KR102356102B1 - Antibacterial zeolite produced by cation exchange reaction and antibacterial PET fiber using the same - Google Patents

Abstract

The present invention relates to a zeolite antibacterial agent produced through a cation exchange reaction and an antibacterial polyester yarn using the same. More specifically, the present invention relates to a method for manufacturing a zeolite antibacterial agent imparted with antibacterial properties through a cation exchange reaction between sodium cations, silver cations, and zinc cations, and also to an antibacterial polyester yarn manufactured using the same.

Description

Zeolite antibacterial agent produced through cation exchange reaction and antibacterial polyester yarn using same { Antibacterial zeolite produced by cation exchange reaction and antibacterial PET fiber using the same }

The present invention relates to a zeolite antibacterial agent produced through a cation exchange reaction and an antibacterial polyester yarn using the same, and specifically, a zeolite antibacterial agent produced through a cation exchange reaction between sodium cations, silver cations and zinc cations, and antibacterial agents manufactured using the same It relates to polyester yarn.

Recently, as interest in hygiene increases, interest in antibacterial materials in foods, medical devices, pharmaceuticals, electronic products, textiles, etc. is increasing. Various harmful microorganisms parasitic on clothes and skin proliferate within a short period of time in an environment where growth is possible, reducing the strength of fibers, causing coloration and odor generation, as well as causing various diseases in the human body. Therefore, as the demand for cleanliness and comfort increases, the antibacterial function is required for textile products including clothes.

Various antibacterial agents have been developed and used according to the needs of the times. Antibacterial agents added to prevent bacterial growth can be broadly classified into organic and inorganic. Organic antibacterial agents mainly use the effect of dissolution of the drug, and act to prevent the formation of bacterial colonies rather than sterilization.

Inorganic antibacterial agents are mainly made by substituting metal ions that have an antibacterial action on inorganic substances such as zeolite, calcium phosphate, zirconium phosphate, silica gel, etc., and are currently used in various fields such as most plastic products, paper, and textiles. The inorganic antibacterial agent has a temporary antibacterial effect lower than that of the organic antibacterial agent, but has high heat resistance and human safety, does not show resistant bacteria, and the antibacterial duration is almost semi-permanent, so its use area is expanding.

As a method of imparting antibacterial properties to textile products, there are a yarn modification processing method that applies an antibacterial agent at the polymer stage of the fiber and a post-treatment processing method applied at the dyeing processing stage. In this case, it must be processed by a post-processing method. Even in the post-treatment method, the process of adsorbing the antibacterial agent to the surface of the fiber has poor washing resistance, and when heat-setting by mixing the antibacterial agent with the reactive resin, the tactile feel is reduced. The organosilicon-based quaternary ammonium salt, a non-dissolving antibacterial agent, has excellent durability due to the dealcoholization reaction with the trialkoxy silyl group and the hydroxyl group on the fiber surface, but is difficult to handle and expensive due to the high reactivity of trialkoxy.

Looking at the antibacterial fiber according to the prior art, Korean Patent Publication No. 10-2003-008122 Horn discloses an antibacterial fiber manufactured by quaternizing the fiber with an antimicrobial composition with enhanced cationic properties by quaternizing chitosan, a natural material, Korean Patent Laid-Open No. 10-1999-030395 discloses an antibacterial fiber manufactured by penetrating an inorganic antibacterial agent, which is an environmentally friendly natural material such as zeolite or ceramic, and treating it with a resin with a binder.

The antibacterial fiber according to the prior art has insignificant antibacterial effect of the antibacterial agent included during manufacture, and has a particularly harmful characteristic to the human body or has a problem in that the coated antibacterial material is removed during manufacture, thereby reducing washing durability. In particular, there is a problem in that spinning workability is reduced when the content of the antibacterial agent is increased when thickly applied to the fiber surface or when the content of the antibacterial agent is increased during melt spinning to improve washing durability. In addition, there is a problem in that the amount of the antibacterial agent is increased and the price of the product becomes high, and other functionalities such as flexibility and lightness of the manufactured antibacterial fiber are deteriorated.

An object of the present invention is to prepare a zeolite antibacterial agent containing sodium cations, silver cations and zinc cations through a cation exchange reaction, and to provide an antibacterial polyester yarn manufactured using the same. However, the technical problem to be achieved by the present invention is not limited to the above-mentioned problems, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

The manufacturing method of the antibacterial polyester yarn according to the present invention is a first step of introducing a zinc cation (Zn ^{2 +} ) through a cation exchange reaction with a sodium cation present in the crystal structure of zeolite used as a carrier (S100) ; a second step (S200) of introducing a silver cation (Ag ⁺ ) through a cation exchange reaction with a sodium cation into the zeolite to which the zinc cation is introduced; a third step (S300) of pulverizing and classifying a zeolite containing a sodium cation, a silver cation and a zinc cation by introducing a zinc cation and a silver cation through the first step (S100) and the second step (S200); a fourth step (S400) of preparing a zeolite antibacterial agent by heat-treating the zeolite containing the sodium cation, silver cation and zinc cation, which has been pulverized and classified in the third step (S300); a fifth step (S500) of mixing the zeolite antibacterial agent with a regenerated polyester resin; and a sixth step (S600) of producing an antibacterial polyester yarn by melt-spinning the regenerated polyester resin and zeolite antibacterial agent mixed in the fifth step (S500); The average particle size of the zeolite containing the classified sodium cations, silver cations and zinc cations is 500 to 800 nanometers, and the sodium cations of the zeolite containing the sodium cations, silver cations and zinc cations prepared in the third step (S300). The molar ratio of : silver cation: zinc cation is 2.3 to 6.3: 0.03 to 0.07: 1.8 to 5.8, and the heat treatment in the fourth step (S400) is preferably performed at 200 to 400° C. for 20 to 40 hours.

In addition, it is preferable to use an air jet mill for the pulverization in the third step (S300), and it is preferable to use an air classifier for the classification in the third step (S300), and the regenerated polyester resin is material regenerated or chemically It is a regenerated polyester resin, and the cation exchange reaction in the first step (S100) and the second step (S200) is performed at pH 6 to 9, and the zeolite used as the carrier in the first step (S100) is Any one or more selected from A-type zeolite, X-type zeolite, and Y-type zeolite is preferable.

The zeolite antibacterial agent according to the present invention has the effect of maximizing antimicrobial properties by controlling the molar ratio of sodium cations, silver cations, and zinc cations present in the zeolite through a cation exchange reaction. In addition, it has good antibacterial durability and high fastness, so it has the effect of maintaining the antibacterial function semi-permanently.

And the antibacterial polyester yarn produced including the zeolite antibacterial agent according to the present invention can prevent the risk of secondary infection by maintaining excellent antibacterial properties even after repeated washing, and can stably produce antibacterial polyester yarn with excellent radioactivity have an effect

In particular, the antibacterial polyester yarn manufactured including the zeolite antibacterial agent according to the present invention is manufactured by recycling waste polyester, thereby saving resources and protecting the environment.

1 is a process diagram of a method for producing a zeolite antibacterial agent and antibacterial fiber produced through a cation exchange reaction according to the present invention;
2 is a schematic diagram of a cation exchange reaction according to the present invention,
3 is a photomicrograph of a zeolite antibacterial agent prepared through a cation exchange reaction according to the present invention;
4 is a schematic view of a spinning apparatus 100 for producing a polyester yarn using the recycled polyester according to the present invention,
5 is an antimicrobial evaluation result after washing 10 times of a textile product containing a zeolite antibacterial agent according to the present invention;
6 is an antimicrobial evaluation result after washing 30 times of a textile product containing a zeolite antibacterial agent according to the present invention.

In the present application, terms such as “comprise”, “have”, or “include” are intended to designate the existence of features, numbers, steps, components, parts, or combinations thereof described in the specification, and one or more other It should be understood that this does not preclude the possibility of addition or presence of features or numbers, steps, operations, components, parts, or combinations thereof.

In addition, unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs. Terms such as those defined in a commonly used dictionary should be interpreted as having a meaning consistent with the meaning in the context of the related art, and should not be interpreted in an ideal or excessively formal meaning unless explicitly defined in the present application. does not

Hereinafter, preferred embodiments of the present invention will be described in more detail with reference to the accompanying drawings. In describing the present invention, in order to facilitate the overall understanding, the same reference numerals are used for the same components in the drawings, and duplicate descriptions of the same components are omitted.

Hereinafter, a zeolite antibacterial agent prepared through a cation exchange reaction according to the present invention and an antibacterial polyester yarn using the same will be described in detail with reference to the accompanying drawings. 1 attached to the present invention is a process chart for a method for producing a zeolite antibacterial agent and antibacterial fiber produced through a cation exchange reaction according to the present invention, Figure 2 is a schematic diagram of a cation exchange reaction according to the present invention, Figure 3 is this It 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 view of a spinning apparatus 100 for producing a polyester yarn using the regenerated polyester according to the present invention, and FIG. The results of evaluation of the antibacterial properties of textile products containing the zeolite antibacterial agent according to the present invention are shown after washing 10 times, and FIG.

According to the present invention, the zeolite antibacterial agent prepared through the cation exchange reaction is, as shown in FIG. 2, a zeolite as a carrier and sodium cations introduced into the crystal structure of the zeolite and sodium cations introduced through a cation exchange reaction. It is preferable to contain a silver cation and a zinc cation.

Typically, the zeolite is a crystalline aluminosilicate, and AlO ₄ and SiO ₄ tetrahedra are combined with each other to form a sodalite unit (β-cage) having 8 hexagonal faces and 6 square faces. In addition, the zeolite has a structural formula of Na ₁₂ {SiO ₂ ·AlO ₂ } ₁₂ ·xH ₂ O.

There are many types of zeolites, and they have adsorption separation and ion exchange capabilities, and are widely used as catalysts, adsorbents, ion exchange resins, catalyst supports, and the like.

The zeolite used to prepare the zeolite antibacterial agent according to the present invention is A-type zeolite, X-type zeolite, Y-type zeolite, P-type zeolite, high silica zeolite, mordenite, clinoptilolite, cavirite And it may be any one selected from the group consisting of eninonite, in particular, A-type zeolite, X-type zeolite, and Y-type zeolite is particularly preferred.

Structural formulas and Si/Al ratios of the A-type zeolite, X-type zeolite and Y-type zeolite are shown in Table 1 below.

constitutional formula Si/Al ratio Type A zeolite Na ₁₂ (AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ 27H ₂ O One Type X zeolite Na ₈₆ (AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ·264H ₂ O 1.2 Y-type zeolite Na ₅₆ (AlO ₂ ) ₅₆ (SiO ₂ ) ₁₃₆ 253H ₂ O 2.4

Since the zeolite is negatively charged by the aluminum atoms in the structure, cations such as sodium are present to adjust the imbalance of these charges to neutralize the total charge.

As shown in FIG. 2, the zeolite antibacterial agent according to the present invention is a silver cation (Ag ⁺ ) ^and It can be prepared by exchanging with zinc cations (Zn ^{2 +} ).

That is, the zeolite produced by exchanging silver cations and zinc cations with sodium cations as described above (hereinafter, Na-Ag-Zn-Zeolite) is a composition ratio of cations included in the structure of the zeolite, and the sodium cation: silver cation: zinc The molar ratio of the cations is preferably 2.3 to 6.3: 0.03 to 0.07: 1.8 to 5.8.

By configuring the molar ratio of the cations as described above, the molecular structural formula of _the zeolite antibacterial agent according to the present invention is Na _{2 .3 to 6.3} Ag 0.03 to _0.07 Zn 1.8 to _{5.8 {} SiO ₂ ·AlO ₂ } _12· xH ₂ O same as By configuring the molar ratio of the cations as described above, it is possible to prepare a zeolite antibacterial agent having the best antibacterial effect.

That is, the zeolite antibacterial agent according to the present invention includes a sodium cation, a silver cation, and a zinc cation, and the sodium cation, the silver cation and the zinc cation are present in an ionic bond in the zeolite. The zeolite containing the sodium cation, silver cation and zinc cation (hereinafter, Na-Ag-Zn-Zeolite) elutes silver cation and zinc cation as an antibacterial material in water, and the silver cation and zinc eluted into water as described above The cation is bound to an atomic group such as a thiol group, an amino group, an imidazole group, and a carboxylate group existing in bacteria or microorganisms. It has been reported that the binding of silver or zinc cations to these atomic groups interferes with the respiration process or electron transfer process of bacteria or microorganisms, thereby killing bacteria or microorganisms due to respiratory and metabolic disorders.

In addition, oxygen bound to the zeolite antibacterial agent or dissolved oxygen in water is partially converted into active oxygen such as O ²⁺ , O ² - or O by the catalytic action of the zeolite antibacterial agent itself. It is reported that these reactive oxygen species exert a strong sterilization effect such as ozone or hydrogen peroxide.

In addition, 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, the antimicrobial activity of the zeolite antibacterial agent can be maximized. In addition, when it is out of the above range, the antibacterial activity may be reduced, and there may be a problem in that the cation exchange reaction does not occur smoothly or the expensive silver cations are wasted.

Hereinafter, a method for manufacturing an antibacterial polyester yarn using the zeolite antibacterial agent according to the present invention will be described.

That is, in the method for producing an antibacterial polyester yarn according to the present invention, as shown in FIG. 1 , zinc cations (Zn ^{2 +} ) through a cation exchange reaction with sodium cations present in the crystal structure of zeolite used as a carrier. The first step of introducing this (S100); a second step (S200) of introducing a silver cation (Ag ⁺ ) into the zeolite to which the zinc cation is introduced through a cation exchange reaction with the sodium cation; Zinc cation and silver cation are introduced through the first step (S100) and the second step (S200) to pulverize and classify zeolite containing sodium cation, silver cation and zinc cation, that is, Na-Ag-Zn-Zeolite a third step (S300); a fourth step of heat-treating the Na-Ag-Zn-Zeolite pulverized and classified in the third step (S400); a fifth step of mixing the heat-treated Na-Ag-Zn-Zeolite with a recycled polyester resin (S500); and a sixth step (S600) of preparing an antibacterial polyester yarn by melt-spinning the recycled polyester resin and Na-Ag-Zn-Zeolite mixed in the fifth step (S600).

First, as a first step (S100), a zeolite introduced with zinc cations (Zn ^{2 +} ) is prepared through a cation exchange reaction with sodium cations present in the crystal structure of the zeolite. At this time, according to the present invention, it is particularly preferable to use any one zeolite selected from the group consisting of A-type zeolite, X-type zeolite, and Y-type zeolite.

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 added to the first reaction tank having a stirrer and temperature control is possible, and the zeolite is added while stirring. At this time, while maintaining the temperature of the first reaction tank at 30 ~ 80 ℃ nitric acid is added to adjust the pH to 6 ~ 9.

In addition, water is added to the second reactor, and zinc sulfate is added while stirring. It is preferable that the second reaction tank also includes a stirrer and temperature control is possible. At this time, while maintaining the temperature of the second reaction tank at 30 to 80 ℃, zinc sulfate is dissolved in the injected water. As described above, water in which zinc sulfate is dissolved in the second reactor is slowly introduced into the first reactor.

As described above, when water in which zinc sulfate is dissolved is added to the first reaction tank and the temperature is maintained at 30 to 80° C. while stirring, 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.

After the cation exchange reaction for introducing the zinc cation is completed as described above, the zeolite to which the zinc cation is introduced is prepared.

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

In addition, distilled water is added to the second reaction tank, 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 tank at 30 to 80 °C. As described above, water in which silver nitrate is dissolved in the second reaction tank is slowly introduced into the first reaction tank into which the zinc cation-introduced zeolite is introduced.

As described above, when water in which silver nitrate is dissolved is added to the first reaction tank and the temperature is maintained at 30 to 80° C. while stirring, the sodium cation and silver cation remaining in the zeolite to which the zinc cation is introduced are exchanged with each other. . At this time, the cation exchange reaction time for exchanging the silver cation and sodium cation to introduce the silver cation into the structure of the zeolite is preferably 4 to 6 hours.

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

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

According to the present invention, when the pH of the first reaction tank is adjusted to 6 to 9 in the first step (S100) and the second step (S200), the formation of H ⁺ ions and OH ^- ions in aqueous solution will occur more easily than water. and they act as catalysts for cation exchange, thereby further increasing the reaction rate. Accordingly, the cation exchange reaction can occur smoothly in the first step (S100) and the second step (S200).

As described above, during the zinc cation exchange reaction in the first step (S100) and during the silver cation exchange reaction in the second step (S200), sodium cation, silver cation and zinc cation through the reaction conditions such as temperature, pH, and reaction time of the reaction tank It becomes possible to control the molar ratio of 2.3 to 6.3: 0.03 to 0.07: 1.8 to 5.8.

Thereafter, a third step (S300) of pulverizing and classifying the dried Na-Ag-Zn-Zeolite is performed. The third step (S300) refers to a step of pulverizing and classifying the Na-Ag-Zn-Zeolite to control the particle size of the Na-Ag-Zn-Zeolite.

The Na-Ag-Zn-Zeolite is agglomerated by attractive forces in the presence of moisture, so that the average particle size has a size of 1 μm or more. As described above, when the average particle size is 1 μm or more, the size of the particles is large and the dispersibility is poor, so it is not suitable for melt spinning by mixing with a polyester resin.

The coarsening or agglomerated shape of the zeolite inevitably halves excellent effects such as antibacterial properties, reduces the physical properties of the produced antibacterial fiber, that is, the performance of the polymer, and in particular makes it impossible to manufacture in the form of fibers or films.

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

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

That is, the Na-Ag-Zn-Zeolite manufactured through the first step (S100) and the second step (S200) can be pulverized and classified as needed, and the average particle size of the Na-Ag-Zn-Zeolite Having a size of 500 to 800 nm is the most excellent in terms of usability.

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 the agglomerated Na-Ag-Zn- It can be done by mutual collision and friction of zeolite.

The air jet mill is pulverized by mutual collision and friction between the Na-Ag-Zn-Zeolites by spraying high-pressure compressed air from a nozzle to the agglomerated Na-Ag-Zn-Zeolite supplied to the grinding chamber.

At this time, Na-Ag-Zn-Zeolite pulverized to less than a certain size is discharged to the outside through the classification chamber, and when it is larger than a certain size, it is put back into the pulverization chamber and re-ground. Accordingly, the aggregated Na-Ag-Zn-Zeolite can be continuously pulverized.

The Na-Ag-Zn-Zeolite pulverized as described above is classified and only Na-Ag-Zn-Zeolite having an average particle size of 500 to 800 nanometers is taken. According to the present invention, it is preferable to use an air classifier for the classification process.

Na-Ag-Zn-Zeolite having the same size range as above is taken and the remaining zeolite is recycled to the grinding process.

As described above, the Na-Ag-Zn-Zeolite pulverized and classified through the third step (S300) is then subjected to a fourth step (S400) of heat treatment.

The fourth step (S400) is an embodiment, and the Na-Ag-Zn-Zeolite pulverized and classified in the third step (S300) is preferably performed at 200 to 400° C. for 20 to 40 hours.

In general, the pulverized and classified Na-Ag-Zn-Zeolite does not agglomerate when dried, but in the presence of moisture, it agglomerates to increase the average particle size. Therefore, aggregation is prevented by removing moisture present in the zeolite through the heat treatment as described above.

By the heat treatment through the fourth step (S400) as described above, as shown in FIG. 3, the Na-Ag-Zn-Zeolite, that is, the preparation of the zeolite antibacterial agent according to the present invention can be completed.

As described above, the Na-Ag-Zn-Zeolite heat-treated as the fourth step (S400) is then subjected to a fifth step (S500) in which it is mixed with the polyester resin.

In the present invention, by mixing the Na-Ag-Zn-Zeolite with a polyester resin, it is possible to make fibers by melt spinning.

As the polyester resin according to the present invention, a general polyester resin may be used, and it is also possible to use a recycled polyester resin regenerated from waste polyester through a material recycling method or a chemical regeneration method.

That is, the polyester yarn can be manufactured by melt spinning and stretching the general polyester resin or the regenerated polyester resin using the melt spinning apparatus 100 as shown in FIG. 4 .

Specifically, the antibacterial polyester yarn according to the present invention uses ethylene glycol or a material recycling method in which a general polyester resin or scrap of waste polyester is simply extruded to produce a polyester chip and recycled. Thus, any recycled polyester produced by a chemical regeneration method of producing an oligomer by glycolysis of the waste polyester can be used.

In addition, when manufacturing an antibacterial polyester yarn using the regenerated polyester, a drying process is essential to suppress hydrolysis during melt spinning by making the water content of the regenerated polyester resin 30 ppm or less.

According to the present invention, the drying process can be carried out at 140 ~ 170 ℃, in this case, when the drying temperature is less than 140 ℃, the drying time for sufficiently drying the regenerated polyester resin becomes long, thereby increasing the energy cost. . And, when the drying temperature exceeds 170 ° C., fusion between the regenerated polyester resins may occur, and the fused regenerated polyester may have a problem in that the degree of crystallinity is lowered, thereby causing non-uniformity in overall physical properties. Therefore, it is most preferable to perform the drying at 140 ~ 170 ℃ as described above.

The regenerated polyester resin dried as described above may be melt-spun using the melt-spinning apparatus 100 as shown in FIG. 4 to manufacture the antibacterial polyester yarn according to the present invention.

The regenerated polyester resin according to the present invention may be regenerated through a material regenerating method or a chemical regenerating method. The polyester resin has high crystallinity and high melting point, so it is one of the representative synthetic resins widely used not only as fibers but also as films, bottles, and injection-type materials.

Conventionally, a material recycle method in which scraps such as waste polyester bottles are simply extruded and recycled by manufacturing a polyester chip has been commercialized, but this material recycle method is a color change due to simple extrusion. It has a disadvantage in that the range of applicable products is narrow because it is difficult to remove foreign substances.

In order to improve this drawback, a chemical recycle method has been developed in which an oligomer is prepared by glycolysis of waste polyester using ethylene glycol, and then recycled.

This chemical regeneration method is a technology of recycling the waste polyester as a raw material such as fibers or molded products by treating the recovered polyester with a chemical method, returning the waste polyester to a starting raw material or an intermediate raw material.

The recycled polyester used in the present invention is a recycled polyester produced by a material regeneration method or a chemical regeneration method in which an oligomer is produced by glycolysis of waste polyester using ethylene glycol. It is possible.

In this case, it is preferable that the intrinsic viscosity of the recycled polyester is 0.60 to 0.70 dl/g. When the intrinsic viscosity (IV) of the regenerated polyester is less than 0.60 dl/g, the viscosity may be low due to a shear rate acting from the wall of the discharge hole during melt spinning, thereby reducing fiber formation. In addition, when the intrinsic viscosity (IV) exceeds 0.70 dl/g, spinning operability may be deteriorated due to too high viscosity.

That is, the antibacterial polyester yarn according to the present invention is mixed with a general polyester resin or regenerated polyester resin and the Na-Ag-Zn-Zeolite, that is, a zeolite antibacterial agent using the melt spinning device 100 as shown in FIG. , it can be produced by melt spinning.

4, the general polyester resin or the regenerated polyester resin is melted at a melting temperature and then spun through the spinneret 10, but to the spinnerette 10 so that an optimal spinning draft is applied. The size of the formed orifice is 0.3 to 0.4 mm, and L/D (length/diameter) is preferably 2.5 to 3.0.

As described above, the polyester yarn 20 exiting the spinneret 10 is cooled by the cooling wind generated by the cooling wind supply device 30 . At this time, the speed of the cooling wind is 0.4 to 0.6 m/sec, and the temperature is preferably 14 to 18 °C.

An emulsion of 8 to 12% by weight based on the weight of the yarn is applied to the cooled yarn 20 as described above through the upper oiling roller 40 and the lower oiling roller 50 .

In the present invention, the amount of oil attached to the upper oiling roller 40 and the lower oiling roller 50 is preferably 8 to 12% by weight, which is because the filament yarn may be broken due to the increase in tension in the subsequent air entanglement process. , this is because it is necessary to minimize the increase in tension due to friction when passing through the guide by increasing the amount of adhesion of the oil agent.

Thereafter, after passing through the first god roller 60 , it is stretched with the second god roller 70 at a draw ratio of 1.20 to 1.40. By winding the stretched polyester yarn in the winder 80 as described above, the production of the antibacterial polyester yarn according to the present invention can be completed.

By mixing Na-Ag-Zn-Zeolite with the polyester resin as described above, the Na-Ag-Zn-Zeolite is present on the surface of the polyester resin. Accordingly, it is possible to sufficiently cause a metabolic disorder of the bacteria in contact with the Na-Ag-Zn-Zeolite. Through this, the effect that the entire polyester resin has an antibacterial function occurs.

The zeolite antibacterial agent according to the present invention having the three-dimensional skeleton structure, that is, Na-Ag-Zn-Zeolite, has a large specific surface area and excellent heat resistance. do. In addition, since the Na-Ag-Zn-Zeolite has semi-permanent antibacterial activity, it can be applied in various ways to textile products.

The Na-Ag-Zn-Zeolite prepared in the fifth step (S500), that is, 0.5 to 2% by weight of the zeolite antibacterial agent according to the present invention and 98 to 99.5% by weight of the polyester resin are mixed and melt-spun.

According to the present invention, a master batch containing Na-Ag-Zn-Zeolite prepared as described above can be prepared and mixed with a polyester resin, and after mixing as described above, a conventional spinneret for melt spinning (10) It is possible to manufacture an antibacterial polyester yarn by putting it into a melt spinning apparatus 100 having a melt spinning.

Since the melt spinning technique as described above is a technique known in the art, further descriptions related thereto will be omitted.

However, since the Na-Ag-Zn-Zeolite has a microporous structure and has a high moisture content due to the microporous structure, in order to prevent a decrease in the degree of polymerization of the polyester resin due to hydrolysis during melt spinning, the Na- It is preferable to remove moisture present in Ag-Zn-Zeolite through heat treatment in the fourth step (S400), and to manage the moisture content of the polyester resin to 30 ppm or less.

In addition, in the present invention, the antibacterial polyester yarn produced using Na-Ag-Zn-Zeolite as the zeolite antibacterial agent has been described, but it is also possible to produce a film or a molded article.

After melt-spinning a regenerated polyester resin containing 1.0 wt% of Na-Ag-Zn-Zeolite, which is a zeolite antibacterial agent prepared as described above, a yarn was prepared, and then weaved in a plain weave using this. Thereafter, as shown in FIGS. 5 and 6, an antibacterial test was performed after washing 10 times and after washing 30 times in accordance with KS K 0693 (antibacterial test method of textile materials), and the results are shown in Table 2.

strain bacteriostatic reduction rate note Staphylococcus aureus ATCC 6538 99.9% After washing 10 times Klebsiella pneumoniae ATCC 4352 99.9% Staphylococcus aureus ATCC 6538 95.3% After washing 30 times Klebsiella pneumoniae ATCC 4352 84.1%

Referring to Table 2, the polyester fabric containing the zeolite antibacterial agent according to the present invention was washed 10 times with Staphylococcus aureus It can be seen that the bacteriostatic reduction rate for ATCC 6538 and Klebsiella pneumoniae ATCC 4352 strains represents 99.9%.

Also, even after washing 30 times, the bacteriostatic reduction rates were 95.3% and 84.1%. That is, it can be seen that the zeolite antibacterial agent according to the present invention is manufactured by melt spinning while being included in the fiber, and thus has excellent antibacterial properties even after washing.

In general, bacteria and the like are distinguished through Gram staining. That is, Gram-negative bacteria refers to a group of bacteria that cannot maintain the color of the crystal violet reagent when Gram staining is performed using the crystal violet reagent. Also, Gram-positive bacteria refer to bacteria that are dyed royal blue or purple when Gram staining with crystal violet reagent.

Silver cations are stronger against gram-negative bacteria, and zinc cations have stronger properties against gram-positive bacteria. Therefore, the zeolite having silver cations and zinc cations alone may have low antibacterial activity.

Na-Ag-Zn-Zeolite, which is a zeolite antibacterial agent according to the present invention, has a silver cation and a zinc cation in its structure at the same time, so it can exhibit excellent antibacterial properties against both gram-negative and gram-positive bacteria. In addition, by providing a silver cation and a zinc cation at the same time, it has a characteristic that the antibacterial property can exhibit a synergistic effect.

Although the present invention has been described with reference to the experimental examples shown in the drawings, which are merely exemplary, those of ordinary skill in the art will understand that various modifications and equivalent other experimental examples are possible therefrom. In addition, those of ordinary skill in the art to which the present invention pertains will be able to understand that it can be easily modified into other specific forms without changing the technical spirit or essential features of the present invention. Therefore, it should be understood that the embodiments described above are illustrative in all respects and not restrictive, and the true technical protection scope of the present invention should be defined by the technical spirit of the appended claims.

10: spinneret
20: polyester yarn
30: cooling air supply device
40: upper oiling roller
50: lower oiling roller
60: 1st Godtroller
70: 2nd Godtroller
80 : winder
100: melt spinning device

Claims (5)

A first step of introducing zinc cations (Zn ²⁺ ) through a cation exchange reaction with sodium cations present in the crystal structure of zeolite used as a carrier (S100);
A silver cation (Ag ⁺ ) is introduced into the zeolite into which the zinc cation is introduced through a cation exchange reaction with a sodium cation, but the molar ratio of sodium cation:silver cation:zinc cation present in the crystal structure of the zeolite is 2.3 to 6.3: 0.03 -0.07: a second step (S200) of 1.8 to 5.8;
Zinc cations and silver cations are introduced through the first step (S100) and the second step (S200) to pulverize and classify the zeolite containing sodium cations, silver cations and zinc cations, but the pulverized and classified sodium cations and a third step (S300) in which the average particle size of the zeolite containing silver cations and zinc cations is 500 to 800 nanometers;
A fourth step of preparing a zeolite antibacterial agent by heat-treating the zeolite containing the sodium cation, silver cation, and zinc cation, pulverized and classified in the third step (S300) at 200 to 400° C. for 20 to 40 hours (S400) ;
a fifth step (S500) of mixing the zeolite antibacterial agent with a regenerated polyester resin; and
The sixth step (S600) of producing an antibacterial polyester yarn by melt-spinning the regenerated polyester resin and the zeolite antibacterial agent mixed in the fifth step (S500);
The method according to claim 1,
The regenerated polyester resin is a method for producing an antibacterial polyester yarn, characterized in that the material regenerated or chemically regenerated polyester resin.
The method according to claim 1,
The cation exchange reaction in the first step (S100) and the second step (S200) is a method for producing an antibacterial polyester yarn, characterized in that it is carried out at a pH of 6 to 9.
The method according to claim 1,
The zeolite used as the carrier in the first step (S100) is a method for producing an antibacterial polyester yarn, characterized in that at least one selected from A-type zeolite, X-type zeolite and Y-type zeolite.
An antibacterial polyester yarn produced by the method for producing an antibacterial polyester yarn according to any one of claims 1 to 4.

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