KR102076894B1 - Transparent conductive film laminate, touch panel obtained by using same, and method for producing transparent conductive film - Google Patents

Abstract

When cycloolefin resin is used for the base material of a transparent conductive film, the transparent conductive film laminated body which can control the curl of a transparent conductive film laminated body after a heating process, and ensures the subsequent process yield, and the touch panel obtained using it, And it provides the manufacturing method of a transparent conductive film.
The transparent resin film 4 in this invention consists of amorphous cycloolefin resin, and the said protective film 1 is a ratio different from the amorphous cycloolefin resin which forms the transparent resin film 4 It is formed from qualitative resin, and the protective film 1 has a glass transition temperature of 130 degreeC or more, cuts a transparent conductive film laminated body to 20 cm x 20 cm, and makes 130 degreeC transparent transparent film 6 into an upper surface The difference (A-B) between the curl value A of the center part and the average curl value B of the four corner parts after heating for 90 minutes at is a transparent conductive film laminate having 0 to 50 mm.

Description

Transparent conductive film laminated body, the touchscreen obtained using the same, and the manufacturing method of a transparent conductive film TECHNICAL FIELD [TECHNICAL FIELD] [TRANCHPARENT CONDUCTIVE FILM LAMINATE, TOUCH PANEL OBTAINED BY USING SAME]

This invention relates to a transparent conductive film laminated body, a touch panel obtained using the same, and a manufacturing method of a transparent conductive film, and is especially a technique useful for generation | generation control of a curl.

Conventionally, in the capacitive touch panel configuration, polyethylene terephthalate (PET) is widely used as a base film of a transparent conductive film. However, since a PET film is stretched into a film and has a high phase difference, it is difficult to use it as a basis of a polarizing plate. Therefore, in patent document 1, the transparent conductive film using cycloolefin resin as a base film for low phase difference is proposed.

When cycloolefin resin is used for a base film, since a base material is very fragile and it is easy to be damaged, a hard-coat process is required for both surfaces of a base film in order to convey by a roll-to-roll manufacturing method. When forming a hard-coat layer on both surfaces of a base film, blocking (sticking of films when winding up a film) will arise, and it is necessary to provide anti blocking property to at least one side. In addition, when forming a transparent conductive layer into a film by sputtering etc. and performing the pattern wiring process of a transparent conductive layer, it is necessary to perform a handling process with a sheet material including a chemical | medical solution / heating process, and is a base material on the opposite side to a transparent conductive layer. It is necessary to laminate | stack a surface protection film on a film back surface.

In patent document 2, the laminated body whose base film and surface protection film of a transparent conductive film are both PET films is disclosed. In such a case, the reduction of curl was realized by adjusting the thermal contraction rate of each film by a heating process so that conveyance may be satisfactorily carried out.

Japanese Unexamined Patent Publication No. 2013-114344 Japanese Laid-Open Patent Publication 2008-251529

However, when a cycloolefin resin film is used as a base film of a transparent conductive film and a PET base material is used as a surface protection film, when a transparent conductive film is comforted after a heating process from the difference of both heat contraction rate and a linear expansion coefficient, Curl | corrugation of the transparent conductive film surface generate | occur | produces, and when a transparent conductive film laminated body is processed and conveyed, problems, such as being unable to adsorb | suck by air or passing through the gate between processes, generate | occur | produce, and it is stable and continuously It becomes difficult to carry out production. Moreover, the roll of a transparent conductive film is cut | disconnected, and also in the subsequent processing process, there exists a difficulty in not being able to adsorb | suck a sheet-like transparent conductive film with air.

Therefore, the objective of this invention is the case where a cycloolefin resin is used for the base material of a transparent conductive film, The transparent conductive film laminated body which can control the curl of a transparent conductive film laminated body after a heating process, and can secure the subsequent process yield And it is providing the touch panel obtained using it and the manufacturing method of a transparent conductive film.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, the present inventors discovered that the said objective can be achieved by employ | adopting the following structure, and came to this invention.

That is, the transparent conductive film laminated body of this invention is a transparent conductive film laminated body containing the carrier film which has an adhesive layer in the at least one surface side of a protective film, and the transparent conductive film laminated | stacked so that peeling was possible through the said adhesive layer. The transparent conductive film includes a transparent resin film and a transparent conductive film, wherein the transparent resin film is made of amorphous cycloolefin resin, and the thickness of the transparent resin film is 20 to 150 μm, and the carrier The film is laminated | stacked on the other surface side with the transparent conductive film of the said transparent conductive film, The said protective film is formed with amorphous resin different from the amorphous cycloolefin resin which forms the said transparent resin film, The glass transition temperature of amorphous resin of the said protective film is 130 degreeC or more, and the thickness of the said protective film is 20-150 micrometers, and the said transparent conductive The difference (A-B) between the curl value A in the center part and the average curl value B in the four corner parts is 0 to 50 after the film laminate is cut to 20 cm × 20 cm and heated at 130 ° C. for 90 minutes with the transparent conductive film as an upper surface. It is a transparent conductive film laminated body which is mm, It is characterized by the above-mentioned. In addition, the various physical property values in this invention are the values measured by the method employ | adopted in an Example etc ..

The cause of curling is considered to be because the thermal contraction rate and linear expansion coefficient of cycloolefin resin and PET differ. For example, when the transparent resin film is cycloolefin-based resin and the protective film is PET, curls in the concave direction are generated when the transparent conductive film is placed upwards, so that it cannot be adsorbed by the adsorption plate, which makes processing difficult. In the present invention, the thermal contraction rate and the coefficient of linear expansion by using an amorphous cycloolefin resin for the transparent resin film as described above and using an amorphous resin different from the amorphous cycloolefin resin for forming the transparent resin film on the protective film. In this case, curl can be generated in the convex direction when the transparent conductive film is placed upward in the temperature lowering step after heating. From this, in the conveyance process, the surface on the protective film side of a transparent conductive film laminated body can be suctioned by air, it can convey stably and continuously, and the metal wiring etc. are possible even after a heating process.

The transparent conductive film laminated body of this invention is the agent in which the glass transition temperature of amorphous cycloolefin resin of the said transparent resin film is 130 degreeC or more, and was formed in one 1st main surface side of the said transparent resin film. It is preferable to have a 1st cured resin layer and the 2nd cured resin layer formed in the 2nd main surface side on the opposite side to the said 1st main surface of the said transparent resin film. By making the glass transition temperature of amorphous cycloolefin resin of a transparent resin film 130 degreeC or more, it can be approximated to the linear expansion coefficient and thermal contraction rate of the amorphous resin used for the protective film, and in heating processes, such as drying, Curling can be further controlled, and the yield of subsequent processes can be ensured. Moreover, since the cured resin layer is formed on both surfaces of a transparent resin film, it becomes difficult to be damaged at each process, such as formation of a transparent conductive film, patterning, or mounting to an electronic device.

The absolute value of the difference (a-b) of glass transition temperature a of amorphous cycloolefin resin of the said transparent resin film of this invention, and glass transition temperature b of amorphous resin of the said protective film is 5 degreeC or more. It is preferable. Thereby, when putting the transparent conductive film side of a transparent conductive film laminated body upward, a transparent conductive film laminated body can be curled in a convex direction in a preferable range, conveyance of a transparent conductive film laminated body becomes easy, and the yield of a subsequent process is improved. It can be secured.

It is preferable that amorphous cycloolefin resin of the said transparent resin film in this invention, and amorphous resin of the said protective film are resin from which a structural unit differs from each other. Thereby, when putting the transparent conductive film side of a transparent conductive film laminated body upward, a transparent conductive film laminated body can be curled in a convex direction in a preferable range, conveyance of a transparent conductive film laminated body becomes easy, and the yield of a subsequent process is improved. It can be secured.

It is preferable that the said protective film in this invention consists of polycarbonate resin, the weight average molecular weight is 2 * 10 <^4> or more, and the heat shrink rate after heating for 90 minutes at 130 degreeC is 0.3% or less in MD and TD directions. Do. Since the protective film is made of polycarbonate resin, a transparent conductive film laminate having good mechanical properties and processability is obtained. Moreover, since excessive thermal contraction at the time of the heating process of a transparent conductive film can be suppressed, generation | occurrence | production of a curl can be controlled at a higher level, and the processing conveyance of a transparent conductive film laminated body can be carried out stably and continuously.

It is preferable that the transparent conductive film laminated body of this invention is equipped with one or more optical adjustment layers further between the said 1st cured resin layer and the said transparent conductive film. Since the refractive index can be controlled by the optical adjusting layer, the difference in reflectance between the pattern forming portion and the pattern opening when the transparent conductive film is patterned can be reduced, and the transparent conductive film pattern is difficult to be seen, such as a display device such as a touch panel. The visibility becomes good in.

It is preferable that the touchscreen of this invention is obtained using the said transparent conductive film laminated body. When the said transparent conductive film laminated body is used, curl generation in a heating process, such as drying, can be controlled more, and the process conveyance of a transparent conductive film laminated body becomes easy, and work efficiency improves.

This invention also includes the manufacturing method of the processed transparent conductive film containing the process of heat-processing the transparent conductive film of the said transparent conductive film laminated body, and the process of peeling a transparent conductive film and a carrier film. According to the manufacturing method of this invention, since the generation amount and direction of curl after a heating process, such as drying, can be controlled, processing conveyance becomes easy and manufacturing efficiency is favorable.

In the manufacturing method of the transparent conductive film in this invention, it is preferable that the process of heat processing is a process of crystallizing the said transparent conductive film. Thereby, since the generation amount and direction of curl after a heating process, such as drying, can be controlled, processing conveyance becomes easy and manufacturing efficiency is favorable.

In the manufacturing method of the transparent conductive film in this invention, it is preferable that the process of heat processing is a process of drying the metal wiring formed with the photosensitive metal paste layer. Thereby, since the generation amount and direction of curl after a heating process, such as drying, can be controlled, processing conveyance becomes easy and manufacturing efficiency is favorable.

BRIEF DESCRIPTION OF THE DRAWINGS It is typical sectional drawing of the transparent conductive film laminated body which concerns on one Embodiment of this invention.

Embodiment of the transparent conductive film laminated body of this invention is described below, referring drawings. However, in part or all of the drawings, parts unnecessary for the description are omitted, and parts shown are enlarged or reduced in order to facilitate explanation. Terms indicating positional relations such as up and down are merely used to facilitate explanation, and there is no intention to limit the configuration of the present invention.

<Structure of laminated body>

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows typically one Embodiment of the transparent conductive film laminated body of this invention. The transparent conductive film laminated body is the transparent conductive film 20 laminated | stacked so that peeling was possible through the carrier film 10 which has the adhesive layer 2 on the at least one surface side of the protective film 1, and the adhesive layer 2. ) The transparent conductive film 20 has the transparent resin film 4 and the transparent conductive film 6, and the 1st cured resin layer formed in the 1st main surface S1 side of the transparent resin film 4 ( 5) and the 2nd cured resin layer 3 formed in the 2nd main surface S2 side opposite to the 1st main surface S1 of the transparent resin film 4 is preferable. The 1st cured resin layer 5 and the 2nd cured resin layer 3 contain what functions as an anti blocking layer and a hard-coat layer. In addition, the carrier film 10 is laminated | stacked on the 2nd main surface S2 side of the transparent conductive film 20. FIG.

(Transparent resin film)

The transparent resin film is formed of amorphous cycloolefin resin and has high transparency and low water absorption characteristics. By employ | adopting amorphous cycloolefin type resin, the control of the optical characteristic of the transparent conductive film used for a transparent conductive film laminated body becomes possible.

As cycloolefin resin which forms amorphous cycloolefin resin, it will not specifically limit, if it is resin which has a unit of the monomer which consists of cyclic olefin (cycloolefin). As cycloolefin resin used for a transparent resin film, any of a cycloolefin polymer (COP) or a cycloolefin copolymer (COC) may be sufficient. A cycloolefin copolymer means amorphous cyclic olefin resin which is a copolymer of cyclic olefin and olefins, such as ethylene.

As said cyclic olefin, polycyclic cyclic olefin and monocyclic cyclic olefin exist. As such polycyclic cyclic olefin, norbornene, methyl norbornene, dimethyl norbornene, ethyl norbornene, ethylidene norbornene, butyl norbornene, dicyclopentadiene, dihydrodicyclopenta Dienes, methyldicyclopentadiene, dimethyldicyclopentadiene, tetracyclododecene, methyltetracyclododecene, dimethylcyclotetradodecene, tricyclopentadiene, tetracyclopentadiene and the like. In addition, examples of the monocyclic cyclic olefin include cyclobutene, cyclopentene, cyclooctene, cyclooctadiene, cyclooctatriene, cyclododecatene, and the like.

Cycloolefin resin can also be obtained as a commercial item, For example, Nippon-Zeon company "ZEONOR", JSR company "ARTON", polyplastics company "TOPAS", Mitsui Chemicals company "APEL", etc. are mentioned.

The cured resin layer, the transparent conductive film, etc. which are formed on a transparent resin film by giving a transparent resin film previously a sputtering, corona discharge, flame, ultraviolet irradiation, electron beam irradiation, chemical conversion, oxidation, etc., to a surface, and are formed on a transparent resin film, etc. You may improve the adhesiveness of the. Moreover, before forming a cured resin layer or a transparent conductive film, you may damp and clean the surface of a transparent resin film by solvent washing, ultrasonic cleaning, etc. as needed.

It is preferable to exist in the range of 20-150 micrometers, it is more preferable to exist in the range of 30-100 micrometers, and, as for the thickness of a transparent resin film, it is still more preferable to exist in the range which is 40-80 micrometers. When the thickness of a transparent resin film is less than the lower limit of the said range, mechanical strength may run short, and the operation which continuously forms a transparent conductive film by making a film base material into a roll may become difficult. On the other hand, when thickness exceeds the upper limit of the said range, the improvement of the scratch resistance of a transparent conductive film and the spot characteristic for a touch panel may not be aimed at.

Although glass transition temperature (Tg) of amorphous cycloolefin resin of the said transparent resin film is not specifically limited, 130 degreeC or more is preferable, 160 degreeC or more is more preferable, 180 degreeC or more is more preferable. Thereby, since the generation amount and direction of curl after a heating process, such as drying, can be controlled, the process conveyance of a transparent conductive film laminated body becomes easy.

The thermal contraction rate of MD direction and TD direction at the time of heating for 90 minutes at 130 degreeC of the resin film original fabric (film before laminating a cured resin layer, etc.) which forms a transparent resin film is 0.3% or less. It is preferable, it is more preferable that it is 0.2% or less, and it is still more preferable that it is 0.1% or less. Thereby, since it becomes a transparent conductive film excellent in workability, transparency, etc., and can generate | occur | produce the amount and direction of curl after a heating process, such as drying, process conveyance of a transparent conductive film laminated body becomes easy.

It is easy to make the said transparent resin film into the film of the low phase difference whose phase difference R0 of in-plane direction is 0 nm-10 nm, and the (lambda) / 4 film whose phase difference of in-plane direction is about 80 nm-150 nm, and with a polarizing plate In the case of being used, visibility can be improved. In addition, in-plane phase difference (R0) says the phase difference value in retardation film (layer) surface measured with the light of wavelength 589nm in 23 degreeC.

(Cured resin layer)

The cured resin layer includes a first cured resin layer formed on one first main surface side of the transparent resin film and a second cured resin layer formed on the second main surface side on the opposite side. Since the transparent resin film formed of cycloolefin resin is easy to be damaged in each process, such as formation of a transparent conductive film, patterning of a transparent conductive film, or mounting to an electronic device, 1st hardening on both surfaces of a transparent resin film as mentioned above It is preferable to form a resin layer and a 2nd cured resin layer.

The cured resin layer is a layer obtained by curing the curable resin. As resin to be used, what has sufficient intensity | strength as a film after hardening resin layer formation, and having transparency can be used without a restriction | limiting especially, A thermosetting resin, an ultraviolet curable resin, an electron beam curable resin, a two-liquid mixed resin, etc. are mentioned. . Among these, the ultraviolet curable resin which can form a cured resin layer efficiently by the hardening process by ultraviolet irradiation by simple processing operation is preferable.

As ultraviolet curable resin, various things, such as polyester type, an acryl type, urethane type, an amide type, silicone type, an epoxy type, etc. are mentioned, A ultraviolet curable monomer, an oligomer, a polymer, etc. are contained. UV-curable resin used preferably is acrylic resin and epoxy resin, More preferably, it is acrylic resin.

The cured resin layer may contain particles. By mix | blending particle | grains with a cured resin layer, a rise can be formed in the surface of a cured resin layer, and blocking resistance can be preferably given to a transparent conductive film.

As said particle | grain, what has transparency, such as various metal oxide, glass, a plastics, can be used without a restriction | limiting in particular. For example, various polymers such as inorganic particles such as silica, alumina, titania, zirconia, calcium oxide, polymethyl methacrylate, polystyrene, polyurethane, acrylic resin, acrylic-styrene copolymer, benzoguanamine, melamine, polycarbonate, etc. And crosslinked or uncrosslinked organic particles, silicon particles, and the like. Although the particle | grains can select suitably 1 type, or 2 or more types, and can use it, Organic type particle | grains are preferable. As organic particle | grains, acrylic resin is preferable from a refractive index viewpoint.

The modest particle diameter of the particle can be appropriately set in consideration of the degree of protrusion of the ridge of the cured resin layer, the relationship with the thickness of the flat region other than the ridge, and the like, and is not particularly limited. Moreover, 0.1-3 micrometers is preferable and 0.5-2.5 micrometers is more preferable from a viewpoint of providing sufficient blocking resistance to a transparent conductive film, and fully suppressing a raise of a haze. In addition, in this specification, "mode of particle diameter" means the particle diameter which shows the maximum value of particle distribution, and it uses the flow particle image analyzer (The product made by Sysmex, product name "FPTA-3000S"), under predetermined conditions (Sheath liquid). : Ethyl acetate, a measurement mode: HPF measurement, a measurement system: a total count). The measurement sample uses what diluted the particle | grains to 1.0 weight% with ethyl acetate, and was disperse | distributed uniformly using the ultrasonic cleaner.

It is preferable that it is 0.05-1.0 weight part with respect to 100 weight part of solid content of a resin composition, It is more preferable that it is 0.1-0.5 weight part, and, as for content of particle | grains, it is still more preferable that it is 0.1-0.2 weight part. When content of the particle | grains in a cured resin layer is small, there exists a tendency for a ridge sufficient to provide blocking resistance or slipperiness to the surface of a cured resin layer to become difficult to form. On the other hand, when content of particle | grains is too big | large, haze of a transparent electroconductive film arises from the light scattering by particle | grains, and there exists a tendency for visibility to fall. Moreover, when content of particle | grains is too big | large, a streak may arise at the time of formation of a cured resin layer (at the time of application | coating of a solution), visibility may be impaired, or the electrical characteristic of a transparent conductive film may become nonuniform.

Cured resin layer apply | coats the resin composition containing each curable resin and the particle, crosslinking agent, initiator, a sensitizer, etc. which are added as needed on a transparent resin film, and when a resin composition contains a solvent, drying of a solvent And hardening by application of heat, an active energy ray, or both. The heat may be a known means such as an air circulation oven or an IR heater, but is not limited to these methods. Examples of active energy rays include ultraviolet rays, electron beams, gamma rays and the like, but are not particularly limited.

A cured resin layer can be formed into a film by the wet coating method (coating method) etc. using the said material. For example, when forming indium oxide (ITO) containing tin oxide as a transparent conductive film, when the surface of the cured resin layer which is an underlayer is smooth, the crystallization time of a transparent conductive film can also be shortened. From such a viewpoint, it is preferable that the cured resin layer is formed into a film by the wet coating method.

The thickness of the cured resin layer is preferably 0.5 µm to 5 µm, more preferably 0.7 µm to 3 µm, and most preferably 0.8 µm to 2 µm. When the thickness of the cured resin layer is in the above range, it is possible to prevent scratches and to prevent film wrinkles in curing shrinkage of the cured resin layer, and to prevent deterioration of visibility such as a touch panel.

(Transparent conductive film)

Although a transparent conductive film can be formed on a transparent resin film, it is preferable to form on the 1st cured resin layer formed in the one 1st main surface side of a transparent resin film. The constituent material of the transparent conductive film is not particularly limited as long as it contains an inorganic material, and is selected from the group consisting of indium, tin, zinc, gallium, antimony, titanium, silicon, zirconium, magnesium, aluminum, gold, silver, copper, palladium, and tungsten. Metal oxides of at least one metal selected are preferably used. The said metal oxide may further contain the metal atom shown to the said group as needed. For example, indium oxide (ITO) containing tin oxide, tin oxide (ATO) containing antimony, etc. are used preferably.

Although the thickness of a transparent conductive film is not specifically limited, In order to make the surface resistance into the continuous film which has the favorable electroconductivity of 1 * 10 <^3> / ohm or less, it is preferable to make thickness 10 nm or more. When the film thickness becomes too thick, it causes a decrease in transparency and the like, and therefore it is preferably 15 to 35 nm, more preferably in the range of 20 to 30 nm. If the thickness of the transparent conductive film is less than 10 nm, the electrical resistance of the film surface is high, and it is difficult to form a continuous film. Moreover, when the thickness of a transparent conductive film exceeds 35 nm, a fall of transparency may be caused.

The formation method of a transparent conductive film is not specifically limited, A conventionally well-known method can be employ | adopted. Specifically, dry processes, such as a vacuum vapor deposition method, a sputtering method, an ion plating method, can be illustrated, for example. Moreover, the appropriate method can also be employ | adopted according to the film thickness required. In addition, when forming a transparent conductive film on a 1st cured resin layer, when a transparent conductive film is formed by dry processes, such as a sputtering method, the surface of a transparent conductive film will hold | maintain substantially the surface shape of the 1st cured resin layer which is the base layer. do. Therefore, when a ridge exists in a 1st cured resin layer, blocking resistance and slipperiness | lubricacy can also be provided preferably also to the transparent conductive film surface.

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

About the definition of "crystalline", after immersing the transparent conductive film in which the transparent conductive film was formed on the transparent resin film in 20 degreeC and 5 weight% hydrochloric acid for 15 minutes, it washes and dries, and the resistance between terminals between 15 mm is made into If the measurement is performed with a tester and the resistance between terminals does not exceed 10 kΩ, the conversion of the ITO film to the crystalline phase is completed.

In addition, the transparent conductive film may be patterned by etching or the like. About patterning of a transparent conductive film, it can implement using the technique of conventionally well-known photolithography. As etching liquid, an acid is used preferably. Examples of the acid include inorganic acids such as hydrogen chloride, hydrogen bromide, sulfuric acid, nitric acid and phosphoric acid, organic acids such as acetic acid, mixtures thereof, and aqueous solutions thereof. For example, in the transparent conductive film used for a capacitive touch panel or a matrix type resistive touch panel, it is preferable that a transparent conductive film is patterned in stripe form. In addition, when patterning a transparent conductive film by etching, when crystallizing a transparent conductive film first, patterning by etching may become difficult. Therefore, it is preferable to perform annealing of a transparent conductive film after patterning a transparent conductive film.

The transparent conductive film may be amorphous or crystalline when laminating a carrier film to be described later. However, when the transparent conductive film laminate of the present invention is used, the transparent conductive film is bonded to a protective film via an adhesive layer on an amorphous transparent conductive film. Even after performing the annealing treatment, the curl generation of the transparent conductive film laminate can be controlled even if it is converted to crystalline.

(Metal nanowires)

The transparent conductive film may include metal nanowires. The metal nanowire refers to a conductive material having a metal, a needle or a real shape, and a nanometer size in diameter. The metal nanowires may be straight or curved. By using the transparent conductive layer composed of the metal nanowires, the metal nanowires are meshed, whereby even a small amount of the metal nanowires can form a good electric conduction path, and a transparent conductive film having a low electric resistance can be obtained. Moreover, since a metal nanowire turns into a mesh, an opening is formed in the clearance gap of a mesh, and the transparent conductive film with high light transmittance can be obtained.

As the metal constituting the metal nanowire, any suitable metal may be used as long as it is a metal having high conductivity. As a metal which comprises the said metal nanowire, silver, gold, copper, nickel etc. are mentioned, for example. Moreover, you may use the material which gave these metal the plating process (for example, gold plating process). Especially, it is silver, copper or gold from a viewpoint of electroconductivity, More preferably, it is silver.

<Transparent conductive film>

A transparent conductive film has a transparent resin film and a transparent conductive film. In the transparent conductive film, the heat shrinkage 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 even more preferably 0.1% or less. Thereby, since it becomes a transparent conductive film excellent in workability, transparency, etc., and can generate | occur | produce the amount and direction of curl after a heating process, such as drying, process conveyance of a transparent conductive film laminated body becomes easy.

(Optical adjustment layer)

One or more optical adjusting layers may be further included between the first cured resin layer and the transparent conductive film. The optical adjustment layer can reduce the transmittance difference and the reflectance difference between the pattern portion in which the pattern remains and the opening in which the pattern does not remain, when the transmittance rise of the transparent conductive film or the transparent conductive film is patterned. It is used to obtain a film.

The optical adjustment layer is formed of an inorganic material, an organic material, or a mixture of inorganic and organic materials. Material in forming an optical adjustment _{layer, 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, ZnO, ZnS, SiO _x (x is 1.5 or more and less than 2), and the inorganic or, acrylic resin, epoxy resin, urethane resin, melamine resin, alkyd resin, and organic material such as siloxane-based polymer and the like. In particular, it is preferable to use a thermosetting resin composed of a mixture of a melamine resin, an alkyd resin, and an organic silane condensate as an organic substance. The optical adjustment layer can be formed using a coating method such as a wet method, a gravure coating method, a bar coating method, a vacuum deposition method, a sputtering method, an ion plating method, or the like using the above materials.

The optical adjustment layer may have nanoparticles whose average particle diameter is 1 nm-500 nm. It is preferable that content of the nano fine particle in an optical adjusting layer is 0.1 weight%-90 weight%. It is preferable that it is the range of 1 nm-500 nm, and, as above-mentioned, as for the average particle diameter of the nanoparticles used for an optical adjustment layer, it is more preferable that it is 5 nm-300 nm. Moreover, it is more preferable that it is 10 weight%-80 weight%, and, as for content of the nano fine particle in an optical adjustment layer, it is still more preferable that it is 20 weight%-70 weight%. By containing nano fine particles in an optical adjusting layer, refractive index adjustment of an optical adjusting layer itself can be performed easily.

As an inorganic oxide which forms nanoparticles, microparticles | fine-particles, such as a silicon oxide (silica), hollow nano silica, titanium oxide, aluminum oxide, zinc oxide, tin oxide, a zirconium oxide, niobium oxide, are mentioned, for example. Among these, fine particles of silicon oxide (silica), titanium oxide, aluminum oxide, zinc oxide, tin oxide, zirconium oxide, and niobium oxide are preferable. These may be used individually by 1 type and may use 2 or more types together.

It is preferable that it is 10 nm-200 nm, as for the thickness of an optical adjustment layer, it is more preferable that it is 20 nm-150 nm, It is still more preferable that it is 30 nm-130 nm. If the thickness of the optical adjustment layer is excessively small, it is difficult to form a continuous coating. Moreover, when the thickness of an optical adjustment layer is excessively large, there exists a tendency for transparency of a transparent conductive film to fall, or a crack becomes easy to occur.

(Metal wiring)

Although a metal wiring can be formed by etching after forming a metal layer on a transparent conductive film, it is preferable to form using a photosensitive metal paste as follows. That is, in the metal wiring, after the transparent conductive film is patterned, a photosensitive conductive paste described later is applied onto the transparent resin film or the transparent conductive film, a photosensitive metal paste layer is formed, and a photomask is laminated or approached. After exposing to a photosensitive metal paste layer through a photomask, and then developing and pattern formation, it is obtained through a drying process. That is, the pattern formation of metal wiring is possible by the well-known photolithography method.

It is preferable that the said photosensitive electrically conductive paste contains electroconductive particle, such as a metal powder, and the photosensitive organic component. As a material of the electroconductive particle of a metal powder, it is preferable to contain at least 1 sort (s) chosen from the group of Ag, Au, Pd, Ni, Cu, Al, and Pt, More preferably, it is Ag. It is preferable that the volume average particle diameter of the electroconductive particle of a metal powder is 0.1 micrometer-2.5 micrometers.

As electroconductive particle other than a metal powder, the metal coating resin particle which coat | covered the resin particle surface with the metal may be sufficient. Although the particle | grains mentioned above are contained as a material of resin particle, acrylic resin is preferable. The metal-coated resin particles are obtained by reacting a silane coupling agent on the surface of the resin particles and coating the surface with a metal. By using a silane coupling agent, dispersion of a resin component can be stabilized and uniform metal coating resin particle can be formed.

The photosensitive electrically conductive paste may further contain the glass frit. It is preferable that volume average particle diameters are 0.1 micrometer-1.4 micrometers, and, as for glass frit, it is preferable that 90% particle diameters are 1-2 micrometers, and top size is 4.5 micrometers or less. The composition of the glass frit is preferably not particularly limited, Bi ₂ O ₃ which is blended in the range of 30% by weight to 70% by weight with respect to the total. An oxide which may include in addition to the Bi ₂ O _3, and may include _{SiO 2, B 2 O 3,} ZrO 2, Al 2 O 3. _{Na 2 O, K 2 O,} Li 2 O is substantially preferable that the alkali-free glass frit that does not contain a.

It is preferable that the photosensitive organic component contains a photosensitive polymer and / or a photosensitive monomer. As the photosensitive polymer, light is applied to the side chains or molecular ends of an acrylic resin comprising a polymer of a component selected from a compound having a carbon-carbon double bond such as methyl (meth) acrylate and ethyl (meth) acrylate or a copolymer thereof. Addition of a reactive group, etc. are used preferably. Preferable photoreactive groups include ethylenically unsaturated groups such as vinyl group, allyl group, acryl group, and methacryl group. It is preferable that content of the photosensitive polymer is 1-30 weight%, and 2-30 weight%.

As a photosensitive monomer, (meth) acrylate type monomers, such as methacrylacrylate and ethyl acrylate, (gamma)-methacryloxypropyl trimethoxysilane, 1-vinyl-2-pyrrolidone, etc. are mentioned, 1 type, or 2 or more types can be used.

In the photosensitive electrically conductive paste, it is preferable that the photosensitive organic component contains 5-40 weight% with respect to 100 weight part of metal powders, More preferably, it is 10 weight part-30 weight part. Moreover, it is preferable to use a photoinitiator, a sensitizer, a polymerization inhibitor, and an organic solvent for the photosensitive electrically conductive paste of this invention as needed.

The thickness of the metal layer is not particularly limited. For example, when a part of the in-plane of the metal layer is removed by etching or the like to form the pattern wiring, the thickness of the metal layer is appropriately set so that the pattern wiring after formation has a desired resistance value. Therefore, it is preferable that it is 0.01-200 micrometers, and, as for the thickness of a metal layer, it is more preferable that it is 0.05-100 micrometers. When the thickness of the metal layer is within the above range, the resistance of the pattern wiring does not become too high, and the power consumption of the device does not increase. Moreover, the production efficiency of film-forming of a metal layer increases, the amount of heat of integration at the time of film-forming becomes small, and it becomes difficult to produce heat wrinkle in a film.

In the case where the transparent conductive film is a transparent conductive film for a touch panel used in combination with a display, the portion corresponding to the display portion is formed of a patterned transparent conductive film, and the metal wiring made from the photosensitive conductive paste is formed of a non-display portion ( For example, it is used for the wiring part of the peripheral part. The transparent conductive film may also be used in the non-display portion, in which case metal wiring may be formed on the transparent conductive film.

<Carrier film>

The carrier film has an adhesive layer on at least one surface side of a protective film. A carrier film bonds together the transparent conductive film which can be peeled through an adhesive layer, and the 2nd main surface side of a transparent conductive film, and forms a transparent conductive film laminated body. When peeling a carrier film from a transparent conductive film laminated body, an adhesive layer may peel with a protective film, and only a protective film may peel.

(Protective film)

As a material which forms a protective film, what is excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy, etc. is preferable. It is preferable to form from amorphous resin different from the amorphous cycloolefin type resin which forms the said transparent resin film from a viewpoint of controlling the generation amount and direction of a curl. Moreover, it is preferable that amorphous cycloolefin resin of a transparent resin film and amorphous resin of the said protective film are resin from which a structural unit differs from each other. Here, the definition of "different" refers to resins in which the structural units are different from each other. However, even if the structural units are the same number, they are different resins if the weight average molecular weight or the like is different.

As amorphous resin, the cycloolefin resin, polycarbonate resin, etc. which were mentioned above are mentioned. Polycarbonate-based resins are preferable from the viewpoint of excellent light transmittance, scratch resistance and water resistance, and good mechanical properties. Examples of the polycarbonate resins include aliphatic polycarbonates, aromatic polycarbonates, aliphatic-aromatic polycarbonates, and the like. Specifically, bisphenol A polycarbonate, branched bisphenol A polycarbonate, expanded polycarbonate, copolycarbonate, block copolycarbonate, polyester carbonate, polyphosphonate carbonate and the like can be given. Polycarbonate resins include those blended with other components such as bisphenol A polycarbonate blends, polyester blends, ABS blends, polyolefin blends, styrene-maleic anhydride copolymer blends. As a commercial item of polycarbonate resin, "Keiwa" Opcon ", Teijin Co., Ltd." Fanlite ", etc. are mentioned.

From a viewpoint of controlling a glass transition temperature, 1.5 * 10 <^4> -3.5 * 10 <^4> is preferable and, as for the weight average molecular weight of the said polycarbonate-type resin, 2 * 10 <^4> -3 * 10 <^4> is more preferable.

The protective film, like the transparent resin film, is subjected to etching treatment and undercoating treatment such as sputtering, corona discharge, flame, ultraviolet irradiation, electron beam irradiation, chemical conversion, oxidation, and the like on the surface in advance, thereby improving adhesion to the pressure-sensitive adhesive layer on the protective film. You may make it possible. Moreover, before forming an adhesive layer, you may damp and clean a protective film surface by solvent washing, ultrasonic cleaning, etc. as needed.

From a viewpoint of controlling curl generation amount and a direction, and improving workability etc., the thickness of a protective film has preferable 20-150 micrometers, 30-100 micrometers is more preferable, 40-80 micrometers is more preferable.

130 degreeC or more is preferable, as for glass transition temperature (Tg) of amorphous resin of a protective film, 135 degreeC or more is more preferable, and 140 degreeC or more is more preferable. Thereby, since the generation amount and direction of curl after a heating process, such as drying, can be controlled, conveyance of a transparent conductive film laminated body becomes easy.

It is preferable that the absolute value of the difference (a-b) of the glass transition temperature a of amorphous cycloolefin type resin of the above-mentioned transparent resin film, and the glass transition temperature b of the amorphous resin of the said protective film is 5 degreeC or more, It is more preferable that it is 7 degreeC or more, and it is still more preferable that it is 10 degreeC or more. Thereby, workability etc. can be improved by controlling the curl generation amount and direction. Moreover, when it is the same structural unit, it is more preferable that the glass transition temperature a of amorphous cycloolefin type resin of a transparent resin film is higher than the glass transition temperature b of amorphous resin of the said protective film. Thereby, workability etc. can be improved more by controlling the curl generation amount and direction.

In the protective film, the heat shrinkage 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 even more preferably 0.1% or less. Thereby, it becomes a protective film excellent in workability, transparency, etc., and since the generation amount and direction of curl after a heating process, such as drying, can be controlled, conveyance of a transparent conductive film laminated body becomes easy.

(Adhesive layer)

As an adhesive layer, if it has transparency, it can use without a restriction | limiting in particular. Specifically, for example, rubbers such as acrylic polymers, silicone polymers, polyesters, polyurethanes, polyamides, polyvinyl ethers, vinyl acetate / vinyl chloride copolymers, modified polyolefins, epoxy-based, fluorine-based, natural rubbers and synthetic rubbers What uses a polymer, such as a base polymer, can be selected suitably and can be used. In particular, an acrylic pressure sensitive adhesive is preferably used in that it is excellent in optical transparency, exhibits proper wettability, cohesiveness and adhesiveness, and also has excellent weather resistance and heat resistance.

The formation method of an adhesive layer is not restrict | limited, The method of apply | coating an adhesive composition to a peeling liner, and after drying, the method of transferring to a base film (transcription method), the method of apply | coating and drying an adhesive composition directly to a protective film (direct yarn method) Or a method by coextrusion. Moreover, a tackifier, a plasticizer, a filler, antioxidant, a ultraviolet absorber, a silane coupling agent, etc. can also be used suitably for an adhesive as needed. Preferable thickness of an adhesive layer is 5 micrometers-100 micrometers, More preferably, they are 10 micrometers-50 micrometers, More preferably, they are 15 micrometers-35 micrometers.

<Transparent conductive film laminated body>

A transparent conductive film laminated body contains the carrier film which has an adhesive layer in the at least one surface side of a protective film, and the transparent conductive film laminated | stacked so that peeling was possible through the said adhesive layer. In addition, the carrier film is laminated | stacked on the other surface side with the transparent conductive film of a transparent conductive film.

The transparent conductive film laminated body cuts the transparent conductive film laminated body into 20 cm x 20 cm, and makes the difference of the curl value A of the center part, and the average curl value B of the four corner parts after heating for 90 minutes at 130 degreeC, making a transparent conductive film an upper surface ( It is preferable that A-B) is 0-50 mm, It is more preferable that it is 5-45 mm, It is more preferable that it is 10-40 mm. Thereby, since the generation amount and direction of curl after a heating process, such as drying, can be controlled, conveyance of a transparent conductive film laminated body becomes easy.

<Touch panel>

The transparent conductive film which peeled a carrier film or a protective film from a transparent conductive film laminated body is applicable suitably as transparent electrodes of electronic devices, such as touch panels, such as a capacitive system and a resistive film system, for example.

At the time of formation of a touch panel, other base materials, such as glass and a polymer film, etc. can be bonded together through the transparent adhesive layer in one or both main surfaces of the above-mentioned transparent conductive film. For example, you may form the laminated body by which the transparent base material was bonded through the transparent adhesive layer in the surface on the side in which the transparent conductive film of the transparent conductive film is not formed. The transparent base may be composed of one base film, or may be a laminate of two or more base films (for example, one laminated through a transparent pressure-sensitive adhesive layer). Moreover, a hard coat layer can also be provided in the outer surface of the transparent base material bonded to a transparent conductive film. As an adhesive layer used for bonding a transparent conductive film and a base material, if it has transparency as mentioned above, it can use without a restriction | limiting in particular.

When the said transparent conductive film is used for formation of a touch panel, since the generation amount and direction of the curl after a heating process, such as drying, can be controlled, conveyance of a transparent conductive film laminated body becomes easy and handling at the time of touch panel formation Excellent in sex Therefore, a touch panel excellent in transparency and visibility can be manufactured with high productivity. If it is other than a touch panel use, it can use for the shield use which shields the electromagnetic wave and noise which generate | occur | produce from an electronic device.

<The manufacturing method of the processed transparent conductive film>

The manufacturing method of the transparent conductive film laminated body of this invention is a protective film through the process of preparing the transparent conductive film in which the transparent conductive film was formed in the transparent resin film, and the adhesive layer on the other surface side with the transparent conductive film of the transparent conductive film via a protective film. It includes a step of laminating. The manufacturing method of the processed transparent conductive film of this invention includes the process of heat-processing the transparent conductive film of the said transparent conductive film laminated body, and the process of peeling a transparent conductive film and a carrier film. It is preferable that the process of heat processing includes the process of crystallizing the said transparent conductive film. It is preferable to include the process of drying the metal wiring formed with the photosensitive metal paste layer as a process to heat-process.

The transparent conductive film used for the process of preparing a transparent conductive film may form a cured resin layer on a transparent resin film, and may then form a transparent conductive film, and the transparent resin laminated body in which the cured resin layer was formed on the transparent resin film may be used. It may obtain and then form a transparent conductive film on a cured resin layer, and may obtain a transparent conductive film in which the cured resin layer and the transparent conductive film were formed on the transparent resin film. Also about the optical adjustment layer mentioned above, you may obtain and use the transparent resin laminated body formed in advance.

The process of laminating | stacking a protective film forms a carrier film by forming an adhesive layer in a release base material, and transfers an adhesive layer to a protective film, and the side in which the transparent resin film of the 2nd cured resin layer of a transparent conductive film is not formed. The protective film is laminated | stacked through an adhesive layer in the. Moreover, an adhesive layer can also be directly formed in a protective film.

After the lamination process, in order to crystallize the constituent components of the transparent conductive film, it is introduced into a heating step. It is preferable to perform this heating temperature at the temperature of 130 degrees C or less, for example, More preferably, at 120 degrees C or less, processing time is 15 minutes-180 minutes, for example. Thereafter, the transparent conductive film is etched, and a pattern portion is formed by etching.

After the transparent conductive film is patterned, the present invention is applied to the above-mentioned photosensitive conductive paste on the transparent resin film or the transparent conductive film to form a photosensitive metal paste layer, and the photomask is laminated or proximate to form the photomask. It is preferable to further include the process of exposing to a photosensitive metal paste layer through metal, or obtaining a metal wiring by screen printing.

It is preferable to perform drying temperature in the process of drying the metal wiring formed by the photosensitive metal paste layer at 130 degrees C or less, More preferably, it is 120 degrees C or less.

Although it is processed by the roll-to-roll manufacturing method until the heating process for crystallizing a transparent conductive film, since the etching process and the metal wiring process after that have a photomask, the alignment of patterning of a transparent conductive film, and a metal wiring, etc., it is performed by a sheet | leaf process. do. In this case, a step of fixing the transparent conductive film, the transparent conductive film laminate, and the like to the adsorption plate is necessary for positioning, but the amount and direction of curl can be controlled even when dried in the above temperature range, so that It can be returned.

Example

EMBODIMENT OF THE INVENTION Hereinafter, although this invention is demonstrated in detail using an Example, this invention is not limited to a following example, unless the summary is exceeded.

Example 1

(Preparation of resin composition for hardening resin layer formation)

0.2 part by weight of 100 parts by weight of the ultraviolet curable resin composition (trade name "UNIDIC (registered trademark) RS29-120" manufactured by DIC Corporation) and acrylic spherical particles (trade name "MX-180TA manufactured by Soken Chemical Co., Ltd.") having a minimum particle diameter of 1.9 µm. The curable resin composition containing spherical particle containing was prepared.

(Formation of Cured Resin Layer)

The prepared spherical particle-containing curable resin composition was applied to one surface of a polycycloolefin film (Nippon Xeon Co., Ltd. product name "ZEONOR (trademark)") having a thickness of 50 µm and a glass transition temperature of 165 ° C, thereby forming an application layer. . Subsequently, the coating layer was irradiated with ultraviolet rays from the side on which the coating layer was formed, and a second cured resin layer was formed so that the thickness became 1.0 μm. On the other side of a polycycloolefin film, the 1st cured resin layer was formed so that thickness might be set to 1.0 micrometer by the same method except not adding spherical particle as the above.

(Formation of Transparent Conductive Film)

Next, input the polycycloolefin films cured resin layer formed on both surfaces, the volume ingestion sputtering apparatus, the surface of the first cured resin layer, indium tin of the amorphous having a thickness of 27 ㎚ oxide layer (composition: SnO ₂ 10 wt%) was formed.

(Formation of carrier film)

By conventional solution polymerization, an acrylic polymer having a weight average molecular weight of 600,000 was obtained in butyl acrylate / acrylic acid = 100/6 (weight ratio). To 100 parts by weight of this acrylic polymer, 6 parts by weight of an epoxy-based crosslinking agent (Mitsubishi Gas Chemical Co., Ltd. brand name "Tetrad C (registered trademark)") was added to prepare an acrylic pressure-sensitive adhesive. The acrylic adhesive obtained as mentioned above was apply | coated on the mold release process surface of the mold release process, and it heated at 120 degreeC for 60 second, and formed the adhesive layer of thickness 20micrometer. Subsequently, PET film was pasted together through the adhesive layer on the single side | surface of the polycarbonate resin film (Kwa manufacture brand name "Opcon PC") of 75 micrometers in thickness, and glass transition temperature of 145 degreeC. Thereafter, the release-treated PET film was peeled off to prepare a carrier film having an adhesive layer on one surface of the protective film.

(Formation of the transparent conductive film laminate)

The adhesive layer of the carrier film was laminated | stacked on the surface side in which the transparent conductive film of a transparent conductive film is not formed, and the transparent conductive film laminated body was formed.

Example 2

In Example 1, the transparent conductive film laminated | stacked by the method similar to Example 1 except having used the polycycloolefin film (Nippon Xeon make brand name "ZEONOR (trademark)") whose glass transition temperature is 136 degreeC as a transparent resin film. A sieve was produced.

Example 3

In Example 1, except having used the polycycloolefin film (The Nippon Xeon make brand name "ZEONOR (trademark)") whose thickness is 50 micrometers and glass transition temperature is 136 degreeC, as a protective film in the same way as Example 1 The transparent conductive film laminated body was produced.

Comparative Example 1

In Example 1, the transparent conductive film laminated body was carried out similarly to Example 1 except having used PET film (Mitsubishi resin make brand name "diafoil") whose thickness is 50 micrometers and glass transition temperature is 70 degreeC as a protective film. Was produced.

Comparative Example 2

In Example 1, the transparent conductive film laminated body was carried out similarly to Example 1 except having used PET film (Mitsubishi resin make brand name "diafoil") whose thickness is 188 micrometers, and glass transition temperature is 70 degreeC as a protective film. Was produced.

<Evaluation>

(1) measurement of thickness

The thickness measured about the thing which has thickness of 1 micrometer or more with the micro gauge type thickness meter (made by Mitsutoyo Corporation). In addition, the thickness of less than 1 micrometer and the thickness (100 nm) of the optical adjustment layer were measured by the instantaneous multi-metering system (MCPD2000 by Otsuka Electronics Co., Ltd.). Like the thickness of an ITO film | membrane, the nano size thickness produced the sample for cross-sectional observation with FB-2000A (made by Hitachi High-Technologies Corporation), and the cross-sectional TEM observation used HF-2000 (made by Hitachi High-Technologies Corporation). The film thickness was measured. The evaluation results are shown in Table 1.

(2) Measurement of curl value

The transparent conductive film laminate obtained in the examples and the comparative examples was cut to a size of 20 cm × 20 cm. After heating at 130 degreeC for 90 minutes in the state which becomes ITO surface, it was left to cool at room temperature (23 degreeC) for 1 hour. Thereafter, the sample was placed on the horizontal plane with the ITO layer facing upwards, and the height (curl value A) from the horizontal plane of the center part was measured. Moreover, the height from the horizontal surface of 4 corner part was measured, respectively, and the average value (curl value B) was computed. The value (A-B) which subtracted the curl value B from curl value A was computed as curl amount. The evaluation results are shown in Table 1.

(3) Thermal contraction rate in MD direction and TD direction

The thermal contraction rate of the longitudinal direction (MD direction) and the width direction (TD direction) of each film of a transparent conductive film and a protective film was measured as follows. Specifically, the transparent conductive film and the protective film are cut out to a width of 100 mm and a length of 100 mm (test piece), and the four corners are scratched with a cross and before heating in the MD direction and the TD direction at the four center portions of the cross scratches. The length (mm) was measured by the CNC three-dimensional measuring machine (LEGEX774 by Mitsutoyo Corporation). Then, it put in oven and heat-processed (130 degreeC, 90 minutes). After cooling for 1 hour at room temperature, the length (mm) after heating in the MD direction and the TD direction of the four corners is measured again by a CNC three-dimensional measuring instrument, and the measured value is substituted into the following equation to determine the MD and TD directions. Each thermal contraction rate was calculated | required. The evaluation results are shown in Table 1. Thermal contraction rate (%) = [[length before heating (mm)-length after heating (mm)] / length before heating (mm)] × 100

(4) Measurement of surface resistance

It measured by the 4-probe method according to JISK7194.

(5) Measurement of glass transition temperature (Tg)

Glass transition temperature (Tg) was calculated | required based on the specification of JISK7121.

(6) Measurement of the weight average molecular weight

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

Measuring instrument: trade name HLC-8120

GPC column: Tosso brand name G4000H _XL + brand name G2000H _XL + brand name G1000H _XL (each 7.8 mmφ × 30 cm, total 90 cm)

Column temperature: 40 ℃

Eluent: tetrahydrofuran

Flow rate: 0.8 ml / min

Inlet pressure: 6.6 MPa

Standard sample: polystyrene

(Results and Discussion)

In the transparent conductive film laminated bodies of Examples 1-3, the direction of curl generation was a convex direction when the transparent conductive film was raised, and the amount of curl generation was controlled to 20-35 mm. On the other hand, in the transparent conductive film laminated body of Comparative Example 1, when the transparent conductive film was placed upward, the film curled large in the concave direction, and the curl value of the four corner portions could not be measured. In the transparent conductive film laminated body of the comparative example 2, when the direction of curl generation made the transparent conductive film upward, curl generate | occur | produced largely in the concave direction, and the edge part floated. As in Comparative Examples 1 to 2, when curled in the concave direction when the transparent conductive film is placed upwards, it cannot be adsorbed by the adsorption board, which makes it difficult to process.

1: protective film
2: adhesive layer
3: 2nd cured resin layer
4: transparent resin film
5: 1st cured resin layer
6: transparent conductive film
10: carrier film
20: transparent conductive film
S1: first principal plane
S2: second principal plane

Claims (10)

As a transparent conductive film laminated body containing the carrier film which has an adhesive layer in the at least one surface side of a protective film, and the transparent conductive film laminated | stacked so that peeling was possible through the said adhesive layer,
The transparent conductive film has a transparent resin film and a transparent conductive film,
The transparent resin film is made of an amorphous cycloolefin resin,
The thickness of the said transparent resin film is 20-150 micrometers,
The said carrier film is laminated | stacked on the other surface side with the transparent conductive film of the said transparent conductive film,
The said protective film is formed from amorphous resin different from the amorphous cycloolefin resin which forms the said transparent resin film,
The glass transition temperature of amorphous resin of the said protective film is 130 degreeC or more,
The thickness of the said protective film is 20-150 micrometers,
The difference (A-B) between the curl value A of the center part and the average curl value B of the four corner parts after cutting the said transparent conductive film laminated body at 20 cm x 20 cm, and heating at 130 degreeC for 90 minutes, making a transparent conductive film an upper surface, The transparent conductive film laminated body which is 5-50 mm. The method of claim 1,
The glass transition temperature of amorphous cycloolefin resin of the said transparent resin film is 130 degreeC or more, the 1st cured resin layer formed in the one 1st main surface side of the said transparent resin film, and the said 1st main surface of the said transparent resin film The transparent conductive film laminated body which has a 2nd cured resin layer formed in the 2nd main surface side on the opposite side. The method of claim 1,
The transparent conductive film lamination whose absolute value of the difference (a-b) of the glass transition temperature a of amorphous cycloolefin resin of the said transparent resin film, and the glass transition temperature b of the amorphous resin of the said protective film is 5 degreeC or more. sieve. The method of claim 1,
Transparent electroconductive film laminated body in which amorphous cycloolefin resin of the said transparent resin film and amorphous resin of the said protective film are resin from which a structural unit differs from each other. The method of claim 1,
The said protective film consists of polycarbonate resin, the weight average molecular weight is 2 * 10 <^4> or more, and the heat shrink rate after heating for 90 minutes at 130 degreeC is 0.3% or less in MD and TD direction, The transparent conductive film laminated body. The method of claim 2,
The transparent conductive film laminated body provided with the 1st or more optical adjustment layer further between the said 1st cured resin layer and the said transparent conductive film. The touch panel obtained using the transparent conductive film laminated body of Claim 1. The manufacturing method of the processed transparent conductive film containing the process of heat-processing the transparent conductive film of the transparent conductive film laminated body of any one of Claims 1-6, and the process of peeling a transparent conductive film and a carrier film. . The method of claim 8,
The said process to heat-process is a manufacturing method of the transparent conductive film which is a process of crystallizing the said transparent conductive film. The method of claim 8,
The said process to heat-process is a manufacturing method of the transparent conductive film which is a process of drying the metal wiring formed with the photosensitive metal paste layer.

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