KR20200114397A - Cationic-dyeable latent crimping polyester fiber with improved dyeing property - Google Patents

Abstract

The present invention relates to cationic-dyeable latent crimping polyester fiber with improved dyeing property in side-by-side type latent crimping fiber formed of high melting viscosity polyester and low melting viscosity polyester. The high melting viscosity polyester is a cationic-dyeable polyester having a melt viscosity of 2,200-2,700 poises by copolymerizing a sulfoisophthalic acid metal salt (SM) and a sulfoisophthalic acid organic salt (SO) as an acid. The low melting viscosity polyester contains 2 to 15% by weight of a polyol having a number average molecular weight of 600 to 1,000 and a melt viscosity of 600 to 1,000 poises.

Description

Latent crimped polyester fiber with cationic flame retardancy with improved dyeability {CATIONIC-DYEABLE LATENT CRIMPING POLYESTER FIBER WITH IMPROVED DYEING PROPERTY}

The present invention relates to a latent crimped polyester fiber having improved dyeability and cationic flame retardant, and to a latent crimped fiber comprising a cation flame retardant polyester copolymerized with an organic sulfoisophthalic acid salt.

Latent crimped fiber is heat-shrinkable by applying heat in a spinning or drawing process after complex spinning of two types of polymers with different heat shrinkage properties in a side-by-side or sheath-core. It is a fiber that physically has a coil shape due to the difference and gives a high degree of elasticity and bulkyness by a principle similar to that of a spring.

Two types of polymers used in the manufacture of polyester-based crimped fibers include two types of polyethylene terephthalate (PET) having a difference in viscosity, or a method using a high-shrink copolymer polyethylene terephthalate. In addition to phthalate, a method using polytrimethylene terephthalate (PTT) or polybutylene terephthalate (PBT) has also been suggested.

Korean Patent Laid-Open No. 2000-0019601 discloses a side-by-side type composite fiber, in which the high and low shrinkage components of two different in situ polymers are in the shape of a taegeuk in cross section, so it has excellent adhesion at the interface and a spiral crimp. It is described about the spontaneous crimped fiber to be made.

However, in the case of manufacturing composite fibers using polymers with different shrinkage ratios, the interface of the positive component is separated by an external force applied to the fibers after spinning due to low adhesion at the interface due to low compatibility between polymers. Can have

Japanese Patent Laid-Open No. 2011-196006 relates to an atmospheric pressure cationic flame retardant polyester composite fiber, and a polyester copolymerized with 5-sodium sulfoisophthalic acid is disposed in a sheath, and 95 mol% or more is ethylene tere. A composite fiber in which a polyester made of a repeating unit of phthalate is disposed in a core portion is disclosed.

However, since the conjugated fiber as described above is a core-sheath type fiber, it is difficult to see a crimp rate such as a side-by-side type, an increase in processing cost in a spinning process, and it is difficult to spin at high speed.

The present invention is invented to solve the problems of the prior art as described above, and provides a latent crimp type polyester fiber having improved dyeability with improved dyeability with a high crimp rate by complex spinning cation flame retardant polyester. It aims to do.

In addition, it is an object of the present invention to provide a latent crimped polyester fiber having improved cation flame retardancy with improved dyeability capable of high-strength and high-strength fineness by composite spinning of cation flame retardant polyester.

In addition, it is an object of the present invention to provide a latent crimp-type polyester fiber having improved dyeability with improved clarity and dyeability while maintaining elasticity by composite spinning cation flame retardant polyester.

In the present invention, in the side-by-side type latent crimped fiber formed of high-melting-viscosity polyester and low-melting-viscosity polyester, the high-melting-viscosity polyester is a sulfoisophthalic acid metal salt (SM) and Sulfoisophthalic acid organic salt (SO) is copolymerized with an acidic component, and the melt viscosity is 2,200-2,700 poise cation-flammable polyester, and the low melting viscosity polyester is a polyol having a number average molecular weight of 600-1,000. It provides a latent crimped polyester fiber having improved dyeability and cation flame retardancy, characterized in that it contains 15% by weight of polyester having a melt viscosity of 600 to 1,000 poise.

In addition, the polyol is poly(tetramethylene ether) glycol (Poly (tetramethylene ether) glycol), polyethylene glycol (Polyethylene glycol), polytrimethylene glycol (Polytrimethylene glycol), characterized in that any one of the improved dyeability cation It provides a latent crimped polyester fiber having flame retardancy.

In addition, the sulfoisophthalic acid organic salt (SO) is dimethyl-5-sulfoisophthalic acid tetraphosphonium or dimethyl-5 sulfoisophthalic acid-tetrabutylammonium, characterized in that the dyeability improved cationic saltability Branches provide latent crimped polyester fibers.

In addition, it provides a latent crimped polyester fiber having improved dyeability and cationic flame retardancy, characterized in that the difference in melt viscosity between the high-melting-point polyester and the low-melting-viscosity polyester is 1500 to 2000 poise.

In addition, it provides a latent crimp-type polyester fiber having improved dyeability and cationic dyeability, characterized in that the crimp rate of the latent crimp-type polyester fiber having cation flame retardancy is 30% or more.

In the latent crimped polyester fiber having cation flame retardancy with improved dyeability according to the present invention as described above, both high melting viscosity polyester and low melting viscosity polyester have the effect of improving dyeability due to cationic flame retardancy, There is an effect of providing a fiber having a high crimp rate.

In addition, there is an effect of providing a latent crimped polyester fiber having cation flame retardancy capable of high elongation and high strength fineness by composite spinning of cation flame retardant polyester.

In addition, there is an effect of providing a latent crimp-type polyester fiber having cation flame retardancy having high clarity and dye retention while maintaining elasticity by composite spinning cation flame retardant polyester.

Hereinafter, a preferred embodiment of the present invention will be described in detail. First, in describing the present invention, detailed descriptions of related known functions or configurations are omitted so as not to obscure the subject matter of the present invention.

The terms'about','substantially', etc. of the degree used in the present specification are used at or close to the numerical value when manufacturing and material tolerances specific to the stated meaning are presented, and are used in the sense of the present invention. To assist, accurate or absolute figures are used to prevent unfair use of the stated disclosure by unscrupulous infringers.

'Polyester' disclosed in the present invention refers to polyester by condensation polymerization using terephthalic acid or its ester-forming derivative as the main acid component and ethylene glycol as the main diol component.

The present invention relates to a side-by-side type latent crimp type fiber formed of high-melting-viscosity polyester and low-melting-viscosity polyester.

The high-solubility-melting-viscosity polyester is formed of a copolymerized polyester with ethylene terephthalate as the main repeating unit, and using a sulfoisophthalic acid metal salt (SM) and a sulfoisophthalic acid organic salt (SO) by copolymerization of an acid component.

The high melting point polyester is a sulfoisophthalic acid metal salt (SM) in which X in the following formula 1 is an alkali cation or an alkaline earth metal cation, and sulfoi in which X in the following formula 1 is a quaternary phosphonium ion or a quaternary ammonium ion. It would be preferred to be a cationic salty polyester containing an organic salt of sophthalic acid (SO).

As the sulfoisophthalic acid organic salt, dimethyl-5-sulfoisophthalic acid tetraphosphonium (DHSP) or dimethyl-5 sulfoisophthalic acid-tetrabutylammonium may be used.

[Formula 1]

[In the above formula, R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a β-hydroxyethyl group.]

As described above, it is preferable that the polyester having a high melting point containing the metal sulfoisophthalic acid (SM) and the organic sulfoisophthalic acid (SO) satisfies the following equations (1) and (2) at the same time.

Equation (1): 0.1≤(SM+SO)≤3.0

Equation (2): 0.01≤(SM/SO)≤100.0

[In the above equation, SM is the copolymerization amount (mol%) of the sulfoisophthalic acid metal salt (SM) based on the total acid components constituting the copolymerized polyester, and SO is based on the total acid components constituting the copolymerized polyester. Represents the copolymerization amount (mol%) of the sulfoisophthalic acid organic salt (SO)]

Equation (1) is a formula related to the cation flame retardancy of polyester with a high melting viscosity. If the SM+SO is less than 0.1, the reactivity with the cation dye may be reduced, thereby reducing the cation flame retardancy, and SM+SO If it exceeds 3.0, the physical properties of the polyester fiber may decrease.

Equation (2) is a formula related to the physical properties of the polyester having a high melting point to be produced. If the content of the sulfoisophthalic acid metal salt increases, the degree of polymerization may decrease during polymerization of the copolymerized polyester, so that the value of SM/SO is 0.01≦( It would be desirable to have SM/SO)≦100.0.

The low-melting-viscosity polyester contains polyol to improve the low-temperature dyeing properties of the low-melting-viscosity polyester and improve the crimp properties of the latent crimped polyester fiber.

The polyol is preferably a polyol having a number average molecular weight of 600 to 1,000, and a low melting point of 2 to 15% by weight of polyester is preferably contained.

When the polyol is contained in less than 2% by weight, there is no low-temperature dyeing effect, and when it is contained in 15% by weight or more, the low-temperature dyeing effect is not further increased. The polyol will most preferably be contained in 5 to 10% by weight of the low melting point polyester.

As for the polyol, it is preferable to use any one of poly(tetramethylene ether) glycol, polyethylene glycol, and polytrimethylene glycol as the polyol.

The low melting viscosity polyester containing the polyol preferably has an intrinsic viscosity (IV) of 0.6 to 0.8, more preferably 0.65 to 0.75.

The latent crimp-type polyester fiber having cationic flame retardancy prepared in the present invention has latent crimp property and the crimp rate of the fiber must be 30% or more to improve the manufacturability of a woven fabric having stretch characteristics.

The crimp properties of the present invention can be expressed by a difference in the melt viscosity of the high-melting-viscosity polyester and the low-melting-viscosity polyester.

Polyesters with high melt viscosity have a relatively larger interaction compared to polyesters with lower melt viscosity, so if two types of polyesters with different melt viscosity are combined and spun, polyesters with relatively high melt viscosity become round. In the heat treatment process after stretching and stretching, it shrinks further by the interaction between molecules, thereby expressing the crimp on the fiber.

Therefore, when the melt viscosity is measured based on 100 rad/s at 290 degrees, the melt viscosity of the high melting point polyester is 2,200 to 2,700 poise (P), and the melt viscosity of the low melting viscosity polyester is 600 to 1,600 poise. It would be desirable to be.

If the melt viscosity of the high-melting viscosity polyester is less than 2200 poise due to the interaction of the polyester, the discharge speed through the nozzle becomes very fast, resulting in howitzer occurs, and if the melt viscosity exceeds 2700 poise, there is a problem in workability during spinning. There may be.

The melt viscosity of the polyester may be controlled by the molecular weight, the copolymer, and the amount of plasticizer added.

In addition, the difference in melt viscosity between the high melting point polyester and the low melting point polyester is preferably 1500 to 2000 poise, and if the difference in viscosity is out of the above range, there is a problem that the adhesion between the interfaces is significantly lowered, and the elasticity of the fiber may be lowered. .

The cross section of the spun yarn due to the difference in melt viscosity as described above forms a cross section as shown in Fig. 1 or 2, and the interface forms a round shape with a high melting point polyester side due to the difference in melt viscosity. do.

In order to better express the crimp property due to the difference in melt viscosity of the polyester, the weight ratio of the high melting point polyester and the low melting point polyester will preferably be 30:60 to 70:40.

If the high melting point polyester content is less than 30% by weight, the shrinkage effect decreases, so that the volume and softness of the fabric decreases rapidly, and if it exceeds 70% by weight, the manufacturing process may be deteriorated.

The latent crimped polyester fiber having cation flame retardancy with improved dyeability according to the present invention is a side-by-side composite fiber using high-melting-viscosity polyester and low-melting-viscosity polyester. It is manufactured and includes a spinning step and a stretching step, and may optionally include a false twist step.

In the spinning step, high-melting-viscosity polyester and low-melting-viscosity polyester are each prepared and spun through each of the discharge holes using a nozzle. The discharged individual fibrous polyester may have a side-by-side cross section after being discharged through a nozzle and bonded by the physical properties of the polymer.

In the stretching step, the spun fibers are stretched through two rollers.

As the draw ratio increases, the crimp rate increases, so when the draw roller is at a temperature of 50 to 100°C, it can be appropriately adjusted between 1.5 and 2.0, and more preferably, it can be stretched to 1.7 to 1.9.

When the stretching ratio is increased by 0.1, it is preferable that the crimp rate increase rate is 5% or more, but when the stretching ratio exceeds 2.0, trimming may occur during the softening operation.

The latent crimped polyester fiber having cationic flame retardancy prepared in the present invention has high strength and draw ratio, because the high-melting-viscosity polyester has a high strength compared to general polyester.

Therefore, it will be preferable that the latent crimp-type polyester fiber having cation flame retardancy prepared by the present invention has a strength of 2.0 to 3.5 g/d.

If the strength is less than 2.0g/d, threading occurs during spinning, and workability may be lowered during fabrication of a woven fabric, and if the strength exceeds 3.5g/denier, the fabric manufacturing feel may be defective.

The false twisting step may include a process of heat treatment by passing the stretched composite fiber through a separate heater plate.

In addition, the latent crimp-type polyester fiber having cation flame retardancy with improved dyeability produced by the above method is capable of expressing a large number of crimps per unit length while undergoing the relaxation heat treatment process of post-processing. The elasticity of the knitted fabric is improved to give a soft and comfortable fit.

Hereinafter, an example of a method for producing a latent crimped polyester fiber having cation flame retardancy with improved dyeability according to the present invention is shown, but the present invention is not limited to the examples.

Examples 1 to 4

The melt viscosity of high-melting-viscosity polyester and low-melting-viscosity polyester is 2400 poise and 800 poise, respectively, and the spinning temperature of high viscosity extruder is 260~290℃, and the temperature range of low viscosity extruder is 240~260℃. It was adjusted and melted through each extruder, spun at a spinning speed of 2,900 m/min in a 50:50 weight ratio, and then stretched and oriented 1.8 times to prepare a latent crimped polyester fiber having cationic flame retardancy according to the present invention. .

The high melting viscosity polyester is di(β-hydroxyethyl)-5-sulfoisophthalate sodium salt (DMS) 1.3 mole% and dimethyl-5-sulfoisophthalate tetra in oligomer having a saponification value of 9.7 KOH mg/g. Phosphonium (DHSP) 0.5mole% After addition, the temperature was raised to 280°C, and condensation polymerization was carried out under high vacuum.

The low-melting-viscosity polyester contained 3% by weight of polyethylene glycol having a number average molecular weight of 800 when preparing polyethylene terephthalate and subjected to a condensation polymerization reaction.

Latent crimped polyester fibers having improved cation flame retardancy were fabricated and dyed using kayacril CD bule, a cation dye.

Example 2

It was prepared in the same manner as in Example 1, but was prepared by containing 6% by weight of polyethylene glycol of the low-melting-viscosity polyester.

Example 3

It was prepared in the same manner as in Example 1, but was prepared by containing 10% by weight of polyethylene glycol of the low-melting-viscosity polyester.

Example 4

It was prepared in the same manner as in Example 1, but was prepared by containing 15% by weight of polyethylene glycol of the low-melting-viscosity polyester.

Comparative example

It was prepared in the same manner as in Example 1, but the low melting point was prepared without containing polyethylene glycol of polyester.

The physical properties of the latent crimped polyester fibers having cationic flame retardancy prepared in Examples 1 to 4 and Comparative Examples were measured and shown in Table 1.

◎ Measurement method

* Intrinsic Viscosity (IV, Intrinsic Viscosity): Each polymer was sufficiently dissolved in ortho-chlorophenol at 120° C. at a concentration of 1%, and then measured using a Ubelrod viscometer in a 30° C. thermostat.

*Melt viscosity (MV, Melt viscosity): Melt viscosity at a shear rate of 100 rad/sec measured at 290°C

* Spinning fairness evaluation: The number of times the fiber is cut and broken during spinning

-Good: less than once/day

-Defective: 1 time/day or more to less than 10 times/day

-Very bad: 10 times/day or more

* Tensile strength was measured by the method of ASTM D3822.

* Dyeability evaluation: Relative sensory evaluation by 5 experts (score given out of 100)

* Fineness (denier): In accordance with ASTM D 1577, it was measured by the Favimat equipment of Textechno.

* Shrinkage rate in boiling water (BWS: Boiling Water Shrinkage)

200 mg weight was suspended in a sample having an initial length of 50 cm, immersed in boiling water for 15 minutes, dried for 5 minutes in air, and the shrinkage rate in boiling water was determined according to the following equation.

* Shrinkage rate (%) = (length of initial sample-length of sample after shrinkage)/length of initial sample × 100

* Crimping rate (Tc, %): Take a sample of skein as much as 3,000 denier in the state that a tension of 50mg/denia is given to the sample. This sample was treated in hot water (100°C) for 20 minutes under a load of 0.5 mg/denia, the load was removed, and left to stand for 24 hours to dry naturally. After natural drying, the length (L1) is measured after 1 minute after applying a load of 2 mg/denia to the sample, and 1 minute after applying a load of 2 mg/denia + 200 mg/denia, the length (L2) is measured. .

The value measured in this way is substituted into the following equation (1) to obtain the crimp rate.

<Equation (1)> Tc(%) = (L2-L1)/L2 × 100

division unit Example 1 Example 2 Example 3 Example 4 Comparative example burglar g/de 2.52 2.58 2.63 2.55 2.48 Shinto % 22.7 23.1 23.9 24.2 20.2 Dyeability point 80 90 95 95 65 Heat shrink % 17.1 16.9 17.5 17.4 16.9 Crimp rate % 32.2 32.8 31.9 33.5 31.4

As can be seen from the results of Table 1, Examples 1 to 4 and Comparative Examples can be seen that there is no significant difference in strength, crimp rate, and heat shrinkage, and Examples containing polyols have improved elongation than Comparative Examples. Can be seen.

When comparing the dyeing properties of the above Examples and Comparative Examples, Examples 1 to 4 containing polyols all received a high evaluation of 80 points or more in dyeability, but the Comparative Example received a lower evaluation of 65 points than the Example.

In addition, when comparing the dyeing properties of Examples 1 to 4, it can be seen that the dyeing property is excellent when the polyol is contained in an amount of 10% by weight or more, and when the polyol is contained in 10% by weight, the dyeing property improvement effect is not improved.

Therefore, it will be preferable that the polyol is contained in a polyester having a low melting point of 5 to 10% by weight.

Claims (5)

In the side-by-side type latent crimped fiber formed of high-melting-viscosity polyester and low-melting-viscosity polyester,
The high melting viscosity polyester is a cationic flame retardant polyester having a melt viscosity of 2,200 to 2,700 poise by copolymerizing a sulfoisophthalic acid metal salt (SM) and an organic sulfoisophthalic acid salt (SO) as an acid,
The low-melting-viscosity polyester contains 2-15% by weight of a polyol having a number average molecular weight of 600-1,000 and a melt viscosity of 600-1,000 poise. Crimped polyester fiber. The method of claim 1,
The polyol is poly(tetramethylene ether) glycol (Poly (tetramethylene ether) glycol), polyethylene glycol (Polyethylene glycol), polytrimethylene glycol (Polytrimethylene glycol), characterized in that any one of the improved dyeability cationic flame retardancy Latent crimped polyester fiber having. The method of claim 1,
The sulfoisophthalic acid organic salt (SO) is dimethyl-5-sulfoisophthalic acid tetraphosphonium or dimethyl-5 sulfoisophthalic acid-tetrabutylammonium, characterized in that it has improved dyeability and cationic saltability. Crimped polyester fiber. The method of claim 1,
Latent crimped polyester fiber having improved dyeability and flame retardancy, characterized in that the difference in melt viscosity between the high-melting-viscosity polyester and the low-melting-viscosity polyester is 1500 to 2000 poise. The method of claim 1,
Latent crimped polyester fiber having improved dyeability, characterized in that the crimp rate of the latent crimped polyester fiber having cation flame retardancy is 30% or more.