• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    1. TECHNICAL FIELD OF THE INVENTION Nickel powder and its manufacturing method 2. The technical problem to be solved by the invention Provides a nickel powder suitable for conductor pastes with a film thickness close to that of the ceramic, with the sintering start temperature approaching the sintering start temperature of the ceramic layer without breaking conductivity and electrical properties. 3. Summary of Solution to Invention Nickel powder which has a complex oxide layer represented by Formula (1) on the surface. A x B y O (x + 2y) (1) (Wherein A represents Ca, Sr, Ba, B represents Ti, Zr, and x and y represent numbers satisfying the following formula: 0.5 ≦ y / x ≦ 4.5) 4. Important uses of the invention Used in novel nickel powders suitable for thick film conductor pastes and their preparation.
    公开号:KR19990036449A
    申请号:KR1019980007930
    申请日:1998-03-10
    公开日:1999-05-25
    发明作者:에이이치 아사다；유지 아키모토；가즈로 나가시마；히로시 요시다；이이 마
    申请人:에이이치 아사다；소에이 가가쿠 고교 가부시키가이샤；
    IPC主号:
    专利说明:

    Nickel powder and its manufacturing method
    BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to novel nickel powders suitable for thick film conductor pastes and a method of manufacturing the same, and to a laminated electronic component having a conductor layer using the nickel powder and a conductor layer formed using the paste. .
    BACKGROUND ART In the field of electronics, thick film pastes such as conductor pastes and resistance pastes are used to manufacture components such as electronic circuits, resistors, capacitors, and IC packages. It is a paste, which is made by uniformly mixing and dispersing conductive powders such as metals, alloys, and metal oxides in an organic vehicle together with a glassy competing agent or other additives as necessary. A resist film is formed.
    BACKGROUND ART Ceramic multilayer electronic components such as multilayer capacitors and multilayer inductors and ceramic multilayer substrates are generally manufactured by alternately stacking a plurality of unbaked ceramic green sheets, such as dielectrics and magnetic bodies, and an inner conductor paste layer, and simultaneously firing at high temperatures. As internal conductors, noble metals such as palladium, silver-palladium, and platinum have been mainstream in recent years, but in recent years, delamination resulting from oxidative expansion during resource saving or firing of palladium or silver-palladium, Since improvement of a crack etc. is calculated | required, nonmetallic materials, such as nickel, attract attention.
    In these laminated parts and multilayer boards, there is a tendency to increase the number of laminations more. For example, as the lamination capacitors, the number of laminations also reaches hundreds of layers. For this reason, it is required to thin a ceramic layer and to further thin an inner conductor layer by this. For example, when the thickness of the ceramic layer is about 3 μm, the inner conductor film thickness is 1 μm or less, preferably about 0.5 μm, otherwise the center portion of the laminate becomes thick, leading to structural defects or poor reliability.
    However, in a conventional paste using a nickel powder, during firing, the internal conductor becomes a discontinuous film due to over sintering, resulting in an increase in resistance value or disconnection, or consequently thickening of the nickel powder results in thick conductor thickness. There was a problem of losing, and there was a limit to thinning. That is, nickel powder, especially when fired in an inert atmosphere or a reducing atmosphere for oxidation prevention, starts sintering and shrinkage at a low temperature of 400 ° C. or less even in a single crystal powder having rapid sintering and relatively low activity. On the other hand, the temperature at which the ceramic layer starts sintering is generally much higher than this, for example, about 1200 ° C. with barium titanate, and does not shrink with the nickel film even when co-fired, so that the nickel film is stretched in the plane direction. . For this reason, small pores generated in the nickel film due to sintering at a relatively low temperature expand as the sintering in the high temperature region progresses, which is likely to be a large hole, and the film tends to grow in the thickness direction by agglomeration of nickel powder. do.
    Therefore, in order to reduce the thickness of the nickel inner conductor layer, it is necessary to make the nickel powder finer and at the same time have good dispersibility, making it difficult to form voids during firing, and matching the shrinkage shrinkage behavior with the ceramic layer. I think it is necessary.
    Such inconsistency of the sintering shrinkage behavior of the conductor layer and the ceramic layer, especially when the film thickness is thick, causes structural defects such as delamination and cracks, resulting in lower consumption and reliability.
    In order to suppress the sintering of a conductor up to the sintering start temperature of a ceramic layer, it has been examined variously. For example, by adding a large amount of ceramic powder having the same composition as that used for the ceramic layer, the start of shrinkage of the conductor film can be delayed to around 800 ° C in appearance. However, since the sintering of the metal powder itself is not suppressed, when firing at a high temperature of about 1300 ° C., the continuity and conductivity of the conductor film are consequently broken.
    An object of the present invention is to effectively suppress sintering of nickel powder at low temperature and to obtain a conductive film having high conductivity even when the film thickness is thin.
    In addition, when used for a conductor paste that is co-fired with an unbaked ceramic layer, such as a laminated electronic component, the sintering start temperature of the nickel powder is as close to the sintering start temperature of the ceramic layer as possible without breaking the electrical characteristics of the conductive and components. In addition, the shrinkage behavior is approximated with ceramics to prevent disconnection and structural defects of the conductor film, and to enable thin film at the same time.
    Another object is to provide a simple and excellent method for producing such nickel powder.
    This invention makes the summary a nickel powder which has a complex oxide layer represented by Formula (1) on at least one part of a surface:
    A x B y O (x + 2y) (1)
    (Wherein A represents one or two or more elements of Ca, Sr and Ba, and B represents one or two elements of Ti and Zr. X and y represent numbers satisfying the following equation. 0.5 ≤y / x≤4.5)
    The nickel powder may include at least one selected from the group consisting of boron oxide, aluminum oxide and silicon oxide.
    In addition, the gist of the present invention is a method for producing the nickel powder,
    (a) one or two or more of pyrolytic nickel compounds,
    (b) one or two or more of pyrolytic calcium compounds, strontium compounds and barium compounds,
    (c) a solution containing one or two or more of pyrolytic titanium compounds and zirconium compounds is added dropwise with a fine liquid;
    The dropwise addition of the liquid was heated to a temperature higher than the decomposition temperature of the nickel compound, the calcium compound, the strontium compound, the barium compound, the titanium compound and the zirconium compound to produce a nickel powder and at the same time, the nickel powder. It is characterized by depositing the composite oxide layer represented by Formula (1) in the vicinity of the surface.
    In addition, the gist of the present invention is a method for producing a nickel powder comprising, as an additive, one or two or more selected from the group consisting of boron oxide, aluminum oxide and silicon oxide,
    (a) one or two or more of pyrolytic nickel compounds,
    (b) one or two or more of pyrolytic calcium compounds, strontium compounds and barium compounds,
    (c) one or two or more of pyrolytic titanium compounds and zirconium compounds,
    (d) a solution containing one kind or two or more kinds of pyrolytic boron compounds, aluminum compounds and silicon compounds is added dropwise into a fine liquid;
    The dropwise addition of the liquid was heated to a temperature higher than the decomposition temperature of the nickel compound, the calcium compound, the strontium compound, the barium compound, the titanium compound, the zirconium compound, the boron compound, the aluminum compound and the silicon compound. And generating a nickel powder and depositing one or two or more of the complex oxide layer represented by formula (1) and boron oxide, aluminum oxide and silicon oxide in the vicinity of the surface of the nickel powder. .
    The present invention is directed to a ceramic laminate electronic component comprising a conductor paste containing one or two or more of the nickel powders and a conductor layer formed using the conductor paste.
    EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.
    The composite oxide represented by the formula (1) may be a type which covers the surface of the nickel powder or a type which segregates with high concentration on the surface and / or the surface of the nickel powder, but inhibits the sintering of the nickel powder. To be effective, it needs to be near the surface. In order to prevent contact between nickel metals, the entire surface is considered to be effective. However, even if the entire surface is not necessarily covered, an effective amount may be present on the surface as needed depending on the use, minor component risk, and required characteristics.
    The composite oxide layer has a phase represented by the formula (1) as a main phase. In the nickel powder having the composite oxide on the surface, sintering in the low temperature region is suppressed, and the amount of oxide can also delay the sintering to the vicinity of the sintering start temperature of the ceramics, and oversintering is prevented. For this reason, an increase in conductor resistance, disconnection, increase in film thickness, determination, etc., which are caused by a mismatch in shrinkage when the conductor layer and the ceramic layer are simultaneously fired, are prevented. Is formed. Thereby, thinning of the conductor layer in laminated parts etc. becomes possible.
    In the case of simultaneous firing with titanate-based or zirconate-based ceramic dielectric green sheets such as barium titanate and strontium titanate, since the composition of the composite oxide layer is the same as that of the dielectric, the sintering behavior is closer to that of the dielectric layer. It hardly affects the electrical properties of the dielectric layer.
    Since the atomic ratio of the constituent elements A and B of the composite oxide is too far from 1: 1, the dielectric characteristics may be broken, so it is preferable to set it in the range of 2: 1 to 1: 2. The ratio of the elements A, B and oxygen may not be necessarily a stoichiometric amount, but may have oxygen deficiency similarly to dielectric ceramics such as titanate-based ceramics that are commonly used. Depending on the composition of the ceramic fluid layer, oxides of various elements, such as manganese, magnesium, vanadium, tungsten, and rare earth elements, which are normally added to titanate and the like for property control, may be appropriately added.
    Although the amount of a composite oxide is effective even if it is a small amount about 0.1 weight% with respect to nickel, it is preferable to set it as 1 weight% or more. Even if the amount is too large, a significant improvement in the sintering inhibiting effect cannot be expected, and the conductivity is lowered by the decrease of the nickel fraction, so that up to about 50% by weight is practical.
    Boron oxide, aluminum oxide, and silicon oxide not only enhance the delayed sintering start effect, but also have an oxidation inhibitory effect on the nickel powder. Accordingly, the organic components of the paste can be removed without oxidizing nickel even in an atmosphere having a relatively high oxygen concentration during firing. It can be burned and removed. In particular, as will be described later, when the powder of the present invention is produced by spray pyrolysis, these oxides lower the melting point of the composite oxide produced at a high temperature and act as a flux that lowers the viscosity of the melt, thereby affecting the nickel powder surface. It is thought to improve the coating efficiency of the composite oxide and to enable uniform coating. In cooling, these precipitate in the amorphous state mainly in the particle system of the composite oxide layer and serve as a binder.
    The amount of boron oxide, aluminum oxide, and silicon oxide (hereinafter referred to as "binder material component") is too large to have an influence on the electrical properties of the dielectric and the like, and therefore it is preferable to set it to about 20% by weight in total with respect to nickel.
    The composite oxide layer may be formed by any method. For example, a method of attaching a calcium compound to the surface of a nickel powder by a wet method such as sol-gel method and calcining to form a composite oxide layer, spray pyrolysis, or mechanically mixing nickel powder and composite oxide The method of mixing and attaching is mentioned.
    Preferably, the powder of the present invention is prepared by spray pyrolysis. In the spray pyrolysis method, as described in JP-A-63-31522 or JP-A-6-279816, etc., a fine liquid is dropped by spraying a solution containing one or more metal compounds. The droplet is dropped to a temperature higher than the decomposition temperature of the metal compound, preferably at a high temperature near or above the melting point of the metal, and thermally decomposes the metal compound to precipitate the metal or alloy powder.
    According to this method, it is possible to obtain nickel powder with good crystallinity, high density and high dispersibility, and to easily control the particle size, and to form a compound element of a complex oxide such as calcium compound in the nickel compound solution of the raw material. By adding, since the nickel powder which has a composite oxide layer of this invention is obtained by one operation, there exists an advantage that a coating process is not required newly. In other words, oxides such as calcium precipitated by pyrolysis are considered to have a good crystallinity, so that they are splashed on the surface to form a composite oxide in the vicinity of the surface. At that time, the bonding interface between the nickel particles and the composite oxide is assumed to form an inclined structure of the metal-ceramic, and not only a firm bonding layer is obtained, but also destruction of the particle structure due to mismatch of the thermal expansion coefficient during firing. Since it prevents, it is thought that about 1000 degreeC maintains the stable metal-ceramic bonded structure even at high temperature, and works effectively for sintering prevention. Furthermore, since the composite oxide is deposited relatively uniformly on the surface, even a small amount can achieve a desired effect. In the spray pyrolysis method, the composition of the produced particles basically coincides with the composition of the starting metal compound in the solution, so that the composition can be easily controlled and is suitable for producing the nickel powder of the present invention.
    In the case of containing a binder component such as boron oxide, one or two or more of pyrolytic boron compounds, aluminum compounds and silicon compounds may be added to the raw solution.
    In the method of the present invention, as a raw material compound of the nickel compound and the composite oxide or the binder component, acetate, sulfate, oxyacetate, oxysulfate, chloride, ammonium complex, phosphate, carbonate, metal alcoholate, resinate, boric acid, silicic acid 1 type, or 2 or more types of thermally decomposable compounds, such as these, are used. Double salts, complex salts, and metal oxide colloidal solutions may also be used.
    A solution obtained by dissolving these metal compounds in water, an organic solvent such as alcohol, acetone, ether, or a mixed solvent thereof is dipped with a fine liquid by an atomizer such as an ultrasonic or two-fluid nozzle type, and then the decomposition temperature of the metal compound is lower than the decomposition temperature. Pyrolysis is performed by heating to high temperature. Although the heat treatment is preferably carried out at a high melting point or higher of nickel, it is possible to obtain the effect of being sufficiently splashed even at a temperature about 200 ° C. below the melting point. Especially when high density and shape uniformity are not required, there is no problem even at a temperature considerably lower than the melting point. The heating is performed in an atmosphere which does not substantially oxidize the nickel powder, such as in a reducing or inert atmosphere, preferably in a weakly reducing atmosphere containing hydrogen, carbon monoxide and the like.
    The conductor paste which uses the nickel powder of this invention as an electroconductive powder is manufactured by uniformly mixing and disperse | distributing in an organic vehicle according to a conventional method. If necessary, other conductive powders, inorganic binders such as glass powder, and other additives may be contained.
    The nickel powder of the present invention is particularly used for internal conductor pastes such as multilayer parts such as multilayer capacitors or multilayer PTC elements using titanium, zirconate and titanium oxide ceramics, composite parts and composite substrates in combination thereof, or external. Although suitable for conductor pastes, it can also be used for other normal film thickness conductor pastes.
    (Example)
    Next, an Example and a comparative example demonstrate this invention concretely.
    Examples 1-5
    Nickel acetate hexahydrate was dissolved in water to a nickel concentration of 50 g / 1. As shown in Table 1, barium acetate and titanyl acetate were added to the nickel element so as to be 0.1 to 20% by weight in terms of BaTiO 3 to prepare a raw material solution.
    A fine liquid was added dropwise to the raw material solution using an ultrasonic atomizer, and a gas adjusted to weak reduction was supplied as a carrier into a ceramic tube heated at 1500 ° C in an electric furnace. The droplets were thermally decomposed through a heating zone to produce nickel powder containing BaTiO 3 .
    Nickel and BaTiO 3 were detected only by analysis of the obtained powder by X-ray diffractometer. As a result of fluorescence X-ray analysis, the content of BaTiO 3 was consistent with the composition of the raw material solution. In addition, it was observed by the field emission-scanning electron microscope (FE-SEM) that the BaTiO 3 layer was present on the nickel powder surface.
    Next, the obtained nickel powder was subjected to thermomechanical analysis (TMA) and thermogravimetric fraction (TG) to evaluate the sintering behavior and oxidation behavior of the powder, and the sinter shrinkage start temperature and oxidation start temperature are shown in Table 1.
    Examples 6 and 7
    A nickel powder having, on the surface, a composite oxide layer having the composition shown in Table 1 was obtained in the same manner as in Example 4 except that the ratio of barium and titanium added was changed.
    The sinter shrinkage start temperature and the oxidation start temperature were measured by TMA and TG.
    Examples 8-12
    One or two or more of barium acetate, calcium acetate and strontium acetate, and one or two or more of titanium acetate and zirconyl acetate are added to the aqueous nickel acetate solution, and are shown in Table 1 in the same manner as in Example 4. A nickel powder having a composite oxide layer of composition was obtained.
    The sinter shrinkage start temperature and the oxidation start temperature were measured by TMA and TG.
    Examples 13-20
    Simultaneously with barium acetate and titanium acetate, one or two of boric acid, aluminum acetate, and cooidal silica are added to an aqueous nickel acetate solution, and the composite oxide and the binder having the composition shown in Table 1 on the surface in the same manner as in Example 1. A nickel powder having a component was obtained.
    Similarly, the sinter shrinkage start temperature and the oxidation start temperature were measured and shown in Table 1 together.
    Observation by FE-SEM confirmed that when the binder component was present, the coating efficiency of the composite oxide layer on the surface of the nickel particles was improved, and the coating was more uniform.
    Comparative Example 1
    Pure nickel powder was obtained like Example 1 except not adding barium acetate and titanyl acetate. Sinter shrinkage start temperature and oxidation start temperature are shown in Table 1.
    Table 1
    Composite Oxide CompositionCompound oxide addition amount (% by weight)BinderBinder addition amount (wt%)Shrink start temperature (℃)Oxidation Initiation Temperature (℃) Example 1BaTiO 3 0.1──590470 Example 2BaTiO 3 1.0──710470 Example 3BaTiO 3 5.0──980470 Example 4BaTiO 3 10.0──1040470 Example 5BaTiO 3 20.0──1090470 Example 6Ba 2 TiO 4 10.0──970460 Example 7BaTi 2 O 5 10.0──980510 Example 8Ba 0.7 Ca 0.3 TiO 3 10.0──1010470 Example 9BaTi 0.8 Zr 0.2 O 3 10.0──1000470 Example 10Ba 0.5 Ca 0.3 Sr 0.2 Ti 0.8 Zr 0.2 O 3 10.0──990470 Example 11CaTiO 3 10.0──1080470 Example 12SrTiO 3 10.0──1090470 Example 13BaTiO 3 10.0B 2 O 3 0.5920530 Example 14BaTiO 3 0.5SiO 2 0.5980520 Example 15BaTiO 3 10.0SiO 2 0.5890510 Example 16BaTiO 3 10.0SiO 2 0.81040530 Example 17BaTiO 3 10.0SiO 2 1.01010560 Example 18BaTiO 3 20.0SiO 2 1.51020600 Example 19BaTiO 3 50.0SiO 2 3.41030600 Example 20BaTiO 3 10.0SiO 2 + Al 2 O 3 0.9 + 0.11080600 Comparative Example 1────330340
    As can be seen from Table 1, while the pure nickel powder gradually started sintering shrinkage at about 300 ° C, the shrinkage start temperature of the nickel powder having the composite oxide layer increased by about 200 to 800 ° C. Incidentally, the inclusion of the binder component increased the oxidation start temperature of the nickel powder.
    The nickel powder of this invention can suppress sintering at low temperature by the composite oxide layer which exists in the surface, and can delay the shrinkage start at the time of baking of nickel paste to near the temperature at which ceramic starts sintering. Therefore, in an electronic component such as a multilayer capacitor, the sinter shrinkage behavior of the nickel conductor layer is close to that of the ceramic layer, whereby disconnection and structural defects of the conductor film are prevented. Moreover, since the composite oxide layer is a dielectric composition, it does not affect the dielectric layer and does not break the characteristics of the electronic component. Therefore, high-performance products with high reliability can be manufactured. In addition, the internal conductor layer can be thinned, and further miniaturization and high lamination of the laminated electronic component can be achieved.
    权利要求:
    Claims (8)
    [1" claim-type="Currently amended] Nickel powder which has a complex oxide layer represented by Formula (1) on one part or whole surface.
    A x B y O (x + 2y) (1)
    (Wherein A is at least one element selected from the group consisting of Ca, Sr and Ba; B represents at least one element selected from the group consisting of Ti and Zr; x and y are numbers satisfying the following formula) 0.5≤y / x≤4.5)
    [2" claim-type="Currently amended] The nickel powder according to claim 1, further comprising at least one member selected from the group consisting of boron oxide, aluminum oxide and silicon oxide.
    [3" claim-type="Currently amended] A method for producing the nickel powder claimed in claim 1,
    (a) at least one pyrolytic nickel compound,
    (b) at least one member selected from the group consisting of pyrolytic calcium compounds, strontium compounds and barium compounds,
    (c) a solution containing at least one member selected from the group consisting of a thermally decomposable titanium compound and a zirconium compound is added dropwise into a fine liquid;
    The dropwise addition of the liquid was heated to a temperature higher than the decomposition temperature of the nickel compound, the calcium compound, the strontium compound, the barium compound, the titanium compound and the zirconium compound to produce a nickel powder and at the same time, the nickel powder. A method for producing a nickel powder, comprising depositing a composite oxide layer represented by the formula (1) in the vicinity of the surface thereof.
    [4" claim-type="Currently amended] A method for producing the nickel powder claimed in claim 2,
    (a) at least one pyrolytic nickel compound,
    (b) at least one member selected from the group consisting of pyrolytic calcium compounds, strontium compounds and barium compounds,
    (c) at least one member selected from the group consisting of pyrolytic titanium compounds and zirconium compounds,
    (d) a solution containing at least one of pyrolytic boron compounds, aluminum compounds and silicon compounds is added dropwise into a fine liquid;
    The dropwise addition of the liquid was heated to a temperature higher than the decomposition temperature of the nickel compound, the calcium compound, the strontium compound, the barium compound, the titanium compound, the zirconium compound, the boron compound, the aluminum compound and the silicon compound. And generating a nickel powder, and depositing at least one selected from the group consisting of a complex oxide layer represented by formula (1) in the vicinity of the surface of the nickel powder, and boron oxide, aluminum oxide and silicon oxide. Method for producing a nickel powder.
    [5" claim-type="Currently amended] A conductor paste comprising nickel powder as claimed in claim 1.
    [6" claim-type="Currently amended] 6. The conductor paste of claim 5, wherein the nickel powder further comprises at least one member selected from the group consisting of boron oxide, aluminum oxide and silicon oxide.
    [7" claim-type="Currently amended] A ceramic laminated electronic component having a conductor layer formed by using a conductor paste containing a nickel powder as claimed in claim 1.
    [8" claim-type="Currently amended] 8. The ceramic laminated electronic component of claim 7, wherein the nickel powder further comprises at least one selected from the group consisting of boron oxide, aluminum oxide, and silicon oxide.
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    同族专利:
    公开号 | 公开日
    CN1214979A|1999-04-28|
    EP0916438B1|2003-05-14|
    US6007743A|1999-12-28|
    MY118457A|2004-11-30|
    EP0916438A1|1999-05-19|
    DE69814560D1|2003-06-18|
    CN1087669C|2002-07-17|
    CA2230506C|2000-05-09|
    JP3475749B2|2003-12-08|
    DE69814560T2|2003-11-20|
    KR100251872B1|2000-04-15|
    JPH11124602A|1999-05-11|
    SG73501A1|2000-06-20|
    CA2230506A1|1999-04-17|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1997-10-17|Priority to JP29963897A
    1997-10-17|Priority to JP299638
    1998-03-10|Application filed by 에이이치 아사다, 소에이 가가쿠 고교 가부시키가이샤
    1999-05-25|Publication of KR19990036449A
    2000-04-15|Application granted
    2000-04-15|Publication of KR100251872B1
    优先权:
    申请号 | 申请日 | 专利标题
    JP29963897A|JP3475749B2|1997-10-17|1997-10-17|Nickel powder and method for producing the same|
    JP299638|1997-10-17|
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