CN101577148B - Transparent conducting film and preparation method thereof - Google Patents
Transparent conducting film and preparation method thereof Download PDFInfo
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- CN101577148B CN101577148B CN2009100745140A CN200910074514A CN101577148B CN 101577148 B CN101577148 B CN 101577148B CN 2009100745140 A CN2009100745140 A CN 2009100745140A CN 200910074514 A CN200910074514 A CN 200910074514A CN 101577148 B CN101577148 B CN 101577148B
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Abstract
The invention discloses a transparent conducting film and a preparation method thereof; the conducting film comprises a supporting body and conductive metal patterns formed on the supporting body; a photosensitive material containing a silver halide emulsion is exposed, chemically developed and chemically plated to form the conductive metal patterns which are metal net-like patterns, wherein the thickness of the silver wire on the net wires is 0.4 to 2.4mum, the homogeneity of the net wire width is larger than or equal to 85 percent; the weight ratio between the silver and gelatin in the silver halide emulsion is 3 to 4; and the surface resistance of the conducting film is 0.1 to 1000 Omega. The products prepared by the invention have the advantages of high transparency, low cost, and goodhomogeneity of surface resistance and the preparation method thereof has simple process and is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of conducting film, particularly the nesa coating of the anode of the anode of plasma display optical filtering screen, touch-screen, organic thin film solar cell, Electronic Paper and flexible OLED use.
Background technology
Nesa coating is a dual-use function material a kind of not only transparent but also conduction, in the electronics and information industry field, is widely used.The light transmittance of nesa coating should reach more than 80%.General sheet resistance can be used as transparent electromagnetic wave shielding (EMI) film that plasm TV (PDP) filters and shields less than the nesa coating of 2.5 Ω/; Sheet resistance is the nesa coating of 300～500 Ω/, can be used for touch-screen; Sheet resistance is the nesa coating of 5～15 Ω/, can be used as the anode of organic thin film solar cell; Sheet resistance is the anode that the nesa coating of 10～30 Ω/ then can be used for Electronic Paper, flexible OLED.In addition, this method may also extend into makes RFID electronic label antenna etc., is with a wide range of applications.
The preparation method of nesa coating can be divided into two big types of sputtering method and metal grid mesh methods usually.Sputtering method is meant indium tin oxide (IT0) directly sputtered on the glass substrate, or sputters on polyester (PET) diaphragm and be compound on the glass substrate.The metal grid mesh method can be divided into the Copper Foil etching method again, metallic fiber weave, print process and silver salt method.Though sputtering method and Copper Foil etching method are the main stream approach of making nesa coating, because apparatus expensive, complex process, factor such as with high costs, its leading position has begun to receive the challenge of other new manufacturing approach at present.
Aspect the new manufacturing approach of exploitation nesa coating, a kind of in recent years method of utilizing the silver salt photographic film to form argent grid conducting film is particularly noticeable.Application number is that 200580025044.9 one Chinese patent application discloses a kind of light-transmitting film shielding electromagnetic wave and manufacturing approach thereof; This preparation method makes public the silver salt photographic film, develop to processing and oxidation processes; Do not implement physical development or electroplating processes, directly make argent grid conducting film; This product is characterised in that, the argent grid of formation contains the silver of 80～100wt%, and the photographic film silver coated amount of enumerating in this patent working example is up to 15g/m
2With the grid percent opening is 85% calculating, in fact stays the argent on the conductive film, and 2.25g/m is only arranged
2, a large amount of argents are lost in the working fluid, cause production cost higher.Application number is that 200680018602.3 one Chinese patent application discloses the light-transmitting film shielding electromagnetic wave that preparation method, conductive metal film and the plasma display of photosensitive material, conductive metal film are used; The silver salt photographic film prepares the transparent electromagnetic wave screened film through physical development and/or electroplating processes at least again after exposure, the processing of developing.This patent proposes, and the expansion rate of making the used photographic film emulsion layer of nesa coating is controlled at more than 150%, and silver is 6-10 with the weight ratio of gelatin, and the silver coated amount is 5.0g/m
2More than, cost is still higher, and is higher than 6 when above when the silver and the weight ratio of gelatin, and emulsion is unstable with film, easy formation " blackspot " shape disadvantage; In addition, the electroplating processes complex process is had relatively high expectations to the conduction homogeneity of grid line, and when electroplating, receives the uneven influence of CURRENT DISTRIBUTION on the grid line, is prone to cause the inhomogeneities of coat of metal live width on the netting twine, and the effect that influence is used.Therefore adopt sheet resistance uniformity, the visual effect of the nesa coating that electroplating technology makes still not ideal enough.
Summary of the invention
Technical problem to be solved by this invention provides a kind of high transparent, low-cost, nesa coating that sheet resistance has good uniformity.
Another technical problem to be solved by this invention provides the preparation method of this nesa coating.
For solving the problems of the technologies described above, the technical scheme that the present invention takes is:
A kind of nesa coating; It comprises support and formed conducting metal pattern above that; Said conducting metal pattern is to handle the metal mesh pattern that the back forms by the photosensitive material that contains silver emulsion through exposure, chemical development and chemical plating; Wherein, the silver-colored line thickness on the netting twine is 0.4～2.4 micron, the homogeneity of netting twine live width >=85%; The silver in the said silver emulsion and the weight ratio of gelatin are 3～4; The sheet resistance of said conductive film is 0.1～1000 Ω/.
Above-mentioned nesa coating, the percent opening of the netted pattern of said conducting metal are greater than 80%, and the main component of netting twine is argent and copper and/or the nickel of going up plating thereof.
Above-mentioned nesa coating, said support are plastic film, glass or pet film.
A kind of preparation method who prepares above-mentioned nesa coating; It is coated with silver emulsion on support photosensitive material carries out lattice exposure and chemical development processing, makes the formation of exposed portion and unexposed portion comprise the grid exposing patterns of argent part and transparent part; Carry out chemical plating then and handle, form transparent electrically-conductive film.
The preparation method of above-mentioned nesa coating, the silver of said silver emulsion and the weight ratio of gelatin are 3～4, the silver coated amount of said silver sensitive material is 3 gram/rice
2Below.
The preparation method of above-mentioned nesa coating; Netting twine main component after said chemical plating is handled is argent and copper and/or the nickel of going up plating thereof; The homogeneity of netting twine live width >=85%; Silver-colored line thickness is 0.4～2.4 micron on the netting twine, and the sheet resistance of transparent conductive film can be regulated and control in 0.1～1000 Ω/ scope.
The preparation method of above-mentioned nesa coating, the reducing agent that said chemical plating is handled in the chemical plating fluid that uses is hypophosphites.
The support that uses among the present invention; It can be plastic film; Such as by PETG fat (PET), PEN class, diacetate resin, triacetate resin, polyethylene, polypropylene, polystyrene, Corvic, polyketone ether, the single or multiple lift film that polysulfones, polyether sulfone, Merlon, polyamide, acrylic resin, Triafol T (TAC) etc. constitute; It also can be glass plate.As plastic film of the present invention, plastic plate or glass plate, hope that it is high to the total visible light light transmittance, be preferably 70～100%, more preferably 85～100%, be preferably 90～100% especially.In the present invention, above-mentioned plastic film and plastic plate are transparent, do not carry out painted processing.Use in the present invention under the situation of glass plate as support, its kind has no particular limits, and considers that from security standpoint preferred surface is made the tempered glass of intensive treatment.
Silver emulsion can be made according to the manufacturing approach of employed silver emulsion in the sensitive photographic material field.Silver emulsion normally through halide solutions such as silver nitrate aqueous solution and sodium chloride or KBr mixing and emulsifying under the condition that gelatin exists is made, can use single notes method, double-jet method or its combination.
Employed silver halide among the present invention is formed; Contained halogen element can be any one or its combination in chlorine, bromine, iodine and the fluorine; For example silver chlorate, silver bromide, silver iodide, chlorine silver bromide, silver chloroiodobromide, bromo-iodide preferably use and contain silver chlorate 50% or higher chlorine silver bromide and the silver chloroiodobromide of silver chloride content.The content of halogen is meant the mole percent of halogen ion in this silver halide composition in this specification.
Silver halide is made up of solid particle, and the silver halide average grain diameter of representing with the equivalent sphere diameter is preferably 0.01～1.2 μ m, more preferably 0.05-0.5 μ m." the equivalent sphere diameter " of silver halide particle is meant the diameter that has the spherical particle of equal volume with silver halide particle.
The not special restriction of the shape of silver halide particle can be a different shape, like cube, octahedron, spheroid, the tetrakaidecahedron, flat particle or laminar twin etc., and the preferred cube or the tetrakaidecahedron.
The employed adhesive of silver emulsion can be polysaccharide, cellulose and derivative, hydroxylated celluloses etc. such as gelatin, polyvinyl alcohol, PVP, starch among the present invention, and preferred gelatin is as the adhesive of silver emulsion.When the silver in the silver salt photographic film and the weight ratio of gelatin are too high, be prone to cause the silver halide particle cohesion, the back of developing forms the argent blackspot, thereby reduces visible light transmittance rate; And cross when low when the silver in the silver salt photographic film and the weight ratio of gelatin; Then can cause silver grid line coating surface metal difficulty, thereby make the sheet resistance of conducting film bigger, or be prone to cause coating discontinuous; Therefore, the weight ratio of preferred silver and gelatin is 3～4 among the present invention.
For preventing that silver halide particle from assembling and deposition, can also add tackifier, like the polyphenyl Sulfonates etc.
In order to obtain higher contrast, need doped metal ion, particularly transition metal ions such as rhodium ion and iridium ion in the silver emulsion.Rhodium ion has different ligand compounds with iridium ion, and ligand comprises cyanide ion, halide ion, thiocyanate ion, nitrosyl radical ion, water and hydroxide ion etc.The preferable amount of every moles of silver is 10
-10～10
-2Mole, more preferably consumption is 10
-9～10
-3Mole.
In order to improve the photosensitivity of silver emulsion, can carry out chemical sensitization to above-mentioned photographic emulsion.As chemical sensitization golden sensitizing capable of using, sulphur sensitizing, reduction sensitization etc.
In the present invention, when the coating silver halide emulsion layer prepares the silver salt photographic film, can adopt modes such as dip-coating, slope stream extrusion coated to be coated with.Preferably sloping stream extrusion coated mode among the present invention, continuous to obtain, uniform coating, the silver coated amount of silver emulsion is lower than 4.0g/m in the coating
2, more preferably 3.0g/m
2Below.
The preparation method of nesa coating is included in and is coated with silver halide magenta-sensitive emulsion on the transparent support, exposure, and development treatment, chemical plating are handled and are covered the metal step.
The method of among the present invention the photosensitive material that contains silver emulsion being made public can utilize photomask to carry out the face exposure, also can carry out scan exposure with laser.The light source that the exposure of photomask face is used can be uviol lamp or high-pressure mercury lamp etc., and the template that will have lattice is printed on the silver halide film; Laser scanning exposure is with laser lattice to be scanned on silver halide film.In order to make the photosensitive material exposure evenly, the exposure sources uniformity of light is preferred more than 80%, more preferably more than 90%, most preferably more than 95%.Photomask masterplate lattice is not done special the qualification; Can be triangular in shape, rhombus, circle, square, rectangle or the like; The live width of grid and spacing can be selected adjustment according to application need; The live width homogeneity of used photomask masterplate grid is preferred more than 90%, most preferably more than 95%.
The processed of need developing after the silver halide emulsion layer exposure among the present invention.Above-mentioned development processed can be used the traditional chemical developing technique that in silver salt photographic or printing paper, printing plate film etc., uses.Developer solution is had no particular limits, can use the developing technique in the traditional photography material, developer is unrestricted, but preferably uses the high contrast developer, like commercially available D-19, D-72, D-11, D-8 and G-48 etc.Form argent part and light transmission part behind the exposure imaging.
In manufacturing approach of the present invention, the development processed also comprises to remove the unexposed portion silver salt handles the photographic fixing that it is stable, printing opacity is purpose, and photographic fixing is handled and can be used the photographic fixing technology of in silver salt photographic or printing paper, printing plate film etc., using.
Among the present invention silver grid is carried out chemical plating and handle, chemical plating is handled and is comprised activation, electroless copper, chemical nickel plating.Wherein the purpose of activation is to be formed with on the silver grid silver thread pattern surface of transparent support to be beneficial to the sufficient active site of electroless copper, with the speed of acceleration electroless copper, and carries out selective chemical plating.Activation can adopt known method to carry out, and like sensitization-activation two-step process, promptly at first carries out sensitization with the stannous chloride aqueous solution and handles, and then carry out activation processing with palladium bichloride, gold trichloride or silver nitrate aqueous solution; Colloid palladium activation method etc.Advantageous applications heavy metal ion of the present invention is carried out activation, promptly carries out activation with palladium bichloride, gold trichloride or silver nitrate aqueous solution, more preferably carries out activation processing with palladium chloride aqueous solution.
Silver grid chemical plating process comprises and carries out activation processing earlier, again at selective deposition metallic particles on grid line, forms conductive metal layer.The metallic particles of conductive metal layer can be metallic particles such as copper, aluminium, nickel, zinc, iron, gold, cobalt, palladium.But took all factors into consideration with becoming originally from conductivity, conducting metal particles is preferably copper, nickel.Chemical plating can adopt electroless copper and/or chemical nickel plating.
Traditional electroless plating technology can use.Printed circuit board (PCB) electroless plating technology for example.The chemical plating first-selection is electroless copper and chemical nickel plating.Chemical bronze plating liquid generally is made up of mantoquita, complexing agent, reducing agent and other additive.Mantoquita provides the copper ion that is deposited, and can use soluble copper salts such as copper sulphate, Schweinfurt green or copper chloride.Reducing agent is that the copper ion with the solubility in the plating bath is reduced into metallic copper and is deposited on the silver-colored thread pattern of transparent support and forms metallic copper coating, and reducing agent can adopt materials such as formaldehyde, boron hydracid sodium, sodium hypophosphite.Complexing agent is to prevent in alkalescence, to take place the Kocide SD deposition to produce, and copper ion is become the complex ion state, helps crystal grain thinning, also helps improving the stability of deposition velocity and solution, improves the performance of chemical deposit.Complexing agent commonly used has tartrate, EDTA, citrate, triethanolamine, 1,2-diaminocyclohexane tetraacetic acid or ethylenediamine etc.General adopt single complexing agent, also have and adopt the mixed twine mixture.The unsteadiness of copper electrolyte is the disadvantage of chemical bronze plating liquid, so generally introduce stabilizer, for example α, α '-bipyridine, three pyridines, thiocarbamide, mercapto benzothiazole.Also add nonionic surface active agent or anionic surfactant in addition and improve coating character, as adding polyethylene glycol (M=1000), polyoxyethylated alkyl phenol etc.
Present commercial chemical bronze plating liquid is nearly all made reducing agent with formaldehyde, but formaldehyde is poisonous, and volatile, unstable, and contaminated environment is detrimental to health.The preferred sodium hypophosphite of the present invention is as the chemical-copper-plating process of reducing agent., environmental protection stable as the chemical bronze plating liquid of reducing agent with sodium hypophosphite help continuous industry production.
In the chemical bronze plating liquid of sodium hypophosphite, need to add minor amount of nickel ion, cobalt ions or palladium ion and do the self-catalysis agent, the preferred nickel ion of the present invention as reducing agent.The temperature of chemical bronze plating liquid is 10～75 ℃, preferred 20～60 ℃.
Chemical nickel-plating liquid with the copper plating bath group categories seemingly generally is made up of nickel salt, complexing agent, reducing agent and other additive.Traditional chemical nickel-plating liquid technology can be applied to the present invention; But take all factors into consideration from aspects such as stability, cost, coating performances; Preferred sodium hypophosphite is as the nickel chemical plating technology of reducing agent among the present invention, and more preferably alkaline sodium hypophosphite is as the nickel chemical plating technology of reducing agent.The temperature of chemical nickel-plating liquid is 10～75 ℃, preferred 20～60 ℃.
Compare with plating, the conducting metal coating that chemical plating forms has good chemical, mechanical stability (fine and close like coating, hardness is high), and thickness of coating is even, and the live width precision is high.In order to ensure the uniformity of coating, plating bath need carry out circulating filtration and stirring, and with stablizing with even of plating bath in the maintenance coating bath, stirring can adopt mechanical agitation or air-flow to stir.
The main component of the conducting metal grid line behind the metal lining is argent and copper and/or the nickel of going up plating thereof, also contains a spot of Metal Palladium in addition.The thickness of conducting metal netting twine can at random be adjusted according to desired characteristic in the lattice behind the metal lining.For a kind of conductive film cheaply is provided, preferred 0.5～10 micron of the conducting metal netting twine thickness among the present invention, silver-colored line thickness wherein is preferably 0.4～2.4 micron, more preferably 0.5～2.0 micron.
The homogeneity of conducting metal netting twine live width is bigger to sheet resistance uniformity, the visual effect influence of nesa coating in the lattice behind the metal lining, thus the effect that influence is used.Be the transparent conductive film that provides a kind of sheet resistance to have good uniformity, the homogeneity of nesa coating live width provided by the invention should be more than or equal to 85%.
The sheet resistance of nesa coating can increase or the attenuate metal layer thickness through adjustment chemical plating treatment process, thereby the sheet resistance of conducting film can correspondingly be regulated and control in 0.1 Ω/～1000 Ω/ scope.
In addition, in order to improve visual effect, the method for preferably using with traditional printing wiring board fields such as acid or alkali etc. or employing plating is carried out melanism with coating surface and is handled.
The nesa coating of making as stated, if make the fine rule narrowed width that constitutes lattice, promptly percent opening increases, its light transmission improves thereupon, and conductivity descends thereupon; If on the contrary the fine rule width is broadened, conductivity but strengthens its light transmission thereupon thereupon descending.Consider that from practicality the percent opening of the netted pattern of conducting metal according to the invention is preferably greater than 80%.Lattice is not done special the qualification, can be triangular in shape, rhombus, circle, square, rectangle or the like, and the live width of grid and spacing can be selected to adjust according to application need.Conducting metal grid part spacing is preferably 50～500 microns among the present invention, more preferably 150～400 microns; Preferred 3～40 microns of live width, more preferably 5～25 microns.
Nesa coating of the present invention can be added with functional coatings such as diaphragm, infrared ray absorbing layer, adhesive layer, hardened layer in the side with conductive layer or in substrate back side.These functional coats can adopt coating method, perhaps the function corresponding film are directly fitted with it.
Nesa coating of the present invention; Can be as required; Through regulating and control its sheet resistance value, and/or increase functional coating, make and be used for electromagnetic shielding film, touch-screen with the anode of anode, Electronic Paper and the flexible OLED of nesa coating, organic thin film solar cell etc.
The nesa coating that the present invention obtains; Its sheet resistance has good uniformity; Have visual impression and result of use admirably; And can be used in filter a plurality of fields such as anode of anode, Electronic Paper and flexible OLED of nesa coating, organic thin film solar cell of transparent electromagnetic wave screened film, touch-screen of screen of plasma display, have a good application prospect and broad range of application.
The preparation method of nesa coating according to the invention uses the silver coated amount to be lower than 3.0g/m
2Silver halide photographic films, greatly reduce the silver coated amount, practiced thrift production cost; Chemical plating fluid adopts hypophosphites to make reducing agent, has reduced environmental pollution; Adopt chemical plating process; Not only can obtain the uniform target product of sheet resistance; And the sheet resistance of target product can be adjustable in 0.1～1000 Ω/ broad range according to the needs that use the field, adapt to the demand of different application field to different surfaces resistance conducting film, and technology is simple; Equipment investment is few, can realize the serialization commercial production.
Embodiment
Hereinafter combines embodiment to describe the present invention in more detail.
Embodiment 1
1. prepare silver halide photographic films 1-1
Manufacturing approach according to employed silver emulsion in the sensitive photographic material field prepares emulsion.Silver is 3.9 with the weight ratio of gelatin in the said silver emulsion, contains that to have the corresponding average grain diameter of spheroid be 0.12 micron silver chloroiodobromide particle (wherein silver chlorate is that 63 moles of % and silver iodide are 0.8 mole of %).Being doped with concentration in the emulsion respectively is 10
-6The K of moles/mole silver
2IrCl
6And K
3RhBr
6, again emulsion is further carried out sulphur gold sensitizing with gold potassium chloride and sodium thiosulfate.The emulsion that will be added with tackifier and hardener then is coated on the PET film, dry back rolling.The sample 1-1 that obtains thus, its silver coated amount be 3.0 the gram/square metre.
2. exposure, the processing of developing, chemical plating are handled
The image processor that the dried samples using of above-mentioned coating is had blue laser makes public to it, makes the photographic film sample after the processing of developing, and can form the silver lattice of live width/spacing=10 micron/290 microns (at interval: 300 microns).Regulate exposure, make it be suitable for each sample most.
Carry out following development processing and chemical plating processing for each sample after the exposure, thereby make corresponding conducting film.
(annotate: in the above-mentioned processing procedure, rinsing 1-2～rinsing 1-1, rinsing 2-2～rinsing 2-1, rinsing 3-2～rinsing 3-1, rinsing 4-2～rinsing 4-1 all adopt the washing of double flute adverse current.)
The composition of various treatment fluids is following:
Black-and-white developer:
Anhydrous sodium sulfite 100 grams,
Disodium ethylene diamine tetraacetate 2 grams,
Hydroquinones 30.0 grams,
Phenidone 1.5 grams,
Potassium hydroxide 25.0 grams,
KBr 3.5 grams,
BTA 0.5 gram,
PH transfers to 10.5,
Add water to 1.0 liters,
Fixing solution is F-5.
Activating solution:
Palladium bichloride 0.5 gram,
37% hydrochloric acid 10ml,
Add water to 1.0 liters,
Chemical bronze plating liquid: (prescription of one liter of liquid)
| Title | Concentration (mmol/L) |
| Copper sulphate | 60 |
| Natrium citricum | 80 |
| Sodium hypophosphite | 270 |
| Boric acid | 300 |
| Bipyridine | 0.13 |
| Nickelous sulfate | 2 |
| PH | Be adjusted to 9.5 |
Chemical nickel-plating liquid: (prescription of one liter of liquid)
| Title | Concentration (mmol/L) |
| Nickelous sulfate | 12 |
| Natrium citricum | 60 |
| Sodium hypophosphite | 270 |
| Boric acid | 300 |
| Bipyridine | 0.10 |
| PH | Be adjusted to 8.0 |
3. performance measurement:
Each conducting film for making carries out performance test according to following method.
1. thickness measuring:
Silver line thickness measuring: the print after the development treatment is carried out drying, and its thickness of test on Thickness measuring instrument is removed silver film test pieces base thickness with protease more then, and the former deducts the latter, is silver-colored line thickness.
The metal plating layer thickness measuring: to the conducting film testing total thickness on Thickness measuring instrument that makes, remove metal plating layer test thickness with rare nitric acid again, the former deducts the latter, is the metal lining layer thickness.
2. sheet resistance:
Test each conducting film conductive grid sheet resistance value with the Estimate of Resistance for DC Low Resistance tester.
3. visible light transmissivity
With each conducting film visible light transmissivity of integrating sphere type haze meter test.
4. live width homogeneity
Getting breadth is above-mentioned each conducting film print of 400 * 700mm; Live width with metallic conduction grid line on the same direction of optics precision aid (U.S. OGP) test; Evenly test 50 positions; Obtain one group of line width values data,, represent the homogeneity of this conducting film live width with the ratio of minimum feature value with the maximum line width value.The homogeneity of big more this conducting film live width of explanation of ratio is good more.
Embodiment 2～4.
Preparation silver halide photographic films 1-2～1-4.
According to preparation silver halide photographic films sample 1-1 same procedure, make sample 1-2～1-4.Different is to change its silver coated amount, as shown in table 1.
To make sample 1-2～1-4 handles according to above-mentioned steps make public, develop processing and chemical plating.
Comparative example 1
Preparation silver halide photographic films 1-5
According to preparation silver halide photographic films sample 1-1 same procedure, make sample 1-5.Different is to change its silver coated amount, as shown in table 1.
To make sample 1-5 handles according to above-mentioned steps make public, develop processing and chemical plating.
Each conducting film sample is listed in table 1 according to the results of property of the test of method described in the embodiment 1.
Table 1: test result
| Sample number | Silver coated amount (g/m 2) | Silver and gelatin weight ratio | Silver line thickness (micron) | Metal layer thickness (micron) | The conductive grid sheet resistance (Ω/) | Visible light transmissivity (%) | Live width uniformity (%) | Remarks |
| 1-1 | 3.0 | 3.7 | 2.4 | 5.5 | 0.12 | 79.3 | 86.6 | Embodiment 1 |
| 1-2 | 2.1 | 3.7 | 1.9 | 5.3 | 0.14 | 80.1 | 86.8 | Embodiment 2 |
| 1-3 | 0.9 | 3.7 | 0.9 | 5.2 | 0.16 | 80.2 | 86.1 | Embodiment 3 |
| 1-4 | 0.5 | 3.7 | 0.4 | 5.2 | 0.15 | 80.1 | 86.2 | Embodiment 4 |
| 1-5 | 7.6 | 3.7 | 5.2 | 5.1 | 0.16 | 76.4 | 83.7 | Comparative example 1 |
Can find out from table 1, be used to make the height of silver coated amount of the silver salt photographic film of nesa coating of the present invention, the light transmission and the conductivity of the conducting film that finally makes is not had influence basically.The present invention considers from the angle that reduces production costs, and is necessary to save the consumption as precious metals silver, therefore preferred silver coated amount≤3g/m
2Photographic film make nesa coating.
Embodiment 5
1. prepare silver halide photographic films 2-1
Manufacturing approach according to employed silver emulsion in the sensitive photographic material field prepares emulsion.Silver is 4 with the weight ratio of gelatin in the said silver emulsion, contains that to have the corresponding average grain diameter of spheroid be 0.30 micron silver chloroiodobromide particle (wherein silver chlorate is that 72 moles of % and silver iodide are 0.5 mole of %).Being doped with concentration in the emulsion respectively is 10
-7The K of moles/mole silver
2IrCl
6And K
3RhBr
6, again emulsion is further carried out sulphur gold sensitizing with gold potassium chloride and sodium thiosulfate.Above-mentioned then emulsion is coated on the PET film after adding tackifier and hardener, dry back rolling.The sample 2-1 that obtains thus, its silver coated amount be 2.6 the gram/square metre.
2. exposure, the processing of developing, chemical plating are handled
The contact printer of high-pressure mercury lamp as light source adopted in exposure; With the above-mentioned emulsion layer that makes sample 2-1 with have wide 15 microns the photomask blank of fine rule and fit with 295 microns lattices of lattice spacing; And vacuumize compress sturdy after; Carry out uniform exposure, making the processing back of developing form live width/spacing=15 micron/295 microns (being spaced apart 310 microns) silver lattices.Regulate exposure, make it be suitable for each sample most.Carry out then handling with embodiment 1 similar development processing and chemical plating.
The performance of the conducting film sample 2-1 that test obtains; And estimate the silver heavy level of each conducting film sample with the silver salt photographic film, and promptly unexposed sample 2-1 is carried out the former state development treatment, obtain slide; Each sample slide of visual observations is apparent again, estimates whether to form the developed silver blackspot.Evaluation criterion is following:
Horizontal A: developed silver blackspot quantity is 0～3/square meter;
Horizontal B: developed silver blackspot quantity is 4～8/square meter;
Horizontal C: developed silver blackspot quantity is greater than 8/square meter;
Test result is listed in table 2.
Embodiment 6
1. prepare silver halide photographic films 2-2
Manufacturing approach according to employed silver emulsion in the sensitive photographic material field prepares emulsion.Silver is 3.5 with the weight ratio of gelatin in the said silver emulsion, contains that to have the corresponding average grain diameter of spheroid be 0.25 micron silver chloroiodobromide particle (wherein silver chlorate is that 72 moles of % and silver iodide are 0.5 mole of %).Being doped with concentration in the emulsion respectively is 10
-7The K of moles/mole silver
2IrCl
6And K
3RhBr
6, again emulsion is further carried out sulphur gold sensitizing with gold potassium chloride and sodium thiosulfate.Be coated on the PET film dry back rolling after then above-mentioned emulsion being added tackifier and hardener.The sample 2-2 that obtains thus, its silver coated amount be 2.6 the gram/square metre.
2. handle according to make public, the develop processing, chemical plating of the step of embodiment 5, and estimate.Test result is listed in table 2.
Embodiment 7
1. prepare silver halide photographic films 2-3
Manufacturing approach according to employed silver emulsion in the sensitive photographic material field prepares emulsion.Silver is 3 with the weight ratio of gelatin in the said silver emulsion, contains that to have the corresponding average grain diameter of spheroid be 0.26 micron silver chloroiodobromide particle (wherein silver chlorate is that 72 moles of % and silver iodide are 0.5 mole of %).Being doped with concentration in the emulsion respectively is 10
-7The K of moles/mole silver
2IrCl
6And K
3RhBr
6, again emulsion is further carried out sulphur gold sensitizing with gold potassium chloride and sodium thiosulfate.Be coated on the PET film dry back rolling after then above-mentioned emulsion being added tackifier and hardener.The sample 2-3 that obtains thus, its silver coated amount be 2.6 the gram/square metre.
2. handle according to make public, the develop processing, chemical plating of the step of embodiment 5, and estimate.Test result is listed in table 2.
Comparative example 2
1. prepare silver halide photographic films 2-4
Manufacturing approach according to employed silver emulsion in the sensitive photographic material field prepares emulsion.Silver is 2 with the weight ratio of gelatin in the said silver emulsion, contains that to have the corresponding average grain diameter of spheroid be 0.18 micron silver chloroiodobromide particle (wherein silver chlorate is that 72 moles of % and silver iodide are 0.5 mole of %).Being doped with concentration in the emulsion respectively is 10
-7The K of moles/mole silver
2IrCl
6And K
3RhBr
6, again emulsion is further carried out sulphur gold sensitizing with gold potassium chloride and sodium thiosulfate.Be coated on the PET film dry back rolling after then above-mentioned emulsion being added tackifier and hardener.The sample 2-4 that obtains thus, its silver coated amount be 2.6 the gram/square metre.
2. handle according to make public, the develop processing, chemical plating of the step of embodiment 5, and estimate.Test result is listed in table 2.
Comparative example 3
1. prepare silver halide photographic films 2-5
Manufacturing approach according to employed silver emulsion in the sensitive photographic material field prepares emulsion.Silver is 1 with the weight ratio of gelatin in the said silver emulsion, contains that to have the corresponding average grain diameter of spheroid be 0.22 micron silver chloroiodobromide particle (wherein silver chlorate is that 72 moles of % and silver iodide are 0.5 mole of %).Being doped with concentration in the emulsion respectively is 10
-7The K of moles/mole silver
2IrCl
6And K
3RhBr
6, again emulsion is further carried out sulphur gold sensitizing with gold potassium chloride and sodium thiosulfate.Be coated on the PET film dry back rolling after then above-mentioned emulsion being added tackifier and hardener.The sample 2-5 that obtains thus, its silver coated amount be 2.6 the gram/square metre.
2. handle according to make public, the develop processing, chemical plating of the step of embodiment 5, and estimate.Test result is listed in table 2.
Comparative example 4
1. prepare silver halide photographic films 2-6
Manufacturing approach according to employed silver emulsion in the sensitive photographic material field prepares emulsion.Silver is 5.6 with the weight ratio of gelatin in the said silver emulsion, contains that to have the corresponding average grain diameter of spheroid be 0.21 micron silver chloroiodobromide particle (wherein silver chlorate is that 72 moles of % and silver iodide are 0.5 mole of %).Being doped with concentration in the emulsion respectively is 10
-7The K of moles/mole silver
2IrCl
6And K
3RhBr
6, again emulsion is further carried out sulphur gold sensitizing with gold potassium chloride and sodium thiosulfate.Be coated on the PET film dry back rolling after then above-mentioned emulsion being added tackifier and hardener.The sample 2-6 that obtains thus, its silver coated amount be 2.6 the gram/square metre.
2. handle according to make public, the develop processing, chemical plating of the step of embodiment 5, and estimate.Test result is listed in table 2.
Table 2: test result
| Sample number | Silver coated amount (g/m 2) | Silver and gelatin weight ratio | Sheet resistance (Ω/) | Visible light transmissivity (%) | Silver line thickness (micron) | Live width uniformity (%) | Developed silver blackspot level is estimated | Remarks |
| 2-1 | 2.6 | 4 | 0.13 | 75.6 | 2.0 | 87.6 | B | Embodiment 5 |
| 2-2 | 2.6 | 3.5 | 0.12 | 75.4 | 2.1 | 88.8 | A | Embodiment 6 |
| 2-3 | 2.6 | 3 | 0.20 | 76.2 | 2.2 | 87.4 | A | Embodiment 7 |
| 2-4 | 2.6 | 2 | 540 | 78.6 | 2.3 | - | A | Comparative example 2 |
| 2-5 | 2.6 | 1 | Coating is discontinuous | 81.1 | 2.5 | - | A | Comparative example 3 |
| 2-6 | 2.6 | 5.6 | 0.12 | 70.2 | 1.6 | 82.7 | C | Comparative example 4 |
Can find out that from table 2 under the too high situation of weight ratio of silver and gelatin in the silver salt photographic film, be prone to cause the silver halide particle cohesion, the back of developing forms the argent blackspot, thus reduction visible light transmittance rate (like sample 2-6); And silver is crossed under the low situation with the weight ratio of gelatin in the silver salt photographic film, then can cause silver grid line coating surface metal difficulty, thereby make the sheet resistance of conducting film bigger, or be prone to cause coating discontinuous (like sample 2-4～2-5).Therefore, the glue weight ratio of preferred silver and gelatin is 3～4 among the present invention.
Embodiment 8
Except the condition that changes chemical plating (actual conditions sees that table 3 is listed), similar with embodiment 1 preparation sample 1-1, make conducting film sample 3-1～3-12.Test its performance then.
The coating uniformity evaluation method is the uniformity of each sample coat of metal of visual observations, and carries out grading evaluation, and evaluation criterion is following:
Horizontal A: it is uneven almost not observe coating surface;
Horizontal B: it is slightly uneven only to observe coating;
Horizontal C: observe admissible uneven portion, trickle activation spot;
Horizontal D: obviously observe the uneven and large stretch of activation spot of coating.
Table 3: test result
| Sample number | The electroless copper time (min) | The chemical nickel plating time (min) | Sheet resistance (Ω/) | Visible light transmissivity (%) | Live width uniformity (%) | Coating uniformity | Remarks |
| 3-1 | 50 | 3 | 0.10 | 79.4 | 86.2 | B | The present invention |
| 3-2 | 45 | 3 | 0.83 | 80.3 | 86.8 | B | The present invention |
| 3-3 | 30 | 2 | 1.4 | 80.6 | 87.1 | B | The present invention |
| 3-4 | 20 | 3 | 2.5 | 80.8 | 87.3 | A | The present invention |
| 3-5 | 15 | 3 | 5 | 80.8 | 87.1 | A | The present invention |
| 3-6 | 10 | 3 | 9 | 80.9 | 87.2 | A | The present invention |
| 3-7 | 8 | 3 | 15 | 81.0 | 87.5 | A | The present invention |
| 3-8 | 6 | 3 | 22 | 81.0 | 87.5 | A | The present invention |
| 3-9 | 5 | 3 | 30 | 81.1 | 87.9 | A | The present invention |
| 3-10 | 3 | 3 | 100 | 81.2 | 88.5 | A | The present invention |
| 3-11 | 2 | 10 | 30 | 81.1 | 87.8 | A | The present invention |
| 3-12 | 2 | 7 | 100 | 81.2 | 87.9 | A | The present invention |
Embodiment 9
Similar with embodiment 1 preparation sample 1-1; Just chemical bronze plating liquid and chemical nickel-plating liquid among the embodiment 1 being diluted 2 times (pH value remains unchanged) back respectively uses; The adjustment bath temperature is 30 ℃, obtains the conducting film sample 4-1～4-15 of different surfaces resistance through the adjustment time.Test its performance then.
Table 4: test result
| Sample number | The electroless copper time (min) | The chemical nickel plating time (min) | Sheet resistance (Ω/) | Visible light transmissivity (%) | Live width uniformity (%) | Coating uniformity | With relation of the present invention |
| 4-1 | 3 | 6 | 320 | 81.8 | 88.2 | A | The present invention |
| 4-2 | 3 | 4 | 420 | 81.8 | 88.8 | A | The present invention |
| 4-3 | 3 | 2 | 550 | 81.9 | 88.8 | A | The present invention |
| 4-4 | 1.5 | 2 | 860 | 82.2 | 88.9 | A | The present invention |
| 4-5 | 1 | 2 | 1000 | 82.1 | 89.1 | A | The present invention |
| 4-6 | - | 10 | 320 | 81.9 | 90.2 | A | The present invention |
| 4-7 | - | 8 | 420 | 81.7 | 90.5 | A | The present invention |
| 4-8 | - | 6 | 550 | 81.8 | 90.5 | A | The present invention |
| 4-9 | - | 5 | 860 | 82.0 | 90.9 | A | The present invention |
| 4-10 | - | 4 | 1000 | 82.0 | 90.5 | A | The present invention |
| 4-11 | 6 | - | 320 | 81.6 | 89.8 | A | The present invention |
| 4-12 | 5 | - | 420 | 81.9 | 89.9 | A | The present invention |
| 4-13 | 4 | - | 550 | 81.7 | 90.2 | A | The present invention |
| 4-14 | 3 | - | 860 | 82.1 | 91.0 | A | The present invention |
| 4-15 | 2.5 | - | 1000 | 82.0 | 91.2 | A | The present invention |
Can find out from embodiment 3 and 4; Utilize method of the present invention; Through adjusting said chemical plating process and prescription, can make the nesa coating of different surfaces resistance, the sheet resistance of nesa coating can be regulated and control in 0.1 Ω/～1000 Ω/ scope; The uniformity of netting twine live width >=85% can satisfy actual use needs.
Embodiment 10
Electromagnetic wave shielding ability to the conducting film sample 3-1～3-4 of preparation among the embodiment 8 is studied; Confirmation its screening ability in the scope of 30MHz～1GHz is 30dB or bigger, and the nesa coating of manufacturing of the present invention can be used to make the transparent electromagnetic wave screened film of plasm TV (PDP) optical filtering screen usefulness effectively.
Embodiment 11
Conducting film sample 3-5～3-7 to preparation among the embodiment 3; Alternative ITO film; Anode as polymer and DSSC; The solar cell photoelectric transfer ratio is significantly improved, so the nesa coating of manufacturing of the present invention can be used to make the anode of organic thin film solar cell effectively.
Embodiment 12
To the conducting film sample 3-7～3-9 and the 3-11 of preparation among the embodiment 4, substitute the ITO film, as the anode of Electronic Paper, flexible OLED, the Electronic Paper of making, flexible OLED, display effect is good.Therefore the nesa coating of manufacturing of the present invention can be used to make the anode of Electronic Paper, flexible OLED effectively.
Embodiment 13
Conducting film sample 4-1～4-3,4-6～4-8 and 4-11～4-13 to preparation among the embodiment 4; Be coated with hardened layer again at the conductive layer back side; With the ITO film in its alternative touch-screen, make touch-screen, its demonstration property and touch-control effect are splendid; And have more pliability and anti-bending property than the ITO film, so the present invention can be used to make touch-screen effectively.
Claims (6)
1. nesa coating; It comprises support and formed conducting metal pattern above that; It is characterized in that; Said conducting metal pattern is to handle the metal mesh pattern that the back forms by the photosensitive material that contains silver emulsion through exposure, chemical development and chemical plating, and wherein, the reducing agent that said chemical plating is handled in the chemical plating fluid that uses is hypophosphites; Silver-colored line thickness on the netting twine is 0.4～2.4 micron, the homogeneity of netting twine live width >=85%; The silver in the said silver emulsion and the weight ratio of gelatin are 3～4; The sheet resistance of said conducting film is 0.1 Ω/～1000 Ω/.
2. according to the said nesa coating of claim 1, it is characterized in that the percent opening of the netted pattern of said conducting metal is greater than 80%, the main component of netting twine is argent and copper and/or the nickel of going up plating thereof.
3. according to the said nesa coating of claim 2, it is characterized in that said support is plastic film or glass.
4. according to the said nesa coating of claim 3, it is characterized in that said support is a pet film.
5. method for preparing like claim 1,2,3 or 4 said nesa coatings; It is characterized in that; On support the photosensitive material of coating silver emulsion, carry out lattice exposure and chemical development processing; Make the formation of exposed portion and unexposed portion comprise the grid exposing patterns of argent part and transparent part, carry out chemical plating then and handle, form transparent electrically-conductive film.
6. according to the preparation method of the said nesa coating of claim 5, it is characterized in that the silver coated amount of said silver sensitive material is 3 gram/rice
2Below.
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| CN103761017A (en) * | 2014-01-10 | 2014-04-30 | 深圳市宇顺电子股份有限公司 | Electronic equipment and manufacturing method for single-layered multipoint capacitive touch screen and touch layer |
| CN104269221A (en) * | 2014-08-29 | 2015-01-07 | 上海蓝沛新材料科技股份有限公司 | Method utilizing ink containing palladium compound for manufacturing transparent conducting film |
| CN105225728B (en) * | 2015-09-29 | 2017-01-04 | 惠州易晖光电材料股份有限公司 | A kind of low resistance transparent conductive film and preparation method thereof |
| CN110093596A (en) * | 2019-04-24 | 2019-08-06 | 南昌大学 | A kind of preparation method of the extra thin copper foil of Automatic-falling |
| CN110247193B (en) * | 2019-05-13 | 2020-06-02 | 华中科技大学 | Flexible gradual-change resistive film, preparation method and application thereof |
| CN111796706A (en) * | 2020-05-22 | 2020-10-20 | 南昌欧菲显示科技有限公司 | Panel, preparation method thereof, touch display screen and electronic equipment |
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