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WO2018087816A1 - Film conducteur photosensible, procédé de formation d'un motif conducteur, et procédé de fabrication de base de motif conducteur - Google Patents

Film conducteur photosensible, procédé de formation d'un motif conducteur, et procédé de fabrication de base de motif conducteur Download PDF

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Publication number
WO2018087816A1
WO2018087816A1 PCT/JP2016/083118 JP2016083118W WO2018087816A1 WO 2018087816 A1 WO2018087816 A1 WO 2018087816A1 JP 2016083118 W JP2016083118 W JP 2016083118W WO 2018087816 A1 WO2018087816 A1 WO 2018087816A1
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WO
WIPO (PCT)
Prior art keywords
conductive
resin layer
photosensitive
photosensitive resin
conductive pattern
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2016/083118
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English (en)
Japanese (ja)
Inventor
昂平 平尾
謙介 吉原
森　拓也
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Resonac Corp
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Hitachi Chemical Co Ltd
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Filing date
Publication date
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Priority to PCT/JP2016/083118 priority Critical patent/WO2018087816A1/fr
Priority to TW106138440A priority patent/TW201829591A/zh
Publication of WO2018087816A1 publication Critical patent/WO2018087816A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • G—PHYSICS
    • G06—COMPUTING OR CALCULATING; 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
    • G06F3/0443—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means using a single layer of sensing 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • G—PHYSICS
    • G06—COMPUTING OR CALCULATING; 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
    • G—PHYSICS
    • G06—COMPUTING OR CALCULATING; 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • 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.
  • Liquid crystal display elements or touch panels are used in large electronic devices such as personal computers and televisions, small electronic devices such as car navigation systems, smartphones, and electronic dictionaries, and display devices such as OA devices and FA devices.
  • a plurality of X electrodes and a plurality of Y electrodes orthogonal to the X electrodes have a two-layer structure in order to express two-dimensional coordinates based on the X and Y axes.
  • a transparent electrode material is used to form these X and Y electrodes.
  • Patent Document 1 proposes a method for forming a conductive pattern using a photosensitive conductive film having a conductive layer containing conductive fibers. If this technique is used, a conductive pattern can be easily formed directly on various substrates by a photolithography process.
  • a conductive pattern is formed using a conductive electrode, particularly a transparent electrode material containing silver fibers such as silver nanowires
  • a transparent electrode material containing silver fibers such as silver nanowires
  • the electric resistance of the electrode material tends to increase, and the reliability as an electrode may not satisfy the required level in the above application.
  • One factor of deterioration with time under high temperature and high humidity conditions is, for example, corrosion of silver fibers such as silver nanowires.
  • Patent Document 2 proposes a method of incorporating a corrosion inhibitor into a transparent conductor having a conductive layer containing metal nanowires.
  • a corrosion inhibitor such as 2-mercaptobenzothiazole or a hydrogen sulfide scavenger such as triazine is disclosed.
  • Patent Document 2 has problems that it may cause aggregation of silver fibers such as silver nanowires, and increase the contact resistance between the fibers and increase the initial resistance. Furthermore, it is difficult to adjust the addition amount of a compound containing a mercapto group such as 2-mercaptobenzothiazole so as to be effective in improving the reliability under high temperature and high humidity conditions. There is also a problem of getting worse.
  • 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.
  • a photosensitive conductive film provided with a conductive network containing conductive fibers adjacent to a photosensitive resin layer containing an iron compound 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 including conductive fibers provided on one main surface side of the photosensitive resin layer, and the photosensitive resin layer contains at least an iron compound.
  • the 1st photosensitive conductive film currently formed from the photosensitive resin composition formed is provided.
  • the first photosensitive conductive film of the present invention exposure to light and development are carried out by placing on a base material, thereby providing sufficient conductivity and increasing electrical resistance even under high temperature and high humidity conditions. A conductive pattern that is difficult to form can be formed.
  • the iron compound may be an iron complex.
  • the photosensitive resin composition may be formed by blending at least an iron complex as a phosphate ester and an iron compound.
  • the iron complex may be an acetylacetone iron complex.
  • the present invention also includes a photosensitive resin layer and a conductive network including conductive fibers provided on one main surface side of the photosensitive resin layer, wherein the photosensitive resin layer is a trivalent iron ion.
  • a second photosensitive conductive film is provided.
  • the second photosensitive conductive film of the present invention exposure to light and development are carried out by placing on a substrate, so that there is sufficient conductivity and electrical resistance is increased even under high temperature and high humidity conditions.
  • a conductive pattern that is difficult to form can be formed.
  • the present invention also includes a step of disposing the first or second photosensitive conductive film according to the present invention on the substrate such that the photosensitive resin layer is positioned on the substrate side, and the photosensitive resin layer.
  • a first method for forming a conductive pattern comprising an exposure step of irradiating actinic rays in a pattern and a development 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 first or second photosensitive conductive film according to the present invention on the substrate such that the photosensitive resin layer is positioned on the substrate side, and the photosensitive resin layer.
  • a second method of forming a conductive pattern comprising an exposure step and a development step of forming a conductive pattern by performing development processing on the photosensitive resin layer that has undergone the second exposure step.
  • the present invention also includes a step of disposing the first or second photosensitive conductive film according to the present invention on the substrate such that the conductive network is located on the substrate side, and a pattern on the photosensitive resin layer.
  • a third method of forming a conductive pattern comprising an exposure step of irradiating actinic rays in a shape and a development step of forming a conductive pattern by removing an unexposed portion of a 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 decrease in reliability due to an increase in electrical resistance under high temperature and high humidity can be sufficiently suppressed.
  • the present invention also includes a base material and a conductive pattern provided on the base material, and the conductive pattern is based on a cured resin layer including trivalent iron ions and a conductive network including conductive fibers.
  • a first conductive pattern base material is provided which is included in this order from the material side.
  • 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 and a cured resin layer including trivalent iron ions.
  • a second conductive pattern base material is provided which is included in this order from the base material 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, a decrease in reliability due to an increase in electrical resistance under high temperature and high humidity can be sufficiently suppressed.
  • 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.
  • 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 in which the photosensitive resin layer is impregnated, (2) an impregnation in the photosensitive resin layer, and a part of the photosensitive resin layer It may exist in the state which protrudes from the main surface of the layer, and the state which exists on the main surface of the (3) photosensitive resin layer.
  • the thickness t of the photosensitive resin layer is a thickness including a part of the conductive network impregnated in 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.
  • 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. It is particularly preferably from 2.0 to 2.0%, and very preferably from 0.01 to 1.5%.
  • the haze value can be measured according to JIS K 7105.
  • 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.
  • 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 fibers included in the conductive network 2 include metal fibers such as gold, silver, copper, and platinum, or carbon fibers such as carbon nanotubes.
  • metal fibers such as gold, silver, copper, and platinum
  • carbon fibers such as carbon nanotubes.
  • silver fibers such as silver nanowires are likely to increase in electrical resistance under high temperature and high humidity conditions, but according to the present invention, even when using conductive fibers containing silver nanowires, An increase in electrical resistance under high humidity conditions can be effectively suppressed.
  • a conductive fiber can be used individually or in combination of 2 or more types.
  • FIG. 2 is a partially cutaway perspective view showing an embodiment of a photosensitive conductive film.
  • the conductive network 2 preferably has a network structure in which conductive fibers are in contact with each other.
  • 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 further preferably 3 nm to 10 nm.
  • 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.
  • 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 can be used without particular limitation, but it is preferable to use a conductive polymer such as a polymer of a thiophene derivative and a polymer of an aniline derivative. Specifically, polyethylenedioxythiophene, polyhexylthiophene, polyaniline, or the like can be used.
  • 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, more preferably 1 nm to 0.5 ⁇ m. Preferably, it is 5 nm 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 conductor dispersion obtained by adding the above-described conductive fibers, 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 a liquid and drying. Further, a metal salt may be added to the conductor dispersion liquid in order to promote the fusion of 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.
  • a conductive network contains the residue after drying derived from the solvent, additive, etc. which are contained in the coating liquid in which the metal nanowire was disperse
  • the photosensitive resin layer 3 can be formed from a photosensitive resin composition containing at least an iron compound.
  • a photosensitive resin composition containing at least an iron compound.
  • the photosensitive resin composition according to the present embodiment (A) a binder polymer, (B) a polymerizable compound having an ethylenically unsaturated bond, (C) a photopolymerization initiator, and (D) an iron compound are blended. be able to.
  • the photosensitive resin layer 3 comprises (A) a binder polymer, (B) a polymerizable compound having an ethylenically unsaturated bond, (C) a photopolymerization initiator, and an iron compound and / or a compound derived from an iron compound. Can be contained.
  • 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 (meth) acrylic acid alkyl ester.
  • 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. Preferably, it is 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 a known compound can be used.
  • 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
  • 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,
  • 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 of the polymerizable compound having an ethylenically unsaturated bond is 30 to 80 masses per 100 parts by mass of the total amount of (A) the binder polymer and (B) the polymerizable compound having an ethylenically unsaturated bond. Parts, preferably 40 to 70 parts by weight, more preferably 40 to 60 parts by weight. 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.
  • iron compound a well-known compound can be used. From the viewpoint of solubility in organic solvents, iron complexes are preferred. Examples of 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. Among these, 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 (1), and is commercially available such as “Narsem Ferric Acid” (product name, manufactured by Nippon Chemical Industry Co., Ltd.). Product can be used.
  • the reliability of the conductive pattern manufactured from the photosensitive conductive film of this embodiment under high temperature and high humidity conditions is improved. Can do.
  • the reason for this is that the iron compound or a compound derived therefrom contributes to the reduction of the conductive fiber deteriorated (corroded) by oxidation or sulfurization and the like, and the increase in the electrical resistance of the conductive fiber can be suppressed. Guess.
  • the iron compound may be present in the photosensitive resin layer as an iron compound or a compound derived from an iron compound obtained by reacting an iron compound with another compound by blending.
  • the photosensitive resin composition according to the present embodiment preferably contains an iron complex and a phosphate ester.
  • the photosensitive resin layer 3 can contain a phosphorus-containing iron complex in which the ligand of the iron complex is substituted with a phosphate ester (ligand exchange).
  • the iron complex can be discolored or colorless, and the reliability of the conductive pattern under high temperature and high humidity conditions and the transparency of the conductive pattern can be compatible at a high level. it can.
  • a combination of tris (2,4-pentanedionato) iron (III) and a phosphate ester is preferable.
  • each of R 1 and R 2 independently represents a hydrogen atom, an oxygen atom, or a hydrocarbon group having 1 to 18 carbon atoms having an ethylenically unsaturated bond.
  • the phosphate ester preferably has an ethylenically unsaturated bond.
  • a phosphate ester can be reacted with a polymerizable compound at the time of irradiation with actinic rays, and the detachment of the component from the photosensitive resin layer in the development process can be prevented.
  • the phosphate ester which has an ethylenically unsaturated group may overlap with the said (B) component, it shall not be contained in (B) component in this specification.
  • Examples of phosphate esters having an ethylenically unsaturated bond include “KAYAMAAR PM-2” (trade name, manufactured by Nippon Kayaku Co., Ltd.) and “KAYAMAAR PM-21” (trade name, manufactured by Nippon Kayaku Co., Ltd.). , “Light Ester P-1M” (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), “Light Ester P-2M” (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) and the like can be used.
  • the compounding amount of the iron compound in the photosensitive resin composition according to this embodiment is 0.1 to 2 parts by mass with respect to 100 parts by mass as a total of (A) the binder polymer and (B) the polymerizable compound.
  • the amount is preferably 0.2 to 1.5 parts by mass, and more preferably 0.5 to 1 part by mass.
  • it is preferably 0.1 parts by mass or more, and from the viewpoint of the color (b * ) of the conductive pattern, it is 2 parts by mass or less. preferable.
  • the blending amount thereof is 1.0: 1.1 to 1.0: 3. 2 is preferred, 1.0: 1.6 to 1.0: 2.6 is more preferred, and 1.0: 1.8 to 1.0: 2.2 is even more preferred.
  • the photosensitive resin layer 3 may contain trivalent iron ions.
  • Such a photosensitive resin layer can be formed from the photosensitive resin composition mentioned above, for example.
  • the trivalent iron ions in the photosensitive resin layer can be measured by X-ray photoelectron spectroscopic analysis (XPS: X-ray Photoelectron Spectroscopy). For example, the presence of trivalent iron ions can be confirmed by performing XPS measurement in the vicinity of 700 to 730 eV from the surface of the photosensitive resin layer in the photosensitive conductive film.
  • XPS X-ray Photoelectron spectroscopic analysis
  • 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) the binder polymer and (B) the polymerizable compound having an ethylenically unsaturated bond.
  • 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 application, but is preferably 1 to 200 ⁇ m, more preferably 1 to 50 ⁇ m, and particularly preferably 1 to 30 ⁇ m after drying. 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 2000 ⁇ / ⁇ or less, and preferably 1000 ⁇ / ⁇ or less, from the viewpoint that it can be effectively used as a transparent electrode. More preferably, it is 500 ⁇ / ⁇ or less.
  • the sheet resistance value can be adjusted to the above range depending on, for example, the types of conductive fibers and organic conductors included in the conductive network 2, or the concentration or coating amount of the conductive dispersion. Also, the sheet resistance value can be varied by adjusting the surface state of the conductive fibers or the contact state between the conductive fibers.
  • the photosensitive conductive film 4 (laminated body of 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. It is preferable that it is 85% 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 (laminated body of the conductive network 2 and the photosensitive resin layer 3) satisfies such a condition, 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.
  • the polymer film exemplified as the above-mentioned support film can be used similarly.
  • 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).
  • the base material 20 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 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. In addition, it is preferable that this process is performed under reduced pressure from the viewpoint of adhesiveness and followability.
  • 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.
  • 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 unexposed areas in the exposure process of the photosensitive resin layer 3 in the photosensitive conductive film 4 are 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 base material 30 obtained by the method of the present embodiment is such that the conductive pattern 6 includes a cured resin layer 3b containing trivalent iron ions and a conductive network 2a containing conductive fibers from the base material side. Can be included in order.
  • the trivalent iron ions in the cured resin layer 3b can be confirmed in the same manner as described above.
  • 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 exposed from the cured resin layer. 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
  • a second 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 A first exposure step of irradiating the layer with actinic rays in a pattern; and a second step of irradiating a part or all of the unexposed portions of at least the first exposure step of the photosensitive resin layer with actinic rays in the presence of oxygen.
  • 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.
  • the second exposure step FIG.
  • 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 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.
  • the step Ha between the conductive network 2a formed on the cured resin layer 3a and the bottom surface of the concave portion of the cured resin layer 3a becomes small, and the conductive pattern with small steps.
  • a conductive pattern substrate 31 having (wiring) 6 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 cured resin layer 3a can contain trivalent iron ions.
  • the trivalent iron ions in the cured resin layer 3a can be confirmed in the same manner as described above.
  • 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.
  • the base material (conductive pattern base material) on which the conductive pattern is formed the same range is preferable from the viewpoint described above.
  • conductive pattern 6 b * is preferably 1.8 or less, more preferably 1.5 or less, and further preferably 1.2 or less.
  • the conductive pattern 6 satisfies such conditions, the visibility on a display panel or the like is further improved.
  • the base material (conductive pattern base material) on which the conductive pattern is formed the same range is preferable from the viewpoint described above.
  • 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, and the lead wire 105 and the transparent electrodes 103 and 104.
  • a connection electrode 106 for connecting the two 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 base material 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 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 the 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. Even if the transparent electrode 104 is formed on the transparent electrode 103 by forming the transparent electrode 104 by the method for forming a conductive pattern according to the present invention, the reduction in aesthetics due to stepping and bubble entrainment is sufficiently suppressed. A touch panel sensor with high smoothness can be created.
  • 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 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 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.
  • 9 includes a first film (protective film) 7, a photosensitive conductive film 4 provided on the first film 7, and a photosensitive conductive film 4.
  • a second film (support film) 8 provided on the top is provided.
  • the photosensitive conductive film 4 includes a conductive network 2 including conductive fibers provided on the 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 protective film and the photosensitive conductive film 11 with a support film may be manufactured by a method of sequentially forming a conductive network and a photosensitive resin layer on the protective film 7, as shown in FIG.
  • the conductive network 2 is formed on the first film (protective film) 7, and the photosensitive resin layer 3 is separately formed on the second film (support film) 8.
  • the two films thus obtained May be manufactured by laminating with the roller 50 so that the conductive network 2 and the photosensitive resin layer 3 are bonded together.
  • 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 forming method of a conductive pattern using the photosensitive conductive film 11 with a protective film and a support film according to this embodiment.
  • the method of the present embodiment is a step of laminating the protective film and the photosensitive conductive film 11 with the support film by the 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, it is also referred to as “lamination process” (FIGS. 11A and 11B), and a predetermined portion of the photosensitive resin layer 3 of the photosensitive conductive film 4 having the support film 8 through the mask pattern 5.
  • the exposure process FIG. 11
  • the conductive pattern substrate 32 having the conductive pattern 9 including the conductive network 2a including the conductive fibers and the cured resin layer 3b in this order from the substrate side is obtained (FIG. 11D). ).
  • 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 cured resin layer 3b can contain trivalent iron ions.
  • the trivalent iron ions in the cured resin layer 3b can be confirmed in the same manner as described above.
  • 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 1.8 or less, more preferably 1.5 or less, and further preferably 1.2 or less.
  • Silver fibers were prepared by the polyol method. In a 2000 mL three-necked flask, 500 mL of ethylene glycol was placed and heated to 160 ° C. with an oil bath while stirring with a magnetic stirrer under a nitrogen atmosphere. A solution prepared by dissolving 2 mg of PtCl 2 separately prepared in 50 mL of ethylene glycol was added dropwise thereto.
  • the reaction solution was allowed to stand at 30 ° C. or lower, diluted 10-fold with acetone, centrifuged at 2000 rpm for 20 minutes with a centrifuge, and the supernatant was decanted. Acetone was added to the precipitate and stirred, followed by centrifugation under the same conditions as described above, and acetone was decanted. Then, it centrifuged twice similarly using distilled water, and obtained the silver fiber. When the obtained silver fiber was observed with a scanning electron micrograph, the fiber diameter (diameter) was about 5 nm, and the fiber length was about 5 ⁇ m.
  • the silver fiber obtained above was dispersed in pure water at a concentration of 0.2% by mass and dodecyl-pentaethylene glycol at a concentration of 0.1% by mass 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 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) >> 63 parts by mass of polymer A in terms of solid content as a binder polymer, 37 parts by mass of “KAYARAD T-1420 (T)” (trade name, manufactured by Nippon Kayaku Co., Ltd.) as a polymerizable compound having an ethylenically unsaturated bond 10 parts by mass of “Lucirin TPO” (trade name, manufactured by BASF Japan Ltd.) as a photopolymerization initiator, and “DOW CORNING 8032 ADDITIVE” (trade name, manufactured by Toray Dow Corning Co., Ltd.) as a leveling agent is 0.00.
  • the photosensitive resin composition solution obtained above was uniformly applied on a conductive network and dried for 10 minutes with a hot air convection dryer at 100 ° C. to form a photosensitive resin layer.
  • the photosensitive resin layer was covered with a protective film (polyethylene film, manufactured by Tamapoly Co., Ltd., trade name “NF-13”) to obtain a photosensitive conductive film with a protective film and a support film.
  • the thickness of the photosensitive conductive film after drying was about 5 ⁇ m.
  • stacked on PET film base material was produced.
  • the obtained base material was cut into a size of 8 cm long ⁇ 16 cm wide.
  • a silver paste (trade name DW-117H-41 manufactured by Toyobo Co., Ltd.) was applied to both ends of the obtained conductive pattern, and dried at 130 ° C./30 minutes. Then, after removing the separator on one side of the optical adhesive sheet (OCA) (product name 8146-1, manufactured by 3M Co., Ltd., thickness 100 ⁇ m), the silver paste is used so that the conductive pattern adheres to the OCA adhesive layer. Is exposed using a laminator (product name: HLM-3000, manufactured by Hitachi Chemical Co., Ltd.) under conditions of a roll temperature of 30 ° C., a substrate feed speed of 1 m / min, and a pressure of pressure (cylinder pressure) of 0.4 MPa. The laminate was prepared by laminating the conductive pattern and OCA on the substrate.
  • OCA optical adhesive sheet
  • the support film side (upper side of the main surface having the conductive network of the photosensitive conductive film) Further, ultraviolet rays were irradiated at an exposure amount of 1 ⁇ 10 4 J / m 2 (measured value in i-line). Thereafter, the support film was removed and heated under the conditions of 80 ° C./10 minutes to form a cured film (thickness: 5.0 ⁇ m) of the photosensitive conductive film on the entire surface of the substrate to obtain a laminate.
  • EXM1201 manufactured by Oak Manufacturing Co., Ltd. a parallel light exposure machine
  • the total light transmittance and haze value of the obtained laminate were measured with a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., trade name NDH5000). Further, the hue (b * , yellowishness) of the obtained laminate was measured with a spectrocolorimeter (manufactured by Konica Minolta, CM-5, measurement mode: transmission). These results are shown in Table 1.
  • (B) component, (C) component, (D) component, phosphate ester and leveling agent are as follows.
  • T-1420 “KAYARAD T-1420 (T)” (trade name, manufactured by Nippon Kayaku Co., Ltd.), ditrimethylolpropane tetraacrylate
  • TPO “Lucirin TPO” (trade name, manufactured by BASF Japan Ltd.), 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide
  • Nursem ferric iron “Narsem ferric iron” (trade name, manufactured by Nippon Chemical Industry Co., Ltd.), acetylacetone iron complex
  • P-1M Light Ester P-1M
  • PM-21 “KAYAMAAR PM-21” (trade name, manufactured by Nippon Kayaku Co., Ltd.)
  • ⁇ Leveling agent> 8032 “DOW CORNING 8032 ADDITIVE” (trade name, manufactured by Toray Dow Corning Co., Ltd.)
  • 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 0.8 parts by mass. The high temperature and high humidity reliability and optical characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 3 A photosensitive conductive film was produced in the same manner as in Example 1 except that 1 part by weight of “light ester P-1M” (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) was added as a phosphate ester compound. The high temperature and high humidity reliability and optical characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 4 Implemented except that the amount of "Narsem Ferric Iron” was 0.8 parts by mass, and 1 part by mass of "Light Ester P-1M” (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) was added as the phosphate ester compound.
  • a photosensitive conductive film was produced.
  • the high temperature and high humidity reliability and optical characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 5 A photosensitive conductive film was produced in the same manner as in Example 1 except that 0.25 parts by mass of “KAYAMAAR PM-21” (trade name, manufactured by Nippon Kayaku Co., Ltd.) was added as the phosphate ester compound. The high temperature and high humidity reliability and optical characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 6 Other than adding 0.8 part by mass of “Nursem Ferric” and adding 0.25 part by mass of “KAYAMAAR PM-21” (trade name, manufactured by Nippon Kayaku Co., Ltd.) as the phosphate ester compound A photosensitive conductive film was prepared in the same manner as in Example 1. The high temperature and high humidity reliability and optical characteristics were 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 no iron compound was blended. The high temperature and high humidity reliability and optical characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • the conductive patterns of Examples 1 to 6 in which the iron compound is blended have good high temperature and high humidity reliability.
  • the resistance increase rate of the conductive pattern of Comparative Example 1 in which no iron compound was blended exceeded 20%.
  • the conductive patterns of Examples 3 to 6 in which the iron compound and the phosphate ester were blended had good b * .
  • 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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  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials For Photolithography (AREA)

Abstract

L'invention concerne un film conducteur photosensible comprenant une couche de résine photosensible 3 formée à partir d'une composition de résine photosensible dans laquelle est mélangé au moins un composé de fer, et un réseau conducteur 2 qui est disposé sur un côté de surface principale de la couche de résine photosensible 3 et contient des fibres conductrices.
PCT/JP2016/083118 2016-11-08 2016-11-08 Film conducteur photosensible, procédé de formation d'un motif conducteur, et procédé de fabrication de base de motif conducteur Ceased WO2018087816A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/JP2016/083118 WO2018087816A1 (fr) 2016-11-08 2016-11-08 Film conducteur photosensible, procédé de formation d'un motif conducteur, et procédé de fabrication de base de motif conducteur
TW106138440A TW201829591A (zh) 2016-11-08 2017-11-07 感光性導電膜、導電圖案的形成方法、導電圖案基材與其製造方法及觸控面板感測器

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2016/083118 WO2018087816A1 (fr) 2016-11-08 2016-11-08 Film conducteur photosensible, procédé de formation d'un motif conducteur, et procédé de fabrication de base de motif conducteur

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WO2018087816A1 true WO2018087816A1 (fr) 2018-05-17

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63124308A (ja) * 1986-11-13 1988-05-27 株式会社フジクラ 透明導電性フイルムの製造方法
JPH06100488A (ja) * 1992-04-29 1994-04-12 Ciba Geigy Ag ポリスチレンを基材としたフォトレジスト材料
JP2007079442A (ja) * 2005-09-16 2007-03-29 Fujifilm Corp 光重合型感光性平版印刷版
JP2011133713A (ja) * 2009-12-25 2011-07-07 Hitachi Chem Co Ltd 感光性樹脂組成物及び感光性永久レジスト
WO2014196154A1 (fr) * 2013-06-04 2014-12-11 日立化成株式会社 Film conducteur photosensible, procédé de formation de motif conducteur mettant en œuvre celui-ci, et substrat de motif conducteur

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63124308A (ja) * 1986-11-13 1988-05-27 株式会社フジクラ 透明導電性フイルムの製造方法
JPH06100488A (ja) * 1992-04-29 1994-04-12 Ciba Geigy Ag ポリスチレンを基材としたフォトレジスト材料
JP2007079442A (ja) * 2005-09-16 2007-03-29 Fujifilm Corp 光重合型感光性平版印刷版
JP2011133713A (ja) * 2009-12-25 2011-07-07 Hitachi Chem Co Ltd 感光性樹脂組成物及び感光性永久レジスト
WO2014196154A1 (fr) * 2013-06-04 2014-12-11 日立化成株式会社 Film conducteur photosensible, procédé de formation de motif conducteur mettant en œuvre celui-ci, et substrat de motif conducteur

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