WO2023228927A1 - Substrat conducteur et panneau tactile - Google Patents

Substrat conducteur et panneau tactile Download PDF

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Publication number
WO2023228927A1
WO2023228927A1 PCT/JP2023/019062 JP2023019062W WO2023228927A1 WO 2023228927 A1 WO2023228927 A1 WO 2023228927A1 JP 2023019062 W JP2023019062 W JP 2023019062W WO 2023228927 A1 WO2023228927 A1 WO 2023228927A1
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Prior art keywords
conductive
group
layer
formula
silver
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PCT/JP2023/019062
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English (en)
Japanese (ja)
Inventor
智史 田中
亜矢 中山
優樹 中川
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富士フイルム株式会社
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Publication of WO2023228927A1 publication Critical patent/WO2023228927A1/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
    • 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
    • B32B7/025—Electric or magnetic properties
    • 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 conductive substrate and a touch panel.
  • Conductive substrates having conductive thin wires are widely used in various applications such as touch panels, solar cells, and EL (electro luminescence) elements.
  • touch panels solar cells
  • EL electro luminescence
  • the mounting rate of touch panels on mobile phones and mobile game devices has increased, and the demand for conductive substrates for capacitive touch panels capable of multi-point detection is rapidly expanding.
  • Patent Document 1 describes an electrode having a plurality of repeating units consisting of an image unit having a conductive pattern made of metal, a peripheral wiring part connected to the conductive pattern, and a non-conductive part that makes it impossible to connect adjacent image units.
  • Techniques related to the manufacturing method of pattern sheets are disclosed, and methods for forming conductive patterns and peripheral wiring portions include a printing method, a photolithography method, and a method using a silver salt photosensitive material as a conductive material precursor. has been done.
  • Such a touch panel includes a conductive substrate and various members mounted around the conductive substrate. Cushioning materials, adhesives, and the like used for these peripheral members may contain sulfur-containing compounds. Further, sulfur components such as H 2 S and SO 2 are also present in the environment in which the touch panel is used. As a result of studying conductive substrates having conductive thin wires with reference to Patent Document 1, the present inventor found that these sulfur sources existing around the conductive substrate cause a sulfurization reaction in the metal thin wires constituting the wiring. It has been found that this causes a problem in that the conductivity of the wiring decreases, causing failures such as decreased sensitivity and malfunction of the touch panel.
  • a conductive substrate having a base material and a conductive layer disposed on the base material, wherein the conductive layer includes a conductive thin wire portion containing a metal and a conductive thin wire portion containing a metal. an adjacent transparent insulating part that does not contain metal, and the conductive layer contains a compound represented by formula (1), formula (2), formula (3) or formula (4) described below.
  • conductive substrate [2] The conductive substrate according to [1], wherein each R 1 independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.
  • the above compound is 5-methyl-1,3,4-thiadiazole-2-thiol, 5-(propan-2-yl)-1,3,4-thiadiazole-2-thiol, 5-phenyl-1 , 3,4-thiadiazole-2-thiol, 3-mercapto-1H-1,2,4-triazole, 3-methyl-4H-1,2,4-triazole-5-thiol, 4-methyl-1,2 , 4-triazole-3-thiol, 1,2,3-benzotriazole, 5-methylbenzotriazole, and 2,2'-(4-methyl-1H-benzotriazol-1-ylmethylimino)bisethanol.
  • FIG. 1 is a schematic cross-sectional view showing an example of the configuration of a conductive substrate of the present invention.
  • FIG. 3 is a plan view showing an example of a mesh pattern of the conductive layer of the conductive substrate of the present invention.
  • a numerical range expressed using " ⁇ ” means a range that includes the numerical values written before and after " ⁇ " as lower and upper limits.
  • the “content” of the component means the total content of the two or more types of components.
  • “g” and “mg” represent “mass g” and “mass mg”, respectively.
  • polymer or “polymer compound” means a compound having a weight average molecular weight of 2000 or more.
  • the weight average molecular weight is defined as a polystyrene equivalent value measured by GPC (Gel Permeation Chromatography).
  • GPC Gel Permeation Chromatography
  • the conductive substrate according to the present invention includes a base material and a conductive layer disposed on the base material.
  • the conductive layer has a conductive thin wire portion and a transparent insulating portion adjacent to the conductive thin wire portion.
  • the conductive thin wire portion contains metal, and the transparent insulating portion does not contain metal.
  • the conductive layer further contains a compound represented by formula (1), formula (2), formula (3), or formula (4) described below.
  • FIG. 1 is a schematic cross-sectional view showing an example of the structure of a conductive substrate according to the present invention.
  • the conductive substrate 10 shown in FIG. 1 includes a base material 12 and a conductive layer 14 disposed on the surface of the base material 12.
  • the conductive layer 14 includes a conductive thin wire portion 16 and a transparent insulating portion 18 adjacent to the conductive thin wire portion 16 .
  • FIG. 1 shows two conductive thin wire portions 16 extending perpendicularly to the paper surface, the arrangement form of the conductive thin wire portions 16 and the number thereof are not particularly limited.
  • the type of the base material is not particularly limited as long as it can support the photosensitive layer and the conductive thin wire portion, and examples thereof include a plastic substrate, a glass substrate, and a metal substrate, with a plastic substrate being preferred.
  • a flexible base material is preferable since the resulting conductive member has excellent bendability.
  • Examples of the flexible base material include the above-mentioned plastic substrate.
  • the thickness of the base material is not particularly limited, and is often 25 to 500 ⁇ m. Note that when the conductive substrate is applied to a touch panel and the surface of the base material is used as a touch surface, the thickness of the base material may exceed 500 ⁇ m.
  • Materials constituting the base material include polyethylene terephthalate (PET) (258°C), polycycloolefin (134°C), polycarbonate (250°C), acrylic film (128°C), polyethylene naphthalate (269°C), polyethylene ( 135°C), polypropylene (163°C), polystyrene (230°C), polyvinyl chloride (180°C), polyvinylidene chloride (212°C), and triacetyl cellulose (290°C), etc. Certain resins are preferred, with PET, polycycloolefin, or polycarbonate being more preferred. Among them, PET is particularly preferable because it has excellent adhesion to the conductive thin wire portion.
  • the numerical value in parentheses above is the melting point or glass transition temperature.
  • the total light transmittance of the base material is preferably 85 to 100%.
  • the total light transmittance is measured using "Plastics - How to determine total light transmittance and total light reflectance" specified in JIS (Japanese Industrial Standard) K 7375:2008.
  • An undercoat layer may be disposed on the surface of the base material.
  • the undercoat layer preferably contains a specific polymer described below. When this undercoat layer is used, the adhesion of the conductive layer described later to the base material is further improved.
  • the method for forming the undercoat layer is not particularly limited, and examples thereof include a method in which a composition for forming an undercoat layer containing a specific polymer, which will be described later, is applied onto a base material and, if necessary, a heat treatment is performed.
  • the undercoat layer forming composition may contain a solvent as necessary.
  • the type of solvent is not particularly limited, and examples include solvents used in the photosensitive layer forming composition described below.
  • the composition for forming an undercoat layer containing a specific polymer a latex containing particles of a specific polymer may be used.
  • the thickness of the undercoat layer is not particularly limited, and is preferably 0.02 to 0.3 ⁇ m, more preferably 0.03 to 0.2 ⁇ m, in terms of better adhesion of the conductive layer to the base material.
  • the conductive layer has a conductive thin wire portion and a transparent insulating portion. That is, on the surface of the base material of the conductive substrate, a conductive thin wire portion containing metal and a transparent insulating portion not containing metal are arranged as a conductive layer.
  • the arrangement of the conductive thin wire portion and the transparent insulating portion in the conductive layer is not particularly limited.
  • the conductive layer may have a pattern formed by conductive thin wire portions and transparent insulating portions.
  • the pattern is not particularly limited, and includes, for example, triangles such as equilateral triangles, isosceles triangles, and right triangles, quadrilaterals such as squares, rectangles, rhombuses, parallelograms, and trapezoids, (regular) hexagons, and (regular) octagons, etc.
  • the shape is a (regular) n-gon, a circle, an ellipse, a star shape, or a geometric figure that is a combination of these figures, and more preferably a mesh shape (mesh pattern).
  • FIG. 2 is a plan view showing an example of a mesh pattern that the conductive layer has.
  • the mesh shape is intended to mean a shape that includes a plurality of non-thin wire portions (grids) 20 that are composed of intersecting conductive thin wire portions 16 and transparent insulating portions 18, and are spaced apart from each other. do.
  • the non-thin line portion 20 has a square shape with one side length L, but the non-thin line portion of the mesh pattern may have another shape, for example, a polygonal shape ( For example, it may be a triangle, a quadrilateral (diamond, rectangle, etc.), a hexagon, or a random polygon.
  • the shape of the side may be a curved shape other than a straight line, or may be an arc shape.
  • an arcuate shape for example, two opposing sides may have an outwardly convex arcuate shape, and the other two opposing sides may have an inwardly convex arcuate shape.
  • the shape of each side may be a wavy line shape in which an outwardly convex circular arc and an inwardly convex circular arc are continuous.
  • the shape of each side may be a sine curve.
  • the length L of one side of the non-thin wire portion 20 is not particularly limited, but is preferably 1500 ⁇ m or less, more preferably 1300 ⁇ m or less, and even more preferably 1000 ⁇ m or less.
  • the lower limit of the length L is not particularly limited, but is preferably 5 ⁇ m or more, more preferably 30 ⁇ m or more, and even more preferably 80 ⁇ m or more. If the length of one side of the non-thin line part is within the above range, it is possible to maintain good transparency, and when the conductive substrate is attached to the front of the display device, the display can be viewed without discomfort. can do.
  • the aperture ratio of the mesh pattern formed by the conductive thin wire portions is preferably 90% or more, more preferably 95% or more, and still more preferably 99% or more.
  • the upper limit is not particularly limited, but may be less than 100%.
  • the aperture ratio means the ratio (area ratio) of the area occupied by the transparent insulating part to the entire area occupied by the mesh pattern in the area where the mesh pattern of the conductive substrate is formed.
  • the thickness of the conductive layer is not particularly limited, but is preferably 0.5 to 3.0 ⁇ m, more preferably 1.0 to 2.0 ⁇ m.
  • the thickness of the conductive layer is determined by selecting five arbitrary points corresponding to the thickness of one conductive thin wire part using a scanning electron microscope, and calculating the arithmetic mean value of the parts corresponding to the thickness of the five points. Therefore, it is required.
  • the conductive thin wire portion is a portion that ensures the conductive properties of the conductive substrate by containing metal.
  • a metal one selected from the group consisting of silver (metallic silver), copper (metallic copper), gold (metallic gold), nickel (metallic nickel), and palladium (metallic palladium) because of its superior conductive properties. Mixtures with the above metals are preferred. Among these, a metal containing silver, ie, simple silver or a mixture of silver and copper is more preferable, and simple silver is even more preferable.
  • the conductive thin wire portion is intended to be a thin wire-shaped region disposed on the surface of the base material and integrally formed of a material containing metal.
  • the silver halide-free layer formed in Step H, which will be described later, and the protective layer, which will be formed in Step I, which will be described later are different from the thin wire-shaped metal-containing layer (silver Containing layer) together with the conductive thin wire portion.
  • the conductive thin wire portion may or may not be electrically connected to a member external to the conductive substrate.
  • a portion of the conductive thin wire portion may be a dummy electrode electrically insulated from the outside.
  • the metal contained in the conductive thin wire portion is usually in the form of solid particles.
  • the average particle diameter of the metal is preferably 10 to 1000 nm, more preferably 10 to 200 nm, in equivalent sphere diameter.
  • the equivalent sphere diameter is the diameter of spherical particles having the same volume, and the average particle diameter of metal particles is obtained as the average value obtained by measuring the equivalent sphere diameters of 100 objects and arithmetic averaging them. It will be done.
  • the shape of the metal particles is not particularly limited, and examples include shapes such as spherical, cubic, tabular, octahedral, and dodecahedral. Further, the metal particles may be partially or entirely bonded by fusion.
  • the conductive thin wire portion may have a structure in which a plurality of metals are dispersed in a polymer compound described below, or metal particles may aggregate in the polymer compound and exist as an aggregate. Further, at least some of the plurality of metals included in the conductive thin wire portion may be bonded to each other by a metal derived from metal ions used in a plating process to be described later.
  • the metal content in the conductive thin wire portion is not particularly limited, and is preferably 3.0 to 20.0 g/m 2 , and 5.0 to 15.0 g/m 2 in terms of better conductivity of the conductive substrate. is more preferable.
  • the conductive thin wire portion may contain a polymer compound in addition to metal.
  • the type of polymer compound contained in the conductive thin wire portion is not particularly limited, and known polymer compounds can be used. Among these, polymer compounds different from gelatin (hereinafter also referred to as "specific polymers") are preferred in that they can form a silver-containing layer with better strength and a conductive thin wire portion.
  • the type of specific polymer is not particularly limited as long as it is different from gelatin, and preferably a polymer that is not decomposed by proteolytic enzymes or oxidizing agents that decompose gelatin, which will be described later.
  • Specific polymers include hydrophobic polymers (water-insoluble polymers), such as (meth)acrylic resins, styrene resins, vinyl resins, polyolefin resins, polyester resins, polyurethane resins, At least one resin selected from the group consisting of polyamide resin, polycarbonate resin, polydiene resin, epoxy resin, silicone resin, cellulose polymer, and chitosan polymer, or comprising these resins Examples include copolymers consisting of monomers.
  • the specific polymer has a reactive group that reacts with a crosslinking agent described below. It is preferable that the specific polymer is in the form of particles. That is, it is preferable that the conductive thin wire portion contains particles of a specific polymer.
  • a polymer (copolymer) represented by the following general formula (1) is preferable.
  • A, B, C, and D each represent a repeating unit represented by the following general formulas (A) to (D).
  • R 11 represents a methyl group or a halogen atom, and preferably a methyl group, a chlorine atom, or a bromine atom.
  • p represents an integer of 0 to 2, preferably 0 or 1, and more preferably 0.
  • R 12 represents a methyl group or an ethyl group, preferably a methyl group.
  • R 13 represents a hydrogen atom or a methyl group, preferably a hydrogen atom.
  • L represents a divalent linking group, and is preferably a group represented by the following general formula (2).
  • X 1 represents an oxygen atom or -NR 30 -.
  • R 30 represents a hydrogen atom, an alkyl group, an aryl group, or an acyl group, each of which may have a substituent (eg, a halogen atom, a nitro group, and a hydroxyl group).
  • R 30 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms (e.g., methyl group, ethyl group, n-butyl group, and n-octyl group), or an acyl group (e.g., acetyl group, and benzoyl group) is preferred.
  • X 1 is preferably an oxygen atom or -NH-.
  • X 2 represents an alkylene group, an arylene group, an alkylene arylene group, an arylene alkylene group, or an alkylene arylene alkylene group, and these groups include -O-, -S-, -CO-, -COO-, -NH -, -SO 2 -, -N(R 31 )-, -N(R 31 )SO 2 -, etc. may be inserted in the middle.
  • R 31 represents a linear or branched alkyl group having 1 to 6 carbon atoms.
  • X 2 is dimethylene group, trimethylene group, tetramethylene group, o-phenylene group, m-phenylene group, p-phenylene group, -CH 2 CH 2 OCOCH 2 CH 2 -, or -CH 2 CH 2 OCO ( C 6 H 4 )- is preferred.
  • r represents 0 or 1.
  • q represents 0 or 1, preferably 0.
  • R 14 represents an alkyl group, an alkenyl group, or an alkynyl group, preferably an alkyl group having 5 to 50 carbon atoms, more preferably an alkyl group having 5 to 30 carbon atoms, and still more preferably an alkyl group having 5 to 20 carbon atoms.
  • R 15 represents a hydrogen atom, a methyl group, an ethyl group, a halogen atom, or -CH 2 COOR 16 , preferably a hydrogen atom, a methyl group, a halogen atom, or -CH 2 COOR 16 ; , or -CH 2 COOR 16 is more preferred, and a hydrogen atom is even more preferred.
  • R 16 represents a hydrogen atom or an alkyl group having 1 to 80 carbon atoms, and may be the same as or different from R 14 , and the carbon number of R 16 is preferably 1 to 70, more preferably 1 to 60.
  • x, y, z, and w represent the molar ratio of each repeating unit.
  • x is 3 to 60 mol%, preferably 3 to 50 mol%, and more preferably 3 to 40 mol%.
  • y is 30 to 96 mol%, preferably 35 to 95 mol%, and more preferably 40 to 90 mol%.
  • z is 0.5 to 25 mol%, preferably 0.5 to 20 mol%, and more preferably 1 to 20 mol%.
  • w is 0.5 to 40 mol%, preferably 0.5 to 30 mol%.
  • x is preferably 3 to 40 mol%
  • y is 40 to 90 mol%
  • z is 0.5 to 20 mol%
  • w is 0.5 to 10 mol%.
  • the polymer represented by the general formula (1) is preferably a polymer represented by the following general formula (2).
  • the polymer represented by the general formula (1) may contain repeating units other than the repeating units represented by the above-mentioned general formulas (A) to (D).
  • monomers for forming other repeating units include acrylic acid esters, methacrylic acid esters, vinyl esters, olefins, crotonic acid esters, itaconic acid diesters, maleic acid diesters, and fumaric acid diesters.
  • examples include acrylamides, unsaturated carboxylic acids, allyl compounds, vinyl ethers, vinyl ketones, vinyl heterocyclic compounds, glycidyl esters, and unsaturated nitriles. These monomers are also described in paragraphs 0010 to 0022 of Japanese Patent No. 3754745.
  • the polymer represented by general formula (1) preferably contains a repeating unit represented by general formula (E).
  • L E represents an alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 2 to 6 carbon atoms, and even more preferably an alkylene group having 2 to 4 carbon atoms.
  • a polymer represented by the following general formula (3) is particularly preferable.
  • a1, b1, c1, d1, and e1 represent the molar ratio of each repeating unit, a1 is 3 to 60 (mol%), b1 is 30 to 95 (mol%), and c1 is 0.5 ⁇ 25 (mol%), d1 represents 0.5 to 40 (mol%), and e1 represents 1 to 10 (mol%).
  • the preferable range of a1 is the same as the above-mentioned preferable range of x
  • the preferable range of b1 is the same as the above-mentioned preferable range of y
  • the preferable range of c1 is the same as the above-mentioned preferable range of z
  • the preferable range of d1 is the same as the above-mentioned preferable range of y.
  • the preferred range is the same as the preferred range for w described above.
  • e1 is 1 to 10 mol%, preferably 2 to 9 mol%, and more preferably 2 to 8 mol%.
  • the specific polymer can be synthesized with reference to, for example, Japanese Patent No. 3305459 and Japanese Patent No. 3754745.
  • the weight average molecular weight of the specific polymer is not particularly limited, and is preferably 1,000 to 1,000,000, more preferably 2,000 to 750,000, and even more preferably 3,000 to 500,000.
  • the conductive thin wire portion may contain other materials than the above-mentioned materials, if necessary.
  • antistatic agents for example, antistatic agents, nucleation accelerators, spectral sensitizing dyes, surfactants, antifoggants, hardeners, black spot prevention agents, as described in paragraphs 0220 to 0241 of JP-A-2009-004348.
  • agents for example, agents, redox compounds, monomethine compounds, and dihydroxybenzenes.
  • the photosensitive layer may contain physical development nuclei.
  • the conductive thin wire portion may contain a crosslinking agent used for crosslinking the above-mentioned specific polymers. By including the crosslinking agent, crosslinking between the specific polymers progresses, and the metals in the conductive thin wire portion are kept connected to each other.
  • the line width Wa of the conductive thin wire portion is preferably less than 5.0 ⁇ m, more preferably 2.5 ⁇ m or less, and even more preferably 2.0 ⁇ m or less, since the conductive thin wire portion is difficult to be visually recognized.
  • the lower limit is not particularly limited, it is preferably 0.5 ⁇ m or more, and more preferably 1.2 ⁇ m or more, since the conductivity of the conductive thin wire portion is more excellent.
  • the line width of the conductive thin wire portion refers to the total length of the conductive thin wire portion in the direction along the surface of the base material and perpendicular to the direction in which the conductive thin wire portion extends.
  • the line width Wa of the conductive thin wire portion described above is determined by selecting five arbitrary points corresponding to the line width of one conductive thin wire portion using a scanning electron microscope, and calculating the arithmetic average of the line widths of the five points. Let the value be the line width Wa.
  • the thickness T of the conductive thin wire portion is not particularly limited, but is preferably 0.5 to 3.0 ⁇ m, more preferably 1.0 to 2.0 ⁇ m.
  • the thickness T of the conductive thin wire portion described above can be measured according to the method for measuring the thickness of a conductive layer.
  • the wire resistance value of the conductive thin wire portion is preferably less than 200 ⁇ /mm. Among these, from the viewpoint of operability when used as a touch panel, it is more preferably less than 100 ⁇ /mm, and even more preferably less than 60 ⁇ /mm.
  • the wire resistance value is the resistance value measured by the four-probe method divided by the distance between the measurement terminals. More specifically, after disconnecting both ends of any one conductive thin wire part constituting the mesh pattern and separating it from the mesh pattern, four microprobes (A, B, C, D) (Co., Ltd.
  • the conductive layer has a transparent insulating portion adjacent to the conductive thin wire portion. As shown in FIG. 1, the conductive thin wire portion and the transparent insulating portion are arranged side by side in the in-plane direction on the surface of the substrate.
  • the transparent insulating portion is a region that does not contain conductive metal and does not exhibit conductivity.
  • the expression that the transparent insulating part "does not contain metal” means that the metal content in the transparent insulating part is 0.1% by mass or less based on the total mass of the transparent insulating part.
  • the metal content in the transparent insulating part is preferably 0.05% by mass or less based on the total mass of the transparent insulating part.
  • transparent means that the average transmittance of visible light with a wavelength of 400 to 700 nm is 80% or more.
  • the average transmittance of the visible light of the transparent insulating portion is preferably 90% or more.
  • the upper limit is not particularly limited, and is, for example, 99% or less. Transmittance can be measured using a spectrophotometer.
  • the transparent insulating portion preferably contains a polymer compound as a main component.
  • the polymer compound contained in the transparent insulating part include those contained in the conductive thin wire part, and specific polymers are preferable. Among these, it is more preferable to include the same polymer compound (preferably a specific polymer) contained in the conductive thin wire portion.
  • the expression that the transparent insulating part "contains a polymer compound as a main component" means that the content of the polymer compound is 50% by mass or more based on the total mass of the transparent insulating part.
  • the content of the polymer compound in the transparent insulating part is preferably 90% by mass or more, more preferably 95% by mass or more.
  • the upper limit is not particularly limited and may be 100% by mass.
  • the method for forming the transparent insulating portion is not particularly limited, and for example, in the method for manufacturing a conductive substrate described below, an unexposed portion may be formed by performing an exposure treatment in which a silver halide-containing photosensitive layer is exposed in a pattern. Then, by performing a development process on the unexposed area, a transparent insulating part containing a polymer compound as a main component is formed. In addition, by performing a treatment to remove gelatin as necessary, a transparent insulating portion containing a specific polymer as a main component is formed.
  • the conductive substrate may include other members in addition to the above-described base material, conductive thin wire portion, and transparent insulating portion.
  • Other members that may be included in the conductive substrate include a conductive portion having a different configuration from the conductive thin wire portion described below.
  • the conductive layer contains a compound represented by the following formula (1), formula (2), formula (3), or formula (4) (hereinafter also referred to as a "specific compound").
  • R 1 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a C 1 to 6 alkyl group. Represents an alkoxy group, an alkylthio group having 1 to 3 carbon atoms, an amino group, a hydroxyl group, or a carboxylic acid group.
  • R 2 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an amino group.
  • R 3 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms and having at least one substituent selected from the group consisting of a carboxylic acid group, a hydroxyl group, and an amino group.
  • the sulfidation resistance of the conductive thin wire portion is improved. More specifically, as mentioned above, in conductive substrates mounted on electronic devices such as touch panels, sulfur compounds originating from surrounding members or the surrounding environment permeate into the conductive layer and cause the conductive thin wires to penetrate into the conductive layer. It is thought that the conductivity of the conductive thin wire portion decreases as a result of reacting with the thin metal wire in the conductive wire portion to form sulfide.
  • the sulfur compound that has penetrated into the conductive layer from the outside reacts with the specific compound and combines with it, resulting in sulfur resistance that suppresses sulfurization of the thin metal wire in the conductive thin wire section. It is assumed that this will improve.
  • the fact that the conductive thin wire portion has excellent sulfurization resistance is also referred to as "the effect of the present invention is excellent.”
  • R 1 is preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and more preferably a hydrogen atom, a methyl group, an ethyl group, or a phenyl group, since the effects of the present invention are more excellent. .
  • R 1 is an alkyl group having 1 to 6 carbon atoms, a phenyl group, an alkoxy group having 1 to 6 carbon atoms, a thioalkyl group having 1 to 3 carbon atoms, an amino group, A hydroxyl group or a carboxylic acid group is preferable, an alkyl group having 1 to 6 carbon atoms, or a phenyl group is more preferable, and a methyl group, a propan-2-yl group, or a phenyl group is preferable because the effects of the present invention are more excellent. More preferred are groups.
  • Specific compounds represented by formula (1) include, for example, 5-methyl-1,3,4-thiadiazole-2-thiol, 5-ethyl-1,3,4-thiadiazole-2-thiol, 5-( propan-2-yl)-1,3,4-thiadiazole-2-thiol, 5-phenyl-1,3,4-thiadiazole-2-thiol, 5-amino-1,3,4-thiadiazole-2-thiol , and 5-(methylthio)-1,3,4-thiadiazole-2-thiol.
  • 5-methyl-1,3,4-thiadiazole-2-thiol, 5-(propan-2-yl)-1,3,4-thiadiazole-2-thiol, or 5-phenyl-1,3 ,4-thiadiazole-2-thiol is preferred, and 5-methyl-1,3,4-thiadiazole-2-thiol is more preferred.
  • Specific compounds represented by formula (2) include 3-mercapto-1H-1,2,4-triazole, 1-methyl-1,2,4-triazole-3-thiol, 5-amino-1H-1 , 2,4-triazole-3-thiol, 5-methyl-1H-1,2,4-triazole-3-thiol, and 5-ethyl-1H-1,2,4-triazole-3-thiol. It will be done. Among them, 3-mercapto-1H-1,2,4-triazole is preferred.
  • Specific compounds represented by formula (3) include 3-methyl-4H-1,2,4-triazole-5-thiol, 4-methyl-1,2,4-triazole-3-thiol, 4,5 -dimethyl-1,2,4-triazole-3-thiol, 4-amino-1,2,4-triazol-3-thiol, 5-mercapto-4H-1,2,4-triazol-3-ol, 4 -Ethyl-1,2,4-triazole-3-thiol, 5-ethyl-4H-1,2,4-triazole-3-thiol, 4-amino-5-methyl-1,2,4-triazole-3 -thiol, 5-amino-4-methyl-1,2,4-triazole-3-thiol, 5-mercapto-4-methyl-1,2,4-triazol-3-ol, 5-ethyl-4-methyl -1,2,4-triazole-3-thiol, 3-isopropyl-4H-1,2,4-triazole-5-thiol, 4-ethyl
  • Specific compounds represented by formula (4) include 1,2,3-benzotriazole, 5-methylbenzotriazole, 4-methylbenzotriazole, 2,2'-(4-methyl-1H-benzotriazole-1 -ylmethylimino)bisethanol, 2,2'-(5-methyl-1H-benzotriazol-1-ylmethylimino)bisethanol, 1-(1',2'-dicarboxyethyl)benzotriazole, 1- Examples include (2,3-dicarboxypropyl)benzotriazole, 5-carboxybenzotriazole, 5,6-dimethylbenzotriazole, and 5-aminobenzotriazole. Among them, 1,2,3-benzotriazole, 5-methylbenzotriazole, 4-methylbenzotriazole, or 2,2'-(4-methyl-1H-benzotriazol-1-ylmethylimino)bisethanol preferable.
  • the specific compound has the above formula (The specific compound represented by 4) is preferable, and 1,2,3-benzotriazole or 5-methylbenzotriazole is more preferable.
  • a compound represented by the following formula (1a) can be mentioned.
  • the specific compound herein includes the compound represented by formula (1) as well as the proton tautomer of the compound represented by formula (1) represented by formula (1a). shall be held.
  • the specific compound in this specification refers to the proton tautomer of the compound represented by the formula (2) represented by the compound represented by the following formula (2a), and the proton tautomer of the compound represented by the following formula (2a).
  • the proton tautomer of the compound represented by formula (3) represented by the compound represented by (3a) is also included.
  • R 1 in formula (1a), formula (2a) and formula (3a) is the same as R 1 in formula (1), formula (2) and formula (3) above.
  • R 2 in formula (2a) and formula (3a) is the same as R 2 in formula (2) and formula (3) above.
  • the number of specific compounds contained in the conductive layer may be one, or two or more.
  • the content of the specific compound contained in the conductive layer is preferably 0.005 ⁇ g/cm 2 or more per area of the conductive layer, more preferably 0.01 ⁇ g/cm 2 or more, in that the effect of the present invention is more excellent. More preferably, it is 0.02 ⁇ g/cm 2 or more.
  • the upper limit of the content of the specific compound is not particularly limited, but it is preferably 8.0 ⁇ g/cm 2 or less per area of the conductive layer, since it is more effective in suppressing color change of the conductive substrate after long-term storage.
  • the mixing ratio when using two or more types of specific compounds may be arbitrarily adjusted as long as the content of the specific compounds contained in the conductive layer is within the above range.
  • the ratio of the content of one specific compound to the content of another specific compound may be, for example, 0.01 to 200 in terms of mass ratio.
  • the specific compound may be contained in both the conductive thin wire portion and the transparent insulating portion that constitute the conductive layer, it is preferably contained in at least the transparent insulating portion.
  • the content of the specific compound contained in the conductive layer can be measured by immersing the conductive substrate having the conductive layer in a solvent, extracting the specific compound, and then quantifying the content of the specific compound in the solvent. .
  • a detailed method for measuring the content of the specific compound will be described in the Examples below.
  • the conductive layer may contain compounds other than the specific compound.
  • examples include benzimidazole, benzoxazole, benzothiazole, 2-mercaptobenzimidazole, sodium 2-mercapto-5-benzimidazole sulfonate, 2-mercaptobenzoxazole, and 2-mercaptobenzothiazole.
  • benzimidazole, benzoxazole, and benzothiazole are preferred.
  • Other compounds are preferably those that suppress the decomposition of the specific compound, and more preferably those that stabilize the specific compound by forming electrostatic interactions with the specific compound such as hydrogen bonds and ⁇ - ⁇ interactions. preferable.
  • the mixing ratio when the specific compound and the above-mentioned other compounds are used together may be arbitrarily adjusted as long as the content of the specific compound contained in the conductive layer is within the above-mentioned content range.
  • the ratio of the content of other compounds to the content of the specific compound is preferably 0.01 to 200 by mass, more preferably 0.1 to 20, and even more preferably 0.5 to 10.
  • the content of other compounds other than the specific compound can be measured according to the method described as a method for measuring the content of the specific compound.
  • a method of bringing a specific compound into contact with the conductive layer is preferred.
  • a method in which a specific compound is brought into contact with the conductive layer in step P described below is more preferable.
  • the content of the specific compound contained in the conductive thin wire portion is not particularly limited, but the ratio A of the content of the specific compound to the metal content in the conductive thin wire portion (metal content)) is preferably from 0.05 to 8.0, more preferably from 0.1 to 5.0, and more preferably from 0.2 to 5.0. More preferred.
  • the sulfurization resistance of the conductive thin wire portion can be further improved, especially when the conductive substrate is stored in the form of a laminate with other members such as an adhesive sheet and a release sheet.
  • the sulfurization resistance of the conductive thin wire portion can be further improved.
  • the ratio A is preferably equal to or less than the above upper limit because the effect of suppressing color change of the conductive substrate after long-term storage is more excellent.
  • the above ratio A in the conductive thin wire portion is measured by analyzing the conductive thin wire portion using a time-of-flight secondary ion mass spectrometer (TOF-SIMS). be exposed.
  • TOF-SIMS time-of-flight secondary ion mass spectrometer
  • the method for measuring the content A of the specific compound will be explained in more detail.
  • secondary ions fragment peaks
  • TOF-SIMS time-of-flight secondary ion mass spectrometer
  • the amount of specific compound and the amount of metal are determined.
  • fragment peaks derived from metals those of zero-valent metals (for example, metallic silver, etc.) and metal anions (for example, silver iodide, etc.) contained in the conductive thin wire are used.
  • the maximum value of the fragment peak intensity of the specific compound present in the conductive thin wire portion is calculated as B, and the maximum value of the fragment peak intensity derived from the metal is calculated as C.
  • the method for manufacturing the conductive substrate is not particularly limited as long as the conductive substrate having the above-mentioned configuration can be manufactured, and a known method may be employed. For example, a method of exposing and developing using silver halide, forming a metal-containing layer on the entire surface of the support, and then removing a part of the metal-containing layer using a resist pattern to form a thin line-shaped metal-containing layer. and a method in which a thin line-shaped metal-containing layer is formed by discharging a composition containing a metal and a resin onto a substrate using a known printing method such as inkjet printing.
  • a method in which exposure and development are performed using silver halide is preferred in terms of productivity and superior conductivity of the conductive thin wire portion.
  • a method for manufacturing a conductive substrate that includes steps A to D which will be described later, in this order.
  • steps A to D which will be described later, in this order.
  • a method for manufacturing a conductive substrate having steps A to D will be described in detail, but the method for manufacturing a conductive substrate according to the present invention is not limited to the following manufacturing method.
  • step A a silver halide-containing photosensitive layer (hereinafter also referred to as "photosensitive layer”) containing silver halide, gelatin, and a specific polymer (a polymer compound different from gelatin) is formed on a base material.
  • photosensitive layer a silver halide-containing photosensitive layer
  • a specific polymer a polymer compound different from gelatin
  • the halogen atom contained in the silver halide may be any of a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom, or a combination of these may be used.
  • silver halide mainly composed of silver chloride, silver bromide or silver iodide is preferred, and silver halide mainly composed of silver chloride or silver bromide is more preferred.
  • silver chlorobromide, silver iodochlorobromide, and silver iodobromide are also preferably used.
  • silver halide mainly composed of silver chloride refers to silver halide in which the molar fraction of chloride ions to all halide ions in the silver halide composition is 50% or more.
  • This silver halide mainly composed of silver chloride may contain bromide ions and/or iodide ions in addition to chloride ions.
  • the silver halide may contain a metal compound other than silver, and compounds described in paragraphs 0031 to 0038 of JP-A No. 2006-332459 can be preferably used.
  • the silver halide is subjected to chemical sensitization treatment using a chemical sensitizer exemplified in paragraphs 0039 to 0045 of JP-A No. 2006-332459.
  • a chemical sensitizer exemplified in paragraphs 0039 to 0045 of JP-A No. 2006-332459.
  • Silver halide is usually in the form of solid particles, and the average particle diameter of silver halide is preferably 10 to 1000 nm, more preferably 10 to 300 nm, in equivalent sphere diameter.
  • the grain size of the silver halide it is possible to reduce light scattering by the silver halide particles when exposing the silver halide photosensitive layer in step B described below, so the line width of the conductive thin line due to light scattering can be reduced. This is preferable because it can suppress the increase in .
  • the silver halide grain size is made too small, the surface area of the developed silver formed in step B will increase, and there is a risk that surface adsorbed matter will increase, which will cause a decrease in conductivity.
  • the average particle diameter is preferably in the above range.
  • the spherical equivalent diameter is the diameter of spherical particles having the same volume.
  • the "equivalent sphere diameter" used as the average particle diameter of the silver halide mentioned above is an average value, which is the arithmetic average of 100 equivalent sphere diameters of silver halide measured.
  • the shape of the silver halide grains is not particularly limited, and examples thereof include spherical, cubic, tabular (hexagonal tabular, triangular tabular, quadrilateral tabular, etc.), octahedral, and tetradecahedral.
  • octahedral octahedral
  • tetradecahedral tetradecahedral
  • gelatin The type of gelatin is not particularly limited, and examples include lime-treated gelatin and acid-treated gelatin. Further, gelatin hydrolysates, gelatin enzymatically decomposed products, gelatin modified with amino groups and/or carboxy groups (phthalated gelatin, acetylated gelatin), etc. may be used.
  • the photosensitive layer contains the above-mentioned specific polymer.
  • this specific polymer By including this specific polymer in the photosensitive layer, the strength of the conductive thin wire portion and the transparent insulating portion formed from the photosensitive layer is further improved.
  • the method for forming the photosensitive layer containing the above-mentioned components in Step A is not particularly limited, but from the viewpoint of productivity, a composition for forming a photosensitive layer containing silver halide, gelatin, and a specific polymer is coated on the base material.
  • a preferred method is to form a photosensitive layer on a substrate by bringing it into contact with the substrate.
  • the composition for forming a photosensitive layer contains the above-mentioned silver halide, gelatin, and specific polymer. Note that, if necessary, the specific polymer may be contained in the composition for forming a photosensitive layer in the form of particles.
  • the composition for forming a photosensitive layer may contain a solvent as necessary. Examples of the solvent include water, organic solvents (for example, alcohols, ketones, amides, sulfoxides, esters, and ethers), ionic liquids, and mixed solvents thereof.
  • the method of bringing the composition for forming a photosensitive layer into contact with the base material is not particularly limited. Examples include a method of dipping the base material. Note that after the above-mentioned treatment, a drying treatment may be performed as necessary.
  • the photosensitive layer formed by the above procedure contains silver halide, gelatin, and a specific polymer.
  • the content of silver halide in the photosensitive layer is not particularly limited, and is preferably 3.0 to 20.0 g/m 2 in terms of silver, and 5.0 to 15 g/m 2 in terms of silver, since the conductive substrate has better conductivity. .0 g/m 2 is more preferred.
  • Silver conversion means conversion into the mass of silver produced by reducing all of the silver halide.
  • the content of the specific polymer in the photosensitive layer is not particularly limited, and is preferably 0.04 to 2.0 g/m 2 and 0.08 to 0.40 g/m 2 in terms of better conductivity of the conductive substrate. m 2 is more preferable, and 0.10 to 0.40 g/m 2 is even more preferable.
  • a single silver halide photosensitive layer may be used, it is also preferable to laminate a plurality of photosensitive layers as necessary.
  • a layer closer to the light source when exposing the photosensitive layer (hereinafter referred to as the "upper layer") is opposed to a layer farther from the light source (hereinafter referred to as the "lower layer”).
  • the sensor it is preferable to design the sensor to increase its sensitivity. The intensity of light reaching the lower layer decreases due to absorption and scattering by the silver halide in the upper layer, so by increasing the sensitivity of the lower layer, the lower photosensitive layer can be exposed to even the lower intensity light. This is preferable because the amount of silver per constant line width of the conductive thin wire can be increased.
  • the grain size of the silver halide grains in the upper layer is smaller than that of the silver halide grains in the lower layer.
  • the problem of the light scattering of the upper layer silver halide grains expanding the irradiation area of the light reaching the lower layer and increasing the line width of the conductive thin wire can be suppressed by reducing the grain size of the upper layer silver halide grains. That's preferable.
  • the surface area of developed silver can be reduced compared to when the grain size of the silver halide grains in the lower layer is made smaller. This is preferable because it can reduce the amount of adsorbed substances.
  • the preferable sensitivity ratio between the upper and lower silver halide photosensitive layers is determined by the light absorption and scattering properties that vary depending on the particle size of the silver halide grains, halogen composition, thickness of the photosensitive layer, wavelength of the light source used for exposure, etc. Therefore, the sensitivity of the lower layer relative to the sensitivity of the upper layer is preferably in the range of 1.1 to 10 times, and more preferably in the range of 1.5 to 4 times, although it cannot be generalized. Further, the average particle diameter of the silver halide is preferably in the range of 40 to 180 nm in the upper layer and 100 to 300 nm in the lower layer.
  • Step B is a step of exposing the photosensitive layer to light and then developing it to form a thin line-shaped silver-containing layer containing metallic silver, gelatin, and a specific polymer.
  • the method of development treatment is not particularly limited, and examples thereof include known methods used for silver salt photographic films, photographic papers, films for printing plates, and emulsion masks for photomasks.
  • a developer is usually used.
  • the type of developer is not particularly limited, and examples include PQ (phenidone hydroquinone) developer, MQ (metol hydroquinone) developer, and MAA (methol ascorbic acid) developer.
  • This step may further include a fixing treatment performed for the purpose of removing and stabilizing silver halide in unexposed areas.
  • the fixing process is performed simultaneously with and/or after the development.
  • the fixing treatment method is not particularly limited, and examples thereof include methods used for silver salt photographic films, photographic paper, printing plate-making films, and emulsion masks for photomasks.
  • a fixing solution is usually used.
  • the type of fixer is not particularly limited, and examples thereof include the fixer described in "Chemistry of Photography" (written by Sasai, published by Photo Industry Publishing Co., Ltd.), p. 321.
  • the width of the silver-containing layer is preferably 1.0 ⁇ m or more and less than 5.0 ⁇ m, and more preferably 2.0 ⁇ m or less since the formed conductive thin wire portion is difficult to be visually recognized.
  • the silver-containing layer obtained by the above procedure is in the form of a thin line, and the width of the silver-containing layer refers to the length (width) of the silver-containing layer in the direction perpendicular to the direction in which the thin line-shaped silver-containing layer extends. means.
  • the superheated steam may be superheated steam or a mixture of superheated steam and other gas.
  • the contact time between the superheated steam and the silver-containing layer is not particularly limited, and is preferably 10 to 70 seconds.
  • the amount of superheated steam supplied is preferably 500 to 600 g/m 3 , and the temperature of superheated steam is preferably 100 to 160°C (preferably 100 to 120°C) at 1 atmosphere.
  • the heating conditions in the method of heating the silver-containing layer etc. with a temperature adjustment device are preferably heating at 100 to 200 °C (preferably 100 to 150 °C) for 1 to 240 minutes (preferably 60 to 150 minutes).
  • the proteolytic enzyme used in Method 1 includes known plant or animal enzymes that can hydrolyze proteins such as gelatin.
  • proteolytic enzymes include pepsin, rennin, trypsin, chymotrypsin, cathepsin, papain, ficin, thrombin, renin, collagenase, bromelain, and bacterial protease, with trypsin, papain, ficin, or bacterial protease being preferred.
  • the procedure in Method 1 may be any method as long as it brings the silver-containing layer etc. into contact with the above-mentioned protease. ).
  • the contact method include a method in which the silver-containing layer, etc.
  • the oxidizing agent used in method 2 may be any oxidizing agent that can decompose gelatin, and preferably has a standard electrode potential of +1.5 V or more.
  • the standard electrode potential herein refers to the standard electrode potential (25° C., E0) relative to a standard hydrogen electrode in an aqueous solution of an oxidizing agent.
  • oxidizing agents include persulfuric acid, percarbonic acid, perphosphoric acid, hypoperchloric acid, peracetic acid, metachloroperbenzoic acid, hydrogen peroxide, perchloric acid, periodic acid, potassium permanganate,
  • Examples include ammonium persulfate, ozone, hypochlorous acid or its salts, but from the viewpoint of productivity and economy, hydrogen peroxide (standard electrode potential: 1.76V), hypochlorous acid or its salts are preferable. , sodium hypochlorite is more preferred.
  • the method for manufacturing a conductive substrate may include a step E in which the silver-containing layer obtained in step D is subjected to a plating treatment. By carrying out this step, the space inside the silver-containing layer formed by removing gelatin can be filled with metal (plated metal), and the conductivity of the conductive thin wire portion can be improved.
  • the type of plating treatment is not particularly limited, but includes electroless plating (chemical reduction plating or displacement plating) and electrolytic plating, with electroless plating being preferred.
  • electroless plating a known electroless plating technique is used.
  • the plating treatment include silver plating treatment, copper plating treatment, nickel plating treatment, and cobalt plating treatment, and silver plating treatment or copper plating treatment is preferable because the conductivity of the conductive thin wire portion is better. , silver plating treatment is more preferred.
  • the components contained in the plating solution used in the plating process are not particularly limited, but usually, in addition to a solvent (for example, water), 1. Metal ions for plating, 2. reducing agent, 3. Additives (stabilizers) that improve the stability of metal ions; 4. Mainly contains pH adjusters.
  • the plating bath may contain known additives such as a plating bath stabilizer.
  • the type of metal ion for plating contained in the plating solution can be appropriately selected depending on the type of metal to be deposited, and examples thereof include silver ion, copper ion, nickel ion, and cobalt ion.
  • the method for manufacturing a conductive substrate may include a step F in which the silver-containing layer obtained in the above step is further subjected to a smoothing treatment.
  • the method of smoothing treatment is not particularly limited, and for example, a calendar treatment step in which a base material having a silver-containing layer or the like is passed between at least a pair of rolls under pressure is preferred.
  • calender process the smoothing process using a calender roll will be referred to as calender process.
  • Rolls used for calendering include plastic rolls and metal rolls, with plastic rolls being preferred from the viewpoint of wrinkle prevention.
  • the pressure between the rolls is not particularly limited, and is preferably 2 MPa or more, more preferably 4 MPa or more, and preferably 120 MPa or less. Note that the pressure between the rolls can be measured using Prescale (for high pressure) manufactured by Fujifilm Corporation.
  • the temperature of the smoothing treatment is not particularly limited, and is preferably 10 to 100°C, more preferably 10 to 50°C.
  • the method for manufacturing a conductive substrate may include a step G of subjecting the silver-containing layer etc. obtained in the above steps to a heat treatment. By carrying out this step, a conductive thin wire portion with better conductivity can be obtained.
  • the method of heat-treating the conductive thin wire portion is not particularly limited, and the method described in Step C may be used.
  • the method for producing a conductive substrate may include, before Step A, Step H of forming a silver halide-free layer containing gelatin and a specific polymer on the base material.
  • Step H of forming a silver halide-free layer containing gelatin and a specific polymer on the base material.
  • a silver halide-free layer is formed between the substrate and the silver halide-containing photosensitive layer.
  • This silver halide-free layer plays the role of a so-called antihalation layer and also contributes to improving the adhesion between the conductive layer and the base material.
  • the silver halide-free layer contains the above-mentioned gelatin and specific polymer. On the other hand, the silver halide-free layer does not contain silver halide.
  • the ratio of the mass of the specific polymer to the mass of gelatin (mass of specific polymer/mass of gelatin) in the silver halide-free layer is not particularly limited, and is preferably 0.1 to 5.0, and 1. More preferably 0 to 3.0.
  • the content of the specific polymer in the silver halide-free layer is not particularly limited, and is often 0.03 g/m 2 or more. 2 or more is preferred.
  • the upper limit is not particularly limited, but is often 1.63 g/m 2 or less.
  • the method for producing a conductive substrate may include, after step A and before step B, step I of forming a protective layer containing gelatin and a specific polymer on the silver halide-containing photosensitive layer.
  • a protective layer By providing a protective layer, the scratch prevention and mechanical properties of the photosensitive layer can be improved.
  • the ratio of the mass of the specific polymer to the mass of gelatin in the protective layer is not particularly limited, and is preferably greater than 0 and less than or equal to 2.0, and more than 0 and less than or equal to 1.0. More preferred.
  • the content of the specific polymer in the protective layer is not particularly limited, and is preferably more than 0 g/m 2 and 0.3 g/m 2 or less, and more preferably 0.005 to 0.1 g/m 2 .
  • the method of forming the protective layer is not particularly limited, and for example, a method of applying a protective layer-forming composition containing gelatin and a specific polymer onto a silver halide-containing photosensitive layer and subjecting it to a heat treatment if necessary. can be mentioned.
  • the composition for forming a protective layer may contain a solvent as necessary. Examples of the solvent include those used in the photosensitive layer forming composition described above.
  • the thickness of the protective layer is not particularly limited, and is preferably 0.03 to 0.3 ⁇ m, more preferably 0.075 to 0.20 ⁇ m.
  • Step H, Step A, and Step I described above may be performed simultaneously by simultaneous multilayer coating.
  • the method for manufacturing a conductive substrate includes a step P of bringing a specific compound into contact with the conductive layer formed on the above-mentioned base material to produce the conductive substrate of the present invention in which the conductive layer contains the specific compound.
  • the method of bringing the conductive layer into contact with the specific compound is not particularly limited, and examples include a method of immersing the base material on which the conductive layer is formed in a treatment solution containing the specific compound, and a method of bringing the conductive layer into contact with the specific compound. Examples include a method of coating the surface of a base material on which a conductive layer is formed.
  • the treatment liquid containing the above-mentioned specific compound is preferably a solution obtained by dissolving the specific compound in a solvent.
  • the type of solvent used is not particularly limited, and examples thereof include the solvents used in the photosensitive layer forming composition described above.
  • Preferred solvents include alcohols and ethers.
  • Specific examples of preferred solvents include ethanol, 1-propanol, 2-propanol, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monopropyl ether, and diethylene glycol monobutyl ether.
  • this conductive substrate other than those mentioned above include, for example, electromagnetic shielding that blocks electromagnetic waves such as radio waves and microwaves (ultra-high frequency waves) generated from electronic devices such as personal computers and workstations, and prevents static electricity. It will be done.
  • electromagnetic shield can be used not only for personal computers but also for electronic equipment such as video imaging equipment and electronic medical equipment.
  • This conductive substrate can also be used for transparent heating elements.
  • the present conductive substrate may be used in the form of a laminate having the conductive substrate and other members such as an adhesive sheet and a release sheet during handling and transportation.
  • the release sheet functions as a protective sheet to prevent scratches on the conductive substrate during transportation of the laminate.
  • the adhesive sheet include sheets made of known adhesives used in optical systems, such as optical clear adhesives (OCA) and acrylic adhesives.
  • the conductive substrate may be handled in the form of a composite body including, for example, a conductive substrate, an adhesive sheet, and a protective layer in this order.
  • Example 1 [Preparation of silver halide emulsion A] To the following liquid 1 maintained at 38°C and pH 4.5, an amount equivalent to 90% of each of the following liquids 2 and 3 was added simultaneously over 20 minutes while stirring the liquid 1 to obtain 0.16 ⁇ m core particles. was formed. Next, the following liquids 4 and 5 were added to the obtained solution over 8 minutes, and the remaining 10% of the following liquids 2 and 3 were added over 2 minutes to grow the core particles to 0.21 ⁇ m. I let it happen. Furthermore, 0.15 g of potassium iodide was added to the obtained solution and aged for 5 minutes to complete particle formation.
  • the final emulsion contains 0.08 mol% of silver iodide, and the ratio of silver chlorobromide is 70 mol% of silver chloride and 30 mol% of silver bromide, and has an average grain size (equivalent sphere diameter). It was a silver chlorobromide cubic grain emulsion with a particle diameter of 200 nm and a coefficient of variation of 9%.
  • the resulting emulsion is also referred to as "silver halide emulsion A" or simply "emulsion A.”
  • a polymer represented by the following structural formula (P-1) (hereinafter also referred to as "polymer 1") and dialkylphenyl PEO (PEO is an abbreviation for polyethylene oxide) sulfuric ester.
  • a polymer latex containing a dispersant and water (the ratio of the mass of the dispersant to the mass of polymer 1 (mass of dispersant/mass of polymer 1, unit: g/g) is 0.02, solid content is 22% by mass), and the ratio of the mass of polymer 1 to the total mass of gelatin in the composition (mass of polymer 1/mass of gelatin, unit g/g) is 0.
  • a polymer latex-containing composition was obtained by adding at a ratio of 25/1.
  • the ratio of the mass of gelatin to the mass of silver derived from silver halide is 0. It was 11. Furthermore, EPOXY RESIN DY 022 (trade name: manufactured by Nagase ChemteX Co., Ltd.) as a crosslinking agent was added to the above polymer latex-containing composition. The amount of the crosslinking agent added was adjusted so that the amount of the crosslinking agent in the silver halide-containing photosensitive layer described below was 0.09 g/m 2 .
  • a composition for forming a photosensitive layer was prepared as described above. In addition, polymer 1 was synthesized with reference to Japanese Patent No. 3305459 and Japanese Patent No. 3754745.
  • undercoat layer The above-mentioned polymer latex was applied to the surface of a base material made of a polyethylene terephthalate film having a thickness of 40 ⁇ m (“rolled long film manufactured by Fuji Film Corporation”) to provide an undercoat layer having a thickness of 0.05 ⁇ m. This treatment was performed roll-to-roll, and the following treatments (steps) were similarly performed roll-to-roll. Note that the roll width at this time was 1 m and the length was 1000 m.
  • the thickness of the silver halide-free layer is 2.0 ⁇ m, and the mixing mass ratio of polymer 1 and gelatin in the silver halide-free layer (polymer 1/gelatin) is 2/1.
  • the content of molecule 1 was 1.3 g/ m2 .
  • the thickness of the silver halide-containing photosensitive layer is 2.5 ⁇ m, and the mixing mass ratio of polymer 1 and gelatin (polymer 1/gelatin) in the silver halide-containing photosensitive layer is 0.25/1.
  • the content of polymer 1 was 0.19 g/m 2 .
  • the obtained sample was developed with a developer described below, and further developed using a fixer (trade name: N3X-R for CN16X, manufactured by Fuji Film Corporation). After that, it is rinsed with pure water at 25°C and dried to form a conductive layer containing a conductive thin wire portion containing metallic silver and a transparent insulating portion, and the conductive thin wire portion is formed in a mesh pattern.
  • Sample A of the substrate was obtained. In sample A, a conductive mesh pattern area with a size of 21.0 cm x 29.7 cm was formed.
  • the obtained above-mentioned sample was immersed in warm water at 50°C for 180 seconds. After this, the water was removed using an air shower and the material was allowed to air dry.
  • Step C1 The sample obtained in step B1 was carried into a superheated steam treatment tank at 110° C., and left to stand still for 30 seconds to perform superheated steam treatment. Note that the steam flow rate at this time was 100 kg/h.
  • proteolytic enzyme aqueous solution 40° C.
  • the sample was taken out from the proteolytic enzyme aqueous solution and washed by immersing it in warm water (liquid temperature: 50°C) for 120 seconds. After this, the water was removed using an air shower, and the sample was air-dried.
  • the protease aqueous solution used was prepared according to the following procedure. Triethanolamine and sulfuric acid were added to an aqueous solution (proteolytic enzyme concentration: 0.5% by mass) of a proteolytic enzyme (Bioplase 30L manufactured by Nagase ChemteX) to adjust the pH to 8.5.
  • step D1 The sample obtained in step D1 was carried into a superheated steam treatment tank at 110° C., and left standing for 30 seconds to perform superheated steam treatment. Note that the steam flow rate at this time was 100 kg/h.
  • step G1 The sample obtained in step G1 was immersed in treatment liquid A (40° C.) for 60 seconds. The sample was taken out from treatment solution A and washed by immersing it in water at 25° C. for 50 seconds.
  • the composition of treatment liquid A (total amount: 1200 g) was as follows. The following components used were all manufactured by Fuji Film Wako Pure Chemical Industries, Ltd. (Composition of treatment liquid A) ⁇ 5-Methyl-1,3,4-thiadiazole-2-thiol 2.4g ⁇ Ethanol 90g ⁇ Water remainder
  • step P1 The sample obtained in step P1 was heated at 65° C. for 90 seconds and dried. Through the above steps, a sample of a conductive substrate having a mesh pattern electrode was produced.
  • Examples 2-14, 18-33 When preparing the treatment liquid used in step P1, the mixed solvent listed in Tables 1 and 2 described below was used, and the type and content of the specific compound contained in the treatment liquid and the content of the mixed solvent. Examples 2 to 2 were carried out in accordance with the procedure described in Example 1, except that the content of the specific compound per area of the conductive layer was adjusted as appropriate to the values listed in Tables 1 and 2 below. Samples of conductive substrates Nos. 14 and 18 to 33 were prepared, respectively. All components of the processing liquid used were manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.
  • Example 15 The sample obtained in step D1 of Example 1 was immersed in a plating solution (30° C.) having the following composition for 5 minutes. The sample was taken out from the plating solution and washed by immersing it in warm water (50° C.) for 120 seconds. The composition of the plating solution (total volume 1200 mL) was as follows. The pH of the plating solution was 9.9, which was adjusted by adding a predetermined amount of potassium carbonate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). The following components used were all manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.
  • composition of plating solution ⁇ AgNO3 2.1g ⁇ Sodium sulfite 86g ⁇ Sodium thiosulfate pentahydrate 60g ⁇ Aron T-50 (manufactured by Toagosei Co., Ltd., solid content concentration 40%) 36g ⁇ Methylhydroquinone 7g ⁇ Prescribed amount of potassium carbonate ⁇ Remainder of water
  • the silver halide emulsion B finally obtained contains 0.08 mol% of silver iodide, the ratio of silver chlorobromide is 70 mol% of silver chloride and 30 mol% of silver bromide, and has an average grain size ( It was a silver chlorobromide cubic grain emulsion with an equivalent sphere diameter of 200 nm and a coefficient of variation of 9%.
  • Emulsion C was prepared by changing the temperature of the first liquid, the addition rate of the second and third liquids, and the amounts of materials added as shown below in the method for preparing silver halide emulsion B described above.
  • the name of the material whose addition amount was changed and the addition amount are as follows.
  • the smoothing by a calender was carried out using metal rolls at 25° C. under the condition that the pressure between the rolls was 10 MPa.
  • the only difference was that photosensitive material C was used instead of photosensitive material B, and the exposure amount in step B1 was changed so that the line width of the conductive thin line portion was 2.5 ⁇ m.
  • Samples of conductive substrates were produced using different methods, and the obtained sample was designated as sample C2.
  • the only difference was that photosensitive material D was used instead of photosensitive material B, and the exposure amount in step B1 was changed so that the line width of the conductive thin line portion was 2.5 ⁇ m.
  • Samples of conductive substrates were produced using different methods, and the obtained sample was designated as sample D2.
  • sample D2 in which the photosensitive layer has a two-layer laminated structure, has improved conductivity compared to sample B2 and sample C2, in which the photosensitive layer has a single-layer structure. Furthermore, since the exposure amount when preparing sample C2 was 2.3 times the exposure amount when preparing sample B2, the photosensitive layer using emulsion B was less sensitive than the photosensitive layer using emulsion C. This suggests that the lower emulsion layer of sample D2 has 2.3 times more sensitivity than the upper emulsion layer.
  • the conductivity was calculated by measuring the resistance value (R0) of a sample having a mesh pattern shape by the method described below, and calculating the reciprocal of the obtained resistance value.
  • the ratio A of the specific compound content to the metal content in the conductive thin wire portion of the sample obtained in each example was measured by the following method.
  • Each sample was analyzed using a time-of-flight secondary ion mass spectrometer (TOF-SIMS, manufactured by ION-TOF) equipped with a Bi ion gun (Bi 3 +) to detect secondary ion species emitted from the conductive thin wire section.
  • TOF-SIMS time-of-flight secondary ion mass spectrometer
  • Bi 3 + Bi ion gun
  • the calculated ratio A for each example sample is shown in Tables 1 to 3 below.
  • ⁇ Sulfidation resistance test 1> The resistance value (R0) of the prepared sample having a mesh pattern shape was measured. In the measurement, the electrical resistance (unit: k ⁇ ) between terminals at a distance of 4 cm was measured for each sample using an Agilent 34405A multimeter device. Next, the vulcanized EPDM (ethylene propylene diene rubber) "E-4408" (manufactured by INOAC Corporation) was cut into pieces with a length of 3.5 cm, a width of 3 mm, and a thickness of 1 mm, and the pieces of EPDM were used as conductive layers. It was fixed to the sample so that it was in contact with the side surface. After the sample with the section fixed thereon was allowed to stand at 80° C.
  • E-4408 ethylene propylene diene rubber
  • the section was removed from the sample, and the resistance value (R1) of the sample was measured by the method described above.
  • the laminate sample was pressurized in an autoclave (40° C., 0.5 MPa, 20 minutes) and irradiated with ultraviolet light (metal halide light source, 200 mW/cm 2 , 3 J/cm 2 ). Furthermore, the laminate sample was cut so that the distance from the cut end to the mesh pattern formed by the conductive thin wire portion was 1 mm to obtain a sample for evaluation.
  • a beaker containing the evaluation sample and 100 g of sulfur was placed in a sealed desiccator and left at 70° C. for 4 days. After taking out the evaluation sample, the OCA film was peeled off while heating the evaluation sample at 70° C., and the resistance value (R1) of the sample was measured in the same manner as above.
  • the sample subjected to the storage test was returned to room temperature, and the b * value (b * 1) of the surface of the sample on the conductive layer side was measured again using a reflection densitometer.
  • Tables 1, 2, and 3 below show whether or not plating treatment (step E1) was performed in the production of the conductive substrate, the type and content of specific compounds contained in the conductive substrate, and the amount of metal contained in the conductive substrate.
  • the ratio A of the content of the specific compound to the content, the type of solvent contained in the treatment liquid used in step P1, and the evaluation results of sulfur resistance and color change ⁇ b * are shown.
  • the "Name” column of "Solvent” in each table indicates the type of solvent contained in the processing liquid used in step P1
  • the conductive layer was made of 1,2,3-benzotriazole or 5-methylbenzo, which is a compound represented by the above formula (4). It was confirmed that when triazole was included, the sulfidation resistance of the conductive thin wire portion was better when stored in the form of a laminate of the conductive substrate and the adhesive sheet.
  • Conductive substrate 12 Base material 14
  • Conductive layer 16 Conductive thin wire portion 18
  • Transparent insulating portion 20 Non-fine wire portion

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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)
  • Non-Insulated Conductors (AREA)

Abstract

La présente invention aborde le problème de la fourniture d'un substrat conducteur dans lequel la résistance à la sulfuration d'une section de fil fin conductrice est excellente, ainsi qu'un panneau tactile ayant ledit substrat conducteur.　Un substrat conducteur selon la présente invention comporte un matériau de base et une couche conductrice qui est positionnée sur le matériau de base, la couche conductrice ayant une section de fil fin conductrice qui comprend du métal, et une section isolante transparente qui est adjacente à la section de fil fin conductrice et ne comprend pas de métal, et la couche conductrice comprend un composé qui est représenté par la formule (1), la formule (2), la formule (3) ou la formule (4).
PCT/JP2023/019062 2022-05-25 2023-05-23 Substrat conducteur et panneau tactile WO2023228927A1 (fr)

Applications Claiming Priority (8)

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JP2022-085224 2022-05-25
JP2022085224 2022-05-25
JP2022131908 2022-08-22
JP2022-131908 2022-08-22
JP2022-204533 2022-12-21
JP2022204533 2022-12-21
JP2023-081195 2023-05-17
JP2023081195 2023-05-17

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009188360A (ja) * 2008-02-08 2009-08-20 Fujifilm Corp 電子回路およびその製造方法
JP2014141592A (ja) * 2013-01-24 2014-08-07 Fujifilm Corp 保護膜形成用組成物、転写材料、導電膜積層体、タッチパネルおよび画像表示装置
JP2015022397A (ja) * 2013-07-17 2015-02-02 富士フイルム株式会社 タッチパネル用積層体、タッチパネル

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009188360A (ja) * 2008-02-08 2009-08-20 Fujifilm Corp 電子回路およびその製造方法
JP2014141592A (ja) * 2013-01-24 2014-08-07 Fujifilm Corp 保護膜形成用組成物、転写材料、導電膜積層体、タッチパネルおよび画像表示装置
JP2015022397A (ja) * 2013-07-17 2015-02-02 富士フイルム株式会社 タッチパネル用積層体、タッチパネル

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