WO2012026791A2 - 전도성 금속 잉크 조성물 및 전도성 패턴의 형성방법 - Google Patents
전도성 금속 잉크 조성물 및 전도성 패턴의 형성방법 Download PDFInfo
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- WO2012026791A2 WO2012026791A2 PCT/KR2011/006343 KR2011006343W WO2012026791A2 WO 2012026791 A2 WO2012026791 A2 WO 2012026791A2 KR 2011006343 W KR2011006343 W KR 2011006343W WO 2012026791 A2 WO2012026791 A2 WO 2012026791A2
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- ink composition
- conductive
- conductive metal
- pattern
- metal ink
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/12—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain a coating with specific electrical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M1/00—Inking and printing with a printer's forme
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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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/52—Electrically conductive inks
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- H—ELECTRICITY
- 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
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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
- H05K1/097—Inks comprising nanoparticles and specially adapted for being sintered at low temperature
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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
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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
- H05K2201/0263—Details about a collection of particles
- H05K2201/0272—Mixed conductive particles, i.e. using different conductive particles, e.g. differing in shape
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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
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/05—Patterning and lithography; Masks; Details of resist
- H05K2203/0502—Patterning and lithography
- H05K2203/0534—Offset printing, i.e. transfer of a pattern from a carrier onto the substrate by using an intermediate member
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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
- H05K3/1275—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 other printing techniques, e.g. letterpress printing, intaglio printing, lithographic printing, offset printing
Definitions
- the present invention relates to a method of forming a conductive metal ink composition and a conductive pattern. More specifically, the present invention relates to a conductive metal ink composition and a method of forming a conductive pattern using the same, which is suitably applied to a roll printing process, enabling the formation of a conductive pattern exhibiting improved conductivity and excellent adhesion to a substrate.
- This application claims the benefit of the filing date of Korean Patent Application No. 10-2010-0083589 filed with the Korea Intellectual Property Office on August 27, 2010, the entire contents of which are incorporated herein.
- the conductive ink composition for forming the conductive pattern should have a low initial viscosity so that it can be well applied to the roller, and after being applied to the roller in a desired pattern form It should be able to transfer well on the substrate.
- the conductive metal included in the conductive ink composition has poor adhesion to the substrate and is easily agglomerated during the firing process, the surface properties of the conductive pattern and the physical properties of the final product may be reduced. Accordingly, there is a need for a conductive ink composition having properties suitable for forming a good conductive pattern by roll printing and high adhesion to a substrate.
- the present invention is applied to a roll printing process or the like, to provide a conductive metal ink composition that allows the formation of a conductive pattern exhibiting improved conductivity and excellent adhesion to a substrate.
- the present invention is to provide a method of forming a conductive pattern using the conductive metal ink composition.
- the present invention is a.
- a non-aqueous solvent comprising a first non-aqueous solvent having a vapor pressure of 3 torr or less at 25 ° C. and a second non-aqueous solvent having a vapor pressure of more than 3 torr at 25 ° C .;
- Adhesion promoters comprising at least one second metal powder or a compound of a second metal selected from the group consisting of tantalum (Ta), niobium (Nb) magnesium (Mg) tungsten (W) and vanadium (V); And
- It provides a conductive metal ink composition comprising a.
- It provides a conductive pattern forming method comprising a.
- a conductive metal ink composition and a method of forming a conductive pattern using the conductive metal ink composition which are suitably applied to a roll printing process and enable the formation of a conductive pattern exhibiting improved conductivity and excellent adhesion to a substrate, Is provided.
- FIG. 1 is a view schematically showing a process of forming a conductive pattern through a roll printing process.
- Example 2 is a view showing an attachment state of a conductive pattern on a substrate according to Example 1 of the present invention.
- FIG 3 is a view showing an adhesion state of a conductive pattern on a substrate according to Comparative Example 1 of the present invention.
- the conductive first metal powder comprising a non-aqueous solvent having a vapor pressure of 3 torr or less at 25 ° C. and a second non-aqueous solvent having a vapor pressure of more than 3 torr at 25 ° C .; Nickel (Ni), bismuth (Bi), tin (Sn), titanium (Ti), palladium (Pd), chromium (Cr), cobalt (Co), germanium (Ge), zinc (Zn), molybdenum (Mo), An adhesion promoter comprising at least one second metal powder or a compound of a second metal selected from the group consisting of tantalum (Ta), niobium (Nb), magnesium (Mg), tungsten (W) and vanadium (V); And a conductive metal ink composition comprising a polymer coating improver can be provided.
- a non-aqueous solvent comprising a first non-aqueous solvent having a vapor pressure of 3 torr or less at 25 °
- the present inventors by using the conductive metal ink composition comprising the non-aqueous solvent and adhesion promoter, it is possible to better transfer the desired pattern shape on the substrate and to form a fine conductive pattern well, such a conductive pattern is Experiments confirmed that it has a high adhesion to the substrate and completed the invention.
- the conductive metal powder does not adhere well to a substrate such as glass, it is difficult to stably form the conductive pattern in the roll printing process using the conventional conductive metal ink composition, and also in the PECVD process under severe conditions. There was a problem that the phenomenon of peeling (peeling) of the film occurs.
- an adhesion promoter including the second metal powder or the compound of the second metal is applied, and the adhesion promoter including the second metal powder or the compound of the second metal is easily applied to a substrate such as glass. Not only can be attached, but also an alloy with the conductive first metal powder can be formed, thereby significantly improving the adhesion of the conductive pattern and the substrate. Accordingly, the conductive pattern formed by using the conductive metal ink composition is firmly attached to the substrate without the phenomenon of peeling of the conductive pattern film even when the PECVD process under the harsh conditions applied in the flat panel display manufacturing process using TFT or the like is applied. The state can be maintained.
- the second metal powder or the compound of the second metal acts as a kind of compatibilizer between the first metal powder and the glass, so that the thin film including the first metal powder having poor adhesion with the glass is formed. It maintains stable contact with glass.
- the adhesion between the second metal powder or the compound of the second metal and the glass should be good. There is a characteristic that can form a positive bond.
- the adhesion stability of the second metal and the glass is better than that of the other metal.
- the second metal can be combined with the first metal to form a stable alloy, the first metal is partially alloyed with the second metal through heat treatment, and a part of the second metal is formed of glass and atoms. It is possible to achieve a positive combination. Through this process, a conductive metal thin film having improved adhesion to glass can be formed.
- metals capable of forming stable silicides include nickel (Ni), bismuth (Bi), tin (Sn), titanium (Ti), palladium (Pd), chromium (Cr), cobalt (Co), and germanium (Ge) , Zinc (Zn), molybdenum (Mo), tantalum (Ta), niobium (Nb), magnesium (Mg), tungsten (W) vanadium (V) and the like.
- the conductive metal ink composition includes, as a medium, first and second non-aqueous solvents having different vapor pressures at room temperature. These first and second nonaqueous solvents have different volatility by different vapor pressures, and in particular, the second nonaqueous solvent exhibits low vapor pressure and thus high volatility at room temperature.
- the conductive metal ink composition comprising these first and second nonaqueous solvents has a low viscosity during storage and until applied to a roller for roll printing, and the medium comprising the first and second nonaqueous solvents.
- a uniform composition such as conductive metal powder can be maintained within. Therefore, the conductive metal ink composition is easy to apply uniformly on the roller.
- the second non-aqueous solvent may immediately volatilize, and the viscosity may be greatly increased in about several minutes. Therefore, it becomes easy to pattern the ink composition applied on the roller into a desired shape, and even after the pattern is formed, the ink composition can maintain a good pattern shape without flowing down on the roller.
- the conductive metal ink composition of one embodiment of the invention includes a first metal powder having conductivity.
- the first metal powder any metal powder known to exhibit electrical conductivity may be used, but at least one of silver (Ag) and copper (Cu) having high conductivity among metals may be selected.
- the first metal powder may have a nano-scale average particle diameter.
- the first metal powder may have an average particle diameter of 1 to 100 nm, preferably 5 to 70 nm, more preferably 5 to 50 nm.
- the first metal powder may be included in an amount of 15 to 30% by weight based on the weight sum of the first metal powder, the first and second non-aqueous solvents, and the polymer coatability improving agent among the components of the ink composition. Can be. When the content of the first metal powder is too small, the conductivity of the conductive pattern formed from the ink composition may not be sufficient. On the contrary, when the content of the first metal powder is too large, the dispersibility of the metal powder in the ink composition may be poor, resulting in poor properties of the conductive pattern. Uniform application of the ink composition can be difficult to achieve.
- the conductive metal ink composition includes first and second non-aqueous solvents.
- the first nonaqueous solvent is a solvent having a vapor pressure of 3 torr or less at 25 ° C. and exhibiting relatively low volatility, and may serve as a dispersion medium of the ink composition before firing.
- any non-aqueous solvent known to have a vapor pressure of 3 torr or less at 25 ° C. may be used.
- an alcohol solvent, a glycol solvent, a polyol solvent, a glycol ether having a vapor pressure of 3 torr or less at 25 ° C. may be used.
- Two or more mixed solvents selected from these solvents, glycol ether ester solvents, ketone solvents, hydrocarbon solvents, lactate solvents, ester solvents, aprotic sulfoxide solvents or nitrile solvents You can also use More specific examples of such a first non-aqueous solvent include ethylene glycol, propylene glycol, glycerol, propylene glycol propyl ether, ethylene glycol monophenyl ether, ethylene glycol monoisopropyl ether, propylene glycol monobutyl ether, diethylene glycol monobutyl ether, Diethylene glycol monobutyl ether acetate, diethylene glycol ethyl ether, N-methylpyrrolidone, hexadecane, pentadecane, tetradecane, tridecane, dodecane, undecane, decane, DMSO, acetonitrile, acetone alcohol or butyl And cellosolves
- the second non-aqueous solvent is a solvent having a vapor pressure of more than 3 torr at 25 ° C. and exhibiting high volatility, and as described above, the low viscosity of the ink composition and the roller together with the first non-aqueous solvent until the ink composition is applied onto the rollers. It is a component that maintains excellent applicability to, but is removed by evaporation to increase the viscosity of the ink composition and to facilitate the formation and maintenance of the pattern on the roller.
- any non-aqueous solvent known to have a vapor pressure of more than 3 torr at 25 ° C. may be used.
- an alcohol solvent, a glycol ether solvent, or a glycol having a vapor pressure of more than 3 tor at 25 ° C. may be used.
- An ether ester solvent, a ketone solvent, a hydrocarbon solvent, a lactate solvent, an ester solvent, an aprotic sulfoxide solvent, a nitrile solvent, or the like may be used, or two or more mixed solvents selected from them may be used. .
- Such a second non-aqueous solvent include methanol, ethanol, propanol, isopropanol, n-butanol, t-butanol, pentanol, hexanol, nonan, octane, heptane, hexane, acetone, methyl ethyl ketone, methyl isobutyl Ketone, methyl cellosolve, ethyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol methyl ether acetate, chloroform, methylene chloride, 1,2-dichloroethane, 1,1,1-trichloroethane , 1,1,2-trichloroethane, 1,1,2-trichloroethene, cyclohexane, tetrahydrofuran, benzene, toluene or xylene, and the like.
- first and second non-aqueous solvents are, for example, 5 to 70% by weight, based on the weight sum of the first metal powder, the first and second non-aqueous solvents, and the polymer coating improver among the components of the ink composition. And it may be included in an amount of 10 to 74% by weight.
- the drying rate may be difficult after transferring the ink composition to the roller, thereby making it difficult to transfer the substrate.
- the drying speed may be slow, resulting in a long process time and difficulty in uniform application of the ink composition.
- the conductive metal ink composition of one embodiment of the invention is to improve the adhesion with a substrate such as glass to form a conductive pattern stably, nickel (Ni), bismuth (Bi), tin (Sn), titanium (Ti) ), Palladium (Pd), chromium (Cr), cobalt (Co), germanium (Ge), zinc (Zn), molybdenum (Mo), tantalum (Ta), niobium (Nb), magnesium (Mg), tungsten (W ), Adhesion promoters comprising a second metal powder or a compound of the second metal of vanadium (V) or mixtures thereof.
- the second metal component included in the second metal powder or the compound of the second metal may not only form an alloy with the first metal powder, but also has a high adhesion to a substrate such as glass, such that the adhesion promoter comprising the The conductive pattern formed using the conductive metal ink composition can be stably attached to the substrate on glass or the like.
- Adhesion promoter a powder of the second metal, a compound of the second metal, or a mixture thereof may be used.
- Adhesion promoters applied in the form of metal powders have a high adhesion to substrates such as glass, can be easily alloyed with the first metal powder, and can be stably dispersed on the ink composition.
- the compound of the second metal may also serve as an adhesion promoter, like the powder of the second metal.
- Specific examples thereof include oxides of the second metals, carboxylates of the second metal, and a second metal. Acetylacetonate or a mixture thereof .
- the powder of the second metal may have an average particle diameter of nanoscale.
- the compound of the second metal may be added after dissolving in a suitable solvent.
- the adhesion promoter may be included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the conductive first metal powder included in the ink composition.
- the adhesion promoter may be included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the conductive first metal powder included in the ink composition.
- the content of the adhesion promoter is too small, the adhesion of the conductive pattern to the substrate may not be sufficiently improved. If the content of the adhesion promoter is too large, the viscosity of the ink composition may be high, which may cause inconvenience in the process.
- any dispersant known to be used in the conductive metal ink composition may be further added.
- the dispersant polyethylene glycol, polyethylene glycol nonylphenyl ether, polyethylene glycol sorbitan trioleate, polyethylene glycol sorbitan monooleate, polyethylene glycol sorbitan monolaurate, polyethylene glycol sorbitan monopalmitate, polyethyleneimine, polyacrylic acid , Polymers of known structures such as polyvinylpyrrolidone, polyacrylamide, sodium polyacrylate and derivatives thereof, or BYK's Disperbyk® 111, Disperbyk® 110, Disperbyk® 106, Disperbyk® 140, Disperbyk® 108, Disperbyk ® 174, Disperbyk® 180, Disperbyk® 183, Disperbyk® 184, Disperbyk® 190, or Tego® 652 from Tego, and the like, may
- the conductive metal ink composition may include a polymer coating improver.
- a coating enhancer is a component that acts as a binder in the ink composition and imparts adhesion to the ink composition, so that the ink composition can be well applied or transferred to the substrate on which the conductive pattern is to be formed as well as the roller.
- An epoxy-based polymer, a phenol-based polymer or an alcohol-based polymer may be used as the coating improver, and a mixture of two or more selected from these may be used. More specific examples of the epoxy-based polymer among these coating improvers include flame-retardant epoxy polymers such as bisphenol A type epoxy polymers, bisphenol F type epoxy polymers, novolac type epoxy polymers, brominated epoxy polymers, epoxy polymers having aliphatic rings, and rubber modifications. Epoxy polymers, aliphatic polyglycidyl epoxy polymers or glycidyl amine epoxy polymers.
- phenolic polymer examples include novolak-type phenolic polymers or resol type phenolic polymers, and the like
- alcohol-based polymers may include cellulose-based polymers, polyvinyl alcohol, ethylene vinyl alcohol polymers, or benzyl alcohol polymers.
- ethylene vinyl acetate, rosin-based resin, styrene-butadiene-styrene polymer or polyester polymer may be used.
- the coating improver As materials belonging to these specific examples, materials well known or commercialized in the art may be used as the coating improver, and in addition to these materials, various polymer materials known to be usable in the conductive ink composition may be used as the coating improver. .
- the ink composition includes these coatability enhancers, such ink composition can exhibit excellent applicability to rollers and good transferability to a substrate, and thus can be suitably applied to roll printing processes and the like.
- the conductive pattern can be formed well.
- the polymer coating improver may be included in an amount of 0.1 to 5 wt% based on the weight sum of the first metal powder, the first and second non-aqueous solvents, and the polymer coating improver among the components of the ink composition. Can be. If the content of the coating improver is too small, the coating property or transferability of the ink composition may not be sufficient, and if too large, the conductivity of the conductive pattern formed from the ink composition may be insufficient.
- the conductive metal ink composition according to the present invention may further include an additive such as a surfactant.
- an additive such as a surfactant.
- the type of the surfactant is not particularly limited, and materials known in the art may be used.
- the conductive metal ink composition of one embodiment of the present invention may further include an organic silver complex in which an organic ligand including an amine group and a hydroxyl group is bonded to an aliphatic carboxylic acid silver (Ag) to form a complex.
- an organic silver complex in which an organic ligand including an amine group and a hydroxyl group is bonded to an aliphatic carboxylic acid silver (Ag) to form a complex.
- Such organic silver complex compounds may be those disclosed in Korean Patent Laid-Open Publication No. 2008-0029826, for example. They have a high solubility in solvents, maintain liquid phase at room temperature, and exhibit excellent stability in ink compositions without a separate dispersant. Can be. In other words, these organic silver complexes can act as a kind of medium and contain silver (Ag) by itself. Incorporation of such organic silver complexes into the conductive metal ink composition can include more conductive metal components, such as silver (Ag) or other conductive powders, while reducing the amount of non-aqueous solvent contained in the ink composition. have. Therefore, the conductive metal ink composition including such an organic silver complex with the first metal powder having conductivity may exhibit more improved conductivity.
- Such an organic silver complex may be one in which an organic ligand selected from the group consisting of primary to quaternary amines substituted with alcohol groups is combined with aliphatic carboxylic acid silver.
- the aliphatic carboxylic acid silver may be selected from the group consisting of primary or secondary fatty acid silver (Ag) salts having 2 to 20 carbon atoms.
- the organic ligand and aliphatic carboxylic acid silver (Ag) constituting such an organic silver complex may be combined at an equivalent ratio of 2: 1 to form a complex.
- organic silver complexes exhibit low crystallinity and thus good solubility in solvents depending on the shape of the complex and can be liquid at room temperature.
- Such organic silver complexes can themselves serve as liquid media, and as such are further included in the ink composition, a higher content of conductive metal can be achieved while reducing the content of the medium, ie, non-aqueous solvent, contained in the ink composition.
- the content of the silver component (eg, Ag) contained in the component, for example, the first metal powder or the complex compound may be increased. Accordingly, it has been found that by applying such an ink composition, a conductive pattern exhibiting improved conductivity can be formed by a roll printing process.
- the organic silver complex compound includes an organic ligand and an aliphatic carboxylic acid silver in an equivalent ratio of 2: 1, and thus has two hydroxyl groups per molecule, and thus, for example, at room temperature (about 25 to 50 cPs at about 25 ° C).
- the organic silver complex may preferably function as a kind of medium of the ink composition, and the ink composition may maintain excellent dispersion stability even under low content of non-aqueous solvent.
- the ink composition further comprises the organic silver complex, it is possible to form a conductive pattern exhibiting a higher density of the conductive metal component and thus excellent conductivity.
- Such organic silver complex compounds may be prepared by a method of reacting the above-described organic ligand and aliphatic carboxylic acid silver under a solvent, as disclosed in Korean Patent Laid-Open Publication No. 2008-0029826, wherein solvents such as methanol and terpineol Or butyl carbitol acetate.
- the organic silver complex may be included in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the conductive first metal powder included in the ink composition.
- the content of the organic silver complex compound is too small, the conductivity of the conductive pattern formed from the ink composition may become insufficient. If the content of the organic silver complex compound is too large, the viscosity of the ink composition may be high, resulting in inconvenience in the process. Can be.
- the conductive metal ink composition according to the embodiment of the present invention may have an initial viscosity of 10 cPs or less, preferably 5 cPs or less.
- the initial viscosity may refer to the viscosity from the time of initial manufacture of the conductive metal ink composition to when applied to a roller for a roll printing process.
- the conductive metal ink composition may have such a low initial viscosity, including the first and second nonaqueous solvents, and thus may exhibit good applicability to the roller.
- the viscosity may be high on the rollers due to the evaporation of the second non-aqueous solvent, which is highly volatile, which results in good pattern formation and retention on the rollers and good transfer of patterns on the substrate. You can.
- the roll printing process using the conductive metal ink composition it is possible to form a finer conductive pattern on the substrate well, such that the conductive pattern can exhibit a superior conductivity.
- the conductive metal ink composition may be preferably applied by a roll printing process to be printed on a substrate, for example, a glass substrate or the like to form a conductive pattern, and in particular, to form an electrode pattern or the like of a flat panel display element. Very preferably.
- a method of forming a conductive pattern using the above-described conductive metal ink composition may include applying the aforementioned conductive metal ink composition to a roller; Contacting the roller with a cliché in which a pattern corresponding to the conductive pattern is engraved to form a pattern of an ink composition corresponding to the conductive pattern on the roller; Transferring the ink composition pattern on the roller onto a substrate; And firing the transferred pattern on the substrate.
- the cliché means a kind of uneven plate used for patterning the ink composition applied on the roller in the form of a desired conductive pattern.
- a pattern corresponding to the conductive pattern may be formed on the cliché.
- FIG. 1 is a view schematically showing a process of forming a conductive pattern through a roll printing process.
- the above-mentioned conductive metal ink composition is formed.
- the components may be mixed and then stirred or shaken to form a uniform ink composition.
- the step of filtering the ink composition may be further performed to remove impurities and allow the conductive pattern to be evenly formed.
- the conductive ink composition 22 is applied to the roller 20.
- the outer surface of the roller 20 may be covered with a blanket 21, the blanket 21 may be made of polymethyl cellulose (PDMS).
- PDMS polymethyl cellulose
- Such PDMS is excellent in viscoelasticity, deformation property or transferability compared to other polymer materials, and thus may be suitably used as the blanket 21.
- the conductive ink composition 22 may be discharged from the discharge port 10 of the supply apparatus and applied onto the blanket 21, from which the second non-aqueous solvent begins to evaporate, and thus the viscosity of the ink composition 22 may be high. It starts to increase at a speed.
- a cliché in which a pattern corresponding to a desired conductive pattern is engraved in contact with the roller is used to contact the roller with a pattern of the ink composition corresponding to the conductive pattern.
- the cliché 30 serves to selectively remove the ink portion 32 which is not necessary for forming the conductive pattern in contact with the blanket 21 to which the ink composition 22 is applied, and as a result, the desired composition on the roller A pattern of the ink composition corresponding to the conductive pattern can be formed.
- the cliché 30 has a shape in which a pattern corresponding to a desired conductive pattern is engraved on the surface in contact with the blanket 21, so that only the protrusions 31 of the cliché 30 are blanket 21.
- the ink portion 32 which is not required for the formation of the conductive pattern in contact with the ink composition 22 on the X-rays), can be transferred to the protrusions 31 and removed.
- the pattern of the ink composition is transferred onto the substrate.
- the blanket 21 of the roller on which the pattern of the ink composition is formed can be brought into contact with the substrate 40, and as a result, the pattern of the ink composition is transferred to the substrate 40 so that a predetermined pattern on the substrate 40 can be obtained. 41 can be formed.
- a firing process may be performed to form a conductive pattern on the substrate.
- the firing process may be performed under appropriate conditions depending on the type of the conductive pattern to be formed. For example, when the conductive pattern is an electrode pattern of a flat panel display device, the firing process may be performed at 400 to 600 ° C. It may proceed for 50 minutes, for example, it may proceed for 10 to 40 minutes at 450 °C.
- the conductive pattern forming method using the above-described roll printing process it is possible to form the conductive pattern on the substrate in a very simple and fast process compared to the photolithography process, etc. previously applied.
- the conductive metal ink composition and the like according to the embodiment of the invention described above in the roll printing process it is possible to form a fine conductive pattern showing excellent conductivity, for example, an electrode pattern of a flat panel display device, etc. Can be.
- the blanket was contacted with a cliché in which a pattern corresponding to a desired conductive pattern was intaglio, thereby forming a pattern of the ink composition on the roller.
- This roller was then contacted with the glass substrate to form a pattern on the glass substrate. This was baked for 10 minutes in a 450 °C thermal kiln to form a conductive pattern.
- An ink composition was prepared in the same manner as in Example 1, except that nickel nanoparticles having an average particle diameter of 100 nm were not added, and a conductive pattern was formed.
- the adhesion of the conductive patterns formed in Examples 1 to 8 and Comparative Example 1 was evaluated according to ASTM D3359 method (cross cutting tape test). Specifically, eleven gold was drawn on the conductive patterns of Examples 1 to 8 and Comparative Example 1 at intervals of 1 mm in width and length, respectively, and the ratio of the area removed when the Nichibang tape was attached and detached was evaluated.
- FIGS. 1 and 2 Attachment states of the conductive patterns on the substrate according to Example 1 and Comparative Example 1 are shown in FIGS. 1 and 2.
- the sheet resistance of the conductive patterns of Examples 1 to 8 and Comparative Example 1 was measured by a 4-point probe, and the thickness thereof was measured using an Alpha step surface profiler to determine the conductive patterns of Examples 1 to 8 and Comparative Example 1. The specific resistance was obtained.
- the conductive patterns of Examples 1 to 8 and Comparative Example 1 were rubbed several times with a soft, dust-free cloth, and measured to the extent that ink appeared on the cloth.
- the removed area is ' ⁇ ' when the ratio is not changed to 0% at all, ' ⁇ ' when it is more than 0% and 5% or less, ' ⁇ ' when it is more than 5% and 20% or less, and 20 Exceeding% is indicated by 'x'.
- the conductive metal ink composition according to the present invention can be suitably applied to a roll printing process, etc., to form a conductive pattern exhibiting more improved conductivity and excellent adhesion to a substrate.
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Abstract
Description
Claims (16)
- 전도성을 갖는 제1 금속 분말;25℃에서 증기압이 3torr 이하인 제1 비수용매 및 25℃에서 증기압이 3torr를 초과하는 제2 비수용매를 포함하는 비수용매;니켈(Ni), 비스무트(Bi), 주석(Sn), 티타늄(Ti), 팔라듐(Pd), 크롬(Cr), 코발트(Co), 게르마늄(Ge), 아연(Zn), 몰리브덴(Mo), 탄탈륨(Ta), 니오븀(Nb), 마그네슘(Mg), 텅스텐(W) 및 바나듐(V)으로 이루어진 군에서 선택된 하나 이상의 제2 금속 분말 또는 제2 금속의 화합물을 포함하는 부착 증진제; 및고분자 코팅성 향상제를 포함하는 전도성 금속 잉크 조성물.
- 청구항 1에 있어서, 상기 제1 금속 분말은 은(Ag) 및 구리(Cu)로 이루어진 군으로부터 선택되는 1종 이상을 포함하는 것을 특징으로 하는 전도성 금속 잉크 조성물.
- 청구항 1에 있어서, 상기 제1 금속 분말의 평균 입경은 1 ~ 100nm인 것을 특징으로 하는 전도성 금속 잉크 조성물.
- 청구항 1에 있어서, 상기 제1 비수용매는 에틸렌글리콜, 프로필렌글리콜, 글리세롤, 프로필렌글리콜 프로필에테르, 에틸렌글리콜 모노페닐에테르, 에틸렌글리콜 모노이소프로필에테르, 프로필렌글리콜 모노부틸에테르, 디에틸렌글리콜 모노부틸에테르, 디에틸렌글리콜 모노부틸에테르 아세테이트, 디에틸렌글리콜 에틸에테르, N-메틸피롤리돈, 헥사데칸, 펜타데칸, 테트라데칸, 트리데칸, 도데칸, 운데칸, 데칸, DMSO, 아세토니트릴, 아세톤알코올 및 부틸셀로솔브로 이루어진 군으로부터 선택되는 1종 이상을 포함하는 것을 특징으로 하는 전도성 금속 잉크 조성물.
- 청구항 1에 있어서, 상기 제2 비수용매는 메탄올, 에탄올, 프로판올, 이소프로판올, n-부탄올, t-부탄올, 펜탄올, 헥산올, 노난, 옥탄, 헵탄, 헥산, 아세톤, 메틸에틸케톤, 메틸이소부틸케톤, 메틸셀로솔브, 에틸셀로솔브, 에틸렌글리콜 디메틸에테르, 에틸렌글리콜 디에틸에테르, 프로필렌글리콜 메틸에테르 아세테이트, 클로로포름, 염화메틸렌, 1,2-디클로로에탄, 1,1,1-트리클로로에탄, 1,1,2-트리클로로에탄, 1,1,2-트리클로로에텐, 시클로헥산, 테트라하이드로푸란, 벤젠, 톨루엔및 자일렌으로 이루어진 군으로부터 선택되는 1종 이상을 포함하는 것을 특징으로 하는 전도성 금속 잉크 조성물.
- 청구항 1에 있어서, 상기 부착 증진제는 제2 금속 분말 단독, 제2 금속의 산화물, 제2 금속의 카르복실레이트 및 제2 금속의 아세틸아세토네이트로 이루어진 군으로부터 선택되는 1종 이상을 포함하는 것을 특징으로 하는 전도성 금속 잉크 조성물.
- 청구항 1에 있어서, 상기 부착 증진제의 함량은 상기 제1 금속 분말의 100 중량부를 기준으로, 0.1 내지 10 중량부인 것을 특징으로 하는 전도성 금속 잉크 조성물.
- 청구항 1에 있어서, 상기 고분자 코팅성 향상제는 에폭시계 고분자, 페놀계 고분자및 알코올계 고분자로 이루어진 군으로부터 선택되는 1종 이상을 포함하는 것을 특징으로 하는 전도성 금속 잉크 조성물.
- 청구항 1에 있어서, 상기 전도성 금속 잉크 조성물은 유기 은 착화합물을 추가로 포함하는 것을 특징으로 하는 전도성 금속 잉크 조성물.
- 청구항 9에 있어서, 상기 유기 은 착화합물은 알코올기로 치환된 1차 내지 4차 아민으로 이루어진 군에서 선택되는 유기 리간드와 지방족 카르복실산 은을 포함하는 것을 특징으로 하는 전도성 금속 잉크 조성물.
- 청구항 9에 있어서, 상기 유기 은 착화합물의 함량은 상기 제1 금속 분말의 100 중량부를 기준으로, 0.1 내지 5 중량부인 것을 특징으로 하는 전도성 금속 잉크 조성물.
- 청구항 1에 있어서, 상기 전도성 금속 잉크 조성물의 점도는 10cPs 이하인 것을 특징으로 하는 전도성 금속 잉크 조성물.
- 청구항 1에 있어서, 상기 전도성 금속 잉크 조성물은 롤프린팅 공정용인 것을 특징으로 하는 전도성 금속 잉크 조성물.
- 청구항 1 내지 청구항 13 중 어느 한 항의 전도성 금속 잉크 조성물을 롤러에 도포하는 단계;전도성 패턴에 대응하는 패턴이 음각으로 형성된 클리셰를 상기 롤러에 접촉시켜, 상기 전도성 패턴에 대응하는 잉크 조성물의 패턴을 상기 롤러 상에 형성하는 단계;상기 롤러 상의 잉크 조성물 패턴을 기판 상에 전사하는 단계; 및상기 기판 상에 전사된 패턴을 소성하는 단계를 포함하는 전도성 패턴의 제조방법.
- 청구항 14에 있어서, 상기 소성하는 단계는 400 ~ 600℃에서 5 ~ 50분 동안 수행되는 것을 특징으로 하는 전도성 패턴의 제조방법.
- 청구항 14의 전도성 패턴의 제조방법에 따라 제조되고, 비저항이 4 μΩ·cm 이하인 것을 특징으로 하는 전도성 패턴.
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US13/819,313 US9449734B2 (en) | 2010-08-27 | 2011-08-26 | Conductive metal ink composition, and method for preparing a conductive pattern |
JP2013525840A JP5788003B2 (ja) | 2010-08-27 | 2011-08-26 | 導電性金属インク組成物および導電性パターンの形成方法 |
CN201180041472.6A CN103080247B (zh) | 2010-08-27 | 2011-08-26 | 导电金属墨水组合物及制备导电图形的方法 |
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- 2011-08-26 CN CN201180041472.6A patent/CN103080247B/zh active Active
- 2011-08-26 WO PCT/KR2011/006343 patent/WO2012026791A2/ko active Application Filing
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Also Published As
Publication number | Publication date |
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JP5788003B2 (ja) | 2015-09-30 |
KR20120020086A (ko) | 2012-03-07 |
CN103080247B (zh) | 2016-05-25 |
JP2013541602A (ja) | 2013-11-14 |
US9449734B2 (en) | 2016-09-20 |
KR101302345B1 (ko) | 2013-08-30 |
US20130277096A1 (en) | 2013-10-24 |
WO2012026791A3 (ko) | 2012-06-28 |
CN103080247A (zh) | 2013-05-01 |
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