KR20190115965A - Poly(1,4-cyclohexylenedimethylene terephthalate) resin, preparation method thereof and fiber comprising thereof - Google Patents

Abstract

The present invention relates to a polycyclohexylenedimethylene terephthalate resin, a manufacturing method thereof, and a fiber comprising the same. The polycyclohexylenedimethylene terephthalate resin of the present invention exhibits excellent hydrolysis resistance, so that a fiber comprising the same does not fuse during delivery or storage and can maintain excellent physical properties even under long-term storage in a high temperature or high humidity environment.

Description

Polycyclohexylenedimethylene terephthalate resin, preparation method thereof and fiber comprising the same

The present invention relates to a polycyclohexylenedimethylene terephthalate resin, a method for producing the same, and a fiber comprising the same, and more particularly, to polycyclohexylene di, which exhibits excellent hydrolysis resistance and shows improved physical property retention in high temperature and high humidity environments. It relates to a methylene terephthalate resin, a preparation method thereof and a fiber comprising the same.

In general, the binder conjugate fiber can produce a nonwoven fabric by thermal bonding by thermal melting using thermal energy. The composite fiber for binder is composed of two components having different melting points, and can easily prepare a nonwoven fabric by melting only one component having a low melting point by heat.

Currently, as a composite fiber for polyester binder, polyethylene terephthalate (Poly (ethylene terephthalate)) resin modified by copolymerization with various diol and diacid components is mainly used, but PET resin has a glass transition temperature of 80 ° C. Since it is lower than below, fusion may occur during transportation and storage of the manufactured composite fiber, and physical properties may be degraded due to hydrolysis.

On the other hand, polycyclohexylenedimethylene terephthalate (Poly (1,4-cyclohexylenedimethylene terephthalate), hereinafter referred to as PCT) resin has better heat resistance, weather resistance, chemical resistance, and hydrolysis resistance than PET resin, and has a glass transition temperature. It is higher than 85 ℃, so there is little problem of fusion during transportation and storage, and the physical property retention is relatively good.

However, ester or transesterification reaction of terephthalic acid (hereinafter referred to as TPA) or dimethylterephthalate (hereinafter referred to as DMT) with 1,4-cyclohexanedimethanol (hereinafter referred to as CHDM). And conventional PCT resin prepared by the polycondensation reaction has a problem that does not exhibit sufficient hydrolysis resistance to maintain physical properties even if stored for a long time in a high temperature and high humidity environment.

It is an object of the present invention to provide a polycyclohexylenedimethylene terephthalate resin having a new composition, which shows remarkably improved hydrolysis resistance as compared to existing PCT resins, a method for preparing the same, and fibers including the same.

The present invention to solve the above problems,

As a polycyclohexylenedimethylene terephthalate resin copolymerized with a diol component containing an acid component and cyclohexanedimethanol,

The acid component comprises at least 65 mol% to less than 72 mol% of terephthalic acid or an alkyl ester thereof as the first component in a total of 100 mol% of the acid component,

A second component comprising more than 28 mol% to 35 mol% of one or more selected from the group consisting of isophthalic acid, cyclohexanedicarboxylic acid, adipic acid, succinic acid and alkyl esters thereof Provided are cyclohexylenedimethylene terephthalate resins.

The diol component may further include one or more selected from the group consisting of ethylene glycol, diethylene glycol, 1,4-butanediol, 1,3-propanediol, and isosorbide.

Specifically, the diol component comprises at least 90 mol% of cyclohexanedimethanol in a total of 100 mol% of the diol component,

It may include one or more selected from the group consisting of ethylene glycol, diethylene glycol, 1,4-butanediol, 1,3-propanediol and isosorbide to 10 mol% or less.

The second component of the acid component may be isophthalic acid or an alkyl ester thereof.

The polycyclohexylenedimethylene terephthalate resin was dissolved in o-chlorophenol at a concentration of 1.2 g / dl, and then measured at 35 ° C. using a Uberod viscous tube at a temperature of 0.50 to 1.20 dl / g. Can be.

When the polycyclohexylenedimethylene terephthalate resin is quantitatively analyzed using a GC chromatogram device, the vinyl end group content represented by the following Chemical Formulas 1 and 2 may be 35 ppm or less.

[Formula 1]

[Formula 2]

In addition, the present invention,

To a diol compound comprising cyclohexanedimethanol dissolved in water, terephthalic acid or dimethyl terephthalate as a first component, and isophthalic acid, dimethylisophthalate, cyclohexanedicarboxylic acid, adipic acid and succinic acid as a second component Preparing a liquid mixture by inputting an acid component including at least one selected from the group consisting of;

Adding nitrogen to the liquid mixture, stirring and bubbling;

Adding a catalyst to the liquid mixture, and raising the temperature to perform esterification or transesterification; And

Performing a polycondensation reaction under reduced pressure,

In the manufacturing step of the liquid mixture, the first component of 100 mol% of the acid component is included in more than 65 mol% to less than 80 mol%, the second component is contained in more than 20 mol% to 35 mol%, poly It provides a method for producing a cyclohexylenedimethylene terephthalate resin.

In this case, the esterification or transesterification may be carried out at 200 to 300 ℃, the polycondensation reaction may be carried out at 250 to 290 ℃.

In addition, the esterification or transesterification may be carried out at a pressure of 0.2 to 3.0 kg / ㎠, the polycondensation reaction may be carried out at a pressure of more than 0 torr less than 5 torr.

The present invention also provides a fiber comprising the polycyclohexylenedimethylene terephthalate resin.

The fiber may further comprise a polyester resin other than polycyclohexylenedimethylene terephthalate, and specifically, the polyester resin other than the polycyclohexylenedimethylene terephthalate is polyethylene terephthalate, polyethylene 2,6- Dinaphthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene isophthalate or mixtures thereof.

Since the polycyclohexylenedimethylene terephthalate resin of the present invention exhibits excellent hydrolysis resistance, fibers containing the same do not have fusion during transportation or storage, and have excellent physical properties even when stored for a long time in a high temperature or high humidity environment. Can be maintained.

Hereinafter, the present invention will be described in detail.

Polycyclohexylenedimethylene Terephthalate (PCT) resins and fibers comprising the same

The present invention is a polycyclohexylenedimethylene terephthalate resin copolymerized diol component containing an acid component and cyclohexane dimethanol,

The acid component comprises at least 65 mol% to less than 72 mol% of terephthalic acid or an alkyl ester thereof as the first component in a total of 100 mol% of the acid component,

A second component comprising more than 28 mol% to 35 mol% of one or more selected from the group consisting of isophthalic acid, cyclohexanedicarboxylic acid, adipic acid, succinic acid and alkyl esters thereof Provided are cyclohexylenedimethylene terephthalate resins.

PCT resin has superior physical properties such as heat resistance, weather resistance, chemical resistance, and hydrolysis resistance compared to PET resin.However, when exposed to high temperature and high humidity environment for a long time, PCT resin has fusion or physical property such as tensile strength due to hydrolysis. There was a problem of this deterioration. Thus, the present inventors studied the composition of the PCT resin that maintains physical properties stably even in a high temperature and high humidity environment, and as a result completed the present invention.

In the present invention, the acid component is a dicarboxylic acid, which contains terephthalic acid or an alkyl ester thereof as a first component, and isophthalic acid, cyclohexanedicarboxylic acid, adipic acid, succinic acid and the like as a second component. It includes one or more selected from the group consisting of alkyl esters of. At this time, the first component of the acid component is included in more than 65 mol% to less than 72 mol% with respect to the total 100 mol% of the acid component and the second component is included in more than 28 mol% to 35 mol% or less.

The alkyl ester of the acid component contains a lower alkyl ester having 1 to 4 carbon atoms and / or acid anhydride thereof, such as monomethyl, monoethyl, dimethyl, diethyl or dibutyl ester of dicarboxylic acid. It is used to mean. Specifically, the alkyl ester of terephthalic acid may be dimethyl terephthalate, diethyl terephthalate, etc., the alkyl ester of isophthalic acid may be dimethyl isophthalate, diethyl isophthalate, etc., but is not limited thereto. In the following, each acid component may be used in the sense including its alkyl ester.

As the acid component includes a second acid component in addition to terephthalic acid in the above content, the polycyclohexylenedimethylene terephthalate resin of the present invention exhibits further improved hydrolysis resistance compared to conventional PCT resins. If the content of the first component in the total 100 mol% of the acid component is too high, more than 72 mol%, the crystallization rate is high, the fiber spinning is difficult, the mechanical properties of the fiber worsens, the hydrolysis resistance may be deteriorated, 65 Too low of less than mole% may lead to the problem of non-fiber spinning as an amorphous polymer.

Particularly, the hydrolysis resistance of the resin is remarkably improved when the first component is included 68 to 72 mol% and the second component is included 28 to 32 mol% of the total 100 mol% of the acid component. It is more preferable because it can show the physical property retention rate.

Specifically, the PCT resin of the present invention may include isophthalic acid or an alkyl ester thereof as the second component of the acid component.

On the other hand, the diol component is a cyclohexane dimethanol as a basic component, in addition to one or more selected from the group consisting of ethylene glycol, diethylene glycol, 1,4-butanediol, 1,3-propanediol and isosorbide It may further include other diol compounds.

When the diol component further includes a diol component other than cyclohexanedimethanol, cyclohexanedimethanol is preferably included at least 90 mol% of 100 mol% of the total diol component, and the other diol compound is preferably included within 10 mol%. . More preferably, at least 95 mol% of cyclohexanedimethanol and at most 5 mol% of other diol compounds may be included. If the content of cyclohexanedimethanol is less than 90 mol% of the total 100 mol% of the diol component, the hydrolysis resistance of the polymer may be lowered.

PCT resin of the present invention having an acid component and a diol component as described above was dissolved in o-chlorophenol at a concentration of 1.2 g / dl, and then measured at 35 ° C. using an Ubbelohde viscosity tube. May range from 0.50 to 1.20 dl / g, or may range from 0.60 to 0.80 dl / g. As the intrinsic viscosity range is satisfied, the PCT resin of the present invention exhibits excellent processability, mechanical properties, and the like. The intrinsic viscosity measuring method can be embodied by the following examples.

On the other hand, the PCT resin of the present invention is low in the content of the vinyl (vinyl) end group is excellent in weather resistance, and exhibits excellent color. Specifically, the PCT resin of the present invention has a vinyl terminal group content of 35 ppm or less, preferably 30 ppm or less, more preferably, when quantitatively analyzed using a GC chromatogram instrument. Or 25 ppm or less. When the vinyl end group content exceeds 35 ppm, the thermal stability of the polymer may be deteriorated and the physical property retention rate may be lowered.

In Formulas 1 and 2 Means a connection with the PCT backbone.

[Formula 1]

[Formula 2]

The above-described PCT resin of the present invention is used by combining two or more kinds of acid components, but exhibits significantly improved hydrolysis resistance as the combination ratio is satisfied within a specific range. In addition, since the PCT resin exhibits crystallinity and alkali resistance, it is suitable for fiberization, and the manufactured fiber maintains excellent tensile strength even in a high temperature, high humidity environment.

Specifically, the fiber containing the PCT resin of the present invention has excellent physical property retention rate of 85% or more, preferably 90% or more after standing in a constant temperature and humidity oven at a temperature of 85 ° C. and a relative humidity of 85% for 12 weeks. appear. The measuring method of the physical property retention can be embodied by the following examples.

The PCT resin of the present invention can be used alone and fiberized, such fibers can be suitably used for applications such as automotive nonwoven fabric, paper filter nonwoven fabric, water treatment filter nonwoven fabric and the like.

In addition, the PCT resin of the present invention may be used as one component of the composite fiber together with the polyester resin that is commonly used. Examples of the polyester resin that can be used together with the PCT resin of the present invention include, but are not limited to, polyester resins other than polycyclohexylenedimethylene terephthalate include polyethylene terephthalate, polyethylene 2,6-dinaphthalate, and polypropylene. And terephthalate, polybutylene terephthalate, polyethylene isophthalate, and mixtures thereof. The composite fiber can be suitably used for applications such as automotive nonwoven fabric, paper filter nonwoven fabric, water treatment filter nonwoven fabric.

Manufacturing method of polyester resin

The present invention provides a method for producing the PCT resin of the present invention described above. Specifically, the present invention is a diol compound containing cyclohexane dimethanol dissolved in water, terephthalic acid or dimethyl terephthalate as a first component, isophthalic acid, dimethyl isophthalate, cyclohexanedicarboxylic acid, Preparing a liquid mixture by inputting an acid component including at least one selected from the group consisting of adipic acid and succinic acid;

Adding nitrogen to the liquid mixture, stirring and bubbling;

Adding a catalyst to the liquid mixture, and raising the temperature to perform esterification or transesterification; And

Performing a polycondensation reaction under reduced pressure,

In the manufacturing step of the liquid mixture, the first component of 100 mol% of the acid component is included in more than 65 mol% to less than 80 mol%, the second component is contained in more than 20 mol% to 35 mol%, poly It provides a method for producing a cyclohexylenedimethylene terephthalate resin.

The acid component and diol component used in the preparation method of the present invention are as described above. The amount of the acid component and the diol component may be appropriately adjusted according to the physical properties of the desired PCT resin, and is not particularly limited. For example, the molar ratio of the diol component and the acid component is 0.5: 1 to 1: 3, or 1: It may range from 1.10 to 1: 1.50.

Cyclohexanedimethanol used as a diol component in the present invention is a solid in wax form at room temperature because its melting point is higher than room temperature, and in order to effectively introduce such cyclohexanedimethanol into the reactor, it is added to the liquid phase and then added to the reactor. Convenient in terms of On the other hand, the method of making cyclohexane dimethanol in the liquid phase by heating and storing the cyclohexane dimethanol at a temperature above the melting point, such as about 100 ℃ and liquefied by using a solvent that is well dissolved in cyclohexane dimethanol There is a method such as input. Here, when the cyclohexane dimethanol is heated by heat for a long time, the method of liquefying and adding is preferable because it may adversely affect the color of the cyclohexane dimethanol or the resin produced therefrom by side reactions such as oxidation reactions. Do. Therefore, in the preparation method of the present invention, cyclohexane dimethanol is dissolved in water, and then solution is added to the reactor.

At this time, the amount of water is preferably 5 to 20 parts by weight, or 10 to 15 parts by weight with respect to 100 parts by weight of cyclohexane dimethanol. If the amount of water added is too high, the reactant concentration may be slowed in the subsequent esterification reaction, and the progress of the reaction may be slow. If the amount of water is added too little, the solution of cyclohexanedimethanol may be difficult to satisfy the above range.

As such, cyclohexanedimethanol is dissolved in water, and then charged into a reactor, and an acid component including a first component and a second component is added to prepare a liquid mixture. At this time, the preparation of the mixture may be made at 20 to 50 ℃, or room temperature (25 ℃), it is preferable to perform the stirring for even mixing.

Next, nitrogen is added to the liquid mixture, followed by bubbling with stirring.

The nitrogen bubbling is performed before the esterification reaction in order to prevent the oxidation reaction by the trace amount of oxygen as much as possible, and the execution time is not particularly limited, but may be performed for example for 1 hour to 10 hours or 2 hours to 5 hours. Can be.

The liquid mixture treated as described above is made of PCT resin through an esterification reaction or a transesterification reaction (hereinafter referred to as an esterification reaction) and a polycondensation reaction.

The esterification reaction can be carried out at a temperature of 200 to 300 ° C., preferably 240 to 280 ° C. and pressure conditions of 0.2 to 3.0 kg / cm 2, preferably 0.5 to 2.0 kg / cm 2. At this time, water or alcohol generated as a by-product during the esterification reaction is continuously flowing out of the reactor to increase the reaction progress rate.

The esterification reaction time (average residence time) may be usually 2 hours to 10 hours, preferably 3 hours to 5 hours, and may vary depending on the reaction temperature, pressure, molar ratio of the acid component and diol component to be used.

The esterification reaction may be performed without a catalyst, but may be performed by adding an appropriate reaction catalyst for shortening the reaction time. The catalyst that can be used may include titanium, aluminum, tin, germanium, antimony-based catalysts, these catalysts may also act as a catalyst of the subsequent polycondensation reaction.

Useful titanium-based catalysts include tetraethyl titanate, acetyltripropyl titanate, tetrapropyl titanate, tetrabutyl titanate, polybutyl titanate, 2-ethylhexyl titanate, octylene glycol titanate, lactate titanate , Triethanolamine titanate, acetyl acetonate titanate, ethyl acetoacetic ester titanate, isostearyl titanate, titanium dioxide, titanium dioxide / silicondioxide copolymer, titanium dioxide / zirconium dioxide copolymer, etc. have. The germanium catalyst may include germanium dioxide, a copolymer using the same, and the like. The tin catalyst may include tetrabutyldibutoxytin oxide, dibutyltin oxide, and the like. These catalysts can be used alone or in combination.

The catalyst is preferably used in the range of 10 to 50 ppm based on the center metal of the catalyst, based on the total weight of acid and diol components as raw materials. If the amount of the catalyst is less than 10 ppm, the reaction rate may be slow due to insufficient amount of the catalyst. If the content of the catalyst exceeds 50 ppm, it may cause side reactions to deteriorate the color of the polymer. Do.

Phosphoric acid stabilizers, such as phosphoric acid, trimethyl phosphate, and triethyl phosphate, can be further added to the said esterification reaction. The amount of the phosphorus stabilizer added may be 10 to 50 ppm relative to the total amount of the raw material based on the amount of phosphorus element. If the amount of the stabilizer is less than 10 ppm, the stabilization effect is insufficient, and the color of the polyester resin may be changed to yellow. If the amount is more than 50 ppm, the desired polymerization reaction rate may be slow and a polymer having a high degree of polymerization may not be obtained.

After completion of the esterification reaction, a polycondensation reaction is carried out. The polycondensation reaction is carried out at a temperature of 250 to 290 ° C., preferably 270 to 280 ° C. and a pressure condition of more than 0 torr and less than 5 torr. The pressure condition is for removing glycol which is a byproduct of the polycondensation reaction. The polycondensation reaction is carried out for the required time until the desired intrinsic viscosity is reached, for example for an average residence time of 1 to 5 hours.

According to the production method of the present invention, since the oxidation and thermal decomposition of the PCT resin is minimized during the production process, it is possible to significantly reduce the content of vinyl end groups, and thus it is possible to improve the color properties and weather resistance of the resin produced.

Hereinafter, the operation and effects of the invention will be described in more detail with reference to specific embodiments of the invention. However, these embodiments are only presented as an example of the invention, whereby the scope of the invention is not determined.

EXAMPLE

Example 1

41 kg of 1,4-cyclohexanedimethanol (CHDM, trans 70%) was dissolved in 4.1 kg of water, and then charged into a reactor. 25 kg of terephthalic acid (TPA) and 11 kg of isophthalic acid (IPA) were added thereto, followed by 5 hours. Nitrogen was introduced into the reactor while stirring to prepare a slurry while bubbling. Into this, 7 g of triethyl phosphate and 20 g of titanium oxide catalyst (Sachtleben's trade name Hombifast PC) (20% (15% effective Ti ratio in the catalyst)) were added to the reactor, and the temperature was raised to 270 ° C. for 4 hours at atmospheric pressure, followed by esterification. (esterification) reaction was performed. Then, polycondensation reaction of polyester was performed for 300 minutes at 275 degreeC and the vacuum degree of 0.5-1 torr, and PCT resin was obtained.

Example 2

PCT resin was obtained in the same manner as in Example 1, except that the polyester polycondensation reaction was performed at 290 ° C. and a vacuum degree of 0.5 to 1 torr for 240 minutes.

Example 3

41 kg of 1,4-cyclohexanedimethanol (CHDM, trans 70%) was dissolved in 4.1 kg of water and added to the reactor, except that 26 kg of terephthalic acid (TPA) and 10 kg of isophthalic acid (IPA) were added thereto. PCT resin was obtained in the same manner as in Example 1.

Example 4

41 kg of 1,4-cyclohexanedimethanol (CHDM, trans 70%) was dissolved in 4.1 kg of water, and then charged into a reactor, followed by 24.5 kg of terephthalic acid (TPA) and 11.5 kg of isophthalic acid (IPA). PCT resin was obtained in the same manner as in Example 1 except that.

Example 5

41 kg of 1,4-cyclohexanedimethanol (CHDM, trans 70%) was dissolved in 4.1 kg of water, and then charged into a reactor, 25 kg of terephthalic acid (TPA) and 11 kg of isophthalic acid (IPA), and triethyl phosphate. ) 7g, 20 g of titanium oxide catalyst (Sachtleben's brand name Hombifast PC) (15% effective Ti ratio in the catalyst) was added to the reactor (no nitrogen bubbling was performed), and then the temperature was raised to 270 ° C. at atmospheric pressure for 4 hours. An esterification reaction was performed. Then, polycondensation reaction of polyester was performed for 300 minutes at 275 degreeC and the vacuum degree of 0.5-1 torr, and PCT resin was obtained.

Comparative Example 1

41 kg of 1,4-cyclohexanedimethanol (CHDM, trans 70%) was dissolved in 4.1 kg of water, and then charged into the reactor. 32 kg of terephthalic acid (TPA) and 4 kg of isophthalic acid (IPA) were added thereto, followed by 5 hours. Nitrogen was introduced into the reactor while stirring to prepare a slurry while bubbling. Into this, 7 g of triethyl phosphate and 20 g of titanium oxide catalyst (Sachtleben's trade name Hombifast PC) (20% (15% effective Ti ratio in the catalyst)) were added to the reactor, and the temperature was raised to 270 ° C. for 4 hours at atmospheric pressure, followed by esterification. (esterification) reaction was performed. Subsequently, a polycondensation reaction of the polyester was carried out at 290 ° C. at a vacuum degree of 0.5 to 1 torr for 300 minutes to obtain a PCT resin.

Comparative Example 2

41 kg of CHDM (trans 70%) was dissolved in 4.1 kg of water, and then charged into a reactor, followed by 22 kg of TPA, 7.3 kg of IPA, and 7.5 kg of 1,4-cyclohexanedicarboxylic acid, followed by nitrogen for 5 hours. The slurry was prepared while bubbling by stirring. Into this, 7 g of triethyl phosphate and 20 g of titanium oxide catalyst (Sachtleben's brand name Hombifast PC) (15% effective Ti ratio in the catalyst) were added to the reactor, and the temperature was raised to 270 ° C. for 4 hours at atmospheric pressure, followed by esterification. The reaction proceeded. Subsequently, a polyester polycondensation reaction was performed at 275 ° C. at a vacuum degree of 0.5 to 1 torr for 300 minutes to obtain a PCT resin.

Comparative Example 3

22 kg of ethylene glycol, 52 kg of TPA, 7 g of triethylphosphate, and 20 g of antimony trioxide catalyst were charged to the reactor, and the temperature was raised to 260 ° C. for 5 hours under a pressure of 2.0 kg / cm ² . An esterification reaction was performed. Subsequently, a polyester polycondensation reaction was performed at 280 ° C. at a vacuum degree of 0.5 to 1 torr for 200 minutes to obtain a PET resin.

Comparative Example 4

22 kg of ethylene glycol, 47 kg of TPA, 5 kg of IPA, 7 g of triethylphosphate, 20 g of antimony trioxide catalyst were charged to the reactor, and the temperature was raised to 260 ° C. for 5 hours under a pressure of 2.0 kg / cm ² and esterified ( esterification). Subsequently, a polyester polycondensation reaction was performed at 280 ° C. at a vacuum degree of 0.5 to 1 torr for 200 minutes to obtain a PET resin.

Comparative Example 5

22 kg of ethylene glycol, 36 kg of TPA, 16 kg of IPA, 7 g of triethylphosphate, 20 g of antimony trioxide catalyst were added to the reactor, and the temperature was raised to 260 ° C. for 5 hours under a pressure of 2.0 kg / cm ² and esterification was performed. ) Proceeded with the reaction. Subsequently, a polyester polycondensation reaction was performed at 280 ° C. at a vacuum degree of 0.5 to 1 torr for 200 minutes to obtain a PET resin.

Comparative Example 6

19 kg of ethylene glycol, 6 kg of diethylene glycol, 36 kg of TPA, 16 kg of IPA, 7 g of triethylphosphate, and 20 g of antimony trioxide catalyst were charged into a reactor, and 260 ° C for 5 hours under a pressure of 2.0 kg / cm ² . The temperature was raised to esterification. Subsequently, a polyester polycondensation reaction was performed at 280 ° C. at a vacuum degree of 0.5 to 1 torr for 200 minutes to obtain a PET resin.

Spinning process

Each resin obtained in Examples and Comparative Examples was dried for a long time in a nitrogen atmosphere to a moisture content of 300 ppm or less, and then injected into an extruder with a nozzle attached to the tip of the extruder, followed by melt spinning using a nozzle of 175 holes. The undrawn yarn of denier was prepared. The prepared non-drawn yarn was drawn in a heating drum drawing apparatus to produce drawn yarns of 4-6 denier, and heat-treated in a heat treatment apparatus.

Test Example 1 (intrinsic viscosity, IV)

Each resin obtained in Examples and Comparative Examples was dissolved in o-chlorophenol at a concentration of 1.2 g / dl, and the intrinsic viscosity was measured using a Ubbelohde viscous tube.

At this time, the temperature of the viscosity tube is maintained at 35 ° C., the time taken for the solution to pass through t is the time required for the solution to pass through the solvent between the sections ab inside the viscosity pipe ab. When t ₀ , specific viscosity is defined as in Equation 1 below, and the intrinsic viscosity is calculated using Equation 2 below.

[Equation 1]

[Equation 2]

In Equation 2, A was 0.247 as a Huggins constant, and c was used as a concentration value of 1.2 g / dl.

Test Example 2 (Glass Transition Temperature, Melting Temperature)

Using a differential scanning calorimeter (DSC), the sample (resin) was filled in an aluminum pan, heated to 320 ° C. at 10 ° C./min, held at 320 ° C. for 5 minutes, and then cooled to 30 ° C. at −300 ° C./min. Then, the glass transition temperature (Tg) and the melting temperature (Tm) were obtained from the heat flow obtained when heating up to 320 degreeC at 10 degreeC / min. Subsequently, after hold | maintaining at 320 degreeC for 5 minutes, the temperature of the exothermic curve peak at the time of temperature-falling -30 degreeC / min to 30 degreeC was made into cooling crystallization temperature (Tmc).

Test Example 3 (vinyl end group)

The vinyl end group content of the following Chemical Formulas 1 and 2 of each resin obtained through Examples and Comparative Examples was quantitatively analyzed under the following conditions using a GC chromatogram.

[Formula 1]

[Formula 2]

<Sample pretreatment>

The sample was pulverized and prepared as a powder, glass wool was placed in an ATD blank tube, and 10 mg of the powder sample was taken at the top, and then again closed with glass wool.

<GC condition>

① Model: Perkin-Elmer Clarus 600

② Column: DB-35MS (30m * 0.25mm * 0.25μm)

③ Oven temperature: 100 ℃ (2 min) → 5 ℃ / min → 260 (5 min)

④ Detector temperature: 250 ℃

<ATD device conditions>

① Model: Perkin-Elmer TurboMatrix ATD

② Tube temperature: 160 ℃

③ Thermo time: 30 min

Test Example 4 (Firm Strength)

Tenacity was measured for a fiber specimen prepared by the spinning process at a measurement rate of 5 mm / min according to ASTM D638 at 25 ° C. Initial physical properties were measured, and the physical properties were measured after being left in a constant temperature and humidity oven at a temperature of 85 ° C. and a relative humidity of 85% for 12 weeks. Based on the measured value was calculated according to the following equation (3).

[Equation 3]

In Equation 3, S0 is the initial physical properties of the fiber sample, S1 is the physical properties measured after standing in a constant temperature and humidity oven for 12 weeks at a temperature of 85 ℃ and 85% relative humidity.

Test Example 5 (-COOH end group concentration)

A fiber sample and a solvent (Benzyl alcohol) were placed in a glass container of a predetermined size, and heated and dissolved at 180 ° C. After adding a small amount of indicator (Indicator, Phenol Red) to the dissolved sample solution, a small amount of dilute sodium hydroxide solution was added to observe the color change of the solution. Subsequently, the injected sample amount, the concentration of sodium hydroxide solution, and the charged amount were substituted into the following formula to calculate the -COOH end group concentration (E).

[Equation 4]

In Equation 4, S is the volume of 0.1N sodium hydroxide-benzyl alcohol solution consumed in the sample titration, B is the volume of 0.1N sodium hydroxide-benzyl alcohol solution consumed in the blank titration. N is the concentration of sodium hydroxide-benzyl alcohol solution (0.1), W is the weight of the sample. f is a factor of 0.1N sodium hydroxide-benzyl alcohol solution, and is a value between 0.95 and 0.99.

Compositions and physical properties of the resins of the above Examples and Comparative Examples are shown in Table 1, and the physical properties of the fibers produced from the respective resins are shown in Tables 2 and 3.

unit Example Comparative example One 2 3 4 5 One 2 3 4 5 6 Di-ol CHDM mol% 100 100 100 100 100 100 100 0 0 0 0 EG mol% 0 0 0 0 0 0 0 100 100 100 85 DEG mol% 0 0 0 0 0 0 0 0 0 0 15 Di-acid TPA mol% 70 70 72 68 70 90 60 100 90 70 70 IPA mol% 30 30 28 32 30 10 20 0 10 30 30 CHDA mol% 0 0 0 0 0 0 20 0 0 0 0 Intrinsic Viscosity (IV) dl / g 0.66 0.64 0.65 0.65 0.69 0.65 0.69 0.66 0.67 0.65 0.63 Glass transition temperature (Tg) ℃ 85 85 86 84 86 88 72 80 74 70 68 Melting temperature (Tm) ℃ 234 235 237 232 234 272 218 255 233 196 - Vinyl end group ppm 16 28 19 14 35 27 28 - - - -

unit Example One 2 3 4 5 Di-ol CHDM mol% 100 100 100 100 100 EG mol% 0 0 0 0 0 DEG mol% 0 0 0 0 0 Di-acid TPA mol% 70 70 72 68 70 IPA mol% 30 30 28 32 30 CHDA mol% 0 0 0 0 0 radiation
Condition Drying temperature ℃ 160 160 160 160 160 Radiation temperature ℃ 270 270 270 270 270 Dead river Early g / d 3.7 3.5 3.8 3.6 3.6 85 ° C., 85%,
12 weeks later g / d 3.4 3.2 3.5 3.4 3.2 Property retention rate % 94.6 91.4 92.1 94.4 88.9 -COOH
Terminal group Early eq / 10 ⁶ g 14 17 16 16 22 85 ° C., 85%,
12 weeks later eq / 10 ⁶ g 18 25 20 19 31 △ eq / 10 ⁶ g 4 8 4 3 9

unit Comparative example One 2 3 4 5 6 Di-ol CHDM mol% 100 100 0 0 0 0 EG mol% 0 0 100 100 100 85 DEG mol% 0 0 0 0 0 15 Di-acid TPA mol% 90 60 100 90 70 70 IPA mol% 10 20 0 10 30 30 CHDA mol% 0 20 0 0 0 0 radiation
Condition Drying temperature ℃ 140 160 140 140 100 50 Radiation temperature ℃ 290 260 290 270 260 260 Dead river Early g / d 3.1 4.0 4.5 4.6 5.0 4.2 85 ° C., 85%,
12 weeks later g / d 2.6 2.9 2.9 3.0 3.1 2.3 Property retention rate % 83.9 72.5 64.4 65.2 62.0 54.8 -COOH
Terminal group Early eq / 10 ⁶ g 21 20 38 45 51 47 85 ° C., 85%,
12 weeks later eq / 10 ⁶ g 33 37 65 68 80 82 △ eq / 10 ⁶ g 12 17 27 23 39 35

As shown in Table 1, the PCT resins of Examples 1 to 5 in which the content of the first component and the second component in the acid component satisfy the scope of the present invention had an intrinsic viscosity ranging from 0.65 to 0.69 dl / g, and vinyl The end group content was as low as 35 ppm or less. In particular, it can be seen that Examples 1 to 4, which performed nitrogen bubbling in the manufacturing process, showed a lower vinyl end group content (30 ppm or less) compared to Example 5, which did not perform nitrogen bubbling.

In addition, the results of Tables 2 and 3 show that the fibers made from such PCT resins are excellent in hydrolysis resistance, and thus, even when stored in a high temperature and high humidity environment, unlike physical properties of PET resin fibers, physical properties such as tensile strength are not changed and stable physical properties. It can be seen that. However, PCT resins (Comparative Examples 1 and 2), which do not satisfy the acid component content of the present invention, showed a significant drop in physical property retention. Specifically, in Comparative Example 1, in which the content of isophthalic acid, which is the second component of the acid component, was only 10 mol%, the crystallization rate of the resin was high, making fiber spinning difficult, and the mechanical properties and hydrolysis resistance of the fiber were deteriorated. appear. On the other hand, in the case of Comparative Example 2 in which the content of the second component in the acid component is 40 mol%, the glass transition temperature and the melting temperature were found to be lower than those in the Examples, and the crystallization of the resin was lowered, which was also difficult to spin the fibers. It was confirmed that mechanical properties and hydrolysis resistance were also inferior.

From the above experimental results, it can be confirmed that it is essential to satisfy the acid component content of the present invention in order to achieve the effect of the present invention, it is possible to obtain a more excellent PCT resin of physical properties when performing the nitrogen bubbling step in the production of PCT resin It can be seen.

Claims (13)

As a polycyclohexylenedimethylene terephthalate resin copolymerized with a diol component containing an acid component and cyclohexanedimethanol,
The acid component comprises at least 65 mol% to less than 72 mol% of terephthalic acid or an alkyl ester thereof as the first component among 100 mol% of the acid component,
A second component comprising more than 28 mol% to 35 mol% of one or more selected from the group consisting of isophthalic acid, cyclohexanedicarboxylic acid, adipic acid, succinic acid and alkyl esters thereof Cyclohexylenedimethylene terephthalate resin. The method of claim 1,
The diol component is a polycyclohexylenedimethylene tere, which further comprises one or more selected from the group consisting of ethylene glycol, diethylene glycol, 1,4-butanediol, 1,3-propanediol and isosorbide Phthalate resin. The method of claim 2,
The diol component comprises at least 90 mol% of cyclohexanedimethanol in a total of 100 mol% of the diol component,
Polycyclohexylenedimethylene tere, containing 10 mol% or less of one or more selected from the group consisting of ethylene glycol, diethylene glycol, 1,4-butanediol, 1,3-propanediol, and isosorbide Phthalate resin. The method of claim 1,
The second component of the acid component is isophthalic acid or an alkyl ester thereof, polycyclohexylenedimethylene terephthalate resin. The method of claim 1,
The polycyclohexylene dimethylene terephthalate resin is dissolved in o-chlorophenol at a concentration of 1.2 g / dl, the intrinsic viscosity measured at a temperature of 35 ℃ using a Uberod viscous tube is 0.50 to 1.20 dl / g, Polycyclohexylenedimethylene terephthalate resin. The method of claim 1,
The polycyclohexylenedimethylene terephthalate resin is a polycyclohexylenedimethylene terephthalate resin having a vinyl end group content of 35 ppm or less represented by the following Chemical Formula 1 and Chemical Formula 2 when quantitatively analyzed using a GC chromatogram instrument. :
[Formula 1]

[Formula 2]

To a diol compound comprising cyclohexanedimethanol dissolved in water, terephthalic acid or dimethyl terephthalate as a first component, and isophthalic acid, dimethylisophthalate, cyclohexanedicarboxylic acid, adipic acid and succinic acid as a second component Preparing a liquid mixture by inputting an acid component including at least one selected from the group consisting of;
Adding nitrogen to the liquid mixture, stirring and bubbling;
Adding a catalyst to the liquid mixture, and raising the temperature to perform esterification or transesterification; And
Performing a polycondensation reaction under reduced pressure,
In the manufacturing step of the liquid mixture, the first component of 100 mol% of the acid component is included in more than 65 mol% to less than 80 mol%, the second component is contained in more than 20 mol% to 35 mol%, poly Method for producing cyclohexylenedimethylene terephthalate resin. The method of claim 7, wherein
The esterification or transesterification is carried out at 200 to 300 ℃, the polycondensation reaction is carried out at 250 to 290 ℃, a method for producing a polycyclohexylenedimethylene terephthalate resin. The method of claim 7, wherein
The esterification or transesterification is carried out at a pressure of 0.2 to 3.0 kg / ㎠, the polycondensation reaction is carried out at a pressure of more than 0 torr less than 5 torr, the preparation of polycyclohexylenedimethylene terephthalate resin Way. A fiber comprising the polycyclohexylenedimethylene terephthalate resin of claim 1. The method of claim 10,
A fiber having a physical property retention rate of 85% or more after standing in a constant temperature and humidity oven at a temperature of 85 ° C. and a relative humidity of 85% for 12 weeks. The method of claim 10,
Fibers further comprising polyester resins other than polycyclohexylenedimethylene terephthalate. The method of claim 12,
The polyester resin other than the polycyclohexylenedimethylene terephthalate is polyethylene terephthalate, polyethylene 2,6-dinaphthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene isophthalate or a mixture thereof.