WO2016103510A1 - Procédé de production d'un substrat en couches dans lequel une couche de polymère conducteur à motifs est disposée sur un substrat transparent, et procédé de production d'un substrat à mailles métalliques - Google Patents

Procédé de production d'un substrat en couches dans lequel une couche de polymère conducteur à motifs est disposée sur un substrat transparent, et procédé de production d'un substrat à mailles métalliques Download PDF

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Publication number
WO2016103510A1
WO2016103510A1 PCT/JP2014/084679 JP2014084679W WO2016103510A1 WO 2016103510 A1 WO2016103510 A1 WO 2016103510A1 JP 2014084679 W JP2014084679 W JP 2014084679W WO 2016103510 A1 WO2016103510 A1 WO 2016103510A1
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conductive polymer
polymer layer
substrate
transparent substrate
resist film
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PCT/JP2014/084679
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English (en)
Japanese (ja)
Inventor
護 日高
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日本テクノリード株式会社
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Priority to CN201480084376.3A priority Critical patent/CN107210097A/zh
Priority to PCT/JP2014/084679 priority patent/WO2016103510A1/fr
Publication of WO2016103510A1 publication Critical patent/WO2016103510A1/fr

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    • 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

Definitions

  • the present invention relates to a method for producing a laminated substrate having a conductive polymer layer patterned on a transparent substrate.
  • the present invention also relates to a method for manufacturing a metal mesh substrate.
  • the present invention relates to a method for manufacturing a metal mesh substrate useful as a touch panel substrate.
  • the touch panel is an input device that enables an operation instruction and data input by detecting the position of a part touched by a finger, a pen, or the like.
  • a position detection method a resistive film method, an infrared method, an ultrasonic method, an electromagnetic induction / coupling method, and the like are known in addition to the mainstream capacitive coupling method.
  • the ITO film which is currently the mainstream touch panel material, is suitable for small display devices, it has a relatively high sheet resistance. For this reason, it cannot be used technically for medium- and large-sized touch panels, so in order to develop and popularize a new market for medium- and large-sized touch panels, we developed a cheaper base material and a touch panel with a more stable manufacturing process. There is a need to. Therefore, a metal mesh in which a sensor pattern used for a touch panel is formed of a highly conductive material such as copper or silver instead of an ITO film has been studied.
  • Patent Document 1 JP 2010-95776 A (Patent Document 1) describes a technique for forming a patterned metal film on a substrate by an electroless plating method.
  • a base coating for forming a metal film patterned by an electroless plating method on a substrate comprising conductive or reducing polymer fine particles, a binder, and an inorganic system
  • a base coating material containing a filler and having a mass ratio of the conductive or reducing polymer fine particles to the binder in the range of 1:11 to 1:60 and having a viscosity of 50 cps or more is disclosed. And it discloses that the said base coating material is pattern-printed on a base material, and the metal film is chemically plated from the electroless-plating liquid to the formed coating film layer.
  • Patent Document 2 JP 2013-257855 A discloses a photo pattern forming method as a pattern forming method when manufacturing a touch panel in which a conductive pattern layer made of a transparent conductive material layer or a metal layer is laminated on a transparent substrate. Lithography (etching), pattern printing, transfer, and self-assembly are disclosed.
  • Patent Document 3 discloses a method of manufacturing a substrate having a patterned conductive polymer film by etching the conductive polymer film in accordance with a resist film pattern. As an etching method, wet etching or dry etching is described.
  • Patent Document 1 does not assume a sensor pattern for a touch panel.
  • the pattern forming method described in Patent Document 1 is a pattern printing method such as gravure printing, screen printing, flexographic printing, offset printing, dry offset printing, and pad printing. A fine sensor pattern required as a sensor pattern for a touch panel is used. It is difficult to form with high accuracy.
  • Patent Document 2 describes photolithography (etching), pattern printing, transfer, self-organization, and the like as a pattern forming method of the conductive pattern layer, but specifically, only an example in which copper foil is chemically etched is described. ing. In this method, most of the copper foil is etched, so that a large amount of waste liquid is generated, which is inefficient and expensive.
  • Patent Document 3 discloses a method of patterning a conductive polymer film by wet etching or dry etching, a fine sensor pattern required as a touch panel sensor pattern is formed with high accuracy in wet etching. It is difficult to do. In addition, an extremely expensive apparatus is required for dry etching, and the substrate is easily damaged due to high temperature processing. In particular, when the substrate is a resin film, the problem that the resin film is deformed by heat tends to occur. Furthermore, it is also difficult to produce while conveying the substrate by roll-to-roll.
  • the present invention was created in view of the above circumstances, and an object of the present invention is to provide a method for producing a laminated substrate having a conductive polymer layer patterned on a transparent substrate with high accuracy at low cost. . Another object of the present invention is to provide a method for producing a metal mesh substrate using the method.
  • the present inventor has intensively studied to solve the above problems, and it is advantageous to adopt ashing instead of pattern printing or etching when forming a fine pattern of the conductive polymer layer using photolithography.
  • Ashing is a technique usually used for resist stripping, but according to the results of the study by the present inventors, the conductive polymer layer masked by the resist is protected by ashing, and is exposed without being masked by the resist. It has been found that the conducting polymer layer can be cut with high accuracy at a low temperature.
  • the present invention has been completed based on the above findings.
  • the present invention provides a step of preparing a laminated substrate having a resist film patterned on a conductive polymer layer formed on one side or both sides of a transparent substrate, and is exposed without being covered with the resist film. Removing the conductive polymer layer by ashing under vacuum conditions while maintaining the temperature of the transparent substrate at 100 ° C. or lower, and removing the resist film remaining on the conductive polymer layer And a process for producing a laminated substrate having a conductive polymer layer patterned on a transparent substrate.
  • ashing is performed by surface wave plasma.
  • ashing is performed by microwave plasma.
  • the plasma is caused by a mixed gas of oxygen and fluorocarbon.
  • the conductive polymer layer is patterned with a line width of 5 ⁇ m or less.
  • the conductive polymer layer has a maximum reflectance in a wavelength region of 400 to 700 nm. 20% or less.
  • the conductive polymer layer formed on one or both surfaces of the transparent substrate is formed by forming a conductive polymer layer on both surfaces of the transparent substrate, and forming a resist film on each of the conductive polymer layers formed on both surfaces of the transparent substrate.
  • the resist films on both sides are simultaneously exposed by a double-sided exposure apparatus, and then developed through a development process.
  • the step of removing the conductive polymer layer by ashing comprises: It is carried out in the middle of conveyance by the to-roll conveyance device.
  • the step of removing the conductive polymer layer by ashing is performed in the same plasma ashing apparatus.
  • the sheet resistance value of the conductive polymer layer is 10 7 ⁇ / ⁇ or less. is there.
  • a laminated substrate having a conductive polymer layer patterned on a transparent substrate manufactured according to the present invention, and then a metal is formed on the patterned conductive polymer layer. It is a manufacturing method of the metal mesh board
  • the method further includes a step of blackening the outer surface of the metal plating layer.
  • the metal mesh substrate is a sensor substrate for a touch panel.
  • the method further includes a step of cleaning the patterned conductive polymer layer before forming the metal plating layer.
  • a photoresist slit coater for forming a resist film on a conductive polymer layer formed on one or both surfaces of a transparent substrate, and the upper and lower surfaces of the transparent substrate are exposed.
  • a manufacturing facility further includes a plating apparatus for forming a metal layer on a patterned conductive polymer layer.
  • the manufacturing facility according to the present invention further includes a blackening treatment device for blackening the outer surface of the metal layer.
  • the ashing apparatus and the resist stripping apparatus are integrated into one plasma ashing apparatus.
  • the present invention it is possible to provide a method for manufacturing a laminated substrate having a conductive polymer layer patterned on a transparent substrate with high accuracy at low cost. Therefore, by selectively forming a metal layer on the conductive polymer layer, it is possible to manufacture a metal mesh substrate for a touch panel that can cope with medium and large size. Since the touch panel using the metal mesh technology is easy to increase in size, it is expected to spread in the future. According to the present invention, for example, a touch panel having a diagonal length of 15 inches or more, and further a diagonal length of 50 inches. The present invention can also be applied to the touch panel described above. That is, the present invention can provide an innovative touch panel production technology that greatly contributes to the market expansion of medium and large touch panels.
  • An example of a manufacturing process of a metal mesh substrate is illustrated. It is an example of the microscope picture (wiring width 2 micrometers) of the metal mesh board
  • the metal mesh pattern is provided on one side or both sides of the transparent substrate.
  • the metal mesh pattern is provided on both surfaces of the transparent substrate.
  • the metal mesh pattern can be typically a sensor pattern for a touch panel.
  • the material of the transparent substrate is not limited, but glass such as soda lime glass, silicate glass, barium glass, phosphate glass, borate glass, fluoride glass and quartz glass, polyethylene terephthalate (PET), Examples thereof include polyester resins such as polybutylene terephthalate (PBT) and polyethylene naphthalate (PEN), and resins such as cycloolefin resins, polycarbonate resins, polyimide resins, and cellulose resins. Among them, resins that can be produced as a flexible substrate and can be produced in a roll-to-roll method are preferable, and polyethylene terephthalate or cycloolefin resins are particularly preferable.
  • the transparent resin substrate can generally be provided in the form of a film.
  • the thickness of the transparent substrate is not limited, but is preferably 10 ⁇ m to 700 ⁇ m, more preferably 25 ⁇ m to 200 ⁇ m. If the thickness is within the above range, the transparent substrate can have durability and appropriate flexibility when made of resin, so that a conductive polymer layer and a metal layer are roll-to-roll on it. Therefore, it is possible to form a film with high productivity.
  • the metal mesh pattern is formed of a laminate in which a conductive polymer layer and a metal layer are sequentially laminated on a transparent substrate.
  • the conductive polymer layer may be transparent, but the reflectance is more preferably 20% or less.
  • the reflectance of the conductive polymer layer is preferably in the range of 20 to 1%, more preferably in the range of 10 to 1%, still more preferably in the range of 7 to 1%, and still more preferably 5%.
  • the range is ⁇ 1%.
  • the color of the conductive polymer layer is preferably black from the viewpoint of reducing the reflectance.
  • the reflectance can be measured with a spectral reflectometer (for example, URE-50 manufactured by USHIO INC.) And refers to the maximum reflectance in visible light (wavelength 400 to 700 nm).
  • the incident angle at the time of reflectance measurement is 30 °, and a 75 W xenon lamp is used.
  • Examples of the polymer material constituting the conductive polymer layer include polyaniline, polythiophene, polypyrrole, polyphenylene, polyfluorene, polybithiophene, polyisothiophene, poly (3,4-ethylenedioxythiophene), polyisothione.
  • Examples include thianaphthene, polyisonaphthothiophene, polyacetylene, polydiacetylene, polyparaphenylene vinylene, polyacene, polythiazyl, polyethylene vinylene, polyparaphenylene, polydodecylthiophene, polyphenylene vinylene, polythienylene vinylene, polyphenylene sulfide, and their derivatives. it can.
  • polythiophene is preferable because of its high ashing rate and easy plating process.
  • a dopant may be used in combination for the purpose of increasing the electrical conductivity of the conductive polymer.
  • dopants include halogens such as iodine and chlorine, Lewis acids such as BF 3 and PF 5 , proton acids such as nitric acid and sulfuric acid, transition metals, alkali metals, amino acids, nucleic acids, surfactants, dyes, chloranil, tetra Well-known things are illustrated, such as cyanoethylene and TCNQ.
  • the sheet resistance value of the conductive polymer layer is preferably 10 7 ⁇ / ⁇ or less, more preferably 10 5 ⁇ / ⁇ or less, still more preferably 10 4 ⁇ / ⁇ or less, such as 10 2 to 10 7 ⁇ / ⁇ . Further, the sheet resistance value varies depending on the thickness of the conductive polymer layer, but a preferable thickness is separately described below.
  • the conductive polymer layer is preferably black from the viewpoint of reducing the reflectance, but can be used even when it is not black.
  • the polymer itself is blue or red, it can be used depending on its color density, or it can be colored by blending a blue or red pigment or dye.
  • polythiophene is blue, it can be used as it is.
  • the color of the conductive polymer itself is not black, it is more desirable to reduce the reflectance by adding a black pigment or dye to improve the visibility.
  • a binder can be blended in order to improve adhesion with the transparent substrate.
  • the binder is not particularly limited.
  • the binder used can be used in an amount of 11 parts by mass or more per 1 part by mass of the conductive polymer, and specifically, in the range of 11 to 60 parts by mass with respect to 1 part by mass of the conductive polymer fine particles. Preferably there is. If the binder exceeds 60 parts by mass, metal plating may be difficult to deposit, and if the binder is less than 11 parts by mass, it is difficult to increase the viscosity of the paint.
  • the conductive polymer layer can be blended with inorganic fillers such as carbon black, titanium oxide and silica particles for promoting the deposition of metal plating.
  • the amount of the inorganic filler used is not particularly limited, but is preferably in the range of 0.1 to 1.5 parts by mass with respect to 1 part by mass of the binder. When the amount of the inorganic filler used exceeds 1.5 parts by mass with respect to 1 part by mass of the binder, peeling between the base material and the coating film layer is likely to occur, and good adhesion may be difficult to obtain. Moreover, when it becomes less than 0.1 mass part, metal plating may become difficult to precipitate.
  • the thickness of the conductive polymer layer is important from the viewpoints of a decrease in reflectance, simultaneous exposure on both sides, and plating properties. It is preferably 0.1 ⁇ m or more for the reason of ensuring a low reflectance, effectively suppressing the exposure influence on the opposite side photoresist during double-sided simultaneous exposure, and facilitating adhesion of the plating film.
  • the thickness is more preferably 0.2 ⁇ m or more, and still more preferably 0.3 ⁇ m or more.
  • the thickness of the conductive polymer layer is preferably 1 ⁇ m or less, more preferably 0.7 ⁇ m or less, and 0.5 ⁇ m or less in order to maintain adhesion with the transparent substrate. Is even more preferred.
  • the material for forming the metal layer is not particularly limited as long as it is a metal, but copper, copper alloy, silver, silver alloy, gold, gold alloy, nickel, nickel alloy and the like having high conductivity are suitable, and relatively Copper is particularly preferred because it is inexpensive and has high conductivity.
  • the thickness of the metal layer is preferably 0.1 ⁇ m or more, more preferably 0.5 ⁇ m or more, and preferably 0.7 ⁇ m or more from the viewpoint of securing low sheet resistance and preventing disconnection. Even more preferred.
  • the thickness of the metal layer is preferably 1 ⁇ m or less, more preferably 0.9 ⁇ m or less, and even more preferably 0.8 ⁇ m or less from the viewpoint of increasing production efficiency.
  • sheet resistance will fall if the thickness of a metal layer becomes large, 1 micrometer or less is sufficient for the thickness of a metal layer in this way for a touch-panel use.
  • the total thickness of the conductive polymer layer and the metal layer is the height of the sensor wiring, if the wiring height becomes too high, there is a high possibility that the wiring will be peeled off during the process.
  • it is 1.3 ⁇ m or less, and more preferably 1.1 ⁇ m or less.
  • the outer surface of the metal layer is preferably blackened. Since the outer surface of the metal layer is black, light reflection from the metal layer is further suppressed, which is advantageous for improving the visibility of the display screen.
  • the low reflectivity conductive polymer layer is interposed between the transparent substrate and the metal layer, so that the reflected light from the metal layer is shielded by the conductive polymer layer and hardly passes through the transparent substrate. As a result, the visibility of the display screen can be improved. However, this alone exposes the outer surface of the metal layer, and light reflection from the outer surface of the metal layer can still occur.
  • the outer surface of the metal layer is blackened.
  • the entire outer surface of the metal layer is preferably blackened.
  • the blackening method is not particularly limited as long as the outer surface of the metal layer is blackened.
  • the outer surface of the metal layer usually a copper layer
  • the surface oxidation process represented by the process to make is illustrated.
  • blackening treatment by chemical conversion treatment, black chrome plating, black nickel plating, etc.
  • blackening by surface oxidation treatment is preferable because it is a process that can be incorporated on the plating process line and the processing speed is fast.
  • the blackening treatment also has a role of imparting a rust prevention function.
  • the line width of the metal mesh pattern is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less from the viewpoint of making the mesh pattern substantially unrecognizable by human vision and significantly improving the visibility of the display screen.
  • it is still more preferably 3 ⁇ m or less, still more preferably 2 ⁇ m or less, for example, about 1 to 5 ⁇ m.
  • the size of the metal mesh substrate is not particularly limited, and can be used for any of small, medium and large touch panels.
  • the river width of the film substrate can be 500 to 600 mm, can be 800 mm or more for a medium or larger panel, and can be 1500 mm or more for a large panel. You can also.
  • the transparent substrate 12 is prepared, and the conductive polymer layer 11 is formed on one side or both sides of the transparent substrate 12 ((1) in FIG. 1).
  • the method for forming the conductive polymer layer 11 on the transparent substrate 12 is not limited, but a dispersion liquid in which fine particles of the conductive polymer are dispersed in an organic solvent is applied on the transparent substrate, followed by heat drying. The method of doing is mentioned.
  • the temperature at the time of heat drying is preferably 90 ° C. or lower.
  • a conductive polymer thin film may be formed by coating a monomer solution on the surface of the transparent substrate 12 and polymerizing the solution.
  • the conductive polymer layer is usually in the form of a flat film having no pattern.
  • the conductive polymer layer is blended with a dark pigment such as black dye or black pigment. The reflectance may be adjusted.
  • the conductive polymer fine particles commercially available fine particles may be used, or they can be produced by the production method described in JP 2010-95776 A.
  • organic solvents examples include aliphatic esters such as butyl acetate, aromatic solvents such as toluene, ketones such as methyl ethyl ketone, cyclohexanone and isophorone, cyclic saturated hydrocarbons such as cyclohexane, and chain saturated hydrocarbons such as n-octane. , Chain saturated alcohols such as methanol, ethanol, n-octanol, aromatic esters such as methyl benzoate, aliphatic ethers such as diethyl ether, and mixtures thereof.
  • the conductive polymer fine particles have a solid content of 5% by mass or less (solid content ratio) of the mass of the dispersion.
  • the average particle diameter of the conductive polymer fine particles used can be, for example, 1 to 500 nm, typically about 10 to 100 nm.
  • the particle size is defined as the diameter of the smallest circle that can surround the fine particles to be measured.
  • various additives such as binders, dispersion stabilizers, thickeners, inorganic fillers and dopants can be added in addition to the conductive polymer fine particles.
  • a resist film 13 is formed on the conductive polymer layer 11 ((2) in FIG. 1).
  • a liquid or solid resist can be used.
  • Photoresists and dry film resists can be suitably used, but liquid photoresists are more preferred because of their good workability and easy application uniformly.
  • a resist film can be formed by baking after applying a liquid photoresist on the conductive polymer layer using a slit coater for photoresist. Baking is preferably performed at 100 ° C. or lower in order to avoid thermal damage to the substrate.
  • the thickness of the resist film is not limited, but can be formed with a thickness of about 0.1 to 10 ⁇ m, and typically with a thickness of about 2 to 4 ⁇ m. What is important here is that when the conductive polymer layer is removed later, the thickness of the resist film is set so that the resist film does not disappear before the conductive polymer layer. Since the resist film generally has a higher removal rate than the conductive polymer layer, it is necessary to ensure a sufficient thickness of the resist film. However, it should be noted that side etching tends to occur if the resist film is too thick. Further, the uniformity of the applied resist film is important, and the thickness accuracy is preferably within ⁇ 10%, and more preferably within ⁇ 5%.
  • Examples of a method for patterning the resist film 13 include a method of transferring the pattern to the resist film by exposing the resist film through a given mask pattern with ultraviolet rays or the like. A portion indicated by reference numeral 14 in FIG. 1 is an exposed portion.
  • a contact exposure system or a non-contact exposure system for example, a proximity exposure system in which a gap is provided between the substrate and the mask and the exposure surface is scanned or exposed in a non-contact manner
  • the contact exposure method is preferable because the apparatus price is low and the resolution is high, and the hard contact exposure method is more preferable.
  • the exposure amount is determined by the respective resist characteristics in order to ensure the optimum line width and development conditions.
  • the upper and lower exposure amounts affect each other and are accurate.
  • a pattern cannot be formed.
  • the conductive polymer layer black, etc. the conductive polymer layer on the transparent substrate sufficiently shields the exposure effect from the top and bottom surfaces, so the accurate pattern is transparent substrate It can be formed on the upper and lower surfaces. Therefore, in the present invention, it is possible to simultaneously expose the upper and lower surfaces of the transparent substrate using a double-side exposure apparatus, and the production efficiency can be remarkably improved.
  • a portion indicated by reference numeral 15 in FIG. 1 is a portion where the conductive polymer layer is exposed.
  • the resist film may be either a positive type or a negative type. In the case of the positive type, the exposed resist film is removed, and the unexposed resist film is left as a pattern portion.
  • the development processing can be performed by a resist development processing apparatus.
  • the exposed conductive polymer layer is removed by patterning the resist film ((5) in FIG. 1).
  • a method for removing the conductive polymer layer a method of ashing in a vacuum condition while maintaining the temperature of the transparent substrate, the resist film and the conductive polymer layer at 100 ° C. or lower is preferable, and a method of plasma ashing is more preferable. preferable.
  • Ashing can be performed by an ashing apparatus, and a plasma ashing apparatus is preferably used.
  • the resist film remaining on the conductive polymer layer functions as a kind of mask, so that the exposed conductive polymer layer can be selectively removed.
  • the resist film is also removed at the time of ashing, but the resist film is removed while removing the conductive polymer layer by optimally setting the resist film thickness by obtaining the selection ratio of the removal amount of the resist and the conductive polymer. It is possible to leave a film. Thereby, since the resist film functions as a kind of mask, the exposed conductive polymer layer can be selectively removed.
  • a portion indicated by reference numeral 16 in FIG. 1 is a portion from which the conductive polymer layer has been removed.
  • ashing has been used to remove unnecessary resist after etching.
  • the resist is left as a protective film without being removed, and this is an innovative method in that it is used for selectively removing the conductive polymer layer.
  • Ashing does not require expensive equipment like etching, and is inexpensive.
  • the present inventor has found that the conductive polymer layer can be removed with high accuracy by ashing the conductive polymer layer.
  • ashing is advantageous in that it can be applied to continuous processing by roll-to-roll, and is suitable for mass production. For this reason, the method of removing the conductive polymer layer by ashing has a very high industrial value as a method of forming the patterned conductive polymer layer.
  • the temperature of the transparent substrate is preferably maintained at 100 ° C. or lower, more preferably 90 ° C. or lower, and even more preferably 80 ° C. or lower.
  • the temperature is preferably maintained at 50 ° C. or higher, more preferably 60 ° C. or higher.
  • the transparent substrate when a resin substrate is used as the transparent substrate, it is possible to suppress the thermal deformation of the resin substrate, thereby obtaining an advantage that high-quality pattern formation can be stably performed.
  • ashing with microwave plasma is preferred. This is because the temperature rises when high-frequency plasma is used.
  • the frequency of the microwave can generally be 300 MHz to 300 GHz, but if the frequency is too small, the removal rate of the conductive polymer layer becomes slow. Therefore, the preferable frequency of the microwave is 1 GHz or more, and more preferable frequency. Is 2 GHz or more.
  • the preferred frequency of the microwave is 10 GHz or less, the more preferred frequency is 5 GHz or less, and even more preferred.
  • the frequency is 3 GHz or less.
  • the degree of vacuum is preferably 500 Pa or less in absolute pressure, and more preferably 200 Pa or less in absolute pressure.
  • the degree of vacuum is preferably 20 Pa or more in absolute pressure and more preferably 50 Pa or more in absolute pressure in order to suppress a decrease in the concentration of gas used.
  • the electron density is preferably 1 ⁇ 10 11 pieces / cm 3 or more, more preferably 5 ⁇ 10 11 pieces / cm 3 or more, and 1 ⁇ 10 12 pieces / cm 3 or more. Even more preferred.
  • the electron density is preferably 1 ⁇ 10 13 pieces / cm 3 or less, and more preferably 5 ⁇ 10 12 pieces / cm 3 or less.
  • the electron density is defined as a value measured by the electrostatic probe method.
  • the plasma source gas it is preferable to use an oxygen gas suitable for ashing organic substances, and in order to increase the reaction rate, in addition to oxygen, carbon fluoride (CxFy (X, Y is a natural number)) or the like is used. It is more preferable to use a mixed gas with an etching gas. Since the ashing time can be shortened by using the etching gas in combination, there is an advantage that the temperature rise of the substrate can be suppressed.
  • the etching gas include CF 4 , C 2 F 6 , C 3 F 8 , C 4 F 8 and the like.
  • the plasma used for ashing is preferably surface wave plasma.
  • Surface wave plasma has high in-plane uniformity, and even a large area substrate can be processed with high uniformity.
  • This step can be performed, for example, by bringing a resist film into contact with a stripping solution, and a resist stripping apparatus can be used.
  • a contact method a method in which the entire substrate on which the patterned resist film remains is placed in a container containing a stripping solution (immersion method), or a method in which the stripping solution is sprayed onto the resist film (spraying method, spraying method).
  • immersion method a method in which the stripping solution is sprayed onto the resist film
  • spraying method spraying method
  • An optional peeling method can be used. In this case, it is not necessary to prepare a resist stripping apparatus separately, and the cost merit is high.
  • the stripping solution is generally used by heating, but the stripping solution may adversely affect the conductivity of the conductive polymer layer in high temperature treatment. Therefore, 50 degrees C or less is preferable. More preferably, it is 40 degrees C or less, More preferably, it is 35 degrees C or less, Most preferably, it is 30 degrees C or less. Moreover, since peeling ability falls at low temperature, 5 degreeC or more is preferable, More preferably, it is 10 degreeC or more.
  • a metal layer 17 is formed on the patterned conductive polymer layer 11 ((7) in FIG. 1).
  • the formation of the metal layer 17 is not limited, but an electroless plating method and an electroplating method can be employed and may be performed by a plating apparatus. Any known method may be used for the electroless plating method and the electroplating method.
  • the conductive polymer particles in the conductive polymer layer are dedoped and reduced.
  • the substrate having the patterned conductive polymer layer is immersed in a catalyst solution for adhering a catalytic metal such as palladium chloride, washed with water, and immersed in an electroless plating bath.
  • a metal layer can be selectively formed on the molecular layer.
  • a reducing agent for example, a borohydride compound such as sodium borohydride or potassium borohydride, an alkylamine borane such as dimethylamine borane, diethylamine borane, trimethylamine borane, triethylamine borane, hydrazine, etc.
  • a borohydride compound such as sodium borohydride or potassium borohydride
  • an alkylamine borane such as dimethylamine borane, diethylamine borane, trimethylamine borane, triethylamine borane, hydrazine, etc.
  • the catalyst solution is a solution containing a noble metal (catalyst metal) having catalytic activity for electroless plating.
  • the catalyst metal include palladium, gold, platinum, rhodium, etc. These metals may be simple substances or compounds.
  • a palladium compound is preferable from the viewpoint of stability including a metal, and palladium chloride is particularly preferable among them.
  • a preferable specific catalyst solution includes 0.05% palladium chloride-0.005% hydrochloric acid aqueous solution (pH 3).
  • the treatment temperature is 20 to 50 ° C., preferably 30 to 40 ° C., and the treatment time is 0.1 to 20 minutes, preferably 1 to 10 minutes.
  • the substrate having the patterned conductive polymer layer is immersed in a plating solution, whereby an electroless plating film can be formed.
  • the plating solution is not particularly limited as long as it is a plating solution usually used for electroless plating. That is, metal, copper, gold, silver, nickel, etc. that can be used for electroless plating can all be applied, but copper is preferred.
  • Specific examples of the electroless copper plating bath include, for example, an ATS add copper IW bath (Okuno Pharmaceutical Co., Ltd.).
  • the treatment temperature is 20 to 50 ° C., preferably 30 to 40 ° C., and the treatment time is 1 to 30 minutes, preferably 5 to 15 minutes.
  • the obtained plated product is preferably cured for several hours or more, for example, 2 hours or more in a temperature range lower than Tg of the substrate used.
  • the substrate may be cleaned with a cleaning solution such as water or an organic solvent before metal plating. Further, in order to improve the adhesion of the metal layer 17 to the conductive polymer layer 11, the surface of the conductive polymer layer 11 can be cleaned before the metal layer 17 is formed.
  • the cleaning method is not limited, and examples thereof include plasma treatment.
  • the blackening process is exemplified by the method described above.
  • the advantages of the blackening process are also as described above.
  • the blackening process can be performed using a blackening apparatus.
  • the plating apparatus may have the function of a blackening apparatus.
  • a metal mesh substrate is manufactured by performing metal plating at the final stage using a thin conductive polymer.
  • This method has an effect of reducing copper consumption by 90% or more compared to a manufacturing method in which a copper foil is etched to form a pattern.
  • the consumed conductive polymer itself is an inexpensive material compared to the copper foil, the manufacturing cost of the metal mesh substrate can be significantly reduced by the present invention.
  • any process from the formation of the conductive polymer layer on the transparent substrate to the formation of the metal layer is performed while transporting the substrate with a roll-to-roll transport device. It is also possible to carry out all the steps while transporting the substrate with a roll-to-roll transport device.
  • the ashing can be performed by repeating the steps of transporting the substrate with a roll-to-roll transport device, transporting it into the ashing chamber, temporarily stopping and performing the ashing process, and then transporting the substrate again. .
  • the metal mesh substrate according to the present invention can be applied to, for example, a capacitively coupled touch panel.
  • Example 1 A substrate in which a polythiophene layer (containing a water-soluble black dye) having a thickness of about 0.3 ⁇ m was formed on the upper and lower surfaces of a polyethylene terephthalate (PET) film having a thickness of 50 ⁇ m was prepared.
  • the sheet resistance value of the polythiophene layer was 5 ⁇ 10 4 ⁇ / ⁇ .
  • the transmittance in the case of a double-side coated product having a thickness of 0.3 ⁇ m of this polythiophene layer was 27%. The measurement method of sheet resistance and transmittance is as described later.
  • the reflectance of the polythiophene layer of the double-side coated product is irradiated with light in the range of 200 nm to 800 nm, and the reflectance is measured with a spectroscopic reflectometer (Ushio URE-50, incident angle 30 °, using 75 W xenon lamp). As a result, the maximum reflectance of the region in visible light (400 to 700 nm) was 7.4%.
  • the defoamed positive photoresist is uniformly (coating uniformity: ⁇ 5.1%) with a thickness of about 2.2 ⁇ m using a slit coater (TL0704) apparatus manufactured by Able Japan. It was applied to the layer (application area 370 mm ⁇ 470 mm). After coating, the photoresist film was dried with hot air / IR heater at 100 ° C. or lower for 15 minutes. Subsequently, a photoresist film was formed in the same manner on the polythiophene layer on the other surface.
  • the coating uniformity of the photoresist is measured by measuring the film thickness of the photoresist film over 45 points by spectral interference method using an Optical NanoGauge film thickness meter manufactured by Hamamatsu Photonics, and ⁇ (maximum film thickness-minimum film) Thickness) / (maximum film thickness + minimum film thickness) ⁇ 100 (%).
  • a mask for a sensor pattern for a touch panel (the line width of the portion where the metal layer is formed is 1, 2, 3, 4, 6, 8 ⁇ m depending on the location) is applied to both the upper and lower photoresist films (Toa Gosei).
  • Hard contact exposure double-sided exposure equipment manufactured by Dainippon Kaken: RA series
  • a positive resist (Clearmage TPR) made by UV irradiation and exposing the photoresist to UV light from the mask to transfer the pattern.
  • the exposure amount was in the range of 100 mJ to 140 mJ / cm 2 .
  • the exposed resist was developed to expose the polythiophene layer.
  • temperature control 25 ° C. ⁇ 1 ° C.
  • concentration management of the chemical solution were controlled by PID parameters.
  • the exposed polythiophene layer was removed by ashing using the patterned resist film as a mask material.
  • the ashing conditions were as follows. Equipment: Microwave surface wave plasma processing equipment manufactured by Nissin Co., Ltd. Frequency: 2.45 GHz Degree of vacuum: 50 to 200 Pa (absolute pressure) Electron density: 1 ⁇ 10 12 / cm 3 Microwave output: 1-5kW Substrate temperature: 70 ° C or less Gas used: Mixed gas of O 2 and CF 4 Plasma irradiation time: 10 to 50 seconds
  • the photoresist film remaining on the polythiophene layer was stripped with an alkaline aqueous solution, and only the pattern portion of the polythiophene layer was exposed on the surface.
  • a copper plating layer was formed only on the polythiophene layer, and a metal mesh substrate having a predetermined sensor pattern was obtained. Then, the blackening process which forms a cuprous oxide on the surface of a copper plating layer was performed. The thickness of the obtained copper plating layer was about 0.5 ⁇ m.
  • the metal mesh substrate obtained by the above method was visually observed, the reflected light from the sensor pattern was hardly confirmed, and it was difficult to visually recognize the sensor pattern.
  • the sensor pattern was observed with a microscope, the metal mesh was patterned on the transparent substrate with a line width of about 1, 2, 3, 4, 6, 8 ⁇ m with high accuracy according to the line width of the sensor pattern.
  • the transmittance in the sensor pattern was 85 to 88%.
  • the sheet resistance value was 1 to 10 ⁇ / ⁇ . Examples of photographs of the substrate after the plating treatment are shown in FIGS. 2 and 3 that the metal wiring pattern is formed with extremely high accuracy.
  • the transmittance is the ratio of visible light passing through the sensor using an ORC UV light source (42 mW / cm 2 ) and an ORC U-35 / U-42 illuminometer. Obtained by measuring.
  • the sheet resistance is a contact-type (4-probe method) resistance measuring instrument. Four needle-shaped electrodes are placed on a measurement sample on a straight line, a constant current is passed between the two outer probes, and the inner two The resistance was determined by measuring the potential difference generated between the probe tips.
  • Example 1 The ashing process was performed under the same conditions as in Example 1 except that the plasma irradiation time during the ashing process was increased to about 100 seconds, but the temperature of the PET film rose to about 120 ° C. For this reason, the PET film after the ashing treatment was waved. Therefore, the subsequent processing was not performed.
  • the touch panel sensors currently produced are mainly substrates using ITO film, but the ITO substrate cannot be applied to medium and large panels due to its high sheet resistance.
  • a low sheet resistance material sensor such as a mesh sensor is required.
  • the touch panel made using the metal mesh substrate according to the present invention has a low electric resistance because the sensor pattern is made of metal. Therefore, according to the present invention, not only a small touch panel but also a medium / large touch panel can be easily manufactured, and high visibility can be secured. For this reason, it is considered that the present invention greatly contributes to the expansion of the medium and large touch panel market, which is a new market.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Laminated Bodies (AREA)
  • Manufacturing Of Electric Cables (AREA)

Abstract

L'invention concerne un procédé de production, à faible coût et avec une précision élevée, d'un substrat en couches dans lequel une couche de polymère conducteur à motifs est disposée sur un substrat transparent. Le procédé de production du substrat en couches dans lequel une couche de polymère conducteur à motifs est disposée sur un substrat transparent comprend : une étape de préparation d'un substrat en couches au cours de laquelle un film de résist à motifs est disposé sur une couche de polymère conducteur formée sur une surface ou sur les deux surfaces d'un substrat transparent ; une étape au cours de laquelle la couche de polymère conducteur exposée qui n'est pas revêtue par le film de résist est éliminée en étant soumise à une incinération dans des conditions de vide tandis que la température du substrat transparent est maintenue à une température inférieure ou égale à 100 °C ; et une étape au cours de laquelle le film de résist restant sur la couche de polymère conducteur est supprimé.
PCT/JP2014/084679 2014-12-26 2014-12-26 Procédé de production d'un substrat en couches dans lequel une couche de polymère conducteur à motifs est disposée sur un substrat transparent, et procédé de production d'un substrat à mailles métalliques WO2016103510A1 (fr)

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PCT/JP2014/084679 WO2016103510A1 (fr) 2014-12-26 2014-12-26 Procédé de production d'un substrat en couches dans lequel une couche de polymère conducteur à motifs est disposée sur un substrat transparent, et procédé de production d'un substrat à mailles métalliques

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