KR20170110064A - Polyester Fiber with Excellent Touch and Color - Google Patents

Abstract

The present invention relates to an acidic component comprising a polyester as a core component and terephthalic acid or an ester-forming derivative thereof as a sheath component; 2-methyl-1,3-propanediol, a diol component consisting of diethylene glycol and ethylene glycol; Methyl-1,3-propanediol is produced by co-spinning a co-polyester produced by copolymerizing 2-methyl-1,3-propanediol with a polyester of the formula To 10% by mole to 50% by mole of the diethylene glycol, and 1 to 25% by mole of the diethylene glycol.

Description

Polyester Fiber with Excellent Touch and Color "

The present invention relates to a polyester-based conjugated fiber. More specifically, the present invention relates to a polyester-based composite fiber excellent in touch and color and excellent in touch and color.

Thermal fused fibers can be used to bond filaments or staple fibers that make up the web or sheet of the nonwoven fabric. The thermally welded fiber should have a glass transition temperature close to that of a general polyethylene terephthalate fiber at a heat bonding temperature of 140 to 150 ° C. In order to do so, the crystal structure in the polymer must be eliminated and the polymer structure should be made amorphous.

Polyesters have excellent mechanical properties, heat resistance and chemical resistance, and are used in fiber and engineering plastic materials. However, they have a semi-crystalline nature due to their molecular structure and are difficult to use for heat fusion because of their high melting point. In order to use polyester as a heat-sealable fiber, a high temperature and pressure are required in the manufacturing process, and therefore, there are many difficulties in the process. Therefore, a lot of research has been continued for development of heat-wearable polyester.

U.S. Patent No. 4,129,675 discloses a low melting point copolymer polyester copolymerized with terephthalic acid and isophthalic acid. However, the copolymerized polyester of this patent has a disadvantage in that it can be thermally fused at a high temperature of 190 캜 or more, and thus consumes a lot of energy in the process.

U.S. Patent No. 4,166,896 discloses a method for producing an unsaturated polyester by copolymerizing unsaturated dicarboxylic acid or the like with a low-molecular weight material having depolymerized polyester. However, this method is not only economical, but also has a high melting point There are disadvantages of high determination.

Korean Patent Laid-Open No. 2001-11548 discloses a polyester resin composition which is obtained by intensifying the dicarboxylic acid component of terephthalic acid and phthalic anhydride and the diol component of ethylene glycol and diethylene glycol to obtain an excellent adhesive strength to polyester, However, this binder is disadvantageous in that the reaction mechanism is complicated by directly using anhydrous phthalic acid, and therefore the condensation polymerization temperature must be lowered in order to prevent the problem of poor color of the copolyester. In addition, such a low temperature polycondensation reaction has a problem in that the productivity is lowered.

The copolyester synthesized by using the phthalic anhydride of Korean Patent Laid-Open No. 2001-11548 has a color of the obtained polymer under the same conditions as the polyethylene terephthalate polycondensation process in which the copolymer polyester is heated to 270 ° C. to 290 ° C. under a reduced pressure of 1 mmHg or lower There is a disadvantage that it becomes defective. This is because the phthalic anhydride charged in the composition of the reaction system under the high temperature and high vacuum polymerization conditions participates in the reaction in the state where the ring opening reaction, the direct esterification reaction and the transesterification reaction are mixed in the reaction process and pyrolysis and side reactions are generated, Because.

In the present invention, in order to solve the problems of the prior art as described above, in the low melting point fusing polyester resin to be used in the present invention, the content of the cyclic compound acting as a foreign substance is small, , And developed polyester composite fiber having excellent thermal fusion, touch and color at low temperature by using this resin.

An object of the present invention is to provide a polyester-based composite fiber excellent in thermal bonding strength at a low process temperature of 140 to 160 ° C and excellent in high-quality new touch and color, excellent in touch and color after bonding .

Another object of the present invention is to solve the problem of poor color due to accumulation of coloring materials due to pyrolysis and side reaction when polymerizing phthalic anhydride as a copolymerization component in the prior art, In contrast to the problem of deterioration of productivity through low-temperature polycondensation reaction, the inclusion of a phenol-phosphorus compound heat stabilizer (hereinafter referred to as "Ph-P compound heat stabilizer") protects the resin at high temperature and prevents discoloration, And a color-b value, which is a numerical value, is low.

These and other objects of the present invention can be achieved by the present invention which is described in detail below.

The present invention relates to an acidic component comprising a polyester as a core component and terephthalic acid or an ester-forming derivative thereof as a sheath component; 2-methyl-1,3-propanediol, a diol component consisting of diethylene glycol and ethylene glycol; Methyl-1,3-propanediol is produced by co-spinning a co-polyester produced by copolymerizing 2-methyl-1,3-propanediol with a polyester of the formula To 10% by mole to 50% by mole of the diethylene glycol, and 1 to 25% by mole of the diethylene glycol.

The present invention also provides a polyester-based composite fiber excellent in tactile feeling and color, characterized in that amorphous characteristics are exhibited in the above-mentioned copolyester.

Also, the polyester-based composite fiber is excellent in touch and color, wherein the sum of the contents of 2-methyl-1,3-propanediol and diethylene glycol is 30 to 50 mol% in the diol component.

The present invention also provides a polyester-based composite fiber having excellent tactile and color characteristics, which further comprises a Ph-P composite heat stabilizer having the following formula of 1 to 1,000 ppm based on phosphorus (P) content.

The present invention also provides a polyester-based composite fiber having excellent tactile and color characteristics, characterized by further adding a polyfunctional component in the range of 10 to 10,000 ppm in order to enhance intermolecular bonding.

The polyfunctional component may be at least one selected from the group consisting of polycarboxylic acid, polyol, polyoxycarboxylic acid, trimellitic acid, trimesic acid, 3,3,4,4-benzophenonetetracarboxylic acid, 1,2,3,4- The present invention provides a polyester-based composite fiber having excellent tactile and color characteristics, which is characterized by being selected from the group consisting of carboxylic acids and derivatives thereof, glycerin, trimethylol propane, pentaerythritol, and sorbitol.

INDUSTRIAL APPLICABILITY As described above, according to the present invention, it is possible to provide a polyester-based composite fiber excellent in low-temperature weldability and excellent in touch feeling and color after contact.

In addition, since the cyclic compound is not involved in the production, it is possible to increase the cycle of pack replacement at the time of spinning. Meanwhile, in order to increase the thermal stability of the resin, Ph-P composite heat stabilizer may be added in an amount of 1 to 1,000 ppm based on phosphorus (P) content.

By this, it is possible to protect the resin by removing radicals under a high temperature polycondensation reaction, and to prevent the discoloration of the resin by decomposing the peroxide. On the other hand, 10 to 10,000 ppm, more preferably 50 to 3,000 ppm, of a multifunctional component having a crosslinking action can be added in order to enhance intermolecular bonding. By doing so, the condensation polymerization reaction time can be shortened, and in the case of spinning and stretching in the form of a fiber, it is possible to improve the fairness by reducing the embossing rate.

TECHNICAL FIELD The present invention relates to a polyester-based composite fiber, and relates to a polyester-based composite fiber excellent in touch and color by using a low-melting-point copolymer polyester excellent in touch and color and containing a small amount of a cyclic compound in a resin.

The polyester-based composite fiber according to the present invention is a composite fiber comprising a general polyester as a core component and a copolymerized polyester as a sheath component, wherein the copolymerized polyester comprises an acid component comprising terephthalic acid and / or an ester- Methyl-1,3-propanediol, diethylene glycol, and ethylene glycol.

The methyl group of the second carbon of the 2-methyl-1,3-propanediol facilitates the rotation of the polymer main chain and acts as a terminal part of the polymer, thereby widening the free space between the main chains. Therefore, it not only enables thermal bonding between fibers even at a low process temperature, but also has excellent form stability even at a high temperature of 100 to 130 DEG C after the production of the nonwoven fabric. However, although the effect of lowering the melting temperature is large, it does not significantly lower the glass transition temperature, and it exhibits a high glass transition temperature of 65 ° C or higher even when it is made into an amorphous polymer when used alone

Methyl-1,3-propanediol is preferably 10 to 50 mol% based on the mole of the ester in the copolymer polyester, and when the content is less than 10 mol%, the melting point is not sufficiently lowered, The resin can not be obtained. When the amount is more than 50 mol%, the crystallinity is sufficiently lowered, so that no further effect can be obtained. On the contrary, when the amount is excessively added, it acts as a main component in the diol component and adversely affects the crystallinity. The content of the diethylene glycol is preferably 1 to 25 mol% based on the ester molar amount. When the content is less than 1 mol%, it is impossible to obtain a polyester resin that inhibits the melting point and the formation of the cyclic compound, %, The glass transition temperature is lowered to 55 ° C or less, which may lead to a problem of change of the fiber over time during spinning.

In the present invention, a Ph-P composite heat stabilizer having the following formula can be used to enhance thermal stability, and the amount of the Ph-P composite heat stabilizer is preferably 1 to 1,000 ppm based on the copolymer polyester.

When the addition amount of the heat stabilizer is 1 ppm, the desired thermal stability is not improved, and when 1,000 ppm or more is added, the reactivity is lowered.

On the other hand, the multifunctional component used in the production of the copolymerized polyester of the present invention is selected from the group consisting of polycarboxylic acids, polyols and polyoxycarboxylic acids, and in particular, trimellitic acid, trimesic acid, 3,3 ' 4'-benzophenonetetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid and derivatives thereof such as acid esters and acid anhydrides thereof, glycerin, pentaerythritol and sorbitol. At this time, the polyfunctional component is used to lower the excessive temperature rise of the resin due to the exothermic reaction during the polycondensation of the copolyester according to the present invention, to shorten the reaction time to improve color defects, It is preferable that 10 to 10,000 ppm is included in each of the copolymer polyester components so as to improve the properties. However, it is more advantageous that the melt viscosity is not too high for the purpose of application, and more preferably 50 to 3,000 ppm is added. If the added amount of the polyfunctional component is less than 10 ppm, the desired crosslinking agent can not be attained. If the added amount exceeds 10,000 ppm, rapid crosslinking causes problems in polymerization, spinning and stretching.

Hereinafter, the present invention will be described in more detail with reference to the following examples, but these examples are only illustrative of the present invention and are not intended to limit or limit the scope of protection of the present invention.

Examples 1 to 3

Terephthalic acid and ethylene glycol were added to the ester reaction tank and reacted at a temperature of 258 ° C by a conventional method to prepare an oligomer having a 96% reaction rate. 2-methyl-1,3-propanediol, diethylene glycol, and ethylene glycol are added to the oligomer obtained from the resultant, together with the Ph-P composite heat stabilizer and the conventional transesterification catalyst, in an amount of, based on the molar amount of polyethylene terephthalic acid, Followed by transesterification at 250 ° C. Trimethylol propane (TMP), which is a kind of multifunctional reaction, and a conventional polycondensation catalyst were added to the esterified oligomer thus obtained, and then the temperature was elevated up to 280 DEG C while gradually reducing the pressure to 0.1 mmHg so that the polycondensation reaction Respectively. The performance of the thus-prepared polyester resin was evaluated as described above, and the results are shown in Table 1 below.

Comparative Examples 1 to 3

In order to verify the effect of the heat stabilizer and the multifunctional reactor, the diol component charging ratio was set in the same manner as in Example 1, and the heat stabilizer type (Ph-P composite system or P system as a general phosphorus thermal stabilizer) Were polymerized in the same manner as in Examples 1 to 3, except that they were not added or introduced as in Examples 1 to 3. The performance of the thus-prepared polyester resin was evaluated as described above, and the results are shown in Table 1 below.

Comparative Examples 4 to 6

Except that 2-methyl-1,3-propanediol was added in an amount of isophthalic acid in each of the amounts and heat stabilizer types and multi-functional reactors were not added or introduced as shown in Table 1, . The performance of the thus-prepared polyester resin was evaluated as described above, and the results are shown in Table 1 below.

MPD: 2-methyl-1,3-propanediol, DEG: diethylene glycol, EG: ethylene glycol

IPA: isophthalic acid, TMP: trimethylol propane

The evaluation items shown in the above Examples and Comparative Examples were measured as follows.

1. Measurement of cyclic compound and TMP content: The molar percentage of the additive of the copolymerized polyester was determined by dissolving the copolymer polyester in trifluoroacetic acid and measuring the content of the copolyester by using DRX-300 proton nuclear magnetic resonance apparatus (1 H NMR) of Bruker Co. Respectively.

2. Measurement of Melting Point / Glass Transition Temperature and Softening Behavior: Measured using a thermal differential scanning calorimeter (Perkin Elmer, DSC-7). When there is no heat absorption peak, that is, when no melting point exists, (Perkin Elmer, DMA-7; TMA mode) was used to measure the softening behavior.

3. Determination of intrinsic viscosity (IV): Copolymer polyester was dissolved in phenol / tetrachloroethane (weight ratio 50/50) to make a 0.5 wt.% Solution and then measured at 35 DEG C with a Uvold viscometer.

4. Adhesion at room temperature: The prepared heat-sealable nonwoven fabric was fixed at a density of 2 g / 100 cm < 2 > and the ambient temperature was measured at 25 DEG C by the method of ASTM D1424.

5. Tactile sensation: Relative evaluation was performed by touching with hand. (Excellent (good), good (good), good (fair), poor (poor))

As shown in Table 1, when Examples 1 to 3 using 2-methyl-1,3-propanediol were compared with Comparative Examples 1 to 4 using isophthalic acid, they had at least an intrinsic viscosity of about the same level, When methyl-1, 3-propanediol is added, the b value indicating yellowing degree is lower, so the color is better and the feel is softer. As can be seen from the results of the room temperature bonding strength, even when polymerization was carried out using 2-methyl-1,3-propanediol, the adhesive strength was comparable to that of Example 1. When the polyfunctional reactor was compared with Example 1 and Comparative Example 1, And thus the adhesive strength was better and the reaction time was reduced. Comparing Example 1 and Comparative Example 2, it can be seen that when the Ph-P composite heat stabilizer is added, b is lower and the color is better than when using a normal P-type heat stabilizer. In addition, isophthalic acid reacts with ethylene glycol to form a cyclic dimer, which acts as a foreign substance, shortening the cycle of pack exchange, not only causing poor radioactivity, but also has a disadvantage that the cost of isophthalic acid is high. 2-methyl-1,3-propanediol and diethylene glycol do not participate in the formation of cyclic dimer, which contributes to lowering the foreign matter content in the polyester and increasing the cycle of the pack exchange. .

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (6)

General polyester as core component: and
An acid component composed of terephthalic acid or an ester-forming derivative thereof as a sheath component;
2-methyl-1,3-propanediol, a diol component consisting of diethylene glycol and ethylene glycol;
In a polyester-based composite fiber having excellent tactile feeling and color, which is produced by co-spinning a copolymer polyester prepared by copolymerizing a polyester-
Methyl-1,3-propanediol is added in an amount of more than 10 to 50 mol% based on the mole of the ester in the copolymer polyester and 1 to 25 mol% of the diethylene glycol. Polyester complex fiber with excellent texture and color. The method according to claim 1,
The polyester-based composite fiber is characterized in that the copolymer polyester exhibits amorphous properties. The method according to claim 1,
Methyl-1,3-propanediol, and diethylene glycol is 30 to 50 mol% of the diol component. The method of claim 1, wherein
Wherein the copolymer polyester further comprises a Ph-P composite heat stabilizer having a composition of 1 to 1,000 ppm based on the phosphorus (P) content of the following formula:

The method according to claim 1,
The polyester-based composite fiber is excellent in tactile and color properties, and further comprises a polyfunctional component in the range of 10 to 10,000 ppm in order to enhance intermolecular bonding. 6. The method of claim 5,
Wherein the polyfunctional component is at least one selected from the group consisting of polycarboxylic acid, polyol, polyoxycarboxylic acid, trimellitic acid, trimesic acid, 3,3,4,4-benzophenonetetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid And derivatives thereof, glycerin, trimethylol propane, pentaerythritol, and sorbitol. The polyester-based composite fiber is excellent in touch and color.