JPS63304024A - Polyester polymer for high-speed spinning - Google Patents

Abstract

PURPOSE:To provide the titled polymer outstanding in dyeability such as to be capable of low-temperature and dense dyeing, giving specified crystallization enthalpy shown by falling temperature crystallization peak in the differential scanning calorimetry. CONSTITUTION:The objective polymer containing >=95mol.% of ethylene terephthalate recurring unit with an intrinsic viscosity pref. >=0.5, giving crystallization enthalpy >=-10J/g determined from the falling temperature crystallization peak resulting from falling temperature crystallization at a falling temperature rate of 20 deg.C/min following keeping 8mg of the polymer sample at 300 deg.C for 3min in the differential scanning calorimetry.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyester polymer that can be used in a method for producing polyethylene terephthalate fibers with good dyeability at high speed. For more details, 7,000m/
When spinning polyethylene terephthalate fibers that have sufficient practical properties and good dyeability using only the melt spinning process without going through a drawing process at a high speed of more than 10 minutes, it is necessary to improve the dyeability even further. The present invention provides a polyester polymer that can be used as a polyester polymer.

Polyethylene terephthalate fibers have a dense molecular structure and do not have polar groups, so they are dyed using disperse dyes at high temperature and high pressure. This is extremely inconvenient not only from the perspective of dyeing costs, but also because when dyeing in the same bath with other fibers, the other fibers become contaminated and become brittle. Many inventions have been made to date.

For example, a method of using a carrier during dyeing is known, but it has drawbacks such as the need for a special carrier and the difficulty in post-treatment of the dyeing solution.

On the other hand, U.S. Pat. , No. 195,051, Journal of the Japan Textile Society, Volume 37, Floor 4, T-
135 to T-142 (1981), etc. U.S. Pat. No. 4,195,051 discloses that a polyethylene terephthalate melt held at a specific temperature is
Polyethylene terephthalate fibers obtained by spinning at spinning speeds ranging from m/min to 7,300 m/min are disclosed. However, although the level of dyeability of these fibers is improved over conventional polyethylene terephthalate fibers, it is still insufficient. In addition, 37 volumes of the Journal of the Textile Society,
In Uo 4, T-135 to T-142 (1981), fibers obtained by spinning at a spinning speed of 9,000 m/min while cooling with -2°C cooling air were found to have high dyeability. Although described, the dyeability of this fiber is still insufficient.

In order to overcome this insufficiency, Japanese Patent Application Laid-Open No. 121.6/1982
13. Japanese Patent Application Laid-Open No. 58-208.415 discloses that polyethylene terephthalate fibers having a certain structure have good dyeability, but the properties of the polymers constituting these fibers are not limited. First, the dyeing properties of the fibers were also outstanding and not limited.

The present inventors have conducted intensive studies on polymers to be used in the production of polyethylene terephthalate fibers that have significantly superior dyeing properties compared to the above-mentioned conventional techniques. The present invention was achieved by discovering that the good dyeability of fibers obtained by conventional techniques is closely related to the enthalpy of crystallization (ΔHc) of the polymer constituting the fibers.

That is, the present invention is capable of spinning polyethylene terephthalate fibers that have sufficient practical properties and good dyeability using only a melt spinning process at a high speed of 7,000 m/min or more without going through a drawing process. The purpose of this invention is to provide a polyester polymer that can further improve the dyeing property.

The polymer for high-speed spinning of the present invention is a substantially polyethylene terephthalate polymer containing 95% or more of ethylene terephthalate repeating units, and in differential scanning calorimetry of the polymer, a molten sample with a sample weight of 8 mg and a sample temperature of 300°C was After holding for 3 minutes, the temperature decrease rate was 20
Crystallization enthalpy (ΔHc) determined from the temperature-falling crystallization peak measured when temperature-cooling crystallizes at a rate of °C/min.
is -IOJ/g or more, which is a polyester polymer for high speed spinning.

One of the particularly important points is that the ethylene terephthalate repeating unit content of this polyester polymer is 95% or more, and when the repeating unit content is 95% or less, the light resistance, heat resistance, etc. that the original polyethylene terephthalate fiber has Since the properties are impaired, the improvement of polyethylene terephthalate fibers, which is the object of the present invention, becomes insufficient.

The characteristics of the polymer provided in the present invention are that in differential scanning calorimetry of the polymer, the sample weight was 8 mg, and the sample temperature was 3.
After holding a molten sample at 00°C for 3 minutes, the enthalpy of crystallization (
ΔHc) is -10 J/g or more. To produce such a polymer, a metal compound of Group 4 of the periodic table, such as germanium oxide, tin oxide, lead oxide, or lead acetate, is used as a polycondensation catalyst in a conventionally known method for polymerizing polyethylene terephthalate. Intrinsic viscosity [η
) is 0.5 or more, and when an antimony compound is used as a polycondensation catalyst, it can be obtained by adjusting the intrinsic viscosity [η] of the polymer to 0.8 or more.

In particular, when a metal compound belonging to Group 4 of the periodic table is used as a polycondensation catalyst, it is preferable that the atomic number of the metal is higher. Furthermore, when an antimony compound is used as a polycondensation catalyst, the intrinsic viscosity [η] of the acid polymer is 0.8
In doing so, it is preferable to suppress the generation of side reaction products such as oligomers by shortening the polycondensation reaction time as much as possible.

The manufacturing method for obtaining such a polymer is not particularly limited, and additives (for example, matting agents, stabilizers, antistatic agents, etc.) may be included as appropriate, and an appropriate intrinsic viscosity may be selected.

More preferably, the top temperature of the temperature-falling crystallization peak determined during the above measurement of the polymer of the present invention is 160° C. or lower, so that the dyeing property is better.

An example of a high-speed spinning manufacturing method using the polymer of the present invention will be described as a method in which the spinning apparatus shown in FIG. 1 is used and the spinning conditions are as follows.

That is, when polyethylene terephthalate is melt-spun through a spinneret 2 having a plurality of spinning holes at a spinning speed of 7,000 m/min or more to produce polyethylene terephthalate fibers, the spun monofilament group 4 is passed through the spinneret. over a length of 51 or more from the bottom surface of 2, 15
The monofilament group 4 is passed through a heating area maintained at a temperature of 0° C. or higher and 300° C. or lower, and is then focused by a focusing guide 5 consisting of a lubricating nozzle located at a position that satisfies both conditions a and b below. , a method characterized by forming a filament bundle 41, which can be produced by appropriately selecting the discharge amount, filament cross-sectional shape, and spinning speed.

a, Area 501 or more below the thinning completion point of monofilament group 4, b, Filament bundle 41 at 5CI+ below guide 5
The tension applied to it is 0.4g/denier or less.

The method for producing polyethylene terephthalate fibers of the present invention will be further explained with reference to FIG. 1, which is an example of the apparatus used for producing the polyethylene terephthalate fibers of the present invention. Molten polyethylene terephthalate is spun from a spinneret 2 with multiple holes in a heated spinning head 1, becomes a monofilament group 4, passes through a heating zone formed in a heating cylinder 3 while gradually becoming thinner, and is exposed to cooling air. 6, the monofilament group 4 is then focused and oiled by a focusing guide 5. At this time, the monofilament group 4 completes rapid thinning above the focusing guide 5 by neck stretching. The focusing guide 5 is arranged 5 (21 or more) lower than the above-mentioned thinning completion point, and
The tension applied to the filament bundle 41 5 cm below the focusing guide 5 is less than 0.4 g/denier.

The filament bundle that has passed through the focusing guide 5 is wound up by a winding roll 7 of a high-speed winding device at a speed of 7,000 m/min or more. If necessary, it is also possible to perform entanglement treatment using an air agitation method before winding.

a focusing guide consisting of a refueling nozzle used in the method;
The winding device and other equipment necessary for melt spinning are as follows:
Any of these may be known. Furthermore, the finishing oil used in the method of the present invention may be either an emulsion type or a straight type, and its components may be known.

Furthermore, another example of the method for manufacturing the fiber of the present invention is shown in FIG.

The molten polyester is spun from a spinneret (not shown) in the heated spinning head 1, and cooled in the atmosphere to form yarn 4. At this time, a tubular heating area 3 surrounding the spun yarn is provided below the spinneret, and a fluid suction device 60 for cooling and suctioning the yarn is provided below it. The yarn that has passed through the tubular heating zone and the fluid suction device passes through an oil application device 50 and a convergence device 51, and then is taken off by a take-off roll 71.

[Measurement method of each characteristic]

The method for measuring the characteristics of the fiber of the present invention will be described below.

<Crystallization enthalpy (ΔHc)> Using a differential scanning calorimeter DSC-7 manufactured by PerkinElmer, sample type M8 was heated at a temperature of 30°C at the start of heating the sample, a temperature at the end of heating at 300°C, and a heating rate of 20°C. Temperature-lowering crystallization measured when the sample was heated at a temperature of 300°C/min, then melted and held for a holding time of 3 minutes, and then the sample was cooled and crystallized at a cooling rate of 20°C/min. The enthalpy of crystallization (ΔHc) is determined from the peak. FIG. 3 shows an outline of the differential scanning calorimetry curve in this measurement. The temperature difference ΔT between the sample and the reference material shows a heating crystallization peak and a crystal melting peak during the heating process, and a cooling crystallization peak during the cooling process.Each enthalpy (ΔH) is calculated from these peaks. Ru.

<Temperature Tma at which the mechanical loss tangent (tan δ) is maximum
x＞Manufactured by Toyo Baldwin Co., Ltd., Rhe Pybron (Rhe
.

Vibron) DDV-HA type dynamic viscoelasticity measuring device was used to measure the tan at each temperature in dry air at a sample of about 0.1 mm, a measurement frequency of 110 Hz, and a heating rate of 5°C/min.
Measure δ and E' (dynamic modulus). As a result, a tan δ -temperature curve is obtained. From this graph, ta
Temperature at which nδ reaches its maximum (Tmax) ('C) and tan
The maximum value of δ (tan δ) wax is obtained.

<Dyeability> Dyeability was evaluated by the equilibrium dyeing rate after raising the temperature to the dyeing temperature and keeping it at that temperature for 1 hour. That is, using disperse dye Resolin Blue (trade name of FB Robinil), 3% 0@f, bath ratio 1:50, 100%
Pl as 0 dispersant dyed at temperatures of 110 °C and 110 °C
Add 1 g/l of aper TL and further dilute with acetic acid.
Adjust to l+=6. The dyeing rate is determined by collecting the dye solution after raising the temperature to the specified dyeing temperature and keeping it at the bundle color temperature for 1 hour, calculating the amount of dye in the remaining solution from the absorbance, and subtracting this from the amount of dye used for dyeing. The dyeing rate (%) was calculated using the amount of dyeing. In addition, as a sample, raw yarn and false twisted processed yarn were knitted in one piece, scoured at 60°C for 20 minutes using a score roll Fc 2 g/l, dried, and humidity conditioned (20°C x 65% RH). .

The expression "good dyeability" as used herein means that the equilibrium dyeing rate reaches 88% or more when dyeing as described above at a predetermined temperature.

<Intrinsic viscosity of polyester [η]> Using ortho-chlorophenol as a solvent and varying the polymer concentration, ηSP/c is measured at 35°C, and the value extrapolated to the concentration O is defined as the intrinsic viscosity.

Initial modulus> Measured using a tensile testing machine under the conditions of yarn length 110C1, tensile speed 5/min and chart speed 250/min in an atmosphere of temperature 25°C and humidity 60%, at 1% elongation. Calculate tensile strength (g/d).

<Strength/Elongation> Using a tensile testing machine, yarn length 25 countries, tensile speed 30 cm
Measurement was carried out by a conventional method under the condition of 1/min.

Departure ship opening The present invention will be further explained with reference to Examples below.

[Examples 1 to 6] To 150 parts of dimethyl terephthalate (hereinafter abbreviated as DMT), 105 parts of ethylene glycol and 0.05% by weight of manganese acetate/DMT were added as a transesterification reaction catalyst, and the mixture was heated with methanol at a temperature of 150 to 240°C for 4 hours. The transesterification reaction was carried out while distilling off.

After that, 0.05 germanium oxide was used as a polycondensation reaction catalyst.
wt%/DMT, add titanium dioxide 0.05 wt%/DMT as a matting agent, temperature 250-285℃, 1mm1
Polycondensation was performed for 3 hours under high vacuum with 1 g or less [η] = 0.6
0, melting point = 249°C, top temperature of cooling crystallization peak = 1
A polymer of the present invention having a crystallization enthalpy (ΔHc) determined from the temperature-falling crystallization peak at 53° C.=−1.5 J/g was obtained. Using the melt spinning apparatus shown in FIG. 1, the polymer is
The length of the heating cylinder 3 is 20c11, the internal temperature of the heating cylinder 3 is 170°C,
Distance 1 from the filament thinning completion point to the focusing guide 5
The fibers were spun at various spinning speeds as shown in Table 1 to obtain filaments of 75 d/36 f. The spinneret used at that time had a hole diameter of 0.2.3 s and a number of holes of 36, and the spinneret temperature during the spinning experiment was 295°C. The thinning completion point is DIAMETPR- manufactured by West German company Zimmer.
This was confirmed by measuring the diameter of the monofilament during spinning using MONITOR 460A/2.

The results are summarized in Table 1.

Table 1 (Table 1) It can be seen from Examples 3, 4, and 5.6 that when the polymer of the present invention is spun at a high speed of 7,000 m/min or more, the resulting fibers have good dyeability.

[Examples 7 to 12] Polymerization and spinning were carried out under the same conditions as in Examples 1 to 6 except that lead oxide was used as the polycondensation reaction catalyst.

The obtained polymer had [η] = 0.61, melting point = 251°C
, top temperature of temperature-falling crystallization peak = 159°C, crystallization enthalpy (ΔHc) determined from temperature-falling crystallization peak =
-1, IJ/g of the polymer of the present invention.

The results are shown in Table 2.

Table 2 It can be seen from Examples 9, 10, 11, and 12 that when the polymer of the present invention is spun at a high speed of 7,000 m/min or higher, the resulting fibers have good dyeability.

[Examples 13 to 18] Polymerization and spinning were carried out under the same conditions as in Examples 1 to 6, except that antimony trioxide was used as a polycondensation reaction catalyst and polycondensation was carried out for 4 hours. The obtained polymer is [η]=
0.82, melting point = 256°C, top temperature of cooling crystallization peak = 150°C, crystallization enthalpy (ΔHc) determined from cooling crystallization peak - 8.7 J/g.

The results are summarized in Table 3.

Table 3 Examples 15, 16, 17, and 18 show that when the polymer of the present invention is spun at a high speed of 7,000 m/min or higher, the resulting fibers have good dyeability.

[Comparative Examples 1 to 6] Polymerization and spinning were performed under the same conditions as in Examples 1 to 6 except that antimony trioxide was used as a polycondensation reaction catalyst. The obtained polymer had [η]=0.61, melting point=2
58℃, the top temperature of the cooling crystallization peak -172℃, the crystallization enthalpy (ΔH
e) = −45,7 J/g for a polymer outside the invention.

The results are summarized in Table 4.

In any of Comparative Examples 1 to 6, the dyeability of the obtained fibers was not good, and especially in the fibers spun at high speeds of 7,000 m/min or more, the fibers were spun at the same spinning speed. Examples 3, 4゜5, 6, 9.10.
A comparison with No. 11, 12, 15, 16, 17, and 18 clearly shows that the dyeability is not good, demonstrating the usefulness of the polymer for high-speed spinning of the present invention.

Table 4 [Examples 19 to 21 and Comparative Example 7] Using each polymer used in Examples 1 to 6, Examples 7 to 12, Examples 13 to 18, and Comparative Examples 1 to 6,
Example 19 Spinning was carried out under the spinning conditions shown below.
, 20, 21 and Comparative Example 7.

The spinning conditions were as follows: The melt spinning device shown in Figure 2 was used, and the spinning temperature was 2.
It was spun at 90°C from a spinneret with a hole diameter of 0.25φ and 36 holes, and a diameter of 151 mm and a length of 20 mm was attached directly below the spinneret.
After passing through the heating cylinder 3, 20CI from the heating cylinder outlet
suction and cooling with a fluid suction device 60 installed at position l;
Furthermore, after cooling and solidifying by running in atmospheric air at room temperature,
Apply a finishing agent and wind up at a speed of 8000 m/min.
A filament of 5 g/36 f was obtained. Note that the temperature of the atmospheric air inside the heating cylinder 3 is 200°C, and the temperature of the atmospheric air inside the heating cylinder 3 is 200°C.
The pressure of the air supplied to 0 is 5. Qkg/ruJG, flow rate is 8Nn? /hr, and the temperature was 30°C. The results are summarized in Table 5.

Examples 19, 20, and 21 are the fibers of the present invention,
Shows better dyeability than Comparative Example 7.

5th Presentation ■ Kuni Kuri The polyester polymer for high speed spinning of the present invention exhibits the following remarkable effects.

(b) The polymer itself has special physical properties, so when the polymer is used for high-speed spinning, the resulting fibers and textile products made from the fibers can be dyed at lower temperatures and have deeper colors. Can be dyed.

(b) Since the polymer itself has special physical properties, polyethylene terephthalate fibers with better dyeability can be produced using only the melt spinning process without going through the stretching process at high spinning speeds of 7,000 m/min or more. A well-manufactured method is easily provided.

(c) Since the obtained fibers can be dyed at lower temperatures and in deeper colors, conventional dyeing costs are further reduced, and when dyeing in the same bath with other fibers, etc. Contamination and embrittlement of other fibers are suppressed.

[Brief explanation of drawings]

FIG. 1 is a diagram showing an example of an apparatus for producing polyethylene terephthalate fibers constituting the present invention. FIG. 2 shows another example of the apparatus for producing polyethylene terephthalate fibers constituting the present invention. FIG. 3 schematically shows a differential scanning calorimetry curve in the measurement of crystallization enthalpy (ΔHc) that specifies the polyethylene terephthalate fiber constituting the present invention. l...Spinning head, 2... Spinneret, 3...
... Heating tube (heating area), 4... Monofilament group 1 41... Filament bundle, 5... Focusing guide, 6... Cooling air, 7...
- Winding roll, 50... Oil application device, 51
...Focusing device, 60...Fluid suction device, 71
...Takeover roll. Below are the margins for Figure 1 and Figure 2.

Claims (1)

[Claims] 1. It is a polyester polymer containing 95% or more of ethylene terephthalate repeating units, and in the differential scanning calorimetry of the polymer, the sample weight was 8 mg and the sample temperature was 300°C.
After holding the molten sample at the temperature for 3 minutes, the temperature decrease rate was 2.
When performing cooling crystallization at 0°C/min, the crystallization enthalpy (ΔHc
) is -10 J/g or more, a polyester polymer for high speed spinning.