JP2002293895A - Polytrimethylene-terephthalate based polyester and fiber formed thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polytrimethylene-terephthalate baed polyester fiber improved in thermosetting property after drawing. SOLUTION: The polytrimethyllene-terephthalate based polyester fiber is a polytrimethylene-terephthalate based polyester polymer, mainly composed of a repeating unit of trimethylene terephthalate, wherein a crystallization peak-temperature is in the range of 180-200 deg.C at temperature-decreasing rate of this polymer of 10 deg.C/min, a L-value of color is 65 or above and a b-value of color is in the range of 3-10.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polytrimethylene terephthalate-based polyester and a fiber comprising the same. More specifically, the fiber is sufficiently fixed in a heat set after a drawing treatment, and a fiber having a low residual elongation can be easily obtained. The present invention relates to a polytrimethylene terephthalate-based polyester and a fiber comprising the same.

[0002]

BACKGROUND OF THE INVENTION As is well known, polyester is
Due to its excellent performance, it is widely used for fibers, resins, films and the like. In particular, polyester fibers made of polyethylene terephthalate have excellent dimensional stability, heat resistance, chemical resistance, light resistance, and the like, and are used in various fields regardless of clothing or non-clothing.

In recent years, attention has been paid to polytrimethylene terephthalate-based polyester fibers and woven or knitted fabrics made of the same in order to develop texture and dyeing properties that are difficult to realize with conventional polyethylene terephthalate (see, for example, Japanese Patent Application Laid-Open No. Hei 11-1999). No. 200175). However, this polytrimethylene terephthalate-based polyester fiber has a problem that since the crystallinity is significantly different from that of polyethylene terephthalate, heat setting after stretching heat treatment is difficult, and the texture of the final woven or knitted product tends to be hard. .

In order to solve such a problem, for example, Japanese Patent Application Laid-Open No. H11-172526 proposes to use special conditions for cooling and winding during spinning.
However, although this method improves the heat setting property of the drawn yarn to some extent, there is a problem that it is not suitable for producing fibers that meet a wide range of requirements because the yarn-making conditions are restricted.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polytrimethylene terephthalate-based polyester fiber which solves the above-mentioned problems of the prior art and has improved heat setting after drawing. And to provide a polytrimethylene terephthalate-based polyester.

Another object of the present invention is to provide a method for producing the above polyester.

[0007]

The present inventors have conducted intensive studies to achieve the above object, and as a result, a fiber obtained by melt-spinning a specific polytrimethylene terephthalate-based polyester has been subjected to heat treatment after stretching. They have found that the setability can be improved, and as a result of further study, they have reached the present invention.

That is, an object of the present invention is to provide a polytrimethylene terephthalate-based polyester polymer mainly composed of trimethylene terephthalate repeating units, wherein the polymer has a crystallization peak temperature at a temperature reduction rate of 10 ° C./min of 180 ° C. to 200 ° C. ° C range and color L
Can be achieved by a polytrimethylene terephthalate-based polyester characterized by having a value of at least 65 and a color b value in the range of -3 to 10.

Another object of the present invention is to use a titanium compound and an antimony compound as a polymerization catalyst in the production of the above polyester, and the relationship between the two is represented by the following formulas (I) to (III): And a process for producing a polytrimethylene terephthalate-based polyester characterized by simultaneously satisfying the following.

[0010]

(Equation 4)

[0011]

(Equation 5)

[0012]

(Equation 6)

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The polytrimethylene terephthalate-based polyester of the present invention is a polytrimethylene terephthalate-based polyester mainly composed of trimethylene terephthalate repeating units.

Here, the term "polytrimethylene terephthalate-based polyester mainly composed of trimethylene terephthalate repeating units" means that the trimethylene terephthalate repeating units constituting the repeating units are 85 mol% or more based on all the repeating unit components. And preferably a polytrimethylene terephthalate polyester occupying 90 mol% or more.

The polytrimethylene terephthalate-based polyester of the present invention needs to have a crystallization peak temperature measured at a cooling rate of 10 ° C./min between 180 ° C. and 200 ° C. When the crystallization peak temperature is less than 180 ° C., the heat setting property after drawing the fiber is lowered, which is not preferable.
In the case described above, the stretchability of the fiber itself deteriorates, which is not preferable.
The range of the crystallization peak temperature measured at a cooling rate of 10 ° C./min is preferably from 180.5 ° C. to 195 ° C. 181 ° C
The range of -190 ° C is more preferable.

Further, the polytrimethylene terephthalate-based polyester of the present invention must have a color L value of 65 or more and a color b value of -3 to 10. When the color value is not within the above range, the hue of the finally obtained fiber or the like deteriorates.

The polyester of the present invention is a GPC (Gel).
Permeation Chromatograph
the degree of dispersion of the polymer (Mw / Mn) measured using y)
Is preferably 2.4 or less. When the degree of dispersion is within this range, the stretchability and fiber properties of the fiber are further improved. The degree of dispersion of the polymer is particularly preferably 2.3 or less.

In the polytrimethylene terephthalate-based polyester of the present invention, components other than the terephthalic acid component and the trimethylene glycol component are copolymerized in a range that does not impair the properties thereof, preferably in a range of 10 mol% or less based on all dicarboxylic acid components. It may be. These copolymerization components include, for example, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenyletherdicarboxylic acid, diphenylsulfondicarboxylic acid, benzophenonedicarboxylic acid, phenylindanedicarboxylic acid, 5-sulfoxyisophthalic acid metal salt,
-Aromatic dicarboxylic acids such as sulfonium isophthalic acid phosphonium salt, ethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, decamethylene glycol, neopentylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol , Polytetramethylene glycol, aliphatic glycols such as cyclohexanediol, alicyclic glycols such as 1,4-cyclohexanedimethanol and 1,4-cyclohexanediol, o-xylylene glycol, m-xylylene glycol, p-xylylene Len glycol, 1,
4-bis (2-hydroxyethoxy) benzene, 1,4
-Bis (2-hydroxyethoxyethoxy) benzene,
4,4'-bis (2-hydroxyethoxy) biphenyl, 4,4'-bis (2-hydroxyethoxyethoxy) biphenyl, 2,2-bis [4- (2-hydroxyethoxy) phenyl] propane, 2,2 -Bis [4-
(2-Hydroxyethoxyethoxy) phenyl] propane, 1,3-bis (2-hydroxyethoxy) benzene, 1,3-bis (2-hydroxyethoxyethoxy)
Benzene, 1,2-bis (2-hydroxyethoxy) benzene, 1,2-bis (2-hydroxyethoxyethoxy) benzene, 4,4′-bis (2-hydroxyethoxy) diphenyl sulfone, 4,4′-bis Aromatic glycols such as (2-hydroxyethoxyethoxy) diphenylsulfone, hydroquinone, 2,2-bis (4-hydroxyphenyl) propane, resorcin, catechol, dihydroxynaphthalene, dihydroxybiphenyl, diphenols such as dihydroxydiphenylsulfone, etc. No. These may be used alone or in combination of two or more.

The polytrimethylene terephthalate-based polyester of the present invention can be produced by a conventionally known method. For example, a terephthalic acid component and a trimethylene glycol component are subjected to an esterification reaction or a terephthalic acid lower alkyl ester component is reacted with a lower alkyl ester component. It is possible to employ a method of subjecting a trimethylene glycol component to a transesterification reaction in the presence of a transesterification catalyst to obtain a bisglycol ester and / or an initial condensate thereof, followed by a polycondensation reaction in the presence of a polycondensation catalyst. I can do it. Further, in order to increase the molecular weight, solid-phase polymerization to reduce the amount of terminal carboxyl groups can also be preferably performed by a conventionally known method,
As a polymerization catalyst used in producing the polytrimethylene terephthalate-based polyester of the present invention, a titanium-based compound (hereinafter, sometimes abbreviated as Ti catalyst) and an antimony-based compound (hereinafter, abbreviated as Sb catalyst) may be used. )). At that time, the respective amounts may be in the range of the compositions of the following formulas (I) to (III).

[0021]

(Equation 7)

[0022]

(Equation 8)

[0023]

(Equation 9)

Here, the amount of the Sb catalyst may be in the range of 10 to 100 mmol%, and if it is within this range, the heat setting property after drawing of the fiber made of the obtained polymer is improved, and Heat resistance is also improved. The amount of Sb catalyst is more preferably from 15 to 90 mmol%, especially from 20 to 80
It is preferably in the range of mmol%.

The amount of the Ti catalyst may be in the range of 10 to 100 mmol%. When the amount is within this range, the polymerization reaction rate of the polymer is increased and the heat resistance of the polymer is improved. The amount of the Ti catalyst is more preferably in the range of 15 to 90 mmol%, particularly preferably in the range of 20 to 80 mmol%.

Further, the value obtained by dividing the amount of the Ti catalyst by the amount of the Sb catalyst may be 0.5 to 3.0. When the value falls within this range, the polymerization rate is sufficiently high and the color of the polymer is good. Further, the heat setting property after drawing when the obtained polymer is used as a fiber is also improved. A more preferable range of the value obtained by dividing the amount of the Ti catalyst by the amount of the Sb catalyst is 0.6 to 2.8, particularly 0.8.
It is preferably in the range of 2.5 to 2.5.

The polytrimethylene terephthalate-based polyester of the present invention may contain, if necessary, a small amount of additives such as a lubricant, a pigment, a dye, an antioxidant, a solid phase polymerization accelerator, a fluorescent brightener, an antistatic agent, and an antibacterial agent. Agents, ultraviolet absorbers, light stabilizers, heat stabilizers, light-blocking agents, matting agents and the like.

The fiber comprising the polytrimethylene terephthalate-based polyester of the present invention is obtained by mixing the polytrimethylene terephthalate-based polyester of the present invention with 238 ° C to 275 ° C.
It is preferable to produce by melt spinning in the range of ° C. When the melt spinning temperature is within this range, no breakage occurs during spinning. The melt spinning temperature is 239-270 ° C
Is more preferably in the range of 240 ° C. to 26 ° C.
Preferably it is in the range of 5 ° C.

The fiber made of the polytrimethylene terephthalate-based polyester of the present invention can be used when melt-spinning the polytrimethylene terephthalate-based polyester of the present invention.
It is preferable to spin at a speed of 00 to 5000 m / min. When the spinning speed is in this range, the strength of the obtained fiber is sufficient and the winding can be performed stably. The spinning speed is more preferably in the range of 500 to 4700 m / min, and particularly preferably in the range of 600 to 4500 m / min.

The drawn yarn made of the polytrimethylene terephthalate-based polyester of the present invention can be obtained by winding the above-mentioned polytrimethylene terephthalate-based polyester fiber or by continuously drawing it once without winding it. A drawn yarn having a boiling water shrinkage of 12% or less after heat treatment in the range of ° C can be obtained.

The polytrimethylene terephthalate-based polyester fiber of the present invention has an intrinsic viscosity of 0.5 to 1.5.
Is preferably within the range. When the intrinsic viscosity is within this range, the mechanical strength of the finally obtained fiber is sufficiently high and the handling becomes good. The intrinsic viscosity is more preferably in the range of 0.52 to 1.4, and particularly preferably in the range of 0.55 to 1.3.

In producing the polytrimethylene terephthalate-based polyester fiber of the present invention, there is no limitation on the shape of the die used at the time of spinning, and any of a circular shape, a deformed shape, a solid shape, and a hollow shape can be employed.

[0033]

The present invention will be described in more detail with reference to the following examples, which should not be construed as limiting the present invention. The parts in the examples are parts by weight. Various characteristics were determined by the following methods. (1) Intrinsic viscosity: measured at 35 ° C. using orthochlorophenol as a solvent, and determined from the relative viscosity by a conventional method. (2) Tensile strength and tensile elongation: Measured according to the method described in JIS L1070. (3) Temperature drop crystallization peak temperature TA Instrument as a differential scanning calorimeter (DSC)
ents DSC2010 Differenti
The sample heated to 260 ° C. at a rate of 10 ° C./min was cooled at a rate of 10 ° C./min using an al Scanning Calorimeter, and the temperature was reduced according to JIS K7.
According to 121, the crystallization peak temperature was measured. (4) Boiling water shrinkage: JIS L1073 6.12
In the method for measuring the hot water shrinkage ratio described in (1), the measurement was performed using boiling water. (5) Molecular weight dispersion of polymer: Waters 48
Using the apparatus was connected to a Waters GPC column μ styrange10 ³ ~10 ⁶ to 6-inch liquid chromatograph, using chloroform as the developing solvent, was diluted to 10ml samples 1mg was dissolved in hexafluoroisopropanol 1ml chloroform Sample And the weight average molecular weight (Mw) in terms of polystyrene,
The number average molecular weight (Mn) was measured, and Mw / Mn was defined as the degree of dispersion.

Example 1 Dimethyl terephthalate 100
Parts, 70.5 parts of trimethylene glycol and 0.0875 parts of titanium tetrabutoxide as a catalyst were charged into a reactor equipped with a stirrer, a rectification column and a methanol distillation condenser, and the temperature was gradually raised from 140 ° C. The transesterification reaction was performed while distilling the methanol generated as a result of the reaction out of the system. Three hours after the start of the reaction, the internal temperature reached 210 ° C.

Next, after adding 0.0375 parts of diantimony trioxide to the obtained reaction product, it was transferred to another reactor equipped with a stirrer and a glycol distilling condenser.
The temperature was gradually raised from 0 ° C to 265 ° C, and
The polymerization reaction was carried out while reducing the pressure to a high vacuum of 0 Pa.
The melt viscosity of the reaction system was monitored, and the polymerization reaction was stopped when the intrinsic viscosity became 0.75.

The molten polymer was extruded into cooling water from the bottom of the reactor in the form of strands, and cut into chips using a strand cutter.

The obtained chip was melted at 250 ° C. using an extrusion spinning machine having a spinneret having 36 circular spinning holes having a hole diameter of 0.27 mm, a discharge rate of 34 g / min, and a take-up speed of 2
The unstretched yarn obtained by spinning at 400 m / min is subjected to a stretching treatment machine having a heating roller at 60 ° C. and a plate heater at 160 ° C., and is stretched at a stretching ratio of 1.7 to 83.
A drawn yarn of dtex / 36 filament was obtained. The results are shown in Tables 1 and 2.

Examples 2 to 4 The same operation as in Example 1 was performed except that the amounts of titanium tetrabutoxide and diantimony trioxide were changed to the amounts shown in Table 1. The results are shown in Tables 1 and 2.

Example 5 The chips obtained in Example 1 were melted at 250 ° C. using an extrusion spinning machine having a spinneret having 36 circular spinning holes having a hole diameter of 0.27 mm, and a discharge rate of 36 g / And the obtained undrawn yarn is subjected to a drawing machine having a heating roller at 60 ° C. and a plate heater at 160 ° C., and is drawn at a draw ratio of 1.5 and 83 dtex. A / 36 filament drawn yarn was obtained. The results are shown in Tables 1 and 2.

Example 6 The chips obtained in Example 1 were melted at 250 ° C. using an extrusion spinning machine having a spinneret having 36 circular spinning holes having a hole diameter of 0.27 mm, and a discharge rate of 34 g / The fiber is spun at a take-up speed of 2400 m / min, and without being wound up, is subjected to a drawing machine having a heating roller at 60 ° C. and a plate heater at 160 ° C., and is drawn at a draw ratio of 2.4 times to obtain 83 dtex / 36 filament. Was obtained. The results are shown in Tables 1 and 2.

Example 7 The intrinsic viscosity in melt polymerization was set at 0.1.
Polymerization was carried out in the same manner as in Example 1 except that the temperature was changed to 45, and the obtained chip was dried at 130 ° C. for 5 hours. The same operation as in Example 1 was performed except that a solid-phase polymerization reaction was performed for 10 hours to obtain a chip having an intrinsic viscosity of 0.75. The results are shown in Tables 1 and 2.

Comparative Examples 1 and 2 In Example 1, the amounts of titanium tetrabutoxide and diantimony trioxide are shown in Table 1.
The same operation was performed except that the amount was changed to the amount shown in FIG. The results are shown in Tables 1 and 2.

Comparative Example 3 The chip obtained in Example 1 was melted at 250 ° C. by using an extrusion spinning machine having a spinneret having 36 circular spinning holes having a hole diameter of 0.27 mm, and a discharge amount of 36 g / The fiber was spun at a take-up speed of 5500 m / min, but the fiber was severely broken and could not be wound up stably. Table 2 shows the results.

[0044]

[Table 1]

[0045]

[Table 2]

[0046]

According to the present invention, the heat setting property of the polytrimethylene terephthalate-based polyester fiber can be improved under relatively easy spinning conditions, and since the spinning conditions are not restricted, the production of fibers meeting a wide range of requirements can be achieved. Suitable for,
A polytrimethylene terephthalate-based polyester can be provided.

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Claims (6)

[Claims] 1. A polytrimethylene terephthalate-based polyester polymer mainly composed of trimethylene terephthalate repeating units, wherein the crystallization peak temperature of the polymer at a temperature reduction rate of 10 ° C./min is 180 ° C. to 200 ° C.
Wherein the color L value is 65 or more and the color b value is in the range of -3 to 10; a polytrimethylene terephthalate-based polyester. 2. The molecular weight dispersity (Mw / Mn) of the polymer
The polytrimethylene terephthalate-based polyester according to claim 1, wherein is less than or equal to 2.4. 3. A process for producing the polyester according to claim 1, wherein a titanium compound and an antimony compound are used as a polymerization catalyst, and the relationship between the two is represented by the following formula (I):
A process for producing a polytrimethylene terephthalate-based polyester, which simultaneously satisfies (III). (Equation 1) (Equation 2) (Equation 3) 4. The polytrimethylene terephthalate-based polyester according to claim 1, which has a melting temperature of 238 to 275 ° C.
Polytrimethylene terephthalate-based polyester fiber obtained by melt spinning at a spinning speed of 400 to 5000 m / min. 5. A drawn polytrimethylene terephthalate-based polyester yarn obtained by winding the fiber according to claim 4 once or continuously without winding the fiber. 6. The drawn yarn according to claim 5, which has a boiling water shrinkage of 12% or less after heat treatment at a temperature of 120 ° C. to 220 ° C.