KR20120024837A - Transparent conductive multilayer film - Google Patents

Abstract

INDUSTRIAL APPLICABILITY The present invention has a low surface resistance value in an electrode film used for a capacitive touch panel or the like, and when the transparent conductive thin film is patterned, the difference in optical characteristics between the portion with and without the transparent conductive thin film is small. It is a subject to provide this inconspicuous transparent conductive laminated film.
In order to solve the said subject, the transparent conductive laminated film of this invention has the structure which laminated | stacked the high refractive index layer, the low refractive index layer, and the transparent conductive thin film layer in this order on the base material which becomes a transparent plastic film, The refractive index is in the range of 1.70 to 2.50, the film thickness is 4 to 20 nm, the refractive index of the low refractive index layer is in the range of 1.30 to 1.60, the film thickness is 20 to 50 nm, and the specific resistance of the transparent conductive thin film layer is 1.0 to 4.6 × 10. ^{It is characterized by -4} ohm-cm and a film thickness of 10-28 nm.

Description

Transparent conductive multilayer film

This invention relates to the transparent conductive laminated film which laminated | stacked the high refractive index layer, the low refractive index layer, and the transparent conductive thin film layer in this order on the base material which becomes a transparent plastic film. In particular, when used as a patterned electrode film such as a capacitive touch panel, the surface resistance value is low, so that the touch panel can be enlarged, and the difference in optical characteristics between the portion having the transparent conductive thin film layer and the removed portion is small. It is related with the transparent conductive laminated film which can improve visibility.

The transparent conductive film which laminated | stacked the transparent and the small resistance thin film on the base material which becomes a transparent plastic film is the use using the electroconductivity, for example, a liquid crystal display or an electroluminescence (it may abbreviate as EL). It is widely used for electric and electronic fields, such as a flat panel display, such as a display, and the transparent electrode of a resistive touch panel.

In recent years, capacitive touch panels have been increasingly installed in mobile devices such as mobile phones and portable music terminals. Such a capacitive touch panel has a structure in which a dielectric layer is laminated on a patterned conductor, and is touched with a finger or the like to ground the capacitive body. At this time, a change occurs in the resistance value between the patterning electrode and the ground point, thereby recognizing the position input. However, when a conventional transparent conductive film is used, since the difference in optical characteristics between the portion having the transparent conductive thin film layer and the removed portion is large, the patterning is conspicuous, when placed on the front surface of a display such as a liquid crystal display. There was a problem that visibility was reduced.

In order to improve the transmittance | permeability or color tone of a transparent conductive film, the method of using the interference of light by laminating | stacking the layer from which the refractive index used by antireflective processing etc. differs is proposed. That is, the method of using an optical interference by providing the layer in which refractive index differs between a transparent conductive thin film layer and a base film is proposed (patent documents 1-3).

However, although the visibility as a transparent conductive film can improve the transparent conductive films of these patent documents 1-3, when the transparent conductive thin film layer is patterned, the difference of the optical characteristic in the part with and without a transparent conductive thin film It is not considered to make small, and the patterned point will stand out.

Moreover, in recent years, the enlargement of the touch panel mounted in mobile devices, such as a mobile telephone, is desired. In particular, since the electroconductive transparent conductive film is patterned and used as above, when the touch panel is enlarged, the wiring resistance of each pattern electrode becomes large, and operation speed falls. For this reason, the transparent conductive film with low surface resistance value and the said patterning not outstanding is desired.

Patent Document 1: Japanese Patent Application Laid-Open No. 11-286066

Patent Document 2: Japanese Patent No. 3826624

Patent Document 3: Japanese Patent Laid-Open No. 2006-346878

That is, an object of the present invention is to provide good visibility when used in a liquid crystal display or the like by reducing the difference between the optical properties of a portion having a transparent conductive thin film layer and a portion having a transparent conductive thin film layer and having a low surface resistance value in view of the above conventional problems. Moreover, it is providing the transparent conductive laminated film which patterning is not outstanding.

This invention is made | formed in view of the above situation, and the transparent electroconductive lamination which solved the said subject becomes the following structures.

1. Laminated | multilayer film which laminated | stacked the high refractive index layer, the low refractive index layer, and the transparent conductive thin film layer in this order on the base material which becomes a transparent plastic film, Comprising: The refractive index of a high refractive index layer is 1.70-2.50, and the film thickness is 4-20 nm. It is in the range, the refractive index of the low refractive index layer is in the range of 1.30 to 1.60, the film thickness is 20 to 50 nm, the specific resistance of the transparent conductive thin film layer is 1.0 to 4.6 × 10 ^-4 Ω · cm, the film thickness is 10 to 28 nm It is a transparent conductive laminated film characterized by the above-mentioned.

2. The transparent conductive thin film layer is a transparent conductive laminated film according to item 1, wherein the transparent conductive thin film layer has a mean grain size of 10 to 1000 nm and a ratio of the amorphous portion to the crystalline portion of 0.00 to 0.90.

3. Transparent conductive thin film layer is indium-tin composite oxide whose content rate of tin oxide is 0.5-8 mass%, The transparent conductive laminated film of said 2 characterized by the above-mentioned.

4. The dielectric layer whose refractive index is 1.40-1.70 was laminated | stacked on the transparent conductive thin film layer side of the transparent conductive laminated film which patterned the transparent conductive thin film layer of the transparent conductive laminated film in any one of said 1-3 characterized by the above-mentioned. film.

5. The difference of the optical characteristic of the part which has a transparent conductive thin film layer by the patterning of the transparent conductive laminated film of said 4, and the part which does not have satisfy | fills following formula (1) and formula (2), The transparent conductive laminated film characterized by the above-mentioned. .

(T1: total light transmittance of the film of the part which has a transparent conductive thin film layer,

b1: the color b value of the film of the part which has a transparent conductive thin film layer,

T0: total light transmittance of the film of the part which does not have a transparent conductive thin film layer,

b0: color b value of the film of the part which does not have a transparent conductive thin film layer)

The transparent conductive laminated film of this invention has the structure which laminated | stacked in order of the high refractive index layer, the low refractive index layer, and the transparent conductive thin film layer on the base material which becomes a transparent plastic film, When a transparent conductive thin film layer is patterned, a transparent conductive thin film layer is Since the difference of the optical characteristic of the part which has and the part which does not have is small, even if it arrange | positions in front of display bodies, such as a liquid crystal display, since the patterning of a transparent conductive thin film layer is not outstanding, the fall of visibility can be suppressed. Moreover, the surface resistance value is low, and it can respond to enlargement of a touchscreen.

1 is an explanatory view of a transparent conductive laminated film of the present invention.

In the transparent conductive laminated film of the present invention, as shown in FIG. It has a laminated structure in order.

Moreover, as a preferable aspect, the dielectric layer 20 may be laminated | stacked on the transparent conductive thin film layer side of the transparent conductive laminated film which patterned the transparent conductive thin film layer of the said transparent conductive laminated film.

Hereinafter, each layer is explained in full detail.

(Base material made of transparent plastic film)

The base material of the transparent plastic film used in the present invention is an organic polymer is melt-extruded or solution-extruded into a film shape to form a film shape, stretched, heat-set, heat-relaxed in the longitudinal direction and / or width direction, if necessary It is the film which processed. Examples of the organic polymer include polyethylene, polypropylene, polyethylene terephthalate, polyethylene-2,6-naphthalate, polypropylene terephthalate, nylon 6, nylon 4, nylon 66, nylon 12, polyimide, polyamideimide, polyethersulfane, Polyether ether ketone, polycarbonate, polyarylate, cellulose propionate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyetherimide, polyphenylene sulfide, polyphenylene oxide, polystyrene, syndiotactic polystyrene And norbornene-based polymers.

Among these organic polymers, polyethylene terephthalate, polypropylene terephthalate, polyethylene-2,6-naphthalate, syndiotactic polystyrene, norbornene-based polymer, polycarbonate, polyarylate and the like are preferable. In addition, these organic polymers may copolymerize a small amount of monomers of other organic polymers, and may mix other organic polymers.

It is preferable that the thickness of the base material which becomes a transparent plastic film used by this invention is 10-300 micrometers, More preferably, it is 20-150 micrometers. If the thickness of the plastic film is less than 10 mu m, the mechanical strength is insufficient, and handling in the pattern forming step of the transparent conductive thin film becomes difficult, which is not preferable. On the other hand, if the thickness exceeds 300 µm, the thickness of the touch panel becomes too thick, which is not suitable for mobile devices and the like.

The base material of the transparent plastic film used by this invention is a corona discharge treatment, a glow discharge treatment, a flame treatment, an ultraviolet irradiation treatment, an electron beam irradiation treatment, an ozone treatment, etc., in the range which does not impair the objective of this invention. You may perform surface activation treatment.

Moreover, the base material which becomes a transparent plastic film used by this invention is a thing which uses curable resin as a main component for the purpose of improving adhesiveness with a high refractive index layer, providing chemical resistance, and preventing precipitation of low molecular weight materials, such as an oligomer. You may provide a cargo layer ((12) of FIG. 1).

The curable resin is not particularly limited as long as it is a resin that is cured by applying energy such as heating, ultraviolet irradiation, electron beam irradiation, and the like, and a silicone resin, an acrylic resin, a methacryl resin, an epoxy resin, a melamine resin, a polyester resin, a urethane resin, and the like. Can be mentioned. From a viewpoint of productivity, curable resin which has ultraviolet curable resin as a main component is preferable.

As such an ultraviolet curable resin, for example, a polyfunctional compound synthesized from a polyfunctional acrylate resin such as acrylic acid or methacrylic acid ester of polyhydric alcohol, diisocyanate, polyhydric alcohol and hydroxyalkyl ester of acrylic acid or methacrylic acid, or the like And urethane acrylate resins. If necessary, monofunctional monomers such as vinylpyrrolidone, methyl methacrylate, styrene, and the like can be added to these polyfunctional resins for copolymerization.

Moreover, in order to improve the adhesive force of a high refractive index layer and hardened | cured material layer, it is effective to surface-treat a hardened | cured material layer further. As a specific method, a polar group such as an amino group, a hydroxyl group or a carbonyl group can be used by using a discharge treatment method for irradiating a glow discharge or a corona discharge, a method of increasing a carbonyl group, a carboxyl group, a hydroxyl group, or a chemical treatment method treated with an acid or an alkali. Increasing method; and the like.

UV-curable resin is normally used by adding a photoinitiator. As a photoinitiator, the well-known compound which absorbs an ultraviolet-ray and generate | occur | produces a radical can be used without a restriction | limiting, As such a photoinitiator, various benzoin, phenyl ketone, benzophenone, etc. are mentioned, for example. It is preferable that the addition amount of a photoinitiator shall be 1-5 mass parts with respect to 100 mass parts of ultraviolet curable resins.

The density | concentration of the resin component in a coating liquid can be suitably selected in consideration of the viscosity etc. by the coating method. For example, the ratio which occupies the total amount of ultraviolet curable resin and a photoinitiator in a coating liquid is 20-80 mass% normally. Moreover, you may add other well-known additives, such as leveling agents, such as a silicone type surfactant and a fluorine type surfactant, to this coating liquid as needed.

In the present invention, the prepared coating liquid is coated on a substrate made of a transparent plastic film. The coating method is not particularly limited, and conventionally known methods such as a bar coating method, a gravure coating method, and a reverse coating method can be used.

Moreover, it is preferable that the thickness of hardened | cured material layer is the range of 0.1-15 micrometers, More preferably, it is 0.5-10 micrometers, Especially preferably, it is 1-8 micrometers. When the thickness of hardened | cured material layer is less than 0.1 micrometer, since a fully crosslinked structure becomes difficult to form, chemical-resistance will fall easily, and adhesive fall by low molecular weight, such as an oligomer, will also occur easily. On the other hand, when the thickness of hardened | cured material layer exceeds 15 micrometers, there exists a tendency for productivity to fall.

(High refractive index layer)

The refractive index of the high refractive index layer which can be used in the present invention is in the range of 1.70 to 2.50, preferably 1.90 to 2.30, and more preferably 1.90 to 2.10. In the case of less than 1.70, since the difference in refractive index with the low refractive index layer is too small, when patterning the transparent conductive thin film layer, it becomes difficult to approximate the optical characteristics of the portion having the transparent conductive thin film layer and the portion not having it. On the other hand, when the refractive index exceeds 2.50, it becomes difficult to make the patterning in the oblique direction inconspicuous, and there is no industrially suitable material. Specific materials of the high refractive index layer include TiO ₂ , Nb ₂ O ₅ , ZrO ₂ , Ta ₂ O ₅ , ZnO, In ₂ O ₃ , SnO ₂ , composite oxides thereof, and zinc sulfide ZnS. Among these are _{ZnO, In 2 O 3, SnO} 2 , and their composite oxides are preferable from the viewpoint of productivity. In addition, from the viewpoint of environmental stability, indium containing SnO ₂ 25 ~ 60% by weight - a tin oxide compound is particularly preferred. Moreover, you may add arbitrary oxides and sulfides to these oxides or sulfides for refractive index adjustment.

The film thickness of a high refractive index layer is 4-20 nm, Preferably it is 7-15 nm, More preferably, it is 8-13 nm. When the film thickness is less than 4 nm, it becomes a discontinuous film and the stability of the film is lowered. On the other hand, when the film thickness exceeds 20 nm, since the reflection of light becomes stronger, when patterning the transparent conductive thin film layer, it becomes difficult to approximate the optical characteristics of the portion having the transparent conductive thin film layer and the portion not having it, and thus the liquid crystal display. When arrange | positioned in front of display bodies, such as these, the patterning of a transparent conductive thin film layer becomes conspicuous and visibility falls. However, it is preferable to control so that an optical film thickness (refractive index x film thickness) may become constant rather than changing the refractive index and film thickness of a high refractive index layer arbitrarily.

As the film formation method of the high refractive index layer in the present invention, a vacuum deposition method, a sputtering method, a CVD method, an ion plating method, a spray method, and the like are known, and the above method can be appropriately used depending on the film thickness required. The sputtering method is preferable from the viewpoint of reducing the unevenness of the thickness.

In the sputtering method, there are generally a reactive sputtering method for preparing a metal oxide by introducing a reactive gas from a metal target and a method for producing a metal oxide from an oxide target. In the reactive sputtering method, there is a transition region in which the film formation speed changes rapidly in accordance with the flow rate of the reactive gas. For this reason, in order to suppress the unevenness of a film thickness, it is preferable to use an oxide target.

(Low refractive index layer)

The refractive index of the low refractive index layer used by this invention is 1.30-1.60, Preferably it is 1.40-1.55, More preferably, it is 1.43-1.50. If the refractive index is less than 1.30, the film becomes a porous film, thereby reducing the electrical properties of the transparent conductive thin film layer formed thereon. On the other hand, when the refractive index exceeds 1.60, since the interference of light with the transparent conductive thin film layer becomes excessively weak, when patterning the transparent conductive thin film layer, it is difficult to approximate the optical characteristics of the portion having the transparent conductive thin film layer and the portion not having the transparent conductive thin film layer. The patterning of the transparent conductive thin film layer becomes outstanding when it arrange | positions in front of display bodies, such as a liquid crystal display, and visibility is reduced.

Specific materials for the low refractive rule layer include transparent metal oxides such as SiO ₂ , Al ₂ O ₃ , composite metal oxides such as SiO ₂ -Al ₂ O ₃ , metal fluorides such as CuF ₂ , CeF ₂ , MnF ₂ , and MgF _2; These polyfluorides can be mentioned. Moreover, you may add arbitrary oxides and sulfides for refractive index adjustment to these oxides or fluorides.

The film thickness of the low refractive index layer is 20-50 nm, Preferably it is 25-45 nm, More preferably, it is 30-40 nm. When the thickness exceeds 50 nm, wavelength dependence becomes excessively strong due to light interference with the transparent conductive thin film layer, so that when the transparent conductive thin film layer is patterned, it is difficult to approximate the optical characteristics of the portion having the transparent conductive thin film layer and the portion having no transparent conductive thin film layer. Become. On the other hand, when the thickness is less than 20 nm, the interference of light with the transparent conductive thin film layer hardly occurs and the transmittance cannot be improved. Therefore, when the transparent conductive thin film layer is patterned, the optical characteristics of the portion having the transparent conductive thin film layer and the portion having no transparent conductive thin film layer are approximated. When it arrange | positions in front of display bodies, such as a liquid crystal display, it becomes difficult, and the patterning of a transparent conductive thin film layer becomes conspicuous, and visibility falls.

However, the refractive index and the thin film of the low refractive index layer are preferably controlled so that the optical film thickness (refractive index x film thickness) becomes constant rather than being arbitrarily changed.

As the method for forming the low refractive index layer in the present invention, a vacuum deposition method, a sputtering method, a CVD method, an ion plating method, a spray method, and the like are known. According to the film thickness required, the above method can be suitably used. The sputtering method is preferable from the viewpoint of reducing the unevenness of the thickness. Generally, when forming by sputtering, reactive DC or AC sputtering method is used. Impedance control to control the reactive gas flow rate to keep the voltage value of DC or AC power source constant to improve the deposition rate, or plasma emission method to control the reactive gas flow rate to keep the emission intensity in the plasma of a specific element constant ( plasma emission method) is used.

Transparent Conductive Thin Film Layer

Specific materials of the transparent conductive thin film in the present invention include indium oxide, tin oxide, zinc oxide, indium-tin composite oxide, tin-antimony composite oxide, zinc-aluminum composite oxide, indium-zinc composite oxide, and the like. . Among these, indium-tin composite oxide is preferable from the viewpoint of environmental stability and circuit workability.

In the present invention, a transparent conductive thin film layer is laminated, and the surface resistance value of the transparent conductive laminated film is preferably 50 to 300 Ω / □, more preferably 100 to 250 Ω / □, more preferably 100 to 220 Ω / By setting it as □, it can be used as a touch panel with a large screen size as a transparent conductive laminated film. The surface resistance value is preferably as low as possible. However, if the thickness is less than 50 Ω / square, the thickness of the transparent conductive thin film layer becomes thick, and the patterning of the transparent conductive thin film layer becomes noticeable, which is not preferable. On the other hand, when it exceeds 300 ohms / square, the position recognition precision of a touch panel will worsen, and it is not preferable.

The film thickness of the transparent conductive thin film is preferably in the range of 10 to 28 nm, more preferably 12 to 25 nm. When the film thickness of a transparent conductive thin film is less than 10 nm, it becomes difficult to become a thin film with a flat surface, and it becomes difficult to obtain favorable electroconductivity. On the other hand, when the film thickness of a transparent conductive thin film is thicker than 28 nm, when patterning a transparent conductive thin film layer, it becomes difficult to approximate the optical characteristic of the part which has a transparent conductive thin film layer, and the part which does not have, and patterning becomes conspicuous. There is.

It is preferable that the specific resistance of a transparent conductive thin film layer is 1.0 * 10 <^{-4> (} ohm) * cm or more and 4.6 * 10 <^{-4> (} ohm) * cm or less. More preferably, it is 2.0 * 10 <^{-4> (} ohm) * cm-4.0 * 10 <^{-4> (} ohm) * cm or less. When the specific resistance is less than 1.0 × 10 ⁻⁴ Ω · cm, the coloring of the transparent conductive thin film layer becomes large, and transparency tends to decrease. On the other hand, when the specific resistance exceeds 4.6 × 10 ⁻⁴ Ω · cm, the wiring resistance at the time of patterning the transparent conductive thin film layer becomes large, which is not preferable.

It is preferable that the transparent conductive thin film layer of this invention is a crystalline thin film layer whose average crystal grain size is 10-1000 nm, and the ratio of an amorphous part with respect to a crystalline part becomes 0.00-0.90.

Here, the definition of the average grain size of the transparent conductive film is as follows.

When the transparent conductive film layer was observed under a transmission electron microscope, what has a polygonal area is defined as a crystal grain, and the area of a crystal grain is given. The crystal grain size is obtained by doubling the square root of the value obtained by dividing the area of the crystal grains by the circumference ratio π.

With respect to the crystal grains observed in the transparent conductive film layer under a transmission electron microscope, all the crystal grains taken in a 40000x enlarged photograph are calculated. The average value of all the grain sizes is taken as the average grain size.

In addition, the method of estimating the ratio of an amorphous part with respect to a crystalline part is computed from the area ratio of a crystalline part and an amorphous part when it observes under a transmission electron microscope.

The average crystal grain diameter of the transparent conductive film of this invention is 10-1000 nm. Especially preferably, it is 20-800 nm, More preferably, it is 30-500 nm. When the average grain size is smaller than 10 nm, it is shown that crystal nucleation hardly occurs when forming a transparent conductive thin film. The transparent conductive thin film in which such crystal nucleation is hard to occur means the presence of many defects in a film, and a specific resistance does not become low.

On the other hand, when the grain size exceeds 1000 nm, the bending resistance deteriorates, so that cracks tend to occur when the transparent conductive thin film layer is patterned.

The ratio of the amorphous portion to the crystalline portion in the transparent conductive film of the present invention is 0.00 to 0.90, preferably 0.00 to 0.70, more preferably 0.00 to 0.50. When the said ratio is larger than 0.90, it shows that crystal nucleation is hard to occur at the time of forming a transparent conductive thin film, and such a transparent conductive thin film which hardly produces such a crystal nucleus means the presence of many defects in a nucleus, and a specific resistance hardly becomes low Therefore, it is not very preferable.

As for the content rate of tin oxide contained in a transparent conductive thin film layer, 0.5-8 mass% is preferable. More preferably, it is 2-6 mass%. When the tin oxide content is less than 0.5% by mass, it is difficult to improve the carrier concentration. On the other hand, when the content of tin oxide exceeds 8% by mass, the amount of dopant not substituted by the In site increases and the mobility of the carrier decreases due to scattering of impurities, which makes it difficult to lower the specific resistance. The amount of tin in the transparent conductive thin film layer can be analyzed by ESCA.

The layer structure of the transparent conductive thin film may be a single layer structure or a laminated structure of two or more layers. In the case of the transparent conductive thin film which has a laminated structure of two or more layers, the said metal oxide which comprises each layer may be same or different.

As the film forming method of the transparent conductive thin film in the present invention, a vacuum deposition method, a sputtering method, a CVD method, an ion plating method, a spray method, and the like are known, and the method can be appropriately used depending on the required film thickness.

For example, in the case of a sputtering method, the usual sputtering method using an oxide target, the reactive sputtering method using a metal target, etc. are used. At this time, oxygen, nitrogen, etc. may be introduce | transduced as a reactive gas, or means, such as ozone addition, plasma irradiation, and ion assist, may be used together. Moreover, you may apply a bias of direct current, alternating current, high frequency, etc. to a board | substrate in the range which does not impair the objective of this invention.

In order to obtain the transparent conductive thin film layer which is low in specific resistance and crystalline of this invention, the following two methods are effective.

(1) The water and organic substance in a film-forming atmosphere are removed.

(2) Increase the energy of the deposited particles.

First, the method of said (1) is demonstrated.

In forming the transparent conductive thin film layer, in the film forming atmosphere where water and organic impurities are removed as much as possible, the energy of the deposited particles is small, so that migration on the surface of the substrate (film) is likely to occur. As a result, a transparent conductive film containing crystals easily occurs in the transparent conductive thin film. For this reason, it becomes possible to obtain the crystalline transparent conductive thin film layer which has a large average grain size and whose ratio of an amorphous part with respect to a crystalline part is 0.00-0.90.

Specifically, the ratio of the water pressure to the inert gas (argon, etc.) in the film forming atmosphere is preferably set to 8.0 × 10 ⁻⁴ to 3.0 × 10 ⁻³ . As a specific achievement means, (1) the water in the plastic film is sufficiently removed before the film formation, and (2) the measures such as providing a water adsorption cryo pump in the film formation space are effective. (1) In order to fully remove the moisture in a plastic film before performing film-forming, it is effective to heat a plastic film, running a plastic film in vacuum. The heating temperature is effective 25 ~ 80 ℃. As a heating method, a heating roll, an infrared heater, etc. are mentioned. If it is less than 25 degreeC, a plastic film cannot be heated effectively, and if it exceeds 80 degreeC, a flaw and a deformation | transformation may arise in a plastic film. (2) As a preferable moisture adsorption cryo pump provided in the film-forming space, POLYCOLD by Hakuto Co., Ltd. is mentioned.

In order to make the ratio of the water pressure to the inert gas (argon, etc.) to be less than 8.0 × 10 ⁻⁴ , in the case of a device in which a large quantity of transparent plastic film is introduced into the deposition chamber, the ratio of the water pressure to the inert gas is lowered. To this end, a long vacuum removal time is required, or a highly capable vacuum pump is required, which makes economic implementation difficult. On the other hand, when the ratio of the water pressure to the inert gas of the film forming atmosphere exceeds 3.0 × 10 ⁻³ , it is difficult to obtain a transparent conductive thin film layer having a low specific resistance and low crystallinity due to the decrease in the energy of the deposited particles.

It is preferable to make the board | substrate (film) temperature at the time of film-forming into -20-80 degreeC. When it exceeds 80 degreeC, since a large amount of impurity gases, such as water and organic gas, generate | occur | produce from a film, energy of a deposited particle falls and it becomes difficult to obtain a transparent conductive thin film which is low in specific resistance and crystalline. Moreover, at the temperature below -20 degreeC, a transparent plastic film recedes and is not preferable. The substrate temperature can be adjusted with a temperature control roll or the like.

Next, the method of said (2) is demonstrated.

When the transparent conductive thin film layer is formed, an activation support method such as an ion assist method or an ion plating method or a high power impulse magnetron sputtering method may be used as a method of improving the energy of the deposited particles. By using these methods, the energy of the deposition atom can be improved, and migration on the surface of the substrate (film) can be easily generated. As a result, the transparent conductive thin film which contains a crystalline part in a transparent conductive thin film and whose specific resistance is small can be obtained.

Among the above methods, the high power impulse magnetron sputtering method can use a conventional sputtering apparatus by replacing the sputtering power supply. For example, the film forming conditions in the high-power impulse magnetron sputtering method include argon gas after introducing oxygen, and the film forming pressure is set to 0.1 to 1.0 kPa, charging voltage of 400 to 1000 V, pulse frequency of 10 to 500 kV, By discharging at a pulse width of 10 to 200 mW, a transparent conductive thin film containing a crystalline portion in the transparent conductive thin film and small specific resistance can be obtained without causing arcing.

In addition, in order to further reduce the specific resistance, energy may be applied after the film formation by means such as heating or ultraviolet irradiation. Of these energy providing means, heat treatment in an oxygen atmosphere is preferred.

The heat treatment temperature is preferably in the range of 80 to 200 ° C. At temperatures below 80 ° C., the dopant is less likely to occur and the carrier concentration is less likely to be improved, which is insufficient to further lower the specific resistance. On the other hand, at the temperature exceeding 200 degreeC, it becomes difficult to maintain the planarity of a film, and also the crystal size in a transparent conductive thin film becomes large too much, and becomes a soft transparent conductive thin film.

Moreover, as heat processing time, the range of 0.2-120 minutes is preferable. Furthermore, the range of 0.5 to 60 minutes is preferable. If it is less than 0.2 minutes, even if it heat-processes at the high temperature of about 220 degreeC, the effect of film | membrane improvement is not enough, and it is unpreferable. On the other hand, in the case of heat processing time exceeding 120 minutes, it is industrially unsuitable.

Moreover, it is preferable to perform the heat processing in the space filled with oxygen, after exhausting to the pressure of 0.2 kPa or less beforehand. It is preferable that the pressure at this time is below atmospheric pressure.

(Dielectric layer (protective layer) with refractive index of 1.40-1.70)

In the present invention, the dielectric layer having a refractive index of 1.40 to 1.70 refers to the purpose of the protective layer laminated to protect the transparent conductive thin film when the transparent conductive laminated film is used as the member of the display, and the capacitance change when touched by a finger or the like. It is a layer which has the purpose of increasing the size and improving the position input accuracy.

As the refractive index of the dielectric layer is 1.40 ~ 1.70, for example, SiO _2, Al ₂ O ₃ such as a transparent metal oxide and SiO ₂ -Al ₂ O _3, such as complex metal oxides, acrylic, silicone, which is a resin of the polyester of Organic matter etc. are used. The refractive index can be measured by an Abbe refractive index meter.

In the conductive laminated film of the present invention, even when such a dielectric layer is provided, patterning is hardly noticeable and is excellent in visibility.

(Optical characteristics of the transparent conductive laminated film)

In this invention, after patterning the transparent conductive thin film layer of a transparent conductive laminated film, in the state which laminated | stacked the dielectric layer whose refractive index is 1.40-1.70 on the transparent conductive thin film layer side, the optical characteristic of the part which has a transparent conductive thin film layer, and a part which does not have a transparent conductive thin film layer It is important that the difference of is small, and it is preferable to satisfy following formula (1) and formula (2).

(T1: total light transmittance of the film of the part which has a transparent conductive thin film layer,

b1: the color b value of the film of the part which has a transparent conductive thin film layer,

T0: total light transmittance of the film of the part which does not have a transparent conductive thin film layer,

b0: color b value of the film of the part which does not have a transparent conductive thin film layer)

It is preferable that T1 is 90% or more, Furthermore, it is preferable that it is 90.5% or more, As for b1, -2-2 are preferable, More preferably, it is -1.0-1.5, More preferably, it is 0-1.5.

The film thickness of each layer of the transparent conductive laminated film thus produced can be seen from the film cross-sectional shape by the transmission electron microscope (TEM), and the refractive index of each layer is obtained by data relating to the wavelength dependence of the transmission and reflectance of the film. This can be seen by optical simulation using the film thickness value by TEM.

Example

Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited at all by these Examples. In addition, the performance of the transparent conductive laminated film was measured by the following method.

(1) total light transmittance

Based on JIS-K7136, total light transmittance was measured using Nippon Denshoku Kogyo Co., Ltd. product NDH-1001DP.

In addition, T1 and T0 in (1) are the part which has a transparent conductive thin film layer measured in the state which laminated | stacked the dielectric layer whose refractive index is 1.52 on the transparent conductive thin film layer side in the patterned transparent conductive laminated film, and there is no transparent conductive thin film layer. The value of the part.

(2) Surface Resistance

In accordance with JIS-K7194, the surface resistance value was measured by the four-terminal method. The tester used Mitsubishi Yuka Co., Ltd. product, Lotest AMCP-T400.

(3) color b value

Based on JIS-K7105, the color b value was measured with the standard light C / 2 using the color difference meter (Nippon Denshoku Kogyo Co., Ltd., ZE-2000).

In addition, b1 and b0 in Formula (2) are the part which has a transparent conductive thin film layer and the transparent conductive thin film layer measured in the state which laminated | stacked the dielectric layer whose refractive index is 1.52 on the transparent conductive thin film layer side to the patterned transparent conductive laminated film. The value of the missing part.

(4) visibility evaluation

After the etching resist was printed on the transparent conductive laminated film, a pattern of 1 × 3 cm was formed by dipping and alkali dipping in 1N hydrochloric acid. A biaxially oriented polyethylene terephthalate (hereinafter abbreviated as PET) film having an acrylic adhesive layer having a refractive index of 1.52 on the transparent conductive thin film side was bonded as a protective film. The screen was made white by using FMV-BIBLOLOOX T70M / T manufactured by Fujitsu Co., Ltd., and the film which bonded the protective film was put in front, and it evaluated that patterning was seen from various angles.

(Circle): Patterning is hardly seen.

(Triangle | delta): Patterning is seen a little.

X: Patterning is seen.

(5) Film thicknesses of the high refractive index layer, the low refractive index layer, and the transparent conductive thin film layer

The film sample piece which laminated | stacked the high refractive index layer, the low refractive index layer, and the transparent conductive thin film layer was cut out to the magnitude | size of 1 mm x 10 mm, and embedded in the epoxy resin for electron microscopes. This was fixed to the sample holder of the ultramicrotome, and the cross-section thin piece parallel to the short side of the embedded sample piece was produced. Subsequently, photographs obtained by photographing at a magnification of 10,000 에서 at a magnification of 200 Hz and a bright field using a transmission electron microscope (JEM-2010, manufactured by JEOL) at the site where there was no significant damage of the thin film of this section. The film thickness was calculated | required from.

(6) the refractive index of the high refractive index layer, the low refractive index layer, the transparent conductive thin film layer

The refractive index of 550 nm was evaluated using the spectroscopic ellipsometer (The FE-5000 by Otsuka Denshi Co., Ltd.) about the sample which each layer formed on the silicon wafer on the same film forming conditions. In addition, the spectral transmittance measurement data of the film provided with each layer was fitted using optical simulation software, and the refractive index was computed. At this time, the film thickness of each layer used the value evaluated by the said film thickness evaluation method. Moreover, it was confirmed that the refractive index of each layer computed in this way does not have a big difference with the refractive index of each layer on a silicon wafer.

(7) Specific resistance of transparent conductive thin film

The specific resistance was calculated using the surface resistance value and the film thickness of the transparent conductive thin film layer.

(8) Average grain size

The film sample piece which laminated | stacked the transparent conductive thin film layer was cut out to the magnitude | size of 1 mm x 10 mm, and was affixed on the upper surface of a suitable resin block with the conductive thin film surface facing outward. After trimming this, ultra-thin sections almost parallel to the film surface were produced by a general ultramicrotome technique.

This section was observed with a transmission electron microscope (JEM-2010, manufactured by JEOL Corporation) to select a conductive thin film surface without significant damage, and photographed at an acceleration voltage of 200 mA and a direct magnification of 40000 times.

When the transparent conductive film layer was observed under a transmission electron microscope, what has a polygonal area is defined as a crystal grain, and the area of a crystal grain is given. The crystal grain size is obtained by doubling the square root of the value obtained by dividing the area of the crystal grains by the circumference ratio π.

All crystal grain sizes are computed with respect to the crystal grain of indium oxide observed in a transparent conductive film layer under a transmission electron microscope. The average value of all the grain sizes is taken as the average grain size.

(9) Ratio of amorphous part to crystalline part

It computed from the area ratio of the crystalline part and the amorphous part when it observes under a transmission electron microscope.

Example 1

Solid content concentration of 50 mass% of mixed solvent of toluene / MEK (80/20: mass ratio) is added to 100 mass parts of photoinitiator containing ultraviolet curable acrylic resin (Daichi Seika Co., Ltd. make, Seikabeam EXF-01J) as a solvent. It added so that it might be stirred, and it melt | dissolved uniformly, and prepared the coating liquid.

The prepared coating liquid was apply | coated to the biaxially-oriented transparent PET film (A4300 by Toyo Boseki Co., Ltd., 100 micrometers in thickness) which has an easily bonding layer on both surfaces so that the thickness of a coating film might be 5 micrometers. After drying at 80 degreeC for 1 minute, the ultraviolet-ray was irradiated (light quantity: 300 mJ / cm <2>) using the ultraviolet irradiation device (The UB042-5AM-W type | mold by I Graphics Corporation), and the coating film was hardened. Subsequently, after providing a coating film similarly to the opposite surface, it heated at 180 degreeC for 1 minute, and reduced volatile matter.

Moreover, in order to remove the moisture in a film before film forming, the rewinding process was performed in the vacuum chamber in order to expose the biaxially oriented transparent PET film which laminated | stacked this hardened | cured material layer in a vacuum. The pressure at this time was 0.002 kPa, and the exposure time was made into 20 minutes. In addition, the temperature of the center roll was 40 degreeC, and the film passed through this.

Next, a transparent conductive thin film made of indium-tin composite oxide was formed as a high refractive index layer on the cured product layer. At this time, the pressure before sputtering was set to 0.0001 kPa, and DC power of 2 W / cm 2 was applied using indium oxide (Sumitomo Kinzoku Kozan Co., Ltd. density, 6.9 g / cm 3) containing 36 mass% of tin oxide as a target. It was. Further, Ar gas was flowed at 130 sccm and O ₂ gas at a flow rate three times the O ₂ flow rate at which the surface resistance value was minimum, and the film was formed by using a DC magnetron sputtering method under an atmosphere of 0.4 kPa.

In addition, the oxygen partial pressure of the atmosphere was always observed with a sputter process monitor (Transicon XPR3, manufactured by Inpicon), and fed back to the flowmeter of the oxygen gas and the DC power supply so that the oxidation degree in the indium-tin composite oxide thin film was constant. As described above, a high refractive index layer made of an indium-tin composite oxide having a thickness of 10 nm and a refractive index of 1.93 was deposited. The surface resistance value of the high refractive index layer thus obtained was 1 × 10 ⁶ Ω / square or more.

In addition, in order to form a SiO ₂ thin film as a low refractive index layer on the high refractive index layer, a direct current magnetron sputtering method using silicon as a target, the vacuum degree of 0.27 kPa, Ar gas as gas, 500 sccm, O ₂ gas as 80 Spilled at a flow rate of sccm.

Moreover, while observing the voltage value during film-forming, it always fed back to the flowmeter of oxygen gas so that a voltage value might become constant. As described above, a low refractive index layer having a thickness of 35 nm and a refractive index of 1.46 was deposited.

Next, a transparent conductive thin film of indium-tin composite oxide was formed on the low refractive index layer. At this time, the pressure before sputtering was set to 0.0001 kPa, and DC power of 2 W / cm 2 was applied using indium oxide (Sumitomo Kinzoku Kozan Co., Density 7.1 g / cm 3) containing 3% by mass of tin oxide as a target. It was. Further, Ar gas was flowed at 130 sccm and O ₂ gas at a flow rate at which the surface resistance value was minimum, and the film was formed using a DC magnetron sputtering method in an atmosphere of 0.4 Pa. The center roll temperature was adjusted to 10 ° C. so as to adjust the film temperature to about 10 ° C.

In addition, while observing the water pressure with respect to argon in the film-forming atmosphere with the sputter process monitor (Transicon XPR3 by Inpicon Co., Ltd.), the transparent conductive thin film which consists of an indium-tin composite oxide of 20 nm in thickness and a refractive index of 1.96 is deposited, and transparent electroconductivity is carried out. A laminated film was produced.

[Example 2]

A transparent conductive laminated film was produced in the same manner as in Example 1 except for changing to indium oxide (1% by mass of Sumitomo Kinzoku Kozan Co., Ltd., density 7.1 g / cm 3) containing 1% by mass of tin oxide as a target when forming a transparent conductive thin film. Was produced.

Example 3

Transparent conductive laminated film in the same manner as in Example 1 except for changing to indium oxide (density 7.1 g / cm 3 manufactured by Sumitomo Kinzoku Kozan Co., Ltd.) containing 5% by mass of tin oxide as a target when forming a transparent conductive thin film. Was produced.

Example 4

The temperature of the center roll at the time of performing a rewinding process in an indium oxide containing 7.5 mass% of tin oxide as a target at the time of forming a transparent conductive thin film (Sumitomo Kinzoku Kozan Co., Density 7.1 g / cm <3>), and a vacuum chamber is 70 A transparent conductive laminated film was produced in the same manner as in Example 1 except that the temperature was changed to ° C.

Example 5

In Example 1, the transparent conductive laminated film was formed like Example 1 except having set the temperature of the center roll at the time of rewinding in a vacuum chamber to 70 degreeC.

[Example 6]

In Example 1, the transparent conductive laminated film was formed like Example 1 except having set the temperature of the center roll at the time of rewinding in a vacuum chamber to 30 degreeC.

Example 7

In Example 1, when forming the transparent conductive thin film which becomes an indium-tin composite oxide on a low refractive index layer, it is not a normal pulse DC power supply but the power supply for high power impulse magnetron sputtering (HMP2 / 3, Whitinger company make). ) Was used. At this time, the pressure before sputtering was set to 0.0001 kPa, and the charging voltage was 500 V and the pulse frequency was 500 kW using an indium oxide (Sumitomo Kinzoku Kozan Co., Density 7.1 g / cm 3) containing 3 mass% of tin oxide as a target. And pulse width of 150 Hz. Further, 130 sccm and Ar ₂ gas were flowed at a flow rate of which the surface resistance value was minimum, and sputtering was performed at a center roll temperature of 10 ° C. under an atmosphere of 0.4 Pa.

Moreover, the transparent conductive thin film which consists of indium-tin composite oxide of thickness 20nm and refractive index 2.01 was deposited, observing the water pressure with respect to argon in a film-forming atmosphere by the sputter process monitor (Transfiber XPR3 by Inpicon Co., Ltd.). Others were carried out similarly to Example 1, and formed the transparent conductive laminated film.

Example 8

A transparent conductive laminated film was formed in the same manner as in Example 1 except that a thin film made of zirconia-silicon composite oxide (ZrO ₂ -SiO ₂ ) was formed on the cured product layer as a high refractive index layer.

At this time, the pressure before sputtering was set to 0.0001 kPa, and DC power of 2 W / cm 2 was applied using ZrSi ₂ (manufactured by Mitsui Ginjoku Co., Ltd.) as a target. The film was formed by flowing 500 sccm and O ₂ gas at a flow rate of 80 sccm. Moreover, while observing the voltage value during film-forming, it always fed back to the flowmeter of oxygen gas so that a voltage value might become constant. As described above, a high refractive index layer having a thickness of 12 nm and a refractive index of 1.75 was deposited.

Example 9

Example 1 If in the high refractive index layer as a layer on the cargo other than the film formation of the thin layer of titanium oxide (TiO ₂₎ is to form a transparent conductive laminate film in the same manner as in Example 1.

At this time, the pressure before sputtering was set to 0.0001 kPa, a DC power of 2 W / cm 2 was applied using Ti (manufactured by Mitsui Ginjoku Co., Ltd.) as a target, and a DC degree of magnetron sputtering method was applied. The film was formed by flowing 500 sccm and O ₂ gas at a flow rate of 80 sccm. Moreover, while observing the voltage value during film-forming, it fed back to the flowmeter of oxygen gas so that a voltage value might become constant. As described above, a high refractive index layer having a thickness of 8 nm and a refractive index of 2.29 was deposited.

Example 10

In Example 1, the transparent conductive laminated film was formed like Example 1 except having formed the thin film which becomes zinc sulfide (ZnS) as a high refractive index layer on the hardened | cured material layer.

At this time, the pressure before sputtering was set to 0.0001 kPa, and zinc sulfide (manufactured by Mitsui Ginjoku Co., Ltd.) was applied as a target, and a high frequency power of 13.56 MHz was applied at 2 W / cm 2, and the magnetron sputtering method was used. Film formation was performed by flowing Ar gas at 500 sccm and O ₂ gas at a flow rate of 80 sccm. Moreover, while observing the voltage value during film-forming, it always fed back to the flowmeter of oxygen gas so that a voltage value might become constant. As described above, a high refractive index layer having a thickness of 7.5 nm and a refractive index of 2.43 was deposited.

Example 11

Example 1, a cured product on the layer other than the film formation of the thin film to be a magnesium fluoride (MgF ₂₎ as the low refractive index layer to form a transparent conductive laminate film in the same manner as in Example 1, in the.

At this time, the pressure before sputtering was set to 0.0001 kPa, using magnesium fluoride (manufactured by Mitsui Ginjoku Co., Ltd.) as a target, and applying a high frequency power of 13.56 MHz at 2 W / cm &lt; 2 &gt; Ar gas was flowed at the flow rate of 500 sccm, and film-forming was performed. Moreover, while observing the voltage value during film-forming, it always fed back to the flowmeter of oxygen gas so that a voltage value might become constant. As described above, the low refractive index layer having a thickness of 40 nm and a refractive index of 1.36 was deposited.

Example 12

A transparent conductive laminated film was formed in the same manner as in Example 1 except that a thin film made of aluminum-silicon composite oxide (Al ₂ O ₃ -SiO ₂ ) was formed as a low refractive index layer on the cured product layer in Example 1. It was.

At this time, the pressure before sputtering was set to 0.0001 kPa, and Al-Si (50:50 wt%) (manufactured by Mitsui Ginjoku Co., Ltd.) was applied as a target, and a DC degree of 2 W / cm 2 was applied to the vacuum degree by the magnetron sputtering method. Film formation was performed by flowing Ar gas as 500 sccm and O ₂ gas at a flow rate of 80 sccm as 0.27 Pa. Moreover, while observing the voltage value during film-forming, it always fed back to the flowmeter of oxygen gas so that a voltage value might become constant. As described above, the low refractive index layer having a thickness of 35 nm and a refractive index of 1.55 was deposited.

Example 13

The transparent conductive laminated film obtained in the same manner as in Example 1 was heat treated at 120 ° C. for 60 minutes. The heat treatment was carried out by reducing the pressure to 0.1 kPa in advance and then performing oxygen substitution.

Comparative Example 1

The transparent conductive laminated film was produced like Example 1 except having set the film thickness of the transparent conductive thin film layer to 22 nm, without providing a high refractive index layer and a low refractive index layer.

Comparative Example 2

A transparent conductive laminated film was produced in the same manner as in Example 1 except that no high refractive index layer was provided.

Comparative Example 3

A transparent conductive laminated film was produced in the same manner as in Example 1 except that the film thickness of the low refractive index layer was set to 10 nm.

[Comparative Example 4]

A transparent conductive laminated film was produced in the same manner as in Example 1 except that the film thickness of the low refractive index layer was set to 100 nm.

[Comparative Example 5]

A transparent conductive laminated film was produced in the same manner as in Example 1, except that indium oxide (density 7.1 g / cm 3 manufactured by Sumitomo Kinzoku Kozan Co., Ltd.) containing 10% by mass of tin oxide was used as a target when forming the transparent conductive thin film. Was produced.

[Comparative Example 6]

A transparent conductive laminated film was produced in the same manner as in Example 1, except that indium oxide (the Sumitomo Kinzoku Kozan Co., Density 7.1 g / cm 3) containing no tin oxide was used as a target when forming the transparent conductive thin film. It was.

Comparative Example 7

In Example 1, the transparent conductive laminated film was formed like Example 1 except having set the temperature of the center roll at the time of rewinding in a vacuum chamber to 20 degreeC.

Comparative Example 8

A transparent conductive laminated film was formed in the same manner as in Example 1 except that a thin film made of aluminum-silicon composite oxide (Al ₂ O ₃ -SiO ₂ ) was formed as a high refractive index layer on the cured product layer in Example 1. It was.

At this time, the pressure before sputtering was set to 0.0001 kPa, and Al-Si (50:50 wt%) (manufactured by Mitsui Ginjoku Co., Ltd.) was applied as a target, and a DC degree of 2 W / cm 2 was applied to the vacuum degree by the magnetron sputtering method. Film formation was performed by flowing Ar gas as 500 sccm and O ₂ gas at a flow rate of 80 sccm as 0.27 Pa. Moreover, while observing the voltage value during film-forming, it always fed back to the flowmeter of oxygen gas so that a voltage value might become constant. As described above, a high refractive index layer having a thickness of 22 nm and a refractive index of 1.55 was deposited.

[Comparative Example 9]

A transparent conductive laminated film was formed in the same manner as in Example 1 except that a thin film made of zirconia-silicon composite oxide (ZrO ₂ -SiO ₂ ) was formed on the cured product layer as a high refractive index layer.

At this time, the pressure before sputtering was set to 0.0001 kPa, and DC power of 2 W / cm 2 was applied using ZrSi ₂ (manufactured by Mitsui Ginjoku Co., Ltd.) as a target. The film was formed by flowing 500 sccm and O ₂ gas at a flow rate of 80 sccm. Moreover, while observing the voltage value during film-forming, it always fed back to the flowmeter of oxygen gas so that a voltage value might become constant. As described above, a low refractive index layer having a thickness of 29 nm and a refractive index of 1.75 was deposited.

[Comparative Example 10]

Indium oxide containing 10 mass% of tin oxide as a target when forming a transparent conductive thin film with a film thickness of a high refractive index layer 13 nm, a film thickness of a low refractive index layer 20 nm, a film thickness of a transparent conductive thin film layer 60 nm, and a transparent conductive thin film. (The Sumitomo Kinzoku Kozan Corporation make, density 7.1 g / cm <3>) The transparent conductive laminated film was produced like Example 1 except having set the temperature of the center roll at the time of rewinding in a vacuum chamber to 20 degreeC.

From the result of Table 1, since the patterned part does not stand out even if the transparent conductive laminated film of Examples 1-13 which satisfy | fills the scope of this invention is patterned, a display, such as a liquid crystal display, When arrange | positioned and used in front of the sieve, it was excellent in visibility. In addition, since the surface resistance value is low, the screen size can be enlarged.

On the other hand, the transparent conductive laminated films according to Comparative Examples 1 to 4 and 8 to 10, in which the high refractive index layer, the low refractive index layer, and the transparent conductive thin film layer are not properly disposed or the film thickness is not appropriate, become the patterned portion. Visibility was reduced because there is not seen part. In addition, the transparent conductive laminated films described in Comparative Examples 5 to 7 in which the content ratio of SnO ₂ and the water pressure are not appropriate have high surface resistance values after heat treatment, and thus cannot be used for increasing the screen size.

Since the transparent conductive laminated film of this invention has a low surface resistance value and the difference of the optical characteristic of the patterning part and the non-patterning part of a transparent conductive thin film layer is small, it is excellent in visibility when arrange | positioned in the front surface of display bodies, such as a liquid crystal display. . For this reason, it is especially preferable as an electrode film for capacitive touch panels.

10: transparent conductive laminated film
11: transparent plastic film (substrate)
12: hardened | cured material layer
13: high refractive index layer
14: low refractive index layer
15: transparent conductive thin film layer
20: dielectric layer

Claims (5)

The laminated film which laminated | stacked the high refractive index layer, the low refractive index layer, and the transparent conductive thin film layer in this order on the base material which becomes a transparent plastic film, Comprising: The refractive index of a high refractive index layer is in the range of 1.70-2.50, and the film thickness is 4-20 nm. The refractive index of the low refractive index layer is in the range of 1.30 to 1.60, the film thickness is 20 to 50 nm, the specific resistance of the transparent conductive thin film layer is 1.0 to 4.6 × 10 ^-4 Ω · cm, and the film thickness is 10 to 28 nm. A transparent conductive laminated film characterized by the above-mentioned. The method of claim 1,
The transparent conductive thin film layer becomes a metal oxide thin film whose average grain size is 10-1000 nm, and the ratio of an amorphous part with respect to a crystalline part becomes 0.00-0.90, The transparent conductive laminated film characterized by the above-mentioned. The method of claim 2,
A transparent conductive laminated film, wherein the transparent conductive thin film layer is an indium-tin composite oxide having a tin oxide content of 0.5 to 8% by mass. The dielectric layer whose refractive index is 1.40-1.70 was laminated | stacked on the transparent conductive thin film layer side of the transparent conductive laminated film which patterned the transparent conductive thin film layer of the transparent conductive laminated film in any one of Claims 1-3, The transparent characterized by the above-mentioned. Conductive laminated film. The difference of the optical characteristic of the part which has a transparent conductive thin film layer by patterning of the transparent conductive laminated film of Claim 4, and the part which does not have satisfy | fills following formula (1) and formula (2), The transparent conductive laminated film characterized by the above-mentioned.

(T1: total light transmittance of the film of the part which has a transparent conductive thin film layer,
b1: the color b value of the film of the part which has a transparent conductive thin film layer,
T0: total light transmittance of the film of the part which does not have a transparent conductive thin film layer,
b0: color b value of the film of the part which does not have a transparent conductive thin film layer)

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