Negative ion antibacterial polyester fiber fabric and preparation method thereof

Abstract

The invention belongs to the technical field of textile fabric preparation, and provides a negative ion antibacterial polyester fiber fabric and a preparation method thereof, wherein the preparation method comprises the following steps: adding a hyperdispersant Solsperse 32500, a dispersant DISPERS 655, and a negative ion powder to ethylene glycol, and stirring to obtain a negative ion slurry; mixing terephthalic acid, ethylene glycol, and a catalyst, and adding them to an esterification polycondensation reactor, and esterifying for 30 to 60 minutes; then adding a negative ion slurry and N, N-dihydroxyethyl-3-aminopropionic acid methyl ester at a uniform speed within 60 minutes; removing excess ethylene glycol, raising the temperature, reacting under low vacuum conditions, cooling and granulating, and obtaining polyester chips; drying the polyester chips and performing spinning treatment, and weaving the obtained fibers to obtain negative ion textile fabrics. The polyester fiber fabric obtained by the present invention has a higher amount of released negative ions and good spinning performance.

Description

Technical Field

[0001] The invention relates to the technical field of textile fabric preparation, and in particular to a negative ion antibacterial polyester fiber fabric and a preparation method thereof. Background Art

[0002] Polyester fiber, commonly known as "polyester", is a synthetic fiber obtained by spinning polyester formed by the polycondensation of organic dibasic acid and diol. Polyester fiber has a series of excellent properties such as excellent wrinkle resistance, elasticity and dimensional stability, excellent heat setting, good heat and light resistance, and acid resistance, and is widely used in clothing, home textiles and other fields.

[0003] Negative ion fiber fabrics are a collection of negative ion fibers, which contain materials that can release negative ions. When negative ion textiles rub against human skin, they will continuously generate negative air ions, which can eliminate odors, purify air, resist bacteria and inhibit bacteria, and resist electromagnetic radiation, thereby improving the air quality of the microenvironment around the human body. Therefore, negative ion textile fabrics are loved and sought after by the public.

[0004] The preparation methods of negative ion antibacterial fiber include the following: ① Surface coating modification method. In the post-processing process of the fiber, the treatment liquid containing inorganic particles such as tourmaline that can excite negative air ions is fixed on the fiber surface through resin finishing technology and surface treatment technology. The negative ion fiber prepared by this method feels hard and is not resistant to washing. ② Co-spinning method. Before polymerization or spinning, negative ion fiber is obtained by adding negative ion powder to the polymer melt or spinning solution for spinning. ③ Copolymerization method. Negative ion additives are added during the polymerization process, and the slices prepared have the function of releasing negative ions, and then spinning. The fibers obtained by the latter two have a softer feel and are more resistant to washing. However, if a high content of negative ion powder is added, it is not easy to disperse in the polymer matrix, resulting in poor spinnability, broken ends, sticking to rollers, etc., and when the amount of negative ions added to the fiber is low, the negative ion release effect of the textile will be poor.

[0005] Therefore, how to obtain a polyester fabric with a higher amount of negative ion powder added and better spinnability and use it in the clothing field is a problem that still exists in the current research on negative ion antibacterial polyester fiber fabrics. Summary of the invention

[0006] The purpose of the present invention is to provide a negative ion antibacterial polyester fiber fabric and a preparation method thereof in view of the above-mentioned problems. The polyester fiber fabric obtained by the method has a higher amount of released negative ions and good spinning performance, and can increase the spinning speed.

[0007] In order to achieve the above object, the technical solution adopted by the present invention is as follows:

[0008] A method for preparing a negative ion antibacterial polyester fiber fabric comprises the following steps:

[0009] (1) By weight, 1-2 parts of superdispersant Solsperse 32500, 2-4 parts of dispersant DISPERS 655, and 40-60 parts of negative ion powder are added to 200-300 parts of ethylene glycol, stirred at high speed, and undispersed particles are separated and removed by a centrifuge to obtain a negative ion slurry; the negative ion powder is a mixture of opal powder and tourmaline powder;

[0010] (2) 120 parts of terephthalic acid, 20-30 parts of ethylene glycol, and 0.2-0.3 parts of a catalyst are mixed uniformly by weight, added to an esterification polycondensation reactor, and esterified at 230-240° C. for 30-60 minutes; then, 50-60 parts of anion slurry and 6-9 parts of N,N-dihydroxyethyl-3-aminopropionic acid methyl ester are uniformly added at the same temperature, and both are added within 60 minutes; thereafter, excess ethylene glycol is removed, the temperature of the reaction system is increased to 265-270° C., the reaction is carried out under low vacuum conditions for 2-3 hours, and the discharged material is granulated in a cooling water tank to obtain in-situ polymerized anion polyester chips;

[0011] (3) After the anion polyester chips are dried, they are put into a spinning machine for spinning at a spinning temperature of 300 to 310° C. and a spinning speed of 3000 to 4500 m / min. The obtained fibers are woven to obtain anion textile fabrics.

[0012] In the present invention, preferably, the weight ratio of the hyperdispersant Solsperse 32500 to the dispersant DISPERS 655 is 1:2.

[0013] In the present invention, preferably, the mass ratio of the opal to the tourmaline is 1 to 5:1.

[0014] In the present invention, preferably, the low vacuum condition refers to the pressure in the reactor being below 100 Pa.

[0015] In the present invention, preferably, the drying treatment of the anion polyester chips is carried out in a vacuum drum, firstly heating to 122-132°C at a rate of 1-2°C / min for pre-crystallization for 2-4h; then heating to 145-160°C at a rate of 8-10°C / min for insulation for 4-5h.

[0016] In the present invention, preferably, the catalyst is antimony trioxide or antimony glycolate.

[0017] In the present invention, preferably, the particle sizes of the opal powder and tourmaline powder are both less than 1.000 μm.

[0018] The present invention also protects the negative ion antibacterial polyester fiber fabric prepared by the above-mentioned preparation method.

[0019] Micron- and nano-scale negative ion powders are in an energy unstable state due to their small particle size, large surface atomic ratio, large specific surface area, and large surface energy. Therefore, they are easy to condense and agglomerate to form secondary particles, which makes the particle size larger and loses the characteristics of nanoparticles. During use, if they cannot be well dispersed, on the one hand, they cannot be evenly dispersed in the polymer matrix, affecting the product quality, and on the other hand, they will break or clog the filter during melt spinning. The present invention obtains a dispersant suitable for such negative ion powder and the use environment through screening, and uses super dispersant Solsperse 32500 and dispersant DISPERS 655 as composite dispersants for negative ion powders. When the two dispersants are matched according to a certain mass ratio, the synergistic effect of the two is very significant, and can have better suspension rate and dispersibility, and can withstand high temperature reactions, which is very suitable for the polyester fiber production of the present invention.

[0020] There are many factors that affect the quality of polyester products during the polyester production process. From the perspective of spinning, the main factors include hue, terminal carboxyl groups, diethylene glycol content and viscosity, among which viscosity has the most significant effect on spinnability. This puts higher requirements on the quality of the melt, especially the stability of the characteristic viscosity of the melt. Generally, it is necessary to stabilize at the characteristic viscosity center value of 0.65, fluctuate within the range of 0.05, and the melt has good spinnability. After adding the dispersant and the negative ion slurry to the present invention, the polyester sheet is unstable during the molding process, and the viscosity drop is large. By adding a certain amount of N, N-dihydroxyethyl-3-aminopropionic acid methyl ester during the polymerization process, the chain structure is changed, so that the characteristic viscosity drop during the molding process is reduced, and the spinnability is improved.

[0021] In summary, due to the adoption of the above technical solution, the beneficial effects of the present invention are:

[0022] 1. The present invention uses super dispersant Solsperse 32500 and dispersant DISPERS 655 as composite dispersants for negative ion powders, which can obtain good suspension rate and dispersibility, and can withstand high temperature reactions, and is very suitable for the production of polyester fibers of the present invention. Compared with conventional polyester fibers, while increasing the amount of negative ion powder incorporated, it can also maintain a high spinning speed, and the phenomenon of broken ends or filter clogging is less likely to occur. The negative ion powder of the present invention can be effectively fused with the polymer matrix, has excellent compatibility with the polymer, does not affect the softness of the high molecular polymer fiber, and makes the fabric have an excellent feel.

[0023] 2. In the present invention, a certain amount of N,N-dihydroxyethyl-3-aminopropionic acid methyl ester is added during the polymerization process to change the polyester chain structure, so that the intrinsic viscosity drop during the molding process is reduced and maintained within 0.05 dL / g, thereby improving the spinnability.

[0024] 3. The negative ion release rate of the negative ion antibacterial polyester fiber fabric prepared by the present invention is relatively high, which is 5900-8100 / cm 3 , has good antibacterial and health-care effects. After 40 washes, the negative ion release can still be maintained at 3500 / cm 3 above. DETAILED DESCRIPTION

[0025] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments in the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention. In the embodiments of the present invention, opal powder was purchased from 14639-88-4 of Hubei Shixing Chemical Co., Ltd., and tourmaline powder was purchased from ZX-022D of Zhengxu Mineral Products Processing Plant. Example 1

[0026] A method for preparing a negative ion antibacterial polyester fiber fabric comprises the following steps:

[0027] (1) By weight, 2 parts of superdispersant Solsperse 32500, 2 parts of dispersant DISPERS 655, and 40 parts of negative ion powder are added to 200 parts of ethylene glycol, stirred at high speed, and undispersed particles are separated and removed by a centrifuge to obtain a negative ion slurry; the negative ion powder is a mixture of opal powder and tourmaline powder in a mass ratio of 1:1; the particle sizes of the opal powder and the tourmaline powder are both less than 1.000 μm.

[0028] (2) 120 parts of terephthalic acid, 20 parts of ethylene glycol, and 0.2 parts of antimony trioxide are mixed uniformly by weight, added to an esterification polycondensation reactor, and esterified at 230-235° C. for 30 minutes; then, 60 parts of anion slurry and 6 parts of N,N-dihydroxyethyl-3-aminopropionic acid methyl ester are added at a uniform rate at the same temperature, and both are added within 60 minutes; thereafter, excess ethylene glycol is removed, the temperature of the reaction system is increased to 265-270° C., the reactor is evacuated to a pressure below 100 Pa, and the reaction is carried out for 2 hours, and the discharged material is granulated in a cooling water tank to obtain in-situ polymerized anion polyester chips;

[0029] (3) After the anion polyester chips are dried, they are heated to 122°C at a rate of 1°C / min in a vacuum drum for pre-crystallization for 2 hours; then they are heated to 145°C at a rate of 8°C / min and kept warm for 4 hours, and then put into a spinning machine for spinning at a spinning temperature of 300-305°C and a spinning speed of 3000 m / min. The obtained fibers are woven to obtain anion textile fabrics.

[0030] In this embodiment, spinning is performed at a relatively high speed, and no breakage, no sticking to the roller, and no clogging of the filter occurs during the spinning process. The intrinsic viscosity drop of the polyester chip melt from before the start of conveying to after the end of extrusion (referring to the absolute value of the difference between the intrinsic viscosity of the polyester melt before the start of conveying and the intrinsic viscosity of the polyester melt after the end of extrusion) does not exceed 0.05 dL / g.

[0031] According to GB / T 30128-2013 "Detection and Evaluation of Negative Ion Generation", the negative ion generation of the prepared fabric is 8100 / cm 3 , after washing 40 times, it can still maintain 4500 pieces / cm 3 The antibacterial effect was tested according to GBT 20944.3-2008 "Evaluation of antibacterial properties of textiles Part 3: Oscillation method", and the inhibition rates of Escherichia coli, Staphylococcus aureus and white streptococci were 100%, 99% and 99% respectively; after washing 40 times, they can still maintain 89%, 88% and 87%. The air permeability was tested according to GB / T5453-1997 "Determination of air permeability of textile fabrics", and the sample area was 20cm 2 , the sample pressure difference was set to 100±2Pa, and the air permeability was 569mm / s. Example 2

[0032] A method for preparing a negative ion antibacterial polyester fiber fabric comprises the following steps:

[0033] (1) By weight, 1.75 parts of superdispersant Solsperse 32500, 3.5 parts of dispersant DISPERS 655, and 60 parts of negative ion powder are added to 300 parts of ethylene glycol, stirred at high speed, and undispersed particles are separated and removed by a centrifuge to obtain a negative ion slurry; the negative ion powder is a mixture of opal powder and tourmaline powder in a mass ratio of 3:1; the particle sizes of the opal powder and the tourmaline powder are both less than 1.000 μm.

[0034] (2) 120 parts of terephthalic acid, 25 parts of ethylene glycol, and 0.25 parts of ethylene glycol antimony were mixed uniformly by weight, added to an esterification polycondensation reactor, and esterified at 232-236° C. for 45 minutes; then, 55 parts of anion slurry and 8 parts of N,N-dihydroxyethyl-3-aminopropionic acid methyl ester were uniformly added at the same temperature, and both were added within 60 minutes; thereafter, excess ethylene glycol was removed, the temperature of the reaction system was increased to 268-270° C., the reactor was evacuated to a pressure below 100 Pa, and the reaction was carried out for 2.5 hours, and the discharged material was granulated in a cooling water tank to obtain in-situ polymerized anion polyester chips;

[0035] (3) After the anion polyester chips are dried, they are heated to 130°C at a rate of 2°C / min in a vacuum drum for pre-crystallization for 3 hours; then they are heated to 150°C at a rate of 9°C / min and kept warm for 4.5 hours. The chips are put into a spinning machine for spinning at a spinning temperature of 305°C and a spinning speed of 3500 m / min. The obtained fibers are woven to obtain anion textile fabrics.

[0036] In this embodiment, spinning is performed at a relatively high speed, and no breakage, no sticking to the roller, and no clogging of the filter occurs during the spinning process. The intrinsic viscosity drop of the polyester chip melt from before the start of conveying to after the end of extrusion (referring to the absolute value of the difference between the intrinsic viscosity of the polyester melt before the start of conveying and the intrinsic viscosity of the polyester melt after the end of extrusion) does not exceed 0.05 dL / g.

[0037] According to GB / T 30128-2013 "Detection and Evaluation of Negative Ion Generation", the negative ion generation of the prepared fabric is 7500 / cm 3 , after washing 40 times, it can still maintain 4000 pieces / cm 3 The antibacterial effect was tested according to GBT 20944.3-2008 "Evaluation of antibacterial properties of textiles Part 3: Oscillation method", and the inhibition rates of Escherichia coli, Staphylococcus aureus and Streptococcus albicans were 100%, 97% and 97% respectively; after washing 40 times, they can still maintain 85%, 84% and 83%. The air permeability was tested according to GB / T5453-1997 "Determination of air permeability of textile fabrics", and the sample area was 20cm 2 , the sample pressure difference is set to 100±2Pa, and the air permeability is 550mm / s. Example 3

[0038] A method for preparing a negative ion antibacterial polyester fiber fabric comprises the following steps:

[0039] (1) By weight, 1 part of super dispersant Solsperse 32500, 4 parts of dispersant DISPERS 655, and 50 parts of negative ion powder are added to 240 parts of ethylene glycol, stirred at high speed, and undispersed particles are separated and removed by a centrifuge to obtain a negative ion slurry; the negative ion powder is a mixture of opal powder and tourmaline powder in a mass ratio of 5:1; the particle sizes of the opal powder and the tourmaline powder are both less than 1.000 μm.

[0040] (2) 120 parts of terephthalic acid, 30 parts of ethylene glycol, and 0.3 parts of ethylene glycol antimony were mixed uniformly by weight, added to an esterification polycondensation reactor, and esterified at 235-240° C. for 60 minutes; then, at the same temperature, 40 parts of anion slurry and 9 parts of N,N-dihydroxyethyl-3-aminopropionic acid methyl ester were uniformly added, and both were added within 60 minutes; thereafter, excess ethylene glycol was removed, the temperature of the reaction system was increased to 270° C., the reactor was evacuated to a pressure below 100 Pa, and the reaction was carried out for 3 hours, and the discharged material was granulated in a cooling water tank to obtain in-situ polymerized anion polyester chips;

[0041] (3) After the anion polyester chips are dried, they are heated to 132°C at a rate of 2°C / min in a vacuum drum for pre-crystallization for 4 hours; then they are heated to 160°C at a rate of 10°C / min and kept warm for 5 hours. The chips are put into a spinning machine for spinning at a spinning temperature of 310°C and a spinning speed of 4500 m / min. The obtained fibers are woven to obtain anion textile fabrics.

[0042] In this embodiment, spinning is performed at a relatively high speed, and no breakage, no sticking to the roller, and no clogging of the filter occurs during the spinning process. The intrinsic viscosity drop of the polyester chip melt from before the start of conveying to after the end of extrusion (referring to the absolute value of the difference between the intrinsic viscosity of the polyester melt before the start of conveying and the intrinsic viscosity of the polyester melt after the end of extrusion) does not exceed 0.05 dL / g.

[0043] According to GB / T 30128-2013 "Detection and Evaluation of Negative Ion Generation", the negative ion generation of the prepared fabric is 5900 / cm 3 , after washing 40 times, it can still maintain 3500 pieces / cm 3 The antibacterial effect was tested according to GBT 20944.3-2008 "Evaluation of antibacterial properties of textiles Part 3: Oscillation method", and the inhibition rates of Escherichia coli, Staphylococcus aureus and Streptococcus albicans were 96%, 94% and 92% respectively; after washing 40 times, they can still maintain 80%, 78% and 76%. The air permeability was tested according to GB / T5453-1997 "Determination of air permeability of textile fabrics", and the sample area was 20cm 2 , the sample pressure difference was set at 100±2Pa, and the air permeability was measured to be 578mm / s.

[0044] Comparative Example 1

[0045] The hyperdispersant Solsperse 32500 used in step (1) was replaced by an equal amount of dispersant DISPERS 655, and the remaining steps were exactly the same as those in Example 2.

[0046] The spinning process of this comparative example showed multiple breakage and filter clogging. The intrinsic viscosity drop of the polyester chip melt from before the start of conveying to after the end of extrusion (the absolute value of the difference between the intrinsic viscosity of the polyester melt before the start of conveying and the intrinsic viscosity of the polyester melt after the end of extrusion) was 0.09 dL / g.

[0047] Comparative Example 2

[0048] The dispersant DISPERS 655 used in step (1) was replaced by an equal amount of the hyperdispersant Solsperse 32500, and the remaining steps were exactly the same as those in Example 2.

[0049] The spinning process of this comparative example has the phenomenon of multiple breakage and filter clogging. The intrinsic viscosity drop of the polyester chip melt before the start of conveying and after the end of extrusion (the absolute value of the difference between the intrinsic viscosity of the polyester melt before the start of conveying and the intrinsic viscosity of the polyester melt after the end of extrusion) is 0.12 dL / g.

[0050] Comparative Example 3

[0051] The hyperdispersant Solsperse 32500 used in step (1) was replaced by an equal amount of sodium pyrophosphate, and the remaining steps were exactly the same as those in Example 2.

[0052] The spinning process of this comparative example has the phenomenon of multiple breakage and filter clogging. The intrinsic viscosity drop of the polyester chip melt before the start of conveying and after the end of extrusion (the absolute value of the difference between the intrinsic viscosity of the polyester melt before the start of conveying and the intrinsic viscosity of the polyester melt after the end of extrusion) is 0.29 dL / g.

[0053] Comparative Example 4

[0054] In step (2), no N,N-dihydroxyethyl-3-aminopropionic acid methyl ester was added, and the remaining operation steps were exactly the same as those in Example 2.

[0055] The spinning process of this comparative example showed the phenomenon of sticking to the roller. The intrinsic viscosity drop of the polyester chip melt from before the start of conveying to after the end of extrusion (the absolute value of the difference between the intrinsic viscosity of the polyester melt before the start of conveying and the intrinsic viscosity of the polyester melt after the end of extrusion) was 0.68 dL / g.

[0056] Comparative Example 5

[0057] The negative ion slurry and N,N-dihydroxyethyl-3-aminopropionic acid methyl ester in step (2) are quickly added within 10 minutes, and the remaining operating steps are exactly the same as those in Example 2.

[0058] The spinning process of this comparative example showed a few breakages and roller sticking. The intrinsic viscosity drop of the polyester chip melt from before the start of conveying to after the end of extrusion (the absolute value of the difference between the intrinsic viscosity of the polyester melt before the start of conveying and the intrinsic viscosity of the polyester melt after the end of extrusion) was 0.25 dL / g.

[0059] From the above preparation test and performance test results, it can be seen that the negative ion antibacterial polyester fiber fabrics prepared in Examples 1-3 have a high negative ion generation amount, up to 8100 / cm 3 , excellent antibacterial effect, good air permeability of fabric. After 40 washes, it can still maintain a high amount of negative ion generation and antibacterial effect. The composition of the dispersant in Comparative Examples 1-3 changed, and blockage and broken ends occurred during the spinning process, indicating that the compounding of the dispersant has a greater impact on the dispersion effect, thereby affecting the preventability of polyester. In Comparative Example 4, N, N-dihydroxyethyl-3-aminopropionic acid methyl ester was not added, and the sticking roller phenomenon occurred, and the characteristic viscosity dropped significantly, which brought instability to the production, indicating that N, N-dihydroxyethyl-3-aminopropionic acid methyl ester can significantly improve the thermal stability of polyester. In Comparative Example 5, the addition of negative ion slurry and N, N-dihydroxyethyl-3-aminopropionic acid methyl ester was added in a short period of time, not gradually added dropwise, which had a certain impact on the dispersion of negative ion powder and the copolymerization of polyester, and ultimately affected the spinnability of polyester chips.

[0060] The above description is a detailed description of the preferred feasible embodiments of the present invention, but the embodiments are not intended to limit the scope of the patent application of the present invention. All equivalent changes or modified changes completed under the technical spirit suggested by the present invention should fall within the patent scope covered by the present invention.

Claims

1. A method for preparing a negative ion antibacterial polyester fiber fabric, characterized in that: The following steps are involved: (1) By weight, 1-2 parts of superdispersant Solsperse 32500, 2-4 parts of dispersant DISPERS 655, and 40-60 parts of negative ion powder are added to 200-300 parts of ethylene glycol, stirred at high speed, and undispersed particles are separated and removed by a centrifuge to obtain a negative ion slurry; the negative ion powder is a mixture of opal powder and tourmaline powder; (2) 120 parts of terephthalic acid, 20-30 parts of ethylene glycol, and 0.2-0.3 parts of a catalyst are mixed uniformly by weight, added to an esterification polycondensation reactor, and esterified at 230-240° C. for 30-60 minutes; then, at the same temperature, 50-60 parts of anion slurry and 6-9 parts of N,N-dihydroxyethyl-3-aminopropionic acid methyl ester are uniformly added, and both are added within 60 minutes; thereafter, excess ethylene glycol is removed, the temperature of the reaction system is increased to 265-270° C., the reaction is carried out under low vacuum conditions for 2-3 hours, and the discharged material is granulated in a cooling water tank to obtain in-situ polymerized anion polyester chips; the low vacuum condition refers to a pressure in the reactor of less than 100 Pa; (3) After the anion polyester chips are dried, they are put into a spinning machine for spinning at a spinning temperature of 300 to 310° C. and a spinning speed of 3000 to 4500 m / min. The obtained fibers are woven to obtain anion textile fabrics.

2. The preparation method according to claim 1, characterized in that: The weight ratio of the hyperdispersant Solsperse 32500 to the dispersant DISPERS 655 is 1:

2.

3. The preparation method according to claim 1, characterized in that: The mass ratio of the opal to the tourmaline is 1 to 5:

1.

4. The preparation method according to claim 1, characterized in that: The drying treatment of the anion polyester chips is carried out in a vacuum drum, firstly heating to 122-132° C. at a speed of 1-2° C. / min for pre-crystallization for 2-4 hours; then heating to 145-160° C. at a speed of 8-10° C. / min for preservation for 4-5 hours.

5. The preparation method according to claim 1, characterized in that: The catalyst is antimony trioxide or antimony glycolate.

6. The preparation method according to claim 1, characterized in that: The particle sizes of the opal powder and tourmaline powder are both less than 1.000 μm.

7. The negative ion antibacterial polyester fiber fabric prepared by the preparation method according to any one of claims 1 to 6.