JP2008285620A - Surfactant derived from soy sauce - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a highly safe surfactant with a good performance by making efficient use of wastewater obtained by desalting soy sauce lees, which is a useful resource. <P>SOLUTION: The surfactant represented by formula (1) (wherein R<SP>1</SP>CO is a fatty acid residue; R<SP>2</SP>is an amino acid side chain; M is a hydrogen atom, a metal atom or ammonium; and n is 1-100) is obtained by acylating a mixture which contains amino acids and peptides derived from soy sauce. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a surfactant obtained by acylating a mixture of amino acids and peptides derived from soy sauce and a method for producing the same.

  Soy sauce is obtained by using soybean and wheat as raw materials, adding salt water and koji mold, fermenting and squeezing the ripened moromi, and about 10 parts by weight of soy sauce cake as a pressing residue is generated with respect to 100 parts by weight of soy sauce. . Soy sauce cake contains abundant proteins, amino acids, and carbohydrates, but its use is limited because it contains 5-7% of salt, and most of it is treated as industrial waste. If the salt content in soy sauce cake is reduced, it can be used as feed and fertilizer. Therefore, studies have been conducted to elute the salt content in soy sauce cake with a solvent such as water. In this case, a large amount of waste liquid containing amino acids and the like in addition to salt is generated, but for its use, in Patent Documents 1 to 3, it is reused as an extraction solvent, and in Patent Document 4, it is used as salt water for soy sauce charging, Patent Document 5 proposes desalting by electrodialysis and using it as a liquid fertilizer. However, when it is reused as an extraction solvent, there is a problem in the treatment of the concentrated waste liquid, and when it is used as a salt water for soy sauce charging, there is a problem of deterioration of the soy sauce flavor. In addition, the desalination waste liquid of soy sauce cake contains volatile basic substances, alkaline earth metals, etc., and often produces by-products with poor cleaning performance, causes of odor, and poorly water-soluble carboxylates. It was not considered to produce a surfactant from desalted waste liquid derived from soy sauce cake.

JP-A-10-295320 JP 2001-69942 A JP 2003-169629 A JP-A 63-219350 Noto 3010650 gazette

  Therefore, the problem to be solved by the present invention is to provide a surfactant having high safety and good performance by effectively utilizing a desalted waste liquid of soy sauce cake which is a useful resource.

  As a result of intensive studies on the above problems, the present inventors have found that acylated products of amino acids and peptides in the desalted waste liquid of soy sauce cake are useful as surfactants, and have completed the present invention. That is, the present invention is a surfactant represented by the following general formula (1) obtained by acylating a mixture containing amino acids and peptides derived from soy sauce.

(In the formula, R ¹ CO represents a fatty acid residue, R ² represents an amino acid side chain, M represents a hydrogen atom, a metal atom or ammonium, and n represents a number of 1 to 100.)

  The effect of the present invention is to provide a surfactant having high safety and good performance by effectively utilizing a desalted waste liquid of soy sauce cake.

  The compound represented by the general formula (1) is a derivative of an amino acid and a peptide, and the amino acid that can be used in this derivative or the amino acid constituting the peptide is represented by the following general formula (2).

(In the formula, R ² represents an amino acid side chain.)
The amino acid represented by the general formula (2) becomes various types of amino acids depending on the type of R ^2. Examples of such amino acids include glycine, alanine, valine, leucine, isoleucine, serine, threonine, cysteine, and cystine. Methionine, asparagine, aspartic acid, glutamine, glutamic acid, lysine, arginine, phenylalanine, tyrosine, histidine, tryptophan, proline, hydroxyproline and the like. Moreover, a peptide is a molecule | numerator which said amino acid condensed by the amide bond, The condensation number is a number of 2-100.

  The surfactant of the present invention uses a mixture containing amino acids and peptides derived from the above-mentioned soy sauce as a raw material. The reason why soy sauce-derived amino acids and peptides are used as raw materials is that the performance of the surfactant is better than when using a mixture of other amino acids and peptides obtained by methods such as chemically degrading proteins. It is. These soy sauce-derived amino acids and peptides may be made from amino acids and peptides derived from soy sauce or soy sauce cake demineralized waste liquid, but it is more preferable to use soy sauce koji desalted waste liquid from the viewpoint of waste utilization.

  The desalted waste liquid of soy sauce cake refers to a solution obtained by extracting salt, amino acids, peptides, etc. from the soy sauce cake with water, and a concentrate thereof. When performing water extraction, you may carry out with the mixed solvent of water and a water-soluble organic solvent. Examples of such water-soluble organic solvents include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, tertiary butanol, acetone, dioxane, tetrahydrofuran, and the like.

  The method for extracting salt, amino acids, peptides, etc. from soy sauce cake is not particularly limited. When performing extraction using water or a water-soluble organic solvent containing water, the soy sauce cake may be used as it is or after pretreatment such as heating, pulverization, and molding. The temperature at which the extraction is performed is not particularly limited, and may be performed at a temperature at which the amino acids and peptides in the soy sauce cake do not change. For example, the extraction can be performed within a range of room temperature to 150 ° C.

  The desalination waste liquid of soy sauce cake usually contains volatile basic substances such as ammonia and lower amines, and alkaline earth metals such as potassium and magnesium. When a volatile basic substance reacts with an acylating agent, it may cause a by-product with poor cleaning performance or an odor component, and an alkaline earth metal reacts with the acylating agent. Then, a hardly water-soluble carboxylate is formed.

Therefore, in the method for producing a surfactant of the present invention, it is preferable to remove these volatile basic substances and alkaline earth metals before acylation. Any method can be used as long as it is a known method. However, since the desalted waste liquid of soy sauce cake is usually weakly acidic at pH 4-5, an alkaline agent is added as a pretreatment to a pH of about 10-13. After making it alkaline,
It is preferable to remove by degassing and filtering. That is, under alkaline conditions, volatile basic substances are easily removed by degassing, and alkaline earth metals produce insoluble precipitates.

  The degree of reduced pressure when degassing is usually 100 hPa or less, preferably 50 hPa or less, more preferably 20 hPa or less. Although the temperature at the time of removing under reduced pressure is not particularly limited, normal temperature to 100 ° C is preferable, and 40 to 80 ° C is more preferable. When removing the alkaline earth metal, after adjusting the pH to about 10 to 13, the generated suspended matter may be filtered.

  As the alkali agent, for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, barium hydroxide and the like can be used, but sodium hydroxide or potassium hydroxide is preferable because it is easy to handle and inexpensive.

  Other amino acids and / or peptides may be added to the mixture of amino acids and peptides thus obtained, but the composition of the amino acid and peptide mixture is 50 to 90% by mass of amino acids and 10 to 50% by mass of peptides. It is preferable to mix so that it may become this range. If this composition ratio is deviated, the performance of the obtained surfactant may deteriorate.

  The desalted waste liquid of soy sauce koji may be used for acylation as it is, but if it is too dilute, the reaction efficiency will deteriorate, so it is preferable to concentrate and use it for acylation. In addition, since it will partly isolate | separate and precipitate when it is too thick, it is preferable to acylate after concentrating to about 50-70% of water | moisture content. Examples of the concentration method include reduced pressure / dehydration, ultrafiltration, and the like.

R ¹ CO in the general formula (1) represents a fatty acid residue. R ¹ CO is determined by the acylating agent used. As the acylating agent, for example, carboxylic acid, carboxylic acid halide, carboxylic acid methyl ester, carboxylic acid ethyl ester, and the like can be used. However, since the reactivity is high, carboxylic acid or carboxylic acid halide should be used. It is preferable to use a carboxylic acid halide. As the carboxylic acid halide, carboxylic acid chloride is preferable because it is easily available.

  Examples of the carboxylic acid or its halide include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, undecanoic acid, undecenoic acid, myristic acid, palmitic acid Examples include acids, stearic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, erucic acid, and chlorides thereof. The carbon number of the carboxylic acid or its halide is preferably 8-22, more preferably 9-20, and most preferably 10-18. The carboxylic acid or its halide may be the same carbon number, but may be a mixture of two or more. In the case of mixing two or more kinds, the average carbon number may be within the above range. In addition, fatty acids obtained from natural fats and oils or fatty acid halides obtained by halides thereof may be used. Examples of natural fats and oils include linseed oil, olive oil, cacao butter, sesame oil, rice bran oil, safflower oil, soybean oil, camellia oil, corn oil, rapeseed oil, palm oil, palm kernel oil, castor oil, cottonseed oil, coconut oil, etc. Vegetable fats and oils; animal fats such as beef tallow, pork tallow, milk fat, fish oil, whale oil and the like.

  The amount of the acylating agent used is preferably 0.8 to 1.5 equivalents, more preferably 0.9 to 1.3 equivalents, and 0.95 to 1.2 equivalents in terms of a molar ratio with respect to amino acids, peptides and the like. Most preferred. The molar content of amino acids, peptides and the like can be measured by a titration method such as a mole hole method, a colorimetric method such as a ninhydrin method, an instrumental analysis method such as high performance liquid chromatography.

  Although the temperature of the acylation reaction is not particularly limited, it is not efficient because the reaction rate is slow when it is performed at too low temperature, and it is preferably performed at 0 to 100 ° C. because it causes decomposition of the raw material fatty acid halide. More preferably, it is performed at 15 to 70 ° C, and most preferably 20 to 50 ° C. Although the time for performing the acylation reaction is not particularly limited, it is preferably 10 minutes to 12 hours, more preferably 20 minutes to 8 hours, and further preferably about 30 minutes to 6 hours. In addition, when carboxylic acid chloride is used for the acylation reaction, it is preferable to adjust the pH in the reaction system to be alkaline with an alkaline agent and to add it to the reaction system in order to accelerate the reaction. More preferably, it is added to the reaction system.

  Examples of such an alkali agent include sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, triethylamine, pyridine and the like in addition to the alkali agents mentioned in the pretreatment, such as sodium hydroxide or potassium hydroxide. Is preferred, and sodium hydroxide is more preferred.

  The acylation reaction may be performed only with an aqueous solvent, but in order to speed up the reaction, it is preferable to use an organic solvent in combination. As an organic solvent for the acylation reaction, in addition to the water-soluble organic solvent mentioned in the extraction of soy sauce cake, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, methoxyethanol, ethoxyethanol, butoxyethanol, methyl ethyl ketone, methyl isobutyl ketone, Examples thereof include dimethyl ether, diethyl ether, and ethyl methyl ether. Of these, 2-propanol, 2-butanol, tertiary butanol, and propylene glycol are preferable. The amount of the organic solvent is not particularly limited. However, when the amount is too small or too large, the reaction rate does not increase. Therefore, the amount of the organic solvent is preferably 5 to 100 parts by weight with respect to 100 parts by weight of water. -80 mass parts is still more preferable, and 15-60 mass parts is the most preferable.

  After completion of the reaction, an acid such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc. is added to make the pH acidic, whereby the acylated product is separated and washed with water to remove unreacted amino acids, peptides, sugars, sodium chloride, etc. It is preferable to remove. When the pH is too high, the separation becomes insufficient, and when the pH is too low, the acylated product may be decomposed. Therefore, pH 1 to 5 is preferable, and pH 1.5 to 4 is more preferable. If the acylated product is difficult to separate, a water-insoluble organic solvent such as ethyl ether, toluene, xylene, or methyl isobutyl ketone may be added. 1-100 mass parts is preferable with respect to 100 mass parts of preparation amounts of the desalination waste liquid of soy sauce cake, and 2-50 mass parts is still more preferable.

  After washing with water, the acylated product may be depressurized and deaerated as necessary to remove the solvent and the like. Although the temperature at the time of depressurization and deaeration is not particularly limited, it is usually about 10 to 120 ° C. The degree of vacuum is usually 100 hPa or less, preferably 50 hPa or less, more preferably 20 hPa or less. Moreover, since salt etc. may precipitate by pressure_reduction | reduced_pressure and deaeration, it can remove by filtration etc.

  In the acylated product thus obtained, M is a hydrogen atom in the general formula (1), but it can be treated with an alkali, an amine or the like to form a salt. In this case, M is determined by the alkali or amine used. Examples of the alkali include those described above, and examples of the amine include ammonia, methylamine, dimethylamine, ethylamine, diethylamine, (iso) propylamine, di (iso) propylamine, ethanolamine, diethanolamine, triethanolamine, 2- Amino-2-methyl-1,3-propanediol, aminoethylethanolamine, N, N, N ′, N′-tetrakis (2-hydroxyethyl) ethylenediamine, N, N, N ′, N′-tetrakis (2 -Hydroxypropyl) ethylenediamine and the like.

  In addition, since the obtained surfactant has odor and coloring derived from the desalination waste liquid of soy sauce cake, it is preferable to perform deodorization and decolorization by a known method in any step in the production method of the present invention, It is more preferable to deodorize and decolorize the acidic desalted waste liquid extracted from soy sauce cake. Examples of deodorizing and decoloring methods include oxidation with hydrogen peroxide, etc .; adsorption with activated carbon, adsorbent, ion exchange resin, etc .; separation by ultrafiltration, etc .; extraction with organic solvent, supercritical gas, etc .; topping by steam distillation, etc. Etc. Among these, adsorption by an ion exchange resin is preferable, adsorption by a phenol / formaldehyde resin is more preferable, and adsorption by a phenol / formaldehyde resin, Hokuetsu HS or Hokuetsu KS (both manufactured by Ajinomoto Fine Techno Co.) is more preferable. .

  The surfactant of the present invention, like conventional acylated amino acids and acylated peptides, is excellent in water solubility and hard water resistance and less irritating to the human body, but is further excellent in foaming properties, foam breakage, and storage stability. Therefore, it is preferably used for so-called toiletries. Examples of toiletries include cleaning agents and cosmetics. Examples of cleaning agents include hair shampoos, hair rinses, hair conditioners, hair treatments, body shampoos, facial cleansers, kitchen detergents, dish cleaners, clothes detergents, and the like. As cosmetics, for example, permanent wave agent, hair cream, hair foam, hair bleach, hair lotion, hair liquid, hair nick, lotion, shaving cream, after shaving lotion, pre-shaving lotion, face lotion, moisture cream, cleansing cream, Examples include cold cream and lipstick.

  When the surfactant of the present invention is used as a cleaning agent or cosmetic, it can be used in combination with other components. Examples of other components include nonionic surfactants such as alcohol ethoxylates, alkylphenol ethoxylates, alkyl polyglycosides, and alkanolamides; alkylbenzene sulfonates, alkyl sulfates, alkyl ether sulfates, α-olefin sulfonates, acylated isethionates Anionic surfactants such as other acylated amino acids or acylated polypeptides, fatty acid soaps, and alkyl ether carboxylates; Cationic surfactants such as stearyltrimethylammonium, cetyltrimethylammonium, and polydimethyldiallylammonium; alkylcarbobetaines , Amphoteric surfactants such as amidopropylcarbobetaine and imidazolinium betaine; semipolar surfactants such as alkylamine oxides Agent: Hydrotrope such as ethylene glycol, propylene glycol, polyethylene glycol, polyalkylene glycol alkyl ether, ethanol, paratoluenesulfonic acid, etc .; ethylenediaminetetraacetate (EDTA), hydroxyethylethylenediaminetriacetic acid (HEDTA), nitrilotriacetic acid (NTA) ), Aminocarboxylic acids such as diethylenetriaminepentaacetic acid (DTPA), aspartic acid-N, N-diacetic acid, N-hydroxyethyliminodiacetic acid or salts thereof, citric acid, gluconic acid, glycolic acid, tartaric acid or salts thereof Sequestering agents such as oxycarboxylic acids such as magnesium sulfate, sodium sulfate (sodium salt), sodium carbonate, sodium bicarbonate, potassium carbonate, sodium silicate, potassium silicate, etc. Rebuilder; Alkaline agent such as sodium hydroxide and potassium hydroxide; monoethanolamine, N-methylmonoethanolamine, N-ethylmonoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, Alkanolamines such as 2-amino-2-methyl-1,3-propanediol and aminoethylethanolamine; dispersants such as sodium polyacrylate and sodium acrylate-olefin copolymer; preservatives, thickeners, enzymes , Antibacterial agents, moisturizers, fragrances, pigments and the like.

Hereinafter, the present invention will be described more specifically with reference to examples. In the following examples, unless otherwise indicated, parts or% is based on mass.
<Soy sauce cake desalination waste liquid>
50 kg of water at 25 ° C. was added to 10 kg of soy sauce cake containing 6.4% of salt, and after stirring for 30 minutes, the solid was separated by centrifugation to obtain 45 kg of soy sauce cake desalting waste liquid.
Analysis value (ignition residue test method) ignition residue 3.43% salt 1.58% nitrogen 0.16%

(Invention product 1)
When 48% sodium hydroxide was added to 10 kg of the soy sauce cake desalting waste solution until pH 12, the solution became thin and turbid and ammonia odor was generated. The thin turbidity of the liquid was removed by suction filtration using filter paper. The filtrate had an ammonia odor, but was removed by degassing at a reduced pressure of 30 hPa for 10 minutes using an evaporator with a liquid temperature of 70 ° C. Subsequently, the mixture was concentrated with an evaporator until the water content became about 70%. The analysis results are described below.
Analytical value Moisture 69.5% Nitrogen 0.16%
Amino acids and peptides: 0.66 mmol / g (by molhole method)
Amino acid / peptide = 69/31 (by GPC analysis)
(GPC column: Shodex. Ashhipak-310, solvent: water / acetonitrile = 1/1)
A glass flask equipped with a thermometer and a stirrer was charged with 500 g of concentrated desalted waste liquid and 100 g of 2-propanol, and 75.9 g (346.5 mmol) of lauric acid chloride was adjusted to 50 ° C. while adjusting the pH to 10 with sodium hydroxide. It was dripped at. After completion of dropping, the mixture was aged at 40 to 50 ° C. for 1 hour. Then, when hydrochloric acid was added until pH 2 was reached, the mixture was separated into two layers. Therefore, the lower layer (aqueous layer) was removed, and the upper layer (oil layer) was washed twice with 100 g of water. After depressurization and deaeration for 1 hour under the conditions of 100 ° C. and 10 hPa, the mixture was neutralized with an aqueous sodium hydroxide solution to pH 7 to obtain Product 1 (sodium salt) of the present invention having a solid content of 30%.

(Invention product 2)
Except that neutralization of the acylated product was performed with an aqueous potassium hydroxide solution, the same operation as in Example 1 was performed to obtain the product 2 (potassium salt) of the present invention having a solid content of 30%.

(Invention product 3)
Except that neutralization of the acylated product was carried out with an aqueous solution of triethanolamine, the same operation as in Example 1 was performed to obtain Product 3 (triethanolamine salt) having a solid content of 30%.

(Invention product 4)
Except that coconut fatty acid chloride was used in place of lauric acid chloride, the same operation as in Example 1 was performed to obtain a product 4 (sodium salt) of the present invention having a solid content of 30%.

(Comparative product 1)
200 g of soybean protein and 200 g of 20% hydrochloric acid were charged into a glass container and refluxed for 8 hours. After cooling, 200 g of water was added, 48% sodium hydroxide was added until pH 12 and then filtered to obtain a soybean protein hydrolyzate. Thereafter, the same operation as in Example 1 was performed to obtain a comparative product 1 (sodium salt) having a solid content of 30%. The analysis results are described below.
Amino acid / peptide = 71/29 (by GPC analysis)

(Comparative product 2)
Coconut oil fatty acid glutamic acid sodium salt

(Evaluation 1: Purity) The purity of the surfactant obtained in the examples was analyzed by GPC (column: Shodex. Ashhipak-310, solvent: water / acetonitrile = 1/1).
Purity = 100 × A / (A + S)
A: Peak area of acylation (amino acid / peptide) S: Peak area of fatty acid salt

(Evaluation 2: Foaming property)
Foaming of the surfactant of the present invention was measured by the Ross Miles method. The measurement conditions were 0.25% as the solid content, and the foam height after 5 minutes at a water temperature of 25 ° C. was measured. Moreover, distilled water and artificial hard water (calcium carbonate concentration 200 ppm) were used as water. The unit is mm.

(Evaluation 3: Compounding stability)
The appearance of the mixed solution having the following composition was visually observed after being stored at 0 ° C. or 25 ° C. for 72 hours.
Invention product or comparative product 15% (solid content conversion)
Lauric acid diethanolamide 5
Lauryldimethylamine oxide 3
Lauryl glucoside 2
Propylene glycol 5
Ion exchange water 70

(Evaluation 4: Hair washing test)
Using the formulation prepared in Evaluation 3, 10 female monitors evaluated the foaming at the time of washing the hair, the loss of foam at the time of rinsing, and the combing after the hair washing, and each result was evaluated according to the following criteria.
A: 8 to 10 people evaluated it as good.
(Triangle | delta): Three to seven people evaluated it favorable.
X: 0-2 people evaluated it favorable.

  From the above results, it can be seen that the present invention is a surfactant that effectively utilizes the desalted waste liquid of soy sauce cake and has high safety and good performance.

Claims (5)

A surfactant represented by the following general formula (1) obtained by acylating a mixture containing amino acids and peptides derived from soy sauce.

(In the formula, R ¹ CO represents a fatty acid residue, R ² represents an amino acid side chain, M represents a hydrogen atom, a metal atom or ammonium, and n represents a number of 1 to 100.)   2. The surfactant according to claim 1, wherein in the mixture containing the soy sauce-derived amino acid and peptide, the amino acid is 50 to 90 mass% and the peptide is 10 to 50 mass%.   The surfactant according to claim 1 or 2, wherein the mixture of amino acids and peptides derived from soy sauce is a mixture of amino acids and peptides extracted from soy sauce cake.   The method for producing a surfactant according to any one of claims 1 to 3, wherein a mixture of amino acids and peptides extracted from the soy sauce cake is acylated.   The production method according to claim 4, wherein the mixture of amino acids and peptides extracted from the soy sauce cake is adjusted to pH 10 to 13 with an alkaline agent, and then decompressed, degassed and / or filtered.