WO2018180926A1 - 導電層付きフィルム、タッチパネル、導電層付きフィルムの製造方法およびタッチパネルの製造方法 - Google Patents

導電層付きフィルム、タッチパネル、導電層付きフィルムの製造方法およびタッチパネルの製造方法 Download PDF

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WO2018180926A1
WO2018180926A1 PCT/JP2018/011518 JP2018011518W WO2018180926A1 WO 2018180926 A1 WO2018180926 A1 WO 2018180926A1 JP 2018011518 W JP2018011518 W JP 2018011518W WO 2018180926 A1 WO2018180926 A1 WO 2018180926A1
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Prior art keywords
film
conductive layer
polyimide
conductive
layer
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PCT/JP2018/011518
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English (en)
French (fr)
Japanese (ja)
Inventor
耕司 上岡
昭典 佐伯
西山　雅仁
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東レ株式会社
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Priority to JP2019509681A priority Critical patent/JP7140108B2/ja
Priority to KR1020197025834A priority patent/KR102524863B1/ko
Priority to CN201880021695.8A priority patent/CN110447005B/zh
Publication of WO2018180926A1 publication Critical patent/WO2018180926A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
    • C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D171/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C09D171/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C09D171/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/10—Glass or silica
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input 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
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F2203/00—Indexing scheme relating to G06F3/00 - G06F3/048
    • G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
    • G06F2203/04103—Manufacturing, i.e. details related to manufacturing processes specially suited for touch sensitive devices

Definitions

  • the present invention relates to a film with a conductive layer, a touch panel, a method for manufacturing a film with a conductive layer, and a method for manufacturing a touch panel.
  • Patent Documents 1 and 2 disclose a transparent conductive film in which a thin film made of ITO is formed on a polyimide film having excellent heat resistance. By patterning the thin film by etching, a film with a conductive layer excellent in visibility and conductivity can be obtained.
  • the ITO wiring is rigid and brittle, there is a problem that bending resistance is low and cracking occurs when bent.
  • metal mesh wiring is attracting attention as a transparent conductive layer having both bending resistance, visibility, and high conductivity.
  • Metal mesh wiring can be obtained by forming a metal wiring that is thin enough to be invisible to the mesh pattern. For example, by using a metal having a small electrical resistance value, such as gold, silver, or copper, a wiring with good conductivity can be obtained. Furthermore, the bending resistance of the wiring can be improved by containing an appropriate amount of an organic component that can be patterned by photolithography and has excellent flexibility. Such metal mesh wiring can sufficiently cope with flexibility.
  • a conductive paste composed of conductive metal particles (hereinafter referred to as conductive particles as appropriate) and an organic component is used, and patterning is performed by screen printing, inkjet, photolithography, or the like.
  • conductive particles conductive metal particles
  • an organic component conductive metal particles
  • patterning is performed by screen printing, inkjet, photolithography, or the like.
  • conductive particles have a problem of being easily fused and aggregated even at room temperature.
  • the surface of the conductive particles reacts with an organic component and the storage stability of the conductive paste is lowered.
  • the conductive particles have light reflectivity, which scatters exposure light, and thus there is a problem that it is difficult to form a fine pattern.
  • a method for solving the above problem by using conductive particles having a coating layer is disclosed (for example, see Patent Document 3).
  • the surface activity of the conductive particles can be reduced by the coating layer, and at least one of the reaction between the conductive particles and the reaction between the conductive particles and the organic component can be suppressed. Even when photolithography is used, scattering of exposure light can be suppressed and wiring can be patterned with high accuracy.
  • the coated conductive particles can be easily removed by heating at a high temperature of about 200 ° C. Therefore, sufficient electrical conductivity can be expressed in the wiring.
  • JP 2016-186936 A Japanese Patent No. 5773090 JP 2013-196997 A
  • Patent Document 3 requires heating at about 200 ° C. in the presence of oxygen in order to remove the coating layer of conductive particles. For this reason, high heat resistance and oxidation resistance are required for the substrate, and substantially only a glass substrate can be applied. As a matter of course, it is difficult to cope with flexibility using a glass substrate. Furthermore, even when a film with excellent heat resistance is used, the color may deteriorate due to the coloration of the film by heating in the presence of oxygen, and the dimensional accuracy of the film may decrease and misalignment may occur. There has been a problem that an appearance defect called moire occurs.
  • This invention is made
  • the place made into the objective is suppressing the yellowing at the time of conductive layer formation, and the film with a conductive layer which was excellent in the dimensional accuracy of the conductive layer, a touch panel, conductive It is providing the manufacturing method of a film with a layer, and the manufacturing method of a touch panel.
  • the inventors of the present invention have a structure in which a gas barrier layer is provided between a conductive film and a resin film (polyimide resin film) containing polyimide having a specific imide group concentration. It has been found that the polyimide resin film can be prevented from coming into contact with oxygen during heating of the layer, and the deterioration of the color and dimensional accuracy of the polyimide resin film can be suppressed.
  • the film with a conductive layer according to the present invention has an imide group concentration defined by the following formula (I) of 20.0% or more and 36.5% or less.
  • the film with a conductive layer according to the present invention is characterized in that, in the above invention, the glass transition temperature of the resin film is 250 ° C. or higher.
  • the film with a conductive layer according to the present invention is characterized in that, in the above invention, the polyimide includes a structural unit represented by the following general formula (1).
  • R 1 has a monocyclic or condensed polycyclic alicyclic structure, a tetravalent organic group having 4 to 40 carbon atoms, or a monocyclic alicyclic structure.
  • R 2 represents a divalent organic group having 4 to 40 carbon atoms.
  • the film with a conductive layer according to the present invention is characterized in that, in the above invention, the polyimide includes a structural unit represented by the following general formula (2).
  • R 3 represents a tetravalent organic group having 4 to 40 carbon atoms.
  • R 4 has a monocyclic or condensed polycyclic alicyclic structure and has 4 to 40 carbon atoms. Or a divalent organic group having 4 to 40 carbon atoms in which organic groups having a monocyclic alicyclic structure are connected to each other directly or via a crosslinked structure, or the following general group A divalent organic group represented by the formula (3) is shown.
  • X 1 is a divalent hydrocarbon group having 1 to 3 carbon atoms which may be substituted with a halogen atom.
  • Ar 1 and Ar 2 are each independently a carbon number. Represents a divalent aromatic group of 4 to 40.
  • the film with a conductive layer according to the present invention is the above invention, wherein the polyimide has a structural unit represented by the following general formula (4) as a main component and is represented by the following general formula (5).
  • the structural unit is characterized by containing 5 mol% or more and 30 mol% or less of all structural units.
  • R 1 represents a monovalent or condensed polycyclic alicyclic structure, a tetravalent organic group having 4 to 40 carbon atoms, or a monocyclic fatty acid.
  • a tetravalent organic group having 4 to 40 carbon atoms in which organic groups having a ring structure are connected to each other directly or via a crosslinked structure R 13 is a divalent group represented by the following general formula (6).
  • R 14 is a structure represented by the following structural formula (7) or the following structural formula (8).
  • R 15 to R 22 each independently represent a hydrogen atom, a halogen atom, or a monovalent organic group having 1 to 3 carbon atoms which may be substituted with a halogen atom.
  • X 2 is selected from a direct bond, an oxygen atom, a sulfur atom, a sulfonyl group, a divalent organic group having 1 to 3 carbon atoms which may be substituted with a halogen atom, an ester bond, an amide bond, and a sulfide bond.
  • the film with a conductive layer according to the present invention is the above invention, wherein the polyimide is represented by the following general formula (9) in at least one of the acid dianhydride residue and the diamine residue constituting the polyimide. It contains the repeating structure represented by these, It is characterized by the above-mentioned.
  • R 23 and R 24 each independently represents a monovalent organic group having 1 to 20 carbon atoms.
  • M is an integer of 3 to 200.
  • the film with a conductive layer according to the present invention is characterized in that, in the above invention, the polyimide contains a triamine skeleton.
  • the film with a conductive layer according to the present invention is characterized in that, in the above invention, the gas barrier layer includes at least one of silicon oxide, silicon nitride, silicon oxynitride, and silicon carbonitride.
  • the gas barrier layer may be SiOxNy (where x and y are 0 ⁇ x ⁇ 1, 0.55 ⁇ y ⁇ 1 and 0 ⁇ x / y ⁇ 1). It is a value which satisfy
  • the film with a conductive layer according to the present invention is the above-described invention, wherein the gas barrier layer is an inorganic film laminated in two or more layers, and the layer in contact with the conductive layer in the inorganic film is SiOz (z Is a value satisfying 0.5 ⁇ z ⁇ 2)).
  • the conductive layer-attached film according to the present invention is characterized in that, in the above invention, the conductive particles are silver particles.
  • the film with a conductive layer according to the present invention is formed from an alkali-soluble resin including a cardo resin having two or more structures represented by the following structural formula (10) on the conductive layer in the above invention. And an insulating layer.
  • a touch panel according to the present invention includes the film with a conductive layer according to any one of the above inventions, and the conductive layer is a wiring layer.
  • the method for producing a film with a conductive layer according to the present invention includes a resin film forming step of forming a resin film containing polyimide on a support substrate, and a gas barrier layer forming step of forming a gas barrier layer on the resin film. And a conductive layer forming step of forming a conductive layer on the gas barrier layer, and a peeling step of peeling the resin film from the support substrate.
  • the conductive layer forming step uses a conductive composition containing conductive particles having a coating layer on at least a part of the surface.
  • the conductive layer is formed.
  • the resin film forming step is performed at 300 ° C. in an atmosphere having an oxygen concentration of 1000 ppm or less.
  • the resin film is formed by heating at a temperature of 500 ° C. or lower, and in the conductive layer forming step, the conductive composition on the gas barrier layer is heated to 100 ° C. or higher in an atmosphere having an oxygen concentration of 15% or higher.
  • the conductive layer is formed by heating at a temperature of 300 ° C. or lower.
  • the manufacturing method of the touchscreen which concerns on this invention is a manufacturing method of the touchscreen using the manufacturing method of the film with a conductive layer as described in any one of said invention, Comprising:
  • the said conductive layer formation process is the said electroconductivity. It is a step of forming a wiring layer as a layer.
  • ADVANTAGE OF THE INVENTION providing the film with a conductive layer which suppressed yellowing at the time of conductive layer formation, and was excellent in the dimensional accuracy of a conductive layer, a touch panel, the manufacturing method of a film with a conductive layer, and the manufacturing method of a touch panel are provided. There is an effect that can be done.
  • FIG. 1 is a schematic cross-sectional view showing a configuration example of a film with a conductive layer according to an embodiment of the present invention.
  • FIG. 2 is a plan view showing a configuration example of a touch panel including a film with a conductive layer according to an embodiment of the present invention according to the embodiment of the present invention.
  • FIG. 3 is a schematic cross-sectional view showing a configuration example of a touch panel including a film with a conductive layer according to an embodiment of the present invention.
  • FIG. 4 is a process diagram showing an example of a method for manufacturing a touch panel including a film with a conductive layer according to an embodiment of the present invention.
  • the film with a conductive layer according to the embodiment of the present invention is a film with a conductive layer having a conductive layer containing conductive particles on a resin film containing polyimide, and between the resin film and the conductive layer. Has a gas barrier layer.
  • this resin film contains polyimide having an imide group concentration defined by the following formula (I) of 20.0% or more and 36.5% or less. (Molecular weight of the imide group) / (Molecular weight of the repeating unit of polyimide) x 100 [%] ... (I)
  • FIG. 1 is a schematic cross-sectional view showing a configuration example of a film with a conductive layer according to an embodiment of the present invention.
  • the film 11 with a conductive layer includes a resin film 1, a gas barrier layer 2, and a conductive layer 3A.
  • the resin film 1 is a polyimide resin film containing polyimide in which the imide group concentration defined by the formula (I) is 20.0% or more and 36.5% or less.
  • the gas barrier layer 2 is formed on the resin film 1.
  • the conductive layer 3 ⁇ / b> A is a conductive layer containing conductive particles, and is formed on the gas barrier layer 2.
  • the gas barrier layer 2 is interposed between the resin film 1 and the conductive layer 3A as shown in FIG. Thereby, the gas barrier layer 2 can prevent the oxygen at the time of heat-forming the conductive layer 3 ⁇ / b> A from coming into contact with the resin film 1. As a result, a decrease in color of the resin film 1 due to heating in the presence of oxygen (for example, a decrease in color due to yellowing) is suppressed.
  • the film 11 with a conductive layer may further include an insulating layer on the conductive layer 3A.
  • FIG. 2 is a plan view showing a configuration example of a touch panel including a film with a conductive layer according to an embodiment of the present invention.
  • FIG. 3 is a schematic cross-sectional view showing a configuration example of a touch panel including a film with a conductive layer according to an embodiment of the present invention.
  • FIG. 3 is a cross-sectional view of the touch panel 10 taken along a broken line I-I ′ in FIG.
  • This touch panel 10 is a touch panel including the film 11 with a conductive layer according to the present embodiment.
  • the touch panel 10 includes a resin film 1, a gas barrier layer 2, a first wiring layer 3, a first insulating layer 4, a second wiring layer 5, and a second wiring layer. And an insulating layer 6.
  • the resin film 1 and the gas barrier layer 2 are the same as the film 11 with a conductive layer shown in FIG.
  • the first wiring layer 3 is an application example of the conductive layer 3A of the film 11 with the conductive layer. That is, the touch panel 10 includes the resin film 1, the gas barrier layer 2, and the first wiring layer 3 as the film 11 with a conductive layer.
  • the first wiring layer 3 is formed on the gas barrier layer 2 on the resin film 1 so as to form a desired wiring pattern.
  • the first insulating layer 4 is formed on the first wiring layer 3 and the gas barrier layer 2 so as to cover the first wiring layer 3 other than the electrode portion.
  • the second wiring layer 5 is a wiring layer different from the first wiring layer 3 and is formed on the first insulating layer 4 and the gas barrier layer 2 so as to form a desired wiring pattern.
  • the first wiring layer 3 and the second wiring layer 5 are insulated by the first insulating layer 4.
  • the second insulating layer 6 is formed on the second wiring layer 5 and the first insulating layer 4 so as to cover the second wiring layer 5 other than the electrode portion.
  • the resin film (for example, the resin film 1 shown in FIG. 1) used for the film with a conductive layer according to the embodiment of the present invention has an imide group concentration defined by the above formula (I) of 20.0% or more and 36.36. Contains polyimide that is 5% or less.
  • the imide group concentration of the resulting polyimide decreases as the molecular weight of each monomer (diamine and tetracarboxylic dianhydride) increases.
  • the imide group concentration is lower than 20.0%, the interaction between polyimide molecules due to the imide group becomes weak, and the glass transition temperature (Tg) of the polyimide decreases.
  • Tg glass transition temperature
  • the imide group concentration is a value obtained by calculation by the following method.
  • the molecular weight of the imide group part is the molecular weight of the (—CO—N—CO—) part contained in the polyimide repeating unit.
  • the molecular weight per imide group is 70.03.
  • the molecular weight of the repeating unit of a polyimide is the molecular weight of the part originating in the tetracarboxylic dianhydride and diamine which comprise one repeating unit.
  • the molecular weight of the imide group portion is the molecular weight of a portion surrounded by a dotted line.
  • the glass transition temperature (Tg) of the resin film containing polyimide is preferably 250 ° C. or higher. This is because deformation of the resin film is suppressed in the heating step when forming the gas barrier layer or conductive layer on the resin film, and as a result, the dimensional accuracy during processing of the conductive layer is further improved. .
  • the glass transition temperature of the resin film containing polyimide is more preferably 300 ° C. or higher, and particularly preferably 350 ° C. or higher.
  • Examples of a method for measuring the glass transition temperature of the resin film include a measurement method using a thermomechanical analyzer (TMA method).
  • TMA method thermomechanical analyzer
  • a resin film piece having a film thickness of 10 ⁇ m to 20 ⁇ m, a width of 15 mm, a length of 30 mm is wound in the length direction, and a cylinder having a diameter of 3 mm and a height of 15 mm
  • the inflection point of the TMA curve when this sample is heated in a compressed mode in a nitrogen stream at a temperature rising rate of 5 ° C./min is defined as the glass transition temperature of the resin film.
  • the polyimide used for the resin film of the film with a conductive layer contains the structural unit represented by following General formula (1).
  • R 1 is a monovalent or condensed polycyclic alicyclic structure, a tetravalent organic group having 4 to 40 carbon atoms, or an organic having a monocyclic alicyclic structure.
  • R 2 represents a divalent organic group having 4 to 40 carbon atoms.
  • the thermal expansion coefficient (CTE) of the polyimide is lowered. Therefore, when polyimide is formed on a support substrate for a process such as formation of a conductive layer, the warp of the polyimide is reduced, and the dimensional accuracy can be improved in processing of the conductive layer.
  • R 1 in the general formula (1) represents the structure of the acid component.
  • the acid dianhydride having an alicyclic structure is not particularly limited, but 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,4,5-cyclopentanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3 4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid Dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,2,3,4-cycl
  • R 1 in the general formula (1) is preferably at least one selected from six structures represented by the following structural formulas (11) to (16).
  • R 1 is a structure represented by the following structural formulas (17) to (19) from the viewpoint of being commercially available and easy to obtain and the reactivity with the diamine compound. It is more preferable.
  • acid dianhydrides that give these structures to R 1 include 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic dianhydride (for example, product name “PMDA” manufactured by Wako Pure Chemical Industries, Ltd.).
  • R 2 represents the structure of the diamine component.
  • Examples of the diamine compound used in R 2 is not particularly limited, aromatic diamine compounds, alicyclic diamine compounds, or aliphatic diamine compounds.
  • the aromatic diamine compound is not particularly limited, but 1,4-bis (4-aminophenoxy) benzene, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis ⁇ 4- (4-aminophenoxyphenyl) ⁇ sulfone, bis ⁇ 4- (3-aminophenoxyphenyl) ⁇ sulfone, bis (4-aminophenoxy) biphenyl, bis ⁇ 4- (4-aminophenoxy) phenyl ⁇ ether, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane 3-aminophenyl-4-aminobenzenesulfonate, 4-aminophenyl-4-a Roh benzenesul
  • the alicyclic diamine compound is not particularly limited, but is cyclobutanediamine, isophoronediamine, bicyclo [2.2.1] heptanebismethylamine, tricyclo [3.3.1.13,7] decane-1,3- Diamine, 1,2-cyclohexyldiamine, 1,3-cyclohexyldiamine, 1,4-cyclohexyldiamine, 4,4′-diaminodicyclohexylmethane, 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane, 3, 3′-diethyl-4,4′-diaminodicyclohexylmethane, 3,3 ′, 5,5′-tetramethyl-4,4′-diaminodicyclohexylmethane, 3,3 ′, 5,5′-tetraethyl-4, 4'-diaminodicyclohexylmethane, 3,5-
  • the aliphatic diamine compound is not particularly limited, but ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1 Alkylenediamines such as 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, bis (aminomethyl) ether, bis (2-aminoethyl) ether, bis (3-aminopropyl) ether, etc.
  • Ethylene glycol diamines and 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (4-aminobutyl) tetramethyldisiloxane, ⁇ , ⁇ -bis (3-aminopropyl) poly Examples include siloxane diamines such as dimethylsiloxane.
  • aromatic diamine compounds alicyclic diamine compounds, and aliphatic diamine compounds can be used alone or in combination of two or more.
  • the polyimide used for the resin film of the film with a conductive layer preferably contains a structural unit represented by the following general formula (2).
  • R 3 represents a tetravalent organic group having 4 to 40 carbon atoms.
  • R 4 has a monocyclic or condensed polycyclic alicyclic structure, a divalent organic group having 4 to 40 carbon atoms, or an organic group having a monocyclic alicyclic structure directly or has a crosslinked structure.
  • X 1 is a divalent hydrocarbon group having 1 to 3 carbon atoms which may be substituted with a halogen atom.
  • Ar 1 and Ar 2 each independently represents a divalent aromatic group having 4 to 40 carbon atoms.
  • the thermal expansion coefficient of the polyimide is lowered. Therefore, when polyimide is formed on a support substrate for a process such as formation of a conductive layer, the warp of the polyimide is reduced, and the dimensional accuracy can be improved in processing of the conductive layer.
  • R 3 in the general formula (2) represents the structure of the acid component.
  • the acid dianhydride used for R 3 but are not limited to, in addition to the acid dianhydride having an alicyclic structure described above, the aromatic dianhydride and aliphatic acid dianhydride.
  • the aromatic dianhydride is not particularly limited, but pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyl Tetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-terphenyltetracarboxylic dianhydride, 3,3 ′, 4 , 4′-oxyphthalic dianhydride, 2,3,3 ′, 4′-oxyphthalic dianhydride, 2,3,2 ′, 3′-oxyphthalic dianhydride, diphenylsulfone-3,3 ′, 4,4′-tetracarboxylic dianhydride, benzophenone-3,3 ′, 4,4′-tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride
  • the aliphatic acid dianhydride is not particularly limited, but 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-pentanetetracarboxylic dianhydride, and derivatives thereof Etc.
  • R 4 represents the structure of the diamine component.
  • the diamine compound used for R 4 that is, the diamine compound having an alicyclic structure is not particularly limited, but is cyclobutanediamine, isophoronediamine, bicyclo [2.2.1] heptanebismethylamine, tricyclo [3.3.
  • the diamine that gives the structure represented by the general formula (3) is not particularly limited, but 2,2-bis (3-aminophenyl) propane, 2,2-bis [4- (4-aminophenoxy) phenyl] Propane, 2,2-bis (3-aminophenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis [3- (3-aminobenzamide) -4-hydroxyphenyl] hexafluoropropane and the like.
  • the polyimide used for the resin film of the film with a conductive layer has a structural unit represented by the following general formula (4) as a main component and the structural unit represented by the following general formula (5). It is preferable to contain 5 mol% or more and 30 mol% or less of the total structural unit of polyimide.
  • R 1 is a monovalent or condensed polycyclic alicyclic structure, a tetravalent organic group having 4 to 40 carbon atoms, or a monocyclic alicyclic ring.
  • R 13 represents a divalent organic group represented by the following general formula (6).
  • R 14 is a structure represented by the following structural formula (7) or the following structural formula (8).
  • R 15 to R 22 each independently represent a hydrogen atom, a halogen atom, or a monovalent organic group having 1 to 3 carbon atoms that may be substituted with a halogen atom.
  • X 2 is selected from a direct bond, an oxygen atom, a sulfur atom, a sulfonyl group, a divalent organic group having 1 to 3 carbon atoms which may be substituted with a halogen atom, an ester bond, an amide bond, and a sulfide bond. It is a structure.
  • the oxazole ring in the structural formula (8) is generated by dehydration ring closure from the structure represented by the structural formula (7).
  • “having the structural unit represented by the general formula (4) as a main component” means that the structural unit represented by the general formula (4) is 50 mol% in the total amount of all structural units of polyimide. It means having the above.
  • polyimide has the structural unit represented by the general formula (4) as a main component, the thermal expansion coefficient of polyimide is lowered. Therefore, when polyimide is formed on a support substrate for a process such as formation of a conductive layer, the warp of the polyimide is reduced, and the dimensional accuracy can be improved in processing of the conductive layer.
  • the total amount of all structural units of polyimide is specifically the total amount (mol basis) of the structural units represented by the general formula (4) and the general formula (5).
  • the total amount is a structural unit represented by the general formula (4) and the general formula (5).
  • the content of the structural unit represented by the general formula (4) is more preferably 70 mol% or more of the total structural unit of polyimide.
  • the polyimide contains the structural unit represented by the general formula (5) in an amount of 5 mol% or more and 30 mol% or less of the entire structural unit, thereby keeping the thermal expansion coefficient of the polyimide low while improving the transparency of the resin film. Can do. Thereby, the color of a film with a conductive layer (and a touch panel including this) can be improved while maintaining the pattern processability of the conductive layer.
  • the content of the structural unit (repeating structural unit) represented by the general formula (5) in the polyimide is more preferably 10 mol% or more and 25 mol% or less of the total structural unit of the polyimide.
  • R 1 in the general formula (4) and the general formula (5) is the same as R 1 in the general formula (1) represents a structure of an acid component having an alicyclic structure. Preferred specific examples of R 1 are as described above.
  • R 13 in the general formula (4) and R 14 in the general formula (5) represent the structure of the diamine component.
  • the diamine that gives the structure represented by the general formula (6) to R 13 is not particularly limited, but 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4, 4'-diaminodiphenylmethane, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis (3-amino-4 -Methylphenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, benzidine, 2,2 '-Bis (
  • R 13 is selected from, for example, four structures represented by the following structural formulas (20) to (23) from the viewpoint of availability, transparency, and reduction of the thermal expansion coefficient of polyimide. It is preferable that there are more types.
  • the polyimide used for the resin film of the film with a conductive layer may contain other structural units as long as the effects of the present invention are not hindered.
  • other structural units include polyimide, which is a polycyclic amide dehydration ring, polybenzoxazole, a polyhydroxyamide dehydration ring closure, and the like.
  • the acid dianhydride used for the other structural unit include the above-mentioned aromatic acid dianhydride or aliphatic acid dianhydride.
  • the polyimide used for the resin film of the film with a conductive layer is represented by the following general formula (9) in at least one of the acid dianhydride residue and the diamine residue constituting the polyimide. It is preferable to contain a repeating structure.
  • R 23 and R 24 each independently represent a monovalent organic group having 1 to 20 carbon atoms.
  • m is an integer of 3 to 200.
  • the polyimide is used as a support substrate for a process such as forming a conductive layer.
  • a process such as forming a conductive layer.
  • the polyimide including the structure represented by the general formula (9) has a low dielectric constant, the film with a conductive layer including the resin film including such a polyimide is used in a device such as a touch panel using the polyimide. Therefore, it is difficult to accumulate charges on the substrate, and ESD resistance is increased. Therefore, it is preferable that the polyimide used for the resin film of the film with a conductive layer includes a repeating structure represented by the general formula (9) as described above.
  • Examples of the monovalent organic group having 1 to 20 carbon atoms represented by R 23 and R 24 in the general formula (9) include, for example, a monovalent hydrocarbon group having 1 to 20 carbon atoms and a group having 1 to 20 carbon atoms.
  • a monovalent aminoalkyl group, an alkoxy group, an epoxy group, and the like can be given.
  • Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms.
  • the alkyl group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 10 carbon atoms. Specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, t- A butyl group, a pentyl group, a hexyl group, etc. are mentioned.
  • the cycloalkyl group having 3 to 20 carbon atoms is preferably a cycloalkyl group having 3 to 10 carbon atoms, and specific examples include a cyclopentyl group and a cyclohexyl group.
  • the aryl group having 6 to 20 carbon atoms is preferably an aryl group having 6 to 12 carbon atoms, and specific examples thereof include a phenyl group, a tolyl group, and a naphthyl group.
  • Examples of the monovalent alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, propoxy group, isopropyloxy group, butoxy group, phenoxy group, propenyloxy group, and cyclohexyloxy group.
  • R 23 and R 24 are preferably a monovalent aliphatic hydrocarbon group having 1 to 3 carbon atoms or an aromatic group having 6 to 10 carbon atoms. This is because the resulting polyimide resin film has higher heat resistance and lower residual stress.
  • the monovalent aliphatic hydrocarbon group having 1 to 3 carbon atoms is particularly preferably a methyl group.
  • the aromatic group having 6 to 10 carbon atoms is particularly preferably a phenyl group.
  • M in the general formula (9) is preferably an integer of 10 to 200, more preferably an integer of 20 to 150, still more preferably an integer of 30 to 100, and particularly preferably an integer of 35 to 80. It is.
  • m 3 or more, the residual stress of the polyimide resin film tends to be reduced.
  • m 200 or less, the cloudiness of the varnish which consists of a polyimide precursor and a solvent which is a composition for obtaining a polyimide can be suppressed.
  • Specific examples of the acid dianhydride having a repeating structure represented by the general formula (9) are not particularly limited, but X22-168AS (manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 1,000), X22-168A (Shin-Etsu) Chemical Company, number average molecular weight 2,000), X22-168B (manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 3,200), X22-168-P5-8 (manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 4,200), DMS-Z21 (manufactured by Gerest, number average molecular weight 600 to 800) and the like can be mentioned.
  • diamine having a repeating structure represented by the general formula (9) are not particularly limited, but both terminal amino-modified methylphenyl silicone (manufactured by Shin-Etsu Chemical Co., Ltd .; X22-1660B-3 (number average molecular weight 4,400 ), X22-9409 (number average molecular weight 1,300)), both-end amino-modified dimethyl silicone (manufactured by Shin-Etsu Chemical Co., Ltd .; X22-161A (number average molecular weight 1,600), X22-161B (number average molecular weight 3,000)) KF8012 (number average molecular weight 4,400), manufactured by Toray Dow Corning; BY16-835U (number average molecular weight 900), manufactured by Chisso; Silaplane FM3311 (number average molecular weight 1000)).
  • the polyimide used for the resin film of the film with a conductive layer preferably contains a triamine skeleton.
  • the toughness of the polyimide can be improved and the yield of the subsequent process can be improved.
  • triamine compound examples include those having no aliphatic group, 2,4,4′-triaminodiphenyl ether (TAPE), 1,3,5-tris (4-aminophenoxy) benzene (TAPOB), Examples thereof include tris (4-aminophenyl) amine, 1,3,5-tris (4-aminophenyl) benzene, 3,4,4′-triaminodiphenyl ether and the like.
  • triamine compounds include tris (2-aminoethyl) amine (TAEA), tris (3-aminopropyl) amine, and the like having aliphatic groups. Of these, 2,4,4'-triaminodiphenyl ether and 1,3,5-tris (4-aminophenoxy) benzene are preferably used from the viewpoint of improving heat resistance.
  • the thickness of the resin film used for the film with a conductive layer of the present invention is preferably 1 ⁇ m or more from the viewpoint of improving the toughness of the film with a conductive layer (and thus the toughness of the touch panel), and is preferably 2 ⁇ m or more. More preferably, it is 5 ⁇ m or more.
  • the thickness of the resin film is preferably 50 ⁇ m or less, more preferably 40 ⁇ m or less, and even more preferably 30 ⁇ m or less.
  • the transmittance at a wavelength of 450 nm of the resin film used for the film with a conductive layer of the present invention is preferably 85% or more from the viewpoint of improving the image quality of the touch panel. Further, the transmittance at a wavelength of 450 nm of the resin film after heat treatment at 150 to 350 ° C. is preferably 80% or more.
  • the resin film used for the film with a conductive layer of the present invention is prepared by adding an organic solvent, a surfactant, a leveling agent, an adhesion improver, a viscosity modifier, an antioxidant, an inorganic pigment to the polyimide or a precursor thereof as necessary. It can be formed using a resin composition formed by blending organic pigments, dyes and the like.
  • One of the methods for obtaining a resin film used in the film with a conductive layer of the present invention is to imide ring closure of polyamic acid which is a precursor corresponding to the polyimide to be obtained. It does not specifically limit as a method of imidation, Thermal imidation and chemical imidation are mentioned. Among these, thermal imidization is preferable from the viewpoint of heat resistance of the polyimide resin film and transparency in the visible light region.
  • Polyimide precursors such as polyamic acid, polyamic acid ester, and polyamic acid silyl ester can be synthesized by a polymerization reaction between a diamine compound and an acid dianhydride or a derivative thereof.
  • the acid dianhydride derivative include tetracarboxylic acid of acid dianhydride, monoester, diester, triester or tetraester of the tetracarboxylic acid, and acid chloride.
  • the reaction method of the polymerization reaction is not particularly limited as long as the target polyimide precursor can be produced, and a known reaction method can be used.
  • a predetermined amount of all diamine components and a solvent are charged into a reactor, and after dissolving the diamine, a predetermined amount of acid dianhydride component is charged at room temperature to 80 ° C. Examples thereof include a method of stirring for 0.5 to 30 hours.
  • the polyimide and polyimide precursor used for the resin film of the film with a conductive layer may be sealed at both ends with a terminal sealing agent in order to adjust the molecular weight to a preferred range.
  • the terminal blocking agent that reacts with the acid dianhydride include monoamines and monohydric alcohols.
  • the end-capping agent that reacts with the diamine compound include acid anhydrides, monocarboxylic acids, monoacid chloride compounds, monoactive ester compounds, dicarbonates, and vinyl ethers.
  • various organic groups can be introduce
  • a well-known compound can be used for terminal blocker.
  • the introduction ratio of the terminal blocking agent on the acid anhydride group side is preferably in the range of 0.1 to 60 mol%, preferably in the range of 0.5 to 50 mol%, relative to the acid dianhydride component. It is more preferable that The introduction ratio of the terminal blocking agent on the amino group side is preferably in the range of 0.1 to 100 mol%, and preferably in the range of 0.5 to 70 mol% with respect to the diamine component. Is more preferable. You may introduce
  • the end sealant introduced into the polyimide precursor or polyimide can be easily detected by the following method.
  • a polymer into which a terminal blocking agent has been introduced is dissolved in an acidic solution and decomposed into an amine component and an acid anhydride component that are constituent units of the polymer.
  • GC gas chromatography
  • NMR nuclear magnetic resonance
  • the end-capping agent can be easily detected.
  • the polymer into which the end-capping agent is introduced is directly subjected to measurement of pyrolysis gas chromatography (PGC), infrared spectrum, 1 H NMR spectrum, 13 C NMR spectrum, etc. It can be easily detected.
  • PPC pyrolysis gas chromatography
  • the composition for obtaining a resin film containing polyimide may contain an appropriate component in addition to the polyimide or the polyimide precursor.
  • the component that may be contained in the polyimide resin composition is not particularly limited, and examples thereof include an ultraviolet absorber, a thermal crosslinking agent, an inorganic filler, a surfactant, an internal release agent, and a colorant. Each of these can be a known compound.
  • a tetravalent organic group having 4 to 40 carbon atoms means a tetravalent organic group having 4 to 40 carbon atoms.
  • the film with a conductive layer according to the embodiment of the present invention has a gas barrier layer as exemplified by the gas barrier layer 2 illustrated in FIG.
  • the gas barrier layer in the present invention refers to a layer that is formed on a resin film serving as a substrate and has a function of preventing direct contact between the resin film and environmental gases.
  • a high temperature of 200 ° C. or higher is applied to the resin film in the presence of oxygen. Therefore, if there is no gas barrier layer, yellowing due to thermal oxidation occurs in the resin film, resulting in deterioration of the color of the film with a conductive layer.
  • By forming a gas barrier layer between the resin film and the conductive layer it is possible to prevent the resin film and oxygen from contacting each other during heating in an oxygen atmosphere. Thus, a film with a conductive layer excellent in color without yellowing can be obtained.
  • the material constituting the gas barrier layer may be an organic material or an inorganic material as long as it prevents the permeation of oxygen when forming the conductive layer, but an inorganic material is preferable from the viewpoint of oxygen barrier properties.
  • the inorganic material include metal oxide, metal nitride, metal oxynitride, and metal carbonitride.
  • the metal element contained in these include aluminum (Al), silicon (Si), titanium (Ti), tin (Sn), zinc (Zn), zirconium (Zr), indium (In), and niobium (Nb). , Molybdenum (Mo), tantalum (Ta), calcium (Ca), and the like.
  • the gas barrier layer preferably contains at least one of silicon oxide, silicon nitride, silicon oxynitride, and silicon carbonitride. This is because by using these materials for forming the gas barrier layer, a uniform and dense gas barrier film can be easily obtained, and the oxygen barrier property of the gas barrier layer is further improved.
  • the gas barrier layer preferably contains a component represented by SiOxNy.
  • x and y are values satisfying 0 ⁇ x ⁇ 1, 0.55 ⁇ y ⁇ 1, and 0 ⁇ x / y ⁇ 1.
  • the gas barrier layer can be produced by a vapor deposition method in which a film is formed by depositing a material from the vapor phase, such as a sputtering method, a vacuum deposition method, an ion plating method, or a plasma CVD method. Among them, it is preferable to use a sputtering method or a plasma CVD method because a more uniform film having a high oxygen barrier property can be obtained.
  • the number of gas barrier layers is not limited, and may be only one layer or a multilayer of two or more layers.
  • Examples of when the gas barrier layer is a multilayer film include a gas barrier layer in which the first layer is made of SiN and the second layer is made of SiO, a gas barrier layer in which the first layer is made of SiON and the second layer is made of SiO, etc. Is mentioned.
  • the gas barrier layer is an inorganic film laminated in two or more layers, and the layer in contact with the conductive layer among the inorganic films is SiOz (z is a value satisfying 0.5 ⁇ z ⁇ 2. It is preferable to form with the component represented by this. This is because the chemical resistance of the gas barrier layer at the time of processing the conductive layer (particularly during development using photolithography) is improved, and the pattern processability and dimensional accuracy of the conductive layer is improved, and the residue is suppressed. This is because an effect can be obtained.
  • the total thickness of the gas barrier layer is preferably 10 nm or more, and more preferably 50 nm or more, from the viewpoint of improving the oxygen barrier property.
  • the total thickness of the gas barrier layer is preferably 1 ⁇ m or less, and more preferably 200 nm or less.
  • the film with a conductive layer according to the embodiment of the present invention has a conductive layer containing conductive particles as exemplified by the conductive layer 3A illustrated in FIG.
  • the conductive layer preferably has a network structure with a line width of 0.1 to 9 ⁇ m.
  • the line width of the network structure of the conductive layer is more preferably 0.5 ⁇ m or more, and further preferably 1 ⁇ m or more.
  • the line width of the network structure of the conductive layer is more preferably 7 ⁇ m or less, and further preferably 6 ⁇ m or less.
  • the film thickness of the conductive layer is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more, and further preferably 0.3 ⁇ m or more.
  • the thickness of the conductive layer is preferably 5 ⁇ m or less, more preferably 3 ⁇ m or less, and even more preferably 1 ⁇ m or less.
  • Examples of the conductive particles contained in the conductive layer include gold (Au), silver (Ag), copper (Cu), nickel (Ni), tin (Sn), bismuth (Bi), lead (Pb), zinc ( Examples thereof include metal particles such as Zn), palladium (Pd), platinum (Pt), aluminum (Al), tungsten (W), and molybdenum (Mo), and metal particles having carbon.
  • the metal particles having carbon are, for example, a composite of carbon black and metal. Two or more of these may be used as the conductive particles. Among these, gold, silver, copper, nickel, tin, bismuth, lead, zinc, palladium, platinum or aluminum metal particles and carbon-containing metal particles are preferable, and silver particles are more preferable.
  • the primary particle diameter of the conductive particles is preferably 10 to 200 nm and more preferably 10 to 60 nm in order to form a fine conductive pattern having desired conductivity.
  • the primary particle size of the conductive particles is determined by observing the cross section of the conductive layer with a scanning electron microscope, selecting 100 particles at random, and measuring the primary particle size of each particle. It is calculated by taking the arithmetic average value of In addition, let the particle diameter of the primary particle of each particle
  • the content of the conductive particles in the conductive layer is preferably 20% by mass or more, more preferably 50% by mass or more, and 65% by mass or more. Further preferred. On the other hand, the content of the conductive particles is preferably 95% by mass or less, and more preferably 90% by mass or less from the viewpoint of improving pattern processability.
  • the conductive layer preferably contains 0.1 to 80% by mass of an organic compound.
  • the conductive layer contains 0.1% by mass or more of the organic compound, the conductive layer can be given flexibility and the bending resistance of the conductive layer can be further improved.
  • the content of the organic compound in the conductive layer is preferably 1% by mass or more, and more preferably 5% by mass or more.
  • the conductivity can be improved.
  • the content of the organic compound in the conductive layer is more preferably 50% by mass or less, and further preferably 35% by mass or less.
  • an alkali-soluble resin As the organic compound contained in the conductive layer, an alkali-soluble resin is preferable.
  • a (meth) acrylic copolymer having a carboxyl group is preferable.
  • the (meth) acrylic copolymer refers to a copolymer of a (meth) acrylic monomer and another monomer.
  • Examples of the (meth) acrylic monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) ) Acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, butoxyethyl (meth) acrylate, butoxytriethylene glycol (meth) ) Acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycerol (meth
  • Examples of the other monomer include compounds having a carbon-carbon double bond.
  • aromatic vinyl compounds such as styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, ⁇ -methylstyrene,
  • Amide unsaturated compounds such as (meth) acrylamide, N-methylol (meth) acrylamide, N-vinylpyrrolidone, (meth) acrylonitrile, allyl alcohol, vinyl acetate, cyclohexyl vinyl ether, n-propyl vinyl ether, i-propyl vinyl ether, n- Examples include butyl vinyl ether, i-butyl vinyl ether, 2-hydroxyethyl vinyl ether, and 4-hydroxybutyl vinyl ether.
  • alkali-soluble resin for example, (meth) acrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, acid anhydrides thereof, etc. ) A method of copolymerizing with an acrylic monomer.
  • the (meth) acrylic copolymer preferably has a carbon-carbon double bond in the side chain or molecular end from the viewpoint of increasing the speed of the curing reaction.
  • the functional group having a carbon-carbon double bond include a vinyl group, an allyl group, and a (meth) acryl group.
  • the carboxylic acid equivalent of the alkali-soluble resin is preferably 400 to 1,000 g / mol.
  • the carboxylic acid equivalent of the acrylic soluble resin can be calculated by measuring the acid value.
  • the double bond equivalent of the alkali-soluble resin is preferably 150 to 10,000 g / mol because both hardness and crack resistance can be achieved at a high level.
  • the double bond equivalent of the acrylic soluble resin can be calculated by measuring the iodine value.
  • the weight average molecular weight (Mw) of the alkali-soluble resin is preferably 1,000 to 100,000. By setting the weight average molecular weight within the above range, good coating characteristics of the alkali-soluble resin can be obtained, and the solubility of the alkali-soluble resin in the developer during pattern formation of the conductive layer can be improved.
  • the weight average molecular weight of the alkali-soluble resin refers to a polystyrene equivalent value measured by gel permeation chromatography (GPC).
  • the conductive layer may contain at least one of an organic tin compound and a metal chelate compound.
  • the conductive layer contains at least one of an organotin compound and a metal chelate compound, adhesion between the conductive layer and the gas barrier layer can be further improved.
  • a metal chelate compound is more preferable because an adhesion improving effect can be obtained without applying an environmental load as compared with an organotin compound.
  • Known compounds can be used as the organotin compound and the metal chelate compound.
  • the total content of the organotin compound and the metal chelate compound in the conductive layer is preferably 0.01% by mass or more and more preferably 0.05% by mass or more from the viewpoint of further improving the substrate adhesion. More preferably, it is more preferably 0.1% by mass or more.
  • the total content of the organotin compound and the metal chelate compound is preferably 10% by mass or less from the viewpoint of improving the conductivity of the conductive layer and forming a finer pattern. More preferably, it is more preferably 3% by mass or less.
  • At least one of a dispersant, a photopolymerization initiator, a monomer, a photoacid generator, a thermal acid generator, a solvent, a sensitizer, a pigment and a dye that absorb visible light, and adhesion improvement It is preferable to contain an agent, a surfactant, a polymerization inhibitor and the like.
  • the conductive layer in the present invention can be formed using a conductive composition.
  • the components contained in the conductive composition include conductive particles, alkali-soluble resins, organotin compounds, metal chelate compounds, dispersants, photopolymerization initiators, monomers, photoacid generators, thermal acid generators, Examples thereof include at least one of a solvent, a sensitizer, a pigment and a dye that absorb visible light, an adhesion improver, a surfactant, or a polymerization inhibitor.
  • the conductive particles contained in the conductive composition preferably have a coating layer on at least a part of the particle surface.
  • the surface activity of the conductive particles can be reduced, and at least one of the reaction between the conductive particles and the reaction between the conductive particles and the organic component can be suppressed, and the dispersibility of the conductive particles can be improved.
  • the coating layer on the surface of the conductive particles can be easily removed by heating at a high temperature of about 150 to 350 ° C. in the presence of oxygen. As a result, the conductive particles in the conductive composition can exhibit sufficient conductivity of the conductive layer.
  • the coating layer on the surface of the conductive particles preferably contains at least one of carbon and a carbon compound.
  • this coating layer contains at least one of carbon and a carbon compound, the dispersibility of the conductive particles in the conductive composition can be further improved.
  • a reactive gas having carbon such as methane gas is brought into contact with the conductive particles by a thermal plasma method. And the like (the method described in JP 2007-138287 A) and the like.
  • the film with a conductive layer preferably has an insulating layer formed from an alkali-soluble resin on the conductive layer.
  • the alkali-soluble in the present invention means that 0.1 g or more dissolves at 25 ° C. in a 0.045 mass% potassium hydroxide aqueous solution (100 g).
  • An insulating layer formed of an alkali-soluble resin is preferable because it can be patterned by photolithography, thereby forming an opening for conduction of the conductive layer.
  • the film with a conductive layer according to the embodiment of the present invention preferably has an insulating layer formed on the conductive layer from an alkali-soluble resin containing the above-mentioned (meth) acrylic copolymer. This is because the flexibility of the insulating layer is increased by the (meth) acrylic copolymer in the alkali-soluble resin.
  • the film with a conductive layer according to the embodiment of the present invention is formed from an alkali-soluble resin containing a cardo resin having two or more structures represented by the following structural formula (10) on the conductive layer. It is preferable to have an insulating layer. This is because the cardo resin increases the hydrophobicity of the insulating layer, thereby improving the insulating property of the insulating layer.
  • the cardo resin can be obtained, for example, by further reacting a reaction product of an epoxy compound and an organic acid containing a radical polymerizable group with an acid dianhydride.
  • the catalyst used for the reaction between an epoxy compound and an organic acid containing a radical polymerizable group and the reaction between the epoxy compound and acid dianhydride include, for example, an ammonium catalyst, an amine catalyst, a phosphorus catalyst, and a chromium catalyst. Etc.
  • Examples of the ammonium-based catalyst include tetrabutylammonium acetate.
  • the amine catalyst include 2,4,6-tris (dimethylaminomethyl) phenol or dimethylbenzylamine.
  • the phosphorus catalyst include triphenylphosphine.
  • the chromium-based catalyst include acetylacetonate chromium and chromium chloride.
  • the following compounds are mentioned, for example.
  • organic acid containing a radical polymerizable group examples include (meth) acrylic acid, mono (2- (meth) acryloyloxyethyl) succinate, mono (2- (meth) acryloyloxyethyl) phthalate, tetrahydrophthal Examples include acid mono (2- (meth) acryloyloxyethyl) and p-hydroxystyrene.
  • acid dianhydrides examples include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, from the viewpoint of improving the chemical resistance of the cured film.
  • 4-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride and the like are preferable.
  • cardo resin having two or more structures represented by the structural formula (10) commercially available products can be preferably used.
  • Examples of commercially available cardo resins include “WR-301 (trade name)” (manufactured by ADEKA), “V-259ME (trade name)” (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), “Ogsol CR-TR1 ( “Product Name)”, “Ogsol CR-TR2 (Product Name)”, “Ogsol CR-TR3 (Product Name)”, “Ogsol CR-TR4 (Product Name)”, “Ogsol CR-TR5 (Product Name)”, “ OGSOL CR-TR6 (trade name) "(manufactured by Osaka Gas Chemical Co., Ltd.).
  • the weight average molecular weights of the (meth) acrylic copolymer and the cardo resin are each preferably 2,000 or more from the viewpoint of improving coating properties. Moreover, these weight average molecular weights are each preferably 200,000 or less from the viewpoint of improving the solubility of the insulating layer in the developer in the pattern formation of the insulating layer.
  • a weight average molecular weight says the polystyrene conversion value measured by GPC.
  • the weight average molecular weight (Mw (A1)) of the (meth) acrylic copolymer and the weight average molecular weight of the cardo resin is preferably 0.14 or more from the viewpoint of suppressing layer separation and forming a uniform cured film.
  • this ratio (Mw (A2) / Mw (A1)) is preferably 1.5 or less, and preferably 1.0 or less from the viewpoint of suppressing layer separation and forming a uniform cured film. It is more preferable.
  • the insulating layer in the present invention can be formed using an insulating composition containing an alkali-soluble resin.
  • the content of the alkali-soluble resin contained in this insulating composition can be arbitrarily selected depending on the desired film thickness and application, but it is 10 parts by mass or more and 70 parts by mass with respect to 100 parts by mass of the solid content. Generally, it is as follows.
  • the above-mentioned insulating composition may contain a hindered amine light stabilizer.
  • said insulating composition contains a hindered amine light stabilizer, coloring of an insulating layer can be reduced more and the weather resistance of an insulating layer can be improved.
  • the above-mentioned insulating composition further includes a polyfunctional monomer, a curing agent, an ultraviolet absorber, a polymerization inhibitor, an adhesion improver, a solvent, a surfactant, a dissolution inhibitor, a stabilizer, an antifoaming agent, etc. It is also possible to contain these additives.
  • the touch panel according to the embodiment of the present invention includes the film with a conductive layer of the present invention as exemplified by the touch panel 10 illustrated in FIGS.
  • the conductive layer of the film with a conductive layer is a wiring layer of the touch panel (for example, the first wiring layer 3 shown in FIGS. 2 and 3).
  • the touch panel of the present invention has an insulating layer (first insulating layer) on the wiring layer (first wiring layer) on the gas barrier layer.
  • the touch panel of the present invention may further include a second insulating layer on the side opposite to the surface in contact with the first insulating layer (that is, the upper surface side) of the second wiring layer. Since the touch panel of the present invention has the second insulating layer as described above, moisture in the atmosphere can be prevented from reaching the second wiring layer. As a result, the reliability of the touch panel can be further improved.
  • the first insulating layer and the second insulating layer may be made of the same material or different materials.
  • the film thicknesses of the first insulating layer and the second insulating layer are preferably 0.1 ⁇ m or more, and more preferably 0.5 ⁇ m or more, from the viewpoint of further improving the insulating properties.
  • the film thicknesses of the first insulating layer and the second insulating layer are preferably 10 ⁇ m or less, and more preferably 3 ⁇ m or less, from the viewpoint of further improving their transparency.
  • the thickness of the film with a conductive layer applied to such a touch panel is preferably 1 to 40 ⁇ m.
  • the thickness of the film with a conductive layer applied to such a touch panel is preferably 1 to 40 ⁇ m.
  • the thickness of the touch panel is more preferably 3 ⁇ m or more, and further preferably 5 ⁇ m or more.
  • the thickness of the touch panel is more preferably 30 ⁇ m or less, and further preferably 25 ⁇ m or less.
  • the film with a conductive layer preferably has a b * value of ⁇ 5 to 5 according to the L * a * b * color system defined by the International Lighting Commission 1976.
  • b * is more preferably ⁇ 4 to 4, and further preferably ⁇ 3 to 3.
  • the manufacturing method of the touchscreen containing the film with a conductive layer which concerns on embodiment of this invention uses this manufacturing method of a film with a conductive layer.
  • This method for producing a film with a conductive layer includes at least a resin film forming step, a gas barrier layer forming step, a conductive layer forming step, and a peeling step.
  • the resin film forming step is a step of forming a resin film containing polyimide on the support substrate.
  • the gas barrier layer forming step is a step of forming a gas barrier layer on the resin film.
  • the conductive layer forming step is a step of forming a conductive layer on the gas barrier layer.
  • the peeling step is a step of peeling the resin film after the gas barrier layer and the conductive layer are formed from the support substrate.
  • the manufacturing method of a touch panel includes a wiring layer formation process as a conductive layer formation process in the manufacturing method of a film with a conductive layer.
  • the wiring layer forming step is a step of forming a wiring layer as a conductive layer on the gas barrier layer.
  • FIG. 4 is a process diagram showing an example of a method for manufacturing a touch panel including a film with a conductive layer according to an embodiment of the present invention.
  • a resin film forming step, a gas barrier layer forming step, a first wiring layer forming step, a first insulating layer forming step, a second wiring layer forming step, The second insulating layer forming step and the peeling step are sequentially performed in this order.
  • the resin film forming step as shown in the state S1 in FIG. 4, the resin film 1 containing polyimide is formed on the support substrate 7.
  • the gas barrier layer forming step the gas barrier layer 2 is formed on the resin film 1 as shown in the state S2 of FIG.
  • the first wiring layer 3 is formed on the gas barrier layer 2 as shown in a state S3 in FIG.
  • the first insulating layer 4 is formed on the gas barrier layer 2 so as to cover the first wiring layer 3 as shown in a state S4 in FIG. .
  • the second wiring layer formation step on the first insulating layer 4 (on the gas barrier layer 2 and the first insulating layer 4 in the present embodiment) as shown in the state S5 in FIG. A second wiring layer 5 is formed.
  • the second insulating layer forming step the second insulating layer 6 is formed on the gas barrier layer 2 so as to cover the second wiring layer 5 as shown in a state S6 in FIG. .
  • the peeling step as shown in a state S7 in FIG. 4, the laminated structure of the resin film 1 and the gas barrier layer 2 is cut at the cut end face 8.
  • the resin film 1 of this laminated structure is mechanically peeled from the support substrate 7. In this way, the touch panel 10 is obtained.
  • each of these steps will be described in detail.
  • the resin film forming step is a step of forming the resin film 1 containing polyimide on the support substrate 7 as described above.
  • the resin film forming step includes a coating step of applying the polyimide resin composition described above on the support substrate 7, a prebaking step of drying the polyimide resin composition on the support substrate 7, and a polyimide resin composition after drying. And a curing step for curing.
  • Examples of the support substrate 7 include a silicon wafer, a ceramic substrate, and an organic substrate.
  • Examples of the ceramic substrate include glass substrates such as soda glass, non-alkali glass, borosilicate glass, and quartz glass, alumina substrates, aluminum nitride substrates, and silicon carbide substrates.
  • Suitable examples of the organic substrate include an epoxy substrate, a polyetherimide resin substrate, a polyether ketone resin substrate, a polysulfone resin substrate, a polyimide film, and a polyester film.
  • Examples of the method for applying the polyimide resin composition onto the support substrate 7 include application using a spin coater, bar coater, blade coater, roll coater, die coater, calendar coater, meniscus coater, screen printing, spray coating, and dip. A coat etc. are mentioned.
  • Examples of the heating method in the pre-bake process and the curing process include a hot plate, a hot air dryer (oven), vacuum drying, vacuum drying, or heating by infrared irradiation.
  • the pre-baking temperature and time of the polyimide resin composition in the pre-baking step may be appropriately determined depending on the composition of the target polyimide resin composition and the film thickness of the coating film to be dried (polyimide resin composition coating film).
  • the curing atmosphere, temperature and time of the polyimide resin composition in the curing step may be appropriately determined depending on the composition of the target polyimide resin composition and the film thickness of the coating film to be cured (polyimide resin composition coating film). . From the viewpoint of suppressing yellowing of the film due to heating, in this curing step, the polyimide resin composition coating film on the support substrate 7 is heated to a temperature of 300 ° C. or more and 500 ° C. or less in an atmosphere having an oxygen concentration of 1000 ppm or less. It is preferable to form the resin film 1 by heating for 5 to 180 minutes.
  • the gas barrier layer forming step is a step of forming the gas barrier layer 2 on the resin film 1 as described above.
  • a method for forming the gas barrier layer 2 in this gas barrier layer forming step for example, a gas phase in which a film is formed by depositing a material from the gas phase, such as a sputtering method, a vacuum evaporation method, an ion plating method, or a plasma CVD method. Deposition methods are mentioned. Among them, it is preferable to use a sputtering method or a plasma CVD method because a more uniform film (gas barrier layer 2) having a high oxygen barrier property can be obtained.
  • the polyimide resin preferably used for the resin film 1 in the present invention has a high glass transition temperature, it is possible to increase the substrate temperature (the temperature of the support substrate 7) when the gas barrier layer 2 is formed. Since the crystallinity of the gas barrier layer 2 is improved as the substrate temperature is higher, the gas barrier performance is improved. On the other hand, if the film forming temperature of the gas barrier layer 2 is too high, the bending resistance of the gas barrier layer 2 is lowered. From these viewpoints, the lower limit of the film forming temperature of the gas barrier layer 2 is preferably 80 ° C. or higher, and more preferably 100 ° C. or higher. Moreover, as an upper limit of the film forming temperature of the gas barrier layer 2, 400 degrees C or less is preferable and 350 degrees C or less is more preferable.
  • the first wiring layer forming step is a step of forming the first wiring layer 3 on the gas barrier layer 2 as described above.
  • the first wiring layer forming step includes a coating step of coating the conductive composition on the gas barrier layer 2, a pre-baking step of drying the coating film of the conductive composition, and the dried coating film (pre-baking It is preferable to include a step of exposing and developing the film) to form a mesh pattern (exposure step and developing step) and a curing step of curing the pre-baked film formed with this pattern.
  • the first wiring layer forming step it is preferable to form the first wiring layer 3 using a conductive composition containing conductive particles having a coating layer on at least a part of the surface. This is because the conductive particles having the coating layer on at least a part of the surface suppress the scattering of the exposure light in the exposure process, whereby the wiring of the first wiring layer 3 can be patterned with high accuracy. Because.
  • the resin described above is used in the first wiring layer forming step.
  • the method illustrated in the polyimide resin composition of a film formation process is mentioned.
  • the light source used in the exposure process of the coating film of the conductive composition for example, j-line, i-line, h-line, and g-line of a mercury lamp are preferable.
  • a known developer can be used as the developer.
  • an alkaline aqueous solution in which an alkaline substance such as sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide (TMAH) is dissolved in water can be used.
  • the developer may be obtained by appropriately adding a water-soluble organic solvent such as ethanol, ⁇ -butyrolactone, dimethylformamide, N-methyl-2-pyrrolidone to the developer.
  • a surfactant such as a nonionic surfactant is further added to the alkaline developer and the developer. It is also preferable to add such that the content thereof is 0.01 to 1% by mass.
  • the curing atmosphere, temperature and time of the conductive composition coating film (patterned pre-baked film) in the curing process are the same as the composition of the conductive composition and the coating film to be cured (conductive composition coating film). What is necessary is just to determine suitably with a film thickness.
  • this curing step for example, it is preferable to heat the coating film of the conductive composition in the temperature range of 100 to 300 ° C. for 5 to 120 minutes.
  • the first wiring layer 3 contains conductive particles having a coating layer on the surface
  • the first wiring layer 3 is formed by heating the coating film of the conductive composition on the gas barrier layer 2 at a temperature of 100 ° C. or higher and 300 ° C. or lower in an atmosphere having an oxygen concentration of 15% or higher. It is preferable to do.
  • the polyimide resin composition is heated at a temperature of 300 ° C. or more and 500 ° C. or less in an atmosphere having an oxygen concentration of 1000 ppm or less. And forming a resin film 1 containing polyimide, and heating the conductive composition at a temperature of 100 ° C. to 300 ° C. in an atmosphere having an oxygen concentration of 15% or more to form a wiring layer (for example, a first layer) A wiring layer forming step of forming one wiring layer 3).
  • the first insulating layer forming step is a step of forming the first insulating layer 4 on the gas barrier layer 2 so as to cover the first wiring layer 3 as described above.
  • the first insulating layer forming step includes a coating step of applying the above-described insulating composition onto the first wiring layer 3, a pre-baking step of drying the coating film of the insulating composition, and the dry coating. It is preferable to include a step (exposure step and development step) of forming a pattern by exposing and developing the film (pre-baked film) and a curing step of curing the pre-baked film (insulating film) formed with this pattern.
  • Exposure step and development step of forming a pattern by exposing and developing the film (pre-baked film) and a curing step of curing the pre-baked film (insulating film) formed with this pattern.
  • Each step included in the first insulating layer forming step can be performed in the same manner as in the first wiring layer forming step described above.
  • the second wiring layer forming step is a step of forming the second wiring layer 5 on the first insulating layer 4 as described above.
  • the second wiring layer 5 can be formed by the same method as the first wiring layer 3 described above.
  • the second insulating layer forming step is a step of forming the second insulating layer 6 so as to cover the second wiring layer 5 as described above.
  • the second insulating layer 6 can be formed by the same method as the first insulating layer 4 described above.
  • the second insulating layer 6 may not be formed on the second wiring layer 5, but the second insulating layer 6 is formed as described above. Is preferred. This is because, by forming the second insulating layer 6, it is possible to suppress moisture in the atmosphere from reaching the second wiring layer 5, thereby improving the moisture and heat resistance of the touch panel 10. It is.
  • the peeling step is a step of peeling the resin film 1 from the support substrate 7.
  • a method of peeling the resin film 1 containing polyimide from the support substrate 7 in this peeling step for example, a method of peeling the resin film 1 by irradiating the resin film 1 from the back surface of the support substrate 7, a support substrate before taking out the touch panel 10 7 (hereinafter referred to as “support substrate with touch panel” as appropriate) is immersed in at least one of a solvent kept at 0 to 80 ° C. and purified water for 10 seconds to 10 hours, and the resin film 1 is removed from the upper surface.
  • Examples of the method include cutting and mechanical peeling from the cut end face 8. Among these, considering the influence on the reliability of the touch panel 10, a method of mechanical peeling from the cut end surface 8 is preferable.
  • the above-mentioned peeling process may be performed directly on the support substrate with a touch panel, or may be performed after a protective film or a transparent adhesive layer (OCA: Optical Clear Adhesive) is bonded to the support substrate with a touch panel. Furthermore, after bonding a support substrate with a touch panel to a member such as a display substrate via OCA, the resin film 1 is peeled off from the support substrate with a touch panel (that is, the touch panel 10 is taken out). It is preferable from the viewpoint of accuracy.
  • the touch panel according to the embodiment of the present invention has good visibility because the gas barrier layer prevents the resin film containing polyimide from being yellowed when the wiring layer is formed. Moreover, since the dimensional change of the resin film at the time of wiring layer formation is suppressed by a gas barrier layer, the touch panel excellent in dimensional accuracy can be provided.
  • the touch panel according to the embodiment of the present invention is suitably used as a display member such as a smartphone or a tablet terminal.
  • the method for producing a film with a conductive layer includes at least a resin film forming step, a gas barrier layer forming step, a conductive layer forming step, and a peeling step.
  • the resin film forming step, the gas barrier layer forming step, and the peeling step are the same as the touch panel manufacturing method described above, as exemplified by the states S1, S3, and S7 in FIG.
  • the conductive layer forming step is a step of forming a conductive layer on the gas barrier layer.
  • This conductive layer forming step is the same as the step in which the first wiring layer in the first wiring layer forming step in the touch panel manufacturing method described above is replaced with a conductive layer.
  • the conductive layer forming step is preferably a step of forming a conductive layer using a conductive composition containing conductive particles having a coating layer on at least a part of the surface.
  • the conductive layer forming step is a step of forming the conductive layer by heating the conductive composition on the gas barrier layer at a temperature of 100 ° C. or higher and 300 ° C. or lower in an atmosphere having an oxygen concentration of 15% or higher. Preferably there is.
  • the manufacturing method of the film with a conductive layer may include an insulating layer forming step of forming an insulating layer on the gas barrier layer so as to cover the conductive layer.
  • This insulating layer forming step can be performed, for example, by the same technique as the first insulating layer forming step in the touch panel manufacturing method described above.
  • BPDA 2,2-bis (4- (3,4-dicarboxyphenoxy) phenyl) propane dianhydride
  • BSAA propane dianhydride
  • ODPA 4,4′-diphenyl ether tetracarboxylic dianhydride
  • PMDA 1,2,4,5-benzenetetracarboxylic dianhydride
  • Diamine compound in the following Examples and Comparative Examples, as a diamine compound, trans-1,4-diaminocyclohexane (CHDA), 2,2′-bis (trifluoromethyl) benzidine (TFMB), 2,2-bis [3 -(3-aminobenzamido) -4-hydroxyphenyl] hexafluoropropane (HFHA), bis (3-aminophenyl) sulfone (3,3'-DDS), bis [4- (3-aminophenoxy) phenyl] sulfone (M-BAPS), a both-end amine-modified methylphenyl silicone oil (X22-1660B-3) manufactured by Shin-Etsu Chemical Co., Ltd. is used as necessary.
  • CHDA trans-1,4-diaminocyclohexane
  • TFMB 2,2′-bis (trifluoromethyl) benzidine
  • HFHA 2,2-bis [3 -(3-aminobenzamid
  • NMP N-methyl-2-pyrrolidone
  • GBL ⁇ -butyrolactone
  • PGMEA propylene glycol monomethyl ether
  • DPM dipropylene glycol monomethyl ether
  • Alkali-soluble resin In the following Examples and Comparative Examples, the alkali-soluble resin AR is used as necessary.
  • the alkali-soluble resin AR has a weight average molecular weight (Mw) of 29,000.
  • conductive particles A-1 and A-2 are used as necessary as conductive particles.
  • the conductive particles A-1 were silver particles (manufactured by Nisshin Engineering Co., Ltd.) having an average thickness of the surface carbon coating layer of 1 nm and a primary particle diameter of 40 nm.
  • the conductive particles A-2 were silver particles (manufactured by Mitsui Metal Mining Co., Ltd.) having a primary particle size of 0.7 ⁇ m.
  • this processed mixture was dispersed using a high-pressure wet medialess atomizer Nanomizer (manufactured by Nanomizer) to obtain a silver dispersion L1 having a silver content of 40% by mass. Further, a silver dispersion L2 was obtained in the same manner as above except that the conductive particles A-2 were used instead of the conductive particles A-1.
  • alkali-soluble resin AR (20 g) as an organic compound
  • ALCH 0.6 g
  • NCI-831 2.4 g
  • PE-3A PGMEA
  • DPM 52.6 g
  • ALCH is a metal chelate compound (ethyl acetoacetate aluminum diisopropylate) manufactured by Kawaken Fine Chemicals
  • NCI-831 is a photopolymerization initiator manufactured by ADEKA.
  • the silver dispersions L1 and L2 and the organic liquid L3 obtained as described above were mixed in the ratios shown in Table 1, respectively, thereby obtaining conductive compositions AE-1 and AE-2.
  • an insulating composition OA-1 was obtained.
  • an insulating composition OA-2 was obtained in the same manner as above except that the alkali-soluble resin AR was used in place of the cardo resin (V-259ME).
  • the prebaked film thus obtained was heated to 350 ° C. at a temperature increase rate of 3.5 ° C./min under a nitrogen stream (oxygen concentration of 20 ppm or less). The temperature was raised and held for 30 minutes. Thereafter, the pre-baked film was cooled to 50 ° C. at a rate of temperature decrease of 5 ° C./min, thereby producing a polyimide resin film T1.
  • the polyimide resin film T1 (attached to the substrate) is immersed in hydrofluoric acid for 1 to 4 minutes, the polyimide resin film T1 is peeled off from the substrate, and air-dried to obtain a polyimide resin film T1 (single unit).
  • the varnish coating film was pre-baked for 4 minutes at a temperature of 140 ° C. using a hot plate (D-SPIN) manufactured by Dainippon Screen.
  • D-SPIN hot plate
  • the inert oven (INH-21CD) manufactured by Koyo Thermo Systems Co., Ltd.
  • the prebaked film thus obtained was heated to 350 ° C. at a temperature increase rate of 3.5 ° C./min under a nitrogen stream (oxygen concentration of 20 ppm or less).
  • the temperature was raised and held for 30 minutes.
  • the pre-baked film was cooled to 50 ° C. at a temperature lowering rate of 5 ° C./min, thereby producing a polyimide resin film T2 attached to a rectangular glass substrate.
  • the prebaked film thus obtained was heated to 350 ° C. at a temperature increase rate of 3.5 ° C./min under a nitrogen stream (oxygen concentration of 20 ppm or less). The temperature was raised and held for 30 minutes. Thereafter, the pre-baked film was cooled to 50 ° C. at a temperature lowering rate of 5 ° C./min. Thereby, a polyimide resin film T3 adhered to a circular glass substrate was produced.
  • the prebaked film thus obtained was heated to 300 ° C. at a temperature rising rate of 3.5 ° C./min under a nitrogen stream (oxygen concentration of 20 ppm or less). The temperature was raised and held for 30 minutes. Thereafter, this pre-baked film was cooled to 50 ° C. at a temperature lowering rate of 5 ° C./min, and thereby a polyimide resin film T4 adhered to the silicon substrate was produced.
  • First measurement example measurement of light transmittance (T)
  • the measurement of light transmittance used as appropriate in the following examples and comparative examples will be described.
  • the light transmittance at a wavelength of 450 nm of the polyimide resin film T2 of the fifth preparation example was measured using an ultraviolet-visible spectrophotometer (MultiSpec 1500) manufactured by Shimadzu Corporation.
  • thermomechanical analyzer EXSTAR6000TMA / SS6000 manufactured by SII Nanotechnology. Measured in compressed mode.
  • the temperature raising method was performed under the following conditions.
  • the sample was heated to 150 degrees at a temperature increase rate of 5 ° C./min to remove the adsorbed water from the sample.
  • the sample was air-cooled to room temperature at a rate of 5 ° C./min.
  • the sample was measured at a rate of temperature increase of 5 ° C./min to determine the glass transition temperature of the polyimide resin film T1.
  • the average value of the linear expansion coefficients of the samples at 50 to 200 ° C. was obtained and used as the linear expansion coefficient of the polyimide resin film T1.
  • this varnish coating film was pre-baked for 4 minutes at a temperature of 140 ° C. using a Mark-7 hot plate.
  • the prebaked film thus obtained was heated to 350 ° C. at a temperature increase rate of 3.5 ° C./min under a nitrogen stream (oxygen concentration of 20 ppm or less). The temperature was raised and held for 30 minutes. Thereafter, the pre-baked film was cooled to 50 ° C. at a temperature decrease rate of 5 ° C./min, thereby producing a silicon wafer with a polyimide resin film. After the silicon wafer was dried at 150 ° C.
  • E is the biaxial elastic modulus (Pa) of the silicon wafer.
  • h is the thickness (m) of the silicon wafer.
  • t is the film thickness (m) of the polyimide resin film.
  • r 1 is a curvature radius (m) of the silicon wafer before the polyimide resin film is produced.
  • r 2 is the radius of curvature (m) of the silicon wafer after the polyimide resin film is produced.
  • the biaxial elastic modulus E of the silicon wafer was determined as 1.805 ⁇ 10 ⁇ 11 (Pa).
  • Evaluation Examples 1 to 12 polyimide resin films T1 to T4 were produced for the varnishes of Synthesis Examples 1 to 12 described above by the methods of the fourth production example to the seventh production example, and the first measurement example to the fourth measurement example.
  • the light transmittance, haze value, glass transition temperature (Tg), linear expansion coefficient, and residual stress were measured by the above method.
  • the results of Evaluation Examples 1 to 12 are shown in Table 2.
  • volume resistivity When the volume resistivity is less than 60 ⁇ ⁇ cm in the evaluation criteria of conductivity evaluation, it is level 5. When the volume resistivity is 60 ⁇ ⁇ cm or more and less than 80 ⁇ ⁇ cm, it is Level 4. When the volume resistivity is 80 ⁇ ⁇ cm or more and less than 100 ⁇ ⁇ cm, it is Level 3. Level 2 when the volume resistivity is 100 ⁇ ⁇ cm or more and less than 150 ⁇ ⁇ cm. Level 1 when the volume resistivity is 150 ⁇ ⁇ cm or more.
  • the transmittance at a wavelength of 400 nm before and after the formation of the first wiring layer in the unexposed portion of the substrate manufactured up to the first wiring layer of the touch panel was measured using an ultraviolet-visible spectrophotometer (“MultiSpec-1500 (trade name)” manufactured by Shimadzu Corporation). Then, when the transmittance before forming the first wiring layer is T0 and the transmittance after forming the first wiring layer is T, the transmittance change represented by the formula (T0-T) / T0 is calculated. did. Using the obtained value of transmittance change, the residue of the conductive composition of the touch panel was evaluated according to the following evaluation criteria. In this evaluation, the case where the evaluation result was level 2 or higher was regarded as acceptable.
  • the value of transmittance change when the value of transmittance change is less than 1%, it is level 5.
  • the value of the transmittance change is 1% or more and less than 2%, it is level 4.
  • the value of the transmittance change is 2% or more and less than 3%, it is level 3.
  • the transmittance change value is 3% or more and less than 4%, it is level 2.
  • the value of the transmittance change is 4% or more, it is level 1.
  • CM-2600d manufactured by Konica Minolta Co., Ltd.
  • the reflectance of the total reflected light is measured from the glass substrate side of the substrate manufactured up to the second insulating layer of the touch panel, and CIE (L *, a *, B *)
  • the color characteristic b * was measured in the color space.
  • the color of the touch panel was evaluated according to the following evaluation criteria. In this evaluation, the case where the evaluation result was level 2 or higher was regarded as acceptable.
  • a D65 light source was used as the light source.
  • the color characteristic b * is ⁇ 2 ⁇ b * ⁇ 2 in the evaluation criteria of the color eye evaluation, it is level 5.
  • Level 4 when the color characteristic b * is ⁇ 3 ⁇ b * ⁇ 2 or 2 ⁇ b * ⁇ 3. If the color characteristic b * is ⁇ 4 ⁇ b * ⁇ 3 or 3 ⁇ b * ⁇ 4, it is level 3. If the color characteristic b * is ⁇ 5 ⁇ b * ⁇ 4 or 4 ⁇ b * ⁇ 5, it is level 2. If the color characteristic b * is b * ⁇ 5 or 5 ⁇ b *, it is level 1.
  • an insulation deterioration characteristic evaluation system “ETAC SIR13” manufactured by Enomoto Kasei Co., Ltd.
  • An electrode was attached to each end of the first wiring layer and the second wiring layer of the touch panel, and the touch panel was placed in a high-temperature and high-humidity tank set at 85 ° C. and 85% RH. After 5 minutes from the stabilization of the environment in the tank, a voltage was applied between the electrodes of the first wiring layer and the second wiring layer, and the change in insulation resistance with time was measured. With the first wiring layer as the positive electrode and the second wiring layer as the negative electrode, a voltage of 10 V was applied, and the resistance value for 500 hours was measured at 5-minute intervals.
  • the measured resistance value reached 10 5 or less, it was judged as a short circuit due to poor insulation, the printing pressure was stopped, and the test time up to that time was defined as the short circuit time.
  • the wet heat resistance of the touch panel was evaluated according to the following evaluation criteria. In this evaluation, the case where the evaluation result was level 2 or higher was regarded as acceptable.
  • the short-circuit time is 1000 hours or more in the evaluation criteria of the wet heat resistance evaluation, it is level 5.
  • the short circuit time is 500 hours or more and less than 1000 hours, it is level 4.
  • the short circuit time is 300 hours or more and less than 500 hours, it is level 3.
  • the short circuit time is 100 hours or more and less than 300 hours, it is level 2. If the short circuit time is less than 100 hours, it is level 1.
  • the horizontal shift was measured at the design portion where the mesh intersection of the first wiring layer and the mesh intersection of the second wiring layer overlapped at the center of the multilayer substrate.
  • the dimensional accuracy of the touch panel was evaluated according to the following evaluation criteria. In this evaluation, the case where the evaluation result was level 2 or higher was regarded as acceptable.
  • the deviation is less than 1 ⁇ m in the dimensional accuracy evaluation criteria, it is level 5.
  • the deviation is 1 ⁇ m or more and less than 2 ⁇ m, it is level 4.
  • the deviation is 2 ⁇ m or more and less than 3 ⁇ m, it is level 3.
  • the deviation is 3 ⁇ m or more and less than 5 ⁇ m, it is level 2.
  • the deviation is 5 ⁇ m or more, it is level 1.
  • ESD electrostatic discharge resistance evaluation
  • the ESD test apparatus Compact ESD Simulator HCE-5000, manufactured by Hanwa Denshi Kogyo Co., Ltd.
  • HCE-5000 High ESD Simulator HCE-5000, manufactured by Hanwa Denshi Kogyo Co., Ltd.
  • Resistance was evaluated. Specifically, an electrode was attached to the end of the first wiring layer, and the voltage was continuously applied once in 100V steps starting from 100V.
  • the resistance value of the leakage current after voltage application is increased by 10% or more compared to before the voltage application, it is considered that the wiring layer is disconnected, and a voltage that is 100V lower than the disconnected voltage is defined as the ESD withstand voltage. did.
  • Example 1 ⁇ Formation of polyimide resin film>
  • the polyimide resin film T3 was produced by the method of the sixth production example using the varnish of Synthesis Example 1 produced in the first production example.
  • Example 1 On the polyimide resin film T3 obtained as described above, by using a target made of SiO 2, performs sputtering in an argon atmosphere, forming a gas barrier layer made of SiO 2 having a thickness of 100nm did.
  • the pressure was 2 ⁇ 10 ⁇ 1 Pa
  • the substrate temperature was 150 ° C.
  • the power source was an AC power source of 13.56 MHz.
  • Example 1 ⁇ Formation of first wiring layer>
  • the conductive composition AE-1 produced in the second production example was placed on a spin coater (“1H-360S (trade name) manufactured by Mikasa Co., Ltd.) on the substrate on which the polyimide resin film T3 and the gas barrier layer were formed. ) "), And spin-coated under the conditions of 300 rpm for 10 seconds and 500 rpm for 2 seconds. Thereafter, the coating film of the conductive composition AE-1 was prebaked at 100 ° C. for 2 minutes using a hot plate (“SCW-636 (trade name)” manufactured by Dainippon Screen Mfg. Co., Ltd.) to prepare a prebaked film. .
  • SCW-636 trade name
  • this pre-baked film was exposed through a desired mask using a parallel light mask aligner (“PLA-501F (trade name)” manufactured by Canon Inc.) using an ultrahigh pressure mercury lamp as a light source. Thereafter, the pre-baked film was subjected to shower development with a 0.045 mass% aqueous potassium hydroxide solution for 60 seconds using an automatic developing device (“AD-2000 (trade name)” manufactured by Takizawa Sangyo Co., Ltd.), and then with water. The pattern was processed by rinsing for 30 seconds. The substrate thus patterned was cured in the air (oxygen concentration 21%) at 250 ° C. for 30 minutes using an oven to form a first wiring layer.
  • Example 1 ⁇ Formation of first insulating layer>
  • the insulating composition OA-1 produced in the third production example was spin-coated at 650 rpm for 5 seconds on the substrate on which the first wiring layer was formed, using a spin coater. Thereafter, the coating film of this insulating composition OA-1 was pre-baked at 100 ° C. for 2 minutes using a hot plate to prepare a pre-baked film. Next, this pre-baked film was exposed through a desired mask using a parallel light mask aligner using an ultrahigh pressure mercury lamp as a light source.
  • the prebaked film was subjected to shower development with a 0.045 mass% potassium hydroxide aqueous solution for 60 seconds using an automatic developing device, and then rinsed with water for 30 seconds to perform pattern processing.
  • the substrate thus patterned was cured in an air (oxygen concentration: 21%) at 250 ° C. for 60 minutes to form a first insulating layer.
  • Example 1 ⁇ Formation of second wiring layer>
  • the second wiring layer was formed on the substrate on which the first insulating layer was formed as described above by the same method as the first wiring layer.
  • Example 1 ⁇ Formation of second insulating layer>
  • the second insulating layer was formed on the substrate on which the second wiring layer was formed as described above by the same method as the first insulating layer.
  • Example 1 the periphery of the area where the first wiring layer and the second wiring layer were formed was cut with a single blade from the upper surface, and mechanically peeled from the cut end surface to obtain the touch panel of Example 1.
  • the conductivity, the residue of the conductive composition, the color (b *), the moist heat resistance, the dimensional accuracy, and the ESD voltage resistance were evaluated by the methods described above.
  • the evaluation results of Example 1 are shown in Table 3 described later.
  • Example 2 In Example 2, the same operation as in Example 1 was repeated except that the varnish of Synthesis Example 2 was used as the varnish for forming a polyimide resin film. As shown in Table 3, in the touch panel of Example 2, since the polyimide contained in the polyimide resin film has the structural unit of the general formula (1), the dimensional accuracy is improved and the level of the evaluation result is “5”. It became. The color was slightly deteriorated due to yellowing during wiring processing, and the evaluation result level was “3”.
  • Example 3 In Example 3, the same operation as in Example 1 was repeated except that the varnish of Synthesis Example 3 was used as the varnish for forming a polyimide resin film. As shown in Table 3, in the touch panel of Example 3, since the polyimide contained in the polyimide resin film has the structural unit of the general formula (2), the dimensional accuracy is improved and the level of the evaluation result is “4”. It became. The color was slightly deteriorated due to yellowing during wiring processing, and the evaluation result level was “3”.
  • Example 4 In Example 4, the same operation as in Example 1 was repeated except that the varnish of Synthesis Example 4 was used as the varnish for forming a polyimide resin film. As shown in Table 3, in the touch panel of Example 4, since the polyimide contained in the polyimide resin film has the structural unit of the general formula (2), the dimensional accuracy is improved and the evaluation result level is “5”. It became. The color was slightly deteriorated due to yellowing during wiring processing, and the evaluation result level was “3”.
  • Example 5 In Example 5, the same operation as in Example 1 was repeated except that the varnish of Synthesis Example 5 was used as the varnish for forming a polyimide resin film. As shown in Table 3, in the touch panel of Example 5, the polyimide contained in the polyimide resin film has a structural unit represented by the general formula (4) as a main component and a structure represented by the general formula (5). Since the unit contained 5 mol% or more and 30 mol% or less of all the structural units, the dimensional accuracy was improved and the evaluation result level was “5”.
  • Example 6 In Example 6, the same operation as in Example 1 was repeated except that the varnish of Synthesis Example 6 was used as the varnish for forming a polyimide resin film. As shown in Table 3, in the touch panel of Example 6, since the polyimide included in the polyimide resin film has a repeating structure represented by the general formula (9), the dimensional accuracy is improved and the level of the evaluation result is “5”. Moreover, ESD withstand voltage improved and became 1200V.
  • Example 7 In Example 7, the same operation as in Example 1 was repeated except that the varnish of Synthesis Example 7 was used as the varnish for forming a polyimide resin film. As shown in Table 3, in the touch panel of Example 7, since the Tg of the polyimide resin film is slightly low (see Evaluation Example 7 in Table 2), the dimensional accuracy deteriorates and the evaluation result level is “2”. However, it was in a usable range.
  • Example 8 In Example 8, the same operation as Example 1 was repeated except that the varnish of Synthesis Example 10 was used as the varnish for forming a polyimide resin film. As shown in Table 3, in the touch panel of Example 8, since the polyimide contained in the polyimide resin film has a repeating structure represented by the general formula (9), the dimensional accuracy is improved and the level of the evaluation result is “5”. Moreover, ESD withstand voltage improved and became 1200V.
  • Example 9 In Example 9, the same operation as in Example 1 was repeated except that the varnish of Synthesis Example 11 was used as the varnish for forming a polyimide resin film. As shown in Table 3, in the touch panel of Example 9, since the polyimide contained in the polyimide resin film has a repeating structure represented by the general formula (9), the dimensional accuracy is improved and the level of the evaluation result is “5”. Moreover, ESD withstand voltage improved and became 1200V.
  • Example 10 In Example 10, the same operation as in Example 1 was repeated except that the varnish of Synthesis Example 12 was used as the varnish for forming a polyimide resin film. As shown in Table 3, in the touch panel of Example 10, since the polyimide contained in the polyimide resin film has a repeating structure represented by the general formula (9), the dimensional accuracy is improved and the level of the evaluation result is “5”. Moreover, ESD withstand voltage improved and became 1100V.
  • Example 11 In Example 11, the same operation as Example 5 was repeated except that the target was changed to a target made of SiON when forming the gas barrier layer. As shown in Table 3, in the touch panel of Example 11, by changing the gas barrier layer, the color was improved and the evaluation result level was “5”. On the other hand, chemical resistance decreased by changing the gas barrier layer. As a result, the conductive composition residue and the dimensional accuracy slightly deteriorated, and the evaluation result level was “4”, but both were in the usable range.
  • Example 12 when forming the gas barrier layer, first, sputtering was performed in an argon atmosphere using a target made of SiON to form a gas barrier layer made of SiON having a thickness of 80 nm. Next, using a target of SiO 2, performs sputtering in an argon atmosphere to form a gas barrier layer made of SiO 2 having a thickness of 20 nm. Except this, the same operation as in Example 5 was repeated. As shown in Table 3, in the touch panel of Example 12, by setting the gas barrier layer on the polyimide resin film side to SiON, yellowing during wiring processing is suppressed, and as a result, the color is improved and the evaluation result The level is now “5”.
  • the barrier property of the gas barrier layer was improved, the heat and humidity resistance was improved, and the evaluation result level was “5”. Furthermore, since the gas barrier layer on the wiring layer side was made of SiO 2 , the conductive composition residue and dimensional accuracy were good, with the evaluation result level remaining at “5”.
  • Example 13 In Example 13, the same operation as in Example 5 was repeated except that the conductive composition was changed from the conductive composition AE-1 to the conductive composition AE-2. As shown in Table 3, in the touch panel of Example 13, the conductive particles (metal fine particles) contained in the conductive composition AE-2 were not coated, and the metal fine particles aggregated non-uniformly in the wiring layer. did. Therefore, although the conductivity deteriorated and the evaluation result level was “3”, it was in a usable range. Moreover, although the conductive composition residue and the dimensional accuracy were slightly deteriorated and the level of the evaluation result was “4”, it was in a range where there was no problem in use.
  • Example 14 In Example 14, the same operation as in Example 5 was repeated except that the insulating composition was changed from the insulating composition OA-1 to the insulating composition OA-2. As shown in Table 3, in the touch panel of Example 14, since the insulating layer does not have a predetermined cardo resin, the heat and humidity resistance is greatly deteriorated and the evaluation result level is “2”. It was possible. The conductivity, the conductive composition residue, and the dimensional accuracy were slightly deteriorated and the evaluation result level was “4”.
  • Example 15 In Example 15, when the wiring layer was formed, the patterned substrate was heated using an inert oven (INH-21CD manufactured by Koyo Thermo Systems Co., Ltd.) under a nitrogen stream (oxygen concentration 14%). The same operation as in Example 5 was repeated. As shown in Table 3, in the touch panel of Example 15, due to the change in the oxygen concentration during the formation of the wiring layer, the color was improved and the evaluation result level was “5”. On the other hand, the conductivity was greatly deteriorated and the evaluation result level was “2”, but it was in a usable range. The dimensional accuracy slightly deteriorated and the evaluation result level was “4”, but it was in a range where there was no problem in use.
  • Example 16 In Example 16, the same operation as in Example 11 was repeated except that the varnish of Synthesis Example 6 was used as the polyimide resin film-forming varnish. As shown in Table 3, in the touch panel of Example 16, since the polyimide contained in the polyimide resin film has a repeating structure represented by the general formula (9), the dimensional accuracy is improved and the level of the evaluation result is “5”. Moreover, ESD withstand voltage improved and became 1300V.
  • Example 17 In Example 17, the same operation as in Example 12 was repeated except that the varnish of Synthesis Example 6 was used as the varnish for forming a polyimide resin film. As shown in Table 3, in the touch panel of Example 17, since the polyimide contained in the polyimide resin film has a repeating structure represented by the general formula (9), the ESD withstand voltage is improved to 1300 V. .
  • Comparative Example 1 In Comparative Example 1, the same operation as in Example 5 was repeated except that the first wiring layer was formed directly on the polyimide resin film without forming the gas barrier layer. In the touch panel of Comparative Example 1, the conductive composition residue, color, and heat-and-moisture resistance were significantly lowered, and the level was unusable (level 1).
  • Comparative Example 2 In Comparative Example 2, the same operation as in Example 5 was repeated except that the varnish of Synthesis Example 8 was used as the varnish for forming a polyimide resin film.
  • the imide group concentration of the polyimide contained in the polyimide resin film was high, and haze was generated after the resin film was formed, and the visibility was greatly impaired. For this reason, the polyimide resin film in Comparative Example 2 was not applicable as a touch panel substrate.
  • Comparative Example 3 In Comparative Example 3, the same operation as in Example 5 was repeated except that the varnish of Synthesis Example 9 was used as the polyimide resin film-forming varnish. In the touch panel of Comparative Example 2, since the imide group concentration of the polyimide contained in the polyimide resin film is low and the Tg of the polyimide resin film is reduced (see Evaluation Example 9 in Table 2), the dimensional accuracy is greatly reduced and cannot be used. Level (level 1). The evaluation results of Comparative Examples 1 to 3 are shown in Table 3 together with the evaluation results of Examples 1 to 17 described above.
  • the method for manufacturing a film with a conductive layer, a touch panel, a film with a conductive layer, and a method for manufacturing a touch panel according to the present invention suppresses yellowing of the resin film during formation of the conductive layer and provides high dimensional accuracy of the conductive layer.
  • a film with a conductive layer, a touch panel, a method for producing a film with a conductive layer, and a method for producing a touch panel is suitable for a film with a conductive layer, a touch panel, a method for producing a film with a conductive layer, and a method for producing a touch panel.

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PCT/JP2018/011518 2017-03-29 2018-03-22 導電層付きフィルム、タッチパネル、導電層付きフィルムの製造方法およびタッチパネルの製造方法 WO2018180926A1 (ja)

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