JP2008013837A - Fine copper powder and its manufacturing method - Google Patents
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本発明は、球状あるいは粒状の微小銅粉、より詳細には、導電ペースト用、例えば電子回路におけるスルーホール用、ビア埋め用、ＭＬＣＣ外部電極用などのペーストに使用される微小銅粉、及びその製造方法に関する。 The present invention relates to a spherical or granular fine copper powder, more specifically, a fine copper powder used for a conductive paste, for example, a paste for an electronic circuit through hole, via filling, MLCC external electrode, and the like. It relates to a manufacturing method.
近年、ＯＡ機器、移動体通信機器等の電子部品実装技術において、配線やビア埋め、スルーホールなどの分野で、耐酸化性や低抵抗値などのために銀が用いられることが多い。しかし、銀を用いた場合、特にマイグレーションの影響などから製品としての不安定面が指摘され、ユーザーサイドで更にオーバーコート等の処理を施すか、完全に銀の使用を拒否するユーザーもある。 In recent years, in electronic component mounting technologies such as OA equipment and mobile communication equipment, silver is often used for oxidation resistance, low resistance value, and the like in the fields of wiring, via filling, and through holes. However, when silver is used, an unstable surface as a product is pointed out particularly due to the influence of migration, and there are some users who further perform processing such as overcoat on the user side or completely refuse the use of silver.
上記のマイグレーション防止ないし抑制のひとつの手段として、パラジウムを添加した銀−パラジウムが良く用いられるが、パラジウムが高価であるため、コスト面が需要拡大のネックになっているのも事実である。そこで、高価な銀や銀−パラジウムに代えて、安価で且つマイグレーションの影響をほとんど無視できる銅微粉の需要が高まってきている。 As one means for preventing or suppressing the migration, silver-palladium to which palladium is added is often used. However, since palladium is expensive, it is a fact that the cost is a bottleneck in demand expansion. Therefore, in place of expensive silver and silver-palladium, there is an increasing demand for copper fine powder that is inexpensive and can almost ignore the influence of migration.
また、最近の電子機器類などの小型化・軽量化に伴い、電子回路のファインピッチ化が進んでおり、配線幅、スルーホール径、ビア径などが微細化される傾向にある。そのため、これらの用途に使用される導電ペースト用の銅粉についても、平均粒径が従来の１０μｍから５μｍ以下へと移行しつつある。更に、スクリーン印刷やスルーホール用の導電ペーストに使用される銅粉は、丸みのある形状のものが求められ、高タップ密度で良好な導電性を示すものが望まれている。 In addition, with recent miniaturization and weight reduction of electronic devices and the like, fine pitches of electronic circuits are progressing, and the wiring width, through-hole diameter, via diameter, etc. tend to be miniaturized. Therefore, also about the copper powder for electrically conductive pastes used for these uses, the average particle diameter is shifting from the conventional 10 micrometers to 5 micrometers or less. Furthermore, the copper powder used for the conductive paste for screen printing and through-holes is required to have a round shape, and a high tap density and good conductivity are desired.
一般に、銅粉の製造方法としては、アトマイズ法、電解法、湿式合成法などが採用されている。銅粉の需要は年間５,０００トンを遥かに超えると言われているが、ほとんどが上記方法で製造された粉末冶金用の銅粉であり、特に非常に安価な電解銅粉が主に使用されている。ただし、電解銅粉は安価であるが、形状が樹脂状であり、タップ密度が低いという問題があるため、導電ペースト用としては不適当である。 Generally, as a method for producing copper powder, an atomizing method, an electrolytic method, a wet synthesis method, or the like is employed. Although the demand for copper powder is said to exceed 5,000 tons per year, most are copper powder for powder metallurgy manufactured by the above-mentioned method. Especially, very cheap electrolytic copper powder is mainly used. Has been. However, although electrolytic copper powder is inexpensive, it has a problem that the shape is resinous and the tap density is low, so that it is unsuitable for a conductive paste.
導電ペースト用としては、従来からアトマイズ銅粉が用いられている。しかしながら、アトマイズ銅粉は平均粒径１０〜数十μｍ程度が主であるため、数μｍのものを得るには分級が必要となり、生産効率が悪く高級品として販売されている。最近では、高圧水アトマイズ法によって平均粒径５μｍ以下のものも製造されているが、分級による製品歩留悪化の改善は十分ではなく、経済的に不利である。また、湿式合成法によれば、平均粒径０.２〜５μｍ程度でよく揃った粒度分布のものが得られやすいが、製造コストが高く、廃液処理等の環境面への配慮が必要である。 Conventionally, atomized copper powder has been used for a conductive paste. However, since the atomized copper powder mainly has an average particle size of about 10 to several tens of μm, classification is necessary to obtain a particle having a size of several μm, and the production efficiency is poor and it is sold as a high-quality product. Recently, products having an average particle size of 5 μm or less have been produced by the high-pressure water atomization method, but the improvement of product yield deterioration by classification is not sufficient, which is economically disadvantageous. In addition, according to the wet synthesis method, it is easy to obtain a well-equalized particle size distribution with an average particle size of about 0.2 to 5 μm, but the production cost is high, and environmental considerations such as waste liquid treatment are necessary. .
一方、特開昭６２−１９９７０５号公報には、比表面積が０.２ｍ２／ｇ以上の樹枝状電解銅粉を、流体エネルギーミルを用いた粒子相互の衝突により解砕、微粉化する微細粒状銅粉の製造方法が開示されている。しかし、具体例として示されている通常のジェットミルのような流体エネルギーミルでは、粒子の衝突により得られるエネルギーが低く、樹枝状に発達した電解銅粉の枝部を折ることによって粒状化するのみであり、粒子内部は密度の低い電解銅粉に近く、高タップ密度の銅粉を得ることはできない。 On the other hand, JP-A-62-199705 discloses a fine granular material in which dendritic electrolytic copper powder having a specific surface area of 0.2 m 2 / g or more is crushed and pulverized by collision between particles using a fluid energy mill. A method for producing copper powder is disclosed. However, in a fluid energy mill such as a normal jet mill shown as a specific example, the energy obtained by the collision of particles is low, and it is only granulated by folding branches of electrolytic copper powder that has developed into a dendritic shape. The inside of the particle is close to the electrolytic copper powder having a low density, and a copper powder having a high tap density cannot be obtained.
また、特開平２−１８２８０９号公報には、比表面積が０.１２ｍ２／ｇ以上の樹枝状電解銅粉の表面を油脂で被覆した後、流体エネルギーミルで微粉化する方法が開示されている。しかしながら、この方法も上記特開昭６２−１９９７０５号公報記載の方法と同様に、通常のジェットミルのような流体エネルギーミルを用いるものであるため、銅粉の高タップ密度化は不可能であり、導電性ペーストにしたときの導電性にも劣るという問題があった。 Japanese Patent Application Laid-Open No. 2-182809 discloses a method in which the surface of a dendritic electrolytic copper powder having a specific surface area of 0.12 m 2 / g or more is coated with oil and then pulverized with a fluid energy mill. . However, this method also uses a fluid energy mill such as an ordinary jet mill as in the method described in JP-A-62-199705, so that it is impossible to increase the tap density of copper powder. There was a problem that the conductivity was inferior when made into a conductive paste.
更に、特開２０００−８０４０８号公報には、平均粒径が２５〜３５μｍ、嵩密度が０.５〜０.８ｇ／ｃｍ３の樹枝状電解銅粉の表面を油脂で被覆した後、衝突板方式のジェットミルを用いて微粉化する方法が記載されている。しかしながら、この方法では、衝突板からの不純物の混入が懸念されるばかりか、得られる銅粉は粒状と枝状の混在したものであり、球形で高タップ密度であることが要求される導電ペースト用銅粉には不適であった。また樹脂を添加して硬化させた後の比抵抗率も１×１０−４Ω・ｃｍに留まり、低抵抗化の要求を満足すべきものではなかった。 Furthermore, JP-A-2000-80408 discloses that a surface of a dendritic electrolytic copper powder having an average particle size of 25 to 35 μm and a bulk density of 0.5 to 0.8 g / cm 3 is coated with an oil and fat, A method of pulverizing using a jet mill of the type is described. However, in this method, not only is there concern about the contamination of impurities from the collision plate, but the obtained copper powder is a mixture of grains and branches, and is a conductive paste that is required to be spherical and have a high tap density. It was unsuitable for copper powder. Further, the specific resistivity after the resin was added and cured remained at 1 × 10 −4 Ω · cm, and the requirement for lowering resistance was not satisfied.
本発明は、上記した従来の事情に鑑み、粒径が微細で形状が球形に近く且つ高タップ密度であり、樹脂を添加して熱硬化させたとき低い抵抗値を示し、導電性ペースト用として好適な銅粉を提供すること、並びに、その銅粉を安価且つ簡便に大量生産することができる製造方法を提供することを目的とする。 In view of the above-described conventional circumstances, the present invention has a fine particle size, a shape close to a sphere, and a high tap density. When the resin is added and thermally cured, it exhibits a low resistance value. An object is to provide a suitable copper powder and to provide a production method capable of mass-producing the copper powder inexpensively and easily.
本発明者らは、上記課題を解決するため、樹枝状電解銅粉の粉砕・微粉化に関する研究を進めた結果、高圧ジェット気流旋回渦方式のジェットミルを用いて樹枝状電解銅粉を粉砕及び緻密化することによって、平均粒径が微細で且つ粒径分布が狭く、球状あるいは粒状の微小銅粉が得られること、しかも従来の流体エネルギーミルや衝突板方式ジェットミルでは不可能であった高タップ密度化が可能であることを見出し、本発明をなすに至ったものである。 In order to solve the above problems, the present inventors have conducted research on pulverization and pulverization of dendritic electrolytic copper powder, and as a result, pulverized dendritic electrolytic copper powder using a jet mill of a high-pressure jet stream swirl vortex method and By densifying, the average particle size is fine, the particle size distribution is narrow, and spherical or granular fine copper powder can be obtained, and the high pressure that was impossible with conventional fluid energy mills and impingement plate type jet mills It has been found that tap density can be increased, and the present invention has been made.
即ち、本発明による微小銅粉の製造方法は、嵩密度０.８〜２.０ｇ／ｃｍ３の樹枝状電解銅粉を、大気雰囲気中又は不活性雰囲気中において高圧ジェット気流旋回渦方式のジェットミルを用いて粉砕及び緻密化し、平均粒径１〜６μｍの球状あるいは粒状の微小銅粉を得ることを特徴とする。 That is, the method for producing a fine copper powder according to the present invention comprises using a dendritic electrolytic copper powder having a bulk density of 0.8 to 2.0 g / cm 3 in a high-pressure jet stream swirl vortex method in an air atmosphere or an inert atmosphere. It is characterized by pulverizing and densifying using a mill to obtain spherical or granular fine copper powder having an average particle diameter of 1 to 6 μm.
上記本発明の微小銅粉の製造方法においては、前記高圧ジェット気流旋回渦方式のジェットミルによる粉砕圧力が６〜１５ｋｇ／ｃｍ２であることを特徴とする。また、前記高圧ジェット気流旋回渦方式のジェットミルによる粉砕後、得られた微小銅粉を酸処理し、同時に又はその後微小銅粉の表面を油脂で被覆することにより、耐防食性及び耐酸化性を向上させることができる。 In the method for producing fine copper powder of the present invention, the pulverization pressure by the high-pressure jet stream swirl vortex jet mill is 6 to 15 kg / cm 2 . In addition, after pulverization by the jet mill of the high-pressure jet airflow swirl vortex method, the obtained fine copper powder is acid-treated, and at the same time or after that, the surface of the fine copper powder is coated with oil and fat, thereby providing corrosion resistance and oxidation resistance. Can be improved.
また、本発明が提供する微小銅粉は、上記本発明方法で得られた平均粒径１〜６μｍで球状あるいは粒状の微小銅粉であって、その表面が油脂で被覆され、タップ密度が４.５ｇ／ｃｍ３以上であることを特徴とするものである。この本発明の微小銅粉は、樹脂を添加して大気雰囲気中において２００℃で硬化することにより、１×１０−５〜１×１０−４Ω・ｃｍの比抵抗値が得られることを特徴とする。 Moreover, the fine copper powder provided by the present invention is a spherical or granular fine copper powder having an average particle diameter of 1 to 6 μm obtained by the method of the present invention, and the surface thereof is coated with oil and fat, and the tap density is 4 It is characterized by being not less than 0.5 g / cm 3 . The fine copper powder of the present invention is characterized in that a specific resistance value of 1 × 10 −5 to 1 × 10 −4 Ω · cm can be obtained by adding a resin and curing at 200 ° C. in an air atmosphere. And
本発明によれば、平均粒径が１〜６μｍと微細で、形状が球形に近く、しかもタップ密度が４.５ｇ／ｃｍ３以上と高タップ密度である微小銅粉を、大量生産可能な方法により製造し、安価に提供することができる。また、本発明の微小銅粉は、上記した特性を有すると共に、硬化後に１×１０−５〜１×１０−４Ω・ｃｍの比抵抗値を示すことから、導電ペースト用などとして極めて好適なものである。 According to the present invention, a method capable of mass-producing fine copper powder having an average particle size as fine as 1 to 6 μm, a shape close to a sphere, and a tap density as high as 4.5 g / cm 3 or more. Can be manufactured at low cost. Moreover, since the micro copper powder of the present invention has the above-described characteristics and exhibits a specific resistance value of 1 × 10 −5 to 1 × 10 −4 Ω · cm after curing, it is extremely suitable as a conductive paste. Is.
本発明の製造方法において出発原料として用いる樹枝状電解銅粉は、嵩密度が０.８〜２.０ｇ／ｃｍ３のものである。嵩密度が０.８ｇ／ｃｍ３未満の樹枝状電解銅粉を用いた場合、大気雰囲気中での粉砕により銅粉が燃えたり、表面に過度の酸化物が形成されるため好ましくない。また、樹枝状電解銅粉の嵩密度が２.０ｇ／ｃｍ３を超えると、平均粒径１〜６μｍの微小銅粉を得ることが困難である。尚、原料として用いる樹枝状電解銅粉は、その平均粒径が２０〜４５μｍであることが好ましい。 The dendritic electrolytic copper powder used as a starting material in the production method of the present invention has a bulk density of 0.8 to 2.0 g / cm 3 . When a dendritic electrolytic copper powder having a bulk density of less than 0.8 g / cm 3 is used, it is not preferable because the copper powder burns by pulverization in an air atmosphere or excessive oxide is formed on the surface. Moreover, when the bulk density of the dendritic electrolytic copper powder exceeds 2.0 g / cm 3 , it is difficult to obtain fine copper powder having an average particle diameter of 1 to 6 μm. In addition, it is preferable that the average particle diameter of the dendritic electrolytic copper powder used as a raw material is 20-45 micrometers.
上記樹枝状電解銅粉は、高圧ジェット気流旋回渦方式のジェットミルを用いて粉砕することによって、球状あるいは粒状の微細な銅粉となると同時に緻密化され、サイクロンやバグフィルターによって回収される。この高圧ジェット気流旋回渦方式ジェットミルによる粉砕・緻密化は、大気雰囲気中あるいは不活性雰囲気中で行うことが出来るが、大気雰囲気中で粒径３μｍ以下の微小銅粉を作製した場合は表面酸化が過度に起こるため、不活性雰囲気中で行うことが好ましい。尚、粒径３μｍ以上の微小銅粉は、大気雰囲気中で粉砕・緻密化することができるため、低コストでの作製が可能である。 The dendritic electrolytic copper powder is pulverized using a high-pressure jet airflow swirl vortex jet mill to become a spherical or granular fine copper powder, which is simultaneously densified and collected by a cyclone or a bag filter. Grinding and densification by this high-pressure jet airflow swirl vortex jet mill can be performed in an air atmosphere or in an inert atmosphere, but surface oxidation occurs when a fine copper powder having a particle size of 3 μm or less is produced in the air atmosphere. Since this occurs excessively, it is preferably performed in an inert atmosphere. Note that a fine copper powder having a particle diameter of 3 μm or more can be pulverized and densified in an air atmosphere, so that it can be produced at low cost.
本発明で用いる高圧ジェット気流旋回渦方式のジェットミルは、大気あるいは不活性ガスによる高圧ジェット気流の同心円状旋回渦を形成し、その高圧ジェット気流旋回渦中で樹枝状電解銅粉の粒子同士を相互に衝突させる。その結果、樹枝状電解銅粉の樹枝部分が微細な粒子に分解された後、更なる衝突を繰り返すことにより粒子の角ばった部分が押しつぶされ、球状あるいは表面凹凸が少ない粒状の微小銅粉が得られる。 The jet mill of the high-pressure jet stream swirl vortex method used in the present invention forms a concentric swirl vortex of the high-pressure jet stream by the atmosphere or an inert gas, and the dendritic electrolytic copper powder particles are mutually connected in the high-pressure jet stream swirl vortex. Collide with. As a result, after the dendritic portion of the electrolytic copper powder is broken down into fine particles, repeated collisions cause the angular portions of the particles to be crushed, resulting in a granular or fine copper powder with less surface irregularities. It is done.
しかも、上記高圧ジェット気流旋回渦方式のジェットミルでは、従来の流体エネルギーミルや衝突板方式ジェットミルよりも粉砕圧力が高く、具体的には６ｋｇ／ｃｍ２を超え１５ｋｇ／ｃｍ２程度までの粉砕圧力が可能であって、気流も均一に制御されている。そのため、高い衝突エネルギーが得られ、樹枝状電解銅粉を容易に粉砕・微粉化すると同時に、内部まで容易に緻密化して、高密度な微小銅粉とすることができる。 Moreover, the jet mill of the high-pressure jet stream swirling vortex method, higher grinding pressure than conventional fluid energy mill or a collision plate type jet mill, specifically grinding until 15 kg / cm 2 about exceed 6 kg / cm 2 Pressure is possible and the airflow is also controlled uniformly. Therefore, high collision energy can be obtained, and the dendritic electrolytic copper powder can be easily pulverized and pulverized, and at the same time, the dendritic electrolytic copper powder can be easily densified into a high-density fine copper powder.
このような高圧ジェット気流旋回渦方式のジェットミルとしては、（株）徳寿工作所製のＮＪ式ナノグラインディングミルを例示することができる。 An example of such a high-pressure jet airflow swirl vortex jet mill is an NJ nanogrinding mill manufactured by Tokuju Factory.
上記した本発明方法によって得られる微小銅粉は、平均粒径が１〜６μｍの球状あるいは粒状であって、表面が非常に平滑で凹凸が少ない。尚、平均粒径が１μｍ未満の場合は高充填できず、逆に平均粒径が６μｍを超え場合には微細なスルーホールなどに使用できない。また、球状あるいは粒状とすることにより、微小銅粉のタップ密度を上げることができ、成膜・硬化後の比抵抗率を低くすることができる。従って、本発明の微小銅粉は、スルーホール用などの導電ペーストのフィラーとして好適であり、スクリーン印刷にも適している。 The fine copper powder obtained by the above-described method of the present invention is spherical or granular with an average particle diameter of 1 to 6 μm, and has a very smooth surface and few irregularities. When the average particle size is less than 1 μm, high filling cannot be performed. Conversely, when the average particle size exceeds 6 μm, it cannot be used for fine through holes. Moreover, by making it spherical or granular, the tap density of the fine copper powder can be increased, and the specific resistivity after film formation and curing can be lowered. Therefore, the fine copper powder of the present invention is suitable as a filler for conductive pastes for through holes and the like, and is also suitable for screen printing.
また、本発明の微小銅粉は、上記した微粉化と緻密化の後に、その粒子表面を油脂により被覆することが好ましい。従来から酸化防止のために粉砕前の原料粉を油脂被覆することは知られているが、流体エネルギーミルや衝突板方式ジェットミルでの粉砕中に油脂が摩擦などで剥ぎ取られ、粒子の表面が酸化することが避けられないため、成膜・硬化したときの低抵抗化が困難であった。 Moreover, it is preferable that the fine copper powder of this invention coat | covers the particle | grain surface with fats and oils after the above-mentioned micronization and densification. Conventionally, it is known to coat raw material powder before grinding to prevent oxidation, but during grinding with a fluid energy mill or a collision plate type jet mill, the grease is stripped off due to friction, etc. Since it is unavoidable that the film is oxidized, it is difficult to reduce the resistance when the film is formed and cured.
一方、本発明では、高圧ジェット気流旋回渦方式ジェットミルでの粉砕後に、得られた微小銅粉を酸処理し、同時に又はその後、微小銅粉の表面を油脂で被覆する。例えば、粉砕後の微小銅粉を酸の水溶液中に投入して撹拌し、続いて、得られたスラリーに脂肪酸のアルカリ金属塩を添加して撹拌保持した後、ろ過・乾燥する。このとき、微小銅粉を水に投入してスラリーとした後に酸を添加してもよいし、酸の水溶液中に脂肪酸のアルカリ金属塩を添加して、酸処理と油脂被覆を同時に行うこともできる。また、脂肪酸のアルカリ金属塩の添加時に、アスコルビン酸などの還元剤を同時に添加してもよい。 On the other hand, in the present invention, after pulverization in a high-pressure jet airflow swirl vortex jet mill, the obtained fine copper powder is acid-treated, and simultaneously or thereafter, the surface of the fine copper powder is coated with oil. For example, the pulverized fine copper powder is put into an acid aqueous solution and stirred. Subsequently, an alkali metal salt of a fatty acid is added to the resulting slurry and held, and then filtered and dried. At this time, the acid may be added after adding the fine copper powder into water to form a slurry, or the acid treatment and the oil / fat coating may be performed simultaneously by adding an alkali metal salt of a fatty acid to the acid aqueous solution. it can. Moreover, you may add reducing agents, such as ascorbic acid, at the time of addition of the alkali metal salt of a fatty acid.
上記酸処理により、微小銅粉の表面酸化膜を取り除くことができる。用いる酸としては、酢酸、ギ酸、硫酸、リン酸、硝酸が好ましい。また、酸の添加量は過剰に入れる必要はなく、粒子表面の酸化膜や汚染層が除去できる程度のものであればよい。次に、この酸処理によって清浄化された微小銅粉の表面に、油脂を被覆することにより、耐酸化性を付与すると同時に、より高タップ密度化を達成でき、導電用ペーストとして成膜・硬化したときの低抵抗化が可能となる。 By the acid treatment, the surface oxide film of the fine copper powder can be removed. As the acid used, acetic acid, formic acid, sulfuric acid, phosphoric acid, and nitric acid are preferable. Further, it is not necessary to add an excessive amount of acid as long as the oxide film and the contamination layer on the particle surface can be removed. Next, the surface of the fine copper powder cleaned by this acid treatment is coated with oils and fats to provide oxidation resistance and at the same time a higher tap density can be achieved. It is possible to reduce the resistance.
微小銅粉の表面に被覆される油脂は、炭素数８以上の脂肪酸が好ましい。かかる脂肪酸としては、例えば、オクタン酸（炭素数８）、デカン酸（炭素数１０）、ラウリン酸（炭素数１２）、ミリスチン酸（炭素数１４）、パルミチン酸（炭素数１６）、ステアリン酸（炭素数１８）、オレイン酸（不飽和、炭素数１８）などが挙げられる。炭素数１８を超える脂肪酸も使用できるが、高価であるうえ、操作性もよくないため、炭素数１８のステアリン酸までが実用的である。 Fats and oils coated on the surface of the fine copper powder are preferably fatty acids having 8 or more carbon atoms. Examples of such fatty acids include octanoic acid (8 carbon atoms), decanoic acid (10 carbon atoms), lauric acid (12 carbon atoms), myristic acid (14 carbon atoms), palmitic acid (16 carbon atoms), stearic acid ( Examples thereof include carbon number 18) and oleic acid (unsaturated, carbon number 18). Fatty acids having more than 18 carbon atoms can be used, but since they are expensive and have poor operability, stearic acid having 18 carbon atoms is practical.
炭素数８以上の脂肪酸は水に対してほとんど溶解しないが、脂肪酸のナトリウム塩やカリウム塩などアルカリ金属塩であれば溶解度があるため、水溶液中で微小銅粉の表面に脂肪酸の被膜を形成することができる。尚、脂肪酸のアルカリ金属塩の添加量は水に対する臨界ミセル濃度付近でよく、未溶解分が発生するほど過剰に添加する必要はない。 Fatty acids having 8 or more carbon atoms are hardly soluble in water, but are soluble in alkali metal salts such as sodium salts and potassium salts of fatty acids. Therefore, a fatty acid film is formed on the surface of fine copper powder in an aqueous solution. be able to. In addition, the addition amount of the alkali metal salt of the fatty acid may be in the vicinity of the critical micelle concentration with respect to water, and it is not necessary to add it excessively so that an undissolved part is generated.
上記した表面被覆処理により、微小銅粉の表面に分子１層分の脂肪酸がイオン配位して、過剰な脂肪酸の付着がない綺麗な油脂被膜を形成することができ、その結果、本発明の微小銅粉はタップ密度が更に向上して４.５ｇ／ｃｍ３以上となる。タップ密度が４.５ｇ／ｃｍ３以上になると、成膜・硬化したときに粒子間の導電パスが増加することや、膜内の銅粉体積が増加することから、一層の低抵抗化を実現することができる。タップ密度は５.０ｇ／ｃｍ３以上が更に好ましく、より低抵抗化が可能となるが、本発明の平均粒径では６.０ｇ／ｃｍ３を超えるものを得ることは実質的に困難である。 By the surface coating treatment described above, the fatty acid for one layer of molecules is ion-coordinated on the surface of the fine copper powder, and a beautiful oil film without excessive fatty acid adhesion can be formed. The fine copper powder further improves the tap density to 4.5 g / cm 3 or more. When the tap density is 4.5 g / cm 3 or higher, the conductive path between the particles increases when the film is formed and cured, and the volume of copper powder in the film increases, further reducing the resistance. can do. The tap density is more preferably 5.0 g / cm 3 or more, and the resistance can be further reduced. However, it is substantially difficult to obtain a tap density exceeding 6.0 g / cm 3 with the average particle diameter of the present invention. .
本発明の微小銅粉は、上記した高いタップ密度に加えて、清浄な表面が脂肪酸で被覆されていて硬化中の粒子表面の酸化が低減されるため、樹脂を添加して大気雰囲気中において２００℃で硬化させたとき、１×１０−５〜１×１０−４Ω・ｃｍの低い比抵抗値を示し、導電ペースト用銅粉として好適なものである。使用する樹脂としては、熱硬化性を持った樹脂であれば特に限定されないが、フェノール樹脂、アクリル樹脂などの硬化時に収縮する樹脂が好ましい。 In addition to the above-described high tap density, the fine copper powder of the present invention has a clean surface coated with a fatty acid so that oxidation of the particle surface during curing is reduced. When cured at 0 ° C., it exhibits a low specific resistance value of 1 × 10 −5 to 1 × 10 −4 Ω · cm and is suitable as a copper powder for conductive paste. The resin to be used is not particularly limited as long as it is a thermosetting resin, but a resin that shrinks upon curing, such as a phenol resin and an acrylic resin, is preferable.
尚、ここで用いる硬化温度では、微小銅粉同士の焼結が進まず、熱硬化性樹脂の収縮によるコンタクトのみで低抵抗化するため、比抵抗値の下限はバルクの比抵抗値に比べて高い１×１０−５Ω・ｃｍ程度である。しかしながら、この大気雰囲気中２００℃での硬化により１×１０−５〜１×１０−４Ω・ｃｍの低抵抗化が実現できれば、ポリイミド基板などに使用可能となる。更に１６０℃以下の硬化温度で同程度の低い比抵抗値が得られれば、ガラスエポキシ基板にも使用することができる。 In addition, at the curing temperature used here, sintering between the fine copper powders does not proceed, and the resistance is reduced only by the contact due to shrinkage of the thermosetting resin, so the lower limit of the specific resistance value is lower than the specific resistance value of the bulk The height is about 1 × 10 −5 Ω · cm. However, if a low resistance of 1 × 10 −5 to 1 × 10 −4 Ω · cm can be realized by curing at 200 ° C. in the air atmosphere, it can be used for a polyimide substrate or the like. Furthermore, if a comparable specific resistance value is obtained at a curing temperature of 160 ° C. or lower, the glass epoxy substrate can be used.
［実施例１］
樹枝状電解銅粉（ネクセルジャパン製、電解銅粉Ｃｕ−３００）を、高圧ジェット気流旋回渦方式ジェットミルである（株）徳寿工作所製のＮＪ式ナノグラインディングミル（ＮＪ−３０）を用いて、空気流量２００リットル／分、粉砕圧力１０ｋｇ／ｃｍ２、約４００ｇ／時間で８パス実施して、粉砕・微粉化した。上記樹枝状電解銅粉の平均粒径は３０.５μｍ、嵩密度は１.６ｇ／ｃｍ３、ＢＥＴ法比表面積は０.２３ｍ２／ｇであった。この出発原料である樹枝状電解銅粉の走査型電子顕微鏡写真を図１に示す。
[Example 1]
Dendritic electrolytic copper powder (manufactured by Nextel Japan, electrolytic copper powder Cu-300) is a high-pressure jet airflow swirl vortex jet mill, using an NJ nanogrinding mill (NJ-30) manufactured by Tokuju Kogakusho Co., Ltd. Then, 8 passes were performed at an air flow rate of 200 liters / minute, a pulverization pressure of 10 kg / cm 2 , and about 400 g / hour, and pulverized and pulverized. The dendritic electrolytic copper powder had an average particle size of 30.5 μm, a bulk density of 1.6 g / cm 3 , and a BET specific surface area of 0.23 m 2 / g. A scanning electron micrograph of the dendritic electrolytic copper powder as the starting material is shown in FIG.
上記微粉化により得られた銅粉は粒状であり、平均粒径は５.６７μｍ、嵩密度は３.１１ｇ／ｃｍ３、ＢＥＴ法比表面積は０.２５ｍ２／ｇであった。尚、平均粒径は、日機装（株）製のＭＩＣＲＯＴＲＡＣ ＨＲＡ９３２０Ｘ−１００を用いて求めた。また、嵩密度は粉体の体積と粒子の質量の比から求めた。上記微粉化により得られた微小銅粉の走査型電子顕微鏡写真を図２に示す。 The copper powder obtained by the pulverization was granular, the average particle size was 5.67 μm, the bulk density was 3.11 g / cm 3 , and the BET specific surface area was 0.25 m 2 / g. In addition, the average particle diameter was calculated | required using Nikkiso Co., Ltd. MICROTRAC HRA9320X-100. The bulk density was determined from the ratio of the powder volume to the particle mass. A scanning electron micrograph of the fine copper powder obtained by the above micronization is shown in FIG.
次に、上記微粉化により得られた微小銅粉に対し、表面被覆処理を行った。即ち、純水２００ｍｌ中にギ酸（和光純薬工業（株）製、和光１級）２５ｍｌを溶解した溶液に、微小銅粉１００ｇを分散させた後、純水５０ｍｌにステアリン酸ナトリウム（和光純薬工業（株）製、試薬）０.２ｇを溶解した溶液を添加し、撹拌しながら１時間保持した。その後、濾過して微小銅粉を回収し、６０℃で真空加熱乾燥した。得られた微小銅粉（ステアリン酸で表面被覆）のタップ密度を測定したところ、５.３ｇ／ｃｍ３であった。 Next, the surface coating process was performed with respect to the fine copper powder obtained by the said fine pulverization. That is, after dispersing 100 g of fine copper powder in a solution in which 25 ml of formic acid (Wako Pure Chemical Industries, Ltd., Wako Grade 1) is dissolved in 200 ml of pure water, sodium stearate (Wako Pure Chemical Industries) is added to 50 ml of pure water. A solution in which 0.2 g of a reagent manufactured by Kogyo Co., Ltd. was dissolved was added and held for 1 hour with stirring. Then, it filtered and collect | recovered micro copper powder, and vacuum-dried at 60 degreeC. When the tap density of the obtained fine copper powder (surface coated with stearic acid) was measured, it was 5.3 g / cm 3 .
このようにして得られた微小銅粉８５重量部に、フェノール樹脂（群栄化学（株）製、ＰＬ−２２１１）１５重量部、ブチルセロソルブ（関東化学（株）製、鹿特級）１０重量部を混合し、小型ニーダー（日本精機製作所製、ノンバブリングニーダーＮＢＫ−１）を用い、１２００ｒｐｍ、３分間の混錬を３回繰り返すことでペースト化した。得られた導電ペーストを金属スキージでガラス上に印刷し、大気雰囲気中にて１５０℃、２００℃でそれぞれ３０分間硬化させた。 To 85 parts by weight of the fine copper powder thus obtained, 15 parts by weight of phenol resin (manufactured by Gunei Chemical Co., Ltd., PL-2211) and 10 parts by weight of butyl cellosolve (manufactured by Kanto Chemical Co., Ltd., deer special grade) are added. Using a small kneader (manufactured by Nippon Seiki Seisakusho, non-bubbling kneader NBK-1), the mixture was kneaded at 1200 rpm for 3 minutes three times to form a paste. The obtained conductive paste was printed on a glass with a metal squeegee and cured at 150 ° C. and 200 ° C. for 30 minutes in an air atmosphere.
上記導電ペーストの硬化により得られた被膜の比抵抗値は、それぞれ１.６×１０−４Ω・ｃｍ（硬化温度１５０℃）、４.３×１０−５Ω・ｃｍ（硬化温度２００℃）であった。尚、被膜の比抵抗値は、低抵抗率計（三菱化学（株）製、Ｌｏｒｅｓｔａ−ＧＰ ＭＣＰ−Ｔ６００）を用いて四端子法によりシート抵抗値を測定し、表面粗さ形状測定器（東京精密（株）製、ＳＵＲＦＣＯＭ１３０Ａ）により被膜の膜厚を測定して、上記シート抵抗値を膜厚で除することによって求めた。 The specific resistance values of the films obtained by curing the conductive paste are 1.6 × 10 −4 Ω · cm (curing temperature 150 ° C.) and 4.3 × 10 −5 Ω · cm (curing temperature 200 ° C.), respectively. Met. In addition, the specific resistance value of a film measured the sheet resistance value by a four-terminal method using a low resistivity meter (Loresta-GP MCP-T600, manufactured by Mitsubishi Chemical Corporation), and a surface roughness shape measuring instrument (Tokyo) The film thickness of the film was measured by SURFCOM130A) manufactured by Seimitsu Co., Ltd., and obtained by dividing the sheet resistance value by the film thickness.
［比較例１］
平均粒径４０.０μｍ、嵩密度２.２ｇ／ｃｍ３、ＢＥＴ法比表面積０.１７ｍ２／ｇの樹枝状電解銅粉（三井金属鉱業（株）製、電解銅粉ＭＤ−１）を、高圧ジェット気流旋回渦方式ジェットミルである（株）徳寿工作所製のＮＪ式ナノグラインディングミル（ＮＪ−３０）を用いて、上記実施例１と同様にして、粉砕圧力１０ｋｇ／ｃｍ２、約４００ｇ／時間で３パス実施して、で粉砕・微粉化した。
[Comparative Example 1]
Dendritic electrolytic copper powder (Mitsui Metal Mining Co., Ltd., electrolytic copper powder MD-1) having an average particle size of 40.0 μm, a bulk density of 2.2 g / cm 3 and a BET specific surface area of 0.17 m 2 / g, Using a NJ-type nanogrinding mill (NJ-30) manufactured by Tokuju Factory, which is a high-pressure jet airflow swirl vortex type jet mill, in the same manner as in Example 1 above, a pulverization pressure of 10 kg / cm 2 , about Three passes were performed at 400 g / hour, and pulverized and pulverized.
得られた銅微粉は粒状であり、平均粒径は１４.８９μｍであった。この比較例１では、出発原料として嵩密度が２.０ｇ／ｃｍ３を超える樹枝状電解銅粉を用いているため、平均粒径１〜６μｍの微小銅粉は作製できなかった。 The obtained copper fine powder was granular, and the average particle size was 14.89 μm. In Comparative Example 1, since a dendritic electrolytic copper powder having a bulk density exceeding 2.0 g / cm 3 was used as a starting material, a fine copper powder having an average particle diameter of 1 to 6 μm could not be produced.
［比較例２］
平均粒径４０.０μｍ、嵩密度２.２ｇ／ｃｍ３、ＢＥＴ法比表面積０.１７ｍ２／ｇの樹枝状電解銅粉（三井金属鉱業（株）製、電解銅粉ＭＤ−１）を、通常のジェットミル（（株）栗本鐵工所社製、ＫＪ−５０）を用いて、粉砕圧力６ｋｇ／ｃｍ２、約２０００ｇ／時間で粉砕・微粉化した。
[Comparative Example 2]
Dendritic electrolytic copper powder (Mitsui Metal Mining Co., Ltd., electrolytic copper powder MD-1) having an average particle size of 40.0 μm, a bulk density of 2.2 g / cm 3 and a BET specific surface area of 0.17 m 2 / g, Using an ordinary jet mill (KJ-50, manufactured by Kurimoto Steel Co., Ltd.), the mixture was pulverized and pulverized at a pulverization pressure of 6 kg / cm 2 and about 2000 g / hour.
得られた銅微粉は粒状であり、平均粒径が３.５８μｍ、嵩密度が２.５５ｇ／ｃｍ３、ＢＥＴ法比表面積が０.６１ｍ２／ｇであった。この銅微粉に上記実施例１と同様にしてステアリン酸を被覆したところ、タップ密度は４.４ｇ／ｃｍ３であった。 The obtained copper fine powder was granular, the average particle size was 3.58 μm, the bulk density was 2.55 g / cm 3 , and the BET specific surface area was 0.61 m 2 / g. When this copper fine powder was coated with stearic acid in the same manner as in Example 1, the tap density was 4.4 g / cm 3 .
更に、得られた銅微粉を、上記実施例１と同様にして、ペースト化し、その導電ペーストを用いて被膜を形成した。得られた被膜の比抵抗値を上記実施例１と同様に測定したところ、それぞれ４.６×１０５Ω・ｃｍ（硬化温度１５０℃）、１.０×１０６Ω・ｃｍ（硬化温度２００℃）であった。この比較例２では、通常のジェットミルを用いて粉砕したことによって、得られた銅微粉の粒度分布が広く且つ粒径１μｍ以下の微粒が酸化されたため、硬化後の比抵抗値が極めて高くなっている。 Further, the obtained copper fine powder was made into a paste in the same manner as in Example 1, and a film was formed using the conductive paste. When the specific resistance value of the obtained film was measured in the same manner as in Example 1, it was 4.6 × 10 5 Ω · cm (curing temperature 150 ° C.), 1.0 × 10 6 Ω · cm (curing temperature 200). ° C). In Comparative Example 2, since the particle size distribution of the obtained copper fine powder was wide and fine particles having a particle size of 1 μm or less were oxidized by pulverization using an ordinary jet mill, the specific resistance value after curing became extremely high. ing.
［実施例２］
平均粒径２０.３μｍ、嵩密度０.８ｇ／ｃｍ３、ＢＥＴ法比表面積０.４０ｍ２／ｇの樹枝状電解銅粉（福田金属箔粉工業（株）製、電解粉ＦＣＣ−１１５）を、高圧ジェット気流旋回渦方式ジェットミルである（株）徳寿工作所製のＮＪ式ナノグラインディングミル（ＮＪ−１００）を用い、上記実施例１と同様にして、粉砕圧力１０ｋｇ／ｃｍ２、約２０００ｇ／時間で８パス実施して、粉砕・微粉化した。
[Example 2]
Dendritic electrolytic copper powder having an average particle size of 20.3 μm, bulk density of 0.8 g / cm 3 and BET specific surface area of 0.40 m 2 / g (made by Fukuda Metal Foil Powder Industry Co., Ltd., electrolytic powder FCC-115) In the same manner as in Example 1 above, a grinding pressure of 10 kg / cm 2 , about 8 passes were performed at 2000 g / hour, and pulverized and pulverized.
上記微粉化により得られた銅粉は粒状であり、平均粒径が３.６７μｍ、嵩密度が２.２７ｇ／ｃｍ３、ＢＥＴ法比表面積が０.７４ｍ２／ｇであった。また、この微小銅粉を、上記実施例１と同様にしてステアリン酸を被覆したところ、表面被覆後のタップ密度は５.０ｇ／ｃｍ３であった。更に、この微小銅粉を、上記実施例１と同様にペースト化し、その導電ペーストを用いて形成した被膜の比抵抗値を上記実施例１と同様に測定したところ、それぞれ７.５×１０−５Ω・ｃｍ（硬化温度１５０℃）、４.３×１０−５Ω・ｃｍ（硬化温度２００℃）であった。 The copper powder obtained by the above pulverization was granular, with an average particle size of 3.67 μm, a bulk density of 2.27 g / cm 3 , and a BET specific surface area of 0.74 m 2 / g. Further, when this fine copper powder was coated with stearic acid in the same manner as in Example 1, the tap density after surface coating was 5.0 g / cm 3 . Furthermore, when this fine copper powder was pasted in the same manner as in Example 1, and the specific resistance value of the film formed using the conductive paste was measured in the same manner as in Example 1, it was 7.5 × 10 − It was 5 Ω · cm (curing temperature 150 ° C.), 4.3 × 10 −5 Ω · cm (curing temperature 200 ° C.).
［実施例３］
粉砕圧力を６ｋｇ／ｃｍ２、１２ｋｇ／ｃｍ２と変化させた以外は、上記実施例１と同様にして、樹枝状電解銅粉を粉砕・微粉化した。上記粉砕圧力６ｋｇ／ｃｍ２で得られた微小銅粉は、平均粒径が２.６４μｍであり、上記実施例１と同様にしてステアリン酸を被覆した後の微小銅粉のタップ密度は４.７ｇ／ｃｍ３であった。
[Example 3]
The dendritic electrolytic copper powder was pulverized and pulverized in the same manner as in Example 1 except that the pulverization pressure was changed to 6 kg / cm 2 and 12 kg / cm 2 . The fine copper powder obtained at the pulverization pressure of 6 kg / cm 2 has an average particle diameter of 2.64 μm, and the tap density of the fine copper powder after coating with stearic acid in the same manner as in Example 1 is 4. It was 7 g / cm 3 .
また、上記粉砕圧力１２ｇ／ｃｍ２で得られた微小銅粉は、平均粒径が２.３９μｍであった。この微小銅粉の粒度分布を図３に示す。図３から、非常に良好な粒度分布を示していることが分る。また、表面被覆後の微小銅粉のタップ密度は４.５ｇ／ｃｍ３であった。 The fine copper powder obtained at the pulverization pressure of 12 g / cm 2 had an average particle size of 2.39 μm. The particle size distribution of the fine copper powder is shown in FIG. It can be seen from FIG. 3 that the particle size distribution is very good. Moreover, the tap density of the fine copper powder after the surface coating was 4.5 g / cm 3 .
Claims (5)
5. The specific resistance value of 1 × 10 −5 to 1 × 10 −4 Ω · cm can be obtained by adding a resin and curing at 200 ° C. in an air atmosphere. Fine copper powder.
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