KR20020003449A - A cation dyeable polyester yarn, and a process of preparing for the same - Google Patents

Abstract

PURPOSE: A process of preparing the titled polyester capable of effectively retarding crystallinity that suddenly increases during spinning at a high wind-up speed is provided, which improves productivity, has improved workability such as spinning and false twisting and can prevent degradation of quality of a yarn. CONSTITUTION: The polyester fiber is prepared by melt spinning of a cation dye dyeable polyester copolymer, wherein 0.5 to 5.0% by weight of an orientation inhibitor is mixed with the above copolyester in a stationery type mixer to produce a master chip, which is uniformly mixed with conventional polyester polymers in a molten state, spun and winded up at a speed of 4,500m/min or more. The glass temperature of the orientation inhibitor is 100deg.C or more.

Description

Cationic dye saltable polyester fiber and its manufacturing method {A cation dyeable polyester yarn, and a process of preparing for the same}

The present invention relates to a cation dye salted polyester fiber which can effectively delay the phenomenon of rapid increase in crystallization on the radiation when the cation dye salted polyester fiber is spun at high speed, and a method of manufacturing the same. .

Cationic (basic) dye salt type polyester fibers are polyester fibers which can be dyed with basic dyes at normal pressure, and are prepared by copolymerizing isophthalic acid component or polyalkylene oxide containing metal sulfone group during polyester polymerization.

When spinning the cationic dye salted polyester polymer at a high speed of 4,000 m / min or more, a "spinning crystallinity" phenomenon occurs due to a sudden increase in the radial tension, which causes process instability such as cutting and wool. Are badly generated and workability is greatly reduced.

As a result, when spinning the polyester fiber, there is a limit of spinning speed, and currently the mass production of polyester partial alignment yarns is usually produced at spinning speeds of 3,500 to 4,000 m / min.

At the spinning speed of 4,000m / min as the critical point, the increase in molecular orientation increases without increasing the crystallinity, but when the spinning speed exceeds 4,000m / min, the molecular orientation and crystallinity increase simultaneously. Therefore, as the spinning speed increases, the crystallinity increases rapidly with the increase of the radial tension and the alignment crystallization accordingly. As the spinning speed increases, the density and birefringence also increase. Ziabicki and H. Kawai Edited, 'High Speed Fiber Spinning', John Wiley & Sons, New York, 1985].

Until now, the process of delaying the rapid increase of the crystallization on the radiation by increasing the spinning speed in the polyester fiber production process overcomes the existing limit spinning speed and spins the polyester partial alignment yarn at a high speed of 4,000 m / min or more. Much research has been conducted on. Known methods to date can be roughly classified into first, through the modification of the raw polymer (copolymerization, molecular chain crosslinking, etc.) and second, by mixing the polymer material.

As a first method, EP 0 263 020 and US Pat. No. 4,518,744 add compounds pentaerythrite, trimethylropropane, melitic acid and trimellitic acid, which have side chains to the molecular chain, before or after transesterification or polymerization. US Patent 4,966,740 proposes a method for adding tetraethyl silicate before or after the transesterification reaction, US Patent 4,092,299 proposes a molecular chain crosslinking method using a tetrafunctional material have. However, the first methods require specially selected polymerization conditions, and the workability in the draw combusting process is deteriorated. In particular, the high cutting rate in the combustion process causes a problem of difficult combustion.

As a second method, US Pat. No. 4,609,710 discloses a method of mixing polystyrene, polyamide, polymethylmethacrylate, or the like as a molecular alignment regulator during or after the polymerization of a polyester. In addition, a method of reducing the radiation orientation by adding a small amount of liquid crystal polymer material, polyethylene, polyethylene glycol, etc. in the conventional polyester polymerization is known. Appl. Polym. Sci., 31 , 2753 1986)]

In this case, the flowability of the polymer melt in the spinning process is drastically changed, which greatly affects the spinning characteristics, in particular, the spinning speed, thereby lowering the spun orientation. However, the method is difficult to spin stably due to the problem of uniformly mixing the added polymer, and the mixed polymer is moved to the fiber surface in the drawing and burning process to inhibit the workability, the occurrence of wool and fine dye stains Occurrence is a cause of deterioration of the final false twist quality.

The present invention provides a method for producing a cation dye salted polyester fiber that can effectively delay the phenomenon of the rapid increase in crystallization on the radiation when spinning the cation dye salted polyester fiber at a winding speed of 4,500m / min or more I will. In addition, the present invention is excellent in the workability of spinning, stretching, and flammability, the crystal orientation inhibitor can be prevented from moving to the fiber surface to reduce the yarn quality, while maintaining the yarn elongation at 120% or more, more than 4,500m / min An object of the present invention is to provide a method for preparing a cationic dye salt-type polyester partial alignment yarn at a winding speed.

The present invention relates to a method for producing a cationic dye salted polyester fiber, which can effectively delay the radiocrystallization phenomenon during high-speed spinning of the cationic dye salted polyester fiber, and has excellent stretching and flammability processability.

More specifically, the present invention is to prepare a master batch chip by mixing a crystal orientation inhibitor in a cationic dye salt-type polyester copolymer, and then uniformly mixing the master batch chip and a conventional polyester polymer in a molten state, and It is characterized by spinning and winding at a speed of 4,500m / min or more continuously.

Hereinafter, the present invention will be described in detail.

First, in the present invention, a master batch chip is prepared by mixing a crystal orientation inhibitor having a glass transition temperature of 100 ° C. or higher during cationic dye salt-type polyester copolymerization. The cationic dye salt-type polyester copolymer may be prepared by copolymerizing isophthalic acid component or polyalkylene oxide containing a metal sulfone group in polyethylene terephthalate. As the crystal orientation suppressor, polymethyl methacrylate resin, polystyrene resin, or methyl methacrylate-styrene copolymer resin is used.

The glass transition temperature (Tg) of the crystal orientation suppressor is 100 ° C. or more. The reason is to maintain the difference in the solidification behavior of the polyester polymer having a glass transition temperature (Tg) of 80 ° C. on the radiation and the crystallization inhibitor, thereby suppressing the crystal orientation behavior of the polyester polymer.

If the glass transition temperature (Tg) of the crystallization inhibitor is less than 100 ℃, the difference in the solidification behavior between the polyester polymer and the crystallization inhibitor is small, it is difficult to effectively suppress the crystal orientation behavior of the polyester polymer on the radiation. As a result, the winding speed cannot be made higher than 4,500 m / min.

Due to the attractive force between the aromatic ring included in the crystallization inhibitor and the aromatic ring included in the polyester molecule, it is possible to more effectively inhibit the orientation crystallization occurring during the spinning and stretching process. It is well known that an aromatic ring is composed of double bonds between constituent carbon atoms, and therefore, an attractive force exists between adjacent aromatic rings.

In addition, the aromatic part is a rigid part inside the molecular chain, while the aliphatic part means a flexible part. Therefore, the presence of an appropriate aromatic part can maintain the mechanical properties of the polymer chain, a crystallization inhibitor, thereby minimizing the loss of mechanical properties, such as a decrease in strength by the crystallization inhibitor fibrils distributed in the polyester. .

From this point of view, by using the crystallization inhibitor of the present invention, it is possible to maintain a similar level of physical properties, particularly strength, to the polyester partial-orientated yarn prepared by the general method.

Next, the master batch chip and the conventional polyester polymer are mixed uniformly in a molten state.

The amount of the crystallization inhibitor added is 0.5 to 5.0% by weight based on the weight of the entire polymer (polyester copolymer + crystallization inhibitor). If the added amount is less than 0.5% by weight, the effect of suppressing radiocrystallization is insignificant, and when the added amount is more than 5.0% by weight, the stretching and flammability processability deteriorate.

In the present invention, the mixture of the cationic dye salt type polyester copolymer and the crystal orientation suppressor is first supplied with the cationic dye salt type polyester copolymer chip to the extruder, followed by melting the melted polyester copolymer. At the same time as feeding to the two-screw screw extruder, the crystallization inhibitor chip (Chip) is supplied to melt and mix them. More preferably, the melt mixed in the two-stage twin screw extruder is continuously kneaded with a stationary kneader.

Meanwhile, the cationic dye salt type polyester copolymer chip and the crystal orientation suppressor chip may be simultaneously supplied to an extruder to melt and mix them, and then the melt may be continuously kneaded with a stationary kneader. Mixing of the master batch chip and ordinary polyester is also performed in the same manner as described above.

The stationary kneader serves to make the crystal orientation suppressor distribution more uniform in the melt. In the case of the present invention, since a more uniform kneading is required, it is preferable to pass 20 or more stages of kneading kneader. In other words, kneading of 1 million (2 ²⁰ ) times or more is possible to uniform distribution of crystallization inhibitors, and is preferable to prevent the occurrence of salt spots in the false twisted state of the final product.

Otherwise, if the stationary kneader of less than 20 stages is adopted, deterioration of the quality may occur due to the occurrence of fine salt spots in the twisted yarn state, deterioration of workability in the stretching and combustion process, and stable workability There is a possibility of becoming difficult.

As described above, the cation dye salt type polyester master batch chip and the conventional polyester resin are uniformly melted and mixed, and then they are continuously spun at a winding speed of 4,500 m / min or more. The take-up speed increases productivity by 40% at least 4,500m / min. Winding speeds of less than 4,500m / min are marginal in productivity, and thus cannot be said to be economical in terms of return on facility investment.

In addition, the elongation at break of the partial oriented yarn wound at a speed of more than 4,500 m per minute was 120% or more. When the elongation is more than 120% crimp frequency (Crimp Frequency) is high, the crimp quality can be obtained good twisted yarn, it is possible to secure excellent flammability workability. Otherwise, it is difficult to perform high-speed operation more than 800 meters per minute in the simultaneous drawing and burning process, and it is difficult to obtain the same twisted yarn with the same physical properties as in the case of the simultaneous drawing and burning of the unstretched yarn spun at ordinary 3,000 to 3,500 meters per minute. It is difficult to secure the stability of the work by obtaining the combustible yarn with reduced varnish (Crimp Liveliness).

In the present invention, it is preferable to maintain the shear rate in the spinneret during spinning at 7,000 to 15,000 per second. The shear rate in the spinneret during spinning is the dominant factor that determines the radial distribution of the crystallization suppressor distributed inside the spun yarn. If the shear rate is low, the degree of orientation of the crystallization inhibitor in the fiber axis direction is lowered, which may cause a problem that the effect of suppressing the orientation crystallization of the polyester fiber is reduced. On the other hand, if the shear rate is too high, The problem that the distribution is concentrated on the surface portion of the fiber occurs, which may cause a problem of lowering the strength.

Therefore, if the shear rate in the spinneret is maintained within the range of 7,000 or more and 15,000 or less per second, the effect of suppressing the orientation crystallization of the polyester fiber is sufficiently exerted, and the distribution of the crystallization suppressor in the radial direction of the fiber is appropriately maintained and partially aligned. The strength of the yarn and the false twisted yarn can be maintained properly.

The cationic dye salt-type polyester fiber of the present invention prepared as described above is composed of 95 to 99.5% by weight of the main cationic dye salt-coated polyester copolymer and polymethyl methacrylate resin, polystyrene resin or methyl as a crystal orientation inhibitor. The methacrylate-styrene copolymer resin is composed of 0.5 to 5.0% by weight, and the elongation at break is 120% or more.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited only to the following examples.

Example 1

Polyethylene terephthalate, 5-sodium sulfone dimethyl isophthalate, and methyl methacrylate / styrene copolymers having a glass transition temperature of 105 ° C. were copolymerized and mixed in an extruder to prepare a master batch chip having an intrinsic viscosity of 0.55. It dried at 155 degreeC for 4.5 hours. The master batch chip and ordinary polyester were introduced into a twin screw extruder having a diameter of 35 mm and melt mixed at 300 ° C. At this time, the methyl methacrylate / styrene-based copolymer content in the total polymer melt was 0.9 wt%, and the 5-sodium sulfone dimethyl isophthalate content was 4 mol%.

In addition, the polymer melt thus mixed is spun through 36 spinneret perforated spinnerets, and a cooling air at 22 ° C. is sent at a rate of 0.5 m per second to cool and solidify. Dye salt type polyester partial alignment yarn was prepared. At this time, the shear rate in the spinneret was 9,000 per second, and the winding speed was 4,600 m / min.

The false twist yarn was manufactured using the Cation dye salt-type partial orientation yarn manufactured as described above using Murada 33H (manufactured by Murada, Japan). The burning rate was 850 m / min, the drawing ratio was 1.671 times, the temperature of the first heating plate was 200 ° C., the angle between the nip belts was 105 degrees, and the speed ratio was 1.5.

The final false twisted yarn was circular knitted using a circular knitting machine, and then dyed at 130 ° C. for 60 minutes using a disperse dye, and then dyeing quality of the plaque was examined. Table 2 shows the results of evaluating the fairness of spinning and combustibility and the properties of partially aligned yarns and combustible yarns.

Example 2 to Example 6 and Comparative Example 1 to Comparative Example 2

Cationic dye salted poly according to the same process and conditions as in Example 1 except that the resin type, glass transition temperature, mixing weight%, and winding speed of the crystal alignment inhibitor used in the manufacture of the master batch chip were changed as shown in Table 1. Ester partial orientation yarn, false twisted yarn and circular knitted fabric were prepared. Table 2 shows the results of evaluating the fairness of spinning and combustibility and the properties of partially aligned yarns and combustible yarns.

Manufacturing Conditions of Cationic Dye Salt-Type Polyester Partial Oriented Yarn division Crystallization Inhibitor Properties Winding speed (m / min) Resin type Glass transition temperature (℃) Addition amount (% by weight) Example 1 Methyl methacrylate-styrene copolymer 105 0.9 4,600 Example 2 Methyl methacrylate-styrene copolymer 105 2.5 4,500 Example 3 Polymethyl methacrylate 106 1.5 4,800 Example 4 Polymethyl methacrylate 106 3.5 4,900 Example 5 polystyrene 107 2.9 4,800 Example 6 polystyrene 107 4.0 5,100 Comparative Example 1 - - - 4,500 Comparative Example 2 Polymethyl methacrylate 106 0.1 4,700

Workability and Yarn Property Evaluation Results division Radiation workability Partial Alignment Elongation (%) Combustible Workability Primp Quality Platter Cream Rigidity (%) Example 1 Good 135 Good 41 none Example 2 Good 142 Good 38 none Example 3 Good 138 Good 39 none Example 4 Good 143 Good 42 none Example 5 Good 147 Good 44 none Example 6 Good 133 Good 43 none Comparative Example 1 Bad 83 Bad 28 has exist Comparative Example 2 Somewhat defective 110 Bad 29 has exist

The present invention effectively delays "radiation crystallization" in which the crystallization on the radiation increases rapidly during high-speed radiation, thereby producing a cationic dye salt type polyester partial alignment yarn at a winding speed of 4,500 m / min or more. As a result, productivity is improved. In addition, the present invention is uniformly mixed with the polyester copolymer and the crystal orientation inhibitor is excellent in stretching and flammability processability. In addition, the present invention can effectively prevent the phenomenon that the crystal orientation inhibitor is moved to the yarn surface to reduce the yarn quality.

Claims (7)

In preparing polyester fibers by melt spinning a cationic dye salt-type polyester copolymer, a crystal alignment inhibitor is mixed with a cationic dye salt-type polyester copolymer to prepare a master batch chip, and then A method for producing a cationic dye saltable polyester fiber, characterized in that a uniform polyester polymer is mixed uniformly in a molten state, which is continuously spun at a speed of 4,500 m / min or more. The method according to claim 1, wherein the content of the crystallization inhibitor relative to the total weight of the fiber is 0.5 to 5.0% by weight. The cationic dye saltable polyester fiber according to claim 1, wherein the cationic dye salted polyester copolymer is copolymerized with an isophthalic acid component or a polyalkylene oxide containing a metal sulfonic acid group in polyethylene terephthalate. Way. The method for producing a cation dye salt-forming polyester fiber according to claim 1, wherein the crystallization inhibitor is a polymethyl methacrylate resin, a polystyrene resin, or a methyl methacrylate-styrene copolymer resin. The method for producing a cation dye chlorinated polyester fiber according to claim 1, wherein the crystal orientation suppressor in the molten state and the cation dye chlorinated polyester copolymer are mixed with a stationary kneader. The method of claim 1, wherein the cationic dye salted polyester copolymer and the crystal orientation suppressor on the solid are melted and mixed in a twin screw extruder. Manufacturing method. The method for producing a cation dye saltable polyester fiber according to claim 1, wherein the crystallization inhibitor has a glass transition temperature of 100 ° C or higher.