KR102115406B1 - Bio-degradable polyester fiber with improved heat resistance and fabric comprising the same - Google Patents

Abstract

The present invention relates to a biodegradable polyester fiber having excellent heat resistance including a biodegradable polyester and a fabric using the same, and more specifically, it has a biodegradability and a high Tg, thereby improving heat resistance and allowing a spinning process to be heat resistant. Excellent biodegradable polyester fiber, fabric comprising biodegradable polyester fiber with improved heat resistance, biodegradable polyester composition for manufacturing polyester fiber with improved heat resistance, and biodegradable polyester chip for fiber production including biodegradable polyester with improved heat resistance It is about.

Description

Biodegradable polyester fiber with improved heat resistance and fabric comprising the same}

The present invention relates to a biodegradable polyester fiber having excellent heat resistance and a fabric using the same, and more specifically, it has a biodegradable and spinning process, and at the same time, has a high glass transition temperature (Tg), thereby improving heat resistance and thermal properties. It relates to a biodegradable polyester fiber excellent in heat resistance and a fabric using the same.

As the culture of mankind developed, clothing became worn, and as the material for such clothing, advanced from leaves of primitive plants or animal furs, fibers were separated from animals and plants, yarns were woven from them, and weaved yarns to make fabrics. The production of fibers began.

As described above, fibers that can be obtained directly from natural products are called natural fibers, and specifically, natural fibers refer to fibers that can be directly obtained from animals, plants, and minerals. The types are largely divided into animal fibers, vegetable fibers, and mineral fibers. It can be used immediately without weaving, such as felt or paper, or it is first made of a thread and then weaving the thread to make a fabric. Vegetable fibers include cotton, flax, and jute made of cellulose. Animal fiber is composed of protein and has hair, mohair, and silk. Mineral fibers have asbestos. All natural fibers are susceptible to mold or rot by microorganisms. Animal fibers are easily damaged by moths or slugs, and cellulose fibers are damaged by termites and moths.

However, as population growth and cultural development rapidly increased the demand for fiber, the use of fiber increased, so that only natural fiber could not meet the increasing fiber demand and newly required characteristics, and thus a new fiber material was required. Artificial fibers or chemical fibers have emerged. 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 have made fibers from these synthetic polymers to use synthetic fibers.

These synthetic fibers have a wide variety of types such as nylon, polyester, acrylic, polypropylene and vinylon fibers, and are used as industrial and industrial materials beyond clothing for their purposes.

However, the synthetic fiber described above does not decompose in nature and exists semi-permanently, which not only causes a number of environmental problems, but recently, when a specific compound is used, it is found that environmental hormones that disturb the endocrine system are released, which is a major social problem. Caused.

In addition, although conventional synthetic fibers are processed through methods such as landfilling, incineration, and recycling, the landfill space is insufficient due to the ever-increasing amount of garbage, and as the phenomenon of collective selfishness by residents in nearby regions intensifies, it is necessary to secure a landfill site. it's difficult. In addition, there are many problems in the use of landfill because the ground is not stable due to synthetic fiber wastes that are difficult to decompose even after landfilling, and when they are incinerated, harmful gases such as dioxins and carbon monoxide as described above are generated along with the generation of scattering dust. It is caused by a large amount of air pollution and serious harm to the human body.

As a method for solving these problems, biodegradation-related research and development to decompose the existing synthetic fiber itself has been variously conducted, and research on biodegradable polyester fibers has been actively conducted as an axis of the research and development.

Korean Patent Publication No. 95-114171 discloses a method for producing a high molecular weight aliphatic polyester by adding a polyhydric alcohol of a trivalent or higher value or a monomer of a polyhydric carboxylic acid having a trivalent value or more during polyester production. According to this method, the reaction time was shortened by introducing the monomer into the reaction system, and the molecular weight distribution was diffused to improve moldability. However, since the low molecular weight polyester is rapidly increased and the physical properties such as tensile strength are lowered, it is difficult to put it into practical use, and there is a problem in that it is difficult to control reactivity due to high risk of gelation.

As described above, the conventional biodegradable polyester fiber has low physical properties, especially heat resistance and thermal properties, and has a low melting point, making it difficult to be made of fibers, especially due to difficulty in spinning, and low glass transition temperature (hereinafter referred to as 'Tg'). Due to this, in the drying process of the biodegradable polymer before melting, the drying time increases and the adhesion of the biodegradable polymer (chip) to dry occurs, resulting in a defect in spinning, and the fiber shrinkage is greatly caused by post-processing such as heat treatment in the manufacturing process. There is a problem that it is difficult to deploy the product to a product group that must maintain thermal stability.

In addition, in the case of the biodegradable polyester fiber, there is a problem that the heat resistance and thermal properties are lowered as the decomposition property, which is one of its main functions, is increased.

Furthermore, when the glass transition temperature (Tg) of the fiber itself is increased through the addition of a specific compound to expand the use of the biodegradable polyester fiber, there is a problem that the biodegradable polyester fiber does not possess the decomposition power required.

The present invention has been devised to solve the above problems, and the first problem to be solved by the present invention is that it has biodegradability and at the same time possesses a high glass transition temperature, thereby improving heat resistance and biodegradability with excellent heat resistance capable of spinning processes. It is to provide a polyester fiber.

The second problem to be solved by the present invention is biodegradable polyester composition and heat resistance for fabrics comprising biodegradable polyester fiber having improved heat resistance by having high glass transition temperature while having biodegradability, and improved heat resistance. It is to provide a biodegradable polyester chip for producing fibers comprising improved biodegradable polyester.

In order to solve the first problem described above, the present invention, in the fiber comprising a biodegradable polyester, the biodegradable polyester is an acid component; And 1,4: 3,6-dianhydrohexitol containing a diol component copolymerized, and the intrinsic viscosity (IV) reduction rate of the biodegradable polyester by the following degradability evaluation method is 20% or more, Provided is a biodegradable polyester fiber having excellent heat resistance that satisfies a glass transition temperature (Tg) of 70 ° C or higher.

-Degradability evaluation method

The sample was immersed in distilled water at 100 ° C., pH 7, and the intrinsic viscosity (IV) was measured after 96 hours, and the intrinsic viscosity (IV) reduction rate (%) was calculated by the following equation (1).

(One)

According to a preferred embodiment of the present invention, the acid component may include any one or more components selected from the group consisting of an aromatic polyvalent carboxylic acid component having 6 to 14 carbon atoms and an aliphatic polyvalent carboxylic acid having 2 to 16 carbon atoms. Can be.

According to another preferred embodiment of the present invention, the aromatic dicarboxylic acid component having 6 to 14 carbon atoms may include any one or more selected from the group consisting of terephthalic acid, isophthalic acid and dimethyl terephthalate.

According to another preferred embodiment of the present invention, the acid component may further include a sulfonic acid metal salt.

According to another preferred embodiment of the present invention, the sulfonic acid metal salt may be sodium 3,5-dicarbomethoxybenzenesulfonate.

According to another preferred embodiment of the present invention, 1,4: 3,6-dianhydrohexitol of the total diol component may include 5 to 30 mol%.

According to another preferred embodiment of the present invention, the diol component may further include ethylene glycol and diethylene glycol.

According to another preferred embodiment of the present invention, the acid component may include terephthalic acid, an aliphatic dicarboxylic acid component having 2 to 16 carbon atoms to improve biodegradability, and a metal salt of sulfonic acid.

According to another preferred embodiment of the present invention, the aliphatic dicarboxylic acid component having 2 to 16 carbon atoms to improve the biodegradability is adipic acid, and the sulfonic acid metal salt is sodium 3,5-dimethoxy benzene. Sulfonate.

According to another preferred embodiment of the present invention, adipic acid to improve the biodegradability may include 2 to 12 mol% relative to the total content of the acid component.

According to another preferred embodiment of the present invention, the acid component is any one or more components selected from the group consisting of an aromatic polyvalent carboxylic acid component having 6 to 14 carbon atoms and an aliphatic polyvalent carboxylic acid component having 2 to 16 carbon atoms 95 ~ 99.9 mol% and sodium 3,5-dicarbomethoxybenzenesulfonate 0.1 ~ 5 mol% , the diol component is at least one component of ethylene glycol, diethylene glycol 70 to 95 mol% and 1,4 : 3,6-dianhydrohexitol 5 to 30 mol% may be included.

According to another preferred embodiment of the present invention, the intrinsic viscosity of the biodegradable polyester may be 0.55 ~ 0.75.

According to another preferred embodiment of the present invention, the acid component may not include a polyvalent carboxylic acid having 2 to 16 carbon atoms.

The present invention to solve the second problem described above, the acid component; And 1,4: 3,6-dianhydrohexitol 5 to 30 mol% of the total diol component, a biodegradable polyester composition for fiber production, comprising a biodegradable polyester copolymerized with a diol component. It provides a biodegradable polyester composition for fiber production that satisfies that the intrinsic viscosity (IV) reduction rate of the biodegradable polyester by the evaluation method is 20% or more and the glass transition temperature (Tg) is 70 ° C or more.

-Degradability evaluation method

The sample was immersed in distilled water at 100 ° C., pH 7, and the intrinsic viscosity (IV) was measured after 96 hours, and the intrinsic viscosity (IV) reduction rate (%) was calculated by the following equation (1).

(One)

In addition, the present invention to solve the second problem described above, the acid component; And a biodegradable polyester copolymerized with a diol component containing 5 to 30 mol% of 1,4: 3,6-dianhydrohexitol among all diol components, and the biodegradable poly by the following degradability evaluation method. It provides a biodegradable polyester chip for fiber production that satisfies that the intrinsic viscosity (IV) reduction rate of the ester is 20% or more and the glass transition temperature (Tg) is 70 ° C or more.

-Degradability evaluation method

The sample was immersed in distilled water at 100 ° C., pH 7, and the intrinsic viscosity (IV) was measured after 96 hours, and the intrinsic viscosity (IV) reduction rate (%) was calculated by the following equation (1).

(One)

In addition, to solve the second problem described above, the present invention provides a biodegradable polyester fabric comprising the biodegradable polyester fiber according to the present invention.

In the case of the biodegradable polyester fiber having excellent heat resistance of the present invention, it has excellent biodegradability and has a high glass transition temperature (Tg), and thus has heat resistance. The shrinkage of the fabric that may occur in the heat treatment process can be minimized, and the spinning can be smoothed by shortening the drying process time of the biodegradable polyester polymer before spinning into fibers and minimizing the adhesion between polymers that may occur in the drying process. In addition, it is possible to provide a polyester fiber having heat resistance and biodegradability, rather than a simple extrusion molding, as it is possible to develop into a product group requiring thermal properties and to perform a spinning process.

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

As described above, the conventional biodegradable polyester fiber has low biodegradable polyester properties, in particular, heat resistance and thermal properties, and is very vulnerable to low melting point. Due to (Tg), there was a problem in that the drying time was increased in the drying process and adhesion occurred between the fibers being dried, thereby making spinning difficult. In addition, there is a problem in that the fiber shrinkage occurs significantly during the post-processing in the manufacturing process after spinning into fibers, or the shrinkage of the fabric occurs in the process of heat-treating the fabric from which the fibers are woven. Furthermore, there has been a problem in that it is difficult to deploy the product to a product group that must maintain thermal stability.

In addition, in the case of the biodegradable polyester fiber, there was a problem that the heat resistance and thermal properties were lowered as the decomposition property, which is one of the main functions, was increased.

Furthermore, when the glass transition temperature (Tg) of the fiber itself is increased through the addition of a specific compound to expand the use of the biodegradable polyester fiber, there is a problem that the biodegradable polyester fiber does not possess the decomposition power required.

Accordingly, in the first embodiment of the present invention, in the fiber containing the biodegradable polyester, the biodegradable polyester comprises an acid component; And 1,4: 3,6-dianhydrohexitol containing a diol component copolymerized, and the intrinsic viscosity (IV) reduction rate of the biodegradable polyester by the following degradability evaluation method is 20% or more, The solution of the above-mentioned problems was sought by providing a biodegradable polyester fiber having excellent heat resistance that satisfies that the glass transition temperature (Tg) is 70 ° C or higher.

-Degradability evaluation method

The sample was immersed in distilled water at 100 ° C., pH 7, and the intrinsic viscosity (IV) was measured after 96 hours, and the intrinsic viscosity (IV) reduction rate (%) was calculated by the following equation (1).

(One)

Through this, it has excellent biodegradability, and at the same time has a high glass transition temperature (Tg), so it is easy to spun and can be made of fibers, and as it has improved thermal properties, it is possible to shorten the drying time of the biodegradable polyester before spinning and drying process. It is possible to prevent spinning defects by minimizing adhesion between polymer chips that may occur, and to minimize fiber shrinkage that may occur during post-processing of the spun fibers.

First, the biodegradable polyester contained in the biodegradable polyester fiber of the present invention will be described.

The biodegradable polyester is an acid component; And a diol component containing 1,4: 3,6-dianhydrohexitol copolymerized.

First, the acid component that can be used in the present invention will be described. The acid component that can be used in the present invention can be used without limitation as long as it is an acid component commonly used in biodegradable polyester fibers, preferably the acid component is an aromatic polyvalent carboxylic acid component, a polyvalent carboxyl containing a heterocycle It may contain any one or more components selected from the group consisting of acids and aliphatic polyhydric carboxylic acids, more preferably the acid component is an aromatic polyhydric carboxylic acid component having 6 to 14 carbon atoms and an aliphatic having 2 to 16 carbon atoms. It may include any one or more components selected from the group consisting of polyvalent carboxylic acid components.

The aromatic polyvalent carboxylic acid component may be any one or more selected from the group consisting of terephthalic acid, isophthalic acid and dimethyl terephthalic acid.

In addition, the polyvalent carboxylic acid containing the heterocycle is any one selected from the group consisting of 2,5-furandicarboxylic acid, 2,5-thiopheniccarboxylic acid and 2,5-pyrroledicarboxylic acid It may be abnormal.

In addition, the aliphatic polycarboxylic acid component is oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, citric acid, pimeric acid, azelaic acid, sebacic acid, nonanoic acid, decanoic acid, dode It may be any one or more selected from the group consisting of canophosphoric acid and hexanodecanoic acid. Preferably, the aliphatic polyvalent carboxylic acid may be adipic acid. The biodegradability can be increased by including the aliphatic polyvalent carboxylic acid component.

Meanwhile, according to a preferred embodiment of the present invention, a sulfonic acid metal salt may be further included. Including the metal salt of the sulfonic acid further induces adsorption of water molecules, thereby improving the biodegradation effect and increasing the degradability. Preferably, the sulfonic acid metal salt may be sodium 3,5-dicarbomethoxybenzenesulfonate.

Further, 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 to improve biodegradability, and a metal salt of sulfonic acid. More preferably, the aliphatic dicarboxylic acid component having 2 to 16 carbon atoms to improve the biodegradability may be adipic acid and the sulfonic acid metal salt may be sodium 3,5-dimethoxy benzene sulfonate.

When adipic acid is included as described above, improved biodegradability can be obtained. However, as the content of adipic acid increases, the thermal properties are remarkably lowered, so there is a problem that desired thermal properties cannot be obtained or cannot be spun into fibers. Preferably, the adipic acid contains 2 to 12 mol% of the total amount of the acid component. can do. If adipic acid is contained in excess of 12 mol%, instead of increasing the biodegradation effect, the glass transition temperature (Tg) is lowered, so that the desired thermal properties of the fiber cannot be obtained, and / or the spinning itself has a lot of cutting during spinning. Depending on the difficulty, there may be a problem that the use of the fiber cannot be developed. In addition, if included in less than 2 mol%, there may be a problem that the desired biodegradability improving effect cannot be seen. When the content range of adipic acid of the present invention is satisfied, there is an advantage of simultaneously obtaining thermal characteristics of a certain level or more and improved biodegradability.

Specifically, in the case of Example 1 below, when adipic acid is not included as an acid component, it can be confirmed that it has degradability and has excellent thermal properties. However, in order to obtain improved biodegradability according to the purpose, adipic acid may be included as an acid component as in Example 2, and in this case, thermal properties of a certain level or higher and improved biodegradability may be simultaneously obtained. However, in the case of Comparative Example 6 in which adipic acid was added excessively, biodegradability was improved, but there was a problem in that spinning was not easy, and it was confirmed that the thermal properties were also significantly reduced.

Meanwhile, another preferred embodiment of the present invention may not include an aliphatic polyvalent carboxylic acid having 2 to 16 carbon atoms as an acid component.

In the case of the conventional biodegradable polyester fiber, in order to improve biodegradability, aliphatic polycarboxylic acids such as adipic acid are included, but in this case, instead of improving biodegradability, the glass transition temperature is very low and thermal properties are significantly reduced. There was a problem in that it was not even spinning, and thus could not be used as a fiber.

Accordingly, the present inventors obtained 1,4: 3,6-dianhydrohexitol, which will be described below, to obtain a biodegradable effect of a certain level or higher without containing an aliphatic polycarboxylic acid such as adipic acid, and It was easy to develop a biodegradable polyester that can be used as a fiber and has improved thermal properties.

Specifically, in the case of Example 1 below, the aliphatic polycarboxylic acid adipic acid is not included as an acid component, and Example 2 is a case where adipic acid is included, while Example 1 has 20% or more degradability. The glass transition temperature is 85.4 ℃, the fabric shrinkage rate is 3.2%, it can be seen that the thermal properties are greatly improved. On the other hand, in Example 2, instead of improving the degradability to 67.1%, the glass transition temperature was lowered to 74.2 ° C, and the fabric shrinkage was also increased to 10.4%, confirming that the thermal properties were reduced compared to Example 1.

According to a preferred embodiment of the present invention, the acid component is 95 to 99.9 moles of any one or more components selected from the group consisting of an aromatic polyvalent carboxylic acid component having 6 to 14 carbon atoms and an aliphatic polyvalent carboxylic acid component having 2 to 16 carbon atoms. % And sodium 3,5-dicarbomethoxybenzenesulfonate 0.1 to 5 mol%.

 Of the acid components, any one or more components selected from the group consisting of an aromatic polyvalent carboxylic acid component having 6 to 14 carbon atoms and an aliphatic polyvalent carboxylic acid component having 2 to 16 carbon atoms is another component that can be included as an acid component, sodium 3 , 5-dicarbomethoxymethoxysulfonate may be included in the remaining molar% except for the molar%.

However, if the content of any one or more of the aromatic polyhydric carboxylic acid component and the aliphatic polyhydric carboxylic acid component is too small, there may be a problem in that radioactivity for applying the biodegradable polyester obtained as a fiber product group is poor. , If the content is too large, there is a problem that the decomposition effect of the biodegradable polyester obtained.

If the sodium 3,5-dicarbomethoxybenzenesulfonate component is contained in an amount of less than 0.1 mol%, there is a problem that biodegradability decreases, and when it exceeds 5 mol%, the pack pressure during spinning is high, and spinning There are difficult problems.

Next, the diol component contained in the biodegradable polyester will be described.

The diol component included in the present invention includes 1,4: 3,6-dianhydrohexitol.

In the case of the conventional biodegradable polyester, in order to increase the biodegradability, the aliphatic polyhydric carboxylic acid was often included, and in this case, as the thermal properties were significantly lowered, there was a problem in that it was very difficult to be made of fibers.

In addition, although it may be made of fibers, the drying process is usually performed at a temperature near or above the glass transition temperature (Tg) of the biodegradable polyester, but the drying efficiency is poor due to low Tg, and the drying time is prolonged. There is a problem.

Furthermore, there is a problem that causes a defect in spinning due to adhesion between biodegradable polyester chips in the drying process, and shrinkage of the fibers in a post-processing process such as heat treatment of the spun fiber or shrinkage of the fabric in a heat treatment process of a fabric woven of the fibers. There was a problem.

The inventor of the present invention was able to obtain a biodegradable polyester fiber having a high Tg by including 1,4: 3,6-dianhydrohexitol in the diol component, through which it is spun into fibers while retaining biodegradability. It is easy to use, and by improving thermal properties, it minimizes shrinkage of fibers or fabrics after processing and prevents mass production of defective products.

In addition, the 1,4: 3,6-dianhydrohexitol improves the thermal properties of the biodegradable polyester and at the same time, when included with the metal salt of the sulfonic acid described above, it causes a synergistic effect in the biodegradability, so that the biodegradability is more excellent. It has the advantage of losing.

Preferably, 1,4: 3,6-dianhydrohexitol of the total diol component may contain 5 to 30 mol%. If it is included in less than 5 mol%, there may be a problem that the thermal properties are insufficient, and if it is included in excess of 30 mol%, there may be a problem that degrades decomposition performance.

According to a preferred embodiment of the present invention, the diol component may further include any one or more of an aliphatic diol component having 2 to 14 carbon atoms and polyethylene glycol.

In the case of the aliphatic diol component having 2 to 14 carbon atoms, ethylene glycol, diethylene glycol, propylene glycol, trimethyl glycol, tetramethylene glycol, pentamethyl glycol, hexamethylene glycol, heptamethylene glycol, octamethylene glycol, nonamethylene glycol , Decamethylene glycol, undecamethylene glycol, dodecamethylene glycol and tridecamethylene glycol, and may include any one or more selected from the group consisting of, preferably, ethylene glycol and diethylene glycol may be any one or more , More preferably, it may be ethylene glycol.

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

According to a preferred embodiment of the present invention, the diol component comprises 70 to 95 mol% of at least one component of ethylene glycol and diethylene glycol and 5 to 30 mol% of 1,4: 3,6-dianhydrohexitol. Can be.

The diol component may include at least one component of ethylene glycol or diethylene glycol by the remaining mole percent excluding mole percent of 1,4: 3,6-dianhydrohexitol included.

According to a preferred embodiment of the present invention, in the biodegradable polyester, the above-described acid component and diol component may be copolymerized in a weight ratio of 1: 1 to 2. More preferably, the acid component and the diol component may be copolymerized in a weight ratio of 1: 1 to 1.4. If the diol component is copolymerized in an amount less than 1 weight ratio compared to the acid component, there is a problem in that there are many acid components in the reaction system, resulting in carbide, and if it exceeds 2 weight ratio compared to the acid component, there is a problem in that the reactivity is poor.

On the other hand, in the present invention, the intrinsic viscosity (IV) reduction rate of the biodegradable polyester by the following degradability evaluation method is 20% or more, and the glass transition temperature (Tg) is 70 ° C or more.

-Degradability evaluation method

The sample was immersed in distilled water at 100 ° C., pH 7, and the intrinsic viscosity (IV) was measured after 96 hours, and the intrinsic viscosity (IV) reduction rate (%) was calculated by the following equation (1).

(One)

In the case of biodegradable polyester fibers, especially the thermal properties of biodegradability and physical properties of the fibers tend to be opposite to each other. If the biodegradability is increased, thermal properties such as the glass transition temperature of the fiber may not be good and spinning may not be smooth. On the contrary, when the thermal properties were increased, the biodegradability was poor and it was very difficult to simultaneously obtain the desired effects of both.

However, the inventors of the present invention have invented biodegradable polyester fibers satisfying the above conditions (reduction rate of intrinsic viscosity, glass transition temperature), while retaining biodegradability while improving thermal properties such as glass transition temperature and at the same time having radiation compatibility.

First, the present invention has an intrinsic viscosity (IV) reduction rate of biodegradable polyester of 20% or more by a degradability evaluation method.

으로 계산된다.The degradability evaluation method is immersed in a sample, i.e., biodegradable polyester before melting, in 100 ℃ distilled water at pH 7, and measures the intrinsic viscosity (IV) after 96 hours, and the intrinsic viscosity (IV) reduction rate (%) is

Is calculated as

The greater the intrinsic viscosity (IV) reduction rate (%), the greater the biodegradability. If the intrinsic viscosity (IV) reduction rate (%) is less than 10%, there is a problem that the decomposition effect of polyester is poor and conventional simple There is a problem that can cause environmental pollution when buried because there is no difference from polyester fiber.

In addition, the glass transition temperature (Tg) of the biodegradable polyester included in the present invention is 70 ° C or higher.

In the case of the conventional biodegradable polyester fiber, the glass transition temperature is less than 60 ° C, so there is a problem of poor thermal properties, but the glass transition temperature of the biodegradable polyester included in the present invention is 70 ° C or higher and 70 ° C during the drying process. The drying time can be shortened because drying is possible at or near the temperature, and fiber shrinkage can be minimized during post-processing such as heat treatment after spinning into fibers. In addition, the shrinkage of the fabric can be minimized in processes such as heat treatment after weaving the fibers.

Specifically, in the case of Example 1 in Table 1, when the 1,4: 3,6-dianhydrohexitol is included as a diol component, the glass transition temperature is 85.4 ° C, which has improved thermal properties than the conventional one, but a diol component. As for Comparative Example 2, which does not contain 1,4: 3,6-dianhydrohexitol, it can be expected that the glass transition temperature is 70.4 ℃, which significantly reduces the thermal properties. However, by including 1,4: 3,6-dianhydrohexitol as a diol component, the object of the present invention cannot be achieved, which is 1,4: 3 as a diol component in Comparative Example 1 below. Although 6-dianhydrohexitol was included, the desired biodegradability and thermal properties could not be obtained at a glass transition temperature of less than 70 ° C.

Preferably, the biodegradable polyester according to an exemplary embodiment of the present invention may have an intrinsic viscosity of 0.55 to 0.75 dl / g. If the intrinsic viscosity is less than 0.55 dl / g, there may be a problem in that it is difficult to spin because the melt viscosity is low in the process of melting and spinning the biodegradable polyester. If the viscosity exceeds 0.75 dl / g, the viscosity is high and the pack pressure is high. There may be a problem that the radiation is difficult.

Next, a method for manufacturing biodegradable polyester fibers according to a preferred embodiment of the present invention will be described.

First, the biodegradable polyester can be used without limitation in the case of a method for preparing a biodegradable polyester contained in a conventional biodegradable polyester fiber. Preferably, the acid component and the diol component may be prepared by esterifying an oligomer to produce an oligomer and polymerizing the prepared oligomer.

First, the step of preparing an oligomer by esterifying an acid component and a diol component is specifically selected from the group consisting of an aromatic polyvalent carboxylic acid component having 6 to 14 carbon atoms and an aliphatic polyvalent carboxylic acid component having 4 to 14 carbon atoms. 95 to 99.9 mol% of one or more ingredients and sodium 3,5-dicarbomethoxybenzenesulfonate, 5-sulfoisophthalic acid monosodium salt and dimethyl5-sodiosulfo isophthalate 70 to 95 mol% and 1,4: 3,6-dianhydrohexitol 5 to 30 mol% of at least one component of ethylene glycol, diethylene glycol, and an acid component containing 0.1 to 5 mol% of at least one of Diol component containing a mixture containing 1: 1 to 2 in a weight ratio of 20 to 40 minutes to raise the temperature from room temperature to 100 to 140 ℃ and while stirring the mixture again the temperature to 200 to 280 ℃ 100 to 150 minutes The oligomer can be prepared through an esterification reaction by heating.

The catalyst and the amount used in the esterification reaction are important in that they can cause discoloration of the polymer and the like, and the reaction times can be determined, and lithium is added when sodium 3,5-dicarbomethoxybenzenesulfonate is added in the metal sulfonate salt. Cobalt compounds can be used to prevent compounds and discoloration.

As the lithium compound, a lithium compound used for manufacturing a conventional biodegradable polyester can be used, but preferably metal lithium or lithium acetate can be used, and the amount of the lithium compound used is the total weight of the theoretical polymer obtained after polymerization. It may be most effective when using an amount in the range of 100 to 600ppm as a reference.

In addition, the cobalt compound may preferably use a metal cobalt or cobalt acetate, and in this case, may be most effective in preventing discoloration, and the amount of the cobalt compound used is 60 to 130 ppm based on the total weight of the theoretical polymer obtained after polymerization. It may be most effective when using. If used below 60ppm, it may not have an effect as a complementary agent, and if it is included in excess of 130ppm, there is a problem that it can act as a foreign material during spinning.

Next, a biodegradable polyester may be prepared by polymerizing the prepared oligomer, and specifically, the oligomer may be prepared through a stirring reaction at 250 to 300 ° C. for 150 to 200 minutes.

It can be prepared by adding a catalyst and a stabilizer in the polymerization step, which can have a great influence on the properties of the polymer, especially the reaction rate and color.

In particular, in the case of a copolymerized polyester polymer containing an aromatic polyhydric carboxylic acid as an acid component, a reaction is required at a high temperature of 250 to 300 ° C, so it is important to select a catalyst and a heat stabilizer. In addition, when a catalyst used as a co-catalyst is added to increase the reaction rate, such as aluminum acetate basic, it is recommended to avoid the use as much as possible because the foreign substance in the polymer increases and causes an increase in initial pack pressure upon spinning.

The catalyst that can be used in the polycondensation reaction in the present invention may be an antimony compound, and a phosphorus compound may be used as a heat stabilizer to suppress discoloration of color due to thermal decomposition at high temperature.

The antimony compounds include antimony trioxide, antimony trioxide, antimony pentoxide, antimony trioxide, antimony trifluoride, antimony trifluoride, antimony trichloride, antimony trichloride, antimony triacetate, antimony benzoate, and antimony tristearate. It may be used, preferably, any one or more of antimony trioxide and antimony triacetate may be used, and the amount thereof may be preferably 100 to 600 ppm based on the total weight of the theoretical polymer obtained after polymerization.

As the phosphorus compound, phosphoric acid such as phosphoric acid, monomethyl phosphoric acid trimethyl phosphoric acid or tributyl phosphoric acid and derivatives thereof may be used, preferably trimethyl phosphoric acid or triphenylphosphoric acid, and the amount of phosphorus compound used is preferably 100 to 500 ppm may be used based on the total weight of the theoretical polymer obtained after polymerization.

The obtained biodegradable polyester is preferably biodegradable polyester is first formed in the form of a chip, and then spun in a fiber form. The biodegradable polyester chip undergoes a drying process within a suitable temperature and humidity to maintain a moisture content below a certain level prior to spinning. At this time, if the process develops in a state where the moisture content is too high, it is spun into fibers due to rapid hydrolysis. A phenomenon in which the physical properties of the yarn is deteriorated may appear. Therefore, it is necessary to manage the polymer at a moisture level below the appropriate level. At this time, when the glass transition temperature (Tg) is low, the drying temperature cannot be increased, so drying efficiency may be reduced, drying time may be extended, and adhesion between the biodegradable polyester chips that may be dried may occur. There is a problem, and when the sticking chip is produced as described above, it is difficult to take out the chip from the drying device or there is a problem in that spinning cannot be stably performed due to clogging of the input line or input port with the sticking chip.

 The drying process of the biodegradable polyester chip may be performed by a drying process of a conventional biodegradable polyester chip, preferably, the biodegradable polyester chip may be dried at or near the glass transition temperature, More preferably, it may be dried at 80 to 120 ° C over 180 to 400 minutes.

Preferably, the biodegradable polyester chip may be melted at 180 to 250 ° C to produce fibers through spinning, and may be spun spinning with heterogeneous synthetic resins or homogeneous polyester-based synthetic resins depending on the purpose.

The fiber as it is spun and solidified the fibrous phase may preferably stretch or partially stretch the spun fiber because the orientation of molecules in the fiber is poor.

Specifically, the method of spinning the fiber with a stretched yarn (SDY) is 1100 to 1700 mpm (m / min) when the fiber to be spun is a composite fiber of biodegradable polyester fiber or homogeneous polyester-based synthetic resin and biodegradable polyester. It can be stretched with a first winding wound at a speed of 4000 and a second winding wound at a speed of 4000 to 4600 mpm (m / min).

The method of spinning the fiber with a partially stretched yarn (POY) is 2500 to 3300 mpm (m / min) when the spinning fiber is a composite fiber of biodegradable polyester fiber or homogeneous polyester-based synthetic resin and biodegradable polyester. ) Can be partially stretched with a first winding wound at a speed of 2 and a second winding wound at a speed of 2500 to 3400 mpm (m / min).

Preferably, when spinning with the stretched yarn (SDY) and the partially stretched yarn (POY), the biodegradable polyester fiber can be spun using a Godet roller (G / R). When the first winding and the second winding are performed using the Godet roller in the drawing of the drawn yarn (SDY), the surface temperature of the Godet roller is preferably 70 to 90 ° C in the first winding and 100 to 140 in the second winding. After maintaining at ℃, it can be wound up. Through this, it is possible to prevent a trimming phenomenon occurring during stretching.

The stretched or partially stretched yarn spun as described above may be preferably made of fineness 50 to 200 denier and 18 to 100 filaments for ease of use and process ease.

The method for producing the biodegradable polyester fiber described above is only an exemplary method, and is not limited by the aforementioned method.

Meanwhile, the second embodiment of the present invention includes an acid component; And 1,4: 3,6-dianhydrohexitol 5 to 30 mol% of the total diol component, a biodegradable polyester composition for fiber production comprising a biodegradable polyester copolymerized with a diol component,

It includes a biodegradable polyester composition for fiber production satisfactory that the intrinsic viscosity (IV) reduction rate of the biodegradable polyester by the above-described degradability evaluation method is 20% or more, and the glass transition temperature (Tg) is 70 ° C or more.

The present invention provides a composition for producing a biodegradable polyester for fiber production as described above, in the case of a biodegradable polyester chip having the composition, shortening of drying time, adhesion between chips does not occur, and spinning is suitable for fiber production and thermal Since the properties are improved, it can have an excellent effect in the prevention of fiber shrinkage in the manufacturing process of fibers or fabrics.

The acid component, the diol component, the intrinsic viscosity reduction rate and the glass transition temperature will be omitted as described in the first embodiment of the present invention.

In addition, the third embodiment of the present invention is an acid component; And a biodegradable polyester copolymerized with a diol component containing 5 to 30 mol% of 1,4: 3,6-dianhydrohexitol among all diol components, and the biodegradable poly by the above-described degradability evaluation method. It includes a biodegradable polyester chip for fiber production that satisfies that the intrinsic viscosity (IV) reduction rate of the ester is 20% or more and the glass transition temperature (Tg) is 70 ° C or more.

The present invention can provide an improved thermal characteristic by maintaining the high Tg while maintaining biodegradability than the conventional biodegradable polyester chip by providing the above-mentioned biodegradable polyester chip for fiber production. In addition, the improved thermal properties when manufacturing the fiber using the chip has the advantage of making the spinning easy and possible. Furthermore, it can be used as a master batch for processing into a desired molded body by melt mixing with other polyester resin compositions.

The acid component, the diol component, the intrinsic viscosity reduction rate and the glass transition temperature will be omitted as described in the first embodiment of the present invention.

In addition, the fourth embodiment of the present invention includes a biodegradable polyester fabric comprising the biodegradable polyester fiber according to the present invention.

In the present invention, unlike the conventional biodegradable polyester fabric, by providing the above biodegradable polyester fabric, it has excellent thermal stability to minimize the shrinkage of the fabric in the heat treatment process after weaving, and can be washed by applying heat like dry. The fabric may not shrink even after washing.

The biodegradable polyester fabric can be woven with only the biodegradable polyester fiber according to the present invention or can be woven like a heterogeneous yarn for imparting the purpose and new function of the fabric to be manufactured.

In addition, when weaving the fabric according to the present invention, biodegradable polyester fibers may be used both as warp and weft yarns, only as warp yarns or warp yarns, as part of warp yarns, or as only some of the weft yarns. When weaving the fabric according to the present invention, the fabric texture and the density of warp and weft are not particularly limited. Fabrics or knitted fabrics can be woven using all or part of the yarn for weaving or knitting. In the present invention, fabrics and knitted fabrics are collectively referred to as fabrics.

The above-described expressions of the first to fourth embodiments should be interpreted to mean various embodiments of the present invention rather than showing the superior relationship of the present invention, and the present invention will be described in more detail through the following examples. However, the following examples are not intended to limit the scope of the present invention, which should be interpreted as to aid understanding of the present invention.

<Example 1>

First, in order to prepare a biodegradable polyester copolymer, an acid component having 90 mol% terephthalic acid and 10 mol% sodium 3,5-dimethoxybenzenesulfonate and 90 mol% ethylene glycol and 1 in a 250 ml flask equipped with a stirrer and a condenser Diol component of 10 mole% of 4: 4,3,6-dianhydrohexitol was added in a ratio of 1: 1.2 based on the acid component. Lithium acetate 500ppm was added as an esterification catalyst, and the temperature in the reactor was stirred while heating from room temperature to 120 ° C over 30 minutes, and the temperature was increased to 250 ° C for 120 minutes. At this time, the produced side reaction products, methanol and water, were discharged through a condenser. Subsequently, after adding 150 ppm of phosphoric acid as a heat stabilizer and 300 ppm of antimony trioxide as a catalyst, the pressure in the tube was gradually reduced to 0.5 mm Hg over 40 minutes, and the temperature of the tube was raised to 285 ° C while stirring reaction was carried out for 180 minutes, followed by stirring. Interrupted and discharged to obtain the biodegradable polyester according to the present invention. The obtained polyester was cooled in water and then cut with a pelletizer to prepare a biodegradable polyester chip.

The obtained biodegradable polyester chips were dried for 2 hours at 80 ° C and 100 ° C, respectively, and then dried for 4 hours at 140 ° C, and then subjected to a spinning process at a spinning temperature of 265 ° C, but in a Godet roller having a surface temperature of 90 ° C. Stretch yarn with a fineness of 75 filaments 36 through a first winding wound at a speed of 1500 mpm (m / min) and a second winding at a speed of 4400 mpm (m / min) at a Godet roller having a surface temperature of 125 ° C ( SDY).

<Examples 2 to 5>

Prepared in the same manner as in Example 1, the biodegradable polyester was prepared with the composition of Table 1 below to prepare a biodegradable polyester yarn.

<Comparative Examples 1 to 4>

Prepared in the same manner as in Example 1, the biodegradable polyester was prepared with the composition of Table 1 below to prepare a biodegradable polyester yarn.

<Experimental Example 1>

-To measure IV, the solvent phenol and TCE were mixed in a flask at a weight ratio of 60:40, and then the polymer sample was read up to 0.1 mg, and then stirred on a hot plate at a solution level of 0.4 g / dl.

-The biodegradable polyester chips obtained in Examples and Comparative Examples were dissolved in a temperature range of 110 to 120 ° C for 40 minutes.

-The prepared polymer solution was placed in a water bath (setting temperature 25.0 ° C) for 30 minutes to equilibrate with the viscosity bath temperature 25.0 ° C.

-For mixed solvents or measurement samples, put the solution in the Ubbelohde type capillary viscometer a tube up to d line, and match the viscometer to the Visco clock.

-The viscometer located on the visco clock is automatically packed with part c, and the polymer solution is filled with a rubber aspirator higher than the e-line of the b tube.

-After pressing the start part of the Visco clock, the number of falling seconds is measured and the intrinsic viscosity value is found by using the Huggins calculation formula or by extrapolation using a graph, and shown in Table 1 below.

<Experimental Example 2>

In order to investigate the melting point and the glass transition temperature, the biodegradable polyester chips obtained in Examples and Comparative Examples were subjected to differential scanning calorimetry (DSC), from -100 ° C to 250 ° C under nitrogen flow (50 ml / min). Table 1 shows the glass transition temperature (Tg) and melting point (Tm) by measuring the heating rate at 10 ° C / min.

<Experimental Example 3>

In the present invention, the easiness of spinning is a yield of biodegradable polyester fibers without truncation when spun by spinning a 9 kg drum of stretched yarn through Examples and Comparative Examples,

로 계산되며

Is calculated as

The yield is 100 to 95%, ◎, and 95 to 90%, ○, and less than 90%, respectively, are shown in Table 1 below.

<Experimental Example 4>

In order to measure the degradability of the biodegradable polyester, the intrinsic viscosity (IV) was measured by immersing the biodegradable polyester chip obtained through Examples and Comparative Examples in distilled water at pH 7 with pH 7 and measuring the intrinsic viscosity (IV) after 96 hours. The reduction rate (%) was calculated by the following equation (1) and is shown in Table 1 below.

(One)

<Experimental Example 5>

28 gauge, cylindrical knitting machine with a diameter of 10 cm using biodegradable polyester stretched yarn (SDY) obtained through Examples and Comparative Examples to measure the shrinkage of fabrics made of biodegradable polyester fibers Furnace was obtained. The above-mentioned knitted fabric was dyed at 110 ° C. for 30 minutes, and the area of the knitted fabric before dyeing was S ₁ , and the area of the knitted fabric after dyeing was S ₂ , and the shrinkage was calculated by the following equation.

Shrinkage (%) = (S ₂ -S ₁ ) × 100 / S ₁

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Acid component Terephthalic acid (mol%) 99 89 99 99 99 79 99 99 79 Sodium 윰 sodium 3,5-dicarbo methoxybenzenesulfonate (mol%) One One One One One One One One One Adipic acid (mol%) 0 10 0 0 0 20 0 10 20 Dior
ingredient Ethylene glycol (mol%) 90 90 80 60 98 90 100 100 100 1,4: 3,6-dianhydrohexitol
(mole%) 10 10 20 40 2 10 0 0 0 Intrinsic viscosity (IV, dl / g)) 0.67 0.64 0.65 0.70 0.67 0.66 0.67 0.69 0.66 Tg (℃) 85.4 74.2 106.7 131.2 75.1 68.1 69.4 56.7 43.1 Tm (℃) 229.3 227.3 205.1 200.6 234.9 201.3 252.3 223.4 204.3 Degradability (%) 31.6 67.1 52.0 2.5 5.6 40.6 4.1 42.7 73.4 Ease of radiation ◎ ◎ ◎ ◎ ○ ○ ○ ○ × Fabric shrinkage (%) 3.2 10.4 4.6 2.4 6.4 9.4 4.1 16.7 Impossibility

Specifically, in Example 1 in Table 1, when adipic acid is not included as an acid component, it can be confirmed that it has degradability and has excellent thermal properties. In addition, in the case of Example 2, when adipic acid was included as an acid component, in this case, thermal properties of a certain level or more and improved biodegradability than Example 1 could be simultaneously obtained. However, in the case of Comparative Example 4 in which adipic acid was added excessively, biodegradability was improved, but there was a problem in that spinning was not easy, thermal properties were remarkably lowered, and it could be confirmed that there was a problem in that weaving itself did not occur.

In addition, in the case of Example 1 in Table 1, when 1,4: 3,6-dianhydrohexitol is included as a diol component, the glass transition temperature is 85.4 ° C, which has improved thermal properties than the conventional one, but as a diol component. In the case of Comparative Example 2, which did not contain 1,4: 3,6-dianhydrohexitol, the glass transition temperature was 69.4 ° C, which markedly reduced the thermal properties.

Furthermore, in the case of Comparative Example 1, 1,4: 3,6-dianhydrohexitol was included as a diol component, but desired biodegradability and thermal properties could not be obtained at a glass transition temperature of less than 70 ° C.

Claims (16)

In the fiber comprising a biodegradable polyester,
The biodegradable polyester is 95 to 99.9 mol% of any one or more components selected from the group consisting of an aromatic polyvalent carboxylic acid component having 6 to 14 carbon atoms and an aliphatic polyvalent carboxylic acid component having 4 to 14 carbon atoms and 3,5 sodium. -An acid component containing 0.1 to 5 mol% of dicarbomethoxybenzenesulfonate; And 70 to 95 mol% of at least one component of ethylene glycol and diethylene glycol, and a diol component comprising 5 to 30 mol% of 1,4: 3,6-dianhydrohexitol.
The biodegradable polyester fiber excellent in heat resistance satisfying that the intrinsic viscosity (IV) reduction rate of the biodegradable polyester by the following degradability evaluation method is 20% or more and the glass transition temperature (Tg) is 70 ° C or more.

-Degradability evaluation method
The sample was immersed in distilled water at 100 ° C., pH 7, and the intrinsic viscosity (IV) was measured after 96 hours, and the intrinsic viscosity (IV) reduction rate (%) was calculated by the following equation (1).
(One)

delete According to claim 1,
The aromatic polyvalent dicarboxylic acid component having 6 to 14 carbon atoms is a biodegradable polyester fiber excellent in heat resistance, characterized in that it comprises any one or more selected from the group consisting of terephthalic acid, isophthalic acid and dimethyl terephthalate. delete delete delete delete The method of claim 1
The acid component is terephthalic acid, a biodegradable polyester fiber having excellent heat resistance, characterized in that it comprises an aliphatic dicarboxylic acid component having a carbon number of 2 to 16 to improve biodegradability and a sulfonic acid metal salt to improve biodegradability. The method of claim 8,
The aliphatic dicarboxylic acid component having 2 to 16 carbon atoms to improve the biodegradability is adipic acic, and the sulfonic acid metal salt to improve biodegradability is sodium 3,5-dimethoxy benzene sulfonate. Biodegradable polyester fiber with excellent heat resistance. The method of claim 9,
The biodegradable polyester fiber excellent in heat resistance, characterized in that the adipic acid to improve the biodegradability is contained 2 to 12 mol% relative to the total content of the acid component. According to claim 1,
Biodegradable polyester fiber excellent in heat resistance, characterized in that it does not contain an aliphatic dicarboxylic acid component having 2 to 16 carbon atoms as the acid component. delete According to claim 1,
The intrinsic viscosity of the biodegradable polyester is 0.55 ~ 0.75 dl / g biodegradable polyester fiber excellent heat resistance, characterized in that. 95 to 99.9 mol% of sodium and 3,5-dicarbomethoxybenzene of at least one component selected from the group consisting of an aromatic polyvalent carboxylic acid component having 6 to 14 carbon atoms and an aliphatic polyvalent carboxylic acid component having 4 to 14 carbon atoms. An acid component containing 0.1 to 5 mol% of sulfonate; And at least one component of ethylene glycol and diethylene glycol, 70 to 95 mol%, and 1,4: 3,6-dianhydrohexitol 5 to 30 mol%. As a biodegradable polyester composition for fiber production comprising,
The biodegradable polyester composition for fiber production satisfies that the intrinsic viscosity (IV) reduction rate of the biodegradable polyester by the following degradability evaluation method is 20% or more and the glass transition temperature (Tg) is 70 ° C or more.

-Degradability evaluation method
The sample was immersed in distilled water at 100 ° C., pH 7, and the intrinsic viscosity (IV) was measured after 96 hours, and the intrinsic viscosity (IV) reduction rate (%) was calculated by the following equation (1).
(One)

95 to 99.9 mol% of sodium and 3,5-dicarbomethoxybenzene of at least one component selected from the group consisting of an aromatic polyvalent carboxylic acid component having 6 to 14 carbon atoms and an aliphatic polyvalent carboxylic acid component having 4 to 14 carbon atoms. An acid component containing 0.1 to 5 mol% of sulfonate; And at least one component of ethylene glycol and diethylene glycol, 70 to 95 mol%, and 1,4: 3,6-dianhydrohexitol 5 to 30 mol%. Includes,
A biodegradable polyester chip for fiber production that satisfies that the intrinsic viscosity (IV) reduction rate of the biodegradable polyester by the following degradability evaluation method is 20% or more and a glass transition temperature (Tg) of 70 ° C or more.

-Degradability evaluation method
The sample was immersed in distilled water at 100 ° C., pH 7, and the intrinsic viscosity (IV) after 96 hours was measured, and the intrinsic viscosity (IV) reduction rate (%) was calculated by the following equation (1).
(One)

A biodegradable polyester fabric comprising the biodegradable polyester fibers according to any one of claims 1, 3, 8 to 11 and 13.