TW201610609A - Silver halide solution physical developing solution and method of use - Google Patents

Abstract

A black-and-white developing solution and a silver halide solution physical developing solution are used in sequence to provide electrically-conductive film elements from conductive film element precursors that contain photosensitive silver halide emulsions on one or both supporting sides of a transparent substrate. The two developing solutions have unique combinations of developing agents and other essential components to provide complete development of imagewise exposed silver halide and highly conductive silver metal in desired patterns on a transparent substrate.

Description

Physical imaging solution of silver halide solution and using method thereof

The present invention is directed to a method of providing a conductive silver film element (or conductive article) using a unique combination of processing features and processing solutions. The conductive silver film elements can be provided with a predetermined conductive silver pattern and used in different electronic devices, or they can be further processed to provide a pattern of other conductive metals plated over the silver. The method can be performed after imagewise exposure of a conductive thin film element precursor using a unique silver halide physical imaging solution.

Various electronic devices, particularly display devices, for various communication, financial, retrieval, and archival purposes have experienced rapid progress. Conductive films are necessary for applications such as touch screen panels, electrochromic devices, light-emitting diodes, field effect transistors, and liquid crystal displays, and considerable efforts are made in the industry to improve the properties of their conductive films and their Production method.

In addition, with the development of the mentioned display device in recent years, its attraction has been greatly increased by means of touch screen technology, whereby a tap on the surface of the screen with a finger or a stylus can generate a signal to cause a screen view. Many other features that are being developed or are being developed, resulting in the receipt or transmission of information, telecommunications, interaction with the Internet, and innovation at an ever-increasing pace. Touch screen technology has largely become possible by using a transparent conductive grid on the main display so that the position of the touch on the surface of the screen can be detected by appropriate circuitry and software.

Currently, most touch screen displays use indium tin oxide (ITO) coatings for production. To distinguish the array of capacitive regions of multi-point contact. ITO coatings have significant drawbacks and efforts are being made to replace their use in various electronic devices. Indium is an expensive rare earth metal and is available in the world from a limited supply from a limited supply. ITO conductivity is relatively low and requires short line lengths to achieve adequate response rates. The touch screen for large displays is split into smaller segments to reduce the length of the conductive trace to an acceptable resistance. ITO is a ceramic material that is not easily bent or bent and requires vacuum deposition at high processing temperatures to prepare a conductive layer.

Silver is an ideal conductor that is 50 to 100 times more conductive than ITO. Silver is used in many commercial applications and is available from a variety of sources. It is highly desirable to use silver as a source of conductivity to fabricate conductive thin film components, but significant development or other processing operations are required to achieve optimal conductive properties.

U.S. Patent Application Publication No. 2011/0308846 (Ichiki) describes the preparation of a conductive film which is formed by reducing the size of a silver halide image in a conductive network by using a silver wire size of less than 10 μm, which can be used to form a display. Touch panel.

In addition, U.S. Patent No. 3,464,822 (Blake) describes the use of a silver halide emulsion for use in photographic elements to form a conductive silver surface image by one or more processing baths after development and development.

U.S. Patent 7,829,270 (Nakahira) describes the use of a photosensitive silver halide material for forming a conductive silver metal pattern. After exposure to the photosensitive silver halide material, it is processed using a black and white imaging solution followed by fixation and physical imaging and electroless plating operations.

Further, a similar method is described in U.S. Patent No. 8,012,676 (Yoshiki et al.), but further includes the operation to enhance the conductivity of the resulting silver metal image.

Accordingly, it is known to provide a conductive silver pattern on a transparent film using a variety of processing solutions and conditions. However, it is furthermore necessary to increase the conductivity of the silver pattern, especially in the form of fine lines, without increasing _Dmin . In other words, it is necessary to balance the improved silver metal conductivity, increased transparency, and low _{Dmin in the} conductive silver image. The present invention has been developed in view of such needs.

The invention provides a physical imaging solution of a silver halide solution, which comprises: (a) a primary imaging agent in an amount of at least 0.01 mol/l and up to and including 1 mol/l, which is hydroquinone or ascorbic acid or a derivative of either, and (c) at least 0.001 mol/l and up to and including The silver halide solution is dissolved in an amount of 0.1 mol/l, and the physical development solution of the silver halide solution contains substantially no (b) catalytic developer.

The present invention also provides a method of providing a conductive silver image on a transparent substrate in a conductive thin film element, the method comprising, in order, imaging exposing a conductive thin film element precursor comprising a transparent substrate having a first support side and a second support side And the conductive film element precursor comprises, in order, on the first support side, a first achromatic hydrophilic photosensitive layer comprising photosensitive silver halide, and optionally disposed above the first achromatic hydrophilic photosensitive layer a first hydrophilic overcoat layer to provide an imagewise exposure precursor comprising a first latent silver image in the first achromatic hydrophilic photosensitive layer, at a pH of at least 8 and up to and including 13 and comprising halogenation Processing the imagewise exposure precursor in the silver imaging solution for at least 10 seconds: (a) at least 0.01 mol/l and up to and including 1 mol/l of the primary imaging agent, which is hydroquinone or ascorbic acid or either a derivative, and (b) a catalytic developer in an amount of at least 0.001 mol/l and up to and including 0.1 mol/l, which is a p-aminophenol or phenidone or a derivative thereof, in the a non-colored hydrophilic layer of light Providing a first silver image corresponding to the first latent silver image, processing the imagewise exposure prior to processing in a physical imaging solution of a silver halide solution according to any of the embodiments described herein at a temperature of at least 20 °C Body for at least 30 seconds to provide conductivity of the silver image, which is at least 2 times greater than the conductivity of the first silver image after processing with only the first imaging solution, processing the image in a fixing solution Exposing the precursor to remove residual silver ions and providing a conductive thin film element containing the first silver image, processing the conductive thin film element to enhance conductivity of the first silver image, and The conductive film member is washed and dried as appropriate.

In some embodiments of the invention, the method is performed using a conductive thin film element precursor, the conductive thin film element precursor further comprising a second achromatic hydrophilic photosensitive layer on the opposite second support side of the transparent substrate, and a second hydrophilic overcoat layer disposed over the second achromatic hydrophilic photosensitive layer, and the method further comprising: imaging exposing the conductive thin film element precursor from the second opposite side of the transparent substrate to Providing a second latent silver image in the second achromatic hydrophilic photosensitive layer of the imagewise exposure precursor, processing the image in a silver halide imaging solution having a pH of at least 8 and up to and including 13 and comprising the same or different silver halide imaging solutions Exposing the precursor for at least 10 seconds: (a) at least 0.01 mol/l and up to and including 1 mol/l of the primary imaging agent for at least 10 seconds, which is hydroquinone or ascorbic acid or a derivative of either, and b) a catalytic developer in an amount of at least 0.001 mol/l and up to and including 0.1 mol/l, which is a p-aminophenol or phenidone or a derivative thereof, to be hydrophilic in the second achromatic hydrophilic Provided in the light layer corresponding to the a second silver image of the second latent silver image, at least 30 after processing the imagewise exposure in a physical imaging solution of the same or different silver halide solution of any of the embodiments described herein at a temperature of at least 20 °C Seconds to provide conductivity of the silver image, which is at least 2 times the conductivity of the second silver image after processing with only the first development solution, before processing the imagewise exposure in the fixing solution a body for removing remaining silver ions and providing a conductive thin film element containing the second silver image, treating the conductive thin film element to enhance conductivity of the second silver image, and optionally washing and drying the conductive thin film element .

The method of the present invention can be used to provide a conductive film element of the present invention having a first silver image on a first support side of a transparent substrate and optionally a second on a second support side of the transparent substrate Silver image. The first and second silver images are electrically conductive It can be used alone or with other conductive metals.

The present invention can be carried out using a unique silver halide imaging solution having a pH of at least 8 and comprising: (a) a primary imaging agent in an amount of at least 0.01 mol/l and up to and including 0.15 mol/l, which is hydroquinone or ascorbic acid Or a derivative of either, (b) a catalytic developer in an amount of at least 0.001 mol/l and up to and including 0.025 mol/l, which is a p-aminophenol or phenidone or a derivative thereof And (c) one or more development inhibitors in a total amount of at least 0.25 mol/l and up to and including 2.5 mol/l.

The present invention provides several advantages of an improved conductive film element comprising a highly conductive silver metal image that can be disposed in a predetermined pattern of fine lines or grids. The resulting conductive film member exhibits high conductivity and high transparency while keeping (visual) D _min as low as possible, for example, less than or equal to 0.3, after processing in the fixing solution. These advantages are achieved by using a unique combination of black and white silver halide imaging solutions prior to fixation.

The following discussion is directed to the various embodiments of the present invention, and the disclosed embodiments are not to be construed as limiting or limiting the scope of the invention. In addition, those skilled in the art will understand that the following disclosures are more broadly described, and the description of any embodiments is not intended to limit the scope of the invention.

definition

Unless otherwise indicated, the singular forms "a" and "the" are used to define the processing solutions and various layers and formulations of the precursors of the conductive film element precursors. Intended to include one or more of these components (in other words, including a plurality of indicators).

Terms that are not explicitly defined in this application are to be understood as having the meaning commonly accepted by those skilled in the art. If the construction of terms makes them meaningless or essentially meaningless in their context, the definition of terms should be taken from English or chemical dictionaries.

The use of numerical values in the various ranges specified herein is considered to be an approximation, as the meaning of the minimum and maximum values within the range. In this way, small variables above and below the range can be used to substantially achieve the same results as the values in the range. Further, the disclosure of such ranges is intended to include a continuation of the various values between the minimum and maximum values.

Unless otherwise indicated, the term "% by weight" refers to the amount of the component or material, based on the total solids of the composition, formulation, solution, or the percentage of the dry weight of the layer. Unless otherwise indicated, the percentages may be the same for the 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 term "mol%" means the molar amount of a particular component (or mixture of components of the same class) within a solution or dispersion.

The "conductive film element precursor" (or "precursor") is intended to mean an article or element for practicing the invention to provide the electroconductive film element of the invention. The conductive thin film element precursors thus comprise a silver metal particle precursor, such as a silver halide that is suitably converted (e.g., by reduction) to a silver metal as described below. Many of the statements regarding the precursors of conductive thin film elements are equally applicable to conductive thin film elements because most of the components and structures do not change when silver cations in silver halide are converted to silver metal particles. Therefore, unless otherwise indicated, the discussion of the substrate, hydrophilic binder and colloid, and any other addenda in the silver halide layer and the hydrophilic overcoat layer for the conductive film element precursor is also intended to describe the resulting conductive film element. Component.

Unless otherwise indicated, the terms "conductive film element/electrically-conductive film elements" and "conductive articles" are intended Refers to the same thing. It refers to a material containing a hydrophilic layer comprising a conductive silver metal image (or other conductive metal image) disposed on one or both of the support sides. Other components of the conductive article or conductive film element are described below.

Unless otherwise indicated, the term "conducting" means "conductivity" rather than thermal conductivity.

The term "first" refers to a layer on one of the support sides of the substrate, and the term "second" refers to the layer on the opposite (opposite) support side of the substrate. The support sides of the substrate are equally applicable and the term "first" does not necessarily mean that one side is the primary or better support side of the support.

The terms "duplex" and "double side" are used herein with respect to conductive thin film element precursors and conductive thin film elements having the layers described on both support sides of the substrate. The relationships and compositions of the various layers on the two support sides of the substrate may be the same or different, unless otherwise indicated herein. In addition, the silver halide disposed on the opposite support side of the substrate can be imaged and processed using the same or different processing solutions and conditions.

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

Unless otherwise indicated, "black and white" refers to black and white materials and formulations that form silver, rather than black-and-white materials and formulations.

use

A conductive film element precursor can be used to practice the invention to form a conductive film element comprising a conductive silver metal pattern on one or both of the support sides of a suitable substrate. These electrically conductive film elements may themselves be used as devices or as components in devices having a variety of applications including, but not limited to, electronic, optical, sensory, and diagnostic applications. Further details of such uses are provided below. In particular, it is desirable to use the conductive thin film element precursor of the present invention to provide a highly conductive silver metal pattern (or other conductive metal pattern) having a line having less than 50 μm or less than 15 μm or even less than 10 μm and as low as 1 μm. Line Resolution (line width).

Particularly suitable is the preparation of a conductive film element comprising a conductive silver pattern on a first and opposite second support side of a transparent substrate. The electronic and optical devices and components include, but are not limited to, radio frequency tags (RFID), sensors, touch screen displays, and memory and back panels for displays.

Conductive film element precursor

The precursor of the conductive film element suitable for use in practicing the present invention is photosensitive but does not contain a chemical sufficient to provide a color photographic image. Therefore, these precursors are regarded as black and white photosensitive materials which form a metallic silver image after exposure and processing, and are "formed by achromatic images".

The conductive thin film element precursor including the transparent substrate and all of the accompanying layers on the support side and the resulting conductive thin film element are considered to be transparent, meaning that the entire element is in the visible region indicated by the electromagnetic spectrum (for example, 410 nm) The overall transmittance on the 700 nm) may be 70% or more, or more preferably at least 85% or even 90% or more. The integrated transmittance can be measured using a spectrophotometer and known procedures.

A conductive thin film element precursor having the same or different necessary layers on both support sides of a transparent substrate may be referred to as a "duplex" or "double-sided" conductive thin film element precursor.

The conductive thin film element precursor can be formed by providing a first achromatic (in other words, a black metal forming black and white) hydrophilic photosensitive layer on at least one of the supporting or planar sides (opposite the unsupported edge) suitable for the transparent substrate in a suitable manner. . The first achromatic hydrophilic photosensitive layer comprises a silver halide or a silver halide mixture having a total silver coverage of at least 2500 mg Ag/m ² , or at least 3500 mg Ag/m ² , and in many embodiments less than 5000 mg Ag/m ² , For example, up to and including 4900 mg Ag/m ² . However, higher silver coverage can be used if necessary. Thus, this achromatic hydrophilic photosensitive layer has sufficient silver halide intrinsic or added spectral sensitization to be photosensitive to selected imaging radiation (described below). The composition and spectral sensitization of the photosensitive layer on the opposite support sides of the transparent substrate may be the same or different.

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

The conductive thin film element precursors are thus treated in one manner (imagewise exposure) to convert the silver cations (such as by reduction) to silver metal particles, and the exposure precursor can then be suitably processed or processed as described below. It is then converted into a conductive film element of the invention.

The conductive thin film element precursor consists essentially of a necessary layer on each of the support sides of the substrate, which is an achromatic hydrophilic photosensitive layer disposed on the transparent substrate. This necessary layer can be disposed on only one of the support sides of the transparent substrate, but in many duplex embodiments it is disposed on both the first and opposite second support sides of the transparent substrate. The hydrophilic overcoats described below are optionally selected but are highly desirable in many embodiments, and the hydrophilic overcoats are disposed directly on the achromatic hydrophilic photosensitive layer. The layers may be disposed on only one of the support sides of the transparent substrate, or they may be disposed in the same order on both the first support and the opposite second support side of the transparent substrate. Other layers, optionally selected, may also be present on either or both of the support sides, as described below.

Transparent substrate:

The choice of transparent substrate will generally depend on the intended utility of the resulting conductive film element. It can be rigid or flexible and is generally transparent as described above. For example, the substrate can be a transparent flexible substrate that has a combined transmittance measured on the visible region indicated by the electromagnetic spectrum using a standard spectrophotometer and program as described above, at least 80% and typically at least 95% .

Suitable transparent substrates include, but are not limited to, glass, glass reinforced epoxy laminate, cellulose triacetate or another cellulose ester, acrylate, polycarbonate, adhesive coated polymer substrate, polymer Substrates (such as polyester film) and composite materials. Polymers suitable for use as polymer substrates include, but are not limited to, polyethylene, polyesters (such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN)), polypropylene, polyacetic acid Ethylene Esters, polyurethanes, polyamines, polyimines, polybenzazoles, and mixtures thereof.

The polymeric substrate may also comprise two or more layers having the same or different polymeric compositions such that the composite substrate (or laminate) has the same or different layer refractive properties. The transparent substrate can be treated on either or both of the support sides to improve the adhesion of the silver salt emulsion or dispersion to one or both of the support sides of the substrate. For example, the transparent substrate can be coated with a layer of polymeric adhesive on one or both of the support sides, or it can be chemically treated or subjected to corona treatment.

Bidirectionally oriented sheets, although described as having at least one layer, may also be provided with additional layers that may be used to alter the optical or other properties of the bidirectionally oriented sheets. The layers may contain a hue, an antistatic or electrically conductive material or a slip agent. If necessary, up to 10 layers can be used for biaxially oriented extrusion to achieve some specific properties.

A transparent substrate that is particularly suitable for use in the manufacture of flexible electronic devices or touch screen assemblies is flexible, which facilitates rapid roll coating. Estar ^® Poly manufacture of flexible material of the transparent substrate used in the present invention (ethylene terephthalate) film and a cellulose triacetate film is particularly suitable.

The transparent substrate can be the same as the support or film that has been incorporated into the flexible display device, which means that the necessary layers described herein are applied to the transparent substrate material within the display device and imaged in situ according to the desired pattern, and subsequently In situ processing.

When a discrete transparent substrate (in other words, a transparent substrate has not been incorporated into a flexible display device) is utilized, a layer (from a formulation) is provided on one or both of its support sides. If different patterns (or grids) are intended for each support side, a substrate containing a filter dye or optionally an intervening filter (or anti-halation) layer may be provided to prevent exposure from one side to the other. . Alternatively, the silver halide emulsion can be sensitized differently for the relatively achromatic hydrophilic photosensitive layer on the opposite support side of the transparent substrate.

The transparent substrate used in the conductive film element precursor may 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 if necessary It is incorporated into a transparent substrate in amounts that are apparent to those skilled in the art.

Achromatic hydrophilic light layer:

The necessary silver halide in such layers comprises one or more silver halide silver cations which can be converted to silver metal particles according to the desired pattern after imagewise exposure of each achromatic hydrophilic photosensitive layer. The latent image can then be imaged into a silver metal image using known silver imaging procedures and chemicals (described below). Silver halide (or silver halide combination) is photosensitive, meaning that UV to visible radiation (eg, at least 200 nm and up to and including 750 nm radiation) is typically used to convert silver cations into silver metal particles in a latent image. In some embodiments, silver halide is present in combination with a thermosensitive silver salt such as silver behenate, and the achromatic photosensitive hydrophilic layer can be photosensitive and heat sensitive (sensitive to imaging heat such as infrared radiation) .

Suitable photosensitive silver halides can be, for example, silver chloride, silver bromide, silver chlorobromide iodide, silver bromide iodide, silver chlorobromide, silver bromochloride or silver iodobromide, which are prepared in the form of individual compositions (or emulsions). The various halides are listed in the silver halide nomenclature as a percentage of halide. Additionally, individual silver halide emulsions can be prepared and mixed to form a silver halide emulsion mixture for the same or different support sides of the substrate. In general, suitable silver halides can comprise 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.

The silver halide grains used in each of the achromatic hydrophilic photosensitive layers may generally have an ESD of at least 30 nm and up to and including 300 nm, or more preferably at least 50 nm and up to and including 200 nm.

The total silver coverage in the silver halide in each of the achromatic hydrophilic photosensitive layers can be at least 2500 mg Ag/m ² and typically at least 3500 mg Ag/m ² and at most any amount but typically less than 5000 mg Ag/m ² , for example at most Includes 4900 mg Ag/m ² . Use higher silver coverage if necessary.

The dry thickness of each achromatic hydrophilic photosensitive layer can generally be 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 achromatic hydrophilic photosensitive layer can be comprised of one or more individually coated achromatic hydrophilic photosensitive sub-layers that can be coated with the same or different silver halide emulsion formulations. Each sublayer may be composed of the same or different silver halides, hydrophilic binders or colloidal additions. The sublayers may have the same or different amounts of silver content.

The photosensitive silver halide used in the first achromatic hydrophilic photosensitive layer may be the same as or different from the photosensitive silver halide used in the second support side achromatic hydrophilic photosensitive layer.

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), poly(vinylpyrrolidone) (PVP), casein, and mixtures thereof. Suitable hydrophilic colloids and ethylene polymers and copolymers are also described in Research Disclosure , Part IX, Project 36544, published by Kenneth Mason Publications, Emsworth, Hants, PO 10 7DQ, UK, September 1994.

The amount of hydrophilic binder or colloid in each of the achromatic hydrophilic optical layers can be adapted to the particular dry thickness desired and the amount of silver halide incorporated. It may also be adapted to satisfy the desired dispersibility, expansion, and adhesion to the layer of the transparent substrate. In general, one or more hydrophilic binders or colloids may be present in an amount of at least 10% by weight and up to and including 95% by weight, based on the total solids in the emulsion formulation or dry layer.

Some suitable achromatic hydrophilic photosensitive layer compositions have a relatively high silver ion/low hydrophilic binder (e.g., gelatin) weight ratio. For example, a particularly suitable weight ratio of silver ions (and final silver metal) to a hydrophilic binder or colloid such as gelatin (or a derivative thereof) can be at least 0.1:1, or even at least 1.5:1 and at most And includes 10:1. A particularly suitable weight ratio of silver ions to hydrophilic binders or colloids can be at least 2:1 and up to and including 5:1. Different ratios can be used for the intended purpose if necessary.

The hydrophilic binder or colloid can be used in combination with one or more hardeners designed to harden a particular hydrophilic binder, such as gelatin. Particularly suitable for hard gelatin and gelatin derivatives Agents include, but are not limited to, non-polymeric vinyl-oximes such as bis(vinyl-indenyl)methane (BVSM), bis(vinyl-mercaptomethyl)ether (BVSME), and 1,2-bis(vinyl) - mercaptoacetamide) ethane (BVSAE). A mixture of hardeners may be used if necessary. The hardener can be incorporated into each achromatic hydrophilic photosensitive layer in any suitable amount as would be apparent to those skilled in the art.

In general, each achromatic hydrophilic photosensitive layer can have an expansion ratio of at least 150% as determined by optical microscopy of the cross-section of the element. The expansion can be controlled by the amount of hardening carried out in a layer of photosensitive silver halide emulsion or in various processing solutions (described below) with an appropriate amount of hardener.

If appropriate, the applicable silver halide described above can be sensitized to exposure radiation of any suitable wavelength. An organic sensitizing dye can be used, but it can be advantageous to sensitize the silver salt to the UV portion of the electromagnetic spectrum without using a visible light sensitizing dye to avoid undesirable dye stains in conductive articles where high transparency is desired. . Alternatively, silver halide can be used without spectral sensitization beyond its inherent spectral sensitivity.

Applicable to addenda included with silver halide (including chemical and spectral sensitizers, filter dyes, organic solvents, thickeners, dopants, emulsifiers, surfactants, stabilizers, hardeners and defenses) Non-limiting examples of aerosols are described in Research Disclosure Project 36544, September 1994 and many of the publications identified therein. Such materials are well known in the art and will be readily adapted or used by those skilled in the art for the purposes described herein. Some suitable silver salt emulsions are described, for example, in U.S. Patent Nos. 7,351,523 (Grzeskowiak), 5,589,318, and 5,512,415 (both to Dale et al.).

Suitable silver halide emulsions containing silver halide grains that can be reduced to silver metal particles can be prepared by any suitable particle growth method, for example by using a feedback system designed to maintain the concentration of silver ions in the growth reactor, using silver nitrate and Double observation of the balance of the salt solution. It is known that dopants can be uniformly introduced from the beginning to the end of the precipitation or can be structured to halogenation. In the area or band within the silver particles. Suitable dopants include, but are not limited to, antimony dopants, antimony dopants, iron dopants, antimony dopants, antimony dopants, and cyanoquinone dopants. Combinations of ruthenium and osmium dopants, such as combinations of nitrosonium ruthenium pentachloride and ruthenium dopants, are suitable. These complexes can alternatively be used as particle surface modifiers in the manner described in U.S. Patent 5,385,817 (Bell). Chemical sensitization can be carried out by any of the known silver halide chemical sensitization methods, for example, using a thiosulfate alone or in combination with a gold complex or another unstable sulfur compound.

Suitable silver halide grains may be circular cubic, cubic circular, octahedral, circular octahedron, polycrystalline, flaked or flaked emulsion particles. The silver halide grains may be regular non-dual, regular twin or irregular twin, having a cubic or octahedral surface. In one embodiment, the silver halide grains may be circular cubes having an edge length of less than 0.5 [mu]m and at least 0.05 [mu]m.

Antifogging agents and stabilizers may be added as appropriate to give the desired sensitivity to the silver halide emulsion. Antifogging agents which may be used include, for example, azaindoles such as tetraazaindene, tetrazole, benzotriazole, imidazole and benzimidazole.

The necessary silver halide grains and hydrophilic binders or colloids and optionally additions may be formulated and coated in the form of a silver halide emulsion using a suitable emulsion solvent (including water and water miscible organic solvents). For example, a solvent suitable for use in the manufacture of a silver halide emulsion or coating formulation can be water; an alcohol such as methanol; a ketone such as acetone; a guanamine such as formamide; an anthracene such as dimethyl hydrazine; Such as ethyl acetate; ether; liquid polyvinyl alcohol; liquid or low molecular weight poly(vinyl alcohol); or a combination of such solvents. The amount of one or more solvents used to prepare the silver halide emulsion may be at least 30% by weight and up to and including 50% by weight of the total formulation. Accordingly, such coating formulations can be prepared using any of the photographic emulsion manufacturing procedures known in the art.

Hydrophilic outer coating

Although the achromatic hydrophilic photosensitive layer can be the outermost layer of the precursor, in many implementations In one example, a hydrophilic outer coating can be placed over each of the achromatic hydrophilic photosensitive layers on either or both of the support sides of the transparent substrate. The hydrophilic outer coating layer may be the outermost layer of the conductive film element precursor (in other words, there is no layer intentionally placed thereon on either or both of the support sides of the transparent substrate). Therefore, generally, if the two supporting sides of the transparent substrate are used to provide a conductive silver pattern, the hydrophilic overcoat layer may be present on the two supporting sides of the transparent substrate. Therefore, the first hydrophilic outer coating layer may be disposed above the first achromatic hydrophilic photosensitive layer, and the second hydrophilic outer coating layer may be disposed on the second achromatic second hydrophilic photosensitive layer on the opposite supporting side of the substrate. Above.

In most embodiments, each hydrophilic overcoat layer can be disposed directly on each of the achromatic hydrophilic photosensitive layers, meaning that no intervening layers are present on the support sides 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 both support sides of the transparent substrate.

In some embodiments, each hydrophilic overcoat (first or second or both) may comprise one or more silver halides of the same or different amounts to provide at least 5 mg Ag/m ² and at most after exposure and processing. Silver metal particles are included in an amount of 150 mg Ag/m ² , or at least 5 mg Ag/m ² and up to and including 100 mg Ag/m ² .

The silver halide may be dispersed (generally uniformly) in one or more hydrophilic binders or gels in each of the hydrophilic outer coatings, including the hydrophilic coloring layer described above for the achromatic hydrophilic layer They are the same. In many embodiments, the same hydrophilic adhesive or colloid can be used in all layers of the conductive film element precursor. However, different hydrophilic binders or gels can be used in the various layers and on either or both of the support sides of the support substrate. The amount of one or more hydrophilic binders or colloids in each hydrophilic overcoat layer may be the same or different and is typically at least 50% by weight and up to and including 97% by weight, based on the total hydrophilic overcoat dry weight.

The hydrophilic overcoat layer can include one or more radiation absorbers, such as a UV radiation absorber, in an amount of at least 5 mg/m ² and up to and including 100 mg/m ² . Suitable UV radiation absorbers can be "fixed" so that they do not readily diffuse from the hydrophilic outer coating.

Each hydrophilic overcoat layer may also comprise one or more hardeners for hydrophilic binders or colloids such as gelatin or gelatin derivatives. Suitable hardeners are described above.

It is also possible that the silver halide in each of the hydrophilic outer coatings is the same as the silver halide in each of the achromatic hydrophilic photosensitive layers on which the upper surface is disposed.

Furthermore, one or more of the silver halides in each hydrophilic overcoat layer can have a particle ESD of at least 30 nm and up to and including 1000 nm, or at least 30 nm and up to and including 300 nm.

In some embodiments, one or more of the silver halides in each hydrophilic overcoat layer has a particle ESD that is greater than the particle ESD of the silver halide in the achromatic hydrophilic photosensitive layer on which it is disposed.

Each hydrophilic overcoat layer 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 many embodiments, the particle ESD to dry thickness ratio in the hydrophilic overcoat layer can be from 0.25:1 to and including 1.75:1 or more likely from 0.5:1 to and including 1.25:1.

In various embodiments, the silver halide in each hydrophilic overcoat layer may comprise up to 100 mol% bromide or up to 100 mol% chloride, and up to and including 3 mol% iodide, all in terms of total silver content. .

In other embodiments, the silver halide in each hydrophilic overcoat layer may comprise more chloride than the silver halide in the achromatic hydrophilic photosensitive layer on which it is disposed. This relationship may be the same or different on the two support sides of the substrate in the precursor of the "duplex" conductive film element.

In a suitable embodiment, the silver halide in each hydrophilic overcoat layer may comprise at least 80 mol% bromide based on the total silver content, and the remainder being chloride or iodide, and the achromatic hydrophilic light disposed thereon is disposed thereon. The silver halide in the layer may have at least 80 mol% bromide and the remainder being iodide or chloride, all based on the total silver content.

It is also applicable in the precursor of the electroconductive thin film element of the present invention that the silver halide in each hydrophilic overcoat layer and the silver halide in each of the achromatic hydrophilic photosensitive layers on which the upper surface layer is disposed are matched in terms of photographic speed. When expressed in units of μJ/m ² , the exposure sensitivity of the silver halide emulsion in the hydrophilic overcoat layer may be the optimum sensitivity of the silver halide emulsion in the underlying achromatic hydrophilic photosensitive layer for providing a conductive silver pattern. This is best achieved at least 10% and up to and including 200%.

Additional layer:

In addition to the layers and components described above on one or both of the support sides of the transparent substrate, the conductive film element precursors used in the practice of the present invention may also include other layers that are not required but may provide some additional properties or benefits. Such as radiation absorbing filter layers, adhesive layers and other layers known in the art of photography. The radiation absorbing filter layer may also be referred to as an "antihalation" layer that can be positioned between the necessary layers on each of the support sides of the transparent substrate. For example, each support side can have a radiation absorbing filter layer disposed directly thereon and disposed directly beneath the achromatic hydrophilic photosensitive layer.

The radiation absorbing filter layer may comprise one or more filter dyes that are absorbed in the UV, red, green or blue regions of the electromagnetic spectrum, or any combination thereof, and may be positioned on one or both of the support sides of the transparent substrate. Between the substrate and the achromatic hydrophilic photosensitive layer.

For example, the conductive thin film element precursor may include a UV radiation absorbing layer between the first support side of the transparent substrate and the first achromatic hydrophilic photosensitive layer.

The duplex conductive film element precursor further includes a second achromatic hydrophilic photosensitive layer on the opposite second support side of the transparent substrate, and a second hydrophilic overcoat layer disposed over the second achromatic hydrophilic photosensitive layer. A radiation (eg, UV) absorbing filter layer can be disposed between the opposite second support side of the transparent substrate and the second achromatic hydrophilic photosensitive layer, the radiation absorbing layer being permeable to radiation absorption on the first support side of the transparent substrate The filter layers are the same or different.

In many duplex embodiments, the second achromatic hydrophilic photosensitive layer and the second hydrophilic outer coating respectively have the same composition as the first achromatic hydrophilic photosensitive layer and the first hydrophilic outer coating.

Therefore, in some embodiments, the conductive thin film element precursor may further include a second achromatic hydrophilic photosensitive layer on the opposite second supporting side of the transparent substrate, and optionally disposed above the second achromatic hydrophilic photosensitive layer. A second hydrophilic outer coating.

For example, the second achromatic hydrophilic photosensitive layer and the second hydrophilic outer coating may have the same composition as the first achromatic hydrophilic photosensitive layer and the first hydrophilic outer coating, respectively.

In other embodiments, the exposure sensitivity of the silver halide emulsion in the first hydrophilic overcoat layer may be the optimal sensitivity of the silver halide emulsion in the first achromatic hydrophilic photosensitive layer, as expressed in μJ/m ^{2 .} At least 10% and up to and including 200%, and as expressed in μJ/m ² , the exposure sensitivity of the silver halide emulsion in the second hydrophilic outer coating layer may be halogenated in the second achromatic hydrophilic photosensitive layer The optimal sensitivity of the silver emulsion is at least 10% and up to and including 200%. The optimal sensitivity of the respective sides of the transparent substrate can be the same or different.

Preparation of conductive film element precursor

The various layers are formulated with the appropriate components and coating solvent and applied to one or both of the support sides of a suitable transparent substrate (as described above) using known coating procedures, including those commonly used in the photographic industry. Etc. (eg, bead coating, knife coating, curtain coating, spray coating, and hopper coating). The layers can be applied to the respective support sides of the transparent substrate in a single channel process or a simultaneous multilayer coating process.

Providing conductive film components

A conductive thin film element precursor suitable for use in the method of the present invention is provided and subsequently imagewise exposed to provide a latent silver metal image in the achromatic hydrophilic photosensitive layer on either or both of the support sides of the transparent substrate. Imagewise exposure also reduces any silver halide present in the hydrophilic overcoat to silver metal particles. The conductive film element precursor can be used immediately for the intended purpose, or it can be stored in the form of a roll or sheet for later use. For example, the precursor can be rolled up during storage and stored for use in roll-to-roll imaging and processing, and then cut to the desired size and shape.

More generally, the photosensitive silver halide in each of the achromatic hydrophilic photosensitive layers can be imagewise exposed to Appropriate actinic radiation (UV to visible radiation) from a suitable source well known in the art is used and subsequently developed as described below (silver ion reduction to silver metal particles). The exposure provides an imagewise exposure precursor comprising a latent silver image in the first achromatic hydrophilic photosensitive layer and a latent silver image in the second achromatic hydrophilic photosensitive layer (if present in the precursor).

In some embodiments, the exposure process is controlled such that any exposure radiation for the achromatic hydrophilic photosensitive layer on one of the support sides of the transparent substrate does not reach any achromatic hydrophilic light on the opposite second support side of the transparent substrate. Floor. This result can be achieved in different ways as described, for example, in U.S. Patent Application Serial No. 2011/0289771 (Kuriki). Particularly suitable for comprising a radiation filter dye layer or an antihalation layer on both sides of the transparent substrate, the layer being disposed between the transparent substrate and each of the (first and second) achromatic hydrophilic photosensitive layers, and used for exposure Radiation is conducted at the precursor of the conductive film element from the first (or second or both) support side of the transparent substrate.

Processing with silver halide imaging solution:

The first processing may be carried out using a silver halide imaging solution (black and silver imaging agent forming a silver metal) having a pH of at least 8 and up to and including 13 or typically at least 10 and up to and including 11. The pH can be provided using known alkaline agents along with the compounds described below.

The first essential component of the silver halide imaging solution is one or more primary imaging agents such as hydroquinone or a derivative thereof or ascorbic acid or a derivative thereof. Suitable hydroquinones or derivatives (also known as polyhydroxybenzenes) include, but are not limited to, hydroquinone, catechol, pyrogallol, methylhydroquinone, chlorinated hydroquinone, hydroquinone monosulfate, 1,2- Naphthalenediol and 1,4-naphthalenediol. Suitable ascorbic acids and derivatives include, but are not limited to, ascorbic acid, isoascorbic acid and its derivatives, sodium ascorbate and sodium erythorbate.

The one or more primary imaging agents may be at least 0.01 mol/l and up to and including 1 mol/l, at least 0.01 mol/l and up to and including 0.15 mol/l, or more typically at least 0.075 mol/l and up to and including 0.14 mol The total amount of /l is present in the silver halide imaging solution. As above As noted, a mixture of primary imaging agents can be used as necessary, and in such embodiments, such concentrations refer to the total amount of primary imaging agent.

The silver halide imaging solution also contains one or more catalytic developers as a second essential component, and the compounds are p-aminophenol or a derivative thereof or phenidone (including derivatives of phenidone). The catalytic developers may be at least 0.001 mol/l and up to and including 0.1 mol/l, at least 0.001 mol/l and up to and including 0.025 mol/l, or typically at least 0.001 and at most and including 0.002 mol/l. The amount is present in the silver halide imaging solution. When a mixture of such compounds is used, the concentration refers to the total amount of the catalytic developer.

In contrast to the primary imaging agent which is the primary silver ion imaging agent (reducing agent), it is desirable to catalyze the presence of the imaging agent to increase the kinetics of imaging, especially by reducing or eliminating imaging induction time.

Suitable p-aminophenols include, but are not limited to, p-methylaminophenol, p-aminophenol, m-chloro-p-aminophenol, m-methyl-aminophenol, and p-hydroxyphenylglycine. Suitable phenidone and derivatives include, but are not limited to, substituted or unsubstituted fenidone, such as 4,4-dimethyl-3-pyrazolone and 4-(hydroxymethyl)- 4-methyl-1-phenyl-3-pyrazolidinone (HMMP).

In general, the concentration of one or more catalytic imaging agents can be less than the concentration of one or more primary imaging agents. More specifically, the total concentration of one or more primary imaging agents can be at least 100 times the total concentration of one or more catalytic imaging agents.

In many embodiments, the silver halide imaging solution has hydroquinone or a derivative thereof as a primary imaging agent, and phenidone as a catalytic imaging agent.

Important components of the silver halide imaging solution include, but are not limited to, one or more alkali metal sulfites; and one or more imaging inhibitors or limiting agents, such as alkali metal halides, substituted or unsubstituted A fluorenyltetrazole, one or more benzotriazoles, one or more aryl or alkyl disulfides, and one or more aryl or alkyl thiols. Mixtures of any of the same or different classes of compounds can be used.

For example, suitable alkali metal sulfites include sodium sulfite, potassium sulfite, and mixtures thereof. The alkali metal sulfite may be present in the silver halide imaging solution in a total amount of at least 0.1 mol/l and up to and including 1 mol/l or typically at least 0.4 mol/l and up to and including 0.8 mol/l. If a mixture of compounds is used, this concentration refers to the total amount of all sulfites.

One or more imaging inhibitors or limiting agents, such as an alkali metal halide, an aryl decyltetrazole, a benzotriazole, and an aryl or alkyl disulfide or an aryl or alkyl thiol At least one of them may be present in the silver halide imaging solution in a total amount of at least 0.25 mmol/l and up to and including 2.5 mmol/l or typically at least 0.5 mmol/l and up to and including 1.5 mmol/l.

Suitable alkali metal halides include, but are not limited to, sodium chloride, sodium bromide, potassium chloride, and potassium bromide.

Suitable substituted or unsubstituted arylmercaptotetrazole includes, but is not limited to, the following compounds: 1-phenyl-5-mercaptotetrazole (PMT), 1-ethyl-5-mercaptotetrazole, 1- Third butyl-5-mercaptotetrazole and 1-pyridyl-5-mercaptotetrazole.

Suitable benzotriazoles include, but are not limited to, substituted and unsubstituted benzotriazole compounds such as benzotriazole, 5-methylbenzotriazole and 5,6-dichlorobenzotriazole.

Suitable aryl or alkyl disulfides include, but are not limited to, 5,5'-(dithiobis(4,1-phenylphenylimino))bis(5-oxo-valeric acid) and Disodium salt, 2,2'-dithiobisbenzoic acid and its disodium salt, and 5,5'-dithiobis(pentanoic acid) and its disodium salt.

Suitable aryl or alkyl thiols include, but are not limited to, 5-mercapto-4,1-phenylimino-5-oxo-pentanoic acid and its sodium salt, and 5-mercaptoic acid and its sodium salt.

Other addenda that may be present in known amounts in the silver halide imaging solution include, but are not limited to, metal chelators, preservatives (other than sulfites), biocides, antioxidants, small amounts of water-miscible organic solvents. (such as benzyl alcohol and diethylene glycol), nucleating agents, acids, bases (such as alkali metal hydroxides), and buffers (such as carbonates, borax, phosphates, and other basic salts).

The silver halide imaging solution can be provided at work strength or in a concentrated form that can be suitably diluted prior to or during processing using known processing equipment and procedures. For example, the silver halide imaging solution can be concentrated at least 5 times compared to the desired working strength concentration.

Therefore, the silver halide imaging solution can be used to process the film at a suitable temperature, under normal atmospheric pressure, or to treat the film for a suitable time before imaging exposure to achieve imagewise exposure in the first (or second) achromatic hydrophilic photosensitive layer. At least 75 mol% of the exposed silver ions and typically at least 90 mol% and at least 90 mol% of any silver ions in each of the hydrophilic overcoat layers that may be present are developed.

For example, the processing temperature using the silver halide imaging solution can be in the range of at least 15 °C and up to and including 60 °C or typically at least 35 °C and up to and including 45 °C. Suitable processing times can be in the range of at least 10 seconds and up to and including 10 minutes but more likely up to and including 1 minute. Skilled workers can use conventional experiments to find optimal processing conditions to achieve the desired result in reducing silver ions to silver metal in the latent image. Washing or rinsing with water or a suitable aqueous solution can be carried out at a suitable temperature after processing the features and prior to processing with the physical imaging solution of the silver halide solution.

Processing with a physical imaging solution of a silver halide solution:

After optional cleaning, the imagewise exposure precursor is then typically processed in a physical imaging solution of a unique silver halide solution to enhance the silver image, such as a predetermined silver metal, on one or both sides of the support side of the substrate. The conductivity of the pattern.

The physical imaging solution of the silver halide solution can generally have a pH of at least 8 and up to and including 13 or typically at least 8 and up to and including 12. The pH can be provided using known alkaline agents along with the compounds described below.

The physical imaging solution of the silver halide solution contains one or more primary imaging agents selected from one or more of the following: anhydroquinone or a derivative thereof or one or more ascorbic acids or derivatives thereof. Examples of such compounds are provided above. The main imaging agent in the physical imaging solution of the silver halide solution can be used as the main imaging agent in the silver halide imaging solution described above Same or different.

One or more primary imaging agents in the physical imaging 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 or typically at least 0.05 mol/l and up to and including 0.2 mol/l. . If a mixture of such compounds is used, this concentration refers to the total amount of the primary imaging agent.

In addition, the physical imaging solution of the silver halide solution comprises at least 0.001 mol/l and up to and including 0.1 mol/l or typically at least 0.005 mol/l and up to and including 0.05 mol/l of one or more silver halide dissolution catalysts As an essential component. When a mixture of such compounds is used, these concentrations refer to the total amount of silver halide dissolution catalyst.

Suitable 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; Cyclothione, such as tetrahydro-4,6-dimethyl-1,3,5-triazine-2(1H)-thione and tetrahydro-3-hydroxyethyl-1,3,5-triazine -2(1H)-thione. These compounds can be easily mismatched with silver.

The physical imaging solution used in the silver halide solution of the present invention is substantially free of catalytic imaging agents such as those described above with respect to silver halide imaging 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 into the solution or are produced in solution.

The physical imaging solution of the silver halide solution may further comprise one or more alkali metal sulfites, including sodium sulfite, potassium sulfite, and mixtures thereof. When potassium sulfite or sodium sulfite is used or in particular when only potassium sulfite is used, the alkali metal sulfite may be at least 0.2 mol/l and up to and including 3 mol/l or typically at least 0.5 mol/l and up to and including 1 mol The total amount of /l is present in the physical imaging solution of the silver halide solution. If a mixture of compounds is used, then these concentrations refer to the total amount of all sulfites.

The physical imaging solution of the silver halide solution may further comprise one or more polyamine polycarboxylates capable of intercalating with silver ions, including but not limited to di-ethyltriamine pentaacetic acid pentasodium salt and Know other similar compounds. When there is no sulfite, the combination The material is particularly suitable. The compounds may be present in an amount of at least 0.001 mol/l and up to and including 0.03 mol/l.

The physical imaging solution of the silver halide solution may also include one or more metal ion intercalating agents that are miscible with silver, calcium, iron, magnesium or other metal ions that may be present. Silver or calcium metal ion intercalators may be particularly useful in a total amount of at least 0.001 mol/l.

Physical imaging solutions of particularly suitable silver halide solutions include, but are not limited to, hydroquinone or a derivative thereof and sodium thiocyanate or potassium thiocyanate, and optionally sulfite and calcium or silver metal ion intercalators.

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

Therefore, the physical imaging solution of the silver halide solution is used to process the film at a suitable temperature, under normal atmospheric pressure, or to treat the film for a suitable time to provide conductivity of the resulting first silver image, which is used only. The silver halide imaging solution is processed to image at least 2 times the conductivity of the first silver image (or second silver image) after exposure to the precursor.

The conductivity measurement of the first silver image was obtained as described in the examples below.

For this processing feature, the temperature can be at least 20 ° C and up to and including 60 ° C, or typically at least 35 ° C and up to and including 45 ° C. Suitable processing times can be in the range of at least 30 seconds and up to and including 6 minutes, but more preferably at least 2 minutes and up to and including 4 minutes. Skilled workers can use well-known experiments to find optimal processing conditions to achieve desired conductivity results. Washing or rinsing with water or a suitable aqueous solution can be carried out at this temperature after the processing of the features and prior to treatment with the fixing solution.

In many embodiments, the same silver halide imaging solution, a physical imaging solution of a silver halide solution, and a fixing solution are used to form the first and second silver images after imagewise exposure on both sides.

Fixing:

After processing with a physical imaging solution of a silver halide solution and optionally washing, The remaining unexposed silver ions (in any layer) can be removed by treating the imagewise exposure with the fixative solution and developing the precursor. Fixing solutions are well known in the art of black and white photography and contain one or more compounds that are misaligned with silver halide in order to remove them from the layers in which they are present. Thiosulfate is commonly used in fixing solutions. The fixing solution may optionally contain a hardener such as hydrazine or chrome. The developed film can be processed in the fixing solution immediately after physical development of the silver halide solution, or there may be an intervening stop solution or water wash or both. Fixing can be carried out at any suitable temperature and time, such as at least 20 ° C for at least 30 seconds.

After fixation, the conductive article containing the first silver image (and optionally the second silver image) can be washed or rinsed in water, which may include surfactants or other materials to reduce the amount of water after drying. Spot formation, which is optionally used prior to the next processing feature. Drying can be accomplished in the environment or by heating at a temperature above 50 ° C but below the glass transition temperature of the substrate, for example in a convection oven.

The fixation then leaves silver metal particles in the first silver image (usually in the silver pattern) in each of the previous achromatic hydrophilic photosensitive layers. This fixation also removes any unexposed silver ions in each of the hydrophilic outer coatings. For the duplex conductive film element precursors described herein, the same effect is provided on the opposite second support side.

It is desirable that the resulting conductive film member after processing in the fixing solution exhibits (visual) _Dmin of less than or equal to 0.03.

After fixation, the article can be washed or rinsed in water, which may optionally include a surfactant or other substance to reduce the formation of water spots after drying.

Enhanced conductivity:

The electrically conductive article comprising the first silver image (and optionally the second silver image) may be further washed or rinsed with water after subsequent fixing and optionally rinsing and prior to drying as described above and subsequently The treatment further enhances the conductivity of the silver metal (or core) in each of the silver images on each of the support sides of the substrate. A variety of approaches have been proposed to perform this "conductivity enhancement" process. For example, US Patent 7,985,527 (Tokunaga) and 8,012,676 (Yoshiki et al.) describes the treatment with a hot water bath, water vapor, reducing agent or halide. Details of such processing are provided in these patents.

It is also possible to repeat the contact (treatment) with the conductivity enhancer, followed by washing and drying as appropriate, and repeating the cycle for the conductivity enhancement treatment and optionally the washing and drying, usually one or more times. To enhance the conductivity of the silver metal particles in each silver image. Suitable conductivity enhancers include, but are not limited to, sulfites, borane compounds, hydroquinones, p-phenylenediamines, and phosphites. This treatment can be carried out at a temperature of at least 30 ° C and up to and including 90 ° C for at least 0.25 minutes and up to and including 30 minutes.

Additional processing:

The anterior bath solution can also be used to treat the exposed silver salt prior to the silver halide imaging described above. The pre-bath solutions may include one or more imaging inhibitors as described above and in the same or different amounts. Effective imaging inhibitors include, but are not limited to, benzotriazole, heterocyclic thioketone, and decyltetrazole. The anterior bath temperature can be within the range as described above with respect to the silver halide imaging step. 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.

It is applicable in some embodiments to treat the conductive film member with a hardening bath after fixing and before drying to improve the physical durability of the resulting conductive film member. Such hardening baths may include one or more suitable amounts of known hardeners that will be apparent to those skilled in the art.

Additional treatment of the conductive film elements, such as treatment with a stabilizing bath, can also be carried out, if necessary, at any suitable time and temperature prior to final drying.

The method of the present invention can be carried out using a conductive thin film element precursor comprising a first and second achromatic hydrophilic photosensitive layer on both the first and second support sides of the substrate, and respectively And first and second hydrophilic outer coatings disposed on the first and second achromatic hydrophilic photosensitive layers, the first and second hydrophilic outer coatings are corresponding first supports and opposite second support sides of the substrate The outermost layer.

In such methods, both the first and second achromatic hydrophilic photosensitive layers are suitably exposed to provide the same or different (usually different) latent silver halide-containing haze in the first and second achromatic hydrophilic photosensitive layers. pattern. These different exposures can be simultaneous or sequential. In many embodiments, both sides are simultaneously exposed.

The silver halide in the latent image formed in the two relatively achromatic hydrophilic photosensitive layers is then converted to silver metal particles on both sides during the processing described above. Therefore, two latent images can be simultaneously imaged and fixed.

The unconverted silver ions are removable from the first and second achromatic hydrophilic photosensitive layers, remaining in the respective first and second patterns corresponding to the first and second latent patterns on the opposite side of the opposite side of the substrate Lower silver metal particles.

During such processes, the same silver halide imaging solution, a physical imaging solution of the silver halide solution, and a fixing solution are used to form both the first and second silver images.

Optionally and desirably, the silver metal particles in the pattern on both sides of the element can be further processed as described above to enhance silver metal conductivity.

In many embodiments, the resulting conductive thin film element has at least one predetermined conductive silver metal electrode grid (pattern) on at least a first support side of the substrate and desirably has a conductive silver metal electrode grid on the opposite second support side of the substrate ( Pattern), the composition of the electrode grid, the pattern configuration, the thickness of the conductive line or the shape of the grid line (for example, hexagonal, rhombic, octagonal, square, circular or irregular). For example, the conductive silver metal electrode grid on the first support side of the substrate may have a square pattern of conductive silver metal electrode grid, and the conductive silver metal electrode grid on the opposite side of the substrate may have a diamond pattern.

The conductive thin film element prepared using the present invention may be used after formation, or it may be further processed, for example, to electrolessly electroplate a conductive metal such as copper, palladium, platinum, aluminum, tin or gold to the first (and second) silver. On the image. Conductive metals of the same or different electroless plating may be provided on the first and second silver images on opposite support sides of the substrate.

Silver management

In the method of using an image developer which readily dissolves silver halide, there is a risk that the resulting soluble silver ions can migrate from the photosensitive silver halide emulsion and which can then be reacted with a black-and-white developer to form metallic silver. Metallic silver in turn causes problems with precipitation or deposition, rendering the developer undesirable. In such cases, it is desirable to remove dissolved silver ions from the developer solution before it accumulates in the processing tank and becomes reduced to metallic silver. The removal of soluble silver ions can be accomplished in a number of different ways, including electrolytic plating, electroless plating onto substrates containing active nucleation sites such as Cary-Lea silver (e.g., as in U.S. Patent 5,188,662 (McGuckin et al)). As described, or using an ion exchange resin having a high affinity for silver ions. Removal by certain ion exchange resins (commonly referred to as chelating resins) is more suitable for a simpler process. A wide variety of chelating resins having high capacity and specificity for silver ions are commercially available from a variety of sources.

The following examples are provided to illustrate the practice of the invention and are not intended to be limiting in any way.

A conductive thin film element precursor (identified as component 1) was prepared using a 125 μm poly(ethylene terephthalate) substrate coated with a non-color photosensitive silver halide emulsion (emulsion 1) containing 98 mol% of silver chloride and 2 mol% of silver iodide And component 2). The emulsion particles have a cubic morphology and an edge length of 0.36 μm, and are coated with BVSM [1,1'-(methylene(fluorenyl))bis-B, which is coated as a part of the following layer 2 with 0.5% by weight of total gelatin. Alkyl] hardened.

The first layer (layer 1) is provided directly on the substrate for UV absorption. The UV absorption at 365 nm is increased to 1.7 optical density units. Layer 1 comprises 1500 mg/m ² of gelatin and 300 mg/m ² of TINUVIN 328 UV absorbing dye.

A photosensitive silver halide emulsion layer (layer 2) comprising emulsion 1 is provided above layer 1. For element 1, the weight ratio of silver (Ag) to gelatin was kept constant at 2.33:1 (or at a volume ratio of about 0.297:1). For element 2, the silver (Ag) to gelatin weight ratio remains constant at 2.45:1 (or at a volume ratio of about 0.313:1).

Both elements 1 and 2 further comprise a hydrophilic overcoat layer (layer 3) above layer 2, the layer 3 comprising 488 mg/m ² of gelatin, 6 mg/m ² of 0.6 μm insoluble polymeric matte particles and conventional coatings Surfactant.

The conductive thin film element precursor of the element 1 was imagewise exposed by a chrome-plated design having a diamond-shaped grid pattern having a corner-to-corner size of 300 μm (vertical) × 500 μm (horizontal). The gate line on the mask is about 3 μm wide. The width of each channel is 4.8 mm. Each channel has a length of 85 mm. Exposure was carried out with UV radiation at a wavelength of 365 nm.

The imagewise exposed silver halide film was processed using the processing sequence shown in Table I below to reduce the silver cations to silver metal and form a conductive film element. The evaluation results of the conductive film elements are also shown in Table I below.

The resistance of the five identical channels described above is measured using a two-point probe located on the contact pads at the ends of each conductive channel, and the two-point probe is connected to the ohmmeter. The X-Rite Model 310 density meter was used to measure the visual _Dmin in the non-exposed areas of the conductive film elements. The visual density is a weighted average of the red, green, and blue densities and is designed to mimic the sensitivity of the human eye. The relative resistance and visual _Dmin values of the six tests are included in Table I to demonstrate the advantages of the present invention. The combination of the developer 1A and the developer 2A (Inventive Example 1) provides both low resistance and low visual _Dmin . Separate developer 1A (Comparative Examples 2 and 3) or Separate Developer 2A (Comparative Example 4) exhibited extremely high electrical resistance. Conventional black and white imaging agent, developer 2B gives low resistance (Comparative Example 5), but extremely high visual _Dmin . The use of the developer 1A in combination with the conventional black-and-white imaging agent and the developer 2B (Comparative Example 6) also gave good resistance, but gave an unacceptable visual _Dmin .

The conductive thin film element precursor of element 2 was exposed as described above and subsequently processed using the processing sequence shown in Table II below. Sheet resistance was obtained using a two-point probe measurement on a 1 x 1 吋 (2.54 cm x 2.54 cm) grid using contact pads that directly contact the grid, resulting in ohms per square. resistance.

The sheet resistance values of the four tests are included in Table II to demonstrate the advantages of the present invention. The combination of the first imaging agent and the second imaging agent used in the practice of the present invention (Inventive Examples 7, 8, and 9) provides and uses a single conventional imaging agent comprising ascorbic acid and N-methyl-p-aminophenol ( Comparative Example 10) is much lower than the sheet resistance.

The compositions of the processing solutions used in these examples are shown in Tables III through IX. All such processing solutions are aqueous solutions prepared using demineralized water.

Claims (23)

A physical imaging solution of a silver halide solution comprising: (a) a primary imaging agent in an amount of at least 0.01 mol/l and up to and including 1 mol/l, which is hydroquinone or ascorbic acid or a derivative thereof And (c) a silver halide dissolution catalyst in an amount of at least 0.001 mol/l and up to and including 0.1 mol/l, and the physical development solution of the silver halide solution is substantially free of (b) a catalytic developer. A physical imaging solution of the silver halide solution of claim 1, which further comprises an alkali metal sulfite in an amount of at least 0.2 mol/l and up to and including 3 mol/l. A physical imaging solution of the silver halide solution of claim 1 or 2, which further comprises at least 0.5 mol/l and up to and including 1 mol/l of sodium sulfite or potassium sulfite. A physical development solution of the silver halide solution of claim 1 or 2, wherein the silver halide dissolution catalyst is an alkali metal thiocyanate in an amount of at least 0.005 mol/l and up to and including 0.05 mol/l. A physical imaging solution of silver halide according to claim 1 or 2, which further comprises one or more metal ion intercalating agents in a total amount of at least 0.001 mol/l. A physical imaging solution of silver halide according to claim 5, which further comprises a total amount of calcium or a silver metal ion intercalating agent of at least 0.001 mol/l as a metal ion intercalating agent. A physical development solution of silver halide according to claim 1 or 2, wherein the main developer is hydroquinone or a derivative thereof, and the silver halide dissolution catalyst is sodium thiocyanate or potassium thiocyanate. A physical imaging solution of silver halide according to claim 7, which further comprises at least 0.5 mol/l and up to and including 1 mol/l of sodium sulfite or potassium sulfite. A physical imaging solution of silver halide according to claim 1 or 2 which is concentrated at least 4 times more than the concentration of the desired working strength. A method of providing a conductive silver image on a transparent substrate in a conductive film element, the method comprising, in order, imaging exposing a conductive thin film element precursor including a transparent substrate having a first support side and a second support side, and The conductive thin film element precursor includes, in order, on the first support side, a first achromatic hydrophilic photosensitive layer containing photosensitive silver halide, and optionally a first hydrophilicity disposed above the first achromatic hydrophilic photosensitive layer An overcoat layer to provide an imagewise exposure precursor comprising a first latent silver image in the first achromatic hydrophilic photosensitive layer, the imagewise exposure processed in a silver halide imaging solution having a pH of at least 8 and comprising: The precursor is at least 10 seconds: (a) at least 0.01 mol/l and up to and including 1 mol/l of the primary imaging agent, which is hydroquinone or ascorbic acid or a derivative of either, and (b) at least 0.001 a catalytic developer of mol/l and up to and including 0.1 mol/l, which is a p-aminophenol or phenidone or a derivative thereof, to provide in the first achromatic hydrophilic photosensitive layer Corresponding to the first latent silver map a first silver image, the imagewise exposure precursor is processed in a physical imaging solution of a silver halide solution according to any one of claims 1 to 9 at a temperature of at least 20 ° C for at least 30 seconds to provide the The conductivity of the silver image, which is at least 2 times the conductivity of the first silver image after processing with only the silver halide imaging solution, and processing the image before exposure in the fixing solution to move In addition to the remaining silver ions and providing a conductive thin film element containing the first silver image, the conductive thin film element is processed to enhance the conductivity of the first silver image, and optionally, the conductive thin film element is washed and dried. The method of claim 10, wherein the conductive film element exhibits (visual) _Dmin less than or equal to 0.03 after processing in the fixing solution. The method of claim 10 or 11, wherein the treating to enhance the cycle of conductivity and optionally the washing and drying cycle is repeated at least once. The method of claim 10 or 11, wherein the first silver image is provided in a predetermined conductive silver pattern. The method of claim 10 or 11, wherein the first achromatic hydrophilic photosensitive layer comprises one or more silver halides to provide a total silver metal coverage of less than 5000 mg Ag/m ² . The method of claim 10 or 11, wherein the conductive thin film element precursor further comprises a first hydrophilic outer coating disposed over the first achromatic hydrophilic photosensitive layer, the first hydrophilic outer coating optionally comprising One or more silver halides to provide a silver metal of at least 5 mg Ag/m ² and up to and including 150 mg Ag/m ² coverage, and the one or more silver halides each have a particle ESD of at least 30 nm and up to and including 300 nm. The method of claim 15, wherein the first hydrophilic outer coating further comprises an ultraviolet light absorber. The method of claim 10 or 11, wherein the silver halide imaging solution further comprises an alkali metal sulfite in an amount of at least 0.1 mol/l and up to and including 1 mol/l. The method of claim 10 or 11, wherein the silver halide imaging solution further comprises one or more of the following: an alkali metal halide, an arylsulfonyltetrazole, a benzotriazole, an aryl or an alkyl disulfide. Or aryl or alkyl mercaptan. The method of claim 10 or 11, wherein the conductive thin film element precursor further comprises a second achromatic hydrophilic photosensitive layer on the opposite second support side of the transparent substrate, and optionally disposed in the second achromatic hydrophilic layer a second hydrophilic overcoat layer over the photosensitive layer, and the method further comprising: imaging exposing the conductive thin film element precursor from the second opposite side of the transparent substrate to the second of the precursor prior to the imagewise exposure Providing a second latent silver image in the achromatic hydrophilic photosensitive layer, processing the imagewise exposure for at least 10 seconds in a solution having a pH of at least 8 and comprising the same or different silver halide imaging solutions: (a) at least 0.01 mol /l and up to and including 1 a primary imaging agent in an amount of mol/l which is hydroquinone or ascorbic acid or a derivative thereof, and (b) a catalytic developer in an amount of at least 0.001 mol/l and up to and including 0.1 mol/l, It is a para-aminophenol or phenidone or a derivative thereof to provide a second silver image corresponding to the second latent silver image in the second achromatic hydrophilic photosensitive layer, at least 20 Processing the imagewise exposure precursor for at least 30 seconds in a physical imaging solution of the same or different silver halide solution according to any one of claims 1 to 9 at a temperature of ° C to provide conductivity of the silver image, It is at least 2 times the conductivity of the second silver image after processing with only the first development solution, and the imagewise exposure precursor is processed in the fixing solution to remove the remaining silver ions and provide the inclusion The conductive film element of the second silver image is processed to enhance the conductivity of the second silver image, and optionally wash and dry the conductive film element. The method of claim 19, the conductive thin film element precursor further comprising a second hydrophilic outer coating disposed over the second achromatic hydrophilic photosensitive layer, the second hydrophilic outer coating optionally comprising one or more Silver halide to provide a silver metal of at least 5 mg Ag/m ² and up to and including 150 mg Ag/m ² coverage, and the one or more silver halides each have a particle ESD of at least 30 nm and up to and including 300 nm. A conductive film element provided by the method of any one of claims 10 to 20, having a first silver image on at least a first support side of the transparent substrate. The conductive film element of claim 21 having a first silver image on a first support side of the transparent substrate and a second silver image on a second opposite support side of the transparent substrate. The conductive film element of claim 21 or 22 further comprising an electrolessly plated conductive metal on the first silver image and optionally the second silver image.