JP2001216842A - Transparent conductive film, transparent conductive sheet and touch panel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transparent conductive film having superior pen-input durability used for a touch panel is, where its transparent conductive thin film will not break, even in a friction test of 100 thousand times under the load of 4.9 N by using especially a pen made of polyacetal (tip shape of 0.8 mmR) in particular. SOLUTION: This transparent conductive film (1) is a transparent plastic film (11) laminated with a transparent conductive thin film (12) with tin oxide as the major component at least on a single face, and featured with specific resistance of the transparent conductive thin film (12) is 8×10-4 to 1×10-1 Ω.cm, and further the light transmittance of the transparent film (1) is not less than 82%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent conductive film using a plastic film, a transparent conductive sheet, and a touch panel using the same. It has excellent properties.

[0002]

2. Description of the Related Art A transparent conductive film in which a transparent and low-resistance compound thin film is formed on a plastic film,
It is widely used in applications in the electrical and electronic fields, such as applications utilizing its conductivity, for example, flat panel displays such as liquid crystal displays, electroluminescence panels (EL), and displays, and transparent electrodes of touch panels.

In recent years, with the spread of portable information terminals and notebook personal computers with a touch panel, a touch panel having better pen sliding resistance than ever has been required.

In order to manufacture such a touch panel excellent in pen sliding resistance, the transparent conductive thin film on the fixed electrode side and the transparent conductive thin film on the movable electrode (film electrode) side come into contact with each other at the time of pen input. However, it is necessary for the transparent conductive thin film to be free from cracking, peeling, and other destruction by pen load when they come into contact with each other.

[0005]

However, the conventional transparent conductive film has the following problems.

A transparent conductive thin film is formed on a transparent plastic film having a thickness of 120 μm or less, and is adhered to another transparent substrate with an adhesive layer (Japanese Patent Laid-Open No.
No.-66809) has been proposed. However, after using the polyacetal pen described in the sliding durability test described below and performing the linear sliding test 100,000 times with a load of 4.9 N, the transparent conductive thin film peels off, and the durability against pen input occurs. Was inadequate. For this reason, the whiteness of the peeled portion lowers the display quality when used for a display with a touch panel. In addition, foreign substances such as dust are mixed during bonding because they are bonded using an adhesive,
It becomes a transparent conductive film with many optical defects.

Also, on a transparent plastic film,
A layer formed by hydrolysis of an organosilicon compound is provided, and a transparent conductive film further laminated with a crystalline transparent conductive thin film is disclosed in, for example, JP-A-60-131711, JP-A-61-79647, JP-A-61-18
3809, JP-A-2-194943, JP-A-2-276630 and JP-A-8-64034.

[0008] However, these transparent conductive films are very brittle because they are crystalline transparent conductive thin films.
Using a polyacetal pen described in the sliding durability test described below, cracks occur in the transparent conductive thin film after 100,000 linear sliding tests with a load of 4.9 N. Further, since a heat treatment at about 150 ° C. is required after sputtering the transparent conductive thin film, there is a disadvantage that processing cost is increased.

In view of the above-mentioned conventional problems, an object of the present invention is to provide an excellent pen input durability when used for a touch panel,
In particular, it is to provide a transparent conductive film in which a transparent conductive thin film is not broken even by a slide test of 100,000 times under a load of 4.9N using a polyacetal pen described in a sliding durability test described below. .

[0010]

SUMMARY OF THE INVENTION The present invention has been made in view of the above situation, and a transparent conductive film, a transparent conductive sheet, and a touch panel which can solve the above-mentioned problems are provided. It is as follows.

That is, the first invention of the present invention is a transparent plus
Tin oxide on at least one surface of the tic film (11)
The transparent conductive thin film (12) mainly composed of
A bright conductive film (1), wherein the transparent conductive thin film is
The specific resistance of (12) is 8 × 10 ^-Four~ 1 × 10^-1Ω · cm
Light transmission of the transparent conductive film (1)
A transparent conductive filter having a ratio of not less than 82%.
Lum.

The second invention is directed to the transparent conductive thin film (1).
2) is the transparent conductive film according to the first invention, wherein the transparent conductive film contains 30% by weight or less of antimony oxide.

A third invention is characterized in that the adhesive force between the transparent plastic film (11) and the transparent conductive thin film (12) is 0.1 N / 15 mm or more.
Or the transparent conductive film according to the second aspect of the invention.

A fourth invention is characterized in that a cured material layer (13) made of a curable resin is provided between the transparent plastic film (11) and the transparent conductive thin film (12). 3. The transparent conductive film according to any one of the third aspect of the invention.

A fifth invention is characterized in that a hard coat layer (14) is provided on the surface of the transparent plastic film (11) on which the transparent conductive thin film (12) is not formed. A transparent conductive film according to any one of the first to fourth aspects.

In a sixth aspect, the hard coat layer (1)
4) The transparent conductive film according to the fifth aspect, wherein the transparent conductive film has an antiglare effect.

According to a seventh aspect of the present invention, there is provided the hard coat layer (1)
The transparent conductive film according to the fifth or sixth aspect of the present invention, wherein a low reflection treatment is applied to 4).

According to an eighth aspect of the present invention, there is provided a transparent conductive film (1) according to any one of the first to seventh aspects, wherein a surface opposite to a surface on which the transparent conductive thin film (12) is laminated is provided. A transparent conductive sheet characterized by laminating a transparent resin sheet via an adhesive.

A ninth invention is a touch panel in which a pair of panel plates having a transparent conductive thin film is disposed via a spacer so that the transparent conductive thin films face each other, and at least one of the panel plates is a touch panel. A touch panel comprising the transparent conductive film (1) or the transparent conductive sheet according to any one of the first to eighth inventions.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION The transparent plastic film (11) in the present invention means that an organic polymer is melt-extruded or solution-extruded, and if necessary, stretched in the longitudinal direction and / or the width direction, cooled, and heat-set. , And organic polymers include polyethylene, polypropylene, polyethylene terephthalate, polyethylene-2,6-naphthalate, polypropylene terephthalate, nylon 6, nylon 4, nylon 66, nylon 12, polyimide, polyamide imide, and polyether. Sulfane, polyether ether ketone, polycarbonate, polyarylate, cellulose propionate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyetherimide, polyphenylene sulfide, polyphenylene oxide, Polystyrene, syndiotactic polystyrene, such as norbornene-based polymer and the like.

Among these organic polymers, polyethylene terephthalate, polypropylene terephthalate, polyethylene-2,6-naphthalate, syndiotactic polystyrene, norbornene-based polymers, polycarbonate, polyarylate and the like are most preferably used. Further, these organic polymers may be obtained by copolymerizing a small amount of a monomer of another organic polymer or blending another organic polymer.

The thickness of the transparent plastic film (11) in the present invention is preferably more than 10 μm and not more than 300 μm, particularly preferably in the range of 70 to 260 μm. If the thickness of the transparent plastic film (11) is 10 μm or less, the mechanical strength is insufficient, and the deformation with respect to pen input when used for a touch panel becomes too large, and the durability becomes insufficient. On the other hand, the thickness is 300 μm
Exceeding the limit results in a large pen load for deforming the film when used for a touch panel, which is not preferable.

The transparent plastic film (11) of the present invention may be obtained by subjecting the film (11) to a corona discharge treatment, a glow discharge treatment, a flame treatment, an ultraviolet irradiation treatment, an electron beam irradiation treatment within a range not to impair the object of the present invention. A surface activation treatment such as an ozone treatment may be performed.

As the transparent conductive thin film (12) in the present invention, a material having both transparency and conductivity, and a material which is less deteriorated by abrasion between the transparent conductive thin films in a sliding test, such as tin oxide, is used. It must be the main component.

The transparent conductive material containing tin oxide as a main component
The specific resistance of the conductive thin film (12) is 8 × 10 ^-Four~ 1 × 10^-1Ω
cm. Transparent conductive thin film
The specific resistance of (12) is 8 × 10^-FourTo be less than Ω · cm
Requires extremely low film-forming speed,
Not suitable. Further, the specific resistance is 1 × 10^-1Ω · cm
If the specific resistance is too high, the conductivity will be insufficient and
When used for a touch panel, the position detection accuracy becomes insufficient.

Further, the transparent conductive film (1) of the present invention needs to have a light transmittance of at least 82%, preferably at least 83%, particularly preferably at least 84%. When the light transmittance is less than 82%, the light transmittance when used for the touch panel is insufficient, and the display quality of the display on the back of the touch panel is insufficient.

The transparent conductive thin film (1) containing tin oxide as a main component
The film thickness of 2) is preferably in the range of 4 to 800 nm, and particularly preferably in the range of 5 to 500 nm. When the film thickness of the transparent conductive thin film (12) is less than 4 nm, it is difficult to form a continuous thin film and does not show good conductivity. On the other hand, if the thickness is more than 800 nm, the transparency is undesirably reduced.

In order to further reduce the deterioration of the transparent conductive thin films due to wear in the sliding test, antimony oxide was added to the transparent conductive thin film (12) containing tin oxide as a main component. It is preferable that the content be contained in a proportion of 30% by weight or less. When the content of antimony oxide in the thin film is more than 30% by weight, a transparent conductive film having insufficient light transmittance or conductivity tends to be obtained.

The method for forming the transparent conductive thin film (12) containing tin oxide as a main component in the present invention includes a vacuum deposition method,
Known methods such as a sputtering method, a CVD method, an ion plating method, and a spray method are known, and the above methods can be appropriately used depending on a required film thickness.

For example, in the case of a sputtering method, a normal sputtering method using an oxide target, a reactive sputtering method using a metal target, or the like is used. At this time, oxygen, nitrogen, water vapor, or the like may be introduced as a reactive gas, or means such as ozone addition, plasma irradiation, or ion assist may be used in combination. Also,
As long as the object of the present invention is not impaired, DC, AC,
A bias such as a high frequency may be applied.

The temperature at which the transparent conductive thin film (12) is formed on the transparent plastic film is preferably 150 ° C. or less. In order to increase the temperature at the time of film formation to a temperature exceeding 150 ° C., it is necessary to extremely reduce the feeding speed of the plastic film, which is industrially unsuitable.

The degree of vacuum at the time of performing the sputtering is preferably in the range of 0.013 to 13 Pa.
If the degree of vacuum is higher than 0.013 Pa, stable discharge cannot be performed, so that sputtering is not stable. Also,
Even if the degree of vacuum is lower than 13 Pa, stable discharge cannot be performed, so that sputtering is not stable. The same applies to other methods such as an evaporation method and a CVD method.

The adhesion between the transparent conductive thin film (12) containing tin oxide as a main component and the plastic film (11) formed as described above is preferably 0.1 N / 15 mm or more. If the adhesive force is less than 0.1 N / 15 mm, the transparent conductive thin film (12) tends to peel off during a linear sliding test when used for a touch panel.

In order to improve the adhesion, it is effective to pre-treat the surface of the plastic film before laminating the transparent conductive layer (12). Specific methods include a physical surface roughening method that increases the surface area of the plastic film by sandblasting or embossing, and a glowing method to increase functional groups such as carbonyl groups, carboxyl groups, and hydroxyl groups on the film surface. A discharge treatment method in which corona discharge is applied to the film surface,
A chemical treatment method of treating the film surface with an acid or alkali to increase polar groups such as amino groups, hydroxyl groups, and carbonyl groups on the film surface may be used.

For example, as the acidic aqueous solution, a chromic acid mixed solution or a hydrochloric acid aqueous solution which is a mixed aqueous solution of sodium dichromate and sulfuric acid is used, and as the alkaline aqueous solution,
An aqueous solution of sodium hydroxide, an aqueous solution of potassium hydroxide, or the like is used. After immersing the plastic film (11) in an acidic or alkaline aqueous solution, the plastic film (11) is immersed in pure water to sufficiently remove acid or alkaline components. Thereafter, nitrogen gas is blown onto the plastic film (11) to dry the moisture remaining on the film surface.

Further, the transparent plastic film (1)
In order to improve the adhesion between 1) and the transparent conductive thin film (12), a curable resin is provided between the plastic film (11) and the transparent conductive thin film (12) containing tin oxide as a main component. It is preferable to provide a cured product layer (13). As the curable resin, a resin alone or a mixture of curable resins such as a polyester resin, a urethane resin, an acrylic resin, a melamine resin, an epoxy resin, a silicon resin, and a polyimide resin is preferable. After adding a known curing agent and catalyst to these curable resins, energy such as heating, ultraviolet irradiation, and electron beam irradiation is applied to form a cured layer (13).

The thickness of the cured layer (13) made of a curable resin is preferably in the range of 0.02 to 10 μm. When the thickness of the cured product layer (13) is less than 0.02 μm, the effect of improving the adhesive force becomes insufficient, and when it exceeds 10 μm, it is not preferable from the viewpoint of productivity.

Further, in order to further improve the scratch resistance of the outermost layer (pen input surface) when a touch panel is formed, the transparent conductive thin film (1) of the transparent plastic film (11) is used.
A hard coat layer (14) is formed on the surface opposite to the surface on which 2) is formed (the outermost pen input surface when a touch panel is formed).
Is preferably provided. The hardness of the hard coat layer is preferably 2H or more in pencil hardness. If the hardness is lower than 2H, the hard coat layer of the transparent conductive film is insufficient in abrasion resistance.

The thickness of the hard coat layer (14) is 0.1.
It is preferably from 5 to 10 μm. 0.5μm thickness
If it is less than 10 μm, the scratch resistance tends to be insufficient, and if it is more than 10 μm, it is not preferable from the viewpoint of productivity.

The film-forming component of the curable resin composition used in the hard coat layer (14) is preferably one having an acrylate-based functional group, for example, a polyester resin or polyether resin having a relatively low molecular weight. Acrylic resin, epoxy resin, urethane resin, alkyd resin,
Spiro acetal resin, polybutadiene resin, polythiol polyene resin, oligomer or prepolymer such as (meth) acrylate of polyfunctional compound such as polyhydric alcohol, and ethyl (meth) acrylate, ethylhexyl (meth) acrylate as reactive diluent, styrene,
Monofunctional monomers and polyfunctional monomers such as methylstyrene and N-vinylpyrrolidone, for example, trimethylolpropane tri (meth) acrylate, hexanediol (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate , Pentaerythritol tri (meta)
Acrylate, dipentaerythritol hexa (meth)
Those containing relatively large amounts of acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate and the like can be used.

In particular, a mixture of a polyester acrylate and a polyurethane acrylate is preferred. The reason is that polyester acrylate has a very hard coating film and is suitable as a hard coat layer. However, a coating film of polyester acrylate alone has low impact resistance and tends to be brittle, so that polyurethane acrylate is used in combination to impart impact resistance and flexibility to the coating film. The mixing ratio of polyurethane acrylate to 100 parts by weight of polyester acrylate is preferably 30 parts by weight or less. If this compounding ratio exceeds 30 parts by weight, the coating film tends to be too soft and the impact resistance tends to be insufficient.

As the method of curing the curable resin composition, a usual curing method, that is, a method of curing by heating, irradiation with an electron beam or ultraviolet rays can be used. For example,
In the case of electron beam curing, 50 to 1000 keV, preferably emitted from various electron beam accelerators such as Cockloft-Walton type, Handie graph type, Resonant transformation type, Insulating core transformer type, Linear type, Dynamitron type, High frequency type, etc. Is 100-3
An electron beam having an energy of 00 keV is used. In the case of ultraviolet curing, ultraviolet rays emitted from light rays such as an ultrahigh-pressure mercury lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, a xenon arc, and a metal halide lamp can be used.

Further, in the case of ionizing radiation curing, acetophenones, benzophenones, Michler benzoyl benzoate, α-amyloxime ester, tetramethylthiuram monosulfide may be used as a photopolymerization initiator in the curable resin composition. , Thioxanthones, n-butylamine, triethylamine, tri-
It is preferable to mix n-butylphosphine and the like. In the present invention, it is particularly preferable to mix urethane acrylate as an oligomer and dipentaerythritol hexa (meth) acrylate as a monomer.

In order to impart antiglare property to the hard coat layer, it is effective to disperse inorganic particles such as CaCO ₃ and SiO ₂ in the curable resin or to form an uneven shape on the surface of the hard coat layer. It is. For example, in order to form irregularities, a coating liquid containing a curable resin composition is applied, a shaped film having a convex shape on its surface is laminated, and ultraviolet light is irradiated from above the shaped film to form a curable resin. After curing, the resin is obtained by peeling off only the shaped film.

The above-mentioned imprinting film may be a film in which a desired convex shape is provided on a base film such as polyethylene terephthalate (hereinafter abbreviated as PET) having releasability, or a base film such as PET. And a delicate convex layer may be used. The formation of the convex layer can be obtained by, for example, applying a resin composition comprising inorganic particles and a binder resin on a base film. As the binder resin, for example, an acrylic polyol crosslinked with a polyisocyanate is used, and as the inorganic particles, CaCO ₃ , SiO _2, or the like can be used. In addition, a mat type PET in which inorganic particles such as SiO ₂ are kneaded during the production of PET can also be used.

When the molding film is laminated on a coating film of an ultraviolet curable resin and then irradiated with ultraviolet rays to cure the coating film, when the molding film is a PET-based film, the film is exposed to ultraviolet light. There is a disadvantage that the short wavelength side is absorbed and curing of the ultraviolet curable resin is insufficient. Therefore, it is necessary to use a shaping film having a transmittance of 20% or more for the shaping film to be laminated on the coating film of the ultraviolet curable resin.

In order to further improve the transmittance of visible light when used in a touch panel, a hard coat layer (1
4) A low reflection process may be performed thereon. In this low reflection treatment, it is preferable that a material having a refractive index different from the refractive index of the hard coat layer (14) is laminated as a single layer or two or more layers. In the case of a single layer structure, it is preferable to use a material having a smaller refractive index than the hard coat layer (14).
In the case of a multilayer structure having two or more layers, a layer having a higher refractive index than the hard coat layer (14) is used for a layer adjacent to the hard coat layer (14), and It is better to select a material having a small refractive index.
The material constituting such a low reflection treatment is not particularly limited, as long as it satisfies the above-described relationship of the refractive index, whether it is an organic material or an inorganic material. For example, CaF ₂ , MgF ₂ , NaAl
F ₄ , SiO ₂ , ThF ₄ , ZrO ₂ , Nd ₂ O ₃ , Sn
It is preferable to use a dielectric such as O ₂ , TiO ₂ , CeO ₂ , ZnS, In ₂ O ₃ or the like.

The low reflection treatment may be a dry coating process such as a vacuum evaporation method, a sputtering method, a CVD method, an ion plating method, or a wet coating process such as a gravure method, a reverse method, or a die method.

Further, prior to lamination of the low reflection treatment layer, known pretreatments such as a corona discharge treatment, a plasma treatment, a sputter etching treatment, an electron beam irradiation treatment, an ultraviolet irradiation treatment, a primer treatment, an easy adhesion treatment, etc. A surface treatment may be applied to the hard coat layer (14).

The transparent conductive film (1) of the present invention is used as a fixed electrode of a touch panel by laminating a surface on which the transparent conductive thin film (12) is not formed and a transparent resin sheet via an adhesive. A transparent conductive laminated sheet is obtained. That is, by making the fixed electrode made of resin from glass, a lightweight and hard-to-break touch panel can be manufactured.

The pressure-sensitive adhesive is not particularly limited as long as it has transparency. For example, acrylic pressure-sensitive adhesives, silicone-based pressure-sensitive adhesives, and rubber-based pressure-sensitive adhesives are suitable. Although the thickness of the pressure-sensitive adhesive is not particularly limited, it is usually desirable to set the thickness in the range of 1 to 100 μm. When the thickness of the pressure-sensitive adhesive is less than 1 μm, it is difficult to obtain practically no problematic adhesion, and when the thickness exceeds 100 μm, it is not preferable from the viewpoint of productivity.

The transparent resin sheet to be bonded through the pressure-sensitive adhesive is used for imparting the same mechanical strength as glass, and the thickness is preferably in the range of 0.05 to 5 mm. When the thickness of the transparent resin sheet is less than 0.05 mm, the mechanical strength is insufficient compared with glass. On the other hand, when the thickness exceeds 5 mm, it is too thick and is not suitable for use in a touch panel. The material of the transparent resin sheet may be the same as the transparent plastic film described above.

FIG. 15 shows an example of a touch panel using the transparent conductive film (1) of the present invention. In a touch panel in which a pair of panel plates having a transparent conductive thin film are arranged via a spacer so that the transparent conductive thin films face each other, the transparent conductive film (1) of the present invention is used for one of the panel plates. Things. In addition, when characters are input to the touch panel with a pen, the opposing transparent conductive thin films come into contact with each other due to pressing from the pen, and are electrically turned on, and the position of the pen on the touch panel is detected. Can be. By continuously and accurately detecting the pen position, characters can be recognized from the locus of the pen. At this time, if the transparent conductive film (1) of the present invention is used for the panel plate on the pen contact side, the touch panel can be made stable over a long period of time because of excellent pen input durability.

FIG. 16 is a cross-sectional view of a plastic touch panel using the transparent conductive film (1) and the transparent conductive sheet of the present invention and not using a glass substrate. Since this plastic touch panel does not use glass, it is extremely lightweight and does not break due to impact.

[0055]

The present invention will be described more specifically below with reference to examples. In addition, the measuring method used for the evaluation of the transparent conductive film (1) and the touch panel used in Examples and Comparative Examples of the present invention is as follows.

<Surface resistivity> The surface resistivity was measured by a four-terminal method in accordance with JIS K7194. Lotest AMCP-T400 manufactured by Mitsubishi Yuka Co., Ltd. was used as a measuring device.

<Light Transmittance> The light transmittance was measured using NDH-1001DP manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with JIS K7105.

<Measurement of Adhesion Force> An ionomer film (HM-07, manufactured by Tamapoly Co., Ltd.) having a thickness of 40 μm was coated with a polyester-based adhesive (Takenate A310 / Takelac A-3, manufactured by Takeda Pharmaceutical Co., Ltd.). 75μ
m biaxially oriented PET film (Toyobo Co., Ltd .: E
5100) to produce a laminate for measuring adhesive force. The ionomer surface of the laminate for measuring adhesion is opposed to the transparent conductive thin film surface of the transparent conductive film, and
Thermocompression bonding was performed at 130 ° C. for 2 seconds under a pressure of MPa. This laminate is bonded to a laminate for measuring adhesive force and a transparent conductive film in one.
Peeling was performed by an 80-degree peeling method, and this peeling force was used as an adhesive force. The peeling speed at this time was 1000 mm / min.

<Calculation of Specific Resistance> Transparent conductive thin film (12)
Of the film thickness D and the surface resistivity Rs, that is, D × Rs
Is the specific resistance.

<Composition Analysis in Thin Film> The composition ratio of tin oxide, antimony oxide, and indium oxide in the thin film was measured by a plasma emission analyzer (ICPS-2000, manufactured by Shimadzu Corporation).

<Sliding durability test> A 4.9 N load was applied to a polyacetal pen (tip shape: 0.8 mmR), and a sliding test of 100,000 times (50,000 reciprocations) was performed on the touch panel. . The sliding distance at this time was 47 mm, and the sliding speed was 240 mm / sec. After this sliding durability test,
It was visually observed whether the sliding portion was whitened. Further, a mark ○ of 20 mmφ was written on the sliding portion with a pen load of 0.78 N, and it was evaluated whether the touch panel could correctly read the mark. In addition, pen load 0.
ON resistance when the sliding part is pressed with 78N (resistance value when the movable electrode (film electrode) and fixed electrode come into contact)
Was measured.

Example 1 Biaxial orientation P having a thickness of 188 μm and having an easily adhesive layer on one side
An ET film (A4140, manufactured by Toyobo Co., Ltd.) was used as the transparent plastic film (11).

Next, the surface of the plastic film (11), which has not been subjected to the easy-adhesion treatment, has a thickness of 25 by DC magnetron sputtering using tin as a target.
nm, a transparent conductive thin film (12) was formed. At this time, the degree of vacuum was 0.4 Pa, and Ar gas was used as a gas for 130 s.
ccm and O ₂ gas were flowed at a flow rate of 70 sccm, the target applied power was 2.5 W / cm ^2, and a pulse of +20 V at 50 kHz and 5 μsec. width was applied to prevent arc discharge. Also, for film cooling,
The film was brought into contact with a cooling roll at 10 ° C., and the line was run at a speed of 5 m / min.

The transparent conductive film (1) was used as one panel plate, and a glass substrate (450 Ω / □, manufactured by Nippon Soda Co., Ltd.) was used as the other panel plate. This 2
The two panel plates were arranged via epoxy beads having a diameter of 30 μm so that the transparent conductive thin films faced each other, to produce a touch panel.

Example 2 Biaxial orientation P having a thickness of 188 μm and having an easily adhesive layer on one side
An ET film (A4140, manufactured by Toyobo Co., Ltd.) was used as the transparent plastic film (11).

Next, a target of tin oxide containing antimony trioxide at 5% by weight, 10% by weight and 25% by weight was placed on the surface of the plastic film (11) which had not been subjected to the easy adhesion treatment. 5.7g / cm
³ , 5.0 g / cm ³ , 4.1 g / cm ³ ) to form a 30 nm thick transparent conductive thin film (12) by DC magnetron sputtering. At this time, the degree of vacuum was 0.4 Pa, and Ar gas was 130 scc as a gas.
m, O ₂ gas was flowed at a flow rate of 15 sccm, the target applied power was 1.5 W / cm ^2, and a +20 V pulse of 100 kHz and 5 μsec. width was applied to prevent arc discharge. Also, for cooling the film, -1
The film was brought into contact with a cooling roll at 0 ° C., and the film was run at a line speed of 3 m / min.

Using this transparent conductive film (1) as one panel plate, a touch panel was produced in the same manner as in Example 1.

Example 3 Biaxial orientation P having an easy-adhesion layer on both sides with a thickness of 188 μm
An ET film (A4340, manufactured by Toyobo Co., Ltd.) was used as the transparent plastic film (11). further,
0.7% by weight of copolymerized polyester resin (manufactured by Toyobo Co., Ltd., Byron RV280), isocyanate-based crosslinking agent (Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd.)
3% by weight, solvent: methyl ethyl ketone 65% by weight, toluene 24% by weight, cyclohexanone 10% by weight
Was obtained. Next, the coating solution was applied on the easy-adhesion layer on one side of the PET film by a bar coating method. 3 used wire bars
It was turn. 130 ° C coated film
For 30 minutes to cure the coating layer. The thickness of the cured product layer (13) made of the curable resin was 0.1 μm after drying.

Next, using a target (density: 5.7 g / cm ³ ) as a target (density: 5.7 g / cm ³ ) tin oxide containing 5% by weight of antimony oxide on the cured curable resin layer (13), A 20 nm transparent conductive thin film (12) was formed. At this time, the degree of vacuum was 0.4 Pa, Ar gas was flowed at a flow rate of 130 sccm and O ₂ gas at a flow rate of 15 sccm, and the power applied to the target was 1.
5 W / cm ² and 100 to prevent arc discharge
A +20 V pulse with a frequency of 5 kHz and a frequency of 5 kHz was applied. Further, for cooling the film, the film was brought into contact with a cooling roll at −10 ° C., and the film was run at a line speed of 3 m / min.

Using this transparent conductive film (1) as one panel plate, a touch panel was produced in the same manner as in Example 1.

Example 4 In the same manner as in Example 3, the plastic film (11)
A laminate having a layer configuration of a cured product layer (13) composed of a curable resin was prepared. On the surface of the laminate opposite to the cured product layer (13), an ultraviolet-curable resin (EXG, manufactured by Dainichi Seika) made of a mixture of polyester acrylate and polyurethane acrylate as an ultraviolet-curable resin was coated with a film thickness of 5 mm.
The solution was applied by a gravure reverse method to a thickness of μm (at the time of drying), and the solvent was dried. Thereafter, the resin was passed under a 160-W ultraviolet irradiation device at a speed of 10 m / min to cure the ultraviolet-curable resin, thereby forming a hard coat layer (14).

This hard coat layer (14) / plastic film (11) / cured material layer (1)
On the cured product layer (13) of the laminate having the layer configuration of 3),
In the same manner as in Example 3, a tin-antimony composite oxide thin film was formed.

Using this transparent conductive film (1) as one panel plate, a touch panel was produced in the same manner as in Example 1.

Example 5 In the same manner as in Example 3, the plastic film (11)
A laminate having a layer configuration of a cured product layer (13) composed of a curable resin was prepared. On the surface of the laminate opposite to the cured product layer (13), an ultraviolet-curable resin (EXG, manufactured by Dainichi Seika) made of a mixture of polyester acrylate and polyurethane acrylate as an ultraviolet-curable resin was coated with a film thickness of 5 mm.
The solution was applied by a gravure reverse method to a thickness of μm (at the time of drying), and the solvent was dried. Thereafter, a mat-shaped PET film (X, manufactured by Toray) having a fine convex shape formed on its surface was laminated so that the mat surface was in contact with the ultraviolet curable resin. The surface shape of this mat-shaped film is as follows: an average surface roughness of 0.40 μm;
μm, and the maximum surface roughness is 25 μm. The film thus laminated was placed under a 160 W ultraviolet irradiation device for 1
The resin was passed at a speed of 0 m / min to cure the ultraviolet curable resin. Next, the mat-shaped film was peeled off, and the surface was subjected to concave processing to form a hard coat layer (14) having an antiglare effect.

The hard coat layer (1) / plastic film (11) / cured material layer (1)
On the cured product layer (13) of the laminate having the layer configuration of 3),
In the same manner as in Example 3, a tin-antimony composite oxide thin film was formed as a transparent conductive thin film (12).

Using this transparent conductive film (1) as one panel plate, a touch panel was produced in the same manner as in Example 1.

Example 6 In the same manner as in Example 5, the antiglare hard coat layer (14)
A laminate having a layer structure of / plastic film (11) / cured material layer (13) composed of curable resin / transparent conductive thin film (12) was produced. Next, TiO ₂ (refractive index: 2.30, film thickness 15 nm) and SiO ₂ (refractive index: 1.46, film thickness 29 n) are sequentially formed on the hard coat layer (14).
m), TiO ₂ (refractive index: 2.30, film thickness 109 n)
m) and SiO ₂ (refractive index: 1.46, film thickness 87 nm) were laminated to form an antireflection treatment layer. In order to form a TiO ₂ thin film, the degree of vacuum is 0.27 P by direct current magnetron sputtering using titanium as a target.
a, Ar gas was flowed at a flow rate of 500 sccm and O ₂ gas at a flow rate of 80 sccm as a gas. Also, 0 on the back of the substrate
The cooling of a plastic film was carried out by providing a cooling roll of ° C. At this time, a power of 7.8 W / cm ² was supplied to the target, and the dynamic rate was 23 nm · m / min.

To form an SiO ₂ thin film, silicon is used as a target and the degree of vacuum is set to 0.27 Pa by Argon gas as a gas by DC magnetron sputtering.
00 sccm and O ₂ gas were flowed at a flow rate of 80 sccm. In addition, a cooling roll of 0 ° C. is provided on the back of the substrate,
The plastic film was cooled. At this time, a power of 7.8 W / cm ² was supplied to the target, and the dynamic rate was 23 nm · m / min.

Using this transparent conductive film (1) as one panel plate, a touch panel was produced in the same manner as in Example 1.

Example 7 A transparent conductive film (1) produced in the same manner as in Example 3 was applied with an acrylic pressure-sensitive adhesive to a thickness of 1.0 mm.
To form a transparent conductive laminated sheet. Using this transparent conductive laminated sheet as a fixed electrode, and using the transparent conductive film of Example 5 as a movable electrode, a touch panel was produced in the same manner as in Example 1.

Comparative Example 1 A transparent conductive film (1) was produced in the same manner as in Example 1 except that the amount of O ₂ gas introduced during sputtering was changed to 100 sccm. Further, in the same manner as in Example 1, a touch panel was produced using the transparent conductive film (1).

Comparative Example 2 Example 2 was repeated except that a tin oxide target (density: 3.2 g / cm ³ ) containing 35% by weight of antimony trioxide was used.
In the same manner as in the above, a transparent conductive film (1) was produced.
Example 1 was prepared using this transparent conductive film (1).
In the same manner as in the above, a touch panel was manufactured.

COMPARATIVE EXAMPLE 3 An alcoholic solution of an organosilicon compound in a mixture of butanol / isopropanol (concentration: 1% by weight) was applied to the easily adhesive surface of a biaxially stretched PET film similar to that in Example 1, and then heated at 100 ° C. Dry for 1 minute. Thereafter, a film was formed on the organosilicon compound at a substrate temperature of 120 ° C. using an indium-tin composite oxide target having a tin oxide content of 5% by weight. The degree of vacuum is 0.2 Pa, and Ar is used as a gas.
A gas was supplied at a flow rate of 130 sccm and an O ₂ gas at a flow rate of 1 sccm, and electric power of 1.5 W / cm ² was applied to the target. After the film formation, a heat treatment was further performed at 150 ° C. for 10 minutes to produce a crystalline indium-tin composite oxide thin film. Further, a touch panel was produced in the same manner as in Example 1 using this transparent conductive film.

Comparative Example 4 A transparent conductive film was produced in the same manner as in Example 3, except that indium oxide containing 35% by weight of tin oxide was used as a target. Further, a touch panel was produced in the same manner as in Example 1 using this transparent conductive film.

Table 1 shows the measurement results of the transparent conductive films obtained above. The results of a sliding durability test when used as a touch panel are shown in FIGS. From these results, the transparent conductive film of the present invention and the touch panel using the same are excellent in transparency and have no deterioration even after a severe sliding durability test of 100,000 times under a load of 4.9 N 100 times. Since the mark is recognized and output, it is understood that the mark is suitable for the pen input touch panel.

[0086]

[Table 1]

[0087]

The transparent conductive film (11) of the present invention
Is characterized in that a transparent conductive thin film (12) containing tin oxide as a main component is laminated on at least one surface of the transparent plastic film (1) and has a low specific resistance and a high light transmittance. The pen input touch panel using the transparent conductive film (11) is excellent in pen input durability such that peeling and cracking do not occur even when opposing transparent conductive thin films come into contact with each other by pressing the pen. Also, it has excellent position detection accuracy and display quality. Therefore, it is suitable as a pen input touch panel.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram illustrating an output shape from a touch panel according to a first embodiment.

FIG. 2 is an explanatory diagram illustrating an output shape from a touch panel according to a second embodiment.

FIG. 3 is an explanatory diagram illustrating an output shape from a touch panel according to a third embodiment.

FIG. 4 is an explanatory diagram illustrating an output shape from a touch panel according to a fourth embodiment.

FIG. 5 is an explanatory diagram illustrating an output shape from a touch panel according to a fifth embodiment.

FIG. 6 is an explanatory diagram illustrating an output shape from a touch panel according to a sixth embodiment.

FIG. 7 is an explanatory diagram illustrating an output shape from a touch panel according to a seventh embodiment.

FIG. 8 is an explanatory diagram showing an output shape from a touch panel of Comparative Example 1.

FIG. 9 is an explanatory diagram showing an output shape from a touch panel of Comparative Example 2.

FIG. 10 is an explanatory diagram showing an output shape from a touch panel of Comparative Example 3.

FIG. 11 is an explanatory diagram showing an output shape from a touch panel of Comparative Example 4.

FIG. 12 is an explanatory diagram showing the layer configuration of the transparent conductive films of Examples 1 and 2.

FIG. 13 is an explanatory diagram showing a layer configuration of a transparent conductive film of Example 3.

FIG. 14 is an explanatory diagram showing a layer configuration of a transparent conductive film of Example 4.

FIG. 15 is a sectional view of a touch panel according to a second embodiment.

FIG. 16 is a sectional view of a touch panel according to a seventh embodiment.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Transparent conductive film 11 Plastic film 12 Transparent conductive thin film 13 Cured material layer made of curable resin 14 Hard coat layer 2 Glass plate 3 Bead 4 Adhesive 5 Transparent resin sheet

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01H 13/70 H01H 13/70 EF term (Reference) 4F100 AA28B AA29B AA29H AK01A AK01C AK01E AK25D AK42A AK51C BA02 BA03 BA04 BA05 BA06 BA07 BA10A BA10B BA10D BA10E BA13 CB05 CC00D EH66B EJ38A GB41 GB90 JB12C JB14D JG01B JG04B JK06 JK12D JM02B JN01 JN01A JN01F JN06D YY00 YY00B YY00 A4BA015 A15 BA15A15 CC 5G307 FA02 FB01 FC02 FC05 FC10

Claims (9)

[Claims] 1. A transparent plastic film (11) having a small amount.
At least one surface has a transparent conductive thin film containing tin oxide as a main component.
A transparent conductive film (1) on which a film (12) is laminated;
Thus, the specific resistance of the transparent conductive thin film (12) is 8 × 10
^-Four~ 1 × 10 ^-1Ω · cm, and the transparent conductive
The light transmittance of the film (1) must be 82% or more.
Characteristic transparent conductive film. 2. The transparent conductive film according to claim 1, wherein the transparent conductive thin film contains 30% by weight or less of antimony oxide. 3. The transparent plastic film (11).
And the transparent conductive thin film (12) has an adhesive force of 0.1 N /
3. The method according to claim 1, wherein the distance is at least 15 mm.
The transparent conductive film according to the above. 4. The transparent plastic film (11).
A cured product layer (13) made of a curable resin is provided between the transparent conductive thin film (12) and the transparent conductive thin film (12).
4. The transparent conductive film according to any one of 1 to 3. 5. The transparent plastic film (11)
The transparent conductive film according to any one of claims 1 to 4, wherein a hard coat layer (14) is provided on a surface on which the transparent conductive thin film (12) is not formed. 6. The transparent conductive film according to claim 5, wherein said hard coat layer has an antiglare effect. 7. The transparent conductive film according to claim 5, wherein the hard coat layer has been subjected to a low reflection treatment. 8. A transparent resin sheet is adhered to the surface of the transparent conductive film (1) according to any one of claims 1 to 7 opposite to the surface on which the transparent conductive thin film (12) is laminated. A transparent conductive sheet characterized by being laminated via an agent. 9. A touch panel in which a pair of panel plates having a transparent conductive thin film are arranged via a spacer so that the transparent conductive thin films face each other, wherein at least one of the panel plates is provided. A touch panel comprising the transparent conductive film (1) or the transparent conductive sheet according to any one of the above.