WO2017208925A1 - 透明導電パターンの形成方法 - Google Patents
透明導電パターンの形成方法 Download PDFInfo
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- WO2017208925A1 WO2017208925A1 PCT/JP2017/019331 JP2017019331W WO2017208925A1 WO 2017208925 A1 WO2017208925 A1 WO 2017208925A1 JP 2017019331 W JP2017019331 W JP 2017019331W WO 2017208925 A1 WO2017208925 A1 WO 2017208925A1
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- transparent conductive
- conductive pattern
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M1/00—Inking and printing with a printer's forme
- B41M1/12—Stencil printing; Silk-screen printing
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/52—Electrically conductive inks
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
- H05K3/1216—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns by screen printing or stencil printing
Definitions
- the present invention relates to a method for forming a transparent conductive pattern.
- Transparent conductive films include liquid crystal displays (LCD), plasma display panels (PDP), organic electroluminescence (OLED), transparent electrodes for solar cells (PV) and touch panels (TP), antistatic (ESD) films, and electromagnetic shielding (EMI). ) It is used in various fields such as film, and (1) low surface resistance, (2) high light transmittance, and (3) high reliability are required.
- LCD liquid crystal displays
- PDP plasma display panels
- OLED organic electroluminescence
- PV transparent electrodes for solar cells
- TP touch panels
- ESD antistatic
- EMI electromagnetic shielding
- the surface resistance is in the range of 10 to 300 ⁇ / ⁇ and the light transmittance is 85% or more in the visible light region. More preferable ranges are a surface resistance of 20 to 100 ⁇ / ⁇ and a light transmittance of 90% or more.
- the transparent electrode of the OLED it is preferable that the surface resistance is in the range of 10 to 100 ⁇ / ⁇ and the light transmittance is 80% or more in the visible light region. More preferable ranges are a surface resistance of 10 to 50 ⁇ / ⁇ and a light transmittance of 85% or more.
- the surface resistance is in the range of 5 to 100 ⁇ / ⁇ and the light transmittance is 65% or more in the visible light region. More preferable ranges are a surface resistance of 5 to 20 ⁇ / ⁇ and a light transmittance of 70% or more.
- the surface resistance is preferably in the range of 100 to 1000 ⁇ / ⁇ , and the light transmittance is preferably 85% or more in the visible light region. More preferably, the surface resistance is in the range of 150 to 500 ⁇ / ⁇ , and the light transmittance is 90% or more in the visible light region.
- ITO indium tin oxide
- ITO film formation a vacuum manufacturing apparatus is required, which requires a long manufacturing time and a high cost.
- ITO is difficult to be applied to a substrate provided with flexibility because cracks are generated due to physical stress such as bending and are easily broken.
- Patent Document 1 a conductive material containing metal nanowires
- Non-Patent Document 1 a conductive material containing a nanostructured conductive component
- the conductive material containing metal nanowires is suitable as an “ITO substitute material” because it exhibits low surface resistance and high light transmittance, and also has flexibility.
- the transparent conductive film requires pattern formation according to the use in order to be used as a transparent electrode.
- a method for forming a pattern with a conductive material containing metal nanowires a resist is formed as in the case of ITO pattern formation.
- a photolithography method using a material is generally used.
- a step of forming a layer having photosensitivity for pattern formation on the layer containing metal nanowires is necessary.
- the development process of the photosensitive layer and the removal process of the layer including the exposed metal nanowires are necessary, so that the silver nanowires in the removal region are wasted and the waste solution treatment of the developer is necessary. There was also a case.
- a step of removing the photosensitive layer may be necessary.
- a pattern directly on the silver nanowires by a printing method such as ink jet printing, screen printing, gravure printing, or flexographic printing.
- a binder resin is required to perform printing, and in order to ensure transparency, it is necessary to reduce the amount of silver nanowires used. Therefore, the binder resin used covers the surface of the silver nanowires and becomes conductive. There was a problem of not expressing. In addition, when the binder resin is not used, there is a problem that the pattern is broken when the solvent is dried, even if the pattern cannot be secured at the time of printing or the pattern can be barely secured immediately after printing.
- An object of the present invention is to reduce damage to metal nanowires and / or metal nanotubes in screen printing using a transparent conductive ink containing metal nanowires and / or metal nanotubes as a conductive component.
- An object of the present invention is to provide a transparent conductive pattern forming method capable of forming a transparent conductive pattern and suppressing manufacturing cost and environmental load.
- the present invention includes the following embodiments.
- a transparent conductive ink containing at least one of metal nanowires and metal nanotubes and a dispersion medium is screen-printed with an attack angle of a squeegee tip contacting the screen mask in the range of 1 to 30 °.
- a method for forming a transparent conductive pattern is
- the organic compound of the shape retaining material is diglycerin, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, xylulose, ribulose, bornylcyclohexanol, borneol, isobornylcyclohexanol.
- a transparent conductive ink containing at least one of metal nanowires and metal nanotubes and a dispersion medium is used, and an attack angle of a squeegee tip contacting the screen mask is in the range of 1 to 30 °.
- screen printing FIG. 1 shows a conceptual diagram when screen printing is performed with an attack angle of the squeegee tip in the range of 1 to 30 °.
- the substrate 1 and the screen mask 2 are arranged with a clearance of a constant interval, and the printing direction is applied while the squeegee 3 is pressed against the screen mask 2 to bring the substrate 1 and the screen mask 2 into close contact with each other. 4, the transparent conductive ink 5 placed on the screen mask 2 is pushed out to the substrate 1 side to perform screen printing.
- the attack angle 6 is determined by both the angle (mounting angle) 8 of the squeegee 3 mounted on the printing apparatus and the angle 7 (see FIG. 2) of the squeegee tip (part contacting the screen mask 2).
- the mounting angle 8 of the squeegee 3 can be adjusted within a range of 60 to 90 °, and the tip end angle 7 of the squeegee 3 can be arbitrarily processed. It is preferable to use a squeegee 3 having a tip processed so as to reduce the attack angle 6.
- the sword squeegee when viewed from the side, has a line-symmetric gradient from the center of the tip in the thickness direction of the squeegee to both principal surfaces.
- An example of a squeegee 3 that can be preferably used in the present embodiment is a sword squeegee having a symmetrical gradient.
- FIG. 2B at least one main squeegee from the tip of the squeegee 3 is used. Any surface having a slope may be used.
- the attack angle 6 is an angle formed by the inclined surface and the flat surface when the squeegee 3 is mounted on the printing apparatus, and is expressed by (Squeegee 3 tip portion angle 7 ⁇ (90 ° ⁇ mounting angle 8)). Calculated. In order to set the attack angle in the range of 1 to 30 °, a squeegee tip portion angle 7 of 10 to 60 ° can be preferably used.
- the mounting angle 8 is an angle formed by the central axis and a plane (the surface of the substrate 1) (see FIG. 1).
- attack angle 6 at the tip of the squeegee is 30 ° or less, the shearing force accompanying the ink rolling is reduced, so that repeated printing can be performed while reducing damage such as bending and cutting of the metal nanowires and metal nanotubes.
- the hardness of the rubber squeegee 3 is not particularly limited.
- a JIS K6031 standard hardness meter having an Hs (Shore) hardness of 55 to 90 can be used.
- Hs Hydraulic Standard hardness meter
- As the squeegee 3 as described above for example, a sword squeegee manufactured by APOLAN International, a sword squeegee manufactured by Bando Chemical Co., Ltd., or a one-sword squeegee can be used.
- the squeegee speed for screen printing when the attack angle 6 at the tip of the squeegee is 1 to 30 ° is preferably 5 to 800 mm / sec, more preferably 10 to 400 mm / sec, and still more preferably 20 to 200 mm / sec. If the squeegee speed is 5 mm / sec or more, the productivity is good, and if the squeegee speed is 800 mm / sec or less, deterioration of the plate separation due to an excessive amount of ink transferred during printing can be suppressed.
- the clearance when screen printing is performed with the attack angle 6 at the tip of the squeegee in the range of 1 to 30 ° is 1/600 to 1/1 of the inner dimension of the screen frame.
- 150 is preferable, and 1/450 to 1/200 is more preferable. If it is 1/600 or more of the inner size of the screen frame, it is possible to suppress deterioration of the plate separation during printing, and if it is 1/150 or less, it is possible to suppress damage to the screen mask 2 in repeated printing. it can. In addition, when a screen mask with high strength is used, damage to the screen mask 2 may be suppressed even if it is 1/100 or less of the inner dimension of the screen frame.
- ink is put on the screen mask 2, and the ink on the screen mask 2 is developed with a scraper, and then printed on the substrate with the squeegee 3.
- the amount of the transparent conductive ink 5 placed on the screen mask is large, damage to the metal nanowires and / or metal nanotubes in the transparent conductive ink 5 is accumulated by a squeegee operation in printing. For this reason, when printing in large quantities repeatedly, an operation of limiting the amount of the transparent conductive ink 5 placed on the screen mask 2 and appropriately replenishing the screen mask 2 with the transparent conductive ink 5 consumed by printing.
- the average length of the metal nanowires and / or metal nanotubes in the transparent conductive ink 5 can be maintained at a desired length.
- the transparent conductive ink 5 for screen printing used in the method for forming a transparent conductive pattern of the present embodiment contains at least one of metal nanowires and metal nanotubes and a dispersion medium, and retains the pattern shape by screen printing. Any suitable viscosity can be applied. It is preferable that the dispersion medium contains the following shape-retaining material because the metal nanowires and / or metal nanotubes can be dispersed well.
- the shape holding material is an organic compound having a molecular weight range of 150 to 500, and the viscosity of the dispersion medium containing the shape holding material at 25 ° C. is 1.0 ⁇ 10 3 to 2.0 ⁇ 10 6 mPa ⁇ s. Preferably there is.
- the organic compound is a liquid in the above viscosity range at 25 ° C.
- the shape-retaining material can be composed only of the organic compound.
- the viscosity at 25 ° C. is higher than the above viscosity range or solid at 25 ° C., it is mixed in advance with an appropriate solvent (a solvent capable of dissolving an organic compound, such as a viscosity adjusting solvent described later). , Dissolved) to form a dispersion medium.
- the viscosity at 25 ° C. of the dispersion medium is more preferably in the range of 5.0 ⁇ 10 4 to 1.0 ⁇ 10 6 mPa ⁇ s.
- the viscosity is a value measured using a conical plate type rotational viscometer (cone plate type).
- the molecular weight of the organic compound used as the shape-retaining material is large, the shape-retaining material cannot be removed efficiently during sintering, and the resistance does not decrease. Therefore, the molecular weight is 500 or less, preferably 400 or less, more preferably 300 or less.
- Such an organic compound is preferably a compound containing a hydroxyl group, for example, a monosaccharide, a polyol, a quaternary carbon atom and / or a compound having an alkyl group having a bridged ring skeleton and a hydroxyl group, such as diglycerin, Examples include 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, xylulose, ribulose, bornylcyclohexanol, borneol, isobornylcyclohexanol, isoborneol and the like.
- the content of the shape-retaining material in the ink is preferably 10 to 90% by mass and more preferably 30 to 80% by mass with respect to the total mass of the dispersion medium.
- the ink has a viscosity suitable for printing, and printing can be performed without problems such as pattern collapse and stringiness during printing.
- the shape-retaining material itself is desirably a viscous liquid that is within the above-described preferred dispersion medium viscosity range, but is mixed with another viscosity adjusting solvent so as to satisfy the above viscosity range.
- a transparent conductive ink may be prepared by preparing a dispersion medium having a viscosity of 5 and dispersing metal nanowires and / or metal nanotubes as a conductive component in the dispersion medium.
- Metal nanowires and metal nanotubes are metals having diameters in the order of nanometers.
- Metal nanowires are conductive materials having a wire shape, and metal nanotubes are porous or nonporous tube shapes.
- wire shape and tube shape are linear, but the former is intended to have a hollow center, and the latter is intended to have a hollow center.
- the property may be flexible or rigid. Either the metal nanowire or the metal nanotube may be used, or a mixture of both may be used.
- An optimal embodiment includes silver nanowires.
- the diameter of the metal nanowire and / or the metal nanotube in the transparent conductive ink, the length of the major axis, and the aspect ratio have a constant distribution. This distribution is selected so that the coating film obtained from the transparent conductive ink of the present embodiment has a high total light transmittance and a low surface resistance.
- the average diameter of the metal nanowire and the metal nanotube is preferably 1 to 500 nm, more preferably 5 to 200 nm, still more preferably 5 to 100 nm, and particularly preferably 10 to 100 nm.
- the average length of the major axis of the metal nanowire and / or metal nanotube is preferably 1 to 100 ⁇ m, more preferably 1 to 50 ⁇ m, still more preferably 2 to 50 ⁇ m, and particularly preferably 5 to 30 ⁇ m.
- the average diameter and the average length of the major axis satisfy the above range, and the average aspect ratio is preferably greater than 5, more preferably 10 or more. 100 or more is more preferable, and 200 or more is particularly preferable.
- the aspect ratio is a value obtained by a / b when the average diameter of the metal nanowire and / or the metal nanotube is approximated to b and the average length of the major axis is approximated to a.
- metal nanowires and / or metal nanotubes As a method for producing metal nanowires and / or metal nanotubes, known production methods can be used. For example, silver nanowires can be synthesized by reducing silver nitrate in the presence of polyvinylpyrrolidone using the Poly-ol method (see Chem. Mater., 2002, 14, 4736). Similarly, gold nanowires can be synthesized by reducing chloroauric acid hydrate in the presence of polyvinylpyrrolidone (see J. Am. Chem. Soc., 2007, 129, 1733). Detailed techniques for the synthesis and purification of silver nanowires and gold nanowires are described in detail in International Publication Nos. WO2008 / 073143 and International Publication No. 2008/046058.
- Gold nanotubes having a porous structure can be synthesized by reducing a chloroauric acid solution using silver nanowires as a template.
- the silver nanowire used as a template is dissolved in a solution by an oxidation-reduction reaction with chloroauric acid, and as a result, a gold nanotube having a porous structure is formed (J. Am. Chem. Soc., 2004, 126, 3892). -3901).
- the content of metal nanowires and / or metal nanotubes in the transparent conductive ink according to this embodiment is good dispersibility and good pattern formation property of the coating film obtained from the transparent conductive ink, high conductivity and good
- the amount of metal nanowires and / or metal nanotubes is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, based on the total mass of the transparent conductive ink. More preferably, the amount is 0.1 to 2% by mass. If the metal nanowires and / or metal nanotubes are 0.01% by mass or more, it is not necessary to print the transparent conductive layer very thick in order to ensure the desired conductivity. Generation
- the transparent conductive ink according to the present embodiment is an optional component other than the above components (shape holding material, viscosity adjusting solvent, metal nanowire, metal nanotube), for example, binder resin, corrosion inhibitor, An adhesion promoter, a surfactant and the like may be included.
- Binder resins include polyacryloyl compounds such as polymethyl methacrylate, polyacrylate and polyacrylonitrile; polyvinyl alcohol; polyesters such as polyethylene terephthalate and polyethylene naphthalate; polycarbonates; highly conjugated polymers such as novolacs; polyimides, polyamideimides and polyethers Imides such as imides; polysulfides; polysulfones; polyphenylenes; polyphenyl ethers; polyurethanes; epoxies; aromatic polyolefins such as polystyrene, polyvinyltoluene and polyvinylxylene; aliphatic polyolefins such as polypropylene and polymethylpentene; alicyclic rings such as polynorbornene Olefin, poly-N-vinylpyrrolidone, poly-N-vinylcaprolactam, poly-N-vinyl Poly-N-vinyl compounds such as cetamide; Acrylon
- examples of the corrosion inhibitor include benzotriazole
- examples of the adhesion promoter include 2-hydroxymethylcellulose
- examples of the surfactant include trade name F-472SF (manufactured by DIC Corporation).
- the transparent conductive ink can be produced by appropriately selecting the above-described components by stirring, mixing, heating, cooling, dissolution, dispersion, or the like by a known method.
- the viscosity of the transparent conductive ink according to this embodiment is preferably 100 to 2 ⁇ 10 5 mPa ⁇ s, more preferably 10 3 to 5 ⁇ 10 4 mPa ⁇ s at 25 ° C.
- the viscosity is a value measured using a conical plate type rotational viscometer (cone plate type).
- the substrate for pattern printing may be rigid (rigid) or bend easily (flexibility). Moreover, it may be colored.
- the substrate include materials such as glass, polyimide, polycarbonate, polyethersulfone, acrylic resin, polyester (polyethylene terephthalate, polyethylene naphthalate, etc.), polyolefin (including cycloolefin polymer), polyvinyl chloride, and the like. These preferably have a high total light transmittance and a low haze value.
- a resin film is preferable in that it has flexibility.
- the film thickness is preferably 1 mm or less, more preferably 500 ⁇ m or less, further preferably 250 ⁇ m or less, and particularly preferably 125 ⁇ m or less.
- Cycloolefin polymers include norbornene hydrogenated ring-opening metathesis polymerization type cycloolefin polymer (ZEONOR (registered trademark, manufactured by ZEON Corporation), ZEONEX (registered trademark, manufactured by ZEON Corporation), ARTON (registered trademark, manufactured by JSR Corporation).
- the amount of the transparent conductive ink applied to the substrate is determined in consideration of the film thickness of the transparent conductive pattern required by the application.
- the film thickness is selected based on the application.
- the desired film thickness can be obtained by adjusting the application amount of the transparent conductive ink and the conditions of the application method.
- the film thickness is preferably as thick as possible from the viewpoint of low surface resistance and as thin as possible from the viewpoint of suppressing the occurrence of display defects due to steps, so that when considering these in total, a film thickness of 5 to 500 nm is preferable.
- a film thickness of 5 to 200 nm is more preferable, and a film thickness of 5 to 100 nm is more preferable.
- the printed (coated) transparent conductive ink is dried by heating the coated material as necessary.
- the heating temperature varies depending on the liquid component constituting the dispersion medium, but if the drying temperature is too high, the formed pattern may not be retained. Therefore, the drying temperature is at most 120 ° C., more preferably 100 ° C. or less. Since the initial drying temperature is particularly important, it is particularly preferable to start the drying from about 40 to 80 ° C. and raise the temperature stepwise within a range not exceeding 120 ° C. as necessary.
- a viscous liquid shape-retaining material generally has a high boiling point, and when a viscosity-adjusting solvent having a lower boiling point than the shape-retaining material coexists in the dispersion medium, the low-boiling viscosity adjusting solvent is preferentially distilled off. Therefore, the viscosity of the dispersion medium increases by drying, and the collapse of the print pattern during drying is suppressed.
- the surface resistance and total light transmittance of the transparent conductive pattern obtained were adjusted for the film thickness, that is, the coating amount of the composition and the conditions of the coating method, and the metal nanowire or metal nanotube in the transparent conductive ink according to this embodiment By adjusting the density, it is possible to obtain a desired value.
- the coating film obtained as described above preferably has a surface resistance value of 5 to 1000 ⁇ / ⁇ , a total light transmittance of 60% or more, and a surface resistance value of 10 to 200 ⁇ / ⁇ . More preferably, the total light transmittance is 80% or more.
- the surface resistance of the transparent conductive ink according to the present embodiment is lowered to some extent even if it is dried, but it is preferable to irradiate with pulsed light in order to make it more efficient.
- pulse light means light having a short light irradiation period (irradiation time).
- the second light irradiation period (on) means light irradiation having a period (irradiation interval (off)) in which light is not irradiated.
- FIG. 3 shows that the light intensity of the pulsed light is constant, the light intensity may change within one light irradiation period (on).
- the pulsed light is emitted from a light source including a flash lamp such as a xenon flash lamp.
- the metal nanowires or metal nanotubes deposited on the substrate are irradiated with pulsed light.
- irradiation is repeated n times, one cycle (on + off) in FIG. 3 is repeated n times.
- an electromagnetic wave having a wavelength range of 1 pm to 1 m can be used, preferably an electromagnetic wave having a wavelength range of 10 nm to 1000 ⁇ m (from far ultraviolet to far infrared), more preferably 100 nm to 2000 nm.
- Electromagnetic waves in the wavelength range can be used. Examples of such electromagnetic waves include gamma rays, X-rays, ultraviolet rays, visible light, infrared rays, microwaves, radio waves on the longer wavelength side than microwaves, and the like. In consideration of conversion to thermal energy, if the wavelength is too short, damage to the shape-retaining material, the resin base material on which pattern printing is performed, etc. is not preferable.
- the wavelength range is preferably the ultraviolet to infrared range, more preferably the wavelength range of 100 to 2000 nm, among the wavelengths described above.
- the irradiation time (on) of one pulsed light is preferably in the range of 20 microseconds to 50 milliseconds, although it depends on the light intensity. If it is shorter than 20 microseconds, the sintering of the metal nanowire or the metal nanotube does not proceed, and the effect of improving the performance of the conductive film is lowered. On the other hand, if it is longer than 50 milliseconds, the base material may be adversely affected by light deterioration and heat deterioration, and the metal nanowire or the metal nanotube is likely to be blown off. More preferably, it is 40 microseconds to 10 milliseconds. For this reason, pulse light is used instead of continuous light in this embodiment.
- the transparent conductive pattern When manufacturing the transparent conductive pattern according to the present embodiment, a pattern of any shape (including a solid shape formed on the entire surface of the substrate) is printed on the appropriate substrate using the transparent conductive ink according to the present embodiment. Then, after drying by heat treatment, the pulse width (on) is 20 microseconds to 50 milliseconds, more preferably 40 microseconds to 10 milliseconds using a xenon pulse irradiation lamp or the like for this pattern. The crossing point between metal nanowires or metal nanotubes is bonded by irradiating pulsed light.
- the term “bonding” means that the nanowire or nanotube material (metal) absorbs the pulsed light at the intersection of the metal nanowires or metal nanotubes, and the internal heat is generated more efficiently at the intersection, so that the part is welded. It is to be done. By this joining, the connection area between the nanowires or nanotubes at the intersections can be increased and the surface resistance can be lowered. In this way, by irradiating pulsed light to join the intersections of the metal nanowires or metal nanotubes, a conductive layer in which the metal nanowires or metal nanotubes are network-like is formed. Therefore, the conductivity of the transparent conductive pattern can be improved, and the surface resistance value is 10 to 800 ⁇ / ⁇ .
- the network formed by the metal nanowires or the metal nanotubes is not preferable in a dense state without a gap. This is because the light transmittance decreases if the interval is not provided.
- light irradiation can be implemented in an air atmosphere, it can also be implemented in inert atmospheres, such as nitrogen, and pressure reduction as needed.
- the conductive film after the pulse light irradiation, it is preferable to protect the conductive film by attaching a protective film on the transparent conductive pattern.
- the press mentioned here refers to applying pressure to the base material, and any form may be used.
- a method in which the base material is pressed between two flat plates or a cylindrical roll is used.
- a method of applying pressure to the material is preferable, and a method using the latter roll is particularly preferable because the pressure is applied uniformly.
- the pressure is not as uniform as the pressure roll, so the pressure is preferably 0.1 MPa to 200 MPa, more preferably 1 MPa to 100 MPa.
- heating may be performed during pressurization.
- pressure By applying pressure, not only the volume resistivity is lowered, but also mechanical properties such as bending strength can be improved.
- the pressure the higher the pressure, the more effective it is to reduce the volume resistivity and improve the mechanical strength.
- the pressure is too high, the cost of the pressurizing device will be very high.
- the upper limit is a desirable value.
- the light irradiation and pressing may be carried out either alone or in combination.
- Example 1 ⁇ Production of silver nanowires> Polyvinylpyrrolidone K-90 (manufactured by Nippon Shokubai Co., Ltd.) (0.49 g), AgNO 3 (0.52 g) and FeCl 3 (0.4 mg) were dissolved in ethylene glycol (125 ml), and 1 at 150 ° C. The reaction was heated for an hour. The obtained precipitate was isolated by centrifugation, and the precipitate was dried to obtain a target silver nanowire (average diameter 36 nm, average length 20 ⁇ m). The ethylene glycol, AgNO 3 and FeCl 3 are manufactured by Wako Pure Chemical Industries, Ltd.
- terpineol manufactured by Nippon Terpene Chemical Co., Ltd.
- tersolve MTPH manufactured by Nippon Terpene Chemical Co., Ltd.
- Isobornylcyclohexanol was added and dispersed well using ARV-310 manufactured by Shinkey Co., Ltd. to obtain a transparent conductive ink.
- thermogravimetric analyzer is a differential ultra high temperature thermobalance TG-DTA galaxy (S) manufactured by Bruker Ax Co., Ltd.
- the obtained ink was measured for viscosity at 25 ° C. using Brookfield Model DV-II + Pro.
- the viscosity measured using rotor number 52 was 1.5 ⁇ 10 4 mPa ⁇ s.
- the silver nanowire content contained in the ink is a small amount of 0.5% by mass, the ink viscosity is substantially equal to the viscosity of the dispersion medium itself.
- ⁇ Printing of transparent conductive ink> Using a transparent conductive ink prepared as described above, a 2.5 cm square solid film was applied to a screen printer MT-320TVZ (manufactured by Microtech Co., Ltd.), a sword squeegee (APOLAN International Co., Ltd., sword squeegee, polyurethane, hardness 70 And printing with a squeegee mounting angle of 60 ° (clearance: 1.0 mm, squeegee speed: 300 mm / sec, squeegee movement distance during printing: 15 cm, squeegee printing pressure: 0.2 MPa, scraper Pressure: 0.15 MPa, back pressure: 0.1 MPa).
- the attack angle of the squeegee tip is 25 °.
- polyester film: Lumirror (registered trademark) T60 (thickness 125 ⁇ m) was used as the substrate. After printing, it was dried with a hot air circulating dryer at 100 ° C. for 1 hour to obtain a printed matter of transparent conductive ink.
- Example 2 Instead of mounting the squeegee at a mounting angle of 60 °, printing was performed in the same manner as in Example 1 except that the squeegee was mounted at a mounting angle of 65 °. In this embodiment, by mounting the squeegee at a mounting angle of 65 °, the attack angle at the tip of the squeegee becomes 30 °.
- Comparative Example 1 ⁇ Printing of transparent conductive ink> Instead of mounting the squeegee at a mounting angle of 60 °, printing was performed in the same manner as in Example 1 except that the squeegee was mounted at a mounting angle of 80 °. In this comparative example, when the squeegee is attached at an attachment angle of 80 °, the attack angle of the squeegee tip is 45 °.
- the average diameter and average length (average diameter: 36 nm, average length: 20 ⁇ m) of the silver nanowires prepared as described above were obtained by using a reaction solution of silver nanowires heated at 150 ° C. for 1 hour as a solvent with dibutyl ether. Part of the substituted silver nanowire suspension was further diluted with dibutyl ether, cast on glass, dried, and then dried with SEM (S-5000, manufactured by Hitachi, Ltd.). The diameter and length of 100 silver nanowires was measured to obtain an average value.
- the length of the silver nanowires before printing was determined by sampling a small amount of the transparent conductive ink obtained as described above, diluting with methanol, casting it on glass, drying, and SEM (stock) The length of 100 silver nanowires was measured with Hitachi S-5000), and the average value was obtained.
- printing was repeated 200 times by the methods of Examples 1 and 2 and Comparative Example 1, and a small amount of ink on the screen mask immediately after printing 5, 50, 100, 150, and 200 and before printing were sampled.
- the number of times of printing is 50 times or more, and Examples 1 and 2 are maintained approximately three times longer than Comparative Example 1, and the surface resistance is stable. You can see that it has changed.
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- Spectroscopy & Molecular Physics (AREA)
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Abstract
Description
<銀ナノワイヤの作製>
ポリビニルピロリドンK-90((株)日本触媒社製)(0.49g)、AgNO3(0.52g)及びFeCl3(0.4mg)を、エチレングリコール(125ml)に溶解し、150℃で1時間加熱反応した。得られた析出物を遠心分離により単離し、析出物を乾燥して目的の銀ナノワイヤ(平均径36nm、平均長さ20μm)を得た。上記エチレングリコール、AgNO3、FeCl3は和光純薬工業株式会社製である。
上記150℃で1時間加熱反応して得られた銀ナノワイヤの反応液に、6倍容量のジブチルエーテルを添加して攪拌後、静置してナノワイヤを沈降させた。ナノワイヤの沈降後、デカンテーションにより上澄み液を分離することにより、溶媒置換を行い、銀ナノワイヤを約20質量%含んだジブチルエーテル(粘度調整溶媒)に分散した銀ナノワイヤの懸濁液を得た。
上記により調製した透明導電性インクを用いて2.5cm角のベタ膜をスクリーン印刷機MT-320TVZ(マイクロテック(株)製)に、剣スキージ(APOLAN International社製剣スキージ、ポリウレタン製、硬度70、先端部角度55°)をスキージ装着角度60°で装着して印刷(クリアランス:1.0mm、スキージ速度:300mm/sec、印刷時のスキージ移動距離:15cm、スキージ印圧:0.2MPa、スクレッパ圧:0.15MPa、背圧:0.1MPa)した。この条件ではスキージ先端部のアタック角度は25°となる。また、基材には東レ(株)社ポリエステルフィルム:ルミラー(登録商標)T60(厚み125μm)を用いた。印刷後、熱風循環乾燥機にて100℃-1時間かけて乾燥し透明導電性インクの印刷物を得た。
透明導電性インクの印刷物はNovaCentrix社製光焼成装置PulseForge 3300を用いて、600V、50マイクロ秒のパルス光を単発照射した。
スキージを装着角度60°で装着した代わりに、装着角度65°でスキージを装着した以外は実施例1と同様に印刷した。本実施例において装着角度を65°でスキージを装着することによりスキージ先端部のアタック角度は30°となる。
<透明導電性インクの印刷>
スキージを装着角度60°で装着した代わりに、装着角度80°でスキージを装着した以外は実施例1と同様に印刷した。本比較例において装着角度を80°でスキージを装着することによりスキージ先端部のアタック角度は45°となる。
上記の通り作製して得られた銀ナノワイヤの平均径及び平均長さ(平均径36nm、平均長さ20μm)は、上記150℃で1時間加熱反応後の銀ナノワイヤの反応液をジブチルエーテルで溶媒置換した銀ナノワイヤの懸濁液の一部をさらにジブチルエーテルで希釈し、ガラス上にキャストし、乾燥後にSEM(株式会社日立製作所製S-5000)にて100本の銀ナノワイヤの径と長さを計測して各々平均値を求めた。
パルス光を照射した後の銀ナノワイヤの堆積層について、三菱化学株式会社製LORESTA-GP MCP-T610 4探針法表面抵抗率、体積抵抗率測定装置を使用して表面抵抗を測定した。測定した結果を表1に示した。測定数は2であり、その平均値を示した。
日本電色工業(株)製濁度計NDH2000を用いて、全光線透過率を測定した。測定した結果を表1に示した。測定数は2であり、その平均値を示した。
Claims (14)
- 金属ナノワイヤと金属ナノチューブの少なくとも一方と分散媒とを含む透明導電性インクを、スクリーンマスクに接触するスキージ先端部のアタック角度が1~30°の範囲でスクリーン印刷することを特徴とする透明導電パターンの形成方法。
- 前記スクリーンマスクに接触するスキージの先端部がアタック角度を小さくするように先端から少なくとも一方の主面に勾配を有するスキージを使用する請求項1に記載の透明導電パターンの形成方法。
- 前記勾配を有するスキージ先端部角度が10~60°である請求項1または2に記載の透明導電パターンの形成方法。
- 前記スキージの材質が合成ゴム、天然ゴム、金属、プラスチックからなる群のいずれかである請求項1から請求項3のいずれか一項に記載の透明導電パターンの形成方法。
- 前記合成ゴムがウレタンゴムまたはシリコーンゴムからなる請求項4に記載の透明導電パターンの形成方法。
- スキージ速度を5~800mm/secとしてスクリーン印刷する請求項1から請求項5のいずれか一項に記載の透明導電パターンの形成方法。
- 前記透明導電性インクが、透明導電性インク総質量に対して、金属ナノワイヤ及び金属ナノチューブの総量として0.01~10質量%含む、請求項1から請求項6のいずれか一項に記載の透明導電パターンの形成方法。
- 前記分散媒が、分子量の範囲が150~500である有機化合物からなる形状保持材を含む請求項1から請求項7のいずれか一項に記載の透明導電パターンの形成方法。
- 前記形状保持材の有機化合物が、単糖類、ポリオール、4級炭素原子及び/または橋かけ環骨格を有するアルキル基と水酸基とを有する化合物のいずれかである請求項8に記載の透明導電パターンの形成方法。
- 前記形状保持材の有機化合物が、ジグリセリン、2,2,4-トリメチル-1,3-ペンタンジオールモノイソブチレート、キシルロース、リブロース、ボルニルシクロヘキサノール、ボルネオール、イソボルニルシクロヘキサノールまたはイソボルネオールのいずれかである請求項9に記載の透明導電パターンの形成方法。
- 前記分散媒が、形状保持材の粘度を調製する粘度調整溶媒をさらに含む請求項8から請求項10のいずれか一項に記載の透明導電パターンの形成方法。
- 前記粘度調整溶媒が、水、アルコール、ケトン、エーテル、脂肪族系炭化水素溶剤及び芳香族系炭化水素溶剤の少なくとも一種である請求項11に記載の透明導電パターンの形成方法。
- 前記粘度調整溶媒のアルコールが、テルピネオールである請求項12に記載の透明導電パターンの形成方法。
- 前記形状保持材の含有量が分散媒総質量に対して10~90質量%である請求項8から請求項13のいずれか一項に記載の透明導電パターンの形成方法。
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