High-efficiency and long-lasting antibacterial real silk fabric and preparation method thereof

Abstract

The application discloses a kind of high-efficiency durable antibacterial silk fabric and preparation method thereof, comprising the following steps: polyhexamethylene biguanide hydrochloride, benzene dialdehyde is added to distilled water and heated for a period of time, control polyhexamethylene biguanide hydrochloride and benzene dialdehyde between aldehyde amine condensation reaction occurs, and reaction type antibacterial finishing liquor is prepared, then silk fabric is immersed in finishing liquor, and high-efficiency durable antibacterial silk fabric is prepared by impregnation method.The silk fabric prepared by the application has excellent antibacterial effect and antibacterial durability, and has the advantages of washing resistance.

Description

Technical Field

[0001] This invention belongs to the field of textile processing technology, and in particular relates to a high-efficiency and durable antibacterial silk fabric and its preparation method. Background Technology

[0002] Silk, hailed as the "Queen of Fibers," possesses excellent properties such as softness, gentle luster, and excellent moisture absorption and breathability. Therefore, silk has long been used as a high-end textile material, widely applied in silk pajamas, cheongsams, scarves, and bedding. However, silk fabrics have poor antibacterial properties, easily breeding bacteria and providing them with nutrients and energy for reproduction, ultimately endangering human health. Consequently, antibacterial finishing of silk fabrics has received widespread attention both domestically and internationally.

[0003] Polyhexamethylene biguanide (PPBQ) is currently a widely used guanidine salt antibacterial agent. Its active guanidine group can react with hydrogen ions in microorganisms to become positively charged, thereby electrostatically adsorbing onto the negatively charged bacterial cell membrane. This disrupts the bacterial cell membrane, leading to "bacterial lysis" and inhibiting bacterial growth and reproduction. It is widely used in medical devices, public environments, home furnishings, textiles, and food. However, PPBQ is a cationic polymer, which repels the amino groups in silk fibers, resulting in weak bonding between PPBQ and silk fibers. Furthermore, PPBQ's high water solubility leads to poor wash resistance in PPBQ modified silk fabrics, making it difficult to meet practical application requirements.

[0004] Yu Xin et al. (Antibacterial and Shrink-resistant Finishing of Wool Fabrics [J]. Journal of Donghua University (Natural Science Edition), 2013, 39(1):77-82,93.) first used potassium persulfate and sodium sulfite to pre-treat wool fabrics with oxidation, which destroyed the cysteine ​​and disulfide bonds in the macromolecular chain of wool fibers and generated active groups. Then, polyhexamethylene biguanide was used for grafting, thereby improving the wash resistance of antibacterial wool fabrics. However, this method has a significant impact on the strength of wool fabrics, and silk fabrics do not contain disulfide bonds, so it cannot be applied to the durable antibacterial modification of silk fabrics.

[0005] Liu Jing et al. (Electrostatic self-assembly of polyhexamethylene biguanide hydrochloride on cotton fabrics and its antibacterial properties [J]. Journal of Textile Research, 2012, 33(4): 86-90.) constructed polyhexamethylene biguanide hydrochloride and sodium polystyrene sulfonate on the surface of cotton fibers through electrostatic self-assembly. The water resistance of polyhexamethylene biguanide hydrochloride antibacterial cotton fabric was improved by layer-by-layer electrostatic self-assembly. However, this method requires multiple assembly to deposit anionic and cationic compounds on the fabric surface, which is complicated and has a serious impact on the hand feel of the fabric. It cannot be applied to the durable antibacterial modification of silk fabrics. Summary of the Invention

[0006] To address the aforementioned issues, this invention provides a method for preparing a highly efficient and durable antibacterial silk fabric. This method enhances the bonding strength between the antibacterial agent and the silk fabric, while simultaneously improving the antibacterial properties of the silk fabric through the synergistic effect of the raw materials, without affecting the strength or feel of the fabric.

[0007] The first objective of this invention is to provide an antibacterial finishing agent for silk fabrics, said antibacterial finishing agent comprising a product obtained by an aldehyde-amine condensation reaction of polyhexamethylene biguanide hydrochloride and phenylene dialdehyde. Due to steric hindrance, each end of the polyhexamethylene biguanide hydrochloride monomer has an amino group that can participate in the reaction.

[0008] Furthermore, the phenylene dialdehyde is selected from one or more of terephthalaldehyde, 1,3-phenylene dialdehyde, 2,5-dihydroxyterephthalaldehyde, 2-hydroxyisophthalaldehyde, and 2,5-dihydroxyterephthalic acid.

[0009] A second objective of this invention is to provide a method for preparing the aforementioned antibacterial finishing agent, comprising the following steps: reacting polyhexamethylene biguanide hydrochloride and phenylene dialdehyde at 75–85°C. Phenylene dialdehyde is poorly soluble in cold water; increasing the temperature helps promote the dissolution of phenylene dialdehyde and facilitates the condensation reaction between polyhexamethylene biguanide hydrochloride and phenylene dialdehyde.

[0010] Further, polyhexamethylene biguanide hydrochloride and benzodialdehyde were added to distilled water and heated to react.

[0011] Furthermore, in the embodiments of the present invention, the amount of polyhexamethylene biguanide hydrochloride is 0.5-3 g / L. Increasing the amount of polyhexamethylene biguanide hydrochloride helps to further improve the antibacterial effect of silk fabric, but too much is wasteful.

[0012] Furthermore, in the embodiments of the present invention, the amount of phenyl dialdehyde is 1-5 g / L. The aldehyde group of phenyl dialdehyde can undergo a condensation reaction with the guanidine group of polyhexamethylene biguanide hydrochloride to prepare a reactive antibacterial finishing agent. Increasing the amount of phenyl dialdehyde helps to promote the condensation reaction between the two, but too much will be wasteful.

[0013] Furthermore, the reaction time is 30–60 min.

[0014] The third objective of this invention is to provide the application of a product obtained by the aldehyde-amine condensation reaction of polyhexamethylene biguanide hydrochloride and phenylene dialdehyde in the preparation of an antibacterial finishing agent for silk fabrics.

[0015] The fourth objective of this invention is to provide a silk fabric treated with the aforementioned antibacterial finishing agent.

[0016] The fifth objective of this invention is to provide a method for antibacterial finishing of silk fabrics, comprising the following steps:

[0017] S1. Mix and react polyhexamethylene biguanide hydrochloride and phenylene dialdehyde to obtain an antibacterial finishing solution;

[0018] S2. Use antibacterial finishing solution to finish silk fabrics.

[0019] Furthermore, in step S2, the mass ratio of silk fabric to antibacterial finishing solution is 1:20 to 50.

[0020] Furthermore, in step S2, the finishing temperature is 75–85°C. During the finishing process, the aldehyde group of the reactive antibacterial finishing agent can undergo an aldehyde-amine condensation reaction with the amino group of the silk fiber to generate a Schiff base structure. Increasing the temperature helps to promote the reaction and makes the antibacterial modification more uniform.

[0021] Furthermore, in step S2, the preparation time is 40–60 min.

[0022] Furthermore, silk fabrics include, but are not limited to, silk crepe de chine, silk power spinning, and silk satin.

[0023] The principle of this invention is as follows: A reactive antibacterial finishing liquid is prepared by condensing the guanidine group of polyhexamethylene biguanide hydrochloride with the aldehyde group containing phenylene dialdehyde. This antibacterial finishing agent contains an active aldehyde group, which can undergo an aldehyde-amine condensation reaction with the amino groups on silk fibers, thereby grafting the antibacterial finishing agent onto the silk fibers to obtain an antibacterial silk fabric with excellent wash resistance. Furthermore, polyhexamethylene biguanide hydrochloride, as a cationic antibacterial finishing agent, has high antibacterial efficiency, mainly by adsorbing bacteria through electrostatic interaction, thus preventing bacterial division and reproduction and rendering them inactive. Simultaneously, the Schiff base structure generated in the finishing agent structure and during the cross-linking process with the fabric also possesses antibacterial properties, which can synergistically enhance the antibacterial performance of the finished silk fabric. Therefore, the antibacterial silk fabric prepared by the method of this invention exhibits excellent antibacterial and wash resistance properties, and the processing conditions are mild and the operation is simple, making it of significant practical application value.

[0024] The beneficial effects of this invention are:

[0025] (1) The reactive antibacterial finishing solution prepared in this invention has excellent antibacterial effect by means of the synergistic antibacterial properties of polyhexamethylene biguanide hydrochloride and Schiff base structure;

[0026] (2) The reactive antibacterial finishing agent in this invention can undergo an aldehyde-amine condensation reaction with silk fibers to form covalent bonds, which makes the antibacterial silk fabric have excellent antibacterial durability.

[0027] (3) The preparation process of the present invention is simple, the reaction conditions are mild, the process is short, and it has broad application prospects and important practical application value. Attached Figure Description

[0028] Figure 1 These are photographs of the antibacterial test results of the antibacterial silk crepe fabric and cotton sample in Example 1 of this invention. Detailed Implementation

[0029] The present invention will be further described below with reference to the accompanying drawings and specific embodiments, so that those skilled in the art can better understand and implement the present invention. However, the embodiments described are not intended to limit the present invention.

[0030] Example 1

[0031] A method for preparing a highly effective and durable antibacterial silk fabric, comprising the following specific steps:

[0032] Polyhexamethylene biguanide hydrochloride and terephthalaldehyde were added to distilled water, with the concentration of polyhexamethylene biguanide hydrochloride being 2 g / L and the concentration of terephthalaldehyde being 3 g / L. The mixture was heated to 80°C and reacted for 50 min to obtain an antibacterial finishing solution. Then, silk crepe fabric was immersed in the antibacterial finishing solution at a mass ratio of 1:40. The mixture was kept at 80°C with shaking for 50 min. After washing and drying, antibacterial silk crepe fabric was obtained.

[0033] Example 2

[0034] A method for preparing a highly effective and durable antibacterial silk fabric, comprising the following specific steps:

[0035] Polyhexamethylene biguanide hydrochloride and 1,3-phenylenedialdehyde were added to distilled water, with the concentration of polyhexamethylene biguanide hydrochloride being 0.5 g / L and the concentration of 1,3-phenylenedialdehyde being 1 g / L. The mixture was heated to 75°C and reacted for 60 min to obtain an antibacterial finishing solution. Then, a silk power-spun fabric was immersed in the antibacterial finishing solution at a mass ratio of 1:20. The mixture was kept at 75°C with shaking for 60 min. After washing and drying, an antibacterial silk power-spun fabric was obtained.

[0036] Example 3

[0037] A method for preparing a highly effective and durable antibacterial silk fabric, comprising the following specific steps:

[0038] Polyhexamethylene biguanide hydrochloride and 2,5-dihydroxyterephthalaldehyde were added to distilled water, with the concentration of polyhexamethylene biguanide hydrochloride being 1 g / L and the concentration of 2,5-dihydroxyterephthalaldehyde being 2 g / L. The mixture was heated to 85°C and reacted for 30 min to obtain an antibacterial finishing solution. Then, a silk crepe fabric was immersed in the antibacterial finishing solution at a mass ratio of 1:50. The mixture was kept at 85°C with shaking for 40 min. After washing and drying, an antibacterial silk crepe fabric was obtained.

[0039] Example 4

[0040] A method for preparing a highly effective and durable antibacterial silk fabric, comprising the following specific steps:

[0041] Polyhexamethylene biguanide hydrochloride and 2-hydroxyisophthalaldehyde were added to distilled water, with the concentration of polyhexamethylene biguanide hydrochloride being 1.5 g / L and the concentration of 2-hydroxyisophthalaldehyde being 3 g / L. The mixture was heated to 83°C and reacted for 45 min to obtain an antibacterial finishing solution. Then, silk crepe fabric was immersed in the antibacterial finishing solution at a mass ratio of 1:30. The mixture was kept at 79°C with shaking for 55 min. After washing and drying, antibacterial silk crepe fabric was obtained.

[0042] Example 5

[0043] A method for preparing a highly effective and durable antibacterial silk fabric, comprising the following specific steps:

[0044] Polyhexamethylene biguanide hydrochloride and 2,5-dihydroxyphenylene glycol were added to distilled water, with the concentration of polyhexamethylene biguanide hydrochloride being 3 g / L and the concentration of 2,5-dihydroxyphenylene glycol being 5 g / L. The mixture was heated to 82°C and reacted for 50 min to obtain an antibacterial finishing solution. Then, silk crepe fabric was immersed in the antibacterial finishing solution at a mass ratio of 1:35. The mixture was kept at 78°C with shaking for 60 min. After washing and drying, antibacterial silk crepe fabric was obtained.

[0045] Comparative Example 1

[0046] A method for preparing a high-efficiency and durable antibacterial silk fabric is basically the same as in Example 1, except that terephthalaldehyde is not added. That is, the antibacterial finishing solution contains only polyhexamethylene biguanide hydrochloride and no terephthalaldehyde.

[0047] Comparative Example 2

[0048] A method for preparing a high-efficiency and durable antibacterial silk fabric is basically the same as in Example 1, except that polyhexamethylene biguanide hydrochloride is not added. That is, the antibacterial finishing solution contains only terephthalaldehyde and no polyhexamethylene biguanide hydrochloride.

[0049] Test case

[0050] The antibacterial properties and washability of the antibacterial silk fabrics prepared in Examples 1-5 and Comparative Examples 1-2 were tested.

[0051] The antibacterial properties of antibacterial silk fabric against Escherichia coli and Staphylococcus aureus were tested in accordance with GB / T20944.3-2008 "Evaluation of antibacterial properties of textiles - Part 3: Vibration method".

[0052] The washing method for antibacterial silk fabrics shall be in accordance with AATCC 61-2006 "Accelerated test for color fastness to washing in household and commercial use".

[0053] The final measured antibacterial properties of the antibacterial silk fabric are shown in the table below:

[0054]

[0055] As can be seen from the table, the antibacterial effect of untreated silk fabric is poor, with inhibition rates of only 22.3% and 21.1% against Escherichia coli and Staphylococcus aureus, respectively. The antibacterial treatment solution of this invention increases the inhibition rates of Escherichia coli and Staphylococcus aureus on silk fabric to 87.3% and 85.4%, respectively. When the concentration of the antibacterial treatment solution increases, the inhibition rate against both Escherichia coli and Staphylococcus aureus can reach 99.9%, indicating that the treated silk fabric has excellent antibacterial effects. Furthermore, after 50 washes, the inhibition rates of the treated silk fabric against Escherichia coli and Staphylococcus aureus remain higher than 81.2% and 80.5%, respectively. Moreover, the wash resistance improves with increasing antibacterial treatment solution concentration, indicating that the treated silk fabric has excellent wash resistance.

[0056] Comparing Example 1 with Comparative Examples 1 and 2, it can be seen that the silk fabric treated in Comparative Example 1 can achieve a good antibacterial effect, but it loses its antibacterial effect after 50 washes. This is because polyhexamethylene biguanide hydrochloride cannot form a stable covalent bond with the silk fabric, and polyhexamethylene biguanide hydrochloride is easily soluble in water. It is easy to fall off the silk fabric during the washing process, thus losing its antibacterial effect and therefore not resistant to washing.

[0057] The above results show that the silk fabric treated by the method of the present invention has excellent antibacterial properties and washability.

[0058] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. An antibacterial finishing agent for silk fabrics, characterized in that: The antibacterial finishing agent comprises a product obtained by aldehyde-amine condensation reaction of polyhexamethylene biguanide hydrochloride and phenylene dialdehyde, wherein the phenylene dialdehyde is selected from one or more of terephthalaldehyde, 2-hydroxy-isophthalaldehyde, and 2,5-dihydroxy-terephthalic acid.

2. A method for preparing the antibacterial finishing agent according to claim 1, characterized in that: The process includes reacting polyhexamethylene biguanide hydrochloride and phenyl dialdehyde at 75-85°C.

3. The preparation method according to claim 2, characterized in that: The reaction time is 30-60 minutes.

4. The application of a product obtained by the aldehyde-amine condensation reaction of polyhexamethylene biguanide hydrochloride and phenylene dialdehyde in the preparation of an antibacterial finishing agent for silk fabrics, characterized in that, The phenylene dialdehyde is selected from one or more of terephthalaldehyde, 2-hydroxy-isophthalaldehyde, and 2,5-dihydroxy-terephthalic acid.

5. Silk fabric treated with the antibacterial finishing agent as described in claim 1.

6. A method for antibacterial finishing of silk fabric, characterized in that, Includes the following steps: S1. Mix and react polyhexamethylene biguanide hydrochloride and phenyl dialdehyde to obtain an antibacterial finishing solution, wherein the phenyl dialdehyde is selected from one or more of terephthalaldehyde, 2-hydroxy-isophthalaldehyde, and 2,5-dihydroxy-terephthalic acid. S2. Use antibacterial finishing solution to finish silk fabrics.

7. The method according to claim 6, characterized in that: In step S2, the mass ratio of silk fabric to antibacterial finishing solution is 1:20~50.

8. The method according to claim 6, characterized in that: In step S2, the finishing temperature is 75~85℃.

9. The method according to claim 6, characterized in that: In step S2, the preparation time is 40~60 minutes.

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