TW201627145A - Transparent conductive film laminate, touch panel obtained by using same, and method for producing transparent conductive film - Google Patents

Abstract

Provided are: a transparent conductive film laminate for controlling curling of the transparent conductive film laminate even after a heating step, and capable of ensuring the yield of a subsequent step, when using a cycloolefin resin in the substrate of a transparent conductive film; a touch panel obtained by using the same; and a method for producing the transparent conductive film. According to the present invention, a transparent resin film 4 comprises an amorphous cycloolefin resin, and a protective film 1 is formed from an amorphous resin which differs from the amorphous cycloolefin resin for forming the transparent resin film 4. The protective film 1 has a glass transition temperature of 130 DEG C or higher. After cutting the transparent conductive film laminate into 20cm x 20cm sections and heating the same for 90 minutes at 130 DEG C with a transparent conductive film 6 as the top surface, the difference (A-B) between the curl value A in the center section and the average curl value B in the four corner sections is 0-50mm.

Description

Transparent conductive thin film laminate and touch panel using the same, and method for producing transparent conductive film Technical field

The present invention relates to a transparent conductive thin film laminate, a touch panel obtained therefrom, and a method for producing a transparent conductive film, and more particularly to a technique for controlling the generation of curl.

Background technique

Conventionally, polyethylene terephthalate (PET) has been widely used as a base film of a transparent conductive film in a capacitive touch panel structure. However, since the PET film is stretched to form a film and has a high phase difference, it is difficult to be used as a substrate of the polarizing plate. Therefore, Patent Document 1 proposes a transparent conductive film using a cycloolefin resin as a base film for low phase difference.

When a cycloolefin-based resin is used as the base film, the base material is very fragile and easily damaged. When the roll-to-roll method is used for transport, it is necessary to perform a hard coat treatment on both surfaces of the base film. If a hard coat layer is provided on both surfaces of the base film, adhesion occurs (the films adhere to each other when the film is taken up), and therefore it is necessary to impart anti-sticking property to at least one side. In addition, when the transparent conductive layer is formed by sputtering or the like, and the pattern of the transparent conductive layer is treated with an acid anhydride, it is necessary to enter The wafer is subjected to a monolithic processing of the chemical/heating step, and a surface protective film must be laminated on the back surface of the substrate film on the side opposite to the transparent conductive layer.

Patent Document 2 discloses that both a base film and a surface protective film of a transparent conductive film are laminated bodies of a PET film. In this case, the heat shrinkage rate of each film in the heating step is adjusted to reduce the curl so that it can be conveyed satisfactorily.

Prior technical literature Patent literature

Patent Document 1: Japanese Laid-Open Patent Publication No. 2013-114344

Patent Document 2: Japanese Laid-Open Patent Publication No. 2008-251529

Summary of invention

However, in the case where a cycloolefin-based resin is used as the base film of the transparent conductive film and a PET substrate is used as the surface protective film, the heat shrinkage rate and the coefficient of linear expansion are different, and after the heating step, When the transparent conductive film is on, the surface of the transparent conductive film is curled in the concave direction, and when the transparent conductive thin film layered body is processed and transported, the air cannot be adsorbed by the air, so that it is difficult to pass the step or the like, and it is difficult to stabilize. Production is carried out continuously. Further, there is a difficulty in that it is not possible to adsorb a single-plate transparent conductive film by air during the processing step after cutting the coil of the transparent conductive film.

Accordingly, an object of the present invention is to provide a transparent olefin-based resin in a substrate of a transparent conductive film, which is also transparent after the heating step. The curl of the conductive thin film laminate ensures a transparent conductive thin film laminate having a subsequent step yield, a touch panel using the same, and a method for producing a transparent conductive film.

The present inventors have intensively reviewed the above problems, and as a result, have found that the above object can be achieved by adopting the following configuration.

That is, the transparent conductive thin film laminate of the present invention comprises: a carrier film having an adhesive layer on at least one side of the protective film; and a transparent conductive film which is releasably laminated through the adhesive layer, the transparent conductive In the film laminate, the transparent conductive film has a transparent resin film and a transparent conductive film, and the transparent resin film is made of an amorphous cycloolefin resin, and the transparent resin film has a thickness of 20 to 150 μm, and the carrier film is laminated. On the other surface side of the transparent conductive film which is different from the transparent conductive film, the protective film is formed of an amorphous resin different from the amorphous cycloolefin resin forming the transparent resin film, and the protective film is amorphous. The glass transition temperature of the resin is 130 ° C or higher, the thickness of the protective film is 20 to 150 μm, and the transparent conductive film laminate is cut into 20 cm × 20 cm, and the transparent conductive film is heated thereon at 130 ° C for 90 minutes. The difference (AB) between the curl value A of the rear central portion and the average curl value B of the four corner portions is 0 to 50 mm. Further, various physical property values in the present invention are values measured by the method employed in the embodiment and the like.

The reason for the occurrence of curling is considered to be due to the difference in heat shrinkage ratio, linear expansion coefficient, and the like of the cycloolefin resin and PET. For example, in the case of a transparent resin film-based cycloolefin-based resin, and a protective film-based PET In the case where the transparent conductive film is placed on the upper side, it is curled in the concave direction, and it is difficult to perform processing by suction by the suction cup. In the present invention, as described above, the transparent resin film uses an amorphous cycloolefin resin, and the protective film uses an amorphous resin different from the amorphous cycloolefin resin which forms the transparent resin film, whereby heat can be used. The shrinkage ratio and the coefficient of linear expansion are close to each other, so that the transparent conductive film can be curled toward the convex direction when the transparent conductive film is on. Thereby, in the conveyance process, the surface of the transparent conductive thin film laminated body on the side of the protective film can be sucked by air, and can be stably and continuously conveyed, and the metal wiring can be processed after the heating step.

The amorphous cycloolefin resin of the transparent resin film of the transparent conductive film laminate of the present invention preferably has a glass transition temperature of 130 ° C or higher, and has a first cured resin layer provided in the transparent resin film. a first main surface side; and a second hardened resin layer provided on a second main surface side opposite to the first main surface of the transparent resin film. When the glass transition temperature of the amorphous cycloolefin resin of the transparent resin film is 130° C. or more, the linear expansion coefficient and the heat shrinkage ratio of the amorphous resin used for the protective film can be made close to each other, and can be further controlled in drying or the like. Curl is produced during the heating step and the yield of subsequent steps is ensured. Further, since the cured resin layer is formed on both surfaces of the transparent resin film, it is less likely to be damaged in the steps of forming, patterning, or the like of the transparent conductive film or mounting on an electronic device.

The absolute value of the difference (a-b) between the glass transition temperature a of the amorphous cycloolefin resin of the transparent resin film of the present invention and the glass transition temperature b of the amorphous resin of the protective film is preferably 5 ° C or higher. Take this When the transparent conductive film side of the conductive thin film laminate is on the side, the transparent conductive thin film laminate can be curled in a convex direction in an appropriate range, and the transparent conductive thin film laminate can be easily transported to ensure the subsequent steps. Yield.

The amorphous cycloolefin resin of the transparent resin film of the present invention and the amorphous resin of the protective film are preferably resins having different constituent units. Therefore, when the transparent conductive film side of the transparent conductive thin film layered body is on the side, the transparent conductive thin film laminated body can be curled in the convex direction in an appropriate range, and the transparent conductive thin film laminated body can be easily transported to ensure The yield of the subsequent steps.

The protective film of the present invention is preferably composed of a polycarbonate resin, and has a weight average molecular weight of 2 × 10 ⁴ or more, and a heat shrinkage ratio after heating at 130 ° C for 90 minutes is 0.3% or less in the MD and TD directions. Since the protective film is made of a polycarbonate resin, a transparent conductive thin film laminate having excellent mechanical properties and workability can be obtained. Further, since excessive heat shrinkage in the heating step of the transparent conductive film can be suppressed, the occurrence of curl can be controlled to a higher degree, and the transparent conductive thin film layered body can be processed stably and continuously.

It is preferable that the transparent conductive thin film laminate of the present invention further has one or more optical adjustment layers between the first cured resin layer and the transparent conductive film. Since the refractive index can be adjusted by the optical adjustment layer, the difference in reflectance between the pattern forming portion and the pattern opening portion during patterning of the transparent conductive film can be reduced, so that the transparent conductive film pattern is not easily seen, and the display device such as a touch panel can be viewed. Good sex.

The touch panel of the present invention preferably uses the aforementioned transparent conductive film Collected by the body. When the transparent conductive film laminate is used, it is possible to further control the occurrence of curl in the heating step such as drying, and the transparent conductive film laminate can be easily processed and conveyed to improve work efficiency.

The present invention also includes a method for producing a processed transparent conductive film, comprising the steps of: heating a transparent conductive film of the transparent conductive film laminate; and peeling off the transparent conductive film and the carrier film. According to the production method of the present invention, the amount and direction of occurrence of the curl after the heating step such as drying can be controlled, so that the processing can be easily carried out and the production efficiency is good.

In the method for producing a transparent conductive film of the present invention, the step of heating is preferably a step of crystallizing the transparent conductive film. Thereby, the amount and direction of occurrence of the curl after the heating step such as drying can be controlled, so that the processing can be easily carried out and the production efficiency is good.

In the method for producing a transparent conductive film of the present invention, the step of the heat processing is preferably a step of drying the metal wiring formed of the photosensitive metal paste layer. Thereby, the amount and direction of occurrence of the curl after the heating step such as drying can be controlled, so that the processing can be easily carried out and the production efficiency is good.

1‧‧‧Protective film

2‧‧‧Adhesive layer

3‧‧‧Second hardened resin layer

4‧‧‧Transparent resin film

5‧‧‧First hardened resin layer

6‧‧‧Transparent conductive film

10‧‧‧ carrying film

20‧‧‧Transparent conductive film

S1‧‧‧ first main face

S2‧‧‧ second main surface

Simple description of the schema

Fig. 1 is a schematic cross-sectional view showing a transparent conductive thin film layered body according to an embodiment of the present invention.

Form for implementing the invention

Hereinafter, an embodiment of the transparent conductive thin film layered body of the present invention will be described with reference to the drawings. However, in part or all of the figure, Parts that are not required to be described are omitted, and parts that are enlarged or reduced for ease of explanation are shown. The terms indicating the positional relationship between the top and bottom are used for ease of explanation, and the intention of the structure of the present invention is not limited at all.

<Structure of laminated body>

Fig. 1 is a cross-sectional view schematically showing an embodiment of a transparent conductive thin film layered body of the present invention. The transparent conductive film laminate includes a carrier film 10 having an adhesive layer 2 on at least one side of the protective film 1 and a transparent conductive film 20 which is detachably laminated through the adhesive layer 2. The transparent conductive film 20 has a transparent resin film 4 and a transparent conductive film 6, and further preferably has: a first hardened resin layer 5 provided on one of the first main faces S1 of the transparent resin film 4; and a transparent resin The second hardened resin layer 3 of the second main surface S2 on the opposite side of the first main surface S1 of the film 4. The first cured resin layer 5 and the second cured resin layer 3 contain functions as an anti-adhesion layer and a hard coat layer. Further, the carrier film 10 is laminated on the second main surface S2 side of the transparent conductive film 20.

(transparent resin film)

The transparent resin film is formed of an amorphous cycloolefin-based resin and has characteristics of high transparency and low water absorption. By using an amorphous cycloolefin resin, the optical characteristics of the transparent conductive film used for the transparent conductive thin film laminate can be controlled.

The cycloolefin-based resin forming the amorphous cycloolefin-based resin is not particularly limited as long as it is a resin having a monomer unit composed of a cyclic olefin (cycloolefin). The cycloolefin resin used for the transparent resin film may be either a cycloolefin polymer (COP) or a cyclic olefin copolymer (COC). Ring The olefin copolymer is a non-crystalline cyclic olefin resin which is a copolymer of a cyclic olefin and an olefin such as ethylene.

The cyclic olefin is a polycyclic cyclic olefin and a monocyclic cyclic olefin. The polycyclic cyclic olefin may, for example, be norbornene, methylnorbornene, dimethylnorbornene, ethylnorbornene, ethylidene norbornene, butylnorbornene or dicyclopentane. Diene, dihydrodicyclopentadiene, methyl dicyclopentadiene, dimethyl dicyclopentadiene, tetracyclododecene, methyltetracyclododecene, dimethylcyclotetradecene , tricyclopentadiene, tetracyclopentadiene, and the like. Further, examples of the monocyclic cyclic olefin include cyclobutene, cyclopentene, cyclooctene, cyclooctadiene, cyclooctanetriene, and cyclododecene.

The cycloolefin-based resin is commercially available, and examples thereof include "ZEONOR" manufactured by ZEON Co., Ltd., "ARTON" manufactured by JSR Corporation, "TOPAS" manufactured by POLYPLASTIC Co., Ltd., and "APEL" manufactured by Mitsui Chemicals Co., Ltd., and the like.

The transparent resin film may be subjected to an etching treatment or a coating treatment such as pre-sputtering, corona discharge, flame, ultraviolet ray irradiation, electron beam irradiation, chemical conversion, oxidation, or the like on the surface to form a cured resin layer formed on the transparent resin film and The adhesion of a transparent conductive film or the like is improved. Further, before the formation of the cured resin layer, the transparent conductive film, or the like, the surface of the transparent resin film may be dusted and purified by solvent washing or ultrasonic cleaning as needed.

The thickness of the transparent resin film is preferably in the range of 20 to 150 μm, more preferably in the range of 30 to 100 μm, and more preferably in the range of 40 to 80 μm. If the thickness of the transparent resin film is less than the lower limit of the above range, the mechanical strength is insufficient, and the film substrate is formed into a roll shape to continuously form a transparent The case where the operation of the conductive film is difficult. On the other hand, when the thickness exceeds the upper limit of the above range, the scratch resistance of the transparent conductive film and the dot characteristics for the touch panel cannot be improved.

The glass transition temperature (Tg) of the amorphous cycloolefin resin of the transparent resin film is not particularly limited, but is preferably 130 ° C or higher, preferably 160 ° C or higher, and more preferably 180 ° C or higher. Thereby, the amount of curl generation and the direction after the heating step such as drying can be controlled, and thus the transparent conductive thin film layered body can be easily processed and transported.

The heat-shrinkage ratio in the MD direction and the TD direction when the resin film raw material forming the transparent resin film (the film before the layering of the cured resin layer and before the heat treatment) is heated at 130 ° C for 90 minutes is preferably 0.3% or less, and is 0.2%. The following is preferred, and is preferably 0.1% or less. In this way, the transparent conductive film having excellent workability and transparency can be obtained, and the amount and direction of curling after the heating step such as drying can be controlled. Therefore, the transparent conductive thin film layered body can be easily processed and transported.

The transparent resin film is easily formed into a low retardation film having a phase difference (R0) of 0 nm to 10 nm in the in-plane direction or a λ/4 film having a phase difference of about 80 nm to 150 nm in the in-plane direction, and is used together with the polarizing plate. In this case, it can have good visibility. Further, the in-plane phase difference (R0) is a phase difference in the retardation film (layer) plane measured by light having a wavelength of 589 nm at 23 °C.

(hardened resin layer)

The cured resin layer includes a first hardened resin layer provided on one of the first main surface sides of the transparent resin film, and a second hardened resin layer provided on the opposite side of the second main surface side Hardened resin layer. Since the transparent resin film formed of the cycloolefin resin is easily damaged in the steps of forming the transparent conductive film, patterning the transparent conductive film, or the like, or mounting it on an electronic device, it is preferable to form the first hardening on both sides of the transparent resin film. a resin layer and a second hardened resin layer.

The hardened resin layer is a layer obtained by hardening a hardening type resin. The resin to be used can be used without any particular limitation. The film after the formation of the cured resin layer has sufficient strength and transparency, and examples thereof include a thermosetting resin, an ultraviolet curing resin, an electron beam curing resin, and a two-liquid mixing type. Resin, etc. Among them, an ultraviolet curable resin which can efficiently form a hardened resin layer by a simple processing operation by a hardening treatment by ultraviolet irradiation is preferably used.

Examples of the ultraviolet curable resin include various resins such as polyester-based, acrylic-based, urethane-based, guanamine-based, polyfluorene-based, and epoxy-based resins, and include ultraviolet curable monomers and oligomers. Materials, polymers, etc. The ultraviolet curable resin to be used is an acrylic resin or an epoxy resin, and an acrylic resin is preferred.

The hardened resin layer may contain particles. By blending the particles in the cured resin layer, ridges can be formed on the surface of the cured resin layer, and the tack resistance can be appropriately imparted to the transparent conductive film.

The particles may be transparent to various metal oxides, glass, plastics or the like without any particular limitation. For example, inorganic particles such as cerium oxide, aluminum oxide, titanium oxide, zirconium oxide, and calcium oxide; and polymethyl methacrylate, polystyrene, polyurethane, acrylic resin, acrylic acid-styrene Copolymer, phenyl tripolyhydrogen diamine, melamine, polycarbon Crosslinked or uncrosslinked organic particles or polyoxynized particles composed of various polymers such as acid esters. The above-mentioned particles may be used singly or in combination of two or more kinds, and organic particles are preferred. From the viewpoint of the refractive index, the organic particles are preferably acrylic resins.

The particle size of the particles is not particularly limited, and may be appropriately set in consideration of the relationship between the degree of protrusion of the cured resin layer and the thickness of the flat region other than the ridge. In addition, from the viewpoint of sufficiently imparting tack resistance to the transparent conductive film and sufficiently suppressing an increase in haze, the particle size of the particles is preferably from 0.1 to 3 μm, more preferably from 0.5 to 2.5 μm. In addition, in the present specification, the "mode particle diameter" is a particle diameter showing the maximum value of the particle size distribution, and a flow type particle image analyzer (product name "FPTA-3000S" manufactured by Sysmex Co., Ltd.) is used. It was determined under the predetermined conditions (protective solution: ethyl acetate, measurement mode: HPF measurement, measurement method: total count). The measurement sample was diluted to 1.0% by weight with ethyl acetate, and uniformly dispersed using an ultrasonic cleaner.

The content of the particles is preferably 0.05 to 1.0 part by weight, and more preferably 0.1 to 0.5 part by weight, and more preferably 0.1 to 0.2 part by weight, per 100 parts by weight of the resin composition. When the content of the particles in the cured resin layer is small, it tends to be difficult to form a swell which sufficiently imparts adhesion resistance or slipperiness to the surface of the cured resin layer. On the other hand, when the content of the particles is too large, the haze of the transparent conductive film is increased by the light scattering of the particles, and the viewing property tends to be lowered. Further, when the content of the particles is too large, when the cured resin layer is formed (at the time of coating the solution), streaks are generated, the visibility is impaired, and the electrical properties of the transparent conductive film are not uniform.

The cured resin layer is obtained by coating a resin composition containing each of the curable resin and optionally added particles, a crosslinking agent, a starter, a sensitizer, and the like on the transparent resin film. When the resin composition contains a solvent, the solvent of the solvent is dried, and then hardened by using heat, an activated energy beam, or both. The heat may use conventional means such as an air circulation type oven or an IR heater, but is not limited to these methods. Examples of the activated energy beam include ultraviolet rays, electron beams, gamma rays, and the like, but are not particularly limited.

As the hardened resin layer, the above materials can be used, and a film can be formed by a wet coating method (coating method) or the like. For example, in the case where indium oxide (ITO) containing tin oxide is formed as a transparent conductive film, if the surface of the cured resin layer of the underlayer is smooth, the crystallization time of the transparent conductive film can be shortened. From this point of view, the cured resin layer is preferably formed by a wet coating method.

The thickness of the hardened resin layer is preferably from 0.5 μm to 5 μm, preferably from 0.7 μm to 3 μm, and most preferably from 0.8 μm to 2 μm. When the thickness of the cured resin layer is within the above range, the film collapse during the hardening and shrinkage of the damaged or cured resin layer can be prevented, and the deterioration of the visibility of the touch panel or the like can be prevented.

(transparent conductive film)

The transparent conductive film may be provided on the transparent resin film, but is preferably provided on the first hardened resin layer provided on one of the first main surface sides of the transparent resin film. The constituent material of the transparent conductive film is not particularly limited as long as it contains an inorganic substance, and is preferably selected from the group consisting of indium, tin, zinc, gallium, antimony, titanium, cerium, zirconium, magnesium, aluminum, gold, silver, copper, and palladium. a metal oxide of at least one metal of the group consisting of tungsten. The metal oxide may further comprise the above group as needed The metal atom shown. For example, indium oxide (ITO) containing tin oxide, indium oxide (ATO) containing cerium oxide, or the like is preferably used.

The thickness of the transparent conductive film is not particularly limited, but a continuous film having a surface resistance of 1 × 10 ³ Ω/□ or less and having good conductivity is preferably 10 nm or more. When the film thickness is too thick, the transparency is lowered, and the like, and therefore it is preferably 15 to 35 nm, and more preferably in the range of 20 to 30 nm. When the thickness of the transparent conductive film is less than 10 nm, the electric resistance of the surface of the film rises and it is difficult to form a continuous film. Further, when the thickness of the transparent conductive film exceeds 35 nm, the transparency may be lowered.

The method for forming the transparent conductive film is not particularly limited, and a conventionally known method can be employed. Specifically, a dry process such as a vacuum deposition method, a sputtering method, or an ion implantation method can be exemplified. Further, an appropriate method can be employed depending on the desired film thickness. Further, in the case where a transparent conductive film is formed on the first hardened resin layer, if the transparent conductive film is formed by a dry process of a sputtering method, the surface of the transparent conductive film can substantially maintain the surface shape of the first hardened resin layer of the base layer. . Therefore, in the case where there is a bulge on the first cured resin layer, the surface of the transparent conductive film can be desirably imparted with adhesion resistance and slipperiness.

The transparent conductive film can be crystallized by performing a heat annealing treatment (for example, at 80 to 150 ° C for about 30 to 90 minutes in an atmospheric environment) as needed. By crystallizing the transparent conductive film, in addition to lowering the resistance of the transparent conductive film, transparency and durability can be improved. The means for converting the amorphous transparent conductive film into crystalline form is not particularly limited, but an air circulating oven, an IR heater or the like can be used.

The definition of "crystal" will be formed on the transparent resin film. The transparent conductive film of the conductive film was immersed in hydrochloric acid at a concentration of 5 wt% at 20 ° C for 15 minutes, washed with water, dried, and measured for resistance between the terminals of 15 mm by a tester, and the resistance between the terminals was not more than 10 kΩ. In the case, the ITO film stops converting to crystalline form.

Further, the transparent conductive film can be patterned by etching or the like. The patterning of the transparent conductive film can be carried out using a conventional photolithography technique. It is preferred to use an acid for the etching solution. The acid may, for example, be an inorganic acid such as hydrogen chloride, hydrogen bromide, sulfuric acid, nitric acid or phosphoric acid; an organic acid such as acetic acid; and a mixture of such acids; and an aqueous solution of the acids. For example, in a transparent conductive film used in a capacitive touch panel or a matrix resistive touch panel, the transparent conductive film is preferably patterned into strips. Further, when the transparent conductive film is patterned by etching, if the crystal of the transparent conductive film is first formed, it may be difficult to pattern by etching. Therefore, the annealing treatment of the transparent conductive film is preferably performed after patterning the transparent conductive film.

The transparent conductive film may be amorphous or crystalline when the film is carried by a film to be described later. However, when the transparent conductive film laminate of the present invention is used, the transparent conductive film adheres the protective film to the non-adhesive layer. After the transparent conductive film in the crystalline state is subjected to annealing treatment and converted into crystal, it is possible to control the generation of curl of the transparent conductive thin film laminate.

(metal nanowire)

The aforementioned transparent conductive film may comprise a metal nanowire. The metal nanowire is made of metal, and has a needle shape or a linear shape and a conductive material having a diameter of a nanometer. The metal nanowires may be linear or curved. If used A transparent conductive film composed of a metal nanowire can form a transparent conductive film having a small electrical resistance by forming a metal nanowire in a mesh shape, even if a small amount of the metal nanowire can form a good electrical conduction path. . Further, by forming the metal nanowires in a mesh shape and forming openings in the gaps between the meshes, a transparent conductive film having a high light transmittance can be obtained.

Any metal constituting the metal nanowire can be any suitable metal as long as it is a metal having high conductivity. Examples of the metal constituting the metal nanowire include silver, gold, copper, nickel, and the like. Further, a material which has been subjected to a plating treatment (for example, a gold plating treatment) with the metals may also be used. Among them, silver, copper or gold is preferred from the viewpoint of conductivity, and silver is more preferable.

<Transparent Conductive Film>

The transparent conductive film has a transparent resin film and a transparent conductive film. In the transparent conductive film, the heat shrinkage ratio in the MD direction and the TD direction when heated at 130 ° C for 90 minutes is preferably 0.3% or less, more preferably 0.2% or less, and still more preferably 0.1% or less. In this way, the transparent conductive film having excellent workability and transparency can be controlled, and the amount or direction of curling after the heating step such as drying can be controlled. Therefore, the transparent conductive thin film layered body can be easily processed and transported.

(optical adjustment layer)

Between the first hardened resin layer and the transparent conductive film, one or more optical adjustment layers may be further included. In the case where the transmittance of the transparent conductive film is increased or the transparent conductive film is patterned, the optical adjustment layer can reduce the transmittance difference or the reflectance difference between the pattern portion where the pattern remains and the opening portion where the pattern does not remain, and can be used to obtain A transparent conductive film with excellent visibility.

The optical adjustment layer is formed of an inorganic substance, an organic substance, or a mixture of an inorganic substance and an organic substance. The material forming the optical adjustment layer may, for example, be NaF, Na ₃ AlF ₆ , LiF, MgF ₂ , CaF ₂ , SiO ₂ , LaF ₃ , CeF ₃ , Al ₂ O ₃ , TiO ₂ , Ta ₂ O ₅ , ZrO ₂ , An inorganic substance such as ZnO, ZnS, or SiO _x (x is 1.5 or more and less than 2); and an organic substance such as an acrylic resin, an epoxy resin, a urethane resin, a melamine resin, an alkyd resin, or a siloxane polymer . In particular, it is preferred to use a thermosetting resin formed of a mixture of a melamine resin, an alkyd resin, and an organic decane condensate. The optical adjustment layer can be formed by a coating method such as a wet method, a gravure coating method or a rod coating method, a vacuum deposition method, a sputtering method, an ion implantation method, or the like.

The optical adjustment layer may have nano fine particles having an average particle diameter of from 1 nm to 500 nm. The content of the nanoparticles in the optical adjustment layer is preferably from 0.1% by weight to 90% by weight. The average particle diameter of the nanoparticles used in the optical adjustment layer is preferably in the range of 1 nm to 500 nm as described above, and more preferably 5 nm to 300 nm. Further, the content of the nanoparticles in the optical adjustment layer is preferably from 10% by weight to 80% by weight, more preferably from 20% by weight to 70% by weight. By including the nanoparticles in the optical adjustment layer, the adjustment of the refractive index of the optical adjustment layer itself can be easily performed.

Examples of the inorganic oxide forming the nanoparticles include fine particles such as cerium oxide (cerium oxide), hollow nano cerium oxide, titanium oxide, aluminum oxide, zinc oxide, tin oxide, zirconium oxide, and cerium oxide. Among the fine particles of the oxide, fine particles of cerium oxide (cerium oxide), titanium oxide, aluminum oxide, zinc oxide, tin oxide, zirconium oxide or cerium oxide are preferred. These fine particles of the oxide may be used alone or in combination of two or more.

The thickness of the optical adjustment layer is preferably from 10 nm to 200 nm, and 20 nm to 150 nm is preferred, and more preferably 30 nm to 130 nm. If the thickness of the optical adjustment layer is too small, it is difficult to form a continuous film. Further, when the thickness of the optical adjustment layer is too large, the transparency of the transparent conductive film is lowered, and cracks tend to occur.

(metal wiring)

Although the metal wiring can be formed by etching after being formed on the transparent conductive film, it is preferable to form it using a photosensitive metal paste as described below. That is, after the transparent conductive film is patterned, a photosensitive conductive paste is formed on the transparent resin film or the transparent conductive film to form a photosensitive metal paste layer, and then the photomask is laminated or close to and transmitted through the mask. The metal paste layer is exposed, then developed, and after patterning, a metal wiring is produced through a drying step. That is, the pattern of the metal wiring can be formed by a conventional photolithography method or the like.

The photosensitive conductive paste preferably contains conductive particles such as metal powder and a photosensitive organic component. The material of the conductive particles of the metal powder preferably contains at least one selected from the group consisting of Ag, Au, Pd, Ni, Cu, Al, and Pt, and is preferably Ag. The volume average particle diameter of the conductive particles of the metal powder is preferably from 0.1 μm to 2.5 μm.

The conductive particles other than the metal powder may be metal-coated resin particles coated on the surface of the resin particles by metal. The material of the resin particles contains particles as described above, but an acrylic resin is preferred. The metal-coated resin particles are obtained by reacting a decane coupling agent on the surface of the resin particles and further coating the surface with a metal. By using a decane coupling agent, the dispersion of the resin component can be stabilized to form uniform metal-coated resin particles.

The photosensitive conductive paste may further comprise a glass frit. The volume average particle diameter of the glass material is preferably from 0.1 μm to 1.4 μm, and the 90% particle diameter is preferably from 1 to 2 μm and the maximum size is preferably 4.5 μm or less. Although the composition of the glass material is not particularly limited, it is preferred to blend Bi ₂ O _{3 in a} range of from 30% by weight to 70% by weight based on the whole. The oxide which may be contained in addition to Bi ₂ O ₃ may include SiO ₂ , B ₂ O ₃ , ZrO ₂ , Al ₂ O ₃ . Preferably, it is an alkali-free glass material which does not substantially contain Na ₂ O, K ₂ O, and Li ₂ O.

The photosensitive organic component preferably contains a photosensitive polymer and/or a photosensitive monomer. The photosensitive polymer is preferably used in an acrylic resin side chain formed of a polymer selected from a compound having a carbon-carbon double bond such as methyl (meth) acrylate or ethyl (meth) acrylate and a copolymer thereof. A photoreactive base or the like is attached to the end of the molecule. A preferred photoreactive group is exemplified by an ethylenically unsaturated group such as a vinyl group, an allyl group, a propenyl group or a methacryl group. The content of the photopolymer is from 1 to 30% by weight, and preferably from 2 to 30% by weight.

The photosensitive monomer may, for example, be a (meth) acrylate monomer such as methacrylic acid acrylate or ethyl acrylate; and γ-methacryloxytrimethoxy decane or 1-vinyl-2-pyrrolidone; Etc., one type or two or more types can be used.

In terms of the sensitivity of light, it is preferred that the photosensitive conductive paste contains 5 to 40% by weight of the photosensitive organic component with respect to 100 parts by weight of the metal powder, and more preferably 10 parts by weight to 30 parts by weight. Further, the photosensitive conductive paste of the present invention is preferably a photopolymerization initiator, a sensitizer, a polymerization inhibitor, or an organic solvent as needed.

The thickness of the metal layer is not particularly limited. For example, when a pattern wiring is formed by removing a part of the surface of the metal layer by etching or the like, the thickness of the metal layer can be appropriately set so that the formed pattern wiring has a desired pattern. resistance. Therefore, the thickness of the metal layer is preferably from 0.01 to 200 μm, and more preferably from 0.05 to 100 μm. If the thickness of the metal layer is within the above range, the resistance of the pattern wiring is not excessively high, and the power consumption of the device is not excessive. Further, the production efficiency of the metal layer film formation is improved, and the accumulated heat at the time of film formation becomes small, so that heat shrinkage is less likely to occur on the film.

When the transparent conductive film is a transparent conductive film for a touch panel used in combination with a display, a portion corresponding to the display portion is formed by a patterned transparent conductive film, and a metal wiring made of a photosensitive conductive paste is used. The wiring portion of the non-display portion (for example, the peripheral portion). The transparent conductive film can also be used for the non-display portion, in which case the metal wiring can be formed on the transparent conductive film.

<bearing film>

The carrier film has an adhesive layer on at least one side of the protective film. The carrier film is adhered to the second main surface side of the transparent conductive film through the adhesive layer and the peelable transparent conductive film to form a transparent conductive film laminate. When the carrier film is peeled off from the transparent conductive film laminate, the adhesive layer may be peeled off together with the protective film, or only the protective film may be peeled off.

(protective film)

The material forming the protective film preferably has excellent transparency, mechanical strength, thermal stability, moisture barrier property, isotropic property and the like. From the viewpoint of controlling the amount and direction of occurrence of the curl, it is preferable to form the amorphous resin which is different from the amorphous cycloolefin resin which forms the transparent resin film. Further, the amorphous cycloolefin resin of the transparent resin film and the amorphous resin of the protective film are preferably resins having different constituent units. Here, the definition of "different" is Although the constituent units are different from each other, even if the resin having the same unit is different, the weight average molecular weight or the like is different.

The amorphous resin may, for example, be a cycloolefin resin or a polycarbonate resin. From the viewpoint of having excellent light transmittance, scratch resistance, water resistance, and good mechanical properties, a polycarbonate resin is preferred. Examples of the polycarbonate resin include aliphatic polycarbonates, aromatic polycarbonates, and aliphatic-aromatic polycarbonates. Specifically, for example, bisphenol A polycarbonate, branched bisphenol A polycarbonate, fired polycarbonate, copolycarbonate, block copolycarbonate, polyester carbonate, polyphosphonate carbonic acid Ester and the like. The polycarbonate resin may also contain, for example, a bisphenol A polycarbonate mixture, a polyester mixture, an ABS mixture, a polyolefin mixture, a styrene-maleic anhydride copolymer mixture, and the like mixed with other components. Commercial products of polycarbonate resin can be exemplified by "OPCON" manufactured by the company and "Panlite" manufactured by Teijin.

The weight average molecular weight of the aforementioned polycarbonate-based resin is preferably from 1.5 × 10 ⁴ to 3.5 × 10 ⁴ and more preferably from 2 × 10 ⁴ to 3 × 10 ⁴ from the viewpoint of controlling the glass transition temperature.

The protective film may be subjected to an etching treatment or a coating treatment such as pre-sputtering, corona discharge, flame, ultraviolet ray irradiation, electron beam irradiation, chemical conversion, oxidation, or the like on the surface, similarly to the transparent resin film, to bond the adhesive on the protective film. The adhesion of layers and the like is improved. Further, before the formation of the adhesive layer, the surface of the protective film may be dedusted and purified by solvent washing, ultrasonic cleaning, or the like as needed.

Improve the workability by controlling the amount and direction of curl generation In other words, the thickness of the protective film is preferably from 20 to 150 μm, more preferably from 30 to 100 μm, still more preferably from 40 to 80 μm.

The glass transition temperature (Tg) of the amorphous resin of the protective film is preferably 130 ° C or more, more preferably 135 ° C or more, and still more preferably 140 ° C or more. Thereby, the amount of curl generation and the direction after the heating step such as drying can be controlled, and thus the transparent conductive thin film layered body can be easily processed and transported.

The absolute value of the difference (ab) between the glass transition temperature a of the amorphous cycloolefin resin of the transparent resin film and the glass transition temperature b of the amorphous resin of the protective film is preferably 5° C. or higher and 7° C. or higher. Preferably, it is more preferably 10 ° C or more. Thereby, the amount and direction of curl generation can be controlled to improve workability and the like. Further, in the case of the same constituent unit, the glass transition temperature a of the amorphous cycloolefin resin of the transparent resin film is preferably higher than the glass transition temperature b of the amorphous resin of the protective film. Thereby, the amount and direction of curl generation can be controlled to improve workability and the like.

In the protective film, the heat shrinkage ratio in the MD and TD directions after heating at 130 ° C for 90 minutes is preferably 0.3% or less, more preferably 0.2% or less, and still more preferably 0.1% or less. In this way, the protective film having excellent workability and transparency can be obtained, and the amount and direction of curling after the heating step such as drying can be controlled, so that the transparent conductive thin film layered body can be easily transported.

(adhesive layer)

The adhesive layer can be used without particular limitation as long as it has transparency. Specifically, an acrylic polymer; a polyoxymethylene polymer; a polyester; a polyurethane; a polyamine; a polyvinyl ether; an ethyl acetate/vinyl chloride copolymer; Polyolefin; epoxy, fluorine, day However, a polymer such as a rubber or a rubber such as a rubber is a base polymer. In particular, an acrylic adhesive is preferably used because it has excellent optical transparency, exhibits adhesive properties such as appropriate wettability, cohesiveness, and adhesion, and also has excellent weather resistance and heat resistance.

The method for forming the pressure-sensitive adhesive layer is not particularly limited, and examples thereof include a method in which an adhesive composition is applied onto a release liner, and after drying, transfer to a base film (transfer method); on the protective film, directly A method of applying an adhesive composition, drying the method (direct printing method), and co-extruding. Further, as the adhesive, an adhesion-imparting agent, a plasticizer, a filler, an antioxidant, an ultraviolet absorber, a decane coupling agent, or the like can be suitably used as needed. The thickness of the adhesive layer is preferably from 5 μm to 100 μm, more preferably from 10 μm to 50 μm, still more preferably from 15 μm to 35 μm.

<Transparent Conductive Thin Film Laminate>

The transparent conductive film laminate includes a carrier film having an adhesive layer on at least one side of the protective film, and a transparent conductive film which is peelably laminated through the adhesive layer. Further, the carrier film is laminated on the other surface side of the transparent conductive film of the transparent conductive film.

In the transparent conductive thin film laminate, the transparent conductive thin film laminate was cut into 20 cm × 20 cm, and the transparent conductive film was heated at 130 ° C for 90 minutes, and the curl value A at the central portion and the average curl at the four corner portions were obtained. The difference (AB) of the value B is preferably from 0 to 50 mm, preferably from 5 to 45 mm, and more preferably from 10 to 40 mm. Thereby, the amount of curl generation and the direction after the heating step such as drying can be controlled, and thus the transparent conductive thin film layered body can be easily conveyed.

<Touch Panel>

The transparent conductive film in which the carrier film or the protective film is peeled off from the transparent conductive film laminate is suitably used as a transparent electrode of an electronic device such as a touch panel such as a capacitive method or a resistive film method.

When the touch panel is formed, other substrates such as glass or polymer film may be adhered to one or both of the main surfaces of the transparent conductive film through the adhesive layer. For example, a laminate may be formed, and the transparent substrate of the laminate system is adhered to the surface of the transparent conductive film on the side where the transparent conductive film is not formed through the transparent adhesive layer. The transparent substrate may be composed of one base film, or may be a laminate of two or more base films (for example, a transparent adhesive layer). Further, a hard coat layer may be provided on the outer surface of the transparent substrate adhered to the transparent conductive film. The adhesive layer for adhering the transparent conductive film and the substrate may be used without any particular limitation as long as it has transparency.

When the touch panel is formed using the transparent conductive film, the amount of curl generated after the heating step of drying can be controlled, and the transparent conductive thin film layered body can be easily conveyed, and the operability at the time of formation of the touch panel can be excellent. Therefore, a touch panel having excellent transparency and visibility can be manufactured with high productivity. In addition to the use of touch panels, it can also be used to shield electromagnetic waves and noise emitted by electronic devices.

<Method for Producing Processed Transparent Conductive Film>

The method for producing a transparent conductive thin film laminate of the present invention comprises the steps of: preparing a transparent conductive film on which a transparent conductive film is formed on a transparent resin film; and laminating the protective film on the transparent conductive film with an adhesive layer through an adhesive layer The other side of the membrane. Transparent conductive processing of the present invention The method for producing a thin film laminate includes the steps of: heating and processing the transparent conductive film of the transparent conductive film laminate; and peeling off the transparent conductive film and the carrier film. The heat processing step preferably includes a step of crystallizing the aforementioned transparent conductive film. The heat processing step preferably includes the step of drying the metal wiring formed of the photosensitive metal paste layer.

The transparent conductive film used in the step of preparing the transparent conductive film can form a cured resin layer on the transparent conductive film, and then form a transparent conductive film, or a transparent resin laminated body in which a cured resin layer is formed on the transparent resin film. Then, a transparent conductive film is formed on the cured resin layer, and a transparent conductive film in which a cured resin layer and a transparent conductive film are formed on the transparent resin film can be obtained. The optical adjustment layer can also be used by obtaining a preformed transparent resin laminate.

The step of laminating the protective film is to form an adhesive layer on the release substrate, and the carrier film is formed by transferring the adhesive layer on the protective film, and then the protective film is laminated on the transparent conductive film through the adhesive layer. The side of the transparent resin film forming the second hardened resin layer. In addition, a direct adhesive layer can also be formed on the protective film.

After the step of laminating, in order to crystallize the constituent components of the transparent conductive film, a heating step is introduced. The heating temperature is preferably carried out at a temperature of, for example, 130 ° C or lower, and more preferably 120 ° C or less, and the treatment time is, for example, 15 minutes to 180 minutes. Then, the transparent conductive film is etched, and the pattern portion is formed by etching.

The present invention preferably further comprises the steps of: coating the transparent conductive film on the transparent resin film or the transparent conductive film after patterning The photosensitive conductive paste is formed by coating the photosensitive conductive paste, and then the photosensitive metal paste layer is exposed by or close to the mask, or the metal wiring is obtained by screen printing or the like.

The drying temperature in the step of drying the metal wiring formed of the photosensitive metal paste layer is preferably carried out at a temperature of 130 ° C or lower, and more preferably 120 ° C or lower.

In the heating step for crystallizing the transparent conductive film, although the roll-to-roll process is used, the subsequent etching step and metal wiring step include patterning alignment of the metal wiring such as a photomask or a transparent conductive film, and the like. Singulation step. In this case, in order to align the transparent conductive film and the transparent conductive thin film laminate, the step of fixing to the adsorption plate is required. However, drying in the above temperature range can control the amount and direction of the curl, and thus The conveyance is carried out in the step of being fixed to the adsorption plate.

Example

Hereinafter, the present invention will be described in detail using examples, but the present invention is not limited to the examples below as long as it does not exceed the gist of the invention.

[Example 1]

(Preparation of a resin composition for forming a hardened resin layer)

In the curable resin composition in which the spherical particles are mixed, the curable resin composition containing the spherical particles contains 100 parts by weight of an ultraviolet curable resin composition (manufactured by DIC Corporation, trade name "UNIDIC (registered trademark) RS29-120). And 0.2 parts by weight of acrylic spherical particles having a mode diameter of 1.9 μm (manufactured by Soken Chemical Co., Ltd., trade name "MX-180TA").

(forming a hardened resin layer)

a curable resin composition prepared by mixing spherical particles into a polycycloolefin film (manufactured by ZEON Co., Ltd., trade name "ZEONOR (registered trademark)") having a thickness of 50 μm and a glass transition temperature of 165 ° C is applied thereto. A coating layer is formed. Next, the coating layer was irradiated with ultraviolet rays from the side on which the coating layer was formed to form a second cured resin layer having a thickness of 1.0 μm. On the other surface of the polycycloolefin film, a first cured resin layer having a thickness of 1.0 μm was formed in the same manner as above except that spherical particles were not added.

(Forming a transparent conductive film)

Next, a polycycloolefin film having a hardened resin layer formed on both sides thereof was placed in a coiling sputtering apparatus, and an amorphous indium tin oxide layer having a thickness of 27 nm was formed on the surface of the first cured resin layer (composition: SnO ₂ 10 wt%) ).

(forming a carrier film)

An acrylic polymer having a weight average molecular weight of 600,000 was obtained by usual solution polymerization in accordance with butyl acrylate/acrylic acid = 100/6 (by weight). To 100 parts by weight of the acrylic polymer, 6 parts by weight of an epoxy-based crosslinking agent (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name "TETRAD-C (registered trademark)" was added to prepare an acrylic adhesive. The acrylic adhesive prepared as described above was applied to the release treated surface of the molded PET film, followed by heating at 120 ° C for 60 seconds to form an adhesive layer having a thickness of 20 μm. Next, the thickness was 75 μm and the glass was applied. The PET film was adhered to one surface of a polycarbonate resin film (trade name "OPCON-PC" manufactured by Hohsen Co., Ltd.) having a transfer temperature of 145 ° C. The PET film was peeled off from the adhesive film, and then the PET film was peeled off. A carrier film having an adhesive layer on one side of the protective film.

(Formation of a transparent conductive thin film laminate)

On the side of the surface of the transparent conductive film where the transparent conductive film is not formed, an adhesive layer carrying the film is laminated to form a transparent conductive thin film layered body.

[Embodiment 2]

In the same manner as in Example 1, except that a polycycloolefin film (trade name "ZEONOR (registered trademark)" manufactured by ZEON Co., Ltd.) having a glass transition temperature of 136 ° C was used as the transparent resin film. A transparent conductive thin film laminate.

[Example 3]

In the same manner as in Example 1, except that a polycycloolefin film (trade name "ZEONOR (registered trademark)" manufactured by ZEON Co., Ltd.) having a thickness of 50 μm and a glass transition temperature of 136 ° C was used as the protective film. Method A transparent conductive thin film laminate was produced.

[Comparative Example 1]

In the same manner as in Example 1, a transparent conductive film was produced in the same manner as in Example 1 except that a PET film (manufactured by Mitsubishi Plastics, trade name "DIAFOIL") having a thickness of 50 μm and a glass transition temperature of 70 ° C was used as the protective film. Thin film laminate.

[Comparative Example 2]

In the same manner as in Example 1, a transparent conductive film was produced in the same manner as in Example 1 except that a PET film (manufactured by Mitsubishi Plastics, trade name "DIAFOIL") having a thickness of 188 μm and a glass transition temperature of 70 ° C was used as the protective film. Thin film laminate.

<evaluation>

(1) Measurement of thickness

The thickness was measured by a micrometer thickness gauge (manufactured by Mittotoyo Co., Ltd.) having a thickness of 1 μm or more. Further, the thickness of less than 1 μm or the thickness of the optical adjustment layer (100 nm) was measured by an instantaneous multi-photometric system (manufactured by Otsuka Electronics Co., Ltd., MCPD2000). For the thickness of the nano-size of the ITO film or the like, a sample for cross-section observation was produced by FB-2000A (manufactured by Hitachi High-Technologies Co., Ltd.), and HF-2000 (Hitachi High-Technologies Co., Ltd.) was used for the cross-sectional TEM observation. The system is used to measure the film thickness. The results of the evaluation are shown in Table 1.

(2) Measurement of curl value

The transparent conductive thin film laminates obtained in the examples and the comparative examples were cut into a size of 20 cm × 20 cm. After heating at 130 ° C for 90 minutes while the ITO surface was on, it was allowed to stand at room temperature (23 ° C) for 1 hour. Then, the sample was placed on a horizontal surface with the ITO surface in the upper state, and the height (curled value A) calculated from the horizontal plane of the central portion was measured. Further, the height from the horizontal plane of the four corners was measured, and the average value (curl value B) was calculated. The value (A-B) obtained by subtracting the curl value B from the curl value A was calculated as the amount of curl. The results of the evaluation are shown in Table 1.

(3) Thermal shrinkage rate in the MD direction and the TD direction

The heat shrinkage ratio in the longitudinal direction (MD direction) and the width direction (TD direction) of each of the transparent conductive film and the protective film was measured as follows. Specifically, a transparent conductive film having a width of 100 mm and a length of 100 mm and a protective film (test piece) were cut out, and a cross was drawn at four corners and measured by a CNC three-dimensional measuring machine (manufactured by Mitotoyo Co., Ltd., LEGEX774). Central of the fork The length in front of the heating in the MD direction of 4 points and the TD direction (mm). Then, it was placed in an oven and heat-treated (130 ° C, 90 minutes). After cooling at room temperature for 1 hour, the MD direction of the 4 corners and the length of the heating in the TD direction (mm) were measured by a CNC three-dimensional measuring machine, and the measured values were substituted into the following equations. The heat shrinkage rate in the MD direction and the TD direction is obtained. The results of the evaluation are shown in Table 1. Heat shrinkage ratio (%) = [[length before heating (mm) - length after heating (mm)] / length before heating (mm)] × 100. The results of the evaluation are shown in Table 1.

(4) Measurement of surface resistance

According to JIS K7194, it is measured by the 4-terminal method.

(5) Measurement of glass transition temperature (Tg)

The glass transition temperature (Tg) is obtained in accordance with the provisions of JIS K7121.

(6) Measurement of weight average molecular weight

The weight average molecular weight is measured by gel permeation chromatography (GPC). The measurement conditions of GPC are as follows.

Measuring machine: TOSOH product name HLC-8120

GPC pipe column: TOSOH product name G4000H _XL + trade name G2000H _XL + trade name G1000H _XL (each 7.8mmΦ×30cm, total 90cm)

Column temperature: 40 ° C

Lysate: tetrahydrofuran

Flow rate: 0.8ml/min

Inlet pressure: 6.6MPa

Standard sample: polystyrene

(Results and investigation)

In the transparent conductive thin film laminates of Examples 1 to 3, the direction in which the curl was generated was convex in the case where the transparent conductive film was on, and the amount of curl generation was controlled to be 20 to 35 mm. On the other hand, in the transparent conductive thin film laminate of Comparative Example 1, in the case where the transparent conductive film was on, the film was largely curled in the concave direction, and the curl value at the four corners could not be measured. In the transparent conductive thin film laminate of Comparative Example 2, the direction in which the curl was generated was in the concave direction in the case where the transparent conductive film was on, and a large curl was generated to cause the end portion to float. When the transparent conductive film was curled in the concave direction in the case of the comparative examples 1 to 2, it was difficult to process by suction by the chuck.

1‧‧‧Protective film

2‧‧‧Adhesive layer

3‧‧‧Second hardened resin layer

4‧‧‧Transparent resin film

5‧‧‧First hardened resin layer

6‧‧‧Transparent conductive film

10‧‧‧ carrying film

20‧‧‧Transparent conductive film

S1‧‧‧ first main face

S2‧‧‧ second main surface

Claims (10)

A transparent conductive thin film laminate comprising: a carrier film having an adhesive layer on at least one side of the protective film; and a transparent conductive film which is releasably laminated through the adhesive layer, the transparent conductive film being transparent a resin film and a transparent conductive film, wherein the transparent resin film is made of an amorphous cycloolefin resin, and the transparent resin film has a thickness of 20 to 150 μm, and the carrier film is laminated on the transparent conductive film and the transparent conductive film. On the other surface side, the protective film is formed of an amorphous resin different from the amorphous cycloolefin resin forming the transparent resin film, and the amorphous resin of the protective film has a glass transition temperature of 130 ° C or higher, and the protective film. The thickness is 20 to 150 μm, and the transparent conductive film laminate is cut into 20 cm × 20 cm, and the curl value A and the average curl of the 4 corner portions of the central portion after the transparent conductive film is heated at 130 ° C for 90 minutes. The difference (AB) of the value B is 0 to 50 mm. The transparent conductive film laminate according to claim 1, wherein the amorphous cycloolefin resin of the transparent resin film has a glass transition temperature of 130 ° C or higher, and has a first cured resin layer provided on the transparent resin film. One of the first major surface sides; and a second hardened resin layer The second main surface side is opposite to the first main surface of the transparent resin film. The transparent conductive thin film laminate according to claim 1, wherein the difference between the glass transition temperature a of the amorphous cycloolefin resin of the transparent resin film and the glass transition temperature b of the amorphous resin of the protective film (ab) The absolute value is above 5 °C. The transparent conductive film laminate according to claim 1, wherein the amorphous cycloolefin resin of the transparent resin film and the amorphous resin of the protective film are different in composition. The transparent conductive film laminate according to claim 1, wherein the protective film is made of a polycarbonate resin, has a weight average molecular weight of 2 × 10 ⁴ or more, and has a heat shrinkage ratio in MD after heating at 130 ° C for 90 minutes. And in the TD direction is 0.3% or less. The transparent conductive thin film laminate according to claim 1, wherein one or more optical adjustment layers are further provided between the first cured resin layer and the transparent conductive film. A touch panel obtained by using the transparent conductive thin film laminate of any one of claims 1 to 6. A method for producing a processed transparent conductive film, comprising the steps of: heating a transparent conductive film of the transparent conductive film laminate according to any one of claims 1 to 6; and peeling off the transparent conductive film and the carrier film. The method for producing a transparent conductive film according to claim 8, wherein the step of heating is a step of crystallizing the transparent conductive film. The method for producing a transparent conductive film according to claim 8, wherein the step of heating is a step of drying the metal wiring formed of the photosensitive metal paste layer.