JP3261833B2 - Method for producing detergent composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a detergent composition containing an N-acylamino acid type anionic surfactant, and more particularly to a method for producing a detergent composition containing an N-acylamino acid type anionic surfactant. The present invention relates to a simple method for producing a detergent composition containing an activator and having a low inorganic salt content.

[0002]

2. Description of the Related Art N-acylamino acid type anionic surfactants have excellent surface activity and high safety and are widely used in various detergent compositions. As a method for producing an N-acylamino acid type anionic surfactant, the Schottenbaumann method of reacting an acid halide and an amino acid under alkaline conditions is widely used because it can be produced easily and at low cost. According to this method, an equimolar amount of an inorganic salt is produced as a by-product with the N-acylamino acid type anionic surfactant.
This inorganic salt causes deterioration of the solution stability of the detergent composition at low temperatures. For this reason, in the cleaning composition,
An N-acylamino acid type anionic surfactant from which an inorganic salt has been removed by some method is used.

[0003] As a method of desalting an N-acylamino acid type anionic surfactant, (a) a strong acid is added to an acylation reaction solution, and the N-acylamino acid type anionic surfactant is crystallized in an acid form; Washing method (JP-A-5-97787, JP-A-5-70418, etc.); (b) desalting using an ultrafiltration membrane; (c) synthesizing a reaction solution containing a hydrophilic organic solvent. A method of separating an aqueous layer and an organic layer and separating the organic layer (Japanese Patent Publication No. 57-47902); (d) crystallization and separation after acidifying a reaction solution containing a hydrophilic organic solvent. A method in which crystals are dissolved in a hydrophilic organic solvent so as to have a concentration of 40 to 60%, an aqueous solution of sodium sulfate is added, the organic layer and the aqueous layer are separated, and the organic solvent in the organic layer is distilled off.
-279354) and the like.

[0004] Of these, the method (a) seems to be widely used, but this method requires a device for crystal separation such as a filter or a centrifugal separator, and requires that the method be used in a crystal. Inorganic salts are likely to remain, and it is necessary to wash the crystals with a large amount of water to remove them. Further, depending on the type of N-acylamino acid type anionic surfactant, there are some which have poor crystallinity and separability. There is a problem. Further, in the method (b), a special device is required, and it takes a long time for desalination. In the method (c), layer separation is not performed when the concentration of the hydrophilic organic solvent is lower than 5%. In the method (d), the crystal must be obtained once as in the method (a), and the organic solvent needs to be distilled off, and the operation is complicated.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a detergent composition containing a desalted N-acylamino acid type anionic surfactant without requiring any special equipment. It is to be.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted various studies to solve the above-mentioned problems. As a result, after reacting a fatty acid halide with an amino acid using water as a solvent, the acid-type melting point was added to the reaction solution. Can be separated into an organic layer and an aqueous layer by simply coexisting an anionic surfactant having a temperature of 100 ° C. or lower, a pH of 1 to 5 and a temperature of 50 to 100 ° C., and can be easily desalted. Further, the present inventors have found that a detergent composition can be easily obtained by neutralizing an organic layer with an alkali, thereby completing the present invention.

That is, the present invention provides the following steps (1) to
(3) A method for producing a detergent composition containing an N-acylamino acid type anionic surfactant, characterized by performing (3). (1) Step of reacting a fatty acid halide with an amino acid in water to synthesize an N-acyl amino acid type anionic surfactant (2) Coexisting an anionic surfactant having an acid type melting point of 100 ° C. or less in a reaction solution PH 1-5, temperature 50-10
Step of separating an organic layer and an aqueous layer at 0 ° C. to obtain an organic layer (3) Step of neutralizing the organic layer with an alkali

Hereinafter, the present invention will be described in detail. The fatty acid halide used in the step (1) of the present invention is a saturated or unsaturated fatty acid halide having 8 to 22 carbon atoms, preferably 10 to 18 carbon atoms, such as lauroyl halide, myristoyl halide, palmitoyl halide,
Halides of naturally-occurring mixed fatty acids such as stearoyl halides, oleoyl halides, etc. fatty acid halides such as oleoyl halides, coconut oil fatty acid halides, tallow fatty acid halides, and hardened tallow fatty acid halides, or synthetic fatty acids (including branched fatty acids) Is mentioned. In the present invention, these fatty acid halides can be used alone or in combination of two or more.

The amino acids used in the present invention include glycine, alanine, β-alanine, threonine, serine, leucine, isoleucine, valine, proline, hydroxyproline, and other neutral amino acids, glutamic acid, aspartic acid, α-aminoadipate. And acidic amino acids such as α-pimelic acid, cysteic acid, homocysteic acid, 2-aminoeicosanedicarboxylic acid and β-hydroxyaspartic acid.

The reaction between the fatty acid halide and the amino acid may be performed according to a known method. For example, JP-A-5-97
787, JP-A-5-70418, Japanese Patent Publication No. Sho 4
Reference can be made to JP-A-8-35058. Water that does not substantially contain a hydrophilic organic solvent is used as the solvent.
Can be The ratio of amino acid to fatty acid halide is 0.
5-2 equivalents, reaction pH 10-14, reaction temperature -10
Preferably it is 60 ° C. The N-acylamino acid thus obtained is desalted and separated in step (2).

The anionic surfactants having a melting point of 100 ° C. or lower in the acid type used in step (2) include higher fatty acid salts, phosphate ester type surfactants, N-alkyl-N-acyl amino acid salts, -Hydroxyalkyl-
Among anionic surfactants such as N-acyl amino acid salts, alkyl ether carboxylate, and sulfosuccinic acid long-chain ester type surfactants, the melting point of the acid type is 100.
C. or lower. These are preferably added in acid form, but may be added in salt form. They may be used as a mixture.

[0012] Specific examples of such anionic surfactants include higher fatty acids such as lauric acid,
In addition to acyl groups formed by fatty acids having a single composition such as myristic acid, palmitic acid, stearic acid, and oleic acid, naturally-occurring mixed fatty acids such as coconut oil fatty acids, tallow fatty acids, and hardened tallow fatty acids or fatty acids obtained by synthesis ( Branched fatty acids), and particularly from the viewpoint of separability, fatty acids having a double bond in the molecule or having 8 carbon atoms.
A mixed fatty acid containing 5 to 10% by weight or more of the fatty acid in the composition is preferred.

Examples of the phosphate type surfactant include those represented by the following general formula (1) or (2).

[0014]

Embedded image

Wherein R ¹ is a saturated or unsaturated hydrocarbon group having 8 to 18 carbon atoms, and R ² is a 5 to 12 carbon atoms.
R ³ is a saturated or unsaturated hydrocarbon group of
X to Y each represents a hydrogen atom, an alkali metal, ammonium or an alkanolamine, and l represents an integer of 0 to 10. )

The N-alkyl-N-acyl amino acids include N-lauroyl-N-isopropylglycine,
Lauroyl sarcosine, N-myristoyl sarcosine,
N-palmitoyl sarcosine, N-lauroyl-N-methyl-β-alanine, N-myristoyl-N-methyl-
β-alanine, N-palmitoyl-N-methyl-β-alanine and the like.

The N-hydroxyalkyl-N-acyl amino acids include N-lauroyl-N-hydroxyethylglycine, N-myristoyl-N-hydroxyethylglycine, N-oleoyl-N-hydroxyethylglycine N-caprinoyl-N- Hydroxyethylglycine, N
-Lauroyl-N-hydroxyethyl-β-alanine,
N-myristoyl-N-hydroxyethyl-β-alanine and N-oleoyl-N-hydroxyethyl-β-alanine.

Examples of the alkyl ether carboxylate include polyoxyethylene alkyl ether acetic acid and polyglyceryl alkyl ether acetic acid.

Examples of the sulfosuccinic acid long-chain ester type surfactant include higher alcohols represented by the following general formula (3) or (4) or sulfosuccinates of ethoxylates thereof or sulfosuccinates derived from higher fatty acid amides. Can be

[0020]

Embedded image

Wherein R ⁴ is R ⁵ —O— or R ⁶ —C
ONH- is represented by the following formula (wherein, R ⁵ represents a linear or branched alkyl or alkenyl group having 8 to 22 carbon atoms, and R ⁶ represents a linear or branched alkyl or alkenyl group having 7 to 21 carbon atoms. , M ¹ and M ² each represent a hydrogen atom, an alkali metal, ammonium or organic ammonium, and p represents an integer of 0 to 20. ]

The amount of coexisting anionic surfactant in step (2) varies depending on the type of N-acylamino acid type anionic surfactant and anionic surfactant.
Usually 5/95 to 95/5 (anionic surfactant / N-acylamino acid type anionic surfactant), preferably 20
/ 80 to 80/20.

The pH in the step (2) is from 1 to 5, preferably from 1.5 to 4. If the pH is out of this range, the organic layer and the aqueous layer are not separated. As the acid for adjusting the pH,
Examples thereof include mineral acids such as sulfuric acid, hydrochloric acid, and phosphoric acid, and organic acids such as citric acid, succinic acid, malic acid, and acetic acid.

Further, the temperature is 50 to 100 ° C., preferably 60 to 90 ° C. If the temperature is lower than 50 ° C., the organic layer and the aqueous layer are not separated. At 60 ° C. or higher, the water content contained in the organic layer can be reduced, and at 80 ° C. or higher, the layer separation can be further improved. If the temperature of the organic layer exceeds 100 ° C., the product is undesirably colored and the N-acylamino acid is decomposed.

The organic layer thus separated is washed with water if necessary, and then the next step (3)
To obtain a detergent composition.

The alkali used in step (3) of the present invention is not particularly limited, and may be an alkanolamine such as sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, triethanolamine, diethanolamine and the like. And alkanol ammoniums such as choline, and basic amino acids such as lysine, ornithine and arginine. The neutralization reaction is performed by setting the temperature of the organic layer to 5
The temperature may be maintained at about 0 to 70 ° C., and an alkali or an aqueous solution thereof may be added.

The cleaning composition obtained by the production method of the present invention may optionally contain other anionic surfactants, amphoteric surfactants, nonionic surfactants, and the like. Also contains humectants, pigments, fragrances, solubilizers, preservatives, conditioning agents, builders, chelating agents, whitening agents, pearling agents, molding agents, etc. used in other ordinary cleaning compositions. can do.

[0028]

EXAMPLES The present invention will be specifically described below with reference to examples.

Example 1 Step (1) 75 g (1 mol) of glycine was dissolved in 1000 ml of water, and the pH was adjusted to 11 with a 30% aqueous potassium hydroxide solution. While maintaining the temperature at around 15 ° C., 218.5 g (1 mol) of lauroyl chloride was slowly added dropwise while adjusting the pH to 11 using a 30% aqueous potassium hydroxide solution. After the dropwise addition, the mixture was further stirred for 2 hours while adjusting the pH to 11. This reaction solution contained 14.3% (244.2 g) of N-lauroylglycine and 4.4% (74.6 g) of potassium chloride. Step (2) 3.7 g of lauric acid (melting point: 43 ° C.) was added to the acylation reaction solution.
g, the temperature was adjusted to 80 ° C., and the pH was adjusted to 2 by adding dilute sulfuric acid with stirring. After stirring for about 10 minutes, the mixture was allowed to stand for 5 minutes and then separated into an organic layer and an aqueous layer. About 1200 ml of the aqueous layer was removed from the lower part of the container. 1250 ml of hot water was added to the remaining organic layer, the temperature was again raised to 80 ° C., and the mixture was stirred for 10 minutes, allowed to stand for 5 minutes, and the separated aqueous layer was removed to obtain an organic layer. Step (3) A 27% aqueous sodium hydroxide solution and water were added to the organic layer to adjust the pH to 8.5 and the surfactant concentration to 30% to obtain a detergent composition. Its inorganic salt content is 3
6 ppm (based on N-lauroylglycine 0.012%)
Met.

Comparative Example 1 In step (2) of Example 1, except that lauric acid was not added, an attempt was made to carry out the same operation. As a result, the whole liquid became creamy and could not be stirred.

Example 2 Step (1) 89 g (1 mol) of β-alanine was dissolved in 1000 ml of water, and the pH was adjusted to 14 using 30% sodium hydroxide. 217.5 g of cocoyl chloride was added to this solution.
(1 mol) was added dropwise while maintaining the temperature at 25 ° C. After completion of the dropwise addition, the mixture was aged at 40 ° C. for 2 hours. This reaction solution contains 1
It contained 4.6% (256.5 g) of N-cocoyl β-alanine and 5.6% (98.5 g) of sodium chloride. Step (2) 1 g of coconut oil fatty acid (melting point 27 ° C., NAA-415, manufactured by NOF CORPORATION) was added to the above reaction solution, the pH was adjusted to 3 with dilute sulfuric acid, and the mixture was allowed to stand at 80 ° C. 1300m of separated water layer
After removing 1, 1300 ml of hot water was added to the organic layer, the temperature was adjusted to 80 ° C. while stirring, and the mixture was allowed to stand, and the aqueous layer was removed to obtain an organic layer. Step (3) Triethanolamine and water were added to the organic layer to adjust the pH to 8 and the surfactant concentration to 30% to obtain a detergent composition. Its inorganic salt content was 61 ppm (based on N-cocoyl β-alanine 0.02%).

Comparative Example 2 In the step (2) of Example 2, an attempt was made in the same manner as in Example 2 except that the temperature was changed to 80 ° C. and the temperature was changed to 40 ° C., but the whole liquid became creamy and could not be separated.

Example 3 Step (1) 89 g (1 mol) of DL-alanine was dissolved in 1000 ml of water, and the pH was adjusted to 14 using 30% potassium hydroxide. To this solution was added myristoyl chloride 257.4.
g (1 mol) was added dropwise while maintaining the temperature at 30 ° C.
After the completion of the dropwise addition, the mixture was further stirred at 50 ° C. for 2 hours. This reaction solution contained 16.7% of N-myristoyl-DL-alanine.
(294.4 g), 4.2% potassium chloride (74.6 g).
g) included. Step (2) To the above reaction solution was added 7.2 g of N-lauroyl-N-methyl-β-alanine (melting point: 70 ° C.), adjusted to pH 3 with dilute sulfuric acid, heated to 75 ° C. and allowed to stand. After removing the separated aqueous layer, 1350 ml of hot water was added to the organic layer, the temperature was adjusted to 75 ° C. with stirring, and the mixture was allowed to stand still to remove the aqueous layer to obtain an organic layer. Step (3) Add 47% aqueous potassium hydroxide solution and water to the organic layer,
The detergent composition was adjusted to 7.0 and a surfactant concentration of 30% to obtain a detergent composition. Its inorganic salt content is 30 ppm
(0.01% of N-myristoyl-DL-alanine).

Comparative Example 3 In step (2) of Example 3, N-lauroyl-N-
When an attempt was made in the same manner except that N-stearoylglutamic acid (melting point 115 ° C.) was used instead of methyl-β-alanine, the whole liquid became creamy and could not be separated.

Example 4 Step (1) 119 g (1 mol) of L-threonine was added to 1000 ml of water.
And the pH was adjusted to 11 using 30% potassium hydroxide. 218.5 lauroyl chloride was added to this solution.
g (1 mol) was added dropwise while maintaining the temperature at 15 ° C.
After completion of the dropwise addition, the mixture was further stirred at 15 ° C. and pH 11 for 2 hours. The reaction mixture contained 16.4% (286 g) of N-lauroyl-L-threonine and 4.3% (7%) of potassium chloride.
4.5 g). Step (2) 7.2 g of lauroyl sarcosine (melting point 32 ° C.) was added to the above reaction solution, the pH was adjusted to 3 with citric acid, and the mixture was heated to 80 ° C. and allowed to stand. After removing the separated aqueous layer, 1300 ml of hot water was added to the organic layer, the temperature was adjusted to 80 ° C. while stirring, and the mixture was allowed to stand still to remove the aqueous layer to obtain an organic layer. Step (3) Triethanolamine and water are added to the organic layer, and pH8.
0, the surfactant concentration was adjusted to 30% to obtain a detergent composition. Its inorganic salt content is 17
ppm (relative to N-lauroyl-L-threonine 0.00
6%).

Comparative Example 4 In step (2) of Example 4, except that the pH was changed to 6, the whole liquid was creamy and could not be separated.

Example 5 Step (1) 147.1 g (1 mol) of L-glutamic acid was added to 100 parts of water.
It was dissolved in 0 ml and the pH was adjusted to 11 using 30% potassium hydroxide. After adding 20 g of triethylamine, 218.5 g (1 mol) of lauroyl chloride was added.
Was added dropwise while maintaining the temperature at 15 ° C. After dropping, 1
The mixture was further stirred at 5 ° C. and pH 11 for 2 hours. This reaction solution contained 17.6% of N-lauroyl-L-glutamic acid (3%).
12.6 g), 4.2% potassium chloride (74.7 g)
Was included. Step (2) Add 10 g of polyoxyethylene lauryl ether carboxylic acid (2 moles of EO added) to the above reaction solution, and add p with dilute hydrochloric acid.
With H being 2, the mixture was heated to 90 ° C. and allowed to stand. After removing the separated aqueous layer, 1300 ml of hot water was added to the organic layer, the temperature was adjusted to 80 ° C. with stirring, and the mixture was allowed to stand still to remove the aqueous layer to obtain an organic layer. Step (3) A 27% aqueous sodium hydroxide solution and water are added to the organic layer, and p
H5.5 was adjusted so that the entire surfactant concentration became 30%, to obtain a detergent composition. Its inorganic salt content is 7 ppm (vs. N-lauroyl-L-glutamic acid 0.1 ppm).
006%).

Comparative Example 5 The same procedure was carried out as in Example 5 except that the amount of polyoxyethylene lauryl ether carboxylic acid was changed to 0.2 g in the step (2). Could not layer.

Example 6 50 parts by weight of the detergent compositions prepared in Examples 1 to 5, 5 parts by weight of alkanolamide laurate, 5 parts by weight of glycerin, 0.5 parts by weight of citric acid, and the balance of purified water A liquid detergent composition was prepared and subjected to a storage test at -5 ° C for one week. As a result, no freezing and solid precipitation were observed in all the detergent compositions.

Example 7 50 parts by weight of the detergent compositions prepared in Examples 1 to 5, 7 parts by weight of potassium myristate, 5 parts by weight of alkanolamide laurate, 5 parts by weight of ethanol and the balance of purified water A liquid detergent composition was prepared and subjected to a storage test at -5 ° C for one week. As a result, no freezing and solid precipitation were observed in all the detergent compositions.

[0041]

The production method of the present invention can provide a detergent composition containing a desalted N-acylamino acid type anionic surfactant without requiring any special equipment. The cleaning composition thus obtained has excellent storage stability at low temperatures.

Continuation of the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C11D 1/10 C07D 231/02 C07D 233/45-233/55

Claims (1)

(57) [Claims] 1. A method for producing a detergent composition containing an N-acylamino acid type anionic surfactant, which comprises performing the following steps (1) to (3). (1) A step of reacting a fatty acid halide with an amino acid in water substantially free of a hydrophilic organic solvent to synthesize an N-acylamino acid type anionic surfactant (2) The reaction solution has an acid type melting point of 100 ° C. The following anionic surfactant is an N-acyl amino acid type anionic surfactant
(5) Step of separating an organic layer and an aqueous layer at pH 1 to 5 and at a temperature of 50 to 100 ° C. to obtain an organic layer by coexisting at a ratio of 5 parts by weight or more to 95 parts by weight of the agent. Of neutralizing methane with alkali