JP2012226841A - Ultrafine copper particle dispersed paste and method of forming conductive film - Google Patents
Ultrafine copper particle dispersed paste and method of forming conductive film Download PDFInfo
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本発明は、銅超微粒子を分散した低温焼成用導電ペーストおよび銅導電膜による配線パターン形成の分野に関するものである。
詳しくは、銅超微粒子の分散ペーストを用いてスクリーン印刷などで耐熱性樹脂基板上に配線パターンを形成し、低温焼成雰囲気で緻密な低抵抗焼成導電膜を形成する銅超微粒子分散ペーストおよびそれを利用した微細な焼成配線パターン形成方法に関するものである。
The present invention relates to the field of low-temperature firing conductive paste in which ultrafine copper particles are dispersed and the formation of a wiring pattern using a copper conductive film.
Specifically, a copper ultrafine particle dispersed paste for forming a dense low resistance fired conductive film in a low temperature firing atmosphere by forming a wiring pattern on a heat resistant resin substrate by screen printing or the like using a dispersion paste of copper ultrafine particles and The present invention relates to a method for forming a fine fired wiring pattern.
電子機器関連分野において、基板上の配線パターンの微細化が進んでいる。その中で、金属超微粒子を利用した微細配線パターン形成方法がある。すでに、金超微粒子、銀超微粒子を分散したペーストを用いて極めて微細な配線パターン描画と、その後の焼成で金属に近い導電性能が得られている。金超微粒子は非常に高価であるため、銀超微粒子による実用化が進められている。 In the field of electronic equipment, miniaturization of a wiring pattern on a substrate is progressing. Among them, there is a method for forming a fine wiring pattern using metal ultrafine particles. Already, a conductive performance close to that of a metal has been obtained by drawing a very fine wiring pattern using a paste in which ultrafine gold particles and ultrafine silver particles are dispersed, and subsequent firing. Since gold ultrafine particles are very expensive, practical application of silver ultrafine particles is being promoted.
しかし、ファインパターン回路などで配線間スペースが狭くなると銀超微粒子の場合、エレクトロマイグレーション問題が浮上してきた。銅超微粒子はエレクトロマイグレーションも少なく、金や銀より素材が安価で、汎用性の高い材料として、近年注目されている。 However, when the inter-wiring space is narrowed by a fine pattern circuit or the like, the electromigration problem has emerged in the case of ultrafine silver particles. Copper ultrafine particles have little electromigration, are cheaper than gold and silver, and have recently attracted attention as highly versatile materials.
しかしながら、銅超微粒子は酸化し易く、焼成温度も３００℃以上でないと焼成膜形成が難しく、樹脂の耐熱性の関係から樹脂基板への配線パターン形成ができなかった。そのため、低温で銅焼成膜を形成する方法として、種々の提案がなされている（例えば、特許文献１〜５）。 However, copper ultrafine particles are easily oxidized, and it is difficult to form a fired film unless the firing temperature is 300 ° C. or higher, and a wiring pattern cannot be formed on the resin substrate because of the heat resistance of the resin. Therefore, various proposals have been made as a method for forming a copper fired film at a low temperature (for example, Patent Documents 1 to 5).
特許文献１においては、塗膜をアルゴンやヘリウムなどのプラズマ励起雰囲気で還元処理する方法が記載されている。特許文献２においては、還元能を有するヒドロキシ基の有機化合物を分散したペーストを利用する方法が記載されている。特許文献３においては、パターン描画後、原子状水素により金属表面酸化膜を還元する方法が記載されている。特許文献４においては、配線パターン塗膜を、１．１気圧以上に加圧した水素ガス雰囲気で、１５０℃〜３００℃に加熱して焼成する方法が記載されている。特許文献５においては、接触水素化反応機能を具える金属触媒粒子などを添加したペーストで、水素ガス雰囲気で焼成膜を形成する方法が記載されている。 Patent Document 1 describes a method of reducing a coating film in a plasma-excited atmosphere such as argon or helium. Patent Document 2 describes a method using a paste in which an organic compound having a hydroxy group having a reducing ability is dispersed. Patent Document 3 describes a method of reducing a metal surface oxide film with atomic hydrogen after pattern drawing. Patent Document 4 describes a method in which a wiring pattern coating film is heated and fired at 150 ° C. to 300 ° C. in a hydrogen gas atmosphere pressurized to 1.1 atm or more. Patent Document 5 describes a method of forming a fired film in a hydrogen gas atmosphere with a paste to which metal catalyst particles having a catalytic hydrogenation reaction function are added.
しかし、これらの方法はプラズマ発生装置、原子状水素発生装置や加圧チャンバーなどが必要であり、生産性やコストに多くの問題を有している。また、ペースト組成においても制約があり、通常の水素含有窒素ガス雰囲気で連続的に緻密な銅焼成膜が形成できるペーストや形成方法が望まれていた。 However, these methods require a plasma generator, an atomic hydrogen generator, a pressurized chamber, and the like, and have many problems in productivity and cost. In addition, the paste composition is also limited, and a paste and a forming method that can form a dense copper fired film continuously in a normal hydrogen-containing nitrogen gas atmosphere have been desired.
以上に述べたように、銅超微粒子を分散した低温焼成用導電ペーストは、素材が安価で、微細な配線パターン形成が可能で、エレクトロマイグレーション問題も回避でき、電極やプリント配線基板の導体層への応用などが検討されている。 As described above, the conductive paste for low-temperature firing, in which ultrafine copper particles are dispersed, is inexpensive, can form fine wiring patterns, avoids electromigration problems, and can be applied to the conductive layers of electrodes and printed wiring boards. The application of is considered.
しかし、銅超微粒子は酸化しやすく、その表面酸化膜層を還元して、良好な導電性を有する焼結層を、連続的に安価に形成するのが困難であった。 However, the ultrafine copper particles are easily oxidized, and it has been difficult to reduce the surface oxide film layer and continuously form a sintered layer having good conductivity at a low cost.
本発明は、銅超微粒子を分散した塗膜の焼結過程を誠意研究した結果、完成したもので、通常の還元性雰囲気の焼成炉を用いて、３００℃以下の低温でも容易に緻密な低抵抗の焼成膜が得られるペースト、および銅導電膜の形成方法を提供するものである。 The present invention has been completed as a result of sincere research on the sintering process of the coating film in which the ultrafine copper particles are dispersed, and it can be easily obtained at a low temperature of 300 ° C. or less using a normal reducing atmosphere firing furnace. The present invention provides a paste from which a fired film of resistance is obtained, and a method for forming a copper conductive film.
本発明は、銅超微粒子をグリコールで湿潤被覆したペーストであって、銅超微粒子１００質量部に対して３〜３０質量部の脂肪酸を含有する低温焼成用導電ペーストである。 The present invention is a paste obtained by wet-coating copper ultrafine particles with glycol and containing 3 to 30 parts by mass of a fatty acid with respect to 100 parts by mass of copper ultrafine particles.
銅超微粒子は平均粒子径が１００ｎｍ以下であって、酸化膜が少なく、粗大凝集物のない超微粒子が好ましい。このような銅超微粒子は物理的気相法あるいは液相還元法で製造できる。 The copper ultrafine particles preferably have an average particle size of 100 nm or less, have a small oxide film, and are free from coarse aggregates. Such copper ultrafine particles can be produced by a physical vapor phase method or a liquid phase reduction method.
銅超微粒子を湿潤被覆するグリコールとは、多価アルコールの一種で１分子中に水酸基を２個もつアルコールで、エチレングリコール、プロピレングリコール、ジエチレングリコールなどがある。グリコールで銅超微粒子を湿潤被覆することで、銅表面の酸化膜生成を防止すると共に、焼成時の温度上昇過程で銅超微粒子の表面酸化膜を還元して焼結を促進する効果がある。グリコールはポリオールとも呼ばれ、金属酸化物を加熱還元する溶媒として良く知られている（例えば特開昭５９−１７３２０６号公報）。また、グリコールは印刷形成した配線パターン形状を焼成膜形成温度まで保持する効果もある。 Glycol that wet coats copper ultrafine particles is an alcohol having two hydroxyl groups in one molecule, such as ethylene glycol, propylene glycol, and diethylene glycol. By wet-coating the copper ultrafine particles with glycol, it is possible to prevent the formation of an oxide film on the copper surface and to promote the sintering by reducing the surface oxide film of the copper ultrafine particles during the temperature rise process during firing. Glycol is also called a polyol, and is well known as a solvent for reducing metal oxides by heating (for example, JP-A-59-173206). Glycol also has the effect of maintaining the printed wiring pattern shape up to the firing film formation temperature.
湿潤被覆するグリコールは銅超微粒子１００質量部に対して２０〜２００質量部添加する。２０質量部未満であると銅超微粒子を均一に被覆することができず、グリコールによる還元促進効果が得られなくなり均一な焼成膜ができなく、好ましくは５０質量部以上である。グリコール量は印刷方法に対応した銅超微粒子分散ペーストの粘度調整剤としてペーストに一定量以上加えれば良く、加える上限量についての制限はない。 The glycol for wet coating is added in an amount of 20 to 200 parts by mass with respect to 100 parts by mass of the copper ultrafine particles. If the amount is less than 20 parts by mass, the copper ultrafine particles cannot be uniformly coated, the reduction promoting effect by glycol cannot be obtained, and a uniform fired film cannot be formed, preferably 50 parts by mass or more. The amount of glycol should just be added to a paste more than a fixed quantity as a viscosity regulator of the copper ultrafine particle dispersion paste corresponding to a printing method, and there is no restriction | limiting about the upper limit amount to add.
しかし、グリコールを２００質量部超えて加えるとペーストが極低粘度となり、印刷パターンの形状保持が難しくなり、好ましくない。さらに、ペースト中のグリコール量でペースト中の銅超微粒子含有量を調整して、目的とする銅焼成膜厚を調整する事も可能である。 However, when the glycol is added in an amount exceeding 200 parts by mass, the paste has an extremely low viscosity, which makes it difficult to maintain the shape of the printed pattern, which is not preferable. Furthermore, it is possible to adjust the target copper fired film thickness by adjusting the content of ultrafine copper particles in the paste with the amount of glycol in the paste.
本発明のペーストの主溶媒であるグリコールに脂肪酸を加えるのは緻密な銅焼成膜を形成するために最も重要である。脂肪酸は飽和脂肪酸のカプリル酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、ベヘン酸が良い。グリコールだけで銅超微粒子を湿潤したペーストはグリコールの還元促進作用により２００℃の焼成温度でも還元され焼成膜が形成される。しかし、得られた焼成膜は銅超微粒子同士が焼結するときに生じる焼結収縮で膜に亀裂が多く発生し、凹凸の多いひび割れ膜となり、低抵抗焼成膜とならない。グリコールに脂肪酸を一定量以上加えることにより銅超微粒子が均一に焼結し、焼結収縮ワレの無い緻密な銅焼成膜が形成できる。また、脂肪酸添加は銅超微粒子を焼結過程で塗膜表面に並べる効果もあり、厚さの非常に薄い焼成膜でも緻密な低抵抗膜が得られる。 It is most important to add a fatty acid to glycol, which is the main solvent of the paste of the present invention, in order to form a dense copper fired film. The fatty acid is preferably a saturated fatty acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, or behenic acid. The paste in which copper ultrafine particles are wetted only with glycol is reduced even at a baking temperature of 200 ° C. due to the action of promoting the reduction of glycol to form a fired film. However, in the obtained fired film, many cracks are generated in the film due to sintering shrinkage that occurs when copper ultrafine particles are sintered together, and it becomes a cracked film with many irregularities and does not become a low resistance fired film. By adding a certain amount or more of fatty acid to glycol, the copper ultrafine particles are uniformly sintered, and a dense copper fired film without sintering shrinkage can be formed. The addition of fatty acid also has an effect of arranging copper ultrafine particles on the surface of the coating film during the sintering process, and a dense low-resistance film can be obtained even with a very thin fired film.
脂肪酸の効果は銅１００質量に対して３質量部から効果がある。３０質量部超えて加えるとペーストの流動特性を阻害し、焼成膜の平滑性や導電性も悪くなり好ましくない。好ましい添加量は銅超微粒子１００質量部に対して５〜２０質量部である。 The effect of fatty acid is effective from 3 parts by mass with respect to 100 parts by mass of copper. If added in excess of 30 parts by mass, the flow characteristics of the paste are hindered, and the smoothness and conductivity of the fired film are also deteriorated. A preferable addition amount is 5 to 20 parts by mass with respect to 100 parts by mass of the copper ultrafine particles.
本発明の銅超微粒子分散ペーストを用いて、樹脂基板上にスクリーン印刷などの印刷方法で配線パターンを形成し、還元性雰囲気焼成炉で３００℃以下の温度で焼成することで、緻密な低抵抗の銅焼成膜が形成できる。還元性雰囲気は汎用の窒素水素混合ガスが利用でき、水素含有量５〜５０％が好ましい。焼成温度は樹脂基板の耐熱性にもよるが、２００〜２５０℃で緻密な銅焼成膜が形成できる。表面改質した樹脂基板を用い、少量の有機ビヒクルをペーストに添加することで目的の塗膜物性にすることも可能である。この場合の有機ビヒクルとしてはエチルセルローズ、メチルセルローズ、アクリル樹脂、アルキッド樹脂、ブチラール樹脂、エポキシ樹脂、フェノール樹脂、ロジン、ワックスなどを挙げることができる。 By using the copper ultrafine particle dispersion paste of the present invention, a wiring pattern is formed on a resin substrate by a printing method such as screen printing, and firing is performed at a temperature of 300 ° C. or less in a reducing atmosphere firing furnace. A copper fired film can be formed. As the reducing atmosphere, a general-purpose nitrogen-hydrogen mixed gas can be used, and the hydrogen content is preferably 5 to 50%. Although the firing temperature depends on the heat resistance of the resin substrate, a dense copper fired film can be formed at 200 to 250 ° C. It is also possible to obtain the desired coating film properties by using a surface-modified resin substrate and adding a small amount of an organic vehicle to the paste. Examples of the organic vehicle in this case include ethyl cellulose, methyl cellulose, acrylic resin, alkyd resin, butyral resin, epoxy resin, phenol resin, rosin, and wax.
本発明の銅超微粒子分散ペーストは通常の還元性雰囲気の焼成炉で、緻密な銅焼成膜が低温で容易に得られ、樹脂基板への配線パターン形成が可能となり、高密度低温焼成型導電回路が連続的に安価に提供できるようになった。 The copper ultrafine particle-dispersed paste of the present invention allows a dense copper fired film to be easily obtained at a low temperature in a normal reducing atmosphere firing furnace, enables a wiring pattern to be formed on a resin substrate, and provides a high density and low temperature fired conductive circuit. Can be continuously provided at low cost.
以下、本発明の実施の形態である実施例を説明する。 Examples of the present invention will be described below.
（実施例１）
化学還元法で製造した平均粒子径１３ｎｍのメタノールに湿潤した銅超微粒子（福田金属箔粉工業(株)製）を利用する。メタノールを室温で蒸発した銅超微粒子１００質量部に対して、直ちに５０質量部のエチレングリコールと３質量部のミリスチン酸を加えペーストを作製した。このようにして作製した本発明の銅超微粒子分散ペーストの性能評価を以下の方法で行った。エポキシ樹脂基板上にスクリーン印刷し、水素０．５L/min＋窒素１L/minの混合ガス雰囲気の焼成炉にて、２００℃で９０分間加熱焼成し銅焼成膜を形成した。その結果、比抵抗が９×１０−５Ω・ｃｍの緻密で平滑な低抵抗の導電性焼成膜が得られた。
Example 1
Copper ultrafine particles (manufactured by Fukuda Metal Foil Powder Co., Ltd.) wetted with methanol having an average particle diameter of 13 nm produced by a chemical reduction method are used. To 100 parts by mass of copper ultrafine particles obtained by evaporating methanol at room temperature, 50 parts by mass of ethylene glycol and 3 parts by mass of myristic acid were immediately added to prepare a paste. The performance evaluation of the copper ultrafine particle-dispersed paste of the present invention thus produced was performed by the following method. Screen printing was carried out on the epoxy resin substrate, and the copper fired film was formed by heating and firing at 200 ° C. for 90 minutes in a firing furnace in a mixed gas atmosphere of hydrogen 0.5 L / min + nitrogen 1 L / min. As a result, a dense and smooth low-resistance conductive fired film having a specific resistance of 9 × 10 −5 Ω · cm was obtained.
（実施例２）
化学還元法で製造した平均粒子径１３ｎｍのメタノールに湿潤した銅超微粒子（福田金属箔粉工業(株)製）を利用する。メタノールを室温で蒸発した銅超微粒子１００質量部に対して、直ちに５５質量部のエチレングリコールと５質量部のミリスチン酸を加えペーストを作製した。このようにして作製した本発明の銅超微粒子分散ペーストの性能評価を以下の方法で行った。エポキシ樹脂基板上にスクリーン印刷し、水素０．５L/min＋窒素１L/minの混合ガス雰囲気の焼成炉にて、２００℃で９０分間加熱焼成し銅焼成膜を形成した。その結果、比抵抗が６×１０−５Ω・ｃｍの緻密で平滑な低抵抗の導電性焼成膜が得られた。
(Example 2)
Copper ultrafine particles (manufactured by Fukuda Metal Foil Powder Co., Ltd.) wetted with methanol having an average particle diameter of 13 nm produced by a chemical reduction method are used. To 100 parts by mass of copper ultrafine particles obtained by evaporating methanol at room temperature, 55 parts by mass of ethylene glycol and 5 parts by mass of myristic acid were immediately added to prepare a paste. The performance evaluation of the copper ultrafine particle-dispersed paste of the present invention thus produced was performed by the following method. Screen printing was carried out on the epoxy resin substrate, and the copper fired film was formed by heating and firing at 200 ° C. for 90 minutes in a firing furnace in a mixed gas atmosphere of hydrogen 0.5 L / min + nitrogen 1 L / min. As a result, a dense and smooth low-resistance conductive fired film having a specific resistance of 6 × 10 −5 Ω · cm was obtained.
（実施例３）
化学還元法で製造した平均粒子径１３ｎｍのメタノールに湿潤した銅超微粒子（福田金属箔粉工業(株)製）を利用する。メタノールを室温で蒸発した銅超微粒子１００質量部に対して、直ちに６０質量部のエチレングリコールと１０質量部のミリスチン酸を加えペーストを作製した。このようにして作製した本発明の銅超微粒子分散ペーストの性能評価を以下の方法で行った。エポキシ樹脂基板上にスクリーン印刷し、水素０．５L/min＋窒素１L/minの混合ガス雰囲気の焼成炉にて、２００℃で９０分間加熱焼成し銅焼成膜を形成した。その結果、比抵抗が５×１０−５Ω・ｃｍの緻密で平滑な低抵抗の導電性焼成膜が得られた。
(Example 3)
Copper ultrafine particles (manufactured by Fukuda Metal Foil Powder Co., Ltd.) wetted with methanol having an average particle diameter of 13 nm produced by a chemical reduction method are used. To 100 parts by mass of copper ultrafine particles obtained by evaporating methanol at room temperature, 60 parts by mass of ethylene glycol and 10 parts by mass of myristic acid were immediately added to prepare a paste. The performance evaluation of the copper ultrafine particle-dispersed paste of the present invention thus produced was performed by the following method. Screen printing was carried out on the epoxy resin substrate, and the copper fired film was formed by heating and firing at 200 ° C. for 90 minutes in a firing furnace in a mixed gas atmosphere of hydrogen 0.5 L / min + nitrogen 1 L / min. As a result, a dense and smooth low-resistance conductive fired film having a specific resistance of 5 × 10 −5 Ω · cm was obtained.
（実施例４）
化学還元法で製造した平均粒子径１３ｎｍのメタノールに湿潤した銅超微粒子（福田金属箔粉工業(株)製）を利用する。メタノールを室温で蒸発した銅超微粒子１００質量部に対して、直ちに７０質量部のエチレングリコールと１５質量部のミリスチン酸を加えペーストを作製した。このようにして作製した本発明の銅超微粒子分散ペーストの性能評価を以下の方法で行った。エポキシ樹脂基板上にスクリーン印刷し、水素０．５L/min＋窒素１L/minの混合ガス雰囲気の焼成炉にて、２００℃で９０分間加熱焼成し銅焼成膜を形成した。その結果、比抵抗が３×１０−５Ω・ｃｍの緻密で平滑な低抵抗の導電性焼成膜が得られた。
Example 4
Copper ultrafine particles (manufactured by Fukuda Metal Foil Powder Co., Ltd.) wetted with methanol having an average particle diameter of 13 nm produced by a chemical reduction method are used. To 100 parts by mass of copper ultrafine particles obtained by evaporating methanol at room temperature, 70 parts by mass of ethylene glycol and 15 parts by mass of myristic acid were immediately added to prepare a paste. The performance evaluation of the copper ultrafine particle-dispersed paste of the present invention thus produced was performed by the following method. Screen printing was carried out on the epoxy resin substrate, and the copper fired film was formed by heating and firing at 200 ° C. for 90 minutes in a firing furnace in a mixed gas atmosphere of hydrogen 0.5 L / min + nitrogen 1 L / min. As a result, a dense and smooth low-resistance conductive fired film having a specific resistance of 3 × 10 −5 Ω · cm was obtained.
（実施例５）
化学還元法で製造した平均粒子径１３ｎｍのメタノールに湿潤した銅超微粒子（福田金属箔粉工業(株)製）を利用する。メタノールを室温で蒸発した銅超微粒子１００質量部に対して、直ちに８０質量部のエチレングリコールと２０質量部のミリスチン酸を加えペーストを作製した。このようにして作製した本発明の銅超微粒子分散ペーストの性能評価を以下の方法で行った。エポキシ樹脂基板上にスクリーン印刷し、水素０．５L/min＋窒素１L/minの混合ガス雰囲気の焼成炉にて、２００℃で９０分間加熱焼成し銅焼成膜を形成した。その結果、比抵抗が４×１０−５Ω・ｃｍの緻密で平滑な低抵抗の導電性焼成膜が得られた。
(Example 5)
Copper ultrafine particles (manufactured by Fukuda Metal Foil Powder Co., Ltd.) wetted with methanol having an average particle diameter of 13 nm produced by a chemical reduction method are used. To 100 parts by mass of copper ultrafine particles obtained by evaporating methanol at room temperature, 80 parts by mass of ethylene glycol and 20 parts by mass of myristic acid were immediately added to prepare a paste. The performance evaluation of the copper ultrafine particle-dispersed paste of the present invention thus produced was performed by the following method. Screen printing was carried out on the epoxy resin substrate, and the copper fired film was formed by heating and firing at 200 ° C. for 90 minutes in a firing furnace in a mixed gas atmosphere of hydrogen 0.5 L / min + nitrogen 1 L / min. As a result, a dense and smooth low-resistance conductive fired film having a specific resistance of 4 × 10 −5 Ω · cm was obtained.
（実施例６）
化学還元法で製造した平均粒子径１３ｎｍのメタノールに湿潤した銅超微粒子（福田金属箔粉工業(株)製）を利用する。メタノールを室温で蒸発した銅超微粒子１００質量部に対して、直ちに９０質量部のエチレングリコールと３０質量部のミリスチン酸を加えペーストを作製した。このようにして作製した本発明の銅超微粒子分散ペーストの性能評価を以下の方法で行った。エポキシ樹脂基板上にスクリーン印刷し、水素０．５L/min＋窒素１L/minの混合ガス雰囲気の焼成炉にて、２００℃で９０分間加熱焼成し銅焼成膜を形成した。その結果、比抵抗が７×１０−５Ω・ｃｍの緻密で平滑な低抵抗の導電性焼成膜が得られた。
(Example 6)
Copper ultrafine particles (manufactured by Fukuda Metal Foil Powder Co., Ltd.) wetted with methanol having an average particle diameter of 13 nm produced by a chemical reduction method are used. To 100 parts by mass of copper ultrafine particles obtained by evaporating methanol at room temperature, 90 parts by mass of ethylene glycol and 30 parts by mass of myristic acid were immediately added to prepare a paste. The performance evaluation of the copper ultrafine particle-dispersed paste of the present invention thus produced was performed by the following method. Screen printing was carried out on the epoxy resin substrate, and the copper fired film was formed by heating and firing at 200 ° C. for 90 minutes in a firing furnace in a mixed gas atmosphere of hydrogen 0.5 L / min + nitrogen 1 L / min. As a result, a dense and smooth low-resistance conductive fired film having a specific resistance of 7 × 10 −5 Ω · cm was obtained.
（実施例７）
化学還元法で製造した平均粒子径１３ｎｍのメタノールに湿潤した銅超微粒子（福田金属箔粉工業(株)製）を利用する。メタノールを室温で蒸発した銅超微粒子１００質量部に対して、直ちに６０質量部のプロピレングリコールと３質量部のカプリン酸を加えペーストを作製した。このようにして作製した本発明の銅超微粒子分散ペーストの性能評価を以下の方法で行った。エポキシ樹脂基板上にスクリーン印刷し、水素０．５L/min＋窒素１L/minの混合ガス雰囲気の焼成炉にて、２００℃で９０分間加熱焼成し銅焼成膜を形成した。その結果、比抵抗が９×１０−５Ω・ｃｍの緻密で平滑な低抵抗の導電性焼成膜が得られた。
(Example 7)
Copper ultrafine particles (manufactured by Fukuda Metal Foil Powder Co., Ltd.) wetted with methanol having an average particle diameter of 13 nm produced by a chemical reduction method are used. To 100 parts by mass of copper ultrafine particles obtained by evaporating methanol at room temperature, 60 parts by mass of propylene glycol and 3 parts by mass of capric acid were immediately added to prepare a paste. The performance evaluation of the copper ultrafine particle-dispersed paste of the present invention thus produced was performed by the following method. Screen printing was carried out on the epoxy resin substrate, and the copper fired film was formed by heating and firing at 200 ° C. for 90 minutes in a firing furnace in a mixed gas atmosphere of hydrogen 0.5 L / min + nitrogen 1 L / min. As a result, a dense and smooth low-resistance conductive fired film having a specific resistance of 9 × 10 −5 Ω · cm was obtained.
（実施例８）
化学還元法で製造した平均粒子径１３ｎｍのメタノールに湿潤した銅超微粒子（福田金属箔粉工業(株)製）を利用する。メタノールを室温で蒸発した銅超微粒子１００質量部に対して、直ちに６０質量部のプロピレングリコールと５質量部のカプリン酸を加えペーストを作製した。このようにして作製した本発明の銅超微粒子分散ペーストの性能評価を以下の方法で行った。エポキシ樹脂基板上にスクリーン印刷し、水素０．５L/min＋窒素１L/minの混合ガス雰囲気中焼成炉にて、２００℃で９０分間加熱焼成し銅焼成膜を形成した。その結果、比抵抗が７×１０−５Ω・ｃｍの緻密で平滑な低抵抗の導電性焼成膜が得られた。
(Example 8)
Copper ultrafine particles (manufactured by Fukuda Metal Foil Powder Co., Ltd.) wetted with methanol having an average particle diameter of 13 nm produced by a chemical reduction method are used. To 100 parts by mass of copper ultrafine particles obtained by evaporating methanol at room temperature, 60 parts by mass of propylene glycol and 5 parts by mass of capric acid were immediately added to prepare a paste. The performance evaluation of the copper ultrafine particle-dispersed paste of the present invention thus produced was performed by the following method. Screen printing was performed on an epoxy resin substrate, and the copper fired film was formed by heating and firing at 200 ° C. for 90 minutes in a firing furnace in a mixed gas atmosphere of hydrogen 0.5 L / min + nitrogen 1 L / min. As a result, a dense and smooth low-resistance conductive fired film having a specific resistance of 7 × 10 −5 Ω · cm was obtained.
（実施例９）
化学還元法で製造した平均粒子径１３ｎｍのメタノールに湿潤した銅超微粒子（福田金属箔粉工業(株)製）を利用する。メタノールを室温で蒸発した銅超微粒子１００質量部に対して、直ちに６５質量部のプロピレングリコールと１０質量部のカプリン酸を加えペーストを作製した。このようにして作製した本発明の銅超微粒子分散ペーストの性能評価を以下の方法で行った。エポキシ樹脂基板上にスクリーン印刷し、水素０．５L/min＋窒素１L/minの混合ガス雰囲気の焼成炉にて、２００℃で９０分間加熱焼成し銅焼成膜を形成した。その結果、比抵抗が５×１０−５Ω・ｃｍの緻密で平滑な低抵抗の導電性焼成膜が得られた。
Example 9
Copper ultrafine particles (manufactured by Fukuda Metal Foil Powder Co., Ltd.) wetted with methanol having an average particle diameter of 13 nm produced by a chemical reduction method are used. To 100 parts by mass of copper ultrafine particles obtained by evaporating methanol at room temperature, 65 parts by mass of propylene glycol and 10 parts by mass of capric acid were immediately added to prepare a paste. The performance evaluation of the copper ultrafine particle-dispersed paste of the present invention thus produced was performed by the following method. Screen printing was carried out on the epoxy resin substrate, and the copper fired film was formed by heating and firing at 200 ° C. for 90 minutes in a firing furnace in a mixed gas atmosphere of hydrogen 0.5 L / min + nitrogen 1 L / min. As a result, a dense and smooth low-resistance conductive fired film having a specific resistance of 5 × 10 −5 Ω · cm was obtained.
（実施例１０）
化学還元法で製造した平均粒子径１３ｎｍのメタノールに湿潤した銅超微粒子（福田金属箔粉工業(株)製）を利用する。メタノールを室温で蒸発した銅超微粒子１００質量部に対して、直ちに７０質量部のプロピレングリコールと１５質量部のカプリン酸を加えペーストを作製した。このようにして作製した本発明の銅超微粒子分散ペーストの性能評価を以下の方法で行った。エポキシ樹脂基板上にスクリーン印刷し、水素０．５L/min＋窒素１L/minの混合ガス雰囲気の焼成炉にて、２００℃で９０分間加熱焼成し銅焼成膜を形成した。その結果、比抵抗が３×１０−５Ω・ｃｍの緻密で平滑な低抵抗の導電性焼成膜が得られた。
(Example 10)
Copper ultrafine particles (manufactured by Fukuda Metal Foil Powder Co., Ltd.) wetted with methanol having an average particle diameter of 13 nm produced by a chemical reduction method are used. To 100 parts by mass of copper ultrafine particles obtained by evaporating methanol at room temperature, 70 parts by mass of propylene glycol and 15 parts by mass of capric acid were immediately added to prepare a paste. The performance evaluation of the copper ultrafine particle-dispersed paste of the present invention thus produced was performed by the following method. Screen printing was carried out on the epoxy resin substrate, and the copper fired film was formed by heating and firing at 200 ° C. for 90 minutes in a firing furnace in a mixed gas atmosphere of hydrogen 0.5 L / min + nitrogen 1 L / min. As a result, a dense and smooth low-resistance conductive fired film having a specific resistance of 3 × 10 −5 Ω · cm was obtained.
（実施例１１）
化学還元法で製造した平均粒子径１３ｎｍのメタノールに湿潤した銅超微粒子（福田金属箔粉工業(株)製）を利用する。メタノールを室温で蒸発した銅超微粒子１００質量部に対して、直ちに８０質量部のプロピレングリコールと２０質量部のカプリン酸を加えペーストを作製した。このようにして作製した本発明の銅超微粒子分散ペーストの性能評価を以下の方法で行った。エポキシ樹脂基板上にスクリーン印刷し、水素０．５L/min＋窒素１L/minの混合ガス雰囲気の焼成炉にて、２００℃で９０分間加熱焼成し銅焼成膜を形成した。その結果、比抵抗が４×１０−５Ω・ｃｍの緻密で平滑な低抵抗の導電性焼成膜が得られた。
(Example 11)
Copper ultrafine particles (manufactured by Fukuda Metal Foil Powder Co., Ltd.) wetted with methanol having an average particle diameter of 13 nm produced by a chemical reduction method are used. To 100 parts by mass of copper ultrafine particles obtained by evaporating methanol at room temperature, 80 parts by mass of propylene glycol and 20 parts by mass of capric acid were immediately added to prepare a paste. The performance evaluation of the copper ultrafine particle-dispersed paste of the present invention thus produced was performed by the following method. Screen printing was carried out on the epoxy resin substrate, and the copper fired film was formed by heating and firing at 200 ° C. for 90 minutes in a firing furnace in a mixed gas atmosphere of hydrogen 0.5 L / min + nitrogen 1 L / min. As a result, a dense and smooth low-resistance conductive fired film having a specific resistance of 4 × 10 −5 Ω · cm was obtained.
（実施例１２）
化学還元法で製造した平均粒子径１３ｎｍのメタノールに湿潤した銅超微粒子（福田金属箔粉工業(株)製）を利用する。メタノールを室温で蒸発した銅超微粒子１００質量部に対して、直ちに９０質量部のプロピレングリコールと３０質量部のカプリン酸を加えペーストを作製した。このようにして作製した本発明の銅超微粒子分散ペーストの性能評価を以下の方法で行った。エポキシ樹脂基板上にスクリーン印刷し、水素０．５L/min＋窒素１L/minの混合ガス雰囲気の焼成炉にて、２００℃で９０分間加熱焼成し銅焼成膜を形成した。その結果、比抵抗が８×１０−５Ω・ｃｍの緻密で平滑な低抵抗の導電性焼成膜が得られた。
(Example 12)
Copper ultrafine particles (manufactured by Fukuda Metal Foil Powder Co., Ltd.) wetted with methanol having an average particle diameter of 13 nm produced by a chemical reduction method are used. To 100 parts by mass of copper ultrafine particles obtained by evaporating methanol at room temperature, 90 parts by mass of propylene glycol and 30 parts by mass of capric acid were immediately added to prepare a paste. The performance evaluation of the copper ultrafine particle-dispersed paste of the present invention thus produced was performed by the following method. Screen printing was carried out on the epoxy resin substrate, and the copper fired film was formed by heating and firing at 200 ° C. for 90 minutes in a firing furnace in a mixed gas atmosphere of hydrogen 0.5 L / min + nitrogen 1 L / min. As a result, a dense and smooth low-resistance conductive fired film having a specific resistance of 8 × 10 −5 Ω · cm was obtained.
（実施例１３）
化学還元法で製造した平均粒子径１３ｎｍのメタノールに湿潤した銅超微粒子（福田金属箔粉工業(株)製）を利用する。メタノールを室温で蒸発した銅超微粒子１００質量部に対して、直ちに４０質量部のジエチレングリコールと１５質量部のカプリル酸を加えペーストを作製した。このようにして作製した本発明の銅超微粒子分散ペーストの性能評価を以下の方法で行った。エポキシ樹脂基板上にスクリーン印刷し、水素０．２L/min＋窒素１L/minの混合ガス雰囲気の焼成炉にて、２２０℃で６０分間加熱焼成し銅焼成膜を形成した。その結果、比抵抗が４×１０−５Ω・ｃｍの緻密で平滑な低抵抗の導電性焼成膜が得られた。
(Example 13)
Copper ultrafine particles (manufactured by Fukuda Metal Foil Powder Co., Ltd.) wetted with methanol having an average particle diameter of 13 nm produced by a chemical reduction method are used. To 100 parts by mass of copper ultrafine particles obtained by evaporating methanol at room temperature, 40 parts by mass of diethylene glycol and 15 parts by mass of caprylic acid were immediately added to prepare a paste. The performance evaluation of the copper ultrafine particle-dispersed paste of the present invention thus produced was performed by the following method. Screen printing was performed on an epoxy resin substrate, and a copper fired film was formed by heating and firing at 220 ° C. for 60 minutes in a firing furnace in a mixed gas atmosphere of hydrogen 0.2 L / min + nitrogen 1 L / min. As a result, a dense and smooth low-resistance conductive fired film having a specific resistance of 4 × 10 −5 Ω · cm was obtained.
（実施例１４）
化学還元法で製造した平均粒子径１３ｎｍのメタノールに湿潤した銅超微粒子（福田金属箔粉工業(株)製）を利用する。メタノールを室温で蒸発した銅超微粒子１００質量部に対して、直ちに６０質量部のジエチレングリコールと１５質量部のカプリン酸を加えペーストを作製した。このようにして作製した本発明の銅超微粒子分散ペーストの性能評価を以下の方法で行った。エポキシ樹脂基板上にスクリーン印刷し、水素０．２L/min＋窒素１L/minの混合ガス雰囲気の焼成炉にて、２２０℃で６０分間加熱焼成し銅焼成膜を形成した。その結果、比抵抗が３×１０−５Ω・ｃｍの緻密で平滑な低抵抗の導電性焼成膜が得られた。
(Example 14)
Copper ultrafine particles (manufactured by Fukuda Metal Foil Powder Co., Ltd.) wetted with methanol having an average particle diameter of 13 nm produced by a chemical reduction method are used. To 100 parts by mass of copper ultrafine particles obtained by evaporating methanol at room temperature, 60 parts by mass of diethylene glycol and 15 parts by mass of capric acid were immediately added to prepare a paste. The performance evaluation of the copper ultrafine particle-dispersed paste of the present invention thus produced was performed by the following method. Screen printing was performed on an epoxy resin substrate, and a copper fired film was formed by heating and firing at 220 ° C. for 60 minutes in a firing furnace in a mixed gas atmosphere of hydrogen 0.2 L / min + nitrogen 1 L / min. As a result, a dense and smooth low-resistance conductive fired film having a specific resistance of 3 × 10 −5 Ω · cm was obtained.
（実施例１５）
化学還元法で製造した平均粒子径１３ｎｍのメタノールに湿潤した銅超微粒子（福田金属箔粉工業(株)製）を利用する。メタノールを室温で蒸発した銅超微粒子１００質量部に対して、直ちに７０質量部のジエチレングリコールと１５質量部のラウリン酸を加えペーストを作製した。このようにして作製した本発明の銅超微粒子分散ペーストの性能評価を以下の方法で行った。エポキシ樹脂基板上にスクリーン印刷し、水素０．２L/min＋窒素１L/minの混合ガス雰囲気の焼成炉にて、２２０℃で６０分間加熱焼成し銅焼成膜を形成した。その結果、比抵抗が３×１０−５Ω・ｃｍの緻密で平滑な低抵抗の導電性焼成膜が得られた。
(Example 15)
Copper ultrafine particles (manufactured by Fukuda Metal Foil Powder Co., Ltd.) wetted with methanol having an average particle diameter of 13 nm produced by a chemical reduction method are used. A paste was prepared by immediately adding 70 parts by mass of diethylene glycol and 15 parts by mass of lauric acid to 100 parts by mass of copper ultrafine particles obtained by evaporating methanol at room temperature. The performance evaluation of the copper ultrafine particle-dispersed paste of the present invention thus produced was performed by the following method. Screen printing was performed on an epoxy resin substrate, and a copper fired film was formed by heating and firing at 220 ° C. for 60 minutes in a firing furnace in a mixed gas atmosphere of hydrogen 0.2 L / min + nitrogen 1 L / min. As a result, a dense and smooth low-resistance conductive fired film having a specific resistance of 3 × 10 −5 Ω · cm was obtained.
（実施例１６）
化学還元法で製造した平均粒子径１３ｎｍのメタノールに湿潤した銅超微粒子（福田金属箔粉工業(株)製）を利用する。メタノールを室温で蒸発した銅超微粒子１００質量部に対して、直ちに７０質量部のジエチレングリコールと１５質量部のミリスチン酸を加えペーストを作製した。このようにして作製した本発明の銅超微粒子分散ペーストの性能評価を以下の方法で行った。エポキシ樹脂基板上にスクリーン印刷し、水素０．２L/min＋窒素１L/minの混合ガス雰囲気の焼成炉にて、２２０℃で６０分間加熱焼成し銅焼成膜を形成した。その結果、比抵抗が３×１０−５Ω・ｃｍの緻密で平滑な低抵抗の導電性焼成膜が得られた。
(Example 16)
Copper ultrafine particles (manufactured by Fukuda Metal Foil Powder Co., Ltd.) wetted with methanol having an average particle diameter of 13 nm produced by a chemical reduction method are used. To 100 parts by mass of copper ultrafine particles obtained by evaporating methanol at room temperature, 70 parts by mass of diethylene glycol and 15 parts by mass of myristic acid were immediately added to prepare a paste. The performance evaluation of the copper ultrafine particle-dispersed paste of the present invention thus produced was performed by the following method. Screen printing was performed on an epoxy resin substrate, and a copper fired film was formed by heating and firing at 220 ° C. for 60 minutes in a firing furnace in a mixed gas atmosphere of hydrogen 0.2 L / min + nitrogen 1 L / min. As a result, a dense and smooth low-resistance conductive fired film having a specific resistance of 3 × 10 −5 Ω · cm was obtained.
（実施例１７）
化学還元法で製造した平均粒子径１３ｎｍのメタノールに湿潤した銅超微粒子（福田金属箔粉工業(株)製）を利用する。メタノールを室温で蒸発した銅超微粒子１００質量部に対して、直ちに８０質量部のジエチレングリコールと１５質量部のパルミチン酸を加えペーストを作製した。このようにして作製した本発明の銅超微粒子分散ペーストの性能評価を以下の方法で行った。エポキシ樹脂基板上にスクリーン印刷し、水素０．２L/min＋窒素１L/minの混合ガス雰囲気の焼成炉にて、２２０℃で６０分間加熱焼成し銅焼成膜を形成した。その結果、比抵抗が３×１０−５Ω・ｃｍの緻密で平滑な低抵抗の導電性焼成膜が得られた。
(Example 17)
Copper ultrafine particles (manufactured by Fukuda Metal Foil Powder Co., Ltd.) wetted with methanol having an average particle diameter of 13 nm produced by a chemical reduction method are used. To 100 parts by mass of copper ultrafine particles obtained by evaporating methanol at room temperature, 80 parts by mass of diethylene glycol and 15 parts by mass of palmitic acid were immediately added to prepare a paste. The performance evaluation of the copper ultrafine particle-dispersed paste of the present invention thus produced was performed by the following method. Screen printing was performed on an epoxy resin substrate, and a copper fired film was formed by heating and firing at 220 ° C. for 60 minutes in a firing furnace in a mixed gas atmosphere of hydrogen 0.2 L / min + nitrogen 1 L / min. As a result, a dense and smooth low-resistance conductive fired film having a specific resistance of 3 × 10 −5 Ω · cm was obtained.
（実施例１８）
化学還元法で製造した平均粒子径１３ｎｍのメタノールに湿潤した銅超微粒子（福田金属箔粉工業(株)製）を利用する。メタノールを室温で蒸発した銅超微粒子１００質量部に対して、直ちに８０質量部のジエチレングリコールと１５質量部のステアリン酸を加えペーストを作製した。このようにして作製した本発明の銅超微粒子分散ペーストの性能評価を以下の方法で行った。エポキシ樹脂基板上にスクリーン印刷し、水素０．２L/min＋窒素１L/minの混合ガス雰囲気の焼成炉にて、２２０℃で６０分間加熱焼成し銅焼成膜を形成した。その結果、比抵抗が５×１０−５Ω・ｃｍの緻密で平滑な低抵抗の導電性焼成膜が得られた。
(Example 18)
Copper ultrafine particles (manufactured by Fukuda Metal Foil Powder Co., Ltd.) wetted with methanol having an average particle diameter of 13 nm produced by a chemical reduction method are used. To 100 parts by mass of copper ultrafine particles obtained by evaporating methanol at room temperature, 80 parts by mass of diethylene glycol and 15 parts by mass of stearic acid were immediately added to prepare a paste. The performance evaluation of the copper ultrafine particle-dispersed paste of the present invention thus produced was performed by the following method. Screen printing was performed on an epoxy resin substrate, and a copper fired film was formed by heating and firing at 220 ° C. for 60 minutes in a firing furnace in a mixed gas atmosphere of hydrogen 0.2 L / min + nitrogen 1 L / min. As a result, a dense and smooth low-resistance conductive fired film having a specific resistance of 5 × 10 −5 Ω · cm was obtained.
（実施例１９）
化学還元法で製造した平均粒子径１３ｎｍのメタノールに湿潤した銅超微粒子（福田金属箔粉工業(株)製）を利用する。メタノールを室温で蒸発した銅超微粒子１００質量部に対して、直ちに８０質量部のジエチレングリコールと１５質量部のべヘン酸を加えペーストを作製した。このようにして作製した本発明の銅超微粒子分散ペーストの性能評価を以下の方法で行った。エポキシ樹脂基板上にスクリーン印刷し、水素０．２L/min＋窒素１L/minの混合ガス雰囲気の焼成炉にて、２２０℃で６０分間加熱焼成し銅焼成膜を形成した。その結果、比抵抗が５×１０−５Ω・ｃｍの緻密で平滑な低抵抗の導電性焼成膜が得られた。
(Example 19)
Copper ultrafine particles (manufactured by Fukuda Metal Foil Powder Co., Ltd.) wetted with methanol having an average particle diameter of 13 nm produced by a chemical reduction method are used. To 100 parts by mass of copper ultrafine particles obtained by evaporating methanol at room temperature, 80 parts by mass of diethylene glycol and 15 parts by mass of behenic acid were immediately added to prepare a paste. The performance evaluation of the copper ultrafine particle-dispersed paste of the present invention thus produced was performed by the following method. Screen printing was performed on an epoxy resin substrate, and a copper fired film was formed by heating and firing at 220 ° C. for 60 minutes in a firing furnace in a mixed gas atmosphere of hydrogen 0.2 L / min + nitrogen 1 L / min. As a result, a dense and smooth low-resistance conductive fired film having a specific resistance of 5 × 10 −5 Ω · cm was obtained.
（実施例２０）
化学還元法で製造した平均粒子径１３ｎｍのメタノールに湿潤した銅超微粒子（福田金属箔粉工業(株)製）を利用する。メタノールを室温で蒸発した銅超微粒子１００質量部に対して、直ちに４０質量部のエチレングリコールと３０質量部のプロピレングリコールを加え混練加工した。その後、１０質量部のミリスチン酸と５重量部のカプリン酸を加えペーストを作製した。このようにして作製した本発明の銅超微粒子分散ペーストの性能評価を以下の方法で行った。エポキシ樹脂基板上にスクリーン印刷し、水素０．５L/min＋窒素１L/minの混合ガス雰囲気の焼成炉にて、２００℃で９０分間加熱焼成し銅焼成膜を形成した。その結果、比抵抗が３×１０−５Ω・ｃｍの緻密で平滑な低抵抗の導電性焼成膜が得られた。
(Example 20)
Copper ultrafine particles (manufactured by Fukuda Metal Foil Powder Co., Ltd.) wetted with methanol having an average particle diameter of 13 nm produced by a chemical reduction method are used. To 100 parts by mass of copper ultrafine particles obtained by evaporating methanol at room temperature, 40 parts by mass of ethylene glycol and 30 parts by mass of propylene glycol were immediately added and kneaded. Thereafter, 10 parts by mass of myristic acid and 5 parts by weight of capric acid were added to prepare a paste. The performance evaluation of the copper ultrafine particle-dispersed paste of the present invention thus produced was performed by the following method. Screen printing was carried out on the epoxy resin substrate, and the copper fired film was formed by heating and firing at 200 ° C. for 90 minutes in a firing furnace in a mixed gas atmosphere of hydrogen 0.5 L / min + nitrogen 1 L / min. As a result, a dense and smooth low-resistance conductive fired film having a specific resistance of 3 × 10 −5 Ω · cm was obtained.
（実施例２１）
化学還元法で製造した平均粒子径５４ｎｍのメタノールに湿潤した銅超微粒子（福田金属箔粉工業(株)製）を利用する。メタノールを室温で蒸発した銅超微粒子１００質量部に対して、直ちに５０質量部のエチレングリコールと１５質量部のミリスチン酸を加えペーストを作製した。このようにして作製した本発明の銅超微粒子分散ペーストの性能評価を以下の方法で行った。エポキシ樹脂基板上にスクリーン印刷し、水素０．５L/min＋窒素１L/minの混合ガス雰囲気の焼成炉にて、２５０℃で６０分間加熱焼成し銅焼成膜を形成した。その結果、比抵抗が３×１０−５Ω・ｃｍの緻密で平滑な低抵抗の導電性焼成膜が得られた。
(Example 21)
Copper ultrafine particles (manufactured by Fukuda Metal Foil Powder Co., Ltd.) wetted with methanol having an average particle diameter of 54 nm manufactured by a chemical reduction method are used. To 100 parts by mass of copper ultrafine particles obtained by evaporating methanol at room temperature, 50 parts by mass of ethylene glycol and 15 parts by mass of myristic acid were immediately added to prepare a paste. The performance evaluation of the copper ultrafine particle-dispersed paste of the present invention thus produced was performed by the following method. Screen printing was performed on an epoxy resin substrate, and a copper fired film was formed by heating and firing at 250 ° C. for 60 minutes in a firing furnace in a mixed gas atmosphere of hydrogen 0.5 L / min + nitrogen 1 L / min. As a result, a dense and smooth low-resistance conductive fired film having a specific resistance of 3 × 10 −5 Ω · cm was obtained.
（実施例２２）
化学還元法で製造した平均粒子径１３ｎｍのメタノールに湿潤した銅超微粒子（福田金属箔粉工業(株)製）を利用する。メタノールを室温で蒸発した銅超微粒子１００質量部に対して、直ちに２００質量部のプロピレングリコールと１５質量部のカプリン酸を加え低粘度ペーストを作製した。このようにして作製した本発明の銅超微粒子分散ペーストの性能評価を以下の方法で行った。エポキシ樹脂基板上にスピンコート印刷し、水素０．５L/min＋窒素１L/minの混合ガス雰囲気の焼成炉にて、２００℃で９０分間加熱焼成し銅焼成膜を形成した。その結果、比抵抗が６×１０−５Ω・ｃｍの緻密で平滑な極薄導電性焼成膜が得られた。
(Example 22)
Copper ultrafine particles (manufactured by Fukuda Metal Foil Powder Co., Ltd.) wetted with methanol having an average particle diameter of 13 nm produced by a chemical reduction method are used. 200 parts by mass of propylene glycol and 15 parts by mass of capric acid were immediately added to 100 parts by mass of copper ultrafine particles obtained by evaporating methanol at room temperature to prepare a low-viscosity paste. The performance evaluation of the copper ultrafine particle-dispersed paste of the present invention thus produced was performed by the following method. It spin-printed on the epoxy resin board | substrate, and it heat-baked at 200 degreeC for 90 minute (s) in the baking furnace of the mixed gas atmosphere of hydrogen 0.5L / min + nitrogen 1L / min, and formed the copper baking film | membrane. As a result, a dense and smooth ultrathin conductive fired film having a specific resistance of 6 × 10 −5 Ω · cm was obtained.
（比較例１）
実施例１と同じ方法で作製した銅超微粒子１００質量部に対して、５０質量部のエチレングリコールを加えペーストを作製し、実施例１と同じ焼成条件にて、２００℃で焼成膜を形成した。その結果、銅超微粒子同士が焼結により粗大粒子化し、焼成膜には多くの亀裂が認められ、比抵抗も５×１０−４Ω・ｃｍと悪いものであった。
(Comparative Example 1)
A paste was prepared by adding 50 parts by mass of ethylene glycol to 100 parts by mass of copper ultrafine particles produced by the same method as in Example 1, and a fired film was formed at 200 ° C. under the same firing conditions as in Example 1. . As a result, the copper ultrafine particles became coarse particles by sintering, and many cracks were observed in the fired film, and the specific resistance was also bad at 5 × 10 −4 Ω · cm.
（比較例２）
実施例７と同じ方法で作製した銅超微粒子１００質量部に対して、６０質量部のプロピレングリコールを加えペーストを作製し、実施例７と同じ焼成条件にて、２００℃で焼成膜を形成した。その結果、銅超微粒子同士が焼結により粗大粒子化し、焼成膜には多くの亀裂が認められ、比抵抗も６×１０−４Ω・ｃｍと悪いものであった。
(Comparative Example 2)
60 parts by mass of propylene glycol was added to 100 parts by mass of copper ultrafine particles produced by the same method as in Example 7, and a fired film was formed at 200 ° C. under the same firing conditions as in Example 7. . As a result, copper ultrafine particles became coarse particles by sintering, and many cracks were observed in the fired film, and the specific resistance was also as bad as 6 × 10 −4 Ω · cm.
（比較例３）
実施例１３と同じ方法で作製した銅超微粒子１００質量部に対して、５０質量部のジエチレングリコールを加えペーストを作製し、実施例１３と同じ焼成条件にて、２２０℃で焼成膜を形成した。その結果、焼成温度が高いので銅超微粒子同士の焼結が進み、焼成膜には多くの亀裂が認められ、しかも亀裂幅も２００℃より大きく、比抵抗も７×１０−４Ω・ｃｍと悪いものであった。
(Comparative Example 3)
A paste was prepared by adding 50 parts by mass of diethylene glycol to 100 parts by mass of copper ultrafine particles produced by the same method as in Example 13, and a fired film was formed at 220 ° C. under the same firing conditions as in Example 13. As a result, since the firing temperature is high, the sintering of the copper ultrafine particles proceeds, and many cracks are observed in the fired film, the crack width is larger than 200 ° C., and the specific resistance is 7 × 10 −4 Ω · cm. It was bad.
（比較例４）
化学還元法で製造した平均粒子径０．５μｍのメタノールに湿潤した銅微粒子（福田金属箔粉工業(株)製）を利用する。メタノールを室温で蒸発した銅微粒子１００質量部に対して、直ちに２５質量部のエチレングリコールと１５質量部のミリスチン酸を加えペーストを作製した。このようにして作製した銅微粒子分散ペーストを、エポキシ樹脂基板上にスクリーン印刷し、水素０．５L/min＋窒素１L/minの混合ガス雰囲気の焼成炉にて、３００℃で６０分間加熱焼成した結果、導電性を有する焼成膜が得られなかった。
(Comparative Example 4)
Copper fine particles (manufactured by Fukuda Metal Foil Powder Co., Ltd.) wetted in methanol with an average particle size of 0.5 μm produced by a chemical reduction method are used. 25 parts by mass of ethylene glycol and 15 parts by mass of myristic acid were immediately added to 100 parts by mass of copper fine particles obtained by evaporating methanol at room temperature to prepare a paste. The copper fine particle dispersion paste thus produced was screen printed on an epoxy resin substrate, and baked at 300 ° C. for 60 minutes in a baking furnace in a mixed gas atmosphere of hydrogen 0.5 L / min + nitrogen 1 L / min. A conductive fired film could not be obtained.
（比較例５）
実施例１と同じ方法で作製した銅超微粒子１００質量部に対して、５０質量部のエチレングリコールと１質量部のミリスチン酸を加えペーストを作製し、実施例１と同じ焼成条件にて、２００℃で焼成膜を形成した。その結果、銅超微粒子同士が焼結により粗大粒子化し、焼成膜には多くの亀裂が認められ、比抵抗も５×１０−４Ω・ｃｍと悪いものであった。
(Comparative Example 5)
A paste was prepared by adding 50 parts by mass of ethylene glycol and 1 part by mass of myristic acid to 100 parts by mass of the ultrafine copper particles produced by the same method as in Example 1, and under the same firing conditions as in Example 1, 200 A fired film was formed at ° C. As a result, the copper ultrafine particles became coarse particles by sintering, and many cracks were observed in the fired film, and the specific resistance was also bad at 5 × 10 −4 Ω · cm.
（比較例６）
実施例２２と同じ方法で作製した銅超微粒子１００質量部に対して、３００質量部のプロピレングリコールと１５質量部のカプリン酸を加え極低粘度ペーストを作製した。このようにして作製した銅超微粒子分散ペーストをエポキシ樹脂基板上にスピンコート印刷した結果、銅含有量が極めて少ない薄膜となり、水素０．５L/min＋窒素１L/minの混合ガス雰囲気の焼成炉にて、２００℃で９０分間加熱焼成しても、比抵抗が測定できる銅焼成膜が形成できなかった。
(Comparative Example 6)
To 100 parts by mass of copper ultrafine particles produced by the same method as in Example 22, 300 parts by mass of propylene glycol and 15 parts by mass of capric acid were added to produce an extremely low viscosity paste. As a result of spin coating printing the copper ultrafine particle dispersion paste thus prepared on an epoxy resin substrate, it becomes a thin film with extremely low copper content, and is applied to a firing furnace in a mixed gas atmosphere of hydrogen 0.5 L / min + nitrogen 1 L / min. Thus, a copper fired film capable of measuring the specific resistance could not be formed even when heated and fired at 200 ° C. for 90 minutes.
（比較例７）
実施例６と同じ方法で作製した銅超微粒子１００質量部に対して、１００質量部のエチレングリコールと４０質量部のミリスチン酸を加えペーストを作製した。このようにして作製した銅超微粒子分散ペーストは粘度が安定せず粘度が増加し、エチレングリコール量を調整しても安定した印刷膜を得ることが難しかった。また、実施例６と同じ焼成条件にて、焼成膜を形成した結果、凹凸の多い焼成膜となり、比抵抗も５×１０−４Ω・ｃｍと悪いものであった。
(Comparative Example 7)
A paste was prepared by adding 100 parts by mass of ethylene glycol and 40 parts by mass of myristic acid to 100 parts by mass of the ultrafine copper particles produced by the same method as in Example 6. The copper ultrafine particle-dispersed paste produced in this way has a viscosity that is not stable and increases in viscosity, and even if the amount of ethylene glycol is adjusted, it is difficult to obtain a stable printed film. Moreover, as a result of forming a fired film under the same firing conditions as in Example 6, the fired film had many irregularities, and the specific resistance was poor at 5 × 10 −4 Ω · cm.
本発明の銅超微粒子分散ペーストの焼成膜が緻密で平滑な状態であることを、レーザ顕微鏡で撮影した焼成膜外観写真（三次元観察）として図１に示す。図２の従来の脂肪酸を加えない銅超微粒子分散ペーストの焼成膜と比較して、本発明による焼成膜は均一で平滑であることが判る。従来のペーストの焼成膜は大きな割れが膜表面にある。 FIG. 1 shows an appearance photograph (three-dimensional observation) of the fired film taken with a laser microscope that the fired film of the copper ultrafine particle-dispersed paste of the present invention is in a dense and smooth state. It can be seen that the fired film according to the present invention is uniform and smooth as compared with the fired film of the copper ultrafine particle dispersed paste of FIG. The conventional paste fired film has large cracks on the film surface.
本発明の銅超微粒子分散ペーストは緻密な焼成膜が容易に得られ、しかも従来の焼成炉で連続生産が可能となった。本発明を応用した微細配線パターンは銅箔をエッチングして形成される厚膜回路より精細な回路導体の形成ができ、製造プロセスの簡素化によるコストダウンと共に、印刷技術を用いた多層厚膜回路形成も可能になってきた。 The copper ultrafine particle-dispersed paste of the present invention can easily obtain a dense fired film and can be continuously produced in a conventional firing furnace. A fine wiring pattern to which the present invention is applied can form a finer circuit conductor than a thick film circuit formed by etching a copper foil, and a multilayer thick film circuit using a printing technique as well as a cost reduction by simplifying a manufacturing process. Formation has also become possible.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2016052275A1 (en) * | 2014-10-01 | 2016-04-07 | 協立化学産業株式会社 | Coated copper particles and production method therefor |
| CN108161027A (en) * | 2014-05-30 | 2018-06-15 | 协立化学产业株式会社 | It is coated copper particle |
| CN110202137A (en) * | 2019-05-29 | 2019-09-06 | 深圳第三代半导体研究院 | A kind of low-temperature sintering copper cream and its sintering process |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008016360A (en) * | 2006-07-07 | 2008-01-24 | Nippon Shokubai Co Ltd | Manufacturing method of conductive metal coating |
| JP2010080438A (en) * | 2008-08-28 | 2010-04-08 | Mitsuboshi Belting Ltd | Conductive substrate, and precursor thereof and manufacturing method therefor |
-
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008016360A (en) * | 2006-07-07 | 2008-01-24 | Nippon Shokubai Co Ltd | Manufacturing method of conductive metal coating |
| JP2010080438A (en) * | 2008-08-28 | 2010-04-08 | Mitsuboshi Belting Ltd | Conductive substrate, and precursor thereof and manufacturing method therefor |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108161027A (en) * | 2014-05-30 | 2018-06-15 | 协立化学产业株式会社 | It is coated copper particle |
| CN108161027B (en) * | 2014-05-30 | 2019-01-08 | 协立化学产业株式会社 | Coating copper particle |
| WO2016052275A1 (en) * | 2014-10-01 | 2016-04-07 | 協立化学産業株式会社 | Coated copper particles and production method therefor |
| JP2016069716A (en) * | 2014-10-01 | 2016-05-09 | 協立化学産業株式会社 | Coated copper particle and method for producing the same |
| TWI648111B (en) * | 2014-10-01 | 2019-01-21 | 日商協立化學產業股份有限公司 | Coated copper particles, a method for producing the same, and a conductive composition and circuit formation |
| CN110202137A (en) * | 2019-05-29 | 2019-09-06 | 深圳第三代半导体研究院 | A kind of low-temperature sintering copper cream and its sintering process |
| CN110202137B (en) * | 2019-05-29 | 2021-07-20 | 深圳第三代半导体研究院 | Low-temperature sintering copper paste and sintering process thereof |
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