CN104115237A - Metal powder paste and method for producing same - Google Patents

Metal powder paste and method for producing same Download PDF

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Publication number
CN104115237A
CN104115237A CN201380010167.XA CN201380010167A CN104115237A CN 104115237 A CN104115237 A CN 104115237A CN 201380010167 A CN201380010167 A CN 201380010167A CN 104115237 A CN104115237 A CN 104115237A
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metal powder
paste
acid
copper powder
powder
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CN104115237B (en
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古泽秀树
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JX Nippon Mining and Metals Corp
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JX Nippon Mining and Metals Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/14—Conductive material dispersed in non-conductive inorganic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • 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
    • B22F1/16—Metallic particles coated with a non-metal
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • 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
    • H01G4/005—Electrodes
    • H01G4/008—Selection of materials
    • H01G4/0085—Fried electrodes
    • 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
    • H01G4/018—Dielectrics
    • H01G4/06—Solid dielectrics
    • H01G4/08—Inorganic dielectrics
    • H01G4/12—Ceramic dielectrics
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/30—Stacked capacitors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/102—Metallic powder coated with organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/10—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/15—Nickel or cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/25—Noble metals, i.e. Ag Au, Ir, Os, Pd, Pt, Rh, Ru

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Physics & Mathematics (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Conductive Materials (AREA)
  • Powder Metallurgy (AREA)
  • Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
  • Manufacturing Of Electric Cables (AREA)
  • Ceramic Capacitors (AREA)

Abstract

Provided are a surface-treated metal powder paste which can be suitably used for producing an electrode for a multilayer ceramic chip capacitor and has excellent sintering delaying properties, and a method for producing the same. The present invention is provided by a metal powder paste which comprises: a surface-treated metal powder in which the adhesion amount of at least one of Si, Ti, Al, Zr, Ce and Sn is 200 to 16000 [mu]g with respect to 1 g of metal powder and N is 0.02% or greater in wt% with respect to the metal powder; and an organic substance having a carboxyl group, the surface-treated metal powder and the organic substance being dispersed in a solvent.

Description

Metal powder is stuck with paste and manufacture method
Technical field
The present invention relates to be suitable for manufacturing metal powder paste and the manufacture method thereof of paster multi-layer ceramic capacitor electrode.
Background technology
Paster multi-layer ceramic capacitor is due to the such feature of small-size high-capacity, because of but the electronic unit that uses in a lot of electronic equipments.Paster multi-layer ceramic capacitor is formed as ceramic dielectric and interior electrode layer to be stacked as stratiform structure it is integrated and that obtain, each layer of lamination forms respectively capacitor element, utilize outer electrode that these elements are connected with electric parallel way, form as a whole a small-sized and jumbo capacitor.
In the manufacture of paster multi-layer ceramic capacitor, manufacture as follows dielectric.That is, first, to BaTiO 3deng the organic bond and the solvent that add in dielectric material powder as dispersant, shaping assistant, through pulverizing, mixing, deaeration operation, obtain slurry.Then, utilize the rubbing methods such as mould Tu Fa, by slurry coating thin spreading in the carrier film such as PET film.Be dried, obtain thin dielectric piece (raw cook (green sheet)).
On the other hand, as the metal dust of the raw material of the internal electrode of paster multi-layer ceramic capacitor, same with the situation of dielectric material powder, through with the mixing of organic bond as dispersant, shaping assistant and solvent, deaeration operation, the copper powder that forms pulp-like is stuck with paste (copper paste).Mainly utilize silk screen print method to be printed on raw cook (dielectric piece) and above form internal electrode, after dry, peeled off the raw cook of printing from carrier film, by stacked such raw cook multilayer.
The raw cook of lamination is in the manner described above applied to the moulding pressure of several 10～number 100MPa and it is integrated, then cut into single paster.Then, use firing furnace sintering interior electrode layer, dielectric layer under the high temperature of 1000 DEG C of left and right.In the manner described above, can manufacture paster multi-layer ceramic capacitor.
For the internal electrode of such paster multi-layer ceramic capacitor, developing this technology at that time, use Pt, but considered from the viewpoint of cost, use Pd, Pd-Ag alloy, at present the main Ni that uses.But, in recent years, consider from the viewpoint of environment control, require gradually Ni to replace with Cu.In addition, if Ni is replaced with to Cu,, in principle, in high-frequency applications, can realize low inductance (inductance).In addition, Cu also has advantages of that cost is lower such compared with Ni.
On the other hand, be accompanied by the miniaturization of capacitor, exist the tendency of internal electrode thin layer, it is said that model of future generation becomes 1 μ m left and right.Therefore the internal electrode of, expecting use in copper powder paste uses the particle size of powder less.
, the fusing point of Cu is lower than Pt, Pd, Ni after all.And then, because causing surface area, the small particle diameter of the above-mentioned particle of expecting like that increases, cause melting point depression, and thus, in the time adopting Cu as internal electrode powder, in the time burning till, Cu powder starts melting at a lower temperature.This causes electrode layer self to produce crack (crack).In addition, after cooling, electrode layer sharply shrinks, and therefore, has the possibility of peeling off (delamination, delamination) that dielectric layer and electrode layer occur.For fear of such unfavorable condition, require internal electrode metal powder to have and the heat shrinkability characteristic of dielectric equal extent, as the index that represents this heat shrinkability characteristic, there is sintering to start temperature.
For such expecting, before this, to stick with paste for the copper powder that obtains the internal electrode that is applicable to paster multi-layer ceramic capacitor, the Cu powder that has proposed to use during copper powder is stuck with paste carries out surface-treated method.
No. 4001438th, patent documentation 1(Japan Patent) be following technology: Cu powder is distributed in liquid, add wherein the aqueous solution of the water soluble salt of metallic element, regulate pH, make metal oxide anchor at Cu powder surface, and then, these surface treatment copper powders are collided mutually, carry out the set of strengthening surface processing layer.But operation is adsorbed onto on copper powder by metal oxide and set strengthening forms, therefore, existing problems aspect productivity ratio.In addition, the particle diameter of copper powder becomes than 0.5 μ m more hour, and the metal oxide particle size of size and absorption approaches, and therefore envisions the absorption of oxide on copper powder and itself becomes difficulty.
No. 4164009th, patent documentation 2(Japan Patent) be the technology of using the silicone oil coating copper powder with specific functional group.But, due to oil and Cu powder are mixed, thus easily aggegation, existing problems aspect operability.In addition, the filtration while being difficult to carry out oil to separate with Cu powder, existing problems aspect operability.
No. 3646259th, patent documentation 3(Japan Patent) be by the alkoxy silane polycondensation being hydrolyzed, formation SiO at Copper Powder Surface ammonia catalyst 2the technology of gel coating film.But, when copper powder below being suitable for particle diameter 1 μ m, in order to prevent the NH as catalyst 3aggegation, must continuous adding, but the quality that depends on concrete interpolation operative skill is controlled in reaction, react to control very difficultly, has problems from the viewpoint of operability and productivity ratio.
Prior art document
Patent documentation
Patent documentation 1: No. 4001438 communique of Japan Patent
Patent documentation 2: No. 4164009 communique of Japan Patent
Patent documentation 3: No. 3646259 communique of Japan Patent.
Summary of the invention
Invent problem to be solved
As mentioned above, expecting manufacture, sintering retardance, operability and productivity ratio excellence, the copper powder that can be applied to suitably the internal electrode of paster multi-layer ceramic capacitor sticks with paste.
Therefore, the object of the invention is to, provide manufacture, sintering retardance excellence, the surface treated copper powder that can be applied to suitably paster multi-layer ceramic capacitor electrode to stick with paste and manufacture method.
For solving the means of problem
The inventor conducts in-depth research, and found that, by by copper powder and amino silane aqueous solution, make amino silane be adsorbed in Copper Powder Surface, thereby the aggegation after surface treatment does not occur, thus, can obtain the copper powder that sintering retardance improved unexpectedly and stick with paste, thereby complete the present invention.And then this copper powder is stuck with paste and coordinated aliphatic acid to obtain by surface treated copper powder is distributed to solvent time, by the cooperation of this aliphatic acid, the aggegation of surface treated copper powder is extremely reduced.These manufacturing operations are very simple, do not need the technical ability of height, operability excellence, productivity ratio excellence.In addition, for the copper powder based on surface treated copper powder obtaining is in the manner described above stuck with paste, even used the copper powder of the copper powder that particle is little to stick with paste, also show that high sintering starts temperature.And then, even in the time similarly the metal powder beyond copper powder being carried out to surface treatment, when the coupling agent beyond utilizing amino silane carries out surface treatment, also can similarly obtain the surface treated metal powder of excellent, hence one can see that, and the metal powder that can obtain excellent specific property is stuck with paste.
Therefore, the invention reside in following (1)～(36).
（1）
Copper powder is stuck with paste, and it disperses and contains in solvent:
Surface treated copper powder, wherein the adhesion amount of Si is to be 500～16000 μ g with respect to copper powder 1g, N is more than 0.05% with respect to the % by weight of copper powder, and
There is the organic substance of carboxyl.
（2）
(1) described copper powder is stuck with paste, and it disperses and contains in solvent:
Surface treated copper powder, wherein the adhesion amount of Si is to be 500～16000 μ g with respect to copper powder 1g, N is more than 0.05% with respect to the % by weight of copper powder, and
There is the organic substance of carboxyl.
（3）
(1) or (2) described copper powder stick with paste, wherein, except surface treated copper powder with have the organic substance of carboxyl, it disperses and contains adhesive resin in solvent.
（4）
(1) copper powder in～(3) described in any one is stuck with paste, and wherein, surface treated copper powder is to carry out surface-treated copper powder with silane coupler.
（5）
(4) described copper powder is stuck with paste, and wherein, silane coupler is amino silane.
（6）
(1) copper powder in～(5) described in any one is stuck with paste, wherein, in surface treated copper powder, N with respect to the % by weight of copper powder in 0.05%～0.50% scope.
（7）
(1) copper powder in～(6) described in any one is stuck with paste, and wherein, surface treated copper powder is that surface treated copper powder is further heat-treated and removed the copper powder of N.
（8）
(1) copper powder in～(7) described in any one is stuck with paste, and wherein, surface treated copper powder is under oxygen atmosphere or inert atmosphere, to heat-treat and removed the copper powder of N.
（9）
(1) copper powder in～(8) described in any one is stuck with paste, and wherein, it is more than 400 DEG C that sintering starts temperature.
（10）
(1) copper powder in～(9) described in any one is stuck with paste, and wherein, surface treated copper powder is dried and solidifies and obtains after the aqueous solution of amino silane and copper powder are mixed, stirred.
（11）
(1) copper powder in～(10) described in any one is stuck with paste, and wherein, surface treated copper powder is to be to be under condition more than 0.01 mL, to have carried out surface-treated copper powder with respect to copper powder 1g for the amount of surface-treated amino silane.
（12）
(11) described copper powder is stuck with paste, and wherein, surface treated copper powder is to be more than 0.05mL in the amount of amino silane, is under following condition, to have carried out surface-treated copper powder in 30 minutes with the mixing of copper powder, mixing time.
（13）
(4) copper powder in～(11) described in any one is stuck with paste, and wherein, amino silane is mono amino silane or diamino silanes.
（14）
(1) copper powder in～(13) described in any one is stuck with paste, and wherein, surface treated copper powder is that the raw material copper powder obtaining utilizing damp process has carried out surface-treated copper powder.
（15）
(1) copper powder in～(14) described in any one is stuck with paste, and wherein, surface treated copper powder is D50≤1.5 μ m.
（16）
(1) copper powder in～(14) described in any one is stuck with paste, and wherein, surface treated copper powder is D50≤1.0 μ m.
（17）
(1) copper powder in～(14) described in any one is stuck with paste, and wherein, surface treated copper powder is D50≤0.5 μ m, Dmax≤1.0 μ m.
（18）
(1) copper powder in～(17) described in any one is stuck with paste, and wherein, the particle size distribution of surface treated copper powder is a crest.
（19）
(1) copper powder in～(18) described in any one is stuck with paste, and wherein, it is that internal electrode copper powder is stuck with paste that copper powder is stuck with paste.
（20）
(1) copper powder in～(18) described in any one is stuck with paste, and wherein, it is that outer electrode copper powder is stuck with paste that copper powder is stuck with paste.
（21）
(1) copper powder in～(20) described in any one is stuck with paste, and wherein, the organic substance with carboxyl is carboxylic acid or amino acid.
（22）
(1) copper powder in～(20) described in any one is stuck with paste, and wherein, the organic substance with carboxyl is aliphatic acid.
（23）
(22) described copper powder is stuck with paste, and wherein, aliphatic acid is the saturated or undersaturated aliphatic acid of C3～C24.
（24）
(22) described copper powder is stuck with paste, and wherein, aliphatic acid is that C3～C24, double key number are the aliphatic acid of 0～2.
（25）
(22) described copper powder is stuck with paste, wherein, aliphatic acid is to be selected from crotonic acid, acrylic acid, methacrylic acid, sad, n-nonanoic acid, capric acid, laurate, myristic acid, pentadecanoic acid, palmitic acid, palmitoleic acid, Heptadecanoic acide, stearic acid, oleic acid, vaccenic acid (vaccenic acid), linoleic acid, (9, 12, 15)-leukotrienes, (6, 9, 12)-leukotrienes, dihomo-gamma-linolenic acid, eleostearic acid, tuberlostearic acid, arachidic acid (arachic acid), 8, 11-eicosadienoic acid, 5, 8, 11-eicosatrienoic acid, arachidonic acid, behenic acid, lignoceric acid, nervonic acid, elaidic acid, sinapic acid, DHA, eicosapentaenoic acid, in parinaric acid more than a kind.
（26）
(22) described copper powder is stuck with paste, wherein, aliphatic acid be selected from stearic acid, oleic acid, linoleic acid more than a kind.
（27）
(1) copper powder in～(26) described in any one is stuck with paste, and wherein, solvent is alcoholic solvent, glycol ether solvent, acetic acid esters solvent, ketone solvent or hydrocarbon solvent.
（28）
(27) described copper powder is stuck with paste, wherein, alcoholic solvent be selected from terpineol, dihydro-terpineol, isopropyl alcohol, butyl carbitol, tyerpinyl ethoxy-ethanol, dihydro tyerpinyl ethoxy-ethanol more than a kind.
（29）
(27) described copper powder is stuck with paste, wherein, glycol ether solvent be selected from butyl carbitol more than a kind.
（30）
(27) described copper powder is stuck with paste, wherein, acetic acid esters solvent be selected from acetate of butyl carbitol, dihydro-terpineol acetic acid esters, terpineol acetic acid esters, acetic acid dihydro Pueraria lobota thread ester, acetic acid Pueraria lobota thread ester more than a kind.
（31）
(27) described copper powder is stuck with paste, and wherein, ketone solvent is methyl ethyl ketone.
（32）
(27) described copper powder is stuck with paste, wherein, hydrocarbon solvent be selected from toluene, cyclohexane more than a kind.
（33）
(1) copper powder in～(32) described in any one is stuck with paste, wherein, aliphatic acid with respect to the mass ratio (aliphatic acid/surface treated copper powder) of surface treated copper powder in 1/1000～1/10 scope.
（34）
(1) copper powder in～(33) described in any one is stuck with paste, wherein, aliphatic acid with respect to the mass ratio (aliphatic acid/solvent) of solvent in 1/100～1/10 scope.
（35）
(1) copper powder in～(34) described in any one is stuck with paste, wherein, solvent phase for the mass ratio (solvent/surface treated copper powder) of surface treated copper powder in 1/4～1/1 scope.
（36）
(1) copper powder in～(35) described in any one is stuck with paste, and wherein, utilizes aperture 5 μ m, effective area 9.0cm 2filter while carrying out the filtration under diminished pressure of 0.3atm, the quality seeing through was more than 35% with respect to the percentage (transmitance) of the ratio of the input quality of 4g after 30 seconds.
In addition, the present invention is also following (41)～(44).
（41）
Paster multi-layer ceramic capacitor, be use pasting described in any in (1)～(36) make and.
（42）
Multilager base plate, it is provided with the paster multi-layer ceramic capacitor (41) Suo Shu at outermost layer.
（43）
Multilager base plate, it is provided with (41) described paster multi-layer ceramic capacitor at internal layer.
（44）
Electronic unit, is equipped with (42) or (43) described multilager base plate.
In addition, the present invention is also following (51)～(59).
（51）
The manufacture method that copper powder is stuck with paste, comprises surface treated copper powder and the organic substance with carboxyl is dispersed in to the operation of preparing paste in solvent:
In described surface treated copper powder, the adhesion amount of Si is to be 500～16000 μ g with respect to copper powder 1g, and N is more than 0.05% with respect to the % by weight of copper powder.
（52）
(51) described method, wherein, the operation that preparation is stuck with paste is that following material is dispersed in to the operation of preparing paste in solvent:
Surface treated copper powder, wherein the adhesion amount of Si is to be 500～16000 μ g with respect to copper powder 1g, N is more than 0.05% with respect to the % by weight of copper powder, and
There is the organic substance of carboxyl.
（53）
(51) described method, wherein, the operation that preparation is stuck with paste is:
Except surface treated copper powder and having the organic substance of carboxyl, also adhesive resin is dispersed in to the operation that solvent is prepared paste.
（54）
(51) method in～(53) described in any one, wherein, the organic substance with carboxyl is aliphatic acid.
（55）
(51) method in～(54) described in any one, wherein, after the operation of sticking with paste in preparation, also comprises:
Filter the operation of the paste of preparing and obtain with filter.
（56）
(55) described method, wherein, filter has the aperture of 1～8 μ m.
（57）
(55) method or described in (56), wherein, the operation of filtering with filter utilizes filtration under diminished pressure or pressure filtration to carry out.
（58）
(57) described method, wherein, the pressure of filtration under diminished pressure is the pressure of the scope of 0.1～1.0atm.
（59）
(57) described method, wherein, the pressure of pressure filtration is the pressure of the scope of 0.1～2.0atm.
In addition, the present invention is also following (61)～(79).
（61）
(51) method in～(59) described in any one, wherein, surface treated copper powder is to utilize the surface treated copper powder of manufacturing the method manufacture of surface treated copper powder and obtain, described manufacture method comprises:
By copper powder and amino silane aqueous solution, prepare the operation of copper powder dispersion liquid.
（62）
(61) described method, wherein, comprises the operation that stirs copper powder dispersion liquid.
（63）
(61) method or described in (62), wherein, comprises the operation of copper powder dispersion liquid being carried out to ultrasonic wave processing.
（64）
(63) described method, wherein, the operation of carrying out ultrasonic wave processing is the operation of carrying out the ultrasonic wave processing of 1～180 minute.
（65）
(61) method in～(64) described in any one, wherein, comprising:
Copper powder dispersion liquid is filtered, reclaims the operation of copper powder,
The copper powder that filtration is recovered is dry, obtains the operation of surface treated copper powder.
（66）
(65) described method, wherein, is dryly undertaken by the heat treated of 30～120 minutes at 50～90 DEG C.
（67）
(65) method or described in (66), wherein, is dried under oxygen atmosphere or inert atmosphere and carries out.
（68）
(61) method in～(67) described in any one, wherein, in copper dispersion liquid, with respect to copper powder 1g, comprises amino silane more than 0.025g.
（69）
(61) method in～(68) described in any one, wherein, the amino silane aqueous solution is the aqueous solution of the amino silane that represents of following formula I.
H 2n-R 1-Si(OR 2) 2(R 3) (formula I)
(wherein, in above-mentioned formula I,
R1 be straight chain shape or have side chain, saturated or undersaturated, replacement or unsubstituted, ring type or non-ring type, there is heterocycle or do not there is the divalent group of hydrocarbon heterocycle, C1～C12,
R2 is the alkyl of C1～C5,
R3 is the alkyl of C1～C5 or the alkoxyl of C1～C5.）。
（70）
(69) described method, wherein, R1 is the divalent group that is selected from the straight chain shape saturated hydrocarbons of replacement or unsubstituted C1～C12, the divalent group of a chain saturated hydrocarbons of replacement or unsubstituted C1～C12, the divalent group of the straight chain shape unsaturated hydrocarbons of replacement or unsubstituted C1～C12, the divalent group of a chain unsaturated hydrocarbons of replacement or unsubstituted C1～C12, the divalent group of the ring type hydrocarbon of replacement or unsubstituted C1～C12, the divalent group of the hetero ring type hydrocarbon of replacement or unsubstituted C1～C12, group in the divalent group of the aromatic hydrocarbon of replacement or unsubstituted C1～C12.
（71）
(69) described method, wherein, R1 is be selected from-(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-in group (wherein, n, m, j are more than 1 integer).
（72）
(69) described method, wherein, R1 is-(CH 2) n-or-(CH 2) n-NH-(CH 2) m-.
（73）
(71) method in～(72) described in any one, wherein, n, m, j are 1,2 or 3 independently of one another.
（74）
(69) method in～(73) described in any one, wherein, R2 is methyl or ethyl.
（75）
(69) method in～(74) described in any one, wherein, R3 is methyl, ethyl, methoxy or ethoxy.
（76）
(61) method in～(75) described in any one, wherein, copper powder be utilize damp process manufacture and copper powder.
（77）
(61) method in～(76) described in any one, wherein,
In surface treated copper powder,
The adhesion amount of Si is to be 500～16000 μ g with respect to copper powder 1g,
N is more than 0.05% with respect to the % by weight of copper powder;
It is more than 400 DEG C that sintering starts temperature.
（78）
The method of manufacturing electrode, comprising:
The copper powder that will utilize the manufacture method manufacture described in any one in (51)～(57), (61)～(77) and obtain is stuck with paste the operation being applied on base material,
The conductivity copper being applied on base material is stuck with paste to the operation that heating is burnt till.
（79）
(78) described method, wherein, electrode is paster multi-layer ceramic capacitor electrode.
In addition, the present invention is also following (81)～(83).
（81）
Copper powder is stuck with paste, be utilize the manufacture method manufacture described in any one in (51)～(57), (61)～(77) and.
（82）
Electrode, be utilize (78) described manufacture method manufacture and.
（83）
Paster multi-layer ceramic capacitor electrode, be utilize (79) described manufacture method manufacture and.
In addition, the present invention is also following (91)～(92).
（91）
Copper powder is stuck with paste, be utilize the method manufacture described in any one in (51)～(57), (61)～(77) and copper powder stick with paste, wherein,
Utilize aperture 5 μ m, effective area 9.0cm 2filter while carrying out the filtration under diminished pressure of 0.3atm, the quality seeing through was more than 35% with respect to the percentage (transmitance) of the ratio of the input quality of 4g after 15 minutes.
（92）
Electrode, be utilize (78) or (79) described manufacture method manufacture and.
And then, the present invention be also following (101)～.
（101）
Metal powder is stuck with paste, and it disperses and contains in solvent:
Surface treated metal powder, wherein the above adhesion amount of any one in Si, Ti, Al, Zr, Ce, Sn is to be 200～16000 μ g with respect to metal powder 1g, N is more than 0.02% with respect to the % by weight of metal powder, and
There is the organic substance of carboxyl.
（102）
(101) described metal powder is stuck with paste, and wherein, except surface treated metal powder with have the organic substance of carboxyl, it disperses and contains adhesive resin in solvent.
（103）
(101) metal powder in～(102) described in any one is stuck with paste, and wherein, metal powder is copper powder.
（104）
(101) metal powder in～(102) described in any one is stuck with paste, and wherein, metal powder is any metal powder in Pt, Pd, Ag, Ni, Cu.
（105）
(101) metal powder in～(104) described in any one is stuck with paste, and wherein, any one the above adhesion amount in Si, Ti, Al, Zr, Ce, Sn is to be 300～16000 μ g with respect to metal powder 1g.
（106）
(101) metal powder in～(104) described in any one is stuck with paste, and wherein, any one the above adhesion amount in Si, Ti, Al, Zr, Ce, Sn is to be 500～16000 μ g with respect to metal powder 1g.
（107）
(101) metal powder in～(106) described in any one is stuck with paste, and wherein, any one the above adhesion amount in Si, Ti, Al, Zr, Ce, Sn is to be below 3000 μ g with respect to metal powder 1g.
（108）
(101) metal powder in～(106) described in any one is stuck with paste, and wherein, any one the above adhesion amount in Si, Ti, Al, Zr, Ce, Sn is to be below 1500 μ g with respect to metal powder 1g.
（109）
(101) the described metal powder in～(108) is stuck with paste, and wherein, N is more than 0.05% with respect to the % by weight of metal powder.
（110）
(101) metal powder in～(109) described in any one is stuck with paste, and wherein, any one in Si, Ti, Al, Zr, Ce, Sn is above is more than any one in Ti, Al, Zr, Ce, Sn.
（111）
(101) metal powder in～(109) described in any one is stuck with paste, and wherein, more than any one in Si, Ti, Al, Zr, Ce, Sn is Si.
（112）
(101) described metal powder is stuck with paste, and wherein, metal powder is copper powder, and the adhesion amount of Si is to be 500～16000 μ g with respect to copper 1g, and N is more than 0.05% with respect to the % by weight of copper powder.
（113）
(101) described metal powder is stuck with paste, and wherein, metal powder is copper powder, and the adhesion amount of Si is to be 500～3000 μ g with respect to copper 1g, and N is more than 0.05% with respect to the % by weight of copper powder.
（114）
(101) the described metal powder in～(113) is stuck with paste, and wherein, surface treated metal powder is with the surface-treated metal powder of coupling agent.
（115）
(101) the described metal powder in～(114) is stuck with paste, wherein, utilize coupling agent treatment and adsorb have Si, more than any one in Ti, Al, Zr, Ce, Sn.
（116）
(101) the described metal powder in～(115) is stuck with paste, and wherein, coupling agent is any in silane, titanate esters (titanate), Aluminate.
（117）
(101) the described metal powder in～(116) is stuck with paste, and wherein, coupling agent is that end is amino coupling agent.
（118）
(101) the described metal powder in～(117) is stuck with paste, and wherein, coupling agent is amino silane.
（119）
(101) metal powder in～(118) described in any one is stuck with paste, and wherein, the organic substance with carboxyl is carboxylic acid or amino acid.
（120）
(101) metal powder in～(119) described in any one is stuck with paste, and wherein, the organic substance with carboxyl is aliphatic acid.
（121）
(120) described metal powder is stuck with paste, and wherein, aliphatic acid is the saturated or undersaturated aliphatic acid of C3～C24.
（122）
(120) described metal powder is stuck with paste, and wherein, aliphatic acid is that the double key number of C3～C24 is the aliphatic acid of 0～2.
（123）
(120) described metal powder is stuck with paste, wherein, aliphatic acid is to be selected from crotonic acid, acrylic acid, methacrylic acid, sad, n-nonanoic acid, capric acid, laurate, myristic acid, pentadecanoic acid, palmitic acid, palmitoleic acid, Heptadecanoic acide, stearic acid, oleic acid, vaccenic acid, linoleic acid, (9, 12, 15)-leukotrienes, (6, 9, 12)-leukotrienes, dihomo-gamma-linolenic acid, eleostearic acid, tuberlostearic acid, arachidic acid (arachic acid), 8, 11-eicosadienoic acid, 5, 8, 11-eicosatrienoic acid, arachidonic acid, behenic acid, lignoceric acid, nervonic acid, elaidic acid, sinapic acid, DHA, eicosapentaenoic acid, in parinaric acid more than a kind.
（124）
(101) metal powder in～(123) described in any one is stuck with paste, and wherein, solvent is alcoholic solvent, glycol ether solvent, acetic acid esters solvent, ketone solvent or hydrocarbon solvent.
（125）
(119) metal powder in～(124) described in any one is stuck with paste, wherein, aliphatic acid with respect to the mass ratio (aliphatic acid/surface treated copper powder) of surface treated metal powder in 1/100～1/10 scope.
（126）
(119) metal powder in～(125) described in any one is stuck with paste, wherein, aliphatic acid with respect to the mass ratio (aliphatic acid/solvent) of solvent in 1/100～1/10 scope.
（127）
(101) metal powder in～(126) described in any one is stuck with paste, and wherein, utilizes aperture 5 μ m, effective area 9.0cm 2filter carry out the filtration under diminished pressure of 0.3atm, the quality seeing through was more than 35% with respect to the percentage (transmitance) of the ratio of the input quality of 4g after 30 seconds.
（128）
Paster multi-layer ceramic capacitor, be use the paste described in any in (101)～(127) and manufacture and.
（129）
(128) described paster multi-layer ceramic capacitor, wherein, on internal electrode section, having diameter is SiO more than 10nm 2, TiO 2, Al 2o 3in any.
（130）
Or (129) described paster multi-layer ceramic capacitor (128), wherein, on internal electrode section with 0.5/cm 2below having maximum diameter is SiO more than 0.5 μ m 2, TiO 2, Al 2o 3in any.
（131）
The manufacture method that metal powder is stuck with paste, wherein, comprises surface treated metal powder and the organic substance with carboxyl is dispersed in to the operation of preparing paste in solvent:
Any one above adhesion amount in described surface treated metal powder in Si, Ti, Al, Zr, Ce, Sn is to be 200～16000 μ g with respect to metal powder 1g, and N is more than 0.02% with respect to the % by weight of metal powder.
（132）
(131) described method, wherein, the operation that preparation is stuck with paste is:
Except surface treated metal powder with have the organic substance of carboxyl, also adhesive resin is dispersed in to the operation that solvent is prepared paste.
（133）
(131) method in～(132) described in any one, wherein, the organic substance with carboxyl is aliphatic acid.
（134）
(131) method in～(133) described in any one, wherein, after preparing the operation of paste, comprising in surface treated metal powder and aliphatic acid are distributed to solvent:
Filter the operation of the paste of preparing and obtain with filter.
（135）
(134) described method, wherein, filter has the aperture of 1～8 μ m.
（136）
(134) method or described in (135), wherein, the operation of filtering with filter is undertaken by filtration under diminished pressure or pressure filtration.
（137）
(131) method in～(136) described in any one, wherein, surface treated metal powder is to utilize the surface treated metal powder of manufacturing the method manufacture of surface treated metal powder and obtain, described manufacture method comprises:
By metal powder with there is amino coupling agent aqueous solution and mix, prepare the operation of metal powder dispersion liquid.
（138）
(137) described method, wherein, metal powder is any metal powder in Pt, Pd, Ag, Ni, Cu.
（139）
(137) described method, wherein, metal powder is copper powder.
（140）
(137) described method, wherein, metal powder is any metal powder in Pt, Pd, Ag, Ni.
（141）
(137) method in～(140) described in any one, wherein, comprises the operation that stirs metal powder dispersion liquid.
（142）
(137) method in～(141) described in any one, wherein, comprises the operation of metal powder dispersion liquid being carried out to ultrasonic wave processing.
（143）
(142) described method, wherein, the operation of carrying out ultrasonic wave processing is the operation of carrying out the ultrasonic wave processing of 1～180 minute.
（144）
(137) method in～(143) described in any one, comprising:
Metal powder dispersion liquid is filtered, reclaims the operation of metal powder,
The metal powder that filtration is recovered is dry, obtains the operation of surface treated metal powder.
（145）
(144) described method, wherein, is dried under oxygen atmosphere or inert atmosphere and carries out.
（146）
(137) method that～(145) are described, wherein, in metal dispersion, with respect to metal powder 1g, contains the amino coupling agent that has more than 0.025g.
（147）
(137) method in～(146) described in any one, wherein, the amino silane aqueous solution is the aqueous solution of the amino silane that represents of following formula I,
H 2n-R 1-Si(OR 2) 2(R 3) (formula I)
(wherein, in above-mentioned formula I,
R1 be straight chain shape there is side chain, saturated or undersaturated, replacement or unsubstituted, ring type or non-ring type, there is heterocycle or do not there is the divalent group of hydrocarbon heterocycle, C1～C12,
R2 is the alkyl of C1～C5,
R3 is the alkyl of C1～C5 or the alkoxyl of C1～C5.）。
（148）
(147) described method, wherein, R1 is be selected from-(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-in group (wherein, n, m, j are more than 1 integer).
（149）
(137) method in～(146) described in any one, wherein, coupling agent aqueous solution is the aqueous solution containing amino titanate esters that Formula Il represents,
(H 2n-R 1-O) pti(OR 2) q(formula II)
(wherein, in above-mentioned formula II,
R1 be straight chain shape there is side chain, saturated or undersaturated, replacement or unsubstituted, ring type or non-ring type, there is heterocycle or do not there is the divalent group of hydrocarbon heterocycle, C1～C12,
R2 is straight chain shape or the alkyl with side chain, C1～C5,
P and q are 1～3 integers, p+q=4.）。
（150）
(149) described method, wherein, R1 is be selected from-(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-in group (wherein, n, m, j are more than 1 integer).
（151）
(131) method in～(150) described in any one, wherein, metal powder be utilize damp process manufacture and metal powder.
（152）
(131) method in～(150) described in any one, wherein,
Surface treated metal powder is that any one the above adhesion amount in Si, Ti, Al, Zr, Ce, Sn is to be 200～16000 μ g with respect to metal powder 1g, and N is more than 0.02% surface treated metal powder with respect to the % by weight of copper powder,
It is more than 400 DEG C that sintering starts temperature.
（153）
Manufacture the method for electrode, comprise that the metal powder paste that will utilize the manufacture method manufacture described in any one in (131)～(152) and obtain is applied to the operation on base material,
The conductive metal being applied on base material is stuck with paste to the operation that heating is burnt till.
（154）
(153) described method, wherein, electrode is paster multi-layer ceramic capacitor electrode.
（155）
Metal powder is stuck with paste, be utilize the manufacture method manufacture described in any one in (131)～(152) and metal powder stick with paste, wherein,
Utilize aperture 5 μ m, effective area 9.0cm 2filter carry out the filtration under diminished pressure of 0.3atm, the quality seeing through was more than 35% with respect to the percentage (transmitance) of the ratio of the input quality of 4g after 15 minutes.
（156）
Electrode, be utilize (153) or (154) described manufacture method manufacture and electrode, wherein,
On electrode section with 0.5/cm 2below having maximum diameter is SiO more than 0.5 μ m 2, TiO 2, Al 2o 3in any.
[invention effect]
Even if the surface treated copper powder that the copper powder the present invention relates to uses in sticking with paste can aggegation after surface treatment yet, sintering retardance excellence, even the little copper powder of particle also shows that high sintering starts temperature.Therefore, the sintering retardance excellence that copper powder of the present invention is stuck with paste, the dispersiveness of the copper powder in paste is also excellent, therefore, can avoid the problem in the manufactures such as stripping electrode, advantageously carries out the manufacture of paster multi-layer ceramic capacitor electrode.In addition, for this surface treated copper powder, can carry out very simple processing to the copper powder as raw material manufactures, for the manufacture of sticking with paste for copper powder of the present invention, can carry out very simple processing to this surface treated copper powder manufactures, therefore, do not need superb technical ability, operability and productivity ratio excellence.In addition, by the present invention, for the metal powder beyond copper powder, also can similarly obtain having the metal powder paste of excellent characteristic.
[brief description of the drawings]
[Fig. 1] Fig. 1 is perpendicular to the TEM image of the surperficial section of surface treated copper powder.
Embodiment
Below enumerate execution mode and explain the present invention.The invention is not restricted to the following embodiment of enumerating.
In the present invention, carry out copper powder and amino silane aqueous solution, prepare the operation of copper powder dispersion liquid, by this copper powder dispersion liquid, can obtain surface treated copper powder, carry out the surface treated copper powder obtaining in the manner described above and the organic substance with carboxyl to be dispersed in the operation of preparing paste in solvent, can manufacture copper powder and stick with paste.
In a preferred embodiment, except surface treated copper powder and having the organic substance of carboxyl, also can, to dispersing binder resin in solvent, according to expectation, also can add other additives.
Specifically, surface treated copper powder can obtain according to the method for hereinafter explanation.From initial as the copper powder of raw material for surface-treated, this raw material copper powder is carried out to surface treatment, then it is distributed in solvent together with having the organic substance etc. of carboxyl, obtain copper powder and stick with paste, this is also within the scope of the invention.And then, from initial for the manufacture of surface-treated raw material copper powder, obtain copper powder and stick with paste, this is also within the scope of the invention.
In the present invention, as the organic substance with carboxyl, be preferably amino acid or carboxylic acid.As carboxylic acid, can enumerate for example aliphatic acid.As amino acid, can enumerate for example alanine, arginine, asparagine, aspartic acid, cysteine, glutamine, glutamic acid, glycine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine.In the present invention, as the organic substance with carboxyl, particularly preferably use aliphatic acid.
As the aliphatic acid using in the present invention, can enumerate carbon number is the saturated or undersaturated aliphatic acid of C3～C24.In a preferred embodiment, can use C3～C24, further preferably use C4～C22, further preferably use C8～C22, further preferably use C12～C22, further preferably use C16～C20, particularly preferably use the aliphatic acid of the carbon number of C18.In a preferred embodiment, can use double key number order is for example 0～4, for example 0～3, for example aliphatic acid of 0～2.Filter fast from the viewpoint of filter, particularly preferably double key number is the aliphatic acid of 1.In a preferred embodiment, as aliphatic acid, can use and there is oil loving aliphatic acid, as such aliphatic acid, can enumerate the aliphatic acid of for example above-mentioned carbon number.
In a preferred embodiment, as such aliphatic acid, can use and be selected from crotonic acid, acrylic acid, methacrylic acid, sad, n-nonanoic acid, capric acid, laurate, myristic acid, pentadecanoic acid, palmitic acid, palmitoleic acid, Heptadecanoic acide, stearic acid, oleic acid, vaccenic acid, linoleic acid, (9, 12, 15)-leukotrienes, (6, 9, 12)-leukotrienes, dihomo-gamma-linolenic acid, eleostearic acid, tuberlostearic acid, arachidic acid (arachic acid), 8, 11-eicosadienoic acid, 5, 8, 11-eicosatrienoic acid, arachidonic acid, behenic acid, lignoceric acid, nervonic acid, elaidic acid, sinapic acid, DHA, eicosapentaenoic acid, in parinaric acid more than a kind.In addition, in particularly preferred embodiments, as aliphatic acid, can use be selected from stearic acid, oleic acid, linoleic acid and acrylic acid, be preferably selected from stearic acid, oleic acid and linoleic acid more than a kind.As aliphatic acid, can use the salt of aliphatic acid, but in a preferred embodiment, aliphatic acid preferably uses aliphatic acid itself, instead of the salt of aliphatic acid.
For the solvent using in the present invention, can use the solvent using in sticking with paste for silk screen printing of electronic material, as such solvent, can enumerate for example alcoholic solvent, glycol ether solvent, acetic acid esters solvent, ketone solvent and hydrocarbon solvent.As alcoholic solvent, can enumerate for example terpineol, isopropyl alcohol, butyl carbitol.As terpineol, can enumerate α-terpineol, β-terpineol, γ-terpineol, particularly preferably α-terpineol.As glycol ether solvent, can enumerate for example butyl carbitol.As acetic acid esters solvent, can enumerate for example acetate of butyl carbitol.As ketone solvent, can enumerate for example methyl ethyl ketone.As hydrocarbon solvent, can enumerate for example toluene, cyclohexane.In a preferred embodiment, as solvent, can use be selected from terpineol, isopropyl alcohol, butyl carbitol, acetate of butyl carbitol, methyl ethyl ketone, toluene, cyclohexane more than a kind, can preferably use be selected from α-terpineol, butyl carbitol and acetate of butyl carbitol more than a kind.
For the copper powder the present invention relates to is stuck with paste, in a preferred embodiment, aliphatic acid can be for example 1/1000～1/10 scope, preferred 1/1000～1/20 scope with respect to the mass ratio (aliphatic acid/surface treated copper powder) of surface treated copper powder.In a preferred embodiment, aliphatic acid can be for example 1/100～1/10 scope, preferred 1/60～1/15 scope with respect to the mass ratio (aliphatic acid/solvent) of solvent.In a preferred embodiment, solvent phase can be for example 1/4～1/1 scope, preferred 1/3～1/1.5 scope for the mass ratio (solvent/surface treated copper powder) of surface treated copper powder.
As the adhesive using in the present invention, can use as long as improving with the adhesive of the adhesion of substrate, as such adhesive, can enumerate cellulose-based resin, epoxy is resin, acrylic resin.In a preferred embodiment, can use for example polyvinyl acetal resin, polyvinyl butyral resin, acrylate.
Surface treated copper powder, aliphatic acid etc. are distributed in solvent and operation that preparation is stuck with paste can utilize known process for dispersing to carry out, according to expectation, can stir, mixing, ultrasonic wave processing.In a preferred embodiment, can be add surface treated copper powder in solvent in, or before adding surface treated copper powder, in solvent, add aliphatic acid.
Of the present invention preferred embodiment in, also can the organic substance preferred fatty acid with carboxyl be directly adsorbed in after surface treated copper powder, then be distributed to the operation of making paste in solvent, but in order to make the treatability in aggegation, drying process good, preferably in surface treated copper powder is distributed to solvent and make in the operation of paste, add organic substance, the preferred fatty acid with carboxyl simultaneously, it is adsorbed onto on copper powder.
Of the present invention preferred embodiment in, prepare the operation of paste in surface treated copper powder and aliphatic acid are distributed to solvent after, carry out with filter filter preparation and the operation of paste.The filtration based on filter like this forms fine wiring in order to utilize copper powder to stick with paste, conductive layer (electrode) as thin as a wafer carries out.In a preferred embodiment, filter for example can use there is 1～8 μ m, the preferred filter in the aperture of 1～5 μ m.In a preferred embodiment, the filtration based on filter can utilize filtration under diminished pressure or pressure filtration to carry out.The pressure of filtration under diminished pressure can be for example 0.1～1.0atm, the preferred pressure of 0.2～0.6 scope.The pressure of pressure filtration can be for example 0.1～2.0atm, the preferred pressure of 0.2～1.0 scope.
In a preferred embodiment, for the copper powder the present invention relates to is stuck with paste, utilize aperture 5 μ m, effective area 9.0cm 2filter while carrying out the filtration under diminished pressure of 0.3atm, the quality seeing through can be for example more than 35%, more than 40%, more than 45%, more than 50%, more than 55% with respect to the percentage (transmitance) of the ratio of the input quality of 4g after 30 seconds, after 1 minute, can be for example more than 35%, more than 40%, more than 45%, more than 50%, more than 55%, after 8 minutes, can be for example more than 40%, more than 45%, more than 50%, more than 55%, more than 60%, can be for example more than 40%, more than 45%, more than 50%, more than 55%, more than 60% after 15 minutes.
From remove the copper powder containing, the excessive copper powder of particle diameter, aspect that the copper powder of aggegation occurs are considered, in order to form fine wiring, conductive layer (electrode) as thin as a wafer, it is preferred that filtered copper powder is stuck with paste, if but copper powder before filtering to stick with paste be not the state that particle diameter is enough little and aggegation is fully reduced that filters the copper powder that contains of the state of being easy to, the rate of recovery of sticking with paste due to filter obstruction, copper powder is low, thereby filter operation itself is difficult to carry out.Even easily carry out, can obtain in the practical operation that is formed as the above-mentioned filtration based on filter the such copper powder of the sufficiently high rate of recovery dispersity aspect consider, it is also excellent that the copper powder that the present invention relates to is stuck with paste.The reason that the copper powder the present invention relates to is stuck with paste the dispersity that is formed as such excellence is still not clear, but the inventor thinks and may be due to the excellent surface state of surface treated copper powder itself, and then also may be due to surface treated copper powder and the combination of carboxyl of organic substance (preferred fatty acid) with carboxyl.
As for surface-treated copper powder, can use the copper powder that utilizes known method manufacture and obtain.For example, copper powder can use utilize dry process manufacture and copper powder, utilize damp process manufacture and copper powder in any.From the viewpoint of until surface treatment of the present invention becomes wet process all the time, preferably utilize damp process manufacture and copper powder.
The amino silane aqueous solution is the aqueous solution that can be used as the amino silane of silane coupler use.In a preferred embodiment, for the use amount of amino silane, can be formed as the aqueous solution of the amino silane of the amino silane that comprises following amount: the quality 1g of the copper powder during with respect to formation copper powder dispersion liquid, the quality of amino silane is more than 0.025g, preferably more than 0.050g, further preferably more than 0.075g, further preferably more than 0.10g, or, can be formed as the aqueous solution of the amino silane of the amino silane that comprises following amount: the quality 1g of the copper powder during with respect to formation copper powder dispersion liquid, be for example 0.025～0.500g, 0.025～0.250g, the amount of the scope of 0.025～0.100g.In a preferred embodiment, for the use amount of amino silane, can be formed as the aqueous solution of the amino silane that comprises following amount, the quality 1g of the copper powder during with respect to formation copper powder dispersion liquid, the volume that is included in the amino silane at 25 DEG C is more than 0.01mL, more than 0.025mL, preferably more than 0.050mL, further preferably more than 0.075mL, further preferably more than 0.10mL, or, also can be formed as the aqueous solution of the amino silane of the amino silane that comprises following amount: the quality 1g of the copper powder during with respect to formation copper powder dispersion liquid, be for example 0.025～0.500mL, 0.025～0.250mL, the amount of the scope of 0.025～0.100mL.
In a preferred embodiment, as amino silane, can use and comprise 1 above amino and/or the silane of imino group.The amino comprising in amino silane and imino group number for example can be respectively 1～4, are preferably respectively 1～3, further preferably 1～2.In a preferred embodiment, the amino comprising in amino silane and imino group number can be respectively 1.The amino silane that can be by the amino comprising in amino silane and imino group number summation 1 is called mono amino silane especially, the amino silane that is 2 by the amino comprising in amino silane and imino group number summation is called diamino silanes especially, and the amino silane that is 3 by the amino comprising in amino silane and imino group number summation is called triamido silane especially.Preferably use in the present invention mono amino silane, diamino silanes.In a preferred embodiment, as amino silane, can use and comprise 1 amino mono amino silane.In a preferred embodiment, amino silane can be to comprise at least 1, for example amino amino silane of 1 in the molecular end of the chain of molecular end, preferably straight chain shape or a chain.
As amino silane, can enumerate for example N-2-(amino-ethyl)-3-aminopropyl methyl dimethoxysilane, N-2-(amino-ethyl)-3-TSL 8330, 3-TSL 8330, 1-TSL 8330, 2-TSL 8330, 1, 2-diaminourea propyl trimethoxy silicane, 3-amino-1-acrylic trimethoxy silane, 3-amino-1-propinyl trimethoxy silane, APTES, 3-triethoxysilyl-N-(1,3-dimethyl-Ding pitches base) propylamine, N-phenyl-3-TSL 8330, N-(vinyl benzyl)-2-amino-ethyl-3-TSL 8330, APTES, 3-TSL 8330, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, 3-(N-phenyl) TSL 8330.
The amino silane that in a preferred embodiment, can use following formula I to represent.　
H 2n-R 1-Si(OR 2) 2(R 3) (formula I)
In above-mentioned formula I,
R1 be straight chain shape there is side chain, saturated or undersaturated, replacement or unsubstituted, ring type or non-ring type, there is heterocycle or do not there is the divalent group of hydrocarbon heterocycle, C1～C12,
R2 is the alkyl of C1～C5,
R3 is the alkyl of C1～C5 or the alkoxyl of C1～C5.
In a preferred embodiment, the R1 of above-mentioned formula I is straight chain shape or has side chain, saturated or undersaturated, replacement or unsubstituted, ring type or non-ring type, there is heterocycle or do not there is heterocycle, the divalent group of the hydrocarbon of C1～C12, further preferably R1 is selected from replacement or unsubstituted, the divalent group of the straight chain shape saturated hydrocarbons of C1～C12, replacement or unsubstituted, the divalent group of a chain saturated hydrocarbons of C1～C12, replacement or unsubstituted, the divalent group of the straight chain shape unsaturated hydrocarbons of C1～C12, replacement or unsubstituted, the divalent group of a chain unsaturated hydrocarbons of C1～C12, replacement or unsubstituted, the divalent group of the ring type hydrocarbon of C1～C12, replacement or unsubstituted, the divalent group of the hetero ring type hydrocarbon of C1～C12, replacement or unsubstituted, group in the divalent group of the aromatic hydrocarbon of C1～C12.In a preferred embodiment, divalent group that the R1 of above-mentioned formula I is C1～C12, saturated or undersaturated chain hydrocarbon, the more preferably divalent group of saturated chain hydrocarbon.More preferably the atom of two ends of chain structure has the divalent group of free valence.In a preferred embodiment, the carbon number of divalent group can be for example C1～C12, preferred C1～C8, preferred C1～C6, preferred C1～C3.
In a preferred embodiment, the R1 of above-mentioned formula I can be selected from-(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-in group (wherein, n, m, j are more than 1 integer).(wherein, above-mentioned (CC) represents the triple bond of C and C.) in a preferred embodiment, R1 can be-(CH 2) n-or-(CH 2) n-NH-(CH 2) m-.(wherein, above-mentioned (CC) represents the triple bond of C and C.) in a preferred embodiment, can be replaced by amino as the hydrogen of the R1 of above-mentioned divalent group, can be that for example 1～3 hydrogen, for example 1～2 hydrogen, for example 1 hydrogen are replaced by amino.
In a preferred embodiment, n, the m of above-mentioned formula I, j can be more than 1 integer below 12 independently of one another, preferably more than 1 integer below 6, further preferred more than 1 integer below 4, can for being selected from the integer in 1,2,3,4, for example, can be for example 1,2 or 3.
In a preferred embodiment, the R2 of above-mentioned formula I can be the alkyl of C1～C5, the preferably alkyl of C1～C3, and the alkyl of further preferred C1～C2, for example, can be methyl, ethyl, isopropyl or propyl group, can be preferably methyl or ethyl.
In a preferred embodiment, for the R3 of above-mentioned formula I, as alkyl, can be the alkyl of C1～C5, the preferably alkyl of C1～C3, the alkyl of further preferred C1～C2, can be for example methyl, ethyl, isopropyl or propyl group, can be preferably methyl or ethyl.In addition, for the R3 of above-mentioned formula I, as alkoxyl, can be the alkoxyl of C1～C5, the preferably alkoxyl of C1～C3, the alkoxyl of further preferred C1～C2, can be for example methoxyl group, ethyoxyl, isopropoxy or propoxyl group, can be preferably methoxy or ethoxy.
Can utilize known method that the amino silane aqueous solution is mixed with copper powder.When mixing, can suitably utilize known method to stir.In a preferred embodiment, mix and for example can carry out at normal temperatures, for example, can at the temperature of the scope of 5～80 DEG C, 10～40 DEG C, 20～30 DEG C, carry out.
In a preferred embodiment, after copper powder dispersion liquid is mixed, can carry out ultrasonic wave processing.The processing time of ultrasonic wave processing is selected according to the state of copper powder dispersion liquid, can be preferably 1～180 minute, and further preferably 3～150 minutes, further preferably 10～120 minutes, further preferably 20～80 minutes.
In a preferred embodiment, ultrasonic wave processing can with every 100mL preferably 50～600W, further preferably the power output of 100～600W is carried out.In a preferred embodiment, ultrasonic wave processing can preferred 10～1MHz, further preferably 20～1MHz, further preferably under the frequency of 50～1MHz, carry out.
For the copper powder in copper powder dispersion liquid, can, utilizing as described above amino silane to carry out, after surface treatment, separating from dispersion liquid, be reclaimed as surface treated copper powder.For this separation and recovery, can use known method, for example, can use filtration, centrifugation, decant (decantation) etc.After separating recovery, according to expectation, can be dried.Be dried and can use known method to carry out, for example, can carry out being dried based on heating.Heat drying can utilize at the temperature of for example 50～90 DEG C, 60～80 DEG C, and the heat treated of for example 30～120 minutes, 45～90 minutes is carried out.After heat drying, for copper powder, can be according to expecting further to carry out pulverization process.In addition, for the surface treated copper powder reclaiming, for antirust or improve the objects such as dispersiveness in paste, also can make organic substance etc. further be adsorbed in the surface of surface treated copper powder.
As mentioned above, in a preferred embodiment, for the copper powder that can utilize damp process to obtain in surface-treated copper powder.In a preferred embodiment, can use the copper powder that utilizes following method to manufacture as the manufacture method of the copper powder that utilizes damp process to obtain, described method comprises: in the aqueous solvent that comprises Arabic gum additive, add cuprous oxide, make the operation of slurry, in 5 seconds, carry out the not operation of homogenizing reaction to disposable interpolation dilute sulfuric acid in slurry.In a preferred embodiment, above-mentioned slurry can be remained on below room temperature (20～25 DEG C), and add the dilute sulfuric acid similarly remaining on below room temperature, carry out not homogenizing reaction.In a preferred embodiment, above-mentioned slurry can be remained on below 7 DEG C, and add the dilute sulfuric acids below similarly remaining on 7 DEG C, carry out not homogenizing reaction.In a preferred embodiment, the interpolation of dilute sulfuric acid can the mode below following, the further preferred pH1.5 of following with pH2.5, preferred pH2.0 be added.In a preferred embodiment, dilute sulfuric acid to the interpolation in slurry can with 5 minutes with interior, preferably 1 minute with interior, further preferably 30 seconds with interior, further preferably 10 seconds with interior, further preferably within 5 seconds, add in interior mode.In a preferred embodiment, can make above-mentioned not homogenizing reaction finish in 10 minutes.In a preferred embodiment, the concentration of the Arabic gum in above-mentioned slurry can be 0.229～1.143g/L.As above-mentioned cuprous oxide, can use the cuprous particle of cuprous oxide, preferential oxidation that utilizes known method to obtain, the particle diameters of this cuprous oxide particle etc., with to utilize homogenizing not to react the particle diameter etc. of the particle of the copper powder generating directly related, therefore, can not use the cuprous oxide particle of coarse grain.This principle that homogenizing is not reacted is as follows:
Cu 2O＋H 2SO 4?→?Cu↓＋CuSO 4＋H 2O
For by this copper powder that homogenizing does not obtain, also can be according to expecting to wash, antirust, filter, dry, broken, classification, then mix with amino silane, but in a preferred embodiment, according to expect wash, antirust, filter after, be not dried, directly by itself and amino silane aqueous solution.
In a preferred embodiment, utilize the reaction of above-mentioned not homogenizing and the average grain diameter of utilizing laser diffraction formula particle size distribution device to record of the copper powder that obtains is below 0.25 μ m.In a preferred embodiment, D10, D90, the Dmax that laser diffraction formula particle size distribution device records that utilize of the copper powder that utilizes above-mentioned not homogenizing reaction and obtain meets [Dmax≤D50 × 3, D90≤D50 × 2, D10 >=D50 × 0.5] relational expression, and particle diameter distributes and has simple spike.In a preferred embodiment, utilize the reaction of above-mentioned not homogenizing and in the mensuration based on laser diffraction formula particle size distribution device of the copper powder that obtains, particle size distribution is a crest (having simple spike).In a preferred embodiment, utilizing the value that laser diffraction formula particle size distribution device records is [D50≤1.5 μ m], is preferably [D50≤1.0 μ m], more preferably [D50≤0.5 μ m, Dmax≤1.0 μ m].As laser diffraction formula particle size distribution device, can use the SALD-2100 processed of for example Shimadzu Seisakusho Ltd..
The surface treated copper powder obtaining in the manner described above has excellent sintering retardance.As the index of sintering retardance, there is sintering to start temperature.It is in reducing atmosphere, the powder compact being formed by metal powder to be heated up that described sintering starts temperature, the temperature while there is certain certain change in volume (contraction).In this specification, the temperature when there is 1% volume contraction starts temperature as sintering.Particularly, as the record of embodiment, measure.Sintering starts the situation that temperature is high and represents sintering retardance excellence.
The sintering of the surface treated copper powder obtaining in the manner described above in a preferred embodiment, start temperature can be 450 DEG C above, preferably 500 DEG C above, further preferably 600 DEG C above, further preferably 700 DEG C above, further preferably 780 DEG C above, further preferably 800 DEG C above, further preferably 810 DEG C above, further preferably 840 DEG C above, further preferably 900 DEG C above, further preferably 920 DEG C above, further preferably more than 950 DEG C.In the past, at the Ni Ultramicro-powder that requires high sintering to start to use at temperature, (average grain diameter 0.2～0.4 μ sintering m) starts temperature in the scope of 500～600 DEG C, compared with this situation, this surface treated copper powder uses the Cu cheap and that easily obtain than Ni, and be fine particle, and there is the sintering retardance of identical or better excellence.
In a preferred embodiment, for surface treated copper powder, can in reducing atmosphere, powder compact be heated up and form sintered body.The sintered body obtaining can be formed as excellent electrode.This sintering process can the suitable especially internal electrode for paster multi-layer ceramic capacitor manufacture.This sintered body can use as the internal electrode of paster multi-layer ceramic capacitor especially suitably.Of the present invention preferred embodiment in, SiO 2particle is scattered in electrode section, makes to form electrode as thin as a wafer, meanwhile, does not reduce the reliability (quality) of electrode.
In a preferred embodiment, for surface treated copper powder, with respect to copper powder 1g, the adhesion amount of Si can be 500～16000 μ g, preferred 500～3000 μ g conventionally.This Si adhesion amount can utilize ICP(ICP-AES) try to achieve.In a preferred embodiment, and then, with respect to copper powder weight, can comprise N more than 0.05wt%.The mechanism that silane coupler is adsorbed in copper powder is still not clear, but the inventor thinks that reason is as follows: between the amino nitrogen of end of silane and copper, produce and interact and adsorb.
In a preferred embodiment, for surface treated copper powder, utilize surface treatment and what form can be 0.6～25nm, preferably 1.0～25nm, further preferred 1.5～20nm containing the thickness (Si thickness) of Si layer conventionally.Should can refer to containing the thickness (Si thickness) of Si layer, in the surperficial section of surface treated copper powder, carry out the Ray Energy Spectrum Analysis based on EDS(X) mensuration, taking Si atom, with respect to the existing than the amount of Si atom that becomes maximum depth as 100% time of whole atoms, the amount that is defined as Si atom is more than 10% scope.For the surperficial section of surface treated copper powder, from more than at least 100 copper powder particle of observing sample section, select 5, respectively it as the surperficial section perpendicular to surface treated copper powder, is measured and added up in border the most clearly.
In a preferred embodiment, for surface treated copper powder, can make N with respect to the % by weight of copper powder for for example 0.05 % by weight is above, preferably 0.06 % by weight above, further preferably more than 0.07 % by weight, for example, can be 0.05～0.50 % by weight, preferably 0.06～0.45 % by weight, the further preferred scope of 0.08～0.40 % by weight.N can calculate as follows with respect to the % by weight of copper powder: at high temperature make copper powder melting, by the NO producing 2calculate the N amount of adhering to.
In a preferred embodiment, for surface treated copper powder, utilizing XPS(X X-ray photoelectron spectroscopy X) the surperficial N that records of the survey of analytic approach is for example more than 1.0%, preferably more than 1.4%, further preferably more than 1.5%, more preferably more than 1.6%, or, for example, 1.0～6.0%, preferably 1.4～6.0%, further preferably 1.5～6.0%, further preferably in 1.6～6.0% scope, the photoelectron of N can be for example 1000cps(count per second) more than, preferably more than 1200cps, or, can be for example 1000～9000cps, the preferably scope of 1200～8000cps.
In a preferred embodiment, for surface treated copper powder, utilizing XPS(X X-ray photoelectron spectroscopy X) the surperficial Si that records of the survey of analytic approach can be for example more than 0.6%, preferably more than 0.8%, further preferably more than 1.0%, further preferably more than 1.1%, further preferably more than 1.2%, further preferably more than 1.3%, further preferably more than 1.4%, or, for example can be 0.6～4.0%, preferably 0.8～4.0%, further preferably 1.0～4.0%, further preferably 1.1～4.0%, further preferably 1.2～4.0%, further preferably 1.3～4.0%, further preferably in 1.4～4.0% scope, the photoelectron of Si can be for example 1000cps(count per second, counting per second) more than, preferably more than 1200cps, or, can be for example 1000～12000cps, the preferably scope of 1200～12000cps.
In a preferred embodiment, for surface treated copper powder, also can, after the surface treatment of carrying out based on amino silane, further carry out surface treatment.As such surface treatment, can enumerate for example antirust processing based on the organic corrosion inhibitor such as BTA, imidazoles, even by so common processing, can not make surface treatment disengaging based on amino silane etc. yet.Therefore, not damaging in the limit of excellent sintering retardance, those skilled in the art can be according to expecting carry out so known surface treatment., not damaging in the limit of excellent sintering retardance, further surface treatment is carried out in the surface of the surface treated copper powder the present invention relates to and the copper powder and the copper powder that obtain are stuck with paste also still within the scope of the invention.
In the present invention, when use beyond copper powder metal powder time, also can be by the surface treatment illustrating hereinbefore for copper powder, and obtain excellent characteristic.When use beyond copper powder metal powder time, also can preferred embodiment implement the present invention by what recorded for above-mentioned copper powder.As metal powder, for example, can use any metal powder in Pt, Pd, Ag, Ni, Cu.Including copper powder, as preferred metal powder, can enumerate any metal powder in Ag, Ni, Cu.
In the present invention, can implement suitably by adhering to as described above of Si, but also can implement by adhering to suitably of the element beyond Si.In the case of adhering to the element beyond Si, also can preferred embodiment implement the present invention by what recorded for above-mentioned Si.As the element beyond Si, more than can enumerating any one in Ti, Al, Zr, Ce, Sn.Including Si, as preferred element, more than can enumerating any one in Si, Ti, Al, Zr, Ce, Sn, more than can further preferably enumerating any one in Si, Ti, Al.
In the present invention, can utilize as described above silane coupler to carry out surface treatment to copper powder and enforcement suitably, but also can utilize the coupling agent beyond silane coupler carry out surface treatment and implement suitably.As the coupling agent beyond silane coupler, can enumerate titanate esters, Aluminate.As coupling agent, respectively, when using in the situation of silane coupler, can adhere to suitably Si, when using in the situation of titanate esters, can adhere to suitably Ti, when using in the situation of Aluminate, can adhere to suitably Al.The occupation mode of these coupling agents, can apply the mode illustrating as described above for silane coupler.With the structure of silane coupler similarly, in the structure of titanate esters and Aluminate, also preferably containing endways amino substituting group is coordinated in the structure as Ti and the Al of central atom.
In a preferred embodiment, as the suitable adhesion amount of the Si based on above-mentioned coupling agent, Ti or Al, as illustrated for copper powder, and then, with respect to metal powder 1g, can enumerate for example scope of 200～16000 μ g, 300～16000 μ g, 500～16000 μ g, for example scope of 200～3000 μ g, 300～3000 μ g, 500～3000 μ g, for example scope of 200～1500 μ g, 300～1500 μ g, 500～1500 μ g.
In a preferred embodiment, the thickness (Si thickness) containing Si layer that utilizes the surface treatment of metal powder and form can be such for what illustrate as mentioned above for copper powder, and then, for containing the thickness (Ti thickness) of Ti layer, containing the thickness (Al thickness) of Al layer, can be also for explanation such as mentioned above of the thickness (Si thickness) containing Si layer.
In a preferred embodiment, for surface treated metal powder, can make to utilize XPS(X X-ray photoelectron spectroscopy X) the surperficial Si that records of the survey of analytic approach be for copper powder as mentioned above explanation like that.And then, the Si adhering to except utilizing surface treatment, for Ti and Al, also can utilize the assay method same with Si, being with the number range specifying for Si is same number range.
In a preferred embodiment, for surface treated metal powder, can make to utilize XPS(X X-ray photoelectron spectroscopy X) the surperficial N that records of the survey of analytic approach be for copper powder as mentioned above explanation like that.
In the case of obtaining surface treated metal powder with the metal powder beyond copper powder, for by surface treated metal powder, with the organic substance such as aliphatic acid and solvent and mix to manufacture according to the adhesive resin of expecting the operation that metal powder is stuck with paste, also can carry out according to sticking with paste for copper powder the operation illustrating as described above.The kind of the organic substances such as the aliphatic acid that can preferably use in this case,, solvent, adhesive resin and mixing ratio are with for copper powder paste, explanation is identical like that hereinbefore.For the metal powder that obtains is in the manner described above stuck with paste, in a preferred embodiment, illustrating hereinbefore as stuck with paste for copper powder, there is the characteristic of same excellence, there are the filter permeability, treatability, sintering retardance of same excellence etc.
As the titanate esters that can use suitably in the present invention, can enumerate that Formula Il represents containing amino titanate esters:
(H 2n-R 1-O) pti(OR 2) q(formula II)
(wherein, in above-mentioned formula II,
R1 be straight chain shape or have side chain, saturated or undersaturated, replacement or unsubstituted, ring type or non-ring type, there is heterocycle or do not there is the divalent group of hydrocarbon heterocycle, C1～C12,
R2 is straight chain shape or has alkyl side chain, C1～C5,
P and q are 1～3 integer, p+q=4.）。
As the R1 of above-mentioned formula II, the R1 of above-mentioned formula I can be preferably used as and the group that lists.As the R1 of above-mentioned formula II, for example, can be selected from-(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-in group (wherein, n, m, j are more than 1 integer).As particularly preferred R1, can enumerate-(CH 2) n-NH-(CH 2) m-(wherein, n+m=4, particularly preferably n=m=2).
As the R2 of above-mentioned formula II, the R2 of above-mentioned formula I can be preferably used as and the group that lists.In a preferred embodiment, the alkyl of C3 can be enumerated, propyl group and isopropyl can be particularly preferably enumerated.
The p of above-mentioned formula II and q are 1～3 integers, p+q=4, the combination that can preferably enumerate p=q=2, the combination of p=3, q=1.As the amino titanate esters that contains that has configured as described above functional group, can enumerate Plain Act KR44(Ajinomoto Fine-Techno company system).
Metal powder of the present invention starts temperature as having as described above high sintering as copper powder of the present invention, by allocating this metal powder, can manufacture excellent conductive metal powder and stick with paste, and sticks with paste by this conductive metal powder of sintering, can manufacture excellent electrode.The sintering of metal powder of the present invention start temperature with illustrate hereinbefore for copper powder identical like that.In a preferred embodiment, the electrode obtaining by the present invention can be the SiO for electrode section 2explanation is such hereinbefore, similarly, and for the TiO of electrode section 2, and the Al of electrode section 2o 3, can be also the SiO for electrode section 2such size, number, density are described hereinbefore.In a preferred embodiment, about the SiO of electrode section 2, be equivalent to use the situation of silane coupler as surface-treated coupling agent, for the TiO of electrode section 2, be equivalent to use the situation of titanate esters as surface-treated coupling agent, for the Al of electrode section 2o 3, be equivalent to use the situation of Aluminate as surface-treated coupling agent.
[embodiment]
Below enumerate embodiment the present invention is described in further detail.The invention is not restricted to following embodiment.
[manufacture of surface treatment copper powder]
Manufacture as described below surface treated copper powder.
[utilizing the powder process of damp process]
Utilize damp process manufacture for surface-treated copper powder 20g.The copper powder obtaining has characteristic as described below.Measure and use laser diffraction formula particle size distribution device (SALD-2100 processed of Shimadzu Seisakusho Ltd.).　
D50?0.12μm
A crest distributes.
[preparation of silane-water solution]
Prepare respectively the silane-water solution that 50mL has used following various silane.
Silane: diamino silanes A-1120(MOMENTIVE company system)
Amino silane A-1110(MOMENTIVE company system)
Epoxy silane Z-6040(Dow Corning Toray company system)
Methyltrimethoxy silane KBM-13(Shin-Etsu Silicones company system)
3-phenyl amino propyl trimethoxy silicane (MOMENTIVE company system)
Be prepared in the scope of 0.5～15vol% with concentration.In addition, except amino is silane, pH is adjusted to 4 with dilute sulfuric acid.
The structural formula of various silane is as follows.　
Diamino silanes A-1120:
H 2N－C 2H 4－NH－C 3H 6－Si（OCH 3） 3
Amino silane A-1110:
H 2N－C 3H 6－Si（OCH 3） 3
Epoxy silane Z-6040:
Methyltrimethoxy silane KBM-13:
H 3C－Si（OCH 3） 3
3-phenyl amino propyl trimethoxy silicane:
C 6H 5－NH－C 3H 6－Si（OCH 3） 3。
[based on the surface treatment mixing of silane-water solution]
Mix and blend copper powder 20g and each silane-water solution 50mL, prepare copper powder dispersion liquid, carry out immediately ultrasonic wave processing (the Tech jam of Co., Ltd. system, the ultrasonic washer of 60 minutes (or 120 minutes), 3 frequency types/W-113) (power output 100W, frequency 100kHz).In table 1, this required time of 60 minutes is recited as to the mix and blend time.Operation is at room temperature carried out.
In addition, as the record of table 1, in some embodiment, use simultaneously utilize that rotating vane carries out be uniformly mixed (300rpm) and the stirring of above-mentioned ultrasonic wave, or only make silane coupler be adsorbed in copper powder by the stirring that utilizes rotating vane to carry out.
Copper powder dispersion liquid is filtered, reclaim surface treated copper powder, at 70 DEG C, heat drying 1 hour, obtains surface treated copper powder.
The processing that surface treated copper powder in each embodiment and comparative example is carried out is summarized in table 1.
[evaluation of surface treated copper powder]
For the surface treated copper powder that utilizes aforesaid operations to obtain, utilize following method to evaluate.
[copper powder dimension measurement]
For the size of copper powder, profit is measured with the following method.Result is summarized in to table 2.
Laser diffraction formula particle size distribution (SLAD-2100 of Shimadzu Seisakusho Ltd.).
[based on the mensuration of TMA]
Make sample by surface treated copper powder, use TMA(Thermomechanical Analyzer, thermomechanical analyzer), measure under the following conditions sintering and start temperature.　
Sample making condition
Powder compact size: 7mm φ × 5mm is high
Briquetting pressure: 1Ton/cm 2(1000kg weight/cm 2)
(adding the zinc stearate of 0.5wt% as lubricant)
Condition determination
Device: the TMA-50 of Shimadzu Seisakusho Ltd.
Heat up: 5 DEG C/min
Atmosphere: 2vol%H 2-N 2(300cc/ minute)
Load: 98.0mN.
Like this, in the copper powder as determination object, add the zinc stearate of 0.5wt% and mix, this mixture being loaded in the cylindrical shell of diameter 7mm, being pressed into drift from top, giving at 1Ton/cm 2the lower maintenance pressurization of 3 seconds, is shaped to and is equivalent to the cylindric of about 5mm height.Be under vertical direction and the condition of load of giving vertically 98.0mN making axle, this formed body be loaded in heating furnace, at 2vol%H 2-N 2in (300cc/ minute) flow, taking programming rate as 5 DEG C/min, in the measurement range of 50～1000 DEG C, heat up continuously, automatically record the height change (variation of dilation) of formed body.The height change of formed body (contraction) is started and the temperature of its shrinkage while reaching 1% is designated as " sintering starts temperature ".The measurement result that the sintering of the surface treated copper powder in each embodiment and comparative example is started to temperature is summarized in table 3.
[analysis]
Analyze under the following conditions lip-deep Si, the N and the C that are attached to surface treated copper powder.Result is summarized in to table 3.
The surface treated copper powder of acid-soluble solution for adhesion amount Si, by ICP(ICP-AES) carry out quantitatively, (μ is g) to obtain the quality of the unit mass with respect to surface treated copper powder (g) of the Si adhering to.
N, C are at high temperature by copper powder melting, by the NO producing 2, CO 2calculate and adhere to N, C amount, be attached to the whole lip-deep N of copper powder, the amount of C by mensuration, obtain the quality of the N, the C that adhere to respect to the quality %(% by weight of the quality of surface treated copper powder).
[table 1]
[table 2]
[table 3]
Except above-mentioned comparative example 1～5, use tetraethoxysilane (TEOS) as silane coupler, use ammonia as catalyst, copper powder is carried out to surface treatment, compare experiment, in the time using tetraethoxysilane, become following state: the surface treatment copper powder generation aggegation obtaining, by visually observing, think and do not obtain uniform surface treatment and particle diameter.Now, before surface treatment, D50=0.13 μ m, Dmax=0.44 μ m, but after surface treatment, D50=0.87 μ m, Dmax=3.1 μ m, all becomes large 7 times of left and right.In addition, particle size distribution is 2 crests that become of 1 crest before surface treatment.
Known according to the above results, for the present invention relates to mixed amino silane-water solution and for the surface treated copper powder manufactured, although its manufacture method is extremely simple, although be to there is minute sized copper powder, there is the high sintering identical or higher with the micro mist of the refractory metals such as nickel and start temperature.In addition we know,, by this surface treated copper powder, the sintering that utilization is same with the manufacturing process of the electrode of paster multi-layer ceramic capacitor, can manufacture sintered body; In the sintered body section that manufacture (formation) obtains in this wise, be dispersed with SiO 2particle.
In addition, from above-mentioned result, in order to realize sufficient sintering retardance, as silane coupler, need for thering is amino amino silane.In addition we know,, as amino silane, preferably there is endways amino amino silane.In comparative example 4, although the visible Si that copper powder adheres to q.s relatively does not realize sufficient sintering retardance.Though its reason is indefinite, but the inventor infers that reason may be as follows: in comparative example 4, amino silane is not formed as having endways amino structure, and, because phenyl ring is present in than amino more by end, therefore produce the state as sterically hindered, in the intensification for sintering midway, the amino silane or the Si that are temporarily attached on copper powder depart from from copper powder in early days.
[utilizing the coherent manufacture of damp process]
Manufacture as described below fine copper powder, so utilize amino silane to manufacture and copper powder carry out surface treatment, the surface treated copper powder that utilizes damp process to manufacture consistently to the present invention relates to.
(1), in Arabic gum 0.2g+ pure water 350mL, add cuprous oxide 50g.
(2) then, disposable interpolation dilute sulfuric acid (25wt%) 50mL.
(3) utilize rotating vane to stir (300rpm × 10 minute) to it, then place 60 minutes.
(4) then, precipitation is washed.
Washing is carried out in the following way, initial, removes supernatant, add pure water 350mL to stir (300rpm × 10 minute), then place 60 minutes, remove supernatant, add pure water 350mL to stir (300rpm × 10 minute), then place 60 minutes, remove supernatant.
(5) then, carry out aminosilane-treated.
For aminosilane-treated, add the amino silane aqueous solution (50mL), stir 60 minutes, now, be rotated the processing of blade (300rpm)+ultrasonic wave (the Tech jam of Co., Ltd. system, ultrasonic washer 3 frequency types/W-113) (power output 100W, frequency 100kHz).Unlike this, only utilize separately the processing of rotating vane (300rpm), only utilize hyperacoustic processing.As amino silane, use respectively diamino silanes A-1120(MOMENTIVE company system), amino silane A-1110(MOMENTIVE company system).
(6) then, filter precipitation and separation.
(7) then, that the precipitation separating is dry.For dry (70 DEG C × 2h), carry out respectively dry and being dried in nitrogen under air atmosphere.
Obtain surface treated fine copper powder by coherent manufacture in the manner described above.The surface treated copper powder obtaining in the manner described above, similarly has excellent sintering retardance with the surface treated copper powder of above-described embodiment, meanwhile, and the SiO existing at its sintered body section 2macroparticle number little.In addition, for this coherent manufacture, can before obtaining final products, not carry out dryly, easy and operability is excellent.
[manufacture that copper powder is stuck with paste]
Will utilize embodiment 2,3,5 and comparative example 1,2 manufacture and each aminosilane-treated copper powder, following each aliphatic acid and adhesive be distributed in solvent, manufactured the copper powder of 20g and stuck with paste.Surface treatment copper powder for now: solvent: adhesive: for the mass ratio of aliphatic acid, in the situation that not adding adhesive, being 65:34.3:0.7, in the situation that adding adhesive, is 65:27.2:7:0.8.Using they respectively as embodiment 9,10,11 and comparative example 5,6 for later mensuration.　
The surface treatment copper powder of embodiment 2: carrying out silane concentration is the diamino silanes processing of 2vol%
The surface treatment copper powder of embodiment 3: carrying out silane concentration is the diamino silanes processing of 4vol%
The surface treatment copper powder of embodiment 5: carrying out silane concentration is the diamino silanes processing of 10vol%
The surface treatment copper powder of comparative example 1: only carry out BTA processing
The surface treatment copper powder of comparative example 2: carrying out silane concentration is the epoxy silane processing of 10vol%
Aliphatic acid: oleic acid (C18,1 two key)
Linoleic acid (C18,2 two keys)
Acrylic acid (C3,1 two key)
Adhesive: polyvinyl butyral resin
Solvent: α-terpineol (TPO) or butyl carbitol
With above-mentioned cooperation, utilize three rollers to come mixing surface treatment copper powder, aliphatic acid, adhesive, solvent, obtain internal electrode with sticking with paste.
[transmitance that filter filters is measured]
Stick with paste for the copper powder of manufacturing as described above, under 0.2atm, carry out filtration under diminished pressure with the glass filter of aperture 5 μ m, measure and from firm input, start until the transit dose (g) after 30 seconds, after 8 minutes, after 15 minutes, calculate with respect to the ratio of putting at first the amount (g) in filter, as transmitance (%) with percentage.By embodiment 9,10,11 and comparative example 5,6(have, adhesive-free resin) in obtain the results are shown in following table 4 and table 5.
[table 4]
*: do not stick with paste and cannot not measure through filter.
[table 5]
*: do not stick with paste and cannot not measure through filter.
Hence one can see that, utilizes diamino silanes to carry out surface-treated copper powder, compared with comparative example, all shows the transmitance of at least 9～10 times of above so obvious excellences under arbitrary condition.
Thickness with approximately 1 μ m is stuck with paste the above-mentioned copper powder filtering through filter to be applied on the sheet of paste of dielectric medium powder, and result, can easily obtain the uniform sheet that copper powder is stuck with paste.By this sheet sintering, result can be manufactured electrode in the case of dielectric layer and the conductive layer being formed by copper are not peeled off.
For copper powder, particle size is less, and aggegation is more obvious.And, as described above, if produce aggegation, just only so make operability, productivity ratio also reduce.And then, in the time forming the internal electrode of paster multi-layer ceramic capacitor, can use the printing technologies such as silk screen printing, therefore need to be before being about to printing, use the copper powder of filter bag filter cupric powder with small aperture to stick with paste., if accurate printing and use the copper powder that particle size is little, aggegation becomes easy generation, if copper powder aggegation in copper powder is stuck with paste becomes and cannot pass through filter, the generation such situation of pattern that cannot print electrode.If filter stops up, the utilization ratio (yield) that not only copper powder is stuck with paste reduces, but also the such situation of whole printing equipment can occur must stop in order to change filter.Therefore the aggegation that, prevents copper powder is important in electrode manufacture.
Under such situation, the known copper powder the present invention relates to is stuck with paste and is formed as, except sintering retardance excellence, also can preventing aggegation, and the filter permeability also copper powder of excellence is stuck with paste, and therefore becomes and can stick with paste for the copper powder that has used the electrode of printing technology to manufacture suitably.
[having carried out the manufacture of the copper powder of antirust processing]
Manufacture the copper powder that surface treated copper powder has further been carried out to antirust processing.After having obtained the copper powder of the above embodiments 4, in order to carry out antirust processing, be distributed in the BTA aqueous solution (0.1g/L) 100 mL, with rotating vane with 500rpm carry out 10 minutes stir, filter, be dried (the lower 70 DEG C × 1h of blanket of nitrogen), and then the copper powder (embodiment 12) that has obtained having carried out antirust processing.
[having carried out the evaluation of the copper powder of antirust processing]
For the copper powder (embodiment 12) that has carried out above-mentioned antirust processing, similarly evaluate with the above embodiments 4, its result is summarized in to table 6～table 8.It should be noted that, the size of the copper powder after treatment in table 7 is in embodiment 12, the size of antirust copper powder after treatment, and each evaluation of table 8 is also for the result of copper powder of having carried out antirust processing.From these results, even in the situation that surface treated copper powder has been carried out to antirust processing, can not lose the excellent characteristic of surface treated copper powder yet.
[embodiment]
Except the embodiment having illustrated hereinbefore, enumerate following embodiment, the present invention is described in further detail.The invention is not restricted to following embodiment.
[metal powder]
As metal powder, prepare copper fine powder, nickel powder, silver powder according to following step.
(copper fine powder)
Embodiment 18～20, comparative example 11
Utilize above-mentioned damp process to manufacture for surface-treated copper powder 20g.,
(1), in Arabic gum 0.4 g+pure water 350 mL, add cuprous oxide 50 g.　
(2) then, disposable interpolation dilute sulfuric acid (25wt%) 50 mL.　
(3) utilize rotating vane to stir (300rpm × 10 minute) to it, then place 60 minutes.　
(4) then, precipitation is washed.
Washing is carried out in the following way, initial, removes supernatant, add pure water 350mL to stir (300rpm × 10 minute), then place 60 minutes, remove supernatant, add pure water 350mL to stir (300rpm × 10 minute), then place 60 minutes, make copper fine powder sedimentation.Under this state, utilize laser diffraction formula particle size distribution device (SLAD-2100 of Shimadzu Seisakusho Ltd.) to carry out granulometry, as the granulometry before surface treatment.
The particle size of the copper powder obtaining (D50, Dmax) is shown in to table 7.In mensuration, use laser diffraction formula particle size distribution device (SALD-2100 processed of Shimadzu Seisakusho Ltd.).
Embodiment 13
According to No. 4164009 communique of Japan Patent, utilize chemical reduction method to obtain copper powder.That is, in the pure water that Arabic gum 2g is added to 2900mL after, add on one side copper sulphate 125g and stir, add 80% hydrazine monohydrate 360mL on one side.Adding after hydrazine monohydrate, be warming up to 60 DEG C through 3 times from room temperature, then made cupric oxide reaction through 3 hours.After reaction finishes, filters the slurry obtaining with Buchner funnel, then, by pure water and methanol wash, and then it is dried and has obtained copper powder.Utilize the step of embodiment 1 that this copper powder is mixed with diamino silanes coupling agent aqueous solution, obtained surface treatment silver powder.Utilize the step of embodiment 1 to evaluate its characteristic.
(nickel powder)
Nickel powder used the NF32(D50 of Toho Titanium system be 0.3 μ m).
(silver powder)
According to TOHKEMY 2007-291513 powder process.That is, in the pure water of 0.8L, dissolve silver nitrate 12.6g, add 25% ammoniacal liquor 24mL, then add nitric acid ammonia 40g, prepare the silver-colored amine complex salt aqueous solution.Ratio with 1g/L is added gelatin wherein, sets it as electrolyte, and anode, negative electrode all use DSE pole plate, with 200A/m 2current density, the solution temperature of 20 DEG C carry out electrolysis, the silver particles of electrocrystallization is scraped to electrolysis on one side 1 hour from pole plate on one side.Filter the silver powder so obtaining with Buchner funnel, wash with pure water, alcohol successively, at 70 DEG C, under air atmosphere, be dried 12 hours.By this silver powder dry classification, finally having obtained D50 is that 0.1 μ m, Dmax are the silver powder of 0.5 μ m.
(preparation of coupling agent aqueous solution)
Prepare respectively 50mL use the silane-water solution of following various silane.　
Silane: diamino silanes A-1120(MOMENTIVE company system)
Methyltrimethoxy silane KBM-13(Shin-Etsu Silicones company system)
Titanate esters: containing amino Plain Act KR44(Ajinomoto Fine-Techno company system)
Not containing amino Plain Act KR TTS (Ajinomoto Fine-Techno company system)
Be prepared in the scope of 1～10vol% with concentration.In addition, except amino is coupling agent, pH is adjusted to 4 with dilute sulfuric acid.
The structural formula of various silane is as follows.　
Diamino silanes A-1120:
H 2N－C 2H 4－NH－C 3H 6－Si（OCH 3） 3
Methyltrimethoxy silane KBM-13:
H 3C－Si（OCH 3） 3
Containing amino Plain Act KR44
The side chain organo-functional group of hydrophobic group
（CH 3） 2CH－O－
The side chain organo-functional group of hydrophilic group
－O－（C 2H 4）－NH－（C 2H 4）－NH 2
Not containing amino Plain Act KR TTS
The side chain organo-functional group of hydrophobic group
（CH 3） 2CH－O－
The side chain organo-functional group of hydrophilic group
－O－CO－（C 17H 35）。
(surface treatment)
From the copper fine powder slurry obtaining according to above-mentioned (copper fine powder) step, remove supernatant, in the situation that not making copper fine powder dry, utilize any method in following methods to mix coupling agent (embodiment 18～20, comparative example 11) prepared by above-mentioned (preparation of coupling agent aqueous solution) through 60 minutes.　
(1) rotating vane (300rpm)+ultrasonic wave (the Tech jam of Co., Ltd. system, ultrasonic washer 3 frequency types/W-113) (power output 100W, frequency 100kHz)
(2) only utilize rotating vane (300rpm)
(3) only utilize ultrasonic wave
Then, utilize aspirator (aspirator) to carry out suction filtration to above-mentioned coupling agent aqueous solution, then, under nitrogen atmosphere at 70 DEG C to its carry out 1 hour dry, pulverized with mortar.Under this state, again carry out granulometry.
The silver powder obtaining for the nickel powder obtaining in above-mentioned (nickel powder), according to above-mentioned (silver powder) step, the coupling agent that utilizes the step of above-mentioned (1) to prepare with above-mentioned (preparation of coupling agent aqueous solution) through 60 minutes mixes, and has carried out surface treatment (embodiment 14～17 and 21～26, comparative example 8,10,12,13).
[manufacture that copper powder is stuck with paste]
Will utilize embodiment 14,16,19,22,25 and comparative example 7～11 manufacture and each aminosilane-treated metal powder, following each aliphatic acid and adhesive be distributed in solvent, manufacture the metal powder of 20g and stick with paste.Surface-treated metal powder for now: solvent: adhesive: for the mass ratio of aliphatic acid, in the situation that not adding adhesive, being 65:34.3:0.7, in the situation that having added adhesive, is 65:27.2:7:0.8.Using they respectively as embodiment 27～31 and comparative example 14～18 for later mensuration.　
The surface treatment nickel powder of embodiment 14: carrying out silane concentration is the diamino silanes processing of 1vol%
The surface treatment silver powder of embodiment 16: carrying out silane concentration is the diamino silanes processing of 1vol%
The surface treatment copper powder of embodiment 19: carrying out titanate esters concentration is the amino titanate esters processing that contains of 6vol%
The surface treatment nickel powder of embodiment 22: carrying out titanate esters concentration is the amino titanate esters processing that contains of 6vol%
The surface treatment silver powder of embodiment 25: carrying out titanate esters concentration is the amino titanate esters processing that contains of 6vol%
The silver powder of comparative example 7: do not carry out surface treatment
The surface treatment silver powder of comparative example 8: carrying out silane concentration is the methyltrimethoxy silane processing of 10vol%
The nickel powder of comparative example 9: do not carry out surface treatment
The surface treatment nickel powder of comparative example 10: carrying out silane concentration is the methyltrimethoxy silane processing of 10vol%
The surface treatment copper powder of comparative example 11: carrying out silane concentration is the amino titanate esters processing of not having of 10vol%
Aliphatic acid: oleic acid (C18,1 two key)
Linoleic acid (C18,2 two keys)
Acrylic acid (C3,1 two key)
Adhesive: polyvinyl butyral resin
Solvent: α-terpineol (TPO) or butyl carbitol
With above-mentioned cooperation, utilize three rollers to come mixing surface treatment copper powder, aliphatic acid, adhesive, solvent, obtain internal electrode with sticking with paste.
[transmitance that filter filters is measured]
Stick with paste for the copper powder of manufacturing as described above, under 0.2atm, carry out filtration under diminished pressure with the glass filter of aperture 5 μ m, measure and from firm input, start until the transit dose (g) after 30 seconds, after 8 minutes, after 15 minutes, calculate with respect to the ratio of putting at first the amount (g) in filter, as transmitance (%) with percentage.Embodiment 27～31 and comparative example 14～18(have, adhesive-free resin) in obtain the results are shown in following table 9 and table 10.
[table 6]
[table 7]
[table 8]
[table 9]
*: do not stick with paste and cannot not measure through filter.
[table 10]
*: do not stick with paste and cannot not measure through filter.
From the above results, use copper powder metal powder in addition, and use amino silane coupling agent in addition, while manufacturing surface treated metal powder, also with to utilize amino silane to carry out the situation of surface-treated copper powder same, utilize extremely simple manufacture method, can form and there is the metal powder that high sintering starts temperature and stick with paste.In addition we know,, by above-mentioned surface treated metal powder, the sintering that utilization is same with the manufacturing process of the electrode of paster multi-layer ceramic capacitor, can manufacture sintered body.In addition we know, the metal powder being obtained by above-mentioned surface treated metal powder manufacture is stuck with paste, same with the situation that copper powder is stuck with paste, be formed as not only sintering retardance excellence, and can prevent aggegation, the filter permeability also metal powder of excellence is stuck with paste, and becomes and can stick with paste for the metal powder that has used the electrode of printing technology to manufacture suitably.
[industrial usability]
Copper powder of the present invention is stuck with paste the also copper powder paste of excellence of dispersiveness that is formed as the copper powder in sintering retardance excellence, paste, therefore can avoid the problem in the manufactures such as stripping electrode, advantageously manufactures the manufacture of paster stacked capacitor electrode.In addition, for the manufacture of copper powder paste of the present invention, this surface treated copper powder is carried out to very simple processing and can manufacture, therefore, do not need superb technical ability, operability and productivity ratio excellence.In addition, metal powder of the present invention is stuck with paste also and is stuck with paste the same excellent characteristic that has with copper powder.The present invention is industrially useful invention.

Claims (56)

1. metal powder is stuck with paste, and it disperses and contains in solvent:
Surface treated metal powder, wherein the above adhesion amount of any one in Si, Ti, Al, Zr, Ce, Sn is to be 200～16000 μ g with respect to metal powder 1g, N is more than 0.02% with respect to the % by weight of metal powder, and
There is the organic substance of carboxyl.
2. metal powder according to claim 1 is stuck with paste, and wherein, except surface treated metal powder with have the organic substance of carboxyl, it disperses and contains adhesive resin in solvent.
3. metal powder according to claim 1 and 2 is stuck with paste, and wherein, metal powder is copper powder.
4. metal powder according to claim 1 and 2 is stuck with paste, and wherein, metal powder is any metal powder in Pt, Pd, Ag, Ni, Cu.
5. stick with paste according to the metal powder described in any one in claim 1～4, wherein, any one the above adhesion amount in Si, Ti, Al, Zr, Ce, Sn is to be 300～16000 μ g with respect to metal powder 1g.
6. stick with paste according to the metal powder described in any one in claim 1～4, wherein, any one the above adhesion amount in Si, Ti, Al, Zr, Ce, Sn is to be 500～16000 μ g with respect to metal powder 1g.
7. stick with paste according to the metal powder described in any one in claim 1～6, wherein, any one the above adhesion amount in Si, Ti, Al, Zr, Ce, Sn is to be below 3000 μ g with respect to metal powder 1g.
8. stick with paste according to the metal powder described in any one in claim 1～6, wherein, any one the above adhesion amount in Si, Ti, Al, Zr, Ce, Sn is to be below 1500 μ g with respect to metal powder 1g.
9. stick with paste according to the metal powder described in claim 1～8, wherein, N is more than 0.05% with respect to the % by weight of metal powder.
10. stick with paste according to metal powder described in any one in claim 1～9, wherein, any one in Si, Ti, Al, Zr, Ce, Sn is above is more than any one in Ti, Al, Zr, Ce, Sn.
11. stick with paste according to the metal powder described in any one in claim 1～9, wherein, more than any one in Si, Ti, Al, Zr, Ce, Sn are Si.
12. metal powders according to claim 1 are stuck with paste, and wherein, metal powder is copper powder, and the adhesion amount of Si is to be 500～16000 μ g with respect to copper 1g, and N is more than 0.05% with respect to the % by weight of copper powder.
13. metal powders according to claim 1 are stuck with paste, and wherein, metal powder is copper powder, and the adhesion amount of Si is to be 500～3000 μ g with respect to copper 1g, and N is more than 0.05% with respect to the % by weight of copper powder.
14. stick with paste according to the metal powder described in claim 1～13, and wherein, surface treated metal powder is with the surface-treated metal powder of coupling agent.
15. stick with paste according to metal powder described in claim 1～14, wherein, utilize coupling agent treatment and adsorb have Si, more than any one in Ti, Al, Zr, Ce, Sn.
16. stick with paste according to the metal powder described in claim 1～15, and wherein, coupling agent is any in silane, titanate esters, Aluminate.
17. stick with paste according to the metal powder described in claim 1～16, and wherein, coupling agent is that end is amino coupling agent.
18. stick with paste according to the metal powder described in claim 1～17, and wherein, coupling agent is amino silane.
19. stick with paste according to the metal powder described in any one in claim 1～18, and wherein, the organic substance with carboxyl is carboxylic acid or amino acid.
20. stick with paste according to the metal powder described in any one in claim 1～19, and wherein, the organic substance with carboxyl is aliphatic acid.
21. metal powders according to claim 20 are stuck with paste, and wherein, aliphatic acid is the saturated or undersaturated aliphatic acid of C3～C24.
22. metal powders according to claim 20 are stuck with paste, and wherein, aliphatic acid is that the double key number of C3～C24 is the aliphatic acid of 0～2.
23. metal powders according to claim 20 are stuck with paste, wherein, aliphatic acid is to be selected from crotonic acid, acrylic acid, methacrylic acid, sad, n-nonanoic acid, capric acid, laurate, myristic acid, pentadecanoic acid, palmitic acid, palmitoleic acid, Heptadecanoic acide, stearic acid, oleic acid, vaccenic acid, linoleic acid, (9, 12, 15)-leukotrienes, (6, 9, 12)-leukotrienes, dihomo-gamma-linolenic acid, eleostearic acid, tuberlostearic acid, arachidic acid (arachic acid), 8, 11-eicosadienoic acid, 5, 8, 11-eicosatrienoic acid, arachidonic acid, behenic acid, lignoceric acid, nervonic acid, elaidic acid, sinapic acid, DHA, eicosapentaenoic acid, in parinaric acid more than a kind.
24. stick with paste according to the metal powder described in any one in claim 1～23, and wherein, solvent is alcoholic solvent, glycol ether solvent, acetic acid esters solvent, ketone solvent or hydrocarbon solvent.
25. stick with paste according to metal powder described in any one in claim 19～24, wherein, aliphatic acid with respect to the mass ratio (aliphatic acid/surface treated copper powder) of surface treated metal powder in 1/100～1/10 scope.
26. stick with paste according to metal powder described in any one in claim 19～25, wherein, aliphatic acid with respect to the mass ratio (aliphatic acid/solvent) of solvent in 1/100～1/10 scope.
27. stick with paste according to the metal powder described in any one in claim 1～26, wherein, utilize aperture 5 μ m, effective area 9.0cm 2filter while carrying out the filtration under diminished pressure of 0.3atm, the quality seeing through was more than 35% with respect to the percentage (transmitance) of the ratio of the input quality of 4g after 30 seconds.
28. paster multi-layer ceramic capacitors, be right to use require pasting described in any one in 1～27 make and.
29. paster multi-layer ceramic capacitors according to claim 28, wherein, on internal electrode section, having diameter is SiO more than 10nm 2, TiO 2, Al 2o 3in any.
30. according to the paster multi-layer ceramic capacitor described in claim 28 or 29, wherein, on internal electrode section with 0.5/cm 2below having maximum diameter is SiO more than 0.5 μ m 2, TiO 2, Al 2o 3in any.
The manufacture method that 31. metal powders are stuck with paste, comprises surface treated metal powder and the organic substance with carboxyl is dispersed in to the operation of preparing paste in solvent:
Any one above adhesion amount in described surface treated metal powder in Si, Ti, Al, Zr, Ce, Sn is to be 200～16000 μ g with respect to metal powder 1g, and N is more than 0.02% with respect to the % by weight of metal powder.
32. methods according to claim 31, wherein, the operation that preparation is stuck with paste is:
Except surface treated metal powder with have the organic substance of carboxyl, also adhesive resin is dispersed in to the operation of preparing paste in solvent.
33. according to the method described in claim 31 or 32, and wherein, the organic substance with carboxyl is aliphatic acid.
34. according to the method described in any one in claim 31～33, surface treated metal powder and aliphatic acid being distributed to after solvent prepares the operation of paste,
Comprise the operation of filtering the paste of preparing and obtain with filter.
35. methods according to claim 34, wherein, filter has the aperture of 1～8 μ m.
36. according to the method described in claim 34 or 35, and wherein, the operation of filtering with filter utilizes filtration under diminished pressure or pressure filtration to carry out.
37. according to the method described in any one in claim 31～36, and wherein, surface treated metal powder is to utilize the surface treated metal powder of manufacturing the method manufacture of surface treated metal powder and obtain, and described manufacture method comprises:
By metal powder with there is amino coupling agent aqueous solution and mix, prepare the operation of metal powder dispersion liquid.
38. according to the method described in claim 37, and wherein, metal powder is any metal powder in Pt, Pd, Ag, Ni, Cu.
39. according to the method described in claim 37, and wherein, metal powder is copper powder.
40. according to the method described in claim 37, and wherein, metal powder is any metal powder in Pt, Pd, Ag, Ni.
41. according to the method described in any one in claim 37～40, wherein, comprises the operation that stirs metal powder dispersion liquid.
42. according to the method described in any one in claim 37～41, wherein, comprises the operation of metal powder dispersion liquid being carried out to ultrasonic wave processing.
43. according to the method described in claim 42, and wherein, the operation of carrying out ultrasonic wave processing is the operation of carrying out the ultrasonic wave processing of 1～180 minute.
44. according to the method described in any one in claim 37～43, wherein, comprising:
Metal powder dispersion liquid is filtered, reclaims the operation of metal powder,
The metal powder that filtration is recovered is dry, obtains surface treated metal powder operation.
45. according to the method described in claim 44, wherein, is dried under oxygen atmosphere or inert atmosphere and carries out.
46. according to the method described in claim 37～45, wherein, in metal dispersion body, with respect to metal powder 1g, comprises the amino coupling agent that has more than 0.025g.
47. according to the method described in any one in claim 37～46, wherein,
The amino silane aqueous solution is the aqueous solution of the amino silane that represents of following formula I,
H 2n-R 1-Si(OR 2) 2(R 3) (formula I)
Wherein, in above-mentioned formula I,
R1 be straight chain shape there is side chain, saturated or undersaturated, replacement or unsubstituted, ring type or non-ring type, there is heterocycle or do not there is the divalent group of hydrocarbon heterocycle, C1～C12,
R2 is the alkyl of C1～C5,
R3 is the alkyl of C1～C5 or the alkoxyl of C1～C5.
48. according to the method described in claim 47, and wherein, R1 is be selected from-(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-in group, wherein, n, m, j are more than 1 integer.
49. according to the method described in any one in claim 37～46, wherein,
Coupling agent aqueous solution is the aqueous solution containing amino titanate esters that Formula Il represents,
(H 2n-R 1-O) pti(OR 2) q(formula II)
Wherein, in above-mentioned formula II,
R1 be straight chain shape there is side chain, saturated or undersaturated, replacement or unsubstituted, ring type or non-ring type, there is heterocycle or do not there is the divalent group of hydrocarbon heterocycle, C1～C12,
R2 is straight chain shape or the alkyl with side chain, C1～C5,
P and q are 1～3 integers, p+q=4.
50. according to the method described in claim 49, and wherein, R1 is be selected from-(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-in group, wherein, n, m, j are more than 1 integer.
51. according to the method described in any one in claim 31～50, wherein, metal powder be utilize damp process manufacture and metal powder.
52. according to the method described in any one in claim 31～50, wherein,
Surface treated metal powder is that any one the above adhesion amount in Si, Ti, Al, Zr, Ce, Sn is to be that 200～16000 μ g, N are more than 0.02% surface treated metal powder with respect to the % by weight of copper powder with respect to metal powder 1g,
It is more than 400 DEG C that sintering starts temperature.
53. manufacture the method for electrode, comprising:
The metal powder that will utilize the manufacture method manufacture described in any one in claim 31～52 and obtain is stuck with paste the operation being applied on base material,
The conductive metal being applied on base material is stuck with paste to the operation that heating is burnt till.
54. according to the method described in claim 53, and wherein, electrode is paster multi-layer ceramic capacitor electrode.
55. metal powders stick with paste, its be utilize the manufacture method manufacture described in any one in claim 31～52 and metal powder stick with paste, wherein,
Utilize aperture 5 μ m, effective area 9.0cm 2filter carry out the filtration under diminished pressure of 0.3atm, the quality seeing through was more than 35% with respect to the percentage (transmitance) of the ratio of the input quality of 4g after 15 minutes.
56. electrodes, its be utilize manufacture method manufacture described in claim 53 or 54 and electrode,
On electrode section with 0.5/cm 2below having maximum diameter is SiO more than 0.5 μ m 2, TiO 2, Al 2o 3in any.
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