CN105093805A - Silver halide solution physical developing solution and use method for same - Google Patents
Silver halide solution physical developing solution and use method for same Download PDFInfo
- Publication number
- CN105093805A CN105093805A CN201510259928.6A CN201510259928A CN105093805A CN 105093805 A CN105093805 A CN 105093805A CN 201510259928 A CN201510259928 A CN 201510259928A CN 105093805 A CN105093805 A CN 105093805A
- Authority
- CN
- China
- Prior art keywords
- silver
- silver halide
- conductive film
- film element
- achromaticity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Manufacturing Of Electric Cables (AREA)
Abstract
The invention relates to a silver halide solution physical developing solution and a use method for the same. 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
Technical field
The present invention relates to a kind of method using the unique combination of machining feature and working fluid to provide conductive silver thin-film component (or conductive articles).This type of conductive silver thin-film component can possess predetermined conductive silver pattern and for different electronic installation, or its can further through processing to provide the pattern of other conducting metal of plating above silver.Described method can be carried out after the unique silver halide physical developer Imagewise exposure conductive film element precursor of use.
Background technology
Rapid progress is there is for various communication, finance, acquisition and the various electronic installations of file object, especially display device.For the purposes of such as touch panel, electrochromic device, light emitting diode, field effect transistor and liquid crystal display, conductive film is required, and makes quite large effort in industry to improve character and its manufacture method of those conductive films.
In addition, along with the exploitation in recent years of mentioned display device, its attractive force increases greatly by means of touch screen technology, thus with finger or stylus touching in screen surface can produce signal with cause screen view to change or cause the reception of information or transmission, telecommunications, to interact with the Internet and continuous increase the innovation of paces under many further features of just developing.Touch screen technology to a great extent by using electrically conducting transparent grid on basic display unit, so that the position of the touch that screen surface indicates can be detected by proper circuit and software, and is become possibility.
Current, most of touch-screen display uses tin indium oxide (ITO) coating to produce the capacitor regions array in order to distinguish Multi-contact.ITO coating has remarkable shortcoming, and is just making great efforts to use to replace it in various electronic installation.Indium is expensive rare earth metal and can obtains with limited supply from few source in the world.ITO electric conductivity is relatively low and need short-term road length to realize the sufficient speed of response.Touch-screen for large display be divided into more small fragment so that electrical path lengths is reduced to acceptable resistance.ITO is stupalith, is not easy bending or warpage, and needs vacuum moulding machine under high processing temperature to prepare conductive layer.
Silver is the perfect conductor of electric conductivity than large 50 to 100 times of ITO.Silver is used in the application of much business and multi-source of can comforming obtains.Highly need to use silver to manufacture conductive film element as electric conductivity, but need tremendous development or other process operation to obtain optimum conduction property.
U.S. Patent Application Publication case 2011/0308846 (city comes (Ichiki)) describes the preparation of conductive film, it is by by the silver-colored line size being less than 10 μm, the silver halide images reduced in conductive network is formed, and described conductive film can in order to form the touch panel in display.
In addition, United States Patent (USP) 3,464,822 (Bu Laike (Blake)) describe the purposes of silver halide emulsion, its for photographic element to form conductive silver surface image by one or more process bath after developing and developing.
United States Patent (USP) 7,829,270 (in flat (Nakahira)) describe the purposes of light sensitive silver halide material, and it is in order to form conductive silver metal pattern.After exposed photosensitive silver halide material, being used black-and-white developer to process, is then fixing and physical development and electroless-plating operation.
In addition, United States Patent (USP) 8,012,676 (people such as Jia Shu (Yoshiki)) also describe similar approach, but comprise the operation of the electric conductivity strengthening gained silver metal image further.
Therefore, the various working fluid of known use and condition provide conductive silver pattern on transparent membrane.But, need in addition to improve silver-colored pattern, silver-colored pattern especially in thin line form electric conductivity and do not increase D
min.That is, the silver metal electric conductivity, the transparency of increase and the low D that improve in balanced conductive silver image is needed
min.Consider these needs, exploitation the present invention.
Summary of the invention
The invention provides a kind of silver halide solution physical developer solution, it comprises:
(a) at least 0.01mol/l and at the most and comprise the main developer of the amount of 1mol/l, it is quinhydrones or ascorbic acid or the derivant of any one, and
(c) at least 0.001mol/l and at the most and comprise the silver halide catalyst-solvent of the amount of 0.1mol/l, and
Described silver halide solution physical developer solution is not in fact containing (b) catalysis developer.
Present invention also offers a kind of method transparent substrates in conductive film element providing conductive silver image, described method comprises in order:
Imagewise exposure comprises the conductive film element precursor with the first support-side and the transparent substrates of relative second support-side, and described conductive film element precursor comprises the first achromaticity water wettability photographic layer comprising light sensitive silver halide and the first hydrophilic outer coating be optionally placed in above described first achromaticity water wettability photographic layer in order in described first support-side, the first presoma of Imagewise exposure of hiding silver-colored image is comprised to be provided in described first achromaticity water wettability photographic layer
Be at least 8 and at the most and comprise 13 and comprise the presoma at least 10 seconds processing described Imagewise exposure in following silver halide developer solution at pH: (a) at least 0.01mol/l and at the most and comprise the main developer of the amount of 1mol/l, it is quinhydrones or ascorbic acid or the derivant of any one, (b) at least 0.001mol/l and at the most and comprise the catalysis developer of the amount of 0.1mol/l, it is para-aminophenol or phenidone or the derivant of any one, to provide the first silver medal image of silver-colored image of hiding corresponding to described first in described first achromaticity water wettability photographic layer,
At the temperature of at least 20 DEG C, according to the presoma at least 30 seconds processing described Imagewise exposure in the silver halide solution physical developer solution of any embodiment described herein, to provide the electric conductivity of described silver-colored image, it is only with at least 2 times of electric conductivity of the described first silver medal image after the first developer solution processing
The presoma of described Imagewise exposure is processed in stop bath, to remove residue silver ion and to provide the conductive film element containing described first silver medal image,
Process described conductive film element, to strengthen the electric conductivity of described first silver medal image, and
Optionally washing and the described conductive film element of drying.
In some embodiments of the invention, described method uses conductive film element precursor to carry out, the second hydrophilic outer coating that described conductive film element precursor comprises the second achromaticity water wettability photographic layer further and is optionally placed in above described second achromaticity water wettability photographic layer in described relative second support-side of described transparent substrates, and described method comprises further:
From conductive film element precursor described in the described second-phase offside Imagewise exposure of described transparent substrates, to provide second to hide silver-colored image in the described second achromaticity water wettability photographic layer of the presoma at described Imagewise exposure,
Be at least 8 and at the most and comprise 13 and comprise the presoma at least 10 seconds processing described Imagewise exposure in following identical or different silver halide developer solution at pH: (a) at least 0.01mol/l and at the most and comprise the main developer at least 10 seconds of the amount of 1mol/l, it is quinhydrones or ascorbic acid or the derivant of any one, (b) at least 0.001mol/l and at the most and comprise the catalysis developer of the amount of 0.1mol/l, it is para-aminophenol or phenidone or the derivant of any one, to provide the second silver medal image of silver-colored image of hiding corresponding to described second in described second achromaticity water wettability photographic layer,
At the temperature of at least 20 DEG C, the presoma at least 30 seconds of described Imagewise exposure is processed in the identical or different silver halide solution physical developer solution of any embodiment described in this article, to provide the electric conductivity of described silver-colored image, it is only with at least 2 times of electric conductivity of the described second silver medal image after the first developer solution processing
The presoma of described Imagewise exposure is processed in stop bath, to remove residue silver ion and to provide the conductive film element containing described second silver medal image,
Process described conductive film element, to strengthen the electric conductivity of described second silver medal image, and
Optionally washing and the described conductive film element of drying.
Method of the present invention can in order to provide a kind of conductive film element of the present invention, and described conductive film element has the first silver medal image and optionally in relative second support-side of transparent substrates, has the second silver medal image in the first support-side of transparent substrates.Described first and second silver medal images are conduction and can be used alone or electroplate with other conducting metal.
The present invention can use pH to be at least 8 and comprise following unique silver halide developer solution and carry out:
(a) at least 0.01mol/l and at the most and comprise the main developer of the amount of 0.15mol/l, it is quinhydrones or ascorbic acid or the derivant of any one,
(b) at least 0.001mol/l and at the most and comprise the catalysis developer of the amount of 0.025mol/l, it is para-aminophenol or phenidone or the derivant of any one, and
(c) at least 0.25mol/l and at the most and comprise one or more development restrainer of the total amount of 2.5mol/l.
The invention provides the several advantages of the conductive film element of the improvement containing the highly conductive silver metal image that can be configured in the predetermined pattern of fine rule road or grid.Gained conductive film element represents high conductivity and the high grade of transparency, is to keep (vision) D after processing in stop bath simultaneously
minlow as far as possible, be such as less than or equal to 0.3.These advantages realize by using the unique combination of black and white silver halide developer solution before fixing.
Embodiment
Below discuss and relate to various embodiment of the present invention, and when some embodiments can cater to the need especially for special-purpose, disclosed embodiment should not be construed as or is otherwise considered as limiting the scope of the invention, required by hereafter.In addition, it will be understood by those skilled in the art that following discloses content has and apply widely than clearly describing, and to the scope that the discussion of any embodiment is not intended to limit the present invention.
Definition
Unless otherwise instructed, otherwise as herein in order to the various components of definition in order to the working fluid and various layer and composite of preparing conductive film element precursor, singulative " one (a/an) " and " described (the) " intend the one or many person (that is, comprising multiple indicant) comprised in described component.
Not clearly defined each term is interpreted as having usual the accepted implication of those skilled in the art in this application.If the construction of term will make its hereinafter meaningless or essentially no meaning thereon, so the definition of term should take from English or chemical dictionary.
Unless clearly indicated in addition, otherwise the use of numerical value in the various scopes of defined is herein considered as approximate value, as being all added with word " about " before the minimum value in described scope and maximal value.In this way, more than described scope and below Small variables can in order to realize the result identical with the value in scope in fact.In addition, the disclosure of these scopes is contemplated to the successive range of each value comprised between minimum value and maximal value.
Unless otherwise instructed, otherwise term " % by weight " refers to that component or material are with the amount of the total solids of composition, composite, solution, or the number percent of the dry weight of layer.Unless otherwise instructed, otherwise number percent for drying layer or pattern or can be identical for the total solid of composite or composition in order to manufacture described layer or pattern.
Unless otherwise instructed, otherwise term " mol% " refers to the molar weight of the concrete component (or potpourri of the component of identical category) in solution or dispersion liquid.
" conductive film element precursor " (or " presoma ") is intended to refer to for putting into practice the present invention to provide article or the element of conductive film element of the present invention.Therefore this type of conductive film element precursor comprises the presoma of silver metal particle, such as, compatibly transform the silver halide that (such as by reduction) is silver metal as described below.Many discussions about conductive film element precursor are equally applicable to conductive film element because when the silver in silver halide is cation ic-converted be silver metal particle time, most of components and structure do not change.Therefore, unless otherwise instructed, otherwise to the component also intending to describe gained conductive film element for substrate, hydrophilic adhesive and the colloid in the silver halide layer of conductive film element precursor and hydrophilic outer coating and other accrete discussion any.
Unless otherwise instructed, otherwise term " conductive film element (conductivefilmelement/electrically-conductivefilmelement) " and " conductive articles " intend to mean identical things.It refers to the material containing the hydrophilic layer comprising the conductive silver metal image (or other conducting metal image) be placed in one or two support-side of applicable substrate.Other component of conductive articles or conductive film element is described in hereinafter.
Unless otherwise instructed, otherwise term " conduction " refers to " electric conductivity ", and non heat conductivity.
Term " first " refers to the layer in a support-side of substrate, and term " second " refers to the layer in relative (on the contrary) support-side of substrate.Each support-side of substrate can be suitable on an equal basis and term " first " need not mean side is the main of stilt or better support-side.
Term " duplex " and " bilateral " are in this article about all having the conductive film element precursor of described layer and conductive film element and use in two support-side of substrate.Unless otherwise indicated herein, relation and the composition of the various layers otherwise in two of substrate support-side can be identical or different.In addition, the silver halide be placed on the relative support side of substrate can use identical or different working fluid and condition to carry out imaging and processing.
ESD refers to " equivalent spherical diameter " and be in order to define the term of the size of particle (such as silver halide particle) in photography.Silver halide particle such as the granularity represented with particle ESD can easily use disc centrifuge Instrument measuring.
Unless otherwise instructed, otherwise " black and white " refers to the black and white material and composite that form silver, but not colour developing black and white material and composite.
Purposes
Conductive film element precursor may be used for putting into practice the present invention one or two support-side being formed in applicable substrate to comprise the conductive film element of conductive silver metal pattern.These conductive film elements itself can be used as device or it can as the assembly had in the device of multiple application, and described application includes but not limited to electronics, optics, sensation and diagnostic uses.The more details of this type of purposes are provided in hereinafter.Specifically, wish to use conductive film element precursor of the present invention to carry out providing package containing as the highly conductive silver metal pattern (or other conductive metal pattern) of line, described circuit has and is less than 50 μm or be less than 15 μm or be even less than 10 μm and the low linear resolution (live width) to 1 μm.
Particularly suitable be prepared in first of transparent substrates with the conductive film element relative second support-side comprising conductive silver pattern.This electron-like and optical devices and assembly include but not limited to radio-frequency (RF) tag (RFID), sensor, touch-screen display and for the memory of display and backplate.
Conductive film element precursor
It is photosensitive for being applicable to put into practice conductive film element precursor of the present invention, but not containing being enough to the chemical substance providing color photographic image.Therefore, these presomas form the black and white photosensitive material of argent image after being considered to be in exposure and processing, and are " achromatic image formation ".
The conductive film element precursor and the gained conductive film element that comprise all layers of enclosing in transparent substrates and one or two support-side are regarded as transparent, meaning by the comprehensive transmissivity on visible range indicated by electromagnetic wave spectrum (such as 410nm to 700nm) of whole element can be more than 70% or 70%, or more may more than at least 85% or even 90% or 90%.Comprehensive transmissivity can use spectrophotometer and known procedure to measure.
The conductive film element precursor that two support-side of transparent substrates have identical or different require layers can be called as " duplex " or " bilateral " conductive film element precursor.
Conductive film element precursor can be formed by providing the first achromaticity (that is, forming the black and white of silver metal) water wettability photographic layer in applicable mode at least one support or planar side (relative with non-supported edge) of applicable transparent substrates.This first achromaticity water wettability photographic layer comprises silver halide or silver halide potpourri, and total silver-colored coverage rate is at least 2500mgAg/m
2, or at least 3500mgAg/m
2, and be less than 5000mgAg/m in many examples
2, such as at the most and comprise 4900mgAg/m
2.But, higher silver-colored coverage rate can be used if desired.Therefore, to have enough silver halides intrinsic or add spectral sensitization with to selected imagewise (described below) tool photonasty for this achromaticity water wettability photographic layer.On the relative support side of transparent substrates, the composition of photographic layer and spectral sensitization can be identical or different.
One or more silver halide is scattered in one or more applicable hydrophilic adhesive or colloid, as hereafter also described.
Therefore this type of conductive film element precursor processes (Imagewise exposure) in one way to be silver metal particle by cation ic-converted for silver (such as by reduction), and then the presoma of this exposure can be converted into conductive film element of the present invention after hereafter described suitable process or procedure of processing.
Conductive film element precursor is made up of a require layers in each support-side of substrate substantially, and described require layers is the achromaticity water wettability photographic layer settled on a transparent substrate.This require layers can be placed in an only support-side of transparent substrates, but in many duplex embodiment, it is placed in first of transparent substrates with in relative second support-side.Hereafter described hydrophilic outer coating is optional but is highly wish in many examples, and this type of hydrophilic outer coating is directly placed on achromaticity water wettability photographic layer.These layers can be placed in an only support-side of transparent substrates, or it can be placed in the first support of transparent substrates with in relative second support-side by same sequence.Other optional layer also may reside in either one or two support-side, as described below.
transparent substrates:
The expected utility of gained conductive film element is depended in the selection of transparent substrates usually.It can be rigidity or flexibility, and normally transparent as described above.For example, substrate can be transparent flexible substrate, and its comprehensive transmissivity using standard spectrophotometers and program to measure on visible range indicated by electromagnetic wave spectrum is as described above at least 80% and usually at least 95%.
Applicable transparent substrates includes but not limited to glass, glass reinforced epoxy resin laminate, cellulosic triacetate or another kind of cellulose esters, acrylate, polycarbonate, the polymer substrate through sticker coating, polymer substrate (such as mylar) and compound substance.Be suitable for the polymkeric substance making polymer substrate and include but not limited to tygon, polyester (such as polyethylene terephthalate (PET) and PEN (PEN)), polypropylene, polyvinyl acetate, polycarbamate, polyamide, polyimide, polysulfones and its potpourri.
Polymeric substrates can also comprise the layer that two or more have identical or different polymeric compositions, so that compound substrate (or laminate) has identical or different layer refractive properties.Transparent substrates can be treated with the stickability of one or two support-side improving silver salt emulsion or dispersion liquid and substrate in either one or two support-side.For example, transparent substrates can be coated with polymeric stickers layer in one or two support-side, or it can through chemical treatment or experience corona treatment.
Bidirectional oriented thin slice, although be described as having at least one layer, can also possess can in order to the additional layer of the optics or other character that change bidirectional oriented thin slice.This type of layer can contain tone, antistatic or conductive material or slip agent.Biaxially oriented extruding can be carried out with nearly 10 layers if desired and want character to realize some concrete institutes.
The transparent substrates being specially adapted to manufacturing flexible electronic installation or touch panel unit is flexible, and described feature contributes to the coating of quick Scroll.
poly-(ethylene glycol terephthalate) film and cellulosic triacetate film are specially adapted to manufacture the material for flexible transparent substrate of the present invention.
Transparent substrates can be identical with the stilt be incorporated in flexible display apparatus or film, and this means require layers described herein and is coated to non-transparent substrate material in display device and according to institute's desirable pattern in situ imaging, and then original position processing.
When utilizing discrete transparent substrates (that is, transparent substrates be not incorporated in flexible display apparatus), providing layer (from composite) in its one or two support-side.If different pattern (or grid) is intended for use each support-side, so opposite side can be arrived to prevent exposure from side containing the substrate of filter dye or optional intervention (or antihalation) layer that filters by providing package.Or silver halide emulsion can through differently sensitization for the relative achromaticity water wettability photographic layer on the relative support side of transparent substrates.
Can at least 20 μm be had and at the most and comprise 300 μm or typically at least 75 μm and at the most and comprise the thickness of 200 μm for the transparent substrates in conductive film element precursor.Antioxidant, brightener, antistatic or conductive agent, plasticiser and other additives known can be incorporated in transparent substrates by apparent amount for those skilled in the art if desired.
achromaticity water wettability photographic layer:
Required silver halide in these layers comprises the silver-colored kation of one or more silver halide, and it can be converted into silver metal particle according to institute's desirable pattern after with imagewise exposure each achromaticity water wettability photographic layer.Then sub-image can use known silver-colored developing programs and chemical substance (described below) to develop to silver metal image.Silver halide (or silver halide combination) is photosensitive, mean UV to visible ray radiation (such as at least 200nm and at the most and comprise 750nm radiation) usually in order to by cation ic-converted for silver be the silver metal particle in sub-image.In certain embodiments, silver halide and temperature-sensitive silver salt (such as Silver behenate) combine to be existed, and achromaticity photonasty hydrophilic layer can be photosensitive and temperature-sensitive (sensitive to the imaging heat energy of such as infrared radiation).
Applicable light sensitive silver halide can be such as silver chloride, silver bromide, silver chloroiodobromide, bromine chlorosulfonylation silver, chlorine silver bromide, bromine silver chloride or bromo-iodide, and it is prepared with individual compositions (or emulsion) form.Various halogenide is listed by halogenide amount descending in silver halide name.In addition, indivedual silver halide emulsion can be prepared and mix to form the silver halide emulsion liquid mixture in the identical or different support-side of substrate.In general, be suitable for silver halide and can comprise at the most and the chloride comprising 100mol%, or at the most and comprise the bromide of 100mol%, and at the most and comprise 5mol% iodide, all in total silver.
Usually at least 30nm can be had and at the most and comprise 300nm or more may at least 50nm and at the most and comprise the ESD of 200nm for the silver halide particle in each achromaticity water wettability photographic layer.
Total silver-colored coverage rate in silver halide in each achromaticity water wettability photographic layer can be at least 2500mgAg/m
2and typically at least 3500mgAg/m
2and any amount but be usually less than 5000mgAg/m at the most
2, such as at the most and comprise 4900mgAg/m
2.Higher silver-colored coverage rate can be used if desired.
The dry thickness of each achromaticity water wettability photographic layer can be at least 0.5 μm and at the most and comprise 12 μm usually, and especially at least 0.5 μm and at the most and comprise 7 μm.
Final drying achromaticity water wettability photographic layer can be made up of one or more achromaticity water wettability photonasty sublayer through indivedual coating, and described sublayer can use identical or different silver halide emulsion composite to apply.Each sublayer can be made up of identical or different silver halide, hydrophilic adhesive or colloid condiment.Sublayer can have the silver content of identical or different amount.
Can with identical or different for the light sensitive silver halide in relative second support-side achromaticity water wettability photographic layer for the light sensitive silver halide in the first achromaticity water wettability photographic layer.
Light sensitive silver halide particle (with relative any condiment as described below) disperses (usually equably) in one or more applicable hydrophilic adhesive or colloid to form water wettability silver halide emulsion.The example of this type of hydrophilic adhesive or colloid includes but not limited to gelatin and gelatine derivative, polyvinyl alcohol (PVA) (PVA), PVP (PVP), casein and its potpourri.Being applicable to hydrophilic colloid and ethene polymers and multipolymer is also described in by Kenneth Mason publishing house (KennethMasonPublications), Eem Butterworth (Emsworth), Hampshire (Hants), PO107DQ, the IX some projects of the disclosed research of Britain (UK) open (ResearchDisclosure) are in 36544,1994 9 months.
The amount of silver halide that in each achromaticity water wettability photographic layer, the amount of hydrophilic adhesive or colloid can be suitable for desired concrete dry thickness and be incorporated to.It can also be suitable for meeting institute want dispersiveness, expansion and with the layer stickability of transparent substrates.In general, one or more hydrophilic adhesive or colloid can by the total solids in emulsion composite or drying layer with at least 10 % by weight and at the most and the amount comprising 95 % by weight exist.
Some applicable achromaticity water wettability photographic layer compositions have relatively high silver ion/low hydrophilic adhesive (such as, gelatin) weight ratio.For example, the weight ratio of the particularly suitable of silver ion (with final silver metal) and hydrophilic adhesive or colloid (such as gelatin (or derivatives thereof)) can be at least 0.1:1, or even at least 1.5:1 and at the most and comprise 10:1.The weight ratio of the particularly suitable of silver ion and hydrophilic adhesive or colloid can be at least 2:1 and at the most and comprise 5:1.Different ratio can be used if desired for set object.
Hydrophilic adhesive or colloid can use with the hardener combination of the concrete hydrophilic adhesive (such as gelatin) that hardens through designing with one or more.The rigidizer being specially adapted to gelatin and gelatine derivative includes but not limited to non-polymeric vinyl-sulfone, two (vinyl-sulfuryl acetamide) ethane (BVSAE) of such as two (vinyl-sulfuryl) methane (BVSM), two (vinyl-sulfuryl methyl) ether (BVSME) and 1,2-.The potpourri of rigidizer can be used if desired.Rigidizer can be incorporated in each achromaticity water wettability photographic layer by apparent any suitable amount for those skilled in the art.
In general, each achromaticity water wettability photographic layer can have as by element cross-section is carried out optical microscopy measure at least 150% expansivity.Expansion can by controlling by the hardening capacity that the rigidizer of appropriate amount carries out in light sensitive silver halide emulsion layer or in various working fluid (described below).
If desired, can make above-describedly to be suitable for the exposing radiation sensitization of silver halide to any applicable wavelength.Organic sensitizing dyestuff can be used, but can advantageously make when not using visible light photoactivated dyestuff silver salt have undesirable dyestuff stain to the UV part sensitization of electromagnetic wave spectrum to avoid having in the conductive articles of the high grade of transparency in hope.Or, silver halide can be used when nothing exceeds the spectral sensitization of its intrinsic spectral response.
The limiting examples of the condiment (comprising chemistry and spectral sensitization agent, filter dye, organic solvent, thickening agent, adulterant, emulsifying agent, surfactant, stabilizing agent, rigidizer and antifoggant) being applicable to be included together with silver halide is described in research and discloses in project in September, 36544,1994 and many publication of wherein identifying.This type of material is known in the art, and will be not difficult allocate or use this type of component for object described herein for skilled people in the industry.Some applicable silver salt emulsions are described in such as United States Patent (USP) 7,351,523 (Ge Ruisikeweiya (Grzeskowiak)), 5,589,318 and 5,512,415 (both giving the people such as Dai Er (Dale)).
Applicable silver halide emulsion containing the silver halide particle that can be reduced to silver metal particle can by any applicable particle growth method preparation, such as by use through design with maintain the concentration of silver ions in growth reactor feedback system, use balance double-run to silver nitrate and salt solusion.Known adulterant can from precipitation initial to end equably introduce or can structuring to the region in silver halide particle or band.Applicable adulterant includes but not limited to osmium adulterant, ruthenium adulterant, Fe2O3 doping agent, rhodium adulterant, iridium adulterant and cyano group ruthenium adulterant.The combination of osmium and iridium adulterant, the combination of the phosphoric osmium of such as nitrosyl radical and iridium adulterant is applicable.This type of complex compound can by United States Patent (USP) 5, and the mode described in 385,817 (Bel (Bell)) is alternately used as particle surface modifier.Chemical sensitization can be undertaken by any one in known silver halide chemical sensitizing method for emulsive, such as, use independent or thiosulfate that is that combine with gold complex or another kind of unstable sulphur compound.
Applicable silver halide particle can be circular cube, cube circle, octahedron, circular octahedron, polymorphic, sheet or laminar emulsion particle.This type of silver halide particle can be regular non-twin crystal, regular twin crystal or irregular twin crystal, to have cube or octahedral plane.In one embodiment, silver halide particle can be circular cube, and edge length is less than 0.5 μm and is at least 0.05 μm.
Antifoggant and stabilizing agent can be added to provide wanted sensitivity to silver halide emulsion time suitable.Operable antifoggant comprises such as azepine indenes (such as the purine), tetrazolium, benzotriazole, imidazoles and benzimidazole.
Must silver halide particle and hydrophilic adhesive or colloid and optional condiment applicable emulsion solvent (comprising the mixable organic solvent of Shui Heshui) can be used with the allotment of silver halide emulsion form and coating.For example, the solvent being applicable to manufacture silver halide emulsion or coating composite can be water; Alcohol, such as methyl alcohol; Ketone, such as acetone; Acid amides, such as formamide; Sulfoxide, such as dimethyl sulfoxide; Ester, such as ethyl acetate; Ether; Liquid polyethylene alcohol; Liquid or low-molecular-weight poly-(vinyl alcohol); Or the combination of these solvents.One or more in order to prepare the amount of the solvent of silver halide emulsion can be total composite weight at least 30 % by weight and at the most and comprise 50 % by weight.Therefore, this type coating composite can use any one preparation in photography emulsion manufacturing course as known in the art.
hydrophilic outer coating
Although achromaticity water wettability photographic layer can be the outermost layer in presoma, in many examples, hydrophilic outer coating can be placed in above each achromaticity water wettability photographic layer in either one or two support-side of transparent substrates.This hydrophilic outer coating can be the outermost layer (that is, either one or two support-side of transparent substrates not existing the layer of the deliberately side of being placed on it) in conductive film element precursor.Therefore, if two support-side of transparent substrates are in order to provide conductive silver pattern usually, so hydrophilic outer coating may reside in two support-side of transparent substrates.Therefore, the first hydrophilic outer coating can be placed in above the first achromaticity water wettability photographic layer, and the second hydrophilic outer coating can be placed in above the second achromaticity second water wettability photographic layer on the relative support side of substrate.
In most embodiments, each hydrophilic outer coating can directly be placed on each achromaticity water wettability photographic layer, means to there is not intervening layer in the described support-side of transparent substrates.The chemical composition of these hydrophilic outer coatings and dry thickness can be identical or different, but in most embodiments, it has substantially the same chemical composition and dry thickness in two support-side of transparent substrates.
In certain embodiments, each hydrophilic outer coating (first or second or both) can comprise the silver halide of one or more identical or different amount to provide at least 5mgAg/m after exposure and processing
2and at the most and comprise 150mgAg/m
2, or at least 5mgAg/m
2and at the most and comprise 100mgAg/m
2the silver metal particle of amount.
This silver halide can disperse in (usually equably) one or more hydrophilic adhesive in each hydrophilic outer coating or colloid, and described hydrophilic adhesive or colloid comprise above for those described in achromaticity water wettability photographic layer.In many examples, identical hydrophilic adhesive or colloid may be used in all layers of conductive film element precursor.But different hydrophilic bonding agent or colloid to may be used in various layer and in either one or two support-side of support substrates.One or more hydrophilic adhesive in each hydrophilic outer coating or the amount of colloid can be identical or different, and with total hydrophilic outer coating dry weight basis normally at least 50 % by weight and at the most and comprise 97 % by weight.
Hydrophilic outer coating can comprise at least 5mg/m
2and at the most and comprise 100mg/m
2one or more radiation absorber of amount, such as UV radiation absorber.Be suitable for UV radiation absorber can " through fixing " so that it is not easy to spread from hydrophilic outer coating.
Each hydrophilic outer coating can also comprise one or more rigidizer for hydrophilic adhesive or colloid (such as gelatin or gelatine derivative).Be suitable for rigidizer to describe above.
Also possibly, the silver halide that the silver halide in each hydrophilic outer coating and top are mounted with in its each achromaticity water wettability photographic layer is identical.
In addition, one or more silver halide in each hydrophilic outer coating can have at least 30nm and at the most and comprise 1000nm or at least 30nm and at the most and comprise the particle ESD of 300nm.
In certain embodiments, one or more silver halide in each hydrophilic outer coating has and is greater than top and is mounted with the particle ESD of the particle ESD of the silver halide in its achromaticity water wettability photographic layer.
The dry thickness of each hydrophilic outer coating can be at least 100nm and at the most and comprise 800nm, or more particularly at least 300nm and at the most and comprise 500nm.In many examples, the particle ESD in hydrophilic outer coating and dry thickness ratio can be 0.25:1 to and comprise 1.75:1 or more may 0.5:1 to and comprise 1.25:1.
In various embodiments, the silver halide in each hydrophilic outer coating can comprise 100mol% bromide or at the most 100mol% chloride at the most, and at the most and comprise 3mol% iodide, is all in the molar weight of total silver content.
In other embodiments, the silver halide in each hydrophilic outer coating can comprise the more chloride of the silver halide be mounted with in its achromaticity water wettability photographic layer than top.This close tie up to substrate in this type of " duplex " conductive film element precursor two support-side on can be identical or different.
In applicable embodiment, silver halide in each hydrophilic outer coating can comprise in total silver content at least 80mol% bromide, and remainder is chloride or iodide, and the silver halide that top is mounted with in its achromaticity water wettability photographic layer can have at least 80mol% bromide, and remainder is iodide or chloride, all in total silver content.
Also be suitable in conductive film element precursor of the present invention, the silver halide that the silver halide in each hydrophilic outer coating and top are mounted with in its each achromaticity water wettability photographic layer mates in picture rate.When such as with μ J/m
2for unit represents, the exposure sensitivity of the silver halide emulsion in hydrophilic outer coating can be provide at least 10% of the optimum sensitivity of the silver halide emulsion in the bottom achromaticity water wettability photographic layer of conductive silver pattern and at the most and comprise 200% time, this is able to best realization.
additional layer:
In one or two support-side of transparent substrates except above-described layer and component, can also to comprise and nonessential but other layer of some additional properties or benefit can be provided, other such as, in radiation absorption filter layer, adhesive coating and photography known layer for putting into practice conductive film element precursor of the present invention.Radiation absorption filter layer can also be called " antihalation " layer, and it can be positioned between the require layers in each support-side of transparent substrates.For example, each support-side can have direct arrangement thereon and the radiation absorption filter layer be directly placed in below achromaticity water wettability photographic layer.
This type of radiation absorption filter layer can comprise the filter dye absorbed in one or more UV at electromagnetic wave spectrum, redness, green or blue region or its any combination, and can be positioned between substrate and achromaticity water wettability photographic layer in one or two support-side of transparent substrates.
For example, conductive film element precursor can comprise UV radiation absorption layer between the first support-side of transparent substrates and the first achromaticity water wettability photographic layer.
Duplex conductive film element precursor comprises the second achromaticity water wettability photographic layer further in relative second support-side of transparent substrates, and is placed in the second hydrophilic outer coating above the second achromaticity water wettability photographic layer.Radiation (such as, UV) absorbing filter layer can be placed between relative second support-side of transparent substrates and the second achromaticity water wettability photographic layer, and described radiation absorption layer can be identical or different with the radiation absorption filter layer in the first support-side of transparent substrates.
In many duplex embodiment, the second achromaticity water wettability photographic layer and the second hydrophilic outer coating have the composition identical with the first hydrophilic outer coating with the first achromaticity water wettability photographic layer respectively.
Therefore, in certain embodiments, conductive film element precursor can comprise the second achromaticity water wettability photographic layer further in relative second support-side of transparent substrates, and is optionally placed in the second hydrophilic outer coating above the second achromaticity water wettability photographic layer.
For example, the second achromaticity water wettability photographic layer and the second hydrophilic outer coating can have the composition identical with the first hydrophilic outer coating with the first achromaticity water wettability photographic layer respectively.
In other embodiments, as with μ J/m
2for unit represents, the exposure sensitivity of the silver halide emulsion in the first hydrophilic outer coating can be the optimum sensitivity of the silver halide emulsion in the first achromaticity water wettability photographic layer at least 10% and at the most and comprise 200%, and as with μ J/m
2for unit represents, the exposure sensitivity of the silver halide emulsion in the second hydrophilic outer coating can be the optimum sensitivity of the silver halide emulsion in the second achromaticity water wettability photographic layer at least 10% and at the most and comprise 200%.The optimum sensitivity of the corresponding side of transparent substrates can be identical or different.
Prepare conductive film element precursor
Various layer uses suitable component and coating solvents allocate and use known coating processes to be coated to one or two support-side of applicable transparent substrates (as described above), described coating processes comprises those (such as, pearl painting, blade coating, curtain coating, spraying and hopper-type coatings) conventional in photography industry.Each layer can in single channel program or each support-side being simultaneously coated to transparent substrates in multi-layer coated program.
Conductive film element is provided
The conductive film element precursor being applicable to method of the present invention is provided, and then makes its Imagewise exposure to provide silver metal image of hiding in either one or two support-side of transparent substrates in achromaticity water wettability photographic layer.Any silver halide be present in hydrophilic outer coating is also reduced to silver metal particles by Imagewise exposure.Conductive film element precursor can at once for expecting object, or it can store for using afterwards by reel or sheet form.For example, presoma can be rolled during manufacture and store for Scroll imaging and process, and is cut into wanted size and shape subsequently.
More generally, light sensitive silver halide in each achromaticity water wettability photographic layer can Imagewise exposure in the suitable actinic radiation (UV is to visible radiation) from applicable source well known in the art, and then to carry out as described below develop (silver ion reduction is silver metal particle).This type of exposure is provided in the first achromaticity water wettability photographic layer to comprise hides silver-colored image and in the second achromaticity water wettability photographic layer (if it is present in presoma), comprises the presoma of the Imagewise exposure of silver-colored image of hiding.
In certain embodiments, the controlled any exposing radiation for use in the achromaticity water wettability photographic layer in a support-side of transparent substrates of exposure process does not arrive any achromaticity water wettability photographic layer in relative second support-side of transparent substrates.This result can as such as realized described in U.S. Patent application 2011/0289771 (Li Cheng (Kuriki)) by different way.Particularly suitable be comprise radiation filtering dye coating or antihalation layer on the both sides of transparent substrates, described layer is configured between transparent substrates and each (first and second) achromaticity water wettability photographic layer, and the radiation that exposure is used in (or second or two) the support-side guiding from first of transparent substrates of conductive film element precursor place is carried out.
process with silver halide developer solution:
First processing process pH can be used to be at least 8 and at the most and comprise 13 or more typically at least 10 and at the most and the silver halide developer solution black-and-white development agent of silver metal (formed) comprising 11 carry out.PH can use known alkaline reagent to provide together with hereafter described compound.
First of this silver halide developer solution must component be one or more main developer, such as quinhydrones or derivatives thereof or ascorbic acid or derivatives thereof.The quinhydrones be suitable for or derivant (also referred to as polyhydroxy benzenes) include but not limited to quinhydrones, catechol, 1,2,3,-thrihydroxy-benzene, methylnaphthohydroquinone, chlorohydroquinone, quinhydrones Monosulfate, 1,2-naphthalenediol and 1,4-Naphthohydroquinone.The ascorbic acid be suitable for and derivant include but not limited to ascorbic acid, different anti-hematic acid and its derivant, sodium ascorbate and different anti-hematic acid sodium.
One or more main developer can by least 0.01mol/l and at the most and comprise 1mol/l, at least 0.01mol/l and at the most and comprise 0.15mol/l or more typically at least 0.075mol/l and at the most and the total amount comprising 0.14mol/l be present in silver halide developer solution.As mentioned above, the potpourri of main developer can be used if desired, and in the described embodiment, these concentration refer to the total amount of main developer.
Silver halide developer solution also comprises one or more catalysis developer as the second required component, and this compounds is para-aminophenol or derivatives thereof or phenidone (comprising the derivant of phenidone).This type of catalysis developer can by least 0.001mol/l and at the most and comprise 0.1mol/l, at least 0.001mol/l and at the most and comprise 0.025mol/l or typically at least 0.001 and at the most and the total amount comprising 0.002mol/l be present in silver halide developer solution.When using the potpourri of these compounds, concentration refers to the total amount of catalysis developer.
Compared with being the main developer of main silver ion developer (reductive agent), need the existence of catalysis developer so that particularly by reducing or eliminating development induction time to increase the dynamics of development.
The para-aminophenol be suitable for includes but not limited to p-methylaminophenol, para-aminophenol, m-chloro para-aminophenol, a methyl-p-aminophenol and p-hydroxybenzene glycocoll.The phenidone be suitable for and derivant include but not limited to the phenidone being substituted or being unsubstituted, such as 4,4-dimethyl-3-pyrazolidones (dimezone) and 4-(hydroxymethyl)-4-methyl isophthalic acid-phenyl-3-pyrazolidone (HMMP).
In general, the concentration of one or more catalysis developer can be less than the concentration of one or more main developer.More particularly, the total concentration of one or more main developer can be at least 100 times of the total concentration of one or more catalysis developer.
In many examples, silver halide developer solution has quinhydrones or derivatives thereof as main developer, and phenidone is as catalysis developer.
The important optional components of silver halide developer solution includes but not limited to one or more alkali metal sulfite; With one or more development restrainer or restriction agent, such as alkali halide, the mercapto-tetrazole being substituted or being unsubstituted, one or more benzotriazole, one or more aryl or alkyl disulfide and one or more aryl or alkyl sulfhydryl.The potpourri of the compound of any identical or different classification can be used.
For example, the alkali metal sulfite be suitable for comprises sodium sulphite, potassium sulfite and its potpourri.Alkali metal sulfite can by least 0.1mol/l and at the most and comprise 1mol/l or typically at least 0.4mol/l and at the most and the total amount comprising 0.8mol/l be present in silver halide developer solution.If use the potpourri of compound, so this concentration refers to the total amount of all sulphite.
One or more development restrainer or restriction agent, at least one in such as, in alkali halide, aryl thiol tetrazolium, benzotriazole and aryl or alkyl disulfide or aryl or alkyl sulfhydryl any one can by least 0.25mmol/l and at the most and comprise 2.5mmol/l or typically at least 0.5mmol/l and at the most and the total amount comprising 1.5mmol/l be present in silver halide developer solution.
The alkali halide be suitable for includes but not limited to sodium chloride, sodium bromide, potassium chloride and potassium bromide.
The aryl thiol tetrazolium being substituted or being unsubstituted be suitable for comprises and includes but not limited to following compound: 1-phenyl-5-mercapto-tetrazole (PMT), 1-ethyl-5-mercapto-tetrazole, the 1-tert-butyl group-5-mercapto-tetrazole and 1-pyridine radicals-5-mercapto-tetrazole.
The benzotriazole be suitable for includes but not limited to the benzotriazole cpd being substituted and being unsubstituted, such as benzotriazole, 5-methylbenzotrazole and 5,6-dichloro benzotriazole.
The aryl be suitable for or alkyl disulfide include but not limited to 5,5'-(dithiobis (4,1-phenylene imino group)) two (5-oxo-pentanoic acid) and its disodium salt, 2,2'-dithiobis benzoic acid and its disodium salt and 5,5'-dithiobis (valeric acid) and its disodium salt.
The aryl be suitable for or alkyl sulfhydryl include but not limited to 5-sulfydryl-4,1-phenylimino-5-oxo-pentanoic acid and its sodium salt and 5-mercaptopentanoic acid and its sodium salt.
Other condiment that can be present in silver halide developer solution by known quantity includes but not limited to metal-chelator, antiseptic (except sulphite), biocide, antioxidant, a small amount of mixable organic solvent of water (such as phenmethylol and diethylene glycol), nucleator, acid, alkali (such as alkali metal hydroxide) and buffering agent (such as carbonate, borax, phosphate and other basic salt).
Silver halide developer solution can provide under working strength, or with can before using known process equipment and program processing or period the conc forms that compatibly dilutes provide.For example, silver halide developer solution can concentrate at least 5 times compared with wanted working strength concentration.
Therefore, silver halide developer solution can be applicable to the time in order to the presoma of processing at applicable temperature, under usual atmospheric pressure or process Imagewise exposure, to realize the development of at least 90mol% of at least 75mol% of the silver ion of the exposure in first (or second) achromaticity water wettability photographic layer of Imagewise exposure and any silver ion typically at least in 90mol% and each hydrophilic outer coating that can exist.
For example, use the processing temperature of silver halide developer solution can at least 15 DEG C and at the most and comprise 60 DEG C or typically at least 35 DEG C and at the most and comprise in the scope of 45 DEG C.Applicable process time can at least 10 seconds and at the most and comprise 10 minutes but more may at the most and comprise within the scope of 1 minute.Skilled staff can use normal experiment to find optimum processing conditions so that silver ion reduction is being wanted result by realizing in the silver metal in sub-image.Use the washing of water or applicable aqueous solution or rinse process and after this machining feature, before with the processing of silver halide solution physical developer solution, the applicable time can be carried out at applicable temperature.
process with silver halide solution physical developer solution:
After optional washing, the presoma of Imagewise exposure is then usual carries out the electric conductivity of processing the silver-colored image, the such as predetermined silver metal pattern that improve on one in the support-side of substrate or both sides in unique silver halide solution physical developer solution.
Silver halide solution physical developer solution usually can have at least 8 and at the most and comprise 13 or typically at least 8 and at the most and comprise 12 pH.PH can use known alkaline reagent to provide together with hereafter described compound.
This silver halide solution physical developer solution comprise one or more be selected from following in the main developer of one or many person as required component: quinhydrones or derivatives thereof or one or more ascorbic acid or derivatives thereof.The example of this compounds is provided in above.Main developer in silver halide solution physical developer solution can be identical or different with the main developer in above-described silver halide developer solution.
One or more main developer in silver halide solution physical developer solution can by least 0.01mol/l and at the most and comprise 1mol/l or typically at least 0.05mol/l and at the most and the total amount comprising 0.2mol/l exist.If use the potpourri of this compounds, so this concentration refers to the total amount of main developer.
In addition, silver halide solution physical developer solution comprise at least 0.001mol/l and at the most and comprise 0.1mol/l or typically at least 0.005mol/l and at the most and one or more silver halide catalyst-solvent comprising the amount of 0.05mol/l as required component.When using the potpourri of this compounds, these concentration refer to the total amount of silver halide catalyst-solvent.
The silver halide catalyst-solvent be suitable for includes but not limited to alkali metal thiocyanate, such as sodium thiocyanate and potassium rhodanide; Thioether, such as 3,6-dithia-1,8-ethohexadiols; With heterocycle thioketones, such as tetrahydrochysene-4,6-dimethyl-1,3,5-triazines-2 (1H)-thioketones and tetrahydrochysene-3-hydroxyethyl-1,3,5-triazines-2 (1H)-thioketones.These compounds can easily with silver-colored complexing.
For the silver halide solution physical developer solution in the present invention in fact not containing catalysis developer, such as, above about those (b) compound that silver halide developer solution describes.This compounds that term " in fact without " means to be less than 0.001mol/l or to be even less than 0.0001mol/l is deliberately incorporated in solution or results from solution.
Silver halide solution physical developer solution can comprise one or more alkali metal sulfite further, comprises sodium sulphite, potassium sulfite and its potpourri.When using potassium sulfite or sodium sulphite or especially when only using potassium sulfite, alkali metal sulfite can by least 0.2mol/l and at the most and comprise 3mol/l or typically at least 0.5mol/l and at the most and the total amount comprising 1mol/l be present in silver halide solution physical developer solution.If use the potpourri of compound, so these concentration refer to the total amount of all sulphite.
Silver halide solution physical developer solution may further include one or more can with the poly-aminopolycarboxylic salt of silver ion complexation, include but not limited to diethylene-triamine pentaacetic acid five sodium-salt and other similar compound as known in the art.When there is not sulphite, this compounds can particularly suitable.This compounds can by least 0.001mol/l and at the most and the amount comprising 0.03mol/l exist.
Silver halide solution physical developer solution can also comprise the complexing of metal ion agent of other complexing of metal ion that one or more maybe can be able to exist with silver, calcium, iron, magnesium.Silver or the agent of calcium complexing of metal ion can particularly suitables with the total amount of at least 0.001mol/l.
The silver halide solution physical developer solution of particularly suitable includes but not limited to quinhydrones or derivatives thereof and sodium thiocyanate or potassium rhodanide, and optionally sulphite and calcium or silver metal ionic complexing agent.
Silver halide physical solution developer solution can provide under working strength, or with before using known process equipment and program processing or period the conc forms that compatibly dilutes provide.For example, silver halide physical developer can concentrate at least 4 times compared with wanted working strength concentration.
Therefore, silver halide solution physical developer solution is applicable to the time in order to the presoma of processing at applicable temperature, under usual atmospheric pressure or process Imagewise exposure, to provide the electric conductivity of gained first silver medal image, it is only with at least 2 times of the electric conductivity of the first silver medal image (or second silver medal image) after the presoma of silver halide developer solution processing Imagewise exposure.
The conductivity measurement of the first silver medal image obtains described in Examples below.
For this machining feature, temperature can at least 20 DEG C and at the most and comprise within the scope of 60 DEG C, or typically be at least 35 DEG C and at the most and comprise 45 DEG C.The process time be suitable for can at least 30 seconds and at the most and comprise 6 minutes, but more may at least 2 minutes and at the most and comprise within the scope of 4 minutes.Skilled staff can use normal experiment to want conductivity results to find optimum processing conditions to realize.Use the washing of water or applicable aqueous solution or rinse process and after this machining feature, before with stop bath process, the applicable time can be carried out at applicable temperature.
In many examples, identical silver halide developer solution, silver halide solution physical developer solution and stop bath are used for after the Imagewise exposure of both sides, form the first and second silver medal images.
fixing:
After with the processing of silver halide solution physical developer solution and optional washing, remaining undeveloped silver ion (in any layer) can by with stop bath process Imagewise exposure and the presoma developed and removing.Stop bath is known in black-and-white photography field, and containing one or more complexing silver halide so that by it from there is the compound removed its layer.Thiosulfate is usually used in stop bath.Stop bath optionally can contain rigidizer, such as alum or chrome alum.Namely the film of development can be engraved in stop bath and processes after the development of silver halide solution physical, maybe can exist intervention stop shadow liquid or washing or both.Fixingly can to carry out under any applicable temperature and time, such as, at least 20 DEG C, to continue at least 30 seconds.
After fixing, conductive articles containing the first silver medal image (with the second optional silver medal image) can wash or rinse in water, described water optionally can comprise surfactant or other material to reduce dried water spot formation, and described drying was optional before next machining feature.Dry can in the environment or by such as heating and realizing at higher than 50 DEG C but lower than the temperature of the glass transformation temperature of substrate in convection oven.
In fixing the first silver medal image then in each previous achromaticity water wettability photographic layer, (in usual silver-colored pattern) leaves silver metal particle.This fixing any undeveloped silver ion also removed in each hydrophilic outer coating.For duplexing conductive film element precursor described herein, relative second support-side provides same effect.
Wish to be that in stop bath, after processing, gained conductive film element represents (vision) D being less than or equal to 0.03
min.
After fixing, article can wash or rinse in water, and described water optionally can comprise surfactant or other material to reduce dried water spot formation.
electric conductivity strengthens:
After fixing and optional flushing and before drying as described above, the conductive articles comprising the first silver medal image (with the second optional silver medal image) can wash with water further or rinse and then treated with the electric conductivity of the silver metal (or core) in each silver-colored image strengthened further in each support-side of substrate.Various ways has proposed to perform this " electric conductivity enhancing " process.For example, United States Patent (USP) 7,985,527 (DS is (Tokunaga) forever) and 8,012,676 people such as () Jia Shu describe and use hot bath, water vapor, reductive agent or halogenide process.The details of this type of process is provided in these patents.
Also then can carry out optional washing and drying by repeating to contact (process) with conductivity enhancer, and this being recycled and reused for process and optional washing that electric conductivity strengthens and drying circulates usual one or repeatedly, strengthens the electric conductivity of the silver metal particle in each silver-colored image.The conductivity enhancer be suitable for includes but not limited to sulphite, borane compound, quinhydrones, p-phenylenediamine (PPD) and phosphite.This process can at least 30 DEG C and at the most and to carry out at least 0.25 minute under comprising the temperature of 90 DEG C and at the most and comprise 30 minutes.
extra process:
Prebath solution also can in order to the silver salt exposed in the pre-treatment of above-described silver halide development.This type of prebath solution can comprise one or more as described above and the development restrainer of identical or different amount.Effective development restrainer includes but not limited to benzotriazole, heterocycle thioketones and mercapto-tetrazole.Front bath temperature can such as above about in the scope described by silver halide development step.The prebath time depends on concentration and concrete inhibitor, but it can at least 10 seconds and at the most and comprise within the scope of 4 minutes.
In certain embodiments it is applicable that after fixing and before the drying with hardening bath process conductive film element to improve the physical durability of gained conductive film element.This type of hardening bath can comprise one or more for those skilled in the art by the known rigidizer of apparent appropriate amount.
To the extra process of conductive film element, such as, can also carry out before in the end drying under any applicable time and temperature if desired with the process of stabilizer bath.
Method of the present invention can use a kind of conductive film element precursor to carry out, described conductive film element precursor substrate first with the first and second hydrophilic outer coatings of comprising applicable first and second achromaticity water wettability photographic layers and being placed in respectively above the first and second achromaticity water wettability photographic layers in relative second support-side, the first and second hydrophilic outer coatings are that corresponding first of substrate supports and the outermost layer in relative second support-side.
In these class methods, both the first and second achromaticity water wettability photographic layers through correct exposure to provide the pattern of hiding containing silver halide of identical or different (usually different) in the first and second achromaticity water wettability photographic layers.Modes of these different exposures can be simultaneously or sequentially.In many examples, both sides are through exposing simultaneously.
Then silver halide in the latent charge image formed in two relative achromaticity water wettability photographic layers is converted into the silver metal particle on both sides during above-described processing process.Therefore, two latent charge images can develop and fixing simultaneously.
Unconverted silver ion can from first and second achromaticity water wettability photographic layers remove, on relative support second side of substrate correspond to first and second hide pattern corresponding first and second patterns in leave silver metal particle.
During this class process, identical silver halide developer solution, silver halide solution physical developer solution and stop bath are for the formation of the first and second silver medal images.
Optionally and desirably, the silver metal particle in the pattern on the both sides of element can be treated to strengthen silver metal electric conductivity further as described above.
In many examples, gained conductive film element has at least one predetermined conductive silver metal electrode grid (pattern) and desirably in relative second support-side of substrate, has conductive silver metal electrode grid (pattern) at least the first support-side of substrate, the composition of described electrode grid, pattern arrangement, conductor wire thickness or grid line shape (such as, sexangle, rhombus, octagon, square, circle or irregular) are different.For example, the conductive silver metal electrode grid in the first support-side of substrate can have the conductive silver metal electrode grid of square pattern, and the conductive silver metal electrode grid on relative support second side of substrate can have argyle design.
Use the conductive film element prepared of the present invention to use after its formation, or its can further treated such as with by conducting metal (such as copper, palladium, platinum, aluminium, tin or gold) electroless-plating on first (with second) silver-colored image.The conducting metal of identical or different electroless-plating can be provided on the first and second silver medal images on the relative support side of substrate.
Silver management
In the method using the developer easily dissolving silver halide, there is following risk, the solvable silver ion of gained can move from light sensitive silver halide emulsion and then it can react to form argent with black-and-white development agent.The problem that argent brings again precipitation or deposition to be formed, causes developer undesirable.In these cases, wish by the silver ion of dissolving its processing tank in gather and become be reduced to argent before remove from developer solution.The removal of solvable silver ion can be realized by multitude of different ways, comprise on metallide, electroless plating to the substrate containing active nucleation site (such as Cary-Lea silver) (such as United States Patent (USP) 5, described in 188,662 people such as () the ancient gold (McGuckin) of Mike) or use ion exchange resin silver ion to high-affinity.Simpler process is more suitable for by the removal of some ion exchange resin (being commonly referred to chelating resin).For silver ion, there is high power capacity and specific multiple chelating resin is commercially available from various source.
There is provided following instance practice of the present invention to be described and not to intend to limit by any way.
125 μm of the achromaticity light sensitive silver halide emulsion (emulsion 1) be coated with containing 98mol% silver chloride and 2mol% silver iodide poly-(ethylene glycol terephthalate) substrates are used to prepare conductive film element precursor (being designated element 1 and element 2).Emulsion particle has cubic morphology and edge length 0.36 μm, and is used with 0.5 % by weight of total gelatin coating as BVSM [1,1 '-(methylene (sulfuryl)) two-ethane] as a part for lower floor 2 hardens.
Ground floor (layer 1) is directly provided in substrate absorbs for UV.UV under 365nm absorbs and is increased to 1.7 ODUs.Layer 1 comprises 1500mg/m
2gelatin and 300mg/m
2tINUVIN328UV absorbing dye.
The light sensitive silver halide emulsion layer (layer 2) comprising emulsion 1 is provided in above layer 1.For element 1, under silver (Ag) and gelatin weight ratio are held constant at 2.33:1 (or under volume ratio of about 0.297:1).For element 2, under silver (Ag) and gelatin weight ratio are held constant at 2.45:1 (or under volume ratio of about 0.313:1).
Both elements 1 and 2 comprise hydrophilic outer coating (layer 3) further above layer 2, and described layer 3 comprises 488mg/m
2gelatin, 6mg/m
20.6 μm of insoluble polymerization dumb light particle and conventional coating surface activating agent.
Make the conductive film element precursor of element 1 by the design shade Imagewise exposure of chromium plating, described shade has the comb mesh pattern of rhombus, and turning is 300 μm of (vertically) × 500 μm (levels) to turning size.Grid line on shade is about 3 μm wide.The width of each passage is 4.8mm.The length of each passage is 85mm.Expose with the UV radiation under 365nm wavelength.
Used by the silver hailde film of Imagewise exposure the processing sequence processing shown in following Table I silver-colored kation is reduced to silver metal and forms conductive film element.The assessment result of conductive film element is also showed in Table I as follows.
Table I: the processing sequence of element 1 and result
Use two point probes be positioned in the contact pad of the end of each conductive channel to measure the resistance of above-described five same channels, and two point probes are connected to ohmmeter.Use the vision D in the non-exposed area of X-Rite model 310 densimeter measurement conductive film element
min.Visual density is weighted mean value that is red, green and blue density, through design with the sensitivity of simulating human eye.Table I comprises relative resistance and the vision D of six tests
minvalue is to represent advantage of the present invention.The combination (invention example 1) of developer 1A and developer 2A provides low resistance and low vision D
minboth.Independent developer 1A (comparative example 2 and 3) or separately developer 2A (comparative example 4) represent high resistance.Conventional black-and-white development agent, developer 2B provides low resistance (comparative example 5), but high vision D
min.Developer 1A and conventional black-and-white development agent, developer 2B combinationally uses, and (comparative example 6) also provides good resistance, but provides unacceptable vision D
min.
The conductive film element precursor of element 2 is exposed as described above, and then uses the processing sequence processing shown in following Table II.Use two point probes to measure and obtain sheet resistance, described measurement uses the contact pad of the directly described grid of contact to carry out on 1 × 1 inch of (2.54cm × 2.54cm) grid, produces the resistance in units of ohm-sq.
Table II: the processing sequence of element 2 and result
Table II comprises the sheet resistance value of four tests to represent advantage of the present invention.First developer used in practice of the present invention and the combination (invention example 7,8 and 9) of the second developer provide and comprise ascorbic acid and compare much lower sheet resistance with the single conventional developer (comparative example 10) of N-methyl-para-aminophenol with using.
Composition for the working fluid in these examples is showed in Table III in IX.All these working fluids are all the aqueous solution using demineralization water to prepare.
Table III: developer 1A
| Component | g/l |
| Potassium hydroxide, 45.5% solution | 10.83 |
| Sodium bromide | 5.00 |
| 4,4-dimethyl-1-phenyl-3-pyrazolidone | 0.33 |
| 1-phenyl-5-mercapto-tetrazole | 0.13 |
| 5-methylbenzotrazole | 0.17 |
| 50% solution of NaOH | 1.82 |
| (nitrogen base three (methylene))-three-phosphonic acids five sodium-salt | 0.29 |
| Two (N-(the carboxymethyl group)-glycocoll of N, N'-1,2-second two base | 1.77 |
| Single sodium carbonate hydrate | 8.33 |
| Potassium sulfite, 45% solution | 83.33 |
| Quinhydrones | 12.50 |
| 5,5'-(dithiobis (4,1-phenylene imino group)) two (5-oxo-pentanoic acid) | 0.12 |
| pH | 10.55 |
Table IV: developer 1B
| Component | g/l |
| Ascorbic acid | 8.00 |
| Sodium carbonate | 17 |
| N-methyl-para-aminophenol | 1.80 |
| 5-methylbenzotrazole | 0.16 |
| pH | 10.10 |
Table V: developer 2A
| Component | g/l |
| Sodium sulphite | 92.54 |
| Quinhydrones | 4.630 |
| N, N-two (2-(two (carboxymethyl group)-amino) ethyl)-glycocoll five sodium-salt | 0.950 |
| Sodium tetraborate pentahydrate | 2.830 |
| Sodium thiocyanate | 0.42 |
| pH | 9.11 |
Table VI: developer 2B
| Component | g/l |
| Sodium sulphite | 92.54 |
| N-methyl-para-aminophenol | 1.85 |
| Quinhydrones | 4.63 |
| N, N-two (2-(two (carboxymethyl group)-amino) ethyl)-glycocoll five sodium-salt | 0.95 |
| Sodium tetraborate pentahydrate | 2.83 |
| Sodium thiocyanate | 0.42 |
| pH | 9.11 |
Table VII: developer 2C
| Component | g/l |
| Ascorbic acid | 8.00 |
| Sodium carbonate | 17 |
| Diethylene-triamine pentaacetic acid five sodium-salt | 7.56 |
| pH | 10.10 |
Table VIII: developer 2D
| Component | g/l |
| Ascorbic acid | 8.00 |
| Sodium carbonate | 17 |
| Sodium sulphite | 12 |
| Potassium rhodanide | 0.10 |
| 5-phenylmercapto tetrazolium | 0.15 |
| pH | 10.10 |
Table I X: stop bath
| Component | g/l |
| Acetic acid | 24.43 |
| NaOH, 50% solution | 10.25 |
| Hyposulfurous acid ammonium | 246.50 |
| Sodium pyrosulfite | 15.88 |
| Sodium tetraborate pentahydrate | 11.18 |
| Aluminium sulphate, 18.5% solution | 36.26 |
| pH | 4.30 |
Claims (23)
1. a silver halide solution physical developer solution, it comprises:
(a) at least 0.01mol/l and at the most and comprise the main developer of the amount of 1mol/l, it is quinhydrones or ascorbic acid or the derivant of any one, and
(c) at least 0.001mol/l and at the most and comprise the silver halide catalyst-solvent of the amount of 0.1mol/l, and described silver halide solution physical developer solution is not in fact containing (b) catalysis developer.
2. silver halide solution physical developer solution according to claim 1, it comprises at least 0.2mol/l and at the most and comprise the alkali metal sulfite of the amount of 3mol/l further.
3. silver halide solution physical developer solution according to claim 1 and 2, it comprises at least 0.5mol/l and at the most and comprise sodium sulphite or the potassium sulfite of the amount of 1mol/l further.
4. silver halide solution physical developer solution according to claim 1 and 2, wherein said silver halide catalyst-solvent is at least 0.005mol/l and at the most and comprise the alkali metal thiocyanate of the amount of 0.05mol/l.
5. silver halide solution physical developer solution according to claim 1 and 2, it comprises one or more complexing of metal ion agent of the total amount of at least 0.001mol/l further.
6. silver halide solution physical developer solution according to claim 5, it comprises the calcium of the total amount of at least 0.001mol/l or silver metal ionic complexing agent further as complexing of metal ion agent.
7. silver halide solution physical developer solution according to claim 1 and 2, wherein said main developer is quinhydrones or derivatives thereof, and described silver halide catalyst-solvent is sodium thiocyanate or potassium rhodanide.
8. silver halide solution physical developer solution according to claim 7, it comprises at least 0.5mol/l and at the most and comprise sodium sulphite or the potassium sulfite of the amount of 1mol/l further.
9. silver halide solution physical developer solution according to claim 1 and 2, it concentrates at least 4 times compared with wanted working strength concentration.
10. the transparent substrates in conductive film element provides a method for conductive silver image, described method comprises in order:
Imagewise exposure comprises the conductive film element precursor with the first support-side and the transparent substrates of relative second support-side, and described conductive film element precursor comprises the first achromaticity water wettability photographic layer comprising light sensitive silver halide and the first hydrophilic outer coating be optionally placed in above described first achromaticity water wettability photographic layer in order in described first support-side, the first presoma of Imagewise exposure of hiding silver-colored image is comprised to be provided in described first achromaticity water wettability photographic layer
Be at least 8 at pH and comprise the presoma at least 10 seconds processing described Imagewise exposure in following silver halide developer solution: (a) at least 0.01mol/l and at the most and comprise the main developer of the amount of 1mol/l, it is quinhydrones or ascorbic acid or the derivant of any one, (b) at least 0.001mol/l and at the most and comprise the catalysis developer of the amount of 0.1mol/l, it is para-aminophenol or phenidone or the derivant of any one, to provide the first silver medal image of silver-colored image of hiding corresponding to described first in described first achromaticity water wettability photographic layer
At the temperature of at least 20 DEG C, the presoma at least 30 seconds of described Imagewise exposure is processed in the silver halide solution physical developer solution according to claim arbitrary in claim 1 to 9, to provide the electric conductivity of described silver-colored image, it is only with at least 2 times of the electric conductivity of the described first silver medal image after the processing of described silver halide developer solution
The presoma of described Imagewise exposure is processed in stop bath, to remove residue silver ion and to provide the conductive film element containing described first silver medal image,
Process described conductive film element, to strengthen the electric conductivity of described first silver medal image, and
Optionally washing and the described conductive film element of drying.
11. methods according to claim 10, wherein said conductive film element is to represent (vision) D being less than or equal to 0.03 after processing in described stop bath
min.
12. methods according to claim 10 or 11, wherein process to strengthen the circulation of electric conductivity and optional washing and drying cycles and repeat at least one times.
13. methods according to claim 10 or 11, wherein said first silver medal image is provided in predetermined conductive silver pattern.
14. methods according to claim 10 or 11, wherein said first achromaticity water wettability photographic layer comprises one or more silver halide, is less than 5000mgAg/m to provide
2total silver metal coverage rate.
15. methods according to claim 10 or 11, wherein said conductive film element precursor comprises the first hydrophilic outer coating be placed in above described first achromaticity water wettability photographic layer further, described first hydrophilic outer coating optionally comprises one or more silver halide, to provide at least 5mgAg/m
2and at the most and comprise 150mgAg/m
2the silver metal of coverage rate, and one or more silver halide described has at least 30nm and at the most and comprise the particle ESD of 300nm separately.
16. methods according to claim 15, wherein said first hydrophilic outer coating comprises UV absorbers further.
17. methods according to claim 10 or 11, wherein said silver halide developer solution comprises at least 0.1mol/l and at the most and comprise the alkali metal sulfite of the amount of 1mol/l further.
18. methods according to claim 10 or 11, wherein said silver halide developer solution comprise further following in one or many person: alkali halide, aryl thiol tetrazolium, benzotriazole, aryl or alkyl disulfide or aryl or alkyl sulfhydryl.
19. methods according to claim 10 or 11, the second hydrophilic outer coating that wherein said conductive film element precursor comprises the second achromaticity water wettability photographic layer further and is optionally placed in above described second achromaticity water wettability photographic layer in described relative second support-side of described transparent substrates, and described method comprises further:
From conductive film element precursor described in the described second-phase offside Imagewise exposure of described transparent substrates, to provide second to hide silver-colored image in the described second achromaticity water wettability photographic layer of the presoma at described Imagewise exposure,
Be at least 8 at pH and comprise the presoma at least 10 seconds processing described Imagewise exposure in following identical or different silver halide developer solution: (a) at least 0.01mol/l and at the most and comprise the main developer of the amount of 1mol/l, it is quinhydrones or ascorbic acid or the derivant of any one, (b) at least 0.001mol/l and at the most and comprise the catalysis developer of the amount of 0.1mol/l, it is para-aminophenol or phenidone or the derivant of any one, to provide the second silver medal image of silver-colored image of hiding corresponding to described second in described second achromaticity water wettability photographic layer,
At the temperature of at least 20 DEG C, the presoma at least 30 seconds of described Imagewise exposure is processed in the identical or different silver halide solution physical developer solution according to claim arbitrary in claim 1 to 9, to provide the electric conductivity of described silver-colored image, it is only with at least 2 times of electric conductivity of the described second silver medal image after the first developer solution processing
The presoma of described Imagewise exposure is processed in stop bath, to remove residue silver ion and to provide the conductive film element containing described second silver medal image,
Process described conductive film element, to strengthen the electric conductivity of described second silver medal image, and
Optionally washing and the described conductive film element of drying.
20. methods according to claim 19, described conductive film element precursor comprises the second hydrophilic outer coating be placed in above described second achromaticity water wettability photographic layer further, described second hydrophilic outer coating optionally comprises one or more silver halide, to provide at least 5mgAg/m
2and at the most and comprise 150mgAg/m
2the silver metal of coverage rate, and one or more silver halide described has at least 30nm and at the most and comprise the particle ESD of 300nm separately.
21. 1 kinds of conductive film elements provided by the method according to claim arbitrary in claim 10 to 20, it has the first silver medal image at least the first support-side of transparent substrates.
22. 1 kinds of conductive film elements provided by the method according to claim arbitrary in claim 19 to 20, it has the first silver medal image and have the second silver medal image in relative second support-side of described transparent substrates in the first support-side of transparent substrates.
23. conductive film elements according to claim 21 or 22, it is further at described first silver medal image and the conducting metal optionally described second silver medal image comprising electroless-plating.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US14/281,984 | 2014-05-20 | ||
| US14/281,968 US9405198B2 (en) | 2014-05-20 | 2014-05-20 | Method for providing conductive silver film elements |
| US14/281,984 US9335635B2 (en) | 2014-05-20 | 2014-05-20 | Silver halide solution physical developing solution |
| US14/281,968 | 2014-05-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105093805A true CN105093805A (en) | 2015-11-25 |
Family
ID=54574553
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510259928.6A Pending CN105093805A (en) | 2014-05-20 | 2015-05-20 | Silver halide solution physical developing solution and use method for same |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN105093805A (en) |
| TW (1) | TW201610609A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105892242A (en) * | 2016-03-30 | 2016-08-24 | 牛灵芝 | Radiological image developing solution and preparation method |
| CN108107668A (en) * | 2017-12-27 | 2018-06-01 | 郑州拓洋生物工程有限公司 | Developer and preparation method thereof and developer solution |
| TWI672080B (en) * | 2017-12-25 | 2019-09-11 | Hongqisheng Precision Electronics (Qinhuangdao) Co., Ltd. | Flexible circuit board with buried resistance and method for manufacturing same |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2662822A (en) * | 1949-04-21 | 1953-12-15 | Polaroid Corp | Photographic transfer processes and compositions for the practice of said processes |
| GB1322409A (en) * | 1971-02-08 | 1973-07-04 | Ilford Ltd | Photographic processes |
| JPS6091354A (en) * | 1983-10-26 | 1985-05-22 | Fuji Photo Film Co Ltd | Photographic element for color diffusion transfer method |
| CN1407410A (en) * | 2001-08-28 | 2003-04-02 | 东京威力科创股份有限公司 | Development treating method and developing liquid coating device |
| CN1436321A (en) * | 2000-06-13 | 2003-08-13 | 伊斯曼柯达公司 | Thermally developable image system comprising blocked color-forming agent in association with hydroxy-substd. aromatic compound for promoting image formation |
| CN1743963A (en) * | 2001-08-28 | 2006-03-08 | 东京威力科创股份有限公司 | Method for developing processing and apparatus for supplying developing solution |
| CN101076572A (en) * | 2004-12-11 | 2007-11-21 | 伊斯曼柯达公司 | Conductive silver dispersions and uses thereof |
| CN102290129A (en) * | 2010-06-18 | 2011-12-21 | 富士胶片株式会社 | Conductive film and method for producing the same |
-
2015
- 2015-05-19 TW TW104115926A patent/TW201610609A/en unknown
- 2015-05-20 CN CN201510259928.6A patent/CN105093805A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2662822A (en) * | 1949-04-21 | 1953-12-15 | Polaroid Corp | Photographic transfer processes and compositions for the practice of said processes |
| GB1322409A (en) * | 1971-02-08 | 1973-07-04 | Ilford Ltd | Photographic processes |
| JPS6091354A (en) * | 1983-10-26 | 1985-05-22 | Fuji Photo Film Co Ltd | Photographic element for color diffusion transfer method |
| CN1436321A (en) * | 2000-06-13 | 2003-08-13 | 伊斯曼柯达公司 | Thermally developable image system comprising blocked color-forming agent in association with hydroxy-substd. aromatic compound for promoting image formation |
| CN1407410A (en) * | 2001-08-28 | 2003-04-02 | 东京威力科创股份有限公司 | Development treating method and developing liquid coating device |
| CN1743963A (en) * | 2001-08-28 | 2006-03-08 | 东京威力科创股份有限公司 | Method for developing processing and apparatus for supplying developing solution |
| CN101076572A (en) * | 2004-12-11 | 2007-11-21 | 伊斯曼柯达公司 | Conductive silver dispersions and uses thereof |
| CN102290129A (en) * | 2010-06-18 | 2011-12-21 | 富士胶片株式会社 | Conductive film and method for producing the same |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105892242A (en) * | 2016-03-30 | 2016-08-24 | 牛灵芝 | Radiological image developing solution and preparation method |
| TWI672080B (en) * | 2017-12-25 | 2019-09-11 | Hongqisheng Precision Electronics (Qinhuangdao) Co., Ltd. | Flexible circuit board with buried resistance and method for manufacturing same |
| CN108107668A (en) * | 2017-12-27 | 2018-06-01 | 郑州拓洋生物工程有限公司 | Developer and preparation method thereof and developer solution |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201610609A (en) | 2016-03-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101647074B (en) | Conductive film and method for producing the same | |
| CN105093805A (en) | Silver halide solution physical developing solution and use method for same | |
| US9235130B2 (en) | Method for preparing transparent conductive silver patterns | |
| CN109564488A (en) | Conductive membrane and touch panel | |
| US9430113B2 (en) | Electrically-conductive article with improved bus region | |
| US20150338740A1 (en) | Method for providing conductive silver film elements | |
| CN105103096A (en) | Touch panel and resin composition for forming protective layer | |
| US20140367620A1 (en) | Method for improving patterned silver conductivity | |
| CN105934714B (en) | Silver halide conducting element precursor and equipment | |
| US9405423B2 (en) | Article with electrically-conductive silver connector wire pattern | |
| US9405419B2 (en) | Electrically-conductive articles with electrically-conductive metallic connectors | |
| CN105592627B (en) | The method of shaping claviform and the offer shaping claviform | |
| US20160133357A1 (en) | Providing electrically-conductive articles with electrically-conductive metallic connectors | |
| US9405196B2 (en) | Method for preparing electrically-conductive silver images | |
| US9335635B2 (en) | Silver halide solution physical developing solution | |
| US9261787B1 (en) | Conductive element precursor and conductive pattern formation | |
| US20130193136A1 (en) | Photonic heating of silver grids | |
| JPWO2016157585A1 (en) | Conductive film, manufacturing method thereof, touch panel | |
| JP2016122517A (en) | Manufacturing method of electric conductive film and electric conductive film | |
| JP2015179623A (en) | Method of manufacturing conductive member, and conductive member | |
| US20150338741A1 (en) | Silver halide developing solution | |
| JP2019121205A (en) | Conductive material and touch panel sensor | |
| US20140231723A1 (en) | Enhancing silver conductivity | |
| JP2012194887A (en) | Electrode sheet, method of manufacturing electrode sheet, and touch panel | |
| US9304395B2 (en) | Conductive element precursor and conductive pattern formation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20151125 |
|
| WD01 | Invention patent application deemed withdrawn after publication |