KR20140055831A

KR20140055831A - Method for preparing controlled-release core skin type composite fiber and composite fiber made thereof

Info

Publication number: KR20140055831A
Application number: KR1020120123179A
Authority: KR
Inventors: 오성진; 이민석; 박종윤
Original assignee: 주식회사 효성; 주식회사 폴리크롬
Priority date: 2012-11-01
Filing date: 2012-11-01
Publication date: 2014-05-09

Abstract

The present invention relates to a method for manufacturing sustained-release core skin type composite fiber. The method includes a step of manufacturing a master batch chip by mixing sustained-release microcapsules comprising a hybrid resin carrying a sustained-release organic matter with a nylon resin with a low-melting point or a polyester resin with a low-melting point and a step of manufacturing yarn through a melt-spinning core skin type spinneret by placing the master batch chip in the core skin and the nylon or polyester chip in the skin. According to the present invention, the method can improve spinning efficiency and productivity while maintaining a sustained-release effect on a human-friendly sustained-release organic matter by improving heat resistance during the spinning of microcapsules.

Description

TECHNICAL FIELD [0001] The present invention relates to a method for preparing a sustained core-sheath type conjugated fiber, and a composite fiber produced by the method.

The present invention relates to a method for producing a sustained-flowing core-sheath type conjugated fiber and a composite fiber produced thereby, and more particularly to a hybrid type composite resin comprising a sustained-release microcapsule composed of a hybrid- To a process for producing a sustained-release core-sheath type conjugate fiber produced by using a low-melting-point polymer as a core, and to a sustained-release core-sheath type conjugate fiber produced thereby.

Recently, various types of functional fibers have been released in accordance with the trend of high-end of the fiber products. Among them, the sustained-release fiber is a fiber using a controlled-release of a specific compound.

. Especially, as interest in health and wellness has increased with the improvement of living standards, researches to develop high value-added human-friendly fibers including aromatic substances beneficial to the human body such as phytoncide, aroma, vitamin, and herb have been actively carried out.

One of the production methods of aromatic fibers is a method of applying a liquid agent containing a directional substance to a fiber through a post-treatment process. However, such a post-treatment process is remarkably deteriorated in performance by dyeing or washing, There is a problem that can not be maintained continuously.

Japanese Unexamined Patent Publication No. 6-322612 discloses a sustained-release core-sheath type conjugate fiber composed of a core portion composed of a polymer comprising a fiber-forming polymer and a polymer including a porous material carrying an sustained-release component. However, in this conventional technique, the dispersibility of the porous material such as silica carrying the sustained organism is poor and the particle distribution is not uniform, so that the spinning is poor. In particular, the production of long fibers by melt spinning There was an inadequate problem.

On the other hand, the present applicant discloses a master batch chip by mixing a microcapsule composed of a melamine resin, a urea resin or a melamine-urea-urea composite resin bearing a sustained release material and a thermoplastic resin in Patent Application Publication No. 2012-78238 And then melt-spinning the resultant mixture with another thermoplastic resin chip to produce a sustained-release core-sheath type conjugate fiber. However, when the slow-releasing organism is microencapsulated using melamine resin, urea resin or a composite resin thereof, there is a limit to improvement in heat resistance. Generally, polyamide-based or polyester-based fibers emit at a spinning temperature of 260 to 300 ° C. When microcapsules are mixed and radiated, more than 50% of the microcapsules containing the directional organism charged are lost due to thermal decomposition, And a toxic gas such as formaldehyde may be generated by pyrolysis of the microcapsules.

SUMMARY OF THE INVENTION It is an object of the present invention to improve the heat resistance of microcapsules and to minimize the thermal decomposition of the microcapsules during the spinning operation and to reduce the amount of toxic gas generated by carbonization of the microcapsules The present invention provides a method for producing a sustained-release core-sheath type conjugated fiber capable of remarkably reducing the yield of the core-sheath type conjugated fiber.

Another method of the present invention is a method for producing a sustained-release core-sheath type conjugate fiber which further improves the western function while using microcapsules containing a small amount of aromatic organics and also provides excellent spinnability, To provide a core-sheath type conjugated fiber.

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

One aspect of the present invention for achieving the above object is to provide a method for producing a master batch microcapsule by mixing a slow release microcapsule composed of a hybrid resin bearing a sustained organism and a polyolefin based low melting point nylon or low melting point polyester resin, Lt; / RTI > And

And a step of preparing a yarn by melt-spinning the yarn through a core-sheath type spinneret using the master batch chip as a core part and the general nylon or polyester chips as an initial part.

Another aspect of the present invention resides in a method for producing a microcapsule comprising a sustained release microcapsule made of a hybrid resin containing a sustained organism carried on a core part and a polyolefin based low melting point nylon based or low melting point polyester resin, To a sustained-release core-sheath type conjugate fiber comprising nylon or a polyester resin.

According to the method of the present invention, it is possible to improve the heat resistance of the microcapsule by using the hybrid type composite resin, to significantly reduce the loss of microcapsules due to mixing with the polyamide or polyester fibers and pyrolysis during the composite spinning, As the thermal decomposition of the microcapsule is reduced, the amount of toxic gas generated during the microcapsule carbonization can be remarkably reduced. In addition, it is possible to remarkably improve the problem of the increase of the radial packing pressure due to the carbonized organic material generated in the thermal decomposition of the microcapsules, and at the same time to manufacture the functional fiber which further improves the western function which is beneficial to the human body.

The sustained-release core-sheath type conjugate fiber produced by the production method of the present invention is excellent in antimicrobial property, deodorization property, moisturizing property, and excellent spinnability while maintaining the sustained effect of the beneficial ingredient on the human body .

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional photograph of a composite fiber produced by a method for producing a sustained-flowing core-sheath type conjugate fiber according to an embodiment of the present invention.

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.

In the method of one embodiment of the present invention, a sustained-release microcapsule composed of a hybrid resin containing 30 to 80 wt% of a human-friendly sustained-release organism is mixed with a polyolefin-based, low-melting-point nylon- A master batch chip containing 1 to 20% by weight of capsules is prepared, and then master nylon or polyester resin is co-extruded at the core portion of the master batch chip.

The master batch chip is a western blot consisting of a melamine-based, urea-based, urethane-based, urethane-based or hybrid-type resin containing 0.3 to 16 wt% of a sustained organism such as phytoncide, aroma, And then 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 30 to 80% by weight. The master batch chip comprises 1 to 20% by weight of sustained release microcapsules. Then, using the master batch chip as a core part and a general nylon or general polyester chip as an initial part,

Melt spinning to produce yarn.

The polyolefin-based, low-melting-point nylon-based or low-melting-point polyester resin constituting the core part forms a prepolymer for the prevention of pyrolysis of slow-releasing organisms (phytoncide, aroma, vitamin, herb, etc.) contained in microcapsules and microcapsules It is preferable to use one having a melting point lower than that of nylon or polyester resin. In this case, the polyolefin-based, low-melting-point nylon-based or low-melting-point polyester-based resin constituting the core part may be the same kind as the nylon or polyester resin constituting the core part or different kinds thereof may be used.

In the present invention, the polyolefin-based low-melting-point nylon-based or low-melting-point polyester-based resin constituting the core part has a melting point of 60 to 220 캜 and the melting point of the nylon or polyester resin constituting the core part is 210 to 260 캜.

Examples of the polyolefin-based, low-melting-point nylon-based or low-melting-point polyester-based resin constituting the core part include low-melting-point olefin polymers such as polyethylene, ethylene-vinyl acetate copolymer and polypropylene, low melting point polyesters, Nylon and the like.

In the method for producing a conjugate fiber according to an embodiment of the present invention, the polyolefin-based, low-melting-point nylon-based or low-melting-point polyester resin constituting the core portion 20 may be a waxy resin composed of a hybrid- And 1 to 20% by weight of the microcapsule. The sustained-release organism refers to a sustained-release substance that gradually volatilizes in the air. The sustained substance that can be used in the present invention is not particularly limited, but preferably a sustained organism useful for the human body such as phytoncide, aroma, vitamin, It is good to do. In this case, when the content of the microcapsules contained in the polyolefin-based, low-melting-point nylon-based or low-melting-point polyester-based resin constituting the core part is less than 0.5% by weight, the sustained- , There is a possibility that problems such as deterioration in radioactivity and defective dyeability may occur without significant improvement in functionality. 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 method for producing the sustained-flowing core-sheath type conjugate fiber according to an embodiment of the present invention, the spinning temperature is preferably about 180 to 290 ° C. If the spinning temperature is lower than 180 ° C, uniform melting does not occur, resulting in melt-fracture, resulting in poor processability and poor dyeability. If the spinning temperature is higher than 290 ° C, the thermal decomposition of the microcapsules and the slow- The functionality is lost.

In the method of producing a conjugate fiber according to an embodiment of the present invention, the hybrid resin constituting the microcapsule may be composed of a melamine resin, a urea resin, an epoxy resin, a urethane resin, or a composite resin thereof. When the melamine-based and urea-based resins are used singly or in combination, it is easy to control the thickness of the outer wall of the microcapsule with excellent heat resistance, and it is easy to support the sustained-release organisms in the desired amount.

Particularly, in the production method according to the present invention, the microcapsules preferably have an average particle diameter of 1.0 to 4.0 μm and a number average distribution of particles having an average particle diameter or less of 55 to 65%. 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,

As the number of coarse particles having an average particle diameter or more is large, the spinning workability is greatly reduced. Therefore, in order to prevent the coagulation phenomenon and improve the radiating processability, it is preferable that the distribution of the microcapsule fine particles is within the above range

.

The sustained-release core-sheath type conjugate fiber produced by the method of the present invention as described above may be a long fiber, and the single fiber fineness is about 1 to 6 denier. When the single fiber fineness is less than 1 denier, If the degree of deterioration is increased and the single fiber fineness exceeds 6 denier, there is a disadvantage that the feeling of touch is not smooth when the application is developed as a garment product.

Another aspect of the present invention relates to a sustained-release core-sheath type conjugate fiber produced by the method of the present invention. The sustained-release core-sheath type conjugate fiber of the present invention is produced by the method of the present invention, and comprises a sustained-release microcapsule (10) composed of a hybrid type resin in which a sustained organism is supported on a core part (20), a polyolefin type low melting point nylon type Or a low-melting-point polyester-based resin, and the initial portion 30 includes a general nylon or a polyester resin. 1, the sustained-release core-sheath type conjugate fiber of the present invention is characterized in that microcapsules 10 containing a human-friendly slow-releasing organism are distributed in the deep portion 20 of the cross-section of the conjugate fiber, and a human- It is continuously released for a sufficiently long period of time to further improve the western functioning.

The sustained release core-sheath type conjugate fiber of the present invention comprises 0.5 to 10% 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.

The sustained release core-sheath type conjugate fiber of the present invention can be used for clothes, bedding, carpets, curtains, etc., for example, when a forest bath flavoring such as phytoncide or other aroma ingredients are used as a sustained- 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, a method of producing the sustained-release core-sheath type conjugate fiber according to the present invention will be described in more detail with reference to examples. It should be understood, however, that the scope of the present invention is not limited to the disclosed embodiments.

Example 1

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 master batch chip and the nylon of the core thus prepared were respectively fed by 60 to 40% by weight, respectively, and spun at a rate of 2,600 m / min at a deep spinning temperature of organic waste and an initial spinning temperature of 260 ° C to prepare 50 denier / 24 filament yarn Respectively. The cross section of the manufactured human-friendly conjugate fiber is shown in FIG. 1, and the properties, processability and functionality of the obtained conjugate fiber are evaluated and shown in Table 1 below. In the case of functional suture knitting, sock knitting and dyeing were performed using a sock knitting machine in a conventional manner, followed by slow release sensory evaluation, antibacterial activity and deodorization.

Example 2

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 solution was dried and filtered to about 325 mesh to prepare human-friendly sustained release phytoncide microcapsules.

The obtained 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 and 50 percent of the particles were melt-blended with a polypropylene resin (MI18) having a melting point of 165 DEG C to obtain a master batch having a fine particle content of 5 wt% (Hereinafter referred to as " MB chip ").

The master batch chip thus prepared was used as a polymer in the deep part of spinning, and general nylon (relative viscosity (RV) 2.6) was used as the polymer of the beginning part. The master batch chip and the nylon of the sole fabric thus prepared were respectively fed by 60 to 40 weight% and radiated at a rate of 2,600 m / min at a deep spinning temperature of organic waste, an initial spinning temperature of 260 ° C, and manufactured into a 70 denier / 24 filament yarn Respectively. The cross section of the manufactured human-friendly conjugate fiber is shown in FIG. 1, and the properties, processability and functionality of the obtained conjugate fiber are evaluated and shown in Table 1 below. In the case of functional suture knitting, sock knitting and dyeing were performed using a sock knitting machine in a conventional manner, followed by slow release sensory evaluation, antibacterial activity and deodorization.

Comparative Example One

500 g of styrene maleic anhydride (4 wt.%) 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 obtained 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 50% of particles having a size of 2.8 mu m or less were melt-blended with a polypropylene resin (MI18) having a melting point of 165 DEG C to obtain a master having a fine particle content of 5 wt% A master batch chip (hereinafter referred to as MB chip) was prepared.

The master batch chip thus prepared was used as a polymer in the deep part of spinning, and general nylon (relative viscosity (RV) 2.6) was used as the polymer of the beginning part. The master batch chip and the nylon of the sole fabric thus prepared were respectively fed by 60 to 40 weight% and radiated at a rate of 2,600 m / min at a deep spinning temperature of organic waste, an initial spinning temperature of 260 ° C, and manufactured into a 70 denier / 24 filament yarn Respectively. The physical properties, processability and functionality of the resultant conjugate 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 in a conventional manner, and then a sustained sensory evaluation, antibacterial property and deodorization property were measured.

Comparative Example 2

Using a general nylon chip (intrinsic viscosity of 0.64 dl / g) of our company, spinning was carried out at 260 ° C at a rate of 4,300 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 amount (3.0 wt%) after sock knitting and dyeing by a usual method using a hosiery knitting machine, and then subjected to a slow release sensory evaluation, Were measured

A typical nylon chip (intrinsic viscosity of 0.64 dl / g) was spun at 260 DEG C at a rate of 4,300 m / min using a conventional spinning apparatus to produce 50 denier / 24 filaments of circular multi-facets. The physical properties of the obtained fibers were measured and are shown together in Table 1 below.

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 (T _d , ° C) Organic waste 240 200 200 Microcapsules in fiber
Amount (wt%) 3.0 3.0 3.0 3.0 Microcapsule processing method Yarn incorporation Yarn incorporation Yarn incorporation Post-processing
process Number of deniers / filaments 50/24 70/24 70/24 50/24 Uniformity (Uster%) 1.0 1.0 1.6 0.9 Spinning performance (Full percentage,%) 96 97 76 98 VOC (Benzaldehyde)
Amount of release (/ / m ³ ) 59 58 151 76 Slow Sensitivity Evaluation
(Before washing) 5 points 5 points 4 points 5 points Slow Sensitivity Evaluation
(Washing 10 times) 5 points 4 points 2 points 1 point Slow Sensitivity Evaluation
(Washing 20 times) 4 points 4 points 1 point 1 point Antimicrobial activity (KS K 0693,
10 times after washing,%) 99.9 99.9 99.0 74.6 Deodorization rate (gas detection method,
10 times after washing,%) 36 32 26 18

[Property evaluation method]

1) Particle size and distribution of microcapsules

To measure the particle size and distribution of the microcapsules injected into the yarn, the cross section of the yarn was photographed 10 times at random using an electron microscope (SEM) equipped with an image analyzer, The distribution was calculated.

2) Heat resistance of microcapsules

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

3) Uniformity ( Uster %)

The uniformity (Uster%) was measured using a device of the Eveness Tester 80 model of Keisokki Co. to measure the uniformity of the fibers.

4) Radiation Operability

The full-cake ratio of the total number of production was measured as the full-scale ratio at a rate of 9 kg by operating the radiator for 120 hours.

5) VOC Detection evaluation

Washing condition: KS K ISO 6330

After washing 10 times, VOC gas (benzaldehyde) emission (EPA 8315 method) was measured.

6) Sue castle Sensory evaluation

Washing condition: KS K ISO 6330

After 10 sensory evaluations, the scores were measured on the basis of the following criteria, and the scores were expressed as average scores.

5 points: Excellent, 4 points: Excellent, 3 points: Average, 2 points: Poor, 1 point: Poor

7) Antimicrobial activity

Washing condition: KS K ISO 6330

After washing 10 times, antimicrobial activity against Staphylococcus aureus (KS K 0693 method) was measured.

8) Deodorization rate ( FITI: gas detection method)

KS K ISO 6330 After washing 10 times in the washing condition, the deodorization rate was measured by the following method by the following formula. At this time, test piece: 10 cm × 10 cm, gas bag: 5 L, gas in-gas amount: 3 L of ammonia, measurement time: after 2 hours, initial concentration: 100 ppm

[Equation]

Deodorization rate: ((C _b C _s ) / C _b ) × 100

In the above formula, C _b _is Blank, After 2 hours and the test gas concentration of the test gas remaining in the bag, C _s is the concentration being in the sample, the test gas remaining in the test gas back after 2 hours.

As can be seen from the results of Table 1, the sustained-release core-sheath type conjugate fiber produced according to the production method of the present invention has the same level of spinning operation as that of Comparative Example 2, which is a conventional polyester fiber subjected to post- It was found that the effect of the sustained release sensory evaluation, antimicrobial activity and deodorization rate after laundry was excellent, while maintaining uniformity and yarn uniformity. In particular, in the slow release sensory evaluation, scores of 4 points or more were maintained even after washing 20 times, so that the western function was further improved by the method of the present invention.

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 exemplary embodiments. This will be obvious.

10: Slow release microcapsule
20: deep
30:

Claims

Preparing a master batch chip by mixing a sustained release microcapsule composed of a hybrid system resin carrying a sustained organism and a polyolefin system, a low melting point nylon system or a low melting point polyester system; And
And a step of preparing a yarn by melt-spinning the core batch type chip as a core part and the general nylon or polyester chips as a core part through a core-sheath type spinneret.

The hybrid resin according to claim 1, wherein the hybrid type resin of the sustained release microcapsule is selected from the group consisting of a melamine resin, a urea resin, an epoxy resin, a urethane resin, A method for manufacturing a core-sheath type conjugated fiber.

The method of producing a sustained-release core-sheath type conjugate fiber according to claim 1, wherein the microcapsules have an average particle diameter of 1.0 to 4.0 占 퐉 and a particle diameter of not more than the average particle diameter is 55 to 65% .

The method of producing the sustained-release core-sheath type conjugate fiber according to claim 1, wherein the melting point of the resin constituting the core part is 60 to 220 占 폚 and the melting point of the resin constituting the starch part is 210 to 260 占 폚.

[3] The method according to claim 1, wherein the conjugate fiber has a monofilament fineness of 1 to 6 denier and a microcapsule content of 0.5 to 10% by weight.

[3] The method according to claim 1, wherein melt spinning is carried out at a spinning temperature of 180 to 290 [deg.] C.

The method according to any one of claims 1 to 6, wherein the conjugated fiber is a long fiber.

A process for producing a sustained release microcapsule comprising a sustained-release microcapsule composed of a hybrid resin bearing a slow-releasing organism on a core part and a polyolefin-based low-melting point nylon-based or low-melting-point polyester resin produced by the method of any one of claims 1 to 6 And a nylon or polyester resin in the beginning thereof.

A warp knitted product using a sustained-release core-sheath type conjugate fiber produced by the method of any one of claims 1 to 6.