JPH0226675B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel detergent composition, and its purpose is to provide a detergent composition that exhibits excellent detergency and foaming properties, and has a mild effect on the skin and hair. . In recent years, as awareness of safety has increased, expectations have increased for the development of safe materials for various cleaning agents, and the materials currently used are also being reviewed from a safety perspective. It is being done. However, when high safety is required,
Functional aspects such as cleaning performance and foaming performance are not always satisfied. Therefore, many attempts have been made to obtain new detergents that are expected to have a synergistic effect through combinations of these conventionally known surfactants. Furthermore, as a matter of course, surfactants, which have not been studied in the past, are now being reviewed from a new perspective. Among these surfactants, in recent years, compounds with an amino acid skeleton in the molecule, especially N-long chain acylamino acid salts, have been reviewed in terms of their excellent functionality and safety.
Furthermore, it has come to be used more frequently due to progress in research on combinations with other surfactants. N to the representative ones
-Long chain acyl sarcosine salts and N-long chain acyl glutamates, which are already widely used in shampoos, solid detergents, kitchen cleaners, etc. Regarding these so-called amino acid-based surfactants, the present inventor seeks compounds with even higher functionality and safety, and also aims to develop new cleaning agents by combining these with other surfactants. As a result of our extensive efforts, we have discovered that the N-methyl derivative of N-long-chain acyl lysine, which was virtually unknown, is water-soluble, has excellent surfactant properties such as foaming properties, and is highly safe for the skin. In addition to confirming that it can be used as a raw material for a new cleaning composition,
It has been discovered that when mixed with an amphoteric surfactant, the properties of the two act synergistically, resulting in a new detergent composition that exhibits unprecedented foaming properties and detergency, and is also highly safe, and has developed the present invention. I was able to complete it. One component used in the detergent composition of the present invention, N〓-long chain acyl N〓, N〓-dimethyllysine or N〓-long chain acyl N〓, N〓, N〓-trimethyllysine, is generally It has a structure represented by the formula [] or []. (However, in the []/[] formula, RCO represents an aliphatic acyl group having 8 to 22 carbon atoms.) Here, N-unmethylated N-long-chain acyl lysine is known as an amphoteric surfactant. However, this substance is extremely poorly soluble in water under neutral conditions, which is the normal usage condition, and cannot be put to practical use (Oil Chemistry 26-30285 ).
110 (1977)). Therefore, in order to develop water solubility, dimethylation or trimethylation at the N-position was first performed, and it was found that the water solubility was improved to the extent that it could be used as a detergent. Also, among these compounds, [ ] is only described as a special cleaning agent or disinfectant (Japanese Patent Publication No. 42-11926, Japanese Patent Publication No. 51-44172, Japanese Patent Publication No. 51-28610), and the compound [ ]
has not been studied at all as a surfactant. When the surfactant ability and skin safety of the compound [ ] or [ ], which could be measured for the first time by imparting water solubility, were measured, it was found that one of the main components of the cleaning composition of the present invention. It was confirmed that it can be used as a raw material. (See Example 1, table)
To obtain these compounds [] or [], N〓,N〓-dimethylated form of lysine or N〓,N〓,N〓-
The so-called Schotten Baumann method uses a trimethylated product with a C ₈ - C ₂₂ fatty acid chloride and an alkali.
Depending on the method of N-acylation by reaction,
Or obtained by heating and dehydrating lysine higher fatty acid salt
The N-long chain acyl lysine may be dimethylated or trimethylated at the N-position using a methylating agent such as methyl iodide. In the formulas [] and [], the acyl group that is RCO is a fatty acid residue having 8 to 22 carbon atoms, such as a single fatty acid acyl such as 2-ethylhexanoyl, lauroyl, palmitoyl, stearoyl, oleoyl, isostearoyl, etc. Others, coconut oil fatty acids,
Mixed fatty acid acyl such as hydrogenated beef tallow fatty acid can be mentioned. The selection of the compound [ ] or [ ] is made depending on the form of the intended detergent, but the solubility in water generally increases as the degree of N-methylation increases. That is, [] is greater than [],
Further, it is used considering that the shorter the acyl group, the larger the size. Further, [ ] and [ ] can be used alone, but a mixture thereof can also be used. The isoelectric point of this compound is near neutrality, and it is usually used at this isoelectric point, but for alkaline cleaning agents, salts of sodium, potassium, ammonium, alkylolamines, basic amino acids, etc. are used. In the case of acidic cleaning agents, salts of hydrochloric acid, sulfuric acid, organic acids, acidic amino acids, etc. are used as appropriate. Although general amphoteric surfactants can be used as the other component of the cleaning composition of the present invention, the following amphoteric surfactants are particularly excellent in their synergistic effects. (1) Alkylamino or iminocarboxylate represented by general formula [] (In the formula, R is an alkyl group or alkenyl group having about 8 to 22 carbon atoms, m and n are integers of 0 to 3, and m+n≦6, l is 1 to 2, M
are hydrogen, alkali metals, alkaline earth metals,
NH ₄ , a cation derived from an alkanolamine, X is hydrogen or CH ₃ , Y is hydrogen, CH ₃ or —CH ₂ COOM ₂ . ) (2) Carboxybetaine type represented by the general formula [], [] (In the formula, R ₁ is an alkyl group or alkenyl group having about 8 to about 22 carbon atoms, R ₂ , R ₃ and R ₄ are each an alkyl group having 1 to 3 carbon atoms or (CH ₂ CH ₂ O) _o H (n is 1 to 10) or -
CH ₂ COOM (M is hydrogen, alkaline earth metal,
NH ₄ , a cation derived from alkanolamines). (3) Aminosulfonic acid type represented by general formula [] (In the formula, R is an alkyl group or alkenyl group having 8 to 22 carbon atoms, and R' is an alkyl group having 1 to 3 carbon atoms or derived from hydrogen, an alkali metal, an alkaline earth metal, NH ₄ , or an alkanolamine. It is a cation. n is an integer from 1 to 3.) (4) Amine oxide type represented by general formula [] (In the formula, R is an alkyl group or alkenyl group having about 8 to 22 carbon atoms, and R ₁ and R ₂ are alkyl groups having about 1 to 3 carbon atoms.) (5) Imidazoline type represented by the general formula [] [] [] [XI] (However, in the formula, R ₁ is an alkyl group or alkenyl group having about 4 to 18 carbon atoms, R ₂ is an alkylene group having 1 to 4 carbon atoms, and R ₃ is R ₂ or OH
an alkylene group substituted with a group, M is a hydrogen atom,
Cations and G are anions derived from alkali metals or alkanolamines. ) (6) Amidamine type represented by general formula [XII] [] (However, in the formula, R ₁ is an alkyl group or alkenyl group having about 8 to 22 carbon atoms, R ₂ is -CH ₂ COOM or -CH ₂ COOM or -CH ₂ CH ₂ COOM, R ₃ is hydrogen, -CH ₂ COOM or ―CH ₂ CH ₂ COOM,
M is a cation that forms a water-soluble salt). (However, in the above formula, R ₁ , R ₂ , R ₃ have the same meanings as the symbols in general formula [XII], and R ₄ is hydrogen, -
CH ₂ COOM or -CH ₂ CH ₂ COOM, where M represents the same meaning as the symbol in general formula [XII]). Blending ratio of N〓-long-chain acyl-N〓,N〓-dimethyl and N〓,N〓,N〓-trimethyllysine derivatives or salts thereof and the above amphoteric surfactant in the cleaning composition of the present invention Although the ratio differs depending on the individual composition, an excellent synergistic effect is usually observed in the range of 1/9 to 9/1, particularly around 8:2 to 2:8. For example, using the representative amphoteric surfactant mentioned above, we conducted a foaming test using the Ross Miles method on aqueous solutions containing various proportions of this N〓-long-chain acyl-N〓-methyllysine derivative. is as shown in Table 1, and as is clear from the table, when N,N-dimethyl-N-alkyl-N-carboxymethylammonium betaine is mixed with betaine at a weight ratio of 8:2,
It is highest when the weight ratio is 8:2 in a mixed system with 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolium salt, and when the weight ratio is 1:1 in a mixed system with dimethylalkylamine oxide. It will be understood that this produces a foaming effect. Detergent compositions can be obtained in various forms such as solid, powder, paste, and liquid, and typical uses include shampoo, cleansing foam, solid detergent, kitchen detergent, and liquid or powder detergent for clothing. It is mentioned as something like that. By the way, regardless of the form of a detergent, it is extremely important for the detergent to be soluble in water during use in order to fully demonstrate its detergency.Therefore, it is important to select a solubilizing agent with excellent blending properties. It also influences the quality of the product. As a result of further investigation as a solubilizing agent for the compound [] or [], which is a component of the present invention, we found that in addition to urea, ethyl alcohol, propylene glycol, and P-toluene sulfonate, which are often used in liquid form, water-soluble alkali Earth metals such as magnesium chloride, magnesium sulfate, and calcium chloride are effective in improving their solubility. The cleaning composition of the present invention may contain other adjuvants such as anionic surfactants such as N-acyl amino acid salts, N-acyl proteins, alkali metal salts of polyoxyethylene higher alcohol sulfate, and fatty acids as foaming enhancers. Organic salts such as alkylolamides, inorganic salts such as sodium sulfate, phosphates, zeolites, proteins as emollients, lanolin, lecithin, or oil-soluble nonionic surfactants such as glycerin fatty acid esters, sugar esters, N-acylamino acids Long-chain alcohol esters, etc., glycerin, propylene glycol, higher alcohols, etc. as form-preserving agents, diluents, etc., drugs such as zinc pyrithione, fragrances, dyes, etc. can be added depending on the intended use and form. . The features of the cleaning composition thus obtained are as follows. (1) A wide variety of liquid, dough, solid, and powder products can be obtained. (2) The resulting detergent has a mild action on the skin, hair, and fibers. (3) When the hair is washed, rinsing is easy and the hair conditionability after washing is excellent. Hereinafter, this will be explained in detail using examples. In the examples, % means weight %. Example 1 N〓-long chain acyl-N〓, N〓-dimethyl (or
N〓,N〓,N〓-trimethyl)lysine and various amphoteric surfactants were mixed and the solubility and foaming power were measured. The measurement conditions and method are as follows. 1 Measurement conditions (1) Solubility The solubility of the surfactant in a 0.25% aqueous solution at room temperature and 40°C was examined. Abbreviations in the table; S:
Dissolution (2) Foaming power Measure a 0.25% aqueous solution of surfactant at 40℃ using the Rothsmiles method, immediately after (0 minute value)
Expressed as the value of 2 Measurement Results As shown in the table, the lysine derivative, which is one of the main components of the cleaning composition of the present invention, has excellent foaming properties and cleaning power even when used alone, and when mixed with various amphoteric surfactants, it has a relatively wide range of foaming properties. The solubility improved within the range, and a complementary effect on foaming power was observed.

【table】 Example 2 Xiampu

[Table] The table shows the results of measuring hair washing power and primary skin irritation using domestic rabbits when the ratio of surfactants was varied in shampoo compositions having the above compositions. As is clear from these results, a system in which both surfactants are mixed has superior hair washing power compared to when each is used alone, and the finish after washing is better than that of imidazoline surfactants alone. It was found that primary skin irritation was improved. Judgment <2...Mild 2~5...Moderate >5...Severe

[Table] Measurement method Hair washing power: 2ml of artificial sludge and 0.05g in hairpiece
Apply clay, drop 0.5ml of the sample shampoo onto it, and press and wash for 15 seconds. If bubbles do not form, lightly rinse the hairpiece with warm water from step 1, drain the water, and repeat the process again. Hot water cannot be replaced. Record the number of drops of shampoo when enough foam has formed. The smaller the value, the better the hair washing power. Primary skin irritation: New Zealand White male rabbits weighing 2.5-3.0 kg per group of 6 animals were used in closed patches. After one day, the adhesive plaster for the patch test was removed, and the irritation was evaluated according to the Draize evaluation criteria. The test sample was prepared by adding 25ml of this cleaning agent to water.
It was diluted with 75 ml and used. Example 3 Shampoo N〓-Hydrogenated beef tallow fatty acid acyl-N〓,N〓-dimethyllysine 5.0% N-Palmitoyl-N〓,N〓,N〓-trimethyllysine 4.0 Dimethylstearylamine oxide 7.0 Coconut oil fatty acid diethanolamide 0.7 Poly Sodium oxyethylene lauryl sulfate
0.7 Propylene Glycol 1.0 PCA.Na 0.5 NaCl 0.4 Water 80.7 With the above formulation, a shampoo was obtained which had excellent foaming properties, a creamy foam feel during use, and a gentle feel on the hair after use. Example 4 Shampoo N〓-Lauroyl-N〓,N〓-dimethyllysine
15.0% Dimethyllaurylamine betaine acetate 4.0 N-cocoyl-L-glutamic acid monotriethanolamine 1.0% Prodeyu #200 (wetting agent manufactured by Ajinomoto KK) 2.0 Calcium chloride hexahydrate 2.0 Water 76.0 The above composition provides rich foaming and cleaning properties A shampoo with strong strength and a moist feel on the hair after use was obtained. Example 5 Solid detergent N〓-hardened beef tallow fatty acid acyl-N〓,N〓-dimethyllysine 37.0% N〓-palmitoyl-N〓,N〓-dimethyllysine
25.0 Dimethylpalmitylcarboxymethylammonium 20.0 Cetyl alcohol 5.0 Polyoxyethylene hydrogenated castor oil monopyroglutamate 3.0 Isostearate water 10.0 After thoroughly kneading each of the above compositions with a small roll, mix them in a small roll with a temperature of 40 to 50°C. The bar-shaped detergent obtained by extrusion using a bar soap prototype device was molded using a foot-type molding machine. The obtained solid soap has cleaning power,
It has excellent foaming power and has an excellent gentle feel on the skin. Example 6 Kitchen detergent N〓-Coconut oil fatty acid acyl-N〓,N〓-Dimethyllysine 13.8% N〓-Coconut oil fatty acid acyl-N〓,N〓,N〓-Trimethyllysine 7.6 2-Undecanyl-N-carboxy Methyl-N
-Hydroxyethylimidazolium betaine
7.6 Coconut oil fatty acid diethanolamide 2.0 Ethanol 3.0 Propylene glycol 2.0 DiNa citrate 1.4 Water 62.6 With the above formulation, a dishwashing detergent composition that has excellent detergency and foaming power and is mild to the skin can be obtained. Obtained.

Claims (1)

[Claims] 1 Represented by the following general formula [] or []
N〓-long chain acyl-N〓, N〓-dimethyllysine or
A cleaning composition comprising at least one of N〓-long-chain acyl-N〓, N〓, N〓-trimethyllysine or a salt thereof and an amphoteric surfactant as main components. (However, in the formula, RCO represents an aliphatic acyl group having 8 to 22 carbon atoms.) 2. The amphoteric surfactant is an alkylamino or iminocarboxylic acid type, a carboxybetaine type, an aminosulfonic acid type, an amine oxide type, an imidazoline type, or an amidoamine type. The cleaning composition according to claim 1, which is an active agent having a type structure.