JP4393573B1 - Transparent conductive laminate and transparent touch panel using the same - Google Patents

Abstract

A transparent conductive laminate capable of preventing Newton's rings occurring between two transparent electrode substrates constituting a transparent touch panel, and a transparent touch panel using such a transparent conductive laminate.
A transparent conductive laminate (14) in which a cured resin layer (15) having an uneven surface and a transparent conductive layer (14) are sequentially laminated on at least one surface of a transparent organic polymer substrate (16). 15 and 16), wherein the cured resin layer is dispersed in the cured resin component and the cured resin component, and the metal oxide ultrafine particles A and the metal fluoride ultrafine particles having an average primary particle diameter of 100 nm or less. The content of these ultrafine particles A and B in the cured resin layer is 1 to 20 parts by mass per 100 parts by mass of the cured resin component, and the ultrafine particles A and B have fine particles B. The transparent conductive laminate is characterized in that the mass ratio (A / B) is larger than 0.3. Moreover, it is set as the transparent touch panel (20) which has such a transparent conductive laminated body (14, 15, 16).
[Selection] Figure 3

Description

  The present invention relates to a transparent touch panel and a transparent conductive laminate suitable for the transparent touch panel. In more detail, it is related with the transparent touch panel excellent in visibility, and the transparent conductive laminated body used for it.

  In recent years, a transparent touch panel that realizes an interactive input method is often used as one of man-machine interfaces. The transparent touch panel includes an optical method, an ultrasonic method, a capacitance method, a resistance film method, and the like depending on the position detection method. Among these, the resistive film method has been rapidly spread in recent years because of its simple structure and good price / performance ratio.

  A resistive film type transparent touch panel is an electronic component configured by holding two films or sheets having a transparent conductive layer on opposite sides at a constant interval, and a movable electrode substrate (viewing side electrode substrate) is a pen. Alternatively, the detection circuit detects the position by pressing and bending with a finger, making contact with the fixed electrode substrate (the electrode substrate on the opposite side) and conducting, and a predetermined input is made. At this time, interference fringes called Newton rings may appear around the pressing portion. Even in a state where the electrode is not pressed, a Newton ring may appear in a portion where the distance between the movable electrode substrate and the fixed electrode substrate is narrowed due to the bending of the movable electrode substrate. The visibility of the display decreases due to the occurrence of Newton rings.

  In order to reduce Newton's ring generated between two transparent electrode substrates constituting such a resistive film type transparent touch panel, a method of forming irregularities of appropriate shape and size on the film surface is effective. . Specifically, a method of forming a coating layer containing a predetermined amount of filler having an average primary particle diameter of 1 to 4 μm and a transparent conductive layer on a plastic film (see Patent Document 1), an average secondary particle diameter of 1.0 A method of forming a protrusion coating layer (coating layer having protrusions) containing silica particles of ˜3.0 μm on a plastic film is disclosed (see Patent Document 2).

  In the case of a transparent touch panel using a transparent conductive laminate in which a coating layer containing particles having an average primary particle size or secondary particle size of about several microns as described above and a transparent conductive layer are formed on a plastic film, Newton rings Occurrence is reduced. However, when the transparent touch panel is installed on a high-definition display in recent years, the resin around the particles in the coating layer plays a lens effect, so that color separation (sparkling) of light coming from the display is achieved. This causes a problem that the visibility of the display is remarkably deteriorated.

  Further, as a coating layer for reducing Newton rings other than the above, inorganic ultrafine particles having an average primary particle size of 100 nm or less are added to a cured resin containing inorganic fine particles having an average primary particle size of 0.5 μm or more and 5 μm or less. Thus, a method has been disclosed in which the uneven shape is controlled to simultaneously reduce the deterioration of visibility due to Newton's ring generation and flickering (see Patent Document 3). However, when the anti-Newton ring layer formed by this method is subjected to the sliding durability and end-press durability test required for the touch panel, the transparent conductive layer deteriorates from the protruding portion formed by these inorganic particles.・ Because it begins to peel, there is a problem that the electrical characteristics of the touch panel deteriorate at the end.

  In addition, when performing a dot durability test, the protrusions formed by inorganic fine particles contained on the transparent conductive layer forming surface of the movable electrode substrate destroy the dot spacers formed on the fixed electrode substrate, and the fragments are in the touch panel. Scatter. There is a problem in that the scattered dot spacer fragments prevent the conduction between the movable electrode substrate and the fixed electrode substrate, and deteriorate the electrical characteristics of the touch panel. Further, the scattered dot spacer fragments may damage the transparent conductive layers of the movable electrode substrate and the fixed electrode substrate, thereby deteriorating the electrical characteristics of the touch panel.

  Further, when an anti-Newton ring layer formed using such inorganic fine particles is used as a fixed electrode substrate, the protrusions formed by the inorganic fine particles damage the transparent conductive layer of the movable electrode substrate, and the touch panel There is also a problem that the characteristics deteriorate. In addition, when a resin layer containing fine particles of about several μm is formed by wet coating using a gravure coater or the like, the fine particles in the coating solution settle out over time, so it is necessary to change the coating solution frequently. There was a problem with productivity.

  As a method not using inorganic fine particles of 1 μm or more in order to form irregularities on the film surface, irradiating the thermoplastic resin and inorganic fine particles having an average primary particle diameter of 0.001 μm or more and less than 1 μm with activation energy rays However, in the layer formed by such a method, the haze becomes extremely high, and there is a problem of deteriorating the visibility of the display (Patent Document 4). reference).

  Further, although a method for forming an uneven shape by dispersing ultrafine particles having an average primary particle diameter of 100 nm or less as an aggregate of less than 1.0 μm or in a state where no aggregate is formed in a cured resin layer is disclosed. Since the anti-Newton ring layer formed by such a method has small unevenness, Newton rings were confirmed when the pressure was strong (see Patent Documents 5, 6, 7, and 8).

Japanese Patent Laid-Open No. 10-323931 JP 2002-373056 A JP 2006-190512 A JP 2002-275391 A JP 2006-056136 A JP 2005-209431 A JP 2004-351744 A JP 2004-195898 A

  An object of the present invention is to provide a transparent touch panel that can prevent Newton's rings from occurring between two transparent electrode substrates constituting a transparent touch panel without causing deterioration of visibility due to flicker even when the transparent touch panel is installed on a high-definition display. It is providing the transparent conductive laminated body for touchscreens.

  Another object of the present invention is to provide a transparent conductive laminate having good visibility and maintaining the above-mentioned visibility.

  Still another object of the present invention is to provide a novel transparent touch panel using the transparent conductive laminate.

  In order to solve the above problems, the present inventors have intensively studied a surface roughening technique using ultrafine particles. As a result, at least one metal oxide ultrafine particle having an average primary particle size of 100 nm or less and at least one kind of metal oxide are used. By mixing and using metal fluoride ultrafine particles having an average primary particle size of 100 nm or less in a specific ratio, a weak associating state is formed in the cured resin layer, and a desired uneven shape is formed. The inventor has conceived the present invention described below.

<1> A transparent conductive laminate in which a cured resin layer having an uneven surface and a transparent conductive layer are sequentially laminated on at least one surface of a transparent organic polymer substrate,
(1) The cured resin layer is a cured resin component, and at least one metal oxide ultrafine particle A having an average primary particle diameter of 100 nm or less and at least one average primary particle diameter dispersed in the cured resin component. Having metal fluoride ultrafine particles B of 100 nm or less,
(2) The content of the metal oxide ultrafine particles A in the cured resin layer is 1 part by mass or more and less than 20 parts by mass per 100 parts by mass of the cured resin component,
(3) The content of the metal fluoride ultrafine particles B in the cured resin layer is 1 part by mass or more and less than 20 parts by mass per 100 parts by mass of the cured resin component,
(4) The mass ratio (A / B) of the metal oxide ultrafine particles A to the metal fluoride ultrafine particles B in the cured resin layer is greater than 0.3, and (5) the metal oxide ultrafine particles A are SiO. ₂ and the metal fluoride ultrafine particle B is MgF ₂ .
Transparent conductive laminate.
<2> The ten-point average roughness (Rz) of the cured resin layer is 300 nm or more and less than 1500 nm, and the arithmetic average roughness (Ra) of the cured resin layer is 50 nm or more and less than 300 nm. The transparent conductive laminate according to <1> above.
<3> The transparent conductive laminate according to <1> or <2>, wherein the thickness of the cured resin layer is 0.1 to 4.5 μm.
<4> The transparent conductive laminate according to any one of <1> to <3>, wherein the haze based on the transparent organic polymer substrate and the cured resin layer is 1% or more and less than 10%.
<5> Any of the above items <1> to <4>, wherein the transparent conductive layer is a crystalline layer containing indium oxide as a main component, and the thickness of the transparent conductive layer is 5 to 50 nm. The transparent conductive laminate described.
<6> The metal compound layer which is in contact with the transparent conductive layer and whose film thickness is thinner than the transparent conductive layer and is less than or equal to 0.5 nm and less than 5.0 nm is provided between the cured resin layer and the transparent conductive layer. The transparent conductive laminate according to any one of <1> to <5>.
<7> The transparent conductive laminate according to <6> , wherein the metal of the metal compound layer is the same as the metal of the metal oxide ultrafine particles A and / or metal fluoride ultrafine particles B.
<8> In a transparent touch panel in which two transparent electrode substrates each provided with a transparent conductive layer on at least one side are arranged so that the transparent conductive layers face each other, the first electrode as the at least one transparent electrode substrate <1>-<7> A transparent touch panel characterized by using the transparent conductive laminate according to any one of items .

  ADVANTAGE OF THE INVENTION According to this invention, even if it installs on a high-definition display, it is a transparent touch panel which does not raise | generate visibility degradation by flickering, Comprising: The Newton ring which generate | occur | produces between the two transparent electrode substrates which comprise a transparent touch panel can be prevented. A transparent conductive laminate for a transparent touch panel is provided. Moreover, according to this invention, the display and optical electronic component which use such a transparent conductive laminated body of this invention are provided.

  More specifically, when the transparent conductive laminate of the present invention is used as an optical electronic component, it is less likely to cause pixel color separation (flicker) even when applied to a high-definition display while reducing Newton rings. The optical characteristics can be balanced, and it can be applied as a completely new touch panel substrate having optical characteristics with excellent visibility that could not be realized by conventional techniques.

  In addition, in the transparent touch panel using the transparent conductive laminate of the present invention, color separation (flicker) of pixels on a high-definition display body can be achieved while suppressing Newton rings generated between the movable electrode substrate and the fixed electrode substrate. Can be suppressed.

  Furthermore, in the transparent conductive laminate of the present invention, the frequency of replacement of the coating liquid during production can be reduced.

  Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following descriptions.

The transparent conductive laminate of the present invention is a transparent conductive laminate in which a cured resin layer having an uneven surface and a transparent conductive layer are sequentially laminated on at least one surface of a transparent organic polymer substrate. As shown in FIG. 3 , one embodiment of the transparent conductive laminate of the present invention comprises a cured resin layer (15) having an uneven surface and a transparent surface on at least one surface of a transparent organic polymer substrate (16). A transparent conductive laminate in which a conductive layer (14) is sequentially laminated. In one embodiment of the transparent conductive laminate of the present invention shown in FIG. 3 , the transparent conductive laminate (14, 15, 16) of the present invention is a glass plate having a transparent conductive layer (12). A transparent touch panel (20) can be formed by disposing the substrate (11) and the transparent conductive layers (12, 14) so that the transparent conductive layers (12, 14) face each other and a spacer (13) disposed therebetween.

<Transparent organic polymer substrate>
The transparent organic polymer substrate used in the transparent conductive laminate of the present invention is an arbitrary transparent organic polymer substrate, particularly a transparent organic polymer substrate excellent in heat resistance and transparency used in the optical field. It's okay.

  Examples of the transparent organic polymer substrate used in the transparent conductive laminate of the present invention include polyester polymers such as polyethylene terephthalate and polyethylene naphthalate, polycarbonate polymers, cellulose polymers such as diacetyl cellulose and triacetyl cellulose, and polymethyl methacrylate. And a substrate made of a transparent polymer such as an acrylic polymer. The transparent organic polymer substrate used in the transparent conductive laminate of the present invention includes polystyrene, styrene-based polymers such as acrylonitrile / styrene copolymer, polyethylene, polypropylene, polyolefin having a cyclic or norbornene structure, and ethylene / propylene copolymer. Examples thereof include substrates made of transparent polymers such as olefin polymers such as polymers, vinyl chloride polymers, amide polymers represented by nylon and aromatic polyamide. Furthermore, as the transparent organic polymer substrate used in the transparent conductive laminate of the present invention, imide polymer, sulfone polymer, polyether sulfone polymer, polyether ether ketone polymer, polyphenylene sulfide polymer, vinyl alcohol type Examples also include substrates made of transparent polymers such as polymers, vinylidene chloride polymers, vinyl butyral polymers, arylate polymers, polyoxymethylene polymers, epoxy polymers and blends of the above polymers.

  For use in the transparent conductive laminate of the present invention, among these transparent organic polymer substrates, those having low optical birefringence, those having birefringence controlled to λ / 4 or λ / 2, and birefringence What is not controlled at all can be appropriately selected according to the application. As described here, when selecting appropriately according to the application, for example, polarizing plates, retardation films, inner type touch panels used in liquid crystal displays, etc., depending on polarized light such as linearly polarized light, elliptically polarized light, circularly polarized light, etc. A case where the transparent conductive laminate of the present invention is used as a display member exhibiting a function can be given.

  The film thickness of the transparent polymer substrate can be appropriately determined, but is generally about 10 to 500 μm, particularly 20 to 300 μm, more preferably 30 to 200 μm from the viewpoint of workability such as strength and handleability.

<Curing resin layer>
The cured resin layer having a concavo-convex shape used in the transparent conductive laminate of the present invention comprises a cured resin component, and at least one metal oxide super particle having an average primary particle diameter of 100 nm or less dispersed in the cured resin component. Fine particles A and metal fluoride ultrafine particles B having an average primary particle diameter of 100 nm or less are contained.

<Hardened resin layer-cured resin component>
As the curable resin component, it is possible to disperse ultrafine particles having an average primary particle diameter of 100 nm or less, and there is no particular limitation to use a transparent material that has sufficient strength as a film after the formation of the cured resin layer and is transparent. Examples include radiation curable resins and thermosetting resins.

  Monomers and polyfunctional acrylates such as polyol acrylates, polyester acrylates, urethane acrylates, epoxy acrylates, modified styrene acrylates, melamine acrylates, and silicon-containing acrylates that give a hard layer other than those described above are examples of monomers that provide ionizing radiation curable resins Can be mentioned.

  Specific monomers that give the ionizing radiation curable resin include, for example, trimethylolpropane trimethacrylate, trimethylolpropylane ethylene oxide-modified triacrylate, trimethylolpropylane propylene oxide-modified triacrylate, isocyanuric acid ethylene oxide-modified triacrylate, pentaerythritol triacrylate. Multifunctional such as acrylate, dipentaerythritol hexaacrylate, dimethylol tricyclodecane diacrylate, tripropylene glycol triacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, epoxy modified acrylate, urethane modified acrylate, epoxy modified acrylate Monomer.

  These monomers that give ionizing radiation curable resins may be used alone or in combination of several kinds, and in some cases, an appropriate amount of various alkoxysilane hydrolysates may be added. In addition, when polymerizing a resin layer by ionizing radiation, generally an appropriate amount of a photopolymerization initiator may be added, and an appropriate amount of a photosensitizer may be added as necessary. Examples of the photopolymerization initiator include acetophenone, benzophenone, benzoin, benzoylbenzoate, and thioxanthone. Examples of the photosensitizer include triethylamine and tri-n-butylphosphine.

  As the thermosetting resin, for example, an organosilane thermosetting resin using a silane compound such as methyltriethoxysilane or phenyltriethoxysilane as a monomer, a melamine thermosetting resin using etherified methylolmelamine or the like as a monomer, Examples thereof include an isocyanate thermosetting resin, a phenol thermosetting resin, and an epoxy curable resin. These thermosetting resins can be used alone or in combination. If necessary, a thermoplastic resin can be mixed with the thermosetting resin.

  In addition, when bridge | crosslinking a resin layer with a heat | fever, a reaction accelerator and / or a hardening | curing agent can be mix | blended in a proper quantity. Examples of the reaction accelerator include triethylenediamine, dibutyltin dilaurate, benzylmethylamine, pyridine and the like. Examples of the curing agent include methylhexahydrophthalic anhydride, 4,4′-diaminodiphenylmethane, 4,4′-diamino-3,3′-diethyldiphenylmethane, diaminodiphenylsulfone, and the like.

  The cured resin layer may contain a third component such as a leveling agent or a photosensitizer.

<Hardened resin layer-ultrafine particles>
(material)
The average primary particle diameter 100nm or less of the metal oxide ultrafine particle A to be blended in the cured resin, it is possible to have use the S iO _2.

As the metal fluoride ultrafine particles B having an average primary particle diameter of 100 nm or less to be blended with the cured resin, MgF ₂ can be used .

(Distributed state)
In the use of the present invention, the cured resin layer that forms the uneven shape is required to maintain good visibility even when placed on a high-definition display, but the metal oxide ultrafine particles A and / or When the metal fluoride ultrafine particles B form a clear aggregate having an optical wavelength or longer, flickering increases and visibility decreases. On the other hand, when the metal oxide ultrafine particles A and the metal fluoride ultrafine particles B are substantially homogeneously dispersed, the height of the unevenness formed becomes low, and the distance between the two transparent electrode substrates constituting the transparent touch panel is reduced. The Newton ring that occurs in this case cannot be prevented, and the visibility during actual use is significantly reduced.

  Therefore, in the transparent conductive laminate of the present invention, it is preferable that the metal oxide ultrafine particles A and the metal fluoride ultrafine particles B do not form secondary aggregates or secondary particles of 1 μm or more, particularly the optical wavelength. It is preferable that the above secondary aggregates or secondary particles, for example, secondary aggregates or secondary particles of 600 nm or more are not formed. However, there may be a state in which the metal oxide ultrafine particles A and / or metal fluoride ultrafine particles B having an average primary particle diameter of 100 nm or less form secondary aggregates having an optical wavelength less than that.

  Further, in the transparent conductive laminate of the present invention, it is desired that the metal oxide ultrafine particles A and the metal fluoride ultrafine particles B are in a weak association state to form irregularities with appropriate shapes on the surface.

(Mixing ratio)
The compounding ratio for dispersing the ultrafine particles in the cured resin is such that the metal oxide ultrafine particles A and the metal fluoride ultrafine particles B are each 1 to 20 parts by mass with respect to 100 parts by mass of the cured resin component. Necessary, preferably 1 to 15 parts by mass, and more preferably 1 to 10 parts by mass. This is because when the metal oxide ultrafine particles A and / or the metal fluoride ultrafine particles B are too small, it is difficult to form a resin layer having irregularities on the surface necessary for the use of the present invention. When is too large, the ratio of the cured resin component is decreased, so that it is difficult to have sufficient strength as a film after the cured resin layer is formed.

  In order to sufficiently increase the unevenness of the cured resin layer, the mass ratio (A / B (%)) of the metal oxide ultrafine particles A to the metal fluoride ultrafine particles B should be larger than 0.3. Required, preferably this ratio is greater than 0.3 and 10.0 or less, more preferably this ratio is greater than 0.3 and 5.0 or less.

<Hardened resin layer-film thickness>
The thickness of the cured resin layer having irregularities on the surface is preferably from 0.1 μm to 4.5 μm, and more preferably from 0.1 μm to 3 μm. When the film thickness is too small, the UV curable resin is not preferable because it is likely to be insufficiently cured due to the influence of oxygen. In general, when the film thickness is too large, curing shrinkage of the ultraviolet curable resin deflects the polymer substrate and causes curling, which is not preferable.

  Since the unevenness on the surface of the cured resin layer is also affected by the film thickness, it is very important to control the film thickness. In particular, in the case of the present invention, when only the film thickness is changed with the metal oxide ultrafine particles A and the metal fluoride ultrafine particles B added to the cured resin component to a certain amount, the surface becomes flatter as the film thickness is reduced. Conversely, the surface tends to become rougher as the film thickness is increased.

<Curing resin layer-other components>
Moreover, the unevenness | corrugation of the surface of the cured resin layer in this invention is dependent also on the thixotropy of the ultrafine particle to be used. Therefore, for the purpose of expressing or controlling thixotropy, a solvent and a dispersant can be appropriately selected and used when forming the cured resin layer. As the solvent, for example, various alcohols, aromatics, ketones, lactates, cellosolves, glycols and the like can be used. Examples of the dispersant include various fatty acid amines, sulfonic acid amides, ε-caprolactone, hydrostearic acid, polycarboxylic acid, and polyesteramine. These solvents and dispersants can be used alone or in combination of two or more.

<Curing resin layer-surface irregularities>
(Ten point average roughness (Rz))
As for the unevenness of the surface of the cured resin layer, the ten-point average roughness (Rz) is preferably 300 nm or more and less than 1500 nm, more preferably 300 nm or more and less than 1000 nm, and particularly preferably 300 nm or more and less than 800 nm. . When the ten-point average roughness (Rz) is too small, Newton's ring occurs when the glass or film substrate is brought into strong contact with the uneven surface of the present invention. On the other hand, if the ten-point average roughness (Rz) is too large, the haze becomes large, and when applied to a high-definition liquid crystal display, the color separation of pixels occurs, causing flickering and so on. It is not preferable.

  In the present invention, the ten-point average roughness (Rz) is defined in accordance with JIS B0601-1982. Specifically, the ten-point average roughness (Rz) is a value obtained by an analog surface roughness measuring instrument, and in the cross-sectional curve (data as measured) of the reference length in descending order from the highest peak. It is a value defined as the sum of the average of the peak heights up to the fifth and the average of the depths of the valleys up to the fifth in order from the deepest valley bottom. Here, the reference length is 0.25 mm.

(Average arithmetic roughness (Ra))
Further, the average arithmetic roughness (Ra) of the unevenness of the surface of the cured resin layer generated in the present invention is preferably 50 nm or more and less than 300 nm, more preferably 50 nm or more and less than 200 nm, and more preferably 50 nm or more and less than 150 nm. It is particularly desirable. If the average arithmetic roughness (Ra) is too large, the haze becomes large, and when it is applied to a high-definition liquid crystal display, it is not preferable as a substrate for display applications because it causes pixel color separation and flickering. On the other hand, when the average arithmetic roughness (Ra) is too small, Newton's ring occurs when the glass or film substrate is brought into strong contact with the uneven surface of the present invention.

  In the present invention, the average arithmetic roughness (centerline average roughness) (Ra) is defined in accordance with JIS B0601-1994. Specifically, the arithmetic average roughness (Ra) is determined by extracting a portion of the reference length L from the roughness curve in the direction of the center line, the center line of the extracted portion being the X axis, and the direction of the vertical magnification being the Y axis. And when the roughness curve is represented by y = f (x), it is represented by the following formula:

<Hardened resin layer-haze>
The cured resin layer having a concavo-convex surface of the present invention is obtained by changing parameters such as the amount of solvent, dispersant, metal oxide ultrafine particles A and / or metal fluoride ultrafine particles B, and the thickness of the cured resin layer. Rz, Ra, and further haze can be controlled freely.

  From the viewpoint of visibility, haze is preferably 1% or more and less than 10%, more preferably 1% or more and less than 8%, and particularly preferably 1% or more and less than 7%.

In the present invention, haze is defined according to JIS K7136. Specifically, haze is a value defined as the ratio of diffuse transmittance τ _d to total light transmittance τ _t , and more specifically can be determined from the following equation:
Haze (%) = [(τ ₄ / τ ₂ ) −τ ₃ (τ ₂ / τ ₁ )] × 100
τ ₁ : incident light beam τ ₂ : total light beam transmitted through the test piece τ ₃ : light beam diffused by the device τ ₄ : light beam diffused by the device and the test piece

<Curing resin layer-forming method>
As a method for forming a cured resin layer having an uneven surface according to the present invention, formation by a wet method is particularly suitable. For example, a doctor knife, bar coater, gravure roll coater, curtain coater, knife coater, spin coater, spray method, immersion Any known method such as a method can be used.

<Transparent conductive layer>
In the present invention, the transparent conductive layer is not particularly limited, and examples thereof include a crystalline metal layer or a crystalline metal compound layer. Examples of the component constituting the transparent conductive layer include metal oxide layers such as silicon oxide, aluminum oxide, titanium oxide, magnesium oxide, zinc oxide, indium oxide, and tin oxide. Of these, a crystalline layer mainly composed of indium oxide is preferable, and a layer made of crystalline ITO (Indium Tin Oxide) is particularly preferably used.

  When the transparent conductive layer is crystalline, the crystal grain size need not be particularly limited, but is preferably 3000 nm or less. A crystal grain size exceeding 3000 nm is not preferable because writing durability is deteriorated. Here, the crystal grain size is defined as the largest diagonal line or diameter in each polygonal or oval region observed under a transmission electron microscope (TEM).

  When the transparent conductive layer is not a crystalline film, the sliding durability and environmental reliability required for the touch panel may be lowered.

  The transparent conductive layer can be formed by a known method. For example, a physical formation method (such as a DC magnetron sputtering method, an RF magnetron sputtering method, an ion plating method, a vacuum deposition method, a pulse laser deposition method) Physical Vapor Deposition (hereinafter referred to as “PVD”)) or the like can be used, but focusing on industrial productivity of forming a metal compound layer having a uniform film thickness over a large area, the DC magnetron sputtering method is desirable. In addition to the physical formation method (PVD), a chemical formation method such as a chemical vapor deposition method (hereinafter referred to as “CVD”) or a sol-gel method may be used. The sputtering method is desirable from the viewpoint of thickness control.

  The film thickness of the transparent conductive layer is preferably 5 to 50 nm from the viewpoints of transparency and conductivity. More preferably, it is 5-30 nm. If the film thickness of the transparent conductive layer is less than 5 nm, the resistance value tends to be inferior in stability over time, and if it exceeds 50 nm, the surface resistance value decreases, which is not preferable as a touch panel.

  When the transparent conductive laminate of the present invention is used for a touch panel, the surface resistance value of the transparent conductive layer is 100 to 2000Ω / □ (Ω at a film thickness of 10 to 30 nm due to reduction of power consumption of the touch panel and circuit processing. / Sq), more preferably a transparent conductive layer having a range of 140 to 1000 Ω / □ (Ω / sq) is preferably used.

<Metal compound layer>
The transparent conductive laminate of the present invention may further have a metal compound layer having a film thickness of 0.5 nm or more and less than 5.0 nm between the cured resin layer having an uneven surface and the transparent conductive layer.

  By sequentially laminating a transparent organic polymer substrate, a cured resin layer having an uneven surface, a metal compound layer having a controlled film thickness, and a transparent conductive layer, the adhesion between the layers is greatly improved. Further, by making the metal of the metal oxide ultrafine particles A and / or metal fluoride ultrafine particles B in the cured resin layer the same as the metal of the metal compound layer, the cured resin layer and the transparent conductive layer having an uneven surface The adhesion between the layers is further improved.

  In the transparent touch panel using the transparent conductive laminate having such a metal compound layer, the writing durability required for the transparent touch panel is improved as compared with the case where there is no metal compound layer. When the thickness of the metal compound layer is 5.0 nm or more, the endurance durability required for the transparent touch panel cannot be improved because the metal compound layer starts to exhibit mechanical properties as a continuum. On the other hand, when the film thickness is less than 0.5 nm, it is difficult to control the film thickness, and it becomes difficult to fully develop the adhesion between the cured resin layer having an uneven surface and the transparent conductive layer, which is required for a transparent touch panel. Improvement in writing durability may be insufficient.

  Examples of the component constituting the metal compound layer include metal oxide layers such as silicon oxide, aluminum oxide, titanium oxide, magnesium oxide, zinc oxide, indium oxide, and tin oxide.

  These metal compound layers can be formed by a known method, for example, physical formation such as DC magnetron sputtering method, RF magnetron sputtering method, ion plating method, vacuum deposition method, pulse laser deposition method, etc. The method (PVD) or the like can be used, but the DC magnetron sputtering method is desirable from the viewpoint of industrial productivity of forming a metal compound layer having a uniform film thickness over a large area. In addition to the physical formation method (PVD), a chemical formation method such as a chemical vapor deposition method (CVD) or a sol-gel method can be used, but the sputtering method is desirable from the viewpoint of film thickness control. .

  As a target used for sputtering, a metal target is preferably used, and a reactive sputtering method is widely employed. This is because the oxide of the element used as the metal compound layer is often an insulator, and in the case of a metal compound target, the DC magnetron sputtering method is often not applicable. In recent years, a power source has been developed that simultaneously discharges two cathodes and suppresses formation of an insulator on a target, and a pseudo RF magnetron sputtering method can be applied.

<Optical interference layer and hard coat layer>
In the transparent conductive laminate of the present invention, an optical interference layer and a hard coat layer that control reflectance by optical interference can be used singly or in combination, if necessary, in an appropriate order. . The order of lamination of the transparent conductive layer, the optical interference layer, and the hard coat layer is not particularly limited as long as the function expected to be exhibited is achieved depending on the application. When these stacking orders are used as, for example, a touch panel substrate, the transparent conductive layer is A, the optical interference layer is B, the cured resin layer having an uneven surface is C, the transparent organic polymer substrate is D, and the hard coat is E. For example, A / B / C / D / E, A / B / C / D / C, A / B / B / C / D / E, A / B / B / C / D / C, A / C / D / E / B, A / C / D / C / B, A / C / D / E / B / B, A / C / D / C / B / B, and the like.

  The optical interference layer refers to a layer that prevents or suppresses reflected light by appropriately combining a high refractive index layer and a low refractive index layer. The optical interference layer is composed of at least one high refractive index layer and at least one low refractive index layer. Two or more combination units of the high refractive index layer and the low refractive index layer may be used. When the optical interference layer is composed of one high refractive index layer and one low refractive index layer, the thickness of the optical interference layer is preferably 30 nm to 150 nm, and more preferably 50 nm to 150 nm. The optical interference layer can be formed by either a wet method or a dry method. For example, in the wet method, doctor knife, bar coater, gravure roll coater, curtain coater, knife coater, spin coater, etc., spray method, dipping method, etc., in dry method, PVD method such as sputtering method, vacuum deposition method, ion plating method, etc. Printing method, CVD method, etc. can be applied.

  As the hard coat layer, a thermosetting resin, an active energy ray curable resin, or the like can be applied. Among these, an ultraviolet curable resin using ultraviolet rays for active energy rays is preferable because it is excellent in productivity and economy.

  Examples of the ultraviolet curable resin for the hard coat layer include 1,6-hexanediol diacrylate, 1,4-butanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, tetraethylene glycol diacrylate, and tripropylene glycol. Diacrylate, neopentyl glycol diacrylate, 1,4-butanediol dimethacrylate, poly (butanediol) diacrylate, tetraethylene glycol dimethacrylate, 1,3-butylene glycol diacrylate, triethylene glycol diacrylate, triisopropylene Diacrylates such as glycol diacrylate, polyethylene glycol diacrylate and bisphenol A dimethacrylate; Triacrylates such as tyrolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol monohydroxytriacrylate and trimethylolpropane triethoxytriacrylate; tetraacrylates such as pentaerythritol tetraacrylate and di-trimethylolpropane tetraacrylate; and Mention may be made of pentaacrylates such as dipentaerythritol (monohydroxy) pentaacrylate. As the ultraviolet curable resin for the hard coat layer, a polyfunctional acrylate having 5 or more functional groups can also be used. These polyfunctional acrylates may be used alone or in combination of two or more. Further, these acrylates are used by adding one or more of third components such as photoinitiators, photosensitizers, leveling agents, fine particles composed of metal oxides and acrylic components, and ultrafine particles. be able to.

<Application>
The transparent conductive laminate of the present invention is a transparent touch panel in which two transparent electrode substrates each provided with a transparent conductive layer on at least one side are arranged so that the transparent conductive layers face each other. Alternatively, it can be used as a transparent electrode substrate for a fixed electrode substrate.

  Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to such examples. In the examples, “parts” and “%” are based on mass unless otherwise specified. Various measurements in the examples were performed as follows.

<Ra (arithmetic mean roughness)>
Measurement was performed using a stylus step meter DEKTAK3 manufactured by Sloan. The measurement was performed according to JIS B0601-1994 edition.

<Rz (10-point average roughness)>
Measurement was performed using Surfcorder SE-3400 manufactured by Kosaka Laboratory. The measurement was performed according to JIS B0601-1982 edition.

<thickness>
Measurement was carried out using a stylus-type film thickness meter Alphatech manufactured by Anritsu Electric.

<Haze>
It measured using the Nippon Denshoku Co., Ltd. haze meter (MDH2000).

<Total light transmittance>
It measured according to JISK7316-1 using the Nippon Denshoku Co., Ltd. haze meter (MDH2000).

<Anti-Newton ring property>
Under a three-wavelength fluorescent lamp, the presence or absence of a Newton ring was visually observed in a region where the movable electrode substrate and the fixed electrode substrate were in contact with each other from a direction of 60 degrees obliquely with respect to the surface of the touch panel (vertical direction 0 degree). . Good (◯) indicates that Newton's ring cannot be observed, slightly good (△) indicates that it is faintly observable, and indicates poor (×) that is clearly observable.

<Sparkling properties>
A touch panel was placed on a liquid crystal display of about 123 dpi (diagonal 10.4 inches, XGA (1024 × 768 dots)), and the presence or absence of flicker was visually confirmed. The case where flicker could not be confirmed was judged as good (◯), the case where it was faintly confirmed as slightly good (Δ), and the case where it could be clearly confirmed was judged as bad (x).

<Image clarity (transmission method)>
Measurement was performed using ICM-1T manufactured by Suga Test Instruments Co., Ltd. The measurement was based on JIS K7105 (1999 edition), and the image sharpness (%) of transmission measured with an optical comb of 0.5 mm was measured. A large value means that the distortion of the transmission image when the transparent conductive film is placed on the display is small.

[Example 1]
A polycarbonate film (C110-100, manufactured by Teijin Chemicals Ltd.) is used for the transparent organic polymer substrate, and a coating liquid R having the following composition is applied to one surface thereof with a wire bar and heated and dried at 40 ° C. for 1 minute. Irradiation with ultraviolet rays of 120 mW / cm ² and 400 mJ / cm ^{2 was performed with} an ultraviolet lamp to form a cured resin layer having an uneven surface with a thickness of about 1.5 μm. In the resulting cured resin layer, it was confirmed that the ultrafine particles formed a weak association state as shown in FIGS. 1 and 2, and a very fine uneven surface was formed due to the difference in density.

Composition of coating solution R Tetrafunctional acrylate: 100 parts by mass “Aronix” M-405 (manufactured by Toagosei Co., Ltd.)
Metal oxide ultrafine particle dispersion liquid: 80 parts by mass (in terms of solid content, 8 parts by mass, manufactured by CI Kasei Co., Ltd. SiO ₂ ultrafine particles 10 mass% isopropyl alcohol dispersion, the average primary particle diameter of ultrafine particle 30nm products)
Metal fluoride ultrafine particle dispersion: 20 parts by mass (4 parts by mass in terms of solid content, MgF ₂ ultrafine particle 20% by mass isopropyl alcohol dispersion manufactured by CI Kasei Co., Ltd., primary average particle size of ultrafine particles is 50 nm)
Photoinitiator: 5 parts by mass “Irgacure” 184 (Ciba Specialty Chemicals)
Diluent: appropriate amount (isobutyl alcohol)

  Next, on the surface on which the cured resin layer is formed, an amorphous transparent by an sputtering method using an indium oxide-tin oxide target having a mass ratio of indium oxide and tin oxide of 95: 5 and a packing density of 98% is used. A conductive layer (ITO layer) was formed. The thickness of the ITO layer was about 20 nm, and the surface resistance value was about 370Ω / □ (Ω / sq).

  Subsequently, a heat treatment was performed at 130 ° C. for 90 minutes, and the transparent conductive layer (ITO layer) was crystallized to produce a transparent conductive laminate. The surface resistance value of the transparent conductive layer after the ITO layer was crystallized was about 450Ω / □ (Ω / sq). The crystal grain size of the transparent conductive layer observed by TEM was in the range of 50 nm to 200 nm. The properties of the produced transparent conductive laminate are shown in Table 1.

  As is clear from Table 1, the touch panel using the transparent conductive laminate of this example was excellent in anti-Newton ring property, flicker resistance, and image sharpness.

  In order to confirm the dispersion of ultrafine particles, the polymer substrate with a cured resin layer having an uneven surface prepared as in Example 1 was embedded with an epoxy resin, and the epoxy resin was completely cured. After that, a thin sample was prepared using a microtome. This sample was observed with a transmission electron microscope, and it was confirmed that the ultrafine particles did not form secondary agglomerated particles having a size of 1 μm or more and formed uneven surfaces due to the difference in density (Attached FIGS. 1 and 1). 2).

[Example 2]
Example 1 except that the metal oxide ultrafine particle dispersion of Example 1 was 20 parts by mass (2 parts by mass in terms of solids) and the metal fluoride ultrafine particle dispersion was 30 parts by mass (6 parts by mass in terms of solids). In the same manner, a transparent conductive laminate was obtained. The properties of the produced transparent conductive laminate are shown in Table 1.

  As is clear from Table 1, the touch panel using the transparent conductive laminate of this example was excellent in anti-Newton ring property, flicker resistance, and image sharpness.

[Example 3]
Example 1 except that the metal oxide ultrafine particle dispersion of Example 1 was 40 parts by mass (4 parts by mass in terms of solids) and the metal fluoride ultrafine particle dispersion was 5 parts by mass (1 part by mass in terms of solids). In the same manner, a transparent conductive laminate was obtained. The properties of the produced transparent conductive laminate are shown in Table 1.

  As is clear from Table 1, the touch panel using the transparent conductive laminate of this example was excellent in anti-Newton ring property, flicker resistance, and image sharpness.

[Example 4]
Example 1 except that the metal oxide ultrafine particle dispersion of Example 1 was 120 parts by mass (12 parts by mass in terms of solids) and the metal fluoride ultrafine particle dispersion was 10 parts by mass (2 parts by mass in terms of solids). In the same manner, a transparent conductive laminate was obtained. The properties of the produced transparent conductive laminate are shown in Table 1.

  As is clear from Table 1, the touch panel using the transparent conductive laminate of this example was excellent in anti-Newton ring property, flicker resistance, and image sharpness.

[Example 5]
80 parts by mass of the metal oxide ultrafine particle dispersion of Example 1 (8 parts by mass in terms of solid content), 20 parts by mass of the metal fluoride ultrafine particle dispersion (4 parts by mass in terms of solids), and a film thickness after curing of 5 μm A transparent conductive laminate was obtained in the same manner as in Example 1 except that. The properties of the produced transparent conductive laminate are shown in Table 1.

  As is clear from Table 1, the touch panel using the transparent conductive laminate of this example was excellent in anti-Newton ring property, flicker resistance, and image sharpness.

[Example 6]
A transparent conductive laminate was obtained in the same manner as in Example 1 except that a polyethylene terephthalate film (OFW manufactured by Teijin DuPont Films Ltd.) having a thickness of 188 μm was used instead of the polycarbonate film of Example 1. The properties of the produced transparent conductive laminate are shown in Table 1.

  As is clear from Table 1, the touch panel using the transparent conductive laminate of this example was excellent in anti-Newton ring property, flicker resistance, and image sharpness.

[Comparative Example 1]
Example 1 except that the metal oxide ultrafine particle dispersion of Example 1 was changed to 10 parts by mass (1 part by mass in terms of solid content) and the metal fluoride ultrafine particle dispersion was changed to 20 parts by mass (4 parts by mass in terms of solid content). In the same manner as in Example 1, a transparent conductive laminate was obtained. The properties of the produced transparent conductive laminate are shown in Table 1.

  Table 1 shows the characteristics of the transparent conductive laminate of this comparative example. The transparent conductive laminate of this comparative example had good flicker resistance but was inferior in anti-Newton ring properties.

[Comparative Example 2]
Transparent electroconductive laminate in the same manner as in Example 1 except that the metal oxide ultrafine particle dispersion of Example 1 is 150 parts by mass (15 parts by mass in terms of solid content) and the metal fluoride ultrafine particle dispersion is not used. Got the body. The properties of the produced transparent conductive laminate are shown in Table 1.

  Table 1 shows the characteristics of the transparent conductive laminate of this comparative example. The transparent conductive laminate of this comparative example had good flicker resistance but was inferior in anti-Newton ring properties.

[Comparative Example 3]
A transparent conductive laminate was obtained in the same manner as in Example 1 except that the metal oxide ultrafine particle dispersion was not used. The properties of the produced transparent conductive laminate are shown in Table 1.

  Table 1 shows the characteristics of the transparent conductive laminate of this comparative example. The transparent conductive laminate of this comparative example had good flicker resistance but was inferior in anti-Newton ring properties.

[Comparative Example 4]
In place of the metal fluoride ultrafine particle component of Example 1, 40 parts by mass of zinc oxide nanoparticles (4 parts by mass in terms of solid content, ZnO ultrafine particles 10 mass% isopropyl alcohol dispersion manufactured by CI Kasei Co., Ltd., primary average particles of ultrafine particles A transparent conductive laminate was obtained in the same manner as in Example 1 except that a product having a diameter of 30 nm was used. The properties of the produced transparent conductive laminate are shown in Table 1.

  Table 1 shows the characteristics of the transparent conductive laminate of this comparative example. The transparent conductive laminate of this comparative example had good anti-Newton ring properties but was inferior in terms of flicker resistance.

[Comparative Example 5]
27 parts by mass of titanium oxide nanoparticles (4 parts by mass in terms of solid content, TiO ₂ ultrafine particles 15% by mass isopropyl alcohol dispersion manufactured by CI Kasei Co., Ltd., primary average particles of ultrafine particles instead of the metal fluoride ultrafine particles component of Example 1 A transparent conductive laminate was obtained in the same manner as in Example 1 except that a product having a diameter of 30 nm was used. The properties of the produced transparent conductive laminate are shown in Table 1.

  Table 1 shows the characteristics of the transparent conductive laminate of this comparative example. The transparent conductive laminate of this comparative example had good anti-Newton ring properties but was inferior in terms of flicker resistance.

[Comparative Example 6]
Example 1 except that the metal oxide ultrafine particle component of Example 1 was changed to silica particles having a primary average particle size of 3.0 μm, the metal fluoride ultrafine particle component was not used, and the film thickness was changed to 2 μm. In the same manner, a transparent conductive laminate was obtained. The properties of the produced transparent conductive laminate are shown in Table 1.

  Table 1 shows the characteristics of the transparent conductive laminate of this comparative example. The transparent conductive laminate of this comparative example had good anti-Newton ring properties, but when placed on a high-resolution liquid crystal display, color separation occurred in the pixels and the flicker resistance was poor.

It is the cross-sectional photograph which image | photographed with the transmission electron microscope after embedding with the cured resin the polymeric substrate with a cured resin layer which has the uneven | corrugated surface formed in Example 1, and making it a thin piece sample with a microtome. 2 is a cross-sectional photograph obtained by further enlarging the cured resin layer having an uneven surface containing the ultrafine particles of FIG. It is a figure which shows the example of the transparent touch panel which has the transparent conductive laminated body of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Embedded resin 2 The cured resin layer which has the uneven | corrugated surface containing ultrafine particles 3 Transparent organic polymer substrate 11 Substrate (glass plate)
12, 14 Transparent conductive layer 13 Spacer 15 Cured resin layer having uneven surface 16 Transparent organic polymer substrate 20 Transparent touch panel

Claims (8)

A transparent conductive laminate in which a cured resin layer having a concavo-convex surface and a transparent conductive layer are sequentially laminated on at least one surface of a transparent organic polymer substrate,
(1) The cured resin layer is a cured resin component, and at least one metal oxide ultrafine particle A having an average primary particle size of 100 nm or less and at least one average primary particle size dispersed in the cured resin component. Having metal fluoride ultrafine particles B of 100 nm or less,
(2) The content of the metal oxide ultrafine particles A in the cured resin layer is 1 part by mass or more and less than 20 parts by mass per 100 parts by mass of the cured resin component,
(3) The content of the metal fluoride ultrafine particles B in the cured resin layer is 1 part by mass or more and less than 20 parts by mass per 100 parts by mass of the cured resin component,
(4) The mass ratio (A / B) of the metal oxide ultrafine particles A to the metal fluoride ultrafine particles B in the cured resin layer is greater than 0.3, and (5) the metal oxide ultrafine particles A are SiO. ₂ and the metal fluoride ultrafine particle B is MgF ₂ .
Transparent conductive laminate.   The ten-point average roughness (Rz) of the cured resin layer is 300 nm or more and less than 1500 nm, and the arithmetic average roughness (Ra) of the cured resin layer is 50 nm or more and less than 300 nm, Item 2. The transparent conductive laminate according to Item 1.   The transparent conductive laminated body of Claim 1 or 2 whose thickness of the said cured resin layer is 0.1-4.5 micrometers.   The transparent conductive laminate according to claim 1, wherein a haze based on the transparent organic polymer substrate and the cured resin layer is 1% or more and less than 10%.   The transparent conductive laminate according to claim 1, wherein the transparent conductive layer is a crystalline layer containing indium oxide as a main component, and the thickness of the transparent conductive layer is 5 to 50 nm.   The metal compound layer which is in contact with the transparent conductive layer and whose film thickness is thinner than the transparent conductive layer and is less than or equal to 0.5 nm and less than 5.0 nm is provided between the cured resin layer and the transparent conductive layer. The transparent conductive laminate according to any one of 5. The transparent conductive laminate according to claim 6 , wherein the metal of the metal compound layer is the same as the metal of the metal oxide ultrafine particles A and / or metal fluoride ultrafine particles B.   The transparent touch panel in which two transparent electrode substrates each having a transparent conductive layer provided on at least one side are arranged so that the transparent conductive layers face each other are used as at least one transparent electrode substrate. A transparent touch panel using the transparent conductive laminate according to any one of the above.