Silicone oil-free shampoo composition containing polyquaternium-51 and preparation method of silicone oil-free shampoo composition

Abstract

The invention relates to the technical field of daily chemicals, and discloses a silicone oil-free shampoo composition containing polyquaternium-51 and a preparation method thereof, the composition comprises a mild surfactant, an ion gradient builder, the polyquaternium-51 and low molecular weight hydrolyzed protein which are specifically combined. The core of the bulking technology is that the preparation method comprises the following steps: preparing a core premix from polyquaternium-51 and a specific synergistic component in advance, blending the core premix into a main water phase containing an ion gradient building agent at a controlled rate, and finally adjusting the pH value to 5.0-6.0. According to the method, an inside and outside synergistic fluffy repairing system is constructed, so that ordered deposition of active matters on the surface of the hair and effective filling of the inside of the hair are ensured. The prepared composition is high in stability, can endow hair with an instant, lasting and non-dry fluffy effect, remarkably improves carding smoothness and natural gloss, and is suitable for fine, soft and collapsed hair so as to realize long-acting fluffy effect after cleaning.

Description

Technical Field

[0001] This invention relates to the field of daily chemical products technology, and in particular to a silicone-free shampoo composition containing polyquaternium-51 and its preparation method. Background Technology

[0002] For fine, limp hair, achieving root lift and volume after cleansing has been a long-standing technical need in the personal care industry. Currently, the common approach to achieving volume in shampoos and conditioners is to add cationic polymers to the composition. These polymers deposit on the hair surface, utilizing the electrostatic repulsion of like charges to increase the distance between hair strands, thus creating a macroscopic sense of volume. However, this conventional method has an inherent technical contradiction: to achieve a visible volume effect, a high concentration of cationic polymers is often required, which can easily lead to excessive deposition on the hair surface, resulting in an oily, sticky feel, and potentially causing tangles, dryness, and reduced combing performance.

[0003] To avoid the aforementioned greasy feeling, another technical solution is to use ingredients that can increase the coefficient of friction on the hair surface, or to adjust the formula to make the hair cuticles open appropriately, physically creating support and roughness between the hair strands. However, this method usually comes at the cost of sacrificing the hair's conditioning properties, easily leading to dryness, reduced shine, and even increased frizz, which runs counter to consumers' expectations for healthy hair.

[0004] Furthermore, another core challenge faced by existing volumizing technologies is the durability of their effects. Many products provide only a temporary volume; under the influence of external moisture, scalp oil, or product residue, the hairstyle quickly flattens, failing to maintain long-lasting volume. From a compositional perspective, stably blending multiple functional components—such as cationic polymers with volumizing properties, anionic surfactants providing cleansing, and proteins with repairing properties—into a homogeneous system presents a significant technical challenge. Improper preparation processes can easily lead to product separation and sedimentation, affecting its stability and final performance.

[0005] Therefore, developing a hair cleaning and care composition and its preparation method that can provide significant and long-lasting volume without causing negative experiences such as oiliness or dryness, while also improving hair smoothness and shine and maintaining a highly stable system, is a technical problem that urgently needs to be solved in this field. Summary of the Invention

[0006] The technical problem to be solved by the present invention is to provide a hair cleaning and care composition and its preparation method. The composition can give fine and soft hair a significant and lasting volumizing effect while overcoming the common defects in the prior art such as oiliness, dryness and loss of shine, and ensuring the physical stability of the composition itself.

[0007] To address the above problems, the present invention provides the following technical solution: In a first aspect, this application provides a silicone-free shampoo composition containing polyquaternium-51, comprising the following components by weight percentage: Mild surfactant: 15-25%; Polyquaternium-51: 0.2%–0.8%; Amphoteric surfactants: 0.5–1.5%; Ion gradient building agent: 0.1–0.4%; Hydrolyzed protein: 0.5–2.0%; Water: Bring the balance to 100%.

[0008] By adopting the above technical solution, this composition utilizes the synergistic effect of specific components to construct a stable microstructure in a liquid system.

[0009] Specifically, the ion gradient builder, as a multivalent anionic substance, pre-establishes a uniform and stable negative charge potential field in an aqueous phase composed of mild surfactants. When the complex formed by the cationic polyquaternary ammonium salt-51 and the amphoteric surfactant is added to the system, the negative charge potential field can regulate the electrostatic interaction rate between the polymer and the main surfactant, inhibiting the rapid and disordered formation of macroscopic flocs. Ultimately, the functional component is stably dispersed in the composition as a fine and uniform colloidal complex.

[0010] When used, these complexes adhere evenly to the hair surface, forming a discontinuous, lightweight mesh support structure, while hydrolyzed proteins penetrate into the hair shaft to provide structural support.

[0011] Therefore, this composition can achieve root lifting and hair separation without adding extra weight to the hair, resulting in a long-lasting voluminous effect.

[0012] Preferably, the mild surfactant is sodium lauroyl glutamate and / or cocamidopropyl betaine; the amphoteric surfactant is sodium lauroyl amphoteric acetate; and the ion gradient builder is sodium phytate and / or gluconolactone.

[0013] By adopting the above technical solution, the selected specific surfactants and ion gradient building agents have good compatibility and biocompatibility, ensuring the mildness of the composition system. At the same time, sodium phytate, as an ion gradient building agent, can effectively build the required negative charge potential field with its multidentate molecular structure.

[0014] Preferably, the hydrolyzed protein is low molecular weight hydrolyzed rice protein with an average molecular weight of 800-1500 Da.

[0015] By adopting the above technical solution, peptides with a specific molecular weight range can effectively penetrate into the hair cortex, replenish internal structural proteins, enhance the rigidity and toughness of the hair itself, and provide a synergistic effect on the external support structure from the inside.

[0016] Preferably, the polyquaternary ammonium salt-51 is a graft copolymer of butyl methacrylate and 2-methacryloyloxyethyl phosphocholine, with a weight-average molecular weight of 300,000 to 600,000 g / mol.

[0017] By adopting the above technical solution, polyquaternary ammonium salt-51 with specific structure and molecular weight has suitable film-forming and conditioning properties. Its phosphorylcholine group provides excellent moisturizing and biocompatibility, and the formed network structure has both support and flexibility.

[0018] Preferably, the composition further comprises one or more cosmetically acceptable excipients selected from thickeners, pH adjusters, preservatives, and fragrances.

[0019] Secondly, this application provides a method for preparing a silicone-free shampoo composition containing polyquaternium salt-51, comprising the following steps: (a) A mild surfactant and an ion gradient builder are dissolved in water to form an A-phase aqueous system; (b) Polyquaternium-51, amphoteric surfactant and hydrolyzed protein are dissolved in a solvent to form a B-phase core premix; (c) The B-phase core premix is ​​slowly added to the A-phase aqueous system and mixed at a controlled rate to obtain the composition.

[0020] By adopting the above technical solution, the sequence of steps in this preparation method is a decisive factor in achieving the stable structure and expected function of the composition.

[0021] Step (a) is performed before step (c) to ensure that a stable ion gradient environment has been pre-established in the host system before the addition of the cation complex.

[0022] The independent premixing in step (b) ensures that the polyquaternium-51 molecule is fully complexed with the amphoteric surfactant and hydrolyzed protein before it comes into contact with the main surfactant system, forming the initial functional unit.

[0023] The rate-controlled blending in step (c) utilizes the ion gradient environment constructed in step (a) to control the physicochemical interaction between phase A and phase B, thereby guiding the formation of the aforementioned uniformly dispersed fine colloidal complex and avoiding component failure or uneven deposition caused by traditional one-step mixing methods.

[0024] Preferably, step (a) is implemented by heating water to 75-85°C, then adding a mild surfactant and an ion gradient building agent, and stirring to dissolve.

[0025] By adopting the above technical solution, this temperature range ensures that all components can be completely dissolved and facilitates the uniform distribution of the ion gradient building agent in the system.

[0026] Preferably, step (c) is implemented as follows: while maintaining the temperature of the A-phase aqueous system at 70-80°C, the B-phase core premix is ​​added at a rate of 0.5-1.5% / minute of the total batch size, and stirring is continued for 15-25 minutes after the addition is complete.

[0027] By adopting the above technical solution, specific temperature and addition rate are the key process parameters for achieving controlled-speed blending, ensuring the gentle and orderly conduct of electrostatic interaction, and providing process assurance for the formation of a uniform and stable final product.

[0028] Preferably, the solvent in step (b) is glycerol and / or butanediol.

[0029] By adopting the above technical solution, the selected solvent can effectively dissolve each component in phase B to form a homogeneous premix, and is itself a commonly used moisturizer in cosmetics.

[0030] Preferably, after step (c), the method further includes the following steps: cooling the composition to below 45°C and adjusting the pH of the composition to 5.0 to 6.0 using a pH adjuster.

[0031] By adopting the above technical solution, the pH value is adjusted to a slightly acidic range, which is conducive to closing the hair cuticle, enhancing the shine of the hair, and helping to maintain the healthy micro-ecological environment of the scalp and the long-term stability of the product system.

[0032] In summary, the present invention has at least one of the following beneficial technical effects: 1. This invention introduces an ion gradient builder during the preparation process to pre-construct a controlled negative charge potential field in the aqueous phase. This potential field guides and regulates the dispersion behavior of the subsequently added polyquaternium-51 complex, inhibiting its disordered flocculation with the main surfactant. This process ensures that the functional components exist stably in a fine and uniform colloidal state in the product, and can uniformly and lightweightly adhere to hair strands during use, forming a discontinuous network support structure. This fundamentally solves the problem of the short-lived fluffiness effect caused by excessive deposition in traditional products without incurring additional weight.

[0033] 2. This invention not only utilizes polyquaternium-51 to form a lightweight support on the outside of the hair strand, but also combines it with low molecular weight hydrolyzed rice protein with an average molecular weight of 800-1500 Da. This specific molecular weight peptide can effectively penetrate into the hair cortex, replenishing lost proteins and enhancing the hair strand's inherent rigidity and elasticity. This dual support mechanism from the inside out means that the voluminous effect no longer relies solely on surface adhesion, but rather stems from the strengthening of the hair strand's own structure, thus exhibiting stronger resistance to pressure and moisture, making the voluminous style more stable.

[0034] 3. This invention employs a specific "controlled-speed blending" preparation method, effectively avoiding incompatibility issues such as flocculation, stratification, or precipitation that may occur between cationic polymers and anionic surfactants during production. This ensures the uniformity of the physical properties of the final product and its long-term storage stability. Simultaneously, the formulation system uses amino acid surfactants as the primary cleaning agent and strictly controls the pH value at 5.0–6.0, close to the scalp environment. This ensures that while providing excellent volume, the product minimizes irritation to the scalp and hair, achieving a balance between high efficiency and gentleness. Detailed Implementation

[0035] To enable those skilled in the art to more clearly understand the technical solutions of this application, the following detailed description of this application will be provided in conjunction with embodiments. It should be noted that the following embodiments and the experimental data therein are products of this application under specific experimental conditions, and the scope of protection should not be limited to the following embodiments without departing from the inventive concept of this application.

[0036] The main raw materials and reagents used in the following examples and comparative examples have the following sources and specifications. Reagents not specifically mentioned are all commercially available analytical grade or higher grade products.

[0037] Polyquaternium-51: The specific polyquaternium-51 used in this invention is prepared in detail in Preparation Example 1 below.

[0038] Low molecular weight hydrolyzed rice protein: prepared by enzymatic hydrolysis, the preparation method of which is detailed in Preparation Example 2 below.

[0039] Sodium phytate (CAS: 14306-25-3): White crystalline powder, purity ≥98%.

[0040] Gluconolactone (CAS: 90-80-2): White crystalline powder, cosmetic grade.

[0041] Sodium Lauroyl Glutamate (CAS: 29923-31-7): White powder, purity ≥95%.

[0042] Cocamidopropyl Betaine (CAS: 61789-40-0): Pale yellow transparent liquid with a solid content of 30%.

[0043] Sodium Lauroamphoacetate (CAS: 156028-14-7): Pale yellow transparent liquid with a solid content of 30%.

[0044] Polyquaternium-10 (CAS: 81859-24-7): Used in the comparative example, model JR-400, degree of cationic substitution 0.7.

[0045] Preparation Examples 1-2: Preparation Example 1: The present invention provides a method for preparing polyquaternary ammonium salt-51, the steps of which are as follows: 1. To a 1000 mL three-necked flask equipped with a mechanical stirrer, a reflux condenser and a nitrogen delivery tube, add 40.0 g of butyl methacrylate (BMA), 10.0 g of 2-methacryloyloxyethyl phosphocholine (MPC) and 250 mL of anhydrous ethanol in sequence, and stir until completely dissolved.

[0046] 2. Purge the reaction system with nitrogen gas for 30 minutes to completely remove oxygen from the system.

[0047] 3. Under nitrogen protection, heat the reaction system to 65°C. After the temperature stabilizes, add 0.5 g of initiator azobisisobutyronitrile (AIBN) dissolved in 10 mL of anhydrous ethanol.

[0048] 4. Maintain the reaction at 65°C for 8 hours. After the reaction is complete, cool the reaction system to room temperature.

[0049] 5. Slowly add the obtained polymer solution dropwise to 2000 mL of anhydrous diethyl ether to induce precipitation. Filter and collect the white solid precipitate, then wash three times with diethyl ether.

[0050] 6. The obtained solid was placed in a vacuum drying oven and dried under vacuum at 40°C for 24 hours to obtain a white powdery polyquaternium-51 copolymer.

[0051] 7. Dissolve the dried copolymer in deionized water to prepare a solution with a solid content of 5.0% (w / w) for later use.

[0052] The weight-average molecular weight (Mw) of the obtained copolymer was determined to be 480,000 g / mol and the molecular weight distribution index (PDI) was 2.1 by gel permeation chromatography (GPC).

[0053] Preparation Example 2: The present invention provides a method for preparing low molecular weight hydrolyzed rice protein, the steps of which are as follows: 1. Add 80.0 kg of deionized water to the reactor, start stirring, add 20.0 kg of rice protein isolate (protein content ≥90%), stir and disperse evenly to form a protein suspension.

[0054] 2. Adjust the pH of the suspension to 8.0 using a 5% (w / w) sodium hydroxide solution and heat to 55°C.

[0055] 3. Add 0.2 kg of alkaline protease (Alcalase® 2.4 L FG from Novozymes) to the reaction system and carry out the enzymatic hydrolysis reaction at 55°C and pH 8.0.

[0056] 4. Take a sample at 45 minutes after the start of the reaction and monitor the process by measuring the degree of hydrolysis (AN / TN) or using a rapid molecular weight determination method.

[0057] 5. When the hydrolysis reaction has been going on for about 60 minutes, quickly heat the reaction solution to 95°C and maintain it for 15 minutes to completely inactivate the protease and terminate the hydrolysis reaction.

[0058] 6. Cool the reaction solution to room temperature, and after filtration, decolorization, and desalting purification, obtain a low molecular weight hydrolyzed rice protein solution.

[0059] The average molecular weight of the product was determined to be 1250 Da by gel permeation chromatography (GPC).

[0060] Examples 1-4: In the following examples, "parts" refers to parts by weight. Polyquaternium-51 raw material is calculated as a 5% solids solution, cocamidopropyl betaine and sodium lauroamphoacetate raw materials are calculated as a 30% solids solution, and all other raw materials are 100% solids unless otherwise specified.

[0061] Example 1: The silicone-free shampoo composition containing polyquaternium-51 of this invention is made from the following raw materials in parts by weight: Phase A contains 18.0 parts of sodium lauroyl glutamate, 0.2 parts of sodium phytate, and the remainder of deionized water to make up to 100 parts. Phase B contains 3.0 parts of glycerol, 8.0 parts of polyquaternium-51 (5% solution), 3.3 parts of sodium lauroamphoacetate (30% solution), and 1.0 part of low molecular weight hydrolyzed rice protein. Phase C contains 0.5 parts xanthan gum and 0.8 parts phenoxyethanol; Phase D contains an appropriate amount of citric acid.

[0062] Its preparation method is as follows: 1. Add the deionized water from phase A to the main pot, turn on the stirring, and heat to 80°C.

[0063] 2. Add sodium lauroyl glutamate and sodium phytate to the main pot, stir until completely dissolved to form a homogeneous and transparent A-phase aqueous system, and maintain the temperature at 75℃.

[0064] 3. In another container, mix the glycerol, polyquaternium-51 solution, sodium lauroamphoacetate solution and low molecular weight hydrolyzed rice protein in phase B thoroughly to form the core premix of phase B.

[0065] 4. The B-phase core premix obtained in step 3 is slowly pumped into the A-phase aqueous system of the main pot at a rate of 1.0% / minute of total batch.

[0066] 5. After adding all the ingredients, continue stirring at 75°C for 20 minutes to ensure the system is thoroughly mixed.

[0067] 6. Turn off the heating and turn on the cooling water to cool the system to below 45°C.

[0068] 7. Add xanthan gum and phenoxyethanol in phase C in sequence, and stir well.

[0069] 8. The pH of the final product was adjusted to 5.5 using an aqueous solution of citric acid in phase D to obtain the composition of Example 1.

[0070] Example 2: The silicone-free shampoo composition containing polyquaternium-51 of this invention is made from the following raw materials in parts by weight: Phase A contains 15.0 parts of sodium lauroyl glutamate, 10.0 parts of cocamidopropyl betaine (30% solution), 0.4 parts of sodium phytate, and the remainder of deionized water to bring the total to 100 parts. Phase B contains 4.0 parts of 1,3-butanediol, 16.0 parts of polyquaternium-51 (5% solution), 5.0 parts of sodium lauroamphoacetate (30% solution), and 2.0 parts of low molecular weight hydrolyzed rice protein. Phase C contains 0.6 parts xanthan gum and 0.8 parts phenoxyethanol; Phase D contains an appropriate amount of citric acid.

[0071] Its preparation method is as follows: 1. Add the deionized water from phase A to the main pot, turn on the stirrer, and heat to 85°C.

[0072] 2. Add sodium lauroyl glutamate, cocamidopropyl betaine and sodium phytate to the main pot in sequence, stir until completely dissolved to form a homogeneous and transparent A-phase aqueous system, and maintain the temperature at 80℃.

[0073] 3. In another container, mix the 1,3-butanediol, polyquaternium-51 solution, sodium lauroamphoacetate solution, and low molecular weight hydrolyzed rice protein in phase B thoroughly to form the core premix of phase B.

[0074] 4. The B-phase core premix obtained in step 3 is slowly pumped into the A-phase aqueous system of the main pot at a rate of 0.5% / minute of total batch.

[0075] 5. After adding all the ingredients, continue stirring at 80°C for 25 minutes to ensure the system is thoroughly mixed.

[0076] 6. Turn off the heating and turn on the cooling water to cool the system to below 45°C.

[0077] 7. Add xanthan gum and phenoxyethanol in phase C in sequence, and stir well.

[0078] 8. The pH of the final product was adjusted to 5.2 using an aqueous solution of citric acid in phase D to obtain the composition of Example 2.

[0079] Example 3: The silicone-free shampoo composition containing polyquaternium-51 of this invention is made from the following raw materials in parts by weight: Phase A contains 50.0 parts of cocamidopropyl betaine (30% solution), 0.1 parts of gluconolactone, and the remainder of deionized water to make up to 100 parts. Phase B contains 2.0 parts of glycerol, 2.0 parts of 1,3-butanediol, 4.0 parts of polyquaternium-51 (5% solution), 1.7 parts of sodium lauroamphoacetate (30% solution), and 0.5 parts of low molecular weight hydrolyzed rice protein. Phase C contains 0.4 parts xanthan gum and 0.8 parts phenoxyethanol; Phase D contains an appropriate amount of citric acid.

[0080] Its preparation method is as follows: 1. Add the deionized water from phase A to the main pot, turn on the stirrer, and heat to 75°C.

[0081] 2. Add cocamidopropyl betaine and gluconolactone to the main pot, stir until completely dissolved to form a homogeneous and transparent A-phase aqueous system, and maintain the temperature at 70℃.

[0082] 3. In another container, mix the glycerol, 1,3-butanediol, polyquaternium-51 solution, sodium lauroamphoacetate solution and low molecular weight hydrolyzed rice protein in phase B thoroughly to form the core premix of phase B.

[0083] 4. The B-phase core premix obtained in step 3 is slowly pumped into the A-phase aqueous system of the main pot at a rate of 1.5% / minute of total batch size.

[0084] 5. After adding all the ingredients, continue stirring at 70°C for 15 minutes to ensure the system is thoroughly mixed.

[0085] 6. Turn off the heating and turn on the cooling water to cool the system to below 45°C.

[0086] 7. Add xanthan gum and phenoxyethanol in phase C in sequence, and stir well.

[0087] 8. The pH of the final product was adjusted to 5.8 using an aqueous solution of citric acid in phase D to obtain the composition of Example 3.

[0088] Example 4: The silicone-free shampoo composition containing polyquaternium-51 of this invention is made from the following raw materials in parts by weight: Phase A contains 18.0 parts of sodium lauroyl glutamate, 0.2 parts of sodium phytate, 1.5 parts of microcrystalline cellulose, and the remainder of deionized water to make up to 100 parts. Phase B contains 3.0 parts of glycerol, 8.0 parts of polyquaternium-51 (5% solution), 3.3 parts of sodium lauroamphoacetate (30% solution), and 1.0 part of low molecular weight hydrolyzed rice protein. Phase C contains 0.5 parts xanthan gum, 0.5 parts p-hydroxyacetophenone, and 0.5 parts ethylene glycol; Phase D contains an appropriate amount of citric acid.

[0089] Its preparation method is as follows: 1. Add the deionized water from phase A to the main pot, turn on the stirring, and heat to 80°C.

[0090] 2. Add sodium lauroyl glutamate, sodium phytate and microcrystalline cellulose to the main pot, stir until completely dissolved and evenly dispersed to form a uniform A-phase aqueous system, and maintain the temperature at 75℃.

[0091] 3. In another container, mix the glycerol, polyquaternium-51 solution, sodium lauroamphoacetate solution and low molecular weight hydrolyzed rice protein in phase B thoroughly to form the core premix of phase B.

[0092] 4. The B-phase core premix obtained in step 3 is slowly pumped into the A-phase aqueous system of the main pot at a rate of 1.0% / minute of total batch.

[0093] 5. After adding all the ingredients, continue stirring at 75°C for 20 minutes to ensure the system is thoroughly mixed.

[0094] 6. Turn off the heating and turn on the cooling water to cool the system to below 45°C.

[0095] 7. Add xanthan gum, p-hydroxyacetophenone and ethylene glycol in phase C in sequence, and stir until well mixed.

[0096] 8. The pH of the final product was adjusted to 5.6 using an aqueous solution of citric acid in phase D to obtain the composition of Example 4.

[0097] Comparative Examples 1-8: Comparative Example 1: Compared with Example 1, the difference is that instead of using polyquaternium-51, sodium phytate and sodium lauroylamphoacetate, the conventional cationic conditioner polyquaternium-10 (0.5 parts) is used and prepared by a conventional one-step method (that is, all surfactants and conditioners are added to water and heated together to dissolve).

[0098] Comparative Example 2: The difference from Example 1 is that sodium phytate, which serves as an ion gradient building agent, is not added to phase A.

[0099] Comparative Example 3: Compared with Example 1, the formula is exactly the same, but the preparation method is different: the traditional one-step mixing method is adopted, that is, all components of phase A and phase B (except water) are added to the water in the main pot at one time, heated together to 80°C and stirred to dissolve, and then the subsequent cooling, thickening and pH adjustment are carried out.

[0100] Comparative Example 4: The difference compared to Example 1 is that low molecular weight hydrolyzed rice protein is not added to phase B.

[0101] Comparative Example 5: The difference compared to Example 1 is that sodium lauroylamphoacetate, an amphoteric surfactant, is not added to phase B.

[0102] Comparative Example 6: The difference from Example 1 is that instead of using low molecular weight hydrolyzed rice protein with an average molecular weight of 800–1500 Da, an equal amount of conventional hydrolyzed wheat protein with an average molecular weight of 10,000 Da is used.

[0103] Comparative Example 7: Compared with Example 1, the formulation is exactly the same, but step 4 in the preparation method is different: the core premix of phase B is poured into the aqueous phase of phase A in one go within 1 minute for shock mixing, instead of being added slowly at a controlled rate.

[0104] Comparative Example 8: Compared with Example 1, the formulation and preparation method are basically the same, but in the final step 8, instead of using citric acid, triethanolamine is used to adjust the pH of the final product to 7.5.

[0105] Test Examples 1-4: Test Example 1: Physical Stability Test of the Composition To evaluate the physical stability of the compositions in Examples 1-4 and Comparative Examples 1-8, the following test procedures were performed: 1. Centrifugation test: Take 50 mL of each sample to be tested, place it in a 50 mL centrifuge tube, and centrifuge at 5000 rpm for 30 minutes. After centrifugation, remove the centrifuge tube, let it stand, and visually observe the macroscopic state of the sample inside the tube.

[0106] 2. Thermal cycling test: Take 50 mL of each sample to be tested and place it in a sealed container. Place the container in an environment of -18℃ for 24 hours, then return it to room temperature, and then place it in a constant temperature environment of 45℃ for 24 hours, and then return it to room temperature. This process constitutes one thermal cycling cycle.

[0107] 3. Repetition and Recording: Repeat step 2 for each sample for a total of three cycles. After all cycles are completed, visually observe the macroscopic state of the samples and record whether there is any stratification, precipitation, flocculation, or phase separation. The test results are recorded in Table 1.

[0108] Table 1. Results of physical stability tests for each sample:

[0109] As shown in Table 1, the samples from Examples 1 to 4 maintained a uniform and stable macroscopic state after undergoing centrifugation at 5000 rpm and three cycles of -18℃ / 45℃ thermal cycling tests, without any stratification, precipitation, or flocculation. This result indicates that by pre-preparing a B-phase core premix of polyquaternium-51, sodium lauroamphoacetate, and low-molecular-weight hydrolyzed protein, and then adding it at a controlled rate to an A-phase aqueous system containing a mild surfactant and an ion gradient builder, a macroscopically stable and uniform colloidal dispersion system can be formed.

[0110] In contrast, Comparative Example 2, lacking sodium phytate as an ion gradient building agent, exhibited slight flocculation as recorded in Table 1 during the thermal cycling test. This indicates that the presence of the ion gradient building agent in phase A plays a role in maintaining the dispersion state and long-term stability of the polyquaternium-51 composite in the final system. The samples from Comparative Examples 3 and 7 were prepared using a one-step mixing method and a rapid impact mixing method, respectively, and both showed significant phase separation as recorded in Table 1 after testing. This confirms that the stepwise, rate-controlled blending method proposed in this technical solution is necessary to ensure that the core premix of phase B can form a stable and finely dispersed structure in phase A. Direct mixing or rapid mixing cannot provide sufficient time and space conditions for the polymer composite to expand and arrange in an ordered manner, thus leading to macroscopic phase separation.

[0111] Comparative Example 5, lacking sodium lauroylamphoacetate, showed decreased system stability and precipitation as recorded in Table 1, indicating that this amphoteric surfactant plays a stabilizing role in the polyquaternium-51 complex in phase B. Comparative Example 1, using conventional polyquaternium-10 to replace the core component of this technical solution, also exhibited instability, as shown by the precipitation and stratification phenomena recorded in Table 1. This further illustrates that the specific component combination (polyquaternium-51, ion gradient builder, and amphoteric surfactant) selected in this technical solution, combined with the specific preparation method, is the technical basis for obtaining this stable composition.

[0112] Test Example 2: Hair Bundle Fluff and Durability Test To quantitatively evaluate the volumizing effect and long-lasting hold of the composition on hair strands, the following test procedures were performed: 1. Sample preparation: 20 sets of natural fine hair strands of the same specifications (20cm in length and 2.0g in weight) were selected as test subjects.

[0113] 2. Hair strand treatment: Take 1.0g of the sample to be tested, mix it with 2.0g of water, and apply it evenly to the moistened hair strand. Rub for 1 minute. Then, rinse the hair strand with water for 2 minutes until no foam residue remains.

[0114] 3. Drying and Initial Measurement: After treatment, use a towel to absorb excess moisture from the hair strands, then hang them in a constant temperature and humidity chamber at 25℃ and 60%RH to air dry naturally. Once the hair strands are completely dry, use calipers to measure their maximum outline width in the naturally hanging state, and record it as W0.

[0115] 4. Durability Measurement: The measured hair strand is placed in the constant temperature and humidity chamber for 24 hours. After 24 hours, its maximum profile width under the same conditions is measured again using vernier calipers and recorded as W. 24 .

[0116] 5. According to the formula: Loft retention rate (%) = (W 24 The fluffiness retention rate of each sample was calculated by multiplying (W0) by 100%. The test results are recorded in Table 2.

[0117] Table 2. Results of tests on the fluffiness and durability of hair strands after treatment for each sample:

[0118] The data in Table 2 show that the hair strands treated with the samples from Examples 1 to 4 exhibited significantly higher immediate voluminous width W0 (ranging from 38.9 mm to 43.5 mm) and voluminousness retention (ranging from 93.0% to 93.8%) compared to the comparative examples. This indicates that polyquaternium-51, under the influence of an ion gradient builder and a specific preparation method, can form a uniform film structure with electrostatic repulsion on the hair surface. This structure increases the electrostatic repulsion between hair strands, macroscopically manifesting as an increase in the spacing between hair strands, thereby achieving a higher immediate voluminous width.

[0119] Meanwhile, low-molecular-weight hydrolyzed rice protein can penetrate into the hair cortex, providing physical structural support. This works synergistically with the external polymer membrane structure, allowing the hair strands to maintain a high volume width even after 24 hours, as shown in the high volume retention rates of Examples 1-3. In contrast, Comparative Example 6 uses high-molecular-weight protein, which cannot effectively penetrate the hair shaft, resulting in a significantly lower volume retention rate (77.5%) compared to the examples. Comparative Example 4 lacks hydrolyzed protein; although its volume retention rate (87.0%) is higher than the conventional formula, it is still lower than the examples, confirming the role of synergistic internal and external support in the longevity of the effect.

[0120] Furthermore, Comparative Example 2 lacked an ion gradient building agent, resulting in a lower WO value (39.1 mm) and significantly reduced retention rate (80.6%) compared to the Example, indicating that the absence of an ion gradient affected the deposition efficiency and stability of the polymer film. Comparative Examples 3 and 7, using either a one-step mixing method or a rapid impact mixing method, also exhibited poor final bulk retention rates (73.3% and 75.6%, respectively). This confirms that stepwise rate-controlled blending is a prerequisite for forming an effective and durable external support structure.

[0121] Test Example 3: Hair Strand Combing Force Test To evaluate the combing performance of the composition on hair strands, a texture analyzer with combing attachments was used to test the combing ability of hair strands. The specific steps are as follows: 1. Sample preparation: Hair strands were treated using the same method as in Test Example 2.

[0122] 2. Wet Hair Test: A clean, damp hair strand (not dried) is fixed on the sample holder of the texture analyzer. The instrument parameters are set so that the comb attachment passes through the hair strand from top to bottom at a constant speed of 100 mm / min. The instrument records the total work required for this process.

[0123] 3. Dry hair test: The same hair bundle was air-dried naturally in a constant temperature and humidity chamber at 25℃ and 60%RH. After the hair bundle was completely dried, it was fixed on the sample holder and combed using the same instrument parameters as in step 2. The combing power in the dry hair state was recorded.

[0124] 4. Data Collection: For each sample, repeat the above steps to test three independent hair strands, and calculate the average value of wet hair combing ability and dry hair combing ability. The test results are recorded in Table 3.

[0125] Table 3. Combing performance test results of hair strands after treatment for each sample:

[0126] The data in Table 3 show that the hair strands treated with the samples from Examples 1-4 exhibited significantly lower combing power (ranging from 82.1 mJ to 88.6 mJ) for wet hair and 53.9 mJ to 59.2 mJ for dry hair compared to most comparative samples. This reduction in combing power directly corresponds to a decrease in the frictional resistance encountered during combing. This result demonstrates that, through the specific components and preparation method of this technical solution, polyquaternium-51 can form a uniform film with a low coefficient of friction on the hair surface, effectively smoothing the hair cuticle and thus reducing the power required for combing.

[0127] The test results of Comparative Example 4 (lacking hydrolyzed protein) and Comparative Example 8 (pH 7.5) provide further evidence for the above mechanism. The dry hair combing power of Comparative Example 4 (115.3 mJ) was significantly higher than that of its wet hair combing power (90.2 mJ) and the dry hair combing power of the Examples. This indicates that even with the presence of a polymer film on the surface, the hair exhibits high friction in the dry state when low molecular weight hydrolyzed protein is lacking to fill the internal structure of the hair strands. The dry hair combing power of Comparative Example 8 (130.7 mJ) was also significantly increased, indicating that under pH 7.5 conditions, the hair cuticles lift, leading to increased surface roughness, and the combing resistance increases significantly even in the presence of conditioning agents. This confirms the importance of a weakly acidic environment and the synergistic effect of internal and external factors for obtaining low combing power.

[0128] Furthermore, the combing work values ​​of Comparative Examples 2, 3, 5, and 7 were all higher than those of the Example. The increased combing work was due to the absence of an ionic gradient builder (Comparative Example 2), the absence of an amphoteric surfactant (Comparative Example 5), or the use of inappropriate preparation methods (Comparative Examples 3 and 7). This indicates that these components and process steps are necessary for forming a high-quality, uniform, low-friction surface film. Failure to form a stable B-phase core premix or failure to achieve its uniform dispersion in the A-phase will result in defects or inhomogeneities in the polymer film ultimately deposited on the hair surface, thus preventing the optimal reduction in combing work.

[0129] Test Example 4: Hair Strand Gloss Test To evaluate the effect of the composition on hair shine, the following test steps were performed: 1. Sample preparation: Hair bundles that had been naturally dried in a constant temperature and humidity chamber at 25°C and 60%RH were used. These hair bundles were prepared using the same treatment method as in Test Example 2.

[0130] 2. Sample fixation: Fix the dried hair strands to be tested flat on a black non-reflective background plate, ensuring that the hair strands are neatly arranged and on the same plane.

[0131] 3. Instrument measurement: Using a gloss meter, the gloss of five different locations in the middle section of the hair strand was measured at an incident angle of 60°.

[0132] 4. Data Processing: Calculate the average of the five measurement readings as the gloss value (unit: GU) for the hair strand. Repeat the above steps for each sample, testing three independent hair strands and calculating the final average gloss value. The test results are recorded in Table 4.

[0133] Table 4. Gloss test results of hair strands after treatment for each sample:

[0134] The data in Table 4 show that the hair strands treated with the samples from Examples 1-4 had gloss values ​​(ranging from 22.9 GU to 24.5 GU) higher than all comparative samples. Gloss is a measure of the ability of a surface to reflect light specularly. The high gloss value indicates that the composition of this invention can form a macroscopically smooth and highly uniform film structure on the hair surface. This structure effectively covers and smooths the hair cuticles, causing regular specular reflection of incident light rather than diffuse reflection, thus macroscopically resulting in increased hair gloss.

[0135] The test results of Comparative Examples 3 and 7 (10.3 GU and 11.5 GU, respectively) confirm the importance of the preparation method. Using a one-step mixing method or a rapid impact mixing method, the aforementioned well-formed surface film cannot be formed, resulting in uneven surface roughness, excessive diffuse reflection of light, and a significant decrease in gloss value. The gloss value of Comparative Example 5 (lacking an amphoteric surfactant) (18.2 GU) is also lower than that of the example, indicating that the stability of the B-phase core premix is ​​a prerequisite for forming a high-quality surface film. The gloss value of Comparative Example 2 (lacking an ion gradient builder) (21.5 GU) is slightly lower than that of the example, indicating that the ion gradient plays a role in promoting uniform film deposition.

[0136] The low gloss value (13.7 GU) of Comparative Example 8 (pH 7.5) indicates that the surface condition of the hair itself is fundamental. Under non-acidic conditions, the hair cuticles are raised, resulting in a rough surface. Even with polymer deposition, an effective specular reflective surface cannot be formed. Therefore, the high gloss effect achieved by this technical solution does not originate from a single component, but from the synergistic effect of multiple technical elements: at a weakly acidic pH value, the hair surface is in a smooth state; based on this, through a specific stepwise rate-controlled blending preparation method, a stable premix containing polyquaternium-51 is uniformly deposited on the hair surface, ultimately forming a regular surface structure capable of producing high specular reflection.

[0137] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A silicone oil-free shampoo composition containing polyquaternium-51, characterized in that, comprises, by weight percentage: mild surfactant 15-25%; polyquaternium-51 0.2-0.8%; amphoteric surfactant 0.5-1.5%; ionic gradient builder 0.1-0.4%; hydrolyzed protein 0.5-2.0%; the balance being water.

2. The polyquaternium-51 containing silicone oil-free shampoo composition according to claim 1, characterized in that, the mild surfactant is sodium lauroyl glutamate and / or cocamidopropyl betaine; the amphoteric surfactant is sodium lauroamphoacetate; the ionic gradient builder is sodium phytate and / or gluconolactone.

3. The polyquaternium-51 containing silicone oil-free shampoo composition according to claim 1, characterized in that, the hydrolyzed protein is low molecular weight hydrolyzed rice protein having an average molecular weight of 800-1500 Da.

4. The polyquaternium-51 containing silicone oil-free shampoo composition according to claim 1, characterized in that, the polyquaternium-51 is a graft copolymer of butyl methacrylate and 2-methacryloyloxyethyl phosphorylcholine having a weight average molecular weight of 300,000-600,000 g / mol.

5. The polyquaternium-51 containing silicone oil-free shampoo composition according to Claim 1, characterized in that, further comprises one or more cosmetically acceptable adjuvants selected from thickening agents, pH adjusting agents, preservatives, fragrances.

6. A process for the preparation of a silicone oil-free shampoo composition containing polyquaternium-51 according to any one of claims 1 to 5, characterized in that, comprises the following steps: (a) dissolving the mild surfactant and the ionic gradient builder in water to form a phase A aqueous system; (b) dissolving the polyquaternium-51, the amphoteric surfactant, and the hydrolyzed protein in a solvent to form a phase B core premix; (c) slowly adding the phase B core premix to the phase A aqueous system to perform a controlled speed blending to obtain the composition.

7. The production method according to claim 6, wherein The specific steps of step (a) comprise: heating water to 75-85°C, then adding the mild surfactant and the ionic gradient builder and stirring to dissolve.

8. The preparation method according to claim 6, characterized in that, The specific steps of step (c) comprise: adding the phase B core premix to the phase A aqueous system at a rate of 0.5-1.5% per minute of the total batch quantity while maintaining the temperature of the phase A aqueous system at 70-80°C, and continuing to stir for 15-25 minutes after the addition is complete.

9. The preparation method according to claim 6, characterized in that, The solvent in step (b) is glycerin and / or butylene glycol.

10. The method of claim 6, wherein, After step (c), the following steps are further included: cooling the composition to below 45°C, and adjusting the pH of the composition to 5.0-6.0 with a pH adjusting agent.

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