JP2001131825A - Polyketone fiber and method for producing the same - Google Patents

Abstract

(57) Abstract: A polyketone fiber composed of a polyketone polymer comprising a copolymer of an olefin and carbon monoxide, wherein the fiber is an aggregate of fibril bundles long in the fiber axis direction, The average diameter of the fibril bundle when observing the longitudinal section of the fiber by an electron microscope is 10 to 1000.
a polyketone fiber having a crystallinity of at least 50% and a crystal orientation of at least 80%. [Effect] It is possible to provide a polyketone fiber having high strength, high elastic modulus, and excellent knot strength and wear resistance.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyketone fiber having high strength and elastic modulus, excellent physical properties in the lateral direction such as bending and folding, and also excellent abrasion resistance, and a method for producing the fiber. .

[0002]

2. Description of the Related Art In recent years, an aliphatic polyketone polymer in which carbon monoxide and olefin are substantially completely alternately copolymerized has been obtained by polymerizing carbon monoxide with an olefin such as ethylene or propene using palladium or nickel as a catalyst. (Industrial Materials, December issue, No. 5
Pp. 1997), and studies on fiberization of polyketone polymers have been conducted. The characteristics of polyketone fibers are that high strength and high modulus fibers can be obtained, and since they have a higher melting point and higher heat resistance than conventional polyolefins, they can be used for industrial materials, especially for automobile tire cords. Expected.

In the field of industrial fibers which require high performance such as high strength, high elastic modulus and heat resistance in polyketone fibers, the use of a completely alternating copolymer of ethylene and carbon monoxide has been studied. Alternating copolymers of ethylene and carbon monoxide have a high melting point and can provide fibers with good heat resistance, but the melting point is higher than the temperature at which the three-dimensional cross-linking reaction occurs. Since it is impossible, it has been considered that the fiberization of the ethylene / carbon monoxide alternating copolymer is carried out by a wet spinning method.

[0004] For example, JP-A-2-112413,
JP-A-4-228613, JP-T-4-50534
4, JP-A-2-112413, JP-A-4-112.
No. 228613, Japanese Patent Publication No. Hei 7-508317,
JP-T 8-507328 discloses fibers spun using a solvent such as hexafluoroisopropanol, m-cresol, resorcin / water, phenol / acetone, hydroquinone / propylene carbonate, resorcin / propylene carbonate, and the like. . In these techniques, after dissolving the polyketone polymer in a solvent, it is discharged into a coagulation bath, coagulated and spun, and after partially or completely removing the solvent, a several times to several tens times hot drawing is performed. It is disclosed to obtain high strength polyketone fibers.

[0005] On the other hand, it has been known that in the case of polyethylene, which is a flexible polymer, a fibril bundle long in the fiber axis direction exists in the fiber by performing a high degree of drawing (Fiber Engineering II; Manufacturing, structure and physical properties,
p228: Japan Society of Textile Machinery, Textile Engineering Publication Committee). Also in the polyketone fiber produced by dissolving in the above-mentioned organic solvent, the fibril bundle structure long in the fiber axis direction is formed on the surface and inside of the fiber by performing the high orientation orientation of the coagulated fiber. Although the fibril structure can provide fibers with high performance in the fiber axis direction such as tensile strength and tensile elastic modulus, the fibers obtained by these techniques have a fibril average diameter larger than 1000 nm and rigid. Due to this, physical properties in directions other than the fiber axis, such as knot strength and bending strength, are extremely low.Furthermore, the bonding surface between fibrils has a low polymer density and fibrils peel off from the fiber surface due to wear and rubbing There is a problem that fluff is easily generated. For this reason, in applications where twisting, weaving, knitting, etc. are performed during processing, fuzzing due to friction occurs at points where fibers and processing machines and fibers intersect and at surfaces where fibers are joined, and thus the processing yield decreases and the final The quality of the product has dropped. Further, even if the processing conditions are limited to suppress the generation of fluff during processing, it is difficult to apply to applications (for example, ropes) that receive friction during use or receive a force in a direction other than the fiber axis direction. Therefore, there is a problem that the usage and the use conditions of the product are limited. In addition, WO9918143 discloses a technique for producing fibers by dissolving a polyketone polymer in a solution containing a metal salt such as an alkali metal, an alkaline earth metal, and zinc chloride. However, this technical document does not disclose any technique for reducing the fibril diameter inside the fiber, nor a polyketone fiber excellent in knot strength and abrasion resistance and a method for producing the fiber. In addition, this document includes ethylene /
Only the propylene / carbon monoxide terpolymer dissolution / spinning / drawing method and fibers obtained therefrom are exemplified, and have excellent mechanical performance of high strength and high elastic modulus, and are used for industrial fibers, especially tire cords. No mention is made of a polyketone fiber suitable for water and a method for producing the same.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a fiber shaft having high tensile strength and elastic modulus, less generation of fluff due to twisting and rubbing during processing and use, and bending and folding. An object of the present invention is to provide a polyketone fiber excellent in fiber physical properties other than the direction at low cost and with high productivity.

[0007]

SUMMARY OF THE INVENTION The present invention is directed to a polyketone fiber comprising a polyketone polymer comprising a copolymer of olefin and carbon monoxide, wherein the fiber is a bundle of fibrils long in the fiber axis direction. A fibril having an average diameter of 10 to 1000 nm when the longitudinal section of the fiber is observed with an electron microscope, and a degree of crystallinity of the fiber of 50% or more and a degree of crystal orientation of 80% or more. A polyketone fiber and a method for producing the same. The polymer used in the fiber of the present invention is a copolymer of olefin and carbon monoxide. From the viewpoints of strength, adhesion, dimensional stability, creep resistance, high-temperature fiber properties, and the like, a polymer containing 1-oxotrimethylene as a main repeating unit in which ethylene and carbon monoxide are bonded is preferable. As the proportion of 1-oxotrimethylene in the repeating unit increases, a fiber having a high melting point and high mechanical properties can be obtained as the proportion increases.
It is preferably at least 0% by weight, more preferably at least 97% by weight.

In the repeating unit in which olefin and carbon monoxide are bonded, ketone groups may be partially bonded to each other and olefins may be bonded to each other, but 90% by weight or more of polyketone in which olefin and carbon monoxide are alternately arranged. Desirably, it is a polymer. From the viewpoint of light resistance, heat resistance, and a decrease in physical properties at high temperatures, the content of the portion where olefins and carbon monoxide are alternately arranged is preferably as high as possible, and preferably 97%.
% Or more, most preferably 100% by weight. Also, if necessary, olefins other than ethylene such as propene, butene, hexene, cyclohexene, pentene, cyclopentene, octene, and nonene, methyl methacrylate, vinyl acetate, acrylamide, hydroxyethyl methacrylate, styrene, sodium styrene sulfonate, allyl sulfone Compounds having an unsaturated hydrocarbon such as sodium acid, vinylpyrrolidone, and vinyl chloride may be copolymerized.

The fiber of the present invention is a bundle of fibrils having an average diameter of 10 to 1000 nm which is long in the fiber axis direction. Here, the fibril is a cylindrical structure elongated in the fiber axis direction when the fiber surface and the longitudinal section of the fiber are observed by an electron microscope, and is a highly oriented polyketone fiber which has been stretched at least 5 times. Exists. Many of these fibrils are arranged in parallel in the fiber axis direction,
Fibers are formed by laminating and joining, and are a unit of the macro structure that forms the fibers. The fibrils can be observed and the diameter can be measured by the method described in Examples of the present invention.

The present inventors have found that the average diameter of fibrils is 1
In particular, it was found that when the thickness is in the range of 0 to 1000 nm, the fiber is excellent in abrasion resistance and also excellent in fiber physical properties against a force applied in a direction perpendicular to the fiber axis such as knot strength. The smaller the average diameter of the fibrils (ie, the smaller the average diameter), the higher the abrasion resistance and the physical properties against bending. On the other hand, the average fibril diameter is 1000 nm.
If it becomes larger, the density of the polymer at the interface between fibrils becomes sparse, so that the abrasion resistance is reduced and the physical properties against bending are reduced. Therefore, the average diameter of fibrils is 10
To 1000 nm, more preferably 20 to 800 nm, particularly preferably 100 to 500 n.
m. The average diameter of the fibrils can be determined by the processing method, observation method, and calculation method described in Examples of the present invention.If the average diameter is within the above range, fibrils having a diameter exceeding 1000 nm in the fiber, Or 10n
There is no problem even if a small amount of fibrils less than m is contained.

The fiber of the present invention is formed by laminating fibrils in a bundle. The boundary region between the fibrils may be filled with a polyketone polymer or may be voids. They may be mixed. When the fiber is manufactured by the usual coagulation and drawing methods, this boundary region is a state in which the polyketone polymer and the voids are mixed, and this portion may become a defect and the abrasion resistance may be reduced. The packing density of the polymer in the region is preferably higher. In addition, the fiber of the present invention must have practical tensile fiber properties, heat resistance, and durability in addition to physical properties in the bending direction in order to use the fiber as a normal industrial fiber or a clothing fiber. is there. In order to express these practical fiber performances, the higher order structure of the fiber is important, and specifically, the degree of crystallinity must be 50% or more and the degree of crystal orientation must be 80% or more. Tensile strength,
From the viewpoints of elastic modulus, dimensional stability, and heat resistance, the higher the crystallinity, the more preferable it is. Preferably, the crystallinity is preferably 50% or more, more preferably 60% or more, and particularly preferably 70% or more. Further, the higher the degree of crystal orientation, the better the tensile elasticity. Therefore, it is preferably at least 80%, more preferably at least 90%, particularly preferably at least 95%.

In order for the fiber of the present invention to be widely used for various garments and industrial uses, it is necessary to have excellent abrasion resistance and practical properties in the transverse and tensile directions. Specifically, as the abrasion resistance, in the abrasion test shown in Examples of the present invention, it is preferable that the fibrils have less than 10 fibrils and single yarn breaks on the fiber surface, and that these fluffs are not particularly observed. Is preferred. The knot strength is 1 cN / dtex or more, and more preferably 2 cN / dtex.
/ Dtex or more, particularly preferably 3 cN / dtex or more. Further, the higher the tensile strength, the better, preferably 3 cN / dtex or more, more preferably 5 cN / dtex or more, particularly preferably 10 cN / dtex.
/ Dtex or more is desirable. The tensile modulus is preferably 50 cN / dtex or more, more preferably 100 cN / dtex or more, and particularly preferably 20 cN / dtex or more.
Desirably, it is 0 cN / dtex or more.

The polyketone fiber having the above-mentioned properties can be widely used as a fiber product for industrial use and clothing use. In the present invention, the term "fiber product" refers to a yarn, hollow fiber, porous yarn, cotton, string, knitted fabric, woven fabric, non-woven fabric, and clothing, medical equipment, and living materials using these, which are composed only of the polyketone fiber of the present invention. , Tire cords, belts, concrete reinforcing materials and the like, as well as fiber products using the polyketone fibers at least in part. The method of producing the fiber of the present invention is not particularly limited as long as the average diameter of the fibrils is in the range of 10 to 1000 nm, and conventionally known melt spinning, dry spinning, wet spinning, and wet spinning with a concentrated salt solvent are also used. Can be applied as it is or after modification, but a dry spinning or wet spinning method that easily produces fibrils is preferable, and a wet spinning method using a concentrated salt solvent that can reduce the average diameter of fibrils is particularly preferable.

The average diameter of the fibrils is 10 to 1000 n.
In order to make m, it is important to control the solidification structure, which is the basic structure of the fiber, to a small structure, and it is very important to control the coagulation speed of the polyketone fiber in production. If the coagulation speed is too high, the diameter of the fibrils increases, and the diameter of the fibrils present in the finally obtained polyketone fiber becomes 1000 nm or more. On the other hand, if the coagulation speed is reduced, fibers having a small average fibril diameter can be obtained. However, if the coagulation speed is too slow, the spinning speed should be 0.1 m
Per minute or less, or the coagulation bath length is several hundred meters
Therefore, it cannot be manufactured under industrial conditions. For this reason, it is important to select the composition and temperature of the solvent, the composition and temperature of the coagulation bath, and to control the coagulation rate in an appropriate range. It is preferable to use an aqueous solution of a concentrated metal salt such as a zinc halide salt as a solvent for the polyketone polymer when performing wet spinning, and to use a metal salt such as a zinc halide, an alkali metal salt, or an alkaline earth metal salt in the coagulation bath. Preferably, an aqueous solution is used.

Hereinafter, the method for producing the polyketone fiber of the present invention will be described, taking as an example a case where an aqueous zinc halide solution is used as a solvent. Examples of the zinc halide compound used for dissolving the polyketone polymer include zinc salts such as zinc chloride, zinc bromide, and zinc iodide. From the viewpoint of solubility of the polyketone polymer, cost of the solvent, and stability of the aqueous solution, zinc chloride and zinc iodide are preferred, and zinc chloride is most preferred. The concentration of the zinc halide is not particularly limited, but is preferably higher from the viewpoint of the solubility of the polyketone polymer. The appropriate range of the concentration of the zinc halide in the aqueous solution varies depending on the composition of the polyketone polymer, the type of the zinc salt, the temperature of the aqueous solution, and the like. For example, a preferred concentration of the aqueous zinc chloride solution for dissolving the polymer is 50
At 80 to 80 ° C, the content is 10 to 80% by weight. From the viewpoints of dope stability, spinnability, recovery cost, etc.
It is particularly preferred that the content be 0 to 70% by weight.

The aqueous solution of the zinc salt may be a mixture of a plurality of zinc halides for the purpose of improving the solubility, reducing the cost and stabilizing the dope. If necessary, an alkali metal or alkaline earth metal halide such as sodium chloride, potassium chloride or calcium chloride may be contained at 60% by weight or less. 10% by weight of other inorganic and organic substances as long as the solubility is not impaired.
It may be contained below. The polymer concentration in the zinc salt aqueous solution dope is preferably 0.005 to 70% by weight. The term “dope” refers to a solution in which a polymer is dissolved in a solvent, and in this case, refers to a solution in which a polyketone polymer is dissolved in a zinc salt aqueous solution. If the polymer concentration is less than 0.005% by weight, the concentration is too low, resulting in a disadvantage that the fiber is not easily formed during coagulation, and that the production cost of the fiber is too high. 70% by weight
Is exceeded, the polymer no longer dissolves in the solvent. From the viewpoint of solubility, ease of spinning, and fiber manufacturing cost,
Preferably 0.5 to 40% by weight, more preferably 1 to 3
0% by weight.

The polyketone zinc halide dope is extruded from a spinneret and subsequently coagulated into a fiber in a coagulation bath. In this coagulation process, it is desirable to employ a so-called air gap spinning method in which the dope discharged from the spinneret once passes through a gas such as air or nitrogen and then enters a coagulation bath. When the spinneret is in contact with the coagulation bath, the polymer precipitates around the spinning and clogging of the spinneret and defects in the yarn are likely to occur, making spinning unstable and difficult to obtain high-performance fibers. . The composition of the coagulation bath may be any organic solvent such as methanol and acetone, water, an organic aqueous solution, an inorganic aqueous solution, and the like, but in the case of the organic solvent alone composition, the coagulation rate is extremely slow. It becomes difficult to spin at industrial speed and equipment,
Preferably, the solution contains at least 1% by weight of water. The temperature of the coagulation bath varies depending on the composition of the coagulation bath, but is usually in the range of -100C to 100C. But,
If the temperature of the coagulation bath is too high, the coagulation rate is increased and the diameter of the fibrils is increased.
It is desirable that the temperature be 0 ° C. or lower, more preferably 50 ° C. or lower, particularly preferably 30 ° C. or lower. On the other hand, if the coagulation bath temperature is too low, the coagulation rate is slowed down and the productivity is reduced.
C. or higher, particularly preferably −10 ° C. or higher.

When the coagulation bath temperature is high or the yarn diameter is large, the coagulation speed of the surface layer of the yarn is increased, and the diameter of the fibrils in the surface layer may be larger than 1000 nm.
When the diameter of the fibrils near the surface layer is too large, the average diameter of the fibrils near the center of the fiber is 100.
Even if it is 0 nm or less, the strength of the entire fiber against bending and knots may be insufficient. In such a case, it is necessary to select solidification conditions so as to reduce the solidification speed difference in the cross-sectional direction.

In the case of the zinc halide solvent system, the present inventors have found that when an aqueous solution containing 0.01 to 50% by weight of zinc halide is used in the coagulation bath, the fibril between the fiber surface and the central portion is reduced. By reducing the diameter difference, the fibril diameter at the surface of the fiber can be reduced to 100 even at a relatively rapid solidification rate.
It has been found that the thickness can be reduced to 0 nm or less. If the zinc halide concentration in the coagulation bath is too low, the solidification rate of the surface layer cannot be reduced, and if the concentration is too high, the coagulation will be too slow, making it difficult to spin at an industrial speed. The concentration is preferably 0.01 to 50% by weight, more preferably 0.1 to 15% by weight, and particularly preferably 1 to 15% by weight.
Desirably, it is in the range of 10 to 10% by weight.

The coagulation bath may contain a compound other than zinc halide as long as the coagulation property is not significantly changed. From the viewpoint of recovery efficiency, a compound having the same composition as the compound contained in the solvent is used. It is recommended that When passing the fibrous material through the coagulation bath, it is preferable to pass the fibrous material while taking it off at a constant speed. The winding speed is 0.001 to
1000 m / min, as a spinning draft, 0.01 to
1000. Here, the spinning draft is a value obtained by dividing the winding speed by the discharge linear speed. Depending on the spinning speed and the coagulation temperature, the zinc salt in the coagulated yarn may not be sufficiently removed in the coagulation bath. Therefore, the coagulated yarn that has exited the coagulation bath may be further washed if necessary. Any liquid may be used for washing as long as it has the ability to dissolve the zinc salt.However, in consideration of safety, solution cost, recovery cost, etc., an aqueous solution is preferable. From the viewpoint of solubility, water or an acidic aqueous solution of sulfuric acid, hydrochloric acid, phosphoric acid or the like is particularly preferable.

The solidified fiber substantially free of the zinc salt can be stretched after drying or stretched while drying to obtain a stretched yarn. As a drying method, a batch drying method in which the coagulated yarn is once wound (cheese, cake or pan) in a dryer, or the coagulated yarn is continuously spun after spinning,
Alternatively, it may be a continuous drying method in which the film is once wound and then run on a heated roll or plate or in a heated gas for drying. The continuous drying method is preferred from the viewpoint of yarn uniformity and production cost. The drying temperature is not particularly limited, but is preferably in the range of 60C to 260C. Also, 10
When drying at a temperature of 0 ° C. or more, it is preferable to flow an inert gas around the yarn. If necessary, treatment such as relaxation and stretching may be performed while drying.

The unstretched yarn thus obtained is continuously heated and stretched to a specific magnification or more, whereby a polyketone fiber having an average diameter of the fibrils of the present invention of 10 to 1000 nm can be obtained. As the heating and drawing method, a conventionally known apparatus or method such as a method of running on a heated roll or plate or in a heated gas, a method of irradiating a running yarn with laser, microwave, or far-infrared light is employed as it is or with improvement. You can do it. In the present invention, in order to form and grow fibrils, it is important to perform stretching at least 5 times in total. When the draw ratio is less than 5 times, the fibril structure does not sufficiently develop and the mechanical properties of the obtained fiber are also insufficient. The higher the draw ratio, the more the fibrils are oriented in the fiber axis direction, the smaller the average diameter, and the better the mechanical properties. The preferred range of the draw ratio varies depending on spinning conditions, drying conditions, applications, and the like, but it is preferable that the drawing be performed at least 5 times, more preferably at least 10 times, and particularly preferably at least 15 times.

The number of stretching stages may be any, and if necessary, multi-stage stretching may be performed. When performing multi-stage stretching, a method of gradually increasing the stretching temperature is preferable. The stretching temperature may be any temperature as long as the yarn can be effectively stretched, and is preferably in the range of 80 ° C. to 300 ° C., and more preferably in the range of the melting point of −50 ° C. to the melting point. The polyketone fiber of the present invention has excellent physical properties against loads and loads applied in directions other than the tensile direction such as bending and knotting, and is used for clothing that is processed into a woven or knitted fabric or processed by twisting or false twisting. The fiber which is suitable for use and industrial materials, and which has been drawn at a high magnification is particularly suitable for industrial materials such as ropes and tire cords. Further, when manufactured using a zinc halide-based solvent and a zinc halide-based coagulation bath, a fiber having a uniform fibril diameter in the cross-sectional direction of the fiber and excellent physical properties against bending can be obtained, and In addition, the safety and the collection efficiency are high, the collection cost and the production cost can be reduced, and the production equipment is simple and inexpensive. Therefore, the fiber of the present invention can be provided at a low cost and with high productivity.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to the following examples, but they do not limit the scope of the present invention. The measuring method of each measured value used in the description of the embodiment is as follows. (1) Intrinsic Viscosity Intrinsic viscosity [η] is a value obtained based on the following definition formula. T and T in the definition formula are 25 ° C. of a diluted solution of hexafluoroisopropanol and a polyketone dissolved in the solvent.
Is the flow time of the viscosity tube at C is the above solution 10
The solute weight value in grams in 0 ml. (2) Strong elongation, elastic modulus, knot strength Measured according to JIS-L-1013. (3) Knot strength ratio K / T is the knot strength ratio, where K is the knot strength and T is the tensile strength.

(4) Abrasion resistance The fiber was treated with tetrachloroethylene at 25 ° C for 1 minute to wash the oil. After bundling the fibers so that the total denier becomes 1000d, the fibers are cut into two pieces, a fixed yarn (yarn length 50cm) and a traveling yarn (yarn length 1m), and both ends of the fixed yarn have a tension of 0.5 cN / dtex. It was fixed to an iron pole. One end of the traveling yarn was fixed to a pendulum motor, and a weight was attached to the other end so that the load was 0.1 cN / dtex. The lower surface of the traveling yarn and the upper surface of the fixed yarn are brought into vertical contact with each other, and the pendulum motor at one end of the traveling yarn is driven to an amplitude of 50 mm, 100 mm.
Vibration was performed for 1 minute at a rate of reciprocation / minute. Here, the angle between the running yarn and the fixed yarn was 150 °. Five points were arbitrarily extracted from the friction portion of the running yarn after the test, and the surface was observed with an optical microscope to determine the rubbing state. FIG. 1 shows an outline of the wear device used for the measurement.

(5) Average diameter of fibrils: A fiber sample is put in a frame made of a PET film, and an epoxy adhesive (Hisuper 5; manufactured by Cemedine Co.) is added to the frame and left standing at room temperature for 5 minutes for fixing. did. : A PET frame on which a fiber sample was fixed was placed in a gelatin capsule, and an epoxy embedding agent (Quetol 812: Nissin EM)
(Manufactured by K.K.) and cured by heating at 60 ° C. for 24 hours. The capsules prepared in (1) were roughly cut with a thread saw, and subsequently trimmed to about 0.5 mm square with a razor. Further, the surface was exposed with an ultramicrotome (Ultracut N: manufactured by Reichert) in which a glass knife was set so that the longitudinal section of the fiber was exposed, and finally the surface was exposed with a sapphire knife. : Of the surfaced sample, only a portion trimmed to 0.5 mm square was cut out and placed on a sample stage for SEM,
It was fixed with a conductive carbon tape.

An ion sputtering apparatus (E103)
0: manufactured by HITACHI) to obtain about 2 n of Pt / Pd.
m coated, UHRSEM (S5000: HIT
The center of the longitudinal section of the fiber was observed at 5,000 times with an accelerating voltage of 3 kV by an ACHI company. : The center part of the fiber longitudinal cross-sectional image observed in was set as the center point, and the fiber axis direction was set as the meridian direction. A line passing through the center point and perpendicular to the fiber axis (in the equator direction) was drawn and used as the center line. : In the image, fibrils long in the equator direction are laminated inside the fiber, and a point of contact between a line joining the fibrils and a center line is taken, and the distance between the points of contact is defined as the diameter of the fibril.

The diameter of five fibrils, five on the right side of the equatorial axis and five on the left side, as measured from the center point, was measured. If the number of fibrils in one observation image is less than 10,
Fibrils were arbitrarily extracted from another image of the same sample, and the diameter was measured. A total of 10 diameters were measured. : The diameters of the fibrils are D1, D2, D3,.
The average diameter D of fibrils was calculated from Equation 1 as D10.

(Equation 1) FIG. 2 shows the outline of the observation photograph.

(6) Crystallinity The crystallinity was measured using a differential heat measurement device Pyris1 manufactured by Perkin Elmer under the following conditions. Measurement temperature: 30 ° C. → 300 ° C. Heating rate: 20 ° C./min Atmosphere: Nitrogen, flow rate = 200 mL / min Calculated from the area of the largest endothermic peak observed in the range of 200 ° C. to 300 ° C. in the obtained endothermic curve. It was calculated from the calorific value ΔH (J / g) obtained by the following equation. Crystallinity = ΔH / 225 × 100 (%)

(7) Crystal orientation degree Imaging plate X-ray diffractometer R manufactured by Rigaku Corporation
Using INT2000, a diffraction image of the fiber was captured under the following conditions. X-ray source: CuKα ray Output: 40 KV 152 mA Camera length: 94.5 mm Measurement time: 3 minutes Observed near 2θ = 21 ° of the obtained image (11
0) Calculated by the following equation from the half width H of the intensity distribution obtained by scanning the surface in the circumferential direction. Crystal orientation = (180−H) / 180 × 100 (%)

[0031]

Example 1 A polyketone polymer having an intrinsic viscosity of 5.9, in which ethylene and carbon monoxide were completely alternately copolymerized by a conventional method, was added to an aqueous solution containing 65% by weight of zinc chloride and 10% by weight of sodium chloride. The mixture was stirred and dissolved at 2 ° C. for 2 hours to obtain a dope having a polymer concentration of 8% by weight. The obtained dope was heated to 80 ° C., filtered with a 20 μm filter, and then passed through an air gap of 0.10 mm in diameter, L / D = 1, 10 mm through a 50-hole spinning hole, and then 5% by weight. Discharge rate 2.5c into 18 ° C water containing zinc chloride
It was extruded at a rate of c / min and solidified. The coagulated yarn was successively washed with a 2% by weight aqueous sulfuric acid solution and further washed with water at 30 ° C., and then wound at a winding speed of 3.2 m / min. The obtained filamentous material was dried at 200 ° C. to obtain an undrawn yarn. After performing the first stage drawing at 240 ° C., the undrawn yarn was subsequently subjected to the second stage drawing at 265 ° C., and a total of 15-fold drawing was performed. This fiber had an average fibril diameter of 420 nm and had excellent abrasion and knot strength. The properties and performances of the obtained fibers are shown in Table 1 together with the following Examples 2 to 6 and Comparative Examples 1 to 6.

[0032]

Example 2 Using the dope of Example 1, spinning was carried out in the same manner as in Example 1 except that the composition of the coagulation bath was 10% by weight of zinc chloride and 90% by weight of water, and the temperature of the coagulation bath was 25 ° C. Stretching was performed.

EXAMPLE 3 Using the dope of Example 1, spinning was carried out in the same manner as in Example 1 except that the composition of the coagulation bath was 1% by weight of zinc chloride and 99% by weight of water, and the temperature of the coagulation bath was 40 ° C. Stretching was performed.

Example 4 The undrawn yarn obtained in Example 1 was drawn 8 times at 240 ° C.

[0033]

EXAMPLE 5 An ethylene / carbon monoxide completely alternating copolymer having an intrinsic viscosity of 9.7 was added to an aqueous solution containing 65% by weight of zinc chloride and 10% by weight of sodium chloride.
The mixture was stirred and dissolved at 6 ° C. for 6 hours to obtain a dope having a polymer concentration of 4% by weight. Using this dope, spinning and stretching were performed in the same manner as in Example 1.

Example 6 A propylene / carbon monoxide alternating copolymer was prepared using 3
% By weight of an ethylene / propylene / carbon monoxide alternating copolymer terpolymer (intrinsic viscosity = 5.4) was added to an aqueous solution containing 65% by weight of zinc chloride and 10% by weight of sodium chloride at 80 ° C. for 2 hours. By stirring and dissolving, a dope having a polymer concentration of 9% by weight was obtained. Using this dope, spinning and stretching were performed in the same manner as in Example 1.

[0034]

Comparative Example 1 The undrawn yarn obtained in Example 1 did not have a fibril structure.

Comparative Example 2 The undrawn yarn obtained in Example 1 was heated at 240 ° C.
Stretching was performed three times. This drawn yarn also did not have a fibril structure.

Comparative Example 3 1% by weight of calcium hydroxyapatite was added to the polymer of Example 1, and the mixture was ground and mixed in a homomixer. The obtained fine powdery polymer was melted at 270 ° C. and extruded from a monohole spinneret having a spinneret diameter of 0.25 mmφ. Immediately after the start of melting, the extrusion pressure increases significantly,
Spinning was not possible.

[0035]

Comparative Example 4 The polymer of Example 1 was added to an aqueous solution containing 75% by weight of resorcinol, stirred at 80 ° C. for 2 hours and dissolved to obtain a dope having a polymer concentration of 8% by weight. Using the same dope as in Example 1, the obtained dope was discharged at a rate of 4.5 c.
The mixture was discharged at a rate of c / min and extruded through a 10 mm air gap into a -5 ° C. methanol bath to obtain a coagulated yarn. After washing the obtained coagulated yarn with methanol, 100 ° C.
To obtain an undrawn yarn. This undrawn yarn was hot drawn in the same manner as in Example 1.

Comparative Example 5 The undrawn yarn obtained in Comparative Example 4 was subjected to hot drawing at 240 ° C. eight times.

[0036]

Comparative Example 6 The polymer of Example 1 was added to hexafluoroisopropanol, and stirred and dissolved at 30 ° C. for 2 hours.
A dope having a polymer concentration of 8% by weight was obtained. The obtained dope was extruded into a 10 ° C. acetone bath at a discharge rate of 4.5 cc / min using the same spinner as in Example 1 to obtain a coagulated yarn. The obtained coagulated yarn was left standing at 30 ° C. for 24 hours and dried. The obtained undrawn yarn was hot drawn according to the same formulation as in Example 1.

Comparative Example 7 Coagulation, drying and stretching were performed in the same manner as in Example 1 except that the coagulation bath was water and the coagulation bath temperature was 60 ° C.

[0037]

[Table 1]

[0038]

According to the present invention, not only the mechanical properties in the tensile direction such as strength and elastic modulus are excellent, but also the physical properties against loads and loads applied in directions other than the tensile direction, such as bending and knots, are further improved. A polyketone fiber having abrasion resistance and a method for producing the same can be provided. The fibers of the present invention are suitable for use in clothing and industrial materials that are processed into woven or knitted fabrics, or processed by twisting, false twisting, or the like. Suitable for industrial materials such as tires and tire cords. In addition, when manufactured using a zinc halide-based solvent and a coagulation bath,
The average diameter of the fibers is small, and the distribution of the fibril diameter in the cross-sectional direction is uniform, so that fibers with better physical properties can be obtained.In addition, safety, recovery efficiency is high, recovery cost and manufacturing cost are low. In addition, the production equipment is simple and inexpensive, so that the fiber of the present invention can be provided at low cost and high productivity.

[Brief description of the drawings]

FIG. 1 is a diagram showing an outline of a test device for a friction test used in the present invention.

FIG. 2 is a diagram illustrating a method of measuring the diameter of a fibril from an electron microscope image of a longitudinal section of a fiber.

Claims (7)

[Claims] 1. A polyketone fiber comprising a polyketone polymer comprising a copolymer of an olefin and carbon monoxide, wherein the fiber is a bundle of fibrils long in the fiber axis direction, and the fiber is obtained by an electron microscope. The average diameter of fibrils when observing the longitudinal section of the fiber is 10 to 1000
a polyketone fiber having a crystallinity of at least 50% and a crystal orientation of at least 80%. 2. The fibril has an average diameter of 20 to 800 n.
The polyketone fiber according to claim 1, wherein m is m. 3. The polyketone fiber has a tensile strength of 10c.
N / dtex or more, tensile modulus of elasticity is 200 cN / dt
The polyketone fiber according to claim 1 or 2, wherein the knot strength is 3 cN / dtex or more. 4. The polyketone fiber according to claim 1, wherein 97% by weight or more of the repeating unit constituting the polyketone polymer is 1-oxotrimethylene. 5. A polyketone polymer is dissolved in an aqueous solution containing 10 to 80% by weight of zinc halide, passed through a spinneret and discharged into a coagulation bath containing 0.01 to 50% by weight of zinc halide. The method for producing a polyketone fiber according to any one of claims 1 to 4, further comprising a step of substantially removing the solvent after fibrillation and performing hot drawing by 5 times or more. 6. The method for producing a polyketone fiber according to claim 5, wherein the hot drawing is one-step drawing and / or multi-step drawing, and the total drawing ratio is 10 times or more. 7. A fiber product comprising the polyketone fiber according to any one of claims 1 to 4.