WO2015030115A1 - Stratifié conducteur à motifs et son procédé de production - Google Patents

Stratifié conducteur à motifs et son procédé de production Download PDF

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WO2015030115A1
WO2015030115A1 PCT/JP2014/072578 JP2014072578W WO2015030115A1 WO 2015030115 A1 WO2015030115 A1 WO 2015030115A1 JP 2014072578 W JP2014072578 W JP 2014072578W WO 2015030115 A1 WO2015030115 A1 WO 2015030115A1
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conductive laminate
conductive
conductor
patterned
conductive layer
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PCT/JP2014/072578
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English (en)
Japanese (ja)
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大井亮
西岡和也
渡邊修
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東レ株式会社
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Priority to JP2014546636A priority Critical patent/JPWO2015030115A1/ja
Priority to CN201480047761.0A priority patent/CN105493206A/zh
Publication of WO2015030115A1 publication Critical patent/WO2015030115A1/fr

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    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F2203/00—Indexing scheme relating to G06F3/00 - G06F3/048
    • G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
    • G06F2203/04103—Manufacturing, i.e. details related to manufacturing processes specially suited for touch sensitive devices

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  • the present invention provides a method for producing a patterned conductive laminate in which at least a base material and a conductive layer are formed in this order, and a conductor in the conductive layer is removed, a conductive laminate patterned by the production method, and
  • the present invention relates to various uses such as a touch panel using the patterned conductive laminate.
  • a conductive laminate including a conductive layer is widely used in electronic display devices such as flat panel displays and touch panels.
  • ITO tin-doped indium oxide
  • indium is a rare metal
  • new conductors that replace ITO have been developed.
  • the conductive laminate using ITO has disadvantages that it is expensive to manufacture because it is formed in a vacuum and is weak against bending.
  • Development of carbon nanotubes, conductive polymers, metal nanoparticles, metal nanowires and the like have been actively conducted as novel conductors that compensate for these disadvantages. Since conductive laminates using these new materials can be produced by a coating method even under atmospheric pressure, cost reduction is expected. It is also known that it is excellent in mechanical durability such as bending and pulling.
  • Patent Document 1 it has been proposed to apply a conductive laminate using carbon nanotubes or silver nanowires as a novel conductor to a touch panel (see, for example, Patent Document 1).
  • Patent Document 2 it has been proposed to apply a conductive polymer to electronic paper as a conductor (see, for example, Patent Document 2).
  • ITO powder together with a binder resin see, for example, Patent Document 3).
  • a conductive laminate is often used by patterning a conductive layer into a linear shape.
  • the patterning method of the conductive layer is important.
  • the conductive layer is required to have a uniform surface resistance.
  • uniformity of light transmittance is also required.
  • the conductor is uniformly provided on the entire surface of the substrate, and then unnecessary portions are removed to obtain a conductive laminate having a desired pattern shape.
  • Patent Document 4 A method of patterning a conductive layer of a conductive laminate including carbon nanotubes by dry etching has been proposed (see, for example, Patent Document 4).
  • an etchant that improves the etching performance of an existing conductive laminate using ITO has been proposed (see, for example, Patent Document 5).
  • ITO and metal thin films In addition to ITO and metal thin films, conductors used in conductive laminates are becoming more diverse, such as carbon nanotubes, silver nanowires, and conductive polymers, but in order to pattern them with a wet process, It was necessary to search for or develop an etchant each time.
  • existing etchants for ITO and metal thin films are often strong acids, mixed acids, highly oxidizing or corrosive chemicals, or strong alkaline chemicals, which are difficult to handle and are expensive to handle. It was necessary.
  • Patent Document 4 describes a general ITO wet process. Iron chloride is a common etchant. However, it is highly corrosive, and there are factors that increase the cost of the equipment, such as the need for anti-corrosion measures for the etching equipment, incidental equipment such as the room where the equipment is installed, and the exhaust duct. Even in Patent Document 5, hydrofluoric acid, which is difficult to handle, was used.
  • the conductive laminates described in Patent Documents 1 to 3 can be patterned using, for example, a dry etching process as described in Patent Document 6, but compared with a wet process, There was a problem of high costs.
  • the patterning for the existing ITO or thin film metal since the conductor is removed, a difference in refractive index or reflectance occurs between the conductor removed portion and the conductor remaining portion, thereby making the pattern easy. There was a problem of being visually recognized. For example, in a capacitive touch panel, since the touch panel is disposed on the screen, it is preferable that the pattern is not visually recognized.
  • the problem to be solved by the present invention is to provide a method for patterning a conductive laminate without using a highly corrosive chemical solution and having excellent handling properties.
  • the present invention comprises the following methods. (1) In order for the conductive laminate having a conductive layer containing a base material and a carbon atom-containing conductor in order, with the electrolyte interposed, A method for producing a patterned conductive laminate comprising a step of applying a voltage with an anode serving as a conductive layer and a cathode as a counter electrode, and removing the conductor in the conductive laminate from the conductive laminate. As a more preferred embodiment, the present invention provides the following embodiments. (2) The above-described masking material that prevents contact between the conductive laminate and the electrolytic solution and is patterned on a part of the surface of the conductive laminate on the conductive layer side when a voltage is applied.
  • a method for producing a patterned conductive laminate (3) When the voltage is applied, the patterned masking material is present in which a part of the surface of the counter electrode on the conductive laminate side prevents the contact between the counter electrode and the electrolyte and is patterned.
  • a method for producing a conductive laminate (4) The method for producing the patterned conductive laminate, wherein the counter electrode has a pattern shape.
  • the conductive layer includes an insulator before voltage application, and the insulator remains in a portion where the conductor is removed even after the conductor in the conductive layer is removed.
  • a method for producing a patterned conductive laminate (7) The method for producing a patterned conductive laminate according to any one of the above, wherein the applied voltage is 5 V or more and 15 V or less. (8) The method for producing a patterned conductive laminate according to any one of the above, wherein the voltage application time is 2 seconds to 60 seconds.
  • a patterned conductive laminate produced by any one of the production methods described above. Furthermore, the present invention provides the following parts using a conductive laminate. (10) A capacitive touch switch using the conductive laminate. (11) A touch panel using the patterned conductive laminate.
  • the patterned conductive laminate manufacturing method of the present invention is a patterning method that does not require the use of highly corrosive chemicals such as strong acids and strong alkalis.
  • a laminate can be manufactured.
  • the conductive laminate obtained by the patterning method of the present invention can be a patterned conductive laminate in which it is difficult to visually distinguish the patterned conductive layer and the portion from which the conductor has been removed.
  • the “conductive layer” in the present invention means a layer including a conductor and an overcoat layer and an undercoat layer provided as necessary.
  • patterning in the conductive layer means that the conductor is removed in a part of the conductive layer, and as a result, there are a part with a lot of conductor and a part with a little conductor, and these parts form a pattern. It means that
  • the conductor used in the present invention contains a carbon atom. Any conductor containing carbon atoms can be patterned by the method of the present invention.
  • a conductive substance containing carbon as a constituent atom such as a carbon nanotube, graphene, or a conductive polymer can be used.
  • Examples of conductive polymers include polyacetylene, poly (p-phenylene), poly (p-phenylene vinylene), polypyrrole, polythiophene, PEDOT-PSS (poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid) ), And a polymer that conducts electricity through a ⁇ -electron conjugated system, such as polyaniline.
  • carbon nanotubes, graphene, and conductive polymers are exemplified as particularly excellent conductors.
  • the conductive laminate used in the present invention is composed of a base material for maintaining a shape and a conductive layer containing a conductor containing a conductor in order. Note that the conductive layer does not need to be formed of only a conductor, and may include, for example, both a conductor and an insulator.
  • Examples of the substrate of the present invention include resin and glass.
  • Examples of the resin include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polycarbonate (PC), polymethyl methacrylate (PMMA), polyimide, polyphenylene sulfide, aramid, polypropylene, polyethylene, polylactic acid, polyvinyl chloride, Polymethyl methacrylate, alicyclic acrylic resin, cycloolefin resin, triacetyl cellulose and the like can be used.
  • As the glass ordinary soda glass can be used.
  • these several base materials can also be used in combination.
  • a composite laminated substrate such as a substrate in which a resin and glass are combined and a substrate in which two or more kinds of resins are laminated may be used.
  • the resin film may be provided with a hard coat.
  • the type of the substrate is not limited to the above, and an optimal one can be selected from the durability, cost, etc. according to the application.
  • the thickness of the substrate is not particularly limited, but when used for display-related electrodes such as a touch panel, a liquid crystal display, organic electroluminescence, and electronic paper, it is preferably between 10 and 1,000 ⁇ m.
  • a dispersion liquid containing a conductor such as a carbon nanotube is applied on the substrate.
  • a hydrophilic functional group is present on the surface of the base material to improve the surface tension of the base material.
  • the hydrophilic functional group include a carboxyl group, a carbonyl group, a hydroxyl group, a sulfone group, and a silanol group.
  • the following method is illustrated as a method of making a hydrophilic functional group exist on the surface of a base material.
  • There are methods for performing physical treatment such as corona treatment, plasma treatment, flame treatment, or chemical treatment such as acid treatment or alkali treatment on the substrate. Among these, providing an undercoat layer and corona treatment are preferable.
  • the hydrophilicity of the undercoat layer is preferably such that the water contact angle is in the range of 5 to 10 °. It is preferable to use an inorganic oxide for the undercoat layer. Among these, those containing titania, alumina, and silica as the main component are more preferable, and those containing silica as the main component are more preferable.
  • the “main component” means a component contained in 50% by mass or more in all components, more preferably 60% by mass or more, and more preferably 80% by mass or more. preferable. (Hereinafter, the same explanation applies to the “main components” of other materials). These substances have a hydroxyl group which is a hydrophilic group on the surface and are preferable because high hydrophilicity can be obtained.
  • the method for providing the undercoat layer on the substrate is not particularly limited.
  • Known wet coating methods such as spray coating, dip coating, spin coating, knife coating, gravure coating, slot die coating, roll coating, bar coating, screen printing, ink jet printing, pad printing, and other printing can be used.
  • a dry coating method may be used.
  • physical vapor deposition such as sputtering or vapor deposition, chemical vapor deposition, or the like can be used.
  • the undercoat may be formed in a plurality of times, or two different types of forming methods may be combined.
  • Preferred forming methods are gravure coating, bar coating, and slot die coating, which are wet coatings.
  • the thickness of the undercoat layer is not limited as long as sufficient hydrophilicity can be obtained, but a thickness of 1 to 120 nm is preferable. A thickness that can effectively obtain the antireflection effect due to optical interference is preferable because the light transmittance is improved. For this reason, it is preferable that the thickness is in the range of 80 to 120 nm together with the thickness of the overcoat layer described later.
  • the carbon nanotube that can be used in the present invention is not particularly limited as long as the carbon nanotube has a substantially graphite structure on the side surface.
  • Both single-walled carbon nanotubes in which one surface of graphite is wound in one layer and multi-walled carbon nanotubes wound in multiple layers can be applied.
  • the conductivity and the dispersibility of the carbon nanotubes in the dispersion medium for coating increase.
  • the double-walled carbon nanotube is preferable from the viewpoint that even if the surface is functionalized by acid treatment or the like, the original functions such as conductivity are not easily impaired.
  • Carbon nanotubes are manufactured as follows, for example.
  • a powdered catalyst in which iron is supported on magnesia is present on a mesh-like metal plate installed horizontally in a vertical reactor. At that time, the catalyst is present on the mesh metal plate without any deviation.
  • methane is supplied into the reactor in the vertical direction, and methane and the catalyst are brought into contact at 500 to 1,200 ° C. to produce carbon nanotubes.
  • carbon nanotubes containing single to five-layer carbon nanotubes can be obtained.
  • the oxidation treatment is performed by a method of treating with nitric acid, for example. Nitric acid is preferred because it acts as a dopant for the carbon nanotubes.
  • a dopant is a substance that gives a surplus electron to a carbon nanotube or takes away an electron to form a hole, and improves the conductivity of the carbon nanotube by generating a carrier that can move freely.
  • the nitric acid treatment method is not particularly limited as long as the carbon nanotube of the present invention is obtained, it is usually carried out in an oil bath at about 140 ° C.
  • the treatment time with nitric acid is not particularly limited, but is preferably in the range of 5 to 50 hr. A method for forming a conductive layer containing carbon nanotubes on the substrate will be described later.
  • a dispersant for applying a conductor such as carbon nanotube can be used.
  • the dispersant include surfactants and various polymer materials (such as water-soluble polymer materials). Of these, ionic polymer materials having high dispersibility are preferred.
  • the ionic polymer material include an anionic polymer material, a cationic polymer material, and an amphoteric polymer material. Any type of carbon nanotube can be used as long as it has high dispersibility and can maintain dispersibility. An anionic polymer material is preferable because of its excellent dispersibility and dispersion retention.
  • carboxymethyl cellulose and its salts for example, sodium salt, ammonium salt, etc.
  • polystyrene sulfonic acid salts are preferable because carbon nanotubes can be dispersed efficiently.
  • examples of the cationic substance constituting the salt include alkali metal cations such as lithium, sodium and potassium, and alkaline earth metal cations such as calcium, magnesium and barium.
  • Ammonium ions, or onium ions of organic amines such as monoethanolamine, diethanolamine, triethanolamine, morpholine, ethylamine, butylamine, coconut oil amine, beef tallow amine, ethylenediamine, hexamethylenediamine, diethylenetriamine, polyethyleneimine, or these Polyethylene oxide adducts can be used. Of course, it is not limited to these.
  • the dispersion medium for dispersing the conductor such as carbon nanotubes is preferably water from the viewpoints that the dispersant can be easily dissolved and that the waste liquid can be easily treated.
  • the method for preparing the dispersion used in the present invention is not particularly limited.
  • the dispersion can be performed by the following procedure. Since the treatment time at the time of dispersion can be shortened, a dispersion liquid containing a conductor such as carbon nanotubes in the dispersion medium in the range of 0.003 to 0.15 mass% is prepared, and then diluted to obtain a predetermined value. It is preferable to use a concentration of In the present invention, the mass ratio of the dispersant to the conductor such as carbon nanotube is preferably 0.1 to 10. Within such a preferred range, it is easy to uniformly disperse and there is little influence on the decrease in conductivity.
  • the mass ratio is more preferably 0.5 to 9, further preferably 1 to 6, and the mass ratio of 2 to 3 is particularly preferable because high transparent conductivity can be obtained.
  • a dispersion means at the time of preparation a carbon nanotube and a dispersing agent are used in a dispersion medium, and a conventional mixing and dispersing machine (for example, a ball mill, a bead mill, a sand mill, a roll mill, a homogenizer, an ultrasonic homogenizer, a high-pressure homogenizer, an ultrasonic device) , An attritor, a resolver, a paint shaker, etc.).
  • the method of preliminarily dispersing with a vibrating ball mill and then dispersing using an ultrasonic device is preferable because the dispersibility of the conductor in the obtained coating dispersion liquid is good.
  • the dispersion of carbon nanotubes preferably used in the production method of the present invention preferably has a pH in the range of 5.5 to 11.
  • acidic functional groups such as carboxylic acid that modifies the surface of the carbon nanotubes, carboxylic acids contained in the dispersant located around the carbon nanotubes, etc. Increases the degree of ionization of acidic functional groups.
  • the carbon nanotube or the dispersant around the carbon nanotube is negatively charged.
  • the carbon nanotubes or the dispersant around the carbon nanotubes repel each other, so that the dispersibility of the carbon nanotubes can be further increased and the bundle diameter can be reduced.
  • the pH of the carbon nanotube dispersion can be adjusted by adding an acidic substance or a basic substance according to the definition of Arrhenius to the carbon nanotube dispersion.
  • Acidic substances include, for example, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, borohydrofluoric acid, hydrofluoric acid, perchloric acid, organic carboxylic acids, phenols, organic sulfonic acids, etc. Is mentioned.
  • organic carboxylic acids include formic acid, acetic acid, succinic acid, benzoic acid, phthalic acid, maleic acid, fumaric acid, malonic acid, tartaric acid, citric acid, lactic acid, succinic acid, monochloroacetic acid, dichloroacetic acid, dichloroacetic acid, trichloroacetic acid, Fluoroacetic acid, nitroacetic acid, triphenylacetic acid and the like can be mentioned.
  • organic sulfonic acid examples include alkylbenzene sulfonic acid, alkyl naphthalene sulfonic acid, alkyl naphthalene disulfonic acid, naphthalene sulfonic acid formalin polycondensate, melamine sulfonic acid formalin polycondensate, naphthalene disulfonic acid, naphthalene trisulfonic acid, dinaphthylmethane.
  • examples include disulfonic acid, anthraquinone sulfonic acid, anthraquinone disulfonic acid, anthracene sulfonic acid, and pyrene sulfonic acid.
  • an acid that is likely to volatilize when dried after being applied such as hydrochloric acid and nitric acid, is preferable.
  • Examples of basic substances include sodium hydroxide, potassium hydroxide, calcium hydroxide, and ammonia.
  • a volatile base that volatilizes during coating and drying, such as ammonia.
  • the pH of the carbon nanotube dispersion liquid is adjusted by adding the acidic substance or basic substance to a desired pH while measuring the pH.
  • the pH measurement method include a method using pH test paper such as litmus test paper, a hydrogen electrode method, a quinhydrone electrode method, an antimony electrode method, and a glass electrode method.
  • the glass electrode method is preferable because it is simple and can provide necessary accuracy.
  • a substance having the opposite characteristics may be added to adjust the pH.
  • Nitric acid is preferable as an acidic substance applied for such adjustment, and ammonia is preferable as a basic substance.
  • a dispersion containing a conductor is applied on a substrate (or on an undercoat layer) and dried to obtain a conductive layer.
  • the conductive layer containing a conductor is formed through a coating process in which a dispersion liquid containing a conductor is applied onto a substrate, and then a drying process in which the dispersion medium is removed.
  • the method for applying the dispersion onto the substrate is not particularly limited. Known application methods such as spray coating, dip coating, spin coating, knife coating, gravure coating, slot die coating, bar coating, roll coating, screen printing, ink jet printing, pad printing, other types of printing, etc. can be used.
  • coating may be performed in multiple times and it may combine two different types of application
  • the most preferred application methods are gravure coating, bar coating, and slot die coating.
  • the drying process to remove the dispersion medium from the carbon nanotube dispersion containing the applied dispersant includes convection hot air drying that applies hot air to the substrate, and absorption of infrared rays into the substrate by radiation from an infrared dryer. Radiant electric heat drying which is heated and dried by changing to heat, conductive electric heat drying which is heated and dried by heat conduction from a wall surface heated by a heat medium, and the like. Of these, convection hot air drying is preferred because of its high drying rate.
  • the coating thickness when applying a dispersion containing a carbon atom-containing conductor such as a carbon tube on the substrate also depends on the concentration of the dispersion, so it can be adjusted as appropriate to obtain the desired surface resistance. Good.
  • the coating amount of the conductor in the present invention can be easily adjusted in order to achieve various uses requiring conductivity. If transparency is required, the preferred thickness is 0.1 to 10 mg / m 2 .
  • overcoat layer In the conductive laminate, there may be an overcoat layer. It is preferable to have an overcoat layer because the transparent conductivity, heat resistance stability, and heat and humidity resistance can be further improved.
  • both organic materials and inorganic materials can be used.
  • an inorganic material is preferable from the viewpoint of stability of resistance value.
  • the inorganic material include metal oxides such as silica, tin oxide, alumina, zirconia, and titania. Of these, silica is preferable from the viewpoint of stability of the resistance value.
  • the method for providing the overcoat layer is not particularly limited.
  • Known wet coating methods such as spray coating, dip coating, spin coating, knife coating, kiss coating, roll coating, gravure coating, slot die coating, bar coating, screen printing, ink jet printing, and pad printing can be used.
  • a dry coating method may be used.
  • physical vapor deposition such as sputtering or vapor deposition, chemical vapor deposition, or the like can be used.
  • the operation of providing the overcoat layer on the conductor may be performed in a plurality of times, or two or more different methods may be combined.
  • Preferred methods are gravure coating, bar coating, slot die coating, which are wet coatings.
  • an organosilane compound is preferably used as a method for forming an overcoat layer made of silica using wet coating.
  • a silica sol produced by hydrolyzing an organosilane compound such as tetraalkoxysilane such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, etc. is used as a solvent.
  • a dissolved solution can be used as a coating solution.
  • the said wet coating is performed using the said coating liquid.
  • the method of producing condensation of silanol groups or silanol groups and an alkoxy group at the time of solvent drying, and forming a silica thin film is mentioned.
  • the thickness of the overcoat layer can be controlled by adjusting the concentration in the coating solution and the thickness of the coating solution during coating. In applications where transparency is required, a thickness that effectively provides an antireflection effect due to optical interference is preferable because the light transmittance is improved. Therefore, the thickness of the overcoat layer is preferably in the range of 80 to 120 nm in total with the thickness of the undercoat layer as described above. In addition, by increasing the thickness of the overcoat layer, scattering of a dopant such as nitric acid that improves the conductivity of the conductor can be suppressed, and heat resistance can be improved.
  • a dopant such as nitric acid that improves the conductivity of the conductor
  • the thickness of the overcoat layer effective for preventing the scattering of the dopant is 40 nm or more, and considering the range of the total thickness of the undercoat layer and the overcoat layer for obtaining the antireflection effect, More preferably, the thickness is 40 to 110 nm.
  • Method for forming pattern from conductive laminate A method of patterning a conductive laminate using the carbon nanotubes produced by the above procedure as a conductor and a conductive laminate using graphene, a conductive polymer, or the like as a conductor will be described.
  • the conductor by applying a voltage in a state where the electrolytic solution is in contact with the conductor, the conductor is reduced and the conductivity of the desired portion is lost.
  • the resistance between the conductive layers separated through the portion from which the conductor is removed exceeds 10 M ⁇ , it is determined that the conductivity is lost.
  • the distance between the two terminals for measuring the resistance is within 10 mm.
  • the conductive layer in the present invention essentially includes a conductive layer containing a conductor, but the conductor may be impregnated in the above-described undercoat layer or overcoat layer.
  • An overcoat layer is also included in the concept of a conductive layer. This is because a conductor containing carbon such as a carbon nanotube has a relatively large shape, and thus easily penetrates into other layers. Furthermore, since carbon nanotubes are fibrous, the ease of leaching into other layers is even more remarkable.
  • the components not removed by the electrochemical reaction that is, the components of the undercoat layer, the conductor, and the components of the overcoat layer may remain in the conductive layer. Even if all the conductors are not removed, it can be determined that the conductivity is lost if the resistance exceeds 10 M ⁇ .
  • the material of the counter electrode is not limited as long as it is an electrochemically stable conductor in order to satisfy the above purpose.
  • Metals such as gold, silver, copper, iron, platinum, ruthenium, and carbons such as glassy carbon are used.
  • the voltage to be applied is not particularly limited as long as the reaction of formula (1) occurs at a sufficiently high speed, but it is preferably in the range of 5 to 15V. More preferably, it is 5 to 10V, and further preferably 5 to 7.5V.
  • examples of the electrolytic solution used in the present invention include pure water and an aqueous solution containing an electrolyte such as a sodium compound or a potassium compound.
  • the electrolytic solution preferably has ionic conductivity.
  • an electrolyte such as calcium chloride or sodium chloride may be added as necessary to improve ionic conductivity.
  • the distance between the conductive layer and the counter electrode is desirably as small as possible so that the conductive layer and the counter electrode do not contact each other.
  • a practical one is 10 to 1,000 ⁇ m.
  • This distance can be controlled by providing a spacer having a specific thickness between the conductive layer and the counter electrode. Therefore, the thickness of the spacer is preferably 10 to 1,000 ⁇ m.
  • the first method is a method in which a masking material is provided on a part of the surface of the conductive layer to prevent a part of the conductive layer from coming into contact with the electrolytic solution.
  • a patterned masking material is provided on the conductive layer of the conductive laminate before being patterned.
  • a photoresist is applied on the conductive laminate, pattern exposure and development are performed, and a photoresist having the obtained pattern is used as a masking material.
  • the photoresist either a solution type or a dry film resist type can be used. In addition, both negative and positive photoresists can be used.
  • FIG. 1 is a schematic view of an apparatus for removing a conductor from a conductive laminate using a patterned resist.
  • a sample composed of the base material 102, the conductive layer 103 and the patterned resist 104 is placed in the electrolytic solution 101.
  • the counter electrode 105 is also installed in the electrolytic solution 101.
  • the conductive layer 103 and the counter electrode 105 are connected by a conductive wire 106, and a voltage is applied using the conductive layer 103 as an anode and the counter electrode 105 as a cathode. Then, the conductor in the conductive layer 103 where the resist 104 does not exist decreases.
  • the second patterning method is a method using a patterned counter electrode. An example of removing the conductor using this method will be described with reference to FIG.
  • a conductive laminate 203 formed of a base material 201 and a conductive layer 202.
  • a patterned counter electrode 207 provided on the lower base member 205 is opposed to the conductive layer 202 with a small gap through the electrolytic solution 206.
  • a voltage is applied using the conductive layer 202 as an anode and the counter electrode 207 as a cathode, a part of the conductor of the conductive layer 202 decreases corresponding to the pattern shape of the counter electrode 207.
  • the conductive layer 202 and the counter electrode 207 be as close as possible within a range where they do not contact each other.
  • the distance between the conductive layer 202 and the counter electrode 207 is adjusted by the spacer 204.
  • a masking material having a pattern shape is provided on the counter electrode, and as a result, the counter electrode has a pattern shape with respect to the electrolytic solution.
  • the patterned spacer 304 serves as a masking material for the conductive layer 302, but it can be said that the spacer 304 forms a pattern of the counter electrode 307.
  • the lower electrode laminate 308 includes a lower substrate 305 and a counter electrode 307 provided thereon.
  • the counter electrode 307 faces the conductive layer 302 with the electrolytic solution 306 interposed therebetween.
  • a voltage is applied using the conductive layer 302 as an anode and the counter electrode 307 as a cathode.
  • the method using a patterned counter electrode and the method using a patterned spacer are superior in that a photolithography process is not necessary as compared to the method using a photoresist.
  • etchants for ITO and metal thin films are often strong acids, mixed acids, highly oxidizing or corrosive chemicals and strong alkalis, which are difficult to handle and require cost for handling equipment. There was.
  • etching is performed by applying a voltage in a state of being immersed in water, so that handling and equipment design are easy.
  • the removal rate and patterning accuracy of the conductor can be controlled by controlling the voltage according to the purpose. If the voltage is lowered, the removal rate of the conductor is reduced, and high patterning accuracy is obtained. Further, if the voltage is increased, the patterning accuracy is lowered, but the conductor removal rate can be increased and the productivity can be increased.
  • the conductive layer includes an insulator that does not undergo an electrochemical reaction with the conductor, the insulator remains even at the portion where the conductor is removed. Therefore, the visual difference between the conductor and the portion from which the conductor has been removed is small, and the patterning trace is difficult to visually recognize.
  • an insulator here, the inorganic material and organic material which comprise the undercoat layer and overcoat layer in a conductive laminated body at the time of using the said carbon nanotube as a conductor are illustrated, for example.
  • the conductive laminate according to the invention of the present invention is suitable for capacitive touch switch, capacitive touch panel or resistive touch panel applications.
  • the conductive laminate When used as a capacitive touch switch or a capacitive touch panel, the conductive laminate is patterned to form a patterned electrode.
  • a finger or the like comes into contact with the patterned electrode, a minute current flows through the conductor, and the capacitance that changes at that time is detected, and the operation or position as a switch is detected.
  • the present invention it is possible to provide a capacitive touch switch and a touch panel with small bone appearance.
  • two transparent electrodes including at least one conductive laminate of the present invention are installed in such a manner that the conductive surfaces face each other.
  • the transparent electrode is pressed with a finger or the like, and the position where the electrodes are in contact with each other is detected. At this time, it is necessary to pattern the ends of the conductive laminate.
  • the patterning method of the present invention can also be used for patterning a conductive laminate for a resistive touch panel.
  • ⁇ Measurement method> Surface resistance value A probe was brought into close contact with the central portion on the conductive layer side of the conductive laminate having a size of 5 cm ⁇ 10 cm, and the surface resistance value was measured at room temperature by a four-terminal method.
  • the apparatus used was a resistivity meter MCP-T360 manufactured by Dia Instruments, and the probe used was a 4-probe probe MCP-TPO3P manufactured by Dia Instruments.
  • FIG. 4 is a conceptual diagram of an apparatus used for a method for determining the presence or absence of insulation in the space portion of the pattern of the conductive laminate produced in Examples 1 to 8 and Comparative Example 1 described later.
  • the space refers to a portion where the conductor is removed and the conduction should be lost.
  • a positive terminal 402 and a negative terminal 403 of an ohmmeter 401 for measuring DC resistance are connected to the remaining conductor portions 404 and 406 separated by a space 405, respectively.
  • As the resistance meter 401 A & D Co., Ltd. digital multimeter AD-5536 was used.
  • the distance between the positive terminal and the negative terminal is 10 mm.
  • the terminal may be connected anywhere in the conductor remaining portion 503 as long as the position is 504A from the line segment a.
  • the distance between the two terminals for measuring the resistance was 10 mm.
  • a & D Co., Ltd. digital multimeter AD-5536 was used as the resistance meter. The resistance value between the terminals was measured, and when it exceeded 10 M ⁇ , it was judged that the terminal was insulated.
  • the thin wire portion 501 was also checked for conduction. Connect the + and-terminals of a resistance meter (not shown) to the two electrode connection parts 504 for confirming the continuity. When the resistance is 100 k ⁇ or less, it is determined that the continuity is established. Otherwise, it is determined that the continuity is not established. .
  • Reference numeral 601 denotes a conductive layer
  • reference numeral 602 denotes a space from which the conductor is removed.
  • the width X of the portion from which the conductor has been removed is about 1 mm.
  • Height measurement at line segment A was performed across the site from which the conductor was removed.
  • the width Y of the measurement site is 5 mm.
  • the thickness of the overcoat layer is about 60 nm, when the difference between the maximum value and the minimum value of the height profile on the line segment A is 10 nm or less, the overcoat layer remains. It was judged.
  • the DM30-26G-4 was adjusted with isopropyl alcohol to a solid content of 1% by mass to obtain a coating solution for forming an undercoat layer.
  • As a substrate a biaxially stretched polyethylene terephthalate film having a thickness of 188 ⁇ m, “Lumirror” (registered trademark) U46 manufactured by Toray Industries, Inc. was used.
  • the rotation ratio of the gravure roll with respect to the line speed was set to 1.5 times, and the coating solution for the undercoat layer was applied onto the substrate. After the application, it was dried in a dryer at 80 ° C. for 1 minute.
  • the thickness of the undercoat layer produced by this method was about 40 nm.
  • Example of catalyst preparation loading of metal salt catalyst on magnesia
  • 2.46 g of ammonium iron citrate was dissolved in 500 mL of methanol.
  • 100.0 g of magnesium oxide MJ-30 manufactured by Iwatani Chemical Industry Co., Ltd.
  • the resulting suspension was concentrated to dryness at 40 ° C. under reduced pressure. did.
  • the obtained solid was made into powder, and the powder was heated and dried at 120 ° C. to remove methanol to obtain a catalyst body in which a metal salt was supported on magnesium oxide powder.
  • the obtained solid content was used with a particle size in the range of 20 to 32 mesh (0.5 to 0.85 mm) while being finely divided in a mortar on a sieve. Content of the iron atom contained in the obtained catalyst body was 0.38 mass%. The bulk density was 0.61 g / mL. The above operation was repeated and subjected to the following experiment.
  • the reactor 703 is a cylindrical quartz tube having an inner diameter of 75 mm and a length of 1,100 mm.
  • a quartz sintered plate 702 is provided at the center of the quartz tube, a mixed gas introduction tube 708 which is an inert gas and source gas supply line is provided at the lower portion of the quartz tube, and an exhaust gas tube 706 is provided at the upper portion.
  • the catalyst layer 704 was formed by taking 132 g of the solid catalyst body prepared in the catalyst preparation example described above and introducing it onto the quartz sintered plate 702 at the center of the reactor installed in the vertical direction. While heating the catalyst layer until the temperature in the reaction tube reaches about 860 ° C., nitrogen gas is supplied at 16.5 L / min from the bottom of the reactor toward the top of the reactor using the mass flow controller 707, and the catalyst layer is It was distributed to pass. After that, while supplying nitrogen gas, methane gas was further introduced at 0.78 L / min for 60 minutes using a mass flow controller 707 and aerated to pass through the catalyst body layer to cause a chemical reaction.
  • the contact time (W / F) obtained by dividing the mass of the solid catalyst body by the flow rate of methane at this time was 169 minutes ⁇ g / L, and the linear velocity of the gas containing methane was 6.55 cm / sec.
  • the quartz reaction tube was cooled to room temperature while the introduction of methane gas was stopped and nitrogen gas was passed through at 16.5 L / min.
  • the heating was stopped and the mixture was allowed to stand at room temperature. After the temperature reached room temperature, the carbon nanotube-containing composition containing the catalyst body and the carbon nanotubes was taken out from the reactor.
  • this carbon nanotube paste was diluted with ion-exchanged water so that the concentration of carbon nanotubes was 0.15% by mass, and adjusted to pH 10 with 28% by mass ammonia aqueous solution again with respect to 10 g of the diluted solution.
  • the aqueous solution was subjected to a dispersion treatment at an output of an ultrasonic homogenizer (manufactured by Ieda Trading Co., Ltd., VCX-130) at 20 W, 1.5 minutes (2 kW ⁇ min / g) at 10 ° C. or lower while cooling with ice.
  • an ultrasonic homogenizer manufactured by Ieda Trading Co., Ltd., VCX-130
  • the obtained liquid was centrifuged at 10,000 G for 15 minutes with a high-speed centrifuge (Tomy Seiko Co., Ltd., MX-300) to obtain 9 g of a carbon nanotube dispersion. Thereafter, water was added to prepare a coating stock solution having a final concentration of 0.04% by mass of the aggregate of carbon nanotubes.
  • This coating liquid was applied on the carbon nanotube layer under the condition of a gravure roll UR150 line and a gravure roll rotation ratio of 1.5 times the line speed, and then dried in a dryer at 115 ° C. for 1 minute.
  • the overcoat thickness produced by this method was about 60 nm.
  • FIG. 3 is a conceptual cross-sectional view showing a configuration for producing a patterned conductive laminate.
  • a conductive laminate 303 obtained by laminating a conductive layer 302 on a substrate 301 was used as an object to be patterned.
  • a copper plating film (“METAL ROYAL” (registered trademark) PI-38N-CCS-08E0 manufactured by Toray Film Processing Co., Ltd.) is used as the lower electrode laminated body 308, and the conductive layer 302 and the counter electrode 307 made of copper are provided with a spacer 304 (Japan) It was made to oppose through a solder resist NPR-3300 (thickness 30 ⁇ m) manufactured by Polytech Co., Ltd.
  • the conductive layer 302 was electrically connected to an electrode outlet (not shown), and the counter electrode 307 was also connected to the electrode outlet (not shown). Each current outlet was connected to an electrode terminal of a DC stabilized power supply PMC-70-1A manufactured by Kikusui Electronics Co., Ltd., and a DC voltage was applied between the conductive layer 302 and the counter electrode 307.
  • a positive voltage is applied to the conductive layer 302
  • it is represented by a positive voltage value.
  • a case where a positive voltage is applied to the counter electrode 307 is represented by a negative voltage value.
  • Method 2 for producing patterned conductive laminate A method for producing a patterned conductive laminate will be described with reference to FIGS. 1 and 8.
  • a dry film negative resist (“SUNFORT” (registered trademark) AQ209A manufactured by Asahi Kasei E-Materials Co., Ltd.) is applied on the conductive layer surface of the conductive laminate, and a roll laminator (VA-700 manufactured by Taisei Laminator Co., Ltd.) with a roll temperature set at 100 ° C. ) And a mask aligner (Mikasa Co., Ltd., MA-) through a photomask shown in FIG.
  • SUNFORT dry film negative resist
  • VA-700 manufactured by Taisei Laminator Co., Ltd.
  • MA- mask aligner
  • the electric circuit shown in FIG. 1 was constructed and a DC voltage was applied.
  • the electrolytic solution 101 was pure water
  • the counter electrode 105 was a 1 mm thick copper plate.
  • the conductive laminate on which the patterned resist is formed is immersed in a 3% by mass aqueous sodium hydroxide solution at 50 ° C. for 30 seconds to remove the dry film resist, thereby forming a patterned conductive laminate. Obtained.
  • a positive voltage is applied to the conductive layer 103, it is represented by a positive voltage value.
  • a case where a positive voltage is applied to the counter electrode 105 is represented by a negative voltage value.
  • Example 1 An undercoat layer was formed in accordance with [Undercoat layer formation example] described above. On the undercoat layer, a carbon nanotube dispersion was applied under the conditions of a gravure roll UR120 line and a gravure roll peripheral speed ratio of 1.2 times the line speed to form a carbon nanotube layer. Since the thickness of the dispersion can be predicted from the number of gravure roll lines and the peripheral speed ratio of the gravure roll to the line speed, the design film thickness of the carbon nanotube can also be calculated.
  • An overcoat layer was formed on the carbon speed ratio carbon nanotube layer by the method of [Overcoat layer formation example] to prepare a conductive laminate.
  • the surface resistance value was 600 ⁇ / ⁇ , and the total light transmittance was 90%.
  • a DC voltage of 10 V was applied to this conductive laminate for 2 seconds in accordance with [Method 1 for producing patterned conductive laminate], it was confirmed that the pattern lines were insulated.
  • Example 1 and Table 2 show the coating conditions of the carbon nanotube dispersion liquid in each example and comparative example (number of gravure roll lines, peripheral speed ratio of gravure roll to line speed), design weight of carbon nanotube, and presence / absence of overcoat layer
  • a conductive laminate was produced in the same manner as in Example 1 except that.
  • the produced conductive laminate was patterned in the same manner as in Example 2 with the applied voltage and voltage application time shown in Table 2.
  • Example 7 Example 1 with an applied voltage and voltage application time shown in Table 2 using a graphene film (size: 50 mm ⁇ 50 mm) manufactured by Itricks Co., Ltd., having a PET film as a base material and graphene as a conductive layer as a conductor Patterning was performed in the same manner as above.
  • Example 8 Using an NCF-100 manufactured by Nagase Sangyo Co., Ltd., which has a film as a base material and a conductive polymer as a conductive layer, the same applied voltage and voltage application time shown in Table 2 as in Example 1. Patterned.
  • Example 9 A conductive laminate was produced in the same manner as in Example 1. The conductive laminate was subjected to a DC voltage of 5 V for 20 seconds in accordance with [Method 2 for producing patterned conductive laminate] described above. It was confirmed that this patterned conductive laminate had the thin wire portion 501 conducting and the space 502 could be insulated.
  • Example 10 A patterned conductive laminate was obtained in the same manner as in Example 9 except that the DC voltage condition to be applied was changed to 5 V and 60 seconds. It was confirmed that the patterned conductive laminate also had the thin wire portion 501 conducting and the space 502 could be insulated.
  • the number of gravure roll lines and the carbon nanotube design weight when forming the carbon nanotube layers of Examples 1 to 6, 9, 10 and Comparative Example 1 are shown in Table 1, and the overcoat layers of Examples 1 to 10 and Comparative Example 1 are compared.
  • Presence / absence, overcoat layer thickness, surface resistance of conductive laminate, total light transmittance, applied voltage, voltage application time, presence / absence of space insulation, presence / absence of thin line conduction, and presence / absence of overcoat layer after patterning It shows in Table 2.
  • the present invention can be applied with or without a layer.
  • the overcoat layer remained even after patterning, and the boundary between the pattern line and the space was hardly visible.
  • this technique is not limited to a conductive laminate using a carbon nanotube as a conductor, but a conductive laminate containing a conductor containing carbon atoms such as graphene or a conductive polymer in the conductive layer. It turns out that it is effective.
  • the conductive laminate can be patterned by forming a patterned resist on the conductive laminate.
  • Example 11 A patterned conductive laminate was manufactured in the same manner as in Example 1 except that the pattern of the photomask was changed to a shape in which the capacitive touch switch operated. When this was used as a capacitive touch switch and a drive circuit was attached, it was confirmed that it operated as a capacitive touch switch.
  • Example 12 A patterned conductive laminate was manufactured in the same manner as in Example 10 except that the pattern of the photomask was changed to a shape in which the capacitive touch panel operated. When this was used as a capacitive touch panel and a drive circuit was attached, it was confirmed that it operated as a capacitive touch panel.
  • the patterned conductive laminate obtained by the production method of the present invention can be widely used for capacitive touch switches, capacitive touch panels, resistive touch panels, solar cell electrodes, and the like.
  • Electrolytic solution 102 Base material 103: Conductive layer 104: Resist 105: Counter electrode 106: Conductive wire 201: Base material 202: Conductive layer 203: Conductive laminated body 204: Spacer 205: Lower base material 206: Electrolyte solution 207: Counter electrode 301: Substrate 302: Conductive layer 303: Conductive laminate 304: Spacer 305: Lower substrate 306: Electrolyte 307: Counter electrode 308: Lower electrode laminate 401: Resistance meter 402: + terminal 403:-terminal 404: Conductor Remaining portion 405: Space 406: Conductor remaining portion 501: Fine wire portion 502: Space 503: Conductor remaining portion 504A, 504B: Conduction confirmation electrode connection portion 601: Conductive layer 602: Space 701: Electric furnace 702: Sintered quartz Plate 703: Reactor 704: Catalyst layer 705: Thermocouple 706: Exhaust gas pipe 7

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  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing Of Electric Cables (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne un procédé pour obtenir un stratifié conducteur, dans lequel la formation de motifs est effectuée en un court laps de temps sans utiliser de liquide très corrosif, tel qu'un acide. Le procédé de production de stratifié conducteur à motifs comprend une étape dans laquelle une tension est appliquée à un stratifié conducteur qui comprend séquentiellement une base et une couche conductrice contenant des conducteurs qui renferment des atomes de carbone dans un état où une contre-électrode agit en présence d'une solution électrolytique, la couche conductrice étant utilisée en tant qu'électrode anode et la contre-électrode en tant qu'électrode cathode, de telle sorte que certains conducteurs de la couche conductrice sont retirés du stratifié conducteur.
PCT/JP2014/072578 2013-09-02 2014-08-28 Stratifié conducteur à motifs et son procédé de production WO2015030115A1 (fr)

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TWI548586B (zh) * 2015-06-10 2016-09-11 國立臺灣科技大學 異維度奈米複材的製造方法及異維度奈米複材
KR101994368B1 (ko) * 2016-09-21 2019-06-28 삼성에스디아이 주식회사 태양전지의 전극 패턴을 형성하는 방법, 이를 이용하여 제조된 전극 및 태양전지
CN106686778B (zh) * 2017-01-13 2023-01-06 无锡格菲电子薄膜科技有限公司 图案化导电膜提升、控制导电膜阻值的方法及其电发热膜

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JPH08144098A (ja) * 1994-11-28 1996-06-04 Asahi Denka Kogyo Kk 酸化錫膜のエッチング方法及び装置
JPH11203963A (ja) * 1998-01-19 1999-07-30 Nippon Sheet Glass Co Ltd 導電膜のエッチング方法
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JP2013008897A (ja) * 2011-06-27 2013-01-10 Toray Ind Inc 導電膜除去方法および導電膜除去剤
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CN1235271C (zh) * 1995-10-17 2006-01-04 佳能株式会社 生产半导体器件的工艺
KR101087829B1 (ko) * 2009-06-12 2011-11-30 한양대학교 산학협력단 전기화학반응을 이용한 탄소 패턴 형성방법
TWI409883B (zh) * 2010-11-29 2013-09-21 E Ink Holdings Inc 圖案化金屬層之方法以及利用其之半導體元件製造方法

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JPS59143320A (ja) * 1983-02-04 1984-08-16 Tdk Corp パタ−ン化された導電性層を形成する方法
JPH08144098A (ja) * 1994-11-28 1996-06-04 Asahi Denka Kogyo Kk 酸化錫膜のエッチング方法及び装置
JPH11203963A (ja) * 1998-01-19 1999-07-30 Nippon Sheet Glass Co Ltd 導電膜のエッチング方法
JP2008243622A (ja) * 2007-03-27 2008-10-09 Gunze Ltd 透明面状体及び透明タッチスイッチ
US20130207294A1 (en) * 2010-07-12 2013-08-15 Hanwha Chemical Corporation Conductive Paint Composition and Method for Manufacturing Conductive Film Using the Same
JP2013008897A (ja) * 2011-06-27 2013-01-10 Toray Ind Inc 導電膜除去方法および導電膜除去剤

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