WO2020021872A1 - Electroconductive paste, electrode, and chip resistor - Google Patents

Electroconductive paste, electrode, and chip resistor Download PDF

Info

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
Authority
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
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/en
Publication of WO2020021872A1 publication Critical patent/WO2020021872A1/en

Links

Images

Classifications

    • 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.

Abstract

The present invention provides a highly chemically resistant electroconductive paste capable of forming a low-resistance electrode. This electroconductive paste contains (A) a silver powder, (B) glass frit, (C) a silica filler, and (D) a thermoplastic resin. Glass frit (B) contains SiO2 and TiO2. The mass ratio between the SiO2 contained in glass frit (B) and the SiO2 contained in silica filler (C) is 1: (0.25‒1.6). The content of glass frit (B) is less than 20 mass parts relative to 100 mass parts of silver powder (A).

Description

導電性ペースト、電極及びチップ抵抗器Conductive paste, electrodes and chip resistors
　本発明は、例えば電子部品の電極の形成に用いられる導電性ペーストに関する。 The present invention relates to a conductive paste used for forming electrodes of electronic components, for example.
　電子部品の１つであるチップ抵抗器の電極の形成には、銀粉を含む導電性ペーストが用いられる。図１３は、チップ抵抗器１００の断面構造の一例を示す。チップ抵抗器１００は、矩形のアルミナ基板１０２を有しており、アルミナ基板１０２の上面には、抵抗体１０４と、抵抗体１０４から電気を取り出すための取り出し電極１０６が形成されている。また、アルミナ基板１０２の下面には、チップ抵抗器１００を基板へ実装するための下面電極１０８が形成されている。さらに、アルミナ基板１０２の端面には、取り出し電極１０６と下面電極１０８とを接続するための接続電極１１０が形成されている。取り出し電極１０６及び下面電極１０８は、アルミナ基板１０２の上面及び下面に導電性ペーストを印刷によって塗布した後に焼成することでそれぞれ形成される。取り出し電極１０６、下面電極１０８、及び接続電極１１０の上には、ニッケルめっき膜１１２及びスズめっき膜１１４が形成されるのが一般的である。 電極 A conductive paste containing silver powder is used to form the electrodes of the chip resistor, which is one of the electronic components. 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. On the lower surface of the alumina substrate 102, a lower electrode 108 for mounting the chip resistor 100 on the substrate is formed. Further, on the end face of the alumina substrate 102, a connection electrode 110 for connecting the extraction electrode 106 and the lower electrode 108 is formed. 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.
　取り出し電極１０６及び下面電極１０８は、それぞれ要求される特性が異なるため、異なる導電性ペーストを用いて形成されるのが一般的である。例えば、取り出し電極１０６の形成には、抵抗体１０４とのマッチング性の良い導電性ペーストが用いられる。また、抵抗体１０４の抵抗値が低い場合、取り出し電極１０６の抵抗値も低いことが要求される。そのため、取り出し電極１０６の形成には、低抵抗の電極を形成することのできる導電性ペーストが用いられる。 (4) Since 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. For example, a conductive paste having a good matching property with the resistor 104 is used for forming the extraction electrode 106. When 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.
　従来、電極の形成に用いられる導電性ペーストとして、特許文献１及び２に開示された銀粉及びガラスフリットを含有する導電性ペーストが知られている。 Conventionally, conductive pastes containing silver powder and glass frit disclosed in Patent Documents 1 and 2 are known as conductive pastes used for forming electrodes.
特開平７－１０５７２３号公報JP-A-7-105723 特表２０１６－５３８７０８号公報JP-T-2016-538708
　電極の表面にめっき膜を形成する場合には、めっき前処理が必要である。めっき不良のうち70％が、前処理に起因していると言われている。めっき前処理は、電極の表面から汚染物質を除去し、電極の表面を活性化し、めっきに適した清浄な状態にすることを目的として行われる。除去すべき汚染物質は、有機系と無機系に大別できる。前処理工程は、単独の工程で全ての汚染物質を除去するものではない。例えば、有機系物質は、アルカリ系洗浄剤を用いた工程で除去する。無機系物質は、酸系洗浄剤を用いた工程で除去する。その為、電極には高い耐薬品性が要求される。 場合 When forming a plating film on the surface of the electrode, 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.
　しかし、特に汚染物質として無機物を除去する場合、酸系洗浄剤を使用するため、電極の耐薬品性が不十分となる問題があった。すなわち、酸系洗浄剤を使用した場合、電極の密着強度を発現させる目的で添加されているガラスフリットが溶解する為、従来の導電性ペーストを用いて形成された電極は、密着強度が低下する問題があった。また、耐薬品性を向上させる目的で、ガラスフリットの量を増加させると、電極の抵抗値が上昇する問題があった。 However, especially when removing inorganic substances as contaminants, there is a problem that the chemical resistance of the electrode becomes insufficient because an acid-based cleaning agent is used. That is, when an acid-based cleaning agent is used, the glass frit added for the purpose of developing the adhesion strength of the electrode dissolves, so that the electrode formed using the conventional conductive paste has reduced adhesion strength. There was a problem. Further, when the amount of glass frit is increased for the purpose of improving chemical resistance, there is a problem that the resistance value of the electrode increases.
　本発明は、高い耐薬品性を有し、かつ低抵抗の電極を形成することのできる導電性ペーストを提供することを目的とする。 An object of the present invention is to provide a conductive paste having high chemical resistance and capable of forming a low-resistance electrode.
　本発明者らは、高い耐薬品性を有し、かつ低抵抗の電極を形成することのできる導電性ペーストについて鋭意研究を行った。その結果、銀粉及びガラスフリットに加えて、導電性ペーストが所定の比率でシリカフィラーを含有することによって耐薬品性が高まることを発見し、本発明を完成させた。 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.
　本発明は、以下の通りである。
（１）（Ａ）銀粉と、（Ｂ）ガラスフリットと、（Ｃ）シリカフィラーと、（Ｄ）熱可塑性樹脂と、を含有し、
　前記（Ｂ）ガラスフリットは、SiO2とTiO2を含み、
　前記（Ｂ）ガラスフリットに含まれるSiO2と、前記（Ｃ）シリカフィラーに含まれるSiO2の質量比率が、1：(0.25～1.6)であり、
　前記（Ｂ）ガラスフリットの含有量は、前記（Ａ）銀粉１００質量部に対して２０質量部未満であることを特徴とする、導電性ペースト。 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).
（２）前記（Ｂ）ガラスフリットは、ZnO、BaO、Na2O、CaO及びAl2O3からなる群から選択される少なくとも１つを含む、（１）に記載の導電性ペースト。 (2) the (B) glass frit, ZnO, BaO, Na 2 O , at least one selected from the group consisting of CaO and Al 2 O 3, (1) a description of the conductive paste.
（３）前記（Ｂ）ガラスフリットは、ZnO、BaO、Na2O及びAl2O3を含む、（１）に記載の導電性ペースト。 (3) The conductive paste according to (1), wherein the (B) glass frit includes ZnO, BaO, Na 2 O, and Al 2 O 3 .
（４）前記（Ｃ）シリカフィラーの粒径が、20nｍ以上5μｍ以下である、（１）から（３）のうちいずれかに記載の導電性ペースト。 (4) The conductive paste according to any one of (1) to (3), wherein the particle size of the silica filler (C) is 20 nm or more and 5 μm or less.
（５）さらに、（Ｅ）溶剤を含む、（１）から（４）のうちいずれかに記載の導電性ペースト。 (5) The conductive paste according to any one of (1) to (4), further comprising (E) a solvent.
（６）（１）から（５）のうちいずれかに記載の導電性ペーストを焼成して得られる電極。 (6) An electrode obtained by firing the conductive paste according to any one of (1) to (5).
（７）シート抵抗が4ｍΩ/□以下である、（６）に記載の電極。 (7) The electrode according to (6), wherein the sheet resistance is 4 mΩ / □ or less.
（８）（６）または（７）に記載の電極を有するチップ抵抗器。 (8) A chip resistor having the electrode according to (6) or (7).
　本発明によれば、高い耐薬品性を有し、かつ低抵抗の電極を形成することのできる導電性ペーストを提供することができる。 According to the present invention, it is possible to provide a conductive paste having high chemical resistance and capable of forming a low-resistance electrode.
角パッドパターンの表面の２０００倍のＳＥＭ写真である。It is a 2000 times SEM photograph of the surface of a square pad pattern. 角パッドパターンの表面の２０００倍のＳＥＭ写真である。It is a 2000 times SEM photograph of the surface of a square pad pattern. 角パッドパターンの表面の２０００倍のＳＥＭ写真である。It is a 2000 times SEM photograph of the surface of a square pad pattern. 角パッドパターンの表面の５００倍のＳＥＭ写真である。It is a 500 times SEM photograph of the surface of a square pad pattern. 角パッドパターンの表面の５００倍のＳＥＭ写真である。It is a 500 times SEM photograph of the surface of a square pad pattern. 角パッドパターンの表面の５００倍のＳＥＭ写真である。It is a 500 times SEM photograph of the surface of a square pad pattern. アルミナ基板上に残存している角パッドパターンの写真である。4 is a photograph of a square pad pattern remaining on an alumina substrate. アルミナ基板上に残存している角パッドパターンの写真である。4 is a photograph of a square pad pattern remaining on an alumina substrate. アルミナ基板上に残存している角パッドパターンの写真である。4 is a photograph of a square pad pattern remaining on an alumina substrate. 引き剥がしたテープの貼着面の写真である。It is a photograph of the sticking surface of the peeled tape. 引き剥がしたテープの貼着面の写真である。It is a photograph of the sticking surface of the peeled tape. 引き剥がしたテープの貼着面の写真である。It is a photograph of the sticking surface of the peeled tape. チップ抵抗器の断面構造を示す。2 shows a cross-sectional structure of a chip resistor.
　以下、本発明を実施するための形態について詳細に説明する。
　本発明の実施形態に係る導電性ペーストは、（Ａ）銀粉と、（Ｂ）ガラスフリットと、（Ｃ）シリカフィラーと、（Ｄ）熱可塑性樹脂と、を含有する。（Ｂ）ガラスフリットは、SiO2とTiO2を含む。（Ｂ）ガラスフリットに含まれるSiO2と、（Ｃ）シリカフィラーに含まれるSiO2の質量比率は、1：(0.25～1.6)である。（Ｂ）ガラスフリットの含有量は、（Ａ）銀粉１００質量部に対して２０質量部未満である。 Hereinafter, embodiments for carrying out the present invention will be described in detail.
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. (B) 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). (B) The content of the glass frit is less than 20 parts by mass relative to 100 parts by mass of the silver powder (A).
（Ａ）銀粉
　本実施形態の導電性ペーストは、導電性粒子として（Ａ）銀粉を含む。銀粉としては、銀または銀を含む合金からなる粉末を用いることができる。銀粉粒子の形状は、特に限定されず、例えば、球状、粒状、フレーク状及び／又は鱗片状の銀粉粒子を用いることが可能である。 (A) Silver powder 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.
　銀粉の平均粒径は、０．１μｍ～１０μｍが好ましく、より好ましくは０．１μｍ～７μｍであり、最も好ましくは０．１μｍ～５μｍである。ここでいう平均粒径は、レーザー回折散乱式粒度分布測定法により得られる体積基準メジアン径（ｄ５０）を意味する。 平均 The average particle size of the silver powder is preferably 0.1 μm to 10 μm, more preferably 0.1 μm to 7 μm, and most preferably 0.1 μm to 5 μm. The average particle diameter here means a volume-based median diameter (d50) obtained by a laser diffraction scattering particle size distribution measuring method.
　銀粉の製造方法は、特に限定されず、例えば、還元法、粉砕法、電解法、アトマイズ法、熱処理法、又はそれらの組合せによって製造することができる。フレーク状の銀粉は、例えば、球状または粒状の銀粒子をボールミル等によって押し潰すことによって製造することができる。 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.
（Ｂ）ガラスフリット
　本実施形態の導電性ペーストは、（Ｂ）ガラスフリットを含有する。（Ｂ）ガラスフリットは、ＳｉＯ２及びＴｉＯ２を含む。導電性ペーストが（Ｂ）ガラスフリットを含有することによって、導電性ペーストを焼成して得られる電極の基板への密着強度が向上する。ガラスフリットは、特に限定されるものではないが、好ましくは軟化点３００℃以上、より好ましくは軟化点４００～９００℃、さらに好ましくは軟化点５００～８００℃のガラスフリットを用いることができる。ガラスフリットの軟化点は、熱重量測定装置（例えば、ＢＲＵＫＥＲ ＡＸＳ社製、ＴＧ－ＤＴＡ２０００ＳＡ）を用いて測定することができる。 (B) Glass frit The conductive paste of the present embodiment contains (B) glass frit. (B) The glass frit contains SiO 2 and TiO 2 . When the conductive paste contains the glass frit (B), the adhesion strength of the electrode obtained by firing the conductive paste to the substrate is improved. Although 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).
　（Ｂ）ガラスフリットの例として、ホウケイ酸チタン系（TiO2系）、及びホウケイ酸バリウム系等のガラスフリットを挙げることができる。また、ガラスフリットの例として、ホウケイ酸ビスマス系、ホウケイ酸アルカリ金属系、ホウケイ酸アルカリ土類金属系、ホウケイ酸亜鉛系、ホウケイ酸鉛系、ホウ酸鉛系、ケイ酸鉛系、ホウ酸ビスマス系、及びホウ酸亜鉛系等のガラスフリットを挙げることができる。これらのガラスフリットは、２種以上を混合して用いることもできる。ガラスフリットは、環境への配慮の点から鉛フリーであることが好ましい。 (B) Examples of the glass frit include a glass frit such as a titanium borosilicate-based (TiO 2 -based) and a barium borosilicate-based. Examples of glass frit include bismuth borosilicate, alkali metal borosilicate, alkaline earth metal borosilicate, zinc borosilicate, lead borosilicate, lead borate, lead silicate, and bismuth borate. And a glass frit such as a zinc borate type. These glass frits can be used as a mixture of two or more kinds. The glass frit is preferably lead-free from the viewpoint of environmental considerations.
　ガラスフリットは、ZnO、BaO、Na2O、CaO及びAl2O3からなる群から選択される少なくとも１つを含むことが好ましい。ガラスフリットは、ZnO、BaO、Na2O及びAl2O3を含むことがより好ましい。 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.
　ガラスフリットの平均粒径は、好ましくは０．１～２０μｍ、より好ましくは０．２～１０μｍ、最も好ましくは０．５～５μｍである。ここでいう平均粒径は、レーザー回折散乱式粒度分布測定法により得られる体積基準メジアン径（ｄ５０）のことを意味する。 平均 The average particle size of the glass frit is preferably 0.1 to 20 μm, more preferably 0.2 to 10 μm, and most preferably 0.5 to 5 μm. The average particle diameter here means a volume-based median diameter (d50) obtained by a laser diffraction scattering particle size distribution measuring method.
　本実施形態の導電性ペーストにおいて、（Ｂ）ガラスフリットの含有量は、（Ａ）銀粉１００質量部に対して２０質量部未満であり、より好ましくは０．１～１５質量部、さらに好ましくは１．０～１０質量部である。ガラスフリットの含有量がこの範囲よりも少ない場合、導電性ペーストを焼成して得られる電極の基板への密着性が低下する。ガラスフリットの含有量がこの範囲よりも多い場合、導電性ペーストを焼成して得られる電極の抵抗値は高くなる。 In the conductive paste of the present embodiment, 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. When 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. When the content of the glass frit is larger than this range, the resistance of the electrode obtained by firing the conductive paste becomes high.
（Ｃ）シリカフィラー
　本実施形態の導電性ペーストは、（Ｃ）シリカフィラーを含有する。シリカフィラーは、例えば、半導体封止材料として市販されている球状シリカ（ＳｉＯ２）粒子を用いることができる。シリカフィラーの形状は、球状以外の形状であってもよい。シリカフィラーの製造方法は特に制限されるものではなく、溶射法などの公知の方法によって製造されたシリカフィラーを用いることができる。シリカフィラーの平均粒径は、２０ｎｍ以上５μｍ以下であることが好ましい。ここでいう平均粒径は、レーザー回折散乱式粒度分布測定法により得られる体積基準メジアン径（ｄ５０）を意味する。 (C) Silica Filler The conductive paste of the present embodiment contains (C) a silica filler. As the 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 μm 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.
（Ｄ）熱可塑性樹脂
　本実施形態の導電性ペーストは、（Ｄ）熱可塑性樹脂を含有する。熱可塑性樹脂は、導電性ペースト中において銀粉同士をつなぎあわせるものである。熱可塑性樹脂としては、導電性ペーストの焼成時に焼失するものを用いることができる。 (D) 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. As the thermoplastic resin, a resin that is burned off when the conductive paste is fired can be used.
　熱可塑性樹脂としては、例えば、エチルセルロース、ニトロセルロース等のセルロース系樹脂、アクリル樹脂、アルキド樹脂、飽和ポリエステル樹脂、ブチラール樹脂、ポリビニルアルコール、ヒドロキシプロピルセルロース等を用いることができる。これらの樹脂は、単独で使用することができ、２種類以上を混合して使用することができる。 As the 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.
　（Ｄ）熱可塑性樹脂の含有量は、（Ａ）銀粉１００質量部に対して好ましくは０．５～３０質量部であり、より好ましくは、１．０～２０質量部である。導電性ペースト中の熱可塑性樹脂の含有量が上記の範囲内の場合、導電性ペーストの基板への塗布性が向上し、微細な電極を高精度に形成することができる。一方、熱可塑性樹脂の含有量が上記の範囲を超えると、導電性ペースト中に含まれる熱可塑性樹脂の量が多すぎる。そのため、微細な電極を高精度に形成することができず、かつ焼成後に得られる電極の緻密性が低下し、抵抗値も上昇する場合がある。 (D) 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). When 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. On the other hand, when 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.
　本実施形態の導電性ペーストにおいて、（Ｂ）ガラスフリットに含まれるSiO2と、（Ｃ）シリカフィラーに含まれるSiO2の質量比率は、1：(0.25～1.6)であることを特徴とする。（Ｂ）ガラスフリットに含まれるSiO2と、（Ｃ）シリカフィラーに含まれるSiO2の質量比率は、より好ましくは1：（0.50～1.3）である。 In the conductive paste of the present embodiment, 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).
（Ｅ）溶剤
　本実施形態の導電性ペーストは、（Ｅ）溶剤を含んでもよい。溶剤としては、例えば、メタノール、エタノール、イソプロピルアルコール（ＩＰＡ）等のアルコール類、酢酸エチレン等の有機酸類、トルエン、キシレン等の芳香族炭化水素類、Ｎ－メチル－２－ピロリドン（ＮＭＰ）等のＮ－アルキルピロリドン類、Ｎ，Ｎ－ジメチルホルムアミド（ＤＭＦ）等のアミド類、メチルエチルケトン（ＭＥＫ）等のケトン類、テルピネオール（ＴＥＬ）、ブチルカルビトール（ＢＣ）等の環状カーボネート類、及び水等が挙げられる。溶剤の含有量は、特に限定されないが、（Ａ）銀粉１００質量部に対して、好ましくは１～１００質量部、より好ましくは５～６０質量部である。 (E) Solvent The conductive paste of the present embodiment may contain (E) a solvent. Examples of 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. No. 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).
　本実施形態の導電性ペーストの粘度は、好ましくは５０～７００Ｐａ・ｓ（せん断速度：４．０ｓｅｃ－１）、より好ましくは１００～３００Ｐａ・ｓ（せん断速度：４．０ｓｅｃ－１）である。導電性ペーストの粘度がこの範囲に調整されることによって、導電性ペーストの基板への塗布性や取り扱い性が良好になり、導電性ペーストを均一の厚みで基板へ塗布することが可能になる。 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 ). By adjusting the viscosity of the conductive paste to this range, the applicability and handleability of the conductive paste to the substrate are improved, and the conductive paste can be applied to the substrate with a uniform thickness.
　本実施形態の導電性ペーストは、その他の添加剤、例えば、分散剤、レオロジー調整剤、顔料などを含有してもよい。 導電 The conductive paste of the present embodiment may contain other additives, for example, a dispersant, a rheology modifier, a pigment, and the like.
　本実施形態の導電性ペーストは、上記の各成分を、例えば、ライカイ機、ポットミル、三本ロールミル、回転式混合機、二軸ミキサー等を用いて混合することで製造することができる。 導電 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.
　次に、本実施形態の導電性ペーストを用いて基板上に電極を形成する方法について説明する。まず、導電性ペーストを基板上に塗布する。塗布方法は任意であり、例えば、ディスペンス、ジェットディスペンス、孔版印刷、スクリーン印刷、ピン転写、スタンピングなどの公知の方法を用いて塗布することができる。 Next, a method for forming an electrode on a substrate using the conductive paste of the present embodiment will be described. First, 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.
　基板上に導電性ペーストを塗布した後、基板を焼成炉等に投入する。そして、基板上に塗布された導電性ペーストを、５００～９００℃、より好ましくは６００～９００℃、さらに好ましくは７００～９００℃で焼成する。これにより、導電性ペーストに含まれる溶剤成分は３００℃以下で蒸発し、樹脂成分は４００℃～６００℃で焼失し、導電性ペーストの焼成体を形成する。このようにして得られた電極は、耐薬品性が高く、基板への密着性が優れている。 (4) After applying the conductive paste on the substrate, 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.
　本実施形態の導電性ペーストは、電子部品の回路の形成や電極の形成、電子部品の基板への接合等に用いることが可能である。また、本実施形態の導電性ペーストは、チップ抵抗器の電極の形成に用いることができる。 導電 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.
　本実施形態の導電性ペーストは、耐薬品性に優れるため、表面にめっき膜が形成される電極の形成に好ましく用いることができる。例えば、本実施形態の導電性ペーストは、チップ抵抗器の抵抗体から電気を取り出すための取り出し電極の形成に特に好ましく用いることができる。 導電 Since 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. For example, 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.
　また、本実施形態の導電性ペーストを焼成して得られた電極は、シート抵抗が４ｍΩ/□（４ｍΩ/square)以下であり、より好ましくは３．４mΩ/□以下である。このため、低抵抗であることが要求される電極の形成に好ましく用いることができる。 The electrode obtained by firing the conductive paste of the present embodiment has a sheet resistance of 4 mΩ / □ (4 mΩ / square) or less, and more preferably 3.4 mΩ / □ or less. Therefore, it can be preferably used for forming an electrode required to have low resistance.
　以下、本発明の実施例及び比較例について説明する。
［導電性ペーストの調製］
　以下の（Ａ）～（Ｆ）成分を、以下の表１～２に示す割合で混合して導電性ペーストを調製した。なお、表１～２に示す各成分の割合は、全て質量部で示している。 Hereinafter, examples and comparative examples of the present invention will be described.
[Preparation of conductive paste]
The following components (A) to (F) were mixed in proportions shown in Tables 1 and 2 below to prepare a conductive paste. The proportions of each component shown in Tables 1 and 2 are all shown in parts by mass.
（Ａ）銀粉
　　（Ａ１）球状銀粉、平均粒径５μｍ
　　（Ａ２）フレーク状銀粉、平均粒径３．５μｍ (A) Silver powder (A1) Spherical silver powder, average particle size 5 μm
(A2) Flaky silver powder, average particle size 3.5 μm
（Ｂ）ガラスフリット
　　（Ｂ１）ホウケイ酸チタン系ガラスフリット（成分組成：ＳｉＯ２－Ｂ２Ｏ３－Ｎａ２Ｏ－ＴｉＯ２系）、軟化点５７０℃、平均粒径１．４μｍ
　　（Ｂ２）ホウケイ酸バリウム系ガラスフリット（成分組成：ＳｉＯ２－Ｂ２Ｏ３－ＢａＯ系）、軟化点５７０℃、平均粒径１．２μｍ (B) Glass frit (B1) Titanium borosilicate glass frit (component composition: SiO 2 —B 2 O 3 —Na 2 O—TiO 2 system), softening point 570 ° C., average particle size 1.4 μm
(B2) Barium borosilicate glass frit (component composition: SiO 2 —B 2 O 3 —BaO system), softening point 570 ° C., average particle size 1.2 μm
（Ｃ）シリカフィラー
　　（Ｃ１）球状シリカ（ＳｉＯ２）粉末、平均粒径０．３μｍ
　　（Ｃ２）球状シリカ（ＳｉＯ２）粉末、平均粒径２μｍ (C) silica filler (C1) spherical silica (SiO 2 ) powder, average particle size 0.3 μm
(C2) Spherical silica (SiO 2 ) powder, average particle size 2 μm
（Ｄ）熱可塑性樹脂
　　（Ｄ１）エチルセルロース樹脂
　　　　（ダウ・ケミカル製、製品名：エトセル（ＳＴＤ－２００））
　　（Ｄ２）エチルセルロース樹脂
　　　　（ダウ・ケミカル製、製品名：エトセル（ＳＴＤ－３００））
　　（Ｄ３）エチルセルロース樹脂
　　　　（ダウ・ケミカル製、製品名：エトセル（ＳＴＤ－４））
　　（Ｄ４）アクリル樹脂
　　　　　　（藤倉化成製、製品名：ＬＳ－７０１、Ｔｇ　１７℃、分子量　９．０万） (D) Thermoplastic resin (D1) Ethyl cellulose resin (manufactured by Dow Chemical, product name: Ethocel (STD-200))
(D2) Ethyl cellulose resin (manufactured by Dow Chemical, product name: Ethocel (STD-300))
(D3) Ethyl cellulose resin (manufactured by Dow Chemical, product name: Ethocel (STD-4))
(D4) Acrylic resin (manufactured by Fujikura Kasei, product name: LS-701, Tg 17 ° C, molecular weight 90,000)
（Ｅ）溶剤
ブチルカルビトール（大伸化学株式会社製、製品名：ブチルカルビトール） (E) Solvent butyl carbitol (manufactured by Daishin Chemical Co., Ltd., product name: butyl carbitol)
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
［試験片の作製］
　調製した導電性ペーストを用いて、以下の手順により、試験片を作製した。まず、２０ｍｍ×２０ｍｍ×１ｍｍ（ｔ）のアルミナ基板上に、スクリーン印刷によって導電性ペーストを塗布した。これにより、一辺が１．５ｍｍの角パッド形状からなるパターンを、アルミナ基板上に２０個形成した。パターンの形成には、ステンレス製の２５０メッシュのマスクを用いた。つぎに、熱風式乾燥機を用いて、１５０℃で１０分間、導電性ペーストを乾燥させた。導電性ペーストを乾燥させた後、焼成炉を用いて、導電性ペーストを焼成した。焼成温度は８５０℃で１０分間キープ、トータル焼成時間６０分である。 [Preparation of test piece]
Using the prepared conductive paste, 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.
［シート抵抗の測定］
　アルミナ基板上に形成された角パッドパターンのシート抵抗を測定した。なお、シート抵抗は、試料を温度２５℃、相対湿度６５％の恒温・恒湿雰囲気下に３０分間静置した後、テスターを用いて４端子法にて測定した。シート抵抗の測定結果を、表１及び表２に示す。 [Measurement of sheet resistance]
The sheet resistance of the square pad pattern formed on the alumina substrate was measured. The sheet resistance was measured by a four-terminal method using a tester after the sample was allowed to stand in a constant temperature and constant humidity atmosphere at a temperature of 25 ° C. and a relative humidity of 65% for 30 minutes. Tables 1 and 2 show the measurement results of the sheet resistance.
［ＳＥＭによる撮影］
　アルミナ基板上に形成された角パッドパターンの表面を、２０００倍及び５００倍の倍率でＳＥＭによって撮影した。撮影したＳＥＭ写真を、図１～図６に示す。 [Shooting with SEM]
The surface of the square pad pattern formed on the alumina substrate was photographed by SEM at 2000 × and 500 × magnification. The taken SEM photographs are shown in FIGS.
［耐薬品性試験］
　上記で作製した試験片を、ｐＨ＝１の酸性の溶液中に５時間浸漬させた後、室温で乾燥させた。その後、試験片にテープを貼着し、そのテープを引きはがした。テープを引きはがした後にアルミナ基板上に残存している角パッドパターンをカメラで撮影した。また、引きはがしたテープの貼着面の状態をカメラで撮影した。アルミナ基板上に残存している角パッドパターンの写真を、図７～９に示す。引き剥がしたテープの貼着面の写真を、図１０～１２に示す。 [Chemical resistance test]
The test piece prepared above was immersed in an acidic solution having a pH of 1 for 5 hours, and then dried at room temperature. Thereafter, a tape was attached to the test piece, and the tape was peeled off. After peeling off the tape, the square pad pattern remaining on the alumina substrate was photographed with a camera. In addition, the state of the attached surface of the peeled tape was photographed with a camera. FIGS. 7 to 9 show photographs of the square pad pattern remaining on the alumina substrate. FIGS. 10 to 12 show photographs of the adhered surface of the peeled tape.
　アルミナ基板上の角パッドパターンが全て残っている場合、耐薬品性が良好である（○）と判定した。アルミナ基板上の角パッドパターンが１つでも剥がれた場合、耐薬品性が良好ではない（×）と判定した。耐薬品性試験の結果を、表１及び表２に示す。 場合 When all the square pad patterns on the alumina substrate remained, it was judged that the chemical resistance was good (（). When even one square pad pattern on the alumina substrate was peeled off, it was judged that the chemical resistance was not good (x). Tables 1 and 2 show the results of the chemical resistance test.
　表１及び表２に示す結果から分かる通り、実施例１～１２の導電性ペーストを焼成して得られた電極パターンは、耐薬品性及び基板への密着性に優れ、シート抵抗値も低かった。これに対し、比較例１～３、５～８の導電性ペーストを焼成して得られた電極パターンは、耐薬品性及び基板への密着性が劣っていた。比較例４の導電性ペーストを焼成して得られた電極パターンは、シート抵抗値が高かった。また、実施例１～８の導電性ペーストを焼成して得られた電極パターンは、シート抵抗値が３．４mΩ/□以下と低いため、低抵抗を要求される電極に好適であった。 As can be seen from the results shown in Tables 1 and 2, 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. . On the other hand, 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. Further, the electrode patterns obtained by firing the conductive pastes of Examples 1 to 8 had a low sheet resistance of 3.4 mΩ / □ or less, and were suitable for electrodes requiring low resistance.
　また、図１～図６を見れば分かる通り、実施例１～１２の導電性ペーストを焼成して得られた電極パターンは、その表面が緻密であった。 Also, as can be seen from FIGS. 1 to 6, the electrode patterns obtained by firing the conductive pastes of Examples 1 to 12 had dense surfaces.

Claims (8)

  1. 　（Ａ）銀粉と、
    　（Ｂ）ガラスフリットと、
    　（Ｃ）シリカフィラーと、
    　（Ｄ）熱可塑性樹脂と、を含有し、
    　前記（Ｂ）ガラスフリットは、SiO2とTiO2を含み、
    　前記（Ｂ）ガラスフリットに含まれるSiO2と、前記（Ｃ）シリカフィラーに含まれるSiO2の質量比率が、1：(0.25～1.6)であり、
    　前記（Ｂ）ガラスフリットの含有量は、前記（Ａ）銀粉１００質量部に対して２０質量部未満であることを特徴とする、導電性ペースト。     (A) silver powder;
    (B) a glass frit,
    (C) a silica filler;
    (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).
  2. 　前記（Ｂ）ガラスフリットは、ZnO、BaO、Na2O、CaO及びAl2O3からなる群から選択される少なくとも１つを含む、請求項１に記載の導電性ペースト。 (B) the glass frit, ZnO, BaO, Na 2 O , at least one selected from the group consisting of CaO and Al 2 O 3, conductive paste according to claim 1.
  3. 　前記（Ｂ）ガラスフリットは、ZnO、BaO、Na2O及びAl2O3を含む、請求項１に記載の導電性ペースト。 (B) the glass frit, ZnO, BaO, including Na 2 O and Al 2 O 3, conductive paste according to claim 1.
  4. 　前記（Ｃ）シリカフィラーの粒径が、20nｍ以上5μｍ以下である、請求項１から請求項３のうちいずれか１項に記載の導電性ペースト。 (4) The conductive paste according to any one of (1) to (3), wherein the particle diameter of the (C) silica filler is 20 nm or more and 5 μm or less.
  5. 　さらに、（Ｅ）溶剤を含む、請求項１から請求項４のうちいずれか１項に記載の導電性ペースト。 (5) The conductive paste according to any one of (1) to (4), further comprising (E) a solvent.
  6. 　請求項１から請求項５のうちいずれか１項に記載の導電性ペーストを焼成して得られる電極。 An electrode obtained by firing the conductive paste according to any one of claims 1 to 5.
  7. 　シート抵抗が4ｍΩ/□以下である、請求項６に記載の電極。 7. The electrode according to claim 6, wherein the sheet resistance is 4 mΩ / □ or less.
  8. 　請求項６または請求項７に記載の電極を有するチップ抵抗器。 A chip resistor having the electrode according to claim 6 or 7.
PCT/JP2019/022355 2018-07-26 2019-06-05 Electroconductive paste, electrode, and chip resistor WO2020021872A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201980042843.9A CN112334996A (en) 2018-07-26 2019-06-05 Conductive paste, electrode and chip resistor

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2018-140128 2018-07-26
JP2018140128A JP7082408B2 (en) 2018-07-26 2018-07-26 Conductive paste

Publications (1)

Publication Number Publication Date
WO2020021872A1 true WO2020021872A1 (en) 2020-01-30

Family

ID=69180519

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2019/022355 WO2020021872A1 (en) 2018-07-26 2019-06-05 Electroconductive paste, electrode, and chip resistor

Country Status (4)

Country Link
JP (1) JP7082408B2 (en)
CN (1) CN112334996A (en)
TW (1) TW202008391A (en)
WO (1) WO2020021872A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112635096A (en) * 2020-12-10 2021-04-09 潮州三环（集团）股份有限公司 Silver paste for sheet resistor

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7434407B2 (en) 2022-04-25 2024-02-20 株式会社ノリタケカンパニーリミテド Paste for external electrodes

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000048643A (en) * 1998-07-28 2000-02-18 Murata Mfg Co Ltd Conductive paste and glass circuit substrate
JP2003338218A (en) * 2002-05-21 2003-11-28 Murata Mfg Co Ltd Conductive paste
JP2016538708A (en) * 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 Composition for forming solar cell electrode and electrode produced thereby
WO2018037746A1 (en) * 2016-08-23 2018-03-01 ナミックス株式会社 Conductive paste and solar cell

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11130459A (en) * 1997-10-28 1999-05-18 Murata Mfg Co Ltd Electrically conductive composition for glass substrate and anti-fog window glass for automobile
WO2012043811A1 (en) * 2010-09-30 2012-04-05 京セラ株式会社 Conductive paste for use in photovoltaic cell and method of producing photovoltaic cell element using the same
CN102290120B (en) * 2011-06-08 2013-10-23 常州斯威克光伏新材料有限公司 Silver paste for solar cell and preparation method thereof
CN105655009A (en) * 2016-03-22 2016-06-08 广西吉宽太阳能设备有限公司 Silver slurry for crystalline silicon solar cell

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000048643A (en) * 1998-07-28 2000-02-18 Murata Mfg Co Ltd Conductive paste and glass circuit substrate
JP2003338218A (en) * 2002-05-21 2003-11-28 Murata Mfg Co Ltd Conductive paste
JP2016538708A (en) * 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 Composition for forming solar cell electrode and electrode produced thereby
WO2018037746A1 (en) * 2016-08-23 2018-03-01 ナミックス株式会社 Conductive paste and solar cell

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112635096A (en) * 2020-12-10 2021-04-09 潮州三环（集团）股份有限公司 Silver paste for sheet resistor

Also Published As

Publication number Publication date
JP7082408B2 (en) 2022-06-08
JP2020017423A (en) 2020-01-30
TW202008391A (en) 2020-02-16
CN112334996A (en) 2021-02-05

Similar Documents

Publication Publication Date Title
JP6242800B2 (en) Sintered conductive paste
CN102026927A (en) Glass compositions used in conductors for photovoltaic cells
EP3121819B1 (en) Conductive paste, processes using the conductive paste and uses of the conductive paste for forming a laminated ceramic component, printed wiring board and electronic device
JP5988124B2 (en) Thick film resistor and manufacturing method thereof
JP5988123B2 (en) Resistance composition
WO2020021872A1 (en) Electroconductive paste, electrode, and chip resistor
TWI746515B (en) Conductive paste
WO2021145269A1 (en) Electroconductive paste, electrode and chip resistor
CN115461825A (en) Thick film resistor paste, thick film resistor, and electronic component
JP2018137131A (en) Conductive paste, aluminum nitride circuit board and method for producing the same
JP2854577B2 (en) Finely ground particles and thick film electronic material composition containing the same
JP3964342B2 (en) Conductive paste
JP6290131B2 (en) Conductive paste for glass substrate, method for forming conductive film, and silver conductive film
JP3701038B2 (en) Thick film copper conductor paste composition and method for producing circuit board using the same
JP7279551B2 (en) Composition for thick film resistor, paste for thick film resistor, and thick film resistor
CN115516578A (en) Thick film resistor paste, thick film resistor, and electronic component
CN113782251A (en) Electrode paste, electrode thick film and preparation method thereof
JP6386398B2 (en) Conductive laminate and method for producing the same
CN115516579A (en) Thick film resistor paste, thick film resistor, and electronic component
JP2006236621A (en) Thick film resistor paste and manufacturing method of the same
TW201423767A (en) Electroplating-free silver paste

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19841205

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19841205

Country of ref document: EP

Kind code of ref document: A1