WO2023248485A1 - Encre de cuivre, procédé de formation de film conducteur et étiquette rfid - Google Patents

Encre de cuivre, procédé de formation de film conducteur et étiquette rfid Download PDF

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Publication number
WO2023248485A1
WO2023248485A1 PCT/JP2022/031645 JP2022031645W WO2023248485A1 WO 2023248485 A1 WO2023248485 A1 WO 2023248485A1 JP 2022031645 W JP2022031645 W JP 2022031645W WO 2023248485 A1 WO2023248485 A1 WO 2023248485A1
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copper
conductive film
fine particles
ink
dispersant
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PCT/JP2022/031645
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English (en)
Japanese (ja)
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祐一 川戸
聡 南原
英俊 有村
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石原ケミカル株式会社
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Publication of WO2023248485A1 publication Critical patent/WO2023248485A1/fr

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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
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24—Electrically-conducting paints
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • 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

Definitions

  • the present invention relates to a copper ink for forming a conductive film, a method for forming a conductive film using the copper ink, and an RF tag having the conductive film.
  • RFID radio frequency identification
  • Non-Patent Document 1 RFID (radio frequency identification) RF tags are used for product tagging.
  • RFID is a system that uses electromagnetic coupling to read data on RF tags.
  • JIS Z0667:2017 “Application of RFID to supply chain - Product tagging” in Non-Patent Document 1 corresponds to the international standard ISO17367:2013 "Supply chain applications of RFID-Product tagging”.
  • An RF tag has an antenna, wiring, and an IC chip on a resin film such as PET (polyethylene terephthalate).
  • the antenna and wiring are made of metal foil such as aluminum, and are formed on a resin film.
  • the manufacture of RF tags involves a process of etching metal foil, and processing of waste liquid generated during etching is costly. Furthermore, there has been a recent demand for a shift away from plastics. However, if the resin film of the RF tag is replaced with a paper base material, the metal foil on the paper base material cannot be etched.
  • the present invention solves the above problems, and aims to form a low-resistance conductive film on a paper base material.
  • the copper ink of the present invention is an ink for forming a conductive film, and includes copper fine particles, a liquid dispersion medium, and a dispersant for dispersing the copper fine particles in the dispersion medium, and the copper fine particles are copper particles having a median diameter of 60 nm or more and 110 nm or less, the concentration of the copper fine particles is 60% by weight or more based on the entire copper ink, and the dispersion medium contains an alcohol having a plurality of hydroxy groups.
  • the dispersant is a polymer compound having a phosphoric acid group or a salt thereof, and the concentration of the dispersant is 3% by weight or more and 6% by weight or less based on the weight of the copper fine particles. shall be.
  • the dispersion medium preferably contains an alcohol selected from the group consisting of 2-methyl 2,4-pentanediol and 3-methyl 1,3-butanediol.
  • the method for forming a conductive film of the present invention is a method for forming a conductive film on a paper base material, and includes a step of forming an ink film on a paper base material using the copper ink described above, and drying the ink film.
  • the method is characterized by comprising the steps of: forming a coated dry film made of fine copper particles on the paper base material; and photo-baking the coated dry film.
  • the RF tag of the present invention is an RFID RF tag, and includes at least a paper base material and an antenna on the paper base material, and the antenna is made of a conductive film formed by the above-described conductive film forming method. It is characterized by becoming.
  • the median diameter of the copper fine particles is 60 nm or more, a thick conductive film can be formed on the paper base material by photo-baking. Since the median diameter of the copper fine particles is 110 nm or less, a conductive film with low volume resistivity can be formed on the paper base material by photo-baking. Since the concentration of copper fine particles is 60% by weight or more based on the entire copper ink, a thick conductive film can be formed. Since the dispersion medium contains an alcohol having a plurality of hydroxy groups, hydrogen bonding with the surface of the copper fine particles provides the copper ink with viscosity and rheological properties (thixotropy) suitable for printing on paper substrates.
  • the concentration of the dispersant is 3% by weight or more based on the weight of copper, the stability of the copper ink is good. Since the concentration of the dispersant is 6% by weight or less, a conductive film with low volume resistivity can be formed. The conductive film formed is thick and has a low volume resistivity, so it has low resistance. Furthermore, since the dispersant has a phosphoric acid group and the concentration of the dispersant is 3% by weight or more, the durability of the conductive film in constant temperature and humidity tests is improved by preventing oxidation of copper by phosphorus. .
  • FIGS. 1A, 1B, and 1C are cross-sectional configuration diagrams chronologically showing the formation of a conductive film using copper ink according to an embodiment of the present invention.
  • a copper ink according to an embodiment of the present invention will be described. Copper ink is used to form the conductive film.
  • the copper ink contains copper fine particles, a liquid dispersion medium, and a dispersant.
  • the dispersant disperses copper fine particles in a dispersion medium.
  • the copper fine particles are copper particles and have a median diameter (D50) of 60 nm or more and 110 nm or less.
  • D50 median diameter
  • the particle size of the copper fine particles is extracted from an image taken by a scanning electron microscope (SEM image), and the median diameter is calculated from the particle size distribution. If the particle size of the copper fine particles is too small, the formed conductive film cannot be made thick. If the particle size is too large, the volume resistivity of the conductive film will increase.
  • the concentration of copper fine particles is 60% by weight or more based on the entire copper ink. If the concentration of copper fine particles is too low, the conductive film formed will be thin.
  • the concentration of copper fine particles is desirably 75% by weight or less.
  • the dispersion medium contains an alcohol having multiple hydroxy groups.
  • the outermost surface of the copper fine particles is oxidized by oxygen contained in the atmosphere, forming a thin surface oxide film made of copper oxide.
  • oxygen contained in the atmosphere forming a thin surface oxide film made of copper oxide.
  • hydrogen bonds occur between the oxygen atoms of the copper oxide in the surface oxide film of the copper fine particles and the hydrogen atoms of the hydroxyl groups of the alcohol. Therefore, alcohol having multiple hydroxy groups has excellent dispersibility of copper fine particles.
  • Alcohols having multiple hydroxy groups include, for example, 2-methyl 2,4-pentanediol (hexylene glycol), 3-methyl 1,3-butanediol (isoprene glycol), and 1,2-ethanediol (ethylene glycol). , propane-1,2-diol (propylene glycol), 1,5-pentanediol, 2,2'-oxydiethanol (diethylene glycol), triethylene glycol, 1,2,3-propanetriol (glycerin), and sorbitol. , but not limited to.
  • the dispersant is a polymer compound having a phosphoric acid group or a salt thereof.
  • a polymer is a molecule with a large molecular weight that has a structure made up of many repetitions of units that are derived substantially or conceptually from molecules with a small molecular weight (International Union of Pure and Applied Chemistry (IUPAC)). Since the surface of the copper fine particles is covered with dispersant molecules, they are dispersed in the dispersion medium.
  • the concentration of the dispersant is 3% by weight or more and 6% by weight or less based on the weight of copper. If the concentration of the dispersant is too low, the dispersibility of the dispersant will be insufficient and the stability of the copper ink will be poor. If the concentration is too high, dispersant residue will remain in the conductive film to be formed, increasing the volume resistivity of the conductive film.
  • the formed conductive film has improved durability in a constant temperature and humidity test.
  • TEM transmission electron microscopy
  • This conductive film forming method is a method of forming a conductive film on a paper base material.
  • an ink film 2 is formed on a paper base material 3 using a copper ink 1.
  • the ink film 2 is formed by a printing method.
  • copper ink is used as the printing ink, and a printing device applies the copper ink in a predetermined pattern onto the paper base material 3 to form an ink film 2 in the pattern.
  • the printing method is flexographic printing. Then, the ink film 2 is dried.
  • the coated dry film 4 made of copper fine particles is formed on the paper base material 3, as shown in FIG. 1(b). Then, the coated dry film 4 made of fine copper particles is irradiated with light, and the coated dry film 4 is photo-sintered.
  • the light source used for photo-baking is, for example, a xenon lamp. A laser device may be used as the light source.
  • the surface oxide film of the copper fine particles in the applied dry film 4 is removed by the energy of the light, and the copper fine particles are melted together to form a bulk. That is, as shown in FIG. 1(c), the applied and dried film 4 forms a conductive film 5 on the paper base material 3 by photo-baking. Note that the drying of the ink film 2 and the photo-baking of the applied dry film 4 may be performed at the same time by irradiation with light.
  • this conductive film forming method includes a step of forming an ink film 2 on a paper base material 3 using a copper ink 1, and a step of drying the ink film 2 to form a coated dry film 4 made of fine copper particles on the paper base material 3. and a step of photo-baking the applied dry film 4.
  • a copper ink having copper fine particles with a median diameter of 40 nm which is smaller than that of this embodiment, is used, a conductive film with a low volume resistivity can be formed, but the conductive film cannot be thickened.
  • the cause of the cracks is that if the particle size of the copper particles is small, the volumetric shrinkage rate when the ink film dries becomes large, and the path through which the dispersion medium is packed by the small copper particles and escapes as gas. is to disappear.
  • the inventor of the present application conducted numerous experiments and found that copper fine particles having a median diameter of 60 nm to 110 nm are suitable for forming a conductive film on a paper base material.
  • the viscosity of the copper ink decreases. This caused the copper ink to spread and sag during flexographic printing, making it necessary to increase the viscosity of the copper ink.
  • inks are thickened with additives such as resins and rheology control agents.
  • additives such as resins and rheology control agents.
  • the inventor of the present application has discovered that copper ink can be produced. If the dispersion medium is a monohydric alcohol, the viscosity of the copper ink will be insufficient.
  • the median diameter of the copper fine particles is 60 nm or more, a thick conductive film can be formed on the paper base material by photo-baking. Since the median diameter of the copper fine particles is 110 nm or less, a conductive film with low volume resistivity can be formed on the paper base material by photo-baking. Since the concentration of copper fine particles is 60% by weight or more based on the entire copper ink, a thick conductive film can be formed. Since the dispersion medium contains an alcohol having a plurality of hydroxy groups, hydrogen bonding with the surface of the copper fine particles provides the copper ink with viscosity and rheological properties (thixotropy) suitable for printing on paper substrates.
  • the concentration of the dispersant is 3% by weight or more based on the weight of copper, the stability of the copper ink is good. Since the concentration of the dispersant is 6% by weight or less, a conductive film with low volume resistivity can be formed. The conductive film formed is thick and has a low volume resistivity, so it has low resistance. Furthermore, since the dispersant has a phosphoric acid group and the concentration of the dispersant is 3% by weight or more, the durability of the conductive film in constant temperature and humidity tests is improved by preventing oxidation of copper by phosphorus. .
  • a coated and dried film with a thickness of 1 to 5 ⁇ m can be formed on a paper base material, and a coated and dried film with a thickness of about 1 to 2 ⁇ m (0.7 to 1.5 ⁇ m) can be formed on the paper base material.
  • a conductive film with a thickness of 8 ⁇ m) can be formed. Since the conductive film formed is thick and has a low volume resistivity, the conductive film has low resistance.
  • the RF tag 6 is an RFID RF tag.
  • the RF tag 6 of this embodiment includes at least a paper base material 3 and an antenna on the paper base material 3.
  • the antenna is made of a conductive film 5 formed by the conductive film forming method of this embodiment.
  • the antenna of the RF tag 6 is made of the conductive film 5 formed by the conductive film forming method of this embodiment.
  • the conductive film is thick and has a low volume resistivity, resulting in a low resistance antenna. Since this RF tag 6 has a low resistance antenna, sufficient signal strength can be obtained.
  • the RF tag 6 may be laminated. Note that an example of laminating an RF tag is described in the Japanese Industrial Standards (see Non-Patent Document 1).
  • a copper ink as an example of the present invention and a copper ink as a comparative example were prepared, and an experiment was conducted to form a conductive film on a paper base material using the copper ink.
  • Coated paper manufactured by Oji Paper Co., Ltd., product name "OK Top Coat + EF"("TopCoat” and “TOPKOTE” are registered trademarks
  • Copper ink was used.
  • a wiring test pattern (0.6 mm wide line) was printed on the paper base material using flexo printing.
  • the printed ink film was 2 to 5 ⁇ m thick.
  • the ink film was dried, and the coated dry film was The coated and dried film was photo-baked using a flash lamp with an energy of 4 J/cm 2 .
  • the resistance (wiring resistance) of the formed conductive film (line) with a measurement length of 37.8 mm was measured using a tester.
  • the cross-sectional area of the conductive film (line) was measured using a laser microscope.Then, the volume resistivity and average thickness of the conductive film were calculated from the resistance value, cross-sectional area, etc.
  • copper ink is transferred from the plate to the paper base.
  • the conductive film is not completely transferred to the material and is randomly split between the plate and the paper base material.For this reason, the cross-sectional shape of the conductive film that is formed is usually not smooth but has irregularities.
  • the average thickness of the conductive film is The thickness is the average thickness of the unevenness, that is, the thickness of the rectangle.
  • the formed conductive film (line) was evaluated by its wiring resistance.
  • the composition range of the copper ink in Examples will be explained.
  • the particle size (median diameter) of the copper fine particles was set to 60 to 110 nm.
  • the median diameter (D50) was calculated from the particle size frequency distribution of 100 or more fine copper particles randomly extracted from a 30,000 times magnified SEM image of the copper ink.
  • the concentration of the copper fine particles was 60 to 75% by weight (hereinafter the same applies to the weight percentage of the copper fine particles) based on the entire copper ink.
  • the dispersant had a phosphoric acid group.
  • the concentration of the dispersion medium was 3 to 6% by weight based on the weight of copper (hereinafter the same applies to the weight% of the dispersant).
  • the dispersion medium was an alcohol having multiple hydroxy groups.
  • the amount of dispersion medium is the balance in the copper ink.
  • Conductive films formed by photo-baking were evaluated by changing the composition of the copper ink. Note that, as described above, the cross-sectional area and wiring resistance of the conductive film are actually measured values, and the average thickness and volume resistivity are calculated values.
  • Copper fine particles with a median diameter of 80 nm were used in the copper ink (same in Examples 2 to 6 and Comparative Examples 1 and 3). The concentration of copper fine particles was 75% by weight.
  • a polymeric phosphate ester manufactured by BYK-Chemie, trade name "DISPERBYK (registered trademark)-102" was used as a dispersant. This dispersant is a polymer compound having a phosphoric acid group. The concentration of the dispersant was 4% by weight. 2-methyl 2,4-pentanediol (dihydric alcohol) was used as a dispersion medium.
  • the formed conductive film had no cracks.
  • the average thickness of the conductive film was 1.8 ⁇ m.
  • the volume resistivity was 5.2 ⁇ cm.
  • the cross-sectional area was 1100 ⁇ m2 .
  • the line width was 600 ⁇ m.
  • the wiring resistance was 1.8 ⁇ . This wiring resistance was the lowest among the examples.
  • the concentration of copper fine particles was 70% by weight, lower than in Example 1.
  • the concentration of the dispersant was 3% by weight, lower than in Example 1.
  • Other conditions were the same as in Example 1.
  • the formed conductive film had no cracks.
  • the average thickness of the conductive film was 1.3 ⁇ m, which was thinner than in Example 1.
  • the volume resistivity was 5.1 ⁇ cm, lower than in Example 1.
  • the cross-sectional area was 800 ⁇ m2 .
  • the line width was 600 ⁇ m.
  • the wiring resistance was 2.4 ⁇ , higher than in Example 1.
  • Example 1 Since the concentration of copper fine particles was lower than in Example 1, the average thickness of the conductive film was thinner and the wiring resistance was higher. Since the concentration of the dispersant was lower than in Example 1, the volume resistivity of the conductive film was lower, but the concentration of copper fine particles had a large influence on the wiring resistance.
  • the concentration of copper fine particles was set to 60% by weight, which is even lower than in Example 2. Other conditions were the same as in Example 2.
  • the formed conductive film had no cracks.
  • the average thickness of the conductive film was 0.7 ⁇ m, which was thinner than in Example 2.
  • the volume resistivity was 5.1 ⁇ cm, the same as in Example 1.
  • the cross-sectional area was 420 ⁇ m2 .
  • the line width was 600 ⁇ m.
  • the wiring resistance was 4.6 ⁇ , higher than in Example 2.
  • Example 2 Since the concentration of copper fine particles was lower than in Example 2, the average thickness of the conductive film was thinner and the wiring resistance was higher.
  • a polymeric phosphate ester (manufactured by BYK-Chemie, trade name "DISPERBYK (registered trademark)-111") was used as a dispersant.
  • This dispersant is a polymer compound having a phosphoric acid group.
  • the concentration of the dispersant was 4% by weight, which is higher than in Example 3.
  • Other conditions were the same as in Example 3.
  • the formed conductive film had no cracks.
  • the average thickness of the conductive film was 0.7 ⁇ m, the same as in Example 3.
  • the volume resistivity was 5.3 ⁇ cm, higher than that of Example 3.
  • the cross-sectional area was 420 ⁇ m2 .
  • the line width was 600 ⁇ m.
  • the wiring resistance was 4.8 ⁇ , higher than in Example 3.
  • Example 3 Since the concentration of the dispersant was higher than in Example 3, the volume resistivity of the conductive film was high, and the wiring resistance was high.
  • an alkylol ammonium salt of a copolymer having an acid group (manufactured by BYK-Chemie, trade name "DISPERBYK (registered trademark)-180") was used.
  • This dispersant is a salt of a polymer compound having a phosphoric acid group.
  • Other conditions were the same as in Example 4.
  • the formed conductive film had no cracks.
  • the average thickness of the conductive film was 0.8 ⁇ m, which was thicker than in Example 4.
  • the volume resistivity was 5.6 ⁇ cm, higher than that of Example 4.
  • the cross-sectional area was 450 ⁇ m2 .
  • the line width was 600 ⁇ m.
  • the wiring resistance was 4.7 ⁇ , which was slightly lower than in Example 4.
  • the dispersant may be a salt of a polymer compound having a phosphoric acid group.
  • the formed conductive film had no cracks.
  • the average thickness of the conductive film was 0.8 ⁇ m, the same as in Example 5.
  • the volume resistivity was 5.4 ⁇ cm, lower than that of Example 5.
  • the cross-sectional area was 450 ⁇ m2 .
  • the line width was 600 ⁇ m.
  • the wiring resistance was 4.5 ⁇ , which was slightly lower than in Example 5.
  • the dispersion medium in Example 6 has a plurality of hydroxy groups as in Examples 1 to 5. Although the dispersion medium in Example 6 had a different carbon skeleton from the dispersion medium in Examples 1 to 5, it could be used in the copper ink of the present invention.
  • the concentration of the dispersant was 4% by weight.
  • Other conditions were the same as in Example 2.
  • the formed conductive film had no cracks.
  • the average thickness of the conductive film was 1.5 ⁇ m, which was thicker than in Example 2.
  • the volume resistivity was 7.1 ⁇ cm, higher than that of Example 2.
  • the cross-sectional area was 900 ⁇ m2 .
  • the line width was 600 ⁇ m.
  • the wiring resistance was 3.0 ⁇ , higher than in Example 2.
  • the average thickness of the conductive film was thicker, and the volume resistivity of the conductive film was higher.
  • the concentration of copper fine particles was set to 60% by weight, lower than in Example 7. Other conditions were the same as in Example 7.
  • the formed conductive film had no cracks.
  • the average thickness of the conductive film was 1.1 ⁇ m, which was thinner than in Example 7.
  • the volume resistivity was 6.9 ⁇ cm, lower than that of Example 2.
  • the cross-sectional area was 650 ⁇ m2 .
  • the line width was 600 ⁇ m.
  • the wiring resistance was 4.0 ⁇ , higher than in Example 7.
  • Example 7 Since the concentration of copper fine particles was lower than in Example 7, the average thickness of the conductive film was thinner and the wiring resistance was higher.
  • the formed conductive film had no cracks.
  • the average thickness of the conductive film was 0.8 ⁇ m, which was thinner than in Example 8.
  • the volume resistivity was 5.0 ⁇ cm, lower than that of Example 8.
  • the cross-sectional area was 450 ⁇ m2 .
  • the line width was 600 ⁇ m.
  • the wiring resistance was 4.2 ⁇ , higher than in Example 8.
  • the formed conductive film had no cracks.
  • the average thickness of the conductive film was 1.2 ⁇ m, which was slightly thicker than in Example 8.
  • the volume resistivity was 6.1 ⁇ cm, lower than that of Example 8.
  • the cross-sectional area was 450 ⁇ m2 .
  • the line width was 600 ⁇ m.
  • the wiring resistance was 3.3 ⁇ , lower than in Example 8.
  • Example 8 Since the median diameter of the copper fine particles was smaller than in Example 8, the volume resistivity of the conductive film was lower than in Example 8.
  • the conductive films (line width 600 ⁇ m, length 37.8 mm) formed using the copper inks of Examples 1 to 10 have electrical resistances in the range of 1.8 ⁇ to 4.8 ⁇ , and are suitable for RF tag antennas. It had suitably low resistance (less than 10 ⁇ ).
  • Example 1 The concentration of copper fine particles was set to 40% by weight, lower than in Examples 1 to 10. Other conditions were the same as in Example 1.
  • the formed conductive film had no cracks.
  • the average thickness of the conductive film was 0.3 ⁇ m, which was thinner than in Examples 1 to 10.
  • the volume resistivity was 5.7 ⁇ cm.
  • the cross-sectional area was 200 ⁇ m2 .
  • the line width was 600 ⁇ m.
  • the wiring resistance was 10.8 ⁇ , higher than Examples 1 to 10.
  • the formed conductive film had cracks.
  • the wiring was broken.
  • Example 3 The concentration of the dispersant was 8% by weight, which is higher than in Examples 1-10. Other conditions were the same as in Example 3.
  • the formed conductive film had no cracks.
  • the average thickness of the conductive film was 0.6 ⁇ m.
  • the volume resistivity was 10.1 ⁇ cm, higher than Examples 1 to 10.
  • the cross-sectional area was 380 ⁇ m2 .
  • the line width was 600 ⁇ m.
  • the wiring resistance was 10.0 ⁇ , higher than in Examples 1 to 10.
  • the concentration of the dispersant was too high, the volume resistivity of the conductive film increased and the wiring resistance increased.
  • the formed conductive film had no cracks.
  • the average thickness of the conductive film was 1.7 ⁇ m.
  • the volume resistivity was 31.7 ⁇ cm, higher than Examples 1 to 10.
  • the cross-sectional area was 1000 ⁇ m2 .
  • the line width was 600 ⁇ m.
  • the wiring resistance was 12.0 ⁇ , higher than Examples 1 to 10.
  • the conductive films (line width 600 ⁇ m, length 37.8 mm) formed using the copper inks of Comparative Examples 1 to 4 were disconnected or had high resistance (10 ⁇ or more) unsuitable for RF tag antennas.
  • a conductive film (line) was formed on a paper base material in the same manner as in the above example, and the wiring resistance was measured before and after a constant temperature and humidity test.
  • the temperature of the constant temperature and humidity test was 85° C., the humidity was 85%, and the holding time was 264 hours.
  • a conductive film was formed using the same copper ink as in Example 4. That is, the median diameter of the copper fine particles is 80 nm, the concentration of the copper fine particles is 60% by weight, the dispersant is a polymeric phosphate ester, the concentration of the dispersant is 4% by weight, and the dispersion medium is 2-methyl 2,4-pentanediol. did. Then, a constant temperature and humidity test was conducted on the formed conductive film.
  • the wiring resistance of the conductive film before the constant temperature and humidity test was 4.8 ⁇ .
  • the wiring resistance after the constant temperature and humidity test was 9.6 ⁇ .
  • the resistance increase rate was 200%.
  • the conductive film was discolored only on the surface due to oxidation.
  • the concentration of the dispersant was 3% by weight, lower than in Example 11. Other conditions were the same as in Example 11.
  • the wiring resistance of the conductive film before the constant temperature and humidity test was 4.6 ⁇ .
  • the wiring resistance after the constant temperature and humidity test was 11.5 ⁇ .
  • the resistance increase rate was 250%.
  • the conductive film was discolored only on the surface due to oxidation.
  • Example 5 The concentration of the dispersant was 2% by weight, lower than in Example 12. Other conditions were the same as in Example 11.
  • the wiring resistance of the conductive film before the constant temperature and humidity test was 2.8 ⁇ .
  • the wiring resistance after the constant temperature and humidity test could not be measured.
  • the resistance increase rate was ⁇ . This conductive film could not withstand the constant temperature and humidity test.
  • the wiring resistance of the conductive film before the constant temperature and humidity test was 1.2 ⁇ .
  • the wiring resistance after the constant temperature and humidity test could not be measured.
  • the resistance increase rate was ⁇ . This conductive film could not withstand the constant temperature and humidity test.
  • the present invention is not limited to the configuration of the above-described embodiments, and various modifications can be made without changing the gist of the invention.
  • copper ink may be printed on a paper substrate using a printing method other than flexography.
  • the RF tag of the present invention is not limited to application to an RFID supply chain.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
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  • Spectroscopy & Molecular Physics (AREA)
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  • Inks, Pencil-Leads, Or Crayons (AREA)
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Abstract

Dans la présente invention, un film conducteur à faible résistance est formé sur un matériau de base en papier.　Une encre de cuivre selon la présente invention comprend de fines particules de cuivre, un milieu de dispersion liquide et un agent dispersant qui disperse les fines particules de cuivre dans le milieu de dispersion. Les fines particules de cuivre sont des particules de cuivre présentant un diamètre moyen de 60 à 110 nm. La concentration des fines particules de cuivre n'est pas inférieure à 60 % en poids relativement à la totalité de l'encre de cuivre. Le milieu de dispersion contient un alcool comprenant une pluralité de groupes hydroxy. L'agent dispersant est un composé polymère comprenant un groupe phosphate, ou un sel correspondant. La concentration du dispersant est de 3 à 6 % en poids relativement au poids du cuivre. L'encre de cuivre forme un film conducteur d'un matériau de base en papier par cuisson optique.
PCT/JP2022/031645 2022-06-22 2022-08-23 Encre de cuivre, procédé de formation de film conducteur et étiquette rfid WO2023248485A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013105605A (ja) * 2011-11-14 2013-05-30 Ishihara Chem Co Ltd 銅微粒子分散液、導電膜形成方法及び回路基板
JP2013104089A (ja) * 2011-11-14 2013-05-30 Ishihara Chem Co Ltd 銅微粒子分散液、導電膜形成方法及び回路基板
JP2013175559A (ja) * 2012-02-24 2013-09-05 Hitachi Chemical Co Ltd 接着剤層と配線層よりなる複合層及びそれを形成するための印刷用接着剤層形成インク
JP2014222611A (ja) * 2013-05-14 2014-11-27 石原ケミカル株式会社 銅微粒子分散液、導電膜形成方法及び回路基板
WO2017057301A1 (fr) * 2015-09-30 2017-04-06 住友電気工業株式会社 Liquide de revêtement permettant de former une couche électroconductrice, et procédé de fabrication d'une couche électroconductrice
JP2018147658A (ja) * 2017-03-03 2018-09-20 三菱マテリアル株式会社 導電性組成物

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013105605A (ja) * 2011-11-14 2013-05-30 Ishihara Chem Co Ltd 銅微粒子分散液、導電膜形成方法及び回路基板
JP2013104089A (ja) * 2011-11-14 2013-05-30 Ishihara Chem Co Ltd 銅微粒子分散液、導電膜形成方法及び回路基板
JP2013175559A (ja) * 2012-02-24 2013-09-05 Hitachi Chemical Co Ltd 接着剤層と配線層よりなる複合層及びそれを形成するための印刷用接着剤層形成インク
JP2014222611A (ja) * 2013-05-14 2014-11-27 石原ケミカル株式会社 銅微粒子分散液、導電膜形成方法及び回路基板
WO2017057301A1 (fr) * 2015-09-30 2017-04-06 住友電気工業株式会社 Liquide de revêtement permettant de former une couche électroconductrice, et procédé de fabrication d'une couche électroconductrice
JP2018147658A (ja) * 2017-03-03 2018-09-20 三菱マテリアル株式会社 導電性組成物

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