Copper ammonia and flax regenerated fiber blended fabric and preparation method thereof

Abstract

The invention relates to the technical field of fabrics, in particular to a copper ammonia and flax regenerated fiber blended fabric and a preparation method thereof.The preparation method comprises the following steps that 1, copper ammonia fibers are added into an ethanol water solution of pyridyltriformic acid, a reaction, heating, continuous reaction, washing and drying are conducted, and pyridyltriformic acid treated copper ammonia fibers are obtained; (2) immersing the pyridyltriformic acid treated copper ammonia fibers into a chitosan quaternary ammonium salt solution, and standing to obtain chitosan quaternary ammonium salt treated copper ammonia fibers; (3) immersing the chitosan quaternary ammonium salt treated copper ammonia fibers into the fucoidin-loaded emulsion, reacting, washing and drying to obtain modified copper ammonia fibers; 4, the modified copper ammonia fiber serves as warp yarn, the linen regenerated fiber serves as weft yarn, the modified copper ammonia fiber and linen regenerated fiber blended fabric is obtained through interweaving. The prepared fabric is smooth and soft, and has good antibacterial property and mechanical property.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of fabrics, and particularly relates to a copper ammonia and flax regenerated fiber blended fabric and a preparation method thereof. BACKGROUND

[0002] Copper ammonia fiber (cupro or cuprammonium rayon) is a regenerated cellulose fiber, which is made by dissolving natural cellulose (such as cotton linters) in a copper ammonia solution, is smooth and soft, similar to silk, has good drape, and is biodegradable. Flax regenerated fiber is a new type of fiber made by dissolving flax raw materials (such as flax chaff, waste linen or flax pulp) through chemical or physical methods and then spinning again. It not only retains the natural properties of flax, but also improves the roughness and wrinkle resistance of traditional flax fibers.

[0003] In the prior art, copper ammonia and flax fiber blended fabrics are mostly directly blended with flax fibers, and do not have good antibacterial properties, so there is an urgent need for a copper ammonia and flax regenerated fiber blended fabric with good comfort and good antibacterial properties. SUMMARY

[0004] The purpose of the present application is to provide a copper ammonia and flax regenerated fiber blended fabric and a preparation method thereof, which solves the technical problem of insufficient antibacterial properties of copper ammonia and flax regenerated fiber blended fabrics in the prior art.

[0005] In order to achieve the above-mentioned purpose, the present application adopts the following technical solutions:

[0006] The present application provides a preparation method of a copper ammonia and flax regenerated fiber blended fabric, comprising the following steps:

[0007] Step (1) adding copper ammonia fiber into an ethanol aqueous solution of pyridine tricarboxylic acid, reacting, warming, continuing to react, washing, and drying to obtain pyridine tricarboxylic acid treated copper ammonia fiber;

[0008] In the above process, the carboxyl group of pyridine tricarboxylic acid and the pyridine N are combined with the Cu in the copper ammonia fiber to form a stable coordination bond, and part of the carboxyl group is esterified with the -OH on the surface of the fiber to enhance the antibacterial properties and stability of the fiber. 2+

[0009] Step (2) immersing the pyridine tricarboxylic acid treated copper ammonia fiber into a chitosan quaternary ammonium salt solution, and standing to obtain chitosan quaternary ammonium salt treated copper ammonia fiber;

[0010] In the above process, the cation of chitosan quaternary ammonium salt is combined with the negative group (free carboxylate) on the surface of the pyridine tricarboxylic acid treated copper ammonia fiber through electrostatic attraction; the hydroxyl group / amino group of chitosan forms a hydrogen bond network with the -OH on the surface of the fiber or the carboxyl group of pyridine tricarboxylic acid, and the emulsion fully penetrates and is fixed on the surface / inside of the fiber. ​

[0011] Step (3) treating the copper ammonia fiber with chitosan quaternary ammonium salt, immersing the copper ammonia fiber into the fucoidan emulsion, reacting, washing, drying, and obtaining the modified copper ammonia fiber;

[0012] In the above process, the chitosan quaternary ammonium salt with positive electricity combines with the negative electricity of the fucoidan emulsion droplet, and the -OH of the fucoidan forms a hydrogen bond with the chitosan.

[0013] Step (4) interweaving the modified copper ammonia fiber as the warp and the flax regenerated fiber as the weft to obtain the copper ammonia and flax regenerated fiber blended fabric.

[0014] Preferably, in the step (1), the copper ammonia fiber is added in an amount of 10-20 g / L; the concentration of the pyridine tricarboxylic acid is 0.2-0.3 mol / L; the volume fraction of the ethanol aqueous solution is 90% (V / V); the reaction conditions are that the reaction temperature is 80-90℃, the reaction time is 1-2 h; the temperature rising temperature is 105-115℃; the continuous reaction time is 8-12 h; and the washing method is washing with ethanol for 3-5 times.

[0015] Preferably, in the step (2), the copper ammonia fiber treated with pyridine tricarboxylic acid is added in an amount of 10-20 g / L; the mass fraction of the chitosan quaternary ammonium salt solution is 1 wt%; and the standing time is 4-6 h.

[0016] Preferably, in the step (3), the reaction conditions are that the reaction temperature is 35-39℃, the reaction rotation speed is 100-200 rpm, and the reaction time is 36-54 h; and the washing method is washing with ethanol for 3-5 times.

[0017] Preferably, in the step (4), the weight of the copper ammonia and flax regenerated fiber blended fabric is 130-170 g / m 2 , and the thickness is 0.2-0.4 mm.

[0018] Preferably, in the step (4), the preparation method of the fucoidan emulsion includes the following steps:

[0019] The fucoidan is dissolved in water to obtain a fucoidan solution, after stirring treatment, cinnamyl aldehyde ethanol solution is added dropwise, and the stirring treatment is continued, followed by ultrasonic treatment, centrifugation, and obtaining the fucoidan emulsion.

[0020] In the above process, the cinnamyl aldehyde is wrapped by the fucoidan to form an O / W type nanoemulsion.

[0021] Preferably, the fucoidan solution concentration is 1% (w / v);the stirring treatment time is 1-2h;the cinnamaldehyde ethanol solution concentration is 20-50mg / mL;the continuous stirring treatment time is 50-90min;the ultrasonic treatment condition is that the ultrasonic treatment power is 150-210w and the ultrasonic treatment time is 10-20min;the centrifugal condition is that the centrifugal speed is 3500-4500rpm and the centrifugal time is 10-20min.

[0022] Preferably, in the step (4), the preparation method of the flax regenerated fiber comprises the following steps.

[0023] The recycled flax fiber is cut into pieces, added into 1-butyl-3-methyl imidazole acetate, stirred and treated, then added into an organic solvent, continuously stirred, defoaming treated, and a spinning solution is prepared, and the flax regenerated fiber is obtained by spinning.

[0024] Preferably, the mass ratio of the recycled flax fiber to 1-butyl-3-methyl imidazole acetate is 1:20;the stirring treatment method is stirring and treating at 75-85℃ with a speed of 550-650r / min for 1-3h;the mass ratio of 1-butyl-3-methyl imidazole acetate to the organic solvent is 1:3;the organic solvent is dimethyl sulfoxide;the continuous stirring method is continuously stirring at 75-85℃ for 2-4h;the defoaming treatment method is defoaming treatment in an oven at 35-45℃ for 10-14h;and the spinning method is that a 21G needle with an inner diameter of 0.52mm is selected, and the needle is extruded into a deionized water coagulation bath at a speed of 25-35mm / h, the coagulation time is 10-20min, then the flax regenerated fiber is obtained by winding to a bobbin and drying at 35-45℃ for 10-14h.

[0025] The copper ammonia and flax regenerated fiber blended fabric is prepared by the preparation method of the copper ammonia and flax regenerated fiber blended fabric.

[0026] In summary, due to the adoption of the above technical solutions, the present application has the following advantages:

[0027] 1. In the present application, the fiber is endowed with multiple antibacterial mechanisms of contact sterilization of quaternary ammonium salt, release sterilization of copper ions and antibacterial property of cinnamaldehyde, and has good biocompatibility;The film-forming property of chitosan protects the copper ions from being lost too quickly, and the fucoidan wraps the cinnamaldehyde to improve the long-acting antibacterial property, and the multiple components synergistically improve the antibacterial effect of the fabric.

[0028] 2. In this invention, 1-butyl-3-methylimidazolium acetate anion and cation (imidazolium cation + acetate anion) can disrupt the hydrogen bond network between cellulose molecules in flax fibers. Combined with the subsequently added dimethyl sulfoxide as a co-solvent, it can reduce the viscosity of the system, improve the fluidity of the spinning solution, and simultaneously maintain the dissolved state of cellulose (preventing re-aggregation). The resulting regenerated flax fiber is finer than traditional flax, reduces itching, and enhances fiber strength. The fabric blended with cupro fiber and regenerated flax fiber combines the advantages of both fibers, retaining the comfort of the natural material while improving functionality; it is smooth and soft, with good antibacterial and mechanical properties.

[0029] 3. This invention uses natural derivatives (fucoidan, chitosan, cinnamaldehyde) to reduce environmental impact, and the ionic liquid used is almost non-volatile, recyclable, and contains no harmful gases, making it environmentally friendly. Attached Figure Description

[0030] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0031] Figure 1 This is a process flow diagram of the preparation process of the cupro and flax regenerated fiber blended fabric of the present invention;

[0032] Figure 2 This is a bar chart showing the antibacterial properties of the cupro and regenerated flax fiber blended fabric of the present invention;

[0033] Figure 3 This is a line graph showing the mechanical properties of the cupro and flax regenerated fiber blended fabric of the present invention. Detailed Implementation

[0034] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0035] The substances and sources involved in the following examples and comparative examples are shown in Table 1:

[0036] Table 1

[0037] Substance Source / product information Recycled flax fibers Hangzhou Shanglu Silk Co., Ltd. Chitosan quaternary ammonium salt Wuhan Kemik Biomedical Technology Co., Ltd. Pyridine tricarboxylic acid Jiangsu Aikang Biomedical Research and Development Co., Ltd. Fucoidan Shaanxi Paniel Biotechnology Co., Ltd. Cinnamaldehyde Wuhan Nengmai Industrial Co., Ltd. 1-Butyl-3-methylimidazole acetate Jinan Xinda Chemical Co., Ltd.

[0038] Example 1

[0039] The embodiment discloses a preparation method of fucoidan-loaded emulsion, comprising the following steps:

[0040] Fucoidan is dissolved in water to obtain a 1% (w / v) fucoidan solution, after stirring for 1.5 h, 35 mg / mL cinnamaldehyde ethanol solution is added dropwise, stirring is continued for 75 min, ultrasonic treatment is performed at a power of 180 W for 15 min, and finally centrifugation is performed at a speed of 4000 rpm for 15 min, to obtain the fucoidan-loaded emulsion.

[0041] Embodiment 2

[0042] The embodiment discloses a preparation method of flax regenerated fiber, comprising the following steps:

[0043] The recycled flax fiber is cut into pieces, stirring treatment is performed at 80 ℃ and a speed of 600 r / min for 2 h according to a mass ratio of recycled flax fiber to 1-butyl-3-methyl imidazole acetate of 1:20, then dimethyl sulfoxide is added according to a mass ratio of 1-butyl-3-methyl imidazole acetate to organic solvent of 1:3, stirring is continued at 80 ℃ for 3 h, and defoaming treatment is performed in an oven at 40 ℃ for 12 h, to obtain a spinning solution, spinning is performed, and the flax regenerated fiber is obtained.

[0044] The spinning method is as follows: a 21G needle with an inner diameter of 0.52 mm is selected, the needle is extruded into a deionized water coagulation bath at a speed of 30 mm / h, the coagulation time is 15 min, and then the flax regenerated fiber is wound onto a bobbin and dried at 40 ℃ for 12 h.

[0045] Embodiment 3

[0046] Referring to Figure 1 The embodiment discloses a preparation method of copper ammonia and flax regenerated fiber blended fabric, comprising the following steps:

[0047] Step (1) copper ammonia fiber is added into a 0.2 mol / L pyridine tricarboxylic acid 90% (V / V) ethanol aqueous solution at an addition amount of 20 g / L, reaction is performed at 90 ℃ for 1 h, then the temperature is increased to 115 ℃ and reaction is continued for 8 h, the copper ammonia fiber is washed with ethanol for 5 times, and drying is performed, to obtain pyridine tricarboxylic acid treated copper ammonia fiber;

[0048] Step (2) the pyridine tricarboxylic acid treated copper ammonia fiber is immersed into a 1 wt% chitosan quaternary ammonium salt solution at an addition amount of 10 g / L, and standing is performed for 6 h, to obtain chitosan quaternary ammonium salt treated copper ammonia fiber;

[0049] Step (3) the chitosan quaternary ammonium salt treated copper ammonia fiber is immersed into the fucoidan-loaded emulsion prepared in embodiment 1, reaction is performed at 39 ℃ and a speed of 100 rpm for 54 h, ethanol washing and drying are performed, and modified copper ammonia fiber is obtained;

[0050] Step (4) interweave the modified cuprammonium fiber as warp and the flax regenerated fiber prepared in Example 2 as weft to obtain the cuprammonium fiber and flax regenerated fiber blended fabric.

[0051] Example 4

[0052] Referring to Figure 1 The present embodiment discloses a preparation method of a cuprammonium fiber and flax regenerated fiber blended fabric, comprising the following steps:

[0053] Step (1) add cuprammonium fiber in an amount of 15 g / L into a 0.25 mol / L pyridine tricarboxylic acid 90% (V / V) ethanol aqueous solution, react at 85°C for 1.5 h, then increase the temperature to 110°C and continue to react for 10 h, wash with ethanol for 4 times, and dry to obtain pyridine tricarboxylic acid treated cuprammonium fiber;

[0054] Step (2) immerse the pyridine tricarboxylic acid treated cuprammonium fiber in an amount of 15 g / L into a 1 wt% chitosan quaternary ammonium salt solution, stand for 5 h to obtain chitosan quaternary ammonium salt treated cuprammonium fiber;

[0055] Step (3) immerse the chitosan quaternary ammonium salt treated cuprammonium fiber into the fucoidan loaded emulsion prepared in Example 1, react at 37°C at a rotation speed of 150 rpm for 48 h, wash with ethanol and dry to obtain modified cuprammonium fiber;

[0056] Step (4) interweave the modified cuprammonium fiber as warp and the flax regenerated fiber prepared in Example 2 as weft to obtain the cuprammonium fiber and flax regenerated fiber blended fabric.

[0057] Example 5

[0058] Referring to Figure 1 The present embodiment discloses a preparation method of a cuprammonium fiber and flax regenerated fiber blended fabric, comprising the following steps:

[0059] Step (1) add cuprammonium fiber in an amount of 10 g / L into a 0.3 mol / L pyridine tricarboxylic acid 90% (V / V) ethanol aqueous solution, react at 80°C for 2 h, then increase the temperature to 105°C and continue to react for 12 h, wash with ethanol for 3 times, and dry to obtain pyridine tricarboxylic acid treated cuprammonium fiber;

[0060] Step (2) immerse the pyridine tricarboxylic acid treated cuprammonium fiber in an amount of 20 g / L into a 1 wt% chitosan quaternary ammonium salt solution, stand for 4 h to obtain chitosan quaternary ammonium salt treated cuprammonium fiber;

[0061] Step (3) immerse the chitosan quaternary ammonium salt treated cuprammonium fiber into the fucoidan loaded emulsion prepared in Example 1, react at 35°C at a rotation speed of 200 rpm for 36 h, wash with ethanol and dry to obtain modified cuprammonium fiber;

[0062] Step (4) interweave the modified cuprammonium fiber as warp and the flax regenerated fiber prepared in Example 2 as weft to obtain the cuprammonium fiber and flax regenerated fiber blended fabric.

[0063] Comparative Example 1

[0064] Comparative Example 1 is compared with Example 4, in the process of preparing the cuprammonium fiber and flax regenerated fiber blended fabric, the modified cuprammonium fiber is replaced by the modified cuprammonium fiber, and other conditions are unchanged.

[0065] Comparative Example 2

[0066] Comparative Example 2 is compared with Example 4, in the process of preparing the cuprammonium fiber and flax regenerated fiber blended fabric, the modified cuprammonium fiber is treated with pyridine trimellitic acid, and other conditions are unchanged.

[0067] Comparative Example 3

[0068] Comparative Example 3 is compared with Example 4, in the process of preparing the cuprammonium fiber and flax regenerated fiber blended fabric, the modified cuprammonium fiber is treated with chitosan quaternary ammonium salt, and other conditions are unchanged.

[0069] Comparative Example 4

[0070] Comparative Example 4 is compared with Example 4, in the process of preparing the cuprammonium fiber and flax regenerated fiber blended fabric, the flax fiber is replaced by the flax regenerated fiber, and other conditions are unchanged.

[0071] Experimental Example

[0072] The conductive polymer materials prepared in Examples 1-3 and Comparative Examples 1-3 are prepared into conductive polymer film samples by pouring method, and are sequentially numbered as Sample 1, Sample 2, Sample 3, Comparative Sample 1, Comparative Sample 2, and Comparative Sample 3. The sample preparation method is as follows:

[0073] The cuprammonium fiber and flax regenerated fiber blended fabrics prepared in Examples 3-5 and Comparative Examples 1-4 are tested, and the test basis is GB / T 16605-2008 "Regenerated Cellulose Silk Fabric"; the antibacterial rate of each group of fabric on Escherichia coli and Staphylococcus aureus is tested according to GB / T 20944.3-2008 "Evaluation of Antibacterial Performance of Textiles Part 3: Oscillation Method"; the results are shown in Table 2.

[0074] Table 2

[0075]

[0076] From the examples 3-5 and the comparative examples 1-4, it can be seen that the copper ammonia and flax regenerated fiber blended fabric prepared in the example 4 has good mechanical and antibacterial properties. From the comparison of the comparative examples 1-3 and the examples 3-5, it can be seen that, in the process of preparing the copper ammonia and flax regenerated fiber blended fabric, the unmodified copper ammonia fiber, the modified copper ammonia fiber treated by pyridine tricarboxylic acid, and the modified copper ammonia fiber treated by chitosan quaternary ammonium salt, the antibacterial property is reduced due to the lack of synergistic sterilization of copper ions, quaternary ammonium salt and cinnamyl aldehyde; the breaking strength is reduced due to the lack of esterification / coordination reaction of pyridine tricarboxylic acid with the cellulose hydroxyl group of the copper ammonia fiber or the copper ammonia complex to form crosslinking or surface modification, or the lack of fiber surface defects of chitosan.

[0077] From the comparison of the comparative example 4 and the examples 3-5, it can be seen that, in the process of preparing the copper ammonia and flax regenerated fiber blended fabric, the use of flax regenerated fiber can improve the mechanical properties of the fabric.

[0078] The above description is only a preferred embodiment of the present application, but the protection scope of the present application is not limited thereto, and any skilled person in the art can make equivalent replacement or change according to the technical solution and the inventive concept of the present application within the technical range disclosed in the present application, which should be covered in the protection scope of the present application.

[0079] The preferred embodiments of the present application disclosed above are only used to help explain the present application. The preferred embodiments do not describe all the details, and the present application is not limited to the specific embodiments. Obviously, many modifications and changes can be made according to the content of the present application. The present application selects and describes these embodiments in order to better explain the principles and practical applications of the present application, so that the skilled person in the art can well understand and utilize the present application. The present application is limited by the claims and the entire scope and equivalents thereof.

Claims

1. A method for preparing a blended fabric of cupro and regenerated flax fibers, characterized in that, Includes the following steps: Step (1) Add cuprammonium fiber to an ethanol-water solution of pyridinetricarboxylic acid, react, heat up, continue the reaction, wash, and dry to obtain pyridinetricarboxylic acid-treated cuprammonium fiber; Step (2) Immerse the pyridine tricarboxylic acid-treated cuprammonium fiber in a chitosan quaternary ammonium salt solution and let it stand to obtain chitosan quaternary ammonium salt-treated cuprammonium fiber; Step (3) The chitosan quaternary ammonium salt-treated cuprammonium fiber is immersed in a fucoidan-loaded emulsion, reacted, washed, and dried to obtain modified cuprammonium fiber; Step (4) The modified cupro fiber is used as the warp and the regenerated flax fiber is used as the weft to make a blended fabric of cupro and regenerated flax fiber.

2. The method for preparing the cupro and flax regenerated fiber blended fabric according to claim 1, characterized in that, In step (1), the amount of cuprammonium fiber added is 10-20 g / L; the concentration of pyridine tricarboxylic acid is 0.2-0.3 mol / L; the volume fraction of the ethanol aqueous solution is 90% (V / V); the reaction conditions are: reaction temperature is 80-90℃, reaction time is 1-2 h; the heating temperature is 105-115℃; the reaction time is 8-12 h; the washing method is to wash with ethanol 3-5 times.

3. The method for preparing the cupro and flax regenerated fiber blended fabric according to claim 1, characterized in that, In step (2), the amount of pyridine tricarboxylic acid added to treat cuprammonium fiber is 10-20 g / L; the mass fraction of chitosan quaternary ammonium salt solution is 1 wt%; and the standing time is 4-6 h.

4. The method for preparing the cupro and flax regenerated fiber blended fabric according to claim 1, characterized in that, In step (3), the reaction conditions are: reaction temperature of 35-39℃, reaction speed of 100-200rpm, and reaction time of 36-54h; the washing method is to wash with ethanol 3-5 times.

5. The method for preparing the cupro and flax regenerated fiber blended fabric according to claim 1, characterized in that, In step (4), the weight of the cupro and flax regenerated fiber blended fabric is 130-170 g / m². 2 The thickness is 0.2-0.4mm.

6. The method for preparing the cupro and flax regenerated fiber blended fabric according to claim 1, characterized in that, In step (3), the method for preparing the fucoidan-loaded emulsion includes the following steps: Fucoidan was dissolved in water to obtain a fucoidan solution. After stirring, cinnamaldehyde ethanol solution was added dropwise, and stirring was continued. Then, the solution was sonicated and centrifuged to obtain a fucoidan-loaded emulsion.

7. The method for preparing the cupro and flax regenerated fiber blended fabric according to claim 6, characterized in that, The fucoidan solution concentration was 1% (w / v); the stirring time was 1-2 h; the cinnamaldehyde ethanol solution concentration was 20-50 mg / mL; the stirring time was 50-90 min; the ultrasonic treatment conditions were: ultrasonic power 150-210 W, ultrasonic treatment time 10-20 min; the centrifugation conditions were: centrifugation speed 3500-4500 rpm, centrifugation time 10-20 min.

8. The method for preparing the cupro and flax regenerated fiber blended fabric according to claim 1, characterized in that, The method for preparing regenerated flax fiber in step (4) includes the following steps: The recycled flax fibers are shredded and added to 1-butyl-3-methylimidazolium acetate. After stirring, an organic solvent is added, and stirring is continued. The mixture is then degassed to obtain a spinning solution. Spinning is performed to obtain regenerated flax fibers.

9. The method for preparing the cupro and flax regenerated fiber blended fabric according to claim 8, characterized in that, The mass ratio of the recycled flax fiber to 1-butyl-3-methylimidazolium acetate is 1:20; the stirring treatment method is as follows: stirring at 550-650 r / min for 1-3 h at 75-85℃; the mass ratio of 1-butyl-3-methylimidazolium acetate to organic solvent is 1:3; the organic solvent is dimethyl sulfoxide; the stirring method is as follows: stirring is continued at 75-85℃ for 2-4 h; the degassing treatment method is as follows: degassing treatment is carried out in an oven at 35-45℃ for 10-14 h; the spinning method is as follows: using a 21G needle with an inner diameter of 0.52 mm, the fiber is extruded into a deionized water coagulation bath at a speed of 25-35 mm / h, the coagulation time is 10-20 min, and then wound into a bobbin and dried at 35-45℃ for 10-14 h to obtain regenerated flax fiber.

10. A cuprammonium and flax regenerated fiber blended fabric prepared by the method according to any one of claims 1-9.

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