KR20170091223A - Mothproof fiber and preparation method thereof - Google Patents

Abstract

A zirconium or zeolite carrier has an average particle size of 0.5 to 5.0 mu m and a zirconium or zeolite support having an average particle size of 0.5 to 5.0 mu m, Characterized by having a specific surface area of 60 to 500 m < 2 > / g and a carrier having a particle diameter not larger than the average particle size of 50 to 70% based on a number average distribution, Fiber and a method of producing the same.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to insect-repellent fibers,

More particularly, the present invention relates to an insect repellent fiber having excellent insect repellency and insect repellent performance, excellent spinnability and dyeability, and a method for producing the insect repellent fiber. .

Usually, when you enjoy leisure time for a long time outdoors, it is often bitten by various kinds of insects such as mosquitoes and ticks. In the case of ticks, it can lead to epidemic hemorrhagic fever or Tsutsugamushi disease, which can be life-threatening. Although mosquito repellent is applied to the body to prevent harmful insects such as mosquitoes, it is not effective and easy to get rid of the mosquito repellent.

Insecticidal fabrics are being developed to fundamentally eliminate access to pests such as mosquitoes and house dust mites. For example, Japanese Patent No. 1998-025618 discloses a technique of adding 0.1 to 3.0 wt% of a terpene resin as a repellent agent for nylon fibers and polyester fibers at the time of melting a fiber material. However, since the terpene insecticide is a liquid at room temperature, there is a problem in that radioactivity is mixed in irregularly mixed in the fiber polymer during mixing and spinning, and the insect repellent component in the polymer is lost during post-spinning and washing.

U.S. Patent No. 5,631,072 discloses a technique in which insecticides are placed on fabrics by impregnation with polymeric binders and crosslinking agents, or by surface coating with polymeric binders and thickeners on fabrics. However, in this technique, a large amount of insect repellent is used for impregnating the fabric, and the repellent composition is destroyed by repetitive washing, and thus the insect repellent effect is drastically deteriorated.

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made keeping in mind the above problems occurring in the prior art, and an object of the present invention is to provide an insect repellent And a method for producing the insect repellent fiber.

Other objects, advantages and novel features of the present invention will become more apparent from the following detailed description and the preferred embodiments.

One aspect of the present invention to attain the above object is to provide an insecticide comprising 10 to 50% by weight of a repellent agent supported on at least one selected from zirconium and zeolite in a polyamide-based yarn, wherein the zirconium or zeolite fume Characterized in that the support has an average particle diameter of 0.5 to 5.0 μm and a specific surface area of 60 to 500 m 2 / g and a support having a particle diameter of not more than the average particle diameter of 50 to 70% based on the number average distribution.

Another aspect of the present invention relates to a method for producing a master batch chip, which comprises melt-mixing an insect repellent containing 10 to 50 wt% of a repellent on a polyamide polymer and carrying at least one repellent on zirconium and zeolite, Wherein the zirconium or zeolite carrier has a mean particle size of 0.5 to 5.0 mu m and a specific surface area of 60 to 500 m < 2 > / g, To 70% by weight of the insecticidal fiber.

Another aspect of the present invention relates to a knitted fabric made using the insect repellent fiber of the present invention.

According to the present invention, it is possible to provide insect repellent, especially insect repellent fiber which is continuously released antimicrobial component and does not deteriorate its functionality by washing or the like, thereby improving washing durability.

In addition, the method of the present invention further improves the insect repellent function and washing durability compared to the conventional method, and improves spinning operation and dyeability, thereby providing a variety of textile products such as clothing, outdoor bedding, and tent useful for sports / outdoor use .

Fig. 1 is a cross-sectional photograph of the insect repellent fiber produced in the embodiment of the present invention. Fig.

Hereinafter, embodiments of the present invention will be described in more detail with reference to examples and the like. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted.

The insect repellent fiber according to one embodiment of the present invention includes an insecticide in which 10 to 50 wt% of a repellent agent is supported on one or more kinds of supports selected from zirconium and zeolite in a polyamide yarn.

The zeolite and zirconium-based carrier is a porous carrier having a very large surface area of particles, which is advantageous for supporting liquid or ionic substances, and is highly heat resistant and suitable for melt spinning. It is colorless and odorless and is suitable for incorporation into fibers Do.

The zirconium or zeolite carrier has an average particle size of 0.5 to 5.0 μm and a specific surface area of 60 to 500 m 2 / g, and a carrier having a particle size of not more than the average particle size is 50 to 70% based on the number average distribution. When the carrier containing the insect repellent component is incorporated into the polyamide polymer, the scattering of the particle size directly affects the dispersibility and spinnability. Here, the average particle diameter of the support is the average particle diameter measured by the laser-scattering method, and the specific surface area of the support is the specific surface area determined by the BET method.

If the average particle diameter of the zirconium or zeolite carrier is less than 0.5 탆, it is difficult to prepare the carrier. If the average particle diameter exceeds 5.0 탆, the particle diameter of the carrier is large.

If the number of particles having a particle size smaller than the average particle size of the carrier is too large, there is a possibility that the spinning workability and pressure rise due to cohesion of the carrier bodies may occur. On the other hand, if the distribution of the carrier particles having a size smaller than the average particle size is too small, the coagulation phenomenon occurs very rapidly due to the attraction force, and the coarse particles having an average particle size or more are present in a large amount. Therefore, in order to prevent the aggregation phenomenon and improve the radiating processability, it is preferable that the particle diameter distribution of the carrier is within the above range.

In a preferred embodiment, the support is a mixture of zeolite and zirconium, and the mixing ratio is from 75:25 to 25:75.

The zeolite carrier is faujasite _{((Na 2, Ca, Mg} ) 29 [Al 58 Si l34 0 384] · 240H 2 0; cube), β- zeolites _{(Na n [Al n Si 64} - n O l28] , n <7; tetragonal), moohdenayiteu zeolites _{(Na 8 [Al 8 Si 40} 0 96] · 24H 2 0; orthorhombic), ZSM zeolites _{(Na n [Al n Si 96} - n O 192] · ~ 16H 2 O, n <27; orthorhombic), and mixtures thereof.

The insecticide is composed of Pyrethrin, Allethrin, phthalthrin, resmethrin, furamethrin, phenothrin and permethrin. &Lt; / RTI &gt; is a pyrethroid insect repellent selected from the group consisting of Such pyrethroid insecticides are more likely to decompose in nature than insecticides such as other organophosphorus compounds, have low toxicity to humans and livestock, and are highly safe.

The insecticidal fiber of the present invention has a single fiber fineness of about 0.2 to 5 pdf. When the single fiber fineness is less than 0.2 pdf, the radioactive degradation due to incorporation of the internal carrier is intensified. When the single fiber fineness exceeds 5 pdf, The disadvantage is that the feeling of touch is not smooth at the time of deployment. The diameter of the insect repellent fiber of the present invention is about 5 to 25 mu m

The addition amount of the insect repellent is required to be 10 to 50% by weight of the carrier. If it is less than 10% by weight, the insecticidal effect becomes insufficient. If it exceeds 50% by weight, the insect repellent bleed out during spinning is high and the viscosity of the polymer is decreased.

A method of adding a repellent is preferably a masterbatch manufacturing method in which a kneaded chip is formed by adding a kneaded chip to a polyamide resin and a kneader after being supported on inorganic particles so as to uniformly disperse the insect repellent component.

The polyamide-based insect repellent fiber is nylon 6, nylon 11, nylon 12, nylon 66 or nylon 610.

As the fiber form of the present invention, it is possible to use an optimal fiber type fiber in accordance with the application, such as multifilament, monofilament, staple fiber, false-twist yarn and flat yarn.

The insect repellent fiber of the present invention may further contain pigments, ultraviolet stabilizers and the like so long as the antifungal effect is not impaired.

Another aspect of the present invention relates to a knitted fabric manufactured using the insect repellent fiber of the present invention. The fabric using the insect repellent fiber of the present invention may be any fabric or knitted fabric, and may be dyed using an acid dye or a disperse dye. It is suitable for outdoor use such as outdoor clothing, sleeping bag, mosquito net and tent fabric. The insect control fiber of the present invention may be used alone, but may be used in combination with other fiber materials as long as insect repellent performance is not deteriorated.

In the method of the present invention, an insect repellent carrier having 10 to 50% by weight of a repellent agent supported on at least one support selected from zirconium and zeolite is melt-mixed with the polyamide polymer to prepare a master batch chip, Wherein the zirconium or zeolite carrier has an average particle size of 0.5 to 5.0 μm and a specific surface area of 60 to 500 m 2 / g and a carrier having a particle size of not more than 50 nm, .

The master batch chip contains zirconium or zeolite carrier carrying pyrethroid insect repellent at 0.1 to 5% by weight of the fiber. If the amount of the carrier is less than 0.1%, the functionality is insufficient, and if it exceeds 5%, the radioactivity may become poor. When the insect repellent carrier in the master batch chip is contained in an amount of less than 0.1% by weight, the insecticidal effect becomes insufficient. When the insect repellent carrier exceeds 5% by weight, radioactivity and dyeability may be deteriorated.

In the preparation of the master batch chip, the polyamide polymer, the repellent-impregnated zirconium or the zeolite carrier are uniformly mixed. Subsequently, this mixture is supplied to a single-screw extruder or a twin-screw extruder, melted and mixed, and then cooled in water to prepare a master batch chip. When the master batch chip is not produced and the respective materials are melt-mixed, the persistence of the insect repellent effect is remarkably lowered, and the insect repellent effect of the insect repellent fiber is greatly lowered.

The spinning using the master batch chip comprising the repellent of the present invention can be exemplified by mixed spinning or direct spinning. The spinning speed and the stretching condition of the insecticidal fiber of the present invention are not particularly limited and may be the same as the conventional methods. For example, a method of spinning at a spinning speed of 1,000 to 3,000 m / min, followed by stretching at a stretching ratio of 1.1 to 5.0, followed by direct stretching and thermal fixation at a spinning speed of 1,000 to 3,000 m / min .

It is possible to produce a multifunctional insecticidal fiber having a content of a double-walled repellent carrier containing a repellent agent in a fiber of 0.510% by weight and a single-fiber fineness of 0.2 to 5 denier. The insecticidal fiber produced by the method of the present invention as described above may be a long fiber and the single fiber fineness is about 0.2 to 5 pdf. When the single fiber fineness is less than 0.2 pdf, the radioactive degradation due to incorporation of the internal carrier is intensified , And when the single fiber fineness exceeds 5 pdf, there is a disadvantage that the touch feeling is not smooth when the application is used as a garment product.

The zirconium or zeolite carrier has an average particle diameter of 0.5 to 5.0 μm and a specific surface area of 60 to 500 m 2 / g, and a carrier having a particle diameter of not more than 50 μm is used.

The insecticide is composed of Pyrethrin, Allethrin, phthalthrin, resmethrin, furamethrin, phenothrin and permethrin. A pyrethroid insect repellent selected from the group consisting of Also, since the pyrethroid insect repellent has a heat-resistant temperature of about 200 to 290 ° C, it is preferable that the polymer temperature is 290 ° C or lower during spinning.

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.

Example

Example  One

Nylon 6 as a polyamide-based polymer, phenoline as a pyrethroid insect repellent, and zirconium as a carrier were mixed and fed to a biaxial extruder, melted and mixed at 240 캜, and then cooled in water to prepare a master batch chip. The master batch chip thus obtained is composed of 80% by weight of a polymer and 20% by weight of a carrier containing an insect repellent. At this time, the average particle size of the insect repellent support is 1.0 占 퐉 and the particles having a size of 1.0 占 퐉 or less are distributed in 65%. The thus prepared master batch chip was mixed and spin-spun at a ratio of nylon 6 (relative viscosity of 2.6) having a melting point of 220 캜 at a master batch chip ratio of 90:10 wt%, and was radiated at a spinning temperature of 260 캜 at a rate of 4,000 m / 70d / 68f yarn. The cross-sections of the insecticidal fibers were as shown in Fig. 1, and the properties, processability and functionality of the insecticidal fibers were evaluated and are shown in Table 1 below. In the case of functionality, sock knitting and dyeing were carried out using a sock knitting machine in a conventional manner, and then evaluation of emptiness, spinnability and dyeability were measured.

Example  2

Nylon 6 as a polyamide-based polymer, phenoline as a pyrethroid insect repellent, and zeolite as a carrier were mixed and fed to a biaxial extruder, melted and mixed at 240 ° C, and then cooled in water to prepare a master batch chip. The master batch chip thus obtained is composed of 80% by weight of a polymer and 20% by weight of a carrier containing an insect repellent. At this time, the average particle size of the insect repellent support is 1.5 占 퐉 and the particle size of 1.5 占 퐉 or less is 65%. The thus prepared master batch chip was mixed and spin-spun at a rate of 95: 5% by weight of master batch chip with nylon 6 (relative viscosity of 2.6) having a melting point of 220 캜 and spinning at a spinning speed of 260 캜 at a rate of 4,000 m / 70d / 24f yarn. The results of physical properties evaluation are shown in Table 1.

Example  3

Except that nylon 6 as a polyamide-based polymer, phenoline as a pyrethroid insect repellent, zeolite as a support, and zirconium at a ratio of 50:50 were used, After the fibers were produced, the physical properties were evaluated and the results are shown in Table 1.

Comparative Example  One

Nylon 6 as a polyamide-based polymer, phenoline as a pyrethroid insect repellent, and silica as a carrier were mixed and fed to a biaxial extruder, melted and mixed at 240 캜, and then cooled in water to prepare a master batch chip. The master batch chip thus obtained is composed of 90% by weight of a polymer and 10% by weight of a carrier containing an insect repellent. At this time, the average particle diameter of the insect repellent support is 3.0 탆, and the particles having a size of 3.0 탆 or less are distributed in 65%. The thus prepared master batch chip was mixed and spin-spun at a ratio of nylon 6 (relative viscosity of 2.6) having a melting point of 220 캜 at a master batch chip ratio of 90:10 wt%, and was radiated at a spinning temperature of 260 캜 at a rate of 4,000 m / 70d / 24f yarn. The properties of the insect repellent fibers were evaluated and the results are shown in Table 1.

Comparative Example  2

Nylon 6 as a polyamide-based polymer, phenoline as a pyrethroid insect repellent, and zeolite as a carrier were mixed and fed to a biaxial extruder, melted and mixed at 240 ° C, and then cooled in water to prepare a master batch chip. The master batch chip thus obtained is composed of 80% by weight of a polymer and 20% by weight of a carrier containing an insect repellent. At this time, the mean particle size of the insect repellent support is 8.0 탆 and the particles having a size of 8.0 탆 or less are distributed in 65%. The thus prepared master batch chip was mixed and spin-spun at a ratio of nylon 6 (relative viscosity of 2.6) having a melting point of 220 캜 at a master batch chip ratio of 90:10 wt%, and was radiated at a spinning temperature of 260 캜 at a rate of 4,000 m / 70d / 24f yarn. The properties of the insect repellent fibers were evaluated and the results are shown in Table 1.

Comparative Example  3

The master batch chip and the insect repellent fiber were produced in the same manner as in Example 1 except that the zirconium carrier had an average particle diameter of 0.1 탆 and the physical properties were evaluated and the results are shown in Table 1 .

Comparative Example  4

The same procedure as in Example 1 was repeated except that the spinning temperature was changed to 300 ° C to prepare insect repellent fibers. The properties of the insect repellent fibers were evaluated and the results are shown in Table 2.

Comparative Example  5

The same procedure was followed as in Example 1 except that terpene resin was used as an insect repellent to prepare insect repellent fibers, and physical properties were evaluated. The results are shown in Table 2.

Comparative Example  6

2% by weight of phenolin was applied to a conventional nylon 6 fabric, followed by evaluation of various physical properties. The results are shown in Table 2.

<< Property evaluation method.

* Average particle size of the carrier: To measure the particle size of the carrier particles charged into the yarn, the capsule was taken 10 times at random using an electron microscope (SEM) equipped with an image analyzer, The average size was calculated.

* Specific surface area of the carrier: The specific surface area of the carrier particle is obtained by the BET method.

(3) Male rats (6 weeks of age, 23 to 34 g) were placed in a stainless steel mesh net (300x300x300 mm) equipped with feed (purina feed) and water feeder, (1 m x 1 m x 1 m) in a transparent acrylic material at a height of 50 cm. The fabric composed of the yarn prepared in Example 1 was cut into a size of 250 x 250 mm, wrapped in a rat, and put into a metal mesh for fixing. As a control, the rats are wrapped in the same fabric with no insect repellent. Each of the rats carrying the functional fabric and the rats carrying the normal fabric were put in different boxes and each of the female moths of the white-lined mosquito * 20 vaginal female female rats were spun into the laboratory for 10 minutes every 30 seconds. Record the number (number of mosques attached to H / M) and the number of mosquitoes that have been vomiting for 10 minutes. This procedure was repeated three times. The test was carried out at room temperature of 27.4 ± 0.2 ° C and 72 ± 2% RH. The insect repellency is considered to be excellent if the repelling rate is 50% or more.

Avoidance rate (%) = (number of vomiting mosquitoes / total number of mosquitoes emitted in a laboratory) × 100.

* Washing durability: The test for evaluating the durability of washing was carried out by carrying out washing tests 10 times and 20 times according to the washing fastness test method according to KS K0430 for insect repellent fabrics and then performing insecticidal performance test.

* Radiation workability: The radiation productivity is calculated as% in terms of the yield of non-cut insecticidal fibers when irradiated with insecticidal fiber 9 kg drum, and when the yield is 100 to 95%, it is ◎, when it is 95 to 90% And × for cases of less than 90%.

* Dyeability:

- Samples: Yarn was knitted to a length of 20 cm with a sock knitting machine.

- Bathing: C.I. ACID BLUE 40 dye was made into a dye concentration of 1% o.w.f.

- Dyeing test: The sample was put in a salt bath, and the dyeing temperature was raised to 100 ° C at a constant rate of 2 ° C / min and maintained at 100 ° C for 30 minutes. After the stained samples were sufficiently dried, the staining non-uniformity was visually evaluated by sensory evaluation.

division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Carrier type zirconium Zeolite zirconium
/ Zeolite Silica Zeolite zirconium Carrier average particle diameter
(탆) 1.0 1.5 1.0 3.0 8.0 0.1 Insect repellent Phenotlein Phenotlein Phenotlein Terpen Teppen Phenotlein Amount of incorporation of carrier in fiber (% by weight) 2.0 1.0 2.0 1.0 2.0 2.0 Method of treating carrier Yarn incorporation Yarn incorporation Yarn incorporation Yarn incorporation Yarn incorporation Yarn incorporation Number of deniers / filaments 70d / 68f 70d / 24f 70d / 68f 70d / 24f 70d / 24f 70d / 68f Insoluble (before washing) 95 85 97 70 98 75 Loneliness
(After washing 10 times) 70 66 74 45 75 42 Loneliness
(After washing 20 times) 58 53 65 25 68 27 Antimicrobial activity
(KS K 0693,
After washing 20%,% 99.9 99.9 99.9 69.0 99.9 71.2 Radiation workability ◎ ○ ◎ ○ × ◎ Dyeability ◎ ◎ ◎ ◎ × ◎

division Comparative Example 4 Comparative Example 5 Comparative Example 6 Carrier type zirconium zirconium zirconium Carrier average particle diameter (占 퐉) 1.0 1.0 1.0 Insect repellent Phenotlein Terpen Phenotlein Amount of incorporation of carrier in fiber (% by weight) 2.0 2.0 2.0 Method of treating carrier Yarn incorporation Yarn incorporation Post-processing Number of deniers / filaments 70d / 68f 70d / 68f 70d / 68f Insoluble (before washing) 46 35 95 Insoluble (after 10 washes) 27 12     36 Insoluble (after 20 washes) 12 3 11 Antimicrobial activity (KS K 0693,
After washing 20%,% 48.3 36.4 45.7 Radiation workability ○ × ◎ Dyeability × × ×

Although the preferred embodiments of the present invention have been described in detail, the present invention is not limited thereto. It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit and scope thereof, Range.

Claims (11)

Wherein the zirconium or zeolite carrier has an average particle diameter of 0.5 to 5.0 占 퐉 and a specific surface area of not less than 10 占 퐉 and a specific surface area of not less than 50 占 퐉, 60 to 500 m &lt; 2 &gt; / g, and the support having a particle diameter not larger than the average particle size is 50 to 70% based on the number average distribution.
The insect control fiber according to claim 1, wherein the carrier is a mixture of zeolite and zirconium, and the mixing ratio is 75:25 to 25:75.
The insect control fiber according to claim 1, wherein the insect repellent fiber has a monofilament fineness of 0.2 to 5 denier and a content of the insect repellent functional carrier in the fiber is 0.1 to 5 wt% based on the weight of the fiber.
The method of claim 1, wherein the carrier is zeolite faujasite _{((Na 2, Ca, Mg} ) 29 [Al 58 Si l34 0 384] · 240H 2 0; cube), β- zeolites (Na _n [Al _n Si _{64-n O l28], n} <7; tetragonal), moohdenayiteu zeolites _{(Na 8 [Al 8 Si 40} 0 96] · 24H 2 0; orthorhombic), ZSM zeolites _{(Na n [Al n Si 96} - n O ₁₉₂ ] .about.16H ₂ O, n <27; orthorhombic), and mixtures thereof.
The insecticidal composition of claim 1, wherein the insecticide is selected from the group consisting of pyrethrin, allethrin, phthalthrin, resmethrin, furamethrin, phenothrin, Wherein the insecticidal fiber is a pyrethroid insect repellent selected from the group consisting of permethrin.
The insect control fiber according to claim 1, wherein the polyamide-based insect repellent fiber is nylon 6 or nylon 66.
A woven fabric produced using the fibers of any one of claims 1 to 6.
A method for producing an insect repellent fiber in which a insect repellent containing 10 to 50% by weight of an insect repellent on a polyamide polymer and at least one carrier selected from zirconium and zeolite is melted and mixed to prepare a master batch chip, Wherein the zirconium or zeolite carrier has an average particle diameter of 0.5 to 5.0 μm and a specific surface area of 60 to 500 m 2 / g and a carrier having a particle diameter of not more than 50 nm, Insecticidal fiber.
The method for producing an insect repellent fiber according to claim 8, wherein the polyamide-based polymer is nylon 6 or nylon 66.
The zirconium or zeolite carrier according to claim 8, wherein the zirconium or zeolite carrier has an average particle diameter of 0.5 to 5.0 占 퐉 and a specific surface area of 60 to 500 m2 / g, Wherein the insect repellent fiber has an average particle size of not more than 100 nm.
8. The method of claim 7, wherein the insecticide is selected from the group consisting of pyrethrin, allethrin, phthalthrin, resmethrin, furamethrin, phenothrin, Wherein the insecticidal composition is a pyrethroid insect repellent selected from the group consisting of permethrin.

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