JP2015141741A - Method of producing patterned transparent conductive laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of producing a patterned transparent conductive laminate having a conductive linear structure, wherein the patterned transparent conductive laminate prevents its bone from being visible.SOLUTION: For a patterned transparent conductive laminate having a conductive linear structure, a step (A) of patterning a conductive layer into a conductive area and an insulative area and a step (B) of applying sandblast treatment to the insulative area are performed in this order.

Description

  The present invention relates to a method for producing a patterned transparent conductive laminate having a conductive layer containing a conductive linear structure. More specifically, the present invention relates to a method for producing a patterned transparent conductive laminate in which a pattern of a conductive region is visually recognized, so-called “bone appearance” is suppressed.

  Transparent conductive laminates are widely used as conductive members for electrodes in fields such as flexible displays and solar cells, in addition to applications such as touch panels, organic EL, liquid crystal displays, and PDPs. In forming such a transparent conductive laminate exhibiting conductivity, there is a method of forming a film by incorporating a conductive linear structure into a resin.

  Carbon nanotubes and metal nanowires are known as the conductive linear structure. A coating film (conductive layer) formed by applying a paint in which these conductive linear structures are dispersed is conductive by constructing a network structure in which the conductive linear structures are in contact with each other in the coating film. Sex develops (Patent Documents 1 and 2).

  When applying a transparent conductive laminated body to a touch panel etc., it is necessary to pattern a conductive layer into the electroconductive area | region which can be conduct | electrically_connected, and a nonelectroconductive insulating area | region. The patterning of the conductive layer is generally performed using a chemical etching method.

JP 2000-26760 A Special table 2009-505358

  As described above, the chemical etching method is generally used as the pattern forming method of the conductive layer. However, the conductive layer patterned into the conductive region and the insulating region by the chemical etching method has both optical characteristics. Depending on the difference (for example, haze value), a so-called “bone appearance” in which the pattern of the conductive region is visually recognized occurs, and there is a problem that the quality is lowered.

  Accordingly, an object of the present invention is to provide a method for producing a patterned transparent conductive laminate having reduced bone appearance in view of the above-described problems of the prior art.

The above object of the present invention has been basically achieved by the following invention.
1) A method for producing a transparent conductive laminate having a conductive layer containing a conductive linear structure on at least one side of a substrate, the conductive layer being patterned into a conductive region and an insulating region, A method for producing a patterned transparent conductive laminate, comprising a step (A) of patterning a layer into a conductive region and an insulating region, and a step (B) of subjecting the insulating region to a sandblast treatment in this order.
2) The step (A) of patterning the conductive layer includes, in this order, a step (A1) of forming a patterned etching resist film on the conductive layer and a step (A2) of etching the conductive layer. The patterning process according to 1), wherein the step (B) of performing sandblasting on the conductive region is performed through an etching resist film, and the step (C) of removing the etching resist film is provided after the step (B). A method for producing a transparent conductive laminate.
3) The manufacturing method of the transparent conductive laminated body as described in said 1) or 2) whose said conductive linear structure is silver nanowire.
4) A touch panel using the transparent conductive laminate according to any one of 1) to 3).

  According to the method for producing a patterned transparent conductive laminate of the present invention, a method for producing a patterned transparent conductive laminate having reduced bone appearance can be provided using a chemical etching method.

FIG. 1 a is a schematic cross-sectional view showing an example of the production process of the patterned transparent conductive laminate of the present invention. FIG. 1 b is a schematic cross-sectional view showing an example of the production process of the patterned transparent conductive laminate of the present invention. FIG. 1c is a schematic cross-sectional view showing an example of the production process of the patterned transparent conductive laminate of the present invention. FIG. 1d is a schematic cross-sectional view showing an example of the production process of the patterned transparent conductive laminate of the present invention. FIG. 1e is a schematic cross-sectional view showing an example of the production process of the patterned transparent conductive laminate of the present invention. FIG. 1f is a schematic cross-sectional view showing an example of the manufacturing process of the patterned transparent conductive laminate of the present invention. FIG. 2 is a schematic cross-sectional view showing an example of a touch panel using the patterned transparent conductive laminate of the present invention.

  The patterned transparent conductive laminate of the present invention has a conductive layer containing a conductive linear structure on at least one surface of a substrate, and the conductive layer is patterned into a conductive region and an insulating region. . Various patterns are adopted as the pattern shape of the conductive layer depending on the application (for example, touch panel application) to which the patterned transparent conductive laminate is applied. Examples of the pattern shape include a stripe shape, a lattice shape, or a combination thereof. Specifically, for example, there are patterns disclosed in JP-A-2006-344163, JP-A-2011-128896, and the like.

  In the patterned transparent conductive laminate of the present invention, a protective layer may be provided on the conductive layer for the purpose of protecting the conductive linear structure of the conductive layer. Such a protective layer is integrated with the conductive layer (the resin of the protective layer component is contained in the conductive linear structure of the conductive layer, and a part of the conductive linear structure is contained in the protective layer). In the case where a protective layer is provided, the conductive layer including the protective layer is referred to as a conductive layer. Details of the protective layer will be described later.

  When a conductive layer containing a conductive linear structure is patterned into a conductive region and an insulating region, the conductive region (the region where the conductive linear structure exists) and the insulating region (conductive linear by etching, etc.) Due to the difference in optical characteristics (for example, haze value) with respect to the region from which the structure has been removed, a “bone appearance” phenomenon in which patterning of the conductive region is visually recognized is likely to occur. The present invention has found that the above-mentioned “bone appearance”, which is a problem, is suppressed by subjecting the insulating region to sandblasting, and has led to the present invention.

  By subjecting the insulating region to sandblasting, a minute dent is formed in the insulating region to increase the haze value, and the haze value of the insulating region is approximately the same as the haze value of the conductive region. It is estimated that “bone appearance” is reduced.

  The manufacturing method of the patterned transparent conductive laminated body of this invention is demonstrated in detail using FIG. FIG. 1a is a schematic cross-sectional view showing an example of a transparent conductive laminate used for producing the patterned transparent conductive laminate of the present invention. The transparent conductive laminate 10 has a conductive layer 2 including a conductive linear structure 3 on a substrate 1. A protective layer (not shown) may be provided on the conductive layer 2 for the purpose of protecting the conductive linear structure.

  The manufacturing method of the patterned transparent conductive laminated body of this invention has the process (A) which patterns a conductive layer into an electroconductive area | region and an insulating area, and the process (B) which performs a sandblast process to an insulating area in this order. .

  A chemical etching method is preferably used in the step (A) of patterning the conductive layer into a conductive region and an insulating region. The chemical etching method includes a step (A1) of forming a patterned etching resist film on the conductive layer and a step (A2) of etching the conductive layer in this order.

  The step (A1) of forming a patterned etching resist film on the conductive layer can be performed using a photolithography method (mask exposure method or laser exposure method) or a printing method.

  The etching resist film is made of an acrylic photoresist material that is cured by exposure to ultraviolet rays or a laser beam, and the unexposed portion can be developed with an alkaline solution. The etching resist film may be laminated by applying a liquid resist material on the conductive layer, or may be laminated by bonding a dry resist film on the conductive layer.

  FIG. 1B and FIG. 1C show an example of the step (A1) of forming a patterned etching resist film on the conductive layer. Here, an example using a photolithography method (mask exposure method) is shown.

  First, an etching resist film (here, a dry resist film is used) 5 is laminated on the surface of the conductive layer 2 of the transparent conductive laminate 10. Next, the etching resist film 5 is exposed (ultraviolet irradiation) through the photomask 8 (FIG. 1b). The photomask 8 is patterned into a light shielding portion 6 and a light transmitting portion 7 in accordance with a predetermined (desired) conductive layer pattern. Note that in such exposure, the region of the conductive layer where light is shielded finally becomes an insulating region, and the region where light is transmitted becomes a conductive region.

  Next, the etching resist film 5 exposed through the photomask 8 is developed. By this development processing, the etching resist film in the unexposed portion (the portion corresponding to the light shielding portion 6 of the photomask 8) is dissolved and removed, and the etching resist in the exposed portion (the portion corresponding to the light transmitting portion 7 of the photomask 8). The film remains without being dissolved and removed, and a patterned etching resist film 5 is formed on the conductive layer 2 (FIG. 1c).

  Next, the step (A2) of etching the conductive layer is performed (FIG. 1d). In this step, the conductive layer is etched through the patterned etching resist film.

  The etching solution acts only on the region 16 where the etching resist film 5 is not covered, and the conductive linear structure 3 of the conductive layer is dissolved and removed to form an insulating region. On the other hand, the conductive layer in the region 17 covered with the etching resist film 5 is not etched and becomes a conductive region (FIG. 1d).

  The etchant can be appropriately selected according to the conductive linear structure. For example, in the case of silver nanowires, an acidic etching solution such as a mixture of hydrochloric acid and nitric acid can be used. The content of the acid contained in the etching solution is preferably 1 to 40% by mass, more preferably 10 to 25% by mass with respect to the total mass of the etching solution. When it is larger than 40% by mass, the etching rate becomes extremely fast, and it may be difficult to control the etching. Moreover, the processing temperature at the time of etching may be appropriately adjusted according to the type and concentration of the etching solution used, but the etching solution component easily acts on the conductive linear structure by processing at 30 to 60 ° C. Therefore, it is preferable. If it is less than 30 ° C, control at low temperatures may be difficult, and the action and penetration of the etching solution component may be slow. If it exceeds 60 ° C, the acid components may react excessively, and the etching solution May change.

  Next, a step (B) of performing a sandblasting process on the insulating region is performed (FIG. 1e). The sand blasting process is performed through an etching resist film. As a result, the conductive region 27 is not subjected to sandblasting because the etching resist film serves as a sandblasting mask, and only the insulating region 26 is sandblasted.

  A minute recess 9 is formed in the insulating region 26 subjected to the sandblasting process. By forming the micro-dent 9 in the insulating region 26 in which the linear structure is dissolved and removed by the etching process, the haze value of the insulating region 26 is approximately equal to the haze value of the conductive region 27. Can be raised. This is considered to reduce the haze value difference (optical characteristic difference) between the conductive region and the insulating region, thereby reducing the “bone appearance”.

  It does not specifically limit as a sandblasting process, A well-known sandblasting process can be used. For example, there is a method in which inorganic particles are used as a projecting material, and this is sprayed from the nozzle tip by the force of compressed air.

  Examples of the projection material used for the sand blasting include inorganic particles such as silica, silicon carbide, zirconia, alumina, and diamond. Among these, particles having high hardness are preferably used.

  In addition, inorganic particles having high electrical insulation are preferably used as the projection material. Even if inorganic particles having high electrical insulation remain on the surface of the insulating region, the insulating properties are not lowered.

  The average particle diameter of the projection material is preferably 1 to 50 μm. When the average particle diameter of the projection material is in the range of 1 to 50 μm, an appropriate collision energy can be obtained, and the dent can be given to the insulating region without damaging the base material. When the particle diameter is larger than 50 μm, the collision energy when spraying the projection material becomes too large, and the dent becomes large, making it difficult to adjust the haze value. Conversely, if the average particle diameter of the projection material is less than 1 μm, the collision energy of the projection material may be too small to form an appropriate dent.

  Here, the average particle diameter of a projection material means a center particle diameter (D50), and is a value measured by a laser diffraction scattering type particle size distribution measuring apparatus.

  After the step (B) of performing the sandblast treatment on the insulating region is performed, the step (C) of removing the etching resist film is performed (FIG. 1f). The etching resist film 5 present on the conductive layer 2 is stripped and removed by alkali treatment. As the alkaline solution used for the alkali treatment, an alkaline aqueous solution containing about 1 to 4% by mass of sodium hydroxide is generally used.

  After the step (C) of removing the etching resist film, a normal water washing process is performed.

  Hereinafter, each component which comprises the patterned transparent conductive laminated body of this invention is demonstrated in detail.

[Base material]
The base material is a material on which a conductive layer is laminated. For example, a base material having rigidity or flexibility can be used. In consideration of application to touch panel applications, etc., the base material has a transparency with a total light transmittance in the visible light region of 80% or more, preferably 85% or more, more preferably 90% or more. preferable. Specifically, a film base material, a glass base material, etc. can be mentioned, Even if it is a film base material which can be wound up with a thickness of 250 micrometers or less, a glass base material exceeding thickness 250 micrometers may be sufficient. From the viewpoints of cost, productivity, handleability, etc., a film substrate of 250 μm or less is preferable, 190 μm or less is more preferable, and 150 μm or less is particularly preferable.

  Film base materials include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyimide, polyphenylene sulfide, aramid, polypropylene, polyethylene, polylactic acid, polyvinyl chloride, polycarbonate, polymethyl methacrylate, and alicyclic. Examples include acrylic resins, cycloolefin resins, triacetylcellulose, and mixtures and / or copolymers of these resins. For example, the resin can be unstretched, uniaxially stretched, or biaxially stretched to form a film.

  As the glass substrate, ordinary soda glass can be used.

  Moreover, these several base materials can also be used in combination. For example, a composite substrate such as a substrate in which a film substrate and a glass substrate are combined, or a substrate in which two or more kinds of films are laminated may be used.

  Furthermore, the substrate may be subjected to a surface treatment as necessary. The surface treatment may be provided with a physical treatment such as glow discharge, corona discharge, plasma treatment, flame treatment, or a resin layer. In the case of a film, it may have an easy adhesion layer. The kind of base material is not limited to the above, and an optimal one can be selected from transparency, durability, flexibility, cost, etc. according to the application.

[Conductive layer]
The conductive layer contains a conductive linear structure, and may additionally contain additives such as a binder, a dispersant, and a leveling agent contained in the conductive linear structure-dispersed paint. good.

  When the conductive linear structure is schematically shown as a three-dimensional structure, the conductive linear structure can be shown as an elliptic cylinder, a curved body of an elliptic cylinder, or a bent body thereof. In the present specification, the length corresponding to the major axis or minor axis at the bottom surface of the elliptical cylinder is referred to as the “short axis length (diameter of the conductive linear structure)” of the conductive linear structure. is there. Further, the length corresponding to the height of the elliptic cylinder may be referred to as “long axis length (length of conductive linear structure)” of the conductive linear structure.

  As the conductive linear structure, the length of the short axis (the diameter of the conductive linear structure) and the length of the long axis (the length of the conductive linear structure) can take various ranges. The length of the short axis is preferably 1 nm to 1000 nm, and the aspect ratio (long axis length / short axis length), which is the ratio of the long axis length to the short axis length, is greater than 10. Any length is acceptable. A large aspect ratio is preferable because a more effective network structure can be formed. Further, the length of the long axis is preferably 1 μm to 100 μm.

  Examples of the shape of the conductive linear structure include a linear shape and an arc shape, which may be a combination thereof, and may have a bent portion. Examples of such conductive linear structures include fibrous conductors, wire conductors, and needle conductors. Here, the fibrous shape is a linear shape and may have a bent portion. The wire shape is a structure having an arc shape, and the needle shape is a structure having a linear shape.

The material of the conductive linear structure in the present invention contains components such as a metal, an alloy, a metal oxide, a metal nitride, and a metal hydroxide. Metals include gold, platinum, silver, nickel, copper, aluminum, gallium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, manganese, antimony, palladium, bismuth, technetium, rhenium, iron, osmium, cobalt, Examples thereof include zinc, scandium, boron, gallium, indium, silicon, germanium, tellurium, tin, and magnesium. Examples of the alloy include alloys containing the metal (stainless steel, brass, etc.). Examples of the metal oxide include InO ₂ , SnO ₂ , ZnO, and the like, and these metal oxide composites (InO ₂ Sn, SnO ₂ —Sb ₂ O ₄ , SnO ₂ —V ₂ O ₅ , TiO _2). (Sn / Sb) O ₂ , SiO ₂ (Sn / Sb) O ₂ , K ₂ O—nTiO ₂ — (Sn / Sb) O ₂ , K ₂ O—nTiO ₂ —C, etc.). These may be subjected to a surface treatment. Further, the conductive linear structure includes those obtained by coating or vapor-depositing the surface of an organic compound (for example, vegetable fiber, synthetic fiber, etc.) or a non-metallic material (for example, inorganic fiber) with the metal or metal oxide. .

  Among the above-described conductive linear structures, silver nanowires can be particularly preferably used from the viewpoints of optical properties such as transparency and conductivity. In addition, the conductive linear structures can be used alone or in combination of a plurality of them, and other micro-to-nano conductive materials may be added as necessary.

  The conductive layer of the present invention can be formed by applying a coating material in which a conductive linear structure is dispersed in a dispersion medium on a substrate.

  The dispersion medium is not particularly limited as long as the conductive linear structure can be stably dispersed, and specifically, water, alcohol, ketone, ether, hydrocarbon, or aromatic can be used. A solvent (benzene, toluene, xylene, etc.) is preferably used. The liquid is preferably volatile, and the boiling point of the liquid is preferably 200 ° C. or lower, more preferably 150 ° C. or lower, and particularly preferably 100 ° C. or lower.

  Moreover, it is preferable that the coating material for forming a conductive layer contains a binder from the viewpoints of applicability, adhesion to a substrate, film forming property of a conductive layer, and the like.

  As the binder, carboxymethylcellulose (CMC), 2-hydroxyethylcellulose (HEC), hydroxypropylmethylcellulose (HPMC), methylcellulose (MC), polyvinyl alcohol (PVA) and the like are preferably used.

  Moreover, various additives can be added to the coating material within a range that does not impair the effects of the present invention. Examples of additives include organic and inorganic fine particles, cross-linking agents, flame retardants, flame retardant aids, heat stabilizers, oxidation stabilizers, leveling agents, ultraviolet absorbers, light stabilizers, nucleating agents, dyes, Examples include fillers, dispersants, and coupling agents.

  A wet coating method is preferably used as a method for applying the coating material for forming the conductive layer on the substrate. As the wet coating method, for example, known methods such as spray coating, bar coating, roll coating, die coating, dip coating, spin coating, gravure coating, extrusion coating, slide bead coating, and curtain coating can be used.

  In the present invention, the conductive linear structure is preferably present in a network structure in the conductive layer. The network structure means that the conductive linear structures are in contact with each other at at least one contact. The smallest network structure is a case where two conductive linear structures have one contact. The contact may be formed by any part of the conductive linear structure, the end parts of the conductive linear structure are in contact with each other, the terminal and the part other than the terminal are in contact, or the part other than the terminal They may be in contact with each other, and may be in contact with each other even if the contacts are joined.

[Protective layer]
A protective layer may be stacked over the conductive layer. The protective layer serves to improve the scratch resistance of the conductive laminate. From the above viewpoint, the protective layer preferably contains a resin. Examples of the resin to be contained in the protective layer include polyester, polyethylene terephthalate (PET), polybutylene terephthalate, polymethyl methacrylate (PMMA), acrylic resin, and polycarbonate. (PC), polystyrene, triacetate (TAC), polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polyethylene, ethylene-vinyl acetate copolymer, polyvinyl butyral, polyurethane, polyolefin, and other resins. The thickness of the protective layer is preferably thicker from the viewpoint of scratch resistance. Specifically, it is preferably 10 nm or more, more preferably 50 nm or more, particularly preferably 100 nm or more, and most preferably 120 nm or more. Moreover, various additives can be added to the protective layer within a range that does not impair the effects of the present invention. Examples of additives include organic and inorganic fine particles, crosslinking agents, flame retardants, flame retardant aids, heat stabilizers, oxidation stabilizers, leveling agents, slip activators, ultraviolet absorbers, light stabilizers, and cores. Agents, dyes, fillers, dispersants, coupling agents and the like can be used. As a method for forming the protective layer, a wet coating method is preferably used. As the wet coating method, the same ones as mentioned in the above-mentioned conductive layer coating method are used.

[Hard coat layer]
The patterned transparent conductive laminate of the present invention can be provided with a hard coat layer on the surface opposite to the side on which the conductive layer is laminated with respect to the substrate. By providing the hard coat layer, wear resistance, high surface hardness, solvent resistance, and contamination resistance can be imparted.

[Patterned transparent conductive laminate]
The patterned transparent conductive laminate of the present invention preferably has a total light transmittance of 80% or more, more preferably 85% or more, and particularly preferably 90% or more.

In the patterned transparent conductive laminate of the present invention, the surface resistance value of the conductive region is preferably ¹ Ω / □ or more and 1 × 10 ⁴ Ω / □ or less, more preferably 1 × 10 ¹ Ω / □ or more, 1.5 × 10 ³ Ω / □ or less. By being in this range, it can be preferably used as a touch panel application. That is, if it is 1 Ω / □ or more, power consumption can be reduced, and if it is 1 × 10 ⁴ Ω / □ or less, the influence of errors in reading coordinates of the touch panel can be reduced.

  The patterned transparent conductive laminate of the present invention can be preferably used as a conductive member for electrodes of touch panels, organic EL, liquid crystal displays, PDPs and the like. In particular, it is preferably used as an electrode member of a touch panel.

  As a touch panel system, a resistance film type and a capacitance type are mainly used, but the present invention is not limited to these systems and can be preferably used in any system. In particular, it is preferably used for a capacitive touch panel.

[Touch panel]
The patterned transparent conductive laminate of the present invention can be preferably used particularly as a touch panel. A touch panel is mounted with a single or a plurality of transparent conductive laminates having a pattern formed thereon, and further in combination with other members, and examples include a resistive touch panel and a capacitive touch panel.

  FIG. 2 is a schematic cross-sectional view showing an example of a capacitive touch panel using the patterned transparent conductive laminate of the present invention.

  Two patterned transparent conductive laminates 31 are laminated via a bonding layer 32 such as an adhesive or an adhesive, and a substrate 33 on the touch surface side is further disposed. A hard coat layer (or hard coat film) 34 is laminated on the surface of the substrate 33.

  Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to the following examples.

[Evaluation method]
First, an evaluation method in each example and comparative example will be described.

(1) Insulation confirmation test The surface resistance value of the etched region (insulating region) was measured using an insulation resistance meter (DG6 manufactured by Sanwa Denki Keiki Co., Ltd.) to confirm the insulation. When the surface resistance value is 25 V, 4 MΩ or more is insulated and less than 4 MΩ is conducted.

(2) Surface observation of the conductive layer (insulating region) of the patterned transparent conductive laminate The conductive layer side surface of the patterned transparent conductive laminate is a color 3D laser microscope (VK-9700 / 9710 manufactured by Keyence Corporation), Conductive linear shape in the insulating region using a standard objective lens 150X (CF IC EPI Plan Apo 150X manufactured by Nikon Co., Ltd.) and an observation application (VK-H1V1 manufactured by Keyence Co., Ltd.) at a magnification of 3000 times. The presence or absence of a structure and the presence or absence of a dent were confirmed.

(3) Evaluation of visibility “bone appearance” of conductive layer pattern (non-visibility test)
The visibility of the boundary between the conductive region and the insulating region of the patterned transparent conductive laminate was visually observed under a fluorescent lamp and evaluated according to the following criteria.
Level 5: The border is invisible Level 4: The border is almost invisible Level 3: The thin border is visible Level 2: The border is visible Level 1: The border is clearly visible

[Example 1]
A transparent conductive laminate was produced as follows.

<Paint for forming conductive layer>
As a conductive linear structure, a silver nanowire dispersion solution (manufactured by Camrios Inc., CleraOhm) using silver nanowires having a short axis length of 50 to 100 nm, a long axis length of 20 to 40 μm, and an aspect ratio of 200 or more. Ink-A AQ) per 30 parts by mass of ultrapure water (Wako Pure Chemical Industries, Ltd., ultrapure water Ultrapure Water), 70 parts by mass, rust preventive (Cambrios, ClearOhm SFT-D) 0.12 mass part was added and the coating material for conductive layer formation was prepared.

<Lamination of conductive layer>
Using an optical polyethylene terephthalate film (Lumirror manufactured by Toray Industries, Inc.) having a thickness of 125 μm as a base material, the coating amount for forming the conductive layer is applied to one side of the film by a die coating method so that the solid content is 1 g / m ^2. And dried at 80 ° C. to laminate a conductive layer on the substrate.

<Coating for forming protective layer>
A protective layer-forming coating material was prepared by adding 95 parts by mass of ethyl acetate to 5 parts by mass of acrylic resin-based paint (Forseed No. 420C, resin concentration 50% by weight, manufactured by China Paint Co., Ltd.).

<Lamination of protective layer>
On the conductive layer laminated on the substrate, the above protective layer-forming coating material is applied by a die coating method so that the thickness of the protective layer (thickness after curing) is 210 nm, dried at 80 ° C., and UV A protective layer was formed by irradiating and curing 200 mJ / cm ² (LH10-70UV lamp manufactured by Fusion UV Systems Japan Co., Ltd.) to prepare a transparent conductive laminate.

<Formation of patterned etching resist film>
An etching resist film (dry resist film; “Sunfort SPG-152” manufactured by Asahi Kasei E-Materials Co., Ltd.) is used on the conductive layer (including the protective layer) of the transparent conductive laminate, and a hot roll laminator is used. Then, heat lamination was performed under the conditions of a roll temperature of 105 ° C., an air pressure of 0.3 MPa, and a lamination speed of 2 m / min to obtain a heat laminate.

Next, a photomask is placed on the dry resist film of the thermal laminate, and exposure is performed on the photomask using a 4.5 kW mercury short arc lamp (HMW-801 parallel light manufactured by Oak Manufacturing Co., Ltd.). The exposure was performed at an amount of 200 mJ / cm ² .

  Next, a developing solution was sprayed on the heat-laminated body after the exposure to develop it. Specifically, using a conveyor type developing machine, a 1 mass% sodium carbonate aqueous solution is used as a developing solution, and the developing process is performed for 26 seconds under the conditions of a liquid temperature of 30 ° C. and a spray pressure of 0.22 MPa. A patterned etching resist film (dry resist film) was formed.

<Etching>
The transparent conductive laminate having the patterned etching resist film formed on the conductive layer was immersed in the following etching solution (45 ° C.) for 5 minutes for etching treatment.

<Etching solution>
100 parts by mass of hydrochloric acid (special grade manufactured by Wako Pure Chemical Industries, Ltd .; hydrogen chloride 36% by mass), 15 parts by mass of nitric acid (special grade manufactured by Sasaki Chemical Co., Ltd .; 60% by mass nitric acid), 85% pure water Mass parts were added to obtain an etching solution. The mass ratio of hydrogen chloride and nitric acid in the etching solution is 4: 1, and the combined acid concentration of hydrogen chloride and nitric acid is 22.5% by mass.

<Sandblasting>
The following sandblast treatment was applied to the surface of the conductive layer of the transparent conductive laminate patterned by etching the conductive layer as described above.

  “Microblaster MB1-ML” manufactured by Shinto Blator Co., Ltd. is used as a sandblasting device, silicon carbide having a center particle diameter of 17 μm is used as a projection material, injection pressure is 0.15 MPa, nozzle moving speed is 10 m / s, and the number of times of projection is four. And blasting was performed.

<Peeling and removal of etching resist film>
After the sandblast treatment, an alkaline stripping solution was sprayed (sprayed) on the transparent conductive laminate, and the etching resist film was peeled and removed from the transparent conductive laminate resist patterning sample. Specifically, an etching resist film is formed by using a conveyor-type peeling machine and using a 3% by mass sodium hydroxide aqueous solution as a peeling liquid and performing a peeling treatment for 34 seconds under the conditions of a liquid temperature of 50 ° C. and a spray pressure of 0.20 MPa. Was completely peeled off. Finally, it was washed with water to obtain the patterned transparent conductive laminate of Example 1.

[Evaluation]
The results of evaluating the patterned transparent conductive laminate of Example 1 are shown below.

<Insulation confirmation test>
When the insulating region of the patterned conductive layer was confirmed by the test method described above, it was insulating (4 MΩ or more).

<Surface observation of insulating region>
When the insulating region of the patterned conductive layer was confirmed by the test method described above, no linear structure was confirmed. In addition, a recess having an average diameter of 400 nm was formed in the insulating region.

<Non-visibility test>
When the boundary between the conductive region and the insulating region of the patterned conductive layer was confirmed by the test method described above, it was Level 5 (the boundary was not visible).

[Comparative Example 1]
A patterned transparent conductive laminate was produced in the same manner as in Example 1 except that the sandblast treatment was not performed.

[Evaluation]
The results of evaluating the patterned transparent conductive laminate of Comparative Example 1 are shown below.

<Insulation confirmation test>
When the insulating region of the patterned conductive layer was confirmed by the test method described above, it was insulating (4 MΩ or more).

<Surface observation of insulating region>
When the insulating region of the patterned conductive layer was confirmed by the test method described above, no linear structure was confirmed. Further, no recess was formed in the insulating region.

<Non-visibility test>
When the boundary between the conductive region and the insulating region of the patterned conductive layer was confirmed by the test method described above, it was Level 1 (the boundary was clearly visible).

  The patterned transparent conductive laminate obtained by the method for producing a patterned transparent conductive laminate of the present invention can be suitably used for electrode members used in displays such as touch panels and electronic paper, solar cell modules, and the like. .

1. Base material 2. 2. Conductive layer 4. Conductive linear structure 5. Etching resist film 6. Light shielding part of photomask 7. Light transmission part of photomask 8. Photomask Dent 10. Transparent conductive laminate 16. 18. Region not covered with etching resist film Region 26 covered with etching resist film 5 Insulating region 27. Conductive region 31. Patterned transparent conductive laminate 32. Bonding layer 33. Substrate on the touch surface side 34. Hard coat layer (hard coat film)

Claims (4)

A method for producing a transparent conductive laminate having a conductive layer containing a conductive linear structure on at least one side of a substrate, the conductive layer being patterned into a conductive region and an insulating region, A method for producing a patterned transparent conductive laminate, comprising a step (A) of patterning a conductive region and an insulating region, and a step (B) of subjecting the insulating region to a sandblast treatment in this order. The step (A) of patterning the conductive layer includes, in this order, a step (A1) of forming a patterned etching resist film on the conductive layer and a step (A2) of etching the conductive layer. 2. The patterned transparent conductive film according to claim 1, wherein the step (B) of performing a sandblasting process is performed through an etching resist film, and the step (C) of removing the etching resist film is provided after the step (B). A manufacturing method of a layered product. The manufacturing method of the transparent conductive laminated body of Claim 1 or 2 whose said electroconductive linear structure is silver nanowire. The touch panel which uses the transparent conductive laminated body in any one of Claims 1-3.

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