阅读说明：本技术 一种抗菌疏水牛仔织物的制备方法 (Preparation method of antibacterial hydrophobic denim fabric ) 是由 梁惠娥 程煜 孙昌 贾蕾蕾 于 2021-08-18 设计创作，主要内容包括：本发明提供了一种抗菌疏水牛仔织物的制备方法,属于牛仔织物改性术领域。包括以下步骤：将牛仔织物酶洗烘干,水洗烘干；将所得牛仔织物在混合溶液中进行二浸二钆处理并烘干；所述混合溶液为季铵盐水溶液和乙醇混合所得；将所得牛仔织物进行真空等离子体接枝处理,烘干晾干得到所述抗菌疏水的牛仔织物。本发明工艺操作简单,成本低。本发明的制备方法应用广泛,可应用于日常服用,军用产品或医疗卫生领域医护人员服装、产品等原材料。(The invention provides a preparation method of an antibacterial hydrophobic denim fabric, and belongs to the field of denim fabric modification. The method comprises the following steps: washing and drying the jean fabric with enzyme, and washing and drying the jean fabric with water; carrying out secondary immersion and secondary gadolinium treatment on the obtained jean fabric in the mixed solution and drying; the mixed solution is obtained by mixing a quaternary ammonium salt aqueous solution and ethanol; and carrying out vacuum plasma grafting treatment on the obtained jean fabric, drying and airing to obtain the antibacterial hydrophobic jean fabric. The invention has simple process operation and low cost. The preparation method of the invention has wide application, and can be applied to raw materials of daily clothing, military products, medical staff clothing, products and the like in the field of medical health.)

1. The preparation method of the antibacterial hydrophobic denim fabric is characterized by comprising the following steps:

(1): washing and drying the jean fabric with enzyme, and then washing and drying;

(2): carrying out secondary gadolinium soaking treatment on the denim fabric obtained in the step (1) in a mixed solution and drying; the mixed solution is obtained by mixing a quaternary ammonium salt aqueous solution and ethanol;

(3): and (3) carrying out vacuum plasma grafting treatment on the denim fabric obtained in the step (2), and drying to obtain the antibacterial hydrophobic denim fabric.

2. The method according to claim 1, wherein in step (1), the denim fabric is a pure cotton denim.

3. The method according to claim 1, wherein in step (1), the enzyme is a cellulase enzyme.

4. The method according to claim 1, wherein in the step (2), the quaternary ammonium salt is one or more selected from the group consisting of (3-acrylamidopropyl) trimethylammonium chloride, 3-chloro-2-hydroxypropyltrimethylammonium chloride, and 2-dimethyl-2-hexadecyl-1-methacryloyloxyethyl ammonium bromide.

5. The method according to claim 1, wherein in the step (2), the volume ratio of the quaternary ammonium salt, the ethanol and the water in the mixed solution is 3-5:0.5-1: 80-100.

6. The preparation method according to claim 1, wherein in the step (2), the liquid retention rate of the fabric after the secondary dipping of gadolinium is 110-120%.

7. The manufacturing method according to claim 1, wherein in the step (2), the bath ratio of the denim fabric to the mixed solution is 1: 15-30.

8. The method according to claim 1, wherein in the step (2), the drying temperature is 30-60 ℃ and the time is 5-15 min.

9. The method according to claim 1, wherein in the step (3), the gas used for the vacuum plasma is oxygen and/or argon.

10. The method as claimed in claim 1, wherein in the step (3), the vacuum plasma is provided with a gas flow of 100-.

Technical Field

The invention belongs to the field of denim fabric modification technology, and particularly relates to a preparation method of an antibacterial hydrophobic denim fabric.

Background

Denim garments have a wide popularity worldwide. The denim fabric is mainly made of pure cotton denim or cotton/polyester/ammonia/hemp blended fabric, wherein the proportion of cotton in the pure cotton or blended fabric accounts for the majority. As the cotton fabric is hydrophilic porous fiber, bacteria are easy to breed and adsorb under the influence of external factors such as sweat stain, dust and the like in the process of taking the fabric, so that the use performance of the fabric is influenced, the health of a human body is threatened, and the antibacterial finishing of the fabric is especially necessary for improving the service performance of the fabric and preventing the fabric and the human body from being harmed by microorganisms.

The currently used antibacterial agents mainly comprise metal salts, quaternary ammonium salts, ammonium halide compounds, chitosan, natural organic matters and the like, or load heavy metal ions (silver, copper and zinc) so as to achieve the safe and healthy performance. However, the absorption and persistence of these compounds is difficult to control and is easily leached from textiles. The traditional padding baking antibacterial finishing process can endow the fabric with better antibacterial performance, but the compatibility of the antibacterial agent and other chemical substances, including toxicity to human beings, animals and organisms, is a disadvantage to be solved urgently. Therefore, finding a universal and effective method for preparing the water-repellent antibacterial jean fabric without affecting the wearability of the jean fabric still remains a great challenge.

Plasma treatment is one of the methods to improve textile production processes, a technique that has been used by the textile industry for surface modification and to impart breathability and biocompatibility. A plasma is a medium composed of ions, free electrons, photons, neutral atoms and molecules in the ground and excited states. These particles are generated by dissociation of an inert gas under the influence of electrical energy. In the textile field, plasmas can graft new functional groups onto the surface of textile substrates and modify the surface properties of polymers with the aid of reactive gases (e.g. oxygen, nitrogen, ammonia or water vapor). The plasma surface modification can improve the air permeability, dyeability, printability and antistatic function of various materials such as natural materials or synthetic fibers. The main advantage is that the process only changes the surface properties of the material without affecting the bulk properties of the substrate. Various dissociated active particles in the plasma can generate etching effect on the surface of the cotton fiber, increase active sites, generate free radicals and activate the surface of the material, so that the finishing agent is more easily attached to the surface of the fiber and generates grafting reaction with the surface of the fiber.

Disclosure of Invention

In order to solve the technical problems, the invention provides a preparation method of an antibacterial hydrophobic denim fabric. The invention has simple process operation and low cost.

A preparation method of an antibacterial hydrophobic denim fabric comprises the following steps:

(1): washing and drying the jean fabric with enzyme, and washing and drying the jean fabric with water;

the enzyme washing process comprises the following steps: neutral cellulase 1.0-1.5 wt%, pH 6-8 (neutral cellulase), treating for 45-120min at 50-60 deg.c;

(2): carrying out secondary gadolinium soaking treatment on the denim fabric obtained in the step (1) in a mixed solution and drying; the mixed solution is obtained by mixing a quaternary ammonium salt aqueous solution and ethanol;

(3): and (3) carrying out vacuum plasma grafting treatment on the denim fabric obtained in the step (2), drying and airing to obtain the antibacterial hydrophobic denim fabric.

In one embodiment of the present invention, in step (1), the denim fabric is a pure cotton denim.

In one embodiment of the present invention, in step (1), the enzyme is cellulase.

In one embodiment of the present invention, in the step (2), the quaternary ammonium salt is one or more of (3-acrylamidopropyl) trimethyl ammonium chloride (APTAC), 3-chloro-2-hydroxypropyltrimethyl ammonium chloride (TX-DF), and 2-dimethyl-2-hexadecyl-1-methacryloyloxyethyl ammonium bromide (DEHMA).

In one embodiment of the invention, the volume ratio of the quaternary ammonium salt, the ethanol and the water in the mixed solution is 3-5:0.5-1: 80-100.

In one embodiment of the invention, in the step (2), the fabric liquid retention rate after the secondary dipping of gadolinium is 110-120%.

In one embodiment of the invention, in the step (2), the bath ratio of the denim fabric to the mixed solution is 1: 15-30.

In one embodiment of the invention, in the step (2), the drying temperature is 30-60 ℃ and the time is 5-15 min.

In one embodiment of the present invention, in the step (2), the gas used in the vacuum plasma is oxygen and/or argon.

In one embodiment of the present invention, the vacuum plasma conditions are a gas flow of 100-.

Compared with the prior art, the technical scheme of the invention has the following advantages:

the invention selects quaternary ammonium salt as an antibacterial agent monomer, carries out plasma grafting modification on the pure cotton jean fabric, discusses the optimal plasma treatment process conditions under different plasma treatment conditions (variables are sputtering gas, flow, power and time), and optimizes the influence on the antibacterial property and wearability of the cotton fabric. The antibacterial denim fabric with good hydrophobic fabric hand feeling performance is prepared, has wide application, and can be applied to daily clothing, military products or raw materials of medical staff clothing, products and the like in the medical health field.

Drawings

In order that the present disclosure may be more readily and clearly understood, reference is now made to the following detailed description of the embodiments of the present disclosure taken in conjunction with the accompanying drawings, in which

FIG. 1 is SEM images of a denim fabric obtained in example 9 of the present invention and a raw denim fabric of comparative example 1; wherein (a) is the jean fabric as it is in comparative example 1, and (b) is the SEM image of the jean fabric obtained in example 9.

FIG. 2 is the water repellent effect of the denim fabric obtained in example 9 of the present invention and the denim fabric as it is of comparative example 1; wherein (a) is the instantaneous contact angle of the denim fabric as it is without hydrophobic treatment of comparative example 1, and (b) is the contact angle of the denim fabric obtained in example 9.

FIG. 3 shows the contact angles of the denim fabric obtained in example 9 of the present invention after contacting 5s, 6s, 8s, 10s, and 15s water drops.

FIG. 4 shows the contact angles of the denim fabric obtained in example 9 of the present invention after contacting drops of water on the fabric for 5s, 6s, 8s, 10s and 15 s.

Detailed Description

The present invention is further described below in conjunction with the following figures and specific examples so that those skilled in the art may better understand the present invention and practice it, but the examples are not intended to limit the present invention.

Examples 1 to 14

The preparation method of the antibacterial hydrophobic denim fabric is as follows, and the specific parameters are shown in table 1:

step 1: washing and drying pure cotton jeans with enzyme, and washing and drying the pure cotton jeans with water;

step 2: carrying out secondary gadolinium soaking treatment on the denim fabric obtained in the step 1 by using a mixed solution and drying;

and step 3: and (3) carrying out vacuum plasma grafting treatment on the denim fabric obtained in the step (2), drying and airing to obtain the antibacterial hydrophobic denim fabric.

TABLE 1 plasma treatment parameters

Test example

Example 9 and comparative example 1 were subjected to a performance test

The fabric of comparative example 1 was virgin denim fabric, which was not modified.

1, the condition of electrostatic charge adsorption degree of methyl orange of jean fabric

Methyl orange is a commonly used acid-base titration indicator in analytical chemistry, and is selected from untreated pure cotton jean fabric, plasma-treated pure cotton jean fabric, plasma-grafted N, N, N-trimethyl-3- [ (1-oxo-2-propenyl) amino ] -propyl chloride (APTAC) double-soaked double-rolled jean fabric, the concentration of a methyl orange solution is 10-5mol/L, the soaking and standing time is 240min, the variable is a plasma treatment condition, corresponding treatment parameters and conditions are shown in the table 1, the methyl orange adsorption electrostatic charge index under the corresponding treatment condition is tested by an ultraviolet-visible spectrophotometer, and the more charges correspond to stronger adsorption performance. According to the formula, the adsorption quantity formula (1) is obtained.

According to the formula adsorption quantity formula (1)

In the formula: co is the concentration (mol/L) before adsorption; c concentration after adsorption (mol/L); v dye solution volume (mL); m mass of adsorbent (g) the degree of adsorption is shown in table 2.

TABLE 2 degree of Electrostatic Charge adsorption of methyl orange

As can be seen from the experimental data in table 2,

wherein comparative example 1 is a comparative reference, it can be seen from Table 2 that the adsorption amount under the plasma treatment condition of example 9 is the largest and is 58.39mol/L, and the plasma condition of the fabric obtained in example 9 under the plasma treatment condition is: the sputtering gas is Ar/O₂The sputtering flow ratio is 50:50, the power is 500W, and the time is 5 minutes.

2, fabric contact Angle test analysis

The denim fabrics obtained in example 9 and comparative example 1 were subjected to a contact angle test, and the contact angle of a water drop on the fabric was measured using a video contact angle measuring instrument model PT-602A (Dataphysics, germany). 10 mu L of water is respectively dripped on different parts of the fabric, and the average value is obtained.

The results are shown in fig. 2-3, fig. 2 is a photograph of the denim fabric before and after the modifier treatment with the liquid droplets, fig. 2(a) shows the instantaneous contact angle as such of the denim fabric without any hydrophobic treatment in comparative example 1, and fig. 2(b) shows the contact angle of the denim fabric finished with the plasma graft modifier APTAC in example 9. The moment deionized water is dripped to the surface of the fabric in the figure 2(a), the fabric has a certain water repellent effect, the contact angle is 78.83 degrees, the hydrophobic angle of the fabric is increased after the fabric is treated by a plasma grafting modifier APTAC in the figure 2(b), the contact angle is 119 degrees, and the fabric has a hydrophobic property.

Fig. 3 shows the change of the contact angles of the 5s, 6s, 8s, 10s and 15s of the water contact angles of the fabric jean obtained by modification in example 9, wherein the contact angles are 109.6 °, 109.1 °, 107.6 °, 105.7 ° and 105.5 °, respectively, and the fabric jean has a good hydrophobic effect.

3, testing the breaking strength of the jean fabric

The antibacterial finishing and finishing process have no damage to the mechanical properties of the denim fabric, the process is mild, the integrity of the fiber structure is well maintained, the result is also confirmed by microscopic SEM structure observation, the result is shown in figure 1, it can be seen from the figure that the surface of the untreated (a) denim fiber in the comparative example 1 is relatively smooth, granular substances exist between the surface of the denim fiber and the fiber of the fabric (b) treated by the plasma in the example 9, the fiber wall has a sticky phenomenon, the surface is not flat and smooth any more, the surface becomes relatively rough, and the obvious damage phenomenon is caused, which indicates that polymers are generated on the surface of the fabric fiber.

The fabrics obtained in example 9 and comparative example 1 were subjected to mechanical property tests such as breaking strength and elongation at break, and the results are shown in table 4, and it can be seen from table 4 that: the breaking strength of the denim fabric after the plasma grafting APTAC antibacterial finishing is not changed greatly and is increased, and the breaking strength values are respectively 1155.36N and 1257.93N, and are increased by 8.89%; the weft breaking strength is 565.56N and 585.54N respectively; compared with untreated denim fabric, the breaking elongation has smaller variation range, the warp direction is changed from 24.75% to 21.7%, the weft direction is changed from 51.04% to 43.82%, the variation range is reduced to 12.3% in the warp direction, and is reduced to 14.14% in the weft direction, so that the finishing process has little influence on the breaking strength performance of the denim fabric.

From the above data, it is known that the antibacterial finishing and finishing process is not destructive to the mechanical properties of the denim fabric, the mildness of the process is good in maintaining the integrity of the fiber structure, which is also confirmed by microscopic SEM structural observation (see fig. 1).

TABLE 4 breaking Strength of denim before and after finishing

4, air permeability of jean fabric

The results of the air permeability tests of the jean fabric obtained in example 9 and the jean fabric obtained in comparative example 1 are shown in table 5, and the data in table 5 show that the air permeability of the jean fabric modified by plasma APTAC grafting (example 9) has little change and the reduction rate is 0.79 percent, and the reason for analyzing the change is that the active ions in the plasma improve the air permeability of the fabric surface, activate the material surface, promote the cross-linking reaction between the material and the finishing agent, and have little influence on the air permeability of the fabric surface.

TABLE 5 air permeability of denim fabric

5, antibacterial property test of denim fabric

The denim fabric obtained in example 9 and comparative example 1 is subjected to antibacterial property detection, the antibacterial activity of the denim fabric is characterized based on AATCC (American style control for control) test method detection, and the concentration of staphylococcus aureus S.aureus in the test is 9.67 multiplied by 10⁶CFU, E.coli O157H 7 concentration 2.50X 10⁷CFU, when the jean fabric obtained in example 9 is contacted with bacteria for 30 minutes, the staphylococcus aureus resistant rate reaches 92.8%, and the escherichia coli resistant rate reaches 94.87% (see the result in Table 6), and the antibacterial test result shows that the pure cotton jean fabric modified by the plasma grafted APTAC has obvious sterilization effect and excellent antibacterial performance. Due to the existence of a large amount of quaternary ammonium salt on the surface of the modified jean fabric, bacteria are quickly attracted by the quaternary ammonium salt molecules with positive charges after contacting the fabric, and the quaternary ammonium salt molecules adsorbed on the surface of the bacteria can penetrate into cell membranes to inactivate the bacteria, so that the aim of sterilization is fulfilled.

TABLE 3 antibacterial test results of virgin denim fabric and APTAC modified denim fabric

APTAC is selected as an antibacterial monomer, and vacuum plasma is adoptedThe body process carries out hydrophobic antibacterial finishing on the pure cotton jean fabric with Ar/O sputtering gas₂And the electrostatic charge of the methyl orange is the most, and the corresponding adsorption performance is the strongest under the conditions of mixing, sputtering flow ratio of 50:50, and processing time of 5min with power of 500W. Under the optimal process conditions, the contact angle of the finished jean fabric reaches 119 degrees, the breaking strength and the fabric air permeability are reduced to a certain extent, but the reduction range is small, and the antibacterial result shows that the jean fabric which is grafted by plasma and is treated by the modifier APTAC can ensure that the concentration is 1.50 multiplied by 10 within 30min⁶The killing rate of the CFU staphylococcus aureus is 92.8 percent, and the concentration is 3.76 multiplied by 10⁶The CFU E.coli kill rate was 94.87%. The results show that argon-oxygen plasma can assist the adhesion of the modifier to the fabric, and successful grafting of the modifier can inhibit bacterial growth, resulting in durable and reproducible antimicrobial performance. The plasma process is simple to operate, easy to control, free of an initiator, short in finishing time, expected to be subjected to industrial batch treatment and obvious in sterilization effect.

It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.