Preparation method of walnut particles and application of walnut particles in scrub cream
Functionalized walnut granules were prepared by lyophilizing the walnut shells and amidating them, and the plant essential oil and tocopherol acetate were attached to the walnut granules by physical adsorption, which solved the existing scrubs. The problem of excessive hardness of frosted particles and poor adsorption performance has achieved deep cleansing of the skin and long-term antibacterial and moisturizing effects.
Patent Information
- Application Number
- CN202411415726.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-11
- Publication Date
- 2025-02-07
AI Technical Summary
The matte particles in existing scrubs are too hard, which can easily cause damage to fragile and sensitive skin, and have poor adsorption performance, making it difficult to provide long-term antibacterial and moisturizing effects.
Functionalized walnut granules were prepared by lyophilizing and pulverizing walnut shells, and the plant essential oil and tocopherol acetate were attached to the walnut granules through physical adsorption to form excellent exfoliation and moisturization A scrub for moisturizing effect.
It achieves deep cleansing of the skin, removes blockage of the cuticle, provides long-term antibacterial and moisturizing effects, while avoiding damage to the skin, and providing a pleasant user experience.
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Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of daily chemical products, and particularly relates to a preparation method of walnut particles and application of the walnut particles in a scrub. Background Art
[0002] As the largest organ in the human body, the skin is mainly composed of the epidermis, dermis and subcutaneous tissue. The research object in the field of cosmetics is mainly the epidermis, which is composed of the stratum corneum, transition layer, granular layer, spinous cell layer and basal layer. The stratum corneum, as the outermost layer of the skin structure, is formed by the division, differentiation, migration and aging of the basal layer cells. It has the function of resisting and alleviating external stimuli and is the first line of defense for the skin. The metabolic renewal cycle of the normal skin stratum corneum is generally about 28 days, but due to topical drugs or bad cosmetics and irregular lifestyle, many people's stratum corneum is not renewed in time, resulting in serious proliferation of the stratum corneum, affecting the beauty of the skin, and even leading to a series of skin problems such as bacterial infection and acne.
[0003] With the development of the personal care products consumer market, scrub cleaning products have gradually entered the lives of consumers. Scrub refers to a personal care product containing fine particles. Currently, the main scrubs on the market are cleansing scrub products, which can remove dirt deep in the skin and remove dead skin and keratin on the surface of the skin through massage, thereby achieving clean and smooth skin. In addition, it also has the effects of relaxation, moisturizing and brightening the skin.
[0004] Walnut shell is one of the main by-products of walnut. It is completely biodegradable, has high specific strength, and can be used as a polymer filler. The walnut shell is crushed and passed through sieves with different apertures to obtain walnut particles of different particle sizes. Walnut particles have rich pore structures and strong adsorption properties. They are natural abrasives and adsorption filters. They are environmentally friendly and degradable. They can replace polyethylene particles as scrub particles in scrubs. The scrub particles in existing scrubs are mostly made of ground fruit shells, but they are hard and have too strong friction, which has certain damage to fragile and sensitive skin. In addition, their adsorption properties are poor, with almost no thickening and adsorption effect, and they are easy to breed bacteria. Summary of the invention
[0005] In order to solve the deficiencies mentioned in the above-mentioned background technology, the purpose of the present invention is to provide a method for preparing walnut particles and the application of walnut particles in a scrub. The walnut shells are freeze-dried and crushed, and then modified with amino acids. The amino-modified walnut particles are further subjected to an amidation reaction with polyacrylic acid under acidic conditions. The prepared functionalized walnut particles are used as carriers to physically adsorb plant essential oils and tocopherol acetate to prepare walnut particles with excellent exfoliating and moisturizing effects and long-lasting antibacterial properties.
[0006] The purpose of the present invention can be achieved through the following technical solutions: A method for preparing walnut particles comprises the following steps: S1. Wash and dry the walnut shells, crush them, and pass them through a 80-100 mesh sieve. The obtained crude particles are freeze-dried and crushed to obtain pretreated walnut particles. S2, taking the pretreated walnut particles and dispersing them in N, N-dimethylformamide to obtain a dispersion, taking the amino acid and morpholineethanesulfonic acid and dissolving them in deionized water respectively and mixing them evenly, then adding 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and 4-dimethylaminopyridine to obtain a mixed solution, adding the dispersion to the mixed solution, placing it at 35-45°C and stirring for reaction for 3-5h, cooling it to room temperature after the reaction is completed, washing it with deionized water, and obtaining amination walnut particles; S3, dissolving polyacrylic acid in a hydrochloric acid aqueous solution and adjusting the pH value of the system to 5-6, adding 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide and stirring for 18-24 hours, then adding the aminated walnut particles and continuing to stir for 20-24 hours, after the reaction is completed, filtering and drying to obtain functionalized walnut particles; S4, taking the functionalized walnut particles, the plant essential oil and the tocopherol acetate, mixing them, ultrasonically treating, filtering and drying them to obtain the walnut particles.
[0007] Preferably, the particle size of the pretreated walnut particles in step S1 is 200-300 meshes.
[0008] Preferably, the amino acids in step S2 are one or more combinations of glycine, L-lysine, D-lysine, L-arginine, and D-arginine.
[0009] Preferably, the molecular weight of the polyacrylic acid in step S3 is 2000-5000.
[0010] Preferably, in step S3, the mass ratio of polyacrylic acid to amino walnut particles is 28-35:1.
[0011] Preferably, the plant essential oil in step S4 is one or more combinations of rose essential oil, litsea cubeba essential oil, tea tree essential oil, and peppermint essential oil.
[0012] Preferably, in step S4, the addition ratio of the functionalized walnut particles, the plant essential oil and the tocopherol acetate is 1 g: 0.5~2 mL: 0.5~1 mL.
[0013] The walnut particles obtained by the preparation method as described above are used in scrub.
[0014] Beneficial effects of the present invention: The present invention freeze-dries and crushes walnut shells to obtain pretreated walnut particles with a mesh size of 200-300. The pretreated walnut particles have a higher mesh size, are more delicate, can deeply clean blocked pores, have a good exfoliating effect, can replace traditional non-degradable polyethylene scrub particles, and then amino acids are used to modify the pretreated walnut particles by aminoation, wherein the amino acids are used as functional factors, 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride is used as a coupling agent, and under the catalysis of 4-dimethylaminopyridine, the carboxyl groups in the amino acids react with the hydroxyl groups on the surfaces of the pretreated walnut particles to undergo an esterification reaction, thereby grafting the amino acids onto the surfaces of the pretreated walnut particles, thereby improving the adhesion of the scrub particles to the skin, and at the same time, the positively charged amino groups can recognize the bacterial outer membrane, thereby giving the scrub particles antibacterial activity, and the amino acid component can gently remove The method further involves the amidation reaction of part of the amino groups on the surface of the amino walnut particles with polyacrylic acid under acidic conditions, thereby tightly combining the two. The prepared functionalized walnut particles are used as carriers to physically adsorb plant essential oils and tocopherol acetate to obtain walnut particles, wherein polyacrylic acid is used as a thickener and dispersant, making the scrub smoother and easier to apply when used. The polyacrylic acid molecular chains are entangled in the pores of the functionalized walnut particles, thereby reducing the release rate of plant essential oils and tocopherol acetate, making them work more lastingly, providing long-term sustained-release antibacterial effects and nourishing and moisturizing effects. In addition, plant essential oils and tocopherol acetate reduce the damage caused by scrubbing, and the aromatic components in plant essential oils can also dispel fatigue, providing a pleasant use experience. DETAILED DESCRIPTION
[0015] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
[0016] Example 1 A method for preparing walnut particles comprises the following steps: S1. Wash and dry the walnut shells, crush them, and pass them through a 80-100 mesh sieve. The obtained crude particles are freeze-dried and crushed to obtain pretreated walnut particles. S2, take 1.2g of pretreated walnut particles and disperse them in 80mL N, N-dimethylformamide to obtain a dispersion, take 1.7g of glycine and 0.8g of morpholineethanesulfonic acid and dissolve them in 20mL of deionized water respectively and mix them evenly, then add 0.4g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and 4.3g of 4-dimethylaminopyridine to obtain a mixed solution, add the dispersion to the mixed solution, place it at 40°C and stir to react for 5h, cool it to room temperature after the reaction is completed, wash it with deionized water, and obtain amination walnut particles; S3, take 16g of polyacrylic acid with a molecular weight of 2000 and dissolve it in 100mL of hydrochloric acid aqueous solution to adjust the pH value of the system to 5, add 1.3g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and 0.6g of N-hydroxysuccinimide and stir for 20h, then add 1g of amino walnut particles and continue stirring for 24h. After the reaction is completed, filter and dry to obtain functionalized walnut particles; S4. Mix rose essential oil and peppermint essential oil in a volume ratio of 4:1 to obtain plant essential oil, mix 1.5 g of functionalized walnut particles, 1.5 mL of plant essential oil and 0.8 mL of tocopherol acetate, and obtain walnut particles after ultrasonic treatment, filtration and drying.
[0017] Example 2 A method for preparing walnut particles comprises the following steps: S1. Wash and dry the walnut shells, crush them, and pass them through a 80-100 mesh sieve. The obtained crude particles are freeze-dried and crushed to obtain pretreated walnut particles. S2, take 1.2g of pretreated walnut particles and disperse them in 80mL N, N-dimethylformamide to obtain a dispersion, take 2.5g of L-lysine and 0.8g of morpholineethanesulfonic acid and dissolve them in 20mL of deionized water respectively and mix them evenly, then add 0.4g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and 4.3g of 4-dimethylaminopyridine to obtain a mixed solution, add the dispersion to the mixed solution, place it at 40°C and stir to react for 5h, cool it to room temperature after the reaction is completed, wash it with deionized water, and obtain amination walnut particles; S3, take 20g of polyacrylic acid with a molecular weight of 3000 and dissolve it in 100mL of hydrochloric acid aqueous solution to adjust the pH value of the system to 5, add 1.4g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and 0.7g of N-hydroxysuccinimide and stir for 20h, then add 1g of amino walnut particles and continue stirring for 24h. After the reaction is completed, filter and dry to obtain functionalized walnut particles; S4. Mix the essential oil of Litsea cubeba and the essential oil of peppermint in a volume ratio of 4:1 to obtain plant essential oil, mix 1.5 g of functionalized walnut particles, 2.5 mL of plant essential oil and 1 mL of tocopherol acetate, and obtain walnut particles by ultrasonic treatment, filtration and drying.
[0018] Example 3 A method for preparing walnut particles comprises the following steps: S1. Wash and dry the walnut shells, crush them, and pass them through a 80-100 mesh sieve. The obtained crude particles are freeze-dried and crushed to obtain pretreated walnut particles. S2, take 1.2g of pretreated walnut particles and disperse them in 80mL N, N-dimethylformamide to obtain a dispersion, take 3.8g of L-arginine and 0.8g of morpholineethanesulfonic acid and dissolve them in 20mL of deionized water respectively and mix them evenly, then add 0.4g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and 4.3g of 4-dimethylaminopyridine to obtain a mixed solution, add the dispersion to the mixed solution, place it at 45°C and stir to react for 5h, cool it to room temperature after the reaction is completed, wash it with deionized water, and obtain aminated walnut particles; S3, take 25g of polyacrylic acid with a molecular weight of 5000 and dissolve it in 100mL of hydrochloric acid aqueous solution to adjust the pH value of the system to 6, add 1.4g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and 0.7g of N-hydroxysuccinimide and stir for 24h, then add 1g of amino walnut particles and continue stirring for 24h. After the reaction is completed, filter and dry to obtain functionalized walnut particles; S4. Mix tea tree essential oil and peppermint essential oil in a volume ratio of 4:1 to obtain plant essential oil, mix 1.5 g of functionalized walnut particles, 3 mL of plant essential oil and 1.2 mL of tocopherol acetate, and obtain walnut particles by ultrasonic treatment, filtration and drying.
[0019] Comparative Example 1 A method for preparing walnut particles comprises the following steps: S1. Wash and dry the walnut shells, crush them, and pass them through a 80-100 mesh sieve. The obtained crude particles are freeze-dried and crushed to obtain pretreated walnut particles. S2. Mix rose essential oil and peppermint essential oil in a volume ratio of 4:1 to obtain plant essential oil, mix 1.5 g of pretreated walnut particles, 1.5 mL of plant essential oil and 0.8 mL of tocopherol acetate, and obtain walnut particles after ultrasonic treatment, filtration and drying.
[0020] Comparative Example 2 A method for preparing walnut particles comprises the following steps: S1. Wash and dry the walnut shells, crush them, and pass them through a 80-100 mesh sieve. The obtained crude particles are freeze-dried and crushed to obtain pretreated walnut particles. S2, take 1.2g of pretreated walnut particles and disperse them in 80mL N, N-dimethylformamide to obtain a dispersion, take 1.7g of glycine and 0.8g of morpholineethanesulfonic acid and dissolve them in 20mL of deionized water respectively and mix them evenly, then add 0.4g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and 4.3g of 4-dimethylaminopyridine to obtain a mixed solution, add the dispersion to the mixed solution, place it at 40°C and stir to react for 5h, cool it to room temperature after the reaction is completed, wash it with deionized water, and obtain amination walnut particles; S3. Mix rose essential oil and peppermint essential oil in a volume ratio of 4:1 to obtain plant essential oil, mix 1.5 g of amino walnut particles, 1.5 mL of plant essential oil and 0.8 mL of tocopherol acetate, and obtain walnut particles after ultrasonic treatment, filtration and drying.
[0021] Performance Testing Preparation of scrub: 10% walnut particles prepared in Examples 1-3 and Comparative Examples 1-2, 20% coconut oil, 20% jojoba oil, 5% glycerol, 5% monoglyceride, 5% glycolic acid, 5% propylene glycol, and the balance deionized water, and the prepared scrub was subjected to performance testing: 30 test volunteers were selected, with an average age of 24±6.5 years old and an age range of 22-45 years old. The test sites were both sides of the nose, which were rubbed and massaged for 2 minutes and then washed. The test indicators were the scores of skin pain, redness, swelling, pulling or burning, using a 10-point system, with 0 indicating no corresponding feeling and 10 indicating a very obvious feeling. The statistical data were averaged, and the larger the number, the more obvious the feeling. The data results are shown in Table 1.
[0022] Table 1 Sensory evaluation results of samples
[0023] As can be seen from Table 1, the scrubs prepared in Examples 1-3 of the present invention and Comparative Examples 1-2 will not cause pain, redness, swelling, pulling or burning during use, and the products are mild and non-irritating.
[0024] In addition, the scrub was applied to the back of the hands and finger joints of the volunteers. The initial value measured before using the scrub was recorded as T0, and the sample was rinsed with water and measured again 15 minutes later as T1. The transepidermal water loss of the skin was tested with a transepidermal water loss instrument. The larger the measured value, the more water was lost per unit time, and the skin barrier was severely damaged. The moisture content change rate of the stratum corneum was used to evaluate the moisturizing effect of the scrub. The larger the test value, the higher the moisture content of the skin. The data results are shown in Table 2.
[0025] Table 2 Test results of sample performance
[0026] From the data in Table 2, it can be seen that the change rate of the moisture content of the stratum corneum of the scrubs prepared in Examples 1-3 of the present invention is greater than 15%, which has a significant moisturizing effect, and the transdermal moisture loss rate is reduced by more than 5%, indicating that after using the sample, no skin barrier damage is caused. In Comparative Example 1, the pretreated walnut particles are not amino-modified and functionalized, and the pretreated walnut particles are not functionalized in Comparative Example 2. The change rate of the moisture content of the stratum corneum measured in Comparative Example 1-2 is lower than that in Example 1-3, and the transdermal moisture loss is more obvious than that in Example 1-3, indicating that the grafting of amino acids and polyacrylic acid can enhance the exfoliation and moisturizing effect of the scrub. And the microbial content of the scrubs prepared in Examples 1-3 is less than 10CFU / g after being placed for 3 months, and the microbial content measured in Comparative Example 1-2 is higher than that in Example 1-3, indicating that the introduction of amino acids can enhance the antibacterial property of the product to a certain extent, and the introduction of polyacrylic acid molecular chains further enhances the long-term sustained-release antibacterial effect.
[0027] In the description of this specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.
[0028] The above shows and describes the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments, and the above embodiments and descriptions are only for explaining the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention may have various changes and improvements, and these changes and improvements all fall within the scope of the present invention to be protected.
Claims
1. A method for preparing walnut particles, characterized in that: The following steps are involved: S1. Wash and dry the walnut shells, crush them, and pass them through a 80-100 mesh sieve. The obtained crude particles are freeze-dried and crushed to obtain pretreated walnut particles. S2, taking the pretreated walnut particles and dispersing them in N, N-dimethylformamide to obtain a dispersion, taking the amino acid and morpholineethanesulfonic acid and dissolving them in deionized water respectively and mixing them evenly, then adding 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and 4-dimethylaminopyridine to obtain a mixed solution, adding the dispersion to the mixed solution, placing it at 35-45°C and stirring for reaction for 3-5h, cooling it to room temperature after the reaction is completed, washing it with deionized water, and obtaining amination walnut particles; S3, dissolving polyacrylic acid in a hydrochloric acid aqueous solution and adjusting the pH value of the system to 5-6, adding 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide and stirring for 18-24 hours, then adding the aminated walnut particles and continuing to stir for 20-24 hours, after the reaction is completed, filtering and drying to obtain functionalized walnut particles; S4, taking the functionalized walnut particles, the plant essential oil and the tocopherol acetate, mixing them, ultrasonically treating, filtering and drying them to obtain the walnut particles.
2. The method for preparing walnut particles according to claim 1, characterized in that: The particle size of the pretreated walnut particles in step S1 is 200-300 meshes.
3. The method for preparing walnut particles according to claim 1, characterized in that: In step S2, the amino acid is one or more combinations of glycine, L-lysine, D-lysine, L-arginine, and D-arginine.
4. The method for preparing walnut particles according to claim 1, characterized in that: The mass ratio of the pretreated walnut particles to the amino acids in step S2 is 1:1.4-3.
2.
5. The method for preparing walnut particles according to claim 1, characterized in that: The molecular weight of the polyacrylic acid in step S3 is 2000-5000.
6. The method for preparing walnut particles according to claim 1, characterized in that: In step S3, the mass ratio of polyacrylic acid to amino walnut particles is 16-25:
1.
7. The method for preparing walnut particles according to claim 1, characterized in that: In step S4, the plant essential oil is one or more combinations of rose essential oil, litsea cubeba essential oil, tea tree essential oil, and peppermint essential oil.
8. The method for preparing walnut particles according to claim 1, characterized in that: In the step S4, the addition ratio of the functionalized walnut particles, the plant essential oil and the tocopherol acetate is 1 g: 1-2 mL: 0.5-1 mL.
9. Walnut particles obtained by the preparation method according to any one of claims 1 to 8 are used in scrub.