CN101964218B - Conductive slurry and its preparation method - Google Patents
Conductive slurry and its preparation method Download PDFInfo
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- CN101964218B CN101964218B CN2010102353851A CN201010235385A CN101964218B CN 101964218 B CN101964218 B CN 101964218B CN 2010102353851 A CN2010102353851 A CN 2010102353851A CN 201010235385 A CN201010235385 A CN 201010235385A CN 101964218 B CN101964218 B CN 101964218B
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Abstract
The invention provides a preparation method of a conductive slurry. A conductive powder containing silver-plated copper powder disperses in an adhesive resin and the silver-plated copper powder is prepared by a first plating step of plating the silver on a raw material copper powder, a crushing step of crushing the silver-plated raw material copper powder and a second plating step of plating the silver on the crushed powder. The conductive slurry has excellent conductivity and storage stability. According to the invention, the invention provides a preparation method of the conductive slurry using the silver-plated copper powder as the conductive powder with excellent conductivity and storage stability and in addition the invention provides a conductive slurry prepared by the above method.
Description
Technical field
The circuit that the present invention relates to be applicable to printed base plate forms or the preparation method and the conductive paste of the conductive paste of the filling of via hole etc.
Background technology
In the past, the circuit that was used for printed base plate form or the conductive paste of the filling of via hole roughly through the method that electroconductive powder is dispersed in as the binding resin of binding agent being prepared with roller mill etc.
In this conductive paste,, use silver powder or copper powder usually as electroconductive powder.Wherein, silver powder obtains excellent conductivity easily, and the reliability of conductivity is also high, but exist expensive, cause shortcoming such as migration easily.On the other hand, copper powder is more cheap than silver powder, is not easy to cause migration, but has easy oxidation and conductivity reduces, or the conductivity problem of unstable that becomes easily.
So,, developed the technology (referenced patent document 1 and 2 etc.) that silver is plated in the silver-plated copper powder that forms on the copper powder of using in order to solve such problem.As the raw material copper powder of silver-plated copper powder, the cheap electrolytic copper powders that use the dendroid shape of the electrolytic preparation through copper sulphate etc. more.In addition, the copper powder of atomization preparation etc. is passed through in use sometimes.
Patent documentation 1: japanese kokai publication hei 9-282935 communique
Patent documentation 2: japanese kokai publication hei 7-138549 communique
But, use the conductive paste conductivity meeting sometimes of silver-plated copper powder insufficient as electroconductive powder.In addition, viscosity rises or gelation during preservation, and exists storage stability to be prone to the problem of variation.
Summary of the invention
In view of this, problem of the present invention is, uses silver-plated copper powder as electroconductive powder though provide, the preparation method of the conductive paste of conductivity and excellent storage stability and the conductive paste for preparing through this method.
The result of the application inventor's further investigation finds; Use the conductivity of the conductive paste of silver-plated copper powder be prone to the to become reason of the easy variation of insufficient, other storage stability to be present in, the copper powder with silver-plated in the preparation section of conductive paste is dispersed in the operation in the binding resin.
That is, in this operation, use roller mill usually as dispersion machine, but this moment, silver-plated copper powder squeezes broken easily between roller and is out of shape.The result is along with this distortion, and silvering breaks or peels off, and the surface that might expose copper powder.Therefore the copper surface oxidation easily of exposing like this is prone to the reduction of the conductivity of generation conductive paste.And then the copper that exposes like this surface active high played the effect of catalyst property when therefore preserving and promoted the reaction of binding resin to cause that the viscosity of conductive paste rises or gelation, is prone to reduce storage stability.
Particularly; When using electrolytic copper powder as the raw material copper powder of silver-plated copper powder and since electrolytic copper powder be shaped as dendroid, between the roller of roller mill, squeeze broken and be out of shape; Become the paper tinsel shape easily, because the reduction of conductivity that surperficial the exposing of copper causes and storage stability is remarkable.
So; The result that the application inventor further studies; Find to pass through with the silver-plated copper powder of specific method for preparing; Even use dendritic electrolytic copper powder, also can obtain in the dispersion step of thereafter use roller mill, being difficult for becoming the paper tinsel shape, the silver-plated copper powder that the copper surface is difficult for exposing as the raw material copper powder.Its result, though find to use the conductive paste of this silver-plated copper powder production to use silver-plated copper powder as electroconductive powder, conductivity and storage stability are good, have so far accomplished the present invention.
The preparation method of conductive paste of the present invention; The electroconductive powder that contains silver-plated copper powder is dispersed in the binding resin; It is characterized in that; Said silver-plated copper powder will carry out the pulverizing process of silver-plated raw material copper powder pulverizing and the second plating operation that silver is plated on the pulverized comminuted powder and prepare through silver is plated in the first plating operation on the raw material copper powder.
Said raw material copper powder can use the raw material copper powder that contains electrolytic copper powder.
Preferably in the said first plating operation, with respect to the said raw material copper powder of 100 mass parts, the silver of plating 5～10 mass parts is in the said second plating operation, with respect to the said raw material copper powder of 100 mass parts, the silver of plating 5～20 mass parts.
Said binding resin can use more than one heat-curing resins that are selected from the group that is made up of epoxy resin, mylar, polyurethane resin, phenolic resins and imide resin.
Preferably with respect to said electroconductive powder 100 mass parts, use the said binding resin of 10～35 mass parts, wherein, said electroconductive powder contains the above silver-plated copper powder of 10 quality %.
Conductive paste of the present invention is characterized in that, through above-mentioned preparation method's preparation.
According to the present invention, use silver-plated copper powder as electroconductive powder although can provide, the preparation method of the conductive paste of conductivity and excellent storage stability in addition, can provide the conductive paste through method for preparing.
Embodiment
Below, the present invention is elaborated.
For the electroconductive powder that will contain silver-plated copper powder is dispersed in the preparation method of the conductive paste in the binding resin, at first prepare silver-plated copper powder as the preparation method of the conductive paste of an embodiment of the invention.
[preparation of silver-plated copper powder]
Silver-plated copper powder is plated in silver first plating operation on the raw material copper powder, will in the first plating operation, have carried out pulverizing process that silver-plated raw material copper powder pulverizes and the preparation section of the second silver-plated once more plating operation of the comminuted powder of pulverizing is prepared through having.
(the first plating operation)
In the first plating operation, silver-plated on the surface of raw material copper powder.
As the restriction especially of raw material copper powder, for example, can use the atomized copper powder through atomization preparation or the copper reduction that copper compound reduction in the aqueous solution separated out obtain with reducing agent etc.But these copper powders are expensive, the therefore preferred more electrolytic copper powder of cheapness that uses.The dendritic copper powder that electrolytic copper powder prepares for the electrolysis through copper sulphate etc.
In addition, consider,, preferably only use cheap electrolytic copper powder, but according to circumstances as the raw material copper powder from the cost aspect, can also be with electrolytic copper powder suitably and with atomized copper powder or copper reduction.
The preferable particle size of raw material copper powder is 5～30 μ m.And the particle diameter here is meant by マ イ Network ロ ト ラ Star Network (Mai Qike) HRA (day machine dress (strain) system) measures 50% particle diameter (D50%) that obtains.
As the method for plating in the first plating operation, can enumerate known method for plating such as electroless plating coating method (for example replacing plating method etc.), electrolysis plating method.
Under the situation of displacement plating method (silver displacement plating); For example can enumerate; The aqueous solution and the raw material copper powder that will contain ammonium carbonate, EDTA and water are mixed with the copper dispersion liquid, add the method for the aqueous solution of silver-plated raw material such as silver nitrate when in this copper dispersion liquid, stirring.Then, with the dispersion liquid filtration, washing, the drying that obtain, thereby can obtain having carried out silver-plated raw material copper powder.
In addition, before the first plating operation,, preferably the raw material copper powder is carried out pickling in advance through for example aqueous sulfuric acid etc. in order to remove the oxide-film on raw material copper powder surface.
In the first plating operation, with respect to raw material copper powder 100 mass parts, the silver of preferred plating 5～10 mass parts.If such plating amount then can all cover the surface of raw material copper powder with silver.At this, if the plating amount of silver, then might can't be used the surface of silver covering raw material copper powder less than 5 mass parts, in addition, when surpassing 10 mass parts, though coverage effect is constant unfavorable aspect cost.
According to the first such plating operation; Not only obtain the effect of conductivity aspect that the silver that conductivity is good is arranged on the surface of raw material copper powder; Can also be silver-plated in advance before the pulverizing process that next carries out, obtain thus in pulverizing process, preventing because frictional heat etc. and the effect of raw material oxidization of copper powder.
(pulverizing process)
Then, to the carrying out that in the first plating operation, obtain silver-plated raw material copper powder (below, be sometimes referred to as the first plating copper powder) pulverize, process the pulverizing process of comminuted powder.
Pulverizing process is meant the operation of pulverizers such as for example using attritor, ball mill, aeropulverizer; When for example using ball mill; With respect to first plating copper powder 100 mass parts; The lubricants such as stearic acid that add 0.1～2 mass parts get final product changeing with per minute 20～90 to pulverize under the condition that rotation waited in 30～180 minutes.
In such pulverizing process, to first the plating copper powder apply shearing (シ エ ア), when using dendritic electrolytic copper powder as the raw material copper powder, the part of bulky branch is cut off.Its result, the comminuted powder after the pulverizing forms the bigger shape of particle of packed density, afterwards, is distributed in the binding resin through dispersion machines such as roller mills, and is also not yielding even be clipped under the situation between the roller, is difficult for becoming the paper tinsel shape.
In the operation of disperseing, if such distortion is suppressed, then be difficult for causing breaking, peeling off of silvering, can prevent that the surface of raw material copper powder from exposing.Its result can prepare the conductive paste of conductivity and excellent storage stability.
And packed density can be estimated tap density as index, and tap density is big, and then packed density also increases.In order to obtain sufficient conductivity, carry out pulverizing process so that the tap density of comminuted powder is preferably 3.5～4.5g/cm
3, 3.7～4.2g/cm more preferably
3
(the second plating operation)
Through above-mentioned pulverizing process, though can obtain the comminuted powder of the big shape of particle of packed density, this comminuted powder can form the state that the surface portion ground of raw material copper powder exposes owing to pulverize.Therefore, in the second plating operation, carry out silver-plated once more to such comminuted powder.
As method for plating, with the first plating operation likewise, can enumerate known method for plating such as electroless plating coating method, electrolysis method for plating, can carry out silver-plated through concrete grammar of in the first plating operation, having explained etc.
In the second plating operation, with respect to raw material copper powder 100 mass parts, the silver of preferred plating 5～20 mass parts.If such plating amount, the silver-plated copper powder that then finally obtains through each operation of above explanation is being distributed in the operation in the binding resin thereafter, even under the situation that supplies to dispersion machines such as roller mill, the surface of raw material copper powder also is difficult for exposing.Its result can form the conductive paste of conductivity and excellent storage stability.At this,, then unfavorable aspect cost if the plating amount of silver surpasses 20 mass parts.
And,,, be preferably the silver of 10～30 mass parts with respect to the raw material copper powder of 100 mass parts as the plating total amount in the first plating operation and the second plating operation.
[preparation of conductive paste]
Then, the electroconductive powder of the silver-plated copper powder of preparation will be dispersed in the operation in the binding resin through containing as stated, can prepare the conductive paste of conductivity and excellent storage stability.
As electroconductive powder, for the electroconductive powder that contains the silver-plated copper powder for preparing through above-mentioned each operation at least gets final product, can only contain silver-plated copper powder, also can contain other electroconductive powders.As other electroconductive powders, can enumerate metals such as silver, tin, lead, bismuth, zinc, indium, nickel, gold or be selected from two or more alloy in them etc.In addition, can also use carbon black.
Other electroconductive powders like this are more expensive than silver-plated copper powder mostly; When therefore using these other electroconductive powders; Through in electroconductive powder, containing the silver-plated copper powder more than the 10 quality %, when can keep the performance as conductive paste, reduce its cost.
As binding resin; If playing the binding resin of effect of the bonding agent of conductive paste gets final product; Can use thermoplastic resins such as mylar, acrylic resin, butyral resin, thermoplasticity imide resin, but consider, preferably use heat-curing resin from stable on heating viewpoint.
As heat-curing resin; Preferably use the epoxy resin such as liquid epoxy compounds that have an above glycidyl in bisphenol A type epoxy resin for example, bisphenol f type epoxy resin, phenolic resin varnish type epoxy resin, the molecule; Mylar such as unsaturated polyester resin; Polyurethane resin, phenolic resins such as resol type phenol resin, phenolic varnish type phenolic resins, imide resin etc.In addition, the curing agent that these heat-curing resins are solidified can also be contained in the binding resin, amine epoxy hardener, anhydrides epoxy hardener, isocyanates curing agent, imidazole curing agent etc. can be enumerated.These heat-curing resins and curing agent can use a kind of separately or and with two or more.
In the dispersion, use dispersion machines such as roller mill, ball mill, spike mill such as triple-roller mill, electroconductive powder is dispersed in the binding resin.At this moment, can also cooperate dilution such as butyl glycol ether acetic acid esters (BCA) with solvent, oxide-film remover, dispersant etc. as required.
To the restriction especially of the use level of binding resin, but, be preferably 10～35 mass parts with respect to the electroconductive powder of 100 mass parts.And when using curing agent, the amount of this curing agent is also contained in the amount of binding resin.
[conductive paste]
Conductive paste through above preparation method's preparation can be used for various uses, is applicable to that the circuit of printed base plate, particularly printed base plate forms.Conductive paste for example is printed on the base material such as film or substrate; At binding resin is under the situation of Thermocurable; Carry out heat treated afterwards and be cured, thus can make between the electroconductive powder with high dispersion state interconnect, conductivity and the good circuit of reliability.
Heat treated can be used known devices such as box hot-blast stove, continous way hot-blast stove, Muffle furnace formula heating furnace, near-infrared line oven, far infrared line oven, vacuum hotpressing machine.
More than the preparation method of the conductive paste of explanation is as the operation of the silver-plated copper powder of preparation, possess with silver be plated in the first plating operation on the raw material copper powder, with first pulverizing process pulverized of plating copper powder and to having carried out the second silver-plated plating operation of pulverizing of comminuted powder.The conductive paste that therefore, can prepare conductivity and excellent storage stability.
That is,,, also can make the silver-plated copper powder that finally obtains form the big shape of particle of packed density even use under the situation of dendritic electrolytic copper powder as the raw material copper powder owing to possess pulverizing process.The silver-plated copper powder of shape is in the operation that is distributed to binding resin of back like this, and is even be clipped between the roller of dispersion machine such as roller mill, also not yielding.Therefore, be difficult for causing resulting from the breaking, peel off of silvering of this distortion, can prevent exposing of raw material copper powder surface, can prepare the conductive paste of conductivity and excellent storage stability.
In addition, the preparation method of this conductive paste possessed the first plating operation before pulverizing process.So if silver-plated before pulverizing process in advance, then not only obtain the effect of conductivity aspect that the silver that conductivity is good is arranged on the surface of raw material copper powder, can also be prevented in pulverizing process because frictional heat etc. and the effect of raw material oxidization of copper powder.
Further, the preparation method of this conductive paste possesses the second plating operation after pulverizing process.Silver-plated once more after pulverizing process through like this, can be effectively with silver-colored plating owing to the surface of pulverizing the raw material copper powder that exposes.
The copper that exposes of raw material copper powder surface is because oxidation easily, if expose, then the conductivity of conductive paste reduces easily, but exposes through preventing, can suppress the reduction of conductivity.
In addition, the surface of exposing of raw material copper powder is because active high, when preserving, plays the effect of catalyst property and promotes the reaction of binding resin to cause that easily the viscosity of conductive paste rises or gelation, and storage stability is reduced.Particularly, when using than the reactive high heat-curing resin of thermoplastic resin, even exposing of the raw material copper powder of a little also exists to cause that easily viscosity rises or the trend of gelation as binding resin.But, through preventing this exposing,, also can suppress viscosity and rise or gelation, thereby can improve the storage stability of conductive paste even when using heat-curing resin as binding resin.
[embodiment]
Below, enumerate embodiment the present invention is elaborated.
[embodiment 1]
According to following (1) and (2) preparation conductive paste, estimate according to following (3).
The cooperation and the evaluation result of conductive paste are organized in the table.
(1) preparation of silver-plated copper powder (pickling)
The dendroid electrolytic copper powder as the raw material copper powder (Mitsui Metal Co., Ltd.'s mining industry (strain) system, trade name " MF-D2 ", diameter 10 μ m) to 60g; Adding is as the aqueous sulfuric acid 100ml of about 5 quality % of washings; Stirring is after 10 minutes down at 20 ℃, and pickling is carried out in filtration.Afterwards, wash repeatedly until filtrating to neutral.Specifically, use the washings of 3L altogether, carried out 6 pickling.
(the first plating operation)
Then, the raw material copper powder after the pickling is moved on in the plastic containers of 1L volume, to wherein adding the aqueous solution that contains ammonium carbonate 31.5g, EDTA 63g and water 250g, preparation copper dispersion liquid.Then, in this copper dispersion liquid, add the aqueous solution that contains silver nitrate 5.25g and water 32.4g while stirring, carry out silver displacement plating.
Then, silver is replaced dispersion liquid filtration, washing, drying behind the plating, obtains raw material copper powder with respect to 100 mass parts, plating the raw material copper powder of silver of 5 mass parts.
To having carried out silver-plated raw material copper powder like this, using Mai Qike HRA (day machine dress (strain) system) to measure 50% particle diameter (D50%) that obtains is 8.39 μ m.In addition, this is used following method measure the tap density that obtains and be 2.99g/cm
3
[tap density]
(i) will carry out silver-plated raw material copper powder (sample) 100g drops in the 100ml graduated cylinder with funnel lentamente.
(ii) graduated cylinder is carried and put on the tap density analyzer, fall the compression sample 600 times apart from 20mm, 60 times/minute speed with drop.Measure the volume of the sample after the compression.
The quality (g) of (iii) using sample is divided by the volume (cm after compressing
3), calculate tap density (g/cm thus
3).
(pulverizing process)
Then,, add stearic acid 0.1 mass parts, it is pulverized in ball mill, obtain comminuted powder as lubricant with respect to first plating copper powder 100 mass parts that obtain in the first plating operation.The condition of pulverizing is made as 20 ℃, revolution: per minute 30 changes, and pulverizes 60 minutes.
In addition, to the comminuted powder that obtains like this, using Mai Qike HRA (day machine dress (strain) system) to measure 50% particle diameter (D50%) that obtains is 8.04 μ m.In addition, use said method to measure the tap density that obtains to this and be 3.85g/cm
3
Mean that through such pulverizing process, tap density increases, packed density also increases.
(the second plating operation)
Then, the comminuted powder that obtains in the pulverizing process is moved on in the plastic containers of 1L volume,, obtain silver-plated copper powder through carrying out silver displacement plating with the identical method of the above-mentioned first plating operation.
And, in the second plating operation, with respect to the raw material copper powder of 100 mass parts, plating the silver of 5 mass parts.
The final so silver-plated copper powder that obtains, with respect to raw material copper powder 100 mass parts, plating the silver of 10 mass parts.
(2) preparation of conductive paste (dispersion step)
Add the as above preparation of 100 mass parts silver-plated copper powder, with solid constituent count 18 mass parts the mylar as binding resin (Japan weaving (strain), trade name " バ イ ロ Application 550 "), (the butyl glycol ether acetic acid esters as solvent (being labeled as BCA in the table) of blocked isocyanate (Japanese Port リ ウ レ タ Application industry (strain) system, trade name " コ ロ ネ one ト 2516 ") and 47 mass parts carries out premixed so that silver-plated copper powder is compatible with other compositions to count the curing agent of 4.5 mass parts with solid constituent.Afterwards, disperse this premix, obtain conductive paste with triple-roller mill.
(3) estimate
Conductive paste to as above obtaining carries out following evaluation.
(i) conductivity evaluation (resistivity)
Conductive paste is coated on the glass plate, in 150 ℃ thermostat, kept 30 minutes, make its curing, drying, as sample.After making this sample get back to room temperature,, obtain resistivity (resistivity before the test) through following formula with the mensuration resistance of filming of digital multimeter to forming by conductive paste.
In addition, conductive paste after preserving 60 days under 23 ℃, likewise is coated on it on glass plate, in 150 ℃ thermostat, kept 30 minutes, make its curing, drying, as sample.After making this sample get back to room temperature,, obtain resistivity (test back resistivity) likewise to this mensuration resistance of filming.
Resistivity=R * S/I (Ω cm)
(in the formula, R: the resistance value of digital multimeter, S: by the sectional area of filming that conductive paste forms, I: interelectrode distance)
The (ii) evaluation of storage stability
Measured with viscosity afterwards before in 60 days conductive paste is preserved down at 23 ℃, obtain the viscosity rate of change through following formula.In the table, initial viscosity is the viscosity before preserving, and keeping quality test back viscosity is the viscosity after preserving.
Determination of viscosity by means of the conductive paste is adjusted to a temperature of 23 ± 2 ℃, with a Brookfield BM type viscometer (Tokyo Keiki (Co., Ltd.) Ltd.).
Viscosity * 100 before viscosity rate of change (%)=(viscosity before the viscosity-preservation after the preservation)/preservation
[embodiment 2～14]
It is as shown in the table, and change cooperates, and likewise prepares conductive paste with embodiment 1, and estimates.
And embodiment 9 and 10 is for using the example of thermoplastic resin as binding resin, and other embodiment are for using the example of heat-curing resin (and using curing agent) as binding resin.
[comparative example 1]
When preparing silver-plated copper powder, after the first plating operation, do not carry out the pulverizing process and the second plating operation, obtain silver-plated copper powder.As the plating amount, with respect to the raw material copper powder of 100 mass parts, the silver of plating 10 mass parts.
Except using this silver-plated copper powder, likewise prepare conductive paste with embodiment 1 and estimate.
[comparative example 2]
The twice plating amount of plating comparative example 1 in first operation promptly with respect to raw material copper powder 100 mass parts, is the silver of 20 mass parts, in addition likewise prepares silver-plated copper powder, conductive paste with comparative example 1 and estimates.
[comparative example 3]
After the first plating operation, and carry out pulverizing process under the same condition of embodiment 1, in addition likewise prepare silver-plated copper powder, conductive paste and estimate with comparative example 1.
[comparative example 4]
Omit the first plating operation, the electrolytic copper powder as the raw material copper powder is carried out pulverizing process, carry out the second plating operation afterwards and obtain silver-plated copper powder.As the plating amount, with respect to raw material copper powder 100 mass parts, the silver of plating 10 mass parts.
Except using this silver-plated copper powder, likewise prepare conductive paste with embodiment 1 and estimate.
[comparative example 5]
After the first plating operation, omit pulverizing process, carry out the second plating operation, obtain silver-plated copper powder, as the plating amount, with respect to raw material copper powder 100 mass parts, the silver of each 5 mass parts of difference plating in the first plating operation and the second plating operation.
Except using this silver-plated copper powder, likewise prepare conductive paste with embodiment 1 and estimate.
Each composition of putting down in writing in the table is following.
Mylar: Japan's weaving (strain), trade name " バ イ ロ Application 550 "
Isocyanates curing agent: Japanese Port リ ウ レ タ Application industry (strain) system, trade name " コ ロ ネ one ト 2516 "
Resol type phenol resin: Sumitomo ベ one Network ラ イ ト (strain) system, trade name " ス ミ ラ Star Network PC-1 "
Bisphenol A type epoxy resin: ジ ヤ パ Application エ Port キ シ レ ジ Application (strain) system, trade name " エ ピ コ one ト 828 "
Imidazole curing agent: four countries change into industry (strain) system, trade name " 2P4MHZ "
Flake silver powder: (strain) Off エ ロ ジ ヤ パ Application system, trade name " SF78 "
Carbon black: エ ボ ニ Star Network デ グ サ ジ ヤ パ Application (strain) system, trade name " プ リ Application テ Star Network ス L "
Result by the resistivity before and after the test in the table can know that according to each embodiment, when the conductivity before the test was good, the conductivity after the test did not almost reduce, and obtained the conductive paste of good electrical conductivity.Does not expose on the copper surface of the silver-plated copper powder of each embodiment of this expression, therefore can not produce because the reduction of the conductivity that the oxidation of copper causes.In addition, the viscosity rate of change of these conductive pastes is little, and storage stability is also excellent.And though the for example conductive paste conductivity of embodiment 8 some reduction slightly, the variation of test back conductivity is little, so long as not the purposes that requires very high conductivity, then can fully use.
Claims (6)
1. the preparation method of a conductive paste is dispersed in the binding resin electroconductive powder that contains silver-plated copper powder, it is characterized in that,
Said silver-plated copper powder is through the first plating operation with respect to the silver of the raw material copper powder of 100 mass parts, plating 5～10 mass parts,
To carry out pulverizing process that silver-plated raw material copper powder pulverizes and
The second plating operation that silver is plated on the pulverized comminuted powder prepares.
2. the preparation method of conductive paste according to claim 1 is characterized in that, said raw material copper powder contains electrolytic copper powder.
3. the preparation method of conductive paste according to claim 1 and 2 is characterized in that, in the said second plating operation, with respect to the said raw material copper powder of 100 mass parts, the silver of plating 5～20 mass parts.
4. the preparation method of conductive paste according to claim 1 and 2; It is characterized in that said binding resin is more than one the heat-curing resin that is selected from the group that is made up of epoxy resin, mylar, polyurethane resin, phenolic resins and imide resin.
5. the preparation method of conductive paste according to claim 1 and 2; It is characterized in that,, use the said binding resin of 10～35 mass parts with respect to said electroconductive powder 100 mass parts; Wherein, said electroconductive powder contains the above silver-plated copper powder of 10 quality %.
6. a conductive paste is characterized in that, through any described preparation method's preparation of claim 1～5.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009173137A JP5402350B2 (en) | 2009-07-24 | 2009-07-24 | Method for producing conductive paste and conductive paste |
| JP2009-173137 | 2009-07-24 |
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| CN101964218A CN101964218A (en) | 2011-02-02 |
| CN101964218B true CN101964218B (en) | 2012-08-29 |
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| JP6377007B2 (en) | 2015-04-20 | 2018-08-22 | 富士フイルム株式会社 | Conductive film, wiring, and touch panel sensor |
| CN105127449A (en) * | 2015-10-20 | 2015-12-09 | 陈键 | Method for preparing copper powder with silver-plated surface |
| CN110853794B (en) * | 2019-10-30 | 2021-12-03 | 上海润势科技有限公司 | Conductive paste |
| JP2021105135A (en) * | 2019-12-26 | 2021-07-26 | 住友金属鉱山株式会社 | Thermally conductive composition |
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| JP2004047421A (en) * | 2002-05-17 | 2004-02-12 | Hitachi Chem Co Ltd | Conductive paste |
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| JPH07138549A (en) * | 1993-11-15 | 1995-05-30 | Tatsuta Electric Wire & Cable Co Ltd | Conductive adhesive |
| JPH09282935A (en) * | 1996-04-09 | 1997-10-31 | Hitachi Chem Co Ltd | Silver-plated copper powder |
| JPH10152630A (en) * | 1996-08-21 | 1998-06-09 | Hitachi Chem Co Ltd | Conductive paste and composite conductive powder |
| JP2002332501A (en) * | 2001-05-11 | 2002-11-22 | Mitsui Mining & Smelting Co Ltd | Method for manufacturing silver-coated copper powder, silver-coated copper powder obtained by the manufacturing method, conductive paste using the silver- coated copper powder, and printed wiring board using the conductive paste |
| WO2008059789A1 (en) * | 2006-11-17 | 2008-05-22 | Nippon Mining & Metals Co., Ltd. | Silver-plated fine copper powder, conductive paste produced from silver-plated fine copper powder, and process for producing silver-plated fine copper powder |
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| JP2004047421A (en) * | 2002-05-17 | 2004-02-12 | Hitachi Chem Co Ltd | Conductive paste |
| CN1425783A (en) * | 2002-12-31 | 2003-06-25 | 西安理工大学 | High temperature resistant anti-oxidant base metal copper-silver alloy composition and its producing method |
| CN101032750A (en) * | 2007-04-06 | 2007-09-12 | 深圳市危险废物处理站 | Method of producing sheet shaped silver-plated copper powder |
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| CN101964218A (en) | 2011-02-02 |
| JP2011028985A (en) | 2011-02-10 |
| JP5402350B2 (en) | 2014-01-29 |
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