CN104115237B

CN104115237B - Metal paste mixing and its manufacturing method

Info

Publication number: CN104115237B
Application number: CN201380010167.XA
Authority: CN
Inventors: 古泽秀树
Original assignee: JX Nippon Mining and Metals Corp
Current assignee: JX Nippon Mining and Metals Corp
Priority date: 2012-02-21
Filing date: 2013-02-21
Publication date: 2018-09-07
Anticipated expiration: 2033-02-21
Also published as: TW201344723A; KR101769337B1; KR20140126731A; CN104115237A; JPWO2013125659A1; WO2013125659A1; TWI527069B; JP6212480B2

Abstract

The present invention provides the manufacture that can be suitably used for patch multi-layer ceramic capacitor electrode and is sintered retardance excellent surface treated metal paste mixing and its manufacturing method, and the metal paste mixing is disperseed and contained in a solvent：It is 200~16000 μ g, N relative to the weight % of metal powder is 0.02% or more that surface treated metal powder, wherein adhesion amount more than any one in Si, Ti, Al, Zr, Ce, Sn, which are relative to metal powder 1g,；With the organic matter with carboxyl.

Description

Metal paste mixing and its manufacturing method

Technical field

The present invention relates to the metal paste mixings and its manufacturing method suitable for manufacturing patch multi-layer ceramic capacitor electrode.

Background technology

Patch multi-layer ceramic capacitor due to feature as small-size high-capacity is made in many electronic equipments Electronic unit.Patch multi-layer ceramic capacitor is formed as ceramic dielectric and internal electrode being laminated for stratiform and by its one Each layer of structure obtained from change, lamination respectively constitutes capacitor element, using external electrode by these elements with electrically in parallel side Formula connects, and is integrally formed small-sized and large capacity a capacitor.

In the manufacture of patch multi-layer ceramic capacitor, dielectric is manufactured as follows.That is, first, to BaTiO₃It is added as dispersant, the organic bond and solvent of shaping assistant, by crushing, mixing in equal dielectric raw materials powder It closes, bubble removal step, obtains slurry.Then, using rubbing methods such as die coating methods, by slurry coating and thin PET film etc. is spread into In carrier film.It is dried, obtains thin dielectric piece（Raw cook（green sheet））.

On the other hand, the metal powder as the raw material of the internal electrode of patch multi-layer ceramic capacitor, with dielectric original The situation at feed powder end is same, by the mixing with organic bond and solvent as dispersant, shaping assistant, bubble removal step, Form the copper powder paste of pulp-like（Copper is pasted）.Mainly raw cook is printed on using silk screen print method（Dielectric piece）Above and in being formed Portion's electrode, after the drying, the raw cook of stripping completion printing from carrier film, by such raw cook laminated multi-layer.

It is to the moulding pressure of raw cook application number 10~number 100MPa of lamination in the manner described above that it is integrated, then Cut into single patch.Then, interior electrode layer, dielectric layer are sintered at a high temperature of 1000 DEG C or so using firing furnace. In the manner described above, patch multi-layer ceramic capacitor can be manufactured.

For the internal electrode of such patch multi-layer ceramic capacitor, was developing the technology at that time, using Pt, but from the viewpoint of cost, using Pd, Pd-Ag alloy, Ni is currently mainly used.But in recent years, from environmental Kuznets Curves From the viewpoint of, it gradually requires Ni replacing with Cu.If, in principle, can in high-frequency applications in addition, Ni is replaced with Cu Realize low inductance（inductance）.In addition, Cu also has the advantages that cost is lower such compared with Ni.

On the other hand, along with the miniaturization of capacitor, exist the thin layer tendency of internal electrode, it is stated that next die Number become 1 μm or so.Therefore, expect the particle size smaller of the internal electrode powder used in copper powder paste.

But fusing point ratio Pt, Pd, Ni of Cu are low after all.In turn, due to the small particle of the above-mentioned particle expected like that Cause surface area to increase, fusing point caused to reduce, as a result, when using Cu as internal electrode powder when, be burnt into when, Cu powder compared with Start to melt under low temperature.This causes electrode layer itself to generate crack（crack）.In addition, after cooling, electrode layer is drastically shunk, Accordingly, there exist the strippings that dielectric layer and electrode layer occurs（Delamination, delamination）Possibility.In order to avoid such Unfavorable condition, it is desirable that internal electrode has the heat shrinkability characteristic with dielectric equal extent with metal powder, and the heat is received as expression The index of contracting characteristic has sintering start temperature.

Expect for such, before this, is suitable for the internal electrode of patch multi-layer ceramic capacitor in order to obtain Copper powder is pasted, it has been proposed that the method that the Cu powder used in being pasted to copper powder is surface-treated.

Patent document 1（Japanese Patent No. 4001438）It is following technology：Cu powder is distributed in liquid, is added thereto Add the aqueous solution of the water soluble salt of metallic element, adjusts pH, so that metal oxide is anchored at Cu powder surface, in turn, make these tables Surface treatment copper powder mutually collides, and carrys out the fixation of strengthening surface process layer.But process be adsorbed onto on copper powder by metal oxide, And fixed strengthen is constituted, therefore, there are problems in terms of productivity.In addition, when the grain size of copper powder is become than 0.5 μm of smaller, ruler The very little metal oxide particle with absorption is closely sized to, therefore is envisioned absorption of the oxide on copper powder itself and become difficult.

Patent document 2（Japanese Patent No. 4164009）It is the skill with the coating copper powder of silicone oil with specific functional group Art.But due to mixing oil and Cu powder, so being easy agglutination, there are problems in terms of operability.In addition, it is difficult into being about to Filtering when oil is detached with Cu powder, there are problems in terms of operability.

Patent document 3（Japanese Patent No. 3646259）It is the alkoxy that will have been hydrolyzed with ammonia catalyst in Copper Powder Surface Silane polycondensation forms SiO₂The technology of gel coating film.But in applicable 1 μm of copper powder below of grain size, it is used as urges in order to prevent The NH of agent₃Agglutination, it is necessary to which continuous addition, but quality of the reaction controlling dependent on specific addition operative skill are reacted Control it is extremely difficult, from operability and productivity from the aspect of there are problems.

Existing technical literature

Patent document

Patent document 1：No. 4001438 bulletins of Japanese Patent No.

Patent document 2：No. 4164009 bulletins of Japanese Patent No.

Patent document 3：No. 3646259 bulletins of Japanese Patent No..

Invention content

Problems to be solved by the invention

As described above, expecting the manufacture for the internal electrode that can be suitably employed in patch multi-layer ceramic capacitor, sintering Retardance, operability and productivity is excellent, copper powder paste.

Therefore, the object of the present invention is to provide the systems that can be suitably employed in patch multi-layer ceramic capacitor electrode It is making, sintering retardance is excellent, surface treated copper powder paste and its manufacturing method.

Means for solving the problems

Present inventor has performed further investigations, as a result, it has been found that, by mixing copper powder with amino silane aqueous solution, make amino Silane is adsorbed in Copper Powder Surface, from without the agglutination after surface treatment, can obtain as a result, sintering retardance unexpectedly The copper powder paste improved, so as to complete the present invention.In turn, copper powder paste is by being distributed to by surface treated copper powder Obtained from coordinating aliphatic acid when in solvent, by the cooperation of the aliphatic acid, the agglutination of surface treated copper powder is extremely dropped It is low.These manufacturing operations are very simple, do not need the technical ability of height, operability is excellent, and productivity is excellent.In addition, for according to For the copper powder paste based on surface treated copper powder that aforesaid way obtains, even with the copper powder of the small copper powder of particle Paste, also shows high sintering start temperature.In turn, even if when being similarly surface-treated to the metal powder other than copper powder, When being surface-treated using the coupling agent other than amino silane, the surface treated of excellent can be also got similarly Metal powder, it follows that the metal paste mixing of excellent specific property can be obtained.

Therefore, the invention reside in following（1）~（36）.

（1）

Copper powder is pasted, and is disperseed in a solvent and is contained：

It is 500~16000 μ g that surface treated copper powder, the wherein adhesion amount of Si, which are relative to copper powder 1g, and N is relative to copper The weight % of powder is 0.05% or more, and

Organic matter with carboxyl.

（2）

（1）The copper powder paste, disperses and contains in a solvent：

Organic matter with carboxyl.

（3）

（1）Or（2）The copper powder paste, wherein other than surface treated copper powder and with the organic matter of carboxyl, It disperses and contains adhesive resin in a solvent.

（4）

（1）~（3）Any one of described in copper powder paste, wherein surface treated copper powder is carried out with silane coupling agent Cross the copper powder of surface treatment.

（5）

（4）The copper powder paste, wherein silane coupling agent is amino silane.

（6）

（1）~（5）Any one of described in copper powder paste, wherein in surface treated copper powder, N is relative to copper powder Weight % is in the range of 0.05%~0.50%.

（7）

（1）~（6）Any one of described in copper powder paste, wherein surface treated copper powder is to surface treated copper Powder is further heat-treated and is eliminated the copper powder of N.

（8）

（1）~（7）Any one of described in copper powder paste, wherein surface treated copper powder is in oxygen atmosphere or indifferent gas The copper powder of N is heat-treated and eliminated under atmosphere.

（9）

（1）~（8）Any one of described in copper powder paste, wherein sintering start temperature be 400 DEG C or more.

（10）

（1）~（9）Any one of described in copper powder paste, wherein surface treated copper powder is by the water of amino silane Obtained from being dried and cure after solution and copper powder mixing, stirring.

（11）

（1）~（10）Any one of described in copper powder paste, wherein surface treated copper powder is for surface treatment The amount of amino silane is the copper powder to be surface-treated under conditions of 0.01 mL or more relative to copper powder 1g.

（12）

（11）The described copper powder paste, wherein it is 0.05mL or more that surface treated copper powder, which is in the amount of amino silane, with The mixing of copper powder, mixing time are the copper powder being surface-treated under the conditions of 30 minutes below.

（13）

（4）~（11）Any one of described in copper powder paste, wherein amino silane is monoamine base silane or diamino silanes.

（14）

（1）~（13）Any one of described in copper powder paste, wherein surface treated copper powder be to using damp process and obtain To the copper powder that is surface-treated of raw material copper powder.

（15）

（1）~（14）Any one of described in copper powder paste, wherein surface treated copper powder is D50≤1.5 μm.

（16）

（1）~（14）Any one of described in copper powder paste, wherein surface treated copper powder is D50≤1.0 μm.

（17）

（1）~（14）Any one of described in copper powder paste, wherein surface treated copper powder is D50≤0.5 μm, Dmax ≤1.0μm。

（18）

（1）~（17）Any one of described in copper powder paste, wherein the size distribution of surface treated copper powder be a wave Peak.

（19）

（1）~（18）Any one of described in copper powder paste, wherein copper powder paste be that internal electrode is pasted with copper powder.

（20）

（1）~（18）Any one of described in copper powder paste, wherein copper powder paste be that external electrode is pasted with copper powder.

（21）

（1）~（20）Any one of described in copper powder paste, wherein with the organic matter of carboxyl be carboxylic acid or amino acid.

（22）

（1）~（20）Any one of described in copper powder paste, wherein with the organic matter of carboxyl be aliphatic acid.

（23）

（22）The copper powder paste, wherein aliphatic acid is the saturated or undersaturated aliphatic acid of C3~C24.

（24）

（22）The copper powder paste, wherein aliphatic acid is C3~C24, the aliphatic acid that double key number is 0~2.

（25）

（22）The described copper powder paste, wherein aliphatic acid be selected from crotonic acid, acrylic acid, methacrylic acid, octanoic acid, n-nonanoic acid, Capric acid, lauric acid, 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, paulownia Acid, tuberlostearic acid, arachidic acid（Arachic acid）, 8,11- eicosadienoic acids, 5,8,11- eicosatrienoic acids, peanut four Olefin(e) acid, behenic acid, lignoceric acid, nervonic acid, elaidic acid, sinapic acid, docosahexaenoic acid, eicosapentaenoic acid, One or more of parinaric acid.

（26）

（22）The copper powder paste, wherein aliphatic acid is selected from one or more of stearic acid, oleic acid, linoleic acid.

（27）

（1）~（26）Any one of described in copper powder paste, wherein solvent is that alcoholic solvent, glycol ether solvent, acetic acid esters are molten Agent, ketone solvent or hydrocarbon solvent.

（28）

（27）The described copper powder paste, wherein alcoholic solvent is must selected from terpineol, dihydro-terpineol, isopropanol, butyl card One or more of alcohol, tyerpinyl ethoxy-ethanol, dihydro tyerpinyl ethoxy-ethanol.

（29）

（27）The copper powder paste, wherein glycol ether solvent is selected from one or more of butyl carbitol.

（30）

（27）The copper powder paste, wherein acetate solvent is selected from acetate of butyl carbitol, dihydro-terpineol acetic acid One or more of ester, terpin alcohol acetic ester, acetic acid dihydro Pueraria lobota thread ester, acetic acid Pueraria lobota thread ester.

（31）

（27）The copper powder paste, wherein ketone solvent is methyl ethyl ketone.

（32）

（27）The copper powder paste, wherein hydrocarbon solvent is selected from one or more of toluene, hexamethylene.

（33）

（1）~（32）Any one of described in copper powder paste, wherein quality of the aliphatic acid relative to surface treated copper powder Than（Aliphatic acid/surface treated copper powder）In the range of 1/1000~1/10.

（34）

（1）~（33）Any one of described in copper powder paste, wherein mass ratio of the aliphatic acid relative to solvent（Aliphatic acid/molten Agent）In the range of 1/100~1/10.

（35）

（1）~（34）Any one of described in copper powder paste, wherein mass ratio of the solvent relative to surface treated copper powder （Solvent/surface treated copper powder）In the range of 1/4~1/1.

（36）

（1）~（35）Any one of described in copper powder paste, wherein using 5 μm of aperture, effective area 9.0cm²Filter into When being filtered under diminished pressure of row 0.3atm, the percentage of the quality of transmission relative to the ratio of the input quality of 4g（Transmitance）At 30 seconds It is 35% or more afterwards.

In addition, the present invention also reside in it is following（41）~（44）.

（41）

Patch multi-layer ceramic capacitor is to use（1）~（36）Any one of described in paste and make obtained by.

（42）

Multilager base plate, outermost layer be equipped with by（41）The patch multi-layer ceramic capacitor.

（43）

Multilager base plate is equipped in internal layer（41）The patch multi-layer ceramic capacitor.

（44）

Electronic unit, equipped with（42）Or（43）The multilager base plate.

In addition, the present invention also reside in it is following（51）~（59）.

（51）

Copper powder paste manufacturing method, include by surface treated copper powder and with carboxyl organic matter dispersion in a solvent Process to prepare paste：

In the surface treated copper powder adhesion amount of Si be relative to copper powder 1g be 500~16000 μ g, N relative to The weight % of copper powder is 0.05% or more.

（52）

（51）The method, wherein the process for preparing paste is disperseed following substance in a solvent to prepare the work of paste Sequence：

Organic matter with carboxyl.

（53）

（51）The method, wherein the process for preparing paste is：

Other than surface treated copper powder and with the organic matter of carboxyl, adhesive resin is also dispersed in solvent The process for preparing paste.

（54）

（51）~（53）Any one of described in method, wherein with the organic matter of carboxyl be aliphatic acid.

（55）

（51）~（54）Any one of described in method, wherein prepare paste process after, further include：

With the process for the paste that filter filtering is prepared.

（56）

（55）The method, wherein filter has 1~8 μm of aperture.

（57）

（55）Or（56）The method, wherein the process utilization being filtered with filter is filtered under diminished pressure or pressure filtration It carries out.

（58）

（57）The method, wherein the pressure being filtered under diminished pressure is the pressure of the range of 0.1~1.0atm.

（59）

（57）The method, wherein the pressure of pressure filtration is the pressure of the range of 0.1~2.0atm.

In addition, the present invention also reside in it is following（61）~（79）.

（61）

（51）~（59）Any one of described in method, wherein surface treated copper powder be using manufacture through surface at Surface treated copper powder obtained by the method manufacture of the copper powder of reason, the manufacturing method include：

Copper powder is mixed with amino silane aqueous solution, the process for preparing copper powder dispersion liquid.

（62）

（61）The method, wherein the process including stirring copper powder dispersion liquid.

（63）

（61）Or（62）The method, wherein include the process that ultrasonication is carried out to copper powder dispersion liquid.

（64）

（63）The method, wherein the process for carrying out ultrasonication is the ultrasonication of carry out 1~180 minute Process.

（65）

（61）~（64）Any one of described in method, wherein including：

Copper powder dispersion liquid is filtered, the process to recycle copper powder,

The copper powder drying that filtering is recovered, the process for obtaining surface treated copper powder.

（66）

（65）The method, wherein dry to be carried out by heat treatment in 30~120 minutes at 50~90 DEG C.

（67）

（65）Or（66）The method, wherein drying carries out under oxygen atmosphere or inert atmosphere.

（68）

（61）~（67）Any one of described in method, wherein in copper dispersion liquid, relative to copper powder 1g, including 0.025g Above amino silane.

（69）

（61）~（68）Any one of described in method, wherein amino silane aqueous solution be following formula I indicate amino silane Aqueous solution.

H₂N-R¹- Si（OR²）₂（R³）（Formulas I）

（Wherein, in above-mentioned Formulas I,

R1 be straight-chain or with branch, saturated or unsaturated, substituted or unsubstituted, ring type or non-ring type, With heterocycle or without heterocycle, the hydrocarbon of C1~C12 bivalent group,

R2 is the alkyl of C1~C5,

R3 is the alkyl of C1~C5 or the alkoxy of C1~C5.）.

（70）

（69）The method, wherein R1 is the divalent of the straight-chain saturated hydrocarbons selected from substituted or unsubstituted C1~C12 Group, the bivalent group of branched saturated hydrocarbons of substituted or unsubstituted C1~C12, substituted or unsubstituted C1~C12 it is straight The bivalent group of chain unsaturated hydrocarbons, substituted or unsubstituted C1~C12 branched unsaturated hydrocarbons bivalent group, substitution or The bivalent group of the ring type hydrocarbon of unsubstituted C1~C12, the hetero ring type hydrocarbon of substituted or unsubstituted C1~C12 bivalent group, Group in the bivalent group of the aromatic hydrocarbon of substituted or unsubstituted C1~C12.

（71）

（69）The method, wherein R1 be selected from-（CH₂）_n,-（CH₂）_n（CH）_m（CH₂）_j-1,- （CH₂）_n（CC）（CH₂）_n-1,-（CH₂）_n- NH-（CH₂）_m,-（CH₂）_n- NH-（CH₂）_m- NH- （CH₂）_j,-（CH₂）_n-1（CH）NH₂（CH₂）_m-1,-（CH₂）_n-1（CH）NH₂（CH₂）_m-1- NH-（CH₂）_j In group（Wherein, the integer that n, m, j are 1 or more）.

（72）

（69）The method, wherein R1 is-（CH₂）_nOr-（CH₂）_n- NH-（CH₂）_m.

（73）

（71）~（72）Any one of described in method, wherein n, m, j are 1,2 or 3 each independently.

（74）

（69）~（73）Any one of described in method, wherein R2 is methyl or ethyl.

（75）

（69）~（74）Any one of described in method, wherein R3 is methyl, ethyl, methoxy or ethoxy.

（76）

（61）~（75）Any one of described in method, wherein copper powder be using damp process manufacture obtained by copper powder.

（77）

（61）~（76）Any one of described in method, wherein

In surface treated copper powder,

It is 500~16000 μ g that the adhesion amount of Si, which is relative to copper powder 1g,

N is 0.05% or more relative to the weight % of copper powder；

It is 400 DEG C or more to be sintered start temperature.

（78）

The method for manufacturing electrode, including：

It will utilize（51）~（57）、（61）~（77）Any one of described in manufacturing method manufacture obtained by copper powder muddle cloth Process on to base material,

The process that the electric conductivity copper being applied on base material is pasted into heating firing.

（79）

（78）The method, wherein electrode is patch multi-layer ceramic capacitor electrode.

In addition, the present invention also reside in it is following（81）~（83）.

（81）

Copper powder is pasted, and is to utilize（51）~（57）、（61）~（77）Any one of described in manufacturing method manufacture obtained by.

（82）

Electrode is to utilize（78）Obtained by the manufacturing method manufacture.

（83）

Patch multi-layer ceramic capacitor electrode is to utilize（79）Obtained by the manufacturing method manufacture.

In addition, the present invention also reside in it is following（91）~（92）.

（91）

Copper powder is pasted, and is to utilize（51）~（57）、（61）~（77）Any one of described in method manufacture obtained by copper powder paste, Wherein,

Utilize 5 μm of aperture, effective area 9.0cm²Filter carry out when being filtered under diminished pressure of 0.3atm, the quality of transmission is opposite In the percentage of the ratio of the input quality of 4g（Transmitance）It is 35% or more over the course of 15 mins.

（92）

Electrode is to utilize（78）Or（79）Obtained by the manufacturing method manufacture.

In turn, the present invention also resides in following（101）~.

（101）

Metal paste mixing, disperses and contains in a solvent：

Surface treated metal powder, wherein adhesion amount more than any one in Si, Ti, Al, Zr, Ce, Sn is phase Be 200~16000 μ g, N for metal powder 1g relative to the weight % of metal powder it is 0.02% or more, and

Organic matter with carboxyl.

（102）

（101）The metal paste mixing, wherein in addition to surface treated metal powder and the organic matter with carboxyl it Outside, disperse in a solvent and contain adhesive resin.

（103）

（101）~（102）Any one of described in metal paste mixing, wherein metal powder is copper powder.

（104）

（101）~（102）Any one of described in metal paste mixing, wherein metal powder is any in Pt, Pd, Ag, Ni, Cu Kind metal powder.

（105）

（101）~（104）Any one of described in metal paste mixing, wherein any one in Si, Ti, Al, Zr, Ce, Sn It is 300~16000 μ g that above adhesion amount, which is relative to metal powder 1g,.

（106）

（101）~（104）Any one of described in metal paste mixing, wherein any one in Si, Ti, Al, Zr, Ce, Sn It is 500~16000 μ g that above adhesion amount, which is relative to metal powder 1g,.

（107）

（101）~（106）Any one of described in metal paste mixing, wherein any one in Si, Ti, Al, Zr, Ce, Sn It is 3000 μ g or less that above adhesion amount, which is relative to metal powder 1g,.

（108）

（101）~（106）Any one of described in metal paste mixing, wherein any one in Si, Ti, Al, Zr, Ce, Sn It is 1500 μ g or less that above adhesion amount, which is relative to metal powder 1g,.

（109）

（101）~（108）The metal paste mixing, wherein N is 0.05% or more relative to the weight % of metal powder.

（110）

（101）~（109）Any one of described in metal paste mixing, wherein any one in Si, Ti, Al, Zr, Ce, Sn It is any one in Ti, Al, Zr, Ce, Sn or more above.

（111）

（101）~（109）Any one of described in metal paste mixing, wherein any one in Si, Ti, Al, Zr, Ce, Sn It is Si above.

（112）

（101）The metal paste mixing, wherein metal powder is copper powder, the adhesion amount of Si be relative to copper 1g be 500~ 16000 μ g, N are 0.05% or more relative to the weight % of copper powder.

（113）

（101）The metal paste mixing, wherein metal powder is copper powder, the adhesion amount of Si be relative to copper 1g be 500~ 3000 μ g, N are 0.05% or more relative to the weight % of copper powder.

（114）

（101）~（113）The metal paste mixing, wherein surface treated metal powder is to use coupling agent surface treatment The metal powder crossed.

（115）

（101）~（114）The metal paste mixing, wherein be adsorbed with using coupling agent treatment Si, Ti, Al, Zr, Ce, It is more than any one in Sn.

（116）

（101）~（115）The metal paste mixing, wherein coupling agent is silane, titanate esters（titanate）, Aluminate Any one of.

（117）

（101）~（116）The metal paste mixing, wherein coupling agent is the coupling agent that end is amino.

（118）

（101）~（117）The metal paste mixing, wherein coupling agent is amino silane.

（119）

（101）~（118）Any one of described in metal paste mixing, wherein with the organic matter of carboxyl be carboxylic acid or amino Acid.

（120）

（101）~（119）Any one of described in metal paste mixing, wherein with the organic matter of carboxyl be aliphatic acid.

（121）

（120）The metal paste mixing, wherein aliphatic acid is the saturated or undersaturated aliphatic acid of C3~C24.

（122）

（120）The metal paste mixing, wherein aliphatic acid is the aliphatic acid that the double key number of C3~C24 is 0~2.

（123）

（120）The metal paste mixing, wherein aliphatic acid is selected from crotonic acid, acrylic acid, methacrylic acid, octanoic acid, nonyl Acid, capric acid, lauric acid, 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, flower Raw acid（Arachic acid）, 8,11- eicosadienoic acids, 5,8,11- eicosatrienoic acids, arachidonic acid, behenic acid, 1 in lignoceric acid, nervonic acid, elaidic acid, sinapic acid, docosahexaenoic acid, eicosapentaenoic acid, parinaric acid Kind or more.

（124）

（101）~（123）Any one of described in metal paste mixing, wherein solvent is alcoholic solvent, glycol ether solvent, acetic acid Ester solvent, ketone solvent or hydrocarbon solvent.

（125）

（119）~（124）Any one of described in metal paste mixing, wherein aliphatic acid is relative to surface treated metal The mass ratio of powder（Aliphatic acid/surface treated copper powder）In the range of 1/100~1/10.

（126）

（119）~（125）Any one of described in metal paste mixing, wherein mass ratio of the aliphatic acid relative to solvent（Fat Acid/solvent）In the range of 1/100~1/10.

（127）

（101）~（126）Any one of described in metal paste mixing, wherein using 5 μm of aperture, effective area 9.0cm²'s Filter carries out 0.3atm and is filtered under diminished pressure, the percentage of the quality of transmission relative to the ratio of the input quality of 4g（Transmitance） It is 35% or more after 30 seconds.

（128）

Patch multi-layer ceramic capacitor is to use（101）~（127）Any one of described in paste and obtained by manufacturing.

（129）

（128）The patch multi-layer ceramic capacitor, wherein on internal electrode section there are a diameter of 10nm with On SiO₂、TiO₂、Al₂O₃Any one of.

（130）

（128）Or（129）The patch multi-layer ceramic capacitor, wherein with 0.5/cm on internal electrode section² Exist below the SiO that maximum diameter is 0.5 μm or more₂、TiO₂、Al₂O₃Any one of.

（131）

The manufacturing method of metal paste mixing, wherein include by surface treated metal powder and organic matter with carboxyl point Dissipate the process to prepare paste in a solvent：

Adhesion amount more than any one in the surface treated metal powder in Si, Ti, Al, Zr, Ce, Sn is phase Be 200~16000 μ g, N for metal powder 1g relative to the weight % of metal powder it is 0.02% or more.

（132）

（131）The method, wherein the process for preparing paste is：

Other than surface treated metal powder and with the organic matter of carboxyl, also adhesive resin is dispersed in molten Agent is come the process for preparing paste.

（133）

（131）~（132）Any one of described in method, wherein with the organic matter of carboxyl be aliphatic acid.

（134）

（131）~（133）Any one of described in method, wherein by surface treated metal powder and aliphatic acid point It is scattered to after the process for preparing paste in solvent, including：

With the process for the paste that filter filtering is prepared.

（135）

（134）The method, wherein filter has 1~8 μm of aperture.

（136）

（134）Or（135）The method, wherein the process being filtered with filter is by being filtered under diminished pressure or pressurizeing It filters and carries out.

（137）

（131）~（136）Any one of described in method, wherein surface treated metal powder be using manufacture through table Surface treated metal powder obtained by the method manufacture of the metal powder of surface treatment, the manufacturing method include：

Metal powder is mixed with the coupling agent aqueous solution with amino, the process for preparing metal powder dispersion liquid.

（138）

（137）The method, wherein metal powder is any metal powder in Pt, Pd, Ag, Ni, Cu.

（139）

（137）The method, wherein metal powder is copper powder.

（140）

（137）The method, wherein metal powder is any metal powder in Pt, Pd, Ag, Ni.

（141）

（137）~（140）Any one of described in method, wherein include stirring metal powder dispersion liquid process.

（142）

（137）~（141）Any one of described in method, wherein including to metal powder dispersion liquid carry out ultrasonication Process.

（143）

（142）The method, wherein the process for carrying out ultrasonication is the ultrasonication of carry out 1~180 minute Process.

（144）

（137）~（143）Any one of described in method, including：

Metal powder dispersion liquid is filtered, the process to recycle metal powder,

The metal powder drying that filtering is recovered, the process for obtaining surface treated metal powder.

（145）

（144）The method, wherein drying carries out under oxygen atmosphere or inert atmosphere.

（146）

（137）~（145）The method, wherein in metal dispersion, relative to metal powder 1g, containing 0.025g with On the coupling agent with amino.

（147）

（137）~（146）Any one of described in method, wherein amino silane aqueous solution be following formula I indicate amino silicone The aqueous solution of alkane,

H₂N-R¹- Si（OR²）₂（R³）（Formulas I）

（Wherein, in above-mentioned Formulas I,

R2 is the alkyl of C1~C5,

R3 is the alkyl of C1~C5 or the alkoxy of C1~C5.）.

（148）

（147）The method, wherein R1 be selected from-（CH₂）_n,-（CH₂）_n（CH）_m（CH₂）_j-1,- （CH₂）_n（CC）（CH₂）_n-1,-（CH₂）_n- NH-（CH₂）_m,-（CH₂）_n- NH-（CH₂）_m- NH- （CH₂）_j,-（CH₂）_n-1（CH）NH₂（CH₂）_m-1,-（CH₂）_n-1（CH）NH₂（CH₂）_m-1- NH-（CH₂）_j In group（Wherein, the integer that n, m, j are 1 or more）.

（149）

（137）~（146）Any one of described in method, wherein coupling agent aqueous solution be Formula Il indicate contain amino Titanate esters aqueous solution,

（H₂N-R¹- O）_pTi（OR²）_q（Formula II）

（Wherein, in above-mentioned Formula II,

R2 is straight-chain or the alkyl with branch, C1~C5,

P and q is 1~3 integer, p+q=4.）.

（150）

（149）The method, wherein R1 be selected from-（CH₂）_n,-（CH₂）_n（CH）_m（CH₂）_j-1,- （CH₂）_n（CC）（CH₂）_n-1,-（CH₂）_n- NH-（CH₂）_m,-（CH₂）_n- NH-（CH₂）_m- NH- （CH₂）_j,-（CH₂）_n-1（CH）NH₂（CH₂）_m-1,-（CH₂）_n-1（CH）NH₂（CH₂）_m-1- NH-（CH₂）_j In group（Wherein, the integer that n, m, j are 1 or more）.

（151）

（131）~（150）Any one of described in method, wherein metal powder be using damp process manufacture obtained by metal Powder.

（152）

（131）~（150）Any one of described in method, wherein

Surface treated metal powder be any one in Si, Ti, Al, Zr, Ce, Sn more than adhesion amount be relative to Metal powder 1g is the surface treated metal powder that 200~16000 μ g, N are 0.02% or more relative to the weight % of copper powder,

It is 400 DEG C or more to be sintered start temperature.

（153）

The method for manufacturing electrode, including will utilize（131）~（152）Any one of described in manufacturing method manufacture obtained by Metal powder paste is applied to the process on base material,

The process that the conductive metal being applied on base material is pasted into heating firing.

（154）

（153）The method, wherein electrode is patch multi-layer ceramic capacitor electrode.

（155）

Metal paste mixing is to utilize（131）~（152）Any one of described in manufacturing method manufacture obtained by metal paste mixing, Wherein,

Utilize 5 μm of aperture, effective area 9.0cm²Filter carry out 0.3atm and be filtered under diminished pressure, the quality of transmission relative to The percentage of the ratio of the input quality of 4g（Transmitance）It is 35% or more over the course of 15 mins.

（156）

Electrode is to utilize（153）Or（154）Electrode obtained by the manufacturing method manufacture, wherein

With 0.5/cm on electrode section²Exist below the SiO that maximum diameter is 0.5 μm or more₂、TiO₂、Al₂O₃In appoint It is a kind of.

[invention effect]

The surface treated copper powder used in copper powder paste of the present invention will not be aggregated after surface treatment, It is excellent to be sintered retardance, even the copper powder that particle is small, also shows high sintering start temperature.Therefore, copper powder of the invention paste Sintering retardance it is excellent, the dispersibility of copper powder in paste is also excellent, therefore, the problem being avoided that in the manufactures such as stripping electrode, Advantageously carry out the manufacture of patch multi-layer ceramic capacitor electrode.It, can be in addition, for the surface treated copper powder It is manufactured to carrying out very simple processing as the copper powder of raw material, it, can be right for the manufacture of the copper powder of present invention paste The surface treated copper powder carries out very simple processing to manufacture, and therefore, there is no need to superb technical ability, operability and production Rate is excellent.In addition, through the invention, for the metal powder other than copper powder, can also get similarly the gold with excellent characteristic Belong to paste mixing.

[description of the drawings]

[Fig. 1] Fig. 1 is perpendicular to the TEM image of the section on the surface of surface treated copper powder.

Specific implementation mode

Embodiment is enumerated below to explain the present invention in detail.The present invention is not limited to the following specific embodiment parties enumerated Formula.

It in the present invention, is mixed into copper powder is about to amino silane aqueous solution, the process to prepare copper powder dispersion liquid, by the copper Surface treated copper powder can be obtained in powder dispersion liquid, into the surface treated copper powder and tool for being about to obtain in the manner described above There is the organic matter dispersion of carboxyl in a solvent come the process for preparing paste, copper powder paste can be manufactured.

It in a preferred embodiment, can also be to other than surface treated copper powder and with the organic matter of carboxyl Dispersing binder resin in solvent can also add other additives according to expectation.

Specifically, surface treated copper powder can be obtained according to the method being explained later.From the work for surface treatment It is originated for the copper powder of raw material, which is surface-treated, then divides itself and the organic matter etc. with carboxyl together It is scattered in solvent, obtains copper powder paste, this is also within the scope of the invention.In turn, from the system of the raw material copper powder for surface treatment Starting is made, obtains copper powder paste, this is also within the scope of the invention.

In the present invention, as the organic matter with carboxyl, preferably amino acid or carboxylic acid.As carboxylic acid, can enumerate for example Aliphatic acid.As amino acid, such as alanine, arginine, asparagine, aspartic acid, cysteine, glutamy can be enumerated Amine, glutamic acid, glycine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, Threonine, tryptophan, tyrosine, valine.In the present invention, as the organic matter with carboxyl, aliphatic acid is particularly preferably used.

Aliphatic acid used in the present invention can enumerate the saturated or unsaturated fat that carbon atom number is C3~C24 Acid.In a preferred embodiment, can be used C3~C24, further preferably use C4~C22, further preferably use C8~ C22 further preferably uses C12~C22, C16~C20 is further preferably used, particularly preferably using the carbon atom number of C18 Aliphatic acid.In a preferred embodiment, it is such as 0~4, such as 0~3, such as 0~2 that number of double bonds, which can be used, Aliphatic acid.From the aspect of filter filtering quickly, particularly preferred double key number is 1 aliphatic acid.In a preferred embodiment, As aliphatic acid, can be used, there is lipophilic aliphatic acid can enumerate for example above-mentioned carbon atom number as such aliphatic acid Aliphatic acid.

In a preferred embodiment, it as such aliphatic acid, can be used selected from crotonic acid, acrylic acid, metering system Acid, octanoic acid, n-nonanoic acid, capric acid, lauric acid, myristic acid, pentadecanoic acid, palmitic acid, palmitoleic acid, Heptadecanoic acide, stearic acid, oil Acid, vaccenic acid, linoleic acid,（9,12,15）Leukotrienes,（6,9,12）Leukotrienes, dihomo-gamma-linolenic acid, eleostearic acid, knot Core stearic acid, arachidic acid（Arachic acid）, 8,11- eicosadienoic acids, 5,8,11- eicosatrienoic acids, arachidonic acid, Behenic acid, lignoceric acid, nervonic acid, elaidic acid, sinapic acid, docosahexaenoic acid, eicosapentaenoic acid, 18 carbon One or more of tetraenoic acid.In addition, in particularly preferred embodiments, as aliphatic acid, can be used selected from stearic acid, oil It is in acid, linoleic acid and acrylic acid, be preferably selected from stearic acid, one or more of oleic acid and linoleic acid.As aliphatic acid, can make With the salt of aliphatic acid, but in a preferred embodiment, aliphatic acid is it is preferable to use aliphatic acid itself, rather than the salt of aliphatic acid.

For the solvent used in the present invention, the solvent used in the silk-screen printing paste of electronic material can be used, As such solvent, such as alcoholic solvent, glycol ether solvent, acetate solvent, ketone solvent and hydrocarbon solvent can be enumerated.It is molten as alcohol Agent can enumerate such as terpineol, isopropanol, butyl carbitol.As terpineol, can enumerate α-terpineol, β-terpineol, γ-terpineol, particularly preferred α-terpineol.As glycol ether solvent, such as butyl carbitol can be enumerated.It is molten as acetic acid esters Agent can enumerate such as acetate of butyl carbitol.As ketone solvent, such as methyl ethyl ketone can be enumerated.As hydrocarbon solvent, can lift Go out such as toluene, hexamethylene.In a preferred embodiment, it as solvent, can be used selected from terpineol, isopropanol, butyl card Must one or more of alcohol, acetate of butyl carbitol, methyl ethyl ketone, toluene, hexamethylene, preferably using being selected from α-terpin One or more of alcohol, butyl carbitol and acetate of butyl carbitol.

For copper powder of the present invention paste, in a preferred embodiment, aliphatic acid is relative to surface treated Copper powder mass ratio（Aliphatic acid/surface treated copper powder）Such as can for 1/1000~1/10 range, preferably 1/ 1000~1/20 range.In a preferred embodiment, mass ratio of the aliphatic acid relative to solvent（Aliphatic acid/solvent）Such as Can be 1/100~1/10 range, preferably 1/60~1/15 range.In a preferred embodiment, solvent is relative to warp The mass ratio of the copper powder of surface treatment（Solvent/surface treated copper powder）Such as can for 1/4~1/1 range, preferably 1/3 ~1/1.5 range.

Adhesive used in the present invention can be used with the adhesive of the adhesion strength of substrate as long as improving, make For such adhesive, cellulose-based resin, epoxy system resin, acrylic resin can be enumerated.In a preferred embodiment, Such as polyvinyl acetal resin, polyvinyl butyral resin, acrylate can be used.

The operation that surface treated copper powder, aliphatic acid etc. are distributed in solvent and prepare paste can utilize well known dispersion Method carries out, and according to expectation, can be stirred, be kneaded, ultrasonication.It in a preferred embodiment, can be into solvent While adding surface treated copper powder, or before the surface treated copper powder of addition, aliphatic acid is added into solvent.

In the preferred embodiments of the present invention, can also it make to have the organic matter preferred fatty acid of carboxyl directly to adsorb After surface treated copper powder, then carry out being distributed to the process that paste is made in solvent, but in order to make agglutination, drying process In treatability it is good, be preferably made in the process of paste surface treated copper powder to be distributed in solvent, add simultaneously Organic matter, preferred fatty acid with carboxyl, make it be adsorbed onto on copper powder.

In the preferred embodiments of the present invention, surface treated copper powder and aliphatic acid are being distributed to solvent After the process for preparing paste, the process for filtering the paste being prepared with filter is carried out.Such filtering based on filter be in order to Pasted using copper powder to be formed it is fine connect up, very thin conductive layer（Electrode）And carry out.In a preferred embodiment, filter example Filter as the aperture with 1~8 μm, preferably 1~5 μm can be used.In a preferred embodiment, the filtering based on filter can Using be filtered under diminished pressure or pressure filtration carry out.The pressure being filtered under diminished pressure for example can be 0.1~1.0atm, preferably 0.2~0.6 The pressure of range.The pressure of pressure filtration can be for example 0.1~2.0atm, the pressure of preferably 0.2~1.0 range.

In a preferred embodiment, for copper powder of the present invention paste, 5 μm of aperture, effective area are utilized 9.0cm²Filter carry out when being filtered under diminished pressure of 0.3atm, the percentage of the quality of transmission relative to the ratio of the input quality of 4g （Transmitance）For example can be 35% or more, 40% or more, 45% or more, 50% or more, 55% or more after 30 seconds, the example after 1 minute Such as can be 35% or more, 40% or more, 45% or more, 50% or more, 55% or more, after 8 minutes for example can be 40% or more, 45% or more, 50% or more, 55% or more, 60% or more, over the course of 15 mins for example can be 40% or more, 45% or more, 50% or more, 55% or more, 60% or more.

It is micro- in order to be formed from the aspect of the excessive copper powder of grain size in the copper powder that removing contains, the copper powder being aggregated It is thin connect up, very thin conductive layer（Electrode）, filtered copper powder paste is preferred, but if the copper powder paste before filtering was not Filter the copper powder that easy state contains grain size is sufficiently small and the state that is decreased sufficiently of agglutination, then since filter blocks, copper The rate of recovery of paste mixing is low, thus filter operation itself is difficult to carry out.Even if in the reality for being formed as the above-mentioned filtering based on filter Operation be easy carry out, the dispersity of copper powder as the sufficiently high rate of recovery can be obtained from the aspect of, it is of the present invention Copper powder paste is also excellent.The reason of copper powder paste of the present invention is formed as dispersity excellent in this way is still not clear, but Inventors believe that may be due to the excellent surface state of surface treated copper powder itself, so be also caused by through The copper powder of surface treatment and the organic matter with carboxyl（Preferred fatty acid）Carboxyl combination.

As the copper powder for surface treatment, it can be used and utilize copper powder obtained by the manufacture of well known method.For example, copper powder can Using copper powder obtained by being manufactured using dry process, manufactured using damp process obtained by any one of copper powder.From until the present invention Surface treatment until always become wet process from the aspect of, copper powder obtained by being manufactured preferably by damp process.

Amino silane aqueous solution is the aqueous solution that can be used as the amino silane that silane coupling agent uses.In preferred embodiment party In formula, for the usage amount of amino silane, it is formed as the aqueous solution of the amino silane comprising the amino silane measured as follows： Relative to the quality 1g of copper powder when forming copper powder dispersion liquid, the quality of amino silane be 0.025g or more, preferably 0.050g with On, further preferred 0.075g or more, further preferred 0.10g or more, alternatively, being formed as comprising the amino silane measured as follows Amino silane aqueous solution：The quality 1g of copper powder when relative to formation copper powder dispersion liquid, for example, 0.025~0.500g, The amount of the range of 0.025~0.250g, 0.025~0.100g.In a preferred embodiment, for the usage amount of amino silane For, it is formed as including the aqueous solution for the amino silane measured as follows, the quality of copper powder when relative to formation copper powder dispersion liquid 1g, the volume for being included in the amino silane at 25 DEG C is 0.01mL or more, 0.025mL or more, preferably 0.050mL or more, into one Preferred 0.075mL or more, further preferred 0.10mL or more are walked, alternatively, may be alternatively formed to comprising the amino silane measured as follows The aqueous solution of amino silane：The quality 1g of copper powder when relative to formation copper powder dispersion liquid, for example, 0.025~0.500mL, The amount of the range of 0.025~0.250mL, 0.025~0.100mL.

In a preferred embodiment, as amino silane, usable includes 1 or more amino and/or imino group Silane.The amino and imino group number for including in amino silane for example can be respectively 1~4, preferably respectively 1~3, into One step preferably 1~2.In a preferred embodiment, the amino and imino group number for including in amino silane can be respectively 1 It is a.The amino silane that the amino for including in amino silane and imino group number summation are 1 can be especially referred to as mono amino silicon The amino silane that the amino for including in amino silane and imino group number summation are 2 is especially referred to as diamino silanes by alkane, will The amino and imino group number summation for including in amino silane are that 3 amino silanes are especially referred to as triamido silane.In this hair It is preferable to use monoamine base silane, diamino silanes in bright.In a preferred embodiment, as amino silane, it includes 1 that can be used The monoamine base silane of a amino.In a preferred embodiment, amino silane can be in molecular end, preferably straight-chain or branch Amino silane of the molecular end of the chain of chain comprising at least one, such as 1 amino.

As amino silane, such as N-2- can be enumerated（Amino-ethyl）- 3- aminopropylmethyldimethoxysilanes, N-2-（Amino-ethyl）- 3- TSL 8330s, 3- TSL 8330s, 1- aminopropyls Trimethoxy silane, 2- TSL 8330s, 1,2- diaminopropyls trimethoxy silane, 3- amino -1- Acrylic trimethoxy silane, 3- amino -1- propinyls trimethoxy silane, 3-aminopropyltriethoxysilane, 3- Triethoxysilyl-N-（1,3- dimethyl-butane）Propylamine, N- phenyl -3- aminopropyl trimethoxy silicon Alkane, N-（Vinyl benzyl）- 2- amino-ethyl -3- TSL 8330s, 3- aminopropyl triethoxies Silane, 3- TSL 8330s, N-（2- amino-ethyls）- 3- TSL 8330s, N- （2- amino-ethyls）- 3- aminopropylmethyldimethoxysilanes, 3-（N- phenyl）TSL 8330.

In a preferred embodiment, the amino silane that following formula I can be used to indicate.

H₂N-R¹- Si（OR²）₂（R³）（Formulas I）

In above-mentioned Formulas I,

R2 is the alkyl of C1~C5,

R3 is the alkyl of C1~C5 or the alkoxy of C1~C5.

In a preferred embodiment, the R1 of above-mentioned Formulas I be straight-chain or with branch, it is saturated or unsaturated, take Generation or unsubstituted, ring type or non-ring type, bivalent group with heterocycle or without heterocycle, the hydrocarbon of C1~C12, into one It can be the bivalent group selected from substituted or unsubstituted, C1~C12 straight-chain saturated hydrocarbons, substitution or unsubstituted to walk preferred R1 , the bivalent group of the branched saturated hydrocarbons of C1~C12, the two of substituted or unsubstituted, C1~C12 straight-chain unsaturated hydrocarbons Valence group, the bivalent group of substituted or unsubstituted, C1~C12 branched unsaturated hydrocarbons, substituted or unsubstituted, C1~ The bivalent group of the ring type hydrocarbon of C12, the bivalent group of substituted or unsubstituted, C1~C12 hetero ring type hydrocarbon, substitution or unsubstituted , group in the bivalent group of the aromatic hydrocarbon of C1~C12.In a preferred embodiment, the R1 of above-mentioned Formulas I be C1~ The bivalent group of C12, saturated or unsaturated chain hydrocarbon, the bivalent group for the chain hydrocarbon being further preferably saturated.Into one Step is preferably the bivalent group that the atom of two ends of chain structure has free valence.In a preferred embodiment, two The carbon atom number of valence group can be such as C1~C12, preferably C1~C8, preferably C1~C6, preferably C1~C3.

In a preferred embodiment, the R1 of above-mentioned Formulas I can be selected from-（CH₂）_n,-（CH₂）_n（CH）_m （CH₂）_j-1,-（CH₂）_n（CC）（CH₂）_n-1,-（CH₂）_n- NH-（CH₂）_m,-（CH₂）_n- NH-（CH₂）_m NH-（CH₂）_j,-（CH₂）_n-1（CH）NH₂（CH₂）_m-1,-（CH₂）_n-1（CH）NH₂（CH₂）_m-1- NH- （CH₂）_jIn group（Wherein, the integer that n, m, j are 1 or more）.（Wherein, above-mentioned（CC）Indicate three keys of C and C.）Preferred Embodiment in, R1 can be-（CH₂）_nOr-（CH₂）_n- NH-（CH₂）_m.（Wherein, above-mentioned（CC）Indicate C and C Three keys.）In a preferred embodiment, the hydrogen as the R1 of above-mentioned bivalent group can be replaced by amino, can be example As 1~3 hydrogen, such as 1~2 hydrogen, such as 1 hydrogen are replaced by amino.

In a preferred embodiment, n, m, j of above-mentioned Formulas I can be 1 or more 12 integer below each independently, excellent 1 or more 6 integer below, further preferred 1 or more 4 integer below are selected, such as can be the integer in 1,2,3,4, Such as can be 1,2 or 3.

In a preferred embodiment, the R2 of above-mentioned Formulas I can be the alkyl of C1~C5, the preferred alkyl of C1~C3, into The alkyl of the preferred C1~C2 of one step, such as can be methyl, ethyl, isopropyl or propyl, preferably can be methyl or ethyl.

In a preferred embodiment, can be the alkyl of C1~C5 as alkyl for the R3 of above-mentioned Formulas I, it is excellent The alkyl of C1~C3, the alkyl of further preferred C1~C2 are selected, such as can be methyl, ethyl, isopropyl or propyl, preferably may be used Think methyl or ethyl.Can be the alkoxy of C1~C5, preferably as alkoxy in addition, for the R3 of above-mentioned Formulas I The alkoxy of C1~C3, the alkoxy of further preferred C1~C2, such as can be methoxyl group, ethyoxyl, isopropoxy or third Oxygroup preferably can be methoxy or ethoxy.

Amino silane aqueous solution is mixed with copper powder using well known method.It, can be suitably with well known when mixing Method is stirred.In a preferred embodiment, mixing can for example carry out at normal temperatures, such as can 5~80 DEG C, 10~40 DEG C, carry out at a temperature of 20~30 DEG C of range.

In a preferred embodiment, after mixing copper powder dispersion liquid, ultrasonication can be carried out.Ultrasonication Processing time selects according to the state of copper powder dispersion liquid, can preferably 1~180 minute, further preferred 3~150 minutes, into One step preferably 10~120 minutes, further preferred 20~80 minutes.

In a preferred embodiment, ultrasonication can be with every 100mL preferably 50~600W, further preferred 100 The output power of~600W carries out.In a preferred embodiment, ultrasonication can preferably 10~1MHz, further it is excellent It selects and is carried out under the frequency of 20~1MHz, further preferred 50~1MHz.

For the copper powder in copper powder dispersion liquid, can after being surface-treated as described above using amino silane, It detaches from dispersion liquid, is recycled as surface treated copper powder.For the separation and recycling, well known side can be used Method, for example, filtering can be used, centrifuge, decantation（decantation）Deng.It, can be into according to expectation after separation and recovery Row drying.It is dry that well known method can be used to carry out, for example, the drying based on heating can be carried out.Heat drying is using for example At a temperature of 50~90 DEG C, 60~80 DEG C, for example, 30~120 minutes, heat treatment in 45~90 minutes carries out.In heat drying Later, for copper powder, processing can further be crushed according to expectation.In addition, for the surface treated copper powder of recycling, go out In antirust or the purpose of improve dispersibility in paste, organic matter etc. can also be made further to be adsorbed in surface treated copper The surface of powder.

As described above, in a preferred embodiment, copper powder for surface treatment can be used to be obtained using damp process Copper powder.In a preferred embodiment, it can be used using following methods as the manufacturing method of the copper powder obtained using damp process And the copper powder manufactured, the method includes：Cuprous oxide is added into the aqueous solvent comprising Arabic gum additive, to make The process of slurry, the process in 5 seconds into slurry disposably adding dilute sulfuric acid not to be homogenized reaction.Preferred real It applies in mode, above-mentioned slurry can be maintained at room temperature（20~25 DEG C）Hereinafter, and add be likewise held in room temperature or less Dilute sulfuric acid, not to be homogenized reaction.In a preferred embodiment, above-mentioned slurry can be maintained at 7 DEG C hereinafter, and Addition is likewise held in 7 DEG C of dilute sulfuric acids below, not to be homogenized reaction.In a preferred embodiment, dilute sulfuric acid Addition can be added in such a way that pH2.5 or less, preferably pH2.0 or less, further preferred pH1.5 are below.Preferably implementing In mode, addition of the dilute sulfuric acid into slurry can within 5 minutes, within preferably 1 minute, it is 30 seconds further preferred within, Within further preferred 10 seconds, it is 5 seconds further preferred within mode add.In a preferred embodiment, can make it is above-mentioned not Homogenizing reaction terminates 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, the cuprous oxide obtained using well known method can be used, preferably aoxidize Cuprous particle, grain size of the cuprous oxide particle etc. be not direct with using grain size of particle of copper powder for reacting and generating etc. is not homogenized Therefore the cuprous oxide particle of coarse grain can be used in correlation.The principle for not being homogenized reaction is as follows：

Cu₂O+H₂SO₄→ Cu ↓+CuSO₄+ H₂O

For as this be not homogenized obtained from copper powder, also can according to it is expected to be washed, it is antirust, filtering, drying, broken It is broken, classification, then mix with amino silane, but in a preferred embodiment, according to expectation washed, antirust, filtering Afterwards, without drying, directly it is mixed with amino silane aqueous solution.

In a preferred embodiment, using it is above-mentioned be not homogenized reaction obtained from copper powder utilization laser diffraction formula granularity The average grain diameter that distribution measurement device measures is 0.25 μm or less.In a preferred embodiment, it is not homogenized reaction using above-mentioned Obtained from D10, D90, Dmax for being measured using laser diffraction formula particle size distribution device of copper powder meet [Dmax≤D50 × 3, D90≤D50 × 2, D10 >=D50 × 0.5] relational expression, and particle diameter distribution have simple spike.In preferred embodiment party In formula, using it is above-mentioned be not homogenized reaction obtained from copper powder the measurement based on laser diffraction formula particle size distribution device in, Size distribution is a wave crest（With simple spike）.In a preferred embodiment, it is filled using laser diffraction formula particle size distribution It is [D50≤1.5 μm] to set the value that measures, preferably [D50≤1.0 μm], further preferably [D50≤0.5 μm, Dmax≤1.0 μm].As laser diffraction formula particle size distribution device, such as Shimadzu Seisakusho Ltd. SALD-2100 can be used.

The surface treated copper powder obtained in the manner described above has excellent sintering retardance.As sintering retardance Index, have sintering start temperature.The sintering start temperature is the powder compact that will be formed in reducing atmosphere by metal powder Heating, occurs certain certain volume change（It shrinks）When temperature.In this specification, temperature when will occur 1% volume contraction Degree is as sintering start temperature.Specifically, being determined as the record of embodiment.It is sintered the high situation of start temperature Indicate that sintering retardance is excellent.

In a preferred embodiment, the sintering start temperature of the surface treated copper powder obtained in the manner described above can Think 450 DEG C or more, preferably 500 DEG C or more, further preferred 600 DEG C or more, further preferred 700 DEG C or more, further it is excellent Select 780 DEG C or more, further preferred 800 DEG C or more, further preferred 810 DEG C or more, further preferred 840 DEG C or more, into one Preferably 900 DEG C or more, further preferred 920 DEG C or more, further preferred 950 DEG C or more of step.In the past, high sintering was being required to open The Ni Ultramicro-powders used in the case of beginning temperature（0.2~0.4 μm of average grain diameter）Sintering start temperature at 500~600 DEG C In range, compared with such case, which is fine using than the Cu that Ni is cheap and is easy to get Particle, and with identical or preferably excellent sintering retardance.

It in a preferred embodiment, can be in reducing atmosphere by powder compact liter for surface treated copper powder Temperature and form sintered body.Obtained sintered body is formed as excellent electrode.The sintering process can be particularly suitable for patch The manufacture of the internal electrode of multi-layer ceramic capacitor.The sintered body can be especially suitably as patch multi-layer ceramic capacitor Internal electrode uses.In the preferred embodiments of the present invention, SiO₂Particle is scattered in electrode section so that can be formed very thin Electrode, meanwhile, the reliability of electrode is not reduced（Quality）.

In a preferred embodiment, for surface treated copper powder, relative to copper powder 1g, the adhesion amount of Si is logical Can be often 500~16000 μ g, preferably 500~3000 μ g.The Si adhesion amounts can utilize ICP（Inductively coupled plasma atom Emission spectrometry）It acquires.In a preferred embodiment, in turn, relative to copper powder weight, it can include 0.05wt%'s or more N.The mechanism that silane coupling agent is adsorbed in copper powder is still not clear, but inventors believe that the reason is as follows that：In end of silane Amino nitrogen and copper between generate interaction and adsorb.

In a preferred embodiment, for surface treated copper powder, what is formed using surface treatment contains Si The thickness of layer（Si thickness）Typically 0.6~25nm, preferably 1.0~25nm, further preferred 1.5~20nm.This contains Si The thickness of layer（Si thickness）Can refer in the section on the surface of surface treated copper powder, carrying out being based on EDS（X-ray energy Spectrum analysis）Measurement, with Si atoms relative to whole atoms presence than the Si atoms as maximum depth amount , it is specified that the range that the amount for being Si atoms is 10% or more when being 100%.For the section on the surface of surface treated copper powder For, at least 100 or more the copper powder particles observed from being sliced in sample, 5 are selected, respectively most clearly by it Boundary is measured and adds up to as the section perpendicular to the surface of surface treated copper powder.

In a preferred embodiment, for surface treated copper powder, can make N relative to the weight % of copper powder for Such as 0.05 weight % or more, preferably 0.06 weight % or more, further preferred 0.07 weight % or more, such as can be 0.05~ The range of 0.50 weight %, preferably 0.06~0.45 weight %, further preferred 0.08~0.40 weight %.Weights of the N relative to copper powder Amount % can be calculated as follows：Copper powder is set to melt at high temperature, by the NO generated₂Calculate attachment N amounts.

In a preferred embodiment, for surface treated copper powder, XPS is utilized（X-ray photoelectron spectroscopy） The N on the surface that the survey of analytic approach is measured be, for example, 1.0% or more, preferably 1.4% or more, further preferred 1.5% with It is upper, further preferably 1.6% or more, alternatively, for example 1.0~6.0%, preferably 1.4~6.0%, it is further preferred 1.5~ 6.0%, in the range of further preferred 1.6~6.0%, the photoelectron of N for example can be 1000cps（count per second） Above, preferably 1200cps or more, alternatively, for example can be the range of 1000~9000cps, preferably 1200~8000cps.

In a preferred embodiment, for surface treated copper powder, XPS is utilized（X-ray photoelectron spectroscopy） The Si on the surface that the survey of analytic approach is measured for example can be 0.6% or more, preferably 0.8% or more, further preferably 1.0% or more, further preferred 1.1% or more, further preferred 1.2% or more, further preferred 1.3% or more, further preferably 1.4% or more, alternatively, for example can 0.6~4.0%, preferably 0.8~4.0%, it is further preferred 1.0~4.0%, further excellent It selects 1.1~4.0%, is further preferred 1.2~4.0%, further preferred 1.3~4.0%, further preferred 1.4~4.0% range Interior, the photoelectron of Si for example can be 1000cps（Count per second, counting per second）Above, preferably 1200cps with On, alternatively, for example can be the range of 1000~12000cps, preferably 1200~12000cps.

In a preferred embodiment, it for surface treated copper powder, can also carry out based on amino silane After surface treatment, further it is surface-treated.As such surface treatment, can enumerate for example based on benzotriazole, imidazoles The antirust treatment of equal organic corrosion inhibitors will not make even if common processing in this way at the surface based on amino silane Reason disengaging etc..Therefore, in the limit for not damaging excellent sintering retardance, those skilled in the art can carry out this according to expectation The well known surface treatment of sample.That is, in the limit for not damaging excellent sintering retardance, further to warp of the present invention Copper powder obtained from the surface of the copper powder of surface treatment is surface-treated and copper powder are pasted also still within the scope of the invention.

It, also can be by the table that was illustrated above for copper powder when using metal powder other than copper powder in the present invention Surface treatment, and obtain excellent characteristic.When using the metal powder other than copper powder, can also be described by being directed to above-mentioned copper powder Preferred embodiment implement the present invention.As metal powder, such as any metal in Pt, Pd, Ag, Ni, Cu can be used Powder.Including copper powder, as preferred metal powder, any metal powder in Ag, Ni, Cu can be enumerated.

In the present invention, can as described above it be suitably carried out by the attachment of Si, but can also pass through the element other than Si Attachment is suitably carried out.It, also can be preferred by being described for above-mentioned Si in the case where adhering to the element other than Si Embodiment implements the present invention.As the element other than Si, any one in Ti, Al, Zr, Ce, Sn or more can be enumerated.Packet Including including Si, as preferred element, any one in Si, Ti, Al, Zr, Ce, Sn or more can be enumerated, it can be further preferred Enumerate any one in Si, Ti, Al or more.

It, can be suitably real by being surface-treated as described above to copper powder using silane coupling agent in the present invention It applies, but the coupling agent other than silane coupling agent can also be used and be surface-treated and be suitably carried out.As silane coupling agent with Outer coupling agent can enumerate titanate esters, Aluminate.It, respectively, can in the case of using silane coupling agent as coupling agent Suitably adhere to Si, in the case of using titanate esters, can suitably adhere to Ti, it, can be suitable in the case of using Aluminate Ground adheres to Al.The occupation mode of these coupling agents can apply the mode illustrated as described above for silane coupling agent.With silicon The structure of alkane coupling agent similarly, in titanate esters and the structure of Aluminate, it is also preferred that the substituent group for containing amino in end is matched The structure of the Ti and Al of atom centered on being located at.

In a preferred embodiment, the suitable adhesion amount as Si, Ti or Al based on above-mentioned coupling agent, is such as directed to Illustrated by copper powder like that, in turn, relative to metal powder 1g, can enumerate such as 200~16000 μ g, 300~16000 μ g, 500~ The range of 16000 μ g, for example, 200~3000 μ g, 300~3000 μ g, 500~3000 μ g range, such as 200~1500 μ g, The range of 300~1500 μ g, 500~1500 μ g.

In a preferred embodiment, the thickness of the si-containing formed using the surface treatment of metal powder（Si thickness）It can Think as illustrating as described above for copper powder, in turn, for the thickness containing Ti layers（Ti thickness）, al-containing layers thickness（Al Thickness）, or it is directed to the thickness of si-containing（Si thickness）As described above as explanation.

In a preferred embodiment, for surface treated metal powder, can make to utilize XPS（X-ray photoelectricity Sub- power spectrum）The Si on the surface that the survey of analytic approach is measured is as illustrating as described above for copper powder.In turn, in addition to Other than the Si adhered to using surface treatment, for Ti and Al, assay method same as Si can also be utilized, makes it be and needle It is same numberical range to numberical range as defined in Si.

In a preferred embodiment, for surface treated metal powder, can make to utilize XPS（X-ray photoelectricity Sub- power spectrum）The N on the surface that the survey of analytic approach is measured is as illustrating as described above for copper powder.

Using the metal powder other than copper powder come in the case of obtaining surface treated metal powder, at will be through surface The metal powder of reason is mixed with organic matters and the solvent such as aliphatic acid and according to desired adhesive resin to manufacture metal paste mixing Process, can also be carried out according to for the process that illustrates as described above of copper powder paste.In this case, the fat preferably used The organic matters such as acid, solvent, the type of adhesive resin and mixing ratio with for copper powder paste be illustrated above like that it is identical.It is right For the metal paste mixing obtained in the manner described above, in a preferred embodiment, such as it is illustrated above for copper powder paste As, there is same excellent characteristic, there is same excellent filter permeability, treatability, sintering retardance etc..

As the titanate esters that can suitably use in the present invention, the amino-containing titanate esters of Formula Il expression can be enumerated：

（H₂N-R¹- O）_pTi（OR²）_q（Formula II）

（Wherein, in above-mentioned Formula II,

R2 be straight-chain or with branch, the alkyl of C1~C5,

The integer that p and q is 1~3, p+q=4.）.

As the R1 of above-mentioned Formula II, the group that is preferably enumerated used as the R1 of above-mentioned Formulas I.As above-mentioned Formula II R1, such as can be selected from-（CH₂）_n,-（CH₂）_n（CH）_m（CH₂）_j-1,-（CH₂）_n（CC）（CH₂）_n-1,-（CH₂）_n- NH-（CH₂）_m,-（CH₂）_n- NH-（CH₂）_m- NH-（CH₂）_j,-（CH₂）_n-1 （CH）NH₂（CH₂）_m-1,-（CH₂）_n-1（CH）NH₂（CH₂）_m-1- NH-（CH₂）_jIn group（Wherein, n, m, j For 1 or more integer）.As particularly preferred R1, can enumerate-（CH₂）_n- NH-（CH₂）_m（Wherein, n+m=4, especially It is preferred that n=m=2）.

As the R2 of above-mentioned Formula II, the group that is preferably enumerated used as the R2 of above-mentioned Formulas I.Preferably implementing In mode, the alkyl of C3 can be enumerated, can particularly preferably enumerate propyl and isopropyl.

The p and q of above-mentioned Formula II are 1~3 integers, and p+q=4 preferably enumerates the combination of p=q=2, p=3, q=1 Combination.As the amino-containing titanate esters for being configured with functional group as described above, Plain Act KR44 can be enumerated （Ajinomoto Fine-Techno corporations）.

The metal powder of the present invention has high sintering start temperature as described above such as the copper powder as the present invention, passes through The metal powder is allocated, excellent conductive metal paste mixing can be manufactured, by being sintered the conductive metal paste mixing, can be manufactured excellent Electrode.The sintering start temperature of the metal powder of the present invention be illustrated above for copper powder it is such identical.Preferably implementing In mode, the electrode obtained through the invention can be the SiO for electrode section₂As being illustrated above, similarly, For the TiO of electrode section₂And the Al of electrode section₂O₃, or it is directed to the SiO of electrode section₂That is illustrated above Size, number, the density of sample.In a preferred embodiment, the SiO about electrode section₂, it is equivalent to using silane coupling agent The case where coupling agent as surface treatment, for the TiO of electrode section₂, it is equivalent to using titanate esters as surface treatment The case where coupling agent, for the Al of electrode section₂O₃, the case where being equivalent to using Aluminate as the coupling agent of surface treatment.

[embodiment]

Embodiment is enumerated below illustrates the present invention in further detail.The present invention is not limited to embodiments below.

[manufacture of surface treatment copper powder]

Surface treated copper powder is manufactured as described below.

[utilizing the powder processed of damp process]

The copper powder 20g for surface treatment is manufactured using damp process.Obtained copper powder has characteristic as described below.It measures Use laser diffraction formula particle size distribution device（Shimadzu Seisakusho Ltd. SALD-2100）.

D50 0.12μm

It is distributed a wave crest.

[preparation of silane-water solution]

The silane-water solution that 50mL has used following various silane is prepared respectively.

Silane：Diamino silanes A-1120（MOMENTIVE corporations）

Amino silane A-1110（MOMENTIVE corporations）

Epoxy silane Z-6040（Dow Corning Toray corporations）

Methyltrimethoxysilane KBM-13（Shin-Etsu Silicones corporations）

3- phenyl amino propyl trimethoxy silanes（MOMENTIVE corporations）

It is prepared in the range of 0.5~15vol% with concentration.In addition, other than amino system silane, dilute sulfuric acid is used PH is adjusted to 4.

The structural formula of various silane is as follows.

Diamino silanes A-1120：

H₂N-C₂H₄- NH-C₃H₆- Si（OCH₃）₃

Amino silane A-1110：

H₂N-C₃H₆- Si（OCH₃）₃

Epoxy silane Z-6040：

Methyltrimethoxysilane KBM-13：

H₃C-Si（OCH₃）₃

3- phenyl amino propyl trimethoxy silanes：

C₆H₅- NH-C₃H₆- Si（OCH₃）₃。

[surface treatment based on the mixing with silane-water solution]

Copper powder 20g and each silane-water solution 50mL is mixed, to prepare copper powder dispersion liquid, carries out 60 minutes immediately（Or 120 minutes）Ultrasonication（Co., Ltd.'s Tech jam systems, ultrasonic washer, 3 frequency types/W-113）（Output power 100W, frequency 100kHz）.In table 1, which is recorded as the time is mixed.Operation is at room temperature It carries out.

In addition, such as the record of table 1, in several embodiments, while being stirred using what is carried out using rotating vane （300rpm）It is stirred with above-mentioned ultrasonic wave, or only so that silane coupling agent is adsorbed in by using the stirring that rotating vane carries out Copper powder.

Copper powder dispersion liquid is filtered, surface treated copper powder is recycled, heat drying 1 hour, obtains through table at 70 DEG C The copper powder of surface treatment.

The processing that surface treated copper powder in each Examples and Comparative Examples is carried out is summarized in table 1.

[evaluation of surface treated copper powder]

For the surface treated copper powder obtained using aforesaid operations, evaluated using the following method.

[copper powder dimension measurement]

For the size of copper powder, profit is measured with the following method.Result is summarized in table 2.

Laser diffraction formula particle size distribution（Shimadzu Seisakusho Ltd. SLAD-2100）.

[measurement based on TMA]

Sample is made by surface treated copper powder, uses TMA（Thermomechanical Analyzer, thermomechanical point Analyzer）, sintering start temperature is measured under the following conditions.

Sample making condition

Powder compact size：7mm φ × 5mm high

Briquetting pressure：1Ton/cm²（1000kg weight/cm²）

（The zinc stearate of 0.5wt% is added as lubricant）

Determination condition

Device：Shimadzu Seisakusho Ltd. TMA-50

Heating：5 DEG C/min

Atmosphere：2vol%H₂- N₂（300cc/ minutes）

Load：98.0mN.

Like this, the zinc stearate of 0.5wt% is added into the copper powder as measure object and is mixed, by the mixing Object is loaded into the cylinder of diameter 7mm, is pressed into punch from top, is assigned in 1Ton/cm²The lower pressurization for being kept for 3 seconds, is shaped to phase When in the cylindric of about 5mm height.Under conditions of so that axis is vertical direction and assigning the load of 98.0mN in an axial direction, by this Formed body is loaded into heating furnace, in 2vol%H₂- N₂（300cc/ minutes）In flow, with heating rate for 5 DEG C/min, 50 It continuously heats up in~1000 DEG C of measurement range, automatically records the height change of formed body（The variation of dilation）.It will be at The height change of type body（It shrinks）Start and temperature of its shrinking percentage when reaching 1% is denoted as " sintering start temperature ".By each implementation The measurement result of example and the sintering start temperature of the surface treated copper powder in comparative example is summarized in table 3.

[analysis]

Analysis is attached to Si, N and C on the surface of surface treated copper powder under the following conditions.Result is summarized in Table 3.

Adhesion amount Si acid dissolves surface treated copper powder, passes through ICP（Inductively coupled plasma atomic emissions Spectroscopic methodology）It is quantified, finds out the unit mass relative to surface treated copper powder of the Si of attachment（g）Quality（μg）.

N, C at high temperature melts copper powder, by the NO generated₂、CO₂Attachment N, C amount is calculated, copper is attached to by measuring The amount of N, C in the whole surface of powder, come find out attachment N, C quality relative to surface treated copper powder quality matter Measure %（Weight %）.

[table 1]

[table 2]

[table 3]

Other than above-mentioned the Comparative Examples 1 to 5, tetraethoxysilane is used（TEOS）As silane coupling agent, ammonia is used As catalyst, copper powder is surface-treated, compares experiment, when using tetraethoxysilane, becomes following shape State：Obtained surface treatment copper powder is aggregated, and is observed by the naked eye, it is believed that is not surface-treated uniformly and grain size.This When, before surface treatment, D50=0.13 μm, Dmax=0.44 μm, but after surface treatment, D50=0.87 μm, Dmax=3.1 μ M becomes larger 7 times or so.In addition, size distribution becomes 2 wave crests before surface treatment for 1 wave crest.

According to the above results it is found that mixed amino silane-water solution of the present invention is manufactured through surface at For the copper powder of reason, although its manufacturing method is extremely simple, despite the copper powder with microsize, have contour molten with nickel Put the same or higher high sintering start temperature of the micro mist of metal.In addition we know, by the surface treated copper powder, using with The manufacturing process of the electrode of patch multi-layer ceramic capacitor is similarly sintered, and can manufacture sintered body；It manufactures in this wise（It is formed） To sintered body section in be dispersed with SiO₂Particle.

In addition, by above-mentioned result it is found that in order to realize adequately sintering retardance, as silane coupling agent, need for Amino silane with amino.In addition we know, as amino silane, preferably there is the amino silane of amino in end.Comparing In example 4, although the Si of visible opposite copper powder attachment sufficient amount, is not carried out adequately sintering retardance.Though its reason is unknown Really, but the present inventor speculates that reason may be as follows：In comparative example 4, amino silane is not formed as having amino in end Structure moreover, because phenyl ring is present in more leans on end than amino, therefore generates the state as steric hindrance, for burning The heating midway of knot, the amino silane or Si being temporarily attached on copper powder are detached from early stage from copper powder.

[the coherent manufacture for utilizing damp process]

Fine copper powder is manufactured as described below, and then copper powder obtained by manufacture is carried out at surface using amino silane Reason, surface treated copper powder of the present invention is consistently manufactured using damp process.

（1）Into Arabic gum 0.2g+ pure water 350mL, cuprous oxide 50g is added.

（2）Then, dilute sulfuric acid is disposably added（25wt%）50mL.

（3）It is stirred using rotating vane（300rpm × 10 minute）, then place 60 minutes.

（4）Then, precipitation is washed.

Washing carries out in the following way, initially, removes supernatant, and pure water 350mL is added and is stirred（300rpm×10 Minute）, then place 60 minutes, remove supernatant, pure water 350mL is added and is stirred（300rpm × 10 minute）, then put It sets 60 minutes, removes supernatant.

（5）Then, aminosilane-treated is carried out.

For aminosilane-treated, amino silane aqueous solution is added（50mL）, stir 60 minutes, at this point, being revolved Rotating vane piece（300rpm）+ ultrasonic wave（Co., Ltd.'s Tech jam systems, 3 frequency types of ultrasonic washer/W-113）（Output work Rate 100W, frequency 100kHz）Processing.Unlike this, it separately carries out merely with rotating vane（300rpm）Processing, only sharp With the processing of ultrasonic wave.As amino silane, diamino silanes A-1120 is used respectively（MOMENTIVE corporations）, amino silicone Alkane A-1110（MOMENTIVE corporations）.

（6）Then, it is filtered and carrys out precipitation and separation.

（7）Then, by the precipitation drying of separation.For drying（70℃×2h）For, it carries out under air atmosphere respectively The dry and drying in nitrogen.

Surface treated fine copper powder has been obtained by coherent manufacture in the manner described above.In the manner described above The surface treated copper powder arrived in the same manner as the surface treated copper powder of above-described embodiment there is excellent sintering to postpone Property, meanwhile, the SiO existing for its sintered body section₂Big number of particles it is small.In addition, for the coherent manufacture, Ke Yi It obtains all carrying out without dry ground before final products, easy and operability is excellent.

[manufacture of copper powder paste]

Each aminosilane-treated copper powder, each fat below obtained by embodiment 2,3,5 and Comparative Examples 1 and 2 manufacture will be utilized Acid and adhesive are distributed in solvent, have manufactured the copper powder paste of 20g.For surface treatment copper powder at this time：Solvent：Adhesive： It is 65 in the case where being added without adhesive for the mass ratio of aliphatic acid：34.3：0.7, in the case where adhesive is added, It is 65：27.2：7：0.8.It is used for later measurement using them as embodiment 9,10,11 and comparative example 5,6.

The surface treatment copper powder of embodiment 2：The diamino silanes that silane concentration is 2vol% are carried out to handle

The surface treatment copper powder of embodiment 3：The diamino silanes that silane concentration is 4vol% are carried out to handle

The surface treatment copper powder of embodiment 5：The diamino silanes that silane concentration is 10vol% are carried out to handle

The surface treatment copper powder of comparative example 1：Only carry out BTA processing

The surface treatment copper powder of comparative example 2：The epoxy silane that silane concentration is 10vol% is carried out to handle

Aliphatic acid：Oleic acid（C18,1 double bond）

Linoleic acid（C18,2 double bonds）

Acrylic acid（C3,1 double bond）

Adhesive：Polyvinyl butyral resin

Solvent：α-terpineol（TPO）Or butyl carbitol

With above-mentioned cooperation internal electricity has been obtained using three rollers come mixing surfaces processing copper powder, aliphatic acid, adhesive, solvent It pastes pole.

[transmitance of filter filtering measures]

For the copper powder paste manufactured as described above, it is filtered under diminished pressure at 0.2atm with 5 μm of the glass filter in aperture, Transit dose measuring after rigid input after 30 seconds, after 8 minutes, after 15 minutes（g）, calculated relative to most with percentage Just put into the amount in filter（g）Ratio, as transmitance（%）.By embodiment 9,10,11 and comparative example 5,6（With and without viscous Mixture resin）In obtained result be shown in following table 4 and table 5.

[table 4]

*：Paste can not measured through filter.

[table 5]

*：Paste can not measured through filter.

It follows that the copper powder being surface-treated using diamino silanes, compared with comparative example, in either case Show at least 9~10 times or more such apparent excellent transmitances.

The above-mentioned copper powder paste through filter filtering is applied to the on piece of the paste of dielectric medium powder with about 1 μm of thickness, as a result, The uniform piece of copper powder paste can be readily derived.The piece is sintered, it as a result can be in dielectric layer and the conductive layer formed by copper Electrode is manufactured in the case of not peeling-off.

For copper powder, particle size is smaller, and agglutination is more apparent.Moreover, as described above like that, if generating agglutination, Then only so operability, productivity is just made also to reduce.It in turn, can when forming the internal electrode of patch multi-layer ceramic capacitor Use the printing technologies such as silk-screen printing, it is therefore desirable to before it will print, include with the filter filtering with small aperture The copper powder of copper powder particle is pasted.But if the copper powder for using particle size small for accurate printing, agglutination becomes easy hair Raw, if copper powder is aggregated in copper powder paste, becoming can not be by filter, and there is a situation where that can not print electrode, pattern is such.If Filter blocks, then the utilization ratio that not only copper powder is pasted（Yield）It reduces, but also can occur stop to replace filter The such situation of entire printing equipment.It is therefore prevented that the agglutination of copper powder is important in electrode manufacture.

In such a case, it is known that copper powder paste of the present invention is formed as other than sintering retardance is excellent, also It can prevent from being aggregated, filter permeability also excellent copper powder paste, therefore as can be suitably used for having used the electrode of printing technology The copper powder of manufacture is pasted.

[manufacture for having carried out the copper powder of antirust treatment]

Manufacture has further carried out surface treated copper powder the copper powder of antirust treatment.Obtaining the above embodiments After 4 copper powder, in order to carry out antirust treatment, benzotriazole aqueous solution is distributed it to（0.1g/L）In 100 mL, with rotation Blade with 500rpm stir within 10 minutes, is filtered, dries（The lower 70 DEG C × 1h of nitrogen atmosphere）, and then prevented Become rusty the copper powder handled（Embodiment 12）.

[evaluation for having carried out the copper powder of antirust treatment]

For having carried out the copper powder of above-mentioned antirust treatment（Embodiment 12）, it is carried out similarly evaluation with the above embodiments 4, Its result is summarized in 6~table of table 8.It should be noted that the size of treated in table 7 copper powder be in embodiment 12, The size of copper powder after antirust treatment, each evaluation of table 8 are also the result for the copper powder for having carried out antirust treatment.By these knots Fruit will not be lost surface treated it is found that even if in the case where having carried out antirust treatment to surface treated copper powder The excellent characteristic of copper powder.

[embodiment]

Other than the embodiment being illustrated above, embodiment below is enumerated, is illustrated in further detail The present invention.The present invention is not limited to embodiments below.

[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

The copper powder 20g for surface treatment has been manufactured using above-mentioned damp process.That is,

（1）Into 0.4 g of Arabic gum+pure water, 350 mL, 50 g of cuprous oxide is added.

（2）Then, dilute sulfuric acid is disposably added（25wt%）50 mL.

（4）Then, precipitation is washed.

Washing carries out in the following way, initially, removes supernatant, and pure water 350mL is added and is stirred（300rpm×10 Minute）, then place 60 minutes, remove supernatant, pure water 350mL is added and is stirred（300rpm × 10 minute）, then put It sets 60 minutes, copper fine powder is made to settle.Laser diffraction formula particle size distribution device is utilized in this state（Shimadzu Seisakusho Ltd. SLAD-2100）Granulometry is carried out, as the granulometry before surface treatment.

By the particle size of obtained copper powder（D50、Dmax）It is shown in table 7.Laser diffraction formula size distribution is used in measurement Measurement device（Shimadzu Seisakusho Ltd. SALD-2100）.

Embodiment 13

According to No. 4164009 bulletins of Japanese Patent No., copper powder has been obtained using chemical reduction method.That is, by Arabic gum After 2g is added in the pure water of 2900mL, copper sulphate 125g is added on one side and is stirred, adds 80% hydrazine monohydrate 360mL on one side. After adding hydrazine monohydrate, copper oxide is set to react from room temperature to 60 DEG C, then through 3 hours through 3 times.After reaction, The slurry obtained with filtered on buchner funnel is then washed with pure water and methanol, and then is made it dry and obtained copper powder.It utilizes The step of embodiment 1, mixes the copper powder with diamino silanes coupling agent aqueous solution, has obtained surface treatment silver powder.Utilize implementation The step of example 1, has rated its characteristic.

（Nickel powder）

Nickel powder has used the NF32 of Toho Titanium（D50 is 0.3 μm）.

（Silver powder）

According to Japanese Unexamined Patent Publication 2007-291513 powder.That is, silver nitrate 12.6g is dissolved in the pure water of 0.8L, addition 25% Ammonium hydroxide 24mL, then nitric acid ammonia 40g is added, prepare silver-colored amine complex salt aqueous solution.Gelatin is added thereto with the ratio of 1g/L, is made For electrolyte, anode, cathode use DSE pole plates, with 200A/m²Current density, 20 DEG C of solution temperature be electrolysed, one It is electrolysed 1 hour on one side while the silver particles of electrocrystallization are scraped from pole plate.With the obtained silver powder of filtered on buchner funnel, use successively Pure water, alcohol are washed, 12 hours dry under air atmosphere at 70 DEG C.By the silver powder dry classification, D50 has been finally obtained The silver powder for being 0.5 μm for 0.1 μm, Dmax.

（The preparation of coupling agent aqueous solution）

The silane-water solution for having used following various silane of 50mL is prepared respectively.

Silane：Diamino silanes A-1120（MOMENTIVE corporations）

Methyltrimethoxysilane KBM-13（Shin-Etsu Silicones corporations）

Titanate esters：Amino-containing Plain Act KR44（Ajinomoto Fine-Techno corporations）

Not amino-containing Plain Act KR TTS（Ajinomoto Fine-Techno corporations）

It is prepared in the range of 1~10vol% with concentration.In addition, other than amino system coupling agent, dilute sulfuric acid is used PH is adjusted to 4.

The structural formula of various silane is as follows.

Diamino silanes A-1120：

H₂N-C₂H₄- NH-C₃H₆- Si（OCH₃）₃

Methyltrimethoxysilane KBM-13：

H₃C-Si（OCH₃）₃

Amino-containing Plain Act KR44

The side chain organo-functional group of hydrophobic group

（CH₃）₂CH-O-

The side chain organo-functional group of hydrophilic group

- O-（C₂H₄）- NH-（C₂H₄）- NH₂

Not amino-containing Plain Act KR TTS

The side chain organo-functional group of hydrophobic group

（CH₃）₂CH-O-

The side chain organo-functional group of hydrophilic group

- O-CO-（C₁₇H₃₅）.

（Surface treatment）

From according to above-mentioned（Copper fine powder）Supernatant is removed in the copper fine powder slurry that step obtains, is dried not making copper fine powder In the case of, it is above-mentioned through mixing in 60 minutes using any one of following methods method（The preparation of coupling agent aqueous solution）The idol of preparation Join agent（Embodiment 18~20, comparative example 11）.

（1）Rotating vane（300rpm）+ ultrasonic wave（Co., Ltd.'s Tech jam systems, 3 frequency type of ultrasonic washer/ W-113）（Output power 100W, frequency 100kHz）

（2）Merely with rotating vane（300rpm）

（3）Merely with ultrasonic wave

Then, aspirator is utilized（aspirator）Above-mentioned coupling agent aqueous solution is filtered, then, in nitrogen atmosphere Under drying in 1 hour is carried out to it at 70 DEG C, crushed with mortar.Granulometry is carried out again in this state.

For above-mentioned（Nickel powder）In obtain nickel powder, according to above-mentioned（Silver powder）The silver powder that step obtains, utilization are above-mentioned（1）'s Step through 60 minutes with it is above-mentioned（The preparation of coupling agent aqueous solution）The coupling agent of preparation mixes, and is surface-treated（Implement Example 14~17 and 21~26, comparative example 8,10,12,13）.

[manufacture of copper powder paste]

Each aminosilane-treated metal obtained by embodiment 14,16,19,22,25 and comparative example 7~11 will be utilized to manufacture Powder, each aliphatic acid below and adhesive are distributed in solvent, manufacture the metal paste mixing of 20g.For surface treatment gold at this time Belong to powder：Solvent：Adhesive：It is 65 in the case where not adding adhesive for the mass ratio of aliphatic acid：34.3：0.7, adding It is 65 in the case of having added adhesive：27.2：7：0.8.It is used them as embodiment 27~31 and comparative example 14~18 In later measurement.

The surface treatment nickel powder of embodiment 14：The diamino silanes that silane concentration is 1vol% are carried out to handle

The surface treatment silver powder of embodiment 16：The diamino silanes that silane concentration is 1vol% are carried out to handle

The surface treatment copper powder of embodiment 19：Carry out the amino-containing titanate esters processing of a concentration of 6vol% of titanate esters

The surface treatment nickel powder of embodiment 22：Carry out the amino-containing titanate esters processing of a concentration of 6vol% of titanate esters

The surface treatment silver powder of embodiment 25：Carry out the amino-containing titanate esters processing of a concentration of 6vol% of titanate esters

The silver powder of comparative example 7：It is not surface-treated

The surface treatment silver powder of comparative example 8：The methyltrimethoxysilane that silane concentration is 10vol% is carried out to handle

The nickel powder of comparative example 9：It is not surface-treated

The surface treatment nickel powder of comparative example 10：The methyltrimethoxysilane that silane concentration is 10vol% is carried out to handle

The surface treatment copper powder of comparative example 11：Carry out the titanate esters processing without amino that silane concentration is 10vol%

Aliphatic acid：Oleic acid（C18,1 double bond）

Linoleic acid（C18,2 double bonds）

Acrylic acid（C3,1 double bond）

Adhesive：Polyvinyl butyral resin

Solvent：α-terpineol（TPO）Or butyl carbitol

[transmitance of filter filtering measures]

For the copper powder paste manufactured as described above, it is filtered under diminished pressure at 0.2atm with 5 μm of the glass filter in aperture, Transit dose measuring after rigid input after 30 seconds, after 8 minutes, after 15 minutes（g）, calculated relative to most with percentage Just put into the amount in filter（g）Ratio, as transmitance（%）.Embodiment 27~31 and comparative example 14~18（With and without viscous Mixture resin）In obtained result be shown in following table 9 and table 10.

[table 6]

[table 7]

[table 8]

[table 9]

*：Paste can not measured through filter.

[table 10]

*：Paste can not measured through filter.

From the above results, using the metal powder other than copper powder, and using the coupling agent other than amino silane, to make When making surface treated metal powder, also with the copper powder being surface-treated using amino silane the case where it is same, utilize pole Its simple manufacturing method can form the metal paste mixing with high sintering start temperature.In addition we know, by above-mentioned through surface The metal powder of reason is similarly sintered using the manufacturing process of the electrode with patch multi-layer ceramic capacitor, can manufacture sintered body.Separately It is outer it is found that the metal paste mixing obtained by above-mentioned surface treated metal powder manufacture, the case where being pasted with copper powder, is same, is formed as Not only sintering retardance is excellent, but also can prevent from being aggregated, and filter permeability also excellent metal paste mixing, becoming can be suitably used for The metal paste mixing for having used the electrode of printing technology to manufacture.

[industrial feasibility]

The copper powder paste of the present invention is formed as the dispersed also excellent copper powder paste for being sintered excellent, in paste the copper powder of retardance, Therefore the problem being avoided that in the manufactures such as stripping electrode advantageously manufactures the manufacture of patch stacked capacitor electrode.In addition, right For the manufacture of the copper powder paste of the present invention, carrying out very simple processing to the surface treated copper powder can manufacture, because This, does not need superb technical ability, and operability and productivity are excellent.In addition, the metal paste mixing of the present invention also pastes same tool with copper powder There is excellent characteristic.The present invention is industrially useful invention.

Claims

1. metal paste mixing, disperses and contains in a solvent：

Surface treated metal powder, wherein adhesion amount more than any one in Si, Ti, Al, Zr, Ce, Sn be relative to Metal powder 1g is 200~16000 μ g, and attachment N is 0.02% or more relative to the weight % of metal powder, and

Organic matter with carboxyl,

5 μm of aperture, effective area 9.0cm are utilized to above-mentioned metal paste mixing²Filter carry out when being filtered under diminished pressure of 0.3atm, penetrate Quality relative to 4g input quality ratio percentage after 30 seconds be 35% or more.

2. metal paste mixing according to claim 1, wherein in addition to surface treated metal powder and with the organic of carboxyl Other than object, disperses in a solvent and contain adhesive resin.

3. metal paste mixing according to claim 1 or 2, wherein metal powder is copper powder.

4. metal paste mixing according to claim 1 or 2, wherein metal powder is any metal in Pt, Pd, Ag, Ni, Cu Powder.

5. metal paste mixing according to claim 1 or 2, wherein more than any one in Si, Ti, Al, Zr, Ce, Sn It is 300~16000 μ g that adhesion amount, which is relative to metal powder 1g,.

6. metal paste mixing according to claim 1 or 2, wherein more than any one in Si, Ti, Al, Zr, Ce, Sn It is 500~16000 μ g that adhesion amount, which is relative to metal powder 1g,.

7. metal paste mixing according to claim 1 or 2, wherein more than any one in Si, Ti, Al, Zr, Ce, Sn It is 3000 μ g or less that adhesion amount, which is relative to metal powder 1g,.

8. metal paste mixing according to claim 1 or 2, wherein more than any one in Si, Ti, Al, Zr, Ce, Sn It is 1500 μ g or less that adhesion amount, which is relative to metal powder 1g,.

9. according to the metal paste mixing of claims 1 or 2, wherein attachment N is 0.05% or more relative to the weight % of metal powder.

10. metal paste mixing according to claim 1 or 2, wherein more than any one in Si, Ti, Al, Zr, Ce, Sn It is any one in Ti, Al, Zr, Ce, Sn or more.

11. metal paste mixing according to claim 1 or 2, wherein more than any one in Si, Ti, Al, Zr, Ce, Sn It is Si.

12. metal paste mixing according to claim 1, wherein metal powder is copper powder, and the adhesion amount of Si is to be relative to copper 1g 500~16000 μ g, attachment N are 0.05% or more relative to the weight % of copper powder.

13. metal paste mixing according to claim 1, wherein metal powder is copper powder, and the adhesion amount of Si is to be relative to copper 1g 500~3000 μ g, attachment N are 0.05% or more relative to the weight % of copper powder.

14. according to the metal paste mixing of claims 1 or 2, wherein surface treated metal powder is with coupling agent surface treatment mistake Metal powder.

15. according to the metal paste mixing of claims 1 or 2, wherein be adsorbed with using coupling agent treatment Si, Ti, Al, Zr, Ce, It is more than any one in Sn.

16. metal paste mixing according to claim 14, wherein coupling agent is any one of silane, titanate esters, Aluminate.

17. metal paste mixing according to claim 14, wherein coupling agent is the coupling agent that end is amino.

18. metal paste mixing according to claim 14, wherein coupling agent is amino silane.

19. metal paste mixing according to claim 1 or 2, wherein the organic matter with carboxyl is carboxylic acid or amino acid.

20. metal paste mixing according to claim 1 or 2, wherein the organic matter with carboxyl is aliphatic acid.

21. metal paste mixing according to claim 20, wherein aliphatic acid is the saturated or unsaturated fat of C3~C24 Acid.

22. metal paste mixing according to claim 20, wherein aliphatic acid is the fat that the double key number of C3~C24 is 0~2 Fat acid.

23. metal paste mixing according to claim 20, wherein aliphatic acid is selected from crotonic acid, acrylic acid, metering system Acid, octanoic acid, n-nonanoic acid, capric acid, lauric acid, myristic acid, pentadecanoic acid, palmitic acid, palmitoleic acid, Heptadecanoic acide, stearic acid, oil Acid, vaccenic acid, linoleic acid,（9,12,15）Leukotrienes,（6,9,12）Leukotrienes, dihomo-gamma-linolenic acid, eleostearic acid, knot Core stearic acid, arachidic acid（Arachic acid）, 8,11- eicosadienoic acids, 5,8,11- eicosatrienoic acids, arachidonic acid, Behenic acid, lignoceric acid, nervonic acid, elaidic acid, sinapic acid, docosahexaenoic acid, eicosapentaenoic acid, 18 carbon One or more of tetraenoic acid.

24. metal paste mixing according to claim 1 or 2, wherein solvent is that alcoholic solvent, glycol ether solvent, acetic acid esters are molten Agent, ketone solvent or hydrocarbon solvent.

25. metal paste mixing according to claim 20, wherein quality of the aliphatic acid relative to surface treated metal powder Than 1/100~1/10 range.

26. metal paste mixing according to claim 25, wherein aliphatic acid relative to solvent mass ratio 1/100~1/ 10 range.

27. patch multi-layer ceramic capacitor is obtained by being made using pasting described in any one of claim 1~26.

28. patch multi-layer ceramic capacitor according to claim 27, wherein there are a diameter of on internal electrode section The SiO of 10nm or more₂、TiO₂、Al₂O₃Any one of.

29. the patch multi-layer ceramic capacitor according to claim 27 or 28, wherein with 0.5 on internal electrode section A/cm²Exist below the SiO that maximum diameter is 0.5 μm or more₂、TiO₂、Al₂O₃Any one of.

30. the manufacturing method of metal paste mixing, include surface treated metal powder and organic matter with carboxyl are dispersed in it is molten The process that paste is prepared in agent：

Adhesion amount more than any one in the surface treated metal powder in Si, Ti, Al, Zr, Ce, Sn be relative to Metal powder 1g is 200~16000 μ g, and attachment N is 0.02% or more relative to the weight % of metal powder,

Surface treated metal powder is surface treated obtained by being manufactured using the method for manufacturing surface treated metal powder Metal powder, the manufacturing method includes：Metal powder is mixed with the coupling agent aqueous solution with amino, prepares metal powder dispersion The process of liquid,

Coupling agent aqueous solution with amino be following formula I indicate amino silane aqueous solution or Formula Il indicate contain amino Titanate esters aqueous solution,

H₂N-R¹- Si（OR²）₂（R³）（Formulas I）

Wherein, in above-mentioned Formulas I,

R¹Be straight-chain or with branch, saturated or unsaturated, substituted or unsubstituted, ring type or non-ring type, with miscellaneous Ring or without heterocycle, the bivalent group of the hydrocarbon of C1~C12,

R²It is the alkyl of C1~C5,

R³It is the alkyl of C1~C5 or the alkoxy of C1~C5,

（H₂N-R¹- O）_pTi（OR²）_q（Formula II）

Wherein, in above-mentioned Formula II,

R²It is straight-chain or the alkyl with branch, C1~C5,

P and q is 1~3 integer, p+q=4.

31. according to the method for claim 30, wherein the process for preparing paste is：

Other than surface treated metal powder and with the organic matter of carboxyl, also in a solvent by adhesive resin dispersion Process to prepare paste.

32. the method according to claim 30 or 31, wherein the organic matter with carboxyl is aliphatic acid.

33. the method according to claim 30 or 31, by surface treated metal powder and with the organic matter of carboxyl After the process that solvent is distributed to prepare paste,

It include the process for the paste being prepared with filter filtering.

34. according to the method for claim 33, wherein filter has 1~8 μm of aperture.

35. according to the method for claim 33, wherein the process being filtered with filter utilizes and is filtered under diminished pressure or pressurizeed Filter carries out.

36. according to the method for claim 30, wherein metal powder is any metal powder in Pt, Pd, Ag, Ni, Cu.

37. according to the method for claim 30, wherein metal powder is copper powder.

38. according to the method for claim 30, wherein metal powder is any metal powder in Pt, Pd, Ag, Ni.

39. according to the method for claim 30, wherein the process including stirring metal powder dispersion liquid.

40. according to the method for claim 30, wherein include the process for carrying out ultrasonication to metal powder dispersion liquid.

41. according to the method for claim 40, wherein the process for carrying out ultrasonication is the super of carry out 1~180 minute The process of sonicated.

42. according to the method for claim 30, wherein including：

The metal powder drying that filtering is recovered, obtains surface treated metal powder process.

43. according to the method for claim 42, wherein drying carries out under oxygen atmosphere or inert atmosphere.

44. according to the method for claim 30, wherein in metal dispersion, relative to metal powder 1g, including 0.025g with On the coupling agent with amino.

45. according to the method for claim 30, wherein R¹Be selected from-（CH₂）_n,-（CH₂）_n（CH）_m （CH₂）_j-1,-（CH₂）_n（CC）（CH₂）_n-1,-（CH₂）_n- NH-（CH₂）_m,-（CH₂）_n- NH-（CH₂）_m NH-（CH₂）_j,-（CH₂）_n-1（CH）NH₂（CH₂）_m-1,-（CH₂）_n-1（CH）NH₂（CH₂）_m-1- NH- （CH₂）_jIn group, wherein n, m, j be 1 or more integer.

46. according to the method for claim 30, wherein R¹Be selected from-（CH₂）_n,-（CH₂）_n（CH）_m （CH₂）_j-1,-（CH₂）_n（CC）（CH₂）_n-1,-（CH₂）_n- NH-（CH₂）_m,-（CH₂）_n- NH-（CH₂）_m NH-（CH₂）_j,-（CH₂）_n-1（CH）NH₂（CH₂）_m-1,-（CH₂）_n-1（CH）NH₂（CH₂）_m-1- NH- （CH₂）_jIn group, wherein n, m, j be 1 or more integer.

47. according to the method for claim 30, wherein metal powder is to utilize metal powder obtained by damp process manufacture.

48. according to the method for claim 30, wherein

Surface treated metal powder be any one in Si, Ti, Al, Zr, Ce, Sn more than adhesion amount relative to metal powder The surface treated metal powder that 1g is 200~16000 μ g, attachment N is 0.02% or more relative to the weight % of copper powder,

It is 400 DEG C or more to be sintered start temperature.

49. the method for manufacturing electrode, including：

It will be applied on base material using metal powder paste obtained by the manufacturing method manufacture described in any one of claim 30~48 Process,

50. according to the method for claim 49, wherein electrode is patch multi-layer ceramic capacitor electrode.

51. metal paste mixing is to utilize metal powder obtained by the manufacturing method manufacture described in any one of claim 30~48 Paste, wherein

5 μm of aperture, effective area 9.0cm are utilized to above-mentioned metal paste mixing²Filter carry out 0.3atm and be filtered under diminished pressure, transmission Quality is 35% or more over the course of 15 mins relative to the percentage of the ratio of the input quality of 4g.

52. electrode is electrode obtained by being manufactured using the manufacturing method described in claim 49 or 50,

With 0.5/cm on electrode section²Exist below the SiO that maximum diameter is 0.5 μm or more₂、TiO₂、Al₂O₃In any Kind.