JPH0867659A - New lysine derivative, its production and detergent composition - Google Patents

Abstract

PURPOSE: To obtain a new lysine derivative having high water-solubility and chelating performance and useful as a chelating agent excellent in biodegradability. CONSTITUTION: The compound of the formula (X1 and X5 are each an alkali metal, an alkaline earth metal or ammonium). The compound is obtained by reacting an epoxysuccinic acid and/or its salts with lysine and/or its salts in an aqueous medium or an organic solvent such as dioxane at 40-150 deg.C. The lysines and epoxysuccinic acids are used at 1.6-2.2 molar ratio of the lysines to the epoxysuccinic acids. This detergent composition is prepared by including 1-40wt.% lysine derivative of the formula as an active ingredient therein. A chelating agent can be used in the field of fibers, paper pulp, detergents, metallic surface treating agents, photography, etc., for the purpose of sequestering.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel lysine derivative and a method for producing the same.

Another invention of the present invention relates to a novel detergent composition containing a novel lysine derivative.

[0003]

2. Description of the Related Art Chelating agents are used in various fields such as fibers, paper pulp, detergents, metal surface treatments, and photography for the purpose of sequestering metal ions, and are indispensable for removing the harmful effects of metal ions. There is no such thing. Among them, removal of calcium and magnesium in hard water is a process required in many fields including detergents, and in the bleaching process of the fiber and paper pulp industry, bleaching agent such as hydrogen peroxide is used. A chelating agent is used to suppress the decomposition of the metal by the metal. Ethylenediaminetetraacetic acid has been widely used as a chelating agent from the past, but it has been pointed out that this compound is not easily biodegraded, and its use is concerned from the viewpoint of environmental protection. Detergent builders have also been converted from phosphates to zeolites due to eutrophication problems, but this compound is insoluble in water and, if used in excess, will cause blockages in sewers and water treatment facilities. have.

[0004]

The present invention has been made in view of the above circumstances and provides a compound having high water solubility and chelating ability and excellent biodegradability. The purpose is to

It is another object of the production method of the present invention to provide a method for producing a compound having high water solubility and chelating ability and excellent biodegradability in good yield.

It is another object of the detergent composition of the present invention to provide a detergent composition having high water solubility and chelating ability and excellent biodegradability.

[0007]

Means for Solving the Problems As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that the novel lysine derivative has excellent performance capable of sufficiently satisfying the above-mentioned problems. The present invention has been completed. That is, the present invention provides a lysine derivative represented by the following general formula (1):

[0008]

[Chemical 3]

(In the formula, X _{1 to} X ₅ represent an alkali metal, an alkaline earth metal or an ammonium group, and they may be the same or different.), A method for producing the same and a lysine derivative thereof. It is a detergent composition.

The lysine derivative represented by the general formula (1) can be produced by, for example, a method of reacting epoxysuccinic acid and / or its salt with lysine and / or its salt. The lysine used in the present invention may be understood to be mainly L-lysine which is a natural amino acid. INDUSTRIAL APPLICABILITY The lysine derivative of the present invention has excellent chelating ability and can be widely used as a powder in a dry state or as an aqueous solution having an arbitrary concentration. In particular, when used in combination with a detergent for cleaning or the like, it exhibits excellent performance as a detergent composition.

The production method of the present invention is a method for producing the lysine derivative represented by the above general formula (1) by reacting epoxysuccinic acid and / or its salt with lysine and / or its salt. Examples of the epoxysuccinic acid salt include sodium salt, potassium salt, and ammonium salt of epoxysuccinic acid.

The raw material epoxysuccinic acid and / or salts thereof may be either a trans isomer or a cis isomer or a mixture thereof. Examples of the method for synthesizing epoxysuccinic acid and / or its salt include a method for producing a cis isomer by reacting maleic acid and hydrogen peroxide in an aqueous medium by a known method.

As the raw material lysine and / or its salt, L-lysine which is a natural amino acid and / or its salt is mainly used. Examples of the lysine salt include sodium salt, potassium salt, and ammonium salt of lysine.

In the production method of the present invention, lysine and / or epoxysuccinic acid and / or salts thereof are used.
Alternatively, the molar ratio of the salts is preferably 1.6 to 2.2, more preferably 1.9 to 2.1. Further, this production method is mainly carried out in an aqueous medium, but it can also be carried out in a medium containing an organic solvent which is inert under the reaction conditions, particularly a hydrophilic organic solvent such as dioxane, ethanol or methanol.

As a preferred production method of the present invention, first, an aqueous slurry and / or aqueous solution containing about 1 molar equivalent of alkali hydroxide and / or alkaline earth metal with respect to lysine and / or its salt is prepared. To do. The alkali hydroxide and / or alkaline earth metal is preferably sodium hydroxide. Then,
A method in which about 2 molar equivalents of cis-epoxysuccinic acid and / or its alkali metal salt and / or alkaline earth metal salt are added to the aqueous slurry and / or aqueous solution, and the mixture is heated and reacted. Is.

In the production method of the present invention, the reaction temperature is usually in the range of 40 to 150 ° C, preferably 70 to 100 ° C.

The reaction is completed by heating and stirring at this reaction temperature for several hours, and when the solvent is distilled off, the desired product is almost quantitatively obtained as an almost colorless solid. When reacting in an aqueous solution, the solvent is not distilled off,
It is preferable in the process because it can be directly used as a product. It is also possible to liberate the acid form by adding a common acid such as hydrochloric acid or sulfuric acid by a known method.

The detergent composition of the present invention has the above general formula (1).
The lysine derivative of The content of the lysine derivative contained in the detergent composition is not particularly limited, but is preferably 1 to 40% by weight, more preferably 3 to 25% by weight.

In addition, the detergent composition of the present invention usually contains a detergent surfactant. There are no particular restrictions on the type of surfactant for detergents used here, alkyl sulphates, alkyl benzene sulphates, alkyl benzene sulphonates, olefin sulphonates, alkoxylated alcohols, alkylphenols, alkylphenol sulphates, fatty acid sulphonates, fatty acid esters. Various conventionally known anionic surfactants such as sulfonates, nonionic surfactants, and cationic surfactants can be used, and they can be used alone, or if necessary. It is of course possible to use two or more kinds in combination. The content of these detergent surfactants in the detergent composition is preferably 1 to 40% by weight, more preferably 10 to 30% by weight.

In the detergent composition according to the present invention, in addition to the compound represented by the general formula (1) and the surfactant,
If desired, well-known cleaning aids, for example, builder compounds such as zeolite, enzymes such as protease, bleaching agents or bleaching aids such as perborate, stain inhibitors, anti-settling agents,
It is also possible to include an appropriate amount of a fabric softening agent or the like.

[0021]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

Example 1 To a four-necked flask containing 14.6 g (0.1 mol) of L-lysine and 100 g of water, 8.3 g of a 48 wt% sodium hydroxide aqueous solution was slowly added dropwise with stirring at room temperature. , 11 wt.g of 30 wt% disodium epoxysuccinate aqueous solution was added, and the mixture was heated at 85 ° C. for 6 hours and stirred. The reaction product (A) obtained after the solvent was distilled off was a colorless solid, and the reaction product (A) was analyzed by IR and ¹ H.
As a result of analysis by -NMR, the main product was a lysine derivative (I) in which all X _{1 to} X ₅ in the structural formula in the above general formula (1) were Na. The reaction product (A) contained about 4% by weight of disodium tartrate. Further, this reaction product (A) was repeatedly recrystallized with water-methanol to isolate a lysine derivative (I) in which X _{1 to} X ₅ are all Na in the structural formula in the general formula (1). .

The analytical results IR lysine derivative (I) (KBr): 3400cm -1 (O-H ^{stretch) 1600cm -1, 1390cm -1 (C} = O _{^{stretch) 1 H-NMR (D 2}} O) (ppm) : 4.10-4.04 (2H, d) 3.37-3.31 (2H, d) 2.91 (1H), 2.37 (2H) 1.44-1.13 (6H) The above lysine While cooling, sulfuric acid was added to the aqueous solution of the derivative (I) until the pH of the aqueous solution became 2 or less, and the solution was allowed to stand. The precipitated solid was filtered off to obtain a lysine derivative (II) in which all of X _{1 to} X ₅ in the structural formula in the general formula (I) are H.

The analysis result Elemental analysis _{C 14 H 22 N 2 O 12} · 2H 2 O C (%) of the lysine derivative (II) H (%) N (%) Calculated 37.67 5.87 6.28 Found Value 37.66 5.81 6.27 Example 2 Example 1 except that 5.6 g of potassium hydroxide was used instead of 8.3 g of 48% by weight aqueous sodium hydroxide solution.
The same operation as the above was performed to obtain a colorless solid reaction product (B). This reaction product (B) was treated with IR and ¹ H—N
When analyzed by MR, the main product was found that in the structural formula in the general formula (1), _one of X _{1 to} X ₅ was K and the remaining 4
Was Na, a monolysine-tetrasodium salt of lysine derivative (III). The reaction product (B) contained tartrate in an amount of about 4% by weight.

Example 3 Measurement of Chelate Stability Constant The reaction product (A) obtained in Example 1 was measured for calcium stability constant (pKCa ²⁺ ) and compared with citric acid and zeolite. The results are shown in Table 1.

[0026]

[Table 1]

Example 4 Detergency Test Using the reaction product (A) obtained in Example 1 as a builder, a linear alkylbenzene sulfonic acid sodium salt (hereinafter referred to as LAS) or the like was used as a surfactant. The detergent compositions shown in Table 2 were prepared, and the detergency was examined under the following washing conditions using an artificial cotton cloth. The surface reflectance of the cloth before and after cleaning was measured, and the cleaning power obtained by the following formula was 107. However, the detergency when using zeolite as a builder compound was set to 100.

Washing conditions Tester: Targotometer Washing liquid concentration: 0.12% by weight Water hardness: 3 degree DH Bath ratio: 4 contaminated cloths 1 L Washing temperature: 25 ° C Rotation speed: 200 times / min Washing time: 10 Rinsing: Once every 5 minutes Detergency = [(surface reflectance of cloth after washing-reflectance of cloth before washing) / (reflectance of original cloth-reflectance of cloth before washing)]

[0029]

[Table 2]

Example 5 Biodegradability Test The reaction product (A) obtained in Example 1 and ethylenediaminetetraacetic acid were subjected to a biodegradability test according to the modified MITI method specified in the OECD test guideline. Compared with ethylenediaminetetraacetic acid, which did not show biodegradability within a predetermined test period, the reaction product (A)
It was found to be biodegradable and easily biodegradable.

[0031]

The lysine derivative of the present invention has high water solubility,
It is useful as a chelating agent having chelating ability and excellent biodegradability.

By using the production method of the present invention, the lysine derivative can be produced in good yield.

Further, the detergent composition of the present invention has high water solubility and chelating ability and is excellent in biodegradability by containing the lysine derivative.

[Brief description of drawings]

FIG. 1 ¹ H of lysine derivative (I) obtained in Example 1
A -NMR (D ₂ O) spectrum chart.

Claims (3)

[Claims] 1. A novel lysine derivative represented by the following general formula (1). Embedded image (In the formula, X _{1 to} X ₅ represent an alkali metal, an alkaline earth metal or an ammonium group, and may be the same or different.) 2. A method for producing a lysine derivative represented by the following general formula (1), which comprises reacting epoxysuccinic acid and / or its salt with lysine and / or its salt. Embedded image (In the formula, X _{1 to} X ₅ represent an alkali metal, an alkaline earth metal or an ammonium group, and may be the same or different.) 3. A detergent composition comprising the lysine derivative according to claim 1.