WO2013118893A1 - Surface-treated metal powder and manufacturing method therefor - Google Patents
Surface-treated metal powder and manufacturing method therefor Download PDFInfo
- Publication number
- WO2013118893A1 WO2013118893A1 PCT/JP2013/053143 JP2013053143W WO2013118893A1 WO 2013118893 A1 WO2013118893 A1 WO 2013118893A1 JP 2013053143 W JP2013053143 W JP 2013053143W WO 2013118893 A1 WO2013118893 A1 WO 2013118893A1
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- WO
- WIPO (PCT)
- Prior art keywords
- metal powder
- copper powder
- powder
- treated
- respect
- Prior art date
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- 239000000843 powder Substances 0.000 title claims abstract description 205
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 190
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Images
Classifications
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- B22F1/16—Metallic particles coated with a non-metal
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- H—ELECTRICITY
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- C—CHEMISTRY; METALLURGY
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- C22C9/00—Alloys based on copper
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- 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
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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
- H01G4/002—Details
- H01G4/228—Terminals
- H01G4/232—Terminals electrically connecting two or more layers of a stacked or rolled capacitor
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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
- H01G4/002—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
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- 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
- B22F1/056—Submicron particles having a size above 100 nm up to 300 nm
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- 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
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- 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
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- 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 applied to a carrier film such as a PET film 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 items (1) to (27).
- the copper powder according to (1) or (2), wherein the copper powder is a copper powder surface-treated with a silane coupling agent.
- (6) (1) A copper powder obtained by heat-treating the copper powder according to any one of (5) to remove N. (7) Copper powder obtained by heat-treating the copper powder according to any one of (1) to (6) in an oxygen atmosphere or an inert atmosphere. (8) The copper powder according to any one of (1) to (7), wherein the sintering start temperature is 400 ° C. or higher.
- (22) A chip multilayer ceramic capacitor manufactured using the paste of (21).
- (23) The chip multilayer ceramic capacitor according to (22), wherein SiO 2 having a diameter of 10 nm or more is present in a cross section of the internal electrode.
- (24) The chip multilayer ceramic capacitor according to (22) or (23), 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.
- (25) (22) A multilayer substrate on which the chip multilayer ceramic capacitor according to any one of (24) is mounted on an outermost layer.
- (26) (22) A multilayer substrate on which the chip multilayer ceramic capacitor according to any one of (24) is mounted on an inner layer.
- (27) An electronic component on which the multilayer substrate according to (25) or (26) is mounted.
- 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), The adhesion amount of Si is 500-16000 ⁇ g per 1 g of copper powder, % By weight of N to copper powder is 0.05% or more, Copper powder having a sintering start temperature of 400 ° C or higher.
- (62) The electroconductive copper paste formed by mix
- the present invention also includes the following (71) to (71).
- (71) Surface treatment was performed in which the adhesion amount of at least one of Ti, Al, Zr, Ce, and Sn was 300 to 1500 ⁇ g with respect to 1 g of copper powder, and the weight percentage of N with respect to metal powder was 0.05% or more. Copper powder.
- (72) Ti, Al, Zr, Ce, Sn are adsorbed by the coupling agent treatment, and the copper powder of (71).
- (73) Either the copper powder of (71) or (72) processed with the coupling agent whose molecular structure terminal is an amino group.
- (74) (73) The copper powder wherein the coupling agent is a titanate or aluminate coupling agent.
- the adhesion amount of any one or more of Ti, Al, Zr, Ce, and Sn is 300 to 1500 ⁇ g with respect to 1 g of copper powder, the weight percentage of N with respect to metal powder is 0.05% or more, and the sintering start temperature Copper powder having a temperature of 400 ° C. or higher.
- a conductive metal paste comprising the surface-treated metal powder according to any one of (71) to (81).
- the present invention also includes the following (101) to (101).
- (101) Surface treatment in which the adhesion amount of any one or more of Si, Ti, Al, Zr, Ce and Sn is 200 to 16000 ⁇ g with respect to 1 g of metal powder, and the weight percentage of N with respect to metal powder is 0.02% or more.
- Metal powder (102) The metal powder according to (101), wherein the metal powder is one of Pt, Pd, Ag, Ni, and Cu. (103) The metal powder according to (101), wherein the metal powder is a copper powder. (104) The metal powder according to (101), wherein the metal powder is any one of Pt, Pd, Ag, and Ni.
- (121) A surface-treated metal powder obtained by further surface-treating the metal powder according to any one of (101) to (121) with an organic compound.
- the metal powder is a metal powder of any one of Pt, Pd, Ag, and Ni, and any one or more of Si, Ti, Al, Zr, Ce, and Sn is attached to 1 g of the metal powder other than Cu. 200 to 1500 ⁇ g, the metal powder according to (101), wherein the weight percentage of N relative to the metal powder other than Cu is 0.02% or more and the sintering start temperature is 400 ° C. or more.
- a method for producing a surface-treated metal powder comprising: (132) The method according to (131), wherein the metal powder is one of Pt, Pd, Ag, Ni, and Cu. (133) The method according to (131), wherein the metal powder is copper powder. (134) The method according to (131), wherein the metal powder is any one of Pt, Pd, Ag, and Ni. (135) The method according to any one of (131) to (134), comprising a step of stirring the metal powder dispersion. (136) The method according to any one of (131) to (135), comprising a step of ultrasonicating the metal powder dispersion.
- (137) The method according to any one of (131) to (136), wherein the sonication step is a sonication step for 1 to 180 minutes.
- (138) A step of collecting the copper powder by filtering the metal powder dispersion, Drying the copper powder recovered by filtration to obtain a surface-treated metal powder, The method according to any one of (131) to (137), comprising: (139) The method according to (138), wherein the drying is performed in an oxygen atmosphere or an inert atmosphere.
- (140) The method according to any one of (131) to (139), wherein the metal powder dispersion contains 0.025 g or more of a coupling agent with respect to 1 g of the metal powder.
- 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 -(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 (141).
- 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 (143).
- 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 of a sintered body obtained from 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 to 1 MHz, more preferably 20 to 1 MHz, more preferably 50 to 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 increased to a rate of 5 ° C./minute and a measurement range: 50 to 1000 ° C., and the height change (expansion / shrinkage change) of the compact 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.
- Adhesion amount Si The surface-treated copper powder is dissolved with an acid, quantified by ICP (inductively coupled plasma atomic emission spectrometry), and adhered to the unit mass (g) of the surface-treated copper powder. The mass ( ⁇ g) of was determined. N, and C ⁇ ⁇ ⁇ copper powder is melted at a high temperature, generated NO 2, deposited from CO 2 N, to calculate the amount of C, to measure the N, the amount of C which stuck to the entire surface of the copper powder The mass% (% by weight) of the mass of N and C adhering to the mass of the surface-treated copper powder was determined.
- tetraethoxysilane (TEOS) was used as a silane coupling agent, and copper powder was surface-treated 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.
- 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
Description
そこで、本発明の目的は、チップ積層セラミックコンデンサー用電極の製造に好適に使用可能な、焼結遅延性に優れた、表面処理された銅粉、及びその製造方法を、提供することにある。 Thus, there is a demand for copper powder that is suitable for the production of internal electrodes of chip multilayer ceramic capacitors and that is excellent in sintering delay, workability, and productivity.
Accordingly, 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.
(1)
Siの付着量が銅粉1gに対して500~16000μg、銅粉に対するNの重量%が0.05%以上である、表面処理された銅粉。
(2)
Siの付着量が銅粉1gに対して500~3000μg、銅粉に対するNの重量%が0.05%以上である、(1)に記載の銅粉。
(3)
銅粉が、シランカップリング剤で表面処理された銅粉である、(1)又は(2)に記載の銅粉。
(4)
シランカップリング剤がアミノシランである、(3)に記載の銅粉。
(5)
銅粉に対するNの重量%が0.05%~0.50%の範囲にある(1)~(4)のいずれかに記載の銅粉。
(6)
(1)~(5)の何れかに記載の銅粉を熱処理してNを除去した銅粉。
(7)
酸素雰囲気または不活性雰囲気下で(1)~(6)のいずれかに記載の銅粉を熱処理して得られる銅粉。
(8)
焼結開始温度が400℃以上である(1)~(7)のいずれかに記載の銅粉。
(9)
アミノシランの水溶液と銅粉を混合、攪拌後に乾固して得られる(1)~(8)のいずれかに記載の銅粉。
(10)
銅粉1 gに対して、表面処理に供するアミノシランの量が0.01 mL以上である(1)~(9)のいずれかに記載の銅粉。
(11)
アミノシランの量が0.05 mL以上で、銅粉との混合、攪拌時間が30分以下である(10)に記載の銅粉
(12)
アミノシランが、モノアミノシラン又はジアミノシランである(1)~(11)のいずれかに記載の銅粉。
(13)
原料銅粉が湿式法で得られた(1)~(12)のいずれかに記載の銅粉。
(14)
D50≦1.5μmである(1)~(13)のいずれかに記載の銅粉。
(15)
D50≦1.0μmである(1)~(13)のいずれかに記載の銅粉。
(16)
D50≦0.5μm、Dmax≦1.0μmである(1)~(13)のいずれかに記載の銅粉。
(17)
粒度分布が一山である(1)~(16)のいずれかに記載の銅粉。
(18)
(1)~(17)のいずれかに記載の特徴を備えた内部電極用銅粉。
(19)
(1)~(17)のいずれかに記載の特徴を備えた外部電極用銅粉。
(20)
(1)~(19)のいずれかに記載の銅粉が、さらに有機化合物で表面処理されてなる、表面処理された銅粉。
(21)
(1)~(20)のいずれかに記載の銅粉を使用した導電性ペースト。
(22)
(21)のペーストを使用して製造されたチップ積層セラミックコンデンサー。
(23)
内部電極断面に直径が10nm以上のSiO2が存在している、(22)に記載のチップ積層セラミックコンデンサー。
(24)
内部電極断面に最大径0.5μm以上のSiO2が0.5個/cm2以下で存在している、(22)又は(23)に記載のチップ積層セラミックコンデンサー。
(25)
(22)~(24)のいずれかに記載のチップ積層セラミックコンデンサーを最外層に実装した多層基板。
(26)
(22)~(24)のいずれかに記載のチップ積層セラミックコンデンサーを内層に実装した多層基板。
(27)
(25)又は(26)に記載の多層基板を搭載した電子部品。 Therefore, the present invention includes the following items (1) to (27).
(1)
A surface-treated copper powder in which the adhesion amount of Si is 500 to 16000 μg with respect to 1 g of copper powder, and the weight percentage of N with respect to copper powder is 0.05% or more.
(2)
The copper powder according to (1), wherein the adhesion amount of Si is 500 to 3000 μg with respect to 1 g of copper powder, and the weight percentage of N with respect to copper powder is 0.05% or more.
(3)
The copper powder according to (1) or (2), wherein the copper powder is a copper powder surface-treated with a silane coupling agent.
(4)
The copper powder according to (3), wherein the silane coupling agent is aminosilane.
(5)
The copper powder according to any one of (1) to (4), wherein the weight percentage of N with respect to the copper powder is in the range of 0.05% to 0.50%.
(6)
(1) A copper powder obtained by heat-treating the copper powder according to any one of (5) to remove N.
(7)
Copper powder obtained by heat-treating the copper powder according to any one of (1) to (6) in an oxygen atmosphere or an inert atmosphere.
(8)
The copper powder according to any one of (1) to (7), wherein the sintering start temperature is 400 ° C. or higher.
(9)
The copper powder according to any one of (1) to (8), which is obtained by mixing an aqueous solution of aminosilane and copper powder and stirring to dryness.
(10)
The copper powder according to any one of (1) to (9), wherein the amount of aminosilane used for the surface treatment is 0.01 mL or more with respect to 1 g of copper powder.
(11)
The copper powder (12) according to (10), wherein the amount of aminosilane is 0.05 mL or more and the mixing and stirring time with the copper powder is 30 minutes or less.
The copper powder according to any one of (1) to (11), wherein the aminosilane is monoaminosilane or diaminosilane.
(13)
The copper powder according to any one of (1) to (12), wherein the raw material copper powder is obtained by a wet method.
(14)
The copper powder according to any one of (1) to (13), wherein D50 ≦ 1.5 μm.
(15)
The copper powder according to any one of (1) to (13), wherein D50 ≦ 1.0 μm.
(16)
The copper powder according to any one of (1) to (13), wherein D50 ≦ 0.5 μm and Dmax ≦ 1.0 μm.
(17)
The copper powder according to any one of (1) to (16), wherein the particle size distribution is a mountain.
(18)
(1) A copper powder for internal electrodes having the characteristics described in any one of (17).
(19)
(1) A copper powder for external electrodes having the characteristics described in any one of (17).
(20)
A surface-treated copper powder obtained by further surface-treating the copper powder according to any one of (1) to (19) with an organic compound.
(21)
(1) A conductive paste using the copper powder according to any one of (20).
(22)
A chip multilayer ceramic capacitor manufactured using the paste of (21).
(23)
The chip multilayer ceramic capacitor according to (22), wherein SiO 2 having a diameter of 10 nm or more is present in a cross section of the internal electrode.
(24)
The chip multilayer ceramic capacitor according to (22) or (23), wherein SiO 2 having a maximum diameter of 0.5 μm or more is present at 0.5 pieces / cm 2 or less on a cross section of the internal electrode.
(25)
(22) A multilayer substrate on which the chip multilayer ceramic capacitor according to any one of (24) is mounted on an outermost layer.
(26)
(22) A multilayer substrate on which the chip multilayer ceramic capacitor according to any one of (24) is mounted on an inner layer.
(27)
An electronic component on which the multilayer substrate according to (25) or (26) is mounted.
(31)
銅粉を、アミノシラン水溶液と混合して、銅粉分散液を調製する工程、
を含む、表面処理された銅粉を製造する方法。
(32)
銅粉分散液を撹拌する工程を含む、(31)に記載の方法。
(33)
銅粉分散液を超音波処理する工程を含む、(31)又は(32)に記載の方法。
(34)
超音波処理する工程が、1~180分間の超音波処理を行う工程である、(33)に記載の方法。
(35)
銅粉分散液をろ過して銅粉を回収する工程、
ろ過して回収された銅粉を乾燥して、表面処理された銅粉を得る工程、
を含む、(31)~(34)のいずれかに記載の方法。
(36)
乾燥が、50~90℃で30~120分間の加熱処理によって行われる、(35)に記載の方法。
(37)
乾燥が、酸素雰囲気又は不活性雰囲気下で行われる、(35)又は(36)に記載の方法。
(38)
銅分散液が、銅粉1gに対してアミノシラン0.025g以上を含んでいる、(31)~(37)のいずれかに記載の方法。
(39)
アミノシラン水溶液が、次の式I:
H2N-R1-Si(OR2)2(R3) (式I)
(ただし、上記式Iにおいて、
R1は、直鎖状又は分枝を有する、飽和又は不飽和の、置換又は非置換の、環式又は非環式の、複素環を有する又は複素環を有しない、C1~C12の炭化水素の二価基であり、
R2は、C1~C5のアルキル基であり、
R3は、C1~C5のアルキル基、又はC1~C5のアルコキシ基である。)
で表されるアミノシランの水溶液である、(31)~(38)のいずれかに記載の方法。
(40)
R1が、置換又は非置換の、C1~C12の直鎖状飽和炭化水素の二価基、置換又は非置換の、C1~C12の分枝状飽和炭化水素の二価基、置換又は非置換の、C1~C12の直鎖状不飽和炭化水素の二価基、置換又は非置換の、C1~C12の分枝状不飽和炭化水素の二価基、置換又は非置換の、C1~C12の環式炭化水素の二価基、置換又は非置換の、C1~C12の複素環式炭化水素の二価基、置換又は非置換の、C1~C12の芳香族炭化水素の二価基、からなる群から選択された基である、(39)に記載の方法。
(41)
R1が、 -(CH2)n-、-(CH2)n-(CH)m-(CH2)j-1-、-(CH2)n-(CC)-(CH2)n-1-、-(CH2)n-NH-(CH2)m-、-(CH2)n-NH-(CH2)m-NH-(CH2)j-、-(CH2)n-1-(CH)NH2-(CH2)m-1-、-(CH2)n-1-(CH)NH2-(CH2)m-1-NH-(CH2)j- からなる群から選択された基である(ただし、n、m、jは、1以上の整数である)、(39)に記載の方法。
(42)
R1が、-(CH2)n-、又は-(CH2)n-NH-(CH2)m-である、(39)に記載の方法。
(43)
n、m、jが、それぞれ独立に、1、2又は3である、(41)~(42)のいずれかに記載の方法。
(44)
R2が、メチル基又はエチル基である、(39)~(43)のいずれかに記載の方法。
(45)
R3が、メチル基、エチル基、メトキシ基又はエトキシ基である、(39)~(44)のいずれかに記載の方法。
(46)
銅粉が、湿式法によって製造された銅粉である、(31)~(45)のいずれかに記載の方法。
(47)
(31)~(46)のいずれかに記載の製造方法によって製造された表面処理された銅粉を、溶媒及び/又はバインダーと配合して、導電性銅ペーストを製造する方法。
(48)
(31)~(46)のいずれかに記載の製造方法によって製造された表面処理された銅粉を、溶媒及び/又はバインダーと配合して、導電性銅ペーストを得る工程、
導電性銅ペーストを基材に塗布する工程、
基材に塗布された導電性銅ペーストを加熱焼成する工程、
を含む、電極を製造する方法。
(49)
電極が、チップ積層セラミックコンデンサー用電極である、(48)に記載の方法。
(50)
表面処理された銅粉を、さらに有機化合物で表面処理する工程、
を含む、(31)~(49)のいずれかに記載の方法。 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.
(34)
The method according to (33), wherein the sonication step is a sonication step of 1 to 180 minutes.
(35)
A step of collecting the copper powder by filtering the copper powder dispersion,
A step of drying the copper powder collected by filtration to obtain a surface-treated copper powder,
The method according to any one of (31) to (34), comprising:
(36)
The method according to (35), wherein the drying is performed by heat treatment at 50 to 90 ° C. for 30 to 120 minutes.
(37)
The method according to (35) or (36), wherein the drying is performed in an oxygen atmosphere or an inert atmosphere.
(38)
The method according to any one of (31) to (37), wherein the copper dispersion contains 0.025 g or more of aminosilane with respect to 1 g of copper powder.
(39)
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. )
The method according to any one of (31) to (38), which is an aqueous solution of an aminosilane represented by:
(40)
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, The method according to (39), which is a group selected from:
(41)
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- The method according to (39), wherein n, m, and j are each an integer of 1 or more.
(42)
The method according to (39), wherein R 1 is — (CH 2 ) n — or — (CH 2 ) n —NH— (CH 2 ) m —.
(43)
The method according to any one of (41) to (42), wherein n, m and j are each independently 1, 2 or 3.
(44)
The method according to any one of (39) to (43), wherein R2 is a methyl group or an ethyl group.
(45)
The method according to any one of (39) to (44), wherein R3 is a methyl group, an ethyl group, a methoxy group, or an ethoxy group.
(46)
The method according to any one of (31) to (45), wherein the copper powder is a copper powder produced by a wet method.
(47)
(31) A method for producing a conductive copper paste by blending the surface-treated copper powder produced by the production method according to any one of (31) to (46) with a solvent and / or a binder.
(48)
A step of blending the surface-treated copper powder produced by the production method according to any one of (31) to (46) with a solvent and / or a binder to obtain a conductive copper paste;
Applying a conductive copper paste to a substrate;
A step of heating and baking the conductive copper paste applied to the substrate;
A method of manufacturing an electrode comprising:
(49)
The method according to (48), wherein the electrode is an electrode for a chip multilayer ceramic capacitor.
(50)
A step of further surface-treating the surface-treated copper powder with an organic compound,
The method according to any one of (31) to (49), comprising:
(51)
(31)~(46)のいずれかに記載の製造方法によって製造された、表面処理された銅粉。
(52)
(45)に記載の製造方法によって製造された、導電性銅ペースト。
(53)
(46)に記載の製造方法によって製造された、電極。
(54)
(47)に記載の製造方法によって製造された、チップ積層セラミックコンデンサー用電極。 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).
(61)
(31)~(46)のいずれかに記載の製造方法によって製造された、表面処理された銅粉であって、
Siの付着量が銅粉1gに対して500~16000μgであり、
銅粉に対するNの重量%が0.05%以上であり、
焼結開始温度が400℃以上である、銅粉。
(62)
(61)に記載の表面処理された銅粉が、配合されてなる、導電性銅ペースト。
(63)
(62)に記載の導電性銅ペーストが塗布されて加熱焼成されてなる、電極であって、
電極断面に最大径0.5μm以上のSiO2が0.5個/cm2以下で存在している、電極。 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),
The adhesion amount of Si is 500-16000 μg per 1 g of copper powder,
% By weight of N to copper powder is 0.05% or more,
Copper powder having a sintering start temperature of 400 ° C or higher.
(62)
The electroconductive copper paste formed by mix | blending the surface-treated copper powder as described in (61).
(63)
(62) An electrode obtained by applying the conductive copper paste according to (62) and baking by heating.
An electrode in which SiO 2 having a maximum diameter of 0.5 μm or more is present at 0.5 pieces / cm 2 or less on the electrode cross section.
(71)
Ti、Al、Zr、Ce、Snのうちいずれか1種以上の付着量が銅粉1gに対して300~1500μg、金属粉に対するNの重量%が0.05%以上である、表面処理された銅粉。
(72)
Ti、Al、Zr、Ce、Snがカップリング剤処理により吸着させられ(71)の銅粉。
(73)
分子構造末端がアミノ基であるカップリング剤で処理された(71)または(72)のいずれかの銅粉。
(74)
カップリング剤がチタネートまたはアルミネートカップリング剤である(73)の銅粉。
(75)
Ti、Al、Zr、Ce、Snのうちいずれか1種以上の付着量が銅粉1gに対して300~1500μg、金属粉に対するNの重量%が0.05%以上であり、焼結開始温度が400℃以上である銅粉。
(76)
Si、Ti、Al、Zr、Ce、Snのうちいずれか1種以上の付着量が金属粉1gに対して200~1500μg、金属粉に対するNの重量%が0.02%以上である、表面処理された、Cu以外の金属粉。
(77)
金属粉がPt、Pd、Ag、Niのいずれかである(71)の金属粉。
(78)
Si、Ti、Al、Zr、Ce、Snをカップリング剤処理で吸着させた(76)または(77)の金属粉。
(79)
カップリング剤がシラン、チタネート、アルミネートのいずれかである(78)の金属粉。
(80)
末端がアミノ基であるカップリング剤で処理された(79)の金属粉。
(81)
Si、Ti、Al、Zr、Ce、Snのうちいずれか1種以上の付着量がCu以外の金属粉1gに対して200~1500μg、Cu以外の金属粉に対するNの重量%が0.02%以上であり、焼結開始温度が400℃以上である、Cu以外の金属粉。
(82)
(71)~(81)に記載の表面処理された金属粉が、配合されてなる、導電性金属ペースト。
(83)
(82)に記載の導電性金属ペーストが塗布されて加熱焼成されてなる、電極であって、
電極断面に最大径0.5μm以上のSiO2、TiO2、Al2O3が0.5個/μm2以下で存在している、電極。 Furthermore, the present invention also includes the following (71) to (71).
(71)
Surface treatment was performed in which the adhesion amount of at least one of Ti, Al, Zr, Ce, and Sn was 300 to 1500 μg with respect to 1 g of copper powder, and the weight percentage of N with respect to metal powder was 0.05% or more. Copper powder.
(72)
Ti, Al, Zr, Ce, Sn are adsorbed by the coupling agent treatment, and the copper powder of (71).
(73)
Either the copper powder of (71) or (72) processed with the coupling agent whose molecular structure terminal is an amino group.
(74)
(73) The copper powder wherein the coupling agent is a titanate or aluminate coupling agent.
(75)
The adhesion amount of any one or more of Ti, Al, Zr, Ce, and Sn is 300 to 1500 μg with respect to 1 g of copper powder, the weight percentage of N with respect to metal powder is 0.05% or more, and the sintering start temperature Copper powder having a temperature of 400 ° C. or higher.
(76)
Surface treatment in which the adhesion amount of any one or more of Si, Ti, Al, Zr, Ce and Sn is 200 to 1500 μg with respect to 1 g of metal powder, and the weight percentage of N with respect to metal powder is 0.02% or more. Metal powder other than Cu.
(77)
The metal powder according to (71), wherein the metal powder is any one of Pt, Pd, Ag, and Ni.
(78)
(76) or (77) metal powder in which Si, Ti, Al, Zr, Ce, and Sn are adsorbed by a coupling agent treatment.
(79)
(78) The metal powder, wherein the coupling agent is any one of silane, titanate, and aluminate.
(80)
(79) The metal powder treated with a coupling agent having a terminal amino group.
(81)
At least one of Si, Ti, Al, Zr, Ce and Sn is attached in an amount of 200 to 1500 μg with respect to 1 g of metal powder other than Cu, and the weight percentage of N with respect to metal powder other than Cu is 0.02%. Metal powder other than Cu having a sintering start temperature of 400 ° C. or higher.
(82)
A conductive metal paste comprising the surface-treated metal powder according to any one of (71) to (81).
(83)
An electrode obtained by applying the conductive metal paste according to (82) and baking by heating,
An electrode in which SiO 2, TiO 2 , and Al 2 O 3 having a maximum diameter of 0.5 μm or more are present on the electrode cross section at 0.5 pieces / μm 2 or less.
(101)
Si、Ti、Al、Zr、Ce、Snのうちいずれか1種以上の付着量が金属粉1gに対して200~16000μg、金属粉に対するNの重量%が0.02%以上である、表面処理された金属粉。
(102)
金属粉が、Pt、Pd、Ag、Ni、Cuのいずれかの金属粉である、(101)に記載の金属粉。
(103)
金属粉が、銅粉である、(101)に記載の金属粉。
(104)
金属粉が、Pt、Pd、Ag、Niのいずれかの金属粉である、(101)に記載の金属粉。
(105)
Si、Ti、Al、Zr、Ce、Snのうちいずれか1種以上の付着量が金属粉1gに対して300~16000μgである、(101)~(104)のいずれかに記載の金属粉。
(106)
Si、Ti、Al、Zr、Ce、Snのうちいずれか1種以上の付着量が金属粉1gに対して500~16000μgである、(101)~(104)のいずれかに記載の金属粉。
(107)
Si、Ti、Al、Zr、Ce、Snのうちいずれか1種以上の付着量が金属粉1gに対して3000μg以下である、(101)~(106)のいずれかに記載の金属粉。
(108)
Si、Ti、Al、Zr、Ce、Snのうちいずれか1種以上の付着量が金属粉1gに対して1500μg以下である、(101)~(106)のいずれかに記載の金属粉。
(109)
金属粉に対するNの重量%が0.05%以上である、(101)~(108)のいずれかに記載の金属粉。
(110)
Si、Ti、Al、Zr、Ce、Snのうちいずれか1種以上が、Ti、Al、Zr、Ce、Snのうちいずれか1種以上である、(101)~(109)のいずれかに記載の金属粉。
(111)
Si、Ti、Al、Zr、Ce、Snのうちいずれか1種以上が、Siである、(101)~(109)のいずれかに記載の金属粉。
(112)
金属粉が銅粉であり、Siの付着量が銅粉1gに対して500~16000μg、銅粉に対するNの重量%が0.05%以上である、(101)に記載の金属粉。
(113)
金属粉が銅粉であり、Siの付着量が銅粉1gに対して500~3000μg、銅粉に対するNの重量%が0.05%以上である、(101)に記載の金属粉。
(114)
金属粉が、カップリング剤で表面処理された金属粉である、(101)~(113)のいずれかに記載の金属粉。
(115)
Si、Ti、Al、Zr、Ce、Snのうちいずれか1種以上が、カップリング剤処理で吸着された、(101)~(114)のいずれかに記載の金属粉。
(116)
カップリング剤がシラン、チタネート、アルミネートのいずれかである、(101)~(115)のいずれかに記載の金属粉。
(117)
カップリング剤が末端がアミノ基であるカップリング剤である、(101)~(116)のいずれかに記載の金属粉。
(118)
カップリング剤がアミノシランである、(101)~(117)のいずれかに記載の金属粉。
(119)
焼結開始温度が400℃以上である、(101)~(118)のいずれかに記載の金属粉。
(120)
アミノシランが、モノアミノシラン又はジアミノシランである、(118)に記載の金属粉。
(121)
(101)~(121)のいずれかに記載の金属粉が、さらに有機化合物で表面処理されてなる、表面処理された金属粉。
(122)
金属粉が、Pt、Pd、Ag、Niのいずれかの金属粉であり、Si、Ti、Al、Zr、Ce、Snのうちいずれか1種以上の付着量がCu以外の金属粉1gに対して200~1500μg、Cu以外の金属粉に対するNの重量%が0.02%以上であり、焼結開始温度が400℃以上である、(101)に記載の金属粉。
(123)
(101)~(122)のいずれかに記載の金属粉を使用した導電性金属粉ペースト。
(124)
(123)に記載の導電性金属ペーストが塗布されて加熱焼成されてなる、電極であって、
電極断面に最大径0.5μm以上のSiO2、TiO2、Al2O3が0.5個/μm2以下で存在している、電極。
(125)
(123)のペーストを使用して製造されたチップ積層セラミックコンデンサー。
(126)
内部電極断面に直径が10nm以上のSiO2、TiO2又はAl2O3が存在している、(125)に記載のチップ積層セラミックコンデンサー。
(127)
内部電極断面に最大径0.5μm以上のSiO2、TiO2又はAl2O3が0.5個/μm2以下で存在している、(125)又は(126)に記載のチップ積層セラミックコンデンサー。
(128)
(125)~(127)のいずれかに記載のチップ積層セラミックコンデンサーを最外層に実装した多層基板。
(129)
(125)~(127)のいずれかに記載のチップ積層セラミックコンデンサーを内層に実装した多層基板。
(130)
(128)又は(129)に記載の多層基板を搭載した電子部品。
(131)
金属粉を、カップリング剤水溶液と混合して、金属粉分散液を調製する工程、
を含む、表面処理された金属粉を製造する方法。
(132)
金属粉が、Pt、Pd、Ag、Ni、Cuのいずれかの金属粉である、(131)に記載の方法。
(133)
金属粉が、銅粉である、(131)に記載の方法。
(134)
金属粉が、Pt、Pd、Ag、Niのいずれかの金属粉である、(131)に記載の方法。
(135)
金属粉分散液を撹拌する工程を含む、(131)~(134)のいずれかに記載の方法。
(136)
金属粉分散液を超音波処理する工程を含む、(131)~(135)のいずれかに記載の方法。
(137)
超音波処理する工程が、1~180分間の超音波処理を行う工程である、(131)~(136)のいずれかに記載の方法。
(138)
金属粉分散液をろ過して銅粉を回収する工程、
ろ過して回収された銅粉を乾燥して、表面処理された金属粉を得る工程、
を含む、(131)~(137)のいずれかに記載の方法。
(139)
乾燥が、酸素雰囲気又は不活性雰囲気下で行われる、(138)に記載の方法。
(140)
金属粉分散液が、金属粉1gに対してカップリング剤0.025g以上を含んでいる、(131)~(139)のいずれかに記載の方法。
(141)
カップリング剤水溶液が、次の式I:
H2N-R1-Si(OR2)2(R3) (式I)
(ただし、上記式Iにおいて、
R1は、直鎖状又は分枝を有する、飽和又は不飽和の、置換又は非置換の、環式又は非環式の、複素環を有する又は複素環を有しない、C1~C12の炭化水素の二価基であり、
R2は、C1~C5のアルキル基であり、
R3は、C1~C5のアルキル基、又はC1~C5のアルコキシ基である。)
で表されるアミノシランの水溶液である、(131)~(140)のいずれかに記載の方法。
(142)
R1が、 -(CH2)n-、-(CH2)n-(CH)m-(CH2)j-1-、-(CH2)n-(CC)-(CH2)n-1-、-(CH2)n-NH-(CH2)m-、-(CH2)n-NH-(CH2)m-NH-(CH2)j-、-(CH2)n-1-(CH)NH2-(CH2)m-1-、-(CH2)n-1-(CH)NH2-(CH2)m-1-NH-(CH2)j- からなる群から選択された基である(ただし、n、m、jは、1以上の整数である)、(141)に記載の方法。
(143)
カップリング剤水溶液が、次の式II:
(H2N-R1-O)pTi(OR2)q (式II)
(ただし、上記式IIにおいて、
R1は、直鎖状又は分枝を有する、飽和又は不飽和の、置換又は非置換の、環式又は非環式の、複素環を有する又は複素環を有しない、C1~C12の炭化水素の二価基であり、
R2は、直鎖状又は分枝を有する、C1~C5のアルキル基であり、
p及びqは、1~3の整数であり、p+q=4である。)
で表されるアミノ基含有チタネートの水溶液である、(131)~(140)のいずれかに記載の方法。
(144)
R1が、 -(CH2)n-、-(CH2)n-(CH)m-(CH2)j-1-、-(CH2)n-(CC)-(CH2)n-1-、-(CH2)n-NH-(CH2)m-、-(CH2)n-NH-(CH2)m-NH-(CH2)j-、-(CH2)n-1-(CH)NH2-(CH2)m-1-、-(CH2)n-1-(CH)NH2-(CH2)m-1-NH-(CH2)j- からなる群から選択された基である(ただし、n、m、jは、1以上の整数である)、(143)に記載の方法。
(145)
金属粉が、湿式法によって製造された銅粉である、(131)~(144)のいずれかに記載の方法。
(146)
(131)~(145)のいずれかに記載の製造方法によって製造された表面処理された金属粉を、溶媒及び/又はバインダーと配合して、導電性金属粉ペーストを製造する方法。
(147)
(131)~(145)のいずれかに記載の製造方法によって製造された表面処理された金属粉を、溶媒及び/又はバインダーと配合して、導電性金属粉ペーストを得る工程、
導電性金属粉ペーストを基材に塗布する工程、
基材に塗布された導電性金属粉ペーストを加熱焼成する工程、
を含む、電極を製造する方法。
(148)
(131)~(145)のいずれかに記載の製造方法によって製造された、表面処理された金属粉。
(149)
(146)に記載の製造方法によって製造された、導電性金属粉ペースト。
(150)
(147)に記載の製造方法によって製造された、電極。
(151)
(131)~(145)のいずれかに記載の製造方法によって製造された、表面処理された金属粉であって、
Si、Ti、Alのいずれかの付着量が金属粉1gに対して200~16000μgであり、
金属粉に対するNの重量%が0.02%以上であり、
焼結開始温度が400℃以上である、金属粉。
(152)
(151)に記載の表面処理された金属粉が、配合されてなる、導電性金属粉ペースト。
(153)
(151)に記載の導電性金属粉ペーストが塗布されて加熱焼成されてなる、電極であって、
電極断面に最大径0.5μm以上のSiO2、TiO2又はAl2O3が0.5個/μm2以下で存在している、電極。 Furthermore, the present invention also includes the following (101) to (101).
(101)
Surface treatment in which the adhesion amount of any one or more of Si, Ti, Al, Zr, Ce and Sn is 200 to 16000 μg with respect to 1 g of metal powder, and the weight percentage of N with respect to metal powder is 0.02% or more. Metal powder.
(102)
The metal powder according to (101), wherein the metal powder is one of Pt, Pd, Ag, Ni, and Cu.
(103)
The metal powder according to (101), wherein the metal powder is a copper powder.
(104)
The metal powder according to (101), wherein the metal powder is any one of Pt, Pd, Ag, and Ni.
(105)
The metal powder according to any one of (101) to (104), wherein the adhesion amount of any one or more of Si, Ti, Al, Zr, Ce, and Sn is 300 to 16000 μg with respect to 1 g of the metal powder.
(106)
The metal powder according to any one of (101) to (104), wherein the adhesion amount of one or more of Si, Ti, Al, Zr, Ce, and Sn is 500 to 16000 μg with respect to 1 g of the metal powder.
(107)
The metal powder according to any one of (101) to (106), wherein the adhesion amount of any one or more of Si, Ti, Al, Zr, Ce, and Sn is 3000 μg or less with respect to 1 g of the metal powder.
(108)
The metal powder according to any one of (101) to (106), wherein an adhesion amount of any one or more of Si, Ti, Al, Zr, Ce, and Sn is 1500 μg or less with respect to 1 g of the metal powder.
(109)
The metal powder according to any one of (101) to (108), wherein the weight percentage of N with respect to the metal powder is 0.05% or more.
(110)
Any one of Si, Ti, Al, Zr, Ce, and Sn is one or more of Ti, Al, Zr, Ce, and Sn, and any one of (101) to (109) The metal powder described.
(111)
The metal powder according to any one of (101) to (109), wherein at least one of Si, Ti, Al, Zr, Ce, and Sn is Si.
(112)
The metal powder according to (101), wherein the metal powder is a copper powder, the adhesion amount of Si is 500 to 16000 μg with respect to 1 g of the copper powder, and the weight percentage of N with respect to the copper powder is 0.05% or more.
(113)
The metal powder according to (101), wherein the metal powder is a copper powder, the adhesion amount of Si is 500 to 3000 μg with respect to 1 g of the copper powder, and the weight percentage of N with respect to the copper powder is 0.05% or more.
(114)
The metal powder according to any one of (101) to (113), wherein the metal powder is a metal powder surface-treated with a coupling agent.
(115)
The metal powder according to any one of (101) to (114), wherein one or more of Si, Ti, Al, Zr, Ce, and Sn are adsorbed by a coupling agent treatment.
(116)
The metal powder according to any one of (101) to (115), wherein the coupling agent is any one of silane, titanate, and aluminate.
(117)
The metal powder according to any one of (101) to (116), wherein the coupling agent is a coupling agent having a terminal amino group.
(118)
The metal powder according to any one of (101) to (117), wherein the coupling agent is aminosilane.
(119)
The metal powder according to any one of (101) to (118), wherein the sintering start temperature is 400 ° C. or higher.
(120)
The metal powder according to (118), wherein the aminosilane is monoaminosilane or diaminosilane.
(121)
A surface-treated metal powder obtained by further surface-treating the metal powder according to any one of (101) to (121) with an organic compound.
(122)
The metal powder is a metal powder of any one of Pt, Pd, Ag, and Ni, and any one or more of Si, Ti, Al, Zr, Ce, and Sn is attached to 1 g of the metal powder other than Cu. 200 to 1500 μg, the metal powder according to (101), wherein the weight percentage of N relative to the metal powder other than Cu is 0.02% or more and the sintering start temperature is 400 ° C. or more.
(123)
A conductive metal powder paste using the metal powder according to any one of (101) to (122).
(124)
(123) An electrode obtained by applying the conductive metal paste according to (123) and baking by heating.
An electrode in which SiO 2, TiO 2 , and Al 2 O 3 having a maximum diameter of 0.5 μm or more are present on the electrode cross section at 0.5 pieces / μm 2 or less.
(125)
A chip multilayer ceramic capacitor produced using the paste of (123).
(126)
The chip multilayer ceramic capacitor according to (125), wherein SiO 2 , TiO 2, or Al 2 O 3 having a diameter of 10 nm or more is present in the cross section of the internal electrode.
(127)
The chip multilayer ceramic capacitor according to (125) or (126), wherein SiO 2 , TiO 2 or Al 2 O 3 having a maximum diameter of 0.5 μm or more is present in the internal electrode cross section at 0.5 pieces / μm 2 or less. .
(128)
(125) A multilayer substrate on which the chip multilayer ceramic capacitor according to any one of (127) is mounted on the outermost layer.
(129)
(125) A multilayer board on which the chip multilayer ceramic capacitor according to any one of (127) is mounted on an inner layer.
(130)
An electronic component on which the multilayer board according to (128) or (129) is mounted.
(131)
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:
(132)
The method according to (131), wherein the metal powder is one of Pt, Pd, Ag, Ni, and Cu.
(133)
The method according to (131), wherein the metal powder is copper powder.
(134)
The method according to (131), wherein the metal powder is any one of Pt, Pd, Ag, and Ni.
(135)
The method according to any one of (131) to (134), comprising a step of stirring the metal powder dispersion.
(136)
The method according to any one of (131) to (135), comprising a step of ultrasonicating the metal powder dispersion.
(137)
The method according to any one of (131) to (136), wherein the sonication step is a sonication step for 1 to 180 minutes.
(138)
A step of collecting the copper powder by filtering the metal powder dispersion,
Drying the copper powder recovered by filtration to obtain a surface-treated metal powder,
The method according to any one of (131) to (137), comprising:
(139)
The method according to (138), wherein the drying is performed in an oxygen atmosphere or an inert atmosphere.
(140)
The method according to any one of (131) to (139), wherein the metal powder dispersion contains 0.025 g or more of a coupling agent with respect to 1 g of the metal powder.
(141)
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. )
The method according to any one of (131) to (140), which is an aqueous solution of an aminosilane represented by:
(142)
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 (141).
(143)
An aqueous coupling agent solution has the following formula II:
(H 2 N—R 1 —O) p Ti (OR 2 ) q (Formula II)
(However, in the above formula II,
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 linear or branched C1-C5 alkyl group,
p and q are integers of 1 to 3, and p + q = 4. )
The method according to any one of (131) to (140), which is an aqueous solution of an amino group-containing titanate represented by:
(144)
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 (143).
(145)
The method according to any one of (131) to (144), wherein the metal powder is a copper powder produced by a wet method.
(146)
(131) A method for producing a conductive metal powder paste by blending the surface-treated metal powder produced by the production method according to any one of (145) and a solvent and / or a binder.
(147)
A step of blending the surface-treated metal powder produced by the production method according to any one of (131) to (145) with a solvent and / or a binder to obtain a conductive metal powder paste;
Applying a conductive metal powder paste to a substrate;
A step of heating and firing the conductive metal powder paste applied to the substrate;
A method of manufacturing an electrode comprising:
(148)
(131) Surface-treated metal powder produced by the production method according to any one of (145).
(149)
(146) The electroconductive metal powder paste manufactured by the manufacturing method of description.
(150)
An electrode manufactured by the manufacturing method according to (147).
(151)
(131) to (145) a surface-treated metal powder produced by the production method according to any one of
The adhesion amount of any one of Si, Ti and Al is 200 to 16000 μg with respect to 1 g of metal powder,
% By weight of N to metal powder is 0.02% or more,
Metal powder having a sintering start temperature of 400 ° C or higher.
(152)
The electroconductive metal powder paste formed by mix | blending the surface-treated metal powder as described in (151).
(153)
(151) It is an electrode formed by applying the conductive metal powder paste according to (151) and baking it.
An electrode in which SiO 2 , TiO 2 or Al 2 O 3 having a maximum diameter of 0.5 μm or more is present in the electrode cross section at 0.5 pieces / μm 2 or less.
本発明においては、銅粉を、アミノシラン水溶液と混合して、銅粉分散液を調製する工程、を行って、この銅粉分散液から、表面処理された銅粉を得ることができる。 The present invention will be described in detail below with reference to embodiments. The present invention is not limited to the specific embodiments described below.
In the present invention, 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.
R1は、直鎖状又は分枝を有する、飽和又は不飽和の、置換又は非置換の、環式又は非環式の、複素環を有する又は複素環を有しない、C1~C12の炭化水素の二価基であり、
R2は、C1~C5のアルキル基であり、
R3は、C1~C5のアルキル基、又はC1~C5のアルコキシ基である。 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.
Cu2O+H2SO4 → Cu↓+CuSO4+H2O
この不均化によって得られた銅粉は、所望により、洗浄、防錆、ろ過、乾燥、解砕、分級を行って、その後にアミノシランと混合することもできるが、好ましい実施の態様において、所望により、洗浄、防錆、ろ過を行った後に、乾燥を行うことなく、そのままアミノシラン水溶液と混合することができる。 As described above, in a preferred embodiment, the copper powder used for the surface treatment can be a copper powder obtained by a wet method. In a preferred embodiment, as a method of producing copper powder 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. In a preferred embodiment, 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. In a preferred embodiment, 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. In a preferred embodiment, 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. In a preferred embodiment, 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. , Can be added. In a preferred embodiment, the disproportionation reaction can be completed in 10 minutes. In a preferred embodiment, the concentration of gum arabic in the slurry can be 0.229 to 1.143 g / L. As the 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.
(H2N-R1-O)pTi(OR2)q (式II)
(ただし、上記式IIにおいて、
R1は、直鎖状又は分枝を有する、飽和又は不飽和の、置換又は非置換の、環式又は非環式の、複素環を有する又は複素環を有しない、C1~C12の炭化水素の二価基であり、
R2は、直鎖状又は分枝を有する、C1~C5のアルキル基であり、
p及びqは、1~3の整数であり、p+q=4である。)
で表されるアミノ基含有チタネートを挙げることができる。 Titanates that can be suitably used in the present invention include the following formula II:
(H 2 N—R 1 —O) p Ti (OR 2 ) q (Formula II)
(However, in the above formula II,
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 linear or branched C1-C5 alkyl group,
p and q are integers of 1 to 3, and p + q = 4. )
The amino group containing titanate represented by these can be mentioned.
[表面処理銅粉の製造]
以下のように表面処理された銅粉を製造した。
[湿式法による製粉]
表面処理に供される銅粉20gを、湿式法によって製造した。得られた銅粉は、次のような特性であった。測定は、レーザー回折式粒度分布測定装置(島津製作所製SALD-2100)を使用した。
D50 0.12μm
分布一山 Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited to the following examples.
[Manufacture of surface-treated copper powder]
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 μm
Distribution
次の各種のシランを使用したシラン水溶液をそれぞれ50ml調製した。
シラン:ジアミノシランA-1120(MOMENTIVE社製)
アミノシランA-1110(MOMENTIVE社製)
エポキシシランZ-6040(東レダウコーニング社製)
メチルトリメトキシシランKBM-13(信越シリコーン社製)
3-フェニルアミノプロピルトリメトキシシラン(MOMENTIVE社製)
濃度は0.5~15vol%の範囲で調製した。また、アミノ系シラン以外は希硫酸でpHを4に調整した。 [Preparation of aqueous silane solution]
50 ml of an aqueous silane solution using the following various silanes was prepared.
Silane: Diaminosilane A-1120 (made by MOMENTIVE)
Aminosilane A-1110 (made by MOMENTIVE)
Epoxy silane Z-6040 (manufactured by Toray Dow Corning)
Methyltrimethoxysilane KBM-13 (manufactured by Shin-Etsu Silicone)
3-Phenylaminopropyltrimethoxysilane (made by MOMENTIVE)
The concentration was adjusted in the range of 0.5 to 15 vol%. Moreover, pH was adjusted to 4 with dilute sulfuric acid except amino silane.
ジアミノシランA-1120:
H2N-C2H4-NH-C3H6-Si(OCH3)3
アミノシランA-1110:
H2N-C3H6-Si(OCH3)3
エポキシシランZ-6040:
メチルトリメトキシシランKBM-13:
H3C-Si(OCH3)3
3-フェニルアミノプロピルトリメトキシシラン:
C6H5-NH-C3H6-Si(OCH3)3
The structural formulas of various silanes are as follows.
Diaminosilane A-1120:
H 2 N—C 2 H 4 —NH—C 3 H 6 —Si (OCH 3 ) 3
Aminosilane A-1110:
H 2 N—C 3 H 6 —Si (OCH 3 ) 3
Epoxysilane Z-6040:
Methyltrimethoxysilane KBM-13:
H 3 C—Si (OCH 3 ) 3
3-Phenylaminopropyltrimethoxysilane:
C 6 H 5 —NH—C 3 H 6 —Si (OCH 3 ) 3
銅粉20gと各シラン水溶液50mlを混合撹拌して、銅粉分散液を調製し、直ちに60分間(又は120分間)の超音波処理を行った(株式会社テックジャム製、超音波洗浄器 3周波タイプ / W-113)(出力100W、周波数100kHz)。この60分間の所要時間を表1では、混合撹拌時間と記載した。操作は室温で行った。
また、表1の記載のように、いくつかの実施例では回転羽による攪拌混合(300rpm)を上記超音波攪拌と併用するか、回転羽による攪拌のみでシランカップリング剤を銅粉に吸着させた。
銅粉分散液をろ過して、表面処理された銅粉を回収し、70℃1時間で加熱乾燥して、表面処理された銅粉を得た。
各実施例及び比較例についての表面処理された銅粉で行った処理を、表1にまとめた。 [Surface treatment by mixing with silane aqueous solution]
20 g of copper powder and 50 ml of each silane aqueous solution were mixed and stirred to prepare a copper powder dispersion, and immediately subjected to ultrasonic treatment for 60 minutes (or 120 minutes) (manufactured by Techjam Co., Ltd., ultrasonic cleaner 3 frequency) Type / W-113) (output 100W, frequency 100kHz). The time required for 60 minutes is described as mixing and stirring time in Table 1. The operation was performed at room temperature.
In addition, as shown in Table 1, in some examples, stirring and mixing (300 rpm) using a rotating blade is used in combination with the above ultrasonic stirring, or the silane coupling agent is adsorbed to copper powder only by stirring using a rotating blade. It was.
The copper powder dispersion was filtered to recover the surface-treated copper powder, and heat-dried at 70 ° C. for 1 hour to obtain a surface-treated copper powder.
The treatments performed with the surface-treated copper powder for each example and comparative example are summarized in Table 1.
上述の操作によって得られた、表面処理された銅粉に対して、以下の方法によって評価を行った。 [Evaluation of surface-treated copper powder]
The surface-treated copper powder obtained by the above operation was evaluated by the following method.
銅粉の大きさについて、次の手段で測定を行った。その結果は、表2にまとめた。
レーザー回折式粒度分布測定(島津製作所SLAD-2100) [Copper powder size measurement]
About the magnitude | size of copper powder, it measured by the following means. The results are summarized in Table 2.
Laser diffraction particle size distribution measurement (Shimadzu SLAD-2100)
表面処理された銅粉によって、サンプルを作製して、TMA(Thermomechanical Analyzer)を使用して、焼結開始温度を、次の条件で測定した。
サンプル作製条件
圧粉体サイズ:7mmφ×5mm高さ
成型圧力:1Ton/cm2(1000kg重/cm2)
(潤滑剤として0.5wt%のステアリン酸亜鉛を添加)
測定条件
装置:島津製作所TMA-50
昇温:5℃/分
雰囲気:2vol%H2-N2(300cc/分)
荷重:98.0mN [Measurement by TMA]
A sample was prepared from the surface-treated copper powder, and the sintering start temperature was measured using the TMA (Thermomechanical Analyzer) under the following conditions.
Sample preparation conditions Compact size: 7 mmφ x 5 mm height Molding pressure: 1 Ton / cm 2 (1000 kg weight / cm 2 )
(0.5 wt% zinc stearate added as lubricant)
Measurement conditions Equipment: Shimadzu Corporation TMA-50
Temperature rise: 5 ° C./min Atmosphere: 2 vol% H 2 —N 2 (300 cc / min)
Load: 98.0mN
装置:STEM
断面TEM像倍率:200000倍(20万倍) For each sintered body formed by heating by the TMA, the cross section thereof was observed by TEM, and counts the number of SiO 2 greater than or equal to the maximum diameter of 0.5 [mu] m. The results obtained are summarized in Table 3.
Equipment: STEM
Cross-sectional TEM image magnification: 200000 times (200,000 times)
表面処理された銅粉の表面に付着したSi、N及びCを次の条件で分析した。この結果は、表3にまとめた。
付着量 Si・・・表面処理された銅粉を酸で溶解し、ICP(誘導結合プラズマ原子発光分析法)で定量して、表面処理された銅粉の単位質量(g)に対する、付着したSiの質量(μg)を求めた。
N、C・・・銅粉を高温で溶融させ、発生したNO2、CO2から付着N、C量を算出して、銅粉の全表面に付いたN,Cの量を測定することで、表面処理された銅粉の質量に対する、付着したN,Cの質量の質量%(重量%)を求めた。 [analysis]
Si, N, and C adhering to the surface of the surface-treated copper powder were analyzed under the following conditions. The results are summarized in Table 3.
Adhesion amount Si: The surface-treated copper powder is dissolved with an acid, quantified by ICP (inductively coupled plasma atomic emission spectrometry), and adhered to the unit mass (g) of the surface-treated copper powder. The mass (μg) of was determined.
N, and C · · · copper powder is melted at a high temperature, generated NO 2, deposited from CO 2 N, to calculate the amount of C, to measure the N, the amount of C which stuck to the entire surface of the copper powder The mass% (% by weight) of the mass of N and C adhering to the mass of the surface-treated copper powder was determined.
上記実施例4で得た表面処理された銅粉に対して、さらに防錆処理を行っても、本発明の焼結遅延性が維持されることを確認するために、以下の実験を行った(実施例9)。 [Anti-rust treatment of surface-treated copper powder]
In order to confirm that the sintering retardancy of the present invention is maintained even if the rust prevention treatment is further performed on the surface-treated copper powder obtained in Example 4, the following experiment was conducted. (Example 9).
実施例4の銅粉を得た後、防錆処理を行うため、ベンゾトリアゾール水溶液(0.1g / L)100 mL中に分散させ、回転羽で500rpmで10分間攪拌し、ろ過、乾燥(窒素雰囲気下で70℃×1h)させ、さらに、防錆処理された銅粉を得た(実施例9)。 [Method of rust prevention treatment]
After obtaining the copper powder of Example 4, it was dispersed in 100 mL of an aqueous benzotriazole solution (0.1 g / L) for rust prevention treatment, stirred at 500 rpm for 10 minutes with a rotating blade, filtered and dried (nitrogen atmosphere) (70 ° C. × 1 h), and a rust-proof copper powder was obtained (Example 9).
上記防錆処理された銅粉に対して、上述した実施例4と同様に評価を行って、その結果を、表1~3にまとめた。なお、表2における処理後の銅粉のサイズは、実施例9については、防錆処理後の銅粉のサイズであり、表3の各評価も、防錆処理した銅粉についての結果である。 [Evaluation of copper powder treated with rust prevention]
The copper powder subjected to the antirust treatment was evaluated in the same manner as in Example 4 described above, and the results are summarized in Tables 1 to 3. In addition, the size of the copper powder after the treatment in Table 2 is the size of the copper powder after the antirust treatment for Example 9, and each evaluation in Table 3 is also the result for the copper powder subjected to the antirust treatment. .
以下のように、微細な銅粉を製造し、さらに製造した銅粉をアミノシランによって表面処理して、本発明に係る、表面処理された銅粉を、湿式法による一貫製造を行った。 [Production example]
As described below, fine copper powder was produced, and the produced copper powder was surface-treated with aminosilane, and the surface-treated copper powder according to the present invention was subjected to integrated production by a wet method.
(2) 次に、希硫酸(25wt%)50 mLを一時に添加した。
(3) これを、回転羽で攪拌後(300rpm×10分)、60分放置した。
(4) 次に、沈殿に対して、洗浄を行った。
洗浄は、最初に、上澄み液を除去し、純水350 mLを加えて攪拌( 300rpm×10分)後、60分放置し、上澄み液を除去し、純水350 mLを加えて攪拌( 300rpm×10分)後、60分放置し、上澄み液を除去することによって行った。
(5) 次に、アミノシラン処理を行った。
アミノシラン処理は、アミノシラン水溶液(50mL)を加えて60分攪拌し、この際に、回転羽(300rpm)+超音波(株式会社テックジャム製、超音波洗浄器 3周波タイプ / W-113)(出力100W、周波数100kHz)の処理を、行った。これとは別に、回転羽のみ(300rpm)の処理、超音波のみの処理を別途行った。アミノシランとして、ジアミノシランA-1120(MOMENTIVE社製)、アミノシランA-1110(MOMENTIVE社製)を、それぞれ使用した。
(6) 次に、ろ過を行って、沈殿を分離した。
(7) 次に、分離した沈殿を、乾燥した。乾燥(70℃×2h)は、大気雰囲気での乾燥、及び窒素中で乾燥を、それぞれ行った。 (1) 50 g of cuprous oxide was added to 0.2 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.
For washing, first remove the supernatant, add 350 mL of pure water and stir (300 rpm × 10 minutes), then leave it for 60 minutes, remove the supernatant, add 350 mL of pure water and stir (300 rpm × 10 minutes) and then left for 60 minutes, and the supernatant was removed.
(5) Next, aminosilane treatment was performed.
For 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,
(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.
すでに上述した実施例に加えて、以下の実施例をあげて、本発明をさらに詳細に説明する。本発明は、以下の実施例に限定されるものではない。
[金属粉]
金属粉として、銅微粉、ニッケル粉、銀粉を以下の手順で用意した。 [Example]
In addition to the examples already described above, the present invention will be described in more detail with reference to the following examples. The present invention is not limited to the following examples.
[Metal powder]
As metal powder, copper fine powder, nickel powder, and silver powder were prepared in the following procedures.
・実施例15~17、比較例9
表面処理に供される銅粉20gを、上述した湿式法によって製造した。すなわち、
(1) アラビアゴム 0.4 g + 純水 350 mL に、亜酸化銅 50 g を添加した。
(2) 次に、希硫酸(25wt%)50 mLを一時に添加した。
(3) これを、回転羽で攪拌後(300rpm×10分)、60分放置した。
(4) 次に、沈殿に対して、洗浄を行った。
洗浄は、最初に、上澄み液を除去し、純水350 mLを加えて攪拌( 300rpm×10分)後、60分放置し、上澄み液を除去し、純水350 mLを加えて攪拌( 300rpm×10分)後、60分放置し、銅微粉を沈降させた。この状態で粒度測定をレーザー回折式粒度分布測定(島津製作所SLAD-2100)で行い、表面処理前の粒度測定とした。
得られた銅粉の粒子サイズ(D50、Dmax)を表3に示す。測定は、レーザー回折式粒度分布測定装置(島津製作所製SALD-2100)を使用した。 (Copper fine powder)
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.
For washing, first remove the supernatant, add 350 mL of pure water and stir (300 rpm × 10 minutes), then leave it for 60 minutes, remove the supernatant, add 350 mL of pure water and stir (300 rpm × 10 minutes), and then left for 60 minutes to allow the copper fine powder to settle. In this state, particle size measurement was performed by laser diffraction particle size distribution measurement (Shimadzu SLAD-2100), and particle size measurement before surface treatment was performed.
Table 3 shows the particle size (D50, Dmax) of the obtained copper powder. For the measurement, a laser diffraction particle size distribution measuring device (SALD-2100 manufactured by Shimadzu Corporation) was used.
特許第4164009号公報に従い、化学還元法によって銅粉を得た。すなわち、アラビアゴム2gを2900mLの純水に添加した後、硫酸銅125gを添加し撹拌しながら、80%ヒドラジン一水和物を360mL添加した。ヒドラジン一水和物の添加後~3時間かけて室温から60℃に昇温し、更に3時間かけて酸化銅を反応させた。反応終了後、得られたスラリーをヌッチェでろ過し、次いで純水及びメタノールで洗浄し、更に乾燥させて銅粉を得た。この銅粉と実施例1の手順でジアミノシランカップリング剤水溶液とを混合し、表面処理銀粉を得た。この特性を実施例1の手順で評価した。 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.
ニッケル粉は東邦チタニウム製のNF32(D50 0.3μm)を用いた。 (Nickel powder)
As the nickel powder, NF32 (D50 0.3 μm) manufactured by Toho Titanium was used.
特開2007-291513に従って製粉した。すなわち、0.8Lの純水に硝酸銀12.6gを溶解させ、25%アンモニア水を24mL,さらに硝酸アンモニウムを40g添加し、銀アンミン錯塩水溶液を調整した。これに1g/Lの割合でゼラチンを添加し、これを電解液とし、陽極、陰極ともにDSE極板を使用し、電流密度200A/m2、溶液温度20℃で電解し、電析した銀粒子を局番から掻き落としながら1時間電解した。こうして得られた銀粉をヌッチェでろ過し、純水、アルコールの順に洗浄を行い、70℃で12時間大気雰囲気下で乾燥させた。この銀粉を乾式分級し、最終的にD50 0.1μm、Dmax 0.5μmの銀粉を得た。 (Silver powder)
Milling according to JP 2007-291513 A. That is, 12.6 g of silver nitrate was dissolved in 0.8 L of pure water, 24 mL of 25% aqueous ammonia and 40 g of ammonium nitrate were added to prepare a silver ammine complex salt aqueous solution. Gelatin was added to this at a rate of 1 g / L, and this was used as an electrolytic solution. Both anode and cathode were DSE plates, electrolyzed at a current density of 200 A / m 2 and a solution temperature of 20 ° C. Electrolysis was performed for 1 hour while scraping off the area code. 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 μm and a Dmax of 0.5 μm.
次の各種のシランを使用したシラン水溶液をそれぞれ50ml調製した。
シラン:ジアミノシランA-1120(MOMENTIVE社製)
メチルトリメトキシシランKBM-13(信越シリコーン社製)
チタネート:アミノ基含有 プレインアクト KR44(味の素ファインテクノ社製)
アミノ基非含有 プレインアクト KR TTS (味の素ファインテクノ社製)
濃度は1~10vol%の範囲で調製した。また、アミノ系カップリング剤以外は希硫酸でpHを4に調整した。 (Preparation of coupling agent aqueous solution)
50 ml of an aqueous silane solution using the following various silanes was prepared.
Silane: Diaminosilane A-1120 (made by MOMENTIVE)
Methyltrimethoxysilane KBM-13 (manufactured by Shin-Etsu Silicone)
Titanate: Amino group-containing plain act KR44 (manufactured by Ajinomoto Fine Techno Co., Ltd.)
Amino group-free plain act KR TTS (Ajinomoto Fine Techno Co., Ltd.)
The concentration was adjusted in the range of 1 to 10 vol%. Further, the pH was adjusted to 4 with dilute sulfuric acid except for the amino coupling agent.
ジアミノシランA-1120:
H2N-C2H4-NH-C3H6-Si(OCH3)3
メチルトリメトキシシランKBM-13:
H3C-Si(OCH3)3
アミノ基含有 プレインアクト KR44
疎水基の側鎖有機官能基
(CH3)2CH-O-
親水基の側鎖有機官能基
-O-(C2H4)-NH-(C2H4)-NH2
アミノ基非含有 プレインアクト KR TTS
疎水基の側鎖有機官能基
(CH3)2CH-O-
親水基の側鎖有機官能基
-O-CO-(C17H35) The structural formulas of various silanes are as follows.
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 )
上記(銅微粉)の手順で得られた銅微粉スラリーから上澄み液を除去し、銅微粉を乾燥させることなく、上記(カップリング剤水溶液の調製)で調整したカップリング剤と60分間、以下のいずれかの方法で混合させた(実施例15~17、比較例9)。
(1)回転羽(300rpm)+超音波(株式会社テックジャム製、超音波洗浄器 3周波タイプ / W-113)(出力100W、周波数100kHz)
(2)回転羽(300rpm)のみ
(3)超音波のみ
次にこれらのカップリング剤水溶液をそれぞれアスピレーターで吸引ろ過したのち、銅微粉の上に純水350mLを加え、さらにろ過した。これを窒素雰囲気下で70℃で1時間乾燥し、乳鉢で粉砕した。この状態で再度粒度測定を行った。
実施例10については、上記(銅微粉)に記載の通りとして、上述の(1)の手順で表面処理を行った。
上記(ニッケル粉)で得られたニッケル粉、上記(銀粉)の手順で得られた銀粉については、上記(カップリング剤水溶液の調製)で調整したカップリング剤と60分間、上述の(1)の手順で混合させて、表面処理を行った(実施例11~14及び18~23、比較例6、8,10、11)。
得られた結果を、次の表4~6に示す。 (surface treatment)
Supernatant liquid is removed from the copper fine powder slurry obtained by the above procedure (copper fine powder), and the copper agent is dried and the coupling agent prepared in the above (preparation of aqueous coupling agent solution) for 60 minutes. They were mixed by any method (Examples 15 to 17, Comparative Example 9).
(1) Rotating feather (300 rpm) + Ultrasound (manufactured by Techjam Co., Ltd., ultrasonic cleaner 3 frequency type / W-113) (output 100W, frequency 100kHz)
(2) Only rotating blades (300 rpm) (3) Only ultrasonic waves Next, each of these aqueous coupling agent solutions was suction filtered with an aspirator, and then 350 mL of pure water was added onto the copper fine powder, followed by further filtration. This was dried at 70 ° C. for 1 hour under a nitrogen atmosphere and pulverized in a mortar. In this state, the particle size was measured again.
About Example 10, as the above-mentioned (copper fine powder), surface treatment was performed in the above-mentioned procedure (1).
For the nickel powder obtained in the above (nickel powder) and the silver powder obtained in the above procedure (silver powder), the coupling agent prepared in the above (preparation of aqueous coupling agent solution) and 60 minutes above (1) The surface treatment was carried out by mixing in the procedure (Examples 11 to 14 and 18 to 23, Comparative Examples 6, 8, 10, and 11).
The results obtained are shown in the following Tables 4-6.
Claims (53)
- Si、Ti、Al、Zr、Ce、Snのうちいずれか1種以上の付着量が金属粉1gに対して200~16000μg、金属粉に対するNの重量%が0.02%以上である、表面処理された金属粉。 Surface treatment in which the adhesion amount of any one or more of Si, Ti, Al, Zr, Ce, and Sn is 200 to 16000 μg with respect to 1 g of metal powder, and the weight percentage of N with respect to metal powder is 0.02% or more. Metal powder.
- 金属粉が、Pt、Pd、Ag、Ni、Cuのいずれかの金属粉である、請求項1に記載の金属粉。 The metal powder according to claim 1, wherein the metal powder is any one of Pt, Pd, Ag, Ni, and Cu.
- 金属粉が、銅粉である、請求項1に記載の金属粉。 The metal powder according to claim 1, wherein the metal powder is a copper powder.
- 金属粉が、Pt、Pd、Ag、Niのいずれかの金属粉である、請求項1に記載の金属粉。 The metal powder according to claim 1, wherein the metal powder is any one of Pt, Pd, Ag, and Ni.
- Si、Ti、Al、Zr、Ce、Snのうちいずれか1種以上の付着量が金属粉1gに対して300~16000μgである、請求項1~4のいずれかに記載の金属粉。 The metal powder according to any one of claims 1 to 4, wherein the adhesion amount of any one or more of Si, Ti, Al, Zr, Ce, and Sn is 300 to 16000 μg with respect to 1 g of the metal powder.
- Si、Ti、Al、Zr、Ce、Snのうちいずれか1種以上の付着量が金属粉1gに対して500~16000μgである、請求項1~4のいずれかに記載の金属粉。 The metal powder according to any one of claims 1 to 4, wherein the adhesion amount of any one or more of Si, Ti, Al, Zr, Ce, and Sn is 500 to 16000 µg with respect to 1 g of the metal powder.
- Si、Ti、Al、Zr、Ce、Snのうちいずれか1種以上の付着量が金属粉1gに対して3000μg以下である、請求項1~6のいずれかに記載の金属粉。 The metal powder according to any one of claims 1 to 6, wherein the adhesion amount of any one or more of Si, Ti, Al, Zr, Ce, and Sn is 3000 µg or less with respect to 1 g of the metal powder.
- Si、Ti、Al、Zr、Ce、Snのうちいずれか1種以上の付着量が金属粉1gに対して1500μg以下である、請求項1~6のいずれかに記載の金属粉。 The metal powder according to any one of claims 1 to 6, wherein the adhesion amount of at least one of Si, Ti, Al, Zr, Ce, and Sn is 1500 µg or less with respect to 1 g of the metal powder.
- 金属粉に対するNの重量%が0.05%以上である、請求項1~8のいずれかに記載の金属粉。 The metal powder according to any one of claims 1 to 8, wherein the weight percentage of N with respect to the metal powder is 0.05% or more.
- Si、Ti、Al、Zr、Ce、Snのうちいずれか1種以上が、Ti、Al、Zr、Ce、Snのうちいずれか1種以上である、請求項1~9のいずれかに記載の金属粉。 10. One or more of Si, Ti, Al, Zr, Ce, and Sn are any one or more of Ti, Al, Zr, Ce, and Sn. Metal powder.
- Si、Ti、Al、Zr、Ce、Snのうちいずれか1種以上が、Siである、請求項1~9のいずれかに記載の金属粉。 The metal powder according to any one of claims 1 to 9, wherein at least one of Si, Ti, Al, Zr, Ce, and Sn is Si.
- 金属粉が銅粉であり、Siの付着量が銅粉1gに対して500~16000μg、銅粉に対するNの重量%が0.05%以上である、請求項1に記載の金属粉。 The metal powder according to claim 1, wherein the metal powder is a copper powder, the amount of Si deposited is 500 to 16000 μg with respect to 1 g of the copper powder, and the weight percentage of N with respect to the copper powder is 0.05% or more.
- 金属粉が銅粉であり、Siの付着量が銅粉1gに対して500~3000μg、銅粉に対するNの重量%が0.05%以上である、請求項1に記載の金属粉。 The metal powder according to claim 1, wherein the metal powder is copper powder, the amount of Si deposited is 500 to 3000 µg with respect to 1 g of copper powder, and the weight percentage of N with respect to copper powder is 0.05% or more.
- 金属粉が、カップリング剤で表面処理された金属粉である、請求項1~13のいずれかに記載の金属粉。 The metal powder according to any one of claims 1 to 13, wherein the metal powder is a metal powder surface-treated with a coupling agent.
- Si、Ti、Al、Zr、Ce、Snのうちいずれか1種以上が、カップリング剤処理で吸着された、請求項1~14のいずれかに記載の金属粉。 The metal powder according to any one of claims 1 to 14, wherein at least one of Si, Ti, Al, Zr, Ce, and Sn is adsorbed by a coupling agent treatment.
- カップリング剤がシラン、チタネート、アルミネートのいずれかである、請求項1~15のいずれかに記載の金属粉。 The metal powder according to any one of claims 1 to 15, wherein the coupling agent is any one of silane, titanate, and aluminate.
- カップリング剤が末端がアミノ基であるカップリング剤である、請求項1~16のいずれかに記載の金属粉。 The metal powder according to any one of claims 1 to 16, wherein the coupling agent is a coupling agent having a terminal amino group.
- カップリング剤がアミノシランである、請求項1~17のいずれかに記載の金属粉。 The metal powder according to any one of claims 1 to 17, wherein the coupling agent is aminosilane.
- 焼結開始温度が400℃以上である、請求項1~18のいずれかに記載の金属粉。 The metal powder according to any one of claims 1 to 18, wherein a sintering start temperature is 400 ° C or higher.
- アミノシランが、モノアミノシラン又はジアミノシランである、請求項18に記載の金属粉。 The metal powder according to claim 18, wherein the aminosilane is monoaminosilane or diaminosilane.
- 請求項1~20のいずれかに記載の金属粉が、さらに有機化合物で表面処理されてなる、表面処理された金属粉。 A surface-treated metal powder, wherein the metal powder according to any one of claims 1 to 20 is further surface-treated with an organic compound.
- 金属粉が、Pt、Pd、Ag、Niのいずれかの金属粉であり、Si、Ti、Al、Zr、Ce、Snのうちいずれか1種以上の付着量がCu以外の金属粉1gに対して200~1500μg、Cu以外の金属粉に対するNの重量%が0.02%以上であり、焼結開始温度が400℃以上である、請求項1に記載の金属粉。 The metal powder is a metal powder of any one of Pt, Pd, Ag, and Ni, and the amount of adhesion of one or more of Si, Ti, Al, Zr, Ce, and Sn is 1 g of metal powder other than Cu. The metal powder according to claim 1, wherein the weight percentage of N with respect to a metal powder other than Cu is from 200 to 1500 μg, 0.02% or more, and the sintering start temperature is 400 ° C. or more.
- 請求項1~22のいずれかに記載の金属粉を使用した導電性金属粉ペースト。 A conductive metal powder paste using the metal powder according to any one of claims 1 to 22.
- 請求項23に記載の導電性金属ペーストが塗布されて加熱焼成されてなる、電極であって、
電極断面に最大径0.5μm以上のSiO2、TiO2、Al2O3が0.5個/μm2以下で存在している、電極。 An electrode obtained by applying the conductive metal paste according to claim 23 and baking it.
An electrode in which SiO 2, TiO 2 , and Al 2 O 3 having a maximum diameter of 0.5 μm or more are present on the electrode cross section at 0.5 pieces / μm 2 or less. - 請求項23のペーストを使用して製造されたチップ積層セラミックコンデンサー。 A chip multilayer ceramic capacitor manufactured using the paste of claim 23.
- 内部電極断面に直径が10nm以上のSiO2、TiO2、又はAl2O3が存在している、請求項25に記載のチップ積層セラミックコンデンサー。 26. The chip multilayer ceramic capacitor according to claim 25, wherein SiO 2 , TiO 2 , or Al 2 O 3 having a diameter of 10 nm or more is present in a cross section of the internal electrode.
- 内部電極断面に最大径0.5μm以上のSiO2、TiO2、又はAl2O3が0.5個/μm2以下で存在している、請求項25又は請求項26に記載のチップ積層セラミックコンデンサー。 27. The chip multilayer ceramic according to claim 25 or 26, wherein SiO 2 , TiO 2 , or Al 2 O 3 having a maximum diameter of 0.5 μm or more is present at 0.5 pieces / μm 2 or less in a cross section of the internal electrode. condenser.
- 請求項25~27のいずれかに記載のチップ積層セラミックコンデンサーを最外層に実装した多層基板。 A multilayer board on which the chip multilayer ceramic capacitor according to any one of claims 25 to 27 is mounted on an outermost layer.
- 請求項25~27のいずれかに記載のチップ積層セラミックコンデンサーを内層に実装した多層基板。 A multilayer board on which the chip multilayer ceramic capacitor according to any one of claims 25 to 27 is mounted on an inner layer.
- 請求項28又は請求項29に記載の多層基板を搭載した電子部品。 An electronic component on which the multilayer substrate according to claim 28 or 29 is mounted.
- 金属粉を、カップリング剤水溶液と混合して、金属粉分散液を調製する工程、
を含む、表面処理された金属粉を製造する方法。 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: - 金属粉が、Pt、Pd、Ag、Ni、Cuのいずれかの金属粉である、請求項31に記載の方法。 32. The method according to claim 31, wherein the metal powder is any one of Pt, Pd, Ag, Ni, and Cu.
- 金属粉が、銅粉である、請求項31に記載の方法。 32. The method according to claim 31, wherein the metal powder is copper powder.
- 金属粉が、Pt、Pd、Ag、Niのいずれかの金属粉である、請求項31に記載の方法。 32. The method according to claim 31, wherein the metal powder is any one of Pt, Pd, Ag, and Ni.
- 金属粉分散液を撹拌する工程を含む、請求項31~34のいずれかに記載の方法。 The method according to any one of claims 31 to 34, comprising a step of stirring the metal powder dispersion.
- 金属粉分散液を超音波処理する工程を含む、請求項31~35のいずれかに記載の方法。 The method according to any one of claims 31 to 35, comprising a step of ultrasonicating the metal powder dispersion.
- 超音波処理する工程が、1~180分間の超音波処理を行う工程である、請求項31~36のいずれかに記載の方法。 The method according to any one of claims 31 to 36, wherein the sonication step is a sonication step of 1 to 180 minutes.
- 金属粉分散液をろ過して銅粉を回収する工程、
ろ過して回収された銅粉を乾燥して、表面処理された金属粉を得る工程、
を含む、請求項31~37のいずれかに記載の方法。 A step of collecting the copper powder by filtering the metal powder dispersion,
Drying the copper powder recovered by filtration to obtain a surface-treated metal powder,
The method according to any of claims 31 to 37, comprising: - 乾燥が、酸素雰囲気又は不活性雰囲気下で行われる、請求項38に記載の方法。 The method according to claim 38, wherein the drying is performed in an oxygen atmosphere or an inert atmosphere.
- 金属粉分散液が、金属粉1gに対してカップリング剤0.025g以上を含んでいる、請求項31~39のいずれかに記載の方法。 The method according to any one of claims 31 to 39, wherein the metal powder dispersion contains 0.025 g or more of a coupling agent with respect to 1 g of the metal powder.
- カップリング剤水溶液が、次の式I:
H2N-R1-Si(OR2)2(R3) (式I)
(ただし、上記式Iにおいて、
R1は、直鎖状又は分枝を有する、飽和又は不飽和の、置換又は非置換の、環式又は非環式の、複素環を有する又は複素環を有しない、C1~C12の炭化水素の二価基であり、
R2は、C1~C5のアルキル基であり、
R3は、C1~C5のアルキル基、又はC1~C5のアルコキシ基である。)
で表されるアミノシランの水溶液である、請求項31~40のいずれかに記載の方法。 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. )
The method according to any one of claims 31 to 40, which is an aqueous solution of aminosilane represented by: - R1が、 -(CH2)n-、-(CH2)n-(CH)m-(CH2)j-1-、-(CH2)n-(CC)-(CH2)n-1-、-(CH2)n-NH-(CH2)m-、-(CH2)n-NH-(CH2)m-NH-(CH2)j-、-(CH2)n-1-(CH)NH2-(CH2)m-1-、-(CH2)n-1-(CH)NH2-(CH2)m-1-NH-(CH2)j- からなる群から選択された基である(ただし、n、m、jは、1以上の整数である)、請求項41に記載の方法。 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- 42. The method of claim 41, wherein n, m, j are integers greater than or equal to 1.
- カップリング剤水溶液が、次の式II:
(H2N-R1-O)pTi(OR2)q (式II)
(ただし、上記式IIにおいて、
R1は、直鎖状又は分枝を有する、飽和又は不飽和の、置換又は非置換の、環式又は非環式の、複素環を有する又は複素環を有しない、C1~C12の炭化水素の二価基であり、
R2は、直鎖状又は分枝を有する、C1~C5のアルキル基であり、
p及びqは、1~3の整数であり、p+q=4である。)
で表されるアミノ基含有チタネートの水溶液である、請求項31~40のいずれかに記載の方法。 An aqueous coupling agent solution has the following formula II:
(H 2 N—R 1 —O) p Ti (OR 2 ) q (Formula II)
(However, in the above formula II,
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 linear or branched C1-C5 alkyl group,
p and q are integers of 1 to 3, and p + q = 4. )
The method according to any one of claims 31 to 40, which is an aqueous solution of an amino group-containing titanate represented by: - R1が、 -(CH2)n-、-(CH2)n-(CH)m-(CH2)j-1-、-(CH2)n-(CC)-(CH2)n-1-、-(CH2)n-NH-(CH2)m-、-(CH2)n-NH-(CH2)m-NH-(CH2)j-、-(CH2)n-1-(CH)NH2-(CH2)m-1-、-(CH2)n-1-(CH)NH2-(CH2)m-1-NH-(CH2)j- からなる群から選択された基である(ただし、n、m、jは、1以上の整数である)、請求項43に記載の方法。 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- 44. The method of claim 43, wherein n, m, j are integers greater than or equal to 1.
- 金属粉が、湿式法によって製造された銅粉である、請求項31~44のいずれかに記載の方法。 The method according to any one of claims 31 to 44, wherein the metal powder is a copper powder produced by a wet method.
- 請求項31~45のいずれかに記載の製造方法によって製造された表面処理された金属粉を、溶媒及び/又はバインダーと配合して、導電性金属粉ペーストを製造する方法。 A method for producing a conductive metal powder paste by blending the surface-treated metal powder produced by the production method according to any of claims 31 to 45 with a solvent and / or a binder.
- 請求項31~45のいずれかに記載の製造方法によって製造された表面処理された金属粉を、溶媒及び/又はバインダーと配合して、導電性金属粉ペーストを得る工程、
導電性金属粉ペーストを基材に塗布する工程、
基材に塗布された導電性金属粉ペーストを加熱焼成する工程、
を含む、電極を製造する方法。 A step of blending the surface-treated metal powder produced by the production method according to any one of claims 31 to 45 with a solvent and / or a binder to obtain a conductive metal powder paste;
Applying a conductive metal powder paste to a substrate;
A step of heating and firing the conductive metal powder paste applied to the substrate;
A method of manufacturing an electrode comprising: - 請求項31~45のいずれかに記載の製造方法によって製造された、表面処理された金属粉。 A surface-treated metal powder produced by the production method according to any one of claims 31 to 45.
- 請求項46に記載の製造方法によって製造された、導電性金属粉ペースト。 A conductive metal powder paste produced by the production method according to claim 46.
- 請求項47に記載の製造方法によって製造された、電極。 An electrode manufactured by the manufacturing method according to claim 47.
- 請求項31~45のいずれかに記載の製造方法によって製造された、表面処理された金属粉であって、
Si、Ti、Alのいずれかの付着量が金属粉1gに対して200~16000μgであり、
金属粉に対するNの重量%が0.02%以上であり、
焼結開始温度が400℃以上である、金属粉。 A surface-treated metal powder produced by the production method according to any one of claims 31 to 45,
The adhesion amount of any one of Si, Ti and Al is 200 to 16000 μg with respect to 1 g of metal powder,
% By weight of N to metal powder is 0.02% or more,
Metal powder having a sintering start temperature of 400 ° C or higher. - 請求項51に記載の表面処理された金属粉が、配合されてなる、導電性金属粉ペースト。 An electroconductive metal powder paste obtained by blending the surface-treated metal powder according to claim 51.
- 請求項51に記載の導電性金属粉ペーストが塗布されて加熱焼成されてなる、電極であって、
電極断面に最大径0.5μm以上のSiO2、TiO2、又はAl2O3が0.5個/μm2以下で存在している、電極。 An electrode obtained by applying the conductive metal powder paste according to claim 51 and baking it,
An electrode in which SiO 2 , TiO 2 , or Al 2 O 3 having a maximum diameter of 0.5 μm or more is present at 0.5 pieces / μm 2 or less in the electrode cross section.
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