JPS5915513A - Production of polyester fiber - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a high speed direct spinning and drawing method for polyester fibers having excellent dimensional stability and fatigue resistance.

In particular, a relatively highly oriented undrawn yarn with a birefringence of 25xIG' or more and a density t of 558 or more is taken at a spinning speed of 1,500 m/min or more, and is continuously drawn without being wound up once.
The present invention proposes a method for efficiently and stably producing polyester yarn having abrasion characteristics by winding at a speed of at least 5500 m/min or more.

Polyester yarn 7i using i IV polymer
'The direct spinning and drawing method, which was used once for sea bream, is now 100
The film was drawn at a relatively low speed of less than 0 m/min, usually around 600 m/min, and then stretched at a stretching ratio of 4.5 times or more, but wound up at a speed of no more than 5,500 m/min. . Then, a method is adopted in which the fibers are subjected to substantial 2Pi stretching, followed by relaxation treatment, and then rolled up. Magnification is 1.5-3.0
However, the winding speed is at least 5500 m/min. For this reason, simply speeding up the conventional method will result in significantly poorer drawing properties, that is, yarn breakage and fuzz will occur significantly, making it virtually impossible to draw the material once. So, what about high-speed spinning and drawing of polyester yarn with excellent dimensional stability and fatigue resistance? Is it stable despite all this? As a result of studying the method for producing this product, it was found that the following method could achieve the following: O The intrinsic viscosity of the polymer is α85 or more, and the polyester 1VtR whose main component is ethylene terephthalate or a reaction product unit. <In the method of spinning fiber with lfL firefly spinning, k) The spinning speed is 1,500 m/min or more, and the refraction is 25
To obtain a drawn yarn of X10' or more and a density of 1558 or more, (b) to obtain a drawn yarn with a density of 1.5 to 1.5
Stretching at 3.0 times with 6 legs and stretching to a residual elongation of 15% or less. At this time, the stretching ratio distribution was made under the following conditions,
Winding at a speed of at least 5500 m7 minutes or more El ≦ 2.0 (1) El −E
2XE3 (The method according to 2J to 7 is adopted.

The present investigation method will be described in detail below with reference to Figure III.

FIG. 1 is a process diagram to which the first method is applied.

The polyester fiber of the present invention is obtained from a polyester in which 90 monoV% or more, preferably 95 mol% or more of the repeating structural units in the molecular chain are ethylene terephthalate units. Examples of such polyesters include terephthalic acid, ethylene glycol, and ethylene oxide components, as well as aromatic dicarboxylic acids such as isophthalic acid, phthanonic acid, naphthalene dicarboxylic acid, and diphenylene dicarboxylic acid;
A copolymer copolymer copolymerized with the diol component of Lengellicol, 5.5g Jl-) I"J, the latter component, or a mixture obtained by melt-mixing a polymer obtained from the former component and the latter component with one polyethylene terephthalate. There are polymers, etc.

In addition, the intrinsic viscosity of the above-mentioned polymer (No. Make it 1.25.1v of polymer
If α is lower than α85, it is impossible to obtain a polyester fiber that maintains a strong 1% elasticity of 7.5 g/α or more and has improved dimensional stability and fatigue resistance as intended by the present invention.

If the inverted t is less than 1.40, stable yarn production is difficult because yarn breakage occurs frequently during the high-speed direct skin spinning and drawing of the present invention.

The intrinsic viscosity in F of the present invention was measured and calculated by the following method.

The relative viscosity η1 of a solution obtained by dissolving 2 g of the sample in bath was measured at 25°C, and the relative viscosity
was calculated.

1V-0,0242η, +0.2654t-Number of falling seconds of solution (seconds) LO-Falling of orthochlorophenono V elf)! <
(sec Jd - Density of solution (g/CC) dO - Density of orthochlorophenol ff (g/Cr+λ
In the present invention, the carboxyl terminal group of the polyester fiber f+1 is 25 eq/+0' g, preferably 20 eq/10' g, or less. In order to do this, the polymer to be spun must be subjected to a previous step, that is, the polymerization step, which is the polyester production step, to obtain a polymer with fewer carboxyl end groups, or the polymer must be remelted during the melt spinning step. An end-capping agent is added to the melt spinning process to reduce carboxyl end groups.

These two methods in this article are based on well-known methods.

The above polymer is spun at spinneret σQ (4 m) and extruded through spinneret UO, i.e., m-spun into spun yarn (Y).

The spinneret θ preferably has spinneret holes (11AJ) on the circumference having a constant radius from the center CG), and 1 to 4 rows of similar spinneret holes are arranged on the outer side. Uses a structured cylindrical ferrule.

A heating cylinder 02 is attached to the spinneret (11), and the atmosphere inside the spinneret (2) is controlled at the melting point of the polymer, usually from 260°C to 400°C, preferably from 280 to 560°C.
It is heated within the temperature range of °C. #1 The length of the heat cylinder is 5
-50G1 preferably 5-25α. .

The passage of the spun yarn through the above-mentioned gas atmosphere reduces the number of breakages during the drawing process of the spun yarn (Y) connected to the cooling cylinder, which will be described later. The reason for this is that the polyethylene terephthalate melt fed through the spinneret θυe has a slight difference in thermal history, but the spun yarn ('Y) that passes through the surrounding air Q4 becomes oriented there. This is because it equalizes the quality of the threads while improving the sex.

The spun yarn (Y) that has passed through the atmosphere 04 is cooled by the cooling air OQ blown into the cooling chamber. The cooled spun yarn (Y) is further cooled by passing through a chimney duct 1-071, and is brought into contact with an oil supply roll θ1 to be coated with an oil agent. The spun yarn (Y) with an oil agent added is a toitoite (not shown)
T31@Roll is concave at a surface speed of +500 m/min or more, preferably +750 m/min or more.
It was taken over in 1994. If the take-up speed is 1500 m/min, even after passing through 14 heat and cooling zones after spinning, relatively highly oriented unstretched paper with a bending rate of 25 x 103 or more and a density of 1.55-8 or more will be produced. 6. Thread is good. TL, as a result,
It is not possible to obtain polyester fibers with improved dimensional stability and fatigue resistance as intended by this 9t4 method (-0
Even if the take-up speed is 1500 m/min, if the condition is to rapidly cool the yarn directly under the spinneret, for example, 9 heating tubes (tin, Based on the fineness, if the single yarn fineness after drawing is 2 denier or less,
Satisfied characteristic power; in some cases it can be obtained, but at this time spinning,
Its stretchability is significantly worse than that of fleas, and it is impossible to use it industrially.

In addition, the said refraction (han) and density are the values obtained by measuring by the following method.

Birefringence (△n): Measured using a JllXTP-11 type polarized microscope manufactured by JllXTP-11, with the D-line of a sodium lamp as the light source, and with a standard Bereck convencator.

A density gradient tube was prepared in which Dongdu, Sifuhua Fuso was used as the liquid, and n-hebutane was used as the liquid.

The undrawn yarn taken by the missing number/drawing roll 4 is not once removed (it is drawn continuously). In order to obtain the spinneret, heat the spinning Nelson roll to form a feed roll (FR), and heat it with 4 pairs of heated Nelson rolls, 2 D R (February, 5 DR (22) J).
After stage stretching, unheated relaxation roll (RR (25
)) Relaxation treatment is performed between the seedlings and sowing. In addition, in the above-mentioned process, the first stage of stretching (Fi+3 is performed at a relatively low temperature and high magnification in row 7.c), and the second stage (E2) and fifth stage (E3) are fully heated at a high temperature. It is necessary to perform the operation at low magnification while giving the following values.That is, E. is preferably 2.0 or less, and T is preferably 1.5 to 1.5.
8, the thickness of E2 and E3 is set to be lower than Br and 1.8 times or less, preferably 1.2 to 1.6 times, and the total stretching ratio (E + X E2X ]!; a is 1.5 ~30 preferably 1.7 to 2.6 times m (medium).

Also, the surface temperature of each Rono V is FRQl: glass transition temperature of polyester ~150'C, preferably 80-120'C
, 1DRgJ: Porie, 7. Glass transition humidity of f/shin ~150℃, preferably 90~150℃, 2DR (21
J: 200-260℃, good *shi (ha 220-250
'C, 5DR (22J: 200-260℃, preferably 250-260℃ RRC25)), 1250
℃ or below, usually using an unheated roll.

The winding degree is 5500m7min or more, usually 4000~6
000 m/min.

As mentioned above, in the conventional direct yarn-protection drawing method of polyester fiber using a high 1cm polymer, the total draw ratio is 4. S y
, above, stretching is normally performed after 5.51 lines 011 Kt
, a two-stage stretching method is often adopted.

- In this case, the high speed IIL welding of the strength wood invention is required to obtain a high bonding elongation with a residual elongation of 15% or less.
0x aff! Although the surface area is cut off by stretching in 2018, the following is a list of cases in which 5-stage stretching is essentially used without changing the single low-magnification stretching.

That is, since the straight V and spinning drawing methods of the present invention involve drawing at a higher speed than the conventional method, it is difficult to draw the material in the straight direction while applying sufficient heat. For example, in the conventional method, a method of inserting a hot plate between the stretching rolls can be adopted, but in the method of the present invention, because of high-speed stretching,
The contact thickness between the yarn and the surface of the hot plate increases (and, as a result, the quality) decreases, yarn breakage and fuzz occur, and the drawability also decreases. Therefore, when drawing, is there a t thread? Is it hot enough? (J
For the purpose of stable stretching, it is effective to divide the second stage of stretching and perform 5-stage stretching using an intermediate E hot low/l/ (HR). I found out. HR (QDR (2+J J is the final drawing low w (5DB(25)) f close to f) V temperature to be incorporated in the middle is preferable, and the second and fifth drawing ratios (E2
, E3), relatively low magnification is adopted.

By employing the above-mentioned method, the spinning stability during the instant drawing process is significantly improved, and polyester (V#) fibers having the characteristics of fibers can be stably obtained.

q) Dry heat shrinkage rate S≧△S≧2% (b) Initial tensile resistance 150≧Mia90g/d
(c) Strength + 0.02T/D, 2 near, 5g/
d) Elongation 151 mouth 2 J096 (e) Birefringence 190xlO"l△na+ 60x1
After twisting two yarns at 0'2500 and applying adhesive to C4,
40~250℃, net stretch -2.0~5.09
When heat-treated at Step 6 to form a processed code, it has the following characteristics. Compared to the conventional processing code t, the "intermediate elongation yield" value is significantly lower. This means that even if a low intermediate elongation cord is made by increasing the modulus, the dry heat shrinkage rate can be lower than that of a conventionally treated cord.

(to) Strength 6.8! T/D25.5 (G) Intermediate elongation ZO and M E 23.0 (Elongation at 4.5kg strength) (A) Dry heat shrinkage rate 50△△S2 and 1.0% (S)
Intermediate elongation + Dry heat retention rate 9% 2ME + △522796 Tires using the above treated coat also have excellent running durability. This model has been shown to have excellent mechanical fatigue properties through the Goodyear Malloro Tube (GY) fatigue test and the Gutdrich Disk Fatigue Test (Mt). This can be understood from the excellent chemical deterioration resistance shown by the retention rate after treatment with 40 sheets.

When used as a tire cord, this material exhibits excellent characteristics of dimensional stability and durability, and exhibits useful performance especially when overused in small tires. This is because dimensional stability is maintained even if the treated cord is designed to have a high modulus.

On the other hand, by designing the modulus to be relatively low, the durability tv t
Good performance can be obtained even when using special tires and bias tires.

In addition to tire cords, applications requiring legal stability, durability characteristics, bending fatigue resistance, and heat resistance, such as ■-
It is also useful as a rubber reinforcing fiber for belts, conveyor belts, etc.

Hereinafter, the present investigation will be described in detail using Example t.

Example 1 Engineering V 1.25, carpoquine terminal group degree 15 eq/
Extract 106 g of polyethylene terephthalate (1 chip) / Spinning temperature (polymer temperature) 295 with radar type spinning machine
Spun at ℃. The spinneret is a cage-shaped array spinneret with five concentric rows arranged from the center of the spinneret, and the hole diameter is 0.61 m.
The one with φ and rL number of 192 holes was used. Discharge amount is 58
It is 4g/min.

There is a heating area at the bottom of the cap, which is made up of a 5-way spin block, and the direct weight of that area, that is, the lower part of the spin lock, was installed for heating with length Z steel and l diameter 22 (7).

The heating direction is the floating surface Z temperature at the central part 35α in the length direction of 550°C? I controlled this. After the spun yarn passed through the Jokikamu area, the heating tube was attached to the bottom through a heat insulating plate with 1α diameter and 20 scratches. -1wtm submerged chimney] for rapid cooling. The chimney wind temperature was 25°C and the wind speed was 45 m/min. The spun yarn was subsequently applied with oil using an oil supply roller, and then guided and passed through a concave surface at a surface temperature of 2250 m/min.
It was taken up with a Nelson roller (rolled 5 times) heated to ℃e.

Next, the yarn is heated to 120°C for 1 hour without being subjected to fatigue.
) Zao'shita jDR (1.60 times between the 5th J,
jDR and 2DR heated at 240℃ IC (multiply of 5 times) 1.25 times, 2DR and 245℃ heated 5 times
In the darkness with DR (number of turns 7), it was completed to 1.18 life, 5DR
and unheated RR (winding 4 times) to give a 2% relaxation, and then thinly plated with a winder.The sample spun under the above conditions was designated as sample plate 1. The yarns were spun from all the yarns, and the results are shown in Table 1 (spinning conditions) and Table 2 (characteristics).

By increasing the spinning conditions, the characteristics of the IFR drawn yarn become ashes, but the spinning discharge amount and drawing ratio are changed according to the characteristics of the drawn yarn, and the drawn yarn fineness + 000D1 residual elongation of the drawn yarn is 1.
It was made to vary from 2 to 15%.

The drawn yarn obtained by the above method was twisted by 49% each.
Two yarns were twisted together at T/10ff to make a raw cord.

Next, use this raw code from Rilla Co., Ltd. (USA)! l! ! ! Combutoritat thus resorcinol-formalin-latex and "PeXuil" manufactured by Kou C Kogyo Co., Ltd. (UK L!II)
Those treated with a shielding agent consisting of a mixed solution of
．． Heat at 250°C for 70 seconds while applying 5-4% tension, and then heat at 240°C at 70°C while applying 1% relaxation.
A treated cord was obtained by heat treatment for seconds. Table 2 also shows the processing code characteristics.

It can be seen that the research method tKoyoroku 1.4 has good yarn reeling properties, and the 2t1 treated cord has a high modulus (IJ'P) and has a low shrinkage rate even at low intermediate elongation, and has excellent fatigue resistance. .

Example IVt29, caleboxy terminal & basic degree 20 eq/10
6g of polyethylene terephthalate chips as in Example 1? It was strained and spun. However, in order to reduce the acceptability of the carboxyl end of the yarn, one ortho-phenyl-phenyl-glycyl is added immediately before the polymer chip is melted in the bath.
Ethyl (Oppo) α 4 51j (
Spinning yarn was carried out with the participation of % of employees. The spinneret has a hole diameter of 0.6 mm,
Kongchang 288 holes were used. Fineness configuration after stretching is 100
The spinning and drawing conditions were carefully studied to obtain a filament of 0 denier-288, and the residual elongation of the drawn yarn was about 12 to 15%. The fifth thread shows the spinning conditions and stretchability. In addition, the characteristics of the drawn yarn and treated cord were shown in the fourth coat. Note that the conditions not specified with the symbol e in Table 6 are the same as those in Medical Case 1.

According to this study, it can be seen that within the range of spinning conditions specified, the drawability is good and the properties are quickly improved.

[Brief explanation of the drawing]

The drawings show a process diagram of the invention. 10... Spin block 11... Base 11A... Base hole 12... Heating interval 15... Heating atmosphere 14... Heat insulation plate 15... ... Cooling direction (circular chimney) 16...
... Cooling air 17 ... Chimney duct Y ... Conflict 18 ... Oil supply roll 19 ・1. - FR (pulling zero roll, feed roll) 20 ...-IDR (first stretching roll) 21
・・・・・・ 2DR (2nd 〃) 22...
・・5DR (5th) 25 ・ ・ ・ ・ RR (relaxed mouth) 24 ・・・Suggestion winder

Claims (1)

[Scope of Claims] The intrinsic viscosity of the polymer (G) is 0.85 or more, and in the method of directly spinning and drawing a polyester fiber whose repeating structural unit is mainly composed of ethylene terephthalate, G (11500+11 To obtain a yarn with a birefringence of 25 x 10" or more and a density of t 5 ! + 8 or more by winding the yarn at a spinning speed of 1.5 mm or more, (0) Do not wind the yarn once (continuously
Stretch it to a residual elongation of 15% or less by 5-stage processing at ~3.0 times.At this time, the stretching ratio distribution was carried out under the following conditions,
A method for producing polyene teno 11, characterized in that El ≦2-0 (1) E+ 2E2 X Es (2).