WO2005036565A1 - Lamine conducteur transparent et ecran tactile transparent - Google Patents

Lamine conducteur transparent et ecran tactile transparent Download PDF

Info

Publication number
WO2005036565A1
WO2005036565A1 PCT/JP2004/015201 JP2004015201W WO2005036565A1 WO 2005036565 A1 WO2005036565 A1 WO 2005036565A1 JP 2004015201 W JP2004015201 W JP 2004015201W WO 2005036565 A1 WO2005036565 A1 WO 2005036565A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
transparent conductive
curable resin
transparent
conductive laminate
Prior art date
Application number
PCT/JP2004/015201
Other languages
English (en)
Japanese (ja)
Inventor
Haruhiko Ito
Hitoshi Mikoshiba
Isao Shiroishi
Original Assignee
Teijin Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2003349317A external-priority patent/JP2007042283A/ja
Priority claimed from JP2003365900A external-priority patent/JP2007042284A/ja
Application filed by Teijin Limited filed Critical Teijin Limited
Publication of WO2005036565A1 publication Critical patent/WO2005036565A1/fr

Links

Classifications

    • GPHYSICS
    • G06COMPUTING; CALCULATING OR COUNTING
    • G06FELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means

Definitions

  • the present invention relates to a transparent conductive laminate having a transparent conductive layer on a transparent organic polymer substrate, and to a transparent touch panel using the transparent conductive laminate. More specifically, a transparent conductive laminate suitable for a transparent touch panel and a transparent conductive laminate using the same.
  • Resistive transparent touch panels which are often used as transparent touch panels, consist of two transparent electrode substrates on which a transparent conductive layer is formed. They are arranged so that they face each other, and the surfaces of the transparent conductive layers come into contact with each other only at the part to which external force is applied to operate as a switch.For example, menu selection on the display screen, figure / character input, etc. It can be performed.
  • Japanese Patent Application Laid-Open No. 08-155,988, Japanese Patent Application Laid-Open No. H11-34207, and Japanese Patent Application Laid-Open No. H11-224,3939 require a transparent touch panel.
  • the material of the curable resin layer is not particularly specified, and only silicone acrylate, epoxy acrylate, and urethane acrylate are mentioned as examples.
  • Alkyl acrylate and alkyl methacrylate are cited as curable resin components in consideration of the adhesion between the crystalline transparent conductive layer and the transparent polymer substrate.
  • Japanese Patent Application Laid-Open No. 2002-169392 also discloses a transparent plastic film base in which a cured product layer mainly composed of a curable resin and a transparent conductive layer are sequentially laminated.
  • the hardness of the transparent conductive layer surface of the conductive film (transparent conductive laminate) is set to 0.
  • the curable resin component Although it is proposed to be 4 to 0.8 GPa, there is no particular designation of the curable resin component and only the hardness of the transparent conductive layer surface is specified.
  • the edge panel has a problem that cracks occur in the cured layer during the edge-pressing durability test, and the electrical characteristics of the transparent sunset panel deteriorate. Further, depending on the hardness of the cured product layer, the volume change accompanying crystallization of the transparent conductive layer cannot be supported, and fine wrinkles are formed on the transparent conductive layer surface, and an interference pattern is observed. There is also a problem that the haze of the film (transparent conductive laminate) increases.
  • the thickness between the transparent conductive layer and the polymer film is 10 to 50 urn, and the Vickers hardness is 38 to 24 ON / mm 2.
  • the transparent conductive layer when a crystalline transparent conductive layer is formed on a hardenable shelf layer that relieves external stress, as described above, the transparent conductive layer
  • An object of the present invention is to improve the writing durability conventionally required for a transparent touch panel, and at the same time, to improve the edge pressing durability, which is the writing durability in the edge region of the transparent touch panel. And to provide a transparent conductive laminate therefor.
  • a curable resin component at least one component selected from the group consisting of (A) a synthetic rubber component and (B) a resin component containing urethane acrylate as a monomer, and a metal having a primary particle diameter of 100 nm or less. At least one selected from the group consisting of the component (A) and the component (B) is 100 to 400 parts by weight of the curable resin component.
  • the sum of the components (A) and (B) is 10 to 400 parts by weight
  • the ultrafine particles C is 10 to 400 parts by weight
  • the indentation hardness tester (Nanoindentation The tester ⁇ Young's modulus W,) is 5.9 GPa ⁇ W x ⁇ 9.8 GPa (600 kgf / mm 2 ⁇ W ⁇ 1,000 kg) when measured at the set indentation depth: 0.5 m) f / mm 2 ) and the plastic deformation hardness (HVi) is 4.7 X 10 7 P a ⁇ ⁇ ⁇ ⁇ . 5 ⁇ 10 8 Pa (5kg f / mm ⁇ HV ⁇ S 5 kg f / mm 2 ) It is in the range,
  • the above object and the ij point of the present invention are:
  • FIG. 1 is a schematic diagram showing the configuration of the transparent touch panel created by the operations of Examples 1 and 5 and Comparative Examples 2, 3, 4, and 5.
  • FIG. 2 A schematic diagram showing the structure of the transparent touch panel created by the operations of Examples 2 and 6 is shown.
  • FIG. 3 is a schematic diagram showing a configuration of a transparent touch panel created by the operation of Comparative Example 1.
  • FIG. 4 is a schematic diagram showing the configuration of a transparent touch panel created by the operations of Examples 3 and 7.
  • FIG. 5 is a schematic diagram showing a configuration of a transparent uchipan panel manufactured by the operations of Examples 4 and 8. Explanation of symbols
  • the first curable resin layer is the resin layer specified in (1-1) or the resin layer specified in (1-2).
  • the first curable resin layer specified by the above (1-1) is made of a curable resin mainly containing (meth) acrylate of N-hydroxyalkyl isocyanuric acid.
  • Examples of the (meth) acrylate of N-hydroxyalkyl isocyanuric acid include a compound represented by the following formula (1).
  • R 2 is an alkylene group having 2 to 5 carbon atoms
  • R 3 is It is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • Examples of the alkyl group of the hydroxyalkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, and a propyl group.
  • R2 is an alkylene group having 2 to 5 carbon atoms. Examples of such an alkylene group include an ethylene group and a propylene group.
  • R 3 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Examples of such an alkyl group include a hydrogen atom and a methyl group.
  • the first hardening resin layer specified by (1-1) is mainly composed of (meth) acrylate of N-hydroxyalkyl isocyanuric acid represented by the above formula (1).
  • the moderate flexibility of the curable resin layer specified in (1-1) greatly contributes to the special effect of the present invention. That is, the (meth) acrylate of N-hydroxyalkyliso and nanuric acid represented by the above formula (1) can support an appropriate hardness, that is, a volume change accompanying the crystallization of the transparent conductive layer.
  • the first curable resin layer having the above hardness and appropriate flexibility can be formed.
  • the (meth) acrylate of N-hydroxyarylalkylisocyanuric acid represented by the above formula (1) may be used alone or in the hardening resin layer-1.
  • Other curable resin components described below other than the isocyanuric acid AO-modified acrylate may be mixed and used. Curing at the time of mixing
  • the isocyanuric acid A-modified acrylate contained in the ife resin layer is 50 to 100% by weight, preferably 60 to 100% by weight, and more preferably 70 to 100] _0. 0% by weight, particularly preferably 100% by weight.
  • the content of the isocyanuric acid AO-modified acrylate is less than 50% by weight, the flexibility of the formed curable resin layer is impaired depending on the foundation resin component to be mixed, and the end-push durability cannot be satisfied. In some cases, it may not be possible to support ⁇ : product change due to crystallization of the transparent conductive layer.
  • the method of forming the first curable resin layer specified in the above (111) includes: Dr. Naif, Nohko One, Gravure Roll Co., Curtain Co. One,! A method using a known coating machine, such as Spin Co., Ltd., etc., a spray method, an immersion method, etc. are used. A method of coating a transparent organic polymer substrate with a coating liquid having the above-mentioned temperature and controlling the cross-linking polymerization mainly by irradiation with ionizing radiation to form a curable shelf layer.
  • the film thickness of the first curable resin layer specified in (1-1) is 10 m or less, preferably 7 m or less, more preferably 5 m or less.
  • the thickness is preferably 0.5 m or more from the viewpoint that the isocyanuric acid AO-modified acrylate is easily cured.
  • the film thickness of the first hardening shelf layer specified in the above (1-1) exceeds 10 m, the workability may be deteriorated, which is not appropriate.
  • the indentation hardness tester (Nano Indentation Tester's set indentation depth: 0.5 m) was used to measure the hardening property of the first hardened shelving layer specified in (1-1).
  • the Young's modulus which is an index of the hardness of the resin layer 1
  • the Young's modulus which is an index of the hardness of the resin layer 1
  • the plastic deformation hardness which is an index of the flexibility of the first curable resin layer
  • the first curable resin layer has sufficient hardness but lacks flexibility, and therefore has the same transparent conductivity.
  • a sunset panel using a laminate is not suitable as the first curable resin layer because cracks occur in the first curable resin layer during the edge-durability test and the electrical characteristics of the transparent sunset panel cannot be satisfied.
  • Newton rings may be observed due to interference between reflected light from the electrode surface of the movable electrode substrate and reflected light from the electrode surface of the fixed electrode substrate.
  • the surface of the first layer may be roughened to optically scatter the reflected light to prevent the occurrence of double-ton's ring.
  • the curable shelf layer 1 roughened by the above method is formed, the ten-point average roughness (R z) defined by JISB 0601-1994 is 100 not less than nm and not more than 450 nm, and the arithmetic average roughness (R a ) is not less than 1 O nm and not more than 500 nm, and the haze defined by JISB 7361 is not more than 5%. .
  • an ionizing radiation-curable resin, a thermosetting resin, or the like can be used in combination as a hardening resin component other than the above-mentioned isocyanuric acid AO-modified acrylate.
  • Examples of the monomer that gives the ionizing radiation-curable resin include polyol acrylate J, polyester acrylate, urethane acrylate, epoxy acrylate, modified styrene acrylate, melamine acrylate, and silicon-containing acrylate. And monofunctional and polyfunctional acrylates.
  • Specific monomers include, for example, trimethyl monopropane trimethacrylate, trimethyl monopropane ethylene oxide modified triacrylate, trimethylolpropane propylene oxide modified triacrylate, Penyu erythritol triacrylate, dimethacrylate Pentaerythritol hexaacrylate, dimethylol tricyclide decane diacrylate, tripropylene dalicol triacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, epoxy-modified acrylate, urethane-modified acrylate, epoxy-modified atari And polyfunctional monomers such as a rate. These may be used alone or as a mixture of several types.
  • a hydrolyzate of various alkoxysilanes may be added in an appropriate amount.
  • a known photopolymerization initiator is added in an appropriate amount. If necessary, an appropriate amount of a photosensitizer may be added.
  • thermosetting resin an organosilane-based thermosetting resin using a silane compound such as methyltriethoxysilane or phenyltriethoxysilane as a monomer is used.
  • examples thereof include a melamine-based thermosetting resin, an isocyanate-based thermosetting resin, a phenol-based thermosetting resin, and an epoxy-based thermosetting resin.
  • thermoplastic resin it is also possible to mix a thermoplastic resin if necessary.
  • a reaction accelerator or curing agent is added.
  • the reaction accelerator include triethylenediamine, dibutyltin dilaurate, benzylmethylamine, pyridine and the like.
  • the curing agent include methylhexahydrophthalic anhydride, 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, diaminodiphenylesulfon, and the like.
  • the first curable resin layer specified in the above (1-2) comprises at least one of a curable resin component and (A) a synthetic rubber component or (B) a resin component containing urethane acrylate as a monomer. And ultrafine particles C of metal oxide or metal fluoride having a primary particle diameter of 100 nm or less.
  • each component in the first curable resin layer specified in the above (1-2) is 100 parts by weight of the curable resin component, (A) the synthetic rubber component and (B) the urethane resin.
  • at least one component selected from the group consisting of resin components having styrene as a monomer is 10 to 400 parts by weight, or the total of the components (A) and (B) is 10 to 400 parts by weight.
  • ultrafine particles C are 10 to 400 parts by weight.
  • the first curable resin layer has no flexibility.
  • the amount is more than 400 parts by weight
  • the amount of the ultrafine particles C is in the range of 100 to 400 parts by weight
  • the hardness of the first curable resin layer is insufficient, so that the volume change due to crystallization of the transparent conductive layer. Cannot be supported, and fine wrinkles are generated in the transparent conductive film layer.
  • the amount is more than 400 parts by weight, if the hardness of the first hardening shelf layer is to be adjusted by adding a large amount of the ultrafine particles C, the first hardening resin layer and the transparent polymer substrate are to be adjusted. A problem that the adhesion to the substrate is insufficient.
  • the curable resin component and the ultrafine particles C are mixed, a harder and more durable shelf layer can be obtained than the layer formed with the curable resin layer component alone, but the formed layer has no flexibility.
  • a transparent touch panel using a transparent conductive laminate in which the curable shelf layer and the transparent conductive layer are laminated cracks are generated during an edge pressing durability test, and the electrical characteristics (linearity) are satisfied. It is difficult.
  • the first hardening resin layer is composed of a curable resin component and (A) a synthetic rubber or / and (B) a resin component having urethane acrylate as a monomer and does not contain ultrafine particles C
  • a curable resin component and (A) a synthetic rubber or / and (B) a resin component having urethane acrylate as a monomer and does not contain ultrafine particles C
  • heat treatment is performed to obtain a crystalline transparent conductive layer, there is a problem that the transparent conductive layer surface is wrinkled and the haze of the transparent conductive laminate increases.
  • the (A) synthetic resin is obtained by mixing a resin component having (A) a synthetic rubber or rubber and (B) a urethane acrylate as a monomer with the ultrafine particles C in a predetermined ratio. It is possible to adjust the hardness of the first hardening resin layer with ultrafine particles C while keeping the flexibility of the rubber component and / or the shelf component that is made of (B) urethane acrylate as the monomer.
  • the transparent conductive laminate in which the first curable resin layer and the transparent conductive layer are laminated the haze of the transparent conductive laminate is increased even when heat treatment is performed to obtain a crystalline transparent conductive layer. None rise. Further, in the transparent sunset panel using the transparent conductive laminate, no crack is generated during the edge pressing durability test.
  • the curable resin layer has sufficient flexibility but no hardness.
  • the Young's modulus ( ⁇ ,) exceeds 9.8 GPa (1,000 kgf / mm 2 ) and the plastic deformation hardness (HV If ⁇ exceeds 8.5 X 10 8 Pa (85 kgf / mm 2 ), the curable swelling layer has sufficient hardness but lacks flexibility, so it is not suitable as a curable resin layer. Absent.
  • the above ranges are more preferably 6.9 GPa ⁇ W 1 ⁇ 8.9 GPa (700 kg f / mm ⁇ W ⁇ Q 00 kg f / mm 2 ) and 2.0 X 10 8
  • Examples of the synthetic rubber component of the present invention 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, and chlorosulfone. Rubber, chlorinated polyethylene, nitrile rubber, hydrogenated acrylonitrile butadiene rubber, polysulfide rubber, acrylate, various synthetic latex, and the like. You may use the block copolymer of these synthetic rubbers. Further, these synthetic rubbers may be used alone or in combination.
  • the content of the synthetic rubber component is preferably from 100 to 400 parts by weight based on 100 parts by weight of the stiffening resin component. More preferably, the amount is 30 to 300 parts by weight, and still more preferably 50 to 250 parts by weight. If the content of the synthetic rubber component is less than 10 parts by weight, sufficient curability of the curable resin layer cannot be imparted to the curable resin layer, so that the transparent conductive layer obtained by laminating the first curable resin layer and the transparent conductive layer is not provided. In the case of a transparent touch panel using a laminate, cracks occur in the first curable resin layer during the edge pressing durability test, and the electrical characteristics of the transparent touch panel cannot be satisfied.
  • the hardness of the first curable shelf layer is insufficient even if ultrafine particles C are added to the first hardening resin layer, so that the volume accompanying the crystallization of the transparent conductive layer is insufficient. Since the change cannot be supported, fine wrinkles are generated in the transparent conductive film layer, and there is a problem that the transparent conductive laminate has a raised haze and whitening.
  • the resin component containing urethane acrylate as a monomer is obtained by reacting a polyol such as a diol with a polyfunctional isocyanate such as diisocyanate, and then capping the end with a hydroxy-functional acrylate.
  • a polyol such as a diol
  • a polyfunctional isocyanate such as diisocyanate
  • the polyol include polyether polyols, polyester polyols, hydrogenated hydrocarbon polyols, and the like. Copolymers of these polyols may be used. These polyols may be used alone or in combination of two or more.
  • the number average molecular weight of the polyol is preferably about 200 to 100,000, more preferably 500 to 50,000.
  • the formed first curable resin layer has too large a Young's modulus, and the first curability of a predetermined Young's modulus and a composition deformation hardness is obtained. It is difficult to obtain a layer of the first curable resin layer in a transparent sunset paneler using a transparent conductive laminate in which the first curable resin layer and the transparent conductive layer are laminated. Cracks enter the panel and the electrical characteristics of the transparent panel cannot be satisfied.
  • the content of the shelf component containing urethane acrylate as a monomer is preferably from 100 to 400 parts by weight, more preferably from 30 to 400 parts by weight, based on 100 parts by weight of the curable luster ingredient.
  • the amount is preferably 300 parts by weight, more preferably 50 to 250 parts by weight.
  • the content of the resin component containing urea acrylate as a monomer is less than 10 parts by weight, it is difficult to obtain sufficient flexibility in the first hardening resin layer.
  • a transparent touch panel using a transparent conductive laminate in which a transparent conductive layer is laminated cracks occur in the first curable resin layer during the edge pressing ffii durability test, and the electrical characteristics of the transparent evening panel cannot be satisfied.
  • the content exceeds 400 parts by weight the hardness of the first curable resin layer is insufficient even if the ultrafine particles C are added, so that the volume change accompanying the crystallization of the transparent conductive layer cannot be supported, and the transparent conductive layer cannot be supported.
  • fine wrinkles are generated in the film layer, and the transparent conductive laminate has a haze rise and whitening.
  • curable resin component in the paragraph of the first curable resin layer, in the paragraph of the first curable resin layer, ionizing radiation hardened resin and thermohardened resin described as a hardenable shelf component other than the isocyanuric acid AO-modified acrylate, etc. And the isocyanuric acid A-modified acreates. It should be understood that the description of the curable resin component which is not described herein is the same as the description of the curable resin component described in the paragraph of the first curable resin layer.
  • the method for forming the first curable resin layer specified in the above (1-2) includes a doctor knife, a bar coater, a gravure mouth, a curtain coater, a curtain coater, a knife coater, and a spin coater. And the like, a known method using a coating machine, a spray method, a dipping method and the like.
  • a resin composition having at least one of (A) a synthetic rubber component or (B) a resin component containing urethane acrylate as a monomer and a primary particle diameter of 1 Ultra fine metal oxide or metal fluoride of 0 nm or less The particles c, etc.
  • a method of forming a fat layer is exemplified.
  • an appropriate amount of a known photopolymerization initiator is added. If necessary, an appropriate amount of a photosensitizer may be added.
  • the photopolymerization initiator include acetophenone, benzophenone, benzoin, benzoylbenzoate, and thioxanthone.
  • the photosensitizer include tritylamine, tri-n-butylphosphine, and the like.
  • the diluting solvent examples include alcohol solvents such as ethanol, isopropyl alcohol, butanol, and 1-methoxy-2-propanol; and hydrocarbon solvents such as hexane, cyclohexane, and ligroin. , Xylene, toluene and the like, aromatic solvents such as methyl ethyl ketone and methyl isobutyl ketone, and water. Since the above coating liquid contains a synthetic rubber component, one of the solvents used is an aromatic solvent such as xylene or toluene, or a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone. Is preferred.
  • alcohol solvents such as ethanol, isopropyl alcohol, butanol, and 1-methoxy-2-propanol
  • hydrocarbon solvents such as hexane, cyclohexane, and ligroin.
  • polar solvents such as cyclohexanone, butyl acetate, and isobutyl acetate can also be used. These solvents can be used alone or as a mixed solvent of two or more kinds.
  • the organic polymer used for producing the transparent organic polymer substrate is not particularly limited as long as it is a transparent organic polymer having excellent heat resistance.
  • polyester resins such as polyethylene terephthalate, polyethylene 1,6-naphthalate, polydiaryl phthalate, polycarbonate resin, polyether sulfone tree A, polysulfone resin, polyarylate resin, acrylic resin, cellulose acetate (I) Toluene, cycloolefin polymer and the like.
  • these may be used as homopolymers or copolymers.
  • the above organic polymers may be used alone or may be used by blending.
  • These transparent organic polymer substrates are suitably molded by a general melt extrusion method or a solution casting method, but if necessary, It is also preferable to carry out uniaxial stretching or biaxial stretching on the molded transparent organic polymer substrate to increase the mechanical strength or enhance the optical function.
  • the transparent organic laminate of the present invention When used as a movable electrode substrate of a transparent touch panel, the transparent organic laminate is required to have a high flexibility and a high strength to maintain flatness for operating the transparent touch panel as a switch.
  • the molecular substrate a film-like one having a thickness of 75 to 400 ⁇ is preferable.
  • a sheet of a transparent organic polymer substrate having a thickness of 0.4 to 4.0 mm is preferable in terms of strength for maintaining flatness, but a thickness of 50 mm is preferable.
  • a film having a thickness of up to 400 m may be bonded to another plastic sheet so that the overall thickness becomes 0.4 to 4.0 mm.
  • the fixed electrode substrate may be a transparent organic polymer substrate, a glass substrate, or a laminate of a transparent organic polymer substrate and a glass substrate.
  • a transparent organic polymer substrate may be used in which a transparent conductive layer is formed on a laminate of a substrate and a plastic sheet. From the viewpoint of strength and weight of the transparent panel and the Sochi panel, the thickness of the fixed electrode substrate consisting of a single layer or a laminate is 0.
  • a new type of transparent touch panel has a structure in which a polarizing plate or a polarizing plate and one or more retardation films are laminated on the input side of the transparent touch panel, that is, on the user side.
  • the advantage of this configuration is that the reflectance of extraneous light inside the transparent touch panel is reduced to less than half by the optical action of the polarizing plate or the polarizing plate and one or more retardation films, and the transparency is reduced.
  • the purpose is to improve the contrast of the display with the evening panel installed.
  • the in-plane retardation value Re is at least 30 nm or less. More preferably, it is 20 nm or less.
  • the in-plane retardation value of the substrate is represented by a value at a wavelength of 590 nm measured by using a spectroscopic ellipsometer (M-150, manufactured by JASCO Corporation).
  • the in-plane retardation value of the transparent electrode substrate is very important.
  • These transparent organic polymer substrates having excellent optical isotropy include, for example, polycarbonate, amorphous polyarylate, polyether sulfone, polysulfone, triacetyl cellulose, diacetyl cellulose, cycloolefin polymer and the like. And a molded substrate of a modified product thereof or a copolymer with another material, a molded substrate of a thermosetting resin such as an epoxy resin, a molded substrate having an ultraviolet curable shelf such as acryl resin, and the like.
  • poly-polynate non-crystalline polyarylate
  • polyethersulfone polysulfone
  • cycloolefin polymer and their modified products or other materials
  • a molded substrate such as a polymerization /.
  • examples of the polycarboxylic acid include bisphenol A, 1,1-di (4-phenol) cyclohexylidene, 3,3,5-trimethyl-1,1-di (4-phenol) cyclo A polymer containing at least one component selected from the group consisting of hexylidene, fluorene-1,9-di (4-phenol), fluorene-1,9,9-di (3-methyl-14-phenol), etc. as a monomer unit Or a mixture of a polymer or a copolymer having at least one component selected from the above group as a monomer unit, and having an average molecular weight of about 150,000 to 100,000.
  • a molded substrate of polycarbonate in the range of 00 (for example, “Panlite” manufactured by Teijin Chemicals Limited and “Apec HT” manufactured by Bayer Corporation) is preferably used.
  • amorphous polyarylate include moldings such as Keliki Co., Ltd. (formerly Kaneka Kagaku Kogyo Co., Ltd.) “Elmec”, Unitika Co., Ltd. “u-Polymer”, and Isonova “Isalil”.
  • a substrate is exemplified.
  • cycloolefin polymer examples include molded substrates such as “Zeonor” manufactured by Zeon Corporation and “ARTON” manufactured by JSR Corporation.
  • Examples of the method for molding these polymer materials include melt extrusion, solution casting, and extrusion molding. From the viewpoint of obtaining excellent optical isotropy, particularly solution casting is preferred. It is preferable to carry out molding using a method—melt extrusion method.
  • the transparent conductive laminate of the present invention comprises: (A) a synthetic resin and (B) a urethane acrylate monomer as a monomer between the transparent organic polymer substrate and the first curable resin layer. It may have a second curable resin layer containing at least one selected from the group consisting of 10% by weight or more.
  • the second rigid resin layer is The end-push durability is further improved as compared with the case in which there is no pressing.
  • the hardening resin containing urethane acrylate as a monomer is a cured product of a resin component containing urethane acrylate as a monomer.
  • At least one resin selected from the group consisting of (A) a synthetic rubber and (B) a urethane acrylate as a monomer is used as the curable resin of the second hardening resin layer.
  • it occupies 10% to 100% by weight of the second curable resin layer, or the total of the components A) and (B) occupies 10 to 100% by weight. More preferably, it occupies 30 to 100% by weight of the second hardening resin layer, and still more preferably 40 to 100% by weight of the second hardening resin layer.
  • the purpose is to use together with ionizing radiation curable resin or thermosetting resin when forming the second curable resin layer. be able to.
  • the monomer that gives the ionizing radiation type resin include polyol acrylate, polyester acrylate, urethane acrylate other than the above, epoxy acrylate, modified styrene acrylate, melamine acrylate, and silicon-containing. Examples thereof include monofunctional and polyfunctional acrylates such as acrylates.
  • Specific monomers include, for example, trimethyl alcohol propane trimethacrylate, trimethylol propane ethylene oxide modified triacrylate, trimethylol propane propylene oxide modified triacrylate, isocyanuric acid ethylene oxide modified triacrylate, Penyu erythritol triacrylate, dipentyl erythritol hexaatalylate, dimethylol tricyclodecane diacrylate, tripropylene glycol J retriacrylate, dimethylene glycol diacrylate, 1,6-hexanediol di
  • polyfunctional monomers such as acrylates, epoxy-modified acrylates, and urethane-modified acrylates. These may be used alone or as a mixture of several types.
  • hydrolysates of various alkoxysilanes may be added.
  • a known photopolymerization initiator is added in an appropriate amount. If necessary, an appropriate amount of a photosensitizer may be added.
  • Examples of the photopolymerization initiator include acetophenone, benzophenone, benzoin, benzoylbenzoate, and thioxanthones.
  • Examples of the photosensitizer include triethylamine and tri-n-butylphosphine.
  • thermosetting resin examples include an organosilane-based thermosetting resin using a silane compound such as methyltriethoxysilane and phenyltriethoxysilane as a monomer, and a melamine-based thermosetting resin using a monomer such as etherified methylolmelamine. Mold resin, isocyanate-based thermosetting resin, phenol-based thermosetting resin, epoxy-curable resin, and the like. These curable resins can be used alone or in combination. It is also possible to mix a thermoplastic resin if necessary. When crosslinking the resin layer by heat, an appropriate amount of a known reaction accelerator or curing agent is added.
  • reaction accelerator examples include triethylenediamine, dibutyltin dilaurate, benzylmethylamine, pyridine and the like.
  • a curing agent for example, Hexahydrofluoric anhydride, 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-getyldiphenylmethane, diaminodiphenylsulfone and the like.
  • the thickness of the second curable resin layer is preferably from 1 to 10 m, and more preferably from 2 to 8 m.
  • the method includes: (A) synthetic rubber or (B) urethane acrylate as a monomer and / or other ionizing radiation-curable resin or thermosetting resin monomer if necessary.
  • the transparent conductive laminate of the present invention between the first curable effect layer and the transparent conductive layer, is in contact with the transparent conductive layer, has a thickness smaller than the thickness of the transparent conductive layer, and has a thickness of 0.5 nm or more. It may further have a metal compound layer having a thickness of less than 10 nm, preferably at least 1.0 O nm and less than 7.0 O nm, more preferably at least 1.0 O nm and less than 5.0 nm.
  • the adhesion is greatly improved, and the transparent touch panel using the transparent conductive laminate is Compared to the case without the metal compound layer, the writing durability and edge pressing durability required for the transparent touch panel in recent years are improved.
  • the thickness of the metal compound layer is 10.0 nm or more, the metal compound layer starts to exhibit mechanical properties as a continuum, so that improvement in the edge pressing durability required for a transparent touch panel cannot be expected.
  • the film thickness is less than 0.5 nm, it is difficult to control the film thickness, and it is difficult to sufficiently develop the adhesion between the first hardening resin layer and the transparent conductive layer. It becomes difficult to improve the push durability.
  • the metal compound layer include metal oxide layers such as silicon oxide, aluminum oxide, titanium oxide, magnesium oxide, zinc oxide, indium oxide, and tin oxide.
  • These metal compound layers can be formed by a known method.
  • physical methods such as a DC magnetron sputtering method, an RF magnetron sputtering method, an ion plating method, a vacuum evaporation method, and a pulse laser deposition method can be used.
  • PVD Physical Vapor Deposition
  • a chemical formation method such as Chemical Vapor Deposition (hereinafter, CVD) and a sol-gel method can be used.
  • Sputtering is preferred. It is desirable to use a metal target as a target for sputtering. It is widely used to use a reactive sputtering method. This is because oxides, nitrides, and oxynitrides of the elements used for the metal compound layer are often insulators, and in the case of metal compounds, the DC magnet sputtering method is often not applicable. . In recent years, power supplies have been developed that simultaneously discharge two power sources and suppress the formation of insulators on the target, making it possible to apply the pseudo RF magnetron sputtering method. Is coming.
  • the pressure (back pressure) in the vacuum chamber for forming the metal compound layer is temporarily reduced to 1.3X. and 10_ 4 Pa or less, can then be formed in the production method of introducing an inert gas and oxygen. Be below once 1.
  • 3X 10- 4 P a pressure in the vacuum tank for film metal compound layer remains in a vacuum tank, is and concerns that affect the formation process of the metal compound layer This is desirable because it can reduce the effects of different molecular species. More desirably, 5X 10- 5 Pa or less, and more preferably not more than 2X 10- 5 P a.
  • the inert gas can be used as the inert gas to be introduced.
  • the inert gas having a larger atomic weight has less damage to the formed metal compound layer and has improved surface flatness. It is said that.
  • Ar is desirable in terms of cost.
  • the 1. 3X 10- 3 ⁇ 7 X 10- 2 P a stand oxygen in terms of partial pressure may also be added pressure Absent.
  • other than oxygen, O 3 , N 2 , N 20 , H 20 , NH 3 and the like can be used according to the purpose.
  • the present invention can be formed by the manufacturing method the partial pressure of water in the vacuum chamber in which film the metal compound layer is less 1. 3X 10- 4 Pa, then introducing an inert gas and oxygen .
  • the partial pressure of water more preferably, 4X10- 5 P a or less, preferably to further can be controlled below 2 X 10- 5 Pa.
  • To mitigate metal compound layer internal stress between Serco incorporated hydrogen in the film it may be introduced in a range of deliberately 1. 3 X 10 one 4 ⁇ 3X 10- 2 Pa water. This adjustment may be performed by once forming a vacuum and then introducing water using a variable leak valve or a mass flow controller. It can also be implemented by controlling the back pressure of the vacuum chamber.
  • a differential exhaust type in-process monitor When determining the water pressure in the present invention, a differential exhaust type in-process monitor may be used. Alternatively, a quadrupole mass spectrometer that has a wide dynamic range and can measure even under a pressure of the order of 0.1 Pa may be used. Also, in general, in the vacuum of about 3 X 10- 5 P a 1., the Ru Mizudea of forming the pressure. Therefore, the value measured by the vacuum gauge may be directly considered as the water pressure. In the present invention, since a transparent organic polymer substrate is used, the substrate temperature cannot be raised above the softening point temperature of the transparent organic polymer substrate. Therefore, in order to form the metal compound layer, the temperature of the transparent organic polymer substrate needs to be from room temperature or lower to the softening point temperature or lower.
  • the metal compound layer In the case of polyethylene terephthalate, which is a typical transparent organic polymer substrate, it is desirable to form the metal compound layer while keeping the substrate temperature at 80 ° C. or lower unless special treatment is performed. More preferably, at a substrate temperature of 50 ° C. or less, more preferably, 20 ° C. or less. In addition, heat-resistant polymer substrates Even above, it is desirable to form at a substrate temperature set at 80 or less, more preferably at 50 or less, more preferably at 20 ° C. or less from the viewpoint of controlling outgas from the polymer substrate.
  • the transparent conductive laminate of the present invention may further comprise a third curable resin between the first hardening shelf layer and the transparent conductive layer or between the first hardening shelf layer and the metal compound layer. It may have a layer.
  • the third curable shelf layer improves the adhesion between the layers and the optical properties of the transparent conductive laminate, particularly the transmittance.
  • Examples of the third curable shelf layer include an ionizing radiation curable resin and a thermosetting resin.
  • ionizing radiation-curable resin examples include monofunctional and polyfunctional acrylates such as polyol acrylate, polyester acrylate, urethane acrylate, epoxy acrylate, modified styrene acrylate, melamine acrylate, and silicon-containing acrylate.
  • monofunctional and polyfunctional acrylates such as polyol acrylate, polyester acrylate, urethane acrylate, epoxy acrylate, modified styrene acrylate, melamine acrylate, and silicon-containing acrylate.
  • examples include ionizing radiation curable resins.
  • thermosetting resin examples include, for example, an organosilane thermosetting resin (alkoxysilane) such as methyltriethoxysilane and phenyltriethoxysilane, and a melamine thermosetting resin such as etherified methylolmelamine. Mold resin, phenol-based thermosetting resin, epoxy-based hard resin, and the like. These thermosetting resins can be used alone or in combination. It is also possible to mix and use a thermoplastic resin if necessary. When the resin layer is crosslinked by heat, an appropriate amount of a known reaction accelerator or curing agent is added. Examples of the reaction accelerator include triethylenediamine, dibutyltin dialolate, benzylmethylamine, pyridine and the like. Examples of the curing agent include methylhexahydrophthalic anhydride and bis (4-amino-3-methyldicyclohexyl).
  • the alkoxysilane forms a third curable resin layer by subjecting it to hydrolysis and condensation polymerization.
  • the alkoxysilane include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ - (3,4-epoxycyclohexyl) Ethyltrimethoxysilane, vinyltrimethoxysilane, ⁇ — / 3 (aminoethyl) aminopropyl trimethoxysilane, ⁇ —] 3 (aminoethyl) aminopropyldimethoxysilane, aminopropyltriethoxysilane And the like.
  • the weight ratio of the alkoxysilane to the total composition of the alkoxysilane is preferable. It is preferable that the alkoxysilane having an amino group in the molecule is contained in the range of 0.5 to 40%.
  • the alkoxysilane may be used as a monomer or after it has been subjected to hydrolysis and dehydration-condensation in advance to be appropriately oligomerized before use.
  • a coating solution dissolved and diluted in an appropriate organic solvent is applied onto a substrate. I do.
  • the coating layer formed on the substrate undergoes hydrolysis due to moisture in the air and the like, and subsequently crosslinking proceeds by dehydration condensation.
  • an appropriate heat treatment is required to promote crosslinking, and it is preferable to perform a heat treatment at a temperature of 10 ° C. or more for several minutes or more in the coating step.
  • 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.
  • alcohol-based or hydrocarbon-based solvents such as ethanol, isopropyl alcohol, butanol, 1-methoxy-2-propanol, hexane, cyclohexane, and rigoin are preferable.
  • 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 types.
  • the refractive index of the third hard resin layer is preferably smaller than the refractive index of the first curable resin layer, and the refractive index is preferably from 1.20 to 1.55, more preferably from 1.20 to 1.45. It is.
  • the thickness of the third hardening resin layer is preferably from 0.05 to 0.5 m, more preferably from 0.05 to 0.3 m.
  • the average primary particle diameter of the ultrafine particles C is preferably 10 Onm or less, more preferably 50 nm or less. If the primary particle diameter of the ultrafine particles C is controlled to 100 nm or less, the coating layer will not be whitened.
  • the ultrafine particles C for example, B i 2 0 3, Ce_ ⁇ 2, ln 2 0 3, ( I n 2 0
  • the content of the ultrafine particles C is preferably from 10 to 400 parts by weight, more preferably from 30 to 400 parts by weight, and still more preferably from 50 to 100 parts by weight, per 100 parts by weight of the thermosetting resin or / and the ionizing radiation-curable resin. 300 parts by weight. If the content of ultrafine particles C exceeds 400 parts by weight, the film strength and adhesion may be insufficient, whereas if the content of ultrafine particles is less than 10 parts by weight, a predetermined refractive index cannot be obtained. There are cases.
  • fluorine resin examples include vinylidene fluoride, hexafluoropropylene, tetrafluoroethylene, fluoroethylene, trifluoroethylene, chlorotrifluoroethylene, 1,2-dichloro-1,2-difluoroethylene. 3,2,3-Trifluoroethylene, 3-Bromo-3,3-difluoropropylene, 3,3,3-Trifluoropropylene, 1,1,2-Trichloro-1,3 And those containing 5-70% by weight of a monomer component having a fluorine atom, such as 1,3-trifluoropropylene or ⁇ -trifluoromethacrylic acid.
  • a monomer component having a fluorine atom such as 1,3-trifluoropropylene or ⁇ -trifluoromethacrylic acid.
  • the content of the fluorine-based resin is preferably 50 to 300 parts by weight, more preferably 100 to 300 parts by weight, based on 100 parts by weight of the thermosetting resin or Z and the ionizing radiation-curable resin. Parts by weight, more preferably 150 to 250 parts by weight.
  • the content of the fluorine-based resin exceeds 300 parts by weight, the film strength and adhesion may be insufficient.
  • the content of the fluorine-based shelf is less than 50 parts by weight, a predetermined refractive index is obtained. May not be possible.
  • the transparent conductive laminate of the present invention has at least one low refractive index layer between the first hardening layer and the transparent conductive layer or between the first curable resin layer and the metal compound layer.
  • An optical interference layer comprising at least one high refractive index layer can be further provided.
  • the low refractive index layer and the transparent conductive layer or the low refractive index layer and the metal compound layer are in contact with each other.
  • the optical interference layer is composed of at least one high refractive index layer and at least one low refractive index layer.
  • the combination unit of the high refractive index layer and the low refractive index layer may be two or more.
  • the thickness of the optical interference layer is preferably from 30 nm to 300 nm, more preferably from 50 nm to 200 nm. 0 nm.
  • the optical interference layer improves the adhesion between the layers and the optical properties of the transparent conductive laminate, particularly the transmittance and the color tone.
  • the high refractive index layer is, for example, a layer formed by hydrolysis and condensation polymerization of a metal alkoxide, or a hydrolysis and condensation polymerization of at least one or more metal alkoxides described in the paragraph of the third hardening layer.
  • a metal oxide or metal fluoride ultrafine particle C having an average primary particle diameter of 100 nm or less.
  • metal alkoxide examples include titanium alkoxide, zirconium alkoxide, and alkoxysilane.
  • titanium alkoxide examples include titanium tetraisopropoxide, tetra-n-propyl orthotitanate, titanium tetra-n-butoxide, tetrakis (2-ethylhexyloxy) titanate and the like.
  • zirconium alkoxide examples include zirconium tetraisopropoxide and zirconium tetra-n-butoxide.
  • alkoxysilane examples include the same ones as described in the paragraph of the third curable resin layer.
  • the above-mentioned ultrafine particles C of metal oxide or metal fluoride having an average primary particle diameter of 100 nm or less can be used alone or in an appropriate amount of two or more.
  • the refractive index of the high refractive index layer can be adjusted.
  • the weight ratio of the ultrafine particles C to the metal alkoxide is preferably 0: 100 to 66.6: 33.3, More preferably, it is 0: 100 to 60:40. If the weight ratio of the ultrafine particles C to the metal alkoxide exceeds 66.6: 33.3, the strength and adhesion required for the optical interference layer may be insufficient, which is not preferable.
  • the thickness of the high refractive index layer is preferably 15 to 25 O nm, more preferably 30 to 150 nm.
  • the refractive index of the high refractive index layer is larger than the refractive indexes of the low refractive index layer and the first curable resin layer described later, and the difference is preferably 0.2 or more.
  • the low refractive index layer constituting the optical interference layer of the present invention can be formed using the resin described in the paragraph of the third curable shelf layer.
  • the thickness of the low refractive index layer is preferably 15 to 250 nm, more preferably 30 to 150 nm.
  • the ultrafine particles C are contained in the third hardening layer or in at least one of the high refractive index layer and the low refractive index layer constituting the optical interference layer.
  • Fine particles (hereinafter, referred to as fine particles B) different from (the average primary particle diameter is 10 O nm or less) may be contained.
  • fine particles B having an average primary particle diameter of at least 1.1 times the film thickness of the third curable resin layer and an average primary particle diameter of 1.2 ⁇ m or less Is preferably used.
  • the average primary particle diameter should be at least 1.1 times the total thickness of the optical interference layer.
  • Fine particles B having an average primary particle diameter of 1.2 m or less are preferably used.
  • the surface of the transparent conductive layer is roughened, and it is possible to suppress a malfunction due to a sticking phenomenon between the surfaces of the transparent electrode layers of the fixed electrode substrate and the movable electrode substrate constituting the transparent touch panel.
  • the surface of the transparent conductive layer can be roughened within a range that does not cause glare due to scattering of RGB primary color light emitted from the liquid crystal.
  • the amount of the fine particles B to be added to at least one of the high refractive index layer and the low refractive index layer constituting the third curable resin layer and the optical interference layer is determined by the curable resin constituting the layer to which the fine particles B are added.
  • the content By setting the content to 0.01 to 0.5% by weight of the components, not only can the third hardening resin layer or optical interference layer having no cloudiness be formed, but also the movable electrode substrate constituting the transparent touch panel. In addition, it is possible to suppress a malfunction due to a phenomenon in which the surfaces of the transparent conductive layers of the fixed electrode substrate stick to each other.
  • the fine particles B When the fine particles B are excessively added to at least one of the high refractive index layer and the low refractive index layer constituting the third curable resin layer or the optical interference layer, the added fine particles B easily fall off, Alternatively, the adhesion between the third curable resin layer or the optical interference layer and the first curable resin layer may be reduced, and the writing durability required for the evening panel may not be satisfied.
  • the fine particles B are preferably contained only in the high refractive index layer, but may be contained in both the high refractive index layer and the low refractive index layer.
  • the fine particles B to be added to at least one of the high refractive index layer and the low refractive index layer constituting the third curable resin layer or the optical interference layer include, for example, fine silica particles, crosslinked acryl fine particles, and crosslinked polystyrene fine particles. Is mentioned.
  • the average primary particle diameter of the fine particles B is preferably at least 1.1 times the total thickness of the third curable resin layer or the optical interference layer, and the average primary particle diameter is preferably at most 1.2 ⁇ m. Better.
  • the average primary particle diameter of the fine particles B is less than 1.1 times the total film thickness of the third hardening resin layer or the optical interference layer, it is difficult to roughen the surface of the transparent conductive layer. .
  • the average primary particle diameter of the fine particles B exceeds 1.2 m, at least one of the high refractive index layer and the low refractive index layer constituting the third curable resin layer or the optical interference layer has such a property.
  • Transparent transparent panel made of transparent conductive laminate with added fine particles
  • the liquid crystal display appears glaring, degrading the display quality.
  • the average primary particle diameter of the fine particles B exceeds 1.2 m
  • the average primary particle diameter is extremely larger than the thickness of the third curable resin layer or the optical interference layer to which the fine particles B are added.
  • the added fine particles B easily fall off from the third curable resin layer or the optical interference layer, making it difficult to satisfy the writing durability required for the transparent touch panel.
  • fine particles B are applied to at least one of the high refractive index layer and the low refractive index layer constituting the third curable resin layer or the optical interference layer. It is preferable to include them.
  • the transparent conductive layer is provided in contact with the first curable resin layer, the third curable resin layer, the optical interference layer, or the metal compound layer.
  • a transparent conductive layer in contact with the first curable resin layer, the third curable shelf layer, the optical interference layer, or the metal compound layer.
  • the transparent conductive layer include an ITO layer containing tin oxide in an amount of 2 to 20% by weight and a tin oxide layer doped with antimony or fluorine.
  • the thickness of the transparent conductive layer is preferably from 5 to 5 O nm, more preferably from 10 to 3 O nm, from the viewpoint of transparency and conductivity. If the thickness of the transparent conductive layer is less than 10 nm, the stability of the resistance value with time tends to be inferior, and if it exceeds 3 O nm, the transmittance of the transparent conductive laminate is undesirably reduced.
  • the surface resistance value should be 100 ⁇ 2, 00 ⁇ square ( ⁇ / sq), more preferably, when the film thickness is 10 ⁇ 3 O nm. It is preferable to use a transparent conductive layer having a range of 140 to 2, ⁇ / square ( ⁇ / s Q). Further, the transparent conductive layer is preferably a crystalline film containing indium oxide as a main component, and in particular, a layer made of crystalline ITO is preferable. It is preferably used. Further, the crystal grain size is preferably not more than 3,000 nm. If the crystal grain size exceeds 3,000 nm, the writing durability deteriorates, which is not preferable. Here, the crystal grain size is defined as the largest diagonal line or diameter in each polygonal or elliptical region observed under a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • mainly containing indium oxide refers to indium oxide containing tin, tellurium, cadmium, molybdenum, tungsten, fluorine, zinc, or the like as a dopant, or tin or tin as a dopant in addition to tin.
  • crystalline film refers to 50% or more, preferably 75% or more, more preferably 95% or more, and particularly preferably about 1% or more of the layer made of indium oxide containing a dopant. It means that 0% is occupied by the crystalline phase.
  • the transparent conductive laminate of the present invention is used as a movable electrode substrate, it is preferable to provide a hard coat layer on the surface of the transparent touch panel to which external force is applied.
  • the material for forming the hard coat layer include, for example, an organosilane-based thermosetting resin J such as methyltriethoxysilane and phenyltriethoxysilane, and a melamine-based thermosetting resin such as etherified methylolmelamine.
  • this S i 0 2 Ya it can be used a mixture of fine particles such as M g F 2.
  • the thickness of the hard coat layer is preferably 2 to 5 m from the viewpoint of flexibility and abrasion resistance.
  • the hard coat layer can be formed by a coating method.
  • a coating method As an actual coating method, the above compound is dissolved in various organic solvents, and a coating solution of which the concentration and viscosity are adjusted is used to apply the solution onto a transparent organic polymer substrate, and then, irradiation with ionizing radiation, heat treatment, etc. This hardens the coating layer.
  • the coating method include a microgravure coating method, a Meyer bar coating method, a direct gravure coating method, a reverse roll coating method, a force coating method, a spray coating method, a comma coating method, and a die coating method. Method, knife coating method, spin coating method and the like.
  • 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 having a negative K value.
  • a phase compensation layer a layer having a function of preventing permeation of moisture or oxygen or a function of absorbing moisture or oxygen, a layer having a function of absorbing ultraviolet light or infrared light, a layer having a function of reducing the chargeability of a substrate, or the like is preferable. It is raised.
  • the methods for measuring the Young's modulus and plastic deformation hardness are as follows.
  • Nano indentation tester ENT—110a manufactured by Elionix
  • Measurement surface The curable resin layer surface is measured.
  • Indenter triangular pyramid (edge spacing 1 15 °)
  • Young's modulus is the composite elastic modulus obtained by adding the elastic modulus of the sample and the elastic modulus of the indenter.
  • Example 1 Perform a writing durability test of 100,000 reciprocations in a straight line with a load of 450 g using a polyacetal pen with the tip 0.8 R diagonally at the center of the movable electrode substrate of the fabricated transparent touch panel. NG was determined if the change in linearity of the transparent touch panel before and after writing durability was 1.5% or more.
  • Example 1 Perform a writing durability test of 100,000 reciprocations in a straight line with a load of 450 g using a polyacetal pen with the tip 0.8 R diagonally at the center of the movable electrode substrate of the fabricated transparent touch panel. NG was determined if the change in linearity of the transparent touch panel before and after writing durability was 1.5% or more.
  • a hard coat layer 1 having a thickness of 4 im was formed on one surface of a polyethylene terephthalate film having a thickness of 188 im (OFW manufactured by Teijin Dupont Film Co., Ltd.) using a UV-curable polyfunctional acrylate resin paint.
  • N- / 3 (aminoethyl) aminopropylmethoxysilane (“KBM603" manufactured by Shin-Etsu Chemical Co., Ltd.) was added to 1 part by weight of solids per 20 parts by weight of solids of alkoxysilane hydrolyzate 1. The mixture was added at a ratio, and further diluted with a mixed solution of isopropyl alcohol and n-butanol to prepare an alkoxysilane coating liquid B.
  • a coating liquid C was prepared by mixing silica fine particles having an average primary particle diameter of 0.5 tm in the coating liquid B so as to be 0.3 parts by weight with respect to 100 parts by weight of the alkoxysilane.
  • An alkoxysilane coating liquid C was coated on the first curable resin layer (a) by a bar coating method, and fired at 130 for 2 minutes to prepare a third curable resin layer. Further, an indium oxide / tin oxide composition having a weight ratio of 95: 5 and a packing density of 98% was obtained on the third hardening resin layer by sputtering using an indium oxide / tin oxide mixture. Was formed, and a transparent conductive laminate serving as a movable 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 ⁇ / ⁇ ( ⁇ / sq).
  • the fabricated movable electrode substrate was heat-treated at 150 ° C for 90 minutes to crystallize the ITO layer. No haze change was observed in the movable electrode substrate before and after the heat treatment, and the surface resistance after the crystallization of the ITO layer was about 280 ⁇ / sq ( ⁇ / s Q).
  • an ITO layer having a thickness of 18 nm was formed by a similar method by a sputtering method.
  • a fixed electrode substrate was fabricated by forming a dot spacer having a height of 7 m, a diameter of 70 ⁇ , and a pitch of 1.5 mm on the ITO layer.
  • a transparent sunset panel shown in FIG. 1 was fabricated.
  • a writing durability test and edge pressing durability test were performed on the fabricated transparent touch panel, and the linearity before and after the test is shown in Table 1.
  • Example 2 A hard coat layer 1 with a thickness of 4 m was formed on one side of a polyethylene terephthalate film (OFW manufactured by Teijin Dupont Film Co., Ltd.) with a thickness of 188 m, using a UV-cure type multifunctional acrylate shelf paint. did.
  • the coating solution A of Example 1 was coated on the surface opposite to the hard coat layer 1 to a thickness of 3.0
  • the first curable resin layer (a) was formed by coating with a bulk coating method and irradiating and curing with ultraviolet light.
  • the weight ratio of the coating solution B and the primary particle diameter of 20 nm rutile T I_ ⁇ 2 fine rutile T i 0 2 particles and alkoxysilane used in Example 1 50 were mixed 50 become by Uni Coating liquid D was prepared. Average primary particle diameter in the coating liquid D were mixed so that 0.3 parts by weight relative to the total weight 1 00 parts by weight of the silica force particles of 0. 5 m alkoxysilane and T i 0 2 particles Coating liquid E was prepared.
  • coating liquid E On the surface of the first curable resin layer (a), coating liquid E was applied by a vacuum coating method, and after baking at 130 ° C for 2 minutes, a high refractive index layer having a thickness of 55 nm was formed. .
  • the coating liquid B used in Example 1 was coated on the high refractive index layer as a low refractive index layer by a bar coating method, and baked at 130 ° C. for 2 minutes to form a low refractive index layer, thereby forming a high refractive index layer.
  • An optical interference layer composed of a refractive index layer and a low refractive index layer was formed.
  • an ITO layer is formed on the optical interference layer by sputtering using indium oxide and tin oxide in a composition of 95: 5 by weight and indium tin oxide having a packing density of 98%, and a movable electrode.
  • a transparent conductive laminate serving as a substrate was produced.
  • the film thickness of the formed ITO layer was about 20 nm, and the surface resistance after film formation was about 350 ⁇ / ⁇ ( ⁇ / sq).
  • the prepared movable electrode substrate was subjected to a heat treatment 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 after crystallization of the ITO was approximately 280 ⁇ / port ( ⁇ / sq).
  • a fixed electrode substrate was produced in the same manner as in Example 1. Using the fabricated fixed electrode substrate and movable electrode substrate, a transparent sunset panel shown in FIG. 2 was fabricated. A writing durability test and an edge pressing durability test were performed on the fabricated transparent touch panel, and the linearity before and after the test is shown in Table 1.
  • Comparative Example 1 A hard coat layer 1 having a thickness of 4 m was formed on one surface of a 188 / m-thick polyethylene terephthalate film (OFW manufactured by Teijin Dupont Film Co., Ltd.) using a UV-curable polyfunctional acrylate resin paint.
  • NK Oligo Ul 5HA manufactured by Shin-Nakamura Chemical Co., Ltd.
  • monofunctional acrylate Aronix TO-1429 manufactured by Toagosei Co., Ltd.
  • irgacure 184 irgacure 184 10 parts by weight
  • MIBK methyl isobutyl ketone
  • the coating liquid F was coated on the surface opposite to the hard coat layer 1 by a bar coating method so as to have a thickness of 4.0 / m, and was irradiated and cured with ultraviolet rays to form a first curable resin layer (b).
  • Table 1 shows the results of the measurement of the Young's modulus and the plastic deformation hardness of the first hardened dangling shelf layer (b).
  • An ITO layer is formed on the first curable resin layer (b) by sputtering using an indium oxide-tin oxide target having a composition of indium oxide and tin oxide in a weight ratio of 95: 5 and a packing density of 98%. Then, a transparent conductive laminate to be a movable electrode substrate was produced.
  • the film thickness of the formed IT ⁇ layer was about 20 nm, and the surface resistance after film formation was about 350 ⁇ / ⁇ ( ⁇ / sq).
  • the fabricated movable electrode substrate was subjected to a heat treatment at 150 ° C for 90 minutes to crystallize the ITO layer. No haze change was observed on the movable electrode substrate before and after the heat treatment, and the surface withdrawal value after ITO crystallization was about 280 ⁇ / ⁇ ( ⁇ / sq).
  • a fixed electrode substrate was produced in the same manner as in Example 1. Using the fabricated fixed electrode substrate and movable electrode substrate, a transparent sunset panel shown in FIG. 3 was fabricated. A writing durability test and an edge pressing durability test were performed on the fabricated transparent touch panel, and the linearity before and after the test is shown in Table 1.
  • a hard coat layer 1 having a thickness of 4 im was formed on one surface of a 188 m-thick polyethylene terephthalate film (OFW manufactured by Teijin Dupont Film Co., Ltd.) using a UV-curable polyfunctional acrylate resin paint.
  • the coating liquid A of Example 1 was coated on the surface opposite to the hard coat layer 1 by a bar coating method so as to have a thickness of 3.0 m, and was irradiated and cured by ultraviolet irradiation to form the first curable resin layer (a). Was formed.
  • the first curable resin layer (a) is coated on the surface with the coating solution E used in Example 2 by a percoat method, and after baking at 30 ° C. for 2 minutes, a high refractive index layer having a thickness of 55 nm is formed. Was formed.
  • the coating liquid B used in Example 1 was coated as a low refractive index layer on the high refractive index layer by a bar coating method, and baked at 130 ° C. for 2 minutes to form a low refractive index layer.
  • An optical interference layer composed of a high refractive index layer and a low refractive index layer was formed.
  • an S i Ox layer was formed on the optical interference layer by a sputtering method using a Si target.
  • the thickness of the formed SiO 2 layer was about 2.0 nm.
  • an ITO layer was formed on the SiO 2 layer by sputtering using indium oxide and tin oxide in a composition of 97: 3 by weight and a packing density of 98% indium oxide monooxide, and a movable electrode was formed.
  • a transparent conductive laminate serving as a substrate was produced.
  • the thickness of the formed ITO layer was about 20 nm, and the surface resistance after film formation was about 550 ⁇ / ⁇ ( ⁇ / s Q).
  • the prepared movable electrode substrate was subjected to a heat treatment at 150 ° C.
  • Example 4 A fixed electrode substrate was produced in the same manner as in Example 1. Using the fabricated fixed electrode substrate and movable electrode substrate, a transparent sunset panel shown in FIG. 4 was fabricated. A writing durability test and edge pressing durability test were performed on the fabricated transparent touch panel, and the linearity before and after the test is shown in Table 1.
  • Example 4 A writing durability test and edge pressing durability test were performed on the fabricated transparent touch panel, and the linearity before and after the test is shown in Table 1.
  • a 4 m-thick hard coat layer 1 was formed on one surface of a 188 m-thick polyethylene terephthalate film (OFW manufactured by Teijin Dupont Film Co., Ltd.) using a UV-curable polyfunctional acrylate resin paint.
  • a synthetic latex (“Ni po 1 LX857X2” manufactured by Zeon Corporation) is coated on the opposite side of the hard coat layer 1 by the per coat method, dried at 100 ° C. for 2 minutes, and then dried to a second thickness of 6 m.
  • a hard dangling shelf layer was formed.
  • the coating liquid A of Example 1 is coated on the second hardening resin layer by a bar coating method so as to have a film thickness of 5.0, and is irradiated and cured by irradiation with ultraviolet rays to form the first hardening resin layer ( a) was formed.
  • the coating liquid E used in Example 1 was coated on the surface of the first curable resin layer (a) by the vacuum coating method, and after baking at 130 for 2 minutes, a high refractive index having a thickness of 55 nm was obtained. A layer was formed.
  • coating liquid B used in Example 1 as a low refractive index layer was coated by a bar coating method and baked for 132 minutes to form a low refractive index layer, thereby forming a high refractive index layer.
  • An optical interference layer composed of a refractive index layer and a low refractive index layer was formed.
  • a Si ⁇ x layer was formed on the optical interference layer by a sputtering method using a Si target. The thickness of the formed SiO 2 layer was about 2. Onm.
  • an ITO layer was formed on the SiO x layer by sputtering using indium oxide and tin oxide in a weight ratio of 97: 3 and a packing density of 98% indium tin oxide, and the movable layer was formed.
  • a transparent conductive laminate serving as 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 550 ⁇ / port ( ⁇ / sq).
  • the fabricated movable electrode substrate was subjected to a heat treatment at 150 ° C. for 60 minutes to crystallize the ITO layer. No haze change was observed on the movable electrode substrate before and after the heat treatment, and the surface resistance after crystallization of the ITO was approximately 450 ⁇ / port ( ⁇ / sq).
  • a fixed electrode substrate was produced in the same manner as in Example 1. Using the fabricated fixed electrode substrate and movable electrode substrate, a transparent sunset panel shown in FIG. 5 was fabricated. A writing durability test and an edge pressing durability test were performed on the fabricated transparent panel and the linearity before and after the test is shown in Table 1. Comparative Example 2 A 4 m-thick hard coat layer 1 was formed on one side of a 188 m-thick polyethylene terephthalate film (O FW manufactured by Teijin DuPont Films Co., Ltd.) using an ultraviolet-curable polyfunctional acrylate resin paint. did. The coating liquid C used in Example 1 was coated on the surface opposite to the hard coat layer 1 by a bar coating method, and heat-treated at 130 ° C. for 1 minute to form a first curable resin layer (c). Table 1 shows the results of the measurement of the Young's modulus and the plastic deformation hardness of the first hardened durable shelf layer (c).
  • the coating liquid C prepared in Example 1 was coated on the first curable resin layer (c) by a bar coating method, baked at 130 ° C. for 2 minutes, and then a third curable resin layer was prepared.
  • a third curable resin layer was prepared.
  • an ITO layer is formed on the third curable resin layer by a sputtering method using an indium oxide-tin oxide target having a composition of indium oxide and tin oxide in a weight ratio of 95: 5 and a packing density of 98%.
  • a transparent conductive laminate serving as a movable electrode substrate was produced.
  • the film thickness of the formed ITO layer was about 20 nm, and the surface resistance after the film formation was about 350 ⁇ / ⁇ ( ⁇ / sq).
  • a fixed electrode substrate was produced in the same manner as in Example 1.
  • a transparent touch panel was fabricated using the fixed electrode substrate and the ITO layer which were not crystallized by heat treatment and remained amorphous as the movable electrode substrate.
  • a writing durability test and edge pressing durability test were performed on the fabricated transparent touch panel, and the linearity before and after the test is shown in Table 1.
  • HV X Plastic deformation hardness of the first curable resin layer by indentation test
  • the ITO layer was peeled and whitened at the written mark after both the writing durability test and the edge pressing durability test. It was confirmed that.
  • a 188 m thick polyethylene terephthalate film (Tijin Tetron Film OFW manufactured by Teijin Dupont Film Co., Ltd.) is coated on one side with a UV-curable multi-functional acrylate resin paint and a 4 m thick hard coat layer 1 Was formed.
  • a curable resin component 100 parts by weight of a tetrafunctional acrylate (“ALONIX” M400 manufactured by Toa Gosei Co., Ltd.) and a radical type “6” polymerization initiator (“IRGACURE” 184) manufactured by Ciba Specialty Chemicals 184) 5 parts by weight was dissolved in methyl isobutyl ketone (MIBK) to prepare a coating solution G.
  • MIBK methyl isobutyl ketone
  • the Uretanakuri rate to prepare a mixed coating solution I as a resin component and monomer is 2 00 parts by weight relative to the coating liquid G and Fluid H and the Kati ⁇ resin component 100 parts by weight.
  • Ultra-fine particles of MgF 2 having a primary particle size of 15 nm were added to Coating Liquid I in an amount of 200 parts by weight based on 100 parts by weight of the curable resin component to prepare Coating Liquid J.
  • the coating liquid J was coated by a percoat method, and was cured by irradiation with ultraviolet rays to form a first curable resin layer (d).
  • the thickness of the formed first curable resin layer (d) was 2 m.
  • a sample (thickness: 5 m) for measuring the Young's modulus of the first curable resin layer (d) was prepared by the same method, and the Young's modulus and the plastic deformation hardness were measured. Table 2 shows the measurement results.
  • the alkoxysilane coating liquid C used in Example 1 was coated by a vacuum coating method and baked at 130 ° C for 2 minutes. Produced. Further, an ITO layer was formed on the third curable resin layer by sputtering using a target of indium oxide and tin oxide having a composition of 95: 5 by weight and a packing density of 98%. The transparent conductor that forms and becomes the movable electrode substrate An electrically conductive laminate was produced. The thickness of the formed ITO layer was about 20 nm, and the surface resistance after film formation was about 350 ⁇ / port ( ⁇ / sq).
  • the prepared movable electrode substrate was subjected to a heat treatment for 150 to 90 minutes to crystallize the IT layer. No haze change was observed in the movable electrode substrate before and after the heat treatment, and the surface resistance after the crystallization of the ITO layer was about 280 ⁇ / ⁇ ( ⁇ / sq).
  • One side of a 188 m thick polyethylene terephthalate film (“Tijin Tetron Film” OFW manufactured by Teijin DuPont Films Co., Ltd.) is coated with a 4 m thick hard coat using UV curable polyfunctional acrylate resin paint.
  • Layer 1 was formed.
  • Acrylonitrile butadiene rubber (“ipo 1 1052 J” manufactured by Zeon Corporation) was dissolved in toluene to prepare a coating solution K.
  • the synthetic rubber component coating solution and the curable shelf component coating solution ⁇ used in Example 1 were mixed and coated so that the synthetic rubber component was 50 parts by weight with respect to 100 parts by weight of the curable resin component.
  • Working liquid L was prepared.
  • the primary particle diameter coating solution L was prepared coating liquid M was added 100 parts by weight relative to S i 0 2 particles curable resin component 10 0 parts by weight of 40 nm.
  • the first coating resin layer is coated with the prepared coating liquid M by the bar coating method and cured by irradiation with ultraviolet rays.
  • the coating liquid E used in Example 2 was coated by a bar coating method on the surface of the first curable resin layer (e), and baked at 130 ° C for 2 minutes. A refractive index layer was formed.
  • the low refractive index layer was formed by coating the alkoxysilane coating solution B used in Example 2 as a low refractive index layer on the high refractive index layer by a bar coating method and firing at 130 ° C for 2 minutes.
  • An optical interference layer composed of a high refractive index layer and a low refractive index layer was formed.
  • an ITO layer was formed on the optical interference layer by a sputtering method in the same manner as in Example 2 to produce a transparent conductive laminate serving as a movable electrode substrate.
  • the thickness of the formed ITO layer was about 20 nm, and the surface resistance after film formation was about 350 Q / ⁇ ( ⁇ / sq).
  • the prepared movable electrode substrate was subjected to a heat treatment at 150 ° C.
  • Example 7 shows the change in linearity between before and after the test.
  • a 188-m-thick polyethylene terephthalate film (Tijin Tetron Film OFW manufactured by Teijin Dupont Film Co., Ltd.) is coated on one side with a UV-curable polyfunctional acrylate resin paint and has a thickness of 4 and a hard coat layer 1 Was formed.
  • the coating liquid J used in Example 5 was coated on the surface opposite to the hard coat layer 1 by a bar coating method so as to have a thickness of 3.0 m, and was irradiated and cured by ultraviolet irradiation to form the first curable resin layer. (D) was formed.
  • the coating liquid E used in Example 2 was coated on the surface of the first curable resin layer (d) in the same manner as in Example 2 by the vacuum coating method, and baked at 130 ° C for 2 minutes. A high refractive index layer with a thickness of 55 nm was formed.
  • the coating liquid B used in Example 2 was coated as a low refractive index layer on the high refractive index layer by a bar coating method, and baked for 130 minutes to form a low refractive index layer, thereby forming a high refractive index layer.
  • An optical interference layer composed of a refractive index layer and a low refractive index layer was formed. Further, a SiO 2 layer was formed on the optical interference layer by a sputtering method using a SiO target.
  • the thickness of the formed SiO 2 layer was about 2. Onm.
  • an ITO layer was formed on the SiO x layer by sputtering using indium oxide and tin oxide in a weight ratio of 97: 3, and a packing density of 98%, and a sputtering density of 98%.
  • a transparent conductive laminate serving as an electrode substrate was produced.
  • the thickness of the formed ITO layer was about 2 Onm, and the surface resistance after film formation was about 550 ⁇ / D ( ⁇ / sq).
  • the prepared movable electrode substrate was subjected to a heat treatment for 150 to 60 minutes to crystallize the ITO layer. No haze change was observed on the movable electrode substrate before and after the heat treatment, and the surface resistance after the crystallization of the ITO was about 450 ⁇ / port ( ⁇ / sq).
  • a fixed electrode substrate was produced in the same manner as in Example 4.
  • the transparent touch panel shown in FIG. 4 was fabricated using the fabricated fixed electrode substrate and movable electrode substrate.
  • Table 2 shows the linearity of the fabricated transparent panel made before and after the test.
  • Example 8
  • a 4 m-thick hard coat layer 1 is formed on one side of a 188 m-thick polyethylene terephthalate film ("Tidin Tetron Film OFW” manufactured by Teijin Dupont Film Co., Ltd.) using a UV-curable multifunctional acrylate resin paint. did.
  • Synthetic latex (Nipo 1 LX857X2J, manufactured by Nippon Zeon Co., Ltd.) is coated on the opposite side of the hard coat layer 1 by the vacuum coating method, dried for 100 minutes, and then cured to a second film thickness of 6 A resin layer was formed.
  • the coating liquid J used in Example 5 was coated on the second curable resin layer by a bar coating method so as to have a film thickness of 5.0 m, and was irradiated and cured with ultraviolet rays to cure the first curable resin.
  • Layer (d) was formed.
  • the Young's modulus of the surface on which the first curable resin layer (d) was formed was determined by an indentation hardness test. The results are shown in Table 2.
  • the coating liquid E used in Example 2 was coated by a bar coating method on the surface of the first curable resin layer (d) in the same manner as in Example 2 and baked at 130 ° C for 2 minutes. A high refractive index layer having a thickness of 55 nm was formed.
  • the coating liquid B used in Example 1 was coated on the high refractive index layer as a low refractive index layer by a bar coating method, and was baked for 130 minutes to form a low refractive index layer.
  • An optical interference layer composed of a refractive index layer and a low refractive index layer was formed.
  • a Si ⁇ x layer was formed on the optical interference layer by a sputtering method using a Si substrate. The thickness of the formed SiO x layer was about 2.0 nm.
  • an ITO layer was formed on the SiO x layer by sputtering using an indium tin oxide target having a composition of indium oxide and tin oxide in a weight ratio of 97: 3 and a packing density of 98%, A transparent conductive laminate serving as a movable electrode substrate was produced.
  • the film thickness of the formed ITO layer was about 20 nm, and the surface resistance after film formation was about 550 ( ⁇ / sq).
  • the prepared movable electrode substrate was subjected to a heat treatment at 150 for 60 minutes to crystallize the ITO layer. No change in haze was observed on the movable electrode substrate before and after the heat treatment, and the surface resistance after the crystallization of the ITO layer was about 450 ⁇ / port ( ⁇ / sq).
  • a fixed electrode substrate was produced in the same manner as in Example 4. Using the fabricated fixed electrode substrate and movable electrode substrate, a transparent sunset panel shown in FIG. 5 was fabricated. Table 2 shows the linearity of the fabricated transparent panel made before and after the test. Comparative Example 3
  • the coating liquid G prepared in Example 5 was coated on the surface opposite to the hard coat layer 1 by a bar coating method so as to have a thickness of 3.0, and was irradiated and cured by irradiation with ultraviolet rays to form the first curable resin layer (f). Was formed.
  • the Young's modulus and plastic deformation hardness of the prepared first curable resin layer (f) were measured. Table 2 shows the measurement results.
  • a third curable resin layer and a second layer were formed on the first curable resin layer ( ⁇ ) in the same manner as in Example 1 to produce a transparent conductive laminate serving as a movable electrode substrate.
  • the film thickness of the formed layer was about 20 nm, and the surface resistance after film formation was about 350 ⁇ ( ⁇ / sq).
  • the prepared movable electrode substrate was subjected to a heat treatment at 150 ° C. for 90 minutes to crystallize the ITO layer. No haze change was observed on the movable electrode substrate before and after the heat treatment, and the surface resistance after the crystallization of the ITO layer was about 280 ⁇ / ⁇ ( ⁇ / sq).
  • a fixed electrode substrate was produced in the same manner as in Example 1. Using the fabricated fixed electrode substrate and movable electrode substrate, a transparent sunset panel shown in FIG. 1 was fabricated. Table 2 shows the linearity of the fabricated transparent panel made before and after the test. Comparative Example 4
  • a 188 m thick polyethylene terephthalate film (Tijin Tetron Film OFW manufactured by Teijin Dupont Film Co., Ltd.) is coated on one side with a UV-curable multi-functional acrylate resin paint and a 4 m thick hard coat layer 1 Was formed.
  • the coating liquid I prepared in Example 5 was coated on the surface opposite to the hard coat layer 1 by a coating method so as to have a thickness of 3.0 m, and was irradiated and cured by ultraviolet irradiation to form a first curable resin layer. (g) was formed.
  • the Young's modulus and plastic deformation hardness of the prepared first curability measurement layer (g) were measured. Table 2 shows the measurement results.
  • a third curable resin layer and an IT layer were formed on the first curable resin layer (g) in the same manner as in Example 1 to produce a transparent conductive laminate serving as a movable electrode substrate.
  • the thickness of the formed ITO layer was about 20 nm, and the surface resistance after film formation was about 350 Q / U ( ⁇ / sq).
  • the prepared movable electrode substrate was heat-treated at 150 ° C for 90 minutes. However, fine wrinkles were formed in the IT ⁇ layer, and the haze of the movable electrode substrate became large (whitened), Comparative Example 5
  • a 4 m thick polyethylene terephthalate film (Tijin Tetron Film OFW manufactured by Teijin Dupont Film Co., Ltd.) with a thickness of 188 wm is coated on one side with an ultraviolet-cured acrylic resin paint.
  • One docot layer 1 was formed.
  • the coating liquid L prepared in Example 6 was coated on the surface opposite to the hard coat layer 1 by a bar coating method so that the film thickness became 3.
  • Layer (h) was formed.
  • the Young's modulus and plastic deformation hardness of the first hardenable shelf layer (h) were measured. Table 2 shows the measurement results.
  • a third curable resin layer and an ITO layer were formed on the first curable resin layer (h) in the same manner as in Example 1, to produce a transparent conductive laminate serving as a movable electrode substrate.
  • the thickness of the formed ITO layer was about 20 nm, and the surface resistance after film formation was about 350 ⁇ / ⁇ ( ⁇ / sq).
  • the prepared movable electrode substrate was subjected to a heat treatment at 150 ° C. for 90 minutes, but fine wrinkles were formed in the ITO layer, and the haze of the movable electrode substrate became large (white shading).
  • HV X Plastic deformation hardness by indentation test of the first curable resin layer alone

Landscapes

  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Human Computer Interaction (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Laminated Bodies (AREA)
  • Position Input By Displaying (AREA)
  • Non-Insulated Conductors (AREA)

Abstract

L'invention concerne un laminé conducteur transparent comprenant un substrat de polymère organique transparent et, superposées de manière séquentielle sur au moins une surface de celui-ci, une couche de résine durcissable et une couche conductrice transparente. La couche de résine durcissable est soit constituée d'une résine durcissable dont le composant principal est un (méth)acrylate d'acide N-hydroxyalkylisocyanurique, avec une épaisseur de 10 νm ou moins, soit une résine constituée d'un composant de résine durcissable, un des composants de la résine au moins étant, comme monomère, constitué d'acrylate d'uréthane (B) ou d'un composant de caoutchouc synthétique (A), et d'ultramicroparticules (C) d'oxyde métallique ou de fluorure métallique de 100 nm ou moins de diamètre de particule principal. Ledit laminé conducteur transparent permet d'améliorer la durabilité d'écriture nécessaire dans les écrans tactiles transparents. L'utilisation de ce laminé conducteur transparent permet d'obtenir un écran tactile transparent amélioré par rapport à la durabilité de dépression de fusion, c'est-à-dire la durabilité d'écriture, au niveau des zones marginales de l'écran tactile transparent.
PCT/JP2004/015201 2003-10-08 2004-10-07 Lamine conducteur transparent et ecran tactile transparent WO2005036565A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2003-349317 2003-10-08
JP2003349317A JP2007042283A (ja) 2003-10-08 2003-10-08 透明導電性積層体及び透明タッチパネル
JP2003365900A JP2007042284A (ja) 2003-10-27 2003-10-27 透明導電性積層体及び透明タッチパネル
JP2003-365900 2003-10-27

Publications (1)

Publication Number Publication Date
WO2005036565A1 true WO2005036565A1 (fr) 2005-04-21

Family

ID=34436902

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2004/015201 WO2005036565A1 (fr) 2003-10-08 2004-10-07 Lamine conducteur transparent et ecran tactile transparent

Country Status (2)

Country Link
TW (1) TW200519977A (fr)
WO (1) WO2005036565A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090315849A1 (en) * 2007-01-16 2009-12-24 Teijin Limited Transparent conductive multilayer body and touch panel made of the same

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101146530B1 (ko) * 2005-08-30 2012-05-25 삼성전자주식회사 스피커 겸용 터치 패널
JP5530743B2 (ja) * 2009-04-14 2014-06-25 リンテック株式会社 凹凸追従性積層部材及びそれを用いたタッチパネル付き表示装置
CN103858182B (zh) * 2012-03-23 2015-06-03 积水纳米涂层科技有限公司 透光性导电性膜、其制造方法及其用途

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08192492A (ja) * 1995-01-17 1996-07-30 Mitsui Toatsu Chem Inc 透明導電性フィルム
JPH09262926A (ja) * 1996-03-27 1997-10-07 Teijin Ltd タッチパネル用透明導電積層体及びその製造方法
JPH09262925A (ja) * 1996-03-27 1997-10-07 Teijin Ltd タッチパネル用透明導電積層体及びその製造方法
JPH11286067A (ja) * 1998-04-03 1999-10-19 Mitsubishi Chemical Corp 導電性プラスチック積層体
JP2001332129A (ja) * 2000-05-19 2001-11-30 Tdk Corp 機能性膜

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08192492A (ja) * 1995-01-17 1996-07-30 Mitsui Toatsu Chem Inc 透明導電性フィルム
JPH09262926A (ja) * 1996-03-27 1997-10-07 Teijin Ltd タッチパネル用透明導電積層体及びその製造方法
JPH09262925A (ja) * 1996-03-27 1997-10-07 Teijin Ltd タッチパネル用透明導電積層体及びその製造方法
JPH11286067A (ja) * 1998-04-03 1999-10-19 Mitsubishi Chemical Corp 導電性プラスチック積層体
JP2001332129A (ja) * 2000-05-19 2001-11-30 Tdk Corp 機能性膜

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090315849A1 (en) * 2007-01-16 2009-12-24 Teijin Limited Transparent conductive multilayer body and touch panel made of the same
US11327621B2 (en) * 2007-01-16 2022-05-10 Teijin Limited Transparent conductive multilayer body and touch panel made of the same

Also Published As

Publication number Publication date
TW200519977A (en) 2005-06-16

Similar Documents

Publication Publication Date Title
EP2109116B1 (fr) Corps multicouche conducteur transparent et écran tactile constitué de ce corps
JP4575384B2 (ja) 透明導電性積層体および透明タッチパネル
KR101521317B1 (ko) 투명 도전성 적층체 및 터치 패널
EP2211356B1 (fr) Stratifié conducteur transparent et panneau tactile transparent
JP4869178B2 (ja) 透明導電性積層体及びこれを用いた透明タッチパネル
WO2005052956A1 (fr) Stratifie conducteur transparent et ecran tactile comprenant ledit stratifie
KR20140016919A (ko) 투명 도전성 적층체 및 투명 터치 패널
JP2007042284A (ja) 透明導電性積層体及び透明タッチパネル
KR20070051307A (ko) 투명 도전성 적층체 및 투명 터치 패널
JP2006252875A (ja) 透明導電性積層体及び透明タッチパネル
JP2005104141A (ja) 透明導電性積層体及び透明タッチパネル
WO2005036565A1 (fr) Lamine conducteur transparent et ecran tactile transparent
JP2007042283A (ja) 透明導電性積層体及び透明タッチパネル
JP2005116515A (ja) 透明導電性積層体及び透明タッチパネル
JP2005014572A (ja) 端押し耐久性に優れた透明導電性積層体
JP2006190512A (ja) 透明導電性積層体及びそれを用いた透明タッチパネル
JP2006190508A (ja) 透明導電性積層体及びそれを用いた透明タッチパネル
JP2006190510A (ja) 透明導電性積層体及びそれを用いた透明タッチパネル
JP2006190511A (ja) 透明導電性積層体及びそれを用いた透明タッチパネル
JP2006190509A (ja) 透明導電性積層体及びそれを用いた透明タッチパネル

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP

WWW Wipo information: withdrawn in national office

Country of ref document: JP