KR20190094172A - Transparent conductive film with carrier film and touch panel using the same - Google Patents

Abstract

By controlling the water content of the protective film of the transparent conductive film in which the carrier film was formed, while preventing the abnormality of the resistance value of a transparent conductive film, the adhesiveness of a transparent conductive film and a base material improves the transparent conductive film with a carrier film which prevents film peeling. And a touch panel using the same. The transparent conductive film in which the carrier film in this invention was formed is the transparent conductive film 20 containing the transparent resin film 3 and the transparent conductive film 4, and the said transparent resin film of the said transparent conductive film 20. The transparent conductive film in which the carrier film containing the carrier film 10 containing the adhesive layer 2 and the protective film 1 which were arrange | positioned at the surface side in which (3) was formed was formed, The said transparent conductive film 4 is indium It is a tin composite oxide, and the water content of the said protective film 1 is 1.0 * 10 <^-3> g or less per 10mm * 10mm.

Description

Transparent conductive film with carrier film and touch panel using the same

This invention relates to the transparent conductive film in which the carrier film containing a transparent conductive film and a carrier film was formed, and a touch panel using the same, and is especially a technique useful for prevention of abnormal resistance value and film peeling.

In the field of a touch panel etc., the thickness reduction is calculated | required more and more recently, and with this, the thickness of the transparent conductive film itself is also desired. As a general touch panel method, a resistive film method, a capacitance method, etc. are mentioned. In the case of the electrostatic capacitive type which has been widely adopted in touch panels in recent years, polyethylene terephthalate (PET) has been used as a base film of a transparent conductive film, in addition to flexibility and workability, and excellent in impact resistance and light weight. It is widely used.

With the base film thinning, in order to ensure the handling property of the base film in a manufacturing process step, the surface protection film bonded together via an adhesive layer on the surface side opposite to the transparent conductive layer of a base film. The need for this is increasing. In general, PET is widely used for a surface protection film similarly to a base film.

Patent Document 1 discloses an amorphous transparent conductive laminate in which a protective film based on PET is bonded to a transparent conductive film based on PET on a surface side on which a transparent conductive layer is not formed, and laminated by bonding an adhesive layer. .

On the other hand, ITO (indium-tin composite oxide) used for capacitive touch panel electrode applications requires a low surface resistance value in order to form a pattern with high sensitivity and high resolution. Patent Document 2 discloses a laminate in which a protective film is laminated on a transparent conductive film using PET as a film substrate. When ITO is used as the transparent conductor layer, crystallization of ITO by heating results in low resistance. However, in this document, indium-based composite oxides having a large proportion of oxides of tetravalent metal elements are deposited and indium oxide or 4 An indium composite oxide having a small proportion of oxides of the valent metal element is deposited to reduce the resistance of the ITO film.

WO 2008-108255 publication Japanese Laid-Open Patent Publication 2012-112031

However, since the PET film contains a lot of moisture in the substrate itself, the moisture affects the crystallization of the transparent conductive film. That is, since the moisture affects the crystal growth of the transparent conductive film, the crystallization rate is not only slowed, the resistance value is increased or the resistance value of the transparent conductive film that is uneven, or more, or the transparent conductive film and the substrate are generated. Adhesiveness is reduced, and film peeling at the interface occurs. According to the examination of the present inventors, it was found that the influence of the moisture content of such a film not only contributes to the base material of a transparent conductive film but also the contribution of a protective film is especially large in the form which a protective film couple | bonded with the transparent conductive film.

Then, the objective of this invention is to control the water content of the protective film of the transparent conductive film in which the carrier film was formed, to prevent abnormality of the resistance value of a transparent conductive film, and to improve the adhesiveness of a transparent conductive film and a base material, and to prevent film peeling. It is providing the transparent conductive film in which the carrier film which is mentioned and the touch panel using the same are provided.

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 with a carrier film of this invention contains the transparent conductive film containing a transparent resin film and a transparent conductive film, the adhesive layer and the protective film arrange | positioned at the surface side in which the said transparent resin film of the said transparent conductive film was formed. A transparent conductive film having a carrier film comprising a carrier film, wherein the transparent conductive film is an indium-tin composite oxide, and the water content of the protective film is 1.0 × 10 ⁻³ g or less per 10 mm × 10 mm. do. In addition, the various physical property values in this invention are the values measured by the method employ | adopted in an Example etc. unless there is particular notice.

According to the transparent conductive film in which the carrier film of this invention was formed, while preventing abnormality of the resistance value of a transparent conductive film, adhesiveness of a transparent conductive film and a base material can be raised and film peeling can be prevented. The mechanism of the resistance value abnormality and the film peeling is considered to be as follows although not sure. It is thought that water content of a protective film will affect especially about resistance value or more. For this reason, in the transparent resin film, the degassing of the base material is carried out by annealing and degassing before the sputtering of the transparent conductive film, but the protective film to be pasted in the later step is constituted in a state of low moisture and outgassing gas. It is thought that this is because moisture of directly affects the transparent conductive film which has been manufactured. Moreover, when a protective film contains a lot of water, crystallization of a transparent conductive film is not fully performed, a desired resistance value cannot be obtained and a nonuniformity of in-plane resistance value worsens. This is considered to be because crystal growth is inhibited because the gas generated when contacting the substrate with moisture, plasma or the like acts as an impurity. About film peeling (adhesiveness), the oxidation reaction in the interface of a transparent conductive film and a base material (transparent resin film etc.) advances, and a crystalline distortion (change of a lattice constant) arises locally in an interface vicinity, and adhesiveness falls. It is estimated that the film peeling occurs. That is, it is considered that the adhesion decreases due to the progress of oxidation at the interface between the transparent conductive film and the substrate under the influence of moisture, and film peeling occurs.

It is preferable that the transparent resin film in this invention has a 1st cured resin layer formed in the surface side of the said transparent conductive film, and the 2nd cured resin layer formed in the surface side opposite to the said transparent conductive film. Since the cured resin layer is formed on both surfaces of the transparent resin film, scratches are less likely to occur in each step such as formation of a transparent conductive film, patterning, or mounting on an electronic device.

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

It is preferable that the thickness of the protective film in this invention is 1 micrometer-150 micrometers. As the thickness of the protective film is thinner, the water content of the protective film can be further suppressed, and the crystallization of the transparent conductive film is sufficiently performed. Therefore, the transparent conductive film and the transparent conductive film are more reliably prevented. It becomes possible to improve the adhesiveness of a base material more, and to prevent film peeling. Moreover, the ease of conveyance by a roll to roll manufacturing method can be improved by setting it as the said range.

It is preferable that the protective film in this invention consists of cycloolefin resin or polycarbonate resin. As a result, a resin having a low water content can be used, and the water content of the protective film can be further controlled, and crystallization of the transparent conductive film is sufficiently performed, thereby more reliably preventing abnormality in the resistance value of the transparent conductive film and making it transparent. It is possible to further improve the adhesion between the conductive film and the substrate to prevent the film from peeling off.

It is preferable that the moisture content of the protective film in this invention is 0.50 weight% or less. As a result, a protective film having a low moisture content can be used, and the water content of the protective film can be further controlled, and crystallization of the transparent conductive film is sufficiently performed, thereby more reliably preventing the resistance value of the transparent conductive film. The adhesiveness of a transparent conductive film and a base material becomes higher, and it becomes possible to prevent film peeling.

In this invention, it is preferable to further provide a conductive layer in the surface side opposite to the surface in which the said adhesive layer of the protective film was formed. This makes it possible to prevent the charge and to suppress unnecessary electric influences.

It is preferable that the touch panel of this invention contains the transparent conductive film in which the said carrier film was formed. This makes it possible to more reliably prevent abnormality in the resistance value of the transparent conductive film and to improve adhesion between the transparent conductive film and the substrate, thereby preventing film peeling, thereby forming a stable high sensitivity and high resolution pattern. Quality such as visibility of the display device of the touch panel can be improved.

BRIEF DESCRIPTION OF THE DRAWINGS It is typical sectional drawing of the transparent conductive film in which the carrier film which concerns on one Embodiment of this invention was formed.
It is typical sectional drawing of the transparent conductive film in which the carrier film which concerns on other embodiment of this invention was formed.

EMBODIMENT OF THE INVENTION Embodiment of the transparent conductive film with a carrier film of this invention is described below, referring drawings. However, in some or all of the drawings, parts unnecessary for the description are omitted, and there are parts shown by enlargement or reduction in order to facilitate the description. 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.

<Transparent conductive film in which carrier film was formed>

1: is sectional drawing which shows typically one Embodiment of the transparent conductive film in which the carrier film of this invention was formed, and FIG. 2 is typical sectional drawing of the transparent conductive film in which the carrier film which concerns on other embodiment of this invention was formed. . As shown in FIG. 1, the transparent conductive film with a carrier film of this invention is the transparent conductive film 20 containing the transparent resin film 3 and the transparent conductive film 4, and the transparent conductive film 20 It is a transparent conductive film in which the carrier film containing the adhesive film 2 arrange | positioned at the surface side in which the transparent resin film 3 was formed, and the carrier film 10 containing the protective film 1 was formed. Moreover, a conductive layer can be further provided in the surface side opposite to the surface in which the said adhesive layer 2 of the protective film 1 was formed.

In addition, as shown in FIG. 2, the transparent resin film 3 has a surface side opposite to the first cured resin layer 6 formed on the surface side of the transparent conductive film 4 and the transparent conductive film 4. Although it can have the 2nd cured resin layer 5 formed in, it is also possible to have any cured resin layer only on one side. In addition, the 1st cured resin layer 6 and the 2nd cured resin layer 5 include what functions as an anti blocking layer and a hard-coat layer. Although the 1st optical adjustment layer 7 can be further provided between the 1st cured resin layer 6 and the transparent conductive film 4, 2 or more layers of optical adjustment layers 7 can also be provided. In addition, in FIG. 2, the transparent conductive film 20 includes the second cured resin layer 5, the transparent resin film 3, the first cured resin layer 6, the optical adjustment layer 7, and the transparent conductive film ( 4) in this order, for example, transparent conductive having the second cured resin layer 5, the transparent resin film 3, the first cured resin layer 6, and the transparent conductive film 4 in this order. It is also the film 20, the transparent conductive film 20 which has the transparent resin film 3, the optical adjustment layer 7, and the transparent conductive film 4 in this order, or it can also be set as arbitrary combinations.

As for the reached resistance value (surface resistance value) when the crystallization is completed from amorphous to crystalline of the transparent conductive film in which the carrier film was formed, 100-130 ohms / square is preferable, 100-120 ohms / square is more preferable, 100 110 ohms / square is more preferable. Thereby, a stable high sensitivity and high resolution pattern can be formed.

As for the standard deviation of the reached resistance value (surface resistance value) when the crystallization is completed from amorphous to crystalline of the transparent conductive film in which the carrier film was formed, 30 ohms / square or less is preferable, 20 ohms / square or less is more preferable, 10 Ω / square or less is more preferable. Thereby, a stable high sensitivity and high resolution pattern can be formed.

<Transparent conductive film>

A transparent conductive film has a transparent resin film and a transparent conductive film. A transparent conductive film can have a transparent resin film which has a 1st cured resin layer formed in the surface side of the said transparent conductive film, and a 2nd cured resin layer formed in the surface side opposite to the said transparent conductive film. The transparent conductive film can further include one or more optical adjusting layers between the first cured resin layer and the transparent conductive film.

It is preferable that the thickness of a transparent conductive film exists in the range of 20-150 micrometers, It is more preferable to exist in the range of 25-100 micrometers, It is still more preferable to exist in the range of 30-80 micrometers. If the thickness of a transparent conductive film is less than the lower limit of the said range, mechanical strength may become inadequate and operation which continuously forms a cured resin layer and 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, improvement of the scratch resistance, such as a transparent conductive film, and other spot characteristics for a touch panel may not be aimed at.

(Transparent resin film)

Although it will not restrict | limit especially if it is transparent in a visible light region as a transparent resin film, Various plastic films which have transparency are used. For example, as the material, polyester resin, cycloolefin resin, polycarbonate resin, acetate resin, polyether sulfone resin, polyamide resin, polyimide resin, polyolefin resin, (meth) Acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl alcohol resin, polyarylate resin, polyphenylene sulfide resin and the like. Polyester resins, cycloolefin resins, and polycarbonate resins are more preferable in terms of improving visibility, but from the viewpoints of high transparency, low water absorption, water barrier property, thermal stability, isotropy, and the like, they are amorphous resins. Cycloolefin resin or polycarbonate resin is especially preferable.

It is preferable that polyester resin is polyethylene terephthalate resin, polyethylene naphthalate resin, etc. from a mechanical characteristic or a heat resistant point.

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. 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 an amorphous cyclic olefin resin which is a copolymer of cyclic olefin and olefins, such as ethylene.

As said cyclic olefin, a polycyclic cyclic olefin and a monocyclic cyclic olefin exist. As such a polycyclic 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, and cyclododecatene.

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, for example. .

The polycarbonate resin is not particularly limited, and examples thereof include aliphatic polycarbonates, aromatic polycarbonates, aliphatic-aromatic polycarbonates, and the like. Specifically, for example, as a polycarbonate (PC) using bisphenols, bisphenol A polycarbonate, branched bisphenol A polycarbonate, expanded polycarbonate, copolycarbonate, block copolycarbonate, polyester carbonate, polyphosphonate Carbonate, diethylene glycol bisallylcarbonate (CR-39), and the like. 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" off cone ", Teijin company" panlite ", Mitsubishi gas chemical company" Eupiron (ultraviolet absorber containing polycarbonate) ", 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 a transparent resin film surface by solvent washing, ultrasonic washing, etc. as needed.

It is preferable that the thickness of a transparent resin film exists in the range of 20-150 micrometers from a viewpoint of improving transparency and the ease of conveyance by a roll-to-roll manufacturing method, while producing a transparent conductive film etc. which are high in transparency and excellent in appearance quality. It is more preferable to exist in the range of -100 micrometers, and it is still more preferable to exist in the range which is 30-80 micrometers. When the thickness of a transparent resin film is less than the lower limit of the said range, mechanical strength may be inadequate, and operation which continuously forms a cured resin layer and a transparent conductive film by making a film base material into a roll shape may become difficult. On the other hand, when thickness exceeds the upper limit of the said range, improvement of the scratch resistance, such as a transparent conductive film, and other spot characteristics for a touch panel may not be aimed at.

The water content of the transparent resin film is preferably 5.0 × 10 ^-3 g or less per 10 mm × 10 mm, more preferably 3.0 × 10 ^-3 g or less per 10 mm × 10 mm, more preferably 1.0 × per 10 mm × 10 mm. More preferably, it is ^10-3 g or less. As a result, the water content of the transparent resin film can be further controlled, and the crystallization of the transparent conductive film is sufficiently performed. Thus, the adhesion between the transparent conductive film and the substrate can be more reliably prevented while preventing the abnormality in the resistance value of the transparent conductive film. It becomes possible to raise and prevent film peeling.

It is preferable that the moisture content of a transparent resin film is 0.50 weight% or less, It is more preferable that it is 0.40 weight% or less, It is further more preferable that it is 0.30 weight% or less.

(Cured resin layer)

A cured resin layer contains the 1st cured resin layer formed in the surface side of the transparent conductive film of a transparent resin film, and the 2nd cured resin layer formed in the other surface side with a transparent conductive film. When a transparent resin film falls easily and it is easy to generate | occur | produce a scratch, since it is easy to generate | occur | produce a scratch in each process, such as formation of a transparent conductive film, patterning of a transparent conductive film, or mounting to an electronic apparatus, as mentioned above, a 1st surface is formed on both surfaces of a transparent resin film. It is preferable to form a cured resin layer and a 2nd cured resin layer.

The cured resin layer is a layer obtained by curing the curable resin or the like. As resin to be used, although the thing which has sufficient intensity | strength as a film after hardening resin layer formation, and transparency can be used without a restriction | limiting in particular, thermosetting resin, ultraviolet curable resin, electron beam curable resin, two-liquid mixed resin, etc. are mentioned. . Among these, the ultraviolet curable resin which can form a cured resin layer efficiently by the simple processing operation in the hardening process by ultraviolet irradiation 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, epoxy resin, or urethane resin, More preferably, it is acrylic resin and urethane resin.

The cured resin layer may contain particles. By mix | blending particle | grains in a cured resin layer, a ridge | flop 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 plastic, can be used without a restriction | limiting in particular. For example, inorganic particles such as silica, alumina, titania, zirconia, calcium oxide, polymethyl methacrylate, polystyrene, polyurethane, acrylic resin, acrylic-styrene resin such as acrylic-styrene copolymer, benzoguanamine, melamine And crosslinked or uncrosslinked organic particles and silicon particles made of various polymers such as polycarbonate. 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 and acrylic-styrene resin are preferable from a refractive index viewpoint.

The 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 of the thickness of the flat region other than the ridge, and the like, and is not particularly limited. Moreover, 0.1-5 micrometers is preferable and, as for the diameter of a particle | grain, from a viewpoint of fully providing blocking resistance to a transparent conductive film and fully suppressing a raise of a haze, 0.5-4 micrometers is more preferable. In addition, in this specification, "diameter" means the particle diameter which shows the maximum value of particle distribution, and it uses the flow type particle image analyzer (The product made by Sysmex, product name "FPTA-3000S"), under predetermined conditions (Sheath liquid). : Ethyl acetate, measuring mode: HPF measurement, measuring system: total count). As a measurement sample, what diluted the particle | grains to 1.0 weight% with ethyl acetate, and disperse | distributed uniformly using the ultrasonic cleaner is used.

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 the ridge | bulb sufficient to provide blocking resistance and the ease of sliding to the surface of a cured resin layer not becoming well formed. On the other hand, when content of particle | grains is too big | large, haze of a transparent conductive film becomes high and there is a tendency for visibility to fall due to the light scattering by a particle | grain. 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, 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. Although heat can use well-known means, such as an air circulation oven and an IR heater, it 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.

The cured resin layer can be formed by a coating method such as a wet coating 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. 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 this 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 the occurrence of scratches and to prevent film wrinkles in curing shrinkage of the cured resin layer, and to prevent visibility of a touch panel and the like from deteriorating.

(Optical adjustment layer)

One or more optical adjusting layers may be further included between the first cured resin layer and the transparent conductive film. Moreover, when not forming a 1st cured resin layer, one or more optical adjustment layers can be included between a transparent resin film and a transparent conductive film. The optical adjustment layer can reduce the transmittance difference or the reflectance difference between the pattern portion in which the pattern remains and the opening in which the pattern does not remain, when the increase in transmittance of the transparent conductive film or the transparent conductive film is patterned, and the transparency is excellent in visibility. It is used to obtain a conductive film.

It is preferable that an optical adjustment layer contains binder resin and microparticles | fine-particles. Examples of the binder resin contained in the optical adjustment layer include acrylic resins, urethane resins, melamine resins, alkyd resins, siloxane polymers and organic silane condensates, and ultraviolet curable resins containing acrylic resins are preferred. .

It is preferable that the refractive index of an optical adjustment layer is 1.6-1.8, It is more preferable that it is 1.61-1.78, It is still more preferable that it is 1.62-1.75. Thereby, a transmittance difference and a reflectance difference can be reduced, and the transparent conductive film excellent in visibility can be obtained.

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

As an inorganic oxide which forms microparticles | fine-particles, microparticles | fine-particles, such as silicon oxide (silica), hollow nano silica, titanium oxide, aluminum oxide, zinc oxide, tin oxide, zirconium oxide, and 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, and zirconium oxide is more preferable. These may be used individually by 1 type and may use 2 or more types together.

The optical adjustment layer can contain another inorganic substance. Minerals include NaF (1.3), Na ₃ AlF ₆ (1.35), LiF (1.36), MgF ₂ (1.38), CaF ₂ (1.4), BaF ₂ (1.3), BaF ₂ (1.3), LaF ₃ (1.55 ), CeF (1.63), etc. (the numerical value in parentheses shows a refractive index).

The optical adjustment layer can be formed using the above-mentioned material by the coating method, such as a wet coating method, the gravure coating method, the bar coating method, the vacuum deposition method, the sputtering method, the ion plating method, etc. For example, when forming indium oxide (ITO) containing tin oxide as a transparent conductive film, if the surface of the optical adjustment layer which is an underlayer is smooth, the crystallization time of a transparent conductive layer can also be shortened. From this viewpoint, it is preferable that the optical adjustment layer is formed into a film by the wet coating method.

It is preferable that it is 40 nm-150 nm, as for the thickness of an optical adjustment layer, it is more preferable that it is 50 nm-130 nm, and it is still more preferable that it is 70 nm-120 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 will become easy to generate | occur | produce.

(Transparent conductive film)

Although a transparent conductive film can also be formed on a transparent resin film, it is preferable to form on the 1st cured resin layer or the optical adjustment layer formed in the one 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 substance, 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 contain the metal atom shown to the said group further as needed. For example, indium tin composite oxide (ITO), 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 / square 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 becomes high, and it becomes 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.

The transparent conductive film can be crystallized by performing heat annealing treatment (for example, about 10 to 90 minutes at 80 to 150 ° C in an air atmosphere) as necessary. By crystallizing the transparent conductive film, in addition to lowering the transparent conductive film, transparency and durability are improved. 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 washed with water and dried, and the interterminal resistance between 15 mm Is measured by a tester, and when the resistance between terminals does not exceed 10 kΩ, it is assumed that the conversion of the ITO film to crystalline is completed. In addition, the measurement of a surface resistance value can be measured by the 4-probe method according to JISK7194.

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.

<Carrier film>

A carrier film contains the adhesive layer and the protective film arrange | positioned at the surface side in which the said transparent resin film of the transparent conductive film was formed, bonds a transparent conductive film and a carrier film, and forms the transparent conductive film with a carrier film. When peeling a carrier film from the transparent conductive film in which the carrier film was formed, an adhesive layer may peel with a protective film and only a protective film may peel.

(Protective film)

Although a protective film peels and discards when laminated | stacked with other films, such as a wave plate and a polarizing plate, in consideration of handleability, water content, etc., such as winding by a roll, as a material which forms a protective film, for example, it mentioned above. The same thing as the material of a transparent resin film is mentioned. Polyester resins, cycloolefin resins, and polycarbonate resins are more preferable in terms of improving visibility, but from the viewpoints of high transparency, low water absorption, water barrier property, thermal stability, isotropy, and the like, they are amorphous resins. Cycloolefin resin or polycarbonate resin is especially preferable. Specific examples of the polyester resin, the cycloolefin resin, and the polycarbonate resin are as described in the above-mentioned transparent resin film, but are selected in consideration of the moisture content therefrom. As a result, a protective film having a low moisture content can be used, and the water content of the protective film can be further controlled, and crystallization of the transparent conductive film is sufficiently performed, thereby more reliably preventing the resistance value of the transparent conductive film. The adhesiveness of a transparent conductive film and a base material becomes higher, and it becomes possible to prevent film peeling.

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 and the like. You may make it possible. Moreover, before forming an adhesive layer, you may damp and clean a protective film surface by solvent washing, ultrasonic washing, etc. as needed.

The water content of the protective film is preferably 1.0 × 10 ^-3 g or less per 10 mm × 10 mm, more preferably 0.9 × 10 ^-3 g or less per 10 mm × 10 mm, and 0.5 × 10 per 10 mm × 10 mm It is more preferable that it is ^-3 g or less. In addition, since the moisture content here varies with an environment with respect to the measured value, it is preferable to satisfy the above-mentioned range at the time of providing it to a sputter film forming or crystallization process. Thereby, while preventing abnormality of the resistance value of a transparent conductive film, adhesiveness of a transparent conductive film and a base material can be raised and film peeling can be prevented. In addition, since the degassing treatment before film-forming, such as passing through a heating process as a pre-treatment, is unnecessary for water removal by this, production efficiency improves.

It is preferable that the moisture content (water content) of a protective film is 0.50 weight% or less, It is more preferable that it is 0.40 weight% or less, It is further more preferable that it is 0.30 weight% or less. As a result, a protective film having a low moisture content can be used, and the water content of the protective film can be further controlled, and crystallization of the transparent conductive film is sufficiently performed, thereby more reliably preventing the resistance value of the transparent conductive film. The adhesiveness of a transparent conductive film and a base material becomes higher, and it becomes possible to prevent film peeling.

1-150 micrometers is preferable, as for the thickness of a protective film, 2-120 micrometers is more preferable, and its 5-100 micrometers are more preferable. As the thickness of the protective film is thinner, the water content of the protective film can be further suppressed, and the crystallization of the transparent conductive film is sufficiently performed. Therefore, the transparent conductive film and the transparent conductive film are more reliably prevented. It becomes possible to improve the adhesiveness of a base material more, and to prevent film peeling. By setting it as the said range, the conveyance ease by a roll to roll manufacturing method can be improved. Moreover, it is preferable that the thickness of a protective film is more than the thickness of a transparent resin film from a viewpoint of preventing breakage of a transparent conductive film laminated body in a roll to roll manufacturing method.

(Conductor Floor)

It is preferable to further provide a conductive layer on the surface side opposite to the surface in which the said adhesive layer of the said protective film was formed from an antistatic viewpoint. The conductive layer can be preferably formed by coating a conductive composition containing a conductive polymer.

Examples of the conductive polymer contained in the conductive composition include polyacetylene polymers, polyparaphenylene polymers, polyaniline polymers, polythiophene polymers, polyparaphenylenevinylene polymers, polypyrrole polymers, and polyphenyls. And polyester polymers modified with a len polymer or an acrylic polymer. Preferably, the conductive polymer is one or more polymers selected from the group consisting of polyacetylene polymers, polyparaphenylene polymers, polyaniline polymers, polythiophene polymers, polyparaphenylenevinylene polymers, and polypyrrole polymers. It contains.

More preferably, a polythiophene-based polymer is used as the conductive polymer. By using a polythiophene-based polymer, it is possible to form a conductive layer excellent in transparency and chemical stability. As a specific example of a polythiophene type polymer, Polythiophene; Poly (3-C _1-8 alkyl-thiophene) such as poly (3-hexylthiophene); Poly (3,4-ethylenedioxythiophene) (PEDOT), poly (3,4-propylenedioxythiophene), poly [3,4- (1,2-cyclohexylene) dioxythiophene] 3,4- (cyclo) alkylenedioxythiophene); Polythienylenevinylene etc. are mentioned.

The conductive layer may be formed by any suitable method. The conductive composition is, for example, a dispersion liquid containing the conductive polymer and any suitable solvent (for example, water) and having the conductive polymer dispersed in the solvent. The dispersion concentration of the conductive polymer in the dispersion is preferably 0.01% by weight to 50% by weight, more preferably 0.01% by weight to 30% by weight.

Arbitrary appropriate methods can be employ | adopted as a coating method of the said electrically conductive composition. For example, the bar coat method, the roll coat method, the gravure coat method, the rod coat method, the slot orifice coat method, the curtain coat method, the fountain coat method, the comma coat method are mentioned. As a drying temperature, it is typically 50 degreeC or more, Preferably it is 90 degreeC or more, More preferably, it is 110 degreeC or more. Drying temperature becomes like this. Preferably it is 200 degrees C or less, More preferably, it is 180 degrees C or less. Drying time becomes like this. Preferably it is 1 minute-1 hour, More preferably, it is 1 minute-30 minutes, More preferably, it is 1 minute-10 minutes.

The thickness of the said conductive layer becomes like this. Preferably it is 1 nm-500 nm, More preferably, it is 1 nm-400 nm, More preferably, it is 1 nm-300 nm. If it is such a range, the electrically conductive layer which can control electrical characteristics favorably will be formed.

The said conductive composition can further contain arbitrary appropriate additives as needed. As a specific example of an additive, a dispersion stabilizer, surfactant, an antifoamer, etc. are mentioned. The kind and quantity of the additive used can be suitably set according to the objective.

(Adhesive layer)

As an adhesive layer, if it has transparency, it can use without a restriction | limiting in particular. Specifically, for example, acrylic polymer, silicone polymer, polyester, polyurethane, polyamide, polyvinyl ether, vinyl acetate / vinyl chloride copolymer, modified polyolefin, epoxy, fluorine, natural rubber, synthetic rubber, etc. What uses a polymer, such as a rubber type, 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 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.

<Touch panel>

The transparent conductive film which peeled a carrier film or a protective film from the transparent conductive film in which the carrier film was formed can be applied suitably as transparent electrodes of electronic devices, such as touch panels, such as a capacitive system and a resistive film system. .

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 which the transparent base material bonded together through the transparent adhesive layer in the surface on the side in which the transparent conductive film of a 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 together to a transparent conductive film. As an adhesive layer used for bonding a transparent conductive film and a base material, as long as it has transparency, it can use without a restriction | limiting in particular.

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.

<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 was measured with the instantaneous multi-metering system (MCPD2000 by Otsuka Electronics Co., Ltd.). Like the thickness of an ITO film etc., 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). Film thickness was measured. The evaluation results are shown in Table 1.

(2) Measurement of water content and moisture content (water content)

The protective film was cut out into a sample of 10 mm × 10 mm square, placed in a heat vaporization device (Mitsubishi Chemical Analyst, VA-200 type), and the carrier gas heated at 150 ° C. was placed in a titration cell (Mitsubishi Chemical Corporation). Nalitech, CA-200 type), the amount of water released during heating was measured by the Karl Fischer method (vaporization method), and the water content and the water content were measured. In addition, a moisture content is a moisture content per 1g, and can be calculated like water content. Also about a transparent resin film, the water content and moisture content were measured by the method similar to the above. The evaluation results are shown in Table 1.

(3) Measurement of Reach Resistance Value

The arrival resistance value at the time of heat-processing the transparent conductive film in which the carrier film was formed at 20 degreeC for 20, 30, and 40 minutes by 120 degreeC by the hot-air circulation type oven was measured. Surface resistance was measured by the four-terminal method according to JIS K7194. The evaluation results are shown in Table 1.

(4) standard deviation of surface resistance

In the measurement of the said arrival resistance value, the surface resistance value of the transparent conductive film in which the carrier film was formed when heat-processing at 120 degreeC for 30 minutes was measured 5 points at 15 cm intervals in the width direction, and the standard deviation is measured Obtained. The evaluation results are shown in Table 1.

(5) crystallization rate

The crystallization rate at which the amorphous transparent conductive film is crystallized was evaluated by the change in the attained resistance value. In addition, the transparent conductive film (reference example 1) without a protective film was made into the reference value of the crystallization rate here. The evaluation results are shown in Table 1.

○: degree to which the crystallization rate is equal to the reference value

X: crystallization rate is slower than reference value

(6) adhesion

The measurement was performed in accordance with JIS K-5600. After heat-processing the transparent conductive film in which the carrier film was formed in the hot-air circulation type oven for 90 minute (s) at 130 degreeC, the sample was cut out to 5 cm and the transparent conductive film (ITO) surface was cut | disconnected by about 1 mm at intervals of 11 mm. Each piece was scratched with a cutter to create 100 masses. A cellophane tape (Sekisui Co., Ltd., # 252) was put thereon, and it squeezed and squeezed 10 times with a spatula, and it peeled rapidly by applying a snap, counting the case where 1/4 or more area | regions of 1 mass peeled, The presence or absence of peeling of the transparent conductive film was confirmed. In addition, the spatula crimping and peeling were repeated twice, changing a direction, and the 2nd crimping was performed by rotating a cellophane tape 90 degrees. The evaluation results are shown in Table 1.

(Circle): There is no peeling (5/100 or less), and adhesiveness is favorable

X: There is peeling (greater than 5/100), and adhesiveness is bad

Example 1

(Formation of Cured Resin Layer)

100 parts by weight of the ultraviolet curable resin composition (trade name "UNIDIC (registered trademark) RS29-120" manufactured by DIC Corporation), urethane-based polyfunctional polyacrylate) and crosslinked acrylic styrene-based spherical particles having a diameter of 3 µm (Sekisui resin Co., Ltd.) One of the 50-micrometer-thick polycycloolefin film (Nippon Xeon make brand name "ZEONOR (registered trademark), in-plane birefringence 0.0001") for curable resin composition containing the spherical particle containing 0.2 weight part of manufacture "SSX105" Was applied to the surface of the film and irradiated with ultraviolet rays from the surface thereof to form a second cured resin layer having a thickness of 1 µm, except that the other surface of the polycycloolefin film did not contain spherical particles. And the 1st cured resin layer was formed so that thickness might be set to 1 micrometer.

(Formation of Optical Control Layer)

A zirconia particle-containing ultraviolet curable composition having a refractive index of 1.62 is applied to the first cured resin layer surface side of the polycycloolefin film having a cured resin layer formed on both surfaces (trade name "Opsta Z7412" manufactured by JSR Corporation) to form an application layer. Subsequently, after drying for 3 minutes at 80 degreeC, an ultraviolet-ray was irradiated to the coating layer with the ozone type high pressure mercury lamp (80 W / cm, 15 cm condensing type: accumulated light quantity 300 mj) from the side in which the coating layer was formed immediately, and thickness The optical adjusting layer was formed so that it might become 0.1 micrometer.

(Formation of Transparent Conductive Film)

A partial pressure of water was 5 × 10 ⁻⁴ Pa by vacuum evacuation while mounting a sintered compact target containing indium oxide and tin oxide in a weight ratio of 90:10 to a parallel plate type wound magnetron sputtering device, and conveying the substrate. Vacuum evacuation was carried out until Thereafter, DC sputtering is performed at an output of 12.5 kW on the optical adjustment layer surface (first cured resin layer) while adjusting the amount of argon gas and oxygen gas introduced, and conveying the substrate at a conveying speed of 7.7 m / min and a conveying tension of 40 to 120 N. It formed into a film and the ITO film | membrane of thickness 22nm was formed. It was 300 ohms / square when the surface resistance of obtained ITO was measured by the four-terminal method.

(Formation of carrier film)

By conventional solution polymerization, an acrylic polymer having a weight average molecular weight of 600,000 was obtained at 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. As a protective film, the said acrylic adhesive is coated on one side to the polycycloolefin film (Nippon Xeon make brand name "ZEONOR (trademark)") of 50 micrometers in thickness, and it heats at 150 degreeC for 90 second, and the adhesive layer of 10 micrometers in thickness is made Formed. Next, the siliconized surface of PET peeling liner (25 micrometers in thickness) which carried out the siliconization on the single side | surface on the surface of the said adhesive layer was bonded together, it preserve | saved at 50 degreeC for 2 days, and the carrier film with a peeling liner was produced. In addition, at the time of use, the said release liner was removed and the carrier film was used.

(Formation of Transparent Conductive Film with Carrier Film)

The protective film in which the adhesive layer of the carrier film was formed 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 with a carrier film was produced.

[Examples 2 to 6]

In Example 1, the transparent conductive film with a carrier film was produced by the method similar to Example 1 except having changed the base material and thickness of a transparent resin film and a protective film as Table 1. In addition, about the base material of Table 1, PET used polycarbonate resin (Tejin make brand name "panlite") for polyethylene terephthalate film (Mitsubishi Resin Co., Ltd. product, T612E25) and PC.

Comparative Example 1

In Example 1, the transparent film in which the carrier film was formed by the same method as Example 1 except having used the polyethylene terephthalate film (Mitsubishi Resin Co., Ltd. product, T612E25) instead of using a polycycloolefin film as a protective film. An electroconductive film was produced.

[Comparative Examples 2-3]

In Example 1, the transparent conductive film with a carrier film was produced by the method similar to Example 1 except having changed the base material and thickness of a protective film as Table 1. In addition, about the base material of Table 1, PET used polycarbonate resin (Teijin make brand name "Pure Ace") for polyethylene terephthalate film (Mitsubishi Resin Co., Ltd. product, T612E25) and PC.

Reference Example 1

In Example 1, only the transparent conductive film was produced without forming a carrier film.

(Results and Discussion)

In the transparent conductive film in which the carrier films of Examples 1-6 were formed, crystallization from amorphous to crystalline was completed after heating at 120 degreeC for about 20 minutes, the nonuniformity of reach | attainment resistance value (surface resistance value) is small, and reach | attainment resistance value is Low. A good result of crystallization rate with respect to the reference (reference example 1) was also obtained. Moreover, adhesiveness with the transparent conductive film was also high, and film peeling did not arise. On the other hand, in the transparent conductive film in which the carrier films of the comparative examples 1-3 were formed, even if it heats at 120 degreeC for about 40 minutes, crystallization from amorphous to crystalline may not be completed, and the nonuniformity of arrival resistance value (surface resistance value) may be Also large, the reached resistance value was high. The rate of crystallization against the reference (Reference Example 1) was also slow. Moreover, adhesiveness with the transparent conductive film was also low, and film peeling occurred.

1: protective film
2: adhesive layer
3: transparent resin film
4: transparent conductive film
5: 2nd cured resin layer
6: 1st cured resin layer
7: optical adjusting layer
10: carrier film
20: transparent conductive film

Claims (8)

The transparent conductive film containing a transparent resin film and a transparent conductive film,
As a transparent conductive film with a carrier film containing the carrier film containing the adhesive layer and the protective film arrange | positioned at the surface side in which the said transparent resin film of the said transparent conductive film was formed,
The transparent conductive film is an indium tin composite oxide,
The transparent conductive film with a carrier film whose water content of the said protective film is 1.0 * 10 <^-3> g or less per 10mm * 10mm. The method of claim 1,
The said transparent resin film is a transparent conductive film with a carrier film which has a 1st cured resin layer formed in the surface side of the said transparent conductive film, and the 2nd cured resin layer formed in the surface side opposite to the said transparent conductive film. The method of claim 2,
The transparent conductive film with a carrier film provided with the 1st or more optical adjustment layer further between the said 1st cured resin layer and the said transparent conductive film. The method according to any one of claims 1 to 3,
The transparent conductive film with a carrier film whose thickness of the said protective film is 1 micrometer-150 micrometers. The method according to any one of claims 1 to 4,
The said protective film is a transparent conductive film with a carrier film which consists of cycloolefin resin or polycarbonate resin. The method according to any one of claims 1 to 5,
The moisture content of the said protective film is a transparent conductive film with a carrier film which is 0.50 weight% or less. The method according to any one of claims 1 to 6,
The transparent conductive film with a carrier film provided with an electroconductive layer further on the surface side opposite to the surface in which the said adhesive layer of the said protective film was formed. The touch panel containing the transparent conductive film in which the carrier film in any one of Claims 1-7 was formed.

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