JPH11302919A - Cheese-like package and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain cheese-like package wound without causing phenomenon incapable of detaching cheese-like package by paper tube fastened by shrinkage force of wound fiber, free from bulge, having small unwinding tension, having extremely good passing property of a weaving or knitting step and a false twist step because of large winding amounts and capable of achieving remarkable reduction of processing cost by reduction of changeover frequency of cheese. SOLUTION: This cheese-like package is obtained by winding multifilament substantially comprising polytrimethylene terephthalate and having >=0.02 double refractive index and 20-150% elongation and has <10% bulge ratio. This method for producing cheese-like package comprises passing melted multifilament extruded from a spinning port through a temperature- retaining area having 2-80 cm length, provided directly under spinning port and kept at 30-200 deg.C to suppress sudden cooling, quenching the melted multifilament to change the filament to solid multifilament, winding the multifilament around a first roll heated at 40-70 deg.C, then winding the multifilament around a second roll heated at 120-160 deg.C without winding up the filament, drawing the multifilament to 1.5-3 times between the first roll and the second roll speed up than that of the second roll, quenching the multifilament (to a temperature lowered by +20 deg.C than glass transition point of the polymer) before winding up and winding up at a lower speed than that of the second roll.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cheese-like package in which polytrimethylene terephthalate fibers having specific physical properties are wound.
A cheese-like package in which polytrimethylene terephthalate fibers having specific physical properties, which can be easily taken out from a winder even if the winding amount is large, and has a small bulge, good winding appearance, and easy to be broken, is provided.

[0002]

2. Description of the Related Art Polytrimethylene terephthalate obtained by polycondensing a lower alkyl ester of terephthalic acid represented by terephthalic acid or dimethyl terephthalate with trimethylene glycol (1,3-propanediol) has a low elastic modulus. (Soft texture), excellent elastic recovery, easy dyeing properties similar to polyamide, and breakthrough properties similar to polyethylene terephthalate such as light resistance, heat setting, dimensional stability, low water absorption The present inventors have studied the use of a polymer as a fiber for clothing by taking advantage of its characteristics (for example, Japanese Patent Application No. 9-339502).

[0003] As a method for obtaining polytrimethylene terephthalate fiber, a molten multifilament extruded from a spinneret is rapidly cooled to be converted into a solid multifilament, and heated to a higher temperature than a first roll heated once without winding and a first roll. The present inventors have found that the spinning method (direct drawing method) in which the film is stretched between the second rolls and then wound into a cheese-like package is a method excellent in terms of soft texture, color development, and productivity. (Japanese Patent Application No. 9-33)
No. 9502). Certainly, when spinning is performed by this method, several tens of
With a winding amount of about 0 g, a fiber having desired physical properties can be obtained,
The fiber wound as a cheese-like package can be easily removed from the spindle of the winder. However, when the winding amount exceeds 2 kg, the wound fiber shrinks, and the shrinking force tightens the paper tube, so that a phenomenon in which the cheese-like package cannot be removed, that is, a so-called winding phenomenon occurs. In addition, even when the package was taken out, there was a case where a phenomenon called bulge swelling of the package side due to the contraction force of the fiber was observed.

In the case of winding a partially oriented yarn (POY), which is a false twist raw yarn obtained by winding at a spinning speed of 2800 to 4000 m / min without substantial stretching, although the degree of tightness is low, Also, the same curling phenomenon as described above was observed.

[0005]

The problem to be solved by the present invention is that even if the winding amount is large, it can be easily taken out from the winding machine, has a small bulge, has a good winding appearance, and has specific physical properties that it is easy to unravel. An object of the present invention is to provide a cheese-like package in which polytrimethylene terephthalate fiber is wound.

[0006]

Means for Solving the Problems The present inventors thoroughly reviewed the spinning conditions in order to suppress the winding in the above-mentioned direct drawing method, and as a result, the tension between the second roll and the winding machine was reduced. The present inventors have found that it is possible to reduce the temperature considerably or to rapidly cool the fiber temperature after passing through the second roll as a countermeasure. As a result of further investigation, the present invention has been reached.
That is, the present invention relates to a method for producing a polymer comprising substantially polytrimethylene terephthalate, having a birefringence of 0.025 or more and an elongation of 20 or more.
A cheese-like package, characterized in that マ ル チ 150% of the multifilament is wound and the bulge ratio is less than 10%.

The polymer used in the present invention is polytrimethylene terephthalate obtained by substantially polycondensing terephthalic acid and 1,3-propanediol. In the present invention, substantially means that it may be a polytrimethylene terephthalate homopolymer or a polytrimethylene terephthalate copolymer shown below. That is, as long as the effects of the present invention are not impaired, isophthalic acid, succinic acid, adipic acid, 2,6-naphthalenedicarboxylic acid, 5-sodium sulfoisophthalic acid and 5
Acid components such as tetrabutylphosphonium sulfoisophthalate, glycol components such as 1,4-butanediol, 1,6-hexanediol and cyclohexanedimethanol, ε-caprolactone, 4-hydroxybenzoic acid,
One or more of polyoxyethylene glycol and polytetramethylene glycol may be copolymerized in an amount of less than 10 wt%.

If necessary, various additives such as matting agents, heat stabilizers, antifoaming agents, tinting agents, flame retardants, antioxidants, ultraviolet absorbers, infrared absorbers, crystal nuclei Agents, optical brighteners and the like may be copolymerized or mixed. The intrinsic viscosity [η] of the polymer used in the present invention is preferably from 0.4 to 1.5, and more preferably from 0.7 to 1.2. Within this range, a fiber having excellent strength and spinnability can be obtained. When the intrinsic viscosity is less than 0.4, it is difficult to develop strength because the molecular weight of the polymer is too low. Conversely, if the intrinsic viscosity exceeds 1.5, the melt viscosity is too high, and melt fracture or poor spinning occurs during spinning, which is not preferable.

The multifilament comprising the polytrimethylene terephthalate of the present invention needs to have a birefringence of 0.025 or more and an elongation of 20 to 150%. If the birefringence is less than 0.025, the curling phenomenon does not occur, and therefore, is not an object of the present invention. Birefringence is 0.0
The range of 25 to 0.055 is obtained by performing stretch false twisting, and if it is 0.055 or more, it can be used as it is and has sufficient mechanical properties as a fiber for clothing.

The elongation of the multifilament of the present invention is 2
It needs to be 0 to 180%. If it exceeds 180%, the passability of the process of false twisting and weaving will be significantly deteriorated. Further, since the crystal elongation of polytrimethylene terephthalate is at least 20%, it is impossible to obtain a multifilament having an elongation of less than 20%.
Preferably, when performing false twisting, 30 to 110% is preferable, and when performing weaving and knitting without performing false twisting, 25 to 40% is preferable.

The cheese-like package of the present invention is wound with a multifilament consisting essentially of polytrimethylene terephthalate and having a birefringence of 0.025 or more and an elongation of 20 to 150%, and a bulge rate of less than 10%. A cheese-like package characterized by the above. The bulge ratio of the cheese-like package of the present invention needs to be 10% or less. The bulge, as shown in FIG. 1, is a bulge on the upper surface of the cheese caused when a tightening force due to shrinkage of the yarn acts on the package due to tight binding. The bulge ratio indicates the ratio of the winding width B of the largest bulge portion of the middle layer to the winding width A of the innermost layer shown in FIG. 1, and is expressed by the following equation. Bulge rate = {(BA) / A} × 100%

The bulge rate is a parameter indicating the degree of tightness. Bulge rate of cheese-like package is 10
If the amount exceeds 100%, the winding is so large that it often does not come off from the spindle of the winder, and yarn breakage, fluff, dyed spots and the like due to uneven deflocculation tend to occur. Preferably, the bulge ratio is 5% or less, and of course, 0% is most preferable. After the cheese-like package of the present invention is used in the weaving and knitting process or the false twisting process, it is very important to reduce the rate of connection to the next cheese-like package in terms of improving work efficiency and reducing costs. Yes, at least the cheese-like package is 2k
g or more, preferably 3 kg or more. Especially in the case of a cheese-like package wrapped with POY, preferably 6 kg
Above, particularly preferably 10 kg or more.

Hereinafter, methods for obtaining a cheese-like package in the present invention will be exemplified, but the cheese-like package of the present invention is not limited by these methods.
First, a preferred example of the straightening method will be described. As a preferred method of the straight drawing method, the molten multifilament extruded from the spinneret is passed through a heat retaining region of 2 to 80 cm in length maintained at an ambient temperature of 30 to 200 ° C. provided immediately below the spinner to perform rapid cooling. After the suppression, the molten multifilament is rapidly cooled to be changed to a solid multifilament,
Between 300 and 3000 m / min with the first roll heated to a temperature of 120-160 ° C. without winding, between the first roll and the second roll at a higher speed than the first roll. After the multifilament is rapidly cooled to (glass transition point of polymer + 20) ° C. or less before winding, the winding is performed using a winding machine at a lower speed than the second roll. is there. In the spinning process, a confounding treatment may be performed as necessary.

[0014] The spinning temperature is from 250 to 290 ° C, more preferably from 260 to 280 ° C. If the spinning temperature is lower than 250 ° C., the developed strength tends to be low. On the other hand, when the spinning temperature exceeds 290 ° C., thermal decomposition becomes severe, and the obtained yarn is colored and does not show satisfactory strength and elongation. The melted multifilaments coming out of the spinneret were not immediately quenched, but were placed immediately below the spinneret.
After passing through a heat-retaining region having a length of 2 to 80 cm maintained at an ambient temperature of 0 ° C. to suppress rapid cooling, it is highly preferable that the molten multifilament be rapidly cooled and converted into a solid multifilament and subjected to a subsequent drawing step. . By allowing the polymer to pass through this heat retaining region, it is possible to suppress the generation of fine crystals and extremely oriented amorphous portions due to quenching of the polymer, and to form an amorphous structure that is easily stretched in the stretching step. Required fiber properties can be achieved.

Since polytrimethylene terephthalate has a much higher crystallization rate than, for example, polyester such as polyethylene terephthalate, such slow cooling requires fine crystals and extremely oriented crystals. This is an extremely effective method for suppressing the formation of an amorphous portion. If the temperature is lower than 30 ° C., rapid cooling occurs, making it difficult to increase the draw ratio. On the other hand, at a temperature of 200 ° C. or higher, yarn breakage is likely to occur. The temperature of such a heat retaining region is preferably from 40 to 200 ° C, more preferably from 50 to 150 ° C. Further, the length of the heat retaining region is preferably 5 to 30 cm.

Regarding the spinning speed of the yarn, the winding speed of the first roll is 300 to 3000 m / min. When the spinning speed is less than 300 m / min, spinning stability is excellent, but productivity is significantly reduced. 3000m / mi
If n exceeds n, the orientation and partial crystallization of the amorphous portion progress before winding, and the stretching ratio cannot be increased in the stretching process, so that the molecules cannot be oriented and sufficient yarn strength is exhibited. Hard to do. Preferably, 1500-2700m
/ Min. Making the speed of the winder lower than that of the second roll is a necessary condition for suppressing winding. If the winding speed is higher than the second roll speed, the filament will be wound in a state where a strong tension is applied, so that winding will occur. Relax ratio (winding speed / second roll speed) is 0.9 ~
0.99, preferably 0.9 to 0.96.

The speed of the second roll is determined by the stretching ratio, but is usually 600 to 6000 m / min. The stretching ratio between the first roll and the second roll is 1.3 to 3 times, and preferably 2 to 2.7 times. If the draw ratio is 1.5 or less, the polymer cannot be sufficiently oriented by drawing, and the strength and elastic recovery of the obtained yarn will be low. On the other hand, if it is three times or more, fluff is severe and stretching cannot be performed stably. The temperature of the first roll is 40-7
The temperature is 0 ° C., and a range in which stretching is easy can be created in this range. Preferably, it is 50 to 60 ° C. Heat setting is performed with the second roll, but the temperature is 120 to 160 ° C.
It is. Below 120 ° C, poor thermal stability, thermal deformation,
In addition to a fiber that easily changes with time, the coloring property is reduced. On the other hand, if the temperature is 160 ° C. or higher, fluff or yarn breakage occurs, and stable spinning cannot be performed. Preferably, it is 120 to 150 ° C.

In order to eliminate the winding, the multifilament (the glass transition point of the polymer +2
0) It is particularly preferable to rapidly cool the mixture to not more than 0 ° C. Polytrimethylene terephthalate, for example, has a characteristic that it has a bent structure and molecules are more easily deformed than amorphous polyesters such as polyethylene terephthalate and polybutylene terephthalate, and the amorphous portion is easily changed over time after heating. Therefore, even while being wound up by the thermal energy applied by the second roll, the amorphous portion is thermally relaxed and it is extremely likely to be rolled up. Thus, it has been found that by performing such rapid cooling, it is possible to freeze the molecular motion of the amorphous portion, and as a result, curling can be suppressed. The yarn temperature after cooling is preferably as low as possible, but is usually from 10 to 70 ° C, preferably from 0 to 4 ° C.
0 ° C. As a cooling method, blowing cold air,
There is no particular limitation, such as immersion in a cooling liquid such as water or an organic solvent, or sliding on a low-temperature plate or roll.

Next, a preferred method for producing POY will be described. P
As a preferred method for producing OY, a molten multifilament extruded from a spinneret is provided directly below the spinnerer at 30 to 200 ° C.
After suppressing the rapid cooling by passing through a heat retaining region of 2-80 cm in length maintained at the ambient temperature of, the molten multifilament is rapidly cooled and changed into a solid multifilament,
Before winding, the multifilament is quenched to (Glass transition temperature of polymer + 20) ° C. or less, and then 2800 to 4000.
There is a method of winding at m / min. The details of each of these conditions are the same as those described in the straightening method. Further, before winding, it is preferable to control the tension before the winding machine by using a roll or the like as necessary, and the tension at this time is 0.1%.
To 0.4 g / d, preferably 0.1 to 0.25 g / d.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to examples. The main measured values in the examples were measured by the following methods. (1) Intrinsic Viscosity This intrinsic viscosity [η] is a value determined based on the following definition formula. Ηr in the definition formula is a value obtained by dividing the viscosity at 35 ° C. of a diluted solution of a polyester polymer dissolved in o-chlorophenol having a purity of 98% or more by the viscosity of the solvent itself measured at the same temperature, and It is defined.
C is the solute weight value in grams in 100 ml of the solution.

(2) Strong Elongation The strong elongation of the yarn was measured according to JIS-L-1013. (3) Birefringence and elastic modulus The birefringence of the yarn was determined from the retardation of polarized light observed on the surface of the fiber using an optical microscope and a compensator. (4) Shrinkage of boiling water The fiber was skeined at 20 cm, immersed in boiling water for 10 minutes, and determined according to the following equation. Here, the original length (L) and the length after processing (L '). Boiling water shrinkage = 100 × (LL ′) / L

(5) Elastic recovery rate The elastic recovery was determined as an elastic recovery rate obtained by the following method. Attach the fiber to a tensile tester with a distance between chucks of 20 cm.
/ Min and let stand for 1 minute. Thereafter, it was returned to the original length (L) again at the same speed, and the moving distance of the chuck (residual elongation: L ') under the condition where stress was applied at that time was read and determined according to the following equation. Elastic recovery rate = 100 × (LL ′) / L

(6) Thermal stress KE-2 manufactured by Kanebo Engineering was used. The measurement was performed at an initial load of 0.05 g / d and a heating rate of 100 ° C./min. The obtained data was plotted with the temperature on the horizontal axis and the thermal stress on the vertical axis. The maximum value of the thermal stress was defined as the peak value of the thermal stress, and the temperature at that time was defined as the peak temperature of the thermal stress. (7) Bulge ratio In FIG. 1, Acm and Bcm when 4 kg were wound were measured, and were obtained according to the following formula. Bulge rate = {(BA) / A} × 100%

[0024]

EXAMPLE 1 Dimethyl terephthalate and 1,3-propanediol were charged at a molar ratio of 1: 2, titanium tetrabutoxide corresponding to 0.1 wt% of dimethyl terephthalate was added, and the temperature was gradually raised to 240 ° C. To complete the transesterification reaction. Titanium tetrabutoxide was further added to the obtained transesterified product at 0.1 wt% of the theoretical polymer amount,
The reaction was performed at 270 ° C. for 3 hours. The intrinsic viscosity of the obtained polymer was 0.9.

The obtained polymer was dried by a conventional method to make the water content 50 ppm, melted at 285 ° C., and extruded through a single-arrayed nozzle having a diameter of 36 and having a diameter of 0.23 mm. The extruded molten multifilament was passed through a heat retaining region having a length of 5 cm and a temperature of 100 ° C., and then rapidly cooled by applying a wind of 0.4 m / min to be converted into a solid multifilament. Next, this solid multifilament was heated to 50 ° C., a first roll having a rotation speed of 1840 m / min, and a rotating speed heated to 140 ° C., 4600 m / min.
Perform hot stretching and heat setting through the second roll of,
Thereafter, it was wound around a third roll having a rotation speed of 4600 m / min at 25 ° C., rapidly cooled, and then wound up at 4300 m / min. It was set so that the obtained fiber became 75d / 36f. The obtained fiber was a 6 kg bulge-free cheese-like package and could be easily taken out from the spindle of the winder. Table 1 shows the obtained fiber properties. The boiling water shrinkage of the obtained fiber was low.

[0026]

Comparative Example 1 Example 1 was repeated except that the third roll was not passed under the conditions of Example 1. In this case, about 1
When it is rolled up into a kg cheese-like shape, roll-up occurs.
The spindle of the winder did not come off. In addition, a large bulge was observed when winding up 6 kg in a state where it could not be removed from the spindle. Table 1 shows the obtained fiber properties.

[0027]

Example 2 The polymer of Example 1 was dried by a conventional method,
After bringing the water content to 50 ppm, the mixture was melted at 285 ° C. and extruded through a single-hole spinneret having a diameter of 36 and having a diameter of 0.23 mm. The extruded molten multifilament passed through a heat-retaining region having a length of 5 cm and a temperature of 100 ° C., and was then rapidly cooled to a solid multifilament by applying a wind of 0.4 m / min, and the solid multifilament was heated to 20 ° C. After passing through a first roll having a rotation speed of 3000 m / min, it was wound up at 3000 m / min. The obtained fiber was a 6 kg bulge-free cheese-like package and could be easily taken out from the spindle of the winder. Table 1 shows the obtained fiber properties.

[0028]

Comparative Example 2 Example 1 was repeated except that the first roll was not passed under the conditions of Example 1. In this case, winding occurred at the stage of winding up to about 1.8 kg cheese, and it became difficult to remove from the spindle of the winding machine, and there were some that did not come off when the experiment was repeated. Table 1 shows the obtained fiber properties.

[0029]

Example 3 Example 1 was repeated except that the yarn passed through the second roll was wound through a cold water bath at 2 ° C. instead of using the third roll. Even after winding 6 kg, it could be easily taken out from the spindle of the winding machine. Table 1 shows the obtained fiber properties. The boiling water shrinkage of the obtained fiber was low.

[0030]

[Table 1]

[0042]

The cheese-like package of the present invention is wound without any tightness, has no bulge, has a small de-tensioning force, and has a large winding amount. The passability is extremely good, and at the same time, the number of times of cheese switching can be reduced, so that a large reduction in processing cost can be achieved.

[Brief description of the drawings]

FIG. 1 shows a schematic diagram of a cheese-like package in which a multifilament is wound around a paper tube.

Claims (3)

[Claims] A birefringence of 0.025 or more and an elongation of 20 to 15 consisting essentially of polytrimethylene terephthalate.
A cheese-like package in which 0% multifilament is wound and a bulge ratio is less than 10%. 2. After the molten multifilament extruded from the spinneret is passed through a heat retaining region having a length of 2 to 80 cm and maintained at an ambient temperature of 30 to 200 ° C. provided immediately below the spinneret to suppress rapid cooling. This molten multifilament is rapidly cooled to be converted into a solid multifilament, wound with a first roll heated to 40 to 70 ° C for 300 to 3000 m / min, and then wound on a second roll heated to 120 to 160 ° C without winding. Winding, stretching 1.5 to 3 times between the first roll and the second roll, the speed of which is faster than the first roll,
2. The multifilament is obtained by quenching the multifilament to a temperature not higher than (glass transition point of polymer + 20) ° C. before winding, and then winding the multifilament at a lower speed than the second roll.
The method for producing a cheese-like package according to the above item. 3. After the molten multifilament extruded from the spinneret is passed through a heat retaining area of 2 to 80 cm in length maintained immediately below the spinner and maintained at an ambient temperature of 30 to 200 ° C. to suppress rapid cooling. The molten multifilament is quenched into a solid multifilament, and before winding, the multifilament is (glass transition point of polymer +20).
The method for producing a cheese-like package according to claim 1, wherein the cheese-like package is obtained by quenching at a temperature of 2800 to 4000 m / min after quenching to a temperature of not more than ℃.