JPWO2010058801A1 - Iron nitride fine particles having Fe16N2 and method for producing the same - Google Patents

Iron nitride fine particles having Fe16N2 and method for producing the same Download PDF

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JPWO2010058801A1
JPWO2010058801A1 JP2010518183A JP2010518183A JPWO2010058801A1 JP WO2010058801 A1 JPWO2010058801 A1 JP WO2010058801A1 JP 2010518183 A JP2010518183 A JP 2010518183A JP 2010518183 A JP2010518183 A JP 2010518183A JP WO2010058801 A1 JPWO2010058801 A1 JP WO2010058801A1
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carbonyl complex
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煥友 呉
煥友 呉
大森　智
智 大森
伊藤　晴彦
晴彦 伊藤
高橋　研
高橋　　研
小川　智之
智之 小川
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Abstract

【課題】Ｆｅ１６Ｎ２を有する窒化鉄粒子、液相においてＦｅ１６Ｎ２を有する窒化鉄粒子を製造する方法、並びにこのような方法のための中間体として用いることができる錯体及び分散液を提供する。【解決手段】平均粒子径が１００ｎｍ以下である、Ｆｅ１６Ｎ２を有する窒化鉄微粒子とする。また、（ａ）有機溶媒中に鉄錯体が分散している分散液を提供すること、及び（ｂ）前記鉄錯体から、Ｆｅ１６Ｎ２を有する窒化鉄粒子を生成することを含む、Ｆｅ１６Ｎ２を有する窒化鉄粒子の製造方法とする。また更に、この方法に用いることができる錯体及び分散液とする。Provided are iron nitride particles having Fe16N2, a method for producing iron nitride particles having Fe16N2 in the liquid phase, and complexes and dispersions that can be used as intermediates for such methods. The iron nitride fine particles have Fe16N2 having an average particle diameter of 100 nm or less. And (a) providing a dispersion in which an iron complex is dispersed in an organic solvent, and (b) generating iron nitride particles having Fe16N2 from the iron complex, and including iron nitride having Fe16N2. A method for producing particles is used. Furthermore, it is set as the complex and dispersion liquid which can be used for this method.

Description

本発明は、Ｆｅ１６Ｎ２を有する窒化鉄微粒子、及びその製造方法に関する。また本発明は、Ｆｅ１６Ｎ２を有する窒化鉄微粒子の製造方法に用いることができる分散液に関する。The present invention relates to iron nitride fine particles having Fe 16 N 2 and a method for producing the same. The present invention relates to dispersions that can be used in the manufacturing method of the iron nitride particles having an Fe 16 N 2.

磁性粉末、例えば高密度記録媒体、磁性塗料、磁性トナー、磁性キャリアー等に適した磁性粉末として、Ｆｅ１６Ｎ２を有する窒化鉄微粒子が知られている。As a magnetic powder suitable for a magnetic powder, for example, a high-density recording medium, a magnetic paint, a magnetic toner, a magnetic carrier, etc., iron nitride fine particles having Fe 16 N 2 are known.

このようなＦｅ１６Ｎ２を有する窒化鉄微粒子の製造に関しては、オキシ水酸化鉄等の還元によってα−Ｆｅを生成し、生成されたα−Ｆｅをアンモニア等によって気相で窒素化することが提案されている（特許文献１等）。Regarding the production of such iron nitride fine particles having Fe 16 N 2 , α-Fe is produced by reduction of iron oxyhydroxide and the like, and the produced α-Fe is nitrogenated in the gas phase with ammonia or the like. It has been proposed (Patent Document 1 etc.).

なお、液相において窒化鉄を合成するためには、鉄カルボニル錯体を原料として用い、この鉄カルボニル錯体を含有する有機溶媒に対してアンモニア等を導入することによって窒化鉄粒子を製造する方法が提案されている。このような液相法では、窒化鉄粒子を高い生産効率で得ることを期待できるものの、従来は比較的窒化の程度が大きいＦｅ３Ｎのみが得られていた（特許文献２）。In order to synthesize iron nitride in the liquid phase, a method for producing iron nitride particles by using iron carbonyl complex as a raw material and introducing ammonia or the like into an organic solvent containing this iron carbonyl complex is proposed. Has been. Although such a liquid phase method can be expected to obtain iron nitride particles with high production efficiency, conventionally, only Fe 3 N having a relatively high degree of nitriding has been obtained (Patent Document 2).

特開２００８−１０３５５１０JP2008-1035510 特開平５−２８６７０５（特に段落００１４〜００１７）JP-A-5-286705 (particularly paragraphs 0014 to 0017)

本発明では、平均粒子径が１００ｎｍ以下のＦｅ１６Ｎ２を有する窒化鉄粒子を提供する。また、上記記載のように、窒化鉄粒子を製造する液相法では、高い生産効率を期待できるものの、従来は比較的窒化の程度が大きいＦｅ３Ｎの生産のためにのみ考慮されていた。したがって本発明では、液相においてＦｅ１６Ｎ２を有する窒化鉄粒子を製造する方法、並びにこのような方法のための中間体として用いることができる錯体及び分散液を提供する。In the present invention, iron nitride particles having Fe 16 N 2 having an average particle diameter of 100 nm or less are provided. In addition, as described above, the liquid phase method for producing iron nitride particles can be expected to have high production efficiency, but has conventionally been considered only for the production of Fe 3 N having a relatively high degree of nitridation. Accordingly, the present invention provides a method for producing iron nitride particles having Fe 16 N 2 in the liquid phase, and complexes and dispersions that can be used as intermediates for such methods.

本願発明者らは、下記の本発明に想到した。   The inventors of the present application have come up with the following present invention.

〈１〉平均粒子径が１００ｎｍ以下である、Ｆｅ１６Ｎ２を有する窒化鉄微粒子。
〈２〉飽和磁化が１４０ｅｍｕ／ｇ以上である、上記〈１〉項に記載の窒化鉄微粒子。
〈３〉平均粒子径が１０ｎｍ以下である、上記〈１〉又は〈２〉項に記載の窒化鉄微粒子。
〈４〉（ａ）有機溶媒中に鉄錯体が分散している分散液を提供すること、及び
（ｂ）上記鉄錯体から、Ｆｅ１６Ｎ２を有する窒化鉄粒子を生成すること、
を含む、Ｆｅ１６Ｎ２を有する窒化鉄粒子の製造方法。
〈５〉上記鉄錯体が、アンモニア配位子及びカルボニル配位子を有する鉄アンモニアカルボニル錯体であり、且つ工程（ａ）で提供される上記分散液において、１３Ｃ−ＮＭＲによる鉄アンモニアカルボニル錯体と鉄カルボニル錯体とのピークの積分比（鉄アンモニアカルボニル錯体／鉄カルボニル錯体）が、１以上である、上記〈４〉項に記載の方法。
〈６〉工程（ｂ）において、外部から窒素含有化合物を供給しないで、Ｆｅ１６Ｎ２を有する窒化鉄粒子を生成する、上記〈５〉項に記載の方法。
〈７〉１３Ｃ−ＮＭＲにおける上記鉄アンモニアカルボニル錯体のピークが２３１ｐｐｍ付近である、上記〈５〉又は〈６〉項に記載の方法。
〈８〉上記鉄アンモニアカルボニル錯体が、式Ｆｅ３（ＣＯ）６（ＮＨ３）６を有する、上記〈５〉〜〈７〉項のいずれかに記載の方法。
〈９〉鉄カルボニル錯体を含有する有機溶媒、又は単独の鉄カルボニル錯体に、アンモニア又はアンモニア発生化合物を導入し、それによって上記鉄カルボニル錯体のカルボニル配位子の一部をアンモニア配位子で交換して、上記鉄アンモニアカルボニル錯体を生成する、上記〈５〉〜〈８〉項のいずれかに記載の方法。
〈１０〉生成した鉄アンモニアカルボニル錯体が沈殿する条件で、上記鉄アンモニアカルボニル錯体の生成を行う、上記〈９〉項に記載の方法。
〈１１〉生成した上記鉄アンモニアカルボニル錯体を他の部分から分離して、有機溶媒中に再分散させることによって、工程（ａ）で用いられる上記分散液を得る、上記〈９〉又は〈１０〉項に記載の方法。
〈１２〉上記鉄アンモニアカルボニル錯体の生成において、鉄カルボニル錯体が有機溶媒中に分散している上記分散液、又は単独の上記鉄カルボニル錯体を、８０℃〜２００℃の温度に加熱する、上記〈９〉〜〈１１〉項のいずれかに記載の方法。
〈１３〉工程（ａ）で提供される上記分散液が、第１〜第３級アミンからなる群より選択される界面活性剤を更に含有している、上記〈１〉〜〈１２〉項のいずれかに記載の方法。
〈１４〉工程（ｂ）において、上記分散液を８０℃〜２００℃の温度に加熱する、上記〈１〉〜〈１３〉項のいずれかに記載の方法。
〈１５〉式Ｆｅ３（ＣＯ）６（ＮＨ３）６を有する、鉄アンモニアカルボニル錯体。
〈１６〉Ｆｅ１６Ｎ２を有する窒化鉄微粒子の製造に用いられる、上記〈１５〉項に記載の鉄アンモニアカルボニル錯体。
〈１７〉１３Ｃ−ＮＭＲによる鉄アンモニアカルボニル錯体と鉄カルボニル錯体とのピークの積分比（鉄アンモニアカルボニル錯体／鉄カルボニル錯体）が、１以上である、鉄アンモニアカルボニル錯体が有機溶媒中に分散している分散液。
〈１８〉Ｆｅ１６Ｎ２を有する窒化鉄微粒子の製造に用いられる、上記〈１７〉項に記載の分散液。<1> Iron nitride fine particles having Fe 16 N 2 having an average particle diameter of 100 nm or less.
<2> The iron nitride fine particles according to <1>, wherein the saturation magnetization is 140 emu / g or more.
<3> The iron nitride fine particles according to <1> or <2>, wherein the average particle size is 10 nm or less.
<4> (a) Providing a dispersion in which an iron complex is dispersed in an organic solvent, and (b) Generating iron nitride particles having Fe 16 N 2 from the iron complex,
Including, method for producing the iron nitride particles having an Fe 16 N 2.
<5> The iron complex is an iron ammonia carbonyl complex having an ammonia ligand and a carbonyl ligand, and in the dispersion provided in the step (a), the iron ammonia carbonyl complex by 13 C-NMR and The method according to <4> above, wherein the peak integration ratio with the iron carbonyl complex (iron ammonia carbonyl complex / iron carbonyl complex) is 1 or more.
<6> The method according to <5>, wherein in step (b), iron nitride particles having Fe 16 N 2 are generated without supplying a nitrogen-containing compound from the outside.
<7> The method according to <5> or <6>, wherein the peak of the iron ammonia carbonyl complex in 13 C-NMR is around 231 ppm.
<8> The method according to any one of <5> to <7>, wherein the iron ammonia carbonyl complex has the formula Fe 3 (CO) 6 (NH 3 ) 6 .
<9> Ammonia or an ammonia generating compound is introduced into an organic solvent containing an iron carbonyl complex or a single iron carbonyl complex, whereby a part of the carbonyl ligand of the iron carbonyl complex is exchanged with the ammonia ligand. The method according to any one of <5> to <8>, wherein the iron ammonia carbonyl complex is produced.
<10> The method according to <9>, wherein the iron ammonia carbonyl complex is produced under conditions where the produced iron ammonia carbonyl complex is precipitated.
<11> The produced iron ammonia carbonyl complex is separated from other parts and redispersed in an organic solvent to obtain the dispersion used in step (a). <9> or <10> The method according to item.
<12> In the production of the iron ammonia carbonyl complex, the dispersion in which the iron carbonyl complex is dispersed in an organic solvent or the single iron carbonyl complex is heated to a temperature of 80 ° C. to 200 ° C. The method according to any one of items 9> to <11>.
<13> The above <1> to <12>, wherein the dispersion provided in step (a) further contains a surfactant selected from the group consisting of primary to tertiary amines. The method according to any one.
<14> The method according to any one of <1> to <13> above, wherein in the step (b), the dispersion is heated to a temperature of 80C to 200C.
<15> An iron ammonia carbonyl complex having the formula Fe 3 (CO) 6 (NH 3 ) 6 .
<16> The iron ammonia carbonyl complex according to the above <15>, which is used for producing iron nitride fine particles having Fe 16 N 2 .
<17> The peak ratio of iron ammonia carbonyl complex to iron carbonyl complex (iron ammonia carbonyl complex / iron carbonyl complex) by 13 C-NMR is 1 or more, and the iron ammonia carbonyl complex is dispersed in an organic solvent. Dispersion.
<18> The dispersion described in the above item <17>, which is used for the production of iron nitride fine particles having Fe 16 N 2 .

本発明の窒化鉄粒子は、大きい飽和磁化の値を有し、したがって磁性粉末としての用途で使用することができる。また、Ｆｅ１６Ｎ２を有する窒化鉄粒子を製造する本発明の方法によれば、Ｆｅ１６Ｎ２を有する窒化鉄粒子を効果的に製造することができる。また更に、本発明の錯体及び分散液は、このような本発明の方法のための中間体として用いることができる。The iron nitride particles of the present invention have a large saturation magnetization value and can therefore be used in applications as magnetic powders. Moreover, according to the method of the present invention for producing iron nitride particles having Fe 16 N 2 , iron nitride particles having Fe 16 N 2 can be effectively produced. Still further, the complexes and dispersions of the invention can be used as intermediates for such inventive methods.

図１は、実施例１で得られた鉄アンモニアカルボニル錯体についての１３Ｃ−ＮＭＲによる分析結果を示す図である。1 is a diagram showing the results of 13 C-NMR analysis of the iron ammonia carbonyl complex obtained in Example 1. FIG. 図２は、実施例及び比較例で得られた窒化鉄粒子について測定された磁化（３００Ｋ）の値を示す図である。FIG. 2 is a diagram showing the value of magnetization (300 K) measured for the iron nitride particles obtained in Examples and Comparative Examples.

〈Ｆｅ１６Ｎ２を有する本発明の窒化鉄微粒子〉
Ｆｅ１６Ｎ２を有する本発明の窒化鉄微粒子は、平均粒子径が、１００ｎｍ以下、５０ｎｍ以下、又は１０ｎｍ以下であってよく、特に５ｎｍ以上１０ｎｍ以下である。<Iron nitride particles of the present invention having the Fe 16 N 2>
The iron nitride fine particles of the present invention having Fe 16 N 2 may have an average particle diameter of 100 nm or less, 50 nm or less, or 10 nm or less, and particularly 5 nm or more and 10 nm or less.

また、本発明の窒化鉄微粒子は、１４０ｅｍｕ／ｇ以上、１５０ｅｍｕ／ｇ以上、１６０ｅｍｕ／ｇ以上、又は１７０ｅｍｕ／ｇ以上の飽和磁化を有することができる。   Further, the iron nitride fine particles of the present invention can have a saturation magnetization of 140 emu / g or more, 150 emu / g or more, 160 emu / g or more, or 170 emu / g or more.

なお、本発明の窒化鉄微粒子にＦｅ１６Ｎ２と共に含有されている可能性がある鉄系材料としては、α−Ｆｅ、Ｆｅ３Ｏ４、Ｆｅ３Ｎが考えられる。ここで、これらの鉄系材料の飽和磁化の値は、以下の通りであることが知られている。Note that α-Fe, Fe 3 O 4 , and Fe 3 N are considered as iron-based materials that may be contained in the iron nitride fine particles of the present invention together with Fe 16 N 2 . Here, it is known that the saturation magnetization values of these iron-based materials are as follows.

Figure 2010058801
Figure 2010058801

本発明の窒化鉄微粒子は、Ｆｅ１６Ｎ２を有する窒化鉄粒子を製造する本発明の方法によって製造することができる。また、本発明の窒化鉄微粒子は、磁性粉末としての用途で使用することができる。The iron nitride fine particles of the present invention can be produced by the method of the present invention for producing iron nitride particles having Fe 16 N 2 . Moreover, the iron nitride fine particles of the present invention can be used for applications as magnetic powder.

〈Ｆｅ１６Ｎ２を有する窒化鉄粒子を製造する本発明の方法〉
Ｆｅ１６Ｎ２を有する窒化鉄粒子を製造する本発明の方法は、（ａ）有機溶媒中に鉄錯体が分散している分散液を提供すること、及び（ｂ）この鉄錯体から、Ｆｅ１６Ｎ２を有する窒化鉄粒子を生成することを含む。<Method of the Present Invention for Producing Iron Nitride Particles Having Fe 16 N 2 >
The method of the present invention for producing iron nitride particles having Fe 16 N 2 comprises (a) providing a dispersion in which an iron complex is dispersed in an organic solvent, and (b) from the iron complex, Fe 16 and generating an iron nitride particle having a N 2.

この本発明の方法では、反応条件を選択して窒化鉄粒子の窒素化の程度を調節することによって、鉄錯体から、Ｆｅ１６Ｎ２を有する窒化鉄粒子を生成することができる。また、この本発明の方法では、反応条件を選択して、平均粒子径が１００ｎｍ以下、５０ｎｍ以下、又は１０ｎｍ以下、例えば５ｎｍ以上１０ｎｍ以下の窒化鉄微粒子を製造することができる。In the method of the present invention, iron nitride particles having Fe 16 N 2 can be produced from an iron complex by selecting the reaction conditions and adjusting the degree of nitrogenation of the iron nitride particles. In the method of the present invention, iron nitride fine particles having an average particle diameter of 100 nm or less, 50 nm or less, or 10 nm or less, for example, 5 nm or more and 10 nm or less can be produced by selecting reaction conditions.

工程（ａ）で提供される分散液に含有される有機溶媒としては、使用する鉄錯体を分散させて保持することができる任意の有機溶媒を用いることができる。この有機溶媒としては例えば、炭化水素、特にＣ１０〜Ｃ３０の炭化水素（例えばＣ１０〜Ｃ２０の炭化水素）、より特にケロシンを用いることができる。As the organic solvent contained in the dispersion provided in the step (a), any organic solvent capable of dispersing and holding the iron complex to be used can be used. As this organic solvent, for example, hydrocarbons, especially C 10 -C 30 hydrocarbons (eg C 10 -C 20 hydrocarbons), more particularly kerosene can be used.

工程（ａ）で提供される分散液に含有される鉄錯体としては、任意の鉄錯体を用いることができ、例えばカルボニル配位子、アンモニア配位子、及び／又はアミン配位子を有する鉄錯体、特にカルボニル配位子及びアンモニア配位子の組み合わせを有する鉄アンモニアカルボニル錯体を用いることができる。   Arbitrary iron complexes can be used as the iron complex contained in the dispersion provided in step (a), for example, iron having a carbonyl ligand, an ammonia ligand, and / or an amine ligand. Complexes, particularly iron ammonia carbonyl complexes having a combination of carbonyl and ammonia ligands, can be used.

工程（ｂ）においては、窒素源として、窒素原子を有する配位子、及び／又は外部から供給される窒素含有化合物、例えばアンモニアを利用することができる。窒素原子を有する配位子としては、例えばアンモニア配位子又はアミン配位子、特にアンモニア配位子を挙げることができる。また、窒素源として外部から供給されるアンモニアを用いる場合、アンモニア自体を直接に外部から供給するだけでなく、アンモニアを発生させるアンモニア発生化合物を外部から供給して、分散液中においてアンモニアを発生させることもできる。   In the step (b), a nitrogen-containing ligand and / or a nitrogen-containing compound supplied from the outside, such as ammonia, can be used as a nitrogen source. Examples of the ligand having a nitrogen atom include an ammonia ligand or an amine ligand, particularly an ammonia ligand. In addition, when using ammonia supplied from the outside as a nitrogen source, not only ammonia itself is directly supplied from the outside, but also an ammonia generating compound that generates ammonia is supplied from the outside to generate ammonia in the dispersion. You can also.

工程（ａ）で提供される分散液は、鉄錯体の分散性を改良するために界面活性剤を更に含有することができる。この界面活性剤としては例えば、第１〜第３級アミン、特にＣ１０〜Ｃ３０の炭化水素基を有する第１級アミン、より特にＣ１０〜Ｃ３０のアルキル基を有する第１級アミン、更により特にオレイルアミンを挙げることができる。The dispersion provided in step (a) can further contain a surfactant in order to improve the dispersibility of the iron complex. As the surfactant for example, first to tertiary amines, especially primary amines having a primary amine, more particularly an alkyl group of C 10 -C 30 having a hydrocarbon group of C 10 -C 30, More particularly, oleylamine can be mentioned.

工程（ｂ）においては、Ｆｅ１６Ｎ２を有する窒化鉄粒子の生成を促進するために、分散液を加熱することができ、例えば分散液を８０℃〜２００℃、特に１２０℃〜２００℃の温度に加熱することができる。In step (b), the dispersion can be heated in order to promote the production of iron nitride particles having Fe 16 N 2 , for example, the dispersion is 80 ° C. to 200 ° C., particularly 120 ° C. to 200 ° C. Can be heated to temperature.

〈Ｆｅ１６Ｎ２を有する窒化鉄粒子を製造する本発明の方法−鉄アンモニアカルボニル錯体を用いる態様〉
Ｆｅ１６Ｎ２を有する窒化鉄粒子を製造する本発明の方法の１つの態様では、鉄錯体として、アンモニア配位子及びカルボニル配位子を有する鉄アンモニアカルボニル錯体を用い、且つ工程（ａ）で提供される分散液において、１３Ｃ−ＮＭＲによる鉄アンモニアカルボニル錯体と鉄カルボニル錯体とのピークの積分比（鉄アンモニアカルボニル錯体／鉄カルボニル錯体）が、１以上であってよい。ここでこの比は例えば、２以上、３以上、４以上、５以上、６以上、８以上、又は１０以上であってよい。<Method of the Present Invention for Producing Iron Nitride Particles Containing Fe 16 N 2 -Aspect Using Iron Ammonium Carbonyl Complex>
In one embodiment of the method of the present invention for producing iron nitride particles having Fe 16 N 2 , an iron ammonia carbonyl complex having an ammonia ligand and a carbonyl ligand is used as the iron complex, and in step (a) In the provided dispersion, the integral ratio (iron ammonia carbonyl complex / iron carbonyl complex) of the iron ammonia carbonyl complex and the iron carbonyl complex by 13 C-NMR may be 1 or more. Here, this ratio may be 2 or more, 3 or more, 4 or more, 5 or more, 6 or more, 8 or more, or 10 or more, for example.

この態様でのように、１３Ｃ−ＮＭＲによる鉄アンモニアカルボニル錯体と鉄カルボニル錯体とのピークの積分比（鉄アンモニアカルボニル錯体／鉄カルボニル錯体）が比較的大きいことは、分散液における鉄アンモニアカルボニル錯体の存在比が比較的大きいことを意味している。分散液における鉄アンモニアカルボニル錯体の存在比が十分に大きい場合、工程（ｂ）において、窒素源として、アンモニア配位子を利用することができ、したがって外部から比較的少量の窒素含有化合物のみを供給して、又は外部から窒素含有化合物を供給しないで、Ｆｅ１６Ｎ２を有する窒化鉄粒子を得ることができる。As in this embodiment, the relatively large integral ratio (iron ammonia carbonyl complex / iron carbonyl complex) between the iron ammonia carbonyl complex and the iron carbonyl complex by 13 C-NMR indicates that the iron ammonia carbonyl complex in the dispersion is This means that the abundance ratio of is relatively large. When the abundance ratio of the iron ammonia carbonyl complex in the dispersion is sufficiently large, an ammonia ligand can be used as a nitrogen source in step (b), and therefore only a relatively small amount of nitrogen-containing compound is supplied from the outside. Thus, iron nitride particles having Fe 16 N 2 can be obtained without supplying a nitrogen-containing compound from the outside.

１３Ｃ−ＮＭＲにおける鉄アンモニアカルボニル錯体のピークとしては、２３１ｐｐｍ付近のピークを観察することができる。なお、１３Ｃ−ＮＭＲにおける鉄カルボニル錯体のピークは、２１２ｐｐｍ付近に現れる。なお、この鉄アンモニアカルボニル錯体は、式Ｆｅ３（ＣＯ）６（ＮＨ３）６を有するものであってよい。 As a peak of the iron ammonia carbonyl complex in 13 C-NMR, a peak around 231 ppm can be observed. In addition, the peak of the iron carbonyl complex in 13 C-NMR appears in the vicinity of 212 ppm. The iron ammonia carbonyl complex may have the formula Fe 3 (CO) 6 (NH 3 ) 6 .

〈Ｆｅ１６Ｎ２を有する窒化鉄粒子を製造する本発明の方法−鉄アンモニアカルボニル錯体を用いる態様−鉄アンモニアカルボニル錯体の製造〉
鉄アンモニアカルボニル錯体の製造のためには、鉄カルボニル錯体を含有する有機溶媒、又は単独の鉄カルボニル錯体に、アンモニア又はアンモニア発生化合物を導入し、それによって鉄カルボニル錯体のカルボニル配位子の一部をアンモニア配位子で交換することができる。<Method of the Present Invention for Producing Iron Nitride Particles Containing Fe 16 N 2 -Aspect Using Iron Ammonia Carbonyl Complex-Production of Iron Ammonia Carbonyl Complex>
For the production of an iron ammonia carbonyl complex, ammonia or an ammonia-generating compound is introduced into an organic solvent containing the iron carbonyl complex or a single iron carbonyl complex, whereby a part of the carbonyl ligand of the iron carbonyl complex. Can be exchanged with ammonia ligands.

鉄アンモニアカルボニル錯体の生成を促進するために、鉄アンモニアカルボニル錯体の生成を加熱条件で行うことができ、例えば鉄アンモニアカルボニル錯体の生成を８０℃〜２００℃、特に１２０℃〜２００℃の温度で行うことができる。   In order to promote the formation of the iron ammonia carbonyl complex, the formation of the iron ammonia carbonyl complex can be carried out under heating conditions. For example, the formation of the iron ammonia carbonyl complex can be carried out at a temperature of 80 ° C. to 200 ° C., particularly 120 ° C. It can be carried out.

また、鉄アンモニアカルボニル錯体の生成においては、生成した鉄アンモニアカルボニル錯体が沈殿する条件、例えば鉄カルボニル錯体を含有する有機溶媒、又は単独の鉄カルボニル錯体が、界面活性剤を実質的に含有していない条件で行うことができる。鉄カルボニル錯体がケロシンのような有機溶媒に溶解するのに対して、生成物である鉄アンモニアカルボニル錯体はケロシンのような有機溶媒に対して不溶性であるので、この場合には、生成した鉄アンモニアカルボニル錯体の分離が容易になる。ただし、必要に応じて、界面活性剤を用いて、生成した鉄アンモニアカルボニル錯体を有機溶媒中に分散させることもできる。   Further, in the production of the iron ammonia carbonyl complex, the conditions under which the produced iron ammonia carbonyl complex precipitates, for example, the organic solvent containing the iron carbonyl complex, or the single iron carbonyl complex substantially contains the surfactant. Can be done under no conditions. The iron carbonyl complex dissolves in an organic solvent such as kerosene, whereas the product iron ammonia carbonyl complex is insoluble in an organic solvent such as kerosene. Separation of the carbonyl complex is facilitated. However, if necessary, the produced iron ammonia carbonyl complex can be dispersed in an organic solvent using a surfactant.

界面活性剤を含有する条件、及び界面活性剤を含有しない条件のいずれにおいて鉄アンモニアカルボニル錯体を生成する場合にも、生成した鉄アンモニアカルボニル錯体を他の部分から分離し、随意に精製、乾燥等を行った後で、有機溶媒中に再分散させることによって、工程（ａ）で用いられる分散液を得ることができる。この場合には、１３Ｃ−ＮＭＲによる鉄アンモニアカルボニル錯体と鉄カルボニル錯体とのピークの積分比（鉄アンモニアカルボニル錯体／鉄カルボニル錯体）を比較的大きくすること、すなわち分散液における鉄アンモニアカルボニル錯体の存在比を比較的大きくすることが容易に達成できる。In the case where the iron ammonia carbonyl complex is produced under any condition containing a surfactant and no surfactant, the produced iron ammonia carbonyl complex is separated from other parts and optionally purified, dried, etc. After performing the above, the dispersion used in step (a) can be obtained by redispersing in an organic solvent. In this case, the peak integration ratio (iron ammonia carbonyl complex / iron carbonyl complex) between the iron ammonia carbonyl complex and the iron carbonyl complex by 13 C-NMR should be relatively large, that is, the iron ammonia carbonyl complex in the dispersion liquid. A relatively large abundance can be easily achieved.

〈本発明の鉄アンモニアカルボニル錯体〉
本発明の鉄アンモニアカルボニル錯体は、式Ｆｅ３（ＣＯ）６（ＮＨ３）６を有する。<Iron ammonia carbonyl complex of the present invention>
The iron ammonia carbonyl complex of the present invention has the formula Fe 3 (CO) 6 (NH 3 ) 6 .

この本発明の鉄アンモニアカルボニル錯体は、Ｆｅ１６Ｎ２を有する窒化鉄微粒子の製造のための中間体として用いることができ、特にＦｅ１６Ｎ２を有する窒化鉄微粒子を製造する本発明の方法のための中間体として用いることができる。この本発明の分散液は、Ｆｅ１６Ｎ２を有する窒化鉄微粒子を製造する本発明の方法に関して上記で説明したようにして、製造することができる。Iron ammonia carbonyl complexes of the present invention, it can be used as intermediates for the preparation of iron nitride particles having an Fe 16 N 2, in particular the inventive method for manufacturing a nitride fine iron particles having an Fe 16 N 2 Can be used as an intermediate for. This dispersion of the present invention can be produced as described above with respect to the method of the present invention for producing iron nitride fine particles having Fe 16 N 2 .

〈鉄カルボニル錯体が有機溶媒中に分散している本発明の分散液〉
本発明の分散液は、１３Ｃ−ＮＭＲによる鉄アンモニアカルボニル錯体と鉄カルボニル錯体とのピークの積分比（鉄アンモニアカルボニル錯体／鉄カルボニル錯体）が、１以上である、鉄アンモニアカルボニル錯体が有機溶媒中に分散している分散液である。ここで、この比は例えば、２以上、３以上、４以上、５以上、６以上、８以上、又は１０以上であってよい。<Dispersion of the present invention in which an iron carbonyl complex is dispersed in an organic solvent>
The dispersion of the present invention has an integral ratio of peaks of iron ammonia carbonyl complex and iron carbonyl complex by 13 C-NMR (iron ammonia carbonyl complex / iron carbonyl complex) of 1 or more, and the iron ammonia carbonyl complex is an organic solvent. It is a dispersion liquid dispersed in the inside. Here, this ratio may be 2 or more, 3 or more, 4 or more, 5 or more, 6 or more, 8 or more, or 10 or more, for example.

この本発明の分散液は、Ｆｅ１６Ｎ２を有する窒化鉄微粒子の製造のための中間体として用いることができ、特にＦｅ１６Ｎ２を有する窒化鉄微粒子を製造する本発明の方法のための中間体として用いることができる。この本発明の分散液は、Ｆｅ１６Ｎ２を有する窒化鉄微粒子を製造する本発明の方法に関して上記で説明したようにして、製造することができる。The dispersion of the present invention, it can be used as intermediates for the preparation of iron nitride particles having an Fe 16 N 2, in particular for the method of the present invention for producing the iron nitride particles having an Fe 16 N 2 It can be used as an intermediate. This dispersion of the present invention can be produced as described above with respect to the method of the present invention for producing iron nitride fine particles having Fe 16 N 2 .

《飽和磁化の測定》
以下の実施例において、飽和磁化は、窒化鉄微粒子中に含まれる鉄の単位質量あたりの飽和磁化の値（ｅｍｕ／ｇ）として表している。ここで、この飽和磁化の値は、ＳＱＵＩＤ（超伝導量子干渉素子）を用いて３００Ｋにおいて測定した。また、鉄の質量は、蛍光Ｘ線分析（ＸＲＦ）の結果から算出した。このようにして得られた飽和磁化値を、得られた鉄の質量の値で割って、その窒化鉄超微粒子中に含まれる鉄の単位質量あたりの飽和磁化（ｅｍｕ／ｇ）を算出した。<Measurement of saturation magnetization>
In the following examples, the saturation magnetization is expressed as the value of saturation magnetization (emu / g) per unit mass of iron contained in the iron nitride fine particles. Here, the value of the saturation magnetization was measured at 300 K using a SQUID (superconducting quantum interference device). The mass of iron was calculated from the result of X-ray fluorescence analysis (XRF). The saturation magnetization value obtained in this manner was divided by the value of the obtained iron mass to calculate the saturation magnetization (emu / g) per unit mass of iron contained in the iron nitride ultrafine particles.

具体的には、窒化鉄微粒子の飽和磁化の大きさは下記のようにして測定した。すなわち、アルゴン雰囲気のグローブボックス内において、窒化鉄微粒子のコロイド溶液をアセトンで洗浄後、ケロシンに再分散させ（３０ｍｇ）、これを石英管（直径：５ｍｍ、内径：３ｍｍ）に入れ、エポキシ樹脂で蓋をして、測定サンプルとした。この測定サンプルを超伝導量子干渉素子（ＳＱＵＩＤ）磁束計（ＱＵＡＮＴＯＭ ＤＥＳＩＧＮ社製ＭＰＭＳ−５）にセットし、測定温度（３００Ｋ）において磁化の測定を行った。測定磁界範囲は−４６〜＋４６ｋＯｅとし、＋４６ｋＯｅでの磁化の測定値を飽和磁化とした。   Specifically, the magnitude of the saturation magnetization of the iron nitride fine particles was measured as follows. That is, in a glove box in an argon atmosphere, a colloidal solution of iron nitride fine particles was washed with acetone, then redispersed in kerosene (30 mg), and placed in a quartz tube (diameter: 5 mm, inner diameter: 3 mm). The sample was covered and used as a measurement sample. This measurement sample was set in a superconducting quantum interference device (SQUID) magnetometer (MPMS-5 manufactured by QUANTOM DESIGN), and magnetization was measured at a measurement temperature (300K). The measurement magnetic field range was −46 to +46 kOe, and the measured value of magnetization at +46 kOe was the saturation magnetization.

《実施例１》
〈鉄アンモニアカルボニル錯体の生成〉
この実施例では、下記に概略を示す反応経路で、鉄アンモニアカルボニル錯体を製造した：
Ｆｅ（ＣＯ）５ ＋ ＮＨ３ → 鉄アンモニアカルボニル錯体Example 1
<Formation of iron ammonia carbonyl complex>
In this example, an iron ammonia carbonyl complex was prepared by the reaction route outlined below:
Fe (CO) 5 + NH 3 → iron ammonia carbonyl complex

具体的にはこの実施例では、４．８ｇの鉄カルボニル錯体（Ｆｅ（ＣＯ）５）を、溶媒としての４５ｍｌのケロシンに加えて鉄カルボニル錯体含有溶液を得た。その後、このようにして得られた鉄カルボニル錯体含有溶液を、４時間にわたって１１０℃の温度に加熱しながら、アンモニア（ＮＨ３）を１００ｍｌ／分の量でバブリングによって供給して、鉄アンモニアカルボニル錯体を生成して沈殿物として得た。すなわち、鉄カルボニル錯体がケロシンに溶解するのに対して、得られた鉄アンモニアカルボニル錯体はケロシンに対して不溶性であり、沈殿物として析出した。Specifically, in this example, 4.8 g of iron carbonyl complex (Fe (CO) 5 ) was added to 45 ml of kerosene as a solvent to obtain an iron carbonyl complex-containing solution. Thereafter, while the iron carbonyl complex-containing solution thus obtained was heated to a temperature of 110 ° C. for 4 hours, ammonia (NH 3 ) was supplied by bubbling in an amount of 100 ml / min to obtain an iron ammonia carbonyl complex. Was obtained as a precipitate. That is, while the iron carbonyl complex was dissolved in kerosene, the obtained iron ammonia carbonyl complex was insoluble in kerosene and deposited as a precipitate.

得られた鉄アンモニアカルボニル錯体を溶媒としてのケロシンから分離し、アルゴン雰囲気のグローブボックス内において１５０ｍｌのヘキサンで遠心洗浄を３回（ヘキサン５０ｍｌ×３回）行って、鉄カルボニル錯体を除去し、乾燥して、鉄アンモニアカルボニル錯体を粉末状の生成物として得た。   The obtained iron ammonia carbonyl complex was separated from kerosene as a solvent, and was subjected to centrifugal washing with 150 ml of hexane three times (hexane 50 ml × 3 times) in a glove box under an argon atmosphere to remove the iron carbonyl complex, followed by drying. As a result, an iron ammonia carbonyl complex was obtained as a powdery product.

粉末状の生成物についてのＦＴ−ＩＲ（フーリエ変換赤外分光分析）を行って、生成物がアンモニア配位子（ＮＨ３）を有していることを確認した。また、ＧＣ−ＭＳ（ガスクロマトグラフ質量分析）を行って、生成物がアンモニア配位子（ＮＨ３）及びカルボニル配位子（ＣＯ）を有していることを確認した。また、ＭＳ（質量分析）を行って、生成物の分子量が約４３８であることを確認した。これらの分析の結果からは、生成物が式Ｆｅ３（ＣＯ）６（ＮＨ３）６（分子量（計算値）：４３８）を有する鉄アンモニアカルボニル錯体であると考えられる。The powdered product was subjected to FT-IR (Fourier transform infrared spectroscopy) to confirm that the product had an ammonia ligand (NH 3 ). Further, by performing a GC-MS (gas chromatography mass spectrometry), the product was confirmed to have an ammonia ligand (NH 3) and carbonyl ligands (CO). Moreover, MS (mass spectrometry) was performed and it confirmed that the molecular weight of the product was about 438. From the results of these analyses, the product is considered to be an iron ammonia carbonyl complex having the formula Fe 3 (CO) 6 (NH 3 ) 6 (molecular weight (calculated value): 438).

粉末状の生成物についての１３Ｃ−ＮＭＲの結果を図１に示す。図１からは、得られた粉末状の生成物において、１３Ｃ−ＮＭＲによる鉄アンモニアカルボニル錯体と鉄カルボニル錯体とのピークの積分比（鉄アンモニアカルボニル錯体／鉄カルボニル錯体）が、約８であることが理解される。The results of 13 C-NMR for the powdered product are shown in FIG. From FIG. 1, in the obtained powdery product, the integral ratio of iron ammonia carbonyl complex and iron carbonyl complex (iron ammonia carbonyl complex / iron carbonyl complex) by 13 C-NMR is about 8. It is understood.

〈窒化鉄粒子の生成〉
上記のようにして得た粉末状の鉄アンモニアカルボニル錯体を用い、下記に概略を示す反応経路で、アンモニアの添加を行わずに、窒化鉄粒子を生成した：
鉄アンモニアカルボニル錯体 ＋ オレイルアミン（界面活性剤）
＋ ケロシン（溶媒）
→ 窒化鉄粒子<Production of iron nitride particles>
The powdered iron ammonia carbonyl complex obtained as described above was used to produce iron nitride particles in the reaction route outlined below, without the addition of ammonia:
Iron ammonia carbonyl complex + oleylamine (surfactant)
+ Kerosene (solvent)
→ Iron nitride particles

具体的にはこの実施例では、実施例１において得られた０．１ｇの粉末状の生成物（鉄アンモニアカルボニル錯体）を、０．１２ｇのオレイルアミン（界面活性剤として）を含有する１０ｍｌのケロシン（溶媒として）に分散させて、鉄アンモニアカルボニル錯体分散液を得た。その後、このようにして得られた鉄アンモニアカルボニル錯体分散液を、２時間にわたって１８０℃の温度に加熱して、窒化鉄粒子を生成した。   Specifically, in this example, 0.1 g of the powdery product (iron ammonia carbonyl complex) obtained in Example 1 was replaced with 10 ml of kerosene containing 0.12 g of oleylamine (as a surfactant). It was dispersed in (as a solvent) to obtain an iron ammonia carbonyl complex dispersion. Thereafter, the iron ammonia carbonyl complex dispersion thus obtained was heated to a temperature of 180 ° C. for 2 hours to produce iron nitride particles.

ＳＱＵＩＤによる測定によれば、得られた窒化鉄粒子の飽和磁化（３００Ｋ）は、１６６ｅｍｕ／ｇであった（図２）。鉄系材料の飽和磁化の値に関する上記の表１によれば、この窒化鉄粒子の飽和磁化の値は、この窒化鉄粒子がＦｅ１６Ｎ２を有することを意味する。電子顕微鏡による観察によれば、得られた窒化鉄粒子は、粒子径約９ｎｍの球形の形状を有していた。また、得られた窒化鉄粒子についての電子線回折分析による測定結果を、下記の表２に示す。According to the measurement by SQUID, the saturation magnetization (300 K) of the obtained iron nitride particles was 166 emu / g (FIG. 2). According to Table 1 above regarding the value of the saturation magnetization of the iron-based material, the value of the saturation magnetization of the iron nitride particles means that the iron nitride particles have Fe 16 N 2 . According to observation with an electron microscope, the obtained iron nitride particles had a spherical shape with a particle diameter of about 9 nm. Moreover, the measurement result by the electron diffraction analysis about the obtained iron nitride particle is shown in the following Table 2.

Figure 2010058801
Figure 2010058801

《実施例２》
〈鉄アンモニアカルボニル錯体の生成〉
この実施例では、鉄アンモニアカルボニル錯体の遠心洗浄を、３回（ヘキサン５０ｍｌ×３回）ではなく、５回（ヘキサン５０ｍｌ×５回）行ったことを除いて、実施例１と同様にして、鉄アンモニアカルボニル錯体を粉末状の生成物として得た。Example 2
<Formation of iron ammonia carbonyl complex>
In this example, centrifugal washing of the iron ammonia carbonyl complex was performed three times (hexane 50 ml × 5 times) instead of three times (hexane 50 ml × 5 times). The iron ammonia carbonyl complex was obtained as a powdery product.

粉末状の生成物についての１３Ｃ−ＮＭＲでは、鉄アンモニアカルボニル錯体のピークのみが検出され、鉄カルボニル錯体のピークが検出されなかった。すなわち、粉末状の生成物の１３Ｃ−ＮＭＲによる鉄アンモニアカルボニル錯体と鉄カルボニル錯体とのピークの積分比（鉄アンモニアカルボニル錯体／鉄カルボニル錯体）は、実質的に無限大（∞）であった。In 13 C-NMR for the powdered product, only the peak of the iron ammonia carbonyl complex was detected, and the peak of the iron carbonyl complex was not detected. That is, the integral ratio (iron ammonia carbonyl complex / iron carbonyl complex) between the iron ammonia carbonyl complex and the iron carbonyl complex by 13 C-NMR of the powdery product was substantially infinite (∞). .

〈窒化鉄粒子の生成〉
上記のようにして得た粉末状の鉄アンモニアカルボニル錯体から、実施例１と同様にして、窒化鉄粒子を生成した。<Production of iron nitride particles>
In the same manner as in Example 1, iron nitride particles were produced from the powdered iron ammonia carbonyl complex obtained as described above.

ＳＱＵＩＤによる測定によれば、得られた窒化鉄粒子の飽和磁化（３００Ｋ）は、１７８ｅｍｕ／ｇであった（図２）。鉄系材料の飽和磁化の値に関する上記の表１によれば、この窒化鉄粒子の飽和磁化の値は、この窒化鉄粒子がＦｅ１６Ｎ２を有することを意味する。電子顕微鏡による観察によれば、得られた窒化鉄粒子は、粒子径約９ｎｍの球形の形状を有していた。According to the measurement by SQUID, the saturation magnetization (300 K) of the obtained iron nitride particles was 178 emu / g (FIG. 2). According to Table 1 above regarding the value of the saturation magnetization of the iron-based material, the value of the saturation magnetization of the iron nitride particles means that the iron nitride particles have Fe 16 N 2 . According to observation with an electron microscope, the obtained iron nitride particles had a spherical shape with a particle diameter of about 9 nm.

《実施例３》
〈鉄アンモニアカルボニル錯体の生成〉
この実施例では、鉄アンモニアカルボニル錯体の遠心洗浄を、３回（ヘキサン５０ｍｌ×３回）ではなく、１回（ヘキサン５０ｍｌ×１回）行ったことを除いて、実施例１と同様にして、鉄アンモニアカルボニル錯体を粉末状の生成物として得た。Example 3
<Formation of iron ammonia carbonyl complex>
In this example, centrifugal washing of the iron ammonia carbonyl complex was performed three times (hexane 50 ml × 3 times) instead of once (hexane 50 ml × 1 time), as in Example 1, The iron ammonia carbonyl complex was obtained as a powdery product.

粉末状の生成物の１３Ｃ−ＮＭＲによる鉄アンモニアカルボニル錯体と鉄カルボニル錯体とのピークの積分比（鉄アンモニアカルボニル錯体／鉄カルボニル錯体）が、約３であった。The integral ratio (iron ammonia carbonyl complex / iron carbonyl complex) of the peak of the iron ammonia carbonyl complex and the iron carbonyl complex by 13 C-NMR of the powdery product was about 3.

〈窒化鉄粒子の生成〉
上記のようにして得た粉末状の鉄アンモニアカルボニル錯体から、実施例１と同様にして、窒化鉄粒子を生成した。<Production of iron nitride particles>
In the same manner as in Example 1, iron nitride particles were produced from the powdered iron ammonia carbonyl complex obtained as described above.

ＳＱＵＩＤによる測定によれば、得られた窒化鉄粒子の飽和磁化（３００Ｋ）は、１５８ｅｍｕ／ｇであった（図２）。鉄系材料の飽和磁化の値に関する上記の表１によれば、この窒化鉄粒子の飽和磁化の値は、この窒化鉄粒子がＦｅ１６Ｎ２を有することを意味する。電子顕微鏡による観察によれば、得られた窒化鉄粒子は、粒子径約８ｎｍの球形の形状を有していた。According to the measurement by SQUID, the saturation magnetization (300K) of the obtained iron nitride particles was 158 emu / g (FIG. 2). According to Table 1 above regarding the value of the saturation magnetization of the iron-based material, the value of the saturation magnetization of the iron nitride particles means that the iron nitride particles have Fe 16 N 2 . According to observation with an electron microscope, the obtained iron nitride particles had a spherical shape with a particle diameter of about 8 nm.

《比較例》
〈鉄アンモニアカルボニル錯体の生成〉
この実施例では、鉄アンモニアカルボニル錯体の遠心洗浄を行わなかったことを除いて、実施例１と同様にして、鉄アンモニアカルボニル錯体を粉末状の生成物として得た。《Comparative example》
<Formation of iron ammonia carbonyl complex>
In this example, an iron ammonia carbonyl complex was obtained as a powdery product in the same manner as in Example 1 except that centrifugal washing of the iron ammonia carbonyl complex was not performed.

粉末状の生成物についての１３Ｃ−ＮＭＲによる鉄アンモニアカルボニル錯体と鉄カルボニル錯体とのピークの積分比（鉄アンモニアカルボニル錯体／鉄カルボニル錯体）は、約０．４であった。The integral ratio (iron ammonia carbonyl complex / iron carbonyl complex) of the peak between the iron ammonia carbonyl complex and the iron carbonyl complex by 13 C-NMR for the powdery product was about 0.4.

〈窒化鉄粒子の生成〉
上記のようにして得た粉末状の鉄アンモニアカルボニル錯体から、実施例１と同様にして、窒化鉄粒子を生成した。<Production of iron nitride particles>
In the same manner as in Example 1, iron nitride particles were produced from the powdered iron ammonia carbonyl complex obtained as described above.

ＳＱＵＩＤによる測定によれば、得られた窒化鉄粒子の飽和磁化（３００Ｋ）は、２７ｅｍｕ／ｇであった。電子顕微鏡による観察によれば、繊維状の生成物と粒径約７ｎｍの球形の形状の窒化鉄粒子が観察された。繊維状の生成物は、鉄カルボニル錯体種由来の生成物であると考えられる。   According to the measurement by SQUID, the saturation magnetization (300 K) of the obtained iron nitride particles was 27 emu / g. According to observation with an electron microscope, fibrous products and spherical iron nitride particles having a particle diameter of about 7 nm were observed. The fibrous product is believed to be a product derived from the iron carbonyl complex species.

Claims (18)

平均粒子径が１００ｎｍ以下である、Ｆｅ１６Ｎ２を有する窒化鉄微粒子。Iron nitride fine particles having Fe 16 N 2 having an average particle diameter of 100 nm or less. 飽和磁化が１４０ｅｍｕ／ｇ以上である、請求項１に記載の窒化鉄微粒子。   The iron nitride fine particles according to claim 1, wherein the saturation magnetization is 140 emu / g or more. 平均粒子径が１０ｎｍ以下である、請求項１又は２に記載の窒化鉄微粒子。   The iron nitride fine particles according to claim 1 or 2, wherein the average particle diameter is 10 nm or less. （ａ）有機溶媒中に鉄錯体が分散している分散液を提供すること、及び
（ｂ）前記鉄錯体から、Ｆｅ１６Ｎ２を有する窒化鉄粒子を生成すること、
を含む、Ｆｅ１６Ｎ２を有する窒化鉄粒子の製造方法。(A) providing a dispersion in which an iron complex is dispersed in an organic solvent; and (b) generating iron nitride particles having Fe 16 N 2 from the iron complex.
Including, method for producing the iron nitride particles having an Fe 16 N 2. 前記鉄錯体が、アンモニア配位子及びカルボニル配位子を有する鉄アンモニアカルボニル錯体であり、且つ工程（ａ）で提供される前記分散液において、１３Ｃ−ＮＭＲによる鉄アンモニアカルボニル錯体と鉄カルボニル錯体とのピークの積分比（鉄アンモニアカルボニル錯体／鉄カルボニル錯体）が、１以上である、請求項４に記載の方法。The iron complex is an iron ammonia carbonyl complex having an ammonia ligand and a carbonyl ligand, and in the dispersion provided in step (a), an iron ammonia carbonyl complex and an iron carbonyl complex by 13 C-NMR are used. 5. The method according to claim 4, wherein an integration ratio of peaks with respect to (iron ammonia carbonyl complex / iron carbonyl complex) is 1 or more. 工程（ｂ）において、外部から窒素含有化合物を供給しないで、Ｆｅ１６Ｎ２を有する窒化鉄粒子を生成する、請求項５に記載の方法。The method according to claim 5, wherein in step (b), iron nitride particles having Fe 16 N 2 are generated without supplying a nitrogen-containing compound from the outside. １３Ｃ−ＮＭＲにおける前記鉄アンモニアカルボニル錯体のピークが２３１ｐｐｍ付近である、請求項５又は６に記載の方法。The method according to claim 5 or 6, wherein a peak of the iron ammonia carbonyl complex in 13 C-NMR is around 231 ppm. 前記鉄アンモニアカルボニル錯体が、式Ｆｅ３（ＣＯ）６（ＮＨ３）６を有する、請求項５〜７のいずれかに記載の方法。Wherein the iron ammonium carbonyl complex has the formula Fe 3 (CO) 6 (NH 3) 6, The method of any of claims 5-7. 鉄カルボニル錯体を含有する有機溶媒、又は単独の鉄カルボニル錯体に、アンモニア又はアンモニア発生化合物を導入し、それによって前記鉄カルボニル錯体のカルボニル配位子の一部をアンモニア配位子で交換して、前記鉄アンモニアカルボニル錯体を生成する、請求項５〜８のいずれかに記載の方法。   Introducing ammonia or an ammonia generating compound into an organic solvent containing an iron carbonyl complex, or a single iron carbonyl complex, thereby exchanging part of the carbonyl ligand of the iron carbonyl complex with an ammonia ligand, The method according to claim 5, wherein the iron ammonia carbonyl complex is produced. 生成した鉄アンモニアカルボニル錯体が沈殿する条件で、前記鉄アンモニアカルボニル錯体の生成を行う、請求項９に記載の方法。   The method of Claim 9 which produces | generates the said iron ammonia carbonyl complex on the conditions which the produced | generated iron ammonia carbonyl complex precipitates. 生成した前記鉄アンモニアカルボニル錯体を他の部分から分離して、有機溶媒中に再分散させることによって、工程（ａ）で用いられる前記分散液を得る、請求項９又は１０に記載の方法。   The method according to claim 9 or 10, wherein the produced iron ammonia carbonyl complex is separated from other parts and redispersed in an organic solvent to obtain the dispersion used in step (a). 前記鉄アンモニアカルボニル錯体の生成において、鉄カルボニル錯体が有機溶媒中に分散している前記分散液、又は単独の前記鉄カルボニル錯体を、８０℃〜２００℃の温度に加熱する、請求項９〜１１のいずれかに記載の方法。   In the production | generation of the said iron ammonia carbonyl complex, the said dispersion liquid in which the iron carbonyl complex is disperse | distributing in the organic solvent, or the said iron carbonyl complex of the single is heated to the temperature of 80 to 200 degreeC. The method in any one of. 工程（ａ）で提供される前記分散液が、第１〜第３級アミンからなる群より選択される界面活性剤を更に含有している、請求項１〜１２のいずれかに記載の方法。   The method according to any one of claims 1 to 12, wherein the dispersion provided in step (a) further contains a surfactant selected from the group consisting of primary to tertiary amines. 工程（ｂ）において、前記分散液を８０℃〜２００℃の温度に加熱する、請求項１〜１３のいずれかに記載の方法。   The method according to any one of claims 1 to 13, wherein in the step (b), the dispersion is heated to a temperature of 80C to 200C. 式Ｆｅ３（ＣＯ）６（ＮＨ３）６を有する、鉄アンモニアカルボニル錯体。An iron ammonia carbonyl complex having the formula Fe 3 (CO) 6 (NH 3 ) 6 . Ｆｅ１６Ｎ２を有する窒化鉄微粒子の製造に用いられる、請求項１５に記載の鉄アンモニアカルボニル錯体。The iron ammonia carbonyl complex according to claim 15, which is used for producing iron nitride fine particles having Fe 16 N 2 . １３Ｃ−ＮＭＲによる鉄アンモニアカルボニル錯体と鉄カルボニル錯体とのピークの積分比（鉄アンモニアカルボニル錯体／鉄カルボニル錯体）が、１以上である、鉄アンモニアカルボニル錯体が有機溶媒中に分散している分散液。Dispersion in which an iron ammonia carbonyl complex is dispersed in an organic solvent, the integral ratio of the iron ammonia carbonyl complex and the iron carbonyl complex measured by 13 C-NMR (iron ammonia carbonyl complex / iron carbonyl complex) being 1 or more liquid. Ｆｅ１６Ｎ２相を有する窒化鉄微粒子の製造に用いられる、請求項１７に記載の分散液。The dispersion according to claim 17, which is used for producing fine iron nitride particles having a Fe 16 N 2 phase.
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