KR20160083516A - low melting polyester complex fiber having soft touch and preparation method of the same - Google Patents

Abstract

More particularly, the present invention relates to a biodegradable shrinkable filament yarn having excellent biodegradability, excellent stretchability and excellent stretchability and a method for producing the same.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a polyester fiber having a soft,

More particularly, the present invention relates to a biodegradable shrinkable filament yarn having excellent biodegradability, excellent stretchability and excellent stretchability and a method for producing the same.

As the culture of mankind developed, clothing was worn. As a material of these clothes, it progressed from the leaves of primitive plants or animal fur to separate the fibers from the root and the plant, pulled the thread from them and made the fabric by weaving thread. Fiber production began.

As described above, fibers that can be directly obtained from natural materials are called natural fibers, and specifically, natural fibers mean fibers that can be obtained directly from animals, plants, and minerals. The types are largely divided into animal fibers, vegetable fibers, and mineral fibers. They can be used immediately without being woven like felt or paper, or they can be made into yarns first, then weaving the yarns to make fabrics. Vegetable fibers include cotton, flax, and jute composed of cellulose. Animal fiber is a component of protein, and there are mohair, mohair, and dog. Mineral fibers have asbestos. All natural fibers are susceptible to mold or decay by microorganisms. Animal fibers are easily damaged by moths or claws, and cellulosic fibers are damaged by termites and mites.

However, due to population growth and cultural development, the demand for fiber rapidly increased, and as the use of Chicago fiber expanded, natural fibers only needed new fiber materials because they could not meet the increasing demand for fibers and the newly required properties. It has come to the artificial fiber or chemical fiber. In line with the development of the petrochemical industry, chemical fibers have been able to synthesize polymers from simple compounds obtained from the petrochemical industry as raw materials, and synthetic fibers are used to make fibers with this synthetic polymer.

Such synthetic fibers include nylon, polyester, acrylic, polypropylene, and vinylon fiber, and they are used as industrial and industrial materials beyond clothing.

However, in the case of the above-mentioned synthetic fibers, since they are not degraded in the natural environment but exist semi-permanently, they cause a lot of environmental problems. In recent years, it has been revealed that environmental hormones that disturb the endocrine system are released when certain compounds are used. .

In the past, synthetic fibers have been treated through landfilling, incineration, and recycling. However, in the case of landfilling, there is a shortage of landfill space due to the increasing amount of garbage, and the collective self-interest caused by residents in the surrounding area is worsening. it's difficult. In addition, since the ground is not stable due to the synthetic fiber waste which is difficult to be decomposed even after landfilling, there are many problems in utilization of the landfill. In case of incineration of the landfill, dusts are scattered and harmful gases such as dioxins and carbon monoxide And it causes air pollution and serious harm to the human body.

As a method for solving all of these problems, researches and developments related to biodegradation for decomposing existing synthetic fibers themselves have been made variously, and researches on biodegradable polyester fibers as one of the above research and development have been actively continued.

Korean Patent No. 1049601 discloses a biodegradable polyester mixture, and Korean Patent No. 0428687 discloses a biodegradable polyester resin composition reinforced with tearing strength.

However, conventional biodegradable polyester fibers have a problem in that it is difficult to develop for various applications due to low physical properties.

On the other hand, stretchability is a characteristic that synthetic fibers can not be easily expressed, and is regarded as an intrinsic property of natural fibers such as wool. Conventional techniques for imparting stretchability to synthetic fibers include (1) a method of producing two kinds of synthetic fibers (yarns) having a large difference in elongation property by compression-twisting-thermo-setting to produce this shrinkable composite false- A method of mixing polyurethane fibers and other synthetic fibers having excellent stretchability in the longitudinal direction at the time of manufacturing, and (3) methods of producing conjugated fibers by complex spinning of two types of polymers.

Among the above methods, the method of producing the shrinkage composite false-twist yarn is a method of giving potential difference in shrinkage ratio by twin-twisted yarns of two kinds of yarns having large differences in elongation properties. In other words, by using the difference of deformation ratio and residual deformation ratio after cracking in the flammable region to the maximum extent, it is more distorted in judging and superimposition, and is intertwined with judging. The shrinkage-warpable warp yarns exhibit good stretchability due to differences in elongation properties between the warp yarn and the warp yarn during heat treatment in the post-treatment process. However, this method is disadvantageous in that the expression state of the crimp is non-uniform and the binding force between the crimp and the superpowder depends on air entanglement or the like, so that one component yarn is separated or removed by the physical force applied during the post- there was.

Therefore, it is an urgent point to develop a shrinkage hybrid fiber which not only maintains or improves the biodegradability of conventional biodegradable polyester fibers but also has excellent stretchability.

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 it is an object of the present invention to provide a biodegradable shrinkable filament yarn excellent in stretchability and biodegradability.

In order to solve the above-described problems, the present invention provides a biodegradable polyester resin composition comprising: a biodegradable polyester resin; And polylactide (PLA) resins; Wherein the biodegradable polyester resin and the polylactide (PLA) resin are bonded in a side-by-side manner, and the biodegradable polyester resin has an intrinsic viscosity (IV) of 0.54 To 0.82 dl / g, and the polylactide (PLA) resin has an intrinsic viscosity (IV) of 1.42 to 2.14 dl / g.

According to a preferred embodiment of the present invention, the biodegradable shrink-fusible fiber according to the present invention may have a reduction rate of intrinsic viscosity (IV) according to the following formula (1): 80% or more.

[Equation 1]

Intrinsic viscosity reduction rate (%) =

At this time, it means that the sample is immersed in distilled water at 100 ° C at pH 7.

According to a preferred embodiment of the present invention, the biodegradable shrink-fusible fiber of the present invention may contain the biodegradable polyester resin and the polylactide (PLA) resin at a weight ratio of 3 to 7: 7 to 3.

According to a preferred embodiment of the present invention, the biodegradable shrink-fusible yarn of the present invention may have a crimp ratio of 8 to 20 / inch and a crimp ratio of 10 to 25 in the biodegradable shrink-fusible yarn.

According to a preferred embodiment of the present invention, the biodegradable shrinkage blend yarn of the present invention may have a shrinkage ratio of 3 to 15% before and after heat treatment at 180 ° C for 20 minutes.

According to a preferred embodiment of the present invention, the biodegradable polyester resin of the biodegradable shrink-fusible fiber according to the present invention comprises a copolymer of an acid component and a diol component, wherein the acid component and the diol component are mixed at a ratio of 1: 1.1 to 2.0 Molar ratio.

According to a preferred embodiment of the present invention, the acid component of the biodegradable shrink-fusible fiber according to the present invention comprises at least one aromatic polycarboxylic acid component having 6 to 14 carbon atoms and at least one aliphatic polyvalent carboxylic acid having 2 to 16 carbon atoms And the diol component may comprise at least one of ethylene glycol, bio-ethylene glycol, diethylene glycol, neopentyl glycol, 1,3-propanediol, 1,4-butanediol and 1,6- have.

According to a preferred embodiment of the present invention, the aromatic polycarboxylic acid component having 6 to 14 carbon atoms of the biodegradable shrinkage fusible yarn of the present invention contains at least one of terephthalic acid, dimethyl isophthalate, isophthalic acid and dimethyl terephthalate can do.

According to a preferred embodiment of the present invention, the aliphatic polycarboxylic acid having 2 to 16 carbon atoms of the biodegradable shrink-fumed synthetic resin of the present invention is selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, And one or more of citric acid, fumaric acid, azelaic acid, sebacic acid, nonanoic acid, decanoic acid, dodecanoic acid, and hexanodecanoic acid.

According to a preferred embodiment of the present invention, the acid component of the biodegradable shrink-fusible yarn of the present invention may further include a sulfonic acid metal salt.

According to a preferred embodiment of the present invention, the sulfonic acid metal salt of the biodegradable shrink-fume fiber of the present invention is sodium 3,5-dicarbomethoxybenzenesulfonate, 5-sulfoisophthalic acid monosodium salt (5 -sulfoisophthalic acid monosodium salt) and dimethyl 5-sodiosulfoisophthalate.

According to a preferred embodiment of the present invention, the acid component of the biodegradable shrink-fusible fiber according to the present invention comprises terephthalic acid, an aliphatic dicarboxylic acid component having 2 to 16 carbon atoms for improving biodegradability and a sulfonic acid metal salt . ≪ / RTI >

According to a preferred embodiment of the present invention, the biodegradable shrink-fusible fiber of the present invention is characterized in that the aliphatic dicarboxylic acid component having 2 to 16 carbon atoms for improving the biodegradability is an adipic acid and improves biodegradability The sulfonic acid metal salt may be sodium 3,5-dimethoxybenzenesulfonate.

According to a preferred embodiment of the present invention, the adipic acid of the present invention for improving the biodegradability of the biodegradable shrink-fusible fiber can be contained in an amount of 5 to 15 mol% based on the total acid content.

According to a preferred embodiment of the present invention, the acid component of the biodegradable shrinkage-resistant synthetic fiber of the present invention comprises an aromatic polycarboxylic acid component having 6 to 14 carbon atoms and an aliphatic polycarboxylic acid component having 2 to 14 carbon atoms 95 to 99.9 mol% of at least one component selected from the group consisting of sodium 3,5-dicarbomethoxybenzenesulfonate, 5-sulfoisophthalic acid monosodium salt and dimethyl 5- Wherein the diol component is selected from the group consisting of ethylene glycol, diethylene glycol, neopentyl glycol, 1,3-propanediol, 1,4-butanediol, and 1,6-hexane And 100 mole% of at least one component of the diol.

Further, the present invention provides a fabric or a nonwoven fabric comprising the above-mentioned biodegradable shrinkable filament yarn.

(1) a biodegradable polyester resin having an intrinsic viscosity (IV) of 0.54 to 0.82 dl / g and a polylactide (PLA) resin having an intrinsic viscosity (IV) of 1.42 to 2.14 dl / Side-by-side type spinning at a spinning speed of 1,000 to 1,500 mpm at 280 ° C, followed by stretching at a stretching ratio of 2.0 to 4.0 in a 60-80 ° C hot bath to produce filaments; (2) heat-treating the filament at a temperature of 100 to 210 DEG C for 5 to 30 seconds under a tension applied state; (3) preparing a crimped fiber using a crimp box capable of passing the heat-treated filament through 300 to 8000 deniers per mm; (4) a relaxation heat treatment step of fixing the crimper by heat-treating the crimped fibers at 40 to 120 ° C for 10 minutes to 30 minutes; And (5) cutting the relaxed heat-treated fiber to produce a biodegradable shrunk horny yarn having a fiber length of 30 to 60 mm; The present invention also provides a method for producing a biodegradable shrinkable filament yarn excellent in stretchability.

On the other hand, the term " horn island yarn " used in the present invention means a yarn produced through spinning in the detention, and the opposite concept is a yarn used as a processed horn yarn. Means manufactured

The biodegradable shrinkable filament yarn excellent in stretchability and excellent in stretchability of the present invention and its manufacturing method have not only biodegradability but also excellent stretchability.

Hereinafter, the present invention will be described in more detail.

As mentioned above, conventional synthetic fibers have been processed through landfilling, incineration, recycling, etc. However, in the case of landfilling, the landfill space becomes short due to the increasing amount of garbage, and the collective self- It is difficult to secure. In addition, since the ground is not stable due to the synthetic fiber waste which is difficult to be decomposed even after landfilling, there are many problems in utilization of the landfill. In case of incineration of the landfill, dusts are scattered and harmful gases such as dioxins, And it causes air pollution and serious harm to the human body.

As a method for solving all of these problems, researches and developments related to biodegradation for decomposing existing synthetic fibers themselves have been made variously, and researches on biodegradable polyester fibers as one of the above research and development have been actively continued.

However, conventional biodegradable polyester fibers have a problem in that it is difficult to develop for various applications due to low physical properties.

On the other hand, stretchability is a characteristic that synthetic fibers can not be easily expressed, and is regarded as an intrinsic property of natural fibers such as wool. As a conventional technique for imparting stretchability to synthetic fibers, there is a method of giving potential difference in shrinkage ratio by twin-yarn twist yarns having a large difference in elongation properties by folding-twisting-twisting. However, this method is disadvantageous in that the expression state of the crimp is non-uniform and the binding force between the crimp and the superpowder depends on air entanglement or the like, so that one component yarn is separated or removed by the physical force applied during the post- there was.

Therefore, it is an urgent point to develop a shrinkage hybrid fiber which not only maintains or improves the biodegradability of conventional biodegradable polyester fibers but also has excellent stretchability.

Accordingly, the present invention relates to a biodegradable polyester resin; And polylactide (PLA) resins; , Wherein the biodegradable polyester resin and the polylactide (PLA) resin are bonded in a side-by-side manner and the intrinsic viscosity (IV) reduction rate according to the following formula The present inventors have sought to solve the above-mentioned problems by providing a biodegradable shrinkable filament yarn excellent in stretchability, which is characterized by having a stretchability of not less than 80%. The present invention provides a biodegradable shrinkable filament yarn excellent in stretchability as well as biodegradability, .

The biodegradable shrinkage fiber of the present invention includes a biodegradable polyester resin and a polylactide (PLA) resin. First, the biodegradable polyester resin will be described.

The biodegradable polyester may include a copolymerized product of an acid component and a diol component.

The acid component may be used without limitation as long as it is an acid component commonly used in a biodegradable polyester resin. Preferably, the acid component is an aromatic polycarboxylic acid component, a polycarboxylic acid including a heterocycle, And more preferably the acid component may include an aromatic polycarboxylic acid component having 6 to 14 carbon atoms and an aliphatic polycarboxylic acid component having 2 to 16 carbon atoms ≪ RTI ID = 0.0 > and / or < / RTI >

The aromatic polycarboxylic acid component may include at least one of terephthalic acid, dimethylisophthalate, isophthalic acid, and dimethyl terephthalic acid.

In addition, the polycarboxylic acid containing the heterocycle may include at least one of 2,5-furandicarboxylic acid, 2,5-ciphopenedicarboxylic acid and 2,5-pyrrole dicarboxylic acid .

The aliphatic polycarboxylic acid component may be at least one selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, citric acid, pimelic acid, azelic acid, sebacic acid, nonanoic acid, decanoic acid, Canoinic acid, and hexanodecanoic acid. Preferably, the aliphatic polycarboxylic acid may include adipic acid, and the biodegradability may be increased by including adipic acid.

Meanwhile, the acid component may further include a sulfonic acid metal salt. By further including the sulfonic acid metal salt, adsorption of water molecules is induced, and the biodegradation effect is improved, thereby increasing the decomposition ability. The sulfonic acid metal salt may be at least one of sodium 3,5-dicarbomethoxybenzenesulfonate, 5-sulfoisophthalic acid monosodium salt, and dimethyl 5-sodiumdiosulfoisophthalate , And preferably the sulfonic acid metal salt may comprise sodium 3,5-dicarbomethoxybenzenesulfonate.

According to a preferred embodiment of the present invention, the acid component may include terephthalic acid, an aliphatic dicarboxylic acid component having 2 to 16 carbon atoms for improving biodegradability, and a sulfonic acid metal salt. More preferably, the aliphatic dicarboxylic acid component having 2 to 16 carbon atoms for improving the biodegradability is adipic acid and the sulfonic acid metal salt may be sodium 3,5-dimethoxybenzenesulfonate.

When adipic acid is included as described above, improved biodegradability can be obtained. However, as the content of adipic acid is increased, the thermal properties are remarkably lowered and the desired thermal properties can not be obtained or the resin can not be spun into fibers. Preferably, the adipic acid is contained in an amount of 5 to 15 mol% can do. If it is contained in an amount exceeding 15 mol%, the glass transition temperature (Tg) is lowered instead of increasing the biodegradation effect, and / There may be a problem. In addition, if it is contained in an amount of less than 5 mol%, there may be a problem that the objective biodegradability improving effect can not be seen. When the content of the adipic acid of the present invention is satisfied, there is an advantage that more improved biodegradability can be obtained.

The acid component of the biodegradable polyester resin of the present invention may comprise from 96 to 99.9 mol% of one or more of the components of terephthalic acid and adipic acid and from 0.1 to 5 mol% of sodium 3,5-dicarbomethoxybenzenesulfonate And preferably 86 to 92 mol% of terephthalic acid, 7 to 13 mol% of adipic acid, and 0.1 to 4 mol% of sodium 3,5-dicarbomethoxybenzenesulfonate.

If the content of any one or more of terephthalic acid and adipic acid is too small, there may be a problem that the resulting biodegradable polyester is poorly radioactive for application as a fiber product group. If the content is too large, There is a problem that the decomposing effect of the biodegradable polyester is deteriorated.

If the sodium 3,5-dicarbomethoxybenzenesulfonate component is contained in an amount of less than 0.1 mol%, the biodegradability is degraded. If the sodium 3,5-dicarbomethoxybenzenesulfonate component is contained in an amount exceeding 5 mol% There is a problem that radiation is difficult.

Next, the diol component may include at least one of an aliphatic diol component having 2 to 14 carbon atoms and polyethylene glycol.

Examples of the aliphatic diol having 2 to 14 carbon atoms include ethylene glycol, bio-ethylene glycol, diethylene glycol, propylene glycol, trimethylglycol, tetramethylene glycol, pentamethylglycol, hexamethylene glycol, heptamethylene glycol, octamethylene glycol , Nonane methylene glycol, decamethylene glycol, undecamethylene glycol, dodecamethylene glycol, and tridecamethylene glycol, and preferably at least one of ethylene glycol and bio-ethylene glycol .

The diol component of the biodegradable polyester resin of the present invention is preferably selected from the group consisting of ethylene glycol, bio-ethylene glycol, diethylene glycol, neopentyl glycol, 1,3-propanediol, 1,4-butanediol and 1,6- May be contained in an amount of 100 mole% or more, preferably 100 mole% of ethylene glycol, or 100 mole% of bio-ethylene glycol.

In the case of the polyethylene glycol, polyethylene glycol having a molecular weight of 300 to 5000 is preferably included.

In the case of the bio-ethylene glycol, the biomass-derived ethylene glycol has the same or similar physical properties as the ethylene glycol obtained from the existing petroleum resources.

On the other hand, in the biodegradable polyester resin, the acid component and the diol component may be copolymerized in a weight ratio of 1: 1.1 to 2.0. More preferably, the acid component and the diol component can be copolymerized in a weight ratio of 1: 1.1 to 1.5. If the diol component is copolymerized in an amount of less than 1.1 parts by weight based on the acid component, there is a problem in that the amount of the acid component in the reaction system increases and carbides are generated. If the diol component exceeds 2 parts by weight,

Further, as mentioned above, the biodegradable shrinkage fiber of the present invention includes a polylactide (PLA) resin, and the biodegradability can be further improved by including the polylactide (PLA) resin.

On the other hand, the biodegradable polyester resin and the polylactide resin of the biodegradable resin of the present invention are adhered in a side-by-side form, and the biodegradable polyester resin has an intrinsic viscosity (IV ) Is from 0.54 to 0.82 dl / g, preferably from 0.60 to 0.76 dl / g, and the polylactide resin has an intrinsic viscosity (IV) of 1.42 to 2.14 dl / g, preferably 1.48 to 2.08 dl / g have.

If the viscosity of the biodegradable polyester resin is less than 0.54 dl / g, the viscosity difference with respect to the polylactide resin is small, which may be disadvantageous in terms of potential winding resistance. If the viscosity exceeds 0.82 dl / g, have. If the viscosity of the polylactide resin is less than 1.42 dl / g, the viscosity difference between the biodegradable polyester resin and the biodegradable polyester resin may be too large to cause complex spinning. If the viscosity is more than 2.14 dl / g, It may be disadvantageous in terms of the potential winding effect.

Further, the biodegradable shrinkage blend yarn of the present invention may contain the biodegradable polyester resin and the polylactide resin at a weight ratio of 3 to 7: 7 to 3, preferably 4.5 to 5.5: 5.5 to 4.5, If the biodegradable polyester resin is out of the above-mentioned weight range, there may be a problem of deterioration of the potential crimp performance of the shrinkage-mixed yarn of the present invention.

Further, the biodegradable shrink-fusible fiber of the present invention may have a fineness of 1.0 to 10.0 denier, preferably 3.0 to 8.0 denier, and a fiber length of 20 to 100 mm, preferably 30 to 80 mm.

Meanwhile, the biodegradable shrinkage fusible fiber according to the present invention may have a reduction rate of intrinsic viscosity (IV) according to the following formula (1): 80% or more.

 [Equation 1]

Intrinsic viscosity reduction rate (%) =

At this time, it means that the sample is immersed in distilled water at 100 ° C at pH 7.

If the intrinsic viscosity (IV) reduction ratio (%) is larger, the biodegradability is greater. If the intrinsic viscosity (IV) reduction ratio is less than 80%, the degradation effect of the biodegradable shrinkage hybridization yarn is inferior.

In addition, the biodegradable shrink-fusible yarn of the present invention is superior in stretchability to yarns using conventional biodegradable polyester fibers as well as high intrinsic viscosity (IV) reduction ratio (%).

Specifically, in the present invention, the biodegradable shrinkage blend yarn may have a crimp number of 8 to 20 / inch and a crimp degree of 10 to 25.

The number of crimp can be adjusted according to the purpose of use, but if the crimp number is too high or low, there is a problem that the carding process is not smooth and the web formation is not uniform. Therefore, the number of crimp is 8 to 20 / inch, Lt; / RTI > to < RTI ID = 0.0 > 25.

At this time, the degree of crimp can be calculated by the following equation (2).

&Quot; (2) "

Crimp degree = (B-A) / B x 100

In Equation (2), A is a length average value in a crimped state, and B is a length average value in a crimped state.

The shrinkage blend yarn of the present invention has a shrinkage ratio of 3 to 15, preferably 7 to 13%, more preferably 8 to 12% in shrinkage ratio before and after a heat treatment at 180 ° C for 20 minutes. have.

At this time, the shrinkage ratio can be calculated by the following equation (3).

&Quot; (3) "

Shrinkage (%) = (C - D) / C x 100

In the above formula (3), C is the average length of the shrinkage mixed yarn before biodegradation, and D is the average length of the shrinkage hybrid yarn after biodegradation after the heat treatment.

On the other hand, the biodegradable shrink-fusible yarn of the present invention comprises (1) a biodegradable polyester resin having an intrinsic viscosity (IV) of 0.54 to 0.82 dl / g and a polylactide having an intrinsic viscosity (IV) of 1.42 to 2.14 dl / (PLA) resin in a side-by-side manner at a spinning speed of 1,000 to 1,500 mpm at 230 to 280 DEG C and then stretching the filament at a stretching ratio of 2.0 to 4.0 in a 60 to 80 DEG C hot bath to prepare filaments ; (2) heat-treating the filament at a temperature of 100 to 210 DEG C for 5 to 30 seconds under a tension applied state; (3) preparing a crimped fiber using a crimp box capable of passing the heat-treated filament through 300 to 8000 deniers per mm; (4) a relaxation heat treatment step of fixing the crimper by heat-treating the crimped fibers at 40 to 120 ° C for 10 minutes to 30 minutes; And (5) cutting the relaxed heat-treated fiber to produce a biodegradable shrinkage fiber having a fiber length of 30 to 60 mm; . ≪ / RTI >

The viscosity difference between the biodegradable polyester resin and the polylactide (PLA) resin used in the composite spinning is preferably 0.9 to 1.3 dl / g, preferably 1.0 to 1.2 dl / g, The flowability is not smooth under the same spinning temperature condition as the biodegradable polyester resin, which may cause a problem of spinning workability.

The combined spinning of the biodegradable polyester resin and the polylactide (PLA) resin at a weight ratio of 7: 3: 3 to 7, preferably 6: 4: 4 to 6: It is advantageous in terms of the accumulation effect and / or the radiation surface.

The heat treatment step is a process of heat-treating stretched fibers at 100 to 210 ° C to open and fix the fibers to improve the safety of the fibers. The hot-drum is contacted with the hot drum for 5 to 30 seconds using a plurality of hot drums Heat treatment is performed to increase the degree of crystallization of the fiber to improve the elastic modulus and compressive restoring force. The heat treatment step is a step of transferring heat to the filament to impart crystallinity along with selective orientation along the fiber axis, thereby increasing the fiber specific strength. In particular, the fiber is treated at a high temperature for a short time, The degree of crystallization is increased to improve the elasticity of the filament, so that the biodegradability can improve the compression recovery rate of the shrinkage mixed yarn. The thermally treated filament can lower the temperature of the filament through a cooling process at 30 to 80 ° C. In the cooling process, cooling water of 10 to 50 ° C. is used to immerse or spray the filament in cooling water to lower the temperature of the filament have.

A crimp box can be formed in the filament by using a crimp box capable of passing the cooled filament through 300 to 8000 deniers per 1 mm.

The relaxation heat treatment step relaxes the fibers with the crimped fibers at 40 to 120 ° C for 10 minutes to 30 minutes to uniformly transfer the heat to the entire fiber, thereby crystallizing the molecular structure of the outside or the inside which is not crystallized in the previous heat treatment step, To improve the morphological stability of the fiber, which can be carried out in a hot air or a hot bath. However, since the fiber needs to be dried when proceeding to a warm bath, the process is increased and the whole process time is increased. .

In the step of producing the biodegradable shrinkable filament yarn, the relaxed thermally treated filament is cut to produce a biodegradable filament yarn having a filament length of 30 to 60 mm.

The thus produced biodegradable shrink-fumed synthetic fiber has an intrinsic viscosity (IV) reduction rate of 80% or more, a number of crimps of 8 to 20 crimps / inch, a crimp degree of 10 to 25 according to Equation 1, The shrinkage ratio before and after the dry heat treatment for 20 minutes may be 3 to 15%, preferably 7 to 13%.

The present invention will now be described more specifically with reference to the following examples. However, the following examples should not be construed as limiting the scope of the present invention, and should be construed to facilitate understanding of the present invention.

Example

Preparation Example  One

(1) A 250 ml flask equipped with a stirrer and a condenser was charged with a diol component containing 89 mol% of terphthalic acid, 10 mol% of adipic acid and 1 mol% of sodium 3,5-dimethoxybenzenesulfonate and 100 mol% of ethylene glycol Was added at a molar ratio of 1: 1.2 based on the acid component. 500 ppm of lithium acetate was added as an esterification catalyst, and the temperature in the reactor was elevated from room temperature to 120 캜 for 30 minutes while stirring, and the temperature was raised to 250 캜 for 120 minutes. At this time, methanol and water, which are generated byproducts, were flowed out through a conduit. Subsequently, 300 ppm of phosphoric acid as a heat stabilizer and 300 ppm of antimony trioxide as a catalyst were added. Then, the pressure in the tube was gradually reduced to 0.5 mmHg over 40 minutes while stirring was carried out for 180 minutes while raising the temperature to 285 ° C. The mixture was stopped and discharged to prepare a biodegradable polyester resin according to the present invention.

The biodegradable polyester resin thus prepared had an intrinsic viscosity (IV) of 0.68 dl / g, a melting point of 213.4 DEG C, a glass transition temperature of 58.9 DEG C, an intrinsic viscosity (IV) measured after immersing at 100 DEG C for 96 hours for evaluation of the biodegradability of the biodegradable polyester resin And a reduction rate (IV) of 45.6%.

Preparation Example  2

The preparation was carried out in the same manner as in Preparation Example 1 except that 100 mol% of bio-ethylene glycol derived from biomass was used as the diol component.

The produced biodegradable polyester resin has a melting point of 215.1 캜, a glass transition temperature of 58.5 캜, an intrinsic viscosity (IV) of 0.68 dl / g, and an intrinsic viscosity reduction rate (IV) of 44.7% which is the same as or similar to that of conventional petroleum ethylene glycol.

Preparation Example  3

The same procedure as in Preparation Example 1 was repeated except that 84 mol% of terphthalic acid was used instead of the acid component of 89 mol% of terphthalic acid, 10 mol% of adipic acid and 1 mol% of sodium 3,5-dimethoxybenzenesulfonate, 15 mole% of sodium 3,5-dimethoxybenzenesulfonate and 1 mole% of sodium 3,5-dimethoxybenzenesulfonate was used. The produced biodegradable polyester resin had a melting point of 200.5 ° C, a glass transition temperature of 55.4 ° C, an intrinsic viscosity (IV) of 0.80 dl / g and an intrinsic viscosity reduction rate (IV) of 60.5%.

Example  One

(PLA) resin having a melting point of 163.2 占 폚, a glass transition temperature of 61.5 占 폚, an intrinsic viscosity (IV) of 1.40 dl / g and an intrinsic viscosity reduction rate (IV) of 87.79% was mixed with the biodegradable polyester resin prepared in Preparative Example 1 : 5 ratio by weight, spinning at a spinning temperature of 265 DEG C at a spinning speed of 1200 m < 2 > at a spinning speed of 3.0 in a hot bath at 70 DEG C to produce filaments, , And then crimped fibers were prepared using a crimp box capable of passing 300 to 8000 deniers per 1 mm. The crimped fibers were thermally treated at 80 DEG C for 15 minutes to fix the crimpers After cutting through the relaxation heat treatment process, the biodegradable shrinkable filament yarn was prepared.

The fineness of the produced biodegradable shrinkage mixed yarn is 4.31 denier and the fiber length is 38 mm.

Example  2

The biodegradable polyester resin prepared in Preparative Example 2 was used instead of the biodegradable polyester resin prepared in Preparation Example 1 to prepare a biodegradable contraction filament yarn.

The fabricated biodegradable shrink-fuseled yarn had a fineness of 4.27 denier and a fiber length of 38 mm

Example  3

The biodegradable polyester resin prepared in Preparative Example 3 was used instead of the biodegradable polyester resin prepared in Preparative Example 1 to prepare a biodegradable shrinkable filament yarn.

The fineness of the produced biodegradable shrinkage mixed yarn is 4.31 denier and the fiber length is 38 mm.

Comparative Example  One

(IV) of 0.65 dl / g and an intrinsic viscosity reduction rate (IV) of 20, instead of the biodegradable polyester resin prepared in Preparation Example 1, with a melting point of 258 캜, a glass transition temperature of 80 캜, % Of polyethylene terephthalate (PET) resin was used and spun at a spinning temperature of 280 占 폚, but yarn was not spinnable and a biodegradable shrinkage fiber was not produced.

Comparative Example  2

(PLA) resin having a melting point of 163.2 占 폚, a glass transition temperature of 61.5 占 폚, an intrinsic viscosity (IV) of 1.40 dl / g and an intrinsic viscosity decreasing rate (IV) of 87.79% was prepared in the same manner as in Example 1, Polyethylene terephthalate (PET) resin having a glass transition temperature of 80 ° C, an intrinsic viscosity (IV) of 0.65 dl / g and an intrinsic viscosity reduction rate (IV) of 20% was used and irradiated at a spinning temperature of 280 ° C, No biodegradable shrinkage fungus was produced.

Experimental Example  One

The following properties of the shrinkable filament yarn prepared through the above Examples and Comparative Examples were measured and are shown in Table 1.

(1) Strength and elongation

When the sample is rotated once, the sample is wound 90m around the sample, and the sample is weighed and weighed to 9,000m. The sample is then loaded into an automatic tensile tester (Textechno), and a speed of 50 cm / min and a grip distance of 50 cm are applied The strength was measured. (G / de) divided by the denier (de) is the strength, the percentage of the initial length as a percentage of the elongated length (%), Was defined as a shinto.

(2) Shrinkage (%)

The length change of the shrinkage mixed yarn before and after the dry heat treatment at 180 DEG C for 20 minutes was measured according to the following formula (3).

&Quot; (3) "

Shrinkage (%) = (C - D) / C x 100

In the above formula (3), C is a length average value of the shrinkage mixed yarn before the heat treatment, and D is an average length value of the shrinkage mixed yarn after the heat treatment.

(3) Number of crimp and crimp

The crimp number of the shrinkage-mixed fiber was measured, and the degree of crimp was measured according to the following formula (2).

&Quot; (2) "

Crimp degree = (B - A) / B x 100

In Equation (2), A is a length average value in a crimped state, and B is a length average value in a crimped state.

(4) Intrinsic viscosity reduction rate

The intrinsic viscosity (IV) after 96 hours was measured by immersing the shrinkage fibrillation yarn in distilled water at 100 ° C at pH 7, and the intrinsic viscosity (IV) reduction rate (%) was calculated by the following formula (1).

Intrinsic viscosity reduction rate (%) =

division Example
One Example
2 Example
3 Comparative Example
One Comparative Example
2 Strength (g / de) 3.15 3.09 2.78
radiation
Impossible


radiation
Impossible

Shinto (%) 73 71 80 Shrinkage (%) 10.3 9.8 20 Number of crimp (pieces / inch) / crimp 15/18 15/18 15/18 Intrinsic viscosity reduction rate 82.35 81.95 95.4

As can be seen from the above Table 1, the biodegradable shrinkage fiber produced in Examples 1 to 3 has biodegradability and excellent stretchability.

On the other hand, Comparative Example 1 using polyethylene terephthalate (PET) resin instead of biodegradable polyester resin and Comparative Example 2 using polyethylene terephthalate (PET) resin instead of polylactide (PLA) It was confirmed that the hybrid fiber was not produced.

Claims (17)

Biodegradable polyester resins; And polylactide (PLA) resins; / RTI >
The biodegradable polyester resin and the polylactide (PLA) resin are bonded in a side-by-side form,
Wherein the biodegradable polyester resin has an intrinsic viscosity (IV) of 0.54 to 0.82 dl / g, and the polylactide (PLA) resin has an intrinsic viscosity (IV) of 1.42 to 2.14 dl / g. Biodegradable, contraction,
The method according to claim 1,
The biodegradable shrinkage fusible fiber according to claim 1, wherein the rate of decrease in intrinsic viscosity (IV) is 80% or more.
[Equation 1]
Intrinsic viscosity reduction rate (%) =

At this time, it means that the sample is immersed in distilled water at 100 ° C at pH 7.
The method according to claim 1,
Characterized in that the biodegradable polyester resin and the polylactide (PLA) resin are contained at a weight ratio of 3 to 7: 7 to 3, and the biodegradable and contractible resin is excellent in stretchability.
The method according to claim 1,
Wherein the biodegradable shrink-fusible yarn has a crimp number of 8 to 20 / inch and a crimp degree of 10 to 25. The biodegradable shrink-fit filament yarn has excellent stretchability.
The method according to claim 1,
Wherein the shrinkage blend yarn has a shrinkage ratio of 3 to 15% before and after the heat treatment at 180 ° C for 20 minutes.
The method according to claim 1,
Wherein the biodegradable polyester resin comprises a copolymer of an acid component and a diol component,
Characterized in that the acid component and the diol component are contained in a molar ratio of 1: 1.1 to 2.0.
The method according to claim 6,
Wherein the acid component comprises at least one of an aromatic polycarboxylic acid component having 6 to 14 carbon atoms and an aliphatic polycarboxylic acid having 2 to 16 carbon atoms,
Wherein the diol component comprises at least one of ethylene glycol, bio-ethylene glycol, diethylene glycol, neopentyl glycol, 1,3-propanediol, 1,4-butanediol and 1,6-hexanediol This is a biodegradable, shrinkable synthetic resin with excellent elasticity.
8. The method of claim 7,
Wherein the aromatic polycarboxylic acid component having 6 to 14 carbon atoms comprises at least one of terephthalic acid, dimethyl isophthalate, isophthalic acid and dimethyl terephthalate.
8. The method of claim 7,
The aliphatic polycarboxylic acid having 2 to 16 carbon atoms is preferably selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, citric acid, pimelic acid, azelaic acid, sebacic acid, Which is characterized by containing at least one of dodecanoic acid and hexanodecanoic acid.
The method according to claim 6,
Wherein the acid component further comprises a sulfonic acid metal salt,
The sulfonic acid metal salt may be at least one of sodium 3,5-dicarbomethoxybenzenesulfonate, 5-sulfoisophthalic acid monosodium salt, and dimethyl 5-sodiumdiosulfoisophthalate Wherein the biodegradable shrinkable filament yarn has excellent stretchability.
The method according to claim 6,
Wherein the acid component comprises terephthalic acid, an aliphatic dicarboxylic acid component having 2 to 16 carbon atoms for improving biodegradability, and a sulfonic acid metal salt for improving biodegradability.
12. The method of claim 11,
Wherein the aliphatic dicarboxylic acid component having 2 to 16 carbon atoms for improving the biodegradability is adipic acid and the sulfonic acid metal salt for improving biodegradability is sodium 3,5-dimethoxybenzenesulfonate This is a biodegradable, shrinkable synthetic resin with excellent elasticity.
13. The method of claim 12,
Wherein the adipic acid for improving the biodegradability is contained in an amount of 5 to 15 mol% based on the total amount of acid components.
The method according to claim 6,
Wherein the acid component comprises 96 to 99.9 mol% of at least one of terephthalic acid and adipic acid and 0.1 to 5 mol% of sodium 3,5-dicarbomethoxybenzenesulfonate,
Wherein the diol component comprises 100 mole% of at least one of ethylene glycol, bio-ethylene glycol, diethylene glycol, neopentyl glycol, 1,3-propanediol, 1,4-butanediol and 1,6- Which is excellent in stretchability.
A fabric as claimed in any one of the preceding claims, characterized in that it comprises a constricted filament yarn.
(1) A biodegradable polyester resin having an intrinsic viscosity (IV) of 0.54 to 0.82 dl / g and a polylactide (PLA) resin having an intrinsic viscosity (IV) of 1.42 to 2.14 dl / Side-by-side type spinning at a spinning speed of 1,000 to 1,500 mpm, stretching at a stretching ratio of 2.0 to 4.0 at a temperature of 60 to 80 캜 in a warm bath to produce filaments;
(2) heat-treating the filament at a temperature of 100 to 210 DEG C for 5 to 30 seconds under a tension applied state;
(3) preparing a crimped fiber using a crimp box capable of passing the heat-treated filament through 300 to 8000 deniers per mm;
(4) a relaxation heat treatment step of fixing the crimper by heat-treating the crimped fibers at 40 to 120 ° C for 10 minutes to 30 minutes; And
(5) a step of cutting the relaxed heat-treated fiber to produce a biodegradable shrinkable filament yarn having a fiber length of 30 to 60 mm;
Wherein the biodegradable shrinkable filament yarn is excellent in elasticity.
17. The method of claim 16,
The biodegradable shrinkage fusible fiber according to the following formula (1) has a reduction rate of intrinsic viscosity (IV) of 80% or more, a number of crimps of 8 to 20 crimps / inch, a degree of crimp of 10 to 25, Characterized in that the shrinkage ratio before and after the heat treatment is 3 to 15%.
[Equation 1]
Intrinsic viscosity reduction rate (%) =

At this time, it means that the sample is immersed in distilled water at 100 ° C at pH 7.