JP4670659B2 - Fluorescently labeled metal powder, anisotropic conductive film containing the fluorescently labeled metal powder, and mounted product - Google Patents
Fluorescently labeled metal powder, anisotropic conductive film containing the fluorescently labeled metal powder, and mounted product Download PDFInfo
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- JP4670659B2 JP4670659B2 JP2006016280A JP2006016280A JP4670659B2 JP 4670659 B2 JP4670659 B2 JP 4670659B2 JP 2006016280 A JP2006016280 A JP 2006016280A JP 2006016280 A JP2006016280 A JP 2006016280A JP 4670659 B2 JP4670659 B2 JP 4670659B2
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- metal powder
- conductive film
- anisotropic conductive
- metal
- fluorescently labeled
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Images
Description
本発明は、蛍光標識金属粉末とその製造方法に関するものである。また、該蛍光標識金属粉末を用いた異方導電膜、実装品に関するものである。 The present invention relates to a fluorescently labeled metal powder and a method for producing the same. Further, the present invention relates to an anisotropic conductive film using the fluorescently labeled metal powder and a mounted product.
プリント配線板上に半導体パッケージを実装したり、あるいは２つのプリント配線板上の導体配線同士を電気的に接続するとともに、両プリント配線板を互いに結合、固定したりするエレクトロニクス実装の方法の１つに、フィルム状の異方導電膜を用いた方法がある。 One of electronic mounting methods for mounting a semiconductor package on a printed wiring board, or electrically connecting conductor wirings on two printed wiring boards, and coupling and fixing both printed wiring boards to each other. In addition, there is a method using a film-like anisotropic conductive film.
例えばガラス基板と半導体パッケージとを実装する場合は、複数の突起電極を配列して接続部を形成した半導体パッケージと、当該半導体パッケージを実装する領域に上記突起電極とピッチを合わせて複数の配線電極を配列して接続部を形成したガラス基板とを用意する。そしてこの両者の接続部を相対向させて、その間に異方導電膜を挟んだ状態で、両接続部の各々の突起電極と配線電極とが１対１で膜の厚み方向に重なるように位置合わせしながら加熱、加圧処理を行うことで、各々の突起電極と配線電極が異方導電膜に含まれる導電成分を介して電気的に接続されるとともに、異方導電膜中の結着剤によって両者が接着、固定される。 For example, when a glass substrate and a semiconductor package are mounted, a semiconductor package in which a plurality of protruding electrodes are arranged to form a connection portion, and a plurality of wiring electrodes that match the pitch of the protruding electrodes and a region in which the semiconductor package is mounted And a glass substrate on which connection portions are formed. Then, with the connecting portions of the two facing each other and the anisotropic conductive film sandwiched between them, the protruding electrodes and the wiring electrodes of both connecting portions are positioned so as to overlap each other in the thickness direction of the film. By performing heating and pressurizing processes while combining, each protruding electrode and the wiring electrode are electrically connected via the conductive component contained in the anisotropic conductive film, and the binder in the anisotropic conductive film To bond and fix both.
また、ガラス基板とフレキシブルプリント基板との接続の場合は、それぞれの接続位置に、互いにピッチを合わせて複数の配線電極を配列して接続部を形成したガラス基板とフレキシブルプリント基板とを用意する。そしてこの両者の接続部を相対向させて、その間に異方導電膜を挟んだ状態で、同様に両接続部の各々の電極が１対１で膜の厚み方向に重なるように位置合わせしながら加熱、加圧処理を行うことで、各々の電極が異方導電膜に含まれる導電成分を介して電気的に接続されるとともに、異方導電膜中の結着剤によって両者が接着、固定される。 In the case of connection between a glass substrate and a flexible printed board, a glass substrate and a flexible printed board in which a plurality of wiring electrodes are arranged at respective connection positions at the same pitch to form connection portions are prepared. Then, with the connecting portions of the two facing each other and sandwiching the anisotropic conductive film between them, the electrodes of both the connecting portions are similarly aligned so as to overlap each other in the thickness direction of the film. By performing heating and pressure treatment, each electrode is electrically connected via the conductive component contained in the anisotropic conductive film, and both are bonded and fixed by the binder in the anisotropic conductive film. The
これらエレクトロニクス実装に用いる異方導電膜中に含まれる導電成分としては、例えば平均粒径が数μｍ〜数十μｍ程度で、かつその形状が粒状、球状、薄片状（鱗片状、フレーク状）などであるものなど、種々の金属粉末が実用化されているが、特に近時、微細な金属粒が直鎖状に繋がれた形状を有する直鎖状金属粉末が注目されている。 Examples of the conductive component contained in the anisotropic conductive film used for electronics mounting include an average particle size of about several μm to several tens of μm, and the shape is granular, spherical, flaky (flaky, flaky), etc. Various metal powders have been put into practical use, and recently, linear metal powders having a shape in which fine metal particles are connected in a straight chain are attracting attention.
直鎖状金属粉末は、粒状のものに比べて比表面積が大きいため、異方導電膜を形成する結着剤に対する分散性に優れており、個々の粉末が凝集することなく、均一に分散することが可能である。 Since the linear metal powder has a larger specific surface area than the granular one, it has excellent dispersibility for the binder that forms the anisotropic conductive film, and the individual powders are uniformly dispersed without agglomeration. It is possible.
また、直鎖状金属粉末を異方導電膜の厚み方向に配向させることで、導電成分の充填率を増加させることなく膜の厚み方向の導電性を上げることができる。このため膜の面方向の絶縁性を保ったまま接続抵抗を下げることができ、接続信頼性が向上する。なお、厚み方向に配向とは、直鎖状金属粉末の長手方向が、膜の面に対して略垂直方向に並んでいる状態をいう。 Further, by orienting the linear metal powder in the thickness direction of the anisotropic conductive film, the conductivity in the thickness direction of the film can be increased without increasing the filling rate of the conductive component. For this reason, the connection resistance can be lowered while maintaining the insulation in the surface direction of the film, and the connection reliability is improved. The orientation in the thickness direction means a state in which the longitudinal direction of the linear metal powder is aligned in a direction substantially perpendicular to the film surface.
異方導電膜を用いて実装した実装品の接続抵抗や接続信頼性を向上させるには、実装品の相対向する電極間により多くの導電成分が存在することが重要である。しかし、導電成分が直鎖状金属粉末である場合は、電極間の導電成分の存在を評価することは容易ではない。 In order to improve the connection resistance and the connection reliability of a mounted product mounted using an anisotropic conductive film, it is important that more conductive components exist between opposing electrodes of the mounted product. However, when the conductive component is a linear metal powder, it is not easy to evaluate the presence of the conductive component between the electrodes.
例えば、特許文献１では、直鎖状金属粉末間の相互作用の粗密の効果による実装品の隣接する電極間の短絡を防止するために、上記金属粉末の鎖の径を１μｍ以下としている。 For example, in Patent Document 1, the chain diameter of the metal powder is set to 1 μm or less in order to prevent a short circuit between adjacent electrodes of the mounted product due to the effect of the density of the interaction between the linear metal powders.
特許文献１に記載の直鎖状金属粉末を含有する異方導電膜を用いて、例えば、ガラス基板と半導体パッケージを実装した場合は、ガラス基板側から半導体パッケージの突起電極に向けて、光学顕微鏡の光源ランプの光を照射し、反射した可視光を光学顕微鏡で観察すると、突起電極上に存在する上記直鎖状金属粉末を確認することができる。直鎖状金属粉末は鎖の径が１μｍ以下であるので黒い線として観察されるが、突起電極の表面の微細な凹凸も同様に黒い線として観察されるため、両者を区別して、直鎖状金属粉末の存在を評価することは困難となる。確かに、異方導電膜を用いて実装した実装品を切断し、実装品の接続部を含む領域の切断面を調製すれば、特許文献１に記載の直鎖状金属粉末の存在を評価することは可能かもしれない。 For example, when the glass substrate and the semiconductor package are mounted using the anisotropic conductive film containing the linear metal powder described in Patent Document 1, the optical microscope is directed from the glass substrate side toward the protruding electrode of the semiconductor package. By irradiating the light from the light source lamp and observing the reflected visible light with an optical microscope, the linear metal powder present on the protruding electrode can be confirmed. Since the linear metal powder has a chain diameter of 1 μm or less and is observed as a black line, fine irregularities on the surface of the protruding electrode are also observed as black lines. It is difficult to evaluate the presence of metal powder. Surely, if the mounted product mounted using the anisotropic conductive film is cut, and the cut surface of the region including the connection part of the mounted product is prepared, the presence of the linear metal powder described in Patent Document 1 is evaluated. It may be possible.
しかし、異方導電膜を用いて実装した実装品を切断した後、実装品の接続部を含む領域の切断面を調整し、しかもそこから鎖の径が１μｍ以下の直鎖状金属粉末を見つけだすことは非常に困難を伴う。また、必然的に製品の抜き取り検査となり、しかも抜き取った製品のごく一部しか評価できないことから、評価結果の信頼性は高くない。 However, after cutting a mounted product mounted using an anisotropic conductive film, the cut surface of the region including the connecting portion of the mounted product is adjusted, and a linear metal powder having a chain diameter of 1 μm or less is found therefrom. That is very difficult. In addition, since the inspection of the product is inevitably performed and only a part of the extracted product can be evaluated, the reliability of the evaluation result is not high.
以上のように、実装品の相対向する電極間に存在する直鎖状金属粉末が、実装品の接続抵抗や接続信頼性に与える影響が大きいことから、実装品の相対向する電極間における直鎖状金属粉末の存在を非破壊で評価する手段が求められていた。 As described above, the linear metal powder existing between the electrodes facing each other in the mounted product has a great influence on the connection resistance and connection reliability of the mounted product. There has been a demand for means for nondestructively evaluating the presence of chain metal powder.
すなわち、本発明の課題は、異方導電膜、または、異方導電膜を用いて実装した実装品の相対向する電極間に存在する導電成分を、評価することができる直鎖状金属粉末を提供することにある。また、このような評価が可能な直鎖状金属粉末の製造方法を提供することにある。 That is, an object of the present invention is to provide a linear metal powder capable of evaluating an anisotropic conductive film or a conductive component existing between opposing electrodes of a mounted product mounted using the anisotropic conductive film. It is to provide. Moreover, it is providing the manufacturing method of the linear metal powder in which such evaluation is possible.
本発明の、別の課題は、また、このような直鎖状金属粉末を含有する異方導電膜、および前記異方導電膜を用いて実装した実装品を提供することにある。 Another object of the present invention is to provide an anisotropic conductive film containing such a linear metal powder, and a mounted product mounted using the anisotropic conductive film.
本発明者達は、前記課題を解決するために鋭意研究開発をした結果、直鎖状金属粉末の表面に蛍光物質が結合した蛍光標識金属粉末を作製することができれば非破壊で評価することができることを見いだした。 As a result of diligent research and development to solve the above problems, the present inventors can evaluate non-destructively if it is possible to produce a fluorescently labeled metal powder in which a fluorescent substance is bonded to the surface of a linear metal powder. I found what I could do.
前記蛍光標識金属粉末を含有する異方導電膜を用いて実装した実装品は、切断して断面を調整する等の破壊をすることなく、基板の外側から励起光を照射すれば、実装品中の蛍光標識金属粉末から蛍光が発せられ、該蛍光を検出することで、実装品の相対向する電極間に存在する導電成分を観察することが可能となる。本発明は、これらの知見に基づいて完成するに至ったものである。 The mounted product mounted using the anisotropic conductive film containing the fluorescently labeled metal powder can be mounted in the mounted product by irradiating excitation light from the outside of the substrate without breaking such as cutting and adjusting the cross section. Fluorescence is emitted from the fluorescent-labeled metal powder, and by detecting the fluorescence, it is possible to observe the conductive component existing between the electrodes facing each other in the mounted product. The present invention has been completed based on these findings.
すなわち本発明は、多数の微細な金属粒から形成された直鎖状の金属粉末であって、該金属粉末の表面に蛍光物質が直接に、または、有機化合物を介して結合していることを特徴とする蛍光標識金属粉末に係わるものである。直接または有機化合物を介して金属粉末に蛍光物質が結合することにより、金属粉末に励起光を照射すると、金属粉末から蛍光を発することができる。そのため、前記金属粉末を含有する異方導電膜を用いて実装した実装品においても、この蛍光を指標に実装品の相対向する電極間における直鎖状金属粉末の存在を非破壊で評価することができる。 That is, the present invention is a linear metal powder formed from a large number of fine metal particles, and the phosphor is bound to the surface of the metal powder directly or via an organic compound. The present invention relates to a characteristic fluorescently labeled metal powder. When the fluorescent substance is bonded to the metal powder directly or via an organic compound, the metal powder can emit fluorescence when irradiated with excitation light. Therefore, in the mounted product mounted using the anisotropic conductive film containing the metal powder, the presence of the linear metal powder between the opposing electrodes of the mounted product is evaluated nondestructively using this fluorescence as an index. Can do.
本発明に係わる前記有機化合物は、アビジン、ストレプトアビジン、ビオチン、グルタルアルデヒド、ヒスチジンおよびシランカップリング剤から選ばれる１種もしくは数種類組み合わせた複合体であることを特徴としている。有機化合物として、前記アビジン、ストレプトアビジン、ビオチン、グルタルアルデヒド、ヒスチジンおよびシランカップリング剤を用いることで種々の蛍光物質を金属粉末に結合することができる。また、有機化合物１分子に対し複数分子の蛍光物質を結合させることも可能であることから、蛍光標識金属粉末の感度を上げることが可能となる。 The organic compound according to the present invention is characterized in that it is a complex in which one or several kinds selected from avidin, streptavidin, biotin, glutaraldehyde, histidine and a silane coupling agent are combined. By using the avidin, streptavidin, biotin, glutaraldehyde, histidine and silane coupling agent as the organic compound, various fluorescent substances can be bound to the metal powder. In addition, since it is possible to bind a plurality of molecules of fluorescent substances to one molecule of the organic compound, it is possible to increase the sensitivity of the fluorescently labeled metal powder.
本発明に係わる前記蛍光物質は、前記有機化合物と結合する官能基を有することを特徴としている。蛍光物質に官能基を導入することで、金属粉末または、有機化合物との結合反応が室温で速やかに進行するとともに、共有結合という強固な結合からなる蛍光標識金属粉末を得ることが可能となる。 The fluorescent substance according to the present invention has a functional group that binds to the organic compound. By introducing a functional group into the fluorescent substance, it becomes possible to obtain a fluorescently labeled metal powder consisting of a strong bond called a covalent bond while the binding reaction with the metal powder or the organic compound proceeds rapidly at room temperature.
また本発明は、多数の微細な金属粒から形成された直鎖状の金属粉末と、（１）蛍光物質を含む溶液、または、（２）蛍光物質と有機化合物の混合物を含む溶液、とを混合して、前記金属粉末の表面に蛍光物質を結合させた後に、前記金属粉末を磁力で沈降させ、溶液から分離することにより蛍光標識金属粉末を回収することを特徴とする蛍光標識金属粉末の製造方法に係わる発明である。金属粉末の磁性を利用し、磁力で金属粉末のみを沈殿させることができるため、過剰に加えられた蛍光物質や、有機化合物を容易に除去できる。このあと例えば、洗浄液を用いて蛍光物質が結合した金属粉末を洗浄すれば、蛍光物質との非特異的な結合を少なくすることができるため、評価の際に、バックグラウンドの蛍光が少なくなり、精度良い評価を行うことが可能となる。 The present invention also includes a linear metal powder formed from a large number of fine metal particles, and (1) a solution containing a fluorescent substance, or (2) a solution containing a mixture of a fluorescent substance and an organic compound. A fluorescent-labeled metal powder is obtained by mixing and binding a fluorescent substance to the surface of the metal powder, and then recovering the fluorescent-labeled metal powder by precipitating the metal powder magnetically and separating from the solution. This invention relates to a manufacturing method. Since only the metal powder can be precipitated by magnetic force using the magnetism of the metal powder, excessively added fluorescent substances and organic compounds can be easily removed. After this, for example, if the metal powder to which the fluorescent substance is bound is washed using a washing solution, non-specific binding with the fluorescent substance can be reduced, so the background fluorescence is reduced during the evaluation, It becomes possible to evaluate with high accuracy.
また本発明は、前記蛍光標識金属粉末を、膜の厚み方向に配向させた状態で含有することを特徴とする異方導電膜に係わる発明である。蛍光標識金属粉末を用いて異方導電膜を作製しているので、異方導電膜を用いて実装した実装品の相対向する電極間に存在する、導電成分である蛍光標識金属粉末を評価する際に、この異方導電膜から発する蛍光を指標に評価することが可能となる。 The present invention also relates to an anisotropic conductive film comprising the fluorescently labeled metal powder in a state of being oriented in the thickness direction of the film. Since the anisotropically conductive film is made using the fluorescently labeled metal powder, the fluorescently labeled metal powder that is a conductive component existing between the opposing electrodes of the mounted product mounted using the anisotropically conductive film is evaluated. At this time, it is possible to evaluate using the fluorescence emitted from the anisotropic conductive film as an index.
さらに本発明は、前記異方導電膜を用いて基板に電子部品を実装したことを特徴とする実装品に係わる発明である。ここでいう基板とは、電子部品を実装する基板であれば特に限定されない。また、蛍光標識金属粉末を、膜の厚み方向に配向させた状態で含有する異方導電膜を用いるため、光を透過する基板が好適で、ガラス基板、単結晶サファイア基板、透明ポリマーからなる透明基板などが例示される。また、電子部品とは、ＩＣチップやボール・グリッド・アレイ（Ｂａｌｌ Ｇｒｉｄ Ａｒｒａｙ；ＢＧＡ）、チップサイズパッケージ（Ｃｈｉｐ Ｓｉｚｅ Ｐａｃｋａｇｅ；ＣＳＰ）などの半導体パッケージの他、フレキシブルプリント配線板やガラス基板も含まれる。従って、本発明に係わる実装品には、ガラス基板に異方導電膜を用いてＩＣチップを実装したものや、ガラス基板に異方導電膜を用いてプリント配線板を実装した（接続した）ものも含まれる。蛍光標識金属粉末を用いて作製した異方導電膜を用いて実装品を作り上げているので、実装品の評価をする際に、この蛍光を指標に実装品の相対向する電極間における直鎖状金属粉末の存在を非破壊で評価することができる。 Furthermore, the present invention relates to a mounted product characterized in that an electronic component is mounted on a substrate using the anisotropic conductive film. The substrate here is not particularly limited as long as it is a substrate on which electronic components are mounted. In addition, since an anisotropic conductive film containing fluorescently labeled metal powder oriented in the thickness direction of the film is used, a substrate that transmits light is suitable, and a glass substrate, a single crystal sapphire substrate, and a transparent polymer are used. Examples include substrates. Electronic components include IC packages, ball grid arrays (BGA), semiconductor packages such as chip size packages (CSP), flexible printed wiring boards and glass substrates. . Therefore, in the mounted product according to the present invention, an IC chip is mounted on a glass substrate using an anisotropic conductive film, or a printed wiring board is mounted (connected) on the glass substrate using an anisotropic conductive film. Is also included. Since the mounting product is made using the anisotropic conductive film produced using the fluorescently labeled metal powder, when evaluating the mounting product, the linearity between the electrodes facing each other is measured using this fluorescence as an index. The presence of metal powder can be evaluated non-destructively.
本発明の蛍光標識金属粉末は、励起光を照射すると、金属粉末から蛍光を発することができるため、実装品に作り上げた後でも、この蛍光を指標に実装品の相対向する電極間における直鎖状金属粉末の存在を非破壊で評価することができる。また、本発明の蛍光標識金属粉末の製造方法によれば、蛍光標識金属粉末の回収を効率よく行うとともに、未反応の蛍光物質を容易に除去できる利点がある。 Since the fluorescent-labeled metal powder of the present invention can emit fluorescence from the metal powder when irradiated with excitation light, even after it is made into a mounted product, the linear chain between the opposing electrodes of the mounted product using this fluorescence as an index. The presence of the metal powder can be evaluated nondestructively. Moreover, according to the method for producing a fluorescently labeled metal powder of the present invention, there are advantages that the fluorescently labeled metal powder can be efficiently recovered and an unreacted fluorescent substance can be easily removed.
次に本発明を実施するための最良の形態について説明する。本発明に用いる金属粉末としては、平均粒径が数μｍ〜数十μｍ程度で、かつその形状が粒状、球状、薄片状（鱗片状、フレーク状）の金属粉末も使えなくはないが、異方導電膜として利用するには、多数の微細な金属粒から形成された直鎖状金属粉末が好ましい。直鎖状金属粉末は、例えば、以下の方法で製造することができる。すなわち、（１）強磁性を有する金属イオンを含む水溶液に一定方向の磁場をかけながら、当該水溶液中で、還元剤の作用によって、上記金属のイオンを還元させて、微細な金属粒として析出させる。（２）析出させた多数の金属粒を、自身の持つ磁性によって、印加した磁場方向に配向させながら直鎖状に繋がらせて直鎖状金属粉末を製造する。このとき、還元析出反応は、金属イオンを還元させる際にガスを発生させる還元剤、または還元剤とガスを発生させる発泡剤とを組み合わせて行うことができる。また、ガスの発生により、水溶液上面に泡の層を生成させる起泡性を有する水溶性化合物の存在下で行い、水溶液上面に形成される泡の層を水溶液から分離して、この泡の層中に含まれる直鎖状金属粉末を回収することで製造することができる。 Next, the best mode for carrying out the present invention will be described. As the metal powder used in the present invention, metal powder having an average particle diameter of about several μm to several tens μm and having a granular shape, a spherical shape, and a flaky shape (scale shape, flake shape) may be used. A linear metal powder formed from a large number of fine metal particles is preferred for use as a method conductive film. The linear metal powder can be produced, for example, by the following method. (1) While applying a magnetic field in a certain direction to an aqueous solution containing metal ions having ferromagnetism, the metal ions are reduced and precipitated as fine metal particles in the aqueous solution by the action of a reducing agent. . (2) A large number of precipitated metal particles are connected in a straight line while being oriented in the direction of the applied magnetic field by the magnetic properties of the metal particles, thereby producing a linear metal powder. At this time, the reduction precipitation reaction can be performed by combining a reducing agent that generates a gas when reducing metal ions, or a reducing agent and a blowing agent that generates a gas. Further, the generation of gas is performed in the presence of a water-soluble compound having a foaming property to generate a foam layer on the upper surface of the aqueous solution, and the foam layer formed on the upper surface of the aqueous solution is separated from the aqueous solution. It can manufacture by collect | recovering the linear metal powder contained in it.
１．直鎖状金属粉末
本発明の製造方法によって製造される本発明の蛍光標識金属粉末に用いる金属粉末としては、例えば、下記（Ａ）〜（Ｄ）のいずれか１種、もしくは２種以上の混合物などを挙げることができる。
（Ａ）強磁性を有する金属単体、強磁性を有する２種以上の金属の合金、または強磁性を有する金属と他の金属との合金から形成したサブミクロンオーダーの金属粒を、多数個繋がらせた直鎖状金属粉末。
（Ｂ）上記（Ａ）の直鎖状金属粉末の表面にさらに、強磁性を有する金属単体、強磁性を有する２種以上の金属の合金、または強磁性を有する金属と他の金属との合金からなる金属層を被覆して、金属粒間を、金属結合と同程度の結合力によって強固に結合した直鎖状金属粉末。
（Ｃ）上記（Ａ）の直鎖状金属粉末の表面にさらに、他の金属や合金からなる被覆層を被覆して、金属粒間を、金属結合と同程度の結合力によって強固に結合した直鎖状金属粉末。
（Ｄ）上記（Ｂ）の直鎖状金属粉末の表面にさらに、他の金属や合金からなる被覆層を被覆して、金属粒間を、金属結合と同程度の結合力によって強固に結合した直鎖状金属粉末。
1. Linear metal powder As a metal powder used for the fluorescent labeling metal powder of the present invention produced by the production method of the present invention, for example, any one of the following (A) to (D), or a mixture of two or more kinds: And so on.
(A) A single metal having ferromagnetism, an alloy of two or more metals having ferromagnetism, or a large number of submicron-order metal particles formed from an alloy of a metal having ferromagnetism and another metal are connected. Straight metal powder.
(B) On the surface of the linear metal powder of (A) above, a single metal having ferromagnetism, an alloy of two or more metals having ferromagnetism, or an alloy of a metal having ferromagnetism and another metal A linear metal powder in which a metal layer is coated and the metal particles are firmly bonded to each other with a bonding strength similar to that of a metal bond.
(C) The surface of the linear metal powder of (A) is further coated with a coating layer made of another metal or alloy, and the metal particles are firmly bonded with the same bonding strength as the metal bond. Linear metal powder.
(D) The surface of the linear metal powder of (B) is further coated with a coating layer made of another metal or alloy, and the metal particles are firmly bonded with the same bonding strength as the metal bond. Linear metal powder.
金属粒を形成する、強磁性を有する金属または合金としては、例えばニッケル、鉄、コバルトおよびこれらのうち２種以上の合金等をあげることができ、とくにニッケル単体やニッケル−鉄合金（パーマロイ）等が好ましい。かかる金属や合金にて形成した金属粒は、直鎖状に繋がる際の磁気的な相互作用が強いため、金属粒間の接触抵抗を低減して、直鎖状金属粉末内での導電性を向上する効果に優れている。 Examples of metals or alloys having ferromagnetism that form metal grains include nickel, iron, cobalt, and two or more of these alloys. Particularly, nickel alone, nickel-iron alloys (permalloy), etc. Is preferred. Since metal particles formed from such metals and alloys have a strong magnetic interaction when connected in a straight chain, the contact resistance between the metal particles is reduced and the conductivity in the straight metal powder is reduced. Excellent improvement effect.
また上記の、強磁性を有する金属や合金とともに直鎖状金属粉末を形成する他の金属としては、Ｃｕ、Ｒｂ、Ｒｈ、Ｐｄ、Ａｇ、Ｒｅ、ＰｔおよびＡｕからなる群より選ばれた少なくとも１種の、導電性に優れた金属やその合金などをあげることができる。直鎖状金属粉末の導電性を向上することを考慮すると、これらの金属で形成する部分は、上記（Ｃ）、（Ｄ）のように、鎖の外表面に露出した被覆層であるのが好ましい。 In addition, the other metal forming the linear metal powder together with the ferromagnetic metal or alloy is at least one selected from the group consisting of Cu, Rb, Rh, Pd, Ag, Re, Pt and Au. Examples thereof include metals having excellent conductivity and alloys thereof. In consideration of improving the conductivity of the linear metal powder, the portion formed of these metals is a coating layer exposed on the outer surface of the chain as in (C) and (D) above. preferable.
被覆層は、析出した金属粉末が直鎖状に繋がって直鎖状金属粉末が形成された後も還元析出を続けることによって形成される。また被覆層は、例えば無電解めっき法、電解めっき法、還元析出法、真空状着法などの種々の成膜方法によって形成できる。被覆層は、上記の導電性に優れた金属や合金からなる単層構造を有していてもよいし、同一または異なる金属や合金からなる２層以上の積層構造を有していてもよい。 The coating layer is formed by continuing the reduction deposition even after the deposited metal powder is connected in a straight chain to form a linear metal powder. The coating layer can be formed by various film forming methods such as electroless plating, electrolytic plating, reduction deposition, and vacuum deposition. The coating layer may have a single-layer structure made of the above-described highly conductive metal or alloy, or may have a laminated structure of two or more layers made of the same or different metals or alloys.
２．還元剤
本発明の製造方法に用いる還元剤としては、水溶液中で、金属のイオンを還元して金属粒を析出させる機能を有する種々の還元剤が、いずれも使用可能であるが、特に、金属のイオンを還元させる際にガスを発生させる還元剤が好ましい。そのような還元剤としては、例えば、下記に示す各種の還元剤が挙げられ、特にＴｉ（ＩＶ）とクラスター化したＴｉ（ＩＩＩ）が好ましい。
2. As the reducing agent used in the production method of the present invention, various reducing agents having a function of reducing metal ions to precipitate metal particles in an aqueous solution can be used. A reducing agent that generates gas when reducing the ions is preferable. Examples of such a reducing agent include various reducing agents shown below, and Ti (IV) clustered with Ti (IV) is particularly preferable.
Ｔｉ（ＩＶ）とクラスター化したＴｉ（ＩＩＩ）は、金属のイオンを還元させる際に、水を還元して水素ガスを発生させる。チタンイオンは、析出させた金属粒中に、不純物として殆ど混入しないため、高純度の直鎖状金属粉末を製造できる。このため、例えば鉄やコバルトなどの、バルク材における飽和磁化の大きい金属だけでなく、例えばバルク材における飽和磁化が小さいニッケルであっても、高純度で磁性の強い金属粒を生成できるため、その金属粒を多数、自身の持つ磁性によって、印加した磁場方向に配向させながら、直鎖状に繋がらせて直鎖状金属粉末を製造することができる。 Ti (IV) clustered with Ti (IV) reduces hydrogen to generate hydrogen gas when reducing metal ions. Since titanium ions are hardly mixed as impurities in the precipitated metal particles, a high-purity linear metal powder can be produced. For this reason, since not only metals with large saturation magnetization in bulk materials, such as iron and cobalt, but also nickel with small saturation magnetization in bulk materials, for example, high purity and strong magnetic metal grains can be generated. A linear metal powder can be produced by connecting a large number of metal particles in a straight line while being oriented in the applied magnetic field direction by the magnetic properties of the metal particles.
また、Ｔｉ（ＩＶ）とクラスター化したＴｉ（ＩＩＩ）を還元剤に用いることにより、金属粒の真球度を高めることができる上、その１次粒子径をより小さくすることができる。すなわち、Ｔｉ（ＩＶ）は金属粒の成長を抑制する機能を有する上、液中で、Ｔｉ（ＩＩＩ）とともに複数個ずつがクラスターを構成して、全体として水和および錯体化した状態で存在するため、この共存した状態で還元析出反応を行うようにすると、１つのクラスター中で、１つの同じ金属粒に、Ｔｉ（ＩＩＩ）による成長促進の機能と、Ｔｉ（ＩＶ）による成長抑制の機能とが作用して、金属粒を通常よりもゆっくり成長させることができ、結果として、金属粒の真球度を高めるとともに、その一次粒子径をより小さくすることができる。 Further, by using Ti (IV) clustered with Ti (IV) as a reducing agent, the sphericity of the metal particles can be increased and the primary particle diameter can be further reduced. That is, Ti (IV) has a function of suppressing the growth of metal grains, and in the liquid, a plurality of Ti (IV) and the Ti (III) form a cluster, and exist in a hydrated and complexed state as a whole. Therefore, when the reduction precipitation reaction is carried out in this coexisting state, the function of promoting growth by Ti (III) and the function of suppressing growth by Ti (IV) are applied to one same metal particle in one cluster. As a result, the metal grains can be grown more slowly than usual, and as a result, the sphericity of the metal grains can be increased and the primary particle diameter thereof can be further reduced.
また、この方法によれば、Ｔｉ（ＩＩＩ）とＴｉ（ＩＶ）の存在比率を調整することによって、クラスター中での、両者の、相反する機能の強弱の割合を変更できるため、金属粒の一次粒子径を任意に制御することも可能である。しかも、直鎖状金属粉末を製造した後の、全てのチタンイオンが４価に酸化した水溶液を電解再生して、チタンイオンの一部を再び３価に還元することによって、液を繰り返し、直鎖状金属粉末の製造に利用可能な状態に再生することができ、直鎖状金属粉末の製造工程のコストダウンを図ることができるという利点もある。 Further, according to this method, by adjusting the abundance ratio of Ti (III) and Ti (IV), it is possible to change the ratio of the strengths of the conflicting functions in the cluster. It is also possible to arbitrarily control the particle size. In addition, after the production of the linear metal powder, the aqueous solution in which all the titanium ions are oxidized to tetravalent is electrolytically regenerated, and a portion of the titanium ions are reduced again to trivalent, whereby the liquid is repeated. There is also an advantage that it can be regenerated into a state that can be used for the production of the chain metal powder, and the cost of the production process of the linear metal powder can be reduced.
次亜リン酸ナトリウムなどの次亜リン酸塩類は、金属のイオンを還元させる際に、水を還元して水素ガスを発生させる。還元析出の際に、リンが不純物として混入するため、特にニッケルの場合は非磁性のリン化合物（Ｎｉ３Ｐ）を生成して、金属粒の飽和磁化が低下するおそれがある。しかし、例えば鉄やコバルト合金などの、バルク材における飽和磁化の大きい金属では、その金属粒を多数、自身の持つ磁性によって、印加した磁場方向に配向させながら、直鎖状に繋がらせて直鎖状金属粉末を製造することができる。 Hypophosphites such as sodium hypophosphite reduce water to generate hydrogen gas when reducing metal ions. Since phosphorus is mixed as an impurity during the reduction precipitation, particularly in the case of nickel, a nonmagnetic phosphorus compound (Ni3P) may be generated, and the saturation magnetization of the metal particles may be reduced. However, for metals with large saturation magnetization in bulk materials, such as iron and cobalt alloys, many metal grains are aligned in the direction of the applied magnetic field by their own magnetism, and are connected in a straight chain. A metal powder can be produced.
ジメチルアミノボランなどの水素化ホウ素化合物は、金属のイオンを還元させる際に、水を還元して水素ガスを発生させる。還元析出の際に、ホウ素が不純物として混入するため、特にニッケルの場合は、金属粒の飽和磁化が低下するおそれがある。しかし、鉄や鉄−コバルト合金などの、バルク材における飽和磁化の大きい金属では、その金属粒を多数、自身の持つ磁性によって、印加した磁場方向に配向させながら、直鎖状に繋がらせて直鎖状金属粉末を製造することができる。 Boron hydride compounds such as dimethylaminoborane reduce water to generate hydrogen gas when reducing metal ions. Since boron is mixed as an impurity during reduction precipitation, particularly in the case of nickel, the saturation magnetization of metal particles may be reduced. However, for metals with large saturation magnetization in bulk materials such as iron and iron-cobalt alloys, a number of metal grains are aligned in the direction of the applied magnetic field by their own magnetism and directly connected in a straight chain. A chain metal powder can be produced.
ヒドラジンは、金属のイオンを還元させる際に、水を還元して水素ガスを発生させる。析出させた金属粒中に、不純物として混入する成分を有しないため、高純度の直鎖状金属粉末を製造できる。このためニッケルなどの、バルク材における飽和磁化が小さい金属であっても、その金属粒を多数、自身の持つ磁性により、印加した磁場方向に配向させながら、直鎖状に繋がらせて直鎖状金属粉末を製造することができる。 Hydrazine reduces water to generate hydrogen gas when reducing metal ions. Since the precipitated metal particles do not have a component mixed as an impurity, a highly pure linear metal powder can be produced. For this reason, even if the metal has a small saturation magnetization in the bulk material, such as nickel, the metal particles are connected in a straight line while being oriented in the applied magnetic field direction by the magnetism of the metal particles. Metal powder can be produced.
ただし、例えばエチレングリコール等のポリオール類その他、金属のイオンを還元させる際にガスを発生しない還元剤を使用することもできる。その際には、例えば、低沸点のアルコール等を、還元剤と別個にガスを発生させる発泡剤として併用し、反応時の熱によってこのアルコール等を気化させてガスを発生させるようにしてもよい。 However, for example, polyols such as ethylene glycol and other reducing agents that do not generate gas when reducing metal ions can be used. In that case, for example, a low-boiling point alcohol or the like may be used in combination as a blowing agent that generates a gas separately from the reducing agent, and the alcohol or the like may be vaporized by heat during the reaction to generate a gas. .
３．起泡性の水溶性化合物
ガスの発生により、水溶液上面に安定な泡の層を生成させる、起泡性を有する水溶性化合物としては、起泡性を有する種々の水溶性化合物が、いずれも使用可能である。中でも特に、析出した金属粒や直鎖状金属粉末の周りを包み込む機能を有する分散剤のうち、起泡性を兼ね備えたものを選択して用いるのが好ましい。
3. Foamable water-soluble compounds A variety of water-soluble compounds with foaming properties are used as the foamable water-soluble compounds that generate a stable foam layer on the upper surface of an aqueous solution by the generation of gas. Is possible. Among them, it is particularly preferable to select and use a dispersant having a foaming property among the dispersing agents having a function of wrapping around the precipitated metal particles and linear metal powder.
起泡性を有する分散剤を用いることにより、起泡性を有する水溶性化合物と分散剤とを併用する場合に比べて、直鎖状金属粉末の製造工程のコストダウンを図ることができる。また分散剤は、還元析出反応によって金属粒を析出させる際に、析出した多数の金属粒が磁場の方向に配向するように繋がって形成される鎖の周りを包み込んで、鎖に枝分かれが発生したり、複数の鎖が凝集したりするのを抑制するため、枝分かれの少ない、ほぼ直鎖状の金属粉末を製造することができる。しかも、製造される直鎖状金属粉末は、分散剤によって包み込まれることで疎水性になって、水よりもガスの気泡に対する親和性が向上し、気泡に付着して泡の層に運ばれやすくなることから、泡の層中に含まれる、鎖長の短い直鎖状金属粉末の回収効率を向上することもできる。 By using the foaming dispersant, it is possible to reduce the cost of the production process of the linear metal powder as compared with the case where the foamable water-soluble compound and the dispersant are used in combination. In addition, when a metal particle is precipitated by a reductive precipitation reaction, the dispersing agent wraps around the chain formed by connecting a number of precipitated metal particles so that they are oriented in the direction of the magnetic field, and branching occurs in the chain. In order to suppress the aggregation of a plurality of chains, it is possible to produce a substantially linear metal powder with few branches. Moreover, the linear metal powder to be produced becomes hydrophobic by being encapsulated by a dispersant, and the affinity for gas bubbles is improved compared to water, so that it adheres to the bubbles and is easily carried to the foam layer. Thus, the recovery efficiency of the linear metal powder having a short chain length contained in the foam layer can also be improved.
起泡性を有する分散剤としては、下記に示す各種の分散剤が挙げられる。スチレン含量、イソブチレン含量の重量％は、該当する繰り返し単位の、全繰り返し単位中に占める重量百分率、個数％は、該当する繰り返し単位の、全繰り返し単位中に占める個数百分率である。
（ｉ）スチレン−無水マレイン酸ランダム共重合体〔数平均分子量１７００、スチレン含量６８重量％〕
（ｉｉ）イソブチレン−無水マレイン酸交互共重合体の部分アンモニウム塩化合物〔重量平均分子量１６５５００、イソブチレン含量５０個数％〕
（ｉｉｉ）セルナＤ−７３５〔中京油脂(株)製の商品名、有効成分であるスチレン−マレイン酸共重合体（重量平均分子量１９０００）とアンモニアと水との混合物〕
Examples of the foaming dispersant include various dispersants shown below. The weight percent of styrene content and isobutylene content is the weight percentage of the corresponding repeating unit in all repeating units, and the number percent is the number percentage of the corresponding repeating unit in all repeating units.
(I) Styrene-maleic anhydride random copolymer [number average molecular weight 1700, styrene content 68% by weight]
(Ii) Partial ammonium salt compound of alternating isobutylene-maleic anhydride copolymer [weight average molecular weight 165500, isobutylene content 50 number%]
(Iii) Serna D-735 [trade name, manufactured by Chukyo Oil & Fat Co., Ltd., a mixture of styrene-maleic acid copolymer (weight average molecular weight 19000) as an active ingredient, ammonia and water]
また、起泡性を有しない分散剤と、起泡性を有する水溶性化合物とを併用しても、コストダウンの効果は得られないが、それ以外は同様の効果が得られる。このうち、起泡性を有しない分散剤としては、下記に示す各種の分散剤が挙げられる。スチレン含量は、前記と同様である。また、起泡性を有しない分散剤と併用される起泡性の水溶性化合物としては、各種石けん系界面活性剤などが挙げられる。
（ｉｖ）スチレン−無水マレイン酸ランダム共重合体〔数平均分子量１９００、スチレン含量７５重量％〕
（ｖ）スチレン−無水マレイン酸ランダム共重合体の部分エステル化物〔数平均分子量１９００、スチレン含量６７個数％、プロピルエステル〕
（ｖｉ）スチレン−マレイン酸ランダム共重合体の部分エステル化物〔重量平均分子量６５０００、スチレン含量５０％超、イソブチルエステル〕
Moreover, even if a dispersant having no foaming property and a water-soluble compound having foaming property are used in combination, the cost reduction effect cannot be obtained, but otherwise the same effect is obtained. Among these, various dispersing agents shown below are mentioned as a dispersing agent which does not have foamability. The styrene content is the same as described above. Moreover, various soap type surfactants etc. are mentioned as a foamable water-soluble compound used together with the dispersing agent which does not have foamability.
(Iv) Styrene-maleic anhydride random copolymer [number average molecular weight 1900, styrene content 75% by weight]
(V) Partially esterified product of styrene-maleic anhydride random copolymer [number average molecular weight 1900, styrene content 67% by number, propyl ester]
(Vi) Partially esterified product of styrene-maleic acid random copolymer (weight average molecular weight 65000, styrene content more than 50%, isobutyl ester)
なお、上記各種分散剤のうち（ｉ）、（ｉｉ）、（ｉｖ）、（ｖ）、（ｖｉ）などの分散剤は、水溶液中に析出した金属粒の周囲を大きく包んで、金属粒同士の近接と、磁性による連結と、それによる鎖の成長とをより良好に制御して、鎖長がほぼ一定の範囲内に揃った直鎖状金属粉末を製造する効果も有している。したがって、これらの分散剤を使用すれば、泡の層中に含まれる、鎖長の短い直鎖状金属粉末の回収効率をより一層、向上することもできる。 Of the various dispersants described above, the dispersants such as (i), (ii), (iv), (v), and (vi) largely wrap around the metal particles precipitated in the aqueous solution. Further, it has an effect of producing a linear metal powder having a chain length in a substantially constant range by better controlling the proximity of each other, magnetic coupling, and chain growth thereby. Therefore, the use of these dispersants can further improve the recovery efficiency of the linear metal powder having a short chain length contained in the foam layer.
分散剤は、起泡性を有するものと、有しないもののいずれの場合も、析出させる直鎖状金属粉末１００重量部に対して０．５〜１００重量部の割合で液に含有させるのが好ましい。また、分散剤を加えることによる、枝分かれの発生を抑制したり、直鎖状金属粉末を疎水性にしたり、鎖長をほぼ一定の範囲内に揃えたりする効果をより一層、良好なものとするためには、その含有割合は、上記の範囲内でも特に、直鎖状金属粉末１００重量部に対して５重量部以上であるのがさらに好ましい。また、液の粘度が高くなりすぎるのを防止して、液中に析出した金属粒がよりスムースに、直鎖状に繋がるのを促進することを考慮すると、分散剤の含有割合は、上記の範囲内でも特に、直鎖状金属粉末１００重量部に対して５０重量部以下であるのがさらに好ましい。 The dispersant is preferably contained in the liquid at a ratio of 0.5 to 100 parts by weight with respect to 100 parts by weight of the linear metal powder to be precipitated, regardless of whether the dispersant has foamability or not. . In addition, the effects of suppressing the occurrence of branching by adding a dispersant, making the linear metal powder hydrophobic, and aligning the chain length within a substantially constant range are further improved. Therefore, the content ratio is more preferably 5 parts by weight or more with respect to 100 parts by weight of the linear metal powder, even in the above range. Further, in consideration of preventing the viscosity of the liquid from becoming too high and promoting that the metal particles precipitated in the liquid are more smoothly and linearly connected, the content of the dispersant is as described above. Even within the range, the amount is more preferably 50 parts by weight or less with respect to 100 parts by weight of the linear metal powder.
４．直鎖状金属粉末の製造
還元剤として、前記のように金属のイオンを還元させる際にガスを発生させる機能を有する、Ｔｉ（ＩＶ）とクラスター化したＴｉ（ＩＩＩ）を用いた、本発明に用いる直鎖状金属粉末の製造方法の、実施の形態の一例においては、まず、（１）金属粒のもとになる１種または２種以上の金属のイオンと錯化剤とを含む水溶液（以下「金属イオン溶液」とする）と、（２）Ｔｉ（ＩＩＩ）とＴｉ（ＩＶ）とを含む水溶液（以下「還元剤溶液」とする）と、（３）起泡性を有する分散剤、もしくは、起泡性を有しない分散剤と起泡性を有する水溶性化合物と、ｐＨ調整剤としてのアンモニア等とを含む水溶液（以下「分散剤溶液」とする）と、を個別に調製する。
4). Production of linear metal powder As the reducing agent, Ti (IV) and clustered Ti (III) having a function of generating gas when reducing metal ions as described above are used in the present invention. In an example of an embodiment of a method for producing a linear metal powder to be used, first, (1) an aqueous solution containing one or two or more kinds of metal ions and a complexing agent that forms metal particles ( Hereinafter referred to as “metal ion solution”), (2) an aqueous solution containing Ti (III) and Ti (IV) (hereinafter referred to as “reducing agent solution”), and (3) a foaming dispersant, Alternatively, an aqueous solution (hereinafter referred to as “dispersant solution”) containing a non-foaming dispersant, a foamable water-soluble compound, and ammonia or the like as a pH adjuster is prepared separately.
次に、金属イオン溶液に還元剤溶液を加えて混合した後、この混合液（以下「反応母液」とする）に一定方向の磁場をかけながら分散剤溶液を加えて、液のｐＨを９〜１０に調整する。そうすると、この混合液（以下「反応液」とする）中で、Ｔｉ（ＩＩＩ）とＴｉ（ＩＶ）と金属イオンとによってクラスターが形成され、このクラスター中で、３価のチタンイオンが錯化剤と結合して配位化合物を形成して、Ｔｉ（ＩＩＩ）からＴｉ（ＩＶ）に酸化する際の活性化エネルギーが低くなり、還元電位が高くなる。 Next, the reducing agent solution is added to the metal ion solution and mixed, and then the dispersing agent solution is added to this mixed solution (hereinafter referred to as “reaction mother liquor”) while applying a magnetic field in a certain direction to adjust the pH of the solution to 9 to 9. Adjust to 10. Then, in this mixed liquid (hereinafter referred to as “reaction liquid”), clusters are formed by Ti (III), Ti (IV), and metal ions, and in this cluster, trivalent titanium ions are complexed. To form a coordination compound, the activation energy when oxidizing from Ti (III) to Ti (IV) is lowered, and the reduction potential is raised.
具体的には、Ｔｉ（ＩＩＩ）とＴｉ（ＩＶ）との電位差が１Ｖを超える。この値は、Ｎｉ（ＩＩ）からＮｉ（０）への還元電位や、Ｆｅ（ＩＩ）からＦｅ（０）への還元電位などに比べて著しく高く、各種の金属のイオンを効率よく還元、析出させることができる値である。そして、Ｔｉ（ＩＩＩ）が還元剤として機能して、自身がＴｉ（ＩＶ）に酸化する際に、同じ液中に存在する１種または２種以上の金属のイオンを還元して液中に析出させる。すなわち反応液中に、前記金属単体または合金からなる微細な金属粒が多数、析出する。また、それとともに、クラスター中において、Ｔｉ（ＩＶ）が、金属粒の、急速でかつ不均一な成長を抑制する結果、析出した金属粒は、真球度が高く、かつ一次粒子径が小さいものとなる。 Specifically, the potential difference between Ti (III) and Ti (IV) exceeds 1V. This value is significantly higher than the reduction potential from Ni (II) to Ni (0), the reduction potential from Fe (II) to Fe (0), etc., and efficiently reduces and precipitates various metal ions. It is a value that can be made to. When Ti (III) functions as a reducing agent and oxidizes itself to Ti (IV), one or more kinds of metal ions present in the same liquid are reduced and deposited in the liquid. Let That is, a large number of fine metal particles made of the single metal or alloy are precipitated in the reaction solution. Along with that, Ti (IV) suppresses rapid and non-uniform growth of metal grains in the cluster. As a result, the precipitated metal grains have a high sphericity and a small primary particle diameter. It becomes.
さらに、析出した金属粒は、液にかけた磁場の作用によって、磁場に対応する方向、具体的には、磁場の磁束線に沿う方向に配列しながら直鎖状に繋がり、それによって、前記（Ａ）の直鎖状金属粉末や、（Ｃ）の、被覆層を被覆する前の直鎖状金属粉末が形成される。またこの際、分散剤の作用によって、鎖に枝分かれが発生したり、複数の鎖が凝集したりするのが抑制されるため、形成される直鎖状金属粉末は、枝分かれがなく、かつ直線性に優れたものとなる。しかも、還元析出反応は系中で均一に進行するため、直鎖状金属粉末を形成する個々の金属粒は粒径が揃っており、１次粒子径の粒度分布がシャープである。したがって、形成される直鎖状金属粉末は、その太さも均一に揃ったものとなる。 Further, the precipitated metal particles are connected in a straight line while being arranged in the direction corresponding to the magnetic field, specifically, the direction along the magnetic flux lines of the magnetic field, by the action of the magnetic field applied to the liquid. ) Linear metal powder and (C) linear metal powder before coating the coating layer. Further, at this time, since the branching of the chain or the aggregation of a plurality of chains is suppressed by the action of the dispersant, the formed linear metal powder has no branching and linearity. It will be excellent. Moreover, since the reduction precipitation reaction proceeds uniformly in the system, the individual metal particles forming the linear metal powder have a uniform particle size, and the particle size distribution of the primary particle size is sharp. Therefore, the formed linear metal powder has a uniform thickness.
また、液中に（Ａ）の直鎖状金属粉末が形成されたあともさらに析出を続けると、その表面にさらに金属層が析出して、金属粒同士を、金属結合と同程度の結合力によって強固に結合する。つまり、前記（Ｂ）の直鎖状金属粉末や、（Ｄ）の、被覆層を被覆する前の直鎖状金属粉末が形成される。 Further, if the precipitation is further continued after the linear metal powder (A) is formed in the liquid, a metal layer is further deposited on the surface, and the metal particles are bonded to each other with the same bonding strength as the metal bond. To bond firmly. That is, the linear metal powder (B) and the linear metal powder (D) before coating the coating layer are formed.
反応液中に生成した直鎖状金属粉末は、Ｔｉ（ＩＩＩ）が還元剤として機能して、自身がＴｉ（ＩＶ）に酸化する際に、水を還元することで発生した水素ガスの気泡と接触する。そうすると、直鎖状金属粉末は、分散剤によって包まれて疎水性になっており、水よりもガスの気泡に対する親和性が向上していることから、気泡の周囲に付着する。そして、比較的鎖長の短い、軽い直鎖状金属粉末は、気泡の上昇に伴って反応液の液面に運ばれて、その上面に形成される泡の層に蓄積される。一方、比較的鎖長の長い、重いものは、気泡に付着しても、その上昇に伴って気泡から脱落したり、気泡の上昇を妨げたりするため反応液中に留まる。 The linear metal powder produced in the reaction solution is composed of hydrogen gas bubbles generated by reducing water when Ti (III) functions as a reducing agent and oxidizes itself to Ti (IV). Contact. Then, the linear metal powder is wrapped with the dispersant and becomes hydrophobic, and the affinity for the gas bubbles is higher than that of water, so that the linear metal powder adheres around the bubbles. The light chain metal powder having a relatively short chain length is transported to the liquid level of the reaction liquid as the bubbles rise, and is accumulated in the foam layer formed on the upper surface thereof. On the other hand, even if a heavy chain having a relatively long chain length adheres to the bubble, it falls out of the bubble as it rises, or prevents the bubble from rising, so that it remains in the reaction solution.
このため、泡の層を液から分離して、この泡の層中に含まれる直鎖状金属粉末を回収すると、鎖長がほぼ一定の範囲内に揃った、鎖長の短い直鎖状金属粉末を製造することができる。また、反応液中に残った直鎖状金属粉末を回収すると、上記鎖長の短い成分が除去されることで、同様に鎖長がほぼ一定の範囲内に揃った、鎖長の長い直鎖状金属粉末を得ることもできる。 For this reason, when the foam layer is separated from the liquid and the linear metal powder contained in the foam layer is recovered, the linear metal with a short chain length in which the chain length is substantially within a certain range. A powder can be produced. In addition, when the linear metal powder remaining in the reaction solution is recovered, the above-described components having a short chain length are removed, and thus a linear chain having a long chain length that is similarly aligned in a substantially constant range. A metal powder can also be obtained.
還元析出反応時に、反応液にかける磁場の強さは特に限定されないが、磁束密度で表して５ｍＴ以上であるのが好ましい。磁場の強さを５ｍＴ以上とすると、地磁気や液の抵抗等に打ち勝って、析出初期の段階の微細な金属粒を、かけた磁場に対応する方向にきれいに配列できるため、直鎖状金属粉末の直線性をさらに向上することができる。 The strength of the magnetic field applied to the reaction solution during the reduction precipitation reaction is not particularly limited, but is preferably 5 mT or more in terms of magnetic flux density. If the strength of the magnetic field is 5 mT or more, it is possible to overcome the geomagnetism and resistance of the liquid, and fine metal particles at the initial stage of precipitation can be neatly arranged in the direction corresponding to the applied magnetic field. Linearity can be further improved.
なお、磁場の強さは、金属粒をできるだけきれいに直線状に配列させることを考慮すると、強ければ強いほど好ましいが、磁場があまりに強すぎてもそれ以上の効果が期待できないだけでなく、強い磁場を発生させるためのコイルや永久磁石が大掛かりになるため、液にかける磁場の強さは、８Ｔ以下であるのがさらに好ましい。 The strength of the magnetic field is preferably as strong as possible, considering that the metal grains are arranged in a straight line as cleanly as possible. However, if the magnetic field is too strong, not only a further effect cannot be expected, but also a strong magnetic field. Since a coil and a permanent magnet for generating a large amount are required, the strength of the magnetic field applied to the liquid is more preferably 8T or less.
また、還元析出反応は、例えば、前記各液を混合して反応液を調製する際に使用したかく拌棒を、混合終了時に、反対方向に数回、回転させるなどして液の流動を停止し、その後は液を実質的にかく拌せずに静置した状態を維持して行う、より詳しくは、かく拌速度で表して０．１ｒｐｍ以下、特に０ｒｐｍとした状態で行うのが好ましい。還元析出反応を上記の条件下で行うようにすると、液中に析出した金属粒やそれが繋がった鎖に、かく拌による応力が影響するのを防止して、直鎖状金属粉末の直線性を向上するとともに、一旦、繋がった鎖が応力によって切れたり、逆に複数の鎖が繋がったりするのを防止して、鎖長がばらつくのを防止することができる。 In addition, the reduction precipitation reaction, for example, stops the flow of the liquid by rotating the stirring rod used when preparing the reaction liquid by mixing each liquid several times in the opposite direction at the end of mixing. Thereafter, the liquid is maintained in a state where it is allowed to stand without being substantially stirred. More specifically, it is preferably carried out in a state of 0.1 rpm or less, particularly 0 rpm, expressed as a stirring speed. When the reduction precipitation reaction is carried out under the above conditions, the linearity of the linear metal powder is prevented by preventing the stress caused by stirring on the metal particles precipitated in the liquid and the chain to which the particles are connected. It is possible to prevent the chain length from varying by preventing the chain that has been once disconnected from being broken by stress or conversely connecting a plurality of chains.
直鎖状金属粉末を製造した後の液は、前記のように電解再生を行うことで、何度でも繰り返し、還元析出法による直鎖状金属粉末の製造に再利用することができる。すなわち、直鎖状金属粉末を製造した後の液を電解処理することで、Ｔｉ（ＩＶ）の一部をＴｉ（ＩＩＩ）に還元してやれば、再び還元剤溶液として使用することができる。これは、還元析出時にチタンイオンが殆ど消費されない、つまり析出させる金属とともに殆ど析出されないためである。 The liquid after the production of the linear metal powder can be reused in the production of the linear metal powder by the reductive precipitation method by repeating the electrolytic regeneration as described above, any number of times. That is, if a part of Ti (IV) is reduced to Ti (III) by electrolytic treatment of the liquid after the production of the linear metal powder, it can be used again as a reducing agent solution. This is because titanium ions are hardly consumed during the reduction deposition, that is, they are hardly deposited together with the metal to be deposited.
還元剤としてのチタンイオンは、例えば三塩化チタンや四塩化チタンなどの、水溶性の塩として供給する。すなわち、還元剤溶液中でのＴｉ（ＩＩＩ）とＴｉ（ＩＶ）の存在比率に応じた量の三塩化チタンと四塩化チタンとを配合するか、あるいは四塩化チタンのみを配合して、上に述べた使用後の液を再生する時と同様に液を電界処理して、Ｔｉ（ＩＶ）の一部をＴｉ（ＩＩＩ）に還元した状態で、還元析出反応に供すればよい。 Titanium ions as a reducing agent are supplied as water-soluble salts such as titanium trichloride and titanium tetrachloride. That is, blend titanium trichloride and titanium tetrachloride in amounts corresponding to the ratio of Ti (III) and Ti (IV) in the reducing agent solution, or blend only titanium tetrachloride, and The liquid may be subjected to a reduction precipitation reaction in a state where a part of Ti (IV) is reduced to Ti (III) by subjecting the liquid to electric field treatment in the same manner as in the case of regenerating the liquid after use.
液の再生時、および四塩化チタンのみを配合した液を電界処理して最初の還元剤溶液を調製する際には、電解処理の条件を調整することによって、還元剤溶液中でのＴｉ（ＩＩＩ）とＴｉ（ＩＶ）の存在比率を任意に調整することができ、それによって、上述したクラスター中での、両者の、相反する機能の強弱の割合を変更できるため、金属粒の一次粒子径を任意に制御することが可能である。 When the liquid is regenerated and when the first reducing agent solution is prepared by electric field treatment of the liquid containing only titanium tetrachloride, the conditions of the electrolytic treatment are adjusted to adjust the Ti (III in the reducing agent solution. ) And Ti (IV) can be arbitrarily adjusted, whereby the ratio of the strengths of the opposing functions in the above-described cluster can be changed. It is possible to control arbitrarily.
錯化剤としては、例えばエチレンジアミン、クエン酸、酒石酸、ニトリロ三酢酸、エチレンジアミン四酢酸などのカルボン酸や、あるいはそのナトリウム塩、カリウム塩、アンモニウム塩などを挙げることができる。また金属のイオンは、当該金属の、水溶性の塩として供給される。 Examples of the complexing agent include carboxylic acids such as ethylenediamine, citric acid, tartaric acid, nitrilotriacetic acid, and ethylenediaminetetraacetic acid, or sodium salts, potassium salts, and ammonium salts thereof. Metal ions are supplied as a water-soluble salt of the metal.
５．蛍光物質
金属粉末に標識する蛍光物質は、特に限定されないが、励起光の波長で蛍光を発する物質を適宜選択すればよい。例えば、４８８ｎｍ近傍の波長で励起する場合は、フルオロセイン及びイソシアネート等の誘導体、フィコエリスリン、ドーダミングリーン、ＧＦＰ（Ｇｒｅｅｎ ｆｌｕｏｒｅｓｅｎｔ ｐｒｏｔｅｉｎ）、ＹＯＹＯ１等を使用することができる。紫外線での励起光の場合は、ダンシルクロリド、カスケードブルー、ヘキスト３３３４２等の蛍光物質を使用することができる。６３３ｎｍ近傍での励起であれば、アロフィコシアニン及びその誘導体等が、好適に使用できる。
5. Fluorescent substance The fluorescent substance labeled on the metal powder is not particularly limited, and a substance that emits fluorescence at the wavelength of the excitation light may be appropriately selected. For example, in the case of excitation at a wavelength near 488 nm, derivatives such as fluorescein and isocyanate, phycoerythrin, dodamine green, GFP (Green fluorescein protein), YOYO1, etc. can be used. In the case of excitation light with ultraviolet light, fluorescent materials such as dansyl chloride, cascade blue, and Hoechst 33342 can be used. In the case of excitation at around 633 nm, allophycocyanin and its derivatives can be preferably used.
蛍光物質中に官能基があると、金属粉末や有機化合物との反応が速やかに進行するので、好適である。蛍光物質中に含まれる好適な官能基としては、イソシアネート基、アミノ基、水酸基、カルボキシル基、スルホニル基、エポキシ基、トシル基等が例示される。 When there is a functional group in the fluorescent material, the reaction with the metal powder or the organic compound proceeds quickly, which is preferable. Examples of suitable functional groups contained in the fluorescent material include isocyanate groups, amino groups, hydroxyl groups, carboxyl groups, sulfonyl groups, epoxy groups, and tosyl groups.
６．有機化合物
金属粉末に結合させる蛍光物質は、上記物質を金属粉末に直接結合させても良いが、有機化合物を介して結合させることも可能である。有機化合物としては、蛍光物質の官能基と容易に反応できるものであれば特に限定されないが、アビジン、ストレプトアビジン、ビオチン、グルタルアルデヒド、ヒスチジン、シランカップリング剤が好適に使用できる。これらの有機化合物は、１種単独で使用しても良いが、複数種を組み合わせても良く、また、複合体を形成しても良い。複合体を形成するときは、金属粉末と反応させる前に蛍光物質と事前に反応させておくこともできる。
6). The fluorescent substance to be bonded to the organic compound metal powder may be bonded directly to the metal powder, but can also be bonded via an organic compound. The organic compound is not particularly limited as long as it can easily react with the functional group of the fluorescent substance, but avidin, streptavidin, biotin, glutaraldehyde, histidine, and a silane coupling agent can be preferably used. These organic compounds may be used alone or in combination of two or more and may form a complex. When forming a complex, it can also be reacted in advance with a fluorescent substance before reacting with the metal powder.
蛍光物質にビオチンを結合させることもできる。この場合は、有機化合物として、アビジンまたはストレプトアビジンを用いると好適である。すなわち、アビジンまたはストレプトアビジンの１分子に４分子のビオチンが結合することから単純計算でも４倍の蛍光物質を結合することができる。また、蛍光物質１分子当たり複数のビオチンを官能基として導入すれば、アビジンまたはストレプトアビジンと複合体を形成するため、より多くの蛍光物質を金属に結合できる。 Biotin can also be bound to the fluorescent substance. In this case, it is preferable to use avidin or streptavidin as the organic compound. That is, since four molecules of biotin bind to one molecule of avidin or streptavidin, a simple calculation can bind four times as many fluorescent substances. If a plurality of biotins are introduced as a functional group per molecule of fluorescent substance, a complex with avidin or streptavidin is formed, so that more fluorescent substance can be bound to the metal.
７．蛍光標識金属粉末の製造
実施形態１〜５に記載した直鎖状金属粉末を用い、蛍光標識金属粉末の製造について以下に説明する。
7). Production of fluorescently labeled metal powder Production of fluorescently labeled metal powder using the linear metal powder described in Embodiments 1 to 5 will be described below.
７−１．有機化合物を介して蛍光物質を標識する場合
金属粉末は、空気中にさらされると、その表面の金属原子に酸素が結合し、酸化膜が形成される。この酸化膜は薄いものの、酸化していない金属部分との分離は困難である。そこで、この酸化膜を利用することで、好適に金属粉末に蛍光物質を標識することができる。
7-1. When a fluorescent substance is labeled through an organic compound When a metal powder is exposed to air, oxygen is bonded to metal atoms on the surface of the metal powder, and an oxide film is formed. Although this oxide film is thin, it is difficult to separate it from an unoxidized metal part. Therefore, by using this oxide film, a fluorescent substance can be suitably labeled on the metal powder.
すなわち、この表面に酸化膜が形成された金属粉末を水溶液中に添加すると、表面酸化膜が水溶液中の水分子と反応し、金属粉末の表面が水和した金属水和物ができる。この金属水和物とシランカップリング剤を水溶液中で反応させると、金属表面がシランカップリング剤で被覆され、金属表面に官能基が導入される。例えばγ−アミノプロピルトリエトキシシランのようなシランカップリング剤と反応させた場合は、下記の化学式（１）で概略されるような反応が進行し、金属表面にアミノ基を導入される。 That is, when a metal powder having an oxide film formed on the surface is added to an aqueous solution, the surface oxide film reacts with water molecules in the aqueous solution, and a metal hydrate is formed in which the surface of the metal powder is hydrated. When this metal hydrate and silane coupling agent are reacted in an aqueous solution, the metal surface is coated with the silane coupling agent, and a functional group is introduced onto the metal surface. For example, when it is made to react with a silane coupling agent such as γ-aminopropyltriethoxysilane, a reaction as outlined by the following chemical formula (1) proceeds, and an amino group is introduced onto the metal surface.
つぎに、このアミノ基が導入された金属粉末化合物に対し、ダンシルクロリドのようなアミノ基との反応性に富む蛍光物質を反応させると、下記の化学式（２）で概略されるような反応が進行し、金属粉末の表面に蛍光物質が標識される。 Next, when a fluorescent substance having a high reactivity with an amino group such as dansyl chloride is reacted with the metal powder compound into which the amino group has been introduced, a reaction represented by the following chemical formula (2) is obtained. As it proceeds, a fluorescent substance is labeled on the surface of the metal powder.
上述の例は、一種類の有機化合物を介した蛍光物質の標識の一例であるが、複数種の有機化合物を介した標識も可能である。 The above example is an example of labeling a fluorescent substance via one kind of organic compound, but labeling via a plurality of kinds of organic compounds is also possible.
例えば、化学式（１）で金属水和物にアミノ基を導入した後、グルタルアルデヒドを反応させ、金属水和物にアルデヒド基を導入することも可能である。その後、アルデヒド基と蛍光物質を反応させることで、金属粉末に蛍光物質を標識することができる。この場合、アルデヒド基との反応を速やかに進行させるため、蛍光物質はアミノ基が導入された物質が好適となる。 For example, it is also possible to introduce an aldehyde group into the metal hydrate by introducing glutaraldehyde after introducing an amino group into the metal hydrate according to the chemical formula (1). Thereafter, the fluorescent substance can be labeled on the metal powder by reacting the aldehyde group with the fluorescent substance. In this case, since the reaction with the aldehyde group proceeds rapidly, the fluorescent material is preferably a material into which an amino group is introduced.
７−２．金属粉末に直接蛍光物質を標識する場合
金属粉末にタンパク質は吸着する性質があるため、有機化合物を介さずとも金属粉末に直接蛍光標識することは可能である。蛍光を発するタンパク質として、フィコエリスリンやアロフィコシアニン等が好適に用いることができる。
7-2. When a fluorescent substance is directly labeled on the metal powder Since the protein is adsorbed on the metal powder, the metal powder can be directly fluorescently labeled without using an organic compound. As the fluorescent protein, phycoerythrin, allophycocyanin, and the like can be suitably used.
８．異方導電膜の調製
本発明の異方導電膜は、金属粉末が蛍光物質で標識されていることを除けば、蛍光物質が標識されていない直鎖状の金属粉末を用いる場合と同じように調製することができる。異方導電膜としては、鎖の長さが、導電接続する、接続部を構成する隣り合う電極間の距離未満とし、導電成分として、膜の厚み方向に配向させた状態で含有するものが好適である。
8). Preparation of anisotropic conductive film The anisotropic conductive film of the present invention is the same as the case of using a linear metal powder not labeled with a fluorescent substance, except that the metal powder is labeled with a fluorescent substance. Can be prepared. An anisotropic conductive film having a chain length less than the distance between adjacent electrodes that form a conductive connection and a connection portion, and containing as a conductive component oriented in the thickness direction of the film is preferable. It is.
直鎖状金属粉末としては、隣り合う電極間の距離の０．９倍以下に調整した種々の直鎖状金属粉末を使用することができる。 As the linear metal powder, various linear metal powders adjusted to 0.9 times or less the distance between adjacent electrodes can be used.
直鎖状金属粉末の鎖の長さを上記の範囲に調整するためには、還元析出法によって直鎖状金属粉末を製造するに際し、液に含有させる分散剤の種類や割合を調整するなどの方法を採用すればよい。ただし、鎖の長さがあまりに短すぎると、膜の厚み方向に配向させた状態としても膜の厚み方向の接続抵抗を十分に低くできない場合がある。このため鎖の長さは、導電接続する、接続部を構成する複数の電極の、高さのばらつきよりも大きいことがさらに好ましい。 In order to adjust the length of the chain of the linear metal powder to the above range, when producing the linear metal powder by the reduction precipitation method, the kind and ratio of the dispersant contained in the liquid are adjusted. The method should be adopted. However, if the length of the chain is too short, the connection resistance in the thickness direction of the film may not be sufficiently lowered even when the chain is oriented in the thickness direction of the film. For this reason, it is more preferable that the length of the chain is larger than the height variation of the plurality of electrodes constituting the connection portion that are conductively connected.
また直鎖状金属粉末は、膜の厚み方向に良好に配向させることを考慮すると、磁場をかけることによって容易に配向するように強磁性を有しているのが好ましく、そのためには前述した（Ａ）〜（Ｄ）のいずれかの構成とするのが好ましい。また、膜の厚み方向の接続抵抗をより一層、低くすることを考慮すると、直鎖状金属粉末は、導電性に優れた金属またはその合金からなる被覆層を有しているのが好ましく、そのためには上記の中でも（Ｃ）、（Ｄ）の構成を採用するのがさらに好ましい。ただし、後述する実施例、比較例の結果から明らかなように、上記被膜を有さない（Ａ）、（Ｂ）などの単純な構造の直鎖状金属粉末であっても、膜の厚み方向の接続抵抗を、十分に実用可能な範囲まで低くすることは可能である。 In consideration of the good orientation in the thickness direction of the film, the linear metal powder preferably has ferromagnetism so that it can be easily oriented by applying a magnetic field. It is preferable that the structure is any one of A) to (D). In consideration of further reducing the connection resistance in the thickness direction of the film, the linear metal powder preferably has a coating layer made of a metal having excellent conductivity or an alloy thereof. Among these, it is more preferable to adopt the configurations (C) and (D). However, as is clear from the results of Examples and Comparative Examples described later, even in the case of a linear metal powder having a simple structure such as (A) or (B) that does not have the above-mentioned film, the thickness direction of the film It is possible to reduce the connection resistance to a practically practical range.
直鎖状金属粉末とともに異方導電膜を形成する結着剤としては、当該用途において結着剤として従来公知の、成膜性および接着性を有する種々の化合物がいずれも使用可能である。かかる結着剤としては、例えば熱可塑性樹脂や硬化性樹脂、液状硬化性樹脂などがあり、特に好ましくはアクリル系樹脂、エポキシ系樹脂、フッ素系樹脂、フェノール系樹脂などを例示することができる。 As the binder for forming the anisotropic conductive film together with the linear metal powder, any of various conventionally known compounds having film-forming properties and adhesiveness can be used as the binder in the application. Examples of such a binder include thermoplastic resins, curable resins, and liquid curable resins. Particularly preferable examples include acrylic resins, epoxy resins, fluorine resins, and phenol resins.
本発明の蛍光標識金属粉末から構成される異方導電膜は、前記のように直鎖状金属粉末の鎖を、膜の厚み方向に配向させた状態で固定している必要がある。かかる異方導電膜は、
（ｉ）下地面と交差する方向に磁場をかけた下地上に、直鎖状金属粉末と結着剤とを、適当な溶媒とともに所定の割合で配合して調製した複合材料を塗布して、直鎖状金属粉末を、上記磁場の方向に沿う膜の厚み方向に配向させた状態で複合材料を固化または硬化させることによって、直鎖状金属粉末の配向を固定するか、あるいは
（ｉｉ）直鎖状金属粉末を、下地面と交差する方向に磁場をかけた下地上に散布して、直鎖状金属粉末を、上記磁場の方向に配向させた状態で、結着剤を含む、流動性を有する塗剤を塗布して固化または硬化させることによって、直鎖状金属粉末の配向を固定したのち、下地からはく離することによって製造できる。なお（ｉ）の方法で使用する複合材料や（ｉｉ）の方法で使用する塗剤は、液状硬化性樹脂等の液状の結着剤を用いることで、溶媒を省略してもよい。
The anisotropic conductive film composed of the fluorescently labeled metal powder of the present invention needs to be fixed in a state where the chain of the linear metal powder is oriented in the thickness direction of the film as described above. Such anisotropic conductive film
(I) Applying a composite material prepared by blending a linear metal powder and a binder together with an appropriate solvent in a predetermined ratio on a base that is applied with a magnetic field in a direction crossing the base surface, Either fixing the orientation of the linear metal powder by solidifying or curing the composite material in a state where the linear metal powder is oriented in the thickness direction of the film along the direction of the magnetic field, or (ii) The chain-like metal powder is dispersed on a base applied with a magnetic field in a direction intersecting the base surface, and the linear metal powder is oriented in the direction of the magnetic field and contains a binder, and has fluidity. It is possible to manufacture by fixing the orientation of the linear metal powder by applying a coating material having a solidity and curing it, and then peeling it from the base. Note that the composite material used in the method (i) and the coating agent used in the method (ii) may be omitted by using a liquid binder such as a liquid curable resin.
これらの方法を実施する場合にかける磁場の強さは、直鎖状金属粉末中に含まれる、強磁性を有する金属の種類や割合等によって異なるものの、異方導電膜中の直鎖状金属粉末を、当該膜の厚み方向に十分に配向させることを考慮すると、磁束密度で表して１ｍＴ以上、中でも１０ｍＴ以上、とくに４０ｍＴ以上であるのが好ましい。 The strength of the magnetic field applied when carrying out these methods varies depending on the type and ratio of the ferromagnetic metal contained in the linear metal powder, but the linear metal powder in the anisotropic conductive film. Is sufficiently oriented in the thickness direction of the film, the magnetic flux density is preferably 1 mT or more, more preferably 10 mT or more, and particularly preferably 40 mT or more.
磁場をかける方法としては、ガラス基板、プラスチック基板などの下地の上下に磁石を配置する方法や、あるいは下地として磁石の表面を利用する方法などをあげることができる。後者の方法は、磁石の表面から出る磁力線が、当該表面から、異方導電膜の厚み程度までの領域では、磁石の表面に対してほぼ垂直であることを利用したもので、異方導電膜の製造装置を簡略化できるという利点がある。 Examples of a method for applying a magnetic field include a method of arranging magnets above and below a base such as a glass substrate or a plastic substrate, or a method of using the surface of a magnet as a base. The latter method utilizes the fact that the lines of magnetic force emerging from the surface of the magnet are substantially perpendicular to the surface of the magnet in the region from the surface to the thickness of the anisotropic conductive film. There is an advantage that the manufacturing apparatus can be simplified.
かくして製造した異方導電膜における、直鎖状の金属粉末の充填量は、０．０５〜２０体積％とするのが好ましい。またその厚みは、異方導電膜を介して配線板と半導体素子、あるいは配線板同士を良好に導電接着させることを考慮すると、１０μｍ〜１００μｍであるのが好ましい。 The amount of linear metal powder filling in the anisotropic conductive film thus manufactured is preferably 0.05 to 20% by volume. Further, the thickness is preferably 10 μm to 100 μm in consideration of good conductive adhesion between the wiring board and the semiconductor element or the wiring boards through the anisotropic conductive film.
９．実装品
上記本発明の異方導電膜を用いて実装した実装品においては、種々の用途に好適に用いることができる。例えば、液晶表示パネルのガラス基板と半導体パッケージとの実装、前記ガラス基板とフレキシブルプリント基板との実装などが好適な例として示される。
9. Mounted product The mounted product mounted using the anisotropic conductive film of the present invention can be suitably used for various applications. For example, preferred examples include mounting of a glass substrate and a semiconductor package of a liquid crystal display panel, mounting of the glass substrate and a flexible printed circuit board, and the like.
半導体パッケージにおいては、接続対象となる電極間のピッチが５０μｍ未満であっても短絡を生じることが無い。このためエレクトロニクス実装の分野における、さらなる高密度実装化の要求に十分に対応することが可能となる。 In a semiconductor package, even if the pitch between electrodes to be connected is less than 50 μm, a short circuit does not occur. Therefore, it is possible to sufficiently meet the demand for higher density mounting in the field of electronics mounting.
例えば、ガラス基板にＩＣチップと同数のＩＴＯ（Ｉｎｄｉｕｍ−Ｔｉｎ−Ｏｘｉｄｅ）電極が形成されたガラスＩＴＯ電極板を用意する。その後、両者の間に前記で得られた異方導電性膜を挟み、加熱しながら、圧力をかけて熱接着させ、ＩＣチップとガラスＩＴＯ電極板とを接合させ、実装品を製造することができる。 For example, a glass ITO electrode plate in which the same number of ITO (Indium-Tin-Oxide) electrodes as the IC chip is formed on a glass substrate is prepared. Thereafter, the anisotropic conductive film obtained above is sandwiched between the two, and while heating, pressure is applied to thermally bond, the IC chip and the glass ITO electrode plate are joined, and a mounted product can be manufactured. it can.
以下に、本発明を、実施例、比較例に基づいて説明する。 Below, this invention is demonstrated based on an Example and a comparative example.
１．直鎖状金属粉末の製造
純水７１５ｍＬに、クエン酸三ナトリウム二水和物９１．５ｇ（０．３０モル）と、硫酸ニッケル六水和物１１．０ｇ（０．０４モル）とを溶解して金属イオン溶液を調製した。また、還元剤溶液としては、四塩化チタンの２０重量％塩酸酸性水溶液（ｐＨ４）を、旭硝子(株)製の陰イオン交換膜で仕切った２槽式の電解槽の、片方の槽に注入するとともに、反対側の槽にはモル濃度０．１Ｍの硫酸ナトリウム水溶液を入れ、それぞれの液にカーボンフェルト電極を浸漬して、四塩化チタンの水溶液側を陰極、硫酸ナトリウム水溶液側を陽極として、３．５Ｖの直流電流を、定電圧制御で通電して水溶液を陰極電解処理することで、Ｔｉ（ＩＶ）の一部をＴｉ（ＩＩＩ）に還元して得た液８０．０ｇを準備した。チタンイオンの総量は０．１モル、Ｔｉ（ＩＩＩ）とＴｉ（ＩＶ）のモル比は４：１であった。
1. Production of linear metal powder In 715 mL of pure water, 91.5 g (0.30 mol) of trisodium citrate dihydrate and 11.0 g (0.04 mol) of nickel sulfate hexahydrate were dissolved. Thus, a metal ion solution was prepared. Moreover, as a reducing agent solution, 20 wt% hydrochloric acid aqueous solution (pH 4) of titanium tetrachloride is injected into one tank of a two-tank electrolytic cell partitioned by an anion exchange membrane manufactured by Asahi Glass Co., Ltd. In addition, a sodium sulfate aqueous solution with a molar concentration of 0.1 M is placed in the opposite tank, and a carbon felt electrode is immersed in each solution, with the titanium tetrachloride aqueous solution side serving as a cathode and the sodium sulfate aqueous solution side serving as an anode. A solution of 80.0 g obtained by reducing a part of Ti (IV) to Ti (III) was prepared by conducting a cathodic electrolytic treatment of the aqueous solution by applying a DC current of .5V under constant voltage control. The total amount of titanium ions was 0.1 mol, and the molar ratio of Ti (III) to Ti (IV) was 4: 1.
さらに、純水に、２５％アンモニア水６０．０ｍＬと、１．０ｇのセルナＤ-７３５（中京油脂：ポリカルボン酸型高分子界面活性剤、成分重量比：主成分＝１５〜２５、アンモニア＝１〜１０，水＝６５〜８４、主成分：スチレン−マレイン酸共重合体，平均分子量（Ｗ）＝１９，０００ ）とを溶解した後、必要に応じて純水を加えて全量を２００ｍＬに調整して分散剤溶液を作製した。なお、アンモニア水の量は、反応液全体のｐＨを１０に調整するために最適な値とした。 Furthermore, in pure water, 60.0 mL of 25% ammonia water and 1.0 g of Serna D-735 (Chukyo oil: polycarboxylic acid type polymer surfactant, component weight ratio: main component = 15-25, ammonia = 1 to 10, water = 65 to 84, main component: styrene-maleic acid copolymer, average molecular weight (W) = 19,000), and then pure water is added as necessary to make the total volume 200 mL. A dispersant solution was prepared by adjusting. The amount of aqueous ammonia was set to an optimum value for adjusting the pH of the entire reaction solution to 10.
次に、上記金属イオン溶液の全量と、還元剤溶液の全量とを混合し、温浴槽中に入れて液温を３５℃に維持しながら２０分間、かく拌した後、一対の対向磁石間に配置した反応槽中に入れて１００ｍＴの磁場をかけながら、液温を３５℃に維持した。そして、反応槽中の液をかく拌棒で４〜５回かく拌しながら、あらかじめ液温を３５℃に昇温しておいた分散剤溶液の全量を一気に加えて、前記のように反応液のｐＨを１０に調整した後、最後にかく拌棒を反対方向に１〜２回、回転させて反応液の流動を停止し、その後は反応液を実質的にかく拌せずに静置した状態（かく拌速度０ｒｐｍ）を維持して還元析出反応を行った。そうすると、液中で気泡が多数、発生し、その多くが液面で割れずに残って、反応液の上面に安定な泡の層が形成された。 Next, the total amount of the metal ion solution and the total amount of the reducing agent solution are mixed, put in a hot tub and stirred for 20 minutes while maintaining the liquid temperature at 35 ° C., and then between a pair of opposed magnets. The liquid temperature was maintained at 35 ° C. while being placed in the arranged reaction vessel and applying a magnetic field of 100 mT. And while stirring the liquid in a reaction tank 4-5 times with a stirring rod, the whole amount of the dispersant solution that had been heated to 35 ° C. in advance was added all at once, and the reaction liquid was used as described above. After adjusting the pH of the mixture to 10, the stirring rod was finally rotated in the opposite direction once or twice to stop the flow of the reaction solution, and then the reaction solution was allowed to stand without substantially stirring. The reduction (precipitation) reaction was performed while maintaining the state (stirring speed: 0 rpm). As a result, many bubbles were generated in the liquid, and many of them remained without being broken at the liquid surface, and a stable foam layer was formed on the upper surface of the reaction liquid.
その後、１０分経過した時点で泡の層を液から分離し、ろ紙上で水洗して固形分を得、この固形分を再びろ紙上で水洗後、純水中でかく拌洗浄（２０分間）−エタノール中で、超音波を照射しながら、かく拌洗浄（３０分間）−ろ別−真空乾燥（２３±１℃）の各工程を経て直鎖状ニッケル粉末を製造した。 Thereafter, the foam layer was separated from the liquid at the time when 10 minutes passed, and washed with water on a filter paper to obtain a solid content. This solid content was again washed with water on the filter paper, and then washed with stirring in pure water (20 minutes) − A linear nickel powder was produced through each step of stirring washing (30 minutes) -filtering-vacuum drying (23 ± 1 ° C.) while irradiating ultrasonic waves in ethanol.
２．蛍光標識反応
上記１で製造した直鎖状ニッケル粉末０．８ｇを、酢酸ジエチレングリコールモノ−ｎ−ブチルエーテル（ＢＣＡ）６０ｍＬに分散し、１０分間かく拌した後、磁石を用いて直鎖状ニッケル粉末を沈降させ、上精のＢＣＡ液を約５０ｍｌ取り除き直鎖状ニッケル粉末溶液１を準備した。また別途、ダンシルクロリド０．１ｇをＢＣＡ５０ｍＬに溶解した溶液２を準備した。
2. Fluorescent labeling reaction 0.8 g of the linear nickel powder produced in 1 above was dispersed in 60 mL of diethylene glycol acetate mono-n-butyl ether (BCA) and stirred for 10 minutes. The linear nickel powder solution 1 was prepared by removing about 50 ml of the supernatant BCA solution. Separately, a solution 2 in which 0.1 g of dansyl chloride was dissolved in 50 mL of BCA was prepared.
次いで、溶液２に、シランカップリング剤ＫＢＭ９０３（γ−アミノプロピルトリメトキシシラン、信越化学工業（株）製）０．４ｇを室温にてかく拌しながら滴下し、添加した。１０分間かく拌し、ダンシルクロリド溶液とシランカップリング剤を混合させた（溶液３）。次いで、溶液１と溶液３を１００℃の温浴層で溶液が暖まるまで保温した。溶液１、３が８０℃以上になった後、溶液３に溶液１をかく拌しながら一気に添加した。その後３００分間、１００℃にて、反応を続けた。３００分後、温浴槽から反応液を取り出し、室温に６０分間静置した。次いで、反応液を入れた容器の底部に磁石を置き、直鎖状ニッケル粉末を沈殿させた後、上清液を取り除いた。次いで、残っている直鎖状ニッケル粉末に対して、ＢＣＡ１００ｍｌに分散−攪拌（１０分間）−磁石を用いて沈降−上清液を除去という一連の工程を２回繰り返し、過剰な蛍光物質とシランカップリング剤を取り除いた。
Next, 0.4 g of silane coupling agent KBM903 (γ-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise to Solution 2 while stirring at room temperature. The mixture was stirred for 10 minutes to mix the dansyl chloride solution and the silane coupling agent (solution 3). Next, the solution 1 and the
その後、上記直鎖状ニッケル粉末を含むＢＣＡ溶液をメンブレンフィルタ上に移し、ＢＣＡで洗浄して固形分を得た後、この固形分を真空乾燥機にて、乾燥した。乾燥は１００℃で一昼夜行い、蛍光標識ニッケル粉末を得た。 Thereafter, the BCA solution containing the linear nickel powder was transferred onto a membrane filter, washed with BCA to obtain a solid content, and then dried with a vacuum dryer. Drying was performed at 100 ° C. all day and night to obtain fluorescently labeled nickel powder.
３．蛍光顕微鏡による評価
前記２で得られた蛍光標識ニッケル粉末を蛍光顕微鏡で評価した。
3. Evaluation by fluorescent microscope The fluorescently labeled nickel powder obtained in 2 above was evaluated by a fluorescent microscope.
蛍光標識ニッケル粉末の評価は、評価用の観察シートを別途調製して行った。すなわち、蛍光標識ニッケル粉末０．０１ｇポリエチレングリコール（重量平均分子量２０，０００）４００ｇを純水１Ｌに溶解した溶液１０ｇに分散し、遠心かく拌ミキサーを用いて均一に分散させることで、評価用の複合材料を調製した。そしてこの複合材料を、ガラス上に、ギャップ２５μｍでドクターナイフを用いて塗布し、蛍光標識ニッケル粉末がシートの面方向に配向した状態で固定された観察シートを調製した。 Evaluation of the fluorescently labeled nickel powder was performed by separately preparing an observation sheet for evaluation. That is, 400 g of fluorescently labeled nickel powder 400 g of polyethylene glycol (weight average molecular weight 20,000) is dispersed in 10 g of a solution dissolved in 1 L of pure water, and uniformly dispersed using a centrifugal stirring mixer. A composite material was prepared. And this composite material was apply | coated on glass using a doctor knife with a gap of 25 micrometers, and the observation sheet fixed in the state which the fluorescent label nickel powder orientated in the surface direction of the sheet | seat was prepared.
この観察シートを、蛍光顕微鏡（オリンパス製、商品名：落射式蛍光システムＢＸ５１）にて観察し評価し、（１）全ての粉末が蛍光標識されたか、および（２）蛍光標識によって寸法や形状のよう似たものとの区別が可能になったか、について評価した。蛍光顕微鏡の光源として水銀ランプを用い、ミラーユニットとしてＵ−ＭＷＵ２を用いることにより、波長が３３０〜３８０ｎｍの紫外光を励起光として観察シートに照射し、観察シートから発せられる波長が４００ｎｍ以上の蛍光を検出して蛍光標識ニッケル粉末の特性を評価した。その結果の写真が、図１（ａ）、（ｂ）である。図１（ａ）のように透過光だけで見ると、蛍光標識ニッケル粉末は黒い線として観察され、寸法や形状がよく似ているゴミ等と区別ができない。一方、図１（ｂ）のように紫外光を照射し、その励起で発生した蛍光を見ると、図１（ａ）で検出された全ての蛍光標識ニッケル粉末が緑の線として検出されており、また大きさや形状がよく似ているゴミ等との区別もできていることがわかった。 This observation sheet was observed and evaluated with a fluorescence microscope (Olympus, product name: epi-illumination fluorescence system BX51). (1) All powders were fluorescently labeled, It was evaluated whether it became possible to distinguish between similar things. By using a mercury lamp as the light source of the fluorescence microscope and U-MWU2 as the mirror unit, the observation sheet is irradiated with ultraviolet light having a wavelength of 330 to 380 nm as excitation light, and the wavelength emitted from the observation sheet is 400 nm or more. Was detected to evaluate the characteristics of the fluorescently labeled nickel powder. The resulting photographs are shown in FIGS. 1 (a) and 1 (b). When viewed only with transmitted light as shown in FIG. 1 (a), the fluorescently labeled nickel powder is observed as a black line and cannot be distinguished from dust having a similar size and shape. On the other hand, when the ultraviolet light is irradiated as shown in FIG. 1B and the fluorescence generated by the excitation is observed, all the fluorescently labeled nickel powders detected in FIG. 1A are detected as green lines. It was also found that it was possible to distinguish it from trash with similar size and shape.
４．異方導電膜の調製
ビスフェノールＡ型の固形エポキシ樹脂〔ジャパンエポキシレジン（株）製、商品名：エピコート１２５６（樹脂Ａとする）、エピコート１００２（樹脂Ｂとする）〕と、ビスフェノールＡ型の液状エポキシ樹脂〔ジャパンエポキシレジン（株）製、商品名：エピコート８２８ＵＳ（樹脂Ｃとする）〕、マイクロカプセル型イミダゾール系硬化剤〔旭化成ケミカルズ(株)製、商品名ノバキュアＨＸ３９４１（硬化剤とする）〕とを、重量比で樹脂Ａ／樹脂Ｂ／樹脂Ｃ／硬化剤＝４０／２０／４０／３５の割合で用いた。これらの材料を、酢酸ブチルに溶解して、樹脂分、すなわち樹脂Ａ、樹脂Ｂ、樹脂Ｃおよび硬化剤の３成分の合計の濃度が４０重量％である樹脂溶液を調製した。
4). Preparation of anisotropic conductive film Bisphenol A type solid epoxy resin [manufactured by Japan Epoxy Resin Co., Ltd., trade names: Epicoat 1256 (referred to as resin A), Epicoat 1002 (referred to as resin B)], and bisphenol A type liquid Epoxy resin [made by Japan Epoxy Resin Co., Ltd., trade name: Epicoat 828US (resin C)], microcapsule type imidazole curing agent [made by Asahi Kasei Chemicals Co., Ltd., trade name Novacure HX3941 (hardener)] Were used at a ratio of resin A / resin B / resin C / curing agent = 40/20/40/35 by weight ratio. These materials were dissolved in butyl acetate to prepare a resin solution having a resin component, that is, a total concentration of three components of resin A, resin B, resin C, and a curing agent of 40% by weight.
次に、この樹脂溶液に、樹脂分と金属粉末の総量に占める割合で表される金属充填率が０．５体積％となるように、前記２で得られた蛍光標識ニッケル粉末を配合し、遠心かく拌ミキサーを用いてかく拌して均一に分散させることで、異方導電膜用の複合材料を調製した。そしてこの複合材料を、離型処理を施したＰＥＴフィルム上にドクターナイフを用いて塗布した後、１００ｍＴの磁場をかけながら６０℃で３０分間、乾燥、固化させることで、蛍光標識ニッケル粉末が膜の厚み方向に配向した状態で固定された、厚み２５μｍの異方導電膜を調製した。 Next, in this resin solution, the fluorescently labeled nickel powder obtained in 2 above is blended so that the metal filling rate represented by the ratio of the resin content and the total amount of the metal powder is 0.5% by volume, A composite material for an anisotropic conductive film was prepared by stirring and uniformly dispersing using a centrifugal stirring mixer. And after apply | coating this composite material on the PET film which performed the mold release process using a doctor knife, it is made to dry and solidify at 60 degreeC for 30 minutes, applying a magnetic field of 100 mT, and fluorescent labeling nickel powder is a film | membrane. An anisotropic conductive film having a thickness of 25 μm, which was fixed in a state of being oriented in the thickness direction, was prepared.
５．実装品
幅１５μｍ、長さ１００μｍ、高さ１６μｍの金めっき電極が１５μｍ間隔で７２６個配列されたＩＣチップと、幅２０μｍ、長さ１００μｍ、高さ０．１５μｍのＩＴＯ電極が１０μｍ間隔でＩＣチップと同数形成されたガラス基板とを用意した。このガラス基板上に前記４で調製した異方導電膜を載置し、５０℃に加熱しながら４ＭＰａの圧力で２秒間加圧して仮接着させた。その後、上記異方導電膜から、離型処理を施したＰＥＴフィルムを剥がし、ＩＣチップを、ＩＴＯ電極と金メッキ電極の位置あわせをしながら異方導電膜上に載置して、１８０℃に加熱しながら、１電極当たり２０ｇｆの圧力で３０秒間加圧して熱接着させ、ＩＣチップとガラス基板とを実装した実装品を得た。
5. Mounted product An IC chip in which 726 gold-plated electrodes with a width of 15 μm, a length of 100 μm, and a height of 16 μm are arranged at intervals of 15 μm, and an ITO chip with a width of 20 μm, a length of 100 μm, and a height of 0.15 μm at an interval of 10 μm And the same number of glass substrates formed. The anisotropic conductive film prepared in 4 above was placed on this glass substrate, and was temporarily bonded by applying pressure at 4 MPa for 2 seconds while heating to 50 ° C. Thereafter, the PET film subjected to the release treatment is peeled off from the anisotropic conductive film, and the IC chip is placed on the anisotropic conductive film while aligning the ITO electrode and the gold plating electrode, and heated to 180 ° C. However, it was pressurized and bonded for 30 seconds at a pressure of 20 gf per electrode to obtain a mounted product on which an IC chip and a glass substrate were mounted.
６．蛍光顕微鏡による実装品の評価
前記５で得られた実装品を蛍光顕微鏡で評価した。
6). Evaluation of Mounted Product by Fluorescence Microscope The mounted product obtained in 5 above was evaluated by a fluorescence microscope.
図２の実装品のガラス基板側の面を励起光で照射し、発生した蛍光を蛍光顕微鏡で観察した。その観察写真が図３であり、実装品の状態でも蛍光観察が可能であることがわかった。 The surface of the mounted product of FIG. 2 on the glass substrate side was irradiated with excitation light, and the generated fluorescence was observed with a fluorescence microscope. The observation photograph is FIG. 3, and it was found that fluorescence observation is possible even in the state of the mounted product.
本発明の蛍光標識金属粉末は、励起光が照射されると、金属粉末から蛍光が発せられる。そのため、エレクトロニクス分野、特に、ガラス基板上に半導体パッケージを実装したり、あるいはガラス基板上にフレキシブルプリント配線板を実装したりする異方導電膜の導電成分として好適に用いられる。 The fluorescently labeled metal powder of the present invention emits fluorescence from the metal powder when irradiated with excitation light. Therefore, it is suitably used as a conductive component of an anisotropic conductive film for mounting a semiconductor package on a glass substrate, or mounting a flexible printed wiring board on a glass substrate, particularly in the electronics field.
１ 蛍光標識金属粉末
２ ゴミ
３ 異方導電膜
４ ＩＣチップ
５ ガラス基板
６ 金めっき電極
DESCRIPTION OF SYMBOLS 1 Fluorescent label metal powder 2
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| JPS57141547A (en) * | 1981-02-25 | 1982-09-01 | Nippon Oil & Fats Co Ltd | Magnetic powder for flaw inspection and its preparation |
| JPS60211358A (en) * | 1984-04-06 | 1985-10-23 | Tokushu Toryo Kk | Manufacture of colored magnetic powder for magnetic powder flaw detection |
| JPH1012044A (en) * | 1996-06-25 | 1998-01-16 | Tokuyama Corp | Curable conductive composition |
| JP2004511511A (en) * | 2000-10-16 | 2004-04-15 | コンセホ・スペリオール・デ・インベスティガシオネス・シエンティフィカス | Nanoparticles |
| JP2005523027A (en) * | 2002-04-22 | 2005-08-04 | ユニヴァーシティ オヴ フロリダ | Functionalized nanoparticles and methods of use |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS57141547A (en) * | 1981-02-25 | 1982-09-01 | Nippon Oil & Fats Co Ltd | Magnetic powder for flaw inspection and its preparation |
| JPS60211358A (en) * | 1984-04-06 | 1985-10-23 | Tokushu Toryo Kk | Manufacture of colored magnetic powder for magnetic powder flaw detection |
| JPH1012044A (en) * | 1996-06-25 | 1998-01-16 | Tokuyama Corp | Curable conductive composition |
| JP2004511511A (en) * | 2000-10-16 | 2004-04-15 | コンセホ・スペリオール・デ・インベスティガシオネス・シエンティフィカス | Nanoparticles |
| JP2005523027A (en) * | 2002-04-22 | 2005-08-04 | ユニヴァーシティ オヴ フロリダ | Functionalized nanoparticles and methods of use |
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