TW201810298A - Laminate, metal mesh, and touch panel - Google Patents

Abstract

The present invention provides the following: a laminate in which a primer layer (B), a metal layer (C) made of metal nanoparticles (c), and a metal plating layer (D) are successively layered onto a transparent substrate (A), the laminate having a brightness (L*) of 55 or less as measured according to an L*a*b* color system from the side of the transparent substrate (A) opposite the surface where the primer layer (B) and the like are formed; and a metal mesh and a touch panel using the laminate. This laminate has excellent adhesion between the transparent substrate and the metal plating layer made of copper or the like, and when forming a mesh conductive pattern, the conductive pattern is difficult to see even when viewing the conductive pattern from the side opposite the surface where the conductive pattern is formed, and the laminate thereby exhibits excellent transparency.

Description

Laminate, metal grid and touch panel

The present invention relates to a laminated body using a transparent substrate, a metal grid, and a touch panel.

The capacitive touch panel can be multi-touched, and it can be used outdoors without making mistakes in sunsets, leaves, insects, etc. Therefore, it is used in vending machines, station guidance panels, and table-type touch panels. The situation has increased.

The capacitance type touch panel has a structure in which a specific electrode pattern is formed and a change in the capacitance value between the electrodes is detected to determine a pressed position. One method of this electrostatic capacitance type is to pattern a two-face electrode, and a controller converts a weak current at a pressing position into a voltage to perform detection. Therefore, the conductive film used in the capacitive touch panel must have a small surface resistivity and high transparency.

Currently, a thin film in which an ITO (Indium Tin Oxide) film is formed on a surface is widely used as a transparent conductive thin film. The ITO film is formed on the surface of the thin film by a vapor deposition method or a sputtering method. Therefore, it is a problem that the increase in size is limited by cost. In addition, since the ITO film system has a high volume resistivity, if the display becomes large, it becomes impossible to detect a weak current or the like at the pressing position, which limits the response speed.

On the other hand, in recent years, it has been proposed to use a polyethylene terephthalate (PET) substrate or a polycarbonate substrate in which a copper layer is formed on one or both sides of a substrate to form a line by a photolithography method. A thin conductive wire with a width of 5 μm or less is a transparent conductive film called a metal mesh that has both low resistivity and transparency (for example, refer to Patent Document 1). The PET substrate on which this copper layer is formed is a method of forming a copper film by vapor-depositing copper on a thin film, and a copper film can be easily obtained. However, since the temperature during the vapor deposition of copper is lower than the temperature in the case of vapor-depositing ITO, the amount of copper trapped in the PET substrate is reduced, and there are disadvantages that the adhesion between the copper layer and the PET substrate is lowered.

In addition, 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 the copper foil to a roughening treatment. This method can obtain high adhesion between the PET substrate and the copper foil. However, the unevenness of the roughened copper foil is transferred to the adhesive layer, and a thin line is formed by the photolithography method. In addition, there is a disadvantage that the transparency of the surface of the PET substrate, which is exposed after copper is etched, is reduced. In addition, the copper foil has irregularities, so that when a fine line having a line width of 5 μm is formed by a photolithography method, there is a disadvantage that the fine line cannot be formed with high accuracy.

In addition, when a copper layer is formed on the surface of the PET base material, and when viewed from the side opposite to the surface on which the copper layer is formed, even if the copper layer is made into a thin wire, high-brightness metallic copper may be used. The color tone is seen by the eyes, and there is a problem that it becomes difficult to see an image of a display provided with a touch panel.

Prior art literature Patent literature

Patent Document 1 Japanese Patent Application Publication No. 2013-129183

The problem to be solved by the present invention is to provide a laminated body, a metal grid using the laminated body, and a touch panel. The laminated system has excellent adhesion between a transparent substrate and a metal layer such as copper plating. In the case of a grid-shaped conductive pattern, even when the conductive pattern is viewed from the side opposite to the formation surface of the conductive pattern, it is difficult to see the conductive pattern and it is excellent in transparency.

The present inventors made intensive research in order to solve the above-mentioned problems, and found that the present invention was completed as follows: A laminated body is formed by sequentially laminating a primer layer and a metal nanoparticle on a transparent substrate. The metal layer and the metal plating layer have a constant brightness (L *) of a value measured in the L * a * b * color system from the side of the transparent substrate opposite to the surface on which the primer layer and the like are formed. A multilayer body having a value of less than or equal to is excellent in adhesion between a transparent substrate and a metal-plated layer, and is excellent in transparency even when a conductive pattern is formed using an etchant, even when a grid-shaped conductive layer is formed. In the case of a conductive pattern, even when viewed from the side opposite to the formation surface of the conductive pattern, it is difficult to see the conductive pattern and it is excellent in transparency.

That is, the present invention is an invention of a laminated body, and a metal grid and a touch panel using the laminated body. The laminated system sequentially has a primer layer (B) and a metal layer on a transparent substrate (A). Rice particle (c) The formed metal layer (C) and the metal-plated layer (D) are characterized in that L * a * is from the side of the transparent substrate (A) opposite to the surface on which the primer layer (B) and the like are formed. The brightness (L *) of the value measured by the b * color system is 55 or less.

Compared with the conventional method for forming a copper layer by a vapor deposition method or a sputtering method, the laminated substrate of the present invention has excellent adhesion between the transparent substrate and the metal plating layer, and the non-pattern after the conductive pattern is formed by an etchant. The part is excellent in transparency. When the grid-shaped conductive pattern is formed using the laminated body of the present invention, the grid-shaped conductive pattern is difficult to see when viewed from a surface on which the aforementioned conductive pattern is not formed. Therefore, the laminated body of the present invention can be suitably used as, for example, a conductive pattern, a conductive film for a touch panel, a metal grid for a touch panel, an electronic circuit, an organic solar cell, an electronic terminal, an organic EL Wiring components such as devices, organic transistors, flexible printed boards, RFIDs such as non-contact IC cards, and electromagnetic wave shields. In particular, it is most suitable for applications such as a touch panel that requires transparency.

1‧‧‧Blackened layer

2‧‧‧ metal plating

3‧‧‧ metal layer

4‧‧‧ primer layer

5‧‧‧ transparent substrate

6‧‧‧ metal grid (touch panel sensor)

7‧‧‧ Top pattern

8‧‧‧ bottom pattern

1 is a cross-sectional view of a laminated body of the present invention in which a primer layer, a metal layer, a metal plating layer, and a blackened layer are sequentially formed on one side of a transparent substrate.

2 is a cross-section of a laminated body of the present invention in which a primer layer, a metal layer, a metallized layer, and a blackened layer are sequentially formed on one side of a transparent substrate, and a primer layer, a metal layer, and a metallized layer are formed on the other side. Illustration.

Figure 3 shows that a primer layer, a metal layer, a metallized layer, and a blackened layer are sequentially formed on one side of a transparent substrate, and a primer layer and a metal layer are formed on the other side. A top view of the metal grid of the present invention in which the metal layer, the metal plating layer, and the blackening layer of the laminated body of the metal plating layer are patterned.

FIG. 4 shows that a primer layer, a metal layer, a metallized layer, and a blackened layer are sequentially formed on one side of a transparent substrate, and a metal layer of a laminate of the primer, metal, and metallized layers is formed on the other side. A perspective view of the metal grid of the present invention with the metallization layer and the blackening layer patterned.

FIG. 5 is a laminated body 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. FIG. 3 is a cross-sectional view of the metal grid of the present invention in which the metal layer, the metal plating layer, and the blackening layer are patterned.

A form for implementing the invention

The multilayer system of the present invention sequentially stacks a primer layer (B), a metal layer (C) formed of metal nano particles (c), and a metallized layer (D) on a transparent substrate (A) in this order. The brightness (L *) of the value measured in the L * a * b * color system from the surface of the transparent substrate (A) opposite to the surface on which the primer layer (B) and the like were formed was 55. the following.

The laminated body of the present invention may be a laminated body such as a primer layer (B) sequentially laminated on one side of the transparent substrate (A), or may be a sequentially laminated primer on both sides of the transparent substrate (A). Layer (B) and the like.

As said transparent base material (A), those with a total light transmittance of 20% or more are preferable, 60% or more are more preferable, and 80% or more are still more preferable.

Examples of the material of the transparent substrate (A) include polyethylene terephthalate, polyethylene terephthalate, polycarbonate, polyimide, cyclic olefin polymer, and polymethylmethacrylate. Methyl acrylate, polyethylene, polypropylene, polyetheretherketone, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyurethane, cellulose nanofiber, glass, quartz, silicon, sapphire Wait.

When the laminated body of the present invention is used as a metal grid for a touch panel, as the material of the transparent substrate (A), polyethylene terephthalate and polyethylene terephthalate are preferred. Ethylene formate, polycarbonate, polyimide, cycloolefin polymer, polymethyl methacrylate, polyethylene, polypropylene, glass.

As the said transparent base material (A), when the laminated system of this invention is used for the use which requires bendable flexibility, it is preferable that it is a soft and flexible transparent base material. Specifically, a film or sheet-like transparent substrate is preferred.

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

In addition, from the viewpoint of improving the adhesion between the transparent substrate (A) and a primer layer (B) described later, it is possible to form a fine degree on the surface of the transparent substrate (A) without loss of transparency. Unevenness; cleaning of contamination attached to the surface; surface treatment for introducing functional groups such as hydroxyl, carbonyl, and carboxyl groups, and the like. Specifically, a plasma discharge treatment such as a corona discharge treatment, a dry treatment such as an ultraviolet treatment, a wet treatment using an aqueous solution such as water, an acid / base, or an organic solvent, and the like can 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 solvents such as an aqueous medium and an organic solvent contained in the primer.

Examples of the method for applying the primer to the surface of the transparent substrate include methods such as a gravure method, a coating method, a screen method, a roll method, a rotation method, and a spray method.

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 or an ultraviolet treatment method is preferred. Dry treatment; wet treatment using water, acidic or alkaline chemicals, organic solvents, etc. for surface treatment.

As a method of removing the solvent contained in the coating layer after the primer is applied to the surface of a transparent substrate, for example, a method of drying the solvent using a dryer and volatilizing the solvent is generally used. The drying temperature may be set to a temperature within a range in which the solvent can be volatilized without adversely affecting the transparent substrate, such as thermal deformation.

The film thickness of the primer layer (B) formed by using the aforementioned primer varies depending on the use of the laminated body of the present invention, but it is preferable to further improve the thickness of the transparent substrate (A) and the metallic layer (C). The thickness of the primer layer is preferably in a range of 10 nm to 30 μm, more preferably in a range of 10 nm to 1 μm, and even more preferably in a range of 10 nm to 500 nm. In the range.

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

Examples of the resin include a urethane resin, an ethylene resin, a urethane-ethylene composite resin, an epoxy resin, a polyimide resin, a polyimide resin, a melamine resin, a phenol resin, Urea formaldehyde resin, blocked isocyanate using phenol or the like as a blocking agent, polyvinyl alcohol, polyvinylpyrrolidone, and the like. Among these resins, in particular, it is preferable to use an aromatic ring-containing resin in view of improving the adhesion between the transparent substrate (A) and the metal layer (C) without reducing the transparency of the transparent substrate (A). Resin composition.

Examples of the aromatic ring-containing resin composition include urethane resins, vinyl resins, epoxy resins, polyimide resins, melamine resins, phenol resins, and blocked isocyanates used for blocking phenol and the like. . Among these, a urethane resin and a vinyl resin are preferably used.

The urethane is preferably one having an aromatic ring, and is preferably a reaction product of a polyol and a polyisocyanate containing an aromatic polyester polyol and a polyol having a hydrophilic group.

The aromatic ring can be introduced into the urethane resin by using a polyol having an aromatic ring as a polyol for producing the urethane resin.

Moreover, it is preferable that the said urethane resin has a hydrophilic group, since the adhesiveness of the said transparent base material (A) and the metal layer (C) can be improved. Examples of the hydrophilic group include an anionic group, a cationic group, and a 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 carboxyl group partially or entirely neutralized with a basic compound or the like. Ester group, sulfonate group, etc. Among these, a carboxyl group and a carboxylic acid ester group are preferable because a resin having good water dispersibility can be obtained.

Examples of the basic compound that can be used to neutralize the anionic group include organic amines such as ammonia, triethylamine, pyridine, and morpholine; alkanolamines such as monoethanolamine; and compounds containing sodium, potassium, lithium, and calcium. Metal base compounds and so on.

Examples of the cationic group include a tertiary amine group. The aforementioned tertiary amine group may be a part or all of which is neutralized by acetic acid, propionic acid, or the like.

Examples of the nonionic group include a polyoxyethylene group, a polyoxypropylene group, and a polyoxyethylene-polyoxypropylene group.

From the viewpoint of better water dispersion stability of the urethane resin in the aqueous medium, the content of the hydrophilic group such as the anionic group and the cationic group in the urethane resin is preferably 15 to 2,000. Within the range of mmol / kg.

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

The weight of the urethane resin having the above-mentioned hydrophilic group from the viewpoint of the primer resin composition (b) capable of obtaining a film excellent in film-forming properties and capable of forming a film having excellent moisture and heat resistance, water resistance, and heat resistance. The average molecular weight is preferably in the range of 5,000 to 500,000, and more preferably in the range of 20,000 to 100,000.

The ethylene resin is preferably an ethylene resin in which an ethylene monomer having an aromatic ring such as styrene or α-methylstyrene is copolymerized. When producing the ethylene resin, various other vinyl monomers such as alkyl (meth) acrylate can be copolymerized with the aromatic ring-containing ethylene monomer. Specific examples of the ethylene resin include a butadiene-styrene copolymer, an acrylic-styrene copolymer, and the like.

From the viewpoint of improving the coatability, as the primer resin composition (b), it is preferred that the primer contains 1 to 70% by mass of the resin, and more preferably contains 1 to 20% by mass.

Examples of the solvent that can be used for the primer resin composition (b) include various organic solvents and aqueous media. Examples of the organic solvent include toluene, ethyl acetate, methyl ethyl ketone, and cyclohexanone. Examples of the aqueous medium include water, an organic solvent mixed with water, and mixtures thereof. .

Examples of the organic solvent mixed with water include alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, ethylcarbitol, ethyl cyrus, butyl cyrus, and the like; , Ketones such as methyl ethyl ketone; alkylene glycol solvents such as ethylene glycol, diethylene glycol, and propylene glycol; polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polybutylene glycol Alcohol solvents; L-amine solvents such as N-methyl-2-pyrrolidone and the like.

The resin may have a crosslinkable functional group such as an alkoxysilyl group, a silanol group, a hydroxyl group, or an amine group, if necessary. The crosslinked structure formed by using these crosslinkable functional groups may be a crosslinked structure formed before the fluid is applied, or may be formed after the fluid is applied, for example, by heating in a firing step or the like. Crosslinked structure.

In the primer resin composition (b), known additives such as a pH adjusting agent including a cross-linking agent, a film-forming aid, a leveling agent, a thickener, a water-repellent agent, and a defoaming agent may be appropriately added as necessary. Pharmacy.

Examples of the cross-linking agent include metal chelate compounds, polyamine compounds, aziridine compounds, metal salt compounds, isocyanate compounds, and the like. The reaction is performed at a low temperature of about 25 to 100 ° C. A thermal crosslinking agent that forms a crosslinked structure; a melamine-based compound, an epoxy-based compound, Thermal crosslinking agents, such as oxazoline compounds, carbodiimide compounds, and blocked isocyanate compounds, which react at a high temperature of 100 ° C or higher to form a crosslinked structure; various photocrosslinking agents.

Although the cross-linking agent varies depending on the type and the like, from the viewpoint of being capable of forming a conductive pattern having excellent adhesion, it is preferably 0.01 to 100 parts by mass of the total resin contained in the primer. It is used in the range of 60 parts by mass, more preferably in the range of 0.1 to 10 parts by mass, and even more preferably in the range of 0.1 to 5 parts by mass.

In the case of using the aforementioned crosslinking agent, a crosslinked structure may be formed in the primer layer (B) before forming the metal layer (C) described later, or after forming the metal layer (C) described later, for example, by using A crosslinked structure is formed in the primer layer (B) by heating such as a firing step.

The metal layer (C) is formed on the primer layer (B). Examples of the metal constituting the metal layer (C) include a transition metal or a compound thereof, and an ionic transition metal is preferred. 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 preferred because a conductive pattern having low resistance and corrosion resistance can be obtained. Also, before The metal layer (C) is preferably porous. In this case, the layer has voids.

Examples of the metal constituting the metal plating layer (D) include copper, nickel, chromium, cobalt, and tin. Among these, copper is preferable because a conductive pattern having low resistance and corrosion resistance can be obtained.

In the laminated body of the present invention, it is preferable that the metal constituting the metal plating layer (D) is filled in the gaps existing in the metal layer (C), and the metal constituting the metal plating layer (D) is filled in the space The void in the metal layer (C) existing near the interface between the transparent substrate (A) and the metal layer (C) is a closer contact force between the metal layer (C) and the metal plating layer (D). Lift and therefore better.

As a method for producing the laminated body of the present invention, the following method may be mentioned: first, a primer layer (B) is formed on a transparent substrate (A), and then, metal nano particles (c ) Fluid, the organic solvent and the like contained in the fluid are removed by drying to form a metal layer (C), and then the aforementioned metal plating layer (D) is formed by electrolytic or electroless plating. When this metal layer (C) is formed, a fluid containing metal nano particles (c) is coated on the primer layer (B), and dried to form a metal layer (C '), and then fired to The dispersant-containing organic compound existing in the metal layer (C ') is removed to form a void to form a porous metal layer (C), thereby improving the adhesion with the metal plating layer (D). It is better.

The metal nanoparticle (c) used to form the metal layer (C) is preferably particulate or fibrous. In addition, when the size of the metal nanoparticle (c) is a nano size, specifically, the metal When the shape of the nanoparticle (c) is particulate, the average particle diameter is preferably in the range of 1 to 100 nm in order to form a fine mesh conductive pattern and further reduce the resistance value. In the range of 1 ~ 50nm. The "average particle diameter" refers to a volume average value measured by diluting the conductive substance with a solvent having a high dispersing power and measuring it by a dynamic light scattering method. For this measurement, "Nanotrack UPA-150" manufactured by Microtrac can be used.

On the other hand, when the shape of the metal nanoparticle (c) is fibrous, in order to form a fine grid-like conductive pattern and further reduce the resistance value, the diameter of the fiber is preferably 5 to In the range of 100 nm, more preferably in the range of 5 to 50 nm. 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 of the metal nanoparticle (c) in the fluid is preferably in a range of 1 to 90% by mass, more preferably in a range of 1 to 60% by mass, and even more preferably in a range of 1 to 10% by mass. %In the range.

Examples of the components that can be blended in the fluid include a dispersant and a solvent for dispersing the metal nanoparticle (c) in a solvent, and a surfactant, a leveling agent, and the like described later as needed, Viscosity adjuster, film-forming aid, defoamer, preservative, etc.

In order to disperse the metal nano particles (c) in a solvent, it is preferable to use a low molecular weight or high molecular weight dispersant. Examples of the dispersant include dodecanethiol, 1-octanethiol, triphenylphosphine, dodecylamine, polyethylene glycol, polyvinylpyrrolidone, and polyethylenimine. , Polyvinylpyrrolidone; myristic acid, caprylic acid, stearic acid And other fatty acids; polycyclic hydrocarbon compounds having a carboxyl group, such as bile acid, glycyrrhizic acid, and rosin acid. Among these, polymer dispersion is preferred because the metal layer (C) can be made porous to improve the adhesion between the metal layer (C) and a metal plating layer (D) described later. Examples of the polymer dispersant include polyalkyleneimines such as polyethylenimine and polypropylimine; and polyalkylene oxides added to the polyalkyleneimines. Compounds; urethane resins; acrylic resins; the aforementioned urethane resins or the aforementioned acrylic resins contain a phosphate group-containing compound, and the like.

As described above, by using a polymer dispersant as the dispersant as compared with a low-molecular dispersant, the dispersant in the metal layer (C) can be removed and made porous, and the void size can be increased. Voids ranging in size from nanometers to submicrons are formed. It becomes easy to fill the gap with the metal constituting the metallized layer (D) described later, and the filled metal becomes an anchor, which can significantly improve the adhesion between the metal layer (C) and the metallized layer (D) described later.

The amount of the dispersant required to disperse the metal nano particles (c) is preferably 0.01 to 50 parts by mass, and more preferably 0.01 to 10 parts by mass relative to 100 parts by mass of the metal nano particles (c). .

In addition, for the purpose of further improving the adhesion between the metal layer (C) and the metal plating layer (D) described later, the dispersant is removed by firing to form the porous metal layer (C). Below, it is preferably 0.1 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, with respect to 100 parts by mass of the metal powder of the aforementioned nanometer size.

As the solvent used in the fluid, an aqueous medium and an organic solvent can be used. Examples of the aqueous medium include steaming. Distilled water, ion-exchanged water, pure water, ultrapure water, etc. Examples of the organic solvent include alcohol compounds, ether compounds, ester compounds, and ketone compounds.

Examples of the alcohol include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, secondary butanol, tertiary butanol, pentanol, hexanol, octanol, and nonanol , Decanol, undecanol, dodecanol, tridecanol, myristyl alcohol, pentadecanol, stearyl alcohol, allyl alcohol, cyclohexanol, terpineol, menenyl alcohol, diol Hydrogenenol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol Alcohol 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 one Butyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, and the like.

In addition to the above-mentioned metal powder and solvent, the fluid can be used as needed: ethylene glycol, diethylene glycol, 1,3-butanediol, isoprenediol, and the like.

As the surfactant, a general surfactant can be used, and examples thereof include di-2-ethylhexylsulfosuccinate, dodecylbenzenesulfonate, and alkyldiphenyl ether disulfonic acid. Salt, alkylnaphthalene sulfonate, hexametaphosphate, etc.

As said leveling agent, a general leveling agent can be used, For example, a silicone type compound, an acetylene glycol type compound, a fluorine type compound, etc. are mentioned.

As the viscosity modifier, a general thickener can be used, and examples thereof include an acrylic polymer that can be thickened by adjusting to alkalinity, a synthetic rubber latex, and an amine group that can be thickened by molecular association. Formate resins, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, polyvinyl alcohol, hydrogenated castor oil, ammonium wax, oxidized polyethylene, metal soap, dibenzylidene sorbitol, and the like.

As the film-forming aid, a general film-forming aid can be used, and examples thereof include anionic surfactants (such as sodium dioctylsulfosuccinate), and hydrophobic nonionic surfactants (Yamanashi Alkyd monooleate, etc.), polyether-modified silicone, silicone oil, etc.

As the antifoaming agent, a general antifoaming agent can be used, and examples thereof include silicone-based antifoaming agents, nonionic surfactants, polyethers, higher alcohols, and polymer-based surfactants.

As the preservative, a general preservative can be used, and examples thereof include an isothiazoline preservative, Preservatives, imidazole preservatives, pyridine preservatives, azole preservatives, iodine preservatives, pyrithione preservatives, etc.

The viscosity of the fluid (value measured using a B-type viscometer at 25 ° C) 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. In addition, when the fluid is applied (printed) by a method such as an inkjet printing method or letterpress reverse printing described later, the viscosity is preferably in a range of 5 to 20 mPa · s.

Examples of the method for coating or printing the fluid on the primer layer (B) include an inkjet printing method, a reverse printing method, a screen printing method, a lithographic method, a spin coating method, and 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 flexographic printing method, and the like.

Among these coating methods, when forming the metal layer (C) which is patterned in a thin line shape of about 0.01 to 100 μm required to achieve high density of electronic circuits and the like, inkjet printing is preferably used. Method, reverse printing method.

As the inkjet printing method, what is generally called an inkjet printer can be used. Specific examples include Konika Minolta EB100, XY100 (produced by Konika Minolta IJ Co., Ltd.); Dimatix‧Material Printer DMP-3000, and Dimatix‧Material Printer DMP-2831 (manufactured by Fujifilm Corporation).

In addition, as a reverse printing method, a letterpress reverse printing method and a gravure reverse printing method are known, and examples thereof include a method in which the above-mentioned fluid is applied to the surface of various blankets to make it non-inking. The protruding plate contacting the portion causes the fluid corresponding to the non-inking portion to be selectively transferred to the surface of the plate, thereby forming the pattern on the surface of the coating or the like, and then transferring the pattern to the transparent substrate. Above layer (A) (surface).

In addition, a pad printing method is known for printing a pattern on a transparent molded product. The method can be mentioned as follows: the ink is placed on the intaglio plate and scraped with a scraper, so that the ink is uniformly filled in the concave portion, and the plate on which the ink is placed is pressed against silicone rubber, urethane rubber A mat, the pattern is transferred to a mat, and it is transferred to a transparent molded article.

The mass per unit area of the metal layer (C) is preferably in the range of 1 ~ 30,000mg / m ^2, preferably in the range 1 ~ 5,000mg / m ² in. The thickness of the metal layer (C) can be adjusted by controlling the processing time, the current density, the amount of plating additives, and the like in the plating processing step when the metal plating layer (C) is formed.

When the laminated body 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 to form a grid-like pattern to produce a metal. Grid method. At this time, since it is easy to remove the metal layer (C) by etching, and the transparency of the non-patterned portion (etched portion) can be further improved, the smaller the mass per unit area of the metal layer (C), the better, specifically, it is preferably in the range of 1 ~ 2,000mg / m ^2, and more preferably in the range of 10 ~ 1,000mg / m ² in.

The metal-plated layer (D) constituting the laminated body of the present invention is formed, for example, when the laminated body is used for a conductive pattern or the like to form a conductive layer that does not cause disconnection or the like over a long period of time and maintains good electrical conductivity. A layer provided for the purpose of a highly reliable wiring pattern.

The metal-plated layer (D) is a layer formed on the metal layer (C). As a method for forming the metal-plated layer (D), a method in which a plating process is used is preferable. Examples of the 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; and the like. In addition, two or more of these plating methods may be combined to form the aforementioned metal plating layer (D).

The above-mentioned electroless plating method is, for example, bringing the metal constituting the metal layer (C) into contact with an electroless plating solution, thereby making the electroless plating solution A method in which a metal such as copper is precipitated to form an electroless plating layer (film) including a metal film.

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

Examples of the reducing agent include dimethylaminoboron, hypophosphite, sodium hypophosphite, dimethylaminoboron, hydrazine, formaldehyde, sodium borohydride, and phenol.

In addition, as the electroless plating solution, monocarboxylic acids containing acetic acid, formic acid, and the like; dicarboxylic acids such as malonic acid, succinic acid, adipic acid, maleic acid, and fumaric acid can be used as needed; apples Acid, lactic acid, glycolic acid, gluconic acid, citric acid and other hydroxycarboxylic acid compounds; glycine, alanine, iminodiacetic acid, arginine, aspartic acid, glutamic acid and other amino acids Compounds; organic acids such as amino polycarboxylic acid compounds such as iminodiacetic acid, nitrilotriacetic acid, ethylenediaminediacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, or the like Soluble salts (sodium salt, potassium salt, ammonium salt, etc.), complex compounds such as amine compounds such as ethylenediamine, diethylenetriamine, and triethylenetetramine.

The electroless plating solution is preferably used in a range of 20 to 98 ° C.

The electrolytic plating method is performed by, for example, 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 the electrolytic plating solution, thereby causing the electrolysis Metals such as copper contained in the plating solution are deposited on a conductive material constituting the metal layer (C) provided on the cathode, or from the electroless treatment station. A method for forming an electrolytic plating layer (metal film) on the surface of the formed electroless plating layer (film).

Examples of the electrolytic plating solution include sulfide, sulfuric acid, and an aqueous medium containing metals such as copper, nickel, chromium, cobalt, and tin. Specific examples include those containing copper sulfate, sulfuric acid, and an aqueous medium.

The electrolytic plating solution is preferably used in a range of 20 to 98 ° C.

Since the above-mentioned electrolytic plating method does not use a highly toxic substance and has good workability, it is preferable to form a metal-plated layer (D) containing copper using the electrolytic plating method.

As the dry plating treatment step, a sputtering method, a vacuum evaporation method, or the like can be used. The sputtering method is to introduce an inert gas (mainly argon) in a vacuum, apply negative ions to the forming material of the metal plating layer (D) to generate a glow discharge, and then ionize the inert gas atoms, and the gas ions are at a high speed. Vigorously hits the surface of the formation material of the metal plating layer (D), ejects the atoms and molecules constituting the formation material of the metal plating layer (D), and makes it strongly adhere to the surface of the metal layer (C), so that A method for forming a metal plating layer (D).

Examples of the material for forming the metal plating layer (D) by a sputtering method include chromium, copper, titanium, silver, platinum, gold, nickel-chromium alloy, stainless steel, copper-zinc alloy, and indium tin oxide. (ITO), silicon dioxide, titanium dioxide, niobium oxide, zinc oxide, etc.

When performing a plating process by the said sputtering method, a magnetron sputtering apparatus etc. can be used, for example.

The film thickness of the metal plating layer (D) is preferably in a range of 1 to 50 μm. The film thickness of the metal plating layer (D) can be adjusted by controlling the processing time, the current density, the amount of plating additives, and the like in the plating processing step when the metal plating layer (D) is formed.

When the metal layer (C) and the metal layer (D) of the multilayer body of the present invention are patterned into a metal grid, the thickness of the metal plating layer (D) is usually preferably 0.1 to 18 μm. In the range, in order to further reduce the width of the wiring after the etching, the metal plating (D) is preferably a thin film, preferably in a range of 0.1 to 5 μm, and more preferably 0.5 to 3 μm. In addition, in order to further improve the transparency, the line width of the metal grid portion is preferably in a range of 0.1 to 10 μm, and more preferably in a range of 0.5 to 3 μm.

The metal layer (C) and the metallized layer (D) of the multilayer body of the present invention are patterned into a metal grid and used as a touch panel. The metallized layer is formed on the transparent substrate (A). When a surface such as (D) is provided on the display as the outer side (viewing side), in order to improve the visibility of the display, it is preferable to further form a blackened layer (E) on the metal plating layer (D). This is, for example, when the metal-plated layer (D) is copper, and the grid-shaped wiring is seen due to reflection of external light caused by copper, black is provided on the metal-plated layer (D). The formation layer (E) is made black to prevent reflection of external light, making it difficult to see the grid-shaped wiring, and the visibility of the display is improved.

As a method for producing the laminated body of the present invention as a metal mesh, a method may be mentioned in which a primer resin composition (b) is applied to both sides or one side of a transparent substrate (A) and Drying to form a primer layer (B), and coating the primer layer (B) with gold A fluid belonging to the nanoparticle (c) is dried to form a metal layer (C), and a metal plating layer is formed on the metal layer (C) by an electrolytic plating method, an electroless plating method, or a combination thereof. After (D), unnecessary portions of the metal layer (C) and the metal plating layer (D) are removed by an etchant to form a grid-shaped conductive pattern. In addition, when the metal plating layer (D) and the like are formed on both sides of the transparent substrate (A), and the metal grid is used as a touch panel of the display, it is preferable to further improve the visibility of the display. A blackened layer (E) is formed on the aforementioned metallized layer (D) provided on the display (outside) side of the display, and an unnecessary portion is removed by an etchant to form a grid-like conductive pattern. .

In addition, as a method for producing a metal mesh, there may be mentioned a method of forming a primer layer by applying a primer resin composition (b) on both sides or one side of a transparent substrate (A) and drying the same ( B), a metal layer (C) is formed by printing a fluid containing metal nano particles (c) on the primer layer (B) and drying to form a grid-like pattern; An electroless plating method or a combination of these is used to form a metal plating layer (D) on the aforementioned metal layer (C). In addition, when the metal plating layer (D) and the like are formed on both sides of the transparent substrate (A), and the metal grid is used as a touch panel of the display, it is preferable to further improve the visibility of the display. A blackening layer (E) is formed on the metal-plated layer (D) provided on the display (outside viewing side) when the display is provided.

On both sides of the transparent substrate (A), a primer layer (B), a metal layer (C), a metal plating layer (D), and the like are formed, and a conductive pattern is formed on both sides, and it is preferable to use it as a metal grid. As shown in FIG. 3, stripe-shaped conductive patterns are formed on one surface and the other surface so that they are formed orthogonally to each other.

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

As the wet method, for example, a method described in Japanese Patent No. 5862916 can be used. Specifically, a method can be mentioned in which a blackening layer is formed by a blackening treatment liquid containing at least one compound selected from the group containing palladium, ruthenium, and silver, and a compound containing a halide and a nitrogen atom. (E). In addition, there can be mentioned a method of generating a black copper oxide by subjecting the copper surface to oxidation treatment using hypochlorite, chlorite, or the like when the metal layer (D) is copper, Alternatively, the method of forming a black copper sulfide using an aqueous sulfide solution to form the blackened layer (E).

The blackening layer (E) can also be formed by a cobalt-copper alloy plating. A chromate treatment as a rust preventive treatment may be further performed thereon. In addition, the chromate treatment is one in which a chromic acid or a dichromate is a main component and is dried to form a rust-preventive film.

Examples of the dry method include a method of forming the blackened 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), it is sufficient if the grid-shaped wiring becomes difficult to see, and it is preferably in the range of 20 to 500 nm, and more preferably in the range of 20 to 100 nm.

The laminated body of this invention obtained by the said method can be used as a conductive pattern. When the laminated body of the present invention is used for a conductive pattern, in order to form a layer corresponding to a desired pattern shape, The metal layer (C) is formed at a position, and a conductive pattern having a desired pattern can be produced by applying a fluid containing the metal powder.

The conductive pattern may be a photolithography method such as a subtractive method, a semi-additive method, or the like; or plating on a printed pattern of the metal layer (C). Method to manufacture.

The aforementioned subtraction method is formed on the metallized layer (D) (the blackened layer (E) in the case where the blackened layer (E) is formed) constituting the pre-manufactured multilayer body of the present invention to form The etching resist layer having a desired pattern shape is removed by dissolving and removing the metal layer (C), the metal plating layer (D), and the like in a portion of the resist removed by a chemical solution through a subsequent development process. A method for forming a desired pattern. As the chemical solution, a chemical solution containing copper chloride, ferric chloride, or the like can be used.

The semi-additive method is to form the primer layer (B) and the metal layer (C) on both sides or one side of the transparent substrate (A), and form a surface corresponding to the desired on the surface of the metal layer (C). A patterned plating resist layer, and then a metal plating layer (D) is formed by an electrolytic plating method, an electroless plating method, or a combination thereof, and then the aforementioned plating resist layer and the aforementioned A method in which a metal layer (C) is dissolved in a chemical solution or the like, and the blackened layer (E) is formed on the formed plating layer (D) as needed to form a desired pattern.

In addition, the method of plating on the printed pattern of the metal layer (C) is performed on the primer layer (B) formed on both or one side of the transparent substrate (A) by using an inkjet method, The pattern of the metal layer (C) is printed by a reverse printing method or the like, and the surface of the metal layer (C) is electrolyzed by electrolysis. A method of forming the aforementioned metal-plated layer (D) by a plating method, an electroless plating method, or a combination of these, and forming the aforementioned blackened layer (E) as needed to form a desired pattern.

Compared with the conventional method of forming a copper layer by a vapor deposition method or a sputtering method, the multilayer substrate transparent substrate of the present invention obtained by the method described above has excellent adhesion to the metal plating layer, and is conductive with an etchant. The non-patterned portion after the pattern is excellent in transparency. When the grid-shaped conductive pattern is formed using the laminated body of the present invention, the grid-shaped conductive pattern is difficult to see when viewed from a surface on which the aforementioned conductive pattern is not formed. Therefore, the laminated body of the present invention can be suitably used as, for example, a conductive pattern, a conductive film for a touch panel, a metal grid for a touch panel, an electronic circuit, an organic solar cell, an electronic terminal, an organic EL Wiring components such as devices, organic transistors, flexible printed boards, RFIDs such as non-contact IC cards, and electromagnetic wave shields. In particular, it is most suitable for applications such as a touch panel that requires 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, and neopentyl glycol were introduced into a reaction vessel equipped with a thermometer, a nitrogen introduction tube, and a stirrer while introducing nitrogen gas. 604 parts by mass and 0.5 parts by mass of dibutyltin oxide were subjected to a polycondensation reaction at 230 ° C for 15 hours until the acid value became 1 or less at 180 to 230 ° C to obtain a polyester polyol having a hydroxyl value of 55.9 and an acid value of 0.2.

100 parts by mass of the above-mentioned polyester polyol was dehydrated under reduced pressure at 100 ° C, and after cooling to 80 ° C, 883 parts by mass of methyl ethyl ketone was added and stirred thoroughly to dissolve, and propionic acid 2,2- 80 parts by mass of dimethylol, and then 244 parts by mass of isophorone diisocyanate were added and reacted at 70 ° C. for 8 hours.

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

The methyl ethyl ketone was removed from the reaction product under a reduced pressure of 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 50,000.

[Preparation of resin composition (R-2)]

90 parts by mass of water, 0.7 parts by mass of sodium alkyldiphenyl ether disulfonate ("Dowfax 2A-1" manufactured by Dow Chemical Co., Ltd.), 0.15 parts by mass of sodium ethylenediamine tetraacetate, 29 parts by mass of butadiene, 68 parts by mass of styrene, 3 parts by mass of acrylic acid, and stirring was started. Then, it heated up to 60 degreeC, and once temperature stabilized, 0.15 mass part of ammonium persulfate was added, and polymerization was started. After polymerization was performed 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, 25 mass% ammonia water and water were added, pH and solid content were adjusted, and the resin composition (R-2) of pH 7 and 10% solid content was obtained.

[Preparation of resin composition (R-3)]

180 parts by mass of ethyl acetate were added to a reaction vessel equipped with a stirrer, a reflux cooling tube, a nitrogen introduction tube, a thermometer, a dropping funnel for dripping a monomer mixture, and a dropping funnel for dripping a polymerization catalyst. While injecting nitrogen, the temperature was raised to 80 ° C. In the reaction vessel that had been heated to 80 ° C, 90 parts by mass of methyl methacrylate and acrylic acid were dropped from the respective dropping funnels while maintaining the temperature in the reaction vessel at 80 ± 1 ° C with stirring. 10 parts by mass of n-butyl ethylene monomer mixture and polymerization initiator solution containing 1 part by mass of azoisobutyronitrile and 20 parts by mass of ethyl acetate were polymerized. After the completion of the dropping, the mixture was stirred at the same temperature for 120 minutes, and then the temperature in the reaction vessel was cooled to 30 ° C. Next, ethyl acetate was added so that the non-volatile content became 10% by mass, and the mixture was filtered through a 200-mesh metal mesh to obtain a resin composition (R-3).

[Modulation of fluid (1)]

According to Example 1 described in Japanese Patent No. 4573138, a cationic silver having a gray-green metallic luster and a flake-like block containing a composite of silver nano particles and an organic compound having a cationic group (amine group) was obtained. Nano particles. 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]

Using a bar coater, the resin composition (R-1) prepared as described above was applied to a transparent substrate ("Lumirror 50T-60" manufactured by Toray Co., Ltd. so that the thickness after drying became 0.5 μm. Ethylene terephthalate film with a thickness of 50 μm; hereinafter referred to as "PET substrate"). Next, using a hot-air dryer, it dried at 80 degreeC for 5 minutes, and formed the primer layer on the surface of PET base material.

Next, the entire surface of the primer layer was coated on the surface of the primer layer with a bar coater to an area of 30 cm in length and 20 cm in width. Next, firing was performed at 80 ° C. for 5 minutes to form a silver layer (mass per unit area: 200 mg / m ² ) corresponding to the metal layer (C).

Next, the silver layer corresponding to the metal layer (C) obtained above is subjected to electroless copper plating. It was immersed in an electroless copper plating solution ("OIC Copper", manufactured by Okano Pharmaceutical Industry Co., Ltd., pH 12.5) at 55 ° C for 20 minutes to perform electroless copper plating. Next, the copper layer obtained by the electroless copper plating was set to the anode side, the phosphorus-containing copper was set to the cathode side, and electrolytic plating was performed using an electrolytic plating solution containing copper sulfate at a current density of 2.5 A / dm ² for 4 minutes. As a result, a copper plating layer (total thickness 2 μm) corresponding to the metal layer (D) was formed on the surface of the silver layer. As the electrolytic plating solution, 70 g / L of copper sulfate, 200 g / L of sulfuric acid, 50 mg / L of chloride ion, and 5 ml / L of an additive ("Top Lucina SF-M" manufactured by Okano Pharmaceutical Industry Co., Ltd.) were used.

Next, the copper-plated 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 at 30 ° C. for 3 minutes. A blackened layer is formed on the surface of the copper plating layer.

According to the above method, a laminated body (each of which is a transparent substrate (A), a primer layer (B), a metal layer (C), a metallized layer (D), and a blackened layer (E)) is obtained. 1).

[Example 2]

A laminated body (2) was obtained in the same manner as in Example 1 except that the resin composition (R-2) was used in place of the resin composition (R-1).

[Example 3]

A laminated body (3) was obtained in the same manner as in Example 1 except that the resin composition (R-3) was used in place of the resin composition (R-1).

[Comparative Example 1]

Using an electron beam (EB) vapor deposition method, a surface of a PET substrate was vapor-deposited so that the thickness of copper became 2 μm to form a copper vapor-deposited layer. At this time, the power of the electron beam was set to 53.5 kW / m with respect to the film formation width.

Next, the copper-plated 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 at 30 ° C. for 3 minutes. A blackened layer is formed on the surface of the copper plating layer.

By the above method, a laminated body (R1) in which each layer is laminated in the order of the transparent substrate (A), the metallized layer (D), and the blackened layer (E) is obtained.

[Comparative Example 2]

A laminated body (R2) was obtained in the same manner as in Example 1 except that the aforementioned resin composition (R-1) was not used, and the primer layer (B) was not formed.

The multilayer bodies (1) to (3), (R1), and (R2) obtained in the above-mentioned Examples 1 to 3 and Comparative Examples 1 to 2 were subjected to the following measurements and evaluations.

<Evaluation of Adhesion Based on Peel Strength Measurement>

The peeling strength was measured by the method according to IPC-TM-650, NUMBER2.4.9. The wire width used for the measurement is set to 1mm, The peeling angle was set to 90 °. In addition, the peeling strength tends to show a higher value as the thickness of the plating layer is thicker. However, the measurement of the peeling strength in the present invention is performed by electrolytic copper plating, and the measured value of the copper film thickness of 15 μm is used as a reference .

<Brightness Evaluation Based on L * a * b * Color System>

Measurement was performed using CM3500d manufactured by Konika Minolta Co., Ltd. in accordance with JIS Z 8722. The measurement is performed from the side of the transparent substrate opposite to the surface on which the primer layer or the like is formed.

<Transmittance measurement of transparent substrate>

A spectrophotometer ("MPC-3100" manufactured by Shimadzu Corporation) was used to measure the transmittance at a wavelength of 500 to 550 nm, and the transmittance at the wavelength with the highest transmittance was used. The transparent substrate ("Lumirror 50T-60", manufactured by Toray Co., Ltd., with a thickness of 50 µm) has a transmittance of 88%.

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

After removing the metal layer (C), the metallized layer (D), and the blackened layer (E) from the laminated body obtained above using an etchant (a 30% by mass aqueous solution of ferric chloride), use The transmittance was measured in the same manner as in the portion (non-patterned portion) from which each layer was removed. Thereafter, from the values of the transmittance of the transparent base material and the transmittance of the non-patterned portion after etching, the retention was calculated using the following formula.

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

<Invisibility of the metal grid part> (Invisibility of the metal grid portion of Examples 1 to 3)

As shown in FIG. 2, a primer layer, a silver layer, and a copper plating layer were sequentially formed on both sides of the PET substrate by the same method as in each example, and a blackened layer was formed only on one side of the copper plating layer to obtain a laminate. body. Thereafter, using an etchant (a 30% by mass aqueous solution of ferric chloride), a conductive pattern as shown in FIGS. 3, 4 and 5 was produced. The size of the conductive pattern was a stripe having a wiring width of 5 μm, a pitch of 250 μm, and a thickness of the copper plating layer of 2 μm. In addition, as shown in FIG. 3, the conductive pattern on the top surface side is made orthogonal to the conductive pattern on the bottom surface side. From the side on which the obtained blackened layer was formed, it was visually confirmed that the invisibility (difficulty) of the metal mesh portion (the conductive pattern on the top surface side and the bottom surface side) was evaluated according to the following criteria.

A: The wiring pattern is not visible as a whole.

B: A faint wiring pattern is seen as a whole.

C: The wiring pattern is seen as a whole.

(Invisibility of the metal grid portion of Comparative Example 1)

In the same manner as in Comparative Example 1, a copper vapor-deposited layer was formed on both surfaces of the PET substrate, and a blackened layer was formed only on one side of the copper-deposited layer to obtain a laminated body. Thereafter, a conductive pattern was formed in the same manner as in Examples 1 to 3 above, and the invisibility of the metal mesh portion was evaluated.

(Invisibility of the metal grid portion of Comparative Example 2)

A conductive pattern was formed in the same manner as in Examples 1 to 3 except that the primer layer was not formed, and the invisibility of the metal mesh portion was evaluated.

The measurement and evaluation results obtained above are arranged and shown in Table 1.

The laminates (1) to (3) obtained in Examples 1 to 3 of the laminated body of the present invention can be confirmed to have sufficiently high peel strength in practical use. In addition, it was confirmed that the transmittance of the non-patterned portion after the etching is high, and even if the etching process is performed, it has high transparency. In addition, it can be confirmed that from the side of the transparent substrate opposite to the surface on which the metal plating layer is formed, the brightness measured by the L * a * b * colorimetric system is as low as 55 or less, and it is black. When the laminated body is used as a metal grid, it is difficult to see its pattern, and it can be used 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 practical grades. In addition, in the multilayer body (R1) obtained in Comparative Example 1, it was confirmed that when the metal grid formed into a copper vapor-deposited layer was formed, the pattern was a hue of metallic copper having a high brightness, and the pattern was easy to see, which was not suitable for use. As a touch panel.

Claims (11)

A laminated body comprising a primer layer (B), a metal layer (C) formed of metal nano particles (c), and a metallized layer (D) on a transparent substrate (A). The laminated body is characterized in that the brightness of the value measured in the L * a * b * color system from the side of the transparent substrate (A) opposite to the surface on which the primer layer (B) is formed ( L *) is 55 or less. A laminated body is formed on the transparent base material (A) of the laminated body as claimed in claim 1 opposite to the surface on which the primer layer (B) is formed, and a primer is further laminated in this order. A layer (B), a metal layer (C) formed of metal nano particles (c), and a metal plating layer (D). The laminated body according to claim 1, wherein a blackened layer (E) is further formed on the metal plating layer (D). For example, the laminated body of claim 2, wherein a blackened layer (E) is further formed on any one of the two-sided metal plating layer (D). The laminated body according to any one of claims 1 to 4, wherein the transparent substrate (A) is selected from the group consisting of polyethylene terephthalate, polyethylene terephthalate, polycarbonate, and polyethylene. Selected from the group of amines, cycloolefin polymers, polymethyl methacrylate, polyethylene, polypropylene, and glass. The laminated body according to any one of claims 1 to 5, wherein the primer layer (B) is formed of a resin having an aromatic ring. The laminated body according to any one of claims 1 to 6, wherein the metal nanoparticle (c) is at least one selected from the group consisting of silver, copper, palladium, gold, nickel, platinum, and cobalt. The laminated body according to any one of claims 1 to 7, wherein the mass per unit area of the metal layer (C) is in the range of 1 to 1,000 mg / m ² . The laminated body according to any one of claims 1 to 8, wherein the metal plating layer (D) is copper. A metal grid characterized by patterning a metal layer (C), a metallized layer (D), and a blackened layer (E) of the laminated body according to any one of claims 1 to 9. A touch panel is characterized by having a metal grid as claimed in claim 10.