CN107077911B - The manufacturing method of nickel cream and nickel cream - Google Patents
The manufacturing method of nickel cream and nickel cream Download PDFInfo
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- CN107077911B CN107077911B CN201580049078.5A CN201580049078A CN107077911B CN 107077911 B CN107077911 B CN 107077911B CN 201580049078 A CN201580049078 A CN 201580049078A CN 107077911 B CN107077911 B CN 107077911B
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- nickel
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- promotor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/228—Terminals
- H01G4/232—Terminals electrically connecting two or more layers of a stacked or rolled capacitor
Abstract
The present invention, which provides one kind, can make the drying film density after nickel powder dispersion, coating excellent in the state that agglutination is few and be suitable as the manufacturing method of the nickel cream of the material of the internal electrode of laminated ceramic capacitor and nickel cream.Nickel cream of the invention at least contains nickel powder, split-up promotor, organic solvent and adhesive resin.The split-up promotor is the specific split-up promotor with anionic interfacial agent structure.Relative to 100 mass parts of nickel powder, it is 0.4 mass parts~4.6 mass parts that this, which has the content of the split-up promotor of anionic interfacial agent structure,.In addition, nickel concentration is the 50 mass % of mass %~70, viscosity is 8Pas~150Pas, and the moisture rate measured by Karl_Fischer method is less than 1 mass %.
Description
Technical field
The nickel cream that is used the present invention relates to the internal electrode for being suitable as such as laminated ceramic capacitor and nickel cream
Manufacturing method.
Background technique
It, will for the nickel cream for the internal electrode of laminated ceramic capacitor (hereinafter also referred to as " MLCC ")
Nickel powder mixing is manufactured in the carrier, the agglutination body containing many nickel powders.Which kind of no matter the side of metal powder is manufactured using
Method (dry method, wet process) usually has drying process in the terminal stage of the manufacturing process of nickel powder, since the drying process promotes nickel
The agglutination of particle, therefore, the agglutination body generated when usually containing dry in obtained nickel powder.
For laminated ceramic capacitor in recent years, in order to realize small-sized and high capacity, to interior electrode layer
The requirement of the stacking number of associated ceramic green blank increases to 1000 layers or so from hundreds of.Therefore, by the thickness of interior electrode layer
It is being carried out always by the research of previous several μm of grades thin to submicron order, at the same time, the electrode as internal electrode
The small particleization of the nickel powder of material is always in propulsion.
However, partial size is smaller, the surface area of nickel powder is bigger, and at the same time, surface can increase, agglutination body easy to form.Separately
Outside, if the bad dispersibility of the metal ultrafine powders such as nickel Ultramicro-powder, there are agglutination body, in the firing process of manufacture ceramic capacitor
When middle sintering nickel powder, ceramic lamella can be penetrated, therefore, becomes the defective products of electric pole short circuit.In addition, even if not penetrating potsherd
In the case where layer, since interelectrode distance shortens, there is portion of electrical current concentration, therefore, lead to the service life of laminated ceramic capacitor
Deteriorate.
As the nickel Ultramicro-powder slurry for MLCC internal electrode, for example, there are slurries disclosed in patent document 1.Tool
For body, which discloses following technology.That is, firstly, relative to 100 mass parts of metal ultrafine powder, with 0.3 mass
The ratio of part adds specific teepol in metal ultrafine powder water slurry (metal ultrafine powder concentration: 50 matter
Measure %) in, implement the decentralized processing of stipulated time to it using technique homogenizer (Process homogenizer) etc., makes water
The agglutination body of middle metal ultrafine powder is separated into primary particle.Then, relative to 100 mass parts of metal ultrafine powder, 10 mass are added
Part such as terpinol is as organic solvent.The pine tar alcohol layer containing metal powder forms pantostrat and becomes sediment as a result, and water is made
It is separated for supernatant, obtains the organic solvent pulps of metal ultrafine powder.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2006-63441 bulletin.
Non-patent literature
Non-patent literature 1: upper Changjiang region field and other people, " chemistry with education " (" chemical と is educated "), Vol.40, No.2,
(1992) p114-117.
Summary of the invention
Problems to be solved by the invention
However, being handled as follows in the method for patent document 1 to manufacture nickel powder organic ink: firstly, in nickel powder water
Specific teepol is directly added in slurry, then, is mixed with organic solvent and is replaced nickel powder, to obtain nickel
Powder organic ink.Micellization is carried out in the presence of due to above-mentioned interfacial agent, so being difficult to be adsorbed in nickel powder interface, inefficient asking
Topic.
The object of the present invention is to provide one kind can make the drying after nickel powder dispersion, coating in the state that agglutination is few
Film density is excellent and is suitable as the manufacture of the nickel cream of the material of the internal electrode of laminated ceramic capacitor and nickel cream
Method.
The means to solve the problem
The inventors of the present invention are to solve the above subject to be careful studied.As a result, it was found that by by particular types
It is added in the water slurry of nickel powder jointly with the split-up promotor and organic solvent of amount, is able to solve the above subject, thus
Complete the present invention.Specifically, the present invention provides the following contents.
(1) first invention of the invention is a kind of nickel cream, at least contains nickel powder, split-up promotor, organic solvent
And adhesive resin, which is characterized in that
The split-up promotor is point with anionic interfacial agent structure indicated with the following general formula (1)
Transfer promotor is dissipated,
Relative to 100 mass parts of nickel powder, the split-up with anionic interfacial agent structure promotes
The content of agent is 0.4 mass parts~4.6 mass parts,
Nickel concentration is the 50 mass % of mass %~70,
Viscosity is 8Pas~150Pas,
The moisture rate measured by Karl_Fischer method is less than 1 mass %.
(wherein, in formula (1), m, n meet the relationship of m+n=12~20.)
(2) the second invention of the invention is a kind of nickel cream, which is characterized in that described to have anion in first invention
The split-up promotor of type surfactant structures is from by N- oleoyl-sarcosine, N- palmitoleoyl-N- first
In the group of base glycine, N- octadecenoyl-sarcosine and N- tetracosene acyl-N-methyl glycine composition
Select more than one.
(3) third invention of the invention be a kind of nickel cream manufacturing method comprising:
Nickel organic ink formation process, the process add organic solvent in the water slurry of nickel powder and have anionic circle
The split-up promotor of face active agent structures, to form nickel organic ink；
Water separation process, the process separate the water layer from the nickel organic ink for being separated into water layer and organic layer,
To obtain organic layer nickel organic ink；And
Compounding procedure, the process are added adhesive resin and are kneaded in the organic layer nickel organic ink,
In the nickel organic ink formation process, turn as the dispersion with anionic interfacial agent structure
Promotor is moved, the split-up promotor indicated with the following general formula (1) is added,
Relative to the nickel powder, the additive amount of the split-up promotor with anionic interfacial agent structure
To make total molecular cross sectional area of the split-up promotor with anionic interfacial agent structure reach the total of the nickel powder
The amount of 1 times of surface area~4 times,
The quality S of the organic solvent1With the ratio between quality W of water S in the water slurry of the nickel powder1/ W meets 0.02 < S1/
The relationship of W < 0.4.
(wherein, in formula (1), m, n meet the relationship of m+n=12~20.)
(4) the 4th invention of the invention is a kind of manufacturing method of nickel cream, which is characterized in that described in third invention
Split-up promotor with anionic interfacial agent structure is from by N- oleoyl-sarcosine, N- palm
Oleoyl-sarcosine, N- octadecenoyl-sarcosine and the sweet ammonia of N- tetracosene acyl-N-methyl
Acid composition group in select more than one.
(5) the 5th invention of the invention is a kind of manufacturing method of nickel cream, which is characterized in that in third or the 4th invention
In, in the compounding procedure, described adhesive resin is made, the adhesive resin is contained with the concentration of 5 mass % or more
Carrier, to be added.
The effect of invention
Nickel cream according to the present invention can be such that nickel powder disperses in the state that agglutination is few, and the drying film density after coating is excellent
It is different, it is suitable as the internal electrode materials'use of laminated ceramic capacitor.
In addition, the manufacturing method of nickel cream according to the present invention, due to not including drying process, it can obtain pressing down
Nickel powder processed oxidation, without dry agglutination and stable cream in terms of quality, simultaneously as not generating the nickel powder as nuisance
Dirt, it is therefore, from the viewpoint of in terms of safety and sanitation and excellent.
Specific embodiment
In the following, a specific embodiment of the invention (hereinafter referred to as " present embodiment ") is described in detail.It needs
Illustrate, the present invention is not limited to following implementation, can be suitably in the range of not changing the gist of the invention
Change.In addition, unless otherwise indicated, in this specification the statement of " x~y " (x, y are any number) refer to " x or more and y with
Under ".
" 1. nickel cream "
The nickel cream of present embodiment is at least containing nickel powder, split-up promotor, organic solvent and adhesive resin
Nickel cream.The split-up promotor is the dispersion with anionic interfacial agent structure indicated with the following general formula (1)
Shift promotor.
(wherein, in formula (1), m, n meet the relationship of m+n=12~20.)
In the nickel cream, relative to 100 mass parts of nickel powder, the above-mentioned dispersion with anionic interfacial agent structure
The content for shifting promotor is 0.4 mass parts~4.6 mass parts.If the content of split-up promotor is relative to nickel powder 100
Mass parts are less than 0.4 mass parts, then the residual moisture in nickel cream, on the other hand, if the content of split-up promotor is opposite
It is greater than 4.6 mass parts in 100 mass parts of nickel powder, then water is locked into split-up promotor when coating nickel powder surface, nickel
Residual moisture in cream, therefore not preferably.
In addition, the nickel concentration in nickel cream is 50 mass of mass %~70 %.Moreover, in the nickel cream, viscosity 8Pas
~150Pas, the moisture rate measured by Karl_Fischer method is less than 1 mass %.
According to above-mentioned nickel cream, the nickel powder as constituent disperses in the state that agglutination is less, the desciccator diaphragm after coating
Density is excellent, be suitable as the internal electrode of for example high laminated ceramic capacitor with substance come using.
[nickel powder]
Nickel powder is the constituent of the nickel cream, and the various nickel powders of any manufacturing method manufacture such as wet process, dry method can be used.
For example, it may be by chemical vapour deposition technique (Chemical Vapor Deposition, CVD), evaporation quenching method and
The nickel powder of the so-called dry method manufacture such as the hydrogen reduction method using nickel salt, nickel hydroxide etc., alternatively, it is also possible to be by for nickel
The nickel powder that salting liquid is manufactured using the so-called wet process such as the wet-type reduction method of reducing agent of hydrazine etc..Wherein, it is preferable to use by wet
The nickel powder of the so-called wet process manufacture such as formula reduction method.
In addition, as nickel powder, preferably average grain diameter be 0.05 μm~0.5 μm ultra micron nickel powder.For example, ultra micron
Nickel powder is adapted as the purposes of the internal electrode of laminated ceramic capacitor.As the internal electrode of MLCC, from in recent years
It is required it is thin layer it is corresponding from the perspective of, need it is preferable to use the nickel powder that average grain diameter is 0.05 μm~0.3 μm or so,
In particular, needing average grain diameter is the nickel powder of sub-micron in order to become 1000 layers of horizontal internal electrode, 0.05 is more preferably used
μm~0.1 μm of nickel powder.
[split-up promotor]
Split-up promotor adsorbs and is covered in the surface of nickel powder, plays and improves effect dispersed in nickel cream.As
The split-up promotor, including the split-up promotor with anionic interfacial agent structure.Herein, in this reality
It applies when manufacturing nickel cream under conditions of the manufacturing method of mode, the whole amount of the split-up promotor containing cooperation in nickel cream.
Herein, the surface of nickel powder has the property of alkalinity.Therefore, as split-up promotor, including with anion
The split-up promotor of type surfactant structures can be improved dispersion thereby, it is possible to effectively be adsorbed in nickel powder surface
Property.
(the split-up promotor with anionic interfacial agent structure)
Specifically, as the split-up promotor with anionic interfacial agent structure, it is, for example, possible to use
There is any one in the compound of specific structure shown in the following general formula (1).As shown in general formula (1), in present embodiment
The split-up promotor used has a double bond in main chain.
Wherein, in general formula (1), m, n meet the relationship of m+n=12~20.If m+n is less than 12, lipophilic insufficient,
Moisture separates insufficient.On the other hand, it if m+n is greater than 20, is difficult to be dissolved in organic solvent.
As the above-mentioned split-up promotor with anionic interfacial agent structure, specifically, can wrap
It includes from sweet by N- oleoyl-sarcosine, N- palmitoleoyl-sarcosine, N- octadecenoyl-N- methyl
One kind for selecting or also may include from above-mentioned in the group of propylhomoserin and N- tetracosene acyl-N-methyl glycine composition
The two or more combinations selected in compound.
For example, may be adapted to as the split-up promotor with anionic interfacial agent structure using molecule
Formula is C21H39NO3, chemistry shown in chemical formula (wherein, in general formula (1), the compound of m=7, n=7) by following (1-1)
Title " N- oleoyl-sarcosine "；Molecular formula is C19H35NO3(wherein, in general formula (1), the chemical combination of m=7, n=5
Object) chemical name " N- palmitoleoyl-sarcosine "；Molecular formula is C21H39NO3(wherein, in general formula (1), m=
9, the compound of n=5) chemical name " N- octadecenoyl-sarcosine "；Molecular formula is C27H51NO3(wherein,
In general formula (1), the compound of m=13, n=7) chemical name " N- tetracosene acyl-N-methyl glycine " etc..
[organic solvent]
Organic solvent is the solvent used usually as conductive paste with solvent, is promoted as long as above-mentioned split-up can be dissolved
Into the solvent of agent, there is no particular limitation.Wherein, it is preferable to use the organic solvents such as terpenol system, aliphatic hydrocarbon system.
Specifically, the organic solvent as terpenol system, for example, can enumerate terpinol (terpineol), dihydroterpineol,
Terpinyl acetate, baras camphor, geraniol, linalool etc..In addition, the organic solvent as aliphatic hydrocarbon system, for example, the positive last of the ten Heavenly stems can be enumerated
Alkane, n-dodecane, mineral spirits etc..For above-mentioned organic solvent, can be used alone, also can be used together two kinds with
On.
[adhesive resin]
As adhesive resin, selected from cellulosic structure, cellulose esters structure and cellulose ether structure for example, having
Structure, and the functional group's (acidic group) for having imported carboxyl etc. can contain at least one.
[other]
In addition, as needed, the nickel cream of present embodiment can add containing various in the range of not influencing above-mentioned effect
Add agent.
Specifically, can add for more improving the dispersing agent of the dispersibility of nickel powder in cream, for adjusting viscosity
Viscosity modifier and for improving thixotropic rheology control agent etc..
" manufacturing methods of 2. nickel cream "
Then, the manufacturing method of nickel cream is illustrated.The manufacturing method of the nickel cream of present embodiment at least has following
Three processes of [A]~[C].
That is, the manufacturing method of the nickel cream includes
[A] nickel organic ink formation process, the process add organic solvent in the water slurry of nickel powder and have anion
The split-up promotor of type surfactant structures, to form nickel organic ink；
[B] water separation process, the process separate water layer from the nickel organic ink for being separated into water layer and organic layer, thus
To organic layer nickel organic ink；And
[C] compounding procedure, the process are added adhesive resin and are kneaded in the organic layer nickel organic ink.Under
Each process is described in detail in face.
< [A] nickel organic ink formation process >
In process [A], organic solvent is added in the water slurry (nickel powder water slurry) of nickel powder and there is anionic circle
The split-up promotor of face active agent structures, is stirred, mixes, and obtains nickel organic ink.
(nickel powder water slurry)
As nickel powder, as set forth above, it is possible to use the various nickel powders of any manufacturing method manufacture such as wet process, dry method.For example,
It is preferable to use the nickel powders by being manufactured with so-called wet processes such as the wet-type reduction methods of the reducing agents such as hydrazine.
In addition, as nickel powder, it is preferable to use the ultra micron nickel for being 0.05 μm~0.5 μm by the average grain diameter that wet process manufactures
Powder.The ultra micron nickel powder that average grain diameter is 0.05 μm~0.5 μm is suitable as the purposes of the internal electrode of laminated ceramic capacitor,
It, can more significant ground expression effect by using above-mentioned nickel powder.
In process [A], it is dispersed in water above-mentioned ultra micron nickel powder by known method, so as to obtain
Nickel powder water slurry.
As the nickel content in nickel powder water slurry, there is no particular limitation, but preferably 20 mass of mass %~75 %.Such as
Fruit content is less than 20 mass %, then amount of moisture is excessive, and organic solvent used in nickel organic ink also largely uses in order to obtain.Separately
Outside, since nickel concentration reduces, so being difficult to generate good nickel cream.On the other hand, if content is greater than 75 mass %, moisture
Amount is reduced, and separates with organic solvent insufficient, and moisture is easy residual.
(the split-up promotor with anionic interfacial agent structure)
As the split-up promotor with anionic interfacial agent structure, as set forth above, it is possible to using following
There is any one in the compound of specific structure shown in general formula (1).Above-mentioned split-up promotor has in main chain
One double bond.
Wherein, in general formula (1), m, n meet the relationship of m+n=12~20.If m+n is less than 12, lipophilic insufficient,
Moisture separates insufficient.On the other hand, it if m+n is greater than 20, is difficult to be dissolved in organic solvent.
(organic solvent)
Organic solvent is the solvent used usually as conductive paste with solvent, as long as split-up promotor can be dissolved
Solvent, there is no particular limitation.As described above, it is preferred to use the organic solvents such as terpenol system, aliphatic hydrocarbon system.
As the organic solvent of terpenol system, terpinol (terpineol), dihydroterpineol, terpinyl acetate, camphane can be enumerated
Alcohol, geraniol, linalool etc..In addition, the organic solvent as aliphatic hydrocarbon system, can enumerate n-decane, n-dodecane, mineral oil
Essence etc..For above-mentioned organic solvent, it can be used alone or and with two or more.
(nickel organic ink)
In process [A], firstly, organic solvent and the split-up with anionic interfacial agent structure are promoted
Agent mixing, obtains the organic solution (split-up containing the split-up promotor with anionic interfacial agent structure
The organic solution of promotor).Then, it by mixing the organic solution of the split-up promotor with nickel powder water slurry, obtains
Nickel organic ink.
Herein, in the manufacturing method of present embodiment, (i) with the split-up of anionic interfacial agent structure
The additive amount of promotor and (ii) make the organic of the split-up promotor dissolution with anionic interfacial agent structure
The amount S of solvent1With the ratio between amount of moisture W " S in nickel powder water slurry1/ W " is important.By by above-mentioned additive amount and " S1/ W " ratio is set
For range appropriate, the split-up promotor with anionic interfacial agent structure can be evenly covered on nickel powder
Surface.
(i) additive amount about the split-up promotor with anionic interfacial agent structure
In the manufacturing method of present embodiment, by the split-up promotor with anionic interfacial agent structure
Additive amount be set as 1 times~4 times of the total surface area for making total molecular cross sectional area of above-mentioned split-up promotor reach nickel powder
Amount.
Specifically, for the above-mentioned split-up promotor with anionic interfacial agent structure additive amount and
Speech, for example, can be calculated using the method recorded using non-patent literature 1 added with anionic interfacial agent
(also referred to as absorption sectional area, is equivalent to and projects to point the molecular cross sectional area of the average per molecule of the split-up promotor of structure
The projected area of sub- plane), as a result, by calculating by the formula " total surface area (m of nickel powder2) × there is anionic interfacial activity
Quality (the g/m of the mean unit molecular cross sectional area of the split-up promotor of agent structure2) " calculate theoretical amount X value (g)
(X is in " the total surface area of nickel powder=split-up promotor with anionic interfacial agent structure total molecule section
The amount of the split-up promotor with anionic interfacial agent structure in the case where area ") it can acquire.The theory
The split-up that calculation amount X value is considered as bottom line needed for being comparable to uniform adsorption and coating entire nickel powder surface promotees
Into the amount of dosage.
Wherein, for molecular cross sectional area, in general, preparing the three of display Van der Waals (vdw) radius of structural optimization
Molecular model is tieed up, atom known to the vdw radius such as carbon atom is shown on same picture with molecule to be determined, as standard song
Line.The points to form the atomic building " circle " of standard curve are measured using image processing software, according to the vdw radius of above-mentioned atom
The area of average each point in picture is found out with round area.Then, pass through the points energy of the molecule of calculating sectional area to be determined
Enough find out molecular cross sectional area.
In addition, more specifically, according to non-patent literature 1, in the three-dimensional conformation of split-up promotor, can calculate
Sectional area in the most stable conformation is as molecular cross sectional area.In the non-patent literature 1, with typical higher fatty acids stearic acid
For illustrate the calculation method of molecular cross sectional area.Stearic structural formula (a) and space-filling model according to shown in the document
Scheme (b) and makes stearic sectional view.With bond length and vdw radius in the upper mapping such as squared paper, cuts the paper and weigh weight, from
And sectional area can be found out.
For example, as the split-up promotor with the anionic interfacial agent structure indicated with general formula (1),
With " N- oleoyl-sarcosine (molecular formula: C21H39NO3) " as an example of in the case where, and shown in above-mentioned non-patent literature 1
The calculation method of molecular cross sectional area be carried out similarly calculating, as a result known to above-mentioned N- oleoyl-sarcosine molecule
Sectional area is 0.00119g/m2.In the following, specifically describing above-mentioned calculating step.
It is 353g/mol firstly, finding out molal weight according to N- oleoyl-sarcosine chemical formula.That is, one point
The weight of son is 5.86E-22(g).For N- oleoyl-sarcosine, there are cis and trans optical isomer,
It is 5.09E when calculating cis- as the sectional area of a molecule-15(cm2)=5.09E-19(m2), it is 2.97E when trans--19
(cm2)=2.97E-19(m2).Herein, as cladding 1m2The accelerant N of split-up needed for nickel powder surface-oleoyl-N- methyl
The quantity of glycine, cis- is 1.96E+18A, trans- is 3.37E+18A, in mass, cis- is 1.15E-3G, it is trans- to be
1.97E-3g.That is, can calculate cis- for 0.00115g/m2, trans- is 0.0019g/m2.Therefore, hereby based on N- oleoyl-
Can to calculate molecular cross sectional area there are ratio be 0.00119g/m for sarcosine cis-, trans-2。
In addition, n (g) specific surface area used is A (m2/ g) Ni powder surface area be nAm2, by the way that above-mentioned value is multiplied,
Split-up accelerant N-oleoyl-sarcosine theory with anionic interfacial agent structure can be calculated
Calculation amount X value is nA × 0.00119 (g).
In the manufacturing method of present embodiment, based on the theoretical amount X value calculated as described above, according to the table of nickel powder
The split-up with anionic interfacial agent structure that area adds~4 times of amounts of 1 times of amount of theoretical amount X value promotes
Agent.If the additive amount of the split-up promotor with anionic interfacial agent structure is less than the 1 of theoretical amount X value
It measures again, then above-mentioned split-up promotor cannot equably coat nickel powder surface, then, implement mixing process and manufacture organic
Water in nickel cream can remain.On the other hand, if additive amount is greater than 4 times of amounts of theoretical amount X value, above-mentioned dispersion turns
Moving promotor, overlapping has coated plurality of layers on nickel powder surface, so water is lockable at this time, the residual quantity of water increases instead.
In addition, although above-mentioned additive amount is different according to the difference of split-up promotor type, but if only with having
The additive amount of the split-up promotor of anionic interfacial agent structure is provided, then as cladding 1m2Nickel powder surface
The additive amount of the required split-up promotor with anionic interfacial agent structure, preferably 0.00119g/m2~
0.00900g/m2, more preferably 0.00150g/m2~0.00900g/m2, particularly preferably 0.00182g/m2~0.00856g/
m2。
(ii) the amount S of organic solvent1With the ratio between amount of moisture W " S1/W”
In addition, after the above-mentioned split-up promotor with anionic interfacial agent structure is dissolved in organic solvent
It is added in nickel powder water slurry again.At this point, in the present embodiment, about organic solvent and nickel powder water slurry, organic solvent
Quality S1With the ratio between the quality W of water in nickel powder water slurry " S1/ W " meets 0.02 < S1The relationship of/W < 0.4.
Herein, if directly adding the split-up promotor with anionic interfacial agent structure in nickel powder water
In slurry, then above-mentioned split-up promotor carries out micellization and is difficult to efficiently be adsorbed in nickel powder surface.Therefore, have in addition
When having the split-up promotor of anionic interfacial agent structure, needs temporarily to be dissolved in after organic solvent and be added again in nickel
In powder water slurry.
When will there is the split-up promotor of anionic interfacial agent structure to be covered in nickel powder, as making to disperse
The mixing method of organic solvent (organic solvent of split-up promotor) and nickel powder water slurry of promotor dissolution is shifted,
There is no particular limitation, for example, can using used as the ball mill of well known decentralized processing device, homogenizer, mortar, from
The method of dynamic mortar, kneader, planetary-type mixer etc..In addition, as needed, can be subtracted using vacuum pump or suction pump
Pressure implements deaeration, dehydration.Alternatively, it is also possible to be heated, cooling treatment.
< [B] water separation process >
In process [B], the water layer is separated from the nickel organic ink for being separated into water layer and organic layer, obtains organic layer
Nickel organic ink.
Nickel powder point in above-mentioned operation [A], after obtaining nickel organic ink by mixing, in the nickel organic ink
It dissipates and is transferred to organic layer, the water for being separated off supernatant by a conventionally known method is adopted, to obtain organic layer nickel organic ink.
Remain the moisture of 15 mass of mass %~50 % or so in the organic layer nickel organic ink separated in this process,
In the manufacturing method of present embodiment, above-mentioned residual water can be efficiently reduced in the compounding procedure [C] of the next step
Point.
< [C] compounding procedure >
In process [C], adhesive resin is added in organic layer nickel organic ink and is kneaded.In the process [C]
In, it, can be effective by so-called developing technique, namely by the way that organic layer nickel organic ink to be kneaded with adhesive resin
Ground is separated off remaining moisture in slurry.As a result, specifically, can obtain small by the moisture rate of Karl_Fischer method measurement
In the nickel cream of 1 mass %.
As adhesive resin, there is no particular limitation, preferably so that resin is dissolved in carrier obtained from organic solvent
Mode add.Wherein, carrier is the substance as obtained from resin is made to be dissolved in organic solvent, can be with as organic solvent
It is the use usually used organic solvent on the way in conductive paste.
For example, can be used as resin containing from by with cellulosic structure, cellulose esters structure and cellulose ether knot
At least one resin selected in the group of the compound composition of structure.In addition, as organic solvent, as long as above-mentioned tree can be dissolved
Rouge, there is no particular limitation, for example, it is preferable to be terpenol system, aliphatic hydrocarbon system equal solvent, is suitable for use and above-mentioned operation
The identical solvent of organic solvent used in the nickel organic ink formation process of [A].
As the concentration of the carrier used, there is no particular limitation, preferably 5 mass % or more, more preferably 10 matter
Measure % or more.If concentration is less than 5 mass %, it is likely that viscosity reduces, and when mixing is difficult to apply torque, moreover, water separates
Must be insufficient, the remnant of moisture content of nickel cream increases.In addition, the upper limit value as carrier concn, there is no particular limitation, Ke Yishe
For such as 30 mass % or less.
In addition, well known method can be used as mixing method, specifically, can be by using roller mill, ball milling
The method of the kneading devices such as machine, homogenizer, mixing and kneading machine, kneader, planetary-type mixer is kneaded, and there is no particular limitation.
In addition, as needed, can be depressurized using vacuum pump or suction pump, implement deaeration, dehydration.Alternatively, it is also possible into
Row heating, cooling treatment.
So, it by making organic solvent and resin force to be adsorbed in nickel water slurry, is replaced using by water and organic solvent
And " developing technique " separated, it so that the moisture rate of obtained nickel cream is reduced.Specifically, can will pass through
The moisture rate of Karl_Fischer method measurement is more effectively set as less than 1 mass %.
In addition, after being separated off remaining moisture, it can be by the obtained nickel cream and as laminated ceramic capacitor
The mixing such as the dielectric such as barium titanate of constituent.It is further possible to add dispersing agent to improve dispersibility, separately
Outside, organic solvent can also be added to adjust viscosity.Furthermore it is also possible to add rheology control agent etc. and be kneaded to generate touching
Denaturation.
As described above, being organic as carboxylic acid, sarcosine as passing through end in the manufacturing method of present embodiment
Therefore there is acid etc. the split-up promotor of anionic interfacial agent structure, which to implement surface cladding, can effectively obtain
The nickel cream to made of dispersing nickel powder in the state that agglutination is few.
According to the obtained nickel cream, for example, being adapted as the high stacking ceramic electrical increased to the requirement of miniaturization
The internal electrode material of container.
Embodiment
In the following, showing the embodiment of the present invention and further specifically describing, but the present invention is not by following embodiment
Any restriction.
" evaluation method "
The nickel cream obtained under the manufacturing condition shown in following embodiments and comparative example is carried out by following evaluation method
Evaluation.
(measurement of residual moisture rate)
Using coulometric titration formula karl Fischer moisture teller (capital of a country electronics industry Co. Ltd. system), to obtained nickel
Cream, the residual moisture rate (quality %) under conditions of 180 DEG C of measurement, as its moisture rate.
(measurement of dry film density)
Obtained nickel cream is coated on polyethylene terephthalate with 200 μm of thickness using coating machine
It is 40 minutes dry under conditions of 120 DEG C on (Polyethylene terephthalate, PET) film.Obtained film is rushed
It is cut into φ 40mm, measurement area, film thickness and weight calculate dry film density according to above-mentioned data.
(evaluation of viscosity)
Using rheometer (MCR-501, Anton Paar company (ア Application ト ン パ ー Le society) system), shear velocity 4.0s is measured-1、
The viscosity (Pas) of nickel cream under conditions of 25 DEG C.
" manufacture of nickel cream in embodiment and comparative example "
[embodiment 1-1]
(1) manufacture of nickel cream
Firstly, by the nickel Ultramicro-powder 90g of Sumitomo Metal Mining Co., Ltd (specification title: NR707, also by wet type
The Ni Ultramicro-powder of former method manufacture, average grain diameter are 0.07 μm, specific surface area 9.6m2/ g) it mixes in water, manufacture 300g slurry
Concentration is the nickel powder water slurry (amount of moisture 70%) of 30 mass %.
Then, prepare 10.5g dihydroterpineol (Japanese fragrance Co. Ltd. system) and be used as organic solvent, using 2.1g as tool
Have the split-up promotor of anionic interfacial agent structure N- oleoyl-sarcosine (product name:
Oleoylsarcosine (オ レ オ イ Le ザ Le U シ Application) 221P) it is dissolved in above-mentioned organic solvent, 12.6g dispersion is made
Shift the organic solution of promotor.
Then, for 300g nickel powder water slurry, the organic solution of split-up promotor made of 12.6g is added,
Use brilliant automatic homogenizer (エ Network セ ル オ ー ト ホ モ ジ Na イ ザ ー) (Japan Precise Machine Co., Ltd's system) with peripheral speed 10m/
The rotation speed of s is mixed 2 minutes, obtains 2.0 times of amounts of calculated value X value having anionic interfacial agent
The split-up promotor of structure is covered in nickel powder organic ink made of nickel powder.In addition, making with anionic circle at this time
The amount S of the organic solvent of the split-up promotor mixed dissolution of face active agent structures1With the ratio between amount of moisture W in nickel powder water slurry
S1/ W is 0.050.
In addition, the surface area of 90g nickel powder is 9.6 × 90=864m as treatment conditions2, as described above for covering 1m2
The additive amount of the split-up promotor with teepol structure on the nickel powder surface is 0.00119g/m2,
Calculating theoretical amount X value is 864m2×0.00119g/m2=1.03g, the 2.1g added in embodiment 1, which is used as, has anion
N- oleoyl-sarcosine of the split-up promotor of type surfactant structures is 2.0 times of theoretical amount X value
Amount.
Then, in organic solvent dihydroterpineol, ethyl cellulose (the DOW Chemical public affairs as adhesive resin are put into
Take charge of (ダ ウ ケ ミ カ Le society) system, specification title: STD300), exist while stirring 80 DEG C under conditions of heat, carrier is made
(10.5 mass % ethyl cellulose).Then, using three rollers by the above-mentioned carrier of 21.5g with as described above manufacture split-up
Promotor is covered in nickel powder organic ink made of nickel powder and is adequately kneaded, and then, is diluted with dihydroterpineol, obtains nickel
Concentration is the nickel cream of 60 mass %, the split-up promotor for containing 2.3 mass parts relative to 100 mass parts of nickel powder.
(2) evaluation of nickel cream
[measurement of moisture rate]
By above-mentioned evaluation method, " residual moisture rate ", " dry film density " are carried out to obtained nickel cream and " glued
The measurement of degree ", and evaluated.
As a result, residual moisture rate is few, it is 0.51 mass %.In addition, obtaining dry film density is up to 5.4g/cm3
Film density.In addition, viscosity is 94.0Pas, it is the viscosity that can be enough to use as cream.
[embodiment 1-2]
N- oleoyl-N- methyl in addition to the split-up promotor with anionic interfacial agent structure will be used as
The additive amount of glycine is set as other than 1.1 times of amounts of theoretical amount X value, is carried out similarly processing with embodiment 1-1, nickel is made
Concentration is the nickel cream of 60 mass %, the split-up promotor for containing 1.3 mass parts relative to 100 mass parts of nickel powder.In addition, tool
For body, the additive amount of the split-up promotor with anionic interfacial agent structure is 1.13g.In addition, organic molten
The amount S of agent1With the ratio between amount of moisture W in nickel powder water slurry S1/ W is 0.050.
Obtained nickel cream is evaluated similarly to Example 1.As a result, moisture rate is few, it is 0.69 matter
Measure %.In addition, obtaining dry film density is up to 4.9g/cm3Film density.In addition, viscosity is 135.0Pas, it is that can be enough
The viscosity used as cream.
[embodiment 1-3]
N- oleoyl-N- methyl in addition to the split-up promotor with anionic interfacial agent structure will be used as
The additive amount of glycine is set as other than 3.5 times of amounts of theoretical amount X value, is carried out similarly processing with embodiment 1-1, nickel is made
Concentration is the nickel cream of 60 mass %, the split-up promotor for containing 4.0 mass parts relative to 100 mass parts of nickel powder.In addition, tool
For body, the additive amount of the split-up promotor with anionic interfacial agent structure is 3.61g.In addition, organic molten
The amount S of agent1With the ratio between amount of moisture W in nickel powder water slurry S1/ W is 0.050.
Obtained nickel cream is evaluated similarly to Example 1.As a result, moisture rate is few, it is 0.94 matter
Measure %.In addition, obtaining dry film density is up to 5.1g/cm3Film density.In addition, viscosity is 53.4Pas, it is that can be enough
The viscosity used as cream.
[embodiment 1-4]
In addition to the adhesive resin that will be kneaded is replaced by ethyl cellulose (Dow Chemical's system, specification title: STD300)
It is changed to other than ethyl cellulose (Dow Chemical's system, specification title: STD45), is carried out similarly processing with embodiment 1-1,
The nickel cream that nickel concentration is 60 mass %, the split-up promotor for containing 2.3 mass parts relative to 100 mass parts of nickel powder is made.
The additive amount of split-up promotor with anionic interfacial agent structure is 2.1g, is the 2.0 of theoretical amount X value
It measures again.In addition, the amount S of organic solvent1With the ratio between amount of moisture W in nickel powder water slurry S1/ W is 0.064.
Obtained nickel cream is evaluated similarly to Example 1.As a result, moisture rate is few, it is 0.79 matter
Measure %.In addition, obtaining dry film density is up to 5.2g/cm3Film density.In addition, viscosity is 25.5Pas, it is that can be enough
The viscosity used as cream.
[embodiment 1-5]
In addition to the adhesive resin that will be kneaded is replaced by ethyl cellulose (Dow Chemical's system, specification title: STD300)
It is changed to other than ethyl cellulose (Dow Chemical's system, specification title: STD4), is carried out similarly processing with embodiment 1-1, make
It is the nickel cream of 60 mass %, the split-up promotor for containing 2.3 mass parts relative to 100 mass parts of nickel powder at nickel concentration.Point
The additive amount for dissipating transfer promotor is 2.1g, is 2.0 times of amounts of theoretical amount X value.In addition, the amount S of organic solvent1With nickel powder
The ratio between amount of moisture W in water slurry S1/ W is 0.050.
Obtained nickel cream is evaluated similarly to Example 1.As a result, moisture rate is few, it is 0.54 matter
Measure %.In addition, obtaining dry film density is up to 5.2g/cm3Film density.In addition, viscosity is 12.8Pas, it is that can be enough
The viscosity used as cream.
[embodiment 1-6]
In addition to the adhesive resin that will be kneaded is replaced by ethyl cellulose (Dow Chemical's system, specification title: STD300)
It is changed to ethyl cellulose (Dow Chemical's system, specification title: STD4), further, there will be anionic interfacial activity
Split-up accelerant N-oleoyl-sarcosine additive amount of agent structure is set as 3.5 times of amounts of theoretical amount X value
In addition, it is carried out similarly processing with embodiment 1-1, nickel concentration is made and is 60 mass %, contains relative to 100 mass parts of nickel powder
The nickel cream of the split-up promotor of 4.0 mass parts.In addition, specifically, point with anionic interfacial agent structure
The additive amount for dissipating transfer promotor is 3.61g.In addition, the amount S of organic solvent1With the ratio between amount of moisture W in nickel powder water slurry S1/W
It is 0.050.
Obtained nickel cream is evaluated similarly to Example 1.As a result, moisture rate is few, it is 0.91 matter
Measure %.In addition, obtaining dry film density is up to 5.2g/cm3Film density.In addition, viscosity is 8.5Pas, it is that can be enough to make
The viscosity used for cream.
[comparative example 1-1]
N- oleoyl-N- methyl in addition to the split-up promotor with anionic interfacial agent structure will be used as
The additive amount of glycine is set as other than 0.5 times of amount of theoretical amount X value, is carried out similarly processing with embodiment 1-1, is attempted system
Make the nickel cream that nickel concentration is 60 mass %, the split-up promotor for containing 0.6 mass parts relative to 100 mass parts of nickel powder.Separately
Outside, specifically, the additive amount of the split-up promotor with anionic interfacial agent structure is 0.52g.In addition, having
The amount S of solvent1With the ratio between amount of moisture W in nickel powder water slurry S1/ W is 0.050.
But under this condition, resin cannot be firmly kneaded, cream cannot be obtained.
[comparative example 1-2]
N- oleoyl-N- methyl in addition to the split-up promotor with anionic interfacial agent structure will be used as
The additive amount of glycine is set as other than 5.0 times of amounts of theoretical amount X value, is carried out similarly processing with embodiment 1-1, nickel is made
Concentration is the nickel cream of 60 mass %, the split-up promotor for containing 5.7 mass parts relative to 100 mass parts of nickel powder.In addition, tool
For body, the additive amount of the split-up promotor with anionic interfacial agent structure is 5.16g.In addition, organic molten
The amount S of agent1With the ratio between amount of moisture W in nickel powder water slurry S1/ W is 0.050.
Obtained nickel cream is evaluated similarly to Example 1.As a result, moisture rate is 1.5 mass %, it cannot
Moisture is fully removed, dry film density is also down to 3.7g/cm3, fine and close film cannot be obtained.In addition, viscosity is 48.6Pa
s。
[comparative example 1-3]
In addition to making dissolution with the amount S of the organic solvent of the split-up promotor of anionic interfacial agent structure1
With the ratio between amount of moisture W in nickel powder water slurry S1/ W reaches other than 0.01, is carried out similarly processing with embodiment 1-1, attempts system
Make the nickel cream that nickel concentration is 60 mass %, the split-up promotor for containing 2.3 mass parts relative to 100 mass parts of nickel powder.Separately
Outside, the additive amount of the split-up promotor with anionic interfacial agent structure is 2.1g, is theoretical amount X value
2.0 times of amounts.
But under this condition, it is difficult to be firmly kneaded resin, in addition, cannot separate to moisture rate substantially and be
18.6%, nickel cream cannot be obtained.
[comparative example 1-4]
In addition to making dissolution with the amount S of the organic solvent of the split-up promotor of anionic interfacial agent structure1
With the ratio between amount of moisture W in nickel powder water slurry S1/ W reaches other than 0.50, is carried out similarly processing with embodiment 1-1, nickel is made
Concentration is the nickel cream of 60 mass %, the split-up promotor for containing 2.3 mass parts relative to 100 mass parts of nickel powder.In addition, tool
The additive amount for having the split-up promotor of anionic interfacial agent structure is 2.1g, is 2.0 times of theoretical amount X value
Amount.
Obtained nickel cream is evaluated similarly to Example 1.As a result, moisture rate is 1.3 mass %, it cannot
Moisture is fully removed, dry film density is also down to 3.9g/cm3, fine and close film cannot be obtained.In addition, viscosity is 30.0Pa
s。
[comparative example 1-5]
N- oleoyl-N- methyl in addition to the split-up promotor with anionic interfacial agent structure will be used as
The additive amount of glycine is set as other than 0.5 times of amount of theoretical amount X value, is carried out similarly processing with embodiment 1-5, is attempted system
Make the nickel cream that nickel concentration is 60 mass %, the split-up promotor for containing 0.6 mass parts relative to 100 mass parts of nickel powder.Separately
Outside, specifically, the additive amount of the split-up promotor with anionic interfacial agent structure is 0.52g.
But under this condition, resin cannot be firmly kneaded, cream cannot be obtained.
[comparative example 1-6]
N- oleoyl-N- methyl in addition to the split-up promotor with anionic interfacial agent structure will be used as
The additive amount of glycine is set as other than 5.0 times of amounts of theoretical amount X value, is carried out similarly processing with embodiment 1-5, is attempted system
Make the nickel cream that nickel concentration is 60 mass %, the split-up promotor for containing 5.7 mass parts relative to 100 mass parts of nickel powder.Separately
Outside, specifically, the additive amount of split-up promotor is 5.16g.
Obtained nickel cream is evaluated similarly to Example 1.As a result, moisture rate is 1.2 mass %, it cannot
Moisture is fully removed, dry film density is also down to 4.1g/cm3, fine and close film cannot be obtained.In addition, viscosity is 7.0Pas,
It cannot function as cream use.
[embodiment 2]
In example 2, the nickel powder used be Sumitomo Metal Mining Co., Ltd nickel Ultramicro-powder 90g (specification title:
NR720, the Ni Ultramicro-powder manufactured by wet-type reduction method, average grain diameter are 0.2 μm, specific surface area 4.46m2/ g), by its
It is mixed in water, the nickel powder water slurry (amount of moisture 70%) that manufacture 300g slurry concentration is 30 mass %.
The theoretical amount X value of above-mentioned nickel powder (NR720) is 0.48g, will be as with anionic interfacial agent knot
N- oleoyl-sarcosine additive amount of the split-up promotor of structure is set as 0.51g, is theoretical amount X value
1.1 times of amounts.In addition, making the amount S of organic solvent1With the ratio between amount of moisture W in nickel powder water slurry S1/ W reaches 0.050.
In addition, being carried out similarly the processing of subsequent handling with the condition of above-described embodiment 1-2, it is 60 matter that nickel concentration, which is made,
Amount %, contain relative to 100 mass parts of nickel powder 0.6 mass parts split-up promotor nickel cream.
Obtained nickel cream is evaluated similarly to Example 2.As a result, moisture rate is few, it is 0.54 matter
% is measured, moreover, obtaining dry film density is up to 5.2g/cm3Film density.In addition, viscosity is 120.0Pas, it is that can be enough
The viscosity used as cream.
[comparative example 2]
Using nickel powder same as Example 2, in addition to the dispersion with anionic interfacial agent structure will be used as to turn
N- oleoyl-sarcosine the additive amount for moving promotor is set as other than 0.5 times of theoretical amount X value, with embodiment 2
It is carried out similarly processing, attempts point that manufacture nickel concentration is 60 mass %, contains 0.3 mass parts relative to 100 mass parts of nickel powder
Dissipate the nickel cream of transfer promotor.In addition, specifically, the additive amount of split-up promotor is 0.23g.
But under this condition, resin cannot be firmly kneaded, cream cannot be obtained.
[comparative example 3]
Using nickel powder same as Example 2, in addition to the dispersion for making dissolution have anionic interfacial agent structure turns
Move the amount S of the organic solvent of promotor1With the ratio between amount of moisture W in nickel powder water slurry S1/ W reaches other than 0.50, with embodiment 2
It is carried out similarly processing, the dispersion turn that nickel concentration is 60 mass %, contains 0.6 mass parts relative to 100 mass parts of nickel powder is made
Move the nickel cream of promotor.In addition, the additive amount of split-up promotor is 0.51g, it is 1.1 times of amounts of theoretical amount X value.
Obtained nickel cream is evaluated similarly to Example 2.As a result, moisture rate is 2.4 mass %, it cannot
Moisture is fully removed, good cream cannot be manufactured.Therefore, the evaluation of film density is not dried.
It will also realize that according to the result of above embodiments and comparative example, for being obtained within the scope of the rated condition shown in embodiment
For the nickel cream arrived, moisture rate is all extremely low, in addition, desciccator diaphragm density also high dense film can be obtained.Moreover, knowing at these
The nickel powder not being aggregated substantially in nickel cream, dispersibility is excellent and has viscosity appropriate.
Claims (3)
1. a kind of manufacturing method of nickel cream, which is characterized in that
It is included
Nickel organic ink formation process, the process add organic solvent in the water slurry of nickel powder and have anionic interface living
The split-up promotor of property agent structure, to form nickel organic ink；
Water separation process, the process separate the water layer from the nickel organic ink for being separated into water layer and organic layer, thus
Obtain organic layer nickel organic ink；And
Compounding procedure, the process are added adhesive resin and are kneaded in the organic layer nickel organic ink,
In the nickel organic ink formation process, promote as the split-up with anionic interfacial agent structure
The split-up promotor indicated into agent, addition with the following general formula (1),
Relative to the nickel powder, the additive amount of the split-up promotor with anionic interfacial agent structure is to make
Total molecular cross sectional area of the split-up promotor with anionic interfacial agent structure reaches the total surface of the nickel powder
The amount of long-pending 1 times~4 times,
The quality S of the organic solvent1With the ratio between quality W of water S in the water slurry of the nickel powder1/ W meets 0.02 < S1/ W <
0.4 relationship,
In formula (1), m, n meet the relationship of m+n=12~20.
2. the manufacturing method of nickel cream as described in claim 1, which is characterized in that
The split-up promotor with anionic interfacial agent structure is from by the sweet ammonia of N- oleoyl-N- methyl
Acid, N- palmitoleoyl-sarcosine, N- octadecenoyl-sarcosine and N- tetracosa carbon enoyl--N-
Methylglycine composition group in select more than one.
3. the manufacturing method of nickel cream as claimed in claim 1 or 2, which is characterized in that
In the compounding procedure, described adhesive resin is made, the adhesive resin is contained with the concentration of 5 mass % or more
Carrier, to be added.
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| PCT/JP2015/077120 WO2016047761A1 (en) | 2014-09-26 | 2015-09-25 | Nickel paste and nickel paste production method |
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| JP2006183066A (en) * | 2004-12-27 | 2006-07-13 | Sumitomo Metal Mining Co Ltd | Nickel powder-dispersed organic slurry and method for producing the same |
| CN1972995A (en) * | 2004-06-21 | 2007-05-30 | 积水化学工业株式会社 | Binder resin composition, paste, and green sheet |
| JP2012107201A (en) * | 2010-10-29 | 2012-06-07 | Sekisui Chem Co Ltd | Modified polyvinyl acetal resin, and modified polyvinyl acetal resin composition |
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| JP4495644B2 (en) * | 2004-07-30 | 2010-07-07 | Ｊｆｅミネラル株式会社 | Metal super fine slurry |
| TW200640596A (en) * | 2005-01-14 | 2006-12-01 | Cabot Corp | Production of metal nanoparticles |
| CN103140970B (en) * | 2010-09-24 | 2015-05-13 | Jsr株式会社 | Binder composition for electrode |
| JP5871762B2 (en) * | 2012-09-27 | 2016-03-01 | 富士フイルム株式会社 | Conductive film forming composition and conductive film manufacturing method |
| JP5856038B2 (en) * | 2012-10-31 | 2016-02-09 | 三ツ星ベルト株式会社 | Conductive adhesive for screen printing, joined body of inorganic material, and manufacturing method thereof |
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| CN1972995A (en) * | 2004-06-21 | 2007-05-30 | 积水化学工业株式会社 | Binder resin composition, paste, and green sheet |
| JP2006183066A (en) * | 2004-12-27 | 2006-07-13 | Sumitomo Metal Mining Co Ltd | Nickel powder-dispersed organic slurry and method for producing the same |
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