KR19980061101A - Method for manufacturing deep color polyester fiber and spinneret thereof - Google Patents

Abstract

The present invention has a very fine and uniform crate on the fiber surface by modifying the polymer composition as a uniform and fine inorganic particles and limiting the hollow ratio and the slit width of the yarn by using circular or oval hollow detentions. The purpose is to obtain deep color polyester fiber by fibril expression during alkali reduction process by improving molecular orientation, and its technical structure is to form the inner particle and the outer particle. 1.0 to 5.0% by weight of a titanium compound having 0.01 to 0.5 µm and 1.0 to 8.0% by weight of a silica compound were added, and the yarns were hollowed out using a circular or elliptical hollow mold satisfying the following formulas (1) and (2). 10 to 35% of slit, 1.5 to 12 μm of slitting width of hollow fiber yarn, and after spinning, the fibrillation is expressed at the level of 100 to 10000 / cm2 during alkali weight loss processing. It is a novel invention regarding the manufacturing method of the polyester fiber excellent in deep color as a gong, and its spinneret.

..................(One)

30 ° ≤θ≤75 ° ...... (2)

Description

Method for manufacturing deep color polyester fiber and spinneret thereof

1 is a schematic process diagram showing an embodiment of the direct radiation drawing method used in the present invention,

2 is a cross-sectional view of a fabric in which fibrillation occurs to express deep color,

3 is a cross-sectional view of the fiber after alkali weight loss processing.

4 and 5 are cross-sectional views showing a circular hollow sphere and an elliptical hollow sphere used in the embodiment of the present invention.

* Description of the symbols for the main parts of the drawings *

1: detention 2: chiller

4: focusing device 5: first drawing roller

6: first separation roller 7: second extension roller

9: Winder 10: Traverse Guide

The present invention relates to a method for producing a polyester fiber that can increase the deep color of the fiber according to the fibrillation, and to the spinneret thereof, and in particular, a part of synthetic fiber such as natural fiber, rayon regenerated fiber and acrylic Fibrillation, which is expressed only in polyester fiber, is expressed in polyester fiber, thereby eliminating metallic gloss peculiar to polyester, and related to a method for producing a fiber which can enhance soft gloss and deep color.

Fibrillation, which is essential for the improvement of deep color, means that one fibrous fiber is separated into fine fibers of several strands, and in terms of its effect and manufacturing process with the ultrafine fiber which is being variously progressed for the purpose of new synthetic island. Not only are they fundamentally different, but there are also many differences in the use of knitted fabrics after high-order processing. In addition, when the fibrillation is expressed on the fabric surface, the shiny metallic luster and the stiff touch unique to synthetic fibers are lost, and a distinctive grayish luster and a soft touch are expressed, which is characteristic of cellulose or wool fibers. It is a great advantage to be able to express the effects of fibril fibers on the biogeosphere. And more advantageously, the fibrillation occurs in the general dyeing process without a separate brushing process for producing such an effect in post processing, which can be considered to be a great help in improving the process performance and quality of synthetic fibers.

However, the conventional method for improving the deep color in the polyester fiber for garments is mainly to maintain the level of unevenness due to the surface loss caused by the modification of the polymer or to maintain the polyester synthetic fiber by the production of some The metallic gloss was removed and the color was imparted. However, if the method is excessively modified during polymerization or a uniform release cross-section yarn is produced, high technology is required during spinning or physical properties such as elongation are deteriorated. However, in this study, in order to improve the color depth of a fiber, a fibrillated fiber in which one raw fiber is separated into several fibrils is separated from the conventional method to improve the color depth of a polyester fiber. do.

However, the expression of fibrillation used as a method for improving color depth has been evaluated to be almost impossible in the existing polyester fiber, and it has been known to be expressed only by compounding with some acrylic fiber or industrial nonwoven fabric and natural fiber. However, the present inventors have conducted various studies, and the fibrillation can be expressed in various forms in polyester fibers, and the most important technique in the production of such fibrillated fibers is hollow having high hollow ratio and high molecular orientation. Found to be in the manufacture of fibers. However, in order to improve the stiffness of the hollow fiber, it is possible to perform excessive alkali reduction at higher processing of the fabric than ordinary yarns or to manufacture a special type of cross-section yarn. In addition, when excessive polymerization reforming is achieved with only a deep color effect, deterioration of physical properties due to excessive alkali reduction occurs in the development of the knitted fabric, which makes it more difficult to develop the use in the knitted fabric. .

Looking at the technology for manufacturing deep color polyester fiber, Japanese special public office 61-152816 shows that when producing microporous polyester for improving color depth, 1.0 wt% of titanium compound is added to the fiber surface to make pores on the fiber surface. The main content is to produce fibers having an average maximum width of 0.1 to 0.7 µm, and in special process 58-144119, 0.5-10 mol% of isophthalic acid or its ester-forming derivative is added during the process of DMT or TPA. 0.3-3 mol% of phosphoric acid or its ester-forming derivative is added and dyed, and the low refractive index resin is coated to improve color depth. In addition, Japanese Patent Application Laid-Open No. 1-298210 describes a hollow fiber manufacturing method of a cross section for directly producing a fiber having different anisotropy in the fiber axis direction. The patent seeks to release the hollow fiber, which has a connection between the inner hollow portion and the outer uneven portion of the detention, in particular to express fibrillation in the polyester fiber. In order to express the feeling of dryness and flexibility in the phase, when the spinneret is designed as a V-shaped or U-shaped release section, excellent physical properties are expressed in the knitted fabric.

In this case, it is shown that fibrillation is expressed on the fiber surface only when the alkali loss is excessively advanced. However, the advantage of the fibrillation of deep color fibers is that the strength and elongation properties are less than that of the yarns produced by the general method by the addition of a microporous modifier that elutes during alkali weight reduction processing or the production of release cross-section yarns. Not only does it fall, but there is an advantage in that it is possible to eliminate problems such as the pack pressure increase that occurs when the modification of the polymerization product exceeds a certain limit.

Therefore, a key technique for improving the properties of knitted fabrics without causing physical degradation, which is a characteristic of this fibrillation, should be carried out very uniformly in the direction of the fiber axis when reducing alkalis and also having very thin slits. It is considered that the preparation of is an essential requirement for improving color depth.

From this point of view, hollow fiber or heterofiber cross-section fiber is more advantageous than the general circular fiber for the production of fibers to be separated into very fine fibrils. For this reason, the results of the study of various cross-section detentions were found to be the most favorable for the fibrillation of hollow detentions rather than the deformed cross-sections. I found that there is a very close relationship with sex. In addition, the slitting width in the manufactured hollow fiber can be fibrillated to a certain level, but if it exceeds a certain level, the fibrillation does not occur at all. That is, fibrillation was expressed only in the range of the slits of the fabrics produced from 1.5 m to 12 m. In fact, fibers less than 1.5 m in width of the slits were impossible to manufacture due to hole closure. Fibers larger than or equal to μm did not exhibit fibril expression in the fiber axis direction at all as the hole width was increased.

Next, as a result of studying the relation between the cross-sectional shape and the hollow ratio of the hollow tool to promote fibrillation and to secure stable spinning workability, the width of the slits is as shown in FIG. ) And the ratio of the inner diameter (R) of the slit In the case of an elliptical hollow sphere, the opening angle (θ) formed by the point where the tangents meet at the outer diameter of the XY axis slits and the inner diameter of the hollow slits on the XY axis is 30 ° ≤θ as shown in FIG. It must be in the range ≤75 °. If the ratio is less than 0.12 or the opening angle θ is greater than 75 °, it is advantageous for fibrillation due to securing the hollow ratio, but it may be caused by multiple trimming due to the decompression washing, the pack pressure increase during the spinning, and the closing of the detention. If the ratio is higher than 0.48 or the angle θ is smaller than 30 °, the slit width of the manufactured hollow fiber becomes incapable of expressing fibrillation, or the cross section of the fiber is extremely deformed as the hollow ratio decreases. There is this.

After reviewing the conditions for the above detention, multifilament was prepared and developed into a woven fabric to reduce alkali, resulting in fibrillation on the fabric at the level of several hundreds to tens of thousands / cm2. The color depth was very good compared to the general microfibers and circular fibers.

Hereinafter, the present invention will be described in detail. The polyester used was prepared by dispersing inorganic particles having an average particle of 20 to 250 nm and a charged content of 1.0 to 10.0% by weight at the beginning of the transesterification reaction in preparing a polyester produced by diol and dicarboxylic acid or ester reaction thereof. External particles are formed, and at the end of the transesterification reaction, a phosphoric acid compound is added 0.1 to 0.3% by weight based on the amount of the polymer as a heat stabilizer to form internal particles by insoluble alkali metal salts. 1.0 to 5.0% by weight of a titanium compound having an average particle diameter of 0.01 to 0.5 µm, which can give rise to formation of fine craters and high specific gravity, was added to the polymerization product. At this time, if the diameter of the inorganic particles is less than 20nm or the input amount is lower than the above range, the radioactivity due to the increase in viscosity is reduced or the fibril is not expressed when the weight is reduced, the particle size is 250nm or more or exceed the above range In the case of radiation, there is a high possibility of multiple trimming due to coagulation or closing of the detention hole.

Using the polymer produced according to the above method, preliminary drying at 120 ° C. for 2 hours and main drying at 160 ° C. for 4 hours were carried out to prepare a fully drawn yarn by direct spinning. At this time, the spinning temperature was 290 ± 2 ℃, the operating ratio was prepared over the range of 2.0 to 3.4. In this case, when the spinning temperature is lower than the set temperature, the yarn physical properties and the uniformity are lowered. When the spinning temperature is higher than the actual temperature, the spinning workability is deteriorated due to the amount of polymer discharge or the production of curvature under the detention. The woven fabric made of the yarn thus prepared was subjected to weight loss processing for 5 minutes in a 5% aqueous alkali solution to confirm the expression level of fibrils and the feel and color of the woven fabric.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples.

Example 1

100 weight percent of dimethyl terephthalate, 60 weight percent of ethylene glycol, 0.083 weight percent of calcium acetate, 0.083 weight percent of antimony trioxide were added to a transesterification reactor and heated slowly at 140 ° C, and then triethylene was reached when the temperature inside the reactor reached 160 ° C. 10 minutes after the addition of 1.5% by weight of glycol, 3.0% by weight of the silica compound having an average size of 120 nm and a concentration of 10% by weight was added to terminate the transesterification reaction.

After the product was transferred to a polymerization reactor, 0.04% by weight of phosphorous acid was added, and the polymerization polymer produced after completion of the polycondensation reaction at a temperature of 280 to 285 ° C. for about 2 hours and 30 minutes under reduced pressure to 0.1 to 0.2 mmHg (intrinsic viscosity) η = 0.655) was melt-discharged at 290 ± 2 ° C through the hollow mold of FIG. 4, cooled to multifilament at a rate of 0.45 m / sec, stretched 2.0 to 3.5 times, and then wound at 5,000 m / min. Wound up.

At this time, the spinneret used was a hollow hollow sphere having a ratio of the width (a) of the slits and the distance (R) of the slits from the center to the diameter of the slits (0.1), as shown in FIG. In order to maintain the constant temperature in the spinning system that can adjust the temperature (Ta) from the detention to the point where the cooling starts, as shown in Figure 1 was wound at a speed of 5000m / min. Thereafter, the multi-filament was used to produce a knitted fabric, and then, the obtained knitted fabric was subjected to alkali reduction processing in an aqueous 5% alkali solution to evaluate the touch and fibril expression after the reduction.

The cross-sectional shape of the short fibers constituting the manufactured multifilament is shown in FIG. 3, and the properties of the fibers were measured for elongation, uniformity and orientation, and the width of the slit and the expression of fibrils on the alkali-reduced fabrics. The degree was measured using SEM (Scanning Electron Microscopy). At this time, the expression level of fibril was 100-10000 / cm2, which was very good (◎), 10-100 / cm2, which was excellent (○), and less than 10 / cm2. The fabric was evaluated on the basis of soft touch and resilience. Final color depth was evaluated by the following method, and the evaluation results are shown in Table 1.

1) How to judge by water supply

After dyeing in the forge state of the same tissue, the visual result is visually compared and judged according to the following criteria.

Level 1: No Deep Color

Level 2: Extremely Weak

Level 3: Small Difference

4th grade; There is a difference

Level 5: Significant differences

2) Method by Instrumental Analysis

A) Method to determine by measuring reflectance by spectrophotometer measurement

(The larger α value, the deeper color.)

α = k / s = (1-2R) ² / 2R

B) L * value measurement by colorimeter measurement

(The lower the L * value, the deeper the color.)

Example 2

Polyester multifilament was prepared using the same spinneret as in Example 1, but was spun using a polymer in which 1.0 wt% of the silica compound was added as a modifier. Evaluation results according to the physical properties and fibrillation expression of the polyester fiber thus produced are shown in Table 1.

Example 3

Polyester multifilament was prepared using the same spinneret as in Example 1, but was spun by using a primer in which the content of the silica compound added as a modifier was 8.0 wt%.

Example 4

It was spun using a polymer modified in the same manner as in Example 1, except that a circular hollow sphere having a ratio of the width (a) of the slits and the distance (R) from the center of the slits to the inner diameter of the slits was 0.36.

Example 5

The polymer modified in the same manner as in Example 1 was used, except that the spinneret used had an opening angle (θ) formed by the point where the tangents met at the outer diameter of the XY axis slits of the oval hollow hole and the inner diameter of the hollow slits on the XY axis. Spinning was carried out using 30 ° of detention.

Example 6

The polymer modified in the same manner as in Example 1 was used, except that the spinneret used was the opening angle (θ) formed by the point where the tangents meet at the outer diameter of the XY axis slits of the oval hollow hole and the inner diameter of the hollow slits on the XY axis. Spinning was carried out using a detention of 75 °.

The comparative example with respect to the said Example is shown below.

Comparative Example 1

A polyester multifilament was prepared under the same conditions as in Example 1, except that a silica compound was not added at all. In addition, the spinneret used was spun using a circular hollow sphere having the same spectra as in Example 1.

Comparative Example 2

Polyester multifilament was prepared under the same conditions as in Example 1, except that 10.0% by weight of the silica compound was used as the polymerization product. In addition, the spinneret used was spun using a circular hollow sphere having the same spectra as in Example 1.

Comparative Example 3

The polymer modified in the same manner as in Example 1 was used, except that the spinneret used was a member whose width (a) of the slits and the distance (R) from the center of the slits to the inner diameter (R) were 0.08. And spun.

Comparative Example 4

The polymer modified in the same manner as in Example 1 was used, except that the spinneret used was a member whose width ratio (a) of the slits and the distance (R) from the center of the slits to the inner diameter of the slits were 0.48. It was spun using.

Comparative Example 5

The polyester multifilament was prepared under the same conditions as in Example 1 except that the spinneret used was an elliptical hollow mold having a non-uniform ratio of the distance (R) from the center of the slit to the slit inner diameter as shown in FIG. Used. At this time, the hollow ratio and fibril expression according to the shape change of the section using an elliptical hollow sphere having an opening angle θ of 20 ° between the tangents of the XY axis slits and the inner diameter of the hollow slits on the XY axis The degree was studied.

Comparative Example 6

A polyester multifilament was prepared under the same conditions as in Example 1 except that the spinneret used had an opening angle θ formed by the point where the tangents meet at the outer diameter of the XY axis slits and the inner diameter of the hollow slits on the XY axis. The study was carried out to investigate the degree of hollowness and fibril expression according to the shape change of the section using the oval hollow sphere.

Comparative Example 7

Polyester multifilament was prepared using a polymerization formulation modified in the same manner as in Example 2. However, microfiber of 0.4 ~ 0.5 denier grade with single yarn fineness was manufactured by using general circular detention, not hollow detention. The polymer was melt-discharged at a spinning temperature of 295 ° C. and finally wound up by direct spinning.

Comparative Example 8

Using the polymerization product modified in the same manner as in Example 2, a polyester multifilament was prepared, but a single yarn fineness of 2-3 denier fibers was prepared using a general round mold rather than a hollow mold. The polymer was melt discharged at a spinning temperature of 290 ° C. and finally wound up by direct spinning.

The evaluation results according to the physical properties and fibrillation expression of the polyester fiber according to the above Examples and Comparative Examples are shown in Table 1.

TABLE 1

Claims (4)

When preparing polyester produced by diol and dicarboxylic acid or ester reaction, inorganic particles having an average particle diameter of 20 to 250 nm and a charged content of 1.0 to 10.0 wt% are added in the form of dispersion to form external particles. At the end of the exchange reaction, when the phosphate compound was added in an amount of 01 to 0.3% by weight relative to the polymer to form internal particles, 1.0 to 5.0% by weight of the titanium compound having an average particle diameter of 0.01 to 0.5 µm and the initial or immediately before the polycondensation reaction 1.0 to 8.0% by weight of silica compound is added, and the circular or oval hollow mold is used to spin the yarn with a hollow ratio of 10 to 35%, and the slitting width of a hollow fiber of 1.5 to 12 μm. A method for producing deep color polyester fibers, characterized by having a very fine and uniform crate on the surface of the fiber by the expression of brill. The method for producing deep color polyester fiber according to claim 1, wherein the fibrillation is expressed at a level of 100 to 10000 / cm 2 when alkali is reduced. Hollow spinning fasteners, characterized in that the inner diameter of the slits and the width of the slits for the expression of fibril during alkali reduction satisfy the following formula (1) ..................(One) Where a is the width of the slits, R is the inner diameter of the slit. 4. The opening angle θ formed by the point where tangents meet each other in the slit outer diameter on the XY axis for fibril expression and the inner diameter of the slit on the XY axis satisfies the following expression (2). Hollow spinnerets 30 ° ≤θ≤75 ° ...... (2) Θ is the opening angle formed by the point where the tangents meet in the slit outer diameter of the X-Y axis and the inner diameter of the hollow slit on the X-Y axis.