JP2005116515A - Transparent conductive laminate and transparent touch panel - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transparent conductive laminate suitable for a transparent touch panel which is improved in writing durability (end pressing durability) in a transparent touch panel end region by improving the writing durability. <P>SOLUTION: The laminate is made of lamination in which two kinds of cured resin layers different in plastic deformation strength are laminated between a polymer film and a transparent conductive layer. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a transparent conductive laminate having a transparent conductive layer on a transparent organic polymer substrate and a transparent touch panel using the transparent conductive laminate. More specifically, a transparent conductive laminate suitable for a transparent touch panel, in which a cured resin layer-1, a cured resin layer-2, and a transparent conductive layer are sequentially laminated on a transparent organic polymer substrate, and the transparent conductive laminate. The present invention relates to a transparent touch panel using a body.

  In recent years, portable information terminals equipped with an information display terminal and a transparent touch panel for information input have begun to spread widely. A resistive touch panel, which is often used as a transparent touch panel, is composed of two transparent electrode substrates on which a transparent conductive layer is formed and is opposed to each other at an interval of about 10 μm to 100 μm. The surfaces of the transparent conductive layers are in contact with each other and operate as a switch. For example, menu selection on the display screen, figure / character input, and the like can be performed.

  Narrowing of the picture frame has progressed with liquid crystal displays and the like, and in the same way, narrowing of the picture frame has progressed for transparent touch panels. Along with the narrowing of the frame, in addition to the writing durability conventionally required for a transparent touch panel, the tendency to require writing durability (end pressing durability) at the end of the transparent touch panel has become stronger.

  In order to improve the writing durability required for the transparent touch panel, in Patent Document 1, Patent Document 2, and Patent Document 3, two transparent film base materials are adhesives or transparent materials that define the hardness (or Young's modulus). There has been proposed a transparent conductive laminate laminated through a resin layer. Although any method is known to improve writing durability, two transparent film substrates are laminated via an adhesive or transparent resin layer, which complicates the production process and lowers production efficiency. If a large-sized transparent touch panel exceeding 10 mm is produced, there is a problem that the transparent conductive laminate is bent because of the configuration in which two transparent film substrates are laminated.

  Further, Patent Document 4 proposes to provide a cushion layer having a specified hardness (dynamic hardness of 0.005 to 2) under the transparent conductive layer. However, in the above hardness range, a crystalline transparent conductive layer is provided. During the heat treatment to obtain, the cushion layer cannot support the volume change accompanying the crystallization of the transparent conductive layer, the haze of the transparent conductive laminate increases, and the transparent conductive laminate is whitened or interference pattern There is a problem that will be observed.

The transparent conductive film surface has a hardness of 0.4 to 0.8 GPa in a transparent conductive film obtained by sequentially laminating a cured product layer mainly composed of a curable resin on a transparent plastic film substrate and a transparent conductive layer. In Patent Document 5, the curable resin component is not specified and only the hardness of the surface of the transparent conductive layer is specified, so that a crack is generated in the cured product layer after the end press durability test, and the electrical characteristics of the transparent touch panel deteriorate. There is a problem. Furthermore, in Patent Document 6, a polymer film / stress relaxation layer / transparent conductive layer are sequentially laminated, and the thickness of the stress relaxation layer is 10 to 50 μm and the Vickers hardness is 38 to 240 N / mm ^2. Depending on the hardness of the stress relaxation layer that relaxes, the volume change accompanying the crystallization of the transparent conductive layer cannot be supported and fine wrinkles are formed on the surface of the transparent conductive layer, and an interference pattern is observed. There is also a problem that the haze increases. Furthermore, when the hardness of the conductive film is 1 GPa or more in a plastic laminate having a cured film layer between the plastic substrate layer and the conductive layer as in Patent Document 7, the cured film layer is cracked during the end-press durability test. There is a problem that the electrical characteristics (linearity) of the transparent touch panel deteriorates.

Japanese Patent Laid-Open No. 2-66809 JP-A-2-129808 JP-A-8-192492 JP-A-11-34206 JP 2002-163932 A JP 2004-158253 A Japanese Patent Laid-Open No. 11-286067

  The present invention provides a transparent conductive laminate for obtaining a transparent touch panel that has improved the writing durability conventionally required for a transparent touch panel, particularly the writing durability (end pressing durability) in the end region of the transparent touch panel. It is intended to do.

When a soft layer, for example, a layer having a plastic deformation hardness of less than 2.0 × 10 ⁸ Pa (20 kgf / mm ² ) is introduced between the transparent organic polymer substrate and the transparent conductive layer as described above, the soft layer Is difficult to support the volume change accompanying crystallization of the transparent conductive layer, and the haze of the transparent conductive laminate is increased, and whitening or interference patterns are observed in the transparent conductive laminate. On the other hand, when a hard layer (for example, a layer having a plastic deformation hardness exceeding 8.5 × 10 ⁸ Pa (85 kgf / mm ² )) is introduced, the transparent organic polymer substrate and the transparent conductive layer between the transparent organic polymer substrate and the end of the endurance durability test are used. Cracks occur in the hard layer, making it impossible to ensure the electrical characteristics of the transparent touch panel.

  Therefore, the present inventors, as a method for improving the end press durability as well as the writing durability required for the transparent touch panel, have two types of cured resin layers having different plastic deformation hardness and a transparent organic polymer substrate. It has been found that by adopting the technical idea of laminating between transparent conductive layers, the endurance durability is improved as well as the writing durability required for the transparent touch panel.

  Furthermore, by controlling the plastic deformation hardness and film thickness of the two types of cured resin layers laminated between the transparent organic polymer substrate and the transparent conductive layer, the volume change accompanying crystallization of the transparent conductive layer can be supported. It was also found that there was no haze change in the laminate, and the electrical properties of the transparent touch panel could be secured without cracks in the cured resin layer during the end-press durability test.

  According to the present invention, it has become possible to provide a transparent conductive laminate and a transparent touch panel that can ensure high reliability not only for writing durability required for a transparent touch panel but also for end-press durability.

That is, the present invention is as follows.
In the first invention, a cured resin layer-1 and a cured resin layer-2 having different plastic deformation hardness are sequentially laminated on at least one surface of a transparent organic polymer substrate, and a transparent conductive layer is formed on the cured resin layer-2. A transparent conductive laminate in which layers are laminated, wherein a thickness d ₁ of the cured resin layer- ₁ and a thickness d 2 of the cured resin layer- ₂ are 0.2 ≦ d ₂ / d ₁ ≦ 3. 0, and the film thickness satisfies ₁ μm ≦ d ₁ ≦ 10 μm, 1 μm ≦ d ₂ ≦ 10 μm, and further satisfies the relationship of HV ₂ > HV ₀ > HV ₁ and HV ₂ > HV ₃ > HV _1. A transparent conductive laminate. (However, the plastic deformation hardness of the transparent organic polymer substrate is HV ₀ , and the plastic deformation hardness when the cured resin layer-1 is formed on the transparent organic polymer substrate is measured as HV ₁ , the transparent organic polymer substrate. The plastic deformation hardness when the cured resin layer-2 is formed and measured is HV ₂ , and the plastic deformation when the cured resin layer-1 and the cured resin layer-2 are sequentially laminated on the transparent organic polymer substrate. Hardness is HV ₃ )

  The second invention is in contact with the transparent conductive layer between the cured resin layer-2 and the transparent conductive layer, and the film thickness is thinner than the transparent conductive layer, and the film thickness is 0.5 nm or more and less than 10.0 nm. It is a transparent conductive laminated body of 1st invention which has a metal compound layer which is.

In the third invention, the plastic deformation hardness HV ₁ is 9.8 × 10 ⁶ Pa ≦ HV ₁ ≦ 2.0 × 10 ⁸ Pa (1 kgf / mm ² ≦ HV ₁ ≦ 20 kgf / mm ² ), and the plastic deformation hardness is The transparent conductive laminate of the first or second invention, wherein the thickness HV ₂ is 5.9 × 10 ⁸ Pa ≦ HV ₂ ≦ 1.1 × 10 ⁹ Pa (60 kgf / mm ² ≦ HV ₂ ≦ 110 kgf / mm ² ) It is.

  4th invention is 1st-3rd in which the cured resin layer-1 contains 10 weight% or more of at least 1 sort (s) chosen from the group which consists of the cured resin which uses (A) urethane acrylate as a monomer, and (B) synthetic rubber. It is a transparent conductive laminate of any invention.

  In a fifth aspect of the present invention, there is provided a cured resin layer-3 having a refractive index of 1.20 to 1.55 and a film thickness of 0.05 to 0.5 μm between the cured resin layer-2 and the transparent conductive layer. It is a transparent conductive laminated body of the invention in any one of 1-4.

  6th invention contains the microparticles | fine-particles B whose average primary particle diameter is 1.1 times or more of the film thickness of the cured resin layer-3, and whose average primary particle diameter is 1.2 micrometers or less in this cured resin layer-3 In the transparent conductive laminate according to the first to fifth inventions, the content of the fine particles B is 0.5% by weight or less of the cured resin component forming the cured resin layer 3 containing the fine particles B.

  The seventh invention has an optical interference layer comprising at least one low refractive index layer and at least one high refractive index layer between the cured resin layer-2 and the transparent conductive layer, and the low refractive index layer is a metal. It is the transparent conductive laminated body of the invention in any one of 1st-4th which contact | connects a compound layer or a transparent conductive layer.

  According to an eighth aspect of the present invention, an average primary particle diameter of at least one of the high refractive index layer and the low refractive index layer forming the optical interference layer is 1.1 times or more of the film thickness of the optical interference layer and an average of 1 Fine particles B having a secondary particle size of 1.2 μm or less are contained, and the content of the fine particles B is 0.5 weight of the cured resin component forming the high refractive index layer and / or the low refractive index layer containing the fine particles B. % Of the transparent conductive laminate according to any one of the first, second, third, fourth and seventh inventions.

  9th invention is a transparent conductive layer of any one of the 1st-8th invention whose transparent conductive layer is a crystalline film | membrane which has indium oxide as a main component, and the film thickness of a transparent conductive layer is 5-50 nm. Is the body.

In a tenth aspect of the invention, the HV ₃ is further in the range of 2.0 × 10 ⁸ Pa ≦ HV ₃ ≦ 8.5 × 10 ⁸ Pa (20 kgf / mm ² ≦ HV ₃ ≦ 85 kgf / mm ² ). The transparent conductive laminate according to any one of the inventions. (The definition of HV ₃ is the same as above)

  According to an eleventh aspect of the present invention, there is provided a transparent touch panel in which two transparent electrode substrates each provided with a transparent conductive layer on at least one side are arranged so that the transparent conductive layers face each other. It is a transparent touch panel using the transparent conductive laminated body of 1st-10th invention.

  According to the present invention, two types of cured resin layers having different plastic deformation hardness are laminated between a transparent organic polymer substrate and a transparent conductive layer, and the plastic deformation hardness and film thickness of the two types of cured resin layers are controlled. As a result, the electrical characteristics of the transparent touch panel could be secured without any change in haze and without causing cracks in the cured resin layer during the end-press durability test.

  That is, according to the present invention, it is possible to provide a transparent conductive laminate and a transparent touch panel that can ensure high reliability not only for writing durability required for a transparent touch panel but also for end-press durability.

Hereinafter, the present invention will be described in detail.
<Laminated structure and coat layer plastic deformation hardness>
In the present invention, the cured resin layer-1 and the cured resin layer-2 having different plastic deformation hardness are sequentially laminated on the transparent polymer substrate. By laminating at least two cured resin layers having different plastic deformation hardness on the transparent polymer substrate, the characteristics of each cured resin layer, that is, the flexibility and low elasticity of the cured resin layer-1, the cured resin layer-2. Both toughness and high elasticity can be reflected, and it has become possible to improve the writing durability and end-press durability required for transparent touch panels in recent years.

Cured resin layer having plastic deformation hardness HV ₁ of 9.8 × 10 ⁶ Pa ≦ HV ₁ ≦ 2.0 × 10 ⁸ Pa (1 kgf / mm ² ≦ HV ₁ ≦ 20 kgf / mm ² ) on a transparent polymer substrate When only 1 is laminated and a transparent conductive layer is formed thereon, it is sufficient to provide the cured resin layer-1 as long as the damage to the transparent conductive layer due to external force is alleviated. However, since the plastic deformation hardness of the cured resin layer-1 is low, the cured resin layer-1 cannot support the transparent conductive layer, and is transparent when the transparent conductive layer is formed or after the transparent conductive layer is crystallized by heat treatment. The conductive layer becomes fine wrinkles. As a result, haze is generated, and whitening or interference patterns are observed in the transparent conductive laminate, which is not suitable as a transparent conductive laminate. In addition, when a transparent touch panel is made with such a transparent conductive laminate and a writing durability test is performed, the dot spacer provided on the fixed electrode is embedded in the transparent conductive layer of the transparent conductive laminate and destroys the transparent conductive layer. This is not suitable because the electrical characteristics (linearity) of the transparent touch panel deteriorate.

Further, a cured resin layer having a plastic deformation hardness HV ₂ of 5.9 × 10 ⁸ Pa ≦ HV ₂ ≦ 1.1 × 10 ⁹ Pa (60 kgf / mm ² ≦ HV ₂ ≦ 110 kgf / mm ² ) on the transparent polymer substrate. -2 is laminated and a transparent conductive layer is formed thereon, the plastic deformation hardness of the cured resin layer-2 is large, so that the transparent conductive layer is crystallized at the time of forming the transparent conductive layer as described above or by heat treatment. The transparent touch panel using the cured resin layer-2 does not have a problem of causing haze after being applied, but cracks occur in the cured resin layer-2 during the end-press durability test, and the electrical characteristics of the transparent touch panel (linearity) It is difficult to ensure.

Plastic deformation hardness HV ₃ is 2.0 × 10 8 ^Pa ≦ HV when are laminated successively at a predetermined thickness in the range in the cured resin layer-1 and the transparent polymer substrate and the cured resin layer-2 of the present invention preferably ^{_{3 ≦ 8.5 × 10 8 Pa (}} 20kgf / mm 2 ≦ HV 3 ≦ 85kgf / mm 2), more preferably _{^{2.0 × 10 8 Pa ≦ HV 3}} ≦ 6.9 × 10 8 Pa (20kgf / mm ² ≦ HV ₃ ≦ 70 kgf / mm ² ). When the cured resin layer-1 and the cured resin layer-2 are sequentially laminated on the transparent polymer substrate within the range of HV ₃ described above, the characteristics of the cured resin layer-1 and the cured resin layer-2 are sufficiently reflected. The various properties required for the transparent conductive laminate and the transparent touch panel can be sufficiently satisfied.

HV ₃ is 2.0 × 10 when the cured resin layer-1 and the cured resin layer-2 is formed by laminating a cured resin layer-2 and the cured resin layer-1 in a transparent polymer substrate in the range of predetermined thickness ^In the case of less than ⁸ Pa (20 kgf / mm ² ), the laminate of cured resin layer-1 and cured resin layer-2 indicates the transparent conductive layer when the transparent conductive layer is formed or after the transparent conductive layer is crystallized by heat treatment. The transparent conductive layer becomes a fine wrinkle pattern. As a result, haze is generated, which is not suitable as a transparent conductive laminate.

On the other hand HV ₃ in the case of the cured resin layer-1 and the cured resin layer-2 is formed by laminating a cured resin layer-2 and the cured resin layer-1 in a transparent polymer substrate in the range of a predetermined thickness is 8.5 When exceeding 10 ⁸ Pa (85 kgf / mm ² ), the endurance durability of the transparent touch panel using this as a transparent conductive laminate shall ensure the electrical characteristics (linearity) of the transparent touch panel due to the occurrence of cracks. I can't.

<Relationship of film thickness>
In the present invention, when the cured resin layer-1 and the cured resin layer-2 having different plastic deformation hardness are sequentially laminated on the transparent polymer substrate, the film thickness d1 of the cured resin layer- ₁ and the film of the cured resin layer-2. The thickness d ₂ is preferably 0.2 ≦ d ₂ / d ₁ ≦ 3, more preferably 0.25 ≦ d ₂ / d ₁ ≦ 2, and the thickness of each layer is 1 μm ≦ d ₁ ≦ 10 μm, 1 μm. ≦ d ₂ ≦ 10 μm. _d 2 _/ d 1 <If the cured resin layer-2 and the cured resin layer-1 in relation to _0.2 was laminated to the transparent organic polymer substrate, the film thickness of the cured resin layer-2 is the cured resin layer-1 Therefore, the plastic deformation hardness after lamination of the cured resin layer-1 and the cured resin layer-2 is reduced, and the transparent conductive layer is cured when formed or after the transparent conductive layer is crystallized by heat treatment. The laminate of the resin layer-1 and the cured resin layer-2 cannot support the transparent conductive layer, and the transparent conductive layer has a fine wrinkle pattern. As a result, haze is generated, which is not suitable as a transparent conductive laminate.

On the other hand, _d 2 _/ d 1> ₃ when a laminate of cured resin layer-2 and the cured resin layer-1 in the transparent organic polymer substrate in relation film thickness of the cured resin layer-2 is a cured resin layer - Since the thickness of the cured resin layer-1 and the cured resin layer-2 does not appear, the plastic deformation hardness after the lamination is the same as the plastic deformation hardness of the cured resin layer-2. . The endurance durability of the transparent touch panel using this transparent conductive laminate is similar to that of the transparent touch panel prepared by laminating only the cured resin layer-2 on the transparent organic polymer substrate, and the cured resin layer-2 has cracks. The electrical characteristics (linearity) of the generated transparent touch panel cannot be ensured.
If d ₁ and d ₂ are less than 1 μm, it is not preferable because of the problem of curability of the cured resin layer.

<Relationship of plastic deformation hardness>
Plastic deformation hardness HV 0 of the transparent organic polymer substrate in the present _invention, the cured resin layer-1 plastic deformation hardness HV 1 alone _layer, cured resin layer-2 alone layer plastic deformation hardness HV 2 of _a transparent organic high curing the molecule on the substrate resin layer-1, each of the plastic deformation hardness HV ₃ when the cured resin layer-2 are sequentially _{stacked, HV 2>} HV 0> of _{HV 1, HV 2> HV 3} > HV 1 There is a relationship. As an example of plastic deformation hardness HV ₀ by an indentation hardness tester (nanoindentation tester / set indentation depth: 0.5 μm) of a transparent organic polymer substrate, a polyethylene terephthalate film (Teijin DuPont Film Co., Ltd.) having a thickness of 188 μm ) OFF) is 5.4 × 10 ⁸ Pa (55 kgf / mm ² ), 100 μm polycarbonate film (Pure Ace manufactured by Teijin Chemicals Ltd.) is 2.4 × 10 ⁸ Pa (24 kgf / mm ² ), etc. . When the plastic deformation hardness of the cured resin layer-1 is larger than that of the transparent organic polymer substrate (HV ₀ <HV ₁ ), the transparent conductive laminate obtained by laminating the cured resin layer-1 and the cured resin layer-2. It is difficult to ensure electrical characteristics (linearity) after an end-press durability test of a transparent touch panel produced using a body. Further, when the plastic deformation hardness of the cured resin layer-2 is smaller than that of the transparent organic polymer substrate (HV ₀ > HV ₂ ), the cured resin layer-2 cannot support the transparent conductive layer, and the transparent conductive layer is formed. At times or after the transparent conductive layer is crystallized by heat treatment, the transparent conductive layer becomes fine wrinkles. As a result, haze is generated, which is not suitable as a transparent conductive laminate.

When the cured resin layer-1 and the cured resin layer-2 are laminated with the above film thickness settings (0.2 ≦ d ₂ / d ₁ ≦ 3, 1 μm ≦ d ₁ ≦ 10 μm, 1 μm ≦ d ₂ ≦ 10 μm), HV ₂ > HV ₃ > HV ₁ When the thickness of the cured resin layer-1 is thin and the thickness of the cured resin layer-2 is thick, the relationship between the plastic deformation hardness is HV ₂ ≈HV ₃ . On the other hand, when the laminated thin film thickness of thick cured resin layer-2 the thickness of the cured resin layer-1, the relationship of the plastic deformation hardness becomes HV ₃ ≒ HV _1. In these cases, when the cured resin layer-1 or the cured resin layer-2 described above is formed on a transparent organic polymer substrate alone, it is in a close state, and it is difficult to ensure the characteristics of the transparent conductive laminate or the transparent touch panel. It becomes.

The plastic deformation hardness HV ₁ of the cured resin layer- ₁ and the plastic deformation hardness HV ₂ of the cured resin layer-2 described in the present specification are a transparent organic polymer substrate (polyethylene terephthalate film having a thickness of 188 μm (Teijin DuPont). After forming the cured resin layer-1 or the cured resin layer-2 with a thickness of 5 μm on the film (OFW), a plastic deformation hardness tester (nanoindentation tester / set indentation depth) : 0.5 μm).

<Description of cured resin layer-1>
The cured resin layer-1 used in the present invention comprises (A) a cured resin obtained by a curing reaction using urethane acrylate as a monomer component in order to obtain a prescribed plastic deformation hardness. (B) At least one of the synthetic rubbers is contained. (A) The cured resin using such urethane acrylate or (B) the synthetic rubber preferably contains at least one of them in the cured resin layer-1 in an amount of 10% by weight or more, more preferably 20% by weight or more. . (A) and (B) may be used alone or in combination to form the cured resin layer-1. When the contents of (A) and (B) are less than 10% by weight, it is difficult to obtain a specified plastic deformation hardness.

A cured resin layer-1 having a thickness of 5 μm is formed on a transparent organic polymer substrate (polyethylene terephthalate film having a thickness of 188 μm (OFW manufactured by Teijin DuPont Films Ltd.)), and an indentation hardness tester (nanoindentation tester / setting) The plastic deformation hardness when measured at an indentation depth of 0.5 μm is 9.8 × 10 ⁶ Pa ≦ HV ₁ ≦ 2.0 × 10 ⁸ Pa (1 kgf / mm ² ≦ HV ₁ ≦ 20 kgf / mm ² ). And more preferably 9.8 × 10 ⁶ Pa ≦ HV ₁ ≦ 1.5 × 10 ⁸ Pa (1 kgf / mm ² ≦ HV ₁ ≦ 15 kgf / mm ² ). If the plastic deformation hardness HV ₁ of the cured resin layer-1 is less than 1 kgf / mm ^2, it is difficult to laminate for the soft cured resin layer cured resin layer-2. On the other hand, when the plastic deformation hardness HV ₁ of the cured resin layer- ₁ exceeds 2.0 × 10 ⁸ Pa (20 kgf / mm ² ), the difference from the plastic deformation hardness HV ₂ of the cured resin layer-2 becomes small. In a transparent touch panel using such a transparent conductive laminate, it is difficult to ensure electrical characteristics (particularly end pressing durability).
The film thickness of the cured resin layer-1 is preferably ₁ μm ≦ d ₁ ≦ 10 μm, more preferably 3 μm ≦ d ₁ ≦ 10 μm.

  The urethane acrylate used as the monomer is obtained by reacting a polyol such as a diol with a polyfunctional isocyanate such as diisocyanate and then sealing the end with a hydroxy functional acrylate. Examples of the polyol include polyether polyol, polyester polyol, hydrocarbon polyol and the like. Copolymers of these polyols may be used, or these polyols may be used alone or in combination. The number average molecular weight of the polyol is preferably about 200 to 10,000, more preferably 500 to 5,000. When the number average molecular weight of the polyol is less than 200, the plastic deformation hardness of the formed cured resin layer becomes large, making it difficult to obtain a predetermined cured resin layer, and further ensuring the electrical characteristics necessary for the transparent touch panel. It becomes difficult. Furthermore, when the number average molecular weight of the polyol exceeds 10,000, the plastic deformation hardness of the formed cured resin layer becomes extremely small and processing becomes difficult. Furthermore, there may be a problem that the transparent conductive layer cannot be supported.

Examples of synthetic rubber include isoprene rubber, butadiene rubber, butyl rubber, ethylene propylene rubber, chloroprene rubber, epichlorohydrin rubber, acrylic rubber, urethane rubber, silicone rubber, fluorine rubber, styrene butadiene rubber, chlorosulfonated rubber, chlorinated polyethylene, Examples thereof include nitrile rubber, hydrogenated acrylonitrile butadiene rubber, polysulfide rubber, acrylate copolymer, and various synthetic latexes. These synthetic rubber block copolymers may be used, or these may be used alone or in combination.
Examples of cured resin components other than the urethane acrylate and synthetic rubber include ionizing radiation curable resins and thermosetting resins.

  Monomers and polyfunctional acrylates such as polyol acrylates, polyester acrylates, urethane acrylates other than those mentioned above, epoxy acrylates, modified styrene acrylates, melamine acrylates, silicon-containing acrylates, and the like can be given as monomers that give ionizing radiation curable resins. .

  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 hexaacrylate. And polyfunctional monomers such as dimethylol tricyclodecane diacrylate, tripropylene glycol triacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, epoxy-modified acrylate, urethane-modified acrylate, and epoxy-modified acrylate. Even if these are used independently, several types may be mixed and used, and depending on the case, hydrolysates of various alkoxysilanes may be added in appropriate amounts. When the resin layer is polymerized by ionizing radiation, an appropriate amount of a known photopolymerization initiator is added. Further, an appropriate amount of a photosensitizer may be added as necessary.

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

  Thermosetting resins include organosilane thermosetting resins using silane compounds such as methyltriethoxysilane and phenyltriethoxysilane as monomers, melamine thermosetting resins using etherified methylol melamine and the like, and isocyanates. System thermosetting resin, phenol type thermosetting resin, epoxy curable resin and the like. These curable resins may 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.

  As the diluting solvent, water, alcohol-based or hydrocarbon-based solvents such as ethanol, isopropyl alcohol, butanol, 1-methoxy-2-propanol, hexane, cyclohexane, ligroin and the like are preferable. When using synthetic rubber, it is preferable to use xylene, toluene, ketones such as methyl ethyl ketone, methyl isobutyl ketone and the like. In addition, polar solvents such as cyclohexanone, butyl acetate, and isobutyl acetate can also be used. These can be used alone or as a mixed solvent of two or more.

Examples of the method for forming the cured resin layer-1 include a method using a known coating machine such as a doctor knife, a bar coater, a gravure roll coater, a curtain coater, a knife coater, and a spin coater, a spray method, and a dipping method. As an actual coating method, the above-mentioned monomer compounds are dissolved in various organic solvents and coated on a transparent organic polymer substrate using a coating liquid whose concentration and viscosity are adjusted, followed by radiation irradiation and heat treatment. The method of hardening a layer by etc. is mentioned.
Further, in order to roughen the surface of the cured resin layer-1 or to adjust the hardness, fine particles having an average primary particle diameter of 0.001 μm or more and 5 μm or less are used alone, or the average primary particle diameter is different. Two or more kinds of fine particles may be combined and contained in the cured resin layer-1.

<Description of cured resin layer-2>
Examples of the cured resin layer-2 used in the present invention include ionizing radiation curable resins and thermosetting resins.
As the ionizing radiation curable resin, the same resin as the cured resin layer-1 can be used. However, it is important that the cured resin layer-2 has a higher plastic deformation hardness than the cured resin layer-1. That is, the plastic deformation hardness of the cured resin layer-2 is defined as follows.

A cured resin layer-2 having a thickness of 5 μm is independently formed on a transparent organic polymer substrate (polyethylene terephthalate film having a thickness of 188 μm (OFW manufactured by Teijin DuPont Films Ltd.)), and an indentation hardness tester (nanoindentation tester). -Plastic deformation hardness when measured at a set indentation depth: 0.5 μm is 5.9 × 10 ⁸ Pa ≦ HV ₂ ≦ 1.1 × 10 ⁹ Pa (60 kgf / mm ² ≦ HV ₂ ≦ 110 kgf / mm) ²⁾ is preferably used, more preferably _{^{6.9 × 10 8 Pa ≦ HV 2}} ≦ 1.1 × 10 9 Pa (70kgf / mm 2 ≦ HV 2 ≦ 110kgf / mm 2). When the plastic deformation hardness HV 2 of the cured resin layer- ₂ exceeds 1.1 × 10 ⁹ Pa (110 kgf / mm ² ), there is no significant problem in characteristics, but the cured resin layer-1 and the cured resin layer-2 are transparent. There is a possibility that HV ₃ in the case where are laminated on a polymer substrate exceeds ^{8.5 × 10 8 Pa (85kgf /} mm 2), the transparent touch panel using such a transparent electroconductive laminate electrical characteristics (in particular, It becomes difficult to ensure end pushing durability. On the contrary, in the cured resin layer having a plastic deformation hardness HV ₂ of less than 5.9 × 10 ⁸ Pa (60 kgf / mm ² ), the difference from the plastic deformation hardness HV ₁ of the cured resin layer-1 In the transparent touch panel using such a transparent conductive laminate, it is difficult to ensure electrical characteristics (particularly end-press durability).
The film thickness of the cured resin layer-2 is preferably 1 μm ≦ d ₂ ≦ 10 μm, more preferably 2.5 μm ≦ d ₂ ≦ 8 μm.

  When both the movable electrode substrate surface and the fixed electrode substrate surface are flat, when a transparent touch panel is produced, Newton rings due to interference between reflected light from the movable electrode substrate surface and reflected light from the fixed electrode substrate surface are observed. Sometimes. In order to prevent Newton's ring by optically scattering the reflected light, the surface of the cured resin layer-1 or the cured resin layer-2 may be roughened. As a method for roughening the surface of the cured resin layer-1 or the cured resin layer-2, fine particles having a primary particle diameter of 0.001 μm or more and 5 μm or less are used alone, or two or more kinds having different primary particle diameters are used. Fine particles are combined and contained in the cured resin layer-1 or the cured resin layer-2. The preferable roughening range roughened by the above-mentioned method has a ten-point average roughness (Rz) defined by JIS B0601-1994 of the cured resin layer-2 of 100.0 nm or more and 400.0 nm or less, and The arithmetic average roughness (Ra) is 10.0 nm or more and 50.0 nm or less, and the haze defined by JIS B7361 is 5% or less.

<Transparent organic polymer substrate>
As the transparent organic polymer substrate used in the present invention, a film made of a thermoplastic or thermosetting organic polymer compound having excellent transparency can be used. Such an organic polymer compound is not particularly limited as long as it is a transparent organic 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. Is mentioned. Of course they can be used as homopolymers, copolymers, or alone or as a blend. These transparent organic polymer substrates are suitably formed by a general melt extrusion method or a solution casting method, etc., but the transparent organic polymer film formed is subjected to uniaxial stretching or biaxial stretching as necessary. It is also preferable to increase the mechanical strength or increase 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 as the substrate shape is from the point of strength to maintain flexibility and flatness for operating the transparent touch panel as a switch. A film shape of 75 to 400 μm is preferable. When used as a fixed electrode substrate, a sheet-shaped sheet having a thickness of 0.4 to 4.0 mm is preferable from the viewpoint of strength for maintaining flatness, but a film-shaped sheet having a thickness of 50 to 400 μm is used as another sheet. It is also possible to use a structure in which the total thickness is 0.4 to 4.0 mm. Or it is also possible to use it by the structure which stuck the film-form thing of thickness 50-400 micrometers on the display surface.

  When the transparent conductive laminate of the present invention is used as a movable electrode substrate of a transparent touch panel, the fixed electrode substrate is formed by forming a transparent conductive layer on the organic polymer film substrate, the glass substrate, or a laminate substrate thereof. May 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.

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

In such a type of transparent touch panel, since polarized light passes through the transparent conductive laminate, it is preferable to use a transparent organic polymer film having a property excellent in optical isotropy. Table in a slow axis direction of the refractive index _{n x,} the refractive index _{n y} in the fast axis direction, Re ₌ when the thickness of the substrate was set to _{d (nm) (n x -n} y) × d (nm) The in-plane retardation value Re is preferably at least 30 nm or less, and more preferably 20 nm or less. 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).

In the application of a transparent touch panel in which polarized light passes through the transparent conductive laminate exemplified above, the in-plane retardation value of the transparent electrode substrate is very important. original refractive index profile, namely in _{K = {(n x + n} y) / 2-n z} × K value represented by d is -250 + 150 nm when the film thickness direction of the refractive index of the substrate was _{n z} It is more preferable that it is in the range of −200 to +100 nm in order to obtain excellent viewing angle characteristics of the transparent touch panel.

  Examples of these transparent organic polymer substrates exhibiting excellent optical isotropy characteristics include polycarbonate, amorphous polyarylate, polyether sulfone, polysulfone, triacetyl cellulose, diacetyl cellulose, cycloolefin polymers, and these. Molded substrate formed by molding a modified product or copolymer with another material into a film shape, a molded substrate made of a thermosetting resin such as epoxy resin, or an ultraviolet curable resin such as an acrylic resin formed into a film or sheet A board | substrate etc. are illustrated. Molded substrates such as polycarbonate, amorphous polyarylate, polyether sulfone, polysulfone, cycloolefin polymer and their modified products or copolymers with different materials from the viewpoint of moldability, production cost, thermal stability, etc. Is most preferable.

  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), fluorene-9,9-di (3-methyl-4-phenol) and the like as a monomer unit Molding of polycarbonate or an average molecular weight in the range of about 15,000 to 100,000 (for example, “Panlite” manufactured by Teijin Chemicals Ltd., “Apec HT” manufactured by Bayer, etc.) A substrate is preferably used.

Examples of the amorphous polyarylate include molded substrates such as “Elmec” manufactured by Kaneka Chemical Co., Ltd., “U Polymer” manufactured by Unitika Co., Ltd., “Isalil” manufactured by Isonova, and the like.
Examples of the cycloolefin polymer include molded substrates such as “ZEONOR” manufactured by Nippon Zeon Co., Ltd. and “ARTON” manufactured by JSR Corporation.
Examples of the method for producing a molded substrate using these polymer compounds include methods such as a melt extrusion method, a solution casting method, and an injection molding method, but particularly from the viewpoint of obtaining excellent optical isotropy. It is preferable to perform molding using a solution casting method.

<Curing resin layer-3>
In the present invention, a cured resin layer-3 may be provided between the cured resin layer-2 and a transparent conductive layer described later in order to improve optical characteristics such as total light transmittance. Examples of the cured resin layer-3 used in the present invention include ionizing radiation curable resins and thermosetting resins.
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 thermosetting resins include organosilane thermosetting resins (alkoxysilane) such as methyltriethoxysilane and phenyltriethoxysilane, melamine thermosetting resins such as etherified methylol melamine, and isocyanate thermosetting resins. , Phenol-based thermosetting resins, epoxy-based curable resins, and the like. These curable resins may 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.

  The alkoxysilane forms a cured resin layer by hydrolysis and condensation polymerization. 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, γ-aminopropyltriethoxysilane, and the like. .

  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 layer 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 layer with actinic rays such as ultraviolet rays in parallel with the heat treatment.

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

As a method for forming the cured resin layer-3, the same method as that for the cured resin layer-1 can be used.
In order to adjust the refractive index of the cured resin layer-3, an ultrafine particle C or a fluorine-based resin composed of a metal oxide or metal fluoride having an average primary particle diameter of 100 nm or less alone or in combination, a cured resin You may mix | blend in layer-3. The refractive index of the cured resin layer-3 is smaller than the refractive index of the cured resin layer-2, and the refractive index is preferably 1.20 to 1.55, more preferably 1.20 to 1.45. . The thickness of the cured resin layer-3 is preferably 0.05 to 0.5 μm, and 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, the cured resin layer-3 can be obtained with good optical characteristics without being whitened.

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 other metal oxides or ultra-fine particles of metal fluoride are exemplified, preferably MgF ₂ , SiO _2, etc. Metal oxide or metal fluoride ultrafine particles having a refractive index of 1.55 or less.

  The content of the ultrafine particles C is 10 to 400 parts by weight, preferably 30 to 400 parts by weight, 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. . If the content of the ultrafine particles C exceeds 400 parts by weight, the film strength and adhesion may be insufficient. On the other hand, if the content of the ultrafine particles is less than 10 parts by weight, a predetermined refractive index may not be obtained. is there.

  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 The thing containing 5-70 weight% of monomer components which have fluorine atoms, such as fluoromethacrylic acid, is illustrated.

  The content of the fluororesin is 50 to 300 parts by weight, preferably 100 to 300 parts by weight, and 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. . If the fluorine resin content exceeds 300 parts by weight, the film strength and adhesion may be insufficient. On the other hand, if the fluorine resin content is less than 50 parts by weight, a predetermined refractive index may not be obtained. is there.

<Optical interference layer>
In the present invention, an optical interference layer can be provided between the cured resin layer-2 and a transparent conductive layer described later in order to control the refractive index and enhance transparency.
The optical interference layer used in the present invention is composed of at least one high refractive index layer and at least one low refractive index layer. Two or more combination units of the high refractive index layer and the low refractive index layer may be used. When the optical interference layer is composed of one high refractive index layer and one low refractive index layer, the thickness of the optical interference layer is preferably 30 nm to 300 nm, and more preferably 50 nm to 200 nm.

  The high refractive index layer constituting the optical interference layer of the present invention is a layer formed by hydrolysis and condensation polymerization of a metal alkoxide, or a component formed by hydrolysis and condensation polymerization of at least one metal alkoxide and This is a layer composed of ultrafine particles C of metal oxide or metal fluoride having an average primary particle size of 100 nm or less as described in cured resin layer-3.

Examples of the metal alkoxide used in the present invention include titanium alkoxide, zirconium alkoxide, and alkoxysilane.
Examples of the titanium alkoxide include titanium tetraisopropoxide, tetra-n-propyl orthotitanate, titanium tetra-n-butoxide, and tetrakis (2-ethylhexyloxy) titanate.
Examples of the zirconium alkoxide include zirconium tetraisopropoxide and zirconium tetra-n-butoxide.
Examples of the alkoxysilane include those described in the cured resin layer-3.

  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 oxide or metal fluoride described in the cured resin layer-3, are added singly or in appropriate amounts. be able to. It is possible to adjust the refractive index of the high refractive index layer by adding the ultrafine particles C.

  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 66.6: 33.3, more preferably 0: 100. ~ 60: 40. When the weight ratio between the ultrafine particles C and the metal alkoxide exceeds 66.6: 33.3, 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 a low refractive index layer constituting the optical interference layer of the present invention, a layer made of an ionizing radiation curable resin or a thermosetting resin described in the curable resin layer-3, and a layer made of these layers to the curable resin layer-3. The ultrafine particles C having an average primary particle diameter of 100 nm or less, which are made of the described metal oxides or metal fluorides, can be used singly or in a suitable amount. The thickness of the low refractive index layer is preferably 15 to 250 nm, more preferably 30 to 150 nm.

<Fine particle B>
Fine particles B may be contained in at least one of the cured resin layer-3 or the high refractive index layer and the low refractive index layer constituting the optical interference layer. In the case of the cured resin layer-3, fine particles B having an average primary particle diameter of 1.1 times or more of the film thickness and an average primary particle diameter of 1.2 μm or less are used in the case of the optical interference layer. Fine particles B having an average primary particle diameter of 1.1 times or more of the total film thickness of the optical interference layer and an average primary particle diameter of 1.2 μm or less are used. As a result, the surface of the transparent conductive layer is roughened, and it is possible to suppress malfunction due to a sticking phenomenon between the transparent conductive layer surface of the fixed electrode substrate and the transparent conductive layer surface of the movable electrode substrate. Further, by controlling the average primary particle size of the fine particles B to be added, the surface of the transparent conductive layer can be roughened in a range in which glare due to scattering of RGB primary color light emitted from the liquid crystal does not occur.

Further, the amount of the fine particles B added is in the range of 0.01 to 0.5% by weight of the cured resin component constituting the layer to which the fine particles B are added, thereby fixing the surface of the movable electrode substrate to the transparent conductive layer. A good optical interference layer free from white turbidity can be formed without impairing the malfunction-suppressing effect of the transparent touch panel due to the sticking phenomenon with the transparent conductive layer surface of the electrode substrate. When the fine particles B are excessively added to the cured resin layer-3 or at least one of the high refractive index layer and the low refractive index layer constituting the optical interference layer, the added fine particles B can easily fall off, The adhesion between the interference layer or the cured resin layer-3 and the cured resin layer-2 may be reduced, and the writing durability required for the touch panel may be impaired.
Examples of the fine particles B include silica fine particles, crosslinked acrylic fine particles, and crosslinked polystyrene fine particles.

In the case of the cured resin layer-3, the average primary particle diameter of the fine particles B is 1.1 times or more of the film thickness and the average primary particle diameter is 1.2 μm or less. The average primary particle diameter of the fine particles B is 1.1 times or more of the total film thickness of the optical interference layer, and the average primary particle diameter is 1.2 μm or less. When the average primary particle diameter of the fine particles B is less than 1.1 times the film thickness of the cured resin layer-3 or the total film thickness of the optical interference layer, it is difficult to roughen the surface of the transparent conductive layer. is there. On the other hand, when the average primary particle diameter of the fine particles B exceeds 1.2 μm, a transparent touch panel using a transparent conductive laminate added with such fine particles is placed on a high-definition color liquid crystal screen, When the liquid crystal screen is observed through the screen, the liquid crystal screen looks glaring and the display quality is degraded. Further, when the average primary particle diameter of the fine particles B exceeds 1.2 μm, the average primary particle diameter is larger than the film thickness of the cured resin layer-3 to which the fine particles B are added or the total film thickness of the optical interference layer. Since it becomes extremely large, the added fine particles easily fall off, and it becomes difficult to ensure the reliability such as writing durability required for the transparent touch panel.
When the fine resin B is contained in the cured resin layer-3 or at least one of the high refractive index layer and the low refractive index layer constituting the optical interference layer, the cured resin layer-2 may contain substantially no fine particles. preferable.

<Metal compound layer>
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 also be used, but the sputtering method is desirable from the viewpoint of film thickness control. .

  As a target used for sputtering, a metal target is preferably used, and a reactive sputtering method is widely employed. This is because 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 desirably 2 × 10 ⁻⁵ Pa or less.

As the inert gas introduced next, for example, He, Ne, Ar, Kr, and Xe can be used, 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 film, 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 first 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 lower, and more desirably 20 ° C. or lower. 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 further desirably 20 ° C. or lower from the viewpoint of controlling outgas from the polymer film. desirable.

<Transparent conductive layer>
In the present invention, a transparent conductive layer is provided in contact with the cured resin layer-2 or the cured resin layer-3, the optical interference layer, or the metal compound layer. By providing the transparent conductive layer in contact with the cured resin layer-2, mechanical properties such as writing durability of the transparent conductive laminate are improved. Here, examples of the transparent conductive layer include an ITO film containing 2 to 20% by weight of tin oxide and a tin oxide film doped with antimony or fluorine. As a method for forming the transparent conductive layer, there are a PVD method such as a sputtering method, a vacuum deposition method, and an ion plating method, a coating method, a printing method, and a CVD method, and 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 10 nm, the resistance value tends to be inferior in stability over time, and if it exceeds 30 nm, the transmittance of the transparent conductive laminate is undesirably reduced. The surface resistance value is 100 to 2000Ω / □ (Ω / sq) at a film thickness of 10 to 30 nm, more preferably 140 to 2000Ω / □ (Ω / sq) due to reduction of power consumption of the transparent touch panel and necessity for circuit processing. It is preferable to use a transparent conductive layer exhibiting the above range. Further, a film made mainly of crystalline (substantially 100% crystal phase) indium oxide is more preferable as the transparent conductive layer. In particular, a layer composed mainly of crystalline indium oxide having a crystal grain size of 3000 nm or less is preferably used. 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 region of polygonal or oval crystal grains observed under a transmission electron microscope (TEM).

<Hard coat layer>
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 during operation of the transparent touch panel, that is, on the surface of the transparent organic polymer substrate opposite to the transparent conductive layer. It is preferable to provide it. Materials for forming the hard coat layer include organosilane thermosetting resins such as methyltriethoxysilane and phenyltriethoxysilane, melamine thermosetting resins such as etherified methylolmelamine, polyol acrylate, polyester acrylate There are polyfunctional acrylate ultraviolet curable resins such as urethane acrylate and epoxy acrylate, and a mixture of ultrafine particles such as SiO ₂ and MgF ₂ can be used as necessary. 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-mentioned compound is dissolved in various organic solvents, and after coating on a transparent organic polymer substrate 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 organic polymer substrate or via an appropriate anchor layer. Examples of such an anchor layer include various layers 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 with a negative K value. Preferred are a phase compensation layer, a layer having a function of preventing the transmission 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 the substrate. Can be mentioned.

  Hereinafter, although the specific example of this invention is given and demonstrated, this invention is not limited to this. In the following examples, the plastic deformation hardness measurement method, linearity measurement method, writing durability test method, and end press durability test method using an indentation hardness tester are as follows.

<Measurement of plastic deformation hardness by indentation hardness tester>
The plastic deformation hardness was measured using the following measuring apparatus and measurement conditions.
Measuring apparatus: Nanoindentation tester ENT-1100a (manufactured by Elionix)
Measurement surface: The cured resin layer surface is measured.
Measurement condition Indentation depth setting test Setting depth 0.5μm
Divided into 250 steps Test load retention time 1 second Working indenter Triangular pyramid (Ridge interval 115 °)
5-point continuous automatic measurement for each sample Plastic deformation hardness calculation method From the load-displacement graph, the following formula is used to calculate the average value of the plastic deformation hardness of the 5-point continuous measurement. The tangent at the maximum displacement of the curve at the time of unloading was obtained, and the amount of plastic deformation was separated from the slope to obtain the hardness equivalent to Vickers hardness. The actual Vickers value varies slightly depending on the shape of the indenter.

Ｐｍａｘ：荷重
ｈｒ：除荷の際の、曲線の最大変位における接線の荷重０の際の変位

Pmax: Load hr: Displacement when the tangential load is 0 at the maximum displacement of the curve during unloading

<Method for measuring film thickness of metal compound layer>
After forming the metal compound layer, the film thickness of the metal compound layer was measured using a fluorescent X-ray analyzer RIX1000 (manufactured by Rigaku Corporation).

<Linearity measurement method>
A DC voltage of 5 V is applied between the parallel electrodes on the movable electrode substrate or the fixed electrode substrate. The voltage is measured at intervals of 5 mm in the direction perpendicular to the parallel electrodes. If the voltage at the measurement start position A is E _A , the voltage at the measurement end position B is E _B , the measured voltage value E _{X at} a distance X from A, the theoretical value is E _T , and the linearity is L,
_{E T = (E B -E A} ) × X / (B-A) + E A
_{L (%) = (| E} T -E X |) / (E B -E A) × 100

<End push durability test method>
Using a polyacetal pen with a tip of 0.8R parallel to the insulating layer at a position of about 2 mm from the insulating layer around the movable electrode substrate of the manufactured transparent touch panel, writing is performed 100,000 times in a straight line with a load of 450 g ( End push durability test). Measure the linearity of the transparent touch panel before and after the end push durability test. NG was defined as a linearity change amount of 1.5% or more before and after the end push durability test.

<Writing durability test method>
Using the polyacetal pen with the tip of 0.8R in the diagonal direction at the center of the movable electrode substrate of the transparent touch panel that was prepared, write a linear reciprocation 100,000 times with a 450g load (writing durability test), writing durability test Measure the linearity of the front and rear transparent touch panels. A transparent touch panel with a linearity change amount of 1.5% or more before and after the writing durability was determined as NG.

[Example 1]
UV curable polyfunctional acrylate on one side of a 188 μm thick polyethylene terephthalate film (OFW manufactured by Teijin DuPont Films Ltd., plastic deformation hardness by indentation hardness tester 5.4 × 10 ⁸ Pa (55 kgf / mm ² )) A hard coat layer 1 having a thickness of 4 μm was formed using a resin paint.

100 parts by weight of urethane acrylate Aronix M1200 (manufactured by Toagosei Co., Ltd.) and 3 parts by weight of Irgacure 184 (manufactured by Ciba Specialty Chemicals) were dissolved in methyl isobutyl ketone (MIBK) to prepare a coating liquid A. The coating liquid A was coated on the surface opposite to the hard coat layer 1 by a bar coating method so as to have a film thickness after curing of 6.0 μm, and cured by irradiation with ultraviolet rays to form a cured resin layer-1 (a).
A sample for measuring the plastic deformation hardness of the cured resin layer-1 (a) (film thickness after curing: 5 μm) was prepared in the same manner, and the plastic deformation hardness was measured. The measured results are shown in Table-1.

A coating solution B was prepared by dissolving 100 parts by weight of tetrafunctional acrylate Aronix M400 (manufactured by Toagosei Co., Ltd.) and 3 parts by weight of Irgacure 184 (manufactured by Ciba Specialty Chemicals) in methyl isobutyl ketone (MIBK). Coating liquid B was coated on cured resin layer-1 (a) by a bar coating method so that the film thickness after curing was 4.0 μm, and was cured by irradiation with ultraviolet rays to form cured resin layer-2 (a). . The plastic deformation hardness after lamination of the cured resin layer-1 (a) and the cured resin layer-2 (a) was measured. The measured results are shown in Table 1.
A sample for measuring the plastic deformation hardness of the cured resin layer-2 (a) (film thickness after curing: 5 μm) was prepared by the same method, and the plastic deformation hardness was measured. The measured results are shown in Table-1.

  Next, γ-glycidoxypropyltrimethoxylane (“KBM403” manufactured by Shin-Etsu Chemical Co., Ltd.) and methyltrimethoxysilane (“KBM13” manufactured by Shin-Etsu Chemical Co., Ltd.) are mixed at a molar ratio of 1: 1, and an acetic acid aqueous solution ( The alkoxysilane was hydrolyzed by a known method according to pH = 3.0). N-β (aminoethyl) γ-aminopropylmethoxysilane (“KBM603” manufactured by Shin-Etsu Chemical Co., Ltd.) was added to the hydrolyzate of alkoxysilane thus obtained at a weight ratio of solid content of 20: 1. Further, dilution with a mixed solution of isopropyl alcohol and n-butanol was performed to prepare an alkoxysilane coating solution C.

  An alkoxysilane coating liquid C was coated on the cured resin layer-2 (a) by a bar coating method, and after baking at 130 ° C. for 2 minutes, a cured resin layer-3 (a) having a film thickness of 65 nm was produced. Further, an ITO layer is formed on this cured resin layer-3 (a) by sputtering using an indium oxide-tin oxide target having a composition of indium oxide and tin oxide of 95: 5 in a weight ratio of 98% and a filling density of 98%. A transparent conductive laminate to be an electrode substrate was produced. The thickness of the formed ITO layer was about 20 nm, and the surface resistance value 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 film. No haze change was observed in the movable electrode substrate before and after the heat treatment, and the surface resistance value after the ITO was crystallized was about 280Ω / □ (Ω / sq).

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 film was formed by the same method 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 film. The transparent touch panel of FIG. 1 was produced using the produced fixed electrode substrate and movable electrode substrate. The prepared transparent touch panel was subjected to a writing durability test and an end press durability test. Table 1 shows the linearity before and after the test.

[Example 2]
UV curable polyfunctional acrylate on one side of a 188 μm thick polyethylene terephthalate film (OFW manufactured by Teijin DuPont Films Ltd., plastic deformation hardness by indentation hardness tester 5.4 × 10 ⁸ Pa (55 kgf / mm ² )) A hard coat layer 1 having a thickness of 4 μm was formed using a resin paint.

The coating liquid A of Example 1 is coated on the surface opposite to the hard coat layer 1 by a bar coating method so that the film thickness after curing is 5.0 μm, and is cured by irradiation with ultraviolet rays to form a cured resin layer-1 (b). Formed.
The coating liquid B of Example 1 was coated on the cured resin layer-1 (b) by a bar coating method so that the film thickness after curing was 5.5 μm, and then cured by irradiation with ultraviolet rays to cure the cured resin layer-2 (b ) Was formed.
The plastic deformation hardness after the cured resin layer-1 (b) and the cured resin layer-2 (b) were laminated was measured. The measured results are shown in Table-1.

Tetrabutoxy titanate (“B-4” manufactured by Nippon Soda Co., Ltd.) was diluted with a mixed solvent of ligroin (grade manufactured by Wako Pure Chemical Industries, Ltd.) and butanol (grade manufactured by Wako Pure Chemical Industries, Ltd.). A coating liquid D was prepared.
In the coating liquid D, silica fine particles having an average primary particle size of 0.5 μm were mixed so as to be 0.3 parts by weight with respect to 100 parts by weight of tetrabutoxy titanate to prepare a coating liquid E.

The alkoxysilane coating liquid C used in Example 1 was mixed so that the mixing ratio of the solid contents of the coating liquid E and the coating liquid C was 70:30 to prepare a coating liquid F. The primary particle diameter coating liquid F was prepared by mixing the coating solution G as the 20nm of TiO2 ultrafine particles weight ratio of TiO ₂ ultrafine particles and the metal alkoxide becomes 30:70. On the surface of the cured resin layer-2 (b), the coating liquid G was coated by a bar coating method, and after baking at 130 ° C. for 2 minutes, a high refractive index layer having a film thickness of 55 nm was formed.

  The alkoxysilane coating liquid C is coated on the high refractive index layer by a bar coating method, and after baking at 130 ° C. for 2 minutes, a low refractive index layer having a film thickness of 65 nm is formed. An optical interference layer composed of layers was prepared. Further, an ITO layer is formed on the optical interference layer by sputtering using an indium oxide-tin oxide target having a composition of indium oxide and tin oxide of 95: 5 in a weight ratio of 98% and a transparent electrode serving as a movable electrode substrate. A conductive laminate was produced. The thickness of the formed ITO layer was about 20 nm, and the surface resistance value 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 film. No haze change was observed in the movable electrode substrate before and after the heat treatment, and the surface resistance value after the ITO was crystallized was about 280Ω / □ (Ω / sq).

  A fixed electrode substrate was produced in the same manner as in Example 1. The transparent touch panel of FIG. 2 was produced using the produced fixed electrode substrate and movable electrode substrate. The prepared transparent touch panel was subjected to a writing durability test and an end press durability test. Table 1 shows the linearity before and after the test.

[Example 3]
UV curable polyfunctional acrylate on one side of a 188 μm thick polyethylene terephthalate film (OFW manufactured by Teijin DuPont Films Ltd., plastic deformation hardness by indentation hardness tester 5.4 × 10 ⁸ Pa (55 kgf / mm ² )) A hard coat layer 1 having a thickness of 4 μm was formed using a resin paint.

75 parts by weight of acrylonitrile butadiene rubber Nipol1052J (manufactured by ZEON Corporation), 25 parts by weight of tetrafunctional acrylate Aronix M400 (manufactured by Toagosei Co., Ltd.), 3 parts by weight of Irgacure 184 (manufactured by Ciba Specialty Chemicals), toluene and methylisobutyl A coating liquid H was prepared by dissolving in a solvent having a ketone mixing ratio of 1: 1. The coating liquid H was coated on the surface opposite to the hard coat layer 1 by a bar coating method so that the film thickness after curing was 5.5 μm, and was cured by irradiation with ultraviolet rays to form a cured resin layer-1 (c).
A sample for measuring the plastic deformation hardness of the cured resin layer-1 (c) (film thickness after curing: 5 μm) was prepared by the same method, and the plastic deformation hardness was measured. The measured results are shown in Table-1.

  The coating liquid B used in Example 1 was coated on the cured resin layer-1 (c) by a bar coating method so that the film thickness after curing was 4.5 μm, and was cured by irradiation with ultraviolet rays to be cured resin layer-2. (C) was formed. The plastic deformation hardness after lamination of the cured resin layer-1 (c) and the cured resin layer-2 (c) was measured. The measured results are shown in Table 1.

  After coating the coating liquid C used in Example 1 on the cured resin layer-2 (c) by a bar coating method and baking at 130 ° C. for 2 minutes, a cured resin layer-3 (c) having a film thickness of 65 nm is obtained. Produced. Further, an ITO layer is formed on the cured resin layer-3 (c) by sputtering using an indium oxide-tin oxide target having a composition of indium oxide and tin oxide of 95: 5 in a weight ratio of 98% and a filling density of 98%. A transparent conductive laminate to be an electrode substrate was produced. The thickness of the formed ITO layer was about 20 nm, and the surface resistance value 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 film. No haze change was observed in the movable electrode substrate before and after the heat treatment, and the surface resistance value after the ITO was crystallized was about 280Ω / □ (Ω / sq).

  A fixed electrode substrate was produced in the same manner as in Example 1. The transparent touch panel of FIG. 1 was produced using the produced fixed electrode substrate and movable electrode substrate. The prepared transparent touch panel was subjected to a writing durability test and an end press durability test. Table 1 shows the linearity before and after the test.

[Example 4]
Thickness using a UV curable polyfunctional acrylate resin coating on one side of a 188 μm thick polyethylene terephthalate film (OFW manufactured by Teijin DuPont Films Ltd., plastic deformation hardness 5.4 × 10 ⁸ Pa (55 kgf / mm ² )) A hard coat layer 1 having a thickness of 4 μm was formed.
Synthetic latex NipolLX857X2 (manufactured by Nippon Zeon Co., Ltd.) was applied to the opposite surface of the hard coat layer 1 and dried at 100 ° C. for 2 minutes to form a cured resin layer-1 (d) having a thickness of 6.0 μm. A sample for measuring the hardness of the cured resin layer-1 (d) (film thickness after drying: 5 μm) was prepared in the same manner, and the hardness was measured. The measured results are shown in Table 1.

  The coating liquid B used in Example 1 was coated on the cured resin layer-1 (d) by a bar coating method so that the film thickness after curing was 4.5 μm, and was cured by irradiation with ultraviolet rays to be cured resin layer-2. (D) was formed. Hardness measurement after lamination of cured resin layer-1 (d) and cured resin layer-2 (d) was performed. The measured results are shown in Table 1.

  After forming the optical interference layer in the same manner as in Example 2, a SiOx layer was formed by sputtering using a Si target on the low refractive index layer of the optical interference layer. The thickness of the formed SiOx layer was about 2.0 nm. Next, an ITO layer is formed on the SiOx layer by sputtering using an indium oxide-tin oxide target having a composition of indium oxide and tin oxide with a weight ratio of 97: 3 and a packing density of 98%. A laminate was produced. The thickness of the formed ITO layer was about 20 nm, and the surface resistance value after film formation was about 550Ω / □ (Ω / sq). The manufactured movable electrode substrate was heat-treated at 150 ° C. for 60 minutes to crystallize the ITO film. No haze change was observed on the movable electrode substrate before and after the heat treatment, and the surface resistance value after the ITO was crystallized was about 450Ω / □ (Ω / sq).

  A fixed electrode substrate was produced in the same manner as in Example 1. The transparent touch panel of FIG. 4 was produced using the produced fixed electrode substrate and movable electrode substrate. The prepared transparent touch panel was subjected to a writing durability test and an end press durability test. Table 1 shows the linearity before and after the test.

[Comparative Example 1]
UV curable polyfunctional acrylate resin on one side of 188 μm thick polyethylene terephthalate film (OFW manufactured by Teijin DuPont Films Ltd., plastic deformation hardness by indentation hardness test 5.4 × 10 ⁸ Pa (55 kgf / mm ² )) A hard coat layer 1 having a thickness of 4 μm was formed using a paint.
The coating liquid A produced in Example 1 is coated on the surface opposite to the hard coat layer 1 by a bar coating method so as to have a film thickness after curing of 5.0 μm, and is cured by irradiation with ultraviolet rays to be cured resin layer-1 (e ) Was formed.

  After coating the coating liquid C produced in Example 1 on the cured resin layer-1 (e) by a bar coating method and baking at 130 ° C. for 2 minutes, a cured resin layer-3 (e) having a film thickness of 65 nm is formed. Produced. Further, an ITO layer is formed on this cured resin layer-3 (e) by sputtering using an indium oxide-tin oxide target having a composition of indium oxide and tin oxide of 95: 5 in a weight ratio of 98% and a filling density of 98%. A transparent conductive laminate to be an electrode substrate was produced. The thickness of the formed ITO layer was about 20 nm, and the surface resistance value after film formation was about 350 Ω / □ (Ω / sq). The manufactured movable electrode substrate was heat-treated at 150 ° C. for 90 minutes, but fine wrinkles entered the ITO layer and the haze of the movable electrode substrate increased (whitened).

[Comparative Example 2]
UV curable polyfunctional acrylate resin on one side of 188 μm thick polyethylene terephthalate film (OFW manufactured by Teijin DuPont Films Ltd., plastic deformation hardness by indentation hardness test 5.4 × 10 ⁸ Pa (55 kgf / mm ² )) A hard coat layer 1 having a thickness of 4 μm was formed using a paint.
The coating liquid B produced in Example 1 is coated on the surface opposite to the hard coat layer 1 by a bar coating method so that the film thickness after curing is 5.0 μm, and is cured by irradiation with ultraviolet rays to be cured resin layer-2 (f ) Was formed.

  After coating the coating liquid C produced in Example 1 on the cured resin layer-2 (f) by a bar coating method and baking at 130 ° C. for 2 minutes, a cured resin layer-3 (f) having a film thickness of 65 nm is formed. Produced. Further, an ITO layer is formed on this cured resin layer-3 (f) by sputtering using an indium oxide-tin oxide target having a composition of indium oxide and tin oxide of 95: 5 in a weight ratio of 98% and a filling density of 98%. A transparent conductive laminate to be an electrode substrate was produced. The thickness of the formed ITO layer was about 20 nm, and the surface resistance value 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 film. No haze change was observed in the movable electrode substrate before and after the heat treatment, and the surface resistance value after the ITO was crystallized was about 280Ω / □ (Ω / sq).

  A fixed electrode substrate was produced in the same manner as in Example 1. The transparent touch panel of FIG. 3 was produced using the produced fixed electrode substrate and movable electrode substrate. The prepared transparent touch panel was subjected to a writing durability test and an end press durability test. Table 1 shows the linearity before and after the test.

[Comparative Example 3]
UV curable polyfunctional acrylate resin on one side of 188 μm thick polyethylene terephthalate film (OFW manufactured by Teijin DuPont Films Ltd., plastic deformation hardness by indentation hardness test 5.4 × 10 ⁸ Pa (55 kgf / mm ² )) A hard coat layer 1 having a thickness of 4 μm was formed using a paint.

  Methyl 100 parts by weight of polyfunctional acrylate NK oligo U15HA (manufactured by Shin-Nakamura Chemical Co., Ltd.), 100 parts by weight of monofunctional acrylate Aronix TO-1429 (manufactured by Toagosei Co., Ltd.) and 10 parts by weight of Irgacure 184 (manufactured by Ciba Specialty Chemicals) A coating liquid I was prepared by dissolving in isobutyl ketone (MIBK). The coating liquid I was coated on the surface opposite to the hard coat layer 1 by a bar coating method so that the film thickness after curing was 4.0 μm, and was cured by irradiation with ultraviolet rays to form a cured resin layer-2 (g). Table 1 shows the results of measuring the Young's modulus and plastic deformation hardness of the produced cured resin layer-2 (g).

  After coating the coating liquid C produced in Example 1 on the cured resin layer-2 (g) by a bar coating method and baking at 130 ° C. for 2 minutes, a cured resin layer-3 (g) having a film thickness of 65 nm is obtained. Produced. Further, an ITO layer is formed on the cured resin layer-3 (g) 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 to be an electrode substrate was produced. The thickness of the formed ITO layer was about 20 nm, and the surface resistance value 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 film. No haze change was observed in the movable electrode substrate before and after the heat treatment, and the surface resistance value after the ITO was crystallized was about 280Ω / □ (Ω / sq).

  A fixed electrode substrate was produced in the same manner as in Example 1. The transparent touch panel of FIG. 3 was produced using the produced fixed electrode substrate and movable electrode substrate. The prepared transparent touch panel was subjected to a writing durability test and an end press durability test. Table 1 shows the linearity before and after the test.

[Comparative Example 4]
UV curable polyfunctional acrylate resin on one side of 188 μm thick polyethylene terephthalate film (OFW manufactured by Teijin DuPont Films Ltd., plastic deformation hardness by indentation hardness test 5.4 × 10 ⁸ Pa (55 kgf / mm ² )) A hard coat layer 1 having a thickness of 4 μm was formed using a paint.
The coating liquid A of Example 1 is coated on the surface opposite to the hard coat layer 1 by a bar coating method so that the film thickness after curing is 6.5 μm, and is cured by irradiation with ultraviolet rays to form a cured resin layer-1 (h). Formed.

  The coating liquid B of Example 1 was coated on the cured resin layer-1 (h) by a bar coating method so that the film thickness after curing was 1.0 μm, and was cured by irradiation with ultraviolet rays to cure the cured resin layer-2 (h ) Was formed. The plastic deformation hardness after lamination of the cured resin layer-1 (h) and the cured resin layer-2 (h) was measured. The measured results are shown in Table 1.

  After coating the coating liquid C produced in Example 1 on the cured resin layer-1 (h) by a bar coating method and baking at 130 ° C. for 2 minutes, a cured resin layer-3 (h) having a film thickness of 65 nm is formed. Produced. Further, an ITO layer is formed on the cured resin layer-3 (h) 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 to be an electrode substrate was produced. The thickness of the formed ITO layer was about 20 nm, and the surface resistance value after film formation was about 350 Ω / □ (Ω / sq). The manufactured movable electrode substrate was heat-treated at 150 ° C. for 90 minutes, but fine wrinkles entered the ITO layer and the haze of the movable electrode substrate increased (whitened).

[Comparative Example 5]
UV curable polyfunctional acrylate resin on one side of 188 μm thick polyethylene terephthalate film (OFW manufactured by Teijin DuPont Films Ltd., plastic deformation hardness by indentation hardness test 5.4 × 10 ⁸ Pa (55 kgf / mm ² )) A hard coat layer 1 having a thickness of 4 μm was formed using a paint.
The coating liquid A of Example 1 is coated on the surface opposite to the hard coat layer 1 by a bar coating method so that the film thickness after curing is 1.5 μm, and is cured by irradiation with ultraviolet rays to form a cured resin layer-1 (i). Formed.

  The coating liquid B of Example 1 was coated on the cured resin layer-1 (i) by a bar coating method so that the film thickness after curing was 6.0 μm, and was cured by irradiation with ultraviolet rays to cure the cured resin layer-2 (i ) Was formed. The plastic deformation hardness after lamination of the cured resin layer-1 (i) and the cured resin layer-2 (i) was measured. The measured results are shown in Table 1.

  After coating the coating liquid C produced in Example 1 on the cured resin layer-2 (i) by a bar coating method and baking at 130 ° C. for 2 minutes, a cured resin layer-3 (i) having a film thickness of 65 nm is formed. Produced. Further, an ITO layer is formed on the cured resin layer-3 (i) by sputtering using an indium oxide-tin oxide target having a composition of indium oxide and tin oxide of 95: 5 in a weight ratio of 98% and a filling density of 98%. A transparent conductive laminate to be an electrode substrate was produced. The thickness of the formed ITO layer was about 20 nm, and the surface resistance after film formation was about 350 Ω / □ (Ω / sq) (Ω / sq). The manufactured movable electrode substrate was heat-treated at 150 ° C. for 90 minutes to crystallize the ITO film. No haze change was observed on the movable electrode substrate before and after the heat treatment, and the surface resistance value after the ITO was crystallized was about 280Ω / □ (Ω / sq) (Ω / sq).

  A fixed electrode substrate was produced in the same manner as in Example 1. The transparent touch panel of FIG. 1 was produced using the produced fixed electrode substrate and movable electrode substrate. The prepared transparent touch panel was subjected to a writing durability test and an end press durability test. Table 1 shows the linearity before and after the test.

It is the schematic diagram showing the structure of the transparent touch panel produced in Example 1, 3 and the comparative example 5. FIG. 6 is a schematic diagram illustrating a configuration of a transparent touch panel manufactured in Example 2. FIG. It is the schematic diagram showing the structure of the transparent touch panel produced by the comparative examples 2 and 3. FIG. 6 is a schematic diagram illustrating a configuration of a transparent touch panel produced in Example 4. FIG.

Explanation of symbols

1 Hard Coat Layer 2 Polyethylene Terephthalate Film 3 Cured Resin Layer-1
4 cured resin layer-2
5 Cured resin layer-3
6 High refractive index layer 7 Low refractive index layer 8 Transparent conductive layer 9 Glass substrate 10 Metal compound layer

Claims (11)

A transparent resin layer-1 and a cured resin layer-2 having different plastic deformation hardness are sequentially laminated on at least one surface of the transparent organic polymer substrate, and a transparent conductive layer is laminated on the cured resin layer-2. a conductive laminate, the thickness _{d 1} and the thickness _{d 2} of the cured resin layer-2 of the cured resin layer-1 is in the relation of 0.2 ≦ _d 2 / _{d 1} ≦ 3.0, The film has a thickness of 1 μm ≦ d ₁ ≦ 10 μm, 1 μm ≦ d ₂ ≦ 10 μm, and further has a relationship of HV ₂ > HV ₀ > HV ₁ and HV ₂ > HV ₃ > HV ₁ Laminated body. (However, the plastic deformation hardness of the transparent organic polymer substrate is HV ₀ , and the plastic deformation hardness when the cured resin layer-1 is formed on the transparent organic polymer substrate is measured as HV ₁ , the transparent organic polymer substrate. HV ₂ is the plastic deformation hardness when measured by forming the cured resin layer-2 thereon, and the plastic deformation when the cured resin layer-1 and the cured resin layer-2 are sequentially laminated on the transparent organic polymer substrate. Hardness is HV ₃ )   Between the cured resin layer-2 and the transparent conductive layer, a metal compound layer in contact with the transparent conductive layer and having a thickness smaller than that of the transparent conductive layer and having a thickness of 0.5 nm or more and less than 10.0 nm. The transparent conductive laminate according to claim 1, comprising: When the cured resin layer-1 is formed on a transparent organic polymer substrate, the plastic deformation hardness HV ₁ is 9.8 × 10 ⁶ Pa ≦ HV ₁ ≦ 2.0 × 10 ⁸ Pa (1 kgf / mm ² ≦ HV ₁ ≦ 20 kgf / mm ² ), and the plastic deformation hardness HV ₂ when the cured resin layer-2 is formed on the transparent organic polymer substrate is 5.9 × 10 ⁸ Pa ≦ HV ₂ ≦ 1.1 × 10 The transparent conductive laminate according to claim 1 or 2, wherein ⁹ Pa (60 kgf / mm ² ≤ HV ₂ ≤ 110 kgf / mm ² ).   The transparent resin according to any one of claims 1 to 3, wherein the cured resin layer-1 contains 10% by weight or more of at least one selected from the group consisting of (A) a cured resin having urethane acrylate as a monomer and (B) a synthetic rubber. Conductive laminate.   5. The cured resin layer 3 having a refractive index of 1.20 to 1.55 and a film thickness of 0.05 to 0.5 μm between the cured resin layer 2 and the transparent conductive layer. The transparent conductive laminate according to 1.   The cured resin layer-3 contains fine particles B having an average primary particle diameter of 1.1 times or more of the film thickness of the cured resin layer-3 and an average primary particle diameter of 1.2 μm or less. The transparent conductive laminate according to claim 1, wherein the content of the fine particles B is 0.5% by weight or less of the cured resin component forming the cured resin layer 3.   There is an optical interference layer comprising at least one low refractive index layer and at least one high refractive index layer between the cured resin layer-2 and the transparent conductive layer, and the low refractive index layer is a metal compound layer or a transparent conductive layer. The transparent conductive laminate according to claim 1, which is in contact with the layer.   On at least one of the high refractive index layer and the low refractive index layer, fine particles B having an average primary particle size of 1.1 times or more of the film thickness of the optical interference layer and an average primary particle size of 1.2 μm or less. And the content of the fine particles B is 0.5% by weight or less of the cured resin component forming the high refractive index layer and / or the low refractive index layer containing the fine particles B. The transparent conductive laminate according to 4 or 7.   The transparent conductive laminate according to claim 1, wherein the transparent conductive layer is a crystalline film containing indium oxide as a main component, and the thickness of the transparent conductive layer is 5 to 50 nm. Further according to any one of claims 1 to 9 HV ₃ is in the range of _{^{2.0 × 10 8 Pa ≦ HV 3}} ≦ 8.5 × 10 8 Pa (20kgf / mm 2 ≦ HV 3 ≦ 85kgf / mm 2) Transparent conductive laminate. (The definition of HV ₃ is the same as above)   The transparent touch panel in which at least one transparent electrode substrate provided with a transparent conductive layer on at least one side is arranged so that the transparent conductive layers face each other, and at least one transparent electrode substrate according to claim 1. The transparent touch panel using the transparent conductive laminated body in any one.

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