JP2004218189A - Polyketone processed cord and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyketone processed cord useful for a tire belt, a rubber-reinforcing material for a hose and the like by using a polyketone fiber excellent in high mechanical strength, high elasticity and having high heat shrinkage stress and high dry heat shrinkage and exhibiting a strong shrink property when heated. <P>SOLUTION: The polyketone fiber processed cord is obtained by processing polyketone fiber with a resorcinol-formalin-latex resin and has the maximum heat shrinkage stress of 0.2-0.4 cN/dtex or more, (the maximum heat shrinkage stress of 500-1079 cN/cord, a heat shrinkage of 1-4% at 150°C) and a dry heat shrinkage of 0.5-6% at 150°C, wherein the heat treatment conditions of the polyketone twisted cord has a specific relation between the heat treating temperature, the tension added in heat treatment and the like. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

The present invention relates to polyketone processing codes and methods for their production using the polyketone fibers having excellent mechanical properties and high thermal shrinkage characteristics.
More particularly, the present invention has excellent mechanical properties of high strength and high modulus of elasticity, and relates to polyketone processing codes and methods for their production using the polyketone fibers having a very high heat shrink.
Polyketone fiber of the present invention is widely applicable, such as clothing use or industrial materials applications, especially during processing and industrial materials Field of expressing a heat-shrinkable and heat shrinkage force is required at the time of use, in particular a belt or tire cord It is useful as a polyketone-treated cord applicable to reinforcing fiber materials such as.

In recent years, it has been found that by polymerizing carbon monoxide and olefins such as ethylene and propene using palladium and nickel as a catalyst, an aliphatic polyketone polymer in which carbon monoxide and olefins are substantially completely alternately copolymerized can be obtained. (Non-Patent Document 1), and studies on fiberization of polyketone polymers have been conducted thereafter.
It is known that polyketone fibers have a higher melting point than conventional polyolefin fibers, and that fibers having high strength and high elastic modulus can be obtained. By utilizing these excellent physical properties, industrial materials, civil engineering materials, Development into a wide range of uses such as materials and clothing is being considered. Above all, it is expected to be used for industrial materials, especially for tire cords by utilizing the excellent mechanical properties of high strength and high elastic modulus and the thermal properties of high melting point.
Even in tire cords, the required performance is completely different depending on the application and use site.For example, in cord applications such as carcass ply used as the core material of the carcass part of the tire, high strength and small heat shrinkage properties are required, For cord applications such as cap plies and edge plies used for the purpose of maintaining the shape of a carcass or a belt, high strength and high heat shrink force are required.

In the case of polyketone fiber, a fiber having a small heat shrinkage, high physical properties and stable heat shrinkage characteristics is obtained even though it is a high strength and high elastic modulus fiber (for example, Patent Documents 1, 2, and 3). It is expected to be applied to applications such as carcass plies. However, on the other hand, no polyketone fiber suitable for a cap ply or an edge ply has been known at all, and the development of a polyketone fiber having a high heat shrink force while having a high strength and a high elastic modulus has been desired. I have.
Hitherto, several techniques have been disclosed for high-strength, high-modulus polyketone fibers. For example, Patent Document 4 and Non-Patent Document 2 disclose a method of performing melt spinning. A method of performing wet spinning using a solvent is disclosed.
These documents disclose a technique of obtaining a high-strength and high-modulus polyketone fiber by highly drawing an undrawn polyketone yarn obtained by melt spinning or wet spinning under heating. However, the polyketone fiber spun and drawn by the method described in these documents can obtain high strength and high elastic modulus of 10 cN / dtex or more and elastic modulus of 200 cN / dtex or more, but strong shrinkage force when heated. Are not disclosed at all.

Further, Patent Literature 13 and the like show a technique relating to a tire cord made of polyketone fiber, in which a tension heat treatment is performed when the polyketone fiber is processed into a tire cord.
However, even if a polyketone fiber having a high heat shrinkage stress and a high heat shrinkage rate is used, the heat shrinkage stress and the heat shrinkage rate of the polyketone fiber are reduced by the heat treatment in the processing step, and the heat shrinkage force of the polyketone treated cord is not improved. It will be enough.
Further, Patent Literature 14 discloses a technique in which a treatment cord made of polyketone fiber is used for a carcass layer of a radial tire. However, this document does not disclose any technique relating to the application of polyketone fibers to a cap ply or an edge ply, or a polyketone treated cord having a high heat shrinkage stress applicable to a cap ply or an edge ply.
As described above, there is no known polyketone fiber or polyketone fiber treated cord having extremely high heat shrinkage stress while having excellent mechanical properties such as high strength and high elastic modulus, and no technique for producing them.

Japanese Patent Application No. 11-77220 Japanese Patent Application No. 11-227035 Japanese Patent Application No. 11-330939 JP-A-1-124617 JP-A-2-112413 Japanese Patent Publication No. 4-505344 JP-A-2-112413 JP-A-4-228613 Japanese Patent Publication No. 7-508317 Japanese Patent Publication No. Hei 8-507328 U.S. Pat. No. 5,550,019 WO9918143 pamphlet JP-A-9-324377 JP-A-11-334313 "Industrial Materials" December 1997 issue, 5 pages Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.), 36, 291-292, Prog. Polym. Sci. , Vol. 22, 8, 1547-1605 (1997)

An object of the present invention is to provide, in the polyketone fibers of the original patent application der Ru high strength and high modulus of elasticity, but provides polyketone fibers and a method of manufacturing the same having high shrinkage force while hot, in the present invention, the cap An object of the present invention is to provide a polyketone-treated cord having a tag performance that suppresses loosening or loosening of a tire form when used as a tire reinforcing material such as a ply or an edge ply, and a method for manufacturing the same.

In order to achieve the above object, the present inventors have, in the earlier application, studied the production conditions of polyketone fiber, and after performing high-temperature drawing of polyketone fiber, treated under temperature and tension under specific conditions. Although the obtained specific polyketone fiber was provided, in the present invention, it was found that an excellent polyketone fiber treated cord and a method for producing the same can be provided by using the specific polyketone fiber , and as a result of further studies, the present invention was achieved. .
That is, the present invention provides:
(1) A polyketone fiber treated cord in which a polyketone fiber is treated with a resorcin-formalin-latex resin, having a maximum heat shrinkage stress of 0.2 to 0.4 cN / dtex and dry heat shrinkage at 150 ° C. A polyketone treated cord having a rate of 0.5-6% is provided. Also,
(2) It is also characterized in that the maximum heat shrinkage stress is 0.3 to 0.4 cN / dtex and the heat shrinkage at 150 ° C. is 1 to 4%. Also,
(3) It is also characterized in that the maximum heat shrink force is 500 to 1079 cN / cord. Also,
(4) A method for producing a polyketone-treated cord in which a polyketone twisted cord is immersed in a resorcinol-formalin-latex liquid and then heat-treated.
When the heat treatment temperature of the twisted cord is T (° C.) and the tension applied during the heat treatment is σ _D (cN / dtex), a method for producing a polyketone-treated cord including a process in which σ _D and T are within the range of the following formula: provide. Also,
1.01 × σ _T ≦ σ _D (cN / dtex) ≦ 10 × σ _T
100 ≦ T (° C.) ≦ 270
(Here, σ _T is the heat shrinkage stress at the temperature T of the polyketone twisted cord.)

The polyketone fiber which is the raw material of the polyketone fiber treatment cord of the present invention not only has excellent mechanical properties of high strength and high elastic modulus, but also has a high heat shrinkage stress and dry heat shrinkage, and exhibits strong shrinkage when heated. .
The twisted cord obtained by twisting the polyketone fiber and the treatment cord to which an adhesive is applied are used in applications where the ability to tighten the material when subjected to heat during processing or use is required, for example, rubber reinforcement for tires, belts, and hoses. The material is extremely useful for industrial materials such as a cord material and FRP used for an outer peripheral portion and a surface portion of a product.
In particular, the polyketone-treated cord using the polyketone fiber of the present invention exhibits superior heat shrinkage power over a cord made of a conventional thermoplastic fiber, so that the number of fibers to be used can be reduced, and a cap ply or a belt can be used. When applied to plies, the weight of tires and belts can be further reduced.

繰返単位中の１−オキソトリメチレンの割合が高いほど高強度・高弾性率、高耐熱性の繊維が得られることから、９７モル％以上、好ましくは９９モル％以上、最も好ましくは１００モル％が１−オキソトリメチレンであることが望ましい。 Hereinafter, the present invention will be described in detail.
The polyketone polymer used in the present invention is a polyketone polymer in which 97 mol% or more of the repeating units are composed of 1-oxotrimethylene.
The repeating unit composed of 1-oxotrimethylene is a group represented by the following structural formula (1).

97% by mole or more, preferably 99% by mole or more, most preferably 100% by mole, since the higher the proportion of 1-oxotrimethylene in the repeating unit, the higher the strength, the high elastic modulus and the high heat-resistant fiber can be obtained. % Is preferably 1-oxotrimethylene.

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

The degree of polymerization of the polyketone polymer is desirably 1 to 20 as the intrinsic viscosity measured by the method described in Examples of the present invention.
When the intrinsic viscosity is less than 1, the molecular weight is too low to obtain a high-strength polyketone fiber, and the physical properties (strength and elongation) of the coagulated yarn are low, so that the fluff during spinning, drying, and stretching is reduced. Troubles in the process such as thread breakage occur frequently. On the other hand, when the intrinsic viscosity is more than 20, polymerization of the polymer takes time and cost, and uniform dissolution is difficult and spinning properties and fiber properties are adversely affected.
Therefore, the intrinsic viscosity of the polyketone polymer used in the present invention is preferably 1 to 20, more preferably 2 to 10, and particularly preferably 3 to 8.

The polyketone fiber, which is a raw material of the polyketone fiber treatment cord of the present invention, needs to have a crystal structure having a crystallinity of 50 to 90% and a crystal orientation of 95% or more. If the degree of crystallinity is less than 50%, the fiber structure is insufficiently formed so that sufficient strength cannot be obtained, and also the shrinkage characteristics and dimensional stability during heating become unstable.
Therefore, the degree of crystallinity is desirably 50 to 90%, preferably 60 to 85%.
When the degree of crystal orientation is less than 95%, the orientation of the molecular chains is insufficient, and a fiber having a sufficient elastic modulus cannot be obtained. Therefore, the degree of crystal orientation is 95% or more, preferably 97% or more. Is desirable.
Moreover, positive Riketon fiber tensile strength of 10 cN / dtex or more, a tensile modulus of elasticity is required to be 200 cN / dtex or more.
The higher the tensile strength, the more it can be used in fields requiring high strength and the weight of the fibers used can be reduced. Therefore, the tensile strength is desirably 15 cN / dtex or more.
The tensile elastic modulus is excellent in dimensional change is small form stability under the same load higher, more desirably at 3 00cN / dtex or more.
Po Riketon fibers it is particularly necessary maximum thermal shrinkage stress is 0.8cN / dtex or more.

When the heat shrinkage stress is less than 0.8 cN / dtex, the heat shrinkage force of the twisted cord or the treated cord is reduced by more than 10% from the value of the original yarn, so that the force for firmly and efficiently tightening the molded product. Is insufficient, and the function as a hammering material for retaining the shape cannot be sufficiently performed.
Therefore, the maximum heat shrinkage stress of the polyketone fiber is desirably 0.8 cN / dtex or more, preferably 0.9 cN / dtex or more. It is particularly desirable that the maximum heat shrinkage stress be 1.0 cN / dtex or more. In this case, the heat shrinkage stress becomes nearly twice as large as that of a conventional fiber material (for example, nylon 6.6 or polyethylene terephthalate), and the amount of fibers used And the weight can be reduced.

To most effectively utilize the high heat shrinkage characteristics of Po Riketon fibers, the temperature of the processing time of the processing temperature and operating time of the molded article, close to the temperature (hereinafter referred to as maximum heat shrinkage temperature) showing a maximum heat shrinkage stress Desirably temperature.
When used as a rubber reinforcing fiber material for tire cords and belts, the processing temperature such as RFL processing temperature and vulcanization temperature is 100 to 250 ° C, and the material for tires and belts due to repeated use and high-speed rotation The maximum heat shrinkage temperature is desirably in the range of 100 to 250 ° C., since the temperature when heat is generated can reach 100 to 200 ° C.
When the maximum heat shrink temperature is less than 100 ° C., a relatively high shrinkage stress is generated even when wound into a package or when a product is used under normal conditions, and problems such as winding and product distortion are likely to occur. Become. Further, the maximum heat shrinkage stress is greatly reduced by the RFL processing performed when processing into the processing cord, and it becomes difficult to obtain a tire cord having a sufficient heat shrinkage stress.
On the other hand, if the maximum heat shrink temperature exceeds 250 ° C., the fiber is likely to be denatured during the heat treatment, making it difficult to effectively utilize the thermal stress characteristics.
For this reason, it is desirable that the maximum heat shrink temperature is preferably 100 to 250 ° C, more preferably 150 to 240 ° C.

Moreover, positive Riketon fibers has high thermal shrinkage stress, has a characteristic of high compared shrinkage during dry heat treatment in a conventional polyketone fibers.
The dry heat shrinkage is difficult to define unconditionally because the required performance varies depending on the processing conditions and applications, but it is desirable that the shrinkage in a dry heat treatment at 150 ° C. for 30 minutes be 1% or more.
More preferably, the shrinkage ratio is 2% or more, more preferably 3% or more, and particularly preferably 4% or more.
On the other hand, if the dry heat shrinkage ratio is too large, a problem occurs in that the rolled-up package becomes remarkably tightly wound. Therefore, it is preferably 7% or less, more preferably 6% or less.

No particular limitation is imposed on the single fiber fineness and single yarn number of ports Riketon fibers, filaments, may be any of long fiber.
The single yarn fineness is preferably in a range of 0.01 to 100 dtex, the number of single yarns is 1 to 10,000 ftex, and the total fineness is 30 to 100,000 dtex. More preferably, the single yarn fineness is 0.1 to 10 dtex, the number of single yarns is 10 to 5,000, Fineness is 100-10000.
In the case of a multifilament, it may be twisted as required. The number of twists cannot be defined unequivocally because it varies according to the fineness of the single yarn, the total fineness, the application, etc., but is usually about 2 to 1000 times per 1 m of fiber length.
In the polyketone fiber, depending on the purpose, an oil agent, an antioxidant, a quenching agent, a radical scavenger, a heavy metal deactivator, a gelling inhibitor, a matting agent, an ultraviolet absorber, a pigment, etc. Agents, other polymers, and the like.

Hereinafter is exemplified a method of manufacturing a port Riketon fibers, Po Riketon fibers is not intended to be limited in any way by these methods.
The polyketone unstretched yarn is spun using the above-described polyketone polymer, but the method for producing the unstretched yarn is not particularly limited, and a conventionally known spinning method can be used as it is or as required, if necessary. .
For example, when the wet spinning method is adopted, a wet spinning method using a zinc halide solution as a solvent is preferably used from the viewpoint of the safety and handleability of the solvent.
As a wet spinning method using zinc halide as a solvent, for example, 2 to 30% by weight of a polyketone polymer is dissolved in a solution containing 15 to 80% by weight of zinc halide to form a dope, and spinning is performed at a temperature of 50 to 130 ° C. The dope is discharged from the die into a coagulation bath, the dope is formed into a thread, and the obtained thread is washed as necessary to remove the solvent, and then taken up at a speed of 0.01 to 100 m / min. can get. Subsequently, by heating and drying the coagulated yarn, an undrawn polyketone yarn can be obtained.
The drawn undrawn yarn is subjected to a drawing step after being wound once by a winder or continuously without winding.

As a method for drawing the polyketone fiber, a heat drawing method in which the yarn is heated to a temperature higher than the glass transition temperature and drawn is suitably used, and the drawing is performed in one step or two or more steps. As the heat drawing method, a conventionally known apparatus or method such as a method of running on a heated roll or plate or in a heated gas, or a method of irradiating a running yarn with laser, microwave, or far-infrared light is used as it is or is improved. Can be adopted.
From the viewpoint of the heat transfer efficiency and the uniformity of the yarn temperature, stretching on a heating roll or a heating plate is preferable, and a stretching method using both a roll and a plate may be used. In addition, it is preferable that the periphery of the roll or the plate is sealed and the sealed space is filled with a heated gas because stretching at a more uniform temperature is possible.
The preferred stretching temperature range is from 110 ° C to the melting point, more preferably from the melting point of -50 ° C to the melting point of -5 ° C.
The total draw ratio from the undrawn yarn to the final drawn yarn is preferably 10 times or more, more preferably 12 times or more, and particularly preferably 15 times or more.

The maximum heat shrinkage stress of a polyketone fiber hot-drawn at a high magnification of 10 times or more by a conventionally known method as described above is usually at most 0.7 to 0.8 cN / dtex. It is not possible to obtain a polyketone fiber having high heat shrinkage characteristics.
The present inventors have (i) drawn at a specific temperature and a draw ratio at the end in the multi-stage hot drawing step, and / or (ii) immediately after the completion of the hot drawing, while applying a high tension to the fiber, It has been found that by cooling, a polyketone fiber having high heat shrinkage characteristics of the present invention can be obtained.

In the multi-stage hot stretching step (i), the method of stretching at the last specific temperature and magnification means that when the final hot stretching temperature is T _L and the final one-stage stretching temperature is T _B ,
At _{110 ℃ ≦ T L ≦ T B} -3 ℃ temperature is to stretched 1.01 to 1.5 times magnification.
If the drawing is performed at a temperature where T _L exceeds T _B -3 ° C. in the multistage hot drawing, it is difficult to obtain a fiber having an extremely high heat shrinkage stress and dry heat shrinkage.
On the other hand, if T _L is lower than 110 ° C., the wound yarn shrinks violently and the package cannot be removed from the winding machine, or the shape of the package is significantly impaired.
Therefore, 110 ℃ ~T _B -3 ℃ as the final heat stretching temperature T _L, preferably 1
50 ℃ ~T _B -5 ℃, further preferably at 200 ℃ ~T _B -10 ℃.
It is important that the stretching ratio in the final stretching at this time is 1.01 to 1.5 times.
When the draw ratio is less than 1.01, the amount of strain applied to the amorphous portion is insufficient, and a polyketone fiber having high heat shrinkage stress and heat shrinkage cannot be obtained. On the other hand, when the draw ratio exceeds 1.5 times, a strong load is applied to the amorphous molecular chains, causing troubles in the process such as fluff and breakage of single yarn, and also causes a decrease in strength of the drawn yarn.
For this reason, it is desirable that the final stretch ratio is 1.01 to 1.5 times, preferably 1.02 to 1.3 times, and more preferably 1.03 to 1.2 times.

Immediately after the completion of the hot drawing of (ii), the method of rapidly cooling while applying a high tension to the fiber means that the hot drawn yarn has a high tension of 0.5 to 4 cN / dtex immediately after the hot drawn yarn is performed. And rapidly cooling to a temperature of 50 ° C. or less at a cooling rate of 30 ° C./sec or more.
The present inventors have found that, when the fiber is rapidly cooled while applying a strong tension to the fiber in the hot drawing immediately after the hot drawing, a polyketone fiber having high heat shrinkage properties with distortion remaining in the amorphous portion can be obtained. I found it.
The tension applied at this time must be 0.5 cN / dtex or more. When the tension is less than 0.5 cN / dtex, the heat shrink force of the fiber from which the distortion remaining in the amorphous portion is small is insufficient. On the other hand, when the tension exceeds 4 cN / dtex, problems such as difficulty in winding the fiber stably and fluff and breakage of single yarn are likely to occur.
Therefore, the applied tension is in the range of 0.5 to 4 cN / dtex, preferably 0.8 to 3 cN / dtex, and more preferably 1 to 2 cN / dtex.
At this time, it is necessary to rapidly cool the drawn yarn to 50 ° C. or less at a speed of 30 ° C./second or more.
When the cooling rate is less than 30 ° C./sec, the heat shrinkage stress of the fiber becomes insufficient. Further, when the temperature at the cooling end point is higher than 50 ° C., the heat shrinkage stress of the fiber obtained similarly becomes insufficient.
Therefore, it is desirable that the cooling rate is 30 ° C./sec or more, more preferably 50 ° C./sec or more, and further preferably 100 ° C./sec or more.

Further, it is desirable that the temperature at the end point of the rapid cooling be 50 ° C. or lower, more preferably 40 ° C. or lower, and further preferably 30 ° C. or lower.
Further, the temperature at the quenching end point is preferably −40 ° C. or more, more preferably 0 ° C. or more, and still more preferably 10 ° C. or more, from the viewpoint of the handling property of the apparatus and the manufacturing cost.
There is no particular limitation on the method of rapidly cooling the drawn yarn, and any method such as contacting with a solid such as a cooled roll or plate, a liquid such as water or oil, or a gas such as air or nitrogen may be employed. These cooling media may be used in combination.
A cooling method using a roll is preferably used in terms of heat transfer efficiency and manufacturing cost. When cooling using rolls, when the rotation speed is high or the total fineness of the drawn yarn is large, the temperature of the roll surface will be increased by the amount of heat brought by the drawn yarn, so keep the roll temperature constant. Is essential.
Specifically, for example, a method of flowing cooling water inside the roll, blowing cooling air to the roll surface, or applying cooling water or cooling oil to the roll surface is suitably used.
In addition, the slip of the drawn yarn on the roll leads to relaxation of the applied tension, and the heat shrinkage stress of the obtained polyketone fiber is reduced. It is important to suppress the slip of the above drawn yarn.

Polyketone fibers having high heat shrinkage stress and heat shrinkage can be obtained by the above method.However, such fibers have a large amount of residual elastic strain. The package is wrapped with a large number of yarns, because the shrinkage of the wound fiber causes the package to be unwound from the take-up device, the package to be disassembled, the fiber to be unable to be released smoothly from the package, and the like. There is a disadvantage that it becomes impossible to obtain.
The inventors of the present invention carry out relaxation heat treatment of a polyketone fiber having a high heat shrinkage stress at a temperature of 50 to 100 ° C., so that the above-described curling and the problem of the package form are hardly impaired. Can be greatly improved. When the heat treatment temperature exceeds 100 ° C., the fiber structure is stabilized by the above-described crystal phase transition, and the heat shrinkage stress is reduced. When the processing temperature is lower than 50 ° C., the elastic strain applied to the fiber is hardly relaxed, and the winding and the package form are not improved.

In the present invention, the relaxation heat treatment means that the relaxation length = L ₀ / L ₁ is less than _1, where L ₀ is the fiber length before heat treatment and L ₁ is the fiber length after heat treatment.
The relaxation ratio is desirably 0.980 to 0.999 times, preferably 0.990 to 0.998 times, and more preferably 0.995 to 0.997 times.
By performing the relaxation heat treatment at such a temperature of 50 to 100 ° C., the polyketone fiber whose strain has been thermally relaxed is wound up via a speed regulating roll or directly by a winder to form a package.
If the tension at the time of winding is too high, the polyketone fiber will be tightly wound due to elastic strain. Further, if the winding tension is too low, the winding form of the package is likely to collapse, so that it is preferably in the range of 0.001 to 0.8 cN / dtex, more preferably 0.01 to 0.3 cN / dtex. It is desirable to take up.
The form of the package is not particularly limited, and may be any form such as a cheese, a cone, a cake, and a pan.
When winding a filament having a large fineness such as a total fineness of 300 dtex or more, a cheese-like or pan-like package is preferably used.

The polyketone fiber may be used as a short fiber, and is obtained by cutting the polyketone filament of the present invention obtained by the above-described drawing and heat treatment method in the yarn length direction.
The length of the short fiber is not particularly limited, and may be cut to any length according to the use environment and the purpose of use, but usually the average length of the short fiber is 0.1 to 100 mm. It is preferably used.
When the average length is less than 0.1 mm, problems arise in workability and handling, such as difficulty in spinning.
On the other hand, if the average length exceeds 100 mm, a problem is likely to occur in the spinning process passability.
The average length of the short fibers in the present invention L (mm) is the length of one longitudinal direction of the short fibers (fiber axis direction) as the fiber length L _i, of the 100 chosen in any short fibers The average length is calculated by the following equation (3).
Such a short fiber is useful as a reinforcing material such as concrete or as a spun yarn in applications such as a knitted fabric and a rope.

The polyketone fiber obtained as described above may be used as it is or as necessary, as a processed yarn that has been subjected to processing such as twisting, false twisting, bulking, crimping, winding, and the like. It can be used as a fiber product processed into a nonwoven fabric.
The twisted product (twisted cord) obtained by twisting the polyketone fiber of the present invention exhibits high heat shrinkage stress and heat shrinkage similarly to the polyketone fiber of the present invention.
There are no particular restrictions on the type of twisted yarn, the method, and the number of twisted yarns, and examples of the type of twisted yarn of the polyketone fiber of the present invention include a single twisted yarn, a multi-twisted yarn, a picco-mother twisted yarn, and a strongly twisted yarn.
The number of twists is not particularly limited, and may be one twist, two twists, three twists, four twists, or five twists, or may be six or more twists.
Also, the number of twisted yarns is not particularly limited since it varies depending on the single yarn fineness or the total fineness, and the number of twisted yarns may be arbitrarily selected according to processing conditions and use environment. For example, in the case of a twisted cord composed of a polyketone multifilament having a single yarn fineness of 0.01 to 10 dtex and a total fineness of 30 to 100,000 dtex, the twist coefficient K represented by the following formula (4) is in the range of 1,000 to 30,000. Is preferably used.
If K is less than 1000, the fatigue resistance of the cord tends to decrease. On the other hand, when K exceeds 30,000, the strength of the cord decreases.
For this reason, the twist coefficient is desirably 1000 to 30,000, preferably 5000 to 25,000.
K = Y × D ^0.5 (4)
[Where Y is the number of twists per meter (T / m · dtex ^0.5 ), and D is the total fineness (dtex) of the polyketone multifilament. ]
It is desirable that the maximum heat shrinkage stress of the polyketone twisted cord having a twist coefficient K within the above-mentioned range is 0.6 cN / dtex or more.
When the maximum heat shrinkage stress of the twisted cord is less than 0.6 cN / dtex, not only is the heat shrinkage of the original yarn not fully utilized, but also the heat shrinkage is significantly increased when processing into a processed cord or into a molded product. And the tightening force of the molded product becomes insufficient.
Although the maximum heat shrinkage stress of the twisted cord varies depending on the twist structure and the number of twists, it is desirable that the maximum heat shrinkage stress is 75% or more, more preferably 80% or more of the maximum heat shrinkage stress of the original yarn. It is desirable to have a maximum heat shrinkage stress of 0.6 to 0.7 cN / dtex , more preferably an upper limit of 0.8 cN / dtex.

The polyketone fiber and the polyketone fiber cord having the above-described properties can be used as they are or processed into a fiber product, and can be applied to a wide range of uses such as clothing, industrial use, and living materials.
In addition, the fiber product according to the present invention is a yarn composed only of the polyketone fiber according to the present invention, a hollow fiber, a porous yarn, cotton, a string, a knit, a woven fabric, a nonwoven fabric, and clothing using these, medical instruments, Living materials, tire cords, belts, concrete reinforcing materials, and the like, as well as fibers using the polyketone fibers at least in part are included.
In the fiber product, polyamide fibers such as nylon 6, nylon 6.6, etc .; polyester fibers such as polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate; polyolefin fibers such as polyethylene and polypropylene; polyvinyl alcohol fibers, aramid fibers, wool, poly It may be used in combination with conventionally known fibers such as acrylonitrile fiber, cellulose fiber such as cotton and viscose rayon.
Fibers of the same kind, fibers having different thermal / mechanical properties, fibers having different fineness or number of filaments, or long fibers, short fibers, spun yarn, or the like may be used in combination.
The polyketone fiber of the present invention is a rubber reinforcing material such as a tire cord, a hose and a belt, a concrete reinforcing material, a nonwoven fabric such as a filter and a house wrap, a woven fabric such as an airbag and a sheet, a knitted fabric such as a fish net, a fishing line, a sewing thread, It can be widely used for industrial materials such as ropes and living materials.

The polyketone-treated cord of the present invention includes a step (so-called Dip treatment) of continuously adhering the polyketone twisted cord to a resorcin-formalin-latex (RFL) solution having a concentration of 10 to 30% by weight and applying heat of at least 100 ° C. Obtained by passing.
The polyketone-treated cord of the present invention has the ability to exhibit strong shrinkage when embedded in a material such as rubber.
Specifically, the dry heat shrinkage maximum thermal shrinkage stress at 0.2 ~0.4 cN / dtex, 150 ℃ is required to be from 0.5 to 6%.
If the maximum heat shrinkage stress of the treated cord is 0.2 to 0.4 cN / dtex , the shrink force is equivalent to that of a conventional material (nylon 6.6 , etc.), and functions as a tag material such as a cap ply or an edge ply. Will be enough to fulfill.
For maximum thermal shrinkage stress of handling code that enables weight reduction of the tire to reduce the use amount of fibers higher, preferably desired to have a maximum thermal shrinkage stress above 0.3 cN / dtex.
In particular, when used as a tire cord for a cap ply or an edge plastic, it is required that the heat shrinkage force per cord is high, and the maximum heat shrinkage force per cord is adjusted by adjusting the fineness and the number of twisted yarns used. 500 to 1079 cN , particularly preferably 600 cN or more.

Further, the treatment code of the present invention is required to have a high heat shrinkage rate in addition to a high heat shrinkage force.
If the heat shrinkage ratio is low while having a high heat shrinkage force, there will be a problem that the shrinkage ratio of the treated cord is impaired due to a slight dimensional change at the time of molding, and a problem that it is difficult to perform stable molding to the same size.
On the other hand, if the heat shrinkage is too large, the dimensional change during molding into a tire is large, and stable molding as designed becomes difficult. Therefore, it is desirable to have a dry heat shrinkage at 150 ° C. of 0.5% to 5%, preferably 1% to 4%, and more preferably 2% to 3%.
In order to obtain a polyketone-treated cord having such a high heat shrinkage property, it is necessary to control the tension applied to the cord to a specific range when applying the RFL liquid to the twisted cord and performing drying and heat treatment. Very important.
That is, when the heat treatment temperature of the twisted cord is T (° C.) and the tension applied during the heat treatment is σ _D (cN / dtex), σ _D falls within the range of the following expression.
1.01 × σ _T ≦ σ _D ≦ 10 × σ _T (cN / dtex)
T = 100-270 ° C
(Here, σ _T is the heat shrinkage stress at the temperature T of the polyketone twisted cord.)

FIG. 1 shows an example of the relationship between the heat shrinkage stress σT and the heat treatment temperature T (° C.) of the polyketone twisted cord of the present invention.
When heat-treating the treatment code, the relaxation of the amorphous molecular chains due to thermal motion occurs, but this relaxation can be suppressed by applying tension during the treatment.
When σ _D is less than 1.01 times σ _T , the relaxation of the amorphous molecular chains occurs predominantly during the heat treatment, and the degree of reduction of the maximum heat shrinkage stress of the processing code increases, and the maximum heat shrinkage stress of the processing code increases. Becomes insufficient. On the other hand, when σ _D exceeds 10 times σ _T, the twist structure becomes unstable, and the twist and shrinkage of the processing cord increase, and in some cases, the cord breaks during processing.
For this reason, the tension (σ _D ) applied to the processing code is preferably 1.01 of σ _T.
It is desirable that the ratio be 10 to 10 times, more preferably 1.03 to 5 times, and still more preferably 1.05 to 2 times.

The adhesion amount of the RFL resin is preferably 2 to 7% by weight based on the weight of the fiber.
The composition of the RFL solution is not particularly limited, and a conventionally known composition can be used as it is or with some modification.
A preferred composition of the RFL solution is 0.1 to 10% by weight of resorcinol, 0.1 to 10% by weight of formalin, and 1 to 28% by weight of latex, and a more preferred composition is 0.5 to 3% by weight of resorcinol. %, Formalin 0.5 to 3% by weight, and latex 10 to 25% by weight are desirable.
Further, the drying temperature of the RFL solution is preferably 100 to 250 ° C., more preferably 140 to 200 ° C., and it is desirable to perform a dry heat treatment for at least 10 seconds, preferably 20 to 120 seconds.

Further, it is desirable that the RFL-attached cord after drying is subjected to heat treatment continuously. The heat treatment temperature after drying is preferably the maximum heat shrinkage temperature of the polyketone twisted cord ± 50 ° C, more preferably the maximum heat shrinkage temperature ± 10 ° C, and most preferably the maximum heat shrinkage temperature ± 5 ° C, and the heat treatment time is preferably 10 ° C. The time is preferably from 300 to 300 seconds, more preferably from 30 to 120 seconds.
The polyketone-treated cord having a high heat shrink force of the present invention is extremely useful as a tire reinforcing material such as a cap ply or an edge ply, or a belt reinforcing material.

The present invention will be described in more detail with reference to the following examples and the like, but they do not limit the scope of the present invention.
The measuring method of each measured value used in the description of the embodiment is as follows.
(1) Intrinsic Viscosity Intrinsic viscosity [η] (dl / g) is a value obtained based on the following definition formula.
[Η] = lim (T−t) / (t · C)
C → 0
(Where t and T in the formula are the flow times of a diluted solution of hexafluoroisopropanol having a purity of 98% or more and a polyketone dissolved in the hexafluoroisopropanol at 25 ° C. through a viscosity tube at 25 ° C. Is the solute weight value in grams.)
(2) Fineness, Tensile strength, Tensile elongation, Tensile modulus Measured according to JIS-L-1013.
The value of the initial elastic modulus calculated from the load at an elongation of 0.1% and the load at an elongation of 0.2% was used as the tensile elastic modulus.
(3) Fineness of twisted cord and treated cord Weight W ₁ (g) per 10 m of the cord was measured, and W ₁ × 1000 was defined as the fineness (dtex) of the twisted cord.
(4) RFL Resin Adhesion Rate The weight W ₂ (g) per 10 m of the cord is measured. Next, the treatment cord is cut into 1 mm lengths, weighed exactly 1.00 g, and dissolved in 200 ml of hexafluoroisopropanol under stirring at 60 ° C. for 2 hours.
The weight W ₃ (g) of the filtration residue after dissolution was precisely weighed, and the RFL resin adhesion rate (%) and the fineness of the treatment code were used from the following equation (6).
RFL resin adhesion rate (%) = W ₃ × 10 / W ₂ × 100 (6)

(5) Heat shrinkage stress, maximum heat shrinkage stress, maximum heat shrinkage temperature Using a CORD-TESTER (Goodrich Type) manufactured by Toyo Seiki Seisaku-Sho, Ltd., the heat shrinkage force of fibers and cords under a constant displacement under the following conditions: The properties were measured.
Temperature Program: EXP mode
Θ _M : 250 ° C
T ₁ : 3 minutes
Initial load: 1/80 (g / dtex)
Initial sample length: 250mm
The contraction force F _T (cN) at the temperature T is read from the measured temperature-contraction force curve, and the F _T is divided by the fineness (dtex) of the sample to obtain a heat contraction stress σ _T ( _T
cN / dtex).
Further, the temperature _Tmax (° C.) showing the maximum contraction force F _max (cN) and the maximum contraction force
) _Was read and _Tmax was taken as the maximum heat shrinkage temperature.
Further, the maximum heat shrinkage stress σ _max (cN / dtex) was determined by dividing the value obtained by dividing F _max by the fineness (dtex) of the sample.
For the processing code, _Fmax was defined as the maximum thermal contraction force of the code (cN / code).
(6) Dry heat shrinkage rate Dry heat treatment was performed in an oven at 150 ° C. for 30 minutes, and the fiber length before and after the heat treatment was measured by applying a load of 1/30 (cN / dtex), and the following formula (7) was used. I asked.
Dry heat shrinkage _{(%) = (L b -L} a) / L b × 100 ··· (7)
(However, L _b is the fiber length before heat treatment, L _a is the fiber length after the heat treatment.)

(7) Crystallinity The crystallinity was measured under the following conditions using a differential heat measurement device “Pyrisl” manufactured by Perkin Elmer.
Measurement temperature: 30 ° C → 300 ° C
Heating rate: 20 ° C./min Atmosphere: nitrogen, flow rate = 200 mL / min Calorific value ΔH (J / g) calculated from the area of the largest endothermic peak obtained in the range of 200 ° C. to 300 ° C. in the obtained endothermic curve. ) Was calculated by the following equation (8).
Crystallinity (%) = ΔH / 225 × 100 (8)
(8) Degree of Crystal Orientation A fiber diffraction image was captured under the following conditions using an imaging plate X-ray diffractometer “RINT” 2000 manufactured by Rigaku Corporation.
X-ray source: CuKα ray
Output: 40KV 152mA
Camera length: 94.5mm
Measurement time: 3 minutes Calculated by the following formula (9) from the half width H of the intensity distribution obtained by scanning the (110) plane observed around 2θ = 21 ° of the obtained image in the circumferential direction.
Crystal orientation (%) = (180−H) / 180 × 100 (9)

( Production Example 1)
A polyketone polymer having an intrinsic viscosity of 5.3, prepared by a conventional method, in which ethylene and carbon monoxide are completely alternately copolymerized, is added to an aqueous solution containing 65% by weight of zinc chloride / 10% by weight of sodium chloride, and stirred at 80 ° C. for 2 hours. Upon dissolution, a dope having a polymer concentration of 8 wt% was obtained. The dope was heated to 80 ° C., filtered through a 20 μm sintering filter, passed through a 10 mm air gap from a 50-hole spinneret kept at 80 ° C., and then 5 wt% zinc chloride. Was extruded at a discharge rate of 2.5 cc / min into water containing 18 ° C., and a coagulated yarn was formed while drawing at a speed of 3.2 m / min.
Subsequently, the coagulated yarn was washed with a sulfuric acid aqueous solution having a concentration of 2% by weight and a temperature of 25 ° C., and further washed with water at 30 ° C., and then the coagulated yarn was wound at a speed of 3.2 m / min. The coagulated yarn was impregnated with IRGANOX1098 (manufactured by Ciba Specialty Chemicals) and IRGANOX1076 (manufactured by Ciba Specialty Chemicals) in an amount of 0.05% by weight (based on polyketone polymer), and then dried at 240 ° C. A finishing agent was applied to obtain an undrawn yarn.
The finishing agent used had the following composition.
Lauryl oleate / bisoxyethyl bisphenol A / polyether (propylene oxide / ethylene oxide = 35/65: molecular weight 20,000) / oleyl ether with addition of 10 moles of polyethylene oxide / castor oil ether with addition of 10 moles of polyethylene oxide / sodium stearyl sulfonate / dioctylline Sodium acid = 30/30/10/5/23/1/1 (weight% ratio).
The first stage of the obtained undrawn yarn was drawn at 240 ° C., then at 258 ° C., at the second stage, at 268 ° C. at the third stage, at 272 ° C. at the fourth stage, and then at the fifth stage at 200 ° C. The film was stretched at 1.08 times (stretching tension 1.8 cN / dtex) in five steps and wound up by a winder. The total draw ratio from the undrawn yarn to the five-stage drawn yarn was 17.1 times.
This fiber has high physical properties such as a strength of 15.6 cN / dtex, an elongation of 4.2%, an elastic modulus of 347 cN / dtex, a dry heat shrinkage of 4.3%, and a maximum heat shrinkage stress of 0.92 cN / dtex. And high heat shrinkage characteristics.
The fiber properties and the heat treatment conditions of polyketone fibers and twisted cord embodiment of the present invention together with the results of preparation 2 Preparation 15 below are summarized in Table 1.

( Production Example 2)
In Production Example 1, the fifth stage was stretched at 150 ° C. at a draw ratio of 1.05 and wound up.
( Production Example 3)
In Production Example 1, the fifth stage was stretched at 250 ° C. at a magnification of 1.10 times and wound up.
( Production Example 4)
In Production Example 1, the fifth step was wound at 265 ° C. as a stretch of 1.14 times.
( Production Example 5)
In Production Example 1, the fourth stage was wound at 263 ° C. as a stretch of 1.17 times.
( Production Example 6)
In Production Example 1, four-step stretching was performed at 272 ° C. with a tension of 2.3 cN / dtex, and the mirror surface whose surface was cooled to 15 ° C. with a cooling wind at a wind speed of 2 m / sec while applying a tension of 2.3 cN / dtex. After rapid cooling by passing through the roll for 7 turns, it was wound up by a winder.

( Production Example 7)
The dope obtained in Production Example 1 was extruded at a rate of 12.5 cc / min from a 250-hole spinneret with a spinner diameter of 0.10 mm, L / D = 1, and solidified. The coagulated yarn is successively washed with a 2% by weight aqueous sulfuric acid solution, further washed with water at 30 ° C., wound up at a winding speed of 2.5 m / min, and further dried at 240 ° C. Thus, an undrawn yarn was obtained.
After performing the first stage drawing at 240 ° C., the undrawn yarn is subjected to the second stage at 260 ° C., the third stage at 270 ° C., and 1.20 times at 265 ° C., for a total of 16.3 times. Was stretched.
( Production Example 8)
A polyketone polymer having an intrinsic viscosity of 2.8, which is obtained by completely alternating ethylene and carbon monoxide by a conventional method, is added to an aqueous solution containing 65% by weight of zinc chloride / 10% by weight of sodium chloride, and stirred at 80 ° C. for 2 hours. Upon dissolution, a dope having a polymer concentration of 18 wt% was obtained. This dope was spun and dried at the same temperature and formulation as in Production Example 1. This unstretched yarn is stretched at 240 ° C. in the first stage, 255 ° C. in the second stage, 268 ° C. in the third stage, and further in the fourth stage at 263 ° C. at 1.22 times, and the total stretching ratio is 4 stages of 17.3 times. Stretching was performed.

( Production Example 9)
A polyketone polymer having an intrinsic viscosity of 9.8, which is obtained by completely alternating ethylene and carbon monoxide by a conventional method, is added to an aqueous solution containing 65% by weight of zinc chloride / 10% by weight of sodium chloride, and stirred at 80 ° C. for 2 hours. Upon dissolution, a dope having a polymer concentration of 5.5% by weight was obtained. This dope was spun and dried at the same temperature and formulation as in Production Example 1.
The unstretched yarn is stretched at 240 ° C. in the first stage, 255 ° C. in the second stage, 268 ° C. in the third stage, and the fourth stage is stretched at 263 ° C. to 1.11 times, and the total stretching ratio is 14.2 times. Stretching was performed.
( Production Example 10)
Spinning and drying were carried out under the same spinning conditions as in Production Example 1, except that an aqueous solution containing 40% by weight of zinc chloride / 30% by weight of calcium chloride was used as a solvent.
This unstretched yarn is stretched at 240 ° C. in the first stage, 255 ° C. in the second stage, 270 ° C. in the third stage, and further in the fourth stage at 265 ° C. at a ratio of 1.20 times and a total stretching ratio of 16.3 times. Stretching was performed.

( Production Example 11)
After 19 dry yarns obtained by the formulation of Production Example 1 were ligated and the finishing agent used in Production Example 1 was applied, the first stage was 240 ° C., and the second stage was 258 ° C., the second stage was 270 ° C. The third stage of stretching is carried out, and then the fourth stage is stretched at 265 ° C. at 1.14 times (stretching tension: 1.5 cN / dtex) and the total stretching ratio is 16.1 times. Wound up.
( Production Example 12)
The 4-stage drawn yarn of Production Example 11 was passed through a mirror roll whose surface was cooled to 15 ° C. for 7 rounds while applying a drawing tension of 1.5 cN / dtex, and then on a satin roll heated to 75 ° C. After a relaxation heat treatment of 0.995 times, it was wound in a cheese-like package by a winder to obtain a cheese-like package having a winding weight of 1.5 kg.
In this package, the tightness was small, it could be easily removed from the winding machine, and the yarn could be easily released from the package.

( Production Example 13)
The drawn polyketone yarn obtained in Production Example 12 was double-twisted and subjected to priming (Z-twisting) and ply-twisting (S-twisting) at 390 twists / m to obtain a twisted cord having a twist coefficient of 20,000. This twisted cord had high heat shrinkage stress and heat shrinkage.
( Production Example 14)
The bottom twist and the top twist were performed in the same manner as in Production Example 13 except that the number of twists was set to 250 times / m, to obtain a twisted cord having a twist coefficient of 12,800.
( Production Example 15)
Except that the number of twists was set to 100 times / m, ply twist and ply twist were performed in the same manner as in Production Example 13 to obtain a twisted cord having a twist coefficient of 5100.

(Example 1 )
The twisted cord obtained in Production Example 13 was immersed in a resorcinol-formalin-latex (RFL) adhesive having the following liquid composition, heat-treated at 160 ° C for 60 seconds, dried at 215 ° C for 60 seconds, and further dried at 215 ° C. A heat set for 60 seconds was performed to obtain a treatment code.
(RFL liquid composition)
Resorcinol 22.0 parts
Formalin (30% by weight) 30.0 parts
Sodium hydroxide (10% by weight) 14.0 parts
570.0 parts of water
364.0 parts of vinylpyridine latex (41% by weight) The performance and Dip treatment conditions of the obtained treatment cord are shown in Table 2 together with the results of Examples 2 to 4 below.

(Examples 2-3 )
A treatment code was obtained using the same prescription as in Example 1 but changing the immersion (Dip) treatment conditions. (Example 4 )
Using a twisted cord obtained by manufacturing Zorei 15, to obtain a treated cord subjected to immersion (Dip) treated in the same formulation as in Example 1.
( Production Example 16 )
The polyketone multifilament obtained in Production Example 13 was converted into a sliver composed of short fibers having an average yarn length of 35 mm using a stapler. This short fiber was spun into a single yarn at a twist factor of 60 (meter count) to obtain a spun yarn. This spun yarn had high heat shrinkability.

(Comparative Production Example 1)
The four-stage stretched yarn obtained in Production Example 1 before the five-stage stretching had a strength of 15.4 cN / dtex, an elastic modulus of 331 cN / dtex and excellent fiber properties, but a maximum heat shrinkage stress of 0.79 cN / dtex. The power was insufficient.
The characteristics and the heat treatment conditions of the polyketone fiber and twisted cord used in Comparative Examples together with the results of Comparative Production Example 2 Comparative Production Example 11 below are summarized in Table 3.
( Production Comparative Example 2)
The undrawn yarn obtained in Production Example 1 was completely inadequate in all of the fiber properties such as strength and elastic modulus and the maximum heat shrinkage stress.
( Production Comparative Example 3)
In Production Example 1, the drawn yarn obtained by subjecting the undrawn yarn to one-stage drawing at 240 ° C. by 6 times had insufficient mechanical properties such as strength and elastic modulus and maximum heat shrinkage stress.

( Production Comparative Example 4)
In Production Example 1, the undrawn yarn was subjected to three-stage drawing at 240 ° C. in the first stage, 255 ° C. in the second stage, and 265 ° C. in the third stage with a total draw ratio of 12 times.
Although the drawn yarn had good fiber properties such as strength and elastic modulus, the maximum heat shrinkage stress was insufficient.
( Production Comparative Example 5)
In Production Example 1, the fifth stage was stretched at 270 ° C. and 1.05 times in five stages, but the maximum heat shrinkage stress was insufficient at 0.78 cN / dtex.
( Production Comparative Example 6)
In Production Example 1, the fifth stage was stretched at 200 ° C. and 1.00 times in five stages, but the maximum heat shrinkage stress was insufficient.

( Production Comparative Example 7)
In Production Example 1, the fifth stage was stretched at 200 ° C. and 0.98 times in five stages, but the maximum heat shrinkage stress was completely insufficient.
( Production Comparative Example 8)
In Production Example 1, the fifth stage was stretched at 80 ° C. and 1.03 times in five stages, but the maximum heat shrinkage stress was not changed.
( Production Comparative Example 9)
In Production Example 1, four-step stretching was performed at 272 ° C. with a tension of 2.3 cN / dtex, and then, while applying a tension of 2.3 cN / dtex, the film was wound around a mirror roll having a surface temperature of 80 ° C. seven times, followed by winding. It was wound by a take-up machine.

( Production Comparative Example 10)
Twenty nine dried yarns obtained by the formulation of Production Example 1 were ligated, and after applying the finishing agent used in Production Example 1, the first stage was at 240 ° C., followed by the second stage at 258 ° C. and the second stage at 268 ° C. After performing stretching at a total draw ratio of 16.6 times at 272 ° C. in the third and fourth stages, heat treatment was subsequently performed on a satin roll heated to 75 ° C., and then the film was wound up by a winder.
( Production Comparative Example 11)
Using the drawn yarn obtained in Production Comparative Example 10, double-twisting was performed in the same manner as in Production Example 13, and priming and ply-twisting were performed at a twist number of 390 times / m to obtain a twisted cord having a twist coefficient of 20,000. This twisted cord had a heat shrinkage stress of 0.58 cN / dtex.

(Comparative Example 1 )
The twisted cord obtained in Production Comparative Example 11 was subjected to a heat treatment using an RFL solution having the same composition as in Example 1 to obtain a polyketone-treated cord. However, the maximum heat shrinkage stress of the obtained treated cord was insufficient. Was. The performance and immersion (Dip) treatment conditions of the obtained treatment cords are shown in Table 4 together with the results of Comparative Examples 2 to 7 below.
(Comparative Examples 2 and 3 )
A treatment code was obtained with the same prescription as in Comparative Example 1 by changing the immersion (Dip) treatment conditions.
(Comparative Examples 4 to 6 )
Using the twisted cord obtained in Production Example 13, a treated cord was obtained in the same manner as in Example 1 except that the immersion (Dip) treatment conditions were changed. The results of Production Examples 1 to 16 , Examples 1 to 4, Production Comparative Examples 1 to 11, and Comparative Examples 1 to 6 are summarized in Tables 1 to 4 below.
Table 1 shows the drawing conditions, fiber properties, and fiber structure of polyketone fibers ( Production Examples 1 to 15) which are the raw materials of the treatment cord of the present invention.

（注）△Ｔ＝（最終の１段前の延伸温度Ｔ₀ ）ー（最終延伸温度Ｔ_L ）

(Note) △ T = (stretching temperature T ₀ one step before final)-(final stretching temperature _TL )

（注）（ｉ）（σ_D ／σ_T ）₁ ＝RFL 浸漬時の張力/ 撚糸コードのRFL 浸漬温度における熱収縮力
（ｉｉ）（σ_D ／σ_T ）₂ ＝乾燥張力/ 撚糸コードの乾燥温度における熱収縮力
（ｉｉｉ）（σ_D ／σ_T ）₃＝セット張力／撚糸コードのセット温度における熱収縮力 Table 2 shows the immersion (Dip) treatment conditions and the characteristics of the polyketone treated cord (Examples 1 to 4 ) of the present invention.

(Note) (i) (σ _D / σ _T ) ₁ = tension during RFL immersion / heat shrinkage of twisted cord at RFL immersion temperature (ii) (σ _D / σ _T ) ₂ = drying tension / drying of twisted cord Heat shrink force at temperature (iii) (σ _D / σ _T ) ₃ = set tension / heat shrink force at set temperature of twisted cord

（注）△Ｔ＝（最終の１段前の延伸温度Ｔ₀ ）ー（最終延伸温度Ｔ_L ） Table 3 shows the polyketone fiber stretching conditions and fiber conditions of Production Comparative Examples 1 to 11 .

(Note) △ T = (stretching temperature T ₀ one step before final)-(final stretching temperature _TL )

（注）（ｉ）（σ_D ／σ_T ）₁ ＝RFL 浸漬時の張力/ 撚糸コードのRFL 浸漬温度における熱収縮力
（ｉｉ）（σ_D ／σ_T ）₂ ＝乾燥張力/ 撚糸コードの乾燥温度における熱収縮力
（ｉｉｉ）（σ_D ／σ_T ）₃＝セット張力／撚糸コードのセット温度における熱収縮力 Table 4 shows the immersion (Dip) treatment conditions and the characteristics of the polyketone treatment cords of Comparative Examples 1 to 6 .

(Note) (i) (σ _D / σ _T ) ₁ = tension during RFL immersion / heat shrinkage of twisted cord at RFL immersion temperature (ii) (σ _D / σ _T ) ₂ = drying tension / drying of twisted cord Heat shrink force at temperature (iii) (σ _D / σ _T ) ₃ = set tension / heat shrink force at set temperature of twisted cord

FIG. 1 is a graph showing the relationship between the heat shrinkage stress and the temperature of the polyketone twisted cord of the present invention.

Claims (4)

A polyketone fiber treated cord in which a polyketone fiber is treated with a resorcin-formalin-latex resin, having a maximum heat shrinkage stress of 0.2 to 0.4 cN / dtex and a dry heat shrinkage at 150 ° C of 0. 0.5 to 6%. Maximum thermal shrinkage stress 0.3 ~0.4 cN / dtex, 150 polyketone processing code according to claim 1, wherein the thermal shrinkage rate is characterized by a 1-4% at ° C.. Wherein the maximum heat shrinkage force is 500 ~1079 cN / cord, according to claim 1 or 2 polyketone processing code according. A method for producing a polyketone-treated cord in which a polyketone twisted cord is immersed in a resorcinol-formalin-latex solution and then heat-treated.
Polyketone treatment including a process characterized in that, when the heat treatment temperature of the twisted cord is T (° C.) and the tension applied during the heat treatment is σ _D (cN / dtex), σ _D and T are within the range of the following formula. Code manufacturing method.
1.01 × σ _T ≦ σ _D (cN / dtex) ≦ 10 × σ _T
100 ≦ T (° C.) ≦ 270
(Here, σ _T is the heat shrinkage stress at the temperature T of the polyketone twisted cord.)

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