EP0667031A1 - Pates resineuses electroconductrices et condensateurs ceramiques multi-couches a electrode terminale composee de ces pates - Google Patents

Pates resineuses electroconductrices et condensateurs ceramiques multi-couches a electrode terminale composee de ces pates

Info

Publication number
EP0667031A1
EP0667031A1 EP94900411A EP94900411A EP0667031A1 EP 0667031 A1 EP0667031 A1 EP 0667031A1 EP 94900411 A EP94900411 A EP 94900411A EP 94900411 A EP94900411 A EP 94900411A EP 0667031 A1 EP0667031 A1 EP 0667031A1
Authority
EP
European Patent Office
Prior art keywords
resin
electrically conductive
terminal electrode
multilayer ceramic
paste
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP94900411A
Other languages
German (de)
English (en)
Inventor
Akira Inaba
Takayuki Oba
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP0667031A1 publication Critical patent/EP0667031A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • 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

Definitions

  • This invention relates to an electrically conductive resin composition and in particular to such composition useful as a terminal for multilayer ceramic chi capacitors .
  • Electrically conductive compositions for the formation of a terminal electrode for multilayer ceramic chip capacitor are prepared in the form of pastes having suitable consistency and rheology, which are formed by admixing metal powders of gold, silver, palladium or alloys thereof, glass frits, inert organic vehicles and resins and dispersing them by a mechanical mixing.
  • Such electrically conductive resin pastes are coated onto the opposing surfaces for taking out an inner electrode in MLC element, dried and fired at a high temperature of about 700 to 860°C to form a terminal electrode.
  • This firing causes glass frits in the paste to disperse into a dielectric layer constituting the MLC element, thus effecting fused binding of the particles.
  • fused metal powders in the paste permit mechanical, electrical connection and fixing of the termina electrode comprised of electrically conductive compositions and the MLC element .
  • soldering is employed in attaching such chip type of circuit board to the patterned surface.
  • fused solder is applied to a round area in a circuit patter on which a terminal for tip parts is situated, to effect a prolonged fixing of a copper-clad laminate for circuit boar thereto.
  • a stress occurs in a joint between a terminal electrode and a capacitor element, in particular a capacitor element area corresponding to the periphery of th terminal electrode due to a sinter shrinkage of metal powders in the paste, diffusion of a glass component in the paste into a dielectric constituting a capacitor element an diffusion of metal powders in the paste into an inner electrode of a capacitor element.
  • a crack occurs due to a rapid temperature change when soldering a chip capacitor to a circuit substrate and "deflection" occurs in the circuit due to the external bending force exerted on the substrate.
  • a terminal of a chip type has less degree of freedom and the strength of an inner electrode and a capacitor element formed of a dielectric is lower than that of the substrate comprised of e.g., a glass fabric based epoxy resin. Therefore, "deflection" or forced bending in the circuit substrate produces a crack in a chip capacitor body after package, thus giving no sufficient terminal strength.
  • it has been extensively performed to connect and fix a chip part to both surfaces of the substrate made of alumina, glass fabric or epoxy resin for the purpose of increasing a package density. In such, a both surface package, the occurrence of crack in the capacitor element becomes an important issue.
  • a technical approach has been demanded to form a terminal electrode without a high temperature firing.
  • the present invention provides an electrically conductive resin composition for the formation of a terminal electrode for a multilayer ceramic chip capacitor with no need of a high temperature firing and a multilayer ceramic chip capacitor formed of the same.
  • the electrically conductive resin composition of the invention is paste, comprising an admixture of an electrically conductive filler consisting of a noble metal powder, a resin under, and a curing agent dispersed in an organic medium, the resin binder comprising a mixture of at least two resins of an epoxy resin and a thermosetting or thermoplastic resin and the weight ratio of the noble metal powder to the thermosetting resin being about 100:5 to 100:45.
  • the present invention also provides a multilayer ceramic chip capacitor formed from the electrically conductive resin paste serving as a terminal electrode for the multilayer ceramic chip capacitor.
  • the multilayer ceramic chip capacitor is formed by laminating alternately a plurality of dielectric sheets having an electrically conductive inner electrode adhered thereon in such manner that the areas for taking out the inner electrode are arranged oppositely, laminating the outmost layer with a dielectric sheet for a protective layer to integrate them, applying the electrically conductive resin paste for the multilayer ceramic chip capacitor to said areas in the integrated laminate and.fixing it to form a terminal electrode.
  • the electrically conductive fillers used in the invention can be any of noble metal powders.
  • all metals referred to as noble metals can be used, but gold, silver, platinum, palladium, rhodium, the mixtures thereof and the alloys thereof are particularly used.
  • the resin binders constituting the conductive resin pastes of the invention comprise a mixture of at least two resins of an epoxy resin and a thermosetting or thermoplastic resin.
  • An epoxy resin which is one component of the resin binder refers to that consisting of a compound containing two or more epoxy groups in the molecule which cures by the action of a curing agent or a catalyst.
  • the epoxy resins can include bisphenol A type epoxy resins, i.e., glycidyl etherified compounds of bisphenol A or its analogous compounds, diglycidyl ester type resins, novolak epoxy resins, glycidyl amine type resins, cycloaliphatic epoxy resins or the like. Those epoxy resins are capable of curing with the curing agents described later on.
  • thermosetting resin which is another component of the resin binder can include phenol resins, melamine resins, alkyd resins, unsaturated polyester resins, diarylphthalate resins or the like.
  • Other components of the resin binder may be a thermoplastic resin which can include phenoxy resins, acryl resins or the like.
  • the ratio of resin solid component in the dispersions to conductive filler can vary considerably. As a matter of course, larger amount of resin solid component provides improved mechanical strength, improved adhesion strength of the coated film and improved resistance to wear, but gives an adverse effect on capacitance and dissipation factor which are important among characteristics of capacitor, capacitance being a constant of proportionality between an electrical charge and an applied voltage and dissipation factor being the tangent of the angle ( ⁇ ) at which current lags from 90° vector relative to voltage and expressed as 100 x tan ⁇ .
  • the elastic modulus of the terminal electrode for a multilayer ceramic chip capacitor fabricated from the compositions of the invention is measured in the range of 2.5-3.0 x 10 ⁇ MPa. On the other hand, it was confirmed by measurement that the elastic modulus of the prior terminal electrode for the same capacitor is more than the above range, which is fabricated by coating a paste composition having silver powder and glass frit dispersed in an inert organic solvent, drying and baking at high temperature.
  • the organic media used for the conductive resin paste of the invention are added in order to reduce the viscosity rising during the milling of the binder and the conductive filler and provide improved workability. It is important to select those having the solubility according to kinds of the binder.
  • the media free from the solubility produces an agglomeration of resin which results in no formation of chain combination of conductive filler, making the electrical conductivity unstable and losing physical and chemical stability of the coated film.
  • the organic media which can be used for the conductive resin paste include'aliphatic alcohols, e.g., ethanol, i-propanol, n-propanol, butanol; esters of these alcohols, e.g., their acetate and propionate; caritol solvents, e.g., methyl carbitol, ethyl carbitol, butyl carbitol, butyl carbitol acetate; cellosolve solvents, e.g., cellosolve, butyl cellosolve, isoamyl cellosolve, hexyl cellosolve, butyl cellosolve acetate; ketone solvents, e.g., acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, cyclohexanone and hydrocarbon solvents, e.g., benzene, toluene, xylene,
  • compositions of the invention can be used including: polyamide curing agents, aliphatic polyamine curing agents, cycloaliphatic polyamine curing agents, aromatic polyamine curing agents, dicyandiamide or the like.
  • the curing agents which initiate a curing reaction at a temperature below 40°C are used.
  • Preferable low-temperature curing agents in the present invention are aliphatic polyamine curing agents and dicyandiamide.
  • high-temperature curing agents can also be used, example of which include those which do not react at ordinary temperature, e.g., aromatic polyamine curing agents, HY 932, HT 972, HY 974, HT 976, NX 11014 (available from Ciba Geigy) ; acid anhydride curing agents, HY 920 (available from Ciba Geigy) and amide curing agents or the like.
  • the electrically conductive resin pastes are coated in one layer onto the opposing surfaces for taking out an inner electrode in MLC element to form a terminal electrode area.
  • th terminal electrode area having a multilayer structure of coated films is thought to form.
  • the ratio of the conductive filler component to the resin solid component can be varied.
  • directly bonding to the surfaces for taking out th ⁇ inner electrode in MLC element electrode bonding layer
  • there is ensured good electrical connection of the chip capacitor element to the inner electrode is ensured and there is inhibited a deterioration of the characteristics such as capacitance an dissipation factor which are important electrical characteristics for capacitor.
  • the proportion of the resin solid component in the paste is reduced so as to provide the range of 100:5 to 100:35 by the weight ratio to noble metal powder as described previously.
  • the proportion of the resin solid component is increased in the paste for the coating formation of the soldering layer.
  • the range of 100:20 to 100:40 by the weight ratio to noble metal powder is preferable.
  • the composition is formed in the form of paste by mixing and milling a conductive filler component consisting of a noble metal powder, a resin binder, a curing agent, and other additives with an inert organic solvent.
  • a conductive filler component consisting of a noble metal powder, a resin binder, a curing agent, and other additives with an inert organic solvent.
  • the conductive resin paste thus produced, can be applied to the area for taking out the inner electrode in MLC, for example by coating, screen-printing or dipping.
  • defoaming is preferably performed by applying vacuum during or after the step of depositing the conductive resin paste. Reducing the air gaps by defoaming can prevent the penetration of a plating solution which may be occurred in the subsequent plating treatment.
  • a cured surface of the terminal electrode tailored by depositing the conductive resin paste may contain a large number of voids, since it is not a sintered body. Depending upon a plating condition to the surface, the plating solution may penetrate into those voids. This surface can be polished for the removal of the voids. This polishing extends the metal on the surface, which results in good plate adhesion. As a polishing method may be employed a barrel polish with a small rubber ball.
  • the resultant conductive resin paste was adjusted to a viscosity suitable for the application of dipping.
  • the silver powder used herein has a particle diameter of 0.2-10 ⁇ m.
  • the viscosity of the paste deposited in the terminal by the application of dipping is preferably in the range of 6 to 9 at 16-30 PA.S. 0.5/10 rpm (viscosity ratio) at 10 rpm when Brookfield rotational viscometer (spindle No. 14) was used. Table 1
  • Silver Powder 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 Epoxy resin 6.75 9 11.25 3.7 4.9 6.1 7.4 8.6 8.8
  • Each of the conductive resin pastes thus prepared was coated onto a capacitor chip using a Palomer machine manufactured by Palomer Co., Ltd. After coating those pastes onto a capacitor chip, the pastes of Examples 1-4 were cured at 250°C for 60 minutes. The pastes of Examples 5-10 were cured at 200°C for 60 minutes or 230°C for 60 minutes or 250°C for 60 minutes. The pastes of Comparative Examples 11-12 as described later were cured at 200°C for 60 minutes and the paste of Example 13 was fired at 850°C.
  • Capacitance and Dissipation Factor, tan ⁇ (%) of the resultant capacitors were measured in the following manner.
  • capacitance can be calculated from the formula
  • C 4d in which K is dielectric constant, A is a play area in cm ⁇ and d is thickness of dielectric layer in cm.
  • Capacitance is measured at a frequency of 120 or 1 KHz and IV (A.C.) using a general radioautomatic RLC bridge model 1683. Capacitance was measured between the cathode coating generally soldered to an anode lead. In some case, the lead was soldered to cathode and used for the measurement .
  • Dissipation Factor is the tangent of the angle ( ⁇ ) of the current lugged from a 90° vector relative to voltage, which is expressed herein as % DF (100 x tan ⁇ ) .
  • DF was measured using the same general radioautomatic bridge as mentioned above for the capacitance. Further, the post strength and elasticity modulus of the cured film were measured. The post strength refers to a force requied for bringing down a post after the conductive resin paste was coated on an aluminum substrate and a small disc with a grasp (post) was placed on a coated surface which was in turn cured.
  • the conductive pastes were prepared by mixing silver powders, phenoxy resin and solvent in the proportions indicated in Table 1 and milling the mixture by the similar procedure as in Examples 1-10.
  • the paste used in Example 13 is a firing type of paste.
  • composition of the pastes is shown in Table 1.
  • the curing condition and the electrical properties of the product are shown in Table 2.

Landscapes

  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Conductive Materials (AREA)
  • Ceramic Capacitors (AREA)
  • Fixed Capacitors And Capacitor Manufacturing Machines (AREA)

Abstract

L'invention se rapporte à une pâte résineuse électroconductrice servant à produire une électrode terminale pour un condensateur céramique pastille multi-couche sans cuisson à température élevée, ainsi qu'à un condensateur céramique pastille multi-couche ainsi formé. La pâte résineuse comprend un mélange d'une charge de remplissage électrconductrice composée d'une poudre de métal précieux, d'un liant résineux et d'un agent de durcissement dispersé dans un milieu organique, le liant résineux comprenant un mélange d'au moins deux résines, dont une résine époxy et une résine thermoplastique ou thermodurcissable, le rapport pondéral poudre de métal précieux/résine thermodurcissable étant compris entre environ 100:5 et 100:45.
EP94900411A 1992-11-04 1993-11-03 Pates resineuses electroconductrices et condensateurs ceramiques multi-couches a electrode terminale composee de ces pates Withdrawn EP0667031A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP4294893A JPH06267784A (ja) 1992-11-04 1992-11-04 導電性樹脂ペースト及びそれにより成る端子電極を有した積層セラミックチップコンデンサ
JP294893/92 1992-11-04
PCT/US1993/010325 WO1994010697A1 (fr) 1992-11-04 1993-11-03 Pates resineuses electroconductrices et condensateurs ceramiques multi-couches a electrode terminale composee de ces pates

Publications (1)

Publication Number Publication Date
EP0667031A1 true EP0667031A1 (fr) 1995-08-16

Family

ID=17813618

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94900411A Withdrawn EP0667031A1 (fr) 1992-11-04 1993-11-03 Pates resineuses electroconductrices et condensateurs ceramiques multi-couches a electrode terminale composee de ces pates

Country Status (5)

Country Link
EP (1) EP0667031A1 (fr)
JP (1) JPH06267784A (fr)
KR (1) KR950704801A (fr)
CN (1) CN1038370C (fr)
WO (1) WO1994010697A1 (fr)

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JP2008255279A (ja) * 2007-04-06 2008-10-23 Walsin Technology Corp 電気コンポーネント用端子組成物
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JP5708009B2 (ja) * 2011-02-17 2015-04-30 セイコーエプソン株式会社 光モジュールおよび電子機器
KR102004759B1 (ko) 2012-06-11 2019-07-29 삼성전기주식회사 외부 전극용 도전성 페이스트 조성물 및 이를 이용한 적층 세라믹 전자부품.
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JP6673273B2 (ja) * 2016-09-28 2020-03-25 株式会社村田製作所 電子部品
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Also Published As

Publication number Publication date
WO1994010697A1 (fr) 1994-05-11
JPH06267784A (ja) 1994-09-22
CN1091854A (zh) 1994-09-07
CN1038370C (zh) 1998-05-13
KR950704801A (ko) 1995-11-20

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