KR102278148B1 - Method for manufacturing high strength dyed-polyethylene terephthalate fiber and dyed fiber produced therefrom - Google Patents

Abstract

An object of the present invention is to provide a method for producing a high-strength polyethylene terephthalate original yarn with improved physical properties and good appearance due to the introduction of a high-viscosity masterbatch, and an original yarn.

Description

Manufacturing method of high-strength polyethylene terephthalate raw yarn and raw yarn manufactured therefrom

An object of the present invention is to provide a method for producing a high-strength polyethylene terephthalate original yarn with improved physical properties while having a good appearance due to the input of a high-viscosity masterbatch, and a dyed yarn prepared therefrom.

In general polyester yarn, the amount of dye is increased in order to express a high-concentration color in the dyeing process, and thus there are problems such as generation of dyeing wastewater and lowering of fastness. In addition, in the case of the polyester microfiber, since the apparent density is decreased due to an increase in the surface area due to the decrease in the thickness of the fiber, more and more dyes must be added to represent a sufficient color density, and thus the problem becomes more serious.

Therefore, in order to solve this problem, a dyed yarn product using carbon black as a pigment has been released, and in the case of a black dyed product, color concentration and fastness are improved.

In the case of polyester dyed yarn, the above problem can be solved to some extent, but in the case of single yarn fineness of 1 or less, due to an increase in surface area due to a decrease in the thickness of the fiber, a decrease in blackness and a decrease in spinning fairness due to the addition of carbon black occur, so it is not commercialized. to be.

Accordingly, in Korean Patent Nos. 531,939, 359,334, and Korean Patent Publication Nos. 2006-0078800, 2007-0056222, etc., by adding carbon black to the sea-island-type or split-type polyester microfiber manufacturing process, polyester raw microfibers are produced. By making it, the color fastness and color intensity of the dyeing were improved. However, in the manufacturing process of the above patents, an additional process for alkali reduction is absolutely necessary, and additional dyeing is required for the expression of a high-concentration color such as black.

In addition, when manufacturing polyester yarns used for industrial webbing, ropes, fabrics, etc., if the content of carbon black and colored inorganic pigments in the yarn is high, the defective rate of the yarn is high due to the yarn cutting in the yarn manufacturing process, and in the weaving process There is a problem in that many defects are generated due to fluff.

On the other hand, the conventional spinning yarn is spinning by mixing a master batch containing carbon black, and at this time, the carbon black is injected into the master batch having a viscosity of about 0.64 dl/g. During work, a lot of heat enters the polyethylene terephthalate and the viscosity of the polyethylene terephthalate decreases. The dropped viscosity is about 0.55 to 0.60 dl/g, and a masterbatch having a low viscosity becomes an obstacle to strength expression when spinning a raw yarn.

An object of the present invention is to provide a method for producing a high-strength polyethylene terephthalate original yarn for excellent strength during raw yarn spinning by increasing the viscosity of the masterbatch chip, and a raw yarn prepared therefrom.

The present invention comprises the steps of preparing a polymer by mixing and melting a polyethylene terephthalate master batch containing carbon black particles and a polyethylene terephthalate chip; and spinning the polymer by a spinning nozzle, stretching it in multiple stages, and then winding it to prepare a polyethylene terephthalate yarn; wherein the polyethylene terephthalate masterbatch has a viscosity (IV) of 0.7 to 1.1 through solid-state polymerization d/g, and the polyethylene terephthalate chip has a viscosity of 1.0 to 1.1 d/g.

Here, the input ratio of the polyethylene terephthalate masterbatch is 2 to 5%, the prepared raw yarn has a strength of 8.5 to 10.0 g/d, the strength is 13.0 to 15.0 kgf, the cut elongation is 16 to 19%, and the toughness is 36 to 42 g/d, and the carbon black particles include 5 to 25 wt% based on 100 wt% of the total polyethylene terephthalate masterbatch.

According to another preferred embodiment of the present invention, there is provided a high-strength polyethylene terephthalate dyed yarn prepared by the above manufacturing method.

The present invention includes a master batch chip of high viscosity containing carbon black in the polyethylene terephthalate dyed yarn, so that it is possible to manufacture a high-strength raw yarn in the yarn manufacturing process.

Hereinafter, the present invention will be described in detail.

The present invention comprises the steps of preparing a polymer by mixing and melting a polyethylene terephthalate master batch containing carbon black particles and a polyethylene terephthalate chip; and spinning the polymer by a spinning nozzle, stretching it in multiple stages, and then winding it to prepare a polyethylene terephthalate yarn; wherein the polyethylene terephthalate masterbatch has a viscosity (IV) of 0.7 to 1.1 through solid-state polymerization d/g, and the polyethylene terephthalate chip has a viscosity of 1.0 to 1.1 d/g.

Here, the input ratio of the polyethylene terephthalate masterbatch is 2 to 5%, the prepared raw yarn has a strength of 8.5 to 10.0 g/d, the strength is 13.0 to 15.0 kgf, the cut elongation is 16 to 19%, and the toughness is 36 to 42 g/d, and the carbon black particles include 5 to 25 wt% based on 100 wt% of the total polyethylene terephthalate masterbatch.

According to another preferred embodiment of the present invention, there is provided a high-strength polyethylene terephthalate dyed yarn prepared by the above manufacturing method.

A method for producing a polyethylene terephthalate original yarn according to the present invention will be described in detail as follows.

First, a polyethylene terephthalate master batch including carbon black particles and the like is prepared.

In the present invention, when manufacturing the master batch, it is preferable to use a chip having a high viscosity of 0.70 to 1.2 dl/g in order to improve spinning operability and deterioration in physical properties due to a decrease in viscosity. If the viscosity of the master batch is less than 0.7 dl/g, the physical properties are deteriorated during spinning, and when it exceeds 1.2 dl/g, a problem of poor spinning such as melt non-uniformity occurs.

The master batch is prepared by solid-state polymerization, and the conditions of solid-state polymerization are drying at less than 1 torr at 120 ° C, crystallizing the surface at 140 ° C, and maintaining the master batch at 235 ° C. keep

In addition, the content of the carbon black particles is preferably 5 to 25% by weight based on 100% by weight of the total polyethylene terephthalate master batch. When the content of carbon black particles is less than 5% by weight, a large amount of master batch must be added to obtain the desired blackness, so there is a problem in that the strength expression of the original yarn and the original yarn cost increases, and the content of the carbon black particles is 25% by weight. When it exceeds, it becomes difficult to manufacture a master batch, and it is difficult to ensure uniform dispersibility.

The average particle diameter of the carbon black particles is not particularly limited, but is preferably 10 to 25 nm, more preferably 16 nm. When the average particle diameter of the carbon black particles is 10 nm or less, the dispersibility is lowered, the yield is lowered in the process of manufacturing the master batch, and the color of the prepared original yarn is not uniform because of the non-uniform dispersion, and the average of the carbon black particles When the particle size exceeds 25 nm, a lot of yarn breakage may occur when manufacturing a raw yarn having a strength of 7.0 g/d or more with a yarn having a single yarn fineness of 10 denier or less.

A polymer is prepared by mixing and melting the polyethylene terephthalate master batch prepared as described above with a polyethylene terephthalate chip having an intrinsic viscosity of 1.0 dl/g or more. Preferably, the intrinsic viscosity of the polyethylene terephthalate chip is in the range of 1.0 to 1.2 dl/g.

As described above, the mixed and melted polymer is spun by a spinning nozzle, and then passed through a cooling zone to be rapidly cooled and solidified. In this case, if necessary, a heating device of a certain length may be installed in the distance from the nozzle directly to the starting point of the cooling zone, that is, in the length section of the hood.

This zone is called a delayed cooling zone or heating zone, which has a length of 150 to 450 mm and a temperature (air contact surface temperature) of 320 to 400°C.

In the cooling zone, depending on the method of blowing cooling air, open quenching method, circular closed quenching method, radial outflow quenching method, and radial inflow quenching method ) law may be applied, but is not limited thereto.

At this time, the temperature of the cooling air injected for rapid cooling in the cooling zone is adjusted to 20 to 50 ℃. The rapid cooling using such a sudden temperature difference between the hood and the cooling zone is to increase the solidification point and spinning tension of the spun polymer to increase the orientation of the undrawn yarn and the formation of a linkage between crystals and crystals.

Thereafter, the solidified yarn passing through the cooling zone can be oiled in an amount of 0.5 to 1.2 wt% with respect to the discharged yarn by an oil agent applying an emulsion having excellent stretchability and thermal efficiency while reducing the friction coefficient between single yarns.

The oiled yarn is spun to form an undrawn yarn.

Thereafter, the undrawn yarn is drawn in multiple stages by passing through a drawing roller to prepare a fiber having a carbon black content of 0.2 to 0.5% by weight in the fiber.

At this time, the winding speed of the drawn yarn is not particularly limited, but is preferably 2,500 to 4,500 m/min. If the winding speed is less than 2,500 m/min, productivity is lowered, and when the winding speed exceeds 4,500 m/min, cutting occurs during winding and workability is reduced.

A fiber having a content of carbon black particles in the fiber of 0.2 to 0.5% by weight is prepared.

When the content of carbon black particles in the prepared fiber is less than 0.2% by weight, it is difficult to sufficiently express the blackness of the original yarn, and when it exceeds 0.5% by weight, the yarn breakage increases during spinning, thereby reducing spinning operability.

Accordingly, the polyethylene terephthalate original yarn prepared by the present invention has a strength of 8.5 to 10.0 g/d, a strength of 13.0 to 15.0 kgf, a cut elongation of 16 to 19%, and a toughness of 36 to 42 g/d. It is possible to express physical properties and spinning operation fairness comparable to general-purpose polyethylene terephthalate fibers while satisfying an appropriate level of high fastness. In addition, the polyethylene terephthalate yarn can be used for seat belts, industrial webbing, ropes, fabrics, and the like.

Hereinafter, the present invention will be described in detail by way of Examples. However, these Examples are for describing the present invention in detail, and the scope of the present invention is not limited to these Examples.

Examples 1 to 4

A master batch containing 5 wt% of carbon black was prepared by solid-state polymerization of the master batch according to the viscosity (0.7 to 1.0 dl/g) shown in Table 1. The conditions of solid-state polymerization are maintained at 100° C. at less than 1 torr, after surface crystallization at 140° C., and then maintained at 235° C. until a certain viscosity or higher, thereby maintaining the viscosity level of the master batch according to Table 1.

After that, 3.0wt% of the prepared master batch was added to a polyethylene terephthalate chip having an intrinsic viscosity (IV) of 1.05 dl/g and spun using a 144 hole nozzle, and the polyethylene terephthalate original yarn was subjected to an appropriate stretching process. was prepared.

Comparative Example 1

A raw yarn was prepared in the same manner as in Example, except that the viscosity of the master batch was 0.6 dl/g previously used.

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Masterbatch Intrinsic Viscosity (dl/g) 0.7 0.8 0.9 1.0 0.6 Masterbatch content (%) 3 3 3 3 3 Denier (d) 1503 1505 1502 1503 1506 Strength (g/d) 8.7 9.0 9.3 9.7 8.3 Strong (kgf) 13.1 13.5 14.0 14.6 12.5 Abstinence (%) 18.2 18.1 18.5 17.9 18.2 Toughness (g/d) 37.1 38.3 40.0 41.0 35.4

Table 2 shows the spinning conditions of the high-strength original yarn at this time.

Nozzle Size 0.63*1.89*144 B/L (mm) inspiration 40 exhaust 50 Finish Type TN-7970 Inv' Hz 20.0 GR Sp' (m/min) GR1 500 GR2 515 GR3 2103 GR4 3100 GR5 3050 Drt 6.20 R/R(%) 1.6 TDR 9.3 GR6-Gr5 0 GR Temp(℃) GR1 OFF GR2 110 GR3 125 GR4 240 GR5 140 WD Sp' Sp' (m/min) 3040

1) Intrinsic Viscosity (I.V.)

After dissolving 0.1 g of the sample in a reagent (90°C) mixed with phenol and 1,1,2,2-tetrachloroethanol 6:4 (weight ratio) for 90 minutes, transfer it to an Ubbelohde viscometer and keep the temperature at 30°C. It is maintained in a thermostat for 10 minutes, and the number of seconds of falling of the solution is calculated using a viscometer and an aspirator. The R.V. value and I.V. value and I.V. The values were calculated.

R.V. = Number of seconds of falling of sample / Number of seconds of falling of solvent

I.V. = 1/4 × [(R.V.- 1)/C] + 3/4 × (In R.V./C)

In the above formula, C represents the concentration (g/100 ml) of the sample in the solution.

2) How to measure the strength

After allowing the yarn to stand for 24 hours in a constant temperature and humidity room with a standard condition, that is, a temperature of 25° C. and a relative humidity of 65% RH, the sample is measured through a tensile tester by the ASTM 2256 method.

As shown in Table 1, the polyethylene terephthalate dyed yarns prepared according to Examples 1 to 4 of the present invention exhibited superior strength, strength, and toughness than the dyed yarns of Comparative Example 1.

Claims (5)

preparing a polymer by mixing and melting a polyethylene terephthalate master batch containing carbon black particles and a polyethylene terephthalate chip; and
spinning the polymer by means of a spinning nozzle, stretching it in multiple stages, and winding it to prepare a polyethylene terephthalate yarn;
including,
The input ratio of the polyethylene terephthalate master batch is 2 to 5% by weight,
The polyethylene terephthalate master batch has a viscosity (IV) of 0.7 to 1.2 dl/g through solid-state polymerization,
The method for producing a high-strength polyethylene terephthalate raw yarn, characterized in that the viscosity of the polyethylene terephthalate chip is 1.0 to 1.2 dl / g.
delete The method of claim 1,
The raw yarn has a strength of 8.5 to 10.0 g/d, a strength of 13.0 to 15.0 kgf, a cut elongation of 16 to 19%, and a toughness of 36 to 42 g/d. .
The method of claim 1,
The method for producing a high-strength polyethylene terephthalate original yarn, characterized in that the carbon black particles include 5 to 25% by weight based on 100% by weight of the total polyethylene terephthalate master batch.
A high-strength polyethylene terephthalate raw yarn manufactured by the manufacturing method of claim 1.