Controllable modified volcanic slime Pickering emulsifier as well as preparation method and application thereof

Abstract

The invention discloses a regulatable modified volcanic slime Pickering emulsifier and a preparation method and application thereof, relates to the field of skin care products, and aims to solve the problem that the emulsifying effect of silicone oil and paraffin with low polarity of the emulsifier is poor. The preparation method of the emulsifier comprises the following steps: drying volcanic slime in the shade, crushing and screening; mixing with a modifier, and carrying out modification treatment; and drying the modified volcano slime to obtain the Pickering emulsifier capable of regulating and controlling the hydrophilic-hydrophobic performance, and preparing the emulsifier into an emulsion. The volcano slime is modified by various fatty acids, so that the emulsifying capacity of the volcano slime is more prominent, and the volcano slime can be widely applied to various oils and fats. And the prepared emulsion has obvious improvement effects on moisture retention, whitening property, freckle removal property, wrinkle resistance and the like, and has no obvious irritation.

Description

Technical Field

[0001] The present invention relates to the field of skin care products, in particular to a controllable modified volcanic mud Pickering emulsifier and its preparation method and application. Background Art

[0002] As a unique natural mineral resource, Wudalianchi volcanic mud has significant advantages in geological composition, physical and chemical properties, and functionality, especially showing its application potential in the development of Pickering emulsifiers. The Wudalianchi volcanic group is one of the youngest volcanic groups in China (about 300 years old). The mud is formed by the weathering and sedimentation of basalt after volcanic eruptions, and is rich in volcanic glass, mineral crystals, and trace elements (such as silicon, aluminum, iron, magnesium, etc.). It has a multi-mineral structure with a natural nano-scale lamellar structure, and it is easy to regulate the surface properties (hydrophilic / hydrophobic) through modification. It has diverse active ingredients, containing various organic acids and mineral elements, endowing the mud with antioxidant, soothing and repairing and other beauty efficacy characteristics, and is suitable for the cosmetics field. Currently, the oils used in the emulsions prepared from volcanic mud are limited, all of which are plant oils with moderate polarity, while the emulsification effect on low-polarity silicone oil and paraffin is not good. Summary of the Invention

[0003] The present invention is to solve the above technical problems, and provides a controllable modified volcanic mud Pickering emulsifier and its preparation method and application.

[0004] A preparation method of a controllable modified volcanic mud Pickering emulsifier of the present invention, the preparation method includes the following steps:

[0005] (1) Pretreatment of volcanic mud: Air-dry, crush and screen the volcanic mud to a particle size of 0.5 - 1 micron for standby;

[0006] (2) Surface modification: Mix the pretreated volcanic mud with a modifier, and react for 5 - 10 hours under the condition that the modification temperature is 40 - 80°C; the modifier is one or more of oleic acid, linoleic acid, stearic acid, and palmitic acid;

[0007] (3) Drying and dispersion: Dry the modified volcanic mud to obtain a Pickering emulsifier with controllable hydrophilic-hydrophobic properties.

[0008] Further, the addition amount of the modifier is 1% - 20% of the mass of the volcanic mud.

[0009] Further, the addition amount of the modifier is 5% - 15% of the mass of the volcanic mud.

[0010] Further, the volcanic mud is Yaoquanshan volcanic mud.

[0011] Furthermore, the modifier is at least two of oleic acid, linoleic acid, stearic acid, and palmitic acid, and each component in the at least two components has the same mass.

[0012] Furthermore, the particle size in step (1) is 0.8 - 1 μm.

[0013] Furthermore, the contact angle between the prepared Pickering emulsifier with adjustable hydrophilic - hydrophobic properties and water is 30° - 150°, and the particle size distribution is 0.5 - 2 μm.

[0014] Regarding the application of the adjustable modified volcanic mud Pickering emulsifier prepared by the present invention, the Pickering emulsifier with adjustable hydrophilic - hydrophobic properties is used to prepare Pickering emulsions.

[0015] Furthermore, the Pickering emulsion is prepared as follows:

[0016] (a) Disperse the Pickering emulsifier with adjustable hydrophilic - hydrophobic properties in the aqueous phase or the oil phase to obtain an emulsifier solution with a mass concentration of 0.1% - 20%.

[0017] (b) Mix the aqueous phase and the oil phase, and the volume ratio of water to oil is 1:9 to 9:1.

[0018] (c) Through homogenization, ultrasonic treatment, or high - speed shear emulsification, form a stable emulsion.

[0019] Furthermore, the droplet size of the emulsion is 1 - 100 μm.

[0020] The present invention has the following beneficial effects:

[0021] The present invention uses multiple fatty acids to modify volcanic mud, which can make its emulsifying ability more prominent and can be widely applied to a variety of oils. It significantly improves the emulsification effect of low - polarity silicone oil and paraffin. The prepared emulsion has obvious improvement effects in terms of moisturizing, whitening, freckle - removing, anti - wrinkle, etc., and has no obvious irritation. Description of the Drawings

[0022] Figure 1 It is a photo of the emulsification effect of the emulsion of the present invention on various oils; in the figure, 1 is olive oil, 2 is sweet almond oil, 3 is grape seed oil, 4 is elderberry fruit oil, 5 is jojoba oil, 6 is liquid paraffin, 7 is white oil, 8 is isopropyl myristate, and 9 is avocado oil;

[0023] Figure 2 It is the FTIR test spectrum of the adjustable modified volcanic mud Pickering emulsifier in Example 1;

[0024] Figure 3 FTIR test spectrum of Pickering emulsifier prepared from volcanic mud not modified with the modifier of Example 1. Detailed implementation manners

[0025] To make the objectives, technical solutions and advantages of the embodiments of the present invention clearer and more understandable, the spirit of the content disclosed by the present invention will be described in detail below. After any person skilled in the art in the relevant technical field understands the embodiments of the content of the present invention, the techniques taught by the content of the present invention can be changed and modified, which does not deviate from the spirit and scope of the content of the present invention.

[0026] The illustrative embodiments of the present invention and their descriptions are used to explain the present invention, but do not limit the present invention.

[0027] Example 1

[0028] A preparation method of a controllable modified volcanic mud Pickering emulsifier in this example, the preparation method includes the following steps:

[0029] (1) Pretreatment of volcanic mud: Air-dry, crush and screen the Yaoquanshan volcanic mud to a particle size of 0.8 microns for standby;

[0030] (2) Surface modification: Mix the pretreated volcanic mud with the modifier, and react for 5 hours under the condition that the modification temperature is 60°C; the modifier is stearic acid and oleic acid in a ratio of 1:1; the dosage of the modifier is 5% of the mass of the volcanic mud.

[0031] (3) Drying and dispersion: Dry the modified volcanic mud to obtain a Pickering emulsifier with controllable hydrophilic-hydrophobic properties;

[0032] (4) Disperse the Pickering emulsifier with controllable hydrophilic-hydrophobic properties to make an O / W emulsion with a water-oil ratio of 7:3, where the oil phase is liquid paraffin, and the average particle size of the emulsion droplets is 30 μm.

[0033] Figure 1 Shows the emulsification effects of the Pickering emulsifier with controllable hydrophilic-hydrophobic properties on different oils. As shown in the figure, the Pickering emulsifier of this example can achieve good emulsification effects on a variety of oils.

[0034] By Figure 2 and Figure 3 Comparing the FTIR test spectra, the controllable modified volcanic mud Pickering emulsifier of Example 1 has 2 more absorption peaks representing fatty acids at a wavelength of 3000 than the emulsifier prepared from volcanic mud not modified with the modifier of Example 1, which proves that the volcanic mud in Example 1 was successfully modified.

[0035] Emulsion Stability Test of Example 1

[0036] To verify the stability difference between the volcanic mud Pickering emulsion prepared in Example 1 and other types of emulsifiers, a comparative test was designed for verification.

[0037] The prepared emulsion above was used to measure the stability by centrifuging at 4000 revolutions per minute for a stable time under different pH values and different NaCl concentrations. The stable time gradients were (5 min, 10 min, 15 min, 20 min, 25 min, greater than 30 min). Each group of samples was tested in triplicate and the average value was taken. The test results are shown in Table 1.

[0038] Table 1 Stability Test of Volcanic Cold Spring Water-in-Oil Pickering Emulsion

[0039]

[0040]

[0041] Note: The unmodified mud in the table is the volcanic mud that has not been modified with the modifier of Example 1, and the others are the same as in Example 1.

[0042] From the above results, it can be seen that under the same preparation process conditions, the stable time of the emulsion prepared by the modified volcanic mud group after centrifuging at 4000 revolutions per minute is greater than 30 min under different pH values and different NaCl concentrations, and its stability is significantly better than that of the unmodified mud group and the synthetic emulsifier group. It can be proved that the Pickering emulsion prepared by relying on the modified volcanic mud in this example has excellent stability.

[0043] Example 2

[0044] Human Test of the Emulsion in Example 1

[0045] 1. Experimental Method:

[0046] 1.1 Volunteer Grouping: 60 healthy volunteers were recruited and randomly divided into 6 groups with 10 people in each group. The Pickering emulsion prepared in Example 1 and the emulsion prepared by the method of Example 1 without using the modifier of Example 1 were respectively tested for their usage effects as a comparative example.

[0047] 1.2 Application Method: One side of each volunteer's face was the test area, and the emulsion of Example 1 and the comparative emulsion were evenly applied; the symmetrical area on the other side was the blank control. It was ensured that the volunteers had not used cosmetics and had no history of allergies in the past 3 days before the experiment.

[0048] 1.3 Experimental Period: Used once a day for 15 consecutive days, and the usage effects and adverse reactions were recorded during this period.

[0049] 2. Evaluation Criteria:

[0050] Moisturizing, Whitening, Freckle Removing, Anti-Wrinkle: Adopt a 0-5 scoring system (0-2 points: poor effect; 2-3 points: average; 3-4 points: good; 4-5 points: significant). Irritation: Record reactions such as skin redness and itching. The lower the score, the less irritation.

[0051] 3. Data Analysis: Take the average value of each group of results and compare the differences between Example 1 and the comparative example.

[0052] 4. Experimental Results:

[0053] 4.1 Skin Care Effects:

[0054] 4.1.1 Emulsion of Example 1: Moisturizing: 4.3 points (significantly improve skin moisture content); Whitening: 4.1 points (obviously improve skin tone uniformity); Freckle Removing: 3.8 points (reduce pigmentation); Anti-Wrinkle: 3.9 points (outstanding effect on fading fine lines).

[0055] 4.1.2 Emulsion of the Comparative Example (without added modified volcanic mud): Moisturizing: 2.5 points; Whitening: 2.1 points; Freckle Removing: 1.8 points; Anti-Wrinkle: 1.9 points.

[0056] 4.2 Irritation Score:

[0057] Emulsion of Example 1: 0.7 points (no significant adverse reactions);

[0058] Emulsion of the Comparative Example: 1.5 points (slight dryness occurred in some volunteers).

[0059] The Pickering emulsion of Example 1 shows significant effects in moisturizing, whitening, freckle removing and anti-wrinkle, and has low irritation. The comprehensive score is significantly better than that of the unmodified comparative example emulsion.

Claims

1. A method for preparing a controllable modified volcanic mud Pickering emulsifier, characterized in that The preparation method comprises the following steps: (1) Pretreatment of volcanic mud: the volcanic mud is dried in the shade, crushed, and sieved to a particle size of 0.5-1 micron for later use; (2) Surface modification: the pretreated volcanic mud is mixed with a modifier and reacted at a modification temperature of 40-80° C. for 5-10 hours; the modifier is one or more of oleic acid, linoleic acid, stearic acid, and palmitic acid; (3) Drying and dispersion: The modified volcanic mud is dried to obtain a Pickering emulsifier with adjustable hydrophilic-hydrophobic properties.

2. The method for preparing a controllable modified volcanic mud Pickering emulsifier according to claim 1, characterized in that The amount of the modifier added is 1%-20% of the mass of the volcanic mud.

3. The method for preparing a controllable modified volcanic mud Pickering emulsifier according to claim 2, characterized in that The amount of the modifier added is 5%-15% of the mass of the volcanic mud.

4. The method for preparing a controllable modified volcanic mud Pickering emulsifier according to claim 3, characterized in that The volcanic mud is Yaoquanshan volcanic mud.

5. The method for preparing a controllable modified volcanic mud Pickering emulsifier according to claim 1, 2, or 3, characterized in that The modifier is at least two of oleic acid, linoleic acid, stearic acid and palmitic acid, and each component of the at least two components is of equal mass.

6. The method for preparing a controllable modified volcanic mud Pickering emulsifier according to claim 1, characterized in that The particle size described in step (1) is 0.8-1 micron.

7. The method for preparing a controllable modified volcanic mud Pickering emulsifier according to claim 1, characterized in that The prepared Pickering emulsifier with adjustable hydrophilic-hydrophobic properties has an antenna angle of 30°-150° with water and a particle size distribution of 0.5-2 μm.

8. Use of the adjustable modified volcanic mud Pickering emulsifier prepared by any one of claims 1 to 7, characterized in that The Pickering emulsifier with adjustable hydrophilic-hydrophobic properties is used to prepare Pickering emulsion.

9. The use according to claim 8, characterized in that The Pickering emulsion is prepared as follows: (a) dispersing a Pickering emulsifier with adjustable hydrophilic-hydrophobic properties in an aqueous phase or an oil phase to prepare an emulsifier solution with a mass concentration of 0.1% to 20%; (b) mixing the water phase with the oil phase in a water-to-oil volume ratio of 1:9 to 9:1; (c) forming a stable emulsion by homogenization, ultrasound or high-speed shear emulsification.

10. The use according to claim 8 or 9, characterized in that The droplet size of the emulsion is 1-100 μm.

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