Plant polysaccharide composite film-forming agent as well as preparation method and application thereof

Abstract

The invention discloses a plant polysaccharide composite film-forming agent as well as a preparation method and application thereof, and belongs to the technical field of natural film-forming agents. The film-forming agent disclosed by the invention is prepared from the following components in parts by weight: 30 to 45 parts of garlic polysaccharide, 10 to 20 parts of oat beta-glucan, 5 to 15 parts of collagen, 3 to 10 parts of sericin and 40 to 45 parts of glycerol, and the prepared composite film-forming agent has the antibacterial property of polysaccharide, the long-chain polymer structure of protein and the hydrophobicity of lipid substances; a thin film with certain gas barrier property and moisture barrier property can be formed, the strength and the adhesion property of the composite film are enhanced, and the composite film can be applied to facial masks, medical use or fresh keeping.

Description

Technical Field

[0001] The invention belongs to the technical field of natural film-forming agents, and in particular relates to a preparation method and application of a plant polysaccharide composite film-forming agent. Background Art

[0002] Film-forming agents are widely used in many fields, but the most commonly used film-forming agents are mainly synthetic raw materials, among which PVA, PVP, glutaraldehyde, acrylate / octyl-acrylamide copolymers, etc. are commonly used film-forming agents. Although such film-forming agents have excellent film-forming properties, they may cause users to suffer from adverse reactions such as acne, allergies, stuffiness, itchy skin, and redness and swelling. And it is difficult for natural film-forming agents to obtain satisfactory film-forming effects. For example, Chinese application No. 201910325727 discloses a method for preparing a polysaccharide nanocrystal-modified collagen film. This application cannot meet the performance indicators due to the relatively simple composition properties and mechanism of action. Another example is Chinese application No. 201910023547.6, which discloses a chitosan-starch composite film and its preparation method and application, but the mechanical properties, water barrier properties, tolerance, antioxidant properties, and photostability of the film are insufficient, which limits its scope of application. Therefore, in order to reduce the possible risks of chemical film formers and improve the film-forming properties of natural film formers, the two are used together to complement each other, but their disadvantages still exist. This patent uses non-toxic and harmless pure natural raw materials to prepare a composite film former matrix. The film former has excellent film-forming properties, is safe and has no side effects, and has broad application prospects.

[0003] Under the action of intrachain hydrogen bonds, garlic polysaccharide folds and curls to form a relatively stable spherical structure. Its molecular chain is relatively flexible and has a low viscosity, which is conducive to diffusion. Garlic polysaccharide has better oil absorption than casein and can absorb vegetable oil equivalent to more than 1.6 times its own volume. Garlic polysaccharide has better hygroscopicity than glycerol and can significantly restore the activity of UVB-damaged cells and promote the proliferation of damaged human immortal cells (HaCaT).

[0004] Oat β-glucan is a non-starch polysaccharide found in the cell walls of oat endosperm and aleurone. It has excellent anti-aging effects, can smooth fine wrinkles, increase skin elasticity, and improve skin texture; it has a unique straight-chain molecular structure and good transdermal absorption properties; it promotes fibroblasts to synthesize collagen, promotes wound healing, and repairs damaged skin.

[0005] Sericin is a globular protein. The amount of amino acids with polar groups in sericin accounts for more than 60%. Due to the presence of these hydrophilic amino acids, sericin gel is very easy to produce hydrogen bonds, forming a β structure and gelling. When exposed to water and heat, the hydrogen bonds of sericin gel are very easy to dissociate and disperse into a solution, which has good oil retention and emulsification properties. In addition, sericin proteins have strong ultraviolet absorption ability. The disadvantage is that sericin has poor film-forming properties.

[0006] Single polysaccharide film-forming agents are highly hydrophilic, but have poor water loss inhibition performance. In addition, single polysaccharide films degrade quickly, have poor water loss inhibition performance, and have a short retention time. Therefore, they need to be compounded with other polymers to maximize their strengths and minimize their weaknesses. Single protein films are hydrophobic, but have poor antibacterial properties. Using polysaccharides with different structures and proteins with different structures as raw materials, and using covalent bonds or hydrogen bonds and electrostatics to form a cross-linked network structure, can improve film-forming properties, swelling and water retention functions, and the mechanical strength of the film, thereby obtaining a composite film-forming agent with better biocompatibility, better performance, and lower cost. Summary of the invention

[0007] In order to make up for the shortcomings of single polysaccharide or single protein film-forming agents, protein is used as a film-forming matrix and the antibacterial properties of garlic polysaccharide are used, and lipid substances are added to form a polysaccharide / protein / lipid composite coating with a porous network structure and better comprehensive performance. The composite film-forming agent has the antibacterial properties of polysaccharides, the long-chain polymer structure of proteins and the hydrophobicity of lipid substances, and can form a film with certain gas and moisture barrier properties, thereby enhancing the strength and adhesion of the composite film.

[0008] The principle of the present application is that the polysaccharide film-forming agent mainly uses polysaccharide substances with high relative molecular mass and their derivatives as film-forming matrix, and forms a semi-permeable film with a network structure through interactions such as intramolecular and intermolecular hydrogen bonds.

[0009] Specifically, the present application utilizes negatively charged polysaccharides and positively charged collagen to combine proteins and polysaccharides through electrostatic effects, or to induce mutual attraction and coagulation of polysaccharides / proteins, and finally to form a coexisting two-phase aggregate protein / polysaccharide complex. The formed polysaccharide / protein complex has a large hydrophobic cavity structure, which can have a good solubilization effect on hydrophobic active ingredients, improve the bioavailability of functional ingredients, and significantly improve water loss performance. It not only retains the original biological activity of polysaccharides and collagen, but also combines the advantages of the two to obtain an emulsion film-forming liquid with good stability and functionality, which can simulate the formation of natural biofilms.

[0010] The first purpose of the present application is to provide a plant polysaccharide composite coating, which comprises the following components by weight: 30-45 parts of garlic polysaccharide, 10-20 parts of oat β-glucan, 5-15 parts of collagen, 3-10 parts of sericin, and 40-45 parts of glycerol.

[0011] The second purpose of this application is to provide a method for preparing a plant polysaccharide composite coating. After a large number of experiments and unremitting efforts, the inventor finally prepared a plant polysaccharide composite coating, which includes the following steps: 1) Take garlic polysaccharide powder, oat β-glucan and glycerol, dissolve them in 0.5-1.5% acetic acid solution in a constant temperature water bath at 40-50°C to prepare a composite polysaccharide solution with a mass concentration of 6-10 g / L, stir at 600-800 rpm overnight at room temperature for later use; 2) Take collagen, sericin and glycerol, dissolve them in ultrapure water in a 40-45°C constant temperature water bath to prepare a protein glue solution with a mass concentration of 4-6 g / L, stir at 600-800 rpm for 20-30 min, and set aside; Slowly add the protein glue solution obtained in step 2) to the composite polysaccharide solution obtained in step 1), stir for 30 min in a magnetic stirrer at a speed of 600-800 r / min, adjust the pH value of the system to 4.5-6.5, and continue stirring for 30 min to obtain a plant polysaccharide composite coating; Preferably, in the method for preparing a plant polysaccharide composite coating as described above, the preparation method of garlic polysaccharide powder in step 1) is as follows: (1) Raw material pretreatment: Wash the whole garlic bulb with skin and boil it in boiling water for 3-7 minutes; (2) beating: add 1-3 times the mass of deionized water to the garlic bulbs in step 1), and beat the garlic bulbs at a speed of 800-1200 rpm for 1-4 minutes to obtain garlic pulp; (3) Filtration: Add edible alcohol to the garlic paste obtained in step 2) until the alcohol content reaches 30-40% of the total volume, filter through a 200-300 mesh filter cloth, and retain the filtrate; (4) Filtration: Add edible alcohol to the filtrate obtained in step 3) until the alcohol content reaches 60-75% of the total volume, filter through a 200-300 mesh filter cloth, and retain the precipitate, which is garlic polysaccharide; (5) Drying: After the alcohol in the garlic polysaccharide in step 4) evaporates naturally for 1-2 hours, the garlic polysaccharide is freeze-dried into powder to obtain garlic polysaccharide powder.

[0012] The final purpose of the present invention is the application of the prepared plant polysaccharide composite film-forming agent, which can be used in cosmetics, food preservation, and medical ointments, creams, lotions, sprays, etc.

[0013] Compared with the prior art, this application has the following advantages and significant progress: 1. The composite film-forming agent uses pure natural, non-toxic and harmless ingredients, avoiding the risks of many side effects that chemical film-forming agents may cause to the human body; 2. Its stability and film-forming property are better than single protein or polysaccharide film-forming agents; 3. The present invention provides a long-lasting moisturizing and oil-balancing film-forming agent. When the film-forming agent is added to a product such as a facial mask, a bright and transparent film can be formed on the surface of the skin, which can isolate the external air and pollution, help to increase the skin temperature, and accelerate metabolism; it can hydrate and lock in moisture from both inside and outside, making the skin soft and naturally bright, and enhancing skin elasticity and anti-wrinkle and skin-rejuvenating effects.

[0014] The following are specific embodiments of the present invention, which further describe the technical solution of the present invention, but the protection scope of the present invention is not limited to these embodiments. Any changes or equivalent substitutions that do not deviate from the concept of the present invention are included in the protection scope of the present invention. Example

[0015] A plant polysaccharide composite film-forming agent comprises the following components by weight: 30-45 parts of garlic polysaccharide, 10-20 parts of oat beta-glucan, 5-15 parts of collagen, 3-10 parts of sericin and 40-45 parts of glycerol.

[0016] The preparation method of the above-mentioned plant polysaccharide composite film-forming agent is as follows: 1) Take 12g of garlic polysaccharide powder, 3g of oat β-glucan, and 15mL of glycerol, stir into a slurry, dissolve in 0.5-1.5% acetic acid solution in a 40-50 ℃ water bath to prepare a polysaccharide solution with a mass concentration of 8g / L, stir at room temperature at a speed of 600-800 rpm overnight, and set aside.

[0017] 2) Take 3.5 g of 2000-5000 Dalton hydrolyzed collagen, 2.5 g of sericin, and 5 mL of glycerol, dissolve them in ultrapure water in a 40-45 °C water bath to prepare a protein solution with a mass concentration of 5 g / L, stir at 600-800 rpm for 20-30 min, and set aside.

[0018] 3) Take the above two solutions in a volume ratio of 1:1, slowly add the protein glue solution into the complex polysaccharide solution, stir for 30 min in a magnetic stirrer at a speed of 600-800 r / min, adjust the pH value of the system to 5, and continue stirring for 30 min to obtain a garlic polysaccharide-oat β-glucan-collagen-sericin-glycerol natural film-forming agent.

[0019] The preparation method of garlic polysaccharide powder in step 1) is as follows: (1) Raw material pretreatment: Wash the whole garlic bulb with skin and boil it in boiling water for 3-7 minutes; (2) beating: add 1-3 times the mass of deionized water to the garlic bulbs in step 1), and beat the garlic bulbs at a speed of 800-1200 rpm for 1-4 minutes to obtain garlic pulp; (3) Filtration: Add edible alcohol to the garlic paste obtained in step 2) until the alcohol content reaches 30-40% of the total volume, filter through a 200-300 mesh filter cloth, and retain the filtrate; (4) Filtration: Add edible alcohol to the filtrate obtained in step 3) until the alcohol content reaches 60-75% of the total volume, filter through a 200-300 mesh filter bag, and retain the precipitate, which is garlic polysaccharide; (5) Drying: After the alcohol in the garlic polysaccharide in step 4) evaporates naturally for 1-2 hours, the garlic polysaccharide is freeze-dried into powder to obtain garlic polysaccharide powder.

[0020] Under this process condition, the natural film former can effectively contain active ingredients, is tasteless and non-irritating, and forms a film quickly. The hydrogel after the composite film swells has a honeycomb-like porous structure. It can be further used to prepare skin care and medical products.

[0021] A plant polysaccharide composite film-forming agent comprises the following components by weight: 15-30 parts of garlic polysaccharide, 5-10 parts of oat beta-glucan, 1-5 parts of collagen, 3-10 parts of sericin, and 40-45 parts of glycerol.

[0022] The preparation method of the above-mentioned plant polysaccharide composite film-forming agent is as follows: 1) Take 6 g of garlic polysaccharide powder, 2 g of oat β-glucan, and 15 mL of glycerol, stir to form a slurry, dissolve in 0.5-1.5% acetic acid solution in a 40-50 ℃ water bath to obtain a polysaccharide solution with a mass concentration of 8 g / L, stir at room temperature at a speed of 600-800 rpm overnight and set aside.

[0023] 2) Take 2.5 g of 2000-5000 Dalton hydrolyzed collagen, 2 g of sericin, and 5 mL of glycerol, dissolve them in ultrapure water in a 40-45 °C water bath to prepare a protein solution with a mass concentration of 5 g / L, stir at 600-800 rpm for 20-30 min, and set aside.

[0024] 3) Take the above two solutions in a volume ratio of 1:1, slowly add the protein glue solution into the complex polysaccharide solution, stir for 30 min in a magnetic stirrer at a speed of 600-800 r / min, adjust the pH value of the system to 5, and continue stirring for 30 min to obtain a garlic polysaccharide-oat β-glucan-collagen-sericin-glycerol natural film-forming agent.

[0025] The preparation method of garlic polysaccharide powder in step 1) is the same as that in Example 1.

[0026] A plant polysaccharide composite film-forming agent comprises the following components by weight: 30-45 parts of konjac polysaccharide, 10-20 parts of oat beta-glucan, 5-15 parts of collagen, 3-10 parts of silk fibroin and 40-45 parts of glycerol.

[0027] The preparation method of the above-mentioned plant polysaccharide composite film-forming agent is as follows: 1) Take 12g of konjac polysaccharide powder, 3g of oat β-glucan, and 15mL of glycerol, stir into a slurry, dissolve in 0.5-1.5% acetic acid solution in a 40-50 ℃ water bath to prepare a polysaccharide solution with a mass concentration of 8g / L, stir at room temperature at a speed of 600-800 rpm overnight, and set aside.

[0028] 2) Take 3.5 g of 2000-5000 Dalton hydrolyzed collagen, 2.5 g of silk fibroin, and 5 mL of glycerol, dissolve them in ultrapure water in a 40-45 °C water bath to prepare a protein solution with a mass concentration of 5 g / L, stir at 600-800 rpm for 20-30 min, and set aside.

[0029] 3) Take the above two solutions in a 1:1 volume ratio, slowly add the protein glue solution into the complex polysaccharide solution, stir for 30 min in a magnetic stirrer at a speed of 600-800 r / min, adjust the pH value of the system to 5, and continue stirring for 30 min to obtain a konjac polysaccharide-oat β-glucan-collagen-sericin-glycerol natural film-forming agent.

[0030] The inventors compared the performance of the prepared film-forming agents, as follows: Test 1: Performance comparison between composite polysaccharide film-forming agent and several facial masks Test conditions: constant temperature water bath 36 0 C, humidity 42%, use plastic film to seal the water bath surface to prevent water vapor from affecting the test results. Diameter 5cm (area about 20cm 2 ) Spread 2g of the sample on the plastic culture dish and place it on the surface of the plastic film without covering it. Each sample was accurately weighed after 20 minutes and 120 minutes. The results are shown in Table 1.

[0031] Table 1 Plant compound polysaccharide film-forming agent and several facial masks water holding test results (n=3) The results showed that compared with several tested products, the mask prepared with the addition of a complex polysaccharide film-forming agent was the best in terms of both short-term and long-term moisturizing and water-retaining effects.

[0032] Experiment 2: Test on the moisture content of the subjects' skin Method: First, test the moisture content on the subject's skin, then apply the test product on the same location. Two hours later, wipe off the product and test the moisture content of the skin at that location. Compare the moisture content of the skin at the same location before and after application. The results are shown in Table 2.

[0033] Table 2 Test of skin moisture content of subjects The results showed that the facial mask prepared with the film-forming agent could significantly improve the skin's dehydration, moisturize the skin tissue, and have more outstanding moisturizing properties for the skin.

[0034] Test 3: Comparison of water holding effects of three composite film-forming agents. Test method: Test 1. See Table 3 for specific results.

[0035] Example 1, Comparative Example 1-2 Film-Forming Agent Water Retention Test Results (n=3) The results showed that reducing the proportion of garlic polysaccharide or replacing garlic polysaccharide with other polysaccharides would lead to a decrease in the water-holding effect of the film.

Claims

1. A plant polysaccharide composite film-forming agent, characterized in that: The composite film-forming agent comprises the following components by weight: 30-45 parts of garlic polysaccharide, 10-20 parts of oat beta-glucan, 5-15 parts of collagen, 3-10 parts of sericin and 40-45 parts of glycerol.

2. The method for preparing the plant polysaccharide composite coating according to claim 1, characterized in that: The following steps are involved: 1) Take garlic polysaccharide powder, oat β-glucan and glycerol, dissolve them in 0.5-1.5% acetic acid solution in a constant temperature water bath at 40-50°C to prepare a composite polysaccharide solution with a mass concentration of 6-10 g / L, stir at 600-800 rpm overnight at room temperature for later use; 2) Take collagen, sericin and glycerol, dissolve them in ultrapure water in a 40-45°C constant temperature water bath to prepare a protein glue solution with a mass concentration of 4-6 g / L, stir at 600-800 rpm for 20-30 min, and set aside; The protein gel solution obtained in step 2) is slowly added to the composite polysaccharide solution obtained in step 1), stirred for 30 min in a magnetic stirrer at a speed of 600-800 r / min, the pH value of the system is adjusted to 4.5-6.5, and stirring is continued for 30 min to obtain a plant polysaccharide composite film-forming agent.

3. The method for preparing the plant polysaccharide composite coating according to claim 2, characterized in that: The preparation method of garlic polysaccharide powder in step 1) is as follows: (1) Raw material pretreatment: Wash the whole garlic bulb with skin and boil it in boiling water for 3-7 minutes; (2) beating: add 1-3 times the mass of deionized water to the garlic bulbs in step 1), and beat the garlic bulbs at a speed of 800-1200 rpm for 1-4 minutes to obtain garlic pulp; (3) Filtration: Add edible alcohol to the garlic paste obtained in step 2) until the alcohol content reaches 30-40% of the total volume, filter through a 150-200 mesh filter bag, and retain the filtrate; (4) Filtration: Add edible alcohol to the filtrate obtained in step 3) until the alcohol content reaches 60-75% of the total volume, filter through a 150-200 mesh filter bag, and retain the precipitate, which is garlic polysaccharide; (5) Drying: After the alcohol in the garlic polysaccharide in step 4) evaporates naturally for 1-2 hours, the garlic polysaccharide is freeze-dried into powder to obtain garlic polysaccharide powder.

4. The use of the plant polysaccharide composite film-forming agent prepared as claimed in claim 1, characterized in that: The film-forming agent can be used in cosmetics, food preservation, and medical ointments, creams, lotions, and sprays.