WO2021192523A1 - Encre de cuivre et procédé de formation d'un film électro-conducteur - Google Patents

Encre de cuivre et procédé de formation d'un film électro-conducteur Download PDF

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Publication number
WO2021192523A1
WO2021192523A1 PCT/JP2021/000997 JP2021000997W WO2021192523A1 WO 2021192523 A1 WO2021192523 A1 WO 2021192523A1 JP 2021000997 W JP2021000997 W JP 2021000997W WO 2021192523 A1 WO2021192523 A1 WO 2021192523A1
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Prior art keywords
copper
copper ink
conductive film
dispersant
firing
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PCT/JP2021/000997
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English (en)
Japanese (ja)
Inventor
三田　倫広
祐一 川戸
英俊 有村
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石原ケミカル株式会社
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Priority to CN202180021070.3A priority Critical patent/CN115298269A/zh
Publication of WO2021192523A1 publication Critical patent/WO2021192523A1/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
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/66—Copper alloys, e.g. bronze
    • 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
    • C09D11/023—Emulsion 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/08—Printing inks based on natural resins
    • 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
    • C09D17/00—Pigment pastes, e.g. for mixing in 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

Definitions

  • the present invention relates to a copper ink suitable for screen printing and a conductive film forming method using the same.
  • a method has been known in which a conductive paste is printed on a substrate by screen printing, and the printed conductive paste is irradiated with light and fired to form a conductive film on the substrate (for example, a patent).
  • the conductive paste contains copper fine particles, copper coarse particles, and a binder resin in a solvent.
  • the copper fine particles are coated with an azole compound.
  • the binder resin is added to improve the adhesion to the substrate (see paragraph 0017 of Patent Document 1 and paragraph 0019 of Patent Document 2).
  • the binder resin is polyvinylpyrrolidone resin
  • the amount is 3 to 9% by mass with respect to the total amount of copper fine particles and coarse copper particles
  • the binder resin is polyvinyl butyral resin
  • the amount is copper fine particles and coarse copper. It is 3 to 6% by mass with respect to the total amount of particles (see paragraph 0007 of Patent Document 1 and paragraph 0020 of Patent Document 2).
  • the binder resin added to the conductive paste has a problem of increasing the electrical resistance of the formed conductive film.
  • the present invention solves the above-mentioned problems, and in copper ink for forming a conductive film by firing, it is possible to print on a base material by screen printing, and the electrical resistance of the formed conductive film is lowered.
  • the purpose is.
  • the copper ink of the present invention is an ink for firing in a formic acid atmosphere, and contains copper fine particles, a dispersion medium containing the copper fine particles, and a dispersant for dispersing the copper fine particles in the dispersion medium.
  • the copper fine particles include those having a median diameter of 10 nm or more and 100 nm or less, the dispersion medium contains an organic solvent having a hydroxy group, and the dispersant is a polymer compound.
  • the dispersant is preferably polyester.
  • the dispersant may be a polymer compound having a basic group.
  • the dispersant is preferably an alkylammonium salt or a block copolymer having a basic group.
  • a binder resin is added, and the binder resin is a resin that is soluble in the organic solvent, and may be 0.1% by weight or more and less than 1% by weight with respect to the entire copper ink.
  • the binder resin is preferably a thermoplastic cellulose ether of ethyl cellulose.
  • the conductive film forming method of the present invention is a conductive film forming method for forming a conductive film pattern on a base material, and forms a copper ink film pattern on a base material by screen printing using the above copper ink. It is characterized by having a step and a step of firing the copper ink film on the base material in a formic acid atmosphere to form a conductive film on the base material.
  • the hydrogen bond between the copper fine particles and the organic solvent provides the rheological characteristics required for screen printing, so that the base material can be printed by screen printing.
  • formic acid promotes the decomposition of the dispersant, so that the electrical resistance of the formed conductive film is lowered.
  • the dispersant is a polymer compound having a basic group
  • the basic group of the dispersant reacts with formic acid, so that the decomposition of the dispersant is further promoted and the electrical resistance of the formed conductive film is lowered.
  • FIG. 1A and 1B are cross-sectional configuration views showing the formation of a conductive film using copper ink according to an embodiment of the present invention in chronological order.
  • the copper ink is for firing in a formic acid atmosphere, and contains copper fine particles, a dispersion medium containing the copper fine particles, and a dispersant.
  • the dispersant disperses the copper fine particles in the dispersion medium.
  • the copper fine particles are copper particles and include those having a median diameter (d50) of 10 nm or more and 100 nm or less.
  • the dispersion medium contains an organic solvent having a hydroxy group.
  • the dispersant is a polymeric compound.
  • This copper ink is an ink suitable for screen printing, contains copper fine particles as conductive particles, and exhibits conductivity by firing.
  • the copper fine particles fine particles having a single median diameter may be used, or fine particles having two or more types of median diameters may be mixed and used.
  • the concentration of the copper fine particles is set to a value at which a sufficient amount of copper fine particles for forming the conductive film can be obtained.
  • the particle size range (median diameter range) of the small particles is 10 nm or more and 100 nm or less, and the large particles.
  • the particle size range is preferably 0.5 ⁇ m or more and 5 ⁇ m or less.
  • the particle shape of the large particles may be spherical or flaky.
  • the small particles are sintered at a relatively low temperature, and the firing proceeds by connecting the large particles, so that the large particles do not greatly contribute to the electrical resistance of the conductive film formed.
  • the film thickness of the conductive film is as thin as 10 ⁇ m or less, large particles are unnecessary. Large particles are necessary for raising the thickness of the conductive film and allowing formic acid to penetrate into the film when the film thickness is thick. If the particle size of the large particles is less than 0.5 ⁇ m, voids for formic acid to penetrate into the film cannot be obtained. When the particle size of the large particles exceeds 5 ⁇ m, the dispersibility of the copper ink is lowered and the screen printability is also lowered.
  • the dispersion medium contains an organic solvent having a hydroxy group.
  • the hydroxy group is familiar because it forms a hydrogen bond with the surface of the copper fine particles, and therefore the organic solvent having a hydroxy group is excellent in the dispersibility of the copper fine particles.
  • the organic solvent of the dispersion medium may have a derivative of a hydroxy group. Derivatives of hydroxy groups are, for example, acetyl groups.
  • a polymer is a molecule with a large molecular weight, and has a structure composed of a large number of repetitions of units that can be obtained substantially or conceptually from a molecule with a small molecular weight (International Union of Pure and Applied Chemistry (IUPAC)).
  • the polymer compound of the dispersant is preferably an organic compound having a weight average molecular weight of 1000 or more.
  • the polymer compound of the dispersant is, for example, polyester.
  • the dispersant may be a polymer compound having a basic group.
  • a dispersant is, for example, an alkylammonium salt, or a block copolymer having a basic group.
  • Binder resin is added to the conventional conductive paste and conductive ink for screen printing. Binder resins are required to adjust the rheological properties (viscoelasticity) of conductive pastes and the like to be suitable for screen printing.
  • the copper ink of the present invention does not require the addition of a binder resin. In the present embodiment, the binder resin is not added to the copper ink.
  • the copper fine particles are dispersed in the dispersion medium because the surface is covered with the dispersant molecules.
  • the dispersion medium contains an organic solvent having a hydroxy group. Therefore, in the copper ink, a hydrogen bond is generated between the oxygen atom of the copper oxide of the surface oxide film and the hydrogen atom of the hydroxy group of the organic solvent.
  • the particle size of the copper fine particles is small, the influence of hydrogen bonds on each copper fine particle becomes large. Appropriate hydrogen bonds occur when the median diameter of the copper fine particles is 10 nm or more and 100 nm or less.
  • the copper ink of the present invention does not require the addition of a binder resin.
  • the binder resin is not added to the copper ink.
  • a small amount of binder resin may be added to the copper ink.
  • the binder resin is a resin that is soluble in the organic solvent of the dispersion medium, and is 0.1% by weight or more and less than 1% by weight with respect to the entire copper ink.
  • the binder resin is, for example, a thermoplastic cellulose ether of ethyl cellulose.
  • the amount of the binder resin is less than 0.1% by weight based on the entire copper ink, the effect at the time of printing is not so much as compared with the case where the binder resin is not added. It is not necessary to increase the amount of the binder resin to 1% by weight or more, and the electric resistance of the conductive film to be formed increases.
  • This conductive film forming method is a method of forming a conductive film pattern on a base material using copper ink.
  • the pattern of the copper ink film 1 is formed on the base material 2 by screen printing using the copper ink.
  • the copper ink film 1 on the base material 2 is fired in a formic acid atmosphere. In the firing, the dispersion medium in the copper ink film 1 is dried, the copper fine particles 11 in the copper ink film 1 are sintered, and the conductive film 3 is formed as shown in FIG. 1 (b).
  • this conductive film forming method includes a step of forming a pattern of a copper ink film 1 on a base material 2 by screen printing using copper ink, and firing the copper ink film 1 on the base material 2 in a formic acid atmosphere. It has a step of forming a conductive film 3 on the base material 2.
  • the base material 2 is a molded insulating material, has a screen-printable surface, and is, for example, a flexible substrate or a rigid substrate.
  • the firing of the copper ink film 1 in a formic acid atmosphere is thermal firing, and is performed using a formic acid reflow device.
  • a formic acid reflow device is generally a device that performs solder reflow using formic acid reduction.
  • a device for performing solder reflow is used for firing the copper ink film 1 in a formic acid atmosphere.
  • the copper ink contains copper fine particles 11 having a small particle size, the temperature required for firing is low and the time is short.
  • the copper ink contains copper fine particles 11 having a small particle size
  • the rheological characteristics required for screen printing can be obtained by hydrogen bonding between the copper fine particles 11 and the organic solvent, and a binder resin is added. You don't have to. Since the copper ink does not contain the binder resin, or even if it contains the binder resin, the amount is very small, so that the electric resistance of the conductive film 3 to be formed becomes low.
  • the copper fine particles 11 having a small particle size reduce the gaps between the copper fine particles 11 and further reduce the electric resistance of the conductive film 3 formed.
  • the volume resistivity of the formed conductive film 3 can be reduced to about 4 to 5 ⁇ ⁇ cm, which is about 1/10 of the resistivity of the conventional conductive film formed by using screen printing, and the resistivity of bulk copper. It is 1.7 ⁇ ⁇ cm, and the resistivity of plated copper is quite close to about 2 ⁇ ⁇ cm.
  • the electrical resistance of the conductive film 3 formed by firing the copper ink does not decrease to this extent simply by using the copper fine particles 11 having a small particle size and reducing the amount of the binder resin added.
  • the inventor of the present application has conducted many experiments to develop a copper ink and a conductive film forming method for forming such a conductive film 3 having a low electric resistance.
  • the dispersant In the conventional conductive paste and conductive ink, the dispersant remains without being decomposed at the time of firing, so that the electric resistance of the formed conductive film becomes high.
  • the copper ink of the present invention is for firing in a formic acid atmosphere, and since the dispersant is a polymer compound, the conductive film formed by promoting the decomposition of the dispersant by formic acid during firing in a formic acid atmosphere. The electrical resistance of 3 becomes low.
  • the dispersant is a polymer compound having a basic group, the basic group of the dispersant reacts with formic acid, so that the decomposition of the dispersant is further promoted and the electrical resistance of the formed conductive film 3 is lowered.
  • the conductive circuit produced by this conductive film forming method will be described with reference to FIG. 1 (b).
  • the conductive circuit 4 has a base material 2 and a pattern of the conductive film 3.
  • the pattern of the conductive film 3 is formed on the base material 2 by the above-described conductive film forming method.
  • a thick conductive film 3 having a thickness of about 10 ⁇ m to 40 ⁇ m can be formed on the base material 2, and the electric resistance of the conductive film 3 can be lowered.
  • a copper ink as an example of the present invention and a copper ink for comparison were prepared, and an attempt was made to form a conductive film using the copper ink.
  • Copper ink was made by the following method. Copper fine particles were gradually added to the dispersion medium and the dispersant measured to a predetermined concentration, and the mixture was stirred by a rotation / revolution mixer and then mixed and stabilized by a disperser such as a disper or a mill.
  • a base material a plate obtained by cutting out 0.5 mm thick non-alkali glass (manufactured by Corning Inc., trade name "Eagle XG") was used. Then, the produced copper ink was screen-printed on the base material, and the printed copper ink film was fired. The feasibility of forming a conductive film, the film thickness of the conductive film, and the volume resistivity were evaluated by changing conditions such as copper ink, firing temperature, and firing time.
  • the copper fine particles small particles having a median diameter of 40 to 50 nm and spherical particles having a median diameter of 0.5 ⁇ m were mixed and used at a weight ratio of 7: 3 (the same applies to Examples 2 to 13 and Comparative Examples).
  • the concentration of the copper fine particles was set to 85% by weight with respect to the entire copper ink (hereinafter, the same in terms of weight%).
  • An organic solvent having a hydroxy group (manufactured by Japan Terpene Chemical Co., Ltd., trade name "Tersolv MTPH”) and an organic solvent having a hydroxy group and an acetyl group (manufactured by Japan Terpene Chemical Co., Ltd., trade name “Tersolv THA-90”) are used as dispersion media. They were mixed and used (weight ratio 1: 1). Polyester (manufactured by Big Chemie, trade name "DISPERBYK (registered trademark) -2152”) was used as the dispersant, and the concentration thereof was set to 3% by weight. No binder resin was added to the copper ink. Next, a copper ink film was formed on the substrate by screen printing using this copper ink.
  • the copper ink film was fired by a formic acid reflow device.
  • the firing temperature was 300 ° C. and the firing time was 10 minutes.
  • a conductive film was formed.
  • the film thickness of the conductive film was 16 ⁇ m, and the volume resistivity was 5 ⁇ ⁇ cm.
  • the copper ink, firing temperature, and firing time were the same as in Example 1, and a thicker conductive film than in Example 1 was formed.
  • the film thickness of the conductive film was 21 ⁇ m, and the volume resistivity was 5 ⁇ ⁇ cm.
  • the copper ink, firing temperature, and firing time were the same as in Example 2, and a thicker conductive film than in Example 2 was formed.
  • the film thickness of the conductive film was 38 ⁇ m, and the volume resistivity was 5 ⁇ ⁇ cm.
  • An alkylammonium salt (manufactured by Big Chemie, trade name "DISPERBYK (registered trademark) -9076") was used as a dispersant, and the concentration was set to 3% by weight.
  • the components other than the dispersant, the firing temperature, and the firing time in the copper ink were the same as in Example 3. After firing, a conductive film was formed. The film thickness of the conductive film was 39 ⁇ m, and the volume resistivity was 10 ⁇ ⁇ cm.
  • a block copolymer having a basic group (manufactured by Big Chemie, trade name "DISPERBYK (registered trademark) -2013”) was used as a dispersant, and the concentration thereof was set to 3% by weight.
  • the components other than the dispersant, the firing temperature, and the firing time in the copper ink were the same as in Example 4. After firing, a conductive film was formed. The film thickness of the conductive film was 7 ⁇ m, and the volume resistivity was 6 ⁇ ⁇ cm.
  • a block copolymer having a basic group (manufactured by Big Chemie, trade name "DISPERBYK (registered trademark) -2155") was used as a dispersant, and the concentration was set to 3% by weight.
  • the components of the copper ink other than the dispersant were the same as in Example 1.
  • the firing temperature was 250 ° C., which was lower than that of Example 5, and the firing time was 30 minutes, which was longer than that of Example 5.
  • a conductive film was formed.
  • the film thickness of the conductive film was 32 ⁇ m, and the volume resistivity was 10 ⁇ ⁇ cm.
  • the copper ink film to be printed is thickened, it becomes difficult to fire the film, so that the volume resistivity of the formed conductive film may increase. However, as the film thickness of the conductive film increases, the electrical resistance of the conductive film decreases.
  • the copper ink and firing temperature were the same as in Example 6, and the firing time was 60 minutes, which was longer than in Example 6.
  • the film thickness of the conductive film was 28 ⁇ m, and the volume resistivity was 10 ⁇ ⁇ cm.
  • the copper ink was the same as in Example 6, and the firing temperature and firing time were the same as in Example 5.
  • the film thickness of the conductive film was 41 ⁇ m, and the volume resistivity was 8 ⁇ ⁇ cm.
  • the copper ink, firing temperature, and firing time were the same as in Example 8, and a conductive film slightly thinner than in Example 8 was formed.
  • the film thickness of the conductive film was 30 ⁇ m, and the volume resistivity was 7 ⁇ ⁇ cm.
  • Example 9 The copper ink and firing time were the same as in Example 9, the firing temperature was 350 ° C., which was higher than in Example 9, and a thinner conductive film than in Example 9 was formed.
  • the film thickness of the conductive film was 3 ⁇ m, and the volume resistivity was 3 ⁇ ⁇ cm, which was lower than that of Example 9.
  • Example 10 The copper ink, firing temperature, and firing time were the same as in Example 10, and a thicker conductive film than in Example 10 was formed.
  • the film thickness of the conductive film was 27 ⁇ m, and the volume resistivity was 5 ⁇ ⁇ cm, which was higher than that of Example 10.
  • the copper ink and firing time were the same as in Example 11, and the firing temperature was set to 300 ° C., which was lower than that in Example 11.
  • the film thickness of the conductive film was 28 ⁇ m, and the volume resistivity was 7 ⁇ ⁇ cm, which was higher than that of Example 11.
  • the copper ink and firing time were the same as in Example 12, and the firing temperature was 350 ° C., which was higher than in Example 12.
  • the film thickness of the conductive film was 32 ⁇ m, and the volume resistivity was 5 ⁇ ⁇ cm, which was lower than that of Example 12.
  • the copper fine particles of the copper ink small particles having a median diameter of 40 to 50 nm and flaky particles having a median diameter of 2 to 3 ⁇ m were mixed and used at a weight ratio of 7: 3 (the same applies to Examples 14 to 31).
  • the other components of the copper ink were the same as in Example 13.
  • the firing temperature was set to 300 ° C., which was lower than that of Example 13, and the firing time was set to 10 minutes, which was the same as that of Example 13.
  • a conductive film was formed.
  • the film thickness of the conductive film was 32 ⁇ m, which was the same as in Example 13, and the volume resistivity was 8 ⁇ ⁇ cm, which was higher than that in Example 13.
  • the copper ink and firing time were the same as in Example 14, the firing temperature was 350 ° C., which was higher than in Example 14, and a thinner conductive film than in Example 14 was formed.
  • the film thickness of the conductive film was 10 ⁇ m, and the volume resistivity was 5 ⁇ ⁇ cm.
  • Example 15 The copper ink, firing temperature, and firing time were the same as in Example 15 to form a thicker conductive film than in Example 15.
  • the film thickness of the conductive film was 36 ⁇ m, and the volume resistivity was 6 ⁇ ⁇ cm.
  • the copper ink, firing temperature, and firing time were the same as in Example 16.
  • the film thickness of the conductive film was 35 ⁇ m, and the volume resistivity was 7 ⁇ ⁇ cm.
  • the volume resistivity is estimated to be in the range of variation as compared with Example 16.
  • Binder resin was added to the copper ink.
  • the other components of the copper ink were the same as in Examples 14 to 17. Specifically, 0.09% by weight of ethyl cellulose thermoplastic cellulose ether (manufactured by Dow Chemical Co., Ltd., trade name "Etocell STD4") was added to the copper ink as a binder resin.
  • the firing temperature was 300 ° C. and the firing time was 10 minutes. After firing, a conductive film was formed. The film thickness of the conductive film was 32 ⁇ m, and the volume resistivity was 8 ⁇ ⁇ cm.
  • Copper ink (binder resin added) and firing time were the same as in Example 18.
  • the firing temperature was 350 ° C.
  • the film thickness of the conductive film was 10 ⁇ m, and the volume resistivity was 5 ⁇ ⁇ cm.
  • Copper ink (added binder resin), firing temperature and firing time were made the same as in Example 19 to form a thicker conductive film than in Example 19.
  • the film thickness of the conductive film was 36 ⁇ m, and the volume resistivity was 6 ⁇ ⁇ cm.
  • Copper ink (added binder resin), firing temperature and firing time were the same as in Example 20.
  • the film thickness of the conductive film was 35 ⁇ m, and the volume resistivity was 7 ⁇ ⁇ cm.
  • the volume resistivity is estimated to be in the range of variation as compared with Example 20.
  • More binder resin than in Example 21 was added to the copper ink.
  • the other components of the copper ink were the same as in Example 21. Specifically, 0.21% by weight of ethyl cellulose thermoplastic cellulose ether was added to the copper ink.
  • the firing temperature and firing time were the same as in Example 21.
  • the film thickness of the conductive film was 37 ⁇ m, and the volume resistivity was 7 ⁇ ⁇ cm.
  • Copper ink (added binder resin), firing temperature and firing time were the same as in Example 22.
  • the film thickness of the conductive film was 36 ⁇ m, and the volume resistivity was 7 ⁇ ⁇ cm.
  • More binder resin than in Example 23 was added to the copper ink.
  • the other components of the copper ink were the same as in Example 23. Specifically, 0.30% by weight of ethyl cellulose thermoplastic cellulose ether was added to the copper ink.
  • the firing temperature was 250 ° C. and the firing time was 10 minutes.
  • the film thickness of the conductive film was 6 ⁇ m, and the volume resistivity was 6 ⁇ ⁇ cm.
  • Copper ink (added binder resin), firing temperature and firing time were the same as in Example 24, and a thicker conductive film than in Example 24 was formed.
  • the film thickness of the conductive film was 41 ⁇ m, and the volume resistivity was 9 ⁇ ⁇ cm, which was higher than that of Example 24.
  • the copper ink (added binder resin) was the same as in Example 24, the firing temperature was 350 ° C., and the firing time was 10 minutes.
  • the film thickness of the conductive film was 4 ⁇ m, and the volume resistivity was 4 ⁇ ⁇ cm.
  • Copper ink (added binder resin), firing temperature and firing time were the same as in Example 26, and a thicker conductive film than in Example 26 was formed.
  • the film thickness of the conductive film was 35 ⁇ m, and the volume resistivity was 6 ⁇ ⁇ cm, which was higher than that of Example 26.
  • Example 27 More binder resin than in Example 27 was added to the copper ink.
  • the other components of the copper ink were the same as in Example 27. Specifically, 0.43% by weight of ethyl cellulose thermoplastic cellulose ether was added to the copper ink.
  • the firing temperature and firing time were the same as in Example 27.
  • the film thickness of the conductive film was 38 ⁇ m, and the volume resistivity was 8 ⁇ ⁇ cm, which was higher than that of Example 27.
  • Copper fine particles were set to 80% by weight with respect to the entire copper ink. More binder resin than in Example 28 was added to the copper ink. The other components of the copper ink were the same as in Example 28. Specifically, 0.80% by weight of ethyl cellulose thermoplastic cellulose ether was added to the copper ink. The firing temperature was 300 ° C. and the firing time was 10 minutes. The film thickness of the conductive film was 32 ⁇ m, and the volume resistivity was 8 ⁇ ⁇ cm.
  • the copper ink (added binder resin) was the same as in Example 29, the firing temperature was 350 ° C., and the firing time was 10 minutes.
  • the film thickness of the conductive film was 6 ⁇ m, and the volume resistivity was 6 ⁇ ⁇ cm.
  • Copper ink (added binder resin), firing temperature and firing time were the same as in Example 30, and a thicker conductive film than in Example 30 was formed.
  • the film thickness of the conductive film was 31 ⁇ m, and the volume resistivity was 7 ⁇ ⁇ cm.
  • Example 1 The copper fine particles and the dispersion medium were the same as in Example 1.
  • a copolymer having an acidic group (manufactured by Big Chemie, trade name "DISPERBYK (registered trademark) -102") was used as a dispersant, and the concentration thereof was set to 3% by weight. No binder resin was added to the copper ink.
  • a copper ink film was formed on the substrate by screen printing using this copper ink. Then, the copper ink film was fired by a formic acid reflow device. The firing temperature was 300 ° C. and the firing time was 10 minutes. After firing, there were cracks in the formed conductive film, and the resistance could not be measured.
  • Comparative Example 2 A polymer salt having an acidic group (manufactured by Big Chemie, trade name "DISPERBYK (registered trademark) -106") was used as a dispersant, and the concentration thereof was set to 3% by weight. The components other than the dispersant, the firing temperature, and the firing time of the copper ink were the same as in Comparative Example 1. After firing, there were cracks in the formed conductive film, and the resistance could not be measured.
  • DISPERBYK registered trademark
  • Comparative Example 3 A polymer having an acidic group (manufactured by Big Chemie, trade name "DISPERBYK (registered trademark) -111") was used as a dispersant, and the concentration thereof was set to 3% by weight. The components other than the dispersant, the firing temperature, and the firing time of the copper ink were the same as in Comparative Example 1. After firing, there were cracks in the formed conductive film, and the resistance could not be measured.
  • Comparative Example 4 An unsaturated polycarboxylic acid polymer (manufactured by Big Chemie, trade name "DISPERBYK (registered trademark) -P105”) was used as a dispersant, and the concentration thereof was set to 3% by weight. The components other than the dispersant, the firing temperature, and the firing time of the copper ink were the same as in Comparative Example 1. After firing, there were cracks in the formed conductive film, and the resistance could not be measured.
  • DISPERBYK registered trademark
  • Comparative Example 5 Phosphonate (dodecylphosphonic acid (reagent)) was used as the dispersant, and the concentration thereof was set to 3% by weight.
  • the components other than the dispersant, the firing temperature, and the firing time of the copper ink were the same as in Comparative Example 1. After firing, there were cracks in the formed conductive film, and the resistance could not be measured.
  • Comparative Example 6 Oleic acid (reagent) was used as the dispersant, and the concentration thereof was set to 3% by weight.
  • the components other than the dispersant, the firing temperature, and the firing time of the copper ink were the same as in Comparative Example 1. After firing, there were cracks in the formed conductive film, and the resistance could not be measured.
  • the dispersant inhibited the formation of the conductive film.
  • a firing device other than the formic acid reflow device may be used in the step of firing the copper ink film in a formic acid atmosphere to form a conductive film on the substrate.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Conductive Materials (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Manufacturing Of Electric Cables (AREA)

Abstract

L'invention concerne une encre de cuivre pour la formation de films électro-conducteurs par cuisson, l'encre de cuivre étant imprimable par sérigraphie sur des substrats et formant des films électro-conducteurs ayant une résistance électrique réduite.　L'encre de cuivre est destinée à une cuisson dans une atmosphère d'acide formique et comprend : de fines particules de cuivre ; un milieu de dispersion qui contient les fines particules de cuivre ; et un dispersant à l'aide duquel les particules fines de cuivre sont dispersées dans le milieu de dispersion. Les particules fines de cuivre en contiennent qui ont un diamètre médian de 10 à 100 nm. Le milieu de dispersion contient un solvant organique ayant un groupe hydroxy. Le dispersant est un polymère.
PCT/JP2021/000997 2020-03-25 2021-01-14 Encre de cuivre et procédé de formation d'un film électro-conducteur WO2021192523A1 (fr)

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JP2020053484A JP6901227B1 (ja) 2020-03-25 2020-03-25 銅インク及び導電膜形成方法

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
WO2017159611A1 (fr) * 2016-03-15 2017-09-21 石原ケミカル株式会社 Liquide de dispersion de fines particules de cuivre, procédé de formation de film électroconducteur, et carte de circuit imprimé
JP2020009554A (ja) * 2018-07-04 2020-01-16 石原ケミカル株式会社 銅ペースト及び導電膜形成方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105658745B (zh) * 2013-10-31 2019-06-04 昭和电工株式会社 薄膜印刷用导电性组合物及薄膜导电图案形成方法
KR20170046164A (ko) * 2014-08-28 2017-04-28 이시하라 산교 가부시끼가이샤 금속질 구리 입자 및 그 제조 방법
JP6884692B2 (ja) * 2015-03-26 2021-06-09 三井金属鉱業株式会社 銅粉及びそれを含む導電性組成物

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
WO2017159611A1 (fr) * 2016-03-15 2017-09-21 石原ケミカル株式会社 Liquide de dispersion de fines particules de cuivre, procédé de formation de film électroconducteur, et carte de circuit imprimé
JP2020009554A (ja) * 2018-07-04 2020-01-16 石原ケミカル株式会社 銅ペースト及び導電膜形成方法

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