阅读说明：本技术 一种抗菌针织面料的制备方法 (Preparation method of antibacterial knitted fabric ) 是由 沈建根 王雪 尹立新 王山水 汤方明 杨超明 于 2020-12-29 设计创作，主要内容包括：本发明涉及一种抗菌针织面料的制备方法,由抗菌聚酯纤维和莫代尔纤维混纺成的混纺纱线添加氨纶织造得到针织单面布后,依次经过预定型、前处理、染色、脱水、剖幅、烘干、定型和预缩得到抗菌针织面料；抗菌针织面料中各组分重量份数为：抗菌聚酯纤维25～40份,莫代尔纤维50～70份,氨纶5～10份；抗菌聚酯纤维的聚酯链段包括对苯二甲酸链段、乙二醇链段和对苯二甲酸-2(4-吡啶)链段,且不同聚酯链段的对苯二甲酸-2(4-吡啶)链段之间经Ag～+配位；对苯二甲酸-2(4-吡啶)链段参与配位的为吡啶上的N原子；本发明利用配位技术使Ag～+被牢牢地控制在聚酯纤维内,从而增强了抗菌剂的抗菌除臭效率及其在聚酯纤维内的永久性,提高了抗菌性的持续性,性能优异,健康环保。(The invention relates to a preparation method of an antibacterial knitted fabric, which is obtained by adding spandex into blended yarns blended by antibacterial polyester fibers and modal fibers for weavingAfter the single-sided cloth is knitted, sequentially carrying out pre-setting, pre-treatment, dyeing, dewatering, slitting, drying, setting and preshrinking to obtain the antibacterial knitted fabric; the antibacterial knitted fabric comprises the following components in parts by weight: 25-40 parts of antibacterial polyester fiber, 50-70 parts of modal fiber and 5-10 parts of spandex; the polyester chain segment of the antibacterial polyester fiber comprises a terephthalic acid chain segment, an ethylene glycol chain segment and a terephthalic acid-2 (4-pyridine) chain segment, and Ag is arranged between the terephthalic acid-2 (4-pyridine) chain segments of different polyester chain segments + Coordination; the terephthalic acid-2 (4-pyridine) chain segment participates in coordination and is an N atom on pyridine; the invention utilizes coordination technology to lead Ag to be + Is firmly controlled in the polyester fiber, thereby enhancing the antibacterial deodorization efficiency of the antibacterial agent and the permanence of the antibacterial agent in the polyester fiber, improving the continuity of the antibacterial property, having excellent performance and being healthy and environment-friendly.)

1. A preparation method of an antibacterial knitted fabric is characterized by comprising the following steps: adding spandex into blended yarns blended by antibacterial polyester fibers and modal fibers to weave a knitted single-sided fabric, and sequentially performing pre-shaping, pre-treatment, dyeing, dehydration, slitting, drying, shaping and preshrinking to obtain an antibacterial knitted fabric;

the antibacterial knitted fabric comprises the following components in parts by weight: 25-40 parts of antibacterial polyester fiber, 50-70 parts of modal fiber and 5-10 parts of spandex;

the polyester chain segment of the antibacterial polyester fiber comprises a terephthalic acid chain segment, an ethylene glycol chain segment and a terephthalic acid-2 (4-pyridine) chain segment, and Ag is arranged between the terephthalic acid-2 (4-pyridine) chain segments of different polyester chain segments⁺Coordination;

the molar ratio of the terephthalic acid chain segment to the terephthalic acid-2 (4-pyridine) chain segment is 1: 0.01-0.02;

the terephthalic acid-2 (4-pyridine) chain segment is coordinated by N atoms on pyridine.

2. The method of claim 1, wherein the terephthalic acid-2 (4-pyridine) segments of different polyester segments are separated by Ag⁺The coordination structure formed by coordination is as follows:

3. the preparation method of the antibacterial knitted fabric according to claim 1, wherein the antibacterial rate of the antibacterial knitted fabric to escherichia coli and staphylococcus aureus is more than 99%, and a precipitation test is as follows: it was not detected.

4. The method for preparing the antibacterial knitted fabric according to claim 1, wherein the fineness of the modal fiber is 75-90 dtex, the thickness of the blended yarn formed by blending the antibacterial polyester fiber and the modal fiber is 30-50S, and the fineness of the spandex is 20-30 dtex.

5. The method for preparing an antibacterial knitted fabric according to claim 1, wherein in the step of weaving the knitted single-face fabric, the weaving is performed on a 30-inch 28-needle circular knitting machine; the dyeing is carried out by one-bath mixed dyeing, and the dyeing temperature is 125-130 ℃; the presetting temperature is 180-190 ℃; the drying temperature is 110-115 ℃; setting temperature is 130-140 ℃; the pre-shrinking temperature is 110-120 ℃.

6. The method for preparing an antibacterial knitted fabric according to claim 1, wherein the antibacterial polyester fiber is prepared from modified polyester by metering, extruding, cooling, oiling, stretching, heat setting and winding;

the preparation method of the modified polyester comprises the following steps: uniformly mixing terephthalic acid, ethylene glycol, terephthalic acid-2 (4-pyridine) and silver-containing zeolite powder, and then carrying out esterification reaction and polycondensation reaction in sequence to obtain the modified polyester.

7. The method for preparing the antibacterial knitted fabric according to claim 6, wherein the modified polyester is prepared by the following steps:

(1) performing esterification reaction;

preparing terephthalic acid, ethylene glycol and terephthalic acid-2 (4-pyridine) into slurry, adding silver-containing zeolite powder, a catalyst and a stabilizer, uniformly mixing, pressurizing in a nitrogen atmosphere to perform esterification reaction, wherein the pressurizing pressure is normal pressure to 0.3MPa, the esterification reaction temperature is 250-260 ℃, and the termination condition of the esterification reaction is as follows: the distilled amount of water in the esterification reaction reaches more than 95 percent of a theoretical value;

(2) performing polycondensation reaction;

after the esterification reaction is finished, starting the polycondensation reaction in a low vacuum stage under the condition of negative pressure, stably pumping the pressure in the low vacuum stage from normal pressure to below 500Pa in 30-50 min at the reaction temperature of 250-260 ℃ for 30-50 min, then continuously pumping the vacuum to perform the polycondensation reaction in a high vacuum stage, further reducing the reaction pressure to below 50Pa at the reaction temperature of 270-282 ℃ for 50-70 min, and thus obtaining the modified polyester.

8. The preparation method of the antibacterial knitted fabric according to claim 7, wherein the molar ratio of the terephthalic acid to the ethylene glycol to the terephthalic acid-2 (4-pyridine) is 1: 1.2-2: 0.01-0.02, the addition amounts of the catalyst and the stabilizer are 0.02-0.03 wt% and 0.01-0.05 wt% of the addition amount of the terephthalic acid, respectively, and the addition amount of the silver-containing zeolite powder is 0.02-0.03 wt% of the addition amount of the terephthalic acid.

9. The method for preparing an antibacterial knitted fabric according to claim 8, wherein the catalyst is antimony trioxide, ethylene glycol antimony or antimony acetate, and the stabilizer is triphenyl phosphate, trimethyl phosphate or trimethyl phosphite.

10. The method for preparing the antibacterial knitted fabric according to claim 6, wherein the fineness of the antibacterial polyester fiber is 50-75 dtex, the breaking strength is more than or equal to 3.5cN/dtex, the elongation at break is 40.0 +/-3.0%, the CV value of the breaking strength is less than or equal to 5.0%, the CV value of the elongation at break is less than or equal to 10.0%, and the shrinkage in boiling water is 7.5 +/-0.5%.

11. The preparation method of the antibacterial knitted fabric according to claim 6, wherein the spinning process parameters of the antibacterial polyester fiber are as follows:

spinning temperature: 287-295 ℃;

cooling temperature: 20-25 ℃;

network pressure: 0.20 to 0.30 MPa;

a roll speed: 3100 to 3200m/min

First roll temperature: 88 to 93 ℃;

two roll speed: 3900 to 4100 m/min;

temperature of the two rolls: 120-130 ℃;

winding speed: 3800-4000 m/min.

Technical Field

The invention belongs to the technical field of antibacterial fabrics, and relates to a preparation method of an antibacterial knitted fabric.

Background

With the improvement of human material civilization, people pay more and more attention to health and seek comfortable clothes. The antibacterial, deodorant and acaricidal fibers have the health care function and the health care function, and are particularly important in the medical and health care industry. The textiles used in medical and pharmaceutical industries can become transmission media of bacteria, so that cross infection is caused, recovery of patients is affected, and other diseases are even caused, so that life safety is threatened. According to the data provided by the Ministry of health, the hospital infection rate of the inpatients is 9.7%, and the nosocomial bacterial infection is related to the nosocomial death cases. Meanwhile, with the improvement of living standard of people, the special requirements on the aspects of human body protection and health care functions are put forward for the civil textiles besides the inherent characteristics of natural fiber fabrics, thereby promoting the development of synthetic fibers from differentiation to functionalization and health care and widening the application of chemical fibers.

The silver-based antibacterial agent has a silver ion contact reaction sterilization mechanism: the silver in the antibacterial material is generally Ag⁺In the form of micro-Ag⁺When contacting with the cell wall of microorganism, the latter is negatively charged, and is adsorbed firmly by Coulomb attraction, Ag⁺Penetrating cell membranes into cells and destroying cellular synthasesActive, the cells lose the ability to divide and multiply and die. Ag⁺Can also destroy electron transfer system, respiratory system, and substance transfer system of microorganism. But Ag in polyester fiber⁺The antibacterial agent migrates to the surface of the fiber under certain time and temperature conditions, so that the antibacterial property is reduced, and simultaneously Ag⁺May enter the human body and cause other problems.

How to improve the continuity of the antibacterial polyester fiber and reduce Ag⁺The migration has important significance for researching and developing polyester products with antibacterial effect, improving the quality of human life and ensuring the health of personal life.

Disclosure of Invention

The invention aims to solve the problems in the prior art and provides a preparation method of an antibacterial knitted fabric.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

a preparation method of an antibacterial knitted fabric comprises the steps of adding spandex into blended yarns blended by antibacterial polyester fibers and modal fibers for weaving to obtain a knitted single-sided fabric, and sequentially carrying out pre-shaping, pre-treatment, dyeing, dewatering, slitting, drying, shaping and preshrinking to obtain the antibacterial knitted fabric;

the antibacterial knitted fabric comprises the following components in parts by weight: 25-40 parts of antibacterial polyester fiber, 50-70 parts of modal fiber and 5-10 parts of spandex;

the polyester chain segment of the antibacterial polyester fiber comprises a terephthalic acid chain segment, an ethylene glycol chain segment and a terephthalic acid-2 (4-pyridine) chain segment, and Ag is arranged between the terephthalic acid-2 (4-pyridine) chain segments of different polyester chain segments⁺Coordination;

the molar ratio of the terephthalic acid chain segment to the terephthalic acid-2 (4-pyridine) chain segment is 1: 0.01-0.02;

the terephthalic acid-2 (4-pyridine) chain segment is coordinated by N atoms on pyridine.

As a preferred technical scheme:

the preparation method of the antibacterial knitted fabric comprises the step of enabling the terephthalic acid-2 (4-pyridine) chain segments of different polyester chain segments to pass through Ag⁺The coordination structure formed by coordination is as follows:

according to the preparation method of the antibacterial knitted fabric, the antibacterial rate of the antibacterial knitted fabric to escherichia coli and staphylococcus aureus is more than 99% (the antibacterial performance is tested by adopting QB/T2591-2003 standard), and a precipitation test is carried out: not detected (precipitation test method: placing the fabric sample in distilled water, soaking at room temperature for 24 hours, and detecting Ag in water by EPA 200.8:1994, ICP-MS test method)⁺Content of (d).

According to the preparation method of the antibacterial knitted fabric, the fineness of the modal fiber is 75-90 dtex, the thickness of the blended yarn formed by blending the antibacterial polyester fiber and the modal fiber is 30-50S, and the fineness of the spandex is 20-30 dtex.

In the preparation method of the antibacterial knitted fabric, in the step of weaving the knitted single-side fabric, weaving is performed on a 30-inch 28-needle circular knitting machine; the dyeing is carried out by one-bath mixed dyeing, and the dyeing temperature is 125-130 ℃; the presetting temperature is 180-190 ℃; the drying temperature is 110-115 ℃; setting temperature is 130-140 ℃; the pre-shrinking temperature is 110-120 ℃.

According to the preparation method of the antibacterial knitted fabric, the antibacterial polyester fiber is prepared by metering, extruding, cooling, oiling, stretching, heat setting and winding the modified polyester;

the preparation method of the modified polyester comprises the following steps: uniformly mixing terephthalic acid, ethylene glycol, terephthalic acid-2 (4-pyridine) and silver-containing zeolite powder (an antibacterial agent), and then carrying out esterification reaction and polycondensation reaction in sequence to obtain the modified polyester.

According to the preparation method of the antibacterial knitted fabric, the preparation steps of the modified polyester are as follows:

(1) performing esterification reaction;

preparing terephthalic acid, ethylene glycol and terephthalic acid-2 (4-pyridine) into slurry, adding silver-containing zeolite powder, a catalyst and a stabilizer, uniformly mixing, pressurizing in a nitrogen atmosphere to perform esterification reaction, wherein the pressurizing pressure is normal pressure to 0.3MPa, the esterification reaction temperature is 250-260 ℃, and the termination condition of the esterification reaction is as follows: the distilled amount of water in the esterification reaction reaches more than 95 percent of a theoretical value;

(2) performing polycondensation reaction;

after the esterification reaction is finished, starting the polycondensation reaction in a low vacuum stage under the condition of negative pressure, stably pumping the pressure in the low vacuum stage from normal pressure to below 500Pa in 30-50 min at the reaction temperature of 250-260 ℃ for 30-50 min, then continuously pumping the vacuum to perform the polycondensation reaction in a high vacuum stage, further reducing the reaction pressure to below 50Pa at the reaction temperature of 270-282 ℃ for 50-70 min, and thus obtaining the modified polyester.

According to the preparation method of the antibacterial knitted fabric, the molar ratio of the terephthalic acid to the ethylene glycol to the terephthalic acid-2 (4-pyridine) is 1: 1.2-2: 0.01-0.02, the addition amounts of the catalyst and the stabilizer are 0.02-0.03 wt% and 0.01-0.05 wt% of the addition amount of the terephthalic acid respectively, and the addition amount of the silver-containing zeolite powder is 0.02-0.03 wt% of the addition amount of the terephthalic acid.

According to the preparation method of the antibacterial knitted fabric, the catalyst is antimony trioxide, ethylene glycol antimony or antimony acetate, and the stabilizer is triphenyl phosphate, trimethyl phosphate or trimethyl phosphite.

According to the preparation method of the antibacterial knitted fabric, the titer of the antibacterial polyester fiber is 50-75 dtex, the breaking strength is more than or equal to 3.5cN/dtex, the elongation at break is 40.0 +/-3.0%, the CV value of the breaking strength is less than or equal to 5.0%, the CV value of the elongation at break is less than or equal to 10.0%, and the shrinkage in boiling water is 7.5 +/-0.5%.

According to the preparation method of the antibacterial knitted fabric, the spinning process parameters of the antibacterial polyester fiber are as follows:

spinning temperature: 287-295 ℃;

cooling temperature: 20-25 ℃;

network pressure: 0.20 to 0.30 MPa;

a roll speed: 3100 to 3200m/min

First roll temperature: 88 to 93 ℃;

two roll speed: 3900 to 4100 m/min;

temperature of the two rolls: 120-130 ℃;

winding speed: 3800-4000 m/min.

The principle of the invention is as follows:

the migration refers to a process of diffusion of the additive in the fiber from the material to the fiber surface, and the additive in the fiber, such as silver ions, and polyester macromolecules do not form chemical bonds, but are connected by van der waals force, maintain independent chemical properties, have certain activity, and are susceptible to the influence of external environments, including use temperature, use environment and the like, and migrate to the fiber surface.

The free volume, i.e., the size of the space in which silver ions freely move between the polyester molecular chains, is greater, and the unbound silver ions are more likely to migrate from the polyester fiber. The movement of the polyester segments is determined by the structure of the segments, the degree of crosslinking, and the degree of crystallinity. The migration process of silver ions is also influenced by the aggregation state of polyester, namely the space network structure of the polyester molecular chain, the saturation of the space network structure tends to limit the movement of the silver ions, and the migration and diffusion of the silver ions in the polyester are also inhibited, so that the higher the saturation of the space network structure of the polyester is, the smaller the diffusion coefficient of the silver ions is, and the more difficult the migration and diffusion of the silver ions in the polyester is.

The antibacterial knitted fabric is woven by adding spandex into blended yarns blended by antibacterial polyester fibers and modal fibers, and Ag in the antibacterial polyester fibers⁺Can form a coordination bond with a terephthalic acid-2 (4-pyridine) chain segment to form a bridge chain structure, and the bond energy of the coordination bond is greater than that of a hydrogen bond, so that the movement of silver ions is limited, and the migration and diffusion of the silver ions in the polyester are more difficult to carry out. On the other hand, Ag⁺Can form coordinate bond with terephthalic acid-2 (4-pyridine) chain segment, so that polyester generates physical cross-linking points and intermolecular action is enhanced, the saturation of a polyester space network structure is correspondingly improved, the freedom degree of chain segment motion is reduced, the rigidity of polyester macromolecules is increased, and the intermolecular free volume of the polyester macromolecule chains is increasedReduce and reduce Ag⁺Penetration route in PET matrix, making Ag⁺Migration within the internal structure is more difficult.

Has the advantages that:

the invention utilizes coordination technology to lead Ag to be⁺The antibacterial knitted fabric is firmly controlled in the polyester fiber and cannot migrate, so that the antibacterial deodorization efficiency of the antibacterial agent and the lasting effect of the antibacterial agent in the polyester fiber are enhanced, the antibacterial property continuity is improved, and the prepared antibacterial knitted fabric has excellent antibacterial performance and meets the requirements of a large trend of health and environmental protection.

Detailed Description

The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.

Example 1

A preparation method of an antibacterial knitted fabric comprises the following specific steps:

(1) preparing modified polyester;

(1.1) esterification reaction;

preparing terephthalic acid, ethylene glycol and terephthalic acid-2 (4-pyridine) into slurry with a molar ratio of 1:1.2:0.01, adding silver-containing zeolite powder, a catalyst (antimony trioxide) and a stabilizer (triphenyl phosphate) and uniformly mixing, wherein the adding amounts of the catalyst and the stabilizer are 0.02 wt% and 0.01 wt% of the adding amount of the terephthalic acid respectively, and the adding amount of the silver-containing zeolite powder is 0.03 wt% of the adding amount of the terephthalic acid; then pressurizing in a nitrogen atmosphere to perform esterification reaction, wherein the pressurizing pressure is 0.1MPa, the temperature of the esterification reaction is 260 ℃, and the termination conditions of the esterification reaction are as follows: the distilled water amount in the esterification reaction reaches 95 percent of a theoretical value;

(1.2) polycondensation reaction;

after the esterification reaction is finished, starting the polycondensation reaction in the low vacuum stage under the negative pressure condition, stably pumping the pressure in the stage from normal pressure to the absolute pressure of 500Pa within 30min, controlling the reaction temperature to be 250 ℃ and the reaction time to be 50min, then continuing pumping vacuum, and carrying out the polycondensation reaction in the high vacuum stage to further reduce the reaction pressure to the absolute pressure of 50Pa, control the reaction temperature to be 274 ℃ and control the reaction time to be 60min, thus obtaining the modified polyester;

(2) preparing antibacterial polyester fibers;

the modified polyester is subjected to metering, extrusion, cooling, oiling, stretching, heat setting and winding to prepare antibacterial polyester fiber;

the spinning process parameters are as follows:

spinning temperature: 287 deg.C;

cooling temperature: 20 ℃;

network pressure: 0.3 MPa;

a roll speed: 3100m/min

First roll temperature: 91 ℃;

two roll speed: 3900 m/min;

temperature of the two rolls: 126 ℃;

winding speed: 3800 m/min.

The polyester chain segment of the prepared antibacterial polyester fiber comprises a terephthalic acid chain segment, an ethylene glycol chain segment and a terephthalic acid-2 (4-pyridine) chain segment, and the molar ratio of the terephthalic acid chain segment to the terephthalic acid-2 (4-pyridine) chain segment is 1: 0.01; between terephthalic acid-2 (4-pyridine) chain segments of different polyester chain segments through Ag⁺The coordination is carried out, and the terephthalic acid-2 (4-pyridine) chain segment participates in coordination, and is N atom on pyridine, and the coordination structure formed by coordination is as follows:the titer of the antibacterial polyester fiber is 50dtex, the breaking strength is 3.5cN/dtex, the elongation at break is 43 percent, the CV value of the breaking strength is 5 percent, the CV value of the elongation at break is 10 percent, and the shrinkage in boiling water is 8 percent;

(3) weaving the knitted single-sided cloth;

adding spandex into blended yarns formed by blending modal fibers and the antibacterial polyester fibers prepared in the step (2) on a 30-inch 28-needle circular knitting machine to weave a knitted single-sided fabric;

wherein the weight parts of the components are as follows: 32 parts of antibacterial polyester fiber, 62 parts of modal fiber and 8 parts of spandex;

the titer of the modal fiber is 75dtex, the thickness of the blended yarn blended by the antibacterial polyester fiber and the modal fiber is 30S, and the titer of the spandex is 20 dtex;

(4) preparing an antibacterial knitted fabric;

the knitted single-sided fabric prepared in the step (3) is sequentially subjected to pre-setting, pre-treatment, dyeing, dehydration, slitting, drying, setting and preshrinking to obtain an antibacterial knitted fabric;

the dyeing adopts one-bath mixed dyeing, and the dyeing temperature is 125 ℃; the presetting temperature is 180 ℃; the drying temperature is 113 ℃; setting temperature is 136 ℃; the preshrinking temperature was 115 ℃.

The prepared antibacterial knitted fabric has 99% of antibacterial rate on escherichia coli and 99.1% of antibacterial rate on staphylococcus aureus, and the precipitation test is as follows: it was not detected.

Example 2

A preparation method of an antibacterial knitted fabric comprises the following specific steps:

(1) preparing modified polyester;

(1.1) esterification reaction;

preparing terephthalic acid, ethylene glycol and terephthalic acid-2 (4-pyridine) into slurry with the molar ratio of 1:1.3:0.01, adding silver-containing zeolite powder, a catalyst (antimony trioxide) and a stabilizer (triphenyl phosphate) and uniformly mixing, wherein the adding amounts of the catalyst and the stabilizer are 0.02 wt% and 0.03 wt% of the adding amount of the terephthalic acid respectively, and the adding amount of the silver-containing zeolite powder is 0.03 wt% of the adding amount of the terephthalic acid; then pressurizing in a nitrogen atmosphere to perform esterification reaction, wherein the pressurizing pressure is 0.3MPa, the temperature of the esterification reaction is 250 ℃, and the termination conditions of the esterification reaction are as follows: the distilled water amount in the esterification reaction reaches 99 percent of the theoretical value;

(1.2) polycondensation reaction;

after the esterification reaction is finished, starting the polycondensation reaction in the low vacuum stage under the negative pressure condition, stably pumping the pressure in the stage from normal pressure to absolute pressure of 480Pa within 32min, wherein the reaction temperature is 259 ℃, the reaction time is 35min, then continuously pumping vacuum, and carrying out the polycondensation reaction in the high vacuum stage to further reduce the reaction pressure to absolute pressure of 40Pa, the reaction temperature is 272 ℃, and the reaction time is 66min, thus obtaining the modified polyester;

(2) preparing antibacterial polyester fibers;

the modified polyester is subjected to metering, extrusion, cooling, oiling, stretching, heat setting and winding to prepare antibacterial polyester fiber;

the spinning process parameters are as follows:

spinning temperature: 288 ℃;

cooling temperature: 21 ℃;

network pressure: 0.25 MPa;

a roll speed: 3100m/min

First roll temperature: 92 ℃;

two roll speed: 3900 m/min;

temperature of the two rolls: 128 ℃;

winding speed: 3800 m/min.

The polyester chain segment of the prepared antibacterial polyester fiber comprises a terephthalic acid chain segment, an ethylene glycol chain segment and a terephthalic acid-2 (4-pyridine) chain segment, and the molar ratio of the terephthalic acid chain segment to the terephthalic acid-2 (4-pyridine) chain segment is 1: 0.01; between terephthalic acid-2 (4-pyridine) chain segments of different polyester chain segments through Ag⁺The coordination is carried out, and the terephthalic acid-2 (4-pyridine) chain segment participates in coordination, and is N atom on pyridine, and the coordination structure formed by coordination is as follows:the fineness of the antibacterial polyester fiber is 54dtex, the breaking strength is 3.6cN/dtex, the elongation at break is 41%, the CV value of the breaking strength is 4.85%, the CV value of the elongation at break is 9.7%, and the boiling water shrinkage rate is 7.8%;

(3) weaving the knitted single-sided cloth;

adding spandex into blended yarns formed by blending modal fibers and the antibacterial polyester fibers prepared in the step (2) on a 30-inch 28-needle circular knitting machine to weave a knitted single-sided fabric;

wherein the weight parts of the components are as follows: 29 parts of antibacterial polyester fiber, 57 parts of modal fiber and 7 parts of spandex;

the titer of the modal fiber is 86dtex, the thickness of the blended yarn blended by the antibacterial polyester fiber and the modal fiber is 38S, and the titer of the spandex is 26 dtex;

(4) preparing an antibacterial knitted fabric;

the knitted single-sided fabric prepared in the step (3) is sequentially subjected to pre-setting, pre-treatment, dyeing, dehydration, slitting, drying, setting and preshrinking to obtain an antibacterial knitted fabric;

the dyeing adopts one-bath mixed dyeing, and the dyeing temperature is 129 ℃; the presetting temperature is 190 ℃; the drying temperature is 114 ℃; setting temperature is 132 ℃; the preshrinking temperature was 116 ℃.

The antibacterial rate of the prepared antibacterial knitted fabric to escherichia coli and staphylococcus aureus is 99.3%, and the precipitation test is as follows: it was not detected.

Example 3

A preparation method of an antibacterial knitted fabric comprises the following specific steps:

(1) preparing modified polyester;

(1.1) esterification reaction;

preparing terephthalic acid, ethylene glycol and terephthalic acid-2 (4-pyridine) into slurry with a molar ratio of 1:1.4:0.01, adding silver-containing zeolite powder, a catalyst (antimony trioxide) and a stabilizer (triphenyl phosphate) and uniformly mixing, wherein the adding amounts of the catalyst and the stabilizer are 0.02 wt% and 0.05 wt% of the adding amount of the terephthalic acid respectively, and the adding amount of the silver-containing zeolite powder is 0.03 wt% of the adding amount of the terephthalic acid; then pressurizing in a nitrogen atmosphere to perform esterification reaction, wherein the pressurizing pressure is 0.2MPa, the temperature of the esterification reaction is 257 ℃, and the termination conditions of the esterification reaction are as follows: the distilled water amount in the esterification reaction reaches 98 percent of the theoretical value;

(1.2) polycondensation reaction;

after the esterification reaction is finished, starting the polycondensation reaction in the low vacuum stage under the negative pressure condition, stably pumping the pressure in the low vacuum stage from normal pressure to absolute pressure of 440Pa within 35min, controlling the reaction temperature to 258 ℃, controlling the reaction time to be 40min, then continuously pumping vacuum, and carrying out the polycondensation reaction in the high vacuum stage to further reduce the reaction pressure to absolute pressure of 15Pa, controlling the reaction temperature to be 278 ℃, and controlling the reaction time to be 55min to obtain the modified polyester;

(2) preparing antibacterial polyester fibers;

the modified polyester is subjected to metering, extrusion, cooling, oiling, stretching, heat setting and winding to prepare antibacterial polyester fiber;

the spinning process parameters are as follows:

spinning temperature: 289 deg.C;

cooling temperature: 22 ℃;

network pressure: 0.23 MPa;

a roll speed: 3100m/min

First roll temperature: 92 ℃;

two roll speed: 4000 m/min;

temperature of the two rolls: 120 ℃;

winding speed: 3900 m/min.

The polyester chain segment of the prepared antibacterial polyester fiber comprises a terephthalic acid chain segment, an ethylene glycol chain segment and a terephthalic acid-2 (4-pyridine) chain segment, and the molar ratio of the terephthalic acid chain segment to the terephthalic acid-2 (4-pyridine) chain segment is 1: 0.01; between terephthalic acid-2 (4-pyridine) chain segments of different polyester chain segments through Ag⁺The coordination is carried out, and the terephthalic acid-2 (4-pyridine) chain segment participates in coordination, and is N atom on pyridine, and the coordination structure formed by coordination is as follows:the fineness of the antibacterial polyester fiber is 68dtex, the breaking strength is 3.54cN/dtex, the elongation at break is 42%, the CV value of the breaking strength is 4.95%, the CV value of the elongation at break is 9.8%, and the boiling water shrinkage rate is 7.7%;

(3) weaving the knitted single-sided cloth;

adding spandex into blended yarns formed by blending modal fibers and the antibacterial polyester fibers prepared in the step (2) on a 30-inch 28-needle circular knitting machine to weave a knitted single-sided fabric;

wherein the weight parts of the components are as follows: 25 parts of antibacterial polyester fiber, 50 parts of modal fiber and 5 parts of spandex;

the titer of the modal fiber is 87dtex, the thickness of the blended yarn blended by the antibacterial polyester fiber and the modal fiber is 40S, and the titer of the spandex is 28 dtex;

(4) preparing an antibacterial knitted fabric;

the knitted single-sided fabric prepared in the step (3) is sequentially subjected to pre-setting, pre-treatment, dyeing, dehydration, slitting, drying, setting and preshrinking to obtain an antibacterial knitted fabric;

the dyeing adopts one-bath mixed dyeing, and the dyeing temperature is 130 ℃; the presetting temperature is 182 ℃; the drying temperature is 112 ℃; setting temperature is 134 ℃; the preshrinking temperature was 112 ℃.

The antibacterial rate of the prepared antibacterial knitted fabric to escherichia coli is 99.3%, the antibacterial rate of staphylococcus aureus is 99.4%, and a precipitation test is as follows: it was not detected.

Example 4

A preparation method of an antibacterial knitted fabric comprises the following specific steps:

(1) preparing modified polyester;

(1.1) esterification reaction;

preparing terephthalic acid, ethylene glycol and terephthalic acid-2 (4-pyridine) into slurry with a molar ratio of 1:1.5:0.02, adding silver-containing zeolite powder, a catalyst (ethylene glycol antimony) and a stabilizer (trimethyl phosphate), and uniformly mixing, wherein the addition amounts of the catalyst and the stabilizer are 0.025 wt% and 0.02 wt% of the addition amount of the terephthalic acid respectively, and the addition amount of the silver-containing zeolite powder is 0.03 wt% of the addition amount of the terephthalic acid; then pressurizing in a nitrogen atmosphere to carry out esterification reaction, wherein the pressurizing pressure is 0.2MPa, the temperature of the esterification reaction is 258 ℃, and the termination conditions of the esterification reaction are as follows: the distilled water amount in the esterification reaction reaches 97 percent of the theoretical value;

(1.2) polycondensation reaction;

after the esterification reaction is finished, starting the polycondensation reaction in the low vacuum stage under the negative pressure condition, stably pumping the pressure in the stage from normal pressure to absolute pressure of 450Pa within 38min, controlling the reaction temperature to be 252 ℃ and the reaction time to be 47min, then continuing pumping vacuum, and carrying out the polycondensation reaction in the high vacuum stage to further reduce the reaction pressure to absolute pressure of 18Pa, control the reaction temperature to be 280 ℃ and control the reaction time to be 53min, thus obtaining the modified polyester;

(2) preparing antibacterial polyester fibers;

the modified polyester is subjected to metering, extrusion, cooling, oiling, stretching, heat setting and winding to prepare antibacterial polyester fiber;

the spinning process parameters are as follows:

spinning temperature: 290 ℃;

cooling temperature: 23 ℃;

network pressure: 0.2 MPa;

a roll speed: 3200m/min

First roll temperature: 88 ℃;

two roll speed: 4000 m/min;

temperature of the two rolls: 122 ℃;

winding speed: 3900 m/min.

The polyester chain segment of the prepared antibacterial polyester fiber comprises a terephthalic acid chain segment, an ethylene glycol chain segment and a terephthalic acid-2 (4-pyridine) chain segment, and the molar ratio of the terephthalic acid chain segment to the terephthalic acid-2 (4-pyridine) chain segment is 1: 0.02; between terephthalic acid-2 (4-pyridine) chain segments of different polyester chain segments through Ag⁺The coordination is carried out, and the terephthalic acid-2 (4-pyridine) chain segment participates in coordination, and is N atom on pyridine, and the coordination structure formed by coordination is as follows:the fineness of the antibacterial polyester fiber is 70dtex, the breaking strength is 3.65cN/dtex, the elongation at break is 40%, the CV value of the breaking strength is 4.78%, the CV value of the elongation at break is 9.4%, and the boiling water shrinkage rate is 7.5%;

(3) weaving the knitted single-sided cloth;

adding spandex into blended yarns formed by blending modal fibers and the antibacterial polyester fibers prepared in the step (2) on a 30-inch 28-needle circular knitting machine to weave a knitted single-sided fabric;

wherein the weight parts of the components are as follows: 38 parts of antibacterial polyester fiber, 68 parts of modal fiber and 10 parts of spandex;

the fineness of the modal fiber is 89dtex, the thickness of blended yarn blended by the antibacterial polyester fiber and the modal fiber is 46S, and the fineness of the spandex is 29 dtex;

(4) preparing an antibacterial knitted fabric;

the knitted single-sided fabric prepared in the step (3) is sequentially subjected to pre-setting, pre-treatment, dyeing, dehydration, slitting, drying, setting and preshrinking to obtain an antibacterial knitted fabric;

the dyeing adopts one-bath mixed dyeing, and the dyeing temperature is 128 ℃; the presetting temperature is 186 ℃; the drying temperature is 115 ℃; setting temperature is 140 ℃; the preshrinking temperature was 114 ℃.

The antibacterial rate of the prepared antibacterial knitted fabric to escherichia coli and staphylococcus aureus is 99%, and a precipitation test is as follows: it was not detected.

Example 5

A preparation method of an antibacterial knitted fabric comprises the following specific steps:

(1) preparing modified polyester;

(1.1) esterification reaction;

preparing terephthalic acid, ethylene glycol and terephthalic acid-2 (4-pyridine) into slurry with the molar ratio of 1:1.6:0.02, adding silver-containing zeolite powder, a catalyst (ethylene glycol antimony) and a stabilizer (trimethyl phosphate), and uniformly mixing, wherein the addition amounts of the catalyst and the stabilizer are 0.03 wt% and 0.04 wt% of the addition amount of the terephthalic acid respectively, and the addition amount of the silver-containing zeolite powder is 0.02 wt% of the addition amount of the terephthalic acid; then pressurizing in a nitrogen atmosphere to perform esterification reaction, wherein the pressurizing pressure is 0.3MPa, the temperature of the esterification reaction is 256 ℃, and the termination conditions of the esterification reaction are as follows: the distilled water amount in the esterification reaction reaches 96 percent of a theoretical value;

(1.2) polycondensation reaction;

after the esterification reaction is finished, starting the polycondensation reaction in the low vacuum stage under the negative pressure condition, stably pumping the pressure in the low vacuum stage from normal pressure to absolute pressure of 430Pa within 42min, controlling the reaction temperature to be 260 ℃ and the reaction time to be 30min, then continuing pumping vacuum, and carrying out the polycondensation reaction in the high vacuum stage to further reduce the reaction pressure to absolute pressure of 28Pa, control the reaction temperature to be 270 ℃ and control the reaction time to be 70min, thus obtaining the modified polyester;

(2) preparing antibacterial polyester fibers;

the modified polyester is subjected to metering, extrusion, cooling, oiling, stretching, heat setting and winding to prepare antibacterial polyester fiber;

the spinning process parameters are as follows:

spinning temperature: 292 deg.C;

cooling temperature: 24 ℃;

network pressure: 0.26 MPa;

a roll speed: 3200m/min

First roll temperature: 89 ℃;

two roll speed: 4100 m/min;

temperature of the two rolls: 130 ℃;

winding speed: 4000 m/min.

The polyester chain segment of the prepared antibacterial polyester fiber comprises a terephthalic acid chain segment, an ethylene glycol chain segment and a terephthalic acid-2 (4-pyridine) chain segment, and the molar ratio of the terephthalic acid chain segment to the terephthalic acid-2 (4-pyridine) chain segment is 1: 0.02; between terephthalic acid-2 (4-pyridine) chain segments of different polyester chain segments through Ag⁺The coordination is carried out, and the terephthalic acid-2 (4-pyridine) chain segment participates in coordination, and is N atom on pyridine, and the coordination structure formed by coordination is as follows:the fineness of the antibacterial polyester fiber is 58dtex, the breaking strength is 3.78cN/dtex, the elongation at break is 38%, the CV value of the breaking strength is 4.82%, the CV value of the elongation at break is 9.6%, and the boiling water shrinkage rate is 7.3%;

(3) weaving the knitted single-sided cloth;

adding spandex into blended yarns formed by blending modal fibers and the antibacterial polyester fibers prepared in the step (2) on a 30-inch 28-needle circular knitting machine to weave a knitted single-sided fabric;

wherein the weight parts of the components are as follows: 27 parts of antibacterial polyester fiber, 54 parts of modal fiber and 6 parts of spandex;

the fineness of the modal fiber is 78dtex, the thickness of the blended yarn blended by the antibacterial polyester fiber and the modal fiber is 32S, and the fineness of the spandex is 22 dtex;

(4) preparing an antibacterial knitted fabric;

the knitted single-sided fabric prepared in the step (3) is sequentially subjected to pre-setting, pre-treatment, dyeing, dehydration, slitting, drying, setting and preshrinking to obtain an antibacterial knitted fabric;

the dyeing adopts one-bath mixed dyeing, and the dyeing temperature is 126 ℃; the presetting temperature is 188 ℃; the drying temperature is 111 ℃; setting temperature is 137 ℃; the preshrinking temperature was 118 ℃.

The prepared antibacterial knitted fabric has 99.2% of antibacterial rate on escherichia coli and 99.3% of antibacterial rate on staphylococcus aureus, and the precipitation test is as follows: it was not detected.

Example 6

A preparation method of an antibacterial knitted fabric comprises the following specific steps:

(1) preparing modified polyester;

(1.1) esterification reaction;

preparing terephthalic acid, ethylene glycol and terephthalic acid-2 (4-pyridine) into slurry with the molar ratio of 1:1.8:0.02, adding silver-containing zeolite powder, a catalyst (antimony acetate) and a stabilizer (trimethyl phosphite) to be uniformly mixed, wherein the addition amounts of the catalyst and the stabilizer are 0.03 wt% and 0.01 wt% of the addition amount of the terephthalic acid respectively, and the addition amount of the silver-containing zeolite powder is 0.02 wt% of the addition amount of the terephthalic acid; then pressurizing in a nitrogen atmosphere to perform esterification reaction, wherein the pressurizing pressure is 0.3MPa, the temperature of the esterification reaction is 255 ℃, and the termination conditions of the esterification reaction are as follows: the distilled water amount in the esterification reaction reaches 96 percent of a theoretical value;

(1.2) polycondensation reaction;

after the esterification reaction is finished, starting the polycondensation reaction in the low vacuum stage under the negative pressure condition, stably pumping the pressure in the stage from normal pressure to absolute pressure of 400Pa within 48min, controlling the reaction temperature to be 256 ℃ and the reaction time to be 43min, then continuing pumping vacuum, and carrying out the polycondensation reaction in the high vacuum stage to further reduce the reaction pressure to absolute pressure of 30Pa, control the reaction temperature to be 276 ℃ and control the reaction time to be 58min, thus obtaining the modified polyester;

(2) preparing antibacterial polyester fibers;

the modified polyester is subjected to metering, extrusion, cooling, oiling, stretching, heat setting and winding to prepare antibacterial polyester fiber;

the spinning process parameters are as follows:

spinning temperature: 294 ℃;

cooling temperature: 25 ℃;

network pressure: 0.27 MPa;

a roll speed: 3200m/min

First roll temperature: 90 ℃;

two roll speed: 4100 m/min;

temperature of the two rolls: 124 ℃;

winding speed: 4000 m/min.

The polyester chain segment of the prepared antibacterial polyester fiber comprises a terephthalic acid chain segment, an ethylene glycol chain segment and a terephthalic acid-2 (4-pyridine) chain segment, and the molar ratio of the terephthalic acid chain segment to the terephthalic acid-2 (4-pyridine) chain segment is 1: 0.02; between terephthalic acid-2 (4-pyridine) chain segments of different polyester chain segments through Ag⁺The coordination is carried out, and the terephthalic acid-2 (4-pyridine) chain segment participates in coordination, and is N atom on pyridine, and the coordination structure formed by coordination is as follows:the fineness of the antibacterial polyester fiber is 64dtex, the breaking strength is 3.74cN/dtex, the elongation at break is 39%, the CV value of the breaking strength is 4.76%, the CV value of the elongation at break is 9.2%, and the boiling water shrinkage rate is 7.1%;

(3) weaving the knitted single-sided cloth;

adding spandex into blended yarns formed by blending modal fibers and the antibacterial polyester fibers prepared in the step (2) on a 30-inch 28-needle circular knitting machine to weave a knitted single-sided fabric;

wherein the weight parts of the components are as follows: 35 parts of antibacterial polyester fiber, 66 parts of modal fiber and 9 parts of spandex;

the fineness of the modal fiber is 83dtex, the thickness of the blended yarn blended by the antibacterial polyester fiber and the modal fiber is 36S, and the fineness of the spandex is 24 dtex;

(4) preparing an antibacterial knitted fabric;

the knitted single-sided fabric prepared in the step (3) is sequentially subjected to pre-setting, pre-treatment, dyeing, dehydration, slitting, drying, setting and preshrinking to obtain an antibacterial knitted fabric;

the dyeing adopts one-bath mixed dyeing, and the dyeing temperature is 127 ℃; the presetting temperature is 184 ℃; the drying temperature is 115 ℃; setting temperature is 138 ℃; the preshrinking temperature was 110 ℃.

The antibacterial rate of the prepared antibacterial knitted fabric to escherichia coli and staphylococcus aureus is 99.1%, and the precipitation test is as follows: it was not detected.

Example 7

A preparation method of an antibacterial knitted fabric comprises the following specific steps:

(1) preparing modified polyester;

(1.1) esterification reaction;

preparing terephthalic acid, ethylene glycol and terephthalic acid-2 (4-pyridine) into slurry with the molar ratio of 1:2:0.02, adding silver-containing zeolite powder, a catalyst (antimony acetate) and a stabilizer (trimethyl phosphite) to be uniformly mixed, wherein the addition amounts of the catalyst and the stabilizer are 0.03 wt% and 0.05 wt% of the addition amount of the terephthalic acid respectively, and the addition amount of the silver-containing zeolite powder is 0.02 wt% of the addition amount of the terephthalic acid; then pressurizing in a nitrogen atmosphere to perform esterification reaction, wherein the pressurizing pressure is 0.3MPa, the temperature of the esterification reaction is 253 ℃, and the termination conditions of the esterification reaction are as follows: the distilled water amount in the esterification reaction reaches 97 percent of the theoretical value;

(1.2) polycondensation reaction;

after the esterification reaction is finished, starting the polycondensation reaction in the low vacuum stage under the negative pressure condition, smoothly pumping the pressure in the stage from normal pressure to absolute pressure of 380Pa within 50min, wherein the reaction temperature is 254 ℃, the reaction time is 45min, then continuing to pump vacuum, and carrying out the polycondensation reaction in the high vacuum stage, so that the reaction pressure is further reduced to absolute pressure of 20Pa, the reaction temperature is 282 ℃, and the reaction time is 50min, thus obtaining the modified polyester;

(2) preparing antibacterial polyester fibers;

the modified polyester is subjected to metering, extrusion, cooling, oiling, stretching, heat setting and winding to prepare antibacterial polyester fiber;

the spinning process parameters are as follows:

spinning temperature: 295 ℃;

cooling temperature: 25 ℃;

network pressure: 0.28 MPa;

a roll speed: 3200m/min

First roll temperature: 93 ℃;

two roll speed: 4100 m/min;

temperature of the two rolls: 130 ℃;

winding speed: 4000 m/min.

The polyester chain segment of the prepared antibacterial polyester fiber comprises a terephthalic acid chain segment, an ethylene glycol chain segment and a terephthalic acid-2 (4-pyridine) chain segment, and the molar ratio of the terephthalic acid chain segment to the terephthalic acid-2 (4-pyridine) chain segment is 1: 0.02; between terephthalic acid-2 (4-pyridine) chain segments of different polyester chain segments through Ag⁺The coordination is carried out, and the terephthalic acid-2 (4-pyridine) chain segment participates in coordination, and is N atom on pyridine, and the coordination structure formed by coordination is as follows:the fineness of the antibacterial polyester fiber is 75dtex, the breaking strength is 3.8cN/dtex, the elongation at break is 37%, the CV value of the breaking strength is 4.7%, the CV value of the elongation at break is 9%, and the shrinkage in boiling water is 7%;

(3) weaving the knitted single-sided cloth;

adding spandex into blended yarns formed by blending modal fibers and the antibacterial polyester fibers prepared in the step (2) on a 30-inch 28-needle circular knitting machine to weave a knitted single-sided fabric;

wherein the weight parts of the components are as follows: 40 parts of antibacterial polyester fiber, 70 parts of modal fiber and 10 parts of spandex;

the titer of the modal fiber is 90dtex, the thickness of the blended yarn blended by the antibacterial polyester fiber and the modal fiber is 50S, and the titer of the spandex is 30 dtex;

(4) preparing an antibacterial knitted fabric;

the knitted single-sided fabric prepared in the step (3) is sequentially subjected to pre-setting, pre-treatment, dyeing, dehydration, slitting, drying, setting and preshrinking to obtain an antibacterial knitted fabric;

the dyeing adopts one-bath mixed dyeing, and the dyeing temperature is 130 ℃; the presetting temperature is 185 ℃; the drying temperature is 110 ℃; setting temperature is 130 ℃; the preshrinking temperature was 120 ℃.

The antibacterial rate of the prepared antibacterial knitted fabric to escherichia coli and staphylococcus aureus is 99.4%, and the precipitation test is as follows: it was not detected.