JPH08169866A - Handling of iminocarboxylate salt - Google Patents
Handling of iminocarboxylate saltInfo
- Publication number
- JPH08169866A JPH08169866A JP7250531A JP25053195A JPH08169866A JP H08169866 A JPH08169866 A JP H08169866A JP 7250531 A JP7250531 A JP 7250531A JP 25053195 A JP25053195 A JP 25053195A JP H08169866 A JPH08169866 A JP H08169866A
- Authority
- JP
- Japan
- Prior art keywords
- aqueous solution
- acid salt
- iminocarboxylic acid
- iminocarboxylic
- handling
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】Detailed Description of the Invention
【０００１】[0001]
【発明の属する技術分野】本発明はイミノカルボン酸塩
の取り扱い方法、詳しくは有機キレート剤、洗剤用ビル
ダー、スケール防止剤などとして有用なイミノカルボン
酸塩を、長期にわたりイミノカルボン酸塩結晶の析出な
どがない、安定かつ均一な水溶液として取り扱う方法に
関する。TECHNICAL FIELD The present invention relates to a method for handling an iminocarboxylic acid salt, and more specifically to depositing an iminocarboxylic acid salt useful as an organic chelating agent, a builder for detergents, a scale inhibitor, etc. The present invention relates to a method of handling as a stable and uniform aqueous solution that does not have
【０００２】本発明における「取り扱う」との用語は、
イミノカルボン酸塩の水溶液のタンクローリーなどによ
る輸送、タンクなどでの貯蔵、パイプ、バルブ、ノズル
などを含めた配管での移送などを意味する。In the present invention, the term "handle" means
It means transportation of an aqueous solution of an iminocarboxylic acid salt by a tank truck, storage in a tank, etc., transportation by a pipe including a pipe, a valve, a nozzle, etc.
【０００３】[0003]
【従来の技術および問題点】本発明に係わる一般式
（１）2. Description of the Related Art General formula (1) according to the present invention
【０００４】[0004]
【化２】 Embedded image
【０００５】（式中、Ｒは水素原子または水酸基を表
し、Ｘはナトリウム、カリウムまたはアンモニウム基を
表す）で表されるイミノカルボン酸塩は、国際公開番号
ＷＯ９２／０２４８９号明細書などにより公知である。
以下、単に「イミノカルボン酸塩」という場合、これは
上記一般式（１）のイミノカルボン酸塩を意味する。イ
ミノカルボン酸塩を粉末あるいは粒状の固体状態で取り
扱う場合には、このイミノカルボン酸塩の吸湿性が高い
ため、取り扱い中に空気中の水分を吸収して固体同士が
融着してしまい粘着性の塊状物となってしまう。The iminocarboxylic acid salt represented by the formula (wherein R represents a hydrogen atom or a hydroxyl group and X represents a sodium, potassium or ammonium group) is known from International Publication No. WO92 / 02489. is there.
Hereinafter, when simply referred to as "iminocarboxylic acid salt", this means the iminocarboxylic acid salt of the general formula (1). When handling the iminocarboxylic acid salt in the powder or granular solid state, the hygroscopicity of this iminocarboxylic acid salt is high, so the water content in the air is absorbed during handling and the solids fuse together to cause stickiness. It becomes a lump of.
【０００６】このため、イミノカルボン酸塩は水溶液と
して取り扱うのが有利であるが、このような水溶液とし
ての取り扱いについての具体的検討は未だなされておら
ず、本発明者らの検討によって初めてイミノカルボン酸
塩を水溶液として取り扱うに際しては種々の問題がある
ことが分かった。その一つはイミノカルボン酸塩の析出
であり、一般にはできるだけ高い濃度および低い温度で
取り扱うのが経済的であるが、このような高濃度、低温
度の条件下ではイミノカルボン酸塩結晶が析出し、特に
時間の経過とともに析出が著しくなる。場合によって
は、水溶液自体が完全に固化してしまうこともある。特
に、イミノカルボン酸のナトリウム塩は、水に対する溶
解性が他の塩に比べて悪いため、析出の問題は深刻なも
のとなる。他の問題は、イミノカルボン酸塩水溶液の粘
度であり、結晶の析出がなくとも、水溶液の粘度が１
０，０００ｃｐｓを超えると取り扱いが著しく困難とな
ることである。さらに他の問題は、イミノカルボン酸塩
の水溶液を加熱濃縮してその濃度を所望の濃度まで高め
ようとすると、イミノカルボン酸塩もしくはその水溶液
が着色して商品価値が著しく損なわれる上に、イミノカ
ルボン酸塩が析出することである。For this reason, it is advantageous to handle the iminocarboxylic acid salt as an aqueous solution, but no specific study on such handling as an aqueous solution has been made yet, and the iminocarboxylic acid is first examined by the present inventors. It has been found that there are various problems in handling the acid salt as an aqueous solution. One of them is precipitation of iminocarboxylate, and it is generally economical to handle it at the highest concentration and the lowest temperature. However, under such conditions of high concentration and low temperature, the iminocarboxylate crystals are precipitated. However, the precipitation becomes remarkable over time. In some cases, the aqueous solution itself may completely solidify. In particular, the sodium salt of iminocarboxylic acid has poorer solubility in water than other salts, so that the problem of precipitation becomes serious. Another problem is the viscosity of the iminocarboxylic acid salt aqueous solution, and the viscosity of the aqueous solution is 1 even if there is no precipitation of crystals.
If it exceeds 10,000 cps, the handling becomes extremely difficult. Still another problem is that when an aqueous solution of an iminocarboxylic acid salt is heated and concentrated to increase its concentration to a desired concentration, the iminocarboxylic acid salt or the aqueous solution thereof is colored and the commercial value is significantly impaired. That is, the carboxylate is precipitated.
【０００７】[0007]
【発明が解決しようとする課題】本発明は前記一般式
（１）で表されるイミノカルボン酸塩を水溶液として取
り扱う際に遭遇する前記のような問題点を解決して、こ
のイミノカルボン酸塩水溶液を長期にわたって安定的に
取り扱う方法を提供しようとするものである。The present invention solves the above-mentioned problems encountered when handling the iminocarboxylic acid salt represented by the general formula (1) as an aqueous solution, and this iminocarboxylic acid salt is solved. It is intended to provide a method for stably handling an aqueous solution for a long period of time.
【０００８】[0008]
【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、イミノカルボン酸塩のアスパ
ラギン酸骨格部分のＤ体およびＬ体の異性体のモル比、
水溶液中のイミノカルボン酸塩の濃度および水溶液のｐ
Ｈを特定範囲とすることにより、イミノカルボン酸塩
を、長期にわたり結晶の析出、水溶液の固化などもな
い、安定かつ均一な水溶液として取り扱えることを知
り、この知見に基づいて本発明を完成するに至った。Means for Solving the Problems As a result of intensive studies on the above problems, the present inventors have found that the molar ratio of the D-isomer and L-isomer of the aspartic acid skeleton portion of the iminocarboxylic acid salt,
Concentration of iminocarboxylate in aqueous solution and p of aqueous solution
By setting H to a specific range, it was found that the iminocarboxylic acid salt can be handled as a stable and uniform aqueous solution without precipitation of crystals and solidification of the aqueous solution for a long period of time, and based on this finding, the present invention was completed. I arrived.
【０００９】すなわち、本発明は、下記一般式（１）That is, the present invention provides the following general formula (1)
【００１０】[0010]
【化３】 Embedded image
【００１１】（式中、Ｒは水素原子または水酸基を表
し、Ｘはナトリウム、カリウムまたはアンモニウム基を
表す）で表されるイミノカルボン酸塩を取り扱うに際し
て、該イミノカルボン酸塩のアスパラギン酸骨格部分の
異性体割合をＤ体／Ｌ体（モル比）＝１／０〜０．７／
０．３またはＤ体／Ｌ体（モル比）＝０／１〜０．３／
０．７とし、かつ該イミノカルボン酸塩を濃度４０〜７
０重量％およびｐＨ７〜１２に調整した水溶液として取
り扱うことを特徴とするイミノカルボン酸塩の取り扱い
方法である。When an iminocarboxylic acid salt represented by the formula (wherein R represents a hydrogen atom or a hydroxyl group and X represents a sodium, potassium or ammonium group), the aspartic acid skeleton portion of the iminocarboxylic acid salt is treated. The isomer ratio is 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 concentration of the iminocarboxylic acid salt is 40 to 7
It is a method for handling an iminocarboxylic acid salt, characterized in that it is handled as an aqueous solution adjusted to 0% by weight and pH 7 to 12.
【００１２】[0012]
【発明の実施の形態】前記一般式（１）で表されるイミ
ノカルボン酸塩は公知の方法により調製することができ
る。一般式（１）においてＲが水酸基の化合物は、アス
パラギン酸塩とエポキシコハク酸塩とを水性媒体中でア
ルカリ条件下に反応させることにより得られる。また、
一般式（１）においてＲが水素原子の化合物は、アスパ
ラギン酸塩とマレイン酸塩とを水性媒体中でアルカリ条
件下に反応させることにより得られる。BEST MODE FOR CARRYING OUT THE INVENTION The iminocarboxylic acid salt represented by the general formula (1) can be prepared by a known method. The compound in which R is a hydroxyl group in the general formula (1) is obtained by reacting an aspartic acid salt and an epoxysuccinic acid salt in an aqueous medium under alkaline conditions. Also,
The compound in which R is a hydrogen atom in the general formula (1) can be obtained by reacting an aspartate and a maleate in an aqueous medium under alkaline conditions.
【００１３】なお、一般式（１）において、４つのＸは
すべて同一である必要はなく、それぞれ異なっていても
よく、一般式（１）で表されるイミノカルボン酸塩に
は、テトラ（４）ナトリウム塩のほかにジ（２）ナトリ
ウムジ（２）カリウム塩、モノ（１）ナトリウムトリ
（３）カリウム塩なども包含される。これら塩のうち、
特にテトラ（４）ナトリウム塩の場合、本発明の取り扱
い方法が効果的に用いられる。In the general formula (1), all four Xs need not be the same and may be different from each other. The iminocarboxylic acid salt represented by the general formula (1) includes tetra (4) ) In addition to sodium salt, di (2) sodium di (2) potassium salt, mono (1) sodium tri (3) potassium salt and the like are also included. Of these salts,
Particularly in the case of tetra (4) sodium salt, the handling method of the present invention can be effectively used.
【００１４】本発明の取り扱い方法の第一の要件は、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
（Ｄ体＋Ｌ体＝１モル）または０／１〜０．３／０．７
（Ｄ体＋Ｌ体＝１モル）の範囲にすることである。イミ
ノカルボン酸塩のアスパラギン酸骨格のＤ体とＬ体とを
上記範囲内とするには、イミノカルボン酸塩の製造前に
あらかじめＤ−アスパラギン酸塩およびＬ−アスパラギ
ン酸塩の仕込モル比を上記範囲内としておくか、あるい
はＤ−アスパラギン酸塩とＬ−アスパラギン酸塩とから
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
比となるように混合してもよい。イミノカルボン酸塩の
アスパラギン酸骨格のＤ体とＬ体との割合が上記範囲外
の組成のイミノカルボン酸塩を水溶液として取り扱う場
合、他の取り扱い要件が満たされていても、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う。こ
れを均一なスラリーとして取り扱うためには撹拌、ポン
プによる強制循環などの特別な混合操作が必要となるだ
けではなく、ポンプなどによる移送時の詰まりなどのト
ラブルの原因となる。The first requirement of the handling method of the present invention is that the molar ratio of the D-form to the L-form of the aspartic acid skeleton of the iminocarboxylic acid salt (D-form / L-form =) is 1/0 to 0.7 /. 0.3
(D form + L form = 1 mol) or 0/1 to 0.3 / 0.7
It is to be in the range of (D form + L form = 1 mol). In order to bring the D- and L-forms of the aspartic acid skeleton of the iminocarboxylic acid salt into the above range, the charged molar ratio of D-aspartic acid salt and L-aspartic acid salt should be set in advance before the production of the iminocarboxylic acid salt. The amount may be kept within the range, or the iminocarboxylic acid salt prepared separately from D-aspartate and L-aspartate may be mixed in the above molar ratio. When an iminocarboxylic acid salt having a composition in which the D-form and the L-form of the aspartic acid skeleton of the iminocarboxylic acid salt are outside the above ranges is treated as an aqueous solution, even if other handling requirements are satisfied, crystals are formed in a short time. It precipitates and becomes a non-uniform slurry state. In order to handle this as a uniform slurry, not only special mixing operations such as stirring and forced circulation by a pump are required, but also troubles such as clogging during transfer by a pump are caused.
【００１５】本発明の取り扱い方法の第二の要件は、イ
ミノカルボン酸塩の水溶液濃度を４０〜７０重量％とす
ることである。水溶液濃度が４０重量％より低い場合に
は、安定な水溶液として取り扱うことができるが、希薄
水溶液なため貯蔵および輸送の設備が大型なものになっ
てしまい不経済である。また、水溶液濃度が７０重量％
を超えると水溶液から結晶が析出して取り扱いが困難と
なる。上記水溶液濃度範囲ではイミノカルボン酸のナト
リウム塩の場合も安定した水溶液として取り扱うことが
できる。The second requirement of the handling method of the present invention is that the aqueous solution concentration of the iminocarboxylic acid salt is 40 to 70% by weight. When the concentration of the aqueous solution is lower than 40% by weight, the aqueous solution can be handled as a stable aqueous solution, but since it is a dilute aqueous solution, the storage and transportation facilities are large and uneconomical. Also, the concentration of the aqueous solution is 70% by weight.
If it exceeds, crystals will precipitate from the aqueous solution and handling will be difficult. In the above aqueous solution concentration range, the sodium salt of iminocarboxylic acid can be handled as a stable aqueous solution.
【００１６】本発明の取り扱い方法の第三の要件は、イ
ミノカルボン酸塩の水溶液のｐＨを７〜１２の範囲に調
整することである。イミノカルボン酸塩水溶液のｐＨが
７より低いとイミノカルボン酸塩が析出し、均一な水溶
液として取り扱うことができない。また、１２を超える
と貯蔵時の水溶液の着色およびイミノカルボン酸塩の分
解が進行して製品品質が劣化する。イミノカルボン酸塩
水溶液のｐＨが高い場合には塩酸、硫酸、リン酸などの
無機酸、あるいはマレイン酸、酒石酸、酢酸などの有機
酸を用いて、またｐＨが低い場合には水酸化ナトリウム
などのアルカリ金属水酸化物を用いて７〜１２の範囲に
調整する。The third requirement of the handling method of the present invention is to adjust the pH of the aqueous solution of the iminocarboxylic acid salt to the range of 7-12. When the pH of the iminocarboxylic acid salt aqueous solution is lower than 7, the iminocarboxylic acid salt is precipitated and cannot be handled as a uniform aqueous solution. On the other hand, if it exceeds 12, the coloring of the aqueous solution during storage and the decomposition of the iminocarboxylic acid salt proceed to deteriorate the product quality. When the pH of the iminocarboxylic acid salt aqueous solution is high, an inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid or an organic acid such as maleic acid, tartaric acid or acetic acid is used, and when the pH is low, sodium hydroxide such as sodium hydroxide is used. Adjust to a range of 7 to 12 using an alkali metal hydroxide.
【００１７】本発明によれば、上記３つの要件を満たす
ことにより、イミノカルボン酸塩を、結晶の析出や水溶
液の固化もなく、長期間安定で均一な水溶液として取り
扱うことが可能である。しかも、このイミノカルボン酸
塩水溶液の粘度は１０，０００ｃｐｓ以下であって取り
扱いが容易である。According to the present invention, by satisfying the above three requirements, the iminocarboxylic acid salt can be treated as a stable and uniform aqueous solution for a long period of time without precipitation of crystals or solidification of the aqueous solution. Moreover, the viscosity of this iminocarboxylic acid salt aqueous solution is 10,000 cps or less, and the handling is easy.
【００１８】本発明におけるイミノカルボン酸塩水溶液
の取り扱い温度には特に制限はなく任意の温度で取り扱
うことができる。しかし、本発明の取り扱い方法によれ
ば、特に−１０〜１０℃あるいは３０〜７０℃の範囲の
低温あるいは高温といった過酷な温度条件において、そ
の作用効果が顕著に発揮される。したがって、本発明の
好ましい形態は、前記イミノカルボン酸塩水溶液を−１
０〜１０℃あるいは３０〜７０℃の範囲の温度で取り扱
うことである。本発明の取り扱い方法によれば、１０℃
以下の低温でも前記のような高濃度のイミノカルボン酸
塩水溶液から結晶の析出や水溶液の固化がなく取り扱い
が容易であり、また３０℃以上の高温でも長期保存中に
イミノカルボン酸塩の分解や着色がなく取り扱いが容易
となる。なお、取り扱い温度が−１０℃より低くなると
水溶液の流動性が極端に低下し移送や輸送が困難となる
ことがある。また、７０℃を超えるとイミノカルボン酸
塩自体が分解してしまい、製品の純度低下の原因となる
ことがある。The handling temperature of the iminocarboxylic acid salt aqueous solution in the present invention is not particularly limited, and it can be handled at any temperature. However, according to the handling method of the present invention, the action and effect are remarkably exhibited particularly under severe temperature conditions such as low temperature or high temperature in the range of -10 to 10 ° C or 30 to 70 ° C. Therefore, a preferred embodiment of the present invention is the above-mentioned aqueous iminocarboxylic acid salt solution -1.
It is handled at a temperature in the range of 0 to 10 ° C or 30 to 70 ° C. According to the handling method of the present invention, 10 ° C
It is easy to handle even at the following low temperatures without precipitation of crystals or solidification of the aqueous solution of the high-concentration iminocarboxylic acid salt as described above, and decomposition of the iminocarboxylic acid salt during long-term storage even at a high temperature of 30 ° C. or higher. It is not colored and easy to handle. If the handling temperature is lower than -10 ° C, the fluidity of the aqueous solution may be extremely reduced, and it may be difficult to transfer or transport the solution. Further, if the temperature exceeds 70 ° C., the iminocarboxylic acid salt itself is decomposed, which may cause a decrease in the purity of the product.
【００１９】イミノカルボン酸塩水溶液は、前記のよう
に、アスパラギン酸塩とエポキシコハク酸塩またはマレ
イン酸塩とを水性媒体中で反応させて得られるが、反応
中における結晶の析出などを防止するために、反応終了
後の反応溶液、すなわち生成イミノカルボン酸塩の水溶
液中のイミノカルボン酸塩の濃度が４０重量％より低く
なるような濃度の出発原料を用いて反応を行う場合もあ
る。この場合、イミノカルボン酸塩水溶液を加熱濃縮し
てイミノカルボン酸塩濃度が４０〜７０重量％の水溶液
とする必要があるが、この加熱濃縮は減圧下に３０〜８
０℃の範囲の温度および７〜１２の範囲のｐＨで行うの
が望ましい。８０℃を超える温度ではイミノカルボン酸
塩の一部が分解して着色し、その製品価値が著しく損な
われる。また、３０℃より低い温度での濃縮は減圧度を
高くする必要があるなどの理由から工業的には望ましく
ない。また、７より低いｐＨで濃縮するとイミノカルボ
ン酸塩が析出し、また１２を超えるｐＨで濃縮するとイ
ミノカルボン酸塩水溶液が着色して好ましくない。The iminocarboxylic acid salt aqueous solution is obtained by reacting an aspartic acid salt with an epoxysuccinic acid salt or a maleic acid salt in an aqueous medium as described above, but prevents precipitation of crystals during the reaction. Therefore, the reaction may be carried out using a starting material having a concentration such that the concentration of the iminocarboxylic acid salt in the reaction solution after completion of the reaction, that is, the aqueous solution of the produced iminocarboxylic acid salt is lower than 40% by weight. In this case, it is necessary to heat and concentrate the aqueous iminocarboxylic acid salt to obtain an aqueous solution having an iminocarboxylic acid salt concentration of 40 to 70% by weight.
It is desirable to operate at a temperature in the range of 0 ° C. and a pH in the range of 7-12. At a temperature of higher than 80 ° C, a part of the iminocarboxylic acid salt is decomposed and colored, and the product value thereof is significantly impaired. Further, concentration at a temperature lower than 30 ° C. is industrially undesirable because it requires a high degree of vacuum. Further, if the pH is lower than 7, the iminocarboxylic acid salt is precipitated, and if the pH is higher than 12, the aqueous solution of the iminocarboxylic acid is colored, which is not preferable.
【００２０】したがって、本発明の一つの形態において
は、アスパラギン酸塩とエポキシコハク酸塩またはマレ
イン酸塩とを反応させて得られる、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Ｄ体／Ｌ体
（モル比）＝１／０〜０．７／０．３またはＤ体／Ｌ体
（モル比）＝０／１〜０．３／０．７であるイミノカル
ボン酸塩の水溶液を温度３０〜８０℃およびｐＨ７〜１
２の条件下に加熱濃縮して濃度４０〜７０重量％および
ｐＨ７〜１２のイミノカルボン酸塩水溶液を調製し、こ
れを３０〜７０℃の範囲の温度で取り扱う。この形態に
よれば、濃縮過程での着色が防止できるとともに、イミ
ノカルボン酸塩を結晶の析出および固化のない安定かつ
均一な水溶液として取り扱うことができる。Therefore, in one embodiment of the present invention, the isomer ratio of the aspartic acid skeleton portion of the iminocarboxylic acid salt obtained by reacting an aspartic acid salt with an epoxysuccinic acid salt or a maleic acid salt is 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 Temperature 30-80 ° C and pH 7-1
It is heated and concentrated under the condition of No. 2 to prepare an iminocarboxylic acid salt aqueous solution having a concentration of 40 to 70% by weight and a pH of 7 to 12, and this is treated at a temperature in the range of 30 to 70 ° C. According to this aspect, coloration in the concentration process can be prevented, and the iminocarboxylic acid salt can be handled as a stable and uniform aqueous solution without crystal precipitation and solidification.
【００２１】本発明の取り扱い方法によれば、イミノカ
ルボン酸塩を常に均一な水溶液として取り扱うことがで
きるため、保温、撹拌など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、貯槽などか
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当
たっての気相部の条件に特に制限はなく、窒素、アルゴ
ンなどの不活性ガス、空気などを用いることができる。According to the handling method of the present invention, since the iminocarboxylic acid salt can be always handled as a uniform aqueous solution, it can be stored in a storage container without requiring a special device such as heat retention or stirring. Liquid can be sent from a reaction tank, a storage tank or the like directly to a desired place through a pipe, or filled in a tank truck, a tank wagon, a container, a drum or the like and transported. The conditions of the gas phase portion for storage or transportation are not particularly limited, and an inert gas such as nitrogen or argon, air or the like can be used.
【００２２】イミノカルボン酸塩水溶液を取り扱う際
の、例えばタンクに貯蔵する場合のタンクの構成材料と
しては炭素鋼、ステンレススチール鋼、ハステロイ鋼、
チタン合金鋼、ニッケル鋼などが用いられるが、イミノ
カルボン酸塩水溶液が接触する部分をグラスライニン
グ、テフロンなどによる樹脂ライニング、ゴムライニン
グなどとしてもよい。特に、ステンレススチール鋼が好
適に用いられる。When handling the iminocarboxylic acid salt aqueous solution, for example, when it is stored in a tank, the constituent material of the tank is carbon steel, stainless steel, Hastelloy steel,
Titanium alloy steel, nickel steel or the like is used, but the portion in contact with the aqueous iminocarboxylate solution may be glass lining, resin lining with Teflon or the like, or rubber lining. Particularly, stainless steel is preferably used.
【００２３】[0023]
【実施例】以下、実施例を挙げて本発明を更に具体的に
説明する。EXAMPLES The present invention will be described in more detail below with reference to 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を撹拌
機、還流冷却器付の４つ口フラスコに仕込み８０℃で８
時間反応させた。反応後の反応液を高速液体クロマトグ
ラフィー（島津製作所製ＬＣ−１０Ａ）を用いて分析し
た結果、前記一般式（１）においてＲ＝ＯＨ、Ｘ＝Ｎａ
であるＬ体（Ｄ／Ｌ（モル比）＝０／１）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。Synthetic Example 1 88 g of epoxysuccinic acid disodium salt, 88.5 g of disodium L-aspartate and 210 g of water were placed in a four-necked flask equipped with a stirrer and a reflux condenser and heated at 80 ° C. for 8 hours.
Allowed to react for hours. The reaction solution after the reaction was analyzed by high performance liquid chromatography (LC-10A manufactured by Shimadzu Corporation), and as a result, in the general formula (1), R = OH and X = Na.
165 g of the tetrasodium salt of the iminocarboxylic acid of the L form (D / L (molar ratio) = 0/1) was contained.
【００２５】合成例２ 合成例１において、Ｌ−アスパラギン酸２ナトリウムの
代わりにＤ−アスパラギン酸２ナトリウムを用いた以外
は合成例１と同様にして、前記一般式（１）においてＲ
＝ＯＨ、Ｘ＝ＮａであるＤ体（Ｄ／Ｌ（モル比）＝１／
０）のイミノカルボン酸４ナトリウムを１６４．５ｇを
含む水溶液を得た。Synthesis Example 2 R in the above general formula (1) was prepared in the same manner as in Synthesis Example 1 except that D-aspartate disodium was used in place of L-aspartate disodium.
= OH, X = Na D-form (D / L (molar ratio) = 1 /
An aqueous solution containing 164.5 g of tetrasodium iminocarboxylate of 0) was obtained.
【００２６】合成例３ Ｌ−アスパラギン酸２ナトリウム塩水溶液（濃度２６．
５重量％）３３４ｇおよびエポキシコハク酸２ナトリウ
ム塩水溶液（濃度３０重量％）２９３ｇを用い合成例１
と同様にして前記一般式（１）においてＲ＝ＯＨ、Ｘ＝
ＮａであるＬ体（Ｄ／Ｌ（モル比）＝０）のイミノカル
ボン酸４ナトリウム塩１６２．４ｇを含む水溶液を得
た。Synthesis Example 3 L-aspartic acid disodium salt aqueous solution (concentration: 26.
5 wt%) and 293 g of epoxysuccinic acid disodium salt aqueous solution (concentration 30 wt%) 293 g
In the general formula (1), R = OH, X =
An aqueous solution containing 162.4 g of an iminocarboxylic acid tetrasodium salt of L-form (D / L (molar ratio) = 0) that is Na was obtained.
【００２７】実施例１〜８、１０〜１５および比較例１
〜５ 合成例１および２で得られたＬ−イミノカルボン酸４ナ
トリウムおよびＤ−イミノカルボン酸４ナトリウムの水
溶液を混合し、表１に示すＤ体／Ｌ体のモル比、ｐＨお
よび濃度を有するイミノカルボン酸４ナトリウムの水溶
液を調製し、この水溶液を表１に示す温度にて保存し
た。調製直後の水溶液の外観および１ケ月間保存した後
の水溶液を外観を観察し、その結果を表１に示した。ま
た、調製直後の水溶液の粘度も表１に示した。Examples 1-8, 10-15 and Comparative Example 1
~ 5 The aqueous solution of tetrasodium L-iminocarboxylate and tetrasodium D-iminocarboxylate obtained in Synthesis Examples 1 and 2 are mixed to have a molar ratio of D-form / L-form, pH and concentration shown in Table 1. An aqueous solution of tetrasodium iminocarboxylic acid was prepared and stored at the temperature shown in Table 1. The appearance of the aqueous solution immediately after preparation and the external appearance of the aqueous solution after storage for 1 month were observed, and the results are shown in Table 1. The viscosity of the aqueous solution immediately after preparation is also shown in Table 1.
【００２８】表１の結果から、前記４つの要件を満足さ
せることにより、イミノカルボン酸４ナトリウム塩を安
定かつ均一な水溶液として取り扱えることが分かる。From the results shown in Table 1, it is understood that by satisfying the above four requirements, the tetrasodium iminocarboxylic acid can be handled as a stable and uniform aqueous solution.
【００２９】実施例９ 合成例３で得られた濃度２６重量％のＬ−イミノカルボ
ン酸４ナトリウム塩水溶液をロータリーエバポレーター
を用いて内温７０℃で濃縮して濃度５５重量％の水溶液
とした。この際水溶液の着色は認められなかった。得ら
れた水溶液を表１に示す条件にて保存した。調製直後の
水溶液の外観および１ケ月間保存した後の水溶液の外観
を観察し、その結果を表１に示した。また、調製直後の
水溶液の粘度も表１に示した。Example 9 The aqueous solution of L-iminocarboxylic acid tetrasodium salt having a concentration of 26% by weight obtained in Synthesis Example 3 was concentrated at an internal temperature of 70 ° C. using a rotary evaporator to obtain an aqueous solution having a concentration of 55% by weight. At this time, no coloring of the aqueous solution was observed. The obtained aqueous solution was stored under the conditions shown in Table 1. The appearance of the aqueous solution immediately after preparation and the appearance of the aqueous solution after storage for one month were observed, and the results are shown in Table 1. The viscosity of the aqueous solution immediately after preparation is also shown in Table 1.
【００３０】[0030]
【表１】 [Table 1]
【００３１】[0031]
【発明の効果】本発明の方法によれば、イミノカルボン
酸塩を水溶液として長期にわたって、イミノカルボン酸
塩結晶の析出あるいは水溶液の固化を生じることなく、
安定的に取り扱うことができる。EFFECTS OF THE INVENTION According to the method of the present invention, an iminocarboxylic acid salt is used as an aqueous solution for a long period of time without causing precipitation of iminocarboxylic acid salt crystals or solidification of the aqueous solution.
It can be handled stably.
【００３２】本発明の方法によれば、イミノカルボン酸
塩水溶液の粘度が１０，０００ｃｐｓ以下なので、この
水溶液の取り扱いが容易である。According to the method of the present invention, since the viscosity of the iminocarboxylic acid salt aqueous solution is 10,000 cps or less, the aqueous solution is easy to handle.
【００３３】本発明の方法によれば、イミノカルボン酸
塩を長期にわたり安定かつ均一な水溶液として取り扱う
ことが可能であり、保温、撹拌などの特別な装置を必要
とすることないので、その取り扱いが簡便かつ容易であ
る。本発明の方法によれば、−１０〜１０℃あるいは３
０〜７０℃という低温あるいは高温においてもイミノカ
ルボン酸塩を安定かつ均一な水溶液として取り扱うこと
ができる。According to the method of the present invention, it is possible to handle the iminocarboxylic acid salt as a stable and uniform aqueous solution for a long period of time, and no special equipment such as heat retention or stirring is required. Simple and easy. According to the method of the present invention, -10 to 10 ° C or 3
The iminocarboxylic acid salt can be treated as a stable and uniform aqueous solution even at a low temperature or high temperature of 0 to 70 ° C.
Claims (4)
ウム、カリウムまたはアンモニウム基を表す）で表され
るイミノカルボン酸塩を取り扱うに際して、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をＤ
体／Ｌ体（モル比）＝１／０〜０．７／０．３またはＤ
体／Ｌ体（モル比）＝０／１〜０．３／０．７とし、か
つ該イミノカルボン酸塩を濃度４０〜７０重量％および
ｐＨ７〜１２に調整した水溶液として取り扱うことを特
徴とするイミノカルボン酸塩の取り扱い方法。1. The following general formula (1): (Wherein R represents a hydrogen atom or a hydroxyl group, and X represents a sodium, potassium or ammonium group), when handling an iminocarboxylic acid salt, the isomer ratio of the aspartic acid skeleton portion of the iminocarboxylic acid salt To D
Body / L body (molar ratio) = 1/0 to 0.7 / 0.3 or D
Body / L body (molar ratio) = 0/1 to 0.3 / 0.7, and the iminocarboxylic acid salt is treated as an aqueous solution adjusted to a concentration of 40 to 70% by weight and a pH of 7 to 12. How to handle iminocarboxylic acid salts.
り扱う請求項１記載の方法。2. The method according to claim 1, wherein the aqueous solution is handled at a temperature in the range of 30 to 70 ° C.
取り扱う請求項１記載の方法。3. The method according to claim 1, wherein the aqueous solution is handled at a temperature in the range of −10 to 10 ° C.
ある請求項１、２または３記載の方法。4. The method according to claim 1, 2 or 3, wherein X in the general formula (1) is sodium.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7250531A JPH08169866A (en) | 1994-10-20 | 1995-09-28 | Handling of iminocarboxylate salt |
| US08/544,784 US6063302A (en) | 1994-10-20 | 1995-10-18 | Method for handling iminocarboxylic acid salt |
| TW084111126A TW296372B (en) | 1994-10-20 | 1995-10-20 |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6-254936 | 1994-10-20 | ||
| JP25493694 | 1994-10-20 | ||
| JP7250531A JPH08169866A (en) | 1994-10-20 | 1995-09-28 | Handling of iminocarboxylate salt |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08169866A true JPH08169866A (en) | 1996-07-02 |
Family
ID=26539808
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7250531A Pending JPH08169866A (en) | 1994-10-20 | 1995-09-28 | Handling of iminocarboxylate salt |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08169866A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1371630A3 (en) * | 2002-06-11 | 2004-07-07 | Nippon Shokubai Co., Ltd. | Aminopolycarboxylic acid aqueous solution composition and stabilization method of aminopolycarboxylic acid |
| WO2005116158A1 (en) * | 2004-05-31 | 2005-12-08 | Nippon Shokubai Co., Ltd. | Chelate compound-containing composition and use as detergents thereof |
| JP2006096978A (en) * | 2004-05-31 | 2006-04-13 | Nippon Shokubai Co Ltd | Chelate compound-containing composition and use as detergent thereof |
| JP2010096950A (en) * | 2008-10-16 | 2010-04-30 | Konica Minolta Business Technologies Inc | Method of manufacturing toner, and toner |
-
1995
- 1995-09-28 JP JP7250531A patent/JPH08169866A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1371630A3 (en) * | 2002-06-11 | 2004-07-07 | Nippon Shokubai Co., Ltd. | Aminopolycarboxylic acid aqueous solution composition and stabilization method of aminopolycarboxylic acid |
| US7319165B2 (en) | 2002-06-11 | 2008-01-15 | Nippon Shokubai Co., Ltd. | Aminopolycarboxylic acid aqueous solution composition and stabilization method of aminopolycarboxlic acid |
| WO2005116158A1 (en) * | 2004-05-31 | 2005-12-08 | Nippon Shokubai Co., Ltd. | Chelate compound-containing composition and use as detergents thereof |
| JP2006096978A (en) * | 2004-05-31 | 2006-04-13 | Nippon Shokubai Co Ltd | Chelate compound-containing composition and use as detergent thereof |
| JP2010096950A (en) * | 2008-10-16 | 2010-04-30 | Konica Minolta Business Technologies Inc | Method of manufacturing toner, and toner |
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