Classifications

• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/22—Secondary treatment of printed circuits
  • H05K3/24—Reinforcing of the conductive pattern
  • H05K3/241—Reinforcing of the conductive pattern characterised by the electroplating method; means therefor, e.g. baths or apparatus
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
  • G03C1/047—Proteins, e.g. gelatine derivatives; Hydrolysis or extraction products of proteins
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
  • G03F7/40—Treatment after imagewise removal, e.g. baking
• • G—PHYSICS
  • G06—COMPUTING OR CALCULATING; COUNTING
  • G06F—ELECTRIC DIGITAL DATA PROCESSING
  • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
  • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
  • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
  • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
  • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/22—Secondary treatment of printed circuits
  • H05K3/24—Reinforcing of the conductive pattern
• • G—PHYSICS
  • G06—COMPUTING OR CALCULATING; COUNTING
  • G06F—ELECTRIC DIGITAL DATA PROCESSING
  • G06F2203/00—Indexing scheme relating to G06F3/00 - G06F3/048
  • G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
  • G06F2203/04103—Manufacturing, i.e. details related to manufacturing processes specially suited for touch sensitive devices
• • G—PHYSICS
  • G06—COMPUTING OR CALCULATING; COUNTING
  • G06F—ELECTRIC DIGITAL DATA PROCESSING
  • G06F2203/00—Indexing scheme relating to G06F3/00 - G06F3/048
  • G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
  • G06F2203/04112—Electrode mesh in capacitive digitiser: electrode for touch sensing is formed of a mesh of very fine, normally metallic, interconnected lines that are almost invisible to see. This provides a quite large but transparent electrode surface, without need for ITO or similar transparent conductive material
• • G—PHYSICS
  • G06—COMPUTING OR CALCULATING; COUNTING
  • G06F—ELECTRIC DIGITAL DATA PROCESSING
  • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
  • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
  • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
  • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
  • G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means
  • G06F3/0446—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means using a grid-like structure of electrodes in at least two directions, e.g. using row and column electrodes
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
  • H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
  • H05K2203/0703—Plating
  • H05K2203/0723—Electroplating, e.g. finish plating

Definitions

• the present invention relates to a method for manufacturing a conductive substrate.
• conductive substrates having conductive thin wires (thin wire-like wiring that exhibits conductivity) are used in a wide variety of applications, including touch panels, solar cells, and EL (electroluminescent) devices. It's being used.
• the conductive thin wire is produced by providing a plating resist pattern for a metal wiring pattern on the surface of the first metal layer using a negative photoresist, performing electrolytic plating, and removing the plating resist. It can be formed by a semi-additive method including a step of removing the first metal layer after peeling off the pattern.
• an object of the present invention is to provide a method for manufacturing a conductive substrate, which can manufacture a conductive substrate having thin conductive wires with a narrow line width and excellent conductivity, in which thickening at intersections is suppressed.
• the present inventor has completed the present invention as a result of intensive studies to solve the above problems. That is, it has been found that the above problem can be solved by the following configuration.
• a method for manufacturing a conductive substrate which can manufacture a conductive substrate having thin conductive wires with a narrow line width and excellent conductivity, in which thickening at intersections is suppressed.
• FIG. 2 is a plan view showing an embodiment of a mesh-like base silver pattern. It is a figure explaining a resist film arrangement process. It is a figure explaining a resist film exposure process. It is a figure explaining a resist film development process. It is a figure explaining the conductive thin line formation process.
• FIG. 2 is an enlarged plan view of the intersection of thin conductive lines for explaining thickening of the intersection.
• FIG. 2 is an enlarged plan view of the intersection of thin conductive lines for explaining thickening of the intersection.
• 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 determined by GPC (Gel Permeation Chromatography) measurement.
• organic group refers to a group containing at least one carbon atom.
• the method for manufacturing a conductive substrate of the present invention includes a step of forming a mesh-like base silver pattern on one surface side of a base material by a photographic method (hereinafter also referred to as "base silver pattern forming step”); A step of arranging a resist film on the surface side of the base material on which the base silver pattern is formed (hereinafter also referred to as “resist film arranging step”); A step of exposing the resist film by irradiating light from the surface side of the base material where the underlying silver pattern is not formed (hereinafter also referred to as “resist film exposure step”); A step of developing the exposed resist film to form a resist pattern (hereinafter also referred to as “resist film development step”); The method includes a step of performing plating using the base silver pattern as a seed layer to form a metal pattern on the base silver pattern to obtain a conductive thin wire (hereinafter also referred to as "conductive thin wire forming step”).
• a conductive substrate having thin conductive lines with a narrow line width and excellent conductivity with the thickening of the intersection points being suppressed.
• the mechanism by which a conductive substrate having the above characteristics can be manufactured by the present invention is not necessarily clear, the inventors of the present invention speculate as follows.
• a mesh-like base silver pattern is formed by a photographic method. At this time, since a photographic process is used, it is possible to form a mesh-like base silver pattern with easy contrast between exposed and unexposed areas and suppressed thickening at intersections.
• the photographic method it is easy to form a base silver pattern with a narrow line width.
• the resist film is exposed using the base silver pattern with suppressed intersection point thickening as a mask, so in the resist film development process that is carried out next, It is possible to generate a resist pattern in which thickening of intersection points in a shape corresponding to a base silver pattern is suppressed.
• the resist pattern has an opening having a shape corresponding to the underlying silver pattern.
• a metal pattern is formed by plating in the openings of the resist pattern.
• a metal pattern can be formed on the base silver pattern without the line width expanding beyond the opening of the resist pattern.
• the metal pattern is formed along the shape of the resist pattern, so it is easy to form conductive thin lines with a narrow line width and excellent conductivity.
• the resist pattern has suppressed thickening at intersections, it is possible to form conductive thin lines with suppressed thickening at intersections.
• the method for manufacturing a conductive substrate of the present invention it is possible to manufacture a conductive substrate having thin conductive lines with a narrow line width and excellent conductivity, with the thickening of the intersection points being suppressed.
• the method for manufacturing a conductive substrate of the present invention includes a step of forming a mesh-like base silver pattern on one surface side of a base material by a photographic method (base silver pattern forming step).
• base silver pattern forming step means reducing silver halide grains contained in a silver halide emulsion layer provided on a support to generate silver grains. This refers to forming a mesh-like base silver pattern with a silver layer.
• the photographic manufacturing method include the following methods (a) and (b). (a) A photographic process in which a material having a layer containing silver halide on a support is developed to reduce silver halide and deposit a silver layer.
• a photographic manufacturing method (silver complex diffusion transfer method) in which the layer containing silver is removed by washing with water.
• the photographic method used in the base silver pattern forming step is not particularly limited, but it is preferably carried out by the method (a) above.
• FIG. 1 is a plan view showing an example of a mesh-like base silver pattern.
• the mesh shape is intended to be a shape that is composed of intersecting thin base silver wires 22, each including a plurality of non-thin wire portions (openings) 32 spaced apart from each other.
• the non-fine line portion 32 has a square shape with the length of one side being L, but the non-fine line portion of the mesh pattern can be used as long as it is an area delimited by the base silver thin wire 22.
• the shape may be a polygon (for example, 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.
• each side may have 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 square lattice-shaped non-thin wire portion 32 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 the display can be viewed without any discomfort when the conductive substrate is attached to the front of the display device. can do.
• the aperture ratio of the base silver pattern is preferably 90% or more, more preferably 95% or more, and even 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 where the mesh-like base silver pattern is not arranged to the total area of the surface of the base material on the side where the mesh-like base silver pattern is formed.
• the base silver pattern forming step is not particularly limited as long as a mesh-like base silver pattern is formed by a photographic method, but a base base silver pattern forming step having the following steps A to D in this order is preferred.
• Step A A silver halide-containing photosensitive layer (hereinafter referred to as "photosensitive layer") containing silver halide, gelatin, and a polymer compound different from gelatin (hereinafter also referred to as "specific polymer”) is formed on the base material.
• Step B Step of exposing the silver halide-containing 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.
• Step C A step of heat-treating the silver-containing layer obtained in Step B.
• Step D A step of removing gelatin in the silver-containing layer obtained in Step C to form a base silver pattern.
• the steps are as follows. Steps A to D will be explained.
• Step A is a step of forming a photosensitive layer (silver halide-containing photosensitive layer) containing silver halide, gelatin, and a specific polymer (a polymer compound different from gelatin) on a substrate.
• a base material with a photosensitive layer is manufactured which is subjected to the exposure treatment described below.
• the materials (base material, silver halide, gelatin, and specific polymer) preferably used for producing the base material with a photosensitive layer will be explained, and then the procedure of step A will be explained in detail.
• the base material is not particularly limited as long as it can transmit the exposure light used in the resist film exposure step, and examples thereof include a plastic base material, a glass base material, and a metal base material, with a plastic base material being preferred.
• the material of the base material may be selected in accordance with the wavelength of exposure light used in the resist film exposure step described below.
• the transmittance at the wavelength of the exposure light used in the resist film exposure process of the base material is preferably 30% or more, more preferably 50% or more, and even more preferably 70% or more.
• the upper limit is not particularly limited, and may be 100%. The above transmittance can be measured with a commercially available spectrophotometer.
• As the base material a flexible base material is preferable since the resulting conductive substrate has excellent bendability.
• Examples of flexible base materials include the above plastic base materials.
• “having flexibility” means a base material that can be bent, and specifically, it means that no cracks occur even when the base material is bent with a bending radius of curvature of 2 mm.
• the flexible base material has workability that allows it to be formed into a three-dimensional shape.
• 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 these, PET is particularly preferred because it has excellent adhesion to the underlying silver pattern.
• the numerical value in parentheses above is the melting point or glass transition temperature.
• polyimide may be selected as the material constituting the base material as long as it transmits the exposure light used in the resist film exposure step.
• 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 thin wire 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 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.
• 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 200 nm in terms of equivalent sphere diameter, and the average particle diameter of silver halide is preferably 10 to 1000 nm, more preferably 10 to 200 nm, and the average particle size of silver halide is preferably 10 to 1000 nm, more preferably 10 to 200 nm, and the average particle diameter of silver halide is preferably 10 to 1000 nm, more preferably 10 to 200 nm. 50 to 150 nm is more preferable since the change in resistance value is smaller.
• 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, gelatins modified with amino groups and/or carboxyl groups (phthalated gelatin, acetylated gelatin), and the like may be used.
• the specific polymer is a polymer compound different from the above-mentioned gelatin.
• the type of specific polymer is not particularly limited as long as it is different from gelatin, and preferably is 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, the silver-containing layer formed by the photosensitive layer preferably 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 further 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.
• the polymer represented by the general formula (1) is preferably a polymer represented by the following general formula (3).
• 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 to 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 from 1,000 to 1,000,000, more preferably from 2,000 to 750,000, even more preferably from 3,000 to 500,000.
• the photosensitive layer may contain materials other than those mentioned above, if necessary.
• examples of other materials include metal compounds belonging to Group 8 or Group 9, such as rhodium compounds and iridium compounds, which are used to stabilize silver halide and increase sensitivity.
• other materials include antistatic agents, nucleation accelerators, spectral sensitizing dyes, surfactants, and antifoggants described in paragraphs [0220] to [0241] of JP-A-2009-004348. , hardeners, anti-black spot agents, redox compounds, monomethine compounds, and dihydroxybenzenes.
• other materials include physical development nuclei.
• examples of the material for the physical development nuclei include colloids such as gold and silver, metal sulfides prepared by mixing sulfides with water-soluble salts such as palladium and zinc, and the like.
• the photosensitive layer may contain a crosslinking agent used to crosslink the above-mentioned specific polymers.
• a crosslinking agent used to crosslink the above-mentioned specific polymers.
• a physical development nucleus layer containing physical development nuclei may be provided between the base material and the photosensitive layer.
• the physical development nuclei contained in the physical development nucleus layer are as described above.
• the descriptions in paragraphs [0007] to [0016] of JP-A-5-265162 can be referred to.
• 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 (eg, 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 (silver halide-containing 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, but it functions as a self-aligning mask pattern in the resist film exposure process described below, and it reduces the line width variation of fine lines in the underlying silver pattern formed after the development process described below. From the point of view of suppressing the amount of silver, it is preferably 1.0 to 10.0 g/m 2 and more preferably 2.0 to 7.0 g/m 2 in terms of silver.
• Silver conversion means that the mass of silver produced by reducing all the silver halide is converted.
• 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 in terms of better flexibility and formation of a plating metal pattern on the surface of the base. , 0.08 to 1.0 g/m 2 is more preferable.
• 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.
• Exposure may be carried out in a pattern.
• Exposure may be carried out in a pattern.
• a method of exposing through a mask having a mesh-like opening pattern and scanning the laser beam An example of this method is to expose the image in a mesh pattern.
• the type of light used during exposure is not particularly limited as long as it can form a latent image on the silver halide, and examples include visible light, ultraviolet light, and X-rays.
• the development method is not particularly limited, and examples thereof include known methods used for silver salt photographic films, photographic paper, printing plate-making films, 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 (methol hydroquinone) developer, and MAA (methol ascorbic acid) developer.
• the developability of the photosensitive layer is determined by the wavelength of the light source, the amount of light, and the sensitivity characteristics of the photosensitive layer, but in order to obtain a base silver pattern with a desired line width, for example, the amount of light during exposure may be adjusted.
• Step B 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.
• a thin line-shaped silver-containing layer containing metallic silver, gelatin, and a specific polymer is formed, and an insulating layer that does not contain metallic silver and contains gelatin and a specific polymer is formed. It is formed.
• An example of a method for adjusting the width of the silver-containing layer is a method of adjusting the opening width of a mask used during exposure.
• the width of the silver-containing layer to be formed can also be adjusted by adjusting the exposure amount. For example, when the opening width of the mask is narrower than the target width of the silver-containing layer, the width of the area where the latent image is formed can be adjusted by increasing the exposure amount more than usual. That is, the line width of the silver-containing layer and the formed conductive thin line can be adjusted by adjusting the exposure amount.
• the exposure area can be adjusted by adjusting the focusing range and/or scanning range of the laser light.
• the width of the silver-containing layer is preferably 0.5 ⁇ m or more and less than 5.0 ⁇ m, more preferably 3.0 ⁇ m or less, and even more preferably 1.4 ⁇ m or less, since the formed conductive thin wire is difficult to visually recognize.
• 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.
• Step C is a step in which the silver-containing layer and the insulating layer (hereinafter both are also referred to as "silver-containing layer etc.") obtained in Step B are subjected to heat treatment.
• the silver-containing layer and the insulating layer hereinafter both are also referred to as "silver-containing layer etc.”
• the heat treatment method is not particularly limited, and examples include a method of bringing superheated steam into contact with the silver-containing layer, etc., and a method of heating with a temperature adjustment device (e.g., a heater).
• a temperature adjustment device e.g., a heater
• 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).
• Step D is a step of removing gelatin in the silver-containing layer etc. obtained in Step C. By carrying out this step, gelatin is removed from the silver-containing layer, etc., and spaces are formed in the silver-containing layer, etc.
• the method for removing gelatin is not particularly limited, and examples include a method using a protease (hereinafter also referred to as "Method 1") and a method of decomposing and removing gelatin using an oxidizing agent (hereinafter referred to as "Method 2"). ).
• 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 content of the protease in the enzyme solution is not particularly limited, and is preferably 0.05 to 20% by mass, and 0.5 to 20% by mass based on the total amount of the enzyme solution, since the degree of gelatin decomposition and removal can be easily controlled. 10% by mass is more preferable.
• the enzyme solution often contains water.
• the enzyme solution may contain other additives (for example, a pH buffer, an antibacterial compound, a wetting agent, and a preservative) as necessary.
• the pH of the enzyme solution is selected so as to maximize the function of the enzyme, and is generally preferably between 5 and 9.
• the temperature of the enzyme solution is preferably a temperature at which the action of the enzyme is enhanced. Specifically, the temperature is preferably 25 to 45°C.
• a cleaning treatment of cleaning the obtained silver-containing layer and the like with warm water may be performed.
• the cleaning method is not particularly limited, and a method of bringing the silver-containing layer, etc. into contact with hot water is preferable; for example, a method of immersing the silver-containing layer, etc. in hot water, and a method of applying hot water on the silver-containing layer, etc. are preferable.
• the optimum temperature of the hot water is selected depending on the type of proteolytic enzyme used, and from the viewpoint of productivity, it is preferably 20 to 80°C, more preferably 40 to 60°C.
• the contact time (cleaning time) between hot water and the silver-containing layer, etc. is not particularly limited, and from the viewpoint of productivity, it is preferably 1 to 600 seconds, more preferably 30 to 360 seconds.
• 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., E 0 ) 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 procedure in Method 2 may be a method of bringing the silver-containing layer etc. into contact with the above-mentioned oxidizing agent, for example, a treatment liquid containing the silver-containing layer etc. and the oxidizing agent (hereinafter also referred to as "oxidizing agent liquid").
• oxidizing agent liquid a treatment liquid containing the silver-containing layer etc. and the oxidizing agent
• Examples of the contact method include a method in which the silver-containing layer, etc. is immersed in an oxidizing agent solution, and a method in which the oxidizing agent solution is applied onto the silver-containing layer, etc.
• the type of solvent contained in the oxidizing agent liquid is not particularly limited, and examples include water and organic solvents.
• the base silver pattern forming step may include a step E of further performing a smoothing treatment after step D.
• a conductive thin wire with better handling resistance film strength
• the method of the 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 base silver pattern forming step may include step Z 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 thin wire 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 of forming the silver halide-free layer is not particularly limited, and for example, a method of applying a layer-forming composition containing gelatin and a specific polymer onto a base material and subjecting it to a heat treatment as necessary is available. Can be mentioned.
• the layer-forming composition 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 silver halide-free layer is not particularly limited, and is often 0.05 ⁇ m or more, preferably more than 1.0 ⁇ m, more preferably 1.5 ⁇ m or more, since the adhesion of the conductive thin wire portion is better. .
• the upper limit is not particularly limited, but is preferably less than 3.0 ⁇ m.
• the line width of the base silver pattern formed by the above-described process is preferably 0.5 ⁇ m or more and less than 5.0 ⁇ m, more preferably 3.0 ⁇ m or less in view of the fact that the formed conductive thin line is difficult to see. More preferably, the thickness is .4 ⁇ m or less.
• the line width of the base silver pattern is determined by observing the film surface of the conductive substrate from the vertical direction using a scanning electron microscope (SEM). A more detailed measurement method is the same method as in the examples described later.
• the thickness of the base silver pattern is preferably 1.7 ⁇ m or less, more preferably 1.5 ⁇ m or less, even more preferably 1.0 ⁇ m or less, from the viewpoint of reducing variations in the line width of the conductive thin lines formed.
• the thickness of the base silver pattern can be obtained by the following method. Ten arbitrary locations on the base material on which the base silver pattern is formed are selected, and at each location, a cross section cut in a direction perpendicular to the extending direction of the base silver thin wire is observed using an SEM. The maximum value in the thickness direction of the base silver thin wire is measured from the obtained observation image. The thickness of the base silver pattern is determined by calculating the arithmetic mean value of the maximum values in the thickness direction measured at the ten selected locations. A more detailed measurement method will be described in Examples below. In addition, in the conductive substrate obtained through the process described later, if the region of the base silver pattern can be determined, the thickness of the base silver pattern may be measured by performing the above measurement on the conductive substrate.
• the method for manufacturing a conductive substrate of the present invention includes the step of arranging a resist film on the surface side of the base material on which the underlying silver pattern is formed (resist film arranging step). More specifically, as shown in FIG. 2, by performing this step, a base silver pattern 12 and a resist film 14 are arranged on the base material 10. The resist film 14 is arranged to cover the underlying silver pattern 12.
• the resist film can be arranged by a known method, for example, by applying a resist composition containing the components contained in the resist film to the surface side of the substrate on which the underlying silver pattern is formed, and A method may be mentioned in which a surface on which a base silver pattern is formed and a film-like resist film are laminated together.
• the resist film placed in the resist film placement step is preferably a negative resist whose exposed portion is insoluble in the developer used in the resist film development step.
• a known negative resist can be used as the negative resist.
• negative resists whose solubility in alkaline developers decreases upon exposure are preferred.
• the method for manufacturing a conductive substrate of the present invention includes a step of exposing a resist film by irradiating light from the surface side of the base material on which the underlying silver pattern is not formed (resist film exposure step).
• resist film exposure step light is irradiated onto the entire surface of the base material from the surface side on which the base silver pattern is not formed, and the resist film is exposed using the base silver pattern as a mask. More specifically, as shown in FIG. 3, when light is irradiated from the direction indicated by the white arrow, the base silver pattern 12 functions as a mask, and the resist film located on the base silver pattern is not exposed.
• the wavelength of the exposure light used in the resist film exposure step is not particularly limited as long as it can expose the resist film and can pass through the base material.
• the exposure light and exposure light source used in the resist film exposure process include g-line (wavelength 436 nm), i-line (365 nm), KrF excimer laser (248 nm), ArF excimer laser (193 nm), and F 2 excimer laser (157 nm). etc.
• the exposure may be performed by scanning the laser so that the entire surface of the base material is irradiated with light.
• the exposure amount in the resist film exposure step can be adjusted as appropriate, but is preferably from 50 to 2000 mJ/cm 2 , more preferably from 100 to 1000 mJ/cm 2 , even more preferably from 200 to 500 mJ/cm 2 .
• the resist film may be heated (prebaked) before exposure, or may be heated (postbaked) after exposure.
• the above-mentioned heating can be appropriately adjusted depending on the resist film used, and examples of the above-mentioned heating conditions include heating at 60 to 150° C. for 10 to 300 seconds.
• the method for manufacturing a conductive substrate of the present invention includes a step of developing an exposed resist film to form a resist pattern (resist film developing step).
• the exposed resist film is developed and the portion of the resist film disposed on the base silver pattern is removed, thereby forming a resist pattern having an opening in a shape corresponding to the base silver pattern. That is, the resist pattern has a shape that covers only the portion where the underlying silver pattern is not formed.
• the resist pattern is exposed by irradiating light from the surface side of the base where the base silver pattern is not formed, using the base silver pattern as a mask, so the resist pattern is self-aligned to the base silver pattern. is formed.
• the resist film can be developed using a known developer, and the developer may be selected depending on the type of resist film. Examples of the developer include an alkaline developer and an organic solvent developer.
• the resist film development step rinsing with a rinsing liquid may be performed after development. As the rinsing liquid, the one used for the developer may be used as the rinsing liquid, or another rinsing liquid may be used.
• the other rinsing liquid examples include water (preferably ion exchange water or ultrapure water).
• the resist pattern formed in the resist film development step preferably has an inverted trapezoidal shape (inverted tapered shape) or a rectangular shape with the short side facing the underlying silver pattern.
• the method for manufacturing a conductive substrate of the present invention includes the steps of performing plating using a base silver pattern as a seed layer, forming a metal pattern on the base silver pattern, and obtaining conductive thin wires (conductive thin wire forming step).
• the resist pattern obtained in the resist film development process is used as a plating resist
• the base silver pattern is used as a seed layer for plating
• a plating film is selectively formed on the base silver pattern to form the metal pattern.
• a metal pattern 18 is formed on the base silver pattern 12, and a conductive thin wire 20 is obtained.
• FIG. 5 by performing this step, a metal pattern 18 is formed on the base silver pattern 12, and a conductive thin wire 20 is obtained.
• the conductive thin wire 20 is composed of a base silver pattern 12 and a metal pattern 20 (plated film).
• the plating method is not particularly limited, and may be electroless plating (chemical reduction plating, displacement plating, etc.) or electrolytic plating, but electroless plating is preferred.
• electroless plating a known electroless plating technique is used. Examples of 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 is more excellent. 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 solution may contain known additives such as a plating solution 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. A commercially available plating solution may be used as the plating solution.
• the above-mentioned plating procedure is not particularly limited, and any method may be used as long as it is a method of bringing the base silver pattern into contact with the plating solution.
• a method of immersing the base silver pattern in the plating solution, or a method of immersing the base silver pattern in the plating solution, and a method of bringing the plating solution into contact with the base silver pattern One method is to apply it to the surface.
• the contact time between the base silver pattern and the plating solution is not particularly limited, and is preferably from 20 seconds to 30 minutes in terms of better conductivity of the conductive thin wire and productivity.
• the resist pattern may be removed.
• methods for removing the resist pattern include a method of stripping using a stripping liquid that has high affinity with the material constituting the resist pattern.
• a known stripping solution can be used as the stripping solution.
• the resist pattern may not be removed, and the portion that becomes insoluble in the developer due to exposure may be used as a component of a product or the like.
• a resist pattern that is used without being removed is also called a permanent resist.
• a resist pattern is used as a permanent resist, it is preferable that the haze and retardation of the permanent resist change little over time.
• An example of a resist film capable of forming such a permanent resist is ATN1021 negative type acrylic resist manufactured by Dow Chemical.
• a blackening layer may be formed on the surface of the formed conductive thin wire opposite to the base material.
• the blackening layer prevents the reflection of light on the conductive thin wire, and improves the visibility of light rays passing through the conductive substrate.
• the blackened layer can be formed by a plating process such as black chrome plating, black nickel plating, or black alumite plating.
• the conductive thin wire forming step may further include a step of performing heat treatment.
• a conductive thin wire with better conductivity can be obtained.
• the method of heat-treating the conductive thin wire is not particularly limited, and examples include the method described in Step C.
• the thickness of the metal pattern to be formed is preferably 0.5 ⁇ m or more, more preferably 1.0 ⁇ m or more, and even more preferably 1.5 ⁇ m or more, in terms of easy formation of conductive thin wires with excellent conductivity. .
• the upper limit is not particularly limited, but is preferably 10 ⁇ m or less, more preferably 8.0 ⁇ m or less, and even more preferably 6.0 ⁇ m or less.
• the thickness of the metal pattern can be measured using the same method as the method for measuring the thickness of the base silver pattern on the conductive substrate. A more detailed measurement method will be described in Examples below.
• the thickness of the metal pattern can be adjusted by the line width of the underlying silver pattern, the thickness of the resist film, the plating time in the conductive thin line forming process, and the like.
• the line width of the conductive thin wire is preferably 0.5 ⁇ m or more and less than 5.0 ⁇ m, more preferably 3.0 ⁇ m or less, and even more preferably 1.4 ⁇ m or less, from the viewpoint that the conductive thin wire is difficult to visually recognize. It is preferably 1.0 ⁇ m or less, particularly preferably 1.0 ⁇ m or less.
• the line width of the conductive thin wire can be measured using the same method as the method for measuring the thickness of the base silver pattern on the conductive substrate. A more detailed measurement method will be described in Examples below.
• the line width of the conductive thin line can be adjusted by the line width of the underlying silver pattern.
• the ratio of the thickness of the metal pattern (thickness of the plating film) to the line width of the conductive thin wire is 0.4 or more in order to form a conductive thin line with a narrow line width and excellent conductivity. It is also preferable.
• the above ratio is more preferably 0.8 or more, and even more preferably 1.0 or more.
• the upper limit of the above ratio is not particularly limited, but is preferably 5.0 or less, more preferably 4.0 or less.
• the height of the conductive thin wire can be measured using the same method as the method for measuring the thickness of the base silver pattern on the conductive substrate. A more detailed measurement method will be described in Examples below.
• the ratio of the height of the conductive thin wire to the line width of the conductive thin wire is preferably 0.80 or more in order to form a conductive thin wire with a narrow line width and excellent conductivity.
• the above ratio is more preferably 1.10 or more, further preferably 1.20 or more, and particularly preferably 2.00 or more.
• the upper limit of the ratio is not particularly limited, but is preferably 5.00 or less, more preferably 4.00 or less.
• the height of the conductive thin wire can be measured using the same method as the method for measuring the thickness of the base silver pattern on the conductive substrate. A more detailed measurement method will be described in Examples below. Note that the height of the conductive thin wire is the total value of the thickness of the base silver pattern and the thickness of the metal pattern (plated film).
• the above ratio can be adjusted by the line width of the underlying silver pattern, the thickness of the resist film, the plating treatment time in the conductive thin line forming process, and the like.
• the intersection point thickening ratio of the conductive thin wires is preferably 1.0 to 1.6, more preferably 1.0 to 1.5.
• FIGS. 6 and 7 are enlarged plan views of the intersections of thin conductive lines for explaining the thickening of the intersections.
• FIG. 6 shows the intersection of the conductive thin wires when the intersection is not thickened.
• the conductive thin wires 22a have a line width Lw, and intersect at an angle ⁇ formed by two conductive thin wires 22a to form an intersection. That is, in FIG. 6, the conductive thin wires 22a extend in four directions from the intersection. However, ⁇ is greater than 0° and less than or equal to 90°.
• FIG. 7 shows the intersection of conductive thin wires when there is a thick intersection. In FIG. 7, the conductive thin wires 22b intersect at an angle ⁇ formed by two conductive thin wires 22b, forming an intersection. That is, in FIG.
• the conductive thin wires 22b extend in four directions from the intersection.
• the dashed-dotted line in FIG. 7 is a virtual line when there is no thickening of the intersection at the intersection formed by the thin conductive wires 22b.
• the line width of the conductive thin line 22b in the area where no thickening at the intersection point has occurred is Lw.
• the diameter Cw of the maximum inscribed circle that is the maximum diameter in the region forming the intersection is determined.
• the intersection point thickening rate is given by the following formula.
• intersection point thickening rate Cw/Ci That is, the intersection point thickening rate corresponds to the ratio of the diameter Cw of the maximum inscribed circle of the intersection point where the intersection point has become thick to the diameter Ci of the maximum inscribed circle of the intersection point when it is assumed that there is no intersection point thickening.
• the diameter Ci of the maximum inscribed circle is determined from the line width Lw of the conductive thin wire measured by the above method and the angle ⁇ formed at the intersection of the two conductive thin wires.
• the diameter Ci of the maximum inscribed circle is ⁇ 2 times the line width Lw of the conductive thin wire when the angle ⁇ is 90°, that is, when the conductive thin wires are perpendicular to each other.
• intersection point thickening is obtained by observing the conductive substrate using a SEM in a direction perpendicular to the plane of the conductive substrate and analyzing the obtained image.
• a more detailed measurement method will be described in Examples below.
• FIG. 6 and FIG. 7 demonstrated the aspect in which the electroconductive thin wire extended toward four directions from an intersection part, as mentioned above, other aspects may be sufficient.
• the diameter Ci of the maximum inscribed circle and the diameter Cw of the maximum inscribed circle are obtained by observing with the SEM and analyzing the obtained image in the same manner as above.
• intersection point thickening rate corresponds to a numerical value that indicates how many times the effective line width of the intersection point becomes due to the intersection point thickening compared to the case where there is no intersection point thickening.
• the intersection point thickening rate is 1. If the intersection point is thick, the intersection point thickening rate will be more than 1, and if the intersection point is thin, the intersection point thickening rate will be less than 1.
• the diameter Cw of the maximum inscribed circle is the average value of the maximum diameters of the circles inscribed at the five intersection points, and Lw is the line width at the midpoint between the two intersection points. Adopt the average value when measured at different locations.
• the conductive substrate obtained by the method for manufacturing a conductive substrate of the present invention can be applied to various uses, such as touch panels (or touch panel sensors), semiconductor chips, various electric wiring boards, FPC (Flexible Printed Circuits), COF ( It can be applied to applications such as Chip on Film), TAB (Tape Automated Bonding), antennas, multilayer wiring boards, and motherboards.
• the conductive substrate is preferably used for a touch panel (capacitive touch panel).
• the conductive thin wire described above can effectively function as a detection electrode.
• examples of the display panel used in combination with the conductive substrate include a liquid crystal panel and an OLED (Organic Light Emitting Diode) panel, and a combination with an OLED panel is preferable.
• OLED Organic Light Emitting Diode
• conductive substrates 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.
• electromagnetic shield can be used not only for personal computers but also for electronic equipment such as video imaging equipment and electronic medical equipment.
• Conductive substrates can also be used in transparent heating elements.
• the 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 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.
• the present invention is basically configured as described above.
• the present invention is not limited to the above-described embodiments, and various improvements or changes may be made without departing from the spirit of the present invention.
• Examples 1 to 10 and Comparative Example 1 conductive substrates were manufactured, and the following evaluation items were evaluated: intersection thickening ratio, line width, line width variation, conductivity, and visibility. Examples 1 to 10 and Comparative Example 1 will be described below.
• Example 1 [Preparation of silver halide emulsion] To the following 1 liquid maintained at a temperature of 38°C and a pH (hydrogen ion index) of 4.5, amounts equivalent to 90% of each of the following 2 and 3 liquids were simultaneously added over a period of 20 minutes with stirring to form a 0.07 ⁇ m core particles were formed. Subsequently, the following liquids 4 and 5 were added to the mixed solution over 8 minutes, and the remaining 10% of the following liquids 2 and 3 were added over 2 minutes to grow the particles to 0.09 ⁇ m. . Further, 0.15 g of potassium iodide was added to the mixed liquid, and the mixture was aged for 5 minutes to complete particle formation.
• the particles were washed with water by a flocculation method according to a conventional method. Specifically, the temperature of the above-mentioned mixed solution was lowered to 35 ° C., and the pH of the mixed solution was lowered using sulfuric acid until the silver halide particles precipitated (pH was in the range of 3.6 ⁇ 0.2). ). Next, about 3 liters of supernatant liquid was removed from the mixture (first water washing). Further, 3 liters of distilled water was added to the mixture from which the supernatant liquid had been removed, and then sulfuric acid was added until the silver halide precipitated. Again, 3 liters of supernatant liquid was removed from the mixture (second water washing).
• the final emulsion contained 0.08 mol% of silver iodide, the ratio of silver chlorobromide was 70 mol% of silver chloride and 30 mol% of silver bromide, and the average grain size was 0.10 ⁇ m. It was a silver iodochlorobromide cubic grain emulsion with a coefficient of variation of 9%.
• composition for forming photosensitive layer contains 1,3,3a,7-tetraazaindene (1.2 ⁇ 10 ⁇ 4 mol/mol Ag), hydroquinone (1.2 ⁇ 10 ⁇ 2 mol/mol Ag), and citric acid (3.0 mol/mol Ag). x10 -4 mol/mol Ag), 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt (0.90 g/mol Ag), and a trace amount of hardening agent, and the composition I got something. Next, the pH of the composition was adjusted to 5.6 using citric acid.
• a dispersion consisting of a polymer represented by the following (P-1) (hereinafter also referred to as "polymer 1”) and dialkylphenyl PEO (PEO is an abbreviation for polyethylene oxide) sulfate ester is added to the above composition.
• Polymer latex containing agent and water ratio of mass of dispersant to mass of polymer 1 (mass of dispersant/mass of polymer 1, unit: g/g) is 0.02, solid content content is 22% by mass
• 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
• 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 Corporation) was added as a crosslinking agent. 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. Note that 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 a polyethylene terephthalate film ("rolled long film manufactured by Fuji Film Corporation") having a thickness of 40 ⁇ m 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.
• Step Z1, Step A1 Next, on the undercoat layer, a silver halide-free layer-forming composition prepared by mixing the above-mentioned polymer latex and gelatin and the above-mentioned photosensitive layer-forming composition are simultaneously coated in a multilayer manner. A silver halide-free layer and a silver halide-containing photosensitive layer were formed.
• 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 2.0 ⁇ m, and the mixing mass ratio of polymer 1 and gelatin in the silver halide-containing photosensitive layer (polymer 1/gelatin) is 0.25/1.
• the content of polymer 1 was 0.15 g/m 2 .
• Process B1 The photosensitive layer prepared above was exposed to light by irradiating parallel light from a high-pressure mercury lamp as a light source through a lattice-shaped photomask.
• a mask for pattern formation was used as the photomask. Note that the photosensitive layer was exposed to light while the photomask was in contact with the photosensitive layer.
• the shape of the photomask and the exposure conditions are such that a unit square lattice having an opening with a side length L of 400 ⁇ m is formed in the conductive substrate formed after the step E1 described below, and the line width Lw of the conductive thin wire is set. was set to be 2.1 ⁇ m.
• a developing solution described below was applied to the exposed photosensitive layer, and further processing was performed using a fixing solution (trade name: N3X-R for CN16X, manufactured by Fuji Film Co., Ltd.). Thereafter, it was rinsed with pure water at 25° C. and dried to obtain a sample A having silver-containing fine wires containing metallic silver formed in a mesh pattern.
• a mesh pattern area (corresponding to the base silver pattern) with a size of 10 cm x 10 cm was formed. Note that the line width of the silver-containing thin line was measured using a microscope "VHX-5000" manufactured by Keyence Corporation.
• composition of developer The following compounds are contained in 1 liter (L) of developer solution. Hydroquinone 0.037mol/L N-methylaminophenol 0.016mol/L Sodium metaborate 0.140mol/L Sodium hydroxide 0.360mol/L Sodium bromide 0.031mol/L Potassium metabisulfite 0.187mol/L
• the obtained sample A described above 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 Sample A treated in step B1 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.
• Sample A treated in step C1 was immersed in a hypochlorous acid-containing aqueous solution (25° C.) for 30 seconds. Sample A was taken out from the aqueous solution, and sample A was immersed in warm water (liquid temperature: 50° C.) for 120 seconds to be washed. After this, the water was removed using an air shower and the material was allowed to air dry.
• a hypochlorous acid-containing aqueous solution a diluted solution prepared by diluting a bleach manufactured by Kao Corporation (trade name "Hiter") twice was used.
• Step E1 Sample A obtained in step E1 was calendered at a pressure of 30 kN using a calender device consisting of a combination of a metal roller and a resin roller. Calendering was performed at room temperature. Through the above steps, a base silver pattern was formed. The line width and thickness of the formed base silver pattern are shown in the table below. A method for evaluating the line width and thickness of the base silver pattern will be explained later.
• a liquid negative resist material "ZPN1150" (manufactured by Zeon Corporation) was applied to almost the entire surface of the conductive substrate obtained in step E1 on the side on which the underlying silver pattern was formed to form a resist film ( resist film placement process).
• the resist film is irradiated with G-rays with a wavelength of 436 nm from the surface of the substrate opposite to the base silver pattern, thereby forming the base silver pattern as a self-aligned mask pattern.
• the resist film was exposed (resist film exposure step). In the exposure treatment, exposure was performed with an ultraviolet ray dose of 320 mJ/cm 2 , followed by PEB (post-exposure bake) at 90° C. for 1 minute.
• the exposed photoresist was developed for 1 minute using a developer ("NMD-3" manufactured by Tokyo Ohka Kogyo Co., Ltd.), and the resist film in the unexposed areas was removed.
• a resist pattern (plating resist pattern) was formed (resist development step), and sample B having a base material, a base silver pattern, and a plating resist pattern was obtained.
• the shape of the opening of the plating resist pattern was almost the same as the mesh pattern of the underlying silver pattern.
• the opening width of the opening in the formed plating resist pattern was approximately the same as the line width of the conductive thin wires constituting the mesh pattern of the underlying silver pattern.
• Step H1 Sample B obtained in step G1 was immersed in plating solution A (30° C.) described below. Thereafter, sample B is taken out from plating solution A, and then sample B is immersed in warm water (liquid temperature: 50°C) for 120 seconds for cleaning, thereby forming a plating film on the base silver pattern using the base silver pattern as a seed layer. was formed. In addition, in step H1, the time for immersing sample B in plating solution A was adjusted so that the thickness of the plating film was 2.0 ⁇ m. The composition of the plating solution A used (total volume 1200 mL) is shown below.
• the amount of potassium carbonate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was adjusted so that the pH of plating solution A was 9.5. Furthermore, the following components of plating solution A were all manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.
• composition of plating solution A ⁇ AgNO3 8.8g ⁇ Sodium sulfite 72g ⁇ Sodium thiosulfate pentahydrate 66g ⁇ Potassium iodide 0.004g ⁇ Citric acid 12g ⁇ Methylhydroquinone 3.67g ⁇ Prescribed amount of potassium carbonate ⁇ Remainder of water
• a conductive thin wire consisting of a base material, a metal pattern consisting of a base silver pattern and a plating film placed on the base material, and an area where the conductive thin wire is not placed on the base material are formed.
• a conductive substrate of Example 1 having a plating resist pattern was manufactured.
• the underlying silver pattern and the plating film have different metal densities, so each layer can be identified using a scanning electron microscope (SEM), and the thickness of each layer and the total thickness can be determined using a scanning electron microscope (SEM). was able to be measured.
• the conductive substrate is cut using an ultramicrotome along a plane perpendicular to the direction in which the conductive thin wires extend, including the width direction and lamination direction (thickness direction) of the conductive thin wires.
• the cut surface was exposed.
• carbon was deposited to a thickness of 10 to 20 nm on the exposed cut surface to prepare a test piece for cross-sectional observation.
• the cut surface of the obtained test piece was observed using a SEM manufactured by Hitachi High-Technologies Corporation to obtain an observed image.
• the observation conditions were an acceleration voltage of 5 kV and a backscattered electron mode. In the observed image, regions containing many elements with high atomic numbers are displayed in white.
• the white and dense area was defined as the area of the plating film, and the white area, which was darker than the area of the plating film, was defined as the area of the base silver pattern and the thickness was measured.
• the method for measuring the thickness is as described above.
• Examples 2 to 9 the exposure amount was changed by adjusting the exposure time in step B1, and the line width of the base silver pattern was adjusted as shown in the table below, or the plating time in step G1 was changed.
• a conductive substrate was manufactured in the same manner as in Example 1, except that the plating film thickness was adjusted to have the thickness shown in the table below.
• Examples 10 and 11 conductive substrates were manufactured in the same manner as in Example 1, except that in step B1, a spacer was provided between the sensitive material layer and the photomask and exposure was performed.
• the thickness of the spacer in Example 10 was 4.6 ⁇ m
• the thickness of the spacer in Example 11 was 6.0 ⁇ m.
• the line width after step E1 in Examples 10 and 11 was 2.5 ⁇ m.
• Example 12 a conductive substrate was manufactured in the same manner as in Example 1, except that during the plating process in step H1, the following electroless copper plating solution was used and electroless copper plating was performed.
• the electroless copper plating solution "OIC Accela” and “OIC Copper” manufactured by Okuno Pharmaceutical Co., Ltd. were used. Electroless copper plating was performed by immersing Sample B in OIC Accela (25°C) for 3 minutes, then in OIC Copper (55°C) for 10 minutes, and then rinsing with 25°C pure water.
• Example 13 the line width of the mask used in step B1 was changed and adjusted to match the line width and thickness of the base silver pattern shown in the table below, and the plating time in step G1 was changed to A conductive substrate was manufactured in the same manner as in Example 1, except that the plating film thickness was adjusted to have the thickness shown in the table.
• Example 14 the exposure amount in step B1 was adjusted to achieve the line width and thickness of the base silver pattern shown in the table below, and the plating time in step G1 was changed to achieve the line width and thickness shown in the table below.
• a conductive substrate was manufactured in the same manner as in Example 13, except that the plating film thickness was adjusted to have the thickness shown.
• Example 15 a conductive substrate was manufactured in the same manner as in Example 1, except that the plating time in step G1 was changed and the plating film thickness was adjusted to be as shown in the table below.
• Conductive substrates of Comparative Examples 1 and 2 were manufactured according to Example 1 of JP-A-2007-287953. That is, after forming a metal layer on a base material by sputtering and forming a negative resist film on the metal layer, a resist pattern is formed using the same pattern as in Example 1 of the present invention, and the openings of the resist pattern are After forming a plating film by electrolytic plating and removing the resist pattern, the metal layer formed by sputtering on which no plating film was formed is removed to form conductive thin wires with a mesh pattern to produce a conductive substrate. did.
• the base material was a polyethylene terephthalate film with a thickness of 40 ⁇ m
• the thickness of the plating film on the base metal pattern in Comparative Example 1 was 3 ⁇ m
• the thickness of the plating film in Comparative Example 2 was 6 ⁇ m.
• intersection point thickening rate The intersection point thickening rate was obtained by observing with a scanning electron microscope (SEM) and obtaining an image according to the following definition. That is, the angle ⁇ between the two conductive thin wires was 90°. A small numerical value of the intersection point thickening rate indicates that the degree of thickening at the intersection point is small.
• (Intersection point thickening rate) Cw/( ⁇ 2 ⁇ Lw)
• Cw is the same as the diameter Cw of the maximum inscribed circle at the intersection point explained above, and is the diameter of the maximum circle inscribed at the intersection point of the conductive thin wires when the conductive substrate is observed from the perpendicular direction of the film surface. It is.
• Lw represents the average line width of the conductive thin wire.
• the diameter Cw of the maximum inscribed circle and the line width Lw were expressed in ⁇ m.
• the diameter Cw of the maximum inscribed circle is the average value of the maximum diameters of circles inscribed at five intersection points, and Lw is the line at the midpoint between the intersection points. The average value when the width was measured at five locations was used.
• the line width W of the conductive thin wire was determined by observing the film surface of the conductive substrate from the vertical direction using a SEM. Specifically, between the intersection points of conductive thin wires formed in a mesh pattern, the line widths are measured at five equally spaced points, the average value is taken as the line width We, and the above measurements are taken as the conductive line width at 10 points. The arithmetic mean value of the line widths We obtained at each of 10 points was taken as the average line width W of the conductive thin wires. Further, the line width variation was determined by the following formula, where Wmax is the maximum line width, Wmin is the minimum line width, and W is the average line width.
• the maximum line width Wmax is determined by selecting the maximum line width at the 10 locations above from the 5 line width values obtained when measuring the line width We.
• the minimum line width Wmin is the arithmetic average of the values, and the minimum line width Wmin is determined by selecting the minimum line width from the five line width values obtained when measuring the line width We at the 10 points above. This value is the arithmetic average of the 10 values obtained. It is preferable that the above-mentioned line width variation is small in terms of excellent conductivity, which will be described later.
• the line width variation is preferably 80% or less, more preferably 60% or less, and even more preferably 50% or less.
• the lower limit of line width variation is not particularly limited, and may be 0% or more.
• the obtained conductive substrates were laminated in the order of glass/conductive substrate/polarizing plate 1/polarizing plate 2/black PET (manufactured by Panac Corporation, industrial black PET (GPH100E82A04)) to obtain a laminate. Ta.
• the polarizing plate 1 and the polarizing plate 2 were linear polarizers, and were arranged and laminated so that the polarization directions were perpendicular to each other.
• the conductive substrate was arranged such that the conductive thin wire side was located on the glass side.
• the obtained laminate was visually observed from the front on the glass side and at an angle of 30° to 60° in an environment of 500 lux. The above observation was performed by 10 observers, and the visibility was evaluated according to the following criteria.
• the conductive substrate has excellent optical properties, and moiré that occurs when the conductive substrate is laminated on a display is reduced.
• the visibility evaluation is preferably 3 to 5 out of the following 1 to 5, more preferably 4 or 5, and even more preferably 5.
• 5 When observing the laminate from a position 15 cm away, no observers visually recognized the mesh pattern.
• 4 When observing the laminate from a position 30 cm away, zero or one observer visually recognized the mesh pattern.
• 3 When observing the laminate from a position 30 cm away, 2 to 4 observers visually recognized the mesh pattern.
• five or more observers visually recognized the mesh pattern.
• observing the laminate from a position 1:50 cm away five or more observers visually recognized the mesh pattern.
• Base material 12 Base silver pattern 14 Resist film 16 Resist pattern 18 Metal pattern 20 Conductive thin wire 22 Base silver thin wire 32 Non-fine wire portion 22a, 22b Conductive thin wire

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• 2023
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