JP2003027333A - Polyketone fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyketone fiber having excellent characteristics such as high strength, high modulus, high melting point and high heat resistance, and further to provide a method for producing the fiber with good productivity. SOLUTION: This polyketone fiber is composed of 1-oxotrimethylene represented by chemical formula (1), and has >=60% crystallinity, >=90% crystal orientation, and >=10 cN/dtex tensile strength. The modified degree represented by L<2> /4&pi;A (wherein, L is a circumference length of a cross section of the polyketone fiber; and A is a cross section area) is >=1.2, and the coefficient (&mu;) of kinetic friction between the fiber and the fiber is 0.01-0.5.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to industrial material applications, particularly, rubber reinforcing materials, cement reinforcing materials, reinforcing materials such as FRP,
The present invention relates to a polyketone fiber, a cord made of the polyketone fiber, and a method for producing the polyketone fiber, which are useful in the field of composite products with other materials such as rubber and resin, such as resin-coated woven and knitted fabrics such as airbags and sail cloths.

[0002]

2. Description of the Related Art In recent years, it has been found that by polymerizing carbon monoxide and an olefin using palladium or nickel as a catalyst, an aliphatic polyketone in which carbon monoxide and an olefin are copolymerized substantially completely can be obtained. The fiber using is excellent in mechanical and thermal properties such as high crystallinity, high strength / high elastic modulus, and high melting point, and is expected as a next-generation general-purpose polymer material.

Polyketone fibers are expected to develop into industrial material applications by taking advantage of their excellent mechanical and thermal properties, and in particular, rubber reinforcing materials for tires, belts, hoses, cement reinforcing materials, tension members, etc. It is expected to be used as a reinforcing material such as a resin reinforcing material such as FRP, and a composite product with a material other than polyketone such as a resin-coated woven or knitted material such as an airbag and a sail cloth. When used in combination with a material such as rubber, resin, or cement, high adhesion between the polyketone fiber and the material forming the molded body is required. In the conventional fiber materials, as a method for increasing the adhesiveness between the fiber and the material, a method for chemically modifying the fiber surface, a method for coating a binder compound having high adhesiveness between the fiber and the material, and a fineness of the fiber It is effective to use a method of making the fiber cross-sectional shape flattened or modified.

The method of chemically modifying the surface of the fiber and the method of coating with a binder compound have a problem that the treatment cost is high, and the method of making the fiber fine has a problem that fluff or yarn breakage is likely to occur. On the other hand, the method of flattening or deforming the fiber cross-sectional shape is an effective means for increasing the adhesiveness with rubber or the like. Up to now, many reports on polyketone fibers have been published (for example, JP-A-2-112).
413, JP-A-4-228613, JP-A-4-505344, JP-A-4-228613, JP-A-7-508317, and JP-A-8-507.
No. 328, US Pat. No. 5,955,019, International Publication 9
9/18143 pamphlet, International publication 00/096
11 pamphlet, JP 2000-345431 A). However, none of the documents disclose a technique relating to a polyketone fiber having a modified cross section and a method for producing the same.

Although many reports have been made so far regarding modified cross-section fibers composed of polymers other than polyketones, even if these techniques are directly applied to polyketones, polyketone fibers having a high degree of modification are industrially produced for the following reasons. Can't get In order to obtain a high-strength polyketone fiber, it is necessary to orient the fiber by performing drawing at a high ratio. However, such highly oriented polyketone fibers are
Consisting of fibril-like fiber bundles (Japanese Patent Laid-Open No. 2001-131
The present inventors have found that there is a property that fibril peeling easily occurs due to friction between fibers and devices or between fibers and fibers during manufacturing. In particular, in the case of a modified cross-section fiber, the problems of the separation of the fibrils and the decrease in the twisting property due to the friction between the fibers and the fiber become remarkable, and the polyketone fiber having a high degree of deformation has a large friction resistance, and the process passability during the twisting is high. Since it is poor, there is a problem that the twisted yarn causes a reduction in strength and a reduction in fatigue resistance.

In order to obtain a polyketone fiber having a high strength, a high elastic modulus and a high heat resistance, a polyketone having a high crystallinity and a high melting point in which the proportion of 1-oxotrimethylene is 95% by mass or more must be used. Must have such high crystallinity
In order to form a high melting point polyketone into a fiber, it is necessary to perform a wet spinning method in which the polyketone is dissolved in an organic solvent or a metal salt solution and then discharged into a coagulation bath to form a yarn, followed by washing, drying and drawing. However, when a polyketone modified cross-section fiber is to be obtained by the wet spinning method, it is only necessary to carry out spinning using a spinneret consisting of modified cross-section discharge holes, (1) deformation of the cross-sectional shape due to variations during discharge, ( 2) Deformation of cross-sectional shape due to swelling / solidification during solidification, (3) Deformation of cross-sectional shape due to sticking of single yarn during drying, (4) Change in cross-sectional shape due to high-magnification / high-strength drawing, etc. It is difficult to obtain high-quality fibers, (5) drawability due to sticking of single yarn, deterioration of twistability, and (6) fibrillation occur frequently, so it is difficult to obtain polyketone fibers with high productivity and high degree of irregularity. there were.

Among the above-mentioned wet spinning methods, the wet spinning method using a metal salt solution as a solvent is the most excellent method for industrially obtaining a high strength polyketone fiber, and the above (3) to (5) ) Problem has become apparent, high strength and high elastic modulus,
It is very difficult to industrially obtain a polyketone fiber having high heat resistance and high degree of deformation. As described above, a polyketone having a high strength, a high elastic modulus, a high melting point, a high quality, a high strength even after twisting, and a high deformability that is excellent in the process passability during drawing and twisting. Nothing has been known so far about the fiber and its manufacturing method.

[0008]

The object of the present invention is to provide a polyketone fiber having excellent mechanical properties and thermal properties such as high strength / high elastic modulus, high melting point, and high heat resistance, and to industrially produce this fiber. It is to provide a method of manufacturing.
Specifically, along with the above performance, the following (1) to (4)
To provide a polyketone fiber and a method for producing the same. (1) The degree of irregularity is high even with the wet spinning method. (2) There is no single yarn sticking even with a high degree of irregularity. (3) Generation of fluff and fibrils is small even when stretched at a high ratio. (4) Even with a high degree of irregularity, the coefficient of friction is small and the twistability and process passability are excellent.

[0009]

The present invention is as follows. (1) 95 to 100% by mass of the repeating unit consists of 1-oxotrimethylene represented by the chemical formula (1), the crystallinity is 60% or more, the crystal orientation is 90% or more, and
A polyketone fiber having a tensile strength of 10 cN / dtex or more, a fiber deformity shown below of 1.2 or more, and a fiber-fiber dynamic friction coefficient (μ) of 0.01 to 0.5.
Polyketone fiber characterized by being. Fiber irregularity = L ² / 4πA (where L is the outer peripheral length of the cross section of the polyketone fiber, A is the cross-sectional area)

[0010]

[Chemical 2]

(2) 100 mass% of the repeating unit consists of 1-oxotrimethylene represented by the chemical formula (1),
The polyketone fiber according to (1), which has a crystallinity of 70% or more, a crystal orientation of 95% or more, a tensile strength of 12 cN / dtex or more, and a single yarn fineness of 0.5 to 2 dtex. . (3) The polyketone fiber according to (1) or (2), characterized in that the degree of fiber irregularity is 3 or more and the cross-sectional shape of the fiber is flat. (4) 0.3 to 10% by mass of the finishing agent is attached to the polyketone fiber (1) to
The polyketone fiber according to any one of (3). (5) The polyketone fiber according to any one of (1) to (4), wherein the polyketone fiber has a single yarn sticking rate of 30% or less.

(6) A cord comprising the polyketone fiber according to any one of (1) to (5), which is twisted in a twist coefficient K of 100 to 30,000 shown below. K = Y × D ^0.5 (T / m · dtex ^0.5 ) (In the formula, Y is the number of twists per meter (T / m), and D is the total fineness (dtex) of the polyketone used for the twisted yarn)

(7) Polyketone is dissolved in a metal salt solution containing zinc halide, the solution is extruded from a spinneret through an air gap into a coagulation bath, and the metal salt is washed and removed from the obtained yarn. In the method for producing a polyketone fiber which is dried and then hot-stretched, the spinneret is a modified spinneret having a spinneret irregularity of 1.2 or more as shown below, and any one of the spinneret from the start of drying to the end of hot stretching is used. Moisture rate is 0-4 at the stage
An external force that causes a deviation between single yarns is applied to 0% by mass of fibers, and 0.1 to 20% by mass of a finishing agent is applied to polyketone fibers at any stage between the end of drying and the end of hot drawing. A method for producing a polyketone fiber, comprising:

(8) Polyketone is dissolved in a metal salt solution containing zinc halide, the solution is extruded from a spinneret through an air gap into a coagulation bath, and the metal salt is washed and removed from the obtained yarn. In the method for producing a polyketone fiber which is dried and then hot-stretched, the spinneret is a modified spinneret having a spinneret irregularity of 1.2 or more as shown below, and the water content between the start of washing and the end of drying is 40%. A method for producing a polyketone fiber, which comprises adding 0.1 to 20% by mass of a mold release agent to the polyketone fiber in an amount of not less than mass%. Deformation degree of spinneret = L ₀ ² / 4πA ₀ (where L ₀ is the outer peripheral length of the spinneret discharge hole, and A ₀ is the cross-sectional area of the spinneret discharge hole)

The present invention will be described in detail below. The polyketone fiber of the present invention contains 95 to 100% by mass of the repeating unit.
Is a polyketone composed of 1-oxotrimethylene represented by the chemical formula (1).

[0016]

[Chemical 3]

The higher the proportion of 1-oxotrimethylene in the repeating unit, the higher the regularity of the molecular chain, and the more highly crystalline and highly oriented the fiber can be obtained.
A fiber having high strength, high elastic modulus and high heat resistance can be obtained.
Therefore, the proportion of 1-oxotrimethylene in the polyketone is more preferably 97 to 100% by mass, and most preferably 100% by mass. If desired, olefins other than ethylene such as propene and hexene, and compounds having unsaturated hydrocarbons such as methyl methacrylate and sodium allyl sulfonate may be copolymerized.

The degree of polymerization of polyketone is 2-1 in terms of intrinsic viscosity.
It is preferably 0 and more preferably 3 to 6. If the intrinsic viscosity becomes too small, the strength and spinnability of the polyketone fiber will tend to decrease, and if the intrinsic viscosity becomes too large, the polymerization cost and fiber cost will increase. In order for the polyketone fiber of the present invention to exhibit excellent mechanical properties and thermal properties, it is necessary that the crystallinity and the crystal orientation are within a specific range.

The degree of crystallinity is a structural parameter representing the quantity ratio of crystal structures. The higher this value, the more
In order to exhibit high strength, high dimensional stability, high heat resistance and high chemical resistance, the crystallinity must be 60% or more, preferably 70% or more, more preferably 80% or more. . The crystal orientation degree is a structural parameter indicating the degree of regularity in which the molecular chains in the fiber are arranged in the fiber axis direction, and the crystal orientation degree needs to be 90% or more,
It is preferably at least 95%, more preferably at least 97%. When the crystal orientation degree is less than 90%, a fiber having a high elastic modulus and excellent dimensional stability cannot be obtained.

It is extremely important that the polyketone fiber of the present invention has a fiber irregularity of 1.2 or more. The degree of fiber irregularity is L, the outer peripheral length of the cross section of the polyketone fiber, and A the cross-sectional area.
Then, it is represented by L ² / 4πA. This value is 1.0 when the cross-sectional shape is a perfect circle. If the degree of fiber irregularity is less than 1.2, the surface area of the fiber per unit fineness becomes too small, and sufficient adhesive force cannot be exhibited. The larger the degree of fiber irregularity, the larger the surface area of the fiber and the better the adhesion to rubber and the like. Therefore, the degree of irregularity must be 1.2 or more, preferably 1.5 or more, more preferably 2 or more. That is all.

The polyketone fiber of the present invention thus has a modified cross section, and the cross-sectional shape is elliptical, square,
Rectangle, diamond, triangle, star, alphabet (C,
Conventionally known shapes such as X-type, Y-type, V-type, W-type, etc., dumbbell-type, etc. may be mentioned. Even if the fiber cross section is circular, the fiber irregularity may be within the scope of the present invention by having a large number of grooves and voids in the fiber surface layer portion. In a flat yarn whose cross-sectional shape is long in the transverse direction, the fiber irregularity is preferably 3 or more, more preferably 5 or more.

The tensile strength of the polyketone fiber is 10c
It needs to be N / dtex or more. If the tensile strength is less than 10 cN / dtex, the strength is insufficient and the weight of the material cannot be reduced. As a result, the toughness of the fiber is insufficient and the fatigue resistance is insufficient. From the viewpoint of development in industrial material applications, the higher the tensile strength, the more preferable, and specifically 12 cN / dtex or more, and more preferably 15 cN / dtex or more. Since the higher the elastic modulus of the polyketone fiber, the more excellent the mechanical dimensional stability, it is preferably 200 cN / dtex or more, more preferably 30
0 cN / dtex or more, most preferably 350 cN / d
tex or more.

When the fiber cross section is irregular, since the specific surface area is larger than that of the polyketone fiber having a circular cross section, the friction resistance between the fibers and between the fibers and the metal is likely to occur, and the single yarn is used during the manufacturing process, the processing process, and the use. Breakage, fluffing, and fibrillation are likely to occur, and the process passability is reduced, and the quality and mechanical properties of the obtained fiber are likely to be reduced. In particular, since polyketone fibers having a large number of filaments are used for industrial material applications, the dynamic friction coefficient (μ) between fibers is 0.01 to
It needs to be 0.5. When the coefficient of dynamic friction (μ) between fibers is less than 0.01, the focusing property in the drawing process is reduced and slippage in the twisting process occurs. If the dynamic friction coefficient (μ) between fibers exceeds 0.5, fluff, single yarn breakage, and fibril separation occur during the drawing and twisting processes.
Preferably, the coefficient of dynamic friction (μ) between fibers is 0.0
3 to 0.4, more preferably 0.05 to 0.3
5, most preferably 0.1 to 0.25.

In order to reduce the frictional resistance, it is extremely effective to attach a finishing agent to the polyketone fiber to reduce the contact resistance by focusing and antistatic of the fiber and reduce the friction coefficient of the fiber surface by forming an oil film. Is. The finishing agent in the present invention is a compound that is applied to the polyketone fiber in any step from the drying step to the winding, and is a compound adhered to the fiber surface or between the fibers, and is washed by washing with water or an organic solvent.
It is a removable compound.

The components of the finishing agent are not limited, and for example, the finishing agent described in Japanese Patent Application No. 2000-19995 can be used. In order to impart smoothness and abrasion resistance to the fiber, it is preferable that the finishing agent contains an ester compound, a mineral oil, a polyether compound or the like. The ester compound is a component that improves the smoothness of the surface of the polyketone fiber and improves the wearability due to the slip,
Specific examples of preferable ester compounds include octyl stearate and lauryl oleate, and the molecular weight thereof is 500 to 3000 from the viewpoints of smoothness and process passability.
Is preferred.

Mineral oil is also a component for improving the smoothness and abrasion resistance of the surface of the polyketone fiber, preferably a paraffin type or naphthene type, and its viscosity is such that the Redwood viscosity at 30 ° C. is 40 to 800 seconds. preferable. Polyether has the function of increasing the strength of the oil film formed on the fiber surface by the finishing agent, and can dramatically improve the wear resistance. Specifically, a polyether whose main component is a polyolefin oxide obtained by copolymerizing propylene oxide and ethylene oxide is preferable, and its molecular weight is 15
00 to 20000 is preferable.

The finishing agent used in the present invention includes an emulsifier (for example, polyoxyethylene stearyl ether),
It is preferable to use an antistatic agent (for example, an anionic surfactant or the like) in order to impart antistatic property, abrasion resistance, emulsifying property, and rust preventive property to the fiber. The adhesion rate of the finishing agent is preferably 0.1 to 20 mass% with respect to the fiber, and more preferably 0.3.
-10 mass%, most preferably 1-5 mass%. If the adhesion rate is less than 0.1% by mass, the effect of reducing the frictional resistance will be reduced, and if it exceeds 20% by mass, the contact resistance between the oil films will increase, and the friction between fibers will easily increase.
The finishing agent can be applied as it is in a straight form, or it can be dispersed in water and attached to the fibers in the form of an emulsion. 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 that it can be dispersed and applied to.

When the polyketone modified cross-section fiber is produced by the wet spinning method, the single yarns are more likely to stick together during spinning, drying and drawing, as compared with a fiber having a circular cross section. Therefore, it is very important to suppress single yarn sticking in order to suppress the process passability during twisting and the reduction in strength after twisting. Therefore, the polyketone fiber of the present invention preferably has a single yarn sticking rate defined by the following formula of 30% or less. Single thread sticking rate = [1- (apparent number of single threads / number of single threads)] x
100 (%) Single thread sticking rate is a value showing the numerical ratio of sticking single thread in a multifilament. To explain with a concrete example,
If there are two sets of fibers produced by using a spinneret having 10 holes and two single yarns are stuck together, the number of single yarns is 10, and the apparent number of single yarns is 8 and the single yarn sticking rate is 20%. Single thread sticking rate is 30%
If the value exceeds the above range, the fiber becomes hard, and excessive force is apt to be applied to the single yarn, so that fluff and yarn breakage are likely to occur during twisting, and the strength after twisting is likely to decrease. The single thread sticking rate is more preferably 20% or less, and most preferably 10%.
% Or less, more preferably 0%.

The polyketone fiber of the present invention may be a short fiber or a long fiber and can be selected according to the application. Generally, short fibers for FRP and cement reinforcement,
Long fibers are used for rubber reinforcements and resin-coated woven and knitted fabrics. The fineness of polyketone fiber is not limited, but strength,
From the viewpoint of adhesiveness to other materials, it is preferable that the single yarn fineness is small, but if the single yarn fineness is too small, it becomes difficult to produce fibers with a high degree of irregularity, and there is clogging of the spine, fluff, and single yarn breakage. Single yarn fineness of 0.1 to 5 dtex
Is preferable, and 0.5 to 2 dtex is more preferable from the viewpoint of fiber physical properties, spinnability, stretchability, and adhesiveness.

In the case of multifilament, the number of filaments is not particularly limited, but usually 10 to 100,000 filaments,
It is preferably 100 to 10,000, and the total fineness is usually 10 to 100,000 dtex, preferably 100 to 10
It is 000 dtex. When a monofilament with a flat cross section is used, the single yarn fineness is 10 to 1 depending on the fiber irregularity.
Those of 00000dtex are preferably used. The polyketone fiber of the present invention, for the purpose of imparting improved weather resistance, improved thermal stability, imparting functionality, shape retention, etc., a pigment, a masking agent,
A matting agent, a heat stabilizer, a flame retardant, a plasticizer, a flameproofing agent, an antiseptic agent, an antibacterial agent, an antifouling agent, a resin and the like may be contained.

When the polyketone fiber of the present invention is used for a rubber reinforcing material for tires, belts, hoses, etc., it is usually twisted and embedded in the material as a cord. The twisted form of the cord is not particularly limited, but the twist coefficient K represented by the following formula is preferably in the range of 100 to 30,000. K = Y × D ^0.5 (T / m · dtex ^0.5 ) In the formula, Y is the number of twists per meter (T / m), and D is the total indicated fineness (dtex) of the polyketone used for the twisted yarn. The total indicated fineness is the sum of the fineness of all polyketone fibers used for the twisted yarn. For example, when three 1670 dtex polyketone fibers are twisted together, the total fineness of the twisted product is 501.
It becomes 0 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.

The surface layer of the twisted yarn cord may be coated with an adhesive such as resorcin-formalin-latex resin (RFL resin). In this case, the adhesion rate of the RFL resin is
It is preferably 2 to 7 mass% with respect to the polyketone fiber. The cord using the polyketone fiber of the present invention has a large surface area as compared with the cord made of the conventional polyketone fiber having a circular cross section in the case of the same fineness, and therefore has excellent adhesive force with a matrix compound such as rubber or resin. The value of the adhesive strength cannot be unconditionally specified because it varies depending on the fineness of the polyketone fiber used and the form of the cord.
In the case of a double twisted cord of polyketone fiber of 00 to 2000 dtex, the adhesive force with rubber is preferably 120 N / c.
m / cord or more, more preferably 140 N / cm / c
ord or more, most preferably 160 N / cm / cord
That is all.

The method for producing the polyketone fiber of the present invention will be described by taking a wet spinning method using a metal salt solution as a solvent as an example. As a method for producing a modified cross-section fiber by a wet spinning method using a metal salt, (a) a method using a modified spinneret, (b)
After performing the composite spinning of polyketone and heterogeneous compound,
A method for removing heterogeneous compounds, (c) a method of sticking and fusing the yarn discharged from the circular spinneret at an arbitrary step after discharging, (d) a process after discharging the yarn discharged from the circular spinneret And a method of deforming the cross-sectional shape with. Industrially, the method (a) is preferably used from the viewpoints of handleability and uniformity of cross-sectional shape.

The metal salt solution used for dissolving the polyketone is
There is no limitation as long as it has the ability to dissolve polyketone, and for example, zinc halide, alkali metal halide salt, alkaline earth metal halide salt and the like are used.
Above all, an aqueous solution containing 10 to 80% by mass of zinc halide (zinc chloride, zinc iodide, etc.) is preferably used. Compounds other than the above metal salts may be mixed within the range not impairing the object of the present invention.

The salt concentration of the metal salt solution is 50 to 80% by mass.
Is preferred. When less than 50 mass% and 80
When it exceeds the mass%, spinning tends to be unstable.
The salt concentration is defined by the following formula. Salt concentration (mass%) = [mass of salt / (mass of salt + mass of solvent)] × 100 The concentration of the polyketone dissolved in the metal salt solution is 1 to 30 mass from the viewpoint of solubility, spinnability and manufacturing cost. % Is preferred, and in order to obtain fibers with high strength and high degree of irregularity, 5 to 25
Mass% is preferred. The polymer concentration is defined by the following formula. Polymer concentration (mass%) = [polymer mass / (polymer mass + metal salt solution mass)] × 100

The solution in which the polyketone is dissolved is filtered through a filter if necessary, and then extruded from the spinneret into a coagulation bath. As the shape of the spinneret, a modified spinneret according to the cross-sectional shape of the final fiber is used. When using the modified spinneret, it is necessary that the spinneret deformity calculated by the following formula is 1.2 or more. Deformation degree of spinneret = L ₀ ² / 4πA ₀ (L ₀ is the outer peripheral length of the spinneret discharge hole, A ₀ is the cross-sectional area of the spinneret discharge hole)

In the case of a metal salt solution, the discharged solution swells due to variability and greatly reduces the degree of irregularity. Therefore, the L / D of the spinneret is set to 1 or more to suppress variability, and the solution once passes through gas. Air gap spinning method in which the air gap is discharged to the coagulation bath, high tension spinning in which the spinning tension reaches the air gap portion, discharge temperature is 80 ° C. or higher, more preferably 90 ° C. or higher, and spinneret It is preferable to keep the surface warm. The L / D of the modified spinneret means L is the length of the spinneret discharge hole, D is the equivalent circle diameter of the discharge hole,
It is a value obtained by dividing L by D. The equivalent circle diameter D is calculated by the following equation with the discharge hole cross-sectional area being S. D = 2 × (S / π) ^0.5

The spinning solution that has passed through the air gap is introduced into the coagulation bath, where it is coagulated into yarn. Since the polymer swells immediately after the start of coagulation to reduce the degree of irregularity, the coagulation bath temperature is preferably 20 ° C. or lower, more preferably 0 ° C. or lower, and the coagulation bath liquid is preferably the same as the salt used with the polyketone solvent. Using an aqueous solution containing 5% by mass or more of the metal salt of (1), the spinning draft (discharge speed from the spinneret / pulling speed) is preferably 1 or more, more preferably 1.2 or more. When the yarn comes into contact with the guide or roll immediately after solidification, the cross-section end of the fiber is deformed. Therefore, the contact with the solid such as guide or roll is preferably 3 seconds or more after the start of solidification, more preferably 5 seconds. After the traveling in the coagulation bath.

The fibrous material 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. Next, the fiber is dried. There is no limitation on the drying method, and a tunnel type dryer, a roll heater, a net process type dryer or the like can be used to perform drying while stretching or at a constant length or while shrinking. From the viewpoint of maintaining the degree of deformation, the tension during drying is preferably 0.03 cN / dtex.
Or more, more preferably 0.06 cN / dtex or more. The drying temperature is not limited, but it is 2 from the viewpoint of strength development.
The temperature is preferably 00 ° C to 240 ° C, and is preferably 120 ° C to 200 ° C from the viewpoint of developing the degree of irregularity and preventing single yarn sticking. Once
After drying at 120-200 ℃, 200-240 ℃ continuously
By carrying out the heat treatment at 1, a polyketone fiber having a high degree of irregularity and high physical properties can be obtained.

Next, the dried fiber is subjected to hot drawing in a single stage or in multiple stages of two or more stages. When performing multi-stage stretching, a method of gradually increasing the stretching temperature is preferable. The stretching temperature is preferably (150 ° C. to melting point of polyketone fiber). 1
If the temperature is lower than 50 ° C., it becomes difficult to obtain a polyketone fiber having high strength and high elastic modulus, and if the temperature exceeds the melting point of the polyketone fiber, the fiber is melted and easily cut during stretching, or the degree of irregularity is easily lowered. From the viewpoints of stretchability, physical properties of fibers and degree of irregularity, the stretching temperature is preferably [(150 ° C to (melting point of polyketone fiber-5 ° C)], more preferably [200 ° C to
(Melting point of polyketone fiber −10 ° C.)]. From the viewpoint of the mechanical properties of the polyketone fiber, the total draw ratio is preferably 10 times or more, more preferably 15 times or more. As the hot stretching apparatus, a conventionally known apparatus such as a method of traveling on a heating roll or a heating plate or in a heated gas, a method of irradiating a running fiber with a laser, a microwave, or infrared rays is adopted as it is or after improvement. be able to.

It is important to take measures to prevent single yarn sticking, because irregularly shaped cross-section fibers having a large specific surface area tend to cause single yarn sticking in the drying process. As a method of preventing single thread sticking, a method of applying an external force to the fibers to shift the single threads, a method of applying a release agent to the fiber surface before sticking occurs, and an electrostatic repulsive force between the single threads are used to separate the single threads. A method of shifting and a method of applying a releasing agent to the fiber surface where a fiber having a highly irregular cross section is easily obtained are preferable. When an external force that causes deviation between single yarns is applied, the water content is 0 at any stage from the start of drying to the end of hot drawing.
An external force is applied to the fibers at -40% by mass, preferably 0-30% by mass, which causes the fibers to shift. Moisture content of fiber is 40% by mass
If it exceeds the range, problems such as deformation of the cross section of the single yarn, damage to the fiber, and slackening are likely to occur when an external force that causes displacement between the single yarns is applied.

As a method for applying an external force that causes a deviation between single yarns, a method of squeezing fibers or a method of applying vibration to fibers is effective. Specifically, a method of squeezing fibers by passing them 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 are mentioned, and a method of blowing a compressed gas to the fiber is preferable from the viewpoint that a fiber having low operability and a single yarn sticking rate is easily obtained. In order to obtain a polyketone fiber having a high degree of irregularity and a low single yarn sticking ratio without damaging the fiber, the tension applied to the fiber is 0 to 1 cN.
/ Dtex in the range, and the compressed gas blowing speed is 0.
The range is preferably 1 to 100 m / sec. There is no limitation on the device and method for spraying the compressed gas and the shape of the spray hole, and a conventionally known device such as an interlacing nozzle can be used.

When the release agent is applied to the surface of the fiber before the single yarn sticking occurs, the release agent is not limited as long as it has a function of preventing sticking by subsequent drying and hot drawing. The release agent is a two-positioned polyketone fiber coated with a compound and then arranged so that the two polyketone fibers are bonded along the fiber axis direction, and a fixed length heat treatment at 225 ° C. for 1 minute is performed. This is a compound having an action of easily defibrating the polyketone fibers with each other when carried out.

Examples of such a releasing agent include particulate materials such as metal oxide fine particles, metal fine particles, silicon compound fine particles, fluorine compound fine particles, and liquid substances such as mineral oil and high molecular weight ester compounds. , High molecular weight ether compounds, and dispersions thereof. A fine particle dispersion containing metal oxide fine particles and silicon fine particles as main components is preferable from the viewpoint of uniform dispersion between polyketone fibers and handling properties. As the average particle size of the fine particle dispersion,
0.1 to 100 μm is preferable, and 0.2 is more preferable.
It is from 10 μm, and application from an aqueous dispersion is preferable from the viewpoint of operability.

The release agent is preferably attached to the polyketone fiber in an amount of 0.1 to 20% by mass. When the adhesion amount is less than 0.1% by mass, a sufficient effect of preventing single yarn sticking is not obtained, and when it exceeds 20% by mass, the physical properties of the obtained polyketone fiber are deteriorated and the processability such as drawability is improved. May be adversely affected. Therefore, the release agent deposition rate is preferably 0.3 to 10% by mass, and more preferably 0.5 to 5% by mass.

When the release agent is applied, it is necessary to apply it at a stage where the water content of the polyketone fiber is 40% by mass or more from the start of washing to the end of drying. If the water content is less than 40% by mass, single yarn sticking will start to occur, and even if a release agent is added, a sufficient single yarn sticking preventing effect cannot be obtained. For this reason, it is necessary to apply the release agent at a stage where the water content of the polyketone fiber is 40% or more, preferably 60% by weight or more, and more preferably 100% by weight or more.

In order to prevent the release agent from being incorporated inside the fiber and deteriorating the physical properties of the fiber, it is preferable to carry out after the start of acid washing, more preferably after the start of washing with water.
Most preferably, it is applied after completion of washing with water. It is important to apply a finishing agent at an arbitrary stage after the completion of the drying step, in addition to the single yarn sticking preventing means, to reduce the dynamic friction between fibers. In particular, the polyketone modified cross-section fiber is likely to be fibrillated or deformed at the end face of the single yarn due to the fiber-fiber friction or the fiber-metal friction during drawing, and therefore it is preferable to apply a smoothing agent before drawing. As the finishing agent applied before stretching, it is particularly preferable to use a mineral oil as a main component from the viewpoint of smoothness and fiber strength to be obtained. Applying the finishing agent
It may be carried out once or a plurality of times. From the viewpoint of modification of the finishing agent at the time of stretching and prevention of stains on rolls, etc., the final finishing agent is applied after the completion of the multi-stage stretching, and the finishing agent application rate before stretching is minimized. Preferably.

When a finishing agent is applied as an aqueous solution, an aqueous emulsion or an aqueous suspension after the completion of hot drawing, the dynamic friction coefficient (μ) between fibers is increased by the water remaining between the fibers, and the twisting strength utilization factor is increased. Therefore, it is preferable to provide a step of drying water after applying the finishing agent. As the finishing agent applying device, a conventionally known device such as nozzle oiling or roll oiling can be used as it is or after being improved according to the purpose.

The polyketone fiber thus obtained is used as it is or after being processed for various purposes.
When the polyketone fiber is processed into a cord and used, the number of twisted yarns is selected according to the application. Generally, the twisting factor K shown below is twisted in the range of 1000 to 30,000. K = Y × D ^0.5 (T / m · dtex ^0.5 ) (In the formula, Y is the number of twists per 1 m (T / m), D is the total fineness of the polyketone used for the twisted yarn (dtex)) Mechanical properties and quality of the cord From the viewpoint of the above, as the twisted yarn tension, both the lower twist tension and the upper twist tension are 0.01 to 0.
It is preferably 2 cN / dtex.

When used for rubber reinforcement, a resorcin / formalin latex (RFL) liquid is adhered to the cord of twisted polyketone fibers, and the resin is passed through the process (so-called Dip treatment process). The preferred composition of the RFL solution is resorcin 0.1 to 10% by mass,
Formalin 0.1-10% by mass and latex 1-28
%, And more preferable compositions are resorcin 0.5 to 3% by mass, formalin 0.5 to 3% by mass, and latex 10 to 25% by mass. R attached to the cord
The temperature for drying the FL liquid is preferably 100 to
The temperature is 250 ° C., more preferably 140 to 200 ° C., and dried for at least 10 seconds, preferably 20 to 120 seconds.

The dried cord is subsequently heat treated in the heat setting zone and the normalizing zone.
The temperature, tension and time in the heat setting zone are preferably 150 to 250 ° C., 0.1 to 0.7 cN / dtex and 10 to 300 seconds, respectively. The temperature, tension and time in the normalizing zone are 15
0 to 250 ° C., 0.01 to 0.3 cN / dtex and 1
It is preferably 0 to 300 seconds.

The polyketone fiber obtained by the above method is
It has excellent mechanical properties such as high strength and high elastic modulus, practically sufficient strength as a cord and processability during twisting. In particular, since it has a large fiber specific surface area, it can be used as a resin, rubber and cement. It has excellent adhesiveness. The polyketone fiber of the present invention is extremely useful particularly in the field of industrial materials such as reinforcing materials for rubber products such as tires, hoses and belts, and FRP and cement reinforcing materials.

[0053]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described with reference to Examples and the like, but these do not limit the scope of the present invention. The measuring method of the measured value used in the present invention is as follows. (1) Intrinsic viscosity Intrinsic viscosity [η] is a value obtained based on the following defining equation. [Η] = lim (T−t) / (t · C) [dl / g] C → 0 In the formula, t and T are hexafluoroisopropanol having a purity of 98% or more and a dilution of polyketone dissolved in hexafluoroisopropanol. Flow-through time of the solution at 25 ° C. in a viscous tube, C is the solute mass in grams above 100 ml.

(2) Fiber strength and elastic modulus Measured according to JIS-L-1013. (3) The crystallinity differential thermal analyzer Pyris1 (trademark) (manufactured by Perkin Elmer) 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 Measuring temperature: 30 ° C. → 300 ° C. Temperature rising rate: 20 ° C./min Atmosphere: Nitrogen, flow rate = 200 mL / min In the endothermic curve obtained, the maximum endothermic peak observed in the range of 200 to 300 ° C. It is calculated by the following formula from the heat quantity ΔH (J / g) calculated from the area. Crystallinity = ΔH / 225 × 100 (%)

(4) Crystal orientation degree Imaging plate X-ray diffractometer manufactured by Rigaku Corporation,
RINT (registered trademark) 2000 is used to capture the diffraction image of the fiber under the following conditions: X-ray source: CuKα ray output: 40 KV 152 mA Camera length: 94.5 mm Measurement time: 3 minutes 2θ = 21 ° of the obtained image Observed nearby (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
(%) The value obtained by dividing the total fineness by the number of holes in the spinner used for producing the fiber is defined as the single yarn fineness.

(5) Sticking rate of single yarn A) Number of single yarns The number of spinners used for producing polyketone fibers or the number of filaments indicated by the brand is the number of single yarns. B) Number of apparent single yarns Polyketone fibers are lightly rubbed with chalk on a black mount 20 times to defibrate the fibers, and the number of filaments is counted with a 100 × magnifying glass. 1 for those that are stuck and cannot be separated
The number of single yarns is counted, and the average value of three measurements is used as the apparent number of single yarns. 1 if the number of polyketone fibers is large
Prior to defibration, the polyketone fiber is divided into n pieces based on the following formula without defibration treatment every time, and fibrillation treatment is performed for each divided unit to measure the number of filaments, and the sum is apparent. The number of single yarns. N / 200 ≧ n ≧ N / 300 N = number of single yarns (measured value in A) From the number of single yarns and the apparent number of single yarns, the single yarn sticking rate is calculated by the following formula. Single thread sticking rate = [1- (apparent number of single threads / number of single threads)] x
100 (%)

(6) Finishing Agent Adhesion Rate The fibers were washed with warm water at 50 ° C. and subsequently washed with methyl ethyl ketone at 50 ° C., and the mass before washing was W ₂ (g),
The mass after cleaning is set to W ₃ (g), and the finishing agent adhesion rate is calculated by the following formula. The weight of the fibers (W ₂ and W ₃ ) is measured by heating at 105 ° C. for 5 hours before being weighed, and is measured as an absolutely dry state. Finishing agent adhesion rate = [(W ₂ −W ₃ ) / W ₃ ] × 100
(%)

(7) Fiber-fiber dynamic friction coefficient (μ) About 690 m of fiber is wound around a cylinder at a traverse angle of 15 ° to be about 10.
g of tension and wrapping, and the same fiber as above.
Hang 5 cm 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 is 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 coefficient of static friction between fibers (μ) is determined according to the following formula. μ = 1 / π × ln (T ₂ / T ₁ ) 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, and π is the circular constant. .

(8) Fiber Degree of Deformation Polyketone fiber is mixed with epoxy monomer (Ketol 812).
(Trademark, manufactured by Nisshin EM)) and a curing agent (dodecyl saxonic unhydride, methyl nadic unhydride), and then the initiator (DMP-3).
0 (trademark), manufactured by Nisshin EM Co., Ltd.) is added, and the mixture is treated under heating at 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. A fiber cross-section photographic image is measured for the outer peripheral length L and the cross-sectional area A of the cross section of the polyketone single yarn with a deformity measuring device FMS-2000 (trademark) (manufactured by Union System Co., Ltd.) to obtain L ² / 4πA.
L ² / 4πA for any 50 single yarns in the cross-section photograph
Is obtained, and the average value is defined as the fiber irregularity.

(9) Resin Adhesion Rate RFL treatment cord 10m is heated at 105 ° C. for 5 hours, and then the absolute dry weight W ₄ (g) is measured. Then the code 1
It is shredded to a length of mm and dissolved in 200 ml of hexafluoroisopropanol under stirring at 60 ° C. for 2 hours. After dissolution, filtration is performed, the obtained residue is heat treated at 105 ° C. for 5 hours, then the weight W ₅ (g) is precisely weighed, and the resin adhesion rate is calculated from the following formula. Resin adhesion rate _{= [W 5 / W 4]} × 100 (%)

(10) Rubber adhesion 70% natural rubber, 15% SBR and carbon black 1
Using an unvulcanized rubber of 5% blending, a polyketone cord was embedded in this for 1 cm, vulcanized under the conditions of 155 ° C., 3.5 MPa and 30 minutes, and then T pull-out strength (N) was obtained at a crosshead speed of 300 mm / min. taking measurement.

[0062]

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 weight calcium chloride / 22% by weight zinc chloride. After stirring at 80 ° C for 2 hours, the mixture was further dissolved at 90 ° C for 1 hour to obtain a dope having a polymer concentration of 6.8% by mass. The obtained dope is heated to 80 ° C., and 20 μm
After filtering with a m filter, the discharge hole shape is a triangular spinner whose side length is 0.25 mm, L / D = 2, and a discharge rate of 4.5 cc / min from a spinneret with 50 holes. did. After the discharge, the mixture was passed through an air gap of 10 mm, 2 mass% calcium chloride, 1.1 mass% zinc chloride and 0.
The yarn was introduced into a coagulation bath consisting of water at −2 ° C. containing 1% by mass of hydrochloric acid.

The yarn drawing speed was 5 m / min (spinning draft was 1.50). Almost no ballast occurred just below the spinneret. The time from the immersion of the yarn in the coagulation bath to the first contact with the solid (ceramic guide) was 6 seconds. Pull the drawn polyketone yarn at a temperature of 3
Wash with an aqueous hydrochloric acid solution having a concentration of 2% by mass at 0 ° C.
After washing with water at ℃, it was wound at a speed of 5 m / min.
After simple dehydration of the obtained yarn, polyketone fiber, IR
GANOX (registered trademark) (manufactured by Ciba Specialty Chemicals Co., Ltd.) 1098 and IRGANOX (registered trademark) (manufactured by Ciba Specialty Chemicals Co., Ltd.) 1076 were impregnated in amounts of 0.05% by mass, respectively, and constant length drying was performed at a temperature of 225 ° C. for 1 minute. It was 0.02 cN / dte to this fiber
With the tension of x applied, the pressure treatment device (HemaJe
t (registered trademark) T-341, manufactured by Japan Hebaline Co., Ltd.) was used to blow compressed air of 0.2 MPa to defibrate the fibers. The water content of the polyketone fiber at this time was 0.2%.

This fiber was drawn in the heating furnace at 225 ° C. for the first step (6.0 times), and then further drawn with 0.05 cN.
/ Dtex tension is applied to the compressed air treatment device (Hem
Using aJet (registered trademark) T-321, manufactured by Nippon Hebaline Co., Ltd., compressed air of 0.1 MPa was blown to defibrate. At this time, the water content of the polyketone fiber was 0%. After defibration, the following finishing agent having an emulsion concentration of 1% by mass was applied, followed by a second stage (1.5 times) in a heating furnace at 240 ° C. and a third stage (1.
(35 times). Apply the same finishing agent as above with an emulsion concentration of 5% by mass to the obtained fiber,
Heat treatment was performed at 160 ° C. for 3 seconds while applying a tension of N / dtex to obtain 84.3 dtex / 50f polyketone fiber.

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 / polyethylene oxide 10 mol addition castor oil ether / sodium stearyl sulfonate / dioctyl phosphorus Sodium acidate = 30/30/10/5/23/1/1 (mass%
ratio).

The process passability in spinning, drying and drawing was extremely good, and no trouble such as fluff or yarn breakage occurred. This polyketone fiber has a fiber irregularity of 1.21.
No single yarn sticking or distorted cross-sectional shape fibers were observed. The shapes of the modified spinnerets used for spinning are shown in Table 1 together with the shapes of the modified spinnerets used in Examples 2 to 7 below. The outline of the cross-sectional shape of the obtained polyketone fiber is shown in Table 2 together with the cross-sectional views of the polyketone fiber obtained in Examples 2 to 7 below. This polyketone fiber has a strength of 16.1 cN
/ Dtex, the elastic modulus was 342 cN / dtex, and had excellent mechanical properties. The structure and properties of the obtained polyketone fiber are shown in Table 3 together with the results of Examples 2 to 10 and Comparative Examples 1 to 5 below.

[0067]

[Example 2] In Example 1, the spinneret was a C-type spinneret,
Spinning, drying and stretching were performed in the same manner except that the spinning draft was set to 1.5. The obtained polyketone fiber was a modified cross-section fiber having a fiber modification degree of 2.40.

[0068]

[Example 3] In Example 1, the spinneret was a Y-type spinneret,
Spinning, drying and stretching were performed in the same manner except that the spinning draft was 1.3. The obtained polyketone fiber was a modified cross-section fiber having a fiber modification degree of 2.07.

[0069]

[Example 4] In Example 1, the spinneret was a W-type spinneret,
Spinning, drying and stretching were performed in the same manner except that the spinning draft was set to 1.4. The obtained polyketone fiber was a modified cross-section fiber having a fiber modification degree of 3.15.

[0070]

[Example 5] In Example 1, the spinneret was an I-type spinneret,
Spinning, drying and stretching were performed in the same manner except that the spinning draft was set to 1.5. The polyketone fiber obtained was a modified cross-section fiber having a fiber modification degree of 1.69.

[0071]

[Embodiment 6] In Embodiment 1, the spinneret has a major axis of 0.3 m.
m, a short diameter of 0.1 mm, and a spinning draft of 1.
Spinning, drying, and stretching were performed in the same manner except that the number was 7.
The obtained polyketone fiber was a modified cross-section fiber having a fiber modification degree of 1.66.

[0072]

[Embodiment 7] In Embodiment 1, the spinneret has a major axis of 1.5 m.
m, rectangular shape with minor axis of 0.1 mm, discharge amount is 25.0 c
Spinning, drying and stretching were performed in the same manner except that the spinning draft was c / min and the spinning draft was 1.5. The obtained polyketone fiber was a modified cross-section fiber having a fiber modification degree of 4.46.

[0073]

Example 8 In Example 1, polyketone fibers (water content = 1200%) had an average particle size of 5 μm at the entrance of the drying process.
Spinning, washing, drying, drawing, and applying a finishing agent were performed in the same manner except that the silica fine particle emulsion was added and the pressure treatment was not performed in the drying step and the drawing step. The degree of fiber irregularity of the obtained polyketone fiber was 1.22.

[0074]

[Embodiment 9] In Embodiment 1, the air gap length is set to 30.
mm, and the spinning speed is 8 m / min (spinning draft = 2.
Spinning, washing, drying, and stretching were performed in the same manner except that the above 4) was performed. The fiber irregularity of the obtained polyketone fiber is 1.
It was 25.

[0075]

Example 10 Ethylene / propylene / comprising 3% by weight of 1-oxo-3-methyltrimethylene unit and 97% by weight of 1-oxotrimethylene unit by a conventional method.
A carbon monoxide terpolymer (intrinsic viscosity 3.9) was prepared. Using this polyketone, spinning, washing, drying and stretching were performed in the same manner as in Example 1 except that spinning was performed as a dope having a polymer concentration of 12% by mass. The degree of fiber irregularity of the obtained polyketone fiber was 1.27.

[0076]

Comparative Example 1 In Example 1, the spinneret shape was 0.15 m.
Spinning, drying and stretching were carried out in the same manner except that the circular spinneret with mφ was used. The polyketone fiber obtained had a fiber irregularity of 1.
02, which was outside the scope of the present invention.

[0077]

Comparative Example 2 In Example 1, the spinning draft was 0.8.
Then, spinning, washing, drying, and stretching were performed in the same manner except that pressure treatment was not performed in the drying step and the stretching step. The polyketone fiber thus obtained had a single yarn gluing ratio of 80%, which was severely gluing, and the fiber irregularity of the portion where the single yarn was loose was 1.16, which was outside the range of the present invention. there were.

[0078]

[Comparative Example 3] In Comparative Example 1, the spinning method was an immersion spinning method without passing through an air gap (the spinneret was immersed in a coagulation bath, and the dope was directly discharged from the spinneret into the coagulation bath).
Spinning was carried out in the same manner except that the above was performed, but the dispersion around the outlet of the spinneret was severe and stable, and spinning could not be carried out.

[0079]

Comparative Example 4 An ethylene / propylene / carbon monoxide terpolymer comprising 5% by weight of 1-oxo-3-methyltrimethylene unit and 95% by weight of 1-oxotrimethylene unit (intrinsic viscosity 1.3 , Melting point 233
C) was prepared. 1% by mass of calcium hydroxyapatite in this polymer, IRGANOX (registered trademark)
(Ciba Specialty Chemicals) 1010
5% by mass was blended, melted at 250 ° C., and melt-spun using a modified cross-section spinneret with a triangular cross section, but the extrusion pressure increased due to polymer modification during melting, and spinning could not be performed.

[0080]

[Comparative Example 5] The same procedure as in Example 1 was carried out except that no finishing agent was applied during and after the stretching, followed by spinning, drying,
Stretching was performed. The obtained fiber had a high degree of irregularity of 1.22, but many fibril-like substances were observed on the surface of the single yarn. The dynamic friction coefficient (μ) between the fibers was as high as 0.55, which is outside the range of the present invention, and a large number of fluffs and fibril-like substances were generated during the measurement of the friction coefficient.

[0081]

Example 11 Polyketone fiber 20 produced in Example 1
The book was twisted into fibers of 1686 dtex / 1000 f, which was twisted in the Z direction, and then twined into two and twisted in the S direction to obtain a raw cord. The number of twists was 390 T / m (twisting coefficient = 22647) for both the lower twist and the upper twist, and there were no problems such as yarn breakage during twisting, and the obtained cords were of excellent quality with no fluff.

This raw cord was dipped in an RFL solution having the following liquid composition, and then dried in a drying zone (tension: 2.8 N, 160 ° C.).
Heat treatment for 120 seconds), heat set zone (tension 4.
The cord was obtained through a normalizing zone (heat treatment at 220 ° C. for 60 seconds at 0 N) and a normalizing zone (heat treatment at 220 ° C. for 60 seconds at a tension of 1.8 N). (RFL liquid composition) Resorcin 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) 364.0 parts

This polyketone cord has a high tensile strength of 392 N / cord and a rubber adhesive strength of 172 N / c.
It was m / cord and showed excellent adhesiveness. The twisting condition, Dip processing condition and performance of this cord are shown in Example 12,
The results are shown in Table 4 together with the results of No. 13 and Comparative Example 6.

[0084]

Example 12 In Example 11, the number of twisted yarns was
Twisted yarn and Dip treatment were performed in the same manner except that the upper twist was 290 times / m (twist coefficient = 16840). The obtained cord has good quality and strength of 464 N / cord,
The rubber had excellent adhesive strength of 166 N / cm / cord.

[0085]

[Example 13] In Example 11, the number of twisted yarns was
Twisted yarn and Dip treatment were carried out in the same manner except that the upper twist was 190 times / m (twist coefficient = 11033). The obtained cord is of good quality and strong, 506 N / cord,
The rubber adhesion was 161 N / cm / cord, which was an excellent performance.

[0086]

Comparative Example 6 Twenty polyketone fibers produced in Comparative Example 1 were combined into a fiber having 1650 dtex / 1000f and twisted in the same manner as in Example 11 (both lower twist / upper twist 390 T / m (twist coefficient = 22404). )) After that, RFL
The code was processed. The strength of the cord was slightly superior to that of the modified cross-section fiber of the same fineness and twisting condition (Example 11), but the adhesive strength with the rubber was 160 N / cm / c.
and the adhesive force was inferior to the cord of the modified cross-section fiber of the present invention.

[0087]

Comparative Example 7 Eighteen polyketone fibers produced in Comparative Example 2 were combined to obtain 1647 dtex / 900 f fibers,
In the same manner as in Example 11, twisted yarn (both twisted / twisted yarn 3
After 90 T / m (twisting coefficient = 22383), RFL treatment was performed to obtain a cord. This polyketone fiber has a low utilization factor of the twisting yarn strength, and the strengths of both the raw cord and the Dip cord are significantly reduced. The strength of the cord is 20% as compared with the modified cross-section fiber of the same fineness and the twisting condition (Example 11). Was low, and the rubber adhesive strength was 155 N / cm / cord, which was inferior.

[0088]

[Table 1]

[0089]

[Table 2]

[0090]

[Table 3]

[0091]

[Table 4]

[0092]

EFFECT OF THE INVENTION The polyketone fiber of the present invention has a cross-sectional shape with a high degree of irregularity, high strength / high elastic modulus, high melting point,
It has excellent mechanical properties such as high heat resistance.
Further, it is excellent in productivity, has no defects in quality and process such as sticking of single yarn, fluff, yarn breakage, etc., and is excellent in process passability and quality in a drawing process and a twisting process. By twisting this fiber, it is possible to obtain a cord having a high-grade and high strength while having a cross-sectional shape with a high degree of irregularity.
In particular, these polyketone fibers and cords have a large specific surface area and are excellent in adhesiveness with resins, rubbers, and cements, and are used in industrial materials such as reinforcing materials for rubber products such as tires, hoses and belts, and FRP and cement reinforcing materials. Is extremely useful in

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Claims (8)

[Claims] 1. 95 to 100% by mass of the repeating unit is composed of 1-oxotrimethylene represented by the chemical formula (1), and has a crystallinity of 60% or more and a crystal orientation of 90% or more,
In addition, the polyketone fiber has a tensile strength of 10 cN / dtex or more, the fiber irregularity degree shown below is 1.2 or more, and the fiber-fiber dynamic friction coefficient (μ) is 0.01 to
Polyketone fiber characterized by being 0.5. Deformation degree of fiber = L ² / 4πA (where L is the outer peripheral length of the cross section of the polyketone fiber, and A is the cross-sectional area) 2. 100% by mass of the repeating unit consists of 1-oxotrimethylene represented by the chemical formula (1), the crystallinity is 70% or more, the crystal orientation is 95% or more, and the tensile strength is 12 cN / dtex. The polyketone fiber according to claim 1, wherein the single yarn fineness is 0.5 to 2 dtex. 3. The polyketone fiber according to claim 1 or 2, wherein the degree of fiber irregularity is 3 or more and the cross-sectional shape of the fiber is flat. 4. 0.3 to 10 relative to the polyketone fiber
The polyketone fiber according to any one of claims 1 to 3, wherein a mass% of a finishing agent is attached. 5. The polyketone fiber according to any one of claims 1 to 4, wherein the single yarn sticking rate of the polyketone fiber is 30% or less. 6. The polyketone fiber according to claim 1, which has a twist coefficient K of 100 shown below.
A cord characterized by being twisted in the range of up to 30,000. K = Y × D ^0.5 (T / m · dtex ^0.5 ) (In the formula, Y is the number of twists per meter (T / m), and D is the total fineness (dtex) of the polyketone used for the twisted yarn) 7. A polyketone is dissolved in a metal salt solution containing zinc halide, the solution is extruded from a spinneret through an air gap into a coagulation bath, and the metal salt is washed off from the obtained yarn and then dried. In the method for producing a polyketone fiber that is then heat-stretched, the spinneret is a modified spinneret having a spinneret irregularity of 1.2 or more as shown below, and any stage from the start of drying to the end of hot stretching is performed. An external force that causes a deviation between single yarns is applied to a fiber having a water content of 0 to 40% by mass, and 0.1 to 20% by mass based on the polyketone fiber at any stage from the end of drying to the end of thermal drawing. A method for producing a polyketone fiber, which comprises applying the above finishing agent. Deformation degree of spinneret = L ₀ ² / 4πA ₀ (where L ₀ is the outer peripheral length of the spinneret discharge hole, and A ₀ is the cross-sectional area of the spinneret discharge hole) 8. A polyketone is dissolved in a metal salt solution containing zinc halide, the solution is extruded from a spinneret through an air gap into a coagulation bath, and the metal salt is washed off from the obtained yarn and then dried. In the method for producing a polyketone fiber that is then heat-stretched, the spinneret is a modified spinneret having a spinneret irregularity of 1.2 or more as shown below, and the water content between the washing start and the drying end is 40 mass. % Of the polyketone fiber is added to the fiber in an amount of 0.1 to 20% by mass of the release agent. Deformation degree of spinneret = L ₀ ² / 4πA ₀ (where L ₀ is the outer peripheral length of the spinneret discharge hole, and A ₀ is the cross-sectional area of the spinneret discharge hole)