TW418142B - Composite nickel fine powder and method for preparing the same - Google Patents

Abstract

Composite nickel fine powder herein disclosed is characterized in that at least one member selected from the group consisting of oxides and complex oxides which comprise at least one metal element having an atomic number ranging from 12 to 56 or 82 and belonging to Group 2 to 14 of Periodic Table is carried on the surface of metal nickel fine particles. The composite nickel fine powder can be prepared by, for instance, adding an aqueous solution containing at least one member selected from the group consisting of water-soluble salts of the foregoing metal elements to a slurry containing metal nickel fine particles or surface-oxidized metal nickel fine particles; and then adjusting the PH of the mixture with an acid or an alkali to thus carry the metal oxide and/or complex oxide derived from the water-soluble salt on the surface of the metal nickel fine particles.

Description

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Health, Japan 1 Α7 Β7 V. Description of the Invention (1) [Technical Field of the Invention] The present invention relates to a composite nickel fine powder and a method for preparing the composite fine powder; wherein the composite nickel fine powder is suitable for use as Significant properties of the internal electrode material for the preparation of laminated ceramic capacitors, which have excellent resistance to metal nickel oxidation and diffusion of nickel oxide, especially during the removal of the adhesive, also has excellent heat shrinkage properties, so when manufacturing large sizes Laminated ceramic capacitors can prevent delamination and crack formation, and can produce thin, small-sized multilayer ceramic capacitors including ceramic dielectric layers and internal electrodes without compromising their dielectric and electrical properties "[技艺Background] Laminated ceramic capacitors are manufactured by placing ceramic dielectric materials and internal electrodes alternately in layers, applying pressure to connect them, and then singulating them by baking. In this regard, the internal electrode of the laminated ceramic capacitor is generally manufactured by forming a paste of the fine metal powder as an internal electrode material, printing a paste layer on a ceramic substrate, and placing a plurality of layers in layers. These printed substrates are then connected to each other by compression and heating to obtain singularized products, and finally heated and baked under reduced pressure. Regarding the material of the internal electrode, for example, platinum and palladium have been used, but a technology of replacing a precious metal (such as platinum and a handle) with a car metal (such as nickel) has been recently developed and promoted. However, although S uses a metallic nickel fine powder as an internal electrode material, although the heat shrinkage tendency depends on the particle size of the powder, it has a tendency to undergo rapid heat shrinkage at a temperature higher than about 400 to 500 ° C. For this reason, Fang uses fine metal nickel powder as the internal electrode material. For example, during the baking process, because the ceramic substrate and the fine metal nickel powder have a common Chinese national standard (CNS) during baking, A4 specification (21G χ 297 male--------- 310997 ------------- install -------- order --------- line (Please read the precautions on the back before filling this page) 4 1 8 1 4 2 A7 —— B7 V. Description of the invention (2) Differences in heat shrinkage characteristics between layers are likely to cause delamination and / or crack formation, And this has become a serious problem. In order to solve these problems, the inventors of the present invention have developed a combination of the town and / or the metal fine powder in a specific amount to improve the heat shrinkage characteristics of the metal nickel fine powder. Technology and has applied for a patent (Japanese Patent Application No. Hei 9-342793). At temperatures above 400 to 500 ° C, this technology can suppress the aforementioned rapid thermal shrinkage (the rapid thermal shrinkage is a conventional metal nickel) (Observed by fine powder), can change the rapid thermal shrinkage onset temperature to approximately 600 to 700t High temperature region. However, 'in order to prevent delamination and / or crack formation during baking, it is desirable to change the rapid thermal shrinkage starting temperature of the internal electrode material to a higher temperature region. This is because of the baking of laminated ceramic capacitors. The temperature may vary depending on the composition of the ceramic dielectric material, but the baking temperature for barium titanate ceramic dielectrics is generally in the range of about 1200 to 1400eC. In addition, when baking is performed and the ceramic substrate begins to contact the metal, it will generally The oxidation of the metal has a diffusion coefficient higher than that of the ceramic magnetic substrate. Therefore, at the grain boundary, it is easy to cause a metal oxide phase with a high diffusion coefficient to diffuse to a ceramic phase with a low diffusion coefficient. More details "When using a paste containing the conventional metal nickel fine particles" part of the metal nickel fine particles will be oxidized, and the obtained nickel oxide will diffuse into the Taumann dielectric material. As a result, some of the internal electrodes to be formed disappear. The tendency is to form defects in the internal electrodes, and due to the formation of ferrites, part of the Taurman dielectric layer has a tendency to damage its dielectric characteristics. It is quite difficult to manufacture a thin, small-size laminated ceramic ceramic including a Taoman dielectric material layer and an internal electrode layer (please read the precautions on the back before filling this page) ------- Order ----- ---- Line — Printed by the Consumers 'Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper is printed in accordance with Chinese National Standards (CNS> G Specification ⑽x 297 Gongchu) 2 310997 A7 V. Description of Invention (3) Capacitors' without damaging its media Electrical properties and charging properties. [Invention of the invention j As discussed in detail above, the phase is used to prepare pastes, and the phase is used as the important metal nickel fine powder as a preparation material (used for the production of laminated ceramics capacitors). ), The material must be oxidized, and during baking, it can prevent any oxidation m and at the same time can change the rapid thermal shrinkage starting temperature of the metal powder to a higher temperature zone ", in order to make the nickel fine powder heat shrink The curve is close to the heat shrinkage curve of the ceramic substrate. Therefore, the object of the present invention is to provide a composite nickel fine powder, which has remarkable properties suitable for use as an internal electrode material for preparing laminated ceramic capacitors, and particularly has excellent resistance to metal nickel oxidation and oxidation during binder removal. Nickel diffusion resistance, which has almost the same heat shrinkage curve as ceramic substrates, can prevent delamination and crack formation when manufacturing large-size laminated ceramic capacitors, and can manufacture ceramic dielectric layers and internal electrodes. Thin, small-sized multilayer ceramic capacitors without compromising their dielectric characteristics and electrical properties. Another object of the present invention is to provide a method for preparing the composite nickel fine powder by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. The inventors of the present invention have carried out extensive research to accomplish the foregoing object, and have found that the composite nickel fine powder having the aforementioned remarkable properties can fix oxides and / or complex oxides of specific metal elements on the surface of the metal nickel fine particles. Obtained, and found that the composite nickel fine powder can be prepared via wet-loaded processing, dry-loaded processing, or semi-dry-loaded processing ', thus completing the present invention based on these findings. '3L0997 This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 418142-A7 --------— B7 —_ 5. Description of the invention (4) According to the first purpose of the present invention The system provides a composite recording fine powder characterized in that at least one member selected from oxides and complex oxides is supported on the surface of metallic nickel fine particles, so that the oxide or complex oxide system includes at least one atomic range A metal element that is 12 to 56 or 82 and belongs to groups 2 to 14 of the periodic table. According to another object of the present invention, there is provided a method for preparing a composite fine powder, comprising the steps of adding at least one member selected from metal elements to a slurry containing fine metal nickel particles or fine metal nickel particles whose surface is oxidized. An aqueous solution of a water-soluble salt (each having an atomic range of 12 to 56 or 82 and belonging to groups 2 to 14 of the periodic table); then the pH of the mixture is adjusted with an acid or a base, thereby oxidizing the metal derived from the water-soluble salt The complex and / or the complex oxide are supported on the surface of the metallic nickel fine particles. According to a further object of the present invention, there is also provided a method for preparing a composite nickel fine powder, including the following steps: temporarily carrying at least one member of ultrafine particles selected from oxides and complex oxides to metal nickel fine particles or the surface of which is oxidized On the surface of metallic nickel fine particles, the oxide or complex oxide system contains at least one metal element having an atomic range of 12 to 56 or 82 and belonging to groups 2 to 14 of the periodic table; making it temporarily bear and adhere to it The nickel fine particles of the ultrafine particles on the collision with each other or with other objects' so that the ultrafine particles can be carried on the surface of the metallic nickel fine particles. According to still another object of the present invention, there is provided a method for preparing a composite nickel fine powder, comprising the steps of: dispersing at least one member of a suspension of ultrafine particles selected from oxides and complex gaseous substances by heating ( Please read the precautions on the back and fill in this page) -I --------- Order --------- line —, printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs China National Standard (CNS) A4 Specification (210 X 297 mm) 4 310997 A7 '--------- §1 ________ V. Description of Invention (5) (Please read the precautions on the back before filling this page) Mixed with metallic nickel fine particles or metallic nickel fine particles whose surface is oxidized, the oxide or complex oxide system contains at least one having an atomic range of 12 to 56 or 82 and belongs to groups 2 to 14 of the periodic table. Metal element, removing the medium of the suspension, so that the ultrafine particles can be temporarily carried on the surface of the metal nickel fine particles; the nickel fine particles temporarily with the ultrafine particles adhered thereto can collide with each other or with other objects Bump, so you can make ultrafine particles Carried to the upper surface of nickel fine particles. [Specific specific example description] The composite nickel fine powder according to the present invention includes metal nickel fine particles and at least one member selected from oxides and complex oxides, the latter being carried on the surface of metal nickel fine particles; The composite oxide contains at least one metal element having an atomic range of 12 to 56 or 82 and belonging to Groups 2 to 14 of the periodic table. Therefore, the composite nickel fine powder of the present invention has a heat shrinkage characteristic very similar to that of a ceramic substrate. In this way, delamination and crack formation can be prevented when manufacturing large-scale laminated ceramic magnetic capacitors. In addition, the composite nickel fine powder has excellent oxidation resistance and diffusion resistance during the removal of the binder, so it can be manufactured including ceramic dielectric materials and internal electrodes. Multilayer multilayer ceramic capacitors without compromising the dielectric characteristics and electrical properties of the capacitors. When manufacturing thin, small-size multilayer laminated ceramic capacitors including ceramic dielectric materials and internal electrodes without compromising the dielectric characteristics and electrical properties of the capacitors, the paste containing the composite nickel fine powder of the present invention can be used in During the removal of the adhesive, 'to fully prevent the oxidation of the fine nickel metal powder and prevent any diffusion of nickel oxide to the ceramic magnetic dielectric layer' or due to the elimination of some internal electrodes to be formed. The paper dimensions are applicable to China National Standard (CNS) A4 specifications (210 X 297 mm) 5 310997 4 Ί 8 1 4 2 ″ from A7 ---- B7 V. Description of the invention (6) Loss of the functional part of the ceramic dielectric layer can also prevent any damage to the internal electrode; the compound of the invention The nickel fine powder preferably includes metal nickel fine particles and at least one member selected from the group consisting of oxides and complex oxides, the oxides or complex oxides containing at least one type * having an atomic range of 12 to 56 or 82 and belonging to the periodic table Group 2 to 7 or Group 13 to 14 metal elements; and the composite nickel fine powder preferably includes metal nickel fine particles and at least one member selected from the group consisting of oxides and complex oxides. The oxide contains at least one metal element having an atomic range of 12 to 56 or 82 and belonging to Group 2, 3, 4, 7, 13 or 14 of the Periodic Table; wherein the oxide or complex oxide is supported on metallic nickel Fine particles on the surface. Furthermore, it is preferable to use a composite nickel fine powder including metal nickel fine particles and at least one member selected from metal element oxides belonging to Group 2, Y, Zr, Ab and Si in the periodic table, the latter being carried to the metal nickel fine On the surface of the particle. Regarding the foregoing composite oxide, the present invention can use a plurality of composite oxides including any one of the foregoing and the following. When the composite nickel fine powder of the present invention is used as the internal electrode material of a laminated ceramic capacitor, the composite chain fine powder of the present invention can be selected from at least-members such as the oxides and complex oxides listed above, and at least _ The oxide is selected from lanthanide oxides and is adhered to the surface of fine particles of metallic nickel. When the composite nickel fine powder of the present invention is used as an internal electrode material of a laminated Taunman capacitor, the composite nickel fine powder of the present invention preferably includes a metal fine powder and at least one member selected from the complex compounds represented by the following general formula: This paper size applies the national standard (CNS) A4 specification (210 «297 mm) (Please also read the precautions on the back before filling out this page)

-I -------- Order · ------- II Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 310997 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 ____________ V. Description of Invention (7 ) (Where 'X represents sr, Ca, Mg or Pb; z represents Zr, γ, Sn or Ge; m is a number in the range of 0 to 1; η is a number in the range of 0 to i), the complex oxidation The object is carried on the surface of fine particles of metallic nickel. In this regard, the aforementioned complex oxides may be used alone or in combination of at least two kinds, or the complex oxides may further include, for example, at least one member selected from the foregoing various halide compounds, oxides of lanthanoids, and oxides Bismuth and oxidation group, as the minor components as appropriate. For example, the aforementioned oxide and complex oxide may be .Mg〇, Ca〇,

SrO, BaO, ZnO, Al2O3, Ga2.03, Y2O3, si02, Ti02, Zr02,

Cr203, Mn02, Mn304, Nb205, BaTi〇3, CaTi03, SrTi03, BaZr03, CaZr03, SrZr03, (Mg, Ca) Ti〇3, (Ba, Ca) (Ti,

Zr) 03, PbTi03, Pb (Zr, Ti) 〇3, (Pb, Ca) Ti03, MgAl2O4, and BaTi4 09 'can be used in combination. In addition, these oxides and complex oxides may be doped with, for example, oxides of Nb, W, La, Y, and Mo. For example, the oxide of the aforementioned lanthanide group element may be Nd203,

Sm203, Dy203, Er203, and Ho203. When the composite micro-recorder of the present invention is used in the form of a paste to manufacture an internal electrode of a laminated ceramic capacitor, it may preferably have a particle size of not more than 5em, more preferably not more than lym. In addition, with respect to the total amount of the composite nickel fine powder, at least one member of the foregoing nickel fine particles to be carried on the metal nickel fine particles is preferably selected from the foregoing oxides or complex oxides in a range of 0.05 to 10% by weight, more preferably. -5 to 10% by weight 'Extremely preferred is 1 to 10% by weight. This is because if the total amount of supported oxides and / or complex oxides is less than 0.055% by weight, then the oxides and / or ------------- install --- I ---- Order ------- line (please read the precautions on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 (21〇x 297) 7 310997 A7 418142 V. Description of the invention (8) The effect of the complex oxide is insufficient, and if it exceeds 10% by weight, and the composite fine powder is used as an internal electrode material for manufacturing a laminated ceramic capacitor, these oxide pairs The dielectric characteristics of the resulting capacitor have an adverse effect. The metallic nickel fine particles used in the method of the present invention or the metallic nickel fine particles whose surface is oxidized may be subjected to dry treatment (for example, vapor phase hydrogen reduction with nickel salt vapor) or wet treatment (under specific conditions, which contains nickel) The aqueous salt solution is reduced with a reducing agent, and the fine particles of the metal particles are allowed to sink. When the composite nickel fine powder of the present invention is used in the form of a paste for manufacturing an internal electrode of a laminated ceramic capacitor, the metal nickel fine powder to be used preferably has a particle size of not more than 5 / zm, more preferably not more than iym. The composite nickel fine powder according to the present invention can be prepared through wet load-bearing processing or dry load-bearing processing, or further semi-dry load-bearing processing, including the following steps. An ultrafine particle aqueous suspension of metal oxide or complex oxide and metal The nickel fine particles are mixed, the ultrafine particles are carried on the surface of the metal nickel fine particles, and then the metal nickel fine particles carrying the ultrafine particles are dried. If the composite nickel fine powder of the present invention is prepared by wet-supporting processing, at least one member selected from metal elements (each having an atomic range) is added to the slurry containing the metal nickel fine particles or the surface-oxidized metal nickel fine particles. It is an aqueous solution of water-soluble salts of 12 to 56 or 82 and belongs to groups 2 to 14 of the periodic table, and then adjusts the value of the mixture with acid or alkali to thereby convert water; metal salts and / or complex gases derived from cereal salts. The compound is carried on the surface of the metal particles. If the composite nickel fine powder of the present invention is prepared by wet load processing, (please read the precautions on the back before filling this page) Order --------- Online 丨 Printed by the staff consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The size of this paper applies Yin National Standard (CNS) A4 (21〇χ 297 mm) 8 310997 A7 V. Description of the invention (9) Fine particles of metal recorded as raw materials can be

^ ^ U. ^ ^ A or I induced by wet treatment. In this respect, the composite recording fine powder can be wound in a low-temperature, uniform wet treatment operation. According to the above-mentioned wet treatment, the fine particles are used as raw materials, and if appropriate, the wet treatment is used to adapt the nickel fine particles of the 2 gens of nickelized metals. Then, according to the method of wet bearing, 4 slightly fine powder. In this regard, when to use? When the complex is prepared, the oxidizing agent a of the metallic nickel fine particles that slightly oxidizes the surface is described as oxides and / or oxides are easily formed on the surface of the metallic nickel fine particles. A kind of water-soluble as (which is performed according to wet-bearing processing) used in the production of the composite nickel fine powder of the present invention is not particularly limited as long as they are soluble: water and can be converted into water-insoluble oxides or complex oxides Just fine. Examples thereof include the dentate, nitrate, sulfate, oxalate, sulfide, and magnetic metal salts of the aforementioned metal elements, such as aluminate and silicate. When the method for manufacturing the composite nickel fine powder according to the present invention is performed by wet-bearing processing, the pH adjuster may be selected as an acid or an alkali depending on the type of the water-soluble salt used above, and the types of these acids and alkalis are not particularly limit. < For example, if the oxides in the parentheses are formed by using the following water-soluble salts, then an aqueous sodium hydroxide solution can be used: titanium sulfate (Ti02); manganese sulfate (Μη02); gasification complex (Cr203) ); Vaporized yttrium (rhenium 203); vaporized samarium oxide (Zr02). In addition, if the oxides in the parentheses are formed by using the following water-soluble compounds, dilute sulfuric acid may be used: sodium aluminum sulfonate (αι2ο3); sodium silicate (Si02). This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Development 310997 4 18 1 5. Description of the invention (10) The aforementioned water-soluble salts will be converted to their oxidation Or complex oxides, and the pH value of the water-soluble salt solution is adjusted as discussed above, deposited and carried on the surface of the metal fine particles to obtain the composite nickel fine powder of the present invention. -The manufacturing method of the composite nickel fine powder and powder according to the present invention is performed according to wet load processing. In addition to the aforementioned processing steps, it may further include subsequent washing and / or drying steps. However, the aforementioned water-soluble dendrite-derived metal oxides and / or complex oxides are carried on the surface of metallic nickel fine particles according to wet-loading processing, and then washed and dried 'followed by carrying oxides and / or complex oxides thereon. Fine particles of metallic nickel carried by the substrate may be subjected to additional steps, such as processing with a device such as a 0ng grinder, a hybrid machine, a mechanofusion, a Coat Mizer, a Disper Coat, or a Jet Mizer, in which the metallic nickel fine particles are made Collision with each other or with other objects, and the ultrafine particles are tightly supported on the surface of the metallic nickel fine particles. In the method for producing a composite nickel fine powder according to the present invention, which is carried out according to dry load processing, at least one member of ultrafine particles selected from oxides and complex oxides is temporarily carried to metal nickel fine particles or metal nickel fine particles having a surface that has been denatured. On the surface, the oxide or complex oxide system contains at least one metal element having an atomic range of 12 to 56 or 82 and belonging to groups 2 to 14 of the periodic table. The nickel fine particles of the particles collide with each other or with other objects, and the ultrafine particles are carried on the surface of the metallic nickel fine particles. When the method for manufacturing the composite nickel fine powder according to the present invention is performed according to dry load processing, and the obtained composite nickel fine powder is used in the form of a paste for wood making paper, the size of the Chinese national standard (CNS) A4 (210x 297 mm) is applicable. By) — (Please read the note on the back · 1 ^ · item before filling out this page) Order --------- line 丨, printed by A7 of the Intellectual Property Bureau Staff Consumer Cooperatives of the Ministry of Economic Affairs V. Invention Description (11 When manufacturing the internal electrode of the laminated ceramic capacitor, the metal particles or surface oxidized metal particles used in the method of the invention preferably have a particle size of not more than m, more preferably not more than these oxides. The smaller the particle size of the ultrafine particles of the complex oxide and / or the smaller the required amount for uniformly supporting the metal nickel fine particles. According to this reason, the particle size is preferably not more than 0.5am, more preferably not more than 0. , The best is not more than 0.05mm.) In order to carry the aforementioned ultrafine particles of metal oxides and / or complex oxides onto the metal fine particles or the surface is oxidized & the surface of the metal fine particles, then mixing is required. Former and later That is, the metallic nickel fine particles temporarily carrying the ultrafine particles collide with each other or with other objects, thereby ensuring that the ultrafine particles adhere to the surface of the metallic nickel fine particles. Alternatively, metal nickel fine particles and ultrafine particles of metal oxides and / or complex oxides are filled in a device, such as a ng mill, a hybrid, a mechanical fusion, a Coat Mizer, a Disper Coat, or a Jet Mizer, while mixing and carrying the latter onto the former. k Member of the Ministry of Economic Affairs, Intellectual Property, X, and Consumer Goods Co., Ltd. Printed the manufacturing method of the composite nickel fine powder according to the present invention, which was carried out according to semi-dry load processing, and used heating to disperse at least one member and selected from oxides and oxides. A suspension of ultrafine particles of a complex oxide is mixed with fine particles of metallic nickel or fine particles of metallic nickel whose surface is oxidized, wherein the oxide or complex oxide contains at least one having an atomic range of 12 to 56 or 82 and Metal elements belonging to groups 2 to 14 of the periodic table are then removed from the suspension medium, and the ultrafine particles are temporarily carried on the surface of the metal nickel fine particles, and the metal records temporarily holding the ultrafine particles adhered thereto Fine particles collide with each other or collide with other objects' while ultrafine particles will be used. 11 This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 male cage) 310997 (Please read the precautions on the back before filling this page)

41 «142 V. Description of the invention (l2) Carried on the surface of fine particles of metal wire. The metal nickel mold fine particles or surface-oxidized metal nickel fine particles and ultrafine particles of metal oxides and / or complex oxides that can be used in the aforementioned semi-dry load processing are the same as those in the aforementioned dry load plus work station. In addition, the medium for suspending ultrafine particles is not particularly limited, and generally, for example, ash, an acidic aqueous solution, a test aqueous solution, an alcohol, or other organic solvents are used. In this manufacturing method, the suspension used can be prepared by dispersing ultrafine particles of the desired oxide or complex oxide to a predetermined solid content concentration, or, for example, commercially available two The silica sol, alumina sol, titania sol, and barium titanate sol can be diluted if necessary to adjust the concentration to a desired level. The following examples, comparative examples, and preparation examples are described in more detail below. The invention is described, but the invention is not limited to these specific embodiments at all. Comparative Example 1 244 g of solid main sodium hydroxide was dissolved in pure water, and the resulting solution was then diluted with pure water to a total volume of 430 ml to obtain a sodium hydroxide aqueous solution. On the other hand, 448 grams of nickel sulfate (NiS04. 0H20; a product with a quality level of 22.2% by weight) was dissolved in pure water (use warm water; ensure immediate and complete dissolution) 'and then the resulting solution was diluted with pure water to the total The volume was 1,000 ml 'to obtain an antimony sulfate aqueous solution. The obtained nickel sulfate aqueous solution was added to the aforementioned sodium hydroxide aqueous solution at a rate of 20 ml / min over a period of 50 minutes. After the temperature of the hydroxide-containing slurry thus prepared rose by up to 60 ° C, 420 g of hydrazine monohydrate was added to the slurry at one time to reduce argon oxide. Wash the obtained metallic nickel fine powder with pure water, and continue washing with water until 1-1 — ^ --- vk -------- Order --------- line < Please read the back ta first ..t matters, please fill out this page again) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Consumption Cooperative, this paper is printed in accordance with China National Standard (CNS) A4 (210 X 297 public love) 12 310997 A7 A7 Μ Consumer Property Cooperative of the Ministry of Economic Affairs Printing 5. Description of the invention (U) The pH value of the washing liquid reaches a level of not more than 10, and then it is filtered and dried according to conventional methods to obtain a fine metal nickel powder. The obtained metallic nickel fine powder was judged by SEM observation to have an average particle size (Feret, s diameter: average particle size of major particles) of 0.2, and it was found to have a microscopic uneven surface. Comparative Example 2 Except that 420 g of the hydrazine monohydrate containing the hydroxide-containing liquid used for reduction heating to 60 ° C. was continuously added to the slurry within 20 minutes, instead of one time addition, the same was used as in Comparative Example 1. The same steps were used to prepare nickel fine powder. The obtained metallic nickel fine powder was judged by SEM observation to have an average particle size (Feret's diameter) of 0,2em, and it was found to have a micro uneven surface. A fine nickel powder (having a micro uneven surface) composed of a fine powder to a Hybridizer (purchased from Nara Kikai Seisakusho), and circulated in the machine at 8000 rpm for 5 minutes, and The treatment was performed. The fine particles of metallic nickel obtained after the treatment were judged to have an average particle size by SEM observation of 0.2 / zm ′ and were found to have a smooth surface. Comparative Example 4 A metallic nickel fine powder prepared in Comparative Example 2 was filled. The composed nickel fine powder (which has a microscopic uneven surface) is passed to a hybrid machine (purchased from Nara Machinery Manufacturing Co., Ltd.) and circulated in the machine for 5 minutes at 8000 rpm. ◎ The metallic nickel fine particles obtained after the treatment have an average particle size (Feret's diameter) of 0.5 (am) and are found to have a smooth surface by SEM observation. I This paper size applies the Chinese National Standard (CNS) A4 specification ( 21G X 297 public meal) 丨 -— 13 310997 Please read the notes of the back first, then I fill in the $ binding page 0142 A7 ---- B7 V. Description of the invention (W) Preparation Example 1 100 g The metallic nickel fine powder prepared in Comparative Example 1 was added to 1 liter of pure water 'followed by stirring to obtain a slurry. After stirring the slurry for 30 minutes, 100 g of an aqueous hydrogen peroxide solution was added thereto at a time. When the generation of air bubbles was terminated (this table When the reaction is not completed), stirring is stopped, followed by filtration and drying to obtain fine metal nickel powder with an oxidized surface. The obtained fine metal nickel powder was found to have an average particle size (Feret, s diameter) of 0.02 by SEM observation. Preparation Example 2 100 g of the metallic nickel fine powder prepared in Comparative Example 2 was added to J liters of pure water, followed by stirring to obtain a slurry. After the slurry was stirred for 30 minutes, 100 g of an aqueous hydrogen peroxide solution was used. It is added twice. When the generation of air bubbles is stopped (the reaction is complete), the stirring is stopped, and then the surface is oxidized to obtain fine metal nickel powder. The obtained fine metal nickel powder is found to have an average particle size by SEM observation. , S diameter) is 0. 5 melons. Example 1 100 g of finely oxidized metal nickel powder prepared in Preparation Example 1 was added to 1 liter of pure water, followed by stirring to obtain a slurry, and the slurry was heated to 6 0t and the slurry was maintained at this temperature. 19 2 g of sulfuric acid '(a product having a Ti a content of 5% by weight) was added to the slurry at one time, and an aqueous sodium hydroxide solution (NaOH ·· 1N) was added to adjust the pH of the mixture to 8. Stirring was continued for another hour], followed by filtration and drying to obtain a composite nickel fine powder with Ti0 2 adhered to the surface of the metal nickel particles. Example 2 __ 100 grams of surface-oxidized metallic nickel fine powder coated paper prepared in Preparation Example 2 was applied to the Chinese National Standard (CNS) A4 specification (2iQ χ ----------- W 310997 A7- —-B7 V. Description of the Invention (I5) Added to 1 liter of pure water, and then searched to obtain the liquid, the liquid was heated to 60 C and the liquid was maintained at this temperature. Dissolved from 5 g of gasification complex The aqueous solution prepared by the pure water was added to the subsequent solution at one time, and an aqueous solution of sodium oxynitride (NaOH: 1N) was added to adjust the pH value of the mixture to 7. Under these conditions, stirring was continued for 1 hour, followed by transition and drying. A composite nickel fine powder with CqO3 adhered to the surface of the metal nickel particles was obtained. Example 3) 100 g of the finely oxidized metal nickel powder prepared on the surface prepared in Preparation Example 1 was added to 1 liter of pure water, and was then given off to A charge was obtained, and the polymer was heated to 60 C and the slurry was maintained at this temperature. An aqueous solution prepared by dissolving 65 g of sodium silicate (water glass) in 60 ml of pure water was added to the slurry and dilute sulfuric acid was added to adjust the pH of the mixture to 6. Under these conditions, the mixture was stirred for 1 hour, followed by drying and drying to obtain a composite nickel fine powder with SiO2 adhered to the surface of the metal recording particles. Example 4 j 100 g of the surface-oxidized metallic nickel fine powder prepared in Preparation Example 1 was added to 1 liter of pure water, followed by stirring to obtain a slurry. The slurry was heated to 60 ° C and the slurry was maintained at this temperature. An aqueous solution prepared by dissolving 35 g of yttrium vaporized solution in 50 ml of pure water, and adding an aqueous solution of sodium hydroxide (NaOH: 1N) to adjust the ipH value of the mixture to 6. Stirring was continued for 1 hour under these conditions, followed by filtration and drying to obtain a composite nickel fine powder with IA adhered to the surface of the metal nickel particles. Example 5 The surface-oxidized metal nickel fine powder 15 310997 prepared in Preparation Example 1 (please read the precautions on the back before filling out this page) ^ Paper size applies Chinese National Standard (CNS) A4 size coffee x 297 male cages ) ---------- Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A 1 〇 ^ A ^ A7 ------____ _ V. Description of the invention (l6) Added to 1 liter of pure water Then, it is taught to obtain the setting liquid, the stimulus is heated to 60 C and the liquid is maintained at this temperature β. The aqueous solution prepared by 35 g of gasification and dissolved in% ml of pure water is added to the beam liquid at a time, and Aqueous sodium oxide solution (NaOH: 1N) was added to adjust the pH value of the mixture to 6. Under these conditions, they were searched and mixed for 1 hour, followed by quenching and drying to obtain a composite nickel fine powder with ZrO2 adhered to the surface of the metal nickel particles. Example 6 100 g of the surface-oxidized metallic nickel fine powder prepared in Example 1 was added to 1 liter of pure water and then 'stirred to obtain a slurry'. The slurry was heated to 60 C, and 3.9 g of an aqueous titanium thiosulfate solution (Ti Content: 5% by weight). An aqueous solution of sodium hydroxide (NaOH: 1N) was further added to the slurry to adjust its pH to 8, followed by stirring for 1 hour. The slurry is then filtered, and once reslurried, it is filtered again. The filter cake thus obtained was added to 1 liter of pure water to obtain a slurry. Then, a solution prepared by dissolving 2.62 g of barium oxide in warm water was added to the slurry at one time, and an aqueous sodium hydroxide solution (NaOH: 1N) was added to adjust the pH of the mixture to not less than 12. Under these conditions, stirring was continued for 1 hour, followed by mashing and drying to obtain a composite fine powder with BaTi03 adhered to the surface of the metallic nickel particles. Example 7 100 g of the finely oxidized metallic nickel powder prepared in Preparation Example 2 was added to 1 liter of pure water, followed by stirring to obtain a slurry. The slurry was heated to 60 ° C and the slurry was maintained at this temperature. An aqueous solution prepared by dissolving 15.7 g of manganese sulfate in 100 ml of pure water was added to the slurry at one time, and an aqueous sodium hydroxide solution (NaOH ·· 1N) was added to adjust the pH of the mixture to 8. The national standard of the ordering country is applied to the size of the paper (4A4 size⑵㈣7⑵㈣⑻ 16 310997 -------- Order --------- line, please read the precautions on the back before filling this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 310997 A7 B7 V. Description of the invention (l7) Continue stirring for 1 hour, and then filter and dry to obtain a composite fine powder with Μπ02 adhered to the surface of the metal record particles . Example 8 100 g of the finely oxidized metallic nickel powder prepared in Preparation Example 2 was added to 1 liter of pure water ', followed by stirring to obtain a slurry. The slurry was heated to 50 ° C and the mash was maintained at this temperature. An aqueous solution prepared by dissolving 55 g of sodium aluminate in 100 ml of pure water was added to the slurry at one time, and dilute sulfuric acid was added to adjust the pH of the mixture to 8. Stirring under these conditions] hours', followed by filtration and drying to obtain a composite fine powder with Al 2 O 3 adhered to the surface of metallic nickel particles. Example 9 100 g of the finely oxidized metallic nickel powder prepared in Preparation Example 2 was added to 1 liter of pure water, followed by stirring to obtain a slurry. The slurry was heated to 60 C and the slurry was maintained at this temperature. An aqueous solution prepared by dissolving 104 g of gallium nitrate in ml of pure water was added to the slurry at one time and an aqueous sodium hydroxide solution (NaOH: 1N) was added to adjust the pH of the mixture to 9. Continue to search under their conditions! After 1 hour, the mixture was dried and dried to obtain a composite nickel fine powder with Ga203 bonded to the surface of the metal nickel particles. Example 10 The finely powdered metal front of the surface prepared by ⑽S Preparation Example 2 was added to 1 liter of pure water ', and then the mixture was obtained to obtain a polymer solution, and the solution was heated to 0 ° C and 39 g of sulfuric acid was added at a time Titanium aqueous solution (τι content: $ weight improvement) Add slurry of sodium argon oxide aqueous solution (NaOf ^ 1N) to adjust its pH to 8, and then stir it for 1 hour. Then filter the slurry,

Refer to the paper f scale for medium ^ boots NS) A4 specifications (heart, male II — — — — — — — — — — — IIIIIII. I — I— I — II (Please read the precautions on the back before filling (This page) A7 4i b 1 4 2 ----- B7 " ---------- V. Description of the invention (IS) Once it is re-slurry ', it will be filtered. The filter cake thus obtained is added to j liters Obtaining a slurry in water "Then a solution prepared by dissolving 2.0 g of strontium gas in warm water was added to the slurry at one time, and an aqueous sodium hydroxide solution (NaOH: 1N) was added to adjust the pH of the mixture to not less than 12. Under these conditions, stirring was continued for 1 hour, followed by filtration and drying to obtain a composite nickel fine powder with SrTi03 adhered to the surface of the metal nickel particles #. The composite nickel fine powder prepared in Examples 1 to 10 above and the aforementioned comparison The fine metal nickel powders of the apparatuses of Examples 1 to 2 were tested for heat using a deformation thermal analyzer (purchased from Rigaku Denki KK ·) under a nitrogen pressure at a heating rate of 10 ° C / min. Shrinkage. The results thus obtained are detailed in Table 1 below. Table 1 Example Fere t ’s oxide adhesion calorimetric shrinkage (〇 / 〇)

Number Diameter Type (%) 500 ° C 700 ° C 900 ° C ll00 ° C 1 0.20 Ti02 0.97 -0.25 -0.17 -1.92 -7.08 2 0.20 Cr, 0, 0.95 -1.25 -2.29 -6.96 -11.96 3 0.20 Si 〇2 0.90 -0.63 -0.02 -0.83 -3.46 4 0.20 Y203 0.95 -1.08 -0.83 -3.06 -4.83 5 0.20 Zr02 0.98 -0.77 -0.58 -6.38 -11.83 6 0.20 BaTi03 0.96 -1.25 -1.45 -3.96 -14.08 7 0.50 Μη02 2.88 -0.92 -0.98 -5.83 -12.92 8 0.50 Α12〇3 0.89 -1.35 -0.98 -1.46 -8.04 9 0.50 Ga203 0.88 -1.28 -2.17 -4.52 -9.58 10 0.50 SrTiO, 0.91 -1.04 -1.99 -2.75 -5.09 1 * 0.20 — — -0.83 -1.98 -9.69 -15.35 2 * 0.50 — — -0.56 -0.69 -7.88 -14.46 氺: Comparative examples can be found from the data listed in the order in Table 1, and gold c in Comparative Examples 1 to 2 please Read the unintentional matter on the back before filling this page) Order --------- line-Printed by the Intellectual Property Bureau Staff Consumer Cooperatives of the Ministry of Economic Affairs This paper applies the national standard (CNS) A4 specification (210 X 297 mm) 18 310997 A7 A7 • Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 310997 V. Description of Invention (i9) Compared with nickel fine powder, implemented Shu to nickel composite fine powder (Invention) 10 having the large heat of a relatively low ratio at a high temperature. Tube Example 11 500 g of the fine metal powder prepared in Comparative Example 2 and 35 g of ultrafine alumina particles (alumina c purchased from Nippon Aerosii Co., Ltd.) ; Average particle size of main particles: 13 nm; Mixing ratio with respect to metal nickel fine powder: 7% by weight) Stir for 4 minutes and mix for 5 minutes to obtain a record including ultrafine particles of oxide particles temporarily carried on the surface of metal nickel fine particles Fine duster. In addition, the powder was filled into a hybrid machine (purchased from Nara Machinery Manufacturing Co., Ltd.), and the powder was processed by circulating the powder in the machine at 8000 rpm for 5 minutes to obtain oxidation including loading on the surface of the fine particles of the metal recorder. Composite nickel fine powder of aluminum ultrafine particles. Since alumina ultrafine particles are supported on the surface of metallic nickel fine particles of the obtained composite nickel fine powder, even if alumina ultrafine particles are added to water (in the case of powder systems obtained by simple mixing with stirring, alumina ultrafine The particles were suspended in water and the water became cloudy), and no removal and floating of any alumina ultrafine particles was observed. In addition, the obtained composite nickel fine powder was examined by SEM observation, and it was confirmed that the alumina ultrafine particles were uniformly carried on the surface of the composite nickel fine particles, and it was confirmed that the particle size of the composite particles was almost equal before and after the adhesion step. Example 12 Except replacing the 35 grams of ultrafine alumina particles used in Example 丨 with 2.5 grams of ultrafine alumina particles (mixing ratio with respect to metallic nickel fine powder: 0-5 weight), repeat the use as in Examples 丨 丨For the same steps, I paper size applies the Chinese National Standard (CNS > A4 specification (21G X 297 public meal — 丨 ·! 1-1111—1 ^^. I —---— I order .---- II ( (Please read the notes on the back before filling out this page) Α7

V. Description of the invention (M) to obtain a composite nickel fine powder including oxidized ultrafine particles carried on the surface of the fine particles of the metal record β. Examples 13 to 26 4! D I ^! · 2 Bureau of Intellectual Property, Ministry of Economic Affairs Employee Consumer Cooperative printed 500 grams of metal nickel fine powder prepared in Comparative Example 2 and 25 grams (mixing ratio with respect to metal recording fine powder: 5% by weight) or 5 grams (mixing ratio with respect to metal recording fine powder: 1 % By weight) The following ultrafine particles are stirred and mixed for 15 minutes: ultrafine titanium oxide particles: f (purchased from Japan Erosin Corporation!> 25; average particle size of main particles: 13nm), ultrafine silicon dioxide particles (300CF purchased from Japan Eros Silicon Co., Ltd .; average particle size of main particles: 7 nm), ultra-fine magnesium oxide particles (1 purchased from Ube Material Co., Ltd.) 〇A; average particle size of main particles: 10 rim), ultrafine yttrium oxide particles (purchased from CI Chemical Industries, Ltd .; average particle size of main particles: 10 nm), ultrafine titanic acid Barium particles Prepared according to the sol-gel method using titanium peroxide and barium peroxide; the average particle size of the main particles: 30 nm), ultrafine gill titanate particles (based on the sol-gel method, using titanium peroxide and barium peroxide) Prepared; average particle size of main particles: 10 nm), or ultrafine barium strontium titanate (Ba〇9Sr () i) Ti03 particles (prepared according to sol-gel method; average particle size of main particles: 10 nm ) To obtain metallic nickel fine particles including any of the foregoing ultrafine particles temporarily carried on the surface of metallic nickel fine particles. In addition, the powder was filled into a hybrid machine (purchased from Nara Machinery Manufacturing Co., Ltd.), and the powder was processed by circulating the powder in the machine at 8000 rpm for 5 minutes to obtain the foregoing including loading onto the surface of metallic nickel fine particles. Any kind of ultra-fine particles of composite nickel fine powder. ------------ II 'I ----- II -------- ^ C Please read the notes on the back before filling this page) This paper size applies to the national standards of the competing countries (CNS) A4 specification (210 × 297 mm) 20 310997 A7 B7, printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention () Example 27 Except for a mechanical melting machine (purchased from Hosokawa Micron Co., Ltd.) (Hosokawa Micron Co., Ltd.)) Instead of the hybrid machine (purchased from Nara Machinery Manufacturing Co., Ltd.) used in Example 11 ', the powder was cycled in the machine for 30 minutes at 3000 rpm, and the process was repeated. The same procedure was used as in Example 11 to obtain a composite nickel fine powder including alumina ultrafine particles supported on the surface of metallic nickel fine particles. Because the oxide ultrafine particles are carried on the surface of the metal fine particles of the obtained composite nickel fine powder, even if the oxide ultrafine particles are added by stirring in water, no removal and floating of alumina ultrafine particles is observed. . In addition, the obtained composite nickel fine powder was examined by SEM observation and confirmed that the alumina ultrafine particles were uniformly carried on the surface of the composite powder 'and that the particle size of the composite particles was almost equal before and after the adhesion step. Example 28 Dioxide of 5 nd sol (Snow Tex 0, purchased from Nissan Chemical Industries, Ltd .; average particle size of major particles: 10 nm) was diluted by 20 times with water to obtain 2.5. In a liter solution (silica dioxide content: 10 g / L), 500 g of the fine metal nickel powder prepared in Preparation Example 2 was added, followed by heating and stirring sufficiently. The water component was gradually evaporated, and finally a dry powder was obtained. The powder was filled into a hybrid machine (purchased from Nara Machinery Manufacturing Co., Ltd.), and the powder was processed by circulating the powder in the machine at 8000 rpm for 5 minutes, thereby obtaining ultrafine silicon dioxide including the surface of fine particles of metallic nickel. Particles of composite nickel fine powder. The obtained composite nickel fine powder was examined by SEM observation and confirmed that the two I -------- installation -------- order --- I ----- line (please read the note on the back first) Please fill in this page again for the items) This paper size applies to the National Standard of China (CNS) A4 (2〗 0 X 297 mm> 21 310997 A7 ^ 10142 • ------ '' ___ B7_ V. Description of the invention (22 ) The silicon oxide ultrafine W particles are uniformly carried on the surface of the composite powder, and it is confirmed that the particles of the noisy particles are almost equal before and after the adhesion step. It is found that the weight relative to the weight of the metal nickel fine powder is carried on the surface of the composite nickel fine particles. The amount of crushed particles of the particles is 5 wt.%. In addition, the ultrafine particles of the silica dioxide are supported on the surface of the metal nickel fine particles of the obtained composite nickel fine powder. Silicon ultrafine particles. No removal or floating of alumina ultrafine particles was observed. Example 29 500 grams of the metallic nickel fine powder prepared in Preparation Example 2 was added to the ultra-disperser container (purchased with sufficient stirring). From Mitsui Mining Co., Ltd.), hot steamed The vessel was heated by gas, and then from the top of the vessel, an alumina sol (125 g; oxidized sol 520 purchased from Japan Chemical Industry Co., Ltd .; particle size: 10 to 20 nm) was obtained to obtain fine particles including a temporary load on metallic nickel. Metal nickel fine powder of alumina ultrafine particles on the particle surface. Fill the powder into a hybrid machine (purchased from Nara Machinery Manufacturing Co., Ltd.), and let the powder be processed in the machine at 8000 rpm for 5 minutes for processing. A composite nickel fine powder including ultrafine aluminum oxide particles carried on the surface of metal nickel fine particles. The obtained composite nickel fine powder was examined by SEM observation and 'confirmed that the ultrafine particles were carried on the surface of metal nickel fine particles' and it was found that the relative Based on the weight of the metal nickel fine powder, the amount of ultrafine particles carried on the surface of the metal nickel fine particles is 5% by weight. The composite nickel fine powder prepared in the above Examples 11 to 29 and the metal nickel prepared in the aforementioned Comparative Examples 3 to 4 Fine powder (it has a smooth surface, but --II---. 1 IIIII ^ i IIIIII ^--------- | ((Please read the back first; note Please fill in this page for further information) Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper is printed in accordance with China National Standard (CNS) A4 (210 X 297 mm) 22 310997 A7 B7 V. Description of the invention (23) Any oxide or complex oxide), using a deformation thermal analyzer (TMA / SS6000 purchased from Seiko Electronic Industries, Ltd.) under a nitrogen pressure at a heating rate of 10 ° C / Minutes, check the thermal large size ratio. The results thus obtained are detailed in Table 2 below. In this regard, the thermal large size ratios of the metal ball fine powders (which do not have a smooth surface and which do not have any oxides or complex oxides adhered thereto) prepared in Comparative Examples 1 to 2 are listed in Table 1 above. Table 2 Mixed thermal shrinkage rate of implementation oxide types (%) Example compilation ratio 50o ° c 70o ° c 90o ° c TToot " No. -------------- equipment— (Please read the precautions on the back before filling this page)-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 11 ai2o3 7 -0.34 -0.41 -0.41 -0.49 12 0.5 -0.52 -0.61 -0.63 -1.81 13 Ti〇2 1 -0.57 -0.63 -2.90 -8.67 14 Τΐ02 5 -0.49 -0.54 -2.41 -7.97 15 Si02 1 -0.52 -0.63 -0.95 -1.46 16 Si〇2 5 -0.49 -0.63 -0.70 -1.13 17 MgO 1 -0.58 -0.30 -0.33 -0.24 18 MgO 5 -0.55 -0.35 -0.39 -0.28 19 Y203 1 -0.32 -0.48 0.53 -1.87 20 Y2〇3 5 -0.45 -0.49 -0.58 -1.52 21 BaTi03 1 -0.48 -0.51 -0.68 -0.69 22 BaTi03 5 -0.51 -0.52 -0.63 -0.66 23 SrTi〇3 1 -0.38 -0.44 -0.81 -2.14 24 SrTi〇3 5 -0.32 -0.39 -0.52 -1.90 25 (B ^ OgSlo 1) Ti〇3 1 -0.25- 0.41 -0.60 -1.86 26 (Ba0 9Sr01) Ti03 5 -0.32 -0.37 0.51 -0.95 27 AI2O3 7 -0.37 -0.46 -0.54 -0.79 28 Si02 5 -0.26 -0.36 -0.59 -0.80 29 Al2〇3 5 -0.43 -0.46 -0.56 -0.59 3 * one--0.81 -1.94 -9.56 -15.08 4 * one -0.54 -0. 66 -7.79 -14.30 氺 ： Comparison setting. The paper size is applicable to Chinese National Standard (CNS) A4 (210x 297 mm) 23 310997 A7 4 I b 1 4 2 ___-____ B7___ V. Description of the invention (24) Details The data listed in Tables 1 and 2 clearly show that the composite nickel fine powders of the examples u to 29 (the present invention) have a relatively low heat large size at high temperatures compared to the metal nickel fine powders of Comparative Examples ι to 4. rate. The composite nickel fine powders obtained in Examples 11 to 26 and the metal nickel fine powders of Comparative Examples 2 and 4 were subjected to thermogravimetric analysis in the air. In more detail, • Determine the weight of each sample before analysis, and then heat the sample at a rate of 0 < > c / min to ucr for 4 0 C 'and maintain it at 4 0 C for 2 hours. At this stage, relative to the weight (starting weight) observed at the beginning of the measurement, determine the weight of each sample 'so that the weight increase rate A (% ρ) can be calculated. Thereafter, the temperature of the sample has increased by 1000 ° C (all nickel at this stage') (Seems to be converted to nickel oxide), relative to the starting weight, determine the weight of each sample at this stage, so that the weight increase rate B (%) can be obtained. The A / B ratio is determined, which is defined as each sample (ie, nickel powder) in The degree of oxidation after maintaining at 400 ° C for 2 hours "The results thus obtained are briefly explained in Table 3 below. ------------- ^ --- I ---- Order.!- ---- | ((Please read the notes on the back before filling out this page) Printed on the paper by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, the paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 24 310997 V. Instructions (25 A7 B7 Table 3 Example No. Oxidation Type Mixing Ratio Each sample is maintained at 400 ° C for 2 hours after oxidation 234567890123456 * * n 1 lx 1 1 IX 11 11 2 2 2 2 2 2 2 4.% / Ό / Ό / Ό / Ό / Ό / Ό / Ό Λ ^ / 7 Ti 1i 11 1X c—w 11 11 3 3 oo ♦ 1 * 1 TT \ ly \) / 1 11 oo: 0 30303o: sr9sr 2o2oo2020202gogoo303aT-aTlTiTiaoao aattssmmyybbss (b (b 25899813013975393 3 56766586765455658 8

I -------------- Shang -------- Order. F Please read the phonetic on the back first? Please fill in this page again: > 'Printed by H Consumer Cooperative, Member of Intellectual Property Bureau, Ministry of Economic Affairs *: The comparative example can be clearly shown by the data detailed in Table 3, compared with the fine nickel metal powders of Comparative Examples 2 and 4. The composite nickel fine powders according to Examples 11 to 26 of the present invention have excellent oxidation resistance. It is particularly clear that the higher the ratio of the oxide and / or complex oxide carried on the surface of the brocade, the higher the acid resistance of the composite nickel fine powder. This is because the oxides and / or complex oxides carried on the surface of the nickel fine powder have an effect of preventing oxidation of the composite nickel fine powder. The composite fine powder obtained in the aforementioned Example 11 and the fine fine powder of the metal recorded in Comparative Example 4 were further subjected to thermogravimetric analysis. After measuring the weight of each sample, the sample was heated at a heating rate of 1.5 ° C / min for 1,000 hours, and the paper size was adapted to the national standard (CNS) A4 specification (21OX 297 public love) 25 310997 A7 B7_______ 5. Description of the invention (26) The measured weight increase rate is made as a function of temperature. Therefore, the temperature at which one-half the weight increase rate observed at 1 000 ° C was measured was measured. This is the temperature at which 50% of oxidation is recorded. It was found that the temperature of the metal powder of Comparative Example 4 was 429 ° C, and the temperature of the composite nickel fine powder obtained in the foregoing Example u was 452 ° C, indicating that the temperature required to oxidize 50% of nickel was increased by 23 ° C. Regarding the above detailed description, the composite nickel fine powder of the present invention has excellent oxidation resistance, chemical resistance, a structure with low sensitivity to oxidation, rapid thermal large-scale starting temperature shift to not less than 700eC, and for most test cases In terms of not less than 900 ° C, the composite powder is quite suitable for use as an internal electrode material for forming a laminated capacitor. In other words, the composite nickel fine powder of the present invention has excellent metal nickel oxidation resistance and nickel oxide diffusion resistance during the removal of the binder, and exhibits a thermal large size property that is almost the same as the thermal large size curve of the ceramic substrate. When manufacturing a large-size laminated ceramic capacitor, delamination and crack formation can be prevented according to the present invention, and a thin, small-sized multilayer ceramic capacitor including a ceramic dielectric layer and an internal electrode can be manufactured without impairing its dielectric characteristics. And electrical properties. >; ------------- Order ----- 1 --- line — {Please read the notes on the back before filling this page) The paper size of the paper is applicable to the national standard (CNS) A4 (210 X 297 public love) 26 310997

Claims (1)

6. Scope of Patent Application 1. A composite nickel fine powder characterized by at least one member selected from oxides and complex oxides supported on the surface of metallic nickel fine particles, wherein the oxide and complex oxides include at least one kind of atom Metal element g elements of the order range 12 to 56 or 82 and belonging to Groups 2 to 14 of the Periodic Table A. 〆. 2. If the nickel fine powder of item i of the patent application 鼯, wherein the oxide and complex oxide include at least one having an atomic range of 12 to 56 or 82 and belongs to the second to the periodic table Group 7 or Group 13 to 14 Group II metal oxides and complex oxides. 3. For example, the composite nickel fine powder in the second scope of the patent application, wherein the oxide and the complex oxide include at least one having an atomic range of 12 to 56 or 82 and belonging to the 2, 3, 4, and Oxides and complex oxides of metal elements of groups 7, 13, or 14. 4. For example, the composite nickel fine powder of item 3 of the patent application scope, wherein the oxide is an oxide of a metal element belonging to Group 2, Y'Zr, A1 & Si in the periodic table. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. A kind of composite nickel fine powder, characterized in that it includes metal nickel fine particles and at least one member carried on the surface of metal fine particles. The oxide of one term and the complex oxide, and the oxide of at least one member selected from the group of elements of the family. 6. —A kind of composite recording fine powder 'characterized by including metallic nickel fine particles' and at least one member carried on the surface of the metal recording fine particles is selected from the complex oxide represented by the following general formula: BamX1.mTi „Z1.n 〇3 310997 28 310997 VI. Patent Application Range (where 'X represents Sr, Ca, Mg or Pb; Z represents Zr, Y, Sn or Ge; m is a number between 0 and is; 11 is a number between 0 and i digital). 7. For example, the composite nickel fine powder in the scope of the patent application No. 6 includes fine particles of gold chain; at least one member carried on the surface of the metal nickel fine teacher is selected from the complex oxides in the scope of the patent application No. 6 j *, and at least one member An oxide selected from any one of claims 1 to '4 in the scope of patent application. 8. If the composite nickel fine powder of item 6 of the patent application includes fine particles of metal chains; and at least one member carried on the surface of the metal nickel fine particles is selected from the complex oxides of item 6 of the patent application, and at least One member is selected from oxides of lanthanoids. 9. The composite nickel fine powder according to any one of claims 1 to 8, in which the at least one member is selected from the group consisting of oxides and complex oxides with respect to the weight of the composite nickel fine particles. weight%. 10. A method for preparing a composite fine powder, comprising the following steps: adding at least one member selected from the group consisting of metal iron microfaceted particles or metal nickel fine particles whose surface is oxidized, each having an atomic range of 12 to 56 Or 82 and a water-soluble salt solution of a metal element belonging to Groups 2 to 14 of the periodic table; then adjusting the pH of the mixture with an acid or base to carry a water-soluble salt-derived metal oxide and / or complex oxide Onto the surface of metallic nickel fine particles. 11. For the method of preparing composite nickel fine powder, such as the scope of application for patent No. 10, the paper size is applicable _ house standard (cn5a4 size ⑽ x 297 public meal 7 -------- ^ --------- line I, ------------------------- (Please read first Note on the back, please fill out this page) * A8 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs d —— ___ 〇8 ___ f. Patent application method, including the following steps: To the slurry of the oxidized metallic nickel fine particles, a water-soluble saline solution containing at least one member selected from the group consisting of metal elements having an atomic range of 12 to 56 or 82 and belonging to Zhous, Groups 2 to 14 in the table is added; Acid or base adjusts the pH of the mixture, and the water-soluble salt-derived metal oxide and / or complex oxide is carried on the surface of the metal nickel fine particles; the particles are washed and dried to oxidize the metal attached to it Fine particles of metal and / or complex oxides collide with each other or collide with other objects, and the metal oxide and / or complex oxides are tightly supported on the surface of the fine particles of the metal record. Item 丨 丨 The method for preparing composite nickel fine powder, which uses an Ong mill, a hybridizer, and a machine. Melting machine (Mechanofusion), Coat Mizer, Disper Coat, or Jet Mizer, the metal nickel fine particles with metal oxide and / or complex oxide adhered to each other or collide with other objects to oxidize the metal Materials and / or complex oxides are tightly supported on the surface of the fine particles of the metal recording β. 13. A method for preparing composite nickel fine powder, including the following steps: at least one member of ultrafine particles selected from oxides and complex oxides Temporarily carried on the surface of metal nickel fine particles or metal nickel fine particles whose surface is oxidized 'wherein the oxide or complex oxide system contains at least one having an atomic range of 12 to 56 or 82 and belongs to the second to the periodic table Metal elements of Group 14; nickel fine particles with ultrafine particles temporarily adhering to them collide with each other or with other objects, but please read the note of the back first and then fill in the gutter on this page. This paper size applies China National Standard (CNS) A4 Specification (210 X 297 Public Love) 29 310997 4 2 4 A8B8C8D8 The daughter is carried on the surface of the metallic nickel fine particles. 14. A method for preparing a composite nickel fine powder, comprising the steps of: using heating to disperse a suspension in which at least one member of ultrafine particles selected from oxides and complex oxides is dispersed with metallic nickel fine particles or the surface is oxidized Metal nickel fine particles, wherein the oxide and the complex oxide contain at least one metal element having an atomic range of 12 to 56 or 82 and belonging to groups 2 to 14 of the periodic table; a medium for removing the suspension , And the ultrafine particles are temporarily carried on the surface of the metal chain fine particles; and the metal particles with the ultrafine particles temporarily adhered to each other collide with each other or with other objects, so that the ultrafine particles can be carried to the metal Fine nickel particles on the surface. 15. For the method for preparing composite nickel fine powder according to item 13 or 14 of the scope of application for patent, 'in which a 0ng mill, a mixer, a mechanical melting machine, a Coat Mizer, a Disper Coat, or a Jet Mizer is used for temporary adhesion The ultrafine particles of the metal nickel fine particles collide with each other or with other objects, and the ultrafine particles are carried on the surface of the metal nickel fine particles "{Please read the precautions on the back before filling this page) • nn ϋ n ϋ ^ eJ · n I n ϋ I n I · 11 nn I Intellectual Property Bureau, Ministry of Economic Affairs, Consumer Consumption Cooperation, Du Printed This paper is sized for China National Standard (CNS) A4 (210 X 297 mm) 30 310997