JPH0340758B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a liquid detergent composition containing a dipeptide compound, and more particularly to a liquid detergent composition characterized by containing an N-(N'-acylglycyl)glycine compound. In recent years, an increasing number of consumers are demanding liquid cleansers that are gentle on the skin and liquid cleansers that are highly biodegradable, and liquid cleansers that meet these demands have become available. . Typical surfactants used as bases in these detergents include N-acylamino acid salts, amidoamine type amphoteric surfactants, and acylated peptides. Among these, acylated peptides are acylated mixtures of peptides produced from natural proteins, and they have disadvantages such as turbidity and peculiar odor when added to liquid detergents. . These drawbacks are thought to be caused by impurities such as lipids and polysaccharides contained in natural peptides, and volatile components such as aldehydes, ketones, keto acids, and sulfides generated when the impurities are oxidized.
In order to improve the drawbacks of acylated natural peptides, it was necessary to remove organic substances such as lipids and polysaccharides contained in natural proteins. However, it is difficult to completely remove these impurities, and all of the obtained products have insufficient improvement effects. The present inventor conducted intensive research with the aim of improving the drawbacks of conventional acylated peptides, and discovered that a specific dipeptide compound does not have these drawbacks, leading to the completion of the present invention. . That is, the present invention relates to the general formula () RCONHCH ₂ CONHCH ₂ COOM () (wherein RCO represents a fatty acid residue having 8 to 22 carbon atoms, and M represents a hydrogen atom, an alkali metal atom, an ammonium group, or an alkanolamine cation. This invention relates to a liquid detergent composition characterized by containing a dipeptide compound represented by (representing an ionic residue). The RCO- group of general formula () of the dipeptide compound in the present invention is at least one selected from residues of saturated fatty acids and unsaturated fatty acids having 8 to 22 carbon atoms, preferably 8 to 18 carbon atoms. Examples of the saturated fatty acids include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, erucic acid, and isostearic acid. Examples of unsaturated fatty acids include linoleic acid, linolenic acid, and oleic acid. Further, the RCO- group may be a residue of a mixed fatty acid, and examples of the mixed fatty acid include coconut oil fatty acid, palm oil fatty acid, palm kernel oil fatty acid, bovine fatty acid, and bran oil fatty acid. M in the general formula () of the dipeptide compound of the present invention represents a hydrogen atom, an alkali metal atom, an ammonium group, or an alkanolamine cation residue. Examples of alkali metals include sodium and potassium, and examples of alkanolamines include monoethanolamine,
Examples include diethanolamine and triethanolamine. The dipeptide compound of the present invention can be easily obtained according to a known method of acylating an amino acid. For example, after dissolving N-glycylglycine in a mixed solution of water and tetrahydrofuran as described in JP-A-54-100317, a fatty acid chloride is added and the acylation reaction is carried out at 30°C or lower. The dipeptide compound of the present invention is thereby obtained. Note that N-glycylglycine, which is a starting material for the dipeptide compound of the present invention, is obtained from glycine by a general method for producing peptides. By blending the dipeptide compound in the composition of the present invention in an amount of usually 3 to 40 wt%, preferably 5 to 30 wt%, a liquid cleansing composition that is not cloudy, has no peculiar odor, is mild to the skin, and has cleansing power can be obtained. It will be done. The composition of the present invention can be used as a kitchen detergent, hard surface cleaner, shampoo, liquid facial cleanser, liquid soap, bubble bath cleaner, etc., depending on the purpose of use. In the composition of the present invention,
Fragrances, such as those commonly used in liquid cleaning products,
Colorants, humectants, builders, hydrotropes,
Auxiliary agents such as preservatives can be added as appropriate.
Furthermore, there is no problem in adding other types of anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants for the purpose of adjusting detergency and foaming. These include fatty acid soaps, higher alcohol sulfate ester salts, polyoxyethylene higher alcohol sulfate ester salts, higher alcohol phosphate esters and their salts, polyoxyethylene higher alcohol phosphate esters and their salts, polyoxyethylene higher fatty acid phosphates, Acid esters and their salts, sulfonated higher fatty acid salts,
Sulfonated higher fatty acid alcohol ester salt, higher alcohol sulfosuccinate ester salt, isethionic acid higher fatty acid ester salt, α-sulfo higher alcohol acetate ester salt, higher alkyl dimethylbenzylammonium salt, higher alkyl amine,
Higher alkyltrimethylammonium salt, lauric acid diethanolamide, stearic acid diethanolamide, lauric acid monoethanolamide,
Condensates of higher fatty acids and alkylolamines such as stearic acid monoethanolamide and their ethylene oxide adducts, polyoxyethylene higher fatty acid monoethanolamide phosphates, N-long chain acyl acidic amino acid salts, N-long chain acyl sarcosines salts, N-long chain acylamino acid salts such as N-long chain acyl-N-alkyl-β-alanine salts, higher alkylaminopropionates such as lauryl aminopropionic acid, higher alkylimino diacetates such as lauryl iminodiacetate; Acetate, higher alkyl dimethyl betaine, higher alkyl dihydroxyethyl betaine, N-alkyloyl-
N'-(2-hydroxyethyl)-N'-carboxymethylethylenediamine salt, N-alkyloyl-
Examples include, but are not limited to, amine amide compounds such as N-(2-hydroxyethyl)-N' and N'-piscarboxymethylethylenediamine. The composition of the present invention has mild skin irritation and high biodegradability, and is less likely to become cloudy even at low temperatures and has no peculiar odor than conventional detergents containing N-acyl peptides. . The reason why the composition of the present invention has such an effect is not clear, but unlike, for example, an acylated product of a peptide derived from the natural protein collagen, the N-(N'-acylglycyl)glycine of the composition of the present invention contains lipids. , does not contain decomposition products such as polysaccharides, and therefore cloudiness caused by these impurities and volatile components such as aldehydes, ketones, keto acids, and sulfides generated by oxidation of impurities. It seems that there is no peculiar odor. Further, the present invention will be explained in detail with reference to Examples. Production example 1 Synthesis of N-(N'-lauroylglycyl)glycine 30.0 g (0.234 mol) of N-glycylglycine and 16.6 g (0.415 mol) of sodium hydroxide were dissolved in a mixed solvent of 240 ml of tetrahydrofuran and 240 ml of water. , kept at 25°C to 30°C. While stirring, add 39.4 g (0.18 g) of lauric acid chloride to this solution.
mol) was added dropwise over 2 hours. After further aging at the same temperature for 1 hour, concentrated hydrochloric acid was added to adjust the pH to 1, and the precipitated solid was removed and dried to obtain 51 g of N-(N'-lauroylglycyl)glycine. The yield is 91.4% and the free fatty acid content in the product is 9.1
It was %. When this product was analyzed by infrared spectroscopy, it was found that an amide absorption occurred at 1640 cm ^-1 in the infrared absorption spectrum, an absorption due to -COOH group occurred at 1730 cm ^-1 , and -COCl due to fatty acid chloride at 1800 cm ^-1 Acylation was confirmed by the disappearance of absorption by the group. Production Example 2 Synthesis of N-(N'-cocoylglycyl)glycine 66.5 g (0.52 mol) of N-glycylglycine and 40.6 g (0.01 mol) of sodium hydroxide were dissolved in a mixed solvent of 567 ml of tetrahydrofuran and 567 ml of water. ,
It was kept at 20℃ to 30℃. 91.6 g (0.42 mol) of cocoyl chloride was added dropwise to this solution over 2 hours while stirring. After further aging at the same temperature for 1 hour, concentrated hydrochloric acid was added to adjust the pH to 1, and the precipitated solid was collected and dried to obtain 116.6 g of N-(N-'cocoigrylcyl)glycine. The yield of this product was 91.0%, and the free fatty acid content was less than 10%. When this product was analyzed by infrared spectroscopy, it was found that the infrared absorption spectrum shows the occurrence of absorption due to amide group at 1640 cm ^-1 , absorption due to -COOH group at 1730 cm ^-1 , and absorption due to -COCl group at 1800 cm ^-1 . Acylation was confirmed from the disappearance of absorption. Production Example 3 Method for producing N-(N'myristoylglycyl)glycine Dissolve 66.5 g (0.52 mol) of N-glycylglycine and 40.6 g (1.01 mol) of sodium hydroxide in a mixed solvent of 600 ml of tetrahydrofuran and 600 ml of water.
While stirring, add 98.6 g (0.4 mol) of myristoyl chloride to the octopus solution kept at 25-30°C.
was added dropwise over 2.5 hours. After aging for another hour,
The same treatment as in Example 1 was carried out to obtain 117.6 g of N-(N'-myristoylglycyl)glycine. The yield was 87.0%, and the free fatty acid content was less than 10%. When this product was analyzed by infrared spectroscopy, it was found that in the infrared absorption spectrum, absorption occurred at 1640 cm ^-1 due to amide group, absorption occurred at 1730 cm ^-1 due to -COOH group, and absorption occurred at 1800 cm ^-1 due to - fatty acid chloride.
Acylation was confirmed by the disappearance of COCl absorption. Example 1 A hypoallergenic shampoo was prepared by mixing the following ingredients. ΓN-(N'-lauroylglycyl)glycine sodium salt ^* (25% aqueous solution) 30 parts Γ2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine (38
% aqueous solution) 20 Γ polyoxyethylene alkyl ether sulfate (30% aqueous solution) 15 Γ lauric acid diethanolamide 2 Γ ethylenediaminetetraacetic acid tetrasodium salt 0.5 Γ citric acid (amount to make pH 7) Appropriate amount Γ water Remaining 100 parts*: Manufacture The product obtained in Example 1 was neutralized with sodium hydroxide. Example 2 A kitchen detergent was manufactured by mixing the following ingredients. ΓN-(N'-cocoylglycyl)glycine sodium salt ^** (25% aqueous solution) 50 parts Sodium Γalkanesulfonate (30%) 30 Γurea 2 Γlauric acid diethanolamide 2 Γwater Remaining 100 parts**: Manufacture The product obtained in Example 2 was neutralized with sodium hydroxide. Example 3 A furniture cleaning agent was manufactured by mixing the following components. ΓN-(N'-myristoylglycyl)glycine sodium salt ^*** (25% aqueous solution) 30 parts Γ Sodium lauryl sulfate 15 Γ Lauric acid diethanolamide 2 Γ Water 53 100 parts ***: Obtained in Production Example 3 neutralized with sodium hydroxide. It was found that each of the liquid detergents of Examples 1 to 3 had good detergency and was less irritating to the skin. Comparative Examples 1 to 3 Examples 1 to 3 except that a commercially available acylated natural peptide was used in place of the N-(N-acylglycyl)glycine compound in each composition of Examples 1 to 3.
A liquid cleaning agent was produced in the same manner as (Comparative Examples 1 to 1).
3). Each of the liquid cleaning agents of Examples 1 to 3 and Comparative Examples 1 to 3 was left at 40°C and 0°C for one week, and the presence or absence of odor and turbidity was examined. The results are shown in Table 1.

[Table] From the results in Table 1, it is clear that the liquid detergent containing the dipeptide compound of the present invention has improved odor and turbidity compared to the conventional liquid detergent containing the acylated product of a natural peptide. It is.

Claims (1)

[Claims] 1 General formula () RCONHCH ₂ CONHCH ₂ COOM () (In the formula, RCO represents a fatty acid residue having 8 to 22 carbon atoms, and M is a hydrogen atom, an alkali metal atom, an ammonium group, or an alkanol. A liquid detergent composition characterized in that it contains a dipeptide compound represented by (representing an amine cationic residue). 2 The compound represented by the general formula () is N-
The composition according to claim 1, which is (N'-cocoylglycyl)glycine sodium salt. 3 The compound represented by the general formula () is N-
The composition according to claim 1, which is (N'-lauroylglycyl)glycine sodium salt. 4 The compound represented by the general formula () is N-
The composition according to claim 1, which is (N'-caproylglycyl)glycine sodium salt. 5 The compound represented by the general formula () is N-
The composition according to claim 1, which is (N'-stearoylglycyl)glycine sodium salt. 6 The compound represented by the general formula () is N-
The composition according to claim 1, which is (N'-oleoylglycyl)glycine sodium salt. 7 The compound represented by the general formula () is N-
The composition according to claim 1, which is (N'-cocoylglycyl)glycine ammonium salt. 8 The compound represented by the general formula () is N-
The composition according to claim 1, which is (N'-cocoylglycyl)glycine triethanolamine salt. 9 The compound represented by the general formula () is N-
The composition according to claim 1, which is (N'-permoylglycyl)glycine sodium salt.