JP2015187977A - Conductive laminate and method for manufacturing the same - Google Patents
Conductive laminate and method for manufacturing the same Download PDFInfo
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- JP2015187977A JP2015187977A JP2015035709A JP2015035709A JP2015187977A JP 2015187977 A JP2015187977 A JP 2015187977A JP 2015035709 A JP2015035709 A JP 2015035709A JP 2015035709 A JP2015035709 A JP 2015035709A JP 2015187977 A JP2015187977 A JP 2015187977A
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- conductive
- metal
- conductive layer
- glass
- layer
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- ZFZQOKHLXAVJIF-UHFFFAOYSA-N zinc;boric acid;dihydroxy(dioxido)silane Chemical compound [Zn+2].OB(O)O.O[Si](O)([O-])[O-] ZFZQOKHLXAVJIF-UHFFFAOYSA-N 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical group [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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Abstract
Description
本発明は、エレクトロニクス分野で使用され、ガラス基板の上に導電膜が形成された導電性積層体及びその製造方法に関する。 The present invention relates to a conductive laminated body used in the field of electronics and having a conductive film formed on a glass substrate, and a method for manufacturing the same.
導電性ペーストは、印刷などにより電極など、種々のパターンを容易に形成できるため、エレクトロニクス分野で広く普及している。最近では、塗布形成したパターンを加熱焼結することにより更なる低抵抗化を図る方法が採用されている。この方法では、導電性ペーストに使用される金属粉末は、焼結の進行により金属粉末間の接触抵抗が下がり、塗布パターンとして、より良好な導電性を発現できる。 Conductive pastes are widely used in the electronics field because various patterns such as electrodes can be easily formed by printing or the like. Recently, a method of further reducing resistance by heating and sintering a pattern formed by coating has been adopted. In this method, the metal powder used for the conductive paste has a lower contact resistance between the metal powders due to the progress of sintering, and can exhibit better conductivity as a coating pattern.
このような方法として、特開2003−132735号公報(特許文献1)に開示されているような導電性ペースト(金属粉末、ガラス粉末、及び有機ビヒクルを含有する導体ペースト)が広く使用されており、アルミナや窒化アルミニウム等のセラミックスを基板としたLEDパッケージの内部又は外部電極、配線形成等に使用されている。また、特許文献1には、メッキについて記載されていないが、前記電極は、密着強度の低下や変色に対する長期信頼性を向上させるため、Ni/AuやNi/Pd/Auなどのメッキを施して使用される場合が多い。 As such a method, a conductive paste (a conductive paste containing a metal powder, a glass powder, and an organic vehicle) as disclosed in Japanese Patent Laid-Open No. 2003-132735 (Patent Document 1) is widely used. In addition, it is used for forming an internal or external electrode of an LED package using a ceramic substrate such as alumina or aluminum nitride, wiring formation, or the like. Further, although Patent Document 1 does not describe plating, the electrode is plated with Ni / Au or Ni / Pd / Au to improve long-term reliability against a decrease in adhesion strength or discoloration. Often used.
また、製品のコストダウンなどを目的としてセラミックス基板の代わりにケイ酸塩ガラスや硼ケイ酸ガラスなどのガラス基板の上に、導電性ペーストを用いて導電膜を形成する方法も提案されている。 In addition, a method of forming a conductive film using a conductive paste on a glass substrate such as silicate glass or borosilicate glass instead of a ceramic substrate has been proposed for the purpose of reducing product costs.
特開2013−182714号公報(特許文献2)には、金属粒子及び軟化点が500℃以下のビスマス系ガラスフリットを含む接着層を介して基板の上に、金属ナノ粒子を含み、かつ軟化点が500℃以下のビスマス系ガラスフリットを実質的に含まない被覆層が形成されている積層体を焼成し、導電接着層を介して基板の上に導電被覆層が形成された導電性積層体を製造する方法が開示されている。この文献には、導電被覆層の上に、さらにメッキ層を形成することが記載されている。 JP 2013-182714 A (Patent Document 2) includes metal nanoparticles and a softening point on a substrate via an adhesive layer containing a metal particle and a bismuth glass frit having a softening point of 500 ° C. or less. A conductive laminate having a conductive coating layer formed on a substrate by firing a laminate in which a coating layer substantially free of bismuth-based glass frit having a temperature of 500 ° C. or less is formed. A method of manufacturing is disclosed. This document describes that a plating layer is further formed on the conductive coating layer.
しかし、基板としてガラス基板を用いる導電性積層体は、アルミナなどのセラミックス基板と比べて強度が低く、脆い性質を有するため、ガラス基板上に導電膜(焼結金属膜)が形成された場合、金属膜とガラス基板との線膨張係数差により生じる熱応力で金属膜直下のガラス部分に亀裂が発生しやすく、耐熱衝撃性(耐熱性)が著しく弱かった。さらに、メッキで増膜した積層体では、リフロー程度の熱衝撃であってもガラスに亀裂が生じてしまい実用的な使用は困難であった。 However, since the conductive laminate using a glass substrate as a substrate has a low strength and a brittle nature compared to a ceramic substrate such as alumina, when a conductive film (sintered metal film) is formed on the glass substrate, The thermal stress generated by the difference in coefficient of linear expansion between the metal film and the glass substrate was likely to cause cracks in the glass portion directly under the metal film, and the thermal shock resistance (heat resistance) was extremely weak. Furthermore, in the laminated body increased in thickness by plating, cracks occurred in the glass even when the thermal shock was about reflow, and practical use was difficult.
従って、本発明の目的は、ガラス基板の上に導電膜を形成しても、耐熱衝撃性(耐熱性)を向上できる導電性積層体及びその製造方法を提供することにある。 Therefore, the objective of this invention is providing the electroconductive laminated body which can improve a thermal shock resistance (heat resistance), and its manufacturing method, even if it forms a electrically conductive film on a glass substrate.
本発明の他の目的は、ガラス基板と導電膜との密着性も向上できる導電性積層体及びその製造方法を提供することにある。 Another object of the present invention is to provide a conductive laminate that can improve the adhesion between a glass substrate and a conductive film, and a method for producing the same.
本発明のさらに他の目的は、半田付け性及び耐変色性などの耐久性も向上できる導電性積層体及びその製造方法を提供することにある。 Still another object of the present invention is to provide a conductive laminate that can improve durability such as solderability and discoloration resistance, and a method for producing the same.
本発明者らは、前記課題を達成するため鋭意検討した結果、ガラス基板の上に、金属及び低融点ガラスを含み、かつ前記金属で形成された連続相を含む相分離構造を有する導電層を積層し、さらにこの導電層の上にメッキ層を積層することにより、ガラス基板の上に導電膜を形成しても、耐熱衝撃性を向上できることを見出し、本発明を完成した。 As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that a conductive layer having a phase separation structure including a metal and a low-melting glass on a glass substrate and including a continuous phase formed of the metal. The inventors have found that the thermal shock resistance can be improved even when a conductive film is formed on a glass substrate by laminating and further depositing a plating layer on the conductive layer, and the present invention has been completed.
すなわち、本発明の導電性積層体は、ガラス基板と、このガラス基板の上に積層された導電層と、この導電層の上に積層されたメッキ層とを含む導電性積層体であって、前記導電層が、金属及び低融点ガラスを含み、かつ前記金属で形成された連続相を含む相分離構造を有する。前記導電層の相分離構造は共連続構造又は海島構造であり、かつメッキ層は、その導電層の表面のうち、金属で形成された連続相の上に積層されていてもよい。前記メッキ層の空隙率は40〜90%程度であってもよい。前記導電層において、金属と低融点ガラスとの体積割合は、前者/後者=93/7〜50/50程度であってもよい。前記低融点ガラスの軟化点は導電層の焼成温度よりも低い温度であってもよい。前記低融点ガラスはビスマス系ガラスフリットの焼成物であってもよい。前記導電層の金属は銀であってもよい。前記メッキ層はニッケルを含んでいてもよい。前記メッキ層の平均厚みは0.3〜2μm程度であってもよい。 That is, the conductive laminate of the present invention is a conductive laminate including a glass substrate, a conductive layer laminated on the glass substrate, and a plating layer laminated on the conductive layer, The conductive layer includes a metal and a low-melting glass, and has a phase separation structure including a continuous phase formed of the metal. The phase separation structure of the conductive layer may be a co-continuous structure or a sea-island structure, and the plating layer may be laminated on a continuous phase formed of metal in the surface of the conductive layer. The porosity of the plating layer may be about 40 to 90%. In the conductive layer, the volume ratio between the metal and the low-melting glass may be the former / the latter = 93/7 to 50/50. The softening point of the low melting point glass may be a temperature lower than the firing temperature of the conductive layer. The low-melting glass may be a fired product of bismuth-based glass frit. The metal of the conductive layer may be silver. The plating layer may contain nickel. The average thickness of the plating layer may be about 0.3 to 2 μm.
本発明には、金属粒子及びガラスフリットを含む導電層前駆体をガラス基板の上に塗布後、焼成して導電層を形成する導電層形成工程、導電層の上に金属をメッキしてメッキ層を形成するメッキ層形成工程を含む前記導電性積層体の製造方法も含まれる。前記導電層前駆体はさらに有機バインダーを含んでいてもよい。 The present invention includes a conductive layer forming step of forming a conductive layer by applying a conductive layer precursor containing metal particles and glass frit on a glass substrate, and then baking the plated conductive layer. The manufacturing method of the said conductive laminated body including the plating layer formation process which forms is also included. The conductive layer precursor may further contain an organic binder.
本発明では、ガラス基板の上に、金属及び低融点ガラスを含み、かつ前記金属で形成された連続相を含む相分離構造を有する導電層が積層され、さらにこの導電層の上にメッキ層が積層されているため、ガラス基板の上に導電膜を形成しても、耐熱衝撃性を向上できる。また、導電層が低融点ガラスを含むため、ガラス基板と導電膜との密着性も向上できる。さらに、ニッケルを含むメッキ膜でメッキ層を形成すると、半田付け性及び耐変色性などの耐久性も向上できる。 In the present invention, a conductive layer having a phase separation structure including a metal and a low melting point glass and including a continuous phase formed of the metal is laminated on a glass substrate, and a plating layer is further formed on the conductive layer. Since they are laminated, the thermal shock resistance can be improved even when a conductive film is formed on a glass substrate. Moreover, since a conductive layer contains low melting glass, the adhesiveness of a glass substrate and a conductive film can also be improved. Furthermore, when the plating layer is formed of a plating film containing nickel, durability such as solderability and discoloration resistance can be improved.
[導電性積層体]
本発明の導電性積層体は、ガラス基板と、このガラス基板の上に積層された導電層と、この導電層の上に積層されたメッキ層とを含む。
[Conductive laminate]
The conductive laminate of the present invention includes a glass substrate, a conductive layer laminated on the glass substrate, and a plating layer laminated on the conductive layer.
(ガラス基板)
ガラス基板としては、慣用のケイ酸塩ガラス(ケイ酸ガラス)、例えば、ソーダガラス、ホウケイ酸ガラス、クラウンガラス、バリウム含有ガラス、ストロンチウム含有ガラス、ホウ素含有ガラス、低アルカリガラス、無アルカリガラス、結晶化透明ガラス、シリカガラス、石英ガラス、耐熱ガラスなどで形成された基板などを利用できる。これらのガラス基板のうち、ソーダガラスや低アルカリガラスなどのアルカリガラス基板、ホウケイ酸ガラス基板が汎用される。
(Glass substrate)
As the glass substrate, conventional silicate glass (silicate glass), for example, soda glass, borosilicate glass, crown glass, barium-containing glass, strontium-containing glass, boron-containing glass, low alkali glass, alkali-free glass, crystal Substrates formed of transparent glass, silica glass, quartz glass, heat-resistant glass, etc. can be used. Among these glass substrates, alkali glass substrates such as soda glass and low alkali glass, and borosilicate glass substrates are widely used.
ガラス基板の表面は、酸化処理[表面酸化処理、例えば、放電処理(コロナ放電処理、グロー放電など)、酸処理(クロム酸処理など)、紫外線照射処理、焔処理など]、表面凹凸処理(溶剤処理、サンドブラスト処理など)などの表面処理がされていてもよい。 The surface of the glass substrate is subjected to oxidation treatment [surface oxidation treatment, for example, discharge treatment (corona discharge treatment, glow discharge, etc.), acid treatment (chromic acid treatment, etc.), ultraviolet irradiation treatment, wrinkle treatment, etc., surface unevenness treatment (solvent Surface treatment such as treatment, sandblast treatment, etc.).
ガラス基板の厚み(平均厚み)は、用途に応じて適宜選択すればよく、例えば、0.001〜10mm、好ましくは0.01〜5mm、さらに好ましくは0.05〜3mm(特に0.1〜1mm)程度であってもよい。 What is necessary is just to select the thickness (average thickness) of a glass substrate suitably according to a use, for example, 0.001-10 mm, Preferably it is 0.01-5 mm, More preferably, it is 0.05-3 mm (especially 0.1-3 mm). 1 mm) or so.
(導電層)
導電層は、金属及びガラス成分を含み、かつ前記金属で形成された連続相を含む相分離構造を有する。本発明では、導電層がこのような相分離構造を有することにより、導電層の表面において、金属で形成された連続相(金属相)に対して、低融点ガラスや空隙で形成された相(非金属相)が分散相及び/又は連続相として存在する。そのため、金属で形成された連続相の上に、容易に網目状のメッキ層を形成できるが、このような構造のメッキ層は、全面が被覆された従来のメッキ層に比べてクッション性(耐衝撃性)に優れたメッキ層である。メッキ層の空隙により、ガラス基板との線膨脹係数差により生じる熱応力を空隙により緩和(吸収)できるためである。
(Conductive layer)
The conductive layer includes a metal and glass component and has a phase separation structure including a continuous phase formed of the metal. In the present invention, since the conductive layer has such a phase separation structure, a phase formed of a low-melting glass or a void (on a continuous phase (metal phase) formed of metal on the surface of the conductive layer ( (Non-metallic phase) exists as a disperse phase and / or a continuous phase. Therefore, a mesh-like plated layer can be easily formed on the continuous phase formed of metal. However, the plated layer having such a structure has a cushioning property (resistance to resistance) compared to a conventional plated layer coated on the entire surface. It is a plating layer with excellent impact properties. This is because the thermal stress generated due to the difference in coefficient of linear expansion from the glass substrate can be relaxed (absorbed) by the voids in the plated layer.
金属相を含む相分離構造には、両連続構造、海島構造が含まれる。非金属相は、低融点ガラスを含む相であり、通常、低融点ガラスで形成された相(ガラス相)に加えて、フリット原料の焼結による収縮やバインダーなどの消失による空隙部(空隙相)を含む。 The phase separation structure including the metal phase includes a bicontinuous structure and a sea-island structure. The non-metallic phase is a phase containing a low-melting glass. Usually, in addition to a phase (glass phase) formed of low-melting glass, a void portion (void phase) due to shrinkage due to sintering of a frit raw material or disappearance of a binder or the like. )including.
導電層表面の相分離構造(導電層の全表面)において、金属相が占める面積割合は、例えば、40〜90%、好ましくは50〜80%、さらに好ましくは55〜75%程度である。金属相の面積割合が小さすぎると、金属で連続相を形成するのが困難となり、導電性積層体の導電性が低下する虞がある。一方、大きすぎると、網目状メッキ層を形成するのが困難となり、導電層の略全面にメッキ層が形成されるため、応力を緩和するのが困難となり、導電性積層体の耐熱衝撃性が低下する虞がある。 In the phase separation structure on the surface of the conductive layer (the entire surface of the conductive layer), the area ratio occupied by the metal phase is, for example, 40 to 90%, preferably 50 to 80%, and more preferably about 55 to 75%. If the area ratio of the metal phase is too small, it is difficult to form a continuous phase with the metal, and the conductivity of the conductive laminate may be reduced. On the other hand, if it is too large, it becomes difficult to form a mesh-like plating layer, and since the plating layer is formed on almost the entire surface of the conductive layer, it becomes difficult to relieve stress, and the thermal shock resistance of the conductive laminate is reduced. May decrease.
金属(金属原子)としては、例えば、遷移金属(例えば、チタン、ジルコニウムなどの周期表第4A族金属;バナジウム、ニオブなどの周期表第5A族金属;モリブデン、タングステンなどの周期表第6A族金属;マンガンなどの周期表第7A族金属;鉄、ニッケル、コバルト、ルテニウム、ロジウム、パラジウム、レニウム、イリジウム、白金などの周期表第8族金属;銅、銀、金などの周期表第1B族金属など)、周期表第2B族金属(例えば、亜鉛、カドミウムなど)、周期表第3B族金属(例えば、アルミニウム、ガリウム、インジウムなど)、周期表第4B族金属(例えば、ゲルマニウム、スズ、鉛など)、周期表第5B族金属(例えば、アンチモン、ビスマスなど)などが挙げられる。これらの金属は、単独で又は二種以上組み合わせて使用でき、合金であってもよい。これらの金属のうち、導電性などの点から、周期表第8族金属(鉄、ニッケル、ロジウム、パラジウム、白金など)、周期表第1B族金属(銅、銀、金など)、周期表第3B族金属(アルミニウムなど)及び周期表第4B族金属(スズなど)などが汎用され、導電性金属、特に銀が好ましい。 Examples of the metal (metal atom) include transition metals (for example, periodic table Group 4A metals such as titanium and zirconium; periodic table Group 5A metals such as vanadium and niobium; periodic table Group 6A metals such as molybdenum and tungsten). Periodic Table Group 7A metals such as manganese; Periodic Table Group 8 metals such as iron, nickel, cobalt, ruthenium, rhodium, palladium, rhenium, iridium and platinum; Periodic Table Group 1B metals such as copper, silver and gold Etc.), Periodic Table Group 2B metals (eg, zinc, cadmium, etc.), Periodic Table Group 3B metals (eg, aluminum, gallium, indium, etc.), Periodic Table Group 4B metals (eg, germanium, tin, lead, etc.) ), Periodic table Group 5B metals (for example, antimony, bismuth, and the like). These metals can be used alone or in combination of two or more, and may be an alloy. Among these metals, from the viewpoint of conductivity, Group 8 metal of the periodic table (iron, nickel, rhodium, palladium, platinum, etc.), Group 1B metal of the periodic table (copper, silver, gold, etc.), periodic table Group 3B metals (such as aluminum) and periodic table Group 4B metals (such as tin) are widely used, and conductive metals, particularly silver, are preferred.
低融点ガラス(溶融性ガラス)としては、慣用のガラスフリット(溶融性ガラス粉又は粒子)の焼成物を利用できる。慣用のガラスフリットとしては、例えば、ホウケイ酸系ガラスフリット、ホウケイ酸亜鉛系ガラスフリット、亜鉛系ガラスフリット、ビスマス系ガラスフリット、鉛系ガラスフリットなどが挙げられる。これらのガラスフリットは、単独で又は二種以上組み合わせて使用できる。これらのガラスフリットのうち、軟化し易く、焼結助剤として作用し、硬質な金属をガラス基板に密着できる点から、ビスマス系ガラスフリットが好ましい。 As the low melting point glass (melting glass), a fired product of a conventional glass frit (melting glass powder or particles) can be used. Examples of conventional glass frit include borosilicate glass frit, zinc borosilicate glass frit, zinc glass frit, bismuth glass frit, and lead glass frit. These glass frit can be used individually or in combination of 2 or more types. Of these glass frits, a bismuth-based glass frit is preferable because it is easily softened, acts as a sintering aid, and can adhere a hard metal to the glass substrate.
ビスマス系ガラスフリットは酸化ビスマス(Bi2O3)を含んでいればよく、酸化ビスマスに加えて、他の酸化物を含んでいてもよい。他の酸化物としては、例えば、他の金属酸化物(例えば、酸化リチウム、酸化ナトリウム、酸化カリウムなどのアルカリ金属酸化物;酸化マグネシウム、酸化カルシウム、酸化ストロンチウム、酸化バリウムなどのアルカリ土類金属酸化物;酸化チタン、酸化ジルコニウムなどの周期表第4A族金属酸化物;酸化クロムなどの周期表第6A族金属酸化物;酸化鉄などの周期表第8族金属酸化物;酸化亜鉛などの周期表第2B族金属酸化物;酸化アルミニウムなどの周期表第3B族金属酸化物;酸化スズ、酸化鉛などの周期表第4B族金属酸化物など)、酸化ケイ素、酸化ホウ素などが挙げられる。これら他の酸化物は、単独で又は二種以上組み合わせて使用できる。これら他の酸化物のうち、酸化リチウム、酸化ナトリウム、酸化バリウム、酸化亜鉛、酸化鉛、酸化ケイ素、酸化ホウ素などを含有している場合が多い。酸化ビスマスの割合は、ガラスフリット全体に対して、例えば、10質量%以上、好ましくは15質量%以上(例えば、15〜95質量%)、さらに好ましくは20〜90質量%(特に30〜80質量%)程度であってもよい。 The bismuth-based glass frit only needs to contain bismuth oxide (Bi 2 O 3 ), and may contain other oxides in addition to bismuth oxide. Examples of other oxides include other metal oxides (for example, alkali metal oxides such as lithium oxide, sodium oxide, and potassium oxide; alkaline earth metal oxides such as magnesium oxide, calcium oxide, strontium oxide, and barium oxide). Periodic Table Group 4A metal oxides such as titanium oxide and zirconium oxide; Periodic Table Group 6A metal oxides such as chromium oxide; Periodic Table Group 8 metal oxides such as iron oxide; Periodic table such as zinc oxide Group 2B metal oxides; periodic table Group 3B metal oxides such as aluminum oxide; periodic table Group 4B metal oxides such as tin oxide and lead oxide), silicon oxide, boron oxide and the like. These other oxides can be used alone or in combination of two or more. Of these other oxides, they often contain lithium oxide, sodium oxide, barium oxide, zinc oxide, lead oxide, silicon oxide, boron oxide, and the like. The ratio of bismuth oxide is, for example, 10% by mass or more, preferably 15% by mass or more (for example, 15 to 95% by mass), more preferably 20 to 90% by mass (particularly 30 to 80% by mass) with respect to the entire glass frit. %) Degree.
低融点ガラスの軟化点は、例えば、導電膜の焼成温度よりも低ければよく、換言すれば、ガラス基板の耐熱温度(軟化点)よりも低い軟化点であればよい。具体的には、低融点ガラスの軟化点は、例えば、350〜600℃程度の範囲から選択でき、例えば、380〜580℃、好ましくは400〜580℃、さらに好ましくは420〜580℃(特に450〜550℃)程度であってもよい。軟化点が高すぎると、溶融流動性が低下するため、共連続構造や海島構造の形成も困難となる上に、ガラス基板との密着性も低下する。 The softening point of the low-melting glass may be, for example, lower than the firing temperature of the conductive film, in other words, the softening point lower than the heat-resistant temperature (softening point) of the glass substrate. Specifically, the softening point of the low-melting glass can be selected from a range of, for example, about 350 to 600 ° C., for example, 380 to 580 ° C., preferably 400 to 580 ° C., more preferably 420 to 580 ° C. It may be about ˜550 ° C.). When the softening point is too high, melt fluidity is lowered, so that it is difficult to form a co-continuous structure or a sea-island structure, and adhesion to the glass substrate is also lowered.
金属と低融点ガラスとの体積割合は、例えば、金属/低融点ガラス=93/7〜50/50、好ましくは90/10〜55/45、さらに好ましくは80/20〜60/40程度である。金属の体積割合が小さすぎると、網目状メッキ層を形成するのが困難となり、導電性積層体の耐熱衝撃性が低下する虞がある。なお、金属相は金属粒子焼結で形成されるため、低融点ガラスが無くても7体積%程度の空隙(ポーラス)を発生する。しかし、この状態でメッキ層を形成すると、メッキ液が容易に空隙に侵入するため、導電層の内部までメッキ膜が成膜され、高い応力が発生する。そのため、空隙へのメッキ液の浸入を防ぐために、金属と低融点ガラスとの総量に対して所定量の低融点ガラスが必要となる。一方、金属の体積割合が大きすぎると、導電性積層体の導電性が低下する虞がある。 The volume ratio between the metal and the low-melting glass is, for example, metal / low-melting glass = 93/7 to 50/50, preferably 90/10 to 55/45, and more preferably about 80/20 to 60/40. . When the volume ratio of the metal is too small, it is difficult to form a mesh-like plating layer, and the thermal shock resistance of the conductive laminate may be reduced. Since the metal phase is formed by sintering metal particles, a void of about 7% by volume is generated even without the low melting point glass. However, if the plating layer is formed in this state, the plating solution easily penetrates into the gap, so that the plating film is formed even inside the conductive layer and high stress is generated. Therefore, in order to prevent the plating solution from entering the gap, a predetermined amount of low melting point glass is required with respect to the total amount of metal and low melting point glass. On the other hand, when the volume ratio of the metal is too large, the conductivity of the conductive laminate may be reduced.
導電層の平均厚みは、導電層前駆体(塗布液)に含まれる原料金属粒子の粒径以上の厚みであればよく、例えば、2〜20μm、好ましくは3〜15μm、さらに好ましくは5〜10μm程度である。導電層の厚みは、蛍光X線膜厚計を用いて測定でき、任意の5点の厚みを測定して平均値を算出する。 The average thickness of a conductive layer should just be the thickness more than the particle size of the raw material metal particle contained in a conductive layer precursor (coating liquid), for example, 2-20 micrometers, Preferably it is 3-15 micrometers, More preferably, it is 5-10 micrometers. Degree. The thickness of the conductive layer can be measured using a fluorescent X-ray film thickness meter, and the average value is calculated by measuring the thickness of any five points.
(メッキ層)
前記導電層の上には、さらにメッキ層が積層されている。メッキ層の製造工程では、前記導電層のうち、金属で形成された連続相の上に選択的にメッキ核が発生して成長し、低融点ガラスの表面や空隙部にはメッキ膜は形成されないため、メッキ層は、前記連続相に略対応した網目形状(ポーラス状)を有している。
(Plating layer)
A plating layer is further laminated on the conductive layer. In the plating layer manufacturing process, plating nuclei are selectively generated and grown on a continuous phase formed of metal in the conductive layer, and no plating film is formed on the surface or voids of the low melting point glass. Therefore, the plating layer has a mesh shape (porous shape) substantially corresponding to the continuous phase.
導電層の全表面に対してメッキ層が占める面積割合であるメッキ層の空隙率(単位面積当たり空隙の面積の比率)は、例えば、40〜90%、好ましくは50〜80%、さらに好ましくは55〜75%程度である。メッキ層の空隙率が大きすぎると、導電性積層体の導電性が低下する虞がある。一方、小さすぎると、導電性積層体の耐熱衝撃性が低下する虞がある。 The porosity of the plating layer (ratio of the area of the void per unit area), which is the area ratio of the plating layer to the entire surface of the conductive layer, is, for example, 40 to 90%, preferably 50 to 80%, and more preferably. It is about 55 to 75%. If the porosity of the plating layer is too large, the conductivity of the conductive laminate may be reduced. On the other hand, when too small, there exists a possibility that the thermal shock resistance of an electroconductive laminated body may fall.
メッキ層のメッキ種は金属(特に導電性金属)で形成されていればよい。導電性金属としては、前記導電層の項で例示された金属を利用できる。前記金属のうち、導電性などの点から、周期表第8族金属(鉄、ニッケル、ロジウム、パラジウム、白金など)、周期表第1B族金属(銅、銀、金など)、周期表第3B族金属(アルミニウムなど)及び周期表第4B族金属(スズなど)などが汎用され、導電性などの点から、ニッケル、パラジウム、金が好ましく、半田付け性及び耐変色性などの耐久性も向上できる点から、ニッケルが特に好ましい。 The plating type of the plating layer may be formed of metal (particularly conductive metal). As the conductive metal, the metal exemplified in the section of the conductive layer can be used. Among the metals, from the viewpoint of conductivity, Group 8 metal of periodic table (iron, nickel, rhodium, palladium, platinum, etc.), Group 1B metal of periodic table (copper, silver, gold, etc.), Periodic table 3B Group metals (such as aluminum) and Group 4B metals (such as tin) are widely used. From the viewpoint of conductivity, nickel, palladium, and gold are preferable, and durability such as solderability and discoloration resistance is also improved. Nickel is particularly preferable because it can be used.
これらの導電性金属は、単独で又は二種以上組み合わせて使用できる。特に、複数種のメッキ膜を組み合わせてもよく、例えば、ニッケルメッキ膜と他の導電性金属膜(金やパラジウムなどのメッキ膜)との積層構造であってもよく、特に、導電層に対して、ニッケルメッキ膜を積層した後、他の金属で形成された金属メッキ膜を積層するのが特に好ましい。ニッケルメッキ膜は、半田付けの際における半田との結合層としての機能に加え、下地の金属への半田の浸食を防ぐ浸食防止層としての役割を担う。 These conductive metals can be used alone or in combination of two or more. In particular, a plurality of types of plating films may be combined. For example, a laminated structure of a nickel plating film and another conductive metal film (plating film such as gold or palladium) may be used. It is particularly preferable to laminate a metal plating film formed of another metal after the nickel plating film is laminated. The nickel plating film plays a role as an erosion preventing layer for preventing erosion of the solder to the underlying metal in addition to a function as a bonding layer with the solder at the time of soldering.
なお、本発明では、導電層の金属相に選択的にメッキを行うため、メッキ用下地層は形成しなくてもよい。 In the present invention, since the metal phase of the conductive layer is selectively plated, it is not necessary to form the plating base layer.
メッキ層の平均厚み(積層構造の場合は総厚み)は、例えば、0.3〜3μm(例えば、0.3〜2μm)、好ましくは0.35〜2μm、さらに好ましくは0.4〜2μm程度である。メッキ層がニッケルメッキ膜を含む場合、ニッケルメッキ膜の平均厚みは、例えば、0.2〜2μm、好ましくは0.25〜1.5μm、さらに好ましくは0.3〜1.5μm程度である。メッキ層の厚みが大きくなると、導電層の非金属相にまでメッキ膜が生成して、メッキ層の空隙が減少し、最終的には隙間の埋まった(網目状でない)メッキ層となる虞がある。一方、メッキ層の厚みが小さすぎると、一般的に使用する半田付けの際に、浸食防止層としての機能が低下する虞がある。メッキ層の厚みも、蛍光X線膜厚計を用いて測定でき、任意の5点の厚みを測定して平均値を算出する。 The average thickness of the plating layer (total thickness in the case of a laminated structure) is, for example, 0.3 to 3 μm (for example, 0.3 to 2 μm), preferably 0.35 to 2 μm, and more preferably about 0.4 to 2 μm. It is. When the plating layer includes a nickel plating film, the average thickness of the nickel plating film is, for example, about 0.2 to 2 μm, preferably about 0.25 to 1.5 μm, and more preferably about 0.3 to 1.5 μm. If the thickness of the plating layer is increased, a plating film may be formed even in the non-metallic phase of the conductive layer, and the plating layer voids may be reduced, eventually resulting in a plating layer having a gap (not a mesh). is there. On the other hand, if the thickness of the plating layer is too small, there is a risk that the function as an erosion preventing layer may be reduced during soldering that is generally used. The thickness of the plating layer can also be measured using a fluorescent X-ray film thickness meter, and the average value is calculated by measuring the thickness of any five points.
[導電性積層体の製造方法]
導電性積層体は、金属粒子及びガラスフリットを含む導電層前駆体をガラス基板の上に塗布後、焼成して導電層を形成する導電層形成工程、導電層の上に金属をメッキしてメッキ層を形成するメッキ層形成工程を経て製造される。
[Method for producing conductive laminate]
The conductive laminate is a conductive layer forming step in which a conductive layer precursor containing metal particles and glass frit is applied on a glass substrate and then baked to form a conductive layer. It is manufactured through a plating layer forming step for forming a layer.
導電層形成工程では、まず、導電層前駆体として、金属粒子及びガラスフリットを含む導電性ペースト(塗布液)が調製される。 In the conductive layer forming step, first, a conductive paste (coating liquid) containing metal particles and glass frit is prepared as a conductive layer precursor.
金属原料である金属粒子の形状は、特に限定されず、球状(真球状又は略球状)、楕円体(楕円球)状、多角体状(多角錘状、正方体状や直方体状など多角方体状など)、板状(扁平、鱗片又は薄片状など)、ロッド状又は棒状、繊維状、不定形状などであってもよい。金属粒子の形状は、通常、球状、楕円体状、多角体状、不定形状などである。 The shape of the metal particles as the metal raw material is not particularly limited, and is a polygonal shape such as a spherical shape (true spherical shape or substantially spherical shape), an elliptical shape (elliptical spherical shape), a polygonal shape (polygonal pyramid shape, a rectangular parallelepiped shape, a rectangular parallelepiped shape, or the like). Etc.), plate-like (flat, scale-like or flake-like), rod-like or rod-like, fiber-like, irregular shape, etc. The shape of the metal particles is usually spherical, ellipsoidal, polygonal, indeterminate.
金属粒子の粒径は、特に制限されないが、多量の非導電性成分(無機バインダー成分及び抵抗調整成分)が配合されているため、例えば、銅粒子とニッケル粒子とをそれぞれ別個の金属粒子として使用する場合、均一な分散性及び焼成時の合金化の点から、小粒径の金属粒子を使用する方が有利である。一方、銅とニッケルとの合金粒子を使用する場合、合金化の均一性に問題はないものの、分散性の点から、同様に小粒径の合金粒子を使用するのが有利である。 The particle size of the metal particles is not particularly limited, but a large amount of non-conductive components (inorganic binder component and resistance adjusting component) are blended. For example, copper particles and nickel particles are used as separate metal particles. In this case, it is advantageous to use metal particles having a small particle size from the viewpoint of uniform dispersibility and alloying during firing. On the other hand, when using alloy particles of copper and nickel, although there is no problem in the uniformity of alloying, it is advantageous to use alloy particles having a small particle size in the same manner from the viewpoint of dispersibility.
金属粒子の中心一次粒径(D50)は、例えば、5nm〜10μm程度の範囲から選択でき、ナノメータサイズの粒子であってもよいが、取り扱い性や経済性などの点から、例えば、0.05〜10μm、好ましくは0.08〜8μm、さらに好ましくは0.1〜5μm(特に0.2〜3μm)程度である。金属粒子の粒径が小さすぎると、取り扱い性や経済性に加えて、ペースト中での分散性も低下し、大きすぎると、ペースト塗布性及び分散性、均一性が低下する虞がある。 The central primary particle size (D50) of the metal particles can be selected from the range of, for example, about 5 nm to 10 μm, and may be nanometer-sized particles. However, from the viewpoint of handleability and economy, for example, 0.05 It is about 10 to 10 μm, preferably 0.08 to 8 μm, more preferably about 0.1 to 5 μm (particularly 0.2 to 3 μm). If the particle size of the metal particles is too small, the dispersibility in the paste is reduced in addition to the handleability and economy, and if too large, the paste coating property, dispersibility, and uniformity may be lowered.
低融点ガラス原料であるガラスフリットの形状も、前記金属粒子の項で例示された形状などが挙げられ、通常、球状、楕円体状、多角体状、不定形状などである。 Examples of the shape of the glass frit which is a low melting point glass raw material include the shape exemplified in the section of the metal particles, and are usually spherical, ellipsoidal, polygonal, indeterminate.
ガラスフリットの中心一次粒径は、例えば、0.1〜10μm、好ましくは0.2〜8μm、さらに好ましくは0.3〜5μm(特に0.5〜3μm)程度であってもよい。ガラスフリットの粒径が大きすぎると、例えば、スクリーン印刷などにおいて目詰まりが発生し易くなる。一方、粒径が小さすぎると、ガラスフリットの分散性が低下するため、ガラスフリットの使用量が増加し、導電性が低下する虞がある。 The central primary particle size of the glass frit may be, for example, about 0.1 to 10 μm, preferably 0.2 to 8 μm, more preferably about 0.3 to 5 μm (particularly 0.5 to 3 μm). When the particle size of the glass frit is too large, clogging is likely to occur in, for example, screen printing. On the other hand, if the particle size is too small, the dispersibility of the glass frit is lowered, so that the amount of the glass frit used is increased and the conductivity may be lowered.
導電層ペーストは、さらに有機バインダーを含んでいてもよい。有機バインダーとしては、慣用のバインダー樹脂、例えば、水溶性高分子系バインダー(例えば、水溶性アクリル系樹脂、水溶性ウレタン樹脂、水溶性アクリルウレタン樹脂、水溶性エポキシ樹脂、水溶性ポリエステル系樹脂、セルロース誘導体、ポリビニルアルコール、ポリアルキレングリコール、天然高分子、ポリエチレンスルホン酸又はその塩、ポリスチレンスルホン酸又はその塩、ナフタレンスルホン酸のホルマリン縮合物、ポリアルキレンイミン、ポリビニルピロリドン、ポリアリルアミン、ポリエーテルポリアミンなど)、ホットメルト樹脂(例えば、脂肪族又は非晶性ポリエステルなどのポリエステル系樹脂、ポリビニルブチラールなどのポリビニルアセタール系樹脂など)、熱硬化性樹脂(例えば、フェノール系樹脂、エポキシ系樹脂、不飽和ポリエステル系樹脂など)などが挙げられる。 The conductive layer paste may further contain an organic binder. Examples of the organic binder include conventional binder resins, such as water-soluble polymer binders (for example, water-soluble acrylic resins, water-soluble urethane resins, water-soluble acrylic urethane resins, water-soluble epoxy resins, water-soluble polyester resins, and celluloses). Derivatives, polyvinyl alcohol, polyalkylene glycol, natural polymer, polyethylene sulfonic acid or its salt, polystyrene sulfonic acid or its salt, formalin condensate of naphthalene sulfonic acid, polyalkyleneimine, polyvinyl pyrrolidone, polyallylamine, polyether polyamine, etc.) , Hot melt resins (for example, polyester resins such as aliphatic or amorphous polyester, polyvinyl acetal resins such as polyvinyl butyral), thermosetting resins (for example, phenol resins, epoxy resins, etc.) Shi resins, such as unsaturated polyester resin) and the like.
これらのバインダー樹脂のうち、高分子分散剤としても作用する点から、セルロース誘導体などの水溶性高分子系バインダー、例えば、セルロースエーテル(例えば、ニトロセルロース;エチルセルロースなどのアルキルセルロース;エチルヒドロキシエチルセルロースなどのアルキル−ヒドロキシアルキルセルロース;ヒドロキシエチルセルロース、ヒドロキシプロピルセルロースなどのヒドロキシアルキルセルロース;カルボキシメチルセルロースなどのカルボキシアルキルセルロースなど)が好ましく、エチルセルロースなどのアルキルセルロースが特に好ましい。 Among these binder resins, water-soluble polymer binders such as cellulose derivatives, for example, cellulose ethers (for example, nitrocellulose; alkylcelluloses such as ethylcellulose; ethylhydroxyethylcellulose, etc.) from the point of acting as a polymer dispersant Alkyl-hydroxyalkyl celluloses; hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose; carboxyalkyl celluloses such as carboxymethyl cellulose) are preferred, and alkyl celluloses such as ethyl cellulose are particularly preferred.
有機バインダーの割合は、金属粒子100質量部に対して、例えば、200質量部以下であってもよく、例えば、1〜150質量部、好ましくは10〜100質量部、さらに好ましくは20〜80質量部(特に30〜60質量部)程度である。 The proportion of the organic binder may be, for example, 200 parts by mass or less with respect to 100 parts by mass of the metal particles, for example, 1 to 150 parts by mass, preferably 10 to 100 parts by mass, and more preferably 20 to 80 parts by mass. Part (particularly 30 to 60 parts by mass).
導電性ペーストには、用途に応じて、慣用の添加剤、例えば、分散媒(オクタノールなどの飽和又は不飽和C6−20脂肪族アルコール、エチレングリコールなどの脂肪族多価アルコール、テルピネオールなどの脂環族アルコールなど)、着色剤(染顔料など)、色相改良剤、染料定着剤、光沢付与剤、金属腐食防止剤、安定剤(酸化防止剤、紫外線吸収剤など)、界面活性剤又は分散剤(アニオン性界面活性剤、カチオン性界面活性剤、ノニオン性界面活性剤、両性界面活性剤など)、分散安定化剤、増粘剤又は粘度調整剤、保湿剤、チクソトロピー性賦与剤、レベリング剤、消泡剤、殺菌剤、充填剤などが含まれていてもよい。これらの添加剤は、単独で又は二種以上組み合わせて使用できる。 In the conductive paste, a conventional additive, for example, a dispersion medium (saturated or unsaturated C 6-20 aliphatic alcohol such as octanol, aliphatic polyhydric alcohol such as ethylene glycol, fat such as terpineol, etc.) Cyclic alcohols, etc.), colorants (dyeing pigments, etc.), hue improvers, dye fixing agents, gloss imparting agents, metal corrosion inhibitors, stabilizers (antioxidants, UV absorbers, etc.), surfactants or dispersants. (Anionic surfactant, cationic surfactant, nonionic surfactant, amphoteric surfactant, etc.), dispersion stabilizer, thickener or viscosity modifier, humectant, thixotropic agent, leveling agent, An antifoaming agent, a disinfectant, a filler and the like may be included. These additives can be used alone or in combination of two or more.
導電性ペーストは、このような組成のペーストを得ることができる限り特に限定されないが、通常、前記金属粒子及びガラスフリットを、前記有機バインダーを用いて分散させることにより調製できる。 The conductive paste is not particularly limited as long as a paste having such a composition can be obtained, but it can be usually prepared by dispersing the metal particles and glass frit using the organic binder.
導電性ペーストの塗布方法(コーティング方法)としては、慣用のコーティング方法、例えば、フローコーティング法、ディスペンサーコーティング法、スピンコーティング法、スプレーコーティング法、スクリーン印刷法、フレキソ印刷法、キャスト法、バーコーティング法、カーテンコーティング法、ロールコーティング法、グラビアコーティング法、ディッピング法、スリット法、フォトリソグラフィ法、インクジェット法などを利用できる。前記コーティング方法のうち、塗膜でパターンを形成(描画)してもよく、形成されたパターン(描画パターン)を焼成処理することにより焼結パターン(焼結膜又は焼結体層)を形成できる。パターン(塗布層)を描画するための描画法(又は印刷法)としては、パターン形成可能な印刷法であれば特に限定されず、例えば、スクリーン印刷法、インクジェット印刷法、凹版印刷法(例えば、グラビア印刷法など)、オフセット印刷法、凹版オフセット印刷法、フレキソ印刷法などが挙げられる。これらの方法のうち、スクリーン印刷法などが好ましい。 As a conductive paste application method (coating method), conventional coating methods such as flow coating method, dispenser coating method, spin coating method, spray coating method, screen printing method, flexographic printing method, casting method, bar coating method, etc. Curtain coating method, roll coating method, gravure coating method, dipping method, slit method, photolithography method, ink jet method and the like can be used. Among the coating methods, a pattern may be formed (drawn) with a coating film, and a sintered pattern (sintered film or sintered body layer) can be formed by firing the formed pattern (drawn pattern). The drawing method (or printing method) for drawing the pattern (coating layer) is not particularly limited as long as it is a pattern forming printing method. For example, a screen printing method, an ink jet printing method, an intaglio printing method (for example, Gravure printing method), offset printing method, intaglio offset printing method, flexographic printing method and the like. Of these methods, the screen printing method and the like are preferable.
塗布後は、乾燥せずに焼成してもよいが、均一な導電膜を形成し易い点から、乾燥するのが好ましい。乾燥方法は、自然乾燥であってもよく、加熱して乾燥してもよい。加熱温度は、例えば、50〜300℃、好ましくは80〜200℃、さらに好ましくは100〜150℃程度である。加熱時間は、例えば、1分〜3時間、好ましくは5分〜2時間、さらに好ましくは10分〜1時間程度である。 After application, the film may be baked without being dried, but is preferably dried from the viewpoint of easily forming a uniform conductive film. The drying method may be natural drying or may be dried by heating. The heating temperature is, for example, about 50 to 300 ° C, preferably about 80 to 200 ° C, and more preferably about 100 to 150 ° C. The heating time is, for example, about 1 minute to 3 hours, preferably about 5 minutes to 2 hours, and more preferably about 10 minutes to 1 hour.
焼成温度は、ガラスフリットの軟化点以上であり、かつガラス基板の耐熱温度未満の温度である。焼成温度(ピーク温度)は、例えば、400℃以上(例えば、400〜1000℃)、好ましくは450〜800℃、さらに好ましくは500〜700℃(特に550〜650℃)程度である。熱処理時間(加熱時間)は、熱処理温度などに応じて、例えば、1分〜3時間、好ましくは5分〜1時間、さらに好ましくは10〜30分程度であってもよい。 The firing temperature is equal to or higher than the softening point of the glass frit and lower than the heat resistance temperature of the glass substrate. The firing temperature (peak temperature) is, for example, about 400 ° C. or more (for example, 400 to 1000 ° C.), preferably 450 to 800 ° C., more preferably about 500 to 700 ° C. (especially 550 to 650 ° C.). The heat treatment time (heating time) may be, for example, 1 minute to 3 hours, preferably 5 minutes to 1 hour, more preferably about 10 to 30 minutes, depending on the heat treatment temperature and the like.
メッキ層の形成方法としては、慣用のメッキ方法を利用でき、導電層の金属相に選択的にメッキ層を形成し易い点から、電気メッキ、無電解メッキなどが好ましい。電気メッキの方法としては、特に限定されず、メッキ種に応じて従来のメッキ薬品メーカの推奨条件で行なえばよい。無電解メッキの方法としては、特に限定されず、メッキ種に応じて慣用の条件で行なえばよい。 As a method for forming the plating layer, a conventional plating method can be used, and electroplating, electroless plating, or the like is preferable because a plating layer can be selectively formed on the metal phase of the conductive layer. The electroplating method is not particularly limited, and may be performed under the conditions recommended by conventional plating chemical manufacturers according to the type of plating. The method of electroless plating is not particularly limited, and may be performed under conventional conditions depending on the type of plating.
以下に、実施例に基づいて本発明をより詳細に説明するが、本発明はこれらの実施例によって限定されるものではない。用いた材料及び器具を以下に示す。 Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. The materials and instruments used are shown below.
[用いた材料及び器具]
ガラス基板:Schott社製「D263T」
銀粉末(SPN20J):三井金属鉱業(株)製「SPN20J」、平均粒径D50:1.82μm
Bi系ガラスフリット(GF3535):Bi2O3−SiO2−R2O(式中、R2O=Li2O,Na2O,K2Oを総称した表記)、奥野製薬工業(株)製「GF3535」、比重4.9
Bi系ガラスフリット(GF3440):Bi2O3−ZnO2−B2O3、奥野製薬工業(株)製「GF3440」、比重6.6
有機バインダー:エチルセルロース、日進化成(株)販売「EC−200FTD」
スクリーン印刷機:(株)ムラカミ製、ステンレスメッシュ(メッシュカウント:325、乳剤10μm)
熱風循環オーブン:ADVANTEC社製「FC−410」
ベルト炉:光洋サーモシステム(株)製。
[Materials and equipment used]
Glass substrate: “D263T” manufactured by Schott
Silver powder (SPN20J): “SPN20J” manufactured by Mitsui Mining & Smelting Co., Ltd., average particle size D50: 1.82 μm
Bi-based glass frit (GF3535): Bi 2 O 3 —SiO 2 —R 2 O (in the formula, R 2 O = Li 2 O, Na 2 O, K 2 O), Okuno Pharmaceutical Co., Ltd. “GF3535” manufactured, specific gravity 4.9
Bi glass frit (GF3440): Bi 2 O 3 —ZnO 2 —B 2 O 3 , “GF3440” manufactured by Okuno Pharmaceutical Co., Ltd., specific gravity 6.6
Organic binder: Ethyl cellulose, sold by Nihon Kasei Co., Ltd. “EC-200FTD”
Screen printer: Murakami Co., Ltd., stainless mesh (mesh count: 325, emulsion 10 μm)
Hot air circulation oven: “FC-410” manufactured by ADVANTEC
Belt furnace: manufactured by Koyo Thermo System Co., Ltd.
[実施例1]
(導電層用導電性ペースト作製)
銀粉末100g、Bi系ガラスフリット(GF3535)20g、有機バインダー51gを自動乳鉢で練り、導電性ペーストを作製した。銀粉末とBi系ガラスフリットとの総量に対して、Biガラスフリットの体積割合は30体積%である。
[Example 1]
(Preparation of conductive paste for conductive layer)
100 g of silver powder, 20 g of Bi glass frit (GF3535), and 51 g of organic binder were kneaded in an automatic mortar to prepare a conductive paste. The volume ratio of Bi glass frit is 30% by volume with respect to the total amount of silver powder and Bi glass frit.
(導電層の形成)
得られた導電性ペーストを、ガラス基板上にスクリーン印刷し、熱風循環オーブン中で、120℃で30分間乾燥を行った後、ピーク温度600℃で10分(In−Out60分間)に設定したベルト炉で焼成し、ガラス基板上に導電性ペーストの焼結膜(平均厚み5μm)が形成された積層体を得た。走査型電子顕微鏡による表面観察を行った結果、図1に示すように、金属とBi系ガラス及び空隙とが「海島構造」又は「共連続構造」を形成していた。なお、写真中で黒く見える部分が空隙である。
(Formation of conductive layer)
The obtained conductive paste was screen-printed on a glass substrate, dried in a hot air circulating oven at 120 ° C. for 30 minutes, and then set at a peak temperature of 600 ° C. for 10 minutes (In-Out 60 minutes). Firing was performed in a furnace to obtain a laminate in which a sintered film (average thickness of 5 μm) of a conductive paste was formed on a glass substrate. As a result of surface observation using a scanning electron microscope, as shown in FIG. 1, the metal, the Bi-based glass, and the voids formed a “sea-island structure” or a “co-continuous structure”. Note that the portion that appears black in the photograph is a void.
(メッキ層の形成)
得られた積層体の導電層の上に、Niメッキ膜(平均厚み0.3μm)、Pdメッキ膜(平均厚み0.1μm)、Auメッキ膜(平均厚み0.05μm)の順に無電解メッキを施し、導電性積層体を得た。走査型電子顕微鏡による表面観察を行った結果、図2に示すように、最表面の金が「網目構造」を形成していることが確認された。
(Formation of plating layer)
On the conductive layer of the obtained laminate, electroless plating was performed in the order of Ni plating film (average thickness 0.3 μm), Pd plating film (average thickness 0.1 μm), and Au plating film (average thickness 0.05 μm). To obtain a conductive laminate. As a result of surface observation with a scanning electron microscope, it was confirmed that the gold on the outermost surface formed a “network structure” as shown in FIG.
得られた導電性積層体を、260℃に設定したホットプレート上で30秒間加熱した後、ホットプレートから取出し、室温まで急冷した。裏面から、導電性積層体を確認したところ、ガラスにクラックなどは発生しなかった。 The obtained conductive laminate was heated on a hot plate set at 260 ° C. for 30 seconds, then taken out of the hot plate and rapidly cooled to room temperature. When the conductive laminate was confirmed from the back side, no cracks or the like occurred in the glass.
更に、熱衝撃試験(−55℃〜150℃、300サイクル)を行った後、裏面から、積層体を確認したところ、ガラスにクラック等は発生しなかった。 Furthermore, after conducting a thermal shock test (-55 ° C. to 150 ° C., 300 cycles), the laminate was confirmed from the back side, and no cracks or the like were generated in the glass.
[実施例2]
実施例1と同様の方法でガラス基板の上に導電性ペーストの焼結膜を形成した積層体の導電層の上に、Niメッキ膜(平均厚み1.5μm)、Pdメッキ膜(平均厚み0.1μm)、Auメッキ膜(平均厚み0.05μm)の順に無電解メッキを施し、導電性積層体を得た。走査型電子顕微鏡による表面観察を行った結果、実施例1と同様に、最表面の金が「網目構造」を形成していることが確認された。
[Example 2]
A Ni plating film (average thickness of 1.5 μm) and a Pd plating film (average thickness of 0.1 μm) were formed on the conductive layer of the laminate in which the sintered film of the conductive paste was formed on the glass substrate by the same method as in Example 1. 1 μm) and Au plating film (average thickness 0.05 μm) were applied in this order to obtain a conductive laminate. As a result of surface observation with a scanning electron microscope, it was confirmed that gold on the outermost surface formed a “network structure” as in Example 1.
得られた導電性積層体を、260℃に設定したホットプレート上で30秒間加熱した後、ホットプレートから取出し、室温まで急冷した。裏面から、導電性積層体を確認したところ、ガラスにクラックなどは発生しなかった。 The obtained conductive laminate was heated on a hot plate set at 260 ° C. for 30 seconds, then taken out of the hot plate and rapidly cooled to room temperature. When the conductive laminate was confirmed from the back side, no cracks or the like occurred in the glass.
更に、熱衝撃試験(−55℃〜150℃、300サイクル)を行った後、裏面から、積層体を確認したところ、ガラスにクラック等は発生しなかった。 Furthermore, after conducting a thermal shock test (-55 ° C. to 150 ° C., 300 cycles), the laminate was confirmed from the back side, and no cracks or the like were generated in the glass.
[比較例1]
(導電層用導電性ペースト作製)
銀粉末100g、Bi系ガラスフリット(GF3440)1g、有機バインダー10gを自動乳鉢で練り、導電性ペーストを作製した。銀粉末とBi系ガラスフリットとの総量に対して、Biガラスフリットの体積割合は1.55体積%である。
[Comparative Example 1]
(Preparation of conductive paste for conductive layer)
100 g of silver powder, 1 g of Bi glass frit (GF3440) and 10 g of organic binder were kneaded in an automatic mortar to prepare a conductive paste. The volume ratio of Bi glass frit is 1.55 volume% with respect to the total amount of silver powder and Bi glass frit.
(導電層の形成)
得られた導電性ペーストを用いて、実施例1と同様の方法でガラス基板上に導電性ペーストの焼結膜(5μm)が形成された積層体を得た。走査型電子顕微鏡による表面観察を行った結果、図3に示すように、焼結膜において、金属とBi系ガラスとの海島構造は見られなかった。写真中において、穴部は空隙であり、その他の領域が金属及びBi系ガラスが均一的に焼結した領域である。
(Formation of conductive layer)
Using the obtained conductive paste, a laminate in which a sintered film (5 μm) of the conductive paste was formed on the glass substrate in the same manner as in Example 1 was obtained. As a result of surface observation with a scanning electron microscope, as shown in FIG. 3, the sea-island structure of metal and Bi-based glass was not seen in the sintered film. In the photograph, the hole is a void, and the other region is a region where the metal and the Bi-based glass are uniformly sintered.
(メッキ層の形成)
得られた積層体の導電層の上に、実施例1と同様の方法で無電解メッキを施し、導電性積層体を得た。走査型電子顕微鏡による表面観察を行った結果、図4に示すように、網目構造のない均一なニッケルメッキ膜(表面が金で被覆されたニッケルメッキ膜)が形成されていることが確認された。
(Formation of plating layer)
On the conductive layer of the obtained laminate, electroless plating was performed in the same manner as in Example 1 to obtain a conductive laminate. As a result of surface observation using a scanning electron microscope, as shown in FIG. 4, it was confirmed that a uniform nickel-plated film (a nickel-plated film whose surface was coated with gold) without a network structure was formed. .
得られた導電性積層体を、260℃に設定したホットプレート上で30秒間加熱した後、ホットプレートから取出し、室温まで急冷した。導電性積層体の状態を確認したところ、ガラスにクラックが発生しており、時間の経過とともにクラックが伸展したことから、回路基板としての実用は困難であった。 The obtained conductive laminate was heated on a hot plate set at 260 ° C. for 30 seconds, then taken out of the hot plate and rapidly cooled to room temperature. When the state of the conductive laminate was confirmed, cracks were generated in the glass, and the cracks extended with the passage of time, so that practical use as a circuit board was difficult.
[参考例1]
実施例1と同様の方法でガラス基板の上に導電性ペーストの焼結膜を形成した積層体の上に、Niメッキ膜(平均厚み5μm)、Pdメッキ膜(平均厚み0.1μm)、Auメッキ膜(平均厚み0.05μm)の順に無電解メッキを施し、導電性積層体を得た。走査型電子顕微鏡による表面観察を行った結果、網目構造のない均一なニッケルメッキ膜(表面が金で被覆されたニッケルメッキ膜)が形成されていることが確認された。すなわち、ニッケルメッキ膜を厚く成長させすぎて、導電層の空隙やBi系ガラス部位にまでメッキ膜が生成して、空隙が減少し、最終的には隙間の埋まった(網目でない)メッキ膜となってしまった。
[Reference Example 1]
A Ni plating film (average thickness 5 μm), a Pd plating film (average thickness 0.1 μm), and Au plating are formed on a laminate in which a conductive paste sintered film is formed on a glass substrate in the same manner as in Example 1. Electroless plating was performed in the order of the film (average thickness 0.05 μm) to obtain a conductive laminate. As a result of surface observation with a scanning electron microscope, it was confirmed that a uniform nickel-plated film (a nickel-plated film whose surface was coated with gold) without a network structure was formed. That is, by growing the nickel plating film too thickly, a plating film is generated even in the gap of the conductive layer and the Bi-based glass part, the gap is reduced, and finally the plating film with a gap filled (not meshed) It is had.
本発明の導電性積層体は、例えば、プラズマディスプレイパネル(PDP)、蛍光表示管(VFD)、液晶ディスプレイ(LCD)、有機エレクトロルミネッセンスディスプレイ(ELD)などの表示装置、タッチパネル式表示装置などの電極、RFIDタグ、電磁波シールド、家庭又は学習用配線キットなどに使用される導電膜などとして利用できる。 The conductive laminate of the present invention includes, for example, electrodes such as a plasma display panel (PDP), a fluorescent display tube (VFD), a liquid crystal display (LCD), an organic electroluminescence display (ELD), and a touch panel display device. It can be used as a conductive film used in an RFID tag, an electromagnetic wave shield, a home or learning wiring kit, and the like.
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