JPH07291984A - Production of iron (iii) complex salt of alkylenediamine-n, n'-disuccinic acid - Google Patents
Production of iron (iii) complex salt of alkylenediamine-n, n'-disuccinic acidInfo
- Publication number
- JPH07291984A JPH07291984A JP10739694A JP10739694A JPH07291984A JP H07291984 A JPH07291984 A JP H07291984A JP 10739694 A JP10739694 A JP 10739694A JP 10739694 A JP10739694 A JP 10739694A JP H07291984 A JPH07291984 A JP H07291984A
- Authority
- JP
- Japan
- Prior art keywords
- alkylenediamine
- disuccinic acid
- complex salt
- iron
- acid
- 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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、写真処理剤として使用
することができる高純度のアルキレンジアミン−Ｎ，
Ｎ’−ジコハク酸第二鉄錯塩の製造方法に関するもので
ある。FIELD OF THE INVENTION The present invention relates to a highly pure alkylenediamine-N, which can be used as a photographic processing agent.
The present invention relates to a method for producing an N'-ferric disuccinate complex salt.
【０００２】[0002]
【従来技術およびその問題点】従来から、エチレンジア
ミン四酢酸（ＥＤＴＡ）第二鉄錯塩、ジエチレントリア
ミン五酢酸（ＤＴＰＡ）第二鉄錯塩、プロパンジアミン
四酢酸（ＰＤＴＡ）第二鉄錯塩などの鉄キレ−ト化合物
は、カラー写真焼き付けの際の酸化剤として用いられる
ことが知られており、最近では、β−アラニン−Ｎ，
Ｎ’−二酢酸およびその類似化合物も用いられることが
報告されている（特開平０３−１８６８４１号公報）。
しかし、従来使用されている鉄キレート化合物は、優れ
た性能を有しているものの微生物による分解が起こりに
くい化合物であるため、環境保護の立場からはその使用
には問題があった。また、β−アラニン−Ｎ，Ｎ’−二
酢酸およびその類似化合物は生分解性があるもののキレ
−ト力が弱く、従来生分解されると言われているニトリ
ロ三酢酸（ＮＴＡ）と同じ程度のキレ−ト化合物であ
る。また、本発明者らは、ニトリロ三酢酸よりもキレー
ト力が強く、且つ微生物による分解能も高い新規な鉄キ
レート化合物としてアルキレンジアミン−Ｎ，Ｎ’−ジ
コハク酸第二鉄錯塩およびその製造法を提案した（特願
平５−５４６００号）。この製法は、鉄原料として硫酸
鉄などの鉄塩を用いるので、目的物に硫酸アンモニウム
などの無機物が混入してくることもあると言う問題点が
ある。2. Description of the Related Art Iron chelate such as ethylenediaminetetraacetic acid (EDTA) ferric complex salt, diethylenetriaminepentaacetic acid (DTPA) ferric complex salt, propanediaminetetraacetic acid (PDTA) ferric complex salt, etc. The compound is known to be used as an oxidizing agent in color photographic printing, and recently, β-alanine-N,
It has been reported that N'-diacetic acid and its analogues are also used (Japanese Patent Laid-Open No. 03-186841).
However, the conventionally used iron chelate compound is a compound that has excellent performance, but is unlikely to be decomposed by microorganisms, and thus its use has been problematic from the standpoint of environmental protection. Further, β-alanine-N, N′-diacetic acid and its similar compounds have biodegradability but weak chelating ability, and are similar to nitrilotriacetic acid (NTA), which is said to be biodegradable in the past. Is a chelate compound. Further, the present inventors have proposed alkylenediamine-N, N′-ferric disuccinate ferric acid complex salt and a method for producing the same as a novel iron chelate compound having a stronger chelating power than nitrilotriacetic acid and having a high ability to be decomposed by microorganisms. (Japanese Patent Application No. 5-54600). Since this manufacturing method uses an iron salt such as iron sulfate as an iron raw material, there is a problem that an inorganic substance such as ammonium sulfate may be mixed into the target product.
【０００３】[0003]
【発明が解決しようとする課題】本発明の目的は、環境
保護を考慮した生分解性に優れているとともにカラー写
真焼き付けの際の酸化剤等として使用することができる
高純度のアルキレンジアミン−Ｎ，Ｎ’−ジコハク酸第
二鉄錯塩の製造法を提供することにある。SUMMARY OF THE INVENTION The object of the present invention is to provide a highly pure alkylenediamine-N which is excellent in biodegradability in consideration of environmental protection and can be used as an oxidizing agent or the like in color photographic printing. An object of the present invention is to provide a process for producing a ferric complex of N, N'-disuccinate.
【０００４】[0004]
【課題を解決するための手段】すなわち、本発明は、炭
素数２〜３のアルキレンジアミン−Ｎ，Ｎ’−ジコハク
酸を〔Ａ〕アンモニアまたはアルカリ金属水酸化物およ
び〔Ｂ〕鉄酸化物と水性媒体中で反応させたのち、その
反応生成物を酸化することを特徴とする一般式に示すア
ルキレンジアミン−Ｎ，Ｎ’−ジコハク酸第二鉄錯塩の
製造方法に関する。 一般式 （Ｍ+ はＫ+ ，Ｎａ+ またはＮＨ4 + を表し、ｎは２〜
３を表す。）That is, according to the present invention, an alkylenediamine-N, N'-disuccinic acid having 2 to 3 carbon atoms is replaced with [A] ammonia or an alkali metal hydroxide and [B] iron oxide. The present invention relates to a method for producing an alkylenediamine-N, N'-ferric disuccinic acid complex salt represented by the general formula, which comprises reacting in an aqueous medium and then oxidizing the reaction product. General formula (M + represents K + , Na + or NH 4 + , and n is 2 to
Represents 3. )
【０００５】以下、詳細に本発明を説明する。本発明の
方法は、まず、炭素数２〜３のアルキレンジアミン−
Ｎ，Ｎ’−ジコハク酸に、アンモニアまたはアルカリ金
属水酸化物と鉄の酸化物とを反応させて対応するアルキ
レンジアミン−Ｎ，Ｎ’−ジコハク酸の第一鉄アンモニ
ウム塩および第二鉄アンモニウム塩の混合物またはアル
キレンジアミン−Ｎ，Ｎ’−ジコハク酸の第一鉄アルカ
リ金属塩および第二鉄アルカリ金属塩の混合物を製造す
る。この反応は、水性媒体中で、温度６５〜１０５℃、
好ましくは７５〜９５℃の範囲で行われる。アンモニア
またはアルカリ金属水酸化物の使用量は、アルキレンジ
アミン−Ｎ，Ｎ’−ジコハク酸に対して０．５〜２．０
当量、好ましくは０．８〜１．３当量の範囲で適宜選択
すればよい。また、鉄酸化物の使用量は、アルキレンジ
アミン−Ｎ，Ｎ’−ジコハク酸に対して０．９〜１．５
当量、好ましくは１．０〜１．３当量の範囲で適宜選択
すればよい。The present invention will be described in detail below. In the method of the present invention, first, an alkylenediamine having 2 to 3 carbon atoms
Corresponding alkylenediamine-N, N'-disuccinic acid ferrous ammonium salt and ferric ammonium salt obtained by reacting N, N'-disuccinic acid with ammonia or an alkali metal hydroxide and iron oxide. Or a mixture of ferrous and ferric alkali metal salts of alkylenediamine-N, N'-disuccinic acid. This reaction is carried out in an aqueous medium at a temperature of 65 to 105 ° C.
It is preferably carried out in the range of 75 to 95 ° C. The amount of ammonia or alkali metal hydroxide used is 0.5 to 2.0 with respect to alkylenediamine-N, N'-disuccinic acid.
The equivalent may be appropriately selected, preferably within the range of 0.8 to 1.3 equivalents. The amount of iron oxide used is 0.9 to 1.5 with respect to alkylenediamine-N, N'-disuccinic acid.
The equivalent may be appropriately selected, preferably in the range of 1.0 to 1.3 equivalents.
【０００６】本反応に用いるアルキレンジアミン−Ｎ，
Ｎ’−ジコハク酸は、公知の方法で合成する事が出来
る。例えば、エチレンジアミンまたはプロピレンジアミ
ンにマレイン酸、あるいは無水マレイン酸とアルカリ金
属水酸化物を作用させ加熱反応する事により合成する事
が出来る（Ｚｈｕｒｎａｌ Ｏｂｓｈｃｈｅｉ Ｋｈｉ
ｍｉｉ ４９（３）６５９−６６３）。鉄の酸化物とし
ては、酸化鉄、水和酸化鉄等が用いられ、具体的には三
二酸化鉄（Ｆｅ2 Ｏ3 ）、四三酸化鉄（Ｆｅ3 Ｏ4 ）、
水和酸化鉄（ＦｅＯ (ＯＨ) ）等が挙げられる。これら
の鉄酸化物は単独で用いてもよく、二種以上を任意の割
合で混合して用いても差支えない。本反応は鉄酸化物が
水性媒体に分散された不均一系であることから、鉄酸化
物は粒径が０．５μ以下のものが好適である。また、反
応性の点から四三酸化鉄が最も好適である。アルカリ金
属水酸化物としては、ナトリウム、カリウム等のアルカ
リ金属水酸化物を用いるのがよい。Alkylenediamine-N used in this reaction,
N'-disuccinic acid can be synthesized by a known method. For example, it can be synthesized by reacting ethylenediamine or propylenediamine with maleic acid or maleic anhydride and an alkali metal hydroxide to cause a heating reaction (Zhurnal Obshchei Khi.
mii 49 (3) 659-663). As the iron oxide, iron oxide, hydrated iron oxide, etc. are used, and specifically, iron sesquioxide (Fe 2 O 3 ), ferrosoferric oxide (Fe 3 O 4 ),
Hydrated iron oxide (FeO (OH)) and the like can be mentioned. These iron oxides may be used alone or as a mixture of two or more kinds at any ratio. Since this reaction is a heterogeneous system in which iron oxide is dispersed in an aqueous medium, iron oxide having a particle size of 0.5 μm or less is preferable. Further, from the viewpoint of reactivity, ferric tetroxide is most suitable. It is preferable to use an alkali metal hydroxide such as sodium or potassium as the alkali metal hydroxide.
【０００７】また、上記反応は、反応液に還元剤を添加
することによって反応を加速することができる。還元剤
としては、亜硫酸のアンモニウム、ナトリウム、カリウ
ム等の塩、ヒドラジン、アスコルビン酸、イソアスコル
ビン酸、蓚酸、鉄粉、メタ燐酸等の無機および有機の還
元作用を有する化合物が用いられる。好ましくは鉄粉、
アスコルビン酸、イソアスコルビン酸等である。還元剤
の使用量は、反応液に対して１０ｗｔ％以下、好ましく
は５ｗｔ％以下、より好ましくは０．０１〜１ｗｔ％の
範囲で適宜選択すればよい。Further, the above reaction can be accelerated by adding a reducing agent to the reaction solution. As the reducing agent, salts of ammonium sulfite, sodium, potassium and the like, and compounds having an inorganic and organic reducing action such as hydrazine, ascorbic acid, isoascorbic acid, oxalic acid, iron powder and metaphosphoric acid are used. Preferably iron powder,
Examples thereof include ascorbic acid and isoascorbic acid. The amount of the reducing agent used may be appropriately selected within the range of 10 wt% or less, preferably 5 wt% or less, and more preferably 0.01 to 1 wt% with respect to the reaction liquid.
【０００８】次いで、得られたアルキレンジアミン−
Ｎ，Ｎ’−ジコハク酸の第一鉄アンモニウム塩および第
二鉄アンモニウム塩の混合物またはアルキレンジアミン
−Ｎ，Ｎ’−ジコハク酸の第一鉄アルカリ金属塩および
第二鉄アルカリ金属塩の混合物は酸化して対応するアル
キレンジアミン−Ｎ，Ｎ’−ジコハク酸第二鉄塩にす
る。この酸化反応は前記第一鉄錯塩を含む鉄錯塩生成水
溶液をそのまま用い、これに分子状酸素、過酸化物等の
酸化剤を作用させることにより行うことができる。分子
状酸素としては、空気、酸素富化空気、酸素等が挙げら
れるが、経済性の見地から通常空気が好んで用いられ
る。空気の使用量は、前記第一鉄塩に対して理論量の１
０〜３０倍程度が適量である。過酸化物としては、過硫
酸のアンモニウム、ナトリウム、カリウム等の過硫酸
塩、過酸化水素、有機過酸化物等が用いられるが、不用
な塩がのこらないことや経済性の見地から過酸化水素を
用いるのがよい。過酸化物の使用量は前記第一鉄錯塩に
対して０．９〜２．０当量、好ましくは１．０〜１．５
当量の範囲で適宜選択すればよい。また、この酸化反応
は反応液のＰＨが酸性側からアルカリ側まで任意のＰＨ
領域で行うことができるが、ＰＨ５〜１０、好ましくは
ＰＨ６〜８の範囲で行うのがよい。ＰＨ調整剤としては
反応に用いたアルキレンジアミン−Ｎ，Ｎ’−ジコハク
酸を用いるのがよい。温度は１０〜９０℃、好ましくは
２０〜５０℃の範囲で行うのがよい。Then, the obtained alkylenediamine-
A mixture of ferrous ammonium and ferric ammonium salts of N, N'-disuccinic acid or a mixture of ferrous alkali metal and ferric alkali metal salts of alkylenediamine-N, N'-disuccinic acid is oxidized. To give the corresponding alkylenediamine-N, N'-disuccinic acid ferric salt. This oxidation reaction can be carried out by using the iron complex salt-forming aqueous solution containing the ferrous complex salt as it is, and reacting it with an oxidizing agent such as molecular oxygen or peroxide. Examples of the molecular oxygen include air, oxygen-enriched air, oxygen and the like, but from the economical point of view, usually air is preferably used. The amount of air used is the theoretical amount of 1 with respect to the ferrous salt.
An appropriate amount is about 0 to 30 times. As the peroxide, persulfates such as ammonium, sodium and potassium persulfates, hydrogen peroxide and organic peroxides are used, but peroxides are used from the standpoint of avoiding unnecessary salts and economical reasons. It is better to use hydrogen. The amount of peroxide used is 0.9 to 2.0 equivalents, preferably 1.0 to 1.5, relative to the ferrous complex salt.
It may be appropriately selected within the equivalent range. In addition, this oxidation reaction is carried out by adjusting the pH of the reaction solution to any pH from the acidic side to the alkaline side.
Although it can be carried out in a region, it is preferably carried out in the range of PH5 to 10, preferably PH6 to 8. As the pH adjuster, alkylenediamine-N, N'-disuccinic acid used in the reaction is preferably used. The temperature is 10 to 90 ° C, preferably 20 to 50 ° C.
【０００９】反応終了後、反応液より不溶物を除去した
のち反応液のＰＨ値を４〜６．５、好ましくは５．５〜
６．１の範囲に調整する。これによって反応液からの目
的とする生成物結晶の晶析を容易にすることができる。
この反応液は濃縮、冷却して目的物であるアルキレンジ
アミン−Ｎ，Ｎ’−ジコハク酸第二鉄錯塩を結晶として
析出させ、これをは遠心分離機等によって母液と分離し
たのち、水洗、乾燥することにより、上記一般式に示す
化合物を得ることができる。結晶を析出させる際、メタ
ノールやエタール等の有機溶剤を添加して溶解度を下げ
ることにより収率はより向上する。かくして得られたア
ルキレンジアミン−Ｎ，Ｎ’−ジコハク酸第二鉄錯塩
は、３８０〜４１５の分子量を有し、微生物で分解する
ことができる。また、該第二鉄錯塩は前記特願平５−５
４６００号の製法に比べて無機物の混入はなく、純度が
高いものである。After completion of the reaction, insoluble matter is removed from the reaction solution, and then the pH value of the reaction solution is 4 to 6.5, preferably 5.5.
Adjust to the range of 6.1. This can facilitate crystallization of the desired product crystals from the reaction solution.
The reaction solution is concentrated and cooled to precipitate the objective alkylenediamine-N, N'-ferric disuccinate ferric complex salt as crystals, which is separated from the mother liquor by a centrifuge or the like, washed with water and dried. By doing so, the compound represented by the above general formula can be obtained. When precipitating the crystals, the yield is further improved by adding an organic solvent such as methanol or etal to lower the solubility. The alkylenediamine-N, N'-ferric disuccinic acid complex salt thus obtained has a molecular weight of 380 to 415 and can be decomposed by microorganisms. Further, the ferric complex salt is the above-mentioned Japanese Patent Application No. 5-5.
Compared to the manufacturing method of No. 4600, there is no mixing of inorganic substances and the purity is high.
【００１０】[0010]
【実施例】以下に実施例を挙げて説明する 実施例１ 撹拌機、温度計および原料投入口を有する１リットル円
筒形フラスコにエチレンジアミン−Ｎ，Ｎ’−ジコハク
酸１４６．１ｇ（０．５モル）、水５００．０ｇ、２４
％アンモニア水２４ｇ（０．４モル）、四三酸化鉄４
７．５ｇ（０．２モル）および鉄粉０．９ｇを仕込み、
温度９０〜９５℃で反応を行った。次いで、反応液を６
０℃まで冷却し不溶の酸化鉄を除去したのち、ボールフ
ィルターを用い７リットル／分の速度で３時間、該反応
液に空気を吹き込み酸化反応を行った。反応終了後、反
応液のＰＨ値をアンモニアで６．０に調整したのち減圧
濃縮した。析出した結晶を遠心分離機で分離し、少量の
水で洗浄して一次晶８０．３ｇを得た。更に、ろ液およ
び洗液を再濃縮して二次晶８３ｇを得て、一二次晶併せ
て１６３．３ｇのエチレンジアミン−Ｎ，Ｎ’−ジコハ
ク酸第二鉄錯体アンモニウム塩を得た。この収率は８５
％（原料のエチレンジアミンジコハク酸に対して）であ
った。EXAMPLES Examples 1 will be described below. Example 1 146.1 g (0.5 mol) of ethylenediamine-N, N'-disuccinic acid was added to a 1-liter cylindrical flask having a stirrer, a thermometer and a raw material inlet. ), Water 500.0 g, 24
% Ammonia water 24 g (0.4 mol), ferric tetroxide 4
Charge 7.5 g (0.2 mol) and 0.9 g of iron powder,
The reaction was carried out at a temperature of 90 to 95 ° C. Then, the reaction solution is added to 6
After cooling to 0 ° C. to remove insoluble iron oxide, air was blown into the reaction solution at a rate of 7 l / min for 3 hours using a ball filter to carry out an oxidation reaction. After the reaction was completed, the pH value of the reaction solution was adjusted to 6.0 with ammonia and then concentrated under reduced pressure. The precipitated crystals were separated by a centrifuge and washed with a small amount of water to obtain 80.3 g of primary crystals. Further, the filtrate and the washing solution were re-concentrated to obtain 83 g of secondary crystals, and the primary and secondary crystals were combined to obtain 163.3 g of ethylenediamine-N, N′-ferric disuccinic acid ferric complex ammonium salt. This yield is 85
% (Relative to the raw material ethylenediaminedisuccinic acid).
【００１１】実施例２〜１８ 表１に示す各反応原料を用い、実施例１と同様の方法で
反応を行った。その結果は表１に示した。なお、アンモ
ニアまたはアルカリ金属水酸化物の使用量は、アルキレ
ンジアミン−Ｎ，Ｎ’−ジコハク酸１モルに対し０．８
モル、鉄酸化物の使用量は、アルキレンジアミン−Ｎ，
Ｎ’−ジコハク酸１モルに対し三二酸化鉄の場合は０．
６モル、四三酸化鉄の場合は０．４モル、水和酸化鉄の
場合は１．２モル、還元剤の使用量は、鉄粉は鉄酸化物
対し２ｗｔ％、アスコルビン酸およびイソアスコルビン
酸は反応液量に対し５００ｐｐｍである。Examples 2 to 18 Reactions were carried out in the same manner as in Example 1 using the respective reaction raw materials shown in Table 1. The results are shown in Table 1. The amount of ammonia or alkali metal hydroxide used is 0.8 with respect to 1 mol of alkylenediamine-N, N'-disuccinic acid.
Mol, the amount of iron oxide used is alkylenediamine-N,
In the case of ferric sesquioxide with respect to 1 mol of N'-disuccinic acid, it is 0.
6 mol, 0.4 mol in the case of ferrosoferric oxide, 1.2 mol in the case of hydrated iron oxide, the amount of reducing agent used is as follows: iron powder is 2 wt% of iron oxide, ascorbic acid and isoascorbic acid. Is 500 ppm with respect to the amount of the reaction solution.
【００１２】[0012]
【表１】 [Table 1]
【００１３】[0013]
【発明の効果】本発明の方法によれば、キレート力が強
く（キレート定数；１９〜２１）、且つ微生物による分
解能も高い炭素数２〜３のアルキレンジアミン−Ｎ，
Ｎ’−ジコハク酸第二鉄錯塩を、高純度、高収率で製造
することができる。また環境保護の立場からはキレート
化合物の蓄積の恐れが無く好ましい。According to the method of the present invention, an alkylenediamine-N having 2 to 3 carbon atoms, which has a strong chelating power (chelate constant; 19 to 21) and is highly decomposed by microorganisms,
The N′-ferric disuccinic acid complex salt can be produced with high purity and high yield. Further, from the standpoint of environmental protection, it is preferable because there is no fear of accumulation of chelate compounds.
Claims (2)
Ｎ’−ジコハク酸を〔Ａ〕アンモニアまたはアルカリ金
属水酸化物および〔Ｂ〕鉄酸化物と水性媒体中で反応さ
せたのち、その反応生成物を酸化することを特徴とする
一般式に示すアルキレンジアミン−Ｎ，Ｎ’−ジコハク
酸第二鉄錯塩の製造方法。 一般式 （Ｍ+ はＫ+ ，Ｎａ+ またはＮＨ4 + を表し、ｎは２〜
３を表す。）1. An alkylenediamine-N having 2 to 3 carbon atoms,
N'-disuccinic acid is reacted with [A] ammonia or an alkali metal hydroxide and [B] iron oxide in an aqueous medium, and then the reaction product is oxidized. A method for producing a diamine-N, N'-ferric disuccinic acid complex salt. General formula (M + represents K + , Na + or NH 4 + , and n is 2 to
Represents 3. )
Ｎ’−ジコハク酸と〔Ａ〕アンモニアまたはアルカリ金
属水酸化物および〔Ｂ〕鉄酸化物との反応を、無機また
は有機の還元剤の存在下で行う請求項１記載のアルキレ
ンジアミン−Ｎ，Ｎ’−ジコハク酸第二鉄錯塩の製造方
法。2. An alkylenediamine-N having 2 to 3 carbon atoms,
The alkylenediamine-N, N according to claim 1, wherein the reaction of N'-disuccinic acid with [A] ammonia or an alkali metal hydroxide and [B] iron oxide is carried out in the presence of an inorganic or organic reducing agent. '-A method for producing a ferric disuccinate complex salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10739694A JP3660370B2 (en) | 1994-04-25 | 1994-04-25 | Process for producing alkylenediamine-N, N'-ferric disuccinate complex salt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10739694A JP3660370B2 (en) | 1994-04-25 | 1994-04-25 | Process for producing alkylenediamine-N, N'-ferric disuccinate complex salt |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07291984A true JPH07291984A (en) | 1995-11-07 |
| JP3660370B2 JP3660370B2 (en) | 2005-06-15 |
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ID=14458088
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10739694A Expired - Lifetime JP3660370B2 (en) | 1994-04-25 | 1994-04-25 | Process for producing alkylenediamine-N, N'-ferric disuccinate complex salt |
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| Country | Link |
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| JP (1) | JP3660370B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999023062A1 (en) * | 1997-10-31 | 1999-05-14 | Mitsubishi Rayon Co., Ltd. | Iron alkali salt of s,s-ethylenediamine-n,n'-disuccinic acid and process for producing the same |
| WO2000066540A1 (en) * | 1999-04-30 | 2000-11-09 | Mitsubishi Rayon Co., Ltd. | Powdery s,s-ethylenediamine-n,n'-disuccinic acid iron complex and process for producing the same |
-
1994
- 1994-04-25 JP JP10739694A patent/JP3660370B2/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999023062A1 (en) * | 1997-10-31 | 1999-05-14 | Mitsubishi Rayon Co., Ltd. | Iron alkali salt of s,s-ethylenediamine-n,n'-disuccinic acid and process for producing the same |
| US6300510B1 (en) | 1997-10-31 | 2001-10-09 | Mitsubishi Rayon Co., Ltd. | Iron alkali salt of S,S-ethylenediamine-N,N′-disuccinic acid and process for producing the same |
| AU743601B2 (en) * | 1997-10-31 | 2002-01-31 | Mitsubishi Chemical Corporation | Iron alkali salt of S,S-ethylenediamine-N,N'-disuccinic acid and process for producing the same |
| US6515159B2 (en) | 1997-10-31 | 2003-02-04 | Mitsubishi Rayon Co., Ltd. | S,S-ethylenediamine-N,N′-disuccinic acid iron alkali salt and a process for production thereof |
| EP1348689A1 (en) * | 1997-10-31 | 2003-10-01 | Mitsubishi Rayon Co., Ltd. | Process for production of s,s-ethylenediamine-n,n'-disuccinic acid iron alkali salt |
| WO2000066540A1 (en) * | 1999-04-30 | 2000-11-09 | Mitsubishi Rayon Co., Ltd. | Powdery s,s-ethylenediamine-n,n'-disuccinic acid iron complex and process for producing the same |
| US6906215B1 (en) | 1999-04-30 | 2005-06-14 | Mitsubishi Rayon Co., Ltd. | Powdery s,s-ethylenediamine-n,n′-disuccinic acid iron complex and process for producing the same |
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| Publication number | Publication date |
|---|---|
| JP3660370B2 (en) | 2005-06-15 |
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