Antibacterial polyester fiber for safety shoes and production method thereof

Abstract

The application discloses antibacterial polyester fiber for safety shoes and a production method thereof, and comprises composite particles, PET polyester and an additive, wherein the composite particles are 0.01-0.1% by mass, the additive is 6-17% by mass, and the rest is PET polyester; the composite particles comprise 70-88% of copper powder, 10-25% of graphene oxide and 2-7% of guanidine derivative for sterilization; the inventor of the application integrates the copper powder, the graphene oxide and the guanidine derivative into one body based on an accident, finds that the antibacterial performance is greatly increased, the antibacterial requirement can be met by adding a small amount, and the influence on the performance of the polyester fiber is reduced.

Description

Technical Field

[0001] This invention relates to the field of footwear materials technology, specifically to antibacterial polyester fibers for safety shoes and their production method. Background Technology

[0002] Polyester fiber is a commonly used synthetic fiber material in the footwear industry. With its high strength, good elasticity, wear resistance, easy processing, and low cost, it is widely used in the production of shoe uppers, soles, linings, and functional components. Common examples include polyester mesh, which is often used as the outer layer of the sloping surface to provide breathability and support, and polyester knitted fabrics, which are often used as the main body of the shoe upper. Polyester fiber is one of the important basic raw materials in the footwear material field.

[0003] Given the inherent properties of polyester, it is prone to microbial growth. Its high hydrophobicity allows sweat, sebum, and dander to easily accumulate on its surface, providing a nutrient-rich microenvironment for bacteria. To address this, companies modify polyester by adding inorganic and organic antibacterial agents. However, this method suffers from the problem of requiring large amounts of antibacterial agents, which can negatively impact the mechanical properties of polyester and requires improvement. Summary of the Invention

[0004] To address at least one of the aforementioned technical deficiencies, the present invention provides the following technical solution:

[0005] This application discloses antibacterial polyester fiber for safety shoes, comprising composite particles, PET polyester and additives. By weight, the composite particles are 0.01-0.1%, the additives are 6-17%, and the remainder is PET polyester. The composite particles include 70-88% copper powder, 10-25% graphene oxide, and 2-7% guanidine derivatives for sterilization.

[0006] The inventors discovered by chance that combining copper powder, graphene oxide, and guanidine derivatives into a single compound significantly increases its antibacterial properties. A small amount of this compound is sufficient to meet antibacterial requirements, thus reducing its impact on the properties of polyester fibers.

[0007] The working principle is as follows: the positive charge of the guanidine group combines with the surface of bacteria through electrostatic interaction; the graphene edge cuts the cell membrane; copper ions destroy the cell interior and hinder its metabolism; the oxygen-containing functional groups on the graphene surface interact chemically with the bacteria; and the guanidine derivatives destroy the cells, all of which work together to achieve the purpose of killing bacteria.

[0008] Furthermore, the guanidine derivative is of the 2-aminoimidazolidinone type, and the additives include lubricants, antioxidants, dispersants, and toughening agents, wherein the mass ratio of lubricants, antioxidants, dispersants, and toughening agents is 5:1-2.5:2-4:2-6, which limits the type of guanidine derivative, helps to reduce the impact on the performance of PET fibers, and at the same time helps to improve the dispersibility of composite particles.

[0009] This application discloses a method for producing the aforementioned polyester fiber, including the following steps:

[0010] First, the preparation of composite particles

[0011] Copper-supported particles are obtained by mixing graphite oxide powder and soluble copper salt in a solvent and spray drying. The copper-supported particles are then grafted with guanidine derivatives used for sterilization to form composite particles through coupling modification.

[0012] Second, the composite particles prepared in the first step are melt-spun with PET polyester and auxiliaries to form polyester fibers.

[0013] In this solution, graphene oxide is used to adsorb and support copper powder, which helps to improve the bonding strength between copper powder and PET fiber, making it washable and durable with antibacterial properties. The graphene oxide is modified with a coupling agent and then grafted with guanidine derivatives, so that the three-dimensional composite is integrated into a single composite particle. The formed composite particle is directly melt-spun with PET polyester to form fiber. The whole process is simple and highly operable.

[0014] Furthermore, in the first step, graphene oxide powder is mixed with a solvent and ultrasonically treated. After adding copper sulfate salt, it is wet-milled and then spray-dried to obtain copper-supported particles. The process is simple and easy to operate.

[0015] Furthermore, the copper sulfate salt is copper sulfate pentahydrate, and the copper-loaded particles are modified by a silane coupling agent or an EDC / NHS coupling system, preferably an EDC / NHS coupling system, wherein EDC refers to 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide and NHS refers to N-hydroxysuccinimide.

[0016] Furthermore, the copper-supported particles were ultrasonically dispersed in water, EDC and NHS were added, and the reaction was carried out at room temperature for 15-30 minutes. Then, guanidine derivatives were added, the pH was adjusted, and the reaction was carried out at room temperature for 4-12 hours. The composite particles were obtained by centrifugation, washing, and drying. Ultrasonic dispersion helps to promote the uniformity of particle dispersion, and washing can remove some unreacted substances.

[0017] Furthermore, the spray drying temperature is 180-220℃, and the mass ratio of graphene oxide powder to solvent is 1:150-200.

[0018] Furthermore, in the second step, the spinning temperature is 240-300℃, the spinning speed is 800-1600m / min, the stretching temperature is 60-80℃, and the total stretching ratio is 3-5. These limiting spinning parameters help improve fiber quality.

[0019] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0020] 1. This invention combines guanidine derivatives, copper powder, and graphene oxide into a single composite particle, which can significantly improve the antibacterial properties of PET fibers and make the antibacterial properties more durable when added to PET fibers. Attached Figure Description

[0021] To more clearly illustrate the technical solutions in the embodiments of the present invention, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0022] Figure 1 This is an SEM image of the copper-loaded particles in Example 1. Detailed Implementation

[0023] The present invention will be further described below with reference to the accompanying drawings and specific embodiments.

[0024] In the following preparation examples, the guanidine derivative is of the 2-aminoimidazolone type, and its specific structural formula is as follows: It can be purchased directly from the market, or it can be obtained by reacting amino acid ethyl ester hydrochloride with carbodiimide at 90°C using zinc trifluoromethanesulfonate as a catalyst, triethylamine as a base, and tetrahydrofuran as a solvent. This type of reaction is quite common and will not be elaborated here.

[0025] The lubricant is PE wax, the antioxidant is antioxidant 1010, the dispersant is YY-502A, the toughening agent is POE, and the intrinsic viscosity of PET polyester is 0.81 dL / g.

[0026] Example 1

[0027] The antibacterial polyester fiber for safety shoes includes composite particles, PET polyester and additives. By mass, the composite particles are 0.04%, the additives are 12%, and the remainder is PET polyester. The additives are lubricant, antioxidant, dispersant and toughening agent in a mass ratio of 5:2:3:4.

[0028] By weight, the composite particles comprise 80% copper powder, 15% graphene oxide, and 5% guanidine derivatives for sterilization.

[0029] The production method of antibacterial polyester fiber for safety shoes is as follows: including the following steps:

[0030] First, the preparation of composite particles

[0031] Graphene oxide was added to 150 times its weight of water, stirred until homogeneous, and then ultrasonically treated for 45 minutes. Anhydrous copper sulfate was then added according to the mass ratio of graphene oxide to copper powder and stirred until homogeneous. The mixture was then wet-milled at 3500 rpm for 7 hours. The milled mixture was then spray-dried to obtain copper-supported composite particles. SEM images are shown below. Figure 1 As shown, the spray drying temperature is 200℃.

[0032] The copper-supported particles obtained above were subjected to coupling modification, with EDC / NHS as the coupling agent. Specifically, the copper-supported particles were mixed with water (1.5 mg / ml), and then EDC and NHS were added. The molar ratio of graphene oxide:EDC:NHS was 1:1.2:1.5. The reaction was carried out at room temperature for 30 min. Then, the guanidine derivative was added to the above reaction solution to adjust the pH to 6.5, and the reaction was carried out at room temperature for 10 h. After centrifugation, washing with deionized water, and freeze-drying, composite particles with a particle size of 5-20 μm were obtained. Infrared detection showed that the carboxyl peak of graphene oxide was weakened, and characteristic peaks of amino and amide bonds appeared at the same time, which confirmed that the guanidine derivative was grafted onto graphene oxide.

[0033] Second, the composite particles prepared in the first step are melt-spun with PET polyester and auxiliaries to form polyester fibers. The spinning parameters are as follows: spinning temperature is 280℃, spinning speed is 1200m / min, stretching temperature is 75℃, and total stretching ratio is 4.

[0034] Example 2

[0035] The antibacterial polyester fiber for safety shoes includes composite particles, PET polyester and additives. By mass, the composite particles are 0.03%, the additives are 14%, and the remainder is PET polyester. The additives are lubricant, antioxidant, dispersant and toughening agent in a mass ratio of 5:2.2:3.2:5.

[0036] By weight, the composite particles comprise 85% copper powder, 12% graphene oxide, and 3% guanidine derivatives for sterilization.

[0037] The production method of antibacterial polyester fiber for safety shoes is as follows: including the following steps:

[0038] First, the preparation of composite particles

[0039] Graphene oxide was added to water at a ratio of 200 times its weight, stirred evenly, and then ultrasonically treated for 30 minutes. Anhydrous copper sulfate was then added according to the mass ratio of graphene oxide to copper powder and stirred evenly. The mixture was then sand-milled at a speed of 3500 r / min for 7 hours. The milled mixture was then spray-dried to obtain copper-supported composite particles at a spray-drying temperature of 200℃.

[0040] The copper-supported particles obtained above were subjected to coupling modification, wherein the coupling agent was EDC / NHS. Specifically, the copper-supported particles were mixed with water (1.4 mg / ml), and then EDC and NHS were added. The molar ratio of graphene oxide:EDC:NHS was 1:1.1:1.6. The reaction was carried out at room temperature for 45 min. Then, the guanidine derivative was added to the above reaction solution to adjust the pH to 6.5, and the reaction was carried out at room temperature for 12 h. After centrifugation, washing with deionized water, and freeze-drying, composite particles with a particle size of 5-20 μm were obtained.

[0041] Second, the composite particles prepared in the first step are melt-spun with PET polyester and auxiliaries to form polyester fibers. The spinning parameters are as follows: spinning temperature is 260℃, spinning speed is 1100m / min, stretching temperature is 70℃, and total stretching ratio is 3.

[0042] Example 3

[0043] The antibacterial polyester fiber for safety shoes includes composite particles, PET polyester and additives. By mass, the composite particles are 1%, the additives are 15%, and the remainder is PET polyester. The additives are lubricant, antioxidant, dispersant and toughening agent in a mass ratio of 5:1.8:3.7:6.

[0044] By weight, the composite particles comprise 86% copper powder, 10% graphene oxide, and 4% guanidine derivatives for sterilization.

[0045] The production method of antibacterial polyester fiber for safety shoes is as follows: including the following steps:

[0046] First, the preparation of composite particles

[0047] Graphene oxide was added to 180 times its weight of water, stirred evenly, and then ultrasonically treated for 35 minutes. Then, anhydrous copper sulfate was added according to the mass ratio of graphene oxide to copper powder and stirred evenly. The mixture was then sand-milled at a speed of 3200 r / min for 6 hours. The milled mixture was then spray-dried to obtain copper-supported composite particles at a spray-drying temperature of 180℃.

[0048] The copper-supported particles obtained above were subjected to coupling modification, with EDC / NHS as the coupling agent. Specifically, the copper-supported particles were mixed with water (1.6 mg / ml), and then EDC and NHS were added. The molar ratio of graphene oxide:EDC:NHS was 1:1.2:1.4. The mixture was reacted at room temperature for 25 min. Then, the guanidine derivative was added to the above reaction solution to adjust the pH to 6.5, and the mixture was reacted at room temperature for 14 h. After centrifugation, washing with deionized water, and freeze-drying, composite particles with a particle size of 5-20 μm were obtained.

[0049] Second, the composite particles prepared in the first step are melt-spun with PET polyester and auxiliaries to form polyester fibers. The spinning parameters are as follows: spinning temperature is 285℃, spinning speed is 1000m / min, stretching temperature is 75℃, and total stretching ratio is 4.

[0050] Comparative Example 1

[0051] Compared with Example 1, the difference is that in this example, no copper is loaded on graphene oxide, and particles formed by grafting guanidine derivatives onto graphene oxide with the same mass as the components in the composite particles, and separately molded copper powder are added to PET polyester in an alternating manner.

[0052] Comparative Example 2

[0053] Compared with Example 1, the difference is that in this example, the guanidine derivative is not grafted onto the copper-loaded particles, and the guanidine derivative and copper-loaded particles of corresponding mass to the components in the composite particles are added to the PET polyester alternately.

[0054] Comparative Example 3

[0055] Compared with Example 1, the difference is that copper powder, graphene oxide, and guanidine derivatives of the same mass as the components in the composite particles are added to the PET polyester in an alternating manner, without loading, grafting, or other steps.

[0056] The fibers prepared above were subjected to antibacterial testing in accordance with GB / T31402-2015. The test strains were Escherichia coli (ATCC8739) and Staphylococcus aureus (ATCC6538P), and the reaction time was 6 hours, as shown in Table 1.

[0057] Table 1

[0058]

[0059] As can be seen from the table above, the three-in-one composite particles in this example can significantly improve the antibacterial properties of polyester fibers. According to the test, when the content of this composite particle in the fiber is greater than 1.5%, it will have a significant impact on the mechanical properties of the fiber.

[0060] The above are merely preferred embodiments of the present invention. The scope of protection of the present invention is not limited to the above embodiments. All technical solutions falling within the scope of the present invention's concept are within the scope of protection of the present invention. It should be noted that for those skilled in the art, any improvements and modifications made without departing from the principle of the present invention should also be considered within the scope of protection of the present invention.

Claims

1. A method for producing antibacterial polyester fiber for safety shoes, characterized in that: Includes the following steps: First, the preparation of composite particles Copper-supported particles were obtained by mixing graphite oxide powder and a soluble salt of copper in a solvent and then spray-drying. These copper-supported particles were then coupled and grafted with a guanidine derivative used for sterilization to form composite particles. The guanidine derivative was a 2-aminoimidazolone type, and its specific structural formula is as follows: In the first step, graphene oxide powder is mixed with a solvent and ultrasonically treated. After adding copper sulfate, it is wet-milled and then spray-dried to obtain copper-supported particles. The copper sulfate is copper sulfate pentahydrate. The copper-supported particles are modified by a silane coupling agent or an EDC / NHS coupling system. The copper-supported particles are ultrasonically dispersed in water, EDC and NHS are added, and the reaction is carried out at room temperature for 15-30 min. Then, a guanidine derivative is added, the pH is adjusted, and the reaction is carried out at room temperature for 4-12 h. The particles are then centrifuged, washed, and dried to obtain composite particles. Second, the composite particles prepared in the first step are melt-spun with PET polyester and auxiliaries to form polyester fibers. By mass, the composite particles are 0.01-0.1%, the auxiliaries are 6-17%, and the remainder is PET polyester. The composite particles include 70-88% copper powder, 10-25% graphene oxide, and 2-7% guanidine derivatives for sterilization.

2. The production method as described in claim 1, characterized in that: The guanidine derivative is of the 2-aminoimidazolone type, and the adjuvants include lubricants, antioxidants, dispersants, and toughening agents, wherein the mass ratio of lubricants, antioxidants, dispersants, and toughening agents is 5:1-2.5:2-4:2-6.

3. The production method as described in claim 1, characterized in that: The spray drying temperature is 180-220℃, and the mass ratio of graphene oxide powder to solvent is 1:150-200.

4. The production method as described in claim 1, characterized in that: In the second step, the spinning temperature is 240-300℃, the spinning speed is 800-1600m / min, the stretching temperature is 60-80℃, and the total stretching ratio is 3-5.

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