Piroctone ethanolamine solid compound as well as composition and application thereof

Abstract

The invention relates to a solid compound of piroctone olamine. The solid compound has a particle size distribution D50 of 31-46 [mu] m; the invention also relates to a composition comprising a solid compound of piroctone olamine having a target particle size range and to the use thereof. Compared with piroctone ethanolamine of which the proportional particle size distribution D50 is less than 30 [mu] m or more than 50 [mu] m, the piroctone ethanolamine solid compound with the particle size distribution D50 of 31-46 [mu] m has the advantages of flocculation and / or deposition.

Description

[0001] This invention claims priority to the earlier application filed on January 6, 2025, with China National Intellectual Property Administration, patent application number 202510016087.X, entitled "Pyrrolidone Ethanolamine Solid Compound, Compositions Thereof and Uses Thereof". The entire contents of the aforementioned earlier application are incorporated herein by reference. Technical Field

[0002] This invention relates to solid compounds of pyrrolidone ethanolamine having a target particle size range; the invention also relates to compositions comprising solid compounds of pyrrolidone ethanolamine having a target particle size range, and their uses. Background Technology

[0003] The efficacy of anti-dandruff agents or conditioners depends primarily on the amount of agent deposited and / or adsorbed onto the scalp and hair. Typically, during application, the contact time between the hair / scalp and any shampoo-free hair care product is very short, e.g., 10–120 seconds, after which the composition is washed off. Therefore, the anti-dandruff agent may not have sufficient time to deposit and / or adsorb. Thus, it is desirable to deposit and / or adsorb as much agent as possible within the limited contact time.

[0004] However, there are technical problems with depositing and / or adsorbing any active ingredients, especially anti-dandruff agents, through wash-out hair care compositions, because a certain amount of anti-dandruff agent particles tend to be washed away rather than deposited and / or adsorbed. To compensate for this loss, increasing the amount of anti-dandruff agent is a possible solution, but this is both technically unreliable and economically infeasible.

[0005] Piroctone ketone ethanolamine (Formula I) is an ethanolamine complex salt (1:1) of pyroctone ketone. It is a widely used and effective antifungal agent against dandruff, possessing anti-dandruff and antipruritic properties. It is commonly used as a preservative, antifungal agent, anti-dandruff agent, acne treatment agent, and deodorant. Compared to ZPT (zinc pyrithione), which is recognized as having good anti-dandruff effects on the market, pyroctone ketone ethanolamine has better safety, lower toxicity, and sustainability. Furthermore, pyroctone ketone ethanolamine can be soluble in surfactant systems to prepare a transparent system, exhibiting low skin irritation and high safety, which is also a significant advantage over similar anti-dandruff products. Therefore, pyroctone ketone ethanolamine has a very wide range of applications in cosmetics and pharmaceuticals.

[0006]

[0007] Pyroxylone ethanolamine is known to have poor solubility in water (0.05%), and its ligand, pyroxylone, has even poorer solubility. Therefore, pyroxylone ethanolamine usually needs to be solubilized in the product system with the help of surfactants. Pyroxylone ethanolamine can also be compounded with various cationic surfactants (quaternary ammonium salts) and cationic active ingredients, and this compounding can further increase its solubility. However, as an active ingredient in anti-dandruff agents, pyroxylone ethanolamine needs to be deposited and / or adsorbed onto the hair to exert its antibacterial effect. During shampooing and rinsing, as the surfactant is continuously diluted, the poorly water-soluble pyroxylone ethanolamine is precipitated out, eventually depositing and / or adsorbing onto the hair to achieve dandruff-removing effects. However, insufficient deposition and adsorption of pyroxylone ethanolamine remains a technical problem.

[0008] WO9823258A1 (Unilever) discloses a shampoo containing pyrrolidone ethanolamine and 0.1 to 5% by weight of polyethyleneimine to enhance the deposition of pyrrolidone ethanolamine.

[0009] CN114072125B (Unilever) discloses a substance containing anti-dandruff agents (such as piroctone olamine, clomiphene citrate, selenium sulfide, zinc pyrithione, or zinc sulfate), wax or waxy substances, and a weight-average molecular weight of 10. 3 Up to 10 7 Da's cationic polymer composite particles. These composite particles not only deposit more anti-dandruff agents on the scalp, but also stabilize anti-dandruff agents, particularly piroctone olamine, in hair care products such as shampoo compositions.

[0010] Currently, there are no research reports on the effect of pyroxol ethanolamine particle size distribution on its deposition and / or adsorption effects. Reports related to pyroxol ethanolamine particle size distribution usually only involve the preparation methods of pyroxol ethanolamine with target particle size.

[0011] For example, Chinese patent applications CN113646298A and CN114126575A (Clariant) describe a method for preparing pyrrolidone ethanolamine salt, which exists in crystalline form and can be added to personal care products. Commercially available pyrrolidone ethanolamine prepared by methods such as those described typically has primary crystals with a width / length ratio of approximately 1:7 and a median diameter D50 of approximately 100 micrometers. These primary crystals of commercially available pyrrolidone ethanolamine are formed during crystallization prior to processing and batch processing steps. After further batch processing, the crystals can change size, and the aggregation of large quantities of pyrrolidone ethanolamine salt crystals can lead to clumping problems during processing and manufacturing.

[0012] Therefore, Clariant disclosed in Chinese patent application CN113646298A a pyrrolidone ethanolamine salt crystal obtained by recrystallization, the crystal having an average width-to-length ratio greater than 1:4 and a D50 greater than 110 micrometers, preferably greater than 140 micrometers; and a D10 greater than 30 micrometers, preferably greater than 50 micrometers.

[0013] In another Chinese patent application, CN114126575A, Clariant disclosed a method for producing piroctone ethanolamine pellets with a target particle size range, comprising: a) compressing piroctone ethanolamine salt crystals to form a compact; and b) grinding the compact to form a large batch of piroctone ethanolamine salt pellets. The piroctone ethanolamine pellets prepared by this method have a D50 of 0.2 mm to 8 mm, preferably 0.3 mm to 6 mm, more preferably 0.3 mm to 2.5 mm, and even more preferably 0.5 mm to 2 mm; and a D90 less than or equal to 1.9 mm; and a D10 greater than or equal to 0.4 mm. Summary of the Invention

[0014] The purpose of this invention is to provide a pyrrolidone ethanolamine solid with greater flocculation and / or deposition advantages.

[0015] This invention provides, in one aspect, a solid compound of pyrrolidone ethanolamine (Formula I). , The particle size distribution D50 of the pyrrolidone ethanolamine solid compound is 31–46 μm.

[0016] Furthermore, the particle size distribution D90 of the pyrrolidone ethanolamine solid compound is 80–130 μm.

[0017] Furthermore, the particle size distribution D10 of the pyrrolidone ethanolamine solid compound is 6–20 μm.

[0018] In at least one embodiment, the particle size distribution of the pyrrolidone ethanolamine solid compound of the present invention is as follows: D50 is 38–45 μm; D90 is 82–120 μm; and D10 is 10–17 μm.

[0019] In at least one embodiment, the particle size distribution of the pyrrolidone ethanolamine solid compound of the present invention is as follows: D50 is 40–45 μm; D90 is 90–120 μm; and D10 is 12–17 μm.

[0020] In at least one embodiment, the solid compound of pyrrolidone ethanolamine according to the present invention has a particle size distribution selected from the following Table 1: Table 1

[0021]

[0022] .

[0023] Another aspect of the present invention provides a composition comprising 0.3 to 1.0% by weight of a pyrrolidone ethanolamine solid compound and at least one surfactant.

[0024] The particle size distribution D50 of the pyrrolidone ethanolamine solid compound in the composition is 31–46 μm.

[0025] Furthermore, the particle size distribution D90 of the pyrrolidone ethanolamine solid compound in the composition is 80–130 μm.

[0026] Furthermore, the particle size distribution D10 of the pyrrolidone ethanolamine solid compound in the composition is 6–20 μm.

[0027] In at least one embodiment, the particle size distribution of the pyrrolidone ethanolamine solid compound in the composition of the present invention is as follows: D50 is 38–45 μm; D90 is 82–120 μm; and D10 is 10–17 μm.

[0028] In at least one embodiment, the particle size distribution of the pyrrolidone ethanolamine solid compound in the composition of the present invention is as follows: D50 is 40–45 μm; D90 is 90–120 μm; and D10 is 12–17 μm.

[0029] In at least one embodiment, the solid compound of pyrrolidone ethanolamine in the composition of the present invention has a particle size distribution selected from the following:

[0030] .

[0031] The surfactant is selected from one or more of the following: sodium cocoyl glutamate, sodium lauroyl glutamate, sodium myristoyl glutamate, sodium palmitoyl glutamate, sodium stearoyl glutamate, disodium capryloyl glutamate, disodium cocoyl glutamate, disodium lauroyl glutamate, disodium stearoyl glutamate, sodium methyl cocoyl taurate, sodium methyl lauroyl taurate, sodium methyl myristoyl taurate, sodium methyl palmitoyl taurate, sodium methyl stearoyl taurate, sodium methyl oleoyl taurate, sodium cocoyl sarcosinate, sodium lauroyl sarcosinate, sodium myristoyl sarcosinate, sodium palmitoyl sarcosinate, or cocamidopropyl betaine.

[0032] In at least one embodiment, the surfactant is selected from one or more of sodium cocoyl glutamate, sodium methyl cocoyl taurate, or cocamidopropyl betaine.

[0033] In at least one embodiment, the composition further comprises 0.1 to 0.5% by weight of a cationic polymer; said cationic polymer is selected from guar hydroxypropyltrimethylammonium chloride, cassia gum hydroxypropyltrimethylammonium chloride, polyquaternium salt-6, polyquaternium salt-10, polyquaternium salt-22, polyquaternium salt-47, polyquaternium salt-53 or polyquaternium salt-74.

[0034] In at least one embodiment, the composition further comprises a pH adjuster selected from inorganic acids, organic acids, or inorganic bases. The inorganic acid is selected from hydrochloric acid, sulfuric acid, carbonic acid, phosphoric acid, sodium hydrogen phosphate, or nitric acid. The organic acid is selected from citric acid, malic acid, tartaric acid, oxalic acid, succinic acid, or acetic acid. The inorganic base is selected from sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate, sodium dihydrogen phosphate, or disodium hydrogen phosphate.

[0035] Another aspect of the present invention provides the use of a pyrrolidone ethanolamine solid compound in personal care compositions or personal care products to increase flocculation and / or deposition.

[0036] The particle size distribution D50 of the pyrrolidone ethanolamine solid compound is 31–46 μm.

[0037] Furthermore, the particle size distribution D90 of the pyrrolidone ethanolamine solid compound is 80–130 μm.

[0038] Furthermore, the particle size distribution D10 of the pyrrolidone ethanolamine solid compound is 6–20 μm.

[0039] In at least one embodiment, the particle size distribution of the pyrrolidone ethanolamine solid compound of the present invention is as follows: D50 is 38–45 μm; D90 is 82–120 μm; and D10 is 10–17 μm.

[0040] In at least one embodiment, the particle size distribution of the pyrrolidone ethanolamine solid compound of the present invention is as follows: D50 is 40–45 μm; D90 is 90–120 μm; and D10 is 12–17 μm.

[0041] In at least one embodiment, the solid compound of pyrrolidone ethanolamine according to the present invention has a particle size distribution selected from the following:

[0042] .

[0043] The personal care composition or personal care product is selected from shampoos, conditioners, hair growth agents, shower gels, cleansing milks, facial cleansers, facial foams, makeup removers, cleansing wipes, soaps, shaving soaps, shaving foams, face masks, face creams, hand creams, or lotions.

[0044] At least one embodiment describes a solid compound of pyrrolidone ethanolamine (Formula I). , The particle size distribution of the pyrrolidone ethanolamine solid compound is D50 of 16–46 μm; D90 of 48–130 μm; and D10 of 3–20 μm; it is prepared by a method comprising the following steps: Pyroxyl ethanolamine solid compound with D50 > 50 μm was added to a vacuum homogenizer at a vacuum of -0.08 MPa and a rotation speed of 3000–8000 rpm for 0.5–2 hours to obtain pyroxyl ethanolamine solid compound (particle size distribution D50 16–46 μm; D90 48–130 μm; D10 3–20 μm).

[0045] Terminology Explanation: Regarding the particle size distribution measurement used in this invention, D50, the median, is defined as the diameter when half of the total population is below this value. Similarly, 90% of the total particles are below the D90 diameter. Similarly, 10% of the total particles are below the D10 diameter.

[0046] The particle size values ​​measured in this invention have an error of ±2%.

[0047] All percentages are by weight of the total composition (w / w). All proportions are by weight. “wt.%” refers to weight percentage. The term “parts”, such as a mixture of 1 part X and 3 parts Y, is by weight.

[0048] Beneficial effects: This invention relates to solid compounds of pyrrolidone ethanolamine having a particle size distribution D50 of 31–46 μm; it also relates to compositions comprising solid compounds of pyrrolidone ethanolamine having a target particle size range and their uses. The pyrrolidone ethanolamine solid compounds of this invention having a particle size distribution D50 of 31–46 μm exhibit greater flocculation and / or deposition advantages compared to comparative pyrrolidone ethanolamines with a particle size distribution D50 < 30 μm or > 50 μm. Detailed Implementation

[0049] The present invention will now be described in more detail through embodiments. However, these specific descriptions are only for illustrating the technical solutions of the present invention and do not constitute any limitation on the present invention.

[0050] Example 1: Preparation of pyrrolidone ethanolamine solid compound The pyrrolidone ethanolamine solid compound was prepared according to the methods described in Examples 1 and 2 of Chinese Invention Patent CN117003694B: Salt formation: Add bottom material II to a dry and clean four-necked flask equipped with a stirrer, thermometer, and condenser. Heat to 45-50°C and add ethanolamine dropwise over 0.5 hours. After the addition is complete, keep the temperature at 45°C for 2 hours, then cool to 0-5°C and keep it at 0-5°C for 1 hour. Filter and wash the filter cake with ethyl acetate at 0-5°C to obtain filter cake I and filtrate I. Filtrate I is recovered.

[0051] Pulping: In a dry, clean four-necked flask equipped with a thermometer, stirrer, and reflux condenser, add filter cake I and ethyl acetate. Reflux for 30 minutes, then cool to 20–25°C and maintain the temperature for 1 hour. Filter, and wash the filter cake with ethyl acetate at 20–25°C to obtain filter cake II and filtrate II. Filter cake II is sent to the drying process, and filtrate II is used in the next batch as salt.

[0052] Drying: Place filter cake II in a dry and clean vacuum oven, control the vacuum degree to 10-15 mmHg, and dry at 25-30℃ for 2 hours, 30-35℃ for 1 hour, and 35-40℃ for 1 hour; then dry at 45℃ for 2 hours with a vacuum degree of 3-5 mmHg, and dry at 65-70℃ until LOD < 0.25% to obtain pyrrolidone ethanolamine salt.

[0053] The particle size range of the pyroxone ethanolamine solid compound prepared by the above method is shown in Table 2.

[0054] Table 2

[0055] The pyrrolidone ethanolamine solid compound (particle size distribution D50 of 54–62 μm) obtained above was added to a vacuum homogenizer at a vacuum of -0.08 MPa and a rotation speed of 3000–8000 rpm for 0.5–2 hours to obtain the pyrrolidone ethanolamine solid compound (particle size distribution D50 of 31–46 μm; D90 of 80–130 μm; D10 of 6–20 μm).

[0056] The pulverized pyroxone ethanolamine solid compound and its particle size range are recorded in Table 3.

[0057] Table 3

[0058]

[0059]

[0060]

[0061]

[0062]

[0063]

[0064] Particle size distribution (PSD) determination method: Dry particle size determination

[0065] Instruments and reagents: Bettersize 2600 laser particle size analyzer

[0066] Software: Mastersizer 3000

[0067] Sample preparation and PSD measurement: Place approximately 0.2 g of the sample to be tested into the syringe funnel, and start the measurement when the light shading is between 0.1% and 6%. The measurement time should be maintained at more than 10 seconds, and each sample should be measured three times.

[0068] The values ​​given in Tables 1, 2 and 3 are the averages of three measurements.

[0069] Comparative Example 1: Preparation of Pyroxyl ethanolamine solid compound

[0070] The pyroxone ethanolamine solid compound (particle size distribution D50 of 54-62 μm) prepared according to the method of Example 1 was added to a vacuum homogenizer at a vacuum of -0.08 MPa and a rotation speed of 3000-8000 rpm for 0.5-2 hours. The pulverized pyroxone ethanolamine solid compound and its particle size range are recorded in Table 4.

[0071] Table 4

[0072] Particle size distribution (PSD) determination method: Dry particle size determination

[0073] Instruments and reagents: Bettersize 2600 laser particle size analyzer

[0074] Software: Mastersizer 3000

[0075] Sample preparation and PSD measurement: Place approximately 0.2 g of the sample to be tested into the syringe funnel, and start the measurement when the light shading is between 0.1% and 6%. The measurement time should be maintained at more than 10 seconds, and each sample should be measured three times.

[0076] The values ​​given in Table 4 are the average of the three measurements.

[0077] Examples 2-3: Shampoo formulations based on sodium cocoyl glutamate system

[0078] The shampoo formulations of the sodium cocoyl glutamate system (each component is given in weight %) are shown in Table 5.

[0079] Table 5

[0080] Comparative Examples 2-3: Shampoo formulations based on the sodium cocoyl glutamate system

[0081] The shampoo formulations of the sodium cocoyl glutamate system (each component is given in weight %) are shown in Table 6.

[0082] Table 6

[0083] Example 4: Shampoo formulation based on sodium methyl cocoyl taurate system

[0084] The shampoo formulations of the sodium methyl cocoyl taurate system (each component is given in weight %) are shown in Table 7.

[0085] Table 7

[0086] Comparative Example 4: Shampoo formulation based on sodium methyl cocoyl taurate system

[0087] The shampoo formulations of the sodium methyl cocoyl taurate system (each component is given in weight %) are shown in Table 8.

[0088] Table 8

[0089] Experimental Example 1: Comparative Experiment on Flocculation of Pyroxanone Ethanolamine with Different Particle Sizes

[0090] i) Based on the shampoo formulations of Examples 2-4 and Comparative Examples 2-4, corresponding shampoo samples were prepared, totaling 18 groups.

[0091] ii) Weigh the corresponding weight (g) of shampoo sample and deionized water into test bottles according to the dilution ratios shown in Table 9 (numbers 1 to 11, where the weight ratio of shampoo sample to deionized water is 1:1, 1:2, 1:3, 1:5, 1:8, 1:10, 1:15, 1:20, 1:50, 1:100, and 1:1000, respectively). Tighten the caps and gently and slowly invert the test bottles to ensure complete mixing of the shampoo sample and deionized water, avoiding the generation of air bubbles during the mixing process. Then, take photos, perform turbidity tests, and conduct quantitative analysis at 0 minutes and 10 minutes, respectively.

[0092] Table 9

[0093] iii) Photographing: Place the test bottles in a horizontal row from left to right in the TILO P60(6) six-source standard light source color matching light box according to the dilution ratio 1 to 11. Place a black and white striped substrate behind the bottles, turn on the D65 light source, and take photos at 0 minutes and 10 minutes respectively using a Canon camera.

[0094] iv) Turbidity test

[0095] a) Calibrate the instrument using calibration fluid

[0096] b) Place the diluted sample from step ii) into the specific container of the turbidity meter and measure the turbidity at 0 minutes and 10 minutes respectively.

[0097] v) Quantitative analysis

[0098] a) Filter the diluted sample from step ii) using a 0.45 μm filter head and collect the filtrate.

[0099] b) Weigh 2.000 g of the collected filtrate and place it in a 25 mL stoppered colorimetric tube. Add 10 mL of methanol, mix thoroughly, and extract ultrasonically for 20 min in an ultrasonic cleaner. Then, bring the volume to 25 mL with methanol and mix well. Filter through an injection solvent filter (organic solvent type, 0.45 μm). Use the filtrate for liquid chromatography analysis.

[0100] The analysis method is as follows: Column: C 18 Column; length 250mm, inner diameter 4.6mm, particle size 5μm.

[0101] Mobile phase: Accurately weigh 1.361 g of NaH2PO4 and 0.186 g of EDTA-disodium to prepare 1 L of aqueous solution, and prepare acetonitrile / NaH2PO4-EDTA disodium buffer solution at a volume ratio of 70:30.

[0102] Flow rate: 0.8 mL / min.

[0103] Detection wavelength: 217nm.

[0104] Column temperature: 35℃.

[0105] Injection volume: 10 μL.

[0106] c) The test was performed three times, and the average value of the parallel tests was taken. The amount of pyroxenone ethanolamine dissolved in the aqueous phase was calculated and denoted as ω.

[0107] Calculation formula: The amount of flocculated and / or deposited piroctone ethanolamine (%) = 1 - ω.

[0108] Tables 5 and 7 show the pyrrolidone ethanolamine in any of the shampoo formulations in Examples 2, 3, and 4. Five batches of pyrrolidone ethanolamine samples with different particle size distributions were tested in parallel, as shown in Tables 10 and 11. Among them, batch CN117003694B_001, the solid compound of pyrrolidone ethanolamine prepared according to the method described in Example 1 of Chinese Invention Patent CN117003694B, is listed below. Table 10

[0109] Table 11

[0110] The components are shown in Tables 12, 13, and 14: Table 12

[0111] Table 13

[0112] Table 14

[0113] The flocculation results of piroctone ethanolamine with different particle sizes in the sodium cocoyl glutamate system are shown in Tables 15-18: Table 15

[0114] Table 16

[0115] Wherein: "---" indicates that the clarification has not precipitated; "+" indicates that a small amount of flocculation has occurred.

[0116] Experimental Conclusion: The shampoo samples of Comparative Examples 2, Examples 2B-2D, and Comparative Examples 2A and 2E are sodium cocoyl glutamate systems without cationic polymers. With continuous dilution of the surfactant sodium cocoyl glutamate by deionized water, the piroctone ketone ethanolamine dissolved in the shampoo samples of Examples 2B-2D, Comparative Examples 2A and 2E should be precipitated out in reverse. However, the inventors unexpectedly discovered that piroctone ketone ethanolamine with different particle size distributions exhibits different flocculation behaviors during reverse precipitation.

[0117] In Comparative Example 2A, pyrrolidone ethanolamine with a particle size distribution D50 of 16 μm did not precipitate within 0–10 minutes. In Comparative Example 2E, pyrrolidone ethanolamine with a particle size distribution D50 of 54 μm did not precipitate within 0 minutes, but after extending the standing time to 10 minutes, a very small amount of precipitation occurred at dilution ratios of 1:50–100.

[0118] In Examples 2B-2D, pyrrolidone ethanolamine with a particle size distribution D50 of 31-45 μm did not precipitate at 0 minutes, but precipitated after 10 minutes at dilution ratios of 1:15-100, demonstrating superior flocculation advantages.

[0119] In Example 2D, pyrrolidone ethanolamine with a particle size distribution D50 of 45 μm began to precipitate at a dilution ratio of 1:15, demonstrating superior flocculation advantages.

[0120] Table 17

[0121] Table 18

[0122] Where: "---" indicates clarification without precipitation; "+" indicates a small amount of flocculation; "++" indicates partial flocculation; "This indicates a large amount of flocculation and the presence of large particles clustered together."

[0123] Experimental conclusions: The shampoo samples of Comparative Examples 3, Examples 3B-3D, Comparative Examples 3A and 3E are sodium cocoyl glutamate systems containing cationic polymers. With the help of the cationic polymer polyquaternium-10, piroctone ketone ethanolamine is more likely to flocculate and / or deposit. However, the inventors unexpectedly discovered that with the help of the cationic polymer polyquaternium-10, piroctone ketone ethanolamine with different particle size distributions also exhibits different performance in flocculation and / or deposition.

[0124] In Examples 3B-3D, pyrrolidone ethanolamine with a particle size distribution D50 of 31-45 μm exhibited significant flocculation and large particle agglomeration at dilution ratios of 1:2-1:10 within 0 minutes. In particular, pyrrolidone ethanolamine with a particle size distribution D50 of 45 μm in Example 3D showed large particle agglomeration and precipitation at dilution ratios of 1:2-100, demonstrating the most significant flocculation and / or deposition advantages. In contrast, pyrrolidone ethanolamine with a particle size distribution D50 of 16 μm in Comparative Example 3A, compared to the blank control of Comparative Example 3, only showed precipitation at a dilution ratio of 1:100 within 0 minutes, and almost no large particle agglomeration was observed, indicating a less pronounced flocculation advantage.

[0125] In Examples 3B-3D, pyrrolidone ethanolamine with a particle size distribution D50 of 31-45 μm, after standing for 10 minutes, mostly exhibited significant flocculation and large particle agglomeration deposition at dilution ratios of 1:2-100. Therefore, compared with pyrrolidone ethanolamine with a particle size distribution D50 of <30 μm or >50 μm in Comparative Examples 3A and 3E, pyrrolidone ethanolamine with a particle size distribution D50 of 38-45 μm showed a significant flocculation and / or deposition advantage. Pyrrolidone ethanolamine with a particle size distribution D50 of 45 μm showed the best flocculation and / or deposition advantage.

[0126] The flocculation results of piroctone ethanolamine with different particle sizes in the sodium methyl cocoyl taurate system are shown in Tables 19-20: Table 19

[0127] Table 20

[0128] Where: "---" indicates clarification without precipitation; "+" indicates a small amount of flocculation; "++" indicates partial flocculation; "This indicates a large amount of flocculation and the presence of large particles clustered together."

[0129] Experimental Conclusions: The shampoo samples of Comparative Examples 4, 4B-4D, 4A, and 4E are sodium methylcocoyl taurate systems containing cationic polymers. The inventors unexpectedly discovered that pyrrolidone ethanolamine with different particle size distributions exhibits different performance in flocculation and / or deposition. In Examples 4B-4D, pyrrolidone ethanolamine with a particle size distribution D50 of 31-45 μm showed a more significant flocculation and / or deposition advantage. In Example 4C, pyrrolidone ethanolamine with a particle size distribution D50 of 38 μm showed an even more significant flocculation and / or deposition advantage.

[0130] The turbidity test results are shown in Tables 21 and 22: Table 21

[0131] Table 22

[0132] Experimental conclusion: (1) The shampoo samples of Comparative Example 2, Examples 2B-2D, Comparative Examples 2A and 2E are sodium cocoyl glutamate systems without cationic polymers. As the surfactant sodium cocoyl glutamate is continuously diluted by deionized water, the pyrrolidone ethanolamine that has been dissolved in the shampoo sample is precipitated out in reverse. The degree of reverse precipitation is different, and the turbidity test results are also different.

[0133] In Comparative Example 2A, the turbidity of the shampoo sample with a particle size distribution D50 of 16 μm showed no significant change from 0 to 10 minutes. In Comparative Example 2E, the turbidity of the pyrrolidone ethanolamine with a particle size distribution D50 of 54 μm significantly increased at dilution ratios of 1:50 to 1:100 after a prolonged standing time of 10 minutes, with turbidity values ​​ranging from 25.7 to 32.2.

[0134] In Examples 2B-2D, pyrrolidone ethanolamine with a particle size distribution D50 of 31-45 μm showed a significant increase in turbidity at dilution ratios of 1:15-1:100 after a standing time of 10 minutes. In Example 2D, pyrrolidone ethanolamine with a particle size distribution D50 of 45 μm had a turbidity value of 30.7 at a dilution ratio of 1:15, demonstrating superior flocculation advantages.

[0135] (2) The shampoo samples of Comparative Examples 3, Examples 3B-3D, Comparative Examples 3A and 3E are sodium cocoyl glutamate systems with cationic polymers. With the help of the cationic polymer polyquaternium-10, pyrrolidone ethanolamine is more likely to flocculate and / or deposit.

[0136] In Examples 3B-3D, pyrrolidone ethanolamine with a particle size distribution D50 of 31-45 μm showed a significant increase in turbidity at 0 minutes when diluted at ratios of 1:1 to 1:1000, and the turbidity value was higher than that of Comparative Examples 3, 3A, and 3E under the same test conditions. In Example 3D, pyrrolidone ethanolamine with a particle size distribution D50 of 45 μm had an overall higher turbidity value than under other test conditions, indicating superior flocculation advantages.

[0137] Extending the placement time to 10 minutes, the trend of the turbidity test results is the same as that of the turbidity test results at 0 minutes.

[0138] (3) The shampoo samples of Comparative Examples 4, Examples 4B-4D, Comparative Examples 4A and 4E are sodium methyl cocoyl taurate systems with cationic polymers.

[0139] In Examples 4B-4D, the turbidity values ​​of pyrrolidone ethanolamine with a particle size distribution D50 of 31-45 μm showed a significant increase at dilution ratios of 1:1 to 1:100, and the turbidity values ​​were higher than those of Comparative Examples 4, 4A, and 4E under the same test conditions. When the standing time was extended to 10 minutes, the trend of the turbidity test results was the same as that of the turbidity test results at 0 minutes.

[0140] The results of the quantitative analysis of flocculated and / or deposited pyrrolidone ethanolamine are shown in Table 23: Table 23

[0141] Where: "-" indicates not detected.

[0142] Experimental conclusion: (1) The shampoo samples of Examples 2B-2D, Comparative Examples 2A and 2E are sodium cocoyl glutamate systems without cationic polymers. As the surfactant sodium cocoyl glutamate is continuously diluted by deionized water, the pyrrolidone ethanolamine that has been dissolved in the shampoo sample is precipitated in reverse. The amount (%) of flocculated and / or deposited pyrrolidone ethanolamine varies depending on the particle size.

[0143] In Examples 2B-2D, the amount (%) of pyrrolidone ethanolamine with a particle size distribution D50 of 31-45 μm and a dilution ratio of 1:1 to 1:5 was higher than that in Comparative Examples 2A and 2E under the same test conditions. In Example 2D, the amount (%) of pyrrolidone ethanolamine with a particle size distribution D50 of 45 μm was higher than that under other test conditions, indicating superior flocculation performance.

[0144] (2) The shampoo samples of Examples 3B-3D and Comparative Examples 3A and 3E are sodium cocoyl glutamate systems with cationic polymers. With the help of the cationic polymer polyquaternium-10, pyrrolidone ethanolamine is more likely to flocculate and / or deposit.

[0145] In Examples 3B-3D, the amount (%) of pyrrolidone ethanolamine with a particle size distribution D50 of 31-45 μm and a dilution ratio of 1:1-1:5 was higher than that of Comparative Examples 3A and 3E under the same test conditions. In Example 3C, the amount (%) of pyrrolidone ethanolamine with a particle size distribution D50 of 38 μm and a dilution ratio of 1:2-1:5 was higher than that under other test conditions, indicating superior flocculation performance.

[0146] (3) The shampoo samples of Examples 4B-4D, Comparative Examples 4A and 4E were sodium methyl cocoyl taurate systems containing cationic polymers. In Examples 4B-4D, the amount (%) of pyrrolidone ethanolamine with a particle size distribution D50 of 31-45 μm and a dilution ratio of 1:1 was higher than that of Comparative Examples 4A and 4E under the same test conditions.

[0147] In summary, pyrrolidone ethanolamine with different particle size distributions exhibits varying performance in flocculation and / or deposition. Pyrrolidone ethanolamine with a particle size distribution D50 of 31–45 μm shows a more significant advantage in flocculation and / or deposition. Pyrrolidone ethanolamine with a particle size distribution D50 of 38–45 μm shows an even more pronounced advantage in flocculation and / or deposition.

[0148] The above specific embodiments further illustrate the purpose, technical solution and beneficial effects of this application. It should be understood that the above are only specific embodiments of this application and are not intended to limit the scope of protection of this application. Any modifications, equivalent substitutions, improvements, etc., made on the basis of the technical solution of this application should be included within the scope of protection of this application.

Claims

1. A solid compound of pyrrolidone ethanolamine (Formula I), ， Its features are, The particle size distribution D50 of the pyrrolidone ethanolamine solid compound is 31–46 μm.

2. The solid compound of pyrrolidone ethanolamine according to claim 1, characterized in that: D90 is 80–130 μm.

3. The solid compound of pyrrolidone ethanolamine according to claim 1, characterized in that: D10 ranges from 6 to 20 μm.

4. The solid compound of pyrrolidone ethanolamine according to claim 1, characterized in that: D50 is 38–45 μm; D90 is 82–120 μm; D10 is 10–17 μm.

5. The solid compound of pyrrolidone ethanolamine according to claim 1, characterized in that: D50 is 40–45 μm; D90 is 90–120 μm; D10 is 12–17 μm.

6. The solid compound of pyrrolidone ethanolamine according to claim 1, characterized in that: The solid compound of pyrrolidone ethanolamine has a particle size distribution selected from the following: ； 。 7. A composition, characterized in that: The compound comprises 0.3 to 1.0% by weight of any one of claims 1 to 6, and at least one surfactant.

8. The composition according to claim 7, characterized in that: The surfactant is selected from one or more of the following: sodium cocoyl glutamate, sodium lauroyl glutamate, sodium myristoyl glutamate, sodium palmitoyl glutamate, sodium stearoyl glutamate, disodium capryloyl glutamate, disodium cocoyl glutamate, disodium lauroyl glutamate, disodium stearoyl glutamate, sodium methyl cocoyl taurate, sodium methyl lauroyl taurate, sodium methyl myristoyl taurate, sodium methyl palmitoyl taurate, sodium methyl stearoyl taurate, sodium methyl oleoyl taurate, sodium cocoyl sarcosinate, sodium lauroyl sarcosinate, sodium myristoyl sarcosinate, sodium palmitoyl sarcosinate, or cocamidopropyl betaine.

9. The composition according to claim 7 or 8, characterized in that: The composition further comprises 0.1 to 0.5% by weight of a cationic polymer; the cationic polymer is selected from guar hydroxypropyltrimethylammonium chloride, cassia gum hydroxypropyltrimethylammonium chloride, polyquaternium salt-6, polyquaternium salt-10, polyquaternium salt-22, polyquaternium salt-47, polyquaternium salt-53 or polyquaternium salt-74.

10. The use of the pyrrolidone ethanolamine solid compound of any one of claims 1 to 6 in personal care compositions or personal care products to increase flocculation and / or deposition.

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