JP2003012917A - Polyketone solution and method for producing polyketone fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyketone solution which is lowly toxic, flame-retardant, uses an excellently recoverable solvent, enables to spin a gel at a high speed, enables to produce a highly strong and highly elastic polyketone fiber at a lower coat, and can be elongated by heat to give an excellently dignified polyketone fiber because the single fiber is free from melting to adhere. SOLUTION: The polyketone solution is produced by dissolving a polyketone having a repeating unit represented by the formula (1) at a content of 95 mol% or more and satisfies the following equations: 0.2<=L/Z<=1.5, 0.2<=(Z+L)/(Z+L+ X+W)<=0.7, 0.5<=(Z+L+X)/(Z+L+X+W)<=0.7 [wherein Z is the mass of zinc chloride, L is the mass of lithium chloride, X is the mass of a metal salt excluding zinc chloride and lithium chloride and W is the mass of water]. The method for producing a polyketone fiber comprises using the solution.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyketone solution suitable for producing a polyketone fiber having high strength and elastic modulus, and a method for producing a polyketone fiber using this solution.

[0002]

2. Description of the Related Art By polymerizing carbon monoxide and an olefin such as ethylene or propylene by using a transition metal complex such as palladium or nickel as a catalyst,
It is known that a polyketone in which carbon monoxide and olefin are copolymerized substantially completely can be obtained (industrial materials, 1
February issue, page 5, 1997). Many researchers have studied the application of polyketones as fibers for industrial materials, and have found that they have high strength, high elastic modulus, high dimensional stability at high temperatures,
It is expected to be applied to fibers for composite materials such as reinforcing fibers for tire cords and belts and fibers for reinforcing plastics by taking advantage of good adhesiveness and high creep resistance.

Particularly, a polyketone composed of repeating units of ethylene and carbon monoxide has the highest dimensional stability at high temperature, and the conformation of the molecular chain is close to a straight line like polyethylene and polyvinyl alcohol.
It can be a so-called super fiber, a high-strength, high-modulus fiber. If such a polyketone fiber can be industrially produced, it is possible to reduce the weight of the tire as an alternative to the steel tire cord, and it is expected that the environmental problems will be improved.

In order to produce the above-mentioned high-performance polyketone fiber, it has been studied to apply the gel spinning method found in the production of polyethylene fiber, polyvinyl alcohol fiber, etc. to the production of polyketone fiber, and a thermoreversible gel. Solvents have been developed for polyketones that form. For example, in JP-A-4-505344 and JP-A-5-504371, pyrrole, phenol, pyridine, benzoic acid,
Formic acid, N-methylpyrrolidine, aniline, phenoxyethanol, N-methylimidazole and the like are shown, and JP-A-8-507328 discloses ethylene carbonate, benzyl alcohol, γ-butyrolactone, dipropylene glycol and the like. These solvents have a problem as an industrial method because of their high toxicity, denaturation of polyketone, low solubility in polyketone, high flammability, and need for explosion-proof equipment.

On the other hand, the applicant of the present invention is
9/18143 pamphlet and International Publication No. 00/09
No. 611 pamphlet suggests that an aqueous solution of a metal salt such as zinc chloride is used as a solvent for polyketone,
Further, JP-A-2001-293928 proposes a gel spinning method using an aqueous metal salt solution as a solvent. In this gel spinning method, a polyketone solution having a phase separation temperature in a temperature range of 0 to 250 ° C. is spun in a bath by using a solvent composed of an aqueous solution of a metal salt of zinc salt, calcium salt, thiocyanate and iron salt. It is cooled and coagulated to form thermoreversible gel fibers. The solvent used in this method has low flammability and toxicity, and dissolves the polyketone without causing chemical crosslinking of the polyketone and reduction in molecular weight. Therefore, according to this method, it is possible to produce a polyketone fiber having high strength and high elastic modulus.

However, Japanese Patent Laid-Open No. 2001-29392
In the gel spinning method using a solvent described in Japanese Patent Publication No. 8, when the spinning speed is slow, it is possible to obtain a polyketone fiber having a high strength and a high modulus of elasticity of 15 cN / dtex or more and an elastic modulus of 350 cN / dtex or more. Possible, but spinning speed is 5
When it was 0 m / min or more, the spinning became unstable such as single yarn breakage and the physical properties were deteriorated. It was considered that the main reason for this was that the gelation rate of the polyketone solution used here was slow, so that the residence time in the cooling bath was shortened as the spinning rate was increased, and sufficient gelation did not proceed. As measures against this, it is possible to lengthen the cooling bath or lower the cooling temperature, but with these methods, the bath resistance increases and unevenness in fiber thickness and single yarn breakage occur, and the temperature control cost of the cooling bath. Also, there are drawbacks such as an increase in solvent recovery cost.

[0007]

DISCLOSURE OF THE INVENTION The present invention aims to solve the following problems. (1) To manufacture polyketone fibers by a gel spinning method using a solvent having low toxicity, nonflammability, and excellent solvent recovery property. (2) Gel spinning can be performed at a spinning speed of 50 m / min or more with a short coagulation bath length. (3) Strength is 15 cN / dtex or more and elastic modulus is 350
Be able to manufacture polyketone fibers with high strength and high elastic modulus of cN / dtex or higher.

[0008]

In order to solve the above problems, the present inventors have studied in detail the solution composition of polyketone and the method for producing polyketone fiber. As a result, surprisingly, zinc chloride and lithium chloride It was found that when an aqueous solution of the specific salt composition of (3) was used as a solvent, the gelation speed was high, and thus high-speed gel spinning was possible, and the present invention was reached.

That is, the present invention provides a repeating unit of 95
In a solution in which a polyketone represented by the chemical formula (1) is dissolved in a solvent in an amount of mol% or more, the solvent has a mass of zinc chloride of Z, a mass of lithium chloride of L, a mass of metal salts other than zinc chloride and lithium chloride. X, a polyketone solution characterized by being an aqueous solution that satisfies the relationship of the following mathematical formula when the mass of water is W, and the polyketone solution at a temperature higher than the phase separation temperature of the polyketone solution from the spinneret. Discharged, extruded into a coagulation bath at a temperature lower than the phase separation temperature by 10 ° C. or more to coagulate to form a fibrous substance, remove part or all of the solvent from the fibrous substance, and then heat draw. A method for producing polyketone fiber. 0.2 ≦ L / Z ≦ 1.5 0.2 ≦ (Z + L) / (Z + L + X + W) ≦ 0.7 0.5 ≦ (Z + L + X) / (Z + L + X + W) ≦ 0.7

[0010]

[Chemical 2]

The polyketone of the present invention comprises 9 repeating units.
5 mol% or more is represented by the above formula (1).
Repeating units other than the above formula (1), for example, those shown in the chemical formula (2) may be contained within the range of less than 5 mol%.

[0012]

[Chemical 3]

In the formula, R is a C1-C3 atom other than ethylene.
0 organic groups such as propylene, butylene, 1
-Phenylethylene and the like. Some or all of these hydrogen atoms may be substituted with a halogen group, an ester group, an amide group, a hydroxyl group, an ether group or the like. of course,
R may be two or more, for example, propylene and 1
-Phenylethylene may be mixed. From the viewpoint that higher strength and higher elastic modulus can be achieved, and strength and retention of elastic modulus at high temperature are excellent, 97 mol% or more of repeating units are polyketones represented by the above formula (1). It is preferably 100 mol%.

The intrinsic viscosity [η] of the polyketone used in the present invention is not particularly limited, but it is preferably 3 or more from the viewpoint of high strength, and 20 or less from the viewpoint of solubility and spinnability. A more preferable range of [η] is 4
-15, most preferably 5-10.

When the mass of zinc chloride is Z, the mass of lithium chloride is L, the mass of metal salts other than zinc chloride and lithium chloride is X, and the mass of water is W, the solvent has the following mathematical relation. It needs to be some aqueous solution. 0.2 ≦ L / Z ≦ 1.5 0.2 ≦ (Z + L) / (Z + L + X + W) ≦ 0.7 0.5 ≦ (Z + L + X) / (Z + L + X + W) ≦ 0.7

L / Z, that is, the mass ratio of lithium chloride to zinc chloride is 0.2 to 1.5, preferably 0.5.
Is about 1.3, more preferably 0.8 to 1.1. L
When / Z is less than 0.2, the gelation rate is slow and a high-strength polyketone fiber cannot be obtained. If L / Z exceeds 1.5, the solubility of the polymer deteriorates and spinning becomes unstable.

(Z + L) / (Z + L + X + W), that is, the mass ratio of zinc chloride and lithium chloride in the solvent to the solvent is 0.2 to 0.7, preferably 0.3 to 0.6. When (Z + L) / (Z + L + X + W) is less than 0.2, the solubility of the polyketone becomes poor and stable spinning cannot be performed.
When it exceeds 0.7, the gelation rate becomes slow and a high-strength polyketone fiber cannot be obtained. (Z + L + X) / (Z + L +
X + W), that is, the mass ratio of the metal salt in the solvent to the solvent is 0.5 to 0.7. (Z + L + X) / (Z
When + L + X + W) is less than 0.5, the solubility of the polyketone is poor and stable spinning cannot be performed, and when it exceeds 0.7, the gelation rate becomes slow and a high-strength polyketone fiber cannot be obtained.

Metal salts other than zinc chloride and lithium chloride are metal salts that dissolve in water at a temperature of 50 ° C. in an amount of 1% by mass or more, and examples thereof include sodium chloride, calcium chloride, barium chloride, potassium chloride and magnesium chloride. Can be mentioned. In particular, a polyketone solution containing calcium chloride forms a more uniform and dense gel structure in a coagulation bath, and it is possible to produce a high-strength polyketone fiber by relatively low-ratio hot drawing. And the effect of reducing the drawing equipment cost by reducing the heating length.

The polymer concentration in the polyketone solution of the present invention is preferably 4 to 30% by mass, more preferably 5 to 20% by mass, most preferably 6 to 15 in order to produce a high strength polyketone fiber. It is% by mass. The polymer concentration is a value defined by the following formula. Polymer concentration (mass%) = [mass of polymer / (mass of polymer + mass of solvent)] × 100

The polyketone solution substantially uniformly dissolved by using the above solvent has a property that when it is gradually cooled, the polyketone is not uniformly dissolved in the solvent and the polyketone solution becomes nonuniform (white turbidity). . The temperature at which this heterogeneous state occurs, that is, the phase separation temperature, differs depending on the metal salt composition of the solvent, the polymer concentration and the polymer molecular weight.
In the present invention, a substantially uniformly dissolved polyketone solution (light transmittance of this solution is T1) is set to 10 per hour.
When gradually cooled at a rate of ℃ (light transmittance of the solution at a predetermined temperature in this cooling process is T2), the decrease rate of light transmittance increases, and the decrease rate of light transmittance decreases. 10%
Is defined as the phase separation temperature. The light transmittance is measured using laser light having a wavelength of 632.8 nm as a light source. The reduction rate of light transmittance is a value defined by the following formula. Reduction rate of light transmittance (%) = (T1−T2) / T1 × 1
00

By lowering the temperature below the phase separation temperature, the polyketone solution solidifies into a gel. A polyketone solution is extruded from a spinneret into a coagulation bath at a temperature lower than the phase separation temperature, and a fiber having a uniform cross section can be produced by solidifying in a gel state, and a stretch orientation with less spots is achieved by a hot drawing in a subsequent step, It becomes possible to exhibit physical properties of high strength and high elastic modulus. The polyketone solution of the present invention has a surprisingly high gelation rate, and particularly, the contact in a low temperature bath solidifies into a gel in a short time, and the gel spinning speed can be improved without increasing the low temperature bath length. Become.

In WO 99/18143 pamphlet and WO 00/09611 pamphlet, it is proposed to use a solution of a zinc salt or a lithium salt as a solvent for polyketone, but it is necessary to specify zinc chloride and lithium chloride. There is no description that an aqueous solution having a salt composition brings about the above-mentioned unique phenomenon or effect. When the phase separation temperature of the polyketone solution is high, it is necessary to make the temperature of the polyketone solution higher than the phase separation temperature when discharged from the spinneret, and when the polymer undergoes chemical cross-linking or decomposition, the physical properties of the polyketone fiber are degraded. There is. On the other hand, when it is low, the gelation rate tends to be low, the effect of increasing the gel spinning speed tends to be small, and the achieved strength tends to be low. From these viewpoints, the phase separation temperature is preferably 10 to 150 ° C, more preferably 20 to 100 ° C, and most preferably 30 to 70 ° C.

The method for dissolving the polyketone in the aqueous metal salt solution is not particularly limited, but the preferred examples will be described below. It is preferable to put the polyketone and the solvent in a dissolver and stir at a temperature higher than the phase separation temperature by 20 ° C. or more. If the stirring temperature is lower than this, it takes a long time to completely dissolve. When the stirring temperature exceeds 200 ° C., the polymer may be modified, so stirring at a temperature of 200 ° C. or lower is preferable. Defoaming is possible by leaving it under reduced pressure or under atmospheric pressure. However, when the viscosity of the polyketone solution is high, the polyketone is put in a dissolver, preferably 10 kPa or less, more preferably 1 kPa or less, By injecting the defoamed solvent and suppressing the mixture of air and stirring, a substantially uniform polyketone solution without bubbles can be obtained.

As the dissolver, a known mixer having a uniaxial or biaxial stirring blade and having excellent stirring efficiency can be applied. As a uniaxial stirring dissolver, one having a spiral or double spiral blade is suitable. The twin-screw batch type dissolver may be, for example, a planetary mixer using a hook having rotation and revolution as stirring blades, a double-arm kneader, a Banbury mixer, etc., and a continuous dissolver may be, for example, a screw extruder or a co-kneader. Etc. are used.

Next, a method for producing a polyketone fiber using the polyketone solution of the present invention will be described. The polyketone solution of the present invention is filtered with a filter as necessary to remove dust,
After removing undissolved polymer, catalyst residue, etc., the polyketone solution is extruded from the spinneret into the coagulation bath and molded into a fibrous form. The temperature at which the polyketone solution is extruded from the spinneret needs to be higher than the phase separation temperature. Below the phase separation temperature, the polyketone solution from the spinneret becomes non-uniform, causing yarn breakage and spinner clogging. Further, considering the long-term stability of extrusion, it is preferable to extrude at a temperature higher than the phase separation temperature by 10 ° C. or more.

The temperature of the coagulation bath is 10 ° C. higher than the phase separation temperature.
It is necessary to be lower than the above. A polyketone solution extruded in a bath below the phase separation temperature forms a wholly or partially gelled fibrous material, above which the spinning speed is increased due to the slower gelation rate. In addition, it is difficult to produce high strength polyketone fibers. The temperature of the coagulation bath is preferably 20 ° C. or more lower than the phase separation temperature, and 50 ° C. or more higher than the phase separation temperature in that the speed of forming the gelled fibrous material is increased and the spinning speed can be increased. Lower is more preferable.

The medium forming the coagulation bath may be one having a low affinity with the solvent or one having a high affinity as long as it is a liquid at the temperature used. As those having low affinity, hydrocarbons such as pentane, hexane, heptane, octane, nonane, toluene, ethylbenzene and decalin, dichloromethane, dichloroethane, trichloroethane, chlorobenzene, 1,1-dichloro-1-fluoroethane, 1,1,1. Examples thereof include halogenated hydrocarbons such as 2-trichloro-1,2,2-trifluoroethane and 2,2-dichloro-1,1,1-trifluoroethane. When these are used in the coagulation bath, since the affinity for the solvent is low, there is almost no diffusion of the solvent from the gelled fibrous material into the bath. Therefore, the fibrous material pulled out of the bath has almost the same composition as the extruded polyketone solution, and becomes a solution again by heating. Those with high affinity include methanol, acetone, acetic acid, acetonitrile,
Organic solvents having a high affinity with water, such as pyridine, N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone, aqueous solutions prepared by mixing the above organic solvents, sulfuric acid, hydrochloric acid, phosphoric acid, and metal salts. Examples thereof include an aqueous solution in which an inorganic substance such as is dissolved, water and the like.

When these are used in the coagulation bath, the solvent is diffused from the gelled fibrous material into the bath due to the high affinity of the polyketone with the solvent. Therefore, some or all of the solvent is removed from the fibrous material pulled out of the bath,
In some cases, it becomes a solution again by heating, and in some cases it does not become a solution again. It is preferable that the fibrous substance pulled out of the bath has a high strength and has a high affinity with a solvent from the viewpoint that the spinning speed can be increased. From the same viewpoint, it is an aqueous solution containing 30% by mass or more of water. Is more preferable. Further, in order to reduce the recovery cost of the solvent, the aqueous solution containing the same metal salt as the solvent is most preferable.

The fibrous material pulled out of the bath needs to be washed with a detergent to remove a part or all of the solvent. When a part of the solvent of the fibrous material that has been pulled out of the bath has already been removed, it can be washed with a cleaning agent if necessary. As the cleaning agent, water or an aqueous solution containing hydrochloric acid, sulfuric acid, phosphoric acid or the like and having a pH of 4 or less can be used. As the cleaning method, there are a method of passing a thread through a bath containing a cleaning agent, a method of spraying the cleaning agent from above and / or below the thread, and of course, these methods may be combined.

The fibrous material thus obtained is then preferably dried. As a drying method, drying may be performed while stretching, at a fixed length, or while shrinking. The temperature at the time of drying is usually 100 to 250 ° C, preferably 150 to 230 ° C. As a device for drying, known equipment such as a tunnel dryer, a roll heater, a net process dryer, etc. is used. Further heat drawing is necessary to obtain fibers of high strength and high elastic modulus. Stretching temperature is 100-300 ° C
Is preferred. It is preferably 150 ° C. or higher, more preferably 180 to 280 ° C. from the viewpoint of easy stretching. Stretch 1
Although it may be carried out in multiple stages or may be carried out in multiple stages by gradually increasing the stretching temperature, multistage stretching is preferred from the viewpoint that the stretching speed can be increased.

In order to suppress the friction between the fiber and the drawing machine and the generation of static electricity to make the drawing smooth, it is preferable to add a finishing agent at any stage from drying to drawing. Known finishing agents can be used. As the hot stretching device, a conventionally known device such as a method of traveling on a heating roll or plate or in a heated gas, or a method of irradiating a traveling yarn with a laser, a microwave, or infrared rays can be used as it is or after improvement. .

According to the production method using the polyketone solution of the present invention, it is possible to produce a polyketone fiber of excellent quality, in which single yarn fusion is unlikely to occur during hot drawing, variation in strength is small. This is also considered to be one of the reasons why the achieved strength after hot drawing is high.

[0033]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described by way of Examples, which do not limit the scope of the present invention. The measuring method of each measured value used in the present invention is as follows. (1) Intrinsic Viscosity The intrinsic viscosity [η] is calculated based on the following defining equation. In the formula, t and T are the flow-through times of a viscous tube at 25 ° C. of a dilute solution of polyketone dissolved in hexaisopropanol and hexafluoroisopropanol having a purity of 98% or more. C is the solute mass value in grams in 100 ml above.

(2) Fiber Strength, Elongation, Elastic Modulus The fiber strength / elongation was measured in accordance with JIS-L-1013 at a sample length of 20 cm and a tensile speed of 20 cm / min.
The average value of 10 measurements is calculated. (3) Light transmittance Laser light scattering photometer LSD-101 (trademark) equipped with a sample cell unit capable of controlling heating and cooling
(Manufactured by Nippon Kagaku Engineering Co., Ltd.). The light source was a He-Ne laser with a wavelength of 632.8 nm, the output was 15 mW, and the beam diameter was 1.50 m / m (1
/ E ² ).

[0035]

Example 1 A mass ratio of zinc chloride / lithium chloride / water is 2
In an aqueous solution of 7/32/41, the intrinsic viscosity is 5.5,
The polyketone represented by formula (1) was mixed at 30 ° C. so that substantially 100 mol% of the repeating unit was 8% by mass, and the pressure was reduced to 6.7 kPa. After leaving it for 30 minutes, it was sealed under reduced pressure and stirred at 85 ° C. for 2 hours to obtain a uniform and transparent polyketone solution. A part of this polyketone solution was transferred to a sample cell, and the light transmittance was measured while cooling the temperature of the solution from 85 ° C. at a rate of 10 ° C. for 1 hour. The phase separation temperature of this polyketone solution was 41 ° C. The solvent component ratio is L / Z = 1.19, (Z +
L) / (Z + L + X + W) = 0.59, (Z + L + X)
/(Z+L+X+W)=0.59.

After passing the obtained polyketone solution through a filter of 20 μm, a spinneret having 50 holes of 0.2 mm in diameter was used to obtain 80 by using a plunger type extruder.
Extruded at 90 ° C. and a speed of 90 m / min. Pass through an air gap of length 10 mm, then soak length 50 cm, temperature 2
After passing through a coagulation bath consisting of water at 0 ° C., it was pulled up using a Nelson roll at a speed of 90 m / min. Then, it was washed by spraying 1% hydrochloric acid and water on a Nelson roll, dried through a roll dryer at 220 ° C., then 90 m /
Rolled up in minutes. This gel spinning was carried out for 1 hour, but no trouble such as single yarn breakage or cutting was observed. This fiber was subjected to four-stage drawing of 7.0 times at 225 ° C., 1.5 times at 240 ° C., 1.4 times at 250 ° C. and 1.3 times at 260 ° C. to obtain a polyketone fiber. The fineness of the obtained fiber is 78 dte.
x, strength 16.7 cN / dtex, elongation 4.9%,
The elastic modulus was 401 cN / dtex.

[0037]

Example 2 An aqueous solution having a mass ratio of zinc chloride / lithium chloride / calcium chloride / water of 22/10/30/38 had an intrinsic viscosity of 5.5 and substantially 10 repeating units.
The polyketone represented by the formula (1) was mixed at 0 mol% at 6.5% by mass at 30 ° C., and the pressure was reduced to 6.7 kPa. After leaving it for 30 minutes, it was sealed under reduced pressure, and this was 85 ° C.
A homogeneous and transparent polyketone solution was obtained by stirring for 2 hours. A part of this polyketone solution was transferred to a sample cell, and the light transmittance was measured while cooling the temperature of the solution from 85 ° C. at a rate of 10 ° C. for 1 hour. The phase separation temperature of this polyketone solution was 52 ° C. The ratio of the solvent component is L / Z = 0.45, (Z + L) / (Z + L + X +
W) = 0.32, (Z + L + X) / (Z + L + X + W)
= 0.62.

The polyketone solution thus obtained was passed through a 20 μm filter, and then a spinneret having 50 holes with a diameter of 0.2 mm was used to obtain 80 by using a plunger type extruder.
It was extruded at a speed of 90 m / min. After passing through an air gap having a length of 10 mm and then passing through a coagulation bath made of water having an immersion length of 50 cm and a temperature of 2 ° C., it was pulled up using a Nelson roll at a speed of 90 m / min. Then
90% of the Nelson roll was washed by spraying with 1% hydrochloric acid and water and dried at 220 ° C in a roll dryer.
Rolled up in minutes. This gel spinning was carried out for 1 hour, but no trouble such as single yarn breakage or cutting was observed. This fiber was subjected to three-stage drawing at 225 ° C. to 7.0 times, 240 ° C. to 1.5 times, and 250 ° C. to 1.4 times to obtain a polyketone fiber. The fiber thus obtained has a fineness of 101 dtex and a strength of 17.9.
cN / dtex, elongation 5.2%, elastic modulus 451 cN
/ Dtex.

[0039]

Comparative Example 1 An aqueous solution having a mass ratio of zinc chloride / lithium chloride / calcium chloride / water of 22/4/36/38,
The polyketone represented by the formula (1) was mixed at 30 ° C. so that the intrinsic viscosity was 5.5 and substantially 100 mol% of the repeating unit was 6.5% by mass, and the pressure was reduced to 6.7 kPa. After leaving it for 30 minutes, it was sealed under reduced pressure and stirred at 85 ° C. for 2 hours to obtain a uniform and transparent polyketone solution. A part of this polyketone solution was transferred to a sample cell, and the light transmittance was measured while cooling the temperature of the solution from 85 ° C. at a rate of 10 ° C. for 1 hour. The phase separation temperature of this polyketone solution was 30 ° C. The ratio of solvent components is
L / Z = 0.18, (Z + L) / (Z + L + X + W) =
0.26, (Z + L + X) / (Z + L + X + W) = 0.
62.

The obtained polyketone solution was passed through a 20 μm filter, and then a spinneret having 50 holes with a diameter of 0.2 mm was used to obtain 80 by using a plunger type extruder.
It was extruded at a speed of 90 m / min. After passing through an air gap having a length of 10 mm and then passing through a coagulation bath made of water having an immersion length of 50 cm and a temperature of 2 ° C., it was pulled up using a Nelson roll at a speed of 90 m / min. Then
The Nelson roll was washed by spraying with 1% hydrochloric acid and water, and dried through a roll dryer at 220 ° C., then 90
It was wound up at m / min. This gel spinning was performed for 1 hour,
Single yarn breakage occurred and spinning was unstable. 2 this fiber
Four-stage drawing was performed at 25 ° C. to 7.0 times, 240 ° C. to 1.5 times, 250 ° C. to 1.3 times, and 257 ° C. to 1.2 times to obtain a polyketone fiber. The fineness of the obtained fiber is 86 dte.
x, strength 12.9 cN / dtex, elongation 5.2%,
The elastic modulus was 325 cN / dtex.

[0041]

Comparative Example 2 An aqueous solution having a zinc chloride / calcium chloride / water mass ratio of 22/40/38 had an intrinsic viscosity of 5.5.
At about 30 ° C. so that substantially 100 mol% of the repeating unit is 6.5% by mass of the polyketone represented by the formula (1).
The mixture was mixed with, and the pressure was reduced to 6.7 kPa. After leaving for 30 minutes,
It was sealed under reduced pressure and stirred at 85 ° C. for 2 hours to obtain a uniform and transparent polyketone solution. Transfer a portion of this polyketone solution to the sample cell and increase the temperature of the solution to 1
The light transmission was measured while cooling from 85 ° C at a rate of 10 ° C over time. The phase separation temperature of this polyketone solution is 2
It was 5 ° C. The ratio of the solvent component is L / Z = 0, (Z +
L) / (Z + L + X + W) = 0.22, (Z + L + X)
/(Z+L+X+W)=0.62.

After passing the obtained polyketone solution through a filter of 20 μm, the polyketone solution was passed through a spinneret having 50 holes of 0.2 mm in diameter to 80 by using a plunger type extruder.
It was extruded at a speed of 90 m / min. After passing through an air gap having a length of 10 mm and then passing through a coagulation bath made of water having an immersion length of 50 cm and a temperature of 2 ° C., it was pulled up using a Nelson roll at a speed of 90 m / min. Then
The Nelson roll was washed by spraying with 1% hydrochloric acid and water, and dried through a roll dryer at 220 ° C., then 90
It was wound up at m / min. This gel spinning was performed for 1 hour,
It was unstable due to single yarn breakage and yarn breakage. This fiber is 7.0 times at 225 ℃, 1.5 times at 240 ℃, 250 ℃
Was stretched at 1.3 times and at 1.1 times at 257 ° C. to obtain a polyketone fiber. The fineness of the obtained fiber is 94 dte.
x, strength 12.4 cN / dtex, elongation 5.2%,
The elastic modulus was 311 cN / dtex.

[0043]

Comparative Example 3 An aqueous solution having a mass ratio of zinc chloride / sodium chloride / water of 58/10/32 had an intrinsic viscosity of 5.5.
At about 30 ° C. so that substantially 100 mol% of the repeating unit is 8.0% by mass of the polyketone represented by the formula (1).
The mixture was mixed with, and the pressure was reduced to 6.7 kPa. After leaving for 30 minutes,
It was sealed under reduced pressure and stirred at 85 ° C. for 2 hours to obtain a uniform and transparent polyketone solution. Transfer a portion of this polyketone solution to the sample cell and increase the temperature of the solution to 1
The light transmission was measured while cooling from 85 ° C at a rate of 10 ° C over time. The phase separation temperature of this polyketone solution is 5
It was 5 ° C. The ratio of the solvent component is L / Z = 0, (Z +
L) / (Z + L + X + W) = 0.58, (Z + L + X)
/(Z+L+X+W)=0.69.

The polyketone solution obtained was passed through a 20 μm filter, and then a spinneret having 50 holes with a diameter of 0.2 mm was used to obtain 80 by using a plunger type extruder.
It was extruded at a speed of 90 m / min. After passing through an air gap having a length of 10 mm and then passing through a coagulation bath made of water having an immersion length of 50 cm and a temperature of 2 ° C., it was pulled up using a Nelson roll at a speed of 90 m / min. Then
The Nelson roll was washed by spraying with 1% hydrochloric acid and water, and dried through a roll dryer at 220 ° C., then 90
It was wound up at m / min. This gel spinning was performed for 1 hour,
The yarn was frequently cut and unstable. 2 this fiber
Four-stage drawing was performed at 25 ° C. to 7.0 times, 240 ° C. to 1.5 times, 250 ° C. to 1.3 times, and 257 ° C. to 1.2 times to obtain a polyketone fiber. The fineness of the obtained fiber is 98 dte.
x, strength is 11.0 cN / dtex, elongation is 5.2%,
The elastic modulus was 270 cN / dtex.

[0045]

The solvent used in the polyketone solution of the present invention has low toxicity, nonflammability, and excellent solvent recoverability.
The polyketone solution using this solvent can perform gel spinning at high speed. Therefore, it is cheaper and has high strength.
High modulus polyketone fibers can be produced. In addition, single yarn fusion does not easily occur during hot drawing, and it is possible to produce a polyketone fiber having excellent quality. The obtained polyketone fiber can be developed as a high performance rubber reinforcing material and a plastic reinforcing material, and is particularly effective in reducing the weight of tires.

Claims (4)

[Claims] 1. A solution in which 95 mol% or more of repeating units are dissolved in a polyketone represented by the chemical formula (1) in a solvent, wherein the solvent has a mass of zinc chloride of Z, a mass of lithium chloride of L, zinc chloride and A polyketone solution that is an aqueous solution that satisfies the following mathematical relationship, where X is the mass of a metal salt other than lithium chloride and W is the mass of water. 0.2 ≦ L / Z ≦ 1.5 0.2 ≦ (Z + L) / (Z + L + X + W) ≦ 0.7 0.5 ≦ (Z + L + X) / (Z + L + X + W) ≦ 0.7 [Formula 1] 2. The polyketone solution according to claim 1, which has a phase separation temperature in a temperature range of 10 to 150 ° C. 3. The polyketone solution according to claim 1, wherein the metal salt other than zinc chloride and lithium chloride is calcium chloride. 4. A coagulation bath in which the polyketone solution according to any one of claims 1 to 3 is discharged from the spinneret at a temperature higher than the phase separation temperature of the polyketone solution, and at a temperature lower than the phase separation temperature by 10 ° C. or more. A method for producing a polyketone fiber, comprising extruding and solidifying to form a fibrous substance, removing a part or all of the solvent from the fibrous substance, and then hot stretching.