A novel antibacterial silk and preparation method thereof

Abstract

The present invention relates to the technical field of silk modification, and in particular, designs a novel antibacterial silk and a preparation method. A preparation method of a novel antibacterial silk comprises the following steps: S11: soaking the silk in a finishing solution A for 5 to 50 minutes, and performing a first antibacterial finishing; S12: alcoholizing the silk after the first antibacterial finishing in 10 to 20°C ethanol for 20 seconds to obtain alcoholized silk; S13: directly soaking the alcoholized silk in step S12 in a finishing solution B for 0.5 to 5 hours at a soaking temperature of 10 to 20°C, and performing a second antibacterial finishing; S14: drying the silk after the second antibacterial finishing to obtain antibacterial silk. The preparation method of the present invention is simple, the process conditions are mild, the prepared silk has a good antibacterial effect, and is widely used in clothing, home textiles, medical and other fields. The prepared antibacterial silk has excellent antibacterial performance, and the antibacterial rates of Staphylococcus aureus and Escherichia coli are both greater than 92% after washing 50 times.

Description

Technical Field

[0001] The invention relates to the technical field of silk modification, and in particular to a novel antibacterial silk and a preparation method thereof. Background Art

[0002] Silk is a high-grade textile raw material, known as the "Queen of Fibers". It is a long fiber among natural fibers, and its length can be directly used for weaving. Silk is strong and elastic, thin and soft, has good moisture absorption and touch, and is especially elegant and beautiful in luster. Silk products have different styles, which can be as thin as gauze or as thick as velvet. In addition to clothing, silk fabrics can also be used to make various decorations such as curtains, headscarves, quilt covers, and mountings, which are even more precious and gorgeous. In industry, it can also be used as materials for parachutes, artificial blood vessels, and electrical insulation.

[0003] However, the growth of harmful bacteria during use not only damages the silk, but also causes unbearable stench and harms public health. In particular, pathogenic bacteria present on the surface of silk can cause serious skin infections such as skin allergies and irritation through direct contact with people, and in some cases even lead to heart problems and pneumonia. The preparation of silk with antibacterial activity is not only a need for daily life, but also a medical need.

[0004] CN 116623427 A discloses an antibacterial silk and a preparation method thereof, which relate to the field of new materials. The antibacterial silk has tea polyphenols attached to the surface of the silk fibers. The preparation method of the antibacterial silk comprises the following steps: Step 1: adding citric acid and theanine additives to soft water, stirring evenly and then adding silk floss, the bath ratio is 1:20-1:30, the soaking time is 50-60 minutes, and the theanine additive contains tea polyphenols; Step 2: dehydrating the soaked silk floss, and moving it to a drying room for drying, the drying room temperature is 90 degrees, and the time is about 5-6 hours. Tea polyphenols are composed of some polyphenols in tea leaves, which have the dual effects of inhibiting and killing bacteria, and have a broad-spectrum antibacterial property, which can give silk antibacterial properties. Summary of the invention

[0005] In view of the shortcomings of the prior art, the present invention provides a new type of antibacterial silk and a preparation method thereof. The preparation method is simple, the process conditions are mild, and the prepared silk has good antibacterial effect, and is widely used in clothing, home textiles, medical treatment and other fields.

[0006] The present invention provides a method for preparing a novel antibacterial silk, characterized in that it comprises the following steps:

[0007] S11: soaking the silk in finishing solution A for 5 to 50 minutes to perform the first antibacterial finishing;

[0008] S12: putting the silk after the first antibacterial treatment into ethanol at 10-20°C for 20s to obtain alcoholized silk; because silk is easy to deteriorate at high temperature, the low-temperature alcoholization step enhances the flexibility and reactivity of the silk, which is conducive to the efficient implementation of the subsequent finishing process. If the temperature is high, the antibacterial performance of the finishing agent decreases, which may be due to the high temperature, the decomposition of peroxide, and the silk will be partially deteriorated;

[0009] S13: directly soaking the alcoholized silk in step S12 in finishing solution B for 0.5 to 5 hours at a temperature of 10 to 20° C., and performing a second antibacterial finishing. During the second antibacterial finishing, the modified lignin simultaneously enters the porous barium sulfate microspheres, and is more tightly bonded to the silk through hydrogen bonds and other forces, thereby enhancing its long-lasting antibacterial ability.

[0010] S14: drying the silk after the second antibacterial treatment to obtain antibacterial silk.

[0011] Furthermore, the preparation of the finishing solution A comprises the following steps:

[0012] The finishing solution A is composed of the following substances in parts by mass:

[0013] 1-2 parts peroxide

[0014] Barium sulfate porous microspheres 1-3 parts

[0015] 3-5 parts of nano copper oxide

[0016] 1 part polyethylene glycol

[0017] 60-80 parts of water;

[0018] The barium sulfate porous microspheres and water in the finishing solution A are mixed evenly, then nano copper oxide and polyethylene glycol are added and mixed evenly, and finally peroxide is added and mixed quickly to obtain the finishing solution A. Nano copper oxide and peroxide can enter the micropores of the barium sulfate porous microspheres and can be slowly released during the silk finishing process to achieve a long-term antibacterial effect. At the same time, the barium sulfate porous microspheres have a larger specific surface area, and the trace amount of barium ions released therein also improve the antibacterial properties of silk to a certain extent.

[0019] Furthermore, the preparation of the finishing solution B comprises the following steps:

[0020] The finishing solution B is composed of the following substances in parts by mass:

[0021] Modified chitosan 3-5 parts

[0022] 1-2 portions of plant powder

[0023] 60-80 parts of water;

[0024] The modified chitosan and water in the finishing solution B are mixed evenly, and then the plant powder is added and mixed evenly to obtain the finishing solution B.

[0025] Furthermore, the peroxide is one of lauryl peroxide, percarbonic acid amide, and peroxybenzoic acid. Lauryl peroxide is used as a better technical means, probably because of the stability of lauryl peroxide, its long chain structure, and large molecular volume, which can enter the porous barium sulfate microspheres and is less likely to escape, thereby achieving a long-term antibacterial effect.

[0026] Furthermore, the preparation method of the porous barium sulfate microspheres is: mixing a barium chloride aqueous solution containing polyvinyl pyrrolidone and a titanium sulfate aqueous solution containing polyvinyl pyrrolidone and hydrogen peroxide, reacting at 150-170° C. for 36 hours, filtering, washing, and drying to obtain the porous barium sulfate microspheres.

[0027] Furthermore, the preparation of the modified chitosan comprises the following steps:

[0028] S21: soaking chitosan in a 1-2 wt % hydrogen peroxide solution for 1-2 h to activate the active groups of the chitosan;

[0029] S22: soaking the activated chitosan in 95% ethanol for 2 to 4 hours at a temperature of 40 to 60°C; S23: filtering the chitosan soaked in ethanol and drying it to obtain modified chitosan. The modified chitosan can enhance the binding force between silk and chitosan derivatives, reduce the amount of chitosan used, and maintain the original softness of silk.

[0030] Furthermore, the preparation method of the plant powder is to extract the plant dry powder with ethanol, remove the solvent ethanol, and obtain the plant powder. The plant dry powder is one of the dry powders of osmanthus, violet, and carnation. Adding natural plant components can enhance the antibacterial properties of the finishing agent.

[0031] Furthermore, the drying process in step S14 is: pre-drying the silk at 50° C. for 3 minutes in vacuum, and then baking it at 65° C. for 15 minutes in vacuum. Vacuum baking can avoid excessively high temperatures and ensure the performance of the antibacterial silk.

[0032] Furthermore, the concentrations of the barium chloride aqueous solution and the titanium sulfate aqueous solution are both 3 mmol / L, the content of polyvinyl pyrrolidone is both 0.2 wt %, and the content of hydrogen peroxide is 0.1 wt %.

[0033] At the same time, the present invention also provides an antibacterial silk prepared by the above method, which has excellent antibacterial performance, and the antibacterial rates of Staphylococcus aureus and Escherichia coli are both greater than 92% after washing 50 times. DETAILED DESCRIPTION

[0034] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in the field without making creative work are within the scope of protection of the present invention.

[0035] It should be understood that the specific embodiments described herein are only used to explain the present invention, and are not used to limit the present invention.

[0036] Example 1

[0037] A method for preparing a novel antibacterial silk comprises the following steps:

[0038] S11: soaking the silk in finishing solution A for 10 minutes to perform the first antibacterial finishing;

[0039] S12: putting the silk after the first antibacterial treatment into ethanol at 10-20° C. for 20 seconds to obtain alcoholized silk;

[0040] S13: directly soak the alcoholized silk in step S12 in finishing solution B for 2 hours at a temperature of

[0041] The temperature is 10-20℃, and the second antibacterial finishing is carried out;

[0042] S14: pre-baking the silk after the second antibacterial treatment at 50° C. for 3 minutes in vacuum, and then baking it at 65° C. for 15 minutes in vacuum to obtain the antibacterial silk.

[0043] The finishing solution A is composed of the following substances in parts by mass:

[0044] 1 part percarbonate

[0045] 1 part of barium sulfate porous microspheres

[0046] 3 parts of nano copper oxide

[0047] 1 part polyethylene glycol

[0048] 60 parts of water;

[0049] The barium sulfate porous microspheres and water in the finishing solution A are mixed evenly, then nano copper oxide and polyethylene glycol are added and mixed evenly, and finally peroxide is added and quickly mixed evenly to obtain the finishing solution A.

[0050] The finishing solution B is composed of the following substances in parts by mass:

[0051] Modified chitosan 3 parts

[0052] 1 part osmanthus powder

[0053] 60 parts water

[0054] The modified chitosan and water in the finishing solution B are mixed evenly, and then the plant powder is added and mixed evenly to obtain the finishing solution B.

[0055] The preparation method of the porous barium sulfate microspheres is as follows: a barium chloride aqueous solution containing polyvinyl pyrrolidone and a titanium sulfate aqueous solution containing polyvinyl pyrrolidone and hydrogen peroxide are mixed and reacted at 150-170° C. for 36 hours, and then filtered, washed, and dried to obtain the porous barium sulfate microspheres. The concentrations of the barium chloride aqueous solution and the titanium sulfate aqueous solution are both 3 mmol / L, the content of polyvinyl pyrrolidone is both 0.2 wt%, and the content of hydrogen peroxide is 0.1 wt%.

[0056] The preparation of the modified chitosan comprises the following steps:

[0057] S21: soaking chitosan in 1 wt % hydrogen peroxide solution for 2 h to activate the active groups of chitosan;

[0058] S22: soaking the activated chitosan in 95% ethanol for 2 hours at a temperature of 40-50° C.;

[0059] S23: filtering and drying the chitosan after soaking in ethanol to obtain modified chitosan.

[0060] The preparation method of the osmanthus powder comprises the following steps: extracting osmanthus dry powder with ethanol, and removing the solvent ethanol to obtain the osmanthus powder.

[0061] Example 2

[0062] A method for preparing a novel antibacterial silk comprises the following steps:

[0063] S11: soaking the silk in finishing solution A for 30 minutes to perform the first antibacterial finishing;

[0064] S12: putting the silk after the first antibacterial treatment into ethanol at 10-20° C. for 20 seconds to obtain alcoholized silk;

[0065] S13: directly soak the alcoholized silk in step S12 in finishing solution B for 4 hours at a temperature of

[0066] The temperature is 10-20℃, and the second antibacterial finishing is carried out;

[0067] S14: pre-baking the silk after the second antibacterial treatment at 50° C. for 3 minutes in vacuum, and then baking it at 65° C. for 15 minutes in vacuum to obtain the antibacterial silk.

[0068] The finishing solution A is composed of the following substances in parts by mass:

[0069] 3 parts of lauroyl peroxide

[0070] 3 parts of barium sulfate porous microspheres

[0071] Nano copper oxide 5 parts

[0072] 1 part polyethylene glycol

[0073] 80 parts water;

[0074] The barium sulfate porous microspheres and water in the finishing solution A are mixed evenly, then nano copper oxide and polyethylene glycol are added and mixed evenly, and finally peroxide is added and quickly mixed evenly to obtain the finishing solution A.

[0075] The finishing solution B is composed of the following substances in parts by mass:

[0076] 5 parts of modified chitosan

[0077] 2 parts violet powder

[0078] 70 parts of water;

[0079] The modified chitosan and water in the finishing solution B are mixed evenly, and then the plant powder is added and mixed evenly to obtain the finishing solution B.

[0080] The preparation method of the porous barium sulfate microspheres is as follows: a barium chloride aqueous solution containing polyvinyl pyrrolidone and a titanium sulfate aqueous solution containing polyvinyl pyrrolidone and hydrogen peroxide are mixed and reacted at 150-170° C. for 36 hours, and then filtered, washed, and dried to obtain the porous barium sulfate microspheres. The concentrations of the barium chloride aqueous solution and the titanium sulfate aqueous solution are both 3 mmol / L, the content of polyvinyl pyrrolidone is both 0.2 wt%, and the content of hydrogen peroxide is 0.1 wt%.

[0081] The preparation of the modified chitosan comprises the following steps:

[0082] S21: soaking chitosan in a 2 wt % hydrogen peroxide solution for 1 h to activate the active groups of chitosan;

[0083] S22: soaking the activated chitosan in 95% ethanol for 3 hours at a temperature of 50-60° C.;

[0084] S23: filtering and drying the chitosan after soaking in ethanol to obtain modified chitosan.

[0085] The preparation method of the violet powder comprises the following steps: extracting osmanthus dry powder with ethanol, and removing the solvent ethanol to obtain the osmanthus powder.

[0086] Example 3

[0087] A method for preparing a novel antibacterial silk comprises the following steps:

[0088] S11: soaking the silk in finishing solution A for 20 minutes to perform the first antibacterial finishing;

[0089] S12: putting the silk after the first antibacterial treatment into ethanol at 10-20° C. for 20 seconds to obtain alcoholized silk;

[0090] S13: directly soak the alcoholized silk in step S12 in finishing solution B for 3 hours at a temperature of

[0091] The temperature is 10-20℃, and the second antibacterial finishing is carried out;

[0092] S14: pre-baking the silk after the second antibacterial treatment at 50° C. for 3 minutes in vacuum, and then baking it at 65° C. for 15 minutes in vacuum to obtain the antibacterial silk.

[0093] The finishing solution A is composed of the following substances in parts by mass:

[0094] 2 parts of benzoic acid

[0095] 2 parts of barium sulfate porous microspheres

[0096] Nano copper oxide 4 parts

[0097] 1 part polyethylene glycol

[0098] 70 parts of water;

[0099] The barium sulfate porous microspheres and water in the finishing solution A are mixed evenly, then nano copper oxide and polyethylene glycol are added and mixed evenly, and finally peroxide is added and quickly mixed evenly to obtain the finishing solution A.

[0100] The finishing solution B is composed of the following substances in parts by mass:

[0101] 4 parts of modified chitosan

[0102] 2 parts carnation powder

[0103] 70 parts of water;

[0104] The modified chitosan and water in the finishing solution B are mixed evenly, and then the plant powder is added and mixed evenly to obtain the finishing solution B.

[0105] The preparation method of the porous barium sulfate microspheres is as follows: a barium chloride aqueous solution containing polyvinyl pyrrolidone and a titanium sulfate aqueous solution containing polyvinyl pyrrolidone and hydrogen peroxide are mixed and reacted at 150-170° C. for 36 hours, and then filtered, washed, and dried to obtain the porous barium sulfate microspheres. The concentrations of the barium chloride aqueous solution and the titanium sulfate aqueous solution are both 3 mmol / L, the content of polyvinyl pyrrolidone is both 0.2 wt%, and the content of hydrogen peroxide is 0.1 wt%.

[0106] The preparation of the modified chitosan comprises the following steps:

[0107] S21: soaking chitosan in a 2 wt % hydrogen peroxide solution for 2 h to activate the active groups of chitosan;

[0108] S22: soaking the activated chitosan in 95% ethanol for 3 hours at a temperature of 50-60° C.;

[0109] S23: filtering and drying the chitosan after soaking in ethanol to obtain modified chitosan.

[0110] The preparation method of the dianthus powder comprises the following steps: extracting osmanthus dry powder with ethanol, and removing the solvent ethanol to obtain the osmanthus powder.

[0111] Comparative Example 1

[0112] The dodecanoyl peroxide component in the finishing solution A of Example 2 was removed, and the rest was the same as Example 2, which will not be repeated here.

[0113] Comparative Example 2

[0114] The barium sulfate porous microsphere component in the finishing solution A of Example 2 is removed, and the rest is the same as Example 2, which will not be repeated here.

[0115] Comparative Example 3

[0116] The modified chitosan in the finishing solution B of Example 2 was replaced by the chitosan before modification, and the rest was the same as Example 2 and will not be described again.

[0117] Comparative Example 4

[0118] The osmanthus powder component of the finishing solution A in Example 1 was removed, and the rest was the same as in Example 1 and will not be described in detail.

[0119] The silk prepared by the preparation methods of the novel antibacterial silk in the above embodiments and comparative examples was subjected to antibacterial tests according to the JIS L-0217-103 method. The test results are shown in Table 1.

[0120] Table 1 Antibacterial performance test results

[0121]

[0122] It can be seen from the data of Examples 1, 2, and 3 that the antibacterial effect of 0 washings is not much different, and the antibacterial effect of 50 washings is more reduced in Example 1, which may be because percarbonic acid amide has poor stability in aqueous solution and decomposes quickly, resulting in too much reduction in active oxygen; from the data of Comparative Example 1, it can be seen that the lack of dodecyl peroxide component and the source of active oxygen significantly reduce the antibacterial effect; from the data of Comparative Example 2, it can be seen that the lack of barium sulfate porous microsphere component ultimately reduces the antibacterial effect the most; from the data of Comparative Example 3, it can be seen that the modified chitosan has better performance than the chitosan before modification; from the data of Comparative Example 4, it can be seen that the antibacterial performance is slightly reduced by removing the osmanthus powder in the finishing solution A of Example 1, and the antibacterial effect is more significantly reduced by 50 washings.

Claims

1. A method for preparing antibacterial silk, characterized in that: The steps include: S11: soaking the silk in finishing solution A for 5 to 50 minutes to perform the first antibacterial finishing; S12: putting the silk after the first antibacterial treatment into ethanol at 10-20° C. for 20 seconds to obtain alcoholized silk; S13: directly soaking the alcoholized silk in step S12 in finishing solution B for 0.5 to 5 hours at a temperature of 10 to 20° C., and performing a second antibacterial finishing; S14: drying the silk after the second antibacterial treatment to obtain antibacterial silk; The finishing solution A is composed of the following substances in parts by mass: 1-2 parts peroxide Barium sulfate porous microspheres 1-3 parts 3-5 parts of nano copper oxide 1 part polyethylene glycol 60-80 parts of water; The peroxide is dodecyl peroxide; The barium sulfate porous microspheres and water in the finishing solution A are mixed evenly, then nano copper oxide and polyethylene glycol are added and mixed evenly, and finally peroxide is added and mixed quickly to obtain the finishing solution A; The preparation of the finishing solution B comprises the following steps: The finishing solution B is composed of the following substances in parts by mass: Modified chitosan 3-5 parts 1-2 portions of plant powder 60-80 parts of water; The modified chitosan and water in the finishing solution B are mixed evenly, and then the plant powder is added and mixed evenly to obtain the finishing solution B; The preparation method of the porous barium sulfate microspheres is as follows: a barium chloride aqueous solution containing polyvinyl pyrrolidone and a titanium sulfate aqueous solution containing polyvinyl pyrrolidone and hydrogen peroxide are mixed and reacted at 150-170° C. for 36 hours, and then filtered, washed, and dried to obtain the porous barium sulfate microspheres; The preparation of the modified chitosan comprises the following steps: S21: soaking chitosan in a 1-2 wt % hydrogen peroxide solution for 1-2 h to activate the active groups of the chitosan; S22: soaking the activated chitosan in 95% ethanol for 2 to 4 hours at a temperature of 40 to 60° C.; S23: filtering and drying the chitosan after soaking in ethanol to obtain modified chitosan.

2. The preparation method according to claim 1, characterized in that: The preparation method of the plant powder comprises the following steps: extracting the plant dry powder with ethanol, removing the solvent ethanol, and obtaining the plant powder. The plant dry powder is one of the dry powders of osmanthus, violet, and dianthus.

3. The preparation method according to claim 1, characterized in that: The drying process in step S14 is as follows: pre-dry the silk at 50° C. in vacuum for 3 minutes, and then bake it at 65° C. in vacuum for 15 minutes.

4. The preparation method according to claim 2, characterized in that: The concentrations of the barium chloride aqueous solution and the titanium sulfate aqueous solution were both 3 mmol / L, the content of polyvinyl pyrrolidone was 0.2 wt %, and the content of hydrogen peroxide was 0.1 wt %.

5. An antibacterial silk prepared by the preparation method according to any one of claims 1 to 4.

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