WO2015111731A1 - Procédé de formation de motif, substrat pourvu d'un film conducteur de l'électricité transparent, dispositif et instrument électronique - Google Patents

Procédé de formation de motif, substrat pourvu d'un film conducteur de l'électricité transparent, dispositif et instrument électronique Download PDF

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Publication number
WO2015111731A1
WO2015111731A1 PCT/JP2015/051924 JP2015051924W WO2015111731A1 WO 2015111731 A1 WO2015111731 A1 WO 2015111731A1 JP 2015051924 W JP2015051924 W JP 2015051924W WO 2015111731 A1 WO2015111731 A1 WO 2015111731A1
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WIPO (PCT)
Prior art keywords
line
substrate
liquid
droplet
pattern
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PCT/JP2015/051924
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English (en)
Japanese (ja)
Inventor
直人 新妻
大屋　秀信
正好 山内
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コニカミノルタ株式会社
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Priority to JP2015559153A priority Critical patent/JP6508062B2/ja
Priority to CN201580005367.5A priority patent/CN106413917B/zh
Publication of WO2015111731A1 publication Critical patent/WO2015111731A1/fr

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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
    • H05K3/1241—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 ink-jet printing or drawing by dispensing
    • H05K3/125—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 ink-jet printing or drawing by dispensing by ink-jet printing
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • 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
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C03C2218/119—Deposition methods from solutions or suspensions by printing
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1343—Electrodes
    • G02F1/13439—Electrodes characterised by their electrical, optical, physical properties; materials therefor; method of making
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/0286—Programmable, customizable or modifiable circuits
    • H05K1/0287—Programmable, customizable or modifiable circuits having an universal lay-out, e.g. pad or land grid patterns or mesh patterns
    • H05K1/0289—Programmable, customizable or modifiable circuits having an universal lay-out, e.g. pad or land grid patterns or mesh patterns having a matrix lay-out, i.e. having selectively interconnectable sets of X-conductors and Y-conductors in different planes
    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • H05K1/092—Dispersed materials, e.g. conductive pastes or inks
    • H05K1/095—Dispersed materials, e.g. conductive pastes or inks for polymer thick films, i.e. having a permanent organic polymeric binder
    • 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
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0104—Properties and characteristics in general
    • H05K2201/0108—Transparent

Definitions

  • the present invention relates to a pattern forming method for forming a coating film in which a functional material is deposited on an edge, a substrate with a transparent conductive film using the coating film formed by the coating film forming method, a device, and an electronic apparatus About.
  • patterning by a printing method has been proposed.
  • pattern formation with a line width of about 20 ⁇ m is the limit, and it is difficult to cope with required miniaturization.
  • Patent Document 1 states that a fine electrical wiring pattern can be formed compared to the size of the coating film by collecting solids contained in the liquid in the periphery of the coating film using convection inside the liquid.
  • the transparent electrode is an essential component.
  • transparent electrodes are an indispensable technique for touch panels, mobile phones, electronic paper, various solar cells, and various electroluminescent light control elements.
  • an ITO transparent electrode in which an indium-tin composite oxide (ITO) film is formed on a transparent substrate such as glass or a transparent plastic film by a sputtering method has been mainly used.
  • indium used for ITO is a rare metal, and due to the rising price, it is desired to remove indium. Furthermore, sputtering has a problem that the tact time is long and the material use efficiency is very bad, and the ITO transparent electrode has a large problem of high cost.
  • Patent Document 2 uses a convection inside the liquid to collect silver nanoparticles contained in the liquid at the periphery of the coating film, thereby forming a fine ring-shaped pattern made of silver nanoparticles.
  • Transparent conductive films connected to each other are described.
  • Patent Document 3 discloses that transparent carbon nanotubes having a plurality of fine ring-shaped patterns connected to each other are collected by collecting the carbon nanotubes contained in the liquid at the periphery of the coating film using convection inside the liquid. A conductive film is described.
  • Non-Patent Documents 1 and 2 after the liquid droplets ejected by the inkjet method are united on a base material to form a line-shaped liquid, silver nano-particles contained in the liquid are utilized by using convection inside the liquid.
  • a transparent conductive film is described in which fine fine line patterns made of silver nanoparticles are arranged in a mesh shape by collecting particles in the periphery of a line-shaped liquid.
  • Non-Patent Document 2 since the amount of applied liquid droplets is small, the interval between the thin line patterns deposited on the edge portion becomes narrow. For this reason, when the fine line pattern is arranged in the plane so as to have the lowest visibility, there is a problem that the transparency is easily impaired.
  • an object of the present invention is to provide a pattern forming method capable of stably forming a pattern including a thin line by suppressing a bulge generated when forming a line-shaped liquid, and achieving both high transparency and low visibility. is there.
  • the further subject of this invention is the base material with a transparent conductive film (transparent electrode) which has the outstanding characteristic which can improve transparency and visibility, when compared by the same resistance value, a device provided with this, and an electronic device To provide equipment.
  • the contact angle of the discharged droplets on the substrate is controlled to be 5 ⁇ 10 ⁇ 10 [m 3 / m] or more and 5.5 ⁇ 10 ⁇ 9 [m 3 / m] or less and 10 [ °] to 45 [°], and the diameter of a single landing droplet of the ejected droplet on the substrate is D [m], and the ejected droplet on the substrate.
  • the discharge interval is p [m]
  • the relationship with the discharge frequency f [1 / s] Is Pattern forming method for controlling discharge so as to satisfy the above condition.
  • a substrate with a transparent conductive film comprising a transparent conductive film containing a pattern formed by the pattern forming method according to any one of 1 to 5 on a substrate surface.
  • the device which has a base material with a transparent conductive film of said 6.
  • a liquid containing a functional material is discharged by a droplet discharge method, and the line-shaped liquid formed on the substrate is evaporated and dried, so that the functionality of the line-shaped liquid is increased.
  • the material is selectively deposited to form a pattern, and a conceptual diagram is shown in FIG.
  • H is a droplet discharge device.
  • the droplet discharge device an inkjet head included in a so-called inkjet recording device can be used, but it is not particularly limited as long as the discharge conditions of the present invention described later can be realized.
  • the droplet discharge mechanism of the droplet discharge device is not particularly limited, but examples thereof include a thermal method, a piezo method, and a continuous method.
  • 1 is a base material
  • 2 is a line-shaped liquid containing a functional material
  • 3 is a pattern formed by selectively depositing a functional material on the edge of the line-shaped liquid 2.
  • a liquid containing a functional material is ejected from the liquid droplet ejection device H, and the liquid droplets are sequentially ejected. Are combined on the substrate to form the line-shaped liquid 2 containing the functional material.
  • the functional liquid is selectively deposited on the edge of the line-shaped liquid 2 by evaporating and drying the line-shaped liquid 2.
  • a pattern 3 made of a thin line containing a functional material is formed on the substrate 1.
  • the pattern 3 formed from one line-shaped liquid 2 is composed of a set of two thin wires 31 and 32.
  • the present invention is preferably used in order to achieve both high transparency and low visibility when the pattern 3 is formed.
  • Transparency and “low visibility” are distinguished. “Transparency” is based on the transmittance of light transmitted through the pattern.
  • low visibility is based on difficulty in recognizing a pattern by visual observation. Suppose that it is excellent in low visibility so that the thin line which comprises a pattern cannot be visually recognized. Even if the transparency is the same, there may be a difference in low visibility. As will be described later with reference to FIG. 4, the present invention is effective not only for transparency but also for realizing low visibility. Used.
  • FIG. 2 is a view for explaining discharge conditions of the pattern forming method according to the present invention.
  • FIG. 2A shows a state in which the droplet discharge state in FIG. 1A is viewed from the side
  • FIG. 2B shows a state in plan view.
  • the droplet discharge device H and the substrate 1 are relatively scanned in the x direction, and droplets containing functional materials are sequentially discharged to To form a line-like liquid 2.
  • the diameter D [m] of the landing droplet can be calculated from the contact angle ⁇ [rad] of the discharged droplet with the substrate and the discharged droplet amount V [m 3 ] by the following equation (2). It can.
  • the contact angle is a static contact angle.
  • the inventor of the present invention pays attention to the fact that such a bulge is generated by the landing droplet flowing into the line-like liquid behind the scanning direction of the droplet discharge device, and the line-like shape behind this landing droplet in the scanning direction. It has been found that the occurrence of bulges can be suppressed by supplying a liquid amount equal to or larger than the amount of liquid flowing into the liquid by ejected droplets.
  • the line-shaped liquid is rearward in the scanning direction as the discharge interval p [m] is reduced.
  • the amount of liquid into which the landing droplets flow increases. That is, the bulge can be suppressed by supplying a larger amount of liquid by the ejected droplets by the amount corresponding to the shortening of the ejection interval p [m].
  • the diameter of a single landing droplet of the discharged droplet on the substrate is D [m]
  • the discharge interval of the discharged droplet on the substrate is p [m. ]
  • the discharge is controlled so that the relationship with the discharge frequency f [1 / s] satisfies the condition of the following formula (3), thereby forming a linear liquid with a uniform line width and high linearity. be able to.
  • a droplet discharge device that discharges a specified droplet amount
  • the number of gradations is the number of ink droplets that are ejected to one dot.
  • FIG. 3 is a principle diagram for explaining the pattern forming method according to the present invention.
  • the composition of the line-shaped liquid 2, the contact angle between the substrate 1 and the line-shaped liquid 2, the functional material concentration, and the drying conditions are selected.
  • the functional material can be selectively deposited on the edge of the line-shaped liquid 2.
  • the convection state in which the functional material can be selectively deposited on the edge of the line-shaped liquid 2 in the present invention will be described with reference to FIG.
  • the drying of the line-shaped liquid 2 arranged on the substrate 1 is faster at the edge than the center part, and the solid concentration reaches a saturated concentration as the drying proceeds, and the solid content locally precipitates at the edge of the line-shaped liquid 2.
  • the edge of the line-shaped liquid 2 is fixed by the deposited solid content, and shrinkage in the width direction of the line-shaped liquid 2 due to subsequent drying is suppressed.
  • the liquid of the line-shaped liquid 2 forms a convection from the central portion toward the edge so as to compensate for the liquid lost by evaporation at the edge.
  • this convection is caused by immobilization of the contact line of the line-shaped liquid 2 accompanying drying and a difference in evaporation amount between the central part and the edge of the line-shaped liquid 2, the solid content concentration, the contact between the line-shaped liquid 2 and the substrate 1. It varies depending on the angle, the amount of the line-shaped liquid 2, the heating temperature of the substrate 1, the arrangement density of the line-shaped liquid 2, or the environmental factors of temperature, humidity, and atmospheric pressure, and can be controlled by adjusting these. .
  • the contact angle of the linear liquid 2 with respect to the substrate 1 is preferably in the range of 10 [°] to 45 [°].
  • the contact angle is less than 10 [°]
  • the contact angle exceeds 45 [°] the difference in evaporation amount between the central portion of the line-shaped liquid 2 and the edge.
  • the convection from the central part to the edge in the line-shaped liquid 2 is not promoted.
  • the contact angle range the contact line of the line-shaped liquid 2 is likely to be fixed, and the difference in evaporation amount between the center of the line-shaped liquid 2 and the edge increases, and the line-shaped liquid 2 moves from the center to the edge. Convection is promoted. As a result, thinning is further promoted, and an effect of further improving transparency can be obtained.
  • the contact angle of the line-shaped liquid 2 with respect to the substrate 1 can be adjusted by setting the composition of the line-shaped liquid 2 or the surface energy of the substrate 1.
  • the difference in evaporation amount between the central portion of the line-shaped liquid 2 and the edge is affected by the degree of diffusion of the gas formed on the droplet surface. From this, the droplet application amount of the line-like liquid 2 greatly contributes to the convection.
  • the amount of droplets applied to the line-shaped liquid 2 increases, the amount of evaporation between the central portion of the line-shaped liquid 2 and the edge due to the influence of the adjacent line-shaped liquid 2 And the convection for selectively depositing the functional material on the edge of the line-shaped liquid 2 does not occur remarkably.
  • the fine line width becomes large, and solid content remains outside the predetermined patterning position of the fine line part, thereby impairing transparency.
  • the droplet amount V [m 3 ] and the discharge interval p [m] are controlled so that the droplet application amount of the line-like liquid 2 is 5.5 ⁇ 10 ⁇ 9 [m 3 / m] or less. By doing so, the said convection can be produced notably.
  • the same number of the same thin lines are arranged (the transparency is the same) by arranging the fine lines so that the distance J between the fine line patterns 32 and 31 arranged on the near side is substantially the same.
  • the effect that the visibility of a thin line becomes the lowest when compared is acquired.
  • the same thin line width by forming the pattern so that the interval I between the two thin line patterns 31 and 32 is widened, the effect of the lowest visibility is obtained while maintaining high transparency. .
  • the interval I between the two thin line patterns 31 and 32 in a set is determined by the line width I ′ of the line-shaped liquid 2 selected from the contact angle of the liquid containing the functional material with the substrate 1 and the applied amount of liquid droplets. .
  • the distance I between the pair of two thin line patterns 31 and 32 is designed to be wide, and high transparency is maintained.
  • the pattern can be formed so that the visibility of the fine line is the lowest.
  • the droplet amount V [m 3 ] and the discharge interval p [m] are preferably selected so that the droplet application amount is 4.5 ⁇ 10 ⁇ 10 [m 3 / m] or more.
  • the interval I can be increased by increasing the droplet application amount while preventing the occurrence of bulges.
  • a value close to the value of the interval J preferably substantially the same value, can be appropriately given to the interval I. That is, it is possible to obtain advantageous effects such as reducing visibility by arranging the thin lines at a desired interval while maintaining the stability of the thin lines. Thus, a remarkable effect can be produced also from the viewpoint of increasing the degree of freedom in forming the thin line.
  • the line liquid is generated.
  • a highly uniform pattern can be stably obtained, and both high transparency and low visibility can be achieved.
  • a substrate with a transparent conductive film (transparent electrode) having excellent properties capable of improving transparency and visibility when compared with the same resistance value, a substrate with a transparent conductive film (transparent electrode) having excellent properties capable of improving transparency and visibility, a device and an electronic apparatus provided with the substrate Can be provided.
  • FIG. 5 is a partially enlarged plan view showing an example of a pattern formed on a substrate by the pattern forming method according to the present invention.
  • FIG. 6 is a cross-sectional view taken along the line vi-vi in FIG. 5, and is a cross-sectional view (longitudinal cross-sectional view) obtained by cutting a set of two thin lines included in the pattern in a direction perpendicular to the line segment direction.
  • the set of two thin lines (segments) 31 and 32 of the pattern 3 generated from one line-shaped liquid do not necessarily have to be island shapes completely independent from each other.
  • the two line segments 31 and 32 are connected by the thin film portion 30 formed between the line segments 31 and 32 at a height lower than the height of the line segments 31 and 32. It is also preferable in the present invention to be formed as a continuous body.
  • the line widths W1 and W2 of the line segments 31 and 32 of the pattern 3 are each preferably 10 ⁇ m or less. If it is 10 micrometers or less, since it will be a level which cannot be visually recognized normally, it is more preferable from a viewpoint of improving transparency. Considering the stability of the line segments 31 and 32, the line widths W1 and W2 of the line segments 31 and 32 are preferably in the range of 2 ⁇ m or more and 10 ⁇ m or less, respectively.
  • the widths W1 and W2 of the line segments 31 and 32 are the height of the thinnest portion where the thickness of the functional material is the thinnest between the line segments 31 and 32, and the Z Is defined as the widths of the line segments 31 and 32 at half the height of Y1 and Y2.
  • the height of the thinnest portion in the thin film portion 30 can be set to Z.
  • the line widths W1 and W2 of the line segments 31 and 32 are the line segments 31 and 32 from the surface of the substrate 1. Are defined as the widths of the line segments 31 and 32 at half the heights h1 and h2.
  • the line widths W1 and W2 of the line segments 31 and 32 constituting the pattern 3 are extremely thin as described above, the surface of the substrate 1 is ensured from the viewpoint of securing a cross-sectional area and reducing resistance. It is desirable that the heights h1 and h2 of the line segments 31 and 32 are higher. Specifically, the heights h1 and h2 of the line segments 31 and 32 are preferably in the range of 50 nm to 5 ⁇ m.
  • the h1 / W1 ratio and the h2 / W2 ratio are preferably in the range of 0.01 or more and 1 or less, respectively.
  • the height Z of the thinnest portion where the thickness of the functional material is the thinnest between the line segments 31 and 32, specifically, the thinnest portion of the thin film portion 30 is preferably in the range of 10 nm or less.
  • the thin film portion 30 is provided in the range of 0 ⁇ Z ⁇ 10 nm in order to achieve a balance between transparency and stability.
  • the h1 / Z ratio and the h2 / Z ratio are each preferably 5 or more, more preferably 10 or more, and particularly preferably 20 or more. preferable.
  • the interval I between the line segments 31 and 32 can be adjusted as appropriate, and is preferably adjusted in the range of 10 ⁇ m to 300 ⁇ m. Further, as described above, the interval I is preferably adjusted to a value close to the interval J described with reference to FIG. 4, and most preferably adjusted to a value substantially equal to the interval J. In the present invention, the interval I between the line segments 31 and 32 is defined as the distance between the maximum protrusions of the line segments 31 and 32.
  • the line segment 31 and the line segment 32 are same shape (similar cross-sectional area), specifically, the height h1 of the line segment 31 and the line segment 32. And h2 are preferably set to substantially equal values. Similarly, it is preferable that the line widths W1 and W2 of the line segment 31 and the line segment 32 are substantially equal values.
  • the line segments 31 and 32 do not necessarily have to be parallel, and it is sufficient that the line segments 31 and 32 are not connected over at least a certain length L in the line segment direction.
  • the line segments 31 and 32 are substantially parallel over at least a certain length L in the line segment direction.
  • the length L of the line segments 31 and 32 in the line segment direction is preferably at least 5 times the interval I between the line segments 31 and 32, and more preferably at least 10 times.
  • the length L and the interval I can be set corresponding to the formation length and formation width of the pattern (line-shaped liquid) 2.
  • the line segments 31 and 32 are connected at the formation start point and end point of the line-shaped liquid 2 (start point and end point over a certain length L in the line segment direction) to form a continuous body. This is preferable in the invention.
  • the line segments 31 and 32 have substantially the same line widths W1 and W2, and the line widths W1 and W2 are sufficiently narrower than the distance between the two lines (interval I).
  • the line segment 31 and the line segment 32 constituting the pattern 3 generated from one line-shaped liquid are formed at the same time.
  • the line segments 31 and 32 satisfy all the following conditions (a) to (d).
  • the substrate with a transparent conductive film including at least a pattern formed on the substrate surface by the pattern forming method according to the present invention has excellent characteristics that can improve transparency and low visibility when compared with the same resistance value. .
  • the substrate used in the present invention is not particularly limited.
  • glass plastic (polyethylene terephthalate, polybutylene terephthalate, polyethylene, polypropylene, acrylic, polyester, polyamide, etc.), metal (copper, nickel, aluminum, iron, etc.) Or an alloy), ceramic, and the like. These may be used alone or in a bonded state.
  • plastic is preferable, and polyethylene terephthalate, polyolefin such as polyethylene and polypropylene, and the like are preferable.
  • the functional material used in the present invention is not particularly limited, but is preferably a conductive material or a conductive material precursor.
  • An electroconductive material precursor refers to what can be changed into an electroconductive material by performing an appropriate process.
  • Preferred examples of the conductive material include conductive fine particles and conductive polymers.
  • the conductive fine particles are not particularly limited, but Au, Pt, Ag, Cu, Ni, Cr, Rh, Pd, Zn, Co, Mo, Ru, W, Os, Ir, Fe, Mn, Ge, Sn, Ga.
  • fine particles such as In can be exemplified, and among them, use of fine metal particles such as Au, Ag, and Cu is more preferable because a circuit pattern having low electrical resistance and strong corrosion can be formed.
  • metal fine particles containing Ag are most preferable.
  • the average particle diameter of these metal fine particles is preferably in the range of 1 to 100 nm, more preferably in the range of 3 to 50 nm.
  • carbon fine particles are used as the conductive fine particles.
  • the carbon fine particles include graphite fine particles, carbon nanotubes, fullerenes and the like.
  • the conductive polymer is not particularly limited, but a ⁇ -conjugated conductive polymer can be preferably exemplified.
  • the ⁇ -conjugated conductive polymer is not particularly limited, and polythiophenes, polypyrroles, polyindoles, polycarbazoles, polyanilines, polyacetylenes, polyfurans, polyparaphenylenes, polyparaphenylene vinylenes, poly Chain conductive polymers such as paraphenylene sulfides, polyazulenes, polyisothianaphthenes, and polythiazyl can be used.
  • polythiophenes and polyanilines are preferable in that high conductivity can be obtained. Most preferred is polyethylene dioxythiophene.
  • the conductive polymer used in the present invention comprises the above-described ⁇ -conjugated conductive polymer and polyanion.
  • a conductive polymer can be easily produced by chemical oxidative polymerization of a precursor monomer that forms a ⁇ -conjugated conductive polymer in the presence of an appropriate oxidizing agent, an oxidation catalyst, and a polyanion.
  • the polyanion is a substituted or unsubstituted polyalkylene, a substituted or unsubstituted polyalkenylene, a substituted or unsubstituted polyimide, a substituted or unsubstituted polyamide, a substituted or unsubstituted polyester, and a copolymer thereof. It consists of a structural unit having a group and a structural unit having no anionic group.
  • This polyanion is a solubilized polymer that solubilizes a ⁇ -conjugated conductive polymer in a solvent.
  • the anion group of the polyanion functions as a dopant for the ⁇ -conjugated conductive polymer, and improves the conductivity and heat resistance of the ⁇ -conjugated conductive polymer.
  • the anion group of the polyanion may be a functional group capable of undergoing chemical oxidation doping to the ⁇ -conjugated conductive polymer.
  • a monosubstituted sulfate group A monosubstituted phosphate group, a phosphate group, a carboxy group, a sulfo group and the like are preferable.
  • a sulfo group, a monosubstituted sulfate group, and a carboxy group are more preferable.
  • polyanions include polyvinyl sulfonic acid, polystyrene sulfonic acid, polyallyl sulfonic acid, polyacrylic acid ethyl sulfonic acid, polyacrylic acid butyl sulfonic acid, poly-2-acrylamido-2-methylpropane sulfonic acid, polyisoprene sulfone. Acid, polyvinyl carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, polyacryl carboxylic acid, polymethacryl carboxylic acid, poly-2-acrylamido-2-methylpropane carboxylic acid, polyisoprene carboxylic acid, polyacrylic acid and the like. . These homopolymers may be sufficient and 2 or more types of copolymers may be sufficient.
  • it may be a polyanion having F (fluorine atom) in the compound.
  • F fluorine atom
  • Nafion made by Dupont
  • Flemion made by Asahi Glass Co., Ltd.
  • perfluoro vinyl ether containing a carboxylic acid group and the like can be mentioned.
  • a compound having a sulfonic acid is more preferable since the ink ejection stability is particularly good when the ink jet printing method is used and high conductivity is obtained.
  • polystyrene sulfonic acid polyisoprene sulfonic acid
  • polyacrylic acid ethyl sulfonic acid and polybutyl acrylate sulfonic acid are preferable.
  • These polyanions have the effect of being excellent in conductivity.
  • the polymerization degree of the polyanion is preferably in the range of 10 to 100,000 monomer units, and more preferably in the range of 50 to 10,000 from the viewpoint of solvent solubility and conductivity.
  • a commercially available material can be preferably used as the conductive polymer.
  • a conductive polymer (abbreviated as PEDOT / PSS) made of poly (3,4-ethylenedioxythiophene) and polystyrene sulfonic acid is used in H.264. C. It is commercially available from Starck as the CLEVIOS series, from Aldrich as PEDOT-PASS 483095, 560598, and from Nagase Chemtex as the Denatron series. Polyaniline is also commercially available from Nissan Chemical as the ORMECON series.
  • liquid containing the functional material water, an organic solvent, or the like can be used alone or in combination.
  • the organic solvent is not particularly limited.
  • alcohols such as 1,2-hexanediol, 2-methyl-2,4-pentanediol, 1,3-butanediol, 1,4-butanediol, propylene glycol
  • ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, and dipropylene glycol monoethyl ether.
  • liquid containing the functional material may contain various additives such as a surfactant as long as the effects of the present invention are not impaired.
  • a surfactant for example, when the line-like liquid 2 is formed using a droplet discharge device, it becomes possible to stabilize discharge by adjusting the surface tension or the like.
  • the surfactant is not particularly limited, but a silicon surfactant or the like can be used. Silicon-based surfactants are those in which the side chain or terminal of dimethylpolysiloxy acid is modified with polyether. For example, KF-351A and KF-642 manufactured by Shin-Etsu Chemical Co., Ltd. ing.
  • the addition amount of the surfactant is preferably 1% by weight or less with respect to the total amount of the liquid that forms the line-like liquid 2.
  • the use of the substrate with a transparent conductive film according to the present invention is not particularly limited, and can be used for various devices included in various electronic devices.
  • a preferred application of the substrate with a transparent conductive film according to the present invention is a transparent electrode for various types of displays such as liquid crystal, plasma, organic electroluminescence, field emission, etc. It can be suitably used as a transparent electrode for use in touch panels, mobile phones, electronic paper, various solar cells, various electroluminescent light control devices, and the like.
  • the substrate with a transparent conductive film according to the present invention is suitably used as a transparent electrode of a device.
  • a device For example, a touch panel sensor etc. can be illustrated preferably.
  • an electronic device provided with these devices For example, a smart phone, a tablet terminal, etc. can be illustrated preferably.
  • Examples 1 to 13, Comparative Examples 1 to 8 An inkjet head (“KM512L” manufactured by Konica Minolta Co., Ltd.); standard droplet volume on the surface of the PET film, glass, and COP film (base material) subjected to corona discharge treatment using PS-1M manufactured by Shinko Electric Instrumentation Co., Ltd. 42 pl, “KM512M”; standard droplet volume 14 pl, or “KM512S”; standard droplet volume 4 pl), so that the liquid has a pitch of 423 ⁇ m between the nozzle rows in the ink and ejection conditions shown in Tables 1 to 5. Drops were discharged to form a line-like liquid in a stripe shape.
  • the pattern was dried and a solid content was deposited on the edge to form a set of two fine line patterns. After rotating the substrate on which the pattern is formed by 90 ° with respect to the ink jet head scanning direction, a plurality of sets of two fine line patterns are formed again under the same conditions, and a mesh as shown in FIG. A pattern was formed.
  • FIG. 7A shows a case where the interval I described with reference to FIG. 4 is small and smaller than the interval J
  • FIG. 7B shows a case where the interval I is large and is close to the interval J.
  • the pitch of the line liquid is 423 ⁇ m
  • the obtained pattern was measured for bulge prevention, double line width, total light transmittance, low visibility and sheet resistance. The results are shown in Tables 1-5.
  • Double line width The double line width ( ⁇ m) shown in Tables 1 to 5 is a measurement of the distance between a set of two thin lines by observation with an optical microscope. The measured value corresponds to the interval I described above.
  • the transmittance (total light transmittance) (% T) shown in Tables 1 to 5 is a value obtained by measuring the total light transmittance using AUTOMATIC ZEZETER (MODEL TC-HIIIDP) manufactured by Tokyo Denshoku. In addition, it corrects using the base material without a pattern (transparent conductive film), and is the value measured as the total light transmittance of the created pattern (transparent conductive film).
  • the low visibility shown in Tables 1 to 5 is such that the samples according to Examples 1 to 13 and Comparative Examples 1 to 9 are viewed from a position 50 cm away on the light table, and the thin lines cannot be visually recognized. Specifically, “A” indicates that the fine line is not visible, “B” indicates that the fine line is slightly visible but has no practical problem, and “C” indicates that the fine line is clearly visible. It was evaluated.
  • Sheet resistance ( ⁇ / ⁇ ) shown in Tables 1 to 5 is a value obtained by measuring a sheet resistance value using a Loresta EP (MODEL MCP-T360 type) series 4-probe probe (ESP) manufactured by Dia Instruments. It is.
  • Loresta EP MODEL MCP-T360 type
  • ESP 4-probe probe
  • DEBE is an abbreviation for diethylene glycol monobutyl ether
  • PET is polyethylene terephthalate
  • COP is an abbreviation for cycloolefin polymer.
  • Comparative Example 1 where the in-plane droplet application amount (droplet application amount in the scanning direction of the droplet discharge device) is less than the range of the present invention, the low visibility is inferior and exceeds the range of the present invention.
  • comparative example 2 it turns out that it is inferior to a total light transmittance, low visibility, and sheet resistance value.
  • Comparative Example 5 where the contact angle is less than the range of the present invention and Comparative Example 6 exceeding the range of the present invention, it can be seen that the total light transmittance, low visibility, and sheet resistance value are inferior.
  • Comparative Examples 7 and 8 that do not satisfy the condition of the above formula (3), the sheet resistance value is inferior, and the in-plane droplet application amount (droplet application amount in the scanning direction of the droplet discharge device) is It can be seen that Comparative Example 9 that is less than the range is inferior in low visibility.
  • These Comparative Examples 7 to 9 are based on the conditions described in Non-Patent Documents 1 and 2.
  • Base material 2 Line-shaped liquid 3: Pattern 30: Thin film part 31, 32: Fine line H: Droplet ejection device

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  • Application Of Or Painting With Fluid Materials (AREA)
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Abstract

L'invention se rapporte à un procédé de formation de motif grâce auquel le renflement, qui a lieu pendant la formation d'un liquide en forme de ligne, est supprimé et un motif comprenant des lignes fines peut être formé de façon stable et une haute transparence et une faible visibilité sont obtenues en même temps. Le procédé de formation de motif comprend les étapes de formation d'un liquide en forme de ligne (2) comprenant une substance fonctionnelle par dépôt du liquide comprenant une substance fonctionnelle grâce à l'utilisation d'un dispositif de dépôt de gouttelettes (H) et amenant les gouttelettes déposées séquentiellement à fusionner sur un substrat (1), et de dépôt sélectif de la substance fonctionnelle au bord du liquide en forme de ligne (2) par évaporation et séchage du liquide en forme de ligne (2). La quantité appliquée des gouttelettes du liquide en forme de ligne est réglée de façon à être de 4,5×10-10 à 5,5×10-9 [m3/m], l'angle de contact des gouttelettes sur le substrat (1) est réglé pour être de 10 à 45[°] et la relation avec la fréquence de dépôt (f) [1/s] satisfait à l'équation (1), dans laquelle D [m] est le diamètre d'une seule gouttelette ayant atterri sur le substrat (1) et p [m] est l'intervalle de dépôt de gouttelettes sur le substrat (1).
PCT/JP2015/051924 2014-01-24 2015-01-23 Procédé de formation de motif, substrat pourvu d'un film conducteur de l'électricité transparent, dispositif et instrument électronique WO2015111731A1 (fr)

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CN201580005367.5A CN106413917B (zh) 2014-01-24 2015-01-23 图案形成方法、带透明导电膜的基材、器件及电子机器

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WO2015199201A1 (fr) * 2014-06-25 2015-12-30 コニカミノルタ株式会社 Procédé de formation de motif fonctionnel en forme de réseau maillé, motif fonctionnel en forme de réseau maillé et substrat fonctionnel
WO2015199204A1 (fr) * 2014-06-25 2015-12-30 コニカミノルタ株式会社 Procédé de formation de motif, substrat pourvu d'un film électroconducteur transparent, dispositif et instrument électronique
WO2016140284A1 (fr) * 2015-03-02 2016-09-09 コニカミノルタ株式会社 Procédé de formation de motif, substrat doté d'un film conducteur transparent, dispositif et appareil électronique
WO2020044404A1 (fr) 2018-08-27 2020-03-05 コニカミノルタ株式会社 Procédé de formation de fil conducteur fin, procédé de production de conducteur transparent, procédé de production de dispositif, et ensemble d'encre conductrice et de matériau de base

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CN112349871B (zh) * 2019-12-09 2023-02-07 广东聚华印刷显示技术有限公司 金属网格电极及其制备方法

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WO2015199204A1 (fr) * 2014-06-25 2015-12-30 コニカミノルタ株式会社 Procédé de formation de motif, substrat pourvu d'un film électroconducteur transparent, dispositif et instrument électronique
KR101779738B1 (ko) 2014-06-25 2017-09-18 코니카 미놀타 가부시키가이샤 패턴 형성 방법, 투명 도전막을 구비한 기재, 디바이스 및 전자 기기
WO2016140284A1 (fr) * 2015-03-02 2016-09-09 コニカミノルタ株式会社 Procédé de formation de motif, substrat doté d'un film conducteur transparent, dispositif et appareil électronique
JPWO2016140284A1 (ja) * 2015-03-02 2017-12-14 コニカミノルタ株式会社 パターン形成方法、透明導電膜付き基材、デバイス及び電子機器
WO2020044404A1 (fr) 2018-08-27 2020-03-05 コニカミノルタ株式会社 Procédé de formation de fil conducteur fin, procédé de production de conducteur transparent, procédé de production de dispositif, et ensemble d'encre conductrice et de matériau de base

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