JP2015028874A - Conductive laminate and method of producing the same, information input device, and display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conductive laminate which can reduce its surface resistance value without reduction in visibility and a method of producing the same, and an information input device and a display device having the conductive laminate.SOLUTION: A conductive laminate has a base material, an inorganic dielectric layer formed on the base material, and a transparent conductive layer formed on the inorganic dielectric layer. The inorganic dielectric layer is subjected to plasma treatment.

Description

  The present invention relates to a conductive laminate, a manufacturing method thereof, an information input device, and a display device.

In recent years, a resistive touch panel for inputting information has been arranged on a display device included in a mobile device, a mobile phone device, or the like. The resistive film type touch panel has a structure in which two conductive laminates are arranged to face each other. The conductive laminate functions as an electrode of a touch panel, and has a transparent base material such as a polymer film and a glass substrate, and ITO (Indium Tin Oxide) formed on the base material. And a transparent conductive layer made of a material having a high refractive index (for example, a refractive index of about 1.9 to 2.1).
In addition, capacitive touch panels are also being arranged and are now becoming mainstream. The capacitive touch panel has a conductive layer covered with an insulating protective layer such as a polymer film or a glass substrate on the input operation surface on the insulating substrate, and approaches the conductive layer through the electrostatic capacitance by the insulating protective layer. An input operation position of an input operation body such as a finger to be detected is detected.

  As described above, since the touch panel is generally arranged on the display device, it is required that the display quality of the display device is not deteriorated. However, the refractive index of the plastic material and glass used as the base material is about 1.5, whereas the refractive index of the transparent conductive layer is about 2.0. When the laminated body is disposed, the reflected light is increased and the display quality of the display device is deteriorated. In particular, in a capacitive touch panel, since the conductive layer is patterned by etching or the like, a difference in reflectance occurs between a portion where the conductive layer is present and a portion where the conductive layer is not present, and a pattern portion having a high reflectance can be seen. The display quality of the device will deteriorate.

Moreover, the surface resistance value calculated | required by a use differs in an electroconductive laminated body. For example, in the case of a digital resistive film type touch panel, an analog resistive film type, etc., a surface resistance value in a wide range of 100Ω / □ to several 100Ω / □ is required. In addition, in a capacitive touch panel, a surface resistance value of about 50Ω / □ to 400Ω / □ is required.
One method for reducing the surface resistance value is to increase the thickness of the transparent conductive layer of the conductive laminate. This is because the surface resistance value depends on the thickness of the transparent conductive layer. However, when the thickness of the transparent conductive layer is increased, absorption increases, and there is a problem that the image quality of the display device is deteriorated due to a decrease in visibility.
Other methods for reducing the surface resistance value include addition of O ₂ in an amount that minimizes the resistance value during ITO film formation. However, even with this method, there is a problem in that the visibility decreases due to an increase in absorption, and the image quality of the display device decreases.

Conventionally, in order to improve the transmission characteristics of the conductive laminate, a technique for forming an antireflection film has been used. For example, a transparent conductive laminate for a touch panel in which an antireflection film is provided between a substrate and a transparent conductive layer has been proposed (see, for example, Patent Document 1). This antireflection film is formed by sequentially laminating a plurality of dielectric films having different refractive indexes.
However, this technique alone cannot lower the surface resistance value.

  That is, in the prior art, a technique capable of reducing the surface resistance value without reducing the visibility has not been obtained.

  Therefore, at present, it is required to provide a conductive laminate that can reduce the surface resistance value without reducing visibility, a method for manufacturing the same, an information input device having the conductive laminate, and a display device. is there.

JP 2003-136625 A

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, an object of the present invention is to provide a conductive laminate capable of reducing the surface resistance value without reducing visibility, a method for manufacturing the same, an information input device having the conductive laminate, and a display device. To do.

Means for solving the problems are as follows. That is,
<1> A substrate, an inorganic dielectric layer formed on the substrate, and a transparent conductive layer formed on the inorganic dielectric layer,
The conductive laminate is characterized in that the inorganic dielectric layer is subjected to plasma treatment.
<2> a substrate, an inorganic dielectric layer formed on the substrate, and a transparent conductive layer formed on the inorganic dielectric layer,
The conductive laminate is characterized in that the NET intensity of the diffraction peak of In ₂ O ₃ (222) in XRD measurement of the transparent conductive layer is 1,200 counts or more.
<3> The conductive laminate according to any one of <1> to <2>, wherein the inorganic dielectric layer contains SiO ₂ .
<4> The conductive laminate according to any one of <1> to <3>, wherein the transparent conductive layer contains ITO.
<5> Between the base material and the inorganic dielectric layer, having a structure disposed at a fine pitch below the wavelength of visible light,
The conductive laminate according to any one of <1> to <4>, wherein the inorganic dielectric layer and the transparent conductive layer have a shape that follows the shape of the structure.
<6> An inorganic dielectric layer forming step of forming an inorganic dielectric layer on the substrate;
A plasma processing step of performing plasma processing on the inorganic dielectric layer;
And a transparent conductive layer formation step of forming a transparent conductive layer on the inorganic dielectric layer.
<7> The method for producing a conductive laminate according to <6>, wherein the transparent conductive layer is formed by sputtering.
<8> An uncured resin layer forming step of applying an active energy ray-curable resin composition on a substrate to form an uncured resin layer;
Adhering a transfer master having either a fine convex part or a concave to the uncured resin layer, irradiating the uncured resin layer to which the transfer master is in contact with an active energy ray to cure the uncured resin layer A structure forming step of forming a structure disposed at a fine pitch below the wavelength of visible light by transferring any of the fine convex portions and concave portions;
It is a manufacturing method of the conductive laminated body in any one of said <6> to <7> included before an inorganic dielectric material layer formation process.
<9> An information input device comprising the conductive laminate according to any one of <1> to <5>.
<10> A display device comprising the conductive laminate according to any one of <1> to <5>.

  According to the present invention, the conventional problems can be solved, the object can be achieved, and the conductive laminate capable of reducing the surface resistance value without deteriorating the visibility, the method for producing the same, and the conductivity An information input device and a display device having a stacked body can be provided.

FIG. 1A is a schematic plan view showing an example of the configuration of the conductive laminate of the present invention. FIG. 1B is an enlarged plan view showing a part of the conductive laminate shown in FIG. 1A. 1C is a cross-sectional view taken along tracks T1, T3,... In FIG. 1D is a cross-sectional view taken along tracks T2, T4,... In FIG. 1E is a schematic diagram showing a modulation waveform of laser light used for forming a latent image corresponding to the tracks T1, T3,... In FIG. FIG. 1F is a schematic diagram illustrating a modulation waveform of laser light used for forming a latent image corresponding to tracks T2, T4,... In FIG. 2 is an enlarged perspective view showing a part of the conductive laminate shown in FIG. 1A. FIG. 3A is a cross-sectional view of the conductive laminate shown in FIG. 1A in the track extending direction. 3B is a cross-sectional view in the θ direction of the conductive laminate shown in FIG. 1A. FIG. 4 is an enlarged perspective view showing a part of the conductive laminate shown in FIG. 1A. FIG. 5 is an enlarged perspective view showing a part of the conductive laminate shown in FIG. 1A. 6 is an enlarged perspective view showing a part of the conductive laminate shown in FIG. 1A. FIG. 7 is a diagram for explaining a method of setting the bottom surface of the structure when the boundary of the structure is unclear. FIG. 8A is a diagram showing a bottom surface shape when the ellipticity of the bottom surface of the structure is changed. FIG. 8B is a diagram illustrating a bottom surface shape when the ellipticity of the bottom surface of the structure is changed. FIG. 8C is a diagram illustrating the shape of the bottom surface when the ellipticity of the bottom surface of the structure is changed. FIG. 8D is a diagram illustrating a bottom shape when the ellipticity of the bottom surface of the structure is changed. FIG. 9A is a diagram illustrating an example of an arrangement of structures having a conical shape or a truncated cone shape. FIG. 9B is a diagram illustrating an example of an arrangement of structures having an elliptical cone shape or an elliptical truncated cone shape. FIG. 10A is a perspective view showing an example of a configuration of a roll master for producing a conductive laminate. FIG. 10B is an enlarged plan view showing a part of the roll master shown in FIG. 10A. FIG. 11 is a schematic diagram showing an example of the configuration of the roll master exposure apparatus. FIG. 12A is a process diagram for describing the manufacturing method of the conductive laminate according to the first embodiment of the present invention. FIG. 12B is a process diagram for describing the method for manufacturing the conductive laminate according to the first embodiment of the present invention. FIG. 12C is a process diagram for describing the manufacturing method for the conductive laminate according to the first embodiment of the present invention. FIG. 13A is a process diagram for describing the manufacturing method of the conductive laminate according to the first embodiment of the present invention. FIG. 13B is a process diagram for describing the manufacturing method for the conductive laminate according to the first embodiment of the present invention. FIG. 13C is a process diagram for describing the manufacturing method of the conductive laminate according to the first embodiment of the present invention. FIG. 14A is a process diagram for describing the manufacturing method of the conductive laminate according to the first embodiment of the present invention. FIG. 14B is a process diagram for describing the manufacturing method for the conductive laminate according to the first embodiment of the present invention. FIG. 15A is a perspective view showing an example of a configuration of a touch panel which is an information input device of the present invention. FIG. 15B is a cross-sectional view showing an example of the configuration of a touch panel which is an information input device of the present invention. FIG. 16 is a cross-sectional view showing an example of the configuration of a liquid crystal display device which is a display device of the present invention. 17 is a cross-sectional photograph of the conductive laminate obtained in Example 1. FIG. FIG. 18 is a graph showing the relationship between the NET intensity of the peak of In ₂ O ₃ (222) and the specific resistance in XRD measurement.

(Conductive laminate)
The conductive laminate of the present invention has at least a substrate, an inorganic dielectric layer, and a transparent conductive layer, preferably has a structure, and further has other members as necessary.

<Base material>
There is no restriction | limiting in particular as said base material, According to the objective, it can select suitably, For example, glass, resin-made base materials, etc. are mentioned.

  Examples of the glass include soda lime glass, lead glass, hard glass, quartz glass, and liquid crystallized glass (see “Chemical Handbook”, Basic Edition, PI-537, The Chemical Society of Japan).

  The material of the resin base material is not particularly limited and may be appropriately selected depending on the purpose. For example, triacetyl cellulose (TAC), polyester, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), Polyimide (PI), polyamide (PA), aramid, polyethylene (PE), polyacrylate, polyethersulfone, polysulfone, polypropylene (PP), polystyrene, diacetylcellulose, polyvinyl chloride, acrylic resin (PMMA), polycarbonate (PC ), Epoxy resin, urea resin, urethane resin, melamine resin, phenol resin, acrylonitrile-butadiene-styrene copolymer, cycloolefin polymer (COP), cycloolefin copolymer (COC), PC / MMA laminate, such as rubber additives PMMA and the like.

  The base material preferably has transparency.

There is no restriction | limiting in particular as a shape of the said base material, According to the objective, it can select suitably, For example, a sheet form, plate shape, block shape etc. are mentioned. Here, the sheet is defined as including a film.
When the substrate is plate-shaped, the average thickness of the substrate is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 5 μm to 1,000 μm, and more preferably 50 μm to 500 μm.

  Characters, patterns, images, etc. may be printed on the surface of the substrate.

  When the base material is a resin base material, an undercoat layer may be provided as a surface treatment in order to further improve the surface energy, coatability, slipperiness, flatness and the like of the plastic surface. Examples of the undercoat layer include organoalkoxy metal compounds, polyesters, acrylic-modified polyesters, polyurethanes, and the like. In order to obtain the same effect as that of providing an undercoat layer, the surface of the resin base material may be subjected to corona discharge and UV irradiation treatment.

<Structure>
The conductive laminate preferably has the structure between the base material and the inorganic dielectric layer.
The structures are arranged on the substrate with a fine pitch equal to or less than the wavelength of visible light.

The structure is a convex portion. Many structures are arranged.
The structures are periodically two-dimensionally arranged with a short arrangement pitch equal to or less than the wavelength band of light for the purpose of reducing reflection, for example, an arrangement pitch equal to or less than the wavelength of visible light. Here, the arrangement pitch means an average arrangement pitch P. The wavelength band of light for the purpose of reducing reflection is, for example, the wavelength band of ultraviolet light, the wavelength band of visible light, or the wavelength band of infrared light. Here, the wavelength band of ultraviolet light means a wavelength band of 10 nm to 360 nm, the wavelength band of visible light means a wavelength band of 360 nm to 830 nm, and the wavelength band of infrared light means a wavelength band of 830 nm to 1 mm. Specifically, the average arrangement pitch of the structures is preferably 180 nm to 350 nm, more preferably 100 nm to 320 nm, and particularly preferably 110 nm to 280 nm. When the average arrangement pitch is less than 180 nm, it tends to be difficult to produce a structure. On the other hand, when the average arrangement pitch exceeds 350 nm, diffraction of visible light tends to occur.

  Each structure 3 of the conductive laminate is arranged in such a manner that a plurality of rows of tracks T1, T2, T3,... (Hereinafter collectively referred to as “tracks T”) are formed on the surface of the base material. (See FIG. 1B). In the present invention, the track refers to a portion where the structures 3 are arranged in a straight line in a row. The column direction means a direction perpendicular to the track extending direction (X direction) on the molding surface of the base material.

  For example, the structure 3 is arranged at a position shifted by a half pitch between two adjacent tracks T. Specifically, between two adjacent tracks T, the structure of the other track (for example, T2) is positioned at the intermediate position (position shifted by a half pitch) of the structure 3 arranged on one of the tracks (for example, T1). 3 is arranged. As a result, as shown in FIG. 1B, a hexagonal lattice pattern or a quasi-hexagonal lattice pattern in which the center of the structure 3 is located at each point a1 to a7 between adjacent three rows of tracks (T1 to T3) is formed. The structure 3 is arranged on the surface. In the embodiment of FIG. 1B, the hexagonal lattice pattern refers to a regular hexagonal lattice pattern. The quasi-hexagonal lattice pattern is a distorted hexagonal lattice pattern that is stretched in the track extending direction (X-axis direction), unlike a regular hexagonal lattice pattern.

  When the structures 3 are arranged so as to form a quasi-hexagonal lattice pattern, as shown in FIG. 1B, the arrangement pitch P1 (distance between a1 and a2) of the structures 3 in the same track (for example, T1). Is the arrangement pitch of the structures 3 between two adjacent tracks (for example, T1 and T2), that is, the arrangement pitch P2 of the structures 3 in the ± θ direction with respect to the track extending direction (for example, a1-a7, a2- It is preferable that the distance is longer than the distance a7). By arranging the structures 3 in this way, the packing density of the structures 3 can be further improved.

  The structure 3 preferably has a cone shape or a cone shape obtained by extending or contracting the cone shape in the track direction from the viewpoint of ease of molding. The structure 3 preferably has an axisymmetric cone shape or a cone shape obtained by extending or shrinking the cone shape in the track direction. When the structure 3 is joined to the adjacent structure 3, the structure 3 extends in the track direction with an axisymmetric cone shape except for the lower part joined to the adjacent structure 3, or a cone shape. It preferably has a contracted cone shape. Examples of the cone shape include a cone shape, a truncated cone shape, an elliptical cone shape, and an elliptical truncated cone shape. Here, the cone shape is a concept including an elliptical cone shape and an elliptical truncated cone shape in addition to the cone shape and the truncated cone shape as described above. Further, the truncated cone shape refers to a shape obtained by cutting off the top portion of the truncated cone shape, and the elliptical truncated cone shape refers to a shape obtained by cutting off the top portion of the elliptical cone.

  The structure 3 preferably has a conical shape having a bottom surface whose width in the track extending direction is larger than the width in the column direction perpendicular to the extending direction. Specifically, as shown in FIGS. 2 and 4, the structure 3 has an elliptical, oval or egg-shaped pyramid structure whose bottom surface has a major axis and a minor axis, and an elliptical cone whose top is a curved surface. The shape is preferred. Moreover, as shown in FIG. 5, it is preferable that the bottom is an elliptical, elliptical, or egg-shaped cone structure having a major axis and a minor axis, and has an elliptic frustum shape with a flat top. This is because such a shape can improve the filling factor in the column direction.

  From the viewpoint of improving the reflection characteristics, a cone shape (see FIG. 4) having a gentle slope at the top and a gradually steep slope from the center to the bottom is preferable. From the viewpoint of improving the reflection characteristics and transmission characteristics, the cone shape is steeper in the center than the bottom and the top (see FIG. 2), or the cone shape is flat in the top (see FIG. 5). It is preferable. When the structure 3 has an elliptical cone shape or an elliptical truncated cone shape, the major axis direction of the bottom surface thereof is preferably parallel to the track extending direction. In FIG. 2 and the like, each structure 3 has the same shape, but the shape of the structure 3 is not limited to this, and two or more types of structures 3 are formed on the surface of the substrate. It may be formed. The structure 3 may be formed integrally with the base material 2.

  In addition, as shown in FIGS. 2 and 4 to 6, it is preferable to provide a protruding portion 6 at a part or all of the periphery of the structure 3. This is because the reflectance can be kept low even when the filling rate of the structures 3 is low. Specifically, for example, the protrusion 6 is provided between the adjacent structures 3 as shown in FIGS. 2, 4, and 5. Further, as shown in FIG. 6, the elongated protrusion 6 may be provided on the entire periphery of the structure 3 or a part thereof. For example, the elongated protrusion 6 extends from the top of the structure 3 toward the bottom. Examples of the shape of the protruding portion 6 include a triangular cross section and a quadrangular cross section. However, the shape is not particularly limited to these shapes, and can be selected in consideration of ease of molding. Further, a part or all of the surface around the structure 3 may be roughened to form fine irregularities. Specifically, for example, the surface between adjacent structures 3 may be roughened to form fine irregularities. Moreover, you may make it form a micro hole in the surface of the structure 3, for example, a top part.

  The height H1 of the structures 3 in the track extending direction is preferably smaller than the height H2 of the structures 3 in the column direction. That is, it is preferable that the heights H1 and H2 of the structure 3 satisfy the relationship of H1 <H2. If the structures 3 are arranged so as to satisfy the relationship of H1 ≧ H2, it is necessary to increase the arrangement pitch P1 in the track extending direction, so that the filling rate of the structures 3 in the track extending direction decreases. is there. Thus, when the filling rate is lowered, the reflection characteristics are lowered.

The aspect ratios of the structures 3 are not limited to the same, and each structure 3 is configured to have a certain height distribution (for example, an aspect ratio in the range of about 0.2 to 1.78). May be. By providing the structure 3 having a height distribution, the wavelength dependence of the reflection characteristics can be reduced. Therefore, the conductive laminate 1 having excellent antireflection characteristics can be realized.
The aspect ratio (height H / average arrangement pitch P) of the structures 3 is preferably 0.2 to 1.78, more preferably 0.2 to 1.28, and particularly preferably 0.3 to 1.0.

  Here, the height distribution means that the structures 3 having two or more heights (depths) are provided on the surface of the substrate 2. That is, it means that the structure 3 having a reference height and the structure 3 having a height different from the structure 3 are provided on the surface of the substrate 2. The structures 3 having a height different from the reference are provided, for example, on the surface of the substrate 2 periodically or aperiodically (randomly). As the direction of the periodicity, for example, a track extending direction, a column direction, and the like can be given.

  It is preferable to provide a skirt 3 a at the peripheral edge of the structure 3. This is because the structure 3 can be easily peeled off from a mold or the like in the manufacturing process of the conductive laminate. Here, the skirt 3 a means a protrusion provided at the peripheral edge of the bottom of the structure 3. From the viewpoint of peeling characteristics, the skirt 3a preferably has a curved surface whose height gradually decreases from the top of the structure 3 toward the lower part. In addition, although the skirt part 3a may be provided only in a part of the peripheral part of the structure 3, it is preferable to provide it in the whole peripheral part of the structure 3 from a viewpoint of the improvement of a peeling characteristic. Moreover, when the structure 3 is a recessed part, a skirt part becomes a curved surface provided in the opening periphery of the recessed part which is the structure 3. As shown in FIG.

  The average height (average depth) of the structures 3 is preferably 60 nm to 320 nm, more preferably 60 nm to 280 nm, and particularly preferably 70 nm to 230 nm. When the average height of the structures 3 is less than 60 nm, the reflectance tends to increase. When the average height of the structures 3 exceeds 320 nm, it tends to be difficult to achieve a predetermined resistance.

In the present invention, the aspect ratio is defined by the following formula (1).
Aspect ratio = H / P (1)
Where H: height of the structure, P: average arrangement pitch (average period)
Here, the average arrangement pitch P is defined by the following equation (2).
Average arrangement pitch P = (P1 + P2 + P2) / 3 (2)
However, P1: Arrangement pitch in the track extending direction (period in the track extending direction), P2: ± θ direction with respect to the track extending direction (where θ = 60 ° −δ, where δ is preferably Is 0 ° <δ ≦ 11 °, more preferably 3 ° ≦ δ ≦ 6 °) (pitch in θ direction)

  When the structures 3 are arranged so as to form a hexagonal lattice pattern or a quasi-hexagonal lattice pattern, the height H of the structures 3 is the height of the structures 3 in the column direction. The height of the structure 3 in the track extending direction (X direction) is smaller than the height in the column direction (Y direction), and the height of the structure 3 other than the track extending direction is the height in the column direction. Therefore, the height of the sub-wavelength structure is represented by the height in the column direction. However, when the structure 3 is a recess, the height H of the structure in the above formula (1) is the depth H of the structure.

  When the arrangement pitch of the structures 3 in the same track is P1, and the arrangement pitch of the structures 3 between two adjacent tracks is P2, the ratio P1 / P2 is 1.0 ≦ P1 / P2 ≦ 2.0, Alternatively, 1.0 <P1 / P2 ≦ 2.0 is preferable, and 1.0 ≦ P1 / P2 ≦ 1.5, or 1.0 <P1 / P2 ≦ 1.5 is more preferable. By setting it as such a numerical value range, since the filling rate of the structure 3 which has an elliptical cone or elliptical truncated cone shape can be improved, an antireflection characteristic can be improved.

  The filling rate of the structures 3 on the substrate surface is preferably 65% or more, more preferably 73% or more, and particularly preferably 86% or more, with 100% being the upper limit. By setting the filling rate within such a range, the antireflection characteristics can be improved. In order to improve the filling rate, it is preferable to apply distortion to the structures 3 by joining the lower portions of adjacent structures 3 or adjusting the ellipticity of the bottom surface of the structures.

Here, the filling rate (average filling rate) of the structures 3 is a value obtained as follows.
First, the surface of the conductive laminated body 1 is image | photographed by Top View using a scanning electron microscope (SEM: Scanning Electron Microscope). Next, the unit lattice Uc is selected at random from the photographed SEM photograph, and the arrangement pitch P1 and the track pitch Tp of the unit lattice Uc are measured (see FIG. 1B). Further, the area S of the bottom surface of the structure 3 located at the center of the unit cell Uc is measured by image processing. Next, using the measured arrangement pitch P1, track pitch Tp, and bottom surface area S, the filling rate is obtained from the following equation (3).
Filling rate = (S (hex.) / S (unit)) × 100 (3)
Unit lattice area: S (unit) = P1 × 2 Tp
Area of bottom surface of structure existing in unit cell: S (hex.) = 2S

  The above-described filling rate calculation processing is performed on 10 unit cells randomly selected from the taken SEM photographs. Then, the measured values are simply averaged (arithmetic average) to obtain an average filling rate, which is used as the filling rate of the structures 3 on the substrate surface.

  The filling rate when the structures 3 are overlapped or when there is a substructure such as the protrusion 6 between the structures 3 is a portion corresponding to a height of 5% with respect to the height of the structures 3 The filling rate can be obtained by a method of determining the area ratio using as a threshold value.

  FIG. 7 is a diagram for explaining a method of calculating the filling rate when the boundaries of the structures 3 are unclear. When the boundary of the structure 3 is unclear, a section corresponding to 5% (= (d / h) × 100) of the height h of the structure 3 is obtained by cross-sectional SEM observation as shown in FIG. The filling factor is obtained by converting the diameter of the structures 3 by the height d and setting the threshold value. When the bottom surface of the structure 3 is an ellipse, the same processing is performed on the long axis and the short axis.

  FIG. 8 is a diagram illustrating a bottom surface shape when the ellipticity of the bottom surface of the structure 3 is changed. The ellipticities of the ellipses shown in FIGS. 8A to 8D are 100%, 110%, 120%, and 141%, respectively. By changing the ellipticity in this way, the filling rate of the structures 3 on the substrate surface can be changed. When the structure 3 forms a quasi-hexagonal lattice pattern, the ellipticity e of the bottom surface of the structure is preferably 100% <e <150% or less. This is because by making it within this range, the filling rate of the structures 3 can be improved and excellent antireflection characteristics can be obtained.

  Here, the ellipticity e is defined as (a / b) × 100, where a is the diameter in the track direction (X direction) of the bottom surface of the structure, and b is the diameter in the column direction (Y direction) perpendicular thereto. Is done. The diameters a and b of the structure 3 are values obtained as follows. The surface of the conductive laminate 1 is photographed with a top view using a scanning electron microscope (SEM), and ten structures 3 are randomly extracted from the photographed SEM photograph. Next, the diameters a and b of the bottom surfaces of the extracted structures 3 are measured. Then, each of the measured values a and b is simply averaged (arithmetic average) to obtain an average value of the diameters a and b, which are set as the diameters a and b of the structure 3.

  FIG. 9A shows an example of the arrangement of the structures 3 having a conical shape or a truncated cone shape. FIG. 9B shows an example of the arrangement of the structures 3 having an elliptical cone shape or an elliptical truncated cone shape. As shown in FIGS. 9A and 9B, it is preferable that the structures 3 are joined so that the lower portions thereof overlap each other. Specifically, it is preferable that the lower portion of the structure 3 is joined to a part or all of the lower portions of the adjacent structures 3. More specifically, it is preferable to join the lower portions of the structures 3 in the track direction, in the θ direction, or in both directions. More specifically, it is preferable to join the lower portions of the structures 3 in the track direction, in the θ direction, or in both directions. 9A and 9B show an example in which all lower portions of the structures 3 that are adjacent to each other are joined. By joining the structures 3 in this way, the filling rate of the structures 3 can be improved. It is preferable that the structures are bonded to each other at a portion equal to or less than ¼ of the maximum value of the wavelength band of the light in the usage environment with an optical path length considering the refractive index. Thereby, an excellent antireflection characteristic can be obtained.

  As shown in FIG. 9B, the lower portions of the adjacent structures 3 in the same track are overlapped to form a first joint a, and the lower portions of the adjacent structures 3 are overlapped between adjacent tracks. Thus, the second joint portion 2 is formed. An intersection c is formed at the intersection of the first joint a and the second joint b. The position of the intersection part c is lower than the positions of the first joint part a and the second joint part b, for example. When the lower portions of the structures 3 having an elliptical cone shape or an elliptical truncated cone shape are joined to each other, for example, the height thereof decreases in the order of the joined part a, the joined part b, and the intersection part c.

  The ratio of the diameter 2r to the arrangement pitch P1 ((2r / P1) × 100) is preferably 85% or more, more preferably 90% or more, and particularly preferably 95% or more. It is because the filling rate of the structures 3 can be improved and the antireflection characteristics can be improved by setting the amount within such a range. When the ratio ((2r / P1) × 100) increases and the overlap of the structures 3 becomes too large, the antireflection characteristics tend to decrease. Therefore, the ratio ((2r / P1) × 100) is set so that the structures are joined at a portion of the optical path length considering the refractive index and not more than ¼ of the maximum value of the wavelength band of the light in the usage environment. It is preferable to set an upper limit value. Here, the arrangement pitch P1 is the arrangement pitch of the structures 3 in the track direction, and the diameter 2r is the diameter of the bottom surface of the structure in the track direction. When the bottom surface of the structure is circular, the diameter 2r is a diameter, and when the bottom surface of the structure is elliptical, the diameter 2r is a long diameter.

<Inorganic dielectric layer>
The material constituting the inorganic dielectric layer is not particularly limited as long as it is an inorganic dielectric, and can be appropriately selected according to the purpose. Examples thereof include metal oxides. Examples of the metal oxide include tantalum oxide (Ta ₂ O ₅ ), tungsten oxide (WO ₃ ), silicon dioxide (SiO ₂ ), silicon monoxide (SiO), bismuth oxide (Bi ₂ O ₅ ), neodymium oxide. (Nd ₂ O ₃ ), titanium oxide (TiO ₂ ), and the like. Among these, silicon dioxide (SiO ₂ ) is preferable because it has low absorption and high transparency, a refractive index close to that of the resin, and low gas and moisture permeability.

  The inorganic dielectric layer 5 is formed following the shape of the structure 3 so as not to hinder the antireflection effect of the structure 3, and the surface shape of the structure 3 and the inorganic dielectric layer 5 is substantially similar. It is preferable. This is because a change in the refractive index profile due to the formation of the inorganic dielectric layer 5 can be suppressed, and excellent antireflection characteristics and / or transmission characteristics can be maintained. The material constituting the inorganic dielectric layer 5 is preferably in a mixed state of amorphous and polycrystalline. This is because even when the height of the structure 3 is lowered, the inorganic dielectric layer 5 can be formed with a thickness that does not hinder the antireflection effect of the structure 3. That is, the inorganic dielectric layer 5 can maintain a shape that follows the shape of the structure 3.

There is no restriction | limiting in particular as average thickness of the inorganic dielectric material layer 5, Although it can select suitably according to the objective, 2 nm-15 nm are preferable and 3 nm-10 nm are more preferable from the point of permeation prevention of degas and a water | moisture content. . If the average thickness is less than 2 nm, the effect of preventing degas and moisture may be insufficient, and if it exceeds 15 nm, the shape of the unevenness may change, and desired reflectance characteristics may not be obtained. . In this specification, when the conductive laminate 1 has the structure 3, the average thickness of the inorganic dielectric layer 5 is the average thickness of the inorganic dielectric layer 5 at the top of the structure 3. The average thickness of the inorganic dielectric layer 5 in the case where the conductive laminate 1 has the structure 3 is obtained, for example, as follows.
First, the conductive laminate 1 is cut so as to include the top of the structure 3, and a cross section thereof is photographed with a transmission electron microscope (TEM), and the top of the structure 3 is taken from the photographed TEM photograph. The thickness of the inorganic dielectric layer 5 is measured. These measurements are repeated at 10 points selected at random from the conductive laminate 1, and the measured values are simply averaged (arithmetic average) to obtain an average thickness. This average film thickness is determined as the inorganic dielectric layer 5 The average thickness.

  There is no restriction | limiting in particular as a formation method of the said inorganic dielectric material layer, According to the objective, it can select suitably, For example, a wet process, a dry process, etc. are mentioned. Examples of the dry process include a sputtering method. Among these, the sputtering method is preferable.

-Plasma treatment-
The inorganic dielectric layer is plasma treated.
Examples of the plasma treatment include plasma bombardment treatment and reverse sputtering treatment. Among these, plasma bombardment is preferable because it is widely used in film production apparatuses and has high productivity.

The plasma bombardment process is performed, for example, using Ar gas under vacuum conditions.
In the plasma bombardment process, for example, an RF power source is used. Moreover, there is no restriction | limiting in particular as irradiation power in the said plasma bombardment process, Although it can select suitably according to the objective, 200W-1,000W are preferable and 300W-800W are more preferable. There is no restriction | limiting in particular as irradiation time in the said plasma bombardment process, Although it can select suitably according to the objective, 10 seconds-30 seconds are preferable, and 13 seconds-25 seconds are more preferable.

<Transparent conductive layer>
Examples of the material constituting the transparent conductive layer include indium tin oxide (ITO), zinc oxide (ZnO), AZO (Al ₂ O ₃ , ZnO), SZO, FTO, SnO ₂ , GZO, and IZO (In _2). O ₃ , ZnO), IGZO (Indium Gallium Zinc Oxide), and the like. Among these, ITO is preferable from the viewpoints of high reliability and low resistivity.

  The transparent conductive layer is in contact with the inorganic dielectric layer.

  The transparent conductive layer 4 is formed following the shape of the structure 3 so as not to hinder the antireflection effect of the structure 3, and the surface shape of the structure 3 and the transparent conductive layer 4 may be substantially similar. preferable. This is because a change in the refractive index profile due to the formation of the transparent conductive layer 4 can be suppressed, and excellent antireflection characteristics and / or transmission characteristics can be maintained. The material constituting the transparent conductive layer 4 is preferably in a mixed state of amorphous and polycrystalline. This is because even when the height of the structure 3 is lowered, the transparent conductive layer 4 can be formed with a thickness that does not impair the antireflection effect of the structure 3. That is, the transparent conductive layer 4 can maintain a shape that follows the shape of the structure 3.

There is no restriction | limiting in particular as average thickness of the transparent conductive layer 4, Although it can select suitably according to the objective, 9 nm-50 nm are preferable from the point of surface resistance, a color taste, and a crack. If the average thickness is less than 9 nm, the surface resistance may be too high, and if it exceeds 50 nm, yellowishness and film cracking may occur. In this specification, when the conductive laminate 1 has the structure 3, the average thickness of the transparent conductive layer 4 is the average thickness of the transparent conductive layer at the top of the structure 3. The average thickness of the transparent conductive layer 4 in the case where the conductive laminate 1 has the structure 3 is determined as follows, for example.
First, the conductive laminate 1 is cut so as to include the top of the structure 3, and a cross section thereof is photographed with a transmission electron microscope (TEM), and the top of the structure 3 is taken from the photographed TEM photograph. The thickness of the transparent conductive layer 4 is measured. These measurements are repeated at 10 locations randomly selected from the conductive laminate 1, and the average thickness is obtained by simply averaging (arithmetic average) the measured values. Average thickness.

  There is no restriction | limiting in particular as a formation method of the said transparent conductive layer, According to the objective, it can select suitably, For example, a wet process, a dry process, etc. are mentioned. Examples of the dry process include a sputtering method. Among these, the sputtering method is preferable in that the surface resistance value can be lowered.

The transparent conductive layer preferably contains In ₂ O ₃ . Examples of the material containing In ₂ O ₃ include ITO, IZO, and IGZO (Indium Gallium Zinc Oxide).
The content of _In 2 _{O 3} in the transparent conductive layer, preferably at least 80 mass%, more preferably at least 90 mass%.

The NET intensity of the diffraction peak of In ₂ O ₃ (222) in the XRD measurement of the transparent conductive layer is not particularly limited and may be appropriately selected depending on the intended purpose, but may be 1,200 counts or more. preferable.
The NET intensity is measured using, for example, X'Pert Pro MPD manufactured by PANalytical. Specifically, a Cu tube (characteristic X-ray CuKα1 λ = 1.540598 mm) is used, and the range is 2θ (10 ° to 80 °) by the parallel method (incident angle: 1 °, flat collimator is used for the light receiving portion). Can be measured by measuring the diffraction intensity and performing peak fitting (fitting function: Pseudo-Voigt function) at the ITO crystal peak (222) (approximately 2θ = 30.6 °).

  There is no restriction | limiting in particular as a method of manufacturing the said electroconductive laminated body, Although it can select suitably according to the objective, The manufacturing method of the electroconductive laminated body of the following this invention is preferable.

(Method for producing conductive laminate)
The method for producing a conductive laminate of the present invention includes at least an inorganic dielectric layer forming step, a plasma treatment step, and a transparent conductive layer forming step, preferably an uncured resin layer forming step and a structure forming step. In addition, other steps are included as necessary.

<Uncured resin layer forming step>
The uncured resin layer forming step is not particularly limited as long as it is a step for forming an uncured resin layer by applying an active energy ray-curable resin composition on the substrate, and is appropriately selected according to the purpose. can do.

  There is no restriction | limiting in particular as said base material, According to the objective, it can select suitably, For example, the said base material etc. which were illustrated in description of the said electroconductive laminated body of this invention are mentioned.

-Active energy ray-curable resin composition-
The active energy ray-curable resin composition is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it contains at least a polyfunctional (meth) acrylic monomer and a photopolymerization initiator, If necessary, an active energy ray-curable resin composition containing other components may be used.

--Polyfunctional (meth) acrylic monomer--
Examples of the polyfunctional (meth) acrylic monomer include 1,3-butylene glycol diacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, ethoxylated (3) bisphenol A diacrylate, and dipropylene. Glycol diacrylate, acrylate ester (dioxane glycol diacrylate), ethoxylated (4) bisphenol A diacrylate, isocyanuric acid EO-modified diacrylate, tricyclodecane dimethanol diacrylate, ethylene glycol dimethacrylate, 1,4-butanediol di Methacrylate, diethylene glycol dimethacrylate, 1,12-dodecanediol dimethacrylate, 1,3-butyleneglycol Dimethacrylate, ethoxylated (4) bisphenol A dimethacrylate, and the like ethoxylated (6) bisphenol A dimethacrylate. These may be used individually by 1 type and may use 2 or more types together.

  Moreover, as said polyfunctional (meth) acryl monomer, bifunctional urethane (meth) acrylate, bifunctional epoxy (meth) acrylate, bifunctional polyester (meth) acrylate, etc. are mentioned, for example.

  A commercial item may be sufficient as the said bifunctional urethane (meth) acrylate. Examples of the commercially available products include CN940, CN963, CN963A80, CN963B80, CN963E75, CN963E80, CN982A75, CN982B88, CN983, CN985C, CN901, CN9711, CN97C, CN97C, C97 Examples include EBECRYL 284 manufactured by company, AT-600, UF-8001G manufactured by Kyoeisha Chemical Co., Ltd., and the like.

  A commercial item may be sufficient as the said bifunctional epoxy (meth) acrylate. Examples of the commercially available products include CN104, CN104A80, CN104B80, CN104D80, CN115, CN117, CN120, CN120A75, CN120B60, CN120B80, CN120C60, CN120C80, CN120D80, CN120E50, CN120E50, CN120E50, CN120E50, E UVE150 / 80, CN2100, EBECRYL 600, EBECRYL 605, EBECRYL 3700, EBECRYL 3701, EBECRYL 3702, EBECRYL 3703, 70FA, 300A, etc. made by Kyoeisha Chemical Co., Ltd. .

  A commercial item may be sufficient as the said bifunctional polyester (meth) acrylate. Examples of the commercially available products include CN2203 and CN2272 manufactured by Sartomer.

There is no restriction | limiting in particular as glass transition temperature (Tg) of the said polyfunctional (meth) acryl monomer, Although it can select suitably according to the objective, It is preferable that it is 50 degreeC or more. For example, the Tg is prepared by blending 5 parts by mass of the polymerization initiator with respect to 100 parts by mass of the polyfunctional (meth) acrylic monomer, and using a mercury lamp to irradiate ultraviolet rays with a dose of 1,000 mJ / cm ² The cured product obtained as described above can be used as a test piece, and can be obtained by a differential scanning calorimeter or a thermomechanical analyzer.

  There is no restriction | limiting in particular as content of the said polyfunctional (meth) acryl monomer in the said active energy ray curable resin composition, Although it can select suitably according to the objective, 15.0 mass%-99.9 % By mass is preferable, 50.0% by mass to 99.0% by mass is more preferable, and 75.0% by mass to 98.0% by mass is particularly preferable.

-Photopolymerization initiator-
Examples of the photopolymerization initiator include a photoradical polymerization initiator, a photoacid generator, a bisazide compound, hexamethoxymethylmelamine, and tetramethoxyglycolyl.
The radical photopolymerization initiator is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include ethoxyphenyl (2,4,6-trimethylbenzoyl) phosphine oxide and bis (2,6-dimethylbenzoyl). ) -2,4,4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,6-dichlorobenzoyl) -2 , 4,4-trimethylpentylphosphine oxide, 1-phenyl 2-hydroxy-2methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane -1-one, 1,2-diphenylethanedione, methylphenylglycone Kishireto and the like.

  There is no restriction | limiting in particular as content of the said photoinitiator in the said active energy ray curable resin composition, Although it can select suitably according to the objective, 0.1 mass%-10 mass% are preferable, 0.5 mass%-8 mass% are more preferable, and 1 mass%-5 mass% are especially preferable.

  The uncured resin layer is formed by applying the active energy ray-curable resin composition on the substrate and drying it as necessary. The uncured resin layer may be a solid film or a film having fluidity due to a low molecular weight curable component contained in the active energy ray curable resin composition.

  There is no restriction | limiting in particular as said application | coating method, According to the objective, it can select suitably, For example, wire bar coating, blade coating, spin coating, reverse roll coating, die coating, spray coating, roll coating, gravure coating , Micro gravure coating, lip coating, air knife coating, curtain coating, comma coating method, dipping method and the like.

  The uncured resin layer is not cured because it is not irradiated with active energy rays.

<Structure formation process>
As the structure forming step, the uncured resin layer is brought into close contact with a transfer master having a fine convex portion or a recess, and the uncured resin layer to which the transfer master is in close contact is irradiated with active energy rays. If there is a step of forming a structure disposed at a fine pitch below the wavelength of visible light by curing the uncured resin layer and transferring any of the fine convex portions and concave portions, there is no particular limitation, It can be appropriately selected according to the purpose.

-Transcription master-
The transfer master has either a fine convex part or a concave part.
There is no restriction | limiting in particular as a material of the said transfer original disc, a magnitude | size, and a structure, According to the objective, it can select suitably.
There is no particular limitation on the method for forming any of the fine convex portions and concave portions of the transfer master, and it can be selected as appropriate according to the purpose. However, the transfer using a photoresist having a predetermined pattern shape as a protective film is possible. It is preferably formed by etching the surface of the master. Further, it is preferable to form the transfer master by irradiating the surface of the transfer master with a laser.

-Active energy ray-
The active energy ray is not particularly limited as long as it is an active energy ray that cures the uncured resin layer, and can be appropriately selected according to the purpose. For example, an electron beam, an ultraviolet ray, an infrared ray, a laser beam, a visible ray Examples include light rays, ionizing radiation (X-rays, α-rays, β-rays, γ-rays, etc.), microwaves, and high frequencies.

<Inorganic dielectric layer formation process>
The inorganic dielectric layer forming step is not particularly limited as long as it is a step of forming an inorganic dielectric layer on a substrate, and can be appropriately selected according to the purpose. The base material may be a base material on which the structure is formed.

As said base material, the said base material etc. which were illustrated in description of the said electroconductive laminated body of this invention are mentioned, for example.
Examples of the inorganic dielectric layer include the inorganic dielectric layer exemplified in the description of the conductive laminate of the present invention.

  There is no restriction | limiting in particular as a method of forming the said inorganic dielectric material layer, According to the objective, it can select suitably, For example, a wet process, a dry process, etc. are mentioned. Examples of the dry process include a sputtering method. Among these, the sputtering method is preferable.

<Plasma treatment process>
The plasma treatment step is not particularly limited as long as it is a step of performing plasma treatment on the inorganic dielectric layer, and can be appropriately selected according to the purpose.

  Examples of the plasma treatment include the plasma treatment exemplified in the description of the conductive laminate of the present invention.

<Transparent conductive layer forming step>
The transparent conductive layer forming step is not particularly limited as long as it is a step of forming a transparent conductive layer on the inorganic dielectric layer, and can be appropriately selected according to the purpose.

  The transparent conductive layer is formed in contact with the surface of the inorganic dielectric layer.

  Examples of the transparent conductive layer include the transparent conductive layer exemplified in the description of the conductive laminate of the present invention.

  There is no restriction | limiting in particular as a method of forming the said transparent conductive layer, According to the objective, it can select suitably, For example, a wet process, a dry process, etc. are mentioned. Examples of the dry process include a sputtering method. Among these, the sputtering method is preferable.

  Here, it is preferable that the inorganic dielectric layer forming step, the plasma treatment, and the transparent conductive layer are continuously performed under reduced pressure, preferably under vacuum. By doing so, mixing of impurities can be prevented.

  An example of the manufacturing method of the electroconductive laminated body of this invention is shown below. The following conductive laminate is a conductive laminate having the structure between the substrate and the inorganic dielectric layer, but the conductive laminate of the present invention has the structure. It is not limited.

[Role master configuration]
10A and 10B show an example of the configuration of a roll master for producing a conductive laminate having the above-described configuration. As shown in FIGS. 10A and 10B, the roll master 11 has, for example, a configuration in which a large number of structures 13 that are concave portions are arranged on the surface of the master 12 at a pitch approximately equal to the wavelength of light such as visible light. ing. The master 12 has a columnar shape or a cylindrical shape. The material of the master 12 can be glass, for example, but is not limited to this material. Using a roll master exposure device, which will be described later, a two-dimensional pattern is spatially linked, and a signal is generated by synchronizing the polarity inversion formatter signal and the rotary controller of the recording device for each track, and patterning with an appropriate feed pitch by CAV To do. Thereby, a hexagonal lattice pattern or a quasi-hexagonal lattice pattern can be recorded. By appropriately setting the frequency of the polarity inversion formatter signal and the rotation speed of the roll, a lattice pattern having a uniform spatial frequency is formed in a desired recording area.

[Method for producing conductive laminate]
Next, an example of a method for manufacturing the conductive laminate 1 configured as described above will be described with reference to FIGS.

<< Configuration of exposure apparatus >>
First, the configuration of a roll master exposure apparatus used in a moth-eye pattern exposure process will be described with reference to FIG. This roll master exposure apparatus is configured based on an optical disk recording apparatus.

  The laser light source 21 is a light source for exposing the resist deposited on the surface of the master 12 as a recording medium, and oscillates a recording laser beam 15 having a wavelength λ = 266 nm, for example. The laser light 15 emitted from the laser light source 21 travels straight as a parallel beam and enters an electro-optic element (EOM: Electro Optical Modulator) 22. The laser beam 15 transmitted through the electro-optical element 22 is reflected by the mirror 23 and guided to the modulation optical system 25.

  The mirror 23 is composed of a polarization beam splitter and has a function of reflecting one polarization component and transmitting the other polarization component. The polarization component transmitted through the mirror 23 is received by the photodiode 24, and the electro-optic element 22 is controlled based on the received light signal to perform phase modulation of the laser beam 15.

  In the modulation optical system 25, the laser light 15 is condensed by an condenser lens 26 onto an acousto-optic element (AOM) 27 made of glass (SiO 2) or the like. The laser beam 15 is intensity-modulated by the acoustooptic device 27 and diverges, and then converted into a parallel beam by the lens 28. The laser beam 15 emitted from the modulation optical system 25 is reflected by the mirror 31 and guided horizontally and parallel onto the moving optical table 32.

  The moving optical table 32 includes a beam expander 33 and an objective lens 34. The laser beam 15 guided to the moving optical table 32 is shaped into a desired beam shape by the beam expander 33 and then irradiated to the resist layer on the master 12 through the objective lens 34. The master 12 is placed on a turntable 36 connected to a spindle motor 35. Then, the resist layer is exposed to light by intermittently irradiating the resist layer with the laser beam 15 while rotating the master 12 and moving the laser beam 15 in the height direction of the master 12. The formed latent image has a substantially elliptical shape having a major axis in the circumferential direction. The laser beam 15 is moved by moving the moving optical table 32 in the arrow R direction.

  The exposure apparatus includes a control mechanism 37 for forming a latent image corresponding to the two-dimensional pattern of the hexagonal lattice or the quasi-hexagonal lattice shown in FIG. 1B on the resist layer. The control mechanism 37 includes a formatter 29 and a driver 30. The formatter 29 includes a polarity reversing unit, and this polarity reversing unit controls the irradiation timing of the laser beam 15 on the resist layer. The driver 30 receives the output from the polarity inversion unit and controls the acoustooptic device 27.

  In this roll master exposure apparatus, the polarity inversion formatter signal is synchronized with the rotation controller of the recording apparatus for each track so that the two-dimensional pattern is spatially linked, and the intensity is modulated by the acoustooptic element 27. . A hexagonal lattice pattern or a quasi-hexagonal lattice pattern can be recorded by patterning at a constant angular velocity (CAV) with an appropriate rotation speed, an appropriate modulation frequency, and an appropriate feed pitch. For example, as shown in FIG. 10B, in order to set the period in the circumferential direction to 315 nm and the period in the direction of about 60 degrees (about −60 degrees) with respect to the circumferential direction to 300 nm, the feed pitch is set to 251 nm. Good (Pythagorean law). The frequency of the polarity inversion formatter signal is changed according to the number of rotations of the roll (for example, 1,800 rpm, 900 rpm, 450 rpm, 225 rpm). For example, the frequency of the polarity inversion formatter signal facing the roll rotation speeds of 1,800 rpm, 900 rpm, 450 rpm, and 225 rpm is 37.70 MHz, 18.85 MHz, 9.34 MHz, and 4, 71 MHz, respectively. A quasi-hexagonal lattice pattern with a uniform spatial frequency (circumferential 315 nm period, circumferential direction approximately 60 degrees direction (approximately −60 degrees direction) 300 nm period) in a desired recording area is obtained by moving far ultraviolet laser light on the moving optical table 32. The beam expander (BEX) 33 enlarges the beam diameter to 5 times, and irradiates the resist layer on the master 12 through the objective lens 34 having a numerical aperture (NA) of 0.9 to form a fine latent image. Can be obtained.

<< Resist film formation process >>
First, as shown in FIG. 12A, a columnar master 12 is prepared. The master 12 is, for example, a glass master. Next, as shown in FIG. 12B, a resist layer 14 is formed on the surface of the master 12. As a material of the resist layer 14, for example, either an organic resist or an inorganic resist may be used. As the organic resist, for example, a novolac resist or a chemically amplified resist can be used. Moreover, as an inorganic type resist, the metal oxide which consists of 1 type, or 2 or more types of transition metals, such as tungsten and molybdenum, for example can be used.

<< Exposure process >>
Next, as shown in FIG. 12C, using the roll master exposure apparatus described above, the master 12 is rotated and the resist layer 14 is irradiated with a laser beam (exposure beam) 15. At this time, the resist layer 14 is irradiated with the laser beam 15 intermittently while moving the laser beam 15 in the height direction of the master 12 (direction parallel to the central axis of the columnar or cylindrical master 12). Is exposed over the entire surface. Thereby, a latent image 16 corresponding to the locus of the laser beam 15 is formed over the entire surface of the resist layer 14 at a pitch approximately equal to the visible light wavelength.

  For example, the latent image 16 is arranged to form a plurality of rows of tracks on the surface of the master and forms a hexagonal lattice pattern or a quasi-hexagonal lattice pattern. The latent image 16 has, for example, an elliptical shape having a major axis direction in the track extending direction.

<< Development process >>
Next, while rotating the master 12, a developer is dropped on the resist layer 14 to develop the resist layer 14 as shown in FIG. 13A. As shown in the figure, when the resist layer 14 is formed of a positive resist, the exposed portion exposed with the laser beam 15 has a higher dissolution rate in the developer than the non-exposed portion, so that the latent image (exposure) Part) A pattern corresponding to 16 is formed on the resist layer 14.

<< Etching process >>
Next, the surface of the master 12 is etched using the pattern (resist pattern) of the resist layer 14 formed on the master 12 as a mask. As a result, as shown in FIG. 13B, an elliptical cone-shaped or elliptical truncated cone-shaped recess having a major axis direction in the track extending direction, that is, a structure 13 can be obtained. The etching method is performed by dry etching, for example. At this time, by alternately performing the etching process and the ashing process, for example, a pattern of the cone-shaped structure 13 can be formed. In addition, a glass master having a depth three times or more of the resist layer 14 (selectivity ratio 3 or more) can be produced, and the structure 3 can have a high aspect ratio. As dry etching, plasma etching using a roll etching apparatus is preferable. The roll etching apparatus is a plasma etching apparatus having a columnar electrode, and the columnar electrode is inserted into the cavity of the cylindrical master 12 so that plasma etching is performed on the column surface of the master 12. Has been.

  As described above, for example, the roll master 11 having a concave hexagonal lattice pattern or quasi-hexagonal lattice pattern having a depth of about 120 nm to about 350 nm is obtained.

  Next, for example, the roll master 11 and a substrate 2 such as a sheet coated with a transfer material are brought into close contact with each other, and are peeled off while being irradiated with ultraviolet rays and cured. Thereby, as shown to FIG. 13C, the some structure which is a convex part is formed in one main surface of the base material 2, and a moth-eye ultraviolet-ray cured replication sheet etc. are produced.

  Next, as shown in FIG. 14A, an inorganic dielectric layer 5 is formed on the uneven surface of the base material 2 on which the structure 3 is formed, as necessary. As a method for forming the inorganic dielectric layer 5, for example, a CVD method (Chemical Vapor Deposition method) such as thermal CVD, plasma CVD, or photo CVD: a technique for depositing a thin film from a gas phase using a chemical reaction ), PVD methods (Physical Vapor Deposition) such as vacuum deposition, plasma-assisted deposition, sputtering, ion plating, etc .: Aggregate materials that are physically vaporized in a vacuum to form a thin film Technology).

  Next, a plasma treatment is performed on the inorganic dielectric layer 5.

Next, as shown in FIG. 14B, the transparent conductive layer 4 is formed on the inorganic dielectric layer 5. As a method for forming the transparent conductive layer 4, for example, a method similar to the method for forming the inorganic dielectric layer described above can be used. Next, the transparent conductive layer 4 is annealed as necessary. Thereby, the transparent conductive layer 4 is in a mixed state of amorphous and polycrystalline.
Thus, the intended conductive laminate 1 is obtained.

  According to this embodiment, since the transparent conductive layer 4 having a film thickness of 9 nm or more and 50 nm or less is formed on the uneven surface of the substrate 2 on which the structure 3 is formed, a wide range of surface resistance can be obtained. In addition, since the aspect ratio of the structure 3 is in the range of 0.3 to 1.0 and the surface shape of the transparent conductive layer 4 is made to follow the shape of the structure 3, excellent transmission characteristics can be obtained. it can. Further, by performing plasma treatment on the inorganic dielectric layer 5, the surface resistance value can be lowered without reducing visibility.

(Information input device)
The information input device of the present invention includes at least the conductive laminate of the present invention, and further includes other members as necessary.
Examples of the information input device include a touch panel.

  FIG. 15A is a perspective view showing a configuration of a touch panel as an example of the information input device of the present invention. FIG. 15B is a cross-sectional view showing a configuration of a touch panel as an example of the information input device of the present invention. The touch panel 50 is a so-called resistive film type touch. The resistive film type touch panel may be either an analog resistive film type touch panel or a digital resistive film type touch panel.

  The touch panel 50 includes a first conductive laminate 51 and a second conductive laminate 52 that faces the first conductive laminate 51. The first conductive laminate 51 and the second conductive laminate 52 are bonded to each other via a bonding portion 55 disposed between their peripheral portions. As the bonding unit 55, for example, an adhesive paste, an adhesive tape, or the like is used. From the viewpoint of improving the scratch resistance, the touch panel 50 preferably includes the hard coat layer 7 on the surface on the touch side of the first conductive laminate 51. The surface of the hard coat layer 7 is preferably provided with antifouling properties. The touch panel 50 is bonded to the display device 54 via the bonding layer 53, for example. As a material of the bonding layer 53, for example, an acrylic, rubber, or silicone pressure sensitive adhesive can be used. From the viewpoint of transparency, an acrylic pressure sensitive adhesive is preferable.

(Display device)
The display device of the present invention includes at least the conductive laminate of the present invention, and further includes other members as necessary.

  Examples of the display device include a liquid crystal display, a CRT (Cathode Ray Tube) display, a plasma display (PDP), an electroluminescence (EL) display, and a surface conduction electron-emitting device display (Surface-conduction). Electron-emitter Display (SED).

  FIG. 16 is a cross-sectional view illustrating an example of the configuration of the liquid crystal display device. As shown in FIG. 16, a liquid crystal display device 70 includes a liquid crystal panel (liquid crystal unit) having first and second main surfaces, a first polarizer 72 formed on the first main surface, A second polarizer 73 formed on the second main surface and a touch panel 50 disposed between the liquid crystal panel 71 and the first polarizer 72 are provided. The touch panel 50 is a liquid crystal display integrated touch panel (so-called inner touch panel).

The first polarizer 72 and the second polarizer 73 are bonded layers 74 and 75 to the first and second main surfaces of the liquid crystal panel 71 so that their transmission axes are orthogonal to each other. It is pasted through. The first polarizer 72 and the second polarizer 73 allow only one of the orthogonally polarized components of incident light to pass through and block the other by absorption. As the 1st polarizer 72 and the 2nd polarizer 73, what arranged the iodine complex and the dichroic dye in the uniaxial direction can be used for a polyvinyl alcohol (PVA) type film, for example. It is preferable to provide protective layers such as a triacetyl cellulose (TAC) film on both surfaces of the first polarizer 72 and the second polarizer 73.
In the present embodiment, since the polarizer 72 is shared by the liquid crystal panel 71 and the touch panel 50, the optical characteristics can be improved.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

<Height H, average arrangement pitch P, aspect ratio>
In the following examples, the height H, the arrangement pitch P, and the aspect ratio of the structure of the conductive laminate were determined as follows.
First, the surface shape of the optical sheet was photographed with an atomic force microscope (AFM) in a state where no ITO film was formed. Then, the arrangement pitch P1, the arrangement pitch P2, and the height H of the structures were obtained from the photographed AFM image and its cross-sectional profile. These measurements are repeated at 10 locations randomly selected from the optical sheet, and the measured values are simply averaged (arithmetic average) to obtain the average arrangement pitch P1, the average arrangement pitch P2, and the average height H, These average values were taken as arrangement pitch P1, arrangement pitch P2, and height H, respectively. Next, the aspect ratio (= height H / average arrangement pitch P) was determined using these (average) arrangement pitch P1, (average) arrangement pitch P2, and (average) height H.
Here, the average arrangement pitch P = (P1 + P2 + P2) / 3.

<Average thickness>
In the following examples, the average thicknesses of the inorganic dielectric layer and the transparent conductive layer were determined as follows.
First, the conductive laminate was cut, and the cross section thereof was photographed with a transmission electron microscope (TEM), and the thickness of the inorganic dielectric layer and the transparent conductive layer was measured from the photographed TEM photograph. These measurements are repeated at 10 locations randomly selected from the conductive laminate, and the average thickness is obtained by simply averaging the measured values (arithmetic average). The average thickness of the transparent conductive layer was used.
The average thickness when the conductive laminate has a structure is the same as the condition for forming the inorganic dielectric layer and the transparent conductive layer on the structure, and the inorganic dielectric layer and the transparent conductive layer on the flat plate. The average thickness of the inorganic dielectric layer and the transparent conductive layer on the flat plate was measured by the above method.

Example 1
First, a glass roll master having an outer diameter of 126 mm was prepared, and a resist layer was formed on the surface of the glass roll master as follows. That is, an inorganic resist material was formed to a thickness of about 50 nm by sputtering. Next, the glass roll master as a recording medium is transported to the roll master exposure apparatus shown in FIG. 11 and exposed to the resist layer, thereby being connected in one spiral and hexagonal between adjacent three rows of tracks. A latent image having a lattice pattern was patterned on the resist layer.

  Specifically, a hexagonal lattice-shaped exposure pattern is formed by irradiating an area where a hexagonal lattice-shaped exposure pattern is to be formed with a laser beam having a power of 0.50 mW / m that exposes the surface of the glass roll master. Formed. The thickness of the resist layer in the row direction of the track row was about 60 nm, and the thickness of the resist in the track extending direction was about 50 nm.

  Next, the resist layer on the glass roll master was subjected to development treatment, and the exposed resist layer was dissolved and developed. Specifically, an undeveloped glass roll master is placed on a turntable of a developing machine (not shown), and a developer is dropped on the surface of the glass roll master while rotating the entire turntable to develop the resist layer on the surface. did. Thereby, a resist glass master having a resist layer opened in a hexagonal lattice pattern was obtained.

Next, plasma etching was performed in a CHF ₃ gas atmosphere using a roll etching apparatus. As a result, only the hexagonal lattice pattern exposed from the resist layer is etched on the surface of the glass roll master, and the resist layer is used as a mask for the other regions and etching is not performed. Formed on the master. At this time, the etching amount (depth) was adjusted by the etching time. Finally, the moth-eye glass roll master having a concave hexagonal lattice pattern was obtained by completely removing the resist layer by O ₂ ashing. The depth of the recesses in the row direction was deeper than the depth of the recesses in the track extending direction.

  Next, the moth-eye glass roll master and the TAC (triacetyl cellulose) sheet coated with the active energy ray-curable resin composition were brought into close contact with each other, and the active energy ray-curable resin composition was peeled off while being irradiated with ultraviolet rays. . Thereby, the base material with which the some structure was arranged in one main surface was obtained. The structure had a height H of 170 nm, an arrangement pitch P of 270 nm, and an aspect ratio of 0.63.

Next, on the base material on which the structure is formed by sputtering (gas species; mixed gas of Ar gas and O ₂ gas, mixed ratio of mixed gas (volume ratio); Ar: O ₂ = 200: 13) An SiO ₂ layer having an average thickness of 5 nm was formed on the substrate.
Subsequently, a plasma bombardment process (RF power supply, irradiation power: 500 W, irradiation time: 20 seconds) using Ar was performed on the SiO ₂ layer.
Next, an average thickness of 36 nm is formed on the SiO ₂ layer by sputtering (gas species; mixed gas of Ar gas and O ₂ gas, mixed gas mixture ratio (volume ratio); Ar: O ₂ = 200: 13). An ITO layer was formed. Thereafter, annealing was performed at 150 ° C. for 1 hour.
By doing so, the electroconductive laminated body was obtained. Note that the SiO ₂ layer and the ITO layer had a shape following the uneven structure of the structure. FIG. 17 shows a cross-sectional photograph of the conductive laminate obtained in Example 1.

The formation of the SiO ₂ layer, the plasma treatment, and the formation of the ITO layer were performed as a series of treatments under vacuum conditions. That is, the formation of the SiO ₂ layer, the plasma treatment, and the formation of the ITO layer were performed while maintaining a vacuum state. By doing so, contamination of impurities could be avoided.

  About the obtained electroconductive laminated body, the measurement of specific resistance, evaluation of a luminous reflectance difference, and the measurement of NET intensity | strength were performed. The results are shown in Table 1.

<Measurement of specific resistance>
The specific resistance was measured by the 4-terminal method.

<Evaluation of luminous reflectance difference>
The measurement sample was produced by sticking a black tape on the surface on the opposite side to the transparent conductive layer side of the base material of the conductive laminate. Next, the reflection spectrum in the visible wavelength region (350 nm to 700 nm) of this measurement sample was measured with a spectrophotometer (trade name: V-550, manufactured by JASCO Corporation). Next, the difference ΔY in luminous reflectance was calculated by the following formula. Table 1 shows the calculation result of the difference ΔY in luminous reflectance. Here, the luminous reflectance is a reflectance at a wavelength of 550 nm.
ΔY = (Reflectance of measurement sample) − (Reflectance of target sample)
As a target sample, a sample produced in the same manner as in Example 1 except that the ITO layer was not formed was used.

<NET strength>
The NET intensity was measured using X'Pert Pro MPD manufactured by PANalytical. Specifically, a Cu tube (characteristic X-ray CuKα1 λ = 1.540598 mm) is used, and the range is 2θ (10 ° to 80 °) by the parallel method (incident angle: 1 °, flat collimator is used for the light receiving portion). Then, the diffraction intensity was measured by the peak fitting (fitting function: Pseudo-Voigt function) at the ITO crystal peak (222) (approximately 2θ = 30.6 °).

(Comparative Example 1)
A conductive laminate was produced in the same manner as in Example 1 except that the plasma bombardment process using Ar was not performed on the SiO ₂ layer.
About the obtained electroconductive laminated body, the measurement of specific resistance, evaluation of a luminous reflectance difference, and the measurement of NET intensity | strength were performed. The results are shown in Table 1.

  When Example 1 was compared with Comparative Example 1, it was confirmed in Example 1 that the specific resistance of the conductive laminate can be lowered by plasma treatment of the inorganic dielectric layer. Further, no decrease in luminous reflectance was observed.

(Example 2)
On the TAC (triacetylcellulose) sheet, the average thickness is obtained by sputtering (gas species; mixed gas of Ar gas and O ₂ gas, mixed ratio of mixed gas (volume ratio); Ar: O ₂ = 200: 13). A 5 nm SiO ₂ layer was formed.
Subsequently, a plasma bombardment process using Ar was performed on the SiO ₂ layer.
Next, an average thickness of 36 nm is formed on the SiO ₂ layer by sputtering (gas species: mixed gas of Ar gas and O ₂ gas, mixed gas mixture ratio (volume ratio); Ar: O ₂ = 200: 13). An ITO layer was formed. Thereafter, annealing was performed at 150 ° C. for 1 hour.
By doing so, the electroconductive laminated body was obtained.
About the obtained electroconductive laminated body, the measurement of specific resistance, evaluation of a luminous reflectance difference, and the measurement of NET intensity | strength were performed. The results are shown in Table 2.

(Comparative Example 2)
In Example 2, a conductive laminate was produced in the same manner as in Example 2 except that the plasma bombardment process using Ar was not performed on the SiO ₂ layer.
About the obtained electroconductive laminated body, the measurement of specific resistance, evaluation of a luminous reflectance difference, and the measurement of NET intensity | strength were performed. The results are shown in Table 2.

  When Example 2 was compared with Comparative Example 2, it was confirmed that in Example 2, the specific resistance of the conductive laminate could be lowered by plasma treatment of the inorganic dielectric layer. Further, no decrease in luminous reflectance was observed.

The relationship between the NET intensity of Examples 1 and 2 and Comparative Examples 1 and 2 and the specific resistance is shown in FIG.
By performing the plasma treatment, the NET intensity increased, and the specific resistance decreased accordingly.

  Since the conductive laminate of the present invention can reduce the surface resistance value without reducing the visibility, it can be suitably used for an information input device such as a touch panel.

DESCRIPTION OF SYMBOLS 1 Conductive laminated body 2 Base material 3 Structure 4 Transparent conductive layer 5 Inorganic dielectric layer 6 Protrusion part 11 Roll master 12 Base material 13 Structure 14 Resist layer 15 Laser beam 16 Latent image 41 Disc master 42 Master disk 43 Structure 50 Touch panel 51 First conductive laminate 52 Second conductive laminate 54 Display device

Claims (10)

A substrate, an inorganic dielectric layer formed on the substrate, and a transparent conductive layer formed on the inorganic dielectric layer,
A conductive laminate, wherein the inorganic dielectric layer is subjected to plasma treatment. A substrate, an inorganic dielectric layer formed on the substrate, and a transparent conductive layer formed on the inorganic dielectric layer,
The conductive laminate, wherein a NET intensity of a diffraction peak of In ₂ O ₃ (222) in XRD measurement of the transparent conductive layer is 1,200 counts or more. The conductive laminate according to claim 1, wherein the inorganic dielectric layer contains SiO ₂ .   The conductive laminate according to claim 1, wherein the transparent conductive layer contains ITO. Between the base material and the inorganic dielectric layer, it has a structure disposed at a fine pitch below the wavelength of visible light,
The conductive laminate according to claim 1, wherein the inorganic dielectric layer and the transparent conductive layer have a shape that follows the shape of the structure. An inorganic dielectric layer forming step of forming an inorganic dielectric layer on the substrate;
A plasma processing step of performing plasma processing on the inorganic dielectric layer;
And a transparent conductive layer forming step of forming a transparent conductive layer on the inorganic dielectric layer.   The method for producing a conductive laminate according to claim 6, wherein the transparent conductive layer is formed by sputtering. An uncured resin layer forming step of forming an uncured resin layer by applying an active energy ray-curable resin composition on a substrate;
Adhering a transfer master having either a fine convex part or a concave to the uncured resin layer, irradiating the uncured resin layer to which the transfer master is in contact with an active energy ray to cure the uncured resin layer A structure forming step of forming a structure disposed at a fine pitch below the wavelength of visible light by transferring any of the fine convex portions and concave portions;
The manufacturing method of the conductive laminated body in any one of Claim 6 to 7 included before an inorganic dielectric material layer formation process.   An information input device comprising the conductive laminate according to claim 1.   A display device comprising the conductive laminate according to claim 1.