KR101439732B1 - Mehtod for preperaing sustained release fiber by direct spinning and sustained release fiber prepared thereby - Google Patents

Abstract

The present invention relates to a method of producing a sustained-release fiber by direct radiation which is excellent in antimicrobial property, deodorizing property, moisturizing property and mosquito repellent effect while maintaining the emission effect of a sustained organic material beneficial to the human body without generating toxic gas upon thermal decomposition And a sustained-release fiber produced thereby.

Description

TECHNICAL FIELD [0001] The present invention relates to a method for producing a sustained-release fiber by direct spinning, and a sustained-release fiber produced by the same. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to a method for producing a sustained-release fiber by direct spinning and a sustained-release fiber produced thereby, and more particularly, to a method for producing a sustained-release fiber by direct spinning, which continuously provides useful functions to the human body, The present invention relates to a process for producing a sustained-release fiber and a sustained-release fiber produced thereby.

Recently, with the advancement of textile products, various kinds of functional fibers have been introduced. Among them, especially, the sustained-release synthetic fibers are synthetic fibers using the sustained release of certain organic compounds. (Aromatic) synthetic fibers. Particularly, as the age of aging increases interest in health, efforts to develop human-friendly fibers including various aromatic organic substances beneficial for human body such as phytoncide, aroma, vitamin, and herb have been continued.

As a part of this effort, there has been known a method of applying a liquid formulation containing a directional organic material to a fiber through a post-treatment process. However, such a post-treatment treatment method has problems in that the performance of the fiber is remarkably lowered by dyeing or washing, There is a problem that it can not be maintained continuously.

Japanese Patent Laid-Open Publication No. 61-201012 and Japanese Patent Laid-Open Publication No. 62-85010 disclose a core-sheath type core material in which a core portion of polyethylene containing a natural essential oil is disposed in a hollow portion of a fiber, Hollow fibers and core-sheath type hollow composite fibers have been disclosed. However, such conventional sustained-release conjugate fibers do not continuously exhibit the effect of releasing the essential oil, and the problem of the orientation degradation due to the post-processing step and the short- there was.

Japanese Unexamined Patent Publication (Kokai) No. 6-322612 discloses a core-sheath type sustained-release composite fiber composed of a core portion made of a polymer including a sheath portion made of a fiber-forming polymer and a porous material having a sustained release material Lt; / RTI > However, in such conventional techniques, the dispersibility of the porous material such as silica carrying the sustained release material is poor, the particle distribution of the porous material is not uniform, and the spinning is poor. Particularly, There is a problem in that it is not suitable for the production of long fibers by the above method.

On the other hand, in Korean Patent Publication No. 2012-0078238, microcapsules are prepared by adding a slow-release organic material to a melamine resin, a urea resin or a composite resin of a melamine resin and a urea resin, Was incorporated into a polyamide-based or polyester-based polymeric material and spinned to prepare a method for producing sustained-release fibers by direct spinning. However, in the case of producing the sustained-release conjugate fiber according to this method, since the heat resistance of the microcapsule itself is limited, the microcapsule can not withstand the high spinning temperature of 260 to 300 ° C., and more than 50% of the microcapsules are thermally decomposed and lost, There is a problem in that the addition effect thereof is not remarkably expressed in the conjugate fiber. In addition, when the microcapsules are thermally decomposed, toxic gases such as formaldehyde (VOC), which can be fatal to the human body, are generated.

It is an object of the present invention to solve the above problems of the prior art, and it is an object of the present invention to provide a method and apparatus for continuously dissolving a sustained organic material, which is advantageous for a human body without generating toxic gas during pyrolysis, , Moisture retention, mosquito repellent effect, and the like.

Another object of the present invention is to provide a method for producing the sustained-release fiber described above.

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

According to an aspect of the present invention,

A master batch chip is prepared by mixing one or more resins selected from the group consisting of a slow release microcapsule composed of a hybrid type resin carrying a sustained organism and a polyolefin type, a low melting point nylon type and a low melting point polyester type resin , And directly spinning the master batch chip. The present invention also relates to a method for producing a sustained-release fiber by direct spinning.

Another aspect of the present invention resides in a method for producing a sustained-release microcapsule comprising a sustained-release microcapsule made of a hybrid resin containing a sustained organism carrying thereon and a sustained-release fiber comprising a polyolefin-based, low melting point nylon- .

According to the present invention, the amount of microcapsules that are pyrolyzed and lost during spinning is remarkably reduced, so that the amount of toxic gas (VOC) generated during microcapsule carbonization is remarkably lowered, and the amount of carbonized organic matter The problem of the increase of the radiation pressure due to the radiation is also remarkably improved.

Further, the method of producing sustained-release fiber by direct spinning according to the present invention exhibits excellent antimicrobial property, deodorizing property, moisturizing property, and mosquito repellent effect while maintaining the emission effect of the sustained-release organic material beneficial to the human body.

1 is a cross-sectional photograph of a sustained-release fiber produced by the method of the present invention.

Hereinafter, the present invention will be described in more detail with reference to examples.

In the method of the present invention, one or more resins selected from the group consisting of a sustained-release microcapsule composed of a hybrid resin bearing a slow-releasing organism and a polyolefin-based, low-melting-point nylon- After the chip is manufactured, the master batch chip is melt-spun directly to produce a sustained-release fiber.

In the present invention, examples of a human-friendly sustained-release organic material carried on a microcapsule made of a hybrid resin include phytoncide, an aroma, a vitamin, a herb, an antibacterial agent, a deodorant, a moisturizer, a mosquito repellent ) And the like.

The master batch chip is prepared by preparing a sustained-release microcapsule composed of a melamine-based, urea-based, epoxy-based, urethane-based or hybrid-type resin which is a composite resin thereof carrying a sustained organism such as phytoncide, aroma, And mixing the slow-release microcapsules with a polyolefin fin system, a low melting point nylon system or a low melting point polyester resin. The sustained-release microcapsule may contain a sustained-release organism in an amount of 10 to 50% by weight. The master batch chip comprises 1 to 20% by weight of sustained release microcapsules. Followed by direct spinning of the master batch chip to produce sustained-release fibers.

If the content of the microcapsules contained in the polyolefin-based, low-melting-point nylon-based or low-melting-point polyester-based resin is less than 0.5% by weight, sustained release to the extent that the human body can feel is not expressed, and if it exceeds 10% by weight, It may cause problems such as deterioration of radioactivity, defective dyeing, and the like. In this case, each of the microcapsules may contain 10 to 50 wt% of the slow-releasing organism. When the content of the slow-releasing organism is less than 10 wt%, the sustained-release property is lowered compared to the microcapsule addition amount. It is difficult to manufacture capsules, and pyrolysis of internal slow-releasing organisms easily occurs.

In the present invention, by using a hybrid resin such as a melamine resin, a urea resin, an epoxy resin and a urethane resin, the heat resistance of the microcapsule, that is, the decomposition temperature, is increased from 200 ° C. to 240 ° C., It is possible to remarkably reduce the amount of microcapsules to be lost due to the presence of the microcapsules. Accordingly, the amount of toxic gas generated in the microcapsule carbonization can be remarkably reduced, and the problem of the increase of the radiation pressure due to the carbonized organic matter generated in the thermal decomposition of the microcapsules can be remarkably improved.

In the present invention, as the fiber-forming thermoplastic polymer resin, polyolefin-based, low-melting-point nylon-based resin or low-melting-point polyester-based resin can be used. Such a polyolefin-based, low-melting-point nylon-based or low-melting-point polyester-based resin has a melting point of 60 to 220 ° C.

Examples of the polyolefin-based, low-melting-point nylon-based, low-melting-point polyester resin that can be used as the fiber-forming thermoplastic polymer resin in the present invention include polypropylene, polyethylene, nylon 6, nylon 11, nylon 12 and nylon 610, Phthalate) (PET), poly (1,3-propylene terephthalate) (PPT), and the like.

The microcapsules carrying the sustained-release organic material preferably have an average particle size of 1.0 to 4.0 μm and a number average distribution of particles having an average particle size or less of 55 to 65% or so. The scattering of particle size upon incorporation of microcapsules directly affects dispersibility and spinnability. If the number of particles having a particle size smaller than the average particle size of the microcapsule is too large, there is a possibility that the spinning workability and the pressure increase due to coagulation of the fine particles may occur. On the other hand, if the distribution of the inorganic 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 as there are many coarse particles having an average particle diameter or more, Therefore, in order to prevent the aggregation phenomenon and improve the radiation processability, it is preferable that the distribution of the microcapsule fine particles is within the above range. When the particle size of the microcapsules is less than 1.0 탆, the problem of insufficient containment of the slow-release organic material occurs. On the other hand, when the size of the microcapsules exceeds 4.0 탆, the surface of the fibers after spinning is cratered Which is undesirable.

Another aspect of the invention relates to sustained release fibers made by the process of the present invention. The sustained-release fiber of the present invention comprises a sustained-release microcapsule made of a hybrid resin bearing a sustained-release organism and a polyolefin-based, low-melting-point nylon-based or low-melting-point polyester resin produced by the method of the present invention. As shown in Fig. 1, the sustained-release fiber of the present invention has a structure in which microcapsules containing a human-friendly slow-release organism are evenly distributed on the cross-section of the conjugate fiber, and a human-friendly slow-release organism is continuously released for a sufficiently long period of time, Is further improved.

The sustained-release fiber of the present invention comprises 1 to 20% by weight of sustained-release microcapsules composed of a hybrid type resin carrying a sustained organism. When the content of the sustained-release microcapsule in the fiber is less than 0.5% by weight, the sustained-release effect is insignificant and the human body is hardly felt. When the sustained-release microcapsule is more than 10% by weight, radioactivity and dyability deteriorate, Which can lead to disadvantages.

500 g of 4 wt.% Of styrene maleic anhydride, 250 g of white oil and 25 g of epoxy resin are mixed well and emulsified in a homogenizer at 6000 rpm for 10 minutes. 33 g of the melamine initial condensate was added during the emulsification, and the mixture was reacted at 85 ° C for about 8 hours at pH 5.5, and then cooled to room temperature. Then, 9.6 g of diethylene triamine was added thereto, and the temperature was raised to 75 ° C. After stirring for about 8 hours, the total amount was adjusted to 1000 g, and the liquid was dried and filtered to about 400 mesh to prepare human-friendly sustained release phytoncide microcapsules.

The resulting human-friendly sustained-release phytoncide microcapsules were mixed with a low melting point nylon copolymer at a concentration of 5% by weight to prepare a master batch chip (hereinafter referred to as "MB chip"). At this time, the fine particles having an average size of 2.6 탆 and a particle size of 2.6 탆 or less having 65% of the microcapsules were copolymerized at a melting point of 160 캜 comprising 45% by weight of caprolactam and 55% by weight of 12- Melting point nylon resin to prepare a master batch chip having a fine particle content of 5% by weight. The master batch chip thus prepared is used as a polymer in the deep portion during spinning. Normal nylon (relative viscosity (RV) 2.6) is used as the shear polymer. The deep master batch chip and nylon nylon thus prepared were respectively fed at a rate of 60 to 40% by weight and spun at a rate of 2,600 m / min at a deep-part spinning temperature of 230 ° C and an initial spinning temperature of 260 ° C to prepare 50 denier / 24 filament yarn .

The sustained-release fiber of the present invention can be used for clothes, bedding, carpets, curtains, and the like, for example, when a forest bath flavoring such as phytoncide or other aroma ingredients are used as the sustained-release component. The process of the present invention can also be applied to the manufacture of products containing insecticidal or antimicrobial substances, which products can be used in various sanitary products.

Hereinafter, the technical structure and operation effects of the present invention will be described in detail on the basis of specific examples, but these embodiments are merely for the purpose of more clearly understanding the present invention and are not intended to limit the scope of the present invention .

Example 1

500 g of 4 wt.% Of styrene maleic anhydride, 250 g of white oil and 25 g of epoxy resin are well mixed and emulsified in a homogenizer at 6000 rpm for 10 minutes. 33 g of the melamine initial condensate was added during the emulsification, and the mixture was reacted at 85 ° C for about 8 hours at pH 5.5, and then cooled to room temperature. Then, 9.6 g of diethylene triamine was added thereto, and the temperature was raised to 75 ° C. After stirring for about 8 hours, the total amount was adjusted to 1000 g, and the liquid was dried and filtered to about 400 mesh to prepare human-friendly sustained release phytoncide microcapsules.

The resultant human-friendly sustained release phytoncide microcapsules were mixed with a polypropylene resin at a concentration of 5% by weight to prepare a master batch chip. At this time, fine particles having an average size of microcapsules of 2.6 占 퐉 and having a size of 2.6 占 퐉 or less were dispersed in a polypropylene having a melting point of 160 占 폚 comprising 45% by weight of caprolactam and 55% by weight of 12- (MI 18) to prepare a master batch chip having a fine particle content of 5% by weight. The master batch chip thus produced was melt-spun directly and spun at a spinning temperature of 230 DEG C at a speed of 2,600 m / min to produce 50 denier / 24 filament yarn.

The cross section of the manufactured human-like orthotropic fibers was as shown in Fig. 1, and the physical properties, processability and functionality of the obtained polypropylene fibers were evaluated and shown in Table 1 below. In the case of functionality, sock knitting and dyeing were performed using a sock knitting machine by a conventional method, and then a sustained sensory evaluation, antibacterial property and deodorization property were measured.

Example 2

500 g of 4 wt.% Of styrene maleic anhydride, 250 g of white oil and 25 g of epoxy resin are mixed well and emulsified in a homogenizer at 6000 rpm for 10 minutes. 33 g of the melamine initial condensate was added during the emulsification, and the mixture was reacted at 85 ° C for about 8 hours at pH 5.5, and then cooled to room temperature. Then, 9.6 g of diethylene triamine was added thereto, and the temperature was raised to 75 ° C. After stirring for about 8 hours, the total amount was adjusted to 1000 g, and the solution was dried and filtered to about 325 mesh to prepare human-friendly sustained release phytoncide microcapsules.

The resulting human-friendly sustained-release phytoncide microcapsules were mixed with a polypropylene resin at a concentration of 5% by weight to prepare a master batch chip. At this time, fine particles having an average size of microcapsules of 2.8 mu m and having a particle size of 2.8 mu m or less were dispersed in a polypropylene having a melting point of 165 DEG C and consisting of 45 wt% of caprolactam and 55 wt% of 12- (MI 18) to prepare a master batch chip having a fine particle content of 5% by weight. The master batch chip thus prepared was directly melt-spun and spun at a spinning temperature of 230 占 폚 at a speed of 2,600 m / min to prepare a 70 denier / 24 filament yarn.

The cross section of the manufactured human-like orthotropic fibers was as shown in Fig. 1, and the physical properties, processability and functionality of the obtained polypropylene fibers were evaluated and shown in Table 1 below. In the case of functionality, sock knitting and dyeing were performed using a sock knitting machine by a conventional method, and then a sustained sensory evaluation, antibacterial property and deodorization property were measured.

Comparative Example  One

500 g of 4 wt.% Of styrene maleic anhydride and 250 g of soft white oil are mixed well and emulsified in a homogenizer at 6000 rpm for 10 minutes. During the emulsification, 44 g of the melamine initial condensate was added, and the mixture was reacted at 85 ° C. for about 8 hours at pH 5.5. The total amount of the melamine condensate was adjusted to 1000 g, and the mixture was then dried to form phytoncide microcapsules at about 325 mesh.

The resulting human-friendly sustained-release phytoncide microcapsules were mixed with a polypropylene resin at a concentration of 5% by weight to prepare a master batch chip. At this time, fine particles having an average size of microcapsules of 2.8 mu m and having a size of 2.8 mu m or less were dispersed in a polypropylene having a melting point of 165 DEG C and consisting of 45 wt% of caprolactam and 55 wt% of 12- (MI 18) to prepare a master batch chip having a fine particle content of 5% by weight. The master batch chip thus prepared was directly melt-spun and spun at a spinning temperature of 230 占 폚 at a speed of 2,600 m / min to prepare a 70 denier / 24 filament yarn.

The physical properties, processability and functionality of the obtained polypropylene fiber were evaluated and are shown in Table 1 below. In the case of functionality, sock knitting and dyeing were performed using a sock knitting machine by a conventional method, and then a sustained sensory evaluation, antibacterial property and deodorization property were measured.

Comparative Example  2

Using a general polypropylene chip (MI 18) of our company, spinning was carried out at 230 ° C at a rate of 2,600 m / min using a conventional spinning apparatus to produce 50 denier / 24 filaments of circular multi-facets. The physical properties, processability and functionality of the prepared fibers were evaluated and are shown in Table 1 below. In the evaluation of the functionality, the same phytoncide microcapsules as in Example 1 were post-treated after the same content (5.0% by weight) after the sock knitting and dyeing by the usual method using a sock knitting machine and then subjected to a sustained- Were measured.

division Example 1 Example 2 Comparative Example 1 Comparative Example 2 Microcapsule average size (탆) 2.6 2.8 2.8 2.6 Particle distribution (%)
(Below average) 65 60 50 65 Heat resistance of microcapsules (Td, ℃) 230 240 200 230 Amount of microcapsule incorporation in fiber (wt%) 5.0 5.0 5.0 5.0 Microcapsule processing method Yarn incorporation Yarn incorporation Yarn incorporation Post-processing Number of deniers / filaments 50/24 70/24 70/24 50/24 Worcester uniformity (%) 1.0 1.0 1.6 0.9 Spinning performance (Full percentage,%) 96 97 90 98 VOC (benzaldehyde)
Amount of release (/ / m ³ ) 59 58 151 76 Slow Sensitivity Evaluation
(Before washing) 5 points 5 points 5 points 5 points Slow Sensitivity Evaluation
(Washing 10 times) 5 points 4 points 3 points 2 points Slow Sensitivity Evaluation
(Washing 20 times) 4 points 4 points 2 points 1 point Antimicrobial activity (KS K 0693,
After washing 10 times,%) 99.9 99.9 99.0 74 Deodorization rate (gas detection method,
After washing 10 times,%) 36 32 26 18

Property evaluation method

1. Particle Size and Distribution of Microcapsules

In order to measure the particle size and the distribution of the microcapsules put into the yarn, the cross section of the yarn was photographed 10 times at random using a transmission electron microscope (SEM) equipped with an image analyzer, and the average particle size of the microcapsules Size and distribution of it.

2. Heat resistance of microcapsule

TGA (Thermal Gravimetric Analysis) is heated from room temperature to 700 ° C at a rate of 20 ° C / min under an air atmosphere, and the weight loss due to pyrolysis is measured. At this time, the temperature at which weight reduction starts is expressed as a thermal decomposition temperature (Td).

3. Worcester Uniformity (%)

Evenness Tester; Manufacturer: Keisokki Kogyo Co., Ltd.; (%) Was measured using a model name: KET-80V / C.

4. Radiation Operability

The radiator was operated for 120 hours, and the ratio of the full cakes to the total number of production was measured based on the volume of 9 kg as the fullness ratio.

5. VOC  Detection evaluation

After washing 10 times according to KS K ISO 6330 for Textile-Domestic Washing and Drying Procedures for Textile Testing, the emission of VOC gas (benzaldehyde) was measured by EPA Protection Agency) 8315 method.

6. Sue castle  Sensory evaluation

Ten people were evaluated for sensory evaluation before washing, 10 times for washing and 20 times for washing according to KS K ISO 6330, and the scores were measured on the basis of the following criteria, and the results were expressed as average scores and evaluated as shown in Table 2 below.

score evaluation 5 points Very good 4 points Great 3 points usually 2 points Inadequate 1 point Bad

7. Antimicrobial activity

The antimicrobial activity against Staphylococcus aureus was measured according to KS K 0693 on Test Method for Antibacterial Activity of Textile Materials after washing 10 times according to KS K ISO 6330.

8. Deodorization rate

According to KS K ISO 6330, washing was performed 10 times and the deodorization rate was measured according to the formula based on the Gas Detecting Tube Method of FITI test institute under the following conditions.

1) Test piece: 10 cm x 10 cm

2) Gas bag capacity: 5L

3) Gas volume in gas bag: Ammonia 3L

4) Measurement time: After 2 hours, initial concentration: 100 ppm

[Equation]

((C _b - C _s ) / C _b ) × 100

In the above formula,

C _b is the blank, represents the concentration of the test gas remaining in the test gas bag after 2 hours, C _s is the sample, and after 2 hours the concentration of the test gas remaining in the test gas bag to be.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, Will be apparent to those skilled in the art. Accordingly, the scope of protection of the present invention should be defined in the appended claims and their equivalents.

Claims (7)

Sustained-release microcapsule composed of a hybrid resin carrying a sustained-organism and a polyolefin, selected from the group consisting of a melting point of low melting point nylon-series 60 ~ 220 ℃ and the melting point is composed of a low-melting polyester resin is 60 ~ 220 ℃ ≪ / RTI > to produce a master batch chip ; And
Directly radiating the master batch chip ,
Wherein the hybrid resin is selected from the group consisting of a melamine resin, a urea resin, an epoxy resin, a urethane resin, and any of these composite resins .
delete The method of claim 1, wherein the slow release organic material is selected from the group consisting of phytoncide, aroma, vitamin, herb, antimicrobial agent, deodorant, moisturizer and mosquito repellent.
The method of claim 1, wherein the sustained-release organic material is supported on the microcapsules in an amount of 10 to 50% by weight based on 100% by weight of the microcapsules.
The method of claim 1, wherein the average particle size of the microcapsules is in the range of 1.0 to 4.0 탆.
A sustained-release microcapsule composed of a hybrid resin carrying a sustained organism and produced by the method of any one of claims 1 to 5 and a polyolefin-based, low-melting-point nylon-based and low-melting-point polyester- And a resin selected from the group consisting of resins.
A fiber product produced by the method of any one of claims 1 to 5.

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