JPS5854018A - Polycapramide fiber and its production - Google Patents

Abstract

PURPOSE:A nylon-6 fiber that is mainly composed of epsilon-caproamide, has a specific polymerization degree and specific properties, high strength and high initial modulas, thus showing high dimensional stability. CONSTITUTION:A polymer that contains more than 95mol% epsilon-caproamide recurring units, has a relative viscosity higher than 3.0 in sulfuric acid and contains a copper salt and/or an inorganic or organic antioxidant other than the copper salt is subjected to melt spinning where the extruded yarn is passed through a zone which is surrounded with a heating chimney whose atmosphere is kept above the melting polymer in a range from the spinneret surface to 10cm beneath and taken up so that the optical birefringence of the yarn becomes higher than 25X10<-3>. Then, the undrawn yarn is drawn under heating at a draw ratio lower than 3.5 to give a yarn with a strength of higher than 7g/d, residual elongation of 15-30%, initial modulas of higher than 25g/d, dry-heat shrinkage of 1-4% at 150 deg.C, crystal orientation of higher than 92 and amorphous orientation of less than 0.70.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to polycabramide (hereinafter also referred to as nylon 6 ice) fibers, particularly nylon 6 fibers suitable as industrial materials, and a method for producing the same.

Polyamide fibers have excellent strength, toughness, and durability, so they can be used in various industrial applications, such as tire cords, power transmission belts, rubber reinforcing cords for conveyance bells, seat belts, sewing thread, fishing nets, etc. Various cover sheets and the like are used.

However, when this fiber is used for industrial yellow body applications, it has the drawbacks of lacking dimensional stability and having a low modulus.

Therefore, in addition to the high strength, toughness, and durability of nylon 6-based fibers, if dimensional stability and high modulus are added, the applications will further expand. As a result of our earnest efforts to obtain a nylon 6-thread fiber with high strength, high initial modulus, and excellent dimensional stability, the present invention has been achieved.

That is, the above object is (1) consisting of a nylon 6 polymer containing 95 mol% or more of ε-caproamide repeating structural units, and having a sulfuric acid relative viscosity of 6
Melt spinning a polyamide having a high degree of polymerization of 0 or more and containing one or more copper salts and/or an inorganic or organic antioxidant other than the copper salts (n) Spun yarn. The birefringence of the yarn passed through a zone surrounded by an extremely heated cylinder, after which the atmosphere under the nozzle was at least 10a++ or above the melting point, was passed through a zone surrounded by an extremely heated cylinder, and then rapidly cooled and taken off, and passed through a take-up roll. Take off at a take-off speed of 25 x 10' or more, and (in) draw the yarn that has passed through the take-up roll at a draw ratio of 35 times or less)! This is achieved by stretching.

According to this method, the repeating structural unit of ε-caproamide is made of a nylon 6 polymer containing 95 mol% or more, has a high polymerization degree of sulfuric acid relative viscosity of 30 or more, and has one or more copper salts and/or A nylon 6 fiber containing an inorganic or organic antioxidant other than the copper salt and having the following properties at the same time is obtained.

(a) T/D≧7 g/d (b)
50 ≧ E ≧ 15%p)) Mi225g/d) 4≧S and 1 h) ra≧092 (to) F≦l170 Considering the above mle, T/D is strength and E is residual elongation ,
Mi is the initial modulus, △S is the dry heat recovery rate at 150°C,
f'c represents the degree of crystal orientation, and i represents the degree of amorphous molecular orientation.

This fiber is distinctly different from conventional nylon 6 fibers in that it has a low shrinkage rate and a low degree of amorphous molecular orientation.

More specifically, the method of the present invention and the characteristics of the fibers obtained thereby will be explained in detail.

In the raw material polymer, 95 mol% or more of the number of repeating units in the molecular chain is ε.
- Caproamide may contain less than 5 mo/l/% of a copolymer component. Examples of the other nophoramide components that can be copolymerized include polyhexanotylene adipamide, polyhexamethylene sebacamide, polyhexamethylene isophthalamide, polyhexamethylene terephthalamide, and polyxylylene phthalamide. If the copolymer component is contained in an amount of 5 mol % or more, crystallinity and dimensional stability are reduced, which is not preferable.

The nylon 6 yarn polymer has a sulfuric acid + 1 viscosity measured at 25°C using an Ontwald viscometer at a polymer concentration of 1N1k%, and in particular, a polymer with a degree of polymerization of 32 or more is suitable for obtaining the high strength yarn of the present invention. This is preferable. Furthermore, since the polyamide of the present study is mainly used for industrial purposes, an antioxidant is added to the polyamide for the purpose of imparting sufficient durability against heat, elements, oxygen, etc. Copper salts such as copper acetate, cuprous chloride, cupric chloride, cuprous bromide, cupric bromide, cuprous iodide, copper phthalate, copper stearate, and Complex salts of various copper salts and organic compounds, such as 8-oxyquinoline copper, copper complex salts of 2-mercapi-benzimidazole, preferably cuprous iodide, copper acetate, cuprous iodide of 2-mercaptobenzimidazole complex salts, etc., halides of alkali or alkaline earth metals such as potassium iodide, potassium bromide, potassium chloride, sodium iodide, sodium bromide, zinc chloride, calcium chloride, etc., organic halides such as halogentayodobenzene, Hexabromobenzene, tetraiodoterephthalic acid, notylene iodide, tributyl ethyl ammonium iodide, etc., and inorganic and organic phosphorus compounds such as sodium pyrophosphate, sodium phosphite, triphenyl phosphite, 9.10-Sibidro 10-(3/ , 5/-G t-buti tI/a/-
Hydroxybenzene tL/) -9-oxaberphosphaphenanthrene-10-oxide, etc., and phenolic antioxidants such as tetrakis-(methylene-3-
(5,5-Gf-7-f)V4-Hil'.

xypheni/L/)-propionate-co-methane, 1.
3.5-)lymethyl-2,4,6-tris(3゜5-
di-t-butyl-4-hydroxybenzyl), -octadecy)l/-3-(5,5-di-t-phthyl-4-hydroxybenzyl/L/)-globionate, 4
-Hydroxy-3,5-di with monobutylbenzyl phosphate diethyl ester, amine antioxidants such as N,
NI-di-β-naphthyl-p-phenylenediamine, 2
-Norcaf 1-benzimidazole, phenyl-β-naphthylamine, N,N'-diphenyl-p-phenylenediamine, a combination reaction product of diphenylamine and allyl ketone, preferably potassium iodide, 2-mercaptobenzimidazole, and the like.

The antioxidant can be added to the polyamide during the polymerization process or after the polyamide is once made into chips and then sprinkled with chips. The content of antioxidant is copper (salt is 1 as copper)
0-500 ppm, preferably 50-200'I
lpm, other antioxidants range from 0.01 to 1%, preferably o, o from 3 to 05%. The antioxidant is preferably a copper salt and one or more other antioxidants used in combination.

The above-mentioned polyamide dried to a moisture content of 0.3% or less is spun using a melt spinning machine as shown in FIG.

The spun yarn Y spun from the spinneret 1 is cooled and solidified, and then taken off by a take-off roller 6. The take-up speed is the take-up roller 6.
After adjusting, the birefringence of the collected yarn was 25X10
or more, preferably so x 1o-'' to 45
[10'Om/min. Birefringence of undrawn yarn is 25Xi
If it is less than 0', the properties intended by the present invention, i.e., the dry heat yield rate of 8-4% or less and the degree of amorphous molecular orientation of 070 or less, cannot be obtained, and as a result, the desired effects of the present invention, i.e., However, polyamide fibers with excellent dimensional stability and fatigue resistance cannot be obtained.

- A drawn yarn obtained with a strain refraction exceeding about 45' x 10-1' cannot be stably produced as a high-strength yarn of 7.0 B/d or more.

In the method e of the present invention, the temperature of the atmosphere 2 directly below the spinneret 1 is extremely important in order to stably maintain high-speed spinning of 2000 m7 minutes or more. The atmosphere refers to an area surrounded by a heating cylinder 3, which will be described later, from the bottom surface of the base 1. A heating cylinder 3 is installed in an area of at least 101 or more from the spinneret surface to maintain the yarn spun from the spinneret at the melting temperature of the polymer. The addition is heated above the melting point of the polymer. At least 1ocPRI/) #Enclosure 2 is 2 from the cap surface
The temperature is 50°C or higher, usually 270 to 550°C.

L] The length Ll and the inner diameter of the heat cylinder 5 (Dl is, for example, the mouthpiece 1
-), L' = 0.1~1 m', D ='
0.0'5 to 0.5"'m, and L/D≧02. A cooling device 4 is provided below the heating cylinder 5 (with or without a heat insulating area), and the spinning Cool the yarn Y.

Although there are various types of cooling device 4, such as a uniflow type, an annular natural suction type, and an annular blowing type, the method suitable for the present invention is an annular blowing type, which facilitates uniform cooling. This system is illustrated in FIG. 2, which is a sectional view taken along line u-1 in FIG.

The spun yarn Y that has been cooled and solidified is fed to a normal oil supply device 5, that is,
After being applied with a lubricant by an oil supply roll or a guide oil supply device, it is taken up by a pair of take-up rolls, for example Nelson Row/I/6.

By the way, the spinning speed of nylon 6 series fiber is about 1500m/
min or more and less than 35 D Om/min, the molecular chain is in the intermediate orientation region t
In this range, moisture absorption and water absorption during winding cause crystallization and significant vertical swelling, making normal winding impossible. Therefore, within the spinning speed range of the present invention, 2000
At m7 minutes or more and less than 3,500 m/min, the spun yarn is taken off by a take-up row/v6, and then continuously stretched by t2o times or less between it and the drawing roll 7, and then wound up. .

At this time, the take-up roll 6 is heated at a temperature of 120° C. or lower, usually 90° C. or lower. As the stretching roll 7, it is preferable to use a heating roll heated to room temperature to 150°C, preferably 60 to 120°C.

On the other hand, if the spinning speed is 4000 m7 minutes or more, the shrinkage rate of the yarn during reverse winding is large, which may cause the paper tube to collapse or
Since the end face of the winding drum is likely to collapse, in order to prevent this, the stretching roll 7 is preferably used at a lower speed than the take-up roll 6, and winding is performed while providing a relaxation of 20% or less. In this case, both the take-up roll and the stretching roll may be kept at room temperature. The take-up chamber and drawing chamber in which the rolls are installed are preferably kept at relatively low humidity, for example at 25° C. and 40° C., for the purpose of obtaining high-strength yarn.
%RH) using a controlled room. -・- As for the drawing method, a multi-stage drawing method is preferable in order to stably obtain nylon 6-based fibers with flat strength, but since the drawn yarn 8' has already achieved a relatively high degree of orientation, the overall drawing ratio is 35. It is also possible to adopt a one-stage stretching method of 60 to 1.4 times or less, usually 60 to 1.4 times. In order to obtain a high-strength yarn, it is drawn at a high draw ratio of 85% or more of the maximum draw ratio, and rubbed so that the residual elongation is 15 to 30%. It is basically determined by the degree t. Note that the maximum stretching ratio refers to the maximum stretching ratio that can be stretched.

An example of the stretching method of the present invention is shown in FIG. The specific details are as follows. 1F'R (first feed roll) 9 is used at a temperature of 60° C. or lower, usually at room temperature. 2FR (second feed roll) V) 10 is room temperature to 90°C, IDR (first draw roll) 11 is 8
0 to 150℃, HP (hot plate) 12 is 150 to 210℃,
The 2DR (second draw roll) 15 is set to a temperature below the melting point of nylon 6, usually 150 to 210°C, and equal to or higher than the temperature of the roll arranged in the previous stage. The temperature of the last placed RR (tension regulator q-tv) 14 is 210°C or lower.

-12- The stretching ratio between 4FR9 and 21B10 is set within the range of 100 to 1.10, at which no substantial stretching occurs. i
FB 9 may be replaced by Tensor, which is a breastplate, and may not be used.

The yarn is 13 to 20 times between 2FR1O and IDR41, i
The range between DH11 and 2 DE 15 is stretched at 12 to 20 times, and the range between 2 DR15 and RB14 is subjected to limited shrinkage in the range of 090 to 100.

Incidentally, when the one-stage stretching method is adopted, the IDRll is removed, and in this case, the installation of the IFR9 is especially advantageous in order to obtain the desired effect of the present invention.

The tension adjustment zone between 2DR15 and RR14 is particularly important in proscene that is stretched at a high magnification, and by installing this zone, the stretching magnification in the previous stage can be set sufficiently high within the allowable range of stretchability. can. 2DR13
If the shrinkage between RF14 and RF14 is 10% or more, the degree of crystal orientation of the nylon 6 fibers achieved by drawing to 2DE13 will decrease, making it impossible to obtain sufficient strength and initial modulus.

In addition, in the method of the present invention, the spun yarn Y is drawn by the method shown in FIG.
It is also possible to obtain a drawn fiber by a so-called direct spinning/drawing method in which the spun yarn Y is drawn continuously without being wound up once. This process is an efficient manufacturing method because fibers are spun at high speed and drawn continuously after spinning. This process is illustrated in FIG. In the direct spinning/drawing method, take-up row fiy 6
The process up to is exactly the same as the above method.

An example of the stretching process is shown in FIG. 4 (t), in which the take-up roll 6 is used at a temperature of 60° C. or lower, usually at room temperature.

FR17 (feed roll) is room temperature to 90℃, IDR1
8 (first draw roll) is 80 to 150°C, 2 DR (
The second draw roll) 19 is made of one point or less of polyamide.

The temperature of each roll is set to be equal to or higher than the temperature of the roll placed in the previous stage.

The temperature of the RR (adjustment roll) 20 placed last is 220°C or lower.

The stretching ratio between the take-up roll 6 and FB+7 is set in a range of 1.0 to 1.10 at which no substantial stretching occurs.

FR47 is installed between the take-up roll 6 and 1'DF 118 in order to give preliminary stretch when drawing the take-up yarn, but by installing this FR4'7, the drawing of the take-up yarn is carried out smoothly. If the yarn is drawn between 1'DR18 immediately after being taken off by the take-up roll 6, the yarn on the take-up roll 6 will not be stable and single yarn breakage will occur during stretching, which will cause Total yarn breakage occurs, leading to a decrease in yield. On the other hand, if a stretch of 10% or more is applied, non-uniform stretching will occur, which is actually more disadvantageous than when FR18 is not installed.

Incidentally, when the one-stage stretching method is adopted, the IDR 19 is removed, but in this case, the installation of the FR 18 is particularly preferable in order to obtain the desired effect of the present invention.

1.5-2. between FB6 and IDR18. Q times, 1-1
Between 5-DR18 and 2DR49, the yarn is stretched by a factor of 1.2 to 2.0, and 2DR+? 090 between ~RR'20
undergoes limited shrinkage in the range ~1.00.

The reason and effect of installing the tension adjustment zone between DB 19 and RR 20 are the same as in the method explained using FIGS. 1 and 2 above.

Each roll unit has over 200'Om7 minutes, up to 600
0 m 7 minutes or more, it is preferable to use a Nelson roll unit suitable for high speeds. Winding speed is 6000
Therefore, when using the method of the present invention, the first threading is carried out at a speed of about 4000 m/min, and then the threading is gradually carried out using the roll and mb machine. It is advantageous to use a flaw removal machine with an automatic switching device so that the speed can be increased and the bobbin automatically switched when a predetermined speed is reached.

The kelamide fiber thus obtained has the following properties.

(a) 1" / D1≧ 70B/d (b)
50 ≧ E ≧ 1596 (c) M1≧25
g/d -16-) 4≧S and 1% (if fc≧092 (f) F≦070) The definitions and measurement methods of the characteristics (a) to (f) above are as follows.

(a) Tensile strength T/D, (b) Residual': i Hollowness E, (c)
Initial modulus %il According to the definition of J Eng 5-L1017. Take the sample in a skein shape and incubate it in a temperature- and humidity-controlled room at 20°C and 6596EH for 24 hours.
After standing for a period of time, using a tensile test frame 117797107M-4L (manufactured by Toyo Baldwin Co., Ltd.), test length 25ag was applied.
, the measurement was carried out at a tensile speed of 50 cm for 1 minute.

2) Dry heat shrinkage rate △Si Take the sample in a sumo wrestler's shape and leave it for more than 24 hours in a 20'C16596RH temperature and humidity control room.
A sample of length 10 measured by applying a load corresponding to /d was placed in a dispersion chamber at +so'CCrJ, t-y-n for 50 hours in a non-tension state, and then taken out from the oven and placed in the temperature/humidity control room mentioned above for 4 hours. After leaving it for a while, the above load was applied again and the measured length Ill was calculated using the following formula.

Dry heat loss △S = ((j?o-111)/(lo)
Xioo (% 1 (E) Crystal orientation degree fc 1 Rigaku Corporation) Measurement was performed using a sea bream wide-angle X-ray scattering apparatus using CuKa as a radiation source.

When the orientation function of the crystal part is fc, (200) the half value TI of the intensity distribution curve along t on the Debye ring of equatorial interference] H
' was calculated using the following formula.

(to) Degree of amorphous molecular orientation Fi Sample fluorescent agent 1l Whitex BP” (Sumitomo Chemical Co., Ltd. 'A) +7) 0.2 M amount% water #J solution 1
The sample was immersed for 12 hours at m20'C, then thoroughly washed and air-dried to prepare a measurement sample. FOM- manufactured by JASCO Corporation
1 Use a polarization photometer to measure the relative intensity of polarized fluorescence i11! I
It was calculated using the following formula.

-B F=1-- However, A: IW versus intensity of polarized fluorescence in the fiber axis direction.

B: Relative strength in the direction perpendicular to the fiber axis.

The nylon 6-based fiber of the present invention, which has the above characteristics, has the following characteristics compared to conventional industrial fibers and nylon 6-based mechanical fibers used. Although the initial modulus is about 10% lower, the initial modulus is the same or even higher, and the dry heat shrinkage rate is significantly lower.

In terms of fiber structure, compared to conventional yarns, the crystal orientation is slightly higher (but the degree of amorphous molecular orientation is lower).

That is, the nodules are perfectly aligned and well oriented, while the crystals are
The molecular chain of the product is relaxed, the crystalline portion and the amorphous portion each have a stable structure, and the two-phase structure is remarkable.

The structure of the newly developed nylon 6 fiber is significantly different from that of rubber reinforcing fibers, which have traditionally been aimed at increasing strength. In addition, the characteristics of such a fiber structure in the drawn yarn are further enhanced when the yarn is used as a tire reinforcing fiber, for example, in a high-order processing step, especially in heat setting after applying an adhesive. A treated cord made of the inventive fiber with a more pronounced two-phase structure has a significantly lower shrinkage rate. If the shrinkage rate is to be designed at the same level as the treated cord made from conventionally known fibers,
The heat-set stretch after applying the adhesive can be increased to a large extent, making it possible to create a cord with a high elastic modulus. At this time,
The strength of the treated cord is restored to a level comparable to cords made of conventional yarn.

Further, the high fatigue resistance, which is another feature of the nylon 6 fiber of the present invention, is also due to this low degree of amorphous molecular orientation. The fatigue resistance is determined by the 1-year Mallory Tube Fatigue Test according to ASTM-D-885e, and shows a fatigue life that is 25 times longer than that of conventional polyamide materials.

In order to improve the fatigue resistance of conventional yarns, in order to achieve low amorphous molecular orientation, it was necessary to use low-magnification drawn yarns or to manufacture yarns by relaxing them at high temperatures. In this case, only a code with a low elastic modulus was necessarily obtained. By using the nylon 6 fiber of the present invention, a treated cord with high elastic modulus, low shrinkage rate, and excellent fatigue resistance can be obtained. is also possible.

Furthermore, noting that the fatigue resistance of the treated cord made of the fibers of the present invention is extremely excellent, the number of twists was reduced and [1"
4) It is also possible to design the yarn so that the fatigue resistance is maintained at the same level as that of conventionally treated cords made of yarn.

In this case, the twisting speed can be increased and there is konutdalit. What has been desired for a long time has become possible for the first time with the provision of the fiber of the present invention.

Bias tires using treated cords manufactured by reducing the number of twists were found to have improved flat spots and improved durability.

In addition, when used as an example of application other than tire cord, 7: ■ A/Togawa cord, the dimensional stability during rubber vulcanization is good, so the yield is greatly improved, and the bending fatigue life is also improved. Eggplant is thick
” improved. When used as a base fabric for resin coached fabrics, it demonstrated its dimensional stability and was well received.

The present invention will be described below in detail with reference to Examples, but characteristics and measurement methods not mentioned above are as follows.

(1) Dry heat shrinkage rate (processing code) Measured in the same manner as for the yarn described above except that the ΔSl treatment temperature was 177°C.

(2) Intermediate elongation (treated cord) Measurement of MEi forefoot measurement T/DSE1 In the same way as for Ml, find the elongation when a stress of 2.25 g/d is applied in the load-extension curve of the treated cord.Intermediate elongation And so.

Examples-1 to 7 and Comparative Examples-(1) to (3) ηr-360 nylon 6 chips containing 005% cuprous iodide and 15% 2-mercaptobenzimidazole were used as Ecnutruda. It was spun using a mold spinning machine. The hole diameter of the cap is 0
The one with 3 mφ and 204 holes was used, and the polymer temperature was 29
The temperature was 0°C. The spun polymer was passed through a heated cylinder at a temperature of 290° C. under an atmosphere of 50 cm below the spinneret, and then passed through a 50 steel length annular chimney attached through a 5 scar length insulation zone. It was rapidly cooled. The annular chimney cooled the yarn from its periphery with cold air at 20° C. at a wind speed of 50 m/min.

After the yarn passed through a duct with a length of about 4 m and was cooled, it was supplied with lubricant using a lubricating device installed in two stages. The yarn is taken up by a Nelson-type take-up roll (6 in Figure 1) that rotates at a predetermined speed, and then stretched or relaxed between it and a drawing roll (7 in Figure 1). I took it. When the spinning speed was 1,500 to 3 QOOm/min, the take-up roll and stretching roll temperatures were changed as shown in Table 1.

Table 1 +r shows the N light conditions and the characteristics of the drawn yarn.

The wound yarn was drawn under the conditions shown in Table 2, and the drawn yarn properties shown in Table 3 were obtained.

24- Next, each drawn yarn is twisted in the first twist Z direction by 59T/1.
0n, ply twisted yarn was twisted once in 8 directions to form a raw cord. Then, an adhesive application process was performed using a dipping machine E manufactured by Riller. The sample was immersed in RFLm solution, and the solution concentration and liquid draining device were adjusted so that the amount of debris was 5%.

The drying zone was passed through at 150° C. for 160 seconds at a constant length, and the heat treatment zone was passed through at 210° C. for 50 seconds while applying a 10% stretch. Normal zone is 5 at 210℃
A 1% relaxation was applied for 0 seconds to allow the passage. Table 4 summarizes the characteristics of the obtained processed codes.

The cord using the fiber of the present invention had a low shrinkage rate and excellent fatigue resistance.

95- 28- Example-8 Heat after adhesive treatment in Example-5 (sample stain 8);-
Set drying zone 150℃, 130 seconds, fixed length treatment heat treatment zone 210℃, 50 seconds, Nutretch 14% normal zone 210℃, soe
, relaxation -i%, the resulting treated cord has a fineness of 2770, a D1 strength of 22.72 kg, and a strength of 8.20.
g/d1 elongation 192%, intermediate elongation 65%, dry heat shrinkage rate 7.8%, strength utilization rate 1069%, GY fatigue life 882
It had the characteristics of This treated cord had high elastic modulus, low shrinkage, and excellent fatigue resistance.

Examples-9 to 10 The raw yarn (sample f8) used in Example-5 was twisted with the number of twists of 34T/10Cu and 29T/10ffl for both the first twist and the second twist, and the adhesive was applied in the same way as in Example-3. Processing and heat treatment were performed to create a processed code. Table 5 shows a comparison of the treated coats with a reduced number of twists (Examples 9 and 10) with the cords obtained by the conventional method 30 (v actual m%) (1)).

Compared to the treated cord made of conventional yarn, the treated cord made of the present invention sample has lower strength (GY fatigue life button erosion, lower intermediate elongation, and lower dry yield), and has a characteristic treated cord. Obtained.

Examples 11 to 14 and Comparative Examples (4) to (5) Extruder type spinning of nylon chips with ηr = 3.96 containing 0.03% by weight of copper acetate and 20% by weight of 2-mercaptobenzimidazole Spun from brass. The cap is hole FF
A material having a diameter of 70.5 wφ and 136 holes was used, and the polymer temperature was 290°C. The 50'tmcO $ surrounding air below the spinneret was passed through a heating cylinder kept at 290°C, the same as the temperature of the spun polymer, and then attached through a heat insulating zone with a length of 5 scratches.
01 length annular chimney for rapid cooling. The annular chimney was cooled by cold air at 20° C. at a speed of 50 m/min starting from the filamentous periphery.

After the yarn passes through a duct with a length of approximately 4 meters and is cooled, it is coated with lubricant using a two-stage oil supply device, and then pulled by a Nelson-type take-up roll 6 that rotates once at a predetermined speed. After taking it, a 3% stretch was applied continuously between FR17 and 1 % between FR17 and IDR18.
After carrying out the first stage of stretching and then performing the second stage of stretching between 2DE19 and 2DE19, 5% relaxation was given between 2DR19 and RR20, and then the film was discarded. Sampling was carried out by changing the ejection tube so that the residual elongation was 840 and had a residual elongation of 20 to 2596. The drawing conditions are shown in Table 7 in Section 6 and Table 7.

The undrawn yarn when taken off by the take-up roll 6 has a spinning speed of 200
0 m for 7 minutes or more, it became 50 x 10-'' or more, and the drawn yarn at this time was a low shrinkage yarn as shown in Table 7. Next, each drawn yarn was first twisted in the Z direction by 47 T/1.
0 m, the first twist was twisted in 8 directions with 47 T/+ Oax to make a raw cord. Then, an adhesive application process was performed using a dipping machine E manufactured by Riller.

It was immersed in an RFL solution and the adhesion amount was adjusted to 5%.

The wire was passed through the wire transfer zone at 150° C. for 150 seconds at a constant length, and the heat treatment zone was passed at 210° C. for 50 seconds while being stretched at 10%.

The normal zone was passed through the normal zone at 210°C with 11jl+% relaxation for 5 (] seconds.The properties of the obtained treated cord were evaluated and shown in Table 8.The cord using the fiber of the present invention retained superelastic modulus. It had a low drawing yield and excellent fatigue resistance.

[Brief explanation of the drawing]

FIG. 1 is a process diagram showing one embodiment of the spinning process of the present invention. FIG. 2 is a 1-1 sectional view in FIG.'fJS1. FIG. 3 is a process diagram showing the same stretching process. Fourth
The figure is a process diagram showing another embodiment of the present invention. Y... Spun yarn 1... Spinneret 2... Atmosphere inside the heating cylinder 5... Heating cylinder 6 ・ ・ ・ ・ ・ Bow 1 Retrieval Roller... ...Stretch roll patent applicant Toshi Co., Ltd. Procedures
Amendment (Method) Haruki Shimada, Commissioner of the Japan Patent Office1, Indication of the case, Patent Application No. 14554'2, filed in 1982,2, Name of the invention, polycabramide fiber and method for manufacturing the same,3 Person making the amendment January 26, 1988 Date (shipment date) 5. Number of inventions to be increased by the amendment Contents of the amendment in Column 7 of "Detailed Arms" of the 06 amendment subject specification (1) Table 5 on page 28 of Meiwa Homare is attached as attachment 1 (2) Table 7 on page 57 of the specification is amended as shown in Attachment 2.

Claims (1)

[Claims] 1. 25 mol% of repeating structural units of ε-caproamide
A polycapramide-based polymer consisting of the above polycapramide-based polymer, having a high degree of polymerization with a sulfuric acid relative viscosity of 50 or more, and containing one or more copper salts and/or an inorganic or organic antioxidant other than the copper salts. A polycapramide fiber having high strength and significantly improved dimensional stability and fatigue resistance, which also has the following properties. (B) T/D≧7g/d (B) 30 and E≧15% (C) M1≧25 g/6°) 42△S≧1% Ei 1 fc≧092 (F) D≦0.70 In the above, T/D is strength, E is residual elongation, Ml
is the initial modulus, △S is the dry heat shrinkage rate at 150°C, fa
represents the degree of crystal orientation, and i represents the degree of amorphous molecular orientation. 2.1] The repeating structural unit of ε-caproamide is 95
A polycapramide consisting of a polycabramide polymer of mol% or more, having a high degree of polymerization with a sulfuric acid relative viscosity of 30 or more, and containing one or more copper salts and/or an inorganic or organic antioxidant other than the copper salts. 11) The melt-spun yarn is passed through a zone surrounded by a tube in which an atmosphere of at least 10 cIM is heated above the melting point of polycapramide under the spinneret, then it is rapidly cooled and taken off. The birefringence of the yarn passing through the take-up roll is 25X10.
and (m) hot-drawing the yarn that has passed through the take-up re-roll at a draw ratio of 35 times or less. An improved method for producing polycapramide fibers.