WO2013118892A1 - Poudre métallique traitée en surface, et procédé de fabrication de celle-ci - Google Patents

Poudre métallique traitée en surface, et procédé de fabrication de celle-ci Download PDF

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WO2013118892A1
WO2013118892A1 PCT/JP2013/053142 JP2013053142W WO2013118892A1 WO 2013118892 A1 WO2013118892 A1 WO 2013118892A1 JP 2013053142 W JP2013053142 W JP 2013053142W WO 2013118892 A1 WO2013118892 A1 WO 2013118892A1
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metal powder
copper powder
treated
powder
coupling agent
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PCT/JP2013/053142
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English (en)
Japanese (ja)
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秀樹 古澤
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Jx日鉱日石金属株式会社
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Priority to JP2013557610A priority Critical patent/JP6285185B2/ja
Publication of WO2013118892A1 publication Critical patent/WO2013118892A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/30—Stacked capacitors
    • 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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/102—Metallic powder coated with organic material
    • 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
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H01B1/026—Alloys based on copper
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/228—Terminals
    • H01G4/232—Terminals electrically connecting two or more layers of a stacked or rolled capacitor
    • H01G4/2325—Terminals electrically connecting two or more layers of a stacked or rolled capacitor characterised by the material of the terminals
    • 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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • 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
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/10—Copper
    • 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
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/15—Nickel or cobalt
    • 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
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/25—Noble metals, i.e. Ag Au, Ir, Os, Pd, Pt, Rh, Ru

Definitions

  • the present invention relates to a surface-treated metal powder suitable for production of an electrode for a chip multilayer ceramic capacitor, and a production method thereof.
  • Chip monolithic ceramic capacitors are electronic components used in many electronic devices due to their small size and large capacity.
  • Chip monolithic ceramic capacitors have a structure in which ceramic dielectrics and internal electrodes are stacked and integrated in layers, and each laminated layer constitutes a capacitor element, and these elements are electrically connected in parallel by external electrodes. As a whole, it becomes one small and large-capacity capacitor.
  • a dielectric sheet is manufactured as follows. That is, first, an organic binder and a solvent as a dispersing agent and a molding aid are added to a dielectric raw material powder such as BaTiO 3 , and a slurry is obtained through pulverization, mixing, and defoaming steps. Thereafter, the slurry is thinly spread on a carrier film such as a PET film and applied by a coating method such as a die coater. It is dried to obtain a thin dielectric sheet (green sheet).
  • the metal powder that is a raw material of the internal electrode of the chip multilayer ceramic capacitor is mixed with an organic binder and a solvent as a dispersing agent or a molding aid and a defoaming step, as in the case of the dielectric raw material powder, It becomes.
  • the internal electrode is printed on a green sheet (dielectric sheet) mainly by screen printing, and after drying, the printed green sheet is peeled off from the carrier film, and a large number of such green sheets are laminated. .
  • the green sheets thus laminated are integrated by applying a pressing pressure of several tens to several hundreds of MPa, and then cut into individual chips. Thereafter, the internal electrode layer and the dielectric layer are sintered at a high temperature of about 1000 ° C. in a firing furnace. In this way, a chip multilayer ceramic capacitor is manufactured.
  • Pt was used for the internal electrode of such a chip multilayer ceramic capacitor.
  • Pd, Pd—Ag alloy, and currently Ni is mainly used from the viewpoint of cost.
  • Ni is replaced with Cu, in principle, low inductance can be realized for high frequency applications.
  • Cu has an advantage that the cost is lower than that of Ni.
  • the melting point of Cu is lower than that of Pt, Pd, and Ni in the first place. Furthermore, when Cu is employed as the internal electrode powder due to a decrease in melting point caused by an increase in surface area due to the reduction in particle diameter as described above, the melting of Cu powder at a lower temperature during firing is performed. Begins. This induces the generation of cracks in the electrode layer itself. Further, since the electrode layer contracts rapidly after the temperature is lowered, there is a possibility that the dielectric layer and the electrode layer are separated (delamination). In order to avoid such inconveniences, the metal powder for internal electrodes is required to have a heat shrinkage characteristic equivalent to that of a dielectric, and an index representing this is a sintering start temperature.
  • Patent Document 1 (Patent No. 4001438) disperses Cu powder in a liquid, adds an aqueous solution of a water-soluble salt of a metal element to this, adjusts the pH to fix the metal oxide to the surface of the Cu powder, This is a technology for strengthening the adhesion of the surface treatment layer by causing these surface treatment copper powders to collide with each other.
  • the process is composed of adsorption of metal oxide to copper powder and adhesion strengthening, there is a problem in terms of productivity.
  • the particle size of the copper powder is further smaller than 0.5 ⁇ m, the size of the metal oxide particles to be adsorbed becomes close, so that it is expected that the adsorption of the oxide itself to the copper powder becomes difficult.
  • Patent Document 2 Japanese Patent No. 4164209 is a technique for coating copper powder with silicone oil having a specific functional group.
  • oil and Cu powder are mixed, it is easy to aggregate and there is a problem in terms of workability.
  • separation of oil and Cu powder is difficult, and there exists a problem in the point of workability
  • Patent Document 3 is a technique for forming an SiO 2 gel coating film by subjecting alkoxysilane hydrolyzed on the surface of copper powder to condensation polymerization using an ammonia catalyst.
  • NH 3 as a catalyst when applied to copper powder having a particle size of 1 ⁇ m or less, NH 3 as a catalyst must be continuously added so as to prevent agglomeration, but reaction control depends on the skill of the specific operation skill of addition. It is very difficult, and there are problems in terms of workability and productivity.
  • an object of the present invention is to provide a surface-treated copper powder excellent in sintering retardancy, which can be suitably used for the production of an electrode for a chip multilayer ceramic capacitor, and a method for producing the same.
  • the present inventors have mixed copper powder and aminosilane aqueous solution and adsorbed aminosilane to the copper powder surface, so that there is no aggregation after the surface treatment, and the sintering delay is dramatically improved. As a result, the present invention has been reached. This operation is very simple, does not require advanced skills, is excellent in workability, and is excellent in productivity. Moreover, although the surface-treated copper powder obtained in this way was a copper powder with small particles, it showed a high sintering start temperature. Furthermore, it can be seen that surface-treated metal powder with excellent characteristics can be obtained both when the surface treatment is performed on a metal powder other than copper powder in the same manner and when the surface treatment is performed with a coupling agent other than aminosilane. It was.
  • the present invention includes the following (1) to (26).
  • (2) The Si thickness is in a range where the Si atom abundance is 10% or more when the abundance of Si atoms at a depth at which the abundance ratio of Si atoms to all atoms is maximized is 100%.
  • (18) (1) A copper powder for external electrodes having the characteristics described in any one of (16).
  • (19) A surface-treated copper powder obtained by further surface-treating the copper powder according to any one of (1) to (18) with an organic compound.
  • (20) (1) A conductive paste using the copper powder according to any one of (19).
  • (21) A chip multilayer ceramic capacitor manufactured using the paste of (20).
  • (23) The chip multilayer ceramic capacitor according to (21) or (22), wherein SiO 2 having a maximum diameter of 0.5 ⁇ m or more is present at 0.5 pieces / cm 2 or less on a cross section of the internal electrode.
  • (24) (21) A multilayer substrate on which the chip multilayer ceramic capacitor according to any one of (23) is mounted on an outermost layer.
  • (25) (21) A multilayer substrate on which the chip multilayer ceramic capacitor according to any one of (23) is mounted on an inner layer.
  • the present invention also includes the following (31) to (50).
  • (31) A step of mixing copper powder with an aminosilane aqueous solution to prepare a copper powder dispersion;
  • a method for producing a surface-treated copper powder comprising: (32) The method according to (31), comprising a step of stirring the copper powder dispersion. (33) The method according to (31) or (32), comprising a step of ultrasonicating the copper powder dispersion.
  • Aminosilane aqueous solution is represented by the following formula I: H 2 N—R 1 —Si (OR 2 ) 2 (R 3 ) (Formula I) (However, in the above formula I, R1 is a linear or branched, saturated or unsaturated, substituted or unsubstituted, cyclic or acyclic, heterocyclic or non-heterocyclic, C1-C12 hydrocarbon. A divalent group, R2 is a C1-C5 alkyl group, R3 is a C1-C5 alkyl group or a C1-C5 alkoxy group.
  • R1 is a substituted or unsubstituted C1-C12 linear saturated hydrocarbon divalent group, a substituted or unsubstituted C1-C12 branched saturated hydrocarbon divalent group, substituted or unsubstituted C1-C12 linear unsaturated hydrocarbon divalent group, substituted or unsubstituted C1-C12 branched unsaturated hydrocarbon divalent group, substituted or unsubstituted C1-C12 ring A group consisting of a divalent group of formula hydrocarbon, a substituted or unsubstituted C1-C12 heterocyclic hydrocarbon divalent group, a substituted or unsubstituted C1-C12 aromatic hydrocarbon divalent group,
  • a step of further surface-treating the surface-treated copper powder with an organic compound comprising:
  • the present invention also includes the following (51) to (54).
  • (51) A surface-treated copper powder produced by the production method according to any one of (31) to (46).
  • (52) The electroconductive copper paste manufactured by the manufacturing method as described in (45).
  • (53) An electrode manufactured by the manufacturing method according to (46).
  • (54) An electrode for a chip multilayer ceramic capacitor manufactured by the manufacturing method according to (47).
  • the present invention also includes the following (61) to (63).
  • (61) A surface-treated copper powder produced by the production method according to any one of (31) to (46), In the EDS concentration profile near the surface obtained by STEM, the Si thickness is 1 to 25 nm, Copper powder having a sintering start temperature of 400 ° C or higher.
  • (62) The electroconductive copper paste formed by mix
  • (63) (62)
  • the present invention also includes the following (71) to (71).
  • (71) Surface-treated metal powder in which the thickness of any of Ti, Al, Si, Zr, Ce, and Sn is 1 to 25 nm in the EDS concentration profile near the surface obtained by STEM.
  • (72) The metal powder according to (71), wherein the metal powder is any one of Cu, Pt, Pd, Ag, and Ni.
  • (73) Metal powder of (71) or (72) in which Ti, Al, Si, Zr, Ce and Sn are adsorbed by a coupling agent treatment.
  • (74) (73)
  • the metal powder in which the coupling agent is any one of silane, titanate, and aluminate.
  • (75) (74) A metal powder treated with a coupling agent having a terminal amino group.
  • (78) (77) An electrode obtained by applying the conductive metal powder paste according to (77) and baking it, An electrode in which SiO 2, TiO 2 , and Al 2 O 3 having a maximum diameter of 0.5 ⁇ m or more are present on the electrode cross section at 0.5 pieces / ⁇ m 2 or less.
  • the present invention also includes the following (101) to (101).
  • (101) Surface-treated metal powder in which the thickness of any of Ti, Al, Si, Zr, Ce, and Sn is 1 to 25 nm in the EDS concentration profile near the surface obtained by STEM.
  • (102) The metal powder according to (101), wherein the metal powder is any one of Cu, Pt, Pd, Ag, and Ni.
  • (103) Metal powder as described in (101) whose metal powder is copper powder.
  • the metal powder according to (104), wherein the coupling agent is any one of silane, titanate, and aluminate.
  • (111) The metal powder according to any one of (109) to (110), wherein the aminosilane is monoaminosilane or diaminosilane.
  • (112) A surface-treated metal powder obtained by further surface-treating the metal powder according to any one of (101) to (111) with an organic compound.
  • (113) A conductive metal powder paste using the metal powder according to any one of (101) to (112).
  • (114) An electrode obtained by applying the conductive metal powder paste according to (113) and baking it. An electrode in which SiO 2, TiO 2 , and Al 2 O 3 having a maximum diameter of 0.5 ⁇ m or more are present on the electrode cross section at 0.5 pieces / ⁇ m 2 or less.
  • (115) A chip multilayer ceramic capacitor manufactured using the paste of (113).
  • (120) (Electronic component mounting the multilayer substrate according to (118) or (119). (121) Mixing metal powder with a coupling agent aqueous solution to prepare a metal powder dispersion; A method for producing a surface-treated metal powder comprising: (122) The method according to (121), wherein the metal powder is any one of Cu, Pt, Pd, Ag, and Ni. (123) The method according to (121), wherein the metal powder is copper powder. (124) The method according to any one of (121) to (123), comprising a step of stirring the metal powder dispersion. (125) The method according to any one of (121) to (124), comprising a step of ultrasonicating the metal powder dispersion.
  • An aqueous coupling agent solution has the following formula I: H 2 N—R 1 —Si (OR 2 ) 2 (R 3 ) (Formula I) (However, in the above formula I, R1 is a linear or branched, saturated or unsaturated, substituted or unsubstituted, cyclic or acyclic, heterocyclic or non-heterocyclic, C1-C12 hydrocarbon. A divalent group, R2 is a C1-C5 alkyl group, R3 is a C1-C5 alkyl group or a C1-C5 alkoxy group.
  • R1 represents — (CH 2 ) n —, — (CH 2 ) n — (CH) m — (CH 2 ) j ⁇ 1 —, — (CH 2 ) n — (CC) — (CH 2 ) n ⁇ 1 -, - (CH 2) n -NH- (CH 2) m -, - (CH 2) n -NH- (CH 2) m -NH- (CH 2) j -, - (CH 2) n-1
  • the group consisting of-(CH) NH 2- (CH 2 ) m-1 -,-(CH 2 ) n-1- (CH) NH 2- (CH 2 ) m-1 -NH- (CH 2 ) j- (Wherein n, m and j are integers of 1 or more), the method according to (130).
  • R1 represents — (CH 2 ) n —, — (CH 2 ) n — (CH) m — (CH 2 ) j ⁇ 1 —, — (CH 2 ) n — (CC) — (CH 2 ) n ⁇ 1 -, - (CH 2) n -NH- (CH 2) m -, - (CH 2) n -NH- (CH 2) m -NH- (CH 2) j -, - (CH 2) n-1 -(CH) NH 2- (CH 2 ) m-1 -,-(CH 2 ) n-1- (CH) NH 2- (CH 2 ) m-1 -NH- (CH 2 ) j- (Wherein n, m, and j are integers of 1 or more), the method according to (132).
  • (140) A surface-treated metal powder produced by the production method according to any one of (121) to (134), In the EDS concentration profile near the surface obtained by STEM, the Si thickness, Ti thickness or Al thickness is 1 to 25 nm, Metal powder having a sintering start temperature of 400 ° C or higher.
  • (141) The conductive metal powder paste by which the surface-treated metal powder as described in (140) is mix
  • (142) (141) It is an electrode formed by applying the conductive metal powder paste described in (141) and baking it. An electrode wherein SiO 2, TiO 2 , or Al 2 O 3 having a maximum diameter of 0.5 ⁇ m or more is present at 0.5 pieces / ⁇ m 2 or less in the electrode cross section.
  • the surface-treated copper powder according to the present invention does not aggregate even after the surface treatment, has an excellent sintering delay property, and exhibits a high sintering start temperature even with a small particle copper powder. Therefore, if a conductive copper paste containing the surface-treated copper powder according to the present invention is used, manufacturing problems such as electrode peeling can be avoided, and the manufacture of an electrode for a chip multilayer ceramic capacitor can be advantageously performed. It can be carried out. Further, the surface-treated copper powder according to the present invention can be produced by performing a very simple treatment on the copper powder, and this production method does not require a high level of skill and is excellent in workability and productivity. It is a thing. Moreover, according to this invention, it has the same outstanding characteristic about metal powders other than copper powder.
  • FIG. 1 is a TEM image of a cross section perpendicular to the surface of the surface-treated copper powder.
  • FIG. 2 is a graph showing an EDS concentration profile in the depth direction of the surface-treated copper powder.
  • FIG. 3 is a TEM image of a cross section of the sintered body obtained from the surface-treated copper powder.
  • the copper powder is mixed with an aminosilane aqueous solution to prepare a copper powder dispersion, and the surface-treated copper powder can be obtained from the copper powder dispersion.
  • the copper powder used for the surface treatment a copper powder produced by a known method can be used.
  • a copper powder manufactured by a dry method or a copper powder manufactured by a wet method can be used as the copper powder.
  • the copper powder produced by the wet method is suitable in that it is a wet process consistently with the surface treatment according to the present invention.
  • the aminosilane aqueous solution is an aminosilane aqueous solution that can be used as a silane coupling agent.
  • the amount of aminosilane used is 0.025 g or more, preferably 0.050 g or more, and more preferably 0 with respect to 1 g of copper powder when the copper powder dispersion is used. 0.075 g or more, more preferably 0.10 g or more, or, for example, in amounts ranging from 0.025 to 0.500 g, 0.025 to 0.250 g, 0.025 to 0.100 g. Can be included.
  • the amount of aminosilane used is such that the volume of aminosilane at 25 ° C.
  • a silane containing one or more amino groups and / or imino groups can be used as the aminosilane.
  • the number of amino groups and imino groups contained in aminosilane can be, for example, 1 to 4, preferably 1 to 3, more preferably 1 to 2, respectively. In a preferred embodiment, the number of amino groups and imino groups contained in aminosilane can be one each.
  • An aminosilane in which the total number of amino groups and imino groups contained in the aminosilane is 1, particularly monoaminosilane, 2 aminosilanes in particular, diaminosilane, and 3 aminosilanes in particular can be called triaminosilane. .
  • Monoaminosilane and diaminosilane can be preferably used in the present invention.
  • monoaminosilane containing one amino group can be used as aminosilane.
  • the aminosilane may comprise at least one, for example one amino group, at the end of the molecule, preferably at the end of a linear or branched chain molecule.
  • aminosilane examples include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 1- Aminopropyltrimethoxysilane, 2-aminopropyltrimethoxysilane, 1,2-diaminopropyltrimethoxysilane, 3-amino-1-propenyltrimethoxysilane, 3-amino-1-propynyltrimethoxysilane, 3- Aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl- 3-a
  • aminosilanes represented by the following formula I can be used.
  • R1 is a linear or branched, saturated or unsaturated, substituted or unsubstituted, cyclic or acyclic, heterocyclic or non-heterocyclic, C1-C12 hydrocarbon.
  • a divalent group R2 is a C1-C5 alkyl group, R3 is a C1-C5 alkyl group or a C1-C5 alkoxy group.
  • R1 of formula I above is straight-chain or branched, saturated or unsaturated, substituted or unsubstituted, cyclic or acyclic, heterocyclic, or heterocyclic.
  • a C1-C12 hydrocarbon divalent group more preferably R1 is a substituted or unsubstituted C1-C12 linear saturated hydrocarbon divalent group, substituted or unsubstituted, C1-C12 branched saturated hydrocarbon divalent, substituted or unsubstituted, C1-C12 straight chain unsaturated hydrocarbon divalent, substituted or unsubstituted, C1-C12 branched Unsaturated hydrocarbon divalent group, substituted or unsubstituted C1-C12 cyclic hydrocarbon divalent group, substituted or unsubstituted C1-C12 heterocyclic hydrocarbon divalent group, substituted or A group selected from the group consisting of unsubstituted C1-C12 aromatic hydrocarbon divalent groups; Rukoto can.
  • R1 in the above formula I is a C1-C12 saturated or unsaturated chain hydrocarbon divalent group, and more preferably, the atoms at both ends of the chain structure are free valence atoms.
  • the carbon number of the divalent group can be, for example, C1 to C12, preferably C1 to C8, preferably C1 to C6, preferably C1 to C3.
  • R 1 in the above formula I is — (CH 2 ) n —, — (CH 2 ) n — (CH) m — (CH 2 ) j ⁇ 1 —, — (CH 2 ) n — ( CC)-(CH 2 ) n-1 -,-(CH 2 ) n -NH- (CH 2 ) m -,-(CH 2 ) n -NH- (CH 2 ) m -NH- (CH 2 ) j -,-(CH 2 ) n-1- (CH) NH 2- (CH 2 ) m-1 -,-(CH 2 ) n-1- (CH) NH 2- (CH 2 ) m-1 -NH It can be a group selected from the group consisting of — (CH 2 ) j — (where n, m and j are integers of 1 or more).
  • R1 is — (CH 2 ) n — or — (CH 2 ) n —NH— (CH 2 ). m- .
  • the hydrogen of R1 as the above divalent group may be substituted with an amino group, for example, 1 to Three hydrogens, for example 1 to 2 hydrogens, for example 1 hydrogen, may be replaced by amino groups.
  • n, m, and j in the above formula I are each independently an integer of 1 to 12, preferably an integer of 1 to 6, more preferably an integer of 1 to 4.
  • it can be an integer selected from 1, 2, 3, 4 and can be, for example, 1, 2 or 3.
  • R2 in formula I above can be a C1-C5 alkyl group, preferably a C1-C3 alkyl group, more preferably a C1-C2 alkyl group, such as a methyl group, an ethyl group, Group, isopropyl group or propyl group, preferably methyl group or ethyl group.
  • R3 in formula I above can be a C1-C5 alkyl group, preferably a C1-C3 alkyl group, more preferably a C1-C2 alkyl group as an alkyl group, for example, It can be a methyl group, an ethyl group, an isopropyl group, or a propyl group, preferably a methyl group or an ethyl group.
  • R3 in the above formula I can be a C1-C5 alkoxy group, preferably a C1-C3 alkoxy group, more preferably a C1-C2 alkoxy group as an alkoxy group. Group, isopropoxy group or propoxy group, preferably methoxy group or ethoxy group.
  • the aminosilane aqueous solution can be mixed with copper powder by a known method.
  • stirring can be appropriately performed by a known method.
  • the mixing can be performed at room temperature, for example, at a temperature in the range of 5 to 80 ° C., 10 to 40 ° C., or 20 to 30 ° C.
  • the copper powder dispersion can be mixed and sonicated.
  • the treatment time of the ultrasonic treatment is selected according to the state of the copper powder dispersion, but is preferably 1 to 180 minutes, more preferably 3 to 150 minutes, further preferably 10 to 120 minutes, more preferably 20 to 80. Can be minutes.
  • the ultrasonic treatment can be performed at an output of preferably 50 to 600 W, more preferably 100 to 600 W per 100 ml.
  • the sonication can be performed at a frequency of preferably 10-1 MHz, more preferably 20-1 MHz, more preferably 50-1 MHz.
  • the copper powder in the copper powder dispersion can be recovered as a surface-treated copper powder after being subjected to a surface treatment with aminosilane and then separated from the dispersion.
  • known means can be used, for example, filtration, centrifugation, decantation, etc. can be used.
  • drying can be performed as desired.
  • a known means can be used for drying, for example, drying by heating can be performed.
  • the heat drying can be performed, for example, at a temperature of 50 to 90 ° C. or 60 to 80 ° C., for example, by a heat treatment for 30 to 120 minutes or 45 to 90 minutes.
  • the copper powder may be further pulverized as desired.
  • the recovered surface-treated copper powder is adsorbed on the surface of the copper powder that has been further surface-treated for the purpose of preventing rust or improving dispersibility in the paste. You may let them.
  • the copper powder used for the surface treatment can be a copper powder obtained by a wet method.
  • a step of preparing a slurry by adding cuprous oxide in an aqueous solvent containing an additive of gum arabic, and dilute sulfuric acid in the slurry within 5 seconds The copper powder manufactured by the method including the process of adding at once and performing a disproportionation reaction can be used.
  • the slurry can be maintained at room temperature (20 to 25 ° C.) or lower, and dilute sulfuric acid held at room temperature or lower can be added to perform the disproportionation reaction.
  • the slurry can be maintained at 7 ° C. or lower, and dilute sulfuric acid maintained at 7 ° C. or lower can be added to perform a disproportionation reaction.
  • dilute sulfuric acid can be added so that the pH is 2.5 or less, preferably pH 2.0 or less, and more preferably pH 1.5 or less.
  • the addition of dilute sulfuric acid to the slurry is within 5 minutes, preferably within 1 minute, more preferably within 30 seconds, more preferably within 10 seconds, more preferably within 5 seconds.
  • the disproportionation reaction can be completed in 10 minutes.
  • the concentration of gum arabic in the slurry can be 0.229 to 1.143 g / L.
  • cuprous oxide it is possible to use cuprous oxide used in a known method, preferably cuprous oxide particles, and the particle size of the cuprous oxide particles is a copper powder produced by a disproportionation reaction. Since it is not directly related to the particle size of the particles, coarse cuprous oxide particles can be used.
  • the principle of this disproportionation reaction is as follows: Cu 2 O + H 2 SO 4 ⁇ Cu ⁇ + CuSO 4 + H 2 O
  • the copper powder obtained by this disproportionation can be washed, rust-proof, filtered, dried, crushed, classified, and then mixed with aminosilane, if desired. Thus, after washing, rust prevention and filtration, it can be directly mixed with the aminosilane aqueous solution without drying.
  • the copper powder obtained by the disproportionation reaction has an average particle size of 0.25 ⁇ m or less as measured by a laser diffraction particle size distribution analyzer.
  • the copper powder obtained by the disproportionation reaction has a D10, D90, and Dmax measured by a laser diffraction particle size distribution measuring apparatus of [Dmax ⁇ D50 ⁇ 3, D90 ⁇ D50 ⁇ 2, D10. ⁇ D50 ⁇ 0.5], and the particle size distribution has a single peak.
  • the copper powder obtained by the disproportionation reaction has a single particle size distribution (having a single peak) as measured by a laser diffraction particle size distribution analyzer.
  • the value measured by a laser diffraction particle size distribution analyzer is [D50 ⁇ 1.5 ⁇ m], preferably [D50 ⁇ 1.0 ⁇ m], and more preferably [D50 ⁇ 0. 5 ⁇ m, Dmax ⁇ 1.0 ⁇ m].
  • a laser diffraction particle size distribution analyzer for example, SALD-2100 manufactured by Shimadzu Corporation can be used.
  • the surface-treated copper powder obtained by the present invention has an excellent sintering delay.
  • a sintering start temperature As an index of the sintering delay property, there is a sintering start temperature. This is the temperature at which a certain volume change (shrinkage) occurs when the green compact made of metal powder is heated in a reducing atmosphere. In the present invention, the temperature at which 1% volume shrinkage occurs is the sintering start temperature. Specifically, it was measured as described in the examples. A high sintering start temperature means that the sintering delay property is excellent.
  • the sintering start temperature of the surface-treated copper powder according to the present invention is 450 ° C. or higher, preferably 500 ° C. or higher, more preferably 600 ° C. or higher, more preferably 700 ° C. or higher, more preferably. Is 780 ° C. or higher, more preferably 800 ° C. or higher, more preferably 810 ° C. or higher, more preferably 840 ° C. or higher, more preferably 900 ° C. or higher, more preferably 920 ° C. or higher, more preferably 950 ° C. or higher. it can.
  • the sintering start temperature of Ni ultrafine powder (average particle size 0.2 to 0.4 ⁇ m), which has been conventionally used when a high sintering start temperature is required, is in the range of 500 to 600 ° C.
  • the surface-treated copper powder according to the present invention uses Cu, which is cheaper and easier to obtain than Ni, and has fine sintering properties, which are equal to or better than that of fine particles. .
  • the surface-treated copper powder according to the present invention can form a sintered body by heating the green compact in a reducing atmosphere.
  • the obtained sintered body is formed as an excellent electrode.
  • This sintering process can be suitably used particularly for the production of the internal electrode of a chip multilayer ceramic capacitor.
  • This sintered body can be suitably used particularly as an internal electrode of a chip multilayer ceramic capacitor.
  • the sintered body may have SiO 2 having a diameter of preferably 10 nm or more in its cross section.
  • the sintered body may have SiO 2 having a maximum diameter of 0.5 ⁇ m or more in a cross section of 0.5 pieces / ⁇ m 2 or less, or, for example, The range of SiO 2 having a maximum diameter of 0.5 ⁇ m or more is 0.0 to 0.5 / ⁇ m 2 , for example, the range of SiO 2 having a maximum diameter of 0.5 ⁇ m or more is 0.1 to 0.5 / ⁇ m 2 . It can be assumed that it exists.
  • This maximum diameter means the diameter of the minimum circumscribed circle of the SiO 2 particles.
  • the deposition of SiO 2 particles is controlled in this way, allowing the formation of an ultrathin electrode and at the same time not reducing the reliability (quality) of the electrode.
  • the surface-treated copper powder has a Si adhesion amount of generally 500 to 16000 ⁇ g, preferably 500 to 3000 ⁇ g, per 1 g of copper powder.
  • This Si adhesion amount can be determined by ICP (inductively coupled plasma atomic emission spectrometry).
  • it may further contain 0.05 wt% or more of N with respect to the weight of the copper powder.
  • the mechanism by which the silane coupling agent is adsorbed on the copper powder is unknown, but the present inventor believes that it is adsorbed by an interaction between the nitrogen of the amino group at the end of the silane coupling agent and copper. .
  • the surface-treated copper powder has a Si-containing layer thickness (Si thickness) formed by the surface treatment of generally 0.6 to 25 nm, preferably 1.0 to 25 nm, more preferably Can be from 1.5 to 20 nm.
  • the thickness of the Si-containing layer refers to the presence of Si atoms with respect to all atoms as measured by EDS (energy dispersive X-ray analysis) in the cross section of the surface of the surface-treated copper powder. It can be defined that the Si atom abundance is 10% or more when the abundance of Si atoms at the depth at which the ratio is maximum is 100%.
  • the cross section of the surface of the surface-treated copper powder is selected from among at least 100 or more copper powder particles observed in the sample section, and the clearest boundary of each is selected and the surface-treated copper powder is cross-sectioned. Measurement and tabulation can be performed by treating the cross section as being perpendicular to the surface.
  • the surface-treated copper powder has a weight percentage of N with respect to the copper powder of, for example, 0.05% by weight or more, preferably 0.06% by weight or more, and more preferably 0.07% by weight or more.
  • N with respect to the copper powder
  • it can be 0.05 to 0.50% by weight, preferably 0.06 to 0.45% by weight, and more preferably 0.08 to 0.40% by weight.
  • the weight% of N with respect to the copper powder can be calculated from the generated NO 2 by melting the copper powder at a high temperature.
  • the surface-treated copper powder has a surface N of, for example, 1.0% or more, preferably 1.4% or more, more preferably, as measured by a survey measurement by XPS (X-ray photoelectron spectroscopy) analysis. Is 1.5% or more, more preferably 1.6% or more, or, for example, 1.0 to 6.0%, preferably 1.4 to 6.0%, more preferably 1.5 to 6.0%. More preferably, it is in the range of 1.6 to 6.0%, and the N photoelectrons are, for example, 1000 cps (count per second) or more, preferably 1200 cps or more, or, for example, 1000 to 9000 cps, preferably 1200 to 8000 cps. It can be assumed that
  • the surface-treated copper powder has a surface Si of, for example, 0.6% or more, preferably 0.8% or more, more preferably, as measured by XPS (X-ray photoelectron spectroscopy) survey.
  • Si X-ray photoelectron spectroscopy
  • the surface-treated copper powder may be further subjected to a surface treatment after being subjected to a surface treatment with aminosilane.
  • a surface treatment for example, a rust prevention treatment with an organic rust inhibitor such as benzotriazole or imidazole can be given, and even with such a normal treatment, the surface treatment with aminosilane is not eliminated. . Therefore, a person skilled in the art can perform such a known surface treatment as desired within a limit not losing the excellent sintering retardance. That is, the copper powder obtained by further subjecting the surface of the surface-treated copper powder according to the present invention to surface treatment within the limit that does not lose the excellent sintering delay property is also within the scope of the present invention. .
  • the present invention even when a metal powder other than the copper powder is used, excellent characteristics can be obtained by the surface treatment described above for the copper powder. Even when a metal powder other than copper powder is used, the present invention can be carried out according to the preferred embodiment described for the copper powder.
  • the metal powder for example, any metal powder of Pt, Pd, Ag, Ni, Cu can be used. Examples of preferable metal powder including copper powder include Ag, Ni, and Cu.
  • the present invention can be suitably implemented as described above by the adhesion of Si, but can also be suitably implemented by the deposition of elements other than Si. Even when an element other than Si adheres, the present invention can be implemented by the preferred embodiment described for Si.
  • an element other than Si one or more of Ti, Al, Zr, Ce, and Sn can be used.
  • Preferable elements including Si include one or more of Si, Ti, Al, Zr, Ce, and Sn, and more preferably any one or more of Si, Ti, and Al.
  • the present invention can be suitably implemented by performing a surface treatment with a silane coupling agent, but also by performing a surface treatment with a coupling agent other than the silane coupling agent, It can implement suitably.
  • Examples of coupling agents other than silane coupling agents include titanate and aluminate.
  • Si when a silane coupling agent is used as the coupling agent, Si, when titanate is used, Ti, and when aluminate is used, Al can be suitably attached.
  • the mode of use of these coupling agents can be as described above for silane coupling agents. Similar to the structure of the silane coupling agent, in the structure of titanate and aluminate, a structure in which a substituent containing an amino group at the terminal is coordinated to Ti and Al as the central atoms is preferable.
  • the suitable adhesion amount of Si, Ti or Al by such a coupling agent is as described above for the copper powder, and for example, 200 g per 1 g of the metal powder.
  • the thickness (Si thickness) of the Si-containing layer formed by the surface treatment of the metal powder can be as described above for the copper powder, and the thickness of the Ti-containing layer (Ti thickness).
  • the thickness of the Al-containing layer (Al thickness) can also be set as described above for the thickness of the Si-containing layer (Si thickness).
  • the surface-treated metal powder can have the surface Si as described above for the copper powder in the survey measurement of the XPS (X-ray photoelectron spectroscopy) analysis method.
  • Ti and Al can be set to a numerical range similar to the numerical range defined for Si by the same measurement method as Si.
  • the surface-treated metal powder may have the surface N as described above for the copper powder in the survey measurement of the XPS (X-ray photoelectron spectroscopy) analysis method.
  • R1 of the above formula II the groups exemplified as R1 of the above formula I can be preferably used.
  • R2 of the above formula II the groups exemplified as R2 of the above formula I can be preferably used.
  • a C3 alkyl group can be exemplified, and particularly preferably, a propyl group and an isopropyl group can be exemplified.
  • plain act KR44 manufactured by Ajinomoto Fine Techno Co.
  • the metal powder according to the present invention has a high sintering start temperature, and by blending this, an excellent conductive metal powder paste can be produced, An excellent electrode can be manufactured by sintering this conductive metal powder paste.
  • the sintering start temperature with the metal powder of the present invention is as described above for the copper powder.
  • the electrode obtained according to the invention can be as described above for the electrode cross section SiO 2 and likewise the electrode cross section TiO 2 and / or the electrode cross section Al 2 O 3.
  • the SiO 2 in the electrode cross section the size, number and density as described above can be used.
  • the SiO 2 in the electrode cross section corresponds to the case where a silane coupling agent is used as the coupling agent for the surface treatment, and the titanate as the coupling agent in the surface treatment for the SiO 2 in the electrode cross section.
  • Al 2 O 3 in the electrode cross section corresponds to the case where aluminate is used as a surface treatment coupling agent.
  • the present invention will be described in more detail with reference to examples.
  • the present invention is not limited to the following examples.
  • the surface-treated copper powder was manufactured as follows. [Milling by wet method] 20 g of copper powder subjected to the surface treatment was produced by a wet method. The obtained copper powder had the following characteristics. For the measurement, a laser diffraction particle size distribution measuring device (SALD-2100 manufactured by Shimadzu Corporation) was used. D50 0.12 ⁇ m Distribution
  • aqueous silane solution 50 ml of an aqueous silane solution using the following various silanes was prepared.
  • the concentration was adjusted in the range of 0.5 to 15 vol%.
  • pH was adjusted to 4 with dilute sulfuric acid except amino silane.
  • the temperature was continuously raised to a rate of 5 ° C./minute and a measurement range: 50 to 1000 ° C., and the height change (change in expansion / contraction) of the molded body was automatically recorded.
  • the temperature at which the height change (shrinkage) of the molded body started and the shrinkage rate reached 1% was defined as “sintering start temperature”.
  • the measurement results of the sintering start temperature of the surface-treated copper powder for each example and comparative example are summarized in Table 3.
  • SiO 2 thickness on the surface of the surface-treated copper powder was analyzed by EDS (energy dispersive X-ray analysis) under the following conditions. The results are summarized in Table 3.
  • SiO 2 thickness Equipment STEM Cross-sectional TEM image magnification: 2000000 times (2 million times)
  • Scanning distance 5-point average of 500 nm (scanning cross section of copper powder)
  • SiO 2 layer definition Region that is 10% of the maximum value of the concentration profile in the depth direction of characteristic X-rays.
  • a comparative experiment was conducted using tetraethoxysilane (TEOS) as a silane coupling agent and surface treatment of copper powder using ammonia as a catalyst.
  • TEOS tetraethoxysilane
  • the surface-treated copper powder obtained was agglomerated, and it was considered that a uniform surface treatment and particle size were not obtained by visual observation.
  • the particle size distribution was one peak before the surface treatment, and two peaks.
  • FIG. 1 a TEM image (4 million times) of a cross section perpendicular to the surface of the surface-treated copper powder of Example 5 is shown in FIG.
  • the bar on the lower left of the TEM image photograph in FIG. 1 indicates 10 nm.
  • the left half (indicated by a left-pointing arrow starting from a vertical dotted line) divided from the center to the left and right is copper powder.
  • a thick horizontal line is shown in the upper center of FIG. 1, and EDS analysis was performed along this line. Each EDS analysis was performed at the position of the thick point connected to the thick line.
  • the result graph of the EDS analysis corresponding to FIG. 1 is shown in FIG.
  • FIG. 2 shows a graph of the results of EDS Depth profile (EDS concentration profile) obtained by performing EDS analysis of the surface-treated copper powder of Example 5. It is shown that a Si layer having a predetermined thickness is formed.
  • EDS Depth profile EDS concentration profile
  • a TEM image (40,000 times) of a cross section of a sintered body obtained from the surface-treated copper powder of Example 5 is shown in FIG.
  • the white part is sintered copper and the black part is SiO 2 particles. It was confirmed by conducting an EDS analysis separately that it was SiO 2 particles. Further, for finishing the cross section, the surface was subjected to precision focused ion beam (FIB) processing to obtain a scanning electron microscope (SIM) photograph, and thereby the number of SiO 2 particles was counted.
  • FIB precision focused ion beam
  • the surface-treated copper powder produced by mixing the aminosilane aqueous solution according to the present invention is a copper powder having a very small size even though the production method is extremely simple. In other words, it was found that the sintering start temperature was higher than or equal to that of the fine powder of the nickel alloy.
  • a sintered body can be produced by sintering similar to the production process of the electrode of the chip multilayer ceramic capacitor, and the sintered body thus produced (formed) is In spite of the use of the above surface-treated copper powder, the number of SiO 2 particles (number / ⁇ m 2 ) having a large diameter (diameter of the minimum circumscribed circle of the particles) is small in the cross section of the sintered body. I found out that
  • the silane coupling agent needs to be an aminosilane having an amino group.
  • an aminosilane it turned out that the aminosilane which has an amino group at the terminal is preferable.
  • Comparative Example 4 although it seems that a sufficient amount of Si is attached to the copper powder, a sufficient sintering delay is not realized. The reason for this is unclear, but in the Comparative Example 4, the present inventor does not have an aminosilane having a structure having an amino group at the terminal, and in addition, the benzene ring is present at the terminal rather than the amino group. Furthermore, it is not because a state like steric hindrance has occurred, and aminosilane or Si once attached to the copper powder is detached from the copper powder at an early stage during the temperature rise for sintering. I guess.
  • the surface-treated copper powder according to the present invention has excellent properties even if it is subjected to surface treatment such as rust prevention treatment after being subjected to surface treatment with aminosilane. I found out that it was maintained. That is, the copper powder obtained by subjecting the surface of the surface-treated copper powder according to the present invention to a surface treatment with an organic substance and the like within the range where the surface treatment with aminosilane is not eliminated is also within the scope of the present invention. Is within.
  • aminosilane treatment an aminosilane aqueous solution (50 mL) was added and stirred for 60 minutes. At this time, rotating blades (300 rpm) + ultrasonic waves (manufactured by Techjam Co., Ltd., ultrasonic cleaner 3 frequency type / W-113) (output) 100 W, frequency 100 kHz) was performed. Separately from this, the processing of only the rotary blade (300 rpm) and the processing of only the ultrasonic wave were separately performed. Diaminosilane A-1120 (manufactured by MOMENTIVE) and aminosilane A-1110 (manufactured by MOMENTIVE) were used as aminosilanes, respectively. (6) Next, filtration was performed to separate the precipitate. (7) Next, the separated precipitate was dried. Drying (70 ° C. ⁇ 2 h) was performed in an air atmosphere and in nitrogen.
  • the surface-treated fine copper powder was obtained by integrated production.
  • the surface-treated copper powder obtained in this way has excellent sintering retardancy and is present in the cross-section of the sintered body as well as the surface-treated copper powder of Examples 1 to 9 above.
  • the number of large SiO 2 particles was small.
  • this integrated production can be performed without drying until a final product is obtained, which is simple and excellent in workability.
  • Examples 15 to 17 and Comparative Example 9 20 g of copper powder subjected to the surface treatment was produced by the wet method described above. That is, (1) 50 g of cuprous oxide was added to 0.4 g of gum arabic + 350 mL of pure water. (2) Next, 50 mL of dilute sulfuric acid (25 wt%) was added at a time. (3) This was stirred with a rotary blade (300 rpm ⁇ 10 minutes) and allowed to stand for 60 minutes. (4) Next, the precipitate was washed.
  • Example 10 According to Japanese Patent No. 4164209, copper powder was obtained by a chemical reduction method. That is, 2 g of gum arabic was added to 2900 mL of pure water, and then 125 mL of copper sulfate was added and 360 mL of 80% hydrazine monohydrate was added while stirring. After the addition of hydrazine monohydrate, the temperature was raised from room temperature to 60 ° C. over 3 hours, and copper oxide was further reacted over 3 hours. After completion of the reaction, the resulting slurry was filtered with Nutsche, then washed with pure water and methanol, and further dried to obtain copper powder. This copper powder and a diaminosilane coupling agent aqueous solution were mixed in the procedure of Example 1 to obtain a surface-treated silver powder. This characteristic was evaluated by the procedure of Example 1.
  • Nickel powder As the nickel powder, NF32 (D50 0.3 ⁇ m) manufactured by Toho Titanium was used.
  • the silver powder thus obtained was filtered with Nutsche, washed with pure water and alcohol in that order, and dried at 70 ° C. for 12 hours in an air atmosphere. This silver powder was dry-classified to finally obtain a silver powder having a D50 of 0.1 ⁇ m and a Dmax of 0.5 ⁇ m.
  • Diaminosilane A-1120 H 2 N—C 2 H 4 —NH—C 3 H 6 —Si (OCH 3 ) 3 Methyltrimethoxysilane
  • KBM-13 H 3 C—Si (OCH 3 ) 3
  • Amino group-containing plain act KR44 Side chain organic functional group of hydrophobic group (CH 3 ) 2 CH—O— Side chain organic functional group of hydrophilic group —O— (C 2 H 4 ) —NH— (C 2 H 4 ) —NH 2 Amino group-free pre-act KR TTS Side chain organic functional group of hydrophobic group (CH 3 ) 2 CH—O— Side chain organic functional group of hydrophilic group —O—CO— (C 17 H 35 )
  • the present invention provides a surface-treated copper powder that does not aggregate even after the surface treatment, has an excellent sintering delay property, and exhibits a high sintering start temperature even with a small-sized copper powder.
  • the surface-treated copper powder according to the present invention can be produced by performing a very simple treatment on the copper powder, and this production method does not require a high level of skill and is excellent in workability and productivity. It is.
  • the present invention is an industrially useful invention.

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Abstract

L'invention concerne une poudre métallique traitée en surface qui présente des propriétés d'inhibition de frittage supérieures, et qui convient à des fins d'utilisation pour la fabrication d'électrodes pour des puces de condensateurs céramiques multicouches. Dans le profil des concentrations de spectroscopie à dispersion d'énergie de la zone à proximité de la surface de la poudre métallique traitée en surface obtenue par STEM, la profondeur de l'un quelconque parmi Ti, Al, Si, Zr, Ce et Sn est de 1 à 25 nm.
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JPWO2019064745A1 (ja) * 2017-09-29 2019-11-14 Ｊｘ金属株式会社 金属積層造形用金属粉及び該金属粉を用いて作製した造形物
US11056279B2 (en) 2018-08-01 2021-07-06 Jx Nippon Mining & Metals Corporation Laminate of ceramic layer and sintered body of copper powder paste
US11069478B2 (en) * 2018-08-01 2021-07-20 Jx Nippon Mining & Metals Corporation Laminate of ceramic layer and sintered body of copper powder paste
CN113707360A (zh) * 2021-10-22 2021-11-26 西安宏星电子浆料科技股份有限公司 一种适用于不同类型不锈钢基体的厚膜电阻浆料

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JP6549298B1 (ja) 2018-09-21 2019-07-24 Ｊｘ金属株式会社 易解砕性銅粉及びその製造方法
JP6866408B2 (ja) * 2019-01-11 2021-04-28 Ｊｘ金属株式会社 表面処理された金属粉及び導電性組成物

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JPWO2019064745A1 (ja) * 2017-09-29 2019-11-14 Ｊｘ金属株式会社 金属積層造形用金属粉及び該金属粉を用いて作製した造形物
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US11056279B2 (en) 2018-08-01 2021-07-06 Jx Nippon Mining & Metals Corporation Laminate of ceramic layer and sintered body of copper powder paste
US11069478B2 (en) * 2018-08-01 2021-07-20 Jx Nippon Mining & Metals Corporation Laminate of ceramic layer and sintered body of copper powder paste
CN113707360A (zh) * 2021-10-22 2021-11-26 西安宏星电子浆料科技股份有限公司 一种适用于不同类型不锈钢基体的厚膜电阻浆料
CN113707360B (zh) * 2021-10-22 2022-02-25 西安宏星电子浆料科技股份有限公司 一种适用于不同类型不锈钢基体的厚膜电阻浆料

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