CN107210097A - There is the manufacture method and the manufacture method of wire netting substrate of the multilayer board of the electroconductive polymer layer of patterning on the transparent substrate - Google Patents
There is the manufacture method and the manufacture method of wire netting substrate of the multilayer board of the electroconductive polymer layer of patterning on the transparent substrate Download PDFInfo
- Publication number
- CN107210097A CN107210097A CN201480084376.3A CN201480084376A CN107210097A CN 107210097 A CN107210097 A CN 107210097A CN 201480084376 A CN201480084376 A CN 201480084376A CN 107210097 A CN107210097 A CN 107210097A
- Authority
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- China
- Prior art keywords
- electroconductive polymer
- polymer layer
- patterning
- substrate
- layer
- Prior art date
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- Pending
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
- B32B3/10—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Laminated Bodies (AREA)
- Manufacturing Of Electric Cables (AREA)
Abstract
The present invention provides a kind of method of the multilayer board for the electroconductive polymer layer for being manufactured with low-cost and high-precision and having patterning on the transparent substrate.The manufacture method on the transparent substrate with the multilayer board of the electroconductive polymer layer of patterning includes：The step of preparing multilayer board, the multilayer board has the etchant resist of patterning on the electroconductive polymer layer being formed on the single or double of transparency carrier；While the temperature of transparency carrier is maintained into less than 100 DEG C, under vacuum by being ashed the step of removing the electroconductive polymer for not covered and exposed by etchant resist layer；The step of removing the etchant resist remained on electroconductive polymer layer.
Description
Technical field
The present invention relates to the manufacture method of the multilayer board of the electroconductive polymer layer on the transparent substrate with patterning.
Moreover, it relates to the manufacture method of wire netting substrate.Especially, the present invention relates to the wire netting as touch panel substrate
The manufacture method of substrate.
Background technology
In recent years, in band touch surface of the preceding surface of display provided with touch panel (following, also referred to as " touch sensor ")
The demand of the display device of plate is whole with the miniature portable of the representatives such as portable phone, portable information terminal and auto-navigation system
The popularization at end and significantly increase.Touch panel refers to the position at the position by detecting the contacts such as finger or pen to enter
The input unit of row operation instruction or data input.As the mode of test position, except the static capacity manifold type of main flow,
Know resistance membrane type, infrared-type, ultrasonic type and electromagnetic induction/manifold type etc..
Although the ito film as the material of the touch panel of current main-stream is adapted to compact display apparatus, sheet resistance
Compare high.Therefore, medium-and-large-sized touch panel is technically not used to, therefore in order to open up popularization towards medium-and-large-sized touch panel
New markets, it is necessary to develop the touch panel by more cheap base material and the manufacture of more stable manufacturing process.Therefore, study
Without using ito film, and the sensing that touch panel is used is formed with the wire netting formed by the high material of the electric conductivity such as copper, silver
Device pattern.
Japanese Unexamined Patent Publication 2010-95776 publications (patent document 1) are described on base material and formed by non-electrolytic plating method
The technology of the metal film of patterning.A kind of base coating is disclosed in the publication, it is used on base material by electroless electricity
The base coating of the metal film of plating method formation patterning, high molecular particle of the base coating comprising electric conductivity or reproducibility
Son, adhesive and inorganic system's filler, high molecular particle and the mass ratio of described adhesive of the electric conductivity or reproducibility
For 1：11 to 1：60 scope, and the viscosity with more than 50cps.Moreover, disclosing pattern printing substrate on base material
Coating, by electroless plating liquid is come electroless plating metal film on the film layer of formation.
Japanese Unexamined Patent Publication 2013-257855 publications (patent document 2) are disclosed when manufacture is laminated by saturating over the transparent substrate
Formed by the conductive pattern layer of bright conductive material layer or metal level formation during touch panel, as pattern formation method, exist
Photoetching (etching), pattern printing, transfer, self-organization.
International Publication 2010/058778 (patent document 3) is disclosed etches electroconductive polymer according to the pattern of etchant resist
Film, the method for the substrate of electroconductive polymer film of the manufacture with patterning.As engraving method, wet etching is recorded and dry
Method is etched.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2010-95776 publications
Patent document 2：Japanese Unexamined Patent Publication 2013-257855 publications
Patent document 3：International Publication 2010/058778
The content of the invention
The invention technical problem to be solved
However, the technology that patent document 1 is recorded is not the technology for the sensor patterns for being envisaged for touch panel.Patent
Pattern formation method described in document 1 is intaglio printing, silk-screen printing, flexible version printing, offset printing, dry type offset printing and bat printing
The method for printing patterns of (pat print) etc., it is difficult to accurately form the sensor patterns as touch panel and demand
Fine sensor patterns.
In patent document 2, although describe photoetching (etching), pattern as the pattern formation method of conductive pattern layer and print
Brush, transfer, self-organization etc., but specifically only describe the example that chemical etching is carried out to copper foil.In the method due to
Etch away the most of of copper foil therefore produce substantial amounts of waste liquid, efficiency is low and cost is high.
Although disclosing by carrying out wet etching or dry etching to electroconductive polymer film to carry out in patent document 3
The method of patterning, but it is difficult to accurately be formed sensor patterns as touch panel in wet etching and demand
Fine sensor patterns.In addition, dry etching needs very expensive device, further, since carrying out high-temperature process so holding
Easily it is damaged substrate.Especially, in the case where substrate is resin film, easily produce resin film and deform this badness feelings because of heat
Condition.Further, it is also difficult to while by volume to volume (roll to roll) carrying substrate while being produced.
The present invention in view of above-mentioned item and create, it will thus provide manufactured with low-cost and high-precision on the transparent substrate have figure
The method of the multilayer board of the electroconductive polymer layer of case is used as one of technical problem.In addition, the present invention's will also provide profit
Another technical problem is used as with the manufacture method of the wire netting substrate of this method.
The method for solving technical problem
In order to solve the above-mentioned technical problem the present inventor has made intensive studies, and as a result sends out and is led now with photoetching process formation
After the fine pattern of electrical macromolecule layer, pattern printing or etching are not used, and use ashing to be favourable.Ashing is typically
The technology used in resist stripping, but according to the result of study of the present inventor, by ashing, can protect against corrosion
While the electroconductive polymer layer that agent (resist) is covered, low temperature, which is accurately eliminated, not to be covered and exposed by resist
Electroconductive polymer layer.The present invention is completed based on above-mentioned discovery.
There is provided a kind of stacking base for the electroconductive polymer layer for having pattern on the transparent substrate in one aspect of the invention
The manufacture method of plate, including：The step of preparing multilayer board, the multilayer board is being formed on the single or double of transparency carrier
Electroconductive polymer layer on have patterning etchant resist；While the temperature of transparency carrier is maintained into less than 100 DEG C,
By being ashed the step of removing the electroconductive polymer for not covered and exposed by etchant resist layer under vacuum condition；Remove electric conductivity
The step of etchant resist remained on macromolecule layer.
In the manufacture of the multilayer board of the electroconductive polymer layer on the transparent substrate with patterning involved in the present invention
In one embodiment of method, implement to be ashed by surface wave plasma.
In the manufacture of the multilayer board of the electroconductive polymer layer on the transparent substrate with patterning involved in the present invention
In another embodiment of method, implement to be ashed by microwave plasma.
In the manufacture of the multilayer board of the electroconductive polymer layer on the transparent substrate with patterning involved in the present invention
In the another embodiment of method, plasma is formed by the mixed gas of oxygen and fluorocarbons.
In the manufacture of the multilayer board of the electroconductive polymer layer on the transparent substrate with patterning involved in the present invention
In the another embodiment of method, electroconductive polymer layer is patterned with less than 5 μm of line width.
In the manufacture of the multilayer board of the electroconductive polymer layer on the transparent substrate with patterning involved in the present invention
In the another embodiment of method, electroconductive polymer layer to the maximum reflectivity in 400~700nm of wavelength region for 20% with
Under.
In the manufacture of the multilayer board of the electroconductive polymer layer on the transparent substrate with patterning involved in the present invention
In the another embodiment of method, there is pattern on the electroconductive polymer layer being formed on the single or double of transparency carrier
The substrate of the etchant resist of change, by forming electroconductive polymer layer on two-sided in transparency carrier, is being formed at transparency carrier
Etchant resist is formed respectively on electroconductive polymer layer on two-sided, using double-side exposure device simultaneously to two-sided etchant resist
It is exposed, it is then subjected to development again and be made.
In the manufacture of the multilayer board of the electroconductive polymer layer on the transparent substrate with patterning involved in the present invention
In the another embodiment of method, it can implement during using the handling device carrying substrate of volume to volume by ashing
The step of removing electroconductive polymer layer.
In the manufacture of the multilayer board of the electroconductive polymer layer on the transparent substrate with patterning involved in the present invention
It is upper residual by being ashed the step of removing electroconductive polymer layer and removing electroconductive polymer layer in the another embodiment of method
The step of etchant resist stayed, implement in same plasma ashing apparatus.
In the manufacture of the multilayer board of the electroconductive polymer layer on the transparent substrate with patterning involved in the present invention
In the another embodiment of method, the sheet resistance of electroconductive polymer layer is 107Ω/below.
In another aspect of this invention there is provided a kind of manufacture method of wire netting substrate, including prepare according to present invention system
That makes has the multilayer board of the electroconductive polymer layer of patterning on the transparent substrate, then, in the electric conductivity of the patterning
The step of coat of metal being formed on macromolecule layer.
In an embodiment of the manufacture method of wire netting substrate involved in the present invention, in addition to the coat of metal
The step of outer surface carries out Darkening process.
In another embodiment of the manufacture method of wire netting substrate involved in the present invention, wire netting substrate is to touch
The sensor base plate of panel.
In the another embodiment of the manufacture method of wire netting substrate involved in the present invention, it is additionally included in form metal
Before coating, the step of cleaning treatment is carried out to the electroconductive polymer of patterning layer.
In still another aspect of the invention there is provided a kind of manufacturing equipment of multilayer board, the multilayer board is on the transparent substrate
Electroconductive polymer layer with patterning, the equipment possesses：Photoresist slit type coater, it is used to formed
In on the single or double of transparency carrier electroconductive polymer layer on form etchant resist；Double-side exposure device, it is used for saturating
The upper and lower surface of bright substrate is exposed；Resist development processing unit, it is used for by being shown to photosensitive etchant resist
Shadow handles to be patterned；Cineration device, it is used to remove the electroconductive polymer layer exposed by the patterning of etchant resist；
Resist lift-off processing device, it is used to remove the etchant resist remained on electroconductive polymer layer.
In an embodiment of manufacturing equipment involved in the present invention, electrolytic plating apparatus is also equipped with, it is used in pattern
Metal level is formed on the electroconductive polymer layer of change.
In another embodiment of manufacturing equipment involved in the present invention, Darkening process device is also equipped with, it is used for gold
The outer surface for belonging to layer carries out Darkening process.
In another embodiment of manufacturing equipment involved in the present invention, cineration device and resist lift-off processing device quilt
It is integrated in a plasma ashing apparatus.
The effect of invention
In accordance with the invention it is possible to provide the electric conductivity for being manufactured with low-cost and high-precision and there is patterning on the transparent substrate
The method of the multilayer board of macromolecule layer.Therefore, by being formed selectively metal level, energy on electroconductive polymer layer
Enough manufactures adapt to the wire netting substrate of the touch panel of medium-and-large-sizedization.Use the touch panel of metal network technology easily big
Type, therefore it is contemplated that can popularize from now on, according to the present invention, it is more than 15 inches that can for example be applied to cornerwise length
Touch panel, can also further be applied to the touch panel that cornerwise length is more than 50 inches.That is, the present invention can be carried
The production technology of the epoch-making touch panel of tremendous contribution is made for the market expansion to medium-and-large-sized touch panel.
Brief description of the drawings
Fig. 1 shows the manufacturing step example of wire netting substrate.
Fig. 2 is the microphotograph example (2 μm of wiring width) for the wire netting substrate that embodiment is obtained.
Fig. 3 is the microphotograph example (4 μm of wiring width) for the wire netting substrate that embodiment is obtained.
Embodiment
The wire netting substrate ＞ of ＜ 1.
In an embodiment of wire netting substrate involved in the present invention, transparency carrier one side or it is two-sided on have
There is metal mesh pattern.In the touch of the projection type electrostatic capacity type as one of the purposes of wire netting substrate involved in the present invention
In panel, two layers of the electrode layer across the overlapping x-axis direction of insulating barrier and y-axis direction, according to interelectrode static capacity
Change detection touch location.Therefore, wire netting substrate involved in the present invention preferred embodiment in, transparency carrier
It is two-sided upper with metal mesh pattern.Metal mesh pattern is typically capable of the sensor patterns as touch panel.In transparent base
The two-sided of plate is gone up with the electrode layer and y-axis direction that in the case of wire netting, can form x-axis direction respectively with wire netting
Electrode layer.
It is used as the material of transparency carrier, although do not limit, but can enumerates：Soda-lime glass, silicate glasses, barium glass,
The category of glass such as phosphate glass, borate glass, fluoride glass and quartz glass, polyethylene terephthalate
(PET), the polyester fiber resin, cyclenes such as polybutylene terephthalate (PBT) (PBT) and PEN (PEN)
Hydrocarbon system resin, polycarbonate resin, polyimide resin, the resinae such as cellulose-based resin.Wherein, flexibility is preferably formed
Substrate and the resinae that can be produced in the way of volume to volume, particularly preferably polyethylene terephthalate or
Cyclic olefine resin.Transparent resin substrate is generally possible to the form offer with film.
The thickness of transparency carrier, although do not limit, but preferably 10 μm~700 μm, more preferably 25 μm~200 μm.
If thickness is within the above range, when using resin manufacture, transparency carrier can have durability and appropriate flexibility, therefore energy
It is enough that electroconductive polymer layer and metal level are filmed with high production rate by way of volume to volume on the transparency carrier.
In an embodiment of wire netting substrate involved in the present invention, by stacking gradually electric conductivity on the transparent substrate
The layered product formation metal mesh pattern that macromolecule layer and metal level are obtained.Although electroconductive polymer layer can be transparent,
But more preferably its reflectivity is less than 20%.By forming the electroconductive polymer layer of antiradar reflectivity on the transparent substrate, come
Covered from the reflected light of metal level by electroconductive polymer layer and be difficult to pass through transparency carrier, thus improve display screen can
Opinion property.Electroconductive polymer layer reflectivity be preferably 20~1% scope, more preferably 10~1% scope, even more preferably from
For 7~1% scope, the even more preferably scope for 5~1%.From the viewpoint of reduction reflectivity, electroconductive polymer
The color of layer is preferably black.In the present invention, can (for example ウ シ オ Electric Co., Ltd manufactures with spectral reflectance meter
URE-50 reflectivity) is measured, reflectivity refers to visible ray (400~700nm of wavelength) maximum reflectivity.During measurement reflectivity
Incident angle chooses 30 °, and uses 75W xenon lamp.
As the high molecular material for constituting electroconductive polymer layer, for example, it can enumerate polyaniline, polythiophene, poly- pyrrole
Cough up, polyphenylene, polyfluorene, poly bis thiophene, gather different thiophene, poly- (3,4-rthylene dioxythiophene), polyisothianaphthene gathers different naphthalene thiophene,
Polyacetylene, polydiacetylene, polyparaphenylene Asia ethene, polyacene, polythiazole, polyethyleneimine ethene gathers to benzene, poly-dodecyl
Thiophene, polyphenylenevinylene, polythiophene ethene, polyphenylene sulfide and their derivative etc..Among these, based on ash rate
It is high, the reasons why electroplating processes are easy, preferred polythiophene.
Based on the purpose for the electrical conductivity for improving electroconductive polymer, dopant can be used together.As dopant, it can enumerate：
The halogens such as iodine, chlorine, BF3、PF5Deng lewis acid, the proton acids such as nitric acid, sulfuric acid, transition metal, alkali metal, amino acid, core
Acid, surfactant, pigment, chloranil, TCNE, dopant known to TCNQ etc..
The electroconductive polymer layer high by forming electric conductivity on the transparent substrate, can hold under wide in range treatment conditions
Change places and be formed uniformly the metal level formed by electroplating processes.The sheet resistance of electroconductive polymer layer is preferably 107
Ω/below, more preferably 105Ω/below, still more preferably 104Ω/below, for example, can use 102~107Ω/
□.In addition, though its sheet resistance changes with the thickness of electroconductive polymer layer, it is preferable that thickness is separately retouched below
State.
In the case where due to macromolecule antiradar reflectivity can not be ensured as the reason such as transparent certainly, by electric conductivity high score
The dark pigment using the black pigment such as black pigment or black dyes as representative of necessary amounts is mixed in sublayer can control reflection
Rate.From the viewpoint of from uniformly dispersed in macromolecule, pigment and dyestuff are preferably water solubility.Although from reduction reflection
From the viewpoint of rate, the color of electroconductive polymer layer is preferably black, but can also be used in the case of non-black.Example
Such as, in the case where macromolecule is certainly as blue series, red colour system, it can be used according to its color depth, can also mix indigo plant
The pigment or dyestuff of colour system or red colour system are dyed.For example, polythiophene is blue series, therefore, it is possible to directly use.However,
In the case that the color of electroconductive polymer itself is not black, more preferably reduce anti-by mixing the pigment or dyestuff of black
Penetrate rate and improve observability.
Can in electroconductive polymer layer mixed adhesive to improve the adaptation with transparency carrier.As adhesive,
Although being not particularly limited, for example, it can enumerate：Polyvinyl chloride, makrolon, polystyrene, polymethyl methacrylate,
Polyester, polysulfones, polyphenylene oxide, polybutadiene, poly- (N- vinyl carbazoles), hydrocarbon resin, ketone resin, phenoxy resin, polyamide, second
Base cellulose, vinyl acetate, ABS resin, urethane resin, melmac, acrylic resin, unsaturated polyester resin, alcohol
Acid resin, epoxy resin, organic siliconresin etc..
The amount of binder used can be used more than 11 mass parts compared with the mass parts of electroconductive polymer 1, specifically,
It is preferred that being in a ratio of the scope of 11~60 mass parts with the mass parts of electroconductive polymer particulate 1.When adhesive is more than 60 mass parts
When, there is a situation where that the coat of metal is difficult to separate out, when adhesive is less than 11 mass parts, it is difficult to improve the viscosity of coating.
In addition, can be mixed for promoting in electroconductive polymer layer the carbon black of precipitation of the coat of metal, titanium oxide and
The inorganic filler of silicon dioxide granule etc..Although the usage amount of inorganic filler is not particularly limited, it is preferred that with the matter of adhesive 1
Amount part is in a ratio of the scope of 0.1~1.5 mass parts.Inorganic filler usage amount compared with the mass parts of adhesive 1 more than 1.5 matter
It is easily peeling-off between base material and film layer, it is difficult to good adaptation to be obtained, in addition, less than 0.1 in the case of measuring part
In the case of mass parts, there is a situation where that the coat of metal is difficult to separate out.
From the reducing of reflectivity, it is two-sided at the same exposure and it is plating resistance from the viewpoint of, the thickness of electroconductive polymer layer
It is critically important.Based on ensuring low reflectivity, when two-sided while effectively suppressing photoresist to opposing face during exposure
(photoresist) exposure influence, and the reasons why easy attachment electroplating film, the thickness of electroconductive polymer layer is preferably
More than 0.1 μm, still more preferably more preferably more than 0.2 μm, more than 0.3 μm.In addition, in order to remain closely sealed with transparent base
Property, the thickness of electroconductive polymer layer is preferably less than 1 μm, more preferably less than 0.7 μm, still more preferably less than 0.5 μm.
As formed metal level material, be metal, be not particularly limited, but the high copper of electric conductivity, copper alloy,
Silver, silver alloy, gold, billon, nickel and nickel alloy etc. be it is suitable, based on it is relatively cheap, electric conductivity is also high the reasons why, copper is special
It is not preferred.
From low sheet resistance is ensured, from the viewpoint of preventing broken string in addition, the thickness of metal level be preferably 0.1 μm with
On, more preferably more than 0.5 μm, still more preferably more than 0.7 μm.In addition, from the viewpoint of production efficiency is improved, metal level
Thickness be preferably less than 1 μm, more preferably less than 0.9 μm, still more preferably less than 0.8 μm.It should be noted that, although golden
The higher sheet resistance of thickness for belonging to layer is lower, but it is as above sufficient for less than 1 μm to be used as the thickness of touch panel purposes metal level
It is enough.
In addition, the aggregate thickness of electroconductive polymer layer and metal level is the height of sensor wiring, therefore when the wiring
The possibility that the wiring is peeled off in processes during excessive height is also uprised, thus it is less than 1.5 μm that this, which adds up to highly preferred, more excellent
Elect less than 1.3 μm, still more preferably less than 1.1 μm as.
The outer surface of preferred pair metal level carries out Darkening process.It is black by the outer surface of metal level, from metal level
Light reflection be further suppressed, therefore be conducive to improve display screen observability.As described above, due in transparency carrier
The electroconductive polymer layer of antiradar reflectivity is inserted between metal level, thus the reflected light from metal level is by electroconductive polymer
Layer covers and is difficult to pass through transparency carrier, the observability thus, it is possible to improve display screen.However, only carrying out metal during the processing
The outer surface of layer is exposed, and the light reflection of the outer surface from metal level can still be produced.
Therefore, Darkening process is carried out to the outer surface of metal level.Thus, additionally it is possible to suppress the outer surface from metal level
Light reflects.From the viewpoint of light reflection is effectively suppressed, the entirety progress of the outer surface of preferred pair metal level is blackened.As
The method of Darkening process, as long as making the processing of the outer surface blackening of metal level, is not particularly limited, but can for example arrange
Lift：The outer surface of metal oxide layer (be usually layers of copper) is grown at the surface oxidation representated by the processing of the film layer of cuprous oxide
Reason.In addition, although can also be handled by chemical synthesis, electroplating black chromium, black nickel plating etc. carries out Darkening process, but is based on
It is the step of being incorporated to plating step production line and the reasons why processing speed is fast, preferably by surface oxidation treatment carry out it is black
Change.Darkening process also has the effect for assigning antirust function.
Net-like pattern can not be substantially recognized from the vision of the mankind, and significantly improves the viewpoint of the observability of display screen
Set out, the line width of metal mesh pattern is preferably less than 10 μm, more preferably less than 5 μm, still more preferably less than 3 μm, and more excellent
Elect less than 2 μm as, for example, can choose 1~5 μm or so.
The size of wire netting substrate is not particularly limited, and can be used in any of small-sized, medium-sized and large-scale touch
Panel.For example in the case of the film substrate of rolled, the width of film substrate can be set to 500~600mm, in being used for
More than 800mm can be set to during more than type panel, more than 1500mm can be set to during for large-scale panel.
The manufacture method ＞ of the wire netting substrates of ＜ 2.
Illustrate the suitable method for manufacturing wire netting substrate involved in the present invention referring to the drawings.First, it is accurate
Standby transparency carrier 12, forms 11 ((1) in Fig. 1) of electroconductive polymer layer on the single or double of transparency carrier 12.As
The method that electroconductive polymer layer 11 is formed on transparency carrier 12, although do not limit, but can enumerate electroconductive polymer
Fine particles dispersion in organic solvent on the transparent substrate, and the method being dried.Stopped loss in order to anti-
Hinder transparency carrier 12, below 90 DEG C of preferred selection during heated drying.It is single alternatively, it is also possible to be coated on the surface of transparency carrier 12
Liquid solution, forms the film of electroconductive polymer by polymerization.Electroconductive polymer layer is typically not have figuratum planar film
Form.As described above, electroconductive polymer be not black or black degree it is inadequate in the case of, can also pass through mixing
Dark pigment representated by the black pigment such as black dyes or black pigment, the reflectivity of adjustment electroconductive polymer layer.It is conductive
The high molecular particulate of property can use commercially available product, can also use according to described in Japanese Unexamined Patent Publication 2010-95776 publications
The particulate of manufacture method manufacture.
As organic solvent, it can enumerate：The aliphatic esters such as butyl acetate, the aromatic solvent such as toluene, methyl ethyl ketone,
The ketones such as cyclohexanone, isophorone, the cyclic saturated hydrocarbons such as hexamethylene, the chain saturated hydrocarbons of normal octane etc., methanol, ethanol,
The chain saturation alcohols such as n-octyl alcohol, the aromatic ester of methyl benzoate etc., the fatty ethers of diethyl ether etc., and their mixing
Thing etc..In order to maintain the dispersion stabilization in dispersion liquid, the particulate preferably as the electroconductive polymer of solid content is this
Below the 5 mass % (solid content ratio) of the quality of dispersion liquid.
The average grain diameter of the particulate of the electroconductive polymer used can for example choose 1~500nm, be typically capable of choosing
Take 10~100nm or so.Herein, particle diameter is defined as that the minimum diameter of a circle of the particulate as measurement object can be surrounded.
In addition to the particulate of electroconductive polymer, adhesive, dispersion stabilizer, thickening can be added in dispersion liquid
The various additives such as agent, inorganic filler, dopant.
Then, etchant resist 13 ((2) in Fig. 1) is formed on electroconductive polymer layer 11.It is used as resist, liquid
Can, solidification also can, any of which can be used.Although photoresist or dry film photoresist can be used suitably,
Be from operability it is excellent, easily be evenly coated with from the viewpoint of, the photoresist of liquid is more preferably.For example, using photic
Resist slit type coater, after the photoresist of liquid is coated in into electroconductive polymer layer above, is toasted, so that
Etchant resist can be formed.In order to prevent the fire damage to substrate, implement baking preferably below 100 DEG C.
Then, etchant resist 13 is patterned ((3) in Fig. 1).Although the thickness of etchant resist is not limited, energy
0.1~10 μm or so of thickness is enough formed, is typically capable of being formed 2~4 μm or so of thickness.It is anti-it is important to set herein
The thickness of film is lost, when electroconductive polymer layer is removed so as to after, etchant resist will not disappear prior to electroconductive polymer layer.Typically
The removal rate of etchant resist than electroconductive polymer layer removal rate faster, it is therefore desirable in advance ensure etchant resist thickness foot
It is enough.It should be noted, however, that when etchant resist is blocked up, easily producing lateral erosion.In addition, the uniformity of the etchant resist of coating is very heavy
Will, preferably make thickness and precision within ± 10%, more preferably within ± 5%.It is used as the side patterned to etchant resist 13
Method, the mask pattern of formation such as can enumerate by ultraviolet is exposed to etchant resist, so as to transfer pattern to against corrosion
Method on film.The position represented by symbol 14 in Fig. 1 is the position exposed.Exposure can use contact exposure method
And contactless exposure method (for example, set gap between substrate and mask, non-contactly plane of exposure is scanned or
Any of the proximity printing method that person is exposed together), but from device is cheap and sight of high resolution
Point sets out, preferably contact exposure method, more preferably hard contact exposure method.Light exposure is determined according to the characteristic of various resists
It is fixed, to ensure most suitable line width and development conditions.
In the case where manufacture is formed with the touch panel of sensor patterns in the upper and lower surface of transparency carrier, it is necessary to use
Exposure device is exposed to upper and lower surface, but for transparent material, light exposure up and down influence mutual face and can not
Form correct pattern.But, by making electroconductive polymer layer be that the modes such as black carry out antiradar reflectivity, can fully it hide
The electroconductive polymer layer on transparency carrier is covered from the exposure influence from upper and lower surface, therefore, it is possible in the upper of transparency carrier
Lower surface forms correct pattern.Therefore, in the present invention, double-side exposure device can be used while above and below to transparency carrier
Surface is exposed, and can significantly improve production efficiency.
Then, when carrying out development treatment to photosensitive etchant resist using developer solution, etchant resist is removed simultaneously according to pattern
Expose electroconductive polymer layer ((4) in Fig. 1).The position that symbol 15 in Fig. 1 is represented is exposing for electroconductive polymer layer
Position.Etchant resist can use any of positive resist film and negativity etchant resist.In the case of positivity, expose
Etchant resist is removed, and unexposed etchant resist is remained as drafting department.Resist development processing unit can be used to be shown
Shadow processing.
Then, the electroconductive polymer layer ((5) in Fig. 1) exposed by the patterning of etchant resist is removed.It is used as removing
The method of electroconductive polymer layer, preferably maintains 100 DEG C by the temperature of transparency carrier, etchant resist and electroconductive polymer layer
While following, the method for the method of (ashing), more preferably plasma ashing is ashed under vacuum.It is ashed energy
Enough carried out by cineration device, preferably use plasma ashing apparatus.During ashing, remain in anti-on electroconductive polymer layer
Erosion film plays a role as a kind of mask, therefore, it is possible to optionally remove the electroconductive polymer exposed layer.Although during ashing
Etchant resist is also removed, but the selection ratio by the removal amount for obtaining resist and electroconductive polymer and sets most suitable
Etchant resist thickness, can remove electroconductive polymer layer and remain etchant resist.Thus, etchant resist is played as a kind of mask
Effect, therefore, it is possible to optionally remove the electroconductive polymer exposed layer.The position that symbol 16 in Fig. 1 is represented is electric conductivity
The position that macromolecule layer has been removed.
In the past, it is ashed after the etching, for removing the resist no longer needed.In the present invention, against corrosion on the contrary
Agent is not removed and remained as diaphragm, and is innovation for optionally removing the point of electroconductive polymer layer
Method.Be ashed needs the device of costliness unlike etching, very cheaply.Moreover, thrilling be, the inventors discovered that passing through
Electroconductive polymer layer can accurately be removed by carrying out ashing to electroconductive polymer layer.In addition, ashing can also adapt to volume
It is favourable on the point for being adapted to largely produce to the continuous processing of volume.Therefore, as the electroconductive polymer for forming patterning
The method of layer, it is high by the industrial value for being ashed the method for removing electroconductive polymer layer.
It is ashed while by the way that the temperature of transparency carrier is maintained into less than 100 DEG C, can prevents from damaging transparent base
Plate.When ashing, the temperature of transparency carrier is preferably kept at less than 100 DEG C, less than 90 DEG C is more preferably maintained, even more preferably from dimension
Hold below 80 DEG C.But, when excessive temperature is reduced, ashing efficiency (reaction speed) is reduced, therefore the temperature is preferably kept at
More than 50 DEG C, more preferably maintain more than 60 DEG C.
Especially, the thermal deformation of resin substrate can be suppressed when using resin substrate as transparency carrier, thus obtained
The advantage of the pattern formation of high-quality can stably be implemented.On the basis of being ashed at low temperature, preferably pass through microwave etc.
Gas ions are ashed.Because temperature can rise when using high-frequency plasma.In addition, by using microwave plasma
Body can remove electroconductive polymer layer with high uniformity.The frequency of microwave is generally possible to choose 300MHz~300GHz, still
When frequency is too small, the removal rate of electroconductive polymer layer is slack-off, therefore the optimized frequency of microwave is more than 1GHz, more preferably
Frequency be more than 2GHz.On the other hand, when frequency is too high, photoelectric transformation efficiency is reduced, in addition, heating causes the temperature of substrate
Easily rise, therefore microwave optimized frequency be below 10GHz, preferred frequency be below 5GHz, even more preferably from frequency
For below 3GHz.
In addition, passing through the plasma attack electroconductive polymer for being ashed under vacuum and passing through high-energy
Layer, being capable of high speed processing.In order to improve the electron density of plasma, preferably vacuum is calculated as below 500Pa with absolute pressure,
Below 200Pa is more preferably calculated as with absolute pressure.In addition, in order to suppress the reduction using gas concentration, preferably vacuum is with exhausted
More than 20Pa is calculated as to pressure, more than 50Pa is more preferably calculated as with absolute pressure.
From the viewpoint of electroconductive polymer layer is expeditiously removed, the higher the better for electron density during ashing.Specifically
Ground, is preferably set to 1 × 10 by electron density11Individual/cm3More than, more preferably it is set to 5 × 1011Individual/cm3More than, even more preferably from being set to
1×1012Individual/cm3More than.On the other hand, when excessively rise electron density, temperature becomes high temperature, therefore preferably by electron density
It is set to 1 × 1013Individual/cm3Hereinafter, 5 × 10 are more preferably set to12Individual/cm3Hereinafter, even more preferably from being set to 2 × 1012Individual/cm3Below.
In the present invention, electron density is defined as the value of electrostatic probe method measurement.
As the gas as plasma source, the oxygen of the ashing suitable for organic matter is preferably used, in order to improve reaction
Speed, more preferably uses the gaseous mixture with the etching gas such as fluorocarbons (being represented with CxFy (X, Y are natural numbers)) in addition to oxygen
Body.It can shorten ashing time by and with etching gas, therefore also obtain the advantage for the temperature rising that can suppress substrate.Make
For the concrete example of etching gas, CF can be enumerated4、C2F6、C3F8、C4F8Deng.
Plasma used in ashing is preferably surface wave plasma.The planar uniformity of surface wave plasma
Height, even the substrate of large area can also be handled with high uniformity.
Then, the etchant resist ((6) in Fig. 1) remained on electroconductive polymer layer is removed.The step can for example pass through
Make etchant resist contact to implement with stripper, and resist lift-off processing device can be used.As contact method, it can arrange
Lift：The method (immersion method) that the substrate of the etchant resist of patterning is integrally immersed in the container equipped with stripper will be remained, will be shelled
Chaotropic is sprayed on the method (spray-on process, spraying process) on etchant resist.Following stripping can be used as further efficient method
From method：By in the case that plasma ashing apparatus is ashed, being filled using the plasma ashing in the step of above
Put, stripping conditions are separately set, remove the etchant resist remained on electroconductive polymer layer.In this case, without separately accurate
Standby resist lift-off processing device, cost advantage is also very high.
Although being used after stripper typically heating, there is stripper in high-temperature process and electroconductive polymer layer is led
Situation about electrically adversely affecting.Therefore, temperature is preferably less than 50 DEG C.More preferably less than 40 DEG C, still more preferably 35
Below DEG C, most preferably less than 30 DEG C.In addition, when low temperature, stripping ability declines, therefore preferably more than 5 DEG C, more preferably
More than 10 DEG C.
Then, metal level 17 ((7) in Fig. 1) is formed on the electroconductive polymer layer 11 of the patterning.Metal level 17
Although formation do not limit, can use non-electrolytic plating method and galvanoplastic, implemented by electrolytic plating apparatus
.Non-electrolytic plating method and the galvanoplastic arbitrary method known to, but for example in non-electrolytic plating method
In the case of, to electroconductive polymer layer in electroconductive polymer particulate carry out dedoping processing become reproducibility it
Afterwards, by with patterning electroconductive polymer layer substrate immerse for adhere to the catalytic metals such as palladium bichloride catalytic solution,
Progress is washed etc., immersed in electroless plating bath, so as to be formed selectively metal level on electroconductive polymer layer.
Handle, can be enumerated using comprising hydroboron, dimethyl such as sodium borohydride, potassium borohydride as dedoping
The reducing agents such as the alkyl amine borine and hydrazine of amine borine, diethylamine borane, Trimethylamine borine, triethylamine borine etc.
The method that solution is handled and reduced, or the method handled using alkaline solution.From operational and economy
Viewpoint is set out, and is preferably used alkaline solution and is handled.
Catalytic solution is the solution for including the noble metal (urging agent metal) to electroless plating with catalytic activity, as urging
Change metal, palladium, gold, platinum, rhodium etc. can be enumerated, these metals can be that simple substance can also be compound, from including catalytic metal
The point of stability sets out, preferably palladium compound, and wherein palladium bichloride is particularly preferred.As preferred, specific catalytic solution, it can arrange
Lift the aqueous hydrochloric acid solution of 0.05% palladium bichloride -0.005% (pH3).Treatment temperature is 20~50 DEG C, preferably 30~40 DEG C, processing
Time is 0.1~20 minute, preferably 1~10 minute.
After the processing of catalyst imparting is carried out, the substrate of the electroconductive polymer layer with patterning is immersed and electroplated
Liquid, thus, it is possible to form electroless plating film.As electroplate liquid, generally, as long as the electroplate liquid available for electroless plating is
Can, it is not particularly limited.I.e., although can be used in metal, copper, gold, silver, nickel of electroless plating etc. can all be applicable, but
It is preferred copper.As the concrete example of electroless copper plating solution, for example, it can enumerate ATS ア De カ ッ パ ー IW baths (open country pharmaceuticals industry difficult to understand
(strain) company manufactures) etc..Treatment temperature is 20~50 DEG C, and preferably 30~40 DEG C, processing time is 1~30 minute, preferably 5
~15 minutes.The electronplate of acquisition carries out more than several hours preferably in the range of the Tg lower temperatures of the substrate than using,
For example, the maintenance of more than 2 hours.
After etchant resist is removed, implement before metal plating, the cleaning fluid cleaning base plate such as water, organic solvent can be used.
In addition, in order to improve adaptation of the metal level 17 to electroconductive polymer layer 11, also can be to conduction before the formation of metal level 17
Cleaned on the surface of property macromolecule layer 11.It is used as the method for cleaning, although do not limit, but can for example enumerates plasma
Processing.
Formed after metal level 17, Darkening process preferably further is carried out to the outer surface of metal level and Darkening process film is formed
18 ((8) in Fig. 1) of layer.The method of Darkening process is illustrated above.In addition, the advantage of Darkening process is also as described above.
Darkening process can use Darkening process device to carry out.Electrolytic plating apparatus can also have the function of Darkening process device.
In the above methods, using the electroconductive polymer of film, metal plating is carried out in final stage, so as to manufacture
Wire netting substrate.This method has the consumption of copper reducing more than 90% compared with the manufacture method of etching copper foil formation pattern
Effect.In addition, the electroconductive polymer of consumption is more cheap material compared with copper foil in itself, therefore can by the present invention
Significantly reduce the manufacturing cost of wire netting substrate.
In addition, according to the above method, additionally it is possible to using volume to volume handling device carrying substrate while, implement from
Either step of the electroconductive polymer layer untill metal level is formed is formed on transparency carrier, also can be in removing using volume to volume
While shipping unit carrying substrate, implement all steps.For example, ashing can repeat to implement the steps of：Use volume to volume
Handling device carrying substrate is simultaneously transported in ashing chamber, temporarily ceases progress ashing processing, hereafter carrying substrate again.
Wire netting substrate involved in the present invention, for example, can be applicable the touch panel of static capacity manifold type.
Embodiment
Below, although show for more fully understand the present invention and its advantage embodiment, but the invention is not restricted to
These embodiments.
(embodiment 1)
Prepare to be formed with about 0.3 μm in the upper and lower surface of polyethylene terephthalate (PET) film of 50 μm of thickness
Thickness polythiophene layer (containing water soluble black dye) substrate.The sheet resistance of polythiophene layer is 5 × 104Ω/□.Should
The thickness of polythiophene layer is that the light transmittance in the case of 0.3 μm of dual coating product is 27%.Sheet resistance and light transmittance
Measuring method is as described later.On the reflectivity of the polythiophene layer of the dual coating product, irradiation 200nm~800nm regions
Light, the light is measured using spectral reflectance meter (ウ シ オ motor manufacturing URE-50,30 ° of incident angle uses 75W xenon lamps)
Reflectivity, the reflectivity in the region of discovery visible ray (400~700nm) is maximum and is 7.4%.
Then, slit coater (TL0704) device manufactured using エ イ Block Le ジ ャ パ Application is handled deaeration just
Property photoresist with about 2.2 μm of thickness equably (coating uniformity：± 5.1%) coating polythiophene layer on one face
Upper (coated area 370mm × 470mm).After coating, 15 points are carried out to photoresist with less than 100 DEG C of hot blast IR heaters
Clock is dried.Then, photoresist is also sequentially formed with same on polythiophene layer on the other surface.Use the loose photon of creek
The Optical NanoGauge film thickness gauges of company's manufacture are integrally measured 45 the photic of point throughout film by spectral diffraction method and resisted
The thickness of film is lost, the formula for passing through ± (maximum film thickness-minimum thickness)/(maximum film thickness+minimum thickness) × 100 (%) is calculated
The coating uniformity of photoresist.
Then, by the sensor patterns of touch panel (line width for being formed with the position of metal level according to place has 1,
2、3、4、6、8μm.) mask vacuum be sealed at photoresist (synthetically produced positive against corrosion in East Asia of upper and lower surface both sides
Agent：Network リ ア マ ー ジ ュ TPR), UV light is irradiated above mask exposes the photosensitive hard contact for carrying out transfer pattern of photoresist
Light (big Japan's scientific research manufacture double-side exposure device：RA series).Light exposure is located at 100mJ~140mJ/cm2In the range of.
Then, using resist development processing unit, development treatment is carried out to photosensitive resist, exposes polythiophene
Layer.For the development treatment stablized, the temperature (25 DEG C ± 1 DEG C) and controlled concentration for controlling liquor using pid parameter are managed.
The etchant resist that will be patterned into is used as mask material, and the polythiophene layer exposed is removed by being ashed processing.Ashing is handled
Condition it is as described below.
Device：The microwave surface wave plasma processing unit of Co., Ltd.'s ニ ッ シ Application manufacture
Frequency：2.45GHz
Vacuum：50~200Pa (absolute pressure)
Electron density：1×1012Individual/cm3
Microwave is exported：1~5kW
Substrate temperature：Less than 70 DEG C
Use gas：O2And CF4Mixed gas
The plasma irradiating time：10~50 seconds
Hereafter, using resist lift-off processing device, with alkaline aqueous solution to the photoresist that is remained on polythiophene layer
Film carries out lift-off processing, only allows the drafting department exposing surface of polythiophene layer.
On the polythiophene layer of patterning, electroless copper facing is carried out, copper coating is thus only formed on polythiophene layer, is obtained
Wire netting substrate with defined sensor patterns.Hereafter, carry out being formed the melanism of cuprous oxide on the surface of copper coating
Processing.The thickness of obtained copper coating is about 0.5 μm.
The wire netting substrate obtained with the aforedescribed process is visually observed, discovery basically can not confirm to come from sensor patterns
Reflected light, it is difficult to visually confirm sensor patterns.In addition, with micro- sem observation sensor patterns, finding and sensor patterns
Line width accordingly, wire netting is with about 1,2,3,4,6,8 μm of line width is accurately patterned on the transparent substrate.In addition,
Light transmittance in sensor patterns is 85~88%.Sheet resistance is 1~10 Ω/.The photo of substrate after electroplating processes
Example is shown in Fig. 2 and Fig. 3.Understood to form metal wiring pattern with extremely high precision by Fig. 2 and Fig. 3.
It should be noted that in embodiment, the UV light sources (42mW/cm manufactured using ORC A.B.2), use ORC A.B.
The U-35/U-42 photometers of manufacture, measure the ratio of visible light-transmissive sensor, thus obtain light transmittance.On sheet resistance,
Using contact (4 sonde method) impedance measuring equipment, by the electrode of the needle-like of 4 it is in alignment be placed on measurement sample,
The potential difference produced between the probe that 2 on the inside of certain electric current, measurement are flowed between the probe of 2 of outside, thus
Obtain impedance.
(comparative example 1)
Although plasma irradiating time lengthening when will be ashed processing is in addition to 100 seconds or so, according to implementation
Untill the identical condition of example 1 is implemented into ashing processing, but the temperature of PET film rises to 120 DEG C or so.Therefore, at ashing
PET film after reason produces fluctuating.Therefore, processing hereafter is not implemented.
It should be noted that, although formed using other electroconductive polymers of polyamide, polypyrrole etc.
The experiment of electroconductive polymer layer, but in result of the test so far, polythiophene can not ensure high ash rate, in electricity
Plating is readily put most preferably.
Utilization possibility in industry
The touch panel sensor produced now, using the base material using ito film as main flow, but in the ITO base materials, by
It is very high and may not apply to medium-and-large-sized panel in its sheet resistance, so needing the low sheet resistance material such as wire netting sensor
Sensor.The touch panel being made using wire netting substrate involved in the present invention, can use metal formation sensor patterns, because
This resistance is low.Therefore, according to the present invention not only small-sized touch panel, medium-and-large-sized touch panel also can be easily manufactured,
It also can ensure that high observability.Thus, it is believed that expansion of the present invention to the medium-and-large-sized touch panel market as new markets
Open and make a significant contribution.
Description of reference numerals
11 electroconductive polymers layer
12 transparency carriers
13 etchant resists
14 exposure positions
The position that 15 electroconductive polymers layer exposes
The position that 16 electroconductive polymers layer has been removed
17 metal levels
18 Darkening process film layers
Claims (18)
1. a kind of manufacture method of the multilayer board of electroconductive polymer layer on the transparent substrate with patterning, including：
The step of preparing multilayer board, the multilayer board is in the electroconductive polymer being formed on the single or double of transparency carrier
There is the etchant resist of patterning on layer,
It is not against corrosion by being ashed removing under vacuum while the temperature of transparency carrier is maintained into less than 100 DEG C
The step of electroconductive polymer layer that film is covered and exposed,
The step of removing the etchant resist remained on electroconductive polymer layer.
2. the method for claim 1, wherein implement to be ashed by surface wave plasma.
3. method as claimed in claim 1 or 2, wherein, implement to be ashed by microwave plasma.
4. method as claimed in claim 3, wherein, plasma is formed by the mixed gas of oxygen and fluorocarbons.
5. such as method according to any one of claims 1 to 4, wherein, electroconductive polymer layer is entered with less than 5 μm of line width
Row patterning.
6. such as method according to any one of claims 1 to 5, wherein, electroconductive polymer layer is to 400~700nm's of wavelength
The maximum reflectivity in region is less than 20%.
7. method as claimed in claim 6, wherein, in the electroconductive polymer being formed on the single or double of transparency carrier
There is the substrate of the etchant resist of patterning on layer, by forming electroconductive polymer layer on two-sided in transparency carrier, formed
In transparency carrier it is two-sided on the electroconductive polymer layer on form etchant resist respectively, using double-side exposure device simultaneously it is right
Two-sided etchant resist is exposed, then subjected to development again and be made.
8. such as method according to any one of claims 1 to 7, wherein, base can carried using the handling device of volume to volume
During plate, implement by being ashed the step of removing electroconductive polymer layer.
9. such as method according to any one of claims 1 to 8, wherein, by being ashed the step of removing electroconductive polymer layer
The step of with the etchant resist remained on electroconductive polymer layer is removed, implement in same plasma ashing apparatus.
10. such as method according to any one of claims 1 to 9, wherein, the sheet resistance of electroconductive polymer layer is 107Ω/
Below.
11. a kind of manufacture method of wire netting substrate, including prepare according to method system according to any one of claims 1 to 10
That makes has the multilayer board of the electroconductive polymer layer of patterning on the transparent substrate, then, in the electric conductivity of the patterning
The step of coat of metal being formed on macromolecule layer.
12. the manufacture method of wire netting substrate as claimed in claim 11, wherein, in addition to the outer surface of the coat of metal is entered
The step of row Darkening process.
13. the manufacture method of wire netting substrate as claimed in claim 12, wherein, wire netting substrate is the biography of touch panel
Sensor substrate.
14. the manufacture method of the wire netting substrate as any one of claim 11~13, wherein, it is additionally included in form gold
Belong to before coating, the step of cleaning treatment is carried out to the electroconductive polymer of patterning layer.
15. a kind of manufacturing equipment of multilayer board, the multilayer board has the electroconductive polymer of patterning on the transparent substrate
Layer, the equipment possesses：Photoresist slit type coater, it is used to be formed at the single or double of transparency carrier
Electroconductive polymer layer on form etchant resist；Double-side exposure device, it is used to be exposed the upper and lower surface of transparency carrier；
Resist development processing unit, it is used to pattern by carrying out development treatment to photosensitive etchant resist；Ash makeup
Put, it is used to remove the electroconductive polymer layer exposed by the patterning of etchant resist；Resist lift-off processing device, it is used for
Remove the etchant resist remained on electroconductive polymer layer.
16. manufacturing equipment as claimed in claim 15, wherein, electrolytic plating apparatus is also equipped with, it is used for leading in patterning
Metal level is formed on electrical macromolecule layer.
17. manufacturing equipment as claimed in claim 16, wherein, Darkening process device is also equipped with, it is used for the outer of metal level
Surface carries out Darkening process.
18. the manufacturing equipment as any one of claim 15~17, wherein, cineration device and resist lift-off processing dress
Put and be integrated in a plasma ashing apparatus.
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| PCT/JP2014/084679 WO2016103510A1 (en) | 2014-12-26 | 2014-12-26 | Method for producing layered substrate in which patterned conductive polymer layer is provided on transparent substrate, and method for producing metal mesh substrate |
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| CN108776423A (en) * | 2018-06-28 | 2018-11-09 | 信利光电股份有限公司 | A kind of production method and equipment of touch control layer |
| CN111210944A (en) * | 2018-11-22 | 2020-05-29 | 日东电工株式会社 | Method for producing conductive thin film |
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| KR102255676B1 (en) * | 2018-09-10 | 2021-05-28 | 동국대학교 산학협력단 | Functional thin film forming method and electronic device manufactured thereby |
| CN113103791A (en) * | 2021-04-21 | 2021-07-13 | 广东星星精密玻璃科技有限公司 | 3D glass multi-pattern merging pad printing process |
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