KR102042566B1 - Conductive paste for internal electrode of multi-layer ceramic capacitor and production method thereof, and multi-layer ceramic capacitor - Google Patents
Conductive paste for internal electrode of multi-layer ceramic capacitor and production method thereof, and multi-layer ceramic capacitor Download PDFInfo
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- KR102042566B1 KR102042566B1 KR1020150101687A KR20150101687A KR102042566B1 KR 102042566 B1 KR102042566 B1 KR 102042566B1 KR 1020150101687 A KR1020150101687 A KR 1020150101687A KR 20150101687 A KR20150101687 A KR 20150101687A KR 102042566 B1 KR102042566 B1 KR 102042566B1
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- 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
- H01G4/005—Electrodes
- H01G4/008—Selection of materials
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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
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- 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
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
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- 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
- H01G4/30—Stacked capacitors
Abstract
In the debonder step and subsequent firing step, the occurrence of structural defects such as interlayer peeling can be prevented, and even when stored for a long time, the viscosity change is small, and a conductive paste suitable for forming the internal electrode of the multilayer ceramic capacitor is low in cost. The purpose is to provide. To the conductive paste containing the conductive powder, the vehicle, and the viscosity modifier containing a petroleum hydrocarbon, at least one compound selected from a modified polyurethane, a modified polyamide, and ammonium phosphate as a thermal decomposition inhibitor is added to 100 parts by mass of the conductive powder. 0.1 mass part-1 mass part with respect to the addition.
Description
The present invention relates to a conductive paste used to form internal electrodes of a multilayer ceramic capacitor and a method of manufacturing the same. Moreover, this invention relates to the multilayer ceramic capacitor which used this electrically conductive paste.
A multi-layer ceramic capacitor (MLCC) has a structure in which a ceramic dielectric layer and an internal electrode layer are alternately overlapped and integrated. As an electroconductive powder for forming the internal electrode of this multilayer ceramic capacitor, noble metal powder, such as palladium, is used conventionally. However, at present, from the viewpoint of cost reduction, it is mainstream to use nickel powder or alloy powder containing nickel as a main component instead of powder of precious metal.
Such a multilayer ceramic capacitor generally prints a conductive paste obtained by dispersing conductive powder in a vehicle on a ceramic green sheet, and heat-presses and integrates the laminate in a state where it is laminated in multiple layers, followed by a temperature of 500 ° C. or lower in an oxidizing atmosphere or an inert atmosphere. It is obtained by baking in (binder process) by removing a binder (debonder process), and baking in a reducing atmosphere so that an internal electrode may not be oxidized subsequently (firing process).
By the way, with the miniaturization of electronic devices, miniaturization of various electronic components is progressing rapidly, and miniaturization and high capacity are progressing also in a multilayer ceramic capacitor. Specifically, multilayered multilayer ceramic capacitors and thinned internal electrode layers have been advanced. However, when nickel powder is used as the conductive powder, there arises a problem that structural defects such as interlayer peeling or cracking, in which the internal electrode layer and the ceramic dielectric layer are peeled off, are accompanied by multilayering and thinning.
It is considered that the cause of such a problem is caused by the catalytic action of nickel in the debonder process. That is, on the surface of the nickel powder and its vicinity, the thermal decomposition temperature of the resin component (binder) contained in the vehicle is lowered by the catalytic action of nickel, and the decomposition product gas is rapidly generated in the debonder process. For example, when ethyl cellulose is used as the binder, pyrolysis originally performed at around 355 ° C. is lowered to about 290 ° C., whereby decomposition decomposition gas is rapidly generated. On the other hand, since the catalytic action does not reach the resin component of the ceramic dielectric layer, thermal decomposition does not proceed at this point. As a result, the decomposition product gas is trapped in the vicinity of the surface of the nickel powder, voids are formed between the internal electrode layer and the ceramic dielectric layer, and it is considered that structural defects such as interlayer peeling and cracking are caused through the subsequent firing process. In particular, in order to reduce the thickness of the internal electrode layer, it is necessary to use a small particle size as the nickel powder, but the catalytic action of nickel is activated by this, and structural defects are more likely to occur.
In view of such a problem, conventionally, it has been attempted to add a component that suppresses the catalytic action of nickel in the debonder process or a component that delays the sintering of nickel to the conductive paste.
For example, Japanese Patent Laid-Open No. 2011-18898 discloses a sulfur-containing titanium in which barium titanate powder is mixed with sulfur as an additive in addition to nickel powder, a binder, and a solvent in a nickel paste used for an internal electrode of a multilayer ceramic capacitor. Techniques for adding barium acid have been described. According to this technique, since the rapid generation of decomposition decomposition gas is suppressed by the effect of inhibiting the catalytic action of nickel by sulfur and the sintering inhibition effect by barium titanate, it is possible to sufficiently suppress the occurrence of structural defects during firing. It is thought to be possible. However, this technique requires a step of containing sulfur in the barium titanate before kneading the respective components, and thus an increase in cost due to the increase in the number of steps is inevitable. In addition, inorganic components other than nickel powder may be present in the nickel paste, which may adversely affect the reliability of electronic components.
On the other hand, Japanese Patent Application Laid-Open No. 2008-223068 discloses a nickel powder having an average particle diameter of 0.05 µm to 1.0 µm as a conductive powder, which contains a nickel oxide particle having a surface oxide layer and containing sulfur. The nickel powder has a sulfur content of 100 ppm to 2000 ppm with respect to the total weight of the powder, and in the surface analysis by ESCA (X-ray photoelectron spectroscopy) of the nickel particles, the intensity of the peak returned to the sulfur atom bonded to the nickel atom has a particle surface. It is changing from the surface to the center direction, The intensity | strength becomes the maximum at the position deeper than 3 nm from a particle surface, It is characterized by the above-mentioned. Further, Japanese Patent Application Laid-Open No. 2008-223068 discloses that such a nickel powder is obtained by contacting a nickel powder containing sulfur dispersed in a non-oxidizing gas atmosphere with an oxidizing gas in a temperature range of 300 ° C to 800 ° C. have.
In addition, Japanese Patent Application Laid-Open No. 2013-87355 discloses, as an electroconductive powder, 0.05% by mass, which is obtained by hydrothermal treatment at a temperature in the range of 300 ° C or lower in excess of 100 ° C in the presence of sulfur compounds such as sodium thiosulfate or thiourea. It is described to use sulfur-containing nickel fine particles containing sulfur in the range of 1.0% by mass.
In these techniques, since inorganic components other than nickel powder do not exist in an electrically conductive paste, it is thought that it does not adversely affect the reliability of an electronic component. However, any technique requires the inclusion of sulfur in the nickel powder, and the cost increase due to the increase in the number of processes cannot be avoided.
On the other hand, Japanese Patent Laid-Open No. 2006-24539 discloses a technique of suppressing the catalytic action of nickel by adding a sulfur-containing organic compound in a conductive paste. Specifically, a technique is disclosed in which nickel powder is dispersed in a vehicle in which a binder is dissolved in a solvent, and triazine thiols, sulfate-containing compounds and the like are contained. According to this technique, it is thought that the above problem can be solved at low cost since the catalytic action of nickel can be suppressed by sulfur without increasing the number of steps.
However, the triazine thiols and sulfate-containing compounds exemplified in Japanese Patent Application Laid-Open No. 2006-24539 have a very low solubility in petroleum solvents and tend to swell when pasted. For this reason, the viscosity of an electrically conductive paste changes with time and may gel. In particular, when the conductive paste is stored for a long time, the viscosity is remarkably increased, and it becomes very difficult to form a desired internal electrode layer.
As a means of improving the stability of the viscosity of the conductive paste, Japanese Patent Laid-Open No. 2001-6434 discloses a technique of adding an amine-based surfactant and an anionic polymer dispersant to a conductive paste containing a conductive powder and an organic vehicle. . However, amine-based surfactants and anionic polymer dispersants have no effect of inhibiting the catalytic action of nickel or delaying sintering, and cannot generate structural defects in the debonder step and the firing step.
The present invention can prevent the occurrence of structural defects such as interlayer peeling in the debonder step and subsequent firing step, and has a small change in viscosity even when stored for a long time, and is suitable for forming the internal electrode of the multilayer ceramic capacitor. It is an object to provide a conductive paste. Moreover, an object of this invention is to provide the manufacturing method which can manufacture such an electrically conductive paste at low cost. Moreover, an object of this invention is to provide the multilayer ceramic capacitor provided with the internal electrode layer formed using this electrically conductive paste.
This invention relates to the electrically conductive paste containing electroconductive powder, the vehicle, the viscosity modifier containing a petroleum hydrocarbon, and a thermal decomposition suppression additive.
In particular, the conductive paste of the present invention contains at least one compound selected from a modified polyurethane, a modified polyamide, and ammonium phosphate as the thermal decomposition inhibitor, and the content of the thermal decomposition inhibitor additive is 100 parts by mass of the conductive powder. It is characterized by the above-mentioned.
It is preferable that the said pyrolysis inhibiting additive is a modified polyamide.
It is preferable that a boiling point of the said viscosity modifier is 150 degreeC-260 degreeC.
It is preferable that the average particle diameter of the said electroconductive powder is 1 micrometer or less.
It is preferable that the said electroconductive powder is at least 1 sort (s) chosen from Ni powder, Pd powder, the alloy powder containing Ni, and the alloy powder containing Pd, and among these, it is more preferable that it is Ni powder.
The electrically conductive paste of this invention can be manufactured by adding the said electroconductive powder, the said viscosity modifier, and the said thermal decomposition suppression additive to the said vehicle, and knead | mixing these mixtures.
In addition, the conductive paste of the present invention can be suitably used when forming the internal electrode layer of the multilayer ceramic capacitor.
According to the present invention, by adding a specific pyrolysis inhibiting additive, it is possible to suppress the thermal decomposition of the binder generated on the surface of the nickel powder in the conductive paste and the generation of a sudden gas accompanying it in the debonder process in the manufacture of the multilayer ceramic capacitor. It is possible to effectively prevent the occurrence of structural defects such as delamination in the subsequent firing step. In addition, according to the present invention, it is possible to improve the stability of the viscosity of the conductive paste without separately adding an additive other than the pyrolysis inhibiting additive, so that the internal electrode layer of the multilayer ceramic capacitor can be stably formed even after a long period of time after the production of the conductive face. can do. Further, according to the present invention, since the conductive paste having such characteristics can be realized by only adding a very small amount of a specific pyrolysis inhibiting additive without controlling the shape or particle size of the conductive powder, it is easy to manufacture and also suppresses pyrolysis. There is also little increase in cost by the addition of additives. For this reason, the industrial significance of this invention is very large.
BRIEF DESCRIPTION OF THE DRAWINGS The figure for demonstrating the effect obtained by adding a thermal decomposition suppression additive to a vehicle.
MEANS TO SOLVE THE PROBLEM As a result of earnestly researching about the electrically conductive paste used for formation of a multilayer ceramic capacitor, the present inventors added specific compounds, such as a modified polyurethane, a modified polyamide, and an ammonium phosphate, as a thermal decomposition inhibitor additive in an electrically conductive paste, We found that we can solve both at the same time. This invention is completed based on this knowledge.
1. Composition
Hereinafter, the electrically conductive paste of this invention is demonstrated for every structural component.
(1) conductive powder
As the conductive powder constituting the conductive paste of the present invention, at least one selected from nickel (Ni) powder, palladium (Pd) powder, alloy powder containing Ni and alloy powder containing Pd may be used as in the prior art. Can be. Among these, it is preferable to use Ni powder of low cost.
Moreover, as alloy powder containing Ni, the alloy powder containing Ni and the metal containing at least 1 sort (s) chosen from chromium (Cr), cobalt (Co), copper (Cu) etc. can be used suitably, for example. As the alloy powder containing Pd, an alloy powder containing Pd and at least one metal selected from silver (Ag), platinum (Pt) and the like can be suitably used. Moreover, in these alloy powders, it is preferable that content of Ni or Pd is 50 mass% or more, and it is more preferable that it is 80 mass% or more.
As mentioned above, the electrically conductive paste of this invention is not restrict | limited by the average particle diameter of an electrically conductive powder. However, in order to reduce the thickness of the internal electrode layer, it is important to use a conductive powder having a smaller particle size than the thickness thereof. Specifically, it is preferable to use 1 µm or less as the conductive powder, and more preferably 0.4 µm or less. In the electroconductive powder of such a small particle size, since the above-mentioned catalytic action is activated, the effect obtained by this invention becomes more remarkable. On the other hand, in the electroconductive powder with an average particle diameter exceeding 1 micrometer, the ratio of a coarse particle becomes large and it is disadvantageous for thinning a laminated ceramic capacitor, and coarse particle in an internal electrode layer electrically shorts through a ceramic dielectric layer, There may be a lack of capacity.
(2) vehicle
The vehicle which comprises the electrically conductive paste of this invention is not restrict | limited, The thing which mixed a solvent and a binder uniformly can be used similarly to a prior art. For example, terpineol, butyl carbitol acetate, butyl carbitol, dihydroterpineol, dihydroterpineol acetate, etc. can be used as a solvent. As the binder, cellulose such as ethyl cellulose, polyvinyl butyral and the like can be used.
In addition, the content of the binder in the vehicle is not particularly limited and should be appropriately selected according to the use or required properties thereof, but it is preferable to adjust the amount to 1 to 7 parts by mass based on 100 parts by mass of the conductive powder described above. It is more preferable to adjust to 1.5 mass parts-6 mass parts.
(3) viscosity modifier
A viscosity modifier is a component added in order to adjust the viscosity of an electrically conductive paste so that it may print to objects, such as a ceramic green sheet, favorably.
As such a viscosity modifier, it is necessary to use petroleum hydrocarbon as a main component from the viewpoint of imparting proper dryness and solubility to the conductive paste. In particular, it is preferable that a boiling point exists in the range of 150 degreeC-260 degreeC, and it is more preferable to exist in the range which is 160 degreeC-200 degreeC. When the boiling point of a viscosity modifier is less than 150 degreeC, since drying time is very short and the viscosity of an electrically conductive paste rises rapidly during printing, it becomes difficult to form a desired internal electrode layer. On the other hand, when a boiling point exceeds 260 degreeC, drying property will remarkably deteriorate, a long time is required for drying after printing, and productivity will remarkably deteriorate.
As a viscosity modifier which satisfy | fills the above conditions, For example, the thing which has methyl ethyl benzene, a trimethyl benzene, a tridecane, a nonane, a cyclohexane etc. as a main component, A solvent made by JX Nikko Niseki Energy Co., Ltd. (brand name Boiling point: 160 ° C to 200 ° C), dry solvent high soft (brand name, boiling point: 160 ° C to 195 ° C), LS Solvent (brand name, boiling point: 200 ° C to 260 ° C), manufactured by JX Nikko Niseki Energy Co., Ltd. Can be mentioned.
The content of the viscosity modifier in the conductive paste is preferably 10 parts by mass to 50 parts by mass, more preferably 10 parts by mass to 40 parts by mass with respect to 100 parts by mass of the conductive powder. When content of a viscosity modifier is less than 10 mass parts, the above-mentioned effect cannot fully be acquired. On the other hand, when content of a viscosity modifier exceeds 50 mass parts, a viscosity will fall remarkably and it will become difficult to smear an electrically conductive paste at the time of printing, or to control the thickness of an internal electrode layer to a desired range.
(4) pyrolysis inhibiting additive
The electrically conductive paste of this invention contains 0.1 mass part-1 mass part with respect to 100 mass parts of electroconductive powders other than the component mentioned above with respect to 100 mass parts of electroconductive powders as a thermal decomposition suppression additive, a modified polyurethane, a modified polyamide, and ammonium phosphate. It features.
In the electrically conductive paste of this invention, the addition of these thermal decomposition suppression additives has suppressed the catalyst function of the electroconductive powder in a debonder process, and the effect which prevents the generation of the abrupt decomposition gas which accompanies it is acquired. The reason why such an effect is obtained is not clear, but the modified polyurethane and the modified polyamide do not contain S in the structure, but the functional groups of the molecules constituting the thermal decomposition suppressing additive are adsorbed on the surface of the conductive powder, so that It is considered that the rapid thermal decomposition is suppressed by inhibiting the contact of the binder. On the other hand, the polyphosphate ester is considered to be because the functional group containing phosphorus decomposes upon heating to form a film, and similarly inhibits contact between the binder and the conductive powder, thereby suppressing partial thermal decomposition of the binder.
Moreover, since these pyrolysis inhibiting additives are unlikely to swell even when mixed with the viscosity modifier mainly containing the petroleum hydrocarbon mentioned above, a mixed state can be maintained for a long time. Therefore, the conductive paste of the present invention has a small change in viscosity even when stored for a long period of time after production, so that the desired internal electrode layer can be easily formed.
Among the above-described pyrolysis inhibiting additives, as the modified polyurethane, urea-modified polyurethane which introduces a diamine skeleton through a urea bond to a urethane bond may be mentioned, but a polyurethane modified through an imide bond, an amide bond, an amideimide bond, or the like. It may be. Specifically, EFKA4046 (trade name), EFKA4047 (trade name), etc., manufactured by Ciba Specialty Chemicals, can be used as appropriate.
As modified polyamide, what substituted the functional group, such as a methoxymethyl group, at least one part of the hydrogen atom of an amide bond is mentioned, for example. Specifically, Dispalon DA-1401 (trade name) manufactured by Kusumoto Kasei Co., Ltd. can be appropriately used.
Examples of the ammonium phosphate include diammonium hydrogen phosphate, type I polyammonium phosphate, type II polyammonium phosphate, and the like. Specifically, Taihe K (trade name) and Taien C = II manufactured by Daihei Chemical Industries, Ltd. (Brand name) etc. can be used suitably.
Content of a thermal decomposition suppression additive is 0.1 mass part-1 mass part with respect to 100 mass parts of electroconductive powder, Preferably it is 0.2 mass part-0.8 mass part, More preferably, you may be 0.4 mass part-0.6 mass part. When content of a thermal decomposition suppression additive is less than 0.1 mass part, the effect of suppressing thermal decomposition of a binder cannot fully be acquired. On the other hand, when the content of the pyrolysis inhibiting additive exceeds 1 part by mass, the effect of suppressing the thermal decomposition of the binder can be obtained, but there is a risk of adversely affecting the characteristics of the electronic component. In addition, when stored for a long period of time, in addition to causing a deterioration in the stability of the viscosity of the conductive paste, there is a risk of causing an increase in cost.
(5) other additives
In the electrically conductive paste of this invention, in addition to the above-mentioned additive, additives, such as a dispersing agent, a flame retardant, and a sedimentation inhibitor, can also be added according to the use. It is preferable that these other additives exist in the range whose decomposition temperature is 150 degreeC-350 degreeC. If the decomposition temperature is less than 150 ° C, it may be easily decomposed at the time of mixing or kneading, and the effect of adding another additive may not be obtained. On the other hand, when the decomposition temperature exceeds 350 deg. C, it remains after the debonding agent step, and there is a possibility that structural defects such as the cracks and interlayer peeling described above are generated by the gas generated by thermal decomposition of these other additives in the firing step.
It is preferable to set it as 1.0 mass part or less in total with respect to 100 mass parts of electroconductive powders, and, as for content of another additive, it is more preferable to set it as 0.5 mass part or less. When content of another additive exceeds 1.0 mass part, the effect of this invention may not be acquired in relation of another structural component.
2. Conductive Paste
(1) Manufacturing Method of Conductive Paste
The electrically conductive paste of this invention can be manufactured by the method similar to a prior art as long as the above-mentioned structural component can be disperse | distributed uniformly. For example, it can manufacture by uniformly kneading each structural component mentioned above with a triaxial roll mill etc.
In addition, the timing of adding the above-mentioned pyrolysis inhibiting additive is not particularly limited and may be dispersed in the vehicle in advance, but it is preferable to mix the conductive powder in the step of dispersing in the vehicle.
Moreover, the timing which adds the other additive mentioned above is not restrict | limited, either, It can add at arbitrary timings. However, depending on the kind of other additives, affinity with electroconductive powder is high, and it may be considered that the adsorption | suction of a thermal decomposition suppressing additive to the surface of electroconductive powder is inhibited by this. In such a case, it is necessary to appropriately adjust the order of adding the pyrolysis inhibiting additive and other additives.
(2) Characteristics of the conductive paste
As mentioned above, according to the electrically conductive paste of this invention, since the catalytic action of the electroconductive powder in a debonder process is suppressed, it can prevent that the thermal decomposition temperature of the binder in this paste falls too much. Therefore, when the internal electrode layer of the multilayer ceramic capacitor is formed using the conductive paste of the present invention, generation of structural defects such as interlayer peeling and cracks can be effectively prevented.
The pyrolysis inhibiting effect of the binder can be determined by measuring the pyrolysis peak intensity of the binder in the vehicle and the pyrolysis peak intensity of the binder contained in the conductive paste using a differential thermal gravimetric system.
In FIG. 1, the amount of change (DELTA) TG (pyrolysis peak intensity) with respect to the temperature of thermogravimetric TG of a vehicle and an electrically conductive paste is shown typically. The conductive paste (2) which does not include the thermal decomposition inhibiting additive, by the catalytic action of the conductive powder in the conductive paste, and a thermal decomposition peak temperature of the binding agent T 2 vehicle (3) shifted toward a temperature lower than 3 thermal decomposition peak temperature of the binding agent T .
On the other hand, in the electrically
Therefore, the pyrolysis peak temperature T 1 of the binder in the vehicle 3 and the pyrolysis peak temperature T 1 of the binder in the
Thermal decomposition strength ratio: α = ΔTG1a/ ΔTG3 (a)
Moreover, the electrically conductive paste of this invention is excellent also in the stability of a viscosity, and even if it is stored for a long time after manufacture, there is little increase of a viscosity. Specifically, the viscosity η 1 at the time when 24 hours have elapsed after the production of the conductive paste, the rate of increase in viscosity when the conductive paste is stored at 25 ° C. for 20 days and the viscosity η 2 after the lapse of this period, That is, the increase rate (beta) of the viscosity computed based on following formula (b) can be made into less than 20%, Preferably it is less than 15%.
Rate of increase of viscosity: β = (η 2 -η 1 ) / η 1 × 100 (b)
Such an electrically conductive paste of this invention can be used suitably for formation of the internal electrode of a multilayer ceramic capacitor. In addition, since the manufacturing method of the multilayer ceramic capacitor of this invention is the same as that of a prior art except using the electrically conductive paste of this invention, description here is abbreviate | omitted.
<Example>
Hereinafter, this invention is demonstrated in detail using an Example and a comparative example. In the following Examples and Comparative Examples, the present invention will be described taking as an example the case where Ni powder having a large catalytic action is used among the above-mentioned conductive powders. However, this invention is not limited to this, It is similarly applicable also when Pd powder, the alloy powder containing Ni, and the alloy powder containing Pd are used.
In the following Examples and Comparative Examples, a mixture of ethyl cellulose and terpineol in a mass ratio of 1:19 was used as the vehicle. The pyrolysis temperature of ethyl cellulose in this vehicle, that is, the pyrolysis peak temperature of ethyl cellulose in the absence of catalysis by the conductive powder was measured by the following method.
Initially, this vehicle was apply | coated so that thickness might be set to 100 micrometers on PET film using an applicator (made by Kodaira Seisakusho, YBA-2), and it dried at 90 degreeC for 6 hours. After confirming that the vehicle was completely dried, only the dry film of the vehicle was peeled from the PET film, and this was ground by pulverization, and the vehicle dried powder was obtained by filtering the sieve having a mesh size of 100 µm.
Subsequently, the obtained vehicle dried powder was analyzed by using a differential thermal gravimetric analyzer (manufactured by Bruker AX Corporation, TG-DTA2000SA) and setting the temperature increase rate in a nitrogen stream of 200 ml / min to 10 ° C / min. And the change amount (DELTA) TG 3 with respect to the thermogravimetric temperature was computed from following Formula (c). The results, it was confirmed that the thermal decomposition of ethyl cellulose of the peak temperature T 3 bar, 355 ℃ determined based on the.
ΔTG = (change amount of thermogravimetric TG) / (heating time) (c)
(Example 1)
As an electroconductive powder, Ni powder (made by Sumitomo Kinzoku Kozan Co., Ltd.) whose average particle diameter is 0.2 micrometer is prepared, and 60 mass parts (ethyl cellulose: 3 mass parts) of the vehicle mentioned above with respect to 100 mass parts of this Ni powder. 0.1 mass part of Dispalon DA-1401 (made by Kusumoto Chemical Co., Ltd.) was weighed as a 40 mass part and a thermal decomposition suppression additive, and the viscosity modifier (made by Idemitsu Koyama Co., Ltd. A solvent). Subsequently, these constituents are mixed at the same time, and the particle diameter measured by a FOG gauge (particle gauge) is 10 micrometers or less using a triaxial roll mill (Inoue Seisakusho, 43/4 * 11S type roll mill). It knead | mixed until it became, and the electrically conductive paste was produced.
[Evaluation of Thermal Degradability]
The pyrolysis peak temperature T 1a is specified by measuring the pyrolysis peak temperature of the ethyl cellulose contained in the conductive paste in the same manner as the pyrolysis peak temperature of the ethyl cellulose in the vehicle described above, and the pyrolysis intensity ratio α is calculated by the formula (a). did. Moreover, based on this result, the thermal decomposition property of the ethyl cellulose in the electrically conductive paste of Example 1, and the grade of gas generation accompanying it were evaluated.
[Stability Evaluation of Viscosity]
First, the viscosity (eta) 1 at the time which passed 24 hours after manufacture of an electrically conductive paste was measured using the viscometer (The Brookfield company make, HBT type | mold viscometer). Subsequently, this electrically conductive paste was stored for 20 days at 25 degreeC constant temperature, and the viscosity (eta) 2 after this period progressed was measured similarly. And the increase rate (beta) of a viscosity was computed from Formula (b). Based on this result, the thing of "good (◎)" and the thing of 15% or more and less than 20% "validated ((circle))" and the thing of 20% or more were evaluated as "impossible (x)" that the increase rate (beta) of viscosity was less than 15%. These results are shown in Table 2.
(Examples 2 to 8)
A conductive paste was prepared in the same manner as in Example 1 except that the kind and content of the pyrolysis inhibiting additives were as shown in Tables 1 and 2, and the pyrolysis peak temperature T 1a and the pyrolysis intensity ratio α were measured. The thermal degradability of the ethyl cellulose in these conductive pastes and the degree of gas generation accompanying them were evaluated. In addition, in the same manner as in Example 1, the rate of increase of viscosity β was measured to evaluate the stability of the viscosity. These results are shown in Table 2.
(Examples 9 and 10)
Except having used what is shown in Table 1 and Table 2 as a viscosity modifier, the electrically conductive paste was produced like Example 2, the thermal decomposition peak temperature T1a and the thermal decomposition intensity ratio (alpha) were measured, and in these electrically conductive pastes, The thermal decomposition property of the ethyl cellulose of and the degree of gas generation accompanying it were evaluated. In addition, in the same manner as in Example 1, the rate of increase of viscosity β was measured to evaluate the stability of the viscosity. These results are shown in Table 2.
(Comparative Example 1)
A conductive paste was prepared in the same manner as in Example 1 except that no pyrolysis inhibiting additive was added, and the pyrolysis peak temperature T 1b and the thermal decomposition strength ratio α were measured to thermally decompose the ethyl cellulose in these conductive pastes. The performance and the degree of gas generation accompanying it were evaluated. In addition, in the same manner as in Example 1, the rate of increase of viscosity β was measured to evaluate the stability of the viscosity. These results are shown in Table 2.
(Comparative Examples 2 and 3)
A conductive paste was prepared in the same manner as in Example 1 except that the kind and content of the pyrolysis inhibiting additives were as shown in Tables 1 and 2, and the pyrolysis peak temperature T 1a and the pyrolysis intensity ratio α were measured. The thermal degradability of the ethyl cellulose in these conductive pastes and the degree of gas generation accompanying them were evaluated. In addition, in the same manner as in Example 1, the rate of increase of viscosity β was measured to evaluate the stability of the viscosity. These results are shown in Table 2.
(General evaluation)
From Table 1 and Table 2, the conductive pastes of Examples 1 to 10 included in the technical scope of the present invention have a thermal decomposition peak temperature of ethyl cellulose in the range of 300 ° C to 315 ° C, and a thermal decomposition strength ratio α of less than 1. It was confirmed that the thermal decomposition of the binder was suppressed. Moreover, it was confirmed that evaluation regarding the stability of a viscosity is also favorable. Therefore, it is thought that the multilayer ceramic capacitor which formed the internal electrode layer using these electrically conductive pastes can greatly reduce the generation | occurrence | production of the structural defect in a debonder process or a baking process. In addition, it is thought that these conductive pastes can form an internal electrode layer without any problem even after a long period of time after production. In addition, in Example 10 using the viscosity modifier whose boiling point exceeds 200 degreeC, although the rate of increase (beta) of viscosity was high compared with another Example, it was a level which was satisfactory practically.
In contrast, in the conductive pastes of Comparative Examples 1 and 2, the pyrolysis peak temperature of ethylene cellulose was lowered to 290 ° C, and it was confirmed that the thermal decomposition strength ratio α was 1 or more. Moreover, although the electrically conductive paste of the comparative example 3 had many addition amounts of the thermal decomposition suppressing additive, and the fall of the thermal decomposition peak temperature was not seen, the increase rate (beta) of viscosity became 20% or more, and it was confirmed that stability of viscosity was low.
1 conductive paste containing pyrolysis inhibiting additive
2 conductive paste without pyrolysis inhibitor additive
3 vehicle
Claims (8)
The electrically conductive paste containing 1 or more types of compounds chosen from a modified polyurethane and a modified polyamide as said pyrolysis inhibiting additive, and whose content of the said pyrolysis inhibiting additive is 0.1 mass part-1 mass part with respect to 100 mass parts of said electroconductive powders.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014153168A JP6365068B2 (en) | 2014-07-28 | 2014-07-28 | Conductive paste for multilayer ceramic capacitor internal electrode, method for producing the same, and multilayer ceramic capacitor |
| JPJP-P-2014-153168 | 2014-07-28 |
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| JP2014029845A (en) * | 2012-06-28 | 2014-02-13 | Nippon Steel & Sumikin Chemical Co Ltd | Method for producing conductive paste |
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| JP2615116B2 (en) * | 1988-02-10 | 1997-05-28 | 日本ケミコン株式会社 | Manufacturing method of multilayer ceramic capacitor |
| JPH06119808A (en) * | 1992-02-27 | 1994-04-28 | Taiyo Yuden Co Ltd | Conductive paste |
| JP4161472B2 (en) | 1999-06-25 | 2008-10-08 | 株式会社村田製作所 | Conductive thick film paste, method for producing the same, and multilayer ceramic capacitor using the same |
| JP4626215B2 (en) * | 2004-06-07 | 2011-02-02 | 住友金属鉱山株式会社 | Nickel paste for multilayer ceramic capacitors |
| JP5180588B2 (en) * | 2005-12-22 | 2013-04-10 | ナミックス株式会社 | Thermosetting conductive paste and multilayer ceramic component having external electrodes formed using the same |
| JP4807581B2 (en) | 2007-03-12 | 2011-11-02 | 昭栄化学工業株式会社 | Nickel powder, method for producing the same, conductor paste, and multilayer ceramic electronic component using the same |
| TWI421882B (en) | 2009-06-08 | 2014-01-01 | Daiken Chemical Co Ltd | Barium titanate powder, nickel paste, preparation method and laminated ceramic capacitors |
| CN101593622B (en) * | 2009-06-30 | 2011-03-30 | 广东风华高新科技股份有限公司 | MLCC copper inner electrode sizing material |
| CN101872679B (en) * | 2010-05-26 | 2012-09-05 | 广东风华高新科技股份有限公司 | Nickel inner electrode slurry |
| JP5724822B2 (en) | 2011-10-21 | 2015-05-27 | 堺化学工業株式会社 | Method for producing sulfur-containing nickel fine particles |
| KR101452186B1 (en) * | 2012-12-26 | 2014-10-21 | 주식회사 누리비스타 | Paste for internal electrode and multi-layer ceramic capacitor using the same |
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| TWI663614B (en) | 2019-06-21 |
| JP6365068B2 (en) | 2018-08-01 |
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