JP2012177044A - Core-shell structure particle, paste composition and magnetic body composition using the same - Google Patents
Core-shell structure particle, paste composition and magnetic body composition using the same Download PDFInfo
- Publication number
- JP2012177044A JP2012177044A JP2011041381A JP2011041381A JP2012177044A JP 2012177044 A JP2012177044 A JP 2012177044A JP 2011041381 A JP2011041381 A JP 2011041381A JP 2011041381 A JP2011041381 A JP 2011041381A JP 2012177044 A JP2012177044 A JP 2012177044A
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- Prior art keywords
- core
- magnetic
- shell
- particles
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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Abstract
Description
本発明はコア−シェル構造粒子およびこれを含むペースト組成物や磁性体組成物に関する。より詳しくは、本発明は、パソコン、自動車、携帯電話や携帯情報端末、フラットパネルテレビ、ゲーム機器、高度道路情報システム、無線ＬＡＮなどに内蔵するインダクタコア用や電磁波吸収体などに含有されるペースト組成物およびそれを硬化させてなる磁性体組成物に関する。 The present invention relates to core-shell structured particles and a paste composition or magnetic composition containing the same. More specifically, the present invention relates to a paste contained in an inductor core or an electromagnetic wave absorber incorporated in a personal computer, an automobile, a mobile phone, a portable information terminal, a flat panel TV, a game device, an intelligent road information system, a wireless LAN, or the like. The present invention relates to a composition and a magnetic composition obtained by curing the composition.
近年、インターネット利用を始めとして、パソコン、自動車、携帯電話や携帯情報端末、フラットパネルテレビ、ゲーム機器、高度道路情報システム、無線ＬＡＮなど、ＧＨｚ帯の高周波を利用した情報通信機器等が普及してきている。高周波は信号にノイズを発生させて情報伝達を悪化させたり、またその高周波に伴い電磁波が情報機器から放射され、他の電子機器への誤作動を引き起こしたりする可能性が指摘されている。それらに対応するため、高周波ノイズを除去し、かつ電圧を安定化させる役割を担うインダクタが情報通信機器に内蔵されている。透磁率の高いコアをインダクタに挿入することで、インダクタンスをさらに向上させることができる。コアとしては磁性体金属や磁性体セラミックスなどの無機材料のほか、樹脂中に磁性体無機粒子を高充填したものが利用されている。 In recent years, information communication devices using high frequency in the GHz band such as personal computers, automobiles, mobile phones and personal digital assistants, flat panel televisions, game machines, intelligent road information systems, wireless LANs, etc. have been widely used. Yes. It has been pointed out that the high frequency may cause noise in the signal to deteriorate information transmission, and the electromagnetic wave may be radiated from the information device along with the high frequency, causing malfunction to other electronic devices. In order to cope with them, an inductor that plays a role of removing high-frequency noise and stabilizing the voltage is built in the information communication device. By inserting a core with high magnetic permeability into the inductor, the inductance can be further improved. As the core, in addition to inorganic materials such as magnetic metal and magnetic ceramics, a resin in which magnetic inorganic particles are highly filled is used.
一般に、樹脂中に金属粒子を高充填に分散させた場合、金属粒子同士は樹脂中で均一に分散せず、凝集体を形成している。その結果、金属粒子同士が凝集し、ペーストを膜とした際の複合材自体の絶縁性が取れないといった問題があった。さらに、磁性体無機粒子を用いた場合、凝集体は一つの大きな磁性粒子として振舞い、高周波では渦電流を生じやすくなる。そして、エネルギー損失の増加を引き起こし、コア材料としての特性が損なわれる場合がある。 Generally, when metal particles are dispersed in a highly filled resin, the metal particles are not uniformly dispersed in the resin and form aggregates. As a result, there is a problem that the metal particles aggregate and the composite material itself cannot be insulated when the paste is used as a film. Furthermore, when magnetic inorganic particles are used, the aggregates behave as one large magnetic particle, and eddy currents are likely to be generated at high frequencies. And an increase in energy loss is caused, and the characteristic as a core material may be impaired.
そこで、樹脂中に磁性体無機粒子の分散性を向上させ、上記特性を満たす材料として、磁性体無機粒子を樹脂と実質的に同一の成分で予め被覆した材料が提案されている（例えば、特許文献１参照）。 Therefore, as a material that improves the dispersibility of the magnetic inorganic particles in the resin and satisfies the above characteristics, a material in which the magnetic inorganic particles are previously coated with substantially the same components as the resin has been proposed (for example, patents). Reference 1).
しかしながら特許文献１に記載の材料では、磁性体無機粒子を樹脂で被覆することにより磁気損失（ｔａｎδ）は低下するものの、比透磁率も小さくなってしまうという問題があった。 However, the material described in Patent Document 1 has a problem that the magnetic permeability (tan δ) is reduced by coating the magnetic inorganic particles with a resin, but the relative permeability is also reduced.
かかる状況に鑑み、本発明は、磁性体材料として優れた性能を示し、絶縁性にも優れた磁性体組成物を提供することを目的とする。 In view of such circumstances, an object of the present invention is to provide a magnetic composition that exhibits excellent performance as a magnetic material and is excellent in insulation.
本発明は、磁性体無機粒子をコアとするコア−シェル構造粒子であって、前記シェルがグリシジルアミン型エポキシ化合物を付加重合させて得られる樹脂を含むことを特徴とするコア−シェル構造粒子である。 The present invention provides a core-shell structured particle having a magnetic inorganic particle as a core, wherein the shell contains a resin obtained by addition polymerization of a glycidylamine type epoxy compound. is there.
本発明のコア−シェル構造粒子を用いることにより、磁性体材料として優れた性能を示し、絶縁性にも優れた磁性体組成物が得られる。 By using the core-shell structured particles of the present invention, a magnetic composition that exhibits excellent performance as a magnetic material and is excellent in insulation can be obtained.
本発明におけるコア−シェル構造粒子のコアである磁性体無機粒子としては、軟磁性金属やフェライトなどが挙げられる。軟磁性金属は電気抵抗が小さく、高周波帯域では渦電流の発生により急激に透磁率が低下するといった特徴がある。また、フェライトは軟磁性金属に比べ電気抵抗は高いものの、材料本来の透磁率が低いといった特徴がある。本発明においては、Ｆｅ（カルボニル鉄）、Ｆｅ−Ｎｉ合金、Ｆｅ−Ｎｉ−Ｍｏ合金、Ｆｅ−Ｃｏ合金、Ｆｅ−Ｃｒ合金、Ｆｅ−Ｓｉ合金、Ｆｅ−Ａｌ合金、Ｆｅ−Ｃｒ−Ｓｉ合金、Ｆｅ−Ｃｒ−Ａｌ合金、Ｆｅ−Ａｌ−Ｓｉ合金などのＦｅ合金類、Ｆｅ基アモルファス、Ｃｏ基アモルファスなどのアモルファス合金、Ｍｇ−Ｚｎフェライト、Ｍｎ−Ｚｎフェライト、Ｍｎ−Ｍｇフェライト、Ｃｕ−Ｚｎフェライト、Ｍｇ−Ｍｎ−Ｓｒフェライト、Ｎｉ−Ｚｎフェライト、Ｂａフェライトなどのフェライトを用いることが好ましい。 Examples of the magnetic inorganic particles that are the cores of the core-shell structured particles in the present invention include soft magnetic metals and ferrite. Soft magnetic metal has a small electric resistance, and has a feature that the permeability is rapidly lowered by the generation of eddy current in a high frequency band. In addition, ferrite has a characteristic that the magnetic permeability inherent to the material is low, although the electrical resistance is higher than that of the soft magnetic metal. In the present invention, Fe (carbonyl iron), Fe—Ni alloy, Fe—Ni—Mo alloy, Fe—Co alloy, Fe—Cr alloy, Fe—Si alloy, Fe—Al alloy, Fe—Cr—Si alloy, Fe alloys such as Fe-Cr-Al alloy and Fe-Al-Si alloy, amorphous alloys such as Fe-based amorphous and Co-based amorphous, Mg-Zn ferrite, Mn-Zn ferrite, Mn-Mg ferrite, Cu-Zn ferrite It is preferable to use ferrite such as Mg—Mn—Sr ferrite, Ni—Zn ferrite, and Ba ferrite.
磁性体無機粒子の製造方法としては、固相反応法、水熱合成法、超臨界水熱合成法、ゾルゲル法、しゅう酸塩法、乾式法、湿式法、共沈法および噴霧熱分解法など公知の方法が挙げられる。得られた磁性体無機粒子は、ハンマーミル、ロールミル、ボールミル、遊星式ボールミル等によって粉砕され、目的の粒径を有する磁性体無機粒子が得られる。 Magnetic inorganic particles can be produced by solid phase reaction method, hydrothermal synthesis method, supercritical hydrothermal synthesis method, sol-gel method, oxalate method, dry method, wet method, coprecipitation method, spray pyrolysis method, etc. A well-known method is mentioned. The obtained magnetic inorganic particles are pulverized by a hammer mill, a roll mill, a ball mill, a planetary ball mill or the like to obtain magnetic inorganic particles having a target particle size.
磁性体無機粒子の形状としては、球状、略球状、楕円球状、針状、板状、鱗片状、棒状などが挙げられるが、特に、限定されるものではない。これらのうち１種を単独で用いたり、２種以上を混合して用いたりすることができる。 Examples of the shape of the magnetic inorganic particles include a spherical shape, a substantially spherical shape, an elliptical spherical shape, a needle shape, a plate shape, a scale shape, and a rod shape, but are not particularly limited. Among these, one kind can be used alone, or two or more kinds can be mixed and used.
本発明に用いられる磁性体無機粒子の平均粒子径は３０μｍ以下であることが好ましい。磁性体無機粒子の平均粒子径が３０μｍ以下であると、ペースト組成物および磁性体組成物の各形態においての膜の平坦性が良好となり、膜厚のばらつきを小さくすることができる。さらに、百ＭＨｚを超える高周波帯域においては、磁性体無機粒子内での渦電流による磁気損失を抑制し、低ｔａｎδ化が可能になることから、平均粒子径は小さい方が好ましい。具体的には、平均粒子径が１５μｍ以下であることが好ましく、１０μｍ以下であることがより好ましく、３μｍ以下であることがさらに好ましい。一方、磁性体無機粒子同士の凝集が抑制され、磁性体組成物とした時の膜のクラックを抑制できる点から、平均粒子径は１０ｎｍ以上であることが好ましい。さらに、磁性体組成物の透磁率が向上する点から、平均粒子径は０．１μｍ以上であることが好ましく、０．５μｍ以上であることがより好ましい。 The average particle diameter of the magnetic inorganic particles used in the present invention is preferably 30 μm or less. When the average particle diameter of the magnetic inorganic particles is 30 μm or less, the flatness of the film in each form of the paste composition and the magnetic composition becomes good, and variations in film thickness can be reduced. Furthermore, in the high frequency band exceeding 100 MHz, the magnetic loss due to the eddy current in the magnetic inorganic particles is suppressed and the tan δ can be reduced. Specifically, the average particle size is preferably 15 μm or less, more preferably 10 μm or less, and even more preferably 3 μm or less. On the other hand, the average particle diameter is preferably 10 nm or more from the viewpoint that aggregation of the magnetic inorganic particles is suppressed and cracking of the film when the magnetic composition is obtained can be suppressed. Furthermore, from the viewpoint of improving the magnetic permeability of the magnetic composition, the average particle diameter is preferably 0.1 μm or more, and more preferably 0.5 μm or more.
ここで、本発明における磁性体無機粒子の平均粒子径とは数平均粒子径である。ペースト組成物や磁性体組成物中の磁性体無機粒子の平均粒子径を測定する方法は以下の通りである。ペースト組成物の場合はこれを任意の基板上に塗布し、後述の方法で磁性体組成物としてから、磁性体組成物中の磁性体無機粒子の平均粒子径の測定方法と同様にして求める。磁性体組成物の場合は、これをＳＥＭ（走査型電子顕微鏡）やＴＥＭ（透過型電子顕微鏡）により少なくとも１００個の粒子が観測できる程度の倍率で観察したときの視野における粒子を観察し、無作為に選んだ１００個の粒子の粒子径の数平均を計算して求めることができる。 Here, the average particle diameter of the magnetic inorganic particles in the present invention is the number average particle diameter. The method for measuring the average particle diameter of the magnetic inorganic particles in the paste composition and magnetic composition is as follows. In the case of a paste composition, this is coated on an arbitrary substrate and made into a magnetic composition by the method described later, and then obtained in the same manner as the method for measuring the average particle diameter of magnetic inorganic particles in the magnetic composition. In the case of a magnetic composition, the particles are observed in the field of view when observed at a magnification such that at least 100 particles can be observed by SEM (scanning electron microscope) or TEM (transmission electron microscope). It can be obtained by calculating the number average of the particle size of 100 particles selected for the purpose.
なお、ペースト組成物中および磁性体組成物中の磁性体無機粒子は、凝集が完全にほぐれた１次粒子の状態にあるものと、複数個の１次粒子が凝集した状態（２次粒子）にあるものが存在する。本発明における磁性体無機粒子の粒子径とは、凝集していない１次粒子はその粒子の粒子径であり、１次粒子が凝集したものはその凝集体を構成している１次粒子の粒子径である。 In addition, the magnetic inorganic particles in the paste composition and the magnetic composition are in a state of primary particles in which aggregation is completely loosened, and in a state where a plurality of primary particles are aggregated (secondary particles). There is something in. The particle diameter of the magnetic inorganic particles in the present invention is the particle diameter of the primary particles that are not aggregated, and the primary particles that constitute the aggregate are the aggregated primary particles. Is the diameter.
また、前処理として磁性体無機粒子の表面処理を行ってもよい。このような処理としては、シラン系、チタン系、アルミニウム系などの各種カップリング剤による処理、脂肪酸による処理、ロジン処理、酸性処理、塩基性処理などが挙げられる。特に、磁性体無機粒子をシランカップリング剤等で前処理するのが好ましい。例えば、シランカップリング剤、磁性体無機粒子、水およびビーズを混合して攪拌する。そこからビーズを除去して得られた分散液を濾過して濾物を得る。その濾物を乾燥することで、シランカップリング剤で処理した磁性体無機粒子が得られる。その結果、磁性体無機粒子を被覆したシランカップリング剤にシェルが付きやすくなり、シェルが厚くなりやすい。 Moreover, you may perform the surface treatment of a magnetic inorganic particle as pretreatment. Examples of such treatment include treatment with various coupling agents such as silane, titanium, and aluminum, treatment with fatty acid, rosin treatment, acid treatment, and basic treatment. In particular, it is preferable to pretreat the magnetic inorganic particles with a silane coupling agent or the like. For example, a silane coupling agent, magnetic inorganic particles, water and beads are mixed and stirred. The dispersion obtained by removing the beads is filtered to obtain a residue. By drying the filtrate, magnetic inorganic particles treated with a silane coupling agent can be obtained. As a result, the shell is easily attached to the silane coupling agent coated with the magnetic inorganic particles, and the shell tends to be thick.
前処理に用いられるシランカップリング剤としては、メチルトリメトキシシラン、ジメチルジエトキシシラン、フェニルトリエトキシシラン、ヘキサメチルジシラザン、３−メタクリロキシプロピルトリメトキシシラン、３−グリシドキシプロピルトリメトキシシラン、ビニルトリメトキシシラン、２−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、３−アミノプロピルトリエトキシシラン、３−アミノプロピルトリメトキシシランなどが挙げられるが、これらに限定されない。 Examples of the silane coupling agent used in the pretreatment include methyltrimethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, hexamethyldisilazane, 3-methacryloxypropyltrimethoxysilane, and 3-glycidoxypropyltrimethoxysilane. Vinyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, and the like, but are not limited thereto.
本発明におけるコア−シェル構造粒子のシェルは、グリシジルアミン型エポキシ化合物を付加重合させて得られる樹脂を含む。グリシジルアミン型エポキシ化合物は熱硬化性の樹脂である。グリシジルアミン型エポキシ化合物を付加重合させて得られる樹脂は、耐熱性や耐溶剤性に優れるため、ペースト組成物の保存安定性に優れ、結果として、それを硬化した磁性体組成物は十分な絶縁性を発現する。また、グリシジルアミン型エポキシ化合物を付加重合させて得られる樹脂は、コアである粒子の表面に容易にシェルを形成する。その理由は、グリシジルアミン型エポキシ化合物が付加重合する際に、分子内の窒素原子が触媒活性となり、粒子表面の水酸基とグリシジルアミン型エポキシ化合物のエポキシ基の付加反応を促進するためであると考えられる。その結果、本発明のコアーシェル構造粒子を有するペースト組成物を用いて得られる磁性体組成物は、十分な絶縁性を発現する。 The shell of the core-shell structured particles in the present invention contains a resin obtained by addition polymerization of a glycidylamine type epoxy compound. The glycidylamine type epoxy compound is a thermosetting resin. The resin obtained by addition polymerization of a glycidylamine type epoxy compound is excellent in heat resistance and solvent resistance, so that the storage stability of the paste composition is excellent, and as a result, the cured magnetic material composition has sufficient insulation. Expresses sex. In addition, a resin obtained by addition polymerization of a glycidylamine type epoxy compound easily forms a shell on the surface of the core particle. The reason for this is thought to be that when the glycidylamine type epoxy compound undergoes addition polymerization, the nitrogen atom in the molecule becomes catalytically active and promotes the addition reaction between the hydroxyl group on the particle surface and the epoxy group of the glycidylamine type epoxy compound. It is done. As a result, the magnetic composition obtained using the paste composition having the core-shell structure particles of the present invention exhibits sufficient insulation.
グリシジルアミン型エポキシ化合物としては、下記に示した構造（基）を有する化合物が上げられる。 Examples of the glycidylamine type epoxy compound include compounds having the structure (group) shown below.
上記一般式（１）中、Ｒ１は、グリシジル基または炭素数１〜５のアルキル基である。一般式（１）で表される構造（基）を有するグリシジルアミン型エポキシ化合物としては、特に制限はないが、例えば以下の構造で表されるものが挙げられる。 In the general formula (1), R 1 is a glycidyl group or an alkyl group having 1 to 5 carbon atoms. Although there is no restriction | limiting in particular as a glycidylamine type epoxy compound which has a structure (group) represented by General formula (1), For example, what is represented with the following structures is mentioned.
一般式（２）〜（３）中、Ｒ２〜Ｒ１７はそれぞれ同一でも異なっていてもよく、グリジシルエーテル基、前記一般式（１）で表される基、水素原子、または、炭素数１〜５のアルキル基である。ただし、一般式（２）においては、Ｒ２〜Ｒ７のうち少なくとも１つがグリシジルエーテル基であって少なくとも１つが前記一般式（１）で表される基であるか、Ｒ２〜Ｒ７のうち少なくとも２つが前記一般式（１）で表される基である。また、一般式（３）においては、Ｒ８〜Ｒ１２のうち少なくとも１つとＲ１３〜Ｒ１７のうち少なくとも１つが前記一般式（１）で表される基である。また、上記一般式（３）中、Ｘは直接結合、炭素数１〜６のアルキレン基、エーテル基、チオエーテル基、スルホニル基またはアリーレン基を表す。アルキレン基は鎖状でも環状でもよい。 In the general formulas (2) to (3), R 2 to R 17 may be the same or different from each other, and are a glycidyl ether group, a group represented by the general formula (1), a hydrogen atom, or a carbon number. 1 to 5 alkyl groups. However, in the general formula (2), at least one of R 2 to R 7 is a glycidyl ether group and at least one is a group represented by the general formula (1), or R 2 to R 7 Among them, at least two are groups represented by the general formula (1). In the general formula (3), at least one of R 8 to R 12 and at least one of R 13 to R 17 are groups represented by the general formula (1). In the general formula (3), X represents a direct bond, an alkylene group having 1 to 6 carbon atoms, an ether group, a thioether group, a sulfonyl group, or an arylene group. The alkylene group may be linear or cyclic.
グリシジルアミン型エポキシ化合物としては、具体的には、Ｎ，Ｎ−ビス（２，３−エポキシプロピル）−４−（２，３−エポキシプロポキシ）アニリン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラキス（２，３−エポキシプロピル）−１，４−フェニレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラキス（オキシラン−２−イルメチル）−４，４’−メチレンジアニリン、ｊＥＲ−６３０、ｊＥＲ−６３０ＬＳＤ、ｊＥＲ−６０４（商品名、三菱化学（株）製）、アデカレジンＥＰ−３９００Ｓ（商品名、（株）アデカ製）、ＹＨ−４３４、ＹＨ−４３４Ｌ（商品名、新日鐵化学（株）製）、ＴＥＰＩＣ−Ｓ（商品名、日産化学工業（株）製）等が挙げられる。これらは単独でまたは２種類以上を組み合わせて使用される。 Specific examples of the glycidylamine type epoxy compound include N, N-bis (2,3-epoxypropyl) -4- (2,3-epoxypropoxy) aniline, N, N, N ′, N′-tetrakis. (2,3-epoxypropyl) -1,4-phenylenediamine, N, N, N ′, N′-tetrakis (oxiran-2-ylmethyl) -4,4′-methylenedianiline, jER-630, jER— 630LSD, jER-604 (trade name, manufactured by Mitsubishi Chemical Corporation), Adeka Resin EP-3900S (trade name, manufactured by Adeka Corporation), YH-434, YH-434L (trade name, Nippon Steel Chemical Co., Ltd.) Product), TEPIC-S (trade name, manufactured by Nissan Chemical Industries, Ltd.) and the like. These may be used alone or in combination of two or more.
さらに本発明のコア−シェル構造粒子のシェルは、上記のグリシジルアミン型エポキシ化合物を付加重合させて得られる樹脂のみから構成されていてもよいし、グリシジルアミン型エポキシ化合物とそれ以外のエポキシ化合物を混合して付加重合させて得られる樹脂でもよい。そのようなエポキシ化合物の具体例としては、ビスフェノールＡ型エポキシ化合物、ビスフェノールＦ型エポキシ化合物、ビスフェノールＳ型エポキシ化合物、水添ビスフェノールＡ型エポキシ化合物、フェノールノボラック型エポキシ化合物、クレゾールノボラック型エポキシ化合物、ビフェニル型エポキシ化合物、ナフタレン型エポキシ化合物、およびトリフェニルメタン型エポキシ化合物等のグリシジルエーテル型エポキシ化合物が挙げられる。 Furthermore, the shell of the core-shell structure particle of the present invention may be composed of only a resin obtained by addition polymerization of the above glycidylamine type epoxy compound, or a glycidylamine type epoxy compound and other epoxy compounds may be used. A resin obtained by mixing and addition polymerization may be used. Specific examples of such epoxy compounds include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, hydrogenated bisphenol A type epoxy compounds, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds, biphenyl. Glycidyl ether type epoxy compounds, such as a type epoxy compound, a naphthalene type epoxy compound, and a triphenylmethane type epoxy compound.
次に、本発明のコア−シェル構造粒子の製造方法について説明する。ただし、以下の方法は一例であり、本発明のコア−シェル構造粒子を得る方法であれば、各工程は適宜変更することができる。 Next, the manufacturing method of the core-shell structured particles of the present invention will be described. However, the following method is an example, and each step can be appropriately changed as long as it is a method for obtaining the core-shell structured particles of the present invention.
まず、磁性体無機粒子（２次粒子、凝集状態のものを含む）、グリシジルアミン型エポキシ化合物および溶媒を所定の分量で混合する。この際、磁性体無機粒子は前処理としてシランカップリング剤等で表面処理が施されていてもよい。また、磁性体無機粒子は混合前に解砕および分散処理として、磁性体無機粒子、溶媒、および必要に応じて分散剤を混合し、分散メディアを用いて処理を行ってもよい。分散および解砕方法としては、ボールミル、ホモジナイザー、ビーズミル、遊星式ボールミルなどが挙げられる。分散メディアには微小ビーズを用いる。本発明においては、ビーズの平均粒子径が０．０３ｍｍ以上５ｍｍ以下のものを用いることが好ましい。ビーズの平均粒子径が５ｍｍ以下である場合、ビーズの間を磁性体無機粒子が通過する際に、磁性体無機粒子がビーズと接触する頻度が高く、十分な分散効果が得られる。ビーズの平均粒子径が０．０３ｍｍ以上である場合、個々のビーズの持つ運動量が十分大きく、磁性体無機粒子の凝集をほぐすのに十分なせん断応力が得られる。 First, magnetic inorganic particles (including secondary particles and aggregated particles), a glycidylamine type epoxy compound and a solvent are mixed in a predetermined amount. At this time, the magnetic inorganic particles may be surface-treated with a silane coupling agent or the like as a pretreatment. In addition, the magnetic inorganic particles may be crushed and dispersed before mixing by mixing the magnetic inorganic particles, a solvent, and, if necessary, a dispersant and using a dispersion medium. Examples of the dispersion and crushing method include a ball mill, a homogenizer, a bead mill, and a planetary ball mill. Micro beads are used as the dispersion medium. In the present invention, it is preferable to use beads having an average particle diameter of 0.03 mm to 5 mm. When the average particle diameter of the beads is 5 mm or less, when the magnetic inorganic particles pass between the beads, the frequency of the magnetic inorganic particles coming into contact with the beads is high, and a sufficient dispersion effect is obtained. When the average particle diameter of the beads is 0.03 mm or more, the momentum possessed by each bead is sufficiently large, and a sufficient shear stress is obtained to loosen the aggregation of the magnetic inorganic particles.
コア−シェル構造粒子の製造に使用する溶媒としては、有機溶媒が好ましく、グリシジルアミン型エポキシ化合物を溶解するものであればよい。具体的には、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、エチレングリコールジブチルエーテルなどのエーテル類、エチレングリコールモノエチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、プロピルアセテート、ブチルアセテート、イソブチルアセテート、３−メトキシブチルアセテート、３−メチル−３−メトキシブチルアセテート、乳酸メチル、乳酸エチル、乳酸ブチルなどのアセテート類、アセトン、メチルエチルケトン、アセチルアセトン、メチルプロピルケトン、メチルブチルケトン、メチルイソブチルケトン、シクロペンタノン、２−ヘプタノンなどのケトン類、ブチルアルコール、イソブチルアルコール、ペンタノ−ル、４−メチル−２−ペンタノール、３−メチル−２−ブタノール、３−メチル−３−メトキシブタノール、ジアセトンアルコールなどのアルコール類、トルエン、キシレンなどの芳香族炭化水素類、その他、Ｎ−メチル−２−ピロリドン、Ｎ−シクロヘキシル−２−ピロリドン、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、ジメチルスルホキシド、γ−ブチロラクトンなどが挙げられる。有機溶媒は１種を単独で用いたり、２種以上を混合して用いたりすることができる。 As the solvent used for the production of the core-shell structured particles, an organic solvent is preferable, as long as it dissolves the glycidylamine type epoxy compound. Specifically, ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoethyl ether Acetate, propylene glycol monomethyl ether acetate, propyl acetate, butyl acetate, isobutyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, acetates such as methyl lactate, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, Acetylacetone, methylpropylketone, methylbutylketone, Ketones such as til isobutyl ketone, cyclopentanone, 2-heptanone, butyl alcohol, isobutyl alcohol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxy Alcohols such as butanol and diacetone alcohol, aromatic hydrocarbons such as toluene and xylene, others, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N, N-dimethylformamide, N, N- Examples thereof include dimethylacetamide, dimethyl sulfoxide, and γ-butyrolactone. An organic solvent can be used individually by 1 type, or can mix and use 2 or more types.
次に、混合した溶液を所定の時間、加熱することで、コア−シェル構造粒子を得ることができる。加熱する温度は、１００〜２００℃が好ましく、加熱時間は１〜１２時間が好ましい。この際、粒子の沈降を防ぐために、攪拌しながら加熱することが好ましい。 Next, core-shell structure particles can be obtained by heating the mixed solution for a predetermined time. The heating temperature is preferably 100 to 200 ° C., and the heating time is preferably 1 to 12 hours. At this time, in order to prevent sedimentation of particles, it is preferable to heat with stirring.
コア−シェル構造粒子のシェルの平均厚さは１０ｎｍ以上１０００ｎｍ以下であることが好ましい。シェルの平均厚さが１０００ｎｍ以下であれば、磁性体無機粒子の高充填が可能となり、比透磁率が高い磁性体組成物を得ることができる。より好ましくは５００ｎｍ以下である。シェルの平均厚さが１０ｎｍ以上であればコア−シェル構造粒子のコア同士の導通を抑えることができ、体積抵抗率を増大させることができる。より好ましくは２０ｎｍ以上である。なお、本発明においては、シェルの平均厚さが１０ｎｍ未満である場合は、ＴＥＭ観察で、シェルであるかどうかの判定が難しいことから、コア−シェル構造粒子ではないとした。 The average shell thickness of the core-shell structured particles is preferably 10 nm or more and 1000 nm or less. When the average thickness of the shell is 1000 nm or less, high filling of the magnetic inorganic particles is possible, and a magnetic composition having a high relative magnetic permeability can be obtained. More preferably, it is 500 nm or less. If the average thickness of the shell is 10 nm or more, the conduction between the cores of the core-shell structured particles can be suppressed, and the volume resistivity can be increased. More preferably, it is 20 nm or more. In the present invention, when the average thickness of the shell is less than 10 nm, it is difficult to determine whether it is a shell or not by TEM observation.
なお、本発明においてシェルの平均厚さとは、以下のようにして得られた値をいう。すなわち、作製したコア−シェル構造粒子のＴＥＭ（透過型電子顕微鏡）観察を行い、得られたＴＥＭ写真から、測定対象としたいコア−シェル構造粒子について１０箇所のシェルの厚さを測定し、最大値と最小値を除いた８つの値の平均値をシェル層の平均厚さとする。なお、複数のコア−シェル構造粒子のシェル部分が接触している場合は、接触している領域については測定点には含めないものとする。 In the present invention, the average thickness of the shell refers to a value obtained as follows. That is, TEM (transmission electron microscope) observation of the produced core-shell structured particles was performed, and the thickness of 10 shells was measured for the core-shell structured particles desired to be measured from the obtained TEM photograph. The average value of the eight values excluding the value and the minimum value is defined as the average thickness of the shell layer. In addition, when the shell part of several core-shell structure particle | grains is contacting, the area | region which is contacting shall not be included in a measurement point.
得られたコア−シェル構造粒子を粉末として取り出すためには、コア−シェル構造粒子分散液を濾過してコア−シェル構造粒子を分離する。また、濾過ではなく、上澄みを捨てて沈殿物を取り出す方法も可能である。また、コア−シェル構造粒子分散液のコア−シェル構造粒子を自然沈降させて得る方法もある。この場合は、一度上澄みを捨て、それから沈殿物に溶媒を加えてかき混ぜ、再び沈殿させ、上澄みを捨てる工程を数回行ってから、沈殿物を得ることで、未反応の樹脂モノマーやコア−シェル構造粒子にならなかった樹脂を除去できる可能性が高くなる。 In order to take out the obtained core-shell structured particles as a powder, the core-shell structured particles dispersion is filtered to separate the core-shell structured particles. Further, instead of filtration, it is possible to discard the supernatant and take out the precipitate. There is also a method obtained by natural sedimentation of the core-shell structured particles of the core-shell structured particle dispersion. In this case, once the supernatant is discarded, the solvent is added to the precipitate, and the mixture is stirred, precipitated again, and the supernatant is discarded several times, and then the precipitate is obtained to obtain unreacted resin monomer and core-shell. There is a high possibility that the resin that has not become structured particles can be removed.
上記の方法によれば、磁性体無機粒子表面が樹脂により効率よく覆われ、容易にコア−シェル構造粒子を得ることができる。 According to the above method, the surface of the magnetic inorganic particles is efficiently covered with the resin, and the core-shell structured particles can be easily obtained.
本発明のペースト組成物はマトリックス樹脂を含有する。マトリックス樹脂としては、電子部品の分野で通常用いられる絶縁材料であれば良い。具体的には、ビニル樹脂、ノルボルネン樹脂、エポキシ樹脂、アクリレート樹脂、メタクリレート樹脂、エポキシアクリレート樹脂、エポキシメタクリレート樹脂、シアネート樹脂、ビスマレイミド−トリアジン樹脂、ベンゾシクロブテン樹脂、シロキサン樹脂などの、重合性基を有する熱硬化型あるいはＵＶ硬化型の樹脂が挙げられる。また、ポリスチレン樹脂、ポリエーテルイミド樹脂、ポリフェニレンエーテル樹脂、ポリイミド樹脂、アラミド樹脂、ノボラック樹脂など重合性基を持たない樹脂も挙げられる。これらの樹脂は、単独で用いてもよいし、複数種を適当な比にて用いてもよい。 The paste composition of the present invention contains a matrix resin. The matrix resin may be any insulating material that is usually used in the field of electronic components. Specifically, polymerizable groups such as vinyl resins, norbornene resins, epoxy resins, acrylate resins, methacrylate resins, epoxy acrylate resins, epoxy methacrylate resins, cyanate resins, bismaleimide-triazine resins, benzocyclobutene resins, and siloxane resins. And a thermosetting or UV curable resin. In addition, resins having no polymerizable group such as polystyrene resin, polyetherimide resin, polyphenylene ether resin, polyimide resin, aramid resin, and novolak resin are also included. These resins may be used singly or plural kinds may be used in an appropriate ratio.
上記の中でも、硬化後の磁性体組成物の耐熱性や基材との接着性に優れる点から、エポキシ樹脂を含有することが好ましい。また、ペースト組成物から得られる磁性体組成物をインダクタ用コアや電磁波吸収体に用いる場合は、ＵＶ硬化型の樹脂を選定すると、フォトリソグラフィー法による磁性体組成物のパターニングが実現でき好ましい。 Among the above, it is preferable to contain an epoxy resin from the viewpoint of excellent heat resistance of the magnetic composition after curing and adhesion to the substrate. In addition, when a magnetic composition obtained from a paste composition is used for an inductor core or an electromagnetic wave absorber, it is preferable to select a UV curable resin because patterning of the magnetic composition by photolithography can be realized.
また、エポキシ樹脂を用いる場合は、エポキシ樹脂と硬化剤を組み合わせることが好ましい。硬化剤を用いることで、ペースト組成物をより低温および短時間で硬化させることができる。さらに、硬化物の耐熱性や靭性を向上することが可能となる。 Moreover, when using an epoxy resin, it is preferable to combine an epoxy resin and a hardening | curing agent. By using the curing agent, the paste composition can be cured at a lower temperature and in a shorter time. Furthermore, the heat resistance and toughness of the cured product can be improved.
このように、硬化剤はエポキシ樹脂の硬化を促進する役割を持つものであるから、公知の硬化剤を特に制限なく用いることができる。例えば、各種脂肪族アミン系化合物、芳香族アミン系化合物、酸無水物系化合物、ジシアンジアミド系化合物、フェノール系化合物、カルボン酸系化合物、チオール系化合物、およびイミダゾール系化合物などが挙げられる。これらは単独でまたは２種類以上を組み合わせて使用される。 Thus, since a hardening | curing agent has a role which accelerates | stimulates hardening of an epoxy resin, a well-known hardening | curing agent can be especially used without a restriction | limiting. Examples include various aliphatic amine compounds, aromatic amine compounds, acid anhydride compounds, dicyandiamide compounds, phenol compounds, carboxylic acid compounds, thiol compounds, and imidazole compounds. These may be used alone or in combination of two or more.
本発明のペースト組成物は、必要に応じて、塗布した膜の表面状態を良好なものとするために、界面活性剤を含有しても良い。また、基材との接着性を高めるために、シランカップリング剤、チタンキレート剤などを含有することもできる。 The paste composition of the present invention may contain a surfactant as necessary in order to improve the surface state of the applied film. Moreover, in order to improve adhesiveness with a base material, a silane coupling agent, a titanium chelating agent, etc. can also be contained.
さらに、本発明のペースト組成物は必要に応じて、架橋剤、架橋促進剤、溶解調整剤、安定剤、消泡剤などを含有することもできる。 Furthermore, the paste composition of this invention can also contain a crosslinking agent, a crosslinking accelerator, a dissolution regulator, a stabilizer, an antifoamer, etc. as needed.
本発明において、ペースト組成物中のコア−シェル構造粒子の含有量は、有機溶媒などの揮発成分を除いた固形成分に対して、５０重量％以上９８重量％以下であることが好ましい。ペースト組成物中の固形成分に対するコア−シェル構造粒子の含有量が５０重量％以上であると、得られる磁性体組成物の透磁率を大きくすることができる。ペースト組成物中の固形成分に対するコア−シェル構造粒子の含有量は、より好ましくは８０重量％以上である。ペースト組成物中の固形成分に対するコア−シェル構造粒子の含有量が９８重量％以下であると、耐クラック性や基板との接着性が向上する。 In the present invention, the content of the core-shell structured particles in the paste composition is preferably 50 wt% or more and 98 wt% or less with respect to the solid components excluding volatile components such as organic solvents. When the content of the core-shell structure particles with respect to the solid component in the paste composition is 50% by weight or more, the magnetic permeability of the obtained magnetic composition can be increased. The content of the core-shell structured particles with respect to the solid component in the paste composition is more preferably 80% by weight or more. When the content of the core-shell structure particles with respect to the solid component in the paste composition is 98% by weight or less, the crack resistance and the adhesion to the substrate are improved.
次に、本発明のペースト組成物を作製する方法を説明する。本発明のペースト組成物は磁性体無機粒子をコアとするコア−シェル構造粒子、マトリックス樹脂を含有し、ペーストの流動性を調整するために必要に応じて有機溶媒を含有することができる。有機溶媒としては特に制限はないが、例えばＮ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ−メチル−２−ピロリドン、ジメチルイミダゾリジノン、ジメチルスルホキシド、γ−ブチロラクトン、乳酸エチル、１−メトキシ−２−プロパノール、１−エトキシ−２−プロパノール、エチレングリコールモノ−ｎ−プロピルエーテル、ジアセトンアルコール、テトラヒドロフルフリルアルコール、プロピレングリコールモノメチルエーテルアセテートなどが挙げられる。有機溶媒は１種を単独で用いたり、２種以上を混合して用いたりすることができる。 Next, a method for producing the paste composition of the present invention will be described. The paste composition of the present invention contains core-shell structured particles having magnetic inorganic particles as a core and a matrix resin, and may contain an organic solvent as necessary in order to adjust the fluidity of the paste. The organic solvent is not particularly limited. For example, N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, dimethylimidazolidinone, dimethyl sulfoxide, γ-butyrolactone, ethyl lactate, 1- Examples include methoxy-2-propanol, 1-ethoxy-2-propanol, ethylene glycol mono-n-propyl ether, diacetone alcohol, tetrahydrofurfuryl alcohol, propylene glycol monomethyl ether acetate and the like. An organic solvent can be used individually by 1 type, or can mix and use 2 or more types.
まず、コア−シェル構造粒子、マトリックス樹脂および必要に応じ有機溶媒を所定量混合する。その後、ペースト組成物を均質にするために、ボールミルやロールミル、ニーダーを用いた処理を行う。このような処理を行える装置としては、例えば、３本ロール（ＥＸＡＫＴ（株）製、ｍｏｄｅｌ−５０）等がある。３本ロールは、高せん断応力を持つため、ペースト組成物をより均質にすることができる。 First, a predetermined amount of core-shell structured particles, a matrix resin, and, if necessary, an organic solvent are mixed. Then, in order to make the paste composition homogeneous, a treatment using a ball mill, a roll mill, or a kneader is performed. As an apparatus capable of performing such processing, for example, there are three rolls (EXAKT, model-50). Since the three rolls have a high shear stress, the paste composition can be made more homogeneous.
このとき必要に応じさらに他の物質を混合してもよい。また、ペースト組成物の粘度を調整するために、さらに有機溶媒を追加したり、加熱や減圧により有機溶媒を適量除去したりしてもよい。また、このとき得られたコア−シェル構造粒子と樹脂溶液を混合する前に、コア−シェル構造粒子を前処理させたものを利用してもよい。 At this time, other substances may be further mixed as necessary. Moreover, in order to adjust the viscosity of the paste composition, an organic solvent may be further added, or an appropriate amount of the organic solvent may be removed by heating or decompression. Moreover, before mixing the core-shell structured particles obtained at this time and the resin solution, the core-shell structured particles pretreated may be used.
さらに、本発明のペースト組成物は、上記の混合物を３本ロール等で混錬後にフィルターで濾過したものであっても構わない。濾過する方法としては、真空濾過、加圧濾過、大気濾過等があるが、この中でも加圧濾過が好ましい。加圧濾過の場合は、圧力は０．１〜０．４Ｍｐａが好ましく、また、濾過フィルターは、捕捉粒子径０．５〜１００μｍのメンブレムフィルターが好ましい。 Furthermore, the paste composition of the present invention may be one obtained by kneading the above mixture with three rolls or the like and then filtering it with a filter. Examples of the filtering method include vacuum filtration, pressure filtration, atmospheric filtration, and the like. Among these, pressure filtration is preferable. In the case of pressure filtration, the pressure is preferably 0.1 to 0.4 Mpa, and the filtration filter is preferably a membrane filter having a trapped particle size of 0.5 to 100 μm.
次に、上記のようにして製造したペースト組成物を硬化させて、磁性体組成物を製造する方法について詳細に説明する。例えば、ペースト組成物をある被着体に塗布し、有機溶媒を除去し、加熱処理などによりペースト組成物を硬化させ、磁性体組成物を製造することができる。ただし、本発明の磁性体組成物は焼結体ではないので、樹脂を完全に分解、除去する必要はなく、電子部品の耐熱温度範囲内（例えば、５００℃以下の温度）で加熱することが好ましい。 Next, a method for producing a magnetic composition by curing the paste composition produced as described above will be described in detail. For example, the magnetic composition can be produced by applying the paste composition to an adherend, removing the organic solvent, and curing the paste composition by heat treatment or the like. However, since the magnetic composition of the present invention is not a sintered body, it is not necessary to completely decompose and remove the resin, and it can be heated within the heat resistant temperature range of the electronic component (for example, a temperature of 500 ° C. or less). preferable.
ペースト組成物を塗布する被着体は、例えば、シリコンウエハー、ガラス類、セラミックス類およびガリウムヒ素などの基板、有機系回路基板、無機系回路基板、ならびにこれらの基板に回路の構成材料が配置されたものなどが挙げられるが、これらに限定されない。有機系回路基板の例としては、ガラス布・エポキシ銅張積層板などのガラス基材銅張積層板、ガラス不織布・エポキシ銅張積層板などのコンポジット銅張積層板、ポリエーテルイミド樹脂基板、ポリエーテルケトン樹脂基板、ポリイミド樹脂基板、ポリサルフォン系樹脂基板などの耐熱・熱可塑性基板、ポリエステル銅張フィルム基板、ポリイミド銅張フィルム基板などのフレキシブル基板が挙げられる。 The adherend to which the paste composition is applied is, for example, a silicon wafer, glass, ceramics, gallium arsenide, or the like, an organic circuit board, an inorganic circuit board, and circuit constituent materials disposed on these boards. However, it is not limited to these. Examples of organic circuit boards include glass-based copper-clad laminates such as glass cloth / epoxy copper-clad laminates, composite copper-clad laminates such as glass nonwoven fabrics / epoxy copper-clad laminates, polyetherimide resin substrates, Examples include heat-resistant / thermoplastic substrates such as ether ketone resin substrates, polyimide resin substrates, and polysulfone resin substrates, and flexible substrates such as polyester copper-clad film substrates and polyimide copper-clad film substrates.
また、無機系回路基板の例は、アルミナ基板、窒化アルミニウム基板、炭化ケイ素基板などのセラミック基板、アルミニウムベース基板、鉄ベース基板などの金属系基板が挙げられる。回路の構成材料の例は、銀、金、銅などの金属を含有する導体、無機系酸化物などを含有する抵抗体、ガラス系材料および／または樹脂などを含有する低誘電体、樹脂や高誘電率無機粒子などを含有する高誘電体、ガラス系材料などを含有する絶縁体などが挙げられる。 Examples of the inorganic circuit board include ceramic substrates such as an alumina substrate, an aluminum nitride substrate, and a silicon carbide substrate, and metal substrates such as an aluminum base substrate and an iron base substrate. Examples of circuit components include conductors containing metals such as silver, gold and copper, resistors containing inorganic oxides, low dielectrics containing glass materials and / or resins, resins and high Examples thereof include high dielectric materials containing dielectric constant inorganic particles, insulators containing glass-based materials, and the like.
また、被着体とペースト組成物との接着性を高めるために、被着体表面にシランカップリング剤などによる表面処理を施してもよい。 Further, in order to enhance the adhesion between the adherend and the paste composition, the surface of the adherend may be subjected to a surface treatment with a silane coupling agent or the like.
ペースト組成物を被着体に塗布する方法としてはスピナーを用いた回転塗布、スプレー塗布、ロールコーティング、スクリーン印刷、ブレードコーター、ダイコーター、カレンダーコーター、メニスカスコーター、バーコーターなどの方法がある。また、塗布膜厚は、塗布手法、組成物の固形分濃度、粘度などによって異なるが、通常、乾燥後の膜厚が、０．１〜３００μｍになるように塗布することが好ましい。 Examples of methods for applying the paste composition to the adherend include spin coating using a spinner, spray coating, roll coating, screen printing, blade coater, die coater, calendar coater, meniscus coater, bar coater and the like. Further, the coating film thickness varies depending on the coating method, the solid content concentration of the composition, the viscosity, and the like, but it is usually preferable that the coating film thickness is 0.1 to 300 μm after drying.
次に被着体上に塗布したペースト組成物膜から有機溶媒を除去する。有機溶媒を除去する方法としては、オーブン、ホットプレート、赤外線などによる加熱乾燥や真空乾燥などが挙げられる。加熱乾燥は５０℃から１８０℃の範囲で１分から数時間行うのが好ましい。なお、本工程はいわゆる乾燥工程に該当するため、ここで有機溶媒を完全に除去する必要はない。 Next, the organic solvent is removed from the paste composition film applied on the adherend. Examples of the method for removing the organic solvent include oven drying, hot plate, heat drying with infrared rays, vacuum drying, and the like. Heat drying is preferably performed in the range of 50 ° C. to 180 ° C. for 1 minute to several hours. In addition, since this process corresponds to what is called a drying process, it is not necessary to remove an organic solvent completely here.
その後、用いたペースト組成物中の樹脂の硬化機構に応じて、加熱処理や光照射などによりペースト組成物の硬化反応を進行させる。なお、加熱処理の場合は、次工程である膜強化のための加熱処理と兼ねてもよい。 Thereafter, the curing reaction of the paste composition is advanced by heat treatment or light irradiation according to the curing mechanism of the resin in the used paste composition. In the case of heat treatment, the heat treatment for film strengthening, which is the next step, may be used.
次に、膜強化のために加熱処理を行う。加熱の処理温度は１２０℃から４００℃の範囲内が好ましく、一定温度あるいは段階的に昇温し、処理時間は５分から５時間の範囲で実施することができる。より好ましくは、１５０℃以上、２５０℃未満である。さらに好ましくは２００℃以下である。２００℃以下であると、コア−シェル構造粒子を製造するにあたり前処理でシランカップリング剤を利用した場合に、そのシランカップリング剤が失活する可能性が低くなり、その結果、コア−シェル構造粒子のシェル膜を維持でき、高体積抵抗率を得ることができる。また、窒素などの不活性雰囲気下での処理とすると、重合体の酸化を抑制するので好ましい。酸素により活性が失われるラジカルを発生させる重合促進剤を用いた組成で硬化を行う場合も、窒素などの不活性雰囲気下での処理とすると、重合を阻害しないので好ましい。 Next, heat treatment is performed to strengthen the film. The heating treatment temperature is preferably in the range of 120 ° C. to 400 ° C., the temperature is raised at a constant temperature or stepwise, and the treatment time can be in the range of 5 minutes to 5 hours. More preferably, it is 150 degreeC or more and less than 250 degreeC. More preferably, it is 200 degrees C or less. When the temperature is 200 ° C. or lower, when the silane coupling agent is used in the pretreatment for producing the core-shell structured particles, the possibility that the silane coupling agent is deactivated becomes low. A shell film of structured particles can be maintained, and a high volume resistivity can be obtained. In addition, treatment under an inert atmosphere such as nitrogen is preferable because oxidation of the polymer is suppressed. Even in the case of curing with a composition using a polymerization accelerator that generates radicals whose activity is lost by oxygen, treatment under an inert atmosphere such as nitrogen is preferable because polymerization is not inhibited.
以上のように作製された、本発明のコアーシェル構造粒子を含むペースト組成物から得られる磁性体組成物は、磁性体無機粒子の樹脂中での分散性が良好で、比透磁率を大きく保ったままｔａｎδが小さくなるなど、磁性体材料として優れた特性を示す。また体積抵抗率も高い。 The magnetic composition obtained from the paste composition containing the core-shell structure particles of the present invention produced as described above has good dispersibility in the resin of the magnetic inorganic particles and maintains a large relative permeability. Excellent characteristics as a magnetic material, such as tan δ being reduced. Also, the volume resistivity is high.
磁性体組成物の体積抵抗率は、１×１０８Ωｃｍ以上であることが好ましい。１×１０８Ωｃｍ以上であると、絶縁性が良好であり、リーク電流を抑制することが可能となる。より好ましくは１×１０１０Ωｃｍ以上であり、さらに好ましくは、１×１０１２Ωｃｍ以上であり、この場合には絶縁性が特に良好となる。 The volume resistivity of the magnetic composition is preferably 1 × 10 8 Ωcm or more. When it is 1 × 10 8 Ωcm or more, the insulation is good and the leakage current can be suppressed. More preferably, it is 1 × 10 10 Ωcm or more, and further preferably 1 × 10 12 Ωcm or more. In this case, the insulating property is particularly good.
本発明のコア−シェル構造粒子含有の磁性体組成物の形態は特に限定されず、膜状、棒状、球状など、用途に合わせて選択することができるが、特に膜状であることが好ましい。ここでいう膜とは、フィルム、シート、板、ペレットなども含まれる。もちろん、導通のためのビアホール形成、インピーダンスや静電容量あるいは内部応力の調整、または、放熱機能付与など、用途にあわせた加工を行うこともできる。 The form of the core-shell structured particle-containing magnetic material composition of the present invention is not particularly limited and can be selected according to the application, such as a film shape, a rod shape, a spherical shape, etc., but a film shape is particularly preferable. The membrane here includes a film, a sheet, a plate, a pellet and the like. Of course, processing according to the application such as formation of a via hole for conduction, adjustment of impedance, capacitance or internal stress, or provision of a heat dissipation function can also be performed.
次に、本発明のコア−シェル構造粒子やペースト組成物の用途として、磁性体組成物を有するインダクタについて説明する。なお近年は様々なインダクタが提案されており、本発明のペースト組成物の用途は以下に限定されるものではない。 Next, an inductor having a magnetic composition will be described as an application of the core-shell structured particles and paste composition of the present invention. In recent years, various inductors have been proposed, and the use of the paste composition of the present invention is not limited to the following.
本発明のコア−シェル構造粒子や、コア−シェル構造粒子を利用したペースト組成物および磁性体組成物の用途は、例えば、高透磁率を有するインダクタ用コアへの適用が好ましい。また、本発明でいうインダクタは、半導体素子、ＩＣチップ、回路基板およびこれらを含む電子部品に形成されていることが好ましい。 The use of the core-shell structured particles of the present invention, the paste composition using the core-shell structured particles, and the magnetic composition is preferably applied to, for example, an inductor core having a high magnetic permeability. Further, the inductor referred to in the present invention is preferably formed in a semiconductor element, an IC chip, a circuit board, and an electronic component including these.
本発明のコア−シェル構造粒子およびペースト組成物の硬化物を有するインダクタの製造方法の例は以下の通りである。ＩＣチップの電子回路が形成されていない面に渦巻き状の巻き線が平面内にスパイラルインダクタを形成する。スパイラルインダクタの製造方法は、公知の製造技術を用いて製造することができ、例えば電解メッキ法を用いて製造することができる。次に、そのスパイラルインダクタ上に本発明のコア−シェル構造粒子を含むペースト組成物を塗布し、乾燥する。その後、加熱処理することによって、本発明のコア−シェル構造粒子を含む磁性体組成物がコアとして用いられたインダクタが得られる。また、別の製造方法としては、例えば、フェライト粉末をポリイミド樹脂等でペースト状にして薄い中空を持つ膜を多数作り、それらの膜に導電パターンを印刷して、重ねて焼成してできたインダクタの中空部に、上記で作製したコア−シェル構造粒子含有のペースト組成物を塗布し、硬化させる。その結果、本発明のコア−シェル構造粒子を含む磁性体組成物がコアとして用いられたインダクタが得られる。 The example of the manufacturing method of the inductor which has the hardened | cured material of the core-shell structure particle | grains and paste composition of this invention is as follows. A spiral winding forms a spiral inductor in the plane on the surface of the IC chip where the electronic circuit is not formed. The manufacturing method of a spiral inductor can be manufactured using a well-known manufacturing technique, for example, can be manufactured using an electrolytic plating method. Next, the paste composition containing the core-shell structured particles of the present invention is applied onto the spiral inductor and dried. Thereafter, by performing a heat treatment, an inductor in which the magnetic composition containing the core-shell structured particles of the present invention is used as a core is obtained. As another manufacturing method, for example, an inductor made by pasting ferrite powder into polyimide resin or the like to make a large number of thin hollow films, printing conductive patterns on those films, and firing them in layers The paste composition containing the core-shell structure particles prepared above is applied to the hollow portion of the material and cured. As a result, an inductor is obtained in which the magnetic composition containing the core-shell structured particles of the present invention is used as a core.
本発明の磁性体組成物の透磁率は、たとえば次のように測定することができる。ガラス基板やフィルム基板等の非磁性基板の上に形成した高透磁率材料の薄膜試料をコイル中に配置し、コイル近傍のストリップ線路からコイルに磁束が鎖交するように交流磁界をかける。測定を行なう周波数に対し、ネットワークアナライザーでＳパラメータの伝達係数Ｓ２１を測定し、試料をコイル中に置くことによって伝達係数Ｓ２１がどの程度変化するかによって透磁率を求めることができる。このような方法で測定できる装置としては、例えば、高周波薄膜透磁率測定装置（（株）東栄科学産業製）がある。 The magnetic permeability of the magnetic composition of the present invention can be measured, for example, as follows. A thin film sample of a high magnetic permeability material formed on a non-magnetic substrate such as a glass substrate or a film substrate is placed in the coil, and an alternating magnetic field is applied so that a magnetic flux is linked to the coil from a strip line near the coil. With respect to the frequency to be measured, the transmission coefficient S21 of the S parameter is measured with a network analyzer, and the permeability can be obtained depending on how much the transmission coefficient S21 changes by placing the sample in the coil. As an apparatus which can measure by such a method, there exists a high frequency thin film magnetic permeability measuring apparatus (made by Toei Scientific Industrial Co., Ltd.), for example.
本発明のコア−シェル粒子含有の磁性体組成物は、パソコン、携帯電話や携帯情報端末、フラットパネルテレビ、ゲーム機器等の小型機器の電子回路に用いられるものである。 The core-shell particle-containing magnetic material composition of the present invention is used in electronic circuits of small devices such as personal computers, mobile phones, personal digital assistants, flat panel televisions, and game devices.
以下、本発明の実施例について説明するが、本発明はこれらによって限定されるものではない。なお、実施例中のコア−シェル構造粒子並びにペースト組成物の評価は以下の方法により行った。 Examples of the present invention will be described below, but the present invention is not limited to these examples. In addition, evaluation of the core-shell structure particle | grains and paste composition in an Example was performed with the following method.
＜シェルの平均厚さの測定＞
作製したコア−シェル構造粒子をＨ−７１００ＦＡ（（株）日立製作所製）を用いてＴＥＭ観察を行い、１００ｎｍが実測で５ｃｍとなるまで拡大した（５０万倍）。この状態で、測定対象としたいコア−シェル構造粒子について１０箇所のシェルの厚さを測定し、最大値と最小値を除いた８つの値の平均値をシェルの平均厚さとした。なお、粒子同士がシェル樹脂を介して接触している場合には、接触している部分については測定個所には含めなかった。
<Measurement of average thickness of shell>
The produced core-shell structured particles were subjected to TEM observation using H-7100FA (manufactured by Hitachi, Ltd.), and expanded to 100 nm until the actual measurement was 5 cm (500,000 times). In this state, the thickness of 10 shells was measured for the core-shell structured particles to be measured, and the average value of 8 values excluding the maximum and minimum values was taken as the average thickness of the shell. In addition, when the particles are in contact with each other via the shell resin, the contacted portion was not included in the measurement location.
＜磁性体組成物の体積抵抗率の測定方法＞
まず、ペースト組成物をＣｒ膜付きシリコン基板上に塗布した後、熱風オーブン炉で６０℃で３０分乾燥した。次いで、イナートオーブン“ＩＮＬ−６０”（商品名、光洋サーモシステム（株）製）を用いて大気雰囲気下、１５０℃で１時間加熱処理し、磁性体組成物を得、さらに、磁性体組成物の上に、Ａｕ電極（電極面積１ｃｍ２）を蒸着した。Ａｕ電極とＣｒ膜付きシリコン基板間で、ＤＣ電圧５Ｖを印加し、その時得られた抵抗値と磁性体組成物の膜厚から、体積抵抗率を求めた。体積抵抗率は、“絶縁抵抗計６５１７Ａ”（商品名、ケースレーインスツルメンツ（株）製）を用いて測定した。磁性体組成物の膜厚は、サンプル断面のＳＥＭ（走査型電子顕微鏡）観察から測定した。
<Method for measuring volume resistivity of magnetic composition>
First, the paste composition was applied onto a silicon substrate with a Cr film, and then dried in a hot air oven furnace at 60 ° C. for 30 minutes. Next, heat treatment was performed at 150 ° C. for 1 hour in an air atmosphere using an inert oven “INL-60” (trade name, manufactured by Koyo Thermo System Co., Ltd.) to obtain a magnetic composition. Further, the magnetic composition On top of this, an Au electrode (electrode area 1 cm 2 ) was deposited. A DC voltage of 5 V was applied between the Au electrode and the silicon substrate with the Cr film, and the volume resistivity was determined from the resistance value obtained at that time and the film thickness of the magnetic composition. The volume resistivity was measured using “insulation resistance meter 6517A” (trade name, manufactured by Keithley Instruments Co., Ltd.). The film thickness of the magnetic composition was measured from SEM (scanning electron microscope) observation of the sample cross section.
＜磁性体組成物の透磁率測定＞
まず、ガラス基板上にペースト組成物を塗布した後、熱風オーブン炉で６０℃で３０分乾燥した。次いで、イナートオーブン“ＩＮＬ−６０”（商品名、光洋サーモシステム（株）製）を用いて大気雰囲気下、１５０℃で１時間加熱処理し、磁性体組成物を得た。磁性体組成物の膜厚は約１００μｍになるようにした。その磁性体組成物を５ｍｍ角にカットした後、そのサンプルを高周波薄膜透磁率測定装置（（株）東栄科学産業製）に入れて、透磁率測定を行った。測定は、その薄膜試料をコイル中に配置し、コイル近傍のストリップ線路からコイルに磁束が鎖交するように１０Ｍ〜２ＧＨｚまでの交流磁界をかけ、ネットワークアナライザーでＳパラメータの伝達係数Ｓ２１を測定し、試料をコイル中に配置しない場合と比べてＳ２１がどの程度変化するかによって透磁率を求めた。また、透磁率の補正には、測定で得られた伝達係数Ｓ１１、Ｓ２２等を用いた。また、磁性体組成物の膜厚は、サンプル断面のＳＥＭ（走査型電子顕微鏡）観察から測定した。
<Measurement of magnetic permeability of magnetic composition>
First, after applying a paste composition on a glass substrate, it was dried in a hot air oven furnace at 60 ° C. for 30 minutes. Subsequently, heat treatment was performed at 150 ° C. for 1 hour in an air atmosphere using an inert oven “INL-60” (trade name, manufactured by Koyo Thermo System Co., Ltd.) to obtain a magnetic composition. The film thickness of the magnetic composition was about 100 μm. After the magnetic composition was cut into 5 mm square, the sample was put into a high-frequency thin film magnetic permeability measuring device (manufactured by Toei Kagaku Sangyo Co., Ltd.) and magnetic permeability was measured. In the measurement, the thin film sample is placed in a coil, an AC magnetic field of 10 M to 2 GHz is applied so that a magnetic flux is linked to the coil from a strip line near the coil, and a transmission coefficient S21 of the S parameter is measured with a network analyzer. The magnetic permeability was determined according to how much S21 changed compared to the case where the sample was not placed in the coil. Moreover, the transmission coefficients S11, S22, etc. obtained by the measurement were used for correcting the magnetic permeability. The film thickness of the magnetic composition was measured from SEM (scanning electron microscope) observation of the sample cross section.
透磁率は、μ＝μ’＋ｉμ”（μ’：実部、μ”：虚部）で表され、各実施例における透磁率はμ’の値を、また、ｔａｎδは、μ”／ μ’の値を記載した。なお、各実施例においては、１ＧＨｚでの値を代表して示した。 The magnetic permeability is expressed as μ = μ ′ + iμ ″ (μ ′: real part, μ ″: imaginary part), the magnetic permeability in each example is a value of μ ′, and tan δ is μ ″ / μ ′. In each example, the value at 1 GHz is shown as a representative.
実施例、比較例で用いた各材料は以下のとおりである。 The materials used in the examples and comparative examples are as follows.
＜磁性体無機粒子＞
ＨＱ粉（商品名、ＢＡＳＦ製カルボニル鉄粉末、平均粒子径１．２μｍ）
アモルファス合金パウダー（商品名、エプソンアトミックス製Ｆｅ基アモルファス、平均粒子径１０．４５μｍ）。
<Magnetic inorganic particles>
HQ powder (trade name, BASF carbonyl iron powder, average particle size 1.2 μm)
Amorphous alloy powder (trade name, Fe-based amorphous manufactured by Epson Atmix, average particle size 10.45 μm).
＜シェル作製に用いた化合物＞
ｊＥＲ−６３０ＬＳＤ（商品名、三菱化学（株）製、グリシジルアミン型エポキシ化合物）
ｊＥＲ−６０４（商品名、三菱化学（株）製、グリシジルアミン型エポキシ化合物）
８５０Ｓ（商品名、ＤＩＣ（株）製、ビスフェノールＡ型エポキシ化合物）
<Compounds used for shell preparation>
jER-630LSD (trade name, manufactured by Mitsubishi Chemical Corporation, glycidylamine type epoxy compound)
jER-604 (trade name, manufactured by Mitsubishi Chemical Corporation, glycidylamine type epoxy compound)
850S (trade name, manufactured by DIC Corporation, bisphenol A type epoxy compound)
＜エポキシ樹脂＞
ＥＸＡ−４８５０−１５０（商品名、ＤＩＣ（株）製）
ＥＸＡ−４８８０（商品名、ＤＩＣ（株）製）
ｊＥＲ−４２５０（商品名、三菱化学（株）製）
８５０Ｓ（商品名、ＤＩＣ（株）製）
＜硬化剤＞
ビス（３−アミノフェニル）スルホン（以下、３，３’−ＤＤＳとする）
＜溶媒＞
Ｎ−メチル−２−ピロリドン（以下、ＮＭＰとする）
プロピレングリコールモノメチルエーテル（以下、ＰＧＭＥとする）
γ−ブチロラクトン（以下、ＧＢＬとする）。
<Epoxy resin>
EXA-4850-150 (trade name, manufactured by DIC Corporation)
EXA-4880 (trade name, manufactured by DIC Corporation)
jER-4250 (trade name, manufactured by Mitsubishi Chemical Corporation)
850S (trade name, manufactured by DIC Corporation)
<Curing agent>
Bis (3-aminophenyl) sulfone (hereinafter referred to as 3,3′-DDS)
<Solvent>
N-methyl-2-pyrrolidone (hereinafter referred to as NMP)
Propylene glycol monomethyl ether (hereinafter referred to as PGME)
γ-butyrolactone (hereinafter referred to as GBL).
各実施例および比較例で用いたコア−シェル構造粒子は以下の方法により合成した。 The core-shell structured particles used in each example and comparative example were synthesized by the following method.
＜コア−シェル型構造粒子Iの合成例＞
磁性体無機粒子ＨＱ粉を５０ｇ、グリシジルアミン型エポキシ化合物ｊＥＲ−６３０ＬＳＤを５ｇ、ＮＭＰ２００ｇを四つ口フラスコに投入した。次に、シリコンオイルバスを用いて、４０℃で１時間攪拌し、その後１６０℃で３時間攪拌を行い、コアーシェル構造粒子分散液を得た。次に、０．４５μｍのメンブレムフィルターを用いて加圧濾過し、濾過後、さらに上からＰＧＭＥを加え、コア−シェル構造粒子を洗浄し、加圧濾過を行った。得られた濾物を熱風オーブン炉で８０℃で１時間乾燥させ、コアーシェル構造粒子４８ｇを得た。シェルの平均厚さは２２ｎｍであった。
<Synthesis example of core-shell type structural particle I>
50 g of magnetic inorganic particles HQ powder, 5 g of glycidylamine type epoxy compound jER-630LSD, and 200 g of NMP were charged into a four-necked flask. Next, using a silicon oil bath, the mixture was stirred at 40 ° C. for 1 hour, and then stirred at 160 ° C. for 3 hours to obtain a core-shell structure particle dispersion. Next, pressure filtration was performed using a 0.45 μm membrane filter, and after filtration, PGME was further added from above to wash the core-shell structure particles, and pressure filtration was performed. The obtained filtrate was dried in a hot air oven furnace at 80 ° C. for 1 hour to obtain 48 g of core-shell structured particles. The average thickness of the shell was 22 nm.
＜コア−シェル型構造粒子IIの合成例＞
磁性体無機粒子アモルファス合金パウダーを５０ｇ、グリシジルアミン型エポキシ化合物ｊＥＲ−６３０ＬＳＤを５ｇ、ＮＭＰ２００ｇを四つ口フラスコに投入した。次に、シリコンオイルバスを用いて、４０℃で１時間攪拌し、その後１６０℃で３時間攪拌を行い、コアーシェル構造粒子分散液を得た。次に、０．４５μｍのメンブレムフィルターを用いて加圧濾過し、濾過後、さらに上からＰＧＭＥを加え、コア−シェル構造粒子を洗浄し、加圧濾過を行った。得られた濾物を熱風オーブン炉で８０℃で１時間乾燥させ、コアーシェル構造粒子４９ｇを得た。シェルの平均厚さは２５ｎｍであった。
<Synthesis example of core-shell type structural particle II>
50 g of magnetic inorganic particle amorphous alloy powder, 5 g of glycidylamine type epoxy compound jER-630LSD, and 200 g of NMP were charged into a four-necked flask. Next, using a silicon oil bath, the mixture was stirred at 40 ° C. for 1 hour, and then stirred at 160 ° C. for 3 hours to obtain a core-shell structure particle dispersion. Next, pressure filtration was performed using a 0.45 μm membrane filter, and after filtration, PGME was further added from above to wash the core-shell structure particles, and pressure filtration was performed. The obtained filtrate was dried in a hot air oven furnace at 80 ° C. for 1 hour to obtain 49 g of core-shell structured particles. The average thickness of the shell was 25 nm.
＜コア−シェル型構造粒子IIIの合成例＞
磁性体無機粒子アモルファス合金パウダーを５０ｇ、グリシジルアミン型エポキシ化合物ｊＥＲ−６０４を５ｇ、ＮＭＰ２００ｇを四つ口フラスコに投入した。次に、シリコンオイルバスを用いて、４０℃で１時間攪拌し、その後１６０℃で３時間攪拌を行い、コアーシェル構造粒子分散液を得た。次に、０．４５μｍのメンブレムフィルターを用いて加圧濾過し、濾過後、さらに上からＰＧＭＥを加え、コア−シェル構造粒子を洗浄し、加圧濾過を行った。得られた濾物を熱風オーブン炉で８０℃で１時間乾燥させ、コアーシェル構造粒子４８ｇを得た。シェルの平均厚さは１９ｎｍであった。
<Synthesis example of core-shell type structural particle III>
50 g of magnetic inorganic particle amorphous alloy powder, 5 g of glycidylamine type epoxy compound jER-604, and 200 g of NMP were charged into a four-necked flask. Next, using a silicon oil bath, the mixture was stirred at 40 ° C. for 1 hour, and then stirred at 160 ° C. for 3 hours to obtain a core-shell structure particle dispersion. Next, pressure filtration was performed using a 0.45 μm membrane filter, and after filtration, PGME was further added from above to wash the core-shell structure particles, and pressure filtration was performed. The obtained filtrate was dried in a hot air oven furnace at 80 ° C. for 1 hour to obtain 48 g of core-shell structured particles. The average thickness of the shell was 19 nm.
＜コア−シェル型構造粒子IVの合成例＞
磁性体無機粒子ＨＱ粉を５０ｇ、ＥＰＩＣＬＯＮ−８５０Ｓを５ｇ、ＮＭＰ２００ｇを四つ口フラスコに投入した。次に、シリコンオイルバスを用いて、４０℃で１時間攪拌し、その後１６０℃で３時間攪拌を行い、コアーシェル構造粒子分散液を得た。次に、０．４５μｍのメンブレムフィルターを用いて加圧濾過し、濾過後、さらに上からＰＧＭＥを加え、コア−シェル構造粒子を洗浄し、加圧濾過を行った。得られた濾物を熱風オーブン炉で８０℃で１時間乾燥させ、コアーシェル構造粒子４８ｇを得た。シェルの平均厚さは１０ｎｍ未満であり、シェルは形成されなかったと判断した。
<Synthesis example of core-shell type structured particle IV>
50 g of magnetic inorganic particle HQ powder, 5 g of EPICLON-850S, and 200 g of NMP were charged into a four-necked flask. Next, using a silicon oil bath, the mixture was stirred at 40 ° C. for 1 hour, and then stirred at 160 ° C. for 3 hours to obtain a core-shell structure particle dispersion. Next, pressure filtration was performed using a 0.45 μm membrane filter, and after filtration, PGME was further added from above to wash the core-shell structure particles, and pressure filtration was performed. The obtained filtrate was dried in a hot air oven furnace at 80 ° C. for 1 hour to obtain 48 g of core-shell structured particles. The average thickness of the shell was less than 10 nm and it was determined that no shell was formed.
実施例１
上記方法で得られた、コア−シェル型構造粒子Iの粉末１０ｇと、マトリックス樹脂および硬化剤としてＥＸＡ−４８５０−１５０と３，３’−ＤＤＳの混合物（３，３’−ＤＤＳを１００重量部に対しＥＸＡ−４８５０−１５０を３６０重量部）のＧＢＬ溶液１．５ｇ（固形分０．５３ｇ）を混ぜ、３本ロール（ＥＸＡＫＴ Ｍ−８０Ｓ）で４００ｒｐｍで１０回通した。その後、ハイブリッドミキサー（ＫＥＹＥＮＣＥ（株）製ＨＭ−５００、攪拌５分＋脱泡２分）で攪拌し、ペースト組成物を得た。
Example 1
10 g of the powder of core-shell type structured particles I obtained by the above method and a mixture of EXA-4850-150 and 3,3′-DDS as a matrix resin and a curing agent (100 parts by weight of 3,3′-DDS) On the other hand, 1.5 g of GBL solution (3603 parts by weight of EXA-4850-150) (solid content 0.53 g) was mixed and passed 10 times at 400 rpm with 3 rolls (EXAKT M-80S). Thereafter, the mixture was stirred with a hybrid mixer (HM-500 manufactured by KEYENCE Corporation, stirring 5 minutes + defoaming 2 minutes) to obtain a paste composition.
次いで、上述の磁性体組成物の体積抵抗率の測定方法に従い、体積抵抗率の測定を行ったところ、８×１０８Ωｃｍであった。さらに、同様に磁性体組成物の透磁率の測定を行ったところ、透磁率（μ’）４．３、ｔａｎδ０．１６であった。 Next, the volume resistivity was measured according to the above-described method for measuring the volume resistivity of the magnetic composition, and found to be 8 × 10 8 Ωcm. Furthermore, when the magnetic permeability of the magnetic composition was similarly measured, the magnetic permeability (μ ′) was 4.3 and tan δ was 0.16.
実施例２〜７、比較例１〜３
表１に示すように、磁性体無機粒子およびマトリックス樹脂を変えた以外は実施例１と同様の方法でペースト組成物を作成し、上述の方法に従って、体積抵抗率と透磁率の評価を行った。その結果を表１〜表２に示した。
Examples 2-7, Comparative Examples 1-3
As shown in Table 1, a paste composition was prepared in the same manner as in Example 1 except that the magnetic inorganic particles and the matrix resin were changed, and volume resistivity and magnetic permeability were evaluated according to the methods described above. . The results are shown in Tables 1 and 2.
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112920353A (en) * | 2021-02-25 | 2021-06-08 | 武汉理工大学 | Preparation method of monodisperse core-shell particles capable of being magnetically assembled into high-color-saturation photonic crystals in oleoresin |
| JP7477603B2 (en) | 2020-04-17 | 2024-05-01 | 富士フイルム株式会社 | Magnetic resin composition, cured product and electronic component |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01267839A (en) * | 1988-04-18 | 1989-10-25 | Fuji Photo Film Co Ltd | Production of magnetic recording medium |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH01267839A (en) * | 1988-04-18 | 1989-10-25 | Fuji Photo Film Co Ltd | Production of magnetic recording medium |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7477603B2 (en) | 2020-04-17 | 2024-05-01 | 富士フイルム株式会社 | Magnetic resin composition, cured product and electronic component |
| CN112920353A (en) * | 2021-02-25 | 2021-06-08 | 武汉理工大学 | Preparation method of monodisperse core-shell particles capable of being magnetically assembled into high-color-saturation photonic crystals in oleoresin |
| CN112920353B (en) * | 2021-02-25 | 2023-09-15 | 武汉理工大学 | Preparation method of monodisperse core-shell particles capable of being magnetically assembled into high-color saturation photonic crystals in oleoresin |
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| JP5927764B2 (en) | 2016-06-01 |
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