JP3313851B2 - Organic magnetic molded article and method for producing the same - Google Patents
Organic magnetic molded article and method for producing the sameInfo
- Publication number
- JP3313851B2 JP3313851B2 JP28451193A JP28451193A JP3313851B2 JP 3313851 B2 JP3313851 B2 JP 3313851B2 JP 28451193 A JP28451193 A JP 28451193A JP 28451193 A JP28451193 A JP 28451193A JP 3313851 B2 JP3313851 B2 JP 3313851B2
- Authority
- JP
- Japan
- Prior art keywords
- organic magnetic
- magnetic material
- organic
- thin film
- solution
- 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.)
- Expired - Fee Related
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/42—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of organic or organo-metallic materials, e.g. graphene
Description
【０００１】[0001]
【技術分野】本発明は、フェロセン構造を有する有機磁
性材料の成形体およびその製造法に関する。TECHNICAL FIELD The present invention relates to a molded article of an organic magnetic material having a ferrocene structure and a method for producing the same.
【０００２】[0002]
【従来技術とその問題点】 磁性材料は、磁石材料をはじめ高透磁率材料、恒透磁
率材料、磁歪材料などとして音響分野、電気・電子分
野、自動車分野、医療用分野、通信分野、磁気記録分野
など多くの分野において幅広く用いられている。このよ
うな磁性材料としては、金属、合金、非晶質合金、酸化
物等の種々の無機材料が使用されてきた。これに対し、
最近、有機磁性材料が軽量かつ軟質であり、さらに溶媒
への溶解性が良い、あるいはバインダー樹脂への分散
性、相溶性が良いとか、あるいは白色ないし淡色系のも
のが多いという利点があり、また、電気的、機械的に無
機材料とはその特性が異なるものが期待できるというこ
とから、その開発が注目されている。このような有機磁
性材料としては、例えば１，４−ビス（２，２′，６，
６′−テトラメチル−１−オキシル）ブタインを加熱又
は紫外線照射することによって製造された黒色粉末状ポ
リマー〔Ｎａｔｕｒｅ，３２６，３７０（１９８
７）〕、１，３，５−トリアミノベンゼンを沃素によっ
て重合した黒色不溶性ポリマー〔Ｓｙｎｔｈ．Ｍｅｔａ
ｌ，１９，７０９（１９８７）〕などが挙げられる。し
かし、従来の有機磁性材料は、（ｉ）合成が困難、（i
i）再現性に問題がある、（iii）強磁性発現の温度が極
めて低温、（iv）磁化の値が著しく小さい、（ｖ）空気
中で不安定である等の実用化に際しての問題点が数多く
あり、実際に有機磁性材料の薄膜化は行われた例はな
い。また、従来用いられていたバルク状の無機磁性材料
は主に圧延、焼結などの製造法が行われており、その製
法上複雑形状のものの作製は非常に困難であり、密度も
Ｆｅ系材料で７．５〜７．９ｇ／ｃｍ3、Ｎｉ系材料で
８．１〜８．６ｇ／ｃｍ3、フェライト系材料で４．５
〜５．４ｇ／ｃｍ3と有機磁性材料（１．０〜１．８ｇ
／ｃｍ3）に比べ大きく、また硬質なことから、使用で
きる分野が限られていた。[Prior art and its problems] Magnetic materials include magnet materials, high-permeability materials, constant-permeability materials, magnetostrictive materials, and the like in the acoustic field, the electric / electronic field, the automobile field, the medical field, the communication field, and the magnetic recording field. It is widely used in many fields such as fields. Various inorganic materials such as metals, alloys, amorphous alloys, and oxides have been used as such magnetic materials. In contrast,
Recently, the organic magnetic material is lightweight and soft, and further has good solubility in a solvent, or dispersibility in a binder resin, has good compatibility, or has the advantage that there are many white or light-colored ones, and Since its properties can be expected to be electrically and mechanically different from those of inorganic materials, its development has attracted attention. As such an organic magnetic material, for example, 1,4-bis (2,2 ', 6,
Black powdery polymer [Nature, 326 , 370 (198) obtained by heating or irradiating 6'-tetramethyl-1-oxyl) butain with ultraviolet rays.
7)], a black insoluble polymer obtained by polymerizing 1,3,5-triaminobenzene with iodine [Synth. Meta
1, 19 , 709 (1987)]. However, conventional organic magnetic materials are difficult to synthesize (i) and (i)
There are problems in practical use such as i) problems in reproducibility, (iii) extremely low ferromagnetic manifestation temperature, (iv) extremely low magnetization value, and (v) instability in air. There are many examples, and there is no example in which an organic magnetic material is actually thinned. In addition, the conventionally used bulk inorganic magnetic materials are mainly manufactured by rolling, sintering, or the like, and it is extremely difficult to manufacture a complicated shape due to the manufacturing method. in 7.5~7.9g / cm 3, Ni-based material in 8.1~8.6g / cm 3, 4.5 in the ferrite material
To 5.4 g / cm 3 and an organic magnetic material (1.0 to 1.8 g)
/ Cm 3 ), and because it is hard, its usable fields are limited.
【０００３】[0003]
【目的】本発明は、前記式（Ｉ）の新規な有機磁性材料
を用いることで、室温で磁性材料として非常に大きな磁
化を有し、空気中でも安定に存在し、さらに磁化の再現
性も良く、また従来の無機磁性材料に比べ、密度が小さ
く軟質で、かつ複雑形状の作成も可能な有機磁性材料の
成形体および該成形体の製造法の提供を目的とする。An object of the present invention is to use the novel organic magnetic material of the above formula (I) to have a very large magnetization as a magnetic material at room temperature, to stably exist in air, and to improve the reproducibility of magnetization. It is another object of the present invention to provide a molded article of an organic magnetic material which has a lower density and is softer than a conventional inorganic magnetic material and which can form a complicated shape, and a method for producing the molded article.
【０００４】[0004]
【構成】本発明の特徴の１つは、下記一般式（Ｉ）One of the features of the present invention is the following general formula (I):
【化２】 （式中、Ｒ1及びＲ2はそれぞれ水素原子又はアルキル基
を表わし、またｎは重合度で１以上の整数を表わす）で
表わされるフェロセン構造を有する有機磁性材料を主成
分とする材料で形成された磁性成形体にある。前記成形
体としては、薄膜、フィルム、 シート、テープ、塊状
物、容器様物等、種々の形状の成形体が挙げられる。こ
れら成形体は、例えば以下のようにして製造することが
できる。Embedded image (Wherein, R 1 and R 2 each represent a hydrogen atom or an alkyl group, and n represents an integer of 1 or more in the degree of polymerization) and is formed of a material mainly composed of an organic magnetic material having a ferrocene structure. In the magnetic molded body. Examples of the molded article include molded articles of various shapes such as a thin film, a film, a sheet, a tape, a lump, and a container. These compacts can be manufactured, for example, as follows.
【０００５】上記式（Ｉ）で表わされるフェロセン構造
を有する有機磁性材料は、テトラヒドロフラン、ジメチ
ルホルムアミド、クロロホルム、トルエン等の有機溶媒
に可溶であり、また溶解しない有機溶媒に対しても、溶
媒に対する分散性が良好なため、上記有機磁性材料を有
機溶媒に溶解あるいは安定に分散させた分散液を容易に
製造することができる。したがって、前記溶液あるいは
分散液を所望の型に充填し、その後溶媒を除去し乾固さ
せることにより、従来無機磁性材料では困難であった複
雑な形状の磁性材料の成形体を製造することができる。
また、前記溶液あるいは分散液をガラス、金属、セラミ
ック、プラスチック等の基板上に塗布後、例えば加熱、
減圧、送風などの方法で基板上の溶液または分散液を凝
固させることにより、有機磁性薄膜を製造することがで
きる。The organic magnetic material having a ferrocene structure represented by the above formula (I) is soluble in an organic solvent such as tetrahydrofuran, dimethylformamide, chloroform, toluene and the like. Since the dispersibility is good, a dispersion in which the organic magnetic material is dissolved or stably dispersed in an organic solvent can be easily produced. Therefore, by filling the solution or dispersion in a desired mold, and then removing and drying the solvent, a molded body of a magnetic material having a complicated shape, which has been difficult with the conventional inorganic magnetic material, can be manufactured. .
Further, after applying the solution or dispersion on a substrate of glass, metal, ceramic, plastic, etc., for example, heating,
The organic magnetic thin film can be manufactured by coagulating the solution or dispersion on the substrate by a method such as decompression and air blowing.
【０００６】前記有機磁性薄膜の製造法において、基板
上への塗布方法としては、浸漬塗工法、スピンコート
法、スプレーコーティング法を用いることができ、この
ような塗布方法を採用すると均一な磁性薄膜を膜厚を制
御して形成することが可能である。浸漬塗工法は、例え
ば図１に示すように溶液中に基板１を浸漬させた後、引
き抜くことにより基板上に溶液を塗布する方法である。
この方法によると、基板１の引き抜き速度、溶液の粘
度、及び基板１と溶液のなす角度などにより膜厚が制御
できる。スピンコート法は、例えば図２に示すようにタ
ーンテーブル２上にのせた基板１上に溶液をノズル３上
より滴下し、ターンテーブル２を高速回転させることに
より基板１上に溶液を塗布する方法である。この方法に
よると溶液の粘度、ターンテーブル２の回転速度などに
より膜厚を制御できる。スプレーコーティング法は、例
えば図３に示すように基板１上にスプレイガン７などに
より溶液を噴霧し、基板１を停止したまま、あるいは一
定速度で移動させることにより基板１上に溶液を塗布す
る方法である。この方法によると、溶液の粘度、基板１
の移動速度などにより膜厚を制御できる。前記塗布方法
で採用する溶液の粘度は、溶媒の粘度、溶液中の有機磁
性材料の濃度または該有機磁性材料の分子量を調節する
ことによりコントロールすることができる。また、基板
上の有機磁性体の溶液または分散液を乾固させた後、該
有機磁性体の軟化点以下の温度で不活性ガス雰囲気下で
熱処理を施すと、塗布溶液を乾固するのみならず、形成
した有機磁性薄膜のひずみを取り除くことができる。こ
のような熱処理は、前記の溶液あるいは分散液を型に充
填し、乾固させたものにも適用することができる。In the method for producing the organic magnetic thin film, a dip coating method, a spin coating method, and a spray coating method can be used as a coating method on the substrate. Can be formed by controlling the film thickness. The dip coating method is, for example, a method in which a substrate 1 is immersed in a solution as shown in FIG.
According to this method, the film thickness can be controlled by the drawing speed of the substrate 1, the viscosity of the solution, the angle between the substrate 1 and the solution, and the like. In the spin coating method, for example, a solution is applied from a nozzle 3 onto a substrate 1 placed on a turntable 2 as shown in FIG. 2 and the turntable 2 is rotated at a high speed to apply the solution onto the substrate 1. It is. According to this method, the film thickness can be controlled by the viscosity of the solution, the rotation speed of the turntable 2, and the like. In the spray coating method, for example, as shown in FIG. 3, a solution is sprayed onto the substrate 1 by a spray gun 7 or the like, and the solution is applied to the substrate 1 while the substrate 1 is stopped or moved at a constant speed. It is. According to this method, the viscosity of the solution, the substrate 1
The film thickness can be controlled by the moving speed or the like. The viscosity of the solution used in the coating method can be controlled by adjusting the viscosity of the solvent, the concentration of the organic magnetic material in the solution, or the molecular weight of the organic magnetic material. When the solution or dispersion of the organic magnetic material on the substrate is dried, and then subjected to a heat treatment in an inert gas atmosphere at a temperature equal to or lower than the softening point of the organic magnetic material, if only the coating solution is dried, In addition, the strain of the formed organic magnetic thin film can be removed. Such a heat treatment can also be applied to a mold filled with the solution or dispersion and dried.
【０００７】上記有機磁性材料の溶液または分散液中に
は、結着樹脂を含有させることが好ましい。ここで結着
樹脂としては、例えばポリスチレン、スチレン−ブタジ
エン共重合体、ポリメチルメタクリレート、ポリブチル
メタクリレート、ポリ塩化ビニル、ポリ酢酸ビニル、ポ
リエチレン、ポリエステル、エポキシ樹脂、フェノール
樹脂、ポリアミド樹脂などが挙げられ、これは単独ある
いは２種以上混合して用いることができる。また、上記
有機磁性材料は上記結着樹脂への分散性も良好であるこ
とから、有機磁性材料と結着樹脂とを混合し加圧成形、
あるいは前記有機磁性材料と結着樹脂の混合物を有機溶
媒に溶解あるいは分散させ、該溶液または分散液を型に
充填し、乾固して成形を行う場合でもバルク状に成形で
きる。この場合、結着樹脂の種類を変更することにより
成形体の強度を大きくすることが可能である。また、前
記成形自体を不活性ガス雰囲気中で加熱しながら行うこ
とによって強度の大きいバルク状の有機磁性材料の成形
体が得られる。また、この結着樹脂を含有するバルク状
成形体も前記のように有機磁性材料の軟化点以下の温度
で不活性ガス雰囲気中で熱処理を施すと成形体のひずみ
を取り除くことができる。It is preferable that a binder resin is contained in the solution or dispersion of the organic magnetic material. Here, examples of the binder resin include polystyrene, styrene-butadiene copolymer, polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polyester, epoxy resin, phenol resin, and polyamide resin. These can be used alone or in combination of two or more. Further, since the organic magnetic material has good dispersibility in the binder resin, the organic magnetic material and the binder resin are mixed and pressure-formed,
Alternatively, even when the mixture of the organic magnetic material and the binder resin is dissolved or dispersed in an organic solvent, the solution or the dispersion is filled in a mold, and then dried to perform molding, bulk molding can be performed. In this case, the strength of the molded article can be increased by changing the type of the binder resin. In addition, by performing the molding itself while heating in an inert gas atmosphere, a molded product of a bulk organic magnetic material having high strength can be obtained. Also, as described above, when the bulk molded article containing the binder resin is subjected to a heat treatment in an inert gas atmosphere at a temperature equal to or lower than the softening point of the organic magnetic material, the distortion of the molded article can be removed.
【０００８】本発明における前記一般式（Ｉ）で示され
るフェロセン構造を有する成分を主成分とする有機磁性
材料を具体的に例示すると、下記構造式〜に示す構
造単位の主成分のものが挙げられる。但し、本発明の有
機磁性材料を構成する構造単位は、これらのものに限定
されるものではない。Specific examples of the organic magnetic material mainly comprising the component having a ferrocene structure represented by the general formula (I) in the present invention include those having the following structural units. Can be However, the structural units constituting the organic magnetic material of the present invention are not limited to these.
【化３】 Embedded image
【化４】 Embedded image
【０００９】また、本発明の有機磁性材料の成形体を形
成する場合、磁性材料としては、前記のような有機磁性
材料に、従来知られている無機磁性材料および／または
他の有機磁性材料を混合して用いることができる。In the case of forming a molded article of the organic magnetic material of the present invention, as the magnetic material, a conventionally known inorganic magnetic material and / or another organic magnetic material may be used in addition to the above-mentioned organic magnetic material. They can be used in combination.
【００１０】以下、実施例により本発明を更に詳細に説
明するが、本発明はこれらに限定されるものではない。Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.
【００１１】合成例１ 具体例のフェロセンポリマー構造を主成分として有す
る縮合重合物の合成 １，１′−フェロセンジカルボキサアルデヒド０．２４
ｇ（１ｍｍｏｌ）とＰ−ベンゼンホスホン酸エステル
０．３８ｇ（１ｍｍｏｌ）とをＮ，Ｎ−ジメチルホルム
アミドに溶解し、そこへカリウム−ｔ−ブトキシド０．
３６ｇ（３ｍｍｏｌ）を投入し、室温で撹拌し、６時間
反応させた。その後、反応混合物を３００ｍｌの水に注
ぎ、撹拌した後、濾取し精製し、減圧乾燥し、赤橙色固
体０．３１ｇを得た。得られた化合物の元素分析値は下
記の通りであった。なお、計算値はＣ20Ｈ16Ｆｅとした
ものである。Synthesis Example 1 Synthesis of Condensation Polymer Having Ferrocene Polymer Structure of Specific Example as Main Component 1,1'-ferrocene dicarboxaldehyde 0.24
g (1 mmol) and 0.38 g (1 mmol) of P-benzenephosphonic acid ester were dissolved in N, N-dimethylformamide, and potassium-t-butoxide 0.1 g was dissolved therein.
36 g (3 mmol) was added, and the mixture was stirred at room temperature and reacted for 6 hours. Thereafter, the reaction mixture was poured into 300 ml of water, stirred, filtered, purified and dried under reduced pressure to obtain 0.31 g of a red-orange solid. The elemental analysis values of the obtained compound were as follows. Incidentally, the calculated value is obtained by a C 20 H 16 Fe.
【表１】 この化合物の赤外線吸収スペクトルを図４に示す。[Table 1] FIG. 4 shows the infrared absorption spectrum of this compound.
【００１２】合成例２ 具体例のフェロセンポリマー構造を主成分として有す
る縮合重合物の合成 ｍ−ベンゼンホスホン酸エステル０．３８ｇ（１ｍｍｏ
ｌ）をＮ，Ｎ−ジメチルホルムアミドに溶解し、そこへ
カリウム−ｔ−ブトキシド０．３６ｇ（３ｍｍｏｌ）を
室温で加えた。しばらく撹拌後、１，１′−フェロセン
ジカルボキサアルデヒド０．２４ｇ（１ｍｍｏｌ）の
Ｎ，Ｎ−ジメチルホルムアミド溶液を滴下した。滴下終
了後、７時間撹拌し、反応させた。その後、反応混合物
を３００ｍｌの水に注ぎ、撹拌した後、濾取し精製し、
減圧乾燥し、赤橙色固体０．２９ｇを得た。得られた化
合物の元素分析値は下記の通りであった。なお、計算値
はＣ20Ｈ16Ｆｅとしたものである。Synthesis Example 2 Synthesis of a condensation polymer having the ferrocene polymer structure of the specific example as a main component 0.38 g of m-benzenephosphonic ester (1 mmol)
l) was dissolved in N, N-dimethylformamide, and 0.36 g (3 mmol) of potassium-t-butoxide was added thereto at room temperature. After stirring for a while, an N, N-dimethylformamide solution of 0.24 g (1 mmol) of 1,1'-ferrocene dicarboxaldehyde was added dropwise. After completion of the dropwise addition, the mixture was stirred for 7 hours to react. Thereafter, the reaction mixture was poured into 300 ml of water, stirred, filtered, and purified,
Drying under reduced pressure gave 0.29 g of a red-orange solid. The elemental analysis values of the obtained compound were as follows. Incidentally, the calculated value is obtained by a C 20 H 16 Fe.
【表２】 この化合物の赤外線吸収スペクトルを図５に示す。[Table 2] FIG. 5 shows the infrared absorption spectrum of this compound.
【００１３】[0013]
実施例１ 合成例１のフェロセンポリマー構造を有する縮合重合物
を主成分とする有機磁性材料をテトラヒドロフラン、重
量比で１：３に混合溶解した。この溶液中に、ガラス基
板を浸漬させた後、液面に対して９０°の方向に１ｃｍ
／ｓｅｃの一定速度で基板を引きあげ、基板上に溶液を
塗布した（図１参照）。これを送風乾燥することにより
基板上に膜厚０．８μｍの有機磁性薄膜が形成できた。Example 1 An organic magnetic material mainly composed of the condensation polymer having a ferrocene polymer structure of Synthesis Example 1 was mixed and dissolved in tetrahydrofuran at a weight ratio of 1: 3. After immersing the glass substrate in this solution, 1 cm in the direction of 90 ° with respect to the liquid surface
The substrate was pulled up at a constant speed of / sec, and the solution was applied onto the substrate (see FIG. 1). This was blow-dried to form an organic magnetic thin film having a thickness of 0.8 μm on the substrate.
【００１４】実施例２ 合成例２のフェロセンポリマー構造を有する縮合重合物
を主成分とする有機磁性材料をテトラヒドロフラン、重
量比で１：３に混合溶解した。図２に示した装置を用い
て、ノズルより石英ガラス基板上に溶液を滴下したの
ち、基板をターンテーブルにより６０００ｒｐｍで回転
させることにより基板上に溶液を塗布した。続いて、こ
の基板をＡｒ雰囲気下で８０℃で２時間熱処理すること
により、基板上に膜厚０．７μｍの有機磁性薄膜が形成
できた。Example 2 An organic magnetic material mainly composed of a condensation polymer having a ferrocene polymer structure of Synthesis Example 2 was mixed and dissolved in tetrahydrofuran at a weight ratio of 1: 3. After the solution was dropped from the nozzle onto the quartz glass substrate using the apparatus shown in FIG. 2, the substrate was rotated at 6000 rpm using a turntable to apply the solution onto the substrate. Subsequently, the substrate was subjected to a heat treatment at 80 ° C. for 2 hours in an Ar atmosphere to form an organic magnetic thin film having a thickness of 0.7 μm on the substrate.
【００１５】実施例３ 合成例２のフェロセンポリマー構造を有する縮合重合物
を主成分とする有機磁性材料とスチレン−ブタジエン共
重合体とをテトラヒドロフラン、重量比１：１：４に混
合溶解した。この溶液をスプレーガンより、噴霧させ、
その中を図３のようにガラス基板を５ｃｍ／ｓｅｃの一
定速度で移動させることにより、基板上に溶液を塗布し
た。これを送風乾燥することにより、基板上に結着樹脂
と有機磁性材料の混合薄膜が膜厚０．５μｍで形成され
た。また、実施例１で形成した有機磁性薄膜を振動試料
型磁化測定装置（ＶＳＭ）にて磁気測定したところ、図
６のようなヒステリシスを示した。Example 3 An organic magnetic material mainly composed of a condensation polymer having a ferrocene polymer structure of Synthesis Example 2 and a styrene-butadiene copolymer were mixed and dissolved in tetrahydrofuran at a weight ratio of 1: 1: 4. Spray this solution from a spray gun,
The solution was applied on the substrate by moving the glass substrate at a constant speed of 5 cm / sec as shown in FIG. This was blow-dried to form a mixed thin film of a binder resin and an organic magnetic material with a thickness of 0.5 μm on the substrate. When the magnetic properties of the organic magnetic thin film formed in Example 1 were measured with a vibration sample type magnetometer (VSM), a hysteresis as shown in FIG. 6 was shown.
【００１６】実施例４ 合成例１のフェロセンポリマー構造を有する縮合重合物
を主成分とする有機磁性材料を図８に示すような加圧成
形装置を用い、圧力２ｔｏｎ／ｃｍ2をかけ、バルク状
の有機磁性材料を成形加工した。この成形体を室温で振
動試料型磁化測定装置（ＶＳＭ）にて、磁化測定を行っ
たところ図７に示すようなヒステリシスを描いた。以上
より、ペレット状の有機磁性材料が成形作製できた。Example 4 An organic magnetic material containing a condensation polymer having a ferrocene polymer structure of Synthesis Example 1 as a main component was applied in a pressure of 2 ton / cm 2 using a pressure molding apparatus as shown in FIG. Was formed. When the magnetization of this molded body was measured at room temperature by a vibration sample type magnetometer (VSM), a hysteresis as shown in FIG. 7 was drawn. From the above, a pellet-shaped organic magnetic material was molded and produced.
【００１７】実施例５ 合成例２のフェロセンポリマー構造を有する縮合重合物
を主成分とする有機磁性材料とポリスチレンをテトラヒ
ドロフランに重量比で１：１：３で混合溶解し、型に注
入し、アルゴン雰囲気中で８０℃、１時間熱処理し、乾
燥し、バルク状固体を得た。これをシリンダーに供給
し、加熱溶融、混練し、図９に示すようなＴ−ダイ、チ
ル・ロール法により、約０．２ｍｍのシートを形成し
た。さらに、このシートを用い図１０に示すドレープ成
形法で容器様のものが成形可能であった。また、これら
成形品の一部を切り取り、磁気的性質を水面凝集法で見
たところ、磁石に感応するため、シート状あるいは容器
様成形品は有機磁性材料成形品であることが判る。Example 5 An organic magnetic material mainly composed of the condensation polymer having a ferrocene polymer structure of Synthesis Example 2 and polystyrene were mixed and dissolved in tetrahydrofuran at a weight ratio of 1: 1: 3, and the mixture was injected into a mold and charged with argon. Heat treatment was performed at 80 ° C. for 1 hour in an atmosphere, followed by drying to obtain a bulk solid. This was supplied to a cylinder, heated and melted and kneaded to form a sheet of about 0.2 mm by a T-die and chill roll method as shown in FIG. Further, using this sheet, a container-like product could be formed by the drape forming method shown in FIG. Further, when a part of these molded products was cut out and the magnetic properties were observed by a water surface aggregation method, it was found that the sheet-like or container-like molded product was an organic magnetic material molded product because it was sensitive to magnets.
【００１８】[0018]
【効果】本発明により形成された新規な有機磁性材料の
成形体は有機磁性材料としては大きな磁化を示し、無機
磁性薄膜と比較し、密度が小さく軽量で軟質であるた
め、従来の磁性材料分野の代替のみならず、無機磁性材
料ではこれまで用いられなかった分野への用途が期待さ
れる。更に、無機磁性薄膜はその製造に多くの時間を要
したのに対し、本発明の有機磁性薄膜の製造は簡易で非
常に速く、かつ均一に膜厚を制御しながら行なえるた
め、生産性にも優れている。The novel organic magnetic material formed according to the present invention exhibits large magnetization as an organic magnetic material, and has a smaller density, lighter weight and softness as compared with an inorganic magnetic thin film. It is expected that inorganic magnetic materials will be used in fields that have not been used before. Furthermore, while the production of the inorganic magnetic thin film took a lot of time, the production of the organic magnetic thin film of the present invention was simple, very fast, and could be performed while controlling the film thickness uniformly. Is also excellent.
【図１】本発明で使用する浸漬塗工装置の１例の概略図
である。FIG. 1 is a schematic view of one example of a dip coating apparatus used in the present invention.
【図２】本発明で使用するスピンコート装置の１例の概
略図である。FIG. 2 is a schematic view of an example of a spin coater used in the present invention.
【図３】本発明で使用するスプレーコーティング装置の
１例の概略図である。FIG. 3 is a schematic view of an example of a spray coating apparatus used in the present invention.
【図４】合成例１で合成した縮合重合物の赤外線吸収ス
ペクトルを示す図である。FIG. 4 is a view showing an infrared absorption spectrum of a condensation polymer synthesized in Synthesis Example 1.
【図５】合成例２で合成した縮合重合物の赤外線吸収ス
ペクトルを示す図である。FIG. 5 is a view showing an infrared absorption spectrum of a condensation polymer synthesized in Synthesis Example 2.
【図６】実施例１で形成した有機磁性薄膜の磁気特性
（ヒステリシス曲線）を示す図である。FIG. 6 is a diagram showing magnetic properties (hysteresis curve) of the organic magnetic thin film formed in Example 1.
【図７】実施例４の成形体の磁気特性（ヒステリシス曲
線）を示す図である。FIG. 7 is a view showing magnetic properties (hysteresis curve) of a molded product of Example 4.
【図８】実施例４で採用した加圧成形装置の概略図であ
る。FIG. 8 is a schematic diagram of a pressure molding device employed in Example 4.
【図９】実施例５で採用したＴ−ダイ、チル・ロール法
の概略図である。FIG. 9 is a schematic diagram of a T-die and chill-roll method employed in Example 5.
【図１０】実施例５で採用したドレープ成形法の概略図
である。 （Ａ）シートをクランプ加熱し、型をシート中に圧入す
る工程を示す。 （Ｂ）下方に空気を抜いて雄型にシートを圧着する工程
を示す。 （Ｃ）最終成形品の形状を示す。FIG. 10 is a schematic view of a drape forming method employed in Example 5. (A) The step of clamping and heating the sheet and press-fitting the mold into the sheet. (B) The step of bleeding air downward and pressing the sheet to the male mold. (C) Shows the shape of the final molded product.
１ 基板 ２ 試料台（ターンテーブル） ３ ノズル ４ スピナーカップ ５ スピナー上ぶた ６ 試料台 ７ スプレーガン ８ 押出機 ９ 冷却ロール １０ 巻取機 １１ ヒータ １２ クランプ １３ プラスチックシート １４ シール １５ 成形品 １６ 加圧棒 １７ 型 １８ 試料 １９ 支持台 DESCRIPTION OF SYMBOLS 1 Substrate 2 Sample stand (turntable) 3 Nozzle 4 Spinner cup 5 Spinner upper lid 6 Sample stand 7 Spray gun 8 Extruder 9 Cooling roll 10 Winding machine 11 Heater 12 Clamp 13 Plastic sheet 14 Seal 15 Molded product 16 Pressure rod 17 type 18 sample 19 support
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) H01F 1/00 - 1/117 C08G 79/00 ──────────────────────────────────────────────────続 き Continuation of front page (58) Field surveyed (Int.Cl. 7 , DB name) H01F 1/00-1/117 C08G 79/00
Claims (8)
を表わし、またｎは重合度で１以上の整数を表わす）で
表わされるフェロセン構造を有する有機磁性材料を主成
分とする材料で形成された磁性成形体。1. A compound represented by the following general formula (I) (Wherein, R 1 and R 2 each represent a hydrogen atom or an alkyl group, and n represents an integer of 1 or more in the degree of polymerization) and is formed of a material mainly composed of an organic magnetic material having a ferrocene structure. Magnetic molded body.
着樹脂を含有するものである請求項１記載の磁性成形
体。2. The magnetic molded article according to claim 1, wherein the material mainly composed of an organic magnetic material contains a binder resin.
理されたものである請求項１または２記載の磁性成形
体。3. The magnetic compact according to claim 1, wherein the magnetic compact has been heat-treated in an inert gas atmosphere.
主成分とする材料で形成された有機磁性薄膜。4. An organic magnetic thin film formed of a material containing the organic magnetic material according to claim 1 as a main component.
に溶解あるいは分散させて作製した溶液あるいは分散液
を基板上に浸漬塗工法、スピンコート法またはスプレー
コーティング法により薄膜を形成し、該薄膜を凝固、さ
らに必要に応じて不活性ガス雰囲気中で熱処理すること
を特徴とする請求項４記載の有機磁性薄膜の製造法。5. A thin film is formed on a substrate by a dip coating method, a spin coating method or a spray coating method, using a solution or a dispersion prepared by dissolving or dispersing a material mainly composed of an organic magnetic material in a solvent, 5. The method for producing an organic magnetic thin film according to claim 4, wherein the thin film is solidified and, if necessary, heat-treated in an inert gas atmosphere.
主成分とする材料で形成されたバルク状有機磁性体。6. A bulk organic magnetic material formed of a material containing the organic magnetic material according to claim 1 or 2 as a main component.
成形、さらに必要に応じて不活性ガス雰囲気中で熱処理
することを特徴とする請求項６記載のバルク状有機磁性
体の製造法。7. The method for producing a bulk organic magnetic material according to claim 6, wherein a material mainly composed of an organic magnetic material is subjected to pressure molding and, if necessary, heat-treated in an inert gas atmosphere. .
あるいは分散液を型中に充填、乾固、さらに必要に応じ
て不活性ガス雰囲気中で熱処理することを特徴とする請
求項６記載のバルク状有機磁性体の製造法。8. The method according to claim 6, wherein a solution or a dispersion of a material containing an organic magnetic material as a main component is filled in a mold, dried, and optionally heat-treated in an inert gas atmosphere. Production method of bulk organic magnetic material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28451193A JP3313851B2 (en) | 1993-05-20 | 1993-10-19 | Organic magnetic molded article and method for producing the same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14151693 | 1993-05-20 | ||
| JP5-141516 | 1993-05-20 | ||
| JP28451193A JP3313851B2 (en) | 1993-05-20 | 1993-10-19 | Organic magnetic molded article and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0799106A JPH0799106A (en) | 1995-04-11 |
| JP3313851B2 true JP3313851B2 (en) | 2002-08-12 |
Family
ID=26473740
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28451193A Expired - Fee Related JP3313851B2 (en) | 1993-05-20 | 1993-10-19 | Organic magnetic molded article and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3313851B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001284123A (en) * | 2000-01-24 | 2001-10-12 | Fuji Electric Co Ltd | Magnetic thin film, magnetic component provided with the same, their manufacturing method, and electric power converter |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5635002B2 (en) * | 1973-03-20 | 1981-08-14 | ||
| DE69032951T2 (en) * | 1989-08-23 | 1999-07-01 | Agency Ind Science Techn | Ferromagnetic organic polymer material |
| JP2972898B2 (en) * | 1990-11-22 | 1999-11-08 | 株式会社リコー | Manufacturing method of organic magnetic material |
| JP3230250B2 (en) * | 1991-08-13 | 2001-11-19 | 日本ゼオン株式会社 | Thermoplastic norbornene-based resin coating agent and coating layer forming method |
-
1993
- 1993-10-19 JP JP28451193A patent/JP3313851B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0799106A (en) | 1995-04-11 |
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