A manufacturing method of an antibacterial and biodegradable PBS fiber and an antibacterial and biodegradable PBS fiber therefrom

Abstract

The present invention relates to a method for manufacturing a polybutylene succinate fiber having antibacterial and biodegradable properties including a zeolite antibacterial agent, and a polybutylene succinate fiber having antibacterial and biodegradable properties manufactured therefrom.

Description

Technology Field

[0001] The present invention relates to a method for manufacturing polybutylene succinate fibers having antibacterial and biodegradable properties and polybutylene succinate fibers having antibacterial and biodegradable properties manufactured therefrom. Specifically, the invention relates to a method for manufacturing polybutylene succinate fibers having antibacterial and biodegradable properties simultaneously by including a zeolite antibacterial agent, and polybutylene succinate fibers having antibacterial and biodegradable properties manufactured therefrom. Background Technology

[0003] With the recent increase in interest in hygiene, there is growing interest in antimicrobial materials in food, medical devices, pharmaceuticals, electronic products, textiles, and more.

[0004] Various harmful microorganisms that parasitize clothing and skin multiply rapidly in a suitable environment, reducing the strength of fibers and causing discoloration or odors, as well as inducing various diseases in the human body. Therefore, as the demand for cleanliness and comfort increases, there is a growing need for antibacterial functions in textile products, including clothing.

[0005] In response to these demands of the times, various antimicrobial agents have been developed and are in use. Antimicrobial agents added to prevent bacterial proliferation can be broadly classified into organic and inorganic types. Organic antimicrobial agents exert their antimicrobial properties through drug release and act to prevent the formation of bacterial colonies rather than to kill bacteria.

[0006] Inorganic antimicrobial agents are primarily produced by substituting antimicrobial metal ions into inorganic materials such as zeolites, calcium phosphate, zirconium phosphate, and silica gel, and are currently utilized in various fields including most plastic products, paper, and textiles. Although the temporary antimicrobial activity of these inorganic agents is lower than that of organic antimicrobial agents, their application areas are expanding because they offer high heat resistance and human safety, do not cause resistant bacteria, and provide almost semi-permanent antimicrobial protection.

[0008] Therefore, methods to impart antimicrobial properties to textile products include yarn modification, which involves applying antimicrobial agents at the polymer stage of the fiber, and post-treatment, which involves applying agents at the dyeing stage. While yarn modification is feasible for synthetic or regenerated fibers, cotton yarns must be processed using post-treatment methods. Even within post-treatment methods, the process of adsorbing antimicrobial agents onto the fiber surface results in poor washability, and heat-setting the antimicrobial agent mixed with a reactive resin degrades the tactile feel. Non-extrusion antimicrobial agents, such as organosilicon quaternary ammonium salts, exhibit excellent durability through dealcoholation reactions between trialkoxysilyl groups and hydroxyl groups on the fiber surface; however, due to the high reactivity of the trialkoxy, they are difficult to handle and expensive.

[0010] Looking at antimicrobial fibers according to the prior art, Korean Published Patent Application No. 10-2003-008122 discloses an antimicrobial fiber manufactured by treating a fiber with an antimicrobial agent composition that has enhanced cationic properties by quaternizing chitosan, a natural substance, and Korean Published Patent Application No. 10-1999-030395 discloses an antimicrobial fiber manufactured by impregnating an inorganic antimicrobial agent, which is an environmentally friendly natural material such as zeolite or ceramic, and binding it by treating it with a resin binder.

[0012] Antimicrobial fibers according to such conventional technology suffer from reduced washing durability as the effectiveness of the antimicrobial agent included during manufacturing continuously diminishes. Furthermore, if a thick coating is applied to the fiber surface or the content of the antimicrobial agent is increased during melt spinning to maintain such durability, the spinning processability deteriorates. Additionally, the increased use of antimicrobial agents leads to higher product prices, and other functionalities of the manufactured antimicrobial fibers, such as flexibility and lightness, are compromised. The problem to be solved

[0014] The present invention aims to provide a method for manufacturing polybutylene succinate fibers having both antibacterial and biodegradable properties by mixing a zeolite antibacterial agent containing sodium cations, silver cations, and zinc cations through a cation exchange reaction with a polybutylene succinate resin and melt-spinning the mixture, and to provide polybutylene succinate fibers having both antibacterial and biodegradable properties produced therefrom. However, the technical problems to be solved by the present invention are not limited to those mentioned above, and other unmentioned problems will be clearly understood by a person skilled in the art from the description below. means of solving the problem

[0016] The method for manufacturing a polybutylene succinate fiber having antibacterial and biodegradable properties according to the present invention comprises a zeolite containing sodium cations, silver cations, and zinc cations to manufacture a polybutylene succinate fiber having antibacterial and biodegradable properties, wherein the zinc cations (Zn) are formed through a cation exchange reaction with sodium cations present within the crystal structure of the zeolite used as a carrier. 2 + A first step (S100) of introducing ) into the zeolite into which the zinc cation has been introduced, and silver cations (Ag) through a cation exchange reaction with sodium cations in the zeolite into which the zinc cation has been introduced. +A second step (S200) of introducing ); a third step (S300) of crushing and classifying a zeolite containing sodium cations, silver cations, and zinc cations by introducing zinc cations and silver cations through the first step (S100) and the second step (S200); a fourth step (S400) of heat-treating the zeolite containing sodium cations, silver cations, and zinc cations crushed and classified in the third step (S300); and a fifth step (S500) of mixing the heat-treated zeolite containing sodium cations, silver cations, and zinc cations with a polybutylene succinate resin; The method comprises a sixth step (S600) of manufacturing a fiber by melt-spinning the polybutylene succinate resin mixed in the fifth step (S500) and a zeolite containing sodium cations, silver cations, and zinc cations; and may further include a step of aging at 0°C to 20°C for 1 hour to 24 hours after the fifth step, wherein the fifth step preferably comprises mixing 1 to 5 weight% of a zeolite containing sodium cations, silver cations, and zinc cations with 95 to 99 weight% of a PBS resin, and the fifth step preferably comprises a first mixing step of mixing at a stirrer speed of 2,500 to 4,500 rpm for 1 to 2 hours; and a second mixing step (S3) of further mixing the first mixed composition at a speed of 5,000 to 6,500 rpm for 1 to 2 hours.

[0018] Additionally, after the above 5th step, a degassing and moisture removal step for removing air and moisture from the PBS resin may be further included; the molar ratio of sodium cation : silver cation : zinc cation of the zeolite containing sodium cation, silver cation, and zinc cation prepared in the above 4th step (S400) is 2.3 to 6.3 : 0.03 to 0.07 : 1.8 to 5.8; the cation exchange reaction in the above 1st step (S100) and 2nd step (S200) is performed at pH 6 to 9; the zeolite used as the carrier in the above 1st step (S100) is one or more selected from Type A zeolite, Type X zeolite, and Type Y zeolite; and the average particle size of the zeolite containing sodium cation, silver cation, and zinc cation crushed and classified in the above 4th step (S300) is 500 to 800 It is preferable that the nanometer is used, and in the fourth step (S400), the heat treatment can be performed at 200 to 400°C for 20 to 40 hours, and in the third step (S300), grinding can be performed using an air jet mill, and in the third step (S300), classification is preferably performed using an air classifier. Effects of the invention

[0020] The polybutylene succinate fiber having antibacterial and biodegradable properties according to the present invention possesses excellent antibacterial properties by including a zeolite antibacterial agent. In particular, by melt-spinning with the zeolite antibacterial agent mixed in, durability is improved, resulting in good persistence of antibacterial properties and high fastness, thereby maintaining the antibacterial function semi-permanently. Therefore, the polybutylene succinate fiber manufactured by including the zeolite antibacterial agent according to the present invention maintains excellent antibacterial properties even after repeated washing, thereby preventing the risk of secondary infection. Furthermore, the polybutylene succinate fiber has an eco-friendly effect as it naturally decomposes in the ecosystem upon disposal after use, thus not causing environmental pollution problems. Brief explanation of the drawing

[0022] FIG. 1 is a process flow diagram for a method of manufacturing a zeolite antimicrobial agent and an antimicrobial fiber produced through a cation exchange reaction according to the present invention, and FIG. 2 is a schematic diagram of a cation exchange reaction according to the present invention, and FIG. 3 is a micrograph of a zeolite antimicrobial agent produced through a cation exchange reaction according to the present invention, and FIG. 4 is a schematic diagram of an apparatus for manufacturing polybutylene succinate fibers having antibacterial and biodegradable properties according to the present invention. Specific details for implementing the invention

[0023] In this application, terms such as “comprising,” “having,” or “having” are intended to specify the existence of the features, numbers, steps, components, parts, or combinations thereof described in the specification, and should be understood as not precluding the existence or addition of one or more other features, numbers, steps, actions, components, parts, or combinations thereof.

[0024] Furthermore, unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as generally understood by those skilled in the art to which the present invention pertains. Terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with their meaning in the context of the relevant technology, and should not be interpreted in an ideal or overly formal sense unless explicitly defined in this application.

[0025] Preferred embodiments of the present invention will be described in more detail below with reference to the attached drawings. To facilitate an overall understanding of the invention, the same reference numerals are used for identical components in the drawings, and redundant descriptions of identical components are omitted.

[0027] Hereinafter, a method for manufacturing a polybutylene succinate fiber having antibacterial and biodegradable properties according to the present invention and a polybutylene succinate fiber having antibacterial and biodegradable properties manufactured therefrom will be described in detail with reference to the attached drawings. FIG. 1 attached to the present invention is a process flow diagram for a method for manufacturing a zeolite antibacterial agent and an antibacterial fiber produced through a cation exchange reaction according to the present invention; FIG. 2 is a schematic diagram of a cation exchange reaction according to the present invention; FIG. 3 is a micrograph of a zeolite antibacterial agent produced through a cation exchange reaction according to the present invention; and FIG. 4 is a schematic diagram of an apparatus for manufacturing a polybutylene succinate fiber having antibacterial and biodegradable properties according to the present invention.

[0029] The polybutylene succinate (hereinafter PBS) fiber having antibacterial and biodegradable properties according to the present invention has sustained antibacterial properties by including a zeolite antibacterial agent produced through a cation exchange reaction.

[0030] In addition, the PBS above is a biodegradable aliphatic polyester having repeating units as shown in [Chemical Formula 1] below, and has self-biodegradability.

[0032] [Chemical Formula 1]

[0033]

[0035] The above PBS is Amycolatopsis ( Amcolatopsis ) strains or penicillin ( Penicillium Because it is biodegradable and naturally decomposes into water and carbon dioxide by microorganisms such as strains, it is being used as a substitute for various plastics, and the range of applications for PBS is still expanding.

[0037] As shown in FIG. 2, the polybutylene succinate fiber having antibacterial and biodegradable properties according to the present invention preferably comprises a zeolite as a carrier, a sodium cation introduced into the crystal structure of the zeolite, and silver cations and zinc cations introduced through a cation exchange reaction with the sodium cation.

[0038] Typically, the above zeolite is a crystalline aluminosilicate in which tetrahedra of AlO4 and SiO4 are bonded to form sodalite units (β-cages) having eight hexagonal faces and six tetragonal faces. In addition, the zeolite is Na 12 {SiO2AlO2} 12 It has the structure of xH2O.

[0039] The above zeolites come in many varieties and possess adsorption separation and ion exchange capabilities, so they are widely used as catalysts, adsorbents, ion exchange resins, catalyst supports, etc.

[0041] The zeolite for producing the zeolite antimicrobial agent according to the present invention may be any one selected from the group consisting of A-type zeolite, X-type zeolite, Y-type zeolite, P-type zeolite, high-silica zeolite, mordenite, clinoptilolite, cavitrite, and eninoite, but A-type zeolite, X-type zeolite, and Y-type zeolite are particularly preferred.

[0042] The structural formulas and Si / Al ratios of the above-mentioned Type A zeolite, Type X zeolite, and Type Y zeolite are as shown in [Table 1] below.

[0044] constitutional formula Si / Al ratio Type A zeolite Na 12 (AlO2) 12 (SiO2) 12 ·27H2O 1 X-type zeolite Na 86 (AlO2) 86 (SiO2) 106 ·264H2O 1.2 Y-type zeolite Na 56 (AlO2) 56 (SiO2) 136 ·253H2O 2.4

[0046] Since the above zeolite forms a negative charge due to aluminum atoms within its structure, cations such as sodium are present to adjust this charge imbalance and neutralize the total charge.

[0048] The zeolite antimicrobial agent according to the present invention comprises sodium cations (Na₂C₆) existing as cations in the skeletal structure of the zeolite used as a carrier, as shown in FIG. 2. + A portion of ) is converted into silver cations (Ag) through a cation exchange reaction + ) and zinc cations (Zn 2 + It can be manufactured by replacing with ).

[0049] That is, the zeolite (hereinafter referred to as Na-Ag-Zn-Zeolite) prepared by exchanging silver cations and zinc cations with sodium cations as described above preferably has a molar ratio of sodium cation : silver cation : zinc cation as the composition ratio of cations provided within the structure of the zeolite, such that the molar ratio of sodium cation : silver cation : zinc cation is 2.3 to 6.3 : 0.03 to 0.07 : 1.8 to 5.8.

[0050] By configuring the molar ratio of cations as described above, the molecular structural formula of the zeolite antibacterial agent according to the present invention is Na2 .3~6.3 Ag0 .03∼0.07 Zn1 .8∼5.8 {SiO2·AlO2} 12· It is equal to xH2O. By configuring the molar ratio of cations as described above, it is possible to manufacture a zeolite antibacterial agent with the best antibacterial effect.

[0051] That is, the zeolite antimicrobial agent according to the present invention comprises sodium cations, silver cations, and zinc cations, and said sodium cations, silver cations, and zinc cations exist in an ionic bonded state within the zeolite. The Na-Ag-Zn-Zeolite leaches silver cations and zinc cations as antimicrobial substances in water, and the silver cations and zinc cations leached into water as described above bind to atomic groups such as thiol groups, amino groups, imidazole groups, and carboxylate groups present in bacteria or microorganisms. It is reported that the binding of silver or zinc cations to these atomic groups disrupts the respiration or electron transfer processes of bacteria or microorganisms, thereby causing the death of bacteria or microorganisms due to respiratory and metabolic disorders. Furthermore, oxygen bound to the zeolite antimicrobial agent or dissolved oxygen in the water is partially oxygenated by the catalytic action of the zeolite antimicrobial agent itself. 2+ , O 2- Alternatively, it is converted into reactive oxygen species such as O. These reactive oxygen species are reported to exert powerful sterilizing effects, such as ozone or hydrogen peroxide.

[0052] In addition, the antibacterial activity of the zeolite antibacterial agent can be maximized when the molar ratio of the sodium cation : silver cation : zinc cation is 2.3 to 6.3 : 0.03 to 0.07 : 1.8 to 5.8. Also, if the ratio falls outside the above range, the antibacterial activity may decrease, and there may be problems such as the cation exchange reaction not proceeding smoothly or the waste of expensive silver cations.

[0054] Below, we examine a method for manufacturing PBS fibers having antibacterial and biodegradable properties by including a zeolite antibacterial agent according to the present invention.

[0056] That is, the method for manufacturing an antimicrobial fiber according to the present invention, as shown in FIG. 1, involves a zinc cation (Zn) through a cation exchange reaction with a sodium cation present within the crystal structure of a zeolite used as a carrier. 2 + A first step (S100) of introducing ) into the zeolite into which the zinc cation has been introduced, and silver cations (Ag) through a cation exchange reaction with sodium cations in the zeolite into which the zinc cation has been introduced. + A second step (S200) of introducing ); a third step (S300) of crushing and classifying a zeolite containing sodium cations, silver cations, and zinc cations by introducing zinc cations and silver cations through the first step (S100) and the second step (S200); a fourth step (S400) of heat-treating the zeolite containing sodium cations, silver cations, and zinc cations crushed and classified in the third step (S300); and the heat-treated zeolite containing sodium cations, silver cations, and zinc cations with PBS resin and It may be preferable to include a fifth step (S500) of mixing; and a sixth step (S600) of manufacturing fibers by melt-spinning the PBS resin mixed in the fifth step (S500) and a zeolite containing sodium cations, silver cations, and zinc cations.

[0058] First, as the first step (S100), zinc cations (Zn) are formed through a cation exchange reaction with sodium cations present within the crystal structure of the zeolite. 2 + A zeolite is manufactured by introducing ). In this case, according to the present invention, it is particularly preferable to use any one of the zeolites selected from the group including A-type zeolite, X-type zeolite, and Y-type zeolite.

[0059] As described above, in order to introduce zinc cations into the zeolite structure through a cation exchange reaction with sodium cations present in the zeolite crystal structure, water is introduced into a first reaction vessel equipped with a stirrer and capable of temperature control, and the zeolite is introduced while stirring. At this time, nitric acid is introduced while maintaining the temperature of the first reaction vessel at 30 to 80 ℃ to adjust the pH to 6 to 9.

[0060] In addition, water is introduced into the second reaction vessel, and zinc sulfate is introduced while stirring. It is preferable that the second reaction vessel is also equipped with a stirrer and capable of temperature control. At this time, zinc sulfate is dissolved in the introduced water while maintaining the temperature of the second reaction vessel at 30 to 80°C. The water in which zinc sulfate has been dissolved in the second reaction vessel as described above is slowly introduced into the first reaction vessel.

[0061] As described above, when water in which zinc sulfate is dissolved is introduced into the first reaction vessel and the temperature is maintained at 30 to 80°C while stirring, the sodium cations and zinc cations present in the zeolite are exchanged with each other. At this time, the cation exchange reaction time for exchanging zinc cations and sodium cations to introduce the zinc cations into the structure of the zeolite is preferably 10 to 12 hours.

[0062] After the cation exchange reaction for introducing zinc cations as described above is completed, the zeolite into which the zinc cations have been introduced is produced.

[0064] Afterward, various impurities present in the first and second reaction vessels are removed using distilled water. After removing impurities from the first and second reaction vessels as described above, silver cations are introduced into the zeolite structure into which zinc cations were introduced through the first step (S100) as a second step (S200). In order to introduce silver cations as described above, water is added to the first reaction vessel and the zeolite into which zinc cations were introduced, prepared through the first step (S100), is added while stirring. At this time, nitric acid is added while maintaining the temperature of the first reaction vessel at 30 to 80°C to adjust the pH to 6 to 9.

[0066] In addition, distilled water is added to the second reaction vessel and silver nitrate is added and dissolved while stirring. At this time, the silver nitrate is dissolved while maintaining the temperature of the second reaction vessel at 30 to 80°C. The water in which the silver nitrate is dissolved in the second reaction vessel as described above is slowly added to the first reaction vessel into which the zeolite into which the zinc cation was introduced is added.

[0067] As described above, after introducing water in which silver nitrate is dissolved into the first reaction vessel, if the temperature is maintained at 30 to 80°C while stirring, the sodium cations and silver cations remaining in the zeolite into which the zinc cations have been introduced are exchanged with each other. At this time, the cation exchange reaction time for exchanging silver cations and sodium cations to introduce the silver cations into the structure of the zeolite is preferably 4 to 6 hours.

[0068] As described above, when the exchange reaction of silver cations is completed as the second step (S200), the introduced silver cations and zinc cations are present in the zeolite, and some unreacted sodium cations remain.

[0069] After the second step (S200) is completed as described above, the zeolite into which zinc cations and silver cations have been introduced, namely Na-Ag-Zn-Zeolite, is collected and dehydrated and dried.

[0071] According to the present invention, when the pH of the first reaction vessel is adjusted to 6 to 9 in the first step (S100) and the second step (S200), H in the aqueous solution + Ions and OH - Ions can be formed more easily than in water, and by acting as catalysts for cation exchange, they increase the reaction rate. Accordingly, the cation exchange reaction can proceed smoothly in the first step (S100) and the second step (S200).

[0072] As described above, during the zinc cation exchange reaction in the first step (S100) and the silver cation exchange reaction in the second step (S200), the molar ratio of sodium cations, silver cations, and zinc cations can be controlled to 2.3–6.3 : 0.03–0.07 : 1.8–5.8 through reaction conditions such as the temperature, pH, and reaction time of the reaction vessel.

[0074] Afterwards, a third step (S300) is performed to crush and classify the Na-Ag-Zn-Zeolite dried as described above. The third step (S300) refers to a step of crushing and classifying the Na-Ag-Zn-Zeolite to control the particle size of the Na-Ag-Zn-Zeolite.

[0076] The above Na-Ag-Zn-Zeolite clumps together due to mutual attraction when moisture is present, resulting in an average particle size of 1 μm or more. As described above, when the average particle size is 1 μm or more, the large particle size results in poor dispersibility, making it unsuitable for melt spinning when mixed with a thermoplastic resin.

[0077] The coarsening or aggregation of such zeolites inevitably reduces excellent effects such as antibacterial properties, degrades the physical properties of the manufactured antibacterial fibers—that is, the performance of the polymer—and, in particular, makes manufacturing in the form of fibers or films impossible.

[0079] Therefore, in the present invention, in order to use the Na-Ag-Zn-Zeolite prepared as described above as a zeolite antimicrobial agent, it undergoes a grinding and classification process as a third step (S300) to have an average particle size of 500 to 800 nm.

[0081] According to the present invention, in the third step (S300), the grinding process can be performed using any one of a grinder selected from an air jet mill, a ball mill, a rod mill, and an attrition mill, and the classification can be performed using any one of a classifier selected from an air classifier and a wet cyclone.

[0082] That is, the Na-Ag-Zn-Zeolite produced through the first step (S100) and the second step (S200) can be ground and classified as needed for use, and the average particle size of the Na-Ag-Zn-Zeolite is 500 to 800 nm, which is excellent in terms of usability.

[0084] The grinding process for grinding the agglomerated Na-Ag-Zn-Zeolite after dehydration according to the present invention is particularly preferably performed by an air jet mill and can be carried out by mutual collision and friction of the agglomerated Na-Ag-Zn-Zeolite.

[0085] The above air jet mill achieves grinding through mutual collision and friction between the Na-Ag-Zn-Zeolite by injecting high-pressure compressed air from a nozzle onto the aggregated Na-Ag-Zn-Zeolite supplied to the grinding chamber.

[0086] At this time, Na-Ag-Zn-Zeolite ground to a size smaller than a certain threshold is discharged to the outside through the classification chamber, while Na-Ag-Zn-Zeolite larger than a certain threshold is fed back into the grinding chamber for re-grinding. Accordingly, the aggregated Na-Ag-Zn-Zeolite can be continuously ground.

[0088] The Na-Ag-Zn-Zeolite ground as described above is classified to obtain only Na-Ag-Zn-Zeolite with an average particle size of 500 to 800 nanometers. According to the present invention, it is preferable to use an air classifier for the classification process.

[0089] Na-Ag-Zn-Zeolite having the size range mentioned above is taken, and the remaining zeolite is recycled to the grinding process.

[0091] As described above, the Na-Ag-Zn-Zeolite that has been crushed and classified through the third step (S300) then undergoes a fourth step (S400) of heat treatment.

[0092] As an embodiment, the above fourth step (S400) is preferably performed on the Na-Ag-Zn-Zeolite crushed and classified in the above third step (S300) at 200 to 400°C for 20 to 40 hours.

[0093] Typically, ground and classified Na-Ag-Zn-Zeolite does not aggregate when dry, but aggregates in the presence of moisture, causing an increase in the average particle size. Therefore, aggregation is prevented by removing the moisture present in the zeolite through the heat treatment described above.

[0095] As described above, by heat treatment through the fourth step (S400), the manufacture of the zeolite antibacterial agent according to the present invention can be completed as shown in FIG. 3.

[0096] The Na-Ag-Zn-Zeolite produced after performing the above fourth step may preferably have a molar ratio of sodium cation : silver cation : zinc cation of 2.3 to 6.3 : 0.03 to 0.07 : 1.8 to 5.8.

[0098] As described above, the Na-Ag-Zn-Zeolite heat-treated in the fourth step (S400) then undergoes the fifth step (S500) of being mixed with PBS resin.

[0099] In the present invention, fiberization is made possible by melt spinning the above-mentioned Na-Ag-Zn-Zeolite by mixing it with PBS resin.

[0100] As described above, by mixing Na-Ag-Zn-Zeolite with PBS resin, the Na-Ag-Zn-Zeolite is present on the surface of the thermoplastic resin. Accordingly, it is possible to sufficiently cause metabolic disorders in bacteria coming into contact with the Na-Ag-Zn-Zeolite. Through this, the entire PBS resin is given the effect of having an antibacterial function.

[0102] According to the present invention, in the fifth step (S500), it may be preferable to add 1 to 5 weight% of the Na-Ag-Zn-Zeolite and 95 to 99 weight% of the PBS resin. If the Na-Ag-Zn-Zeolite is included in an amount of less than 1 weight%, it may be difficult to achieve antibacterial properties, and if it exceeds 5 weight%, the manufacturing cost of the polybutylene succinate fiber having antibacterial and biodegradable properties increases, which may reduce economic feasibility.

[0104] In addition, according to the present invention, it may be preferable to include a first mixing step in which the PBS resin and Na-Ag-Zn-Zeolite are mixed at 70 to 85°C at a stirrer speed of 2,500 to 4,500 rpm for 1 to 2 hours during the mixing of the PBS resin and Na-Ag-Zn-Zeolite in the fifth step; and a second mixing step in which the first mixed composition is further mixed at 100 to 105°C at a speed of 5,000 to 6,500 rpm for 1 to 2 hours.

[0106] As described above, by mixing PBS resin and Na-Ag-Zn-Zeolite through first and second mixing steps, the dispersibility of the Na-Ag-Zn-Zeolite can be improved. As the dispersibility of Na-Ag-Zn-Zeolite is improved as described above, the mechanical properties of the manufactured antibacterial and biodegradable polybutylene succinate fiber can be improved more effectively.

[0108] After performing the fifth step as described above, a low-temperature aging step to increase the dispersion stability of the Na-Ag-Zn-Zeolite and a degassing and moisture removal step to remove air and moisture from the PBS resin mixed with the Na-Ag-Zn-Zeolite may be additionally included.

[0109] That is, the above low-temperature aging step refers to a step of aging the PBS resin mixed with Na-Ag-Zn-Zeolite as described above at 0 to 20 ℃ for 1 hour to 24 hours.

[0110] By undergoing the low-temperature aging step as described above, the dispersion stability of the Na-Ag-Zn-Zeolite is improved, thereby preventing the precipitation of the Na-Ag-Zn-Zeolite during long-term storage.

[0112] In addition, the degassing and moisture removal steps for removing air and moisture from the PBS resin mixed with Na-Ag-Zn-Zeolite can be performed using a vacuum degassing machine. That is, by degassing and removing moisture while stirring the PBS resin mixed with Na-Ag-Zn-Zeolite at low speed in a vacuum degassing machine, a PBS resin in which the Na-Ag-Zn-Zeolite is more uniformly dispersed and mixed can be obtained.

[0113] In addition, the above Na-Ag-Zn-Zeolite has a microporous structure, and since the moisture content is high due to the microporous structure, it is desirable to manage the moisture content of the thermoplastic resin to 30 ppm or less in order to prevent a decrease in the degree of polymerization of the thermoplastic resin due to hydrolysis during melt spinning.

[0115] As described above, the PBS resin mixed with Na-Ag-Zn-Zeolite produced through the 5th step can subsequently be manufactured into fibers through a melt spinning process as the 6th step.

[0117] That is, the sixth step above preferably involves melt spinning a mixture of 1 to 5 weight percent of Na-Ag-Zn-Zeolite prepared as above and 95 to 99 weight percent of a thermoplastic resin.

[0118] According to the present invention, a master batch containing Na-Ag-Zn-Zeolite prepared as described above can be prepared and mixed with a thermoplastic resin, and after mixing as described above, fiberization can be achieved by introducing the mixture into a PBS fiber manufacturing apparatus (100) equipped with a conventional melt spinning spinneret and melt spinning.

[0120] That is, in the above 6th step, it is preferable that the melt spinning be performed at a spinning temperature of 150 to 200 ℃. That is, if the spinning temperature is below 150 ℃, melt extrusion becomes difficult, and if it exceeds 200 ℃, thermal decomposition of the polymer occurs, making it difficult to manufacture PBS fibers with desired physical properties.

[0121] In addition, the spinning speed is preferably 3,000 to 5,000 m / min, and by controlling the spinning speed within the above range, the PBS fiber can be manufactured in the form of partially oriented yarn (POY) or fully drawn yarn (FDY). More specifically, when manufacturing the PBS fiber as partially oriented yarn (POY), the spinning speed can be set to 3,000 to 4,000 m / min, and when obtaining the fully drawn yarn (FDY), the spinning speed can be set to exceed 4,000 m / min.

[0123] Hereinafter, FIG. 4 is a schematic diagram of a PBS fiber manufacturing apparatus (100) according to the present invention, and with reference to FIG. 4, the sixth step for manufacturing a PBS multifilament (200) according to the present invention will be described in more detail.

[0125] The PBS resin mixed with the zeolite antibacterial agent produced through the above 5th step is discharged through the spinneret (10) in a molten state, and the PBS multifilament (200) discharged from the spinneret (10) is cooled in the cooling section (20) and then supplied with an emulsion in the lubrication guide (30).

[0126] Afterwards, the extruded PBS multifilament (200) is drawn out by the first godet roll (40), heated by the first godet roll (40), and then stretched and heat-set between the first godet roll (40) and the second godet roll (50).

[0127] In addition, after the above stretching and heat setting, the PBS multifilament (200) according to the present invention can be manufactured by using the heat of the second godet roll (50) to perform relaxation heat treatment between the second godet roll (50) and the cold roll (60), and then winding it by a winder (80).

[0128] At this time, in order to make the relaxation heat treatment more efficient, it is possible to use a heat treatment device (not shown) that uses heated air or steam as a heat medium between the second godet roll (50) and the cold roll (60), or to install a third godet roll (not shown) to perform the relaxation treatment in two stages.

[0130] Additionally, if necessary, the cold roll (60) can be excluded during the above relaxation heat treatment and an entanglement nozzle (not shown) can be used, thereby controlling the cooling and tension gradient of the PBS multifilament (200) by the entanglement nozzle.

[0132] In the method for manufacturing a PBS multifilament (200) according to the present invention, when stretching by the first godet roll (40) and the second godet roll (50), it is preferable to maintain the stretching temperature at 70°C or lower so that the PBS multifilament (200) can be manufactured stably without breaking. In addition, to obtain an orientation effect of the internal structure of the PBS multifilament (200) due to stretching, it is preferable to maintain the temperature at least 10°C higher than the glass transition temperature of PBS.

[0134] In addition, the heat-setting and relaxation heat treatment temperature should be set in the range of 30 to 100°C to achieve the desired heat shrinkage rate, but it is more desirable to set it to 50 to 90°C to relieve residual deformation formed by stretching without staining.

[0136] In addition, the anti-static agent is provided with a leveling agent, an emulsifier, an antistatic agent, etc. Specifically, mineral oils such as liquid paraffin; fatty acid esters such as octyl palmitate, lauryl oleate, and isotridecyl stearate; dibasic acid diesters such as dioleyl adipate and dioctyl sebacate; polyhydric alcohol esters such as trimethylolpropane trilaurate and palm oil; aliphatic sulfur-containing esters such as laurylthiodipropionate; nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene castor oil ether, polyoxyethylene nonylphenyl ether, and trimethylolpropane trilaurate; anionic surfactants such as metal salts or amine salts such as alkylsulfonates and alkyl phosphates; tetramethylene oxide / ethylene oxide copolymers such as sodium dioctylsulfosuccinate and sodium alkanesulfonate; propylene oxide / ethylene oxide copolymers; nonionic surfactants, etc., can be listed, and each process of actual fabrication, warp threading, and fabric manufacturing, particularly A formulation is adopted to improve the permeability of the loom and heddle during fabric manufacturing. If necessary, rust inhibitors, antibacterial agents, antioxidants, penetrating agents, surface tension lowering agents, phase viscosity lowering agents, anti-abrasive agents, and other modifiers may be used together.

[0138] When manufacturing the PBS multifilament (200) according to the present invention, the amount of lubricant applied is preferably 0.3 to 1.2 weight% with respect to the total weight of the PBS multifilament (200) in terms of post-processing.

[0140] In the method for manufacturing a PBS multifilament (200) according to the present invention, the stretching of the PBS multifilament (200) can be performed in multiple stages. Preferably, first, a preliminary stretching is performed by applying a low stretching ratio of about 1.01 to 1.08 times, and second, cold stretching or hot stretching is performed so that a predetermined strength and elongation at break can be obtained.

[0141] In particular, when dimensional stability is required, it is desirable to apply a warm roller or similar treatment following the stretching. At this time, although the total stretching ratio varies depending on the spinning speed, it is desirable to cold-stretch or hot-stretch the unstretched yarn spun at a relatively low speed to a ratio of 1.05 or more.

[0143] As described above, although the method for manufacturing a PBS multifilament (200) according to the present invention has been explained, the processing conditions in each process for manufacturing the PBS multifilament (200) are not specifically limited to the above-described contents, and can be performed under previously known process conditions depending on the purpose of production of the PBS multifilament (200).

[0145] The PBS multifilament (200) of the present invention can be applied to various clothing or interiors as is, but may also be used in the form of a processed yarn that has undergone a specific processing process as needed.

[0147] The PBS fiber having antibacterial and biodegradable properties according to the present invention, manufactured as described above, has excellent antibacterial and biodegradable properties by including a zeolite having a molar ratio of sodium cation : silver cation : zinc cation of 2.3 to 6.3 : 0.03 to 0.07 : 1.8 to 5.8.

[0148] That is, the PBS fiber having antibacterial and biodegradable properties according to the present invention has good persistence of antibacterial properties and high fastness, so the antibacterial function is maintained semi-permanently. In particular, excellent antibacterial properties are maintained even after repeated washing, thereby preventing the risk of secondary infection, and it has an eco-friendly effect that does not cause environmental pollution problems as it naturally decomposes in the ecosystem when discarded after use.

[0150] The present invention will be examined in more detail below through examples and comparative examples. However, the present invention is not limited to the following examples.

[0152] <Example 1>

[0154] Type A zeolite and purified water were added to a reaction vessel and maintained at 80°C for 10 hours, and nitric acid was added to adjust the pH to 6 to 9. Subsequently, zinc sulfate was added to the reaction vessel to introduce zinc cations into the structure of the zeolite.

[0155] Subsequently, the zeolite into which zinc cations were introduced was washed with water, and the zeolite into which zinc cations were introduced and purified water were introduced into a reaction vessel. After maintaining the temperature at 80°C for 6 hours, nitric acid was added to adjust the pH to 6 to 9, and then silver nitrate was added to introduce silver cations into the structure of the zeolite into which zinc cations were introduced, thereby producing a Na-Ag-Zn-Zeolite having a molar ratio of sodium cations, silver cations, and zinc cations of 2.5:0.05:3.2. The Na-Ag-Zn-Zeolite prepared as above was ground and classified to have an average particle size of 500 nanometers, and then heat-treated at 400°C for 24 hours to produce a zeolite antimicrobial agent according to the present invention.

[0156] 1 wt% of Na-Ag-Zn-Zeolite prepared as described above was mixed with PBS resin in a first mixing step at 120°C at a stirrer speed of 2,500 rpm for 1 hour, and the composition mixed in the first step was further mixed at 130°C at a stirrer speed of 6,500 rpm through a second mixing step. Subsequently, the PBS resin mixed with Na-Ag-Zn-Zeolite as described above was aged at a low temperature of 0°C for 12 hours, after which degassing and moisture removal were performed to reduce the moisture content to 20 ppm.

[0157] As described above, a PBS resin mixed with Na-Ag-Zn-Zeolite, from which degassing and moisture had been removed, was melt-spun at a spinning temperature of 150°C to produce a 75 denier / 36 filament multifilament. The multifilament produced as described above was subjected to heat-setting and relaxation heat treatment at 75°C. During the melt-spinning process, the lubricant was applied at 0.5 wt% relative to the total weight of the PBS fiber to produce a fully drawn yarn. The fully drawn yarn produced as described above was woven in a plain weave and used as a test specimen.

[0159] <Example 2>

[0161] A test specimen was prepared in the same manner as in <Example 1> above, but with 3% by weight of the Na-Ag-Zn-Zeolite mixed with the PBS resin.

[0163] <Example 3>

[0165] A test specimen was prepared in the same manner as in <Example 1> above, but with 5% by weight of the Na-Ag-Zn-Zeolite mixed with the PBS resin.

[0167] <Comparative Example 1>

[0169] A test specimen was prepared in the same manner as in <Example 1> above, but a multifilament was prepared by melt-spinning only PBS resin that does not contain Na-Ag-Zn-Zeolite and weaving it in a plain weave to prepare the test specimen.

[0171] And the physical properties of these test specimens, namely antibacterial and biodegradable properties, were evaluated as follows.

[0173] 1) Antibacterial properties

[0175] Antibacterial tests were conducted after 10 and 30 washes in accordance with KS K 0693 (Test Method for Antibacterial Properties of Textile Materials), and the results are shown in [Table 2]. At this time, the strains were Staphylococcus aureus ATCC 6538 (hereinafter, ATCC 6538) and Klebsiella pneumoniae ATCC 4352 (hereinafter, ATCC 4352) used

[0177] 2) Biodegradable

[0179] In accordance with ASTM D6954 (Standard Guide for Exposing and Testing Plastics that Degrade in the Environment by a Combination of Oxidation and Biodegradation), the appearance and elongation were measured after UV pretreatment for 200 hours, and biodegradability was evaluated. The results of the biodegradability evaluation are shown in [Table 3].

[0181] Test piece Normal reduction rate After 10 washes After 30 washes ATCC 6538 ATCC 4352 ATCC 6538 ATCC 4352 Example 1 99.9 % 99.9 % 95.3 % 90.6 % Example 2 99.9 % 99.9 % 97.2 % 92.8 % Example 3 99.9 % 99.9 % 98.8 % 94.1 % Comparative Example 1 23. 7 % 18.6 % 22.5 % 19.2 %

[0183] Referring to [Table 2] above, the test specimens of Examples 1 to 3 according to the present invention, i.e., the PBS test specimens containing a zeolite antibacterial agent, after 10 washes ATCC 6538 and ATCC 4352 It can be seen that the bacteriostatic reduction rate for the strain is 99.9%.

[0184] In addition, it can be confirmed that although the bacteriostatic reduction rate decreases slightly after 30 washes, all exhibit a bacteriostatic reduction rate of 90% or more. That is, since the PBS test specimen containing Na-Ag-Zn-Zeolite according to the present invention is manufactured by melt spinning with the material incorporated into a fiber, it can be seen that the antibacterial properties remain excellent even after washing.

[0185] In addition, although it does not appear after 10 washes, when examining the bacteriostatic reduction rate after 30 washes, it can be confirmed that the bacteriostatic reduction rate gradually increases as the amount of zeolite antibacterial agent mixed into the PBS resin in the test specimens of Examples 1 to 3 increases.

[0186] It can be seen that the test specimen of Comparative Example 1, which does not contain the zeolite antibacterial agent according to the present invention, has a poor bacteriostatic reduction rate compared to the test specimens of Examples 1 to 3.

[0187] Typically, bacteria are distinguished through Gram staining. That is, Gram-negative bacteria refer to a group of bacteria that do not retain the color of the crystal violet reagent when Gram stained with the crystal violet reagent. Gram-positive bacteria refer to bacteria that stain indigo or purple when Gram stained with the crystal violet reagent.

[0188] Silver cations are more resistant to Gram-negative bacteria, while zinc cations are more resistant to Gram-positive bacteria. Therefore, zeolites containing silver cations and zinc cations individually may exhibit low antibacterial activity.

[0189] Na-Ag-Zn-Zeolite, a zeolite antimicrobial agent according to the present invention, has silver cations and zinc cations simultaneously within its structure, and thus can exhibit excellent antimicrobial activity against both Gram-negative and Gram-positive bacteria. In addition, by having silver cations and zinc cations simultaneously, it has the characteristic of being able to exhibit a synergistic effect in antimicrobial activity.

[0191] division Oxidative biodegradation appearance Shin Yul Example 1 Fracture 5% or less Example 2 Fracture 5% or less Example 3 Fracture 5% or less Comparative Example 1 Fracture 5% or less

[0193] In addition, as can be seen in [Table 3] above, Examples 1 to 3 showed high initial biodegradability because fracture occurred while maintaining an elongation of 5% or less after 200 hours of UV pretreatment. Also, in the case of the specimen of Comparative Example 1, it was confirmed that it had similar biodegradability characteristics as it was a specimen prepared using PBS.

[0195] As examined above, the PBS fiber having antibacterial and biodegradable properties according to the present invention possesses excellent antibacterial properties by including a zeolite antibacterial agent. Furthermore, by melt-spinning with the zeolite antibacterial agent mixed in, durability is improved, resulting in good persistence of antibacterial properties and high fastness, thereby maintaining the antibacterial function semi-permanently. Additionally, it can be seen that the polybutylene succinate fiber having antibacterial and biodegradable properties according to the present invention has excellent biodegradability and naturally decomposes in the ecosystem upon disposal after use, thus possessing an environmentally friendly effect that does not cause environmental pollution problems.

[0197] The present invention has been described with reference to the experimental examples illustrated in the drawings, but this is merely illustrative, and those skilled in the art will understand that various modifications and equivalent alternative experimental examples are possible therefrom. Furthermore, those skilled in the art will understand that the present invention can be easily modified into other specific forms without altering the technical spirit or essential features of the invention. Therefore, the embodiments described above should be understood as illustrative in all respects and not restrictive, and the true scope of technical protection of the present invention should be determined by the technical spirit of the appended claims. Explanation of the symbols

[0199] 10: Radiation 20 : Cooling section 30: Refueling Guide 40: 1st Godetroll 50: 2nd Godetroll 80 : Winder 200: Polybutylene succinate fiber

Claims

Claim 1 zinc cations (Zn) through a cation exchange reaction with sodium cations present within the crystal structure of the zeolite used as a carrier 2+ A first step (S100) of introducing ) into the zeolite into which the zinc cation has been introduced, and silver cations (Ag) through a cation exchange reaction with sodium cations in the zeolite into which the zinc cation has been introduced. + A second step (S200) of introducing ); a third step (S300) of crushing and classifying a zeolite containing sodium cations, silver cations, and zinc cations by introducing zinc cations and silver cations through the first step (S100) and the second step (S200); a fourth step (S400) of heat-treating the zeolite containing sodium cations, silver cations, and zinc cations crushed and classified in the third step (S300); and a fifth step (S500) of mixing the heat-treated zeolite containing sodium cations, silver cations, and zinc cations with a polybutylene succinate resin; A method for manufacturing a polybutylene succinate fiber having antibacterial and biodegradable properties, comprising: a sixth step (S600) of manufacturing a fiber by melt-spinning a polybutylene succinate resin mixed in the fifth step (S500) and a zeolite containing sodium cations, silver cations, and zinc cations; wherein the fifth step further comprises a step of aging at 0°C to 20°C for 1 to 24 hours after the fifth step; wherein the fifth step comprises a first mixing step of mixing at a stirrer speed of 2,500 to 4,500 rpm for 1 to 2 hours; and a second mixing step (S3) of further mixing the first mixed composition at a speed of 5,000 to 6,500 rpm for 1 to 2 hours. Claim 2 A method for manufacturing a polybutylene succinate fiber having antibacterial and biodegradable properties, wherein, in claim 1, the zeolite used as the carrier in the first step (S100) is one or more selected from A-type zeolite, X-type zeolite, and Y-type zeolite. Claim 3 A method for manufacturing polybutylene succinate fibers having antibacterial and biodegradable properties, wherein the fifth step is characterized by mixing 1 to 5 weight% of zeolite containing sodium cations, silver cations, and zinc cations with 95 to 99 weight% of PBS resin. Claim 4 A method for manufacturing a polybutylene succinate fiber having antibacterial and biodegradable properties, characterized in that, in claim 1, the molar ratio of sodium cation : silver cation : zinc cation of the zeolite containing sodium cation, silver cation, and zinc cation prepared in the fourth step (S400) is 2.3 to 6.3 : 0.03 to 0.07 : 1.8 to 5.

8. Claim 5 A method for manufacturing polybutylene succinate fibers having antibacterial and biodegradable properties, characterized in that, in the third step (S300), the average particle size of the zeolite containing sodium cations, silver cations, and zinc cations, which is crushed and classified, is 500 to 800 nanometers. Claim 6 A method for manufacturing polybutylene succinate fibers having antibacterial and biodegradable properties, characterized in that, in the third step (S300) of claim 1, grinding is performed using an air jet mill. Claim 7 Polybutylene succinate fiber having antibacterial and biodegradable properties, produced by the method for producing a polybutylene succinate fiber having antibacterial and biodegradable properties according to any one of claims 1 to 6.

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