CN115162007B - Self-crosslinking type antibacterial ultraviolet-proof finishing agent for textiles and preparation method thereof - Google Patents
Self-crosslinking type antibacterial ultraviolet-proof finishing agent for textiles and preparation method thereof Download PDFInfo
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- CN115162007B CN115162007B CN202210992192.3A CN202210992192A CN115162007B CN 115162007 B CN115162007 B CN 115162007B CN 202210992192 A CN202210992192 A CN 202210992192A CN 115162007 B CN115162007 B CN 115162007B
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/59—Polyamides; Polyimides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/48—Polymers modified by chemical after-treatment
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/32—Polyesters
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/25—Resistance to light or sun, i.e. protection of the textile itself as well as UV shielding materials or treatment compositions therefor; Anti-yellowing treatments
Abstract
The invention discloses a self-crosslinking type antibacterial ultraviolet-proof finishing agent for textiles and a preparation method thereof, and belongs to the technical field of functional textiles. According to the invention, firstly, through condensation reaction between carboxyl and amino, amino on polylysine and carboxyl on levodopa are utilized to graft the levodopa on the polylysine, so as to obtain a polylysine solution containing dopa side groups; then adding silver nitrate into the solution of the polylysine containing the dopa side group, generating nano silver on the polylysine containing the dopa side group in situ through the reducibility and the adhesiveness of the dopa group, and firmly combining the nano silver with the nano silver to obtain the antibacterial ultraviolet-proof finishing agent of the polylysine/nano silver complex containing the dopa side group; and finally, spontaneously forming a firm network-shaped adhesive coating on the surface of the fabric by utilizing an antibacterial ultraviolet-proof finishing agent containing the polylysine/nano silver complex with the dopa side group, wherein the polylysine and the nano silver jointly endow the fabric with excellent antibacterial performance, and the benzene ring structure in the dopa structure endows the fabric with ultraviolet-proof performance.
Description
Technical Field
The invention relates to a self-crosslinking type antibacterial ultraviolet-proof finishing agent for textiles and a preparation method thereof, belonging to the technical field of functional textiles.
Background
Textiles are closely related to people's life and are one of direct or indirect vehicles for the transmission of microorganisms. Since the human body has a temperature, food, living environment, etc. required for growth and reproduction of microorganisms, a part of microorganisms are propagated in large amounts under appropriate conditions, and serious diseases or abnormal skin irritation are caused to cause unpleasant sensation. To prevent such problems, people have begun to perform antimicrobial finishing on textiles. Antibacterial finishing is generally to treat fiber products with processing aids having antibacterial capabilities, which not only inhibit the deterioration of textiles under the action of microorganisms, but also ensure that microorganisms living with sweat and dirt as nutrient sources are inhibited from propagating when taken.
The common antibacterial agents are inorganic, organic and natural products; wherein the inorganic antibacterial agent comprises antibacterial zeolite, silver silicate, phosphate, etc.; the organic antibacterial agent comprises organosilicon quaternary ammonium salt, parachlorometacresol, copper polyacrylate and the like; natural product based antimicrobial agents include some plant based extracts such as: mugwort, aloe, licorice, tea, etc.; animal extracts: chitin, chitosan, insect-antibacterial proteins, and the like.
At present, the method for performing antibacterial modification on the textile mainly comprises an blended yarn method, a coating method, a grafting modification method and the like. The blending spinning method is to add an antibacterial agent during fiber spinning, mix the antibacterial agent with spinning solution, and obtain antibacterial fibers or filaments through spinning. The coating method is to carry out coating after-treatment on the fabric, fix the antibacterial agent on the surface of the fabric and endow the fabric with antibacterial performance. The graft modification method is a processing method of grafting a substance having an antibacterial effect on the surface of a fabric through a chemical reaction. From these methods, it can be seen that: the antibacterial modification of the textile is carried out in the textile processing links, such as spinning, dyeing and finishing, after finishing and other procedures, and the textile antibacterial agent which is convenient for consumers is lacked.
Therefore, with the increase of the demands of people on textile antibiosis, the textile antibiosis agent which is convenient to use and efficient for bacteriostasis has good application prospect.
Disclosure of Invention
[ technical problem ]
The technical problem to be solved in practice is to provide the self-crosslinking antibacterial ultraviolet-proof finishing agent for the textiles, which can endow the textiles with excellent antibacterial and ultraviolet-proof performances by self-crosslinking and fixing on the surfaces of the textiles through simple dipping or spraying without using other chemical reagents, and can still keep excellent antibacterial and ultraviolet-proof performances after washing for many times.
Technical scheme
In order to solve the problems, the invention provides a method for preparing an antibacterial and ultraviolet-proof finishing agent for self-crosslinking textiles, which comprises the steps of firstly grafting levodopa to polylysine by utilizing amino groups on the polylysine and carboxyl groups on the levodopa through condensation reaction between carboxyl groups and amino groups to obtain a polylysine solution containing dopa side groups; then adding silver nitrate into the solution of the polylysine containing the dopa side group, generating nano silver on the polylysine containing the dopa side group in situ through the reducibility and the adhesiveness of the dopa group, and firmly combining the nano silver with the nano silver to obtain the antibacterial and ultraviolet-proof finishing agent of the polylysine/nano silver compound containing the dopa side group; finally, spontaneous Schiff base or Michael addition reaction between the quinone formed by oxidation of the dopa group and the polylysine amino is utilized, the antibacterial ultraviolet-proof finishing agent containing the polylysine/nano silver complex with the dopa side group can spontaneously form a firm network-shaped adhesive coating on the surface of the fabric, wherein the polylysine and the nano silver jointly endow the fabric with excellent antibacterial performance, and the benzene ring structure in the dopa structure endows the fabric with ultraviolet-proof performance.
A first object of the present invention is to provide a method for preparing a self-crosslinking antimicrobial uv-protective finish for textiles, comprising the steps of:
(1) Preparation of solution of polylysine containing DOPA side group
Adding levodopa and carbodiimide hydrochloride into a polylysine solution, performing condensation reaction, and grafting the levodopa on a polylysine macromolecular chain through the reaction of amino groups on the polylysine and carboxyl groups on the levodopa to prepare a polylysine solution containing a dopa side group;
(2) Preparation of self-crosslinking antibacterial ultraviolet-proof finishing agent for textiles
Adding silver nitrate into the poly-lysine solution containing the dopa side group obtained in the step (1), and reducing the poly-lysine containing the dopa side group in situ to generate nano silver through the reducibility and adhesiveness of the dopa group, so as to prepare the antibacterial finishing agent containing the dopa side group poly-lysine/nano silver complex, namely the self-crosslinking textile antibacterial anti-ultraviolet finishing agent solution.
In one embodiment of the present invention, the concentration of the polylysine solution in step (1) is 5-50 g/L; the solvent is phosphate buffer solution, and the pH range is 5.5-6.5.
In one embodiment of the invention, the polylysine of step (1) has a molecular weight of 2000-5000 Da.
In one embodiment of the present invention, the mass ratio of polylysine to levodopa in step (1) is 5:1-30:1.
In one embodiment of the present invention, the concentration of L-dopa in the polylysine solution described in step (1) is 1-10 g/L.
In one embodiment of the present invention, the concentration of carbodiimide hydrochloride described in step (1) in the polylysine solution is 0.5-4 g/L.
In one embodiment of the present invention, the condensation reaction conditions in step (1) are a temperature of 20 to 40 ℃ and a constant temperature oscillator for 0.5 to 12 hours.
In one embodiment of the invention, the concentration of silver nitrate in the solution of poly-lysine containing dopa side groups in step (2) is 0.1 to 0.5g/L.
In one embodiment of the invention, the reaction condition of in-situ reduction to form nano silver on the polylysine containing the dopa side group in the step (2) is that the pH range is 8.0-8.5, and the reaction is carried out for 4-10 hours at room temperature (20-30 ℃).
In one embodiment of the invention, the concentration of the self-crosslinking textile antibacterial and anti-ultraviolet finishing agent solution in the step (2) is 5-50 g/L.
The second purpose of the invention is to prepare the self-crosslinking type antibacterial ultraviolet-proof finishing agent for textiles.
The third object of the invention is to provide a method for preparing the antibacterial ultraviolet-proof dual-function fabric by using the self-crosslinking antibacterial ultraviolet-proof finishing agent for textiles, wherein the method is to deposit the self-crosslinking antibacterial ultraviolet-proof finishing agent solution for the self-crosslinking textile on the surface of the fabric by adopting an immersion method or a spraying method, so as to obtain the antibacterial ultraviolet-proof dual-function fabric.
In one embodiment of the present invention, the impregnation method specifically includes;
soaking the fabric in a self-crosslinking antibacterial ultraviolet-proof finishing agent solution for textiles, spontaneously crosslinking and depositing the finishing agent on the surface of the fabric, and washing and drying after the soaking is finished to obtain an antibacterial ultraviolet-proof dual-function fabric; wherein the mass ratio of the fabric to the self-crosslinking textile antibacterial ultraviolet-proof finishing agent solution is 1:5-1:50, the dipping temperature is 20-60 ℃, the pH is 8.0-8.5, and the dipping time is 1-60 minutes; after the impregnation is finished, the water washing is carried out, and then the water washing is carried out, and the water washing is dried at room temperature or is dried at 60-100 ℃.
In one embodiment of the present invention, the spraying method specifically includes:
spraying a self-crosslinking antibacterial ultraviolet-proof finishing agent solution of the textile on the surface of the fabric, spontaneously crosslinking and depositing the finishing agent on the surface of the fabric, and drying to obtain an antibacterial ultraviolet-proof dual-function fabric; wherein the mass ratio of the finishing agent solution to the fabric is 1:10-1:100, and the fabric is dried at room temperature or at 60-100 ℃ after being sprayed.
In one embodiment of the present invention, the fabric includes any one of cotton, hemp, mulberry silk, wool, terylene, nylon, knitted fabric, filling material, non-woven fabric, clothing, apparel, home textile, ornament and medical and health products.
The fourth purpose of the invention is to obtain the antibacterial ultraviolet-proof double-function fabric.
The invention provides an antibacterial ultraviolet-proof finishing method for fabrics, which is to modify and finish the fabrics by adopting the self-crosslinking antibacterial ultraviolet-proof finishing agent for textiles.
The sixth object of the invention is the application of the self-crosslinking textile antibacterial ultraviolet-proof finishing agent and the antibacterial ultraviolet-proof dual-function fabric in textiles for clothing, household textiles, ornaments and medical and health products.
[ advantageous effects ]
According to the invention, the polylysine side group is modified, the dopa side group is introduced, so that the polylysine has adhesiveness and reducibility, and then the polylysine is used for in-situ reduction of silver nitrate to form the antibacterial ultraviolet-proof finishing agent containing the polylysine/nano silver complex of the dopa side group, and the antibacterial and ultraviolet-proof effects are given to textiles by adopting a dipping or spraying finishing agent mode.
Compared with the traditional antibacterial and ultraviolet-proof finishing method for textile products such as functional finishing agent, coating, grafting modification and the like added in spinning, the invention has the following advantages:
(1) The antibacterial ultraviolet-proof finishing agent has simple preparation process and mild conditions: in the preparation process of the anti-bacterial ultraviolet-proof finishing agent containing the dopa side group polylysine/nano silver complex, main reagents are polylysine, levodopa, carbodiimide hydrochloride and silver nitrate, the reaction is carried out in aqueous solution, the operation is simple, a high-temperature high-pressure reactor is not needed, the reaction pH value is weak acid or weak alkaline, the reaction temperature is 20-40 ℃, and the condition is mild.
(2) The use method of the antibacterial ultraviolet-proof finishing agent is simple: the application method of the anti-bacterial ultraviolet-proof finishing agent containing the poly-lysine/nano-silver complex with the dopa side group is simple, the finishing agent solution is soaked or sprayed on the surface of the fabric, and the anti-bacterial and ultraviolet-proof modification of the textile can be finished by airing or drying at room temperature, and professional equipment and personnel are not needed in the application process.
(3) The antibacterial ultraviolet-proof textile has good fastness: the anti-bacterial ultraviolet-proof finishing agent containing the poly-lysine/nano-silver complex with the dopa side group has self-crosslinking performance, and the antibacterial textile obtained by modification of the finishing agent has good washing fastness and durable antibacterial effect.
(4) The antibacterial ultraviolet-proof finishing agent is safe and environment-friendly: the invention does not use adhesives, organic solvents and the like, and does not generate substances harmful to human bodies in the processing or taking process, thereby ensuring the safety and environmental protection of fabrics from the source.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for better illustration of the invention, and should not be construed as limiting the invention.
The testing method comprises the following steps:
1. antibacterial effect test: the method comprises the steps of selecting gram-negative bacteria such as escherichia coli and gram-positive bacteria such as staphylococcus aureus as experimental strains, and referring to GB/T20944.3-2008 part 3 of evaluation of antibacterial properties of textiles: the vibration method evaluates the antibacterial effect of the textile.
2. Wash fastness test:
according to GB/T12490-2014 'fastness to washing of textiles in families and business' test of color fastness to washing, soap solution with the mass concentration of 4g/L is prepared by using ECE phosphorus-containing detergents, and after the prepared antibacterial fabric is washed for 20 times under the operation procedure of A1M, the antibacterial effect is tested, and the fastness to washing is evaluated.
3. Ultraviolet resistance test:
the UPF value of the sample was tested using a YG (B) 912E fabric uv resistance tester.
4. Air and moisture permeability test:
the air permeability of the fabric is measured by using a YG461E-III full-automatic fabric air permeability meter, and the air permeability of the fabric is expressed by air permeability (mm/s);
according to GB/T12704.1-2009 part 1 of the textile fabric moisture permeability test method: moisture absorption method is used for moisture permeability test.
The raw materials used in the examples:
cotton fabric: pure cotton twill woven cloth, 120g/m 2 ；
Polyester fabric: pure polyester woven cloth, 80g/m 2 ；
Polylysine: molecular weight 2000-5000 Da, purity more than or equal to 95%.
Example 1
A method for preparing a self-crosslinking antibacterial ultraviolet-proof finishing agent for textiles, comprising the following steps:
(1) Preparation of polylysine containing dopa side group
Preparing a polylysine solution with the concentration of 20g/L by using phosphate buffer solution with the pH of 6.5; then adding 1g/L of levodopa and 1g/L of carbodiimide hydrochloride into the polylysine solution, and placing the mixture in a constant-temperature oscillator at 30 ℃ for condensation reaction for 6 hours; preparing a polylysine solution containing dopa side groups;
(2) Preparation of self-crosslinking antibacterial ultraviolet-proof finishing agent for textiles
Adding 0.1g/L of silver nitrate into the solution (20 g/L) containing the dopa side group polylysine obtained in the step (1), regulating the pH to 8.5, and treating for 5 hours at room temperature to prepare the antibacterial ultraviolet-proof finishing agent containing the dopa side group polylysine/nano silver complex, namely the self-crosslinking textile antibacterial ultraviolet-proof finishing agent solution (20 g/L).
Example 2
A method for preparing a self-crosslinking antibacterial ultraviolet-proof finishing agent for textiles, comprising the following steps:
(1) Preparation of polylysine containing dopa side group
Preparing a polylysine solution with the concentration of 50g/L by using phosphate buffer solution with the pH of 6.0; then adding 2g/L of levodopa and 3g/L of carbodiimide hydrochloride into the polylysine solution, and placing the mixture in a constant-temperature oscillator at 40 ℃ for condensation reaction for 12 hours; preparing a polylysine solution containing dopa side groups;
(2) Preparation of self-crosslinking antibacterial ultraviolet-proof finishing agent for textiles
Adding 0.4g/L of silver nitrate into the solution (50 g/L) containing the dopa side group polylysine obtained in the step (1), regulating the pH to 8, and treating at room temperature for 6 hours to obtain the antibacterial ultraviolet-proof finishing agent solution (50 g/L) containing the dopa side group polylysine/nano silver complex, namely the self-crosslinking textile antibacterial ultraviolet-proof finishing agent solution.
Example 3
A method for preparing an antibacterial and anti-ultraviolet dual-function cotton fabric by using the self-crosslinking textile antibacterial and anti-ultraviolet finishing agent of the embodiment 1, comprising the following steps:
1g of cotton fabric is added into 20mL of the self-crosslinking textile antibacterial ultraviolet-proof finishing agent solution prepared in the embodiment 1 for soaking, the soaking temperature is 30 ℃, the pH is 8.5, the soaking time is 10 minutes, after the soaking is finished, the cotton fabric is taken out, and the cotton fabric is dried at 60 ℃ after washing, so that the antibacterial ultraviolet-proof dual-function cotton fabric is obtained.
Example 4
A method for preparing an antibacterial and anti-ultraviolet dual-function cotton fabric by using the self-crosslinking textile antibacterial and anti-ultraviolet finishing agent of the embodiment 1, comprising the following steps:
and (3) taking 0.5mL of the self-crosslinking type textile antibacterial ultraviolet-proof finishing agent solution prepared in the embodiment 1, spraying the self-crosslinking type textile antibacterial ultraviolet-proof finishing agent solution on the surface of 1g of cotton fabric, and naturally airing to obtain the antibacterial ultraviolet-proof dual-function cotton fabric.
Example 5
A method for preparing an antibacterial and anti-ultraviolet dual-function polyester fabric by using the self-crosslinking textile antibacterial and anti-ultraviolet finishing agent of the embodiment 2, comprising the following steps:
1g of polyester fabric is added into 10mL of the self-crosslinking textile antibacterial ultraviolet-proof finishing agent solution prepared in the embodiment 2 for soaking, the soaking temperature is 40 ℃, the pH is 8.0, the soaking time is 5 minutes, after the soaking is finished, the polyester fabric is taken out, washed by water and dried at room temperature, and the antibacterial ultraviolet-proof dual-function polyester fabric is obtained.
Example 6
A method for preparing an antibacterial and anti-ultraviolet dual-function polyester fabric by using the self-crosslinking textile antibacterial and anti-ultraviolet finishing agent of the embodiment 2, comprising the following steps:
1mL of the self-crosslinking type antibacterial ultraviolet-proof finishing agent solution for textiles, which is prepared in example 2, is sprayed on the surface of 5g of polyester fabric, and is dried at 60 ℃ to obtain the antibacterial ultraviolet-proof dual-function polyester fabric.
Comparative example 1 omits silver nitrate
A method for preparing an antibacterial anti-ultraviolet double-function cotton fabric, comprising the following steps:
(1) Preparation of polylysine containing dopa side group
Preparing a polylysine solution with the concentration of 20g/L by using phosphate buffer solution with the pH of 6.5; then adding 1g/L of levodopa and 1g/L of carbodiimide hydrochloride into the polylysine solution, and placing the mixture in a constant-temperature oscillator at 30 ℃ for condensation reaction for 6 hours; preparing a polylysine solution containing dopa side groups;
(2) Impregnating cotton fabric:
1g of cotton fabric is added into 20mL of solution containing dopa side group polylysine with concentration of 20g/L for impregnation, the temperature of impregnation is 30 ℃, the pH is 8.5, the impregnation time is 10 minutes, after the impregnation is finished, the cotton fabric is taken out, and the cotton fabric is dried at 60 ℃ after washing to obtain the antibacterial anti-ultraviolet dual-function cotton fabric.
Comparative example 2 omitting silver nitrate
The method for preparing the antibacterial anti-ultraviolet dual-function polyester fabric comprises the following steps of:
(1) Preparation of polylysine containing dopa side group
Preparing a polylysine solution with the concentration of 50g/L by using phosphate buffer solution with the pH of 6.0; then adding 2g/L of levodopa and 3g/L of carbodiimide hydrochloride into the polylysine solution, and placing the mixture in a constant-temperature oscillator at 40 ℃ for condensation reaction for 12 hours; preparing a polylysine solution containing dopa side groups;
(2) Spraying polyester fabric:
and (3) spraying 1mL of a solution containing the dopa side group polylysine with the concentration of 50g/L on the surface of 5g of polyester fabric, and drying at 60 ℃ to obtain the antibacterial ultraviolet-resistant dual-function polyester fabric.
Comparative example 3 omitting Levodopa
Omitting levodopa from example 1, otherwise consistent with example 1, to give a textile finish solution; an antibacterial uv-protective bifunctional cotton fabric was then prepared as in example 3.
Comparative example 4 omitting Levodopa
Omitting levodopa from example 2, otherwise consistent with example 2, to give a textile finish solution; then, the antibacterial and ultraviolet-proof dual-functional polyester fabric was prepared according to the method of example 6.
The fabric samples of examples 3 to 6 and comparative examples 1 to 4 were subjected to antibacterial and ultraviolet-proof performance tests, and the results are shown in table 1.
TABLE 1
As can be seen from table 1: the antibacterial ultraviolet-resistant difunctional fabrics prepared by the method have the antibacterial rate of more than 95% on escherichia coli and staphylococcus aureus in examples 3, 4, 5 and 6, and the antibacterial rate is kept to be more than 90% after 20 times of washing, so that the antibacterial ultraviolet-resistant difunctional fabrics have good washing fastness, and in addition, the following can be seen: the self-crosslinking type antibacterial ultraviolet-proof finishing agent for textiles can obtain better antibacterial effect by treating fabrics by adopting an impregnation method and a spraying method; the antibacterial rates of the comparative example 1 and the comparative example 2 are lower than those of the examples, which shows that the antibacterial performance of the solution containing the dopa side group polylysine is weaker than that of the solution containing the dopa side group polylysine/nano silver complex, and the in-situ generation and combination of nano silver on the polylysine containing the dopa side group are the key of the efficient antibacterial of the antibacterial agent of the invention; the comparative examples 3 and 4 have a bacteriostasis rate of more than 86% on escherichia coli and staphylococcus aureus, show a certain antibacterial property, but after 20 times of washing, the bacteriostasis rate of the fabric is reduced to 60% -70%, and the fact that the binding fastness of the polylysine obtained by the polylysine without the dopa side group on the surface of the fabric is poor indicates that the polylysine side group is modified, so that the polylysine side group has self-crosslinking property, and is the key of the antibacterial ultraviolet-resistant finishing agent with good washing fastness.
In addition, from the ultraviolet resistance test results in table 1, it can be seen that: the UPF values of the examples 3, 4, 5 and 6 are all greater than 50 and still greater than 50 after 20 times of washing, which shows that the difunctional fabrics of the examples 3 to 6 have good ultraviolet resistance and washing fastness. The UPF values of comparative example 1 and comparative example 2 are greater than 50, indicating that the UV protection performance of the fabric is independent of nano-silver. The UPF value of comparative example 3 is 8 and the UPF value of comparative example 4 is 22, indicating that the incorporation of dopa groups in the polylysine structure is critical for the UV protection properties of the finish.
The air and moisture permeability of the unmodified cotton fabric, the polyester fabric and examples 3, 4, 5 and 6 were tested, and the results are shown in table 2.
TABLE 2
As can be seen from table 2: compared with the unmodified cotton fabric and the unmodified polyester fabric, the air permeability of the examples 3, 4, 5 and 6 is unchanged, which shows that the finishing agent and the finishing method prepared by the invention can not block pores in the fabric and do not influence the air permeability of the fabric. In addition, it can be seen from the moisture permeability results of example 5 and example 6 that: compared with unmodified polyester fabric, the antibacterial ultraviolet-proof finishing agent prepared by the invention has the advantage that the moisture permeability of the polyester fabric is greatly improved after being modified. The finishing agent contains a large number of hydrophilic groups of amino and hydroxyl, so that the hydrophobic polyester fabric is endowed with good moisture permeability and moisture permeability, and the wearing comfort of the fabric is improved.
Comparative example 5 polylysine having too large a molecular weight
The polylysine (molecular weight 2000-5000 Da) in example 1 was replaced with polylysine (molecular weight 100000 Da), and the other conditions were kept the same as in example 1 to obtain a textile finishing agent; an antibacterial uv-protective bifunctional cotton fabric was then prepared as in example 3.
The performance test is carried out on the obtained difunctional cotton fabric, and the test results are as follows:
the antibacterial rate of the difunctional cotton fabric of the comparative example 5 on escherichia coli is 96%, the antibacterial rate on staphylococcus aureus is 95%, but the antibacterial rate is reduced to 75% and 68% after 20 times of water washing, which shows that the selection of proper polylysine molecular weight is the key of the invention, and the polylysine molecular weight is large, so that the construction of the antibacterial ultraviolet-proof self-crosslinking coating is not facilitated.
Comparative example 6 too little Levodopa
The amount of L-dopa in example 1 was adjusted to 0.5g/L, and the other conditions were kept the same as in example 1 to obtain a textile finishing agent; an antibacterial uv-resistant cotton fabric was then prepared as in example 3.
The performance test is carried out on the obtained difunctional cotton fabric, and the test results are as follows:
the antibacterial rate of the difunctional cotton fabric of the comparative example 6 on escherichia coli is 85%, the antibacterial rate on staphylococcus aureus is 88%, and the antibacterial rate is reduced to 65% and 60% after 20 times of water washing, which shows that the use amount of levodopa is too low, and the antibacterial property and the fastness of the modified fabric are obviously reduced. The proper dosage of the levodopa is the key of the invention, and the little levodopa is unfavorable for the in-situ reduction of nano silver and the formation of the self-crosslinking network antibacterial ultraviolet-proof coating.
Comparative example 7 excessive Levodopa
The amount of L-dopa in example 1 was adjusted to 20g/L, and the other conditions were kept the same as in example 1 to obtain a textile finishing agent; an antibacterial uv-protective bifunctional cotton fabric was then prepared as in example 3.
The performance test is carried out on the obtained difunctional cotton fabric, and the test results are as follows:
the antibacterial rate of the difunctional cotton fabric of the comparative example 7 on escherichia coli is 82%, the antibacterial rate on staphylococcus aureus is 80%, and the antibacterial rate after 20 times of water washing is 75% and 72%, which shows that the antibacterial property of the modified fabric is reduced due to excessive use of levodopa, because the levodopa reacts with amino in polylysine, and the amino in polylysine is a key group for the antibacterial property of the modified fabric; when the amino group is reacted in a large amount, the antibacterial property of polylysine is lowered, resulting in a decrease in the antibacterial effect of the finishing agent. The choice of the appropriate amount of levodopa is critical to the invention and excessive levodopa results in reduced antibacterial properties of the polylysine.
Comparative example 8 use of nanosilver solution
Replacing silver nitrate added with 0.1g/L in the embodiment 1 with nano silver (with the particle size of 10-15 nm) added with 0.1g/L, and keeping the other conditions consistent with the embodiment 1 to obtain a textile finishing agent; an antibacterial uv-protective bifunctional cotton fabric was then prepared as in example 3.
The performance test is carried out on the obtained difunctional cotton fabric, and the test results are as follows:
the antibacterial rate of the bifunctional cotton fabric of the comparative example 8 on escherichia coli is 93%, the antibacterial rate on staphylococcus aureus is 92%, and the antibacterial rate after 20 times of water washing is 82% and 75%, which shows that the in-situ reduction and combination of nano silver on a polylysine molecular chain are key points of excellent antibacterial property of the antibacterial agent. The antibacterial agent directly added with the nano silver particles can not form strong binding force with the polylysine containing the dopa side group, and can not form a polylysine/nano silver complex containing the dopa side group, so that after multiple water washing, the nano silver particles which are not firmly combined can be separated from the fabric, and the antibacterial performance of the fabric is obviously reduced after multiple water washing.
While the invention has been described with reference to the preferred embodiments, it is not limited thereto, and various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A method for preparing a self-crosslinking antibacterial ultraviolet-proof finishing agent for textiles, which is characterized by comprising the following steps:
(1) Preparation of solution of polylysine containing DOPA side group
Adding levodopa and carbodiimide hydrochloride into a polylysine solution, performing condensation reaction, and grafting the levodopa on a polylysine macromolecular chain through the reaction of amino groups on the polylysine and carboxyl groups on the levodopa to prepare a polylysine solution containing a dopa side group; wherein the molecular weight of the polylysine is 2000-5000 Da; the concentration of the levodopa in the polylysine solution is 1-10 g/L; the concentration of the polylysine solution is 5-50 g/L; the solvent is phosphate buffer solution, and the pH range is 5.5-6.5;
(2) Preparation of self-crosslinking antibacterial ultraviolet-proof finishing agent for textiles
Adding silver nitrate into the poly-lysine solution containing the dopa side group obtained in the step (1), and reducing the poly-lysine containing the dopa side group in situ to generate nano silver through the reducibility and adhesiveness of the dopa group, so as to prepare the antibacterial finishing agent containing the dopa side group poly-lysine/nano silver complex, namely the self-crosslinking textile antibacterial anti-ultraviolet finishing agent solution.
2. The method according to claim 1, wherein the concentration of carbodiimide hydrochloride in the polylysine solution in step (1) is 0.5-4 g/L.
3. The method of claim 1, wherein the silver nitrate in step (2) is present in the solution of poly-lysine containing pendant dopa groups at a concentration of 0.1 to 0.5g/L.
4. The self-crosslinking type antibacterial ultraviolet-proof finishing agent for textiles, which is prepared by the method according to any one of claims 1-3.
5. A method for preparing an antibacterial ultraviolet-resistant dual-function fabric by using the self-crosslinking textile antibacterial ultraviolet-resistant finishing agent, which is characterized in that the self-crosslinking textile antibacterial ultraviolet-resistant finishing agent solution is self-crosslinked and deposited on the surface of the fabric by adopting an immersion method or a spraying method to obtain the antibacterial ultraviolet-resistant dual-function fabric.
6. The method according to claim 5, wherein the impregnation method comprises;
soaking the fabric in a self-crosslinking antibacterial ultraviolet-proof finishing agent solution for textiles, spontaneously crosslinking and depositing the finishing agent on the surface of the fabric, and washing and drying after the soaking is finished to obtain an antibacterial ultraviolet-proof dual-function fabric; wherein the mass ratio of the fabric to the self-crosslinking textile antibacterial ultraviolet-proof finishing agent solution is 1:5-1:50, the dipping temperature is 20-60 ℃, the pH is 8.0-8.5, and the dipping time is 1-60 minutes; and after the impregnation is finished, washing with water, and then airing at room temperature or drying at 60-100 ℃.
7. The method according to claim 5, wherein the spraying method specifically comprises:
spraying a self-crosslinking antibacterial ultraviolet-proof finishing agent solution of the textile on the surface of the fabric, spontaneously crosslinking and depositing the finishing agent on the surface of the fabric, and drying to obtain an antibacterial ultraviolet-proof dual-function fabric; the mass ratio of the finishing agent solution to the fabric is 1:10-1:100, and the fabric is dried at room temperature or at 60-100 ℃ after being sprayed.
8. The antibacterial ultraviolet-resistant double-function fabric prepared by the method of any one of claims 5-7.
9. Use of the self-crosslinking textile antibacterial uv-protective finish of claim 4 in textiles for clothing, household textiles, decorations or medical and hygienic products.
10. Use of the antimicrobial uv resistant difunctional fabric of claim 8 in apparel textiles, household textiles, upholstery or medical and hygienic products.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07238272A (en) * | 1994-02-28 | 1995-09-12 | Hitachi Chem Co Ltd | Polyamino acid adhesive containing dopa |
| KR101539389B1 (en) * | 2014-04-07 | 2015-07-28 | 한국과학기술원 | Method for Regenerating Cofactors Using Polydopamine Induced Plasmonic Nanohybrids |
| CN110373899A (en) * | 2019-06-27 | 2019-10-25 | 浙江理工大学 | A kind of washable antibacterial cotton fabric and preparation method thereof |
| CN110578253A (en) * | 2019-09-17 | 2019-12-17 | 常州大学 | Preparation method of antibacterial textile based on polydopamine/nano-silver |
| CN110735319A (en) * | 2019-09-17 | 2020-01-31 | 常州大学 | preparation method of copper antibacterial textile based on polylysine/cyclodextrin |
| CN114517417A (en) * | 2022-01-06 | 2022-05-20 | 常州大学 | Preparation method of vegetable dye dyed antibacterial textile |
| CN114561810A (en) * | 2022-03-07 | 2022-05-31 | 中国科学院长春应用化学研究所 | Antibacterial anti-mite fabric and preparation method thereof |
| CN114672995A (en) * | 2022-04-19 | 2022-06-28 | 江南大学 | Fiber product with continuous antibacterial and rapid sterilization functions and preparation method thereof |
-
2022
- 2022-08-18 CN CN202210992192.3A patent/CN115162007B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07238272A (en) * | 1994-02-28 | 1995-09-12 | Hitachi Chem Co Ltd | Polyamino acid adhesive containing dopa |
| KR101539389B1 (en) * | 2014-04-07 | 2015-07-28 | 한국과학기술원 | Method for Regenerating Cofactors Using Polydopamine Induced Plasmonic Nanohybrids |
| CN110373899A (en) * | 2019-06-27 | 2019-10-25 | 浙江理工大学 | A kind of washable antibacterial cotton fabric and preparation method thereof |
| CN110578253A (en) * | 2019-09-17 | 2019-12-17 | 常州大学 | Preparation method of antibacterial textile based on polydopamine/nano-silver |
| CN110735319A (en) * | 2019-09-17 | 2020-01-31 | 常州大学 | preparation method of copper antibacterial textile based on polylysine/cyclodextrin |
| CN114517417A (en) * | 2022-01-06 | 2022-05-20 | 常州大学 | Preparation method of vegetable dye dyed antibacterial textile |
| CN114561810A (en) * | 2022-03-07 | 2022-05-31 | 中国科学院长春应用化学研究所 | Antibacterial anti-mite fabric and preparation method thereof |
| CN114672995A (en) * | 2022-04-19 | 2022-06-28 | 江南大学 | Fiber product with continuous antibacterial and rapid sterilization functions and preparation method thereof |
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