JP2644977B2 - Iminocarboxylate aqueous solution composition - Google Patents
Iminocarboxylate aqueous solution compositionInfo
- Publication number
- JP2644977B2 JP2644977B2 JP25493594A JP25493594A JP2644977B2 JP 2644977 B2 JP2644977 B2 JP 2644977B2 JP 25493594 A JP25493594 A JP 25493594A JP 25493594 A JP25493594 A JP 25493594A JP 2644977 B2 JP2644977 B2 JP 2644977B2
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- Prior art keywords
- iminocarboxylate
- aqueous solution
- solution composition
- aspartic acid
- present
- Prior art date
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、有機キレート剤、洗剤
用ビルダー、スケール防止剤等として有用なイミノカル
ボン酸塩の水溶液組成物に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous solution composition of an iminocarboxylic acid salt which is useful as an organic chelating agent, a detergent builder, a scale inhibitor and the like.
【０００２】[0002]
【従来の技術】本発明に係わる下記一般式（１）2. Description of the Related Art The following general formula (1) according to the present invention:
【０００３】[0003]
【化２】 Embedded image
【０００４】（式中、Ｒは水素原子または水酸基を表わ
し、Ｘはナトリウムまたはアンモニウム基を表わす。）
で示されるイミノカルボン酸塩は、粉末あるいは粒状に
して固体状態で取り扱う場合には、該イミノカルボン酸
塩の吸湿性が高いため、貯蔵あるいは輸送中に空気中の
水分を吸収して固体どうしが融着してしまい粘着性の塊
状物となってしまう。そのため、一般に前記イミノカル
ボン酸塩は、水溶液として貯蔵あるいは輸送する方が有
利であり、また、水溶液として貯蔵あるいは輸送する場
合、できるだけ高濃度、低温下での取り扱いが経済的で
ある。(Wherein, R represents a hydrogen atom or a hydroxyl group, and X represents a sodium or ammonium group.)
When the iminocarboxylate represented by the formula is powdered or granulated and handled in a solid state, the iminocarboxylate absorbs moisture in the air during storage or transportation, and the solids are separated from each other due to the high hygroscopicity of the iminocarboxylate. It fuses and becomes a sticky mass. For this reason, it is generally advantageous to store or transport the iminocarboxylate as an aqueous solution, and when storing or transporting it as an aqueous solution, it is economical to handle it at the highest possible concentration and low temperature.
【０００５】しかしながら、前記一般式（１）における
Ｘがカリウムであるイミノカルボン酸塩は、４０重量％
以上の水溶液も知られている（国際公開番号ＷＯ９２／
０２４８９号明細書）が、前記イミノカルボン酸のナト
リウム塩およびアンモニウム塩については安定な水溶液
とならず、該水溶液はこれまで報告されていなかった。However, the iminocarboxylic acid salt in which X is potassium in the general formula (1) is 40% by weight.
The above aqueous solutions are also known (International Publication No. WO92 /
Patent No. 02489) does not provide a stable aqueous solution of the sodium salt and ammonium salt of the iminocarboxylic acid, and the aqueous solution has not been reported so far.
【０００６】また前記イミノカルボン酸のカリウム塩に
ついても低温流動性が悪いという問題があり、４０重量
％以上の濃厚溶液で取り扱うのが困難であった。事実、
本発明者らが前記イミノカルボン酸塩の水溶液について
低温における安定性について検討したところ、該イミノ
カルボン酸塩は結晶として析出し、場合によっては水溶
液自体が完全に固化してしまうという問題があることが
判明した。[0006] Also, the potassium salt of iminocarboxylic acid has a problem that its low-temperature fluidity is poor, and it has been difficult to handle it with a concentrated solution of 40% by weight or more. fact,
The present inventors examined the stability of the aqueous solution of the iminocarboxylate at low temperature, and found that the iminocarboxylate was precipitated as crystals, and in some cases, the aqueous solution itself was completely solidified. There was found.
【０００７】このように前記イミノカルボン酸塩の水溶
液の安定性や取扱方法に関する検討は全くなされていな
かったのが現状である。As described above, no study has been made on the stability and handling method of the aqueous solution of the iminocarboxylate at present.
【０００８】[0008]
【発明が解決しようとする課題】本発明は、前記のごと
き状況に鑑みてなされたものであり、貯蔵および輸送が
容易に行え、またキレート剤等として使用する場合に均
一な溶液として取り扱うことのでき、低温においても結
晶の析出のない安定なイミノカルボン酸塩水溶液組成物
を提供することを目的とする。DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances, and can be easily stored and transported, and can be handled as a uniform solution when used as a chelating agent. An object of the present invention is to provide a stable iminocarboxylate aqueous solution composition which can be produced and does not precipitate crystals even at low temperatures.
【０００９】[0009]
【課題を解決するための手段】本発明者らは、上記課題
について鋭意検討した結果、前記イミノカルボン酸塩の
アスパラギン酸骨格部分のＤ体とＬ体の異性体のモル比
が特定の範囲内において、低温、高濃度においても結晶
の析出のない安定な水溶液組成物が得られることを見い
だした。Means for Solving the Problems As a result of intensive studies on the above-mentioned problems, the present inventors have found that the molar ratio of the isomers of the D-form and the L-form of the aspartic acid skeleton of the iminocarboxylate is within a specific range. It was found that a stable aqueous solution composition free of crystals even at low temperature and high concentration was obtained.
【００１０】即ち、本発明は、下記一般式（１）That is, the present invention provides the following general formula (1)
【００１１】[0011]
【化３】 Embedded image
【００１２】（式中、Ｒは水素原子または水酸基を表わ
し、Ｘはナトリウムまたはアンモニウム基を表わす。）
で示されるイミノカルボン酸塩のアスパラギン酸骨格の
Ｄ体とＬ体の異性体のモル比が１／０〜０．７／０．３
または０／１〜０．３／０．７の範囲内とすることを特
徴とする低温安定性イミノカルボン酸塩水溶液組成物で
ある。(Wherein, R represents a hydrogen atom or a hydroxyl group, and X represents a sodium or ammonium group.)
The molar ratio of the isomers of the D-form and the L-form of the aspartic acid skeleton of the iminocarboxylate represented by the formula is 1/0 to 0.7 / 0.3
Or a low-temperature-stable iminocarboxylate aqueous solution composition characterized by being in the range of 0/1 to 0.3 / 0.7.
【００１３】[0013]
【作用】以下、本発明を詳しく説明する。Hereinafter, the present invention will be described in detail.
【００１４】前記一般式（１）で示されるイミノカルボ
ン酸塩は、式中のＲが水素原子の場合にはアスパラギン
酸とマレイン酸とを、式中のＲが水酸基の場合にはアス
パラギン酸とエポキシコハク酸とを水を媒体としてアル
カリ条件下で反応させて得るのが一般的である。従っ
て、原料のアスパラギン酸をＤ−アスパラギン酸とＬ−
アスパラギン酸あるいはそれらの混合物とすることによ
り、アスパラギン酸骨格のＤ体とＬ体のモル比が任意の
組成のイミノカルボン酸塩を得ることができる。The iminocarboxylic acid salt represented by the above general formula (1) is prepared by using aspartic acid and maleic acid when R in the formula is a hydrogen atom, and aspartic acid when R in the formula is a hydroxyl group. It is generally obtained by reacting epoxysuccinic acid with water as a medium under alkaline conditions. Therefore, the raw material aspartic acid is replaced with D-aspartic acid and L-aspartic acid.
By using aspartic acid or a mixture thereof, it is possible to obtain an iminocarboxylic acid salt having a composition in which the molar ratio of the D-form and the L-form of the aspartic acid skeleton is arbitrary.
【００１５】本発明は、これらのイミノカルボン酸塩の
アスパラギン酸骨格のＤ体とＬ体のモル比（Ｄ体／Ｌ体
＝）を１／０〜０．７／０．３または０／１〜０．３／
０．７の範囲内とする低温安定性イミノカルボン酸塩水
溶液組成物である。According to the present invention, the molar ratio of the D-form to the L-form of the aspartic acid skeleton of these iminocarboxylates (D-form / L-form =) is from 1/0 to 0.7 / 0.3 or 0/1. ~ 0.3 /
It is a low-temperature-stable iminocarboxylate aqueous solution composition within the range of 0.7.
【００１６】前記イミノカルボン酸塩のアスパラギン酸
骨格のＤ体とＬ体のモル比を上記範囲内とするには、該
イミノカルボン酸塩の製造前にあらかじめＤ−アスパラ
ギン酸およびＬ−アスパラギン酸の仕込モル比を上記範
囲内としておくか、あるいはＤ−アスパラギン酸とＬ−
アスパラギン酸よりそれぞれ単独に製造したイミノカル
ボン酸塩を上記モル比となるよう混合してもよい。In order to make the molar ratio of the D-form and the L-form of the aspartic acid skeleton of the iminocarboxylate within the above range, the D-aspartic acid and L-aspartic acid must be prepared before the production of the iminocarboxylate. The charging molar ratio is kept within the above range, or D-aspartic acid and L-
Iminocarboxylates each produced independently from aspartic acid may be mixed in the above molar ratio.
【００１７】一方、前記イミノカルボン酸塩のアスパラ
ギン酸骨格部分のＤ体とＬ体の異性体の割合が上記範囲
外の組成の水溶液は、その濃度が３０重量％の濃度にお
いても、低温下において短時間で結晶が析出し、不均一
なスラリー状態となってしまい、均一なスラリーとして
取り扱うためには、攪拌、ポンプによる強制循環等の特
別な混合が必要なばかりでなくポンプ等による移送時の
詰まり等のトラブルの原因となる。On the other hand, an aqueous solution having a composition in which the proportion of the isomers of the aspartic acid skeleton portion of the iminocarboxylate D and L isomers is out of the above range, even at a concentration of 30% by weight and at a low temperature. Crystals are precipitated in a short time, resulting in a non-uniform slurry, and in order to handle it as a uniform slurry, not only special mixing such as stirring, forced circulation by a pump, etc. is necessary, but also It may cause troubles such as clogging.
【００１８】本発明のイミノカルボン酸塩の濃度は、４
０〜７０重量％、好ましくは４０〜６０重量％の濃度で
あり、公知の方法により調製される。前記イミノカルボ
ン酸塩の濃度が前記の範囲より高い場合には、組成物が
高粘度のスラリー状になってしまい、取扱が困難になっ
てしまう。また、イミノカルボン酸塩濃度が前記の範囲
より低濃度の場合には、取扱は容易であるが貯蔵あるい
は輸送時の容器が大型なものとなってしまい不経済であ
る。The concentration of the iminocarboxylate of the present invention is 4
It has a concentration of 0 to 70% by weight, preferably 40 to 60% by weight, and is prepared by a known method. If the concentration of the iminocarboxylate is higher than the above range, the composition becomes a slurry having a high viscosity, and handling becomes difficult. When the concentration of the iminocarboxylic acid salt is lower than the above range, the handling is easy, but the container for storage or transportation becomes large, which is uneconomical.
【００１９】このようにして調製されたイミノカルボン
酸塩水溶液組成物は、２０〜−１０℃の低温条件下にお
いても結晶の析出もなく、長期間安定で均一な溶液とし
て取り扱うことが可能である。The iminocarboxylate aqueous solution composition thus prepared does not precipitate even under low temperature conditions of 20 to -10 ° C., and can be handled as a long-term stable and uniform solution. .
【００２０】以上、本発明のイミノカルボン酸塩水溶液
組成物は、低温、高濃度下においても安定であり、常に
均一な水溶液として取り扱うことが可能なため、保温や
攪拌等の特別な装置を必要とすることなく、貯蔵容器に
蓄えられたり、反応槽、貯槽から直接目的とする場所へ
配管を経由して送液したり、タンクローリー、タンク貨
車、コンテナ、ドラム缶などに充填して輸送することが
できる。貯蔵あるいは輸送にあたっての気層部条件にも
特に制限はなく、チッソ、アルゴン等の不活性ガス、酸
素、空気などを用いることができる。As described above, since the iminocarboxylate aqueous solution composition of the present invention is stable even at low temperatures and high concentrations and can always be handled as a uniform aqueous solution, it requires special equipment such as heat retention and stirring. Can be stored in a storage container, sent directly from a reaction tank or storage tank to a target location via a pipe, filled in a tank truck, tank wagon, container, drum, etc. and transported. it can. There are no particular restrictions on the gas layer conditions for storage or transportation, and inert gases such as nitrogen and argon, oxygen, and air can be used.
【００２１】また、本発明のイミノカルボン酸塩水溶液
組成物と接触する部分の材料の材質は炭素鋼、ステンレ
ススチール、ガラスライニング、テフロン等の樹脂ライ
ニング、ゴムライニング、ハステロイ、チタン合金、ニ
ッケルなどいずれの材質でもよいが、ステンレススチー
ルが好ましい。The material of the material in contact with the iminocarboxylate aqueous solution composition of the present invention may be any of carbon steel, stainless steel, glass lining, resin lining such as Teflon, rubber lining, Hastelloy, titanium alloy, nickel and the like. , But stainless steel is preferred.
【００２２】本発明のイミノカルボン酸塩水溶液組成物
の貯蔵あるいは輸送に際しての温度は、７０℃以下好ま
しくは５０℃以下であれば特に制限はない。The temperature for storing or transporting the aqueous iminocarboxylate composition of the present invention is not particularly limited as long as it is 70 ° C. or lower, preferably 50 ° C. or lower.
【００２３】[0023]
【実施例】以下に本発明を実施例により更に詳しく説明
する。The present invention will be described in more detail with reference to the following examples.
【００２４】合成例１ エポキシコハク酸２ナトリウム塩８８ｇ、Ｌ−アスパラ
ギン酸２ナトリウム８８．５ｇおよび水２１０ｇを攪拌
機、還流冷却器付きの４つ口フラスコに仕込み、８０℃
で８時間反応させた。Synthesis Example 1 88 g of disodium salt of epoxysuccinic acid, 88.5 g of disodium L-aspartate and 210 g of water were charged into a four-necked flask equipped with a stirrer and a reflux condenser.
For 8 hours.
【００２５】反応後の反応液を高速液体クロマトグラフ
ィーにて分析した結果、前記一般式（１）におけるＲが
ＯＨ、ＸがＮａであるＬ体のイミノカルボン酸の４ナト
リウム塩が１６５ｇ含まれていた。The reaction solution after the reaction was analyzed by high performance liquid chromatography. As a result, it was found that 165 g of L-form iminocarboxylic acid tetrasodium salt in which R is OH and X is Na in the general formula (1) was contained. Was.
【００２６】合成例２ Ｌ−アスパラギン酸２ナトリウムのかわりにＤ−アスパ
ラギン酸２ナトリウムを使用した他は、合成例１と同様
に反応・分析を行い、前記一般式（１）におけるＲがＯ
Ｈ、ＸがＮａであるＤ体のイミノカルボン酸の４ナトリ
ウム塩１６４．５ｇを含む水溶液を得た。Synthesis Example 2 A reaction and analysis were conducted in the same manner as in Synthesis Example 1 except that disodium D-aspartate was used instead of disodium L-aspartate.
An aqueous solution containing 164.5 g of tetrasodium salt of D-form iminocarboxylic acid in which H and X are Na was obtained.
【００２７】実施例１〜１０ 合成例１および２で合成したＬ体とＤ体のイミノカルボ
ン酸の４ナトリウム塩（前記一般式（１）においてＲ＝
ＯＨ、Ｘ＝Ｎａ）の混合比率および水溶液濃度を表１の
ように種々変更して、イミノカルボン酸塩水溶液組成物
を得た。Examples 1 to 10 L-form and D-form iminocarboxylic acid tetrasodium salts synthesized in Synthesis Examples 1 and 2 (wherein R =
The mixing ratio of OH, X = Na) and the concentration of the aqueous solution were variously changed as shown in Table 1 to obtain an iminocarboxylate aqueous solution composition.
【００２８】比較例１〜５ 合成例１および２で合成したＬ体とＤ体のイミノカルボ
ン酸の４ナトリウム塩（前記一般式（１）においてＲ＝
ＯＨ、Ｘ＝Ｎａ）の混合比率および水溶液濃度を表１の
ように種々変更して、イミノカルボン酸塩水溶液組成物
を得た。Comparative Examples 1 to 5 L-form and D-form iminocarboxylic acid tetrasodium salts synthesized in Synthesis Examples 1 and 2 (wherein R =
The mixing ratio of OH, X = Na) and the concentration of the aqueous solution were variously changed as shown in Table 1 to obtain an iminocarboxylate aqueous solution composition.
【００２９】参考例１ 実施例および比較例で合成したイミノカルボン酸の４ナ
トリウム塩の水溶液組成物の低温条件下での１カ月間の
溶液の変化を表１に示した。REFERENCE EXAMPLE 1 Table 1 shows the change of the solution of the aqueous solution of tetrasodium salt of iminocarboxylic acid synthesized in Examples and Comparative Examples for one month under low temperature conditions.
【００３０】[0030]
【表１】 [Table 1]
【００３１】[0031]
【発明の効果】本発明のイミノカルボン酸塩水溶液組成
物は、貯蔵および輸送が容易に行え、低温においても結
晶の析出のない安定な組成物である。また本発明のイミ
ノカルボン酸塩水溶液組成物は、均一な溶液として取り
扱うことのできるため、各種キレート剤等として有用で
ある。The aqueous iminocarboxylate composition of the present invention is a stable composition which can be easily stored and transported and does not precipitate crystals even at low temperatures. Further, the iminocarboxylate aqueous solution composition of the present invention can be handled as a homogeneous solution, and is therefore useful as various chelating agents.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 喜多 裕一 兵庫県姫路市網干区興浜字西沖992番地 の１ 株式会社日本触媒 機能開発研究 所内 (56)参考文献 特開 平８−169866（ＪＰ，Ａ) ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Yuichi Kita 992, Nishioki, Okihama-shi, Abashiri-ku, Himeji-shi, Hyogo Japan Nippon Shokubai Functional Development Laboratory Co., Ltd.
Claims (1)
リウムまたはアンモニウム基を表わす。）で示されるイ
ミノカルボン酸塩を含有し、該イミノカルボン酸塩のア
スパラギン酸骨格部分の異性体割合が、下記の割合であ
り、 Ｄ体／Ｌ体（モル比）＝１／０ 〜 ０．７／０．３ 又は、 Ｄ体／Ｌ体（モル比）＝０／１ 〜 ０．３／０．７ かつ、該イミノカルボン酸塩の含有量が４０重量％〜７
０重量％の範囲であることを特徴とするイミノカルボン
酸塩水溶液組成物。[Claim 1] The following general formula (1) (Wherein, R represents a hydrogen atom or a hydroxyl group, and X represents a sodium or ammonium group), wherein the ratio of isomers of the aspartic acid skeleton portion of the iminocarboxylic acid salt is as follows: The ratio is as follows: D-form / L-form (molar ratio) = 1/0 to 0.7 / 0.3 or D-form / L-form (molar ratio) = 0/1 to 0.3 / 0.7 And, the content of the iminocarboxylate is 40% by weight to 7%.
An iminocarboxylic acid salt aqueous solution composition in an amount of 0% by weight.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25493594A JP2644977B2 (en) | 1994-10-20 | 1994-10-20 | Iminocarboxylate aqueous solution composition |
| KR1019950035855A KR100254103B1 (en) | 1994-10-20 | 1995-10-17 | Aqueous iminocarboxylic acid salt solution composition and method for handling iminocarboxylic acid salt |
| US08/544,784 US6063302A (en) | 1994-10-20 | 1995-10-18 | Method for handling iminocarboxylic acid salt |
| DE69500491T DE69500491T2 (en) | 1994-10-20 | 1995-10-19 | Composition of an aqueous solution of the salt of iminocarboxylic acid and method for treating this salt |
| EP95307462A EP0708078B1 (en) | 1994-10-20 | 1995-10-19 | Aqueous iminocarboxylic acid salt solution composition and method for handling iminocarboxylic acid salt |
| TW084111126A TW296372B (en) | 1994-10-20 | 1995-10-20 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25493594A JP2644977B2 (en) | 1994-10-20 | 1994-10-20 | Iminocarboxylate aqueous solution composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08119915A JPH08119915A (en) | 1996-05-14 |
| JP2644977B2 true JP2644977B2 (en) | 1997-08-25 |
Family
ID=17271907
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25493594A Expired - Fee Related JP2644977B2 (en) | 1994-10-20 | 1994-10-20 | Iminocarboxylate aqueous solution composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2644977B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7319165B2 (en) | 2002-06-11 | 2008-01-15 | Nippon Shokubai Co., Ltd. | Aminopolycarboxylic acid aqueous solution composition and stabilization method of aminopolycarboxlic acid |
| US8173588B2 (en) | 2005-07-27 | 2012-05-08 | Nippon Shokubai Co., Ltd. | Iminocarboxylic acid salt-containing solid composition and production method thereof |
-
1994
- 1994-10-20 JP JP25493594A patent/JP2644977B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7319165B2 (en) | 2002-06-11 | 2008-01-15 | Nippon Shokubai Co., Ltd. | Aminopolycarboxylic acid aqueous solution composition and stabilization method of aminopolycarboxlic acid |
| US8173588B2 (en) | 2005-07-27 | 2012-05-08 | Nippon Shokubai Co., Ltd. | Iminocarboxylic acid salt-containing solid composition and production method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08119915A (en) | 1996-05-14 |
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