KR20070071763A - Manufacturing method of antibacterial, deodorant split type composite fiber - Google Patents

Abstract

The present invention is to produce a composite fiber having a split cross-section by complex spinning two different polymers, a liquid containing an inorganic particulate ceramic substituted with metal ions in one component or two components constituting the composite fiber It relates to a method for producing an antibacterial, deodorant split composite fiber comprising the step of adding a functional agent. According to the method of the present invention, it is possible to produce a split type composite fiber having excellent antibacterial and deodorizing properties and excellent manufacturing processability and low manufacturing cost.

Description

 METHOD FOR PREPARING SPLITTABLE COMPOSITEFIBERS HAVING ANTIMICROBIAL AND DEODORANT PROPERTIES}

1 is a scanning electron micrograph of the antimicrobial, deodorant split composite fiber of the present invention. Figure 2 is a schematic diagram of a liquid functional agent dosing device comprising an inorganic particulate ceramic substituted with metal ions used in the method for producing an antimicrobial, deodorant split type composite fiber according to an embodiment of the present invention.

* Description of the symbols for the main parts of the drawings *

1: pumping shaft control instrument board 2: pumping shaft

3: liquid functional storage tank 4: liquid functional transport pipe

5: liquid functional inlet 6: extruder

The present invention relates to a method for producing an antibacterial, deodorant split composite fiber, and more particularly, in the production of a composite fiber having a split cross section by complex spinning two different polymers, one component in the weaving process. Or it relates to a method for producing an antimicrobial, deodorant split type composite fiber characterized in that a liquid functional agent in which the porous inorganic fine particles substituted with metal ions are dispersed in two components.

Among the fibers, because the microorganisms propagate due to sweat and external pollution of the human body, a large amount of ammonia is generated, causing an unpleasant odor and harming the human body. For this reason, many attempts have been made to give a fiber material a function of suppressing the growth of bacteria that are harmful to the human body.

 Organic silicone quaternary ammonium salts are widely used as an antimicrobial agent for imparting antimicrobial properties to fibers. However, the yellowing of the organic silicones is impaired by yellowing of laundry durability and chlorine-based detergents.

For this reason, Japanese Patent Application Laid-Open No. 54-38951 proposes a method of preparing an ion exchange copolymer and treating it with an aqueous solution of copper and silver salts to express metal ions on the fiber surface to impart antimicrobial properties. However, when treated with an aqueous solution of copper and silver salts, since the metal ions react with the polymer and the physical properties thereof are deteriorated, problems of poor process passability may occur in the subsequent processes such as fiber manufacturing and dyeing.

On the other hand, Japanese Patent Application Laid-Open No. 8-325844 provided antimicrobial properties by containing an antimicrobial agent containing a silver inorganic antimicrobial agent in a fiber, and in Japanese Patent Laid-Open No. 7-109672, a silica gel, a zirconium phosphate salt, Disclosed is a method for producing fibers having antimicrobial performance by using an antimicrobial agent substituted with an inorganic ion exchanger such as zeolite.

As a method of imparting antibacterial and deodorant in the making step, a method of preparing a master batch containing a high concentration of inorganic antibacterial and deodorant and mixing the specific content with a polymer of one component has been developed and used.

For example, the applicant's Korean Patent No. 488622 describes an antimicrobial, deodorizing split type composite fiber by using a master batch in which porous inorganic particulate ceramic fine particles powder substituted with metal ions are mixed with one of two components of the composite fiber. The technique is disclosed.

However, this method can lead to an increase in production costs due to master batch manufacturing. In addition, the smaller the particle size of the antimicrobial and deodorant material is, the more effective the passability of the microfiber yarn is.The smaller the particle size, the stronger the tendency of particles to aggregate in the master batch manufacturing process. The problem that process workability deteriorates.

The present invention is to overcome the problems of the prior art described above, one object of the present invention is to produce an antimicrobial, deodorant split type composite fiber excellent in the process passability, improved productivity of the split type composite fiber To provide a way.

Another object of the present invention is to provide a method for producing a split type composite fiber having improved splitting characteristics in refining and dyeing processes.

Still another object of the present invention is to provide an antibacterial, deodorant split composite fiber having excellent washing durability and excellent process passability.

One aspect of the present invention for achieving the above object is to produce a composite fiber having a split cross-section by complex spinning two different polymers, one component or two components constituting the composite fiber It relates to a method for producing an antimicrobial, deodorant split composite fiber comprising the step of adding a liquid functional agent containing an inorganic particulate ceramic substituted with ions.

In the present invention, the liquid functional agent may include a vehicle composed of one or more components selected from the group consisting of vegetable oils, plasticizers, nonionic surfactants, and polyesters. Two components constituting the composite fiber may be polyester and polyamide.

Hereinafter, with reference to the accompanying drawings will be described in more detail with respect to the present invention.

The method for producing the antimicrobial and deodorizing split composite fiber of the present invention is a method of producing a composite fiber having a split cross section by complex spinning two different polymers. It characterized in that it comprises the step of adding a liquid functional agent containing the inorganic fine particle ceramic substituted metal ions. The split composite fiber produced by the method of the present invention has a structure as shown in FIG. 1 and has antibacterial and deodorant function by porous inorganic fine particles substituted with metal ions exposed to the surface of the split fiber by physical or chemical splitting. Exert.

In the present invention, in the case of incorporating the inorganic fine particles substituted with the metal ions in the spinning process, after preparing a liquid functional agent in which the inorganic fine particle ceramics in which the metal ions are substituted are added, it is added to the polymer. Inorganic particulate ceramics substituted with metal ions dispersed in a liquid vehicle have significantly less reaggregation of particles compared to the master batch method, thereby improving process passability and workability during weaving.

Odor compounds that can cause odors in fibers include many kinds of odor components such as ammonia, hydrogen sulfide, trimethylamine, acetaldehyde and methyl mercaptan. The odor removal method may be classified into a physical adsorption method using a porous material, a chemical adsorption method using an acid, alkali, and the like. In the present invention, in the removal of the odor, the microorganisms of the odor component and the microorganisms of fine inorganic inorganic particles are used. By combining physicochemically, not only to have deodorant performance, but also to produce stable type antimicrobial and deodorant composite fiber which is stable to temperature and humidity conditions and has excellent performance durability.

Metals chemically bonded to malodorous components generally include iron, copper, silver, mercury, tin, and lead. However, when the metal component alone is used, there may be problems such as economic reasons and toxicity. In the present invention, porous inorganic particulate ceramics in which metal ions such as copper, silver, and iron are substituted are used.

Porous inorganic particulate ceramics used in the present invention is used as a binder of metal ions, and the component composition is silica alumina-based inorganic material and has a specific surface area of 100 to 800 m 2 / g. The particle size is preferably adjusted to a size of 1 micron or less in order to apply to the split type composite fiber, and in the case of porous inorganic particulate ceramics, it is preferable to use it by drying at 200 to 600 ° C. before use.

It is preferable that the particle size of the inorganic fine particle ceramic particle used by this invention is 0.05 micrometer-1 micrometer, More preferably, it is 0.1-0.5 micrometer. When the particle size of the inorganic fine particle ceramic particles is less than 0.05 μm, problems of aggregation during dispersion in a liquid vehicle are likely to occur. In contrast, when the particle size of the inorganic fine particles is larger than 1 μm, process permeability and workability may be reduced.

In the present invention, the liquid functional agent includes a vehicle composed of one component or a mixture of two or more components selected from the group consisting of vegetable oils, plasticizers, nonionic surfactants, and polyesters. And other additives such as dispersants.

The vegetable oil may be any kind of vegetable oil, such as seed oil, coconut oil, olive oil, etc., and the plasticizer may be selected from the group consisting of dioctyl phthalate, tricresyl phosphate and diisononyl phthalate. However, it is not necessarily limited to these. As the thermal stabilizer, Ba-Zn-based or Ca-Zn-based thermal stabilizers are preferable, and as antioxidants, phenol-based, thio-based, and phosphorus-based antioxidants may be used. As the nonionic surfactant, all kinds of nonionic surfactants such as ether type, ester ether type, ester type and nitrogen type can be used.

The content of the inorganic fine particle ceramic substituted with metal ions added to the liquid functional agent is preferably 10 to 70 wt% based on the weight of the liquid functional agent. In addition, it is preferable that the viscosity of the liquid functional agent is 20 to 100 poise, but when the viscosity of the liquid functional agent is less than 20 poise or exceeds 100 poise, the measurement accuracy is not uniform and defects may occur.

The amount of the liquid functional agent added to one component or two components of the composite fiber is preferably 0.2 to 5% by weight, more preferably 0.5 to 3% by weight based on the total weight of the composite fiber. If the added amount of the liquid functional agent is less than 0.2% by weight, the content of the liquid functional agent is low, so that the antibacterial and deodorant properties cannot be sufficiently exhibited. When the amount of the liquid functional agent is more than 5% by weight, slippage occurs at the inlet of the extruder, and thus it is not easy to introduce the polymer. It may not be.

In the present invention, the amount of the porous inorganic fine particle ceramic substituted with metal ions is 0.05 to 10% by weight based on the resin of one component of the composite fiber or 0.05% of the porous inorganic fine particle ceramic substituted with the metal ion to the two components of the composite fiber. It is good to add -10 weight%. If the amount of the porous inorganic fine particle ceramic substituted with metal ions is less than 0.05% by weight, the antimicrobial and deodorizing effect is insufficient in the final yarn. If the content is more than 10% by weight, the process permeability is not only lowered but also economically advantageous. none.

In the inorganic ion ceramics substituted with the metal ions used in the present invention, the antibacterial and deodorant performance is largely dependent on the amount of the metal ions substituted on the surface of the porous inorganic particulate ceramics. In the present invention, in order to effectively exhibit the antibacterial and deodorizing performance, the amount of metal ions substituted in the porous inorganic particulate ceramics is 1 to 50% by weight, preferably 5 to 30% by weight, based on the total weight of the porous inorganic particulate ceramics. . If the amount of metal ions substituted on the surface of the porous inorganic particulate ceramics is less than 1% by weight, the antimicrobial and deodorizing effect is insufficient in the final fiber. If the amount is more than 50% by weight, the color of the final fiber added with the inorganic particulate ceramics is changed. After weaving, a problem may occur that dyeing the desired color is impossible. Therefore, the appropriate amount of metal ions is treated with a water-soluble metal salt solution before being added to the polymer for inclusion in the porous inorganic particulate ceramics, and excess metal ions remaining on the ceramic surface are washed with water, removed by vacuum drying, and dried without treatment. It is desirable to adjust the content of the appropriate metal ions by calculating the difference in the weight fraction of the porous inorganic particulate ceramics.

Preferred examples of the two components constituting the antimicrobial, deodorant split composite fibers in the present invention are polyesters having an absolute viscosity of 0.55 to 0.9 dl / g and polyamides having a relative viscosity of 2.3 to 0.5dl / g, and composites thereof The ratio is preferably 60:40 to 40:60.

In the present invention, the method of adding a liquid functional agent containing an inorganic particulate ceramic in which one component or two components constituting the split composite fiber is substituted with a metal ion is not particularly limited. One method is to add a liquid functional agent, for example using an apparatus as shown in FIG. 2. The apparatus shown in FIG. 2 is a liquid pump of a liquid functional agent storage tank 3 containing a liquid functional agent, a pumping shaft 2 and a pumping shaft adjusting instrument panel 1, and a liquid functional agent in the liquid phase of the extruder 6. It includes a liquid functional transport pipe 4 to be delivered to the functional agent inlet (5). The liquid functional agent is supplied through a pore pump connected to the liquid functional inlet 5 at the inlet of the extruder 6 and kneading of the supplied liquid functional agent and the polymer is performed in the extruder.

Compared with the method of using a master batch, which is a method for producing a conventional functional fiber, the method of incorporating the functional agent in the liquid form of the present invention does not require premixing with a polymer because the functional agent is directly supplied to an extruder, There is no thermal decomposition problem, the dispersion of the functional particles is easy, and has the advantage that the functional particles do not aggregate.

The liquid vehicle is discharged through the spinning line and affects the process of solidifying the polymer, thereby improving the fluidity of the polymer chain and thus improving the elongation. Therefore, even if the yarn is produced with a high discharge amount, sufficient stretching is possible, so that the functional finely divided fiber of low fineness can be manufactured, thereby improving productivity.

In addition, in the product family using split composite yarns, the cross-sectional splitting characteristics are improved by reducing the polyester by NaOH input in the refining process, and the cross-sectional splitting is performed due to the difference in shrinkage of the two constituent polymers and stress applied in the dyeing process. In addition, the liquid vehicle in which the metal ion-substituted inorganic fine particle ceramics are dispersed has good fluidity and shows the property of being pushed out to the surface of the fiber after the fiber is solidified. The liquid vehicle pushed out between the two constituent polymers increases the fluidity of the polymer chain. As the liquid vehicle exits the refining and dyeing processes, the cross-sectional splitting characteristics are improved.

The antimicrobial and deodorant split type composite fiber produced by the present invention has a high fluidity remaining at the interface between the two constituent polymers in the refining and dyeing process, and the interface separation property is improved to obtain a product having improved cross-sectional partitioning. There is a number.

 The stretched yarn obtained in the present invention may use a variety of additives, such as known additives, pigments, stabilizers, lubricants, for example, for the purpose of dyeing, antistatic, etc. in a later step.

Hereinafter, the present invention will be described in more detail with reference to Examples, but these are merely for the purpose of explanation and are not intended to limit the scope of the present invention.

Example  One

Partially spun in a spherical form at a ratio of 50/50 by weight of polyamide having a relative viscosity of 3.0 dl / g as one component and a polyamide having a relative viscosity of 3.0 dl / g as one component. A liquid vegetable oil in which 30 wt% of silver-substituted silica alumina was dispersed was added to 1.6 wt% based on the weight of polyamide using the apparatus as shown in FIG. 2. The prepared composite fiber was stretched and flammed 1.75 times, squeezed and refined in a circular knit machine, and then evaluated for overall physical properties. The results are shown in Tables 1 and 2 below.

Example  2

Using a polyester having an intrinsic viscosity of 0.64 dl / g as one component and a polyamide having a relative viscosity of 3.0 dl / g as another component, the composite is spun at a ratio of 50/50 by weight. A liquid vegetable oil in which 30 wt% of the substituted silica alumina was dispersed was added so as to be 2.3 wt% based on the weight of polyester using the apparatus as shown in FIG. 2. The prepared composite fiber was stretched and flammed 1.7 times, squeezed and refined in a circular knit machine, and evaluated for physical properties. The results are shown in Tables 1 and 2 below.

Example  3

Using a polyester having an intrinsic viscosity of 0.64 dl / g as one component and a polyamide having a relative viscosity of 3.0 dl / g as another component, the composite is spun at a ratio of 50/50 by weight. A liquid vegetable oil obtained by dispersing 30 wt% of substituted silica alumina was added to 0.7 wt% of the polyester weight, and at the same time, a polyamide weight was applied to a liquid vegetable oil obtained by dispersing 30 wt% of silica alumina substituted with silver. 0.7 wt% of the solution was added. The prepared composite fiber was stretched and twisted 1.8 times and squeezed and refined in a circular knit machine to evaluate physical properties, and the results are shown in Tables 1 and 2 below.

Comparative example  One

90% by weight of intrinsic viscosity of 0.54 dl / g polyester and 10% by weight of 30% by weight of silver-substituted silica alumina vacuum dried at 150 to 300 ° C and 1 mmHg or less were melt-mixed in a twin screw compound to prepare pellets. . At this time, the temperature of the heating zone was set to 230 to 245 ° C in one area, 250 to 280 ° C in two areas, 260 to 280 ° C in three areas, 260 to 280 ° C in four areas and 260 to 285 ° C in five areas. The pellets were dried at 140 ° C. for 8 hours, and then mixed with a polyester resin having an intrinsic viscosity of 0.65 dl / g and 5 wt% of the total polyester in a V-type mixer to form one component and a relative viscosity of 3.3 dl / g. A composite fiber was prepared using phosphorus polyamide as another component. The composite ratio was 50% by weight of the polyester containing 1.4 wt% of the master batch containing the metal ion-substituted inorganic particulate ceramics and 50% by weight of polyamide to prepare a split composite fiber as shown in FIG. 1.5 times stretched and twisted the prepared composite fiber was squeezed and refined in a circular knit machine and the physical properties were evaluated and the results are shown in Table 1 and Table 2 together.

Comparative example  2

10 wt% of 30 wt% silver-substituted silica alumina vacuum dried at 150 to 300 ° C and 1 mmHg to 90 wt% of polyamide having a relative viscosity of 2.6 dl / g was melt-mixed in a twin screw compound to produce pellets. It was. At this time, the temperature of the heating zone was set to 230 to 245 ° C in one area, 250 to 280 ° C in two areas, 260 to 280 ° C in three areas, 260 to 280 ° C in four areas and 260 to 285 ° C in five areas. After drying the pellets at 140 ° C. for 8 hours, the polyamide resin having a relative viscosity of 3.0 dl / g was mixed with 3% by weight of the total polyamide in a V-type mixer to form one component, and the intrinsic viscosity was 0.65 dl / g. Composite fibers were prepared using polyester as another component. The composite ratio was 50 wt% of polyamide containing 5 wt% of a master batch containing a metal ion-substituted inorganic particulate ceramic, and 50 wt% of polyester to prepare a composite fiber as shown in FIG. 1. 1.55 times the drawn and twisted composite fiber prepared in a circular knit machine and squeezed and refined to evaluate the physical properties and the results are shown in Table 1 and Table 2 together.

Antibacterial content① (%) Fineness② Antibacterial rate Deodorant Laundry durability Process passability Number of cuts Example 1 0.48 0.52 Great usually Great Great 0.7 Example 2 0.7 0.52 Great usually Great Great 1.2 Example 3 0.42 0.52 Great Great Great Good 0.6 Comparative Example 1 0.5 0.52 Great usually Bad Good 2.7 Comparative Example 2 0.5 0.52 Great usually Bad Good 2.4

 Note) ① Content of inorganic fine ceramics with metal ions substituted by fiber weight

    ② Fineness of monofilament

[Property evaluation method]

* Antibacterial rate : The antibacterial effect was tested against Staphylococcus aureus by test standard AATCC-100 test method. Inoculate the agar medium with the bacteria and inoculate the specimen with the incubator for 24 hours at 37 ° C, and then add a certain amount of liquid to extract the bacteria from the specimen. The percentage of bacteria remaining due to the addition of porous inorganic particulate ceramics containing metal ions was then calculated by measuring the number of bacteria remaining in the treated and untreated fabrics. Usually, 95% or less was determined as bad.

* Deodorant : Place a glass evaporation tube containing odorous gas such as ammonia and hydrogen sulfide under the desiccator, place the test specimen on the plate of the passageway connected and seal the desiccator and leave it at 25 ℃ for 2 hours. After measuring the odor concentration of the grass evaporation tube in the detector tube to calculate the odor concentration reduction rate according to the following equation 1, excellent when the percentage is more than 99%, usually 95 to 99%, it is determined to be bad when less than 95%. It was.

Odor concentration reduction rate (%) = (1- remaining odor concentration (ppm) / odor concentration before reduction (ppm)) X 100

* Wash durability : 100 g of the test cloth was placed in a washing bath containing 20 g of water and 35 g of a detergent and washed 20 times at a temperature of 40 ° C. for 12 minutes, and then the antibacterial performance was evaluated by the above method.

    * Process Permeability: The process permeability was evaluated to the degree of increase in the spin pack pressure for 7 days of spinning. Excellent 30 ~ 50kgf / ㎠ rise, 50 ~ 100kgf / ㎠ rise: Good, Bad more than 100kgf / ㎠

* Number of thread trimmings : The number of thread trimmings produced during production of 1 ton of yarn was evaluated.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 290 290 290 290 290 3200 3200 3200 3200 3200 90 87 94 78.8 78.8 POY Properties Fineness (d) 263.3 254.5 274.9 231 233 Strength (g / d) 2.43 2.61 2.26 2.64 2.85 Elongation (%) 148 140.3 151 128 127.8 Combustible property Elongation ratio 1.75 1.7 1.8 1.51 1.54 Fineness (d) 151.2 152.3 150.6 153 151.3 Strength (g / d) 3.87 3.77 3.92 3.33 3.27 Elongation (%) 36 38 34 37 38 95 94 94 91 90 91 93 89 88 89 86 84 92 67 71

* Radiation Workability: Actual Full Cheese Number / Theory Full Cheese × 100

* Flammability: Actual Full Cheese Number / Theory Full Cheese × 100

* Cross-sectional division: Number of independent phases in cross section / 1152 (Fila number (72) × Number of divisions (16)) × 100

Although the preferred embodiments of the present invention have been described in detail above, it will be apparent to those skilled in the art that various changes and modifications can be made within the scope of the technical idea of the present invention, and such variations and modifications should also be interpreted as belonging to the appended claims. something to do.

Since the antimicrobial and deodorant split composite fibers produced by the present invention are micronized by physical and chemical splitting, the surface area increases, and thus the probability of the presence of inorganic fine particles substituted with metal ions on the surface of the fiber increases. It is economical because it can exhibit sufficient antibacterial and deodorant even if low content of inorganic fine particle ceramic substituted with ions is added.

In addition, the antimicrobial, deodorant split type composite fiber produced by the present invention has superior process passability than adding antibacterial and deodorant additives using a master batch, and has a cross section in a post process (refining and dyeing process). It is easy to divide, and the productivity is excellent to reduce the manufacturing cost.

When the antimicrobial agent is treated on the surface of the fiber by post-treatment, the antimicrobial and deodorant properties after washing are reduced. However, the antimicrobial deodorant split composite fiber prepared by the present invention is a metal ion-substituted inorganic material that gives antimicrobial and deodorant properties. Since the particulate ceramic is included in the yarn, there is an advantage that the antibacterial and deodorizing properties are not deteriorated even after washing.

When the fiber produced by the present invention is applied to a cleaning cloth used for water or dust removal, the product can exhibit sufficient antibacterial and deodorizing effect even with a smaller amount of antimicrobial agent than a general yarn. Can be.

Claims (9)

In producing a composite fiber having a split cross-section by complex spinning two different polymers, a liquid functional agent containing an inorganic particulate ceramic substituted with metal ions in one component or two components of the composite fiber Method for producing an antimicrobial, deodorant split type composite fiber comprising the step of adding. 2. The antimicrobial and odor deodorizing type according to claim 1, wherein the liquid functional agent comprises a vehicle composed of at least one component selected from the group consisting of vegetable oils, plasticizers, nonionic surfactants and polyesters. Method for producing a composite fiber. The method according to claim 1 or 2, wherein the two components constituting the composite fiber are a polyester having an absolute viscosity of 0.55 to 0.9 dl / g and a polyamide having a relative viscosity of 2.3 to 3.5 dl / g. 60:40 to 40:60, characterized in that the antimicrobial, deodorant split type composite fiber manufacturing method. The method of claim 1 or 2, wherein the content of the liquid functional agent is 0.2 to 5% by weight based on the total weight of the composite fiber. The method of claim 1 or 2, wherein the addition amount of the porous inorganic particulate ceramic substituted with the metal ions is 0.05 to 10% by weight based on the resin of one component, the production of antimicrobial, deodorant split type composite fiber Way. The method of claim 1 or claim 2, wherein the amount of metal ions substituted in the porous inorganic particulate ceramics is 1 to 50% by weight of the total weight of the porous inorganic particulate ceramics, the production of antimicrobial, deodorant split type composite fiber Way. The method of claim 1 or 2, wherein the viscosity of the liquid functional agent is 20 to 100 psi. The method of claim 2, wherein the plasticizer is selected from the group consisting of dioctyl phthalate, tricresyl phosphate and diisononyl phthalate. An antibacterial, deodorant split composite fiber prepared by the method of claim 1 or 2.

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