JP2002352624A - Conductive metal compound paste, metal compound for the paste, layered ceramic capacitor using the paste, and method of manufacturing the capacitor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide conductive paste, a layered ceramic capacitor using said paste, and a method of manufacturing for the layered ceramic capacitor capable of preventing problems in the conventional method such as inferior dispersion of conductive paste-containing metal fine powder, the uneven film thickness of an inside electrode formed by printing on a ceramic green sheet, decrease in capacitance yield of the ceramic capacitor, low reliability of the capacitor, and generation of cracks and delamination of the layered ceramic capacitor in baking. SOLUTION: This conductive metal compound paste comprising a metal compound, and if required, metal fine powder, ceramic fine powder, an organic binder, a viscosity control agent, and an organic solvent is printed on a dielectric ceramic green sheet, after removing the solvent, plural pieces of the printed sheets are laminated, the laminated sheets are baked and sintered to manufacture a layered ceramic capacitor.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a conductive metal compound paste for forming internal electrodes of a laminated ceramic capacitor, a metal compound for producing the paste, a method for producing a laminated ceramic capacitor using the paste, and a method for manufacturing the same. The present invention relates to a laminated ceramic capacitor obtained by a manufacturing method. In the present invention, “conductive” of the conductive metal compound paste means that “internal electrodes can be formed” when used for manufacturing a laminated ceramic capacitor.

[0002]

2. Description of the Related Art A laminated ceramic capacitor has a structure in which dielectric ceramic layers and internal electrodes are alternately laminated, and each dielectric ceramic layer is sandwiched by internal electrodes. A capacitor provided with a pair of external electrodes. Here, the dielectric porcelain layer is formed by firing an unsintered porcelain sheet (ceramic green sheet) at a high temperature to form a dielectric, and the internal electrodes are formed by sintering a conductive paste at a high temperature to form a conductor. Consists of

[0003] The conductive paste is generally a paste obtained by dispersing fine metal powder with an organic binder and an organic solvent. Here, as the metal fine powder, a noble metal (P
d, Ag, Cu, etc.) or a base metal (Ni, etc.) fine powder, and an acrylic resin, a phenolic resin, an alkyd resin, a rosin ester resin, etc. are used as an organic binder. Examples of the solvent include alcohol-based, aliphatic or aromatic hydrocarbon-based, ether-based, and ester-based solvents.

This conductive paste is usually printed on a ceramic green sheet in a predetermined pattern by a screen printing method. After drying the organic solvent, the printed ceramic green sheet is laminated and pressed in the same direction after drying the organic solvent, and then cut into dice,
It is fired at a high temperature of 1,200 to 1,400 ° C. By this baking, the organic binder in the conductive paste is burned and removed, and the fine metal powder is sintered to become an internal electrode. A pair of external electrodes connected to the internal electrodes are provided.

When an internal electrode is to be formed using such a conventional conductive paste, metal ions on the surface of the metal fine powder gradually react with hydroxyl groups present in the organic binder, and the organic binder is degraded with time. As a result, the dispersibility of the metal fine powder in the conductive paste deteriorates, and when the internal electrodes are printed on the ceramic green sheet, the thickness of the internal electrodes becomes non-uniform, and the capacity yield of the laminated ceramic capacitor is reduced. However, there has been a problem that the reliability of the capacitor performance deteriorates.

When an internal electrode is formed using a conventional conductive paste, the difference in shrinkage between the dielectric ceramic layer and the internal electrode during firing is often large.
For this reason, the laminated ceramic capacitor has a serious disadvantage that cracks and delaminations are easily generated. In order to compensate for these problems and disadvantages, a method of producing a metal powder having good dispersibility when formed into a paste is disclosed in Japanese Patent Laid-Open No. 7-2073.
No. 07 gazette. Japanese Patent Laid-Open No. 5-242724 discloses a method for incorporating an organic phosphorus compound into a conductive paste.
No. 6,086,045. Japanese Patent Laid-Open No. 5-2427 discloses a method in which a conductive paste contains fine metal powder and a small amount of an organic nitrogen compound which forms a chelate complex with the fine metal powder.
No. 26 is disclosed.

However, the various methods according to the above proposals are insufficient to greatly improve the conventional level of dispersibility of the metal fine powder in the conductive paste. As a result, the internal electrodes are formed on the ceramic green sheet by printing. It cannot be said that the non-uniformity of the film thickness of the internal electrodes, the low level of the capacitance yield of the multilayer ceramic capacitor, and the low reliability have not yet been improved.

Japanese Patent Application Laid-Open No. 11-269186 discloses the use of a palladium alkyl mercaptide or the like for the paste of a multilayer ceramic capacitor. However, this technique has problems that the content of palladium in the compound is small and the synthesis route is complicated, which is economically disadvantageous.

[0009]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to reduce the dispersibility of fine metal powder in a conductive paste due to a change with time during the formation of internal electrodes, which is often caused by the conventional method. Non-uniform film thickness of the internal electrodes printed on the sheet, reduced capacity yield of multilayer ceramic capacitors, low reliability of multilayer ceramic capacitors, cracks and delamination of multilayer ceramic capacitors during firing and sintering It is an object of the present invention to provide a conductive paste free from various problems such as the above.

[0010]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have found that the use of a paste containing a specific metal compound can solve the above-mentioned drawbacks and problems. To complete the present invention. The gist of the present invention is as follows. The first aspect of the present invention is that a metal compound (MC) or a metal compound (M
A conductive metal compound paste comprising: C) and an organic solvent (S). A second aspect of the present invention is that a metal compound (MC) is a metal salt, a metal complex, an organic metal compound having a metal-carbon bond, a metal compound in which a metal and an organic group are bonded via an oxygen atom, The conductive metal compound paste according to the first aspect of the present invention, which is at least one selected from the group consisting of a metal compound in which a metal and an organic group are bonded and a metal-organic compound interlayer compound, is provided. A third aspect of the present invention is that the metal compound (MC) is a metal salt or a metal complex (both are referred to as “metal salts”). A metal compound paste is provided. A fourth aspect of the present invention provides the conductive metal compound paste according to the third aspect, wherein the metal compound (MC) is a metal salt of an organic carboxylic acid or an anhydride thereof. A fifth aspect of the present invention provides the conductive metal compound paste according to the third aspect, wherein the metal compound (MC) is a metal salt of an organic nitrogen compound. The sixth aspect of the present invention provides
The conductive metal compound paste according to the third aspect of the present invention, wherein the metal compound (MC) is a metal complex of a dicarbonyl compound represented by the following general formula [1]. R ¹ -C (＝ O) -R ² -C (＝ O) -R ³ [1] (wherein, R ¹ and R ³ are each independently a straight-chain or branched alkyl group having 1 to 6 carbon atoms) , A phenyl group or an alkyl-substituted phenyl group, and R ² is an alkylene group which may be branched.) In the seventh aspect of the present invention, the metal of the metal compound (MC) is a noble metal and / or a base metal. 7. A conductive metal compound paste according to any one of the first to sixth aspects. An eighth aspect of the present invention provides the conductive metal compound paste according to the seventh aspect, wherein the noble metal is at least one selected from the group consisting of palladium, gold, silver, and copper. A ninth aspect of the present invention provides the conductive metal compound paste according to the seventh aspect, wherein the base metal is at least one selected from the group consisting of nickel, cobalt, aluminum, tungsten, and molybdenum. A tenth aspect of the present invention is a metal compound (MC) or the metal compound (MC) and an organic solvent (S).
The present invention provides the conductive metal compound paste according to any one of the first to ninth aspects of the present invention, which is in a gel state and / or a sol state. An eleventh aspect of the present invention provides the conductive metal compound paste according to any one of the first to ninth aspects of the present invention, wherein the metal compound (MC) is dissolved in the organic solvent (S). I do. Twelfth Embodiment of the Present Invention
Is an organic solvent (S) at least one selected from the group consisting of an aromatic hydrocarbon compound, an aliphatic hydrocarbon compound, an alcohol compound, an ether compound and an ester compound; A conductive metal compound paste according to any one of the above. A thirteenth aspect of the present invention provides the conductive metal compound paste according to any one of the first to twelfth aspects of the present invention, further comprising a metal fine powder (MP). Fourteenth aspect of the present invention
Provides the conductive metal compound paste according to the thirteenth aspect of the present invention, wherein an addition amount of the metal fine powder (MP) is 2 to 50 parts by weight based on 100 parts by weight of the metal compound (MC). . A fifteenth aspect of the present invention is the first aspect of the present invention, which further comprises a ceramic fine powder (CP).
15. A conductive metal compound paste according to any one of Items 14 to 14. A sixteenth aspect of the present invention provides the conductive metal compound paste according to the fifteenth aspect of the present invention, wherein the ceramic fine powder (CP) is at least one selected from barium titanate and strontium titanate. A seventeenth aspect of the present invention provides the conductive metal compound paste according to the fifteenth or sixteenth aspect, wherein the amount of the ceramic fine powder (CP) is 5 to 50 parts by weight based on 100 parts by weight of the metal compound (MC). I do. The eighteenth aspect of the present invention is the first to the first aspects of the present invention, which further comprises an organic binder (B).
7. A conductive metal compound paste according to any one of 7. In a nineteenth aspect of the present invention, the organic binder (B) is at least one selected from the group consisting of an acrylic resin, a phenolic resin, an alkyd resin, an epoxy resin, and a rosin ester resin. The present invention provides a conductive metal compound paste of the above. A twentieth aspect of the present invention provides the conductive metal compound paste according to any one of the first to nineteenth aspects, further comprising a viscosity modifier (N). A twenty-first aspect of the present invention
The conductive metal compound paste according to the twentieth aspect of the present invention, wherein the viscosity modifier (N) is a cellulosic compound.
A twenty-second aspect of the present invention provides the conductive metal compound paste according to any one of the first to twenty-first aspects of the present invention, which is used for manufacturing a laminated ceramic capacitor. A twenty-third aspect of the present invention provides a metal compound (MC) used for producing the conductive metal compound paste according to any one of the first to twenty-second aspects of the present invention.
In a twenty-fourth aspect of the present invention, the conductive metal compound paste according to any one of the first to twenty-second aspects of the present invention is printed on one surface of a dielectric ceramic green sheet, and after removing the organic solvent (S), The present invention provides a method for manufacturing a laminated ceramic capacitor, wherein a plurality of such laminated sheets are stacked in the same direction, fired and sintered to obtain a laminate in which conductive internal electrodes and dielectric ceramic layers are alternately formed. The twenty-fifth aspect of the present invention is the twenty-fourth aspect of the present invention.
The present invention provides a multilayer ceramic capacitor obtained by the method for manufacturing a multilayer ceramic capacitor described in (1). A twenty-sixth aspect of the present invention provides the multilayer ceramic capacitor according to the twenty-fifth aspect, wherein the thickness of the conductive internal electrode is 0.1 to 2 μm.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the contents of the present invention will be described in detail. Metal compound (MC) In the present invention, the metal compound (MC) which gives a metal by firing in the presence of oxygen may be an inorganic compound or an organic compound, and may be a metal salt, a metal complex, or an organic metal having a metal-carbon bond. Examples include compounds, metal compounds in which a metal and an organic group are bonded through an oxygen atom, metal compounds in which a metal and an organic group are bonded through a nitrogen atom, and metal-organic compound interlayer compounds.

Metal As the metal used for the metal compound (MC), specifically, one kind selected from noble metals such as palladium, platinum, gold, silver and copper, preferably palladium, gold, silver and copper Or two or more or alloys thereof; nickel, cobalt,
Base metals such as aluminum, tungsten, molybdenum,
Preferably, one or more selected from nickel and cobalt, or an alloy thereof; an alloy of the above-mentioned noble metal and base metal, and the like are included. In the present invention, metals and alloys may be collectively referred to as “metals” unless they cause confusion.

(I) Metal salts and metal complexes (metal salts) Examples of the above metal salts include metal salts obtained from a basic metal compound and an acid or an anhydride thereof, or metals obtained from an acidic metal compound and a base. Metal salts in a narrow sense such as salts are mentioned. Examples of the metal complex include a metal complex in which a ligand is coordinated around a metal ion or an atom. In the present specification, metal salts or metal complexes in a narrow sense may be collectively referred to as "metal salts" unless confusion occurs.

Acid or its anhydride The acid or its anhydride used for obtaining the above-mentioned metal salt or metal complex is preferably an organic carboxylic acid having 1 to 50, more preferably 4 to 30 carbon atoms or an anhydride thereof. And phosphoric acid compounds such as 2-ethylhexyl phosphate mono-2-ethylhexyl ester and di- (2-ethylhexyl) phosphoric acid; formic acid, acetic acid, propionic acid, butanoic acid, heptanoic acid, octanoic acid, -Monocarboxylic acids such as ethylhexanoic acid, naphthenic acid and stearic acid; hydroxycarboxylic acids such as glycolic acid, lactic acid and salicylic acid; versatic acid, oxalic acid, maleic acid, maleic anhydride, malonic acid, poly (meth) acrylic acid Acids, polycarboxylic acids such as phthalic acid, and the like, and mixtures thereof, but are not limited thereto. Any other acid or anhydride thereof may be used as long as it has a property of forming a salt or a complex with the metal.

Bases The bases used for obtaining the above metal salts and metal complexes include, for example, ethylenediamine, polyaminocarboxylic acid (eg, ethylenediaminetetraacetic acid, etc.), triethylenetetramine, N- (2-hydroxyethyl) ethylenediamine, Bis (2,2,6,6-tetramethyl-4-
Piperidyl) sebacate, N, N'-disalicylidene-
1,2-propanediamine, N, N'-disalicylidene-1,2-butanediamine, 1,2,3-benzotriazole, tolyltriazole, decamethylenedicarboxylic acid disalicyloylhydrazide, 3- (N- Salicyloyl) amino-1,2,4-triazole, salicylaldehyde oxime, dimethylglyoxime, diethylglyoxime, o-phenanthroline, 2,2′-dipyridine, p, p′-dioctyldiphenylamine, N,
N'-diphenyl-p-phenylenediamine can be mentioned. As long as the compound can form a metal complex with a noble metal or a base metal, an organic nitrogen-containing compound other than these may be used.

Diketone Compound for Complex Formation Preferred organic compounds used for obtaining the above metal complex include the diketone compounds represented by the general formula [1]. In the formula, the linear or branched alkyl represented by R ¹ or R ³ has 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, methyl, ethyl, n-propyl,
Isopropyl, butyl, isobutyl, sec-butyl,
t-butyl and the like; examples of the alkyl group of the alkyl-substituted phenyl group include the above-mentioned alkyl groups; and alkylenes that may be branched include methylene, methylmethylene, dimethylene, trimethylene, propylene, and tetramethylene. . As the compound represented by the general formula [1], for example, acetylacetone (CH ₃ COCH ₂ C
OCH ₃ ), acetonylacetone (CH ₃ COCH ₂ CH ₂₎
COCH ₃ ), dipropionylmethane (CH ₃ CH ₂ CO
_{CH 2 COCH 2 CH 3),} n- butyryl acetone (CH _{3
CH 2 CH 2 COCH 2 COCH 2} ), isobutyryl acetone _{(CH 3 CH (CH 3)} COCH 2 COCH 3), 3- methyl-2,4-hexane - dione (CH ₃ COCH (C
_{H 3) COCH 2 CH 3)} , diacetyl ethyl methane _{((CH 3 CO) 2 CHCH} 2 CH 3), can be exemplified dibenzoyl methane, and are not intended to be limited thereto.

(Ii) Organometallic compound having a metal-carbon bond Examples of the above-mentioned organometallic compound having a metal-carbon bond include the following. The metal compound is M, its valence is m, the organic group is R, and the alkylene group is (CH ₂ ) _k (k is 1 to
6) When X is a halogen atom, it is represented as follows.
However, R is an aliphatic group, an alicyclic group, an aromatic group, or a heterocyclic group, and the number of carbon atoms is not particularly limited, but is preferably 1 to 20, more preferably 1 to 6. And all Rs in one molecule may be the same or different. Organometallic or organometallic hydride: R _n
MH _mn organometallic alkylene: [R _m-1 M]-(CH ₂ ) _k- [M
R _m-1 ] Organohalometal: R _n MX _mn Organometallic hydroxide: R _n M (OH) _mn Organometallic alkyl (and / or allyl) oxide: R _n M (OR) _mn Organometallic carboxylate: R _n M (OCO
R) _mn organoamino metal: R _n M (NH ₂ ) _mn organo metal isocyanate: R _n M (NCO) _mn organo metal thiane: [R _m-1 M] -S- [MR _m-1 ] Preferred are organometals, organometallic hydrides, organometallic alkylenes, organometallic alkoxides, and allyl oxides. More specifically, the base metals include triphenylchromium tris (tetrahydrofuranate), benzenechromium tricarbonyl; bis (cyclopentadienyl) hexacarbonyl-ditungsten;
Ethyl aluminum diethoxide and the like can be mentioned. Examples of the noble metal include methyl silver, ethyl silver, n-propyl silver, and phenyl silver; trimethyl gold, dimethyl gold phenyl mercaptide: tetramethyl platinum, di (trimethyl platinum), and the like.

(Iii) a metal and an organic group are linked via an oxygen atom
Metal compound to be bonded
Metal alkoxide and / or allyl oxide
Sid. In addition, R is the same as the above (ii)
No. Organometallic alkyl (and / or allyl) oxy
Do: M (OR)_m Organometallic alkyl (and / or allyl) oxy
Droxide: (RO) _nM (OH)_mn Organometallic alkyl (and / or allyl) oxyca
Ruboxylate: (RO)_nM (OCOR)_mn The metal salt in which the metal and the carboxyl group are bonded is
Not included.

(Iv) A metal and an organic group are bonded via a nitrogen atom.
Metal compound which combines with metal and organic group via nitrogen atom
The following amino compounds of metal and / or isocyanate
Or a card. In addition, R is the same as the above (ii)
No. The organoamino metal: R_nM (NHR)_mn, R_n
M (NR_Two)_mn Alkyl (and / or allyl) oxyamino metal:
(RO)_nM (NHR)_{m -n}, (RO)_nM (NR_Two)_mn Alkyl (and / or allyl) carboxyamino meta
Le: (RCOO)_nM (NHR)_mn, (RCOO)_nM
(NR_Two)_mn Organometallic isocyanate: R_nM (NCO)_mn More specifically, glyoxime complex, N, N-bis
(1-methyl-3-oxobutylidene) ethylene diamine
Nart complexes and the like.

(V) Metal-organic compound intercalation compound Examples of the metal-organic compound intercalation compound include compounds in which a metal, a metal halide or the like is interposed between ring layers of cyclopentadiene, indene or the like. In these compounds, 1 to 5 alkyl groups having 1 to 4 carbon atoms may be substituted.

Organic Solvent (S) As the organic solvent (S) used in the present invention, various organic compounds can be applied. Among them, aromatic hydrocarbon compounds, alicyclic hydrocarbon compounds, and aliphatic One or more solvents selected from the group consisting of solvents of hydrocarbon compounds, alcohol compounds, ketone compounds, ether compounds, and ester compounds are used alone or as a mixed solvent. Examples of these include aliphatic hydrocarbons such as hexane, heptane and kerosene; alicyclic hydrocarbons such as cyclohexane; aromatic hydrocarbons such as toluene and xylene; aliphatics such as acetone, cyclohexanone and cyclopentanone; Alicyclic ketones; aliphatic alcohols such as methanol, ethanol, 2-propanol, n-butanol; ethers or glycol ethers such as tetrahydrofuran, diethylene glycol monobutyl ether, butyl cellosolve; ethyl acetate;
Esters such as propyl acetate, butyl acetate, and butyl phthalate, and mixtures thereof; and terpene, terpene alcohol, terpene aldehyde, terpene ketone, terpineol, and the like, and terpene oil that is a mixture thereof. However, it is not limited to these examples as long as they have characteristics capable of dissolving the metal compound (MC), and organic compounds other than these can also be used.

In the present invention, the amount of the organic solvent (S) to be used with respect to the metal compound (MC) varies depending on the type of the metal compound (MC) and the use of the organic binder, and is not particularly limited. Any material may be used as long as it can be printed as a paste on a sheet or in a predetermined thickness and shape. Usually, it is in the range of 0.01 to 10 parts by weight based on 100 parts by weight of the metal salt. If the amount is more than the appropriate usage range, the paste will not be printed because it is not a paste. If the amount is too small, the paste will not be formed, or if the paste is formed, the viscosity will be too high to print. Gel Metal Compound In the present invention, the gel metal compound is a metal compound (MC) which is in a jelly state with a substantially minimum amount of the above-mentioned solvent, and which can be printed as a paste by itself as described below. Say. In practice, an amount of the solvent (S) exceeding the minimum amount may be added. Sol-like metal compound In the present invention, the sol-like metal compound is a compound in which the metal compound (MC) is dispersed in the solvent (S) in a colloidal state and exhibits a fluidity. It refers to a paste that can be printed as a paste containing a fine powder (MP), a ceramic fine powder (CP), an organic binder (B), a viscosity modifier (N), and the like. In practice, an amount of the solvent (S) exceeding the minimum amount may be added. Metal Compound Solution The metal compound (MC), the gel-like metal compound and the sol-like metal compound can be used in a state in which the solvent (S) is added and dissolved.

Diluent solvent (D) In addition to these organic solvents (S), petroleum hydrocarbons (such as mineral spirits) and / or terpineol are used as diluent solvents for the purpose of improving the adhesion to the ceramic green sheet. May be. The diluting solvent (D) is preferably used in an amount of 0 to 30 parts by weight based on 100 parts by weight of the metal compound (MC).

Organic Binder (B) The organic binder (B) imparts printability such as the viscosity and interfacial tension of the metal compound paste, adheres to a ceramic green sheet, and forms a metal compound during firing and sintering. MC) are used to appropriately add the binding performance between them, and the type thereof is not particularly limited as long as they can be dissolved in the organic solvent (S). Usually, one or more selected from acrylic resin, phenol resin, aryl resin, phenol-formaldehyde resin, unsaturated polyester resin, alkyd resin, epoxy resin, and rosin ester resin can be mentioned as suitable ones. The organic binder (B) can be used in an amount of usually 1 to 90 parts by weight, preferably 10 to 90 parts by weight, based on 100 parts by weight of the metal compound (MC).

Metal Fine Powder (MP) The metal fine powder (MP) optionally used in the conductive metal compound paste of the present invention includes the metal compound (MC).
And fine powders of the same or different metals, fine powders of metal oxides, and mixtures thereof. Fine powders of metals conventionally dispersed with an organic binder and an organic solvent to produce a laminated ceramic capacitor, Fine powder of a metal oxide such as nickel is used as it is. The particle size of the metal fine powder (MP) is 0.01 to 10 μm, preferably 0.04 to 8 μm. Metal fine powder (MP)
Although the addition amount of is not particularly limited, the metal compound (MC) 1
2 to 50 parts by weight, preferably 5 to 100 parts by weight
It is added in the range of 40 parts by weight. The use of the metal fine powder (MP) has an effect that delamination hardly occurs as compared with the case where the metal fine powder (MP) is not used. In the present invention, a fine powder of a metal compound (MC) or a gel-like metal compound (MC) can be added instead of the fine metal powder.

Other additives and ceramic fine powder (C
P) The conductive metal compound paste according to the present invention includes a metal compound (MC), a fine metal powder (MP), and an organic solvent (S).
Is preferably used, and furthermore, an organic binder (B), a viscosity modifier (N) and the like are used. Further, as other additives, metal oxides such as barium oxide and titanium oxide, and ceramics of the same quality as the ceramic dielectric are used. Fine powder (CP), for example,
Silicon nitride, silicon carbide, alumina, zirconia, aluminum titanate, strontium titanate, barium titanate, mullite, boron nitride and the like can be mentioned, and one kind or a mixture of two or more kinds may be used. Among these, ceramic fine powder (CP) having the same or similar properties as the ceramic constituting the dielectric ceramic layer is preferable from the viewpoint of preventing delamination. Therefore, barium titanate or strontium titanate is preferred. The average particle diameter of the ceramic fine powder (CP) measured by SEM (scanning electron microscope) is preferably 0.05 to 1.0 μm,
In particular, the range of 0.1 to 0.8 μm is more preferable. In addition,
The use amount of these materials is not particularly limited as long as the effect of the present invention is not impaired, but the amount of the ceramic fine powder (CP) is based on 100 parts by weight of the metal compound (MC).
Usually, it is added in the range of 5 to 80 parts by weight, preferably 8 to 70 parts by weight. In the present invention, when adding various additives to the gel-like and / or sol-like metal compound, the gel-like and / or sol-like metal compound may be once produced, and then the additive may be added. The production of the metal compound in the form of a gel and / or a sol and the addition of additives may be carried out simultaneously.

Viscosity Modifier (N) and Adhesion Improver (E) The viscosity modifier optionally used in the present invention comprises a conductive metal compound paste together with a metal compound, a fine metal powder, and an organic solvent. Is added for the purpose of adjusting so as to have a viscosity suitable for printing. The adhesion improver is added for the purpose of having the paste adhere to the green sheet. The conductive metal-metal compound paste of the present invention may be added with a fine metal powder, an organic binder or the like as described above, but the adhesion improver alone, and the viscosity modifier plays the above role together with the organic binder. Things. As the viscosity modifier and the adhesion improver, for example, a cellulosic compound is preferable, and examples thereof include methylcellulose, ethylcellulose, and ethylhydroxyethylcellulose. Among them, ethylcellulose is preferable. The amount of the viscosity modifier and the adhesion improver used depends on the type of the metal compound (MC) and the use of the organic binder, and is not limited to a specific one. It is used so as to have a viscosity that can be printed in a thickness and a shape and to have an adhesion improving property. Usually, 1 to 20 parts by weight, preferably 4 to 10 parts by weight is used per 100 parts by weight of the metal compound (MC).

Method for Producing Conductive Metal Compound Paste The method for producing the conductive metal compound paste is not particularly limited. For example, a metal compound (MC) and an organic solvent (S) are first mixed and then mixed. Metal fine powder (M
P), method of adding ceramic fine powder (CP) and other additives, organic solvent (S) and ceramic fine powder (CP)
, And then a method of adding and mixing a metal compound (MC), a method of collectively mixing the respective components, and the like.

Use of conductive metal compound paste The conductive metal compound paste of the present invention can be used as an internal electrode of a laminated ceramic capacitor.

A method of manufacturing a laminated ceramic capacitor The method of manufacturing a laminated ceramic capacitor using the above paste is not particularly limited, but a typical manufacturing method is an unfired or unsintered ceramic sheet (ceramic green sheet). After the organic solvent is removed in a predetermined pattern by a screen printing method or the like and the organic solvent is removed, a desired number of sheets are alternately sandwiched without changing the vertical direction. And pressurizing in the laminating direction to completely eliminate voids between the laminations, and heating and baking in this state. As a result, a laminated ceramic capacitor in which thin-film internal electrodes, which are sintered bodies of metal, are formed between dielectric ceramic layers formed by sintering and firing is obtained. The ceramic green sheet is not particularly limited, and a known or commercially available ceramic green sheet is used. The firing conditions mainly depend on the firing conditions of the ceramic green sheet, and also vary depending on the metal of the metal compound, the type of the organic group, etc., and also the catalytic action of the metal. In some cases, a metal is generated by elimination or decomposition of a group.In the case where a metal is generated without being subjected to such oxidation, the metal can be generated even in the air. Is in existence. The firing temperature and firing time are preferably within the range of firing conditions for the ceramic green sheet. Therefore, in the present invention, the term “metal compound (MC) that becomes a metal upon firing” means “printing a paste on a ceramic green sheet as described above and firing it under firing conditions for manufacturing a laminated ceramic capacitor. And a metal compound (MC) which is a metal exhibiting conductivity.

Since the laminated ceramic capacitor of the present invention has thin-film internal electrodes, it can be laminated in multiple layers, and the overall thickness of the capacitor can be reduced. Regarding the thickness of the internal electrode, it may be a thick film (more than 5 μm to 20 μm) or a thin film (5 μm or less), but if the conductive metal compound paste of the present invention is used, it is 5 μm or less, preferably 0.1 to 2 μm, more preferably 0.1
It is possible to form a thin-film internal electrode of about 1.0 μm. The multilayer ceramic capacitor of the present invention has an acquired capacity (that is, an electrostatic capacity per 1 cm ³ ) of, for example, 0.1, although it depends on the size, the number of layers, the applied voltage, and the frequency.
nF to 30 μF, preferably 0.1 nF to 22 μF, and the standard deviation is 30 nF or less, preferably 25 nF.
Or less, more preferably 20 nF or less. In addition, despite the fact that it is possible to stack such thin layers in multiple layers, voids or cracks due to delamination (peeling of the internal electrode from the dielectric ceramic layer) are generated in the internal electrodes, and pinholes are generated. Almost no formation occurs, and the reliability of the obtained capacitor as an electronic component is high. These characteristics are found not only in the internal electrodes of the laminated ceramic capacitor, but also when applied to the other examples described above. For example, when used for wiring of a circuit board, a fine circuit with excellent resolution is formed. be able to.

[0032]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
In each example, a multilayer ceramic capacitor was prepared and the capacitor was evaluated as follows.・ Preparation of multilayer ceramic capacitor The obtained conductive paste is printed on a ceramic green sheet (commercially available) by screen printing to form internal electrodes, and the solvent contained in the printed layer is removed. 30 sheets were laminated and pressed under pressure to obtain a laminate. Next, the laminate is sized as required for a capacitor (3.2 mm in length, 1.6 mm in width, 1.0 m in thickness).
m), and fired and sintered in a firing furnace, and external electrodes were baked to produce a multilayer ceramic capacitor.
The thickness of the obtained internal electrode was about 2 μm. -Evaluation of multilayer ceramic capacitor The standard deviation of the obtained capacity of the obtained multilayer ceramic capacitor was examined. The standard deviation of the acquired capacity was measured for 100 multilayer ceramic capacitors using an electric capacity meter 4278A manufactured by Hewlett-Packard Company. Further, the obtained multilayer ceramic capacitor was cut along a plane perpendicular to the internal electrodes, and after mirror polishing, the number of delaminations in 100 multilayer ceramic capacitors was examined using an optical microscope.

Examples according to the present invention I (Synthesis Example I-1) (1) 2,908 parts by weight of nickel sulfate was dissolved in 2,000 parts of distilled water.
An aqueous solution dissolved in parts by weight was prepared. (2) 8,500 parts by weight of versatic acid (Versatic acid C10 manufactured by Yuka Shell Epoxy Co., Ltd.) was mixed with xylene 100
A solution dissolved in 0 parts by weight was prepared. The solutions (1) and (2) were mixed at 50 ° C. and stirred. After stirring for a while, the upper xylene layer and the lower water layer were separated by decantation, and the xylene of the xylene layer was distilled. Leave to remove about 2.0 nickel versatate
00 parts by weight were obtained.

(Synthesis Example I-2) Nickel carbonate 8 was added to an aqueous solution obtained by dissolving 116 parts by weight of maleic acid in 180 parts by weight of distilled water.
After adding 0 parts by weight and precipitating nickel maleate,
After filtration and drying, about 60 parts by weight of nickel maleate was obtained.

(Synthesis Example I-3) 100 parts by weight of polyacrylic acid (Schrimer AC-10P, manufactured by Nippon Pure Chemical Co., Ltd.) was dissolved in 25 parts by weight of methyl alcohol, and then 5 parts by weight of 20% aqueous ammonia was added. A solution prepared by dissolving 50 parts by weight of nickel carbonate in 50 parts by weight of water was added, and the mixture was sufficiently stirred.
Thereafter, the precipitate was filtered and dried to obtain 130 parts by weight of a nickel polyacrylate salt.

(Synthesis Example I-4) Basic aqueous solution of polyacrylic acid (40% aqueous solution, manufactured by Nippon Junyaku Co., Ltd., Schrimer AC-1)
(0SL) 40 parts by weight of nickel carbonate was added to 200 parts by weight, and after sufficiently stirring, water was distilled off and dried to obtain 115 parts by weight of a nickel polyacrylate salt.

(Synthesis Example I-5) 2-ethylhexanoic acid 28
To a solution in which 8 parts by weight of xylene was dissolved in 1,200 parts by weight of xylene, a solution in which 150 parts by weight of nickel carbonate was dissolved in 1,000 parts by weight of distilled water was added, and the mixture was sufficiently stirred at 50 ° C. and allowed to stand. The xylene layer was separated from the aqueous layer, and the solid of nickel carbonate was separated by filtration.
300 parts by weight of nickel ethylhexanoate were obtained.

Example I-1 50 parts by weight of nickel versatate obtained in Synthesis Example I-1 was dissolved in 50 parts by weight of xylene, and 10 parts by weight of terpineol was added to produce a paste. Printing was performed on a barium strontium-based ceramic green sheet to produce a multilayer ceramic capacitor, which was evaluated.

Example I-2 15 parts by weight of nickel maleate obtained in Synthesis Example I-2 was dissolved in 30 parts by weight of xylene, and 10 parts by weight of terpineol was added to produce a paste. A multilayer ceramic capacitor was prepared and evaluated in the same manner as in -1.

(Example I-3) 20 parts by weight of the nickel polyacrylate metal salt obtained in Synthesis Example I-3 was mixed with 50 parts of ethyl acetate.
Dissolved by weight, 10 parts by weight of terpineol is added,
A paste was produced by adding 15 parts by weight of an acrylic resin (Acrypet MD, manufactured by Mitsubishi Rayon Co., Ltd.) as an organic binder, and a multilayer ceramic capacitor was prepared and evaluated in the same manner as in Example I-1.

Example I-4 20 parts by weight of the nickel polyacrylate metal salt obtained in Synthesis Example I-4 was dissolved in 50 parts by weight of methanol / ethyl acetate (1/1 weight ratio), and terpineol was added in an amount of 10 parts by weight. And a paste was prepared by adding 15 parts by weight of acrylic resin Acrypet MD as an organic binder, and a multilayer ceramic capacitor was prepared and evaluated in the same manner as in Example I-1.

(Comparative Example I-1) Nickel powder (having a particle size of 0.1
50 parts by weight, 1 part by weight of ethylcellulose (thickener) (manufactured by Dow Chemical Company, Ethocel STD-100), 2 parts by weight of mineral spirits
0 parts by weight and 30 parts by weight of butyl carbitol were put into a roll mill, and kneaded well to prepare a conductive nickel powder paste for an internal electrode. A multilayer ceramic capacitor was prepared and evaluated in the same manner as in Example I-1. Was done.

The results of Examples I-1 to I-4 and Comparative Example I-1 are shown in Table I.

[0044]

[Table 1]

Examples according to the present invention II (Synthesis Example II-1) to (Synthesis Example II-3), (Synthesis Example II-5)
Are the same as (Synthesis Example I-1) to (Synthesis Example I-3) and (Synthesis Example I-5), respectively.

Example II-1 100 parts by weight of nickel versatate obtained in Synthesis Example II-1 was mixed with acrylic resin 1
2 parts by weight of xylene / ethyl acetate (1/1 weight ratio) 25
The paste was prepared by adding 10 parts by weight of terpineol, and printing was performed on a barium strontium titanate-based ceramic green sheet to produce a multilayer ceramic capacitor, which was evaluated.

(Example II-2) 15 parts by weight of nickel maleate obtained in Synthesis Example II-2 and 12 parts by weight of an acrylic resin were dissolved in 25 parts by weight of xylene / ethyl acetate (1/1 weight ratio). A paste was prepared by adding 10 parts by weight of terpineol, and a multilayer ceramic capacitor was prepared and evaluated in the same manner as in Example II-1.

Example II-3 20 parts by weight of the nickel polyacrylate metal salt obtained in Synthesis Example II-4 was mixed with methanol /
Dissolved in 50 parts by weight of ethyl acetate (1/1 weight ratio), added 10 parts by weight of terpineol, added 15 parts by weight of an acrylic resin as an organic binder to produce a paste,
A multilayer ceramic capacitor was prepared and evaluated in the same manner as in Example II-1.

Example II-4 2 obtained in Synthesis Example II-5
A paste was prepared by dissolving 20 parts by weight of nickel ethylhexanoate in 50 parts by weight of isopropyl alcohol (IPA), adding 10 parts by weight of terpineol, and adding 15 parts by weight of an acrylic resin as an organic binder. In the same manner as in -1, a multilayer ceramic capacitor was prepared and evaluated.

Comparative Example II-1 50 parts by weight of the nickel powder, 4 parts by weight of ethylcellulose, 60 parts by weight of mineral spirit and 30 parts by weight of butyl carbitol were put into a roll mill, kneaded well, and then mixed with a conductive material for an internal electrode. A nickel powder paste was prepared, and a multilayer ceramic capacitor was prepared and evaluated in the same manner as in Example I-1.

Examples II-1 to II-3 and Comparative Example II-1
The results are shown in Table II.

[0052]

[Table 2]

Examples (Synthesis Example III-1) to (Synthesis Example III-4) according to the present invention III are the same as (Synthesis Example I-1) to (Synthesis Example I-4), respectively.

Example III-1 100 parts by weight of nickel versatate obtained in Synthesis Example III-1, 6 parts by weight of mineral spirit, 10 parts by weight of ethyl alcohol, and 10 parts by weight of terpineol were put into a roll mill and kneaded well. Then, a conductive paste of a gel-like metal salt was produced, and printing was performed on a barium strontium titanate-based ceramic green sheet to produce a multilayer ceramic capacitor, which was evaluated.

(Example III-2) To 15 parts by weight of nickel maleate obtained in Synthesis Example III-2, 10 parts by weight of a xylene / ethyl acetate mixed solvent (1/1 weight ratio) and 10 parts by weight of terpineol were added. To prepare a gel-like metal salt,
A multilayer ceramic capacitor was prepared and evaluated in the same manner as in I-1.

(Example III-3) A gel-like metal salt was produced by adding 50 parts by weight of ethyl acetate and 10 parts by weight of terpineol to 20 parts by weight of the nickel polyacrylate metal salt obtained in Synthesis Example III-3. A multilayer ceramic capacitor was prepared and evaluated in the same manner as in Example III-1.

Example III-4 50 parts by weight of methanol / ethyl acetate (1/1 weight ratio) and 10 parts by weight of terpineol were added to 20 parts by weight of the nickel polyacrylate metal salt obtained in Synthesis Example III-4. A gel-like metal salt was produced, and a multilayer ceramic capacitor was prepared and evaluated in the same manner as in Example III-1.

Comparative Example III-1 50 parts by weight of the nickel powder, 4 parts by weight of ethylcellulose, 60 parts by weight of mineral spirit and 30 parts by weight of butyl carbitol were put into a roll mill, sufficiently kneaded, and then kneaded. A nickel powder paste was prepared, and a multilayer ceramic capacitor was prepared and evaluated in the same manner as in Example III-1.

Examples III-1 to III-4 and Comparative Example III-
The results of 1 are shown in Table III.

[0060]

[Table 3]

Examples according to the present invention IV (Synthesis Example IV-1) (1) 2,908 parts by weight of nickel sulfate was dissolved in 2,000 parts of distilled water.
An aqueous solution dissolved in parts by weight was prepared. (2) A solution was prepared by adding 5,000 parts by weight of anhydrous acetylacetone to 100 parts by weight of toluene. After mixing and stirring the solutions of (1) and (2), the mixture was allowed to stand for a while, and then the upper toluene layer and the lower aqueous layer were separated by decantation. Acetonate nickel complex about 2,000
0 parts by weight were obtained.

(Synthesis Example IV-2) (1) 2,908 parts by weight of nickel sulfate was added to 2,000 parts of distilled water.
An aqueous solution dissolved in parts by weight was prepared. (2) 5,500 parts by weight of acetonylacetone in toluene 1
A solution added to 00 parts by weight was prepared. After mixing and stirring the solutions of (1) and (2), the mixture was allowed to stand for a while, and then the upper toluene layer and the lower aqueous layer were separated by decantation. Nylacetonate nickel complex about 2,0
00 parts by weight were obtained.

(Synthesis Example IV-3) (1) 2,908 parts by weight of nickel sulfate was dissolved in 2,000 parts of distilled water.
An aqueous solution dissolved in parts by weight was prepared. (2) 8,500 parts by weight of dibenzoylmethane is added to toluene 1
A solution added to 00 parts by weight was prepared. After mixing and stirring the solutions of (1) and (2), the mixture is left to stand for a while, and then the upper toluene layer and the lower aqueous layer are separated by decantation. Benzoylmethane nickel complex about 2,000
Parts by weight were obtained.

Example IV-1 100 parts by weight of the acetylacetonate nickel complex obtained in Synthesis Example IV-1 and 12 parts by weight of an acrylic resin were dissolved in 30 parts by weight of acetone, and 10 parts by weight of terpineol was added. A conductive paste was manufactured, printed on a barium strontium titanate-based ceramic green sheet, and a multilayer ceramic capacitor was prepared and evaluated.

Example IV-2 100 parts by weight of the acetylacetonate nickel complex obtained in Synthesis Example IV-1 and 1 part by weight of ethyl cellulose as a viscosity modifier were added to 30 parts by weight of methyl ethyl ketone and 10 parts by weight of terpineol. A conductive paste was manufactured and, in the same manner as in Example IV-1,
A multilayer ceramic capacitor was prepared and evaluated.

Example IV-3 In the same manner as in Example IV-1, 50 parts by weight of the acetonylacetonate nickel complex obtained in Synthesis Example IV-2 was dissolved in 100 parts by weight of tetrahydrofuran, and 10 parts by weight of terpineol was added. And a paste was prepared by adding 10 parts by weight of an acrylic resin as an organic binder. A multilayer ceramic capacitor was prepared and evaluated in the same manner as in Example IV-1.

Example IV-4 In the same manner as in Example IV-1, 50 parts by weight of the acetylacetonatonickel complex obtained in Synthesis Example IV-1 was dissolved in 100 parts by weight of tetrahydrofuran, and 10 parts by weight of terpineol was obtained. Was added, and 10 parts by weight of an acrylic resin as an organic binder and 1 part by weight of ethyl cellulose as a viscosity modifier were added to produce a paste. A multilayer ceramic capacitor was prepared and evaluated in the same manner as in Example IV-1. .

Example IV-5 In the same manner as in Example IV-1, 10 parts by weight of the dibenzoylmethane nickel complex obtained in Synthesis Example IV-3 was dissolved in 100 parts by weight of toluene, and 10 parts by weight of terpineol was obtained. Was added, and 10 parts by weight of an acrylic resin was added as an organic binder, and the mixture was sufficiently stirred to produce a paste. A multilayer ceramic capacitor was prepared and evaluated in the same manner as in Example IV-1.

Example IV-6 80 parts by weight of the acetylacetonate nickel complex obtained in Synthesis Example IV-1 and nickel powder (particles having a particle size of 0.1 to 1 μm are distributed. 5 parts by weight of metal fine powder) and 12 parts by weight of an acrylic resin were added to 10 parts by weight of methyl ethyl ketone and 10 parts by weight of terpineol, and the mixture was sufficiently stirred to produce a paste. In the same manner as in Example IV-1, A multilayer ceramic capacitor was prepared and evaluated.

Example IV-7 80 parts by weight of the acetylacetonate nickel complex obtained in Synthesis Example IV-1, 5 parts by weight of palladium fine powder, 12 parts by weight of acrylic resin, 20 parts by weight of methyl ethyl ketone, 10 parts by weight of terpineol And the mixture was sufficiently stirred to produce a paste. Using this paste, a multilayer ceramic capacitor was prepared and evaluated in the same manner as in Example IV-1.

(Example IV-8) 80 parts by weight of the acetylacetonate nickel complex obtained in Synthesis Example IV-1, 3 parts by weight of palladium fine powder, 2 parts by weight of nickel powder, and 12 parts by weight of acrylic resin were mixed with 20 parts by weight of methyl ethyl ketone. And 10 parts by weight of terpineol, and sufficiently stirred to produce a paste. Using this paste, a multilayer ceramic capacitor was prepared and evaluated in the same manner as in Example IV-1.

(Comparative Example IV-1) 50 parts by weight of the nickel powder, 4 parts by weight of ethyl cellulose (thickener), 60 parts by weight of mineral spirit and 30 parts by weight of butyl carbitol were put into a roll mill, thoroughly kneaded, and then kneaded. A conductive nickel powder paste for an electrode was prepared, and a multilayer ceramic capacitor was prepared and evaluated in the same manner as in Example IV-1.

The above Examples IV-1 to IV-8 and Comparative Example IV-1
Are shown in Table IV.

[0074]

[Table 4]

Examples according to the present invention V (Synthesis Example V-1) to (Synthesis Example V-4) are the same as (Synthesis Example I-1) to (Synthesis Example I-4), respectively.

Example V-1 100 parts by weight of the nickel versatate obtained in Synthesis Example V-1 and the nickel powder 5
Parts by weight, ethyl cellulose 2 parts by weight, acrylic resin 12
Parts by weight, 3 parts by weight of mineral spirit, 30 parts by weight of ethyl alcohol, and 10 parts by weight of terpineol are kneaded and sufficiently kneaded in a roll mill to produce a conductive paste, which is printed on a barium strontium titanate-based ceramic green sheet, and laminated ceramics Create a condenser,
An evaluation was performed.

Example V-2 15 parts by weight of nickel maleate, 5 parts by weight of nickel powder, and 12 parts by weight of acrylic resin obtained in Synthesis Example V-2 were mixed with xylene / ethyl acetate (1/1).
(Weight ratio) 10 parts by weight and terpineol 10 parts by weight and sufficiently stirred to produce a conductive paste.
In the same manner as in Example 1, printing was performed on a barium strontium titanate-based ceramic green sheet to produce a multilayer ceramic capacitor, which was evaluated.

Example V-3 20 parts by weight of the nickel polyacrylate metal salt obtained in Synthesis Example V-3 was mixed with ethyl acetate 40
The paste was dissolved in parts by weight, and 10 parts by weight of terpineol was added to produce a paste, and a multilayer ceramic capacitor was prepared and evaluated in the same manner as in Example V-1.

Example V-4 20 parts by weight of the nickel polyacrylate metal salt obtained in Synthesis Example V-4 was dissolved in 50 parts by weight of methanol / ethyl acetate (1/1 weight ratio), and terpineol was added to 10 parts by weight. Was added, 15 parts by weight of an acrylic resin and 5 parts by weight of nickel powder were added as an organic binder, and the mixture was sufficiently stirred to produce a paste. A multilayer ceramic capacitor was prepared and evaluated in the same manner as in Example V-1. Was done.

(Comparative Example V-1) 50 parts by weight of nickel powder
1 part by weight of ethyl cellulose (organic binder), 20 parts by weight of mineral spirit and 30 parts by weight of butyl carbitol were put into a roll mill and kneaded well to prepare a conductive nickel powder paste for an internal electrode. Similarly, a multilayer ceramic capacitor was prepared and evaluated.

Table V shows the results of Examples V-1 to V-4 and Comparative Example V-1.

[0082]

[Table 5]

Examples according to the present invention VI (Synthesis Example VI-1) to (Synthesis Example VI-4) are the same as (Synthesis Example I-1) to (Synthesis Example I-4), respectively.

Example VI-1 30 parts by weight of IPA and 10 parts by weight of terpineol were added to 100 parts by weight of the nickel versatate obtained in Synthesis Example VI-1, and mixed to obtain a gel-like metal salt. Thereafter, 5 parts by weight of the nickel powder,
Ethyl cellulose 2 parts by weight, acrylic resin 12 parts by weight,
3 parts by weight of mineral spirits were put into a roll mill and sufficiently kneaded to produce a conductive paste, and printing was performed on barium strontium titanate-based ceramic green sheets to produce multilayer ceramic capacitors, which were evaluated.

Example VI-2 15 parts by weight of nickel maleate obtained in Synthesis Example VI-2 was mixed with 10 parts by weight of a mixed solvent of xylene / ethyl acetate (1/1 weight ratio) and terpineol 1
0 parts by weight were added and mixed to obtain a gel-like metal salt. Thereafter, 5 parts by weight of nickel powder and 12 parts by weight of acrylic resin were added to produce a conductive metal salt paste composed of a gel-like metal salt and fine metal powder, and barium titanate was produced in the same manner as in Example VI-1. Printing was performed on a strontium-based ceramic green sheet to produce a multilayer ceramic capacitor, which was evaluated.

Example VI-3 Ethyl acetate 4 was added to 20 parts by weight of the nickel polyacrylate metal salt obtained in Synthesis Example VI-3.
0 parts by weight and 10 parts by weight of terpineol were added and mixed to produce a gel metal salt. To this, 15 parts by weight of an acrylic resin and 3 parts by weight of nickel powder as an organic binder were added and stirred to produce a paste.
In the same manner as in the above, printing was performed on the barium strontium titanate-based ceramic green sheet to prepare a multilayer ceramic capacitor, which was evaluated.

Example VI-4 Methanol / 20 parts by weight of the nickel polyacrylate metal salt obtained in Synthesis Example VI-4 was added.
50 parts by weight of ethyl acetate (1/1 weight ratio) and 10 parts by weight of terpineol were added to produce a gel metal salt. Thereafter, 15 parts by weight of an acrylic resin and 5 parts by weight of nickel powder were added as an organic binder, and the mixture was sufficiently stirred to produce a paste. In the same manner as in Example VI-1, printing was performed on a barium strontium titanate-based ceramic green sheet. Then, a multilayer ceramic capacitor was prepared and evaluated.

(Comparative Example VI-1) Nickel powder 50 parts by weight, ethyl cellulose 4 parts by weight, mineral spirit 6
0 parts by weight and 30 parts by weight of butyl carbitol are put into a roll mill and sufficiently kneaded to prepare a conductive nickel powder paste for an internal electrode. In the same manner as in Example VI-1, barium strontium titanate-based ceramic green is used. Printing was performed on the sheet to produce a multilayer ceramic capacitor, which was evaluated.

Examples VI-1 to VI-4 and Comparative Example VI-1
Table VI shows the results.

[0090]

[Table 6]

Examples according to the present invention VII (Synthesis Example VII-1) to (Synthesis Example VII-4) are the same as (Synthesis Example I-1) to (Synthesis Example I-4), respectively.

(Example VII-1) 100 parts by weight of the nickel versatate obtained in Synthesis Example VII-1 was dissolved in 12 parts by weight of an acrylic resin and 2 parts by weight of ethyl cellulose in 30 parts by weight of ethyl alcohol, and 10 parts by weight of terpineol was obtained. Then, a paste was produced by adding a portion, and printing was performed on a barium strontium titanate-based ceramic green sheet to produce a multilayer ceramic capacitor, which was evaluated.

Example VII-2 15 parts by weight of the nickel maleate obtained in Synthesis Example VII-2, 12 parts by weight of an acrylic resin, and 1 part by weight of ethylcellulose were 25 parts by weight of xylene / ethyl acetate (1/1 weight ratio). Was added to 10 parts by weight of terpineol to prepare a paste.
A multilayer ceramic capacitor was prepared and evaluated in the same manner as described above.

Example VII-3 20 parts by weight of the nickel polyacrylate metal salt obtained in Synthesis Example VII-3 was dissolved in 40 parts by weight of ethyl acetate, and 10 parts by weight of terpineol was added. A paste was prepared by adding 15 parts by weight of a resin and 2 parts by weight of ethyl cellulose,
A multilayer ceramic capacitor was prepared and evaluated in the same manner as in Example VII-1.

(Example VII-4) 20 parts by weight of the nickel polyacrylate metal salt obtained in Synthesis Example VII-4 was dissolved in 50 parts by weight of methanol / ethyl acetate (1/1 weight ratio), and 10 parts by weight of terpineol was added. Was added, and 15 parts by weight of an acrylic resin and 1 part by weight of ethyl cellulose were added as an organic binder to produce a paste. A multilayer ceramic capacitor was prepared and evaluated in the same manner as in Example VII-1.

(Comparative Example VII-1) 50 parts by weight of the nickel powder, 4 parts by weight of ethyl cellulose, 60 parts by weight of mineral spirit and 30 parts by weight of butyl carbitol were put into a roll mill, sufficiently kneaded, and kneaded. A nickel powder paste was prepared, and a multilayer ceramic capacitor was prepared and evaluated in the same manner as in Example VII-1.

Examples VII-1 to VII-4 and Comparative Example VII-
The results of 1 are shown in Table VII.

[0098]

[Table 7]

Examples (Synthesis Example VIII-1) to (Synthesis Example VIII-4) according to the present invention VIII are the same as (Synthesis Example I-1) to (Synthesis Example I-4), respectively.

Example VIII-1 To 100 parts by weight of the nickel versatate obtained in Synthesis Example VIII-1, 30 parts by weight of ethyl alcohol and 10 parts by weight of terpineol were added and mixed to obtain a gel metal salt. Ethyl cellulose 1
The conductive metal salt paste was manufactured by adding the parts by weight and thoroughly mixed, and printing was performed on a barium strontium titanate-based ceramic green sheet to produce a multilayer ceramic capacitor, which was evaluated.

Example VIII-2 To 15 parts by weight of the nickel maleate obtained in Synthesis Example VIII-2, 25 parts by weight of a xylene / ethyl acetate mixed solvent (1/1 weight ratio) and 10 parts by weight of terpineol were added. The resulting mixture was converted into a gel-like metal salt, and then 2 parts by weight of ethyl cellulose was added to produce a conductive metal salt paste. A multilayer ceramic capacitor was prepared and evaluated in the same manner as in Example VIII-1.

Example VIII-3 To 20 parts by weight of the nickel polyacrylate metal salt obtained in Synthesis Example VIII-3, 40 parts by weight of ethyl acetate and 10 parts by weight of terpineol were added to produce a gel-like metal salt. Then, 1 part by weight of ethyl cellulose was further added to produce a paste, and a multilayer ceramic capacitor was prepared and evaluated in the same manner as in Example VIII-1.

Example VIII-4 To 20 parts by weight of the nickel polyacrylate metal salt obtained in Synthesis Example VIII-4, 50 parts by weight of methanol / ethyl acetate (1/1 weight ratio) and 10 parts by weight of terpineol were added. A paste was produced by adding 7 parts by weight of ethylcellulose, and a multilayer ceramic capacitor was prepared and evaluated in the same manner as in Example VIII-1.

(Comparative Example VIII-1) The Nickel Powder 50
Parts by weight, 4 parts by weight of ethylcellulose, 60 parts by weight of mineral spirit and 30 parts by weight of butyl carbitol were put into a roll mill and kneaded well to prepare a conductive nickel powder paste for an internal electrode, as in Example VIII-1. Then, a multilayer ceramic capacitor was prepared and evaluated.

Examples VIII-1 to VIII-4 and Comparative Example VI
The results of II-1 are shown in Table VIII.

[0106]

[Table 8]

Examples according to the present invention IX (Synthesis Example IX-1) are the same as (Synthesis Example I-1).

Example IX-1 100 parts by weight of the nickel versatate obtained in Synthesis Example IX-1 having an average particle size of 0.1 part by weight.
40 parts by weight of 1 μm barium titanate fine powder, 1 part by weight of ethyl cellulose, 3 parts by weight of mineral spirit, 5 parts by weight of isopropyl alcohol, and 10 parts by weight of terpineol were sufficiently kneaded in a roll mill to obtain a conductive paste. This conductive paste was printed on a ceramic green sheet of barium titanate to produce a multilayer ceramic capacitor, which was evaluated.

Example IX-2 100 parts by weight of the nickel versatate obtained in Synthesis Example IX-1 having an average particle size of 0.1 part by weight.
40 parts by weight of 1 μm strontium titanate fine powder, 1 part by weight of ethyl cellulose, 3 parts by weight of mineral spirit, 5 parts by weight of isopropyl alcohol, and 10 parts by weight of terpineol were sufficiently kneaded in a roll mill to obtain a conductive paste. This conductive paste was printed on a ceramic green sheet of barium titanate to produce a multilayer ceramic capacitor, which was evaluated.

Example IX-3 100 parts by weight of the nickel versatate obtained in Synthesis Example IX-1 having an average particle size of 0.1 part by weight.
A 5 μm barium titanate fine powder (40 parts by weight), ethyl cellulose (1 part by weight), mineral spirit (3 parts by weight), isopropyl alcohol (5 parts by weight), and terpineol (10 parts by weight) were put in a roll mill and sufficiently kneaded to obtain a conductive paste. This conductive paste was printed on a ceramic green sheet of barium titanate to produce a multilayer ceramic capacitor, which was evaluated.

Example IX-4 100 parts by weight of the nickel versatate obtained in Synthesis Example IX-1 having an average particle diameter of 0.1 part by weight.
40 parts by weight of a mixture of 20 parts by weight of 1 μm barium titanate fine powder and 20 parts by weight of strontium titanate fine powder having an average particle diameter of 0.1 μm, 1 part by weight of ethyl cellulose, 3 parts by weight of mineral spirit, 5 parts by weight of isopropyl alcohol Parts and 10 parts by weight of terpineol were put in a roll mill and sufficiently kneaded to obtain a conductive paste. This conductive paste was printed on a ceramic green sheet of barium titanate to prepare a multilayer ceramic capacitor, which was evaluated.

Comparative Example IX-1 50 parts by weight of nickel powder, 1 part by weight of ethyl cellulose (organic binder), 20 parts by weight of mineral spirit, and butyl carbitol 3
0 parts by weight were put into a roll mill, and kneaded well to prepare a conductive nickel powder paste for an internal electrode.
Create a multilayer ceramic capacitor in the same manner as in 1,
An evaluation was performed.

Examples IX-1 to IX-4 and Comparative Example IX-1
Are shown in Table IX.

[0114]

[Table 9]

Examples according to the present invention X (Synthesis example X-1) Nickel chloride hexahydrate 59.4 g
(0.25 mol) was dissolved in 250 ml of water, and while stirring, 72.5 g of dimethylglyoxime (0.625 mol) was dissolved.
l) and a solution of 250 ml of ethanol were added, and the mixture was vigorously stirred. The precipitated crystals were filtered and washed with ethanol to obtain 50 g of a nickel glyoxime complex.

(Synthesis Example X-2) Acetylacetone 200
When 60 g (1 mol) of anhydrous ethylenediamine was slowly added to g (2 mol), heat was generated, and 112 g of N, N-bis (1-methyl-3-oxobutylidene) ethylenediamine solidified by cooling was obtained. 56 g of the obtained N, N-bis (1-methyl-3-oxobutylidene) ethylenediamine
To a solution of (0.25 mol) in acetone was added 27.8 g (0.3 mol) of nickel hydroxide in excess of an equal amount, and the mixture was refluxed for 3 hours. Water was added to the solution, and N, N-bis (1-methyl-3
(Oxobutylidene) ethylenediaminato nickel complex 43 g was obtained.

(Example X-1) 100 parts by weight of the nickel glyoxime complex obtained in (Synthesis example X-1), 40 parts by weight of barium titanate fine powder having an average particle diameter of 0.1 μm, and 1 part by weight of ethyl cellulose , 3 parts by weight of mineral spirit, 5 parts by weight of isopropyl alcohol, and 10 parts by weight of terpineol were put in a roll mill and sufficiently kneaded to obtain a conductive paste. This conductive paste was printed on a ceramic green sheet of barium titanate to prepare a multilayer ceramic capacitor, which was evaluated.

(Example X-2) N, N-bis (1-methyl-3-oxobutylidene) obtained in (Synthesis Example X-2)
100 parts by weight of ethylenediaminato nickel complex, 40 parts by weight of barium titanate fine powder having an average particle diameter of 0.1 μm, 1 part by weight of ethylcellulose, mineral spirit 3
Parts by weight, 5 parts by weight of isopropyl alcohol, and 10 parts by weight of terpineol were put in a roll mill and sufficiently kneaded to obtain a conductive paste. This conductive paste was printed on a ceramic green sheet of barium titanate to produce a multilayer ceramic capacitor, which was evaluated.

Table X shows the results of Examples X-1 and X-2.

[0120]

[Table 10]

[0121]

According to the present invention, a conductive paste for forming an internal electrode of a multilayer ceramic capacitor is formed on a ceramic green sheet by using an organic solvent-soluble metal compound (MC) instead of a conventional metal powder. The thickness of the printed internal electrode became uniform, the capacitance yield and the delamination of the multilayer ceramic capacitor were reduced, and the effect of improving the reliability of the capacitor performance was obtained.

 ──────────────────────────────────────────────────続 き Continued on front page (31) Priority claim number Japanese Patent Application No. 2000-321568 (P2000-321568) (32) Priority date October 20, 2000 (2000.10.20) (33) Priority claim country Japan (JP) (31) Priority claim number Japanese Patent Application No. 2000-321571 (P2000-321571) (32) Priority date October 20, 2000 (2000.10.20) (33) Priority claim country Japan (JP) (31) Priority claim number Japanese Patent Application No. 2000-321573 (P2000-321573) (32) Priority date October 20, 2000 (2000.10.20) (33) Priority claim country Japan (JP) (31) ) Priority claim number Japanese Patent Application No. 2000-321581 (P2000-321581) (32) Priority date October 20, 2000 (2000.10.20) (33) Priority claiming country Japan (JP) (31) Priority Claim Number Japanese Patent Application No. 2000-321584 (P2000-321584) (32) Priority Date October 20, 2000 (2000.10.20) (33) Priority Claim Country Japan (JP) (31) Priority Claim Number Application No. 2001-83641 (P2001-83641) (32) Priority Date March 22, 2001 (2001.3.22) (33) Priority Country Japan (JP) (72) Inventor Tatsuya Kanno Himeji, Hyogo Prefecture 3-7-3 Shirodaidai (72) Inventor Koichi Okuda 500, Kamiyube, Yobe-ku, Himeji-shi, Hyogo (72) Inventor Masaaki Shimada 4-1-1, Kiyomidai, Kawachinagano-shi, Osaka (72) Inventor Takahiro Sakazaki 2-18-35, 18-18, Yodojo-ku, Yokogawa-ku, Osaka-shi Inside Yamanaka Chemical Industry Co., Ltd. F term in the company (reference) 5E001 AB03 AE02 AH01 AH09 AJ01 5G301 DA03 DA04 DA05 DA06 DA09 DA10 DA11 DA14 DA33 DA55 DA57 DA60 DD01

Claims (26)

[Claims] 1. A metal compound (MC) which becomes a metal upon firing.
Alternatively, a conductive metal compound paste containing the metal compound (MC) and an organic solvent (S). 2. A metal compound (MC) is a metal salt, a metal complex, an organic metal compound having a metal-carbon bond, a metal compound in which a metal and an organic group are bonded via an oxygen atom, and a metal via a nitrogen atom. The conductive metal compound paste according to claim 1, wherein the paste is at least one selected from the group consisting of a metal compound to which an organic group binds and a metal-organic compound interlayer compound. 3. The conductive metal compound paste according to claim 1, wherein the metal compound (MC) is a metal salt or a metal complex (both are referred to as “metal salts”). 4. The conductive metal compound paste according to claim 3, wherein the metal compound (MC) is a metal salt of an organic carboxylic acid or an anhydride thereof. 5. The conductive metal compound paste according to claim 3, wherein the metal compound (MC) is a metal salt of an organic nitrogen compound. 6. The metal compound (MC) is represented by the following general formula [1]:
The conductive metal compound paste according to claim 3, which is a metal complex of a dicarbonyl compound represented by the following formula: R ¹ —C (＝ O) —R ² —C (＝ O) —R ³ [1] (wherein, R ¹ and R ³ are each independently a straight-chain or branched alkyl group having 1 to 6 carbon atoms) , A phenyl group or an alkyl-substituted phenyl group, and R ² is an optionally branched alkylene group.) 7. The conductive metal compound paste according to claim 1, wherein the metal of the metal compound (MC) is a noble metal and / or a base metal. 8. The conductive metal compound paste according to claim 7, wherein the noble metal is at least one selected from the group consisting of palladium, gold, silver and copper. 9. The conductive metal compound paste according to claim 7, wherein the base metal is at least one selected from the group consisting of nickel, cobalt, aluminum, tungsten and molybdenum. 10. The method according to claim 1, wherein the metal compound (MC) or the metal compound (MC) and the organic solvent (S) are in the form of a gel and / or a sol. Item 7. The conductive metal compound paste according to item 1. 11. The method according to claim 1, wherein the metal compound (MC) is an organic solvent (S).
The conductive metal compound paste according to any one of claims 1 to 9, wherein the conductive metal compound paste is dissolved in a conductive metal compound paste. 12. An organic solvent (S) comprising an aromatic hydrocarbon compound, an aliphatic hydrocarbon compound, an alcohol compound,
The conductive metal compound paste according to any one of claims 1 to 11, wherein the paste is at least one selected from the group consisting of an ether compound and an ester compound. 13. The conductive metal compound paste according to claim 1, further comprising a metal fine powder (MP). 14. The conductive metal compound paste according to claim 13, wherein the amount of the fine metal powder (MP) is 2 to 50 parts by weight based on 100 parts by weight of the metal compound (MC). 15. The conductive metal compound paste according to claim 1, further comprising a ceramic fine powder (CP). 16. The conductive metal compound paste according to claim 15, wherein the ceramic fine powder (CP) is at least one selected from barium titanate and strontium titanate. 17. The conductive metal compound paste according to claim 15, wherein the amount of the ceramic fine powder (CP) is 5 to 50 parts by weight based on 100 parts by weight of the metal compound (MC). 18. The conductive metal compound paste according to claim 1, further comprising an organic binder (B). 19. The conductive metal according to claim 18, wherein the organic binder (B) is at least one selected from the group consisting of an acrylic resin, a phenolic resin, an alkyd resin, an epoxy resin, and a rosin ester resin. Compound paste. 20. The conductive metal compound paste according to claim 1, further comprising a viscosity modifier (N). 21. The conductive metal compound paste according to claim 20, wherein the viscosity modifier (N) is a cellulosic compound. 22. The conductive metal compound paste according to claim 1, which is used for manufacturing a laminated ceramic capacitor. 23. A metal compound (MC) used for producing the conductive metal compound paste according to any one of claims 1 to 22. 24. The conductive metal compound paste according to claim 1 is printed on one surface of a dielectric ceramic green sheet, and after removing an organic solvent (S), the plurality of sheets are printed. A method for manufacturing a laminated ceramic capacitor, comprising stacking in the same direction, firing and sintering to obtain a laminate in which conductive internal electrodes and dielectric ceramic layers are alternately formed. 25. A multilayer ceramic capacitor obtained by the method for manufacturing a multilayer ceramic capacitor according to claim 24. 26. The conductive internal electrode has a thickness of 0.1 to 2 μm.
26. The multilayer ceramic capacitor according to claim 25, wherein m is m.