KR101559605B1 - Thermosetting conductive paste and laminated ceramic electronic component possessing external electrodes formed using same - Google Patents
Thermosetting conductive paste and laminated ceramic electronic component possessing external electrodes formed using same Download PDFInfo
- Publication number
- KR101559605B1 KR101559605B1 KR1020107019666A KR20107019666A KR101559605B1 KR 101559605 B1 KR101559605 B1 KR 101559605B1 KR 1020107019666 A KR1020107019666 A KR 1020107019666A KR 20107019666 A KR20107019666 A KR 20107019666A KR 101559605 B1 KR101559605 B1 KR 101559605B1
- Authority
- KR
- South Korea
- Prior art keywords
- conductive paste
- silver
- weight
- component
- external electrode
- Prior art date
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- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 52
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- 238000003860 storage Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/228—Terminals
- H01G4/232—Terminals electrically connecting two or more layers of a stacked or rolled capacitor
- H01G4/2325—Terminals electrically connecting two or more layers of a stacked or rolled capacitor characterised by the material of the terminals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/30—Stacked capacitors
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Abstract
The present invention solves the problem of the bonding property of the inner and outer electrodes of the thermosetting conductive paste and can lead to good electrical characteristics (tan?), High reliability (resistance to heat cycle and moisture resistance) And a multilayer ceramic electronic component having an external electrode formed by using the thermally curable conductive paste. (A) 45 to 85 parts by weight of silver powder having an average particle diameter of 0.2 to 30 탆, (B) 5 to 35 parts by weight of tin having an average particle diameter of 0.2 to 15 탆, (C) (A), 5 to 25 parts by weight of silver (II) and / or silver (II) and / or silver and tin alloy fine powder, and (D) 6 to 18 parts by weight of a thermosetting resin. This is a thermosetting conductive paste.
Description
The present invention relates to a multilayer ceramic electronic component having a thermosetting conductive paste and an external electrode formed using the same. In particular, the present invention relates to a multilayer ceramic electronic component such as a multilayer ceramic capacitor having a thermosetting conductive paste capable of forming an external electrode suitable for a plating process, and an external electrode formed using the same.
A multilayer
In the first method, for example, a small-sized conductive paste obtained by mixing conductive particles such as silver powder or copper powder with a glass frit in a vehicle is applied to the take-out surface of the internal electrode 3 of the laminated ceramic composite, To 900 캜, thereby forming the external electrode 4.
In the second method, a thermosetting conductive paste obtained by mixing conductive particles such as silver powder with a thermosetting resin is coated on the take-out surface of the internal electrode 3 of the multilayer ceramic composite body and then thermally cured at a low temperature of 150 to 250 DEG C, Thereby forming the electrode 4 (see, for example, Patent Document 1).
In the third method, a thermosetting conductive paste obtained by mixing thermosetting resin and conductive particles such as a thermally decomposable organometallic compound or silver powder such as acetic acid silver is applied onto the take-out surface of the internal electrode 3 of the multilayer ceramic composite body, C to form the external electrode 4 (see, for example, Patent Document 2).
The fourth method is a method in which a thermosetting conductive paste containing conductive particles having a high melting point and a metal powder having a melting point of 300 DEG C or lower is applied to the thermosetting resin on the take-out surface of the internal electrode 3 of the multilayer ceramic composite, The external electrode 4 is formed by thermosetting at a low temperature of 100 占 폚 (see, for example, Patent Document 3).
In either method, a plating 5 is applied to the surface of the electrode layer as necessary in order to increase the bonding strength when soldering the resulting capacitor element to a substrate or the like. For example, nickel plating is performed on the surface of the external electrode by electroplating with a watt bath or the like, and then solder plating or Sn plating is further performed by electrolytic plating.
However, the capacitor having the external electrode obtained in the first method has a problem that glass frit components in the conductive paste diffuse into the capacitor element at high temperature firing, thereby causing cracking during soldering and mounting on the substrate. Further, there is a problem in the reliability of the capacitor performance that the electrostatic capacity is lower than the designed value or the insulation resistance is deteriorated due to the penetration of the plating liquid into the sintered body during the plating treatment.
On the other hand, the capacitor having the external electrode obtained by the second method can solve the above-described problems in mounting the substrate on the substrate or in the plating process. However, since the curing temperature is low, the conductive particles, such as silver powder in the conductive paste, The solid-state diffusion of the metals does not progress, and the electrical characteristics such as the electrostatic capacity designed by the defective junction of the inner and outer electrodes can not be obtained and the reliability is lowered.
Further, the capacitor having the external electrode obtained by the third method has drawbacks such that the available time of the paste is shortened by the added acetic acid silver and the amine, and insulation deterioration occurs in the wet life time.
In the capacitor having the external electrode obtained in the fourth method, the solder reflow temperature at the time of mounting the electronic component on the board is increased in the lead-free movement due to the recent lead problem, and the solder reflow temperature of the metal powder having a low melting point There is a possibility that solder exposure due to melting occurs.
The present invention has been made for the purpose of solving the above-mentioned problems in the prior art in the formation of the external electrode and the subsequent plating process. Recently, multilayer ceramic electronic parts such as capacitors have been required to have high performance, There is room for improvement in electrical characteristics (tan?), Reliability (heat cycle resistance, moisture resistance), and the like (see Patent Document 4).
An object of the present invention is to solve the above-described problems in the prior art in the formation of the external electrode and the subsequent plating process. That is, the problem of the bonding property of the inner and outer electrodes of the thermosetting conductive paste is solved, and it is possible to bring about good electric characteristics (tan?) And high reliability (resistance to heat cycle and moisture resistance) And a multilayer ceramic electronic component having an external electrode formed by using the thermally curable conductive paste.
(B) 45 to 85 parts by weight of silver powder having an average particle diameter of 0.2 to 30 탆, (B) 5 to 35 parts by weight of tin having an average particle diameter of 0.2 to 15 탆 of an alloy powder, (C) 5 to 25 parts by weight of silver and / or silver tin alloy fine powder of 15 to 150 nm and (D) 6 to 18 parts by weight of a thermosetting resin, wherein the sum of the components (A), (B) Is 100 parts by weight.
The present invention also relates to a multilayer ceramic electronic component having external electrodes formed using the thermosetting conductive paste.
The curing of the thermosetting conductive paste of the present invention makes it possible to cure the thermosetting conductive paste of the present invention and to provide a laminated ceramic electronic part having excellent bonding properties to the inner and outer electrodes and having good electrical characteristics (tan?) And high reliability (resistance to heat cycle and moisture resistance) / RTI > In the present invention, 45 to 85 parts by weight of silver powder having an average particle diameter of 0.2 to 30 탆, 5 to 35 parts by weight of tin having an average particle diameter of 0.2 to 15 탆, silver and silver powder having an average particle diameter of 15 to 150 nm, It is presumed that the diffusion between the metal powder in the conductive paste and the metal powder in the conductive paste and the internal electrode is progressing in the formation of the external electrode. As a result, It is considered that good bonding properties and electrical characteristics of the inner and outer electrodes are obtained.
In addition, a multilayer ceramic electronic component having excellent electrical characteristics (tan?) And high reliability (resistance to heat cycle and moisture resistance) in which the external electrode is formed is provided.
1 is a schematic diagram of a conventional structure for a multilayer ceramic capacitor which is an example of a multilayer ceramic electronic component.
2 is a schematic view of an upper portion of a multilayer ceramic capacitor when a thermosetting conductive paste is applied to the multilayer ceramic capacitor.
3 is a cross-sectional observation result of the sample of Example 2. Fig.
4 is a cross-sectional observation result of the sample of Comparative Example 1. Fig.
(A) 45 to 85 parts by weight of silver powder having an average particle diameter of 0.2 to 30 占 퐉, (B) 5 to 35 parts by weight of tin having an average particle diameter of 0.2 to 15 占 퐉 of an alloy powder, (C) 5 to 25 parts by weight of silver and / or silver tin alloy fine powder having an average particle diameter of 15 to 150 nm and (D) 6 to 18 parts by weight of a thermosetting resin, (C) is 100 parts by weight.
By mixing the component (A), the resistivity of the thermosetting conductive paste after curing can be lowered. The shape of the component (A) may be any shape such as a spherical shape, a flake shape, a scaly shape, a needle shape and the like.
The average particle diameter of the component (A) is preferably from 0.2 to 30 mu m, more preferably from 0.2 to 20 mu m, in view of providing an excellent surface state after printing or application and also providing the formed electrode with excellent conductivity. Further, in terms of conductivity and printing or coating, it is preferable to use silver particles in combination with spherical and flake-like silver particles. In the present specification, the average particle diameter refers to an average of particle diameters in the case of spherical particles, a diameter of the longest particles in the case of flakes, a long diameter of particle flakes in the case of scales, and a length in the case of beds. Unless otherwise specified, the average particle diameter of the metal particles is determined by a scanning electron microscope (SEM) and determined by image analysis.
It is particularly preferable that the component (A) contains a spherical silver powder having an average particle diameter of 0.2 to 5 占 퐉 and a silver powder of a flaky average particle diameter of 5 to 30 占 퐉 in a weight ratio of 99: 1 to 75:25 on the conductive surface.
(A) and / or the component (C) of the thermosetting conductive paste and the internal electrode yarn of the multilayer ceramic electronic component or between the components (A) and (C) of the thermosetting conductive paste by blending the component Diffusion is promoted.
The shape of the component (B) may be any shape such as spherical shape, flake shape, scaly shape, needle shape and the like. When the average particle diameter of the component (B) is 0.2 to 15 탆, antioxidation and conductivity are achieved.
The weight ratio of tin to silver in the component (B) is preferably from 89:11 to 25.5: 74.5, and particularly preferably from 89:11 to 50:50 in terms of the connection with the internal electrode. Thus, it is particularly preferred that the tin alloy contains at least 50 wt% of tin. The component (B) may have a composition of not less than 5% by weight of three or more components including Cu, In, Bi, Ni and the like within a range where the melting point is not higher than 500 캜.
The presence of the component (C) accelerates the formation of an intermetallic compound of Sn-Ni-Ag at the interface between the external electrode formed of the thermosetting conductive paste of the present invention and the ceramic composite, Heat cycle resistance, moisture resistance) is obtained. In particular, it is presumed that the low resistance of the thermosetting conductive paste after curing, good electrical characteristics (tan?), And high reliability (resistance to heat cycle and humidity resistance) are attained by the coexistence of component (A) and component (C) do.
The shape of the component (C) is preferably spherical, scaly, needle-shaped or the like. The component (C) preferably contains a silver tin alloy fine powder having a silver content of 25.5% by weight or more and less than 100% by weight in view of prevention of oxidation and diffusion, and silver tin alloy fine powder having silver content of 50% by weight or more and less than 100% is particularly preferable. As described above, it is particularly preferable that the silver tin alloy fine powder contains at least 50% by weight of silver. The component (C) may be a three or more component including 5 wt% or less of Cu, In, Bi, Ni or the like.
The component (C) is particularly preferably a (a) in that it promotes diffusion between the component (A) and / or the component (B) and the internal electrode of the multilayer ceramic electronic component and diffusion between the component (A) (B) the crystallite diameter is 15 to 50 nm, preferably 20 to 50 nm, and (c) the crystallite diameter is in the range of It is preferable to use a silver fine powder having an average particle size ratio of 1 to 10, preferably 1 to 7.5. Here, the crystallite diameter is obtained by calculating the half width of the peak of the surface index (1,1,1) plane from the measurement by the powder X-ray diffractometry using the Kα line of Cu as a source and calculating the half width of the peak by the Scherrer equation .
The above-mentioned silver powder and silver-tin alloy powder can be produced by a conventional wet reduction method, a vapor-phase method, or a commercially available product.
The silver fine powder can be obtained by, for example, mixing a silver salt of a carboxylic acid and an aliphatic primary amine in the presence or absence of an organic solvent, then adding a reducing agent, and reacting the silver fine powder at a reaction temperature of 20 to 80 ° C .
The silver salt of the carboxylic acid is not particularly limited, but is preferably a silver salt of an aliphatic monocarboxylic acid, more preferably acetic acid, propionic acid or butyric acid. These may be used alone or in combination of two or more.
The aliphatic primary amine is not particularly limited, but may be a chain aliphatic primary amine or a cyclic aliphatic primary amine. Preferably 3-methoxypropylamine, 3-aminopropanol or 1,2-diaminocyclohexane. These may be used alone or in combination of two or more.
The amount of the aliphatic primary amine to be used is preferably at least 1 equivalent based on 1 equivalent of the silver salt of the carboxylic acid, more preferably 1.0 to 3.0 equivalents in view of the effect of the excess aliphatic primary amine in the environment and the like, Is 1.0 to 2.0 equivalents, more preferably 1.0 to 1.5 equivalents, particularly preferably 1.0 to 1.1 equivalents.
The silver salt of the carboxylic acid and the aliphatic primary amine can be mixed in the presence or absence of an organic solvent. Examples of the organic solvent include alcohols such as ethanol, propanol and butanol, ethers such as propylene glycol dibutyl ether, And aromatic hydrocarbons such as toluene. These may be used alone or in combination of two or more. The amount of the organic solvent to be used may be arbitrary in terms of convenience of mixing and productivity of the silver fine powder in the subsequent step.
The mixing of the silver salt of the carboxylate and the aliphatic primary amine is preferably carried out at a temperature of 20 to 80 캜, more preferably 20 to 60 캜.
As the reducing agent, formic acid, formaldehyde, ascorbic acid or hydrazine is preferable from the viewpoint of controlling the reaction, and more preferred is formic acid. These may be used alone or in combination of two or more.
The amount of the reducing agent to be used is usually not less than the redox equivalent to the silver salt of the carboxylic acid, and the redox equivalent is preferably from 0.5 to 5 times, more preferably from 1 to 3 times. When the silver salt of the carboxylic acid is a silver salt of a monocarboxylic acid and when formic acid is used as a reducing agent, the amount of formic acid to be used in terms of moles of the carboxylic acid is preferably 0.5 to 1.5 moles per mol of the silver salt of the carboxylic acid, Is 0.5 to 1.0 mol, and more preferably 0.5 to 0.75 mol.
In the addition of the reducing agent and the subsequent reaction, the temperature is maintained at 20 to 80 캜, preferably 20 to 70 캜, and more preferably 20 to 60 캜.
The silver fine powder precipitated by the reaction may be precipitated, and the supernatant liquid may be removed by inclining or the like, or a solvent such as alcohol such as methanol, ethanol, terpineol, etc. may be added. Further, the layer containing the silver fine powder may be used as it is for the thermosetting conductive paste. This manufacturing method is excellent in productivity because the silver microparticles can be efficiently produced without using a large apparatus, and the silver fine powder obtained by this method is excellent in the diffusibility at low temperatures.
The thermosetting resin of the component (D) functions as a binder and includes an amino resin such as a urea resin, a melamine resin and a guanamine resin; Epoxy resins such as bisphenol A type, bisphenol F type, phenol novolac type, tetra (hydroxyphenyl) ethane type or tris (hydroxyphenyl) methane type, which is a polyfunctional type having many benzene rings; Oxetane resin; Phenol resins such as resol type, alkyl resol type, novolac type, alkyl novolac type, and aralkyl novolac type; Silicone-modified organic resins such as silicone epoxy and silicone polyester, bismaleimide, polyimide resin and the like are preferable. Also, for example, a BT resin can be used. An epoxy resin is preferable in view of the improvement of the conductivity of the thermosetting conductive paste due to the volume shrinkage at the time of curing and the improvement of the adhesion between the thermosetting conductive paste and the multilayer ceramic electronic component, more preferably an epoxy resin of two or more functionalities, Is more preferable, and a 1,1,2,2-tetrakis (hydroxyphenyl) ethane type epoxy resin represented by the general formula (2) in which p is 0 in the general formula (1) is particularly preferable. These resins may be used alone or in combination of two or more.
(Wherein X represents (CH 2 ) p and p is an integer of 0 to 3)
Use of a resin that is liquid at room temperature as the resin is preferable because the amount of the organic solvent used as the diluent can be reduced. Examples of such liquid resins include liquid epoxy resins, liquid phenolic resins, and the like. Further, it is also possible to further add and mix the resin having compatibility with these liquid resins and exhibiting a solid or ultra-high viscosity at room temperature within the range of exhibiting fluidity. As such a resin, an epoxy resin such as a high molecular weight bisphenol A type epoxy resin, diglycidylbiphenyl, novolak type epoxy resin, tetrabromobisphenol A type epoxy resin; Resole-type phenol resins, novolac-type phenol resins, and aralkyl novolac-type phenol resins.
When an epoxy resin is used, a hardening agent such as amines, imidazoles, acid anhydrides or onium salts may be used as the hardening mechanism, or an amino resin or a phenol resin may be used as a hardening agent of an epoxy resin Function. From the standpoint of storage stability, 2-phenyl-4-methyl-5-hydroxymethylimidazole is particularly preferred.
The epoxy resin used for the thermosetting conductive paste is preferably cured with a phenol resin. The phenol resin may be an early condensation product of a phenol resin which is generally used as a curing agent for an epoxy resin, and may be a resol type or novolac type. In order to obtain excellent heat cycle resistance, at least 50% , An aralkyl novolak type phenol resin, a xylene resin or an allyl phenol resin. An aralkyl novolak type phenol resin, which is a polycondensation product of phenol / p-xylylene glycol dimethyl ether represented by the following formula (3), is also preferable. Further, in the case of an alkylresol-type phenol resin, an average molecular weight of 2,000 or more is preferable in order to obtain excellent printability. In the alkylol solvolol type or alkyl novolac type phenol resin, the alkyl group having 1 to 18 carbon atoms can be used, and the alkyl group having 2 to 10 carbon atoms such as ethyl, propyl, butyl, pentyl, hexyl, Do.
(Wherein n is 0 to 300)
Of these resins, tetrakis (hydroxyphenyl) ethane type epoxy resin, aralkyl novolak type phenol resin, resol type phenol resin, xylene resin or allylphenol resin and the like are preferable because of excellent adhesiveness and excellent heat resistance , And a combination of 1,1,2,2-tetrakis (hydroxyphenyl) ethane type epoxy resin with an aralkyl novolak type phenol resin, a resol type phenol resin, a xylene resin or an allyl phenol resin is particularly preferable desirable. When a combination of tetrakis (hydroxyphenyl) ethane type epoxy resin and aralkyl novolac type phenol resin, resol type phenol resin, xylene resin or allyl phenol resin is used, the weight ratio of epoxy resin to phenol resin is 4: Is preferably in the range of 1: 4, more preferably in the range of 4: 1 to 1: 2. Polyimide resins and the like are also effective in terms of heat resistance.
A thermoplastic resin may also be used in combination with the thermosetting resin within the range not to impair the effects of the present invention. As the thermoplastic resin, polysulfone, polyethersulfone, maleimide resin and the like are preferable.
(A) 45 to 85 parts by weight, the component (B) 5 to 35 parts by weight, the component (C) to 100 parts by weight of the total of 100 parts by weight of the component (A) 5 to 25 parts by weight of the component (D) and 6 to 18 parts by weight of the component (D), whereby the printability of the thermosetting paste, the conductivity of the obtained external electrode layer and the bonding property of the inner and outer electrodes are achieved.
Component (B) is particularly preferably used in an amount of 15 to 25 parts by weight based on 100 parts by weight in total of the component (A), the component (B) and the component (C) in terms of conductivity of the external electrode layer obtained from the thermosetting conductive paste, By weight.
Component (C) is particularly preferably used in an amount of from 7 to 15 parts by weight per 100 parts by weight of the total of the component (A), the component (B) and the component (C) in terms of the conductivity of the external electrode layer obtained from the thermosetting conductive paste, By weight.
(D) is preferably 8 to 15 parts by weight, based on 100 parts by weight of the total of the component (A), the component (B) and the component (C) in terms of the printability of thermosetting conductivity and the bonding property of the inner and outer electrodes.
The thermosetting conductive paste is a method of printing or applying ceramic compositions of desired electronic components by selecting the kind and amount of the components (A), (B), (C) and (D) Therefore, it can be produced with an appropriate viscosity. For example, when used for screen printing, the apparent viscosity of the conductive paste at room temperature is preferably from 10 to 500 Pa · s, more preferably from 15 to 300 Pa · s. As the diluent, an organic solvent is used. The organic solvent is selected according to the kind of the resin, and the amount of the organic solvent to be used is selected depending on the kind and composition ratio of the components (A), (B), (C) The method of printing or coating, and the like.
Examples of the organic solvent include aromatic hydrocarbons such as toluene, xylene, mesitylene and tetralin; Ethers such as tetrahydrofuran; Ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and isophorone; Lactones such as 2-pyrrolidone and 1-methyl-2-pyrrolidone; Ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and corresponding propylene glycol derivatives Alcohols; Esters such as acetic acid esters corresponding thereto; And diesters such as methyl esters and ethyl esters of dicarboxylic acids such as malonic acid and succinic acid. The amount of the organic solvent to be used is arbitrarily selected depending on the kind and amount ratio of the components (A), (B), (C) and (D) used and the method of printing or applying the conductive paste.
The heat-curable conductive paste may further contain, if necessary, an aluminum chelate compound such as diisopropoxy (ethylacetate) aluminum as a dispersion aid; Titanate esters such as isopropyl triisostearoyl titanate; Aliphatic polycarboxylic acid esters; Unsaturated fatty acid amine salts; Surfactants such as sorbitan monooleate; Or a polymer compound such as a polyester amine salt or a polyamide may be used. Inorganic and organic pigments, silane coupling agents, leveling agents, thixotropic agents, antifoaming agents and the like may also be added.
The thermosetting conductive paste can be produced by uniformly mixing the components to be mixed by a mixing means such as a Leica (brain ball), a propeller stirrer, a kneader, a roll, a pot mill or the like. Although the production temperature is not particularly limited, it can be produced, for example, at room temperature and 20 to 30 占 폚.
The thus-obtained thermosetting conductive paste can be used to form a multilayer ceramic electronic component having external electrodes according to a known method. For example, the thermosetting conductive paste is printed or applied to the internal electrode lead-out surface of the ceramic composite body of the multilayer ceramic capacitor by an arbitrary method such as screen printing, transfer, or dipping. Usually, the thickness of the external electrode after curing is preferably printed or applied to a thickness of 1 to 300 mu m, more preferably 20 to 100 mu m. When an organic solvent is used, it is dried at room temperature or by heating after printing or coating. Then, in order to obtain an external electrode, it may be cured at 80 to 450 ° C, specifically 200 to 350 ° C, for example. After drying at 80 to 160 ° C, it may be cured at 200 to 350 ° C. In order to sufficiently exhibit the effect of the blending of the component (B) and the component (C), the curing temperature is preferably 250 to 350 ° C. The heat-curable conductive paste of the present invention is easy to cure because it does not need to be placed under an inert gas atmosphere.
The curing time may vary depending on the curing temperature and the like, but is preferably 1 to 60 minutes in view of workability. However, in the case of curing at 250 DEG C or less, it is preferable that the curing time is 10 to 60 minutes from the viewpoint of bonding with the internal electrode. For example, when the resin in the paste is an epoxy resin using a phenol resin as a curing agent, external electrodes can be obtained by performing curing at 200 to 350 DEG C for 10 to 60 minutes. It is preferable to avoid abrupt heating (for example, rapid heating to 300 DEG C or higher) in order to prevent the volatile components in the paste from evaporating at once and causing the coating film to undergo expansion and cracking. The temperature of the ceramic composite body was set to the temperature of the alumina substrate when the K type thermocouple was fixed on an alumina substrate having a width of 20 mm, a length of 20 mm, and a thickness of 1 mm by means of polyimide tape and placed in a reflow furnace. The holding time was set to the time after the temperature of the alumina substrate reached the holding temperature.
The ceramic composite body of the multilayer ceramic electronic component used in the present invention may be manufactured by any one of known methods. In the present invention, the ceramic composite body refers to a laminate obtained by sintering a laminate in which ceramic layers and internal electrode layers are alternately laminated, or a laminate in which resin-ceramic hybrid materials and internal electrodes are alternately laminated. The ceramic layer or the resin / ceramic hybrid material may have any properties suitable for the desired electronic component, for example, a dielectric material if it is a capacitor, and may be obtained by any one of known methods. Also, the internal electrode layer is not particularly limited, but it is preferable that a nonmetal such as nickel, copper or the like which is inexpensive and easy to obtain is used as the internal electrode. In addition, when a Sn-Ag-Ni compound is formed at the interface between the external electrode and the ceramic composite body at the time of forming the external electrode, good electrical characteristics (tan?) And high reliability (resistance to heat cycle and humidity resistance) The surface of the inner electrode of the composite preferably includes nickel, and particularly, a ceramic composite in which the internal electrode is nickel is preferable. The multilayer ceramic electronic component of the present invention may be, for example, a capacitor, a capacitor array, a thermistor, a varistor, an inductor, and an LC, CR, LR and LCR composite component.
The obtained multilayer ceramic electronic component is plated on the surface of the electrode layer as necessary in order to further increase the bonding strength when soldered to a substrate or the like. The plating treatment is performed according to a known method, and it is preferable that lead-free plating is performed in consideration of the environment. For example, nickel plating is performed on the surface of the external electrode by electrolytic plating or electroless plating such as a watt bath, and then solder plating or tin plating is further performed by electrolytic plating or electroless plating.
The multilayer ceramic electronic component obtained by plating the surface of the external electrode formed of the thermosetting conductive paste of the present invention thus obtained is excellent in electrical properties such as bonding properties of the inner and outer electrodes and is useful for mounting on a circuit board or the like.
[Example]
Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. But the present invention is not limited to these examples.
[Production of conductive paste]
The compositions of the conductive pastes used in Examples and Comparative Examples (the numbers in the tables are weight parts unless otherwise specified) are shown in Table 1 below. Component (C) represents the part by weight in terms of the metal.
The silver fine powder having an average particle diameter of 130 nm in Table 1 is produced as follows. 3.0 kg (30.9 moles) of 3-methoxypropylamine was placed in a 10 L glass reaction vessel. With stirring, 5.0 kg (30.0 mol) of acetic acid was added while maintaining the reaction temperature at 45 占 폚 or lower. Immediately after the addition, the solution became a transparent solution and dissolved. As the addition progressed, the solution became turbid gradually, and when the whole amount was added, it became a viscous solution of a grayish brown color. 1.0 kg (21.0 mol) of 95 wt% formic acid was slowly added dropwise thereto. Significant exotherm immediately after dropping was observed, while the reaction temperature was maintained at 30 to 45 캜. Initially, the turbid solution of turbid gray changed from brown to black. After the entire amount was added, the reaction was terminated. The reaction mixture was allowed to stand at 40 占 폚 and separated into two layers. The upper layer was a transparent yellow liquid, and black silver fine particles precipitated in the lower layer. The solution in the upper layer contained no silver component. The solution in the upper layer was removed by tilting and layer separation was carried out using methanol to obtain a silver fine powder having a silver content of 89% by weight.
The obtained silver fine powder is as follows. Average particle diameter 130 nm, crystallite diameter 40 nm, average particle diameter / crystallite diameter = 3.25. Here, the average particle diameter was an average value of the haze diameter obtained by image analysis and observed with a scanning electron microscope (SEM). The crystallite diameter was measured by an X-ray diffraction measurement apparatus (M18XHF22) (1, 1, 1) plane peak with a ray as a source, and is calculated from Scherr's equation.
Next, the silver fine powder having an average particle diameter of 30 nm and 80 nm and the silver fine tin powder having an average particle diameter of 30 nm in Table 1 are prepared as follows. The inside of the plasma reaction chamber was reduced in pressure, replaced with argon atmosphere, and then the pressure was adjusted to 500 Torr to generate an RF plasma frame. From the raw material supply apparatus, argon was used as a carrier gas, and silver foil or silver silicate having a thickness of 5 탆 and a width of 10 mm was fed continuously from the inlet to the reaction chamber at a feeding rate of 1 to 3 g / min while cooling the inlet . The silver or silver tin evaporated in the plasma frame recycled outside the plasma frame to form a silver or silver tin powder. The resulting silver or silver tin powder was sent to the collector together with the carrier gas and collected by a filter. The obtained silver or silver tin powder was in a spherical shape. A supply rate of the raw material foil was varied to prepare silver or silver tin fine powder having an average particle diameter of 30 nm and 80 nm.
[Application test]
The conductive paste having the composition shown in Table 1 was applied to the internal electrode lead-out surface of the ceramic composite body (3216 type, B characteristic, nickel internal electrode, theoretical capacity 10 μF) of the chip lamination capacitor to an ESi After uniformly immersing in a Paloma printing press (Model No. MODEL 2001), the unevenness of the coated surface was observed with an optical microscope 10 times. As shown in Fig. 2, when the thickness B of the convex portion at the center of the film thickness A was less than 25 占 퐉, the case of?, The case of 25 to 30 占 퐉 being?, And the case of being thicker than 30 占 퐉 being x. Examples 1 to 13 were?. Comparative Example 3 was?, And Comparative Examples 4 and 5 were?.
[Preparation of Multilayer Ceramic Capacitor Samples]
The conductive paste having the composition shown in Table 1 was applied to the inner electrode lead-out surface of the ceramic composite body (3216 type, B characteristic, nickel internal electrode, theoretical capacity 10 μF) of the chip lamination capacitor to a thickness of about 90 μm after curing, And then dried at 150 DEG C for 30 minutes and then cured in a reflow furnace at 300 DEG C for 40 minutes to form an external electrode. Subsequently, nickel plating was performed by a watt bath, and then tin plating was performed by electrolytic plating to obtain a chip-laminated capacitor.
[Measurement of resistivity]
A zigzag pattern printing of 71 mm in length, 1 mm in width and 20 탆 in thickness was carried out on an alumina substrate having a width of 20 mm, a length of 20 mm and a thickness of 1 mm using a stainless steel screen of 250 mesh and dried at 150 캜 for 10 minutes After that, it was cured in the air at 300 DEG C for 40 minutes to form an external electrode. The thickness of the zigzag pattern was determined from the average of six points measured so as to intersect the pattern with a surface roughness shape measuring instrument (trade name: Surfcom 1400, manufactured by Tokyo Seimitsu Co., Ltd.). After curing, the resistivity was measured by a four-terminal method using an LCR meter. The results are shown in Table 2. And Examples 1 to 13 were 0.3 to 2.7 x 10 < -4 > And Comparative Example 7 was 3.7 x 10 < -4 >
[Measurement of Capacitance and Dielectric Tangent]
The initial capacitance and dielectric tangent (tan?) Of the chip-stacked capacitor element obtained above were measured at room temperature and a frequency of 1 kHz using 4278A manufactured by Agilent. Next, the test piece was subjected to a humidity resistance test (autoclave test: 121 ° C (20 hours) at 2 atmospheres), a heat cycle test (-55 ° C / 125 ° C (30 minutes / 30 minutes) ) Were measured in the same manner as the initial characteristics. The results are shown in Table 2. The electrostatic capacities of Examples 1 to 13 were 9.89 to 10.40 μF. The electrostatic capacity of Comparative Example 6 was 9.07 占.. In addition, the initial dielectric tangent of Examples 1 to 13 was 3.2 to 3.9%. The dielectric tangent of Comparative Examples 1, 2, 6 and 7 were 4.9, 4.5, 6.1 and 4.3%, respectively. The dielectric loss tangent after the humidity resistance test after Examples 1 to 13 was 3.2 to 4.0%. The dielectric loss tangent of each of the comparative examples 1, 2, 6 and 7 after the internal heat cycle test was 5.1, 4.6, 6.2 and 4.5, and the dielectric loss tangent after the moisture resistance test was 5.1, 4.8, 6.4 and 4.7%.
[Measurement of bonding strength]
5 mm in width, 1.5 mm in width, 1.5 mm in length, and 25 m in thickness on an alumina substrate having a width of 20 mm, a length of 20 mm and a thickness of 1 mm using a stainless steel screen of 250 mesh, Ten randomly sized alumina chips of 3216 were loaded on the pattern. Dried at 150 DEG C for 10 minutes, and cured at 300 DEG C for 40 minutes in the air to form an external electrode. After curing, the bonding strength (shear strength) of the external electrode to the substrate was measured at a load speed of 12 mm / min using a table strength tester (Model: 1605HTP) manufactured by Ico Engineering. The results are shown in Table 2. Examples 1 to 13 were 2.4 to 3.7 kN / cm < 2 & gt ;.
[Observation of cross section of sample]
The cross section of the sample used for the measurement of electrostatic capacity was observed by reflection electron microscopy with FE-SEM (model number: JSM-7500F) manufactured by Nippon Denshi Kabushiki Kaisha and subjected to EDS analysis to obtain a layer formed of a thermosetting conductive paste and a chip stacked capacitor The interface part of the ceramic composite was observed. (E) a distribution of Ti; and (f) a graph showing the distribution of Ni, the distribution of Ni, the distribution of Ni, The distribution of Ba is shown. 4 shows a cross section of the sample of Comparative Example 1 as shown in Fig. In Fig. 3, it was confirmed that the silver of the thermosetting conductive paste, Ni of the tin and the ceramic composite was diffused to form a Sn-Ag-Ni compound. As a result of quantitative analysis, the weight ratio of Sn: Ag: Ni was 64.6: 6.1: 29.3. It is presumed that the Sn-Ag-Ni compound achieves low resistance, fixed capacitance, low dielectric loss tangent, and high bonding strength of the ceramic composite material having the external electrode formed of the thermosetting conductive paste of the present invention. On the other hand, in the portion shown in FIG. 4, the weight ratio of Sn: Ag: Ni was 54.1: 0: 45.9, and no Sn-Ag-Ni compound was produced.
1: Multilayer Ceramic Capacitor
2: Ceramic dielectric
3: internal electrode layer
4: external electrode layer
5: Plated layer
6: Thermally curable conductive paste
Claims (14)
(a) the primary particles have an average particle diameter of 50 to 150 nm,
(b) a crystallite diameter of 20 to 50 nm, and
(c) a ratio of the average particle diameter to the crystallite diameter is 1 to 7.5
Thermally curable conductive paste.
≪ Formula 1 >
(Wherein X represents (CH 2 ) p and p is an integer of 0 to 3)
(2) A thermosetting conductive paste is printed or applied to the internal electrode lead-out surface of the ceramic composite, and if necessary, dried;
(3) A multilayer ceramic electronic device obtained by holding the ceramic composite obtained in (2) at 200 to 350 DEG C for 10 to 60 minutes to form an external electrode.
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| KR101595035B1 (en) * | 2010-11-18 | 2016-02-17 | 주식회사 엘지화학 | Ag paste composition for forming electrode and Silicon Solar Cell using the same |
| TWI564381B (en) * | 2011-03-31 | 2017-01-01 | 納美仕有限公司 | Thermal conductive composition and thermal conductive body |
| JP5689773B2 (en) * | 2011-10-01 | 2015-03-25 | 株式会社フジクラ | Photoelectric conversion element electrode, photoelectric conversion element, and silver paste used for manufacturing photoelectric conversion element electrode |
| KR101508838B1 (en) * | 2013-08-09 | 2015-04-06 | 삼성전기주식회사 | Multilayer ceramic device and mounsting structure with the same |
| KR102097329B1 (en) | 2013-09-12 | 2020-04-06 | 삼성전기주식회사 | Multi-layered ceramic capacitor, manufacturing method thereof and board for mounting the same |
| KR102007295B1 (en) | 2013-12-12 | 2019-08-05 | 삼성전기주식회사 | Multi-layered ceramic capacitor, manufacturing method thereof and board for mounting the same |
| KR101477430B1 (en) | 2013-12-30 | 2014-12-29 | 삼성전기주식회사 | Multi-layered ceramic electronic part, manufacturing method thereof and board having the same mounted thereon |
| KR20150089276A (en) | 2014-01-27 | 2015-08-05 | 삼성전기주식회사 | Multi-layered ceramic electronic part and conductive paste for external electrode |
| JP6380852B2 (en) * | 2015-12-17 | 2018-08-29 | 株式会社伊東化学研究所 | Heat resistant, acid resistant, conductive metal material |
| JP6804286B2 (en) * | 2015-12-28 | 2020-12-23 | Ｄｏｗａエレクトロニクス株式会社 | Silver alloy powder and its manufacturing method |
| WO2017115462A1 (en) * | 2015-12-28 | 2017-07-06 | Ｄｏｗａエレクトロニクス株式会社 | Silver alloy powder and method for producing same |
| US10446320B2 (en) | 2016-04-15 | 2019-10-15 | Samsung Electro-Mechanics Co., Ltd. | Multilayer capacitor having external electrode including conductive resin layer |
| KR101973433B1 (en) | 2016-04-15 | 2019-04-29 | 삼성전기주식회사 | Multilayered capacitor and method of manufacturing the same |
| KR101892819B1 (en) * | 2016-07-26 | 2018-08-28 | 삼성전기주식회사 | Coil Component |
| US10580567B2 (en) | 2016-07-26 | 2020-03-03 | Samsung Electro-Mechanics Co., Ltd. | Coil component and method of manufacturing the same |
| JP6849374B2 (en) * | 2016-10-06 | 2021-03-24 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーＥ．Ｉ．Ｄｕ Ｐｏｎｔ Ｄｅ Ｎｅｍｏｕｒｓ Ａｎｄ Ｃｏｍｐａｎｙ | Conductive paste for joining |
| KR101892849B1 (en) | 2017-03-02 | 2018-08-28 | 삼성전기주식회사 | Electronic component |
| US10770230B2 (en) | 2017-07-04 | 2020-09-08 | Samsung Electro-Mechanics Co., Ltd. | Multilayer ceramic capacitor and method of manufacturing the same |
| KR101912291B1 (en) | 2017-10-25 | 2018-10-29 | 삼성전기 주식회사 | Inductor |
| JP7379899B2 (en) * | 2019-07-22 | 2023-11-15 | Tdk株式会社 | ceramic electronic components |
| KR20210074610A (en) * | 2019-12-12 | 2021-06-22 | 삼성전기주식회사 | Multi-layer ceramic electronic component and manufacturing method thereof |
| CN113168931B (en) * | 2020-06-24 | 2022-04-05 | 千住金属工业株式会社 | Conductive paste, laminate, and method for bonding Cu substrate or Cu electrode and conductor |
| DE102022114552A1 (en) * | 2022-06-09 | 2023-12-14 | Tdk Electronics Ag | Process for producing a multilayer varistor |
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| JP2002075052A (en) | 2000-08-31 | 2002-03-15 | Mitsubishi Plastics Ind Ltd | Conductive resin composition and sheet |
| JP2002265920A (en) | 2001-03-13 | 2002-09-18 | Namics Corp | Electroconductive adhesive and circuit using the same |
| JP2005310972A (en) | 2004-04-20 | 2005-11-04 | Bridgestone Corp | Electromagnetic wave shielding light transmission window material and its manufacturing method |
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| KR20100110891A (en) | 2010-10-13 |
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