CN119686109B - A flame-retardant silk fabric and its preparation method - Google Patents
A flame-retardant silk fabric and its preparation methodInfo
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- CN119686109B CN119686109B CN202411850459.0A CN202411850459A CN119686109B CN 119686109 B CN119686109 B CN 119686109B CN 202411850459 A CN202411850459 A CN 202411850459A CN 119686109 B CN119686109 B CN 119686109B
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Abstract
本发明公开了一种阻燃蚕丝织物的制备方法，包括如下步骤：将没食子酸水溶液和聚乙烯亚胺水溶液混合均匀，加入碱液调节pH值至碱性，得到整理液；采用所述整理液对脱胶蚕丝织物进行第一次处理，得到整理液处理的蚕丝织物；配置多价金属盐溶液，并采用所述多价金属盐溶液对整理液处理后的蚕丝织物进行第二次处理，得到阻燃整理的蚕丝织物；将所述阻燃整理的蚕丝织物进行干燥，得到所述阻燃蚕丝织物。本发明的制备方法，通过在织物表面形成PEI和GA的自交联网络，并与金属离子(Me)螯合，制备了PEI‑GA/Me复合涂层蚕丝织物，解决了阻燃剂的环保问题以及天然分子阻燃剂的耐久性问题，在满足阻燃性能的同时为织物提供了抗菌功能。
This invention discloses a method for preparing flame-retardant silk fabric, comprising the following steps: mixing gallic acid aqueous solution and polyethyleneimine aqueous solution evenly, adding alkali solution to adjust the pH value to alkaline, obtaining a finishing solution; using the finishing solution to perform a first treatment on degummed silk fabric, obtaining a finishing solution-treated silk fabric; preparing a polyvalent metal salt solution, and using the polyvalent metal salt solution to perform a second treatment on the finishing solution-treated silk fabric, obtaining a flame-retardant finished silk fabric; drying the flame-retardant finished silk fabric, obtaining the flame-retardant silk fabric. The preparation method of this invention, by forming a self-crosslinking network of PEI and GA on the fabric surface and chelating with metal ions (Me), prepares a PEI-GA/Me composite coated silk fabric, solving the environmental protection problem of flame retardants and the durability problem of natural molecular flame retardants, providing antibacterial function to the fabric while satisfying flame-retardant performance.
Description
Technical Field
The invention belongs to the technical field of flame retardance and textile functional finishing, and particularly relates to a preparation method of durable flame retardance silk fabric and the flame retardance silk fabric prepared by the preparation method.
Background
Silk is widely used in high-end clothing and household textiles because of its excellent breathability, skin-friendly and moisture absorption properties, as well as its smooth and soft properties. However, common silks are flammable and burn rapidly, threatening the safety of the user. The flammability of silk itself limits its potential and safety. The flame retardant silk fabric can enhance fire safety while maintaining its aesthetic appearance, making it an ideal choice for luxurious home textiles and high-end fashion. In addition, since the protein structure of silk provides a favorable environment for bacterial growth, it has poor antibacterial performance, which further highlights the need for multifunctional silk fabrics that integrate flame retardancy and other functions.
Halogen-containing compounds have been widely used for their excellent flame retardant properties, but are eventually limited or disabled due to their toxicity, bioaccumulation and environmental pollution problems. Phosphorus-based flame retardants commonly used in the market may release formaldehyde during use. In addition, phosphorus accumulation in natural environments may also cause eutrophication of lakes and other bodies of water, not only destroying the aquatic ecosystem, but also constituting a long-term threat to the overall environment. Because of these serious problems, the textile flame retardant field is actively exploring new alternatives, and phosphorus and halogen-independent compounds have become the dominant trend of future development. This transition aims at balancing the requirements of textile flame retardant properties and environmental protection as well as human health, pushing the textile industry to develop towards a more green and safer direction.
In recent years, natural compounds and derivatives thereof have become important research hotspots as environmental protection textile flame retardants. Biomolecules, such as biomass-based proteins, deoxyribonucleic acid (DNA), have been used as sustainable flame retardant coatings. The natural polyphenol is the most abundant and widely distributed bioactive molecule in plants, and has the advantages of low cost, no toxicity, safety, reproducibility and the like. For example, by adsorbing bioflavonoids and then mordant-dyeing with metal salts, the resulting composite exhibits flame retardant properties [Flavonoids-metal salts combination:A facile and efficient route for enhancing the flame retardancy of silk,Ind.Crops Prod.130(2019)580-591.]. on silk fabrics, however, the treated fabrics perform poorly in terms of wash fastness due to non-covalent deposition of biomacromolecules on the surface.
Gallic Acid (GA) is a widely existing natural polyphenol with a phenolic hydroxyl structure, and endows the natural polyphenol with various functions of antibiosis, antioxidation, antivirus, anti-inflammatory and the like. The gallic acid has low cost and high reactivity, so that the gallic acid can be widely applied to the functional modification of materials. In addition, GA has good flame retardancy and crosslinking properties. For example, two modified gallic acids (GAP and GAN) have been prepared as reactive flame retardants and cross-linking agents for the production of flame retardant polyurethane elastomers (PUEs). The GAP and GAN introduced significantly improves the coke yield and LOI values of the PUE [Modified gallic acids as both reactive flame retardants and cross-linkers for the fabrication of flame-retardant polyurethane elastomers,ChemistrySelect 8(39)(2023)e202302496].
Amino-quinone network (AQN) coating is a new advance in mussel heuristic chemistry in recent years. The method forms a self-crosslinking coating by Michael addition/Schiff base reaction between a polyamine compound and a quinone compound produced by oxidation of a polyphenol compound. Advantages of the AQN coating process include a one-step reaction process, mild conditions and durability of the resulting coating. Polyethyleneimine (PEI) is rich in reactive primary amino groups and is capable of reacting with GA to form a self-crosslinking network. The AQN system can remove a hydration layer on the surface of the material to obtain strong adhesive force. In addition, studies have shown that nitrogen-modified polyphenols have a good effect in reducing the peak heat release rate of cellulose fibers. This supports the application of AQN in textile flame retardance.
For example, patent CN201910565152.9, a preparation method of formaldehyde-free washable flame-retardant fabric, which is to put the fabric fixed by natural polyphenols into metal salt solution for digestion, and obtain formaldehyde-free washable flame-retardant fabric. However, in the preparation process, the fabric deposited with the natural polyphenol compound is placed in a fixing agent solution for digestion, and the fixing agent solution is at least one of a tartaric acid solution, a chitosan solution, a fixing agent Y solution and a water-soluble polyurethane fixing agent solution. The free formaldehyde content of the color fixing agent Y is high, and the flame retardance durability of the fabric is improved by a method of forming a film on the surface of the fabric, so that the hand feeling of the fabric is affected.
And as for the patent CN201811270759.6, a preparation method and application thereof, the silk is immersed in tannic acid and metal salt solution for treatment, and the flame-retardant silk fabric is prepared. However, the limiting oxygen index of the unwashed silk fabric is only 27.5%, the effect is to be improved, and the treatment temperature of the method is high, so that batch preparation is not realized.
The foregoing background is only for the purpose of providing an understanding of the inventive concepts and technical aspects of the present application and is not necessarily prior art to the present application and is not intended to be used to evaluate the novelty and creativity of the present application in the event that no clear evidence indicates that such an aspect has been disclosed prior to the filing date of the present application.
Disclosure of Invention
In view of the above, in order to overcome the defects in the prior art, the present invention aims to provide an improved flame retardant silk fabric with better flame retardant durability.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a preparation method of flame-retardant silk fabric comprises the following steps:
uniformly mixing gallic acid aqueous solution and polyethyleneimine aqueous solution, and adding alkali liquor to adjust the pH value to be alkaline to obtain finishing liquid;
Carrying out first treatment on the degummed silk fabric by adopting the finishing liquid to obtain a silk fabric treated by the finishing liquid;
Preparing a multivalent metal salt solution, and performing secondary treatment on the silk fabric treated by the finishing liquid by adopting the multivalent metal salt solution to obtain a flame-retardant finished silk fabric;
And drying the flame-retardant finished silk fabric to obtain the flame-retardant silk fabric.
According to some preferred implementation aspects of the invention, the gallic acid aqueous solution is prepared by mixing gallic acid with deionized water at 40-60 ℃ to completely dissolve the gallic acid in the deionized water, thereby obtaining the gallic acid aqueous solution with the concentration of 5-10 g/L.
According to some preferred implementation aspects of the invention, the polyethyleneimine aqueous solution is prepared by mixing polyethyleneimine with deionized water at 30-50 ℃ to completely dissolve the polyethyleneimine in the deionized water, thereby obtaining the polyethyleneimine aqueous solution with the concentration of 5-50 g/L.
According to some preferred embodiments of the invention, the weight average molecular weight of the polyethyleneimine is 500-5000.
According to some preferred embodiments of the present invention, the volume ratio between the gallic acid aqueous solution and the polyethyleneimine aqueous solution is 1:2-1:4.
According to some preferred implementation aspects of the invention, the alkali liquor is sodium hydroxide solution with the concentration of 5 g/L-20 g/L, and the pH of the finishing liquor is 8-10.
According to some preferred embodiments of the present invention, the multivalent metal salt is one or more selected from ferrous sulfate, ferric sulfate, aluminum sulfate and titanium sulfate, and the concentration of the multivalent metal salt solution is 5 g/L-50 g/L.
According to some preferred implementation aspects of the invention, the first treatment is that the finishing liquid is added into a dyeing tank of a jig dyeing machine, the temperature is raised to 35-50 ℃, the degummed silk fabric is wound on a cloth roller through the dyeing tank, the silk fabric treated by the finishing liquid is obtained after jig dyeing, and the bath ratio during jig dyeing is 1:3-1:5.
According to some preferred implementation aspects of the invention, the second treatment is that the multivalent metal salt aqueous solution is added into a dyeing tank of a jig dyeing machine, the temperature is raised to 40-60 ℃, the silk fabric treated by the finishing liquid is moved into the jig dyeing machine, the flame-retardant finished silk fabric is obtained after jig dyeing, and the bath ratio during jig dyeing is 1:3-1:5.
According to some preferred embodiments of the present invention, the drying temperature is 50-90 ℃ and the drying time is 20-40 minutes.
In some embodiments of the present invention, a method for preparing durable flame retardant silk fabric, using silk fabric as a base material, comprises the following steps:
(1) Preparation of finishing liquid
And mixing gallic acid with deionized water at 40-60 ℃ to completely dissolve the gallic acid in the deionized water to obtain a gallic acid aqueous solution with the concentration of 5-10 g/L.
And mixing the polyethyleneimine with deionized water at the temperature of 30-50 ℃ to ensure that the polyethyleneimine is completely dissolved in the deionized water, so as to obtain a polyethyleneimine aqueous solution with the concentration of 5-50 g/L.
And uniformly mixing the gallic acid aqueous solution and the polyethyleneimine aqueous solution according to the volume ratio of 1:2-1:4, and adding alkali liquor to adjust the pH value to 8-10 to obtain the finishing liquid.
(2) Finishing of fabrics
And adding the finishing liquid into a dyeing tank of a jig dyeing machine, heating to 35-50 ℃, winding the degummed silk fabric on a cloth roller through the dyeing tank at a bath ratio of 1:3-1:5, and carrying out reciprocating 2 times and 1 time of water washing to obtain the silk fabric treated by the finishing liquid.
(3) Preparing a polyvalent metal salt solution
In another jig dyeing machine, a polyvalent metal salt aqueous solution with the concentration of 5 g/L-50 g/L is prepared, and the temperature is raised to 40 ℃ to 60 ℃. The polyvalent metal salt is one or more selected from ferrous sulfate, ferric sulfate, aluminum sulfate and titanium sulfate.
(4) Treatment of metal salts
And (3) moving the silk fabric treated by the finishing liquid into a jig dyeing machine of the multivalent metal salt solution, wherein the rotating speed of the jig dyeing machine is 5-10 m/min, the bath ratio during jig dyeing is 1:3-1:5, and after 2 times of reciprocation, 3 times of washing are carried out, and the silk fabric subjected to flame-retardant finishing is obtained.
(5) Drying
And (3) moving the flame-retardant finished silk fabric to a drying room, and drying at 50-90 ℃ for 20-40 minutes to obtain the durable flame-retardant silk fabric.
The invention also provides the flame-retardant silk fabric prepared by the preparation method, which comprises the silk fabric and a coating on the surface of the silk fiber, wherein the coating is formed by reacting gallic acid with polyethyleneimine and polyvalent metal salt.
The principle of the invention is that the durable flame retardant is obtained by combining Gallic Acid (GA), polyethyleneimine (PEI) and metal ions and is used for silk fabrics. PEI and GA form a self-crosslinking network through Schiff base reaction or Michael addition, and further complex with metal ions to construct a PEI-GA/Me flame retardant system, so that the silk fabric is endowed with durable flame retardant performance.
The specific flame-retardant mechanism is that GA and PEI are decomposed first to generate nonflammable gases (such as H 2O、NH3 and CO 2), and the gases dilute the flammable gases and oxygen and take away heat generated by combustion. Furthermore, catechol groups in GA exhibit a strong scavenging ability towards free radicals. During combustion, it can trap highly reactive free radicals (H.and OH.) interrupting the combustion reaction, thereby providing a gas phase flame retardant effect. At the same time, the metal ions and catechol groups act synergistically in the coacervate phase to accelerate the formation of a dense carbon layer. The metal ions combine with oxygen to form metal oxides which are uniformly distributed on the surface of the carbon residue, so that the carbon layer is more compact and stable. The carbon layer can prevent heat and oxygen from entering the silk matrix, increase the carbon residue and reduce further thermal degradation of the matrix. Therefore, the PEI-GA/Me system synergistically acts in the GAs phase and the condensed phase, so that the silk fabric has excellent flame retardant property. Wherein GA has stronger chelating ability, and can react with metal ions through coordination bonds to form ternary complex with silk, thereby improving the washing fastness of the fabric. In addition, the silk fabric treated by the GA and Fe3+ compound also has excellent antibacterial performance.
Compared with the prior art, the preparation method of the flame-retardant silk fabric has the advantages that the obtained PEI-GA/Me flame-retardant system provides excellent and stable flame retardance for the silk fabric, overcomes the defect of poor flame retardance and durability of natural molecular flame retardants on the fabric, is environment-friendly and pollution-free, accords with the ecological concept of energy conservation and emission reduction, is low in treatment temperature and simple to operate, realizes batch production in a dyeing mode, integrates flame retardance and antibacterial property, can increase the added value of products, has a vertical burning damage length of 15cm after 50 times of washing, has an LOI value of higher than 27%, has good flame retardance, has 99.8% of antibacterial property on staphylococcus aureus, and has no change in hand feeling.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for the description of the embodiments will be briefly described below, and it is apparent that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a photograph of a vertical burning test of durable flame retardant silk fabrics prepared in examples 1-4 of the present invention with silk as is (untreated silk fabrics) and carbon length and LOI values destroyed;
FIG. 2 is a photograph of a vertical burning test and a broken charcoal length and LOI value of the durable flame retardant silk fabrics prepared in examples 1-4 of the present invention after 20 washes;
FIG. 3 is the results of vertical char length and LOI test before and after washing of durable flame retardant silk fabric prepared in example 2 of the present invention;
Fig. 4 is a photograph showing antibacterial properties of the durable flame retardant silk fabric prepared in example 2 of the present invention and untreated silk fabric.
Detailed Description
In order to make the technical solution of the present invention better understood by those skilled in the art, the technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
According to the durable flame-retardant silk fabric and the preparation method thereof, the PEI-GA/Me composite coating silk fabric is prepared by forming the self-crosslinking network of PEI and GA on the surface of the fabric and chelating with metal ions (Me), so that the environmental protection problem of a flame retardant and the durability problem of a natural molecular flame retardant are solved, and the flame retardant performance is met and meanwhile an antibacterial function is provided for the fabric.
The invention successfully applies the flame-retardant antibacterial coating which does not contain phosphorus and halogen to silk fabrics under mild conditions through simple volume dyeing and drying processes. The preparation process is simple, mass production can be realized, the volume dyeing process is adopted, the bath ratio is low, the cost is saved, and the silk fabric is not easy to wrinkle. Provides a new strategy for preparing durable and multifunctional flame-retardant silk by using renewable biomass resources. Specifically, the preparation method of the durable flame-retardant silk fabric provided by the invention takes the silk fabric as a base material and comprises the following steps:
(1) Preparation of finishing liquid
And mixing gallic acid with deionized water at 40-60 ℃ to completely dissolve the gallic acid in the deionized water to obtain a gallic acid aqueous solution with the concentration of 5-10 g/L.
And mixing the polyethyleneimine with deionized water at the temperature of 30-50 ℃ to ensure that the polyethyleneimine is completely dissolved in the deionized water, so as to obtain a polyethyleneimine aqueous solution with the concentration of 5-50 g/L. The Mw molecular weight of the polyethyleneimine is 500-5000.
And uniformly mixing the gallic acid aqueous solution and the polyethyleneimine aqueous solution according to the volume ratio of 1:2-1:4, and adding alkali liquor to adjust the pH value to 8-10 to obtain the finishing liquid. The alkali liquor is 5 g/L-20 g/L sodium hydroxide solution.
(2) Finishing of fabrics
And adding the finishing liquid into a dyeing tank of a jig dyeing machine, heating to 35-50 ℃, winding the degummed silk fabric on a cloth roller through the dyeing tank at a bath ratio of 1:3-1:5, and carrying out reciprocating 2 times and 1 time of water washing to obtain the silk fabric treated by the finishing liquid.
(3) Preparing a polyvalent metal salt solution
In another jig dyeing machine, a polyvalent metal salt aqueous solution with the concentration of 5 g/L-50 g/L is prepared, and the temperature is raised to 40 ℃ to 60 ℃. The polyvalent metal salt is one or more selected from ferrous sulfate, ferric sulfate, aluminum sulfate and titanium sulfate.
(4) Treatment of metal salts
And (3) transferring the silk fabric treated by the finishing liquid into a jig dyeing machine of the multivalent metal salt solution, wherein the rotating speed of the jig dyeing machine is 5-10 m/min, after 2 times of reciprocation, 3 times of water washing and discharging to obtain the flame-retardant finished silk fabric, and the bath ratio during jig dyeing is 1:3-1:5.
(5) Drying
The flame-retardant finished silk fabric is moved to a drying room and dried for 20-40 minutes at 50-90 ℃ to obtain the durable flame-retardant silk fabric, the flame-retardant silk fabric comprises silk fabric and a coating on the surface, wherein the coating is formed by reacting gallic acid with polyethyleneimine and multivalent metal salt, PEI and GA form a self-crosslinking network through Schiff base reaction or Michael addition, and the self-crosslinking network is further complexed with metal ions, so that a PEI-GA/Me flame-retardant system is constructed, and the durable flame-retardant performance of the silk fabric is endowed.
Example 1
The preparation method of the durable flame-retardant silk fabric (ferrous sulfate, fe 2+) in the embodiment comprises the following specific steps:
(1) Preparation of finishing liquid, namely uniformly mixing 10g/L of gallic acid aqueous solution and 10g/L of polyethyleneimine (Mw molecular weight is 1000) aqueous solution according to a volume ratio of 1:2, and adding 20g/L of sodium hydroxide solution to adjust the pH value to 9.5.
(2) And (3) finishing the fabric, namely adding the finishing liquid into a dyeing tank of a jig dyeing machine, heating to 50 ℃, winding the degummed silk fabric on a cloth roller through the dyeing tank at a bath ratio of 1:4, and carrying out reciprocating 2 times and 1 time of water washing at the rotating speed of 10 meters/min of the jig dyeing machine, so as to obtain the silk fabric treated by the finishing liquid.
(3) Preparing a polyvalent metal salt solution, namely preparing a ferrous sulfate aqueous solution in another jig dyeing machine, wherein the concentration is 20g/L, and heating to 50 ℃.
(4) And (3) treating metal salt, namely moving the silk fabric treated by the finishing liquid obtained in the step (2) into a jig dyeing machine, wherein the bath ratio is 1:4, the rotating speed of the jig dyeing machine is 10 m/min, and after 2 times of reciprocation, washing with 3 times of water, and discharging the silk fabric to obtain the flame-retardant finished silk fabric.
(5) And (3) drying, namely moving the flame-retardant finished silk fabric to a drying room, and drying for 30 minutes at 50 ℃ to obtain the durable flame-retardant silk fabric.
Example 2
The preparation method of the durable flame-retardant silk fabric (ferric sulfate, fe 3 +), in the embodiment, comprises the following specific steps:
(1) Preparation of the finishing liquid, namely uniformly mixing 5g/L of gallic acid aqueous solution and 5g/L of polyethyleneimine (Mw molecular weight is 600) aqueous solution according to a ratio of 1:4, and adding 5g/L of sodium hydroxide to adjust the pH value to 8.5.
(2) And (3) finishing the fabric, namely adding the finishing liquid into a dyeing tank of a jig dyeing machine, heating to 40 ℃, immersing the degummed silk fabric into the finishing liquid at a bath ratio of 1:5, and taking out the silk fabric treated by the finishing liquid after the dyeing liquid is repeatedly washed for 2 times and 1 time at the rotating speed of 5 meters/min of the jig dyeing machine.
(3) Preparing a polyvalent metal salt solution, namely preparing an aqueous solution of sulfuric acid in another jig dyeing machine, wherein the concentration is 10g/L, and heating to 40 ℃.
(4) And (3) treating metal salt, namely moving the silk fabric treated by the finishing liquid obtained in the step (2) into a jig dyeing machine, wherein the bath ratio is 1:5, the rotating speed of the jig dyeing machine is 5 m/min, and after 2 times of reciprocation, washing with 3 times of water, and discharging the silk fabric to obtain the flame-retardant finished silk fabric.
(5) And (3) drying, namely moving the flame-retardant finished silk fabric to a drying room, and drying at 40 ℃ for 40 minutes to obtain the durable flame-retardant silk fabric.
Example 3
The preparation method of the durable flame-retardant silk fabric (aluminum sulfate, al 3 +), in this embodiment, comprises the following specific steps:
(1) Preparation of finishing liquid, namely uniformly mixing 5g/L of gallic acid aqueous solution and 15g/L of polyethyleneimine (Mw molecular weight is 2000) aqueous solution according to a ratio of 1:4, and adding 5g/L of sodium hydroxide to adjust the pH value to 9.
(2) And (3) finishing the fabric, namely adding the finishing liquid into a dyeing tank of a jig dyeing machine, heating to 60 ℃, immersing the degummed silk fabric into the finishing liquid at a bath ratio of 1:4, and taking out the silk fabric treated by the finishing liquid after the dyeing liquid is repeatedly washed for 2 times and 1 time at the rotating speed of 5 meters/min of the jig dyeing machine.
(3) Preparing a polyvalent metal salt solution, namely preparing an aluminum sulfate aqueous solution in another jig dyeing machine, wherein the concentration is 10g/L, and heating to 60 ℃.
(4) And (3) treating metal salt, namely moving the silk fabric treated by the finishing liquid obtained in the step (2) into a jig dyeing machine, wherein the bath ratio is 1:4, the rotating speed of the jig dyeing machine is 5 m/min, and after 2 times of reciprocation, washing with 3 times of water, and discharging the silk fabric to obtain the flame-retardant finished silk fabric.
(5) And (3) drying, namely moving the flame-retardant finished silk fabric to a drying room, and drying for 20 minutes at 60 ℃ to obtain the durable flame-retardant silk fabric.
Example 4
The preparation method of the durable flame-retardant silk fabric (titanium sulfate, ti 4 +), in the embodiment, comprises the following specific steps:
(1) Preparation of finishing liquid, namely uniformly mixing 10g/L of gallic acid aqueous solution and 20g/L of polyethyleneimine (Mw molecular weight is 2500) aqueous solution according to a ratio of 1:3, and adding 10g/L of sodium hydroxide to adjust the pH value to 9.3.
(2) And (3) finishing the fabric, namely adding the finishing liquid into a dyeing tank of a jig dyeing machine, heating to 50 ℃, immersing the degummed silk fabric into the finishing liquid at a bath ratio of 1:3, and taking out the silk fabric treated by the finishing liquid after the dyeing liquid is repeatedly washed for 2 times and 1 time at the rotating speed of the jig dyeing machine of 10 meters/min.
(3) Preparing a polyvalent metal salt solution, namely preparing a titanium sulfate aqueous solution with the concentration of 10g/L in another jig dyeing machine, and heating to 50 ℃.
(4) And (3) treating metal salt, namely moving the silk fabric treated by the finishing liquid obtained in the step (2) into a jig dyeing machine, wherein the bath ratio is 1:3, the rotating speed of the jig dyeing machine is 10 m/min, and after 2 times of reciprocation, washing with 3 times of water, and discharging the silk fabric to obtain the flame-retardant finished silk fabric.
(5) And (3) drying, namely moving the flame-retardant finished silk fabric to a drying room, and drying for 30 minutes at 50 ℃ to obtain the durable flame-retardant silk fabric.
Testing and results
The flame retardant property of the silk fabric prepared in the embodiment of the invention is measured according to GB/T5454-1997 oxygen index method for textile combustion property experiment and GB/T5455-2014 determination of flame retardant length and continuous flame time of the vertical damage length of the textile combustion property. The washing method of the flame-retardant silk fabric is carried out according to GB/T3921-2008 standard of the fastness to soaping of textile color fastness test, 2g/L of special detergent for the silk and wool fabric is used, and the washing is carried out for 30min at the temperature of 40 ℃ at the bath ratio of 1:50. The water washing is repeated until the required water washing times.
(1) Flame retardant test
The results of the vertical burning test photographs and the carbon length and LOI values of the durable flame retardant silk fabrics prepared in examples 1 to 4 with the silk as it is (untreated silk fabric) are shown in fig. 1.
As can be seen from fig. 1, the untreated silk fabric burns rapidly after contact with the flame and is completely burned in 12 seconds, and almost the whole sample (30 cm) is burned. In contrast, the treated fabric rapidly self-extinguishes after contact with the flame, the spread of the flame is completely suppressed, and the fabric carbonizes at high temperature. The damage lengths of the fabrics treated with Fe 2+、Fe3+、Al3+ and Ti 4+ were 9.2 cm, 8.3 cm, 9.3 cm and 8.2 cm respectively, which were significantly shorter than those of the untreated silk fabrics. The flame retardant property of the treated silk fabric is obviously improved, the B1-level flame retardant standard is achieved, and the carbonization length is smaller than 15 cm according to the Chinese standard GB/T17591 and the B1-level flame retardant requirement.
Meanwhile, the LOI values of the treated fabrics increased to 29.8%, 30.2%, 27.4% and 33.0%, respectively, compared to 25.0% for untreated silk. The significant increase in LOI values is attributable to the formation of a char layer that serves as an insulator that impedes the transfer of heat and combustible materials, thereby slowing the combustion process.
(2) Durability test
The vertical burning test photographs and the results of the carbon length and LOI values of the durable flame retardant silk fabrics prepared in examples 1-4 after 20 washes are shown in FIG. 2.
As can be seen from fig. 2, after 20 times of washing, the damage length of the fabric treated by the four metal salts is less than 15 cm after the vertical burning test. In particular, the Fe 3+ ion treated fabrics had no significant flame spread and little change in damage length, indicating that the fabrics still had good flame retardant durability after washing.
Further washing tests were performed on the Fe 3+ ion treated fabric (example 2), as shown in FIG. 3 (the vertical burning charcoal length and LOI test results before and after washing the durable flame retardant silk fabric prepared in example 2), after 50 washing, the LOI value of the silk fabric still exceeded 27%, the charring damage length was close to 15 cm, but the fabric still met the B1 grade flame retardant standard. These results indicate that the flame retardancy and wash fastness of the modified silk fabric can be effectively improved by co-depositing GA, PEI and metal ions.
(3) Antibacterial test
Fig. 4 is a photograph showing antibacterial properties of the durable flame retardant silk fabric prepared in example 2 and untreated silk fabric.
As can be seen from fig. 4, the antibacterial properties of the untreated silk fabric are poor, because silk proteins provide nutrition for bacteria. In contrast, by counting the number of colonies on the petri dishes and calculating the antibacterial rate, the antibacterial rate of the durable flame-retardant silk fabric of example 2 against escherichia coli was 78.6%, and the antibacterial rate against staphylococcus aureus was 99.8%. The durable flame-retardant silk fabric has excellent durable flame-retardant performance and antibacterial performance.
The application relates to a durable flame-retardant silk fabric and a preparation method thereof, belonging to the field of functional finishing of textiles. The preparation method comprises the following steps of adopting Gallic Acid (GA), polyethyleneimine (PEI) and metal ions to combine, and preparing the flame-retardant silk fabric through a simple volume dyeing-drying method. Silk fabrics modified with different metal ions (Fe 2+、Fe3+、Al3+ and Ti 4+) all show self-extinguishing properties in vertical burning tests, the damaged coke lengths are 9.2, 8.3, 9.3 and 8.2cm respectively, and the Limiting Oxygen Index (LOI) values are 29.8%, 30.2%, 27.4% and 33.0% respectively. After 50 washing cycles, the length of the silk injury coke treated by Fe 3+ is still kept below 15 cm. The Fe 3+ treated silk also shows excellent antibacterial properties. The simple and environment-friendly preparation method of the functionalized silk fabric provides a new way for developing advanced and sustainable silk fabrics.
The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the present invention and to implement the same, but are not intended to limit the scope of the present invention, and all equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of the present invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
Claims (10)
1. The preparation method of the flame-retardant silk fabric is characterized by comprising the following steps of:
uniformly mixing gallic acid aqueous solution and polyethyleneimine aqueous solution, and adding alkali liquor to adjust the pH value to be alkaline to obtain finishing liquid;
Carrying out first treatment on the degummed silk fabric by adopting the finishing liquid to obtain a silk fabric treated by the finishing liquid;
Preparing a multivalent metal salt solution, and performing secondary treatment on the silk fabric treated by the finishing liquid by adopting the multivalent metal salt solution to obtain a flame-retardant finished silk fabric;
drying the flame-retardant finished silk fabric to obtain the flame-retardant silk fabric;
The polyvalent metal salt is one or more selected from ferrous sulfate, ferric sulfate, aluminum sulfate and titanium sulfate.
2. The preparation method of the gallic acid aqueous solution according to claim 1 is characterized in that the gallic acid aqueous solution is prepared by mixing gallic acid with deionized water at 40-60 ℃ to completely dissolve the gallic acid in the deionized water, and the gallic acid aqueous solution with the concentration of 5-10 g/L is obtained.
3. The preparation method of the polyethyleneimine water solution is characterized by comprising the steps of mixing the polyethyleneimine with deionized water at 30-50 ℃ to enable the polyethyleneimine to be completely dissolved in the deionized water, and obtaining the polyethyleneimine water solution with the concentration of 5 g/L-50 g/L, wherein the weight average molecular weight of the polyethyleneimine is 500-5000.
4. The preparation method of claim 1, wherein the volume ratio between the aqueous gallic acid solution and the aqueous polyethyleneimine solution is 1:2-1:4.
5. The preparation method of claim 1, wherein the alkali solution is sodium hydroxide solution with a concentration of 5 g/L-20 g/L, and the pH of the finishing solution is 8-10.
6. The method of claim 1, wherein the concentration of the multivalent metal salt solution is 5g/L to 50 g/L.
7. The preparation method according to claim 1, wherein the first treatment is to add finishing liquid into a dyeing tank of a jig dyeing machine, heat up to 35-50 ℃, wind degummed silk fabric on a cloth roller through the dyeing tank, and obtain the silk fabric treated by the finishing liquid after jig dyeing.
8. The preparation method according to claim 1, wherein the second treatment is to add a metal salt aqueous solution into a dyeing tank of a jig dyeing machine, heat up to 40-60 ℃, move the silk fabric treated by the finishing liquid into the jig dyeing machine, and obtain the flame-retardant finished silk fabric after jig dyeing.
9. The method according to claim 1, wherein the drying temperature is 50-90 ℃ and the drying time is 20-40 minutes.
10. A flame retardant silk fabric prepared by the preparation method of any one of claims 1-9.
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| CN109371660A (en) * | 2018-10-29 | 2019-02-22 | 南通纺织丝绸产业技术研究院 | A kind of flame retardant silk and its preparation method and application |
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| CN117364475A (en) * | 2023-11-21 | 2024-01-09 | 安徽贺赢新材料科技有限公司 | Antibacterial conductive fiber and preparation method thereof |
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| CN109174040A (en) * | 2018-10-12 | 2019-01-11 | 浙江理工大学 | A kind of preparation method of polyfunctional group metal absorbent |
| CN109371660A (en) * | 2018-10-29 | 2019-02-22 | 南通纺织丝绸产业技术研究院 | A kind of flame retardant silk and its preparation method and application |
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