WO2020021872A1 - 導電性ペースト、電極及びチップ抵抗器 - Google Patents

導電性ペースト、電極及びチップ抵抗器 Download PDF

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Publication number
WO2020021872A1
WO2020021872A1 PCT/JP2019/022355 JP2019022355W WO2020021872A1 WO 2020021872 A1 WO2020021872 A1 WO 2020021872A1 JP 2019022355 W JP2019022355 W JP 2019022355W WO 2020021872 A1 WO2020021872 A1 WO 2020021872A1
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WO
WIPO (PCT)
Prior art keywords
conductive paste
glass frit
electrode
silver powder
silica filler
Prior art date
Application number
PCT/JP2019/022355
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
喜昭 吉井
Original Assignee
ナミックス株式会社
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 ナミックス株式会社 filed Critical ナミックス株式会社
Priority to CN201980042843.9A priority Critical patent/CN112334996A/zh
Publication of WO2020021872A1 publication Critical patent/WO2020021872A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern

Definitions

  • the present invention relates to a conductive paste used for forming electrodes of electronic components, for example.
  • FIG. 13 shows an example of a cross-sectional structure of the chip resistor 100.
  • the chip resistor 100 has a rectangular alumina substrate 102, and on the upper surface of the alumina substrate 102, a resistor 104 and an extraction electrode 106 for extracting electricity from the resistor 104 are formed.
  • a lower electrode 108 for mounting the chip resistor 100 on the substrate is formed.
  • a connection electrode 110 for connecting the extraction electrode 106 and the lower electrode 108 is formed on the end face of the alumina substrate 102.
  • the extraction electrode 106 and the lower electrode 108 are formed by applying a conductive paste to the upper and lower surfaces of the alumina substrate 102 by printing and then firing the paste. Generally, a nickel plating film 112 and a tin plating film 114 are formed on the extraction electrode 106, the lower electrode 108, and the connection electrode 110.
  • the required characteristics of the extraction electrode 106 and the lower electrode 108 are different from each other, they are generally formed using different conductive pastes.
  • a conductive paste having a good matching property with the resistor 104 is used for forming the extraction electrode 106.
  • the resistance value of the resistor 104 is low, the resistance value of the extraction electrode 106 is also required to be low. Therefore, a conductive paste that can form a low-resistance electrode is used for forming the extraction electrode 106.
  • conductive pastes containing silver powder and glass frit disclosed in Patent Documents 1 and 2 are known as conductive pastes used for forming electrodes.
  • pre-plating treatment is required. It is said that 70% of plating failures are caused by pretreatment.
  • the plating pretreatment is performed for the purpose of removing contaminants from the surface of the electrode, activating the surface of the electrode, and bringing the electrode into a clean state suitable for plating.
  • Pollutants to be removed can be broadly classified into organic and inorganic.
  • the pretreatment step does not remove all contaminants in a single step. For example, organic substances are removed in a step using an alkaline cleaning agent. The inorganic substance is removed in a step using an acid-based cleaning agent. Therefore, the electrode is required to have high chemical resistance.
  • An object of the present invention is to provide a conductive paste having high chemical resistance and capable of forming a low-resistance electrode.
  • the present inventors have conducted intensive research on a conductive paste having high chemical resistance and capable of forming a low-resistance electrode. As a result, they discovered that the conductive paste contained a silica filler at a predetermined ratio in addition to the silver powder and the glass frit, thereby increasing the chemical resistance, and completed the present invention.
  • the present invention is as follows. (1) containing (A) silver powder, (B) glass frit, (C) silica filler, and (D) a thermoplastic resin,
  • the (B) glass frit includes SiO 2 and TiO 2 ,
  • the mass ratio of SiO 2 contained in the (B) glass frit and SiO 2 contained in the (C) silica filler is 1: (0.25 to 1.6)
  • the conductive paste, wherein the content of the glass frit (B) is less than 20 parts by mass with respect to 100 parts by mass of the silver powder (A).
  • a chip resistor having the electrode according to (6) or (7) A chip resistor having the electrode according to (6) or (7).
  • the conductive paste according to the embodiment of the present invention contains (A) silver powder, (B) a glass frit, (C) a silica filler, and (D) a thermoplastic resin.
  • the glass frit contains SiO 2 and TiO 2 .
  • the mass ratio of (B) SiO 2 contained in the glass frit to (C) SiO 2 contained in the silica filler is 1: (0.25 to 1.6).
  • the content of the glass frit is less than 20 parts by mass relative to 100 parts by mass of the silver powder (A).
  • the conductive paste of the present embodiment contains (A) silver powder as conductive particles.
  • As the silver powder a powder made of silver or an alloy containing silver can be used.
  • the shape of the silver powder particles is not particularly limited, and for example, spherical, granular, flake, and / or flaky silver powder particles can be used.
  • the average particle size of the silver powder is preferably 0.1 ⁇ m to 10 ⁇ m, more preferably 0.1 ⁇ m to 7 ⁇ m, and most preferably 0.1 ⁇ m to 5 ⁇ m.
  • the average particle diameter here means a volume-based median diameter (d50) obtained by a laser diffraction scattering particle size distribution measuring method.
  • a method for producing silver powder is not particularly limited, and for example, it can be produced by a reduction method, a pulverization method, an electrolytic method, an atomizing method, a heat treatment method, or a combination thereof.
  • Flaky silver powder can be produced, for example, by crushing spherical or granular silver particles with a ball mill or the like.
  • the conductive paste of the present embodiment contains (B) glass frit.
  • the glass frit contains SiO 2 and TiO 2 .
  • the adhesion strength of the electrode obtained by firing the conductive paste to the substrate is improved.
  • the glass frit is not particularly limited, a glass frit having a softening point of 300 ° C. or higher, preferably 400 to 900 ° C., more preferably 500 to 800 ° C. can be used.
  • the softening point of the glass frit can be measured using a thermogravimetric device (for example, TG-DTA2000SA manufactured by BRUKER AXS).
  • the glass frit examples include a glass frit such as a titanium borosilicate-based (TiO 2 -based) and a barium borosilicate-based.
  • glass frit examples include bismuth borosilicate, alkali metal borosilicate, alkaline earth metal borosilicate, zinc borosilicate, lead borosilicate, lead borate, lead silicate, and bismuth borate.
  • a glass frit such as a zinc borate type.
  • Glass frit, ZnO, BaO it is preferred to include at least one selected from Na 2 O, the group consisting of CaO and Al 2 O 3. Glass frit, ZnO, BaO, and more preferably contains Na 2 O and Al 2 O 3.
  • the average particle size of the glass frit is preferably 0.1 to 20 ⁇ m, more preferably 0.2 to 10 ⁇ m, and most preferably 0.5 to 5 ⁇ m.
  • the average particle diameter here means a volume-based median diameter (d50) obtained by a laser diffraction scattering particle size distribution measuring method.
  • the content of the glass frit (B) is less than 20 parts by mass, more preferably 0.1 to 15 parts by mass, and still more preferably 100 parts by mass of the silver powder (A). 1.0 to 10 parts by mass.
  • the content of the glass frit is less than this range, the adhesion of the electrode obtained by firing the conductive paste to the substrate is reduced.
  • the content of the glass frit is larger than this range, the resistance of the electrode obtained by firing the conductive paste becomes high.
  • the conductive paste of the present embodiment contains (C) a silica filler.
  • a silica filler for example, spherical silica (SiO 2 ) particles commercially available as a semiconductor sealing material can be used.
  • the shape of the silica filler may be a shape other than a spherical shape.
  • the method for producing the silica filler is not particularly limited, and a silica filler produced by a known method such as a thermal spraying method can be used.
  • the average particle size of the silica filler is preferably 20 nm or more and 5 ⁇ m or less.
  • the average particle diameter here means a volume-based median diameter (d50) obtained by a laser diffraction scattering particle size distribution measuring method.
  • Thermoplastic resin The conductive paste of the present embodiment contains (D) a thermoplastic resin.
  • the thermoplastic resin joins silver powders together in the conductive paste.
  • a resin that is burned off when the conductive paste is fired can be used as the thermoplastic resin.
  • thermoplastic resin for example, a cellulosic resin such as ethyl cellulose and nitrocellulose, an acrylic resin, an alkyd resin, a saturated polyester resin, a butyral resin, polyvinyl alcohol, and hydroxypropyl cellulose can be used. These resins can be used alone or in combination of two or more.
  • the content of the thermoplastic resin is preferably from 0.5 to 30 parts by mass, more preferably from 1.0 to 20 parts by mass, per 100 parts by mass of the silver powder (A).
  • the content of the thermoplastic resin in the conductive paste is within the above range, the applicability of the conductive paste to the substrate is improved, and fine electrodes can be formed with high precision.
  • the content of the thermoplastic resin exceeds the above range, the amount of the thermoplastic resin contained in the conductive paste is too large. For this reason, a fine electrode cannot be formed with high accuracy, and the electrode obtained after firing may have reduced denseness and may have increased resistance.
  • the mass ratio of (B) SiO 2 contained in the glass frit to (C) SiO 2 contained in the silica filler is 1: (0.25 to 1.6). .
  • the mass ratio of (B) SiO 2 contained in the glass frit to (C) SiO 2 contained in the silica filler is more preferably 1: (0.50 to 1.3).
  • the conductive paste of the present embodiment may contain (E) a solvent.
  • the solvent include alcohols such as methanol, ethanol and isopropyl alcohol (IPA), organic acids such as ethylene acetate, aromatic hydrocarbons such as toluene and xylene, and N-methyl-2-pyrrolidone (NMP).
  • N-alkylpyrrolidones amides such as N, N-dimethylformamide (DMF), ketones such as methyl ethyl ketone (MEK), cyclic carbonates such as terpineol (TEL), butyl carbitol (BC), and water.
  • the content of the solvent is not particularly limited, but is preferably 1 to 100 parts by mass, more preferably 5 to 60 parts by mass, per 100 parts by mass of the silver powder (A).
  • the viscosity of the conductive paste of the present embodiment is preferably from 50 to 700 Pa ⁇ s (shear rate: 4.0 sec ⁇ 1 ), more preferably from 100 to 300 Pa ⁇ s (shear rate: 4.0 sec ⁇ 1 ).
  • the conductive paste of the present embodiment may contain other additives, for example, a dispersant, a rheology modifier, a pigment, and the like.
  • the conductive paste of the present embodiment can be produced by mixing the above components using, for example, a raikai machine, a pot mill, a three-roll mill, a rotary mixer, a twin-screw mixer, or the like.
  • a method for forming an electrode on a substrate using the conductive paste of the present embodiment will be described.
  • a conductive paste is applied on a substrate.
  • the coating method is arbitrary, and for example, coating can be performed using a known method such as dispensing, jet dispensing, stencil printing, screen printing, pin transfer, and stamping.
  • the substrate is put into a firing furnace or the like. Then, the conductive paste applied on the substrate is fired at 500 to 900 ° C., more preferably 600 to 900 ° C., and even more preferably 700 to 900 ° C. As a result, the solvent component contained in the conductive paste evaporates at a temperature of 300 ° C. or lower, and the resin component burns off at a temperature of 400 ° C. to 600 ° C. to form a sintered body of the conductive paste.
  • the electrode thus obtained has high chemical resistance and excellent adhesion to the substrate.
  • the conductive paste of this embodiment can be used for forming a circuit of an electronic component, forming an electrode, joining an electronic component to a substrate, and the like. Further, the conductive paste of the present embodiment can be used for forming electrodes of a chip resistor.
  • the conductive paste of the present embodiment has excellent chemical resistance, it can be preferably used for forming an electrode having a plating film formed on the surface.
  • the conductive paste of the present embodiment can be particularly preferably used for forming an extraction electrode for extracting electricity from the resistor of the chip resistor.
  • the electrode obtained by firing the conductive paste of the present embodiment has a sheet resistance of 4 m ⁇ / ⁇ (4 m ⁇ / square) or less, and more preferably 3.4 m ⁇ / ⁇ or less. Therefore, it can be preferably used for forming an electrode required to have low resistance.
  • A Silver powder (A1) Spherical silver powder, average particle size 5 ⁇ m (A2) Flaky silver powder, average particle size 3.5 ⁇ m
  • C silica filler (C1) spherical silica (SiO 2 ) powder, average particle size 0.3 ⁇ m
  • a test piece was prepared according to the following procedure. First, a conductive paste was applied on a 20 mm ⁇ 20 mm ⁇ 1 mm (t) alumina substrate by screen printing. As a result, 20 patterns each having a square pad shape with one side of 1.5 mm were formed on the alumina substrate. A 250 mesh stainless steel mask was used to form the pattern. Next, the conductive paste was dried at 150 ° C. for 10 minutes using a hot-air dryer. After drying the conductive paste, the conductive paste was fired using a firing furnace. The firing temperature is 850 ° C. for 10 minutes, and the total firing time is 60 minutes.
  • the electrode patterns obtained by firing the conductive pastes of Examples 1 to 12 were excellent in chemical resistance and adhesion to the substrate, and had low sheet resistance.
  • the electrode patterns obtained by firing the conductive pastes of Comparative Examples 1 to 3, 5 to 8 were inferior in chemical resistance and adhesion to the substrate.
  • the electrode pattern obtained by firing the conductive paste of Comparative Example 4 had a high sheet resistance.
  • the electrode patterns obtained by firing the conductive pastes of Examples 1 to 8 had a low sheet resistance of 3.4 m ⁇ / ⁇ or less, and were suitable for electrodes requiring low resistance.
  • the electrode patterns obtained by firing the conductive pastes of Examples 1 to 12 had dense surfaces.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Dispersion Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Conductive Materials (AREA)
  • Glass Compositions (AREA)
  • Parts Printed On Printed Circuit Boards (AREA)
  • Non-Insulated Conductors (AREA)
PCT/JP2019/022355 2018-07-26 2019-06-05 導電性ペースト、電極及びチップ抵抗器 WO2020021872A1 (ja)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201980042843.9A CN112334996A (zh) 2018-07-26 2019-06-05 导电膏、电极和片状电阻器

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JP2018-140128 2018-07-26
JP2018140128A JP7082408B2 (ja) 2018-07-26 2018-07-26 導電性ペースト

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112635096A (zh) * 2020-12-10 2021-04-09 潮州三环（集团）股份有限公司 一种片式电阻用银浆

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Publication number Priority date Publication date Assignee Title
JP7434407B2 (ja) 2022-04-25 2024-02-20 株式会社ノリタケカンパニーリミテド 外部電極用ペースト

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000048643A (ja) * 1998-07-28 2000-02-18 Murata Mfg Co Ltd 導電性ペースト及びガラス回路基板
JP2003338218A (ja) * 2002-05-21 2003-11-28 Murata Mfg Co Ltd 導電性ペースト
JP2016538708A (ja) * 2013-03-27 2016-12-08 チェイル インダストリーズ インコーポレイテッド 太陽電池電極形成用組成物およびそれにより製造された電極
WO2018037746A1 (ja) * 2016-08-23 2018-03-01 ナミックス株式会社 導電性ペースト及び太陽電池

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11130459A (ja) * 1997-10-28 1999-05-18 Murata Mfg Co Ltd ガラス基板用導電性組成物および自動車用防曇窓ガラス
WO2012043811A1 (ja) * 2010-09-30 2012-04-05 京セラ株式会社 太陽電池用導電性ペーストおよびこれを用いた太陽電池素子の製造方法
CN102290120B (zh) * 2011-06-08 2013-10-23 常州斯威克光伏新材料有限公司 一种太阳能电池用银浆及其制备方法
CN105655009A (zh) * 2016-03-22 2016-06-08 广西吉宽太阳能设备有限公司 一种晶体硅太阳能电池用银浆

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000048643A (ja) * 1998-07-28 2000-02-18 Murata Mfg Co Ltd 導電性ペースト及びガラス回路基板
JP2003338218A (ja) * 2002-05-21 2003-11-28 Murata Mfg Co Ltd 導電性ペースト
JP2016538708A (ja) * 2013-03-27 2016-12-08 チェイル インダストリーズ インコーポレイテッド 太陽電池電極形成用組成物およびそれにより製造された電極
WO2018037746A1 (ja) * 2016-08-23 2018-03-01 ナミックス株式会社 導電性ペースト及び太陽電池

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112635096A (zh) * 2020-12-10 2021-04-09 潮州三环（集团）股份有限公司 一种片式电阻用银浆

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JP2020017423A (ja) 2020-01-30
TW202008391A (zh) 2020-02-16
JP7082408B2 (ja) 2022-06-08
CN112334996A (zh) 2021-02-05

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