Deoiling, moisturizing and low-irritation hair cleaning surfactant and preparation method thereof

Abstract

The invention belongs to the field of hair cleaning agent preparation, and particularly relates to an oil-removing moisturizing low-irritation hair cleaning surfactant and a preparation method thereof. By optimizing a formula and a process, multi-functionalization and high efficiency of a hair care product are realized. Firstly, the walnut protein enzymatic hydrolysate, the oat beta-glucan and other natural components are adopted, the components are rich in high protein and bioactive peptide, can provide rich nutrition for hair and scalp, promote hair growth and repair damaged hair cuticles, also have good biocompatibility and safety, and are suitable for long-term use; the composition is especially friendly to sensitive scalp. Secondly, various surfactants such as sodium laureth sulfate and cocamidopropyl betaine are combined, so that a mild cleaning effect is provided, a protective layer can be formed on the surface of hair, static electricity is reduced, and the hair is softer and more glossy.

Description

Technical Field

[0001] The invention belongs to the field of hair cleaning agent preparation, and particularly relates to an oil-removing, moisturizing and low-irritation hair cleaning surfactant and a preparation method thereof. Background Art

[0002] As people's demand for personal care products continues to increase, shampoo products not only need to have a cleaning function, but also need to meet consumers' pursuit of multiple functions such as fluffy, soft, and easy to comb hair. In order to achieve the smooth effect of hair, traditional formulas often rely on silicone oil (such as polydimethylsiloxane) or cationic conditioning agents (such as cationic guar gum), which wrap the surface of hair to form a smooth film layer to reduce friction. However, such ingredients tend to accumulate on the hair and scalp, causing the hair to flatten and lose its fluffy feeling. Long-term use may also cause pore blockage or scalp sensitivity. In addition, some anionic surfactants may destroy the hair keratin structure due to their strong degreasing power, leading to problems such as hair scale damage, frizzy split ends, etc. Therefore, it is difficult for the existing technology to achieve an ideal balance between cleaning power, fluffy feeling and softness.

[0003] The main contradiction of the existing technology is that it is difficult to balance the cleaning and conditioning functions. In order to achieve a fluffy effect, the use of silicone oil or cationic conditioning agents needs to be reduced, but this will lead to a lack of lubrication protection on the hair surface, increased friction, making the hair more frizzy and difficult to comb; while over-reliance on softening ingredients sacrifices the fluffy feeling, causing the hair to stick to the scalp and lack a three-dimensional sense. On the other hand, although traditional surfactants (such as sulfates) have strong cleaning power, they are highly irritating and may damage the scalp barrier function, causing dryness, itching and other discomforts, and their environmental residue problems are also subject to increasingly stringent regulatory restrictions. In addition, the existing technology has a weak ability to integrate natural ingredients, and it is difficult to achieve long-term nutrition and repair through bioactive ingredients (such as plant proteins and polysaccharides), which limits the comprehensiveness of product functions.

[0004] The development of new surfactants requires overcoming the following core challenges: 1) Designing a molecular structure that has both mild cleansing and conditioning effects, which can not only effectively remove dirt, but also form a lightweight protective layer on the hair surface through physical or chemical effects (such as electrostatic adsorption and hydrogen bonding), thereby avoiding the heavy residue of traditional silicone oil; 2) Optimizing the formula system so that the fluffy ingredients (such as thickening polymers) and the softening ingredients (such as natural oil derivatives) work synergistically, and by regulating the interaction forces between hair fibers, the flatness is reduced while the smoothness is improved; 3) Reducing dependence on petrochemical raw materials, using bio-based surfactants (such as glycosides, amino acids) or enzymatic hydrolysis of natural protein products, combined with environmentally friendly preparation processes, to meet consumers' demand for "pure beauty" and sustainable development. Summary of the invention

[0005] To solve the above technical problems, the present invention provides a preparation method of a degreasing, moisturizing and low-irritation hair cleaning surfactant, comprising the following steps:

[0006] Step 1: Mix walnut protein and distilled water in a mass ratio of 1:10 to 1:35, and adjust the pH value of the mixed solution to neutral with sodium hydroxide or citric acid; add papain, and the mass ratio of it to walnut protein is 3-10:100. Place the mixed solution in a water bath at 45°C to 60°C for hydrolysis reaction, and the hydrolysis time is 60-180 minutes; during the hydrolysis process, continuously adjust the pH value of the solution with NaOH or HCl to keep it stable at 7.0; subject the collected hydrolysis product to heat treatment in a water bath at 95°C for 15 minutes, adjust the pH value of the hydrolysis product to 7.0, centrifuge to separate the supernatant, and freeze-dry the supernatant to obtain the walnut proteinase hydrolysis product, and store it at 20°C for subsequent use;

[0007] Step 2: Heat deionized water to 40-50°C, slowly add sodium lauryl polyether sulfate, and stir until it is completely dissolved; add cocamidopropyl betaine, and continue to stir until evenly mixed; add sodium cocoyl glutamate and sodium cocoyl sarcosinate in sequence, and stir for 20-60 minutes; add oat β-glucan, and stir until it is completely dissolved; add the walnut proteinase hydrolysis product prepared in Step 1 into the system, continue to stir for 30-80 minutes after mixing evenly; add polydimethylsiloxane and cationic guar gum, and stir until completely dissolved; then add xanthan gum, and stir until the system reaches the required viscosity; adjust the pH value to 5.5-6.5 with citric acid or sodium hydroxide; then add phenoxyethanol, and stir until evenly mixed; finally, cool the mixture to room temperature, transfer the finished product to a sealed container, and store it away from light;

[0008] Wherein, based on the mass ratio of the raw materials, deionized water: sodium lauryl polyether sulfate: cocamidopropyl betaine: sodium cocoyl glutamate: sodium cocoyl sarcosinate: oat β-glucan: walnut proteinase hydrolysis product: polydimethylsiloxane: cationic guar gum: xanthan gum: phenoxyethanol

[0009] = 100:8-12:3.5-4.5:2-2.5:2-2.5:0.4-1:1-5:0.8-1.2:0.3-0.8:0.1-0.3:0.1-0.3.

[0010] Further, the concentration of the oat β-glucan is 0.5%-1.0%.

[0011] Further, the walnut proteinase hydrolysis product is prepared by freeze-drying and stored at 20°C.

[0012] Further, the pH value of the surfactant is adjusted to 5.5 - 6.5 with citric acid or sodium hydroxide to adapt to the physiological environment of hair and scalp.

[0013] Further, after the surfactant is prepared, it is transferred to a sealed container for storage in the dark to maintain its stability and activity.

[0014] The beneficial effects of the present invention are as follows: Through multi-step fine design, the preparation method of the present invention realizes the moisturizing performance and low irritation of the hair cleaning agent. By mixing walnut protein with distilled water in proportion and performing efficient hydrolysis with papain under neutral pH conditions, bioactive small peptides and amino acids are generated, providing rich nutritional components for hair and scalp. During the hydrolysis process, by precisely controlling the pH value and temperature, the optimal enzyme activity is ensured. At the same time, through heat treatment, the product is stabilized and residual enzymes are inactivated, ensuring that a variety of essential amino acids and bioactive peptides rich in walnut protein are decomposed into smaller molecules during enzymatic hydrolysis, which can more easily penetrate into the interior of hair and the surface layer of scalp, thereby providing necessary nutritional support for hair follicles, promoting hair growth and repairing damaged hair scales. In addition, the antioxidant components in the walnut protein hydrolysis product can effectively scavenge free radicals, reduce the damage of oxidative stress to scalp cells, improve the microenvironment of the scalp, reduce inflammatory reactions, and create good conditions for the healthy growth of hair. These components are easily absorbed by the skin, exerting multiple effects such as moisturizing, repairing the barrier, antioxidant, and anti-inflammatory. Oat β-glucan forms a protective film on the scalp surface with its excellent moisturizing performance, locking in moisture, preventing scalp dryness and itching. At the same time, its anti-inflammatory and antibacterial properties help inhibit the growth of microorganisms such as Malassezia, reducing the production of dandruff. In addition, the protective film formed by oat β-glucan on the hair surface can also reduce static electricity, making the hair smoother and easier to comb, improving the overall texture. By combining the walnut protein hydrolysis product with a variety of surfactants (such as sodium lauryl polyether sulfate, cocoamidopropyl betaine) and functional components (such as oat β-glucan, xanthan gum), a multifunctional composition is formed, which not only has good cleaning ability and mildness, but also can further improve the use experience and efficacy of the product through the moisturizing and repairing effects of oat β-glucan, the thickening and stabilizing effects of xanthan gum, and the smoothing and protecting effects of polydimethylsiloxane. Finally, by adjusting the pH value to 5.5 - 6.5, it is close to the natural pH value of the skin, reducing irritation and maintaining the skin barrier function. At the same time, phenoxyethanol is added as a preservative to ensure the safety and stability of the product. This method has strong process controllability, natural and mild raw materials, is applicable to various personal care products such as body wash and shampoo, and has broad market application prospects. Detailed implementation mode

[0015] In order to make the purpose, technical solution and advantages of the present invention clearer, the technical solution of the present invention will be clearly and completely described below in combination with the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0016] The following is a detailed description of an oil-removing, moisturizing, low-irritation hair cleaning surfactant and a preparation method thereof provided by the present invention through examples.

[0017] Embodiment 1:

[0018] Step 1: the mass ratio of walnut protein to distilled water is 1:25, the amount of papain added is 6% (protein mass), the hydrolysis temperature is 50°C, the hydrolysis time is 120 minutes, and during the hydrolysis process, the pH value of the solution is continuously adjusted by NaOH to stabilize it at 7.0; the collected hydrolyzate is heat-treated in a 95°C water bath for 15 minutes, the pH value of the hydrolyzate is adjusted to 7.0, the supernatant is separated by centrifugation, the supernatant is freeze-dried to obtain a walnut protease hydrolyzate, and the supernatant is stored at 20°C.

[0019] Step 2: deionized water (100g), sodium laureth sulfate (10g), cocamidopropyl betaine (4g), sodium cocoyl glutamate (2.3g), sodium cocoyl sarcosinate (2.3g) were stirred for 60 minutes, oat β-glucan (0.5%, 0.7g), walnut enzymatic hydrolysate (3g) were stirred for 60 minutes, polydimethylsiloxane (1.0g), cationic guar gum (0.5g), xanthan gum (0.2g), phenoxyethanol (0.2g), pH was adjusted to 6.0, and the surfactant was transferred to a sealed container after preparation and stored away from light to maintain its stability and activity.

[0020] Cleansing power (92%), sodium laureth sulfate (10%) and cocamidopropyl betaine (4%) are in a moderate proportion to form a dense micelle structure, which synergizes with the hydrophobic peptides of the walnut hydrolysate to enhance the oil encapsulation ability. Moisturizing (88%), the hydrophilic amino acids in the hydrolysate (3%) and oat β-glucan form a moisturizing network through hydrogen bonds, enhancing the hydration of the stratum corneum. Low irritation (95% cell survival rate), the neutral protein hydrolysis process avoids the risk of protein residue sensitization, and the surfactant compounding reduces the monomer concentration and reduces lipid dissolution. In terms of antioxidant performance, the product exhibits a DPPH free radical scavenging rate of 76%. This effect mainly comes from the bioactive short peptides (especially 2-3 peptides containing tyrosine) generated during the walnut enzymatic hydrolysis process. These short peptides effectively neutralize free radicals through a hydrogen supply mechanism to provide antioxidant protection.

[0021] Example 2:

[0022] Step 1: The mass ratio of walnut protein to distilled water is 1:10, the addition amount of papain (800 u / mg) is 10% (protein mass), the hydrolysis temperature is 60 °C, and the hydrolysis time is 180 minutes. During the hydrolysis process, the pH value of the solution is continuously adjusted by NaOH to keep it stable at 7.0; the collected hydrolysis product is heat-treated in a water bath at 95 °C for 15 minutes, the pH value of the hydrolysis product is adjusted to 7.0, the supernatant is separated by centrifugation, and the supernatant is freeze-dried to obtain the walnut proteinase hydrolysis product, which is stored at 20 °C.

[0023] Step 2: Deionized water (100 g), sodium lauryl polyether sulfate (12 g), cocamidopropyl betaine (3.5 g), sodium cocoyl glutamate (2.5 g), sodium cocoyl sarcosinate (2.0 g) are stirred for 60 minutes, oat β-glucan (0.5%, 1.0 g), walnut enzymolysis product (5 g) are stirred for 60 minutes, polydimethylsiloxane (1.2 g), cationic guar gum (0.8 g), xanthan gum (0.3 g), phenoxyethanol (0.3 g), and the pH is adjusted to 5.8. The surfactant is transferred to a sealed container and stored in the dark after preparation to maintain its stability and activity.

[0024] Outstanding antioxidant property (84%). High enzyme addition amount (10%) and long hydrolysis time (180 minutes) release more small molecule antioxidant peptides (<1 kDa), improving the free radical scavenging efficiency. The highest moisturizing property (92%). The high-concentration enzymolysis product and oat β-glucan form a multi-layer moisturizing film.

[0025] Example 3:

[0026] Step 1: The mass ratio of walnut protein to distilled water is 1:35, the addition amount of papain (800 u / mg) is 3% (protein mass), the hydrolysis temperature is 45 °C, and the hydrolysis time is 60 minutes. During the hydrolysis process, the pH value of the solution is continuously adjusted by NaOH to keep it stable at 7.0; the collected hydrolysis product is heat-treated in a water bath at 95 °C for 15 minutes, the pH value of the hydrolysis product is adjusted to 7.0, the supernatant is separated by centrifugation, and the supernatant is freeze-dried to obtain the walnut proteinase hydrolysis product, which is stored at 20 °C.

[0027] Step 2: Deionized water (100 g), sodium lauryl polyether sulfate (8 g), cocamidopropyl betaine (4.5 g), sodium cocoyl glutamate (2.0 g), sodium cocoyl sarcosinate (2.5 g) are stirred for 60 minutes, oat β-glucan (0.5%, 0.4 g), enzymolysis product of walnut (1 g) are stirred for 60 minutes, polydimethylsiloxane (0.8 g), cationic guar gum (0.3 g), xanthan gum (0.1 g), phenoxyethanol (0.1 g), and the pH is adjusted to 6.5. After preparation, the surfactant is transferred to a sealed container and stored away from light to maintain its stability and activity.

[0028] The lowest irritation (98% cell survival rate), the reduced amount of enzymolysis product reduces potential allergens, and the increased proportion of cocamidopropyl betaine further neutralizes the anionic surfactant charge and reduces the damage to barrier proteins. The detergency is slightly weaker, the amount of sodium lauryl polyether sulfate is reduced, and the micelle density decreases, but the auxiliary cleaning of sodium cocoyl sarcosinate makes up for some losses.

[0029] Comparative Example 1:

[0030] Step 1: The mass ratio of walnut protein to distilled water is 1:25, the addition amount of papain is 2% (lower than the recommended value), and the hydrolysis time is 30 minutes (too short), and the others are the same as in Example 1.

[0031] Step 2: The same formulation as in Example 1.

[0032] The addition amount of papain is only 2% and the hydrolysis time is 30 minutes, resulting in insufficient protein hydrolysis degree (molecular weight > 5 kDa), and the peptide segments cannot effectively penetrate the stratum corneum. The moisturizing property (72%) decreases significantly. The large molecular peptides are difficult to form a composite network with oat β-glucan, and the water retention ability is weak. After testing, the antioxidant property is 48%, not enough active peptide segments are released, and the free radical scavenging efficiency is insufficient.

[0033] Comparative Example 2:

[0034] Step 1: The same as in Example 1.

[0035] Step 2: Sodium lauryl polyether sulfate (15 g, in excess), cocamidopropyl betaine (2 g, insufficient), and the others are the same as in Example 1.

[0036] The amount of sodium lauryl polyether sulfate is in excess and the amount of cocamidopropyl betaine is insufficient, which destroys the charge balance of anionic / zwitterionic surfactant monomers. The irritation increases (82% cell survival rate). The excessive anionic surfactant monomers damage the lipid arrangement of the stratum corneum, resulting in barrier damage. The moisturizing property (68%) drops sharply. The micelle structure is loose, unable to effectively load the moisturizing components, and the pH increases (6.0 → 6.8), weakening the stability of the enzymolysis product.

[0037] Comparative Example 3:

[0038] Step 1: Omit the enzymatic hydrolysis step of walnut protein and directly use unhydrolyzed walnut protein raw material.

[0039] Step 2: Prepare according to the basic formula of Example 1 (excluding walnut protein hydrolysate).

[0040] Since walnut protein hydrolysate was not added, the formula lacked small molecule active peptides with synergistic effects. The experimental results showed that the moisturizing performance of the product was significantly reduced, with a moisturizing rate of only 58%. This phenomenon was mainly attributed to the lack of the composite moisturizing mechanism between the key small molecule peptides and oat β-glucan in the formula. At the same time, due to its large molecular hydrophobic properties, unhydrolyzed walnut protein easily forms residues on the skin surface, resulting in obvious dryness and roughness after use, and a lower skin feel score in the sensory evaluation.

[0041] The cell survival rate of Comparative Example 3 was still as high as 90%, but the skin feel score (dry and rough) was significantly deteriorated in actual use. There may be the following two reasons.

[0042] Limitations of cytotoxicity experiments: The MTT method mainly reflects acute cell membrane damage, while the drying and barrier destruction caused by the lack of enzymatic products are long-term physical stimulations that cannot be fully reflected by short-term cell experiments.

[0043] Impact of surfactant residues: The hydrophobic residues of unhydrolyzed walnut protein compete with anionic surfactants for adsorption, destroying the integrity of the sebum membrane and causing a subjective feeling of dryness, but do not directly cause cell death.

[0044] Performance Test:

[0045] 1. Cleaning power (grease removal rate) test method:

[0046] In vitro sebum simulation method:

[0047] Artificial sebum preparation: simulated sebum was prepared according to ISO 11930 standard.

[0048] Substrate treatment: Artificial sebum was evenly coated on the surface of the glass slide (coating amount 1.0 mg / cm 2 ).

[0049] Cleaning process: Use a standard cleaning device (such as a rotary scrubber) to clean the substrate with the product to be tested.

[0050] Grease removal rate calculation: Calculate the removal rate by weight method (difference in substrate mass before and after cleaning):

[0051]

[0052] 2. Moisture retention (water retention rate) test method:

[0053] In vitro stratum corneum water retention experiment:

[0054] Ex vivo skin model: Use porcine ear skin or artificial reconstituted stratum corneum membrane Pretreat to the initial water content (about 20% - 30%).

[0055] Sample treatment: Uniformly apply the test product on the skin surface (dosage 2 mg / cm 2 ), leave it standing at room temperature for 10 minutes, rinse and dry after rinsing.

[0056] Water content determination: Use the desiccator method or dynamic vapor sorption instrument (DVS), weigh every 1 hour under constant temperature and humidity conditions (25°C, 40% RH), and continuously measure for 4 hours.

[0057] Calculation of water retention rate:

[0058]

[0059] 3. Irritation (cytotoxicity) test method:

[0060] Cytotoxicity experiment (MTT method):

[0061] Cell culture: Use immortalized human keratinocytes (HaCaT), culture them at 37°C, 5% CO 2 until the logarithmic growth phase.

[0062] Sample treatment: Dilute the product to the working concentration (5%), and co - incubate with the cells for 24 hours.

[0063] Survival rate determination: Add MTT reagent (0.5 mg / mL), dissolve the formazan crystals (DMSO) after incubating for 4 hours, measure the absorbance at 570 nm, and calculate the cell survival rate:

[0064]

[0065] 4. Antioxidant property (DPPH free radical scavenging rate) test method:

[0066] DPPH free radical scavenging experiment:

[0067] Reagent preparation: Dissolve DPPH (1,1 - diphenyl - 2 - picrylhydrazyl) in absolute ethanol to prepare a 0.1 mM solution (store in the dark).

[0068] Reaction system: Take 2 mL of DPPH solution and 2 mL of the test sample (diluted to an appropriate concentration), mix and react in the dark for 30 minutes.

[0069] Absorbance measurement: Use an ultraviolet spectrophotometer to measure the absorbance at 517 nm, and the calculation of the clearance rate:

[0070] Repeat the tests for the examples and comparative examples, and the specific test results are shown in Table 1.

[0071] Table 1 Performance test data of Examples 1-3 and Comparative Examples 1-3

[0072] Cleaning power Moisturizing property (4 hours) Irritation Example 1 92％±1.5％ 88％±2％ 95％±3％ Example 2 89％±2％ 92％±1.5％ 90％±2％ Example 3 85％±3％ 82％±3％ 98％±1％ Comparative Example 1 88％±2％ 72％±4％ 93％±2％ Comparative Example 2 95％±1％ 82％±5％ 68％±3％ Comparative Example 3 90％±2％ 58％±5％ 90±2％

Claims

1. A method for preparing a degreasing, moisturizing and low-irritation hair cleaning surfactant, characterized in that: The following steps are involved: Step 1: walnut protein and distilled water are mixed in a mass ratio of 1:10 to 1:35, and the pH value of the mixed solution is adjusted to neutral using sodium hydroxide or citric acid; papain is added in a mass ratio of 3 to 10:100 to walnut protein, and the mixed solution is placed in a water bath at 45° C. to 60° C. for hydrolysis reaction, and the hydrolysis time is 60 to 180 minutes; During the hydrolysis process, the pH value of the solution is continuously adjusted by NaOH or HCl to stabilize it at 7.0; the collected hydrolyzate is heat-treated in a water bath at 95° C. for 15 minutes, the pH value of the hydrolyzate is adjusted to 7.0, the supernatant is separated by centrifugation, the supernatant is freeze-dried to obtain a walnut protease hydrolyzate, and the supernatant is stored at 20° C. for subsequent use; Step 2: Heat deionized water to 40-50°C, slowly add sodium laureth sulfate, and stir until it is completely dissolved; add cocamidopropyl betaine, and continue to stir until it is evenly mixed; add sodium cocoyl glutamate and sodium cocoyl sarcosinate in sequence, and stir for 20-60 minutes; add oat β-glucan, and stir until it is completely dissolved; add the walnut protein hydrolysate prepared in step 1 to the system, mix evenly, and continue to stir for 30-80 minutes; add polydimethylsiloxane and cationic guar gum, and stir until they are completely dissolved; then add xanthan gum, and stir until the system reaches the required viscosity; adjust the pH value to 5.5-6.5 using citric acid or sodium hydroxide; then add phenoxyethanol and stir until it is evenly mixed; finally, cool the mixture to room temperature, transfer the finished product to a sealed container, and store it away from light; The raw materials are calculated by mass ratio as follows: deionized water: sodium laureth sulfate: cocamidopropyl betaine: sodium cocoyl glutamate: sodium cocoyl sarcosinate: oat β-glucan: walnut protein hydrolysate: polydimethylsiloxane: cationic guar gum: xanthan gum: phenoxyethanol ＝100:8～12:3.5～4.5:2～2.5:2～2.5:0.4～1:1～5:0.8～1.2:0.3～0.8:0.1～0.3:0.1～0.3。 2. The method for preparing a degreasing, moisturizing and low-irritation hair cleaning surfactant according to claim 1, characterized in that: The concentration of the oat beta-glucan is 0.5% to 1.0%.

3. The method for preparing a degreasing, moisturizing and low-irritation hair cleaning surfactant according to claim 1, characterized in that: The walnut proteinase hydrolysate was prepared by freeze drying and stored at 20°C.

4. The method for preparing a degreasing, moisturizing and low-irritation hair cleaning surfactant according to claim 1, characterized in that: The pH value of the surfactant is adjusted to 5.5-6.5 by citric acid or sodium hydroxide to adapt to the physiological environment of hair and scalp.

5. The method for preparing a degreasing, moisturizing and low-irritation hair cleaning surfactant according to claim 1, characterized in that: After the preparation, the surfactant is transferred to a sealed container and stored away from light to maintain its stability and activity.

6. A degreasing, moisturizing and low-irritation hair cleaning surfactant, characterized in that: The method is prepared by any one of claims 1 to 5.

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