JP2011231060A - Malic acid structure containing amino compound and its production method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a malic acid structure containing amino compound which has a sufficient iron ion chelating ability as compared with a conventional chelating agent.SOLUTION: The malic acid structure containing amino compound is a compound shown by General Formula (1) (wherein R, Rand Rare each independently hydrogen, hydroxyl alkyl, 1-20C alkyl or -CHCHCOOM; Rand Rare each independently hydrogen or hydroxy; and Ms are each independently hydrogen, alkali metal atom, alkaline earth metal atom, ammonium ion or amine salt).

Description

  The present invention relates to a malic acid structure-containing amino compound and a method for producing the same. More specifically, the present invention relates to a malic acid structure-containing amino compound having a plurality of malic acid structures and a method for producing the same.

  Since chelating agents can sequester metal ions by forming two or more coordination bonds, detergents, fibers, paper pulp, metal surfaces are used to remove the harmful effects of the presence of metal ions. It is used in various fields such as processing and photography, and is now indispensable for the chemical industry and daily life. For example, in the field of detergents, etc., it is used to remove metal ions such as calcium and magnesium in hard water in the preparation of water to be used. It is used to suppress decomposition by metal ions.

As such a chelating agent, for example, ethylenediaminetetraacetic acid (EDTA) or the like has been conventionally used. In recent years, N-bishydroxyalkylamino acids, particularly N-bishydroxyethylaspartic acids, are used in various applications. It attracts attention because it exhibits chelating performance (for example, Patent Document 1).
However, in recent years, for example, in the detergent field, there has been a strong demand for a compact detergent. Along with this, chelating agents have been required to have a plurality of functions. For example, there is a problem that yellowing of fibers occurs due to adsorption of iron ions to the fibers in the wash water, but the chelating agent has a function of removing heavy metal ions such as iron ions in addition to calcium ions (iron Ion chelating ability) is required. However, the iron ion chelating ability of the conventional chelating agent is not always satisfactory under the washing conditions, and a chelating agent having higher iron ion chelating ability is required.

JP 2003-252839 A

  An object of the present invention is to provide a malic acid structure-containing amino compound having sufficient iron ion chelating ability as compared with conventional chelating agents. Another object of the present invention is to provide a production method capable of easily producing a malic acid structure-containing amino compound having sufficient iron ion chelating ability as compared with conventional chelating agents.

  The present inventors have intensively studied to solve the above problems. As a result, the inventors have found that a specific malic acid structure-containing amino compound exhibits an iron ion chelating ability superior to that of the prior art, and has completed the present invention.

  That is, the malic acid structure-containing amino compound of the present invention is represented by the following general formula (1).

In the general formula (1), R ₁ , R ₂ and R ₃ are each independently a hydrogen atom, a group represented by the following general formula (2), an alkyl group having 1 to 20 carbon atoms, —CH ₂ CH _2. COOM is represented, R ₄ and R ₅ each independently represent a hydrogen atom or a hydroxyl group, and M independently represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium ion, or an amine salt.

In the said General formula (2), Z represents a C2-C4 alkylene group, n represents the average number of repeating units, and represents the number of 0-5.

  According to another aspect of the present invention, a method for producing a malic acid structure-containing amino compound is provided. The production method of the present invention is a production method characterized by comprising a step of reacting a compound selected from epoxy succinic acid, maleic acid and salts thereof with a compound represented by the following general formula (3).

In the general formula (3), R ₁ , R ₂ and R ₃ are each independently a hydrogen atom, a group represented by the following general formula (4), an alkyl group having 1 to 20 carbon atoms, —CH ₂ CH _2. COOM (wherein M represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium ion, or an amine salt).

In the said General formula (4), Z represents a C2-C4 alkylene group, n represents the average number of repeating units, and represents the number of 0-5.

ADVANTAGE OF THE INVENTION According to this invention, the malic acid structure containing amino compound excellent in the iron ion chelating ability than the conventional compound can be provided.
ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method which can manufacture the said malic acid structure containing amino compound simply can be provided.

[Malic acid structure-containing amino compound]
The malic acid structure-containing amino compound of the present invention is represented by the following general formula (1).

In the general formula (1), R ₁ , R ₂ and R ₃ are each independently a hydrogen atom, a group represented by the following general formula (2), an alkyl group having 1 to 20 carbon atoms, —CH ₂ CH _2. COOM is represented, R ₄ and R ₅ each independently represent a hydrogen atom or a hydroxyl group, and M independently represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium ion, or an amine salt.

In the said General formula (2), Z represents a C2-C4 alkylene group, n represents the average number of repeating units, and represents the number of 0-5.

  In the general formula (1), each M independently represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium ion, or an amine salt, specifically, an alkali metal such as lithium, sodium, or potassium; And alkaline earth metals such as magnesium; ammonium salts; organic amine salts. Among these, the form which is a sodium salt is particularly preferable.

In the general formula (1), when any of R ₁ , R ₂ and R ₃ is represented by the group represented by the general formula (2), Z in the general formula (2), that is, the number of carbon atoms Specifically, the alkylene group of 2-4 represents an ethylene group, a propylene group, and a butylene group.
Among these, the alkylene group having 2 to 4 carbon atoms is preferably an ethylene group or a propylene group, and particularly preferably an ethylene group, since iron ion chelating ability tends to be improved. In addition, since it is possible to produce with less impurities, the alkylene group having 2 to 4 carbon atoms is an ethylene group (—CH ₂ CH ₂ —), an isopropylene group (—CH (CH ₃ ) CH ₂ —, —CH ₂ CH (CH ₃ ) —), isobutylene group (—CH (C ₂ H ₅ ) CH ₂ —, —CH ₂ CH (C ₂ H ₅ ) —) is preferable, ethylene group, isopropylene group More preferably.

  In the general formula (2), n represents the average number of repeating units of the —Z—O— structure, and is preferably a number of 0 to 1 because the iron ion chelating ability tends to be improved. A number of ˜0.5 is more preferred.

In the general formula (1), the alkyl group having 1 to 20 carbon atoms that R ₁ , R ₂ , and R ₃ can take is an unsubstituted alkyl group as long as it has 1 to 20 carbon atoms. An alkyl group substituted with a functional group of When the other functional group is produced by reacting a compound selected from the epoxy succinic acid, maleic acid, and salts thereof (referred to as compound A) and the compound represented by the general formula (3), Although there is no limitation as long as the reaction between the compound A and the compound represented by the general formula (3) is not adversely affected, for example, a hydroxyl group, a sulfonic acid group, an acyl group, an ether group, an amide group, an ester Group.

In the malic acid structure-containing amino compound of the present invention, R ₁ , R ₂ and R ₃ represented by the general formula (1) are a hydrogen atom, a group represented by the following general formula (2), and a carboxyethyl group. It is preferably a hydrogen atom, and most preferably a hydrogen atom.

The malic acid structure-containing amino compound of the present invention has a hydroxyl group in the vicinity of the succinic acid structure because the iron ion chelating ability is improved when R ₄ and R ₅ are hydroxyl groups in the general formula (1). Therefore, for example, when added to a detergent composition, compatibility with a surfactant or the like is improved, which is preferable.

[Method for Producing Malic Acid Structure-Containing Amino Compound]
Although the malic acid structure-containing amino compound of the present invention may be produced by any method, it is represented by a compound (compound A) selected from epoxy succinic acid, maleic acid, and salts thereof, and the following general formula (3). What was manufactured from the manufacturing method which makes the compound made to react is preferable. According to this method, by-products are reduced, the purification process of the reaction product can be simplified, and physical properties such as iron ion chelating ability are good even when the product is not purified.

In the general formula (3), R ₁ , R ₂ and R ₃ are each independently a hydrogen atom, a group represented by the following general formula (4), an alkyl group having 1 to 20 carbon atoms, —CH ₂ CH _2. COOM (wherein M represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium ion, or an amine salt).

In the said General formula (4), Z represents a C2-C4 alkylene group, n represents the average number of repeating units, and represents the number of 0-5.

Among the compounds selected from epoxy succinic acid, maleic acid, and salts thereof used in the production method of the present invention, since by-products are reduced, epoxy succinic acid and epoxy succinic acid salts are preferable.
Examples of the salt include alkali metal salts, alkaline earth metal salts, ammonium salts, and amine salts. Specifically, alkali metals such as lithium salts, sodium salts, and potassium salts; alkaline earth metals such as calcium salts and magnesium salts. Examples include metals; ammonium salts; organic amine salts. Among these, the form which is a sodium salt is particularly preferable.

In the production method of the present invention, the preferred embodiments of R ₁ , R ₂ and R ₃ in the general formula (3) and the preferred embodiments of Z and n in the general formula (4) are as described above unless otherwise specified below. This is the same as in general formula (1) and general formula (2).

  Specific examples of the compound represented by the general formula (3) include diethylenetriamine, N ′-(2-hydroxyethyl) diethylenetriamine, N ′-(2-carboxyethyl) diethylenetriamine and the like.

When the compound represented by the above general formula (3) has a group represented by the general formula (2), for example, a method of adding an alkylene oxide to diethylenetriamine is preferably used. When the compound represented by the general formula (3) has a carboxyethyl group (—CH ₂ CH ₂ COOH) or a salt thereof, for example, Michael can be added to diethylenetriamine with acrylic acid or acrylate. Is preferably used.
From the viewpoint of reducing impurities, when the malic acid structure-containing amino compound of the present invention has a group represented by the general formula (2) and / or a carboxyethyl group, after reacting the compound A with diethylenetriamine, an alkylene oxide and It is preferable to produce by adding acrylic acid (salt).

(Reaction conditions)
In the production method of the present invention, the ratio of the compound A used in the reaction to the compound represented by the general formula (3) is preferably 180: 100 to 220: 100, more preferably 190. : 100 to 210: 100, and more preferably 195: 100 to 205: 100. If it exceeds the said range, it exists in the tendency for the yield of the malic acid structure containing amino compound of this invention to fall.

(Reaction solvent)
The solvent used in the production method of the present invention is preferably one that can dissolve the compound A and / or the compound represented by the general formula (3). From the viewpoint of improving the reaction yield, an aqueous solvent is preferable, and water is particularly preferable. In addition, depending on the application, mixing of the organic solvent into the malic acid structure-containing amino compound (containing composition) of the present invention is severely restricted. However, if it is water, the process of removing the solvent is unnecessary, so the production efficiency is high. In addition, it is preferable because coloring of the malic acid structure-containing amino compound (containing composition) of the present invention due to the thermal history at the stage of reducing the residual amount of solvent is suppressed. In addition, if water is used, the waste liquid and the like can be remarkably reduced as compared with the case where an organic solvent is used.

(Neutralization degree of raw materials during reaction)
In the production method of the present invention, since the reaction yield is improved, when the compound A is unneutralized or partially neutralized, it is preferably neutralized during the reaction. “Neutralize at the time of reaction” may be added to the reactor after neutralization in advance, and the compound A and the neutralizing agent are separately added to the reactor and the neutralization reaction and the above in the reactor. It represents that the reaction with the compound represented by the general formula (3) may be performed simultaneously. In the point which can improve a yield more, when the compound A is unneutralized or partially neutralized, it is preferable to neutralize with a basic substance beforehand before reaction. The compound A to be neutralized in advance before the reaction is preferably 50 mol% or more, more preferably 95 mol% or more, and more preferably 100 mol% (total amount) of all acid groups in the total amount of compound A used. It is particularly preferred. The compound A may be charged into the reactor in advance or may be gradually added to the reactor after the start of the reaction.

The neutralizing agent may be a basic compound, but potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and the like are preferable because the reaction yield is improved.
The ratio used of the neutralizing agent (excluding the compound represented by the general formula (3) and the reaction product thereof, the same shall apply hereinafter) and the compound A is the acid group (acid group + neutralization) of the compound A in a molar ratio. The acid group is preferably used so that the neutralized acid group is 50 mol or more and 100 mol or less, preferably 80 mol or more and 100 mol or less, 90 mol or more, 100 mol The following is more preferable, and 95 mol or more and 100 mol or less are further preferable. By making the neutralized acid group within the above range, the yield of the malic acid structure-containing amino compound of the present invention is improved.

(PH of the reaction solution during the reaction)
In the production method of the present invention, the pH during the reaction is 7.5 or more, preferably 9 or more, and more preferably 10 or more. If the pH during the reaction is less than 7.5, the yield decreases, which is not preferable.

(Method of adding reaction raw materials, etc.)
In the production method of the present invention, the neutralizing agent, the compound represented by the general formula (3), and the compound A may be previously charged in the reactor or may be gradually added to the reactor after the start of the reaction. I do not care. Since the raw material concentration at the time of the reaction can be increased and the reaction efficiency can be improved, it is preferable that at least one of the compound represented by the general formula (3) or the compound A is charged in the reactor in advance.
In the case where the compound represented by the general formula (3) is charged into the reactor before the start of the reaction, 50% by mass or more of the total amount of the compound represented by the general formula (3) is reacted before the start of the reaction. It is preferable to charge the container, more preferably 80% by mass or more, and most preferably the total amount.
When the compound A is gradually added to the reactor after the start of the reaction, it is preferable that 80% by mass or more of the total amount used is gradually added to the reactor after the start of the reaction, more preferably 90% by mass or more. The total amount is most preferred.
The compound A is preferably mixed with a solvent such as water and added dropwise to prevent side reactions.
In the present invention, the time of starting the reaction is the time when at least part of the compound represented by the general formula (3) and at least part of the compound A are both added to the reactor.

(Reaction temperature, reaction time)
In the production method of the present invention, the reaction temperature is preferably 50 ° C. or higher and 120 ° C. or lower.
When it is less than 50 ° C., the reaction rate becomes slow and the reaction efficiency becomes poor. Also, the reaction yield tends to decrease. If it exceeds 120 ° C., side reactions proceed and coloring of the reaction product increases.
In the production method of the present invention, the reaction time is preferably 0.5 hours or more and 10 hours or less. More preferably, it is 1 hour or more and 4.5 hours or less.

(Pressure and atmosphere during reaction)
In the production method of the present invention, the reaction may be performed under normal pressure, reduced pressure, or increased pressure. Since the reaction yield tends to improve, it is preferable to carry out the reaction under normal pressure or while removing the solvent under reduced pressure.
In the production method of the present invention, the reaction may be performed in an atmosphere of an inert gas such as nitrogen gas. Moreover, you may preserve | save in the atmosphere of inert gas, such as nitrogen gas, after reaction.
In the production method of the present invention, a reaction catalyst may be added.
In the production method of the present invention, a further neutralization step may be provided after the reaction for the purpose of improving storage stability.
In the production method of the present invention, it is also possible to use a compound in which the carboxyl group of compound A is changed to the corresponding ester or amide instead of compound A, and it is included in the production method of the present invention. An ester group or amide group hydrolysis step may be provided. From the viewpoint of simplifying the production process and reducing by-products, it is preferable to use Compound A.

In the production method of the present invention, when the malic acid structure-containing amino compound of the present invention is produced using a solvent, a concentration adjustment step such as a drying step and / or a concentration step or a further dilution step is provided as desired. Also good.

[Malic acid structure-containing amino compound-containing composition]
The malic acid structure-containing amino compound-containing composition of the present invention contains the malic acid structure-containing amino compound of the present invention as an essential component, and is represented as an optional component by a residual raw material (the above compound A or the above general formula (3)). Compounds), by-products, water, methanol and other solvents.

  The malic acid structure-containing amino compound of the present invention contained in the malic acid structure-containing amino compound-containing composition of the present invention is preferably based on 100% by mass of the solid content of the malic acid structure-containing amino compound-containing composition of the present invention. And preferably 1% by mass or more and 99% by mass or less. When the malic acid structure-containing amino compound of the present invention contained in the malic acid structure-containing amino compound-containing composition of the present invention is 99% by mass or less, handling such as solubility when solidified becomes easy.

  The residual raw material contained in the malic acid structure-containing amino compound-containing composition of the present invention is preferably 0% by mass or more with respect to 100% by mass of the solid content of the malic acid structure-containing amino compound-containing composition of the present invention. 30% by mass or less.

A preferable content when the malic acid structure-containing amino compound-containing composition of the present invention contains water is 0.5% by mass or more when the malic acid structure-containing amino compound-containing composition of the present invention is solid. It is below mass%. It is preferable that the water content falls within the above range because handling becomes easy.
In addition, when the malic acid structure-containing amino compound-containing composition of the present invention is liquid, the content of water of the malic acid structure-containing amino compound-containing composition of the present invention is preferably the malic acid structure-containing amino compound-containing composition of the present invention. 30 mass% or more and 95 mass% or less with respect to 100 mass% of things. If the water content exceeds 95% by mass, the efficiency during transportation and storage may be significantly reduced. On the other hand, if the content of water is less than 30% by mass, the viscosity will increase and handling as a liquid will be difficult, and the storage stability will deteriorate, such as the formation of precipitates. More preferably, it is 40 mass% or more and 75 mass% or less.

[Carboxyethylation of malic acid structure-containing amino compound]
As described above, when the malic acid structure-containing amino compound of the present invention has a hydrogen atom in a part of R ₁ , R ₂ , or R _{3 in} the general formula (1), an acrylic compound (salt) or the like You may make it react with saturated carboxylic acid and introduce | transduce a carboxyl group and / or its salt.
In this case, the total amount of R ₁ , R ₂ and R ₃ (limited to those which are hydrogen atoms) in the above general formula may be carboxyethylated, or a part thereof may be carboxyethylated. The use ratio of the hydrogen atom and acrylic acid in the carboxyethylation reaction is preferably 10 to 105 mol with respect to 100 mol of the hydrogen atom.
As the reaction conditions in this case, for example, the compound A can be reacted under the reaction conditions of the compound represented by the general formula (3). Within the above range, the chelating ability of calcium ions tends to increase.

[Production Process of Acid-Type Malic Acid Structure-Containing Amino Compound]
In the production method of the present invention, when the carboxyl group of the resulting malic acid structure-containing amino compound is produced in a neutralized form, the acid-type malic acid structure-containing amino compound (apple with neutralized amino group) You may provide the process of manufacturing an acid structure containing amino compound.
The step of producing the acid type malic acid structure-containing amino compound is preferably produced by (i) adding an acid to the malic acid structure-containing amino compound aqueous solution or the like to make the pH acidic. In addition, if precipitation of the salt etc. which generate | occur | produces in this case arises, you may remove by filtration etc.
Further, in the step of producing the acid type malic acid structure-containing amino compound, (ii) an organic solvent is added to the aqueous solution of the malic acid structure-containing amino compound in order to isolate the acid type malic acid structure-containing amino compound. Then, a step of precipitating the malic acid structure-containing amino compound and filtering the precipitated malic acid structure-containing amino compound may be included. The step (ii) is preferably performed after the step (i).
The steps (i) and (ii) can be repeated as necessary.
In the step (i), the acid may be any of a mineral acid and an organic acid, and examples thereof include hydrochloric acid, sulfuric acid, nitric acid, sulfurous acid, phosphoric acid, boric acid, carbonic acid, acetic acid, and citric acid. From this point of view, it is preferable to use hydrochloric acid. In the step (i), the pH is preferably less than 2 because production efficiency is high. More preferably, the pH is about 1.
The addition amount of the acid in the step (i) is preferably equimolar or more, preferably 1.3 times mol or more with respect to the carboxyl group.
In the above steps (i) and (ii), an aqueous solution of a malic acid structure-containing amino compound or the like refers to an aqueous solution or aqueous solution of a malic acid structure-containing amino compound, and preferably the malic acid structure-containing amino compound is water or water. And a solution dissolved in a mixed solvent composed of an organic solvent compatible with water such as lower alcohol.
After producing an aqueous solution of an acid-type malic acid structure-containing amino compound, it may be dried and solidified.

[Use]
The malic acid structure-containing amino compound of the present invention (hereinafter, the compound of the present invention) or the malic acid structure-containing amino compound-containing composition (hereinafter, the composition of the present invention) can be used as a chelating agent. It can be used as an additive for fiber treatment agents, dispersants, detergent compositions and the like. As a detergent additive, it can be used by being added to detergents for various uses such as clothing, tableware, dwelling, hair, body, toothpaste, and automobile.

<Water treatment agent>
The compound of the present invention or the composition of the present invention can be added to a water treatment agent. If necessary, the water treatment agent may contain a polymerized phosphate, phosphonate, anticorrosive, slime control agent, and chelating agent as other compounding agents.

  The water treatment agent is useful for scale prevention in a cooling water circulation system, a boiler water circulation system, a seawater desalination apparatus, a pulp digester, a black liquor concentration tank, and the like. Further, any appropriate water-soluble polymer may be included as long as it does not affect the performance and effects.

<Fiber treatment agent>
The compound of the present invention or the composition of the present invention can be added to a fiber treatment agent. The fiber treatment agent includes at least one selected from the group consisting of a dye, a peroxide and a surfactant, and the composition of the present invention.

  The content of the compound of the present invention in the fiber treatment agent is preferably 1 to 100% by weight, more preferably 5 to 100% by weight, based on the entire fiber treatment agent. Further, any appropriate water-soluble polymer may be included as long as the performance and effects are not affected.

  Below, the compounding example of the fiber processing agent which is closer to embodiment is shown. This fiber treatment agent can be used in the steps of refining, dyeing, bleaching and soaping in fiber treatment. Examples of dyeing agents, peroxides and surfactants include those usually used for fiber treatment agents.

  The compounding ratio of the compound of the present invention to at least one selected from the group consisting of a dye, a peroxide and a surfactant is, for example, for improving the whiteness, color unevenness and dyeing tempering degree of the fiber. The ratio of 0.1 to 100 parts by weight of at least one selected from the group consisting of a staining agent, a peroxide and a surfactant with respect to 1 part by weight of the composition of the present invention in terms of a pure amount of the fiber treatment agent. It is preferable to use the composition blended in as a fiber treatment agent.

  Arbitrary appropriate fiber can be employ | adopted as a fiber which can use the said fiber processing agent. Examples thereof include cellulosic fibers such as cotton and hemp, chemical fibers such as nylon and polyester, animal fibers such as wool and silk, semi-synthetic fibers such as human silk, and woven fabrics and blended products thereof.

  When the fiber treatment agent is applied to the refining process, it is preferable to blend the compound of the present invention or the composition of the present invention with an alkali agent and a surfactant. When applied to the bleaching step, it is preferable to blend the compound of the present invention or the composition of the present invention, a peroxide, and a silicic acid-based agent such as sodium silicate as a decomposition inhibitor for the alkaline bleaching agent.

<Inorganic pigment dispersant>
The compound of the present invention or the composition of the present invention can be added to an inorganic pigment dispersant. In the inorganic pigment dispersant, condensed phosphoric acid and its salt, phosphonic acid and its salt, and polyvinyl alcohol may be used as other compounding agents as required.

  The content of the compound of the present invention in the inorganic pigment dispersant is preferably 5 to 100% by weight with respect to the whole inorganic pigment dispersant. Further, any appropriate water-soluble polymer may be included as long as it does not affect the performance and effect.

  The inorganic pigment dispersant can exhibit good performance as a dispersant for heavy or light calcium carbonate or clay inorganic pigment used in paper coating. For example, by adding a small amount of an inorganic pigment dispersant to an inorganic pigment and dispersing it in water, high concentration calcium carbonate having low viscosity and high fluidity and good aging stability of their performance. High concentration inorganic pigment slurries such as slurries can be produced.

  When the inorganic pigment dispersant is used as a dispersant for an inorganic pigment, the amount of the inorganic pigment dispersant used is preferably 0.05 to 2.0 parts by weight with respect to 100 parts by weight of the inorganic pigment. When the amount of the inorganic pigment dispersant used is within the above range, a sufficient dispersion effect can be obtained, and an effect commensurate with the addition amount can be obtained, which can be economically advantageous.

<Detergent composition>
The compounds of the invention or the compositions of the invention can also be added to detergent compositions.
The content of the compound of the present invention in the detergent composition is not particularly limited. However, from the viewpoint that it can exhibit excellent iron ion chelating ability, the content of the compound of the present invention is preferably 0.1 to 15% by mass, more preferably based on the total amount of the detergent composition. It is 0.3-10 mass%, More preferably, it is 0.5-5 mass%.
Detergent compositions used in detergent applications usually include surfactants and additives used in detergents. Specific forms of these surfactants and additives are not particularly limited, and conventionally known knowledge can be appropriately referred to in the detergent field. The detergent composition may be a powder detergent composition or a liquid detergent composition.
The surfactant is one or more selected from the group consisting of an anionic surfactant, a nonionic surfactant, a cationic surfactant and an amphoteric surfactant. When two or more kinds are used in combination, the total amount of the anionic surfactant and the nonionic surfactant is preferably 50% by mass or more, more preferably 60% by mass with respect to the total amount of the surfactant. It is above, More preferably, it is 70 mass% or more, Most preferably, it is 80 mass% or more.
Examples of the anionic surfactant include alkylbenzene sulfonate, alkyl ether sulfate, alkenyl ether sulfate, alkyl sulfate, alkenyl sulfate, α-olefin sulfonate, α-sulfo fatty acid or ester salt, alkane sulfonate. , Saturated fatty acid salt, unsaturated fatty acid salt, alkyl ether carboxylate, alkenyl ether carboxylate, amino acid type surfactant, N-acyl amino acid type surfactant, alkyl phosphate ester or salt thereof, alkenyl phosphate ester or Its salts are preferred. An alkyl group such as a methyl group may be branched from the alkyl group or alkenyl group in these anionic surfactants.
Nonionic surfactants include polyoxyalkylene alkyl ethers, polyoxyalkylene alkenyl ethers, polyoxyethylene alkyl phenyl ethers, higher fatty acid alkanolamides or alkylene oxide adducts thereof, sucrose fatty acid esters, alkyl glycoxides, fatty acid glycerin monoesters. Esters, alkylamine oxides and the like are preferred. An alkyl group such as a methyl group may be branched from the alkyl group or alkenyl group in these nonionic surfactants.
As the cationic surfactant, a quaternary ammonium salt or the like is suitable. As the amphoteric surfactant, a carboxyl type amphoteric surfactant, a sulfobetaine type amphoteric surfactant, and the like are suitable. The alkyl group and alkenyl group in these cationic surfactants and amphoteric surfactants may be branched from an alkyl group such as a methyl group.
The blending ratio of the surfactant is usually 10 to 60% by mass, preferably 15 to 50% by mass, more preferably 20 to 45% by mass, particularly preferably based on the total amount of the detergent composition. Is 25-40 mass%. If the surfactant content is too small, sufficient detergency may not be achieved, and if the surfactant content is too high, the economy may be reduced.
Additives include anti-redeposition agent to prevent redeposition of contaminants such as alkali builder, chelate builder, sodium carboxymethyl cellulose, stain inhibitor such as benzotriazole and ethylene-thiourea, soil release agent, color transfer Inhibitors, softeners, alkaline substances for pH adjustment, fragrances, solubilizers, fluorescent agents, colorants, foaming agents, foam stabilizers, polishes, bactericides, bleaching agents, bleaching aids, enzymes, dyes A solvent or the like is preferable. In the case of a powder detergent composition, it is preferable to blend zeolite.
The detergent composition may include a detergent builder. Other detergent builders are not particularly limited, but include, for example, alkali builders such as carbonates, bicarbonates and silicates, tripolyphosphates, pyrophosphates, bow nitrate, nitrilotriacetate, ethylenediaminetetraacetate, Examples thereof include acid salts, (meth) acrylic acid copolymer salts, acrylic acid-maleic acid copolymers, chelate builders such as fumarate and zeolite, and carboxyl derivatives of polysaccharides such as carboxymethylcellulose. Examples of the counter salt used in the builder include alkali metals such as sodium and potassium, ammonium and amine.
The total blending ratio of the additive and other builder for detergent is usually preferably 0.1 to 50% by mass with respect to 100% by mass of the cleaning composition. More preferably, it is 0.2-40 mass%, More preferably, it is 0.3-35 mass%, Most preferably, it is 0.4-30 mass%, Most preferably, it is 0.5-20 mass% or less. It is. If the additive / other detergent builder content is less than 0.1% by mass, sufficient detergent performance may not be achieved, and if it exceeds 50% by mass, the economy may be reduced.
In addition, the concept of the above-mentioned detergent composition includes specific detergents such as synthetic detergents for household detergents, textile industry and other industrial detergents, hard surface cleaners, and bleaching detergents that enhance one of the components. Detergents that are only used are also included.
When the detergent composition is a liquid detergent composition, the amount of water contained in the liquid detergent composition is usually preferably 0.1 to 75% by mass, more preferably based on the total amount of the liquid detergent composition. Is 0.2 to 70% by mass, more preferably 0.5 to 65% by mass, even more preferably 0.7 to 60% by mass, particularly preferably 1 to 55% by mass, Preferably it is 1.5-50 mass%.
When the detergent composition is a liquid detergent composition, the detergent composition preferably has a kaolin turbidity of 200 mg / L or less, more preferably 150 mg / L or less, and even more preferably 120 mg / L or less. Especially preferably, it is 100 mg / L or less, Most preferably, it is 50 mg / L or less.
Further, the change (difference) in kaolin turbidity when the compound of the present invention or the composition of the present invention is added to the liquid detergent composition is preferably 500 mg / L or less, more preferably It is 400 mg / L or less, more preferably 300 mg / L or less, particularly preferably 200 mg / L or less, and most preferably 100 mg / L or less. As the kaolin turbidity value, a value measured by the following method is adopted.

<Measurement method of kaolin turbidity>
A sample (liquid detergent) uniformly stirred in a 50 mm square cell having a thickness of 10 mm was removed and air bubbles were removed. Then, a NDU2000 manufactured by Nippon Denshoku Co., Ltd. Kaolin turbidity: mg / L) is measured.
Proteases, lipases, cellulases, and the like are suitable as enzymes that can be incorporated into the cleaning composition. Of these, proteases, alkaline lipases, and alkaline cellulases that are highly active in an alkaline cleaning solution are preferred.
The amount of the enzyme added is preferably 5% by mass or less with respect to 100% by mass of the cleaning composition. If it exceeds 5% by mass, improvement in detergency cannot be seen, and the economy may be reduced.
Even when the detergent composition is used in an area of hard water (for example, 100 mg / L or more) having a high concentration of calcium ions and magnesium ions, salt precipitation is small and has an excellent cleaning effect. This effect is particularly pronounced when the detergent composition contains an anionic surfactant such as LAS.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples. Unless otherwise specified, parts and% in the examples are based on weight.
The compound A and the compound represented by the general formula (3) were quantified by high performance liquid chromatography. The production of the malic acid structure-containing amino compound was confirmed by liquid chromatography mass spectrometry (LC-MS). The analysis conditions are as follows.

(Measurement conditions for high performance liquid chromatography)
Analysis conditions:
Column: ODS-80TM (manufactured by Tosoh Corporation)
Mobile phase: 5 mM ammonium dihydrogen phosphate (pH = 2.4)
Mobile phase flow rate: 0.5 ml / min
Detection wavelength: UV, 210 nm
Column temperature: 20 ° C.

(Measurement of solid content)
The solid content concentration of the reaction solution and the like was calculated from the change in mass before and after drying in an oven at 170 ° C. for 1 hour.

(Evaluation of iron ion chelating ability)
In a container that can be sealed, a 5% by mass chelating agent aqueous solution, a 0.135M iron ion 0.1N nitric acid aqueous solution, and a 30% by mass sodium hydroxide aqueous solution, the test solution chelating agent concentration being 0.2% by mass, iron ion A solution of 50 ml diluted with water was prepared so as to have a concentration of 300 ppm and a sodium hydroxide concentration of 3% by mass. When preparing the solution, an iron ion nitric acid aqueous solution is added last. The solution was shaken and allowed to stand at room temperature for 4 hours. After standing, the supernatant was filtered off, and the filtrate was quantified for iron ions using an ICP emission spectrometer (manufactured by Shimadzu Corporation). The soluble iron ion concentration (%) calculated by the following formula was defined as the iron ion chelating ability.

In the above formula, the initial iron ion concentration is 300 ppm.

Example 1
A glass reactor equipped with a thermometer and a stirrer was charged with 397.4 parts by mass of an aqueous solution of disodium epoxy succinate (purity of disodium epoxy succinate of 31.0%), and slowly stirred while stirring 36.2 parts by mass of diethylenetriamine. It was dripped. Thereafter, the temperature of the reaction solution was raised to 75 ° C., and the reaction was carried out at the same temperature for 5 hours to obtain the compound (1) of the present invention (the obtained reaction solution was mixed with the compound (salt) composition of the present invention). (Referred to as (1)).
When the epoxy succinic acid in the compound (salt) composition (1) of the present invention was analyzed by high performance liquid chromatography and the conversion was calculated, the conversion of epoxy succinic acid was 100%.
When ¹ H-NMR of the compound (salt) composition (1) of the present invention was measured, peaks of 2.5, 3.3, and 4.1 ppm were assigned, and the compound (1) of the present invention (that is, the above) In general formula (1), it was confirmed that R ₁ , R ₂ , R ₃ are H, R ₄ , R ₅ are hydroxyl groups, and M is Na.
It was 38.9 mass% when solid content concentration of the compound (salt) composition (1) of this invention was measured.

(Example 2)
Table 1 shows the results obtained by measuring the iron ion chelating ability of the compound (1) of the present invention obtained in Example 1 according to the above evaluation method.

(Comparative Example 1)
Table 1 shows the results of measuring the iron ion chelating ability of ethylenediaminetetraacetic acid tetrasodium (EDTA) (manufactured by Dojindo Laboratories), which is a typical chelating agent, according to the above evaluation method.

From the above results, it became clear that the malic acid structure-containing amino compound of the present invention has a higher iron ion chelating ability than conventional chelating agents.

  The malic acid structure-containing amino compound of the present invention has a high iron ion chelating ability. Therefore, when it uses for additives, such as a water treatment agent, a builder for detergents, a detergent composition, a dispersing agent, a cleaning agent, it can exhibit the especially outstanding performance.

Claims (3)

A compound represented by the following general formula (1).

In the general formula (1), R ₁ , R ₂ and R ₃ are each independently a hydrogen atom, a group represented by the following general formula (2), an alkyl group having 1 to 20 carbon atoms, —CH ₂ CH _2. COOM is represented, R ₄ and R ₅ each independently represent a hydrogen atom or a hydroxyl group, and M independently represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium ion, or an amine salt.

In the said General formula (2), Z represents a C2-C4 alkylene group, n represents the average number of repeating units, and represents the number of 0-5. A production method comprising a step of reacting a compound selected from epoxy succinic acid, maleic acid and salts thereof with a compound represented by the following general formula (3).

In the general formula (3), R ₁ , R ₂ and R ₃ are each independently a hydrogen atom, a group represented by the following general formula (4), an alkyl group having 1 to 20 carbon atoms, —CH ₂ CH _2. COOM (wherein M represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium ion, or an amine salt).

In the said General formula (4), Z represents a C2-C4 alkylene group, n represents the average number of repeating units, and represents the number of 0-5. A chelating agent comprising the compound of claim 1.