JPH0845717A - Organic magnetic material and manufacture thereof - Google Patents
Organic magnetic material and manufacture thereofInfo
- Publication number
- JPH0845717A JPH0845717A JP6199124A JP19912494A JPH0845717A JP H0845717 A JPH0845717 A JP H0845717A JP 6199124 A JP6199124 A JP 6199124A JP 19912494 A JP19912494 A JP 19912494A JP H0845717 A JPH0845717 A JP H0845717A
- Authority
- JP
- Japan
- Prior art keywords
- magnetic material
- group
- organic
- magnetic susceptibility
- organic magnetic
- 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
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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は有機磁性材料の製造方法
及び本方法によって得られる有機磁性材料に関し、更に
詳しくは、トリアリールメタン基本構造を有する磁化率
の大きな有機磁性材料及び本方法によって得られる温度
センサー、磁気シールド等の磁性材料として有用な有機
磁性材料に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an organic magnetic material and an organic magnetic material obtained by this method. More specifically, the present invention relates to an organic magnetic material having a basic structure of triarylmethane and a high magnetic susceptibility and obtained by this method. The present invention relates to an organic magnetic material useful as a magnetic material such as a temperature sensor and a magnetic shield.
【０００２】[0002]
【従来の技術】磁性材料は、高透磁率材料、磁石材料、
磁歪材料、磁気記録材料をはじめ、多種多様のものがあ
り、通信分野、音響分野など多くの電気関連分野におい
て幅広く用いられている。しかし、従来その材料は無機
磁性材料に限られていた。これに対し、最近、有機磁性
材料が軽量で軽質であり、更に溶媒への溶解性が良い、
あるいは溶媒、結着樹脂への分散性、相溶性が良いなど
の利点を有し、電気的、機械的に無機磁性材料とは異な
るものが期待できることから、その開発が注目されてい
る。2. Description of the Related Art Magnetic materials include high magnetic permeability materials, magnet materials,
There are a wide variety of materials including magnetostrictive materials and magnetic recording materials, and they are widely used in many electrical fields such as communication and acoustic fields. However, conventionally, the material has been limited to the inorganic magnetic material. On the other hand, recently, the organic magnetic material is lightweight and light, and further has good solubility in a solvent.
Alternatively, it has advantages such as good dispersibility in a solvent and a binder resin and good compatibility, and it can be expected to be electrically and mechanically different from an inorganic magnetic material, and therefore its development is drawing attention.
【０００３】ただ、従来の有機強磁性材料は、強磁性の
再現性が満足されるものではなかった。また、有機常磁
性材料は磁化率が著しく小さく、磁性材料としての実用
化は困難であった。また、その磁化率を大きくするため
には、スピン濃度を増加させるか、あるいはスピン多重
度を増加させる必要があり、そのために合成あるいは種
々の処理工程が複雑になる。そのため、磁化率の大きい
有機磁性体についての研究開発が活発に行なわれてい
る。例えば、縮合多環芳香族系樹脂（いわゆるＣＯＰＮ
Ａ樹脂）系の有機磁性材料については、特開平２−１６
０７３１号、特開平３−１７４７０３号、特開平４−７
３１６号各公報に提案されている。However, conventional organic ferromagnetic materials have not been satisfactory in reproducibility of ferromagnetism. Moreover, the magnetic susceptibility of the organic paramagnetic material was extremely small, and it was difficult to put it into practical use as a magnetic material. Further, in order to increase the magnetic susceptibility, it is necessary to increase the spin concentration or increase the spin multiplicity, which complicates synthesis or various processing steps. Therefore, research and development have been actively conducted on organic magnetic materials having a high magnetic susceptibility. For example, a condensed polycyclic aromatic resin (so-called COPN
Regarding the (A resin) -based organic magnetic material, Japanese Patent Application Laid-Open No. 2-16
0731, JP-A-3-174703, JP-A-4-7.
No. 316 is proposed.
【０００４】即ち、特開平２−１６０７３１号公報に
は、トリアリールメタン基本構造を有し、そのメチン炭
素部位におけるラジカル濃度が少なくとも１０17／ｇで
ある強磁性有機物質及びその製造方法が報告され、また
特開平４−７３１６号公報には、上記トリアリールメタ
ン基本構造を有するポリマーにおいて、そのメチン炭素
にハロゲン原子が結合している有機強磁性前駆体及び上
記ポリマーから４量体以下の低分子を除去、メチン炭素
にハロゲン原子を結合させ、更に金属と反応させ、メチ
ン炭素部位にラジカルを発生させる有機強磁性体の製造
方法が報告されている。That is, JP-A-2-160731 reports a ferromagnetic organic substance having a triarylmethane basic structure and a radical concentration of at least 10 17 / g at the methine carbon site, and a method for producing the same. Further, in JP-A-4-7316, in a polymer having the above basic structure of triarylmethane, an organic ferromagnetic precursor having a halogen atom bonded to its methine carbon and a low molecular weight tetramer or less from the above polymer. It has been reported that a method for producing an organic ferromagnet in which a halogen atom is bonded to a methine carbon and a radical is generated at the methine carbon site by reacting the metal with a halogen atom is removed.
【０００５】また、特開平３−１７４７０３号公報に
は、下記一般式（ＩＩ）で示される繰り返し単位を有す
るポリマーがある温度範囲（実際には低温）に保持され
ると磁化率が向上し、このとき常磁性から強磁性への転
移のあることが報告されている。Further, in JP-A-3-174703, the magnetic susceptibility is improved when a polymer having a repeating unit represented by the following general formula (II) is kept in a certain temperature range (actually low temperature), At this time, it is reported that there is a transition from paramagnetism to ferromagnetism.
【化２】 （式中、Ｒ1、Ｒ2の少なくとも一方が置換若しくは未置
換の芳香族環、又は、置換若しくは未置換の複素環であ
る）。Embedded image (In the formula, at least one of R 1 and R 2 is a substituted or unsubstituted aromatic ring or a substituted or unsubstituted heterocycle).
【０００６】[0006]
【発明が解決しようとする課題】上記の報告から明らか
なように、大きな磁化率を有する常磁性体を、複雑な合
成や処理を行なうことなく、再現性よく得る方法は、未
だ見い出されていないのが現状である。As is clear from the above report, a method for obtaining a paramagnetic material having a large magnetic susceptibility with good reproducibility without complicated synthesis or treatment has not been found yet. is the current situation.
【０００７】従って、本発明の目的は、上記課題を解決
し、常磁性材料でありながら、複雑な合成や処理を行な
うことなく、再現性よく大きい磁化率を有する有機磁性
材料及びその製造方法を提供することにある。Therefore, an object of the present invention is to solve the above-mentioned problems and to provide an organic magnetic material which is a paramagnetic material and has a high magnetic susceptibility with good reproducibility without complicated synthesis or treatment, and a method for producing the same. To provide.
【０００８】[0008]
【課題を解決するための手段】本発明によれば、下記一
般式（Ｉ）According to the present invention, the following general formula (I)
【化１】 〔式中、Ｒ1、Ｒ2及びｎはそれぞれ以下のものを示す。 Ｒ1：２環以上の置換若しくは非置換の縮合多環アリー
レン基（但し、環員にＮ、Ｓ若しくはＯよりなるヘテロ
原子を含むことができる）又は電子供与基置換フェニレ
ン基、 Ｒ2：置換若しくは非置換のアリール基、 ｎ：１以上の整数。〕で示されるトリアリールメタン基
本構造よりなる有機磁性材料において、臨界温度Ｔｃ以
下の特定温度Ｔ1まで徐冷を行なう操作により磁化率を
増大させることを特徴とする有機磁性材料の製造方法が
提供される。Embedded image [In formula, R < 1 >, R < 2 > and n show the following, respectively. R 1 : a substituted or unsubstituted fused polycyclic arylene group having two or more rings (provided that a ring member can contain a hetero atom consisting of N, S, or O) or an electron-donating group-substituted phenylene group, R 2 : substituted Or an unsubstituted aryl group, n: an integer of 1 or more. ] In the organic magnetic material having the basic structure of triarylmethane represented by the above, there is provided a method for producing an organic magnetic material, characterized in that the magnetic susceptibility is increased by an operation of gradually cooling to a specific temperature T 1 below a critical temperature Tc. To be done.
【０００９】また、本発明によれば、好ましい態様とし
て、前記徐冷を−１．０Ｋ／分より小さい冷却速度で行
なうことを特徴とする有機磁性材料の製造方法が提供さ
れ、また前記徐冷を５０〜１５０Ｋの温度範囲で行なう
ことを特徴とする有機磁性材料の製造方法が提供され
る。Further, according to the present invention, as a preferred embodiment, there is provided a method for producing an organic magnetic material, characterized in that the slow cooling is performed at a cooling rate lower than -1.0 K / min. Is performed in a temperature range of 50 to 150 K, and a method for producing an organic magnetic material is provided.
【００１０】更に、本発明によれば、前記の製造方法に
より形成された大きい磁化率を有する有機磁性材料が提
供され、また前記有機磁性材料において、そのメチン炭
素部位におけるラジカル濃度が少なくとも１０17／ｇで
あることを特徴とする有機磁性材料が提供される。Further, according to the present invention, there is provided an organic magnetic material having a large magnetic susceptibility formed by the above manufacturing method, and in the organic magnetic material, the radical concentration at the methine carbon site is at least 10 17 /. An organic magnetic material is provided which is characterized by being g.
【００１１】以下、本発明について詳細に説明する。本
発明の製造方法においては、前記一般式（Ｉ）で示され
るトリアリールメタン基本構造よりなる有機磁性材料
（常磁性体）が出発原料となる。The present invention will be described in detail below. In the production method of the present invention, an organic magnetic material (paramagnetic material) having the basic structure of triarylmethane represented by the general formula (I) serves as a starting material.
【００１２】前記一般式（Ｉ）において、Ｒ1の２環以
上の非置換の縮合多環アリーレン基の具体例としては、
ナフチル基、アントリル基、フェナントリル基、ピレニ
ル基、クリセン基、ナフタセン基、ベンゾフェナントリ
ル基、ペリレン基、ベンゾピレニル基、コローネン基、
アセナフチレン基、デカシクレン基などが挙げられる。
また、その置換基としては、水酸基、メチル基などが挙
げられる。なお、環員にＮ，Ｓ，Ｏなどのヘテロ原子を
含んでも良い。更に、電子供与基置換フェニレン基は、
ヒドロキシ基、メトキシ基、メチル基、エチル基などを
置換基としてもつフェニレン基であって、その具体例と
しては、フェノール基、レゾルシン基などが挙げられ
る。In the above general formula (I), specific examples of the fused polycyclic arylene group having 2 or more rings and not represented by R 1 include
Naphthyl group, anthryl group, phenanthryl group, pyrenyl group, chrysene group, naphthacene group, benzophenanthryl group, perylene group, benzopyrenyl group, coronene group,
Examples thereof include an acenaphthylene group and a decacyclene group.
Further, examples of the substituent include a hydroxyl group and a methyl group. Incidentally, the ring member may contain a hetero atom such as N, S or O. Further, the electron-donating group-substituted phenylene group is
It is a phenylene group having a hydroxy group, a methoxy group, a methyl group, an ethyl group or the like as a substituent, and specific examples thereof include a phenol group and a resorcin group.
【００１３】また、Ｒ2の非置換のアリール基の具体例
としては、フェニル基などが挙げられ、その置換基とし
ては、ニトロ基、メチル基、イソプロピル基、ｔ−ブチ
ル基、水酸基、アミノ基などが挙げられる。なお、ｎは
重合度を意味し、１以上の整数を示す。Further, specific examples of the unsubstituted aryl group of R 2 include phenyl group and the like, and the substituents thereof are nitro group, methyl group, isopropyl group, t-butyl group, hydroxyl group, amino group. And so on. In addition, n means a polymerization degree and shows an integer of 1 or more.
【００１４】このトリアリールメタン構造を有する有機
磁性材料（常磁性体）は、次のようにして得ることがで
きる。即ち、２環以上の置換若しくは非置換の縮合多環
芳香族化合物又は電子供与基を持つ単環芳香族と、置換
若しくは非置換芳香族アルデヒドとを酸触媒の存在下で
縮合させ、トリアリールメタン構造を有する初期縮合体
を生成させる。続いて、生成物を脱水素処理し、更に未
反応物の除去処理を行なうことにより、目的とする生成
物が形成される。The organic magnetic material (paramagnetic material) having the triarylmethane structure can be obtained as follows. That is, a substituted or unsubstituted fused polycyclic aromatic compound having two or more rings or a monocyclic aromatic compound having an electron-donating group and a substituted or unsubstituted aromatic aldehyde are condensed in the presence of an acid catalyst to give a triarylmethane. An initial condensate having a structure is formed. Subsequently, the product is subjected to dehydrogenation treatment and further unreacted matter removal treatment to form the desired product.
【００１５】ここで、縮合多環芳香族化合物としては、
環数２〜１０個程度までのもの、例えばナフタレン、ア
ントラセン、フェナントレン、ピレン、クリセン、ナフ
タセン、ベンゾフェナントレン、ペリレン、ベンゾピレ
ン、コローネンなどベンゼン環縮合型の他に、アセナチ
フレン、デカシクレンなどの５員環などを含んでいても
よく、また環員にＮ、Ｓ、Ｏなどのヘテロ原子を含んで
もよい。更に水酸基、メチル基などの置換誘導体も用い
ることができる。もちろん、これらの混合物でもいいこ
とは言うまでもない。また、単環芳香族の場合には、ヒ
ドロキシ基、低級アルコキシ基、例えばメトキシ基、エ
トキシ基、低級アルキル基、例えばメチル基、エチル基
などの電子供与基の１又は２置換体を用いることができ
る。連結剤として用いる芳香族アルデヒドとしては、ベ
ンズアルデヒドが最も一般的であり、また芳香族アルデ
ヒドの置換基としては、ニトロ基、水素原子、メチル
基、イソプロピル基、ｔ−ブチル基、水酸基、アミノ基
などを用いることができる。縮合反応の酸触媒として
は、各種の酸触媒、例えばｐ−トルエンスルホン酸をは
じめとする各種の芳香族スルホン酸、フルオロメタンス
ルホン酸その他の超強酸、硫酸などを用いることができ
る。Here, as the condensed polycyclic aromatic compound,
Those having up to about 2 to 10 rings, such as naphthalene, anthracene, phenanthrene, pyrene, chrysene, naphthacene, benzophenanthrene, perylene, benzopyrene, and coronene, as well as benzene ring condensed types, as well as 5-membered rings such as acenatifrene and decacyclene. May be included, and the ring member may include a hetero atom such as N, S or O. Further, a substituted derivative such as a hydroxyl group or a methyl group can also be used. Of course, it goes without saying that a mixture of these may be used. In the case of a monocyclic aromatic group, a 1- or 2-substituted product of an electron-donating group such as a hydroxy group, a lower alkoxy group, for example, a methoxy group, an ethoxy group, a lower alkyl group, for example, a methyl group, an ethyl group or the like is used. it can. As the aromatic aldehyde used as the linking agent, benzaldehyde is the most common, and as the substituent of the aromatic aldehyde, nitro group, hydrogen atom, methyl group, isopropyl group, t-butyl group, hydroxyl group, amino group, etc. Can be used. As the acid catalyst for the condensation reaction, various acid catalysts, for example, various aromatic sulfonic acids including p-toluenesulfonic acid, fluoromethanesulfonic acid and other super strong acids, and sulfuric acid can be used.
【００１６】脱水素処理としては（これはメチン炭素に
つく水素を脱水素することにより、ラジカル濃度を高め
るために行なうものである）、通常用いられる方法がい
ずれも有効であり、特に方法を限定されることはない。
例えば、加熱、光照射、放射線照射、電磁波の照射、電
解酸化、直流又は低周波無声放電、グロー放電、高周波
放電、マイクロ波放電による方法などがあり、もちろん
これらは組み合わせても問題ない。脱水素処理時には、
上述した初期縮合体は例えば液体、固体あるいは溶媒に
溶解した状態などどのような状態でもよく、必要に応じ
て、脱水素剤、光増感剤などを適切量使用する。未反応
物の除去処理としては、通常用いられる方法は、いずれ
も有効であり、特に方法を限定されることはない。As the dehydrogenation treatment (this is carried out in order to increase the radical concentration by dehydrogenating hydrogen attached to methine carbon), any of the commonly used methods is effective, and the method is particularly limited. It will not be done.
For example, there are methods such as heating, light irradiation, radiation irradiation, electromagnetic wave irradiation, electrolytic oxidation, direct current or low frequency silent discharge, glow discharge, high frequency discharge, and microwave discharge. Of course, these methods may be combined. During the dehydrogenation process,
The above-mentioned initial condensate may be in any state such as liquid, solid or dissolved in a solvent, and if necessary, a dehydrogenating agent, a photosensitizer and the like are used in appropriate amounts. As a treatment for removing unreacted substances, any of the methods usually used is effective, and the method is not particularly limited.
【００１７】以上のようにして得られた生成物は常磁性
体であるが、本発明によりその磁化率を増大させること
が可能になる。通常、有機常磁性体の磁化率から、分子
自体の反磁性磁化率を差し引いた磁化率：χは、下記の
式（ＩＩＩ）で表わせる。（キュリー則）The product obtained as described above is a paramagnetic substance, but the present invention makes it possible to increase its magnetic susceptibility. Usually, the magnetic susceptibility: χ obtained by subtracting the diamagnetic magnetic susceptibility of the molecule itself from the magnetic susceptibility of the organic paramagnetic material can be expressed by the following formula (III). (Curie rule)
【数１】 （式中、Ｔ：温度、Ｎ：スピン数、ｇ：ｇ値、ＭB：ボ
ーア磁子、ｋ：ボルツマン定数、Ｓ：スピン量子数） しかしながら、上述の製造方法で得られた有機常磁性生
成物は、臨界温度：Ｔｃより低温に冷却した場合、式
（ＩＩＩ）で得られる理論値より大きい値を示すことが
本発明者らの研究により判明し、更にこの低温への冷却
速度を小さくすることにより（冷却をゆっくり行なうこ
とにより）、ある温度以下で、本来の磁化率より更に大
きい磁化率が得られることが明らかになった。[Equation 1] (In the formula, T: temperature, N: spin number, g: g value, MB: Bohr magneton, k: Boltzmann constant, S: spin quantum number) However, the organic paramagnetic product obtained by the above production method Is found to be larger than the theoretical value obtained by the formula (III) when cooled to a temperature lower than the critical temperature: Tc, and further reduction of the cooling rate to this low temperature is revealed. It was revealed that (by slow cooling), a magnetic susceptibility higher than the original magnetic susceptibility can be obtained at a certain temperature or lower.
【００１８】即ち、前述の有機常磁性生成物を徐冷する
だけで低温における磁化率を増加させることが可能にな
った。冷却速度はできるだけゆっくり冷却した場合に磁
化率を増加させる効果が大きく、特に−１．０Ｋ／分よ
りゆっくり冷却した場合にその効果は顕著である。もち
ろん、更にゆっくりした場合その効果はより顕著にな
る。また、この冷却方法は、一定の速度で冷却する必要
はなく、種々の冷却速度を組み合わせても問題ない。ま
た、一定の温度で一定の時間保持することを繰り返すこ
とにより冷却する方法や、冷却−昇温を組み合わせなが
ら冷却する方法でも効果があることはいうまでもない。
また、磁化率を増加させるのに有効な徐冷温度範囲は生
成物の種類によって異なるが、特に５０〜１５０Ｋの温
度範囲が好ましい。That is, it becomes possible to increase the magnetic susceptibility at low temperature simply by gradually cooling the above-mentioned organic paramagnetic product. When the cooling rate is as slow as possible, the effect of increasing the magnetic susceptibility is large, and particularly when the cooling rate is slower than -1.0 K / min, the effect is remarkable. Of course, if it is slowed down, the effect becomes more remarkable. Further, in this cooling method, it is not necessary to cool at a constant rate, and there is no problem even if various cooling rates are combined. Further, it goes without saying that a method of cooling by repeating holding at a constant temperature for a certain time or a method of cooling while combining cooling and temperature rise is also effective.
Further, the slow cooling temperature range effective for increasing the magnetic susceptibility varies depending on the kind of the product, but a temperature range of 50 to 150 K is particularly preferable.
【００１９】また、有機常磁性生成物のスピン濃度は、
１０17スピン／ｇ以上が好ましい。特に、本来の磁化率
の値及び増加する磁化率の絶対値の両方を大きくするた
めに、スピン濃度として１０19スピン／ｇ以上が好まし
く、更には１０20スピン／ｇ以上が好ましい。The spin concentration of the organic paramagnetic product is
10 17 spin / g or more is preferable. In particular, in order to increase both the original value of the magnetic susceptibility and the absolute value of the increasing magnetic susceptibility, the spin concentration is preferably 10 19 spins / g or more, more preferably 10 20 spins / g or more.
【００２０】[0020]
【実施例】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。EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.
【００２１】実施例１ ピレン１０．１３ｇとベンズアルデヒド６．６３ｇに
０．８８ｇのパラトルエンスルホン酸を加え、撹拌しな
がら加熱し、系内を１６０℃に保つ。２０分間反応させ
ると、粘性を帯びてきて、やがて固化する。室温まで冷
却後クロロホルムにて生成物を抽出し、メタノールより
再沈精製を行ない、濾取した後この生成物を減圧乾燥す
ることにより、初期縮合体を得た。続いて、この縮合体
をニトロベンゼンに３．５×１０-2ｍｏｌ／ｌの濃度で
溶解し、Ａｒ雰囲気中で１５０℃まで加熱した。これに
ジクロロジシアノベンゾキノンを５．２×１０-2ｍｏｌ
／ｌの濃度になるように添加し、そのまま２００分間反
応させた（脱水素処理）。Example 1 Pyrene (10.13 g) and benzaldehyde (6.63 g) were mixed with 0.88 g of paratoluenesulfonic acid and heated with stirring to maintain the system temperature at 160 ° C. After reacting for 20 minutes, it becomes viscous and eventually solidifies. After cooling to room temperature, the product was extracted with chloroform, purified by reprecipitation from methanol, collected by filtration, and dried under reduced pressure to obtain an initial condensate. Then, this condensate was dissolved in nitrobenzene at a concentration of 3.5 × 10 -2 mol / l and heated to 150 ° C. in an Ar atmosphere. Dichlorodicyanobenzoquinone (5.2 × 10 -2 mol)
It was added so as to have a concentration of 1 / l, and the reaction was allowed to proceed for 200 minutes (dehydrogenation treatment).
【００２２】この溶液を室温まで冷却した後、メタノー
ルより再沈精製を行ない、濾取後生成物を減圧乾燥し
た。この生成物の磁気特性は、超伝導量子干渉式磁化測
定装置（ＳＱＵＩＤ；Ｑｕａｎｔｕｍ ｄｅｓｉｇｎ
社製 Ｍｏｄｅｌ ＭＰＭＳ−２）を用いて行なった。This solution was cooled to room temperature, purified by reprecipitation from methanol, filtered, and the product was dried under reduced pressure. The magnetic properties of this product are as follows: Superconducting Quantum Interferometry Magnetometer (SQUID; Quantum design)
It was performed using Model MPMS-2) manufactured by the same company.
【００２３】図１に磁化率（χ）の温度依存性を示す。
磁化率の測定は最初に５Ｋまで冷却し、昇温しながら行
なった。ここで、黒丸（●）は、５Ｋまでの冷却を−
０．４Ｋ／分で行なったもの、また、白丸（○）は−
４．５Ｋ／分で行なった場合である。このように−０．
４Ｋ／分で徐冷した場合は、−４．５Ｋ／分の場合と比
較しておよそ１１０Ｋ以下で磁化率の値が大きくなり、
５Ｋにおいては、４倍以上の大きい磁化率が得られてい
る。尚、磁化率の値は分子自体の反磁性磁化率を差し引
いたものである。FIG. 1 shows the temperature dependence of the magnetic susceptibility (χ).
The magnetic susceptibility was measured by first cooling to 5K and raising the temperature. Here, black circles (●) are for cooling up to 5K
What was done at 0.4 K / min, and white circles (○) are-
This is the case when it is performed at 4.5 K / min. Thus, -0.
In the case of slow cooling at 4 K / min, the value of magnetic susceptibility increases at about 110 K or less as compared with the case of -4.5 K / min,
At 5K, a magnetic susceptibility of 4 times or more is obtained. The value of the magnetic susceptibility is obtained by subtracting the diamagnetic magnetic susceptibility of the molecule itself.
【００２４】また、図２に上記と同様の生成物を、５Ｋ
まで−４．５Ｋ／分で急冷後５Ｋに保持した場合の磁化
率の時間依存性を示す。このように、５Ｋで保持して
も、磁化率は７６０分経過後も変化しない。即ち、冷却
速度により低温における磁化率の絶対値が決まってしま
い、徐冷した場合に磁化率が大きくなることがわかる。In addition, in FIG.
Shows the time dependence of the magnetic susceptibility when rapidly cooled at −4.5 K / min and then held at 5 K. Thus, even if held at 5K, the magnetic susceptibility does not change even after 760 minutes. That is, it can be seen that the absolute value of the magnetic susceptibility at a low temperature is determined by the cooling rate, and the magnetic susceptibility increases when gradually cooled.
【００２５】実施例２ 実施例１で得られた生成物を５Ｋまで−１．５Ｋ／分で
冷却した後、磁化率の温度依存性を測定した。−４．５
Ｋ／分で冷却した場合と比較して、やはり１１０Ｋ以下
で磁化率の値は大きくなるが、−０．４Ｋ／分で冷却し
た場合ほど顕著ではなかった。Example 2 After cooling the product obtained in Example 1 to 5K at -1.5K / min, the temperature dependence of the magnetic susceptibility was measured. -4.5
As compared with the case of cooling at K / min, the value of the magnetic susceptibility also increased at 110 K or less, but it was not so remarkable as when cooling at -0.4 K / min.
【００２６】実施例３ 実施例１で得られた生成物を１５０Ｋまで−０．４Ｋ／
分で徐冷した後、５Ｋまで急冷した。この温度プロファ
イル（概念図）を図３に示した。徐冷から急冷に変化さ
せる温度をＴｑとすると、この場合はＴｑ＝１５０Ｋで
ある。この場合の磁化率の温度依存性を図４に示す。磁
化率の大きさは−４．５Ｋ／分で、５Ｋまで急冷した場
合と殆ど同程度の値を示した。Example 3 The product obtained in Example 1 is used up to 150K at -0.4K /
After gradually cooling in minutes, it was rapidly cooled to 5K. This temperature profile (conceptual diagram) is shown in FIG. Assuming that the temperature for changing from slow cooling to rapid cooling is Tq, Tq = 150K in this case. The temperature dependence of the magnetic susceptibility in this case is shown in FIG. The magnitude of the magnetic susceptibility was -4.5 K / min, which was almost the same value as when it was rapidly cooled to 5 K.
【００２７】実施例４ Ｔｑ＝１００Ｋの場合の磁化率の温度依存性を図５に示
す。磁化率の大きさは−４．５Ｋ／分で、５Ｋまで急冷
した場合と比較して１１０Ｋ以下で大きくなり、５Ｋの
値は２倍以上になっている。Example 4 FIG. 5 shows the temperature dependence of the magnetic susceptibility when Tq = 100K. The magnitude of the magnetic susceptibility is -4.5 K / min, which is larger at 110 K or less as compared with the case of quenching to 5 K, and the value at 5 K is twice or more.
【００２８】実施例５ Ｔｑ＝５０Ｋの場合の磁化率の温度依存性を図６に示
す。磁化率の大きさは−０．４Ｋ／分で５Ｋまで急冷し
た場合とほぼ同程度となり、５Ｋにおける値は−４．５
Ｋ／分で５Ｋまで冷却した場合の４倍程度の大きさとな
っている。Example 5 FIG. 6 shows the temperature dependence of the magnetic susceptibility when Tq = 50K. The magnitude of magnetic susceptibility is almost the same as when it is rapidly cooled to 5K at -0.4K / min, and the value at 5K is -4.5K.
It is about four times as large as when it is cooled to 5K at K / min.
【００２９】[0029]
【発明の効果】請求項１の有機磁性材料の製造方法は、
前記一般式（Ｉ）で示されるトリアリールメタン基本構
造を有する有機磁性材料を臨界温度Ｔｃ以下の特定温度
Ｔ1まで徐冷を行なう操作により磁化率を増大させると
いう構成にしたことから、簡単な操作により再現性良く
磁化率の大きい有機磁性材料の製造が可能となる。The method for producing an organic magnetic material according to claim 1 is
Since the organic magnetic material having the basic structure of triarylmethane represented by the general formula (I) is gradually cooled to a specific temperature T 1 equal to or lower than the critical temperature Tc, the magnetic susceptibility is increased. By the operation, it becomes possible to manufacture an organic magnetic material having good reproducibility and a large magnetic susceptibility.
【００３０】請求項２の有機磁性材料の製造方法は、前
記徐冷を−１．０Ｋ／分より小さい冷却速度で行なうこ
ととしたことから、より磁化率の大きい有機磁性材料の
製造が可能となる。In the method for producing an organic magnetic material according to claim 2, since the slow cooling is performed at a cooling rate lower than -1.0 K / min, it is possible to produce an organic magnetic material having a higher magnetic susceptibility. Become.
【００３１】請求項３の有機磁性材料の製造方法は、前
記徐冷を５０〜１５０Ｋの温度範囲まで行なうこととし
たことから、より磁化率の大きい有機磁性材料の製造が
可能となる。In the method for producing an organic magnetic material according to the third aspect, since the slow cooling is performed up to a temperature range of 50 to 150 K, it is possible to produce an organic magnetic material having a higher magnetic susceptibility.
【００３２】請求項４の有機磁性材料は、前記製造方法
を採用したことから、磁化率の大きいものとなる。The organic magnetic material of claim 4 has a large magnetic susceptibility because it adopts the manufacturing method.
【００３３】請求項５の有機磁性材料は、そのメチン炭
素部位におけるラジカル濃度が少なくとも１０17／ｇで
あるものとしたことから、磁化率の大きなものとなる。The organic magnetic material according to claim 5 has a large magnetic susceptibility because the radical concentration at the methine carbon site is at least 10 17 / g.
【図１】実施例１で得られた生成物の磁化率（χ）の温
度依存性を示すグラフである。FIG. 1 is a graph showing the temperature dependence of the magnetic susceptibility (χ) of the product obtained in Example 1.
【図２】実施例１で得られた生成物を５Ｋまで−４．５
Ｋ／分で急冷後、５Ｋに保持した場合の磁化率の時間依
存性を示すグラフである。FIG. 2 shows the product obtained in Example 1 at −4.5 up to 5K.
It is a graph which shows the time dependence of the magnetic susceptibility when it is kept at 5K after being rapidly cooled at K / min.
【図３】実施例３における冷却の温度プロファイルであ
る。3 is a cooling temperature profile in Example 3. FIG.
【図４】実施例３における磁化率の温度依存性を示すグ
ラフである。FIG. 4 is a graph showing temperature dependence of magnetic susceptibility in Example 3.
【図５】実施例４における磁化率の温度依存性を示すグ
ラフである。FIG. 5 is a graph showing temperature dependence of magnetic susceptibility in Example 4.
【図６】実施例５における磁化率の温度依存性を示すグ
ラフである。FIG. 6 is a graph showing temperature dependence of magnetic susceptibility in Example 5.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 谷内 將浩 東京都大田区中馬込１丁目３番６号 株式 会社リコー内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masahiro Taniuchi 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Co., Ltd.
Claims (5)
レン基（但し、環員にＮ、Ｓ若しくはＯよりなるヘテロ
原子を含むことができる）又は電子供与基置換フェニレ
ン基、 Ｒ2：置換若しくは非置換のアリール基、 ｎ：１以上の整数。〕で示されるトリアリールメタン基
本構造よりなる有機磁性材料において、臨界温度Ｔｃ以
下の特定温度Ｔ1まで徐冷を行なう操作により磁化率を
増大させることを特徴とする有機磁性材料の製造方法。1. A compound represented by the following general formula (I) [In formula, R < 1 >, R < 2 > and n show the following, respectively. R 1 : a substituted or unsubstituted fused polycyclic arylene group having two or more rings (provided that a ring member can contain a hetero atom consisting of N, S, or O) or an electron-donating group-substituted phenylene group, R 2 : substituted Or an unsubstituted aryl group, n: an integer of 1 or more. ] In the organic magnetic material having the triarylmethane basic structure shown in [3], the magnetic susceptibility is increased by an operation of gradually cooling to a specific temperature T 1 below the critical temperature Tc.
却速度で行なうことを特徴とする請求項１に記載の有機
磁性材料の製造方法。2. The method for producing an organic magnetic material according to claim 1, wherein the slow cooling is performed at a cooling rate lower than −1.0 K / min.
行なうことを特徴とする請求項１又は２に記載の有機磁
性材料の製造方法。3. The method for producing an organic magnetic material according to claim 1, wherein the slow cooling is performed in a temperature range of 50 to 150K.
法により形成された大きい磁化率を有する有機磁性材
料。4. An organic magnetic material having a large magnetic susceptibility formed by the method according to claim 1.
て、そのメチン炭素部位におけるラジカル濃度が少なく
とも１０17／ｇであることを特徴とする有機磁性材料。5. The organic magnetic material according to claim 4, wherein the radical concentration at the methine carbon site is at least 10 17 / g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19912494A JP3358012B2 (en) | 1994-08-01 | 1994-08-01 | Method for producing organic magnetic material and organic magnetic material obtained by this method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19912494A JP3358012B2 (en) | 1994-08-01 | 1994-08-01 | Method for producing organic magnetic material and organic magnetic material obtained by this method |
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| Publication Number | Publication Date |
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| JP3358012B2 JP3358012B2 (en) | 2002-12-16 |
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Cited By (1)
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|---|---|---|---|---|
| KR100382766B1 (en) * | 2001-07-02 | 2003-05-09 | 삼성전자주식회사 | Apparatus and method for measuring change of capacitance |
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|---|---|
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