by mass of water, sodium alkyldiphenyl ether disulfonate ("Dowfax 2A-1" manufactured by Dow Chemical) 0.7 parts by mass, 0.15 parts by mass of sodium ethylenediamine 4 acetate, 29 parts by mass of butadiene Parts, 68 parts by mass of styrene, and 3 parts by mass of acrylic acid were injected, and stirring was started. Then, the temperature was raised to 60°C, and when the temperature was stabilized, 0.15 parts by mass of ammonium persulfate was added to initiate polymerization. After proceeding the polymerization at 60° C. for 3 hours, the temperature was raised to 75° C., and the polymerization was further performed for 6 hours. Then, it cooled to 30 degreeC, and pH and solid content were adjusted by adding 25 mass% aqueous ammonia and water, and the resin composition (R-2) of pH 7 and 10% solid content was obtained.

[Preparation of resin composition (R-3)]

Into a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen introduction tube, a thermometer, a dropping funnel for dropping a monomer mixture, and a dropping funnel for dropping a polymerization catalyst, 180 parts by mass of ethyl acetate was placed, and the temperature was raised to 80°C while blowing nitrogen. In a reaction vessel heated to 80°C, under stirring, a vinyl monomer mixture containing 90 parts by mass of methyl methacrylate and 10 parts by mass of n-butyl acrylate, 1 part by mass of azoisobutyronitrile and 20 parts by mass of ethyl acetate are contained. The polymerization initiator solution was added dropwise over 240 minutes while maintaining the temperature in the reaction vessel at 80 ± 1°C from separate dropping funnels to perform polymerization. After completion of the dropwise addition, after stirring at the same temperature for 120 minutes, the temperature in the reaction vessel was cooled to 30°C. Next, ethyl acetate was added so that the non-volatile content became 10 mass %, and the resin composition (R-3) was obtained by filtering with a 200 mesh wire mesh.

[Preparation of fluid (1)]

According to Example 1 described in Japanese Patent Publication No. 4573138, cationic silver nanoparticles composed of flake-like lumps with gray-green metallic luster, which are complexes of silver nanoparticles and organic compounds having cationic groups (amino groups), were obtained. . Thereafter, this silver nanoparticle powder was dispersed in a mixed solvent of 45 parts by mass of ethylene glycol and 55 parts by mass of ion-exchanged water to prepare a fluid 1 having a solid content of 3% by mass.

[Example 1]

The resin composition (R-1) prepared above was prepared on the surface of a transparent substrate ("Lumor 50T-60" manufactured by Toray Corporation, a polyethylene terephthalate film, 50 µm in thickness; hereinafter abbreviated as "PET substrate"). , Using a bar coater, coating was performed so that the thickness after drying became 0.5 µm. Subsequently, a primer layer was formed on the surface of the PET substrate by drying at 80° C. for 5 minutes using a hot air dryer.

Next, on the surface of the primer layer, the fluid (1) obtained above was completely coated on an area of 30 cm in length and 20 cm in width using a bar coater. Subsequently, by firing at 80°C for 5 minutes, a silver layer (mass per unit area: 200 mg/m 2) corresponding to the metal layer (C) was formed.

Next, electroless copper plating was applied to the silver layer corresponding to the metal layer (C) obtained above. It was immersed in an electroless copper plating solution ("OIC Kappa" by Okuno Pharmaceutical Co., Ltd., pH 12.5) for 20 minutes at 55 degreeC, and electroless copper plating was performed. Next, the copper layer obtained by this electroless copper plating was set on the cathode side, the phosphorus-containing copper was set on the anode side, and electrolytic plating was performed for 4 minutes at a current density of 2.5 A/dm ² using an electrolytic plating solution containing copper sulfate. By doing so, a copper plating layer (total thickness of 2 µm) corresponding to the metal plating layer (D) was formed on the surface of the silver layer. As the electrolytic plating solution, copper sulfate 70 g/L, sulfuric acid 200 g/L, chlorine ion 50 mg/L, and additives ("Toprucina SF-M" manufactured by Okuno Pharmaceutical Co., Ltd.) 5 mL/L were used. .

Next, the copper plating layer was immersed in an aqueous solution of 0.1 mol/l of palladium chloride, 100 g/l of hydrochloric acid, 100 g/l of ammonium chloride, and 5 g/l of diethylenetetramine for 3 minutes at 30°C. A blackening layer was formed on the surface of the copper plating layer.

By the above method, a laminate (1) in which each layer was laminated in the order of a transparent substrate (A), a primer layer (B), a metal layer (C), a metal plating layer (D), and a blackening layer (E) was obtained.

[Example 2]

Except having used the resin composition (R-2) instead of the said resin composition (R-1), it was by the method similar to Example 1, and obtained the laminated body (2).

[Example 3]

Except having used the resin composition (R-3) instead of the said resin composition (R-1), it was by the method similar to Example 1, and obtained the laminated body (3).

[Comparative Example 1]

On the surface of the PET substrate, vapor deposition was performed by an electron beam (EB) vapor deposition method so that the thickness of copper became 2 µm to form a copper vapor deposition layer. At that time, the output of the electron beam was 53.5 kW/m with respect to the film formation width.

Next, the copper plating layer was immersed in an aqueous solution of 0.1 mol/l of palladium chloride, 100 g/l of hydrochloric acid, 100 g/l of ammonium chloride, and 5 g/l of diethylenetetramine for 3 minutes at 30°C. A blackening layer was formed on the surface of the copper plating layer.

By the above method, a laminate (R1) in which each layer was laminated in the order of a transparent substrate (A), a metal plating layer (D), and a blackening layer (E) was obtained.

[Comparative Example 2]

A laminate (R2) was obtained by the same method as in Example 1 except that the resin composition (R-1) was not used and the primer layer (B) was not formed.

About the laminates (1) to (3), (R1) and (R2) obtained in Examples 1 to 3 and Comparative Examples 1 to 2, the following measurements and evaluations were performed.

<Adhesion evaluation by measuring peel strength>

Peel strength was measured by a method in accordance with IPC-TM-650 and NUMBER 2.4.9. The lead width used for measurement was 1 mm, and the angle of the peel was 90°. In addition, the peeling strength tends to show a higher value as the thickness of the plating layer increases, but the measurement of the peeling strength in the present invention is measured in a copper film thickness of 15 μm by additionally performing electrolytic copper plating. It was carried out based on the value.

<L ^* a ^* b ^* lightness evaluation by color system>

Using the Konica Minolta Corporation CM3500d, it measured according to JIS Z 8722. The measurement was performed from the side opposite to the surface on which the primer layer or the like of the transparent substrate was formed.

<Measurement of transmittance of transparent substrate>

Using a spectrophotometer ("MPC-3100" manufactured by Shimadzu Corporation), the transmittance of a wavelength of 500 to 550 nm was measured, and the transmittance of the wavelength having the highest transmittance was adopted. In addition, the transmittance|permeability of the transparent base material ("Lumor 50T-60" manufactured by Toray Corporation, 50 micrometers in thickness) used by this invention was 88 %.

<Measurement of transmittance of non-patterned part after etching>

After removing the metal layer (C), the metal plating layer (D), and the blackening layer (E) using an etching agent (a 30% by mass aqueous solution of ferric chloride) from the laminate obtained above, the portion from which each layer was removed (non The transmittance of the pattern part) was measured in the same manner as the transmittance of the transparent substrate. Thereafter, the retention rate was calculated by the following equation from the transmittance of the transparent substrate and the transmittance of the non-patterned portion after etching.

Formula: retention (%) = transmittance of non-patterned portion after etching/transmittance of transparent substrate

<Non-visibility of the metal mesh part>

(Non-visibility of the metal mesh portion of Examples 1 to 3)

As shown in Fig. 2, in the same manner as in each of the Examples, a primer layer, a silver layer, and a copper plating layer were sequentially formed on both sides of the PET substrate, and a blackening layer was formed only on one side of the copper plating layer to obtain a laminate. Then, conductive patterns as shown in Figs. 3, 4, and 5 were produced using an etching agent (30% by mass aqueous solution of ferric chloride). In addition, the size of the conductive pattern was a stripe shape having a wiring width of 5 µm, a pitch of 250 µm, and a thickness of a copper plating layer of 2 µm. In addition, as shown in Fig. 3, the conductive pattern on the upper surface side was made to be orthogonal to the conductive pattern on the lower surface side. It was confirmed visually from the side where the blackening layer was formed of the obtained one, and the non-visibility (something invisible) of the metal mesh portion (the conductive pattern on the upper and lower surfaces) was evaluated according to the following criteria.

A: The wiring pattern was not seen as a whole.

B: The wiring pattern was confirmed thinly as a whole.

C: The wiring pattern was confirmed as a whole.

(Non-visibility of the metal mesh portion of Comparative Example 1)

In the same manner as in Comparative Example 1, a copper vapor deposition layer was formed on both surfaces of the PET substrate, and a blackening layer was formed only on one surface of the copper vapor deposition layer to obtain a laminate. After that, a conductive pattern was formed in the same manner as in Examples 1 to 3, and the non-visibility of the metal mesh portion was evaluated.

(Non-visibility of the metal mesh portion of Comparative Example 2)

Except that the primer layer was not formed, a conductive pattern was formed in the same manner as in Examples 1 to 3, and the non-visibility of the metal mesh portion was evaluated.

Table 1 shows the summary of the measurement and evaluation results obtained above.

It was confirmed that the laminates (1) to (3) obtained in Examples 1 to 3, which are the laminates of the present invention, have sufficiently high peel strength in practical use. Further, it was confirmed that the retention rate of the transmittance of the non-patterned portion after etching was high, and the etching treatment had high transparency. In addition, the lightness measured by the L ^* a ^* b ^* colorimeter from the side opposite to the surface on which the metal plating layer of the transparent substrate was formed, is as low as 55 or less and is black, and the pattern when the laminate of the present invention is a metal mesh. Was not well seen, and it was confirmed that it was sufficiently usable as a touch panel.

On the other hand, it was confirmed that the laminates (R1) and (R2) obtained in Comparative Examples 1 and 2 had low peel strength and were not at a practical level. In addition, the layered product (R1) obtained in Comparative Example 1, when used as a metal mesh in which a copper evaporation layer was formed, is a color tone of metallic copper with high brightness, and the pattern is easily visible, and it is used as a touch panel. It could be confirmed that it was inappropriate.

1: blackening layer
2: metal plating layer
3: metal layer
4: primer layer
5: transparent substrate
6: Metal mesh (touch panel sensor)
7: pattern on the top surface
8: pattern on the bottom surface

Claims (11)

As a laminate in which a primer layer (B), a metal layer (C) formed of metal nanoparticles (c), a metal plating layer (D), and a blackening layer (E) are sequentially stacked on the transparent substrate (A). , From the side opposite to the surface on which the primer layer (B) of the transparent substrate (A) is formed, the brightness (L ^* ) of the value measured by the L ^* a ^* b ^* colorimeter is 55 or less,
The layered product, wherein the blackening layer (E) is formed by a blackening treatment liquid comprising at least one compound selected from the group consisting of palladium, ruthenium, and silver, and a compound containing a halide or a nitrogen atom. The method of claim 1,
On the transparent substrate (A) on the side opposite to the surface on which the primer layer (B) of the laminate is formed, a primer layer (B), a metal layer (C) formed of metal nanoparticles (c), and a metal A laminate in which a plating layer (D) and a blackening layer (E) are sequentially laminated. delete delete The method of claim 1,
The transparent substrate (A) is selected from the group consisting of polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyimide, cycloolefin polymer, polymethyl methacrylate, polyethylene, polypropylene, and glass. The method of claim 1,
The layered product wherein the primer layer (B) is formed of a resin having an aromatic ring. The method of claim 1,
The metal nanoparticle (c) is at least one type selected from the group consisting of silver, copper, palladium, gold, nickel, platinum, and cobalt. The method of claim 1,
A laminate having a mass per unit area of the metal layer (C) in the range of 1 to 1,000 mg/m 2. The method of claim 1,
The laminated body in which the said metal plating layer (D) is copper. Metal, characterized in that the metal layer (C), the metal plating layer (D), and the blackening layer (E) of the laminate according to any one of claims 1, 2 and 5 to 9 are patterned. Messi. A touch panel comprising the metal mesh according to claim 10.

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