JP2006190510A - Transparent conductive laminate and transparent touch panel using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To prevent degradation of visibility due to flicker and prevent Newton rings generated between two transparent electrode substrates constituting a transparent touch panel, even if the touch panel is installed on a high-definition display. <P>SOLUTION: The transparent conductive laminate is made by arranging a cured resin layer with ruggednesses on at least one face of a transparent polymer substrate and providing a transparent conductive layer on the cured resin layer directly or through another layer. The cured resin layer contains fine particles A with an average primary particle size of 0.5 to 5 μm, and ultrafine particles C consisting of metal oxide and/or metal fluoride with an average primary particle size of 100 nm or less. The transparent conductive laminate has an image definition of 75% or more and 95% or less as measured by a transmission method in the case of use of an optical comb of 2.0 mm. <P>COPYRIGHT: (C)2006,JPO&NCIPI

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.

  As a method of reducing Newton's ring generated between two transparent electrode substrates constituting such a resistive film type transparent touch panel, a coating layer and a transparent conductive layer containing a predetermined amount of filler having an average primary particle diameter of 1 to 4 μm Is formed on a plastic film (see Patent Document 1). Further, a method of forming a protrusion coating layer (a coating layer having protrusions) containing silica particles having an average secondary particle diameter of 1.0 to 3.0 μm on a plastic film is disclosed (Patent Document 2). reference).

  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 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 recent high-definition display, the resin around the particles in the coating layer exerts a lens effect, thereby causing color separation (flickering) of light coming from the display, There has been a problem that the visibility is remarkably deteriorated.

  In addition, as a coating layer for reducing Newton rings other than the above, a Newton ring prevention layer (anti-Newton rings layer) using a resin comprising two or more kinds of matting agents and binders having different average particle diameters. (See Patent Document 3).

  The Newton ring prevention layer formed by such a method can suppress flickering on a high-definition display, but the average particle diameter of 1 to 15 μm is different from that of 5 to 50 nm. Is also added for the purpose of matting. Originally, since the fine particles of 5 to 50 nm are significantly lower than the optical order of visible light, no haze is generated even when particles of this size are added to the resin serving as the binder, but the examples and comparative examples described in Patent Document 3 In comparison, since the haze is increased by adding fine particles of 5 to 50 nm, it is presumed that the particles form secondary aggregates. It can be seen that flicker is controlled by the increase in haze, that is, matting. In the Newton ring prevention layer formed by such a method, since haze becomes extremely high, there is a problem of deteriorating the visibility of the display.

Furthermore, a resin layer having dot-like projections with an average density of 100 to 5000 / mm ² is provided on a transparent plastic film, and an optical comb having a transmitted image definition of 0.125 mm is provided on the transparent conductive film. By using a transparent conductive film of 70% or more when used, there are no sticking (adhesion between electrodes), excellent sliding writing characteristics, high light transmittance, and no character blurring. Although there is a transparent conductive film that suppresses glare while maintaining the above (see Patent Document 4), the effect of suppressing the occurrence of Newton rings is not achieved in this invention.

Japanese Patent Laid-Open No. 10-323931 JP 2002-373056 A JP 2001-84839 A Japanese Patent Laid-Open No. 11-291382

  As a result of earnestly examining the problems with respect to the present situation, the present inventors have found that the transparent conductive laminate has irregularities such that the image sharpness when using an optical comb of 2.0 mm is 75% or more and 95% or less. It was found that it is necessary to form, but as an optimal method for forming such irregularities, the cured resin containing fine particles A having an average primary particle size of 0.5 μm or more and 5 μm or less has an average primary particle size of By adding ultrafine particles C of 100 nm or less, we found a method of creating a cured resin layer that can control the uneven shape, and succeeded in simultaneously reducing the generation of Newton rings and reducing the deterioration of visibility due to the occurrence of flickering. .

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 that maintains the visibility and has a low haze.
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-mentioned problems, the present inventors have added a metal oxide having an average primary particle size of 100 nm or less to a mixture of at least one kind of fine primary particles A and a curable resin having an average primary particle size of 0.5 μm to 5 μm. Or, by adding ultrafine particles C made of fluoride, it has been surprisingly found that the leveling state of the curable resin layer is changed, and the uneven shape on the surface of the curable resin layer can be freely controlled. The present invention has been completed. That is, the present invention is as follows.

1st invention is the transparent conductive laminated body by which the cured resin layer-1 which forms an uneven | corrugated shape, and the transparent conductive layer were laminated | stacked in order on the at least one surface of the transparent organic polymer board | substrate, JIS K7105 ( 1999), a transparent conductive laminate having an image clarity of 75% or more and 95% or less when a 2.0 mm optical comb is used, and the cured resin layer 1 is a transparent conductive laminate that simultaneously satisfies the following requirements (A) to (E).
(A) The cured resin layer-1 includes (i) a cured resin component, (ii) at least one fine particle A having an average primary particle size of 0.5 to 5 μm, and (iii) a metal oxide and a metal fluoride. It has at least one selected from the group consisting of ultrafine particles C having an average primary particle size of 100 nm or less.
(B) The content of the fine particles A in the cured resin layer-1 is 0.3 part by weight or more and less than 1.0 part by weight per 100 parts by weight of the cured resin component (i).
(C) The content of the ultrafine particles C in the cured resin layer-1 is 1 to 20 parts by weight per 100 parts by weight of the cured resin component (i).
(D) The thickness of the cured resin layer-1 is 0.5 to 4.5 μm.
(E) The haze defined by JIS K7136 based on the transparent polymer substrate and the cured resin layer-1 is 1% or more and less than 6%.

  2nd invention is the transparent touch panel comprised by arrange | positioning so that two transparent electrode layers with which the transparent conductive layer was formed in at least one surface might face each other, Comprising: At least one transparent electrode substrate Is a transparent touch panel characterized by being the transparent conductive laminate of the present invention.

  According to the present invention, as described above, the cured resin layer having the unevenness constituting the transparent conductive laminate has a predetermined ratio of the curable resin component and two kinds of fine particles having a specific particle diameter different from the curable resin component. In addition to preventing display degradation due to flickering and preventing Newton rings from occurring between the two transparent electrode substrates that constitute the transparent touch panel, the haze value is low and transparent. Transparent conductive laminate and a transparent touch panel using the same can be obtained.

Hereinafter, preferred embodiments of the present invention will be described.
In the transparent conductive laminate of the present invention, it is necessary to form a concavo-convex surface on which at least one surface has an image definition of 75% to 95% when a 2.0 mm optical comb is applied. The method for forming the surface may be any method.

  For example, the surface of the transparent polymer substrate can be realized by embossing, sandblasting, imprinting, a method of curing with an electron beam after transferring a mold, or coating of a cured resin layer mixed with fine particles. Image sharpness is an important characteristic for suppressing flickering, but flickering is less likely to occur as the image sharpness is higher.

  On the other hand, an object of the present invention is not only to prevent flicker but also to prevent Newton's ring (anti-Newton ring) at the same time. The anti-Newton ring property is easier to obtain when the image definition is lower.

  As a result of intensive studies on the contradictory properties of anti-flickering and anti-Newton ring properties, the present inventors have used a 2.0 mm optical comb as defined in JIS K7105 (1999 edition), and image clarity measured by transmission. It was concluded that it is optimal that the degree (hereinafter simply referred to as image definition) is 75% or more and 95% or less.

  This means that when the image definition is less than 75%, a substrate excellent in anti-Newton ring property can be formed, but a film that easily causes display flickering can be formed. On the other hand, when the image definition exceeds 95%, it means that a film having a poor anti-Newton ring property can be formed although it is difficult for the display to flicker. When the image definition is 75% or more and 95% or less, a substrate that can simultaneously satisfy the anti-flickering property and the anti-Newton ring property can be obtained, but 70% or more and 90% or less are preferable, and 75% or more and 85% or less. It is more preferable.

  In particular, in the present invention, as a method for forming irregularities such that the image definition is 75% or more and 95% or less, a curable resin component and at least one fine particle A having an average primary particle size of 0.5 to 5 μm are used. Further, this can be easily achieved by laminating the cured resin layer-1 composed of ultrafine particles C made of a metal oxide or metal fluoride having an average primary particle diameter of 100 nm or less on a transparent polymer substrate. Examples of the curable resin component include ionizing radiation curable resins and thermosetting resins.

  The ionizing radiation curable resin can be obtained by polymerizing a monofunctional or polyfunctional acrylate such as polyol acrylate, polyester acrylate, urethane acrylate, epoxy acrylate, modified styrene acrylate, melamine acrylate, or silicon-containing acrylate.

  Preferred specific monomers include, for example, trimethylolpropane trimethacrylate, trimethylolpropane ethylene oxide modified triacrylate, trimethylolpropane propylene oxide modified triacrylate, isocyanuric acid ethylene oxide modified triacrylate, pentaerythritol triacrylate, dipentaerythritol hexa Examples include polyfunctional monomers such as acrylate, dimethylol tricyclodecane diacrylate, tripropylene glycol triacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, epoxy-modified acrylate, and urethane-modified acrylate. These may be used alone or as a mixture of several kinds. In some cases, an appropriate amount of various alkoxysilane hydrolysates may be added to the acrylate as described above. For polymerization by ionizing radiation, it is preferable to add an appropriate amount of a known photopolymerization initiator, and an appropriate amount of a photosensitizer may be added if necessary.

  Examples of the photopolymerization initiator include acetophenone, benzophenone, benzoin, benzoylbenzoate, and thioxanthone. Examples of the photosensitizer include triethylamine and tri-n-butylphosphine.

  In addition, as the thermosetting resin, for example, an organosilane-based thermosetting resin obtained by polymerizing a silane compound such as methyltriethoxysilane or phenyltriethoxysilane as a monomer, an etherified methylol melamine, or the like is used as a monomer. Examples thereof include melamine-based thermosetting resins, isocyanate-based thermosetting resins, phenol-based thermosetting resins, and epoxy-based thermosetting resins. These thermosetting resins can be used alone or in combination. For polymerization or crosslinking by heat, it is preferable to add an appropriate amount of a known reaction accelerator or curing agent.

  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.

  Even if only the above-mentioned curable resin component is used as the resin component, the cured resin layer-1 can ensure sufficiently good adhesion with the transparent conductive layer, but more firmly secure the adhesion with the transparent conductive layer. The cured resin layer-1 can contain a thermoplastic resin. Examples of such thermoplastic resins include cellulose derivatives such as acetylcellulose, nitrocellulose, acetylbutylcellulose, ethylcellulose and methylcellulose, vinyl acetate homopolymers and copolymers thereof, vinyl chloride homopolymers and copolymers thereof. Polymers, vinyl resins such as vinylidene chloride homopolymers and copolymers thereof, acetal resins such as polyvinyl formal and polyvinyl butyral, acrylic resins such as acrylic resins (including copolymers) and methacrylic resins (including) Resins, polystyrene resins, polyamide resins, polycarbonate resins and the like can be mentioned.

The fine particles A used in the present invention can be used without particular limitation as long as the average primary particle diameter is 0.5 to 5 μm. For example, SiO ₂ , fine particles containing SiO ₂ as a main component or a crosslinking component, and fine particles containing a styrene-based, acrylic-based, or butadiene-based polymer as main components can be given. Fine particles subjected to a treatment such as surface modification may be used. Also, two or more kinds of such fine particles A can be mixed and used. For example, as the fine particles A, fine particles having different average primary particle sizes can be mixed to have a wide particle size distribution. The content of the fine particles A is 0.3 part by weight or more and less than 1.0 part by weight, preferably 0.3 part by weight to 0.9 part by weight, based on 100 parts by weight of the curable resin component. More preferably, it is from 3 to 0.8 parts by weight. When the content is less than 0.3 parts by weight, the haze can be lowered, so that the visibility of the transparent touch panel is improved, but the function of preventing Newton rings is poor. On the other hand, if it is 1.0 part by weight or more, the Newton ring prevention function is excellent, but since haze is increased, when a transparent touch panel is installed on the display, information such as video and characters on the display is blurred.

As the ultrafine particles C having an average primary particle diameter of 100 nm or less, a metal oxide or a metal fluoride is used. Specific examples thereof include, for example, Al ₂ O ₃ , Bi ₂ O ₃ , CeO ₂ , In ₂ O ₃ , (In ₂ O ₃ .SnO ₂ ), HfO ₂ , La ₂ O ₃ , MgF ₂ , Sb _2. Examples include O ₅ , (Sb ₂ O ₅ .SnO ₂ ), SiO ₂ , SnO ₂ , TiO ₂ , Y ₂ O ₃ , ZnO, and ZrO ₂ . These may be used alone or in combination of two or more. Of course, metal oxides and metal fluorides can be used together. In addition, regarding the refractive index of the ultrafine particles C, when the refractive index of the ultrafine particles C is larger than the refractive index of the curable resin component, the resulting cured resin layer-1 tends to have a high haze. The lower the refractive index, the better the choice of curable resin component.

Preferred examples of such ultrafine particles C include SiO ₂ and MgF ₂ . Since these ultrafine particles C have a very large specific surface area and generally easily aggregate, they are often available as a slurry in which a dispersant is added and dispersed in a solvent. As such a dispersant, for example, various types such as fatty acid amine, sulfonic acid amide, ε-caprolactone, hydrostearic acid, polycarboxylic acid, and polyesteramine can be used. Moreover, as a dispersion medium (solvent), the general thing represented by alcohol type | system | group, water, a ketone type | system | group, an aromatic type etc. can be used.

  Here, one of the important points forming the basis of the present invention is that the ultrafine particles C level the cured resin layer. For this purpose, the ultrafine particles C are dispersed so as not to cause secondary aggregation. It is necessary to be. Although the ultrafine particles C can form an aggregate depending on the production conditions and the like, such fine particles are not suitable as the ultrafine particles C. The ultrafine particles C are preferably dispersed and do not form a secondary aggregate having a major axis of 1 μm or more. Such a state can be confirmed by observing with the same method as the measurement method of the average primary particle diameter using the below-mentioned transmission electron microscope.

  The average primary particle diameter of the ultrafine particles C needs to be 100 nm or less so that the cured resin layer does not whiten due to the generation of internal haze. The average primary particle diameter of the ultrafine particles C is preferably 80 nm or less, more preferably 60 nm or less. The lower limit is not particularly limited, but is preferably 5 nm. The average primary particle diameter of the ultrafine particles C can be measured using a laser diffraction / scattering particle size distribution analyzer. In order to easily measure the particle size, the actual size can be measured by using a transmission electron microscope or the like. Specifically, a cured resin layer containing ultrafine particles C is embedded with an epoxy resin, etc., and the epoxy resin layer is completely cured and then sliced with a microtome to prepare a measurement sample. Observe with a microscope. The average primary particle size can be obtained by measuring the size of the ultrafine particles C at random at 10 points or more and averaging the measured values.

  The content of the ultrafine particles C dispersed in the cured resin layer-1 is 1 to 20 parts by weight, preferably 2 to 10 parts by weight, based on 100 parts by weight of the curable resin component. Preferably it is 3-7 weight part. When the amount of the ultrafine particle C component is less than 1 part by weight, the effect of leveling the cured resin layer-1 is insufficient, so that the surface roughness is large and the image sharpness is 75% or less. -1 is not preferable because flickering occurs. On the other hand, when the amount exceeds 20 parts by weight, the leveling of the cured resin layer-1 becomes excessive, so that the surface roughness becomes small and the image definition exceeds 95%. Therefore, the Newton ring of the transparent electrode substrate used for the transparent touch panel It is not suitable as a prevention layer.

  It is very important to control the thickness of the cured resin layer-1 in order to form the cured resin layer-1 that has no flickering and has a Newton ring prevention function. Moreover, in order to form unevenness in the cured resin layer-1, it is desirable that the thickness of the cured resin layer-1 be smaller than the average primary particle diameter of the fine particles A to be contained. The thickness of the cured resin layer-1 having irregularities is 0.5 to 4.5 μm, preferably 1.0 to 4.0 μm, and more preferably 1.5 to 3.0 μm. When the thickness is less than 0.5 μm, the mechanical strength of the Newton ring prevention layer becomes weak, which is not suitable for use as a transparent electrode substrate for a transparent touch panel. When the thickness exceeds 4.5 μm, fine particles having an average primary particle diameter larger than 5 μm must be used to form irregularities on the surface of the cured resin layer-1, so that the cured resin layer is formed by the large fine particles. The haze of -1 is increased and the visibility of the display is deteriorated.

  The ten-point average roughness (Rz) defined in accordance with JIS B0601-1982 of the cured resin layer-1 is preferably 100 nm or more and less than 1000 nm, more preferably 100 nm or more and less than 800 nm, and further preferably 150 nm or more. It is less than 500 nm. When the ten-point average roughness (Rz) is less than 100 nm, Newton rings may easily occur between the movable electrode substrate and the fixed electrode substrate of the transparent touch panel, and the ten-point average roughness (Rz) is 1000 nm or more. In such a case, it is not preferable to install a transparent touch panel on a high-definition display because haze increases and pixel color separation occurs and flickering occurs.

  The arithmetic average roughness (Ra) defined in accordance with JIS B0601-1994 of the cured resin layer-1 is preferably 50 nm or more and less than 500 nm, more preferably 50 nm or more and less than 400 nm, and further preferably 50 nm. It is more than 300 nm and particularly preferably 60 nm or more and less than 200 nm. When the arithmetic average roughness (Ra) is less than 50 nm, Newton rings may easily occur between the movable electrode substrate and the fixed electrode substrate of the transparent touch panel.

  The haze defined by JIS K7136 based on the cured resin layer-1 having irregularities and the transparent polymer substrate is 1% or more and less than 6%, preferably 1% or more and less than 5%, more preferably 1% or more. Less than 3%. When the haze is less than 1%, Newton's rings may easily occur between the movable electrode substrate and the fixed electrode substrate of the transparent touch panel, which is not preferable. On the other hand, when the haze is 6% or more, information such as images and characters is blurred when the transparent touch panel is installed on the display.

  As a method for forming the cured resin layer-1 having irregularities in the present invention, the formation by a coating method is particularly suitable. In this case, for example, any known coating method such as a doctor knife, a bar coater, a gravure roll coater, a curtain coater, a knife coater, a spin coater, a spray method, or a dipping method can be used.

  Specifically, for example, a dispersion of fine particles A, a dispersion of ultrafine particles C, and a reaction initiator are added to a monomer (solution) or oligomer (solution) of a curable resin, and viscosity adjustment is performed as necessary. Add solvent and mix well. Next, this solution composition is applied to the surface of the transparent polymer substrate using the above method, and the resin is reacted and cured by irradiation with heat or light to form a cured resin layer.

  As the transparent polymer substrate used in the present invention, a thermoplastic or thermosetting polymer film preferably having excellent transparency can be used. Such a polymer is not particularly limited as long as it is a transparent polymer excellent in heat resistance. For example, polyester resins such as polyethylene terephthalate, polyethylene-2,6-naphthalate, polydiallyl phthalate, polycarbonate resin, polyether sulfone resin, polysulfone resin, polyarylate resin, acrylic resin, cellulose acetate resin, amorphous polyolefin, etc. Can be mentioned. Of course they can be used as homopolymers, copolymers, or alone or as a blend. These transparent polymer substrates are suitably formed by a general melt extrusion method or a solution casting method, etc., and the transparent polymer film formed is subjected to uniaxial stretching or biaxial stretching as necessary, It is also preferable to increase the optical strength and the optical function.

  When the transparent conductive laminate of the present invention is used as a movable electrode substrate of a transparent touch panel, the thickness of the substrate shape from the point of strength for maintaining flexibility and flatness for operating the transparent touch panel as a switch. A film shape of 75 to 400 μm is preferable.

  When the transparent conductive laminate of the present invention is used as a movable electrode substrate for a transparent touch panel, the fixed electrode substrate is a polymer film substrate, a glass substrate, or a laminate in which a transparent conductive layer is formed on the laminate substrate. Can be used. From the viewpoint of the strength and weight of the transparent touch panel, the thickness of the fixed electrode substrate made of a single layer or a laminate is preferably 0.4 to 4.0 mm.

  When the transparent conductive laminate of the present invention is used as a fixed electrode substrate for a transparent touch panel, a sheet having a thickness of 0.4 to 4.0 mm is preferable from the viewpoint of strength to maintain flatness, but a thickness of 50 A film-like film having a thickness of ˜400 μm may be bonded to another sheet, and the total thickness may be 0.4 to 4.0 mm. Alternatively, a film having a thickness of 50 to 400 μm can be attached to the display surface for use.

  Recently, a new type of transparent touch panel having a configuration in which a polarizing plate or a polarizing plate and a retardation film are laminated on the input side (user side) of the transparent touch panel has been developed. The advantage of this configuration is that the contrast of the display with the transparent touch panel installed is reduced mainly by the optical action of the polarizing plate or the polarizing plate and the retardation film to reduce the reflectance of external light inside the transparent touch panel to less than half. Is to improve.

  In such a type of transparent touch panel, since the polarized light passes through the transparent conductive laminate, it is preferable to use a transparent polymer film having excellent optical isotropy characteristics. A surface represented by Re = (nx−ny) · d (nm) where the refractive index in the slow axis direction is nx, the refractive index in the fast axis direction is ny, and the thickness of the substrate is d (nm). The internal retardation value Re is preferably at least 30 nm or less, more preferably 20 nm or less, further preferably 10 nm or less, and even more preferably 5 nm or less. Ideally, it is preferably 0 nm. Here, the in-plane retardation value of the substrate is represented by a value at a wavelength of 590 nm measured using a spectroscopic ellipsometer (M-150 manufactured by JASCO Corporation).

  Thus, in the application of the transparent touch panel in which polarized light passes through the illustrated transparent conductive laminate, the in-plane retardation value of the transparent electrode substrate becomes very important. It is preferable that the K value represented by K = {(nx + ny) / 2−nz} · d is −250 to +150 nm, where nz is the three-dimensional refractive index characteristic, ie, the refractive index in the thickness direction of the substrate, It is more preferably −200 to +130 nm, further preferably −100 nm to +100 nm, and even more preferably −50 nm to +50 nm in order to obtain excellent viewing angle characteristics of the transparent touch panel. Ideally, it is preferably 0 nm.

  Examples of the transparent polymer substrate exhibiting excellent optical isotropy characteristics include polycarbonate, amorphous polyarylate, polyether sulfone, polysulfone, triacetyl cellulose, diacetyl cellulose, cycloolefin polymer, and modified products thereof. Alternatively, a molded substrate in which a copolymer with another kind of material is molded into a film, a molded substrate of a thermosetting resin such as an epoxy resin, or a molded substrate in which an ultraviolet curable resin such as an acrylic resin is molded into a film or sheet Is particularly preferred. From the viewpoints of moldability, production cost, thermal stability, etc., among others, polycarbonate, amorphous polyarylate, polyether sulfone, polysulfone, cycloolefin polymer and copolymers with these modified or different materials, etc. A molded substrate is most preferred.

  More specifically, examples of the polycarbonate include bisphenol A, 1,1-di (4-phenol) cyclohexylidene, 3,3,5-trimethyl-1,1-di (4-phenol) cyclohexylidene, Polymer or copolymer having at least one component selected from the group consisting of fluorene-9,9-di (4-phenol) and fluorene-9,9-di (3-methyl-4-phenol) as a monomer unit Or a mixture of these. Among these polycarbonates, in particular, a molded substrate of a polycarbonate having an average molecular weight in the range of about 15,000 to 100,000 (eg, “Panlite” manufactured by Teijin Chemicals Ltd., “Apec HT” manufactured by Bayer Co., Ltd.), etc. Is preferably used.

Amorphous polyarylate can be obtained as a molded substrate such as “Elmec” manufactured by Kaneka Corporation (former Kaneka Chemical Co., Ltd.), “U Polymer” manufactured by Unitika Co., Ltd., “Isaril” manufactured by Isonova.
The cycloolefin polymer can be obtained as a molding substrate such as “ZEONOR” manufactured by Nippon Zeon Co., Ltd. or “ARTON” manufactured by JSR Corporation.

  Examples of the method for producing a molded substrate using these polymer compounds include a melt extrusion method, a solution casting method, and an injection molding method. From the viewpoint of obtaining excellent optical isotropy, a melt extrusion method and a solution casting method are preferable.

  In the present invention, a transparent conductive layer is provided directly or via a cured resin layer-2 or an optical interference layer on the uneven cured resin layer-1. By providing the transparent conductive layer via the cured resin layer-2, mechanical properties such as writing durability of the transparent conductive laminate can be improved. Examples of the transparent conductive layer include an ITO layer containing 2 to 20% by weight of tin oxide and a tin oxide layer doped with antimony or fluorine. Examples of the method for forming the transparent conductive layer include a PVD (Physical Vapor Deposition) method such as a sputtering method, a vacuum deposition method, and an ion plating method, a coating method, a printing method, and a CVD (Chemical Vapor Deposition) method. Of these, the PVD method or the CVD method is preferable.

  In the case of the PVD method or the CVD method, the thickness of the transparent conductive layer is preferably 5 to 50 nm, more preferably 10 to 30 nm from the viewpoint of transparency and conductivity. If the 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 transmittance of the transparent conductive laminate decreases, which is not preferable. The surface resistance value is preferably 100 to 2000 Ω / □ (Ω / sq), more preferably 140 to 2000 Ω / □ (Ω) at a thickness of 10 to 30 nm due to reduction of power consumption and circuit processing of the transparent touch panel. It is preferable to use a transparent conductive layer exhibiting a range of / sq).

  Further, the transparent conductive layer is preferably a crystalline film mainly composed of indium oxide, and a layer made of crystalline ITO is particularly preferably used. The crystal grain size 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).

  In the present invention, “based on indium oxide” means indium oxide containing tin, tellurium, cadmium, molybdenum, tungsten, fluorine, zinc or the like as a dopant, or in addition to tin as a dopant, silicon, titanium, It means indium oxide containing zinc or the like.

  The “crystalline film” means that 50% or more, preferably 75% or more, more preferably 95% or more, and particularly preferably almost 100% of the layer made of indium oxide containing a dopant is occupied by the crystalline phase. Means that

  In the present invention, the cured resin layer-2 may be provided between the cured resin layer-1 having irregularities and the transparent conductive layer as described above in order to improve optical characteristics such as total light transmittance. The cured resin layer-2 can be formed using the same method as the cured resin layer-1.

  Examples of the resin used for forming the cured resin layer-2 include an ionizing radiation curable resin and a thermosetting resin. Examples of the ionizing radiation curable resin include monofunctional and polyfunctional acrylate ionizing radiation curable resins such as polyol acrylate, polyester acrylate, urethane acrylate, epoxy acrylate, modified styrene acrylate, melamine acrylate, and silicon-containing acrylate.

  Examples of the thermosetting resin include organosilane thermosetting resins (alkoxysilane) such as methyltriethoxysilane and phenyltriethoxysilane, melamine thermosetting resins such as etherified methylol melamine, and isocyanate thermosetting resins. Examples thereof include resins, phenolic thermosetting resins, and epoxy thermosetting resins. These thermosetting resins can be used alone or in combination. Moreover, it is also possible to mix a thermoplastic resin as needed. When the resin layer is crosslinked by heat, an appropriate amount of a known reaction accelerator and curing agent is added. 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.

  About the said alkoxysilane, the cured resin layer-2 is formed by hydrolyzing and condensation-polymerizing this. Examples of the alkoxysilane include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and β- (3,4 epoxy cyclohexyl) ethyl. Examples include trimethoxysilane, vinyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyldimethoxysilane, and γ-aminopropyltriethoxysilane.

  These alkoxysilanes are preferably used in a mixture of two or more from the viewpoints of the mechanical strength, adhesion and solvent resistance of the layer, and in particular from the viewpoint of solvent resistance, It is preferable that the alkoxysilane which has an amino group in a molecule | numerator is contained in the range of 0.5-40% of a ratio.

  Alkoxysilane may be used as a monomer or may be used after being hydrolyzed and dehydrated and condensed into a suitable oligomer. Usually, a coating solution dissolved and diluted in an appropriate organic solvent is applied onto a substrate. . The coating film formed on the substrate is hydrolyzed by moisture in the air and the like, and subsequently cross-linked by dehydration condensation.

  In general, an appropriate heat treatment is required to promote crosslinking, and it is preferable to perform a heat treatment for several minutes or more at a temperature of 100 ° C. or higher in the coating process. In some cases, the degree of crosslinking can be further increased by irradiating the coating film with actinic rays such as ultraviolet rays in parallel with the heat treatment.

  As the diluting solvent, for example, an alcohol solvent or a hydrocarbon solvent is used. Examples thereof include ethanol, isopropyl alcohol, butanol, 1-methoxy-2-propanol, hexane, cyclohexane, ligroin and the like. In addition, polar solvents such as xylene, toluene, cyclohexanone, methyl isobutyl ketone, and isobutyl acetate can also be used. These solvents can be used alone or as a mixed solvent of two or more.

  In order to adjust the refractive index of the cured resin layer-2, the cured resin layer is composed of ultrafine particles C or fluorine-based resins made of metal oxide or metal fluoride having an average primary particle diameter of 100 nm or less, alone or in combination. -2 can be contained. The refractive index of the cured resin layer-2 is preferably smaller than the refractive index of the cured resin layer-1 and is 1.20 to 1.55, more preferably 1.20 to 1.45. The thickness of the cured resin layer-2 is preferably 0.05 to 0.5 μm, more preferably 0.05 to 0.3 μm.

  The average primary particle diameter of the ultrafine particles C is preferably 100 nm or less, more preferably 50 nm or less. By controlling the primary particle diameter of the ultrafine particles C to 100 nm or less, it is possible to form a good cured resin layer-2 without whitening.

Examples of the ultrafine particles C include Bi ₂ O ₃ , CeO ₂ , In ₂ O ₃ , (In ₂ O ₃ .SnO ₂ ), HfO ₂ , La ₂ O ₃ , MgF ₂ , Sb ₂ O ₅ , (Sb ₂ O ₅ · SnO ₂ ), SiO ₂ , SnO ₂ , TiO ₂ , Y ₂ O ₃ , ZnO, ZrO _{2 and the} like. Of these, ultrafine particles of metal oxide or metal fluoride having a refractive index of 1.55 or less such as MgF ₂ and SiO ₂ are preferable.

  The content of the ultrafine particles C is preferably 10 to 400 parts by weight, more preferably 30 to 400 parts by weight, still more preferably 50 to 300 parts by weight with respect to 100 parts by weight of the thermosetting resin and / or ionizing radiation curable resin. Part. When the content of ultrafine particles C is more than 400 parts by weight, the layer strength and adhesion may be insufficient. On the other hand, when the content of ultrafine particles C is less than 10 parts by weight, a predetermined refractive index is obtained. It may disappear.

  Examples of the fluorine resin include vinylidene fluoride, hexafluoropropylene, tetrafluoroethylene, fluoroethylene, trifluoroethylene, chlorotrifluoroethylene, 1,2-dichloro-1,2-difluoroethylene, 2-bromo-3, 3,3-trifluoroethylene, 3-bromo-3,3-difluoropropylene, 3,3,3-trifluoropropylene, 1,1,2-trichloro-3,3,3-trifluoropropylene, α-tripropylene A polymer containing 5 to 70% by weight of a polymerization component of a monomer having a fluorine atom such as fluoromethacrylic acid may be mentioned.

  The content of the fluororesin is preferably 50 to 300 parts by weight, more preferably 100 to 300 parts by weight, and still more preferably 150 to 250 parts by weight with respect to 100 parts by weight of the thermosetting resin and / or ionizing radiation curable resin. Parts by weight. When the content of the fluororesin is more than 300 parts by weight, the layer strength and adhesion may be insufficient. On the other hand, when the content of the fluororesin is less than 50 parts by weight, a predetermined refractive index may not be obtained. is there.

In the present invention, an optical interference layer can be provided between the cured resin layer-1 having irregularities and the transparent conductive layer as described above in order to control the refractive index and enhance the transparency.
The optical interference layer used in the present invention is preferably 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 300 nm, and more preferably 50 nm to 200 nm.

Examples of the high refractive index layer constituting the optical interference layer of the present invention include a layer formed mainly by hydrolysis and condensation polymerization of a metal alkoxide.
Examples of the metal alkoxide include titanium alkoxide and zirconium alkoxide.

Examples of the titanium alkoxide include titanium tetraisopropoxide, tetra-n-propyl orthotitanate, titanium tetra-n-butoxide, tetrakis (2-ethylhexyloxy) titanate, and the like.
Examples of the zirconium alkoxide include zirconium tetraisopropoxide and zirconium tetra-n-butoxide.

In the case where the refractive index is adjusted by adding metal oxide ultrafine particles C described later, it is also possible to use alkoxysilane as the metal alkoxide.
In the high refractive index layer, ultrafine particles C having an average primary particle diameter of 100 nm or less, which are made of the metal oxides or metal fluorides described above, can be added singly or in appropriate amounts. By adding ultrafine particles C, it is possible to adjust the refractive index of the high refractive index layer.

When the ultrafine particles C are added to the high refractive index layer, the weight ratio of the ultrafine particles C to the metal alkoxide is preferably 0: 100 to 60:40, more preferably 0: 100 to 40:60. is there. When the weight ratio between the ultrafine particles C and the metal alkoxide exceeds 60:40, the strength and adhesion necessary for the optical interference layer may be insufficient, which is not preferable.
The thickness of the high refractive index layer is preferably 15 to 250 nm, more preferably 30 to 150 nm.
Further, the refractive index of the high refractive index layer is larger than those of the low refractive index layer and the cured resin layer-2 described later, and the difference is preferably 0.2 or more.

  As the low refractive index layer constituting the optical interference layer of the present invention, the same layer as the cured resin layer-2 can be used. The thickness of the low refractive index layer is preferably 15 to 250 nm, more preferably 30 to 150 nm.

  In the present invention, a metal compound layer can be provided between the cured resin layer-2 and the transparent conductive layer in contact with the transparent conductive layer. The film thickness of the metal compound layer is smaller than the film thickness of the transparent conductive layer and is 0.5 nm or more and less than 10.0 nm, preferably 1.0 nm or more and less than 7.0 nm, more preferably 1.0 nm or more and 5.0 nm. Is less than. Adhesiveness is greatly improved by sequentially laminating the cured resin layer-2, metal compound layer with controlled film thickness, and transparent conductive layer, and the writing durability and endurance durability required for transparent touch panels in recent years have been improved. To do. When the thickness of the metal compound layer is 10.0 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 sufficiently express the adhesiveness with the cured resin layer-2 and the transparent conductive layer, thereby improving the endurance durability. Becomes difficult.

Examples of the metal compound layer include layers of metal oxides 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, a DC magnetron sputtering method, an RF magnetron sputtering method, an ion plating method, a vacuum deposition method, a pulse laser deposition method, or a combination thereof. Although physical forming methods (Physical Vapor Deposition, hereinafter referred to as PVD) can be used, 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 Chemical Vapor Deposition (hereinafter referred to as CVD) or a sol-gel method can be used. However, from the viewpoint of controlling the thickness of the metal compound layer, A sputtering method is desirable.

  As a target used for sputtering, a metal target is preferably used, and a reactive sputtering method is widely employed. This is because oxides, nitrides, and oxynitrides of elements used as the metal compound layer are often insulators, and 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.

Present In the invention, when forming a film of the metal compound layer by DC magnetron sputtering using a metal target, the metal compound layer pressure in the vacuum tank for film (the back pressure) once 1.3 × 10 ^- It can be formed by a manufacturing method in which the pressure is ⁴ Pa or less and then an inert gas and oxygen are introduced. There is a concern that once the pressure in the vacuum chamber for forming the metal compound layer is reduced to 1.3 × 10 ⁻⁴ Pa or less, it remains in the vacuum chamber and affects the formation process of the metal compound layer. This is desirable because it can reduce the influence of molecular species. More desirably, it is 5 × 10 ⁻⁵ Pa or less, and further preferably 2 × 10 ⁻⁵ Pa or less.

Next, for example, He, Ne, Ar, Kr, and Xe can be used as the inert gas to be introduced, and it is said that an inert gas having a larger atomic weight causes less damage to the formed film and improves surface flatness. ing. However, Ar is desirable in terms of cost. In order to adjust the oxygen concentration taken into the film, this inert gas may be added with 1.3 × 10 ^{−3 to} 7 × 10 ⁻² Pa of oxygen in terms of partial pressure. Furthermore, in addition to oxygen, O ₃ , N ₂ , N ₂ O, H ₂ O, NH _{3 and the} like can be used depending on the purpose.

Moreover, in this invention, it forms by the manufacturing method which makes partial pressure of the water in the vacuum chamber which forms a metal compound layer into 1.3 * 10 <^-4> Pa or less, and introduces an inert gas and oxygen next. it can. The partial pressure of water is more desirably controlled to 4 × 10 ⁻⁵ Pa or less, and further desirably 2 × 10 ⁻⁵ Pa or less.

In order to relieve stress inside the metal compound layer by incorporating hydrogen into the layer, water may be intentionally introduced in the range of 1.3 × 10 ^{−4 to} 3 × 10 ⁻² Pa. This adjustment may be performed by introducing water using a variable leak valve or a mass flow controller after forming a vacuum once. Moreover, it can implement also by controlling the back pressure of a vacuum chamber.

When determining the water pressure in the present invention, a differential exhaust type in-process monitor may be used. Alternatively, a quadrupole mass spectrometer having a wide dynamic range and capable of measurement even under a pressure of 0.1 Pa level may be used. In general, in a degree of vacuum of about 1.3 × 10 ⁻⁵ Pa, it is water that forms the pressure. Therefore, the value measured by the vacuum gauge may be considered as the moisture pressure as it is.

  In the present invention, since a polymer film is used as the substrate, the substrate temperature cannot be raised above the softening point temperature of the polymer film. Therefore, in order to form the metal compound layer, the temperature of the polymer film needs to be about room temperature or lower to the softening point temperature or lower. In the case of polyethylene terephthalate, which is a typical polymer film, it is desirable to form the metal compound layer while keeping the substrate temperature at 80 ° C. or lower when no special treatment is performed. More desirably, the substrate temperature is 50 ° C. or less, and more desirably 20 ° C. or less. Further, even on a heat-resistant polymer, it can be formed at a substrate temperature set to 80 ° C. or lower, more desirably 50 ° C. or lower, and even more desirably 20 ° C. or lower from the viewpoint of controlling outgas from the polymer film. desirable.

When the transparent conductive laminate of the present invention is used as a movable electrode substrate, a hard coat layer is provided on the surface to which an external force is applied when used for a transparent touch panel, that is, on the surface of the transparent organic polymer substrate opposite to the transparent conductive layer. Is preferably provided. Examples of the material for forming the hard coat layer include organosilane thermosetting resins such as methyltriethoxysilane and phenyltriethoxysilane, melamine thermosetting resins such as etherified methylolmelamine, polyol acrylate, and polyester acrylate. And polyfunctional acrylate ultraviolet curable resins such as urethane acrylate and epoxy acrylate. If necessary, these can be used a mixture of fine particles such as SiO ₂ or MgF _2. At that time, the fine particles are uniformly dispersed in the hard coat layer. The thickness of the hard coat layer is preferably 2 to 5 μm from the viewpoint of flexibility and friction resistance.

  The hard coat layer can be formed by a coating method. As an actual coating method, the above compounds are dissolved in various organic solvents, and after coating on a transparent organic polymer film using a coating liquid whose concentration and viscosity are adjusted, radiation irradiation, heat treatment, etc. Harden the layer. Examples of the coating method include micro gravure coating method, Mayer bar coating method, direct gravure coating method, reverse roll coating method, curtain coating method, spray coating method, comma coating method, die coating method, knife coating method, spin coating method, etc. These various coating methods are used.

  The hard coat layer is laminated directly on the transparent polymer substrate or via an appropriate anchor layer. Examples of the anchor layer include various phases such as a layer having a function of improving the adhesion between the hard coat layer and the transparent organic polymer substrate, and a layer having a three-dimensional refractive index characteristic having a negative K value. Preferred examples include a compensation layer, a layer having a function of preventing permeation of moisture and air or a function of absorbing moisture and air, a layer having a function of absorbing ultraviolet rays and infrared rays, and a layer having a function of reducing the chargeability of a substrate. It is done.

As the hard coat layer, a cured resin layer-3 having an anti-glare (anti-glare) function can be used.
Usually, an antiglare function can be imparted by roughening the surface of the hard coat layer. As a method for roughening the surface of the hard coat layer, for example, whether at least one kind of fine particles having an average primary particle size of 0.001 μm to 5.0 μm is contained in the resin component for forming the hard coat layer Alternatively, the resin component for forming the hard coat layer may include a method in which ultrafine particles C having an average primary particle size of 100 nm or less are contained in a state of forming an aggregate having a size of less than 1.0 μm.

When the cured resin layer-3 having an antiglare (antiglare) function is used as the hard coat layer, the haze of the transparent conductive laminate is usually increased, but can be used as long as the object of the present invention is achieved. In this case, the haze defined by JIS K7136 based on the transparent polymer substrate, the cured resin layer-1, and the cured resin layer-3 is preferably 4% or more and less than 18%.
More preferably, it is 4% or more and less than 15%, and particularly preferably 4% or more and less than 12%.

  EXAMPLES 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 weight unless otherwise specified. Various measurements in the examples were performed as follows.

Arithmetic mean roughness (Ra): Measured using a stylus step meter DEKTAK3 manufactured by Sloan. The measurement was performed according to JIS B0601-1994 edition.
Ten-point average roughness (Rz): Measured using Surfcorder SE-3400 manufactured by Kosaka Laboratory Ltd. The measurement was performed according to JIS B0601-1982 edition.
Image clarity: 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 clarity of transmission was measured. The image definition optical comb in the present invention is defined as a value measured at 2.0 mm.
Haze: The haze value was measured using a hedometer (MDH 2000) manufactured by Nippon Denshoku Co., Ltd.
Evaluation of flickering property: A transparent 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 flickering was visually confirmed. Those that could not be confirmed flickering were judged good, and those that could be confirmed were judged defective.
Newton ring prevention evaluation: Newton ring in a region where the movable electrode substrate and the fixed electrode substrate are in contact with each other from the direction of 60 degrees obliquely to the surface of the transparent touch panel (vertical direction 0 degrees) under a three-wavelength fluorescent lamp. The presence or absence was visually observed and evaluated. What Newton's ring cannot be observed is good, and what can be observed is bad.
Evaluation of Leveling State of Cured Resin Layer-1: The leveling property of the resin was observed using a laser microscope 1LM21D manufactured by Lasertec Corporation.

[Example 1]
100 parts by weight of tetrafunctional acrylate Aronix M405 (manufactured by Toagosei Co., Ltd.), 5 parts by weight of Irgacure 184 (manufactured by Ciba Specialty Chemicals), Ube Nitto Kasei Co., Ltd. (High Plessica 3.0 μm product grade N3N) 7 parts by weight was dissolved in a 1: 1 mixed solvent of isopropyl alcohol and 1-methoxy-2-propanol to prepare a coating solution A. The solid content of coating liquid A and MgF ₂ fine particles having an average primary particle diameter of 30 nm (20% by weight, a mixed solvent dispersion of ethyl alcohol and n-butyl alcohol, manufactured by C-I Kasei Co., Ltd.) with respect to 100 parts by weight of the cured resin component As a result, a coating solution B was prepared by mixing to 5 parts by weight.

Bar coating so that the thickness of the coating liquid B after curing is 2.5 μm on one surface of a polyethylene terephthalate film (made by Teijin DuPont Films, OFW-188) on a transparent polymer substrate After coating by the method and drying at 50 ° C. for 1 minute, a cured resin layer-1 having irregularities was formed by irradiating with ultraviolet rays and curing. The photograph of the laser microscope of the surface of the cured resin layer-1 is shown in FIG. Comparing the leveling state of FIG. 1 with FIG. 2 of Comparative Example 1 and FIG. 3 of Comparative Example 2 described later, it can be seen that FIG. 2 is insufficiently leveled, whereas FIG. 3 is excessively leveled. That is, FIG. 1 shows that the interference fringes indicating the degree of the concavo-convex shape draw a ring having an appropriate size and is in an appropriate leveling state.
A hard coat layer 1 having a thickness of 4 μm was formed on the surface opposite to the surface on which the cured resin layer-1 was formed using an ultraviolet curable polyfunctional acrylate resin coating.

Next, γ-glycidoxypropyltrimethoxysilane (“KBM403” manufactured by Shin-Etsu Chemical Co., Ltd.) and methyltrimethoxysilane (“KBM13” manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed at a molar ratio of 1: 1. Then, the alkoxysilane hydrolyzate 1 was obtained by hydrolysis of the alkoxysilane with an acetic acid aqueous solution (pH = 3.0) by a known method. N-β (aminoethyl) γ-aminopropylmethoxysilane (“KBM603” manufactured by Shin-Etsu Chemical Co., Ltd.) is added at a ratio of 1 part by weight of solid content to 20 parts by weight of solid content of alkoxysilane hydrolyzate 1.
Furthermore, it diluted with the mixed solution of isopropyl alcohol and n-butanol, and produced the alkoxysilane coating liquid C.

  The alkoxysilane coating liquid C was coated on the cured resin layer-1 by a bar coating method, and after baking at 130 ° C. for 2 minutes, a cured resin layer-2 was produced. Further, an ITO layer is formed on the cured resin layer-2 by sputtering using an indium oxide-tin oxide target having a composition of indium oxide and tin oxide of 95: 5 by weight and a filling density of 98%. A transparent conductive laminate was produced. The thickness of the formed ITO layer was about 20 nm, and the surface resistance value immediately after film formation was about 350 Ω / □ (Ω / sq). The manufactured movable electrode substrate was heat-treated at 150 ° C. for 90 minutes to crystallize the ITO layer. The surface resistance value after crystallization of ITO was about 280Ω / □ (Ω / sq). Table 1 shows the measurement results of haze, Ra, Rz, and image definition of the transparent conductive laminate.

On the other hand, after SiO ₂ dip coating was performed on both surfaces of a 1.1 mm thick glass plate, an 18 nm thick ITO layer was formed by sputtering. Next, a fixed electrode substrate was prepared by forming dot spacers having a height of 7 μm, a diameter of 70 μm, and a pitch of 1.5 mm on the ITO layer. A transparent touch panel was produced using the produced fixed electrode substrate and the transparent conductive laminate as a movable electrode substrate. Table 1 shows the evaluation results of the flickering property and Newton's ring prevention property of the produced transparent touch panel.

[Example 2]
The coating liquid A of Example 1 was further added with 0.2 parts by weight of Ube Nitto Kasei Co., Ltd. (Hi-Plesica 2.0 μm product grade N3N), and the cured film thickness of the cured resin layer-1 was A transparent conductive laminate and a transparent touch panel were produced in the same manner as in Example 1 except that the coating was set to 1.9 μm. Table 1 shows the measurement results of the haze, Ra, Rz, and image clarity of the transparent conductive laminate, and the evaluation results of the flickering property and Newton ring prevention property of the transparent touch panel.

[Example 3]
A transparent conductive laminate and a transparent touch panel were produced in the same manner as in Example 1 except that the transparent polymer substrate of Example 1 was changed to ZEONOR (ZF14-100) manufactured by Nippon Zeon Co., Ltd. Table 1 shows the measurement results of the haze, Ra, Rz, and image clarity of the transparent conductive laminate, and the evaluation results of the flickering property and Newton ring prevention property of the transparent touch panel.

[Example 4]
The transparent conductive laminate and the transparent touch panel are the same as in Example 1 except that the transparent polymer substrate of Example 1 is changed to a polycarbonate film ("Pure Ace" C110-100) manufactured by Teijin Chemicals Ltd. Was made. Table 1 shows the measurement results of the haze, Ra, Rz, and image clarity of the transparent conductive laminate, and the evaluation results of the flickering property and Newton ring prevention property of the transparent touch panel.

[Comparative Example 1]
The cured resin layer-1 was formed using the coating liquid A instead of the coating liquid B of Example 1. A photograph of a laser microscope of the produced cured resin layer-1 is shown in FIG. Compared with FIG. 1 of Example 1, the leveling of the cured resin layer-1 is insufficient, and the interference fringes indicating the degree of unevenness are very strong. Subsequently, a transparent conductive laminate and a transparent touch panel were produced in the same manner as in Example 1 except for the cured resin layer-1.
Table 1 shows the measurement results of the haze, Ra, Rz, and image clarity of the transparent conductive laminate, and the evaluation results of the flickering property and Newton ring prevention property of the transparent touch panel.

[Comparative Example 2]
Instead of the coating liquid B of Example 1, the cured resin layer-1 was formed using the coating liquid B in which MgF ₂ fine particles were mixed so as to be 20 parts by weight with respect to 100 parts by weight of the cured resin component. A photograph of a laser microscope of the produced cured resin layer-1 is shown in FIG. Compared with FIG. 1 of Example 1, the cured resin layer-1 is excessively leveled. There is no ring of interference fringes indicating the degree of unevenness.
Subsequently, a transparent conductive laminate and a transparent touch panel were produced in the same manner as in Example 1 except for the cured resin layer-1. Table 1 shows the measurement results of the haze, Ra, Rz, and image clarity of the transparent conductive laminate, and the evaluation results of the flickering property and Newton ring prevention property of the transparent touch panel.

[Reference Example 1]
A transparent laminate was produced in the same manner as in Example 1 except that the transparent conductive layer (ITO) was not formed. Table 1 shows the haze of the transparent laminate. Comparison between Example 1 and Reference Example 1 revealed that there was no haze effect due to the transparent conductive layer.

  From the table, by using the transparent conductive laminate of the present invention, it is possible to suppress flicker when a transparent touch panel is installed on a high-definition display and improve visibility, and to prevent the occurrence of Newton rings. I understand. The transparent conductive laminate of the present invention is useful as a transparent electrode substrate for a transparent touch panel.

2 is a laser microscope photograph of the surface of cured resin layer-1 in Example 1. FIG. 2 is a laser microscope photograph of the surface of a cured resin layer-1 in Comparative Example 1. 6 is a laser microscope photograph of the surface of a cured resin layer-1 in Comparative Example 2.

Claims (13)

  It is a transparent conductive laminate in which a cured resin layer-1 and a transparent conductive layer that form an uneven shape are sequentially laminated on at least one surface of a transparent organic polymer substrate, and is defined by JIS K7105 (1999 edition). A transparent conductive laminate having an image clarity of 75% or more and 95% or less when a 2.0 mm optical comb is used. The transparent conductive laminate according to claim 1, wherein the cured resin layer-1 satisfies the following requirements (A) to (E).
(A) The cured resin layer-1 includes (i) a cured resin component, (ii) at least one fine particle A having an average primary particle size of 0.5 to 5 μm, and (iii) a metal oxide and a metal fluoride. It has at least one selected from the group consisting of ultrafine particles C having an average primary particle size of 100 nm or less.
(B) The content of the fine particles A in the cured resin layer-1 is 0.3 part by weight or more and less than 1.0 part by weight per 100 parts by weight of the cured resin component (i).
(C) The content of the ultrafine particles C in the cured resin layer-1 is 1 to 20 parts by weight per 100 parts by weight of the cured resin component (i).
(D) The thickness of the cured resin layer-1 is 0.5 to 4.5 μm.
(E) The haze defined by JIS K7136 based on the transparent polymer substrate and the cured resin layer-1 is 1% or more and less than 6%.   The transparent conductive laminate according to claim 1, wherein the cured resin layer-1 does not contain a thermoplastic resin. The ultrafine particles C are Al ₂ O ₃ , Bi ₂ O ₃ , CeO ₂ , In ₂ O ₃ , (In ₂ O ₃ .SnO ₂ ), HfO ₂ , La ₂ O ₃ , MgF ₂ , Sb ₂ O ₅ , ( The transparent conductive laminate according to claim 2, which is at least one selected from the group consisting of Sb ₂ O ₅ .SnO ₂ ), SiO ₂ , SnO ₂ , TiO ₂ , Y ₂ O ₃ , ZnO, and ZrO ₂ .   The arithmetic average roughness (Ra) defined in accordance with JIS B0601-1994 of the cured resin layer-1 is 50 nm or more and less than 500 nm, and the ten-point average roughness defined in accordance with JIS B0601-1982 of the cured resin layer-1 The transparent conductive laminate according to claim 2, wherein (Rz) is 100 nm or more and less than 1000 nm.   Between the cured resin layer-1 and the transparent conductive layer, it further has a cured resin layer-2 having a refractive index of 1.20 to 1.55 and a thickness of 0.05 to 0.5 μm. The transparent conductive laminate according to claim 1.   An optical interference layer comprising at least one low refractive index layer and at least one high refractive index layer is provided between the cured resin layer-1 and the transparent conductive layer, and the low refractive index layer is a transparent conductive layer. The transparent conductive laminate according to claim 1, which is in contact with the transparent conductive laminate.   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.   Between the cured resin layer-2 and the transparent conductive layer, it has a metal compound layer that is in contact with the transparent conductive layer and is thinner than the transparent conductive layer, and further has a thickness of 0.5 nm or more and less than 10.0 nm. The transparent conductive laminate according to claim 1.   The transparent conductive laminated body of Claim 1 which forms the cured resin layer-3 which has a glare-proof function in the surface on the opposite side to the surface in which the transparent conductive layer of the transparent polymer substrate was formed.   The transparent conductive laminate according to claim 9, wherein the haze defined by JIS K7136 based on the transparent polymer substrate, the cured resin layer-1 and the cured resin layer-3 is 4% or more and less than 18%.   2. A transparent touch panel comprising at least two transparent electrode substrates each having a transparent conductive layer formed on at least one surface, the transparent conductive layers being arranged so that the transparent conductive layers face each other, and at least one of the transparent electrode substrates is defined in claim 1. A transparent touch panel characterized by being a transparent conductive laminate.   The transparent touch panel is configured by arranging two transparent electrode substrates each having a transparent conductive layer formed on at least one side so that the transparent conductive layers face each other, and at least one of the transparent electrode substrates is defined in claim 9. A transparent touch panel characterized by being a transparent conductive laminate.

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