JPH0693514A - Production of thick and thin yarn of polyester - Google Patents

Abstract

PURPOSE:To stably produce thick and thin yarn of polyester having excellent dispersibility of thick part and contrast in dyeing CONSTITUTION:A polyester flow having difference in flow velocity is delivered from a spinneret prepared by connecting plural delivery holes having different delivery sectional areas with a slit. A high-speed polymer flow extruded from a hole having a smaller delivery sectional area is collided against, bound and bonded to a low-speed polymer flow extruded from a hole having a larger delivery sectional area to produce thick and thin yarn. In the production, a polyester copolymerized with 1.0-3.0mol% ester-forming functional group- containing phosphonium benzene sulfonate derivative of the formula (X1 is ester-forming functional group; X2 is H or X1; R2 to R4 are alkyl or aryl; n is positive integer) is used as the polyester.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing thick yarn. More specifically, the present invention relates to a method for producing thick and thin yarns in which thick details are randomly dispersed, exhibiting an excellent span-like texture and having excellent bathochromic properties.

[0002]

2. Description of the Related Art Conventionally, polyester thick and thin yarns such as polyethylene terephthalate are mainly 500 to 3
An unstretched yarn spun at a speed of 500 m / min is non-uniformly stretched at a stretch ratio not higher than a natural stretch ratio to generate stretch unevenness. In such a method, the thick-fine ratio and the proportion of large details are determined by selection of the production conditions of the undrawn yarn, the drawing conditions during the drawing, and the like. For example, from the undrawn yarn spun at a low speed near 1000 m / min. A thick yarn having a large thick-to-fine ratio is obtained, while a thick yarn having a small thick-to-fine ratio is obtained from the undrawn yarn spun at a speed of around 3000 m / min.

However, the thick and thin yarn obtained by such a method has a problem that it is inferior in the dispersibility of the thick portion and the detail and is apt to be unevenly distributed. Moreover, since the thick portion is deeply dyed and the details are lightly dyed, the deeply dyed portion is likely to appear in a streak in the woven or knitted fabric, and the texture is likely to be hard.

In order to improve such a defect, Japanese Patent Laid-Open No. 49-5 / 1988
Japanese Patent Laid-Open No. 4626 and Japanese Patent Laid-Open No. 51-147616 propose a method of non-uniformly stretching under extremely specified stretching conditions to disperse the stretching points. However, the stretching points are likely to concentrate even with a slight impact, and it is extremely difficult to maintain the state where the stretching points are randomly dispersed. Therefore, there is a limit to industrially obtain thick thin yarns in which thick details are randomly dispersed by the above method.

As another method for producing thick and thin yarns,
JP-A-60-151310, JP-A-61-194
In Japanese Patent Publication No. 205, etc., a polyester stream having two flow velocity differences is discharged through a spinneret in which a pair of discharge holes having different discharge cross-sectional areas are connected to each other by a slit, and a low-speed heavy jet discharged from a discharge hole having a large discharge cross-sectional area is disclosed. A method (hereinafter referred to as a pulsing yarn) in which a high-speed polymer flow discharged from a discharge hole having a small discharge cross-sectional area is collided with the coalesced flow, bound and bonded, and then cooled and solidified (hereinafter referred to as pulsing yarn) has been proposed. According to such a method, a thick and fine yarn having a good dispersibility of thick and fine details can be obtained as compared with the above method, and further, a dyeing difference (contrast) between a thick portion and a fine portion can be controlled by a spinning speed, and Since the filaments have a difference in the degree of orientation in the cross-sectional direction, they are characterized by exhibiting bulkiness and a span-like texture by heat treatment. However, the stability of the cross-sectional shape and the stability of the spinning tone are poor, and there is a limit to industrial production.

[0006]

SUMMARY OF THE INVENTION The present invention has been made on the basis of the above-mentioned prior art, and the object thereof is to solve the above-mentioned drawbacks of the conventional pulsing yarn manufacturing method, and to disperse and dye large details. It is an object of the present invention to provide a manufacturing method capable of stably obtaining a thick and thin yarn having excellent time contrast.

[0007]

Means for Solving the Problems As a result of intensive studies aimed at achieving the above object, the present inventors have found that the use of a polyester in which a specific component is copolymerized suppresses the change with time of spinning and results in an extremely long time. The present invention has been achieved by finding that thick and thin yarns can be obtained stably for a period of time.

That is, according to the present invention, a polyester flow having a flow velocity difference is discharged through a spinneret in which a plurality of discharge holes having different discharge cross-sectional areas are connected by slits, and the discharge cross-sectional areas of the discharge holes connected by the slits are increased. Manufacture of polyester thick and thin yarns in which a low-speed polymer stream discharged from a large discharge hole is made to collide with a high-speed polymer stream discharged from a discharge hole having a small discharge cross-sectional area, bound while bouncing, and then cooled and solidified. In the method, a polyester in which a phosphonium sulfonate compound represented by the following general formula is copolymerized in an amount of 1.0 to 3.0 mol% based on all acid components is used as the polyester. A manufacturing method is provided.

[0009]

[Chemical 2]

[Wherein X ₁ is an ester-forming functional group, X ₁ is
₂ is an ester-forming functional group or a hydrogen atom which is the same as or different from X ₁ , R ₁ , R ₂ , R ₃ and R ₄ are the same or different groups selected from an alkyl group and an aryl group, and n is a positive integer . The present invention will be described below with reference to the drawings. 1 is a cross-sectional view of a discharge hole of a spinneret used in the present invention, FIG. 2 is a graph showing the relationship between the spinning take-up speed and the Worcester spot (u%) of the obtained thick and thin yarns, and FIG. 3 is the production of the present invention. Fig. 4 is a cross-sectional view of a filament constituting the thick yarn obtained by the method, Fig. 4 is a perspective view in the length direction of the filament constituting the thick yarn obtained by the present invention, and Figs. 5a and 5b are the thick yarn of the present invention and The stress-elongation curves of thick and thin yarns obtained by conventional non-uniform drawing are shown respectively.

In FIG. 1, reference numerals 1 and 2 respectively denote discharge holes for discharging a polymer stream. In FIG. 1A, a plurality of slits 1a to 1c form a hollow discharge hole having a large discharge area and are connected to each other. The holes 3 are connected to the discharge holes 2. On the other hand, in (b), 1a to 1c are 3a to 3c, respectively.
The slit is connected to the discharge hole 2. However, the shapes of the spinneret holes used in the present invention are not limited to these, and the shapes of the discharge holes 1 and 2 are irregular,
It may be hollow or the like.

In the present invention, the discharge hole as described above is adopted, and the polymer stream discharged from 1 is collided with the polymer stream discharged from the discharge hole 2 which is faster than the flow rate of the polymer stream. It is bound while being bound, then cooled and solidified, and then taken up.

Since the flow rate of the polymer flow discharged from the discharge hole 1 is slower than that of the polymer flow discharged from the discharge hole 2, the spinning draft is concentrated on the polymer flow discharged from the discharge hole 1. In particular, in the high-speed spinning at a spinning take-up speed of 2500 m / min or more, the polymer flow discharged from the discharge hole 1 is 500
Since the above high draft is concentrated, the degree of orientation becomes extremely higher than that of the polymer discharged from the discharge holes 2.

Further, the ink is discharged from the discharge holes 1 and 2.
The polymer flow to be caused has a flow velocity difference,
Since it is connected by the polymer flow discharged from the
The low-speed polymer flow discharged from the hole 1 is discharged from the discharge hole 2.
The resulting high-speed polymer flow collides with each other while colliding and bouncing.
As a result, it is possible to obtain a thick thin yarn having a thickness unevenness in the length direction.
It Further, the discharge hole 1 and the discharge hole 2 are connected by the slit 3.
Therefore, both holes should have the same pressure loss.
There is a difference in the flow rate of the polymer stream passing through. Because of this, this
By adjusting the shape of these holes, the difference in flow velocity can be easily
Can be made larger. By the slit 3,
Of the pair of connected discharge holes, the discharge hole with the largest discharge cross-sectional area
Velocity of the low-speed polymer flow discharged from the outlet 1 (V₁) And vomiting
The high-speed polymer flow discharged from the discharge hole 2 with a small output area
Flow velocity (V₂) And speed ratio (V₁/ V ₂) Is 1 / 1.5 ~
1/7, especially about 1 / 2.3 to 1 / 3.4 is preferable,
Polymer discharge amount ratio at this time (discharge amount Q of discharge hole 1₁/ Vomiting
Discharge rate Q of outlet 2₂) Is 3/1 to 1/5, especially 1.5 /
It is preferably about 1/1 / 3.3.

In the present invention, the polymer stream thus discharged and joined is cooled and solidified, and then collected at various collecting speeds according to the purpose. Here, the take-up speed is 2500 m
If it is less than / minute, the thickness ratio of the thick yarn finally obtained becomes large. On the other hand, when it exceeds 2500 m / min, the thickness ratio sharply decreases. This relationship is shown in FIG. 2, which is 5 denier / 3 obtained according to the examples described later.
It is shown about a drawn filament of 6 filaments. Note that u% as used herein was measured with a model e using a Worcester Evenestester manufactured by Worcester.

The undrawn yarn taken up has a take-up speed of 40.
If it is less than 00 m / min, the mechanical properties are insufficient and it cannot be put to practical use. Therefore, it is preferable to further carry out the drawing heat treatment. Even if the drawing heat treatment operation is applied to the undrawn yarn that has been once wound up. Of course, the stretching heat treatment operation may be continuously applied without once winding.

When the take-up speed is 4000 m / min or more, particularly 4500 m / min to 6500 m / min, the undrawn yarn obtained can be practically used as it is or by simply applying a heat treatment operation without drawing.

The unstretched yarn before stretching is preferably entangled by an entanglement imparting device, which is preferable because it can improve the dispersion of thick portions and fine details.

The present invention is most characterized in that the above-mentioned yarn making method uses a polyester copolymerized with a phosphonium sulfonate compound represented by the following general formula.

[0020]

[Chemical 3]

[Wherein X ₁ is an ester-forming functional group, X ₁ is
₂ is an ester-forming functional group or a hydrogen atom which is the same as or different from X ₁ , R ₁ , R ₂ , R ₃ and R ₄ are the same or different groups selected from an alkyl group and an aryl group, and n is a positive integer . ] Specific examples of such compounds include 3,5-dicarboxybenzenesulfonic acid tetrabutylphosphonium salt, 3,5-dicarbomethoxybenzenedicarboxylic acid tetrabutylphosphonium salt, and 3,5-di (β-hydroxyethoxycarbonyl). Benzenesulfonic acid tetraphenylphosphonium salt, etc., and others
Among the compounds exemplified in 162822, a benzene derivative can be mentioned.

The copolymerization amount of phosphonium sulfonate is
The amount is preferably 1.0 to 3.0 mol% with respect to the difunctional carboxylic acid component constituting the polyester, and if it is less than this range, the effect of suppressing foreign matter on the spinneret surface cannot be obtained and the stability of the cross-sectional shape and the stability of the spinning tone are achieved. Tends to decrease, and the dispersibility of large details and the contrast when dyed tend to decrease. On the other hand, if it exceeds this range, the mechanical properties of the obtained thick and thin yarn are often insufficient.

Next, the polyester copolymerized with the above components, which is the object of the present invention, is a polyester having terephthalic acid as a main acid component and ethylene glycol as a main glycol component. Here, the term "mainly" means that the difunctional carboxylic acid component other than the terephthalic acid component and / or the diol component other than ethylene glycol is 1 with respect to the total acid component.
It means that the polyester may be 5 mol% or less, preferably 5 mol% or less.

The intrinsic viscosity of such polyester is 0.45
It is desirable to be in the range of 1.2 to 1.2, and when it is less than 0.45, the physical properties of the molded product tend to be deteriorated, while 1.
If it exceeds 20, the melt viscosity tends to be too high to attain the object of the present invention.

The melt spinning apparatus used in the present invention is
A commonly used apparatus can be used, and in order to use the resulting multifilament for clothing, the denier of the filament is 0.5 to 8 de, particularly preferably 1.0 to 5.0 de, and the total denier is 30 to 20
It is preferable to set 0 de, particularly preferably 40 to 150 de in terms of texture.

[0026]

When the pulsing yarn is spun, the high-speed polymer stream discharged from the discharge hole having a small discharge cross-sectional area is
The low-speed polymer flow discharged from the discharge hole with a large discharge cross-section is joined while colliding and bouncing. However, if normal polyester is used, foreign matter easily accumulates around the discharge hole, and it takes a very short time. There is a problem that the cross-sectional shape of the fiber is deformed and the spinnability is deteriorated. That is, when melt spinning ordinary polyethylene terephthalate, it depends on the type of catalyst used and additives or the melt spinning temperature, but the height around the discharge hole is about 72 hours after the start of spinning. Foreign matter of 20 to 100 μm is deposited. In the case of producing a normal polyester fiber, even if such a foreign matter deposit reaches about 50 μm, it can be spun without any trouble, but when spinning a pulsing yarn, even a foreign matter deposit of about 2 to 3 μm at most is possible. The flow direction of the polymer flow changes delicately, and stable fiber cross-sectional shape and spinnability can no longer be obtained. Therefore, it is necessary to clean the surface of the spinneret frequently to remove the accumulated foreign matter.

On the other hand, in the melt-spinning of the thick and thin yarn of the present invention, since the polyester in which the organic sulfonate compound having a specific structure is copolymerized in a specific amount is used, the detailed reason therefor is used. It is unknown, however, that the growth of foreign matter deposited around the discharge holes is suppressed, stable spinning can be performed for a very long time, and the cross-sectional shape of the obtained thick and thin yarn is extremely stable.

Moreover, since the spinneret having the discharge holes as shown in FIG. 1 is adopted, it is possible to generate vibrations due to collision and bouncing of the polymer stream, and uneven distribution of spinning drafts acting on the polymer stream. The thick and thin yarns as shown in FIGS. 3 and 4 are obtained.

The thick and thin yarn obtained in this manner has large unevenness in the cross-sectional direction and the longitudinal direction, and therefore has a structure in which filaments having a difference in shrinkage are mixed, and the load-expansion curve thereof is also shown in FIG. 5a. It will be something that will be done.

[0030]

EFFECTS OF THE INVENTION According to the method of the present invention, the deposition of foreign matter on the spinneret is remarkably suppressed, so that thick and thin yarns of stable quality for a very long time can be obtained, and its industrial significance is extremely large.

Moreover, the woven or knitted product using the thick and thin yarn obtained in the present invention can be obtained as a spun-like product which exhibits bulkiness and has a large bulge and a natural appearance only by heat treatment. In addition, since the voids between the single fibers are large, it exhibits excellent water absorption due to the capillary phenomenon, and also has a feature that it has a dry touch and is also excellent as a cool feeling material.

Further, since the compound having a phosphonium sulfonate group is copolymerized, the deep color sharpness of dyeing is also excellent.

[0033]

EXAMPLES The present invention will be further described below with reference to examples.
Physical properties and the like used in this example are measured by the following methods.

(1) Elongation at maximum stress (L
₂) And the final elongation at break (L₁) Using a normal tensile tester, room temperature 25 ° C, humidity 60%
With a sample length of 10 cm and a tensile speed of 20 cm / min
Obtain the elongation curve and calculate the elongation that maximizes the stress (L ₂), O
The elongation at which the force becomes 0 is the final elongation at break (L₁).

(2) Shrinkage rate The obtained multifilament "cassette" was made, and a load equivalent to 2.0 mg / de was applied to this "cassette" to reduce the shrinkage rate when treated in boiling water for 30 minutes. Calculated from the formula. [(A ₀ −a ₁ ) / a ₀ ] × 100 (%) = shrinkage rate (%) a ₀ : length of “cassette” before treatment a ₁ : length of “cassette” after treatment

(3) Dispersibility The thick multifilament obtained was knitted into a cylinder, dyed by a conventional method with a cationic dye, washed with water, and dried.
The sample was set at 0 ° C. for 1 minute, and the length of the deeply dyed part was evaluated for this sample of 10 cm × 10 cm. ◯: All the length of the deep-dyeing part is less than 0.5 cm Δ: The length of the deep-dyeing part is 0.5 to 1.0 cm ×: The length of the deep-dyeing part exceeds 1.0 cm

(4) Contrast The above samples were visually evaluated for contrast of light and shade. ◯: Clear in the deeply dyed part to the lightly dyed part Δ: There is a deeply dyed part and a lightly dyed part but it is unclear ×: The darkly dyed part does not seem to

(5) Deposition height of polymer foreign matter around the discharge hole Immediately before stopping the discharge of the molten polymer, silicone oil is sprayed on the surface of the spinneret, and after removing the spinneret and cooling, the polymer adhering to the periphery of the discharge hole is removed. Then, the height of the deposited foreign matter was randomly measured with a microscope at 10 holes (5 holes per hole, including maximum and minimum), and a total average value was calculated.

[0039]

Example 1 Manufactured using manganese acetate as a transesterification catalyst and antimony trioxide as a polymerization catalyst, 3,
A polyethylene terephthalate polyester having an intrinsic viscosity of 0.64, which is obtained by copolymerizing 5-dicarboxybenzenesulfonic acid tetrabutylphosphonium salt with 1.5 mol% of all acid components, is melted at 290 ° C. and described in Table 1. It is discharged from a spinneret hole as shown in FIG. 1 having a size shown in FIG. 1, taken out at a speed shown in Table 2, and then drawn and heat-treated at a preheating temperature of 85 ° C. and a heat treatment temperature of 220 ° C. for 75 denier / 36.
A thin yarn of filament was obtained. The results are shown in Table 2. In addition, FIG. 6 shows a change with time of foreign matter deposition when spinning was performed at 3000 m / min using the spinning hole type (a).

[0040]

[Table 1]

[0041]

[Table 2]

[0042]

Comparative Example 1 The procedure of Example 1 was repeated, except that manganese acetate was used as the transesterification catalyst and polyethylene terephthalate having an intrinsic viscosity of 0.642 was prepared using antimony trioxide as the polymerization catalyst. The results are shown in Table 3. Further, as in the case of Example 1, changes over time in the deposition of foreign matter are shown in FIG.

[0043]

[Table 3]

As is clear from the above results, according to the method of the present invention, the accumulation of foreign matters around the spinning holes can be suppressed, stable spinning can be carried out for a long period of time, and the occurrence of abnormal cross-sectional shape is reduced. Become.

[Brief description of drawings]

1A and 1B are plan views showing an example of discharge holes of a spinneret used in the present invention.

FIG. 2 is a graph showing the relationship between the spinning speed when using the spinning hole (a) type and the Worcester spot (u%) of the obtained thick and thin yarns.

FIG. 3 is a cross-sectional view of a filament constituting a thick yarn obtained by the present invention.

FIG. 4 is a perspective view in the longitudinal direction of filaments that compose a thick yarn obtained by the present invention.

FIG. 5 (a) shows the stress of the thick and thin yarn obtained by the present invention.
It is an elongation curve, and (b) shows the stress-loading curve of the thick part (a) and the detail (b) of the thick thin yarn obtained by the conventional nonuniform drawing.

FIG. 6 is a graph showing changes with time in the height of foreign matter accumulated in the spinning holes, where a is the present invention and b is a comparative example.

Claims (1)

[Claims] 1. A polyester flow having a flow velocity difference is discharged through a spinneret in which a plurality of discharge holes having different discharge cross-sectional areas are connected by a slit, and the discharge is performed from a discharge hole having a large discharge cross-sectional area of the discharge holes connected by a slit. In the method for producing a polyester thick yarn, the high-speed polymer flow discharged from a discharge hole having a small discharge cross-section is bonded to the low-speed polymer flow that has been discharged, bound while being bound, and then cooled and solidified to obtain polyester. The sulfonic acid phosphonium salt compound represented by the following general formula is 1.
A method for producing a polyester thick yarn, which comprises using a polyester copolymerized with 0 to 3.0 mol%. [Chemical 1] [Wherein, X ₁ is an ester-forming functional group, X ₂ is the same or different from X ₁ , an ester-forming functional group or a hydrogen atom,
R ₁ , R ₂ , R ₃ and R ₄ are the same or different groups selected from an alkyl group and an aryl group, and n is a positive integer. ]