JP2003013326A - Polyketone fiber, method of producing the same and polyketone twisted yarn - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyketone fiber having excellent mechanical properties such as high strength, high elastic modulus, together with free from agglutination of single yarns, low in coefficient of dynamic friction between fiber-fiber, homogeneous and low in defects, having an excellent utilization factor of twisted yarn strength, expressing high strength after twisting and excellent in fatigue resistance, and twisted yarn of the fiber is expected to have a wide range of applications as a high strength industrial material, especially useful as a reinforcing material for rubber, FRP or the like. SOLUTION: This polyketone fiber is made of a polyketone comprising 1- oxotrimethylene composing 95 to 100 wt.% of repeating units and possesses properties meeting the following (a) to (e): (a) a degree of crystallization >=60%; (b) a degree of crystalline orientation >=90%; (c) tensile strength >=10 cN/dtex; (d); rate of agglutination of single yarn <=30%, (e); deposit efficiency of finishing materials = 0.3 to 15 wt.%.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyketone fiber having excellent mechanical properties such as high strength and high elastic modulus, a high melting point, and excellent thermal properties such as high heat resistance, which are fatigue resistance, twist resistance, and
Polyketone fiber with excellent tenacity factor after twisting, and excellent processability during drawing, twisting, and post-processing, and its manufacturing method,
And polyketone twists therefrom. The polyketone fiber of the present invention can be processed into a twisted product and applied to a wide range of applications such as household materials, daily life materials, industrial materials, and particularly industrial material applications where high strength is required as a twisted product, specifically tires. It is extremely useful as a rubber-reinforcing fiber material for ropes, belts, hoses, and ropes.

[0002]

2. Description of the Related Art Recently, it has been known that a polyketone in which carbon monoxide and an olefin are completely alternating-copolymerized can be obtained by polymerizing carbon monoxide and an olefin such as ethylene or propylene using palladium, nickel or the like as a catalyst. Has been. Fibers made of polyketone have high strength,
It has high elastic modulus, high heat resistance, adhesiveness and creep resistance,
It is expected to be applied to industrial materials such as rubber cords for tire cords and belts and fibers for concrete reinforcement. In particular, repeating units of ethylene and carbon monoxide (1
The polyketone containing (-oxotrimethylene) as a main component has high crystallinity and melting point, and has the highest thermal stability such as high strength and high elastic modulus, small change in physical properties at high temperature and small shrinkage. As for this polyketone fiber, many fiberizations have been studied so far.

Specifically, JP-A-2-112413, JP-A-4-228613 and JP-A-4-505
In Japanese Patent No. 344, Japanese Patent Publication No. 7-508317, etc.,
Hexafluoroisopropanol, m-cresol, chlorophenol, resorcin / water, phenol / acetone, propylene carbonate / hydroquinone, pyrrole, resorcin / propylene carbonate, pyridine,
There is known a polyketone fiber which is wet-spun using an organic solvent such as formic acid. However, in these documents, although there is disclosure of a technology for high-strength / high-modulus, high-melting-point polyketone fiber, there is a problem of polyketone fiber having a problem of single thread sticking of polyketone fiber and fiber-fiber friction. There is no disclosure. Only Tokuhyo 7-50831
No. 7 discloses a high-strength polyketone fiber in which single yarn sticking is suppressed by pre-stretching at room temperature after coagulation using a solvent of resorcin / water and a methanol coagulation bath. Only high-strength polyketone multifilaments with low thread sticking are shown,
No mention is made of reducing the frictional resistance of the fibers.

Although such polyketone fiber is certainly high in strength and high in elastic modulus, it does not have a single yarn sticking property, so that the converging property of the fiber is rather deteriorated and the fiber-fiber friction and the fiber-
Friction resistance between metals becomes large, single yarn breaks due to friction resistance during drawing and twisting, fibril-like material is generated by rubbing the fiber surface and entanglement between single yarns, and further the quality of twisted yarn is poor. There is a problem that the mechanical strength and fatigue resistance of the twisted yarn are reduced. In addition, WO99 / 1814
3, WO 00/09611, JP 2001-115A.
In Japanese Patent Laid-Open No. 007, etc., there is known a technique related to a high-strength, high-modulus polyketone fiber that is wet-spun using a metal salt solution such as a zinc salt, a calcium salt, and an iron salt.

However, it has been revealed that when wet spinning of multifilaments is carried out using a metal salt solution as a solvent, severe single yarn sticking occurs during drying. Such single yarn sticking remains in the fiber after hot drawing and in the final fiber product after processing, which not only causes fluff, yarn breakage, etc. in process stability and quality, but also twists when twisted. There is a problem that the strength of is significantly reduced. In the inventions related to wet spinning using a metal salt solution known so far, there is no description about the problem of single yarn sticking and a solution thereof, and further, reduction of friction between fibers and fiber-metal. There is no mention of any technique relating to improvement of processability during drawing or twisting by reduction of friction between fibers and improvement of physical properties of a twisted product after twisting. As described above, regarding the polyketone fiber, until now, there is no problem of single yarn sticking, and the fiber-fiber has less friction and excellent passability in the twisting process, and even after twisting, excellent quality and mechanical properties, resistance No polyketone fiber capable of exhibiting fatigue properties is known.

[0006] On the other hand, several documents are known about a twisted yarn made of polyketone fiber. JP-A-9-32
No. 9198 discloses a twisted product composed of polyketone fibers obtained by a melt spinning method and polyketone fibers obtained by a wet spinning method using hexafluoroisopropanol as a solvent. There is no description regarding friction, and no knowledge is given regarding the present invention. Further, in JP-A-1-124617, there is a description in which polyketone fibers are twisted together, but the present invention uses polyketone fibers having low mechanical properties and heat resistance obtained by melt spinning a low melting point polyketone. Moreover, there is no description about a technique relating to single thread sticking of polyketone fiber and friction of fiber.
Further, JP-A-11-334313 and JP-A-11-33413
In 336957, there is a description of a twisted yarn composed of a polyketone fiber obtained by a melt spinning method and a polyketone fiber consisting of only 1-oxotrimethylene (ECO fiber), but also in these inventions, a single yarn There is no suggestion of a technique for suppressing sticking, reducing fiber-fiber friction, and increasing the twisting strength utilization rate of polyketone fibers. As described above, a polyketone twisted yarn comprising a polyketone fiber having no single yarn sticking and having a small fiber-fiber friction, and having excellent twisting process passability, twisting yarn strength utilization factor, and fatigue resistance. Until now, no technology related to goods has been known.

[0007]

One of the problems to be solved by the present invention is that it has excellent mechanical properties such as high strength and high elastic modulus, and has no single yarn sticking and fiber-to-fiber and fiber-to-fiber bonding. To provide a polyketone fiber having small friction between metals, excellent passability in a twisting process, a high twist yarn utilization factor, and fatigue resistance, and a method for producing the same, and a second problem is high strength, and The present invention provides a polyketone twisted yarn having a high twist yarn tenacity utilization ratio and excellent fatigue resistance.

[0008]

Means for Solving the Problems As a result of intensive studies on the structure and manufacturing method of the polyketone fiber in order to achieve the above-mentioned objects, the inventors of the present invention have found that as a result of the high strength technology, the reduction of single yarn sticking, the fiber-to-fiber It was found that the reduction of the friction coefficient, homogenization of the fiber cross-sectional shape, and optimization of the single yarn fineness are the countermeasures, and as a result of further studies, the present invention was reached. That is, the present invention is basically a polyketone fiber in which 95 to 100% by mass of repeating units are composed of 1-oxotrimethylene represented by the following structural formula (1), and the following (a) to (e) )
The present invention relates to a polyketone fiber characterized by satisfying the above requirement. (a): Crystallinity ≧ 60% (b): Crystal orientation ≧ 90% (c): Tensile strength ≧ 10 cN / dtex (d): Single yarn sticking rate ≦ 30% (e): Finishing agent adhesion rate = 0.3-15% by mass

[Chemical 3]

The polyketone fiber of the present invention is a polyketone in which 95 to 100% by mass of the repeating unit is composed of 1-oxotrimethylene. The higher the proportion of 1-oxotrimethylene in the repeating unit, the higher the regularity of the molecular chain, and the higher the degree of crystallinity, the higher the degree of orientation of the fiber can be obtained.
As a result, a fiber having high strength, high elastic modulus and high heat resistance can be obtained. Therefore, the proportion of 1-oxotrimethylene is preferably 97 to 100% by mass, most preferably 100% by mass.
Is desirable. Also, if necessary, propene,
An olefin other than ethylene such as hexene, or a compound having an unsaturated hydrocarbon such as methyl methacrylate or sodium allylsulfonate may be copolymerized.

The degree of polymerization of polyketone is 2-1 in terms of intrinsic viscosity.
It is preferably 0. If the intrinsic viscosity is less than 2, the strength and spinnability of the polyketone fiber will decrease. Further, when the intrinsic viscosity exceeds 10, the polymerization cost and the spinning cost become high, and it becomes difficult to obtain the polyketone fiber at a practical price. Therefore, the degree of polymerization of the polyketone is preferably such that the intrinsic viscosity is in the range of 2 to 10, more preferably 3 to 6.

The polyketone fiber of the present invention is required to have crystallinity and crystal orientation in a specific range in order to exhibit high strength / high elastic modulus and high heat resistance. Crystallinity
(a) is a structural parameter representing the amount ratio of the crystal structure,
If this value is less than 60%, the polyketone fiber cannot exhibit sufficient strength, elastic modulus, and heat resistance. The higher the crystallinity (a), the higher the strength, the high dimensional stability, the high heat resistance and the high chemical resistance. Therefore, the crystallinity (a) needs to be 60% or more, more preferably 70% or more, and particularly preferably 80%
The above is desirable. The crystal orientation degree (b) is
It is a structural parameter that represents the degree of regularity in which the molecular chains in the fiber are arranged in the fiber axis direction. If this value is less than 90%, the molecular chains are not well arranged and the elastic modulus is low, resulting in poor dimensional stability under load. Will be enough. The higher the degree of crystal orientation (b), the higher the elastic modulus and the more excellent the dimensional stability.
It is necessary that the content be not less than 100%, more preferably not less than 95%, particularly preferably not less than 97%.
Further, the polyketone fiber of the present invention is a fiber having excellent tensile strength. The higher the tensile strength (c) is, the higher the strength of the twisted yarn is obtained, and the more the fluff and the yarn breakage due to the tension during the drawing and the twisting are less likely to occur. Therefore, the tensile strength (c) is 1
It is necessary to be 0 cN / dtex or more, more preferably 13 cN / dtex or more, and further preferably 1
5 cN / dtex or more, particularly preferably 17 cN / dt
It is desirable to be ex or more.

Since the high-strength polyketone fiber is highly oriented in the fiber axis direction, when twisted,
Frequently, there is a problem that the strength decreases due to the force other than the fiber axis direction, the single yarn breaks or fibrils are generated due to the rubbing between the fiber surfaces, and the single yarns are entangled with each other and the process passability and quality deteriorate. Come to do. The most important technical problem of the present invention is to provide a fiber which does not cause the problem of irritation even if it is a highly crystallized and oriented high-strength polyketone fiber. To solve, (i) no single yarn sticking, (ii) small friction between fibers, (iii) small single yarn fineness,
(iv) It is important that there are no fluffs or fibrils, and in particular, polyketone fibers satisfying (i) and (ii) at the same time have extremely excellent properties against a reduction in strength due to twisting and a reduction in process passability. I found something to show.

Regarding the single thread sticking of the polyketone fiber of the present invention, the single thread sticking rate (d) defined by the following formula (4) is 30% or less. Single thread sticking rate (d) = [1- (apparent single thread number / single thread number)] x 100 (%) (4) (Here, single thread sticking rate (d) means This is a value representing the numerical ratio of the stuck single yarns.) Explaining in a concrete example, two single yarns are stuck together in a fiber manufactured by using a spinneret having 10 holes. If there are two sets, the number of single yarns is 10, the apparent number of single yarns is 8, and the single yarn sticking rate (d) is 20%. If the sticking rate (d) of the single yarn is more than 30%, the fiber becomes hard, and excessive force is easily applied to the single yarn to cause fluffing and breakage during the twisting, and the strength after twisting decreases. Such problems become apparent. The single thread sticking ratio (d) is more preferably 20% or less, particularly preferably 10% or less, and most preferably 0%.

It is also important that the fiber-to-fiber friction is small.
It is extremely effective to contain a finishing agent in an amount of 1 to 20% by mass to reduce wasteful contact resistance due to fiber focusing and antistatic, and to reduce the friction coefficient of the fiber surface by forming an oil film. The components of the finishing agent are not particularly limited, and for example, the finishing agent described in Japanese Patent Application No. 2000-19995 can be used. Specifically, at least one selected from (1) ester compound, (2) mineral oil, and (3) polyether is an essential component as a component of the finishing agent, and the total amount thereof is 30% in the finishing agent. ~ 100% by weight, preferably 5
A finish containing 0 to 80% by weight is preferred. By applying such a finishing agent, a strong oil film is formed on the surface of the polyketone fiber, and the surface of the fiber is slipped by this oil film, so that the fiber is not worn in a short period of time during drawing or twisting.

The ester compound (1) is a component for improving the smoothness and abrasion resistance of the surface of the polyketone fiber, and specific examples thereof include octyl stearate and lauryl oleate, the molecular weight of which is smooth. From the viewpoint of process passability, it is preferably 500 to 3000. Mineral oil (2) is also
It is a component that improves the smoothness and abrasion resistance of the polyketone fiber surface, and is preferably a paraffin-based or naphthene-based component having a redwood viscosity of 40 at 30 ° C.
~ 800 seconds is preferred. Polyether (3) has the function of increasing the strength of the oil film formed on the surface of the fiber by the finishing agent, and specifically, a polyether whose main component is polyolefin oxide formed by copolymerization of propylene oxide and ethylene oxide is used. The molecular weight is preferably 1500 to 20000 from the viewpoint of wear resistance.

The finishing agent used in the present invention preferably contains an emulsifier (eg, polyoxyethylene stearyl ether), an antistatic agent (eg, anionic surfactant), and an antioxidant. Adhesion rate of finishing agents as above
When (e) is less than 0.3% by mass, the effect of reducing the frictional resistance is insufficient, and when it exceeds 15% by mass, the contact resistance between the oil films increases and conversely the friction between the fibers increases. Therefore, the adhesion rate (e) of the finishing agent is preferably 0.3 to 15 mass% with respect to the polyketone fiber, and more preferably 0.5.
It is -10% by mass, more preferably 1-5% by mass.
Finishing agent can be applied straight as it is, or
It can be dispersed in water and attached to the fiber as an emulsion finish. In particular, for polyketone fibers with a large number of single yarns, it is important to uniformly permeate the oil agent between the fibers, and if an activator having an ester group, a ketone group, or an ether group is used as a penetrant, a finishing agent will be evenly distributed between the polyketone fibers. It is effective because it can be dispersed and applied to.

Further, as a means for reducing the resistance between fibers, it is effective to make the cross-section of the fiber into a shape that does not easily rub. The cross-sectional shape of the polyketone fiber of the present invention is not particularly limited, and can be selected according to the purpose such as circle, ellipse, triangle, square, rhombus, alphabet, star, and hollow.
A circular shape (round cross section or elliptical shape) is desirable in order to obtain extremely high twisting yarn strength utilization ratio and process passability during twisting, and a circular cross section with a roundness (g) of 1.0 to 1.2. Is more preferable. Here, the circularity (g) is a value obtained from the minimum circumscribed circle radius / maximum inscribed circle radius of the polyketone fiber cross section, and the closer to 1.0, the closer to the perfect circle. The closer the circularity (g) is to 1.0, the smaller the contact area between single yarns, the less the friction resistance between fibers, the higher the fatigue resistance of twisted yarns and the higher utilization factor of twisted yarns. The time passability is improved. The roundness (g) is more preferably 1.
It is desirable that it is 0 to 1.1.

The polyketone fiber of the present invention has a fiber-to-fiber dynamic friction coefficient (f) (hereinafter may be abbreviated as μ) of 0.01 to depending on the addition of a finishing agent and the design of the fiber cross-sectional shape.
It is desirable to set it to 0.5. When μ exceeds 0.5, a load is applied during twisting, fluffing and yarn breakage occur frequently, and the twisting yarn strength utilization factor is greatly reduced. On the other hand, when μ is less than 0.01, the bundle-converging property of the multifilament is deteriorated and sagging is caused, whereby the twisting yarn strength utilization ratio (h) and the quality are deteriorated, and the processability and handleability are deteriorated. Therefore, the value of μ is preferably 0.03 to 0.4, and more preferably 0.0.
It is desirable to be 5 to 0.3.

Further, it is of course important that the polyketone fiber of the present invention has a small amount of fluff and fibrils. Here, the fluff is a fiber whose one end is not constrained, which is generated by cutting a single yarn. In addition, the fibrillar material is a cylindrical material made of polyketone having a diameter of 0.01 to several μm and a length of 1 μm to several tens of mm, which is peeled off due to impact or abrasion. These fluffs and fibrils not only reduce the strength of the polyketone fiber, but also the adjacent single yarn and the adjacent two yarns.
Entangled with more than one single yarn to form knot points and reduce the twisting yarn strength utilization rate (h). The number of fluffs is preferably 1 piece / 10 m or less, more preferably 1 piece / 100 m or less, and further preferably 1 piece / 10,000 m or less. The fibril number is 1 or less, preferably 1 in 100 fields of view when the fiber bundle is observed with an optical microscope.
It is desirable that there be 0 in 00 fields of view.

The single yarn fineness of the polyketone fiber is not particularly limited, but it is 0.
It is preferably 1 to 10 dtex. If the single yarn fineness is less than 0.1 dtex, fluff or yarn breakage occurs during spinning or twisting, and the product quality and process passability deteriorate. Further, if the single yarn fineness exceeds 10 dtex, there is a problem that the twisting yarn strength utilization ratio during strong twisting is lowered. Therefore, the single yarn fineness is more preferably 0.5 to 5 dtex, and particularly preferably 0.8 to 2 dtex. Further, the total fineness of the polyketone fiber is not particularly limited because it depends on the application and the site to be used, but usually 10 to 10,000 d
tex, preferably 300 to 3000 dtex.

The polyketone fiber of the present invention has high strength but no single yarn sticking, has a finishing agent, and has a dynamic friction coefficient.
(f) A fiber having a small μ and excellent in twistability, but as a specific range of the twistability, the twisting strength utilization factor (h) when twisted so that the twisting coefficient K becomes 10,000 is 65% or more. Is desirable. In the present invention, the twisting yarn strength utilization ratio (h) is a 100-percentage obtained by dividing the strength of the twisted polyketone product by the strength of the untwisted polyketone fiber. For example, when twisting multiple polyketone fibers,
The strength of the twisted polyketone twisted product is divided by the sum of the strengths of the twisted polyketone fibers to obtain a 100-percentage ratio as the twisted yarn strength utilization rate (h). K is the twist coefficient of the twisted yarn defined by the following formula (1). K = Y × D ^0.5 (T / m · dtex ^0.5 ) (1) [In the formula (1), Y is a polyketone twisted product 1 m
The number of twists per unit (T / m) and D are the total indicated fineness (dtex) of the twisted polyketone yarn. ]

Here, the total indicated fineness is the sum of the fineness of all polyketone fibers used for the twisted yarn. For example, 1670dt
When three polyketone fibers of ex are twisted together, the total fineness of the twisted yarn product is 5010 dtex (1670/3). When a plurality of polyketone fibers are twisted together and a multi-stage twist such as a lower twist and an upper twist is added, the twisting coefficient is calculated by setting the number of twists added last as the twist number Y. When used for rubber reinforcing materials such as tire cords, belts and hoses, or for applications such as ropes, nets and fishing nets, the twist coefficient K is 10
The twisted yarn in the range of 000 to 30,000 is often used. In the polyketone fiber, the twisting yarn strength utilization factor (h) decreases as the twisting coefficient K increases, and K is 10000.
Utilization rate (h) of polyketone fiber in polyester is 65%
If it is less than K, the twisting yarn strength utilization factor (h) at K of 10,000 to 30,000 becomes smaller than 65%. Therefore, in most applications, the strength of twisted yarns will not have practical strength even if high-strength polyketone fibers are used, and troubles such as fluffs and yarn breakage frequently occur during the twisting process, resulting in process passability and quality. Lowering occurs. Therefore, the twist coefficient K
It is preferable that the twisting yarn tenacity utilization ratio (h) at 10000 is 65% or more, more preferably 75%, and further preferably 80% or more.

Further, the twisting strength utilization factor of the polyketone fiber
(h) varies greatly depending on the twisting conditions (fineness of the polyketone fiber used, number of twisted yarns, etc.). The smaller the fineness of the polyketone fiber and the smaller the number of twisted yarns, the higher the yarn twisting strength utilization rate (h)
Becomes higher. Therefore, the polyketone fiber of the present invention preferably has a twist coefficient K within the range of the following formula (2). Twisted yarn strength utilization rate (h) (%) ≧ 100-K / 300 ・ ・ ・ (2)

The polyketone fiber is expected to be applied to applications such as tires, belts, hoses and the like, which are subjected to a high load such as rubber reinforcing materials. In these applications, usually two or three or more twisted fibers are twisted together, and further twisted in the opposite direction to the twisted twist to obtain a twisted yarn, and the obtained twisted yarn requires high strength. . The inventors of the present invention are extremely excellent over conventional polyketone fibers by performing the above-mentioned single yarn sticking rate, finish composition / applying method, fiber cross-sectional shape, fibril suppression, and single yarn fineness under optimum conditions. A polyketone fiber having a high twist utilization factor (h) was found. The polyketone fiber having a high utilization factor of the high twisted yarn has a high utilization factor of the twisted yarn (h) in the range of the following formula (3), and is extremely useful for applications such as rubber reinforcing materials and ropes under high load. Twisted yarn strength utilization factor (%) ≧ 100 × (1−4.79 × 10 ⁻⁹ × K ^1.78 ) (3) As the value of the twisted yarn strength utilization factor (h) shown by the above formula (3), Specifically, when the twist coefficient K is 5000, 98% or more, when the twist coefficient K is 10,000, 94% or more, when the twist coefficient K is 15000, 87% or more, and the twist coefficient K is 20% or more.
It is 78% or more at 000, and 68% or more at a twist coefficient K of 25,000, and maintains a high twisting yarn strength utilization rate (h) from sweet twist to strong twist.

The polyketone fiber of the present invention may be used as a short fiber. The polyketone short fiber is obtained by cutting the above-mentioned polyketone filament in the yarn length direction. The length of the short fibers is not particularly limited and may be cut to any length depending on the use environment and purpose of use, but the average length of the short fibers is usually 0.1 to 100 mm, preferably 0.5. Those having a length of up to 50 mm are preferably used. In the present invention, the average length L of the short fibers is an average length of 100 short fibers arbitrarily selected, where the length of one short fiber in the longitudinal direction (fiber axis direction) is the fiber length L _i. It is calculated by the following equation (5). Such short fibers are useful as a reinforcing material for concrete or as a spun yarn in applications such as knitting and ropes.

[Equation 1]

Another aspect of the present invention is a polyketone twisted product obtained by twisting the above-mentioned polyketone fiber having high strength and high elastic modulus and excellent twistability. In the present invention, the twisted yarn means a fiber material in which fibers are twisted at a rate of 10 times / m or more, and the fiber material is 10
If it is less than 0% by mass, it may contain substances other than fiber materials such as resins, adhesives and oils. The twisted product of the present invention contains the polyketone fiber of the present invention in at least a part of the fiber material constituting the twisted product.

The higher the proportion of the polyketone fiber in the twisted yarn, the higher the strength, the high mechanical properties and the high heat resistance. Therefore, the twisted yarn preferably has 50 to 100% by mass, more preferably 80 to 100%. It is desirable that the mass% is the polyketone fiber of the present invention. Among them, 10 of fiber materials
A polyketone twisted yarn composed of 0% by mass of the polyketone fiber of the present invention is useful as a high-strength fiber material. In particular, polyketone twisted yarns having a twisting yarn strength utilization ratio (h) in the range of the following formula (3) show extremely high mechanical properties in a wide twisting yarn range, and have high tenacity that cannot be obtained by conventional polyketone twisted yarn products. Is. Twisted yarn strength utilization rate (h) (%) ≧ 100 × (1-4.79 × 10 ⁻⁹ × K ^1.78 ) ... (3)

Strength (strength) of the twisted polyketone of the present invention
Is difficult to unconditionally define depending on the twisting condition, application, use part, etc., but when the twisting coefficient K is 10,000, preferably 10 cN / dtex or more, more preferably 13 cN / dtex or more, particularly preferably 15 cN / d.
tex or more, and when the twist coefficient K is 20,000, preferably 8 cN / dtex or more, more preferably 10 c
N / dtex or more, particularly preferably 12 cN / dtex
The above is desirable. Here, the strength of the twisted product is
It is a value obtained by dividing the strength of the twisted yarn by the total fineness of the fibers used in the twisted yarn.

If desired, fibers other than polyketone fibers (for example, polyester fibers, aramid fibers, cellulose fibers, polyamide fibers, polyvinyl alcohol fibers, etc.) may be contained. There is no particular limitation on the twisted form of the polyketone twisted product, and as the type of twisted yarn, for example,
Examples of the single twisted yarn, the twisted yarn, the picco-twisted yarn, the strong twisted yarn, and the like, the number of twisted yarns may be one twisted, two twisted, three twisted, or four or more twisted. The thickness of the twisted yarn is appropriately selected according to the application, and a diameter of 0.1 to 10 mm is suitably used for the rubber reinforcing material application, and a diameter of 1 to 100 mm is suitably used for the rope or net application. The number of twisted yarns can also be appropriately selected according to the application, part, etc., but the twisting coefficient K is 100 to 500.
A range of 00 is preferably used, more preferably 1000
The range of up to 30,000 is preferably used.

When the twisted yarn of polyketone of the present invention is used as a rubber reinforcing material, an adhesive may be attached in order to improve the adhesiveness with rubber. The type of adhesive is not particularly limited, and a conventionally known adhesive may be used as it is, or the conditions may be changed according to the purpose. As the adhesive, resorcin-formalin-latex (RF
L) resin is preferably used, and the adhesion rate of the RFL resin is preferably 0.1 to 10% by mass, more preferably 1 to 7% by mass with respect to the fiber.

A molded product containing the polyketone fiber and the twisted polyketone product of the present invention has high mechanical properties, and
Fatigue resistance is also excellent because there is little sticking of single yarns and fluff and the coefficient of friction between fibers is low. In the present invention, the molded article includes not only fiber products such as ropes, woven fabrics, knitted fabrics, nets and nets, but also tires, belts, hoses,
It means artificial products such as rubber products such as endless tracks and resin products such as FRP.

Next, the method for producing the polyketone fiber and the twisted polyketone product of the present invention will be described. The production method of the polyketone fiber of the present invention is not particularly limited, handleability,
From the viewpoint of toxicity, flammability, modification of polyketone, cost, etc., a wet spinning method using a metal salt solution as a solvent is preferable. Hereinafter, a method for producing the polyketone fiber of the present invention by a wet spinning method using a metal salt solution as a solvent will be described. The metal salt solution used for dissolving the polyketone is not particularly limited as long as it has the ability to dissolve the polyketone, and examples thereof include zinc halide, alkali metal halide salt, and alkaline earth metal halide salt. The metal salt solution is preferably an aqueous solution from the viewpoint of explosiveness, handleability, and cost, and an aqueous solution containing 10 to 80% by mass of zinc halide (zinc chloride, zinc iodide, etc.) is particularly preferably used. In addition, compounds other than the above metal salts may be mixed within a range that does not impair the object of the present invention.

The salt concentration of the metal salt solution is preferably 50 to 80% by mass. At salt concentrations below 50% by weight, or above 80% by weight, spinning becomes unstable. The salt concentration is a value defined by the following formula (6). Salt concentration (mass%) = [mass of salt / (mass of salt + mass of solvent)] × 100 (6) The polymer concentration of the polyketone dissolved in the metal salt solution is solubility, spinnability, and manufacturing cost. From the viewpoint of 0.1 to 40% by mass, more preferably 3 to 20% by mass. The polymer concentration is a value defined by the following formula (7). Polymer concentration (mass%) = [polymer mass / (polymer mass + metal salt solution mass)] × 100 (7)

The polyketone solution obtained is filtered with a filter as required, and then extruded from the spinneret into a coagulating bath,
Form into fibrous form. When there is a large difference between the temperature of the polyketone solution at the time of extrusion and the temperature of the coagulation bath, the so-called air gap method is preferred, in which the fibrous material discharged from the spinneret enters the bath through the air phase. The composition and temperature of the coagulation bath are not particularly limited, but an aqueous solution of the salt used as the solvent is preferable from the viewpoint of reducing the recovery cost of the solvent. The fibrous material that has been pulled out of the coagulation bath is washed with water and, if necessary, the metal salt is substantially removed using an aqueous solution containing hydrochloric acid, sulfuric acid, phosphoric acid and the like and having a pH of 4 or less. In particular, the metal salt solution is an aqueous solution of calcium chloride / zinc chloride (mass ratio 68/32 to 61/39) having a salt concentration of 59 to 64% by mass,
The temperature of the polyketone solution when extruding from the spinneret is 60
When the coagulation bath temperature is ˜150 ° C., and the coagulation bath temperature is −50 to 20 ° C., the effect of lowering the single thread sticking ratio (d) is large and the strength is also increased, which is preferable.

Next, drying is performed to remove water contained in the fibers. The drying method is not particularly limited, and drying can be performed while stretching, while keeping a constant length or shrinking, using known equipment such as a tunnel dryer, a roll heater, and a net process dryer. The drying temperature is not particularly limited, but is preferably 100 ° C to 260 ° C, more preferably 120 ° C to 250 ° C, most preferably 150 ° C to 24 ° C.
It is 0 ° C. Then, the dried yarn is subsequently subjected to hot drawing by multi-step drawing of one step or two or more steps.

Stretching may be performed in any number of stages, and when performing multi-stage stretching, it is preferable to gradually increase the stretching temperature. The stretching temperature is preferably 150 ° C. to the melting point of the polyketone fiber. At a temperature lower than 150 ° C., it is difficult to obtain a polyketone fiber having high strength and a high elastic modulus, and at a temperature higher than the melting point of the polyketone fiber, the yarn is melted and cut during drawing. From the viewpoint of stretchability and fiber physical properties, the melting point of the polyketone fiber is preferably 150 ° C., more preferably 200 ° C. to the melting point of the polyketone fiber −5 ° C. From the viewpoint of mechanical properties of the obtained polyketone fiber, the total draw ratio is preferably 10 times or more, more preferably 15 times or more.
As the hot drawing apparatus, a method of running on a heating roll or a heating plate or in a heated gas, or a conventionally known apparatus such as irradiating a running yarn with a laser, a microwave, or infrared rays may be used as it is or after improvement. it can.

In the wet spinning method using a metal salt, single yarn sticking is apt to occur in the drying step, and therefore it is extremely important to take measures to prevent single yarn sticking. As a method of preventing single yarn sticking, a method of applying an external force to the fibers to shift the single yarns,
Examples include a method of applying a release agent to the fiber surface before sticking occurs, a method of shifting the single yarns by electrostatic repulsion between the single yarns, and the like. Particularly, from the viewpoint of physical properties and process passability of the obtained fiber. A method of applying an external force to the fiber to shift the distance between the single yarns and a method of applying a release agent to the fiber surface are preferably used.

When applying an external force that causes deviation between single yarns,
External force can be applied once or multiple times at any stage until the completion of the drying process and / or the stretching process,
At this time, it is important to treat fibers having a water content of 0 to 40% by mass. In the present invention, the moisture content is
Defined in (8). Moisture content (mass%) = [(mass of residual water fiber−mass of absolutely dry fiber) / mass of residual water fiber] × 100 (8) Here, the mass of absolutely dry fiber means drying at 105 ° C. for 5 hours, It is the fiber mass when water is completely removed. If the moisture content of the fiber is higher than 40% by mass, problems such as deformation of the cross section of the single yarn, damage to the fiber, and slack are likely to occur when an external force is applied to cause displacement between the single yarns. It is more preferable that the water content is 30% by mass or less. on the other hand,
When the moisture content is as low as 0 to 1% by mass, static electricity is easily generated due to friction between fibers and between fibers and a manufacturing apparatus. Therefore, it is possible to use a conductive material for the apparatus and have an antistatic effect. It is desirable to take measures to remove static electricity, such as applying an oil agent.

The deviation between the single yarns means that the relative positional relationship between the single yarns that are in contact with each other changes (the side faces between the single yarns that are in contact with each other are separated from each other, and the side faces between the single yarns that are in contact with each other are separated from each other. Slipping) and thereby preventing sticking between single yarns or removing sticking that has occurred once, and a polyketone fiber having a low sticking rate of single yarns can be obtained. As the external force that causes the displacement between the single yarns, it is effective to squeeze the fibers or to give vibration to the fibers. Specifically, a method of squeezing the fiber through a pin guide or a roll, a method of vibrating the fiber with an ultrasonic generator, a method of blowing a compressed gas to the fiber and the like can be mentioned. Circularity (g) that is unlikely to cause deformation or scratches on the single yarn cross section
The method of blowing a compressed gas to the fibers is preferably used in that fibers having a high fiber density can be obtained, and that the operability is good and the fibers having a low single yarn sticking rate are easily obtained. The composition of the compressed gas is not particularly limited, but from the viewpoint of safety and handleability, air,
Nitrogen is preferred and air is most preferred.

In order to obtain a polyketone fiber having a low single thread sticking ratio (d) without damaging the fiber, it is important to set the tension applied to the fiber and the blowing speed of the compressed gas within an appropriate range. Specifically, the tension applied to the fiber is 0 to 1c.
N / dtex range, spraying speed 0.1-1
The range is 00 m / sec, preferably 10 to 50 m / sec. When the single thread sticking ratio (d) is high, it is effective to reduce the tension applied to the fiber and to increase the gas blowing speed. There is no particular limitation on the device for spraying the compressed gas, the method, and the shape of the spray hole, and any shape (round shape, elliptical shape, rectangular shape) at the tip of the conventionally known compressed air processing device such as an interlacer or a false twist nozzle or compressed air piping can be used. , Rectangle, etc.) may be attached.

When the release agent is applied to the surface of the fiber before the single yarn sticking occurs, the release agent is not particularly limited as long as it has an action of preventing sticking by subsequent drying and hot drawing. In the present invention, the term "releasing agent" means that after the releasing agent compound is applied to the surface of two polyketone fibers positioned in parallel,
When the polyketone fibers are arranged so as to be bonded along the fiber axis direction and subjected to a fixed length heat treatment at 225 ° C. for 1 minute, a compound having an action of easily defibrating the polyketone fibers from each other is used as a release agent. And Examples of such release agents include:
For example, water-insoluble particles (metal oxide particles, metal particles, silicon compound particles, fluorine compound particles), water-insoluble organic materials (mineral oil, high molecular weight ester compounds, high molecular weight ether compounds) and dispersions thereof. Examples thereof include liquids, and from the viewpoint of uniform dispersion between polyketone fibers and handleability, a fine particle dispersion liquid containing metal oxide fine particles or silicon-based fine particles as a main component is preferably used. The average particle size of the fine particle dispersion is preferably 0.1 to 100 μm, more preferably 0.2 to 10 μm. The dispersion medium of the fine particle dispersion liquid is preferably water from the viewpoint of handleability and safety.

The amount of the release agent attached is preferably 0.1 to 20% by mass with respect to the polyketone fiber. When the amount of the release agent attached is less than 0.1% by mass, the effect of preventing single thread sticking is not obtained, and when it exceeds 20% by mass, the physical properties of the obtained polyketone fiber are deteriorated and the stretchability is also increased. It also has an adverse effect. Therefore, the amount of the release agent deposited is preferably 0.3 to 10% by mass, more preferably 0.5 to 5% by mass. An important point in applying the release agent is to apply the release agent at a stage where the water content of the polyketone fiber exceeds 40% at any stage from the washing process to the end of the drying process.

When the water content is 40% or less, single thread sticking starts to occur and a sufficient effect of preventing single thread sticking cannot be obtained even if a release agent is added. Therefore, it is necessary to apply the release agent at a stage where the water content of the polyketone fiber exceeds 40%, more preferably at a water content of 60% or more, further preferably at a water content of 100% or more. Is desirable. Further, if the release agent is applied before the completion of solidification, the release agent enters the inside of the single yarn and the physical properties of the fiber are extremely deteriorated. Therefore, it is desirable to perform after the acid washing step inlet, and more preferably after the water washing step inlet. It is more preferable to apply after the washing step. The release agent may be applied in one step or in multiple steps, and other components may be mixed with the release agent as long as the single yarn sticking does not occur.

In addition to the means for preventing single yarn sticking, it is necessary to add a finishing agent at any stage after the completion of the drying process to the end of the hot drawing to reduce μ. The finishing agent may be applied once or plural times, and may be applied before or during the hot stretching step. The composition of the finishing agent is not particularly limited, and it may be applied straight, diluted with a solvent, or supplied as an emulsion or suspension. When a finishing agent is applied as an aqueous solution, an aqueous emulsion or an aqueous suspension after the completion of hot drawing, μ may increase due to moisture remaining between the fibers and the twisting yarn strength utilization rate (h) may decrease, so the finishing agent It is desirable to provide a step of drying water after application. The device for applying the finishing agent is not particularly limited, and conventionally known devices such as nozzle oil supply and roll oil supply can be used as they are or after being modified according to the purpose.

Further, in order to suppress the generation of fluff and fibril-like substances during the drawing process, the device (excluding the speed regulating roll) that comes into contact with the fibers during the drawing process is made of a material having a small friction coefficient with the polyketone fiber. Is preferable, and specifically, a material having a dynamic friction coefficient between fiber and metal of 0.1 or less, preferably 0.01 to 0.08 (for example, metal oxide or metal having a large surface roughness) is preferable. . In addition, it is desirable that these materials be electrically conductive so that static electricity generated by friction is gradually discharged.

The polyketone fiber after the hot drawing step is continuously wound as it is, or is once wound and then twisted. The number of twisted yarns is selected according to the application and the usage environment, and generally, the above twist factor K is twisted in the range of 1000 to 30,000. From the viewpoint of the mechanical properties and quality of the twisted yarn, the twisting yarn tension is 0.01 to 0.01 for both the lower twisting tension and the upper twisting tension.
It is preferably 0.2 cN / dtex.

In the case of using a rubber-reinforcing fiber, the twisted polyketone twisted product is passed through a step of adhering an RFL liquid having a concentration of 10 to 30 mass% and fixing a resin (so-called Dip treatment step). The preferable composition of the RFL solution is 0.1 to 10% by mass of resorcin, 0.1 to 10% by mass of formalin, and 1 to 28% by mass of latex.
And a more preferred composition is resorcin 0.5-
3% by weight, formalin 0.5 to 3% by weight, latex 1
0 to 25 mass% is desirable. The drying temperature of the RFL solution is preferably 100 to 250 ° C., more preferably 140 to 200 ° C., and it is desirable that the RFL liquid be subjected to a drying heat treatment for at least 10 seconds, preferably 20 to 120 seconds.

The dried twisted yarn is subsequently subjected to heat treatment in the heat setting zone and the normalizing zone. The temperature, tension and time in the heat setting zone are 150 to 250 ° C. and 0.1 to 0.7 cN / dte, respectively.
x, preferably 10 to 300 seconds. Also, the temperature, tension and time in the normalizing zone are
150-250 ° C, 0.01-0.3 cN / dtex,
It is desirable to set it to 10 to 300 seconds.

The polyketone fiber obtained by the above method has excellent mechanical properties such as high strength, high elastic modulus and high twist yarn strength utilization factor, and when it is used as a twisted yarn, the strength of the raw yarn is at a high level. It is useful as a high-strength fiber material that maintains and has excellent fatigue resistance. In particular, it is extremely useful in the field of industrial materials in which rubber reinforcing materials such as tire cords, hoses and belts, and fibers such as ropes, nets and fishing nets are strongly twisted and used.

[0050]

The present invention will be described in more detail with reference to the following examples, which are not intended to limit the scope of the present invention. The measuring method of each measured value used in the description of the examples is as follows. (1) Intrinsic viscosity Intrinsic viscosity [η] is a value calculated based on the following definition formula. (In the definition formula, t and T are the flow-through time of a viscous tube at 25 ° C. of a dilute solution of hexafluoroisopropanol having a purity of 98% or more and polyketone dissolved in the hexafluoroisopropanol. Further, C is 100 ml above. (2) Crystallinity (a) Crystallinity (a) A differential thermal analyzer Pyris1 (trademark; manufactured by Perkin Elmer Co., Ltd.) is used for measurement under the following conditions. As the sample, short fibers whose thread length is cut to 5 mm are used. Sample mass: 1 mg Measurement temperature: 30 ° C. → 300 ° C. Temperature rising rate: 20 ° C./min Atmosphere: Nitrogen, flow rate = 200 mL / min The maximum endothermic peak observed in the range of 200 to 300 ° C. in the obtained endothermic curve It is calculated by the following formula from the heat quantity H (J / g) calculated from the area. Crystallinity = ΔH / 225 × 100 (%)

(3) Crystal orientation (b) Imaging plate X-ray diffractometer manufactured by Rigaku Corporation,
RINT (registered trademark) 2000 is used to capture a diffraction image of the fiber under the following conditions. X-ray source: CuK soot output: 40KV 152mA Camera length: 94.5mm Measurement time: 3 minutes Observed around 2θ = 21 ° in the obtained image (11
0) Calculated by the following formula from the half value width H of the intensity distribution obtained by scanning the surface in the circumferential direction. Crystal orientation degree = [(180−H) / 180] × 100
(%) (4) Fineness, strength, and strength Fineness is measured by allowing the sample to stand at 25 ° C. and 55% humidity for 48 hours, measuring the mass W _{1 of the} sample 100 m, and measuring W ₁ × 100 as the total fineness of the fiber ( dtex). This sample is sample length 2
Tensile strength and strength are measured at 50 mm and a crosshead speed of 300 mm / min. Further, a value obtained by dividing the total fineness by the number of holes of the spinneret used for producing the fiber is defined as a single yarn fineness.

(5) Single yarn sticking rate (d) (A) Number of single yarns Polyketone fiber is replaced with epoxy monomer [Ketol 812
(Commercial name, manufactured by Nisshin EM Co., Ltd.)] and a curing agent (dodecyl saxonic unhydride, methyl nadick unhydride), and then the initiator [DMP-3
0 (trade name, manufactured by Nisshin EM Co., Ltd.)] is added, and the mixture is treated under heating conditions of 60 ° C. for 24 hours for polymerization, and the fibers are embedded in the resin. The resin-embedded fiber is cut with a microtome, and the cross section of the fiber is photographed with an electron microscope. The photographed negative image is measured by the following method using an image analyzer (IP1000-PC: trade name, manufactured by Asahi Kasei Corp.). A negative image is captured in 256 gray levels in black and white using a scanner.
Binarization processing is performed on the captured 256 gradation image. The parameters to be set at this time are (1) threshold value (= automatic), (2) shading correction processing (= present),
(3) Fill-in processing (= Yes), (4) Gamma correction processing (= correction value γ = 2.2), (5) Small figure area (1 μm or less removed)
Is. From the obtained binarized image, the number of single yarns is calculated using particle analysis software.

(B) Apparent number of single yarns Polyketone fibers are lightly rubbed with chalk 20 times on a black mount to defibrate the fibers, and the number of filaments is counted with a 100 × magnifying glass. Those that cannot be separated due to sticking are counted as one single yarn, and the average value of three measurements is used as the apparent number of single yarns. If the number of single polyketone fiber filaments is large, do not perform defibration treatment at one time, divide the polyketone fiber into n pieces based on the following formula (9) before defibration, and defibration treatment for each divided unit Perform the above procedure to measure the number of filaments, and use the sum as the apparent number of single yarns. N / 200 ≧ n ≧ N / 300 (9) [where N = number of single yarns (measured value at A)] Measured number of single yarns, apparent number of single yarns from the following formula (10) Ask for. Single thread sticking rate = [1- (apparent number of single threads / number of single threads)] × 100 (%) (10)

(6) Finishing agent adhesion rate (e) The fiber was washed with methyl ethyl ketone at 50 ° C., the mass before cleaning was W ₂ (g), and the mass after cleaning was W ₃ (g).
Obtain the finish adhesion rate (e) from (11). The mass of the fibers (W ₂ and W ₃ ) is measured by heating at 105 ° C. for 5 hours before being weighed in an absolutely dry state. Finish adhesion rate _{(e) = (W 2 -W} 3) / W 3 × 100 (%) ··· (11) (7) bone dry weight of the resin adhesion rate twisting was 1m after heating for 5 hours at 105 ° C. W
₄ Weigh (g). Then, the rope was chopped into 1 mm lengths, and the mixture was stirred with hexafluoroisopropanol for 6 minutes under stirring.
Dissolve at 0 ° C for 2 hours. After dissolution, the mixture is filtered, the obtained residue is heat-treated at 105 ° C. for 5 hours, the mass W ₅ (g) is precisely weighed, and the resin adhesion rate is calculated from the following formula (12). Resin adhesion rate = [W ₅ / (W ₄ −W ₅ )] × 100 (%) (12)

(8) Fiber-Fiber Dynamic Friction Coefficient (f) About 690 m of fiber is wound around a cylinder at a traverse angle of 15 ° to be about 10
g of the same fiber 30.g.
5 cm was hung on this cylinder. At this time, the fibers are on the cylinder and are parallel to the winding direction of the cylinder. The value of the load, expressed in grams, is 0.
Tie one weight to one end of the fiber on the cylinder,
A strain gauge was connected to the other end. Next, the cylinder is rotated at a peripheral speed of 18 m / min, and the tension is measured with a strain gauge. From the tension thus measured, the fiber-fiber static friction coefficient (f) was determined according to the following equation (13). μ = 1 / π × ln (T ₂ / T ₁ ) ... (13) (where T ₁ is the weight of the weight applied to the fiber, T ₂ is the tension when measured, ln is the natural logarithm, π indicates the pi.)

(9) Roundness (g) (5) The cross-sectional photographic image of the polyketone fiber obtained in (A) was used to measure the minimum circumscribing of a single yarn by using a deformity measuring device FMS-2000 (trade name, manufactured by Union System Co.). The circle diameter R ₁ and the maximum inscribed circle diameter R ₂ are determined. R ₁ / R ₂ was calculated for any 50 single yarns in the cross-sectional photograph, and the average value was calculated as the circularity (g).
And

(10) Twisted yarn strength utilization ratio (h) The twisted yarn strength utilization ratio (%) is expressed by F / F ₀ × 100. (However, F is strong after twisting,
F ₀ is the sum of the tenacities of all the polyketone fibers used for the twisted yarn. It should be noted that the twisted yarn strength utilization ratio after RFL treatment corresponds to the sum of the strength of the RFL-treated twisted product / the strength of the polyketone fiber used for the twisted yarn.

(Polyketone fiber)

Example 1 A polyketone having an intrinsic viscosity of 5.9, which was prepared by a conventional method and in which ethylene and carbon monoxide were completely alternating-polymerized,
It was added to an aqueous solution containing 40% by mass of calcium chloride / 22% by mass of zinc chloride, and the mixture was stirred at 80 ° C. for 2 hours and further 90 minutes.
It was melted at 0 ° C. for 1 hour to obtain a dope having a polymer concentration of 6.8% by mass. The obtained dope was heated to 80 ° C., filtered with a filter having a diameter of 20 μm, and then the spinneret diameter was 0.15 mmφ, L
/ D = 1, after passing through an air gap of 10 mm from a round spinneret with 50 holes, it contains 2% by mass of calcium chloride, 1.1% by mass of zinc chloride, and 0.1% by mass of hydrochloric acid-2 A coagulated yarn was extruded into a coagulation bath composed of water at 0 ° C. at a discharge rate of 4.5 cc / min. Further, the polyketone coagulated yarn is washed with a hydrochloric acid aqueous solution having a temperature of 30 ° C. and a concentration of 2% by mass,
After further finishing washing with water at 40 ° C, speed 5m /
Rolled up in minutes. After the obtained coagulated yarn is simply dehydrated, IR
GANOX (registered trademark, manufactured by Ciba Specialty Chemicals) 1098 and IRGANOX (registered trademark, manufactured by Ciba Specialty Chemicals) 1076 are each 0.0.
It was impregnated with 5% by mass (relative to polyketone) and then dried at a temperature of 225 ° C. for 1 minute.

With a tension of 0.02 cN / dtex applied to the fiber, a pressure treatment device (HemaJet (registered trademark, manufactured by Japan Hebaline Co., Ltd.) T-341) was used to give a value of 0.
The compressed air of 2 MPa was blown to disintegrate. The water content of the polyketone fiber at this time was 0.2%. This fiber was drawn at the first stage (7 times) in a heating furnace at 225 ° C., and then the drawn yarn was further tensioned with 0.05 cN / dtex to obtain a pressure treatment device [HemaJet (registered trademark, T-321] (manufactured by Japan Hebaline Co., Ltd.).
It was disintegrated by blowing compressed air of 1 MPa. At this time, the water content of the polyketone fiber was 0%. After disintegration, continue to the second stage (1.8 times) in a heating furnace at 240 ° C, and further 25
The third stage (1.35 times) stretching was performed in a heating furnace at 8 ° C.

A finishing agent was added to the obtained drawn yarn, and
Heat treatment was performed at 180 ° C. for 10 seconds while applying a tension of 5 cN / dtex to obtain a polyketone fiber of 50.1 dtex / 50 f. The finishing agent used had the following composition. Oleic acid lauryl ester / bisoxyethyl bisphenol A / polyether (propylene oxide /
Ethylene oxide = 35/65: molecular weight 20000) /
Polyethylene oxide 10 mol addition oleyl ether /
Addition of 10 mol of polyethylene oxide Castor oil ether /
Sodium stearyl sulfonate / sodium dioctyl phosphate = 30/30/10/5/23/1/1 (mass% ratio).

The processability of spinning, drying and drawing was extremely good, and no trouble such as fluff or yarn breakage occurred. This polyketone fiber has a tensile strength of 9.27 N and strength of 1
It had a very excellent strength of 8.5 cN / dtex. The single thread sticking ratio (d) of this fiber is 0%, μ
Is 0.11, and when a twist of 1500 times / m is applied to the fiber with a load of 0.05 cN / dtex (twist coefficient = 10617), the twisting yarn strength utilization rate (h) is 8
An extremely excellent value of 6.5% was shown. The structure and twisting properties of the polyketone fibers of the examples of the present invention are shown in Example 2 below.
Table 1 together with the results of Example 13 and Comparative Examples 1 to 11
Are shown together.

[0062]

Example 2 The polyketone fiber obtained in Example 1 has 10 parts.
When twisted at 00 times / m (twist coefficient = 707
8), the twisting yarn strength utilization factor (h) was 90.6%, which was an extremely excellent value.

Example 3 The polyketone fiber obtained in Example 1 was added with 20
When twisted at 00 times / m (twist coefficient = 1415
6), the twisting yarn strength utilization rate (h) was 78.2%, which was an excellent value.

[Example 4] In Example 1, the water content was 25 during the drying process.
% Fiber with a tension of 0.04 cN / dtex to squeeze and defibrate it with a ceramic guide, and perform spinning, drying, drawing, and applying a finishing agent in the same manner except that defibration is not performed during drawing. went. The polyketone fiber obtained had a single thread sticking ratio (d) of 6%, which was good, and a twisting yarn strength utilization ratio (h) of 1,500 twists / m (twisting coefficient = 10532).
Showed an extremely excellent performance of 81.8%.

[0063]

[Example 5] In Example 1, except that silica fine particle emulsion having an average particle size of 5 µm was applied to polyketone fiber (water content = 1200%) at the entrance of the drying step, and no pressure treatment was performed in the drying step and the stretching step. In the same manner, spinning, washing, drying, drawing, and finishing agent application were performed. The polyketone fiber obtained had a single thread sticking ratio (d) of 10%, which was good.
When twisted 1500 times / m (twist coefficient = 108
The strength utilization factor (h) of the twisted yarn 37) was 81.2%, which was an extremely excellent performance.

Example 6 A polyketone fiber was obtained in the same manner as in Example 1, except that a finishing agent was applied after the defibration treatment after one-stage drawing and two steps were added together with the finishing agent application after the stretching. . The single thread sticking ratio (d) of the obtained polyketone fiber was 4
%, The twisting yarn strength utilization rate (h) when twisted at 1500 times / m (twist coefficient = 10817) is 74.7%.
And showed good performance.

[0064]

[Embodiment 7] In Embodiment 1, the amount of the finish applied is 2.
A polyketone fiber was obtained in the same manner except that the amount was increased from 2% to 5.2% (relative to the polyketone fiber). Μ of the obtained polyketone fiber decreased from 0.11 to 0.08,
When twisted at 00 times / m (twist coefficient = 1076
The twisting yarn strength utilization ratio (h) of 5) was 87.3%, which was an extremely excellent performance.

Example 8 A polyketone fiber was obtained in the same manner as in Example 1, except that the finishing agent having the following composition was used. Oleic acid sorbitan ester / polyethylene oxide 10 mol addition castor oil ester / bisphenol A
Lauric acid ester / polyethylene oxide hydrogenated castor oil maleic acid ester / polyether (propylene oxide / ethylene oxide = 35/65: molecular weight 2000
0) / sodium stearyl sulfonate / sodium dioctyl phosphate = 30/30/20/13/5/5/1
(Mass ratio). The polyketone fiber obtained was 1500 times /
When the twist of m was applied (twisting coefficient = 10638), the twisting yarn strength utilization ratio (h) was 83.9%, which was an extremely excellent performance.

[0065]

Example 9 Spinning was carried out in the same manner as in Example 1 except that the solvent of polyketone was an aqueous solution containing zinc chloride / sodium chloride = 65% by mass / 10% by mass and the concentration of polyketone was 8.2% by mass. , Washing, drying, defibration treatment, stretching, and finishing agent application. The single yarn sticking rate of the obtained polyketone fiber was reasonably good at 16%, 1500 times / m.
When twisted (twisting coefficient = 11165), the twisting yarn strength utilization ratio (h) was 74.5%, which was a good performance.

[Example 10] In Example 1, the spinneret diameter was 0.18 m.
Spinning, washing, drying, defibration treatment, stretching and application of finishing agent were performed in the same manner except that mφ was used and the discharge rate was 6.75 cc / min. The single thread sticking rate of the obtained polyketone fiber is 0.
%, The twisting yarn strength utilization rate (h) when twisted at 1200 times / m (twisting coefficient = 10475) is 79.5%.
And showed good performance.

[0066]

[Embodiment 11] In Embodiment 1, the spinneret diameter is 0.25 m.
Spinning, washing, drying, defibration treatment, stretching, and application of a finishing agent were performed in the same manner except that mφ was used and the discharge rate was 11.25 cc / min. Single yarn sticking rate of the obtained polyketone fiber
(d) is as good as 0%, and when the yarn is twisted 1000 times / m (twisting coefficient = 11203), the yarn utilization factor (h) is 7
The performance was as good as 6.2%.

[Example 12] The same procedure as in Example 1 except that the number of spins was 300, the discharge rate was 27 cc / min, and the drying conditions were a treatment at 160 ° C for 20 seconds and a constant length drying at 225 ° C for 1 minute. Spinning, washing, drying, defibration treatment, stretching, and finish application were performed. Single yarn sticking rate of the obtained polyketone fiber
(d) is as good as 1%, and the twisting yarn tenacity utilization rate (h) is 8 when twisted at 600 times / m (twist coefficient = 10775).
The performance was extremely good at 3.2%.

[0067]

Example 13 Five polyketone fibers which had been subjected to the one-step drawing and defibration treatment in Example 12 were combined to form 3890d.
tex / 1500f, followed by 2-stage drawing, 3-stage drawing,
A polyketone fiber was produced in the same manner except that a finishing agent was applied. The polyketone fiber obtained had a single yarn sticking ratio (d) as good as 1%, and a twisting yarn strength utilization ratio (h) of 84.3% when a twist of 250 times / m was applied (twisting coefficient = 10078).
And showed extremely good performance.

[0068]

Comparative Example 1 Spinning, washing, drying and stretching were carried out in the same manner as in Example 1 except that no defibration treatment was performed and no finishing agent was applied after stretching. The obtained polyketone fiber has a poor single thread sticking ratio (d) of 55% and is 1400 times / m.
The twisting yarn strength utilization factor (h) when twisted (twisting coefficient = 9919) was as low as 59.3%, which was outside the range of the present invention.

Comparative Example 2 Spinning, washing, drying and stretching were carried out in the same manner as in Example 9 except that no defibration treatment was performed and no finishing agent was applied after stretching. The obtained polyketone fiber had a very poor single thread sticking ratio (d) of 72%, which was 1400.
The twisting yarn high-strength utilization factor (h) when twisted at twists / m (twisting coefficient = 9880) was also extremely low at 53.2%, which was outside the range of the present invention.

[0069]

[Comparative Example 3] In Example 1, the pressure was 0.2 MPa at the entrance of the drying process (water content of polyketone fiber = 1100%).
However, when the same air pressure treatment as in Example 1 was performed, yarn breakage, fluff, and sagging frequently occurred, and stretching could not be performed.

Comparative Example 4 In Example 1, after completion of the washing step, polyketone fiber (water content = 59%) dried at a temperature of 150 ° C. for 35 seconds was subjected to the same pressure treatment as in Example 1 at a pressure of 0.2 MPa. Then, a polyketone fiber was produced in the same manner except that the pressure treatment after the first stage drawing was not performed and the finish agent was not applied after the drawing. The obtained polyketone fiber has a poor single yarn sticking ratio (d) of 44% and a twisting yarn strength utilization ratio (h) of 62.0% when twisted at 1400 turns / m (twisting coefficient = 9969). Sufficient and outside the scope of the invention.

[0070]

Comparative Example 5 A polyketone fiber was produced in the same manner as in Example 5, except that the silica fine particle emulsion was applied at the outlet of the drying step (water content of polyketone fiber = 0.2%). The obtained polyketone fiber has a single yarn sticking rate (d)
Is poor at 59%, and when twisted at 1400 turns / m (twist coefficient = 10047), the twisting yarn strength utilization rate (h) is also 5
It was completely insufficient at 4.5%, which was outside the scope of the present invention.

[Comparative Example 6] In Example 5, washing, drying and stretching were performed in the same manner except that the silica fine particle emulsion was applied at the coagulation bath outlet (before the washing process inlet). It could not be stretched.

[0071]

Comparative Example 7 In Comparative Example 1, Example 1 was performed after the stretching was completed.
A polyketone fiber was produced in the same manner except that the same finishing agent was applied and heat treatment was performed at 180 ° C. for 10 seconds. The obtained polyketone fiber had a good μ of 0.11, but had a poor single yarn sticking ratio (d) of 65% and a twisting strength of 1400 turns / m (twisting coefficient = 10211). The utilization factor (h) was 58.3%, which was completely inadequate, which was outside the scope of the present invention.

Comparative Example 8 In Example 1, the polyketone fiber was wound up without applying a finishing agent after the completion of stretching. Thirty obtained polyketone fibers were aligned and combined with a tension of 0.2 cN / dtex. When this polyketone fiber was twisted 250 times / m (twist factor = 9614), the twisting yarn strength utilization factor (h) was 74.8%, which was good, but many fluffs were observed in the twisted yarn. It was Since this polyketone fiber did not have a finishing agent attached thereto, μ was high, and when the fibers were rubbed together, yarn breakage easily occurred. When the scraped portion was observed with an electron microscope, many fibril-like substances having a diameter of 0.1 to 1 μm were observed.

[0072]

Comparative Example 9 The polyketone used in Example 1 was added to an aqueous solution containing 75% by mass of resorcin, and stirred and dissolved at 80 ° C. for 2 hours to obtain a dope having a polymer concentration of 8% by mass.
The obtained dope was made with a spinneret diameter of 0.15 mmφ, L / D = 1,
The coagulated yarn was obtained by ejecting from a spinneret having 50 holes at a discharge rate of 5.8 cc / min, and extruded through a 10 mm air gap into a methanol bath at -5 ° C. The obtained coagulated yarn was washed while being drawn 1.2 times in methanol at 20 ° C. and then dried at 100 ° C. for a fixed length to obtain an undrawn yarn. This unstretched yarn was drawn on a heating plate 5 times at 225 ° C, 2.5 times at 240 ° C, and 1.3 times at 258 ° C to obtain a drawn yarn. The 24 drawn yarns were combined and wound. This fiber had a single yarn sticking ratio (d) of 12%, and a twisting yarn strength utilization ratio (h) of 69.5% when a twist of 250 times / m was applied (twisting coefficient = 10293).

[0073]

Comparative Example 10 The polyketone used in Example 1 was added to hexafluoroisopropanol and dissolved by stirring at 30 ° C. for 2 hours to obtain a dope having a polymer concentration of 7% by weight. The dope thus obtained was discharged from the spinneret having a spinneret diameter of 0.15 mmφ and L / D = 1 and a hole number of 50 at a discharge rate of 6.3 cc / min.
A coagulated yarn was obtained by extruding into an acetone bath at 0 ° C. The obtained coagulated yarn was passed through a chamber having a temperature of 40 ° C. and a nitrogen flow rate of 1 m / min and a length of 10 m and a winding coagulated yarn at a speed of 4 m / min. The obtained coagulated yarn was allowed to stand at 30 ° C. for 24 hours and dried to obtain an undrawn yarn. This unstretched yarn was drawn on a heating plate 5 times at 225 ° C, 2.5 times at 240 ° C, and 1.3 times at 258 ° C to obtain a drawn yarn. Twenty-four of these drawn yarns were combined, and the same finishing agent as in Example 1 was applied and wound up. This fiber has a single yarn sticking rate (d) of 38%, which is outside the range of the present invention, and when twisted at 250 times / m (twisting coefficient = 10338), the twisting strength utilization rate (h) is 6
It was insufficient at 4.2%.

[0074]

[Comparative Example 11] The polyketone fiber prepared in Comparative Example 2 was combined with 30 fibers to which the finishing agent used in Example 1 was applied, and the finishing agent used in Example 1 was applied again.
Heat treatment was performed at 0 ° C. for 10 seconds to obtain a polyketone fiber.
This fiber has a single yarn sticking ratio (d) of 72% and is 250 times /
When the twist of m was applied (twisting coefficient = 9906), the twisting yarn strength utilization factor (h) was 58.1%, which was completely inadequate and out of the range of the present invention.

(Polyketone twisted product)

Example 14 The polyketone fiber prepared in Example 13 was pretwisted in the Z direction at 390 times / m (pretwisting tension 0.05c).
N / dtex), and two twin yarns of this were twisted in the S direction 390 times / m (twisting tension 0.05 cN / dtex) to obtain a twisted product. The twist coefficient of this polyketone twisted product is 22.
233, the twisting yarn strength utilization ratio (h) was 80.1%, which was extremely high, and the twisted yarn strength was 14.2 cN / dtex, which was extremely excellent. Furthermore, after twisting the polyketone twisted product in an RFL liquid having the following liquid composition, a drying zone (heat treatment at a tension of 3N at 160 ° C. for 120 seconds) and a heat setting zone (heat treatment at a tension of 4.2N at 220 ° C. for 60 seconds) , Normalizing zone (220 ℃, tension 2.8N, 60
RFL-treated polyketone twisted product was obtained through a heat treatment for 2 seconds.

(RFL liquid composition) Resorcinol 22.0 parts Formalin (30% by mass) 30.0 parts Sodium hydroxide (10% by mass) 14.0 parts Water 570.0 parts Vinyl pyridine latex (41% by mass) 364. The RFL resin-adhered polyketone twisted yarn obtained in 0 parts had a very high twisting yarn utilization factor (h) of 79.5%, and the twisted yarn strength was 1 as well.
It was an extremely excellent value of 4.1 cN / dtex.

In the examples of the present invention, twisting conditions, RF
The L treatment conditions and the performance of the twisted yarn are shown in Examples 15 to 1 below.
7 and the results of Comparative Examples 12 to 17 are collectively shown in Table 2.

Example 15 A polyketone twisted yarn was produced in the same formulation as in Example 14, except that the twisting conditions were the number of lower twists and the number of upper twists of 290 T / m, respectively. The obtained polyketone twisted yarn (twisting factor 16533) has a high twisting yarn utilization factor (h).
Is extremely high at 90.5%, and the strength of the twisted product is 16.0c.
N / dtex is extremely excellent, and the polyketone twisted product after RFL treatment is also very excellent. Twisted yarn strength utilization rate (h)
And had strength.

Example 16 A polyketone twisted yarn was produced in the same formulation as in Example 14 except that the twisting conditions were a lower twist number and an upper twist number of 190 T / m, respectively. The obtained polyketone twisted product (twisting factor 10832) has a high twisting yarn utilization factor (d).
Is as high as 97.1%, and the strength of the twisted product is 17.2c.
N / dtex is extremely excellent, and the polyketone twisted product after RFL treatment is also very excellent. Twisted yarn strength utilization rate (h)
And had strength.

[0078]

Example 17 A twisted yarn was prepared in the same manner as in Example 14 except that three twisted polyketone twisted yarns which were twisted underneath were twisted over. The obtained polyketone twisted product (twisting factor 20248) has a twisting yarn strength utilization ratio (h) of 84.
Extremely high at 1% and the strength of the twisted yarn is 14.9 cN / dt
It was extremely excellent as ex, and the twisted polyketone product after RFL treatment also had a very good twist yarn strength utilization ratio (h) and strength.

[0079]

COMPARATIVE EXAMPLE 12 Using the polyketone fiber produced in Comparative Example 9, both upper twist and lower twist were 39 under the same conditions as in Example 14.
Twisting was performed 0 times / m. The twistability was poor and many fluffs were generated during twisting. In addition, the obtained polyketone twisted yarn (twisting coefficient 22714) has a twisted yarn strength utilization ratio (h) of 60.
It was 5%, which was insufficient as compared with the twisted yarn of the polyketone of the present invention. Further, the twisting strength utilization factor (h) and the twisted product strength of the twisted product after the RFL liquid treatment were insufficient as compared with the polyketone twisted product of the present invention.

COMPARATIVE EXAMPLE 13 A twisted yarn was prepared in the same manner as in Comparative Example 12 except that the number of times of twisting was 290 times / m for both upper twisting and lower twisting. The twistability was poor and many fluffs were generated during twisting. The obtained polyketone twisted product (twist coefficient 16890)
The twist utilization factor (h) was 77.9%, which was insufficient as compared with the twisted yarn of the polyketone of the present invention. Also, RFL
The twisting strength utilization factor (h) and the strength of the twisted product of the twisted product after the liquid treatment were also insufficient as compared with the polyketone twisted product of the present invention.

[0080]

[Comparative Example 14] Using the polyketone fiber produced in Comparative Example 10, under the same conditions as in Example 14, both upper twist and lower twist were 3
90 times / m of twisted yarn was performed. The obtained polyketone twisted product (twisting coefficient 22807) had a twisting yarn strength utilization ratio (h) of 62.
The strength of the twisted yarn was 5%, which was 5.1 cN / dtex, which was significantly inferior to the twisted yarn of the polyketone of the present invention. Also, the twist strength utilization factor (h) and the twisted product strength of the twisted product after the RFL liquid treatment were significantly inferior to the polyketone twisted product of the present invention.

Comparative Example 15 Polyketone Fiber 30 Produced in Comparative Example 2
The books were combined, and under the same conditions as in Example 14, both upper twisting and lower twisting were performed at 390 times / m. There was a large amount of slack in the twisted yarn, and fluffs frequently occurred during twisting, and a twisted yarn of sufficient quality could not be obtained.

[0081]

[Comparative Example 16] Using the polyketone fiber produced in Comparative Example 8, both the upper twist and the lower twist were 39 under the same conditions as in Example 14.
Twisting was performed 0 times / m. The twistability was poor and many fluffs were generated during twisting. The obtained polyketone twisted yarn (twisting coefficient 21211) had a twisting yarn high-strength utilization rate (h) of 64.9%, which was inferior to the polyketone twisted yarn product of the present invention, and had a large number of fluffs, resulting in poor quality and It was entwined with fluff and fibrils.

[Comparative Example 17] Using the polyketone fiber produced in Comparative Example 11, under the same conditions as in Example 14, both upper twist and lower twist were 3
90 times / m of twisted yarn was performed. The obtained polyketone twisted yarn (twisting coefficient 21854) had a twisting yarn strength utilization ratio (h) of 63.
1%, which was significantly inferior to the twisted polyketone of the present invention. Although the strength of the raw yarn was the same as that of Example 14, the strength of the twisted yarn was 10.6 cN / dtex, which was completely inferior. Further, the twisting strength utilization factor (h) and the twisted product strength of the twisted product after the RFL liquid treatment were significantly inferior to the polyketone twisted product of the present invention.

[0082]

[Table 1] Table 1 is a table showing characteristics of the polyketone fiber of the present invention and the polyketone fiber of the comparative example.

[0083]

[Table 2]

(Note) *; Strength utilization factor of twisted yarn after REL treatment
(h) = strength of REL-treated twisted yarn / sum of strength of polyketone fiber used for twisted yarn **; Formula (3) = 100 x (1-4.79 x ^10-9 x K
^1.78 ) Table 2 is a table showing characteristics of the twisted polyketone polyketone of the present invention and the twisted polyketone of Comparative Example.

[0085]

EFFECT OF THE INVENTION The polyketone fiber of the present invention has excellent mechanical properties such as high strength and high elastic modulus, has no single yarn sticking, has a small dynamic friction coefficient between fibers, is homogeneous, and has few defects. It is a fiber that has an excellent utilization factor of twisted yarn strength, exhibits high strength even after twisted yarn, and is also excellent in fatigue resistance. By using the polyketone fiber of the present invention as a twisted product, it can be used in a wide range of fields as high-strength industrial materials (for example, nets, nets, ropes, cables, and other civil engineering / industrial materials, tires,
It is expected to be applied to rubber reinforcing materials such as belts and hoses, reinforcing materials such as plastic reinforced fibers, etc.). In particular,
It is extremely useful as a reinforcing material such as a rubber reinforcing material for tires, belts and hoses, and FRP for applications in which a twisted yarn that is a reinforcing material is required to have high strength under a high mechanical load.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) D02G 3/26 D02G 3/26 4L048 3/36 3/36 3/48 3/48 D03D 1/00 D03D 1 / 00 D 3/02 3/02 15/00 15/00 A D06M 15/41 D06M 15/41 15/693 15/693 // C08L 73:00 C08L 73:00 D06M 101: 30 D06M 101: 30 F term (Reference) 4F072 AA02 AA04 AA07 AA08 AB02 AB24 AC04 AD02 4L033 AA06 AB03 AB05 AC11 CA34 CA68 4L035 AA04 BB03 BB04 BB10 BB15 BB16 BB22 BB60 BB61 PA36 MA01EE01 DD24 PA21 RA24 4L038 AA09 AB07 AB08 BA11 BB07 CA01 DA10 4L048 AA19 AA42 AA48 AB01 AB12 AC09 BB04 CA01 CA09

Claims (19)

[Claims] 1. A polyketone fiber in which 95 to 100% by mass of the repeating unit is composed of 1-oxotrimethylene represented by the following structural formula (1) and which satisfies the following requirements a to e: Characteristic polyketone fiber. (a): Crystallinity ≧ 60% (b): Crystal orientation ≧ 90% (c): Tensile strength ≧ 10 cN / dtex (d): Single yarn sticking rate ≦ 30% (e): Finishing agent adhesion rate = 0.3 to 15 mass% [Chemical formula 1] 2. A polyketone fiber composed of 1-oxotrimethylene represented by the following structural formula (1), wherein 100% by mass of the repeating unit satisfies the following requirements a to e: The polyketone fiber according to claim 1. (a): Crystallinity ≧ 70% (b): Crystal orientation ≧ 95% (c): Tensile strength ≧ 15 cN / dtex (d): Single yarn sticking rate ≦ 10% (e): Finishing agent adhesion rate = 1-5% by mass 3. The single yarn sticking ratio (d) is 30% or less, and the fiber-fiber dynamic friction coefficient (f) is 0.01 to 0.5. Polyketone fiber. 4. The polyketone fiber is an aggregate of single yarns having a round cross section, and the circularity (g) of the cross section is 1.0 to 1.2. The polyketone fiber according to Crab. 5. The polyketone fiber according to claim 1, wherein the single yarn fineness is 0.1 to 10 dtex. 6. The polyketone fiber according to claim 1, wherein a twisting yarn strength utilization factor (h) when twisted so that a twisting coefficient K becomes 10,000 is 65% or more. [Here, the twisting yarn strength utilization rate (h) is a 100-percentage obtained by dividing the strength of the polyketone twisted product after twisting by the strength of the polyketone fiber before twisting, and K is the twisting yarn defined by the following formula (1). It is the twist coefficient of the product. K = Y × D ^0.5 (T / m · dtex ^0.5 ) (1) In the formula (1), Y is the number of twists per 1 m of polyketone twisted yarn (T / m), and D is the total indication of polyketone twisted yarn. The fineness (dtex). ] 7. The polyketone fiber according to any one of claims 1 to 6, wherein the twisting yarn tenacity utilization factor (h) is within the range of the following formula (2). Twisted yarn strength utilization rate (h) (%) ≧ 100-K / 300 ・ ・ ・ (2) 8. The polyketone fiber according to claim 1, wherein the twisting strength utilization factor (h) of the polyketone fiber is in the range of the following formula (3). Twisted yarn strength utilization rate (h) (%) ≧ 100 × (1-4.79 × 10 ⁻⁹ × K ^1.78 ) ... (3) 9. A short fiber comprising the polyketone fiber according to claim 1, having an average fiber length of 0.1.
Polyketone short fibers characterized by having a length of -100 mm. 10. A polyketone obtained by copolymerizing an olefin and carbon monoxide is dissolved in a metal salt solution, the solution is extruded from a spinneret into a coagulation bath, and then the metal salt is washed from the obtained fibrous material. In the method for producing a polyketone fiber, in which the fiber that has undergone the drying step after being removed is subjected to hot drawing, the water content is 0 to 4 at any stage between the drying step and the end of the hot drawing step.
0.1 to 20 with respect to the polyketone fiber at any stage between the step of applying an external force that causes a deviation between single yarns to the fiber at 0% by mass, and the end of the drying step to the end of the hot drawing step.
A method for producing a polyketone fiber, comprising the step of applying a mass% of a finishing agent. 11. A polyketone obtained by copolymerizing an olefin and carbon monoxide is dissolved in a metal salt solution, the solution is extruded from a spinneret into a coagulation bath, and then the metal salt is washed from the obtained fibrous material. In the method for producing a polyketone fiber in which the fiber that has been subjected to a drying step and then subjected to a hot drawing is hot-stretched in the stage where the water content of the polyketone fiber exceeds 40% by mass from the washing step to the end of the drying step in the polyketone fiber. 1-2
A method for producing a polyketone fiber, comprising the step of applying 0% by mass of a release agent. 12. The polyketone fiber according to any one of claims 1 to 9 is contained in at least a part thereof, and the fibers constituting the twisted product are twisted at a rate of 10 times / m or more. Twisted yarn. 13. The twisted yarn according to claim 12, wherein 50 to 100% by mass of the twisted yarn is the polyketone fiber according to any one of claims 1 to 9. 14. A polyketone twisted product obtained by twisting a polyketone fiber having 95 to 100% by mass of repeating units of 1-oxotrimethylene with a twisting coefficient K of 100 to 50,000, and having a low twisting yarn strength utilization factor (h). A polyketone twisted yarn characterized by being in the range of formula (3). Twisted yarn strength utilization rate (h) (%) ≧ 100 × (1-4.79 × 10 ⁻⁹ × K ^1.78 ) ... (3) 15. A polyketone twisted product having a twisting coefficient K of 10,000 or more, wherein the twisted product has a strength of 15 cN / d.
A twisted yarn of polyketone characterized by having a tex or more.
(However, the strength of the twisted product is the strength of the twisted product divided by the total indicated fineness of the polyketone fiber used for the twisted yarn.) 16. A polyketone twisted product having a twisting coefficient K of 20,000 or more, wherein the twisted product has a strength of 12 cN / d.
A twisted yarn of polyketone characterized by having a tex or more.
(However, the strength of the twisted product is the strength of the twisted product divided by the total indicated fineness of the polyketone fiber used for the twisted yarn.) 17. A polyketone fiber with respect to 0.1 to 10
Mass% of resorcin-formalin-latex resin is attached, The twisted polyketone product according to any one of claims 12 to 16, wherein 18. A molded article comprising the polyketone fiber according to any one of claims 1 to 9 and / or the twisted polyketone product according to any one of claims 12 to 17. 19. The molded product according to claim 18, wherein the molded product is a rubber product selected from the group consisting of tires, belts, hoses, and endless tracks.