HK1181917A - Transparent conductive laminated body and transparent touch panel - Google Patents

Description

Transparent conductive laminate and transparent touch panel

The present application is a divisional application of an invention patent application having chinese application No. 2009801526558 (the original application was named "transparent conductive laminate and transparent touch panel", and the original application date was 2009, 10 months and 7 days).

Technical Field

The present invention relates to a transparent conductive laminate. More specifically, the present invention relates to a transparent conductive laminate used for a Liquid Crystal Display (LCD), a transparent touch panel, an organic electroluminescent element, an inorganic electroluminescent lamp, an electromagnetic wave shield, and the like, and particularly to a transparent conductive laminate used for an electrode substrate of a transparent touch panel. The present invention also relates to a transparent touch panel including such a transparent conductive laminate.

Background

As a transparent organic polymer substrate used for optical applications, for example, a transparent organic polymer substrate used for a Liquid Crystal Display (LCD), a touch panel, and the like, a cellulose-based film such as triacetyl cellulose (TAC), a polyester-based film such as a polyethylene terephthalate (PET) film, and the like are known.

Since these transparent organic polymer substrates are insufficient in lubricity and poor in handleability when they are used as they are, a method of forming a slippery layer on the surface to improve the slippery property has been considered. Here, in order to form the slip-susceptible layer, it is known to use an adhesive containing inorganic particles such as silica, calcium carbonate, and kaolin, and/or organic particles such as silicone and crosslinked polystyrene.

However, when such an easy-slip layer made of an adhesive containing inorganic particles and/or organic particles is used, there is a problem that these particles contained in the adhesive cause light scattering, and the transparency or haze characteristics of the obtained transparent organic polymer substrate are impaired.

In order to solve this problem, for example, patent document 1 discloses an optical laminate in which fine particles derived from a catalyst are present under specific conditions in a polyester film having an easily slidable layer containing inorganic particles and/or organic particles.

Documents of the prior art

Patent document

Patent document 1: international publication No. WO2003/093008

Disclosure of Invention

The problem of handling as described above is also present in a transparent conductive laminate having a transparent conductive layer on one surface of a transparent organic polymer substrate, and therefore, it is considered to use an easy-to-slip layer made of an adhesive containing inorganic particles and/or organic particles for such a transparent conductive laminate. However, since the transparency and the haze property of a transparent conductive laminate, particularly a transparent conductive laminate used for an electrode substrate of a transparent touch panel, are very important, a transparent conductive laminate having excellent slipperiness in handling properties and achieving necessary transparency and haze properties is required.

In general, a transparent organic polymer substrate used for optical applications is provided to a user in a form in which a temporary surface protection film for protecting a surface is attached to the surface, and the user performs an operation of peeling off and removing the temporary surface protection film before or after use. Therefore, it is preferable that a transparent conductive laminate excellent in haze characteristics and the like is obtained by using a temporary surface protective film to protect the surface during transportation and storage, and peeling off and removing the unnecessary temporary surface protective film, in the same manner as a transparent conductive laminate having a conventional easy-to-slip layer made of an adhesive containing inorganic particles and/or organic particles having an average primary particle diameter of 200nm or more.

The transparent conductive laminate of the present invention comprises: a transparent organic polymer substrate, a transparent conductive layer on one surface of the transparent organic polymer substrate, and a cured resin layer having an uneven surface on the other surface of the transparent organic polymer substrate, the cured resin layer having an uneven surface formed from a coating composition containing at least 2 components that phase separate due to differences in physical properties.

In particular, in the transparent conductive laminate according to claim 1 of the present invention, the cured resin layer does not contain inorganic fine particles and/or organic fine particles having an average primary particle diameter of 200nm or more, the cured resin layer contains metal oxide and/or metal fluoride ultrafine particles having an average primary particle diameter of less than 200nm, and the amount of the ultrafine particles contained in the cured resin layer is 0.01 to 7.5 parts by mass per 100 parts by mass of the cured resin component.

In the transparent conductive laminate according to claim 2 of the present invention, the cured resin layer does not contain inorganic fine particles and/or organic fine particles for forming an uneven surface, the arithmetic average roughness (Ra) of the uneven surface of the cured resin layer is 5nm or more and less than 500nm, and the ten-point average roughness (Rz) of the uneven surface of the cured resin layer is 50nm or more and less than 2,000 nm.

The transparent conductive laminate of the present invention, particularly the transparent conductive laminates according to the 1 st and 2 nd aspects of the present invention, has excellent slipperiness in handling property and can achieve good transparency and haze characteristics. In addition, according to the transparent conductive laminate of the 1 st aspect of the present invention, the temporary surface protective film can be peeled off and removed in the same manner as the transparent conductive laminate having the conventional easy-to-slip layer. Further, according to the present invention, a transparent touch panel having such a transparent conductive laminate can be provided.

Drawings

Fig. 1 is a schematic view of 1 transparent conductive laminate of the present invention.

Fig. 2 is an enlarged view of a portion of the transparent conductive laminate of the present invention shown in fig. 1, regarding the 1 st embodiment of the transparent conductive laminate of the present invention.

Fig. 3 is another schematic view of the transparent conductive laminate of the present invention.

Fig. 4 is another schematic view of the transparent conductive laminate of the present invention.

Fig. 5 is a schematic view of a transparent touch panel of the present invention.

Detailed Description

< transparent conductive laminate >

The transparent conductive laminate of the present invention comprises a transparent organic polymer substrate, a transparent conductive layer on one surface of the transparent organic polymer substrate, and a cured resin layer having an uneven surface on the other surface of the transparent organic polymer substrate. In the transparent conductive laminate of the present invention, the pressure-sensitive adhesive layer and the 2 nd transparent substrate may be sequentially laminated on the uneven surface of the cured resin layer on the transparent organic polymer substrate (the 1 st transparent substrate).

Fig. 1 to 4 show examples of the transparent conductive laminate of the present invention.

The transparent conductive laminate 10 of the present invention illustrated in fig. 1 includes a transparent organic polymer substrate 1, a transparent conductive layer 2 on one surface of the transparent organic polymer substrate 1, and a cured resin layer 3 having an uneven surface on the other surface of the transparent organic polymer substrate 1.

In embodiment 1 of the transparent conductive laminate according to the present invention, as shown in the enlarged view of fig. 2, the cured resin layer 3 having an uneven surface on the surface of the transparent organic polymer substrate 1 contains metal oxide and/or metal fluoride ultrafine particles 3a having an average primary particle diameter of less than 200nm, and at least a part of these ultrafine particles 3a is present on the uneven surface of the cured resin layer 3.

The transparent conductive laminate 50 of the present invention illustrated in fig. 3 has a temporary surface protective film 30 attached to the uneven surface of the cured resin layer 3, in addition to the structure (1, 2, 3) of the transparent conductive laminate 10 of the present invention illustrated in fig. 1. The temporary surface protection film 30 has a plastic film 6 as a base material and an adhesive layer 7 used on one surface of the plastic film.

The transparent conductive laminate 20 of the present invention illustrated in fig. 4 has a pressure-sensitive adhesive layer 4 and a2 nd transparent substrate 5 laminated in this order on the uneven surface of the cured resin layer 3, in addition to the structure (1, 2, 3) of the transparent conductive laminate 10 of the present invention illustrated in fig. 1.

< transparent conductive laminate-transparent organic Polymer substrate >

The transparent organic polymer substrate used in the transparent conductive laminate of the present invention may be any transparent organic polymer substrate, and particularly a transparent organic polymer substrate used in the optical field and having excellent heat resistance, transparency, and the like.

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

The transparent conductive laminate of the present invention can be produced by appropriately selecting, among these transparent organic polymer substrates, a substrate having little optical birefringence, a substrate having birefringence controlled to λ/4 or λ/2, or a substrate having no birefringence controlled at all, depending on the application. Examples of the case where the transparent conductive laminate is appropriately selected depending on the application include a case where the transparent conductive laminate of the present invention is used as a display member which functions by using polarized light such as linearly polarized light, elliptically polarized light, or circularly polarized light, such as a polarizing plate, a retardation film, or a built-in touch panel used in a liquid crystal display.

The thickness of the transparent organic polymer substrate can be suitably determined, and is generally about 10 to 500 μm, particularly preferably 20 to 300 μm, and more preferably 30 to 200 μm, from the viewpoint of strength, workability, and the like.

< transparent conductive laminate-transparent conductive layer >

In the transparent conductive laminate of the present invention, a transparent conductive layer is disposed on one surface of a transparent organic polymer substrate.

In the present invention, the transparent conductive layer is not particularly limited, but examples thereof include a crystalline metal layer and a crystalline metal compound layer. Examples of the component constituting the transparent conductive layer include a layer of metal oxide such as silicon oxide, aluminum oxide, titanium oxide, magnesium oxide, zinc oxide, indium oxide, and tin oxide. Among them, a crystalline layer containing Indium Oxide as a main component is preferably used, and a layer made of crystalline ITO (Indium Tin Oxide) is particularly preferably used.

When the transparent conductive layer is made of a crystalline material, the crystal grain size is not particularly limited, but is preferably 3000nm or less. When the crystal particle diameter exceeds 3000nm, writing durability is not preferable. Wherein the crystal grain size is defined as the maximum value among the diagonal lines or diameters of each region of a polygon or ellipse 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 reduced.

The transparent conductive layer can be formed by a known method, and a Physical formation method (hereinafter referred to as "PVD") such as a DC magnetron sputtering method, an RF magnetron sputtering method, an ion plating method, a vacuum Deposition method, or a pulsed laser Deposition method can be used. In addition to the above-described physical Deposition method (PVD), a Chemical Vapor Deposition method (hereinafter, referred to as "CVD") or a Chemical formation method such as a sol-gel method may be used, but a sputtering method is still preferable from the viewpoint of controlling the film thickness.

The thickness of the transparent conductive layer is preferably 5 to 50nm in view of transparency and conductivity. More preferably 5 to 30 nm. When the thickness of the transparent conductive layer is less than 5nm, the stability of the resistance value with time tends to be poor, and when it exceeds 50nm, the surface resistance value is lowered, which is not preferable as a touch panel.

When the transparent conductive laminate of the present invention is used for a touch panel, it is preferable to use a transparent conductive layer having a surface resistance value of 100 to 2000 Ω/□ (Ω/sq), more preferably 140 to 1000 Ω/□ (Ω/sq), when the thickness is 10 to 30nm, in order to reduce power consumption of the touch panel and the need for circuit processing.

< transparent conductive laminate-cured resin layer having uneven surface >

In the transparent conductive laminate of the present invention, a cured resin layer having an uneven surface is disposed on the surface of the transparent organic polymer substrate on the opposite side of the transparent conductive layer. Wherein the cured resin layer has a concave-convex surface formed from a coating composition containing at least 2 components that phase separate due to differences in physical properties.

In the transparent conductive laminate of the present invention, the uneven surface of the cured resin layer is formed from a coating composition containing at least 2 components that cause phase separation based on differences in physical properties, and thus a transparent conductive laminate that achieves good transparency or haze characteristics when the pressure-sensitive adhesive layer and the 2 nd transparent substrate are laminated in this order on the uneven surface of the cured resin layer can be provided.

< transparent conductive laminate-cured resin layer having uneven surface-embodiment 1>

In the first aspect of the transparent conductive laminate of the present invention, the cured resin layer does not contain inorganic fine particles and/or organic fine particles having an average primary particle diameter of 200nm or more, the cured resin layer contains metal oxide and/or metal fluoride ultrafine particles having an average primary particle diameter of less than 200nm, and the amount of the ultrafine particles contained in the cured resin layer is 0.01 to 7.5 parts by mass per 100 parts by mass of the cured resin component.

In the first aspect of the transparent conductive laminate of the present invention, the uneven surface of the cured resin layer is formed of a coating composition containing at least 2 components that cause phase separation based on differences in physical properties, and the cured resin layer does not contain inorganic fine particles and/or organic fine particles having an average primary particle diameter of 200nm or more, particularly 150nm or more, and more particularly 100nm or more, that is, inorganic fine particles and/or organic fine particles conventionally used for forming an uneven surface, whereby a transparent conductive laminate having good transparency or haze characteristics can be provided when the pressure-sensitive adhesive layer and the second transparent substrate are laminated in this order on the uneven surface of the cured resin layer. That is, in this case, in the transparent conductive laminate of the invention according to the 1 st aspect, haze due to the inorganic fine particles and/or the organic fine particles does not occur in the cured resin layer having the uneven surface.

This is because an object having a size of 1/4 or less of the wavelength of light to be targeted generally appears to be optically transparent, that is, an object having a size of less than 150nm appears to be optically transparent to visible light of 600nm, for example. But this also relates to the density, degree of dispersion etc. of the objects present and does not mean that an object of this size always appears to be a completely transparent object.

In the present invention, "inorganic fine particles and/or organic fine particles having an average primary particle diameter of 200nm or more are not contained" means that inorganic fine particles and/or organic fine particles having such an average primary particle diameter are not intentionally added.

In the transparent conductive laminate of the invention according to claim 1, the cured resin layer contains ultrafine metal oxide and/or metal fluoride particles having an average primary particle diameter of less than 200 nm. The ultrafine particles having such a size do not contribute significantly to the irregularities on the surface of the cured resin layer, but are present on the surface of the cured resin layer, whereby the peeling force at the time of peeling the temporary surface protective film can be adjusted, and thus the peeling force can be provided as in the case of a conventional easy-to-slip layer comprising a cured resin layer made of an adhesive containing inorganic particles and/or organic particles having an average primary particle diameter of 200nm or more.

In the transparent conductive laminate of the invention of claim 1, the uneven surface formed by the coating composition containing at least 2 components that phase separate due to differences in physical properties can provide excellent slipperiness and optical properties in the handling of the transparent conductive laminate. In particular, the arithmetic average roughness (Ra) of the uneven surface of the cured resin layer is 5nm or more and less than 500nm, and the ten-point average roughness (Rz) of the uneven surface of the cured resin layer is 50nm or more and less than 2,000nm, whereby particularly excellent slipperiness and optical properties can be provided in the handling properties of the transparent conductive laminate.

For example, the arithmetic average roughness (Ra) of the uneven surface of the cured resin layer and the ten-point average roughness (Rz) of the uneven surface of the cured resin layer can be controlled to fall within the above ranges by controlling the SP value and the amount ratio of at least 2 components causing phase separation, the type and the amount ratio of the metal oxide and/or metal fluoride ultrafine particles having an average primary particle diameter of less than 200nm, the type and the amount ratio of the solvent used, the temperature at the time of drying, the drying time, the curing conditions, the film thickness after curing, and the like.

It is preferable that the arithmetic average roughness (Ra) of the uneven surface of the cured resin layer is 5nm or more and the ten-point average roughness (Rz) of the uneven surface of the cured resin layer is 50nm or more because sufficient slipperiness can be obtained. In order to prevent haze increase and flickering of the transparent conductive laminate, it is preferable that the arithmetic average roughness (Ra) of the uneven surface of the cured resin layer is less than 500nm, and the ten-point average roughness (Rz) of the uneven surface is less than 2,000 nm. In particular, when the haze of a transparent conductive laminate in which a pressure-sensitive adhesive layer and a transparent substrate are laminated on a cured resin layer having an uneven surface is low, it is important that the haze increase and the flicker caused by the cured resin layer having an uneven surface are small.

The arithmetic average roughness (Ra) is preferably 5nm or more and less than 400nm, more preferably 5nm or more and less than 300nm, still more preferably 5nm or more and less than 200nm, and particularly preferably 10nm or more and less than 200 nm.

In the present invention, the average arithmetic roughness (center line average roughness) (Ra) is defined in accordance with JIS B0601-1994. Specifically, the arithmetic average roughness (Ra) is represented by the following formula when a portion of a roughness curve having a reference length L is extracted along the center line direction, the center line of the extracted portion is defined as the X axis, the direction of the vertical magnification is defined as the Y axis, and the roughness curve is represented by Y = f (X):

the ten-point average roughness (Rz) is preferably 50nm or more and less than 1500nm, more preferably 50nm or more and less than 1000nm, still more preferably 70nm or more and less than 800nm, and still more preferably 100nm or more and less than 500 nm.

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 a simulated surface roughness meter, and is a value defined as the sum of the average of the peak heights from the highest peak to the 5 th peak in descending order and the average of the valley depths from the deepest valley to the 5 th valley in descending order in a cross-sectional curve (data to be measured) of the reference length. Wherein the reference length is 0.25 mm.

(ultrafine particles of a metal oxide and/or a metal fluoride having an average primary particle diameter of less than 200nm contained in a cured resin layer having an uneven surface)

The type of the metal oxide and/or metal fluoride ultrafine particles having an average primary particle diameter of less than 200nm contained in the cured resin layer of embodiment 1 of the transparent conductive laminate of the present invention is not limited per se. The metal oxide and/or metal fluoride ultrafine particles may have an average primary particle diameter of, for example, less than 150nm, less than 100nm, less than 90nm, less than 80nm, less than 70nm, or less than 60nm, depending on the magnitude of the peeling force of the temporary surface protective film, the haze characteristics of the transparent conductive laminate, and the like.

As the metal oxide and/or metal fluoride ultrafine particles, those selected from MgF can be favorably used₂、Al₂O₃、Bi₂O₃、CeO₂、In₂O₃、In₂O₃·SnO₂、HfO₂、La₂O₃、Sb₂O₅、Sb₂O₅·SnO₂、SiO₂、SnO₂、TiO₂、Y₂O₃ZnO and ZrO₂At least one of (1), and in particular MgF may be used₂、Al₂O₃、SiO₂More particularly, MgF can be used₂。

In the transparent conductive laminate of the invention 1, in order to provide excellent transparency and haze characteristics, it is preferable that the ultrafine particles contained in the cured resin layer are substantially homogeneously dispersed, and in particular, it is preferable that secondary aggregates or secondary particles having an optical wavelength or longer are not formed.

The releasability from the temporary surface protective film can be adjusted to a desired level by adjusting the amount of the ultrafine particles contained in the cured resin layer. Further, if the amount of the ultrafine particles is too large, the phase separation state of the 2-component forming the irregularities of the cured resin layer changes, and the desired slipperiness may not be obtained, and therefore, the amount of the ultrafine particles can be determined within a range that does not impair the slipperiness of the 1 st aspect of the transparent conductive laminate of the present invention.

Specifically, the amount of the ultrafine particles contained in the cured resin layer may be 0.1 to 7.5 parts by mass, for example, 1 to 5 parts by mass.

(Components 1 and 2 constituting the cured resin layer having an uneven surface)

For a coating composition containing at least 2 components that phase separate due to differences in physical properties, which are materials constituting a cured resin layer having an uneven surface, for example, international publication No. WO2005/073763 can be referred to.

For example, as described in international publication No. WO2005/073763, when the coating composition is applied to a transparent organic polymer substrate to form a cured resin layer, the 1 st component and the 2 nd component are phase-separated due to the difference in physical properties between the 1 st and 2 nd components contained in the coating composition, and a resin layer having irregular irregularities on the surface is formed. The specific 1 st and 2 nd components contained in the coating composition may be independently selected from monomers, oligomers, and resins.

In order to cause phase separation of the 1 st component and the 2 nd component based on the difference in physical properties between the 1 st component and the 2 nd component, the difference in specific physical property values of the 1 st and the 2 nd components, for example, the difference in values such as an SP value (Solubility Parameter), a glass transition temperature (Tg), a surface tension, and/or a number average molecular weight, may be made to have a certain magnitude. Wherein, the 1 st and 2 nd components contained in the coating composition may be as follows: 99-99: 1. preferably 1: 99-50: 50. more preferably 1: 99-20: 80 in proportion.

(Components 1 and 2-SP values of the cured resin layer having an uneven surface)

When the phase separation of the component 1 and the component 2 is caused by the difference in SP value (solubility parameter), the difference between the SP value of the component 1 and the SP value of the component 2 is preferably 0.5 or more, more preferably 0.8 or more. The upper limit of the difference in the SP value is not particularly limited, but is generally 15 or less. When the difference between the SP value of the component 1 and the SP value of the component 2 is 0.5 or more, the compatibility between the two resins is low, and it is considered that the phase separation between the component 1 and the component 2 is caused after the coating composition is applied.

The SP value indicates that the polarity is higher as the numerical value is larger, and the polarity is lower as the numerical value is smaller. In the present invention, the SP value is a value measured by the method described in SUH, CLARKE, J.P.S.A.1, 5,1671 to 1681(1967) and the above International publication WO2005/073763 cited therein.

Examples of the 1 st and 2 nd components in this case include a case where the 1 st component is an oligomer or a resin and the 2 nd component is a monomer. The oligomer or resin of component 1 is more preferably an acrylic copolymer having an unsaturated double bond, and the monomer of component 2 is more preferably a monomer having a polyfunctional unsaturated double bond. The term "oligomer" as used herein means a polymer having a repeating unit, and the number of the repeating unit is 3 to 10.

Further, as another example of the components 1 and 2, there is a case where both the components 1 and 2 are an oligomer or a resin. The 1 st and 2 nd components are preferably resins containing a (meth) acrylic resin in the skeleton structure. The component 1 is more preferably an acrylic copolymer component containing an unsaturated double bond, and the component 2 is more preferably a monomer containing a polyfunctional unsaturated double bond.

In addition, the coating composition for the cured resin layer of the present invention may further contain an organic solvent. Preferable examples of the organic solvent include ketone solvents such as methyl ethyl ketone, alcohol solvents such as methanol, and ether solvents such as anisole. These solvents may be used alone in 1 kind, or 2 or more kinds of organic solvents may be used in combination.

(glass transition temperature (Tg) of Components 1 and 2 constituting the cured resin layer having an uneven surface.)

When the phase separation of the 1 st component and the 2 nd component is caused by the difference in glass transition temperature (Tg), it is preferable that either one of the 1 st and the 2 nd components has a Tg lower than the ambient temperature at the time of application of the composition, and the other has a Tg higher than the ambient temperature at the time of application of the composition. In this case, it is considered that the resin having a Tg higher than the ambient temperature is in a glass state in which the molecular motion is controlled at the ambient temperature, and therefore, the resin is aggregated in the coating composition after coating, thereby causing phase separation of the 1 st component and the 2 nd component.

(Components 1 and 2-surface tension of the cured resin layer having an uneven surface)

When the phase separation of the component 1 and the component 2 is caused by a difference in surface tension, the difference between the surface tension of the component 1 and the surface tension of the component 2 is preferably 1 to 70dyn/cm, and the difference is more preferably 5 to 30 dyn/cm. When the difference in surface tension is within this range, the resin having a higher surface tension tends to aggregate, and therefore, the phase separation of the 1 st component and the 2 nd component is likely to occur after the coating composition is applied.

The surface tension can be measured by obtaining the static surface tension measured by a cyclic method using a Dynometer manufactured by BYK Chemie.

(Components other than the 1 st and 2 nd Components constituting the cured resin layer having an uneven surface)

The coating composition for a cured resin layer having an uneven surface may contain a generally used resin in addition to the above-mentioned components 1 and 2. The coating composition for the cured resin layer having an uneven surface can also be prepared by mixing the 1 st and 2 nd components together with a solvent, a catalyst, and a curing agent as necessary.

The solvent used in the coating composition for the cured resin layer having an uneven surface is not particularly limited, and is appropriately selected in consideration of the 1 st and 2 nd components, the material of the substrate to be coated, the coating method of the composition, and the like. Specific examples of the solvent to be used include aromatic solvents such as toluene; ketone solvents such as methyl ethyl ketone; ether solvents such as diethyl ether; ester solvents such as ethyl acetate; amide solvents such as dimethylformamide; cellosolve solvents such as methyl cellosolve; alcohol solvents such as methanol; halogen-based solvents such as methylene chloride. These solvents may be used alone, or 2 or more of them may be used in combination.

< transparent conductive laminate-cured resin layer having uneven surface-embodiment 2>

In embodiment 2 of the transparent conductive laminate according to the present invention, the cured resin layer does not contain inorganic fine particles and/or organic fine particles for forming the uneven surface. Further, the arithmetic average roughness (Ra) of the uneven surface of the cured resin layer is 10nm or more and less than 500nm, and the ten-point average roughness (Rz) of the uneven surface of the cured resin layer is 100nm or more and less than 2,000 nm.

In the 2 nd aspect of the transparent conductive laminate of the present invention, the uneven surface of the cured resin layer is formed of a coating composition containing at least 2 components that phase separate due to differences in physical properties, and the cured resin layer does not contain inorganic fine particles and/or organic fine particles for forming the uneven surface, whereby a transparent conductive laminate that achieves good transparency or haze characteristics when the pressure-sensitive adhesive layer and the 2 nd transparent substrate are laminated in this order on the uneven surface of the cured resin layer can be provided. That is, in this case, in the transparent conductive laminate according to the 2 nd aspect of the present invention, haze due to the inorganic fine particles and/or the organic fine particles does not occur in the cured resin layer having the uneven surface.

In addition, in the mode 2 of the transparent conductive laminate according to the present invention, the arithmetic average roughness (Ra) of the uneven surface of the cured resin layer is 5nm or more and less than 500nm, and the ten-point average roughness (Rz) of the uneven surface of the cured resin layer is 50nm or more and less than 2,000nm, whereby excellent slipperiness can be provided in terms of handling of the transparent conductive laminate. The arithmetic average roughness (Ra) of the uneven surface of the cured resin layer and the ten-point average roughness (Rz) of the uneven surface of the cured resin layer can be controlled within these ranges by controlling, for example, the SP value and the amount ratio of at least 2 components causing phase separation, the kind and amount of the solvent used, the temperature at the time of drying, the drying time, the curing conditions, the film thickness after curing, and the like.

The dimensions of the inorganic fine particles and/or organic fine particles for forming the uneven surface, preferably the arithmetic average roughness (Ra) and the ten-point average roughness (Rz), the 1 st and 2 nd components constituting the cured resin layer having the uneven surface, the components other than the 1 st and 2 nd components constituting the cured resin layer having the uneven surface, and the like can be referred to the description of the 1 st aspect of the transparent conductive laminate of the present invention.

< transparent conductive laminate-temporary surface protective film >

The transparent conductive laminate of the present invention may further comprise a temporary surface protective film attached to the uneven surface of the cured resin layer. The temporary surface protective film generally has a structure in which a plastic film is used as a base material and an adhesive layer is provided on one surface of the base material. The temporary surface protective film is attached to the uneven surface of the cured resin layer of the transparent conductive laminate of the present invention, and is used to protect the transparent conductive laminate of the present invention during transportation, storage, processing, and the like, and then peeled off and removed.

In the first aspect of the transparent conductive laminate of the present invention, the same temporary surface protective film as that used in the transparent conductive laminate having a conventional easy-to-slide layer, that is, the same temporary surface protective film as that used in the transparent conductive laminate having a conventional easy-to-slide layer made of an adhesive containing inorganic particles and/or organic particles having an average primary particle size of 200nm or more is used, and the temporary surface protective film can be peeled off in the same manner as the temporary surface protective film is peeled off from the transparent conductive laminate having a conventional easy-to-slide layer.

As the substrate of the temporary surface protective film, a transparent olefin film such as polyethylene and polypropylene, and a polyester film such as polyethylene terephthalate and polycarbonate can be generally used. The surface protective film may have a single-layer structure or a multilayer structure. In the case of a multilayer structure, a multilayer structure having an arbitrary number of layers can be obtained by coextrusion, for example. The surface of the protective film may be subjected to an easy-slip treatment such as embossing.

The adhesive layer of the temporary surface protective film is composed of an adhesive. In order to bond and fix the base film of the temporary surface protective film to the transparent conductive laminate of the present invention, an adhesive layer is formed on one surface of the base film. The adhesive may be suitably selected from general adhesives such as ethylene vinyl acetate copolymer (EVA) adhesives, special polyolefin adhesives, and acrylic adhesives. In general, an acrylic adhesive is preferably used in consideration of indoor and outdoor use, various light rays, particularly ultraviolet rays, in consideration of detection, and further in consideration of prevention of migration of components from an adhesive layer to a mating substrate to be bonded, but the invention is not limited thereto.

For example, japanese patent application laid-open No. 2005-66919 can be referred to as a temporary surface protective film.

< transparent conductive laminate-adhesive layer and No. 2 transparent substrate >

The transparent conductive laminate of the present invention may further comprise a pressure-sensitive adhesive layer and a2 nd transparent substrate which are sequentially laminated on the uneven surface of the cured resin layer. The pressure-sensitive adhesive layer and the 2 nd transparent substrate of the transparent conductive laminate of the present invention may be any pressure-sensitive adhesive layer and the 2 nd transparent substrate, and particularly any pressure-sensitive adhesive layer and the 2 nd transparent substrate used for optical applications.

The pressure-sensitive adhesive layer and the 2 nd transparent substrate may be selected according to the use of the transparent conductive laminate of the present invention. That is, in applications where high transparency is desired as the entire transparent conductive laminate of the present invention, it is needless to say that a pressure-sensitive adhesive layer and a2 nd transparent substrate having high transparency are preferably used.

< transparent conductive laminate-adhesive layer and No. 2 transparent substrate-adhesive layer >

Examples of the material constituting the pressure-sensitive adhesive layer include known pressure-sensitive adhesives and curable resins, for example, radiation-curable resins such as thermosetting resins and ultraviolet-curable resins. Among them, acrylic pressure-sensitive adhesives can be preferably used.

Preferably, the refractive index of the cured resin layer having the uneven surface is substantially the same as the refractive index of the adhesive layer. This is because, when the values of these refractive indices are substantially the same, reflection, scattering, and the like of light at the interface between the cured resin layer and the pressure-sensitive adhesive layer can be suppressed. Here, the refractive indices "substantially the same" means that, for example, the difference in average refractive index is 0.05 or less, particularly 0.03 or less, more particularly 0.02 or less, further 0.01 or less, particularly 0.005 or less, and preferably 0.002 or less. The average refractive index used herein is a value measured by, for example, Abbe refractometer (product name: Abbe refractometer 2-T, manufactured by ATAGO Co., Ltd.).

< transparent conductive laminate-adhesive layer and No. 2 transparent substrate-No. 2 transparent substrate >

As the 2 nd transparent substrate, a transparent plastic film, a transparent plastic plate, a glass plate, or the like can be used. Examples of the material used for the transparent plastic film or sheet include substrates made of transparent polymers such as polyester polymers such as polyethylene terephthalate and polyethylene naphthalate (PET), polycarbonate polymers, cellulose polymers such as diacetyl cellulose, triacetyl cellulose (TAC) and cellulose acetate butyrate, and acrylic polymers such as polymethyl methacrylate. Further, there can be mentioned substrates composed of a styrene polymer such as polystyrene and an acrylonitrile-styrene copolymer, an olefin polymer such as polyethylene, polypropylene, a polyolefin having a cyclic or norbornene structure, and an ethylene-propylene copolymer, a vinyl chloride polymer, and a transparent polymer such as an amide polymer typified by nylon and aromatic polyamide. Further, there may be mentioned substrates comprising a transparent polymer such as an imide polymer, a sulfone polymer, a polyether ether ketone polymer, a polyphenylene sulfide polymer, a vinyl alcohol polymer, a vinylidene chloride polymer, a vinyl butyral polymer, an allyl ester polymer, a polyoxymethylene polymer, an epoxy polymer, or a blend of these polymers.

The specific material and thickness of the 2 nd transparent substrate of the transparent conductive laminate of the present invention may have any thickness depending on the use of the transparent conductive laminate. For example, when the transparent conductive laminate of the present invention is used as a movable electrode substrate of a transparent touch panel, a transparent plastic film may be used as the 2 nd transparent substrate, and the thickness of the entire transparent conductive laminate having the pressure-sensitive adhesive layer and the 2 nd transparent substrate may be 50 to 400 μm, in order to ensure the flexibility and the strength of flatness for operating the movable electrode substrate as a switch. In addition, when the transparent conductive laminate of the present invention is used as a fixed electrode substrate of a transparent touch panel, a transparent glass plate or a transparent plastic plate may be used as the 2 nd transparent substrate in view of strength for ensuring flatness, and the thickness of the entire transparent conductive laminate including the pressure-sensitive adhesive layer and the 2 nd transparent substrate may be 0.2 to 4.0 mm.

< transparent conductive laminate-other layer >

The transparent conductive laminate of the present invention may have a layer such as an adhesive layer, a hard layer, or an optical interference layer between and/or on each layer constituting the transparent conductive laminate of the present invention, for example, between the transparent organic polymer substrate and the cured resin layer having an uneven surface, and/or between the transparent organic polymer substrate and the transparent conductive layer, and/or on the cured resin layer having an uneven surface, and/or on the transparent conductive layer, within a range not to impair the object of the present invention.

For example, a cured resin layer having an uneven surface is laminated on a transparent organic polymer substrate directly or via an appropriate fixing layer. Examples of such a fixing layer include a layer having a function of improving adhesion between a cured resin layer having an uneven surface and a transparent organic polymer substrate; a layer having a function of preventing permeation of moisture and air; a layer having a function of absorbing moisture and air; a layer having a function of absorbing ultraviolet rays and infrared rays; a layer having a function of reducing the charging property of the substrate, and the like.

< transparent conductive laminate-haze >

As described above, the transparent conductive laminate of the present invention has excellent slipperiness in handling properties due to the cured resin layer having the uneven surface, and can achieve excellent transparency and haze characteristics when the pressure-sensitive adhesive layer and the 2 nd transparent substrate are laminated in this order on the uneven surface of the cured resin layer.

The haze property at this time is a property that satisfies the following relationship, for example, when a transparent conductive laminate similar to the transparent conductive laminate of the present invention except for having a reference cured resin layer having no haze instead of the cured resin layer having the uneven surface is used as the reference transparent conductive laminate.

-0.1<H1-H2<1.0

Preferably-0.1 < H1-H2<0.5

More preferably-0.1 < H1-H2<0.3

More preferably-0.1 < H1-H2<0.1

(H1: haze value (%) of transparent conductive laminate when laminating adhesive layer and the 2 nd transparent substrate in this order on the uneven surface of the cured resin layer having uneven surface,

h2: haze value (%) of the reference transparent conductive laminate when the pressure-sensitive adhesive layer and the 2 nd transparent substrate were laminated in this order on the surface of the reference cured resin layer.

The "reference cured resin layer without haze" of the reference transparent conductive laminate means a cured resin layer substantially without internal haze, and can be defined as a cured resin layer having a measured internal haze of less than 0.1, for example.

The small difference (H1-H2) means that when the pressure-sensitive adhesive layer and the 2 nd transparent substrate are laminated in this order on the uneven surface of the cured resin layer of the transparent conductive laminate of the present invention, transparency or haze characteristics equivalent to those of a corresponding transparent conductive laminate having no slipping layer (i.e., a reference transparent conductive laminate), that is, good transparency or haze characteristics can be achieved.

In the present invention, the haze is defined according to JIS K7136. In particular, haze is taken as the diffuse transmittance τ_dAnd total light transmittance tau_tMore specifically, the value defined by the ratio of (a) to (b) can be obtained by the following equation:

haze (%) = [ (tau)₄/τ₂)-τ₃(τ₂/τ₁)]×100

τ₁: beam of incident light

τ₂: total light beam of transmission test piece

τ₃: light beam diffused in the device

τ₄: light beam diffused in device and test piece

< transparent touch Panel >

In the transparent touch panel of the present invention, 2 transparent electrode substrates each having a transparent conductive layer on at least one surface thereof are arranged such that the transparent conductive layers thereof face each other, and at least one of the 2 transparent electrode substrates has the transparent conductive laminate of the present invention.

Fig. 5 shows an example of the transparent touch panel of the present invention. The transparent touch panel 100 of the present invention illustrated in fig. 5 includes a fixed electrode substrate 20', a movable electrode substrate 20 ″, and a dot spacer 9 between the electrodes.

The gap between the movable electrode substrate 20 'and the fixed electrode substrate 20' is set to a distance of 10 to 100 μm by the dot spacers 9. When the movable electrode substrate 20 ″ is pressed from the surface of the movable electrode substrate 20 ″ with a finger or a pen (pen), the movable electrode substrate 20 ″ and the fixed electrode substrate 20' are brought into electrical contact at the pressed position, and thus the input position can be detected as a potential difference. The dot spacer 9 suppresses the movable electrode substrate 20' from being bent by natural force to be in contact with the fixed electrode substrate 20 ″, and is provided for enabling input with a finger or a pen, but is not necessarily required.

The transparent touch panel of the present invention may be mounted in a liquid crystal display device. In this case, for example, in the transparent touch panel 100 of the present invention shown in fig. 5, one of the glass substrates sandwiching the liquid crystal layer of the liquid crystal display device may be used as the 2 nd transparent substrate 5 'on the fixed electrode substrate 20' side.

The fixed electrode substrate 20 'includes a transparent organic polymer substrate 1', a transparent conductive layer 2 on one surface of the transparent organic polymer substrate, a cured resin layer 3 having an uneven surface on the other surface of the transparent organic polymer substrate, a pressure-sensitive adhesive layer 4 'laminated on the uneven surface of the cured resin layer, and a2 nd transparent substrate 5' such as a glass plate. The movable electrode substrate 20 "has a transparent organic polymer substrate 1", a transparent conductive layer 2 on one surface of the transparent organic polymer substrate ", a cured resin layer 3 having an uneven surface on the other surface of the transparent organic polymer substrate", an adhesive layer 4 "and a2 nd transparent substrate 5" such as a plastic film, which are sequentially stacked on the uneven surface of the cured resin layer.

Examples

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the examples, "part(s)" and "%" are based on mass unless otherwise specified. In addition, various measurements in examples were performed in the following manner.

< Ra (arithmetic mean roughness) >

The measurement was performed using a probe height difference meter DEKTAK3 manufactured by Sloan corporation. The assay was performed according to JISB0601-1994 edition.

< Rz (ten-point average roughness) >

The measurement was carried out using SurfcorderSE-3400, manufactured by K.K.K.. The measurement was carried out in accordance with JIS B0601-1982 edition.

< thickness >

The measurement was carried out using a probe type film thickness meter アルファステック manufactured by Anritsu Electric Co.

< haze >

The measurement was carried out using a haze meter (MDH2000) manufactured by Nippon Denshoku Kogyo Co., Ltd.

< contact Angle >

A flat plate-like sample piece was placed horizontally, the surface of the cured resin layer was faced upward, 1 drop of water was dropped using a syringe having a capacity of 1ml according to the static drop method of JISR3257, and 1 to 4. mu.l of water drop was left standing on the sample piece. Subsequently, the water contact angle θ after standing for 1 minute was read using a microscope equipped with an goniometer.

< peeling force >

The transparent conductive laminate was fixed to an acrylic plate using a tensile tester (55R4302) manufactured by Instron Japan Company Limited, and the peel force of the protective film was measured under the following conditions.

Peeling angle: 180 degrees

Stripping speed: 300mm/min

Width of the sample: 30mm

< slipperiness >

The slipperiness of the cured resin layer was evaluated by a sensory test as whether the slipperiness was good (O) or poor (X).

Examples A1 to A4, reference example A1 and comparative examples A1 to A2

The transparent conductive laminates of examples a1 to a4, reference example a1, and comparative examples a1 to a2 were configured as shown in fig. 3, and a test was performed on the peel force when the temporary surface protective film was peeled off and removed. The transparent conductive laminates were configured as shown in fig. 4, and haze values of the transparent conductive laminates were measured before and after laminating the pressure-sensitive adhesive layer and the 2 nd transparent substrate. The results are shown in table 1 below. Specifically, these transparent conductive laminates were produced as follows.

Example A1

(formation of cured resin layer)

The transparent conductive laminate of example A1 was prepared in the following mannerThe method is used for manufacturing. That is, the following coating liquid R was used on one surface of a carbonate (PC) film (C110, manufactured by Denko chemical industries, Ltd.) (No. 1 transparent substrate, haze value 0.11%) having a thickness of 100 μm_AThe coating was carried out by a bar coating method, dried at 30 ℃ for 1 minute, and then cured by irradiation with ultraviolet light to form a cured resin layer having a thickness of 3.0 μm and a refractive index of 1.50.

Coating liquid R_AIs prepared by the following steps: an unsaturated double bond-containing acrylic copolymer component (Sp value: 10.0, Tg: 92 ℃ C.) as a1 st component constituting a cured resin layer having an uneven surface was added in an amount of 4.5 parts by weight, pentaerythritol triacrylate (Sp value: 12.7) as a2 nd component constituting a cured resin layer having an uneven surface was added in an amount of 100 parts by weight, and a metal fluoride ultrafine particle dispersion was added in an amount of 10 parts by weight (2 parts by weight in terms of solid content, manufactured by C.I. KASEI K Co., Ltd., MgF₂20% by mass of ultrafine particles, an isopropyl alcohol dispersion liquid having a primary average particle diameter of 50nm, and 7 parts by weight of IRGACURE184 (Ciba specialty Chemicals) as a photopolymerization initiator were dissolved in an isobutanol solvent so that the solid content was 30% by weight.

The unsaturated double bond-containing acrylic copolymer (Sp value: 10.0, Tg: 92 ℃ C.) as component 1 was prepared in the following manner.

A mixture consisting of isobornyl methacrylate 171.6g, methyl methacrylate 2.6g and methyl acrylate 9.2g was mixed. This mixed solution was added dropwise to 330.0g of propylene glycol monomethyl ether heated to 110 ℃ under a nitrogen atmosphere in a 1000ml reaction vessel equipped with a stirring paddle, a nitrogen introduction tube, a cooling tube and a dropping funnel simultaneously with 80.0g of propylene glycol monomethyl ether containing 1.8g of t-butylperoxy-2-ethylhexanoate over 3 hours at a constant rate, and then reacted at 110 ℃ for 30 minutes.

Then, a solution containing 17.0g of propylene glycol monomethyl ether containing 0.2g of t-butylperoxy-2-ethylhexanoate was added dropwise, a solution containing 5.0g of propylene glycol monomethyl ether containing 1.4g of tetrabutylammonium bromide and 0.1g of hydroquinone was added, a solution containing 22.4g of 4-hydroxybutylacrylate glycidyl ether and 5.0g of propylene glycol monomethyl ether was added dropwise over 2 hours while blowing air, and the reaction was further carried out over 5 hours, whereby an unsaturated double bond-containing acrylic copolymer as the component 1 was obtained.

The obtained acrylic copolymer containing an unsaturated double bond had a number average molecular weight of 5,500, a weight average molecular weight of 18,000, an Sp value: 10.0, Tg: 92 ℃ and surface tension: 31 dyn/cm.

(formation of ITO layer)

Next, on the other surface on which the cured resin layer was formed, a cured resin layer was formed using a composition in which the weight ratio of indium oxide to tin oxide was 95: 5 and a 98% packing density, and a transparent conductive layer-1 (ITO layer) was formed by a sputtering method. The ITO layer had a thickness of about 20nm and a surface resistance value of about 350. omega./□ (Ω/sq).

(measurement of peeling force)

A protective film (PAC-2-70 manufactured by Sun A. Kaken) was pressure-bonded to the cured resin layer at room temperature, and heat-treated at 130 ℃ for 90 minutes. Then, the protective film was peeled off, and the peel strength (adhesion strength) of the protective film was measured.

(preparation of transparent conductive laminate)

Further, an acrylic pressure-sensitive adhesive (refractive index: 1.50) and a Polycarbonate (PC) film (C110, manufactured by sumiki chemical corporation, haze value: 0.11%) having a thickness of 100 μm (No. 2 transparent substrate) were sequentially laminated on the cured resin layer to prepare a transparent conductive laminate.

The properties of the transparent conductive laminate thus produced are shown in table 1.

Example A2

Except that the amount of the metal fluoride ultrafine particle dispersion of example A1 used was 25 parts by mass (5 parts by mass in terms of solid content, manufactured by C.I. KASEI K.K., MgF.)₂20% by mass of ultrafine particles having a primary average particle diameter of 50nm, and an isopropyl alcohol dispersion) A transparent conductive laminate was obtained in the same manner as in example a 1. The properties of the transparent conductive laminate thus produced are shown in table 1. The refractive index of the obtained cured resin layer was 1.50.

Example A3

A transparent conductive laminate was obtained in the same manner as in example a1, except that a 188 μm thick polyethylene terephthalate (PET) film (OFW manufactured by Teijin DuPont Films, ltd.) was used instead of the transparent substrate a of example a1, and the drying temperature of the coating liquid R was set to 50 ℃. The properties of the transparent conductive laminate thus produced are shown in table 1. The refractive index of the obtained cured resin layer was 1.50.

Example A4

A transparent conductive laminate was obtained in the same manner as in example a1, except that the cured resin layer of example a1 was changed to a film thickness of 1.0 μm. The properties of the transparent conductive laminate thus produced are shown in table 1. The refractive index of the obtained cured resin layer was 1.50.

[ reference example A1]

The transparent conductive laminate of reference example a1 was produced in the following manner.

A transparent conductive laminate was obtained in the same manner as in example a1, except that the metal fluoride ultra-fine particle dispersion of example a1 was not used. The properties of the transparent conductive laminate thus produced are shown in table 1. The refractive index of the obtained cured resin layer was 1.50.

Comparative example A1

Except that the coating liquid R was replaced when the cured resin layer of example A1 was formed_AThe following coating liquid S was used_AA transparent conductive laminate was obtained in the same manner as in example a1, except that the film thickness was changed to 2 μm. The properties of the transparent conductive laminate thus produced are shown in table 1. The cured resin layer obtainedThe refractive index was 1.51.

(coating liquid S)_AComposition of

4-functional acrylate: 100 parts by mass of "Aronix" M-405 (manufactured by Toyo Seisaku-Sho Co., Ltd.) (refractive index after polymerization: 1.51)

Silica particles having a primary average particle diameter of 3.0 μm (refractive index: 1.48): 1 part by mass

A photoreaction initiator: 5 parts by mass of "IRGACURE" 184 (product of Ciba specialty Chemicals Co., Ltd.)

Diluting liquid: appropriate amount (isobutyl alcohol)

Comparative example A2

Except that the coating liquid R was replaced when the cured resin layer of example A1 was formed_AThe following coating liquid T was used_AA transparent conductive laminate was obtained in the same manner as in example a 1. The properties of the transparent conductive laminate thus produced are shown in table 1. Wherein the coating liquid T is used_ASince the formed cured resin layer was a standard cured resin layer having no haze, the transparent conductive laminate of comparative example a2 was set as a standard transparent conductive laminate, and the haze thereof was set as a standard haze (H2). The refractive index of the obtained cured resin layer was 1.51.

(coating liquid T)_AComposition of

4-functional acrylate: 100 parts by mass of "Aronix" M-405 (manufactured by Toyo Seisaku-Sho Co., Ltd.) (refractive index after polymerization: 1.51)

A photoreaction initiator: 5 parts by mass of "IRGACURE" 184 (product of Ciba specialty Chemicals Co., Ltd.)

Diluting liquid: appropriate amount (isobutyl alcohol)

[ Table 1]

As is clear from table 1, the transparent conductive laminates of examples a1 to a4 were excellent in slipperiness. The transparent conductive laminates of examples a1 to a4, in which the pressure-sensitive adhesive layer and the 2 nd transparent substrate were laminated in this order, also had excellent haze characteristics. More specifically, the haze value (H1) of the transparent conductive laminate of examples a1, a2, and a4 in which the pressure-sensitive adhesive layer and the 2 nd transparent substrate were laminated in this order was equivalent to and superior to the haze value (H2) of the standard transparent conductive laminate of comparative example a2 in which a standard cured resin layer having no haze was used instead of the cured resin layer having irregularities.

Further, since the transparent conductive laminates of examples a1 to a4 have the same surface properties, particularly the peeling force of the temporary surface protective film, as the transparent conductive laminate having the conventional easy-to-slide layer (comparative example a 1), the peeling operation of the surface protective film and the like can be performed as in the transparent conductive laminate having the conventional easy-to-slide layer (comparative example a 1).

On the other hand, the transparent conductive laminate of reference example a1 is excellent in slipperiness and haze characteristics, but unlike the transparent conductive laminate having a conventional slipperiness layer (comparative example a 1), the surface characteristics, particularly the peeling strength of the temporary surface protective film, is significantly higher than that of the transparent conductive laminate having a conventional slipperiness layer (comparative example a 1). Therefore, the transparent conductive laminate of reference example a1 was not subjected to the surface protective film peeling operation and the like in the same manner as the transparent conductive laminate having the conventional easy-to-slip layer (comparative example a 1).

The transparent conductive laminate having the conventional easy-to-slide layer of comparative example a1 is excellent in easy-to-slide property, but has poor haze characteristics when the pressure-sensitive adhesive layer and the 2 nd transparent substrate are laminated in this order due to light scattering caused by the inorganic fine particles. The transparent conductive laminate of comparative example a2 was excellent in haze characteristics when the pressure-sensitive adhesive layer and the 2 nd transparent substrate were laminated in this order, but was not easy to slip and poor in handleability.

< examples B1 to B3 and comparative examples B1 to B2>

The transparent conductive laminates of examples B1 to B3 and comparative examples B1 to B2 were configured as shown in fig. 4, and haze values of the transparent conductive laminates were measured before and after laminating the pressure-sensitive adhesive layer and the 2 nd transparent substrate. The results are shown in table 2 below. Specifically, these transparent conductive laminates were produced as follows.

< example B1>

The transparent conductive laminate of example B1 was produced in the following manner.

(formation of cured resin layer)

A coating liquid R was applied to one surface of a 100 μm thick carbonate (PC) film (C110, manufactured by Denko chemical industries, Ltd.) (1 st transparent substrate, haze value 0.11%)_BCoating by bar coating method, drying at 30 deg.C for 1 min, and curing by irradiating with ultraviolet ray to form a cured resin layer with thickness of 3.0 μm and refractive index of 1.50, wherein the coating liquid R_BExcept that the dispersion liquid does not contain metal fluoride ultrafine particles, and a coating liquid R_AThe same is true.

(formation of ITO layer)

Next, on the other surface on which the cured resin layer was formed, a cured resin layer was formed using a composition in which the weight ratio of indium oxide to tin oxide was 95: 5 and a 98% packing density, and a transparent conductive layer-1 (ITO layer) was formed by a sputtering method. The ITO layer had a thickness of about 20nm and a surface resistance value of about 350. omega./□ (Ω/sq).

(preparation of transparent conductive laminate)

Further, an acrylic pressure-sensitive adhesive (refractive index: 1.50) and a Polycarbonate (PC) film (C110, manufactured by sumiki chemical corporation, haze value: 0.11%) having a thickness of 100 μm (No. 2 transparent substrate) were sequentially laminated on the cured resin layer to prepare a transparent conductive laminate.

The properties of the transparent conductive laminate thus produced are shown in table 2.

Example B2

Except that the coating liquid R of example B1 was used_BWas carried out in the same manner as in example B1 except that the drying temperature of (1) was changed to 70 ℃. The properties of the transparent conductive laminate thus produced are shown in table 2. The refractive index of the obtained cured resin layer was 1.50.

Example B3

Except that a 188 μm thick polyethylene terephthalate (PET) film (Teijin DuPont Films, Inc. OFW, haze value 0.73%) was used in place of the 1 st transparent substrate (PC) of example B1, and a coating liquid R was used_BWas carried out in the same manner as in example B1 except that the drying temperature of (a) was changed to 70 ℃. The properties of the transparent conductive laminate thus produced are shown in table 2. The refractive index of the obtained cured resin layer was 1.50.

Comparative example B1

The transparent conductive laminate of comparative example B1 was produced in the following manner.

Except that the coating liquid R was replaced when the cured resin layer of example B1 was formed_BThe following coating liquid S was used_BA transparent conductive laminate was obtained in the same manner as in example B1, except that the film thickness was changed to 2 μm. The properties of the transparent conductive laminate thus produced are shown in table 2. The refractive index of the obtained cured resin layer was 1.51.

(coating liquid S)_BComposition of

4-functional acrylate: 100 parts by mass of "Aronix" M-405 (manufactured by Toyo Seisaku-Sho Co., Ltd.) (refractive index after polymerization: 1.51)

Silica particles having a primary average particle diameter of 3.0 μm (refractive index: 1.48): 1 part by mass

A photoreaction initiator: 5 parts by mass of "IRGACURE" 184 (product of Ciba specialty Chemicals Co., Ltd.)

Diluting liquid: appropriate amount (isobutyl alcohol)

Comparative example B2

Except that the coating liquid R was replaced when the cured resin layer of example B1 was formed_BThe following coating liquid T was used_BA transparent conductive laminate was obtained in the same manner as in example B1. The properties of the transparent conductive laminate thus produced are shown in table 2. Wherein the coating liquid T is used_BSince the formed cured resin layer was a standard cured resin layer having no haze, the transparent conductive laminate of comparative example B2 was set as a standard transparent conductive laminate, and the haze thereof was set as a standard haze (H2). The refractive index of the obtained cured resin layer was 1.51.

(coating liquid T)_BComposition of

4-functional acrylate: 100 parts by mass of "Aronix" M-405 (manufactured by Toyo Seisaku-Sho Co., Ltd.) (refractive index after polymerization: 1.51)

A photoreaction initiator: 5 parts by mass of "IRGACURE" 184 (product of Ciba specialty Chemicals Co., Ltd.)

Diluting liquid: appropriate amount (isobutyl alcohol)

[ Table 2]

As is clear from table 2, the transparent conductive laminates of examples B1 to B3 were excellent in slipperiness. The transparent conductive laminates of examples B1 to B3, in which the pressure-sensitive adhesive layer and the 2 nd transparent substrate were laminated in this order, also had excellent haze characteristics. More specifically, the haze values (H1) of the transparent conductive laminates of examples B1 and B2 when the pressure-sensitive adhesive layer and the 2 nd transparent substrate were laminated in this order were equivalent to and excellent as the haze value (H2) of the standard transparent conductive laminate of comparative example B2 in which a standard cured resin layer having no haze was used instead of the cured resin layer having irregularities.

On the other hand, the transparent conductive laminate of comparative example B1 is excellent in slipperiness, but the haze characteristics when the pressure-sensitive adhesive layer and the transparent substrate B are laminated in this order are poor due to light scattering caused by the inorganic fine particles. The transparent conductive laminate of comparative example B2 has excellent haze properties when the pressure-sensitive adhesive layer and the transparent substrate B are laminated in this order, but has poor slipperiness because the surface of the cured resin layer is flat.

Description of the symbols

1. 1 ', 1' transparent organic polymer substrate

2. 2 ', 2' transparent conductive layer

3. 3 ', 3' cured resin layer having uneven surface

4. 4 ', 4' adhesive layer

5. 5 ', 5' No. 2 transparent substrate

6 base material (Plastic film)

7 adhesive layer

10. 20, 50 transparent conductive laminate

20' transparent conductive laminate (fixed electrode substrate)

20' transparent conductive laminate (movable electrode substrate)

30 temporary surface protective film

100 transparent touch panel

Claims (4)

1. A transparent conductive laminate comprising a transparent organic polymer substrate, a transparent conductive layer on one surface of the transparent organic polymer substrate, and a cured resin layer having an uneven surface on the other surface of the transparent organic polymer substrate,

the cured resin layer has a concave-convex surface formed from a coating composition containing at least 2 components that undergo phase separation due to differences in physical properties,

the cured resin layer does not contain inorganic fine particles and/or organic fine particles for forming an uneven surface, the arithmetic average roughness Ra of the uneven surface of the cured resin layer is 5nm or more and less than 500nm, and the ten-point average roughness Rz of the uneven surface of the cured resin layer is 50nm or more and less than 2000 nm.

2. The transparent conductive laminate according to claim 1, wherein a pressure-sensitive adhesive layer and a2 nd transparent substrate are laminated in this order on the uneven surface of the cured resin layer.

3. The transparent conductive laminate according to claim 1 or 2, wherein the same transparent conductive laminate as the transparent conductive laminate except that the reference cured resin layer having no haze is provided instead of the cured resin layer having the uneven surface is used as the reference transparent conductive laminate, the following relationship is satisfied:

-0.1<H1-H2<1.0

h1: haze value (%) of the transparent conductive laminate when a pressure-sensitive adhesive layer and a2 nd transparent substrate are laminated in this order on the uneven surface of the cured resin layer having an uneven surface,

h2: a haze value (%) of the reference transparent conductive laminate when the pressure-sensitive adhesive layer and the 2 nd transparent substrate are laminated in this order on a surface of the reference cured resin layer.

4. A transparent touch panel characterized in that 2 transparent electrode substrates each having a transparent conductive layer on at least one surface are arranged so that the transparent conductive layers face each other,

at least one of the 2 transparent electrode substrates has the transparent conductive laminate according to any one of claims 1 to 3.