WO2015064567A1 - 薄膜印刷用導電性組成物及び薄膜導電パターン形成方法 - Google Patents
薄膜印刷用導電性組成物及び薄膜導電パターン形成方法 Download PDFInfo
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- WO2015064567A1 WO2015064567A1 PCT/JP2014/078617 JP2014078617W WO2015064567A1 WO 2015064567 A1 WO2015064567 A1 WO 2015064567A1 JP 2014078617 W JP2014078617 W JP 2014078617W WO 2015064567 A1 WO2015064567 A1 WO 2015064567A1
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- thin film
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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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- 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
- C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
-
- 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
-
- 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
- C09D11/10—Printing inks based on artificial resins
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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
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
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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
- 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
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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
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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
- H05K3/1283—After-treatment of the printed patterns, e.g. sintering or curing methods
- H05K3/1291—Firing or sintering at relative high temperatures for patterns on inorganic boards, e.g. co-firing of circuits on green ceramic sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41F—PRINTING MACHINES OR PRESSES
- B41F15/00—Screen printers
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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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0242—Shape of an individual particle
- H05K2201/0245—Flakes, flat particles or lamellar particles
Definitions
- the present invention relates to a conductive composition for thin film printing and a thin film conductive pattern forming method.
- a step due to the thickness of the wiring itself formed on the substrate often becomes a problem, and a wiring having a very thin thickness is required as the wiring.
- a technique for producing a fine wiring pattern a technique of patterning a metal thin film produced by a heat vapor deposition method or a sputtering method by a photolithography method has been applied.
- a vacuum environment is indispensable for the thermal evaporation method and the sputtering method, and the burden of wastewater treatment and waste liquid treatment in the subsequent photolithography is large, and environmental improvement is desired, and the number of processes is long and the price is high. It becomes very expensive and it is difficult to reduce the manufacturing cost when applied to the manufacture of a wiring pattern.
- gravure printing is used to print a thin film, but gravure printing is a large-scale facility and cannot be said to be a printing method suitable for a small variety of products.
- the printing speed is slow, and when printing ink containing metal particles, it is necessary to use metal particles having a particle diameter of several tens of nm or less, and the cost of raw materials becomes very high.
- An object of the present invention is to provide a conductive composition for thin film printing and a method for forming a thin film conductive pattern, in which thin film printing with a thickness of 3 ⁇ m or less is easy and conductivity can be easily improved by heating and baking at 300 ° C. or lower or light irradiation. It is to provide.
- one embodiment of the present invention is a conductive composition for thin film printing, comprising metal particles, a binder resin, and a solvent, and a hydrocarbon group and a hydroxyl group having a bridged ring skeleton in the solvent.
- the metal particles have a content of 5 to 98% by mass, the metal particles have a content of 15 to 60% by mass, and the metal particles contain 20% by mass or more of flat metal particles.
- the binder resin is contained in an amount of 0.5 to 10 parts by mass with respect to 100 parts by mass, and the viscosity at 25 ° C. is 1.0 ⁇ 10 3 to 2 ⁇ 10 5 mPa ⁇ s.
- the organic compound having a hydrocarbon group having a bridged ring skeleton and a hydroxyl group is preferably isobornylcyclohexanol, tricyclodecane dimethanol or hydroxydicyclopentadiene, or a mixture thereof. .
- the metal particles contain 40% by mass or more of flat metal particles.
- the flat metal particles are preferably silver flat particles, and the aspect ratio (width / thickness of the flat metal particles) is preferably 5 to 200.
- the metal particles are preferably a mixture of a plurality of types of metal particles. It is preferable that the plurality of types of metal particles include flat particles and spherical nanoparticles.
- the binder resin includes poly-N-vinylamide, polyalkylene glycol, polyurethane, cellulose resin and derivatives thereof, polyester resin, chlorinated polyolefin resin, polyacrylic resin, polyvinyl acetal (butyral) resin, epoxy resin, epoxy acrylate resin. , Phenol resin, melamine resin, or urea resin is preferable.
- the poly-N-vinylamide is poly-N-vinylformamide, poly-N-vinylacetamide, poly-N-vinylpyrrolidone and poly-N-vinylcaprolactam, or a copolymer of these monomers with other vinyl compounds.
- it is at least one selected from the group consisting of polymers
- the polyalkylene glycol is polyethylene glycol, polypropylene glycol, a copolymer of ethylene glycol and propylene glycol (having an ethylene oxide unit and a propylene oxide unit). Copolymer) and at least one selected from the group consisting of polyTHF (polybutylene glycol) is preferred.
- the cellulose resin is preferably at least one selected from the group consisting of methylcellulose, ethylcellulose, hydroxycellulose, methylhydroxycellulose, and cellulose acetate.
- the epoxy resin is a bisphenol-A-type epoxy resin, It is preferably at least one selected from the group consisting of bisphenol-F-type epoxy resins, novolac type epoxy resins, aliphatic polyvalent epoxy resins, and alicyclic glycidyl type polyvalent epoxy resins.
- the polyurethane is at least one polyol selected from polyether polyol, polycarbonate polyol, polyester polyol, or at least one polyol selected from pentaerythritol, dipentaerythritol, trimethylolpropane, ditrimethylolpropane, glycerin or At least one hydroxyl group-containing compound selected from ethylene oxide and / or propylene oxide adduct of paratoluenesulfonic acid, dicyclohexylmethane-4,4′-diisocyanate, isophorone diisocyanate, hexamethylene-1,6-diisocyanate, Preferably it is a reaction product with at least one isocyanate group-containing compound selected from diisocyanates. .
- Another embodiment of the present invention is a method for forming a thin film conductive pattern, the step of screen printing a pattern of any shape on a substrate with any of the above-described conductive compositions for thin film printing, and the pattern And heating and baking at 300 ° C. or lower or irradiating the pattern with pulsed light.
- thin film printing with a thickness of 3 ⁇ m or less by screen printing is easy, and even a substrate with low heat resistance is easily conductive by heating and baking at a relatively low temperature of 300 ° C. or less or light irradiation.
- the conductive composition for printing which can form a conductive thin film, and / or the thin film conductive pattern formation method is realizable.
- the conductive composition for thin film printing according to the embodiment includes metal particles, a binder resin, and a solvent, and includes 5 to 98% by mass of an organic compound having a hydrocarbon group having a bridged ring skeleton and a hydroxyl group in the solvent.
- the metal particle content is 15 to 60% by mass
- the metal particle contains 20% by mass or more of flat metal particles
- the binder resin is contained in an amount of 0.5 to 10 parts by mass with respect to 100 parts by mass of the metal particles.
- the viscosity at 25 ° C. is 1.0 ⁇ 10 3 to 2 ⁇ 10 5 mPa ⁇ s.
- examples of the organic compound having a hydrocarbon group having a bridged ring skeleton and a hydroxyl group include isobornylcyclohexanol, tricyclodecane dimethanol, and hydroxydicyclopentadiene. These may be used alone or in combination.
- a thin film (conductive pattern) can be satisfactorily formed by screen printing, and a dispersion medium (mainly a solvent). By evaporating and removing the film, a coating film exhibiting conductivity can be formed.
- the “thin film” means a film having a thickness of 3 ⁇ m or less.
- the metal particles that are the conductive component of the conductive composition (ink) according to the present embodiment need to include flat metal particles, but include metal particles having an average particle diameter of 500 nm or less and shapes corresponding thereto. You can also However, when the amount of non-flat metal particles exceeds 80% by mass, it becomes difficult to achieve thickness uniformity and conductivity, so that the flat metal particles are contained in the metal particles by 20% by mass or more. More preferably, it is 40 mass% or more.
- the flat metal particles contained in the metal particles used in the conductive composition (ink) of the present invention are flat (flat) particles, and include scale-like metal particles.
- the shape of the tabular grains was changed by observing 10 points with a magnification of 30,000 times, and the thickness and width of the grains were measured, and the thickness was obtained as the number average value.
- the range of 10 to 600 nm is preferable, and the range of 20 to 200 nm is more preferable.
- the width is preferably 0.2 to 5 ⁇ m.
- the aspect ratio does not exhibit the effect of connecting the particles unless it is large to some extent, but if it is too large, there is a problem that the printing accuracy is lowered. Therefore, the preferred aspect ratio is in the range of 5 to 200, more preferably in the range of 5 to 100. If the aspect ratio is less than 5, conductivity is difficult to develop, and if it is greater than 200, it may be difficult to print a fine pattern. Note that the fibrous metal nanowires or metal nanotubes cannot be distinguished in the width and thickness of the particles (the aspect ratio is 1), and are not included in the flat metal particles according to the present embodiment. Further, it is not used as metal particles contained in the conductive composition (ink).
- the conductive composition (ink) using flat metal particles has a lower viscosity than that using spherical particles, and the film thickness of the thin film (conductive pattern) formed by orientation well during printing is reduced. be able to.
- the thickness of the flat metal particles exceeds 600 nm, thin film printing is difficult in the first place, and if it is less than 10 nm, deformation or the like is likely to occur during ink preparation.
- a preferable range of the width is 0.2 to 5 ⁇ m, and a more preferable range is 0.25 to 3 ⁇ m.
- the material of the metal particles is, for example, at least one selected from the group consisting of gold, silver, platinum, copper, nickel, iron, cobalt, zinc, ruthenium, rhodium, palladium, cadmium, osmium, iridium, and aluminum.
- the alloy etc. which combined these metals are mentioned.
- a silver flat particle is mentioned.
- metal particles made of different materials or metal particles made of the same or different materials and having different shapes may be mixed and used.
- the mixing of metal particles having different shapes means mixing of flat metal particles and non-flat metal particles.
- flat metal particles are mixed in an amount of 20% by mass or more, preferably 40% by mass or more.
- non-flat metal particles examples include spherical and cubic particles, but it goes without saying that coarse particles cannot be used for thin film printing.
- Preferable metal particles to be mixed (combined with) flat metal particles are spherical nanoparticles having an average particle diameter of 5 to 600 nm, more preferably an average particle diameter of 10 to 300 nm.
- the average particle size referred to here is, for example, measured by a particle size distribution measuring apparatus manufactured by Nikkiso Co., Ltd., MT3000II series, USVR (laser diffraction / scattering method), or nanotrack UPA-EX150 (dynamic light scattering method).
- spherical nanoparticles By using flat metal particles and spherical nanoparticles together, spherical nanoparticles intervene between the flat metal particles, and the spherical nanoparticles play a role in connecting the flat metal particles during firing. Thus, a conductive pattern having a lower resistance can be obtained.
- the metal particles are contained in the conductive composition (ink) in an amount of 15 to 60% by mass, preferably 20 to 55% by mass, and more preferably 25 to 50% by mass. If the amount is less than 15% by mass, uneven printing tends to occur in the formed conductive pattern. Moreover, when it exceeds 60 mass%, the thickness of the thin film obtained by printing will become thick.
- binder resin used in the conductive composition (ink) examples include poly-N-vinylformamide, poly-N-vinylacetamide, poly-N-vinylpyrrolidone, and poly-N-vinylcaprolactam.
- Poly-N-vinyl amides, or poly-N-vinyl amide copolymers such as copolymers of these monomers with other vinyl compounds (such as vinyl acetate), polyethylene glycol, polypropylene glycol, ethylene glycol and propylene glycol Copolymer (copolymer having ethylene oxide unit and propylene oxide unit), polyalkylene glycol such as polyTHF (polybutylene glycol), polyurethane, methylcellulose, ethylcellulose, hydroxycellulose, methyl Cellulose resins such as droxycellulose and cellulose acetate and their derivatives, polyester resins such as aliphatic diol and aliphatic dicarboxylic acid copolymerized number average molecular weight: 10,000 to 100,000, glass transition point (Tg): -10 to Thermoplastic resin such as chlorinated polyolefin resin, polyacrylic resin, polyvinyl acetal (butyral) resin, bisphenol-A-type epoxy resin, bisphenol-
- the polyurethane is generally a reaction product of a compound having a hydroxyl group and an isocyanate group.
- a preferable compound having a hydroxyl group include polyether polyols having a number average molecular weight of 500 to 2000, more preferably 800 to 1500.
- Polyethylene glycol, polypropylene glycol, etc.) at least one polyol selected from polycarbonate polyol, polyester polyol, or at least one polyol selected from pentaerythritol, dipentaerythritol, trimethylolpropane, ditrimethylolpropane, glycerin or paratoluene.
- Examples of the compound having a preferred isocyanate group include ethylene oxide and / or propylene oxide adducts of sulfonic acid.
- Carboxy group-containing diols such as dimethylolpropionic acid and dimethylolbutanoic acid can also be used as part of the polyol component in order to improve the adhesion to the substrate and the like.
- binder resin is 10 mass parts or less with respect to 100 mass parts of metal particles, Preferably it is 5 mass parts or less, More preferably, it is 3 mass parts or less.
- the content rate in an electroconductive composition (ink) is 5 mass% or less, More preferably, it is 2 mass% or less, More preferably, it is 1 mass% or less.
- the binder resin is too small, the mechanical strength of the thin film itself and the adhesion strength with the substrate are lowered, so usually 0.5 parts by mass or more, preferably 1 part by mass or more with respect to 100 parts by mass of the metal particles. is there.
- an organic compound having a hydrocarbon group having a bridged ring skeleton and a hydroxyl group as a solvent for adjusting the viscosity of the conductive composition (ink), such as isobornylcyclohexanol, tricyclodecane dimethanol and / or Contains hydroxydicyclopentadiene.
- Isobornylcyclohexanol imparts appropriate tackiness to the conductive ink by the hydrogen bond of the hydroxyl group in addition to the complicated three-dimensional structure of the isobornyl group.
- the compound having an isobornyl group and a hydroxyl group has a high viscosity even though the volatilization temperature is not so high, it is possible to increase the viscosity of the conductive composition (ink).
- the residue can be reduced by appropriate heating, light baking, or the like after completion of printing and drying.
- tricyclodecane dimethanol and hydroxydicyclopentadiene also give appropriate conductivity to the conductive ink due to the hydrogen bond of the hydroxyl group in addition to the complicated three-dimensional structure of the norbornyl group.
- the compound having a norbornyl group and a hydroxyl group has a high viscosity despite the fact that the volatilization temperature is not so high, so that the viscosity of the conductive composition (ink) can be increased.
- the residue can be reduced by appropriate heating, light baking, or the like after completion of printing and drying.
- the content of organic compounds having a hydrocarbon group and a hydroxyl group having a bridged ring skeleton such as isobornylcyclohexanol, tricyclodecane dimethanol and / or hydroxydicyclopentadiene in the solvent depends on the other solvent used. However, it is in the range of 5 to 98% by mass, more preferably 20 to 97% by mass, and still more preferably 50 to 95% by mass.
- the content of the organic compound having a hydrocarbon group having a bridged ring skeleton such as isobornylcyclohexanol, tricyclodecane dimethanol and / or hydroxydicyclopentadiene and a hydroxyl group is less than 5% by mass, thin film printing
- the conductive composition for ink (ink) cannot have an appropriate viscosity and the shape of the printed pattern cannot be maintained, and the amount exceeds 98% by mass, the viscosity of the conductive ink becomes too high, and at the time of printing. In some cases, the stringiness becomes so bad that it cannot be printed.
- the solvent is prepared by mixing an organic compound having a hydrocarbon group having a bridged ring skeleton such as isobornylcyclohexanol, tricyclodecane dimethanol and / or hydroxydicyclopentadiene with a hydroxyl group and another appropriate solvent. Adjusted to desired viscosity.
- solvents examples include alcohols, ketones, esters, ethers, aliphatic hydrocarbon solvents, and aromatic hydrocarbon solvents.
- ethanol isopropyl alcohol, 1-methoxy-2-propanol (PGME), ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol , Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, diacetone alcohol, ethylene glycol monobutyl ether, propylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monopropyl ether, diethylene glycol monobutyl ether, Tripropylene glycol, triethylene glycol monoethyl ether Terpineol, dihydroterpineol, dihydroterpinyl monoacetate, methyl
- the conductive composition (ink) according to this embodiment has wettability with an optional component other than the above components (binder resin, viscosity adjusting solvent, flat metal particles), for example, a base material, as long as the properties are not impaired.
- an improving wetting and dispersing agent, surface conditioner, antifoaming agent, thixotropic agent, leveling agent, corrosion inhibitor, adhesion promoter, surfactant, rheology control agent and the like may be included.
- DISPERBYK registered trademark
- DISPERBYK registered trademark
- DISPERBYK registered trademark
- DISPERBYK registered trademark
- -108 manufactured by Big Chemie Japan Co., Ltd.
- BYK registered trademark
- BYK registered trademark
- BYK registered trademark
- the conductive composition (ink) according to this embodiment can be produced by appropriately performing the above-described components by appropriately selecting stirring, mixing, heating, cooling, dissolution, dispersion, and the like by a known method.
- the preferred viscosity of the conductive composition (ink) according to the present embodiment is preferably 1.0 ⁇ 10 3 to 2 ⁇ 10 5 mPa ⁇ s at 25 ° C. in the case of screen printing. Preferably, it is 3.0 ⁇ 10 3 to 5 ⁇ 10 4 mPa ⁇ s.
- the conductive pattern forming method includes a step of screen-printing a pattern of an arbitrary shape on a substrate using the conductive composition (ink) prepared as described above, and 300 ° C. or less on the pattern. Heating and / or irradiating with pulsed light (photo baking).
- the “pattern” in this specification includes a solid pattern applied to the entire surface of the substrate. Moreover, although it is a screen mesh to be used, it is needless to say that a smaller permeation volume is advantageous, and is 25 cm 3 / cm 2 or less, more preferably 20 cm 3 / cm 2 or less. When it is larger than 25 cm 3 / cm 2 , the film thickness becomes thick. If the screen is too fine, the metal particles are easily clogged, and if it is too rough, pattern printing cannot be performed. Therefore, the mesh count (the number of lines (wires) constituting the mesh in 1 inch) is preferably 100 to 800, more preferably 200 to 700.
- the wire diameter also depends on the mesh count, but if it is too thick, the transmission volume will be small, and if it is too thin, the strength will be low and it will be easily broken. Therefore, when the mesh count is 500, a wire diameter of 10 to 30 ⁇ m, more preferably 15 to 25 ⁇ m is preferable.
- the screen plate is preferably made of stainless steel in terms of printing accuracy, and can be calendered if necessary.
- the emulsion thickness for forming a pattern on the screen plate a thinner one is better for thin film printing.
- the trace of the screen is transferred, so preferably 1 to 30 ⁇ m, more preferably 2 to 20 ⁇ m. It is.
- the substrate for pattern printing may be rigid (rigid) or bend easily (flexible). Moreover, it may be colored.
- the substrate include a rigid substrate such as a glass substrate, an alumina substrate, a glass epoxy substrate, a paper phenol substrate, an insulating resin-coated metal substrate, a polyimide film, a polycarbonate film, a polyethersulfone film, an acrylic film, a polyester (polyethylene terephthalate, Examples thereof include materials such as flexible substrates such as polyethylene naphthalate) film, polyolefin film, cycloolefin polymer film, and cycloolefin copolymer film.
- the “base material having low heat resistance” means a substrate mainly composed of a resin having a glass transition temperature (Tg) of 200 ° C. or lower.
- the amount of the conductive composition (ink) applied to the substrate is determined in consideration of the thickness of the 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 coating amount of the conductive ink and the conditions of the coating method.
- the film thickness is preferably as thick as possible from the viewpoint of low surface resistance, and as thin as possible to reduce the thickness of the member, the film thickness is preferably 200 to 3000 nm, and considering the above, the film thickness is preferably 500 to 2000 nm. More preferably, the film thickness is 700 to 1500 nm.
- the printed (coated) conductive ink layer can be dried by heat treatment as necessary.
- drying means removing the solvent by evaporation.
- the heating temperature for drying varies depending on the liquid component constituting the dispersion medium, but if the drying temperature is too high, foaming occurs when the solvent evaporates and voids are generated, which is not preferable. Therefore, the drying temperature is 120 ° C. or lower, more preferably 100 ° C. or lower. 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.
- Viscous liquids such as isobornylcyclohexanol, tricyclodecane dimethanol, hydroxydicyclopentadiene, etc.
- organic compounds having a hydrocarbon group and a hydroxyl group having a bridging ring skeleton have a high boiling point and lower boiling points than these.
- the diluting solvent coexists in the dispersion medium, the diluting solvent having a low boiling point is preferentially evaporated and removed. For this reason, the viscosity of the dispersion medium is increased by drying, and the collapse of the conductive pattern during drying is suppressed.
- a pattern is printed on the substrate in an arbitrary shape by screen printing using the conductive composition (ink), and this pattern is as described above. Then, the dried pattern is further subjected to a heat firing treatment or pattern of 300 ° C. or lower, and pulse light is irradiated (photo-baked).
- the conductive composition (ink) of the present invention it is possible to form a low-resistance thin film (thickness of 3 ⁇ m or less, 1 ⁇ m or less) that could not be realized by screen printing with the conventional conductive composition (ink). ) Can be formed.
- the heat treatment is preferably a heat treatment in the range of 100 ° C. to 300 ° C., more preferably 120 ° C. to 200 ° C. If the temperature is lower than 100 ° C, it is difficult to develop conductivity. If the temperature is higher than 300 ° C, the substrate that can be used is restricted, and the member may be damaged. Needless to say, it is preferable in terms of freedom and energy.
- a hot plate, a hot-air circulating thermostatic chamber, an IR furnace, or the like can be used, and the atmosphere can be changed from air to an inert gas atmosphere or a reducing gas atmosphere as necessary.
- 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. 1 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 thin film printed on the substrate is irradiated with pulsed light.
- irradiation is repeated n times, one cycle (on + off) in FIG. 1 is repeated n times.
- it is preferable to cool from the substrate side so that the substrate can be cooled to near room temperature when the next pulse light irradiation is performed.
- 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 and the like.
- 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 particles does not proceed and the effect of improving the performance of the conductive film is reduced. On the other hand, if it is longer than 50 milliseconds, the substrate and the binder resin may be adversely affected by light deterioration and heat deterioration, and metal particles are likely to blow off. More preferably, it is 40 microseconds to 10 milliseconds. For this reason, pulse light is used instead of continuous light in this embodiment. Irradiation with pulsed light is effective even if performed in a single shot, but can also be performed repeatedly as described above.
- the irradiation interval (off) is preferably in the range of 20 microseconds to 5 seconds, more preferably 2 milliseconds to 2 seconds. If it is shorter than 20 microseconds, it becomes close to continuous light and is irradiated without being allowed to cool after a single irradiation, so that there is a possibility that the substrate will be heated and the temperature will rise and deteriorate. Further, if it is longer than 5 seconds, the process time becomes longer, which is not preferable.
- the conductive characteristics of the obtained conductive pattern can be obtained by adjusting the film thickness, that is, the coating amount of the composition and the conditions of the coating method, and by adjusting the concentration of the metal particles in the conductive composition (ink) according to this embodiment. Value.
- the thinner the film thickness the higher the surface resistivity even if the volume resistance is the same.
- the higher the concentration of the flat metal particles in the conductive composition (ink) the lower the volume resistivity. Therefore, in order to reduce the resistivity of the conductor circuit even if the film thickness is small, it is necessary to reduce the volume resistivity, to increase the concentration of the flat metal powder, and to select appropriate firing conditions. .
- the conductive pattern obtained as described above preferably has a volume resistivity value of 1 ⁇ 10 ⁇ 3 to 2 ⁇ 10 ⁇ 6 ⁇ ⁇ cm, and further has a volume resistivity value of 1 ⁇ 10 ⁇ 4. More preferably, it is ⁇ 2 ⁇ 10 ⁇ 6 ⁇ ⁇ cm.
- a protective layer that protects the conductive pattern by applying a protective film on top of the conductive pattern, or applying and drying resin ink, and curing as necessary.
- a protective layer for example, a thermosetting resin having a thickness of 0.5 to 30 ⁇ m, an ultraviolet curable resin, or a thermoplastic resin can be used.
- PET polyethylene with an adhesive layer
- PEN polyethylene naphthalate
- the thermosetting resin include an epoxy resin, a urethane resin, an acrylic resin, a phenol resin, and a silicone resin.
- Examples of the ultraviolet curable resin include an acrylic resin and an alicyclic epoxy resin.
- Examples of the thermoplastic resin include a cycloolefin polymer, a cycloolefin copolymer, and PMMA (polymethyl methacrylate).
- Example 1 Preparation of conductive composition (ink)> As flat silver particles, 47.3 g of Ag Nano Flake N300 (Tokusen Kogyo Co., Ltd., terpineol-dispersed paste having an Ag content of 84.5% by mass), terpineol C (Nippon Terpene Chemical (PVP K30)) Co., Ltd.) 3.00 g of solution and 49.6 g of tersolve MTPH (manufactured by Nippon Terpene Chemical Co., Ltd., isobornylcyclohexanol) as a solvent were added, and a planetary vacuum stirrer (ARV-310, manufactured by Sinky Corporation) was used. Samples were prepared by mixing for about 30 minutes at a maximum stirring speed of 2000 rpm.
- ⁇ Viscosity measurement> The viscosity of the solvent and the conductive composition (ink) was measured at 25 ° C. using a Brookfield B-type viscometer DV-II + Pro. Incidentally, the rotor number 52 if the viscosity exceeds 1.0 ⁇ 10 4 mPa ⁇ s, in the following cases 1.0 ⁇ 10 4 mPa ⁇ s rotor No. 40, were measured using, respectively.
- ⁇ Printing of conductive composition (ink)> A screen plate having a 2 cm square pattern produced by performing a film hardening process at a film thickness of 5 ⁇ m using an emulsion IC-10000 (manufactured by Murakami Co., Ltd.) using a mesh with a mesh count of 640 and a wire diameter of 15 ⁇ m ⁇ calendered product. was used for printing.
- the base material used was Teijin Teonex (registered trademark) Q51 (PEN (polyethylene naphthalate) film, 100 ⁇ m thickness, manufactured by Teijin DuPont Films).
- the conductive composition (ink) prepared as described above was printed on the surface of the substrate with a 2 cm square pattern using the screen plate, the film was heated and baked at 140 ° C. for 60 minutes without pre-drying. A conductive pattern was formed.
- volume resistivity LORESTA (registered trademark) -GP MCP-T610 manufactured by Mitsubishi Chemical Corp.
- the volume resistivity of the conductive pattern formed using a 4-probe method surface resistivity and volume resistivity measuring device was measured.
- Examples 2 to 15 and Comparative Examples 1 to 5 Compositions of conductive compositions (inks) of Examples 2 to 15 and Comparative Examples 1 to 5 prepared using various metal (silver) particles, a binder resin, and a solvent in the same manner as in the ink preparation example of Example 1.
- Tables 1 to 3 collectively show the evaluation results of the conductive patterns produced using them and the results of Example 1.
- Tables 1 and 2 show the contents of used silver particles 1 (Examples 1 to 15 and Comparative Examples 1 to 5 do not use silver particles 2), binder solution, solvent 1 and solvent 2, and Table 3 shows the contents. The evaluation result of each electroconductive composition (ink) and each electroconductive pattern produced using this is shown.
- grains of the raw material used by each Example and the comparative example was put together in Table 6, and was described.
- conductive materials were prepared as follows by mixing two types of materials constituting the binder by heat treatment.
- the synthetic binders (A) and (B) used in Examples 14 and 15 were synthesized as follows.
- ⁇ Preparation of conductive composition of Example 11> As flat silver particles, Ag Nano Flake N300 (manufactured by Toxen Industries Co., Ltd., 53.3 g of terpineol dispersion paste having an Ag content of 84.5% by mass), ethylene oxide adduct PTSA-40X of paratoluenesulfonamide (Meisei Chemical Industries ( 0.543 g, block isocyanate BL4265SN (manufactured by Sumika Bayer Urethane Co., Ltd.) 0.812 g, and Telsolve MTPH (manufactured by Nippon Terpene Chemical Co., Ltd., isobornylcyclohexanol) 45.3 g as a solvent, A sample was prepared by mixing with a planetary vacuum stirrer (ARV-310, manufactured by Sinky Corporation) at a maximum stirring speed of 2000 rpm for about 30 minutes.
- ARV-310 planetary vacuum stirrer
- ⁇ Preparation of conductive composition of Example 12> As flat silver particles, Ag Nano Flake N300 (manufactured by Toxen Industries Co., Ltd., 53.4 g of a terpineol dispersion paste with an Ag content of 84.5% by mass), paratoluenesulfonamide ethylene oxide adduct PTSA-40X (Meisei Chemical Industries ( Co., Ltd.) 0.592 g, blocked isocyanate 17B-60P (Asahi Kasei Co., Ltd.) 0.766 g, Tersolve MTPH (Nihon Terpene Chemical Co., Ltd., isobornylcyclohexanol) 45.4 g as a solvent is added, and planetary A sample was prepared by mixing for about 30 minutes at a maximum stirring speed of 2000 rpm with a mold vacuum stirrer (ARV-310, manufactured by Sinky Corporation).
- ARV-310 mold vacuum stirrer
- ⁇ Preparation of conductive composition of Example 13> As flat silver particles, Ag Nano Flake N300 (manufactured by Toxen Industries Co., Ltd., 53.3 g of terpineol dispersion paste having an Ag content of 84.5% by mass), ethylene oxide adduct PTSA-40X of paratoluenesulfonamide (Meisei Chemical Industries ( 0.641 g), Block isocyanate SBB-70P (Asahi Kasei Co., Ltd.) 0.756 g, Tersolve MTPH (Nihon Terpene Chemical Co., Ltd., isobornylcyclohexanol) 45.6 g as a solvent, and planet A sample was prepared by mixing for about 30 minutes at a maximum stirring speed of 2000 rpm with a mold vacuum stirrer (ARV-310, manufactured by Sinky Corporation).
- ARV-310 mold vacuum stirrer
- the conductive compositions in Examples 14 and 15 were prepared in the same manner as Example 1 except that the silver particles, binder solution, and solvent shown in Table 1 were used.
- Examples 16-20 Table 4 summarizes the compositions of the conductive compositions (inks) of Examples 16 to 20 prepared using various metal (silver) particles, a binder resin, and a solvent in the same manner as in the ink preparation example of Example 1. Indicated. Table 4 shows the contents of the used silver particles (silver particles 1, silver particles 2), binder solution, solvent 1, and solvent 2. Table 5 shows the evaluation results of the conductive compositions (inks) of Examples 16 to 20 and the conductive patterns produced using the conductive compositions (inks). The shapes of the raw material metal (silver) particles used in Examples 16 to 20 are summarized in Table 6.
- Examples 16 and 17 as a solvent, instead of tersolve MTPH, two types of tricyclodecane dimethanol and dihydroterpineol (Example 16) and two types of tricyclodecane dimethanol and hydroxydicyclopentadiene (Example 17) ) Is used. In Examples 18 and 19, two types of solvents, tersolve MTPH and terpineol, are used as solvents. Also, for Comparative Examples 3 and 5 (Table 2), two types of Telsolve MTPH and C terpineol are used.
- Example 18 two types of silver particles are used.
- Example 18 Ag Nano Flake N300 and T5A-A01 (spherical silver particles manufactured by DOWA Electronics Co., Ltd.) were mixed and carried out.
- Example 19 and 20 AgC-204B (Fukuda Metal Foil Powder Co., Ltd. flat silver particles) and T5A-A01 (DOWA Electronics Co., Ltd. spherical silver particles) were mixed and used.
- C terpineol is an isomer mixture of ⁇ -, ⁇ -, and ⁇ -terpineol, manufactured by Nippon Terpene Chemical Co., Ltd.
- PVP polyvinylpyrrolidone (K30)
- etosel registered trademark
- STD100CPS cellulose acetate manufactured by Nisshin Kasei Co., Ltd.
- PTSA-40X is an ethylene oxide adduct of paratoluenesulfonamide manufactured by Meisei Chemical Industry Co., Ltd.
- BL4265SN is a block isocyanate manufactured by Sumika Bayer Urethane Co., Ltd., 17B-60P and SBB-70P are manufactured by block isocyanate Asahi Kasei Co., Ltd.
- BRG556 is a phenol novolac resin manufactured by Showa Denko KK (Registered trademark)
- BL-2H is butyral resin Sekisui Is made Manabu Kogyo Co.
- MTPH is Terusorubu MTPH Nippon Terpene Chemicals Co.
- THF is tetrahydrofuran
- PGMEA is propylene glycol methyl ether acetate.
- T5A-A01 was a relatively beautiful spherical shape.
- N300 and M13 were plate-like flat powders.
- N300 was obtained as a solvent-dispersed paste.
- LM1 has a small amount of fine powder mixed in a plate-like flat powder.
- SF-K and Ag-XF301K are flake powders, but flat powders with an aspect ratio of 5 or more.
- AgC-204B was a plate-like flat powder.
- the flakes in Table 6 mean foil powder with undulations, not plate-like.
- Example 21 Photo-baking Using the conductive composition (ink) prepared in Example 1, printing on Teijin Theonex Q51 (100 ⁇ m thickness) in the same manner, using a xenon irradiation device Pulse Forge 3300 manufactured by NovaCentrix, and air-dried overnight. Then, pulsed light irradiation was performed. The pulsed light was irradiated 30 times at a 4 Hz interval with a light source driving voltage of 400 V and an irradiation time of 100 ⁇ sec. As a result, a low resistance thin film conductive pattern having a thickness of 0.75 ⁇ m after irradiation and a volume resistivity of 8.2 ⁇ 10 ⁇ 6 ⁇ ⁇ cm was obtained.
- Comparative Example 1 only spherical particles (T5A-A01) were used as silver particles, and the volume resistivity was high (4.8 ⁇ 10 ⁇ 3 ⁇ ⁇ cm). Further, Comparative Example 2 using SF-K having an aspect ratio of silver particles smaller than 5 also had a high volume resistivity (1.1 ⁇ 10 ⁇ 2 ⁇ ⁇ cm). Further, in Comparative Example 3, since the silver particle content in the ink was as low as 10% by mass, a uniform coating film could not be obtained and some blurring occurred. Moreover, in the comparative example 4, the ratio (binder / total metal) of the binder mass with respect to 100 mass parts of metal particles was as high as 15 mass parts, and the volume resistivity became high (320 ohm * cm). In Comparative Example 5, since the silver particle content in the ink was as high as 80% by mass, the film thickness after firing was thick (6.32 ⁇ m).
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Abstract
Description
<導電性組成物(インク)の作製>
扁平銀粒子としてAg Nano Flake N300(トクセン工業(株)製、Ag含有量84.5質量%のターピネオール分散ペースト)47.3g、40質量%ポリビニルピロリドン(PVP K30)のターピネオールC(日本テルペン化学(株)製)溶液3.00g、溶媒としてテルソルブ MTPH(日本テルペン化学(株)製、イソボルニルシクロヘキサノール)49.6gを加え、遊星型真空攪拌装置(ARV-310、シンキー社製)にて最大攪拌速度2000rpmで30分程度混合して、サンプルを調製した。
ブルックフィールド社製B型粘度計DV-II+Proを用いて溶媒及び導電性組成物(インク)の粘度を25℃にて測定した。なお、粘度が1.0×104mPa・sを超える場合はロータ番号52を、1.0×104mPa・s以下の場合はロータ番号40を、各々用いて測定した。
スクリーン版としてメッシュカウント640で線径15μmΦ カレンダー加工品のメッシュを用いて、乳剤IC-10000(ムラカミ社製)を用いて膜厚5μmで 硬膜処理して作製した2cm角のパターンを有するスクリーン版を用いて印刷した。なお、基材はテイジン テオネックス(登録商標) Q51(帝人デュポンフィルム社製PEN(ポリエチレンナフタレート)フィルム、100μm厚)を用いた。前記の通り調製した導電性組成物(インク)を前記スクリーン版を用いて2cm角のパターンを基材表面に印刷した後、予備乾燥をせずに、140℃で60分間加熱焼成処理して薄膜導電パターンを形成した。
日立ハイテク株式会社製 FE-SEM S-5200により測定した。
三菱化学株式会社製LORESTA(登録商標)-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形成された導電パターンの体積抵抗率を測定した。
実施例1におけるインク作製例と同様にして、種々の金属(銀)粒子、バインダー樹脂、溶媒を用いて作製した実施例2~15および比較例1~5の導電性組成物(インク)の組成およびそれらを用いて作製した導電パターンの評価結果を実施例1の結果とともに表1~表3にまとめて示した。表1、表2には、使用した銀粒子1(実施例1~15、比較例1~5では銀粒子2は使用しない)、バインダー溶液、溶媒1、溶媒2の内容を、表3には、各導電性組成物(インク)及びこれを用いて作製した各導電パターンの評価結果を示す。なお、各実施例、比較例で用いた原料の金属(銀)粒子の形状を表6にまとめて記載した。
扁平銀粒子としてAg Nano Flake N300(トクセン工業(株)製、Ag含有量84.5質量%のターピネオール分散ペースト)53.3g、パラトルエンスルホンアミドのエチレンオキサイド付加物PTSA-40X(明成化学工業(株)製)0.543g、ブロックイソシアネートBL4265SN(住化バイエルウレタン(株)製)0.812g、溶媒としてテルソルブ MTPH(日本テルペン化学(株)製、イソボルニルシクロヘキサノール)45.3gを加え、遊星型真空攪拌装置(ARV-310、シンキー社製)にて最大攪拌速度2000rpmで30分程度混合して、サンプルを調製した。
扁平銀粒子としてAg Nano Flake N300(トクセン工業(株)製、Ag含有量84.5質量%のターピネオール分散ペースト)53.4g、パラトルエンスルホンアミドのエチレンオキサイド付加物PTSA-40X(明成化学工業(株)製)0.592g、ブロックイソシアネート17B-60P(旭化成(株)製)0.766g、溶媒としてテルソルブ MTPH(日本テルペン化学(株)製、イソボルニルシクロヘキサノール)45.4gを加え、遊星型真空攪拌装置(ARV-310、シンキー社製)にて最大攪拌速度2000rpmで30分程度混合して、サンプルを調製した。
扁平銀粒子としてAg Nano Flake N300(トクセン工業(株)製、Ag含有量84.5質量%のターピネオール分散ペースト)53.3g、パラトルエンスルホンアミドのエチレンオキサイド付加物PTSA-40X(明成化学工業(株)製)0.641g、ブロックイソシアネートSBB-70P(旭化成(株)製)0.756g、溶媒としてテルソルブ MTPH(日本テルペン化学(株)製、イソボルニルシクロヘキサノール)45.6gを加え、遊星型真空攪拌装置(ARV-310、シンキー社製)にて最大攪拌速度2000rpmで30分程度混合して、サンプルを調製した。
500mlのセパラブルフラスコにジオール((株)クラレ製クラレポリオール、C-1015N(ポリカーボネートジオール、数平均分子量1000))30.25g、ジメチロールブタン酸13.08g、テトラヒドロフラン(THF)71.77gを入れ、オイルバスで80℃に加熱しながら十分に溶解させた。滴下ロートを用いてジイソシアネート(住化バイエルウレタン(株)製、デスモジュール(登録商標)W(ジシクロヘキシルメタン-4,4′-ジイソシアネート))28.74gをゆっくり滴下して、100℃で2時間、次いで110℃で1時間加熱撹拌し、合成バインダー(A)を得た。
1000mlのセパラブルフラスコにジオール(日油(株)製ポリプロピレングリコール、ユニオールD-1000(数平均分子量1000))38.21g、ジメチロールブタン酸30.03g、プロピレングリコールメチルエーテルアセテート(PGMEA)125.96gを入れ、オイルバスで80℃に加熱しながら十分に溶解させた。滴下ロートを用いてジイソシアネート(住化バイエルウレタン(株)製、デスモジュール(登録商標)W(ジシクロヘキシルメタン-4,4′-ジイソシアネート))57.86gをゆっくり滴下して、100℃で2時間、次いで110℃で1時間加熱撹拌し、合成バインダー(B)を得た。
実施例1におけるインク作製例と同様にして、種々の金属(銀)粒子、バインダー樹脂、溶媒を用いて作製した実施例16~20の導電性組成物(インク)の組成を表4にまとめて示した。表4には、使用した銀粒子(銀粒子1、銀粒子2)、バインダー溶液、溶媒1、溶媒2の内容を示す。また、表5には、実施例16~20の各導電性組成物(インク)及びこれを用いて作製した各導電パターンの評価結果を示す。なお、実施例16~20で用いた原料の金属(銀)粒子の形状を表6にまとめて記載した。
光焼成
実施例1で作製した導電性組成物(インク)を用いて、テイジン テオネックス Q51(100μm厚)に同様に印刷して、NovaCentrix社製のキセノン照射装置Pulse Forge3300を使用し、一晩風乾後に、パルス光照射を行った。なお、パルス光の照射条件は、光源の駆動電圧400V、照射時間100μsecで4Hzの間隔で30回照射した。その結果照射後の厚みが0.75μmで体積抵抗率が8.2×10-6Ω・cmである低抵抗の薄膜導電パターンが得られた。
Claims (10)
- 金属粒子、バインダー樹脂及び溶媒を含み、前記溶媒中に橋かけ環骨格を有する炭化水素基と水酸基とを有する有機化合物を5~98質量%含み、前記金属粒子含有率が15~60質量%であり、かつ、前記金属粒子が扁平金属粒子を20質量%以上含み、前記金属粒子100質量部に対して前記バインダー樹脂を0.5~10質量部含有し、25℃における粘度が1.0×103~2×105mPa・sであることを特徴とする薄膜印刷用導電性組成物。
- 前記橋かけ環骨格を有する炭化水素基と水酸基とを有する有機化合物が、イソボルニルシクロヘキサノール、トリシクロデカンジメタノールまたはヒドロキシジシクロペンタジエンのいずれか、またはこれらの混合物である請求項1に記載の薄膜印刷用導電性組成物。
- 前記金属粒子が扁平金属粒子を40質量%以上含む、請求項1または2に記載の薄膜印刷用導電性組成物。
- 前記扁平金属粒子が銀の扁平粒子であり、そのアスペクト比(扁平金属粒子の幅/厚さ)が5~200である、請求項1から3のいずれか一項に記載の薄膜印刷用導電性組成物。
- 前記金属粒子が、複数種類の金属粒子を混合したものである、請求項1から4のいずれか一項に記載の薄膜印刷用導電性組成物。
- 前記複数種類の金属粒子が、扁平粒子と球状ナノ粒子とを含む、請求項5に記載の薄膜印刷用導電性組成物。
- 前記バインダー樹脂が、ポリ-N-ビニルアミド、ポリアルキレングリコール、ポリウレタン、セルロース樹脂およびその誘導体、ポリエステル樹脂、塩素化ポリオレフィン樹脂、ポリアクリル樹脂、ポリビニルアセタール(ブチラール)樹脂、エポキシ樹脂、エポキシアクリレート樹脂、フェノール樹脂、メラミン樹脂、尿素樹脂のいずれかである、請求項1から6のいずれか一項に記載の薄膜印刷用導電性組成物。
- 前記ポリ-N-ビニルアミドがポリ-N-ビニルホルムアミド、ポリ-N-ビニルアセトアミド、ポリ-N-ビニルピロリドンおよびポリ-N-ビニルカプロラクタム、もしくはそれらのモノマーと他のビニル化合物との共重合体からなる群から選択される少なくとも一種であり、前記ポリアルキレングリコール化合物がポリエチレングリコール、ポリプロピレングリコール、エチレングリコールとプロピレングリコールの共重合体(エチレンオキサイドユニットとプロピレンオキサイドユニットを有する共重合体)、ポリTHF(ポリブチレングリコール)からなる群から選択される少なくとも一種であり、前記セルロース樹脂がメチルセルロース、エチルセルロース、ヒドロキシセルロース、メチルヒドロキシセルロース、セルロースアセテートからなる群から選択される少なくとも一種であり、前記エポキシ樹脂がビスフェノール-A-型エポキシ樹脂、ビスフェノール-F-型エポキシ樹脂、ノボラック型エポキシ樹脂、脂肪族多価エポキシ樹脂、脂環族グリシジル型多価エポキシ樹脂等からなる群から選択される少なくとも一種である、請求項7に記載の薄膜印刷用導電性組成物。
- 前記ポリウレタンがポリエーテルポリオール、ポリカーボネートポリオール、ポリエステルポリオールから選択される少なくとも一種のポリオール、あるいはペンタエリスリトール、ジペンタエリスリトール、トリメチロールプロパン、ジトリメチロールプロパン、グリセリンから選択される少なくとも一種のポリオールまたはパラトルエンスルホン酸の、エチレンオキサイド及び/またはプロピレンオキサイド付加物から選択される少なくとも一種の水酸基含有化合物と、ジシクロヘキシルメタン-4,4′-ジイソシアネート、イソホロンジイソシアネート、ヘキサメチレン-1,6-ジイソシアネート、トリレンジイソシアネートから選択される少なくとも一種のイソシアネート基含有化合物との反応物である、請求項7に記載の薄膜印刷用導電性組成物。
- 請求項1から請求項9のいずれか一項に記載の薄膜印刷用導電性組成物により、基板上に任意の形状の薄膜パターンをスクリーン印刷する工程と、
前記薄膜パターンに300℃以下の加熱焼成及び/または薄膜パターンにパルス光を照射する工程と、
を有することを特徴とする薄膜導電パターン形成方法。
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US15/032,388 US9845404B2 (en) | 2013-10-31 | 2014-10-28 | Conductive composition for thin film printing and method for forming thin film conductive pattern |
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