Collagen membrane, preparation method and application thereof

Abstract

The application discloses a collagen membrane and a preparation method and application thereof, and belongs to the cosmetic field. The preparation method of the collagen membrane comprises the following steps: using lime to pickle a cowhide, washing the cowhide, then using hydrochloric acid to acidify the cowhide, washing the cowhide, washing away the interstitial substance, until the hardness of the cowhide is less than 0.1-0.3 mmol / 100g; cutting the obtained cowhide into pieces, crushing the pieces by using a fiber removing machine, obtaining collagen fibers, then adding a gelatinized acetic acid ester starch solution and a chitosan solution into the collagen fibers, uniformly mixing and rubbing the collagen fibers, and obtaining a collagen fiber slurry with a water content of 95-97%; casting the obtained collagen fiber slurry into a film, drying the film at 50-55 DEG C. for 2-4h, then soaking the film in a mixed solution of baking soda and glutamine transaminase for 2-3s, drying the film at 50-55 DEG C., then washing the film by using a sodium thiosulfate solution, and washing away the salt, so that the collagen membrane is obtained. The preparation method enhances the crosslinking between the collagen fibers, and improves the structural stability of the film.

Description

Technical Field

[0001] This application relates to a collagen membrane, its preparation method, and its application, and belongs to the field of cosmetics. Background Technology

[0002] Collagen is a natural fibrous protein, mainly found in the skin, tendons, and bones of animals. It is also the most abundant functional protein in mammals, accounting for 25-30% of total protein. Collagen is now widely used in the food industry, cosmetics, medical materials, and other fields.

[0003] Chinese invention patent CN201710241239.1 discloses a bio-collagen mask substrate and its application. Using bio-collagen as a raw material, it is made into a mask substrate, replacing existing non-woven fabric mask substrates which suffer from allergies and other problems. This mask substrate has good permeability, is natural and non-irritating, and utilizes its unique structural characteristics and perfect skin-fitting ability to better penetrate the essence into the skin without reverse absorption or residue, providing highly effective moisturizing and allowing for more thorough absorption of the mask's skincare essence. However, existing collagen fibers, due to their inherent characteristics, are difficult to form a stable and continuous membrane structure, or the film-forming process requires high temperatures, which easily damages collagen activity, resulting in poor film-forming properties and easily damaged membranes. Summary of the Invention

[0004] To address the aforementioned issues, a collagen membrane, its preparation method, and its application are provided. The membrane formation process does not require high temperatures, enhances the cross-linking between collagen fibers, and improves the structural stability of the membrane.

[0005] This invention provides the following technical solution:

[0006] According to one aspect of this application, a method for preparing a collagen membrane is provided, comprising the following steps:

[0007] (1) The cowhide is pickled with lime, washed with water, then acidified with hydrochloric acid, washed with water to remove the interstitial fibers, until the cowhide hardness is <0.1-0.3mmol / 100g;

[0008] (2) Cut the cowhide obtained in step (1) into pellets, crush it with a defibering machine to obtain collagen fibers, and then add gelatinized acetate starch solution and chitosan solution to the collagen fibers, mix and knead evenly to obtain collagen fiber slurry with a water content of 95-97%.

[0009] (3) Cast the collagen fiber slurry obtained in step (2) into a film, dry it at 50-55℃ for 2-4 hours, then soak the film in a mixed solution of sodium bicarbonate and transglutaminase for 2-3 seconds, dry it at 50-55℃, and then rinse it with sodium thiosulfate solution to remove the salt, thus obtaining the collagen film.

[0010] Optionally, in step (3), the concentration of the baking soda solution is 1-3 wt%;

[0011] The concentration of the transglutaminase solution is 0.1-0.3 wt%.

[0012] The concentration of the sodium thiosulfate solution is 0.05-0.15 wt%.

[0013] Optionally, in step (2), the concentration of the acetate starch solution is 1-3 wt%;

[0014] The concentration of the chitosan solution is 1-3 wt%.

[0015] Optionally, the weight ratio of the collagen fiber, starch acetate solution and chitosan solution is 1:(0.5-1):(0.5-1).

[0016] Optionally, in step (2), the grain size of the cowhide is 0.5-1.5 cm;

[0017] The collagen fibers are 10-15 mm in length and 10-20 nm in diameter.

[0018] Optionally, in step (1), the amount of lime used is 15-25 wt% of the weight of the cowhide, and the curing time is 2-4 days.

[0019] Optionally, in step (1), the concentration of hydrochloric acid is 0.5-1.5 wt%, and the acidification time is 5-7 h.

[0020] Optionally, in step (1), the cowhide is made from cow head hide.

[0021] According to another aspect of this application, a collagen membrane obtained by any of the preparation methods described above is provided.

[0022] According to another aspect of this application, the use of collagen membranes obtained by any of the above preparation methods in the preparation of facial masks, eye masks, nose masks, forehead masks, lip masks, cheek masks, hand masks, foot masks, back masks, or chest masks is provided.

[0023] The beneficial effects of this application include, but are not limited to:

[0024] 1. The preparation method of the collagen membrane in this application selects soft bovine head hide, which is relatively easy to process and yields higher purity collagen fibers. Through lime curing and acidification, non-collagenous proteins, fats, pigments, and interfibrous matrix are effectively removed from the hide, ensuring the complete separation of collagen fibers while maintaining their purity and uniformity. The low gelatinization temperature of acetate starch prevents damage to collagen activity, while chitosan has antibacterial properties, reducing microbial growth during storage or use and improving product safety. The synergistic effect of acetate starch and chitosan is utilized... The film-forming effect enhances the cross-linking between collagen fibers, forming a highly liquid-holding three-dimensional gel network, significantly improving the adsorption, retention, and sustained-release properties of the essence. Baking soda not only adjusts the pH value of the membrane material to make it more suitable for the acid-base environment of the skin surface and reduce irritation, but also enables transglutaminase to promote full cross-linking between proteins within a suitable activity range. This cross-linking effect increases the strength and stability of the membrane, while also helping to improve the membrane's water resistance. Sodium thiosulfate can disrupt the disulfide bond structure of collagen, thereby increasing the membrane's breathability.

[0025] 2. The preparation method of the collagen membrane in this application involves coordinated and interconnected steps. By optimizing the parameters and processes of each step, the obtained collagen membrane is not only structurally stable and has good film-forming properties, but is also soft, smooth, and has excellent affinity with the skin. In addition, when mixed with the mask liquid, the essence adheres well. Attached Figure Description

[0026] The accompanying drawings, which are included to provide a further understanding of this application and form part of this application, illustrate exemplary embodiments of this application and are used to explain this application, but do not constitute an undue limitation of this application. In the drawings:

[0027] Figure 1 This is a schematic diagram of the collagen membrane semi-finished product involved in Embodiment 2 of this application. Detailed Implementation

[0028] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0029] Unless otherwise specified in the examples, the procedures shall be performed under standard conditions or conditions recommended by the manufacturer. Raw materials or instruments whose manufacturers are not specified are all commercially available products.

[0030] Example 1

[0031] A method for preparing a collagen membrane includes the following steps:

[0032] (1) The cow head hide was pickled with lime. The amount of lime used was 15wt% of the cow hide weight. The pickling time was 2 days. After washing with water, the cow hide was acidified with 0.5wt% hydrochloric acid for 5 hours. After washing with water, the interstitial fibers were washed away until the hardness of the cow hide was <0.1mmol / 100g.

[0033] (2) Cut the cowhide obtained in step (1) into pellets with a particle size of 0.5 cm. Roll them in a defibering machine to obtain collagen fibers with a length of 10 mm and a diameter of 10 nm. Then add a gelatinized starch acetate solution with a concentration of 1 wt% and a chitosan solution with a concentration of 1 wt% to the collagen fibers. The weight ratio of collagen fibers, starch acetate solution and chitosan solution is 1:0.5:0.5. Mix and knead evenly to obtain a collagen fiber slurry with a water content of 97%.

[0034] (3) Cast the collagen fiber slurry obtained in step (2) into a film, dry it at 50°C for 4 hours, then soak the film in a mixed solution of sodium bicarbonate with a concentration of 1 wt% and transglutaminase with a concentration of 0.1 wt% for 3 seconds, dry it at 50°C, and then rinse it with a sodium thiosulfate solution with a concentration of 0.05 wt% to remove the salt, thus obtaining the collagen film.

[0035] Example 2

[0036] A method for preparing a collagen membrane includes the following steps:

[0037] (1) The cow head hide was pickled with lime. The amount of lime used was 20wt% of the cow hide weight. The pickling time was 3 days. After washing with water, the cow hide was acidified with 1wt% hydrochloric acid for 6 hours. After washing with water, the interstitial fibers were washed away until the cow hide hardness was <0.2mmol / 100g.

[0038] (2) Cut the cowhide obtained in step (1) into pellets with a particle size of 1 cm. Roll them in a defibering machine to obtain collagen fibers with a length of 12 mm and a diameter of 15 nm. Then add a gelatinized starch acetate solution with a concentration of 2 wt% and a chitosan solution with a concentration of 2 wt% to the collagen fibers. The weight ratio of collagen fibers, starch acetate solution and chitosan solution is 1:1:1. Mix and knead evenly to obtain a collagen fiber slurry with a water content of 96%.

[0039] (3) Cast the collagen fiber slurry obtained in step (2) into a film, such as Figure 1As shown, the membrane was dried at 53°C for 3 hours, then immersed in a mixed solution of 2 wt% sodium bicarbonate and 0.2 wt% transglutaminase for 2 seconds, dried at 53°C, and then rinsed with a 0.1 wt% sodium thiosulfate solution to remove the salt, thus obtaining the collagen membrane.

[0040] Example 3

[0041] A method for preparing a collagen membrane includes the following steps:

[0042] (1) The cow head hide was pickled with lime. The amount of lime used was 25wt% of the cow hide weight. The pickling time was 4 days. After washing with water, the cow hide was acidified with 1.5wt% hydrochloric acid for 7 hours. After washing with water, the interstitial fibers were washed away until the cow hide hardness was <0.3mmol / 100g.

[0043] (2) Cut the cowhide obtained in step (1) into pellets with a particle size of 1.5 cm. Roll them in a defibering machine to obtain collagen fibers with a length of 15 mm and a diameter of 20 nm. Then add a gelatinized starch acetate solution with a concentration of 3 wt% and a chitosan solution with a concentration of 3 wt% to the collagen fibers. The weight ratio of collagen fibers, starch acetate solution and chitosan solution is 1:1:1. Mix and knead evenly to obtain a collagen fiber slurry with a water content of 95%.

[0044] (3) Cast the collagen fiber slurry obtained in step (2) into a film, dry it at 55°C for 2 hours, then soak the film in a mixed solution of sodium bicarbonate with a concentration of 3 wt% and transglutaminase with a concentration of 0.3 wt% for 2 seconds, dry it at 55°C, and then rinse it with a sodium thiosulfate solution with a concentration of 0.15 wt% to remove the salt, thus obtaining the collagen film.

[0045] Example 4

[0046] The difference from Example 2 is that the weight ratio of collagen fibers, starch acetate solution and chitosan solution is 1:2:2.

[0047] Comparative Example 1

[0048] The difference from Example 2 is that step (3) is:

[0049] The collagen fiber slurry obtained in step (2) was cast into a film, dried at 53°C for 3 hours, and then the film was immersed in a mixed solution of 2 wt% sodium bicarbonate and 0.2 wt% transglutaminase for 2 seconds and dried at 53°C to obtain the collagen membrane.

[0050] Comparative Example 2

[0051] The difference from Example 2 is that step (3) is:

[0052] The collagen fiber slurry obtained in step (2) is cast into a film and dried at 53°C for 3 hours to obtain a collagen membrane.

[0053] Comparative Example 3

[0054] The difference from Example 2 is that the acetate starch is replaced with hydroxypropyl starch.

[0055] Test case

[0056] The collagen membranes prepared in Examples 1-4 and Comparative Examples 1-3 were subjected to comprehensive performance tests.

[0057] pH test method: Cut the collagen membrane into small pieces in a clean sampling bag; weigh 1g of sample into a 100mL beaker, add 50mL of distilled water, stir well with a glass rod, let stand, and time for 10min.

[0058] Use a pH meter to measure the pH value. When using a pH meter, do not touch the cup wall or bottom. Place the probe into the water sample and gently shake the water sample until the screen reading stabilizes. Record the reading. After the measurement is complete, remove the water sample, rinse the probe, and absorb the residual distilled water from the probe. Repeat the operation.

[0059] Water absorption test method: Cut the collagen membrane into 5cm×5cm pieces and place them on a balance, recording their initial weight (dry weight). Then, quickly immerse the collagen membrane in 20mL of purified water for 5 minutes to ensure that the collagen membrane fully absorbs water. Gently remove the collagen membrane with tweezers, wipe off excess water with filter paper, and place it back on the balance, recording its weight (wet weight). Repeat the above operation until a constant weight is achieved. Calculate the water absorption rate of the collagen membrane using the following formula:

[0060] Water absorption rate = (wet weight - dry weight) / dry weight × 100%.

[0061] Mechanical properties: Cut a strip (length × width) of 120mm × 15mm as a sample, soak it in room temperature water for 5 minutes, drain and set aside.

[0062] Adjust the clamping distance of the tensile testing machine to 100 mm, clamp the prepared collagen membrane sample in the clamp, and perform the tensile test at a speed of 100 mm / min ± 10 mm / min. If the sample breaks at the clamp, it should be resampled and tested. Three parallel tests should be performed for each group of samples, and the final result should be the average value. Record the tensile force and elongation at break values.

[0063] The test results are shown in Table 1 below.

[0064] Table 1

[0065]

[0066] The above description is merely an embodiment of this application, and the scope of protection of this application is not limited to these specific embodiments, but is determined by the claims of this application. Various modifications and variations can be made to this application by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the technical concept and principles of this application should be included within the scope of protection of this application.

Claims

1. A method for preparing a collagen membrane, characterized by, The method comprises the following steps: (1) Curing the cowhide with lime, washing with water, and then acidifying the cowhide with hydrochloric acid, washing with water to remove the interstitial substance until the hardness of the cowhide is less than 0.3 mmol / 100g; (2) Cutting the cowhide obtained in step (1) into pieces, crushing the pieces with a fiber removing machine to obtain collagen fibers, then adding gelatinized acetate starch solution and chitosan solution to the collagen fibers, and mixing and kneading uniformly to obtain a collagen fiber slurry with a water content of 95-97%; (3) Casting the collagen fiber slurry obtained in step (2) into a film, drying the film at 50-55°C for 2-4h, then soaking the film in a mixed solution of baking soda and glutamine transaminase for 2-3s, drying at 50-55°C, and then rinsing with a sodium thiosulfate solution to remove salt, thereby obtaining a collagen protein film; The cowhide is made of cow head leather.

2. The collagen membrane production method according to claim 1, characterized by, In step (3), the concentration of the baking soda solution is 1-3wt%; The concentration of the glutamine transaminase solution is 0.1-0.3wt%; The concentration of the sodium thiosulfate solution is 0.05-0.15wt%.

3. The collagen membrane production method according to claim 1, characterized by, In step (2), the concentration of the acetate starch solution is 1-3wt%; The concentration of the chitosan solution is 1-3wt%.

4. The collagen membrane production method according to claim 3, characterized by, In step (2), the weight ratio of the collagen fibers, acetate starch solution and chitosan solution is 1:(0.5-1):(0.5-1).

5. The collagen membrane production method according to claim 1, characterized by, In step (2), the particle size of the cowhide is 0.5-1.5cm; The length of the collagen fibers is 10-15mm, and the diameter is 10-20nm.

6. The collagen membrane production method according to claim 1, characterized by, In step (1), the amount of lime used is 15-25wt% of the mass of the cowhide, and the curing time is 2-4 days.

7. The method for preparing a collagen membrane according to claim 1, characterized in that, In step (1), the concentration of the hydrochloric acid is 0.5-1.5wt%, and the acidification time is 5-7h.

8. The collagen protein film obtained by the preparation method of any one of claims 1-7.

9. Use of the collagen protein film obtained by the preparation method of any one of claims 1-7 in the preparation of face masks, eye masks, nose masks, forehead masks, lip masks, cheek masks, hand masks, foot masks, back masks or chest masks.

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