WO2020203447A1 - Substrat à couches électroconductrices, et panneau tactile - Google Patents

Substrat à couches électroconductrices, et panneau tactile Download PDF

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Publication number
WO2020203447A1
WO2020203447A1 PCT/JP2020/012921 JP2020012921W WO2020203447A1 WO 2020203447 A1 WO2020203447 A1 WO 2020203447A1 JP 2020012921 W JP2020012921 W JP 2020012921W WO 2020203447 A1 WO2020203447 A1 WO 2020203447A1
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Prior art keywords
conductive layer
base material
insulating layer
layer
conductive
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PCT/JP2020/012921
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English (en)
Japanese (ja)
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三井博子
此島陽平
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東レ株式会社
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Priority to JP2020529660A priority Critical patent/JP6773258B1/ja
Priority to CN202080016616.1A priority patent/CN113474167B/zh
Publication of WO2020203447A1 publication Critical patent/WO2020203447A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—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
    • B32B7/023—Optical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • 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
    • 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 base material with a conductive layer and a touch panel.
  • touch panels for mobile devices and tablets have been desired to be flexible and thin from the viewpoint of design, convenience, and durability.
  • a method for forming touch wiring a method of forming a thin film made of a transparent conductive metal such as ITO on a base material such as glass or film and patterning by etching has been widely used from the viewpoint of improving visibility. It was.
  • ITO wiring has low bending resistance, there is a problem that cracks occur in order to make it flexible. Therefore, silver mesh wiring, silver nanowire wiring, and the like are attracting attention as touch wiring having bending resistance, invisibility, and high conductivity.
  • Wiring using metal nanowires such as silver nanowires had a problem of high haze and easy coloring.
  • a base material with a transparent electrode having a colored layer see, for example, Patent Document 1
  • a first base material having a first detection electrode provided on one surface and having isoluminous properties and a first base. It is composed of a material having a negative chromaticity b *, which is provided on the surface of the material on the side where the first detection electrode is provided and is electrically insulated from the first detection electrode.
  • An input device including a conductive shield layer and a cover panel having isoluminous properties provided on a surface of the shield layer opposite to the surface facing the first base material see, for example, Patent Document 2 and the like. Has been proposed.
  • a touch panel that can be flexibly supported, for example, a touch panel including a portion in which a transparent layer, a first conductive layer, a first insulating layer, and a second conductive layer are laminated in this order has been proposed (for example, a patent). Reference 3).
  • the touch panel has a second electrode that faces the first electrode via an insulating layer.
  • the base materials with transparent electrodes disclosed in Patent Documents 1 and 2 are laminated as the first electrode and the second electrode. It is difficult to make the touch panel configuration thin. For this reason, in recent years, a multi-layer touch panel configuration in which a plurality of conductive layers are laminated on one side of a transparent layer, as disclosed in Patent Document 3, has been studied. However, the multilayer touch panel disclosed in Patent Document 3 has a problem in color because the base material turns yellow due to heating during lamination.
  • the object of the present invention is to provide a base material with a conductive layer having a good color and excellent migration resistance, and a touch panel using the same.
  • the substrate with a conductive layer of the present invention mainly has the following configurations.
  • a second conductive layer (A-2), a second insulating layer (OC-2), a first conductive layer (A-1) and a first insulation A base material with a conductive layer having layers (OC-1) at least in this order, and the base material (S-1) according to the L * a * b * color system specified by the International Commission on Illumination 1976.
  • the b * value is b * (S-1)
  • the b * value of the first insulating layer (OC-1) is b * (OC-1)
  • the b * value of the entire base material with the conductive layer is b * (
  • a base material with a conductive layer that satisfies all of the following formulas (1) to (3) when T) is used.
  • B * is b * (S-1)
  • the b * value of the first insulating layer (OC-1) is b * (OC-1)
  • a base material with a conductive layer that satisfies the following formulas (4) and (5) when the value is b * (OC-2).
  • the ratio of the film thickness of the first insulating layer (OC-1) to the film thickness of the base material (S-1) ((OC-1) / (S-1)) is 0.05 to 0.
  • the base material (S-1) contains at least one polymer selected from the group consisting of polyimide, polyimidesiloxane, polyether sulfone, polybenzoxazole, aramid and epoxy (1) to (8).
  • the substrate with a conductive layer according to any one.
  • a touch panel provided with the base material with a conductive layer according to (1) to (10).
  • the base material with a conductive layer and the touch panel of the present invention are excellent in color and migration resistance.
  • the base material with a conductive layer of the present invention has a second conductive layer (A-2), a second insulating layer (OC-2), and a first conductive layer (A-) on the base material (S-1). 1), the first insulating layer (OC-1) is provided at least in this order.
  • the base material (S-1) acts as a support.
  • the first conductive layer (A-1) and the second conductive layer (A-2) act as electrodes in two directions orthogonal to each other, for example.
  • the first insulating layer (OC-1) and the second insulating layer (OC-2) are placed between the first conductive layer (A-1) and the ambient atmosphere, respectively, and the first conductive layer (A-1). )
  • the second conductive layer (A-2) have an insulating effect.
  • a second conductive layer (A-2) and a second insulating layer (OC-2) are placed on the base material (S-1). ), The first conductive layer (A-1), and the first insulating layer (OC-1) in this order.
  • an insulating layer (OC-0) and a second conductive layer (A-2) are placed on the base material (S-1).
  • the polymer containing the above-mentioned structure has high heat resistance, yellowing due to heating in a subsequent step can be reduced and the color tone can be further improved.
  • the base material (S-1) contains such a polymer, the residue can be suppressed in the processing of the conductive layer (A-2) in the subsequent step, so that a fine pattern can be formed.
  • the migration resistance of the base material with a conductive layer can be further improved.
  • R 1 and R 2 independently represent monovalent organic groups, and m and n independently represent integers of 0 to 4, respectively. m number of R 1 and n pieces of R 2 may be identical to or different from each other.
  • R 1 and R 2 are preferably an alkyl group having 1 to 10 carbon atoms, a carboxyl group, a phenyl group or a substituted phenyl group, or a trifluoromethyl group from the viewpoint of further improving the color.
  • m and n are preferably 0 or 1, and more preferably 0 from the viewpoint of further improving the color.
  • substituent of the substituted phenyl group a fluorine, a trifluoromethyl group, an alkyl group having 1 to 10 carbon atoms, an allyl group, and an aryl group having 3 to 13 carbon atoms are preferable.
  • the polymer preferably further contains fluorine, which can further improve transparency.
  • a structure represented by the following structural formula (3) or the following general formula (4) is preferable.
  • the transparency can be further improved, and by including the structure represented by the following general formula (4), the substrate (S-1) The elongation at break can be improved.
  • R 7 and R 8 each independently represent fluorine or a group containing fluorine.
  • the group containing fluorine include a trifluoromethyl group.
  • R 7 and R 8 are preferably fluorine or trifluoromethyl groups.
  • x and y each independently represent an integer of 1 to 4. x number of R 8 and y-number of R 7 may be the same or different from each other.
  • Examples of the structure represented by the general formula (4) include a structure represented by any of the following structural formulas (5) to (8).
  • the content of the repeating unit having such a structure is preferably 3 mol% or more in all the repeating units from the viewpoint of further improving the elongation at break. More preferably mol% or more, and even more preferably 8 mol% or more. On the other hand, from the viewpoint of further improving the color, the content is preferably 50 mol% or less, more preferably 45 mol% or less, still more preferably 40 mol% or less.
  • the polymer preferably further contains a structure represented by the following structural formula (9).
  • a structure represented by the following structural formula (9) By including the structure represented by the following structural formula (9), the toughness of the transparent layer can be improved, and the yield of the post-process and the bending resistance of the base material with the conductive layer can be significantly improved.
  • the content of the repeating unit having such a structure is 0.01 mol% in all the repeating units in the polymer from the viewpoint of further improving the elongation at break.
  • the above is preferable, 0.1 mol% or more is more preferable, and 0.3 mol% or more is further preferable.
  • the content is preferably 10 mol% or less, more preferably 3 mol% or less, still more preferably 2 mol% or less.
  • resins such as polyimide, polyimidesiloxane, polyether sulfone, polybenzoxazole, aramid, and epoxy are preferable. Two or more of these may be contained.
  • heat resistance can be further improved, coloring due to heating in a subsequent step can be further suppressed, and color can be further improved.
  • polyimide, polyimidesiloxane, polyether sulfone, and polybenzoxazole are more preferable.
  • polyimide, polyimidesiloxane, and polybenzoxazole are more preferable.
  • polyimide and polyimidesiloxane are particularly preferred. Since polyimide and polyimidesiloxane absorb ultraviolet light, it is possible to suppress the arrival of ultraviolet rays on the insulating layer and the conductive layer, and reduce the yellowing of the insulating layer and the conductive layer due to the ultraviolet light and the resulting decrease in the total light transmittance. Light resistance is significantly improved.
  • Polyimide preferably has a structural unit represented by the following general formula (10).
  • R 3 represents a 4- to 10-valent organic group
  • R 4 represents a 2- to 8-valent organic group
  • R 5 and R 6 represent a monovalent organic group, which may be the same or different.
  • R 3 and / or R 4 contains a structure represented by the general formula (1) and a structure represented by the general formula (2).
  • at least a part of R 3 and / or R 4 further includes a structure represented by the general formula (4) and / or a structure represented by the structural formula (9).
  • p and q are each independently an integer of 0 ⁇ 6, p number of R 5, shown to have q pieces of R 6.
  • At least a part of R 5 and / or R 6 may include a structure represented by the general formula (1) and a structure represented by the general formula (2). At least a part of R 5 and / or R 6 may include a structure represented by the general formula (4) and / or a structure represented by the structural formula (9).
  • R 3 and R 4 is an aromatic hydrocarbon group or a derivative thereof in the general formula (10). More preferably R 3 and at least 80 mol% of R 4 is an aromatic hydrocarbon group or its derivative, it is more preferable that all of R 3 and R 4 is an aromatic hydrocarbon group or a derivative thereof.
  • Polyimide preferably has 5 to 100,000 structural units represented by the general formula (10) in one polymer molecule.
  • the toughness of the base material (S-1) can be improved.
  • coatability can be maintained.
  • R 3- (R 5 ) p represents a residue of acid dianhydride.
  • R 3 is a tetravalent to 10-valent organic group, and among them, an organic group having 5 to 40 carbon atoms including an aromatic ring or a cyclic aliphatic group is preferable.
  • R 5 is preferably a phenolic hydroxyl group, a sulfonic acid group or a thiol group.
  • Examples of the acid dianhydride include an acid dianhydride containing a structure represented by the general formula (1), an acid dianhydride containing a structure represented by the general formula (2), and a general formula (3). Examples thereof include acid dianhydrides containing the structures to be treated. Two or more of these may be used.
  • Examples of the acid dianhydride containing the structure represented by the general formula (1) include bis (3,4-dicarboxyphenyl) sulfonic acid dianhydride and 4,4'-[p-sulfonylbis (phenylensulfanilic acid). )] Diphthalic anhydride (DPSDA) and isomers thereof and the like.
  • Examples of the acid dianhydride having the structure represented by the general formula (2) include 3,3', 4,4'-diphenyl ether tetracarboxylic dianhydride (ODPA) and its isomers.
  • ODPA 3,3', 4,4'-diphenyl ether tetracarboxylic dianhydride
  • Examples of the acid dianhydride containing the structure represented by the structural formula (3) include 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA), 4,4'-. Examples thereof include (hexafluoroisopropyridene) diphthalic anhydride and 3,3′- (hexafluoroisopropyridene) diphthalic anhydride.
  • R 4 - ( R 6) q represents a residue of a diamine.
  • R 4 is a 2- to 8-valent organic group, and an organic group having 5 to 40 carbon atoms including an aromatic ring or a cyclic aliphatic group is preferable. Phenolic hydroxyl groups, sulfonic acid groups or thiol groups are preferably mentioned for R 6 , and a single group or a mixture of different groups may be used.
  • Examples of the diamine include a diamine containing a structure represented by the general formula (1), a diamine containing a structure represented by the general formula (2), a diamine containing a structure represented by the general formula (3), and a general formula.
  • Examples thereof include a diamine containing a structure represented by (4), a diamine containing a structure represented by the general formula (9), and the like. Two or more of these may be used.
  • diamines may be used as the corresponding diisocyanate compounds or trimethylsilylated diamines.
  • Examples of the diamine containing the structure represented by the general formula (1) include 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, and bis [4-( Examples thereof include 4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [3- (3-aminophenoxy) phenyl] sulfone, and isomers thereof.
  • Examples of the diamine containing the structure represented by the general formula (2) include 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether and isomers thereof. ..
  • Examples of the diamine containing the structure represented by the structural formula (3) include 2,2-bis (4-aminophenyl) hexafluoropropane.
  • Examples of the diamine containing the structure represented by the general formula (4) include 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl and 2,2'-difluoro- (1,1'. -Biphenyl) -4,4'-diamine, 2,2', 6,6'-tetrafluoro- (1,1'-biphenyl) -4,4'-diamine, 4,4'-diaminooctafluorobiphenyl, Examples thereof include 4,4'-oxybis (2,3,5,6-tetrafluoroaniline) and 3,3'-bis (trifluoromethyl) -4,4'-diaminobiphenyl.
  • 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl is particularly preferable, and the elongation at break of the transparent layer can be further improved.
  • Examples of the amine containing the structure represented by the general formula (9) include 1,3,5-tris (4-aminophenoxy) benzene and the like.
  • Examples of the method for producing polyimide include a method of thermosetting a polyamic acid or a polyamic acid ester.
  • Examples of the method for producing a polyamic acid or a polyamic acid ester include a method of reacting a tetracarboxylic acid dianhydride with a diamine at a low temperature, a diester obtained with a tetracarboxylic acid dianhydride and an alcohol, and then an amine and a condensing agent.
  • Examples thereof include a method of reacting in the presence of a tetracarboxylic acid dianhydride and an alcohol to obtain a diester, and then the remaining dicarboxylic acid is acid chlorided and reacted with an amine.
  • the content of the above-mentioned polymer in the base material (S-1) is preferably 50 to 100% by mass, and transparency and heat resistance can be further improved.
  • the content of the heat-resistant polymer is more preferably 75 to 100% by mass, further preferably 90 to 100% by mass.
  • the base material (S-1) may further contain a surfactant, a leveling agent, an adhesion improver, a viscosity modifier, an antioxidant, an inorganic pigment, an organic pigment, a dye and the like.
  • the thickness of the base material (S-1) is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more, still more preferably 5 ⁇ m or more, from the viewpoint of improving the toughness of the base material with a conductive layer.
  • the thickness is preferably 50 ⁇ m or less, more preferably 40 ⁇ m or less, and further preferably 30 ⁇ m or less.
  • the total light transmittance of the base material (S-1) at a wavelength of 400 nm is preferably 50% or more, more preferably 60% or more, from the viewpoint of suppressing yellowness and further improving the color.
  • the total light transmittance of the base material (S-1) at a wavelength of 400 nm is such that it absorbs external light and the like to absorb external light from the first insulating layer (OC-1) and the second insulating layer (OC-2). From the viewpoint of suppressing discoloration due to the above, 85% or less is preferable, and 80% or less is more preferable.
  • a resin such as polyimide, polyimidesiloxane, polyether sulfone, polybenzoxazole, aramid, or epoxy
  • absorption can be controlled and such characteristics can be satisfied.
  • the base material (S-1) contains, for example, a polymer, and if necessary, an organic solvent, a surfactant, a leveling agent, an adhesion improver, a viscosity modifier, an antioxidant, an inorganic pigment, an organic pigment, a dye, etc. It can be formed by molding the compounded resin composition.
  • the first conductive layer (A-1) (hereinafter, may be referred to as “conductive layer (A-1)") and the second conductive layer (hereinafter, referred to as “conductive layer (A-2)").
  • a network structure composed of a network having a line width of 0.1 to 9 ⁇ m.
  • the line width of the network structure is more preferably 0.5 ⁇ m or more, further preferably 1 ⁇ m or more.
  • the line width of the network structure is more preferably 7 ⁇ m or less, and further preferably 6 ⁇ m or less.
  • the film thickness of the conductive layer (A-1) and the conductive layer (A-2) is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more, still more preferably 0.3 ⁇ m or more.
  • the film thicknesses of the conductive layer (A-1) and the conductive layer (A-2) are preferably 5 ⁇ m or less, more preferably 3 ⁇ m or less, and further preferably 1 ⁇ m or less from the viewpoint of non-visibility.
  • the conductive layer (A-1) and / or the conductive layer (A-2) preferably contains conductive particles.
  • the conductive particles include gold (Au), silver (Ag), copper (Cu), nickel (Ni), tin (Sn), bismuth (Bi), lead (Pb), zinc (Zn), and palladium ( Examples thereof include metal particles made of metals such as Pd), platinum (Pt), aluminum (Al), tungsten (W), and molybdenum (Mo). Two or more of these may be contained. Among them, gold, silver, copper, nickel, tin, bismuth, lead, zinc, palladium, platinum and aluminum are more preferable, and silver particles are further preferable.
  • the conductive particles have a coating layer on at least a part of the surface thereof.
  • the presence of the coating layer on at least a part of the surface of the conductive particles can reduce the surface activity and suppress the reaction between the conductive particles or between the conductive particles and the organic component. Further, when the photosensitive paste method is used, it is possible to suppress the scattering of the exposure light by the conductive particles and to process the wiring with higher accuracy. On the other hand, by heating at a high temperature of about 150 to 350 ° C., the coating layer can be easily removed and sufficient conductivity can be exhibited.
  • the surface of the conductive particles is preferably completely covered with a coating layer.
  • the coating layer contains carbon and / or a carbon compound.
  • the dispersibility of the conductive particles can be further improved.
  • the average thickness of the coating layer is preferably 0.1 to 10 nm. Within this range, fusion of conductive particles can be suppressed and a finer pattern can be formed. Further, the desired conductivity can be exhibited by heat treatment at a temperature of 350 ° C. or lower.
  • the average primary particle diameter of the conductive particles is preferably 10 to 60 nm in order to form a fine conductive pattern having desired conductivity.
  • the average primary particle diameter of the conductive particles can be calculated from the average value of the particle diameters of 100 primary particles randomly selected using a scanning electron microscope.
  • the particle size of each primary particle can be calculated from the average value obtained by measuring the major axis and the minor axis of the primary particle.
  • the content of the conductive particles in the conductive layer (A-1) and / or the conductive layer (A-2) is preferably 65% by mass or more from the viewpoint of improving the conductivity.
  • the content of the conductive particles is preferably 90% by mass or less from the viewpoint of improving the pattern processability.
  • the conductive layer (A-1) and / or the conductive layer (A-2) further contains an organic compound.
  • the organic compound is preferably contained in an amount of 5 to 35% by mass. By containing 5% by mass or more of the organic compound, the conductive layer is imparted with flexibility and the bending resistance of the conductive layer is improved. On the other hand, the conductivity of the conductive layer can be improved by containing 35% by mass or less of the organic compound.
  • an alkali-soluble resin is preferable.
  • a (meth) acrylic copolymer having a carboxyl group is more preferable.
  • the (meth) acrylic copolymer means a copolymer of a (meth) acrylic monomer and another monomer.
  • the (meth) acrylic monomer include methyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and 2-ethyl.
  • examples thereof include xyl (meth) acrylate, glycidyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate.
  • Examples of other monomers include compounds having a carbon-carbon double bond, and examples thereof include aromatic vinyl compounds such as styrene and ⁇ -methylstyrene; and amide-based unsaturated compounds such as (meth) acrylamide.
  • a method of introducing a carboxyl group that imparts alkali solubility to an alkali-soluble resin for example, a method of copolymerizing (meth) acrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and their acid anhydrides is used. Can be mentioned.
  • the weight average molecular weight (Mw) of the alkali-soluble resin is preferably 1,000 to 100,000. By setting the weight average molecular weight (Mw) in the above range, good coating characteristics can be obtained, and the solubility in a developing solution at the time of pattern formation is also good.
  • Mw of the alkali-soluble resin refers to a polystyrene-equivalent value measured by gel permeation chromatography (GPC).
  • the content of the alkali-soluble resin is preferably 5 to 30% by mass in the conductive layer (A-1) and / or the conductive layer (A-2), respectively.
  • the conductive layer (A-1) and the conductive layer (A-2) may contain an organotin compound and / or a metal chelate compound.
  • the conductive layer contains an organotin compound and / or a metal chelate compound, the adhesion to the base material (S-1), the insulating layer (OC-1), and (OC-2) can be further improved.
  • the metal chelate compound is more preferable than the organic tin compound because the effect of improving the adhesion can be obtained without imposing an environmental load.
  • An organotin compound is a compound in which at least one carbon atom is bonded to an organic acid salt of tin or a tin atom.
  • organic acid salts such as tin dilaurate; compounds such as dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, dioctyltin maleate, dimethyltin dilaurate, dimethyltin maleate, allyltributyltin, allyltriphenyltin, diethyltin Can be mentioned. Two or more of these may be contained.
  • the metal chelate compound refers to a compound having a central metal and a ligand coordinated to the central metal at two or more sites.
  • the ligand is easily desorbed and the adhesion can be improved by forming a complex with the alkali-soluble functional group of the alkali-soluble resin.
  • the metal element of the metal chelate compound include Au (gold), Ag (silver), Cu (copper), Cr (chromium), Fe (iron), Co (cobalt), Ni (nickel), and Bi (bismuth).
  • Mg manganesium
  • Al aluminum
  • Ti titanium
  • Zr zirconium
  • W tungsten
  • Mo molybdenum
  • a metal selected from Mg (magnesium), Al (aluminum), Ti (titanium) and Zr (zirconium) is preferable from the viewpoint of easiness of desorption of the ligand, and a complex with an alkali-soluble functional group is preferable.
  • a metal selected from Al (aluminum) and Zr (zirconium) is more preferable.
  • the metal chelate compound examples include magnesium chelate compounds such as bis (acetylacetonet) magnesium and bis (ethylacetoneacetate) magnesium; ethylacetoacetate aluminum diisopropylate, aluminum trisethylacetone acetate, alkylacetate acetate aluminum di
  • Aluminum chelate compounds such as isopropylate, aluminum monoacetylacetone bis (ethylacetoneacetate), aluminum tris (acetylacetoneate); titanium chelate compounds such as tetrakis (acetylacetonate) titanium; zirconium tetracetylacetonate, zirconium tributoxy Examples thereof include zirconium chelating compounds such as monostearate.
  • the total content of the organotin compound and the metal chelate compound in the conductive layer (A-1) and the conductive layer (A-2) is preferably 0.1% by mass or more from the viewpoint of further improving the adhesion to the substrate. On the other hand, from the viewpoint of improving conductivity and forming a finer pattern, 5% by mass or less is preferable.
  • the conductive layer (A-1) and the conductive layer (A-2) are further absorbed by a dispersant, a photopolymerization initiator, a monomer, a photoacid generator, a thermoacid generator, a solvent, a sensitizer, and visible light. It preferably contains a pigment and / or a dye, an adhesion improver, a surfactant, a polymerization inhibitor and the like.
  • the conductive layer (A-1) and the conductive layer (A-2) may be made of the same material or may be made of different materials.
  • the conductive layer (A-1) and the conductive layer (A-2) can be formed by using, for example, a conductive composition.
  • a conductive composition a composition containing the above-mentioned conductive particles, an alkali-soluble resin and a solvent can be used.
  • Conductive compositions include organic tin compounds, metal chelate compounds, dispersants, photopolymerization initiators, monomers, photoacid generators, thermoacid generators, sensitizers, pigments and / or dyes that absorb visible light. Adhesion improver, surfactant, polymerization inhibitor and the like can be contained as required.
  • a second insulating layer (OC-2) (hereinafter, “insulating layer (OC-2)" is formed between the conductive layer (A-1) and the conductive layer (A-2). ) ”).
  • the second insulating layer (OC-2) imparts insulation between the conductive layer (A-1) and the conductive layer (A-2).
  • the first insulating layer (OC-1) is on the upper surface of the conductive layer (A-1), that is, on the surface of the conductive layer (A-1) opposite to the surface in contact with the insulating layer (OC-2).
  • the insulating layer (OC-1) can prevent moisture in the atmosphere from reaching the conductive layer (A-1), and can improve the migration resistance of the conductive layer (A-1).
  • the film thickness of the insulating layer (OC-1) and the insulating layer (OC-2) is preferably 0.1 ⁇ m or more, and more preferably 0.5 ⁇ m or more from the viewpoint of further improving the migration resistance.
  • the film thickness of the insulating layer (OC-1) and the insulating layer (OC-2) is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, and particularly 3 ⁇ m or less, from the viewpoint of further improving transparency and bending resistance. preferable.
  • the ratio of the film thickness of the insulating layer (OC-1) to the film thickness of the base material (S-1) ((OC-1) / (S-1)) is preferably 0.05 to 0.5.
  • the film thickness ratio is more preferably 0.3 or less.
  • the film thickness can be measured using, for example, "Surfcom (registered trademark)" 1400 (manufactured by Tokyo Seimitsu Co., Ltd.) stylus type profilometer. More specifically, the film thickness at three random positions can be measured with a stylus type step meter (measurement length: 1 mm, scanning speed: 0.3 mm / sec), and the average value can be used as the film thickness. it can.
  • “Surfcom (registered trademark)” 1400 manufactured by Tokyo Seimitsu Co., Ltd.
  • the film thickness at three random positions can be measured with a stylus type step meter (measurement length: 1 mm, scanning speed: 0.3 mm / sec), and the average value can be used as the film thickness. it can.
  • the variation of b * is preferably within 1.5. More preferably, it is within 1.0.
  • the variation in b * can be evaluated by measuring a total of 5 points at the center and four corners of the sample and calculating the difference between the maximum value and the minimum value.
  • the insulating layer (OC-1) preferably contains a colorant in order to adjust b * to the range described later.
  • the colorant By containing the colorant, the yellowness of the base material with the conductive layer can be reduced and the color tone can be further improved.
  • colorants include pigments and dyes. Of these, pigments are preferable from the viewpoint of heat resistance and light resistance. A blue colorant is preferable from the viewpoint of adjusting b * to the range described later.
  • the colorant preferably contains a metal complex.
  • the metal complex include phthalocyanine or a compound in which a metal is coordinated with phthalocyanine having a substituent at least partially.
  • the substituent include halogens such as chlorine, sulfonic acid groups, amino groups and the like.
  • the coordinating metal include copper, zinc, nickel, cobalt, and aluminum. Two or more of these metal complexes may be contained.
  • a copper complex of phthalocyanine is preferable because it can suppress the reaction between the colorant and other organic components and can further improve the color without fading during high temperature treatment in the process.
  • the colorant is a copper phthalocyanine sulfonic acid ammonium salt, a copper phthalocyanine tertiary amine compound, or a copper phthalocyanine sulfonic acid amide compound.
  • the colorant can be detected by MASS spectrum analysis of the insulating layer (OC-1) or the like.
  • PigmentBlue 15: 1 which is a copper phthalocyanine blue pigment having ⁇ -type and ⁇ -type structures, from the viewpoint of improving light resistance, discoloration does not occur even when exposed to sunlight, and a good appearance can be maintained.
  • Pigment Blue 15: 6 is preferred.
  • the insulating layer (OC-1) may further contain a colorant having various colors such as a red colorant, a yellow colorant, and a green colorant for the purpose of adjusting the color more precisely.
  • red colorant examples include anthraquinone pigment, azo pigment, quinacridone pigment, perylene pigment, diketopyrrolopyrrole pigment and the like.
  • the color indexes are Pigment Red 48, Pigment Red 57, Pigment Red 122, Pigment Red 168, Pigment Red 170, Pigment Red 177, Pigment Red 188, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209, Pigment Red. 221, Pigment Red 242, Pigment Violet 19, Pigment Violet 42, etc.
  • yellow colorant examples include azo pigments, pyrazolone pigments, benzimidazolone pigments, quinoxaline pigments, azomethine pigments and the like.
  • the color indexes are PigmentYellow1, PigmentYellow3, PigmentYellow74, PigmentYellow65, PigmentYellow111, PigmentYellow81, PigmentYellow83, PigmentYellow151, PigmentYellow13, PigmentYellow154, PigmentYellow 34 etc. can be mentioned.
  • green colorant examples include phthalocyanine pigments and perylene pigments.
  • color index examples include PigmentGreen7, PigmentGreen36, PigmentGreen58, PigmentBlack31 and the like.
  • the content of the colorant in the insulating layer (OC-1) is preferably 0.01 to 0.5% by mass based on 100% by mass of the total solid content in the insulating layer (OC-1).
  • the content of the colorant is more preferably 0.05% by mass or more.
  • the content of the colorant is more preferably 0.4% by mass or less.
  • the content of the colorant can be quantified by TG-MASS.
  • the insulating layer (OC-1) and the insulating layer (OC-2) are preferably formed from a cured product of an insulating composition containing an alkali-soluble resin.
  • alkali-soluble resin examples include the above-mentioned (meth) acrylic copolymer and cardo-based resin.
  • the (meth) acrylic copolymer is preferable from the viewpoint of improving the crosslink density and the light resistance
  • the cardo-based resin is preferable because it can improve the hydrophobicity and the migration resistance of the insulating layer. ..
  • a cardo-based resin containing two or more structural units represented by the following chemical formula (11) and containing a polymerizable group and an alkali-soluble group is preferable.
  • cardo-based resin a commercially available product can be preferably used, and for example, "V-259ME” (trade name, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) and the like can be preferably used.
  • the weight average molecular weight (Mw (A1)) of the (meth) acrylic copolymer and the weight average molecular weight (Mw (A2)) of the cardo resin are preferably 2,000 or more from the viewpoint of improving the coating characteristics, and the pattern. From the viewpoint of improving the solubility in the developing solution in the formation, 200,000 or less is preferable.
  • the weight average molecular weight refers to a polystyrene-equivalent value measured by GPC.
  • Mw (A2) / Mw (A1) is preferably 1.5 or less, more preferably 1.0 or less, from the viewpoint of suppressing layer separation and forming a uniform insulating layer.
  • the total content of the (meth) acrylic copolymer and the cardo-based resin can be arbitrarily selected depending on the desired film thickness and application, but is 10% by mass in 100% by mass of the total solid content. It is preferably% or more and 70% by mass or less.
  • the insulating composition may contain a hindered amine-based light stabilizer.
  • a hindered amine-based light stabilizer By containing the hindered amine-based light stabilizer, the coloring of the insulating layer can be further reduced, and the color and light resistance can be further improved.
  • the content of the hindered amine-based light stabilizer is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, based on 100% by mass of the total solid content.
  • the content of the hindered amine-based light stabilizer is preferably 10% by mass or less, more preferably 5% by mass or less.
  • the insulating composition further contains, if necessary, a polyfunctional monomer, a curing agent, an ultraviolet absorber, a polymerization inhibitor, an adhesion improver, a solvent, a surfactant, a dissolution inhibitor, a stabilizer, an antifoaming agent and the like. It can also contain an agent.
  • a polyfunctional monomer e.g., ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, ethylene glycol dimethacrylate, terpolymer, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, poly(ethylene glycol dimethacrylate), ethylene glycol dimethacrylate,
  • the base material with a conductive layer of the present invention may have an insulating layer (OC-0) between the base material (S-1) and the second conductive layer (A-2). ..
  • OC-0 insulating layer
  • the pattern processability of the second conductive layer (A-2) and the like can be improved.
  • the above-mentioned insulating composition can be used, and an inorganic film may be used.
  • the pattern processability of the second conductive layer (A-2) and the like can be further improved. Further, it is preferable because it can suppress the movement of metal impurities, water and the like from the base material (S-1) to the second conductive layer (A-2) and improve the reliability of the conductive layer.
  • Examples of the type of inorganic film include Si-based thin film, C-based thin film, and metal thin film.
  • a Si-based thin film is more preferable from the viewpoint of improving the pattern processability of the second conductive layer (A-2) and the like.
  • Examples of the Si-based thin film include Si, SiO x , SiC x , SiN x , SiO x Cy, SiO x N y , SiO x F y and the like.
  • the thickness of the inorganic film is preferably 5 to 20 nm. By setting the nm to 5 nm or more, the movement of metal impurities, water, etc. from the base material (S-1) to the second conductive layer (A-2) can be sufficiently suppressed. By setting the thickness to 20 nm or less, the bending resistance of the substrate with a conductive layer of the present invention is not impaired.
  • the base material with a conductive layer of the present invention sets the b * value of the base material (S-1) to b * according to the L * a * b * color system defined by the International Commission on Illumination 1976. (S-1), when the b * value of the first insulating layer (OC-1) is b * (OC-1) and the b * value of the entire base material with the conductive layer is b * (T), All of the following equations (1) to (3) are satisfied.
  • the base material with a conductive layer of the present invention has the b of the first insulating layer (OC-1) according to the L * a * b * color system defined by the International Commission on Illumination 1976.
  • the * value is b * (OC-1) and the b * value of the second insulating layer (OC-2) is b * (OC-2)
  • the following equations (4) and (5) are satisfied.
  • the L * value, a * value, and b * value in the L * a * b * color system are such that the L * value is the brightness and the a * value and the b * value are the hue and the color. It represents the degree. Specifically, if the a * value is a positive value, it indicates a red hue, and if it is a negative value, it indicates a green hue. If the b * value is a positive value, it indicates a yellow hue, and if it is a negative value, it indicates a blue hue.
  • the larger the absolute value the larger the saturation of the color, and the smaller the absolute value, the smaller the saturation. Since the measured value of b * is neutral in the vicinity of 0, the color tone when observed is preferable because it is visually colorless and easily visible.
  • Equation (1) represents the color of the entire base material with a conductive layer, and is 4.3 ⁇ b * (T) ⁇ 2.0.
  • b * (T) By setting b * (T) to -4.3 or more, the bluish tint is suppressed, and by setting b * (T) to 2.0 or less, the yellowish tint is suppressed, and it becomes easy to be visually recognized as colorless as a whole.
  • Equation (2) represents the color of the base material (S-1), and 0.8 ⁇ b * (S-1) ⁇ 5.0.
  • b * (S-1) By setting b * (S-1) to 0.8 or more, the blueness of the base material (S-1) is suppressed, and by setting b * (S-1) to 5.0 or less, the base material (S-) is suppressed.
  • the yellowness of 1) can be suppressed. As a result, it becomes easy to adjust the color of the entire base material with the conductive layer.
  • the formula (3) expresses the relationship between the color of the entire base material with the conductive layer and the color of the insulating layer (OC-1), and is 1.5 ⁇ b * (T) ⁇ b * (OC-1) ⁇ 5. It is .5.
  • the base material (S-1) tends to be colored yellow by heating during lamination.
  • the b * of the base material (S-1) that is easily colored yellow is within the range of the formula (2), while the b * value of the insulating layer is made smaller (negative value).
  • a method of reducing the b * value of the insulating layer a method of reducing the b * value of the insulating layer (OC-1) and a method of reducing the b * value of the insulating layer (OC-2) can be mentioned. Be done. However, according to the study by the present inventors, when the insulating layer (OC-2) contains a blue colorant in order to reduce the b * value of the insulating layer (OC-2), the blue colorant interacts with Ag ions. It was found that by doing so, the movement of Ag ions when a voltage was applied between the conductive layer (A-1) and the conductive layer (A-2) was accelerated, and the migration resistance was lowered.
  • the insulating layer (OC-1) is added with an appropriate amount of a colorant to the insulating layer (OC-1).
  • the formula (4) represents the relationship between the color of the base material (S-1) and the color of the insulating layer (OC-1), and 0.8 ⁇ b * (S-1) ⁇ b * (OC-1). ) ⁇ 8.0.
  • b * (S-1) -b * (OC-1) By setting b * (S-1) -b * (OC-1) to 0.8 or more, the yellowness of the entire base material with the conductive layer can be suppressed.
  • the b * (S-1) -b * (OC-1) is more preferably 1.0 or more.
  • By setting b * (S-1) -b * (OC-1) to 8.0 or less the total light transmittance of the entire base material with the conductive layer can be increased.
  • the b * (S-1) -b * (OC-1) is more preferably 5.0 or less.
  • Equation (5) expresses the relationship between the color of the insulating layer (OC-1) and the color of the insulating layer (OC-2), and 0.5 ⁇ b * (OC-2) -b * (OC-1). ) ⁇ 7.0.
  • the insulating layer (OC-2) contains a blue colorant in order to reduce the b * value of the insulating layer (OC-2)
  • the conductive layer (A) in the subsequent step is added.
  • -1 It was found that the migration resistance was reduced by heating during formation. Therefore, in the second aspect of the present invention, attention was paid to reducing only the b * value of the insulating layer (OC-1), and the relationship of the equation (5) was found.
  • b * (OC-2) -b * (OC-1) By setting b * (OC-2) -b * (OC-1) to 0.5 or more, the yellowness of the entire base material with the conductive layer can be suppressed and the migration resistance can be improved.
  • b * (OC-2) -b * (OC-1) is more preferably 0.8 or more.
  • b * (OC-2) -b * (OC-1) is more preferably 5.0 or less.
  • the reflection chromaticity b * is a characteristic value defined in the L * a * b * color system.
  • the L * a * b * color system is a color method defined by the International Commission on Illumination (CIE) in 1976, and the L * value, a * value, and b * value in the present invention are JIS-.
  • the measurement can be performed by the measurement method by reflection. More specifically, it can be calculated by measuring the reflectance of the total reflected light of each layer using a spectrophotometer (CM-2600d; manufactured by Konica Minolta Co., Ltd.) and measuring the reflected chromaticity b *. it can.
  • CM-2600d manufactured by Konica Minolta Co., Ltd.
  • the method for producing the base material with the conductive layer of the present invention will be described.
  • the method for producing a base material with a conductive layer of the present invention at least the above-mentioned base material (S-1), conductive layer (A-2), and insulating layer (OC-2) are placed on a temporary support having a peeling function.
  • the base material (S-1) has a peeling function. Having a peeling function means that the temporary support and the base material with a conductive layer can be peeled off at the interface between the temporary support and the base material (S-1).
  • Examples of the temporary support include a silicon wafer, a ceramic substrate, an organic substrate, and the like.
  • Examples of the ceramic substrate include a glass substrate made of glass such as soda glass, non-alkali glass, borosilicate glass, and quartz glass; an alumina substrate, an aluminum nitride substrate, a silicon carbide substrate, and the like. Soda glass is often used because it is inexpensive and easily available. However, since the alkaline component may elute from the soda glass and cause problems such as poor conductivity, an inorganic film such as SiO 2 is used to suppress the elution of the alkaline component. Is preferably formed on the surface.
  • the organic substrate include an epoxy substrate, a polyetherimide resin substrate, a polyetherketone resin substrate, a polysulfone resin substrate, a polyimide film, a polyester film and the like.
  • the high transmittance of the laser light of the temporary support is a viewpoint of reducing the laser light irradiation time. Is preferable.
  • a base material (S-1) is formed on the temporary support.
  • the method for forming the base material (S-1) may include a coating step of applying the resin composition onto the temporary support, a prebaking step of drying the applied resin composition, and a curing step of curing the applied resin composition. preferable.
  • Examples of the method of applying the resin composition on the temporary support include spin coater, bar coater, blade coater, roll coater, die coater, calendar coater, coating using meniscus coater, screen printing, spray coating, and dip coating. And so on.
  • drying method in the pre-baking step and the curing step include heat drying, vacuum drying, vacuum drying, and infrared irradiation.
  • heat-drying device examples include a hot plate and a hot air dryer (oven).
  • the temperature and time of the prebaking step can be appropriately set depending on the composition of the resin composition and the film thickness of the coating film to be dried.
  • the heating temperature is preferably 50 to 150 ° C., and the heating time is preferably 10 seconds to 30 minutes.
  • the atmosphere, temperature and time of the curing step can be appropriately set depending on the composition of the resin composition and the film thickness of the coating film to be dried, but it is preferable to cure in air.
  • the heating temperature is preferably 150 ° C. or higher, more preferably 180 ° C. or higher, from the viewpoint of sufficiently advancing curing.
  • the heating temperature is preferably 350 ° C. or lower, more preferably 300 ° C. or lower, still more preferably 245 ° C. or lower.
  • the heating time is preferably 5 minutes or more, more preferably 20 minutes or more, from the viewpoint of sufficiently advancing the curing.
  • the heating time is preferably 120 minutes or less, more preferably 80 minutes or less.
  • the base material (S-1) thus formed may be further surface-treated.
  • the surface treatment By applying the surface treatment, the surface state of the base material (S-1) is changed, and the deterioration of the pattern processability due to the development residue in the subsequent forming step of the second conductive layer (A-2) and the like is suppressed. Can be done.
  • the surface treatment method for example, corona discharge treatment, plasma treatment, UV ozone treatment and the like are preferably mentioned. Corona discharge treatment or plasma treatment is preferable, and plasma treatment is more preferable, from the viewpoint of modifying the surface state while suppressing deterioration of the surface and further reducing the residue.
  • corona discharge treatment or UV ozone treatment is preferable, and UV ozone treatment is more preferable.
  • an insulating layer (OC-0) may be further formed on the formed base material (S-1).
  • the forming method preferably includes a coating step of applying the insulating composition on the base material (S-1), a prebaking step of drying the applied insulating composition, and a curing step of curing the coated insulating composition.
  • a second conductive layer (A-2) is formed on the obtained base material (S-1) or the insulating layer (OC-0).
  • the method for forming the second conductive layer (A-2) is a coating step of applying the conductive composition on the substrate surface, a prebaking step of drying the applied conductive composition, and exposing and developing the mesh. It is preferable to include a pattern forming step (exposure step and developing step) and a curing step of curing the obtained mesh pattern.
  • Examples of the method of applying the conductive composition on the substrate surface include the methods exemplified as the method of applying the resin composition.
  • drying method in the pre-baking step and the curing step include the methods exemplified as the drying method of the resin composition.
  • the prebake temperature and time can be appropriately set depending on the composition of the conductive composition and the film thickness of the coating film to be dried.
  • the heating temperature is preferably 50 to 150 ° C., and the heating time is preferably 10 seconds to 30 minutes.
  • the light source used in the exposure process for example, j-line, i-line, h-line, g-line and the like of a mercury lamp are preferable.
  • Examples of the developing solution used in the developing step include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; Primary amines such as ethylamine and n-propylamine; Secondary amines such as diethylamine and di-n-propylamine; Tertiary amines such as triethylamine and methyldiethylamine; Tetraalkylammonium hydroxides such as tetramethylammonium hydroxide (TMAH); Quaternary ammonium salts such as choline; Alcohol amines such as triethanolamine, diethanolamine, monoethanolamine, dimethylaminoethanol, diethylaminoethanol; Organic alkalis such as pyrrole, piperidine, 1,8-diazabicyclo [5,4,0] -7-undecene, 1,5-diazabicyclo [4,3,0] -5-non
  • An alkaline aqueous solution in which the alkaline substance of the above is dissolved in water can be mentioned.
  • a water-soluble organic solvent such as ethanol, ⁇ -butyrolactone, dimethylformamide, or N-methyl-2-pyrrolidone may be appropriately added thereto.
  • a surfactant such as a nonionic surfactant is added to these alkaline developers with respect to 100% by mass of the alkaline developer. Is also preferable.
  • the atmosphere, temperature and time of the curing step can be appropriately set depending on the composition of the conductive composition and the film thickness of the coating film to be dried, but it is preferable to cure in air.
  • the heating temperature is preferably 100 to 300 ° C, more preferably 200 to 300 ° C.
  • the heating time is preferably 5 minutes to 120 minutes.
  • a second insulating layer (OC-2) is formed on the formed second conductive layer (A-2).
  • the method for forming the second insulating layer (OC-2) is a coating step of applying the insulating composition on the conductive layer (A-2), a prebaking step of drying the applied insulating composition, and exposing the insulating composition. It is preferable to include a step of developing and forming a pattern (exposure step, a developing step), and a curing step of curing the obtained pattern. Each step can be performed in the same manner as in the conductive layer (A-2).
  • the first conductive layer (A-1) is formed on the second insulating layer (OC-2).
  • the first conductive layer (A-1) can be formed by the same method as the second conductive layer (A-2).
  • a first insulating layer (OC-1) is further formed on the first conductive layer (A-1).
  • OC-1 By forming the first insulating layer (OC-1), it is possible to suppress the moisture in the atmosphere from reaching the conductive layer (A-1), and to further improve the moist heat resistance.
  • the first insulating layer (OC-1) above the lead-out portion of the electrode. By precisely removing this portion in advance, it is possible to facilitate the connection with the external electrode later.
  • the first insulating layer (OC-1) can be formed in the same manner as the second insulating layer (OC-2).
  • the surface of the base material with a conductive layer opposite to the temporary support may be attached to the opposing member via the transparent adhesive layer.
  • the facing member is preferably a glass substrate or a film substrate, and the member may be formed on the glass substrate or the film substrate. Specific examples of such facing members include cover glass, cover film, polarizing film, color filter substrate, display substrate and the like.
  • a method of peeling the base material (S-1) and the temporary support for example, a method of irradiating the base material (S-1) with a laser from the back surface of the temporary support to peel the base material (S-1) and a base material with a conductive layer are provided.
  • the base material (S-1) is cut from the upper surface and mechanically peeled from the cut end face. Examples thereof include a method, but from the viewpoint of improving the moisture and heat resistance of the base material with a conductive layer, a method of mechanically peeling from the cut end face is preferable.
  • the above-mentioned peeling step is performed on the base material with the conductive layer with the temporary support to peel off the base material with the conductive layer and the temporary support, and then the side opposite to the temporary support.
  • the touch panel may be completed by sticking the surface of the surface to the opposing member via the transparent adhesive layer.
  • OCA transparent adhesive layer
  • the above laminating step and peeling are performed. The process may be performed. From the viewpoint of bonding accuracy, it is preferable to perform the peeling step after bonding the base material with the conductive layer with the temporary support to the opposing member such as a glass substrate.
  • the base material with a conductive layer of the present invention is preferably produced by being formed on a temporary support having excellent dimensional accuracy, and then peeling and removing the temporary support. By this manufacturing method, it is possible to apply a processing method having excellent dimensional accuracy.
  • the base material with a conductive layer of the present invention since the base material (S-1) contains a polymer containing the above-mentioned specific structure, the residue of the conductive composition is suppressed, and the base material (S-1) is excellent in color and moisture and heat resistance. According to the present invention, it is possible to provide a base material with a conductive layer and a touch panel capable of supporting fine pattern formation and flexibility.
  • Examples of applications of the base material with a conductive layer of the present invention include touch panels, wiring of curved displays such as micro LEDs, and various flexible sensors such as RFID. Of these, it is preferably used for a touch panel.
  • the touch panel of the present invention includes the above-mentioned base material with a conductive layer.
  • a flexible printed circuit board is attached to the above-mentioned base material with a conductive layer via an anisotropic conductive film (ACF), and a cover glass or the like is attached via an optical adhesive sheet (OCA).
  • a touch module can be manufactured by sticking to.
  • TAPOB 1,3,5-tris (4-aminophenoxy) benzene (a compound containing a structure represented by the general formula (9)).
  • PE-3A Pentaerythritol triacrylate.
  • A-1 Silver particles with an average thickness of the surface carbon coating layer of 1 nm and an average primary particle diameter of 40 nm (manufactured by Nisshin Engineering Co., Ltd.)
  • A-2 Silver particles with an average primary particle diameter of 0.7 ⁇ m (manufactured by Mitsui Mining & Smelting Co., Ltd.).
  • Color-1 Phthalocyanine copper compound "Pigment Blue 15: 6" (manufactured by Dainichiseika Kogyo Co., Ltd.)
  • color-2 Phthalocyanine copper compound "Pigment Blue 15: 1" (manufactured by Dainichiseika Kogyo Co., Ltd.)
  • color-3 Aluminosodium sulfosilicate (manufactured by Holiday).
  • Production Example 1 (Synthesis of Polyimide Solution-1 and Polyimide Solution-2) (Polyimide solution-1) Under a dry nitrogen stream, 100 mol parts of ODPA was dissolved in GBL to prepare a solution having a concentration of 10% by mass. To this, 50 mol parts of DDS and 48 mol parts of TFMB as diamine and 2 mol parts of TAPOB as triamine were added and reacted at 20 ° C. for 1 hour and then at 50 ° C. for 2 hours. The concentration of the polyimide solution-1 in which the reaction was completed was 20 to 25% by mass.
  • Production Example 2 Preparation of transparent composition (s-1, s-2) 100 g of the polyimide solution-1 prepared in Production Example 1 and a surfactant (F-477: manufactured by DIC Corporation) in a clean bottle. 0.03 g was added and stirred for 1 hour to obtain a transparent composition s-1.
  • the polyimide solution-1 was replaced with the polyimide solution-2, and the transparent composition s-2 was obtained by the same operation.
  • an organic compound 20 g of an alkali-soluble resin (A), 0.6 g of ethylacetacetate aluminum diisopropylate (ALCH: manufactured by Kawaken Fine Chemical Co., Ltd.) as a metal chelate compound, and a photopolymerization initiator (NCI-831:)
  • An organic I solution for a conductive composition was obtained by adding 132.6 g of PGMEA and 52.6 g of DPM to a mixture of 2.4 g of (made by ADEKA Co., Ltd.) and 12.0 g of PE-3A and stirring.
  • the silver dispersion liquid 1 and the organic I liquid were mixed to obtain a conductive composition (a-1). Further, the conductive particles A-2 were used instead of the conductive particles A-1 to obtain a conductive composition (a-2).
  • the color of the base material with the conductive layer was evaluated according to the following criteria. 2 or more was passed. 5: -1.0 ⁇ b * (T) ⁇ 1.0 4: -2.0 ⁇ b * (T) ⁇ -1.0, or 1.0 ⁇ b * (T) ⁇ 1.5 3: -3.0 ⁇ b * (T) ⁇ -2.0, or 1.5 ⁇ b * (T) ⁇ 1.8 2: -4.3 ⁇ b * (T) ⁇ -3.0, or 1.8 ⁇ b * (T) ⁇ 2.0 1: b * (T) ⁇ -4.3 or 2.0 ⁇ b * (T).
  • the variation in color was defined by the difference between the maximum value and the minimum value of b * (hereinafter referred to as b * (MAX) -b * (MIN)), and evaluated according to the following criteria. 2 or more was passed.
  • a D65 light source was used as the light source. 5: b * (MAX) -b * (MIN) ⁇ 1.0 4: 1.0 ⁇ b * (MAX) -b * (MIN) ⁇ 1.5 3: 1.5 ⁇ b * (MAX) -b * (MIN) ⁇ 2.0 2: 2.0 ⁇ b * (MAX) -b * (MIN) ⁇ 2.5 1: 2.5 ⁇ b * (MAX) -b * (MIN).
  • the base material (S-1) transmits all light at a wavelength of 400 nm.
  • the rate was measured by using an ultraviolet-visible spectrophotometer (“MultiSpec-1500 (trade name, manufactured by Shimadzu Corporation)”) for the total light transmittance of the substrate with a conductive layer at a wavelength of 450 nm.
  • the total light transmittance was evaluated according to the following evaluation criteria. 2 or more was passed. 5: 90% or more and 4: 80% or more and less than 90% 3: 70% or more and less than 80% 2: 50% or more and less than 70% 1: 50% or less.
  • the wet heat resistance of the base material with a conductive layer prepared in each Example and each Comparative Example was evaluated by the following method.
  • the insulation deterioration characteristic evaluation system "ETAC SIR13" (trade name, manufactured by Kusumoto Kasei Co., Ltd.) was used for the measurement. Electrodes were attached to the terminal portions of the conductive layer (A-1) and the conductive layer (A-2), respectively, and the laminated substrate was placed in a high-temperature and high-humidity tank set to 85 ° C. and 85% RH conditions.
  • Example 1 ⁇ Formation of base material (S-1)>
  • the above-mentioned transparent composition (s-1) is placed on a glass substrate having a length of 210 mm and a width of 297 mm, which is a temporary support, at 600 rpm using a spin coater "1H-360S (trade name, manufactured by Mikasa Co., Ltd.)".
  • a prebaked film was prepared by prebaking at 100 ° C. for 2 minutes using a hot plate "SCW-636 (trade name, manufactured by Dainippon Screen Mfg. Co., Ltd.)”.
  • the prepared substrate with a prebaked film was cured in air at 240 ° C.
  • the conductive composition (a-1) is placed on a glass substrate on which the base material (S-1) is formed at 300 rpm using a spin coater (“1H-360S (trade name, manufactured by Mikasa Co., Ltd.)”). After spin coating for 10 seconds at 500 rpm for 2 seconds, prebaking at 100 ° C. for 2 minutes using a hot plate (“SCW-636 (trade name, manufactured by Dainippon Screen Mfg. Co., Ltd.)”) is performed to prebak the film. Was produced. A parallel light mask aligner (“PLA-501F (trade name, manufactured by Canon Inc.)”) was used as a light source, and a prebake film was exposed through a desired mask.
  • a spin coater (“1H-360S (trade name, manufactured by Mikasa Co., Ltd.)”.
  • AD-2000 (trade name, manufactured by Takizawa Sangyo Co., Ltd.)
  • the patterned substrate was cured in air at 220 ° C. for 30 minutes using an oven to form a second conductive layer (A-2).
  • the line width of the formed second conductive layer (A-2) was measured at five points using a digital microscope (“VHX-5000 (trade name, manufactured by KEYENCE CORPORATION)”) and averaged. The width was 3.8 ⁇ m.
  • the result of the film thickness measurement measured using the stylus type step meter was 0.5 ⁇ m.
  • the insulating composition shown in Table 2 was spin-coated on a glass substrate on which the second conductive layer (A-2) was formed at 650 rpm for 5 seconds using a spin coater, and then spin-coated at 100 ° C. using a hot plate. Prebaking was performed for a minute to prepare a prebaked film. The prebake film was exposed through a desired mask using an ultra-high pressure mercury lamp as a light source using a parallel light mask aligner. Then, using an automatic developing apparatus, shower development was carried out with a 0.045 mass% potassium hydroxide aqueous solution for 60 seconds, and then rinse with water for 30 seconds to perform pattern processing.
  • the patterned substrate was cured in air at 220 ° C. for 50 minutes using an oven to form a second insulating layer (OC-2).
  • First conductive layer (A-1)> Using the conductive composition (a-1), the first conductive layer (A-1) is formed on the insulating layer in the same manner as in the above ⁇ formation of the second conductive layer (A-2)>. did. Further, as a result of measuring the line width in the same manner as in the second conductive layer (A-2), the line width was 4.1 ⁇ m. The result of the film thickness measurement was 0.5 ⁇ m.
  • the first insulation is formed on the first conductive layer (A-1) in the same manner as in the above ⁇ formation of the second insulating layer (OC-2)>.
  • a layer (OC-1) was formed to prepare a base material with a conductive layer.
  • Table 2 shows the results of evaluation by the above method. The yellowness was slightly strong and the evaluation of b * (T) was "3", but it was within the range where it could be used without problems. The color variation, bending resistance, migration resistance and light resistance were good at "5".
  • Examples 2 to 5 The same operation as in Example 1 was carried out except that the insulating composition used for the first insulating layer (OC-1) was changed as shown in Table 2. As the amount of coloring added increased, the color became closer to neutral.
  • Example 6 The same operation as in Example 1 was carried out except that the insulating composition used for the first insulating layer (OC-1) was changed as shown in Table 2. Since the amount of coloring added was further increased, the bluish color was strong and the color evaluation was "2", and the total light transmittance was reduced to the evaluation "3", but it was within the range where it could be used without any problem.
  • Example 7 The same operation as in Example 1 was carried out except that the insulating composition used for the first insulating layer (OC-1) was changed as shown in Table 2.
  • Example 8 The same operation as in Example 1 was carried out except that the insulating composition used for the first insulating layer (OC-1) was changed as shown in Table 3. Since the light resistance of the colorant was low, the light resistance evaluation was "3", but it was within the range where it could be used without any problem.
  • Example 9 The same operation as in Example 6 was performed except that the coating conditions of the base material (S-1) were changed and the film thickness was changed as shown in Table 3. The variation of b * became large, and the evaluation became "4". Further, as the film thickness of the base material (S-1) became thicker, the total light transmittance decreased, and the evaluation was "2", but it was within the range where it could be used without any problem.
  • Example 10 The same operation as in Example 9 was carried out except that the coating conditions of the base material (S-1) were changed and the film thickness was changed as shown in Table 3. The variation of b * was even larger, and the evaluation was "3", but it was within the range where it could be used without problems.
  • Example 11 The same operation as in Example 4 was performed except that the film thickness of the first insulating layer (OC-1) was changed as shown in Table 3. The first insulating layer (OC-1) became too rigid and the bending resistance decreased, and the evaluation was "4", but it was within the range where it could be used without any problem.
  • Example 12 The same operation as in Example 11 was performed except that the film thickness of the first insulating layer (OC-1) was changed as shown in Table 3. The first insulating layer (OC-1) became too rigid and the bending resistance decreased, and the evaluation was "3", but it was within the range where it could be used without any problem.
  • Example 13 The same operation as in Example 7 was performed except that the transparent composition (s-2) was used instead of the transparent composition (s-1).
  • the color and total light transmittance of the base material (S-1) were measured, b * was 0.8 and the total light transmittance at 400 nm was 77%.
  • the base material (S-1) formed using the transparent composition (s-2) had good transparency and low b *, and the total light transmittance evaluation of the base material with a conductive layer was "5". ..
  • Example 14 The same operation as in Example 5 was carried out except that PET (heat resistant PET film, Toray's “Lumirror” film thickness 50 ⁇ m) was used instead of the transparent composition (s-1).
  • the total light transmittance of PET at 400 nm was as high as 82%, and the light was passed through during the light resistance test, so that the insulating layer was colored and the light resistance evaluation was "3".
  • the water permeability was high and the migration resistance was "2", but it was within the range where it could be used without problems.
  • Example 15 The same operation as in Example 8 was carried out except that the insulating compositions used for the first insulating layer (OC-1) and the second insulating layer (OC-2) were changed as shown in Table 2. Since the (meth) acrylic copolymer of the alkali-soluble resin (A) had low absorbance and good light resistance, the light resistance evaluation was as good as “5”.
  • Example 16 The same operation as in Example 4 was performed except that the conductive composition (a-2) was used instead of the conductive composition (a-1).
  • the formed second conductive layer (A-2) has a line width of 8.8 ⁇ m and a film thickness of 1.2 ⁇ m
  • the first conductive layer (A-1) has a line width of 8.4 ⁇ m and a film thickness of 8.4 ⁇ m. It was 1.2 ⁇ m. Since the line width was thick, the total light transmittance evaluation was "2", and because the film thickness was thick, the bending evaluation was "4", but it was within the usable range without any problem.
  • Example 1 The same operation as in Example 1 was carried out except that the insulating composition used for the first insulating layer (OC-1) was changed as shown in Table 4. Since the b * of the first insulating layer (OC-1) changed significantly to 0.5, the evaluation of the color was "1", which was an unusable level.
  • Example 2 The same operation as in Example 1 was carried out except that the insulating composition used for the first insulating layer (OC-1) was changed as shown in Table 4. Since the b * of the first insulating layer (OC-1) changed significantly to 0.4, the evaluation of the color was "1", which was an unusable level.
  • Example 3 The same operation as in Example 1 was carried out except that the insulating composition used for the first insulating layer (OC-1) was changed as shown in Table 4. Since the b * of the first insulating layer (OC-1) changed significantly to -7.2, the evaluation of the color was "1", which was an unusable level. In addition, since the amount of the colorant added was large, the variation of b * became large, and the total light transmittance was reduced.
  • Example 5 The same operation as in Example 10 was performed except that the film thicknesses of the base material (S-1) and the insulating layer (OC-1) were changed. The value of b * (T) -b * (OC-1) increased, and the total light transmittance of the base material with the conductive layer decreased accordingly.
  • Tables 2 to 4 show the evaluation results of each example and comparative example.
  • the base material with a conductive layer of the present invention can be suitably used not only for conventional flat displays but also for flexible displays.

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Abstract

La présente invention concerne un substrat ayant des couches électroconductrices qui a une bonne couleur et une excellente résistance à la migration, ainsi qu'un panneau tactile dans lequel le substrat est utilisé. Un substrat ayant des couches électroconductrices selon l'invention a au moins une seconde couche électroconductrice (A-2), une seconde couche isolante (OC-2), une première couche électroconductrice (A-1) et une première couche isolante (OC-1) sur un substrat (S-1). Le substrat ayant des couches électroconductrices satisfait toutes les équations (1) à (3) lorsque la valeur b* du substrat (S-1), telle que définie par le système de couleur L*a*b* fourni par la Commission internationale de l'éclairage 1976, est b*(S-1), la valeur b* de la première couche isolante (OC-1) est b*(OC-1), et la valeur b* de l'ensemble du substrat ayant des couches électroconductrices est b*(T). (1) : -4,3 ≤ b*(T) ≤ 2,0 (2) : 0,8 ≤ b*(S-1) ≤ 5,0 (3) : 1,5 ≤ b*(T) - b*(OC-1) ≤ 5,5
PCT/JP2020/012921 2019-04-02 2020-03-24 Substrat à couches électroconductrices, et panneau tactile WO2020203447A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012133367A1 (fr) * 2011-03-28 2012-10-04 東レ株式会社 Corps stratifié conducteur et écran tactile
WO2018084067A1 (fr) * 2016-11-01 2018-05-11 東レ株式会社 Panneau tactile et procédé de fabrication d'un panneau tactile

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US20080049413A1 (en) * 2006-08-22 2008-02-28 Idemitsu Kosan Co., Ltd. Organic electroluminescence device
EP1935633A1 (fr) * 2006-12-21 2008-06-25 AGC Flat Glass Europe SA Panneau translucide pour connecter des composants electroniques
US10042481B2 (en) * 2009-03-31 2018-08-07 Teijin Limited Transparent electroconductive laminate and transparent touch panel
JP5515567B2 (ja) * 2009-09-29 2014-06-11 凸版印刷株式会社 透明導電性フィルム
JP5645581B2 (ja) * 2010-10-05 2014-12-24 富士フイルム株式会社 タッチパネル
JP5520785B2 (ja) * 2010-11-10 2014-06-11 日東電工株式会社 絶縁テープ
JP6563497B2 (ja) * 2015-07-24 2019-08-21 富士フイルム株式会社 タッチパネル用導電フィルム、タッチパネル、および、タッチパネル付き表示装置

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012133367A1 (fr) * 2011-03-28 2012-10-04 東レ株式会社 Corps stratifié conducteur et écran tactile
WO2018084067A1 (fr) * 2016-11-01 2018-05-11 東レ株式会社 Panneau tactile et procédé de fabrication d'un panneau tactile

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