CN102254585B - Method for manufacturing conductive paste - Google Patents
Method for manufacturing conductive paste Download PDFInfo
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- CN102254585B CN102254585B CN2011100975046A CN201110097504A CN102254585B CN 102254585 B CN102254585 B CN 102254585B CN 2011100975046 A CN2011100975046 A CN 2011100975046A CN 201110097504 A CN201110097504 A CN 201110097504A CN 102254585 B CN102254585 B CN 102254585B
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 34
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- 238000010438 heat treatment Methods 0.000 claims abstract description 16
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
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Images
Classifications
-
- 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
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/005—Electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/30—Stacked capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Conductive Materials (AREA)
Abstract
The invention provides a method for manufacturing a conductive paste which has high dispersivity and excellent viscosity stability as a paste for an internal electrode of a laminated porcelain capacitor. The method for manufacturing the conductive paste is characterized by including one to three steps of: a preliminary treatment dispersion step, heating and mixing the coarse conductive paste including the conductive metallic powders, a dispersant, an organic adhesive and an organic solvent, permitting it to pass through a nozzle having an orifice; a dispersion step, dispersing the heated conductive paste by a high-pressure homogenizer; and a filtering step, filtering the conductive paste after dispersion treatment by a filter.
Description
Technical field
The present invention relates to a kind ofly in the multi-layer ceramic capacitor internal electrode paste, keep polymolecularity, the manufacture method of the conductive paste of viscosity stability excellence simultaneously.
Background technology
Be accompanied by the frivolous compact of the electronic equipments such as mobile phone and digital device, for as the multi-layer ceramic capacitor of chip part (below be called MLCC) also at expectation its miniaturization, high capacity and high performance.Effective method that be used for to realize these is that attenuate interior electrode layer and dielectric layer are sought multiple stratification.
This MLCC generally makes by following operation.In order to form dielectric layer, at first with barium titanate (BaTiO
3) comprise on the dielectric raw cook of the organic bonds such as barium titanate and polyvinyl butyral resin for principal component, will be take electroconductive powder as principal component, make its be dispersed in form in the carrier that comprises resin binder and solvent, print as the conductive paste pattern in accordance with regulations of internal electrode, and make its drying come desolventizing, form desciccator diaphragm.Then, the dielectric raw cook that will be formed with desciccator diaphragm adds thermo-compressed and carries out integrated under multilayer laminated state, then cut off, in oxidizing atmosphere or inert atmosphere, carrying out the unsticking mixture below 500 ℃, thereafter, not make the mode of internal electrode oxidation, in reducing atmosphere, about 1300 ℃, carry out heating and calcining.Then, will calcine chip coating, calcining after, externally implement nickel plating etc. on the electrode, make MLCC.
But, in this calcination process, the temperature that dielectric ceramic powder begins sintering is about 1200 ℃ because with the sintering of the conductive metal powder such as nickel, shrink the beginning temperature and produce sizable inconsistently, therefore easily produce the faults of construction such as delamination (splitting) or crackle.Particularly be accompanied by small-sized, high capacity, stacked number thickness more or the ceramic dielectric layer is thinner, and it is more obvious that the generation of fault of construction just becomes.
For example, use in the nickel paste at common internal electrode, at least until dielectric layer begin near the temperature of sintering, contraction, in order to control its sintering, contraction, the perofskite type oxide that is added with to be similar to the barium titanate class of composition of dielectric layer or strontium zirconate class etc. is the ceramic powders of main component.Its result can control the sintering behavior of nickel by powder, suppresses sintering shrinkage behavior inconsistent of interior electrode layer and dielectric layer.In addition, add ceramic powders can alleviate Constitution Elements difference when the dielectric medium powder that comprises in the Constitution Elements of the principal component of dielectric layer and the electrode paste agent when large dielectric absorption increase etc. bring the such trouble of impact to electrical characteristics.
In recent years, the requirement of, high capacity more small-sized along with MLCC is used the interior electrode layer of the conductive metal powder such as nickel and is used the further thin layerization rapid progress of dielectric layer of the ceramic powders of barium titanate etc.Therefore, just need the conductive metal powder such as nickel for conductive paste and micronize, the enhancement of dispersion of ceramic powders.
Yet; owing to being accompanied by the micronize progress of conductive metal powder and ceramic powders; the easness of aggegation increases gradually; therefore; only shear with the existing mechanicalness of 3 roller machines of utilizing; the conductive paste of required dispersity be can not make, level and smooth dry coating or high dry film density are difficult to obtain.Thereby, as patent documentation 1,2, for being processed, fine-particle powder until obtain required dispersiveness, makes conductive paste in the time of must increasing worker, and manufacturing time is elongated as a result.
In addition, common to utilize the manufacture method of the conductive paste of 3 roller machines be that raw material is mixing, then makes its dispersion, then carrying out viscosity such as needs regulates, but in this manufacture method, even when considering worker, disperse also limited for conductive metal powder or the ceramic powders that makes particulate.
On the other hand, method as beyond the 3 roller machines that are distributed to carrier and solvent for inorganic powders such as the conductive metal powder that makes dry aggegation or ceramic powders discloses the method that makes its mechanical dispersion, pulverizing with ball mill or ball mill etc. in the patent documentation 3,4.
But, in utilizing the process for dispersing of ball mill, there is the problem of the conductive metal powder distortion that is caused by medium, in utilizing the process for dispersing of ball mill, in the situation that the conductive metal powder is firm aggegation, limited for it is disperseed fully.
Recently, as the process for dispersing beyond above-mentioned 3 roller machines, ball mill, the ball mill, the manufacture method (for example, with reference to patent documentation 5,6) that has proposed to use the conductive metal slurry of high-pressure homogenizer and used its conductive paste.
In this patent documentation 5, behind the moistened surface with metallic particles and ceramic particle, use high-pressure homogenizer, by the injection stream of spraying from the nozzle that is arranged at relative direction is run foul of each other, make conductive paste, but in the method, the slurry viscosity that the injection stream of utilizing high-pressure homogenizer to spray from nozzle is produced limits, and then process the problem that occurs in the situation of the high viscosity slurry be added with organic carrier with high-pressure homogenizer at normal temperatures and be, hindered by organic carrier owing to giving the impact force of conductive metal powder or ceramic powder, therefore the impact force that is produced by high-pressure homogenizer can't play a role to conductive metal powder or ceramic powder effectively, can not disperse fully.
In addition, patent documentation 6 has reported that the thick slurry that premixed inorganic particle and organic solvent are formed utilizes high-pressure homogenizer to carry out dispersion treatment and makes the conductivity slurry, uses this conductivity slurry to make conductive paste.
But, the common ground of the compounding process in the existing conductive paste manufacturing process is, use the above devices such as planetary mixer of high speed shear mixer or 2 axles, the inorganic powder such as conductive metal powder or ceramic powder and organic substance (organic solvent, dispersant, organic carrier etc.) are mixed.Yet, in these compounding process, the surface that often becomes organic carrier undercompounding, conductive metal powder or ceramic powders becomes fully not wetting etc. state, in the situation of the dispersion treatment of utilizing high-pressure homogenizer of carrying out lower operation through these compounding process, easily produce following problem.
The first, because adding organic carrier, the viscosity of the thick paste of conductivity raises, its as a result flowability become not enough, thereby be difficult to utilize the dispersion treatment of high-pressure homogenizer.
The second, there is the organic carrier that does not mix fully in the thick paste of conductivity, when it was put in the high-pressure homogenizer, the solid constituent that includes organic carrier was attached in the device, became to be difficult to normal operation.
The 3rd, hindered by organic carrier, (organic carrier becomes cushion pad by can not bringing into play to greatest extent the impact force of conductive metal powder or ceramic powder or shearing force of producing of high-pressure homogenizer, mechanical shear stress can't play a role to conductive metal powder or ceramic powders effectively, can not obtain sufficient dispersiveness).
The 4th, because the surface of conductive metal powder or ceramic powders is not wetting fully, so conductive paste is almost lackluster, in addition, owing to have the agglutinator larger than nozzle diameter, and so the frequency gets higher of obstruction occurs in nozzle.
In addition, though different from purposes of the present invention, as the method for the dispersiveness that improves solder paste, patent documentation 7 has been reported and has been made it by the method for throttle orifice, but in this way, particulate conductive metal powder or ceramic powders can not disperse.
Also have, in the situation that process with 3 roller machines and since just begun rear conductive metal powder form laminar, or because a little less than the mechanical shear stress, therefore in the wetting inadequate situation on the surface of material powder, there is limit to obtaining required dispersiveness.
Usually, the dispersion process of conductive metal powder and ceramic powders comprises following process:
(1) " wetting " of conductive metal powder and ceramic powders, namely be present in air in the space of 2 particle surfaces and 2 granule interior by the process of organic solvent and dispersant displacement;
(2) 2 times particle is dispersed the process that machine disperses, pulverizes;
(3) dispersant adsorption is carried out the process of particle " preventing again aggegation " at the particle surface through disperseing, pulverizing.
In this dispersion process, utilize the pretreatment procedure of the mixing stirring of mixer etc. to affect the wetability of conductive metal powder and ceramic powders or the time of processing in next step dispersion step, utilize the dispersion step of the dispersion machines such as 3 roller machines to affect the dispersiveness of conductive metal powder and ceramic powders, in the situation of the bad dispersibility of particle after the dispersion step, because the part that exists dispersant not adsorbed by particle surface is therefore owing to being difficult to prevent that again aggegation from descend dispersion stabilization.
On the other hand, the micronize of conductive metal powder or ceramic powders is becoming main flow, but except making particulate inorganic powder disperses, in the conductive paste that uses particulate inorganic powder, exist because of through the time viscosity that the causes problem that changes.This is because when paste viscosity changes, because the variation of generation printing, meeting be so that can not obtain suitable thickness or shape when printing, and causes can not quality bills of materials stable electrode etc.
To this, as the method that suppresses the viscosity variation, patent documentation 8 has proposed to use Ni/Ni (OH)
2The conductive paste that/NiO obtains than being controlled at the nickel by powder in the distinctive composition ratio scope.
But, be accompanied by the micronize of nickel by powder, for control because of through the time conductive paste that causes viscosity change, the selection of dispersant or dispersant become important to the absorption of nickel surface.Especially, for using the conductive paste of the particulate nickel powder below the 0.2 μ m, only make its dispersion have limit by the present mechanical shearing that utilizes 3 roller machines because dispersant becomes insufficient to the absorption of nickel surface, the result just be difficult to control because of through the time viscosity that causes change.
The prior art document
Patent documentation
Patent documentation 1: JP 2006-351348 communique
Patent documentation 2: JP 2003-86449 communique
Patent documentation 3: JP 2006-156204 communique
Patent documentation 4:WO2005-043568 communique
Patent documentation 5: JP 2004-288528 communique
Patent documentation 6: JP 2005-104070 communique
Patent documentation 7: JP 2002-001528 communique
Patent documentation 8: JP 2004-330247 communique
Summary of the invention
Invent problem to be solved
Point in view of the above problems, for the full-bodied conductive paste that includes organic carrier, the present invention can utilize the high-pressure homogenizer manufacturing to be difficult at present the method for the full-bodied conductive paste made, can obtain polymolecularity, and can obtain the paste characteristic of viscosity stability excellence.It can improve " wetting " and " viscosity " in the pretreatment procedure by in the presence of organic carrier, and " viscosity " improved in addition when carrying out dispersion treatment with high-pressure homogenizer is made.
Namely, in existing pre-treating method, in the presence of organic carrier, the surface of conductive metal powder or ceramic powders is difficult to wetting, but in the present invention, even in the presence of organic carrier, make it have flowability by heating reduction viscosity, when having the nozzle of throttle diameter, can not cushioned by organic carrier and make the particle surface of conductive metal powder or ceramic powders easily wetting.And then, in pretreatment procedure, the moistened surface of conductive metal powder or ceramic powders, even under the state that organic carrier exists, make it have mobile conductive paste so long as heat, even if put in the high-pressure homogenizer of lower operation, the powerful shearing force that acts on conductive metal powder or ceramic powders is not cushioned by organic carrier yet and effectively plays a role, and dispersion efficiency improves.
Like this, by improving present pre-treating method and the process for dispersing that utilizes high-pressure homogenizer, even in the presence of organic carrier, utilize high-pressure homogenizer also can make conductive paste, utilize the conductive paste of the conductive metal slurry of high-pressure homogenizer manufacturing to compare with the conductive paste that utilizes 3 roller machines or use, obtain the conductive paste that dispersiveness is high and viscosity stability is excellent.In addition, with regard to viscosity stability, " wetting " of particle surface improves, and obtains polymolecularity in utilizing the dispersion process of high-pressure homogenizer.At this moment, because dispersant adsorption at particle surface, can prevent " the again aggegation " of particle, therefore, even long preservation also can be kept the dispersion stabilization of conductive paste.
As above, the object of the invention is to, the conductive paste that provides the multilayer ceramic electronic component of a kind of polymolecularity and viscosity stability excellence to use, it is for for the miniaturization of multilayer ceramic electronic component, slimming and conductive metal powder or the ceramic powder of miniaturization, even there is the full-bodied conductive paste of organic carrier, also available high-pressure homogenizer manufacturing.
Be used for solving the means of problem
The 1st invention of the present invention is the manufacture method of conductive paste, it is characterized in that, has following the 1st operation to the 3 operations.
[the 1st operation]: while after will containing at least the thick paste of conductivity of conductive metal powder, dispersant, organic bond and organic solvent and heating mix and blend, make it by possessing the nozzle of throttle orifice, carry out thus the pre-treatment dispersion step of dispersion treatment.
[the 2nd operation]: will utilize high-pressure homogenizer to carry out the dispersion step of dispersion treatment by the conductive paste through heating that the 1st operation pre-treatment disperses.
[the 3rd operation]: the filter progress that will utilize filter to filter by the conductive paste of the 2nd operation dispersion treatment.
The 2nd invention of the present invention be characterised in that, the nozzle that possesses throttle orifice of the 1st operation in the 1st invention in series arrange 2 with on the thick paste of conductivity is disperseed.
The 3rd invention of the present invention be characterised in that, the throttle diameter of the throttle orifice of the 1st operation in the 1st invention is 0.2～0.5mm.
The 4th invention of the present invention be characterised in that, the viscosity of the thick paste of conductivity in the 1st invention is below the 10Pas.
The 5th invention of the present invention be characterised in that, the high-pressure homogenizer in the 1st invention carries out dispersion treatment with the pressure of 50～250MPa.
The 6th invention of the present invention be characterised in that, the throttle diameter of the throttle orifice that possesses in the high-pressure homogenizer that the conductive paste of the 2nd operation in the 1st invention flows is 0.05～0.2mm.
The 7th invention of the present invention be characterised in that, the high-pressure homogenizer in the 1st invention possesses cooler in export department's side of throttle orifice.
The 8th invention of the present invention be characterised in that, the viscosity through the conductive paste of heating of the 2nd operation in the 1st invention is below the 10Pas.
The 9th invention of the present invention for utilize the 1st the invention formed conductive paste, it is characterized in that, the content of conductive metal powder is 30～70 % by weight with respect to the conductive paste total amount.
The 10th invention of the present invention be characterised in that, in the conductive paste of the 9th invention, conductive paste comprises ceramic powders as sintering inhibitor.
The invention effect
According to the present invention, in the manufacture method of the conductive paste in multilayer ceramic electronic component, give conductive paste is finished the conductive paste that the paste characteristic of excellence is specialized with polymolecularity formation by utilizing the mechanical shearing effect, and then as the multi-layer ceramic capacitor internal electrode paste, realized keeping the conductive paste of polymolecularity, while viscosity stability excellence.
Description of drawings
Fig. 1 is the manufacturing flow chart according to conductive paste of the present invention.
Fig. 2 is the generalized section of the nozzle that possesses throttle orifice that uses in the pre-treatment dispersion step of the 1st operation.
Fig. 3 is the key diagram for the dispersal device of the pre-treatment dispersion step of the 1st operation.
Fig. 4 is the figure of the relation of expression viscosity and paste temperature.
Symbol description
1 tank
2 heaters
3 stirrer paddles
4 pumps
5 nozzles
The diameter of D nozzle (external diameter)
Distance between the L throttle orifice
6 throttle orifices
D throttle diameter (internal diameter of throttle orifice)
Embodiment
The conductive paste that the internal electrode of the multi-layer ceramic capacitor among the present invention forms usefulness is a kind ofly conductive metal powder and ceramic powders to be dispersed in adhesive is dissolved in the organic carrier that forms in the organic solvent and the paste that makes.
Such conductive paste is to form through 3 following procedures.
1. the 1st operation (pre-treatment dispersion step)
After heat mix and blend, make it carry out dispersion treatment by the nozzle that possesses throttle orifice the thick paste of the conductivity that contains at least conductive metal powder, dispersant, organic bond and organic solvent.
2. the 2nd operation (dispersion step)
To carry out the dispersion treatment that conductive paste that pre-treatment disperses uses high-pressure homogenizer that it is further disperseed by the 1st operation.
3. the 3rd operation
To use filter to filter by the conductive paste that the 2nd operation has been carried out dispersion treatment.
Below, explain these operations.
(the 1st operation)
The 1st operation be with the thick paste of the conductivity that contains at least conductive metal powder, dispersant, adhesive and organic solvent after heat mix and blend, make it by being installed in the nozzle that possesses throttle orifice on the drive-type pump, give thus mechanical shearing and carry out the operation that pre-treatment disperses.Need to prove, be for the viscosity of the thick paste of conductivity when reducing pre-treatment and disperse while heat the reason that stirs, and gives flowability.
The mix and blend that carries out in this operation can use the common mixed stirring devices such as propeller type agitating device.The high speed mixing stirring device such as dispersion machine (デ イ ス パ one) particularly preferably.
In the pre-treatment dispersion process of the 1st operation, by the thick paste of conductivity being sent into the nozzle of the throttle orifice with specified diameter, by throttle orifice the time, give this conductivity thick paste shearing force, carry out thus dispersion treatment.
Make it by the carrying method of throttle orifice as being used for that the thick paste of this conductivity is sent into nozzle, can be from the various pumps such as charge pump, single-screw (single screw) pump (モ one ノ Port Application プ), membrane pump, gear pump suitable choice for use.The pressure that is imposed on the thick paste of conductivity by these pumps is not particularly limited, but preferably uses 5kg/cm in the scope of not bringing impact to productivity ratio
2More than be advisable.
Fig. 2 represents for the nozzle 5 of pre-treatment dispersion and an example of throttle orifice 6.
To making the thick paste of conductivity be subject to the internal diameter (below be called throttle diameter, among Fig. 2 with symbol " d " expression) of the throttle orifice of shear action, the preferred nozzle that uses the throttle diameter with 0.2～0.5mm.
In the situation that spray nozzle clogging less than 0.2mm, might occur in this throttle diameter in the pre-treatment dispersion step, in the situation that greater than 0.5mm, in the presence of organic carrier, the wetting of the surface of conductive metal powder or ceramic powders becomes insufficient.In addition, as long as throttle diameter is the nozzle of internal diameter 0.2～0.5mm, just can make up.
Nozzle with throttle orifice both can be the nozzle that possesses a throttle orifice in the nozzle, also can be the nozzle that has as shown in Figure 2 a plurality of throttle orifices in nozzle.The number of its throttle orifice preferably is connected in series with more than 2.When setting like this, only the number of throttle orifice just can give conductivity thick paste mechanical shearing.Need to prove, the number of throttle orifice is not stipulated especially, but is selected to possess the nozzle number that gives the throttle orifice of the number of the mechanical shearing of necessity in the pre-treatment dispersion step.And then the distance L between throttle orifice can consider that also the paste characteristics such as viscosity of conductive paste suitably set.
As shown in Figure 2, be connected in series by the throttle orifice with a plurality of narrow gaps, the thick paste of conductivity is passed through, produce the shearing force of the stream internal face of the thick paste of conductivity and throttle orifice, make the surface of conductive metal powder or ceramic powders easily wetting.Need to prove, in the present embodiment, the size of the nozzle that possesses throttle orifice that the pre-treatment dispersion step is used is that diameter (external diameter) is 4.7mm (being shown in the D of Fig. 2), and length is 10mm (being shown in the L of Fig. 2).
The shape preferably drum shape of this nozzle, there is not the nonabradable linearity of bend or flexing section, and then as the material that forms throttle orifice, such as enumerating: diamonds such as sintered diamond and single-crystal diamonds; The ceramic materials such as aluminium oxide, zirconia, carborundum; The metals such as stainless steel, iron, titanium.
Pre-treatment for the 1st operation disperses, as present pre-treating method, when only stirring when mixing with high speed shear mixer or the agitating devices such as planetary mixer more than 2 axles, because the surface of conductive metal powder or ceramic powder is not wetting fully in organic carrier, the large agglutinator that has the organic carrier, conductive metal powder and the ceramic powders that do not mix fully, therefore the dispersion efficiency that utilizes high-pressure homogenizer in the 2nd operation descends.And the remaining organic carrier that does not mix fully in the thick paste of conductivity descends the glossiness of desciccator diaphragm.
One of the pre-treatment dispersion step of the conductive paste among the present invention is illustrated in Fig. 3.As shown in Figure 3, while use heater 2 heating use interior thick paste Jie of conductivity of tank that stirrer paddle 3 stirs 1 by the nozzle 5 of the throttle orifice of pump 4 by having a plurality of narrow gaps that are connected in series.
(the 2nd operation)
In the 2nd operation, will further be disperseed with high-pressure homogenizer by the conductive paste that the 1st operation pre-treatment disperses to form.
Preferred 50～the 250MPa of the pressure of high-pressure homogenizer of the present invention more preferably processes with 100～200MPa.When this insufficient pressure 50MPa, owing to the speed of the injection stream that sprays from throttle orifice is inadequate, therefore, act on a little less than the energy of handled thing, so cause dispersion bad.In addition, pressure is that the following reason of 250MPa is the wearing and tearing from the parts that suppress dispersion machine, makes its viewpoint that can tolerate long use consider and select.
The high-pressure homogenizer of bearing dispersion treatment in the 2nd operation is the equipment that utilizes fine throttle orifice in order to produce high velocity jet, its throttle diameter is considered to be preferably set to about 0.05～0.2mm from the efficiency of productivity ratio or device, in addition, its shape does not preferably have the nonabradable linearity of bend or flexing section.And then the material that forms throttle orifice can be enumerated the diamonds such as sintered diamond or single-crystal diamond; The ceramic materials such as aluminium oxide, zirconia, carborundum; The metals such as stainless steel, iron, titanium, the wherein material of preferred nonabradable high-hardness.
Usually, the faster then shearing force of the Negotiation speed of paste in throttle orifice also becomes larger, can make the particle diameter of particle finer.Yet, when particle diameter becomes too small, owing to becoming and easily cause aggegation, therefore for particle being maintained under the state of suitable particle diameter, need to regulate this throttle orifice Negotiation speed so that in the throttle orifice and throttle orifice by after act on paste stress be optimum.
The adjusting of this Negotiation speed is carried out according to conditions such as throttle diameter, processing pressure, by the throttle orifice Negotiation speed of paste being adjusted in the scope of 100～1000m/sec, can making particle be in suitable fine particle size state and prevents aggegation.
In addition, in order to prevent causing paste by behind the throttle orifice collision of spatial portion inwall and the uneven homogenize of shearing force being produced bubble, make paste while also can apply counter-pressure.In addition, the stability decreases owing to particle when the paste temperature uprises produces the problems such as again aggegation, so not preferred, therefore for anti-paste suppressing agent temperature rises, preferably be equipped with cooling device.
Dispersion number of pass times in the high-pressure homogenizer can suitably be selected according to desired particle diameter, particle size distribution etc.It should be noted that, disperse number of pass times preferably to be undertaken by the structure that makes the such device of paste circulation.
The putting into of the 2nd operation carried out dispersion treatment in the high-pressure homogenizer conductive paste expectation is for evenly and low viscosity, but below the preferred 10Pas of viscosity of the conductive paste when implementing the high pressure homogenizing, more preferably below the 5Pas.
For example, shown in the relation of the temperature of the conductive paste of Fig. 4 and viscosity, the paste temperature 25 ℃ viscosity be the conductive paste of 30Pas when being heated, viscosity descends when the temperature of conductive paste rises.
In the situation that this viscosity is higher than 10Pas, conductive paste does not have flowability, and therefore, in the time of in putting into high-pressure homogenizer, processing pressure can not get improving, and can't implement dispersion treatment.In addition, be higher than in the temperature of conductive paste in 70 ℃ the situation, the viscosity of conductive paste becomes below the 10Pas, but the Compositional balance of the secure context such as the volatility of the organic solvent that uses, inflammability and conductive paste easily changes, and is therefore not preferred.
As the high-pressure homogenizer that uses, microjet homogenizer (マ イ Network ロ Off Le イ ダ イ ザ one) (manufacturings of マ イ Network ロ Off Le イ デ イ Network ス society), Na ノ マ イ ザ one (the industrial strain formula of Jitian's machinery can shut out manufacturings), Nano3000 (beautiful manufacturing of Co., Ltd.), ア Le テ イ マ イ ザ one (manufacturing of the ス ギ ノ マ シ of Co., Ltd. Application) etc. are arranged.
(the 3rd operation)
The 3rd operation operation that to be the conductive paste that will carry out dispersion treatment through the high-pressure homogenizer that utilizes the 2nd operation filter with the filter of regulatory specifications.
Filter as filter, with 99% filtering filtering accuracy (カ Star ト ろ
Precision), be that the following filter of 5 μ m filters with mesh.Using mesh to surpass in the situation of filter of 5 μ m, can not remove not dispersion, the big particle etc. of inorganic matter, when the material of sneaking into greater than the thickness of dielectric layer, because the paste film coated surface produces projection, flatness descends.Therefore, can not obtain the conductive paste of flatness excellence.
Need to prove, so-called take 99% filtering filtering accuracy mesh as the filter below the 5 μ m filters, refer to replenish the particle that surpasses 5 μ m more than 99% with 99% filtering precision.For example, can enumerate based on the one way test of 7 kinds of JIS z 8901 regulations tests with powder (5mg/L dispersion liquid, 10L/min).In addition, as filter materials, metal, PTFE (polytetrafluoroethylene), polypropylene etc. are arranged, but be not limited to these materials.And then, as the structure of filter used herein, can the illustration membrane type, rivel formula, degree of depth formula (デ プ ス タ イ プ) etc., but be not limited to these structures.
(conductive paste construct)
For the conductive paste of the flatness and the desciccator diaphragm density that obtain to improve dry coating, nickel by powder preferably uses the micropowder of particle diameter 0.03～0.5 μ m.Nickel by powder produces big particle because of aggegation sometimes, when the particle diameter of nickel powder surpasses 0.5 μ m, film forming variation during with the coated film thin layer of paste, the static capacity that not only can not obtain to stipulate, and the probability of sneaking into of big particle increases, and the bad phenomenon that disintegration voltage (BDV) reduces easily occurs.In addition, in the time will forming such electrode film of corresponding thin layer, the flatness of desciccator diaphragm is inadequate, and the filling of nickel by powder particle becomes insufficient, can not guarantee required desciccator diaphragm density.
On the other hand, be set as reason below the 0.5 μ m as the particle diameter with nickel by powder, be because this be for the electrode film that in the thin layer of stacked capacitor, forms the continuity excellence necessary.And then when particle diameter was lower than 0.03 μ m, the specific area of particle became excessive, the surface activity of metallic particles becomes too high, not only dry, unsticking mixture characteristic are brought harmful effect, and might can not obtain suitable viscosity characteristics, or at the long preservation mesometamorphism of conductive paste.
In the present invention, the particle diameter of nickel by powder is based on namely that BET method contrast table area calculates and the particle diameter that draws unless otherwise specified.Its calculating formula is shown in mathematical expression 1.
[mathematical expression 1]
The particle diameter of nickel by powder=6/ (SA
1* ρ
1)
ρ
1=8.9 (real densities of nickel)
SA
1: the specific area of nickel powder (BET method)
The ratio of the conductive gold metal particles in the conductive paste of the present invention is preferably 30～70 % by weight.When the conductive gold metal particles was lower than 30 % by weight, the obvious attenuation of the thickness of electrode after the calcining, resistance value were risen, or the formation of electrode film is insufficient and lose conductivity, sometimes can not obtain the static capacity as target.When surpassing 70 % by weight, electrode film becomes and is difficult to thin layer.The conductive metal powder is 40～60 % by weight with respect to the paste set overall more preferably.
In the situation that ceramic powders is added in the conductive paste as sintering inhibitor, can be from being generally the BaTiO of perofskite type oxide
3Deng or wherein be added with in the perofskite type oxide of various additives and select.In addition, go back the employed ceramic powders same composition of the principal component as the dielectric layer raw cook or similar composition the preferred and that MLCC uses.
This ceramic powders can use the ceramic powders of various method for making manufacturings such as utilizing solid phase method, hydrothermal synthesis method, alkoxide process, sol-gal process.In addition, as required, for ceramic powders, the ceramic slurry that devices such as utilizing ball mill or high-pressure homogenizer can have been implemented dispersion, pulverization process is added in the conductive paste as sintering inhibitor.
The particle diameter of ceramic powders is preferably in the scope of 0.01 to 0.2 μ m.When the particle diameter of ceramic powders surpassed 0.2 μ m, desciccator diaphragm density descended.In desciccator diaphragm, in the formed gap of torulose nickel by powder particle packing, fill ceramic powders.When the particle diameter of ceramic powders surpasses 0.2 μ m, become and be difficult to enter between the contact point of torulose nickel by powder particle, therefore, be difficult to obtain required desciccator diaphragm density, and then the sintering of conductive paste is begun the effect that temperature delay to the sintering of ceramic layer begins temperature die down.
On the other hand, when the particle diameter of ceramic powders was lower than 0.01 μ m, the sintering carryover effects of conductive paste was difficult to manifest, and produced the faults of construction such as delamination or crackle.In addition, occur that above-mentioned desciccator diaphragm density descends or wait the problem (insulation resistance decline or short circuit ratio rising etc.) of the reliability variation of capacitor take the aggegation powder of ceramic powders as the thin layer change of the dielectric layer of cause is difficult.
In the present invention, the particle diameter of ceramic powders is based on namely that BET method contrast table area calculates and the particle diameter that draws unless otherwise specified.Calculating formula as an example of barium titanate example is as follows.
[mathematical expression 2]
The particle diameter of barium titanate powder=6/ (SA
2* ρ
2)
ρ
2=6.1 (real densities of barium titanate)
SA
2: the specific area of barium titanate powder (BET method)
In addition, the containing ratio of ceramic powders is 3～25 weight portions with respect to conductive metal powder 100 weight portions preferably.Be 5～15 weight portions with respect to conductive metal powder 100 weight portions more preferably.In the situation of containing ratio less than 3 weight portions of ceramic powders, for example can not control the sintering of nickel by powder, the inconsistent of the sintering shrinkage behavior of interior electrode layer and dielectric layer becomes remarkable.On the other hand, when the containing ratio of ceramic powders surpasses 25 weight portion, for example because of with dielectric layer in the sintering of ceramic particle, the thickness of dielectric layer expands from interior electrode layer, composition is offset, and therefore brings degradation harmful effect under the permittivity to electrical characteristic.In addition, when the content of ceramic powders is less than 3 weight portion since the sintering of internal electrode from low temperature just, it is large that the difference of the sintering temperature of interior electrode layer and dielectric layer becomes, and therefore produces the calcining crackle.
In conductive paste of the present invention, adhesive resin uses with the form of the organic carrier that is pre-mixed with organic solvent.Though adhesive resin uses the material that is dissolved in organic solvent, but because of need fully stirring etc. for it is dissolved equably, the result is the time of the mixing process overspending of the 1st operation, consider from the viewpoint that makes productivity ratio decline or undermixing, there is the danger that causes quality variation, on the meaning of its eliminating, preferably uses organic carrier.
Can enumerate the organic resins such as methylcellulose, ethyl cellulose, EHEC, nitrocellulose, acrylate, polyvinyl butyral resin in this adhesive resin, from these organic resins, select more than a kind.For its molecular weight, for being dissolved in the resin of organic solvent, preferably use the resin of 20000～200000 molecular weight.It should be noted that the preferred 1.0～5.0wt% of the amount of resin in the conductive paste, more preferably 2.0～4.0wt% especially.In the situation that not enough 1.0wt%, be difficult to obtain to be suitable for the viscosity of silk screen printing, when surpassing 5.0wt%, because the residual carbon amount increases during the unsticking mixture, cause the delamination of laminated chips, therefore not preferred.
In the organic solvent of conductive paste, can use terpineol (α, β, γ and their mixture), dihydro-terpineol, dihydrokainic acid terpinyl acetate, isobornyl acetate, isobonyl propionate (isobornyl propionate), butyric acid isobornyl thiocyanoacetate, isobutyric acid isobornyl thiocyanoacetate, ethylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetic acid esters of dissolved adhesive resin etc.
As the dispersant that comprises in the conductive paste, be not particularly limited, so long as cationic dispersant, anionic species dispersant, nonionic class dispersant, amphoteric surfactant, high score subclass dispersant etc. can make conductive metal powder or ceramic powders get final product with the dispersant that is dispersed in adhesive and the organic solvent of miniaturization in stable conditionly, can use known dispersant.Especially, preferred anionic class dispersant in these dispersants is such as enumerating: carboxylic acids dispersant, phosphoric acid class dispersant, phosphoric acid salt dispersant etc.These dispersants can use a kind or make up more than 2 kinds and to use.The anionic species dispersant helps to improve the dispersiveness of inorganic constituents owing to large to the absorption affinity of inorganic surfaces by this surface modification effect, therefore also be improved the flatness of filming, the effect of desciccator diaphragm density.
The mean molecule quantity of this dispersant is preferably 200～20000.More preferably 300～10000.When mean molecule quantity less than 200 the time, particle can not obtain sufficient electrostatic repulsion, the dispersiveness of particle or storage stability descend sometimes.Usually, dispersant adsorption forms the adsorption layer of dispersant at particle surface, by giving particle with electrostatic repulsion or three-dimensional repulsion, obtains the paste of excellent dispersion.But, owing to thinking along with the process of time, owing to the collision between the particle, surpass the repulsion of adsorption layer, aggegation between the particle, so mean molecule quantity is being advisable more than 200.In addition, when molecular weight greater than 20000 the time, the compatibility with organic carrier and organic solvent descends sometimes, or causes the aggegation between the particle, causes the decline of dispersiveness, storage stability.In addition, also produce the problem that paste viscosity uprises.
For the addition of dispersant, as the addition with respect to the conductive metal powder, be preferably 0.01～2.00 mass parts, 0.20～1.00 mass parts more preferably with respect to inorganic content 100 mass parts.If dispersant less than 0.01 mass parts has to be difficult to obtain dispersed fully tendency.On the other hand, when surpassing 2.00 mass parts, produce degradation problem under drying property variation and the desciccator diaphragm density.
Regulate or the viscosity characteristics of appropriateness etc. for the viscosity of giving conductive paste, also can add organic solvent or organic bond according to purpose in the conductive paste among the present invention.As this organic solvent or organic bond, basically preferably consist of the material of conductive paste.And then, can also add as required known additive in the conductive pastes such as defoamer, plasticizer, thickener.
Embodiment
Below, according to embodiment more specifically, explain the present invention.Need to prove, scope of the present invention is not subjected to any restriction of embodiment.
[characteristic of conductive paste]
(1) viscosity of conductive paste
The viscosity of conductive paste of the present invention uses the Brookfield viscometer of Block Le Star Network Off イ one Le De society manufacturing at 10rmp (sliding speed=4sec
-1) condition under measure.Need to prove, the viscosity shown in the embodiment represent paste make after viscosity during through 8 hours.
(2) conductive paste through the time viscosity rate of change
For conductive paste through the time viscosity rate of change, viscosity after the conductive paste manufacturing during through 8 hours is as initial viscosity, after leaving standstill 30 days under the normal temperature (25 ℃), the viscosity variable quantity of initial viscosity with the viscosity of again measuring removed with initial viscosity, with percentage (%) expression.Need to prove, conductive paste through the time viscosity rate of change preferably the smaller the better.
(3) surface roughness (Ra)
After glass substrate coating Ni paste, under 120 ℃, make it air drying 5 minutes with spreader (the thick 5 μ m in gap), make the approximately desciccator diaphragm of 3 μ m of thickness.
Projection to the optical method measuring surface of this desciccator diaphragm by utilizing the phase shift interference mode.Particularly, from the light source that is defined in particular wavelength region with irradiation on sample and reference mirror, the interference of light striped that utilization is radiated on sample and the reference mirror is observed surface state, further specifying, then is to make the direction that sample shines along light every 1/4 wavelength move from interference of light striped observation surface state.The surface roughness of this desciccator diaphragm uses light interference type surface-profile measuring instrument (WYCO makes NT-1100) to measure.
(4) glossiness and desciccator diaphragm density (DFD)
The assay method of desciccator diaphragm density is measured by following method.
The area of conductive paste with 5 * 10cm is printed on the PET film, make become 30 μ m thickness after, make it air drying 40 minutes under 120 ℃, (the hole field makes manufacturing グ ロ ス チ エ Star カ one: the glossiness (60 ℃) of IG-320) measuring the paste desciccator diaphragm of drying to use Grossmeters.Further, the paste desciccator diaphragm is cut to 1 * 1cm, measures its thickness and quality, calculate desciccator diaphragm density.
The mensuration of desciccator diaphragm density is conductive paste to be printed on the PET film carry out, and certainly, even conductive paste of the present invention is printed on the dielectric layer raw cook, also can bring into play same characteristic.
At this, so-called desciccator diaphragm density is to make the dried density of conductive paste.
(5) organic carrier
Organic carrier A for using in an embodiment cooperates 13 quality % ethyl celluloses as the adhesive resin composition, cooperates 87 quality % terpineols as organic solvent, is heated to 60 ℃ and makes.
Similarly, for organic carrier B, cooperate 18 quality % EHECs as the adhesive resin composition, cooperate 82 quality % isobonyl propionates as organic solvent, be heated to 60 ℃ and make.
Embodiment 1
The nickel by powder (Ni), the 21.69 quality % organic carrier A that in the conductive metal powder, cooperate 47 quality % particle diameters, 0.4 μ m, and then cooperate the dispersant of 0.2 quality %, the terpineol of 31.11 quality %, after heating mix and blend, in being installed on the nozzle that throttle orifice drive-type delivery side of pump section, that to make 6 throttle diameters be 0.5mm is connected in series, make 60 ℃ the thick paste of conductivity by giving mechanical shearing, the conductive paste that pre-treatment disperses was implemented in making, measured the glossiness of this paste desciccator diaphragm.To the results are shown in table 1～table 3.
Embodiment 2
The nickel by powder (Ni) that in the conductive metal powder, cooperates 47 quality % particle diameters, 0.4 μ m, the barium titanate (BT), the 19.88 quality % organic carrier A that in ceramic powders, cooperate 11.75 quality % particle diameters, 0.1 μ m, and then cooperate the dispersant of 0.3 quality %, the terpineol of 21.07 quality %, after heating mix and blend, in being installed on the nozzle that throttle orifice drive-type delivery side of pump section, that be 0.5mm with 6 throttle diameters is connected in series, make 60 ℃ the thick paste of conductivity by giving mechanical shearing, implement pre-treatment and disperse.
Then, with 60 ℃ through conductive paste utilizations that pre-treatment disperses according to throttle diameter 0.19mm, processing pressure 100MPa, to disperse number of pass times be after high-pressure homogenizer that 1 time condition is set is implemented dispersion treatment and made conductive paste, take 99% filtering filtering accuracy, utilize mesh to carry out filtration treatment as the filter below the 3 μ m, make required conductive paste, measure paste characteristic (viscosity, surface roughness, DFD), reach the viscosity rate of change.To the results are shown in table 1～table 3.
Embodiment 3
Except the dispersion number of pass times that will utilize high-pressure homogenizer is set as 3 times, by making required conductive paste with embodiment 2 the same terms, measure paste characteristic and viscosity rate of change.To the results are shown in table 1～table 3.
Embodiment 4
Except the dispersion number of pass times that will utilize high-pressure homogenizer is set as 5 times, by making required conductive paste with embodiment 2 the same terms, measure paste characteristic and viscosity rate of change.To the results are shown in table 1～table 3.
The nickel by powder (Ni) that in the conductive metal powder, cooperates 48.12 quality % particle diameters, 0.2 μ m, the barium titanate (BT) that in ceramic powders, cooperates 4.81 quality % particle diameters, 0.04 μ m, 16.06 quality % organic carrier B, and then with the dispersant of 0.43 quality %, 21.93 the isobonyl propionate of quality %, 8.65 the ethylene glycol monomethyl ether acetate of quality % cooperates, after heating mix and blend, be installed on drive-type delivery side of pump section, in the nozzle that the throttle orifice that to make 11 throttle diameters be 0.2mm is connected in series, make 60 ℃ the thick paste of conductivity by giving mechanical shearing, implement pre-treatment and disperse.
Then, with 60 ℃ through conductive paste utilizations that pre-treatment disperses according to throttle diameter 0.13mm, processing pressure 200MPa, to disperse number of pass times be after high-pressure homogenizer that 5 times condition is set is implemented dispersion treatment and made conductive paste, carry out take 99% filtering filtering accuracy, utilize mesh as the filtration treatment of the filter below the 1 μ m, make required conductive paste, measure its paste characteristic and viscosity rate of change.To the results are shown in table 1～table 3.
The nickel by powder (Ni) that in the conductive metal powder, cooperates 48.12 quality % particle diameters, 0.08 μ m, the barium titanate (BT) that in ceramic powders, cooperates 4.81 quality % particle diameters, 0.03 μ m, 16.06 quality % organic carrier B, and then cooperate the dispersant of 0.43 quality %, 21.93 the isobonyl propionate of quality %, 8.65 the ethylene glycol monomethyl ether acetate of quality %, after heating mix and blend, be installed on drive-type delivery side of pump section, in the nozzle that the throttle orifice that to make 11 throttle diameters be 0.2mm is connected in series, make 60 ℃ the thick paste of conductivity by giving mechanical shearing, implement pre-treatment and disperse.
Then, with 60 ℃ through conductive paste utilizations that pre-treatment disperses according to throttle diameter 0.09mm, processing pressure 250MPa, to disperse number of pass times be after high-pressure homogenizer that 10 times condition is set is implemented dispersion treatment and made conductive paste, carry out take 99% filtering filtering accuracy, utilize mesh as the filtration treatment of the filter below the 1 μ m, make required conductive paste, measure its paste characteristic and viscosity rate of change.To the results are shown in table 1～table 3.
(comparative example 1)
The nickel by powder (Ni), the 21.69 quality % organic carrier A that in the conductive metal powder, cooperate 47 quality % particle diameters, 0.4 μ m, and then cooperate the dispersant of 0.2 quality %, the terpineol of 31.11 quality %, after heating mix and blend, be installed on drive-type delivery side of pump section, to make throttle diameter be in each 6 nozzle that are connected in series of throttle orifice of 1.0mm, make 60 ℃ the thick paste of conductivity by giving mechanical shearing, the conductive paste that pre-treatment disperses was implemented in making, measured the glossiness of this paste desciccator diaphragm.To the results are shown in table 1～table 3.
(comparative example 2)
The nickel by powder (Ni), the 21.69 quality % organic carrier A that in the conductive metal powder, cooperate 47 quality % particle diameters, 0.4 μ m, and then cooperate the dispersant of 0.2 quality %, the terpineol of 31.11 quality %, use planetary mixer (プ ラ イ ミ Network ス Co., Ltd. makes T.K. Ha イ PVC ス デ イ ス パ one ミ Star Network ス 3D-125 type) mix and blend to make conductive paste, measure the glossiness of this paste desciccator diaphragm.To the results are shown in table 1～table 3.Need to prove, the mixing time of planetary mixer is set as 30 minutes.
(comparative example 3)
The nickel by powder (Ni), the 21.69 quality % organic carrier A that in the conductive metal powder, cooperate 47 quality % particle diameters, 0.4 μ m, and then cooperate the dispersant of 0.2 quality %, the terpineol of 31.11 quality %, use planetary mixer (プ ラ イ ミ Network ス Co., Ltd. makes T.K. Ha イ PVC ス デ イ ス パ one ミ Star Network ス 3D-125 type) mix and blend to make conductive paste, measure the glossiness of this paste desciccator diaphragm.To the results are shown in table 1～table 3.Need to prove, the mixing time of planetary mixer is set as 120 minutes.
(comparative example 4)
The nickel by powder (Ni) that in the conductive metal powder, cooperates 47 quality % particle diameters, 0.4 μ m, the barium titanate (BT) that in ceramic powders, cooperates 11.75 quality % particle diameters, 0.1 μ m, 19.88 quality % organic carrier A, and then cooperate the dispersant of 0.3 quality %, 21.07 the terpineol of quality %, after using planetary mixer (プ ラ イ ミ Network ス Co., Ltd. makes T.K. Ha イ PVC ス デ イ ス パ one ミ Star Network ス 3D-125 type) mix and blend, utilize 3 roller machines to implement dispersion treatment and make conductive paste, measure paste characteristic (viscosity, surface roughness, DFD), and viscosity rate of change.To the results are shown in table 1～table 3.
(comparative example 5)
The nickel by powder (Ni) that in the conductive metal powder, cooperates 47 quality % particle diameters, 0.4 μ m, the barium titanate (BT), the 19.88 quality % organic carrier A that in ceramic powders, cooperate 11.75 quality % particle diameters, 0.1 μ m, and then cooperate the dispersant of 0.3 quality %, the terpineol of 21.07 quality %, after heating mix and blend, in being installed on the nozzle that throttle orifice drive-type delivery side of pump section, that be 0.5mm with 6 throttle diameters is connected in series, make 60 ℃ the thick paste of conductivity by giving mechanical shearing, implement pre-treatment and disperse.Then, utilize 3 roller machines to implement dispersion treatment and make conductive paste, measure paste characteristic (viscosity, surface roughness, DFD), reach the viscosity rate of change.To the results are shown in table 1～table 3.
(comparative example 6)
The nickel by powder (Ni) that in the conductive metal powder, cooperates 48.12 quality % particle diameters, 0.2 μ m, the barium titanate (BT) that in ceramic powders, cooperates 4.81 quality % particle diameters, 0.04 μ m, 16.06 quality % organic carrier B, and then cooperate the dispersant of 0.43 quality %, 21.93 the isobonyl propionate of quality %, 8.65 the ethylene glycol monomethyl ether acetate of quality %, after using planetary mixer (プ ラ イ ミ Network ス Co., Ltd. makes T.K. Ha イ PVC ス デ イ ス パ one ミ Star Network ス 3D-125 type) mix and blend, utilize 3 roller machines to implement dispersion treatment and make conductive paste, measure its paste characteristic and viscosity rate of change.To the results are shown in table 1～table 3.
(comparative example 7)
The nickel by powder (Ni) that in the conductive metal powder, cooperates 48.12 quality % particle diameters, 0.08 μ m, the barium titanate (BT) that in ceramic powders, cooperates 4.81 quality % particle diameters, 0.03 μ m, 16.06 quality % organic carrier B, and then cooperate the dispersant of 0.43 quality %, 21.93 the isobonyl propionate of quality %, 8.65 the ethylene glycol monomethyl ether acetate of quality %, after using planetary mixer (プ ラ イ ミ Network ス Co., Ltd. makes T.K. Ha イ PVC ス デ イ ス パ one ミ Star Network ス 3D-125 type) mix and blend, with through the heating the conductive paste utilization according to throttle diameter 0.09mm, processing pressure 250MPa, the dispersion number of pass times is that the high-pressure homogenizer enforcement dispersion treatment that 10 times treatment conditions are set is made conductive paste, measures its paste characteristic and viscosity rate of change.To the results are shown in table 1～table 3.
Table 1
Table 2
Table 3
(effect of the pre-treatment dispersion step of the 1st operation)
About the effect of pre-treatment dispersion step, describe with the glossiness of the dry coating of the conductive paste of the pre-treatment dispersity of the 1st operation of making in embodiment 1 and comparative example 1～3 that is shown in table 4.
Table 4
As shown in Table 4, be that the nozzle of the thick throttle orifice of 1.0mm carries out in the situation of the comparative example 1 that pre-treatment disperses with possessing throttle diameter, the glossiness of filming is 3, is the mixing state identical with the comparative example 2 that carries out mix and blend with planetary mixer, 3 o'clock.In addition, will be set as with the time of planetary mixer mix and blend as can be known in the situation of 30 minutes and 120 minutes, the glossiness of filming does not have large variation.On the other hand, be that the nozzle of the throttle orifice of 0.5mm carries out in the situation of the embodiment 1 that pre-treatment disperses with possessing throttle diameter as can be known, it is 32 that the glossiness of filming raises, and compares and utilizes at present the mixing of mixer to process, melting effect is high.
Like this, be that the nozzle of the 0.5mm mechanical shear stress when carrying out pre-treatment and disperseing is large when comparing the nozzle that uses throttle diameter 1.0mm or use mixer in the past and carrying out that pre-treatment disperses with throttle diameter, by the difference of glossiness as can be known the desciccator diaphragm wettability of the surface obviously improve.
(the 2nd operation is on the impact of paste characteristic)
The embodiment 2～4 that is shown in the dispersion treatment that high-pressure homogenizer is used for the 2nd operation of table 5 is carried out in the situation of dispersion treatment of the 2nd operation impact on the paste characteristic with in the past the high-pressure homogenizer that utilizes comparative example 4 that 3 roller machine methods implement, 5 paste characteristic to compare to illustrate to use.
Table 5
As shown in table 5, when the viscosity of using high-pressure homogenizer and 3 roller machines to carry out the conductive paste of dispersion treatment in the 2nd operation is compared, if utilizing as can be known the number of pass times (number of times of dispersion treatment) of high-pressure homogenizer is 1 time, then be 27Pas (referring to embodiment 2), but when number of processes being increased to 3 times (referring to embodiment 3) or 5 times (referring to embodiment 4), viscosity drops to 24Pas.This is because the strong shearing force of high-pressure homogenizer has improved the dispersiveness of nickel powder or ceramic powder.In addition, then be 0.26 μ m and 5.8g/cm if surface roughness and DFD process 1 time
3, but when number of processes being increased to 3 times or 5 times, then become 0.24 μ m and 6.0g/cm
3, thus also as can be known the dispersiveness of nickel powder or ceramic powder improved.
But, be higher than significantly the viscosity of utilizing the conductive paste that high-pressure homogenizer makes with the viscosity of the conductive paste of 3 roller machine manufacturings, surface wetting poor, reason is because a little less than the shearing of 3 roller machines, therefore nickel powder or ceramic powder can not disperse fully, become the poor result of surface roughness or DFD.
In addition, even use throttle diameter as the nozzle of 0.5mm after the pre-treatment that utilizes throttle orifice to shear under the condition identical with embodiment 2～4 disperses, utilize 3 roller machines to carry out in the situation of dispersion treatment (with reference to comparative example 5), also present nickel powder and disperse bad, surface roughness or the poor result of DFD.
The embodiment 2～4 that is shown in the dispersion treatment that high-pressure homogenizer is used for the 2nd operation of table 6 is compared with the comparative example 4 that utilizes the enforcement of 3 roller machine methods in the past, 5 viscosity rate of change.
Table 6
Because the conductive paste of the use high-pressure homogenizer of embodiment has improved " wetting " of particle surface, and obtained polymolecularity, dispersant adsorption is at particle surface thus, prevent " the again aggegation " of particle, even preserve the dispersion stabilization that 30 day time also can keep conductive paste, so its viscosity rate of change is little.But, in the dispersion treatment of the 2nd operation, use the comparative example 4,5 conductive paste of 3 roller machines because " wetting " of particle surface is poor, and dispersiveness is also low, therefore dispersant is not adsorbed on particle surface effectively, therefore, can not keep dispersion stabilization, the viscosity rate of change is large.
(impact of the dispersion treatment in the 1st operation and the 2nd operation)
The combination of the dispersion treatment of the 1st operation and the 2nd operation is shown in table 7, the impact of viscosity rate of change is shown in table 8 impact of paste characteristic.
Table 7
Table 8
As shown in Table 7, implement the conductive paste (with reference to comparative example 6) that in the past the pre-treatment that utilizes mixer disperses, makes with the dispersion treatment of utilizing 3 roller machines owing to comparing and utilize the wetting poor of conductive paste surface that high-pressure homogenizer makes shown in the embodiment 5,6, a little less than the shearing of other 3 roller machines, therefore become nickel powder or ceramic powder can not disperse fully, surface roughness or DFD are poor, and then also large result of viscosity rate of change.
On the other hand, as shown in Table 8, the pre-treatment that utilizes mixer of implementing in the past disperses, compares with the conductive paste of making among the dispersion treatment of utilizing the high-pressure homogenizer conductive paste (with reference to comparative example 7) of making and the embodiment 6 that carries out under the same conditions the high pressure homogenizing, because the wetability of particle surface is poor, and dispersiveness is also poor, dispersant can not be adsorbed onto particle surface fully, can not prevent " the again aggegation " of particle, therefore the dispersion stabilization of conductive paste is poor, so it is large that the viscosity rate of change becomes.
Claims (10)
1. the manufacture method of a conductive paste is characterized in that, has following the 1st operation to the 3 operations:
[the 1st operation]
After heat mix and blend, make it by having the nozzle of throttle orifice the thick paste of the conductivity that contains at least conductive metal powder, dispersant, organic bond and organic solvent, carry out thus the pre-treatment dispersion step of dispersion treatment;
[the 2nd operation]
The high-pressure homogenizer that will have by the conductive paste utilization through heating that the 1st operation pre-treatment disperses throttle orifice carries out the dispersion step of dispersion treatment;
[the 3rd operation]
The filter progress that will utilize filter to filter by the conductive paste of the 2nd operation dispersion treatment.
2. the manufacture method of conductive paste claimed in claim 1 is characterized in that, the nozzle that possesses throttle orifice of described the 1st operation in series arrange 2 with on the thick paste of conductivity is disperseed.
3. the manufacture method of conductive paste claimed in claim 1 is characterized in that, the throttle diameter of the throttle orifice of described the 1st operation is 0.2～0.5mm.
4. the manufacture method of conductive paste claimed in claim 1 is characterized in that, the viscosity of the thick paste of described conductivity is below the 10Pas.
5. the manufacture method of conductive paste claimed in claim 1 is characterized in that, described high-pressure homogenizer carries out dispersion treatment with the pressure of 50～250MPa.
6. the manufacture method of conductive paste claimed in claim 1 is characterized in that, the throttle diameter of the throttle orifice that possesses in the described high-pressure homogenizer that the conductive paste of described the 2nd operation flows is 0.05～0.2mm.
7. the manufacture method of conductive paste claimed in claim 1 is characterized in that, described high-pressure homogenizer possesses cooler in export department's side of its throttle orifice.
8. the manufacture method of conductive paste claimed in claim 1 is characterized in that, the viscosity of the conductive paste through heating in described the 2nd operation is below the 10Pas.
9. the formed conductive paste of the manufacture method of conductive paste according to claim 1 is characterized in that, the content of conductive metal powder is 30～70 % by weight with respect to the conductive paste total amount.
10. conductive paste claimed in claim 9 is characterized in that, described conductive paste comprises ceramic powders as sintering inhibitor.
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| JP5429491B2 (en) * | 2010-06-17 | 2014-02-26 | 住友金属鉱山株式会社 | Conductive paste using inorganic material slurry and method for producing the paste |
| JP5772621B2 (en) * | 2012-01-19 | 2015-09-02 | 住友金属鉱山株式会社 | Conductive paste for internal electrodes |
| EP2947711A4 (en) * | 2013-01-17 | 2016-08-31 | Zeon Corp | Method for manufacturing conductive adhesive composition for electrochemical element electrode |
| CN105408246B (en) * | 2013-07-31 | 2019-01-01 | 日本瑞翁株式会社 | Carbon nano tube dispersion liquid, the composite material of the manufacturing method of composite material composition and composite material and its preparation, formed body |
| JP6136785B2 (en) * | 2013-09-05 | 2017-05-31 | トヨタ自動車株式会社 | Conductive paste evaluation method and positive electrode plate manufacturing method |
| JP6638393B2 (en) * | 2014-01-22 | 2020-01-29 | 東洋紡株式会社 | Conductive paste for laser etching, conductive thin film, conductive laminate |
| KR102312236B1 (en) * | 2014-01-22 | 2021-10-14 | 도요보 가부시키가이샤 | Conductive paste for laser etching, conductive thin film and conductive laminate |
| JP6292014B2 (en) * | 2014-05-12 | 2018-03-14 | 株式会社村田製作所 | Conductive paste and ceramic electronic components |
| KR102410080B1 (en) * | 2014-07-31 | 2022-06-16 | 스미토모 긴조쿠 고잔 가부시키가이샤 | Conductive paste |
| CN104399378A (en) * | 2014-11-10 | 2015-03-11 | 华玉叶 | Method for dispersing conductive powder and monomers |
| JP6809280B2 (en) * | 2017-02-21 | 2021-01-06 | 株式会社村田製作所 | Method of manufacturing conductive paste |
| KR102613114B1 (en) * | 2017-11-30 | 2023-12-12 | 스미토모 긴조쿠 고잔 가부시키가이샤 | Conductive pastes, electronic components, and multilayer ceramic capacitors |
| JP6637097B2 (en) * | 2018-03-30 | 2020-01-29 | 株式会社ノリタケカンパニーリミテド | Conductive paste |
| TWI834389B (en) * | 2022-11-18 | 2024-03-01 | 國巨股份有限公司 | Metal electrode of ceramic capacitor and method of forming the same |
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| JP2011228106A (en) | 2011-11-10 |
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