WO1991008330A1 - Crimped multifilament and production thereof - Google Patents

Abstract

A crimped multifilament produced from thermoplastic polymer, wherein the birefringence measured at an outer layer part of the constituent monofilament is larger than that measured at a central part thereof, the distribution of the birefringence is such that the position of the smallest birefringence is deviated from the center of the fiber axis, and the number of random crimps per unit inch is at least ten. The degree of crystal growth as determined by wide-angle X-ray diffractometry is at least 0.2 in the case of polyamide and at least 0.4 in the case of polyester. A preferable method of producing the crimped multifilament comprises cooling multifilaments extruded through spinnerets (2) to a given temperature by applying (5) aqueous liquid to one side of each of the multifilaments, stretching (7') them 1.0- to 1.5- fold, and subjecting them to liquid jet treatment (in the case of nylon) or relaxation heat treatment at 105 °C or above.

Description

 Technical field of crimped multifilament and its manufacturing method

 The present invention relates to a crimped multifilament having a random form of crimp (hereinafter referred to as a random crimp) and a method for producing the same.

 The crimped multifilament in the present invention includes a tow used for producing a stable fiber.

 More specifically, it is useful for multifilament stable fibers obtained by a method based on high-speed spinning, instead of crimping obtained by mechanical processing such as false twisting. TECHNICAL FIELD The present invention relates to a random crimped filament that can be used for a method and a production method for providing the same at low cost. Background art

 A crimped filament obtained by crimping a thermoplastic polymer fiber by a mechanical processing method such as false twisting or indentation is converted into a multifilament or spun yarn. Widely used.

However, in the production of crimped multifilaments by such mechanical processing, the processing speed is limited to several hundred mZ min. Energy It takes gi and labor. Therefore, the resulting crimped multifilament is extremely costly.

 Japanese Patent Publication No. 64-6282 (corresponding to US Pat. No. 4,542,063) ゃ Japanese Patent Publication No. 64-8086 (corresponding to US Pat. No. 4,415,726) states that high-speed spinning of polyamide polyester increases the spinning speed. At the same time, molecular orientation and crystallization increase, and as-spun multifilaments exhibit sufficient mechanical properties to be comparable to conventional low-speed spun-drawn yarns, and knitted fabrics without drawing It is known that it can be used for However, high-speed spun multifilaments are expected to be inexpensive if subjected to crimping, but since crystals are growing too much, they are randomized even if crimped. It became clear that a large winding could not be applied. Furthermore, high-speed spinning of a multifilament having a denier of 10 to 30 deniers required for power output using a raw material such as boriamid having an extremely high crystallization rate as a dog. When manufactured, spherulites were formed in the spun single fibrils, and the filaments were found to be markedly devitrified, lost smoothness, and impaired commercial value. This spherulite is generated by combining a method of spinning in a non-aqueous system disclosed in JP-A-58-36213 and a method of retaining an inorganic metal salt disclosed in JP-A-63-99324. Could not be resolved.

As one method for obtaining a crimped multifilament by high-speed spinning, Japanese Patent Application Laid-Open No. 55-107511, Journal of Arrowhead Society Vol.37, No.4 (1981), T-135 to T-142, By performing partial cooling with low-temperature air during the high-speed spinning process of 8,000 m / min or more of polyester. Thus, a method for obtaining a crimped multifilament is shown. The multifilament obtained in the publication has a structure in which the constituent single fibers have a difference in birefringence in the cross section between the outer layer and the inner layer, and have a distribution eccentric from the center of the fiber axis of the single fiber. It has a structure, and a weak rasin-like crimp is exhibited in the as-spun single fiber. However, the filaments obtained by the publication also have excessively grown crystals, as is clear from the crystal structure determined by the wide-angle X-ray diffraction method. Therefore, a random crimp could not be imparted by the subsequent heat treatment, and the crimp remained a spiral crimp, and a practical crimped multifilament could not be obtained. Further, USP 4,238,439 to speed spinning polyamide mi de as a raw material, even with the method according to (iSP 4, 619, 803, the results obtained are similar to a Atsuako ₀

 On the other hand, USP 4,038,357, USP 4,301,102 and JP-A-62-23816 disclose that an aqueous liquid is applied to a multifilament before solidification in a spinning process. A method of Spin Texturizing to obtain a crimped yarn is shown.

 The occurrence of these crimps causes a substantially eccentric birefringence distribution to obtain a helical crimped multifilament.

The above-mentioned US Pat. Nos. 4,038,357 and 4,301,102 relate to polyamides, but the spinning take-off speed is disclosed only up to 2,300 m / min. Further, the eccentric birefringence distribution is caused by asymmetric cooling by a crossed air flow, and is essentially the same as that of US Pat. No. 4,238,439. here The application of the aqueous liquid in the above is merely performed for the purpose of sufficiently immersing the single fiber. Furthermore, the crimped multifilament obtained in the publication is a racen crimp that is inverted after fluid injection processing is performed, so that the crimped multifilament has low crimp elasticity and is used for force sheets and the like. However, sufficient bulkiness cannot be obtained.

Japanese Patent Application Laid-Open No. 62-23816 relates to polyester, which is a method of cooling the vicinity of a point at which the discharge filament has been thinned at a spinning speed of δ, ΟΟΟηη minutes or more with a liquid. How the publication also because of the high speed spinning peculiar significantly crystals are One Do and growth structure and, therefore _c spiral crimp is made to that manifested, even strainer facilities the subsequent heat treatment, La No crimp can be applied.

 As described above, the production of known crimped multifilaments based on high-speed spinning at a spinning speed of about 4,000 m / min or more is all helical crimping with low bulkiness and low rebound. In addition, a crimped multi-filament having a random shape sufficient for practical use is obtained even if crimping such as fluid jetting is hindered by excessive growth of crystals. In the case of helical crimps, if crimped multifilaments are used for the carpet yarns, the crimps can be easily extended in the tufting process. Insufficient coverage of the pet.

Also, when a stable fiber is manufactured by cutting a crimped multi-filament (toe in this case) into a spun yarn, card drop occurs frequently during card processing, and processability is increased. Failure to do so could result in significant damage. Therefore, there has been a strong demand for a random crimped multifilament having excellent crimp fastness and a method for producing the multifilament at high speed and at low cost. Disclosure of the invention

 A first object of the present invention is to provide a crimped thermoplastic synthetic fiber multi-layer having a random crimp having a firm crimp.

 A second object of the present invention is to provide a polyamide crimped multifilament having a random crimp having a firm crimp and having surface smoothness.

 A third object of the present invention is to provide a ballistic crimped multifilament provided with a random crimp having a robust crimp.

 A fourth object of the present invention is to provide a polyester stable fiber having a random crimp having a strong crimp.

 A fifth object of the present invention is to provide a method for producing a multilayer crimped multifilament having a random crimp having a firm crimp and having surface smoothness. is there.

 A sixth object of the present invention is to provide a method for producing a polyester crimped filament having a robust crimp.

The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems. As a result, the filament spun at high speed under special cooling conditions suppresses the growth of crystals by itself. Heat treatment It has been found that a highly grown crystal structure equivalent to that of a normal high-speed spinning filament of 4,000 m / min or more can be developed.

 This fact makes it possible for the first time to form a crimp in a random shape into filaments spun at a high speed of 4,000 m / min or more.

 Moreover, the obtained random crimped filament has a surface smoothness, a highly grown crystal structure unique to high-speed spinning filaments, and a unique birefringence distribution. Because of this, they have found that they have excellent crimp fastness, and have completed the present invention.

 The first object of the present invention is that the outer layer portion has a larger birefringence than the birefringence measured at the center of the monofilament constituting the thermoplastic polymer. This is achieved by a crimped multifilament having a distribution where the position showing the minimum birefringence is eccentric from the center of the fiber axis and having a random crimp of 10 kenoin or more. .

 A second object of the present invention is that the birefringence of the outer layer portion is larger than the birefringence index measured at the center of the monofilament constituting the boriamid, and the minimum is The position showing the birefringence has a distribution in which it is eccentric from the center of the fiber axis, the crystal growth degree determined by wide-angle X-ray diffraction is 0.2 or more, and the This is achieved by a boriamid crimped multifilament having a random crimp.

A third object of the present invention is to provide a method comprising: Distribution where the birefringence of the outer layer is larger than the refractive index measured at the center of the single fiber, and the position where the minimum birefringence is present is eccentric from the center of the fiber. The degree of crystal growth obtained by wide-angle X-ray diffraction is 0.4 or more, and is achieved by a polyester crimped multifilament having a random crimp of 10 or more / in.

 The fourth object of the present invention is that the birefringence of the outer layer portion is larger than the birefringence index measured at the center of the monofilament, which is composed of polyester, and has a minimum value. The position showing the birefringence has a distribution in which it is eccentric from the center of the fiber axis, and the degree of crystal growth determined by wide-angle X-ray diffraction is 0 or more, and 10 or more Achieved by polyester stable fiber with random crimp.

 A fifth object of the present invention is to produce a random crimped multifilament by melt-spinning a polyamide, a single fiber constituting a multifilament extruded from a spout. Apply an aqueous liquid from one side and cool asymmetrically until the temperature is reduced to 100 ° C, take it at 4000 m / min or more, stretch it by 1.0 to 1.5 times, This is achieved by a method for manufacturing a crimped multifilament, which is characterized by performing liquid jet processing at a temperature of 150 or more.

A sixth object of the present invention is to produce a random crimped multifilament by melt-spinning a polyester, and to determine the temperature of a single fiber constituting the multifilament extruded from a spout. Apply an aqueous liquid from one side until the A symmetrically cooled, crimped multifilament characterized by drawing at a rate of 5000 m / min or more, stretching at 1.0 to 1.5 times, and then performing a relaxation heat treatment at a temperature of 150 ° C or more This is achieved by the manufacturing method described above. BRIEF DESCRIPTION OF THE FIGURES

 FIG. 1A is a photograph showing random crimping of the crimped multifilament of the present invention. FIG. 1B is a diagram schematically showing a random crimp, and FIG. 2 is a diagram schematically showing a lacy-like crimp. <FIGS. 3A to 3C are simple drawings of the present invention. FIG. 3 is a pattern diagram of a transmission quantitative interference microscope photograph showing various modes of a birefringence distribution of a fiber. FIG. 4A is a photograph of a cross section of a dyed single fiber of the present invention, and FIG. 4B is a photograph of a cross section of a dyed single arrowhead of a conventional crimped filament.

 5A and 5B are electron micrographs showing the smoothness of a single arrowhead fiber surface, FIG. 5A is a photograph of a crimped filament according to the present invention, and FIG. This is a photograph of a conventional crimped filament.

 6 and 7 are schematic front views each showing an example of a spinning machine and a processing machine for implementing the present invention.

 FIGS. 8-9 and FIGS. 9B and 9B are schematic front views each showing an example of a water application device used for asymmetric cooling according to the present invention.

10 and 11 show examples of X-ray diffraction intensity curves in the crystal growth measurement of the crimped multifilament of the present invention, respectively. FIG.

 FIG. 12 is a view showing a crimp expression rate of a crimped multifilament. BEST MODE FOR CARRYING OUT THE INVENTION

 A fundamental feature of the crimped multifilament of the present invention is that the constituent single fibers have a random crimp. The term “random crimp” as used in the present invention refers to a crimp that is three-dimensional, non-rotating, and has irregular crimps. It is clearly distinguished from swirling crimps by false twisting and helical crimps obtained by composite spinning or mechanical scraping.

 FIG. 1A shows a photograph of the random crimp of the present invention. FIG. 1B is a schematic diagram of FIG. 1A. FIG. 2 schematically shows a spiral crimp not according to the present invention in comparison with FIG. 1B.

 A random configuration is a requirement to have sufficient resilience to tensile or compressive loads. When used for carpets and the like, the crimps in the form of Lasine are inferior in compressibility and have poor stiffness, which is not suitable.

 In the present invention, the number of crimps is required to be 10 / in or more. If it is less than this, the compressibility cannot be satisfied for applications such as carpet.

Also, when a crimped multifilament is cut into a stable fiber, card drop occurs frequently in the carding process and process performance is impaired. In a crimped filament for a carpet, the crimp elongation ratio is required to be about 10% or more together with the number of crimps. However, in the crimped filament of the present invention, the number of crimps is Is 10 or more / in, the crimp elongation becomes about 10% or more, and the above requirements are satisfied.

 The preferred number of crimps is 15 kenoin or more, and the crimp elongation is preferably about 20% to 50%.

 In the crimped multifilament of the present invention, the birefringence of the outer layer is larger than the birefringence measured at the center of the constituting single fiber, and the birefringence is the minimum. It has a unique birefringence index distribution in which the position indicating the index exists eccentrically from the center of the fiber axis.

 The distribution of birefringence and the eccentricity are observed by a method described later using a transmission interference microscope when the cross section of the single fiber is circular. The birefringence distribution is measured from U-shaped or V-shaped interference fringes as shown in Figs. 3A and 3B. If the birefringence distribution is eccentric from the center of the fiber, the lowest point LP (Lower Point) of the interference fringe as shown in Fig. 3C is the center axis of the filament (X-X ).

 When the cross-sectional shape of a single fiber is irregular, it is impossible to observe the birefringence with a transmission interference microscope as in the case of a circular cross-section. <In this case, the Journal of the Japan Society of Arrowhead Machinery Vol. 33, Να11 (1980) As illustrated on pages 551 to 55, the cross section of a dyed single arrowhead is measured using an optical microscope to measure the penetration distance of the dye from the surface of the single arrowhead. The presence or absence of a wick is measured.

In addition, in practice, a circular cross-section is By spinning, it is also possible to infer the birefringence distribution of the irregular-section fiber from the observation of the circular section fiber with a transmission interference microscope. FIG. 4A is a photograph of a cross section of a single fiber of the present invention stained by a method described later. It can be seen that the dye penetration distance is largely eccentric with respect to the geometric center of the cross section.

 FIG. 4B is a cross-sectional photograph of a dyed single fiber of a conventional crimped filament.

In the present invention, the definition of eccentricity when the cross-sectional shape of a single fiber is asymmetric and complicated is based on the geometric center of gravity of the cross-sectional shape. Action with crimped Maruchifui lame down bets consuming special birefringence distribution of the present invention are possible to exhibit superior robustness crimped ₀

 The thermoplastic polymer referred to in the present invention includes polyamides such as Nylon 66, Nylon 6, Nylon 12, and Nylon 46, polyethylene terephthalate, polybutylene terephthalate, and the like. In addition to polyesters such as polyethylene isophthalate, it refers to polymers capable of forming fibers, such as polypropylene and polyethylene. If necessary, additives such as an antistatic agent, an anti-glare agent, and a flame retardant may be provided.

 In general, the present invention provides particularly excellent effects when applied to polyamide polyester.

In the case of polyamide, when the cross-section of a single arrowhead is circular, the birefringence is the outer layer and inner layer (minimum point). ^{5 X 1 0- 3 ~45 X 1} 0- 3 has a difference, and it is desirable to have a eccentric distribution from the center of the fiber axis. If off I lame down bets sectional birefringence difference 5 (delta eta) is less than 5 X 10- ³ is insufficient crimp number, can not sufficiently reach made object of the present invention.

 In the present invention, in the case of polyamide, the degree of crystal growth determined by wide-angle X-ray diffraction is 0.2 or more. When the polyamide is polyhexamethylene dipamide, the crystal integrity coefficient is desirably 70% or more.

 The crystal growth degree and the crystal perfection coefficient are measured by wide-angle X-ray diffraction according to the method described later. The crystal growth degree is an index indicating the degree of crystal growth, and the closer to 1, it means that the crystal is growing. This value is 0.15 or less in the case where the polyamide is subjected to ordinary low-speed spinning-stretching, which indicates that the crimped multifilament force of the present invention has extremely grown crystals. The preferred degree of crystal growth is 0.25 or more.

 The crystal perfection coefficient is an index mainly indicating the size of the constituent crystals, and the closer to 100%, the higher the perfection. Since this value is 40 to 60% in the ordinary low-speed spinning-drawn polyamide multifilament, it can be seen that the crimped multifilament of the present invention has extremely high crystal integrity. The crimped multifilament made of the polyimide of the present invention has no spherulites at all, and has good filament surface smoothness.

In the case of a polyamide spun at high speed, spherulites are generated on the surface of the spun single fiber due to the particularly high crystallization speed, and the smoothness of the surface is impaired. Devitrification, staining In this case, it is not possible to obtain clear color development and high-grade gloss. In the crimped multifilament of the present invention, such spherulites are not observed at all and have excellent transparency. This feature becomes even more pronounced when the single yarn denier is 10 denier or more.

 The smoothness of the filament surface can be easily observed with a normal electron microscope at a magnification of about 500 to about 2000.

 FIG. 5 shows an electron micrograph of a nylon 66 crimped single fiber. FIG. 5A is a crimped filament of the present invention, in which no spherulite is present. FIG. 5B shows a conventional crimped filament, in which the presence of spherulites can be confirmed.

 The case where the thermoplastic polymer is used for a polyester represented by polyethylene terephthalate or polybutylene terephthalate will be described.

When the cross-sectional shape of the monofilament of a circular, de birefringence outer and inner layer portion (minimum ^{point), 20 X l 0- 3 ~} 100 X 10 - has a difference of ^3, and the center of the fiber axis It is desirable to have a distribution that is eccentric from the center.

If the birefringence difference is 30 × 10 ⁻³ or more, more excellent crimps will appear.

Moreover, when the degree of crystal growth determined by wide-angle X-ray diffraction is 0.4 or more, the crimp fastness becomes excellent. The degree of crystal growth of the polyester is a force measured by the method described below. The closer the value is to 1, the more the crystal grows. Since this value is 0.3 or less in the ordinary low-speed spinning and drawing of polyester, the crimped filament of the present invention is extremely bound. It can be seen that crystals are growing. The preferred degree of crystal growth is 0.5 or more.

 As described above, the crimped multifilament of the present invention

(1) Eccentric birefringence distribution (2) Random crimp (3) Satisfaction of highly grown crystal structure at the same time.

 The crimped multifilament of the present invention exhibits excellent bulkiness and crimp fastness based on such a structure.

 Crimp fastness is indicated by the antagonism of the tensile stress applied to the fiber and the crimp restoring force under load.

 For example, when a crimped multi-filament is used in a unit of force in a state of bulky continuous filament (Blucked Continuous i 1 aments 5 B * F), a twisting process is performed.ゃ Even if an excessive elongation stress is applied in the tufting process, the crimp hardly decreases, showing excellent bulkiness.

 It also has an excellent effect on crimp restoring force.

In general, when B.F is used as a force piece by tufting, the crimped multifilaments are densely packed with each other, so that the amount of the cargo equivalent to about 0.2 mZg is obtained. I am being restrained. On the other hand, B.F is handled in a form wound on a package, and is tufted while unwinding from this package in a tufting process. At this time, B.F. has creased in the package, and the crimp has been greatly reduced. Therefore, when the crimp restoring force is small, the crimp does not sufficiently recover due to the restraint after the tuft, and the performance of the force kit is significantly reduced. In the crimped multifilament of the present invention, even if crimping is greatly reduced by creep, crimping is again exhibited by boiling water treatment or the like. Even under constraint, it has a crimp restoring force that far surpasses conventional B.C.F.

 Also, when the crimped multifilament (in this case, toe) of the present invention is cut into a stable fiber and subjected to a carding process, a good card without crimp extension is obtained. Has workability.

 The cross-sectional shape of the crimped multifilament of the present invention is not limited to a circular shape, but also includes irregularly-shaped cross-section yarns such as trilobal and square, and hollow fibers. The single yarn denier is not particularly limited as long as it is not more than about 50 denier.

 In addition, confounding such as interlacing may be added to the crimped multi-filament as needed.

 Hereinafter, a method for producing a crimped multifilament of the present invention will be described.

 FIG. 6 shows an example of a spinning heat treatment apparatus for performing the production method of the present invention.

 The filament 13 extruded from the spinneret 2 attached to the spin head 1 is cooled by the cooling chamber 4. In an area where the filament maintains a high temperature, the aqueous liquid is applied from one side by the aqueous liquid applying device 5a (in this case, the constituent monofilaments are separated from each other), and asymmetric cooling is performed. Is done.

After focusing and refueling by refueling nozzle 6, it is taken off by high-speed take-off port 7. Filament 13 is then After being relaxed and heat-treated by a treatment device 8 (in this case, a fluid jet processing nozzle) to give a random crimped form, confounding is given by a cooling drum 9 and a confounding nozzle 10, and the package is passed through a tension adjusting roll 11. Wound on 12.

 FIG. 6 is a schematic view in the case where a stretching device is added to the device of FIG. 5, and the filament 13 is stretched between the take-up roll 7 and the stretching port 7 ′.

 FIGS. 8 and 9 are schematic views of an apparatus for performing water application according to the present invention, and FIG. 8A is a plan view of a separation nozzle that separates single fibers from each other and applies an aqueous liquid. . FIG. 8B is a cross-sectional view taken along line EE ′ of FIG. 8A. Fig. 9A is an example of a "roll type" in which the single fibers are applied in one plane while the single fibers are arranged in a plane, and Fig. 9B shows water from one side in a state where the single fibers are bundled. FIG. 3 is a diagram of a “nozzle method” for applying a liquid.

 In the production method of the present invention, the multifilament extruded from the spinneret is asymmetrically cooled by applying an aqueous liquid from one side in an area until the temperature of the constituent single fiber is cooled to 100 ° C. It is necessary to spin at a spinning speed of 4, OOO m Z minutes or more.

 If the spinning speed is less than 4,000 m / min, the difference in the birefringence (Δn) between the outer layer and the inner layer of the filament cross section, which is the object of the present invention, does not increase, and the spinning speed due to subsequent stretching etc. The birefringence index difference (Δn) once generated disappears. Furthermore, in the filament after the heat treatment, the crystal growth is insufficient, and the robustness of the obtained crimped multifilament is insufficient.

The spinning speed of the present invention is from 5,000 m / min to 8,000 m / min. The object of the present invention is effectively achieved. Even if the spinning speed is about 8,000 m / min or more, it is possible to obtain the multifilament of the present invention by applying an extremely large amount of aqueous liquid, etc. It is necessary to apply a large amount of aqueous liquid to adjust the growth degree, which causes problems such as scattering of the aqueous liquid.

 The most preferred spinning speed is from 5,500 to 7,500 mZ, based on the mechanical properties and structure formation of the filament.

In the case of polyesters, the appearance of a non-uniform cross-section structure reported in the Journal of the Textile Society of Japan, Vol. 37, No. 4 (198DT-135 to T-142) requires a spinning speed of about δ, ΟΟΟπιΖ minutes or more, the Mi-de, as shown in Japanese Patent Tokuoyake Akira 64- 6283, when compared to not express at most about 6 X 10- ³ at 10, 000 m Zeta fraction are different from one rather large.

 Within the speed range of the present invention, there is no problem such as remarkable increase in spinning tension and yarn breakage during spinning, and the operation can be stably and industrially performed.

 The present invention has a major feature in that asymmetric liquid is applied by applying an aqueous solution from one side before the temperature of the single fiber constituting the multifilament extruded from the spinneret is cooled to 100'C. Have. By performing asymmetric cooling with an aqueous liquid at a high temperature where the temperature of a single arrowhead is high, an eccentric birefringence distribution characteristic of the filament of the present invention is developed. If the filament temperature at the time of applying the aqueous liquid is less than 100'C, the object of the present invention will not be achieved no matter how the conditions such as the amount of applied water are selected.

Higher filament temperature when applying aqueous liquid The birefringence difference (Δn) increases as the value increases, but if it exceeds about 250'C, problems such as thread breakage during application of the aqueous liquid may occur. Therefore, the preferred filament temperature is between 250 and 100.

 Generally, in melt spinning, the polymer is extruded from the spinneret at 260'C to 320 • C.

 In the method of the present invention, the cooling of the filament until the application of the aqueous liquid is achieved by cooling with cooling air generally employed in melt spinning. The position from the spinning surface where the filament temperature is 100 or more required to carry out the present invention differs depending on the spinning speed and the denier of the filament. If it is more than 4,000 m / min and 1 to 5 denier, which is usually used for clothing, it is within about 100 cm below the spout. Therefore, the application of the aqueous liquid of the present invention is performed during this time.

 In the case of polyamide, it is necessary that the temperature of the single fiber at the time of applying the aqueous liquid is 100 ° C. or higher. Most preferably, it is at least 130 • C.

For boria mid, spinning used for carpets uses about 10 to 30 denier for single fiber denier. In this case, the application of the aqueous liquid is within about 300 η below the spinneret. In the case of polyamide, unlike polyester, in high-speed spinning without water, rapid thinning deformation of the yarn diameter is generally not observed during the spinning process. In the spinning with water application according to the present invention, clear thinning deformation was confirmed at the water application point. That is, applying an aqueous liquid to a single fiber at a high temperature imposes a thinning deformation point. The present invention for the first time has revealed that it is expressed in a specific manner.

 The effect of the application of the aqueous liquid makes it possible for the first time to increase the birefringence index difference 5 (Δn) and achieve an eccentric structure, which is the object of the present invention.

 In the case of polyester, it is necessary to apply an aqueous liquid at a single fiber temperature of 150'C or higher. In the case of polyester, when the spinning speed exceeds about 6,000 m / min, it is known that a sharp reduction in the yarn diameter is observed during the spinning process. , No.ll (1982) P.499-P.507). The application position of the aqueous liquid of the present invention is, based on this thinning deformation position (neck point), about 5 on or more above the deformation position, more preferably about 10 cm or more above. You. For example, a multifilament having a denier of 3 monofilaments is spun at a spinning speed of 6,000 m / min, and the thinning deformation position is 70 cm below the spinning surface (single fiber temperature is about 100'C). In this case, the aqueous liquid is applied within 65 cm below the spinning surface (single fiber temperature of 150 ° C or more), preferably within 60αη (single fiber temperature of 200 • C or more).

In high-speed spinning of polyester, oriented crystallization occurs very easily, so the microstructure of single fibers varies greatly depending on the difference of the application position (yarn temperature) of the aqueous liquid by only 1 to 2 cm. Therefore, it is necessary to determine the position of the assignment strictly. When an aqueous liquid is applied at a single fiber temperature of less than 150'C, the birefringence index difference 5 (A n) becomes insufficient, and the obtained multifilament has a weak actual crimp. Crimped multi-filament and Become. However, even if this crimped multifilament is subjected to a subsequent relaxation heat treatment, the crimp no longer increases and the object of the present invention cannot be achieved.

 As the aqueous liquid used for cooling the filament in the present invention, water, an ordinary oil agent for spinning, and the like can be applied. For convenience, water is used. Further, the temperature of the aqueous liquid is preferably as low as possible, but the present invention can be attained even if the temperature is not cooled to room temperature or lower.

 The method for applying the aqueous liquid is a method in which the single fibers are separated from each other, a method in which the single fibers are arranged in a plane, or a method in which several to a dozen or more single fibers are bundled. The method is adopted.

 The method in which the single fibers are separated from each other is preferably applied to spinning with a single fiber denier of about 10 denier or more in the medium. In the present invention, this method is referred to as a “separated nozzle method”.

 Figure 8A shows an example of the “separated nozzle method”. In this method, the aqueous liquid is independently applied to each single fiber by the nozzle group 5a separated from each other.

 FIG. 8B is a cross-sectional view taken along the line EE ′ of FIG. 8A to further clarify the state of application of the aqueous liquid to the single fiber. The tip of the nozzle has a sharp pointed shape, which reduces the resistance due to contact with a single arrowhead, and is suitable for asymmetrically cooling a single fiber.

The method of flattening the single fibers is preferable when the polyester is applied to spinning with a single fiber denier of about 10 denier or less. No. This method is referred to as "roll method" in the present invention.

 Figure 9A shows an example of the “roll method”. Even with the roll method, it is preferable that the resistance due to contact with the filament be small. For this purpose, the roll diameter is selected from 10 to 50 mm.

 A method of bundling several to several tens of single fibers is preferably applied to spinning of a single fiber denier of 1 to 5 deniers. This method is referred to as "nozzle method" in the present invention. Figure 9B shows an example of the “nozzle method”.

 As long as the object of the present invention is not impaired, a water dispenser of another shape can be employed.

 The amount of the aqueous liquid applied to the filament is indicated by a weight percentage with respect to the filament.

 In the present invention, by applying an aqueous liquid to a high-temperature filament, the filament is asymmetrically cooled and the crystal growth is suppressed. .

 In the present invention, the larger the amount of applied water, the more the degree of crystal growth can be reduced even at the same filament temperature. The object of the present invention is achieved when the applied water amount is about 10% by weight or more. When the water volume exceeds 500% by weight, it is necessary to prevent the excess aqueous solution from scattering.

 The preferred amount of applied water is 20 to 300 weight percent.

 In the “separated nozzle method” and “roll method”, the applied water amount is 20 to 50 weight percent.

As in the “nozzle method,” multiple filaments are focused. In the case of applying by water, since the filament temperature is as high as 100'C or higher, troubles such as breakage of yarns and yarn breakage easily occur. ₍ However, in the present invention, the applied water amount is about 50% by weight. By setting it to be greater than or equal to the percentage, the above-mentioned fusion phenomenon is completely solved, and extremely stable spinning is achieved.

 Specifically, when the aqueous liquid is applied by the “nozzle method” as shown in Fig. 9B, even if the number of filaments is 3 to 20, the single yarn does not adhere, and the spinning is performed. Stability is also good.

 In the present invention, the combination of the high-speed spinning of 4000 mZ or more and the application of the aqueous liquid from one side to a single fiber achieves the asymmetric cooling as the object of the present invention. That is, the asymmetric cooling by the aqueous liquid causes the single fiber to run at high speed in the contact between the aqueous liquid supplied from one side and the single arrowhead, thereby destroying the liquid film (surface tension) of the aqueous liquid. This is achieved by applying the aqueous liquid to only one side of the single fiber.

 This fact can be easily confirmed by observing the contact portion between the single fiber and the aqueous liquid.

 If the spinning speed is less than 4,000 m / min, even if the aqueous liquid is applied from one side, the liquid film of the aqueous liquid will not break, and the aqueous liquid will be immersed so as to cover the entire circumference of the single fiber. Asymmetric cooling is difficult to achieve.

In the present invention, after the asymmetric cooling, it is necessary to perform elongation by 1.0 to 1.5 times and then heat-treat at 150'C or more. The spinning speed is about 4,000 mZ min. In the case of about 5,000 mZ, stretching up to 1.5 times or less improves mechanical properties Above.

 When the spinning speed is about 5,000 m / min or more, the crimped filament has mechanical properties suitable for practical use without stretching. For the purpose of obtaining a simple process and high productivity, it is most preferable to spin at a spinning speed of about 5,000 mZ min or more and to make a crimped multifilament as it is undrawn.

 When the spinning speed is about 4,000 m / min to about 5,000 m / min.- When the draw ratio exceeds 1.5, the birefringence index distribution disappears, and the object of the present invention is not achieved. .

 The stretching is preferably performed by heating at a temperature equal to or higher than the glass transition temperature of the polymer.

 The heat treatment requires at least about 150 and must be performed in a substantially relaxed manner.

 In the present invention, the multifilament before the heat treatment has only low crystal growth, but is characterized in that the crystal grows large by such heat treatment. This is a surprising and unexpected change. The reason for this is not clear, but it is speculated that the high crystal growth specific to high-speed spinning is latent in the frozen state by the application of water, and this has been revealed by the high-temperature heat treatment.

Fig. 10 and Fig. 11 schematically show the growth of crystals by heat treatment. FIG. 10 shows an example in which the polymer is nylon 66, (I) in FIG. 10 shows the wide-angle X-ray diffraction pattern of the filament before the heat treatment, and (H) in FIG. ) Is a wide-angle X-ray diffraction pattern after heat treatment of this filament. Figure 11 shows that the polymer This is an example of ethylene terephthalate. Similarly, (I) is a crimped multi-filament before heat treatment, and (Π) is a crimped multi-filament after heat treatment. The broken line in (m) is a conventional low-speed spun-drawn yarn.

 Such a change in the crystal structure was first discovered by the present invention. This discovery has made it possible for the first time to obtain random crimped multifilaments, whereas previously, only high speed spun multifilaments could be obtained.

 When the heat treatment temperature is lower than about 150 ° C., the crystals cannot be sufficiently grown, and the random crimped multifilament excellent in robustness, which is the object of the present invention, cannot be obtained. Preferably, the heat treatment temperature is about 180 ° C or higher.

 Preferably, the heat treatment is carried out under a substantial relaxation, preferably under a relaxation of about 5% or more, to achieve the object of the present invention. If the operation is performed under substantially tension, a reduction in the number of crimps ゃ a decrease in the birefringence.

 Such a relaxation heat treatment apparatus is, for example, an injection processing apparatus using a fluid nozzle disclosed in JP-A-59-71440 or an injection processing apparatus using a net drum disclosed in JP-B-58-30423. The method is appropriately selected from methods such as the above.

 High-temperature air and saturated or unsaturated steam are generally used as the heating fluid for the blasting.

When the crimped multifilament is polyamide and is used as B.C.F, the injection processing method using fluid nozzle is adopted. In this case, the fiber structure formed by asymmetric cooling And fluid Combination of blasting gives a random crimped multifilament with excellent robustness.

 When the crimped multifilament is a polyester and is used as a stepper fiber, the fiber is deposited on a moving net, for example, without being necessarily sprayed, and heated. It is also possible to perform relaxation heat treatment through a zone.

 In the case of polyester, it is non-crimped before the relaxation heat treatment, but can be sufficiently crimped in a random shape by the relaxation heat treatment on the net as described above, not by injection processing. It becomes a multifilament. This is a surprising thing, and is a big difference compared to the fact that only a racinous crimped multifilament was obtained in JP-A-62-23816.

 According to the method of the present invention, in the case of a crimped multifilament for a carpet, the discharge amount per hole at the time of spinning can be 7 to 25 g / min. Compared to the conventional discharge rate of 3-6 g per hole in this field, productivity is about 2-3 times higher than that of conventional products.

 In order to effectively carry out the production method of the present invention, high-speed spinning-one heat treatment or high-speed spinning-drawing-heat treatment is continuously performed. The most effective is high-speed spinning-crimping, in which heat treatment is performed in an undrawn state after high-speed spinning.

The process itself of continuously producing a crimped filament by spinning, drawing and crimping is disclosed in, for example, US Pat. No. 3,854,177. However, the maximum speed of the known continuous process is At most 4,000 m / min. In contrast, according to the present invention, for the first time, a continuous process at 4,000 m or more was possible. <Examples of the present invention will be described below along with comparative examples. The method for measuring the properties of the crimped filament of the present invention is described below.

 (A) Filament temperature

 The single yarn temperature was measured in a non-contact manner along the spinning line using a scanning infrared thermometer.

 (B) Strong elongation

 It was measured at an initial length of 20 cnu at a pulling speed of 20 cm Z minute using a TENS I LON UTM-II-20 type tensile tester manufactured by Toyo Ball Douin Company.

 (C) Birefringence distribution and eccentricity

 When the cross section of a single fiber is circular, the distribution of birefringence and eccentricity are measured using a transmission quantitative interference microscope. If the cross section of a single arrowhead is irregular, the single fiber can be dyed and the distribution of birefringence and eccentricity can be observed using an optical microscope.

 (When the cross section of single fiber is circular)

 It is measured by the interference fringe method using a transmission quantitative interference microscope (interferometer, Interferco manufactured by Carl Zeiss Jena). Uses a green ray with a wavelength of 5 9π. 封入, has a refractive index (与 え る) that shifts interference fringes in the range of 0.2 to 2 wavelengths, and is an inert material for textiles. Soak the fiber in it. A photograph of the interference fringe pattern formed when the fiber axis is perpendicular to the optical axis of the interference microscope and the interference fringes is taken and analyzed at a magnification of about 1500 times.

Details of the breaking were in accordance with the method of the working example of Japanese Patent Publication No. 64-8686. When the filament is circular, V-shaped or U-shaped interference fringes are observed as shown in FIG. FIG. 3C is a schematic diagram showing the eccentric distribution of the birefringence of the crimped filament of the present invention. The difference between the outer layer and the inner layer in the birefringent filament is calculated from Fig. 3A obtained by rotating the filament in Fig. 3C by 90 ° about the fiber axis XX. Minode was.

 Here, the outer layer indicates a position of 0.8 R when the radius R of the filament is from the filament center in FIG. 3A and is represented by An 0.8. The inner layer indicates the minimum point L.P of the birefringence,

Δη. Is represented by The birefringence index difference (Δη) is calculated by the following equation.

Birefringence index difference <5 (Δη) = Δη. · ₈ — Δη. It is.

 (When the cross-section of a single arrowhead is irregular)

 Dyeing was performed under the following conditions in a state where the single fibers did not overlap each other during the dyeing.

◎ Polyamide filament staining

 Sample weight: 0.5 g

 Dye: Kayartis Supra Gray VGN 300% of

 Bath ratio: 1: 500 Dyeing temperature: 98'C

 Staining time: 30 minutes

◎ Polyester filament dyeing

 Samburu weight: 0.5 g

 Dye: Resolin Blue FBL 300% owf

 Bath ratio: 1: 500 Dyeing temperature: 85'C

Staining time: 90 minutes An optical micrograph of the cross section of the dyed single fiber was taken. When the birefringence distribution and its eccentricity exist in the single fiber, the permeation distance of the dye from the surface of the single fiber is not uniform with respect to the center of the single fiber.

 (D) Crystal growth IWR

 Determined by wide-angle X-ray diffraction.

 Measurements were made by Rigaku Denki's X-ray generator (BU-200PL), arrowhead sample analyzer (FS-3), goniometer (SG-9), and a scintillation counter for the counter tube and a counting section. Is measured by a CuX-ray (λ = 1.5418 mm) monochromatized by a Nikel filter using a wave height analyzer. The X-ray generator operates at 30kV, 80mA.

 At this time, scanning speed 4 No., chart speed 10 麵 Z, time constant 1 second, collimator 2 mm, receiving slit vertical width 1.9 驄, width 3.5 mm.

 (In the case of a medium)

 In the case where the polyamide is polyhexamethylene dipamide, it generally has two major reflections on the equator, as shown in FIG.

 From the low angle side, it is the reflection of the (100) plane and {(010) + (110)} plane of the crystal. The strength curve between 20 = 7 ° and 35 ° is connected by a straight line and used as the baseline. A perpendicular is drawn between each beak and the baseline, and this perpendicular is used as the diffraction intensity.

 The crystallinity (IWR) of the polyamide is given by the following equation.

 2 H,

 I W R = 1

nz + H 3 Is H, and in here is the minimum value of the intensity between the {(010) ten (110)} plane reflection (100) surface reflection, the maximum strength of the the H ₂ (100) plane reflection, H ₃ Is the maximum intensity of the {(010) + (110)} surface reflection.

 The closer the value of IWR is to 1, the higher the crystal growth.

 When the polyamide is polycaproamide, the degree of crystal growth is defined as the growth of r-type crystals.

 Polycaproamide generally takes two crystal forms, α-type and r-type. It has three major reflections on the equator. These are reflections from the (200) plane of the α-type crystal, the (020) plane of the r-type crystal, and the {(202) + (002)} plane of the α-type crystal from the low angle side.

 Here, based on the method of RFSTEPANIAK (Journal of Applied Polymer Science. Vol. 23, 1747-1757, 1979), a 7 "crystal Fraction was used as the IWR. The separation of the X-ray diffraction beak Using the RAD-C System Multiple peak separation program manufactured by Denki Co., Ltd.

(For polyester)

 Polyesters generally have three major reflections on the equator, as shown in Figure 11.

The three main reflections drawn in the range of 26 = 17 ° to 26 ° are (100), (010), and (110) from the low angle side. Folding strength curves between 20 = 7 ° and 35 ° are connected by a straight line to form a single line. A perpendicular is drawn between each beak and the baseline, and this perpendicular is used as the diffraction intensity. The Eori intensity at a point corresponding to the valley between (010) and (lio) H, and, when a diffraction intensity of beak of the H ₂ (110), crystal Growth (IWR) is given by

 H!

 I W R = 1

H ₂

 The closer the IWR value is to 1, the higher the crystal growth.

The maximum intensity of surface reflection, H ₃ , is the maximum intensity of {(010) + (110)} surface reflection.

 The closer the value of 1 WR is to 1, the higher the crystal growth.

 (E) Crystal perfection coefficient CPI (Cristal Perfection Index) (for polyamide)

 The crystal perfection (CPI) is measured using the X-ray diffraction intensity curve obtained from the ACS measurement method.

 The method used to determine ASC is based on, for example, the formula of X-ray drawing of macromolecules by LE Alexander, published by Kagaku Dojin, Chapter 7, Scherrer's equation.

2 The line between the diffraction intensity curves between θ = と ° and 35 ° is connected by a wire and used as the baseline. Descend perpendicular to the baseline from the top of the diffraction beak and mark the midpoint between the beak and the baseline. A horizontal line passing through the midpoint is drawn between the diffraction intensity curves. This line intersects the two beaks of the curved beak if the two major reflections are well separated, but only one if the separation is poor. Measure the width of this peak. If it crosses only one shoulder, measure the distance from the intersection to the middle point and double it. If they cross two shoulders, measure the distance between them. These values are converted to radians and used as the line width. Further, this line width is corrected by the following method. β = / B ^¾ -b '

B is the measured line width, b is the broadening constant, and the line width in radians of the beak of the (111) plane reflection of the Si single crystal.

 (Half width). The apparent crystallite size is

 To determine crystal perfection (CPI), the method of Dismore and Statton is used.

 C P I is given by:

 (100) Spacing of surface reflection 100 C P I (%) = C 1) X ()

 {(010) + (110)} The spacing A of the surface reflection where A is 0.189, and the closer Cp I is to 100, the higher the perfection of is.

 (F) Number of crimps

 The number of crimps was measured according to JIS L 1015 using a photograph as shown in FIG. 1A.

 When a crimped filament is left under a high tension for a long period of time while being wound around a package, the apparent number of crimps and crimp elongation may decrease. Is not shown. Therefore, in the present invention, these crimps are measured using 98 crimped filaments.

 X After treating with hot water for 5 minutes, leave in a room at constant temperature and humidity (temperature: 20 ± 2 • C, relative humidity: 65% ± 2%) for 24 hours.

 The number of crimps per inch was measured while a load of 2 Zd was applied to the conditioned crimped filament.

The measurement was performed with 10 points for each sample, taking into account the sample variation. The measurement was performed and the average value was shown.

 (G) Crimp elongation

 Using a measuring machine with a frame circumference of 1.125 m, make a small skein with 20 turns. The skein obtained is heat-treated with boiling water at 98'C for 5 minutes under no load, and then left in a room at constant temperature and humidity (temperature 20 ± 2, relative temperature 65 ± 2%) for 24 hours.

A 2 d load is applied to the conditioned fiber, and after 1 minute, the length is measured. Next, a load of 0.1 g / d was applied to the small skein, and the skein length was measured after 1 minute, and the skein length was £ ₂ . The crimp elongation is expressed by the following equation.

£ _2- £ I

 Crimp elongation = X100 () In addition, the measurement was performed at 10 points for each sample in consideration of the variation of the sample, and the average value was shown.

 (H) Crimp fastness

A 250 mg / d load was applied to the sample for which the crimp elongation was measured for 1 minute to remove the load. Next, the crimp elongation was measured again. When the value of the initial crimp elongation was CE, and the latter crimp elongation was CE ₂ , the crimp fastness was expressed by the following equation.

CE ₂

 Crimp fastness = X100 (%)

 CE,

 If this value is about 60% or more, practically no trouble occurs. 70% or more is preferable.

 (I) Crimp rate with respect to applied load

This is a method for measuring the crimp development force under load. Wrap the filament eight times on a 1.0 m wrap reel and fold it Length shall be 50CBI. Increasing the lead load from 0.1 mg / d and 0.2 mg / d to 0.2 mg / d in increments of 0.2 mg / d, and 60 ° C soil under each load 1 Immerse in the adjusted warm water. After 1 minute from the start of the immersion, the length of recognition was measured 1 cm.

 50— £

 Crimp rate-X100 (%)

 50

 (J) Irregularities on fiber surface

 Using a scanning electron microscope, a photograph of the surface of the fiber was taken at a magnification of 2,000 times by a conventional method and measured.

 (K) Deformity

 The anisotropy of a single fiber cross section with a single opening was determined by the following formula, and the diameter of the circle inscribed in the concave portion of the single curtain section was defined as a, and the diameter of the circle circumscribed in the convex portion was defined as b.

 b

 Deformity---

(L) Carpet performance evaluation

 The performance evaluation of the carpet was evaluated by visual inspection and touch by a skilled person, and measured by the Rug Inspection Association (Foundation) based on JIS L 1021.

 Example 1

Using the spinning and crimping device shown in Fig. 6, the relative viscosity? ? _rel = 2. were spun substantially Nai b plane 66 consisting Kisame Chirenjiajibami de to poly 9 (measured at _{95% H 2 S0 4, 1} % solution) The spigot is a rectangular spigot with a length of 0.70nra, a side width of 0.70nra, a slit width of 0.15, and a trilobal hole drilled equally into three holes, with a spinning hole of 68 holes, at a spinning temperature of 300'C and per hole. The extruded material was extruded at a discharge rate of 9.8 g / min and holes, and was spun and taken off at a speed of 6,000 m / min at 1000 denier.

 At the bottom of the spout, a 20-cm-long non-heated heat-insulating cylinder sealed with the spout surface was provided. It was cooled with a cold air of 0.3 msec from the cold air chamber.

 Next, in the method shown in Fig. 6, the asymmetric cooling is performed by applying water from one side of the filament using a separation nozzle J from the direction facing the chamber cooling air blowing direction. The amount of water applied at this time was about 30 weight percent relative to the filament, then, after refueling with a refueling nozzle, without stretching, at a peripheral speed of 6,000 mZ and temperature. After passing through the 200'C take-off port, it was continuously supplied to the ditto sfer nozzle and was crimped. 5 kg ZciS heated compressed gas was used.

 After cooling, the crimped filament was wound into a cheese-like package at 5,100 m / min. The relaxation rate at this time was about 15%.

 Table 1 shows the properties of the crimped multifilament having a random morphology obtained by changing the position of the water imparting roll from the spinning surface in this processing.

In Table 1, the properties of the multi-filament before crimping were determined by directly winding it from a take-up roll into a cheese-like package. It is a measurement of multifilament.

 Next, we compare the performance of the crimped multifilament in the case of a cartridge. For each of the No. 1 to No. 6 1150 d / 68 mm crimped multi-filaments, each was twisted 40 S, twisted three and then further twisted 40 mm to form a tufted yarn. Prepared. Using this tufted thread, the vial length is 6 mm and the number of stitches is 7.4. 1! I made a loop cart of this. The viscous dye was dyed with a ternary color combination of dyes manufactured by Ciba-Geigy and Tectilon Yellow 4R, Red 2B, Blue 4G.

 The No. 6 crimped multifilament carpet lacked product lineability due to disordered via row and low bulkiness.

 No. 1 to No. 5 crimped multi-quilt cartridges all had piles aligned and good bulkiness. The compression ratio is 41 to 42% for all No.1 to No.5, the compression elasticity is 90 to 91%, and the thickness reduction rate by dynamic load (10,000 times) is 14 to: 15% As a pet, it had sufficient performance.

 In this example, No. 2 crimped multi-filament was compared with Japanese Patent Publication No. 58-30423. For the filaments, the rate of crimping was measured.

 FIG. 12 shows the rate of crimp development with respect to both applied loads. In the figure, curve I is the value of No. 2 in this example, and curve II is a comparative example.

As is clear from FIG. 12, the crimped multifilament of the present invention has an extremely high crimp expression rate as compared with the conventional crimped multifilament. Table 1 Filament m Strength Elongation Irregularity ® Core IWR CPI m Crimped Crimped filament

No. Elongation before temperature

 CO IWR (g / d) (%) Yes (%) (q / in) (%) (%) Unevenness

1 115 205 0.118 1.4 26 1.88 Yes 0.340 74 27 48 80 No

 2 155 188 0.151 1,9 31 1.85 Yes 0.344 75 23 37 82 No

 3 195 170 0.166 2; 7 37 1.85 Yes 0.330 75 20 28 81 No

 4 235 153 0.182 3.2 40 1.83 Yes 0.288 75 15 24 79 No

 5 275 120 0.195 3.4 51 1.82 Yes 0.239 76 11 17 71

 CO

 6 Granted 0.193 2.9 56 1.81 No 0.199 72 7 13 54 Yes

Without

Example 2

 This example was performed for the purpose of measuring the birefringence distribution in a single fiber of the crimped multifilament of Example 1.

 Relative viscosity? ? A crimped multifilament was obtained in the same manner as in Example 1 except that nylon 66 having a re L of 2.6 was used as a hole having a hole diameter of 0.35 mm and spinning was performed at 295.

Table 2 shows the properties of the obtained crimped multifilament.

Table 2

CO

oo

No. 6 is i

Example 3

 In the same manner as in Example 1, monowoven denier 20d nylon 66 was spun at a high speed.

The discharge rate per hole at each spinning speed is 12.0 g Z / hole at 3000 m / min, 12.4 g / min at 4,000 min, 11.1 g / min at 5,000 m / hole, and 6000 m / min. The hole was defined as 13.3 _g hole for mZ, and 15.6 g hole for 7000 m.

 During spinning, water was applied by the “separated nozzle method” 200 η below the spinneret.

 For spinning, a water application roll was installed 200 cm below the spinneret, and the spinning speed was varied from 3,000111 / min to 7,00 () mZ. In this spinning speed range, the filament temperature during water application was about 170 to about 180. Next, after lubricating with a lubrication nozzle, it is supplied to a jet-stuffer device shown in Fig. 6 without winding once, and crimped at a relaxation rate of 12% in the same manner as in Example 1. Processing was performed. In this example, the spinning speed was 3,000 mZ min.

At 4,000 mZ, the roll 7 in FIG. 6 was stretched 1.8 times and 1.4 times, respectively, with 150 rolls. 5,000m / min,

 Stretching was not performed for 6,000 m and 7,000 mZ.

 Table 3 shows the properties of the obtained crimped multifilament. Comparative Examples 6, 7 and 8 in Table 3 show crimped multifilaments obtained without performing asymmetric cooling with an aqueous liquid. In the table, No. 2 to No. 5 each had an eccentric birefringence index distribution.

The degree of irregularity of the cross section of each single fiber is 1.7 to I.8. It was a mouthful bar.

As is clear from Table 3, the crimped multifilament of the present invention obtained by applying water at a spinning take-off speed of 4,000 m / min or more has good crimp appearance and robustness. Was. In addition, there were no irregularities on the surface of the single fiber, and the transparency was excellent.

Table 3

NO.1, 6, 7, 8 mrn

Example 4

 This example was performed for the purpose of measuring the birefringence distribution in a single fiber of the crimped multifilament of Example 3.

Relative viscosity? ? _A crimped multifilament was obtained in the same manner as in Example 3 except that nylon 66 having _rel = 2.6 was spun at 295'C using a hole having a hole diameter of 0.35 mmø.

Table 4 shows the properties of the obtained crimped multifilament. As is evident from Table 4, the crimped multifilament obtained by watering with Boren OOOmZ or more has good crimping and robustness. Also, there was no irregularity on the filament surface.

Example 5

 For No. 3 in Example 1 and No. 6 in Comparative Example, crimping was performed with the processing temperature of the jet stuffer varied as shown in Table 5. The pressure of the heated compressed gas was fixed at 5 kg / ciS.

 As is clear from Table 5 which shows the properties of the obtained crimped multifilament, when the processing temperature was 150 or more, a good crimped multifilament was obtained.

 Table 5

 Nos. 1 and 6 7 are comparative examples

 Example 6

Using the spinning crimping device shown in Fig. 6, the relative viscosity is 7 ?. = 3. Nye B emissions 6 consisting essentially of poly force blower Mi de 2 (measured in _{95% H 2 S0 4, 1} % solution), at a spinning temperature of 290'C, pore size 0.35删ų, number hole It was extruded from a 68-hole spinneret, and the spinning was performed at a speed of δ, ππιΖ with a crimped multifilament of 1,000 denier. On the other hand, in the same manner, spinning and take-off were performed from a 68-hole spinneret having a trilobal shape with three sides of a slit width of 0.15πιπι. The discharge amount per hole was 9.8 g / hole.

 A heating cylinder with a length of 20 cni and an internal temperature of 200'C was installed below the spinneret, and cooled with a cold air of 0.3 msec from the cold air chamber.

 Next, according to the method shown in Fig. 6, water is applied from one side of the filament at a position 250 cm below the spinneret (filament temperature 155'C) by a "separation nozzle". Cooling was performed. The amount of water supplied at this time was about 20% by weight with respect to the filament. Next, after lubricating with a lubricating nozzle, it is supplied to the jet staff nozzle continuously without stretching through a take-up roll at a peripheral speed of 6,000 mZ and a temperature of 180, and is crimped. Was performed. The processing conditions at this time were a temperature of 230'C, a pressure of 5 kg / dl, and a relaxation rate of 9%. The resulting crimped multifilament had a random form of crimp.

Table 6 shows the properties of the obtained crimped multifilament. 6th eclectic

 Example 7

 Polyethylene phthalate having an intrinsic viscosity of [] = 0.62 was spun with a spinning machine similar to Fig. 6 using a spinneret having a hole diameter of 0.35mmφ and 24 holes. At a spinning temperature of 300 ° C, a heating cylinder with an inner diameter of 12 η and a length of 25 cm was installed under the spinner with a built-in aluminum heater with no gap between the spinning surface and the cylinder. Was adjusted to 250.

The multifilament coming out of the heating cylinder is cooled by a cooling air with a cooling air temperature of 20'C and a wind speed of 0.30 m / sec by a side-blowing type cooling air chamber, and then as shown in Fig. 9A. Asymmetric cooling was achieved by applying room temperature water at 40 weight percent per yarn weight. water The position of asymmetric cooling by the application was set at 50 η below the spinneret. As shown in Table 7, the yarn temperature at this position was about 180'C to 190 in this spinning speed range.

 The multi-filament subjected to asymmetric cooling was wound at a spinning speed of 50 d / 24 f without applying the oil agent and at different spinning speeds as shown in Table 7.

 The position below the spin point at the neck point in the spinning shown in Table 7 is a value measured without water application. The measurement was carried out using a wire measuring instrument manufactured by ZIMMER Co., Ltd., 460 Ω / 2 type, and by visual observation, and the two agreed well.

 When water was applied, it was confirmed that necking occurred 50 cm below the spinneret. It was confirmed that each of the multi-filaments subjected to water application had an eccentric birefringence distribution, but before the heat treatment, the multi-filaments were non-crimped multi-filaments. there were.

 Next, these multifilaments were crimped without stretching using the equipment shown in FIG. The processing conditions at this time were such that the rolls 7 and 7 'were both unheated and had a constant peripheral speed of 3,000 m. The jetstat nozzle supplied heated compressed air at a temperature of 240'C and a pressure of 2 kg. The distance between Roll 7 'and Roll 11 was adjusted so that the boiling water shrinkage of the crimped multifilament was about 1% or less.

 Table 7 shows the IWR of the multifilament before crimping and the properties of the crimped multifilament.

The surface of the crimped multi-filament of the present example No unevenness was observed, and the surface was smooth.

As is evident from Table 7, the polyester crimped multifilament of the present invention had good crimping and fastness based on the eccentricity of the birefringence.

Neck point translation strength strength eccentric IWR crimp crimp

No. δ (A n)

(cm) before the IWR (g / d) (% ) X10- 3门(Ke / in) (%) (% ) amorphous

 1 5,000 50 3.7 3.7 57 Yes 0.491 28 35 91 Impossible

 2 6,000 50 0.130 4.1 58 59 Yes 0.561 23 24 88

3 7,000 50 0.324 4.3 46 63 Yes 0.655 16 17 82

4 8, 000 50 0.502 3.9 37 • 70 Yes 0.718 13 12 78

5 5,000 68 0.511 3.9 59 2 None 0.570 7 6 54

6 6,000 63 0.642 4.2 48 4 RR 0.651 5 7 58

7 7,000 60 0.673 4.4 42 7 None 0.685 6 6 56

8 8, 000 57 0.717 4.1 33 7 None 0.722 4 3 51

Nos. 5 to 8 are the powers that do not apply water, ivy, Jtl ^ iJo

Example 8

 The present embodiment is an example in which a polyester crimped multifilament is cut into a step to form a spun yarn.

 In Example 1, a 250-hole rectangular spout was used in which 50 holes were arranged in series in a row with 6 holes between holes, and 5 rows were perforated at intervals of 6 mm. Below the spinneret, a heating cylinder with a length of 35 cm and a width of 15π-25 cm was provided.

 In Example 7, No. 2 in Table 7 (spinning speed of 6,000 m / min) and No. 6 were spun in the same manner, and a non-crimped multifilament of 500 d / 250 f was used. I got

 When water was applied, a roll having a diameter of 3 cm and a length of 35 cm was used in the “roll method” in FIG. Next, the obtained non-crimped multifilament was heat-treated in the same manner as in Example 7 to obtain a crimped multifilament.

 The crimped multi-filaments of each of them were cut by 80 bells to 110 mm, respectively, to make them stable fibers. These were supplied to a 60-inch roller-card machine and subjected to a card test.

 Regarding No. 2 of Example 7, forging was performed without any problem, and a sliver was obtained. The sliver also has a nep

 1

Then, spinning was continued, and a spun yarn of ——N n was obtained.

 40

On the other hand, in No. 6 of Example 7, cotton was frequently dropped at the outlet of the breast cylinder during card processing, and spinning with a card was impossible. 9

 This example corresponds to Example 7 and shows a case where the cross section of a single fiber is irregular.

 A spinneret with 24 holes perforated in a trilobal with three sides equal length of 0.28 thigh and 0.06 mm slit width was used.

 The spinning conditions were the same as in Example 7. The measurement of the neck point during spinning was carried out by visual observation.

Table 8 shows the properties of the obtained polyester crimped multifilament. The degree of irregularity of the single fibers was 1.8 to 1.9 in each case.

Table 8

t

Να5 ~ 8 are i ^ without water application,

Example 10

 The same spinning as in Example 7 was performed, asymmetric cooling was performed, and the spinning was performed at β, δΟΟπιΖ without stretching after applying the oil agent. When applying water, use the “nozzle method” shown in Fig. 9 (1) to apply water at room temperature of 100 weight percent per yarn weight, and position the asymmetric cooling as shown in Table 9 It was done differently.

 When water was applied, the yarn was changed at the application position in all cases, and it was confirmed that a neck had occurred.

 Each of the multifilaments to which water was applied had an eccentric birefringence distribution and was non-crimped.

 Following water application, crimping was performed continuously without winding using the processing device shown in Fig. 6 to obtain a crimped multi-filament of 50 d 24 f. The processing conditions used were jet staff nozzles, and the temperature was 250 · (: pressure 4 kg / c—constant. The relaxation rate was about the shrinkage rate of the crimped multi-filament boiling water. It was adjusted to be 1% or less.

Table 9 shows the IWR of the multifilament before crimping and the properties of the crimped multifilament. Incidentally, both surface of Mekuchijimima Ruchifu I lame down bets in this embodiment irregularities not observed, was smooth ₀

As is clear from Table 9, the polyester crimped multifilament of the present invention had good crimping and fastness. In addition, this polyester crimped multifilament had a feature that the initial modulus was small. This property, when knitted fabric, Demonstrated a flexible and bulky texture

Table 9

CJi CJ1

o.5 «itt ^ iJ

Example 1 1

 Regarding No. 2 in Table 9 of Example 10 (water application at a yarn temperature of 200'C), except that the water application amount was changed as shown in Table 10, the same procedure as in Example 10 was carried out. A crimped multifilament was obtained.

Table 10 shows the properties of the obtained crimped multifilament.

Industrial applications

 INDUSTRIAL APPLICABILITY The crimped multifilament of the present invention has transparency and bulkiness as a continuous filament, and has high robustness and high quality when used in fields such as carpet and brushed fabric. , Performance is exhibited. When used as a cut fiber, it can be mixed with other materials such as wool and cotton without any problems in card passing properties and spinning properties.

 In addition, the production method of the present invention has high productivity and is industrially extremely high since the above-described crimped multifilament can be produced at high speed and easily without any trouble during spinning and crimping. It has value.

Claims

The scope of the claims

1. Made of a thermoplastic polymer, the birefringence of the outer layer is larger than the birefringence measured at the center of the constituent single fibers, and shows the minimum birefringence A crimped multifilament having a distribution in which the position is eccentric from the center of the fiber and having a random crimp of 10 / in or more.

 2. The position where the birefringence of the outer layer is higher than the birefringence measured at the center of the monofilament, which is made of polyamide, and shows the minimum birefringence. Has a distribution that is eccentric from the center of the fiber axis, has a crystal growth rate of 0.2 or more determined by wide-angle X-ray diffraction, and has a random crimp of 10 or more Zin. Polyamide crimped multifilament.

3. In the above-described polyamide crimped multifilament, when the cross section of the single fiber constituting the fiber is circular, the difference in the birefringence between the single layer and the inner layer is 5 mm. ^10-3 Helsingborg a mi de of the claims, characterized in that 45 10 _ ³ Dearu second claims crimping Maruchifi lame down Bok.

 4. The polymer according to claim 2, wherein the crystal growth degree obtained by wide-angle X-ray diffraction is 0.25 or more in the polyamide crimped multifilament. Mid crimped multifilament.

5. The polymid crimped multifilament according to claim 2, wherein the boride mid crimped multifilament has a number of crimps of 12 or more / in. Hint.

6. The polycrystalline crimped multi-filament according to claim 2, wherein the surface of the constituting single fiber is smooth in the polyamide crimped multi-filament. .

 7. In the polyimide crimped multifilament, when the polyamide is polyhexamethylene azibamide, the crystal integrity coefficient determined by wide-angle X-ray diffraction is 70% or more. 3. The polyamide crimped masoretic filament according to claim 2 characterized by the above-mentioned.

 8. The position where the birefringence of the outer layer is higher than the birefringence measured at the center of the monofilament that is made of polyester and has the minimum birefringence. Has a distribution eccentric from the center of the fiber axis, a crystal growth degree determined by wide-angle X-ray diffraction of 0.4 or more, and a random crimp of 10 / in or more. Crimped multifilament ho

9. In the polyester crimped multifilament, when the cross section of the single arrowhead fiber is circular, the difference in birefringence between the outer layer and the inner layer of the single fiber is 20 X lO. - ³ claims to feature the ~ a 100 X 10- ³ of paragraph 8, wherein the poly ester crimp multiframe Lee la e n t.

 10. The polyester roll according to claim 8, wherein in the polyester crimped multifilament, the degree of crystal growth determined by wide-angle X-ray drawing is 0.5 or more. Reduced multifilament.

11. Made of polyethylene, and located at the center of the monofilament The birefringence of the outer layer portion is larger than the birefringence measured in the measurement, and the distribution having the minimum birefringence is eccentric from the center of the fiber. Polyester step fiber having a crystal growth degree determined by wide-angle X-ray diffraction of 0.4 or more and having a random crimp of 10 η or more <

12. In producing a random crimped multifilament by melt-spinning a polyamide, the temperature of the single fiber constituting the multifilament extruded from the spout is cooled to 100'C. Asymmetrical cooling by applying an aqueous liquid from one side until it is completed, withdrawing at a rate of at least 4000 m / "min, stretching at a ratio of 1.0 to 1.5 times, and then at a temperature of 150 ° C or more A method for producing a crimped multifilament, characterized by performing liquid jetting.

 13. The method according to claim 12, wherein the aqueous liquid is applied from one side until the temperature of the single fiber is cooled to 130'C.

 14. The method according to claim 12, wherein the aqueous liquid is applied from one side while the constituent single fibers are separated from each other.

 13. The production method according to claim 12, wherein the liquid is jetted in an unstretched state after drawing at a drawing speed of 15.5, OOO m Z minutes or more.

 16. The manufacturing method according to claim 12, wherein the fluid jet processing is performed at a temperature of 180 or more.

17. The manufacturing method according to claim 12, wherein said taking-off and said blasting are performed continuously.

18. In producing random crimped multifilaments by melt-spinning polyester, the multifilaments extruded from the spinneret are cooled until the temperature of the monofilaments constituting them is cooled to 150'C. After applying an aqueous liquid from one side and asymmetric cooling, drawing at 5000 m / min or more, stretching at 1.0 to 1.5 times, and then performing relaxation heat treatment at a temperature of 150 ° C or higher. Characteristic method for producing crimped multifilament.

 19. The production method according to claim 18, wherein the asymmetric cooling is performed by applying an aqueous liquid from one side until the temperature of the constituent single fibers is cooled to 200'C.

 20. The production method according to claim 18, wherein an aqueous liquid is applied from one side and asymmetric cooling is performed in a state where a plurality of single fibers are arranged in a plane.

 The manufacturing method according to claim 18, wherein after drawing at 21.5 000 m / min or more, a relaxation heat treatment is performed in an undrawn state.

22. The manufacturing method according to claim 18, wherein the relaxation heat treatment is a fluid jet processing.

 23. The manufacturing method according to claim 18, wherein the relaxation heat treatment is performed continuously with the take-off.