WO2018138879A1 - Film conducteur photosensible, procédé de formation de motif conducteur, procédé de production de substrat à motif conducteur, substrat à motif conducteur et capteur à panneau tactile - Google Patents

Film conducteur photosensible, procédé de formation de motif conducteur, procédé de production de substrat à motif conducteur, substrat à motif conducteur et capteur à panneau tactile Download PDF

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Publication number
WO2018138879A1
WO2018138879A1 PCT/JP2017/002984 JP2017002984W WO2018138879A1 WO 2018138879 A1 WO2018138879 A1 WO 2018138879A1 JP 2017002984 W JP2017002984 W JP 2017002984W WO 2018138879 A1 WO2018138879 A1 WO 2018138879A1
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Prior art keywords
conductive
resin layer
photosensitive
conductive pattern
photosensitive resin
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PCT/JP2017/002984
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English (en)
Japanese (ja)
Inventor
謙介 吉原
昂平 平尾
森　拓也
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日立化成株式会社
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Priority to PCT/JP2017/002984 priority Critical patent/WO2018138879A1/fr
Priority to TW107102815A priority patent/TW201840595A/zh
Publication of WO2018138879A1 publication Critical patent/WO2018138879A1/fr

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    • 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
    • G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means
    • G06F3/0446—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means using a grid-like structure of electrodes in at least two directions, e.g. using row and column electrodes
    • 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
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • 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

Definitions

  • the present invention relates to a photosensitive conductive film, a method for forming a conductive pattern using the same, a method for manufacturing a conductive pattern substrate, and a conductive pattern substrate and a touch panel sensor, and in particular, a flat panel display such as a liquid crystal display element and a touch panel.
  • the present invention relates to a method for forming a conductive pattern used as an electrode wiring of a device such as a sensor, a solar cell, or an illumination.
  • Liquid crystal display elements or touch panels are used for large electronic devices such as personal computers and televisions, small electronic devices such as car navigation systems, smart phones and electronic dictionaries, display devices such as OA devices and FA devices.
  • display devices such as OA devices and FA devices.
  • a part of wiring, pixel electrodes, or terminals that are required to be transparent are formed from a transparent conductive film.
  • ITO Indium-Tin-Oxide
  • indium oxide Indium oxide
  • tin oxide Tin oxide
  • Patent Documents 1 and 2 a conductive film containing conductive fibers such as silver fibers and a photosensitive resin layer are provided on a substrate, and exposure and development through a pattern mask are performed on these.
  • a method of forming a conductive pattern is disclosed (for example, see Patent Document 1 or 2 below).
  • conductive networks made of conductive fibers are susceptible to deterioration due to external factors such as water and heat. Under high-temperature and high-humidity conditions, the conductive fibers are deteriorated, and the conductive network including them tends to increase the electrical resistance.
  • a touch panel sensor in which a sensor electrode is formed from a conductive network including a conductive fiber, there is a possibility that it does not operate normally when exposed to a hot and humid environment for a long time.
  • the present invention relates to a photosensitive conductive film capable of forming a conductive pattern in which electrical resistance is unlikely to increase even under high-temperature and high-humidity conditions, a method for forming a conductive pattern using the same, and a method for manufacturing a conductive pattern substrate,
  • An object of the present invention is to provide a conductive pattern substrate and a touch panel sensor.
  • the present inventors have found that a photosensitive conductive film provided with a photosensitive resin layer containing a specific compound adjacent to a conductive network containing conductive fibers is provided. Based on this finding, it was found that a conductive pattern having sufficient conductivity could be formed by a simple method by exposure and development, and that the formed conductive pattern hardly increased in electrical resistance even under high temperature and high humidity conditions.
  • the present invention has been completed.
  • the present invention includes a photosensitive resin layer, and a conductive network using conductive fibers provided on one main surface side of the photosensitive resin layer, and the photosensitive resin layer is (A) a binder.
  • a photosensitive conductive film containing a polymer (B) a polymerizable compound, (C) a photopolymerization initiator, and (D) a metal complex and / or a heteroatom compound.
  • the photosensitive conductive film of the present invention by conducting exposure and development while being placed on a substrate, the conductive film has sufficient conductivity and does not easily increase in electrical resistance even under high temperature and high humidity conditions.
  • a pattern can be formed.
  • the conductive pattern formed by the photosensitive conductive film of the present invention has a conductive fiber agglomeration as compared with a conductive network containing conductive fibers and a corrosion inhibitor blended into the patterned conductive pattern. And the visibility of light transmittance, haze, and the like can be further improved.
  • the component (D) preferably contains a metal complex and a heteroatom compound in that the increase in electrical resistance under high temperature and high humidity conditions can be further suppressed to a high level.
  • the photosensitive resin layer can contain an iron complex as a metal complex.
  • the photosensitive resin layer can contain a heterocyclic compound as a heteroatom compound.
  • the heteroatom of the above heterocyclic compound may be nitrogen.
  • the photosensitive resin layer may contain a metal complex and a nitrogen-containing heterocyclic compound as a heteroatom compound.
  • the total content of the component (D) in the photosensitive resin layer is 0.01 to 10 with respect to 100 parts by mass of the total content of the component (A), the component (B), and the component (C). It can be a mass part.
  • excellent conductivity (low resistance value) and transparency in the formed conductive pattern, and an effect of suppressing increase in electrical resistance under high temperature and high humidity conditions Can be made compatible at a higher level.
  • the present invention also includes a step of disposing the photosensitive conductive film according to the present invention on the substrate such that the photosensitive resin layer is positioned on the substrate side, and actinic rays in a pattern on the photosensitive resin layer.
  • a first method for forming a conductive pattern comprising an exposing step of irradiating and a developing step of forming a conductive pattern by removing an unexposed portion of a photosensitive resin layer.
  • the present invention also includes a step of disposing the photosensitive conductive film according to the present invention on the substrate such that the photosensitive resin layer is positioned on the substrate side, and actinic rays in a pattern on the photosensitive resin layer.
  • a development method for forming a conductive pattern is provided by performing development processing on the photosensitive resin layer that has undergone the exposure step, and a second method for forming a conductive pattern is provided.
  • the present invention also includes a step of disposing the photosensitive conductive film according to the present invention on the substrate such that the conductive network is located on the substrate side, and irradiating the photosensitive resin layer with active light in a pattern.
  • a third method for forming a conductive pattern comprising: an exposing step for performing, and a developing step for forming a conductive pattern by removing an unexposed portion of the photosensitive resin layer.
  • the electrical resistance is increased even on a base material having sufficient conductivity and high temperature and high humidity.
  • a difficult conductive pattern can be formed.
  • the exposed portion in the first exposure step is a resin cured layer having a conductive network
  • the first of the exposed portions in the second exposure step can be a cured resin layer that does not have a conductive network.
  • the step of the conductive pattern can be reduced compared to the case where only the conductive pattern is provided on the base material.
  • a pattern can be made difficult to visually recognize.
  • the third method for forming a conductive pattern according to the present invention when an electrode is provided on the base (for example, when the substrate has an electrode), the conductive pattern connected to the electrode is used. Can be easily formed.
  • the present invention also provides a method for producing a conductive pattern base material comprising a step of forming a conductive pattern on the base material by the first, second or third method for forming a conductive pattern according to the present invention.
  • a conductive pattern substrate having a conductive pattern in which the electrical resistance is hardly increased even under high temperature and high humidity conditions can be produced.
  • a conductive pattern base material is applied to a touch panel sensor, it is possible to sufficiently suppress a decrease in reliability due to an increase in electrical resistance under high temperature and high humidity.
  • the present invention also includes a base material and a conductive pattern provided on the base material, wherein the conductive pattern includes a cured resin layer containing a metal complex and / or a heteroatom compound and a conductive fiber.
  • a first conductive pattern base material including a network in this order from the base material side is provided.
  • the resin cured layer may include a portion that does not have a conductive network on the side opposite to the substrate.
  • the present invention also includes a base material and a conductive pattern provided on the base material, wherein the conductive pattern includes a conductive network including conductive fibers, a metal complex, and / or a heteroatom compound. Are provided in this order from the substrate side.
  • the first and second conductive pattern base materials according to the present invention can have a conductive pattern in which the electrical resistance hardly increases even under high temperature and high humidity conditions. Thereby, for example, when a conductive pattern base material is applied to a touch panel sensor, it is possible to sufficiently suppress a decrease in reliability due to an increase in electrical resistance under high temperature and high humidity.
  • the present invention also provides a touch panel sensor including the first or second conductive pattern base material according to the present invention.
  • the touch panel sensor according to the present invention is less likely to increase in electrical resistance even when the conductive pattern is under a high temperature and high humidity condition, and can have excellent reliability.
  • the photosensitive conductive film which enables formation of the conductive pattern which is hard to raise an electrical resistance even under high temperature, high humidity conditions, the formation method of a conductive pattern using this, and manufacture of a conductive pattern base material
  • a method, a conductive pattern base material, and a touch panel sensor can be provided.
  • FIG. 6 is a partial cross-sectional view taken along the line a-a ′ shown in FIG. 5.
  • FIG. 6 is a partial cross-sectional view taken along the line b-b ′ shown in FIG.
  • (meth) acrylate means “acrylate” or “methacrylate” corresponding thereto.
  • (meth) acrylic means “acrylic” or “methacrylic” corresponding thereto
  • (meth) acrylic acid means “acrylic acid” or “methacrylic acid” corresponding thereto
  • (Meth) acryloyl means “acryloyl” or the corresponding “methacryloyl”.
  • (Meth) acrylic acid alkyl ester” means “acrylic acid alkyl ester” or “methacrylic acid alkyl ester” corresponding thereto.
  • a or B only needs to include one of A and B, and may include both.
  • the exemplary materials may be used alone or in combination of two or more unless otherwise specified.
  • a numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
  • the photosensitive conductive film according to the present invention includes a photosensitive resin layer and a conductive network including conductive fibers provided on one main surface side of the photosensitive resin layer.
  • FIG. 1 is a schematic cross-sectional view showing a preferred embodiment of the photosensitive conductive film of the present embodiment.
  • a photosensitive conductive film 10 with a support film shown in FIG. 1 includes a support film 1 and a photosensitive conductive film 4 provided on the support film 1.
  • the photosensitive conductive film 4 includes a conductive network 2 provided on the support film 1 and a photosensitive resin layer 3 provided on the conductive network 2.
  • the photosensitive conductive film 4 has the conductive network 2 and the photosensitive resin layer 3 in this order from the support film 1 side.
  • a polymer film can be used as the support film 1.
  • the polymer film include a polyethylene terephthalate film, a polyethylene film, a polypropylene film, and a polycarbonate film.
  • a polyethylene terephthalate film is preferable from the viewpoints of transparency and heat resistance.
  • the above polymer film may be subjected to a release treatment so that it can be easily peeled off from the photosensitive conductive film 4 later.
  • the thickness of the support film 1 is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, and further preferably 15 ⁇ m or more from the viewpoint of mechanical strength.
  • a step of applying a conductive fiber dispersion or a conductive fiber solution in order to form the conductive network 2 by setting the thickness of the support film 1 to the above numerical value or more It is possible to prevent the support film 1 from being broken in the step of applying the photosensitive resin composition. Further, the same effect can be expected in the step of peeling the support film 1 from the photosensitive conductive film 4 in the second exposure step or development step described later.
  • the thickness of the support film 1 is preferably 300 ⁇ m or less, and 200 ⁇ m or less. More preferably, it is more preferably 100 ⁇ m or less.
  • the thickness of the support film 1 is preferably 5 to 300 ⁇ m, more preferably 10 to 200 ⁇ m, and particularly preferably 15 to 100 ⁇ m.
  • the haze value of the support film 1 is preferably 0.01 to 5.0%, more preferably 0.01 to 3.0%, from the viewpoint of improving sensitivity and resolution. More preferably, it is more preferably from 2.0% to 2.0%, and particularly preferably from 0.01% to 1.5%.
  • the haze value can be measured according to JIS K 7105. For example, the haze value can be measured with a commercially available turbidimeter such as NDH5000 (manufactured by Nippon Denshoku Industries Co., Ltd., trade name).
  • the conductive network 2 includes conductive fibers, and can be formed from a plurality of conductive fibers. Such a conductive network can achieve both conductivity and transparency, developability is further improved, and a conductive pattern with excellent resolution can be formed.
  • the conductive network is, for example, (1) a state in which the conductive fibers are separated from each other in a conductive range, (2) a state in which the conductive fibers are in contact, or (3) a state in which the conductive fibers are fused at the contact points. It can be a fiber assembly in a worn state.
  • Examples of the conductive fiber included in the conductive network include metal fibers such as gold, silver, copper, and platinum, or conductive fibers such as carbon fibers such as carbon nanotubes. From the viewpoint of conductivity, it is preferable to use gold fibers and / or silver fibers, and from the viewpoint of easily adjusting the conductivity, it is more preferable to use silver fibers such as silver nanowires.
  • the metal fiber can be prepared by, for example, a method of reducing metal ions with a reducing agent such as NaBH 4 or a polyol method.
  • the conductive fibers containing silver nanowires can also be prepared by a method of reducing silver ions with a reducing agent such as NaBH 4 or a polyol method.
  • the carbon nanotubes may be commercial products such as Hipym single-walled carbon nanotubes from Unidim.
  • the fiber diameter of the conductive fiber is preferably 1 nm to 50 nm, more preferably 2 nm to 20 nm, and even more preferably 3 nm to 10 nm from the viewpoint of achieving both static resistance and visibility.
  • the fiber length of the conductive fiber is preferably 1 ⁇ m to 100 ⁇ m, more preferably 2 ⁇ m to 50 ⁇ m, and even more preferably 3 ⁇ m to 10 ⁇ m from the viewpoint of achieving both conductivity and visibility. .
  • the fiber diameter and fiber length can be measured with a scanning electron microscope.
  • an organic conductor can be used in combination with the conductive fiber.
  • the organic conductor include a conductive polymer.
  • the conductive polymer at least one polymer selected from the group consisting of polythiophene, polythiophene derivatives, polyaniline, and polyaniline derivatives can be used.
  • polythiophene, polythiophene derivatives, polyaniline, and polyaniline derivatives can be used.
  • polyethylenedioxythiophene, polyhexylthiophene, polyaniline and the like can be mentioned.
  • the conductive layer preferably further includes a photosensitive resin composition.
  • the photosensitive resin composition can use the component which comprises the photosensitive resin layer mentioned later.
  • a conductive network is provided on one main surface side of the photosensitive resin layer 3.
  • the boundary between the conductive network and the photosensitive resin layer is not necessarily clear.
  • the conductive network only needs to have conductivity in the surface direction of the photosensitive resin layer.
  • the conductive network provided on one main surface side of the photosensitive resin layer is, for example, (1) a state embedded in the photosensitive resin layer, (2) embedded in the photosensitive resin layer, and a part thereof is the photosensitive resin.
  • the state exposed from the main surface of the layer, (3) may be present in the state exposed entirely on the main surface of the photosensitive resin layer.
  • the thickness of the photosensitive resin layer described below refers to the thickness including a part of the conductive network when the conductive network is buried in the photosensitive resin layer. In addition, when at least a part of the conductive network is exposed from the photosensitive resin layer, it indicates the thickness of the photosensitive resin itself excluding the part.
  • FIG. 2 is a partially cutaway perspective view showing an embodiment of a photosensitive conductive film.
  • the conductive network 2 using conductive fibers preferably has a network structure in which the conductive fibers are in contact with each other.
  • the thickness of the conductive network 2 varies depending on the use of the conductive pattern formed using the photosensitive conductive film and the required conductivity, but is preferably 1 ⁇ m or less, and preferably 0.001 ⁇ m to 0.5 ⁇ m. Is more preferably 0.005 ⁇ m to 0.1 ⁇ m, and particularly preferably 0.01 to 0.1 ⁇ m.
  • the thickness of the conductive network 2 is 1 ⁇ m or less, the light transmittance in the wavelength region of 450 to 650 nm is high, the pattern forming property is excellent, and it is particularly suitable for the production of a transparent electrode.
  • the thickness of the electroconductive network 2 points out the value measured by a scanning electron micrograph.
  • the conductive network 2 is, for example, a conductive fiber obtained by adding the above-described conductive fiber, water and / or an organic solvent, and, if necessary, a dispersion stabilizer such as an organic conductor and a surfactant to the support film 1. It can be formed by applying the dispersion and drying. When the conductive fiber dispersion contains metal nanowires, a metal salt may be added in order to promote fusion between the metal nanowires. After drying, the conductive network 2 formed on the support film 1 may be laminated as necessary.
  • Coating can be performed by a known method such as a roll coating method, a comma coating method, a gravure coating method, an air knife coating method, a die coating method, a bar coating method, or a spray coating method.
  • the drying can be performed at 30 to 150 ° C. for about 1 to 30 minutes with a hot air convection dryer or the like.
  • the conductive fiber and the organic conductor may coexist with the surfactant and the dispersion stabilizer.
  • the conductive network includes a residue after drying derived from a solvent, an additive, and the like contained in a coating liquid in which conductive fibers are dispersed.
  • the photosensitive resin layer 3 is composed of a photosensitive resin composition containing (A) a binder polymer, (B) a polymerizable compound, (C) a photopolymerization initiator, and (D) a metal complex and / or a heteroatom compound. Can be formed.
  • Binder polymer for example, obtained by reaction of acrylic resin, styrene resin, epoxy resin, amide resin, amide epoxy resin, alkyd resin, phenol resin, ester resin, urethane resin, epoxy resin and (meth) acrylic acid
  • acrylic resin styrene resin
  • epoxy resin amide resin
  • amide epoxy resin alkyd resin
  • phenol resin ester resin
  • urethane resin epoxy resin
  • acrylic acid examples thereof include epoxy acrylate resins, acid-modified epoxy acrylate resins obtained by reaction of epoxy acrylate resins and acid anhydrides, and the like.
  • the acrylic resin has a structural unit derived from (meth) acrylic acid and a (meth) acrylic acid alkyl ester as a structural unit.
  • the “acrylic resin” means a polymer mainly having a structural unit derived from a polymerizable monomer having a (meth) acryloyl group.
  • acrylic resin those produced by radical polymerization of a polymerizable monomer having a (meth) acryloyl group can be used.
  • Examples of the polymerizable monomer having a (meth) acryloyl group include acrylamide such as diacetone acrylamide, (meth) acrylic acid alkyl ester, (meth) acrylic acid tetrahydrofurfuryl ester, and (meth) acrylic acid dimethylamino.
  • Ethyl ester (meth) acrylic acid diethylaminoethyl ester, (meth) acrylic acid glycidyl ester, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, (Meth) acrylic acid, ⁇ -bromo (meth) acrylic acid, ⁇ -chloro (meth) acrylic acid, ⁇ -furyl (meth) acrylic acid, ⁇ -styryl (meth) acrylic acid and the like.
  • the acrylic resin is substituted at the ⁇ -position or aromatic ring such as styrene, vinyltoluene, ⁇ -methylstyrene and the like.
  • Polymerizable styrene derivatives esters of vinyl alcohol such as acrylonitrile and vinyl-n-butyl ether, maleic acid monoesters such as maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid
  • one or two or more polymerizable monomers such as cinnamic acid, ⁇ -cyanocinnamic acid, itaconic acid, and crotonic acid may be copolymerized.
  • Examples of the (meth) acrylic acid alkyl ester include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, (meth) acrylic acid butyl ester, and (meth) acrylic acid.
  • Pentyl ester (meth) acrylic acid hexyl ester, (meth) acrylic acid heptyl ester, (meth) acrylic acid octyl ester, (meth) acrylic acid 2-ethylhexyl ester, (meth) acrylic acid nonyl ester, (meth) acrylic acid Examples include decyl ester, (meth) acrylic acid undecyl ester, and (meth) acrylic acid dodecyl ester.
  • the binder polymer preferably has a carboxyl group from the viewpoint of improving the alkali developability.
  • the polymerizable monomer having a carboxyl group for obtaining such a binder polymer include (meth) acrylic acid as described above.
  • the ratio of the carboxyl group in the binder polymer is 10 to 50% by mass as the ratio of the polymerizable monomer having a carboxyl group to the total polymerizable monomer used for obtaining the binder polymer. It is preferably 12 to 40% by mass, more preferably 15 to 30% by mass, and particularly preferably 15 to 25% by mass. In terms of excellent alkali developability, the content is preferably 10% by mass or more, and in terms of excellent alkali resistance in the non-developed portion, it is preferably 50% by mass or less.
  • the acid value of the binder polymer is preferably in the range of 50 to 150 mgKOH / g, and preferably in the range of 60 to 120 mgKOH / g, from the viewpoint of improving developability for various known developing solutions in the development step. More preferably, it is more preferably in the range of 70 to 100 mg KOH / g.
  • the weight average molecular weight of the binder polymer is preferably 5,000 to 300,000, more preferably 20,000 to 150,000, from the viewpoint of balancing mechanical strength and alkali developability. More preferably, 30,000 to 100,000.
  • the weight average molecular weight is preferably 5,000 or more from the viewpoint of excellent developer resistance of the non-development part. Further, from the viewpoint of development time, it is preferably 300,000 or less.
  • the measurement conditions of a weight average molecular weight shall be the same measurement conditions as the Example of this-application specification.
  • the above-described resins can be used alone or in combination of two or more.
  • a binder polymer made of a mixture containing two or more kinds of resins composed of different copolymerization components, or a mixture containing two or more kinds of resins having different weight average molecular weights examples thereof include a binder polymer and a binder polymer composed of a mixture containing two or more kinds of resins having different degrees of dispersion.
  • a polymerizable compound having an ethylenically unsaturated bond is preferable.
  • a known compound can be used as the polymerizable compound having an ethylenically unsaturated bond.
  • a compound obtained by reacting a polyhydric alcohol with an ⁇ , ⁇ -unsaturated carboxylic acid a compound obtained by reacting a glycidyl group-containing compound with an ⁇ , ⁇ -unsaturated carboxylic acid, or having a urethane bond (meth) Urethane monomers such as acrylate compounds, ⁇ -chloro- ⁇ -hydroxypropyl- ⁇ '-(meth) acryloyloxyethyl-o-phthalate, ⁇ -hydroxyethyl- ⁇ '-(meth) acryloyloxyethyl-o-phthalate, ⁇ Examples include phthalic acid compounds such as -hydroxypropyl- ⁇ '-(meth) acryloyloxyethyl-o-phthalate, and (meth) acrylic acid alkyl esters.
  • a known compound can be used as the compound obtained by reacting the polyhydric alcohol with an ⁇ , ⁇ -unsaturated carboxylic acid.
  • a known compound can be used.
  • the content ratio of the (B) polymerizable compound is preferably 30 to 80 parts by mass, and preferably 40 to 70 parts by mass with respect to 100 parts by mass of the total amount of the (A) binder polymer and (B) polymerizable compound. More preferred is 40 to 60 parts by mass. It is preferably 30 parts by mass or more in terms of excellent photocurability and coatability on the formed conductive network 2, and 80 parts by mass in terms of excellent storage stability when wound as a film. The following is preferable.
  • benzophenone N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2 Aromatic ketones such as benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1, benzoin Benzoin ether compounds such as methyl ether, benzoin ethyl ether and benzoin phenyl ether; benzoin compounds such as benzoin, methyl benzoin and ethyl benzoin; 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O -Benzoyloxime), 1- [
  • an oxime ester compound or a phosphine oxide compound is preferable from the viewpoints of transparency and pattern forming ability when the thickness of the photosensitive resin layer 3 is 10 ⁇ m or less.
  • the content ratio of (C) the photopolymerization initiator is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the total amount of (A) binder polymer and (B) polymerizable compound. More preferably, it is more preferably 1 to 5 parts by mass. In terms of excellent photosensitivity, it is preferably 0.1 parts by mass or more, and in terms of excellent photocurability inside the photosensitive resin layer 3, it is preferably 20 parts by mass or less.
  • Metal complex and / or heteroatom compound examples include acetylacetone metal complex, ammine metal complex, cyano metal complex, chloro metal complex, fluoro metal complex, bromo metal complex, sulfato metal complex, thiocyanate metal complex, acetate metal complex, and the like. From the viewpoint of solubility and stability in the photosensitive resin layer, an acetylacetone metal complex is preferable.
  • Examples of the metal of the metal complex include aluminum, chromium, manganese, nickel, secondary cobalt, copper, ferric iron, zirconium, and titanium.
  • Aluminum and zirconium are preferable from the viewpoint of the transparency of the formed conductive pattern.
  • Ferric iron is preferable in that it has excellent solubility in the photosensitive resin layer and can maintain transparency relatively.
  • the metal complex is preferably an iron complex from the viewpoint of solubility in an organic solvent.
  • iron complexes include tris (2,4-pentanedionato) iron (III) (also referred to as “acetylacetone iron complex”) and its analogs, ferrocene and its analogs, tris (dibenzoylmethanato) iron (III ) And the like.
  • tris (2,4-pentanedionato) iron (III) is preferable from the viewpoint of solubility in organic solvents and oxidation resistance.
  • Tris (2,4-pentanedionato) iron (III) is a compound represented by the following formula, and a commercially available product such as “Narsem Ferric Acid” (product name, manufactured by Nippon Chemical Industry Co., Ltd.) is used. be able to.
  • cobalt complex commercially available products such as “Narsem second cobalt” (product name, manufactured by Nippon Chemical Industry Co., Ltd.) can be used.
  • Commercially available products such as “Narsem Copper” (manufactured by Nippon Chemical Industry Co., Ltd., product name) can be used as the copper complex.
  • a known metal complex used as a metal corrosion inhibitor can also be used.
  • the content of the metal complex in the photosensitive resin layer according to the present embodiment is 0. 0 with respect to 100 parts by mass of the total content of (A) the binder polymer, (B) the polymerizable compound, and (C) the photopolymerization initiator.
  • the amount is preferably 01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, and still more preferably 0.1 to 2 parts by mass.
  • the content of the metal complex is preferably 0.01 parts by mass or more. From the viewpoint of sufficiently reducing the initial resistance value of the pattern and obtaining sufficient transparency, it is preferably 5 parts by mass or less.
  • the heteroatom compound means a compound containing at least one atom (heteroatom) other than carbon and hydrogen.
  • the heteroatom compound include a heterocyclic compound having a heteroatom as an atom constituting a ring, a compound having a heteroatom-containing group, and the like.
  • the heterocyclic compound include nitrogen-containing heterocyclic compounds such as 5-phenyl-1H-tetrazole, mercaptobenzothiazole, 1-phenyl-5-mercapto-1H-tetrazole, 1H-benzotriazole, 5-amino-1H-tetrazole, etc. Etc.
  • Examples of the compound having a hetero atom-containing group include thiol compounds such as pentafluorobenzenethiol and dodecanethiol. From the viewpoint of suppressing an increase in electrical resistance of the conductive pattern under high temperature and high humidity conditions, 1H-benzotriazole and 5-amino-1H-tetrazole are preferable.
  • the content of the heteroatom compound in the photosensitive resin layer according to this embodiment is 0 with respect to 100 parts by mass of the total content of (A) the binder polymer, (B) the polymerizable compound, and (C) the photopolymerization initiator. 0.01 to 5 parts by mass is preferable, 0.05 to 3 parts by mass is more preferable, and 0.1 to 2 parts by mass is even more preferable. From the viewpoint of suppressing the deterioration of the conductive fiber, in particular, the deterioration of the conductive fiber in a high-temperature and high-humidity environment, the content of the heteroatom compound is preferably 0.01 parts by mass or more and formed. From the viewpoint of sufficiently reducing the initial resistance value of the conductive pattern, it is preferably 5 parts by mass or less.
  • the photosensitive resin layer contains both the metal complex and the heteroatom compound from the viewpoint of suppressing deterioration of the conductive fibers, in particular, deterioration of the silver nanowires in a high-temperature and high-humidity environment.
  • the total content of the component (D) in the photosensitive resin layer is 0 with respect to 100 parts by mass of the total content of the (A) binder polymer, (B) polymerizable compound, and (C) photopolymerization initiator. 0.01 to 5 parts by mass is preferable, 0.05 to 3 parts by mass is more preferable, and 0.1 to 2 parts by mass is even more preferable.
  • the content ratio of the metal complex and the heteroatom compound suppresses an increase in the electrical resistance of the conductive pattern under high temperature and high humidity conditions.
  • the mass ratio (metal complex: heteroatom compound) is preferably 1: 1 to 20: 1, more preferably 1: 1 to 10: 1, and further preferably 1: 1 to 8: 1. preferable.
  • additives can be contained in the photosensitive resin layer 3 as needed.
  • Additives include plasticizers such as p-toluenesulfonamide, fillers, antifoaming agents, flame retardants, adhesion promoters, leveling agents, peeling accelerators, antioxidants, fragrances, imaging agents, thermal crosslinking agents, A rust preventive agent or the like can be contained.
  • the addition amount of these additives is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the total amount of (A) binder polymer and (B) polymerizable compound.
  • the photosensitive resin layer 3 is formed on the conductive network 2 formed on the support film 1, as required, with methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, It can be formed by applying a solution of a photosensitive resin composition having a solid content of about 10 to 60% by mass dissolved in a solvent such as propylene glycol monomethyl ether or a mixed solvent thereof and then drying. However, in this case, the amount of the remaining organic solvent in the photosensitive resin layer after drying is preferably 2% by mass or less in order to prevent the organic solvent from diffusing in the subsequent step.
  • another layer may be interposed between the photosensitive resin layer and the conductive network.
  • Coating can be performed by a known method. Examples thereof include a roll coating method, a comma coating method, a gravure coating method, an air knife coating method, a die coating method, a bar coating method, and a spray coating method. After coating, drying to remove the organic solvent and the like can be performed at 70 to 150 ° C. for about 5 to 30 minutes with a hot air convection dryer or the like.
  • the thickness of the photosensitive resin layer 3 varies depending on the use, it is preferably 1 to 200 ⁇ m, more preferably 1 to 50 ⁇ m, and further preferably 1 to 30 ⁇ m in thickness after drying. A thickness of 10 ⁇ m is particularly preferable. When this thickness is 1 ⁇ m or more, layer formation by coating tends to be easy, and when it is 200 ⁇ m or less, light transmittance is good and sufficient sensitivity can be obtained, and the photosensitive resin layer 3 From the viewpoint of photo-curing property.
  • the thickness of the photosensitive resin layer 3 can be measured with a scanning electron microscope. Further, the thickness of the photosensitive resin layer after curing is also preferably within the above range.
  • the sheet resistance value of the conductive resin layer 3 or the conductive pattern formed using the photosensitive resin layer 3 is preferably 200 ⁇ / ⁇ or less, and preferably 100 ⁇ / ⁇ or less from the viewpoint that it can be effectively used as a transparent electrode. More preferably, it is 50 ⁇ / ⁇ or less.
  • the sheet resistance value is adjusted to the above range depending on, for example, the type of conductors (for example, conductive fibers and organic conductors) included in the conductive network 2, or the concentration or coating amount of the conductive dispersion. Can do.
  • the photosensitive conductive film 4 (the conductive network 2 and the photosensitive resin layer 3) has a minimum light transmittance of 80% or more in a wavelength region of 450 to 650 nm. Preferably, it is 85% or more, more preferably 90% or more. When the photosensitive conductive film 4 satisfies such a condition, it is easy to increase the brightness in a display panel or the like. Further, when the thickness of the photosensitive conductive film 4 is 1 to 10 ⁇ m, the minimum light transmittance in the wavelength region of 450 to 650 nm is preferably 80% or more, more preferably 85% or more, and 90%. More preferably, it is the above. When the photosensitive conductive film 4 (the conductive network 2 and the photosensitive resin layer 3) satisfies such conditions, it is easy to increase the brightness in a display panel or the like.
  • the photosensitive conductive film of the present invention may be provided with other appropriately selected layers as long as the effects of the present invention are obtained.
  • the said photosensitive conductive film may have these layers individually by 1 type, and may have 2 or more types. Moreover, you may have 2 or more of the same kind of layers.
  • a protective film may be further provided on the surface of the photosensitive resin layer 3 opposite to the support film 1 side.
  • a polymer film having heat resistance and solvent resistance can be used.
  • a polyethylene terephthalate film, a polypropylene film, and a polyethylene film are mentioned.
  • the thickness of the protective film is preferably 1 to 100 ⁇ m, more preferably 5 to 50 ⁇ m, still more preferably 5 to 40 ⁇ m, and particularly preferably 15 to 30 ⁇ m.
  • the thickness of the protective film is preferably 1 ⁇ m or more from the viewpoint of excellent mechanical strength, and preferably 100 ⁇ m or less from the viewpoint of being relatively inexpensive.
  • the adhesive force between the protective film and the photosensitive resin layer 3 is such that the support film 1 and the photosensitive conductive film 4 (the conductive network 2 and the photosensitive resin are used in order to facilitate the peeling of the protective film from the photosensitive resin layer 3. It is preferably less than the adhesive strength with the layer 3).
  • the photosensitive conductive film 10 with a support film may further have layers such as an adhesive layer and a gas barrier layer on the protective film.
  • the photosensitive conductive film 10 with a support film can be stored, for example, in the form of a flat plate as it is, or in the form of a roll wound around a cylindrical core. At this time, it is preferable that the support film 1 is wound up so as to be the outermost side.
  • the photosensitive conductive film 10 with a support film does not have a protective film
  • the photosensitive conductive film 10 with a support film can be stored as it is in the form of a flat plate.
  • a first method for forming a conductive pattern according to the present invention includes a step of disposing a photosensitive conductive film according to the present invention on a substrate such that the photosensitive resin layer is positioned on the substrate side, and a photosensitive resin An exposure step of irradiating the layer with actinic rays in a pattern; and a development step of forming a conductive pattern by removing an unexposed portion of the photosensitive resin layer.
  • this method will be described.
  • FIG. 3 is a schematic cross-sectional view for explaining an embodiment of a method for forming a wiring (conductive pattern) using the photosensitive conductive film of the present embodiment.
  • the above-described photosensitive conductive film 10 with a support film is disposed so that the photosensitive resin layer 3 is in close contact with the base material 20 (FIG. 3A), and the support film 1.
  • the conductive pattern base material 30 is obtained through these steps (FIG. 3C).
  • ⁇ Base material> Although it can use without a restriction
  • the resin base material include a polyester resin, a polystyrene resin, an olefin resin, a polybutylene terephthalate resin, a polycarbonate resin, and an acrylic resin base material.
  • the thickness of the base material 20 can be appropriately selected according to the purpose of use, and a film-like base material may be used.
  • the film-like substrate include a polyethylene terephthalate film, a polycarbonate film, and a cycloolefin polymer film.
  • the substrate 20 preferably has a minimum light transmittance of 80% or more in the wavelength region of 450 to 650 nm, more preferably 85% or more, and further preferably 90% or more. When the base material 20 satisfies such a condition, it is easy to increase the brightness in a display panel or the like.
  • the photosensitive conductive film 10 with a support film is laminated by removing the protective film, if present, and then pressing the photosensitive resin layer 3 side against the substrate 20 while heating the substrate. it can.
  • this process is performed under reduced pressure from the viewpoint of adhesiveness and followability.
  • the degree of vacuum is preferably 10 hPa or less, but this condition is not particularly limited.
  • the lamination of the photosensitive conductive film 10 with the support film is preferably performed while heating the photosensitive resin layer 3 and / or the substrate 20 to 70 to 130 ° C., and the pressure bonding pressure is about 0.1 to 1.0 MPa ( 1 to 10 kgf / cm 2 ) is preferable, but these conditions are not particularly limited. Further, if the photosensitive resin layer 3 is heated to 70 to 130 ° C. as described above, it is not necessary to pre-heat the base material 20 in advance, but the pre-heat treatment of the base material 20 is required in order to further improve the lamination property. Can also be done.
  • Exposure process As an exposure method in the exposure step, there is a method (mask exposure method) in which an actinic ray L is irradiated in a pattern through a negative or positive mask pattern 5 called an artwork as shown in FIG.
  • the pattern includes a stripe shape, a shape in which diamond shapes are connected in series, and the like.
  • a carbon arc lamp, a mercury vapor arc lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, or a xenon lamp that can effectively radiate ultraviolet rays, visible light, or the like is used.
  • Ar ion lasers and semiconductor lasers are also used.
  • emits visible light such as a flood bulb for photography, a solar lamp, is used.
  • a method of irradiating actinic rays in a pattern by a direct drawing method using a laser exposure method or the like may be employed.
  • Exposure at the exposure step may vary depending on the composition of the device and the photosensitive resin composition used, preferably 5mJ / cm 2 ⁇ 1000mJ / cm 2, more preferably 10mJ / cm 2 ⁇ 200mJ / cm 2 is there. In terms of excellent photocurability, it is preferably 10 mJ / cm 2 or more, and in terms of resolution, it is preferably 200 mJ / cm 2 or less.
  • the exposure process can be performed in air, vacuum, etc., and the exposure atmosphere is not particularly limited.
  • the photosensitive conductive film 4 is exposed without peeling off the support film 1, thereby reducing the influence of oxygen and facilitating curing.
  • the unexposed area in the exposure process of the photosensitive conductive film 4 is removed. Specifically, the uncured portion (unexposed portion) of the photosensitive resin layer 3 is removed together with the conductive network 2 by wet development. Thereby, the conductive pattern base material 30 which has the conductive pattern 6 which consists of the resin cured layer (cured film) 3b hardened
  • the wet development can be performed by a known method such as spraying, rocking dipping, brushing, or scrubbing using, for example, an alkaline aqueous solution, an aqueous developer, or an organic solvent developer.
  • an alkaline aqueous solution is preferably used because it is safe and stable and has good operability.
  • the alkaline aqueous solution include 0.1 to 5% by mass sodium carbonate aqueous solution, 0.1 to 5% by mass potassium carbonate aqueous solution, 0.1 to 5% by mass sodium hydroxide aqueous solution, and 0.1 to 5% by mass sodium tetraborate.
  • An aqueous solution or the like is preferable.
  • the pH of the alkaline aqueous solution used for development is preferably in the range of 9 to 11, and the temperature can be adjusted according to the developability of the photosensitive resin layer.
  • a surfactant, an antifoaming agent, a small amount of an organic solvent for accelerating development, and the like may be mixed.
  • Examples of the developing method include a dip method, a paddle method, a high-pressure spray method, brushing, and slaving. Among these, it is preferable to use a high-pressure spray system from the viewpoint of improving the resolution.
  • the conductive pattern is further cured by performing heating at about 60 to 250 ° C. or exposure at about 0.2 to 10 J / cm 2 as necessary after development. Also good.
  • the conductive pattern 6 includes the resin cured layer 3b containing the metal complex and / or the heteroatom compound and the conductive network 2a in this order from the base material side. it can.
  • the content of the metal complex in the cured resin layer according to this embodiment is preferably 0.01 to 5% by mass, more preferably 0.01 to 3 parts by mass based on the total amount of the cured resin layer. More preferably, the content is 0.01 to 2 parts by mass. From the viewpoint of suppressing deterioration of conductive fibers, in particular, deterioration of silver nanowires in a high-temperature and high-humidity environment, the content of the metal complex is preferably 0.01% by mass or more. From the viewpoint of sufficiently reducing the initial resistance value of the pattern and obtaining sufficient transparency, it is preferably 5% by mass or less.
  • the content of the heteroatom compound in the cured resin layer according to this embodiment is preferably 0.01 to 5% by mass, more preferably 0.01 to 3 parts by mass based on the total amount of the cured resin layer.
  • the amount is preferably 0.01 to 2 parts by mass.
  • the content of the heteroatom compound is preferably 0.01% by mass or more. From the viewpoint of sufficiently reducing the initial resistance value of the conductive pattern and obtaining sufficient transparency, it is preferably 5% by mass or less.
  • the cured resin layer may contain both the metal complex and the heteroatom compound from the viewpoint of suppressing deterioration of the conductive fiber, in particular, deterioration of the silver nanowire in a high temperature and high humidity environment.
  • the total content of the component (D) in the cured resin layer is preferably 0.01 to 5% by mass, more preferably 0.01 to 3 parts by mass based on the total amount of the cured resin layer.
  • the amount is preferably 0.01 to 2 parts by mass.
  • the content ratio of the metal complex and the heteroatom compound is a mass from the point of suppressing an increase in electrical resistance of the conductive pattern under high temperature and high humidity conditions.
  • the ratio (metal complex: heteroatom compound) is preferably 1: 1 to 1:20, more preferably 1: 1 to 1:10, and still more preferably 1: 1 to 1: 8. .
  • the surface resistance of the conductive network 2a is preferably 200 ⁇ / ⁇ or less, more preferably 100 ⁇ / ⁇ or less, and further preferably 50 ⁇ / ⁇ or less.
  • the surface resistance can be adjusted by, for example, the type of conductive fiber, the concentration of the conductive fiber dispersion or solution, or the coating amount.
  • the conductive pattern 6 preferably has a minimum light transmittance of 80% or more in the wavelength region of 450 to 650 nm, more preferably 85% or more, and further preferably 90% or more. When the conductive pattern 6 satisfies such a condition, it is easy to increase the brightness in a display panel or the like.
  • b * is preferably 0.1 to 2.0, more preferably 0.1 to 1.0, and further preferably 0.1 to 0.7.
  • the visibility on a display panel or the like is further improved.
  • the conductive pattern obtained above has the thickness of the cured resin layer (cured film) 3b in addition to the thickness of the conductive network 2a. These thicknesses form a step Hb with the base material, and if this step is large, it becomes difficult to obtain the smoothness required for a display or the like. Moreover, since a conductive pattern will be easily visually recognized if a level
  • the preferable range of the thickness of the conductive network in the conductive pattern is the same as the preferable range of the thickness of the conductive network in the photosensitive conductive film. Moreover, the preferable range of the thickness of the resin cured layer in a conductive pattern is the same as the preferable range of the thickness of the photosensitive resin layer in a photosensitive conductive film.
  • the thickness of the conductive pattern 6 varies depending on the application, but is preferably 1 to 200 ⁇ m, more preferably 1 to 50 ⁇ m, still more preferably 1 to 30 ⁇ m, and particularly preferably 1 to 10 ⁇ m. .
  • the thickness is 1 ⁇ m or more, the conductivity is good, and when it is 200 ⁇ m or less, the light transmittance is good, which is preferable from the viewpoint of the touch panel visibility.
  • the thickness of the conductive pattern 6 can be measured with a scanning electron microscope.
  • a photosensitive conductive film having a laminated structure of a conductive network and a photosensitive resin layer is formed on a substrate, and the photosensitive resin layer is positioned on the substrate side.
  • the resin cured layer (cured film) and the conductive network are included on the substrate in this order from the substrate side, and the resin cured layer (cured film) has the conductive network on the side opposite to the substrate.
  • a conductive pattern including a portion having no conductive portion and a portion having a conductive network can be provided, and a conductive pattern in which the cured resin layer (cured film) and the conductive network have the same pattern is provided on the substrate. Compared to the case, the step of the conductive pattern can be reduced. Hereinafter, this method will be described.
  • FIG. 4 is a schematic cross-sectional view for explaining another embodiment of the conductive pattern forming method using the photosensitive conductive film of the present embodiment.
  • the above-described photosensitive conductive film 10 with a support film is disposed so that the photosensitive resin layer 3 is in close contact with the base material 20 (FIG. 4A), and the support film 1.
  • a second exposure step (FIG.
  • the conductive pattern base material 31 is obtained through these steps (FIG. 4D).
  • the laminating step can be performed in the same manner as in the first method described above.
  • First exposure process As an exposure method in the first exposure step, there is a method (mask exposure method) of irradiating actinic rays L in a pattern through a negative or positive mask pattern 5 called an artwork as shown in FIG. Can be mentioned.
  • the conditions such as the light source of actinic rays and the exposure amount in the first exposure step can be the same as those in the first forming method.
  • the actinic ray L can be irradiated in a pattern through the mask pattern 5.
  • the exposed portion in the first exposure step is also exposed in the second exposure step, but by performing such exposure twice, the portion exposed in the first exposure step is Compared to the case where no exposure is performed in the second exposure step, it is possible to prevent and form a boundary portion between the portion exposed in the first exposure step and the portion exposed in the second exposure step. It can suppress that the level
  • the conditions such as the actinic ray light source and the exposure amount in the second exposure step can be the same as those in the first forming method.
  • the photosensitive conductive film 4 (the conductive network 2 and the photosensitive resin layer 3 is exposed by removing the support film 1 and exposing the photosensitive conductive film 4 in the presence of oxygen. ),
  • the reactive species generated from the initiator are deactivated by oxygen, and an insufficiently cured region can be provided on the conductive network 2 side of the photosensitive resin layer 3. Since excessive exposure sufficiently cures the entire photosensitive resin composition, the exposure amount in the second exposure step is preferably within the above range.
  • the second exposure step is performed in the presence of oxygen, for example, preferably in the air. Further, the condition of increasing the oxygen concentration may be used.
  • the surface layer portion that is not sufficiently cured of the photosensitive resin layer 3 exposed in the second exposure process is removed.
  • the surface layer portion of the photosensitive resin layer 3 that is not sufficiently cured is removed together with the conductive network 2 by wet development.
  • it consists of the photosensitive resin layer hardened
  • the conductive network 2a having a predetermined pattern remains on the cured resin pattern, and the portion where the surface layer portion of the photosensitive resin layer is removed in the development process has no conductive network, and the concave portion has the cured resin layer 3a as the bottom surface. Is formed.
  • FIG. 4D a step between the conductive network 2a formed on the cured resin layer 3a containing the metal complex and / or the heteroatom compound and the bottom surface of the concave portion of the cured resin layer 3a.
  • a conductive pattern substrate 31 having a conductive pattern (wiring) 6 having a small Ha and a small step is obtained.
  • the developing process of this embodiment can be performed in the same manner as the first forming method described above.
  • the conductive pattern is further cured by performing exposure at about 0.2 to 10 J / cm 2 or heating at about 60 to 250 ° C. as necessary after development. May be.
  • the surface resistance of the conductive pattern is preferably 200 ⁇ / ⁇ or less, more preferably 100 ⁇ / ⁇ or less, and further preferably 50 ⁇ / ⁇ or less.
  • the conductive pattern 6 preferably has a minimum light transmittance of 80% or more in the wavelength region of 450 to 650 nm, more preferably 85% or more, and further preferably 90% or more. When the conductive pattern 6 satisfies such a condition, it is easy to increase the brightness in a display panel or the like.
  • b * is preferably 0.1 to 2.0, more preferably 0.1 to 1.0, and further preferably 0.1 to 0.7.
  • the visibility on a display panel or the like is further improved.
  • a touch panel sensor according to the present invention includes the conductive pattern base material.
  • FIG. 5 is a schematic top view showing an example of a capacitive touch panel sensor.
  • the touch panel sensor shown in FIG. 5 has a touch screen 102 for detecting a touch position on one surface of a base material 101 such as a transparent substrate. A transparent change is made in this region by detecting a change in capacitance and using it as an X position coordinate.
  • An electrode 103 and a transparent electrode 104 having Y position coordinates are provided.
  • Each of the transparent electrodes 103 and 104 having the X and Y position coordinates includes a lead wire 105 for connecting to a driver element circuit for controlling an electric signal as a touch panel sensor, and the lead wire 105 and the transparent electrode 103.
  • a connection electrode 106 for connecting 104 is disposed. Further, a connection terminal 107 connected to the driver element circuit is disposed at the end of the lead-out wiring 105 opposite to the connection electrode 106.
  • FIG. 6 is a schematic diagram showing an example of a manufacturing method of the touch panel sensor shown in FIG.
  • the transparent electrodes 103 and 104 are formed by the conductive pattern forming method according to the present embodiment.
  • a transparent electrode (X position coordinate) 103 is formed on a transparent substrate 101.
  • the photosensitive conductive film 10 with a support film is laminated so that the photosensitive resin layer 3 is in close contact with the transparent substrate 101.
  • the transferred photosensitive conductive film 4 (conductive network 2 and photosensitive resin layer 3) is irradiated with actinic rays in a desired shape through a light-shielding mask (first exposure step).
  • FIG. 6B is a schematic cross-sectional view taken along the line II in FIG.
  • FIG. 6C a transparent electrode (Y position coordinate) 104 (conductive pattern) is formed.
  • the substrate 101 having the transparent electrode 103 formed by the above process is further laminated with a photosensitive conductive film 10 with a new support film, and the transparent electrode 104 for detecting the Y position coordinate is formed by the same operation as described above.
  • FIG. 6D is a schematic cross-sectional view taken along the line II-II in FIG.
  • a lead wire 105 for connecting to an external circuit and a connection electrode 106 for connecting the lead wire and the transparent electrodes 103 and 104 are formed on the surface of the transparent substrate 101.
  • the lead line 105 and the connection electrode 106 are shown to be formed after the formation of the transparent electrodes 103 and 104, but they may be formed simultaneously with the formation of the transparent electrodes.
  • the lead line 105 can be formed at the same time as the connection electrode 106 is formed by screen printing using a conductive paste material containing flaky silver, for example.
  • FIGS. 7 and 8 are partial cross-sectional views taken along lines a-a 'and b-b' shown in FIG. 5, respectively. These indicate the intersections of the transparent electrodes at the XY position coordinates.
  • the transparent electrode is formed by the conductive pattern forming method according to the present invention, so that a touch panel sensor with small steps and high smoothness can be obtained.
  • the touch panel sensor according to the present embodiment includes the conductive pattern according to the present invention, so that the electrical resistance hardly increases even under high temperature and high humidity, and can be excellent in reliability.
  • the conductive pattern forming method can be changed as follows, and the method can be applied to the manufacture of the touch panel sensor.
  • FIG. 9 is a schematic cross-sectional view showing an example of a photosensitive conductive film suitably used in this embodiment.
  • a photosensitive conductive film 11 shown in FIG. 9 includes a first film (protective film) 7, a photosensitive conductive film 4 provided on the first film 7, and a first film provided on the photosensitive conductive film 4.
  • a second film (support film) 8 is provided.
  • the photosensitive conductive film 4 is composed of a conductive network 2 containing conductive fibers provided on a protective film 7 and a photosensitive resin layer 3 provided on the conductive network 2.
  • the first film 7 and the second film 8 can be the same as the support film 1 described above.
  • the photosensitive conductive film 11 may be manufactured by a method in which a conductive network and a photosensitive resin layer are sequentially formed on the protective film 7, and the conductive network 2 is formed as shown in FIG.
  • One film (protective film) 7 is formed, and the photosensitive resin layer 3 is separately formed on the second film (support film) 8.
  • the two films thus obtained are formed into the conductive network 2.
  • the photosensitive resin layer 3 may be laminated by a roller 50 so as to be laminated.
  • Lamination is preferably performed by heating to 60 to 130 ° C., and the pressing pressure is preferably about 0.2 to 0.8 MPa.
  • FIG. 11 is a schematic cross-sectional view for explaining a third method of forming a conductive pattern using the photosensitive conductive film 11 according to the present embodiment.
  • the above-described photosensitive conductive film 11 is laminated with a roller 60 so that the protective film 7 is peeled off and the conductive network 2 is in close contact with the substrate 20 (hereinafter referred to as “lamination step”).
  • laminate step an exposure step of irradiating a predetermined portion of the photosensitive conductive film 4 having the support film 8 with actinic rays through the mask pattern 5 (FIG. 11 (c). )
  • a development step of peeling the support film 8 to develop the photosensitive conductive film 4.
  • a conductive pattern substrate having a conductive pattern 9 including a conductive network 2a containing conductive fibers and a cured resin layer 3b containing a metal complex and / or a heteroatom compound in this order from the substrate side. 32 is obtained (FIG. 11 (d)).
  • the exposure step and the development step can be performed in the same manner as in the first method for forming a conductive pattern described above.
  • the conductive pattern is further cured by performing exposure at about 0.2 to 10 J / cm 2 or heating at about 60 to 250 ° C. as necessary after development. May be.
  • the surface resistance of the conductive pattern is preferably 200 ⁇ / ⁇ or less, more preferably 100 ⁇ / ⁇ or less, and further preferably 50 ⁇ / ⁇ or less.
  • the conductive pattern 9 preferably has a minimum light transmittance of 80% or more in the wavelength region of 450 to 650 nm, more preferably 85% or more, and further preferably 90% or more. When the conductive pattern 9 satisfies such a condition, it is easy to increase the brightness in a display panel or the like.
  • b * is preferably 0.1 to 2.0, more preferably 0.1 to 1.0, and further preferably 0.1 to 0.7.
  • the visibility on a display panel or the like is further improved.
  • a diluted solution was prepared by adding 0.1 kg of isopropyl alcohol to 0.9 kg of purified water.
  • 500 g of silver nano ink “T2G-F12” (manufactured by DOWA Electronics, trade name, fiber diameter (diameter): about 16 nm, fiber length: about 30 ⁇ m) is stirred with a three-one motor (rotation speed: 300 rpm). It was added little by little, and then stirred for about 3 minutes to obtain a silver fiber dispersion.
  • solution a a solution prepared by mixing 12 g of methacrylic acid, 58 g of methyl methacrylate, 30 g of ethyl acrylate, and 0.8 g of azobisisobutyronitrile was prepared as a monomer.
  • Solution a was uniformly added dropwise over 4 hours to solution s kept at 80 ° C. ⁇ 2 ° C. The solution after dropping was continuously stirred at 80 ° C. ⁇ 2 ° C. for 6 hours, and polymer A was produced by polymerization of the monomers.
  • the binder polymer solution containing the polymer A was obtained by adding acetone so that a non-volatile component (solid content) might be adjusted to 50 mass%.
  • the weight average molecular weight (Mw) of the obtained polymer A was 65000, and the acid value was 78 mgKOH / g.
  • the weight average molecular weight (Mw) was measured by gel permeation chromatography (GPC), and was derived by conversion using a standard polystyrene calibration curve.
  • GPC gel permeation chromatography
  • the acid value was measured by a neutralization titration method based on JIS K0070 as shown below. First, the binder polymer solution was heated at 130 ° C. for 1 hour to remove volatile components, thereby obtaining a solid content. Then, after accurately weighing 1 g of the solid binder polymer, 30 g of acetone was added to the binder polymer, and this was uniformly dissolved to obtain a resin solution. Next, an appropriate amount of an indicator, phenolphthalein, was added to the resin solution, and neutralization titration was performed using a 0.1 mol / L potassium hydroxide aqueous solution. And the acid value was computed by following Formula.
  • Acid value 0.1 ⁇ V ⁇ f1 ⁇ 56.1 / (Wp ⁇ I / 100)
  • V is a titration amount (mL) of a 0.1 mol / L potassium hydroxide aqueous solution used for titration
  • f1 is a factor (concentration conversion factor) of a 0.1 mol / L potassium hydroxide aqueous solution
  • Wp is the mass (g) of the measured resin solution
  • I shows the ratio (mass%) of the non volatile matter in the measured said resin solution.
  • Example 1 Preparation of photosensitive resin composition solution (photosensitive resin layer forming solution) >> 60 parts by mass of polymer A in terms of solid content as binder polymer, 40 parts by mass of ditrimethylolpropane tetraacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD T-1420) as a polymerizable compound, as a photopolymerization initiator 10 parts by mass of 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (manufactured by BASF Japan Ltd., trade name: IRGACURE TPO), 0.1 part by mass of octamethylcyclotetrasiloxane as a leveling agent, and As a metal complex, “Narsem Ferric Acid” (trade name, manufactured by Nippon Chemical Industry Co., Ltd.) was added to 0.8 part by mass, and 120 parts by mass of methyl ethyl ketone was added to obtain a photosensitive resin composition
  • the photosensitive resin composition solution prepared above After stirring the photosensitive resin composition solution prepared above, it is uniformly coated on the conductive network, and dried for 2 minutes while increasing the temperature stepwise in the range of 40 to 90 ° C. with a hot air convection dryer. Thus, a photosensitive resin layer was formed. The thickness of the photosensitive resin layer after drying was 5 ⁇ m. The formed photosensitive resin layer was covered with a protective film (polypropylene film, product name “ES-201” manufactured by Oji F-Tex Co., Ltd.) to obtain a photosensitive conductive film with a protective film and a support film.
  • a protective film polypropylene film, product name “ES-201” manufactured by Oji F-Tex Co., Ltd.
  • stacked on the base material was produced.
  • the obtained base material was cut into a size of 8 cm long ⁇ 16 cm wide.
  • the support film side (main surface having a conductive network of the photosensitive conductive film)
  • the support film was removed, and the whole was irradiated with ultraviolet rays at an exposure amount of 100 mJ / cm 2 from the upper side of the main surface having a conductive network in the air.
  • the film was developed with a 1 wt% aqueous sodium carbonate solution at 30 ° C. for 40 seconds, and further irradiated with 1 J / cm 2 of ultraviolet light.
  • a silver paste (trade name “3350C”, manufactured by ThreeBond Co., Ltd.) was applied in the range of 1 mm ⁇ 10 mm so that 5 mm at the end of the line was covered at both ends of the obtained line pattern, and dried at 80 ° C. for 5 minutes. .
  • the optical transparent adhesive layer (OCA) (manufactured by 3M, trade name # 8146, thickness 50 ⁇ m) is bonded with a hand roller so that the conductive pattern is in close contact with the OCA and the silver paste is exposed 3 mm. (See FIGS. 12 (a) and 12 (b)).
  • Nursem Fe “Narsem Ferric Iron” (trade name, manufactured by Nippon Chemical Industry Co., Ltd.)
  • Nursem Co “Narsem Cobalt Cobalt” (trade name, manufactured by Nippon Chemical Industry Co., Ltd.)
  • 1H-benzotriazole 1H-benzotriazole 5-aminotetrazole: 5-amino-1H-tetrazole
  • Example 2 A photosensitive conductive film was produced in the same manner as in Example 1 except that the blending amount of “Narsem Ferric Iron” was 0.4 parts by mass in the preparation of the photosensitive resin composition solution. The high temperature and high humidity reliability was evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 3 Example except that 0.8 part by mass of “Narsem Ferric Cobalt” (trade name, manufactured by Nippon Chemical Industry Co., Ltd.) was added in place of “Narsem Ferric Iron” in the preparation of the photosensitive resin composition solution
  • a photosensitive conductive film was produced.
  • the high temperature and high humidity reliability was evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 4 Example 1 except that 1.0 part by mass of 1H-benzotriazole (trade name, manufactured by Wako Pure Chemical Industries, Ltd.) was added in place of “Narsem Ferric Acid” in the preparation of the photosensitive resin composition solution. In the same manner as described above, a photosensitive conductive film was produced. The high temperature and high humidity reliability was evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • 1H-benzotriazole trade name, manufactured by Wako Pure Chemical Industries, Ltd.
  • Example 5 Example except that 1.0 part by mass of 5-amino-1H-tetrazole (trade name, manufactured by Chiyoda Chemical Co., Ltd.) was added in place of “Narsem Ferric Acid” in the preparation of the photosensitive resin composition solution In the same manner as in Example 1, a photosensitive conductive film was produced. The high temperature and high humidity reliability was evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 6 The photosensitive conductive composition was prepared in the same manner as in Example 1 except that 1.0 part by mass of 5-amino-1H-tetrazole (trade name, manufactured by Chiyoda Chemical Co., Ltd.) was further added in the preparation of the photosensitive resin composition solution. A film was prepared. The high temperature and high humidity reliability was evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 7 The photosensitive conductive composition was prepared in the same manner as in Example 1 except that 0.1 parts by mass of 5-amino-1H-tetrazole (trade name, manufactured by Chiyoda Chemical Co., Ltd.) was further added in the preparation of the photosensitive resin composition solution. A film was prepared. The high temperature and high humidity reliability was evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 1 A photosensitive conductive film was produced in the same manner as in Example 1 except that “Narsem Ferric Acid” was not blended in the preparation of the photosensitive resin composition solution. A photosensitive conductive film was prepared. The high temperature and high humidity reliability was evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • the photosensitive conductive film which enables formation of the conductive pattern which is hard to raise an electrical resistance even under high temperature, high humidity conditions, the formation method of a conductive pattern using this, and manufacture of a conductive pattern base material
  • a method, a conductive pattern base material, and a touch panel sensor can be provided.
  • SYMBOLS 1 Support film, 2 ... Conductive network, 2a ... Conductive network, 3 ... Photosensitive resin layer, 3a, 3b ... Resin hardened layer, 4 ... Photosensitive conductive film, 5 ... Mask pattern, 6,9 ... Conductive pattern DESCRIPTION OF SYMBOLS 10 ... Photosensitive conductive film with a support film, 11 ... Photosensitive conductive film with a protective film and a support film, 20 ... Base material, 30, 31, 32 ... Conductive pattern base material, 101 ... Base material, 102 ... Touch screen, DESCRIPTION OF SYMBOLS 103 ... Transparent electrode (X position coordinate), 104 ... Transparent electrode (Y position coordinate), 105 ... Lead-out wiring, 106 ... Connection electrode, 107 ... Connection terminal

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Abstract

L'invention concerne un film conducteur photosensible comprenant une couche de résine photosensible 3 et un réseau conducteur 2 qui est disposé sur un côté de surface principale de la couche de résine photosensible 3 et obtenu à l'aide de fibres conductrices. La couche de résine photosensible 3 comprend (A) un polymère liant, (B) un composé polymérisable, (C) un photo-initiateur et (D) un complexe métallique et/ou un composé hétéroatomique.
PCT/JP2017/002984 2017-01-27 2017-01-27 Film conducteur photosensible, procédé de formation de motif conducteur, procédé de production de substrat à motif conducteur, substrat à motif conducteur et capteur à panneau tactile WO2018138879A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/JP2017/002984 WO2018138879A1 (fr) 2017-01-27 2017-01-27 Film conducteur photosensible, procédé de formation de motif conducteur, procédé de production de substrat à motif conducteur, substrat à motif conducteur et capteur à panneau tactile
TW107102815A TW201840595A (zh) 2017-01-27 2018-01-26 感光性導電膜、導電圖案的形成方法、導電圖案基材的製造方法、導電圖案基材、觸控面板感測器

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PCT/JP2017/002984 WO2018138879A1 (fr) 2017-01-27 2017-01-27 Film conducteur photosensible, procédé de formation de motif conducteur, procédé de production de substrat à motif conducteur, substrat à motif conducteur et capteur à panneau tactile

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007079442A (ja) * 2005-09-16 2007-03-29 Fujifilm Corp 光重合型感光性平版印刷版
WO2015056445A1 (fr) * 2013-10-16 2015-04-23 日立化成株式会社 Fibre conductrice contenant un stratifié, film conducteur photosensible, procédé de fabrication de tracé conducteur, substrat de tracé conducteur et écran tactile
JP2015199300A (ja) * 2014-04-09 2015-11-12 トッパン・フォームズ株式会社 積層体、データ受送信体、通信機器及び透明導電膜

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007079442A (ja) * 2005-09-16 2007-03-29 Fujifilm Corp 光重合型感光性平版印刷版
WO2015056445A1 (fr) * 2013-10-16 2015-04-23 日立化成株式会社 Fibre conductrice contenant un stratifié, film conducteur photosensible, procédé de fabrication de tracé conducteur, substrat de tracé conducteur et écran tactile
JP2015199300A (ja) * 2014-04-09 2015-11-12 トッパン・フォームズ株式会社 積層体、データ受送信体、通信機器及び透明導電膜

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