JP3983255B2 - Fiber reinforced composite material - Google Patents

Description

The present invention relates to a polyketone solution, a fiber using the same, and a method for producing the same. More specifically, the present invention relates to a polyketone solution which is excellent in low toxicity, nonflammability, spinning stability and solvent recoverability and is inexpensive, a wet spinning method using the solution, and a fiber obtained by the method.

In recent years, carbon monoxide and olefins such as ethylene and propylene are polymerized using a transition metal complex such as palladium or nickel as a catalyst to obtain a polyketone in which carbon monoxide and the olefin are substantially alternately copolymerized. (Non-Patent Document 1)
. Many researchers have studied the application of polyketone as a fiber for industrial materials. Reinforcing fibers such as tire cords and belts that utilize high strength, high elastic modulus, dimensional stability at high temperatures, adhesion, and creep resistance. Application to composite material fibers such as concrete reinforcing fibers is expected.

When polyketone is melted, it easily undergoes thermal crosslinking. Therefore, it is preferable to apply wet spinning when making fibers. In particular, a polyketone (poly (1-oxotrimethylene), hereinafter abbreviated as ECO), which is obtained only from carbon monoxide and ethylene, which can exhibit high mechanical properties, is easily melted by heat. Spinning is extremely difficult, and the fiber can be obtained substantially only by wet spinning.
When the polyketone is wet-spun, hexafluoroisopropanol, phenolic solvents such as m-cresol and resorcin / water, and organic solvents such as resorcin / carbonate are known. However, these solvents have had great problems when implemented on an industrial scale.

For example, Patent Document 1 and Patent Document 2 disclose a wet spinning method of an aliphatic polyketone and disclose the use of hexafluoroisopropanol, m-cresol and a mixture thereof as a solvent. In particular, Patent Document 2 discloses that the characteristics of solvents including these solvents include a dipole moment of 3 × 10 −30 to 9 × 10 −30 coulomb meter, and a Hildebrand solubility parameter of 16 to 27 MPa-1 / 2. It is disclosed that a solvent becomes a polyketone solvent. However, hexaisofluoropropanol is very expensive, and it cannot be industrially profitable even with a slight loss in recovery, and it is highly toxic and has a low boiling point. Because it is necessary, it cannot be used industrially.
In addition, m-cresol can be a solvent for aliphatic polyketone, but it has poor dissolving power and must be shared with hexafluoroisopropanol. It is highly toxic and has a strong phenol odor. There is a need to. Furthermore, the mechanical properties of fibers obtained using these solvents are low, and the rate of desolvation from a solution using these solvents is too low. there were.

Patent Document 3, Patent Document 4, and Patent Document 5 disclose the use of at least one solvent that is an aromatic alcohol. Specific examples include resorcin / water, phenol / acetone, and hydroquinone. / Propylene carbonate, resorcin / propylene carbonate. However, these aromatic alcohols are also highly toxic and have a strong phenol odor. Therefore, it is necessary to make the spinning equipment completely sealed. Further, when a flammable organic solvent is used as a co-solvent, explosion-proof equipment is required. Further, the solubility of ECO in these solvents is not always sufficient, and the polymer concentration of the obtained dope cannot be increased, and it is difficult to obtain high strength. Also, with resorcin / water, the water removal rate is too slow for water coagulation,
Methanol had to be used in the coagulation bath, and the spinning equipment and solvent recovery equipment had to use expensive and complicated equipment.

JP-A-2-112413 Japanese National Patent Publication No. 4-505344 JP-A-4-228613 Japanese National Patent Publication No. 7-508317 Japanese National Patent Publication No. 8-507328 Industrial Materials, December Issue, Page 5, 1997

The problems to be solved by the present invention are not achieved with the known polyketone solvents described above, and are low in toxicity, nonflammability, spinning stability, excellent solvent recoverability, and inexpensive to industrially wet spinning. It is to provide a polyketone solution that can be applied, a method for producing polyketone fiber by applying wet spinning to the polyketone solution, and a polyketone fiber.

In order to solve the above-mentioned problems, the present inventors have studied in detail the solubility of polyketones for a large number of solvents, and as a result, an aqueous solution containing a very limited specific salt even though the polyketone is hydrophobic. As a result of further investigation, the present inventors have reached the present invention.
That is, according to the present invention, in a polyketone solution that is a copolymer of carbon monoxide and olefin, 90% by weight or more of the copolymer is a carbon monoxide unit and an olefin unit.
The present invention relates to a solution of the polyketone, which is at least one aqueous solution selected from the group consisting of zinc salts, calcium salts, thiocyanates, and iron salts, a method for producing polyketone fibers using the same, and polyketone fibers.

The polyketone used in the present invention is a copolymer comprising 90% by weight or more of carbon monoxide units and olefin units. Here, the carbon monoxide unit refers to a carbonyl group generated by reaction of carbon monoxide, and the olefin unit is an alkylene group generated by reaction of olefin. Accordingly, the polyketone used in the present invention is a polymer comprising 90% by weight or more of a carbonyl group and an alkylene group. The hydrogen of the alkylene group may be substituted with a hydroxyl group, a carboxyl group, an ester group, an ether group, a halogen element or the like. If it is less than 10% by weight, it may have units other than ketones. Carbon monoxide units and olefin units may be random or alternating, but the strength, elastic modulus, adhesion, dimensional stability as fibers,
In view of excellent creep resistance and light resistance, a polyketone obtained by alternating copolymerization of carbon monoxide and olefin represented by the structural formula (1) is particularly preferable.

ここで、Ａはアルキレン基を示す。 Structural formula (1)

Here, A represents an alkylene group.

That is, the preferred polyketone of the structural formula (1) is a polymer in which carbonyl groups derived from carbon monoxide are alternately arranged with alkylene groups derived from olefins. In this polymer, carbonyl groups and alkylene groups may be partially connected, but 95% by weight or more is a completely alternating copolymer of carbon monoxide and olefin, that is, an alkylene group is followed by a carbonyl group. From the viewpoint of improving heat resistance and light resistance, a polyketone composed of a copolymer in which is bonded and an alkylene group is bonded next to the carbonyl group is preferred. Of course, the higher the content of the part in which the carbon monoxide and the olefin are completely alternately copolymerized in the polymer, the better, preferably 97% by weight or more, and most preferably 100% by weight.

The polyketone used in the present invention may be a copolymer of carbon monoxide and one olefin or a copolymer of two or more olefins. Specific examples of the olefin used include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, dodecene, styrene, methyl acrylate, methyl methacrylate, vinyl acetate, undecenoic acid, undecenol, 6-chlorohexene. , N-vinylpyrrolidone and the like. As a polyketone obtained by using these olefins, a polyketone substantially composed of alternating copolymer units of only carbon monoxide and ethylene has a viewpoint of high strength, high elastic modulus, and excellent dimensional stability at high temperature. To most preferred. Further, from the viewpoint that the solubility in the solvent of the present invention is particularly excellent, the olefin constituting the polyketone is 0.
. A polyketone containing 1 to 10 mol%, preferably 4 to 8 mol% of propylene, in which alternating units of carbon monoxide and ethylene and alternating units of carbon monoxide and propylene are mixed is preferable.

These polyketones may contain additives such as antioxidants, gelation inhibitors, matting agents, flame retardants, ultraviolet absorbers, optical brighteners, and metal soaps depending on the purpose.
About the manufacturing method of the polyketone used for this invention, a well-known method can be used as it is or amended. For example, carbon monoxide and an olefin such as ethylene or propylene, a Group VIII transition metal compound such as palladium, nickel or cobalt, structural formula (2)
The polyketone used in the present invention can be synthesized by polymerizing in the presence of a phosphorus bidentate ligand represented by the formula (1) and a catalyst comprising an anion of an acid having a pKa of 4 or less.
Structural formula (2) R1R2P-R-PR3R4
(Here, R1, R2, R3 and R4 are different or similar organic groups having 1 to 30 carbon atoms, and R is an organic group having 2 to 5 carbon atoms.)

Examples of the Group VIII transition metal compound include palladium, nickel, cobalt, iron, rhodium, ruthenium, osmium, iridium, platinum and the like. From the viewpoint of polymerization activity, palladium, nickel, and cobalt are preferable, and palladium is particularly preferable. is there. The catalyst is preferably used as a carboxylate, in particular as acetate.
As for the phosphorus-based bidentate ligand of the structural formula (2), R1, R2, R3 and R4 are unsubstituted phenyl groups, or at least one of R1, R2, R3 and R4 is bonded to the phenyl group. It is preferably a phenyl group containing one or more alkoxy groups located in the ortho position relative to the phosphorus element. R connecting two phosphorus atoms is preferably a trimethylene group. Examples of the acid having a pKa of 4 or less include trifluoroacetic acid, difluoroacetic acid, trichloroacetic acid, p-toluenesulfonic acid, and the like.

The specific example of the manufacturing method of the polyketone used for this invention is illustrated below.
Polymerization is carried out in a lower alcohol such as methanol or ethanol, a Group VIII transition metal compound such as palladium, nickel or cobalt, a phosphorus bidentate ligand represented by the structural formula (2), and a pKa of 4 or less. A catalyst comprising an acid anion is added, and carbon monoxide and an olefin are introduced into this solution. The molar ratio of carbon monoxide to olefin is preferably 5: 1 to 1: 2. The Group VIII transition compound used for the catalyst is, per mole of olefin used for the polymerization,
It is preferable from the viewpoint of catalytic activity that the amount of metal element is 10-8 to 0.1 molar equivalent. In particular, the purpose of the present invention is to set the amount of the Group VIII transition metal compound so that the total amount of palladium, nickel and cobalt contained in the resulting polyketone is 100 ppm or less in the polyketone. Is preferred.

The phosphorus bidentate ligand represented by the structural formula (2) is used in an amount of 0.1 to 20 mol, preferably 1 to 3 mol, per mol of the Group VIII transition metal compound from the viewpoint of polymerization activity. preferable. The acid having a pKa of 4 or less is preferably 0.01 to 150 equivalents, particularly preferably 1 to 50 equivalents, per gram atom of the Group VIII transition metal compound. Also, polymerization is
It is preferable to carry out at 50 to 150 ° C. and a pressure of 4 to 10 MPa, usually 10 minutes to 20 days.
In order to maintain the catalytic activity during polymerization and to increase the heat resistance of the obtained polyketone, quinones such as 1,4-benzoquinone and 1,4-naphthoquinone are added to the number of moles of the catalytic metal element. On the other hand, you may add 0.1-100 times.
The obtained polyketone-containing composition is filtered, washed to wash away the catalyst, quinone and the like, and then dried and isolated.
The production of the polyketone is carried by supporting the catalyst shown above on a polymer, an inorganic powder, etc.
So-called gas phase polymerization may be used, and this method is rather preferable because the catalyst hardly remains in the polyketone.

The polyketone thus obtained is subjected to elemental analysis and the like, and the elemental amounts of palladium, nickel and cobalt contained in the polyketone are measured. If the total amount is 100 ppm or less, it can be used as it is in the spinning step described later. However, if it exceeds 100 ppm,
It is recommended to perform an operation to reduce the amount of palladium, nickel and cobalt contained in the polyketone. The method for reducing the amount of these metals is not particularly limited. For example, the obtained polyketone is repeatedly washed 1 to 20 times using a solvent, and the amount of palladium, nickel and cobalt is reduced to 100 ppm or less. Examples of the method and other methods include a method in which a polyketone is dispersed in a solvent and carbon monoxide or a phosphorus-based ligand is introduced to form a metal carbonyl complex or a metal phosphorus complex to elute the metal.

Examples of the solvent used in the above method include alcohols such as methanol, ethanol and propanol, ethers such as dioxane, tetrahydrofuran and diethyl ether, acetone,
Examples include ketones such as methyl ethyl ketone, hydrocarbons such as pentane, hexane, and petroleum ether. The washing temperature is not particularly limited, but is, for example, 0 to 80 ° C. Although the washing time is not limited, for example, it is 10 seconds to 1 hour per time. Performing the washing operation in this way, again measuring the amount of palladium, nickel and cobalt, if the total amount is 100 ppm or less,
It can be used for the spinning process.

The polyketone solution of the present invention is a polyketone solution which is a copolymer of carbon monoxide and an olefin, wherein 90% by weight or more of the copolymer is a carbon monoxide unit and an olefin unit, and the solvent is a zinc salt or a calcium salt. , Thiocyanate, and at least one aqueous solution selected from the group consisting of iron salts. Here, the solution is an aqueous solution containing a salt in which a polyketone is dissolved, and the solvent is an aqueous solution in which a salt is dissolved for dissolving the polyketone. The Hildebrand solubility parameter of these aqueous solutions is 47 MPa-1 / 2 or more. As the zinc salt, calcium salt, thiocyanate, and iron salt, those that dissolve in water at 30% by weight or more, preferably 50% by weight or more are preferable.

Specifically, zinc salts include zinc chloride, zinc bromide, zinc iodide, zinc nitrate, zinc sulfate, zinc chlorite, etc., and calcium salts include calcium bromide, calcium iodide,
Examples include thiocyanate such as zinc thiocyanate, aluminum thiocyanate, ammonium thiocyanate, calcium thiocyanate, potassium thiocyanate, magnesium thiocyanate, sodium thiocyanate, and barium thiocyanate. Includes iron bromide, iron iodide, iron chloride and the like. Among these salts, zinc chloride, zinc bromide, zinc iodide, and calcium bromide are more preferable in terms of the solubility of the polyketone, the cost of the solvent, and the stability of the aqueous solution, and zinc chloride is particularly preferable.

The polyketone solution of the present invention may be mixed with a plurality of salts for the purpose of improving solubility, reducing costs, stability of the polyketone solution, and the like. Moreover, other inorganic substance and organic substance may be included in the range which does not inhibit the objective of this invention. For example, a polymer other than polyketone and / or an organic substance may be included. Although there is no restriction | limiting in particular as these content, Usually, it is 70 weight% or less.
The water used in the solution is not particularly limited as long as it can be used industrially, and any water such as drinking water, river water, ion-exchanged water can be used. Furthermore, an organic solvent such as methanol, ethanol, ethylene glycol, acetone, dimethyl sulfoxide, or N-methylpyrrolidone may be contained within 50% by weight of water as long as the ability to dissolve the polyketone is not impaired.

The concentration of zinc salt, calcium salt, thiocyanate, and iron salt in the solvent used in the polyketone solution of the present invention is 5 to 85% by weight, preferably 3 in order to obtain sufficient solubility.
It is 0-85 weight%, More preferably, it is 45-75 weight%, More preferably, it is 67-75 weight%. In addition, the density | concentration of each salt said here is a value defined by the following formula | equation. The weight of the solvent is
The polyketone is not contained, and the weight of the aqueous solution containing the salt is shown.
Salt concentration (% by weight) = (weight of salt / weight of solvent) × 100

Among the solvents used in the present invention, the aqueous zinc halide solution is the most excellent solvent for polyketone due to its high solubility, but when an aqueous solution containing only a salt of zinc halide is used as the solvent for the polyketone, the polymer obtained When the viscosity of the solution tends to be too high, increasing the polymer concentration makes it difficult to defoam or requires an expensive and special extruder or dissolution device to prepare a high viscosity solution There is. Further, when coagulation is performed through an aqueous coagulation bath, yarn breakage tends to occur because the strength of the coagulated yarn containing moisture is low.
Furthermore, when the polyketone was dissolved in an aqueous zinc halide solution, the solution became yellowish, and the degree of coloration became worse over time, and the coloration of such a polyketone solution resulted in fiber coloration. It becomes a factor of degrading the quality of the fiber.

Such a problem can be solved by adding a specific water-soluble salt to the aqueous zinc halide solution. That is, an aqueous solution containing at least one kind of zinc halide as a solvent and at least one kind of metal salt other than the zinc halide and dissolved in water at 50 ° C. in an amount of 1% by weight or more is used.
Here, at least 1 which is other than zinc halide and dissolves 1% by weight or more in water at 50 ° C.
The seed metal salt is not particularly limited as long as it is a metal salt other than zinc halide and dissolves in water at 50 ° C. in an amount of 1 wt% or more. Halogenated salts and sulfates of typical metal elements or transition metal elements Any of inorganic salts such as phosphates and nitrates, and organic metal salts such as acetates, formates and sulfonates may be used. However, when zinc halide and anion elements are used in common, there is an advantage that they can be easily recovered. Metal halide salts other than zinc halide are preferred. In addition, as a kind of metal,
From the viewpoint that the degree of decrease in the solution viscosity of the resulting polymer solution is large, alkali metal halides and alkaline earth metal halides are preferred.

In this case, from the viewpoint of facilitating recovery, the same halogen as that used for zinc halide is preferably used for the anion, and chloride is particularly preferable. Preferred examples include sodium chloride, calcium chloride, lithium chloride, barium chloride, sodium bromide, calcium bromide, lithium bromide, barium bromide, sodium iodide, calcium iodide, lithium iodide, barium iodide and the like. In particular, sodium chloride, calcium chloride from the viewpoint of the magnitude of viscosity reduction of the polymer solution, spinning stability, low coloration of the resulting fiber, ease of recovery, metal salt stability, and cost. Barium chloride is preferable, and sodium chloride and calcium chloride are particularly preferable. Further, as defined as at least one metal salt, a plurality of types of metal salts may be used in combination.

The amount of at least one zinc halide contained in the solvent is 5 because of its good solubility.
-75% by weight is preferred, more preferably 20-70% by weight, particularly preferably 45-70%.
% By weight. Alternatively, the ratio of zinc halide to at least one metal salt other than the zinc halide and dissolved in water of 50 ° C. in an amount of 1% by weight or more is 98 from the viewpoint of reduction in polymer solution viscosity and suppression of coloring. / 2 to 20/80 is preferable, more preferably 90/10 to 66/3.
4. At least one zinc halide in the solution and at least one metal salt other than the zinc halide and dissolved in water of 50% by weight or more may react in the solution. For example, when zinc chloride and sodium chloride are used, a zinc tetrachloride complex is formed depending on dissolution conditions, but such a state may be obtained.

The polymer concentration in the polyketone solution of the present invention is preferably 0.005 to 70% by weight. If the polymer concentration is less than 0.005% by weight, the concentration is too low, and there is a drawback that it is difficult to become a fiber at the time of coagulation. On the other hand, if it exceeds 70% by weight, the polymer no longer dissolves in the solvent. From the viewpoints of solubility, ease of spinning, and fiber production cost, it is preferably 0.5 to 40% by weight, more preferably 1 to 30% by weight.
The polymer concentration referred to here is a value defined by the following equation.
Polymer concentration (wt%) =
(Weight of polymer / (weight of polymer + weight of solvent)) × 100

The polyketone solution of the present invention comprises at least 90% by weight of a polyketone, which is a copolymer of carbon monoxide units and olefin units, selected from the group consisting of zinc salts, calcium salts, thiocyanates, and iron salts. It can be added to an aqueous solution containing one species at a time or in several batches while stirring, and then the stirring operation is continued to dissolve substantially completely. The form of the polyketone is not particularly limited, such as powder and chips, but powder is preferable from the viewpoint of dissolution rate and a small amount of thermal cross-linked product generated in the polymerization process.

Although the temperature at the time of dissolution is not particularly limited, it is usually 5 to 5 from the viewpoint of dissolution rate and solvent stability.
200 degreeC, Preferably it is the range of 30-150 degreeC. Depending on the type and combination of metals, the added metal salt itself, or a metal salt or complex produced by reaction of two or more metal salts with each other may crystallize and precipitate when the temperature is lowered. In such a case,
It is important to perform melting and spinning at a temperature at which crystals do not precipitate. The dissolution is preferably performed under reduced pressure so that bubbles do not enter the obtained polyketone solution. The degree of decompression is not particularly limited, but is preferably 700 torr or less, more preferably 100 torr or less, and most preferably 50 torr or less.

As a dissolution method, for example, a known method such as stirring with a stirring blade, stirring using a single or twin screw extruder, stirring using ultrasonic waves, and the like can be applied.
The polyketone solution thus obtained becomes a homogeneous solution through a filter as necessary in order to remove dust, gelled products, a small amount of undissolved polymer, catalyst residues and the like.
The polyketone solution of the present invention becomes a fiber excellent in strength and elastic modulus by wet spinning. That is, after extruding the polyketone solution of the present invention from the spinneret and subsequently removing some or all of the salt from the obtained fibrous material, the fibrous material is stretched in the range of 0 to 300 ° C. High performance fibers can be produced.

As a method for removing the metal salt from the fibrous material, for example, a method of extruding into a solvent that is less soluble in polyketone than the solvent used in the present invention is preferable. As such a low-solubility solvent, a metal salt solution having a lower concentration than the solvent used in the present invention is preferable, and water, an acidic aqueous solution, an alkaline aqueous solution, or the like is particularly preferable. When passing the fibrous material through the coagulation solvent, it is preferable to pass it while pulling at a constant speed. The speed at this time is not particularly limited, but is usually 0.001 to 3000 m / min.

The fiber from which the metal salt has been removed is preferably subjected to a drying step in order to remove a liquid typified by water. When performing the drying, the fiber from which the metal salt containing moisture is removed,
Even if it winds up once and dries, after drying without winding up, you may use for an extending process as it is. The drying step is preferably performed in an atmosphere of 10 to 300 ° C., and not only drying of the foot length but also stretching and relaxation of 1.1 to 10 times may be performed as necessary. The fiber that has undergone the drying step is subjected to a drawing step to become drawn yarn. The draw ratio is 1.1 times or more, preferably 3 times or more, and more preferably 6 times or more. Stretching is performed at 0 to 300 ° C., preferably 150 to
It can be carried out at a temperature of 300 ° C. in one or more stages.

More preferable wet spinning methods include the following methods.
The polyketone solution of the present invention is passed through a filter as necessary to remove dust, gelled product, a small amount of undissolved polymer, catalyst residue, etc. Use fibrous material. The coagulation bath has a role of removing a part or all of the metal salt from the polyketone solution and changing the state so that the polyketone is not dissolved in the solvent filled in the coagulation bath to maintain the fiber shape. As the solvent used in the coagulation bath, a solvent composed of 50% by weight or more of water is preferable in that the desalting rate is high. For example, when an aqueous solution containing zinc halide and at least one metal salt other than the zinc halide and dissolved in water at 50 ° C. by 1 wt% or more is used as the solvent, the solvent used in the coagulation bath is water, It is an aqueous solution containing less than 50 wt% of zinc halide and / or at least one metal salt other than the zinc halide and dissolved in water of 50 ° C. by 1 wt% or more.

Of course, it may contain an organic solvent such as methanol, acetone and methyl ethyl ketone, hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid and the like in the range of 50% by weight of droplets. Two or more of these solvents may be mixed as necessary. Particularly preferred is a substantially 100% water or an aqueous solution containing 1 to 45% by weight of the salt used in the solvent from the viewpoint that the salt used in the solvent can be removed from the fibrous material as much as possible. The temperature of the coagulation bath is not particularly limited, but is preferably 20 ° C. or higher, particularly preferably 4 from the viewpoint that the salt used in the solvent can be removed quickly from the fibrous material.
It is 0 degreeC or more, More preferably, it is 50-95 degreeC. The amount of the solvent used in the coagulation bath is preferably at least 1 time, more preferably at least 30 times the amount of polyketone discharged per hour.

The fibrous material thus solidified may be washed at least once with water or an aqueous solution having a pH of 4 or less as necessary. Such washing is a preferred method for dissolving metal salts that could not be removed in the coagulation bath. In particular, when an aqueous zinc chloride solution is used as a polyketone solvent, a zinc salt that is difficult to dissolve in water is produced when zinc chloride is once dissolved in water and then diluted with water. In order to remove this zinc salt, it is very effective to further wash with a large amount of water, or preferably with an aqueous solution having a pH of 4 or less, such as an aqueous solution of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or the like. It is. Moreover, in order to improve the solubility of the zinc salt which is difficult to dissolve in water, the temperature of the washing water is set to 40 ° C. or higher, preferably 50 to 95 ° C.

In the coagulation and washing as described above, zinc, calcium contained in the obtained fibrous material,
The amount of at least one element selected from the group consisting of iron is 10000 out of the total dry fiber content.
It is preferable to make it ppm or less, which is an important condition for increasing the strength and elastic modulus of the finally obtained fiber. This is because if the amount of the metal element used in the solvent is more than 10,000 ppm, it is difficult to stretch at a high magnification for expressing high strength and elastic modulus in the next stretching process.

Since the fibrous material from which the salt has been removed in this manner contains a large amount of water, it is preferably dried at a temperature of 50 ° C. or higher to remove a part or all of the water. As a drying method, drying may be performed while stretching, at a constant length, or while shrinking. Although it can set arbitrarily as temperature at the time of drying according to the target degree of drying, it is 50-250 degreeC normally, Preferably, it is 50-15.
0 ° C. The apparatus for drying may be a known facility such as a tunnel dryer, a roll heater, or a net process dryer. The fiber thus dried is stretched 3 times or more, and further 6 times or more to be a drawn yarn. The stretching is preferably performed at 50 ° C. or more for ease of stretching, and more preferably at a temperature of 150 to 300 ° C., in one or more stages. In order to suppress the friction between the fiber and the drawing machine and the generation of static electricity and smooth the drawing, it is preferable to apply a finish at any stage from drying to drawing. A well-known thing can be used as a finishing agent.

The above-described method for producing a polyketone fiber of the present invention is extremely effective in consideration of a recovery step of a salt used as a solvent. That is, the salt used in the solvent can be reused again as a polyketone solvent with almost no loss by removing moisture even when diluted through a coagulation and washing process. Of course, the partially lost salt can be added only in the required amount when reused. That is, at least 1 ppm of salt that has escaped from the fibrous material
A coagulation bath containing, an aqueous solution having a pH of 4 or less, a part or all of the water used as necessary is concentrated, and the salt used in the polyketone solvent is added to the concentrated aqueous solution as necessary to compensate for the loss. The aqueous solution can be reused as a polyketone solvent again. As the concentration operation, a known method can be used, for example, concentration by evaporation of water by heating, concentration using an ultrafiltration membrane method or ion exchange method, neutralization, etc., once insoluble in a solvent, There is no particular limitation on the method of filtering back to the original salt structure.

The polyketone fiber of the present invention thus obtained is a polyketone fiber comprising 90% by weight or more, preferably 95% by weight or more of a complete alternating copolymer of carbon monoxide units and olefin units, preferably ethylene units. The amount of palladium, nickel, and cobalt element contained in is preferably 100 ppm or less.
If the amount of these metal elements exceeds 100 ppm, even if the polyketone is dissolved in an aqueous solution containing zinc halide, the polyketone is thermally crosslinked and the viscosity of the solution increases remarkably. Since the solution viscosity gradually increases, the properties of the obtained fiber may change with the spinning time. Moreover, when the obtained polyketone fiber is heated, problems such as strength, elongation, elastic modulus, reduction in molecular weight, and coloring easily occur. In order not to cause such a problem, it is preferable to reduce the amount of these metal elements as much as possible, specifically 50 ppm or less, more preferably 20 ppm or less, still more preferably 10 ppm or less.

Furthermore, the polyketone fiber of the present invention is a polyketone fiber containing a copolymer of carbon monoxide and an olefin, and 90% by weight or more of the copolymer is a carbon monoxide unit and an olefin unit, and is contained in the fiber. The amount of palladium, nickel and cobalt elements is 100pp
It is preferable that the total content of at least one element selected from the group consisting of zinc, calcium and iron is 10000 ppm or less at the same time. These metal elements remain in the polyketone fiber without being removed from the metal salt aqueous solution used as a solvent.
If the amount of these metal elements exceeds 10,000 ppm, it becomes a fiber that is difficult to be stretched, and it is difficult to increase the stretch ratio, resulting in a disadvantage that the strength and elastic modulus are lowered. The reason for this is not clear, but it is assumed that stretching is difficult because the metal element crosslinks between or within the polymer molecules. The smaller the amount of metal element, the better. However, in order to achieve a high stretch ratio, it is preferably 3000 ppm or less, more preferably 2000 ppm or less,
More preferably, it is 200 ppm or less.

The fibers with little catalyst residue and metal salt residue obtained in this way exhibit excellent dimensional stability and elastic modulus retention particularly at high temperatures. For example, in dynamic viscoelasticity measurement at a frequency of 110 Hz, 1
The fiber has a storage elastic modulus at 80 ° C. of 80 g / d or more. When polyethylene terephthalate fiber or nylon 66 fiber, which is often used as a fiber for industrial materials, is measured under the same conditions, the storage elastic modulus at 180 ° C. is 50 g / d or less. This difference in storage elastic modulus is extremely large when used at high temperatures. From the viewpoint that physical properties at higher temperatures can be expressed, 18
The storage elastic modulus at 0 ° C. is preferably 100 g / d or more, more preferably 150 g / d.
d or more, most preferably 200 g / d or more.

Moreover, it is preferable that the intrinsic viscosity of the polyketone fiber of this invention is 0.3 or more. This is because if the intrinsic viscosity is less than 0.3, it is difficult to increase the strength because the molecular weight is too low. From the balance of strength, solubility and spinnability of the obtained fiber, it is preferably 0.5 to 15, and most preferably 2 to 13.
Further, the fineness of the polyketone fiber of the present invention is not particularly limited, but usually the single yarn fineness is 0.01 to
10d, the total fineness is 5-5000d. Moreover, any of a long fiber, a short fiber, a monofilament, and a multifilament may be sufficient.

The polyketone fiber of the present invention exhibits characteristics such as high strength, high elastic modulus, high adhesion, dimensional stability at high temperature, excellent creep properties, solvent resistance, and wet heat resistance properties, and at the same time promotes deterioration of polyketone. Because there are few catalyst residues such as palladium, cobalt, nickel and metal salt residues used in solvents, fiber reinforced rubber such as tires and belts, fiber reinforced resin used in building materials, building materials,
It can be used as a reinforcing fiber of a fiber reinforced composite material such as a fiber reinforced resin used in automobiles, ships, sports equipment and the like. That is, when the catalyst residue and the metal salt residue used in the solvent increase,
When used for a long time, the fiber gradually deteriorates and the reinforcing effect is lost. Using polyketone fibers with the catalyst residue or metal amount below a specific amount according to the present invention, the performance of the fiber reinforced composite material exhibiting the excellent mechanical properties and thermal properties of the polyketone fibers is demonstrated for a long time without degrading the durability. It becomes possible to do. The amount of polyketone fiber used is necessary so that 1% by weight or more of the fiber weight used in the composite material exhibits its performance, preferably 20% or more, more preferably 50%.
% Or more.

When the polyketone fiber of the present invention is used as a tire cord, a known method can be used. When used as a tire cord, the single yarn fineness is preferably 1 to 4d, and the total fineness is 500.
~ 3000d is preferred. If necessary, it may be mixed with other fibers such as rayon, polyester fiber, aramid fiber, nylon fiber, steel fiber, etc., but preferably 20% by weight of the total tire cord contained in the tire, preferably 50% by weight or more is preferably used from the viewpoint of performance. The obtained polyketone fiber is twisted to 100 to 10
After applying a twist of 00 T / m, preferably 200 to 500 T / m, and making a weave weave, 10 to 30% of RFL (phenol / formalin latex) liquid is adhered and fixed at least at 100 ° C. The adhesion amount of the RFL resin is preferably 2 to 7% by weight with respect to the fiber weight. The tire cord thus obtained is particularly useful as a carcass material for radial tires. As a method of processing the obtained tire cord into a tire, a known method can be used.

定義式中のｔ及びＴは、純度９８％以上のヘキサフルオロイソプロパノール及び該ヘキ
サフルオロイソプロパノールに溶解したポリケトンの希釈溶液の２５℃での粘度管の流過
時間である。また、Ｃは上記１００ｍｌ中のグラム単位による溶質重量値である。 The present invention will be described in more detail with reference to the following examples, etc., but these do not limit the scope of the present invention.
The measurement method of each measurement value used in the description of the examples is as follows.
(1) Intrinsic viscosity The intrinsic viscosity [η] was determined based on the following defining formula.

In the definition formula, t and T are the flow times of a viscosity tube at 25 ° C. of a diluted solution of hexafluoroisopropanol having a purity of 98% or more and a polyketone dissolved in the hexafluoroisopropanol. C is the solute weight value in grams in 100 ml.

(2) Amounts of elements such as palladium, nickel, cobalt, zinc, etc. Measured by high-frequency plasma emission spectroscopic analysis using a known method.
(3) Strength, strength, elongation and elastic modulus of fiber The strong elongation of the fiber was measured according to JIS-L-1013.
(4) Storage elastic modulus at 180 ° C. Using a sample in which both ends of a fiber 30 mm are tied so as not to sag, using a dynamic viscoelasticity measuring apparatus (RheoVibronDDV-01FP: manufactured by ORIENTEC Co., Ltd.) Measured under conditions. Frequency: 110 Hz, temperature: 20 → 260 ° C., heating rate: 5 ° C./min, measurement interval: 1 time / ° C., amplitude: 16 μm, single waveform, preload weight: 0.1 g
/ D

[ Reference Example 1]
An olefin / carbon monoxide alternating terpolymer composed of ethylene / propylene / carbon monoxide obtained by copolymerizing 6 mol% of propylene having an intrinsic viscosity of 0.5, represented by the following structural formula, at 60 ° C.
Was added to a 70 wt% aqueous solution of zinc chloride with stirring. The polymer dissolved very easily, and a dope having a polymer concentration of 10% by weight was obtained within 30 minutes. The resulting solution showed a slight yellow color. The obtained dope was immediately dropped into a large amount of water, and a fibrillated polymer was recovered. The recovered polymer was thoroughly washed with water to completely remove zinc chloride and dried.
There was no change in the color of the recovered polymer, and when the infrared absorption spectrum and NMR spectrum of the polymer were measured, there was no change in the starting polymer. This indicates that the raw material polymer is completely dissolved without being decomposed into the zinc chloride aqueous solution.

[ Reference Example 2]
Using the same polymer as in Reference Example 1, this was added to a 75 wt% aqueous zinc chloride solution with stirring at 70 ° C. The polymer dissolved very easily, and a dope having a polymer concentration of 20% by weight was obtained within 30 minutes. The resulting dope showed a slight yellow color. The obtained solution was immediately dropped into a large amount of water, and a fibrillated polymer was recovered. The recovered polymer was thoroughly washed with water to completely remove zinc chloride and dried. There was no change in the color of the recovered polymer, and when the infrared absorption spectrum and NMR spectrum of the polymer were measured, there was no change in the starting polymer. This means that the raw polymer does not decompose into an aqueous zinc chloride solution,
It shows complete dissolution.

[ Reference Example 3]
An alternating ethylene / carbon monoxide copolymer (ECO) having an intrinsic viscosity of 2.0 was added to a 75% aqueous zinc chloride solution with stirring at 70 ° C. The polymer dissolves very easily and has a dissolution time of 3
A dope having a polymer concentration of 15% by weight was obtained within 0 minutes. The resulting solution showed a slight yellow color. The obtained solution was immediately dropped into a large amount of water, and a fibrillated polymer was recovered. The recovered polymer was thoroughly washed with water to completely remove zinc chloride and dried. There was no change in the color of the recovered polymer, and when the infrared absorption spectrum and NMR spectrum of the polymer were measured, there was no change in the starting polymer. This indicates that the raw material polymer is completely dissolved without being decomposed into the zinc chloride aqueous solution.
[ Reference Example 4]
The solution obtained in Reference Example 3 was passed through a 20 μm filter, and then passed through a plunger-type extruder with a nozzle diameter of 0.5 mm, and sequentially through a 30% zinc chloride aqueous solution and a water bath at a rate of 5 m / min. The obtained undrawn yarn was drawn in a 250 ° C. oven at a draw ratio of 7 times.
The obtained fiber had a strength of 6 g / d and an elongation of 20%.

[ Reference Examples 5 to 10]
Using an alternating terpolymer of ethylene / propylene / carbon monoxide having an intrinsic viscosity of 0.4 and copolymerized so that the amount of propylene contained in the olefin is 10 mol%, the solvent composition shown in Table 1, the polymer concentration, It melt | dissolved, stirring under temperature conditions, and obtained the polymer solution of each composition within 30 minutes of melt | dissolution time. The obtained polymer solution was immediately dropped into a large amount of water, and a fibrillated polymer was recovered. The recovered polymer was thoroughly washed with water and dried. There was no change in the color of the recovered polymer, and when the infrared absorption spectrum and NMR spectrum of the polymer were measured, there was no change in the starting polymer. Further, as shown in Table 1, there was almost no change in the intrinsic viscosity. This is because the raw material polymer is not decomposed, and Reference Example 5
The aqueous solution of 10 indicates that it can be a solvent for polyketone.

[ Reference Example 11]
An alternating ethylene / carbon monoxide copolymer (ECO) having an intrinsic viscosity of 4.0 was added to a 75 wt% aqueous solution of calcium bromide with stirring at 90 ° C. The polymer dissolves very easily,
A polymer solution having a polymer concentration of 10% by weight was obtained within 30 minutes. The obtained solution was immediately dropped into a large amount of water, and a fibrillated polymer was recovered. The recovered polymer was thoroughly washed with water to completely remove calcium bromide and dried. There was no change in the color of the recovered polymer, and when the infrared absorption spectrum and NMR spectrum of the polymer were measured, there was no change in the starting polymer. Further, the intrinsic viscosity was 4.0 and was not changed. This indicates that the raw polymer is completely dissolved without being decomposed into a 75 wt% calcium bromide aqueous solution.

[ Reference Example 12]
The dope obtained in Reference Example 11 was passed through a 20 μm filter, and then coagulated with a 10 wt% aqueous solution of calcium bromide directly from a spinneret having 50 holes with a diameter of 0.1 mm using a plunger-type extruder. Extruded into the bath at a speed of 2 m / min. Subsequently, it wash | cleaned through the water-washing bath, and wound up on the pipe | tube in the state containing water. This was put into a drier, dried in batches, and the obtained dried yarn was stretched in a 240 ° C. oven at a stretch ratio of 6 times.
The obtained fiber had a strength of 6 g / d and an elongation of 10%.

[ Reference Examples 13 to 22]
While using an alternating ethylene / carbon monoxide copolymer having an intrinsic viscosity of 7.0 and stirring at an aqueous solution mainly composed of zinc chloride having the solvent composition shown in Table 2 so that the polymer concentration does not exceed 80 ° C. at 7% by weight. Dissolved. Dissolution was complete within 30 minutes in each case. Thereafter, the solution viscosity of the obtained solution was measured. Sodium chloride, calcium chloride, sodium sulfate, and barium chloride all dissolve in water at 1% by weight or more at 50 ° C. When an aqueous solution containing them is used as a solvent ( Reference Examples 14 to 22), these are not used ( It can be seen that the solution viscosity (measured at 80 ° C.) is greatly reduced as compared with Reference Example 13). In addition, coloring did not progress greatly even when the solutions of Reference Examples 14 to 22 were allowed to stand at room temperature, but coloring progressed in Reference Example 13 and turned brown after several days. The polymer solutions of Reference Examples 13 to 22 were dropped into a large amount of water and washed sufficiently to completely remove the metal salt and collect the polymer. The recovered polymer had an intrinsic viscosity of about 7.0, and when the infrared absorption spectrum and NMR spectrum were measured, there was no change with respect to the starting polymer. This indicates that the aqueous solutions shown in Reference Examples 13 to 22 can be polyketone solvents.

[ Reference Example 23]
Using the polyketone solution of Reference Examples 13 and 14, extruded from 20 holes with a nozzle diameter of 0.16 mm at a discharge linear velocity of 6.2 m / min, passed through an air gap length of 20 mm, and passed through a water coagulation bath as it was. Further, after passing through a 2% sulfuric acid washing bath, it was further washed with water and wound up. The wound fibers contained water in each case about 400 times the amount of polymer. The mechanical properties of the coagulated yarn were measured. As a result, in the case of Reference Example 13, the strength was 21 g and the elongation was 35%, and in Reference Example 14, the strength was 52 g and the elongation was 115%. Thus, when using an aqueous solution containing only zinc chloride,
Since the toughness of the coagulated yarn was low, yarn breakage occurred during spinning. In contrast, when the polymer solution of Reference Example 14 was used, stable spinning was achieved without yarn breakage. Reference Example 1
When the coagulated yarn obtained from the polymer solution No. 4 was dried at 100 ° C. and then stretched 10 times at 215 ° C., a fiber having a strength of 10 g / d, an elongation of 4%, and an elastic modulus of 300 g / d was obtained. It was.
In addition, the obtained fiber was slightly yellowish. Incidentally, the fiber obtained from the polyketone solution of Reference Example 13 was quite yellow.

[Reference Example 24 ]
Add 1 liter of methanol to a 20 liter autoclave.
. A catalyst solution prepared by previously stirring 141 mmol, bis (2-methoxyphenyl) phosphinopropane 0.0821 mmol, and 1.333 mmol of trifluoroacetic acid in 10 mL of methanol was added. Thereafter, a mixed gas containing 1: 1 mol of carbon monoxide and ethylene was charged, and this mixed gas was continuously added so as to maintain a pressure of 5 MPa.
The reaction was performed at 0 ° C. for 3.5 hours.
After the reaction, the pressure was released, and the obtained white polymer was repeatedly washed with methanol and then isolated. The yield was 73g. The obtained polyketone was ECO by analysis of nuclear magnetic resonance spectrum, infrared absorption spectrum and the like. The intrinsic viscosity was 5.5, and the Pd content was 41 ppm.

Similarly, by changing the amount of catalyst, an intrinsic viscosity of 5.6, an ECO with a Pd content of 105 ppm, an intrinsic viscosity of 5.7 ppm. An ECO with a Pd content of 5 ppm was obtained. In these polyketones, substantially no Group VIII transition metal elements other than Pd element were detected.
The three polyketones obtained in Reference Example 1 were mixed with zinc chloride / sodium chloride / water (weight ratio 65/15
/ 20) was dissolved so that the polymer concentration was 6% by weight. The resulting polymer solution was 80 ° C.
And the increase in solution viscosity was measured for 30 hours. E with a Pd content of 5 ppm and 41 ppm
An increase in viscosity of the polymer solution using CO was hardly observed even after 30 hours.
However, ECO with a Pd remaining amount of 105 ppm increased the solution viscosity by about 40% after holding for 20 hours and about 100% after 30 hours.

[ Reference Examples 25 and 26 ]
ECO having an intrinsic viscosity of 5.6 and a Pd content of 41 ppm prepared in Reference Example 24 was dissolved in zinc chloride / sodium chloride / water (weight ratio: 65/10/25) so that the polymer concentration was 12% by weight. Ejected from a nozzle diameter of 0.16 mm × 20 holes at 80 ° C., passed through a 10 mm air gap, passed through a 1.2 m coagulation bath filled with 10 ° C. water, and then a 2 m wash bath containing 2% aqueous sulfuric acid. Through a Nelson roll that is continuously sprayed with water and then through a drying line at a constant length of 240 ° C. and then listed in Table 3 using a stretcher equipped with a hot plate between the two feed rolls. The film was wound up after first-stage stretching at 240 ° C. and further second-stage stretching at 260 ° C. so that the total draw ratio was reached. Even when spinning was carried out continuously for 20 hours, there was no particular change in spinnability and stretchability, which was good.
The obtained polyketone fibers exhibited excellent mechanical properties as shown in Table 3.
Also, the storage modulus of 180 ° C. was 96 g / d, in Reference Example 26 150 g / d in Reference Example 25.

[Comparative Example 1]
The spinning experiment shown in Reference Example 25 was performed using ECO having an intrinsic viscosity of 5.6 and a Pd content of 105 ppm prepared in Reference Example 24 . Although spinning was able to be performed stably for about 5 hours after the start of spinning, the yarn breakage increased thereafter. Presumably, the thermal cross-linked product partially accumulates, preventing smooth discharge of the polymer solution. In addition, the total stretch ratio could not be increased to the same ratio as in Reference Examples 25 and 26 because the thermal cross-linked product hinders stretching. Moreover, although the strength was lower than that of Reference Example 25 , the elongation was low. Further, the storage elastic modulus at 180 ° C. was 46 g / d.

[ Reference Example 27 ]
The spinning experiment shown in Reference Example 25 was performed using ECO having an intrinsic viscosity of 5.7 and a Pd content of 5 ppm prepared in Reference Example 24 . The drawability was good, and the physical properties of the obtained fiber were good.
[ Reference Example 28 ]
The spinning experiment shown in Reference Example 25 was conducted using the polymer shown in Reference Example 25 through 70 ° C. warm water instead of the 2% sulfuric acid aqueous solution. Compared with Reference Examples 25 and 26 , the amount of zinc contained in the fibers increased, but substantially the same stretchability was exhibited.

[Comparative Example 2]
The spinning experiment shown in Reference Example 25 was performed using the polymer shown in Reference Example 25 , using cold water at 15 ° C. instead of the 2% sulfuric acid aqueous solution as the liquid used in the washing bath. Zinc could not be sufficiently removed from the obtained fiber, and the stretchability was thus inhibited. Therefore, when the total draw ratio was increased to 5 times or more, yarn breakage occurred. The physical properties of the fiber wound up to the limit that can be drawn are shown in Table 3. Since the draw ratio was low, the fiber was low in strength and elastic modulus. Moreover, the storage elastic modulus in 180 degreeC was 75 g / d.

[ Reference Example 29 ]
The liquid used in the coagulating bath in place of 10 ° C. water, zinc chloride 32.5 wt%, sodium chloride 5% by weight, with an aqueous solution of 10 ° C., the length of the coagulation bath in the 4m, Example The spinning method shown in Reference Example 25 was performed using the polymer obtained in 25 . The obtained fiber properties are shown in Table 3. As in Reference Example 25 , fibers excellent in strength and elastic modulus could be obtained stably.
Further, after spinning for 5 hours continuously, the coagulation bath was an aqueous solution containing 35% by weight of zinc chloride and 6% by weight of sodium chloride. This coagulation bath was heated at 120 ° C., boiled off by distilling water, and zinc chloride was added to adjust the concentration to obtain an aqueous solution of zinc chloride / sodium chloride / water (weight ratio 65/15/20). . The polymer used in Reference Example 25 was dissolved again in this aqueous solution, and the spinning experiments of Reference Examples 25 and 26 were repeated. The spinning properties and stretchability were almost the same, and the obtained fiber properties were not changed. This indicates that the solvent used in the present invention is excellent in recoverability.

[Example 1 ]
A 1500 d / 750 f fiber obtained in the same manner as in Reference Example 27 was subjected to 390
Twisting was performed at T / m to obtain a raw cord. RFL having a resin amount of 20% was adhered to this, and passed through a dryer at 130 ° C. and 225 ° C. so that the resin adhesion rate was 5% by weight. A radial tire was created using the tire cord thus obtained.
The radial tire thus obtained was brought into contact with the asphalt surface at 35 ° C. while applying the same contact pressure as that when a 1-ton passenger car traveled at 200 km / hr on the asphalt surface.
The same rotation as when running for hr was performed, and a rotation test for 96 hours was performed as it was.
After 96 hours, the tire cord was taken out from the tire and the strength retention was measured. Example 26
When the polyketone fiber was used, there was almost no decrease in strength compared to the tire cord after RFL treatment. For comparison, the same experiment was conducted using the polyketone fiber of Comparative Example 1, but the strength of the tire cord after the experiment was reduced by about 6%.

[Example 2 ]
The 1500 d / 750 f fiber obtained by the same method as in Reference Example 27 was cut into 50 mm short fibers. After mixing 2 parts by weight of this short fiber, 3 parts by weight of pulp, 57 parts by weight of portlan cement, and 38 parts by weight of silica, wet papermaking was performed and molding at 120 ° C. in an autoclave to prepare a slate plate. The slate plate thus obtained was excellent in strength, and the cross section was observed. As a result, the polyketone fibers were uniformly dispersed. When the solution viscosity of the polyketone fiber taken out from the slate plate was measured, no decrease in viscosity was observed. However, as a comparison, the same experiment was conducted using the polyketone fiber of Comparative Example 1, but the viscosity of the polyketone fiber after the experiment was reduced by about 12%. It is thought that viscosity reduction occurred at the autoclave molding stage.

[Example 3 ]
The polyketone fiber of Reference Example 25 was twisted at 390 T / m for both the lower twist and the upper twist to obtain a raw cord. An epoxy resin was adhered thereto, and a 230 ° C. dryer was passed so that the resin adhesion rate was 5% by weight. A treated cord obtained in this manner was used to produce a B-shaped cogged V-belt having a length of 1016 mm comprising the upper canvas, the compressed rubber layer made of chloroprene rubber, and the lower canvas. This V belt was passed between two pulleys and rotated at 2000 rpm for 24 hours.
After the experiment, the polyketone fiber was taken out of the V-belt and the strength was measured. As a result, the strength did not substantially decrease with respect to the strength after the epoxy treatment. For comparison, the same experiment was performed in Comparative Example 1.
The same experiment was conducted using the polyketone fiber, but the strength of the polyketone fiber after the experiment was about 15%.
% Declined.

[ Reference Example 30 ]
Add 0.33 mmol of bis (cyclooctadiene) nickel (0), 0.33 mmol of 2-mercaptobenzoic acid, 2 mol of toluene, and a mixed gas containing 1: 1 mol of carbon monoxide and ethylene to the autoclave. Filled and polymerized at 5 MPa and 80 ° C. for 15 hours. The resulting polyketone was thoroughly washed with acetone to have an intrinsic viscosity of 4.2 and a nickel content of 12p.
Alternating copolymer of ethylene / carbon monoxide substantially free of pm, palladium and cobalt (E
CO) was obtained.
This polyketone was subjected to wet spinning as in Reference Example 25 . The obtained fiber contained 10 ppm of nickel and 300 ppm of zinc, and showed a strength of 10.2 g / d and an elongation of 4%.

[ Reference Example 31 ]
Reference Example 24 and Reference Example 25 were repeated using cobalt acetate instead of palladium acetate. The resulting polyketone obtained an ethylene / carbon monoxide alternating copolymer (ECO) having an intrinsic viscosity of 3.0, a cobalt content of 41 ppm, and substantially free of palladium and nickel. This polyketone was subjected to wet spinning as in Reference Example 25 . The obtained fiber contained 57 ppm of cobalt and 512 ppm of zinc, showed a strength of 7.2 g / d, and an elongation of 4%.

[ Reference Example 32 ]
An alternating ethylene / carbon monoxide copolymer (ECO) having an intrinsic viscosity of 6.0 was added to an aqueous solution containing 25% zinc chloride and 40% calcium chloride with stirring at 100 ° C. The polymer dissolved very easily, and a solution having a polymer concentration of 3% by weight was obtained. The resulting solution was clear. The obtained solution was immediately dropped into a large amount of water, and a fibrillated polymer was recovered. The recovered polymer was thoroughly washed with water to completely remove zinc chloride and calcium chloride and dried. There was no change in the color of the recovered polymer, and when the infrared absorption spectrum and NMR spectrum of the polymer were measured, there was no change in the starting polymer. This indicates that the raw material polymer is completely dissolved without being decomposed into the aqueous solution.

The present invention provides a low-toxicity, non-flammability, spinning stability, solvent recoverability, inexpensive, industrially useful polyketone solution, a wet spinning method using the solution, and a fiber obtained. It is. Since the polyketone fiber obtained by the present invention is excellent in strength, elastic modulus, durability, and adhesiveness, a tire cord, belt, radiator hose, sling belt, sewing thread, rope,
In addition to being used as an industrial material such as cement reinforcement, it can also be used for general clothing and films.

Claims (4)

A fiber reinforced composite material, wherein a polyketone fiber obtained by wet-spinning a polyketone solution using a metal salt aqueous solution satisfying the following (a) to (d) as a solvent is used: Composite material.
(A) 95 weight% or more is comprised from the polyketone which consists of a complete alternating copolymer of carbon monoxide and ethylene (b) The single yarn fineness is 1-4d (c) Palladium in polyketone fiber, The total content of at least one element selected from the group consisting of nickel and cobalt is 10 ppm or less. (D) The storage elastic modulus at 180 ° C. is 80 g / d or more in the dynamic viscoelasticity measurement at 100 Hz. thing   2. The fiber reinforced composite material according to claim 1, wherein the fiber reinforced composite material is a tire including a tire cord obtained by twisting polyketone fibers at a twist number of 100 to 1000 T / m.   The fiber reinforced composite material according to claim 2, wherein the tire cord is treated with phenol / formalin latex so that the adhesion amount of the phenol / formalin latex resin is 2 to 7% by weight with respect to the fiber weight.   The fiber-reinforced composite material according to claim 1, wherein the fiber-reinforced composite material is a belt including a cord obtained by twisting polyketone fibers at a twist number of 100 to 1000 T / m.