CN102266939A - Metal powder and manufacturing method thereof, and conductive paste using metal powder and laminated ceramic electronic component using conductive paste - Google Patents
Metal powder and manufacturing method thereof, and conductive paste using metal powder and laminated ceramic electronic component using conductive paste Download PDFInfo
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- CN102266939A CN102266939A CN201110147813XA CN201110147813A CN102266939A CN 102266939 A CN102266939 A CN 102266939A CN 201110147813X A CN201110147813X A CN 201110147813XA CN 201110147813 A CN201110147813 A CN 201110147813A CN 102266939 A CN102266939 A CN 102266939A
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Abstract
The invention provides a metal powder and a manufacturing method thereof, and a conductive paste using the metal powder and a laminated ceramic electronic component using the conductive paste. A solution containing a metal salt and a solution containing a reducing agent are mixed together and a suspension containing metal particles and the reducing agent is obtained via an oxidation-reduction reaction. Then the suspension is added with an organic sulfur compound and then is subject to drying. Then metal powders are obtained, wherein the surface of the metal particles are formed with metal atoms and sulfur atoms. The conductive paste made of the metal powders is subject to lamination and firing so as to product ceramic green sheets with inner electrode patterns. Then a substrate (12) equipped with a ceramic layer (14) and an inner electrode (16) is obtained. The two ends of the substrate (12) are formed with external electrodes (18) so as to obtain a laminated ceramic capacitor (10).
Description
Technical field
The present invention relates to metal dust and its manufacture method and use the conductive paste of metal dust and the monolithic ceramic electronic component of this cream of use, especially for example relate to, be used for metal dust and its manufacture method of internal electrode materials such as laminated ceramic capacitor and use the conductive paste of metal dust and the monolithic ceramic electronic component of this cream of use.
Background technology
Monolithic ceramic electronic component contains the matrix that constitutes with a plurality of ceramic layers and the internal electrode that forms between these ceramic layers.For example, in laminated ceramic capacitor etc., in the both sides of the ceramic layer that is laminated, internal electrode forms in mode respect to one another.And in the stacked direction of ceramic layer, the internal electrode of adjacency is alternately distolateral and another distolateral being drawn of the long axis direction of matrix.And, in the both end sides of the long axis direction of matrix,, between 2 outer electrodes, form static capacity thus by forming the outer electrode that is connected with derivative internal electrode.
In order to make such monolithic ceramic electronic component, prepare to have ceramic green sheet.Mixing metal dust and resin etc. obtain conductive paste on this ceramic green sheet, use the conductive paste that obtains, and form a plurality of internal electrode patterns.The ceramic green sheet that forms internal electrode pattern is stacked by multi-disc, and at this stacked ceramic green sheet that does not form internal electrode pattern in stacked direction outside, forms duplexer.Corresponding internal electrode pattern separately cuts off duplexer, is formed for obtaining the chip of the matrix of monolithic ceramic electronic component.By burning till this chip, form matrix thus with ceramic layer and internal electrode.And, form outer electrode by both ends of the surface at the long axis direction of matrix, make monolithic ceramic electronic component thus.
Illustrated, before burning till chip, needed through heat-treating the degreasing process of removing the resinous principle that contains in the chip.When using metal, in degreasing process, utilize the violent burning of the catalytic effect generation resin of metal herein, as the material of conductive paste with catalytic effect.At this moment, because flash fire gas takes place, the pressure of chip internal increases, so produce faults of construction such as separation or crackle.
Therefore, on the surface of the contained metallic of conductive paste, form the sulfide of this metal, perhaps form the material that this metal and sulphur compound chemical bonding form, suppress the catalytic effect of metal thus.So, prevent the violent burning of the resin in the degreasing process of chip, the fault of construction that is suppressed in the matrix produces.
About the making of conductive paste, reducing metal compound in the presence of macromolecule dispersing agent is disclosed, make the method (with reference to patent documentation 1) of the metal particle dispersion of high concentration.In addition, disclose to nickel by powder and added thiocarbamide, be heated to 200～300 ℃, be produced on the technology (with reference to patent documentation 2) that its surface forms the nickel by powder of the compound layer that contains nickel and sulphur thus.
In addition, disclose when utilizing the gas phase hydrogen reduction method to carry out the making of nickel micro mist,, made the method (with reference to citing document 3) of the nickel by powder that contains element sulphur thus by following sulphur compound.
In addition, disclose, made the method (with reference to patent documentation 4) of the nickel by powder that contains the nickel element sulphur thus by nickel by powder is handled with the solution of sulphur compound.
Patent documentation
Patent documentation 1: TOHKEMY 2003-103158 communique
Patent documentation 2: the world discloses the 2005/123307th
Patent documentation 3: Japanese kokai publication hei 11-80817 communique
Patent documentation 4: TOHKEMY 2007-191771 communique
Summary of the invention
Yet in the method as patent documentation 1, dispersant is adsorbed on the metal surface with the ionic adsorption site of anion, cation, nonionic etc.The absorption of these macromolecule dispersing agents is reversible reactions, by the easy adsorption desorptions that take place such as additive that add afterwards.The dispersant of adsorption desorption swims in the suspension, and the dispersiveness of metal microparticle is worsened.
In addition, in the method for patent documentation 2,, form the compound layer that contains nickel and sulphur on the surface of nickel by powder thus by heat-treating with 200～300 ℃ temperature.Utilize this heat treatment, solidify between the nickel by powder, the dispersed reduction.Therefore, when using nickel by powder to make conductive paste, can't obtain high the filming of flatness, the covering property that is brought by conductive paste reduces, and produces when perhaps burning till and separates.
In addition, in the method for patent documentation 3, the high-temperature when utilizing the manufacturing of the nickel micro mist that is undertaken by the gas phase hydrogen reduction method, when forming the nickel micro mist, form metal sulfide in the metal surface, but the gas phase hydrogen reduction method is the manufacture method under the high temperature, therefore, produce between the nickel by powder and solidify, the dispersed reduction when making conductive paste, can't obtain high the filming of flatness, the covering property that is brought by conductive paste reduces, and perhaps produces when burning till and separates.
In addition, in the method for patent documentation 4, be the method for mixed Ni powder and sulphur compound in solvent only.Usually, the surface of particle metal powder is by oxidation in advance, and metal oxide is difficult to react with sulphur compound.Therefore, nickel and sulphur compound do not form sulfide, and only at the surperficial adsorption of sulfur compounds of nickel micro mist.When using such nickel micro mist to make conductive paste, absorbing molecules breaks away from, and can't suppress the catalytic effect of metal, produces fault of construction in degreasing process.
Therefore, favorable dispersibility when main purpose of the present invention is to provide a kind of making conductive paste, and can suppress metal dust and its manufacture method of the catalytic effect of metal during the heat treatment conductive paste.
In addition, the object of the present invention is to provide a kind of monolithic ceramic electronic component that uses the conductive paste of such metal dust and use this conductive paste.
The present invention is, contains metallic, and on the surface of metallic, the metal dust that the metallic atom of metallic and the sulphur atom in the organosulfur compound form by chemical bonding.
On the surface of metallic, the metallic atom of metallic and the sulphur atom in the organosulfur compound be by chemical bonding, comprised in the organosulfur compound that can obtain thus playing a role as dispersant metal dust.And then, surface at metallic, because metallic atom and sulphur atom carry out chemical bonding,, prevent the violent burning of resin so in the degreasing process of the chip that the conductive paste formation internal electrode pattern that uses this metal dust uses, can suppress the catalytic effect of metal.Therefore, the burning gases that can prevent to be accompanied by the violent burning of resin take place, and can suppress to produce and separate or faults of construction such as crackle.
In such metal dust, organosulfur compound preferably has the organosulfur compound of the functional group that is selected from mercaptan, thiocarbamide (チ オ カ Le バ ミ De), disulphide (ジ ス Le Off イ De), thioesters, thiocyanates (チ オ シ ア ネ one ト), thiazole (チ ア ゾ one Le) in its structure.
In addition, the sulphur that preferably contains 0.01～5 quality % with respect to metallic.
In addition, preferably contain carbon below the 5 quality % with respect to metallic.
In addition, the particle diameter of metallic is preferably in the scope of 0.010 μ m～1 μ m.Aforesaid functional group is owing to easy and metal surface bonding, so can effectively form the chemical bond of the sulphur atom in metallic atom and the sulphur compound on the surface of metallic.
In addition, by can contain the sulphur of suitable amount with respect to metallic, the surface of metallic is coated with organosulfur compound fully, and in the good dispersiveness that obtains metal dust, can suppress the catalytic effect of metal.
In addition, the carbon in the organosulfur compound is owing to the dispersiveness of giving metal dust, and by can contain the carbon of suitable amount with respect to metallic, the metal dust that obtains that thus can be good gets dispersed.
By the particle diameter that makes metallic is suitable size, can make the surface area of metallic be made as suitable value thus, can coat with the organosulfur compound of the suitable amount surface to metallic.
In addition, the present invention is, comprise: mix solution that contains slaine and the solution that contains reducing agent, utilize redox reaction to obtain containing the manufacture method of metal dust that the step of suspension of metallic and reducing agent and mixing suspension and organic sulfur oxide form the step of the water slurry that contains above-mentioned any described metal dust.
In the step of the water slurry that obtains containing metal dust, mixed solution only, and do not need the high temperature heating.Therefore, can obtain not solidifying between the metallic metal dust of ground favorable dispersibility.
In the manufacture method of such metal dust, the pH of the solution that preferred mixed metal particle, reducing agent and organosulfur compound form is more than 2.
The pH of the solution that hybrid metal particle, reducing agent and organosulfur compound form can see the dissolving of metal less than 2 o'clock, and the effectiveness of reducing agent reduces.
In addition, the present invention is to contain above-mentioned each described ground metal dust and organic vehicle ground conductive paste.
The made from metal powder conductive paste on the application of the invention ground can obtain the conductive paste that the even dispersion of metal dust forms.In addition, on the surface of metal dust, because the sulfur atom linkage in metallic atom and the organosulfur compound can suppress the catalytic effect that is brought by metal.Therefore, when using this conductive paste to make monolithic ceramic electronic component, in the degreasing process of the chip that forms internal electrode pattern, can prevent the violent burning of the resin in the chip, can suppress to separate, the fault of construction of chip such as crackle takes place.
In addition, the present invention is to contain a plurality of ceramic layers that are laminated and the internal electrode that forms between ceramic layer, the monolithic ceramic electronic component that described internal electrode forms by the above-mentioned conductive paste of sintering.
By adopting the conductive paste that uses metal dust of the present invention, can suppress the generation of the fault of construction of chip, therefore can reduce the fraction defective of the monolithic ceramic electronic component that obtains.
According to the present invention, can obtain the metallic atom of metallic and the metal dust that the sulphur atom in the organosulfur compound forms by the chemical bond combination on the surface of metallic.Organosulfur compound when using this made from metal powder conductive paste, can obtain the dispersiveness in water slurry owing to can be used as the dispersant effect well.In addition, when adopting the conductive paste that uses this metal dust to make monolithic ceramic electronic component, in the degreasing process of the chip that the formation internal electrode pattern forms, can suppress the catalytic effect of metal, prevent the violent burning of resin.Therefore, can suppress to separate or the generation of the fault of construction of chip such as crackle.
In addition, the method according to this invention owing to can obtain having the metal dust of aforesaid structure, can obtain not solidifying between the metal dust metal dust of ground, favorable dispersibility with not being heated to high temperature.
In addition, the made from metal powder conductive paste of the application of the invention can obtain the conductive paste that the even dispersion of metal dust forms.Therefore,, obtain high the filming of flatness thus, can prevent that the covering property that is brought by conductive paste from reducing, and produces problems such as separation when perhaps burning till by using this conductive paste.
In addition, form the internal electrode of monolithic ceramic electronic component, can prevent the fault of construction of chip, so the fraction defective of monolithic ceramic electronic component is descended by using such conductive paste.
Above-mentioned purpose of the present invention, other purpose, feature and advantage, the explanation of implementing the preferred plan of following invention from reference accompanying drawing being used for of carrying out should be clearer and more definite.
Description of drawings
Fig. 1 is the stereogram of expression as the laminated ceramic capacitor of an example of monolithic ceramic electronic component of the present invention.
Fig. 2 is the diagram figure of the internal structure of the laminated ceramic capacitor shown in the presentation graphs 1.
Fig. 3 is the surface that is illustrated in the Ni particle, and the S of Ni and thiomalic acid carries out the diagram figure of the example of the metal dust that chemical bonding forms.
Reference numeral
10 laminated ceramic capacitors
12 matrixes
14 ceramic layers
16 internal electrodes
18 outer electrodes
The specific embodiment
Fig. 1 is the stereogram of expression as the laminated ceramic capacitor of an example of monolithic ceramic electronic component of the present invention, and Fig. 2 is the diagram figure that its internal structure is shown.Laminated ceramic capacitor 10 comprises matrix 12.Matrix 12 has the structure that forms with a plurality of ceramic layers 14 of dielectric material formation and a plurality of internal electrode 16 interaction cascadings.Draw alternately at distolateral and another distolateral quilt of the long axis direction of matrix 12 at the internal electrode 16 of the stacked direction adjacency of matrix 12.At the both ends of the matrix 12 of being drawn internal electrode 16, with separately with internal electrode 16 ways of connecting, form outer electrode 18.Thereby 2 18 of outer electrodes form static capacity.
Prepare ceramic green sheet in order to make such laminated ceramic capacitor 10.Ceramic green sheet contains for example BaTiO
3Be base material, SiO
2Deng sintering aid, the rare earth element that is used to regulate electrical characteristics, alkaline-earth metal, Mn, V etc.These carry out slurryizatioies with resin, solvent, obtain ceramic green sheet.
On the ceramic green sheet that obtains, utilize conductive paste to become a plurality of internal electrode patterns of internal electrode 16.Conductive paste contains metal dust and organic vehicle, particularly, by mixed metal powder, ceramic powders, resin, dispersant, solvent etc., uses three rollers to carry out dispersion treatment and obtains.Here, metal dust is for containing metallic, and the metallic atom of metallic and the sulphur atom in the organosulfur compound form by chemical bonding on the surface of metallic.In addition, can use for example brium carbonate etc. as ceramic powders.In addition, as resin, can use for example ethyl cellulose (エ チ Le セ Le one ス), acrylic resin, butyral resin etc.In addition, as dispersant, for example can using, polypropylene glycol is a dispersant etc.In addition, as solvent, for example can use ester series solvents such as terpenic series solvent such as terpineol, dihydro-terpineol, australene, p-cymol or butyl acetate.
Becoming the metal dust of base material herein, can be with making such as liquid phase reduction or vapor phase methods.For example, when utilizing liquid phase reduction to make the Ni powder, in containing the solution of reducing agent (60 ℃), mix the solution (60 ℃) that contains slaine, stirred 30 minutes, obtain containing the suspension of Ni particle and reducing agent thus.The solution that contains slaine can be by for example with respect to water 170g dissolving nickelous sulfate 70g, and is warmed up to 60 ℃ and obtain.Can use the complex compound of organic acid etc. to form agent (Wrong as the particle size adjustment agent herein, and form drug).In addition, can add water 185g with respect to hydrazine hydrate (purity 60%) 60g by the solution that contains reducing agent obtains.Can use complex compound such as organic acid to form agent as the particle size adjustment agent herein.
Adjusting contains the pH of the suspension of the metallic that obtains and reducing agent, limit paddle agitating solution, and the limit is added with organic sulfur compound.And, behind pure water cleaning impurity, suspension after the cleaning in the suction filtration groove, separate pure water and metal dust, carry out drying with heated-air drying formula baking oven then, form metal dust thus on the surface of metallic with metal surface that the sulfur atom linkage in metallic atom and the organosulfur compound forms.For example, use the Ni particle, when using thiomalic acid, as shown in Figure 3,, form the chemical bond of Ni and S on the surface of Ni particle as organosulfur compound as metallic.Illustrated, as reducing agent according to the kind of the kind of metal, organosulfur compound and without limits, can use for example hydrazine, sodium borohydride etc. as concrete example.
The metal dust that uses operation like this to obtain is made conductive paste with method as described above, forms a plurality of internal electrode patterns on ceramic green sheet.Stacked multi-disc forms the ceramic green sheet of internal electrode pattern, and in its both sides the stacked ceramic green sheet that does not form internal electrode pattern, obtain duplexer.And, lump together the cut-out duplexer with separately internal electrode pattern, obtain being used to obtain a plurality of chips of matrix 12.
The chip that obtains carries out one through degreasing process and burns till, and obtains the matrix 12 that ceramic layer 14 and internal electrode 16 interaction cascadings form thus.At the two ends of this matrix 12, with internal electrode 16 ways of connecting coatings electrode cream, and form outer electrode 18 by burning till.Laminated ceramic capacitor 10 is made in operation like this.
At this laminated ceramic capacitor 10, in order to form internal electrode 16, use the conductive paste of the metal dust that the sulphur atom chemical bonding of the metallic atom that utilizes metallic and organosulfur compound forms on the surface of metallic, therefore in the degreasing process of chip, can suppress the catalytic effect of metal.Therefore, in degreasing process, the violent burning of resin can be prevented, the generation of the fault of construction of chips such as the separation that causes by burning gases or crackle can be suppressed.In addition, utilize the organosulfur compound on the surface of metallic can be in water slurry favorable dispersibility ground, obtain the covering property that brings by conductive paste.
Like this, when adopt using the conductive paste of metal dust, because the covering property that is brought by conductive paste is good and can suppress the fault of construction of the chip in the degreasing process, so can be so that the fraction defective of the monolithic ceramic electronic component that arrives.
In addition, the solution and the solution that contains reducing agent that contain slaine by mixing, make the suspension that contains metallic and reducing agent by redox reaction, by in the suspension that obtains, being added with organic sulfur compound, can not be heated to high temperature ground thus, make the metal dust of the metal surface that sulfur atom linkage with metallic atom and organosulfur compound forms, can prevent solidifying between the metal dust.
The organosulfur compound that uses during as the making metal dust, the preferred material with the functional group that is selected from mercaptan, thiocarbamide, disulphide, thioesters, thiocyanates, thiazole that uses are described.The structure of these functional group so reactivity is excellent, makes the key of metallic atom and sulphur atom form owing to improve the activity of sulphur atom in the metal surface.
In addition, as the amount of organosulfur compound, be located at the scope of 0.01～5 quality % with respect to the content of the preferred sulphur of metallic.For in this scope the time, can not form the key of metallic atom and sulphur atom excessive or insufficiently in the metal surface.When the organosulfur compound that plays a role as dispersant is less than this scope, owing to do not remain on the dispersion stabilization in the water slurry, so organosulfur compound clad metal of no use surface, expose metal surface with catalytic effect, therefore the violent burning that suppresses resin in the degreasing process of chip becomes insufficient, may produce fault of construction.In addition, the amount of organosulfur compound is during more than this scope, and the contained sulphur composition of the internal electrode of monolithic ceramic electronic component increases, and metal ratio descends, and therefore may generating electrodes lose (Electricity
Cut れ, electrode breakage), produce fault of construction.
In addition, as the amount of organosulfur compound, be made as scope below the 5 quality % with respect to the content of the preferred carbon of metallic.Though carbon is relevant with the dispersion in water, in this scope, the favorable dispersibility in the water slurry can suppress the generation of aggegation powder.In addition, carbon is during more than this scope, and when making monolithic ceramic electronic component, the carbon component of volatilization is many during the burning till of chip, and becomes the reason of fault of construction, but be in this scope the time, the carbon component minimizing of volatilization in the time of can making the burning till of chip.
In addition, as the particle diameter of metallic, in the scope of preferred 0.01～1 μ m.The particle diameter of metallic is during less than 0.01 μ m, and it is big that the surface area of metallic becomes, and in order to coat whole metal surfaces, and the interpolation quantitative change of organosulfur compound is many.At this moment, when making monolithic ceramic electronic component, the sulphur composition of conductive paste increases, and metal ratio reduces, so may produce the defective of electrode scrap etc.
In addition, when making metal dust, the pH of regulator solution is more than 2.PH is 2 when above, form the key of metallic atom and sulphur atom on the metallic surface, but pH sees the dissolving of metal less than 2 o'clock, at the making monolithic ceramic electronic component, may produce defective.
[embodiment 1]
Use Ni as metallic, make the suspension that contains metallic and reducing agent with aforesaid method, be adjusted to pH14 after, the various organosulfur compounds that add with the sulphur conversion are 1 quality % with respect to metallic, obtain metal dust.The metal dust that use obtains is made conductive paste, and makes monolithic ceramic electronic component with above-mentioned method.And when adopt using the metal dust of various organosulfur compounds, observe formation, Mai Qike (microtrac) particle diameter, cream ratio of viscosities, the fault of construction of the key of metal and sulphur, and the results are shown in table 1.
In table 1,, use the size distribution of Mai Qike particle size analyzer determination suspension for the strange gram particle of wheat footpath.As the index of expression size distribution, calculate the value of D50, D99.In addition,, utilize TG/MS, judge the situation of metallic atom and the chemical bond formation of sulphur atom, have zero mark the Ni powder that the volatilization at sulphur composition more than 800 ℃ produces about the formation of the key of metal and sulphur.In addition, to the ratio of viscosities of cream, use E type viscosimeter that the viscosity under the 50rpm is measured.Measure its viscosity and mensuration behind the making cream immediately through the viscosity behind 1 time-of-week herein.And, the viscosity of measuring immediately after making as ratio of viscosities=, estimate through the viscosity behind 1 time-of-week/cream.In addition, for fault of construction, the fault of construction of the monolithic ceramic electronic component of making of microscopic examination is calculated the fault of construction rate.And, the fault of construction rate less than the situation of 100ppm be zero, the situation of 100ppm～not enough 1000ppm is △, situation more than the 1000ppm for *.
[table 1]
As shown in Table 1, when use has the organosulfur compound of functional groups such as mercaptan, thiocarbamide, disulphide, thioesters, rhodanate/ester, thiazole, because sulphur atom is active high, so reactive excellent, the organosulfur compound with these functional groups forms the key of metallic atom and sulphur atom in the metal surface.Have metal dust that these organosulfur compounds carry out the metal surface that chemical bonding forms and can the dispersiveness in water slurry improve and suppress the generation of aggegation powder.In addition,, do not exchange absorption with the dispersant that is used for cream even if in cream, and the viscosity stability excellence.In addition, utilize the metallic atom of metal surface and the key of sulphur atom, can suppress the catalytic effect of metal, the fault of construction incidence of chip is reduced.
On the other hand, thioether (ス Le Off イ De) is reactive poor, and sulfonic acid is stable as the sulfonic group that contains aerobic and sulphur, is not the chemical constitution of the direct and metal bonding of sulphur atom.Therefore, can not form the key with metal, not have effect as described above.
[embodiment 2]
Use Cu as metallic, use thiocarbamide, make monolithic ceramic electronic component similarly to Example 1 and estimate as organosulfur compound.Herein, the addition of change organosulfur compound and adjusting are estimated the influence that is brought by the sulfur content in the organosulfur compound with respect to the amount of the sulphur of metallic.Illustrated, with respect to the amount of the carbon of metallic in all test portions, the amount that makes the mode in its scope below 5 quality % regulate organosulfur compound.And will obtain the results are shown in table 2.
[table 2]
As can be known, when the sulfur content of metallic is in the scope of 0.01～5 quality %, form the key of metallic atom and sulphur atom in the metal surface shown in test portion numbering 15～17, the incidence of the fault of construction of chip is few.Relative therewith, shown in test portion numbering 13, when being 0 quality % with respect to the sulfur content of metallic, just when not being added with organic sulfur compound, in the degreasing process of chip, because the catalytic effect of metal makes resin produce violent burning, the generation fault of construction.In addition, owing to non-cohesive organosulfur compound, so the dispersed variation of metal dust in the metal surface.May produce the aggegation powder.
In addition, shown in test portion numbering 14, with respect to the sulfur content of metallic during, because the amount of the organosulfur compound that plays a role as dispersant is few less than 0.01 quality %, the dispersion stabilization of the metal dust in the water slurry can not be remained on, the aggegation powder may be produced.In addition, the metal surface can't be coated with organosulfur compound fully, expose the metal surface with catalytic effect, therefore in the degreasing process of chip, can't suppress the violent burning of resin, produces fault of construction on chip.In addition, shown in test portion numbering 18, when surpassing 5 quality % with respect to the sulfur content of metallic, the contained sulphur composition of the internal electrode of monolithic ceramic electronic component increases, and metal ratio descends, and therefore produces electrode scrap, produces fault of construction.
[embodiment 3]
Use Ni as metallic, use thiocarbamide, make monolithic ceramic electronic component similarly to Example 1 and estimate as organosulfur compound.Herein, change the addition of organosulfur compound and regulate amount, the influence that is brought by the carbon content in the organosulfur compound is estimated with respect to the carbon of metallic.Illustrated,, in all test portions, regulated the amount of organosulfur compound in the mode in the scope of 0.01～5 quality % with respect to the amount of the sulphur of metallic.For test portion numbering 19, add 1 quality % as the vulcanized sodium that does not contain the sulphur compound of carbon with respect to Ni, estimate.In addition, to test portion numbering 20,21,, use thiocarbamide as organosulfur compound.In addition, to test portion numbering 22～24, use thiomalic acid as organosulfur compound.And will obtain to such an extent that the results are shown in table 3.
[table 3]
Shown in test portion numbering 21～23, the organosulfur compound that carries out chemical bonding with metal plays the effect of dispersant in water, and the dispersiveness of the metal dust in water slurry is good.Therefore, can suppress the generation of aggegation powder.Relative therewith, shown in test portion numbering 19, carbon content with respect to metallic is 0 quality %, perhaps shown in test portion numbering 20, when being less than 0.01 quality % with respect to the carbon content of metallic, owing to disperseing contributive carbon amount few, so can't guarantee the dispersiveness of water slurry, the aggegation powder may take place.In addition, shown in test portion numbering 24, when surpassing 5 quality % with respect to the carbon content of metallic, when burning till the chip that forms internal electrode pattern, the contained carbon component of the sulphur compound of performance is many, therefore becomes the reason of fault of construction.
[embodiment 4]
As the contained metallic of suspension that is added with before the organic sulfur compound, use the different Cu particle of primary particle size, use thioacetic acid potassium as organosulfur compound, make monolithic ceramic electronic component similarly to Example 1 and estimate.Illustrated that the primary particle size of metallic is observed with FE-SEM, and what obtain the results are shown in table 4.
[table 4]
Shown in test portion numbering 26～28, when using the Cu metallic of particle diameter of 0.01～1 μ m, can form the key of Cu metallic atom and sulphur atom in the Cu metal surface, in the degreasing process of chip, can suppress the violent burning of resin, suppress the generation of fault of construction.Relative therewith, the particle diameter of Cu metallic is during less than 0.01 μ m, and the surface area of metallic increases, and when coating all metal surfaces, needs to increase the addition of organosulfur compound.Therefore, the sulphur composition of the internal electrode portion of monolithic ceramic electronic component increases, and metal ratio descends, so faults of construction such as generation electrode scraps.
[embodiment 5]
Use the Ni particle as metallic, use thiomalic acid, regulate the pH of the suspension that contains metallic and reducing agent, make monolithic ceramic electronic component similarly to Example 1 and estimate as organosulfur compound.And what obtain the results are shown in table 5.
[table 5]
Can confirm shown in test portion numbering 30～32, be 2 when above at the pH of the suspension that contains metallic and reducing agent, forms the key of Ni metallic atom and sulphur atom in the Ni metal surface, can suppress the fault of construction generation of chip.Relative therewith, shown in test portion numbering 29, the pH of suspension that contains metallic and reducing agent can see the dissolving of Ni metal less than 2 o'clock, produced fault of construction.
[embodiment 6]
Use the Ni metallic adjusting suspension of average grain diameter 0.5 μ m as metallic after, be not added with organic sulfur compound, add the nonionic macromolecule dispersing agent, regulate aqueous slurry.This slurry with heated-air drying formula oven drying, is obtained metal dust.Use this made from metal powder conductive paste, make monolithic ceramic electronic component.And what obtain the results are shown in table 6.
[table 6]
In water dispersiveness is improved contributive nonionic macromolecule dispersing agent and hinder dispersion in the cream solvent, the stability of cream viscosity worsens.In addition, owing to do not have the key of sulphur compound and metal, so multiple fault of construction.
Claims (9)
1. a metal dust is characterized in that, contains metallic, and on the surface of described metallic, the metallic atom of described metallic and the sulphur atom in the organosulfur compound pass through chemical bonding.
2. metal dust as claimed in claim 1, wherein, described organosulfur compound is for having the organosulfur compound of the functional group of mercaptan, thiocarbamide, disulphide, thioesters, thiocyanates, thiazole in its structure.
3. metal dust as claimed in claim 1 or 2 wherein, contains the sulphur of 0.01～5 quality % with respect to described metallic.
4. as each described metal dust in the claim 1～3, wherein, contain carbon below the 5 quality % with respect to described metallic.
5. as each described metal dust in the claim 1～4, wherein, the particle diameter of described metallic is in the scope of 0.010 μ m～1 μ m.
6. the manufacture method of a metal dust, it comprises following step:
Mix the solution contain slaine and the solution that contains reducing agent, obtain containing by redox reaction metallic and reducing agent suspension step and
Mix described suspension and organic sulfur oxide, form the step that contains the water slurry of each described metal dust in the claim 1～5.
7. the manufacture method of metal dust as claimed in claim 6, wherein, the pH that mixes the solution of described metallic, described reducing agent and described organosulfur compound is more than 2.
8. conductive paste, it contains each described metal dust and organic vehicle in the claim 1～5.
9. monolithic ceramic electronic component, it contains stacked a plurality of ceramic layers and the internal electrode that forms between described ceramic layer, and described internal electrode forms by the described conductive paste of sintering claim 8.
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| JP2010126149A JP2011252194A (en) | 2010-06-01 | 2010-06-01 | Metal powder and method for producing the same, electrically conductive paste using metal powder, and laminated ceramic electronic component using the same |
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Cited By (5)
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| CN102950280A (en) * | 2012-10-11 | 2013-03-06 | 宁波广博纳米新材料股份有限公司 | Treatment method of nano nickel powder for sulfur-containing multi-layer ceramic chip capacitor |
| CN103390442A (en) * | 2012-05-10 | 2013-11-13 | 三星电机株式会社 | Conductive paste composition for internal electrode, multilayer ceramic electronic component, and method of manufacturing the same |
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| CN103390442A (en) * | 2012-05-10 | 2013-11-13 | 三星电机株式会社 | Conductive paste composition for internal electrode, multilayer ceramic electronic component, and method of manufacturing the same |
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| CN104575943B (en) * | 2013-10-16 | 2017-09-01 | 三星电机株式会社 | Common-mode filter |
| CN109416508A (en) * | 2016-07-21 | 2019-03-01 | 株式会社村田制作所 | Photoelectric sensitivity conductive cream, the manufacturing method of laminated electronic component and laminated electronic component |
| CN109416508B (en) * | 2016-07-21 | 2022-03-15 | 株式会社村田制作所 | Photosensitive conductive paste, method for producing laminated electronic component, and laminated electronic component |
| CN109554692A (en) * | 2017-09-27 | 2019-04-02 | 财团法人金属工业研究发展中心 | The manufacturing method of metal-base composites |
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| JP2011252194A (en) | 2011-12-15 |
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