Dressing with skin repairing function and production process thereof

Abstract

The invention relates to the technical field of dressings, and discloses a dressing with a skin repair function and a production process thereof, the dressing with the skin repair function comprises the following raw materials: antibacterial cellulose, anti-inflammatory repair type carrageenan, diallyldimethylammonium chloride, an initiator and deionized water; wherein the antibacterial cellulose is prepared from bacterial cellulose and oleanolic acid; the anti-inflammatory repair type carrageenan is prepared from alkenyl carrageenan and baicalin; the alkenyl carrageenan is prepared from carrageenan and glycidyl methacrylate; the dressing prepared by the invention has an excellent and long-acting antibacterial effect, can effectively inhibit the reproduction of bacteria in a moist environment, provides a good living environment for repairing skin cells, does not easily cause inflammation, avoids scars, accelerates the wound healing rate, and can effectively promote the regeneration and repairing of the skin cells.

Description

Technical Field

[0001] The invention relates to the technical field of dressings, and in particular to a dressing with skin repairing function and a production process thereof. Background Art

[0002] The skin is the largest organ of the human body and the first line of defense. It is responsible for resisting external interference. However, in the face of a complex and changing external environment, it is inevitable that it will be damaged due to various reasons, forming wounds on the skin surface. The wounds are exposed to the air and are easily contaminated by microorganisms in the air. High temperature and high humidity environments can easily cause inflammation, which will not only delay the healing of the wound, but may also cause scar hyperplasia and skin pigmentation after the wound heals, affecting the beauty of the human body.

[0003] Dressing is a key auxiliary tool that comes into direct contact with wounds and plays a promoting role in the wound healing process. It can isolate the wound from the external environment, avoid the adverse effects of microorganisms and dust in the air, and secondary damage caused by friction of clothing, sheets, etc. Although ordinary dressings can currently play a protective and barrier role, they lack antibacterial activity. Although some dressings have antibacterial effects, their antibacterial durability is poor and they often need to be replaced when acting on the wound. They are prone to causing secondary or even multiple injuries to the wound, thereby affecting the healing of the wound, which is not conducive to skin repair and has the risk of leaving scars.

[0004] The patent with announcement number CN107325592B discloses an antibacterial dressing, which improves the photocatalytic performance by doping nano-titanium dioxide with potassium and fluorine, and forms a network structure by cross-linking and modifying the nano-titanium dioxide sol with polyisocyanate, polyethylene glycol and tetraethylene glycol, which is more conducive to improving the antibacterial performance. The prepared dressing has better thermal stability and dispersibility, and also has a long-lasting antibacterial effect. Although this patent solves the problem of low antibacterial durability of ordinary dressings, the dressing prepared by this patent may cause irritation when directly applied to the wound, which has an adverse effect on the repair of the wound skin. Summary of the invention

[0005] The purpose of the present invention is to provide a dressing with skin repair function and a production process thereof, which solves the following technical problems: (1) Ordinary dressings do not have a long-term antibacterial effect, are prone to cause inflammation, and need to be replaced frequently; (2) Ordinary dressings have a general wound healing rate and poor skin repair function.

[0006] The purpose of the present invention can be achieved through the following technical solutions:

[0007] A dressing with skin repair function, comprising the following raw materials in parts by weight:

[0008] 20-30 parts of antibacterial cellulose;

[0009] 18-22 portions of anti-inflammatory and restorative carrageenan;

[0010] 8-10 parts of diallyldimethylammonium chloride;

[0011] 2-5 parts of initiator;

[0012] 80-100 parts of deionized water;

[0013] The antibacterial cellulose is prepared from bacterial cellulose and oleanolic acid; the anti-inflammatory repair carrageenan is prepared from olefinic carrageenan and baicalin; and the olefinic carrageenan is prepared from carrageenan and glycidyl methacrylate.

[0014] Furthermore, the initiator is any one of ammonium persulfate and potassium persulfate.

[0015] Furthermore, the method for preparing the antibacterial cellulose comprises the following steps:

[0016] Place bacterial cellulose in deionized water, add oleanolic acid, mix and stir thoroughly, add composite catalyst, heat to 50-60°C, stir and react for 4-6 hours, cool to room temperature and collect the product to obtain antibacterial cellulose.

[0017] In this scheme, under the action of the composite catalyst, the hydroxyl group in the bacterial cellulose structure and the carboxyl group in the oleanolic acid structure undergo esterification reaction to obtain antibacterial cellulose. Oleanolic acid is a natural antibacterial compound with a broad-spectrum antibacterial effect, which can inhibit the growth of various bacteria, but it is difficult to exert a lasting antibacterial effect. Bacterial cellulose has good biocompatibility, excellent hygroscopicity and moisturizing properties, can effectively absorb exudate, and create a moist environment, which is conducive to the growth and repair of skin cells. Oleanolic acid is connected to the structure of bacterial cellulose by chemical bonding, which can enhance the stability of oleanolic acid and enable it to continuously release antibacterial components, so that the prepared antibacterial cellulose has long-lasting antibacterial ability, can effectively avoid the problem of wound inflammation in a moist environment, and promote the repair rate of the wound. At the same time, the antibacterial cellulose structure also has multiple olefin groups, which can participate in the preparation process of the dressing, so that the prepared dressing has long-lasting antibacterial properties and a good service life.

[0018] Furthermore, the composite catalyst is 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and 4-dimethylaminopyridine in a mass ratio of 0.2-1:2.6-12.

[0019] Furthermore, the preparation method of the anti-inflammatory and restorative carrageenan comprises the following steps:

[0020] S1: Place carrageenan and glycidyl methacrylate in deionized water, stir and mix thoroughly, add tetrabutylammonium bromide, heat to 80-90°C and stir to react for 6-8h, collect the product after reduced pressure distillation to obtain olefinic carrageenan;

[0021] S2: Place olefinated carrageenan in N,N-dimethylformamide, add baicalin and a catalyst, raise the temperature to 90-105°C and stir to react for 5-8h, remove the solvent by distillation under reduced pressure, and collect the product to obtain anti-inflammatory and repairing carrageenan.

[0022] In this scheme, under the action of tetrabutylammonium bromide, the hydroxyl group in the carrageenan structure and the epoxy group in the glycidyl methacrylate structure undergo a ring-opening reaction to obtain olefinic carrageenan, and then under the action of a catalyst, the hydroxyl group in the olefinic carrageenan structure and the carboxyl group in the baicalin structure undergo an esterification reaction to obtain an anti-inflammatory repair type carrageenan. This anti-inflammatory repair type carrageenan has an olefinic group in its structure, which can participate in the preparation process of the dressing, and has excellent biocompatibility, good moisturizing effect, can maintain the moistening environment of the skin surface, and is conducive to the growth and repair of cells. At the same time, the anti-inflammatory ingredient baicalin is introduced into its structure. Baicalin is one of the effective ingredients of the traditional Chinese medicine scutellaria baicalensis, has a significant anti-inflammatory effect, can inhibit the release of multiple inflammatory factors, reduce inflammatory reactions, thereby accelerating the disappearance of inflammation, reducing the risk of wound infection, and promoting cell regeneration and repair. In the process of wound healing, it can stimulate the proliferation and differentiation of cells around the wound, accelerate the repair and regeneration of skin tissue, help shorten the wound healing time, prevent the formation of scars, and make the prepared dressing have good skin repair ability.

[0023] Furthermore, in step S1, the carrageenan is k-carrageenan.

[0024] Furthermore, in step S2, the catalyst is p-toluenesulfonic acid.

[0025] A production process of a dressing with skin repair function, comprising the following steps:

[0026] Step 1: placing antibacterial cellulose, anti-inflammatory repair carrageenan, and diallyldimethylammonium chloride in deionized water, and mixing and stirring thoroughly to form a dressing precursor mixture;

[0027] Step 2: Add the initiator to the dressing precursor mixture, heat up and stir, and collect the product after cooling to room temperature to obtain a dressing.

[0028] Furthermore, in step 2, the temperature of the heating and stirring is 65-75° C., and the time is 5-8 hours.

[0029] In this scheme, under the action of the initiator, the antibacterial cellulose, the anti-inflammatory repair carrageenan and the diallyldimethylammonium chloride undergo a free radical polymerization reaction, cross-link with each other, and form a cross-linked network structure, so that the prepared dressing has a gel property, good mechanical strength and is not easy to collapse. When the dressing is used directly, it can form a barrier layer to prevent contamination by pathogenic microorganisms and effectively protect the skin wound. Since human skin carries a negative charge, this scheme introduces a quaternary ammonium group with a positive charge into the dressing, which can not only enhance the antibacterial ability of the dressing, but also enhance the bonding force between the dressing and the skin, which helps the penetration of the dressing, thereby exerting a more excellent antibacterial and repairing effect.

[0030] Beneficial effects of the present invention:

[0031] The present invention prepares antibacterial cellulose and anti-inflammatory repair carrageenan and participates in the preparation process of the dressing, so that the prepared dressing has good and long-lasting antibacterial effect, can effectively inhibit the reproduction of bacteria in a moist environment, and provides a good living environment for the repair of skin cells. It is not easy to cause inflammation, can effectively accelerate the rate of wound healing, is gentle and non-irritating, can fit closely to the skin, and effectively promotes the regeneration and repair of skin cells.

[0032] Of course, any product implementing the present invention does not necessarily need to achieve all of the advantages described above at the same time. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings required for describing the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other accompanying drawings can be obtained based on these accompanying drawings without paying creative work.

[0034] Figure 1 This is a scanning electron microscope image of the dressing in Example 1 of the present invention. DETAILED DESCRIPTION

[0035] The following will be combined with the drawings in 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.

[0036] The preparation methods of the antibacterial cellulose and anti-inflammatory repairing carrageenan in the following examples and comparative examples of the present invention are as follows:

[0037] 1. Preparation of antibacterial cellulose

[0038] Place 3 g of bacterial cellulose in 50 ml of deionized water, add 2.8 g of oleanolic acid, mix thoroughly, then add 0.2 g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and 2.6 g of 4-dimethylaminopyridine, heat to 50 °C and stir for 4 h, cool to room temperature and collect the product to obtain antibacterial cellulose.

[0039] The content of hydroxyl groups in bacterial cellulose and antibacterial cellulose was tested by titration method, and the specific method was as follows: 1g bacterial cellulose and 1g antibacterial cellulose were weighed as samples, 80ml ethyl acetate reagent, 1ml perchloric acid with a mass fraction of 70% and 3ml acetic anhydride were mixed, and the mixture was placed in a water bath at 12°C for 35min, and then 20ml acetic anhydride reagent was added, and the mixture was shaken to prepare an acylation reagent for use, 30ml pyridine was placed in 10ml distilled water, and the mixture was shaken to prepare a hydrolysis reagent for use, the sample was placed in a titration bottle, 10ml ethyl acetate reagent and 3ml acetylation reagent were added, and the reaction was fully reacted for 25min, then 2ml distilled water was added ... 5ml hydrolysis reagent was added, and after standing for 10min, 2 drops of phenolphthalein indicator were added, and the mixture was titrated to 400 μL with 0.5mol / L standard potassium hydroxide titration solution. At the end point of the reaction, a blank experiment was performed at the same time, and the hydroxyl value of the sample was calculated according to the following formula; Hydroxyl value (mgKOH / g) = (V-V1) × 56.11 × C / m; where V is the volume of standard potassium hydroxide titration solution consumed in the blank experiment, ml; V1 is the volume of standard potassium hydroxide titration solution consumed by the sample in the experiment, ml; 56.11 is the molar mass fraction of potassium hydroxide, g / mol; C is the actual molar concentration of the standard titration solution, 1 mol / L; m is the sample mass, g; After calculation, the hydroxyl value of bacterial cellulose is 95.12 mgKOH / g; the hydroxyl value of antibacterial cellulose is 46.23 mgKOH / g. The content of hydroxyl groups in antibacterial cellulose is significantly lower than that in bacterial cellulose, which is caused by the reaction of hydroxyl groups in bacterial cellulose with carboxyl groups in the oleanolic acid structure.

[0040] 2. Preparation of anti-inflammatory and restorative carrageenan

[0041] S1: 2.5 g of k-carrageenan and 2 g of glycidyl methacrylate were placed in 60 ml of deionized water, stirred and mixed thoroughly, and then 0.06 g of tetrabutylammonium bromide was added. The temperature was raised to 80 ° C and stirred for 6 h. The product was collected after vacuum distillation to obtain olefinic carrageenan;

[0042] S2: Place 3.2 g of olefinated carrageenan in 80 ml of N,N-dimethylformamide, add 3 g of baicalin and 0.5 g of p-toluenesulfonic acid, raise the temperature to 90°C and stir to react for 5 h, remove the solvent by vacuum distillation, and collect the product to obtain anti-inflammatory and repairing carrageenan.

[0043] The hydroxyl content in olefinic carrageenan and anti-inflammatory restorative carrageenan was tested by titration method. The specific testing method was the same as the method for testing the hydroxyl content in bacterial cellulose and antibacterial cellulose. After testing, the hydroxyl value of olefinic carrageenan was 106.23 mgKOH / g; the hydroxyl value of anti-inflammatory restorative carrageenan was 51.45 mgKOH / g; the hydroxyl value of anti-inflammatory restorative carrageenan was significantly lower than that of olefinic carrageenan, which was caused by the reaction between the hydroxyl group in the olefinic carrageenan structure and the carboxyl group in the baicalin structure.

[0044] Example 1

[0045] Dressing production process

[0046] Step 1: Add 20 parts of antibacterial cellulose, 18 parts of anti-inflammatory repair carrageenan, and 8 parts of diallyldimethylammonium chloride into 80 parts of deionized water, and mix and stir thoroughly to form a dressing precursor mixture;

[0047] Step 2: Add 2 parts of ammonium persulfate to the dressing precursor mixture, heat to 65° C., stir for 5 hours, cool to room temperature, collect the product, and obtain a dressing.

[0048] The dressing was used as a sample, and after gold spraying, the microstructure of the sample was observed using a TM3030 scanning electron microscope. Figure 1 As shown, the sample has a large number of three-dimensional pore structures, which can provide sufficient space to absorb wound tissue fluid and effectively promote wound healing and skin repair.

[0049] Example 2

[0050] Dressing production process

[0051] Step 1: Add 25 parts of antibacterial cellulose, 20 parts of anti-inflammatory repair carrageenan, and 9 parts of diallyldimethylammonium chloride into 90 parts of deionized water, and mix and stir thoroughly to form a dressing precursor mixture;

[0052] Step 2: Add 3 parts of ammonium persulfate to the dressing precursor mixture, heat to 70° C., stir for 6.5 hours, cool to room temperature, collect the product, and obtain a dressing.

[0053] Example 3

[0054] Dressing production process

[0055] Step 1: Add 30 parts of antibacterial cellulose, 22 parts of anti-inflammatory repair carrageenan, and 10 parts of diallyldimethylammonium chloride into 100 parts of deionized water, and mix and stir thoroughly to form a dressing precursor mixture;

[0056] Step 2: Add 5 parts of potassium persulfate to the dressing precursor mixture, heat to 75° C., stir for 8 hours, cool to room temperature, collect the product, and obtain a dressing.

[0057] Comparative Example 1

[0058] Dressing production process

[0059] Step 1, placing 25 parts of antibacterial cellulose and 9 parts of diallyldimethylammonium chloride in 90 parts of deionized water, and mixing and stirring thoroughly to form a dressing precursor mixture;

[0060] Step 2: Add 3 parts of ammonium persulfate to the dressing precursor mixture, heat to 70° C., stir for 6.5 hours, cool to room temperature, collect the product, and obtain a dressing.

[0061] Comparative Example 2

[0062] Dressing production process

[0063] Step 1: Add 20 parts of anti-inflammatory and repairing carrageenan and 9 parts of diallyldimethylammonium chloride into 90 parts of deionized water, and mix and stir thoroughly to form a dressing precursor mixture;

[0064] Step 2: Add 3 parts of ammonium persulfate to the dressing precursor mixture, heat to 70° C., stir for 6.5 hours, cool to room temperature, collect the product, and obtain a dressing.

[0065] Comparative Example 3

[0066] Dressing production process

[0067] Step 1: Place 25 parts of bacterial cellulose, 20 parts of anti-inflammatory repair carrageenan, and 9 parts of diallyldimethylammonium chloride in 90 parts of deionized water, and mix and stir thoroughly to form a dressing precursor mixture;

[0068] Step 2: Add 3 parts of ammonium persulfate to the dressing precursor mixture, heat to 70° C., stir for 6.5 hours, cool to room temperature, collect the product, and obtain a dressing.

[0069] Comparative Example 4

[0070] Dressing production process

[0071] Step 1: Add 25 parts of antibacterial cellulose, 20 parts of olefinated carrageenan, and 9 parts of diallyldimethylammonium chloride into 90 parts of deionized water, and mix and stir thoroughly to form a dressing precursor mixture;

[0072] Step 2: Add 3 parts of ammonium persulfate to the dressing precursor mixture, heat to 70° C., stir for 6.5 hours, cool to room temperature, collect the product, and obtain a dressing.

[0073] Comparative Example 5

[0074] Dressing production process

[0075] Step 1: Add 25 parts of antibacterial cellulose and 20 parts of anti-inflammatory repair carrageenan into 90 parts of deionized water, and mix and stir thoroughly to form a dressing precursor mixture;

[0076] Step 2: Add 3 parts of ammonium persulfate to the dressing precursor mixture, heat to 70° C., stir for 6.5 hours, cool to room temperature, collect the product, and obtain a dressing.

[0077] Performance Testing

[0078] ① 80 mice weighing 25-30 g were randomly divided into eight groups, with 10 mice in each group. The left side of the back spine of each mouse was shaved to expose a 2 cm × 2 cm bare skin area, anesthesia was injected, and a circular wound with a diameter of 1 cm and a depth of 2 mm was cut in the bare skin area. The dressings prepared in Example 1 to Example 3 and Comparative Example 1 to Comparative Example 5 were used for treatment, respectively. The healing of the wounds of the mice was observed on the 3rd, 5th, 7th and 10th days, and the dressings were changed at the same time. The wound area was measured, and the wound healing rate was calculated by the following formula: E=(S-S1)×100% / S; where E is the wound healing rate, %; and S is the wound area before treatment, cm 2 ; S1 is the area of ​​unhealed wound after treatment, cm 2 After the wound of the mice healed, the skin repair of the mice was observed. The skin repair was complete when there was no obvious color difference between the wound and the rest of the body and the wound was less than 1mm above the normal skin surface. The skin repair grade was set. The skin repair days ≤50d was grade I; 50d≤skin repair days≤70d was grade II; >70d was grade III. The specific test results are shown in Table 1:

[0079] Table 1

[0080]

[0081] As can be seen from Table 1, the dressings prepared in Examples 1 to 3 have good skin repair ability, can effectively accelerate the wound healing process, and have good use effects. The dressings prepared in Comparative Examples 1 and 4 do not contain anti-inflammatory repair carrageenan, so the ability to promote wound healing is poor. The dressings prepared in Comparative Examples 2 and 3 do not contain antibacterial cellulose. Although anti-inflammatory repair carrageenan is added, the effect is still not as good as that of the embodiments. In the dressing prepared in Comparative Example 5, diallyldimethylammonium chloride is not added, the dressing is negatively charged, and it is difficult to closely combine with the skin, which affects the wound healing efficiency and skin repair ability of the dressing.

[0082] ② Antibacterial performance test: Take the dressings prepared in Examples 1 to 3 and Comparative Examples 1 to 5 as samples, and mix 1 ml of the dressings with a concentration of 10 -5CFU / ml activated Escherichia coli and Staphylococcus aureus strains were added dropwise to the sterilized sample surface, cultured at 37°C for 12 hours, 0.02 ml of the cultured bacterial solution was evenly spread on the solid culture medium, and cultured at 37°C for 24 hours. The number of colonies on the culture medium was counted, and a blank experiment was performed at the same time. The antibacterial rate was calculated according to the following formula: Antibacterial rate (%) = (the number of colonies on the culture medium counted in the blank experiment - the number of colonies on the culture medium counted in the sample experiment) × 100% / the number of colonies on the culture medium counted in the blank experiment; the calculation results are shown in Table 2:

[0083] Table 2

[0084]

[0085] It can be seen from Table 2 that, compared with the comparative example, the samples prepared in Examples 1 to 3 all have broad-spectrum and excellent antibacterial ability, can effectively prevent the contamination of pathogenic microorganisms during the use and storage of the dressing, can provide a good repair environment for the skin, and effectively improve the healing rate of the wound.

[0086] In the description of this specification, the description with reference to the terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" 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 representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described may be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art may combine and combine the different embodiments or examples described in this specification and the features of the different embodiments or examples, without contradiction.

[0087] The above contents are merely examples and explanations of the concept of the present invention. The technicians in this technical field may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the scope defined by the concept of the invention, they should all fall within the protection scope of the present invention.

Claims

1. A dressing with skin repair function, characterized in that: The invention comprises the following raw materials in parts by weight: 20-30 parts of antibacterial cellulose; 18-22 portions of anti-inflammatory and restorative carrageenan; 8-10 parts of diallyldimethylammonium chloride; 2-5 parts of initiator; 80-100 parts of deionized water; The antibacterial cellulose is prepared from bacterial cellulose and oleanolic acid; the anti-inflammatory repair carrageenan is prepared from olefinic carrageenan and baicalin; and the olefinic carrageenan is prepared from carrageenan and glycidyl methacrylate.

2. The dressing with skin repair function according to claim 1, characterized in that: The initiator is any one of ammonium persulfate and potassium persulfate.

3. The dressing with skin repair function according to claim 1, characterized in that: The preparation method of the antibacterial cellulose comprises the following steps: Place bacterial cellulose in deionized water, add oleanolic acid, mix and stir thoroughly, add composite catalyst, heat to 50-60°C and stir to react for 4-6 hours, cool to room temperature and collect the product to obtain antibacterial cellulose.

4. The dressing with skin repair function according to claim 3, characterized in that: The composite catalyst is 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and 4-dimethylaminopyridine in a mass ratio of 0.2-1:2.6-12.

5. The dressing with skin repair function according to claim 1, characterized in that: The preparation method of the anti-inflammatory and restorative carrageenan comprises the following steps: S1: Place carrageenan and glycidyl methacrylate in deionized water, stir and mix thoroughly, add tetrabutylammonium bromide, heat to 80-90°C and stir to react for 6-8h, collect the product after reduced pressure distillation to obtain olefinic carrageenan; S2: Place olefinated carrageenan in N,N-dimethylformamide, add baicalin and a catalyst, raise the temperature to 90-105°C and stir to react for 5-8h, remove the solvent by distillation under reduced pressure, and collect the product to obtain anti-inflammatory and repairing carrageenan.

6. The dressing with skin repair function according to claim 5, characterized in that: In step S1, the carrageenan is k-carrageenan.

7. The dressing with skin repair function according to claim 5, characterized in that: In step S2, the catalyst is p-toluenesulfonic acid.

8. A process for producing a dressing with skin repair function as claimed in claim 1, characterized in that: The following steps are involved: Step 1: placing antibacterial cellulose, anti-inflammatory repair carrageenan, and diallyldimethylammonium chloride in deionized water, and mixing and stirring thoroughly to form a dressing precursor mixture; Step 2: Add the initiator to the dressing precursor mixture, heat up and stir, and collect the product after cooling to room temperature to obtain a dressing.

9. The production process of a dressing with skin repair function according to claim 8, characterized in that: In step 2, the temperature of the heating and stirring is 65-75° C., and the time is 5-8 hours.

Images