Fabric fiber surface multifunctional coating preparation method and product

Abstract

The invention discloses a preparation method of a multifunctional coating on the surface of a fabric fiber, which comprises the following steps: contacting the fabric fiber with a coating liquid to form a stable functional nano coating on the surface of the fiber; the coating liquid is a mixed liquid of amyloid-like protein, a protein disulfide bond reducing agent and a functional antibacterial material. The invention also provides the modified fabric fiber obtained by the preparation method. On the basis of not destroying the molecular structure and the mechanical property of the fiber, the rapid multifunctional surface modification of the polyamide fiber can be realized, and the modified fiber shows better anti-pollution, antibacterial and skin-friendly properties.

Description

Technical Field

[0001] The invention relates to the technical field of nylon, and in particular to a fast, simple and damage-free method for preparing a multifunctional coating of fabric fibers. Background Art

[0002] The modification of nylon fiber can give it new functional properties and enhance its added value. At present, common methods for preparing functional fibers include copolymerization modification, blending modification and surface modification. Copolymerization modification requires complex chemical synthesis reactions and faces the problems of poor controllability and high cost. The blending modification process is relatively simple, but it will reduce the physical and mechanical properties of the fiber. In contrast, surface modification can achieve rapid multifunctionalization of fibers without destroying the molecular structure and mechanical properties of the fiber. However, existing surface modification technologies, such as plasma treatment, ultraviolet radiation, alkali reduction modification and aminolysis treatment, generally have the disadvantages of high energy consumption, high cost, complex process, single function and poor stability. Therefore, the development of a simple, efficient and stably adhered multifunctional coating has become the key to the preparation of high-performance functional fibers.

[0003] Surface modification coating is one of the simplest and most commonly used methods for surface treatment of functional materials. However, there are some problems with traditional surface modification systems, such as the modified surface or interface is brown or black, the polymerization process takes a long time (more than 10 hours), the biodegradability and compatibility of the cross-linked product are unclear, the coating has poor stability, and the coating surface or interface is relatively rough. These problems limit the practical application of modification systems such as polydopamine in the fiber field. Considering the actual needs of current technological development, the ideal material surface functionalization technology should have the following characteristics: strong adaptability, simple and efficient preparation method, green and environmentally friendly, mild, and controllable and diverse surface functions. Summary of the invention

[0004] In view of this, the present invention proposes a novel fiber surface functionalization strategy based on protein adhesion mechanism. A stable functionalized coating can be formed on the fiber surface simply by soaking the fiber at room temperature.

[0005] The technical problem to be solved by the present invention is that nylon fiber has poor stain resistance, poor hygroscopicity, is not as skin-friendly as natural fibers as underwear, and is prone to bacteria growth after sweating. At present, the modification of nylon has the disadvantages of complex modification process, poor coating stability, insufficient functionality, etc. The present invention performs a multifunctional coating modification treatment based on protein adhesion on the fiber to improve the antibacterial, stain-resistant and skin-friendly properties of the fiber, and has potential application prospects in the development of high-quality functional nylon fabrics.

[0006] A method for preparing a multifunctional coating on the surface of a fabric fiber comprises contacting the fabric fiber with a coating liquid to form a stable functional nano coating on the fiber surface; the coating liquid is a mixture of amyloid-like protein, a protein disulfide bond reducing agent, functional nanoparticles and a solvent.

[0007] The fiber has multiple functionalities such as anti-fouling, antibacterial, skin-friendly and the like after modification.

[0008] Furthermore, a method for preparing a multifunctional coating on a fabric fiber surface comprises the following steps:

[0009] Step 1: Take an amyloid protein aqueous solution, add a functional nanoparticle solution, and after 1-3 hours, add a protein disulfide bond reducing agent solution to obtain a coating solution for textile fibers;

[0010] Step 2: spray the prepared coating liquid onto the fabric fiber or immerse the fabric fiber in it, and dry it at 60-90° C. to obtain the fabric fiber with the multifunctional modified coating.

[0011] Preferably, the concentration of the amyloid protein aqueous solution is 0.05-0.1 g / L; the concentration of the functional nanoparticle solution is 0.01-0.05 g / L; and the concentration of the protein disulfide bond reducing agent solution is 0.005-0.02 g / L.

[0012] Preferably, the masses of amyloid-like protein, protein disulfide bond reducing agent, functional nanoparticles and textile fiber in the coating solution required for 100 g textile fiber are 1-10 mg, 0.1-1 mg and 0.01-0.1 mg respectively.

[0013] Preferably, the amyloid-like protein is selected from one or more proteins such as whey protein, lactoferrin, α-lactalbumin, bovine serum albumin, lysozyme, etc.

[0014] Furthermore, the protein disulfide bond reducing agent is selected from one or more of sodium borohydride, tris(2-carboxyethyl)phosphine, β-mercaptoethanol, 1,4-dithiothreitol and the like.

[0015] Furthermore, the functional nanoparticles can be inorganic powder materials such as zinc oxide and silver oxide, or high molecular weight antibacterial functional modified materials such as catechol, caffeic acid, catechin, 4-methylcatechol, or a mixture of the above materials.

[0016] Furthermore, the fabric fiber refers to one or more of polyester fiber, nylon fiber, polypropylene fiber, etc., or corresponding fiber filaments (such as drawn textured yarn (DTY), fully drawn yarn (FDY)).

[0017] Furthermore, the masses of amyloid protein, protein disulfide bond reducing agent, functional nanoparticles and textile fiber in the coating liquid required for 100g textile fiber are 1-6mg, 0.1-0.6mg and 0.03-0.1mg respectively; the textile fiber refers to polyester fiber; the functional nanoparticles are one or more of catechol, caffeic acid, catechin and 4-methylcatechol.

[0018] As a specific preference, the present invention provides a simple and rapid fiber coating finishing method, the method comprising the following steps:

[0019] The first step is to prepare the coating (impregnation) solution, and mix the whey protein phase conversion aqueous solution with catechol. Catechol reacts with whey protein, and their phenolic hydroxyl groups undergo oxidation reactions or combine through nucleophilic reactions to form quinone polymers. The cross-linking of catechol and whey protein can not only improve the film-forming properties and mechanical properties of the membrane material, but also has good antibacterial properties. Subsequently, sodium borohydride solution is added to continue the reaction. Sodium borohydride acts as a disulfide bond reducing agent, which causes the α-helical structure of whey protein to transform and aggregate into oligomers based on β-sheet stacking. This structural transformation makes it have the adhesion of mussel-like substances. The solution is arranged on nylon fiber by spraying or dipping, and the β-sheet stacking oligomers form a multifunctional protein coating on the fiber surface. The nylon fiber after the reaction is vacuum oven dried to finally obtain protein-coated nylon fiber.

[0020] Furthermore, a method for preparing a multifunctional coating on the surface of nylon fiber is provided, wherein the nylon fiber is immersed in a mixture of a whey protein phase transition aqueous solution, a catechol solution, and a disulfide bond reducing agent, sodium borohydride, to form a stable functional nano coating on the fiber surface at room temperature.

[0021] Furthermore, a method for preparing a multifunctional coating on a fabric fiber surface comprises the following steps:

[0022] Step 1: Take 30-100 mL of whey protein aqueous solution (0.05-0.1 g / L), add 5-15 mL of catechol (0.01-0.05 g / L), and after 1-3 hours, add 1-5 mL of sodium borohydride solution (0.005-0.02 g / L) to obtain a coating (impregnation) solution for nylon;

[0023] Step 2: Spray or immerse the above prepared solution on 50-100 g of nylon fiber, and dry it at 60-90° C. to obtain nylon fiber with a multifunctional modified coating.

[0024] A modified textile fiber is prepared by any of the methods described above.

[0025] In view of the shortcomings of the current nylon fiber surface functionalization strategy, such as complex modification process, poor coating stability, and insufficient functionality, a new fiber surface functionalization strategy based on stable protein adhesion is proposed. The nylon fiber is passed through a mixed solution containing a whey protein phase transition aqueous solution, a functional nanoparticle solution (such as a catechol solution), and a disulfide bond reducing agent (such as sodium borohydride), and a stable functionalized nano coating can be formed on the fiber surface at room temperature. The present invention can achieve rapid multifunctional surface modification of nylon fibers without destroying the molecular structure and mechanical properties of the fibers, and the modified fibers show good anti-fouling, antibacterial, and skin-friendly properties.

[0026] The beneficial technical effects of the present invention are:

[0027] The present invention performs multifunctional modification on nylon fiber. The finishing liquid can quickly and gently gather on the fiber surface under the action of the reducing agent to form a uniform coating. The coating can not only effectively inhibit bacteria for a long time, but also effectively improve the anti-fouling and skin-friendly properties of nylon fiber. The specific advantages are as follows:

[0028] (1) Long-lasting spectrum antibacterial property: As an effective and broad-spectrum antibacterial agent, catechol oxidation can release reactive oxygen species (ROS), and the presence of its hydroxyl groups can cause damage to bacterial proteins and cell membranes. The resulting coating material can completely eradicate Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus, MRSA, Enterococcus faecalis, and fungi (Candida albicans and Candida aureus). In addition, catechol is mostly extracted from a variety of plant species and will not cause drug resistance in microorganisms.

[0029] (2) Good skin-friendliness: Nylon fiber has a low water absorption rate, and water is difficult to be absorbed and conducted, resulting in poor hygroscopicity. It may feel stuffy and airtight when worn, which makes chemical fibers such as nylon have poor skin-friendliness. The fiber modified with protein coating is soft and comfortable, delicate in touch, breathable, and has good moisture permeability, providing a very comfortable wearing experience.

[0030] (3) Improved anti-fouling performance: The main reason why protein coatings can resist fouling is that the charged functional groups on their surface can bind to water molecules to form a hydration layer, thereby preventing other biological molecules such as proteins, enzymes and metabolites from adsorbing and depositing on their surface, thereby achieving an anti-fouling effect.

[0031] (3) Simple preparation process: In view of the shortcomings of the current polymer fiber surface functionalization strategy, which has complex modification process and poor coating stability, a new fiber surface functionalization strategy based on protein cross-linked catechol coating is proposed. This preparation process does not require high chemical reaction conditions and complex preparation process. The functional modification of the fiber can be achieved by dipping or spraying at room temperature, which has the potential for large-scale and low-cost. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 Figure 1. Antibacterial test results of unmodified fiber (a is Staphylococcus aureus and b is Escherichia coli); Figure 2 Example 1: Antibacterial test results of modified fibers (a is Staphylococcus aureus and b is Escherichia coli);

[0033] Figure 3 The results of the ink drop test on the unmodified fabric (left); The results of the ink drop test on the modified fabric (right);

[0034] Figure 4 Stain resistance test results of modified and unmodified fibers. DETAILED DESCRIPTION

[0035] The sources of materials in the embodiments are shown in the following table:

[0036] materials source Whey protein Shanghai MacLean Biochemical Technology Co., Ltd. Nylon fiber Yiwu Huading Nylon Co., Ltd. BSA Shanghai MacLean Biochemical Technology Co., Ltd.

[0037] The specific method for testing Staphylococcus aureus and Escherichia coli in the embodiment is as follows:

[0038] Staphylococcus aureus and Escherichia coli testing - colony count method

[0039] Wash the nylon fiber with deionized water to remove the oil and impurities on the surface of the nylon fiber, then cut it into small pieces, weigh 0.1g of the sample, and sterilize it in an autoclave (121℃) for 180min for later use. 3 CFU / mL concentration, put the sample into the bacterial solution, shake and culture at a rate of 150r / min for 18h, and set the temperature to 24℃. In a 24-well culture plate, add 900μL PBS buffer to 100μL fiber / bacteria solution and perform gradient dilutions of different concentrations to prepare concentrations of 10 3 CFU / mol, 10 2 CFU / mL concentration of bacterial solution (multi-layer gradient is used to find the optimal bacterial solution concentration). The final bacterial wave concentration tested in this experiment is 10 2 CFU / mL. Inject the bacterial solution into the nutrient agar culture dish and spread it evenly with a glass coating rod. Incubate in a water-tight constant temperature incubator for 24 hours. After the experiment is completed, count the colonies and calculate the inhibition rate using the formula.

[0040]

[0041] Where: Y is the antibacterial rate of the sample; A is the colony count of the pure sample; B is the colony count of the sample. According to the national standard, if the antibacterial rate against E. coli and S. aureus is higher than 70%, it means that the sample has an antibacterial effect.

[0042] The specific method for testing the stain resistance of the fabric made of the fiber in the embodiment is as follows:

[0043] Fabric anti-fouling performance test - washing method (

[0044] Cut at least 5 samples of 10cm×10cm from the fabric to be tested. Condition the samples for at least 4 hours under standard atmospheric conditions (temperature 20±2℃, humidity 65±4%). Use standard oil stains (specific oils in GB / T19977) or other liquid dyes (such as coffee, tea, juice, etc.). Use a burette or pipette to drop 0.1mL-0.2mL of pollutants to the center of the sample surface, and let it stand for 30s-5min. This experiment uses WSD-3C fully automatic whiteness colorimeter (Beijing Instrument Kangguang Optical Instrument) to detect the L*, a*, b* and CIE whiteness value (W) of the contaminated fabric.

[0045] Before and after washing. During the test, the wavelength of the light source is 360-700nm, and the sample is measured at least 5 times to obtain the average value. Calculate the corresponding degree of decontamination (D)

[0046] According to equation (1):

[0047]

[0048] Where ΔE represents color difference, L* represents brightness, a* represents color components in the red and green directions, and b* represents color components in the yellow and blue directions. The subscript W represents the stained area after washing, and S and B represent the stained area and blank area of ​​fabric before washing, respectively.

[0049] The specific method for detecting the hydrophilicity of the fabric in the embodiment is as follows:

[0050] Fabric hydrophilicity test method - droplet diffusion method (refer to AATCC 79:1995)

[0051] Cut a fabric sample of 10cm×10cm size, make sure the sample is free of stains and wrinkles, dry the treated fabric first, and then balance it in a standard environment (relative humidity of 65±2%, temperature of 21±1℃) for 24 hours. Test under standard environment. Fix the fabric to the mouth of the beaker with a rope or rubber band so that it is wrinkle-free and twist-free. Make the beaker mouth about 1.0±0.1cm away from the tip of the burette, and drop a drop of blue ink (21±3℃) on the surface of the fabric. Immediately use a stopwatch to time and record the time required for the mirror reflection of the water drop to disappear. Measure 5 representative points on the fabric surface and take the average value. The shorter the average time, the better the hydrophilicity of the fabric. Less than 5 seconds means that the hydrophilicity of the fabric is particularly good.

[0052] Embodiment 1:

[0053] Take 50mL of whey protein aqueous solution (0.06g / L), add 10mL of catechol aqueous solution (0.03g / L), react at room temperature for 1 hour, and then add 5mL of sodium borohydride aqueous solution (0.01g / L). The above prepared solution was impregnated on 100g of nylon fiber (about 5 minutes, the same as other embodiments), and dried at 70℃ for 1 hour to obtain functional modified fiber. The cross-linked protein modified fiber was tested for Staphylococcus aureus and Escherichia coli, and the results are as follows: Figure 1 and Figure 2 The results show that the antibacterial properties of the fibers are greater than 85%. The antifouling properties of the fabrics made of the fibers were tested, and the antifouling properties of the modified fibers were significantly improved, such as Figure 4 As shown. The fabric has better hydrophilicity, such as Figure 3 As shown, the skin-friendliness of nylon fibers and fabrics is ultimately improved.

[0054] Embodiment 2:

[0055] Take 50mL of bovine serum albumin solution (0.06g / L), add 10mL of catechol (0.03g / L), react at room temperature for 1 hour, then add 5mL of sodium borohydride solution (0.01g / L). The above prepared solution is impregnated on 100g of nylon fiber, and dried at 70℃ for 1 hour to obtain functional modified fiber.

[0056] Embodiment 3:

[0057] Take 50 mL of whey protein aqueous solution (0.06 g / L), add 10 mL of caffeic acid (0.03 g / L), react at room temperature for 1 hour, then add 5 mL of sodium borohydride solution (0.01 g / L). The prepared solution is impregnated on 100 g of nylon fiber, and dried at 70°C for 1 hour to obtain functional modified fiber.

[0058] Embodiment 4:

[0059] Take 50mL of whey protein aqueous solution (0.06g / L), add 10mL of caffeic acid (0.03g / L), react at room temperature for 1 hour, then add 5mL of β-mercaptoethanol solution (0.01g / L). The prepared solution is impregnated on 100g of nylon fiber, and dried at 70°C for 1 hour to obtain functional modified fiber.

[0060]

[0061] Comparative Example 1:

[0062] Take 50mL of whey protein aqueous solution (0.06g / L), add 5mL of sodium borohydride solution (0.01g / L). The solution prepared above is impregnated on 100g of nylon fiber, and dried at 70℃ for 1 hour to obtain functional modified fiber. The obtained protein modified fiber has poor film-forming property, the utilization rate of protein film is less than 30%, and a large number of large particle protein aggregates are produced in the bulk phase.

[0063] Comparative Example 2:

[0064] 50 mL of catechol (0.03 g / L) was taken and the solution was impregnated on 100 g of nylon fiber, and then dried at 70° C. for 1 hour to obtain comparative fiber. Since catechol and fiber cannot be directly cross-linked, the fiber has no functionality.

Claims

1. A method for preparing a multifunctional coating on a fabric fiber surface, characterized in that: The fabric fiber is brought into contact with a coating liquid to form a stable functionalized nano coating on the fiber surface; the coating liquid is a mixture of amyloid-like protein, a protein disulfide bond reducing agent, functional nano particles and a solvent.

2. The method for preparing a multifunctional coating on a fabric fiber surface according to claim 1, characterized in that: The steps include: Step 1: Take an amyloid protein aqueous solution, add a functional nanoparticle solution, and after 1-3 hours, add a protein disulfide bond reducing agent solution to obtain a coating solution for textile fibers; Step 2: spray the prepared coating liquid onto the fabric fiber or immerse the fabric fiber in it, and dry it at 60-90° C. to obtain the fabric fiber with the multifunctional modified coating.

3. The method for preparing a multifunctional coating on a fabric fiber surface according to claim 2, characterized in that: The concentration of the amyloid protein aqueous solution is 0.05-0.1 g / L; the concentration of the functional nanoparticle solution is 0.01-0.05 g / L; and the concentration of the protein disulfide bond reducing agent solution is 0.005-0.02 g / L.

4. The method for preparing a multifunctional coating on a textile fiber surface according to claim 1, characterized in that: The masses of the amyloid protein, the protein disulfide bond reducing agent, the functional nanoparticles and the textile fiber in the coating liquid required for 100g of textile fiber are 1-10mg, 0.1-1mg and 0.01-0.1mg respectively.

5. The method for preparing a multifunctional coating on a textile fiber surface according to claim 1, characterized in that: The amyloid-like protein is selected from one or more of whey protein, lactoferrin, α-lactalbumin, bovine serum albumin, and lysozyme.

6. The method for preparing a multifunctional coating on a textile fiber surface according to claim 1, characterized in that: The protein disulfide bond reducing agent is selected from one or more of sodium borohydride, tris(2-carboxyethyl)phosphine, β-mercaptoethanol, and 1,4-dithiothreitol.

7. The method for preparing a multifunctional coating on a textile fiber surface according to claim 1, characterized in that: The functional nanoparticles are selected from one or more of zinc oxide, silver oxide, catechol, caffeic acid, catechin, and 4-methylcatechol.

8. The method for preparing a multifunctional coating on a textile fiber surface according to claim 1, characterized in that: The fabric fiber refers to one or more of polyester fiber, nylon fiber, polypropylene fiber, or their corresponding stretched textured yarns and fully stretched yarns.

9. The method for preparing a multifunctional coating on a textile fiber surface according to claim 1, characterized in that: The masses of amyloid protein, protein disulfide bond reducing agent, functional nanoparticles and textile fiber in the coating liquid required for 100g textile fiber are 1-6mg, 0.1-0.6mg and 0.03-0.1mg respectively; the textile fiber is polyester fiber; the functional nanoparticles are one or more of catechol, caffeic acid, catechin and 4-methylcatechol.

10. A modified textile fiber, characterized in that: The method is prepared by any one of claims 1 to 9.

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