WO2015005665A1 - 탄소나노튜브 또는 탄소나노류브 -금속 복합체를 이용한 세라믹 페이스트 조성물 및 이를 포함하는 도전성 필름 - Google Patents

탄소나노튜브 또는 탄소나노류브 -금속 복합체를 이용한 세라믹 페이스트 조성물 및 이를 포함하는 도전성 필름 Download PDF

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WO2015005665A1
WO2015005665A1 PCT/KR2014/006141 KR2014006141W WO2015005665A1 WO 2015005665 A1 WO2015005665 A1 WO 2015005665A1 KR 2014006141 W KR2014006141 W KR 2014006141W WO 2015005665 A1 WO2015005665 A1 WO 2015005665A1
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Prior art keywords
ceramic paste
paste composition
weight
carbon nanotube
disperbyk
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PCT/KR2014/006141
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English (en)
French (fr)
Inventor
박한오
김재하
김준표
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(주)바이오니아
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Application filed by (주)바이오니아 filed Critical (주)바이오니아
Priority to US14/904,358 priority Critical patent/US10249404B2/en
Priority to JP2016525278A priority patent/JP6173581B2/ja
Priority to EP14822163.3A priority patent/EP3021328B1/en
Priority to CN201480039822.9A priority patent/CN105493198B/zh
Publication of WO2015005665A1 publication Critical patent/WO2015005665A1/ko

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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
    • 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
    • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/71—Ceramic products containing macroscopic reinforcing agents
    • C04B35/74—Ceramic products containing macroscopic reinforcing agents containing shaped metallic materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/71—Ceramic products containing macroscopic reinforcing agents
    • C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
    • C04B35/80—Fibres, filaments, whiskers, platelets, or the like
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • 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
    • H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
    • 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
    • H01B1/14—Conductive material dispersed in non-conductive inorganic material
    • H01B1/18—Conductive material dispersed in non-conductive inorganic material the conductive material comprising carbon-silicon compounds, carbon or silicon
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
    • H05B3/12—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
    • H05B3/14—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B2214/00—Aspects relating to resistive heating, induction heating and heating using microwaves, covered by groups H05B3/00, H05B6/00
    • H05B2214/04—Heating means manufactured by using nanotechnology

Definitions

  • Ceramic paste compositions using carbon nanotubes or carbon nanotubes-metal composites and conductive films comprising them Paste compositions and conductive films comprising the same
  • Silicon binder-based ceramic paste compositions and conductive films containing them even at high temperatures above 300 ° C, do not cause desorption or film degeneration of the electrode coated in film form.
  • Conventional techniques related to carbon materials include the production of heat-generating sheets using fiber heating elements of carbon materials, such as Korean Patent Publication No. 10-2012-0000878, or liquid phase heating compositions, such as Korean Patent No. 10-1029147.
  • the heating composition is manufactured and applied to the sheet or further includes a heat generating layer on the base layer, desorption of the heat generating layer or coating film in a high temperature environment of 300 ° C or higher There is a disadvantage that this occurs or the coating film is easily broken.
  • the carbon nanotube-metal composite is used, and there is no change in physical properties even at high temperatures above 300 ° C, and the ceramic paste composition using carbon nanotube or carbon nano-rubbe-metal composite, which does not occur when the conductive film in the form of a coating film, is produced.
  • the purpose of providing a conductive film containing is for this purpose. '' Task solution
  • the present invention is a ceramic using carbon nanotubes or carbon nanotube-metal complexes.
  • An aspect of the present invention is a ceramic paste composition
  • a ceramic paste composition comprising a carbon nanotube or a carbon nanotube-metal composite and a silicone pressure-sensitive adhesive, wherein the silicone adhesive contains 0.1 to 10 weight percent of total 100% by weight of silanol groups.
  • the ratio of phenyl groups to methyl groups is about 0.3 to 2.5 molar ratios of ceramic paste compositions.
  • the metal contained in the carbon nano-rubber-metal complex may be one or two or more selected from silver, platinum, gold, copper, nickel, iron, cobalt, and aluminum, and the content of the metal is carbon nanocarbon. It can contain 1 to 80 parts by weight for 100 parts by weight of the tube-metal complex.
  • the ceramic paste composition may be a carbon nano-leube or a carbon nano-leube-metal
  • Another aspect of the present invention is a ceramic paste composition, wherein the ceramic paste composition further comprises an organic binder, a dispersant, and an organic solvent.
  • the organic binder is any one selected from ethyl cellulose, nitro sal and a mixture thereof; the dispersant is an amino-containing oligomer or a phosphorus ester salt of a polymer, a monoester or diester of phosphoric acid, an acidic dicarboxylic acid
  • Organic solvents include acetone, methyl ethyl ketone, methyl alcohol, ethyl alcohol, isopropyl alcohol, Butyl alcohol, ethylene glycol, polyethylene glycol, tetrahydrofuran, dimethylformamide, dimethylacetamide, N-methyl-2-pyridone, nucleic acid,
  • the ceramic paste composition may include 1 to 50% by weight of carbon nano-leubu or carbon nanotube-metal composite, 1 to 20% by weight of organic binder, 1 to 30% by weight of silicone adhesive, 1 to 20% by weight of dispersant, and 1 to 20% by weight of organic solvent. It can be made up to 90 weight 1 3 ⁇ 4.
  • Another aspect of the invention relates to a conductive film including the ceramic paste composition.
  • the conductive film in a thickness of 10 to 600 when the applied voltage of 1.5 to 220V the heat temperature that is 40 to 400 ⁇ C With all the features. Effects of the Invention
  • the ceramic paste composition according to the present invention is characterized by low surface resistance, which can provide excellent heat generation, shielding, absorption, and conduction characteristics. Although very high at ° C, the physical properties of the paste composition can be stably maintained to realize the unique characteristics of the ceramic paste.
  • the ceramic paste can be easily manufactured with a conductive film on a plane by a simple process, and is widely used in various fields such as heating, heat generating products, electromagnetic shielding and absorption articles, electrodes, electronic circuits, and antennas. Can be Brief description of the drawings
  • FIG. 1 illustrates a conductive film using a ceramic paste composition according to an embodiment of the present invention.
  • FIG. 2 is a diagram illustrating measurement of a heat generation effect when an applied voltage of 100 V is applied to a conductive film manufactured according to an embodiment of the present invention using a thermal imaging camera (Ti32, Fluke).
  • Example 3 shows the temperature change according to the applied voltage of the conductive film prepared in Example 1.
  • FIG. 4 shows the temperature change depending on the applied voltage over three times of the conductive film manufactured in Example 2.
  • paste composition used in the present invention encompasses the state of solid solids and liquids, and may be, for example, a mixture paste having an adhesive or adhesive property.
  • the ceramic paste composition may include carbon nanotubes (CNTs) or carbon nanotube-metal composites, organic binders, silicone adhesives, dispersants, and organic solvents. It may include.
  • the carbon nano-lube has a cylindrical composite structure in which a graphite layer is wound and S p2 bonds, such as graphite, and is used as a heat generating and high conductive material in the ceramic paste composition.
  • the carbon nano-lube or carbon nano-lube-metal complex is effective as a heat-generating and high-conducting material by effectively lowering the contact resistance of the ceramic paste composition in a relatively small amount compared to the existing heating element composition, and is effective in shielding and absorbing electromagnetic waves. outstanding.
  • the carbon nanotubes that can be used in the present invention are not limited to the manufacturing method and the diameter of the column.
  • the single-wall carbon nanotubes such as single wall carbon nanotubes and double wall carbon nanotubes can be used.
  • CNTs multi-walled CNTs or combinations thereof.
  • the carbon nanotube-metal composite may be formed of the carbon nanotubes.
  • Metal ions are uniformly mixed to mean nano composite powders produced through a molecular level process, and carbon nano-orb-metal composites that can be used in the present invention are not limited to the manufacturing method and the shape of the diameter column.
  • the carbon nano-lube-metal composite can effectively lower the contact resistance of the ceramic paste composition with a relatively small content, so it is effective as a heat generating and high conductive material, and has excellent electromagnetic shielding and absorption ability, thereby realizing a large area.
  • the specific synthesis process for the carbon nano-leube-metal complex can be found in Korean Patent No. 10-1095840.
  • metals such as silver (Au), platinum (Pt), silver (Ag), copper (Cu), nickel (Ni), iron (Fe), cobalt (Co) and aluminum ( Any one or a mixture thereof selected from A1) may be a compound containing the above metal in addition to the metal ion.
  • silver or platinum is preferably used as the above metal.
  • the carbon content of the carbon nanotube-metal complex is carbon nanotube-metal complex.
  • 1 to 80 parts by weight is preferred for 100 parts by weight, preferably 20 to 60 parts by weight for excellent conductivity and excessive conductivity.
  • the silicone adhesive acts as a dispersant to promote the dispersion of the carbon nanotubes or carbon nanoleube-metal complexes, and may also act as a viscosity agent to stabilize the ceramic paste mixture solution prepared.
  • Adhesives commonly used in combination with carbon nanotubes or carbon nanotube-metal complexes provide good control for stabilization of carbon nanotubes or carbon nanotube-metal complexes during processing (coating or thin film formation) of the prepared paste compositions. It has been used to include N, 0, S or other functional groups with lone pair electrons to provide coordination bonds, especially polymer binders with high oxygen content such as hydroxyl and carboxyl groups.
  • adhesives include epoxy resins, phenol resins, phenol resins, urethane resins, polyester resins, polyvinylchloride resins, and urea resins.
  • Polyethylene resins, acrylic resins, these polymers have a strong affinity for the surface of the carbon nano- or carbon nano-rubber-metal complex. It said, can enhance the dispersibility and stability, but these resins are therefore not jokhaji layer heat resistance required in the invention, it is preferable to use a pressure-sensitive adhesive of the silicone series.
  • Silicone adhesives according to the present invention alternately form silicon (Si) atoms and oxygen (0)
  • silicon is usually a structure in which two organic atoms of alkyl or phenyl (-CeH 5 ) such as methyl, ethyl, and propyl are bonded to each silicon atom.
  • the pressure sensitive adhesive may have hydrogen, hydroxy, methyl, or phenyl groups bonded to the polysiloxane backbone, wherein the content of the polysiloxane backbone, ie, Si0 2 , is 45 to 65% by weight, preferably 47 to 63% by weight, relative to 100% by weight of the total silicone adhesive. good.
  • the silicone adhesive improves dryness and provides excellent flexibility.
  • the content of silanol having a hydroxyl group as a functional group has a certain range, preferably 0.1 to 10 % by weight, and more preferably 1 to 6% by weight, based on 100% by weight of the total silicone adhesive. If the content of the knol is less than 0.1 % by weight, the dryness and strength may drop, and if it is more than 10 % by weight, the flexibility and the processability are deteriorated.
  • the silicone adhesive according to the present invention is prepared from a ceramic paste composition.
  • the ratio of the methyl group and the phenyl group is constant.
  • the ratio of the methyl group and the phenyl group is in the range of 03 to 2.5 molar ratio of phenyl group relative to 1 molar ratio of methyl group, preferably 0.4 to 2.0 molar ratio of phenyl group relative to 1 molar ratio of methyl group. If the phenyl group is less than 0.3 molar ratio, the mechanical strength and heat resistance are lowered. If the phenyl group is more than 0.3 molar ratio, the water repellency is lowered and the elasticity is high, resulting in poor workability.
  • the silicone adhesive according to the present invention can be cured by heating in the functional period due to the bonding.
  • the preferred type of curing is 55 to 80% of the crosslinking weight, and the weight average molecular weight.
  • the range of 1,000 to 400,000 is preferable in terms of processability and mechanical properties.
  • silicone adhesives for example, Dow Corning's silicone
  • Resin (XIAMETER), RSN-0409 HS, RSN-0431 HS, RSN-0804, RSN-0805, RSN-0806, RSN-0808, RSN-0840, liquid resin or RSN-0217, RSN-0220, RSN- 0233, RSN-0249
  • RSN-0409 HS RSN-0431 HS
  • RSN-0804, RSN-0805, RSN-0806, RSN-0808, RSN-0840 liquid resin or RSN-0217, RSN-0220, RSN- 0233, RSN-0249
  • the ceramic paste composition according to the present invention is a carbon nanotube or
  • the effective dispersion of carbon nanotubes or carbon nano-leube-metal complexes results in the excellent heat generation and electromagnetic shielding properties desired by the present invention. And it is desirable to be able to express conductivity.
  • the paste composition according to the present invention may further include an organic binder, a dispersant, and an organic solvent, if necessary.
  • the organic binder, the dispersant, and the organic solvent may add only one, but may add two or more as necessary. It is preferable to include all organic binders, dispersants and organic solvents.
  • composition ratio of the paste composition is carbon nano-orb or
  • Carbon nano ryubeu - it comprises a metal complex of 1 to 50% by weight, 1 to 30% by weight of an organic binder 1 to 20 parts by weight silicone pressure-sensitive adhesive, a dispersing agent 1 to 20 parts by weight ⁇ 3 ⁇ 4 and organic solvent 1 to 90 wt «3 ⁇ 4 preferred.
  • the organic binder is a ceramic paste composition prepared according to the present invention.
  • the type of organic binder is not particularly limited, and it is preferable to use a cellulose derivative.
  • the cellulose derivative may be a part or all of three hydroxy groups present in ⁇ -glucose, a cell repeating unit. For example, there is one or a combination of these selected from ethylcellulose, nitrocellulose, and the like.
  • the organic binder is not limited to the manufacturing method, but the viscosity of a certain range.
  • the organic binder is preferably 10 to 50,000 cps (centipoise), preferably 1,000 to 35,000 cps, at 25 ° C. If the viscosity is outside the above range, the tissue will not be densely formed during processing of the composition. Or cracks may occur, resulting in poor storage stability.
  • the organic binder is preferably 1 to 20 weights, preferably 3 to 15 weights, based on 100% by weight of the ceramic paste composition, to maintain the processability of the composition and to maintain the mechanical properties of the thin film and the coating.
  • the dispersing agent may be prepared by manufacturing carbonaceous paste, It is a composition that atomizes particles through the stabilization of the carbon nanotube-metal complex, improves dispersibility, and has the same surface resistance value during surface coating.
  • the dispersant does not act as a binder, and if added too much, it prevents hardening. In the case of too high a polymer, it is difficult to obtain compatibility with the binder, and a compound having a number average molecular weight of 2,000 to 20,000 is preferable.
  • the dispersant according to the present invention can be obtained by using an acid to salt an amine functional compound.
  • the amine functional compound is disclosed in Korea Patent Publication.
  • lactone polyesters e.g. caprolactone polyesters or mixed caprolactones / valeroles
  • Monoesters or diesters of phosphoric acid containing lactone polyesters Termini of the round phosphate monoester or diester, (c) alkyl, aryl, aralkyl or alkylaryl alkoxylates (e.g.,
  • Acidic dicarboxylic acid monoesters which may be exemplified as monoesters (more specifically succinic acid, maleic acid or phthalic acid), (d) poly-urethane-polyamine adducts, (e) polyalkoxylated monoamines or diamines (eg, To exemplified oleylamines or alkoxylated ethylenediamines) and (f) monoamines, diamines and polyamines, aminoalcohols and unsaturated 1,2-dicarboxylic acids and their anhydrides, and their salts and their counter-products with unsaturated fatty acids and It may be any one or more than one selected from the group consisting of semi-products of alcohols and / or amines and unsaturated fatty acids.
  • Dispersants of the above kind are made from bezel materials.
  • the dispersant is preferably 1 to 20% by weight relative to 100% by weight of the ceramic paste composition, and preferably 2 to 10% by weight is excellent in the dispersing effect even with a small amount of addition, and does not interfere with curing.
  • the organic solvent is not particularly limited as long as it is a material commonly used in the art.
  • acetone methyl ethyl ketone, methyl alcohol, ethyl alcohol, iso Propyl alcohol (isopropyl alcohol), butyl alcohol, ethylene glycol (ethyleneglycol),
  • Diethyleneglycolethylether, terpineol It may be any one or a mixture thereof, preferably using a solvent having a high volatilization temperature such as terpineol, so that the solvent composition is low, making the paste composition easy to use, and as a general purpose solvent. It has the advantage of high compatibility.
  • the content of the organic solvent may be 1 to 90% by weight relative to 100% by weight of the total silicon paste composition, preferably 40 to 80% by weight to prevent the electrical properties from deteriorating during thinning or coating film production, At the same time, it is possible to prevent a problem that the formed coating film or thin film is detached.
  • the ceramic paste composition according to the present invention is a carbon nanotube or
  • a mixed solution containing 1 to 50% by weight of the carbon nano-leucom-metal complex, 1 to 20% by weight of organic binder, 1 to 30% by weight of silicone adhesive, 1 to 20% by weight of dispersant, and 1 to 90% by weight of organic solvent can be prepared by dispersing the mixed solution.
  • the ceramic paste composition according to the present invention is
  • the step of dispersing the mixed solution in the present invention may include performing a three -roll mill method five times.
  • the ceramic paste composition according to the present invention is not limited to the method and form of application.
  • a conductive film on the surface by coating on the base layer, which can exhibit heat generation, shielding, absorption and conductivity characteristics.
  • the coating process can be carried out by methods commonly known in the art, for example, screen-printing, doctor blade, bar-coating, spin coating. -coating), 3 ⁇ 4-coating (dip-coating),
  • Spray coating, electrophoretic deposition, offset-printing, vacuum filtration or normal casting may be applied, but is not limited to this. .
  • the base layer may be used for displays ordinarily used in the art.
  • Printed circuit boards can be used.
  • Polycarbonate polycarbonate
  • Polyvinyliden fluoride or glass can be used.
  • the base layer can be freely selected according to the product use and application temperature, and the present invention is not limited to the examples listed above.
  • the conductive film prepared from the ceramic paste composition according to the present invention may vary depending on the manufacturing conditions, the size, shape and thickness of the film, but may have a sheet resistance in the range of 0.1 to 1,000 ohm / sq, preferably 1 It is preferable to have a range of from 300 ohm / sq, more preferably 1 to 150 ohm / sq.
  • the conductive film according to the present invention has a low sheet resistance, and thus has excellent heat generation, shielding and absorption characteristics. If too low, heat generation can be greatly reduced, so that high heat generation characteristics can be realized with a power consumption that is substantially lower than the surface resistance of the above range.
  • the applied voltage may be in the range of 1.5 to 220 V, preferably 10 to 220 V, More preferably, it can be 10 to 100 V. In the above range, it is possible to induce even heat generation, and at the same time prevent burns, fire and product damage caused by heat generation.
  • the ceramic paste composition according to the present invention may have a heat generation temperature of 40 to 400 ° C. when the applied voltage of the range is applied at the thickness of the range.
  • the heat generation temperature may vary according to the applied voltage.
  • the heat generation temperature may be in the range of 297 to 328 ° C.
  • the ceramic paste composition according to the present invention when the heat generation temperature exceeds 400 ° C, oxidation of carbon nanotubes occurs, polymer base layer is burned, and the coating film is peeled off, or the decomposition of the binder occurs. This can cause problems with the inherent properties of the paste composition not being implemented.
  • the conductive film manufactured from the ceramic paste composition according to the present invention may be included in a heat generating product, an electromagnetic shielding and absorbing product, and a conductive product.
  • the heat generating product may be manufactured in a variety of forms and uses for heat or heating. For example, it can be used as a heating sheet, a heating pipe, a heating vial bottle or a heating radiator, etc. Also, it can be used in all kinds of electronic products that emits electromagnetic waves such as mobile phones, televisions, and automobiles. It can be used in various circuits where electronic circuits, antennas and high conductivity are required.
  • silver paste was coated on both ends of the coating film prepared according to the following Examples and Comparative Examples, and the copper foil was coated to form the electrode. Then, the applied voltage was 0 V. The voltage was applied at 10 V intervals from to 100 V at and the heat generation temperature was measured.
  • the sheet resistance of the coating film prepared in the following Examples and Comparative Examples was measured using a surface low resistance measuring system (Loresta-GP.MCP-T610, Mitsubishi chemical analytech).
  • a surface low resistance measuring system Liesta-GP.MCP-T610, Mitsubishi chemical analytech.
  • ethyl cellulose EthylcelMose, Sigma-Aldrich
  • silicone adhesive RSN-0806, Dow Corning
  • DISPERBYK-192, BYK a dispersant
  • the ceramic paste composition was administered onto a 10 mi surface on a polyimide film of 100 mm ⁇ 100 mm, and then coated using a bar coater.
  • Coating was carried out three times, and the average thickness of the coating film per run was 100.
  • the prepared coating was prepared to 2 ° C / min uiseung the temperature was raised to an on speed to 300 o C, and then a coating film was heat-treated at 300 ° C 30 minutes at dry of the temperature change of the produced coating film, the conductivity and desorption whether The measurements are shown in Table 1.
  • a coating membrane was prepared under the same conditions as in Example 1 except that 5 g of a carbon nanotube-silver nanocomposite (Hanwha Nanotech Co., Ltd.) was used instead of carbon nanoleube.
  • the temperature change, electrical conductivity, electromagnetic shielding and desorption of the coating film were measured and shown in Table 1.
  • a coating film was prepared under the same conditions as Example 1 except that the same amount of methyl methacrylate (Da Ad Molecule Co., Ltd.) was added instead of the silicone adhesive, and the temperature change, electrical conductivity, and electromagnetic shielding of the prepared coating film were prepared. And the elimination was measured and shown in Table 1.
  • methyl methacrylate Da Ad Molecule Co., Ltd.
  • the exothermic coating film manufactured according to the present invention can be seen that the exothermic temperature also increases in proportion to the applied voltage, and using other adhesives or silicone adhesives having different physical properties. It was found that the heat resistance exceeded the degree range and the temperature change measurement was not possible above the specific voltage in Comparative Example 1. In addition, it was confirmed that the heat generation was similarly generated even after repeated experiments under the same conditions to confirm the heat durability. It was confirmed that the exothermic coating film produced in the examples was stably maintained without detachment even though the high temperature was maintained.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Conductive Materials (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Non-Insulated Conductors (AREA)

Abstract

본 발명에 따른 세라믹 페이스트 조성물은 탄소나노튜브 또는 탄소나노류브 -금속 복합체 및 실리콘 점착제를 포함하며, 상기 실리콘 점착제는 이산화규소 45 내지 65 중량 %, 실라놀기 0.1 내지 10 중량 %를 포함하며, 메틸기 : 페닐기가 1중량비 : 0.3 내지 2.5 중량비인 것을 특징으로 한다. 본 발명에 따른 세라믹 페이스트 조성물은 면저항이 낮다는 특징이 있으며, 이를 통해 우수한 발열 특성 및 차폐, 흡수, 전도특성을 구현할 수 있다. 또한 일반적인 탄소나노튜브 기반의 페이스트에 비해 발열온도가 400oC로 매우 높음에도 불구하고 페이스트 조성물의 물성이 안정적으로 유지되어 세라믹 페이스트 고유의 특성이 구현될 수 있다. 또한 상기 세라믹 페이스트는 간단한 공정으로 쉽게 면상의 도전성 필름으로 제조할 수 있으며, 이를 이용하여 보온, 난방 등 발열제품과 전자파 차폐 및 흡수용 물품, 전극, 전자회로, 안테나 등 다양한 분야에 폭넓게 이용될 수 있다.

Description

명세서
발명의명칭:탄소나노튜브또는탄소나노튜브 -금속복합체를 이용한세라믹페이스트조성물및이를포함하는도전성필름 기술분야 페이스트조성물및이를포함하는도전성필름에관한것으로,상세하게는
300°C이상의고온에서도상기페이스트가필름형태로코팅된전극의 탈리현상이나필름의변성이일어나지않는실리콘바인더기반세라믹 페이스트조성물및이를포함하는도전성필름에관한것아다.
배경기술
[2] 고분자의내열성과화학안정성의한계를극복하기위한방안으로최근고성능 및신기능세라믹발열체소재에대한기술개발이활발히이루어지고있다. 이러한발열체는주로은 (Ag),팔라듐 (Pd),루테늄 (Ru)계산화물을포함하는 페이스트형태로제조되는데，이중은의경우낮은저항의도전성물질로양의 온도저항계수를갖기때문에자체로는발열저항으로사용하기어렵다.따라서 이를보완하기위해세라믹페이스트에팔라듐과루테늄을첨가하고있다. 그러나루테늄의경우은에비해비저항이높기때문에낮은저항값올갖기위해 첨가량이많아질수밖에없다.또한루테늄의 첨가량이많아질수록페이스트 자체의저항이증가하기때문에저항증가에따라온도가상승하게되며,결국 전력소모량이증가할수밖에없다는문제가있다.
[3] 이러한금속산화물의단점때문에대체소재로카본,메탈코팅파우더또는 이들의혼합물탄소나노류브등으로대체하는방안이검토되고있다.
[4] 카본소재와관련된종래기술로는대한민국공개특허 10-2012-0000878둥과 같이카본소재의섬유발열체를이용하여발열시트를제조하거나,대한민로 둥록특허 10-1029147등과같이액상의발열조성물을제조하여시트상에 도포하는기술,또는대한민국공개특허 10-2010-0053434둥과같이면직물， 부직포둥의기초재에카본소재로이루어진발열층올더구비하는형태둥이 있다.
[5] 이중섬유발열체의경우낮은신장율로인하여섬유상으로가공하기
어려우며,탄성율이높아섬유발열체가쉽게파열되는문제점이있다.또한 발열조성물올제조하여시트상으로도포하거나기저층에발열층을더 구비하는경우， 300°C이상의고온환경에서발열층또는코팅막의탈리현상이 발생하거나코팅막이쉽게부서지는단점이존재한다.
[6] 이러한단점들올극복하기위해카본소재에세라믹바인더를첨가하는기술도 있으나,세라믹바인더에첨가되는카본소재는큰흡유량과난이한작업성 때문에흔합이어려워 50증량 %이상의 첨가가거의불가능하며，이를보완하기 위해바인더의함량올증가시키면물리적성질과적업성은좋아지나전도성이 저하되는문제점이 있다.
[7] 따라서 이러한단점을극복하여높은내열성올가지면서물성에변화없이
높은발열효율올가지는페이스트조성물의개발이요구되고있다.
[8] <선행기술문헌 >
[9] 대한민국공개특허 10-2012-0000878 (2012년이월 04일)
[10] 대한민국등록특허 10-1029147 (2011년 04월 06일)
[11] 대한민국공개특허 10-2010-0053434 (2010년 05월 20일)
발명의상세한설명
기술적과제
[12] 본발명은상기와같은문제점올해결하기위해탄소나노류브또는
탄소나노류브 -금속복합체를이용하며 , 300°C이상의고온에서도물성변화가 없으며，코팅막형태의도전성필름제조시탈리가일어나지않는탄소나노튜브 또는탄소나노류브 -금속복합체를이용한세라믹페이스트조성물및이를 포함하는도전성필름의제공올목적으로한다. ' 과제해결수단
[13] 본발명은탄소나노튜브또는탄소나노튜브 -금속복합체를이용한세라믹
페이스트조성물및이를포함하는도전성필름에관한것이다.
[14] 본발명의일양태는탄소나노튜브또는탄소나노튜브 -금속복합체및실리콘 점착제를포함하는세라믹페이스트조성물로，상기실리콘점착제는전체 100 중량 %중실라놀기를 0.1내지 10중량 %함유하며,메틸기에대한페닐기의 비율이 0.3내지 2.5몰비인세라믹페이스트조성물에관한것이다.
[15] 또한상기탄소나노류브 -금속복합체에함유된금속은은,백금，금,구리,니켈, 철，코발트및알루미늄에서선택되는어느하나또는둘이상일수있으며，상기 금속의함량은상기탄소나노튜브 -금속복합체 100증량부에대하여 1내지 80 중량부포함할수있다.
[16] 또한상기세라믹페이스트조성물은탄소나노류브또는탄소나노류브 -금속
복합체 20내지 80중량 %및실리콘점착제 20내지 80중량 %를포함하여
이루어질수있다.
[17] 본발명의다른양태는상기세라믹페이스트조성물에유기바인더，분산제및 유기용매를더포함하는것인세라믹페이스트조성물이다.이때상기
유기바인더는에틸셀를로스,니트로샐를로스및이들의흔합물로부터선택되는 어느하나이며；상기분산제는아미노함유을리고머또는폴리머의포스포러스 에스테르염，인산의모노에스테르또는디에스테르,산성디카르복실산
모노에스테르,폴리우레탄-폴리아민부가물，폴리알콕실화모노아민또는 디아민으로이루어진군에서선택되는어느하나또는둘이상이며;상기
유기용매는아세톤,메틸에틸케톤，메틸알콜,에틸알콜，이소프로필알콜， 부틸알콜,에틸렌글리콜,폴리에틸렌글리콜,테트라하이드로퓨란, 디메틸포름아미드，디메틸아세트아미드， N-메틸 -2-피를리돈,핵산,
사이클로핵사논，를루엔，클로로포름，디클로로벤젠，디메틸벤젠，트리메틸벤젠 피리딘，메틸나프탈렌，니트로메탄,아크릴로니트릴，옥타데실아민,아닐린， 디메틸설폭사이드，디에틸렌글리콜에틸에테르및터피네올에서선택되는어느 하나또는둘이상일수있다.
[18] 또한상기세라믹페이스트조성물은탄소나노류브또는탄소나노튜브 -금속 복합체 1내지 50중량 %,유기바인더 1내지 20중량 실리콘점착제 1내지 30 중량 %,분산제 1내지 20중량 %및유기용매 1내지 90중량1 ¾를포함하여 이루어질수있다.
[19] 본발명의또다른양태는상기세라믹페이스트조성물을포함하는도전성 필름에관한것이다.이때상기도전성필름은두께 10내지 600 일때， 인가전압 1.5내지 220V에서발열온도가 40내지 400ᄋ C인것올특징으로한다. 발명의효과
[20] 본발명에따른세라믹페이스트조성물은면저항이낮다는특징이있으며 , 이를통해우수한발열특성및차폐,흡수，전도특성을구현할수있다.또한 일반적인탄소나노류브기반의페이스트에비해발열온도가 400°C로매우 높음에도불구하고페이스트조성물의물성이안정적으로유지되어세라믹 페이스트고유의특성이구현될수있다.
[21] 또한상기세라믹페이스트는간단한공정으로쉽게면상의도전성필름으로 제조할수있으며，이를이용하여보은,난방둥발열제품과전자파차폐및 흡수용물품，전극，전자회로，안테나둥다양한분야에폭넓게이용될수있다. 도면의간단한설명
[22] 도 1은본발명의일실시예에따른세라믹페이스트조성물올이용한도전성 필름을도시한것이다.
[23] 도 2는본발명의일실시예에따라제조된도전성필름에 100 V의인가전압을 걸었을때의발열효과를열화상카메라 (Ti32, Fluke)로측정하여도시한것이다.
[24] 도 3은실시예 1을통해제조된도전성필름의인가전압에따른온도변화를 도시한것이다ᅳ
[25] 도 4는실시예 2를통해제조된도전성필름의 3회에걸친인가전압에따른 온도변화를도시한것이다.
발명의실시를위한최선의형태
[26] 이하구체예또는실시예를통해본발명에따른세라믹페이스트조성물및 이의제조방법을더욱상세히설명한다.다만하기구체예또는실시예는본 발명을상세히설명하기위한하나의참조일뿐본발명이이에한정되는것은 아니며，여러형태로구현될수있다.
[27] 또한달리정의되지않은한，모든기술적용어및과학적용어는본발명이 속하는당업자증하나에의해일반적으로이해되는의미와동일한의미를 갖는다.본원에서설명에사용되는용어는단지특정구체예를효과적으로 기술하기위함이고본발명을제한하는것으로의도되지않는다.
[28] 또한명세서및첨부된특허청구범위에서사용되는단수형태는문맥에서
특별한지시가없는한복수형태도포함하는것으로의도할수있다.
[29] 본발명에서사용되는용어 '페이스트조성물''은고체와액체의증간굳기를 갖는상태를포괄하는의미로,예를들어점착성또는접착성을갖는흔합물 반죽일수있다.
[30] 본발명의일실시예에따른세라믹페이스트조성물은탄소나노류브 (carbon nano tube, CNT)또는탄소나노튜브 -금속복합체 (CNT-metal nano composite), 유기바인더，실리콘점착제,분산제및유기용매를포함할수있다.
[31] 본발명에서상기탄소나노류브는흑연한층이감겨있으며,흑연과같은 Sp2 결합올하고있는원통형태의복합구조를의미하며,상기세라믹페이스트 조성물에서발열및고전도성물질로사용된다.특히탄소나노류브또는 탄소나노류브-금속복합체는기존의발열체조성물에비해상대적으로적은 양에도불구하고,세라믹페이스트조성물의접촉저항을효과적으로낮출수 있어발열및고전도성물질로효과적이며，전자파차폐와흡수능도뛰어나다.
[32] 본발명에사용될수있는탄소나노튜브는제조방법및직경둥에한정하지 않는다.상기탄소나노튜브로예를들면단일벽탄소나노류브 (single wall CNT), 이증벽탄소나노류브 (double wall CNT),다증벽탄소나노류브 (multi wall CNT) 또는이들의흔합물로부터선택될수있다.
[33] 본발명에서상기탄소나노튜브 -금속복합체는상기탄소나노류브와
금속이온이균일하게혼합되어분자수준공정을통해제조된나노복합분말 (nano composite powder)을의미하며,본발명에사용될수있는탄소나노류브 -금속 복합체는제조방법및직경둥의형태에한정하지않는다.
[34] 특히상기탄소나노류브 -금속복합체는상대적으로적은함량으로도세라믹 페이스트조성물의접촉저항을효과적으로낮출수있어발열및고전도성 물질로효과적이며,전자파차폐와흡수능도뛰어나며,이를통해대면적화를 구현할수있는장점이 있다.상기탄소나노류브-금속복합체에대한구체적인 합성과정은대한민국둥록특허 10-1095840둥올참조할수있다.
[35] 상기탄소나노류브 -금속복합체에서금속은금 (Au),백금 (Pt),은 (Ag),구리 (Cu), 니켈 (Ni),철 (Fe),코발트 (Co)및알루미늄 (A1)증에서선택되는어느하나또는 이들의혼합물이며，금속이온이외에상기금속을포함하는화합물인경우에도 무방하다.상기금속으로바람직하게는은또는백금을사용하는것이좋다.
[36] 상기탄소나노튜브 -금속복합체에서금속의함량은탄소나노튜브 -금속복합체
100중량부에대하여 1내지 80중량부인것이좋으며，바람직하게는 20내지 60 중량부인것이우수한전도성을구현할수있으며，전도성이지나치게
높아지거나저하되는현상을방지할수있다. [37] 상기실리콘점착제는상기탄소나노튜브또는탄소나노류브 -금속복합체의 분산을촉진하기위한분산제로작용하며,또한제조되는세라믹페이스트 흔합용액을안정화하기위한점성제로작용할수있다.
[38] 보통탄소나노류브또는탄소나노튜브 -금속복합체와함께사용되는점착제는 제조된페이스트조성물을가공 (코팅또는박막형성)하는동안탄소나노튜브 또는탄소나노튜브-금속복합체의안정화를위해양호한조정 (coordination) 결합을제공하도록유일의페어전자들 (lone pair electrons)을갖는 N, 0, S또는 다른작용기를포함하는것을사용해왔다.특히히드록시기및카르복실기등과 같은높은산소함량을갖는폴리머바인더를사용하였는데,이러한점착제로 예를들면에폭시수지 (epoxy resin),페놀수지 (phenol resin),우레탄수지 (urethane resin),폴리에스터수지 (polyester resin),염화비닐수지 (polyvinylchloride resin), 요소수지 (urea resin),폴리에틸렌수지 (polyethylene resin),아크릴수지 (acryl resin) 둥이있다.이들폴리머는탄소나노류브또는탄소나노류브 -금속복합체의 표면에대한강한친화력을가지며 ,분산성과안정성을높일수있다.그러나 이들수지는본발명에서요구하는내열성을층족하지못하므로,실리콘계열의 점착제를사용하는것이바람직하다.
[39] 본발명에따른실리콘점착제는규소 (Si)원자와산소 (0)원자가교대로
되어있는폴리실록산주쇄를가지는고분자로서，대게실리콘은각각의규소 원자에보통두개의메틸,에틸,프로필등의알킬또는페닐 (-CeH5)의유기 원자단이결합되어있는구조로，본발명에따른실리콘점착제는폴리실록산 주쇄에수소,히드록시기，메틸기또는페닐기가결합되어있을수있다.이때 폴리실록산주쇄,즉 Si02의함량은전체실리콘점착제 100중량%에대하여 45 내지 65중량 바람직하게는 47내지 63증량 %인것이좋다.
[40] 상기실리콘점착제는건조성을향상시키면서도우수한유연성을위해
관능기인히드록시기를가지는실라놀 (silanol)의함량이일정범위를갖는것이 좋으며 ,바람직하게는전체실리콘점착제 100중량 %에대하여 0.1내지 10 중량 %，더욱바람직하게는 1내지 6중량 %인것이좋다.실라놀의함량이 0.1 중량 %미만인경우，건조성및강도가하락할수있으며, 10중량 %초과인경우, 유연성및가공성이떨어지게된다.
[41] 본발명에따른실리콘점착제는제조되는세라믹페이스트조성물의
열안정성을더욱향상시키기위해메틸기와페닐기의비율이일정한것이 바람직하다.상기메틸기와페닐기의비율은메틸기 1몰비에대하여페닐기 03 내지 2.5몰비，바람직하게는메틸기 1몰비에대하여페닐기 0.4내지 2.0몰비인 것이좋다.상기페닐기가 0.3몰비미만인경우,기계적인강도및내열성이 하락하며，페닐기가 0.3몰비초과인경우，발수성이떨어지고탄성이높아져 가공성이하락한다.
[42] 본발명에따른실리콘점착제는가열에의해관능기간에결합이발생하여 경화될수있는데，바람직한경화형태는가교도 55내지 80%,중량평균분자량 1,000내지 400,000인것이가공성및기계적인물성측면에서바람직하다.
[43] 상기실리콘점착제로예를들면,다우코닝 (Dow corning)사의실리콘
레진 (XIAMETER)으로, RSN-0409 HS, RSN-0431 HS, RSN-0804, RSN-0805, RSN-0806, RSN-0808, RSN-0840둥의 액상수지또는 RSN-0217, RSN-0220, RSN-0233, RSN-0249둥의고상수지에서선택되는어느하나또는이들의 흔합물을최종적용온도및코팅막의경도에따라자유롭게선택하여사용할수 있다.
[44] 본발명에따른세라믹페이스트조성물은탄소나노튜브또는
탄소나노류브 -금속복합체 20내지 80증량 %및실리콘점착제 20내지 80 중량 %를포함하여이루어지는것이탄소나노튜브또는탄소나노류브 -금속 복합체의분산이효과적으로이루어지면서본발명에서원하는층분한발열성, 전자파차폐성및전도성올발현할수있어바람직하다.
[45] 또한본발명에따른페이스트조성물은필요에따라유기바인더 ,분산제및 유기용매를더포함할수있다.상기유기바인더,분산제및유기용매는어느 하나만을첨가할수있으나,필요에따라둘이상을첨가하여도무방하며,가장 바람직하게는유기바인더,분산제및유기용매를모두포함하는것이좋다.
[46] 상기와같이페이스트조성물에유기바인더，분산제및유기용매를모두
포함하는경우상기페이스트조성물의조성비는탄소나노류브또는
탄소나노류브 -금속복합체 1내지 50중량 %，유기바인더 1내지 20중량 실리콘점착제 1내지 30중량 %，분산제 1내지 20중량 <¾및유기용매 1내지 90 중량 «¾를포함하여이루어지는것이바람직하다.
[47] 상기유기바인더는본발명에따라제조되는세라믹페이스트조성물의
가공성올향상시키고,코팅또는박막가공시에도포성을향상시키거나 기판과의밀착성올향상시키는역할올수행할수있다.
[48] 상기유기바인더의종류는특별히제한되지않으며,바람직하게는셀를로스 유도체를사용하는것이좋다.상기 샐를로스유도체는셀를로스반복단위인 β-글루코스에존재하는 3개의하이드록시기중일부또는전부가치환된것으로， 예를들어에틸셀를로스 (ethylcellulose),니트로셀롤로스 (nitrocellulose)등에서 선택되는어느하나또는이들의흔합물이 있다.
[49] 상기유기바인더는제조방법둥에한정하지않지만,일정범위의 점도를
가지는것이좋다.상기유기바인더는 25°C에서 10내지 50,000 cps(centipoise), 바람직하게는 1,000내지 35,000cps인것이바람직하다.상기점도범위를 벗어나는경우，조성물의가공시조직이치밀하게형성되지못하거나,균열이 발생할수있으며,저장안정성이떨어지게된다.
[50] 상기유기바인더는세라믹페이스트조성물 100중량 %»에대하여 1내지 20 중량 바람직하게는 3내지 15중량부인것이조성물의가공성을유지하고， 박막및코팅의기계적인물성이떨어지지않고유지되어좋다.
[51] 상기분산제는세라믹페이스트제조시 ,탄소나노류브또는 탄소나노튜브-금속복합체의입체적안정화를통하여입자를미립화하고， 분산성을향상시켜,표면코팅시동일한면저항값을갖게하는조성물이다. 다만상기분산제는바인더로서는작용하지않으므로，지나치게첨가하면 경화를방해하게된다.또한너무고분자인경우,바인더와의상용성을얻기 어려우므로,수평균분자량이 2,000내지 20,000인화합물이바람직하다.
[52] 본발명에따른분산제는산을사용하여아민작용성화합물을염화함으로써 얻을수있는데，상기아민작용성화합물은대한민국공개특허
10-2011-0099679에기재된화합물이바람직하다.
[53] 상기아민작용성화합물을염화하여얻은분산제로예를들면, (a)임의로
지방산으로변형되었거나알콕실화된 (더욱구체적으로는에톡실화된) 폴리아민의포스포러스에스테르염,에폭사이드-폴리아민부가물의포스포러스 에스테르염,아미노함유아크릴레이트또는메타크릴레이트공중합체의 포스포러스에스테르염및아크릴레이트-폴리아민부가물의포스포러스 에스테르염등의아미노함유올리고머또는폴리머의포스포러스에스테르 염과， (b)알킬，아릴,아르알킬또는알킬아릴알콕실레이트 (예컨대，노닐페놀 에록실레이트,이소트리데실알콜에록실레이트，부탄올로부터제조한알킬렌 옥사이드폴리에테르)를함유하는인산의모노에스테르또는디에스테르， 폴리에스테르 (예컨대，락톤폴리에스테르，예컨대，카프로락톤폴리에스테르 또는흔합형카프로락톤 /발레로 -락톤폴리에스테르)를함유하는인산의 모노에스테르또는디에스테르둥의인산의모노에스테르또는디에스테르， (c) 알킬，아릴，아르알킬또는알킬아릴알콕실레이트 (예컨대，
노닐페놀에록실레이트，이소트리데실알콜에록실레이트또는부탄올로부터 제조된알킬렌옥사이드폴리에테르)를함유하는산성디카르복실산
모노에스테르 (더욱구체적으로는숙신산，말레산또는프탈산)로예시될수 있는산성디카르복실산모노에스테르와， (d)폴리 -우레탄-폴리아민부가물， (e) 폴리알콕실화모노아민또는디아민 (예컨대，에특실화올레일아민또는 알콕실화에틸렌디아민)및 (f)모노아민,디아민및폴리아민，아미노알콜및 불포화 1,2-디카르복실산및이들의무수물및이들의염과불포화지방산과의 반웅생성물및알콜및 /또는아민과불포화지방산과의반웅생성물로이루어진 군에서선택되는어느하나또는둘이상일수있다.
[54] 상기종류의분산제는예컨대베젤소재의비와이케이
게엠베하사 (BYK-CHEMIE GMBH)로부터생산되는상품명 BYK-220 S, BYK-9076, BYK-9077, BYK-P 104, BYK-P 104 S, BY -P 105, BYK-W 9010, BYK-W 920, BYK-W 935, BYK-W 940， BYK-W 960, BYK-W965, BY -W 966， BYK-W 975, BYK-W 980, BYK-W 990, BYK-W 995, BYK-W 996, BYKUMEN, LACTIMON, ANTI-TERRA-202, ANTI-TERR A-203, ANTI-TERRA-204,
ANTI-TERRA-205, ANTI-TERRA-206, ANTI-TERRA-207, ANTI-TERRA-U 100, ANTI-TERRA-U 80, ANTI-TERRA-U, DISPERBYK, DISPERBYK-101, DISPERBYK-102, DISPERBYK-103, DISPERBYK-106, DISPERBYK-107, DISPERBYK-108, DISPERBYK-109, DISPERBYK-110, DISPERBYK-111, DISPERBYK-112, DISPERBYK-115, DISPERBYK-116, DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK— 160，
DISPERBYK-161, DISPERBYK- 162, DISPERBYK- 163, DISPERBYK- 164, DISPERBYK- 165, DISPERBYK- 166, DISPERBYK- 167, DISPERBYK- 168, DISPERBYK- 169, DISPERBYK- 170, DISPERBYK- 171, DISPERBYK- 174, DISPERBYK- 176, DISPERBYK- 180, DISPERBYK- 181, DISPERBYK- 182, DISPERBYK- 183, DISPERBYK- 184, DISPERBYK- 185, DISPERBYK- 187, DISPERBYK- 190, DISPERBYK- 191, DISPERBYK- 192, DISPERBYK- 193, DISPERBYK- 194, DISPERBY -2000, DISPERBYK-2001, DISPERBY -2009, DISPERBYK-2010, DISPERBY -2020, DISPERBYK-2025, DISPERBYK-2050, DISPERBYK-2070, DISPERBYK-2090, DISPERBY -2091, DISPERBYK-2095, DISPERBYK-2096, DISPERBYK-2150, DISPERBYK-2155, DISPERBYK-2163, DISPERBYK-2164, DISPERPLAST-1010, DISPERPLAST-1011,
DISPERPLAST-1012, DISPERPLAST-1018, DISPERPLAST-I,
DISPERPLAST-P으로서이증바람직하게는유용성도료및수계도료용 고분자량습윤분산제인 DISPERBYK- 180， DISPERBYK- 182, DISPERBYK- 184 둥이나，수계도료와고농도착색제용습윤분산제인 DISPERBYK- 190,
DISPERBYK- 191, DISPERBYK- 192, DISPERBYK- 194등에서선택되는어느 하나또는이들의혼합물을사용하는것이좋다.
상기분산제는상기세라믹페이스트조성물 100중량%에대하여 1내지 20 중량 %인것이바람직하며,좋게는 2내지 10증량 %인것이소량의첨가로도 분산효과가탁월하며,경화를방해하지않아바람직하다.
상기유기용매는당업계에서통상적으로사용되는물질이라면특별히 제한하지않으며,예를들어 ,아세론 (acetone),메틸에틸케톤 (methylethylketone), 메틸알콜 (methyl alcohol),에틸알콜 (ethyl alcohol),이소프로필알콜 (isopropyl alcohol),부틸알콜 (butyl alcohol),에틸렌글리콜 (ethyleneglycol),
폴리에틸렌글리콜 (polyethyleneglycol),테트라히드로퓨란 (tetrahydrofiiran), 디메틸포름아미드 (dimethylformamide),디메틸아세트아미드 (dimethylacetamide) N-메틸 -2-피롤리돈 (N-methyl-2-pyrrolidone),핵산 (hexane),
시"이클로핵시"논 (cyclohexanone),를루엔 (toluene),클로로포름 (chloroform), 디클로로벤젠 (dichlorobenzene),디메틸벤젠 (dimethylbenzene),
트리메틸벤젠 (trimethylbenzene),피리딘 (pyridine),
메틸나프탈렌 (methylnaphthalene)，니트로메탄 (nitromethane) ,
아크릴로니트릴 (acrylonitrile),옥타데실아민 (octadecylamine),아닐린 (aniline), 디메틸설폭사이드 (dimethylsulfoxide),
디에틸렌글리콜에틸에테르 (diethyleneglycolethylether),터피네을 (terpineol) 등에서선택되는어느하나또는이들의혼합물일수있으며，바람직하게는 터피네올과같은높은휘발온도를갖는용매를사용하는것이용매의휘발성이 낮아페이스트조성물의제조가용이하며，범용적으로사용하는용매로서 호환성이높다는장점이있다.
[57] 상기유기용매의함량은전체실리콘페이스트조성물 100중량 %에대하여 1 내지 90중량%일수있으며,바람직하게는 40내지 80증량 %인것이박막화또는 코팅막제조시전기적특성이저하되는것을방지하고,동시에형성된코팅막 또는박막이탈리되는문제점을방지할수있다.
[58] 본발명에따른세라믹페이스트조성물은탄소나노튜브또는
탄소나노류브 -금속복합체 1내지 50중량 %，유기바인더 1내지 20중량 %, 실리콘점착제 1내지 30중량 %，분산제 1내지 20증량 %및유기용매 1내지 90 중량 %를포함하는흔합용액을제조하고，상기흔합용액을분산하여제조할수 있다.
[59] 하나의예로서본발명에따른세라믹페이스트조성물은，
[60] 탄소나노류브，실리콘점착제,유기바인더,분산제및유기용매를포함하는 흔합용액올제조하는단계;및
[61] 제조된흔합용액올분산하는단계;를포함하여제조되거나，
[62] 탄소나노류브-금속복합체，실리콘점착제,유기바인더，분산제및유기용매를 포함하는흔합용액을제조하는단계 ;및
[63] 제조된흔합용액을분산하는단계 ;를포함하여제조될수있다ᅳ
[64] 상기흔합용액을분산하는단계는당해기술분야에서통상적으로사용되는 다양한방법들이적용될수있다.상기방법으로예를들면,
초음파처리 (ultra-sonication),호모믹서 (homo-mixer),롤밀 (roll-mill),
볼밀 (ball-mill),아트리션밀 (attrition mill),수직밀 (vertical-mill)또는
수평밀 (horizontal-mill)에서선택되는어느하나의방법으로수행할수있다. 하나의예로서，본발명에서혼합용액을분산하는단계는 3-롤밀법을 5회 수행하는것을포함할수있다.
[65] 본발명에따른세라믹페이스트조성물은적용방법및형태에한정하지
않는다.예를들어기저층상에코팅하는방법으로면상의도전성필름제조가 가능하며,이를통해발열，차폐，흡수및전도특성을나타낼수있다.
[66] 상기코팅과정은당업계에서통상적으로알려진방법으로수행할수있는데, 예를들어，스크린프린팅 (screen-printing),닥터블레이드 (doctor blade), 바코팅 (bar-coating),스핀코팅 (spin-coating), ¾코팅 (dip-coating),
스프레이코팅 (spray-coating),전기영동증착 (electrophoretic deposition), 옵셋프린팅 (offset-printing),감압여과 (vacuum filtration)또는노멀캐스팅 (normal casting)등의방법이적용될수있으나，이에한정하는것은아니다.
[67] 상기기저층은당업계에서통상적으로사용되는디스플레이용또는
인쇄회로용기판둥올사용할수있으며，예를들어, 폴리카보네이트 (polycarbonate),
폴리에틸렌테레프탈레이트 (polyethyleneterephthalate),폴리아미드 (polyamide), 샐를로스에스테르 (celluloseester),재생셀를로스 (regenerated cellulose), 폴리프로필렌 (polypropylene),폴리아크릴로니트릴 (polyacrylonitrile),
폴리술폰 (polysulfone),폴리에스테르술폰 (polyestersulfone),
폴리비닐리덴플루오라이드 (polyvinylidenfluoride)또는유리등올사용할수 있다.그라나상기기저층은제품용도및적용온도에따라서자유롭게선택할수 있으며，앞서열거된예시에본발명이한정되는것은아니다.
[68] 본발명에따른세라믹페이스트조성물로제조된도전성필름은제조조건， 필름의크기및형태,두께에따라달라질수있으나,면저항이 0.1내지 1,000 ohm/sq의범위를가질수있으며,바람직하게는 1내지 300 ohm/sq,더욱 바람직하게는 1내지 150 ohm/sq의범위를가지는것이좋다.본발명에따른 도전성필름은면저항이낮으며，이를통해우수한발열，차폐,흡수특성등올 가진다.그러나면저항이지나치게낮아지면,발열성이크게하락할수 있으므로,상기범위의면저항올갖는것이상대적으로낮은소비전력으로높은 발열특성을구현할수있다.
[69] 본발명에따른도전성필름이전극둥전자제품에사용되는경우,상기도전성 필름의두께가 10내지 600 zm일때，인가전압이 1.5내지 220 V범위일수 있으며，바람직하게는 10내지 220 V,더욱바람직하게는 10내지 100 V일수 있다.상기범위에서층분한발열구동을유도하면서,동시에발열에따른화상, 화재발생및제품손상을예방할수있다.
[70] 또한본발명에따른세라믹페이스트조성물은상기범위의두께에서상기 범위의인가전압을가할때，발열온도가 40내지 400°C일수있다.상기 발열온도는상기인가전압에따라변화할수있는데,하나의예로서,본발명에 따른페이스트조성물에가해지는인가전압의범위가 90내지 100 V인경우， 발열온도가 297내지 328°C범위일수있다.
[71] 다만본발명에따른세라믹페이스트조성물은발열온도가 400°C를초과하는 경우，탄소나노튜브의산화가발생하거나，폴리머기저층이연소되어코팅막이 벗겨지는탈리현상이발생하거나,바인더의분해로인한페이스트조성물 고유의특성이구현되지않는문제점이발생할수있다.
[72] 본발명에따른세라믹페이스트조성물로제조된도전성필름은발열제품， 전자파차폐및흡수제품,전도성제품에포함될수있다.상기발열제품은보온 또는난방둥의용도및다양한형태로제품화될수있으며,일예로발열시트, 발열파이프,발열보은병또는발열라디에이터등으로이용될수있다 또한 전자파차폐및흡수제품의일예로핸드폰,텔레비전,자동차둥전자파가 나오는모든전자제품둥에이용될수있으며，전극용바인더,전자회로，안테나 둥높은전도도가요구되는다양한제품에이용될수있다.
[73] [74] 이하실시예및비교예를통하여본발명에따른세라믹페이스트조성물및 제조방법을더욱상세히설명한다.
[75] 하기실시예및비교예를통해제조된세라믹페이스트조성물의물성을
다음과같이측정하였다.
[76]
[77] (은도변화)
[78] 인가전압에따른온도변화를비교하기위하여，하기실시예및비교예를통해 제조된코팅막의양끝부분에실버페이스트를코팅하고，구리동박을입혀 전극올형성하였다.그후인가전압을 0 V에서 100 V까지 10 V간격으로전압을 인가하고그에대한발열온도를측정하였다.
[79] (전기전도도)
[80] 전기전도도비교하기위하여，하기실시예및비교예를통해제조된코팅막의 면저항을표면저저항측정시스템 (Loresta-GP. MCP-T610, Mitsubishi chemical analytech)을이용하여측정하였다.표면저저항측정시스템으로코팅막의 면저항을측정할때코팅막을 4분할하여측정한후평균값을취하였다.
[81] (탈리여부)
[82] 코팅막의탈리여부를판단하기위하여，하기실시예및비교예를통해제조된 코팅막의표면을 3M사의스카치매직테이프를코팅막에붙였다떼면서 테이프에코팅막이묻어나는지를보고탈리여부를판단하였으며，탈리되지 않은경우 X，탈리되지않았으나코팅막에변형이일어난경우ᅀ，코팅막이 탈리된경우 O로나타내었다.
[83]
[84] (실시예 1)
[85] 500 mi삼각플라스크에탄소나노튜브 ((주 )한화나노텍) 1.5g을넣고，
유기용매인터피네을 (ot-terpineol, Sigma- Aldrich) 33.75g,
에틸셀롤로스 (EthylcelMose, Sigma- Aldrich) 1.25g,실리콘점착제 (RSN-0806, 다우코닝) 5g및분산제 (DISPERBYK-192, BYK) 0.75g을첨가하였다.교반기에 삼각플라스크를장착하여 60분간교반하고， 3를밀 (3-rollmill, EXAKT 50)을 이용하여 5회분산처리를수행하여세라믹페이스트조성물을제조하였다.
[86] 이와는별개로 100薩 X 100 mm의폴리이미드필름상에상기세라믹페이스트 조성물을 10 mi표면에투여한후,바코터를이용하여코팅을수행하였다.
코팅은 3회수행하였으며 , 1회수행당코팅막의평균두께는 100 이었다.
제조된코팅막은드라이오브에서 2°C/min의승온속도로 300oC까지승온한다음， 300°C에서 30분간열처리하여코팅막을제조하였다.제조된코팅막의온도변화， 전기전도도및탈리여부를측정하여표 1에나타내었다.
[87] (실시예 2)
[88] 탄소나노류브대신에탄소나노튜브-은나노복합체 ((주 )한화나노텍) 5g넣은 것을제외하고실시예 1과동일한조건에서코팅막올제조하였다.제조된 코팅막의온도변화，전기전도도，전자파차폐및탈리여부를측정하여표 1에 나타내었다.
[89]
[90] (비교예 1)
[91] 실리콘점착제대신에동일한양의메틸메타아크릴레이트( (주)대광고분자)를 넣은것을제외하고실시예 1과동일한조건에서코팅막을제조하였다.제조된 코팅막의온도변화,전기전도도,전자파차폐및탈리여부를측정하여표 1에 나타내었다.
[92]
[93] 표 1
[Table 1]
Figure imgf000014_0001
상기표 1및도 3, 4와같이본발명에따라제조된발열코팅막은인가전압이 상승함에따라발열온도또한이에비례하여상승함을알수있으며，다른 점착제를사용하거나,물성이다른실리콘점착제를사용한비교예 1이특정 전압이상에서내열은도범위를넘어온도변화측정이불가능한것올알수 있었다.또한열내구성을확인하기위해동일조건에서반복실험을하였음에도 모두비슷하게발열이됨을확인할수있었다.또한발열에따른고온이계속 유지됨에도실시예를통해제조된발열코팅막은탈리없이안정적으로 유지됨올확인할수있었다.

Claims

청구범위
탄소나노튜브또는탄소나노류브 -금속복합체및실리콘 점착제를포함하는세라믹페이스트조성물로,
상기실리콘점착제는전체 100증량 %중실라놀기를 0.1내지 10 중량 %함유하며，메틸기에대한페닐기의비율이 0.3내지 2.5 몰비인세라믹페이스트조성물.
제 1항에있어서,
상기탄소나노튜브 -금속복합체에함유된금속은은,백금，금， 구리,니켈，철，코발트및알루미늄에서선택되는하나또는둘 이상인세라믹페이스트조성물.
제 2항에있어서，
상기금속의함량은상기탄소나노류브 -금속복합체 100중량부에 대하여 1내지 80증량부포함하는것인세라믹페이스트조성물. 제 1항에있어서,
상기세라믹페이스트조성물은탄소나노류브또는
탄소나노류브 -금속복합체 20내지 80증량 %및실리콘점착제 20 내지 80증량 %를포함하는것인세라믹페이스트조성물.
제 1항에있어서,
상기세라믹페이스트조성물에유기바인더,분산제및
유기용매를더포함하는것인세라믹페이스트조성물.
제 5항에있어서，
상기유기바인더는에틸셀롤로스,니트로셀를로스및이들의 흔합물로부터선택되는어느하나이며;
상기분산제는아미노함유올리고머또는폴리머의포스포러스 에스테르염，인산의모노에스테르또는디에스테르，산성 디카르복실산모노에스테르,폴리우레탄-폴리아민부가물， 폴리알콕실화모노아민또는디아민으로이루어진군에서 선택되는어느하나또는둘이상이며;
상기유기용매는아세톤,메틸에틸케톤,메틸알콜，에틸알콜， 이소프로필알콜,부틸알콜，에틸렌글리콜，폴리에틸렌글리콜， 테트라하이드로퓨란，디메틸포름아미드,디메틸아세트아미드, Nᅵ메틸 -2-피를리돈,핵산，사이클로핵사논,를루엔，클로로포름， 디클로로벤젠，디메틸벤젠，트리메틸벤젠，피리딘，메틸나프탈렌, 니트로메탄,아크릴로니트릴,옥타데실아민,아닐린,
디메틸설폭사이드，디에틸렌글리콜에틸에테르및터피네을에서 선택되는어느하나또는둘이상인세라믹페이스트조성물. 제 5항에있어서， 상기세라믹페이스트조성물은탄소나노류브또는
탄소나노튜브 -금속복합체 1내지 50중량 %，유기바인더 1내지 20 중량 실리콘점착제 1내지 30증량 %，분산제 1내지 20중량 «¾ 및유기용매 1내지 90증량 %를포함하는것인세라믹페이스트 조성물.
[청구항 8] 제 1항내지제 7항에서선택되는어느하나의세라믹페이스트 조성물을포함하는도전성필름.
[청구항 9] 제 8항에있어서,
상기도전성필름은두께 10내지 600 일때，인가전압 1.5내지 220V에서발열온도가 40내지 400oC인도전성필름.
PCT/KR2014/006141 2013-07-12 2014-07-09 탄소나노튜브 또는 탄소나노류브 -금속 복합체를 이용한 세라믹 페이스트 조성물 및 이를 포함하는 도전성 필름 WO2015005665A1 (ko)

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