TW201626407A - Providing electrically-conductive articles with electrically-conductive metallic connectors - Google Patents

Abstract

Electrically-conductive articles are prepared to have electrically-conductive metallic grids and electrically-conductive metallic connectors (BUS lines) on one or both supporting sides of a transparent substrate. The electrically-conductive metallic connectors are designed with one metallic main wire that comprises two or more adjacent metallic micro-wires in bundled patterns. These bundled patterns and metallic micro-wires are designed with specific dimensions and configurations to provide optimal fidelity (or correspondence) to the mask image used to provide such patterns. The electrically-conductive articles can be prepared using various manufacturing technologies and can be used as parts of various electronic devices including touch screen devices. The electrically-conductive metallic grids and connectors can be prepared and designed using various technologies that are amenable to obtaining very fine lines in predetermined patterns.

Description

Providing a conductive member having a conductive metal connector

The present invention relates to a method for preparing a transparent conductive article having a conductive metal electrode grid and a conductive metal connector attached thereto. The inventive conductive articles have a specially arranged conductive metal (thin wire) grid in one of the touch regions on a transparent substrate and a conductive metal connector in a non-touch region.

Various electronic devices, especially display devices for various communication, financial, and archival purposes, are rapidly advancing. For applications such as touch screen panels, electrochromic devices, light emitting diodes (LEDs), field effect transistors, solid state lighting, organic light emitting diode (OLED) displays, and liquid crystal displays, conductive film is necessary And the industry has made considerable efforts to improve the properties of these conductive films, and in particular to improve the metal grid or wire conductivity and provide as much correspondence as possible between the mask design and the resulting user metal pattern. Sex.

Conductive objects used in various electronic devices including electronic, optical, sensing, and diagnostic devices including, but not limited to, telephones, computing devices, and other display devices have been designed to make a touch on a person's fingertip or mechanical stylus Respond.

In particular, there is a need to provide touch screen displays and devices that include improved conductive film elements. Currently, capacitive touch screen displays use an indium tin oxide (ITO) coating to create an array of capacitive regions for distinguishing multiple contact points. ITO coatings have significant drawbacks and efforts are being made to replace the use of ITO coatings in various electronic devices.

In the known printed circuit board (PCB) and integrated circuit processes, the preferred method of mass production is to directly print a circuit from a master object onto a suitable substrate to produce a circuit image on a suitable PCB photosensitive film. A copy or a laser of a master circuit image (or negative pattern) is directly written onto the photosensitive film of the PCB. The imaged PCB photosensitive film is then used as a "mask" for imaging multiple copies onto one or more substrates coated with a photoresist.

One of the essential characteristics of these methods is that the PCB photosensitive film and photoresist composition are optimized in formulation and development such that the imaged copy represents the master image as faithfully as possible in terms of circuit size and nature. This property is sometimes referred to as "fidelity" (or "correspondence"), and the worse the fidelity, the worse the performance of the resulting copy. However, in the mass production of such circuits having a design pattern with extremely fine size features, there are a variety of compositions and operations that are inherently unfavorable for fidelity or that are not conducive to faithfully reproducing the master circuit image (eg, chemical processing). situation.

Conductive silver articles have been described for use in touch screen panels having conductive silver grid patterns on both sides of a transparent substrate, for example, as disclosed in US Patent Application Publication No. 2011/0289771 (Kuriki) And 2011/0308846 (Ichiki).

However, the presence of a conductive silver grid pattern only on one or both sides of the transparent substrate is not sufficient to provide one of the responses needed for sensing touches of various electronic devices. The conductive metal grid must be connected to each other in some manner and to the appropriate electronic components and software in the device so that the desired function can be achieved in response to a touch of one finger or stylus. Thus, the conductive article is also designed to have a conductive "bus bar" line (or conductive connection or termination wiring area) that is external to the conductive touch area for the touch design. A representation of such a conductive article is shown in Figure 8 of U.S. Patent Application Serial No. 2011/0289771 (mentioned above).

Typically, conductive metal connectors in conductive articles are not designed for high transparency or sensitivity to touch. It will likely have different electrical conductivities and sizes than conductive metal grids in the touch area. These differences further make it more difficult to achieve the required fidelity of a master circuit image and the resulting copy.

Known, low-cost methods for fabricating thin wires suitable for use in an apparently transparent touch area of a touch design are not always suitable for making large and large bus lines suitable for use in conductive metal connectors or terminal wiring areas. A thick wire that is external to the conductive touch area containing the conductive metal grid. The use of different manufacturing methods for each of these areas is expensive and prone to various problems.

Accordingly, there is a need for one way to provide a transparent conductive article having both a conductive metal mesh in a touch sensitive area and a conductive metal connector that is as close as possible to the master circuit as close as possible to the master circuit The reproduction of the image.

The present invention provides a method for providing a conductive article, the method comprising: providing a transparent substrate having a first support side and a second support side; providing on the first support side of the transparent substrate: a) a conductive metal mesh, (b) a conductive metal connector electrically connected to the conductive metal mesh, and optionally, (c) a transparent region in which both the conductive metal mesh and the conductive metal connector Externally, wherein: (i) the electrically conductive metal connector comprises at least one metal main conductor, the at least one metal main conductor comprising two of the metal end conductors electrically connected to one end of the at least one metal main conductor or a plurality of metal micro-wires, the two or more metal micro-wires of the at least one metal main conductor and the metal-side wires forming a bundle pattern; (ii) the average length of each metal micro-wire is at least 1 mm; and (iii) the conductive metal connector has a combined transmittance of less than 68%.

In many embodiments, the method of the present invention further comprises: providing on the opposite second support side of the transparent substrate: (a) a relatively conductive metal mesh, (b) a relatively conductive metal connector electrically connected to the relatively conductive metal mesh, and optionally, (c) a transparent region at which the opposite conductive Both the metal mesh and the relatively conductive metal connector are external, wherein: (i) the relatively conductive metal connector comprises at least one metal bus, the at least one metal bus including electrical connection to the at least one metal One or more metal microwires of one of the metal end conductors at one end of the line, the two or more metal microwires of the at least one metal main conductor and the metal end conductor forming a bundle pattern (ii) each metal microwire has an average length of at least 1 mm; and (iii) the relatively conductive metal connector has a combined transmittance of less than 68%.

One or more conductive articles provided by any of the embodiments of the present methods can be used to fabricate a variety of touch screen devices.

The present invention provides a conductive article comprising a conductive metal grid (for "touch sensitive" or "touch" areas) having a higher transparency and a higher conductivity. The conductive objects also include conductive metal connectors (also identified as busbar lines, busbar regions, or terminal electrodes), and the matching of the images in the regions with the images in the original mask components (correspondence or fidelity) is obtained. Improved and has a high electrical conductivity. The conductive metal lines in the two regions can be fabricated in a common process (or step) using a common material.

Aligning at least one (such as silver) main conductor (for example, two or more metal main conductors) into two or more metal micro-wires for the conductive metal wire pattern in the (electrode) connector region The bundled pattern and various metal (such as silver) end wires of each bundled pattern achieve these advantages. Additionally, adjacent metal microwires in the bale pattern can be configured with both electrical connection metal (such as silver) jumper wires and metal (such as silver) end wires. The bundled pattern and the metal micro-wire are obtained from exposure and processing and have the most used in the touch screen device. Specific size, spacing and conductivity properties of superior performance. Even in the presence of some manufacturing defects, the metal master wire and the metal microwire bundled pattern can increase conductivity, manufacturability and robustness. In other words, the use of the present invention at least reduces the possible effects of manufacturing defects or inconsistencies.

5‧‧‧Electrical objects

6‧‧‧ Conductive metal grid

8‧‧‧ Conductive metal connectors

10‧‧‧ metal main line

15‧‧‧Parts of the photosensitive silver halide emulsion layer

20‧‧‧Metal microwires

22‧‧‧Metal end wire

24‧‧‧Metal jumper wires

40‧‧‧Transparent substrate

42‧‧‧ (transparent substrate) first support side

44‧‧‧ (transparent substrate) relative to the second support side

50‧‧‧(several) transparent areas

60‧‧‧Unexposed and undeveloped silver halide grains

62‧‧‧ Silver particles

64‧‧‧Hydrophilic adhesive

Conductive film element precursor provided by 100‧‧‧

105‧‧‧Previous image of conductive film element exposed by image

107‧‧‧Image-wise exposure of the first side of the precursor of the conductive film element

109‧‧‧Image-wise exposure of the second side of the precursor of the conductive film element

110‧‧‧Developed exposed conductive film components

112‧‧‧Exposure of the first side of the precursor before exposure to the image

114‧‧‧Exposure of the second side of the precursor by imagewise exposure

D1‧‧‧Maximum height of metal microwires

D2‧‧‧Metal microwire minimum height

L‧‧‧Metal microwire length

S1‧‧‧Distance between adjacent metal conductor lines

S2‧‧‧Distance between adjacent metal microwires

W‧‧‧Metal microwire width

1 is a schematic illustration of one of a conductive metal connector wire pattern on a support side of a transparent substrate, the conductive metal connector wire pattern being incorporated into a conductive article or a conductive article thereof prepared using the present invention or Part of it.

Figure 2 is a schematic cross-sectional view of one of the electrically conductive articles prepared in accordance with the present invention.

3A is a schematic cross-sectional view of a conductive film element precursor comprising a portion of a photosensitive silver halide emulsion layer disposed on a transparent substrate, the portion of the photosensitive silver halide emulsion layer being included, in accordance with a preferred embodiment. Undeveloped photosensitive silver halide grains.

3B is a schematic cross-sectional view of one of the conductive film element precursors including one of the developed photosensitive silver halide grains disposed in a representative silver microwire on a transparent substrate, the silver microwire being obtainable from FIG. 3A. A portion of the photosensitive silver halide emulsion layer.

4 and 5 are schematic illustrations of conductive metal (such as silver) connector wire patterns on a support side of a transparent substrate, showing metal (such as silver) ends in a variety of bundled patterns. The wires are configured with jumper wires with different metals, such as silver.

6 through 9 are flow diagrams showing the options for forming a conductive article from a single-sided or dual conductive film element precursor.

Figure 10 is a schematic cross-sectional view of one of a metal (e.g., silver) microwire on a transparent substrate having a maximum height at substantially the center thereof.

Figure 11 is a schematic cross-sectional view of one of the metal (e.g., silver) microwires on a transparent substrate having a maximum height closer to its outer edge than its center.

Figure 12 is a schematic illustration of one of the electrically conductive articles in accordance with at least one embodiment of the present invention.

The following discussion is directed to the various embodiments of the present invention, and although some embodiments may be more suitable for the particular use, the disclosed embodiments should not be construed or construed as limiting the scope of the invention as claimed. Thus, those skilled in the art should understand that the following disclosure and the illustrative drawings are more broadly applicable to the application, and the discussion or illustration of the embodiments is not intended to limit the scope of the invention.

definition

The singular forms "a" and "the" are intended to include one or more of the components (ie, include, unless otherwise indicated). Multiple refers to the object).

Unless otherwise indicated, the term "% by weight" means the amount of the component or material based on the total solids of the composition, formulation, solution, or the dry weight of the layer. Unless otherwise indicated, the percentage is the same for a dry layer or pattern or for the total solids of the formulation or composition used to make the layer or pattern.

Unless otherwise indicated, the terms "conductive film element" and "conductive article" are intended to mean the same thing. It refers to a material comprising a conductive metal mesh and a conductive metal connector disposed on either or both of the support sides of a suitable transparent substrate. Other components of the conductive article are described below.

The term "first" refers to a layer on the support side of one of the transparent substrates (first flat), and the term "second" refers to the layer on the opposite (relatively flat) second support side of the transparent substrate. The support sides of the transparent substrate can be equally useful, and the term "first" does not necessarily mean that one side is the primary or better support side of the conductive article.

The terms "dual" and "double side" are used herein to refer to an electrical object having the described conductive metal mesh and conductive metal connectors on the two support sides of the transparent substrate.

ESD refers to the "equivalent spherical diameter" and is a term used in the field of photography to define the size of particles, such as silver halide grains. Particles of silver halide grains expressed by particle ESD The size can be easily determined using a disc centrifuge instrument.

Unless otherwise instructed, "black and white" means black and white materials and formulations that form a black and white material and are not colored.

In most embodiments, a transparent substrate comprising one or both of the support sides and all of the conductive objects accompanying the conductive metal grid and the transparent regions are considered transparent, meaning that they are in the visible region of the electromagnetic spectrum ( For example, the integrated transmittance from 410 nm to 700 nm is 70% or greater, or more likely at least 85% or even 90% or greater, as measured, for example, using a spectrophotometer and known techniques. Therefore, the touch area in the resulting conductive article will have this high overall transmittance. However, the transparency of the region containing the conductive connectors is typically much less than the remainder of the conductive article and typically has a combined transmission of less than 68% or less than 50% or even less than 40% when using the same equipment and processes mentioned above. ratio.

Alternatively, the integrated transmittance can be associated with a calculated percentage of the transparent substrate area that is not covered by the electrically conductive metal grid or the electrical connection metal connections in the connector region.

In defining the various dimensions of the metal (such as silver) main conductor and the metal (such as silver) microwire provided in the electrically conductive article, appropriate measurement techniques and equipment known to those skilled in the art are used at least 2 times from the specific dimensions. The "average value" of each size is determined.

Unless otherwise indicated, the terms "connector", "busbar line" and "busbar area" mean the same thing.

Unless otherwise indicated herein, the term "metal" means a single pure metal, metal alloy, metal oxide, metal sulfide, a composite of a metal with an organic or inorganic material, and containing metal particles (such as microparticles, Material of the material of nano particles or particles.

use

Conductive articles have a variety of uses. For example, a conductive article can be used as the device itself or the like for use in a variety of applications including, but not limited to, electronic, optical, sensing, and diagnostic applications. The components in the device. In particular, it is desirable to use a conductive film element precursor to provide a highly conductive metal grid and conductive metal connectors comprising metal lines of appropriate height, width and conductivity for use in touch screen displays or for use as touch A component of a screen device. Such electronic and optical devices and components include, but are not limited to, radio frequency tags (RFID), sensors, touch screen displays and memory, and backplanes of displays.

Conductive object

The conductive article provided by the present invention comprises a transparent substrate having a first support side and a second opposite support side. These opposing support sides refer to the flat side of the transparent substrate rather than its edges.

The choice of a transparent substrate generally depends on the desired utility of the resulting conductive article for a predetermined device. The transparent substrate can be rigid or flexible and typically has an integrated transmittance of at least 90% and typically at least 95% within the visible region of the electromagnetic spectrum (eg, at least 410 nm and up to and including 700 nm). The integrated transmittance can be determined using a spectrophotometer as described above and known procedures.

Suitable transparent substrates include, but are not limited to, glass, glass reinforced epoxy laminates, cellulose triacetate, acrylates, polycarbonates, polymeric transparent substrates coated with adhesives, polyester films, and transparent composite materials. Suitable transparent polymers for use as transparent polymer substrates include, but are not limited to, polyethylene and other polyolefins, polyesters such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN). , polybutylene terephthalate 1,4-cyclohexanedimethyl ester, polybutylene terephthalate) and copolymers thereof, polypropylene, polyvinyl acetate, polyurethane, polyamine, polyphthalamide Amines, polybenzazoles, polycarbonates, and the like. Other useful transparent substrates may be cellulose derivatives (such as cellulose esters, cellulose triacetate, cellulose diacetate, cellulose acetate propionate, cellulose acetate butyrate, polyacrylates, polyether phthalimides) and It is composed of a mixture of the same.

The transparent polymer substrate may also comprise two or more layers of the same or different polymeric compositions such that the composite transparent substrate (or laminate) has the same or different layer refractive properties. Any one or both of the support sides of the transparent substrate can be treated to probabilize any adhesion of the placement layer or pattern. For example, the transparent substrate may be coated with a polymeric adhesion layer on one or both of the support sides, may be chemically treated or subjected to a corona treatment.

Commercially available oriented and non-oriented transparent polymeric films such as biaxially oriented polypropylene or polyester can be used. These transparent substrates may contain pigments, air gaps or foam voids, provided that the desired overall transmittance is achieved.

The flexible transparent substrate used to fabricate flexible electronic devices or touch screen assemblies facilitates rapid scroll manufacturing. Estar ^® polyethylene terephthalate film, a cellulose triacetate film system for producing a flexible transparent substrate material of particularly useful pair.

The transparent substrate can have a thickness of at least 20 μm and up to and including 300 μm or typically at least 75 μm and up to and including 200 μm. Antioxidants, brighteners, antistatic or conductive agents, plasticizers, and other known additives can be incorporated into a transparent substrate if desired by those skilled in the art, provided that the desired overall transmittance is maintained. .

The electrically conductive article may have on the at least first support side of the transparent substrate: (a) a conductive metal (such as silver) grid, (b) a conductive metal (such as silver) connector electrically connected to the conductive metal grid And optionally, (c) a transparent region external to both the conductive metal mesh and the conductive metal connector, wherein: (i) the conductive metal connector comprises at least one metal (eg, silver) main conductor, The at least one metal (eg, silver) main conductor includes two or more metal microwires electrically connected to the metal end conductor at one end of the at least one metal main conductor, the at least one of the metal main conductors Two or more metal microwires and the metal end wires form a bundle pattern; (ii) each metal microwire has an average length of at least 1 mm; (iii) The conductive metal connector has a combined transmittance of less than 68%.

Conductive articles comprising a transparent substrate and all of the accompanying layers on one or both of the support sides are considered to be in the touch area (where the conductive metal grid is formed) and the conductive metal grid and other transparent areas outside the conductive metal connectors Transparent, which means that the integrated transmittance of such touch regions and other transparent regions that pass through the entire conductive object in the visible region of the electromagnetic spectrum (eg, from 410 nm to 700 nm) is 70% or greater, or more likely at least 85%. Or even 90% or more. The overall transmittance is measured as described above.

However, the transparency of the conductive metal connector is small due to the higher coverage area of the metallic material formed in the connector region. For example, such conductive metal connectors composed of conductive metal patterns typically have a combined transmittance of less than 68% or less than 50% or even less than 40%.

The conductive metal mesh and the conductive metal connectors can be formed on a suitable transparent substrate in accordance with various processes as described below. Various necessary and optional features (i) through (v) are also described below. While the following discussion is primarily directed to the use of light sensitive silver halide to practice the invention, it should be understood that the inventive methods described herein for preparing conductive articles of the invention are not limited to this particular technique. Those skilled in the art will readily appreciate how to use various chemical and material techniques to achieve desired results, as taught by those skilled in the art to understand the desired characteristics of conductive articles.

Technology for providing conductive objects

The electrically conductive article can be prepared in a variety of ways, including using a silver halide emulsion precursor article that includes imaging through a suitable mask to form a conductive silver metal pattern (described in detail below), using "imprint and fill" techniques, and A composition (eg, a photocurable composition) that can be printed (eg, as a conductive ink) or subsequently electrolessly plated to form a pattern of conductive patterns (eg, a photocurable pattern) can be used.

"embossing and filling" technology:

The "embossing and filling" technique typically involves forming a microwire pattern on a transparent substrate using an embossing procedure, such as embossing lithography. For example, conductive microwires can be formed in the microchannels, The microchannels have been embossed or imprinted into a photocurable composition on a substrate such as one of the materials described below. One of the microchannels may be imprinted (embossed) onto the photocurable composition layer by a master (or mold) having an inverted pattern of one of the ridges formed on the surface. The embossable curable composition can then be cured by light prior to release of the master (mold). An additional thermal cure step can be used to further cure the composition. A conductive composition can be applied over the substrate to flow into the formed microchannels. It is generally desirable to remove excess conductive composition between the microchannels, for example by wiping. The remaining conductive composition in the microchannel can be cured, for example, by heating and exposure to hydrochloric acid vapor. The microchannels are provided and filled to form both a conductive metal mesh and a conductive metal connector in a common step. Excessive cured conductive composition can then be removed using known treatments.

For example, in the United States Public Notice No. 2015/0064426, which was jointly pending and jointly granted by March 5, 2015 (Wang et al. applied for September 4, 2013), and on March 5, 2015 (Wang et al. The application is described in US Publication No. 2015/0060113 and June 4, 2015 (Wang et al., filed on Dec. 3, 2013), US Publication No. 2015/0156886. Some useful procedures and compositions for making conductive articles using this technique.

Additional light curable technology:

Some other useful photocurable compositions and their use in the preparation of electrically conductive articles, including transparent continuous rolls of such articles, are described, for example, in WO 2013/062630 (Petcavich) and in WO 2013/063051 (Petcavich et al.).

For example, a conductive metal mesh and a conductive metal connector can be formed on one or both of the support sides using a photocurable composition that provides a seed metal catalyst for an electrodeless plating process. For example, the photocurable composition can include an acid catalyzed photocurable chemical, a free radical photocurable chemical, or both types of chemicals, although the invention is not limited to the photocurable chemicals described and can be used It is further practiced to include any known photocurable composition of a seed metal catalyst.

In some embodiments, useful photocurable compositions include one or more UV curable components, at least one of which is an acid catalyzed photocurable component. These photocurable compositions may further comprise a photoacid generator that participates in the formation of an acid group that causes photocuring of the photocurable component.

Some useful acid catalyzed photocurable components are photocurable epoxy materials. The cationic photocurable epoxy material can be an organic compound having at least one oxirane ring. These epoxy materials comprise a monomeric epoxy compound and a polymeric type of epoxide, and may be aliphatic, alicyclic, aromatic or heterocyclic. Such materials typically have an average of at least one polymerizable epoxy group per molecule, or typically at least about 1.5 or even at least about 2 polymerizable epoxy groups per molecule.

Various compounds can be used as photoacid generators to produce a suitable acid to participate in photocuring of the epoxy material. Some of these "photoacid generators" are acidic in nature and others are non-ionic in nature. An alkali salt photoacid generator suitable as a photoacid generator in the practice of the present invention includes, but is not limited to, a diazonium salt, a phosphorus salt, an iodide salt or a sulfur salt, and includes a polyaryl diazonium salt, a phosphorus salt, and an iodine salt. Salt and sulfur salts.

Nonionic photoacid generators are also useful, including but not limited to diazomethane derivatives, glyoxal hydrazine derivatives, biguanide derivatives, and disulfono derivatives.

Some photocurable compositions (especially compositions comprising a photopolymerizable epoxy material and a photoacid generator) described herein may contain one or more electron donor photosensitizers to improve photocuring efficiency.

In other embodiments of the photocurable technology, the photocurable composition can include one or more UV curable components, at least one of which is a free radical photocurable component, and the photocurable composition can be further A free radical photoinitiator is included to provide free radicals during photocuring.

The one or more free radical polymerizable compounds may be present to provide a free radical polymerizable officer Energy, comprising an ethylenically unsaturated polymerizable monomer, oligomer or polymer, such as a monofunctional or polyfunctional acrylate (also comprising methacrylate). Such free radical polymerizable compounds include at least one ethylenically unsaturated polymerizable chemical bond (half group) and such may, in many embodiments, include both or more of such unsaturated halves.

One or more free radical photoinitiators may also be present in the photocurable composition to generate free radicals. Such free radical photoinitiators comprise any compound capable of generating free radicals upon exposure to photocuring radiation, such as ultraviolet light or visible radiation.

The photocurable compositions described herein typically comprise suitable metal particles that can serve as a seed metal catalytic site for electroless plating. Usually only one type of metal particle is used, but it is also possible to contain a mixture of metal particles from the same or different classes of metals that do not interfere with each other.

Useful metal particles can be selected from one or more of the classes of precious metals, semi-precious metals, Group IV metals, or combinations thereof. Useful noble metal particles include, but are not limited to, particles of gold, silver, palladium, platinum, rhodium, ruthenium, iridium, mercury, osmium, and iridium. Useful particles of semi-precious metals include, but are not limited to, particles of iron, cobalt, nickel, copper, carbon, aluminum, zinc, and tungsten. Useful particles of Group IV metals include, but are not limited to, particles of tin, titanium, and ruthenium. Precious metal particles such as particles of silver, palladium and platinum are particularly useful, and semi-precious metal particles of nickel and copper are also particularly useful. Tin particles are particularly useful in the Group IV metal category. In many embodiments, silver or copper particles are used in the photocurable composition.

The metal particles can be dispersed in various organic solvents and have improved dispersibility in the presence of other components of the photocurable composition. Useful dispersing agents are well known in the art and may be present if desired. Methods for dispersing metal particles include, but are not limited to, ball milling, magnetic agitation, high speed homogenization, high pressure homogenization, and ultrasonic treatment.

When carbon coated metal particles are used, the particles may be designed to have a median particle diameter equal to or less than 0.6 μm or less than 0.2 μm or more likely to be less than 0.1 μm. These carbon-coated metal particles typically have a minimum median diameter of one of 0.005 μm. Median particle size [Dv (50%)] can be determined using a dynamic light scattering method. For example, such a method can be carried out using a Malvern Zetasizer Nano ZS available from Malvern Instruments, Ltd.

The photocurable composition is typically provided in a combination of a suitable organic diluent which acts as one of an anhydrous (organic) solvent or a solvent in which the components of the photocurable composition are dissolved or dispersed. When one or more photocurable components (as described above) are present as a liquid organic compound, the one or more photocurable components can act as an organic diluent, and a separate inert organic solvent is not necessarily required.

Light sensitive silver halide technology:

Conductive article members in accordance with the present invention can be implemented using conductive film element precursors that include (several) light sensitive silver halide but which typically do not contain sufficient chemicals to provide color photographic images. Therefore, these "precursors" are considered to be black and white photosensitive materials that form metallic silver images after exposure and development, and do not form color images.

Formed by providing a non-color (ie, black-and-white) black-sensitive light-sensitive silver halide emulsion layer on one or both of the support sides (or the flat side rather than the unsupported edge) on a suitable transparent substrate in a suitable manner Precursor. Each photosensitive layer comprises a suitable silver cover (eg, at least 2500 mg Ag/m ² or at least 3500 mg Ag/m ² but typically less than 5000 mg Ag/m ² (eg, up to and containing 4950 mg Ag/m ² ) of total silver coverage) A mixture of one silver halide or silver halide. However, as is well known in the art, a greater amount of silver coverage can be used. Thus, each photosensitive layer has sufficient silver halide inherent or external spectral sensitization to be photosensitive to pre-selected imaging radiation (described below). The photosensitive layers can have the same or different compositions and spectral sensitization on the opposite support sides of the transparent substrate.

The one or more silver halides are dispersed in one or more suitable hydrophilic binders or gels as described below.

These precursors are thus imagewise exposed and processed (or processed) in this manner to convert silver cations into silver metal particles (by reduction), and the treated precursor is then processed Can become a conductive object.

The precursor may have a necessary layer on each of the support sides of the transparent substrate, the necessary layer being a light-sensitive silver halide emulsion layer. This necessary layer may be disposed only on one of the support sides of the transparent substrate, but in many dual embodiments it is disposed on both the first and opposite second support sides of the transparent substrate. The optional layers, such as hydrophilic outer coatings and filter dye layers, may also be present on either or both of the support sides and are described below, but it is not necessary to achieve the desired advantages of the present invention.

The (several) silver halide in such layers includes silver cations that can be converted to one or more silver halide grains according to a desired pattern upon exposure of each photosensitive silver halide emulsion layer. This exposure is typically achieved by imaging through a masking element that is designed with a predetermined pattern for both the conductive metal electrode grid and the conductive metal connector wire pattern. The (several) latent image provided by this exposure can then be developed into (several) desired silver metal images using known silver development processes and chemicals (described below). Silver halide (or a combination of silver halides) is photosensitive, which means that radiation from UV to visible light (eg, at least 200 nm and up to and including 750 nm radiation) is typically used to convert silver cations into silver in a latent image. Metal particles. In some embodiments, the silver halide is present in combination with a heat sensitive silver salt such as silver behenate, and the light sensitive silver halide emulsion layer can be photosensitive and heat sensitive (ie, sensitive to thermal imaging energy such as infrared radiation).

Useful photosensitive silver halides can be, for example, silver chloride, silver bromide, silver chlorobromide iodide or silver bromide iodide, silver chlorobromide, silver bromochloride or silver iodobromide, which are prepared as individual compositions (or emulsions). ). In the name of silver halide, various halides are listed in descending order of halide content. Additionally, individual silver halide emulsions can be prepared and mixed to form a mixture of one of the silver halide emulsions used on the same or different support sides of the transparent substrate. In general, useful silver halides include up to and including 100 mole percent chloride or up to and including 100 mole percent bromide, and up to and including 5 mole percent iodide, all based on Total silver. These silver halides are often referred to as "high chloride" or "high bromide" halogenation. Silver, and can be used to form "high chloride" or "high bromide" emulsions, respectively.

The silver halide grains used in each of the photosensitive silver halide emulsion layers typically have an ESD of at least 30 nm and up to and including 300 nm or more likely at least 50 nm and up to and including 200 nm.

The coverage of the total silver in each of the light sensitive silver halide emulsion layers is desirably at least 2500 mg Ag/m ² and typically at least 3500 mg Ag/m ² and may be less than 5000 mg Ag/m ² , although higher amounts may be used.

The dry thickness of each photosensitive silver halide emulsion layer is typically at least 0.5 μm and up to and including 12 μm, and especially at least 0.5 μm and up to and including 7 μm.

The final dried photosensitive silver halide emulsion layer can be made from one or more individual coated light sensitive silver halide emulsion sub-layers that can be used with the same or different silver halide emulsion formulations. Each sublayer may be composed of (several) identical or different silver halides, hydrophilic binders or colloids and addenda. The light sensitive silver halide emulsion sublayers can have the same or different amounts of silver content.

The (several) photosensitive silver halide used in the photosensitive silver halide emulsion layer on the first support side may be the same as or different from the photosensitive silver halide (s) used in the photosensitive silver halide emulsion layer on the second support side.

The photosensitive silver halide grains (and any addenda associated therewith as described below) are dispersed (generally uniformly) in one or more suitable hydrophilic binders or colloids to form a hydrophilic silver halide emulsion. Examples of such hydrophilic binders or colloids include, but are not limited to, gelatin and gelatin derivatives, polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), casein, and the like. Kenneth by PO10 7DQ, Emsworth, Hants, UK. Research Disclosure, published by Kenneth Mason, Section IX, September 26, 464, also describes suitable hydrocolloids and vinyl polymers and copolymers. Particularly useful hydrophilic gel system gelatin or a gelatin derivative, several of which are well known in the art.

The amount of hydrophilic binder or colloid in each photosensitive silver halide emulsion layer can be suitably adapted The particular dry thickness desired and the amount of silver halide incorporated. It can also be adapted to meet the desired dispersibility, swelling, and adhesion of the layer to the transparent substrate. The amount of hydrophilic binder or colloid is typically controlled to maximize the conductivity of the resulting silver metal particles in the electrically conductive article.

In general, the one or more hydrophilic binders or gum systems are present in an amount of at least 10% by weight and up to and including 95% by weight or more likely at least 10% by weight and up to and including 70% by weight, All based on the total solids in the dried photosensitive silver halide emulsion layer.

Some useful light sensitive silver halide emulsion layer compositions have a relatively high weight ratio (or volume) of silver ion/hydrophilic binder (e.g., gelatin). For example, one of the silver ions (and the final silver metal) and the hydrophilic binder or colloid (such as gelatin) (or a derivative thereof) is particularly useful in a weight ratio of at least 0.1:1 or even at least 1.5:1 and up to and including 10: 1. A particularly useful weight ratio of silver ion to hydrophilic binder or colloid may be at least 2:1 and up to and including 5:1. Other weight ratios can be readily adapted to a particular application and dry layer thickness. A particularly useful silver ion/hydrophilic binder (gelatin) volume ratio is less than 0.5:1 or even less than 0.35:1.

Hydrophilic binders or gels can be combined with one or more hardeners designed to harden a particular hydrophilic binder such as gelatin. Particularly useful hardeners for gelatin and gelatin derivatives include, but are not limited to, non-polymeric vinyl hydrazines such as bis(vinylsulfonyl)methane (BVSM), bis(vinylsulfonylmethyl)ether (BVSME) and 1 , 2-bis(vinylsulfonylacetamide)ethane (BVSAE). A mixture of hardeners can be used if desired. The hardener can be incorporated into each of the light sensitive silver halide emulsion layers in any suitable amount that will be readily apparent to those skilled in the art.

In general, each photosensitive silver halide emulsion layer can be hardened such that it has an expansion ratio of at least 150% but less than 300% as determined by optical microscopy of the cross-section of the element, and the expansion ratio can be achieved by using an appropriate amount A hardener in the photosensitive silver halide emulsion layer or a hardener in various treatment solutions (described below) is provided.

If desired, the useful silver halide described above can be exposed to any suitable wavelength Radiation sensitization. An organic sensitizing dye can be used, but if it is desired that the conductive article containing the silver metal particles be transparent, it is advantageous to prevent the silver salt from being sensitive to the UV portion of the electromagnetic spectrum without using a visible light sensitizing dye. Spot. Alternatively, silver halide can be used without spectral sensitization beyond its inherent spectral sensitivity.

Addenda that can be included with silver halide (including chemical and spectral sensitizers, filter dyes, organic solvents, thickeners, dopants, emulsifiers, surfactants, stabilizers, hardeners, and anti-fogging agents) Non-limiting examples of this are described in Research Disclosure, September 26, 354, and many of the publications identified therein.

Useful silver halide emulsions containing silver halide grains that can be reduced to silver metal particles can be carried out by any suitable method of particle growth (eg, by using a feedback system designed to maintain silver ion concentration in the growth chamber) It is prepared by the balance of silver nitrate and salt solution. Known dopants may be introduced uniformly from the beginning to the end of the precipitation or may be structured into regions or zones within the silver halide grains. Useful dopants include, but are not limited to, antimony dopants, antimony dopants, iron dopants, antimony dopants, antimony dopants, and cyanophthalate dopants. A combination of a cerium dopant and one of the cerium dopants, such as one of pentachloronitrite and one of the cerium dopants, is useful. Chemical sensitization can be carried out by any of the known silver halide chemical sensitization methods, such as thiosulfate or another unstable sulfur compound, for example, alone or in combination with a gold complex.

Useful silver halide grains can be round cubes, octahedrons, circular octahedrons, polyhedrons, tubular or fine tubular emulsion particles. These silver halide grains may be regular non-bimorphous, regular twin or irregular twin, having a cubic or octahedral surface. In one embodiment, the silver halide grains can be a circular cube having an ESD of less than 0.5 [mu]m and at least 0.05 [mu]m.

Antifogging agents and stabilizers may be added where appropriate to impart the desired sensitivity to the silver halide emulsion. Useful antifogging agents include, for example, azaindoles such as tetraazaindene, tetrazole, benzotriazole, imidazole and benzimidazole. The specific antifogging agent which can be used individually or in combination comprises 6-methyl-1,3,3a,7-tetrazinium, 1-(3-acetamidophenyl)-5-mercaptotetrazole, 6-nitrate Benzomidazole Oxazole, 2-methylbenzimidazole and benzotriazole.

The necessary silver halide grains and hydrophilic binders or colloids and optional additions may be formulated and coated as silver halide emulsions using a suitable emulsion solvent comprising water and a mixed organic solvent. For example, useful solvents for making silver halide emulsion or coating formulations can be water, monoalcohol (such as methanol), monoketone (such as acetone), monoamine (such as formamidine), monoterpene (such as dimethyl). Amine, a monoester (such as ethyl acetate), a liquid or low molecular weight polyvinyl alcohol, or a monoether, or a combination of such solvents. The amount of one or more solvents used to prepare the silver halide emulsion can be at least 30% by weight and up to and including 50% by weight of the total formulation weight. These coating formulations can be prepared using any of the photographic emulsion manufacturing procedures well known in the art.

While the photosensitive silver halide emulsion layer on either or both of the support sides of the transparent substrate can be the outermost layer of the precursor, in many embodiments, a hydrophilic outer coating can be disposed over each of the photosensitive silver halide emulsion layers. The hydrophilic outer coating can be the outermost layer of the precursor (i.e., any layer that is not specifically placed thereon on either or both of the support sides of the transparent substrate). If both support sides of the transparent substrate comprise a photosensitive silver halide layer, a hydrophilic outer coating may be present on the two support sides of the transparent substrate. Therefore, a first hydrophilic overcoat layer is disposed over the first photosensitive silver halide emulsion layer, and a second hydrophilic outer coating layer is disposed on the second photosensitive silver halide emulsion layer on the opposite second support side of the transparent substrate. Above. In most embodiments, each hydrophilic overcoat layer is disposed directly on each of the light sensitive silver halide emulsion layers, which means that there is no intervening layer on the support side of the transparent substrate. The chemical composition and dry thickness of the hydrophilic outer coatings may be the same or different, but in most embodiments, they have substantially the same chemical composition and dry thickness on the two support sides of the transparent substrate.

In some embodiments, each hydrophilic overcoat (first or second or both) comprises one or more silver halides of the same or different amounts to have at least 5 mg Ag/m ² and the highest after exposure and treatment. Silver metal particles are provided in an amount comprising 150 mg Ag/m ² or in an amount of at least 5 mg Ag/m ² and up to and comprising 75 mg Ag/m ² . When present, the one or more silver halides in each hydrophilic overcoat layer can have a particle ESD of at least 100 nm and up to and including 1000 nm or at least 150 nm and up to and including 600 nm. In some embodiments, the one or more silver halides in each of the hydrophilic outer coatings have a particle ESD that is greater than one of the silver halide particles ESD in the achromatic hydrophilic photosensitive layer on which the hydrophilic outer coating is disposed. In various embodiments, the silver halide(s) in each hydrophilic overcoat comprises up to 100 mole percent bromide or up to 100 mole percent chloride and up to and including 3 mole percent iodide, all Mo The amount of ear is based on total silver content. In other embodiments, the silver halide (s) in each of the hydrophilic outer coatings comprises more chloride than the silver halide in the achromatic hydrophilic photosensitive layer in which the hydrophilic outer coating is disposed. This relationship may be the same or different on the two support sides of the transparent substrate in the "dual" conductive film element precursor.

When present, the silver halide is (usually uniformly) dispersed in one or more hydrophilic binders or gels in each of the hydrophilic outer coatings, the hydrophilic binders or gels comprising the bonding described above for the achromatic hydrophilic photosensitive layer Agent or colloid. In many embodiments, the same hydrophilic binder or colloid can be used in all layers of the precursor. However, different hydrophilic binders or gels can be used in various layers and on either or both of the support sides of the transparent substrate. The amount of one or more hydrophilic binders or colloids in each hydrophilic overcoat layer is the same or different, and is typically at least 50% by weight and up to and including 100% by weight or typically at least 75% by weight and up to and including 98 weights %, which are all based on the total dry weight of the hydrophilic outer coating.

In some embodiments, the hydrophilic overcoat layer may further comprise one or more radiation absorbers, such as a UV radiation absorber of at least 5 mg/m ² and up to and including 100 mg/m ² .

If silver halide is not present, the same hydrophilic binder or colloid is used, and in such embodiments, the hydrophilic binder or colloid may comprise up to 100% by weight of the total hydrophilic overcoat dry weight.

Each hydrophilic overcoat may also include one or more hardeners (eg, gelatin or gelatin derivatives) for a hydrophilic binder or colloid. Useful hardeners are described above.

Each of the hydrophilic outer coatings may have a dry thickness of at least 100 nm and up to and including 800 Nm or more specifically at least 300 nm and up to and including 500 nm. In embodiments containing silver halide, the ratio of particle ESD to dry thickness in the hydrophilic overcoat can range from 0.25:1 to 1.75:1 and comprises 1.75:1 or more likely from 0.5:1 to 1.25:1 and contains 1.25 :1.

In addition to the layers and components described above on one or both of the support sides of the transparent substrate, the precursor and conductive article may also include other layers that are not necessary but may provide additional properties or benefits, and such other layers include However, it is not limited to radiation absorbing filter layers, adhesion layers, and other layers known in the art of black and white photography. The radiation absorbing filter layer may also be referred to as an "antihalation" layer, which may be located between the necessary layers and the respective support sides of the transparent substrate. For example, each support side can have a radiation absorbing filter layer disposed directly above it and disposed directly beneath the photosensitive silver halide emulsion layer. Such a radiation absorbing filter layer may comprise one or more filter dyes or any combination thereof absorbed in the UV, red, green or blue regions of the electromagnetic spectrum, and may be located on each or both of the transparent substrate and the transparent substrate. Between the light-sensitive silver halide emulsion layers on the support side.

A dual conductive film element precursor useful in the practice of the present invention may include a second photosensitive silver halide emulsion layer on the opposite second support side of the transparent substrate and optionally include one disposed above the second photosensitive silver halide emulsion layer Two hydrophilic outer coatings. A radiation absorbing filter layer may be disposed between the opposite second support side of the transparent substrate and the second photosensitive silver halide emulsion layer, and the radiation absorbing filter layer and the radiation absorbing filter layer on the first support side of the transparent substrate Same or different. For example, such radiation absorbing filter layers can comprise one or more UV radiation absorbing compounds.

In many dual conductive film element precursors, the second photosensitive silver halide emulsion layer and a second hydrophilic outer coating (if present) have the same composition as the first photosensitive silver halide emulsion layer and the first hydrophilic outer coating, respectively.

The various layers described above can be formulated using suitable components and coating solvents and using known coating procedures including those commonly used in the photographic industry (eg, droplet coating, knife coating, curtain coating, spray coating, and funnel coating). Applied to one or both of the support sides of a suitable transparent substrate (as described above). Each layer of the formulation can be applied in a single pass or in a simultaneous multi-layer coating process. Each support side of the transparent substrate. Known drying techniques can be used to dry each of the applied formulations.

The resulting conductive film element precursor can be used immediately for the intended purpose, or it can be stored in rolls or sheets for subsequent use. For example, the precursor can be rolled up during manufacture and stored for use in a scrolling imaging and processing procedure, and then cut to the desired size and shape.

In order to expose a precursor image by image, a suitable masking element or group of masking elements is designed with a predetermined pattern for both the conductive metal mesh and the conductive metal connector that are ultimately formed in the conductive article. As mentioned above, the photosensitive silver halide emulsion layer in the precursor is typically designed to accommodate both the touch area having the desired conductive metal grid and the conductive metal connector trace pattern to provide the designed circuit. Both the touch area and the electrode connector area are formed, for example, simultaneously in the same photosensitive silver halide emulsion layer on one or both of the support sides of the transparent substrate in a common process step. The conductive metal mesh and the transparent regions outside the conductive metal connectors are typically free of silver metal particles.

Thus, one or both sides of a precursor are designed to be exposed to appropriate radiation to provide in each photosensitive silver halide emulsion layer: (a) a latent conductive silver grid, and (b) a different potential conductive silver grid Potentially conductive silver connectors. Each side of the precursor can be exposed imagewise at the same time or its image can be exposed imagewise at different times using different mask elements, so the relative latent image in all areas is designed, sized, surface area covered by silver metal particles or The sheet resistivity is different. The relatively light sensitive silver halide emulsion layers can also be designed to have different wavelength sensitivities such that different imaging (exposure) radiation wavelengths can be used for exposure on the opposite support side.

Thus, the photosensitive silver halide in the photosensitive silver halide emulsion layer can be imagewise exposed to appropriate actinic radiation (UV to visible radiation) from a suitable source, such sources being well known in the art, such as xenon lamps, mercury. The lamp is either from 200 nm and up to and including 700 nm other sources of radiation.

The precursor can be treated with various water-based treatment solutions before exposure (including at least a solution) Physical development and silver halide fixing) are provided in each exposed photosensitive silver halide emulsion layer: (a) a conductive silver grid from a potential conductive silver grid, (b) a conductive silver connection from a potential conductive silver connector And (c) a transparent region that is external to both the conductive silver mesh and the conductive silver connector.

The resulting conductive silver grid formed in the touch area typically has an overall transmittance of at least 75% (eg, the conductive silver grid covers 25% or less of the total touch area surface area). In contrast, the resulting conductive silver connector formed in the electrode connector region has a combined transmittance of 68% or less (or 50% or less). Therefore, the conductive silver connector typically covers more than 32% of the total electrode connector area. The overall transmittance is determined as described above. These equal amounts may be the same or different on the opposite support sides of the transparent substrate.

The pre-bath solution can also be used to treat the exposed silver salt prior to development. Such solutions may comprise one or more development inhibitors as described above for the development solution and having the same or different amounts. Effective inhibitors include, but are not limited to, benzotriazole, heterocyclic thiols, and tetrazolium. The front bath temperature can be in the range as described for development. The anterior bath time depends on the concentration and the particular inhibitor, but it can be in the range of at least 10 seconds and up to and including 4 minutes.

The exposure of the exposed silver halide in the latent image is typically achieved first by one or more development steps during which silver ions in the silver halide latent image are reduced to silver metal (or silver particles). Such development steps are typically carried out using an aqueous developing solution known to be commonly used in the formation of silver metal images in black and white photography, and typically comprise at least one solution physical developing solution.

It is known to develop a plurality of exposed silver halides (including latent images) to form a plurality of silver metal image black and white developing solutions (also identified as "developers") of silver metal particles. Silver metal image of a monochrome useful silver halide developing a commercial system Accumax ^® silver halide developing agents. The black and white developing solution forming the silver metal image is usually an aqueous solution containing one or more silver halide developers of the same or different types, including but not limited to (December 1978) Research Disclosure No. 17643, (November 1979) Research Disclosures Developers disclosed in Research Disclosure No. 18716 and (December 1989) Research Disclosure No. 308119, such as polyhydroxybenzene (such as dihydroxybenzene or its like hydroquinone, catechol, pyroic acid, methylhydroquinone) And the form of chlorohydroquinone), aminophenols (such as p-aminophenol, p-aminophenol and p-hydroxyphenylglycine, p-phenylenediamine), ascorbic acid and its derivatives, reducing ketones, isoascorbic acid and its derivatives, 3- Pyrazolone (eg 1-phenyl-4,4-dimethyl-3-pyrazolone, 1-phenyl-3-pyrazolidinone and 1-phenyl-4-methyl-4-hydroxyl) Methyl-3-pyrazolidinone), pyrazolone, pyrimidine, dithionite and hydroxylamine. These developers can be used individually or in combination. The one or more developers may be present, for example, in an amount of at least 0.01 mol/l and up to and including 1 mol/l.

The black and white developing solution may also contain an auxiliary silver developer which exhibits superadditive properties together with a developer. Such auxiliary developers may include, but are not limited to, p-aminophenol and substituted or unsubstituted phenidone such as at least 0.001 mol/l and up to and including 0.1 mol/l.

The concentration of the one or more auxiliary silver developers may be less than the concentration of the one or more auxiliary developers as described above.

Useful black and white developing solutions may also contain one or more silver complexing agents (or silver ligands), including but not limited to sulfites, thiocyanates, thiosulfates, thioureas, thiosemicarbazides. , tertiary phosphines, thioethers, amines, thiols, aminocarboxylates, triazole thiolates, pyridines (including dipyridines), imidazoles and aminophosphonates. For example, one or more alkali metal sulfites may be present in an amount of at least 0.1 mol/l and up to and including 1 mol/l.

For various purposes, the black and white developing solution may also include an appropriate amount of one or more alkyl or aryl substituted or unsubstituted perylene tetrazoles, such as at least 0.25 mmol/l and up to and including 2.5 mmol/l. Useful tetrazole includes, but is not limited to, alkyl, aryl and heterocyclic substituted oxatetrazole. Examples of such compounds include, but are not limited to, 1-phenyl-5-indolyltetrazole (PMT), 1-ethyl-5-indolyltetrazole, 1-tert-butyl-5-indolyltetrazole, and 1-pyridine. Base-5-tetrazolium.

Further, the black-and-white developing solution may also contain an appropriate amount of one or more development inhibitors. Useful development inhibitors include, but are not limited to, substituted and unsubstituted benzotriazole compounds, for example 5-methylbenzotriazole, imidazole, benzimidazole thione, benzothiazole thione, benzoxazole thione, and thiazolidine, all having the same or different amounts as described above for quaternary tetrazole.

Other addenda that may be present in known amounts in the black and white developing solution include, but are not limited to, metal chelating agents, preservatives (such as sulfites), antioxidants, small amounts of mixed organic solvents (such as benzyl alcohol and diethylene glycol), Nucleating agents as well as acids, hydrazines (such as alkali metal hydroxides) and buffers (such as carbonates, borax, phosphates, and other basic salts) to establish at least 8 and usually at least 9.5 or at least 11 and up to and including 14 one of the pH values.

The silver halide developing solution can be supplied at a working strength or in a concentrated form diluted up to 5 times with water before or during use.

Multiple development steps can be used if desired. For example, a first developing solution can provide initial development to form a silver metal core and then a second developing solution can be used to provide "solution physical development" that improves the conductivity of the resulting silver metal image.

A solution physical development step can be carried out using a solution having at least 8 and up to and containing one of the pHs of one of 13. The silver halide solution physical developing solution may include one or more main developers selected from one or more of hydroquinone or a derivative thereof or one or more ascorbic acids or derivatives thereof. The main developer in the physical development solution of the silver halide solution may be the same as or different from the main developer in the silver halide developing solution described above.

The one or more primary developers in the physical development solution of the silver halide solution may be present in a total amount of at least 0.01 mol/l and up to and including 1 mol/l.

Further, the silver halide solution physical development solution includes at least 0.001 mol/l and up to and including 0.1 mol/l or usually at least 0.005 mol/l and up to and including 0.05 mol/l as one of the essential components or A variety of silver halide dissolution catalysts.

Useful silver halide dissolution catalysts include, but are not limited to, alkali metal thiocyanates (such as sodium thiocyanate and potassium thiocyanate), thioethers (such as 3,6-dithia-1,8-octanediol). And heterocyclic thiols (such as tetrahydro-4,6-dimethyl-1,3,5-triazine-2(1H)-thione and tetrahydro-3-carboxyethyl-1,3,5- Triazine-2(1H)-thione). These compounds can be easily complexed with silver.

In some embodiments, the silver halide solution physical development solution is substantially free of catalytic developer, such as those described above for silver halide development solutions. The term "substantially free" means that less than 0.001 mol/l or even less than 0.0001 mol/l of such compounds are intentionally incorporated or produced in the solution.

The silver halide solution physical development solution may further comprise one or more alkali metal sulfites, including sodium sulfite, potassium sulfite, and the like. When potassium sulfite or sodium sulfite is used or particularly when only potassium sulfite is used, the alkali metal sulfite may be present in the physical development solution of the silver halide solution in a total amount of at least 0.2 mol/l and up to and including 3 mol/l. .

The silver halide solution physical development solution may further comprise one or more polyaminopolycarboxylates capable of complexing with silver ions, including but not limited to diethylenetriaminepentaacetic acid, pentasodium salt, and other similarities known in the art. Compound. Such compounds may be useful especially when monosulfite is not present. These compounds may be present in an amount of at least 0.001 mol/l and up to and including 0.03 mol/l.

The silver halide solution physical development solution may also comprise one or more metal ion complexing agents which may be complexed with silver, calcium, iron, magnesium or other metal ions which may be present. Silver or calcium metal ion complexing agents in a total amount of at least 0.001 mol/l may be particularly useful.

Particularly useful silver halide solution physical development solutions include, but are not limited to, hydroquinone or a derivative thereof and sodium thiocyanate or potassium thiocyanate and, optionally, a sulfite and a calcium or silver metal ion complexing agent.

The silver halide solution physical development solution can be provided at a working strength or in a concentrated form suitably diluted prior to or during treatment with known processing equipment and procedures. For example, a silver halide solution physical development solution can be concentrated at least 4 times compared to a desired working strength concentration.

Useful development temperatures can range from at least 15 °C and up to and including 60 °C. Useful development times can range from at least 10 seconds and up to and including 10 minutes, but are more likely to be up to and including 1 minute. The same time or temperature can be used for individual development steps, and It is adapted to develop at least 90 mole percent of exposed silver halide in all potential silver halide images. If a pre-bath solution is not used, the development time can be appropriately extended. Any exposed silver halide(s) in a hydrophilic overcoat layer is also developed during the development step. Washing or rinsing can be carried out with water after or between any of the developing steps.

After the exposed silver halide is developed into a silver metal, the undeveloped silver halide in all of the light sensitive silver halide emulsion layers is typically removed by treating the developed silver-containing article with a silver halide fixing solution. Silver halide fixing solutions are well known in the art of black and white photography and contain one or more compounds that complex silver ions to remove silver ions from the layers. A thiosulfate is usually used in a silver halide fixing solution. The silver halide fixing solution may optionally contain a hardener such as alum or chrome. The developed film may be treated with a silver halide fixing solution immediately after development, or there may be an interventional stop solution or water wash or rinse, or both stop solution and water rinse. Fixing can be carried out at any suitable temperature and time, such as at least 20 ° C for at least 30 seconds.

The fixing then leaves silver metal particles in the conductive silver metal electrode grid and the conductive silver connector in each of the preceding photosensitive silver halide emulsion layers. Fixing also removes any undeveloped silver halide in any hydrophilic outer coating.

After fixing, the resulting intermediate article can be washed or rinsed in water, which may optionally include a surfactant or other material to reduce water stain formation after drying.

After fixing, the intermediate article can be further processed to further enhance the conductivity of the silver metal (or core) on each of the support sides of the transparent substrate. Various ways have been proposed to implement this "conductivity enhancement" procedure. For example, U.S. Patent Nos. 7,985,527 (Tokunaga) and 8,012,676 (by Yoshiki et al.) describe the conductivity enhancement treatment using a hot water bath, water vapor, reducing agent or halide.

The conductivity of the silver metal particles can also be enhanced by repeated cycles of contact, washing, drying, and one or more repeated treatments, washings, and drying with a conductivity enhancer. Useful conductivity enhancers include, but are not limited to, sulfites, borane compounds, hydroquinone, p-phenylene Amines and phosphites. The treatment can be carried out for at least 15 seconds and up to and including 30 minutes at a temperature of at least 30 ° C and up to and including 90 ° C.

In some embodiments, treating the electrically conductive article with a hardening bath after fixing and prior to drying can be used to improve the physical durability of the resulting electrically conductive article. Such hardening baths may comprise one or more of the known hardeners in an appropriate amount which will be readily apparent to those skilled in the art. It may be desirable to control the expansion of the conductive film element precursor at one or more of the processing stages such that the expansion is limited to the desired amount of one of the original precursor dry thicknesses.

Additional processing such as a stabilization process can be performed at any suitable time and temperature, if desired, prior to final drying.

Drying at any stage can be accomplished in ambient conditions or by heating in a convection oven, for example, at a temperature above 50 ° C but below the glass transition temperature of the transparent substrate.

While imagewise exposure and processing of the various sides of the precursor can be performed at different times or in a different order, in many embodiments, the imagewise exposure and processing of the photosensitive silver halide emulsion layer on the first support side can be performed simultaneously The image-wise exposure and processing of the photosensitive silver halide emulsion layer on the opposite second support side of the transparent substrate is performed.

The result of the processing steps is a conductive article as described herein.

Conductive metal grid:

a conductive metal grid on the first support side and a selected conductive metal grid on the second support side in composition, pattern configuration, conductive line thickness or grid line shape (eg, polygonal pattern, including but not limited to: rectangle, triangle , hexagonal, diamond, octagon or square pattern), circular or other curved or random structure (all of which correspond to a predetermined pattern in the mask element used during image-wise exposure) may be the same Or different. For example, in one embodiment, the conductive metal grids on the first support side may be arranged in a square pattern and the conductive metal connectors on the opposite side of the support side may be arranged in a diamond pattern. In each case, the metal grid lines in the conductive metal grid form a network structure. In other embodiments, the various patterns on the opposite support sides can be configured in an alternate configuration such that The conductive metal grid on one of the support sides only partially covers the conductive metal grid on the opposite support side, as shown in Figure 14 of U.S. Patent Application Publication No. 2011/0289771 (mentioned above).

Conductive metal wires (such as silver or copper wires) in a conductive metal grid may have any desired length of typically at least 1 cm and up to and including 10 meters, and the like may have the same or different average dry thickness (one outer The line width to the other outer edge) and the dry height, and the average dry thickness and dry height are generally less than 50 μm, but are more likely to be at least 1 μm and up to and including 20 μm, or in particular at least 5 μm, and particularly less than 15 μm or even less than 10 μm or less.

Conductive metal connectors:

Each conductive metal connector wire pattern includes at least one and more likely at least two adjacent (eg, at least first and second) metal (such as silver) main conductors, and up to 1000 may be present in each conductive metal connector Or even more of these metal lines. The number of metal main conductors may vary on the opposite support sides of the transparent substrate. Each metal conductor includes two or more metal (eg, silver) end conductors electrically connected to one end of the at least one (typically at least two adjacent) metal conductors (and up to 10 or even more) Root) Metal (such as silver) microwires. Therefore, the two or more metal microwires and the metal end wires of each metal (such as silver) main conductor form a bundle type. Many bundled patterns include a plurality of metal conductor wires, each of which includes a plurality of metal microwires and all of which are electrically connected to the appropriate metal terminal wires at both ends. As described below, such bundled patterns may also include one or more metal (such as silver) jumper wires.

In some embodiments, each metal conductor may comprise two to eight metal microwires, etc., together with the appropriate metal end conductors to form a bundle pattern. Accordingly, each of the bundled patterns in the embodiments includes at each end of the at least two adjacent metal main conductors electrically connected to the two to eight metal microwires of each of the bundled patterns (and thus Conductive metal (eg, silver) end conductors at the ends of adjacent pairs of adjacent metal conductors in the bundled pattern.

The average distance between any two adjacent metal conductors is greater than the average distance between any two adjacent metal microwires in each bundle pattern. For example, the average distance between any two adjacent metal conductors can be at least 30% greater or more typically at least 100% greater than the average distance between any two adjacent metal microwires in each bundle pattern. For example, the average distance between two adjacent metal conductors can be at least 5 [mu]m or at least 10 [mu]m or even at least 20 [mu]m. These "average distances" are measured from a given metal microwire to the nearest outer edge of an adjacent metal microwire, or from the outermost metal microwire of a given metal conductor. The outermost edge of the outermost metal microwire of the adjacent metal main conductor is measured.

Within each metal conductor, the average total length of each metal microwire may be at least 1 mm or typically at least 5 mm and up to and including 1000 mm.

The average distance between any two adjacent metal microwires in each of the bundled patterns (each and any metal conductor) may be at least 2 μm and up to and including 10 μm (where "average distance" is defined above ). In particular, the average distance between any two adjacent metal microwires of each bundled pattern (or each and any metal conductor) may be at least 5 [mu]m and up to and including 8 [mu]m.

The ratio of the average width (outer edge to opposite outer edge) of each metal microwire to the average distance between two adjacent metal microwires of each bundle pattern (or each and any metal conductor line) may be at least 0.5 :1 but less than 2:1 or usually at least 1:1 and highest and contains 2:1.

It is also desirable for each metal microwire to have a ratio of maximum height to minimum height of at least 1.05:1 or typically at least 1.1:1.

In some embodiments of at least one of the silver microwires (and in most embodiments, each of the metal microwires), the maximum height of the metal microwires can be equal to the center height of the metal microwires (with a difference of less than 10%). The "center" is determined to be substantially equidistant between the two outer edges of the metal microwire. "Substantially equidistant" means that the distance from the two outer edges does not differ by more than 10%.

In other embodiments of at least one of the silver microwires (and in most embodiments, each metal microwire), the maximum height may be closer to the outer edge of the microwire than to the center height of the microwire (with the center of the phase) More close to the outer edge than at least 51%). For example, the maximum height may actually be at one or both of the outer edges of some of the metal microwires.

It is also possible that for each metal microwire, the ratio of the maximum height to the average height may be at least 1.01:1 or more typically at least 1.01:1 and comprise 1.05:1.

The average width (from one outer edge to the other outer edge) of each of the metal microwires in each of the bundled patterns may be at least 2 μm and up to and including 20 μm or typically up to and including 15 μm, or typically from 2 μm and up to And contains 12μm.

Additionally, each bundle pattern can include at least one metal (such as silver) jumper wire between adjacent metal microwires that is not at the end of the adjacent metal microwire. Typically, adjacent metal microwires include a plurality of metal jumper wires that are not at the ends of adjacent metal microwires. A skilled worker can design each bundle to have as many metal jumper wires as may be required for a given conductive metal connector.

The metal jumper wires can be configured in any suitable frequency or orientation configuration, and this configuration can be the same or different for each set of adjacent metal microwires.

For example, each bundle pattern can include a plurality of (two or more) metal jumper wires between adjacent metal microwires, wherein the plurality of metal jumper wires are configured to be at a distance of at least 100 [mu]m from each other.

In addition, a plurality of (two or more) metal jumper wires of one of the adjacent sets of metal microwires in each of the bundled patterns may be offset from the plurality of metal jumper wires of the other set of adjacent metal microwires (For example, alternating adjacent metal microwires along adjacent groups). All metal jumper wires can thus be arranged in the same or different manner between adjacent metal microwires of all adjacent groups.

In some embodiments, each of the plurality of metal jumper wires is substantially perpendicular to the adjacent metal microwires (intersecting at an angle of substantially 90°). In other embodiments, each of the plurality of metal jumper wires intersects an adjacent metal microwire at an angle greater than or less than 90°. The two or more metal microwires can be substantially parallel (eg, adjacent metal microwires are substantially parallel).

The invention may also be exemplified with reference to Figs. 1 through 12, and Figs. 1 through 12 will now be explained.

Considering first Figure 12, a general schematic diagram of one embodiment of the present invention is provided. Thus, FIG. 12 shows a conductive article 5 comprising a conductive metal grid 6 and a conductive metal connection 8 electrically connected to the conductive metal grid 6. Each of the conductive metal connectors 8 includes one or a plurality of metal conductor wires 10 forming a bundle pattern. Each metal conductor line 10 includes one or more metal micro-wires 20. The metal end wires 22 are electrically connected to the metal micro wires 20 in each of the metal main wires 10. Metal jumper wires 24 can be electrically connected to metal microwires 20 within metal master wires 10.

In FIG. 1, the conductive article 5 has a transparent substrate 40 on which a conductive metal connector 8 is disposed, the conductive metal connector 8 comprising a plurality of metal wires 10. Each metal conductor line 10 includes a plurality of adjacent metal micro-wires 20 (four metal micro-wires 20 are shown in FIG. 1 for each metal conductor line 10). Metal end wires 22 are shown at the ends of the respective metal main conductors 10. The outer portion of the conductive metal connector 8 is a transparent region 50 (referenced in some but not all locations). Transparent regions (not shown in additional numbers) are also present between (or outside) adjacent metal main conductors 10 and between adjacent metal microwires 20 in each metal main conductor 10. All transparent areas do not contain significant metallic materials. In the conductive article 5, the distance between adjacent metal main conductors (at least one identified as 10) separated by a distance S1 and the adjacent metal microwires (one identified as 20) is shown by S2. As described above, the average value S1 is larger than the average value S2 (metal main line 10) in each bundle pattern. The width of the representative average metal microwire 20 is shown as W and the average metal microwire length is shown as L. Each of the metal microwires 20 can have substantially the same or different L and W dimensions. In most embodiments, these dimensions are the same for each of the metal microwires in a given metal conductor.

2 shows a schematic cross section of one of the electrically conductive articles 5 comprising a transparent substrate 40 having a first support side 42 and a second support side 44. A representative metal microwire 20 is shown on both the first support side 42 and the opposite second support side 44.

In the cross-sectional view shown in FIG. 3A, one portion of the photosensitive silver halide emulsion layer 15 is disposed on one of the support sides (the first support side or the transparent substrate 40 having the first support side 42 and the opposite second support side 44) Relative to the second support side). This portion of the photosensitive silver halide emulsion layer 15 contains a plurality of unexposed and undeveloped silver halide grains 60 surrounded by a hydrophilic binder 64.

3B shows a view similar to FIG. 3A, but the silver (metal) microwire 20 is disposed on a transparent substrate 40 having a first support side 42 and a second support side 44, the silver (metal) microwire 20 comprising a plurality of silver metal developed from a plurality of silver halide grains 60 surrounded by a hydrophilic binder 64, which may be derived from the portion of the photosensitive silver halide emulsion layer 15 illustrated in FIG. 3A, and silver halide developed Particle 62.

4 is similar to FIG. 1 and shows a conductive article 5 comprising a transparent substrate 40 on which a conductive metal connector 8 is disposed. The conductive metal connector 8 includes a plurality of metal conductor wires 10. The metallic silver main conductor 10 is shown, but the conductive metal connector 8 can have as few as two metal main conductors. Moreover, although only four metal microwires 20 are shown for each metal conductor line 10, the number of metal microwires in each metal conductor line can be as few as two and up to and including 10. Metal end wires 22 are shown at the ends of each set of adjacent metal microwires 20, and various metal jumper wires 24 (only some of which are numbered) are shown with the same spacing along metal microwires 20. The outer portion of the conductive metal connector 8 is a transparent region 50 (labeled only at some locations), but a transparent region (no label) may also be present between adjacent metal microwires and between adjacent metal conductors.

5 is similar to FIG. 4, but the metal jumper wires 24 are disposed at different intervals along the metal microwires 20 and are offset between pairs of adjacent metal microwires 20. Thus, each bundled pattern or metal conductor 10 includes a plurality of metal jumper wires 24 of a plurality of adjacent metal microwires 20 that are offset from a plurality of adjacent metal microwires 20 of an adjacent group. The metal bridges the wires 24.

Figure 6 shows a representative portion of some embodiments of the method of the present invention in which a photosensitive film element precursor is provided in the feature 100 using a photosensitive silver halide technique ("Precursor The precursor is imagewise exposed to appropriate radiation in feature 105, and the resulting potential silver is processed in the precursor 110 in feature 110 [including development using a suitable black and white developing solution that forms a silver metal image].

Figure 7 illustrates a representative portion of another embodiment using a photosensitive silver halide technique in which two individual features are featured in feature 105 (image-wise exposure of the first side of one of the dual conductive film element precursors in feature 107) A dual-conducting film element precursor ("precursor") provided by imagewise exposure of the second (or opposite) side of the dual conductive film element precursor in feature 109 is subsequently imaged in feature 110. The resulting potential silver in the two imagewise exposed sides of the precursor (including development).

Figure 8 illustrates a representative portion of yet another variation in which image-wise exposure features 105 are simultaneously applied to the first and second sides of a dual conductive film element precursor ("precursor") (e.g., features 107 and 109) Shown), and then processed (including development) in feature 110 to expose the potential silver on both sides of the precursor by imagewise.

Further representative portions of the method of the present invention are shown in FIG. 9, wherein imagewise exposure of a first side of a dual conductive film element precursor ("precursor") is provided at 107. The first side is then processed (e.g., developed) in feature 112 to provide silver metal particles from the latent silver. The second (or opposite) side of the dual conductive film element precursor is also imagewise exposed in 109, followed by subsequent processing (including development) of the potential silver in the precursor into silver metal particles in feature 114. If necessary, image-by-image exposure and processing on both sides can be performed simultaneously.

10 is a schematic cross-sectional view of one of the typical metal microwires 20 having a circular upper surface and outer surface and disposed on a transparent substrate 40 having a first support side 42 and a second opposite support side 44. The metal (such as silver) microwire 20 is thus composed of a plurality of silver metal cores (particles) 62 surrounded by a hydrophilic binder 64, such as the chemical composition described above, suitably The exposure and processing chemicals are derived from suitable silver halide grains. As shown in FIG. 10, the metal (such as silver) microwire 20 has an average width W, metal (such as silver) microwire maximum height D1 and metal (such as silver) microwire minimum height D2, wherein metal (such as silver) microwire maximum height D1 is greater than metal (such as silver) microwire minimum height D2, such as at least 1.05:1 ratio. Although FIG. 10 illustrates a metal (such as silver) microwire having a uniform size and shape, those of ordinary skill in the art will appreciate that the illustrated illustration is merely representative and actual metal microwires produced in the practice of the present invention. It can have a more irregular outer surface and shape.

Figure 11 is another schematic cross-sectional view showing a different shape of a metal (such as silver) microwire 20 containing a plurality of silver metal particles 62 enclosed in a hydrophilic binder 64, the silver microwire 20 being placed On the transparent substrate 40 having the first support side 42 and the opposite second support side 44. The metal (such as silver) microwire minimum height D2 is at or near the center of the metal (such as silver) microwire 20, and the metal (such as silver) microwire minimum height D2 is less than either close to or located in the metal (such as silver) microwire 20 Or the metal (for example, silver) microwires of the two outer edges have a maximum height D1. Those skilled in the art will appreciate that the illustration of metal (such as silver) microwires 20 is merely representative and that the actual metal microwires produced in the practice of the present invention can exhibit a higher than the height shown. The maximum and minimum heights are quite large and can therefore have a more irregular outer surface.

The present invention provides at least the following embodiments and combinations thereof, but as will be apparent to those skilled in the art from this disclosure, other combinations of features are considered to be within the scope of the invention:

A method for providing a conductive member, the method comprising: providing a transparent substrate having a first support side and a second support side; and providing on the first support side of the transparent substrate: a) a conductive metal grid, (b) a conductive metal connector electrically connected to the conductive metal grid, and optionally, (c) a transparent region, which is external to both the electrically conductive metal mesh and the electrically conductive metal connector, wherein: (i) the electrically conductive metal connector comprises at least one metal main conductor, the at least one metal main conductor comprising Two or more metal microwires electrically connected to one of the metal end wires at one end of the at least one metal main conductor, the two or more metal microwires of the at least one metal main conductor and the The metal end wires form a bundled pattern; (ii) each metal microwire has an average length of at least 1 mm; and (iii) the conductive metal connector has a combined transmittance of less than 68%.

2. The method of embodiment 1, wherein: (iv) for each metal microwire, the ratio of the maximum height to the minimum height is at least 1.05:1.

3. The method of embodiment 1 or 2 wherein: (v) the ratio of the average width of each of the metal microwires in each of the bundled patterns to the average distance between the two adjacent metal microwires is at least 0.5:1 but Less than 2:1.

The method of any one of embodiments 1 to 3, wherein the conductive metal connector comprises at least two adjacent metal main conductors, and an average distance between the at least two adjacent metal main conductors is greater than each bundle The average distance between any two adjacent metal microwires in the pattern.

5. The method of embodiment 4 wherein the average distance between any two adjacent metal microwires in each of the bundled patterns is at least 2 [mu]m and up to and including 10 [mu]m.

The method of any of embodiments 1 to 5, further comprising: providing on the opposite second support side of the transparent substrate: (a) a relatively conductive metal mesh, (b) a relatively conductive metal a connector electrically connected to the relatively conductive metal mesh and, as the case may be, (c) a transparent region, the equal conductive metal mesh and the opposite conductive metal An outer portion of the connector, wherein: (i) the relatively conductive metal connector comprises at least one metal bus, the at least one metal bus including one of the metal ends electrically connected to one of the ends of the at least one metal conductor Two or more metal microwires of the wire, the two or more metal microwires of the at least one metal conductor wire and the metal end wire forming a bundle pattern; (ii) each metal microwire The average length is at least 1 mm; and (iii) the relatively conductive metal connector has an overall transmittance of less than 68%.

7. The method of embodiment 6, wherein in the relatively conductive metal connector: (iv) for each metal microwire, the ratio of the maximum height to the minimum height is at least 1.05:1.

8. The method of embodiment 6 or 7, wherein in the relatively conductive metal connector: (v) an average width of each of the metal microwires in each of the bundled patterns and an average distance between two adjacent metal microwires The ratio is at least 0.5:1 but less than 2:1.

The method of any one of embodiments 6 to 8, wherein the relatively conductive metal connector comprises at least two adjacent metal wires, and an average distance between the at least two adjacent metal wires is greater than each bundle The average distance between any two adjacent metal microwires in the package.

10. The method of embodiment 9, wherein the average distance between any two adjacent metal microwires in each of the bundles of the relatively conductive metal connectors is at least 2 [mu]m and is at most and comprises 10 [mu]m.

11. The method of any one of embodiments 6 to 10, comprising simultaneously forming the conductive metal connector and the conductive metal grid on the first support side, and simultaneously forming the opposite conductive metal connector and the opposite conductive Metal grid.

12. The method of any of embodiments 1 to 11, wherein for each metal microwire, the ratio of the maximum height to the minimum height is at least 1.1:1.

The method of any one of embodiments 1 to 12, wherein the at least one metal microwire has a maximum height that is the same as its center height.

14. The method of any of embodiments 1 to 12, wherein one of the at least one metal microwire has a maximum height that is closer to its outer edge than its center height.

The method of any of embodiments 1 to 14, wherein each metal microwire has a ratio of a maximum height to an average height of at least 1.05:1.

16. The method of any of embodiments 1 to 15, wherein each metal microwire has an average width of at least 5 μm and a maximum of and including 20 μm.

17. The method of any of embodiments 1 to 16, wherein each bundle pattern comprises at least one metal bridge between adjacent metal microwires that is not at the end of the adjacent metal microwires wire.

The method of any of embodiments 1 to 17, wherein each of the bundled patterns comprises a plurality of metal jumper wires between adjacent metal microwires, wherein the plurality of metal jumper wires are configured to each other One distance apart by at least 100 μm.

19. The method of any of embodiments 1 to 18, wherein each bundle pattern comprises a plurality of metal jumper wires in a set of adjacent metal microwires, the plurality of metal jumper wires being offset from adjacent metal A plurality of metal jumper wires in adjacent groups of microwires.

20. The method of embodiment 19, wherein each of the plurality of metal jumper wires is substantially non-perpendicular to the adjacent metal microwires.

21. The method of any one of embodiments 1 to 20, wherein the average distance between any two adjacent metal main conductors is greater than the average distance between any two adjacent metal microwires in each of the bundled patterns At least 30% larger.

The method of any one of embodiments 1 to 21, wherein the ratio of the average width of each of the metal microwires in each of the bundled patterns to the average distance between two adjacent metal microwires is at least 1: 1 and the highest is and contains 2:1.

The method of any one of embodiments 1 to 22, wherein the conductive metal connector has There is an integrated transmittance of less than 50% and the conductive metal grid has an integrated transmittance of at least 90%.

24. The method of embodiment 6, wherein the relatively conductive metal connector has a combined transmittance of less than 50% and the relatively conductive metal mesh has an integrated transmittance of at least 90%.

The method of any of embodiments 1 to 24, wherein the transparent substrate is a continuous polymeric film.

The present invention also provides a conductive article of the method of any one of embodiments 1 to 25, the conductive article comprising a transparent substrate having a first support side and a second support side And the conductive object comprises on the first support side: (a) a conductive metal mesh, (b) a conductive metal connector electrically connected to the conductive metal mesh, and optionally, (c) transparent a region, which is external to both the conductive metal mesh and the conductive metal connector, wherein: (i) the conductive metal connector includes at least one metal bus, the at least one metal bus including the electrical connection to the Two or more metal microwires of the metal end conductor at one end of the at least one metal main conductor, the two or more metal microwires of the at least one metal main conductor and the metal end conductor forming a The bundled pattern; (ii) each metal microwire has an average length of at least 1 mm; and (iii) the conductive metal connector has a combined transmittance of less than 68%.

Other embodiments include touch screen devices, each of which includes a conductive article of embodiment 26, or more specifically:

A touch screen module, comprising: a conductive object, the conductive object comprising a first support side and a second opposite a transparent substrate on the support side; and the conductive object comprises on the first support side: (a) a conductive metal mesh, (b) a conductive metal connector electrically connected to the conductive metal mesh, and a case, (c) a transparent region, which is external to both the conductive metal mesh and the conductive metal connector, (d) two or more separate conductors that are electrically connected to the conductive metal connector a metal main conductor, and (e) a carrier support adhered to the electrically conductive article, wherein: (i) the electrically conductive metal connector comprises at least one metal main conductor, the at least one metal main conductor comprising an electrical connection Two or more metal micro-wires of one of the metal end wires at one end of the at least one metal main conductor, the two or more metal micro-wires of the at least one metal main conductor and the metal end wire Forming a bundle of patterns; (ii) each metal microwire has an average length of at least 1 mm; and (iii) the conductive metal connector has an overall transmittance of less than 68%.

2. The touch screen module of embodiment 1, wherein the carrier support is adhered to the second support side of the conductive article.

3. The touch screen module of embodiment 1, wherein the carrier support is adhered to the first support side of the conductive article.

4. The touch screen module of any of embodiments 1 to 3, wherein the two or more separate guiding systems are wires in a ribbon cable.

5. The touch screen module of any of embodiments 1 to 4, wherein the carrier support is light from a display passing through a transparent cover or film.

6. The touch screen module of any one of embodiments 1 to 5, wherein the carrier support member is a transparent cover or film of a display, and the conductive member is adhered to the transparent cover or film The display is on one side.

The touch screen module of any one of embodiments 1 to 5, wherein the carrier support is a transparent cover or film of a display, and the conductive object is located between the transparent cover or film and the display .

The touch screen module of any one of embodiments 1 to 7, wherein the carrier support is a transparent cover of a display, and the transparent cover is adhered to the display.

The touch screen module of any of embodiments 1 to 8, wherein the two or more separate conductors are electrically connected to a controller.

10. The touch screen module of any of embodiments 1 to 9, wherein the at least one metal bus is electrically connected to a controller.

11. The touch screen module of embodiment 10, wherein the controller is adhered to the carrier support.

12. The touch screen module of embodiment 10, wherein the controller is adhered to the first support side of the transparent substrate.

Other useful embodiments are:

A method for preparing a touch screen module, the method comprising: providing a conductive object, the conductive member comprising a transparent substrate having a first support side and a second support side; and the conductive The object on the first support side comprises: (a) a conductive metal mesh, (b) a conductive metal connector electrically connected to the conductive metal mesh, and optionally, (c) a transparent region, etc. Outside the electrically conductive metal mesh and the electrically conductive metal connector, wherein: (i) the electrically conductive metal connector comprises at least one metal main conductor, the at least one metal main conductor comprising an electrical connection to the at least one metal One of the ends of the main wire Two or more metal microwires of the wire, the two or more metal microwires of the at least one metal conductor wire and the metal end wire forming a bundle pattern; (ii) each metal microwire The average length is at least 1 mm; and (iii) the conductive metal connector has an overall transmittance of less than 68%; each of the metal conductors in the conductive metal connector is electrically connected to a separate conductor; One of the electrically conductive articles is laminated to a carrier support.

2. The method of embodiment 1, wherein laminating the electrically conductive article comprises laminating the second support side of the electrically conductive article to the carrier support.

3. The method of embodiment 1 or 2, wherein laminating the electrically conductive article comprises laminating the first support side of the electrically conductive article to the carrier support.

4. The method of any of embodiments 1 to 3, comprising using two or more separate conductors as the wires in a ribbon cable.

5. The method of any of embodiments 1 to 4, wherein the carrier support is light from a display through a transparent cover or film.

The method of any of embodiments 1 to 5, wherein the carrier support is a transparent cover or film of a display, and the method further comprises positioning the conductive article to the transparent cover or film and the display On one side of the opposite side.

The method of any of embodiments 1 to 6, wherein the carrier support is a transparent cover or film of a display, and the method further comprises positioning the conductive article on the transparent cover or film and the display between.

The method of any of embodiments 1 to 7, wherein the carrier support is a transparent cover of a display, and the method further comprises adhering the transparent cover to the display.

The method of any of embodiments 1 to 8, further comprising electrically connecting the individual conductors to a controller.

10. The method of any of embodiments 1 to 9, further comprising the at least one The root metal bus is electrically connected to a controller.

11. The method of embodiment 9 or 10, further comprising adhering the controller to the carrier support.

5‧‧‧Electrical objects

8‧‧‧ Conductive metal connectors

10‧‧‧ metal main line

20‧‧‧Metal microwires

22‧‧‧Metal end wire

40‧‧‧Transparent substrate

50‧‧‧(several) transparent areas

L‧‧‧Metal microwire length

S1‧‧‧Distance between adjacent metal conductor lines

S2‧‧‧Distance between adjacent metal microwires

W‧‧‧Metal microwire width

Claims (24)

A method for providing a conductive article, the method comprising: providing a transparent substrate having a first support side and a second support side; and providing on the first support side of the transparent substrate: (a) a conductive metal mesh, (b) a conductive metal connector electrically connected to the conductive metal mesh, and optionally, (c) a transparent region, the conductive metal mesh and the conductive metal connector Externally, wherein: (i) the conductive metal connector comprises at least one metal main conductor, the at least one metal main conductor comprising two of the metal end conductors electrically connected to one end of the at least one metal main conductor Or more metal micro-wires, the two or more metal micro-wires of the at least one metal main conductor and the metal-side wires form a bundle type; (ii) the average length of each metal micro-wire At least 1 mm; and (iii) the conductive metal connector has a combined transmittance of less than 68%. The method of claim 1, wherein: (iv) for each of the metal microwires, the ratio of the maximum height to the minimum height is at least 1.05:1. The method of claim 1 or 2, wherein: (v) the ratio of the average width of each of the metal microwires in each of the bundled patterns to the average distance between the two adjacent metal microwires is at least 0.5:1 but less than 2 :1. The method of claim 1 or 2, wherein the conductive metal connector comprises at least two phases An adjacent metal main conductor, and an average distance between the at least two adjacent metal main conductors is greater than the average distance between any two adjacent metal micro-conductors in each of the bundled patterns. The method of claim 4, wherein the average distance between any two adjacent metal microwires in each of the bundled patterns is at least 2 μm and up to and including 10 μm. The method of claim 1 or 2, further comprising: providing on the opposite second support side of the transparent substrate: (a) a relatively conductive metal mesh, (b) a relatively conductive metal connector, electrically connected Up to the relatively conductive metal mesh, and optionally, (c) a transparent region, external to both the opposing conductive metal mesh and the opposing conductive metal connector, wherein: (i) the relatively conductive metal connector comprises At least one metal main conductor, the at least one metal main conductor comprising two or more metal micro-wires electrically connected to one of the metal end conductors at one end of the at least one metal main conductor, the at least one metal leading The two or more metal microwires in the wire and the metal end wire form a bundle pattern; (ii) the average length of each metal microwire is at least 1 mm; and (iii) the relatively conductive metal connector It has an integrated transmittance of less than 68%. The method of claim 6, wherein in the relatively conductive metal connector: (iv) for each metal microwire, the ratio of the maximum height to the minimum height is at least 1.05:1. The method of claim 6, wherein in the relatively conductive metal connector: (v) the average width of each of the metal microwires in each of the bundled patterns and two adjacent metals The ratio of the average distance between the microwires is at least 0.5:1 but less than 2:1. The method of claim 6, wherein the relatively conductive metal connector comprises at least two adjacent metal wires, and the average distance between the at least two adjacent metal wires is greater than any two of the bundle patterns This average distance between adjacent metal microwires. The method of claim 9, wherein the average distance between any two adjacent metal microwires in each of the bundles of the relatively conductive metal connectors is at least 2 μm and up to and including 10 μm. The method of claim 6, comprising simultaneously forming the conductive metal connector and the conductive metal mesh on the first support side, and simultaneously forming the opposite conductive metal connector and the opposite conductive metal mesh. The method of claim 1, wherein for each metal microwire, the ratio of the maximum height to the minimum height is at least 1.1:1. The method of claim 1, wherein the at least one metal microwire has a maximum height that is the same as its center height. The method of claim 1, wherein one of the at least one metal microwire has a maximum height that is closer to its outer edge than its center height. The method of claim 1, wherein each of the metal microwires has a ratio of a maximum height to an average height of at least 1.05:1. The method of claim 1, wherein each of the bundle patterns comprises at least one metal jumper wire between adjacent metal microwires that is not at the end of the adjacent metal microwires. The method of claim 1, wherein each of the bundled patterns comprises a plurality of metal jumper wires between adjacent metal microwires, wherein the plurality of metal jumper wires are configured to be at a distance of at least 100 μm from each other. The method of claim 1, wherein each of the bundled patterns comprises a set of adjacent metal microwires A plurality of metal jumper wires, the plurality of metal jumper wires being offset from the plurality of metal jumper wires in an adjacent group of the adjacent metal microwires. The method of claim 18, wherein each of the plurality of metal jumper wires is substantially non-perpendicular to the adjacent metal microwires. The method of claim 1, wherein the ratio of the average width of each of the metal microwires in each of the bundled patterns to the average distance between the two adjacent metal microwires is at least 1:1 and is at least 2 :1. The method of claim 1, wherein the transparent substrate is a continuous polymeric film. A conductive article of the method of any one of claims 1 to 21, the conductive article comprising a transparent substrate having a first support side and a second opposite support side, and the first support The side includes: (a) a conductive metal mesh, (b) a conductive metal connector electrically connected to the conductive metal mesh, and optionally, (c) a transparent region, etc. in the conductive metal mesh And the outer side of the conductive metal connector, wherein: (i) the conductive metal connector comprises at least one metal bus, the at least one metal bus comprises an electrical connection to one end of the at least one metal conductor Two or more metal microwires of a metal end conductor, the two or more metal microwires of the at least one metal conductor line and the metal end conductor form a bundle type; (ii) each The metal microwires have an average length of at least 1 mm; and (iii) the conductive metal connectors have an overall transmittance of less than 68%. The conductive article of claim 22, wherein each of the metal microwires has an average width of at least 5 μm and a maximum of 20 μm. A touch screen device comprising a conductive article as claimed in claim 22 or 23.