WO2022130892A1 - 銅ニッケル合金電極用導電性インク、銅ニッケル合金電極付基板、および、それらの製造方法 - Google Patents

銅ニッケル合金電極用導電性インク、銅ニッケル合金電極付基板、および、それらの製造方法 Download PDF

Info

Publication number
WO2022130892A1
WO2022130892A1 PCT/JP2021/042517 JP2021042517W WO2022130892A1 WO 2022130892 A1 WO2022130892 A1 WO 2022130892A1 JP 2021042517 W JP2021042517 W JP 2021042517W WO 2022130892 A1 WO2022130892 A1 WO 2022130892A1
Authority
WO
WIPO (PCT)
Prior art keywords
amino
copper
nickel
conductive ink
butanol
Prior art date
Application number
PCT/JP2021/042517
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
万里 李
剛生 三成
Original Assignee
国立研究開発法人物質・材料研究機構
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 国立研究開発法人物質・材料研究機構 filed Critical 国立研究開発法人物質・材料研究機構
Priority to JP2022569801A priority Critical patent/JPWO2022130892A1/ja
Priority to KR1020227046040A priority patent/KR20230019148A/ko
Priority to CN202180068292.0A priority patent/CN116323044A/zh
Publication of WO2022130892A1 publication Critical patent/WO2022130892A1/ja

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • 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
    • 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
    • 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 conductive ink for a copper-nickel alloy electrode, a substrate with a copper-nickel alloy electrode, and a method for manufacturing the same.
  • Non-Patent Document 1 copper particles and a silver complex are used to enable metal wiring having a core-shell structure in which copper particles are coated with a copper-silver alloy.
  • Non-Patent Document 2 a copper complex and a silver complex are used to enable metal wiring made of a copper-silver alloy.
  • the oxidation resistance is improved as compared with the metal wiring of copper alone, but further improvement is required for practical use.
  • unevenness, bumps, and cracks may occur on the electrode during use, and the stability is not sufficient.
  • the material contains silver, which makes it expensive.
  • Nickel particles are also used for electrodes because they are chemically more stable than copper particles and cheaper than silver particles (see, for example, Patent Document 1). According to Patent Document 1, it is disclosed that a nickel complex obtained from nickel formate dihydrate and an aliphatic amine can obtain nickel particles, and by changing the chain length of the alkyl group of the aliphatic amine. We report that the particle size of nickel particles can be controlled.
  • Patent Document 2 Copper nanoparticles having a nickel-copper alloy on the surface layer have been developed (see, for example, Patent Document 2). According to Patent Document 2, it is disclosed that the nickel-copper alloy on the surface layer has improved oxidation resistance and is used for fine wiring by a printing method or a coating method. However, even if such copper nanoparticles are used, there are problems that the ink stability is still not at a practical level, the firing temperature is high, and the cost is high.
  • the subject of the present invention is a conductive ink for a copper-nickel alloy electrode, a substrate with a copper-nickel alloy electrode, and a method for manufacturing them, which are inexpensive, have excellent atmospheric stability, and enable smooth metal wiring on the surface. Is to provide.
  • the conductive ink for a copper-nickel alloy electrode according to the present invention contains a copper complex represented by the general formula A and a nickel complex represented by the general formula B, and the content ratio of nickel to the total mass of copper and nickel. Is in the range of 5% by mass or more and less than 80% by mass, thereby solving the above-mentioned problems.
  • m and n are natural numbers of 2 to 6, respectively, L 1 is an amino alcohol having one amino group of the same or different, and L 2 is an amino of the same or different. It is an aliphatic amine having one group, or vice versa.
  • the amino alcohol has one primary amino group, at least one hydroxyl group, and is a saturated or unsaturated linear, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms. May have.
  • the amino alcohols include 2-aminoethanol, 2-amino-2-methyl-1-propanol, 1-amino-2-propanol, 2-amino-1-propanol, 1-amino-2-methyl-2-propanol, and the like.
  • 2-Amino-1-butanol 1-amino-2-butanol, 2-amino-3,3-dimethyl-1-butanol, 2-amino-3-methyl-1-butanol, 2-amino-4-methyl- 1-pentanol, 3-amino-1-propanol, 5-amino-1-pentanol, 6-amino-1-hexanol, 3-amino-2,2-dimethyl-1-propanol, 4-amino-1- Butanol, 8-amino-1-octanol, 10-amino-1-decanol, 12-amino-1-dodecanol, 2-aminocyclohexanol, 4-amino-2-methyl-1-butanol, 2-amino-1, Group consisting of 3-propanediol, 2-amino-2-methyl-1,3-propanediol, 3-amino-1,2-propanediol, and 2-amino-2
  • the aliphatic amine may have one primary amino group and a saturated or unsaturated, linear, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms.
  • the aliphatic amine may be selected from the group consisting of 2-ethylhexylamine, n-butylamine, tert-butylamine, benzylamine, n-hexylamine, 2-heptylamine, cyclohexylamine, and n-dodecylamine. ..
  • the nickel content may be in the range of 10% by mass or more and 70% by mass or less.
  • the nickel content may be in the range of 19% by mass or more and 67% by mass or less.
  • the conductive ink may further contain copper particles and / or nickel particles.
  • the conductive ink may further contain a monohydric alcohol and / or a polyhydric alcohol.
  • the monohydric alcohols include methanol, ethanol, 1-propanol, 1-butanol, 2-butanol, 2-methyl-1-butanol, 1-pentanol, 2-pentanol, 3-pentanol and 3-methyl-1. It may be selected from the group consisting of -butanol, 2-methyl-1-butanol, 2,2-dimethyl-1-propanol, 3-methyl-2-butanol, and 2-methyl-2-butanol.
  • the polyhydric alcohol may be selected from the group consisting of ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, butylene glycol, pentanediol, dipropylene glycol, tripropylene glycol, polyethylene glycol, polypropylene glycol, and glycerin. ..
  • the method for producing the above conductive ink according to the present invention comprises mixing copper formate and an amine ligand represented by L1 to form a copper complex, and nickel formate and an amine represented by L2. Mixing with the amine to form a nickel complex, and mixing the copper complex and the nickel complex so that the mass ratio of the nickel complex to the copper complex is 0.05 or more and less than 6.
  • a polyhydric alcohol may be further mixed.
  • the polyhydric alcohol may be selected from the group consisting of ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, butylene glycol, pentanediol, dipropylene glycol, tripropylene glycol, polyethylene glycol, polypropylene glycol, and glycerin. ..
  • a monohydric alcohol may be further added.
  • copper particles and / or nickel particles may be further mixed.
  • the substrate with a copper-nickel alloy electrode according to the present invention includes a substrate and an electrode containing a copper-nickel alloy located on the substrate, and the content ratio of nickel to the total mass of copper and nickel in the copper-nickel alloy is The range is 5% by mass or more and less than 80% by mass, thereby solving the above-mentioned problems.
  • the substrate may be selected from the group consisting of polyethylene naphthalate, polyimide, and polyolefin resin.
  • the method for manufacturing a substrate with a copper-nickel alloy electrode according to the present invention includes applying the conductive ink to the substrate and heating the substrate to which the conductive ink is applied, thereby solving the above-mentioned problems. solve.
  • the coating is a spin coating method, a spray coating method, a dip coating method, a slit coating method, a slot coating method, a bar coating method, a roll coating method, a curtain coating method, a gravure printing method, an inkjet method, and a screen printing method.
  • a method selected from the group consisting of may be used.
  • the heating may be performed in a temperature range of 170 ° C. or higher and 250 ° C. or lower in a time range of 1 minute or more and 60 minutes or less.
  • the above method may further include heating by light irradiation following the heating.
  • the conductive ink for a copper-nickel alloy electrode of the present invention contains the copper complex represented by the above-mentioned general formula A and the nickel complex represented by the general formula B, and is contained in the copper in the copper complex and the nickel complex.
  • the content ratio of nickel to the total mass with nickel is in the range of 5% by mass or more and less than 80% by mass.
  • a copper-nickel alloy can be easily formed at a low temperature, so that a polymer substrate with a copper-nickel alloy electrode can be provided and can be applied to a wearable device.
  • a flowchart showing a process of manufacturing the conductive ink of the present invention Schematic diagram showing a substrate with a copper-nickel alloy electrode of the present invention
  • a flowchart showing a process of manufacturing a substrate with a copper-nickel alloy electrode of the present invention The figure which shows the appearance of the electrode of Example 1.
  • the figure which shows the nickel content ratio dependence of the electric resistance of an electrode The figure which shows the result of the oxidation resistance test
  • the conductive ink for a copper-nickel alloy electrode of the present invention contains a copper complex represented by the general formula A and a nickel complex represented by the general formula B.
  • m and n are natural numbers of 2 to 6, respectively
  • L 1 and L 2 are amine ligands.
  • L 1 is an amino alcohol having one amino group, which is the same or different
  • L 2 is an aliphatic amine having one amino group, which is the same or different.
  • L 1 is an aliphatic amine having one amino group of the same or different
  • L 2 is an amino alcohol having one amino group of the same or different.
  • the conductive ink of the present invention satisfies the range in which the content ratio of nickel to the total mass of copper and nickel contained is 5% by mass or more and less than 80% by mass.
  • the nickel content is less than 5% by mass, the surface becomes uneven and smooth metal wiring cannot be obtained.
  • the nickel content is 80% by mass or more, the copper-nickel alloy cracks and the electric resistance increases, so that the copper-nickel alloy cannot function as an electrode.
  • the amino alcohol having one amino group of L 1 is preferably saturated or unsaturated, preferably having one primary amino group, at least one hydroxyl group, and having 1 or more and 20 or less carbon atoms. , Straight chain, branched chain or cyclic hydrocarbon group. By having a primary amino group, it coordinates with a copper ion and forms a complex. By having one or more hydroxyl groups, the affinity with the nickel complex is excellent. When the number of carbon atoms is 1 or more and 20 or less, a copper-nickel alloy can be obtained. From the viewpoint of affinity with the nickel complex and promotion of formation of the copper-nickel alloy, the number of carbon atoms is more preferably 2 or more and 10 or less, still more preferably 2 or more and 5 or less. L 1 may be the same or different, but may be the same from the viewpoint of yield.
  • the amino alcohol having one amino group the amino alcohol used for forming a copper complex in the production of ink using conventional copper nanoparticles can be applied.
  • the amino alcohol having one amino group is 2-aminoethanol, 2-amino-2-methyl-1-propanol, 1-amino-2-propanol, 2-amino-1-propanol, 1-amino-.
  • 2-Methyl-2-propanol 2-amino-1-butanol, 1-amino-2-butanol, 2-amino-3,3-dimethyl-1-butanol, 2-amino-3-methyl-1-butanol, 2-Amino-4-methyl-1-pentanol, 3-amino-1-propanol, 5-amino-1-pentanol, 6-amino-1-hexanol, 3-amino-2,2-dimethyl-1- Propanol, 4-amino-1-butanol, 8-amino-1-octanol, 10-amino-1-decanol, 12-amino-1-dodecanol, 2-aminocyclohexanol, 4-amino-2-methyl-1- Butanol, 2-amino-1,3-propanediol, 2-amino-2-methyl-1,3-propanediol, 3-amino-1,2-propanedi
  • Aliphatic amines having one amino group, L2 have linear, branched or cyclic hydrocarbon groups that have a primary amino group and are saturated or unsaturated with 1 to 20 carbon atoms. Have. By having a primary amino group, it coordinates with nickel ions and forms a complex. When the number of carbon atoms is 1 or more and 20 or less, a copper-nickel alloy can be obtained. From the viewpoint of affinity with the copper complex and promotion of formation of the copper-nickel alloy, the number of carbon atoms is more preferably 2 or more and 10 or less, still more preferably 2 or more and 7 or less. L 2 may be the same or different, but may be the same from the viewpoint of yield.
  • the aliphatic amine having one amino group is preferably from 2-ethylhexylamine, n-butylamine, tert-butylamine, benzylamine, n-hexylamine, 2-heptylamine, cyclohexylamine, and n-dodecylamine. It is selected from the group of They are readily available and promote the formation of nickel complexes.
  • some of the above - mentioned aliphatic amines which are L2 may have a hydroxyl group or may be an amino alcohol.
  • the above-mentioned amino alcohol can be adopted as the amino alcohol.
  • L 2 may be an amino alcohol and L 1 may be an aliphatic amine as long as it is a combination of the above-mentioned amino alcohol and an aliphatic amine.
  • L 1 may be an aliphatic amine as long as it is a combination of the above-mentioned amino alcohol and an aliphatic amine.
  • a copper-nickel alloy is formed, resulting in smooth metal wiring.
  • L 1 is an aliphatic amine
  • some of the aliphatic amines may have a hydroxyl group, and may be, for example, the above-mentioned amino alcohol.
  • the range of m and n may be 2 or more and 6 or less.
  • AMP 2-amino-2-methyl-1-propanol
  • L 1 when 2-amino-2-methyl-1-propanol (AMP) is selected as L 1 , it becomes a bidentate coordination and m is 2, but in the general formula B, L 2
  • 2-amino-2-methyl-1-propanol (AMP) is selected as, it becomes a tetradentate coordination, and n becomes 4.
  • the range of m and n is preferably 2 or more and 4 or less. This is preferable because the metal content in the conductive ink increases.
  • the content ratio of nickel to the total mass of copper and nickel preferably satisfies the range of 10% by mass or more and 70% by mass or less. Within this range, the surface may have less unevenness and smooth metal wiring can be obtained.
  • the nickel content is more preferably in the range of 19% by mass or more and 67% by mass or less. Within this range, the surface unevenness is extremely small, and the metal wiring can be very smooth.
  • the nickel content is still more preferably in the range of 30% by mass or more and 50% by mass or less. Within this range, it has oxidation resistance, has very few surface irregularities, and can be a very smooth metal wiring.
  • the conductive ink of the present invention preferably further contains copper particles and / or nickel particles. This enables thick metal wiring of several ⁇ m or more.
  • the particle size of these particles is preferably in the range of 50 nm or more and 1 ⁇ m or less, and more preferably in the range of 50 nm or more and 400 nm or less. This enables thick metal wiring with less surface irregularities and no cracks.
  • the copper particles When the copper particles are further contained, the copper particles may be contained so that the content ratio of nickel to the total mass of copper and nickel satisfies the above range. This enables thick metal wiring with excellent coatability, less surface irregularities, and no cracks. The same applies to nickel particles. The same applies when both particles are contained.
  • the conductive ink of the present invention may further contain a monohydric alcohol and / or a polyhydric alcohol. As a result, the viscosity is adjusted and the copper complex and the nickel complex are uniformly mixed, so that the ink has excellent coatability.
  • the monohydric alcohol is preferably an alkyl alcohol having 5 or less carbon atoms, an alkenyl alcohol, or a cycloalkyl alcohol, and specifically, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-. Butanol, 2-methyl-1-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 3-methyl-1-butanol, 2-methyl-1-butanol, 2,2-dimethyl-1-propanol , 3-Methyl-2-butanol, 2-methyl-2-butanol, cyclopropanol, cyclobutanol, cyclopentanol and the like.
  • the monohydric alcohol is preferably methanol, ethanol, 1-propanol, 1-butanol, 2-butanol, 2-methyl-1-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 3-methyl. It is selected from the group consisting of -1-butanol, 2-methyl-1-butanol, 2,2-dimethyl-1-propanol, 3-methyl-2-butanol, and 2-methyl-2-butanol. These are easily available and have a boiling point of 150 ° C. or lower, which is preferable for adjusting the viscosity.
  • the polyhydric alcohol may be a dihydric alcohol or a trihydric alcohol.
  • the polyhydric alcohol is preferably selected from the group consisting of ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, butylene glycol, pentanediol, dipropylene glycol, tripropylene glycol, polyethylene glycol, polypropylene glycol, and glycerin. .. These are easily available, and are conductive inks in which a copper complex and a nickel complex are uniformly mixed.
  • the viscosity of the conductive ink may be appropriately adjusted according to the intended use.
  • the viscosity of the conductive ink is 1 mPa ⁇ s for the monovalent alcohol and / or the polyhydric alcohol. It may be added so as to be 20 mPa ⁇ s or less.
  • FIG. 1 is a flowchart showing a process of manufacturing the conductive ink of the present invention.
  • Step S110 Copper formate and an amine ligand represented by L1 are mixed to form a copper complex. Since L 1 is the same as the above-mentioned amino alcohol having one amino group, the description thereof will be omitted.
  • the obtained copper complex has the above-mentioned general formula A.
  • the mixing ratio (mass ratio) of amino alcohol to copper formate is preferably in the range of 0.6 or more and 1.5 or less. More preferably, the mixing ratio of the amino alcohol is in the range of 0.6 or more and 1.0 or less. When two or more kinds of amino alcohols are used, the total amount of amino alcohols is adjusted to be within the above range. Mixing may be carried out at room temperature with a stirrer or the like. If a deep blue color is visually confirmed, it can be determined that the copper complex has been obtained.
  • Step S120 Nickel formate and an amine ligand represented by L2 are mixed to form a nickel complex. Since L 2 is the same as the above-mentioned aliphatic amine having one amino group, the description thereof will be omitted.
  • the obtained nickel complex has the above-mentioned general formula B.
  • the mixing ratio (mass ratio) of the aliphatic amine to nickel formate is preferably in the range of 0.75 or more and less than 2.4. More preferably, the mixing ratio of the aliphatic amine is in the range of 1.0 or more and 2.0 or less. When two or more kinds of aliphatic amines are used, the total amount of the aliphatic amines is adjusted to be within the above range. Mixing may be carried out at room temperature by a stirrer or the like. If light blue, purple, light green, or dark green is visually confirmed, it can be determined that the nickel complex has been obtained.
  • a polyhydric alcohol may be added as a solvent. This facilitates mixing of nickel formate and aliphatic amines and promotes the formation of nickel complexes.
  • the polyhydric alcohol the above-mentioned polyhydric alcohol can be used.
  • Step S130 The copper complex obtained in step S110 and the nickel complex obtained in step S120 are mixed.
  • the mixing is performed so that the mass ratio of the nickel complex to the copper complex satisfies 0.05 or more and less than 6.
  • the content ratio of nickel to the total mass of copper and nickel in the conductive ink satisfies the range of 5% by mass or more and less than 80% by mass, and a metal wiring having less surface irregularities and no cracks can be obtained.
  • Mixing may be carried out at room temperature by a stirrer or the like.
  • the mixing is more preferably carried out so that the mass ratio of the nickel complex to the copper complex satisfies 0.15 or more and 3.5 or less.
  • the content ratio of nickel to the total mass of copper and nickel in the conductive ink satisfies the range of 10% by mass or more and less than 70% by mass, and a metal wiring having less surface irregularities and no cracks can be obtained. Be done.
  • the mixing is more preferably performed so that the mass ratio of the nickel complex to the copper complex is 0.3 or more and 3 or less.
  • the content ratio of nickel to the total mass of copper and nickel in the conductive ink satisfies the range of 19% by mass or more and less than 67% by mass, and a metal wiring having less surface irregularities and no cracks can be obtained. Be done.
  • Copper particles and / or nickel particles may be added in step S130. This enables thick metal wiring of several ⁇ m or more. Since the addition amount and particle size of these particles are as described above, the description thereof will be omitted.
  • copper particles When copper particles are added, they may be added so that the content ratio of nickel to the total mass of copper and nickel in the final conductive ink satisfies the range of 5% by mass or more and less than 80% by mass. .. The same applies when adding nickel particles and when adding both particles.
  • step S130 monohydric alcohol may be added.
  • the viscosity of the conductive ink is adjusted, and the ink has excellent coatability. Since the monohydric alcohol is as described above, the description thereof will be omitted.
  • step S110 an amino alcohol is used as the amine ligand L1 in step S110 and an aliphatic amine is used as the amine ligand L2 in step S120.
  • the aliphatic amine is used in step S110 and the amino alcohol is used in step S120. You may use it. In this case as well, the above-mentioned mass ratio can be adopted.
  • FIG. 2 is a schematic view showing a substrate with a copper-nickel alloy electrode of the present invention.
  • the substrate with a copper-nickel alloy electrode (hereinafter, simply referred to as a substrate with an electrode) 200 of the present invention includes a substrate 210 and an electrode 220 containing a copper-nickel alloy located on the substrate 210.
  • the electrode 220 is formed of the conductive ink described in the first embodiment. Therefore, the content ratio of nickel to the total mass of copper and nickel in the copper-nickel alloy satisfies the range of 5% by mass or more and 80% by mass or less. This makes it possible to provide a substrate having a smooth, crack-free electrode or metal wiring. In particular, since the copper-nickel alloy is formed, it is inexpensive and has excellent atmospheric stability.
  • the electrode 220 may contain copper particles and / or nickel particles in addition to the copper-nickel alloy. As a result, the electrode 220 can be a thick electrode of several ⁇ m or more. The particle size of these particles is preferably in the range of 50 nm or more and 1 ⁇ m or less, and more preferably in the range of 50 nm or more and 400 nm or less. This enables thick metal wiring with less surface irregularities and no cracks.
  • the electrode 220 may be a surface electrode that covers the entire substrate 210, or may have a predetermined pattern such as a comb shape or a grid shape.
  • a polymer substrate As the substrate 210, a polymer substrate, a Si wafer, glass, ceramic, a metal plate, or the like can be used.
  • the polymer substrate is not particularly limited as long as it is resistant to a temperature of about 170 ° C., but a polyester resin typified by polyethylene naphthalate, a polyimide, a polyolefin resin and the like may be preferable.
  • the substrate is not limited to a plate shape, and may have a surface having a curvature. Further, the substrate may be a self-supporting film. An underlayer such as a semiconductor film, a metal film, a dielectric film, or an organic film may be formed on the surface of the substrate.
  • the conductive ink of the present invention can also form a copper-nickel alloy by heating at a relatively low temperature of 170 ° C., so that a polymer substrate can be adopted.
  • the substrate 210 is a polymer substrate selected from the group consisting of polyethylene naphthalate, polyimide, and polyolefin resin
  • a flexible substrate with electrodes can be provided. Such a substrate with electrodes is advantageous for wearable devices.
  • FIG. 3 is a flowchart showing a process of manufacturing the substrate with a copper-nickel alloy electrode of the present invention.
  • Step S310 The conductive ink for a copper-nickel alloy electrode of the present invention is applied to a substrate. Since the conductive ink is as described in the first embodiment, the description thereof will be omitted. As the substrate, the above-mentioned substrate can be adopted.
  • the application of the conductive ink to the substrate is not particularly limited as long as it can form a film, but for example, the spin coating method, the spray coating method, the dip coating method, the slit coating method, the slot coating method, the bar coating method, and the roll coating method are used.
  • a method selected from the group consisting of a method, a curtain coating method, a gravure printing method, an inkjet method, and a screen printing method is adopted. When these are used, a uniform film is formed.
  • Step S320 The substrate coated with the conductive ink obtained in step S310 is heated (baked). As a result, copper is precipitated from the copper complex in the conductive ink, nickel is precipitated from the nickel complex, and copper and nickel react with each other to form a copper-nickel alloy. In addition, amino alcohols and aliphatic amines are decomposed by heating.
  • the precipitation of copper from the copper complex occurs first, so that it is used as an amino alcohol which is an amine ligand used for forming the copper complex. Can be widely applied to the materials used in the production of inks using the conventional copper nanoparticles exemplified above.
  • the precipitated nickel is a dense film-like body, the reactivity with copper is improved, and a sufficiently alloyed copper-nickel alloy can be easily obtained. Therefore, it is preferable to use the material exemplified above as the aliphatic amine which is an amine ligand used for forming the nickel complex because the nickel precipitated from the nickel complex tends to form a denser film-like body.
  • the heating is preferably performed in a temperature range of 170 ° C. or higher and 250 ° C. or lower in a time range of 1 minute or longer and 60 minutes or lower. Within this temperature range and heating time, a copper-nickel alloy is formed. A hot plate, a constant temperature bath, an oven, or the like can be used for heating.
  • the heating atmosphere is preferably an inert gas atmosphere such as nitrogen or argon. This suppresses the production of copper oxide.
  • step S320 heating (firing) by light irradiation may be performed.
  • the sintering of the particles of the copper-nickel alloy further progresses, and the electrical resistance is reduced. Further, the adhesion between the electrode and the substrate can be improved.
  • Intense pulsed light (IPL) or near-infrared laser may be used for such light irradiation.
  • Examples 1 to 21 In Examples 1 to 21, various conductive inks are produced using copper formate dihydrate, nickel formate dihydrate, and various amine ligands L shown in Table 1. Formed an electrode.
  • copper formate dihydrate was mixed with 2-amino-2-methyl-1-propanol (AMP) or 2-ethylhexylamine (2EHA) to form a copper complex (2EHA).
  • Mixing was carried out at room temperature (25 ° C.) using a stirrer (manufactured by Shinky Co., Ltd., model number ARE-310). After stirring, it turned dark blue as shown in Table 2 and a copper complex was formed.
  • the obtained copper complexes are referred to as Cu-AMP and Cu-2EHA, respectively.
  • nickel formate dihydrate and 2-amino-2-methyl-1-propanol (AMP), 2-ethylhexylamine (2EHA), ethylenediamine (ED), triethylenetetramine (TETA), Hexylamine (HEA) or 2-heptylamine (2HEPA) was mixed with ethylene glycol (0.5 g) as a solvent to form a nickel complex (step S120 in FIG. 1).
  • AMP 2-ethylhexylamine
  • ED ethylenediamine
  • TETA triethylenetetramine
  • HEPA Hexylamine
  • HEPA 2-heptylamine
  • the copper complex and the nickel complex were mixed (step S130 in FIG. 1). Mixing was carried out at room temperature (25 ° C.) using a stirrer.
  • the conductive inks of Examples 11 to 16 were the same as the conductive inks of Example 1, but the conditions for forming the following electrodes were different.
  • 1 g of copper particles (average of median diameter D50: 350 nm) was added to a mixture (4.4 g) of a copper complex and a nickel complex.
  • the conductive ink of Example 21 was not mixed with the nickel complex, but was a single copper complex. Table 4 shows the nickel content ratio to the total mass of copper and nickel contained in the conductive ink thus obtained.
  • the conductive inks of Examples 1 to 21 were applied to a polyimide substrate (manufactured by Toray Industries, Inc.) and a glass substrate (manufactured by CORNING) by a screen printing method (step S310 in FIG. 3).
  • the substrate was washed with an ultrasonic bath of ethanol for 15 minutes and then with distilled water for 1 minute to remove stains on the surface.
  • the substrate coated with the conductive ink was heated (baked) under the conditions shown in Table 5 (step S320 in FIG. 3). The heating was maintained at the temperature of the conditions shown in Table 5 for a predetermined time in a nitrogen atmosphere, and allowed to cool.
  • an intense pulsed light IPL, manufactured by NovaCentrick, PulseForge Invent
  • the electrodes of Examples 1 to 21 thus obtained were evaluated.
  • the thickness of the electrode was measured by a fine shape measuring machine (manufactured by Kosaka Laboratory, model number ET200).
  • the surface of the electrode was observed with an optical microscope (manufactured by Nikon Corporation) and a scanning electron microscope (SEM, manufactured by Hitachi High-Tech Co., Ltd., S-4800).
  • Element mapping was performed by the energy dispersive X-ray spectrometer (EDS) attached to the SEM.
  • the metal of the electrodes of Examples 1 to 21 was identified using an X-ray diffraction measuring device (XRD, manufactured by Rigaku Co., Ltd., SmartLab). The results are shown in FIG.
  • the electrical resistance of the electrodes of Examples 1 to 21 was measured by the four-terminal method (RM3545 manufactured by Hioki Electric Co., Ltd.). These results are shown in FIGS. 12, 13 and 6.
  • Example 1 The oxidation resistance test of the electrodes of Example 1, Example 6 to Example 8 and Example 21 was performed. In the test, each electrode was heated to 180 ° C. in the atmosphere and held for a predetermined time, and then the electric resistance was measured. The results are shown in FIG.
  • FIG. 4 is a diagram showing the appearance of the electrode of Example 1.
  • FIG. 4 shows the electrodes on the glass substrate, and the lower part of FIG. 4 shows the electrodes on the polyimide substrate. According to FIG. 4, all the electrodes on the substrate showed metallic luster, and no unevenness or cracks were visually observed. Although not shown, the same was true for the electrodes of Examples 6 to 9 and Examples 11 to 20. If the conductive ink of the present invention is used, electrodes can be formed at a relatively low temperature, so that a polymer substrate can also be used.
  • FIG. 5 is a diagram showing optical micrographs of the electrodes of Examples 1 to 6.
  • FIG. 6 is a diagram showing optical micrographs of the electrodes of Examples 7 to 10.
  • the surface of the electrode of Example 1 was uniform, smooth without unevenness. Although not shown, the surfaces of the electrodes of Examples 19 and 20 were also uniform, smooth and smooth. On the other hand, those of the electrodes of Examples 2 to 5 are non-uniform despite the same nickel content ratio as the electrodes of Example 1 (nickel content ratio to the total mass of copper and nickel contained in the conductive ink). There were irregularities, spots, cracks, etc. From this, the conductive ink containing a copper complex composed of copper formate and a predetermined amino alcohol and a nickel complex composed of nickel formate and a predetermined aliphatic amine having one amino group has a smooth surface. It has been shown to be effective for metal wiring. The electrical characteristics of the electrode of Example 5 having cracks were not measured.
  • FIG. 7 is a diagram showing an SEM image of the electrode of Example 1.
  • FIG. 8 is a diagram showing EDS element mapping of the electrode of Example 1.
  • FIG. 9 is a diagram showing SEM images of the electrodes of Examples 7 to 9.
  • FIG. 10 is a diagram showing SEM images of the electrodes of Examples 17 to 18.
  • the electrode of Example 1 was composed of particles having an average particle size of 75 nm or more and 150 nm or less. According to FIG. 8, it was found that the particles were composed of copper (Cu) and nickel (Ni), and Cu and Ni were uniformly dispersed in the particles.
  • the electrodes of Examples 7 to 9 are all composed of particles having a particle size in the range of 10 nm or more and 1 ⁇ m or less, but the particle sizes of the electrodes of Examples 1 and 7 to 9 are the same.
  • the particle size depends on the nickel content, and the smaller the nickel content, the larger the particle size, and the larger the nickel content, the smaller the particle size.
  • FIG. 11 is a diagram showing XRD patterns of the electrodes of Examples 1 to 4.
  • the electrodes of Examples 1 to 3 showed only the peaks of Cu (111) and Cu (200). From this, it was found that the electrodes of Examples 1 to 3 contained an alloy in which copper and nickel were uniformly mixed. This result was in agreement with the result of FIG. Although not shown, the electrodes of Examples 6 to 9 and Examples 11 to 20 also showed the same XRD pattern as the electrodes of Example 1. On the other hand, the electrodes of Example 4 showed peaks of Cu (111) and Cu (200) and peaks of Ni (111) and Ni (200), and alloying was insufficient.
  • FIG. 12 is a diagram showing the electrical resistance of the electrodes of Examples 1 to 4.
  • FIG. 13 is a diagram showing the dependence of the electrical resistance of the electrode on the nickel content ratio.
  • FIG. 12 it was shown that the electric resistance of the electrode of Example 1 was the smallest and it was effective as an electrode.
  • FIG. 13 shows the relationship between the electrical resistance of the electrodes of Examples 1, 6 to 10 and 21 and the nickel content ratio. According to FIG. 13, the electrical resistance increased in the electrode of Example 10 in which cracks occurred, but the electrodes of Examples 1 and 6 to 9 in which cracks did not occur were the same as the electrodes of Example 21 containing no nickel. Showed low electrical resistance. From this, it contains a copper complex composed of copper formate and a predetermined amino alcohol, and a nickel complex composed of nickel formate and a predetermined aliphatic amine having one amino group, and the content ratio of nickel is 5% by mass. Conductive inks in the range of more than 80% by mass have been shown to be effective for metal wiring.
  • Table 6 it contains a copper complex composed of copper formate and a predetermined amino alcohol, and a nickel complex composed of nickel formate and a predetermined aliphatic amine having one amino group, and the content ratio of nickel is 5. It has been shown that the use of conductive inks in the range of mass% or more and less than 80% by mass can provide smooth metal wiring with no irregularities.
  • FIG. 14 is a diagram showing the results of the oxidation resistance test.
  • the electrodes of Examples 1 and 6 to 8 obtained by the conductive ink of the present invention maintained low resistance even after heating in the atmosphere, but the electrodes of Example 21 containing no nickel were found. As the heating time in the atmosphere increased, the resistance increased and it no longer functioned as an electrode. This is because the electrodes of Examples 1 and 6 to 8 are made of a copper-nickel alloy, so that copper oxide was not produced even when heated in the atmosphere. From this, it was shown that the conductive ink of the present invention is advantageous for producing an electrode made of a copper-nickel alloy having excellent oxidation resistance.
  • the conductive ink of the present invention By using the conductive ink of the present invention, it is possible to provide metal wiring having an excellent atmospheric stability at a low price and a smooth surface by using an inexpensive material.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Dispersion Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
PCT/JP2021/042517 2020-12-15 2021-11-19 銅ニッケル合金電極用導電性インク、銅ニッケル合金電極付基板、および、それらの製造方法 WO2022130892A1 (ja)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2022569801A JPWO2022130892A1 (zh) 2020-12-15 2021-11-19
KR1020227046040A KR20230019148A (ko) 2020-12-15 2021-11-19 구리 니켈 합금 전극용 도전성 잉크, 구리 니켈 합금 전극 부착 기판, 및 그것들의 제조 방법
CN202180068292.0A CN116323044A (zh) 2020-12-15 2021-11-19 铜镍合金电极用导电性墨、带铜镍合金电极的基板及这些的制造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2020-207192 2020-12-15
JP2020207192 2020-12-15

Publications (1)

Publication Number Publication Date
WO2022130892A1 true WO2022130892A1 (ja) 2022-06-23

Family

ID=82058734

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2021/042517 WO2022130892A1 (ja) 2020-12-15 2021-11-19 銅ニッケル合金電極用導電性インク、銅ニッケル合金電極付基板、および、それらの製造方法

Country Status (4)

Country Link
JP (1) JPWO2022130892A1 (zh)
KR (1) KR20230019148A (zh)
CN (1) CN116323044A (zh)
WO (1) WO2022130892A1 (zh)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005537386A (ja) * 2001-10-05 2005-12-08 スーペリア　マイクロパウダーズ　リミテッド　ライアビリティ　カンパニー 導電性電子フィーチャを堆積するための低粘度前駆体組成物および方法
JP2013125655A (ja) * 2011-12-14 2013-06-24 Hitachi Chemical Co Ltd 導電性接着材、導電性積層体、導電性積層体の製造方法、配線基板、表示装置及び太陽電池モジュール
JP2014139893A (ja) * 2013-01-21 2014-07-31 Fujifilm Corp 導電層含有積層体の製造方法
JP2014162966A (ja) * 2013-02-26 2014-09-08 Nippon Steel & Sumikin Chemical Co Ltd 金属微粒子組成物、接合材、電子部品、接合層の形成方法、導体層の形成方法及びインク組成物
JP2016141860A (ja) * 2015-02-03 2016-08-08 古河電気工業株式会社 微粒子、微粒子分散溶液、及び微粒子の製造方法
JP2016183296A (ja) * 2015-03-26 2016-10-20 東ソー株式会社 導電性インク組成物
JP2017107524A (ja) * 2015-11-30 2017-06-15 住友金属鉱山株式会社 積層体基板、導電性基板、積層体基板の製造方法、導電性基板の製造方法

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100658492B1 (ko) * 2005-03-21 2006-12-15 주식회사 잉크테크 도전성 잉크 조성물 및 이를 이용한 박막 형성방법
KR100727434B1 (ko) * 2005-03-04 2007-06-13 주식회사 잉크테크 투명 은 잉크 조성물 및 이를 이용한 박막 형성방법
JP4924812B2 (ja) * 2006-12-19 2012-04-25 住友金属鉱山株式会社 ニッケル膜形成用塗布液、及びニッケル膜とその製造方法
JP2010064983A (ja) 2008-09-11 2010-03-25 Nippon Steel Chem Co Ltd ニッケル粒子の製造方法及びそれに適したニッケル錯体
JP5486886B2 (ja) 2009-09-15 2014-05-07 Ｄｏｗａエレクトロニクス株式会社 銅−ニッケルナノ粒子とその製造方法
JP2011214144A (ja) * 2010-03-17 2011-10-27 Nippon Steel Chem Co Ltd 金属複合ニッケルナノ粒子の製造方法
JP2012131894A (ja) * 2010-12-21 2012-07-12 Tosoh Corp 導電性インク組成物、及びそれを用いて製造された電気的導通部位
KR101855121B1 (ko) * 2016-05-02 2018-06-11 서울대학교산학협력단 공기 중 열처리가 가능한 금속 유기 전구체 및 다가 알코올을 포함하는 전도성 잉크 조성물 및 이를 이용한 금속배선 형성방법

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005537386A (ja) * 2001-10-05 2005-12-08 スーペリア　マイクロパウダーズ　リミテッド　ライアビリティ　カンパニー 導電性電子フィーチャを堆積するための低粘度前駆体組成物および方法
JP2013125655A (ja) * 2011-12-14 2013-06-24 Hitachi Chemical Co Ltd 導電性接着材、導電性積層体、導電性積層体の製造方法、配線基板、表示装置及び太陽電池モジュール
JP2014139893A (ja) * 2013-01-21 2014-07-31 Fujifilm Corp 導電層含有積層体の製造方法
JP2014162966A (ja) * 2013-02-26 2014-09-08 Nippon Steel & Sumikin Chemical Co Ltd 金属微粒子組成物、接合材、電子部品、接合層の形成方法、導体層の形成方法及びインク組成物
JP2016141860A (ja) * 2015-02-03 2016-08-08 古河電気工業株式会社 微粒子、微粒子分散溶液、及び微粒子の製造方法
JP2016183296A (ja) * 2015-03-26 2016-10-20 東ソー株式会社 導電性インク組成物
JP2017107524A (ja) * 2015-11-30 2017-06-15 住友金属鉱山株式会社 積層体基板、導電性基板、積層体基板の製造方法、導電性基板の製造方法

Also Published As

Publication number Publication date
JPWO2022130892A1 (zh) 2022-06-23
KR20230019148A (ko) 2023-02-07
CN116323044A (zh) 2023-06-23

Similar Documents

Publication Publication Date Title
US8999204B2 (en) Conductive ink composition, method for manufacturing the same, and method for manufacturing conductive thin layer using the same
Farraj et al. Plasma-induced decomposition of copper complex ink for the formation of highly conductive copper tracks on heat-sensitive substrates
JP4844805B2 (ja) 金属被膜の形成方法
Joo et al. Laser sintering of Cu paste film printed on polyimide substrate
JP5715851B2 (ja) ナノ粒子インク組成物を用いた印刷物の製造方法
JP7316414B2 (ja) 分散体並びにこれを用いた導電性パターン付構造体の製造方法及び導電性パターン付構造体
JP2007314866A (ja) 導電体の作製方法
JP7403512B2 (ja) 酸化銅インク及びこれを用いた導電性基板の製造方法、塗膜を含む製品及びこれを用いた製品の製造方法、導電性パターン付製品の製造方法、並びに、導電性パターン付製品
JP2012131894A (ja) 導電性インク組成物、及びそれを用いて製造された電気的導通部位
EP3494184B1 (en) Formulations and processes for producing highly conductive copper patterns
JP2019006903A (ja) 導電性銅インク組成物
EP3248713B1 (en) Electroconductive microparticles
WO2022130892A1 (ja) 銅ニッケル合金電極用導電性インク、銅ニッケル合金電極付基板、および、それらの製造方法
EP3246115B1 (en) Silver powder
JP4931063B2 (ja) 金属ナノ粒子ペーストの製造方法
JP2019160689A (ja) 分散体、塗膜を含む製品、導電性パターン付き構造体の製造方法、及び、導電性パターン付き構造体
KR20170019157A (ko) 저온 소성용 구리 나노잉크 제조를 위한 구리 나노 입자 제조방법
US20100178434A1 (en) Conductive ink composition for printed circuit board and method of producing printed circuit board
KR20170133658A (ko) 구리나노잉크 및 레이저 소결법을 이용하는 투명 전자파 차폐 필름 제조방법
JP7193433B2 (ja) 分散体及びこれを用いた導電性パターン付構造体の製造方法
JP2012144755A (ja) 金属銅膜の作製方法及び印刷金属銅パターン
JP5991459B2 (ja) 銀微粒子とその製造法並びに該銀微粒子を含有する導電性ペースト、導電性膜及び電子デバイス
KR20170122009A (ko) 롤투롤 인쇄용 구리잉크 및 레이저 소결법을 이용한 투명 전자파차폐 필름 제조방법
JP2015069750A (ja) 導電性ペースト、金属薄膜の製造方法並びに金属薄膜

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21906255

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2022569801

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 20227046040

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21906255

Country of ref document: EP

Kind code of ref document: A1