WO2004053901A1 - 外部電極を備えた電子部品 - Google Patents
外部電極を備えた電子部品 Download PDFInfo
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- WO2004053901A1 WO2004053901A1 PCT/JP2003/015745 JP0315745W WO2004053901A1 WO 2004053901 A1 WO2004053901 A1 WO 2004053901A1 JP 0315745 W JP0315745 W JP 0315745W WO 2004053901 A1 WO2004053901 A1 WO 2004053901A1
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- melting point
- conductive paste
- multilayer ceramic
- resin
- metal powder
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
-
- 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 OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/005—Electrodes
Definitions
- the present invention relates to a multilayer ceramic electronic component.
- the present invention relates to a multilayer ceramic electronic component such as a multilayer ceramic capacitor having high reliability, which is suitable for mounting on a board and performing a plating process.
- Figure 1 shows a multilayer ceramic capacitor, which is an example of multilayer ceramic electronic components.
- the external electrodes 4 formed on the internal electrode take-out surface of the ceramic composite of the multilayer ceramic capacitor 1 in which the ceramic dielectrics 2 and the internal electrodes 3 are alternately laminated generally have a firing type conductive paste or a thermosetting conductive paste. And is formed by the following method.
- the first method is to apply, for example, a fired conductive paste obtained by mixing a vehicle and conductive particles such as Ag and Cu and a glass frit to a surface where the internal electrode 3 of the multilayer ceramic composite is taken out, and to dry the paste. Then, the external electrodes 4 are formed by firing at a high temperature of 500 to 900 ° C. in an atmosphere of an inert gas such as nitrogen.
- a fired conductive paste obtained by mixing a vehicle and conductive particles such as Ag and Cu and a glass frit to a surface where the internal electrode 3 of the multilayer ceramic composite is taken out, and to dry the paste.
- the external electrodes 4 are formed by firing at a high temperature of 500 to 900 ° C. in an atmosphere of an inert gas such as nitrogen.
- the second method is to apply a thermosetting conductive paste in which conductive particles such as Ag powder are mixed with a thermosetting resin to the take-out surface of the internal electrode 3 of the multilayer ceramic composite,
- the third method is to use a thermosetting conductive paste obtained by mixing a thermosetting resin with a thermally decomposable organometallic substance such as silver acetate or conductive particles such as Ag powder.
- This is a method of forming the external electrode 4 by applying the heat to the substrate at 350 ° C. (see, for example, Japanese Patent Application Laid-Open No. 2000-188283).
- a plating layer 5 is formed on the surface of the electrode layer as necessary in order to increase the adhesive strength when the obtained capacitor element is soldered and mounted on a substrate or the like.
- the surface of the external electrode is electroplated with a Ni After that, solder plating and Sn plating are further performed by electric plating.
- the capacitor having the external electrode obtained by the first method described above has a problem in that the glass frit component in the conductive paste diffuses into the inside of the capacitor element at the time of high-temperature baking, resulting in poor adhesion due to glass floating and a problem with the substrate. There is a defect such as cracking during solder mounting.
- the penetration of the plating liquid into the sintered body during plating processing causes a problem with the reliability of the capacitor performance, such as a decrease in the capacitance below the design value and a deterioration in the insulation resistance.
- capacitors with external electrodes obtained by a method of thermosetting at a low temperature using a second thermosetting conductive paste can solve the above-mentioned problems of mounting on a board and plating. Since the curing temperature is low, the solid phase diffusion between the metal and the conductive particles such as Ag powder in the conductive paste and the internal electrode does not progress, and the capacitance etc. designed due to poor connection between the internal and external electrodes Cannot be obtained and the reliability is inferior.
- a capacitor having an external electrode formed using a thermosetting conductive paste containing a third thermally decomposable organometallic has a reduced pot life of the paste due to the added silver acetate and amine. There is a problem such as insulation deterioration during the humidity resistance life.
- An object of the present invention is to solve the above-mentioned problems of the prior art in the formation of external electrodes and subsequent plating. That is, an object of the present invention is to solve the problem of the bonding property between the internal electrode and the external electrode of the thermosetting conductive paste and to provide a multilayer ceramic electronic component having high reliability suitable for mounting on a board and plating. It shall be. Disclosure of the invention
- the present invention relates to a multilayer ceramic electronic component having an external electrode formed of a thermosetting conductive paste containing conductive particles having a high melting point, metal powder having a melting point of 30 or less, and resin.
- the present invention provides a thermosetting conductive paste for forming an external electrode by using metal powder having a melting point of 300 ° C. or less in addition to conventionally used high-melting conductive particles.
- the present inventors have found that a multilayer ceramic electronic component having excellent bonding properties between an internal electrode and an external electrode and suitable for mounting on a substrate and plating can be obtained.
- the present invention provides (1) a thermosetting conductive paste containing conductive particles having a high melting point, a metal powder having a melting point of 300 ° C. or less and a resin, and a ceramic composite for providing an external electrode; 2) A thermosetting conductive paste is printed or coated on the internal electrode take-out surface of the ceramic composite; and (3) the ceramic composite obtained in (2) is heated at 80 ° C to 400 ° C.
- the present invention relates to a multilayer ceramic electronic component obtained by holding an external electrode for 1 minute to 60 minutes and forming the external electrode.
- thermosetting conductive paste contains a metal powder with a melting point of 300 ° C or lower in addition to the conventionally used conductive particles with a high melting point, so that it can be used at a low curing temperature of about 80 ° C to 400 ° C. Even so, solid phase diffusion between the conductive particles in the conductive paste and the metal of the internal electrode progresses, and it becomes possible to obtain excellent bonding properties between the internal electrode and the external electrode.
- FIG. 1 is a schematic diagram of a multilayer ceramic capacitor, which is an example of a multilayer ceramic electronic component.
- the multilayer ceramic electronic component of the present invention is characterized by having external electrodes formed of a thermosetting conductive paste containing conductive particles having a high melting point, metal powder having a melting point of 300 ° C. or lower, and a resin.
- the thermosetting conductive paste used in the present invention may further contain a curing catalyst, a curing agent, Z or an organic solvent, if desired.
- the high-melting conductive particles include Ag, Cu, Ni, Zn, Al, Pd, Au, Pt, and high-melting metal powders composed of these alloys. These may be used alone or in combination of two or more.
- the metal powder having a high melting point has a melting point of 400 or more, and particularly preferably has a melting point of 600 ° C. or more.
- metal powders of Cu, Ni, Ag, and Ag alloys are preferable because excellent conductivity can be obtained relatively easily, and metals of Ag and Ag alloys are preferable. Powders are particularly preferred.
- Ag alloys include AgCu alloys containing Ag as a main component and AgAu alloys. Gold, AgPd alloy, AgNi alloy and the like.
- metal powder having a melting point of 300 ° C or less As a metal powder having a melting point of 300 ° C or less, Sn, SnZn, SnAg, SnCu, SnAl, SnPb, In, InAg, InZn, InSn, Bi, Biag, BiNi, B i Sn, BiZn or BiPb. These may be used alone or in combination of two or more. From the viewpoint of the bondability between the internal electrode and the external electrode, metal powders of Sn and Sn alloy are particularly preferable.
- the shape of the conductive particles having a high melting point and the metal powder having a melting point of 300 ° C. or less may be any shape such as a spherical shape, a scaly shape, and a needle shape.
- the average particle size is preferably from 0.05 to 30 im, because it gives an excellent surface condition after printing or coating and gives an excellent conductivity to the formed electrode. ra is more preferred.
- the average particle size means the average of the particle diameter in the case of a spherical shape, the major axis of the particle flake in the case of a scale, and the average of the length in the case of a needle shape.
- the mixing amount of the high-melting conductive particles and the metal powder having a melting point of 300 ° C or less in the thermosetting conductive paste indicates that the thermosetting conductive paste has good printability and that the obtained electrode layer has good conductivity. From the viewpoint of the properties, it is preferably 60 to 98% by weight, more preferably 70 to 95% by weight, based on the total weight of the high melting point conductive particles, the metal powder having a melting point of 300 ° C or lower and the resin.
- the amount of the metal powder having a melting point of 300 ° C. or less is preferably 0.1 to 20% by weight, and more preferably 1 to 20% by weight based on the total weight of the high melting point conductive particles and the metal powder having a melting point of 300 ° C. or less. %, More preferably 5 to 20% by weight.
- the resin used for the thermosetting conductive paste functions as a binder and includes a thermosetting resin.
- the thermosetting resin include amino resins such as urea resin, melamine resin, and guanamine resin; bisphenol A type, bisphenol F type, phenol novolak type, alicyclic epoxy resin; oxetane resin; A phenolic resin such as a mold; and a silicone-modified organic resin such as silicone epoxy and silicone polyester are preferable. These resins may be used alone or in combination of two or more. Further, a thermoplastic resin may be used in combination with these thermosetting resins. As the thermoplastic resin, polysulfone, polyethersulfone, maleimide resin and the like are preferable.
- a resin that is liquid at normal temperature is preferable to use as the resin because the amount of the organic solvent used as a diluent can be reduced.
- a liquid resin include a liquid epoxy resin and a liquid phenol resin.
- a resin having compatibility with these liquid resins and exhibiting a solid or ultra-high viscosity at room temperature may be further added and mixed within a range where the mixing system shows fluidity.
- Such resins include epoxy resins such as high molecular weight bisphenol A type epoxy resin, diglycidyl biphenyl, novolak epoxy resin, tetrabromobisphenol A type epoxy resin; resole phenol resin, novolak phenol Noll resins and the like are exemplified.
- the curing mechanism may be a self-curing resin, a curing agent such as amines, imidazoles, acid anhydrides or onium salts, or a curing catalyst, such as an amino resin or phenol. Resin may function as a curing agent for epoxy resin.
- the epoxy resin used for the thermosetting conductive paste is preferably one that is cured by a phenol resin.
- the phenolic resin may be any phenolic resin initial condensate that is commonly used as a curing agent for epoxy resins, and may be a resole type or a novolak type. Stress during curing is relaxed, and excellent heat cycle resistance is achieved.
- 50% by weight or more of the phenolic resin is preferably an alkyl resol type or alkyl novolac type phenol resin.
- the average molecular weight is preferably at least 2,000 to obtain excellent printability.
- alkyl resole type or alkyl novolak type phenol resins an alkyl group having 1 to 18 carbon atoms can be used, and ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, Those having 2 to 10 carbon atoms, such as decyl, are preferred.
- bisphenol-type epoxy resins and resole-type phenolic resins are preferred because of excellent adhesiveness and excellent heat resistance, and a combination of bisphenol-type epoxy resins and resole-type phenolic resins is preferred. Is particularly preferred.
- the weight ratio of the epoxy resin to the phenol resin is preferably in the range of 4: 1 to 1: 4, and 4: 1 :! to 1: 2 is more preferred.
- the amount of the resin contained in the thermosetting conductive paste is determined based on the suitability for printing and the conductivity of the electrode layer obtained by curing, because of the high melting point of conductive particles, metal powder and melting point of 300 ° C or less. 2 to 40% by weight, and more preferably 5 to 30% by weight, based on the total weight of
- thermosetting conductive paste the type and amount of conductive particles and resin are selected, and if necessary, a diluent is used, so that the ceramic composite of the desired electronic component can be printed or coated.
- a diluent is used, so that the ceramic composite of the desired electronic component can be printed or coated.
- the apparent viscosity of the conductive paste at room temperature is preferably from 10 to 50 OPa's, and more preferably from 15 to 30 OPa's.
- an organic solvent is used as the diluent.
- the organic solvent is selected according to the type of the resin, and the amount of the organic solvent used is selected from the high melting point conductive particles used, the metal powder having a melting point of 300 ° C or less, and the resin. It is arbitrarily selected depending on the kind and composition ratio thereof, and the method of printing or applying the conductive paste.
- organic solvent examples include aromatic hydrocarbons such as toluene, xylene, mesitylene, and tetralin; ethers such as tetrahydrofuran; ketones such as methylethyl ketone, methyl isobutyl ketone, cyclohexanone, and isophorone; Ratatatones such as 2-pyrrolidone and 1-methyl-2-pyrrolidone; Ether alcohols such as monomethinooleatenole, diethyleneglyconelemonoethenolateneolete, diethyleneglyconelemonobutynoate ether, and the corresponding propylene glycol derivatives; acetate esters corresponding thereto Such esters; and Malo phosphate, methyl esters of dicarboxylic acids such as succinic acid, di esters such as Echiruesuteru are exemplified.
- aromatic hydrocarbons such as toluene, xylene, mesitylene, and
- thermosetting conductive paste may further include, if necessary, a dispersing aid such as aluminum chelate compounds such as diisopropoxy (ethyl acetate) aluminum; isopropylinoletriisostearoyl titanate.
- a dispersing aid such as aluminum chelate compounds such as diisopropoxy (ethyl acetate) aluminum; isopropylinoletriisostearoyl titanate.
- surfactants such as sorbitan monooleate
- polyester amine salts such as polyamides and the like.
- Such a high molecular compound may be used.
- inorganic and organic pigments such as inorganic and organic pigments,
- thermosetting conductive paste can be prepared by uniformly mixing the components by a mixing means such as a raikai machine, a propeller stirrer, a kneader, a roll, a pot mill and the like.
- the preparation temperature is not particularly limited, but for example, it can be prepared at normal temperature, 20 ° C to 30 ° C.
- thermosetting conductive paste containing a metal powder having a melting point of 300 ° C. or less and a resin, the laminated ceramic electronic component having the external electrodes of the present invention is: It is formed according to a known method.
- a thermosetting conductive paste can be directly printed or coated on the surface of the ceramic composite of the multilayer ceramic capacitor from which the internal electrodes are taken out by screen printing, transfer, dip coating, or the like.
- a fired copper electrode may be first formed on the internal electrode extraction surface, and the paste may be printed or applied thereon.
- printing or coating is performed so that the thickness of the external electrode after curing is preferably 1 to 300 / zm, more preferably 20 to 100 ⁇ .
- the solvent is volatilized at normal temperature or by heating after printing or coating.
- the external electrode formed of the thermosetting conductive paste of the present invention can be formed by curing at a relatively low temperature and for a short time, but in order to obtain sufficient reliability in mounting on a substrate and plating process.
- the 80-400:,:! It is preferably formed by curing for up to 60 minutes.
- the resin in the paste is an epoxy resin using a phenol resin as a curing agent
- curing is performed at 150 to 300 ° C. for 1 to 60 minutes to obtain an external electrode.
- the multilayer ceramic electronic component of the present invention comprises: (1) a thermosetting conductive paste containing conductive particles having a high melting point, a metal powder having a melting point of 300 ° C. or lower, and a resin; and a ceramic composite for providing an external electrode.
- a thermosetting conductive paste containing conductive particles having a high melting point, a metal powder having a melting point of 300 ° C. or lower, and a resin
- a ceramic composite for providing an external electrode.
- diffusion bonding is understood to mean “a method of bonding without melting the base material (that is, the conductive particles and the metal of the internal electrode) itself or its state”.
- the ceramic composite of the multilayer ceramic electronic component used in the present invention may be manufactured by any known method.
- the ceramic composite refers to a laminate obtained by firing a laminate in which ceramic layers and internal electrode layers are alternately laminated, or a laminate in which a resin / ceramic hybrid material and internal electrodes are alternately laminated.
- the ceramic layer or the resin / ceramic hybrid material has properties suitable for the desired electronic component, for example, dielectric properties for a capacitor, and may be obtained by any known method.
- the internal electrode layer is not particularly limited, but it is preferable to use an inexpensive and easily available base metal such as Ni or Cu as the internal electrode.
- the multilayer ceramic electronic component of the present invention includes, for example, capacitors, capacitor arrays, thermistors, varistors, inductors, LCs, CRs,
- It may be an L R and L C R composite part or the like.
- the obtained multilayer ceramic electronic component is subjected to plating on the surface of the electrode layer as necessary in order to increase the bonding strength when soldering and mounting on a substrate or the like.
- the plating process is performed according to a known method, but it is preferable to perform Pb-free plating in consideration of the environment. For example, a Ni plating is applied to the surface of the external electrode by an electric plating in a watt bath or the like, and then a solder plating or a Sn plating is further applied by the electric plating.
- composition of the conductive paste used in the examples and comparative examples is as shown in Table 1 below.
- spherical silver powder A has an average particle size of 0.5 and a purity of 99.5% or more; spherical silver powder B has an average particle size of 0.5 ra and a purity of 99.5% or more; Grain size 1 2; / ra, purity 99% or more; Limpen silver powder D has an average particle size of 5 / m, purity 99% or more (silver powders A to D are manufactured by Namics Corporation), and tin powder A spherical powder having an average particle size of 4 / im and a purity of 99% or more was used.
- the resin-type phenol resin used had a number average molecular weight of 3000, and the bisphenol A-type epoxy resin used had a number average molecular weight of 900.
- Comparative Example 1 Comparative capacitor: preparation of fired electrode
- the conductive paste A (fired type) having the composition shown in Table 1 was connected to the inside of a ceramic composite (2125 type, B characteristics, Ni internal electrode, theoretical capacity lOOnF) of a chip laminated capacitor. Uniformly dip-coat on the electrode extraction surface so that the thickness after firing is about 50 / ra, dry at 150 ° C for 10 minutes, and then dry in air at 65 ° C, 10 ° C.
- the resultant was baked by heating for about 60 minutes, including the time required for raising and lowering the temperature to a predetermined temperature and before and after that, for about 60 minutes to form an external electrode. Subsequently, Ni plating was performed in a Watts bath, and then Sn plating was performed by electric plating to obtain a multilayer chip capacitor.
- Conductive paste B (thermosetting) shown in Table 1 is dip-coated on the surface of the ceramic composite of the above-mentioned chip multilayer capacitor, from which the internal electrodes are taken out, so that the thickness after curing becomes 40-80. After drying at 150 ° C. for 10 minutes, curing was performed at 300 ° C. for 10 minutes in a belt furnace in the atmosphere to form external electrodes. Subsequently, Ni plating was performed in a hot water bath, and then Sn plating was performed by electric plating to obtain a multilayer chip capacitor.
- the conductive paste C (thermosetting) shown in Table 1 was applied, dried, cured, and plated under the conditions of Comparative Example 2 to obtain a multilayer chip capacitor.
- the chip multilayer capacitor element obtained above is placed on a Pb-free solder paste printed on a copper-clad electrode on a glass epoxy substrate, and the temperature is such that the solder paste is sufficiently melted, for example, 250 to 26.
- Solder bonding was performed at a temperature of 0 ° C to obtain test samples for electrical characteristics and bonding strength.
- the initial electrical characteristics (capacitance, tan 5) of the sample were measured with Agient 428 A, and the bonding strength (shear strength) with the substrate electrode was measured with a desktop strength tester manufactured by Eikoichi Engineering. After the heat cycle resistance test (at -55 / 125 ° C (30 minutes 30 minutes); 141,265 and 545 cycles), the same electrical properties and bonding strength was measured. Table 2 shows the results. Table 2
- the electrical characteristics of the capacitor obtained in the example of the present invention after the application of the 545 f-curve show a small decrease in the capacitance even at the initial stage and after the heat cycle, indicating that the capacitor is excellent.
- the capacitor obtained in Comparative Example 1 did not have any electrical characteristics because no contact with the Ni internal electrode was obtained due to poor bonding.
- the capacitance of the capacitor obtained from the conventional thermosetting conductive paste obtained in Comparative Example 2 decreased to about 60% of the initial value after the heat cycle resistance test (545 cycles). However, ta ⁇ ⁇ increased to about 30 times the initial value, and the reliability as a capacitor was poor.
- thermosetting conductive paste was prepared in the same manner.
- the compounding amount of the high-melting conductive particles and the metal powder having a melting point of 300 ° C or less in the thermosetting conductive paste is as follows. The content was 60 to 98% by weight, and a capacitor sample was prepared in the same manner as in Example 1 using the prepared paste, and its electrical characteristics and bonding strength were measured.
- the capacitors obtained in Examples 1a to 1d exhibited good electrical properties and bonding strength as in Example 1, but in particular, high melting point conductive particles and metal powders having a melting point of 300 ° C or less. More preferable electric characteristics and bonding strength were shown at a compounding amount of powder (metal powder ratio in the table) of 70 to 95% by weight.
- thermosetting conductive paste was prepared by the same method as described above with the composition shown in Table 4 below.
- the mixing amount of the metal powder having a melting point of 300 ° C. or less was 1 to 25% by weight based on the total weight of the high melting point conductive particles and the metal powder having a melting point of 300 ° C. or less.
- Sensor samples were prepared and their electrical properties and bonding strength were measured.
- Example 1 The capacitors obtained in e to lg exhibited good electrical properties and bonding strength as in Example 1, but in particular, the amount of the metal powder having a melting point of 300 ° C. or less (tin in the table) In the range of 5 to about 20% by weight, more preferable electric characteristics and bonding strength were exhibited. Table 4
- thermosetting conductive paste was prepared by the same method as described above with the compositions shown in Tables 5 and 6, and a capacitor sample was prepared in the same manner as in Example 1 using the prepared paste. The electrical characteristics and bonding strength were measured. The obtained capacitor showed good electrical properties and bonding strength as in Example 1. Table 5
- thermosetting conductive paste C used in Example 1.
- Metal powders of C or less are converted from tin powder to SnAg (9/1), SnCu (9/1), SnA1 (9/1), SnPb (9/1) InAg (8/2), InZn (8/2), BiPb (8/2) powder (average particle size 4 ⁇ 6 / ira) except that a thermosetting conductive paste was prepared in the same way, and the prepared paste was used to prepare a sample in the same manner as in Example 1, and its electrical characteristics and bonding The strength was measured.
- the obtained capacitor exhibited good electrical characteristics and bonding strength with a capacitance of 99 to 101 nF, a ta ⁇ of 1.4%, and a bonding strength of 10 mm.
- a ceramic composite of a chip laminated thermistor using an Ag-Pd electrode as an internal electrode was prepared.
- the fired conductive paste A used in Comparative Example 1 was immersed in both 3 X 3 X 5 ram prism-shaped terminals (outside surfaces of the internal electrodes) so that the cured thickness was 40 to 80 // m. It was applied, dried at 150 ° C for 10 minutes, and baked at 600 ° C for 10 minutes to form external electrodes. Subsequently, the surface of the obtained external electrode was subjected to Ni plating in a hot water bath, followed by Sn plating by electric plating, to obtain a chip laminated thermistor.
- thermosetting conductive paste B and the thermosetting conductive paste B used in Comparative Example 2 and Example 1 were applied to both terminals of the ceramic composite of the above-mentioned chip laminated thermistor so that the thickness after curing was 40 to 80 / m.
- C was applied by dip coating, dried at 150 ° C for 10 minutes, and cured in an air belt furnace at 300 ° C for 10 minutes to form external electrodes. Subsequently, Ni plating was performed on the surface of each of the obtained external electrodes in a watt bath, and then Sn plating was performed using an electric plating to obtain a chip laminated thermistor.
- the chip laminated thermistor element obtained above is placed on a Pb-free solder paste printed on a copper-clad electrode on a glass epoxy substrate, and the temperature is such that the solder paste is sufficiently melted, for example, 250 to 260 ° C. Soldering was performed at this temperature and used as a test sample. After measuring the initial electrical characteristics (resistance) of the sample with Ag 1ent 4278 A, the resistance after the heat cycle resistance test (-55 ° C / 1 25 ° C (30 minutes 30 minutes); 1000 cycles) The values were measured similarly. Table 7
- Example 17 of the present invention showed no change in the resistance value even after the heat cycle test, indicating that it was an excellent thermistor.
- a ceramic composite of a zinc oxide-based laminated varistor using an Ag-Pd electrode as an internal electrode was prepared. Created.
- the fired conductive paste A used in Comparative Example 1 was dip-coated on both of the 3 ⁇ 3 ⁇ 5 mm prismatic terminals so that the thickness after curing was 40 to 80 m. After drying at 0 ° C. for 10 minutes, firing was performed at 600 ° C. for 10 minutes to form external electrodes. Subsequently, Ni plating was performed on the surface of the obtained external electrode in a watt bath, and then Sn plating was performed by electric plating to obtain a chip laminated varistor.
- thermosetting conductive paste B and the thermosetting conductive paste B used in Comparative Example 2 and Example 1 were applied to both terminals of the ceramic composite of the above-mentioned chip laminated varistor so that the thickness after curing was 40 to 80 im.
- C was applied by dip coating, dried at 150 ° C for 10 minutes, and then cured in an air belt furnace at 300 ° C for 10 minutes to form external electrodes. Subsequently, Ni plating was performed on the surface of each of the obtained external electrodes in a watt bath, and then Sn plating was performed using an electric plating to obtain a chip laminated varistor.
- the chip laminated varistor element obtained above is placed on a Pb-free solder paste printed on a copper-clad electrode of a glass epoxy substrate, and the temperature at which the solder paste sufficiently melts, for example, 250 to Solder joining was performed at a temperature of 260 ° C, which was used as a test sample. After measuring the initial electrical characteristics (varistor voltage) of the sample, applying in moisture: 85 ° C, 85 RH%, electrical characteristics after applying constant current for 100 hours (varistor voltage) was similarly measured. The number of cracks generated was determined by observing the above sample with a 50-fold optical microscope after the wet charging test.
- the chip laminated varistor obtained in Example 18 of the present invention has a small change in the varistor voltage even after the wet charging test, has a small number of cracks in the element body, and is excellent as a varistor. Indicated.
- thermosetting conductive pastes ⁇ and C used in Comparative Example 2 and Example 1 were applied to both terminals of the ceramic composite of the above-mentioned LCR laminated chip so that the thickness after curing was 40 to 80 / ⁇ .
- Each was applied by dip coating, dried at 150 ° C for 10 minutes, and then cured in an air belt furnace at 300 ° C for 10 minutes to form external electrodes. Subsequently, Ni plating was performed on the surface of each of the obtained external electrodes in a watt bath, and then Sn plating was performed by an electric plating to obtain an LCR laminated component.
- the LCR laminated component obtained above is soldered to a 0.8 mm thick FR4 board at a temperature at which the solder paste is sufficiently melted, for example, at a temperature of 250-260 ° C, and a heat cycle resistance test ( One 55 ° C + 125 (30 minutes / 30 minutes); 2000 cycles) was performed.
- the transmission and reception characteristics of the antenna before and after the heat cycle resistance test were measured using an Agient E 5071A network analyzer, and the input loss on the transmission side was 1.5 dB or more, and the attenuation factor on the reception side was 30. Less than dB is shown as the number of defects.
- Table 9 The LCR laminated component obtained in Example 19 of the present invention showed little change in antenna characteristics even after the heat cycle resistance test, indicating that it was excellent as an LCR laminated component.
- the multilayer ceramic electronic component having the external electrodes formed of the thermosetting conductive paste of the present invention can be cured at a low temperature, so that it can be fired at a high temperature found in a conventional firing type conductive paste.
- a multilayer ceramic electronic component can be obtained without causing any trouble and without using a nitrogen atmosphere during firing. Also, there is no deterioration in electrical characteristics unlike the conventional thermosetting 14 conductive paste. Therefore, it has become possible to obtain a multilayer ceramic electronic component that has excellent electrical characteristics and is suitable for mounting on a board and plating.
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JP2004558447A JPWO2004053901A1 (ja) | 2002-12-09 | 2003-12-09 | 外部電極を備えた電子部品 |
AU2003289277A AU2003289277A1 (en) | 2002-12-09 | 2003-12-09 | Electronic part with external electrode |
EP03777414A EP1571680B1 (en) | 2002-12-09 | 2003-12-09 | Electronic part with external electrode |
US10/538,136 US7751174B2 (en) | 2002-12-09 | 2003-12-09 | Electronic part with external electrode |
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JP2002356545 | 2002-12-09 | ||
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EP (1) | EP1571680B1 (ja) |
JP (1) | JPWO2004053901A1 (ja) |
CN (1) | CN100552838C (ja) |
AU (1) | AU2003289277A1 (ja) |
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Cited By (23)
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TWI408702B (zh) * | 2005-12-22 | 2013-09-11 | Namics Corp | 熱硬化性導電性糊膏及具有使用該導電性糊膏而形成之外部電極之積層陶瓷質電子組件 |
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Also Published As
Publication number | Publication date |
---|---|
US7751174B2 (en) | 2010-07-06 |
AU2003289277A1 (en) | 2004-06-30 |
US20060044098A1 (en) | 2006-03-02 |
CN1723514A (zh) | 2006-01-18 |
EP1571680A1 (en) | 2005-09-07 |
CN100552838C (zh) | 2009-10-21 |
EP1571680A4 (en) | 2008-07-09 |
EP1571680B1 (en) | 2012-09-12 |
JPWO2004053901A1 (ja) | 2006-04-13 |
AU2003289277A8 (en) | 2004-06-30 |
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