Compositions, polyquaternium-11, and shampoos

Abstract

The application relates to the technical field of daily chemicals, and discloses a composition, polyquaternium-11 and a shampoo, wherein the composition comprises N-vinyl pyrrolidone, dimethylaminoethyl methacrylate and sodium citrate. By adding a certain amount of sodium citrate in the composition, ions (Na + and C5H7O5COO ‑ ) in the solution can destroy the hydrogen bond and dipole interaction between water molecules and dimethylaminoethyl methacrylate through a salting-out effect, reduce the solubility of dimethylaminoethyl methacrylate and inhibit the diffusion rate of dimethylaminoethyl methacrylate, thereby reducing the reactivity of dimethylaminoethyl methacrylate and making polyquaternium-11 more transparent.

Description

Technical Field

[0001] This application relates to the field of daily chemical products technology, and more particularly to a composition, polyquaternium-11, and shampoo. Background Technology

[0002] Transparent shampoos have become a market trend in recent years, with consumers increasingly relying on visual perception to identify a product's "purity" and "technological sophistication." A transparent texture directly reflects claims of being silicone-free and residue-free, aligning with the modern demand for simple and natural hair care products. However, designing transparent formulas presents several technical challenges, including ingredient compatibility, transparency stability, rheological property control, and balancing functionality and aesthetics. Conditioning agents are a key challenge in transparent formulas; while providing wet-wet smoothness, anti-static effects, and styling hold, the formula system must maintain high transparency to prevent cloudiness from affecting the product's appearance.

[0003] Among numerous cationic polymers, polyquaternium-11's high transparency makes it an ideal choice for transparent shampoos. Due to its high solubility and transparency, it can be used directly in transparent systems, avoiding the impact of conditioning agent turbidity on product appearance. Although polyquaternium-11 theoretically possesses excellent optical transparency, systematic analysis of commercially available products reveals significant turbidity issues in practical applications (haze value approximately 20-25 NTU), a considerable difference from the ideal aqueous transparent system (haze value less than 5 NTU). Summary of the Invention

[0004] In view of this, this application provides a composition, polyquaternium-11, and shampoo that can improve the transparency of polyquaternium-11, so as to at least partially solve the above-mentioned technical problems.

[0005] In a first aspect, embodiments of this application provide a composition comprising N-vinylpyrrolidone, dimethylaminoethyl methacrylate, deionized water, and sodium citrate.

[0006] In some embodiments of this application, the ratio of the sum of the mass concentrations of N-vinylpyrrolidone and dimethylaminoethyl methacrylate to the mass concentration of sodium citrate is 1:(0.01~0.9).

[0007] In some embodiments of this application, the ratio of the sum of the mass concentrations of N-vinylpyrrolidone and dimethylaminoethyl methacrylate to the mass concentration of sodium citrate is 1:(0.2~0.9).

[0008] In some embodiments of this application, the N-vinylpyrrolidone in the composition has a mass concentration ranging from 0.01 g / L to 0.09 g / L; and / or, the dimethylaminoethyl methacrylate in the composition has a mass concentration ranging from 0.01 g / L to 0.09 g / L; and / or, the sodium citrate in the composition has a mass concentration ranging from 0.001 g / L to 0.09 g / L.

[0009] In some embodiments of this application, the mass concentration of sodium citrate in the composition ranges from 0.02 g / L to 0.07 g / L.

[0010] In some embodiments of this application, the composition further includes:

[0011] A quaternizing agent, wherein the quaternizing agent in the composition has a mass concentration ranging from 0.003 g / L to 0.006 g / L; and

[0012] An initiator, wherein the initiator in the composition is present in a mass concentration ranging from 0.00001 g / L to 0.03 g / L.

[0013] In some embodiments of this application, the quaternizing agent includes at least one selected from dimethyl sulfate, diethyl sulfate, haloalkanes, ethylene oxide, methyl chloride, and dimethyl carbonate; and / or

[0014] The initiator includes at least one of thermal decomposition initiator, redox initiator and photoinitiator. The thermal decomposition initiator is selected from at least one of azobisisobutyronitrile, azobisisoheptanenitrile, azobisisobutylamidine and benzoyl peroxide. The redox initiator is selected from at least one of a combination of potassium persulfate and sodium bisulfite, a combination of ammonium persulfate and sodium bisulfite, and a combination of hydrogen peroxide and ascorbic acid. The photoinitiator is selected from at least one of benzophenone and photoinitiator 2959.

[0015] Secondly, embodiments of this application provide a polyquaternary ammonium salt-11, which is prepared from the composition described in any of the above embodiments.

[0016] In some embodiments of this application, the polyquaternium-11 includes repeating quaternium salt units, the structural formula of which is shown in formula (I) below:

[0017] (I);

[0018] Where x and y are greater than 0;

[0019] The viscosity of the aqueous solution of the polyquaternary ammonium salt-11 ranges from 20,000 mPa·s to 60,000 mPa·s.

[0020] Thirdly, embodiments of this application provide a shampoo comprising the polyquaternium-11 described in any of the above embodiments.

[0021] Beneficial effects: This application, by adding a certain amount of sodium citrate to the composition, reduces the concentration of ions (Na+) in the solution. + and C5H7O5COO - The salting-out effect disrupts the hydrogen bonds and dipole interactions between water molecules and dimethylaminoethyl methacrylate, reducing the solubility of dimethylaminoethyl methacrylate and inhibiting its diffusion rate, thereby reducing its polymerization rate and making polyquaternium-11 more transparent. Detailed Implementation

[0022] In this application, "and / or" describes the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, A and B existing simultaneously, or B existing alone. A and B can be singular or plural.

[0023] In this application, "at least one" means one or more, and "more than one" means two or more. "One or more", "at least one", or similar expressions refer to any combination of these items, including any combination of single or multiple items. For example, "at least one of a, b, or c", or "at least one of a, b, and c", can both mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can be single or multiple.

[0024] Various embodiments of this application may exist in the form of a range; it should be understood that the description in the form of a range is merely for convenience and brevity and should not be construed as a hard limitation on the scope of this application; therefore, it should be considered that the range description has specifically disclosed all possible sub-ranges and single numerical values ​​within that range. For example, it should be considered that the range description from 1 to 6 has specifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., and single numbers within the range, such as 1, 2, 3, 4, 5, and 6, regardless of the range. Furthermore, whenever a numerical range is referred to herein, it means including any referenced number (fraction or integer) within the range referred to.

[0025] Among numerous cationic polymers, polyquaternium-11 stands out as an ideal choice for transparent shampoos due to its high solubility and transparency. According to the mechanism of action of polyquaternium, high charge density cationic conditioners readily form flocculants with anionic surfactants, potentially leading to system turbidity. Polyquaternium-11, by optimizing charge density and molecular weight, reduces excessive flocculant formation, thereby maintaining the transparency of the shampoo formula. The balanced design of polyquaternium-11's molecular weight (approximately 1 million) and charge density ensures conditioning performance while avoiding system instability caused by polymer chain entanglement. However, the inventors discovered that although polyquaternium-11 theoretically possesses excellent optical transparency, systematic analysis of commercially available products revealed significant turbidity issues in practical applications (haze value approximately 20-25 NTU), a significant difference from the ideal transparent aqueous system (haze value less than 5 NTU).

[0026] The applicant's in-depth research revealed that this phenomenon may be caused by the difference in the reactivity ratios of monomers, leading to a gradient distribution of monomer units in the copolymer chain and forming a microphase-separated structure. Polyquaternium-11 is prepared by copolymerizing N-vinylpyrrolidone and dimethylaminoethyl methacrylate. Although both monomers have excellent water solubility, during free radical copolymerization, dimethylaminoethyl methacrylate readily forms quaternary ammonium salts in an acidic aqueous phase, exhibiting higher self-growth activity. This results in a difference in the reactivity ratios of the two monomers; specifically, dimethylaminoethyl methacrylate has a higher reactivity ratio than vinylpyrrolidone. In the microphase-separated structure caused by this difference in reactivity ratios, microregions composed of different monomer units separate at the nanoscale and form specific particle morphologies, such as spherical, columnar, and layered structures, with particle diameters typically ranging from 50 to 200 nm. This nanoscale structural heterogeneity induces significant Rayleigh scattering, leading to a decrease in the material's transmittance and an increase in haze.

[0027] To address the aforementioned problems, this application provides a composition for preparing polyquaternary ammonium salt-11. The composition comprises N-vinylpyrrolidone, dimethylaminoethyl methacrylate, deionized water, and sodium citrate. By adding a certain amount of sodium citrate to the composition, the ions (Na+) in the solution... + and C5H7O5COO - The salting-out effect disrupts the hydrogen bonds and dipole interactions between water molecules and dimethylaminoethyl methacrylate, reducing the solubility of dimethylaminoethyl methacrylate and inhibiting its diffusion rate, thereby reducing its polymerization rate and making polyquaternium-11 more transparent.

[0028] Specifically, in copolymerization reactions, the polymerization rate of monomers is determined by their chemical structure, polarity, steric hindrance, and environmental conditions (such as solvent, pH, and temperature). The dimethylamino group (-N(CH3)2-N(CH3)2) in the dimethylaminoethyl methacrylate molecule is a weakly basic group. After adjusting the pH to acidity, it is protonated to form a positively charged quaternary ammonium salt structure (-NH). + (CH3)2-NH + (CH3)2). Upon addition of sodium citrate to the composition, the citrate ions in the solution pair with the cationic groups of dimethylaminoethyl methacrylate, reducing its effective charge. Simultaneously, the presence of sodium ions increases the ionic strength of the system, further enhancing the salting-out effect and significantly decreasing the solubility of dimethylaminoethyl methacrylate. This process alters the monomer concentration distribution in the solution, inhibiting its polymerization rate and making dimethylaminoethyl methacrylate and N-vinylpyrrolidone more prone to alternating copolymerization. Ultimately, the polyquaternary ammonium salt-11 aqueous solution prepared using the above composition exhibits higher macroscopic transparency.

[0029] In some embodiments, the ratio of the sum of the mass concentrations of N-vinylpyrrolidone and dimethylaminoethyl methacrylate to the mass concentration of sodium citrate is 1:(0.01~0.9). It is worth noting that any value within the range of the sum of the mass concentrations of N-vinylpyrrolidone and dimethylaminoethyl methacrylate to the mass concentration of sodium citrate is within the scope of protection of this application. Within the above-mentioned mass concentration ratio range, citrate ions in the solution can undergo ion pairing with the cationic groups of dimethylaminoethyl methacrylate, thereby reducing the solubility of dimethylaminoethyl methacrylate, inhibiting its polymerization rate, changing the difference in polymerization reactivity between the two monomers, and making dimethylaminoethyl methacrylate and N-vinylpyrrolidone more inclined to copolymerize.

[0030] Compositions with the aforementioned mass concentration ratios, when applied to shampoos, can simultaneously enhance the shampoo's cleansing power, oil control, smoothness, and foam richness. Specifically, the strong hydrophilicity of N-vinylpyrrolidone enhances its ability to encapsulate oils, while the cationic dimethylaminoethyl methacrylate assists in removing negatively charged dirt (such as dust and silicone oil residue). Furthermore, sodium citrate reduces the repulsion of negative charges on the hair surface through ion shielding, promoting dirt removal, thereby improving the overall cleansing power, oil control, and smoothness of the shampoo. The hydrogen-bonded network of N-vinylpyrrolidone and the cationic dimethylaminoethyl methacrylate synergistically stabilize the bubble film and extend foam life, while sodium citrate, by adjusting the ionic strength of the solution and reducing surface tension, promotes the synergistic foaming efficiency of the foaming agent, thereby improving the overall foam richness of the shampoo. Dimethylaminoethyl methacrylate has a uniformly distributed cationic structure that binds to hair keratin (negatively charged) at multiple points, forming a thin and uniform cationic film that supports the hair's voluminous structure. Sodium citrate inhibits polymer chain aggregation, avoiding the stiffness caused by an excessively thick film, thus achieving "flexible styling" and improving the overall volume and styling effect of the shampoo.

[0031] In some embodiments, the ratio of the sum of the mass concentrations of N-vinylpyrrolidone and dimethylaminoethyl methacrylate to the mass concentration of sodium citrate is further 1:(0.2~0.9). Within the above-mentioned mass concentration range, the transparency of the shampoo can be effectively improved. Specifically, the mass concentration ratio can be 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, or 1:0.9. It is worth noting that the specific value of the ratio of the sum of the mass concentrations of N-vinylpyrrolidone and dimethylaminoethyl methacrylate to the mass concentration of sodium citrate is given only as an example; any value within the range of 1:(0.2~0.9) or any value between any two values ​​is within the scope of protection of this application.

[0032] In some embodiments, the mass concentration of N-vinylpyrrolidone in the composition ranges from 0.01 g / L to 0.09 g / L. In some embodiments, the mass concentration of dimethylaminoethyl methacrylate in the composition ranges from 0.01 g / L to 0.09 g / L. Controlling the mass concentrations of N-vinylpyrrolidone and dimethylaminoethyl methacrylate within the above ranges, and adjusting the ratio of the sum of the mass concentrations of N-vinylpyrrolidone and dimethylaminoethyl methacrylate to the mass concentration of sodium citrate, can balance the smoothness, styling effect, foam richness, and volumizing effect of the shampoo. Sodium citrate can reduce the repulsion of negative charges on the hair surface through ion shielding, promoting dirt removal and improving cleaning power; it can also adjust the ionic strength of the solution, reduce surface tension, promote the synergistic foaming efficiency of foaming agents, and improve foam richness and volumizing effect; in addition, sodium citrate can also inhibit polymer chain aggregation, avoid the stiffness caused by excessively thick film, and improve styling effect. The hydrogen-bonded network of N-vinylpyrrolidone can synergistically stabilize the bubble film with the cationic form of dimethylaminoethyl methacrylate, extending the foam's lifespan. The uniformly distributed cationic form of dimethylaminoethyl methacrylate can bind to hair keratin (negatively charged) at multiple points, forming a thin, uniform cationic film that supports the hair's voluminous structure.

[0033] The mass concentration of N-vinylpyrrolidone in the composition can be 0.01 g / L, 0.015 g / L, 0.02 g / L, 0.025 g / L, 0.03 g / L, 0.035 g / L, 0.04 g / L, 0.045 g / L, 0.05 g / L, 0.055 g / L, 0.06 g / L, 0.065 g / L, 0.07 g / L, 0.075 g / L, 0.08 g / L, 0.085 g / L, or 0.09 g / L, or any range of two of the above values. It is worth noting that the specific mass concentration values ​​of N-vinylpyrrolidone are given only as examples; any value within the range of 0.01 g / L to 0.09 g / L, or any range between two of the above values, is within the scope of protection of this application.

[0034] The mass concentration of dimethylaminoethyl methacrylate in the composition can be 0.01 g / L, 0.015 g / L, 0.02 g / L, 0.025 g / L, 0.03 g / L, 0.035 g / L, 0.04 g / L, 0.045 g / L, 0.05 g / L, 0.055 g / L, 0.06 g / L, 0.065 g / L, 0.07 g / L, 0.075 g / L, 0.08 g / L, 0.085 g / L, or 0.09 g / L, or any range of two of the above values. It is worth noting that the specific mass concentration of dimethylaminoethyl methacrylate in the composition is given only as an example; any value or any range between two values ​​of dimethylaminoethyl methacrylate within the range of 0.01 g / L to 0.09 g / L is within the scope of protection of this application.

[0035] In some embodiments, under the condition that the ratio of the sum of the mass concentrations of N-vinylpyrrolidone and dimethylaminoethyl methacrylate to the mass concentration of sodium citrate is 1:(0.01~0.9), the mass concentration of N-vinylpyrrolidone in the composition ranges from 0.04 g / L to 0.06 g / L, and the mass concentration of dimethylaminoethyl methacrylate in the composition is from 0.04 g / L to 0.06 g / L. This combination can improve the overall performance of the shampoo in terms of transparency, cleansing power, smoothness, foam richness, volumizing effect, and styling effect.

[0036] In some embodiments, the mass concentration of sodium citrate in the composition is from 0.001 g / L to 0.09 g / L. When the mass concentration of sodium citrate in the composition is designed within the above range, it can inhibit the hydrophobic association of the molecular chains of polyquaternary ammonium salt-11 during the copolymerization reaction through the salt-dissolution effect, reducing aggregation and thus improving transparency. When the mass concentration of sodium citrate is below the above range, sodium citrate may not be able to effectively inhibit the hydrophobic association of the molecular chains, and the effect of improving transparency is not significant. When the mass concentration of sodium citrate exceeds the above range, excessive sodium citrate may trigger a salting-out effect, damaging the polymer hydration layer, leading to molecular chain aggregation and precipitation, and a decrease in transparency. The mass concentration of sodium citrate in the composition can be 0.001 g / L, 0.002 g / L, 0.003 g / L, 0.006 g / L, 0.008 g / L, 0.01 g / L, 0.015 g / L, 0.02 g / L, 0.025 g / L, 0.03 g / L, 0.035 g / L, 0.04 g / L, 0.045 g / L, 0.05 g / L, 0.055 g / L, 0.06 g / L, 0.065 g / L, 0.07 g / L, 0.075 g / L, 0.08 g / L, 0.085 g / L, or 0.09 g / L, or any range of two of the above values. It is worth noting that the specific values ​​of the mass concentration of sodium citrate in the composition are given only as examples, and any value or any two values ​​of the mass concentration of sodium citrate in the range of 0.001 g / L to 0.09 g / L are within the scope of protection of this application.

[0037] In some embodiments, the concentration of sodium citrate in the composition ranges from 0.02 g / L to 0.09 g / L, which can significantly improve the transparency of the shampoo. Even further, the concentration of sodium citrate in the composition ranges from 0.02 g / L to 0.07 g / L, which can further significantly improve the transparency of the shampoo.

[0038] In some embodiments, the composition further includes a quaternizing agent, the mass concentration of which ranges from 0.003 g / L to 0.006 g / L. The quaternizing agent, having a mass concentration range within the above range, can react with amino groups or other groups in the copolymer to convert tertiary amines into quaternary ammonium salt structures, thereby giving the polymer a positive charge. The introduction of quaternary ammonium salt groups alters the polymer's solubility, surface activity, antibacterial properties, etc. The quaternary ammonium salt groups have good hydrophilicity, increasing the polymer's solubility in water. The quaternized polymer structure is more stable and less susceptible to external environmental factors such as pH and temperature. The mass concentration of the quaternizing agent in the composition can be 0.003 g / L, 0.0035 g / L, 0.004 g / L, 0.0045 g / L, 0.005 g / L, 0.0055 g / L, or 0.006 g / L, or any range of two of the above values. It is worth noting that the specific value of the mass concentration of the quaternizing agent in the composition is given only as an example. Any value or any two values ​​of the mass concentration of the quaternizing agent within the range of 0.003 g / L to 0.006 g / L are within the protection scope of this application.

[0039] In some embodiments, the quaternizing agent may include at least one of dimethyl sulfate, diethyl sulfate, haloalkanes, methyl chloride, and dimethyl carbonate.

[0040] In some embodiments, the composition further includes an initiator, the initiator having a mass concentration in the composition ranging from 0.00001 g / L to 0.03 g / L. The initiator decomposes under reaction conditions (such as heating, light exposure, etc.), generating free radicals, which undergo addition reactions with other monomer molecules to form new free radicals, initiating the polymerization reaction. This process is repeated continuously, causing the polymer chain to gradually grow. Furthermore, an initiator with the above-mentioned mass concentration range can control the rate of the polymerization reaction, obtaining polymers within a predetermined molecular weight range. The mass content of the initiator in the composition can be 0.00001 g / L, 0.00005 g / L, 0.0001 g / L, 0.01 g / L, 0.015 g / L, 0.02 g / L, 0.025 g / L, 0.03 g / L, or any range of two of the above values. It is worth noting that the specific value of the mass concentration of the initiator in the composition is given only as an example. Any value of the mass concentration of the initiator in the range of 0.00001 g / L to 0.03 g / L, or any value between any two values, is within the protection scope of this application.

[0041] In some embodiments, the initiator includes at least one of a thermally decomposable initiator, a redox initiator, and a photoinitiator. The thermally decomposable initiator is selected from at least one of azobisisobutyronitrile (AIBN), azobisisobutyronitrile (ABVN), azobisisobutyramidine (AIBA), and benzoyl peroxide (BPO). The redox initiator is selected from at least one of a combination of potassium sulfate and sodium bisulfite, a combination of ammonium persulfate and sodium bisulfite, and a combination of hydrogen peroxide and ascorbic acid. The photoinitiator is selected from at least one of benzophenone and photoinitiator 2959.

[0042] Based on the above composition, this application also provides a polyquaternary ammonium salt-11, which is prepared using the composition in any of the above embodiments.

[0043] This polyquaternium-11 can be applied to, but is not limited to, transparent shampoos and serums, is compatible with anionic surfactants (such as SLES), and does not cause flocculation. Its cationic gradient distribution enhances hair adhesion, increasing volume by 40% (compared to traditional random copolymers). Regarding mildness: it passes skin irritation tests (EPI model), and residual monomers are less than or equal to 50 ppm (HPLC verification). Optionally, in some embodiments, the quaternizing agent may be diethyl sulfate, and the initiator may be azobisisobutyronitrile (AIO).

[0044] Polyquaternium-11 comprises repeating quaternary ammonium salt units as shown in formula (1):

[0045] (1).

[0046] The viscosity of the aqueous solution of polyquaternary ammonium salt-11 prepared from the above composition is in the range of 20,000 mPa·s to 60,000 mPa·s, wherein the active ingredient accounts for 19% to 21% of the mass fraction of the aqueous solution, and the active ingredient refers to the components in the aqueous solution other than deionized water.

[0047] The aqueous solution of polyquaternium-11 prepared from the above composition has better transparency than the conventional aqueous solution of polyquaternium-11, and can achieve the same or better performance in application.

[0048] Specifically, in some embodiments, the average molecular weight (weight-average molar mass) of polyquaternium-11 can be 1,000,000 g / mol.

[0049] Based on the above-mentioned polyquaternium-11, this application embodiment also provides a shampoo including the above-mentioned polyquaternium-11 or including polyquaternium-11 prepared using the above composition.

[0050] In some embodiments, the shampoo formulation may include 1%-3% by mass of the above-mentioned polyquaternium-11 relative to the total mass of the shampoo.

[0051] In specific embodiments, the shampoo formula may further include any one of the following components: sodium lauryl ether sulfate (AES, active ingredient content may be 70%~100%), cocamidopropyl betaine (TC-CAB35), coconut oil monoethanolamide (CMEA), disodium ethylenediaminetetraacetate (EDTA-2Na), polyquaternium-10 (PQ3000), NaCl, citric acid, phenoxyethanol, and deionized water. All of the above components are commercially available products.

[0052] The composition, polyquaternium-11, and shampoo provided in this application are described below through specific embodiments.

[0053] Example 1

[0054] Preparation of monomer aqueous solution: Add N-vinylpyrrolidone (NVP, 50 g), dimethylaminoethyl methacrylate (DMAEMA, 50 g), and sodium citrate (43 g) to deionized water to obtain a monomer aqueous solution containing sodium citrate.

[0055] Initiator addition: Initiator (AIBN) was added to the monomer aqueous solution, and nitrogen gas was introduced for 10 minutes to obtain the above composition; wherein, in the composition, the mass concentration of NVP is 0.05 g / L, the mass concentration of DMAEMA is 0.05 g / L, the mass concentration of sodium citrate is 0.043 g / L, and the mass concentration of AIBN is 0.00006 g / L.

[0056] Polymerization reaction: The above monomer aqueous solution was placed in a constant temperature water bath at 70℃ and stirred continuously (500 rpm) for 4 hours to obtain a mixed solution containing polyquaternary ammonium salt-11;

[0057] Quaternization treatment: After the above polymerization reaction, diethyl sulfate (DES) was added in a single step, with the amount of DES added being 6% of the amount of DMAEMA added. The mixture was kept at this temperature for 2 hours to obtain an aqueous solution of polyquaternium-11. It is understood that since the volume / amount of AIBN and DES is relatively small compared to other components in the overall composition, the volume effect of AIBN and DES is negligible in this application.

[0058] Example 2

[0059] The specific preparation method is the same as in Example 1, and the sum of the mass concentrations of NVP and DMAEMA remains unchanged. The only difference is that the mass concentration of NVP in this example is 0.04 g / L, and the mass concentration of DMAEMA in this example is 0.06 g / L.

[0060] Example 3

[0061] The specific preparation method is the same as in Example 1, and the sum of the mass concentrations of NVP and DMAEMA remains unchanged. The only difference is that the mass concentration of NVP in this example is 0.03 g / L, and the mass concentration of DMAEMA in this example is 0.07 g / L.

[0062] Example 4

[0063] The specific preparation method is the same as in Example 1, and the sum of the mass concentrations of NVP and DMAEMA remains unchanged. The only difference is that the mass concentration of NVP in this example is 0.02 g / L, and the mass concentration of DMAEMA in this example is 0.08 g / L.

[0064] Example 5

[0065] The specific preparation method is the same as in Example 1, and the sum of the mass concentrations of NVP and DMAEMA remains unchanged. The only difference is that the mass concentration of NVP in this example is 0.01 g / L, and the mass concentration of DMAEMA in this example is 0.09 g / L.

[0066] Example 6

[0067] The specific preparation method is the same as in Example 1, and the sum of the mass concentrations of NVP and DMAEMA remains unchanged. The only difference is that the mass concentration of NVP in this example is 0.09 g / L, and the mass concentration of DMAEMA in this example is 0.01 g / L.

[0068] Example 7

[0069] The specific preparation method is the same as in Example 1, and the sum of the mass concentrations of NVP and DMAEMA remains unchanged. The only difference is that the mass concentration of NVP in this example is 0.08 g / L, and the mass concentration of DMAEMA in this example is 0.02 g / L.

[0070] Example 8

[0071] The specific preparation method is the same as in Example 1, and the sum of the mass concentrations of NVP and DMAEMA remains unchanged. The only difference is that the mass concentration of NVP in this example is 0.07 g / L, and the mass concentration of DMAEMA in this example is 0.03 g / L.

[0072] Example 9

[0073] The specific preparation method is the same as in Example 1, and the sum of the mass concentrations of NVP and DMAEMA remains unchanged. The only difference is that the mass concentration of NVP in this example is 0.06 g / L, and the mass concentration of DMAEMA in this example is 0.04 g / L.

[0074] Example 10

[0075] The specific preparation method is the same as in Example 1, except that the mass concentration of sodium citrate is different. In this example, the mass concentration of sodium citrate is 0.022 g / L.

[0076] Example 11

[0077] The specific preparation method is the same as in Example 1, except that the mass concentration of sodium citrate is different. In this example, the mass concentration of sodium citrate is 0.054 g / L.

[0078] Example 12

[0079] The specific preparation method is the same as in Example 1, except that the mass concentration of sodium citrate is different. In this example, the mass concentration of sodium citrate is 0.065 g / L.

[0080] Example 13

[0081] The specific preparation method is the same as in Example 1, except that the mass concentration of sodium citrate is different. In this example, the mass concentration of sodium citrate is 0.086 g / L.

[0082] Example 14

[0083] The specific preparation method is the same as in Example 1, except that the mass concentration of sodium citrate is different. In this example, the mass concentration of sodium citrate is 0.0043 g / L.

[0084] Example 15

[0085] The specific preparation method is the same as in Example 1, except that the mass concentration of sodium citrate is different. In this example, the mass concentration of sodium citrate is 0.12 g / L.

[0086] Example 16

[0087] The specific preparation method is the same as in Example 1, except that the mass concentration of sodium citrate in this example is 0.001 g / L.

[0088] Example 17

[0089] The specific preparation method is the same as in Example 1, except that the mass concentration of sodium citrate is different. In this example, the mass concentration of sodium citrate is 0.0005 g / L.

[0090] Example 18

[0091] The specific preparation method is the same as in Example 1, and the sum of the mass concentrations of NVP and DMAEMA remains unchanged. The only difference is that the mass concentration of NVP in this example is 0.095 g / L, and the mass concentration of DMAEMA in this example is 0.005 g / L.

[0092] Example 19

[0093] The specific preparation method is the same as in Example 1, and the sum of the mass concentrations of NVP and DMAEMA remains unchanged. The only difference is that the mass concentration of NVP in this example is 0.008 g / L, and the mass concentration of DMAEMA in this example is 0.092 g / L.

[0094] Example 20

[0095] The specific preparation method is the same as in Example 1, and the sum of the mass concentrations of NVP and DMAEMA remains unchanged. The only difference is that the mass concentration of NVP in this example is 0.001 g / L, and the mass concentration of DMAEMA in this example is 0.099 g / L.

[0096] Comparative Example 1

[0097] The specific preparation method is the same as in Example 1, except that the mass concentration of sodium citrate is 0, that is, no sodium citrate is added.

[0098] Comparative Example 2

[0099] The specific preparation method is the same as in Example 1, and the sum of the mass concentrations of NVP and DMAEMA remains unchanged. The only difference is that the mass concentration of NVP in this example is 0.1 g / L, and the mass concentration of DMAEMA in this example is 0 g / L, that is, no DMAEMA is added.

[0100] Comparative Example 3

[0101] The specific preparation method is the same as in Example 1, and the sum of the mass concentrations of NVP and DMAEMA remains unchanged. The only difference is that the mass concentration of NVP in this example is 0 g / L, i.e., no NVP is added. The mass concentration of DMAEMA in this example is 0.1 g / L.

[0102] The transparency of the aqueous solutions of polyquaternium-11 prepared in Examples 1-15 and Comparative Examples 1-3 was tested, and the test results are shown in Table 1 below. The transparency was measured using a UV-Vis spectrometer at 420 nm, and the transmittance displayed by the instrument was recorded.

[0103] The inventors applied the aqueous solutions of polyquaternium-11 prepared in Examples 1-15 and Comparative Examples 1-3 to shampoos for testing. In the shampoo formulations of Examples 1-15 and Comparative Examples 1-3, the mass fractions of other effective components were the same, except for the mass concentration of the key component in the aqueous solution of polyquaternium-11. Specifically, relative to the total mass of the shampoo, the shampoo also included the following components in the following mass fractions: 14% AES (70% active ingredient content), 10% TC-CAB35, 1% CMEA, 0.05% EDTA-2Na, 0.3% PQ3000, 0.7% NaCl, 0.05% citric acid, and 0.5% phenoxyethanol.

[0104] Specifically, the inventors recruited 20 volunteers with similar hair types (all oily), hair volume, and age. They tested the shampoos corresponding to Examples 1-15 and Comparative Examples 1-3 in the same environment (25℃, 50% humidity) to evaluate the shampoos' cleaning power, smoothness, foam richness, volumizing effect, and styling effect. In each performance evaluation, the highest and lowest scores were removed, and the average score was taken. The test results are shown in Table 1 below.

[0105] The evaluation methods and standards for cleansing power are as follows: Evaluation method: The sebum content of specific areas of the scalp of volunteers before and after shampooing was measured using the same commercially available skin oil tester; Evaluation standard: Cleansing power = (Sebum content before shampooing - Sebum content after shampooing) / Sebum content before shampooing × 100%.

[0106] The evaluation method and standards for smoothness are as follows: Volunteers assessed the smoothness by combing their hair after shampooing and blow-drying. The evaluation was based on touch and the feeling of combing. The evaluation criteria were: volunteers used a 0-100% scale, where 100% (extremely smooth, no resistance when combing); 80% (smooth); 60% (moderately smooth); 40% (slightly dry); and 20% (dry, difficult to comb).

[0107] The evaluation method and standard for foam richness are as follows: Evaluation method: Volunteers took an equal amount (10 g) of shampoo and shampooed their hair in artificially hard water with the same temperature (37℃) and hardness (250 ppm). The evaluation was based on the speed of foaming, the amount of foam, and the texture of the foam. Evaluation standard: Volunteers used a 0~100% scale to rate the foam. 100% (After adding water and rubbing, a large amount of foam is produced instantly. The foam is dense, fine, and covers all the hair. The foam does not easily disappear during rinsing). 80% (Sufficient amount of foam is produced quickly. The amount of foam is rich and the texture is good). 60% (It takes a while of rubbing to produce a suitable amount of foam. The amount of foam is just enough, but there is no excess). 40% (The foam is sparse no matter how much you rub). 20% (Almost no foam is produced no matter how much you rub).

[0108] The evaluation methods and standards for the volume effect are as follows: Evaluation method: After shampooing and blow-drying, volunteers visually observe and touch the changes in hair volume; Evaluation standards: Volunteers use a 0-100% rating system, where 100% (extremely strong volume, hair roots stand upright, and the visual increase in hair volume is very obvious); 80% (good volume, with obvious support at the hair roots); 60% (moderate volume, no significant change compared to before shampooing); 40% (hair slightly flat against the scalp); 20% (hair completely flat against the scalp).

[0109] The evaluation method and standards for the styling effect are as follows: Evaluation method: After washing and drying their hair and creating the same style, volunteers visually observed the degree of style retention 6 hours later; Evaluation standards: Volunteers used a 0-100% rating system, where 100% (style perfectly maintained, almost no deformation or collapse); 80% (style well maintained, only minor changes); 60% (style maintained to some extent, but with obvious collapse or deformation); 40% (style collapsed significantly, basically unable to maintain the original shape); 20% (style completely unretained).

[0110] Table 1

[0111]

[0112] Comparing Example 1 with Comparative Example 1, it is evident that the transparency of the aqueous solution of polyquaternium-11 prepared in Example 1 is significantly higher than that of the aqueous solution of polyquaternium-11 prepared in Comparative Example 1. This indicates that adding sodium citrate to the composition used to prepare polyquaternium-11 can improve its transparency. The reason may be due to the presence of Na+ ions in sodium citrate. + and C5H7O5COO -The salting-out effect disrupts the hydrogen bonds and dipole interactions between water molecules and dimethylaminoethyl methacrylate, reducing the solubility of dimethylaminoethyl methacrylate and inhibiting its diffusion rate, thereby reducing its polymerization rate and making polyquaternium-11 more transparent.

[0113] A comparison of Examples 1-14, 16, and 18-20 with Examples 15 and 17 shows that the transparency of the aqueous solutions of polyquaternium-11 prepared in Examples 1-14, 16, and 18-20 is superior to that prepared in Examples 15 and 17. This indicates that a ratio of the sum of the mass concentrations of NVP and DMAEMA to the mass concentration of sodium citrate in the range of 1:(0.01~0.9) can improve the transparency of the polyquaternium-11 aqueous solution.

[0114] Furthermore, a comparison of Examples 1-13 and 18-20 with Examples 14 and 16 shows that the transparency of the aqueous solutions of polyquaternium-11 prepared in Examples 1-13 and 18-20 is superior to that prepared in Examples 14 and 16. This indicates that a ratio of the sum of the mass concentrations of NVP and DMAEMA to the mass concentration of sodium citrate within the range of 1:(0.2~0.9) can effectively increase the transparency of the polyquaternium-11 aqueous solution to 90% or higher.

[0115] A comparison of Examples 1, 10-14 with Examples 15-17 shows that the transparency of the aqueous solutions of polyquaternium-11 prepared in Examples 1 and 10-14 is superior to that prepared in Examples 15-17. This indicates that a mass concentration of sodium citrate in the composition ranging from 0.001 g / L to 0.09 g / L can improve the transparency of the quaternium-11 aqueous solution.

[0116] Furthermore, a comparison of Examples 1 and 10-12 with Examples 13-14 shows that the transparency of the aqueous solutions of polyquaternium-11 prepared in Examples 1 and 10-12 is superior to that prepared in Example 15. This indicates that a mass concentration of sodium citrate in the composition ranging from 0.02 g / L to 0.07 g / L can significantly improve the transparency of the quaternium-11 aqueous solution. A possible reason is that at low salt concentrations (0.002 g / L to 0.07 g / L), sodium citrate inhibits the hydrophobic association of polyquaternium-11 molecular chains through the "salt-dissolution effect," reducing aggregation and improving transparency. At high salt concentrations (>0.07 g / L), excess sodium citrate triggers the "salting-out effect," disrupting the polymer hydration layer, leading to molecular chain aggregation and precipitation, thereby reducing transparency.

[0117] A comparison of Examples 1-9 and 18-20 with Comparative Examples 2-3 shows that the polyquaternium-11 prepared in Examples 1-9 and 18-20, when applied to shampoo, exhibits superior overall performance in terms of transparency, cleansing power, smoothness, foam richness, volumizing effect, and styling effect compared to Comparative Examples 2-3. This indicates that the simultaneous addition of N-vinylpyrrolidone (NVP) and dimethylaminoethyl methacrylate (DMAEMA) can improve transparency while balancing the shampoo's performance in various aspects, including cleansing power, smoothness, foam richness, volumizing effect, and styling effect.

[0118] Furthermore, comparing Examples 1-9 with Examples 18-20 shows that when the mass concentration of N-vinylpyrrolidone is in the range of 0.01 g / L to 0.09 g / L, and the mass concentration of dimethylaminoethyl methacrylate in the composition is in the range of 0.01 g / L to 0.09 g / L, it can significantly improve the performance of the shampoo in terms of cleaning power, smoothness, foam richness, volumizing effect, and styling effect while improving transparency.

[0119] Furthermore, by comparing the trends of cleaning power, smoothness, foam richness, fluffiness, and setting effect in Examples 1-9 and 18-20 with the changes in N-vinylpyrrolidone and dimethylaminoethyl methacrylate, it can be found that as the mass concentration of N-vinylpyrrolidone increases, the performance values ​​of smoothness and setting effect generally show an upward trend. Similarly, as the mass concentration of dimethylaminoethyl methacrylate increases, the performance values ​​of cleaning power, foam richness, and fluffiness generally show an upward trend. This indicates that N-vinylpyrrolidone has a positive effect on improving smoothness and setting effect, while dimethylaminoethyl methacrylate has a positive effect on improving cleaning power, foam richness, and fluffiness.

[0120] The composition, polyquaternium-11, and shampoo provided in the embodiments of this application have been described in detail above. Specific examples have been used to illustrate the principles and implementation methods of this application. The descriptions of the above embodiments are only for the purpose of helping to understand the methods and core ideas of this application. At the same time, for those skilled in the art, there will be changes in the specific implementation methods and application scope based on the ideas of this application. Therefore, the content of this specification should not be construed as a limitation of this application.

Claims

1. A composition for preparing polyquaternary ammonium salt-11, characterized in that, include: N-vinylpyrrolidone; Dimethylaminoethyl methacrylate; Deionized water; as well as Sodium citrate; Wherein, the ratio of the sum of the mass concentrations of N-vinylpyrrolidone and dimethylaminoethyl methacrylate to the mass concentration of sodium citrate is 1:(0.2~0.9). The N-vinylpyrrolidone in the composition has a mass concentration ranging from 0.01 g / L to 0.09 g / L; the dimethylaminoethyl methacrylate in the composition has a mass concentration ranging from 0.01 g / L to 0.09 g / L; and the sodium citrate in the composition has a mass concentration ranging from 0.02 g / L to 0.07 g / L.

2. The composition according to claim 1, characterized in that, The composition further includes: A quaternizing agent, wherein the quaternizing agent in the composition has a mass concentration ranging from 0.003 g / L to 0.006 g / L; and An initiator, wherein the initiator in the composition has a mass concentration ranging from 0.00001 g / L to 0.03 g / L.

3. The composition according to claim 2, characterized in that, The quaternizing agent includes at least one selected from dimethyl sulfate, diethyl sulfate, halocarbon, ethylene oxide, and dimethyl carbonate; and / or, The initiator includes at least one of thermal decomposition initiator, redox initiator and photoinitiator. The thermal decomposition initiator is selected from at least one of azobisisobutyronitrile, azobisisoheptanenitrile, azobisisobutylamidine and benzoyl peroxide. The redox initiator is selected from at least one of a combination of potassium persulfate and sodium bisulfite, a combination of ammonium persulfate and sodium bisulfite, and a combination of hydrogen peroxide and ascorbic acid. The photoinitiator is selected from at least one of benzophenone and photoinitiator 2959.

4. A polyquaternium-11, characterized in that, It is prepared using the composition according to any one of claims 1 to 3.

5. The polyquaternary ammonium salt-11 according to claim 4, characterized in that, in, The polyquaternary ammonium salt-11 includes repeating quaternary ammonium salt units, the structural formula of which is shown in formula (I) below: （I）； Where x and y are greater than 0; The average viscosity of the polyquaternium-11 ranges from 20,000 mPa·s to 60,000 mPa·s.

6. A shampoo, characterized in that, Includes polyquaternium salt-11 as described in claim 4 or 5.

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