JPS62238815A - Polyester fiber for clothing use - Google Patents

Abstract

PURPOSE:The titled polyester fibers, having the cooling crystallization peak temperature, peak half-width value thereof, birefringence, residual elongation and intrinsic viscosity present within respective specific ranges and suitable for high-speed warping, knitting and weaving. CONSTITUTION:Polyester fibers obtained by specifying the cooling crystallization peak temperature measured by a differential scanning calorimeter at >=195 deg.C, preferably >=200 deg.C, half-width value thereof at <=10 deg.C, preferably <=7 deg.C, birefringence at 0.09-0.130, preferably 0.09-0.120, residual elongation at 40-60% and intrinsic viscosity at 0.50-0.635, preferably 0.50-0.61. The above- mentioned fibers are produced by a method for adding a phosphonic acid compound in an amount of 0.01-1.0mol% based on an acid component constituting the polyester, spinning the resultant blend at a high speed of >=5,000m/min, etc. A high strength is attained while sustaining a high elongation.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a polyester fiber for clothing suitable for high-speed warping, high-speed weaving and weaving.

[Conventional technology]

Polyester, especially polyethylene terephthalate fiber, has many excellent properties such as high strength, high Young's modulus, and heat-resistant dimensional stability, and is therefore widely used in the clothing field.

Such polyester fibers are generally produced by esterifying or transesterifying terephthalic acid or dialkyl terephthalate and ethylene glycol as starting materials, and then
It is obtained by extruding the polyester obtained through the polycondensation reaction from a spinning nozzle in a molten state, winding it up at a spinning speed of 1000 to 5500 m15+, and then stretching it.

[Problem that the invention seeks to solve]

The polyester drawn yarn thus obtained generally has a yarn strength of 52/d and an elongation of 30 to 35%, and has an extremely strong and stable molecular structure, so it can speed up the processing speed of higher-order processes. In particular, when the warping speed is 1000 m/min or more or the weaving speed is 800 rpm or more, yarn breakage or single yarn breakage tends to occur. For this reason, in recent years, countermeasures have been taken to achieve high-speed processing in such high-order steps, such as applying extremely sophisticated confounding processing. Since such a drawn yarn production process requires two steps, a spinning step and a drawing step, adding a more advanced entanglement treatment step is not necessarily a useful method from a production standpoint. In addition, the highly entangled treatment tends to cause entangled portions to remain in the fabric, which is one of the causes of degrading the quality of the fabric.

On the other hand, in recent years, the spinning speed has been increased to 5000 as a streamlining process.
By spinning at high speeds of m/min or higher, polyester fibers with practical fiber properties that can be produced only through the spinning process are about to be industrialized.

However, although this is an extremely advantageous and practical method for producing polyester fiber from the viewpoint of productivity, for example,
The polyester fiber wound around 00 m/m, in has a lower strength, a lower Young's modulus, and is inferior in mechanical properties than the above-mentioned two-step drawn yarn. However, although the strength and Young's modulus are low, the elongation of the yarn obtained is approximately 5.
Since it has a higher zero-chip than a drawn yarn, it has the advantage of easily absorbing impact force and being less prone to yarn breakage and single yarn breakage when performing high-speed processing.

Therefore, it would be extremely advantageous industrially if the drawn yarn could have physical properties such as high strength by the two-step method described above and high elongation by the high-speed spinning method, which are favorable for passing through higher steps.

In order to produce polyester fibers having the above-mentioned physical properties, the present inventors investigated not only the spinning and drawing processes but also the molecular weight and crystallization properties of the supplied polyester.As a result, the molecular weight of the resulting polyester fibers, They discovered that there is a close relationship with crystallization properties and arrived at the present invention.

An object of the present invention is to provide a polyester fiber suitable for high-speed warping, high-speed weaving, and improved process passability during high-order processing.

[Structure of the invention]

The object of the present invention described above is that the cooling crystallization peak temperature (Tc') measured by a differential scanning calorimeter is 195 degrees Celsius or higher, the cooling crystallization peak half width (W) is 10 degrees Celsius or lower,
Birefringence (Δn) is 0.09 or more. +30 or less,
The residual elongation is 40% or more and 60% or less, and the intrinsic viscosity ([η
]) is 0.50 or more and 0.635 or less.

The present invention will be explained in more detail. The first constituent feature of the present invention lies in the definition of the cooling crystallization peak temperature (Tc') and the half width (W) of the cooling crystallization peak measured with a differential scanning calorimeter. The cooling crystallization peak temperature (Tc') of the polyester fiber of the present invention measured by a differential scanning calorimeter must be 195°C or higher, and preferably 200°C or higher to prevent thread breakage during weaving. This is preferable in that it exhibits the following effects more effectively.

Next, the second component of the present invention is that the half width (W) of the cooling crystallization peak measured by a differential scanning calorimeter must be 10°C or less, preferably 7°C or less, and even more The effects of the present invention are exhibited.

If the half width (W) of the cooling crystallization peak is greater than 10°C, even if the cooling crystallization peak temperature (Tc') is 19
Even at temperatures above 5°C, thread breakage and single thread breakage occur during warping or weaving.

The cooling crystallization peak temperature specified in the present invention will be described in detail later, but when measured with a differential scanning calorimeter, the peak temperature of cooling crystallization specified in the present invention is determined by melting the polyester fiber at 300°C for 5 minutes, and then lowering the temperature at a cooling rate of 16°C/min. This is the temperature of the cooling crystallization peak that appears during the temperature-lowering process, and the half-width (W) of the cooling crystallization peak is the half-width of the cooling crystallization peak, which will be described in detail later.

The fiber physical properties of the polyester fiber in the present invention are birefringence Δ
It is necessary to set n to 0.09 or more and 0.130 or less,
Preferably it is 0.09 or more and 0.120 or less. 0.
If it is less than 09, the resulting polyester fiber may have mechanical properties high enough to withstand practical use, but the quality of the resulting fabric will also be poor. In addition, it is more likely than 0.130 to cause single yarn fuzz and yarn breakage in higher-order processes. Further, the residual elongation is 40% or more and 60% or less. Residual elongation is 4
If it is less than 0%, it has little ability to absorb various shocks during high-order processing, and single thread breakage and thread breakage are likely to occur, impairing process passability. If it exceeds 60%, the structure of the fiber is unstable and easily deforms even under the slightest external force, making it impossible to provide a practical fiber for woven or knitted fabrics.

Furthermore, the intrinsic viscosity [η] of the polyester fiber of the present invention is 0.
．． It is essential that it be 50 or more and 0.635 or less. Preferably it is 0.50 or more and 0.61 or less. If the intrinsic viscosity [η] is less than 0.50, the yarn will have poor mechanical properties, and will easily break due to various impacts during high-order processing, impairing process passability. Intrinsic viscosity [η] is 0.
If it exceeds 635, even if the cooling crystallization peak temperature is 195
℃ or more, even if the cooling crystallization peak half width (W) is 10'C or less, the yarn will have low birefringence Δn and low elongation, and will have no ability to absorb shock during high-order processing, resulting in single yarn breakage and thread breakage. Occur. Further, a polymer having an intrinsic viscosity [η] of more than 0.635 has unstable melt spinnability, especially high-speed spinnability, and it is difficult to obtain a uniform yarn for textiles without yarn breakage.

As mentioned above, the polyester fiber of the present invention has a high cooling crystallization peak temperature (Tc') and a small half-width ( W), the yarn strength is high, and the low birefringence Δn is thought to keep the elongation of the yarn high and improve the toughness of the yarn.

The polyester constituting the polyester fiber of the present invention is mainly polyethylene terephthalate consisting of a terephthalic acid component and an ethylene glycol component, but a portion (usually 20 moles or less) of the terephthalic acid component is replaced with other difunctional carbon dioxide. It may be a polyester in which an acid component is substituted, or a polyester in which a part of the ethylene glycol component (usually 20 molt or less) is replaced with another diol component. Furthermore, various additives such as matting agents,
It is a polyester that is copolymerized or mixed with lubricant, flame retardant, antistatic agent, hydrophilic agent, coloring agent, etc. as necessary.

A specific example of the method for producing this polyester fiber will be described below.

When producing polyethylene terephthalate using masterphthalic acid and ethylene glycol as starting materials, it is desirable to appropriately select the type and amount of the phosphorus compound added in the polyester polycondensation reaction step. However, it is difficult to generally specify the type of phosphorus compound and the amount used. For example, it is preferable to use a polyester obtained by adding 0.01 to 1.0 mole of a 7-phonic acid compound to the acid component constituting the entire polyester as the raw material polyester for spinning the polyester fiber of the present invention.

The polyester fiber targeted by the present invention can be obtained by ultra-high-speed spinning such polyester at a spinning speed of 5000 m/min or more.

The spinning raw material polyester is produced by adding phosphonic acid compounds represented by the following general formulas [I] and [■] during the polycondensation reaction step of polyester.

[I] [■] Specific examples of the phosphonic acid compound represented by the general formula CI) include phenylphosphonic acid, methylphosphonic acid,
Phenylphosphonic acid monomethyphosphonic acid dimethyl ester, ethylphosphonic acid dimethyl ester, phenylphosphonic acid diphenyl ester, phenylphosphonic acid diethylene glycol ester, phenylphosphonic acid cyglobylene glycol ester, phenylphosphonic acid cyphthylene glycol ester, methylphosphonic acid diethylene glycol ester , methylphosphonic acid dipropylene glycol ester, and the like.

Further, specific examples of the phosphonic acid compound represented by the general formula [■] include cyclic esters of phenylphosphonic acid and ethylene glycol, propylene gelicol or butylene glycol, methylphosphonic acid and ethylene glycol, propylene glycol or butylene glycol, etc. Examples include cyclic esters of.

However, the phosphonic acid compound of the present invention may be any compound represented by the general formulas CI) and [■], and is not limited to the above specific examples. These phosphonic acid compounds may be used alone or in combination of two or more, and other phosphorus compounds commonly used as color preventive agents for polyesters may also be used in combination as long as the purpose of the present invention is met. Even if you do, there is nothing wrong with that.

The addition of such phosphonic acid diester to polyester is 0.01% relative to the acid component constituting the polyester.
By appropriately selecting the range of ~1.0 molty, preferably 0.03~0.5 molty, there will be no insoluble foreign matter in the polyester, and the pack internal pressure increase during the melt spinning process will be small, and it will be stable for a long time. Makes spinning possible. Moreover, the obtained polyester fiber has satisfactory birefringence and strength.

Further, in order to further exhibit the effects of the present invention, an alkali and/or alkaline earth metal compound may be added in combination, or fine particles such as silicon dioxide may be added in combination as a crystal nucleating agent. However, yarns that become colored due to the addition of fine particles are not preferred as yarns for clothing.

Next, one example of a specific embodiment from which the polyester fiber of the present invention can be obtained will be described with reference to FIG.

The molten polyester is filtered through the pack 1 in the pack housing 2 and discharged to form yarn. The discharged yarn is cooled and solidified in a cooling cylinder 3, and then supplied with oil in an oil supply device 4, and then passed through a first Godey roll (hereinafter referred to as "first GD") 5 and a second Godey roll (hereinafter referred to as "first GD") which rotate at a spinning speed of 5000 m/min or more.
(hereinafter referred to as No. 20D) 5', and is wound up by winding machine B. At this time, the yarn is entangled by the interlacing device 7. Here, the spinning speed refers to the surface speed of the drive roll (first GD) with which the yarn discharged from the spinneret first contacts, and is not the winding speed. However, when +GD and 20D are not used, the winding speed becomes the spinning speed.

In addition, in the present invention, so-called direct spinning drawing, etc., in which drawing is performed continuously in the first GD and the 20th D, is also applied.

〔Example〕

The present invention will be explained in detail below using Examples.

In addition, the cooling crystallization peak temperature (TO'
), cooling crystallization peak half width (W), intrinsic viscosity, and each fiber physical property were determined by the following method.

A. Cooling Crystallization Peak Temperature (Tc') A 1610 cm polyester fiber was sampled, and a thermogram was obtained using a differential scanning calorimeter (Model DSC-4, manufactured by PerkinElmer) according to the following measurement method. The sample was pretreated at 300° C. for 5 minutes using a differential scanning calorimeter, then rapidly cooled, and the temperature was raised to 500° C. at a temperature increase rate of 16 c/min, followed by immediately lowering the temperature at a cooling rate of 16° C./min. The cooling crystallization temperature (Tc') C of the recrystallization peak that appears during cooling was determined using a PerkinElmer data processing system.

B, Cooling crystallization peak half-width (W) C Figure 2 passes through the midpoint C of the line segment AB that connects the perpendicular line passing through the intersection A of PerkinElmer's data processing tangents 1 and 20 and the intersection B of the tangent 3. Intersection point DIlii of the straight line parallel to tangent 3 and the cooling crystallization peak
The difference in temperature D'E' of cooling crystallization peak half width (W) °C
I asked for it as.

C1 Birefringence Δn Measured by compensator method using D-line monochromatic light t- from an Na bulb using a polarizing microscope.

D, intrinsic viscosity The measurement was performed in an orthochlorophenol solvent at 30°C.

80 Strength and elongation were determined from a load-elongation curve using a Tensilon tensile tester manufactured by Toyo Baldwin.

F. Boiling water shrinkage rate (73w) Wound 10 times on a skein remover with a circumference of 1.0. After measuring the original length to while applying a weight of IP/d, the sample is treated in boiling water for 15 minutes. After air drying, the sample length 1+ is measured while applying a weight of 0.15'/d and calculated using the following formula.

Example 1 100 parts of terephthalic acid and 50 parts of ethylene glycol were placed in a reaction vessel and a normal esterification reaction was carried out.
-Hydroxyethyl) terephthalate low polymer was obtained, and then 0.04 part of antimony trioxide and 0.16 part of phenylphosphonic acid dimethyl ester were added to carry out a polycondensation reaction to obtain polyethylene terephthalate. The obtained polyethylene terephthalate was processed using the apparatus shown in FIG.
Spun at a spinning temperature of 300°C using a spinneret with a nozzle diameter of 0.30 mφ and 18 nozzle holes, cooled and solidified by a 25C air flow supplied orthogonally to the running direction of the yarn, An oil agent is applied, further entangling treatment is performed, and the yarn is wound at a spinning speed of 6200 m/min to 50 d/min.
A polyethylene terephthalate fiber of i'8f was obtained.

4, 7 y/d, residual elongation 53%, birefringence Δno, 1
The fibers had a shrinkage rate of 2.6% in 10° boiling water and a number of entanglements of 7/m. Next, when the wound yarn was warped at 1200 m/min, the number of warping fluffs was extremely small at 0.20 times/107 m. WJL (
When trial weaving was carried out at a rotational speed of 800 rprn, the number of occurrences of ciliary feathers was 0.52/h, which was good, and there was no problem with the quality of the fabric.

Comparative Example 1 100 parts of terephthalic acid and 50 parts of ethylene glycol were placed in a reaction vessel, and a normal esterification reaction was carried out to produce bis-(
β-hydroxyethyl) terephthalate low polymer is obtained,
Next, 0.04 part of antimony dioxide and 0.03 part of trimethyl phosphate were added to carry out a polycondensation reaction to obtain polyethylene terephthalate. Then, in exactly the same manner as in Example 1, a 50d/18f polyethylene terephthalate fiber was obtained. The obtained fiber has an intrinsic viscosity of 0.6+, a cooling crystallization peak temperature (Tc') of 190°C, and a half width of 111°C.
The strength is 4.07/d1, the residual elongation is 49%, the birefringence Δno is 097, the boiling water shrinkage is 2.5%, and the number of entanglements is 7/
It had fiber physical properties of m and low strength. Next, when the wound yarn was warped at 1200 m/min, the number of warping fluffs was 2.3 / 10'm, and as a warp yarn, WJL
When trial weaving was carried out at a rotational speed of 80 orpm, the number of occurrences of fluff during fabrication was 13 times/h, both of which were high, and there was a problem with process passability in higher-order processes. In addition, the obtained fabric had many vertical lines.

Example 2 When obtaining a polymer, various polyethylene terephthalate fibers were obtained using the following spinning method as a polyethylene terephthalate t-raw material obtained by changing the amount of phenylphosphonic acid dimethyl ester added as shown in Table 1.

Manufacturing method/manufacturing method A of polyethylene terephthalate fiber Using a nozzle having a nozzle diameter of 0.37 aφ and 18 nozzle holes, the fiber was wound at a spinning temperature of 290° C. and a winding speed of 1300 m/min. Next, drawing was carried out at a draw ratio of 3.05 and a bottle temperature of 100°C, followed by heat treatment using a hot plate at 150°C to obtain a drawn yarn of 50d/18f.

・Manufacturing method B Using the device shown in Figure 1, nozzle hole diameter 0, 3712φ
Using a nozzle with 18 nozzle holes, various polyethylene terephthalate fibers of 50 d/18 f were obtained by changing the winding speed in the range of 4,500 to 7,000 m/min at a spinning temperature of 300°C.

Cold crystallization peak temperature (TC') of the fiber obtained in Table 1,
Table 2 shows the cold crystallization peak half-width (W) and fiber physical properties that indicate passability in higher processing steps.

Among Table 1, only the polyester fibers of level 3.6.9 satisfying the present invention exhibited good high-order passability as shown in Table 2, and the fabric quality was also good.

〔Effect of the invention〕

The polyester fiber of the present invention exhibits the following effects.

In other words, although it maintains the high elongation characteristic of fibers obtained by ultra-high speed spinning, it has high strength, making it a polyester fiber with high toughness, which allows for high processing speeds in various higher-order processes. It is possible to fully respond to the changes.

For example, 10 D Om/min warping or 800 rpm
Even when the above M and TL weaving is performed, there is extremely little fuzz generation, there is almost no stopping of the weaving machine, and high-order processes can be significantly streamlined. Moreover, the obtained fabric can also maintain good quality.

[Brief explanation of drawings]

Figure 1 is a schematic diagram showing the melt spinning process of the present invention, and Figure 7 and Figure 2 are diagrams illustrating a method for measuring the half width (W) of the cooling crystallization peak of poly-11 ester, which has not yet been invented. 1: Pack 2: Bank housing 3: Cooling cylinder 4: Oil supply device 5: 1st GD, s': 2nd GD 6: Winding machine 7: Entangling device Patent application Daito Shi Co., Ltd. Figure 1 Temperature (°C) Figure 2

Claims (1)

[Claims] Cooling crystallization peak temperature (T
c') is 195℃ or higher, cooling crystallization peak half width (W)
is 10℃ or less, birefringence (Δn) is 0.09 or more and 0.1
30 or less, a residual elongation of 40% or more and 60% or less, and an intrinsic viscosity ([η]) of 0.50 or more and 0.635 or less.