A cleaning composition containing supramolecular amino acid derivatives, and a method for preparing and using the same

Abstract

The application provides a cleaning composition containing supramolecular amino acid derivatives and a preparation method and application thereof, and relates to the technical field of cleaning products. The cleaning composition comprises 0.5-20% of supramolecular amino acid derivatives, 0.1-10% of auxiliary surfactants, 0.1-5% of neutralizing agents, 0.1-5% of thickening agents, 1-15% of polyhydric alcohols, 0.5-2% of preservatives and the balance of water, wherein the pH value of the cleaning composition is 5.5-8.0. The composition has the advantages of synergistic effect between the supramolecular structure and each component, significantly improved cleaning force, low irritation, low risk of causing acne, easy rinsing, no false slip feeling, excellent skin feeling after washing, good formula stability and rich and delicate foam.

Description

Technical Field

[0001] This invention relates to the field of cleaning product technology, and more specifically, to a cleaning composition containing supramolecular amino acid derivatives, its preparation method, and its application. Background Technology

[0002] Daily skin and hair cleaning primarily relies on cleaning products containing surfactants. As consumers increasingly demand gentleness and safety, amino acid surfactants have become the mainstream choice for personal care products due to their mildness, low irritation, and good biodegradability.

[0003] However, existing cleaning systems based on amino acid surfactants still have the following technical shortcomings in practical applications: The contradiction between cleansing power and gentleness: Traditional amino acid surfactants have relatively weak detergency and oil emulsification abilities, making it difficult to meet the needs of deep cleansing. In addition, their rinsing process tends to produce a "slippery" feeling, and the skin often feels tight after washing, resulting in a poor user experience.

[0004] Potential acne-causing risks: Some amino acid surfactants or their compound systems have been reported to increase the risk of pimples and acne during long-term use, limiting their application in people with acne-prone skin.

[0005] Formula development is challenging: Amino acid surfactants are sensitive to pH, making it difficult to thicken the system. They also have poor compatibility with many commonly used additives, which increases the development threshold and cost of the product.

[0006] Patent CN 119792114 A discloses a composition containing lauroyl alanine, mainly comprising lauroyl alanine, sodium cocoyl methyl taurate taurate, hydroxyethyl deacetylated chitosan, basic amino acids, and water, which has the advantages of rich and delicate foam and mild irritation. Patent CN 119745711 A discloses a shampoo containing lauroyl alanine surfactant, obtained by neutralizing arginine with sodium hydroxide.

[0007] While existing technologies (such as CN119792114A and CN119745711A) disclose compositions containing amino acid surfactants such as lauroyl alanine, they have not solved the fundamental problem of balancing cleansing power and gentleness, nor have they provided a cleansing composition that simultaneously possesses strong cleansing power, low irritation, low comedogenicity, excellent skin feel (easy to rinse, no slippery residue, no tightness), and excellent stability. Summary of the Invention

[0008] A first aspect of the present invention provides a cleaning composition containing supramolecular amino acid derivatives, wherein the cleaning composition comprises, by mass fraction: The composition includes 0.5-20% supramolecular amino acid derivatives, 0.1-10% auxiliary surfactants, 0.1-5% neutralizing agents, 0.1-5% thickeners, 1-15% polyols, 0.5-2% preservatives, and the balance being water. The pH value of the cleaning composition is 5.5-8.0.

[0009] The sum of the mass fractions of supramolecular amino acid derivatives, auxiliary surfactants, neutralizers, thickeners, polyols, preservatives, and the remaining water is 100%.

[0010] Optionally, the supramolecular amino acid derivative can be any point value or a range between any two points from 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5%, 5.0%, 5.5%, 6.0%, 6.5%, 7.0%, 7.5%, 8.0%, 8.5%, 9.0%, 9.5%, 10.0%, 10.5%, 11.0%, 11.5%, 12.0%, 12.5%, 13.0%, 13.5%, 14.0%, 14.5%, 15.0%, 15.5%, 16.0%, 16.5%, 17.0%, 17.5%, 18.0%, 18.5%, 19.0%, 19.5%, or 20.0%.

[0011] Optionally, the auxiliary surfactant can be any point value or a range between any two points from 0.1%, 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5%, 5.0%, 5.5%, 6.0%, 6.5%, 7.0%, 7.5%, 8.0%, 8.5%, 9.0%, 9.5%, or 10.0%.

[0012] Optionally, the neutralizing agent can be any point value or a range between any two points from 0.1%, 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5%, or 5.0%.

[0013] Optionally, the thickener can be any point value or a range between any two points from 0.1%, 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5%, or 5.0%.

[0014] Optionally, the polyol can be any point value or a range between any two points from 1%, 1.5%, 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5%, 5.0%, 5.5%, 6.0%, 6.5%, 7.0%, 7.5%, 8.0%, 8.5%, 9.0%, 9.5%, 10.0%, 10.5%, 11.0%, 11.5%, 12.0%, 12.5%, 13.0%, 13.5%, 14.0%, 14.5%, or 15.0%.

[0015] Optionally, the preservative can be any point value or a range between any two points from 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, or 2.0%.

[0016] Optionally, the pH value of the cleaning composition can be any point value or a range between any two points from 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, or 8.0.

[0017] Optionally, the cleaning composition has a pH of 6.0-8.0, a viscosity of 2000-10000 cp, and a foam height of ≥500 mm. Preferably, the viscosity is 3000-8000 cp.

[0018] Optionally, the supramolecular amino acid derivative is lauroyl alanine. Produced and supplied by Suzhou Weimei, its molecules self-assemble into a supramolecular structure through non-covalent interactions, including one or more of hydrogen bonding, π-π stacking, and electrostatic interactions.

[0019] Optionally, the auxiliary surfactant is selected from one or more of cocamidopropyl betaine, alkyl glycosides, sodium alkyl taurate, cocamidopropyl arginine, sodium amphoteric acetate, lauryl hydroxysulfonate betaine, and sodium laurate taurate. Optionally, the alkyl glycoside is a C8-16 alkyl glycoside. Preferably, the auxiliary surfactant is a compound of cocamidopropyl arginine and sodium laurate taurate. Further, the compound of cocamidopropyl arginine and sodium laurate taurate specifically comprises, by mass fraction, 20-25% cocamidopropyl arginine, 5-8% sodium laurate taurate, and 69-73% water. Preferably, the compound of cocamidopropyl arginine and sodium laurate taurate specifically comprises, by mass fraction, 23% cocamidopropyl arginine, 6% sodium laurate taurate, and 71% water.

[0020] Optionally, the neutralizing agent may be one or more selected from arginine, triethanolamine, aminomethylpropanol, sodium hydroxide, and potassium hydroxide. The neutralizing agent has a good synergistic effect with the supramolecular structure of lauroyl alanine, further improving mildness and user experience.

[0021] Preferably, the neutralizing agents are arginine and potassium hydroxide, and the pH value of the cleaning composition is 7.0-7.6.

[0022] Optionally, the thickener is selected from one or more of hydroxyethyl cellulose, xanthan gum, carbomer, acrylate copolymers, hydrophobic modified acrylate copolymers, guar gum, nonionic thickeners, and acrylate / stearyl ether-20-methacrylate crosspolymers. Preferably, the thickener is an acrylate / stearyl ether-20-methacrylate crosspolymer (this substance is from Dow Chemical, trade name Aculyn98). The thickener exhibits good compatibility and thickening efficiency with supramolecular amino acid derivative systems.

[0023] Optionally, the polyol is selected from one or more of glycerol, butylene glycol, propylene glycol, sorbitol, and polyethylene glycol.

[0024] Optionally, the preservative is selected from one or more of phenoxyethanol, p-hydroxyacetophenone, sodium benzoate, potassium sorbate, ethylhexylglycerin, and 1,2-hexanediol. The preservative is used to ensure the microbial stability of the composition. Preferably, the preservative is a mixture of phenoxyethanol and ethylhexylglycerin, which has excellent compatibility with supramolecular amino acid derivative systems, achieving good preservative effects at low dosages, and exhibiting low irritation.

[0025] Optionally, the mass ratio of the supramolecular amino acid derivative to the auxiliary surfactant is (1-3):1. For example, the mass ratio of the supramolecular amino acid derivative to the auxiliary surfactant can be any value in 1:1, 2:1 or 3:1 or a range between any two values.

[0026] Optional, the water is deionized water.

[0027] A second aspect of the present invention provides a method for preparing a cleaning composition containing supramolecular amino acid derivatives, comprising the following steps: Water and polyol are mixed, then thickener, auxiliary surfactant and supramolecular amino acid derivative are added in sequence, mixed evenly, heated to a certain temperature, neutralizer is added, and then cooled. Finally, preservative is added and mixed evenly to obtain a cleaning composition.

[0028] Optionally, the temperature is heated to a certain temperature, which is 70-85℃, and then cooled down to below 45℃.

[0029] A third aspect of the present invention provides the use of a cleansing composition containing supramolecular amino acid derivatives in the preparation of cosmetics for skin or hair cleansing.

[0030] Optionally, the cosmetic product may be in the form of any one of facial cleanser, facial foam, shampoo, or shower gel.

[0031] Compared with the prior art, the present invention achieves at least one of the following beneficial effects: This invention achieves synergistic effects and unexpected technical results by screening specific supramolecular amino acid derivatives and compounding them with specific types and proportions of auxiliary surfactants, neutralizers, thickeners, and other components. 1. Excellent balance between cleaning power and gentleness: Example data shows that the compositions of this invention (such as formulation 28) achieve a stain removal rate of up to 92% on standard soiled cloths, significantly superior to commercially available amino acid facial cleansers (75% and 73%). This is attributed to the supramolecular structure of lauroyl alanine itself, which enhances the surfactant molecules' ability to encapsulate and remove grease. HET-CAM test results show that the irritation scores of the compositions of this invention (0.4-0.6) are significantly lower than those of commercially available products (2.0 and 1.5), reaching a level of non-irritation or very slight irritation, demonstrating their excellent gentleness and safety.

[0032] 2. Excellent Formulation Stability and Skin Feel: The composition of this invention exhibits no stratification, precipitation, or discoloration after 30 days of cyclic storage at -10℃ to 45℃, and a viscosity change rate of less than 10% after 30 days at a high temperature of 50℃, demonstrating excellent storage stability. In particular, by screening specific hydrophobic modified acrylate thickeners (such as Aculyn 98), the technical challenges of thickening and poor stability in amino acid systems have been overcome. The composition has a suitable viscosity of 3000-8000 cP, produces abundant foam (foam height ≥ 500 mm), and has a fine texture. Consumer testing shows excellent rinsing performance, no slippery feeling, and no tightness after washing. Specifically, when the neutralizing agent is replaced with potassium hydroxide and the pH is controlled at 7.0-7.6, rinsing performance and the slippery feeling are significantly improved.

[0033] 3. Low risk of acne-causing: Through in vitro sebaceous gland cell model and rabbit ear test, the acne-causing risk of the composition of the present invention is significantly lower than that of existing amino acid systems, making it particularly suitable for people with acne-prone skin.

[0034] 4. Excellent compatibility and simple formulation: This invention has found that by controlling the weight ratio of lauroyl alanine to cocoyl arginine salt / sodium laurate within a specific range of 3:1 to 1:1, not only can the best cleaning power and skin feel be obtained, but the problem of precipitation in the composition when diluted with tap water can also be solved, ensuring the stability of the product in actual use.

[0035] 5. Simple formulation: The formulation does not require the addition of complex supramolecular forming agents, which reduces the cost and complexity of raw materials and facilitates industrial production. Attached Figure Description

[0036] The accompanying drawings, which are included to provide a further understanding of the invention and form part of this invention, illustrate exemplary embodiments of the invention and are used to explain the invention, but do not constitute an undue limitation of the invention. In the drawings: Figure 1 This invention illustrates an exemplary embodiment of the ease of rinsing under tap water rinsing conditions, simulating the rinseability of lauroyl alanine and cocoyl arginine salt / sodium lauroate at different ratios. Figure 2 The following diagram shows the foam height test results of formulations 28 and 29 of the present invention, as well as comparative examples 1, 2, 3, and 4. Detailed Implementation

[0037] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.

[0038] Unless otherwise specified, the raw materials used in the embodiments and comparative examples of this application were all purchased commercially.

[0039] Unless otherwise specified, the methods used in the embodiments and comparative examples of this application are conventional methods in the prior art.

[0040] In the following examples, the compound of cocoate arginine salt and sodium laurate taurate specifically includes, by mass fraction, 23% cocoate arginine salt, 6% sodium laurate taurate, and 71% water.

[0041] Example 1: Thickener Screening Experiment A method for preparing a cleaning composition containing supramolecular amino acid derivatives includes the following steps: Add some water and polyol to the main pot, stir well, then add the thickener and stir until evenly dispersed. Add the auxiliary surfactant and stir until evenly dispersed, then add the supramolecular amino acid derivative. Heat to 80°C, continue stirring until evenly dispersed, then add the neutralizing agent. Stir until the system is clear and transparent. Cool to below 45°C, add the preservative, stir until evenly dispersed, and then discharge.

[0042] In this embodiment, the appearance, flow properties, and viscosity of the composition were evaluated by screening different thickeners. See Table 1 for reference.

[0043] In this composition, A1 is water, A2 is a polyol, B is a thickener, C1 is a supramolecular amino acid derivative, C2 and C3 are auxiliary surfactants, D is a neutralizer, and E is a preservative.

[0044] Table 1

[0045] Referring to Table 1, it can be seen that when the thickener is an acrylic (ester)-based / stearyl polyether-20 methacrylate crosspolymer, the prepared clean composition can simultaneously meet the requirements of transparent appearance, good flowability, and viscosity in the range of 2000-10000 cp.

[0046] Neutralizer Screening Experiment in Example 2 To further improve the feel, rinsing performance, and slippery sensation of the cleaning composition, this example screens the neutralizing agents arginine and potassium hydroxide under the preferred conditions of Example 1. The preparation method is the same as in Example 1, as shown in Table 2.

[0047] Table 2

[0048] As shown in Table 2, it can be seen that using potassium hydroxide results in a better skin feel, significantly improving rinsing performance and reducing the slippery feeling. Further analysis of the amount of potassium hydroxide added revealed that good foaming performance was achieved when the pH was controlled between 7.0 and 7.6. Further analysis of the amount of surfactant added showed that when the amount of surfactant added to the composition exceeded that of Formulation 17, the viscosity of the system was too low, making it inconvenient for daily use.

[0049] Example 3: Screening experiment on the ratio of supramolecular amino acid derivatives to auxiliary surfactants. To further improve rinsing performance and reduce the slippery feeling and tightness after washing, based on the preferred conditions of Examples 1 and 2, the ratio of supramolecular amino acid lauroyl alanine (LA) and cocoyl arginine salt / sodium laurate taurate CRT-30 was studied in depth, as shown in Table 3.

[0050] Table 3

[0051] As shown in Table 3, when the ratio of supramolecular amino acid derivative lauroyl alanine to auxiliary surfactant (cocoyl arginine salt / sodium laurate taurate CRT-30) is 1:1-3:1, the overall performance of the cleaning composition is optimal, improving rinsing performance and reducing the slippery feeling and tightness after washing.

[0052] Example 4 Based on Example 3, the cleaning compositions of formulas 19-24 were added to 5 wt% tap water. (Reference) Figure 1 As shown, Figure 1In the middle, 1' is formula 19, 2' is formula 20, 3' is formula 21, 4' is formula 22, 5' is formula 23, and 6' is formula 24.

[0053] from Figure 1 As can be seen from Formula 20 onwards, precipitates appear in the aqueous solution, indicating that insoluble substances are produced in the composition under tap water dilution conditions, which further explains the improvement in the skin feel after rinsing.

[0054] Example 5 Based on formulation 23 in Example 3, the amount of thickener was further investigated to obtain a suitable composition viscosity for easy daily use. The test results are shown in Table 4.

[0055] Table 4

[0056] As shown in Table 4, it can be seen that when the amount of thickener acrylate / stearyl alcohol polyether-20 methacrylate crosspolymer added is 3.5%-4%, better viscosity and foaming properties can be obtained.

[0057] Comparative Example Comparative Example 1: Based on Formula 28, when lauroyl alanine was replaced with an equal amount of lauroyl sarcosine, as shown in Table 5, the viscosity and foaming properties deteriorated.

[0058] Comparative Example 2: Based on Formula 28, without adding thickener, the viscosity difference is shown in Table 5.

[0059] Comparative Example 3: Based on Formula 28, without the addition of glycerin, the stability is poor, as shown in Table 5.

[0060] Comparative Example 4: Based on Formula 28, when lauryl hydroxysulfobetaine was replaced with sodium lauroyl amphoteric acid, the viscosity was poor and it became irritating.

[0061] Table 5

[0062] Test case Formulas 28, 29, 30, Comparative Example 1, Comparative Example 2, Comparative Example 3, Comparative Example 4, commercially available amino acid 1 (Ximuyuan Fertilizer Cleansing Honey), and commercially available amino acid 2 (Fuyu Manpu Tuberose Light-Sensing Fermented Essence Cleansing Honey) were tested for their cleansing power, foam height, irritation, and stability. The test results are shown in Table 6.

[0063] Cleaning power test: Microscopic images of volunteers' skin were obtained before, after, and after cleaning with the sample. The L*, a*, and b* values ​​of the images were analyzed using IPP software. The color difference after applying the dirt was calculated compared to before the dirt application, denoted as ΔE(after application); the color difference after cleaning with the product was calculated compared to after the dirt application, denoted as ΔE(after cleaning). ΔE reflects the three-dimensional change in color; a larger ΔE value indicates a more significant color difference, while a smaller ΔE value indicates a closer color. The product's cleaning ability is calculated using the ΔE value. The cleaning rate calculation formula is: .

[0064] Irritation Test: Referring to the standards for the chicken embryo chorioallantoic membrane test for eye irritation / corrosiveness of cosmetics in the Entry-Exit Inspection and Quarantine Industry Standards, this study adopted the reaction time method. Nine-day-old chicken embryos were candled, and the air cell location was marked on the eggshell surface. The marked portion of the eggshell was peeled off using dental serrated forceps to expose the white egg membrane. An appropriate amount of 0.9% NaCl solution was drawn with a pipette to moisten the egg membrane, and then the solution was poured out. The inner membrane was carefully removed with forceps, ensuring no damage to the vascular membrane. 0.3 mL of the test reagent was added to the surface of the chorioallantoic membrane, and the average time to onset of bleeding (secH), the average time to vascular dissolution (secL), and the average time to onset of clotting (secC) were recorded within 5 minutes. Video and photographs were taken during this period. Each sample was tested in 6 parallel trials. IS < 1 indicated no irritation, 1 ≤ IS < 5 indicated mild irritation, 5 ≤ IS < 9 indicated moderate irritation, and IS > 9 indicated severe irritation.

[0065] .

[0066] Stability test: The temperature was cyclically placed between -10℃ and 45℃ for 30 days. Specifically, the high temperature was 45℃±2℃ and the low temperature was -8℃ to -10℃ for 5 cycles, with an interval of at least 24 hours between each cycle. The temperature was then restored to room temperature for observation, for a total duration of 30 days.

[0067] Viscosity change rate test: The viscosity change rate was measured after being placed at a high temperature of 50°C for 30 days.

[0068] Table 6

[0069] Referring to Table 6, the compositions of the present invention (such as Formulation 28) achieved a stain removal rate of up to 92% on standard soiled cloths, significantly superior to commercially available amino acid facial cleansers (75% and 73%). This is attributed to the supramolecular structure of lauroyl alanine itself, which enhances the surfactant molecules' ability to encapsulate and remove grease. HET-CAM test results showed that the irritation scores of the compositions of the present invention (0.4-0.6) were significantly lower than those of commercially available products (2.0 and 1.5), reaching a level of non-irritation or very slight irritation, demonstrating their excellent gentleness and safety.

[0070] The composition of the present invention exhibits good storage stability, showing no stratification, precipitation, or discoloration after being cyclically stored at -10℃ to 45℃ for 30 days, and a viscosity change rate of less than 10% after being stored at a high temperature of 50℃ for 30 days.

[0071] refer to Figure 2 As shown, Figure 2 The images, from left to right, show the foam height test results for Formula 28, Formula 29, Comparative Example 1, Comparative Example 2, Comparative Example 3, and Comparative Example 4, respectively. It can be seen that the compositions produce abundant foam (foam height ≥ 500 mm) and have a fine texture.

[0072] The above description is merely an embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principle of the present invention should be included within the scope of the claims of the present invention.

Claims

1. A cleaning composition containing supramolecular amino acid derivatives, characterized in that, The cleaning composition comprises, by mass fraction: The composition includes 0.5-20% supramolecular amino acid derivatives, 0.1-10% auxiliary surfactants, 0.1-5% neutralizing agents, 0.1-5% thickeners, 1-15% polyols, 0.5-2% preservatives, and the balance being water. The pH value of the cleaning composition is 5.5-8.

0.

2. The cleaning composition containing supramolecular amino acid derivatives according to claim 1, characterized in that, The cleaning composition has a pH of 6.0-8.0, a viscosity of 2000-10000cp, and a foam height of ≥500mm.

3. The cleaning composition containing supramolecular amino acid derivatives according to claim 1, characterized in that, The supramolecular amino acid derivative is lauroyl alanine; And / or the auxiliary surfactant is selected from one or more of cocamidopropyl betaine, alkyl glycoside, sodium alkyl taurate, arginine cocoate, sodium amphoteric acetate, and lauryl hydroxysulfonate; And / or the neutralizing agent is one or more selected from arginine, triethanolamine, aminomethylpropanol, sodium hydroxide, and potassium hydroxide; The thickener is selected from one or more of hydroxyethyl cellulose, xanthan gum, carbomer, acrylate copolymers, hydrophobic modified acrylate copolymers, guar gum, and nonionic thickeners. And / or the polyol is selected from one or more of glycerol, butylene glycol, propylene glycol, sorbitol, and polyethylene glycol; And / or the preservative is selected from one or more of phenoxyethanol, p-hydroxyacetophenone, sodium benzoate, potassium sorbate, ethylhexylglycerin, and 1,2-hexanediol.

4. The cleaning composition containing supramolecular amino acid derivatives according to claim 3, characterized in that, The neutralizing agents are arginine and potassium hydroxide, and the pH of the cleaning composition is 7.0-7.

6.

5. The cleaning composition containing supramolecular amino acid derivatives according to claim 3, characterized in that, The mass ratio of supramolecular amino acid derivatives to auxiliary surfactants is (1-3):

1.

6. The cleaning composition containing supramolecular amino acid derivatives according to claim 3, characterized in that, The thickener is an acrylic (ester) / stearyl polyether-20 methacrylate crosspolymer.

7. A method for preparing the cleaning composition according to any one of claims 1-6, characterized in that, Includes the following steps: Water and polyol are mixed, then thickener, auxiliary surfactant and supramolecular amino acid derivative are added in sequence, mixed evenly, heated to a certain temperature, neutralizer is added, and then cooled. Finally, preservative is added and mixed evenly to obtain a cleaning composition.

8. The preparation method according to claim 7, characterized in that, Heating to a certain temperature, which is 70-85℃, and cooling down to below 45℃.

9. Use of the cleaning composition according to any one of claims 1-6 in the preparation of cosmetics for cleansing skin or hair.

10. The application according to claim 9, characterized in that, The cosmetic product is any one of the following formulations: facial cleanser, facial foam, shampoo, or shower gel.

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