Manufacturing method of antibacterial polyester fiber

Abstract

The present invention relates to a manufacturing method of antibacterial polyester fibers, mainly solving the problems such as poor antibacterial durability of the antibacterial polyester fibers obtained by the existing methods for preparing antibacterial polyester fibers. The manufacturing method of the antibacterial polyester fibers includes: (1) melt spinning using polyethylene terephthalate and a modifier as raw materials to obtain a nascent fiber, where polyethylene terephthalate is abbreviated as PET; (2) applying a fiber finish emulsion to the surface of the nascent fiber to obtain an oil-containing fiber; (3) performing hot drawing on the oil-containing fiber; (4) finishing the fiber with an antibacterial guanidine salt finishing solution to obtain the antibacterial polyester fiber; the technical solution where the modifier includes a polyester containing a polyethylene glycol segment and a polyester containing an anionic group can be used in the production of antibacterial polyester fibers.

Description

[0001] This application is a divisional application of the patent application with the application date of February 7, 2023, application number 202310069756.0, and invention title "Manufacturing Method of Antibacterial Polyester Fabric". Technical Field

[0002] The present invention relates to a manufacturing method of antibacterial polyester fibers. Background Art

[0003] In recent years, the functionalization of textiles has become an important development direction. Fiber materials are the basic units that make up textiles, and the realization of many functions of textiles depends on the modification of fiber materials. The antibacterial function of textiles is closely related to our daily life. Textiles such as our home furnishings, clothing, and ornaments are widely used. Polyester fibers have high strength, good elastic recovery performance, good wear resistance, and stable chemical properties. As an important variety of fiber materials, they have the characteristics of large production volume and wide application. However, due to its high surface area, conventional polyester fibers are conducive to the attachment of bacteria and microorganisms, serving as a good habitat and transmission medium. At the same time, the secretions of microorganisms have a degradation effect on the fibers, and they do not have antibacterial functions. Therefore, it is of great significance to provide certain methods or processes to achieve the antibacterial properties of polyester fibers.

[0004] Chinese invention patent CN105332078B discloses an antibacterial polyester fiber based on silver-loaded zirconium phosphate and its preparation method. First, silver-loaded zirconium phosphate nanopowder is prepared; the silver-loaded zirconium phosphate nanopowder, terephthalic acid, and diol are added to a polyester reaction kettle for in-situ polymerization to prepare silver-loaded zirconium phosphate antibacterial polyester, and melt direct spinning is used to prepare antibacterial polyester fibers based on silver-loaded zirconium phosphate. Alternatively, the silver-loaded zirconium phosphate antibacterial polyester is granulated to obtain a silver-loaded zirconium phosphate antibacterial polyester masterbatch, and the antibacterial polyester fibers based on silver-loaded zirconium phosphate are prepared by the method of masterbatch blending spinning. Chinese invention patent CN111155198B discloses a preparation method of antibacterial polyester fibers, which is to blend and granulate tetra-hydroxy titanium as an antibacterial agent with spinning-grade polyester into chips or masterbatches, and then fiberize by spinning. Chinese invention patent CN109252240B discloses a melt direct spinning preparation method of flame-retardant antibacterial polyester fibers. During the melt direct spinning process of polyester, a flame-retardant antibacterial masterbatch is added online to obtain flame-retardant antibacterial polyester fibers; the flame-retardant antibacterial masterbatch is uniformly dispersed with a metal-modified hyperbranched polymer; the metal-modified hyperbranched polymer is a network polymer formed by crosslinking a hyperbranched polymer with carboxyl groups at the end with metal ions.

[0005] Chinese invention patent CN111020734B discloses a preparation method of a long-acting antibacterial polyester fiber. First, the chemical structure of PHMG is modified by p-carboxybenzenesulfonamide, and then the modified PHMG reacts with the terminal alcohol hydroxyl group and ester group in the polyester fiber. Therefore, the modified PHMG can be used as an antibacterial additive and added to the spinning dope to prepare polyester fibers with long-term stable and excellent antibacterial properties.

[0006] As can be seen from the above, in the existing public technologies, the most common method for preparing antibacterial polyester fibers is by polymerization or blending modification. Among them, the polymerization modification method is to introduce specific copolymer components or antibacterial components during the polyester synthesis stage; the blending modification method is to add antibacterial masterbatches in polyester spinning for mixed spinning. In order to ensure the spinnability and basic physical and chemical properties of the fibers such as mechanical properties, the antibacterial components involved in both the polymerization modification method and the blending modification method need to be evenly dispersed in the fibers. Therefore, the content of the introduced antibacterial components is often relatively high. However, the antibacterial modified components dispersed inside the fibers cannot play an antibacterial role during application and will have an adverse impact on the basic properties such as the strength of the fibers. Therefore, how to distribute the antibacterial modified components on the surface layer of the fiber material as much as possible according to the structural characteristics of the fiber material to reduce the usage amount of antibacterial components is of great significance for actual production.

[0007] Chinese invention patent CN113122958B discloses a long-acting and low-toxicity antibacterial polyester fiber. The antibacterial polyester fiber is composed of a skin layer and a core layer from the outside to the inside. The skin layer is composed of a polyester fiber grafted with a guanidine antibacterial agent, and the core layer is composed of ordinary polyester fibers. Chinese invention patent CN105603560B discloses a flame-retardant and antibacterial polyester fiber for mattress filling and its manufacturing method. Nano-montmorillonite, nano-silica powder, hexakis(4-formylphenoxy)cyclotriphosphazene and PET resin are used for blending modification to obtain a polyester fiber with permanent flame-retardant properties, and then it is impregnated with a treatment liquid, and the impregnation treatment liquid is composed of citrus essential oil, lavender essential oil, ethanol and water. Chinese invention patent CN113026341B discloses a preparation method of a copper and titanium coupled long-acting antibacterial polyester fiber based on an efficient pretreatment process. First, an ultrasonic alcohol washing-high temperature alkali dipping composite pretreatment process is carried out. The pretreated spare polyester fiber is arranged in a complexing solution for impregnation treatment, and the complexing solution is composed of CuSO4 and polyhexamethylene guanidine. Finally, the polyester fiber cloth is taken out and dried at a certain temperature to obtain an antibacterial polyester fabric.

[0008] From the above disclosed technical analysis, it can be seen that in order to achieve more efficient antibacterial modification of polyester fibers or fabrics, methods such as core-sheath composite spinning and post-treatment impregnation have been formed. Among them, the core-sheath composite spinning method uses an antibacterial component as the skin layer and conventional polyester as the core layer. Although the utilization rate of the antibacterial component is improved to a certain extent, the current forming speed of core-sheath composite fibers is generally low, and the fiber strength is not high, mainly for hot melt bonding applications; although the post-treatment impregnation method can achieve the enrichment of antibacterial components on the fiber surface, the chemical structure of polyester fibers themselves is stable, and it is difficult to achieve strong bonding between the modified components and the surface of polyester fibers. Usually, polyester fibers are etched with strong alkali to form exposed groups or micropores on the fiber surface, thereby improving the bonding force with the modified components. However, the etching with strong alkali will cause a significant reduction in the mechanical strength of the fibers.

[0009] Generally speaking, the antibacterial fibers on the current market still have problems such as inconsistent antibacterial properties, poor durability and antibacterial persistence, and relatively high processing costs of antibacterial fibers. Therefore, there is an urgent need to develop a stable antibacterial polyester fiber with excellent antibacterial properties prepared in an economically feasible way. Summary of the Invention

[0010] The technical problem to be solved by the present invention is the technical problem that the antibacterial polyester fibers obtained by the existing methods for preparing antibacterial polyester fibers have poor antibacterial durability, and a new manufacturing method of antibacterial polyester fibers is provided. The antibacterial polyester fibers obtained by this method have the advantage of good antibacterial durability.

[0011] To solve the above technical problems, the technical solution of the present invention is as follows:

[0012] A manufacturing method of antibacterial polyester fibers, comprising:

[0013] (1) Melting and spinning poly(ethylene terephthalate) and a modifier as raw materials to obtain nascent fibers, and poly(ethylene terephthalate) is abbreviated as PET;

[0014] (2) Applying a fiber oil agent emulsion to the surface of the nascent fibers to obtain oil-containing fibers;

[0015] (3) Thermally stretching the oil-containing fibers;

[0016] (4) Treating the obtained fibers with an antibacterial guanidine salt finishing solution to obtain antibacterial polyester fibers;

[0017] Its characteristics are:

[0018] The modifier includes a polyester containing a polyethylene glycol segment and a polyester containing an anionic group;

[0019] In the raw materials of step (1), the weight ratio of the modifier to PET is 0.01 - 0.30;

[0020] In polyesters containing polyethylene glycol segments, the structural unit derived from polyethylene glycol─(CH2CH2O) m The molar ratio of ─CH2CH2O─, a structural unit derived from ethylene glycol, is 0.004 to 0.04;

[0021] The anion in the polyester containing anionic groups is derived from isophthalic acid sulfonate;

[0022] The molar ratio of the terephthalic acid structural unit to the isophthalic acid sulfonate structural unit in the anionic group-containing polyester is 1-9.

[0023] The use of the modifier improves the antibacterial durability of the fiber.

[0024] The process of applying fiber oil emulsion to spun fibers is also referred to as "oiling" in the art.

[0025] In the above technical solution, step (4) can be to perform antibacterial finishing on the fiber to obtain antibacterial fiber, and the antibacterial fiber can be further made into fabric containing the antibacterial fiber according to methods well known in the art; or, the fiber can be first made into fabric containing the fiber, and then the fabric containing the fiber is subjected to the antibacterial finishing, and antibacterial polyester fabric can also be obtained. Therefore, those skilled in the art can infer that the embodiment of manufacturing antibacterial fiber by performing antibacterial finishing on the fiber can represent the above step (4) of finishing the obtained fiber or the fabric containing the fiber with an antibacterial guanidine salt finishing liquid to obtain an antibacterial product. Only for comparison, the specific embodiments of the present invention are all based on the antibacterial finishing of the fiber to manufacture antibacterial fiber.

[0026] In the above technical scheme, as a non-limiting example, the weight ratio of the modifier to PET in the raw material is 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.20, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, etc. For comparison only, the weight ratio of the modifier to PET in the embodiments of the present invention is generally 0.12.

[0027] In the above technical solution, preferably, the intrinsic viscosity of PET is 0.60 to 0.70 dl / g. As a non-limiting example, for instance but not limited to, the intrinsic viscosity of PET is 0.61 dl / g, 0.62 dl / g, 0.63 dl / g, 0.64 dl / g, 0.65 dl / g, 0.66 dl / g, 0.67 dl / g, 0.68 dl / g, 0.69 dl / g, and so on. Only for comparison, the polyethylene terephthalate (PET) used in the specific embodiments of the present invention is of type SB500 from Sinopec Yizheng Chemical Fiber Co., Ltd., with an intrinsic viscosity of 0.67 dl / g, and the actually measured intrinsic viscosity is 0.67 dl / g.

[0028] In the above technical solution, preferably, the intrinsic viscosity of the polyester containing polyethylene glycol segments is 0.70 to 0.90 dl / g. For example but not limited to, the intrinsic viscosity of the polyester containing polyethylene glycol segments is 0.71 dl / g, 0.72 dl / g, 0.73 dl / g, 0.74 dl / g, 0.75 dl / g, 0.76 dl / g, 0.77 dl / g, 0.78 dl / g, 0.79 dl / g, 0.80 dl / g, 0.81 dl / g, 0.82 dl / g, 0.83 dl / g, 0.84 dl / g, 0.85 dl / g, 0.86 dl / g, 0.87 dl / g, 0.88 dl / g, 0.89 dl / g, and so on.

[0029] In the above technical solution, as a non-limiting example, in the polyester containing polyethylene glycol segments, the molar ratio of the structural unit ─(CH2CH2O)─ from polyethylene glycol m ─ to the structural unit ─CH2CH2O─ from ethylene glycol is 0.006, 0.008, 0.01, 0.015, 0.02, 0.025, 0.03, 0.035, and so on.

[0030] In the above technical solution, preferably, the polyester containing polyethylene glycol segments is composed of ethylene glycol structural units, polyethylene glycol structural units, and terephthalic acid structural units.

[0031] Those skilled in the art know that the synthesis of polyesters generally consists of an esterification stage and a polycondensation stage. The esterification reaction is easy to carry out and can be catalyzed or uncatalyzed. In the polycondensation stage, as the molecular chain grows, the mobility of reactive groups is restricted, and a polymerization catalyst is usually required. The polymerization catalyst can be added in the esterification stage and enter the polycondensation stage together with the esterification product, or it can be added in the polycondensation stage, and comparable technical effects can be achieved without creative labor. Regarding the polymerization catalyst, those skilled in the art can use known polymerization catalysts such as, but not limited to, antimony-based polymerization catalysts (such as, but not limited to, antimony trioxide, antimony acetate, ethylene glycol antimony), titanium-based polymerization catalysts, etc. There is no limitation, and comparable technical effects can be achieved. Only for comparison, when the polymerization in the examples of the present invention is self-made, ethylene glycol antimony is used in all cases where a polymerization catalyst is used.

[0032] Those skilled in the art know that the esterification rate is used to indicate the completion degree of the esterification reaction. In polyester production, the esterification rate is defined as the mole fraction of the carboxyl groups that form ester groups to the carboxyl groups in the feedstock. The esterification rate can be controlled by measuring and collecting the amount of water generated and distilled out during the esterification reaction. The method for measuring the esterification rate is based on the actual weight of water generated during the esterification reaction and the weight of water generated by complete esterification of the carboxyl groups in the reaction raw materials according to the stoichiometry, that is, calculated according to the following formula:

[0033] Esterification rate % = (Actual weight of water generated during the esterification reaction / Weight of water generated by complete esterification of the carboxyl groups in the reaction raw materials according to the stoichiometry) × 100%.

[0034] Only by way of example, the polyester containing poly(ethylene glycol) segments can be obtained by a synthesis method including the following steps:

[0035] Esterification reaction I

[0036] Terephthalic acid and a diol compound are added to a reactor for an esterification reaction; preferably, the molar ratio of the diol to terephthalic acid is 1.05 to 1.50 (such as but not limited to the molar ratio of the diol to terephthalic acid being 1.1, 1.15, 1.2, 1.25, 1.3, 1.35, 1.4, 1.45, etc.); and / or preferably, the diol compound includes polyethylene glycol and a dihydric alcohol, and / or the dihydric alcohol is preferably ethylene glycol, and more preferably the molar ratio of polyethylene glycol to ethylene glycol is 0.005 to 0.05 (such as but not limited to 0.006, 0.007, 0.008, 0.009, 0.01, 0.015, 0.02, 0.025, 0.03, 0.035, 0.04, 0.045, etc.); and / or preferably, the number-average molecular weight of polyethylene glycol is 500 to 4000 (such as but not limited to 600, 700, 800, 900, 1000, 1500, 2000, 2500, 3000, 3500, etc.); preferably, the esterification rate is controlled to be 95 to 99% (such as but not limited to the esterification rate being controlled to be 95.5%, 96%, 96.5%, 97%, 97.5%, 98%, 98.5%, etc.) to obtain an esterification product;

[0037] The pressure and temperature of the esterification reaction are not particularly limited. For example, but not limited to, the pressure of the esterification reaction in gauge pressure is 0.1 to 1.0 MPa (such as but not limited to 0.15 MPa, 0.2 MPa, 0.25 MPa, 0.3 MPa, 0.35 MPa, 0.4 MPa, 0.45 MPa, 0.5 MPa, 0.55 MPa, 0.6 MPa, 0.65 MPa, 0.7 MPa, 0.75 MPa, 0.8 MPa, 0.85 MPa, 0.9 MPa, 0.95 MPa, etc.), and / or the esterification reaction temperature is 235 to 245 °C (such as but not limited to 236 °C, 237 °C, 238 °C, 239 °C, 240 °C, 241 °C, 242 °C, 243 °C, 244 °C, etc.);

[0038] Polycondensation reaction II

[0039] A polymerization catalyst is added to the esterification product and polycondensed until the intrinsic viscosity reaches 0.70 - 0.90 dl / g (such as but not limited to 0.71 dl / g, 0.72 dl / g, 0.73 dl / g, 0.74 dl / g, 0.75 dl / g, 0.76 dl / g, 0.77 dl / g, 0.78 dl / g, 0.79 dl / g, 0.80 dl / g, 0.81 dl / g, 0.82 dl / g, 0.83 dl / g, 0.84 dl / g, 0.85 dl / g, 0.86 dl / g, 0.87 dl / g, 0.88 dl / g, 0.89 dl / g, etc.); preferably, first polycondense at an absolute pressure of 400 - 600 MPa (such as but not limited to 420 MPa, 440 MPa, 460 MPa, 480 MPa, 500 MPa, 520 MPa, 540 MPa, 560 MPa, 580 MPa, 590 MPa, etc.) and a temperature of 255 - 265 °C (such as but not limited to 256 °C, 257 °C, 258 °C, 259 °C, 260 °C, 261 °C, 262 °C, 263 °C, 264 °C, etc.) for 30 - 60 minutes (such as but not limited to 35 minutes, 40 minutes, 45 minutes, 50 minutes, 55 minutes, etc.), and then polycondense at an absolute pressure below 100 Pa (such as but not limited to an absolute pressure of 5 Pa, 10 Pa, 20 Pa, 30 Pa, 40 Pa, 50 Pa, 60 Pa, 70 Pa, 80 Pa, 90 Pa, etc.) until the desired intrinsic viscosity is reached. Regarding the polymerization catalyst, those known to those skilled in the art can be used, such as but not limited to antimony-based polymerization catalysts, titanium-based polymerization catalysts, etc., and there is no limitation, and comparable technical effects can be achieved. Only for comparison, antimony-based catalysts are used as the polymerization catalyst. The amount of the antimony-based catalyst expressed in terms of antimony and by weight is 100 - 300 ppmw relative to the terephthalic acid input in the esterification reaction I (such as but not limited to 110 ppmw, 120 ppmw, 130 ppmw, 140 ppmw, 150 ppmw, 160 ppmw, 170 ppmw, 180 ppmw, 190 ppmw, 200 ppmw, 210 ppmw, 220 ppmw, 230 ppmw, 240 ppmw, 250 ppmw, 260 ppmw, 270 ppmw, 280 ppmw, 290 ppmw, etc.).

[0040] More specifically, only for comparison, the polyesters containing poly(ethylene glycol) segments used in the specific embodiments of the present invention are all prepared by the following method:

[0041] Terephthalic acid and a diol compound are added (where the molar ratio of the diol to terephthalic acid is 1.10, the diol compound is ethylene glycol and polyethylene glycol, the molar ratio of polyethylene glycol to ethylene glycol is 0.01, and the number-average molecular weight of polyethylene glycol is 2000 g / mol) to a reactor for an esterification reaction. The esterification reaction pressure (gauge pressure) is 0.2 MPa, the esterification reaction temperature is 240 °C, and the water generated and distilled out during the esterification is collected. The esterification rate is calculated based on the amount of water discharged. When the esterification rate reaches 97%, 200 ppmw of antimony glycolate (calculated as antimony, relative to the weight of terephthalic acid input in the reaction raw materials) is added, the vacuum is pumped to an absolute pressure of 500 Pa, and the temperature is raised to 260 °C for a polycondensation reaction time of 45 min. Then, the vacuum is pumped to an absolute pressure of 50 Pa, and the polycondensation is continued until the intrinsic viscosity of the polyester reaches 0.83 dl / g to obtain a polyester containing polyethylene glycol segments. After analysis, the molar ratio of the diol compound structural unit to the terephthalic acid structural unit in the copolyester is 1, and the molar ratio of the polyethylene glycol structural unit to the ethylene glycol structural unit is 0.01.

[0042] In the above technical solution, preferably, the isophthalic acid sulfonate is selected from isophthalic acid-5-sulfonic acid or an alkali metal salt of isophthalic acid-5-sulfonic acid, more preferably an alkali metal salt of isophthalic acid-5-sulfonic acid, and the alkali metal is preferably sodium or potassium.

[0043] In the above technical solution, preferably, the polyester containing an anionic group is composed of a terephthalic acid structural unit, an isophthalic acid sulfonate structural unit, and a C2-C4 diol unit. The diol is selected from at least one of the substances consisting of ethylene glycol, 1,3-propanediol, and 1,4-butanediol. For the sake of comparison only, ethylene glycol is used as the C2-C4 diol in the examples of the present invention.

[0044] In the above technical solution, by way of non-limiting example, the molar ratio of the terephthalic acid structural unit to the isophthalic acid sulfonate structural unit in the polyester containing an anionic group is 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, and so on.

[0045] In the above technical solution, preferably, the intrinsic viscosity of the polyester containing an anionic group is 0.50-0.70 dl / g, such as but not limited to 0.51 dl / g, 0.52 dl / g, 0.53 dl / g, 0.54 dl / g, 0.55 dl / g, 0.56 dl / g, 0.57 dl / g, 0.58 dl / g, 0.59 dl / g, 0.6 dl / g, 0.61 dl / g, 0.62 dl / g, 0.63 dl / g, 0.64 dl / g, 0.65 dl / g, 0.66 dl / g, 0.67 dl / g, 0.68 dl / g, 0.69 dl / g, and so on, and more preferably 0.55-0.65 dl / g.

[0046] The polyester containing anionic groups can be obtained by Preparation Method 1 including the following steps:

[0047] Esterification reaction i

[0048] Terephthalic acid and a diol are subjected to an esterification reaction in the presence of a polymerization catalyst to obtain an intermediate mixture i; preferably, the molar ratio of the diol to terephthalic acid is 1.05 to 1.50 (for example, but not limited to, the molar ratio of the diol to terephthalic acid being 1.1, 1.15, 1.2, 1.25, 1.3, 1.35, 1.4, 1.45, etc.), and / or preferably the esterification reaction temperature is 235 to 250 °C (for example, but not limited to 236 °C, 237 °C, 238 °C, 239 °C, 240 °C, 241 °C, 242 °C, 243 °C, 244 °C, 245 °C, 246 °C, 247 °C, 248 °C, 249 °C, etc.), and / or preferably the esterification rate is controlled to be 95 to 99% (for example, but not limited to the esterification rate being controlled to be 95.5%, 96%, 96.5%, 97%, 97.5%, 98%, 98.5%, etc.); and / or the pressure of the esterification reaction is preferably 0.1 to 1.0 MPa in gauge pressure (for example, but not limited to 0.15 MPa, 0.2 MPa, 0.25 MPa, 0.3 MPa, 0.35 MPa, 0.4 MPa, 0.45 MPa, 0.5 MPa, 0.55 MPa, 0.6 MPa, 0.65 MPa, 0.7 MPa, 0.75 MPa, 0.8 MPa, 0.85 MPa, 0.9 MPa, 0.95 MPa, etc.); the polymerization catalyst is, taking the antimony-based catalyst as an example, 100 to 300 ppmw based on the weight of terephthalic acid in terms of antimony (for example, but not limited to 110 ppmw, 120 ppmw, 130 ppmw, 140 ppmw, 150 ppmw, 160 ppmw, 170 ppmw, 180 ppmw, 190 ppmw, 200 ppmw, 210 ppmw, 220 ppmw, 230 ppmw, 240 ppmw, 250 ppmw, 260 ppmw, 270 ppmw, 280 ppmw, 290 ppmw, etc.); the diol is selected from at least one of the group consisting of ethylene glycol, 1,3-propanediol, and 1,4-butanediol. Only for the sake of comparison, ethylene glycol is used as the diol in the esterification reaction i in the examples;

[0049] Esterification reaction ii

[0050] The alkali metal salt of isophthalic acid-5-sulfonic acid reacts with a diol in the presence of a polymerization catalyst to obtain an intermediate mixture ii; preferably, the molar ratio of the diol to the alkali metal salt of isophthalic acid-5-sulfonic acid is 1.05 to 1.50 (for example, but not limited to, the molar ratio of the diol to the alkali metal salt of isophthalic acid-5-sulfonic acid being 1.1, 1.15, 1.2, 1.25, 1.3, 1.35, 1.4, 1.45, etc.), and / or preferably the esterification reaction temperature is 235 to 255 °C (for example, but not limited to 236 °C, 237 °C, 238 °C, 239 °C, 240 °C, 241 °C, 242 °C, 243 °C, 244 °C, 245 °C, 246 °C, 247 °C, 248 °C, 249 °C, 250 °C, 251 °C, 252 °C, 253 °C, 254 °C, etc.), and / or preferably the esterification rate is controlled to be 95 to 99% (for example, but not limited to the esterification rate being controlled to be 95.5%, 96%, 96.5%, 97%, 97.5%, 98%, 98.5%, etc.), and / or preferably the pressure of the esterification is 0.1 to 1.0 MPa in gauge pressure (for example, but not limited to 0.15 MPa, 0.2 MPa, 0.25 MPa, 0.3 MPa, 0.35 MPa, 0.4 MPa, 0.45 MPa, 0.5 MPa, 0.55 MPa, 0.6 MPa, 0.65 MPa, 0.7 MPa, 0.75 MPa, 0.8 MPa, 0.85 MPa, 0.9 MPa, 0.95 MPa, etc.); the polymerization catalyst is, for example, an antimony-based catalyst, and in terms of antimony, it is preferably 100 to 300 ppmw relative to the weight of the alkali metal salt of isophthalic acid-5-sulfonic acid (for example, but not limited to 110 ppmw, 120 ppmw, 130 ppmw, 140 ppmw, 150 ppmw, 160 ppmw, 170 ppmw, 180 ppmw, 190 ppmw, 200 ppmw, 210 ppmw, 220 ppmw, 230 ppmw, 240 ppmw, 250 ppmw, 260 ppmw, 270 ppmw, 280 ppmw, 290 ppmw, etc.); the alkali metal salt of isophthalic acid-5-sulfonic acid is preferably potassium isophthalate-5-sulfonate and / or sodium isophthalate-5-sulfonate; the diol is selected from at least one of the group consisting of ethylene glycol, 1,3-propanediol, and 1,4-butanediol. Only for the sake of comparison, ethylene glycol is used as the diol in the esterification reaction ii in the examples; the alkali metal salts of isophthalic acid-5-sulfonic acid are all sodium isophthalate-5-sulfonate;

[0051] Polycondensation reaction iii

[0052] The intermediate mixture i and the intermediate mixture ii are mixed and subjected to a polycondensation reaction together until the required intrinsic viscosity is obtained, to obtain the polyester containing anionic groups; preferably, the ratio of the intermediate mixture i (calculated based on the number of moles of terephthalic acid required for synthesizing it) to the intermediate mixture ii (calculated based on the number of moles of sodium 5-sulfoisophthalate required for synthesizing it) is 1 to 9 (for example, but not limited to, this ratio being 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, etc., only for the sake of comparison, and this ratio is 4 in the examples of the present invention). And / or preferably, first carry out polycondensation at an absolute pressure of 400 to 600 MPa (for example, but not limited to, 420 MPa, 440 MPa, 460 MPa, 480 MPa, 500 MPa, 520 MPa, 540 MPa, 560 MPa, 580 MPa, 590 MPa, etc.) and a temperature of 255 to 265 °C (for example, but not limited to, 256 °C, 257 °C, 258 °C, 259 °C, 260 °C, 261 °C, 262 °C, 263 °C, 264 °C, etc.) for 30 to 60 minutes (for example, but not limited to, 35 minutes, 40 minutes, 45 minutes, 50 minutes, 55 minutes, etc.), and then carry out polycondensation at an absolute pressure below 100 Pa (for example, but not limited to, the absolute pressure being 5 Pa, 10 Pa, 20 Pa, 30 Pa, 40 Pa, 50 Pa, 60 Pa, 70 Pa, 80 Pa, 90 Pa, etc.) until the required intrinsic viscosity is reached.

[0053] When the polyester containing anionic groups is prepared by Method 1, only for the sake of comparison, the specific preparation process conditions in the specific embodiments of the present invention are as follows, and the polyester containing anionic groups obtained is called polyester containing anionic groups 1:

[0054] Esterification reaction (i)

[0055] Ethylene glycol and terephthalic acid are subjected to an esterification reaction in the presence of antimony glycolate. The molar ratio of ethylene glycol to terephthalic acid is 1.10, and the dosage of antimony glycolate is 200 ppmw (calculated based on antimony, relative to the weight of terephthalic acid input in the reaction raw materials). The esterification reaction pressure (gauge pressure) is 0.2 MPa, and the esterification reaction temperature is 240 °C. The water generated and distilled out during esterification is collected, and the esterification rate is calculated through the amount of water discharged; when the esterification rate reaches 97%, the esterification reaction (i) is completed to obtain the intermediate mixture (i).

[0056] Esterification reaction (ii)

[0057] The esterification reaction is carried out with ethylene glycol and sodium 5-sulfoisophthalate in the presence of antimony glycolate. The molar ratio of ethylene glycol to sodium 5-sulfoisophthalate is 1.10, and the dosage of antimony glycolate is 200 ppmw (in terms of antimony, relative to the weight of sodium 5-sulfoisophthalate input in the reaction raw materials). The esterification reaction pressure (gauge pressure) is 0.2 MPa, and the esterification reaction temperature is 240 °C. The water generated by esterification and distilled out is collected, and the esterification rate is calculated through the amount of water discharged; when the esterification rate reaches 97%, the esterification reaction (ii) is completed to obtain the intermediate mixture (ii).

[0058] Polycondensation reaction (iii)

[0059] The intermediate mixture (i) and the intermediate mixture (ii) are mixed in a reactor. The ratio of the intermediate mixture (i) (in terms of the molar number of terephthalic acid required for synthesizing it) to the intermediate mixture (ii) (in terms of the molar number of sodium 5-sulfoisophthalate required for synthesizing it) is 4. The pressure is evacuated to an absolute pressure of 500 Pa, and the temperature is raised to 260 °C. The reaction time is 45 min. Then, the pressure is evacuated to an absolute pressure of 50 Pa, and polycondensation continues at this pressure until the intrinsic viscosity reaches 0.59 dl / g, completing the polycondensation reaction (iii) to obtain the polyester 1 containing anionic groups.

[0060] Upon analysis, in the polyester 1 containing anionic groups, the molar ratio of the molar number of ethylene glycol structural units to (the molar number of terephthalic acid structural units + the molar number of sodium 5-sulfoisophthalate) is 1, and the molar ratio of the molar number of terephthalic acid structural units to the molar number of sodium 5-sulfoisophthalate is 4.

[0061] The polyester containing anionic groups is obtained by a preparation method 2 including the following steps:

[0062] First, a diesterification reaction is carried out between a diacid and a diol in the presence of a polymerization catalyst to obtain an intermediate mixture; the molar ratio of the diol to the diacid is preferably 1.05 to 1.50 (for example, but not limited to, the molar ratio of the diol to the diacid being 1.1, 1.15, 1.2, 1.25, 1.3, 1.35, 1.4, 1.45, etc.), the diacid is preferably terephthalic acid and sodium 5-sulfoisophthalate, and more preferably the molar ratio of terephthalic acid to sodium 5-sulfoisophthalate is 1 to 9 (for example, but not limited to, this ratio being 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, etc., only for the sake of comparison, this ratio is 4 in the examples of the present invention), the temperature of the diesterification reaction is preferably 235 to 250 °C (for example, but not limited to, 236 °C, 237 °C, 238 °C, 239 °C, 240 °C, 241 °C, 242 °C, 243 °C, 244 °C, 245 °C, 246 °C, 247 °C, 248 °C, 249 °C, etc.), the esterification rate is preferably 95 to 99% (for example, but not limited to, controlling the esterification rate to be 95.5%, 96%, 96.5%, 97%, 97.5%, 98%, 98.5%, etc.), the pressure of the diesterification reaction in gauge pressure is preferably 0.1 to 1.0 MPa (for example, but not limited to, 0.15 MPa, 0.2 MPa, 0.25 MPa, 0.3 MPa, 0.35 MPa, 0.4 MPa, 0.45 MPa, 0.5 MPa, 0.55 MPa, 0.6 MPa, 0.65 MPa, 0.7 MPa, 0.75 MPa, 0.8 MPa, 0.85 MPa, 0.9 MPa, 0.95 MPa, etc.); taking an antimony-based catalyst as an example for the polymerization catalyst, the amount of the catalyst is calculated as antimony, and is preferably 100 to 300 ppmw relative to the weight of the diacid (for example, but not limited to, 110 ppmw, 120 ppmw, 130 ppmw, 140 ppmw, 150 ppmw, 160 ppmw, 170 ppmw, 180 ppmw, 190 ppmw, 200 ppmw, 210 ppmw, 220 ppmw, 230 ppmw, 240 ppmw, 250 ppmw, 260 ppmw, 270 ppmw, 280 ppmw, 290 ppmw, etc.); the diol is selected from at least one of the group consisting of ethylene glycol, 1,3-propanediol, and 1,4-butanediol. Only for the sake of comparison, ethylene glycol is selected as the diol in the esterification reaction in the examples.Then, polycondense to the desired intrinsic viscosity; preferably, first polycondense at an absolute pressure of 400-600 MPa (such as but not limited to 420 MPa, 440 MPa, 460 MPa, 480 MPa, 500 MPa, 520 MPa, 540 MPa, 560 MPa, 580 MPa, 590 MPa, etc.) and a temperature of 255-265 °C (such as but not limited to 256 °C, 257 °C, 258 °C, 259 °C, 260 °C, 261 °C, 262 °C, 263 °C, 264 °C, etc.) for 30-60 minutes (such as but not limited to 35 minutes, 40 minutes, 45 minutes, 50 minutes, 55 minutes, etc.), and then polycondense at an absolute pressure below 100 Pa (such as but not limited to an absolute pressure of 5 Pa, 10 Pa, 20 Pa, 30 Pa, 40 Pa, 50 Pa, 60 Pa, 70 Pa, 80 Pa, 90 Pa, etc.) to the desired intrinsic viscosity.

[0063] When the polyester containing anionic groups is prepared by Method 2, only for comparison, the specific preparation process conditions in the specific embodiments of the present invention are as follows, and the obtained polyester containing anionic groups is called polyester containing anionic groups 2:

[0064] Ethylene glycol, terephthalic acid and sodium 5-sulfoisophthalate are subjected to an esterification reaction in the presence of antimony glycolate. The molar ratio of ethylene glycol to diacid is 1.10, the molar ratio of terephthalic acid to sodium 5-sulfoisophthalate is 4, and the dosage of antimony glycolate is 200 ppmw (calculated as antimony, relative to the weight of terephthalic acid + sodium 5-sulfoisophthalate input in the reaction raw materials). The esterification reaction pressure (gauge pressure) is 0.2 MPa, and the esterification reaction temperature is 240 °C. The water generated and distilled out during the esterification reaction is collected, and the esterification rate is calculated through the water output; when the esterification rate reaches 97%, the esterification reaction is completed to obtain an intermediate mixture. First, polycondense at an absolute pressure of 500 Pa and 260 °C for 45 min, and then continue to polycondense at an absolute pressure of 50 Pa until the intrinsic viscosity reaches 0.58 dl / g to complete the polycondensation reaction and obtain polyester containing anionic groups 2.

[0065] After analysis, the molar ratio of ethylene glycol structural units to diacid structural units in polyester containing anionic groups 2 is 1, and the molar ratio of terephthalic acid structural units to sodium 5-sulfoisophthalate structural units is 4.

[0066] We found that the fibers prepared by using the above Preparation Method 1 for the polyester containing anionic groups have better antibacterial properties and better antibacterial durability than those prepared by using the above Preparation Method 2.

[0067] In the above technical solution, it is more preferable that the modifier includes a polyester containing a polyethylene glycol segment and a polyester containing an anionic group. These two modifiers have a synergistic effect in improving the antibacterial performance of the fiber. There is no particular limitation on the dosage ratio of the polyester containing a polyethylene glycol segment to the polyester containing an anionic group, and comparable synergistic effects can be achieved. Only as a non-limiting example, the weight ratio of the polyester containing an anionic group to the polyester containing a polyethylene glycol segment is 1 to 9. More specifically, as a non-limiting example, the weight ratio of the polyester containing an anionic group to the polyester containing a polyethylene glycol segment is 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, etc. Only for comparison, in the specific embodiments of the present invention, when both the polyester containing a polyethylene glycol segment and the polyester containing an anionic group are used, the weight ratio of the polyester containing an anionic group to the polyester containing a polyethylene glycol segment is 2.

[0068] In the specification of the present invention, for the measurement method of the intrinsic viscosity of all polyesters (including PET, the polyester containing a polyethylene glycol segment, and the polyester containing an anionic group), method A in section 5.1.1 of GB / T 14190-2017 (Test methods for fiber-grade polyester (PET) chips) is adopted, and the solvent used is a mixture of phenol and 1,1,2,2-tetrachloroethane with a mass ratio of 50:50.

[0069] The key technology of the present invention is the selection of the spinning raw materials in step (1). When the spinning raw material PET contains a polyester containing a polyethylene glycol segment or a polyester containing an anionic group as a modifier, compared with pure PET spinning, the antibacterial fiber obtained by finishing with an antibacterial guanidine salt finishing solution has better antibacterial properties and antibacterial durability.

[0070] There are no particular limitations on other process conditions for specific spinning, and comparable technical effects can be achieved.

[0071] Only as an example, the temperature of melt spinning in step (1) is 260 to 290 °C. For example, but not limited to, 265 °C, 270 °C, 275 °C, 280 °C, 285 °C, etc. Only for comparison, 280 °C is used as the spinning temperature in the specific embodiments of the present invention.

[0072] The key steps of the technology of the present invention are the use of the modifier in the spinning raw materials in step (1) and the presence of antibacterial guanidine salt in the finishing solution in step (4), while there are no particular requirements for the oil agent and the oil agent emulsion in step (2), and those commonly used in the art and mature commercial oil agents can be selected. Those skilled in the art will use different oil agents according to the type of target fiber, such as filament yarns and staple fibers, as well as the fiber manufacturing process. The present invention can be applied to all of them, and comparable technical effects can be achieved without creative labor. Only for comparison, the type of target fiber in the examples and comparative examples of the present invention is polyester filament yarns produced by the FDY process.

[0073] In the above technical solution, preferably, by weight, the content of the active substance in the oil agent emulsion is 5-15% (such as but not limited to 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5%). Only for comparison, in the examples and comparative examples of the present invention, the content of the active substance in the oil agent emulsion in step (2) is 10%.

[0074] In the specific implementation manner of the present invention, the method for preparing the commercial oil agent into an oil agent emulsion is not particularly limited, and those well-known to those skilled in the art can be adopted, and there is no obvious difference in achieving the effects of the present invention. Only for comparison, in the examples and comparative examples in the specific implementation manner of the present invention, the oil agent emulsions used are all obtained by adding the required amount of water to the commercial oil agent under shear and mixing evenly.

[0075] Those skilled in the art know that the active substances of commercial polyester filament oil agents and oil agent emulsions are similar in composition among different manufacturers. The main active substance components are nothing but leveling agents, non-ionic surfactants and anionic surfactants. Therefore, the active substance is the general term for leveling agents, non-ionic surfactants and anionic surfactants. The composition of polyester filament oil agents has been reported in the prior art. For example, the patent CN114921958A applied by Tianjin Polytechnic University Textile Auxiliary Co., Ltd., the patent CN106087406A applied by Shanghai Duolun Chemical Co., Ltd., and so on. Examples of commercially available polyester filament oil agents include, for example but not limited to, the TFDY-500 type spinning oil agent of Tianjin Polytechnic University Textile Auxiliary Co., Ltd., the polyester FDY oil agent JDF-5101 provided by Shanghai Duolun Chemical Co., Ltd., and so on. Only for comparison, the oil agent used in the specific implementation manner and comparative example of the present invention is the TFDY-500 type spinning oil agent of Tianjin Polytechnic University Textile Auxiliary Co., Ltd.

[0076] In the above technical solution, preferably, the oil content of the oil-containing fiber in step (2) is 0.5-3%, such as but not limited to 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, etc. Only for comparison, the oil content used in the examples and comparative examples of the present invention is 2.0%.

[0077] Those skilled in the art know that the measurement and calculation method of the oil content of the oil-containing fiber is:

[0078] The oil content of the oil-containing fiber is measured by the nuclear magnetic resonance method specified in Section 5.4 of "GB / T 6504-2017 Test Method for Oil Content of Chemical Fibers".

[0079] In the above technical solution, it is preferred that the temperature of the drawing in step (3) is 120-160 °C. For example but not limited to 120 °C, 125 °C, 130 °C, 135 °C, 140 °C, 145 °C, 150 °C, 155 °C, 160 °C. For the sake of comparison only, the drawing temperature in the specific embodiment of the present invention is 140 °C.

[0080] In the above technical solution, it is preferred that the draw ratio of the drawing in step (3) is 3.0-5.0. For example but not limited to 3.1 times, 3.2 times, 3.3 times, 3.4 times, 3.5 times, 3.6 times, 3.7 times, 3.8 times, 3.9 times, 4.0 times, 4.1 times, 4.2 times, 4.3 times, 4.4 times, 4.5 times, 4.6 times, 4.7 times, 4.8 times, 4.9 times, 5.0 times. For the sake of comparison only, the draw ratio in the specific embodiment of the present invention is 4.0 times.

[0081] The specification of the filament is usually 50-200 D. For example but not limited to 50 D, 60 D, 70 D, 80 D, 90 D, 100 D, 110 D, 120 D, 130 D, 140 D, 150 D, 160 D, 170 D, 180 D, 190 D, 200 D. The specification of the fiber is not the key of the present invention. No matter what specification, comparable technical effects can be achieved. For the sake of comparison only, the specification of the filament in the specific embodiment of the present invention is 150 D.

[0082] In the above technical solution, it is preferred that the antibacterial guanidine salt finishing solution in step (4) includes the following components by weight:

[0083] Antibacterial guanidine salt, 0.1-5 parts;

[0084] Water, 100 parts.

[0085] In the above technical solution, the antibacterial guanidine salt is not particularly limited, but preferably those antibacterial guanidine salts that are easily soluble in water. For example but not limited to at least one selected from the group consisting of polyhexamethylene biguanide sulfate, polyhexamethylene biguanide hydrochloride (PHMG), polyhexamethylene biguanide nitrate, polyhexamethylene biguanide phosphate, polyhexamethylene biguanide acetate, biguanide octanoate, dodecyl guanidine salt, etc. The function of this type of guanidine salt is to provide antibacterial properties. Only by way of example, polyhexamethylene biguanide hydrochloride is used in both the examples and comparative examples of the present invention.

[0086] In the above technical solution, by way of non-limiting example, the finishing liquid contains 0.15 parts, 0.2 parts, 0.25 parts, 0.3 parts, 0.35 parts, 0.4 parts, 0.45 parts, 0.5 parts, 0.55 parts, 0.6 parts, 0.65 parts, 0.7 parts, 0.75 parts, 0.8 parts, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, etc. of the antibacterial guanidine salt by weight.

[0087] In the above technical solution, preferably, the steps of the finishing in step (4) include:

[0088] (I) Impregnating the fiber as the fiber to be antibacterial finished with the finishing liquid containing the antibacterial guanidine salt to obtain the liquid-carrying fiber I;

[0089] (II) Drying;

[0090] (III) Heat setting.

[0091] In the above technical solution, during impregnation, the ratio between the finishing liquid and the fiber to be antibacterial finished is not particularly limited, and those skilled in the art can reasonably grasp it, and comparable technical effects can be obtained without creative labor. For example, but not limited to, the weight ratio between the finishing liquid and the fiber to be antibacterial finished is 10-50, and more specific weight ratios are 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 25, 30, 35, 40, 45, etc. Only for the sake of comparison, this weight ratio is 15 in both the examples and comparative examples of the present invention.

[0092] In the above technical solution, the liquid-carrying rate in the liquid-carrying fiber I in step (I) is not particularly limited, and those skilled in the art can reasonably control the liquid-carrying rate according to the concentration of the antibacterial guanidine salt contained in the finishing liquid, the specific type of the antibacterial guanidine salt and the strength of the antibacterial property, the ability of the fiber to adsorb the finishing liquid, the amount of the antibacterial guanidine salt loaded in the antibacterial fiber to be obtained, and whether and the degree of extrusion after impregnation.

[0093] The present invention specification adopts the common meaning of the liquid-carrying rate in the art. The liquid-carrying rate, that is, the ratio of the finishing liquid contained in the fiber to be antibacterial finished, is based on the dry weight of the fiber to be antibacterial finished by weight, that is, it refers to the percentage of the weight of the liquid carried by the fiber relative to the dry weight of the fiber.

[0094] By way of example only, the liquid-carrying rate in the liquid-carrying fiber I can be 40-70%, for example but not limited to, the liquid-carrying rate of the liquid-carrying fiber I is 45%, 50%, 55%, 60%, 65%, etc. Only for the sake of comparison, the liquid-carrying rate is controlled at 50% in both the examples and comparative examples.

[0095] In the above technical solution, preferably, the drying temperature in step (II) is 80 - 110°C, such as but not limited to 85°C, 90°C, 95°C, 100°C, 105°C. Only for comparison, the drying temperature in the examples and comparative examples of the present invention specification is both 100°C.

[0096] In the above technical solution, preferably, the drying time in step (II) is 3 - 10 minutes, such as but not limited to 3.5 minutes, 4 minutes, 4.5 minutes, 5 minutes, 5.5 minutes, 6 minutes, 6.5 minutes, 7 minutes, 7.5 minutes, 8 minutes, 8.5 minutes, 9 minutes, 9.5 minutes, etc. Only for comparison, the drying time in the examples and comparative examples of the present invention specification is both 5 minutes.

[0097] In the above technical solution, preferably, the heat setting temperature in step (III) is 120 - 180°C, such as but not limited to 125°C, 130°C, 135°C, 140°C, 145°C, 150°C, 155°C, 160°C, 165°C, 170°C, 175°C, etc. Only for comparison, the heat setting temperature in the examples and comparative examples of the present invention specification is both 150°C.

[0098] In the above technical solution, preferably, the heat setting time in step (III) is 1 - 5 minutes, such as but not limited to 1.5 minutes, 2 minutes, 2.5 minutes, 3 minutes, 3.5 minutes, 4 minutes, 4.5 minutes, etc. Only for comparison, the heat setting time in the examples and comparative examples of the present invention specification is both 3 minutes.

[0099] The determination of the breaking strength and elongation of the fiber is carried out according to the method for determining dry - state breaking and breaking elongation in "GB / T 14344 - 2008 Test Method for Drafting Properties of Chemical Fiber Filaments".

[0100] The durability evaluation of the antibacterial property of the fiber product is carried out in accordance with "GBT20944.3 - 2008 Evaluation of Antibacterial Properties of Textiles - Part 3: Oscillation Method". Before testing the fiber product, it is washed 50 times according to the method 10.1.2 in this standard. The test strains used are Staphylococcus aureus (ATCC 6538), Escherichia coli (8099) and Candida albicans (ATCC10231) adopted in this standard. The higher the antibacterial rate measured after washing 50 times by the above method, the better the antibacterial property and antibacterial property durability of the fiber product.

[0101] The present invention will be described in detail below through specific embodiments. Specific Embodiments

[0102]

Comparative Example

[0103] 1. Preparation of Antibacterial Fibers

[0104] 1.1 Melt Spinning

[0105] The polyethylene terephthalate is melt-spun to obtain the as-spun fiber, and the temperature of melt spinning is 280 °C.

[0106] 1.2 Fiber Oiling and Drawing

[0107] The as-spun fiber obtained by melt spinning is oiled to obtain the oil-containing fiber. The way of oiling the as-spun fiber is oiling through the nozzle, and the oil content rate of the oil-containing fiber is 2.0%. The oil-containing fiber is thermally drawn, the draw ratio is 4.0 times, and the drawing temperature is 140 °C. Then the FDY fiber is spun, and the FDY fiber specification is 150D.

[0108] 1.3 Fiber Antibacterial Finishing

[0109] The fiber obtained in Section 1.2 is impregnated in an aqueous solution of polyhexamethylene biguanide hydrochloride with a weight concentration of 0.4% for 10 minutes. The weight ratio of the fiber to the aqueous solution of polyhexamethylene biguanide hydrochloride is 1:15. Then, it is extruded to make the liquid holding rate 50%, and then dried at 100 °C for 5 minutes and shaped at 150 °C for 3 minutes by a shaping and drying machine to obtain the antibacterial fiber.

[0110] 2. Antibacterial Fiber Testing

[0111] After testing, the breaking strength of the fiber is 4.42 cN / dtex; the breaking elongation is 22.1%; the antibacterial rate against Staphylococcus aureus is 18.3%, the antibacterial rate against Escherichia coli is 17.6%, and the antibacterial rate against Candida albicans is 17.5%.

[0112]

Example 1

[0113] 1. Preparation of Antibacterial Fibers

[0114] 1.1 Melt Spinning

[0115] The polyethylene terephthalate and the polyester containing polyethylene glycol segments are melt-spun together to obtain the as-spun fiber, and the temperature of melt spinning is 280 °C. The dosage of the polyester containing polyethylene glycol segments is 12% of the weight of the polyethylene terephthalate.

[0116] 1.2 Fiber Oiling and Drawing

[0117] The as-spun fiber obtained by melt spinning is oiled to obtain the oil-containing fiber. The way of oiling the as-spun fiber is oiling through the nozzle, and the oil content rate of the oil-containing fiber is 2.0%. The oil-containing fiber is thermally drawn, the draw ratio is 4.0 times, and the drawing temperature is 140 °C. Then the FDY fiber is spun, and the FDY fiber specification is 150D.

[0118] 1.3. Fiber antibacterial finishing

[0119] The fibers obtained in Section 1.2 above are impregnated in an aqueous solution of polyhexamethylene biguanide hydrochloride with a weight concentration of 0.4% for 10 minutes. The weight ratio of the fibers to the aqueous solution of polyhexamethylene biguanide hydrochloride is 1:15. Then, extrusion is carried out to make the liquid holding rate 50%. Then, drying is carried out at 100 °C for 5 minutes and setting is carried out at 150 °C for 3 minutes using a setting and drying machine to obtain antibacterial fibers.

[0120] 2. Antibacterial fiber testing

[0121] After testing, the breaking strength of the fiber is 4.71 cN / dtex; the breaking elongation is 21.9%; the antibacterial rate against Staphylococcus aureus is 48.4%, the antibacterial rate against Escherichia coli is 48.2%, and the antibacterial rate against Candida albicans is 48.5%.

[0122]

Example 2

[0123] 1. Preparation of antibacterial fibers

[0124] 1.1. Melt spinning

[0125] Polyethylene terephthalate and polyester 1 containing anionic groups are melt-blended and spun to obtain primary fibers. The temperature of the melt spinning is 280 °C. The amount of polyester 1 containing anionic groups is 12% of the weight of polyethylene terephthalate.

[0126] 1.2. Fiber oiling and drawing

[0127] The primary fibers obtained by melt spinning are oiled to obtain oil-containing fibers. The method of oiling the primary fibers is oiling at the oil nozzle. The oil content of the oil-containing fibers is 2.0%. The oil-containing fibers are thermally drawn with a draw ratio of 4.0 times and a draw temperature of 140 °C. Then, FDY fibers are spun, and the FDY fiber specification is 150D.

[0128] 1.3. Fiber antibacterial finishing

[0129] The fibers obtained in Section 1.2 above are impregnated in an aqueous solution of polyhexamethylene biguanide hydrochloride with a weight concentration of 0.4% for 10 minutes. The weight ratio of the fibers to the aqueous solution of polyhexamethylene biguanide hydrochloride is 1:15. Then, extrusion is carried out to make the liquid holding rate 50%. Then, drying is carried out at 100 °C for 5 minutes and setting is carried out at 150 °C for 3 minutes using a setting and drying machine to obtain antibacterial fibers.

[0130] 2. Antibacterial fiber testing

[0131] After testing, the breaking strength of the fiber is 4.80 cN / dtex; the elongation at break is 21.6%; the antibacterial rate against Staphylococcus aureus is 61.2%, the antibacterial rate against Escherichia coli is 63.4%, and the antibacterial rate against Candida albicans is 64.9%.

[0132]

Example 3

[0133] 1. Preparation of antibacterial fiber

[0134] 1.1 Melt spinning

[0135] Polyethylene terephthalate and polyester 2 containing anionic groups are melt-blended and spun to obtain nascent fibers. The temperature of melt spinning is 280 °C. The amount of polyester 2 containing anionic groups is 12% by weight of polyethylene terephthalate.

[0136] 1.2 Fiber oiling and drawing

[0137] The nascent fibers obtained by melt spinning are oiled to obtain oil-containing fibers. The method of oiling the nascent fibers is oiling at the oil nozzle, and the oil content of the oil-containing fibers is 2.0%. The oil-containing fibers are hot-drawn, the draw ratio is 4.0 times, and the drawing temperature is 140 °C. Then FDY fibers are spun, and the FDY fiber specification is 150D.

[0138] 1.3 Fiber antibacterial finishing

[0139] The fibers obtained in Section 1.2 above are immersed in an aqueous solution of polyhexamethylene biguanide hydrochloride with a weight concentration of 0.4% for 10 minutes. The weight ratio of the fibers to the aqueous solution of polyhexamethylene biguanide hydrochloride is 1:15. Then, extrusion is carried out to make the liquid-carrying rate 50%. Then, drying is carried out at 100 °C for 5 minutes with a shaping dryer, and shaping is carried out at 150 °C for 3 minutes to obtain antibacterial fibers.

[0140] 2. Antibacterial fiber testing

[0141] After testing, the breaking strength of the fiber is 2.59 cN / dtex; the elongation at break is 20.1%; the antibacterial rate against Staphylococcus aureus is 65.8%, the antibacterial rate against Escherichia coli is 66.6%, and the antibacterial rate against Candida albicans is 61.5%.

[0142]

Example 4

[0143] 1. Preparation of antibacterial fiber

[0144] 1.1 Melt spinning

[0145] Polyethylene terephthalate, a polyester containing polyethylene glycol segments, and a polyester 1 containing anionic groups are melt-blended and spun to obtain as-spun fibers. The temperature of the melt spinning is 280 °C. The dosage of the modifier (the polyester containing polyethylene glycol segments and the polyester 1 containing anionic groups) is 12% of the weight of polyethylene terephthalate. The mass ratio of the polyester 1 containing anionic groups to the polyester containing polyethylene glycol segments is 2.

[0146] 1.2 Fiber oiling and drawing

[0147] The as-spun fibers obtained by melt spinning are oiled to obtain oil-containing fibers. The method of oiling the as-spun fibers is oiling at the oil nozzle, and the oil content of the oil-containing fibers is 2.0%. The oil-containing fibers are heat-drawn. The draw ratio is 4.0 times, and the drawing temperature is 140 °C. Then FDY fibers are spun, and the FDY fiber specification is 150D.

[0148] 1.3 Fiber antibacterial finishing

[0149] The fibers obtained in Section 1.2 above are immersed in an aqueous solution of polyhexamethylene biguanide hydrochloride with a weight concentration of 0.4% for 10 minutes. The weight ratio of the fibers to the aqueous solution of polyhexamethylene biguanide hydrochloride is 1:15. Then, extrusion is carried out to make the liquid-carrying rate 50%. Then, it is dried at 100 °C for 5 minutes and shaped at 150 °C for 3 minutes with a shaping and drying machine to obtain antibacterial fibers.

[0150] 2 Antibacterial fiber testing

[0151] After testing, the breaking strength of the fiber is 4.87 cN / dtex; the breaking elongation is 20.1%; the antibacterial rate against Staphylococcus aureus is 76.7%, the antibacterial rate against Escherichia coli is 72.8%, and the antibacterial rate against Candida albicans is 73.5%.

[0152]

Example 5

[0153] 1 Preparation of antibacterial fibers

[0154] 1.1 Melt spinning

[0155] Polyethylene terephthalate, a polyester containing polyethylene glycol segments, and a polyester 2 containing anionic groups are melt-blended and spun to obtain as-spun fibers. The temperature of the melt spinning is 280 °C. The dosage of the modifier (the polyester containing polyethylene glycol segments and the polyester 2 containing anionic groups) is 12% of the weight of polyethylene terephthalate. The mass ratio of the polyester 2 containing anionic groups to the polyester containing polyethylene glycol segments is 2.

[0156] 1.2 Fiber oiling and drawing

[0157] The as-spun fibers obtained by melt spinning are oiled to obtain oil-containing fibers. The method of oiling the as-spun fibers is oiling through an oil nozzle. The oil content of the oil-containing fibers is 2.0%. The oil-containing fibers are hot drawn with a draw ratio of 4.0 times and a draw temperature of 140 °C. Then, FDY fibers are spun, and the FDY fiber specification is 150D.

[0158] 1.3. Fiber antibacterial finishing

[0159] The fibers obtained in Section 1.2 above are immersed in an aqueous solution of polyhexamethylene biguanide hydrochloride with a weight concentration of 0.4% for 10 minutes. The weight ratio of the fibers to the aqueous solution of polyhexamethylene biguanide hydrochloride is 1:15. Then, extrusion is carried out to make the liquid-carrying rate 50%. Then, drying is carried out at 100 °C for 5 minutes and shaping is carried out at 150 °C for 3 minutes with a shaping and drying machine to obtain antibacterial fibers.

[0160] 2. Antibacterial fiber testing

[0161] After testing, the breaking strength of the fiber is 3.56 cN / dtex; the breaking elongation is 21.3%; the antibacterial rate against Staphylococcus aureus is 78.9%, the antibacterial rate against Escherichia coli is 77.7%, and the antibacterial rate against Candida albicans is 75.8%.

[0162] It should be noted that the above-described embodiments are only used to explain the present invention and do not constitute any limitation to the present invention. The present invention has been described by referring to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory words rather than limiting words. Modifications can be made to the present invention within the scope of the claims of the present invention as specified, and the present invention can be revised without departing from the scope and spirit of the present invention. Although the present invention described therein relates to specific methods, materials, and embodiments, it does not mean that the present invention is limited to the specific examples disclosed therein. On the contrary, the present invention can be extended to all other methods and applications with the same functions.

Claims

1. Method for manufacturing antibacterial polyester fiber, comprising: (1)Using polyethylene terephthalate and a modifier as raw materials, melt spinning is carried out to obtain nascent fibers. Polyethylene terephthalate is abbreviated as PET; (2)Applying a fiber oil agent emulsion to the surface of the nascent fibers to obtain oil-containing fibers; (3)Performing hot drawing on the oil-containing fibers; (4)Treating the obtained fibers with an antibacterial guanidine salt finishing solution to obtain antibacterial polyester fibers; It is characterized in that: The modifier includes a polyester containing a polyethylene glycol segment and a polyester containing an anionic group; In the raw materials of step (1), the weight ratio of the modifier to PET is 0.01~0.30; In the polyester containing a polyethylene glycol segment, the molar ratio of the structural unit ─(CH2CH2O) from polyethylene glycol m ─ to the structural unit ─CH2CH2O─ from ethylene glycol is 0.004 to 0.04; The anionic group in the polyester containing an anionic group comes from isophthalic acid sulfonate; The molar ratio of the terephthalic acid structural unit to the isophthalic acid sulfonate structural unit in the polyester containing an anionic group is 1~9.

2. The manufacturing method according to claim 1, characterized in that PET The intrinsic viscosity is 0.60~0.70 dl / g.

3. The manufacturing method according to claim 1, characterized in that The intrinsic viscosity of the polyester containing a polyethylene glycol segment is 0.70~0.90 dl / g.

4. The manufacturing method according to claim 1, characterized in that The isophthalic acid sulfonate is selected from isophthalic acid-5-sulfonic acid or an alkali metal salt of isophthalic acid-5-sulfonic acid.

5. The manufacturing method according to claim 4, characterized in that The alkali metal is sodium or potassium.

6. The manufacturing method according to claim 1, characterized in that The intrinsic viscosity of the polyester containing an anionic group is 0.50~0.70 dl / g.

7. The manufacturing method according to claim 6, characterized in that The intrinsic viscosity of the polyester containing an anionic group is 0.55~0.65 dl / g.

8. The manufacturing method according to claim 1, characterized in that The temperature of melt spinning in step (1) is 260~290°C.

9. The manufacturing method according to claim 1, characterized in that By weight, the effective content in the oil agent emulsion in step (2) is 5~15%.

10. The manufacturing method according to claim 1, characterized in that By weight, the oil content of the oil-containing fibers in step (2) is 0.5~3%.

11. The manufacturing method according to claim 1, characterized in that The temperature of drawing in step (3) is 120~160°C.

12. The manufacturing method according to claim 1, characterized in that The draw ratio of drawing in step (3) is 3.0~5.

0.

13. The manufacturing method according to claim 1, characterized in that In step (4), the antibacterial guanidine salt finishing solution includes the following components by weight: Antibacterial guanidine salt, 0.1~5 parts; Water, 100 parts.

14. The manufacturing method according to claim 1, characterized in that The steps of finishing in step (4) include: (I)Impregnating the obtained fibers as fibers to be antibacterial finished with the antibacterial guanidine salt finishing solution to obtain liquid-carrying fibers I; (II)Drying; (III)Heat setting.

15. The manufacturing method according to claim 14, wherein The liquid-carrying rate of the liquid-carrying fibers I is 40~70%.

16. The manufacturing method according to claim 14, wherein The drying temperature in step (II) is 80~110°C.

17. The manufacturing method according to claim 14, wherein The drying time in step (II) is 3~10 minutes.

18. The manufacturing method according to claim 14, wherein The heat setting temperature in step (III) is 120~180°C.

19. The manufacturing method according to claim 14, wherein The heat setting time in step (III) is 1~5 minutes.