JPH0733720A - Iron complex salt of 2-hydroxyethyliminodiacetic acid and its production - Google Patents
Iron complex salt of 2-hydroxyethyliminodiacetic acid and its productionInfo
- Publication number
- JPH0733720A JPH0733720A JP22492793A JP22492793A JPH0733720A JP H0733720 A JPH0733720 A JP H0733720A JP 22492793 A JP22492793 A JP 22492793A JP 22492793 A JP22492793 A JP 22492793A JP H0733720 A JPH0733720 A JP H0733720A
- Authority
- JP
- Japan
- Prior art keywords
- iron
- hydroxyethyliminodiacetic acid
- complex salt
- acid
- atom
- 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.)
- Pending
Links
- JYXGIOKAKDAARW-UHFFFAOYSA-N N-(2-hydroxyethyl)iminodiacetic acid Chemical compound OCCN(CC(O)=O)CC(O)=O JYXGIOKAKDAARW-UHFFFAOYSA-N 0.000 title claims abstract description 28
- -1 Iron complex salt Chemical class 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 59
- 150000003839 salts Chemical class 0.000 claims abstract description 41
- 229910052742 iron Inorganic materials 0.000 claims abstract description 29
- YYVDMLFBWPXOGX-UHFFFAOYSA-N 2-[carboxymethyl(2-hydroxyethyl)amino]acetic acid;iron Chemical compound [Fe].OCCN(CC(O)=O)CC(O)=O YYVDMLFBWPXOGX-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 6
- JGFUYLLPOTVEFR-UHFFFAOYSA-L [O-]C(CN(CCO)CC([O-])=O)=O.[Fe+3] Chemical compound [O-]C(CN(CCO)CC([O-])=O)=O.[Fe+3] JGFUYLLPOTVEFR-UHFFFAOYSA-L 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- JDQQVHUDPRIQMD-UHFFFAOYSA-N 2-(carboxymethylamino)acetic acid;iron Chemical compound [Fe].OC(=O)CNCC(O)=O JDQQVHUDPRIQMD-UHFFFAOYSA-N 0.000 claims 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims 1
- 150000001340 alkali metals Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 241001465754 Metazoa Species 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 230000033116 oxidation-reduction process Effects 0.000 abstract description 2
- 235000013311 vegetables Nutrition 0.000 abstract 1
- 239000002351 wastewater Substances 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 6
- 238000004448 titration Methods 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- PMVSDNDAUGGCCE-TYYBGVCCSA-L Ferrous fumarate Chemical group [Fe+2].[O-]C(=O)\C=C\C([O-])=O PMVSDNDAUGGCCE-TYYBGVCCSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000004455 differential thermal analysis Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910021575 Iron(II) bromide Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 229940046149 ferrous bromide Drugs 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 description 1
Landscapes
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】本発明は、２−ヒドロキシエチルイミノ二
酢酸の金属錯塩乃至その製造方法に係わるものである。
本発明によって提供される金属錯塩は、動植物体が必須
不可欠の要素として必要とする金属を易吸収状態で提供
することができることや、写真産業とりわけ、カラー写
真の現像処理における脱銀操作のために有用な化合物と
なるものである。The present invention relates to a metal complex salt of 2-hydroxyethyliminodiacetic acid and a method for producing the same.
INDUSTRIAL APPLICABILITY The metal complex salt provided by the present invention is capable of providing a metal required by animals and plants as an indispensable element in an easily absorbed state, and for the desilvering operation in the photographic industry, especially in the development processing of color photography. It is a useful compound.
【０００２】[0002]
【従来の技術】２−ヒドロキシエチルイミノ二酢酸は、
生物による分解が可能であるところから、廃液の処理が
容易となるので、これを使用して、金属イオンを不活性
化することや、これと鉄との錯塩を、カラー写真の漂白
工程に従来使用されているエチレンジアミン四酢酸（Ｅ
ＤＴＡ）やジエチレントリアミン五酢酸の代わりに、使
用することが知られている。2. Description of the Prior Art 2-Hydroxyethyliminodiacetic acid is
Since it can be decomposed by organisms, it is easy to treat the waste liquid, so it is used to inactivate metal ions and complex salts with iron are used in the bleaching process of color photography. Used ethylenediaminetetraacetic acid (E
It is known to be used instead of DTA) or diethylenetriaminepentaacetic acid.
【０００３】現在、カラー写真の脱銀処理のために、Ｅ
ＤＴＡ−鉄錯塩が使用されている状況にあるが、ＥＤＴ
Ａが微生物による分解において、その可能性が殆んど，
ないために、廃液中に累積するので、その処理方法が問
われているところである。Currently, E is used for desilvering color photographs.
In the situation where DTA-iron complex salt is used, EDT
When A is decomposed by microorganisms, the possibility is almost
Since it does not exist, it is accumulated in the waste liquid, and therefore its treatment method is being questioned.
【０００４】２−ヒドロキシエチルイミノ二酢酸は、Ｅ
ＤＴＡと同様に、金属イオンを捕獲し、これを不活性化
することが可能であることは、夙に知られているところ
であり、また、２−ヒドロキシエチルイミノ二酢酸鉄錯
塩を含有する漂白定着液を使用したカラー写真感光材料
の処理方法が公知となっている。特開昭６２−１９８５
１号、特開昭６２−１１５１５９号、特開昭６２−１１
５１５８号参照。2-Hydroxyethyliminodiacetic acid is E
It is well known that, like DTA, it is possible to capture metal ions and inactivate them, and also to bleach-fix containing 2-hydroxyethyliminodiacetic acid iron complex salt. A method of processing a color photographic light-sensitive material using a liquid is known. JP 62-1985
1, JP-A-62-115159, JP-A-62-11
See 5158.
【０００５】しかしながら、これら公知文献において開
示されている２−ヒドロキシエチルイミノ二酢酸鉄錯塩
は、それを含有する漂白定着液を用いたテスト結果を開
示するに止まり、当該錯塩それ自体の取得や、物性値に
ついては何一つ開示されていない。However, the 2-hydroxyethyliminodiacetic acid iron complex salt disclosed in these known documents merely discloses the test results using a bleach-fixing solution containing it, and the acquisition of the complex salt itself, None of the physical property values are disclosed.
【０００６】一例を示せば、特開昭６２−１９８５１号
公報には、本発明の漂白定着液には、漂白剤として有機
酸第２鉄錯塩が含有される。有機酸第２鉄錯塩を形成す
る有機酸としては…２−ヒドロキシエチルイミノ二酢酸
（ＭＷ＝１７７．１６）…とあり、また、有機酸第２鉄
錯塩はフリーの酸、ナトリウム塩、カリウム塩…アンモ
ニウム塩…等として使われる等との開示がなされている
にすぎない。（同公報２８〜２９ページ参照）。[0006] As an example, in JP-A-62-119851, the bleach-fixing solution of the present invention contains a ferric organic acid complex salt as an bleaching agent. The organic acid forming the ferric iron complex salt is 2-hydroxyethyliminodiacetic acid (MW = 177.16), and the ferric organic acid complex salt is a free acid, sodium salt, or potassium salt. It is only disclosed that it is used as ... ammonium salt ... etc. (See pages 28 to 29 of the same publication).
【０００７】特開昭６２−１１５１５８号公報にも、上
記と同様の記載がなされているにすぎない（同公報 ５
０〜５１ページ参照）このように、２−ヒドロキシエチ
ルイミノ二酢酸鉄錯塩に係わる開示は、単に化合物名を
例示的に列挙して示しているだけに止まっているだけで
ある。実施例におけるテスト結果の欄にも当該錯塩の名
称が記載されているけれども、それが如何ように造られ
たか、又は、公知文献等で合成方法が明らかにされてい
るとかについては明らかにされていないのである。１９
７３年のケミカルアブストラクト７８巻４８７５３Ｋに
はＦｅＣｌ３を用い、２−ヒドロキシエチルイミノ二酢
酸鉄錯塩を鉄とリガンドの比１：１のものを得たとある
が、この記述には誤りがあることを本発明者らは見つけ
た。従ってまた、当該錯塩の合成方法も確立されていな
いのである。Japanese Unexamined Patent Publication (Kokai) No. 62-115158 only discloses the same as above (Patent Document 5).
As described above, the disclosure regarding the 2-hydroxyethyliminodiacetic acid iron complex salt is limited to merely listing and showing the compound names. Although the name of the complex salt is also described in the column of test results in the examples, it has not been clarified how the complex salt was produced, or whether the synthetic method was clarified in publicly known documents or the like. There is no. 19
It is said that the chemical abstract of 1973, Vol. 78, 48753K, used FeCl 3 to obtain a 2-hydroxyethyliminodiacetic acid iron complex salt having a ratio of iron to ligand of 1: 1. The inventors have found. Therefore, the method for synthesizing the complex salt has not been established.
【０００８】かかる状況下において、本発明者らは、２
−ヒドロキシエチルイミノ二酢酸鉄錯塩の確たる合成方
法の検討を行い、試行錯誤のすえ、遂に、その合成方法
の確立と、それにより提供される２−ヒドロキシエチル
イミノ二酢酸鉄錯塩の取得に成功したのである。Under these circumstances, the present inventors
-Study of a certain synthetic method of hydroxyethyliminodiacetic acid iron complex salt, trial and error, finally establishment of the synthetic method, and succeeded in obtaining 2-hydroxyethyliminodiacetic acid iron complex salt provided thereby. Of.
【０００９】[0009]
【発明が解決しようとする課題】本発明は２−ヒドロキ
シエチルイミノ二酢酸二分子と鉄一原子とから成るヒド
ロキシエチルイミノ二酢酸鉄錯塩及びその合成方法を提
供するものである。The present invention provides a hydroxyethyliminodiacetic acid iron complex salt composed of two molecules of 2-hydroxyethyliminodiacetic acid and one iron atom, and a method for synthesizing the same.
【００１０】[0010]
【課題を解決するための手段】本発明により提供される
２−ヒドロキシエチルイミノ二酢酸鉄錯塩及びその製造
方法は、以下に述べる方法に従い実施される。即ち、２
−ヒドロキシエチルイミノ二酢酸を適宜溶媒に溶解乃至
分散せしめ、これに鉄源を加え液性を整え、反応させ
る。The 2-hydroxyethyliminodiacetic acid iron complex salt provided by the present invention and the method for producing the same are carried out according to the method described below. That is, 2
-Hydroxyethyliminodiacetic acid is appropriately dissolved or dispersed in a solvent, and an iron source is added to this to adjust the liquidity and react.
【００１１】使用される鉄源としては、金属鉄粉、鉄塩
例えば塩化第一鉄、臭化第一鉄、硝酸第一鉄、硫酸第一
鉄、塩化第二鉄、臭化第二鉄、硝酸第二鉄、硫酸第二鉄
等があり、更に、酸化鉄（第一、第二）、水酸化鉄（第
一、第二）、水酸化第一第二鉄、酸化第一第二鉄、四三
酸化鉄が挙げられ、これらは、単独で又は他と併用して
使用される。The iron sources used include metallic iron powder, iron salts such as ferrous chloride, ferrous bromide, ferrous nitrate, ferrous sulfate, ferric chloride, ferric bromide, There are ferric nitrate, ferric sulfate, etc., and further iron oxide (first and second), iron hydroxide (first and second), ferric hydroxide, ferric oxide. , Iron tetroxide, which are used alone or in combination with others.
【００１２】２−ヒドロキシエチルイミノ二酢酸と鉄源
との割合は少なくともヒドロキシエチルイミノ二酢酸２
分子に対し、鉄一原子が対応するように量関係を選択し
て、反応させる。反応は水又は水と任意に混合し合うも
のとの混合溶媒を使用し、両方を室温乃至加熱下混合撹
拌して実施される。特に、反応時における液性は、本発
明において重要な意義を有しており、反応液のｐＨが４
を越えない範囲において反応を実行するとき、２−ヒド
ロキシエチルイミノ二酢酸と鉄源との反応が進行し目的
とする２−ヒドロキシエチルイミノ二酢酸鉄錯塩を得る
ことができる。好ましくはｐＨ２〜３で反応させるのが
よい。The ratio of 2-hydroxyethyliminodiacetic acid to the iron source is at least 2% of hydroxyethyliminodiacetic acid.
The quantity relation is selected so that one iron atom corresponds to the molecule and the reaction is performed. The reaction is carried out by using water or a mixed solvent of water and any mixture thereof, and mixing and stirring both of them at room temperature or under heating. In particular, the liquidity during the reaction has an important meaning in the present invention, and the pH of the reaction liquid is 4
When the reaction is carried out in a range not exceeding the above range, the reaction between 2-hydroxyethyliminodiacetic acid and the iron source proceeds to obtain the desired iron 2-hydroxyethyliminodiacetic acid complex salt. The reaction is preferably carried out at pH 2-3.
【００１３】反応液の液性をコントロールするために
は、酸性化合物を添加すればよいが、塩酸、硫酸、硝酸
等の無機酸や、酢酸、蓚酸等の有機カルボン酸のほか、
２−ヒドロキシエチルイミノ二酢酸それ自体を加えるこ
とも有効である。In order to control the liquidity of the reaction solution, an acidic compound may be added. In addition to inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, organic carboxylic acids such as acetic acid and oxalic acid,
It is also effective to add 2-hydroxyethyliminodiacetic acid itself.
【００１４】反応生成物として、三価鉄錯塩を希望する
場合、鉄源として三価鉄を使用するときはともかく二価
鉄を使用するときは、反応が終わった後、生成した２−
ヒドロキシエチルイミノ二酢酸鉄（二価）錯塩を水に分
散せしめ、液性をｐＨ５〜８（好ましくは６〜７）に調
整し、酸素源（酸素又は空気あるいは酸化物（例えば過
酸化水素、過マンガン酸塩、有機過酸化物）等）を加え
酸化反応を行うことによって目的とする２−ヒドロキシ
エチルイミノ二酢酸鉄（三価）錯塩に変えることができ
る。液性の調整にはアルカリ性物質を使用すればよい
が、アンモニア水を使用するのが好都合である。When a trivalent iron complex salt is desired as a reaction product, and when divalent iron is used regardless of whether trivalent iron is used as an iron source, 2-
Hydroxyethyliminodiacetic acid iron (divalent) complex salt is dispersed in water, the liquidity is adjusted to pH 5 to 8 (preferably 6 to 7), and the oxygen source (oxygen or air or oxide (for example, hydrogen peroxide, peroxide) is adjusted. The target 2-hydroxyethyliminodiacetic acid iron (trivalent) complex salt can be obtained by adding a manganate, an organic peroxide, etc.) and conducting an oxidation reaction. An alkaline substance may be used to adjust the liquidity, but it is convenient to use aqueous ammonia.
【００１５】また、得られた２−ヒドロキシエチルイミ
ノ二酢酸鉄錯塩を更にアルカリ塩に導くことができ、そ
れらの中には、アルカリ金属塩、アンモニウム塩、アミ
ン塩などが含まれる。これらは、２−ヒドロキシエチル
イミノ二酢酸と鉄源との反応を終えた後、アルカリ金属
水酸化物（ＮａＯＨ，ＫＯＨなど），アンモニア、アミ
ン（トリエタノールアミン、トリエチルアミン、ジメチ
ルアニリン、ピリジンなど）を添加することにより、誘
導される。The obtained 2-hydroxyethyliminodiacetic acid iron complex salt can be further converted into an alkali salt, and among these, alkali metal salts, ammonium salts, amine salts and the like are included. These are alkali metal hydroxides (NaOH, KOH, etc.), ammonia, amines (triethanolamine, triethylamine, dimethylaniline, pyridine, etc.) after the reaction between 2-hydroxyethyliminodiacetic acid and the iron source is completed. Induced by adding.
【００１６】かくして得られた２−ヒドロキシエチルイ
ミノ二酢酸鉄錯塩又はそのアルカリ塩は、酸化−還元電
位差を利用し、例えばカラー写真の脱銀処理に使用さ
れ、２−ヒドロキシエチルイミノ二酢酸の生分解性の故
に、廃液の処理が容易となる。The 2-hydroxyethyliminodiacetic acid iron complex salt thus obtained or its alkali salt is used for desilvering processing of color photographs, for example, by utilizing the oxidation-reduction potential difference, to produce 2-hydroxyethyliminodiacetic acid. Due to the degradability, the waste liquid can be easily treated.
【００１７】以下、本発明を更に具体的に説明するた
め、実施例を記述する。Examples will be described below in order to more specifically describe the present invention.
【００１８】実施例１ ２−ヒドロキシエチルイミノ二酢酸鉄錯塩の製造 ２００ｍｌ４経コルベンに、水８０ｍｌ、２−ヒドロキ
シエチルイミノ二酢酸６２．０２ｇを加え、撹拌を行
い、この懸濁液に２８％アンモニア水を加え、ｐＨ＝
３．０に調整する。次いで、８０℃に加熱し、四三酸化
鉄１０．０８ｇを加え、さらに、沸点若しくは近傍温度
にて、３時間加熱撹拌を続けると時間の経過と共に結晶
が析出した。この混合物を、室温まで冷却し、析出結晶
（ＨＩＭＤＡ２Ｆｅ）を濾取する（得量４９．３ｇ）。
このものは淡黄緑色の結晶であり、示差熱解析の結果２
３３．５℃で分解した。 ＩＲ吸収スペクトル（ＫＢｒ法）：１７３２ｃｍ−１、
１５７７ｃｍ−１ 結晶中の鉄（ＩＩ）含量：１３．３３％（滴定法によ
る） 元素分析：実測値（％）Ｃ：３４．６４７ Ｈ：４．８
５３ Ｎ：６．７８６ 計算値（％）Ｃ：３５．３１４ Ｈ：４．９３９ Ｎ：６．８６４ Ｏ：３９．６８３ Ｆｅ：１３．６８３ これより２−ヒドロキシエチルイミノ二酢酸と鉄の割合
が２分子：１原子の割合となっていることが判る。この
結晶を水９０ｇに懸濁し、２８％アンモニア水を加え、
ｐＨ＝６．５〜７．０に調整する。その結果、結晶は溶
解し、暗褐色の溶液となる。この溶液に、空気を吹き込
むと、暗赤色澄明な水溶液となり２−ヒドロキシエチル
イミノ二酢酸鉄（ＩＩＩ）錯塩水溶液を得た。得られた
水溶液についてヨウ素滴定法により含まれている鉄が３
価であることを確かめた。 Example 1 Preparation of 2-hydroxyethyliminodiacetic acid iron complex salt 80 ml of water and 62.02 g of 2-hydroxyethyliminodiacetic acid were added to 200 ml of 4-cobbene and stirred, and 28% ammonia was added to this suspension. Add water, pH =
Adjust to 3.0. Then, the mixture was heated to 80 ° C., 10.08 g of ferric tetroxide was added, and the mixture was further heated and stirred at the boiling point or in the vicinity of the temperature for 3 hours, and crystals were deposited over time. The mixture is cooled to room temperature, and the precipitated crystals (HIMDA2Fe) are collected by filtration (yield 49.3 g).
This is a pale yellow-green crystal, and the result of differential thermal analysis is 2
Decomposed at 33.5 ° C. IR absorption spectrum (KBr method): 1732 cm -1 ,
Iron (II) content in 1577 cm −1 crystal: 13.33% (by titration method) Elemental analysis: measured value (%) C: 34.647 H: 4.8
53 N: 6.786 Calculated value (%) C: 35.314 H: 4.939 N: 6.864 O: 39.683 Fe: 13.683 From this, the ratio of 2-hydroxyethyliminodiacetic acid and iron was calculated. It can be seen that the ratio is 2 molecules: 1 atom. The crystals were suspended in 90 g of water, 28% aqueous ammonia was added,
Adjust to pH = 6.5-7.0. As a result, the crystals dissolve into a dark brown solution. When air was blown into this solution, a dark red clear aqueous solution was obtained, and an aqueous solution of 2-hydroxyethyliminodiacetic iron (III) complex salt was obtained. The obtained aqueous solution contained 3 iron by the iodometric titration method.
I confirmed that it was worth it.
【００１９】実施例２ ２−ヒドロキシエチルイミノ二酢酸鉄錯塩の製造 ２００ｍｌ４経コルベンに、水８０ｍｌ、２−ヒドロキ
シエチルイミノ二酢酸６２．０２ｇを加え、撹拌を行
い、この懸濁液に２８％アンモニア水を加え、ｐＨ＝
３．０に調整する。次いで、８０℃に加熱し、鉄粉７．
１５ｇを加え、さらに、沸点若しくは近傍温度にて、３
時間加熱撹拌を続けると時間の経過と共に淡黄緑色結晶
が析出した。。この混合物を、室温まで冷却し、析出し
た結晶を濾取する（得量５９．２ｇ）。示差熱分析の結
果分解点２２９℃ＩＲ吸収スペクトル（ｃｍ−１）：１
７３２，１５７３ この結晶を水９０ｇに懸濁し、２８％アンモニア水を加
え、ｐＨ＝６．５〜７．０に調整する。その結果、結晶
は溶解し、暗褐色の溶液となる。この溶液に、酸素ガス
を吹き込むと、暗赤色澄明な水溶液となり２−ヒドロキ
シエチルイミノ二酢酸鉄（ＩＩＩ）錯塩水溶液を得た。
ヨウ素滴定法により含まれている鉄が３価であることを
確かめた。 Example 2 Preparation of 2 -Hydroxyethyliminodiacetic acid iron complex salt 80 ml of water and 62.02 g of 2-hydroxyethyliminodiacetic acid were added to 200 ml of 4-coluben and stirred, and 28% ammonia was added to this suspension. Add water, pH =
Adjust to 3.0. Then, it is heated to 80 ° C. and iron powder 7.
Add 15 g, and then add 3 at the boiling point or near temperature.
When heating and stirring were continued for a while, pale yellowish green crystals were deposited with the passage of time. . The mixture is cooled to room temperature, and the precipitated crystals are collected by filtration (yield 59.2 g). As a result of differential thermal analysis, decomposition point was 229 ° C. IR absorption spectrum (cm- 1 ): 1
732, 1573 The crystals are suspended in 90 g of water, and 28% aqueous ammonia is added to adjust the pH to 6.5 to 7.0. As a result, the crystals dissolve into a dark brown solution. When oxygen gas was blown into this solution, a dark red clear aqueous solution was obtained, and an aqueous solution of 2-hydroxyethyliminodiacetic iron (III) complex salt was obtained.
It was confirmed by the iodometric titration method that the iron contained was trivalent.
【００２０】実施例３ ２−ヒドロキシエチルイミノ二酢酸鉄錯塩の製造 ２００ｍｌ４径コルベンに、水３０ｍｌ、２−ヒドロキ
シエチルイミノ二酢酸６２．０２ｇを加え、撹拌を行
い、この懸濁液にＦｅＳＯ４・７Ｈ２Ｏ３５．５８ｇを
水５０ｍｌに溶解させた溶液を加える。さらに、２８％
アンモニア水を加えｐＨ＝３．０に調整する。次いで、
沸点若しくは、近傍温にて３時間加熱撹拌を続けると時
間の経過と共に途中、内容物は一旦溶けるが、その後淡
黄緑色結晶が析出した。得量５５ｇ ＩＲ吸収スペクト
ル（ｃｍ−１）：１７３２，１５９５この結晶を水に懸
濁し、２８％アンモニア水を加え、ｐＨ＝６．５〜７．
０に調整する。その結果、析出した結晶は溶解し、暗褐
色の溶液となる。この溶液に空気を吹き込むと赤褐色澄
明な水溶液となり、２−ヒドロキシエチルイミノ二酢酸
鉄（ＩＩＩ）錯塩を得た。ヨウ素滴定法により含まれて
いる鉄が３価であることを確かめた。 Example 3 Preparation of 2-hydroxyethyliminodiacetic acid iron complex salt To 30 ml of water and 62.02 g of 2-hydroxyethyliminodiacetic acid were added to 200 ml of 4-diameter Kolben, and the mixture was stirred, and FeSO 4 ·. A solution of 35.58 g of 7H 2 O in 50 ml of water is added. Furthermore, 28%
Ammonia water is added to adjust the pH to 3.0. Then
When heating and stirring was continued for 3 hours at the boiling point or near temperature, the contents once melted during the course of time, but light yellow-green crystals precipitated thereafter. Obtained amount 55 g IR absorption spectrum (cm- 1 ): 1732, 1595 This crystal was suspended in water, 28% aqueous ammonia was added, and pH = 6.5 to 7.
Adjust to 0. As a result, the precipitated crystals dissolve and become a dark brown solution. When air was blown into this solution, it became a clear reddish brown aqueous solution, and iron (III) 2-hydroxyethyliminodiacetic acid complex salt was obtained. It was confirmed by the iodometric titration method that the iron contained was trivalent.
【００２１】実施例４ ２−ヒドロキシエチルイミノ二酢酸鉄錯塩の製造 １０００ｍｌ４径コルベンに、水５０ｍｌ，２−ヒドロ
キシエチルイミノ二酢酸２２６．０８ｇを加え、これ
に、ＦｅＣｌ３・６Ｈ２Ｏ１４４．９３ｇを水１００ｍ
ｌに溶解させた溶液を加える。さらに、撹拌下２８％ア
ンモニア水を加え、ｐＨ＝３．０に調整する。次いで、
室温下、３時間撹拌を続けると、内容物は一旦溶け、さ
らに撹拌を続けると結晶析出した。この混合物に２８％
アンモニア水を加え、ｐＨ＝６．５〜７．０に調整す
る。その結果、析出した結晶は溶解し赤褐色澄明な水溶
液となり、２−ヒドロキシエチルイミノ酢酸鉄（ＩＩ
Ｉ）錯塩を得た。ヨウ素滴定法により含まれている鉄が
３価であることを確かめた。[0021] Example 4 2-hydroxyethyliminodiacetic acid iron complex salt of manufacturing 1000ml4 diameter flask, water 50 ml, 2-hydroxyethyl imino diacetate 226.08g added thereto, the FeCl 3 · 6H 2 O144.93g 100m of water
Add the solution dissolved in 1. Further, 28% ammonia water is added with stirring to adjust the pH to 3.0. Then
When stirring was continued at room temperature for 3 hours, the content once melted, and when stirring was continued, crystals were precipitated. 28% to this mixture
Ammonia water is added to adjust the pH to 6.5 to 7.0. As a result, the precipitated crystals were dissolved into a clear reddish brown aqueous solution, and iron 2-hydroxyethyliminoacetate (II
I) A complex salt was obtained. It was confirmed by the iodometric titration method that the iron contained was trivalent.
【００２２】参考例１ ２００ｍｌ４径コルベンに、水８０ｍｌ，２−ヒドロキ
シエチルイミノ二酢酸６２．０２ｇを加え、撹拌を行
い、この懸濁液に、２８％アンモニア水を加え、ｐＨ＝
４．５に調整する。次いで、８０℃に加熱し、四三酸化
鉄１０．０８ｇを加え、さらに、沸点若しくは、近傍温
度にて、８時間加熱撹拌を続けたが、四三酸化鉄が残
り、反応は進行しなかった。 Reference Example 1 80 ml of water and 62.02 g of 2-hydroxyethyliminodiacetic acid were added to 200 ml of 4 diameter Kolben, and the mixture was stirred. To this suspension, 28% aqueous ammonia was added to adjust pH =
Adjust to 4.5. Then, the mixture was heated to 80 ° C., 10.08 g of triiron tetraoxide was added thereto, and the mixture was further heated and stirred at the boiling point or near temperature for 8 hours, but triiron tetraoxide remained and the reaction did not proceed. .
Claims (6)
の塩２分子と鉄１原子とから成る２−ヒドロキシエチル
イミノ二酢酸鉄錯塩。1. An iron complex salt of 2-hydroxyethyliminodiacetic acid comprising two molecules of 2-hydroxyethyliminodiacetic acid or a salt thereof and one atom of iron.
ヒドロキシエチルイミノ二酢酸鉄錯塩。2. The iron according to claim 1, which is divalent iron.
Hydroxyethyliminodiacetic acid iron complex salt.
ヒドロキシエチルイミノ二酢酸鉄錯塩。3. The iron according to claim 1, which is trivalent iron.
Hydroxyethyliminodiacetic acid iron complex salt.
と鉄１原子とから成る２−ヒドロキシエチルイミノ二酢
酸鉄錯塩のアルカリ金属又はアンモニウム塩若しくはア
ミン塩。4. An alkali metal or ammonium salt or amine salt of a 2-hydroxyethyliminodiacetic acid iron complex salt consisting of two molecules of 2-hydroxyethyliminodiacetic acid and one atom of iron.
ノ二酢酸が少なくとも２分子以上の割合になるように組
み合わせ、液性をｐＨ４を超えないように調整し、反応
させることにより、鉄１原子と２−ヒドロキシエチルイ
ミノ二酢酸２分子とからなる２−ヒドロキシエチルイミ
ノ二酢酸鉄錯塩を得ることを特徴とする２−ヒドロキシ
エチルイミノ二酢酸鉄錯塩の製造方法。5. Iron 1 atom is prepared by combining 2-hydroxyethyliminodiacetic acid in a ratio of at least 2 molecules per 1 atom of iron, adjusting the liquidity so as not to exceed pH 4, and reacting. A method for producing a 2-hydroxyethyliminodiacetic acid iron complex salt, comprising obtaining a 2-hydroxyethyliminodiacetic acid iron complex salt consisting of and 2 molecules of 2-hydroxyethyliminodiacetic acid.
酸と１原子の二価鉄とから成る２−ヒドロキシエチルイ
ミノ二酢酸鉄（ＩＩ）錯塩を、水中に分散せしめ、液性
をｐＨ５〜８に調整し、酸素源の存在で酸化することに
より、鉄原子を酸化し、鉄原子が三価である２−ヒドロ
キシエチルイミノ二酢酸鉄（ＩＩＩ）錯塩を得ることを
特徴とする２−ヒドロキシエチルイミノ二酢酸鉄（ＩＩ
Ｉ）錯塩の製造方法。6. A 2-hydroxyethyliminodiacetic acid iron (II) complex salt composed of two molecules of 2-hydroxyethyliminodiacetic acid and one atom of divalent iron is dispersed in water to obtain a liquid having a pH of 5-8. 2-hydroxyethyl, wherein the iron atom is oxidized to obtain a 2-hydroxyethyliminodiacetic acid iron (III) complex salt in which the iron atom is trivalent Iron iminodiacetic acid (II
I) Method for producing complex salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22492793A JPH0733720A (en) | 1993-07-20 | 1993-07-20 | Iron complex salt of 2-hydroxyethyliminodiacetic acid and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22492793A JPH0733720A (en) | 1993-07-20 | 1993-07-20 | Iron complex salt of 2-hydroxyethyliminodiacetic acid and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0733720A true JPH0733720A (en) | 1995-02-03 |
Family
ID=16821357
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22492793A Pending JPH0733720A (en) | 1993-07-20 | 1993-07-20 | Iron complex salt of 2-hydroxyethyliminodiacetic acid and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0733720A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1651237A4 (en) * | 2003-08-04 | 2008-10-01 | Johnson & Johnson Consumer | METHOD FOR THE TREATMENT OF DERMATOLOGICAL ILLNESSES |
| US8757249B2 (en) | 2005-10-21 | 2014-06-24 | Toyota Jidosha Kabushiki Kaisha | Cooling device including a solar radiation blocking unit for a vehicle-mounted electrical apparatus |
-
1993
- 1993-07-20 JP JP22492793A patent/JPH0733720A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1651237A4 (en) * | 2003-08-04 | 2008-10-01 | Johnson & Johnson Consumer | METHOD FOR THE TREATMENT OF DERMATOLOGICAL ILLNESSES |
| US7737179B2 (en) | 2003-08-04 | 2010-06-15 | J&J Consumer Companies, Inc. | Methods for treatment of dermatological conditions |
| US8757249B2 (en) | 2005-10-21 | 2014-06-24 | Toyota Jidosha Kabushiki Kaisha | Cooling device including a solar radiation blocking unit for a vehicle-mounted electrical apparatus |
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