JP2002339275A - Polyketone cord and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyketone cord having excellent mechanical characteristics of high strength and high toughness and having excellent dimensional stability under load and under heating and a method for producing the polyketone cord. SOLUTION: This polyketone comprises >=80 wt.% polyketone fiber composed of polyketone in which 97-100 wt.% of recurring unit is constituted of 1- oxotrimethylene and has characteristics satisfying the following (a) to (e): (a) tensile strength >=8 cN/dtex; (b) toughness >=20+14.6×K/10<4> -14.1×(K/10<4> )<2> +-2.7×(K/10<4> )<3> (cN.%/dtex) wherein K is a twist coefficient of cord represented by the formula K=Y×D<0.5> ; (c) intermediate elongation <=1.5×exp(5.5×K/10<5> ) (%); (d) dry heat shrinkage factor = 0-3% and (e) thermal intermediate elongation <=1.8×exp(5.5×K/10<5> ) (%).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a polyketone cord having excellent mechanical properties and extremely excellent dimensional stability under load and under heat. More specifically, it has excellent mechanical properties of high strength and high toughness, and has a small elongation under load, hardly causes thermal shrinkage even under heating,
Furthermore, the present invention relates to a polyketone cord having extremely small dimensional stability, which has a small elongation when subjected to a load under heating, and a method for producing the same. The polyketone cord of the present invention is applicable to a wide range of uses such as household materials, living materials, and industrial materials, and is particularly applied to industrial materials that are exposed to high loads and high temperatures during processing and use, specifically, tires and belts. It is extremely useful as a fiber material for rubber reinforcement of hoses and the like.

[0002]

2. Description of the Related Art Conventionally, in rubber products such as tires, belts, hoses, etc., fiber reinforced materials have been used as materials for providing the strength of the products. These fiber reinforcement materials are mainly metal fiber materials such as steel, rayon and nylon 6.
6. Organic fiber materials such as polyethylene terephthalate have been used. However, a metal material such as steel is excellent in mechanical performance, but has a large specific gravity, so that there is a problem that the weight of the material increases. On the other hand, conventional general-purpose organic materials also suffer from the problem that rayon has low mechanical strength and physical properties deteriorate under water or humidity. Nylon 6.6 has low elastic modulus, low dimensional stability under load, and Polyethylene terephthalate has a problem that heat shrinkage under heating is large.

As an alternative to these conventional organic fiber materials, carbon monoxide and olefins such as ethylene and propene are polymerized using palladium and nickel as catalysts, whereby carbon monoxide and olefins are substantially completely alternately copolymerized. Was found to be obtained (industrial materials, December issue, page 5, 1997).
), And studies on fiberization of polyketone have been conducted.
It is known that polyketone fibers have a higher melting point than conventional polyolefin fibers, and that fibers with 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. Among them, high strength, excellent mechanical properties of high elastic modulus and high melting point thermal properties, good adhesion to rubber, industrial materials applications, especially tires and belts,
It is expected to be used as a rubber reinforcing material for hoses and the like.

When a polyketone fiber is used as a rubber reinforcing material, usually, after twisting, it is embedded in a rubber material in the form of a cord or a blind by applying an adhesive thereto. A code to which an adhesive has been applied (hereinafter sometimes referred to as a “processing code”)
Various performances are required depending on the application.However, rubber reinforcement materials such as carcass plies for tires, conductive belts, and reinforcing layers for pressure-resistant and heat-resistant hoses are subject to high loads during use, and Since the cord is in a high temperature environment due to heat generated by contact and friction with the object, not only the performance required of the cord is high strength, but also the deformation and dimensional change under load are small, It is extremely important that the dimensional change is small and that the dimensional change when subjected to a load in a high temperature environment is small.

[0005] Several techniques have been disclosed for polyketone fibers (for example, see Japanese Patent Application Laid-Open No. Hei 4-50).
No. 5,344, JP-A-2-112413, JP-A-4-228613, JP-T-7-508317, JP-T-8-507328, U.S. Pat.
No. 5019, JP-A-11-072091).
These patent documents disclose a technique of obtaining a high-strength, high-modulus polyketone fiber by stretching a polyketone undrawn yarn obtained by melt spinning or wet spinning at a high magnification. However, these patent documents do not disclose any requirements relating to the polyketone cord or any technique relating to the production of the cord.

Japanese Patent Application Laid-Open No. 1-124617 discloses a technique in which a cord is formed by twisting polyketone fibers obtained by copolymerizing propylene at 8 mol% and dipping them in an adhesive. However, the melt-spinnable polyketone fibers used in the present invention have low crystallinity and low melting point and low strength and elastic modulus, and cords made of these low-physicality polyketone fibers have strength, thermal dimensional stability and mechanical dimensional stability. Is completely inadequate. Further, in JP-A-9-324377, a polyketone fiber having a strength of 10 g / denier or more and an initial elastic modulus of 120 g / denier or more is used.
A technique of a polyketone cord having a bending hardness of 10 to 80 g is disclosed. However, this document does not describe any technical requirements for cords having excellent dimensional stability under heating and under load, and also has low crystallinity and low melting point obtained by copolymerizing 7 mol% of propylene in Examples. Only a code with low physical properties and low dimensional stability using a polyketone fiber with low physical properties is disclosed.

Japanese Patent Application Laid-Open No. 9-329198 describes a cord composed of an ethylene / carbon monoxide copolymer in Example 2. The polyketone fiber used in the cord has a large elongation at a load of 2 g / denier of 1.6%, and even if a cord is produced from such a fiber, only a cord having insufficient dimensional stability under load is obtained. I can't do that. Such a cord can be used in applications where the mechanical load is relatively small, but cannot be used in applications requiring a high level of dimensional stability, such as tires and heat-resistant hoses. Further, JP-A-11-33
No. 4313 and Japanese Unexamined Patent Application Publication No. 11-336957 have a cord strength of 10 g / denier or more and 2.25 g / denier.
The requirement that the elongation under a denier load is 3% or less is described. Although this invention refers to the mechanical dimensional stability of the cord, it does not disclose any technique relating to a polyketone cord having excellent thermal dimensional stability and dimensional stability against a load under heating.

On the other hand, Japanese Patent Application Laid-Open No. 2000-14024 discloses that a cord made of polyketone fiber has an elastic modulus of 588.
A technical requirement of 0 MPa or more is disclosed.
Also, Japanese Patent Application Laid-Open No. 2000-142025 discloses that a load made of a cord made of polyketone fiber at 2% elongation is 13.2.
Technical requirements that are less than or equal to mN / dtex are disclosed.
Further, Japanese Patent Application Laid-Open No. 2000-190705 discloses that the polyketone cord has an Ed modulus of 250 to 400 (gf).
/ Denier) is disclosed. However, these inventions only disclose the mechanical properties (mainly properties relating to elastic modulus) of cords, but do not disclose a polyketone cord having excellent dimensional stability under heating and a method for producing the cord. .

In Japanese Unexamined Patent Publication No. 2000-264012, the physical property of a cord is 2.03 g / dte.
The intermediate elongation under x load is 4% or less, 177 ° C x 30 minutes (1
It is described that the heat shrinkage rate under a load of / 60 g / dtex) is preferably 5% or less. However, the technical requirements relating to a cord satisfying this property and a method for producing the cord are completely specified. Not. Further, in the present invention, no technique relating to a polyketone cord which is excellent in dimensional stability when subjected to a load at a high temperature, which is most important in practical use, is not known at all. Actually, in the present invention, a cord manufactured using a polyketone terpolymer (96% by mass of 1-oxotrimethylene unit) in which propylene is copolymerized by 3 mol% is disclosed in Examples, but 1-oxotrimethylene unit is used. A cord having a methylene unit of less than 97% by mass has a high intermediate elongation and a low dimensional stability at the time of heating, and is a cord having completely insufficient mechanical dimensional stability and thermal dimensional stability. In particular, the cord made of such a polyketone terpolymer has a remarkable decrease in physical properties at high temperature (particularly, a decrease in intermediate elongation).
tex × 2 twists, 390T / m for both top and bottom twists
In the case of the cord, the intermediate elongation at the time of heat specified in the present invention is 4% or more, and only an extremely insufficient cord equivalent to polyester can be obtained. As described above, while having high strength, and having excellent mechanical properties of high toughness, it also has excellent dimensional stability under load, and even when heated and under load under heating. There is no known polyketone cord having excellent dimensional stability and any technique for producing the cord.

[0010]

An object of the present invention is to provide a polyketone cord comprising a polyketone fiber, which has excellent mechanical properties of high strength and high toughness, and under load, under heating, and under heating. It is an object of the present invention to provide a polyketone cord having excellent dimensional stability when a load is applied thereto, and a method for producing the same.

[0011]

Means for Solving the Problems In order to achieve the above object, the present inventors have conducted intensive studies on the production conditions of a polyketone cord, and as a result, have specified a highly crystalline polyketone after wet spinning, drying and hot stretching. Using polyketone fibers treated under the conditions of temperature and tension, it was found that selecting twisting conditions and RFL treatment conditions may be countermeasures, and as a result of further investigation, the present invention has been reached. That is, in the present invention, 97 to 100% by mass of the repeating unit is 1-
A cord containing at least 80% by mass of a polyketone fiber made of a polyketone composed of oxotrimethylene, wherein the cord has characteristics satisfying the following (a) to (e). (A) Tensile strength ≧ 8 cN / dtex (b) Toughness ≧ 20 + 14.6 × K / 10 ⁴ -14.1 × (K / 10 ⁴ ) ² + 2.7 × (K / 10 ⁴ ) ³ (cN ·% / Dtex) where K is the twist coefficient of the cord represented by the following equation 1. K = Y × D ^0.5 (Equation 1) where Y is the number of twists per meter of cord (T / m), D
Is the total indicated fineness (dtex) of the polyketone cord. (C) Intermediate elongation ≦ 1.5 × exp (5.5 × K / 10 ⁵ ) (%) (d) Dry heat shrinkage = 0 to 3% (e) Hot intermediate elongation ≦ 1.8 × exp (5.5 × K / 10 ⁵ ) (%) Here, the intermediate elongation is the elongation under a load of 2.0 cN / dtex, and the dry heat shrinkage is before and after heat treatment at 150 ° C. for 30 minutes. The shrinkage ratio, and the intermediate elongation under heat is the elongation under a load of 2.0 cN / dtex at 150 ° C.

The polyketone used in the present invention is a polyketone in which 97 to 100% by mass of the repeating unit is composed of 1-oxotrimethylene. The repeating unit composed of 1-oxotrimethylene is a group represented by the following structural formula 1.

Embedded image

The higher the proportion of 1-oxotrimethylene in the repeating unit, the higher the regularity of the molecular chain and the higher the crystallinity.
As a result, a fiber having a high degree of orientation can be obtained, and as a result, a cord having high strength, high elastic modulus and high heat resistance can be obtained. For this reason, it is preferably 97% by mass or more, most preferably 100% by mass.
It is desirable that the mass% is 1-oxotrimethylene. If the proportion of 1-oxotrimethylene in the repeating unit is within the range of 97% by mass or more, copolymers of olefins other than ethylene, such as propene and butene, and other compounds having an unsaturated hydrocarbon may be used as necessary. May be done.

The degree of polymerization of the polyketone in the polyketone cord is preferably 2 to 10 in intrinsic viscosity.
When the intrinsic viscosity is less than 2, the strength and toughness of the polyketone cord are reduced, and a polyketone cord having high mechanical properties cannot be obtained. On the other hand, when the intrinsic viscosity exceeds 10, the polymerization cost and the spinning cost increase, and it is difficult to obtain a polyketone fiber at a practical price. Therefore, the polymerization degree of the polyketone in the polyketone cord is such that the intrinsic viscosity is 2
It is desirably in the range of 10 to 10, more preferably in the range of 3 to 6.

The proportion of the polyketone fibers in the polyketone cord of the present invention must be at least 80% by mass. When the proportion of the polyketone fiber is less than 80% by mass, mechanical properties and mechanical dimensional stability are reduced. Since the higher the proportion of polyketone fibers in the cord, the better the mechanical properties and mechanical dimensional stability of the cord, the proportion of polyketone fibers is preferably 90% by mass or more. If the content is within the range of 20% by mass or less, a compound other than the polyketone fiber such as an adhesive or a coating agent or a fiber other than the polyketone fiber may be contained as necessary.

The polyketone cord of the present invention needs to have a tensile strength of 8 cN / dtex or more. If the tensile strength is 8 cN / dtex or more, it is possible to use a smaller (lighter) amount of cord compared to general-purpose organic fiber cord of polyester or rayon which has been conventionally used as a reinforcing material for tires, belts and hoses. In addition, the weight of the material can be reduced, and an economically excellent reinforcing material can be obtained. The higher the tensile strength of the polyketone cord, the better from the viewpoints of weight reduction and economical efficiency of the molded article, and it is particularly desirable that the tensile strength be 10 cN / dtex or more.

In the tensile test, the polyketone cord of the present invention needs to have a toughness determined from the area of the stress-elongation curve within the range of the following equation (2). Toughness ≧ 20 + 14.6 × K / 10 ⁴ −14.1 × (K / 10 ⁴ ) ² +2. 7 × (K / 10 ⁴ ) ³ (cN ·% / dtex) (Equation 2) where K is a twist coefficient of the cord represented by the following Equation 1. K = Y × D ^0.5 (Equation 1) where Y is the number of twists per meter of cord (T / m), D
Is the total indicated fineness (dtex) of the polyketone cord.
The total display fineness of the cord is the sum of the fineness of all the polyketone fibers used in the cord. For example, when a cord is formed by using three 1670 dtex polyketone fibers, the total display fineness of the cord is 5010 dtex (1670 × 3).

Toughness is a parameter indicating the breaking energy, and the higher the value, the better the toughness against a tensile load. Since the toughness of the polyketone cord greatly changes depending on the twisting coefficient, it is important to design the number of twisted yarns according to the application and purpose so that the toughness falls within the range of the above-described formula 1. If the toughness is below the above range, the toughness as a rubber reinforcing material becomes insufficient, and it is necessary to increase the amount of cord used to maintain the toughness,
Codes with excellent lightweight and economical efficiency cannot be obtained. The higher the toughness of the cord, the better, and it is particularly desirable that the cord falls within the range of the following equation (3). Toughness ≧ 30 + 14.6 × K / 10 ⁴ -14.1 × (K / 10 ⁴ ) ² +2. 7 × (K / 10 ⁴ ) ³ (cN ·% / dtex) (Equation 3)

Further, the polyketone cord of the present invention needs to have an intermediate elongation in the range of the following formula 4. Intermediate elongation ≦ 1.5 × exp (5.5 × K / 10 ⁵ ) (%) (Equation 4) Here, the term “intermediate elongation” means a value obtained when a 2.0 cN / dtex load is applied in a stress-elongation curve of a tensile test. Elongation (%), where K is the twist coefficient of the above-described cord. The smaller the intermediate elongation, the smaller the dimensional change with respect to the load, indicating better mechanical dimensional stability. Generally, the intermediate elongation increases as the twisting coefficient K increases, but even when the twisting coefficient increases, it is possible to select the raw yarn performance and the twisting / resorcin-formalin-latex treatment conditions so as to be within the range of the above formula 4. is important. The intermediate elongation of the polyketone cord of the present invention is more preferably in the range of the following formula 5, and particularly preferably in the range of the formula 6. Intermediate elongation ≦ 1.2 × exp (5.5 × K / 10 ⁵ ) (%) (Equation 5) Intermediate elongation ≦ 1.0 × exp (5.5 × K / 10 ⁵ ) (%) (Equation ⁵ ) 6)

In order to obtain a polyketone cord having excellent mechanical dimensional stability as described above, it is necessary to use a highly drawn polyketone fiber, but such a highly drawn polyketone fiber is usually strong. In many cases, thermal shrinkage is likely to occur, and there is a problem in thermal dimensional stability. The polyketone cord of the present invention has a thermally excellent dimensional stability, and specifically, the dry heat shrinkage ratio needs to be 0 to 3%. Here, the dry heat shrinkage is 150 ° C.
Is the rate of change of the yarn length before and after the heat treatment for 30 minutes (a positive value during shrinkage). The closer this value is to 0, the more excellent the thermal dimensional stability is. The dry heat shrinkage is preferably from 0 to
It is desirable to be 2%, more preferably 0 to 1%.

As an index of the mechanical and thermal dimensional stability of the cord, the dimensional stability parameter represented by the sum of the intermediate elongation and the dry heat shrinkage is preferably 0 to 5%.
The smaller the dimensional stability parameter, the more excellent both the mechanical dimensional stability and the thermal dimensional stability, preferably 0 to 4%, more preferably 0 to 3%, particularly preferably 0 to 2%. It is desirable that Further, when a rubber reinforcing material such as a tire, a belt, or a hose is used, there is frequently an opportunity to be placed not only in an environment only under load or only under heating but also in a severe environment receiving a load under heating. For this reason, it is extremely important that the dimensional stability with respect to the load under heating is excellent, and the polyketone cord of the present invention needs to have a hot intermediate elongation in the range of the following formula 7. Hot elongation ≦ 1.8 × exp (5.5 × K / 10 ⁵ ) (%) (Formula 7)

In the present invention, the hot elongation is 150.
In a stress-elongation curve of a tensile test performed at ℃, it is an elongation (%) under a load of 2.0 cN / dtex, and K is a twist coefficient of the cord described above. The smaller the intermediate elongation during heating, the better the dimensional stability against a load under heating. The intermediate elongation during heating increases as the twisting coefficient K increases, but even if the twisting coefficient increases, the polyketone fiber used, the twisting conditions, and the resorcinol-formalin-latex treatment conditions are selected so as to be within the range of the above formula 6. It is important to. The hot elongation of the polyketone cord of the present invention is more preferably in the range of the following formula 8, particularly preferably in the range of the following formula 9. Hot elongation ≦ 1.5 × exp (5.5 × K / 10 ⁵ ) (%) (Equation 8) Hot intermediate elongation ≦ 1.0 × exp (5.5 × K / 10 ⁵ ) ( %) (Equation 9)

The cord of the present invention is suitable for applications in which a high load and high heat are applied during use. In particular, the cord has excellent performance as a rubber reinforcing material. In order to enhance the adhesiveness with the fiber, a twisted cord to which an adhesive is attached is used. The kind of the adhesive contained in the polyketone cord of the present invention is not particularly limited, and a conventionally known adhesive can be used as it is or by appropriately selecting a composition ratio. Above all, it is common to use an adhesive containing an RFL (resorcin-formalin-latex) liquid as a main component. In this case, the RFL liquid may be used alone, or if necessary, an epoxy compound, an isocyanate compound, or a phenol compound. May be used by mixing with other chemicals such as.

The amount of the adhesive in the polyketone cord is not particularly limited, and a desired amount may be given according to the use and purpose. However, from the viewpoint of the mechanical properties of the cord, processability, and adhesion to rubber. To 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, and particularly preferably 1 to 7% by mass. In particular,
When using the RFL solution, it is desirable to select the processing conditions of the RFL solution so that the polyketone cord contains at least 90 to 99.9% by mass of the polyketone fiber and 0.1 to 10% by mass of the RFL resin. Although the total fineness of the polyketone cord of the present invention is not particularly limited, tires, belts,
For rubber-reinforced fibers such as hoses, usually 100 to 1
0000dtex, more generally 1000-8000
dtex, especially generally 2000-6000 dtex
It is.

The total fineness of the polyketone cord is from 2000 to 6
In the case of 000 dtex, the polyketone cord preferably has a strength of 250 N / cord or more, a rubber adhesive force of 100 N / cord or more, more preferably a strength of 300 N / cord or more and a rubber adhesive force of 150 N / c.
ord or more, particularly preferably 350 N / cord.
As described above, the rubber adhesive strength is desirably 200 N / cord or more. The stronger the rubber adhesive force, the less likely the rubber and the cord to separate during use, and the higher the mechanical properties and fatigue resistance of the molding material. Further, although the polyketone cord of the present invention is based on a cord in which polyketone fibers are twisted, the number of twisted cords is not particularly limited,
If the fatigue resistance of the cord is important, increase the number of twisted yarns.
When the mechanical strength of the cord is emphasized, it can be arbitrarily selected according to the use and purpose, such as reducing the number of twisted yarns. When used as a rubber reinforcing material, the twist coefficient K represented by the above formula 1 is generally set to 1,000 to 30,000, and particularly, the range of K to 5,000 to 25,000 is preferably used.

Next, a method for producing the polyketone cord of the present invention will be described. The polyketone fiber used for the polyketone cord needs to have the following characteristics (1) to (6). (1) Amount of 1-oxotrimethylene unit ≧ 97 mass% (2) Tensile strength ≧ 10 cN / dtex (3) Toughness ≧ 20 cN ·% / dtex (4) Intermediate elongation ≦ 1.5% (5) Dry heat shrinkage Rate = 0 to 2.5% (6) Intermediate elongation at heat ≦ 1.8%

The production method of the polyketone fiber is not particularly limited as long as it has the above-mentioned properties (1) to (6). Hereinafter, a method for producing a polyketone fiber will be briefly described using a wet spinning method using a zinc halide solution as a solvent. The polyketone to be spun has 1-oxotrimethylene of 97% by mass or more, and has an intrinsic viscosity of 3 to
Those having a range of 20 are preferably used. This polymer is dissolved in a zinc halide solution to form a dope. As the solvent, a solution of zinc halide alone or a complex salt of zinc halide and another salt is used. Polyketone at a concentration of 0.
It dissolves in a solvent at 005 to 70% by mass to obtain a polyketone dope.

The dope is discharged from a spinneret, and the discharged dope is coagulated into a fiber in a coagulation bath. The dope temperature at the time of discharge is 50 to 150 ° C., and the temperature of the coagulation bath is −1.
The range of 00 ° C to 100 ° C is common. The composition of the coagulation bath may be any, but an aqueous solution is preferred. The coagulated yarn that has left the coagulation bath is washed with water or an acidic aqueous solution of sulfuric acid, hydrochloric acid, phosphoric acid, or the like to remove metal salts remaining in the coagulated yarn, and finally the remaining amount of the metal salt contained in the yarn is preferably 10,000 ppm or less, more preferably 1000 ppm
It is desirable to repeatedly wash until the concentration becomes less than 100 ppm, most preferably less than 100 ppm. By drying the solidified fiber substantially free of metal salt, an undrawn polyketone yarn is obtained. The drying temperature is preferably 1
00 ° C to 260 ° C.

The undrawn yarn thus obtained is subsequently subjected to hot drawing by single-stage drawing or multi-stage drawing. Stretching may be performed in any number of stages, and when performing multi-stage stretching, a method of gradually increasing the stretching temperature is preferred. From the viewpoint of the mechanical properties of the obtained polyketone fiber, the total draw ratio is preferably at least 10 times, more preferably at least 15 times. If the hot stretching temperature is too high or the hot stretching time is too long, the toughness of the polyketone fiber is reduced, so the stretching temperature is from the melting point of the polyketone fiber −30 ° C.
It is desirable that the melting point is −5 ° C. and the thermal stretching time is in the range of 0.1 second to 1 minute.

Further, by performing a heat treatment by applying tension after the hot stretching, both the above-mentioned performance excellent in the mechanical properties (2) to (4) and the performance excellent in the thermal properties (5) and (6) are achieved. A polyketone fiber is obtained. As the heat treatment conditions after the hot drawing, the drawn yarn is tensioned at a temperature of 100 to 280 ° C under a tension of 0.00.
Treated at 1 to 1 cN / dtex, more preferably at a temperature of 150 to 250 ° C. and a tension of 0.1 to 0.8 cN / dtex
Is preferred. There is no particular limitation on the single-filament fineness of the polyketone fiber, but if it is too thin, fluff or breakage tends to occur, and if it is too thick, the physical properties and fatigue resistance due to the skin-core structure are reduced.
It is desirable that the single yarn fineness is in the range of 10 detx, more preferably in the range of 0.5 to 2 dtex.

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. , And other polymers. A raw cord is obtained by twisting the polyketone fibers thus obtained. There are no particular limitations on the type of twisted yarn, method, and number of ply twists. Examples of the type of twisted yarn of the polyketone fiber of the present invention include, for example, a single twisted yarn,
There may be mentioned a twisted yarn, a picco twisted yarn, a strongly twisted yarn, and the like. The number of ply twists is not particularly limited either, but may be any of one twist, two twists, three twists, four twists, and five twists.
More than two ply twists may be used.

The number of twists may be arbitrarily selected according to the application and the use environment. In general, the number of twists is in the range of 1,000 to 30,000. In order to obtain a cord having excellent dimensional stability, it is important that the twist tension is within an appropriate range. If the twist tension is too low, the slack and uniformity of the cord are impaired, and the mechanical dimensional stability represented by intermediate elongation is deteriorated. on the other hand,
If the twisting tension is too high, the cord will be overly distorted, resulting in poor mechanical and thermal dimensional stability. For this reason, the twisting tension is 0.01 to 0.01% for both the primary twist tension and the primary twist tension.
It is preferably 0.2 cN / dtex, and more preferably the ply twist tension is 0.02 to 0.1 cN / dtex,
It is desirable that the twisting tension be 0.03 to 0.08 cN / dtex.

The obtained polyketone twisted cord (raw cord) is subsequently subjected to a polyketone treatment by passing a step of applying an RFL solution having a concentration of 10 to 30% by weight and fixing by applying heat of at least 100 ° C. (so-called Dip treatment). Code is obtained. The preferred composition of the RFL solution is 0.1 to 10% by weight of resorcinol and 0.1 to 10% by weight of formalin.
10% by weight and 1 to 28% by weight of latex, more preferably 0.5 to 3% by weight of resorcinol, 0.5 to 3% by weight of formalin, and 10 to 25% by weight of latex. Further, the drying temperature of the RFL solution is preferably 100 to 250 ° C, more preferably 140 to 20 ° C.
0 ° C. for at least 10 seconds, preferably 20-12
It is desirable to perform a dry heat treatment for 0 second.

The dried cord is subsequently subjected to a heat treatment in a heat setting zone and a normalizing zone. It is important that the heat treatment conditions (heat treatment temperature, heat treatment tension, heat treatment time) at this time be within a specific range. The heat treatment temperature in the heat setting is preferably the maximum heat shrinkage temperature of the polyketone twisted cord ± 50 ° C, more preferably the maximum heat shrinkage temperature ± 10 ° C, still more preferably the maximum heat shrinkage temperature ± 5 ° C, and most preferably the maximum heat shrinkage temperature. It is desirable to process at a temperature. The heat treatment tension in the heat setting is preferably the maximum heat shrinkage stress ± 0.5.
2 cN / dtex, more preferably the maximum heat shrinkage stress ±
It is desirable to process at 0.1 cN / dtex, more preferably at the maximum heat shrinkage stress ± 0.05 cN / dtex, most preferably at the maximum heat shrinkage stress. The heat treatment time of the heat set is preferably in the range of 10 to 300 seconds, more preferably 30 to 120 seconds. Here, the maximum heat shrinkage temperature and the maximum heat shrinkage stress are physical property values of the raw cord measured by the method described in Examples of the present invention, and the temperature at which the raw cord exhibits the strongest shrinkage force against heat, And the shrinkage stress at that temperature.

The heat treatment temperature and the heat treatment time in the normalizing zone are preferably within the above-mentioned heat setting temperature and time ranges. The heat treatment tension in the normalizing zone is 10 to 8 times the heat treatment tension in the heat set zone.
It is preferable to set it to about 0%. As described above, the polyketone cord of the present invention has excellent mechanical properties with high strength and high toughness, excellent mechanical dimensional stability and dimensional stability against heat, and excellent dimensional stability against load under high temperature, Rubber reinforcing materials such as tire cords, hoses and belts, concrete reinforcing materials, non-woven fabrics such as filters and house wraps, woven fabrics such as airbags and sheets, knitting such as fishing nets, fishing line, sewing thread, rope and other industrial materials, It can be widely used for living materials and the like, and is particularly useful as a rubber reinforcing fiber material such as a tire reinforcing material, a belt reinforcing material, and a hose reinforcing material.

[0036]

The present invention will be described in more detail with reference to the following examples, which 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] is a value obtained based on the following definition formula. In the definition formula, t and T are the flow times of hexafluoroisopropanol having a purity of 98% or more and a diluted solution of polyketone dissolved in the hexafluoroisopropanol at 25 ° C. through a viscosity tube. C is the solute weight value in grams per 100 ml.

(2) Composition of polyketone The quantitative ratio of 1-oxotrimethylene groups was determined by NMR. (3) fineness, tensile strength, intermediate elongation, toughness fineness, sample 25 ° C., 48 hours after standing under 55% humidity, and weighed W ₁ of the sample 100 m, the fineness of the W ₁ × 100 (dtex ). This sample was prepared for a sample length of 250 m.
m, tensile strength, intermediate elongation, and toughness were measured at a crosshead speed of 300 mm / min.

(4) Intermediate elongation during heating A tensile test was performed in the same manner as in (3) except that the sample was kept in an air atmosphere at 150 ° C., and the intermediate elongation was measured. (5) Resin Adhesion Rate A cord having a length of 3 m is cut into 1 mm lengths, heated at 105 ° C. for 5 hours, and then the absolute dry weight W ₂ (g) is measured. The weighed cord is dissolved in 200 ml of hexafluoroisopropanol under stirring at 60 ° C. for 2 hours. After dissolving and filtering, the obtained residue was subjected to a heat treatment at 105 ° C. for 5 hours, and then precisely weighed in weight W ₃ (g), and the resin adhesion rate was determined from the following equation. Resin adhesion rate = (W ₃ / W ₂ ) × 100 (%)

(6) Maximum heat shrinkage stress and maximum heat shrinkage temperature CORD-TESTER (G, manufactured by Toyo Seiki Seisaku-sho, Ltd.)
The thermal shrinkage force characteristics of the twisted cord under constant displacement under the following conditions were measured using an O.O.D. Temperature Program: EXP mode Θ _M : 250 ° C. T ₁ : 3 minutes Initial load: 1/80 (g / dtex) Initial sample length: 250 mm Maximum contraction force F _max from measured temperature-contraction force curve
(CN) and the temperature T _max (° C.) at which the maximum contraction force was exhibited were read, and T _max was _defined as the maximum heat contraction temperature. Further, F
_The maximum heat shrinkage stress σ _max (cN / dtex) was obtained by dividing _max by the sample fineness (dtex).

(7) Dry Heat Shrinkage Dry heat treatment was performed in an oven at 150 ° C. for 30 minutes, and the fiber length and / or cord length before and after the heat treatment were reduced to 1/30 (cN
/ Dtex) with a load applied, and measured by the following equation. Dry heat shrinkage rate = _{[(L b -L a) / L} b ] × 100 (%) but L _b is the fiber length before the heat treatment and / or code length, L
_a is the fiber length and / or cord length after heat treatment.

(8) Dimensional stability parameter The sum of the intermediate elongation measured in (3) and the dry heat shrinkage measured in (7) was used as the dimensional stability parameter. (9) Rubber Adhesive Strength Adhesive strength was determined by using an unvulcanized rubber containing 70% of natural rubber, 15% of SBR, and 15% of carbon black.
After vulcanization for 30 minutes, T-pull strength (N) was measured at a crosshead speed of 300 mm / min.

[Preparation of Polyketone Fibers] The preparation method and characteristics of the polyketone fibers used in the examples of the present invention (comparative examples) will be described below. <ECO1> A polyketone polymer having an intrinsic viscosity of 6.5, in which ethylene and carbon monoxide were completely alternately copolymerized by a conventional method, was added to an aqueous solution containing 40% by mass of calcium chloride / 22% by mass of zinc chloride, and the polymer concentration was adjusted. A dope of 6.5% by mass was obtained. The obtained dope is heated to 80 ° C.,
It was extruded into a coagulation bath consisting of water at -2 ° C to form a coagulated yarn.
The coagulated polyketone yarn was washed with an aqueous hydrochloric acid solution having a concentration of 2% by mass and further washed with water. After the obtained coagulated yarn is simply dehydrated, IRGANOX (registered trademark, manufactured by Ciba Specialty Chemicals) 1098 and IRGANOX (registered trademark, manufactured by Ciba Specialty Chemicals) 1076
Was impregnated by 0.05% by mass (based on polyketone), followed by drying at 225 ° C. for 1 minute at a constant length to obtain an undrawn yarn.

This undrawn yarn was drawn at 225 ° C. in the first stage (7 times) on a ceramic plate having a length of 1 m, and then at 240 ° C. in the second stage (1.8 times), and further drawn at 2 ° C. (1.8 times).
The third stage (1.35 times) stretching is performed at 58 ° C. and the fineness is 5
A drawn yarn of 3.4 dtex / 50f was combined with 30 of the drawn yarns and a finishing agent was applied.
Heat treatment was performed at 220 ° C. for 10 seconds while applying a tension of N / dtex to obtain a polyketone fiber of 1653 dtex / 1500f. 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 10 moles of polyethylene oxide added /
Castor oil ether with 10 mol of polyethylene oxide added /
Sodium stearyl sulfonate / sodium dioctyl phosphate = 30/30/10/5/23/1/1 (mass% ratio). The obtained polyketone fiber has a tensile strength of 1
Excellent mechanical properties and dimensional stability: 7.1 cN / dtex, middle elongation 0.85%, toughness 45.1 cN ·% / dtex, dry heat shrinkage 0.3%, hot middle elongation 0.83% It had a property.

<ECO2> In the method for preparing ECO1,
The solvent was an aqueous solution containing zinc chloride / sodium chloride at a ratio of 65% by mass / 10% by mass, and the coagulation bath temperature was 20 ° C.
Spinning and drying were carried out in the same manner except that the total stretching ratio was subsequently increased to 15 times, followed by hot stretching and laying in the same manner, and then applying a tension of 0.5 cN / dtex to 160 ° C. And heat treatment for 10 seconds.
A polyketone fiber of 0detx / 1500f was obtained. This polyketone fiber had high mechanical properties and excellent dimensional stability.

<ECO3> In the preparation of the above-mentioned drawn yarn of ECO2, after drawing by a factor of 15 times, it was further heated at 260 ° C. for 1.2 hours.
Spinning, drying, stretching, twining, and heat treatment were performed in the same manner except that stretching was performed twice. Although the polyketone fiber had excellent dimensional stability, it had insufficient mechanical properties (particularly toughness).

<ECO4> The polyketone polymer used in ECO1 was added to an aqueous solution containing 75% by mass of resorcinol, stirred at 80 ° C. for 2 hours and dissolved to obtain a dope having a polymer concentration of 8% by mass. The obtained dope was extruded into a -5 ° C methanol bath to obtain a coagulated yarn. The obtained coagulated yarn was washed with methanol at 20 ° C. and then dried at 100 ° C. at a constant length to obtain an undrawn yarn. The unstretched yarn was stretched 5 times at 225 ° C., 2.5 times at 240 ° C., and 1.3 times at 258 ° C. on a 25 cm heated copper plate to obtain a drawn yarn. Twenty-four of the drawn yarns were combined, applied with the finishing agent used in the preparation of ECO1, and wound up. This polyketone fiber
Although excellent in tensile strength, dimensional stability such as intermediate elongation and intermediate elongation during heating was insufficient.

<EPCO1> 1-oxo-3 by a conventional method
An ethylene / propene / carbon monoxide terpolymer having an intrinsic viscosity of 3.9 containing 4% by mass of -methyltrimethylene unit was prepared. Spinning was carried out in the same recipe as ECO1, except that the concentration of this polyketone was 10% by mass. The obtained coagulated yarn was dried at a constant length at 200 ° C. to obtain an undrawn yarn, and subsequently 5 times at 210 ° C., 2.8 times at 225 ° C., 243 ° C.
Draw 1.8 times to obtain a drawn yarn. This drawn yarn 24
The book was combined, wound with the finish used in the preparation of ECO1. Although the mechanical properties such as tensile strength and toughness of this polyketone fiber were moderate, the dimensional stability such as intermediate elongation, dry heat shrinkage, and intermediate elongation during heating was quite insufficient.

<EPCO2> 1-oxo-3 by a conventional method
An ethylene / propene / carbon monoxide terpolymer having an intrinsic viscosity of 1.6 and containing 7% by mass of -methyltrimethylene unit was prepared. 0.3 mass% of calcium hydroxyapatite was added to this terpolymer, and after melting at 235 ° C., the mixture was extruded from a spinneret. The discharged yarn is cooled and solidified, wound at a speed of 400 m / min, and has a total fineness of 153.
An undrawn yarn of 1 dtex was obtained. This undrawn yarn has a length of 1
First stage (4 times) at 200 ° C on ceramic plate
After stretching, the second step (2
) And a third step (1.19 times) at 225 ° C. for a total of 9.5 times multi-step stretching to obtain 161.1 dtex / 7.
5f polyketone fibers were produced. After 10 fibers of this fiber were combined, the finishing agent used in the preparation of ECO1 was applied to give 1
A 650 detx / 750f polyketone fiber was obtained. This fiber had completely poor mechanical properties and dimensional stability. Table 1 summarizes the properties of these polyketone fibers. Table 1 is a table showing the characteristics of the polyketone fibers used in the polyketone cords of the examples and the comparative examples.

[0049]

[Table 1]

[Preparation of polyketone cord]

Example 1 Using ECO1 as a polyketone fiber, using a ring twisting machine manufactured by Kaji Tekko Co., Ltd., twisting in the Z direction, then twin-twisting the two yarns and twisting in the S direction to obtain a raw cord (under twisting tension) 0.8N (0.05 cN / dtex), ply twist tension 1.8 N (0.05 cN / dtex), 390 T / m for both ply twist and ply twist). The maximum heat shrink temperature of this raw cord is 218 ° C. and the maximum heat shrink stress is 0.12 cN / dte.
x. This raw cord was immersed in an RFL solution having the following composition, and then dried in a drying zone (1 N at 160 ° C. under a tension of 3 N).
20 seconds heat treatment), heat set zone (tension 4.2N)
The cord was obtained through a normalizing zone (heat treatment at 220 ° C. for 60 seconds with a tension of 2.8 N) at 220 ° C. for 60 seconds. (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 Vinylpyridine latex (41% by mass) 364.0 parts

The obtained polyketone cord had a tensile strength of 11.8 cN / dtex and a toughness of 30.9 cN ·%.
/ Dtex, intermediate elongation 3.2%, dry heat shrinkage 0.3%,
The intermediate elongation at heat was 3.1%, which was extremely excellent in mechanical properties and dimensional stability. Table 2 shows the twisting conditions, Dip treatment conditions and performance of this cord together with the results of Examples 2 to 4 below. Table 2 shows the twisting conditions and RFL treatment conditions of the polyketone cord of the present invention, cord properties, and the range specified by the present invention (toughness and intermediate elongation,
It is a table | surface which shows the intermediate elongation at the time of a heat.

[0052]

Example 2 A cord was prepared in the same manner as in Example 1, except that the twisting conditions were set to 290 T / m for the number of twists and the number of twists, respectively. The obtained polyketone cord had very excellent characteristics in both mechanical properties and dimensional stability.

Example 3 A cord was prepared in the same manner as in Example 1, except that the twisting conditions were set to 190 T / m for the number of twists and the number of twists, respectively. The obtained polyketone cord had very excellent characteristics in both mechanical properties and dimensional stability.

Example 4 ECO2 was used as a polyketone fiber and treated under the conditions shown in Table 2 to prepare a cord. The resulting cord had reasonable mechanical properties and high dimensional stability.

[0053]

[Table 2]

[0054]

Comparative Example 1 A cord was prepared by using ECO3 as a polyketone fiber and treating it under the conditions shown in Table 3. Although the obtained cord had excellent dimensional stability, it had a small tensile strength and toughness as compared with the range specified in the present invention, and the mechanical properties were completely insufficient. Twisting conditions of the cord of the comparative example,
Table 3 summarizes the Dip processing conditions and performance together with the results of Comparative Examples 2 to 6 below. Table 3 shows the twisting conditions and RFL treatment conditions of the cords of the comparative examples, cord characteristics, and the range specified by the present invention (toughness and intermediate elongation, intermediate elongation during heating).
FIG.

[0055]

Comparative Example 2 ECO4 was used as a polyketone fiber and treated under the conditions shown in Table 3 to prepare a cord. Although the obtained cord had high strength, the intermediate elongation was larger than the range specified in the present invention, and the mechanical dimensional stability was insufficient.
In addition, the dimensional stability parameter was as large as 8%, and the balance between the total dimensional stability of mechanical and thermal was insufficient.

Comparative Example 3 EPCO1 was used as a polyketone fiber,
The cord was prepared by treating under the conditions shown in Table 3. The obtained cord had insufficient strength, and particularly had an intermediate elongation during heating larger than the range specified in the present invention and had insufficient mechanical dimensional stability at high temperatures. In addition, the dimensional stability parameter was as large as 7.7%, and the balance between dimensional stability of mechanical and thermal total was insufficient.

[0056]

Comparative Example 4 A cord was prepared in the same manner as in Comparative Example 3, except that the twisting conditions were set to 290 T / m for the number of twists and for the number of twists, respectively. The obtained cord had insufficient mechanical dimensional stability at high temperatures.

Comparative Example 5 A cord was prepared in the same manner as in Comparative Example 3, except that the twisting conditions were 190 T / m and the number of twists was 190 T / m. The obtained cord had insufficient mechanical dimensional stability at high temperatures.

Comparative Example 6 Using EPCO2 as a polyketone fiber,
The cord was prepared by treating under the conditions shown in Table 3. The obtained cord had a low strength, and all of the dimensional stability of the intermediate elongation, the dry heat shrinkage, and the intermediate elongation during heating were extremely insufficient.

[0057]

[Table 3]

[0058]

The polyketone cord of the present invention has not only excellent mechanical properties such as high strength and high toughness, but also excellent mechanical dimensional stability, thermal dimensional stability, and mechanical dimensional stability at high temperatures. . The polyketone cord of the present invention can be used as a high-performance industrial material in a wide range of fields (for example, civil and industrial materials such as nets, nets, ropes, and cables, ribbons, core materials for clothing and daily necessities, tires, belts, hoses, and the like). Rubber reinforcement, cement reinforcement, plastic reinforcement fiber, etc.). In particular, applications that receive high mechanical loads and impacts during processing and use, high mechanical loads in high-temperature environments and high temperatures, such as tires and belts,
It is extremely useful as a rubber reinforcing material for hoses or a reinforcing material such as FRP.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) D03D 1/00 D03D 1/00 D 15/00 15/00 A E 15/02 15/02 E D06M 15 / 693 D06M 15/693 // D06M 101: 16 101: 16 F-term (reference) 3B153 AA08 AA47 AA50 BB01 CC12 CC24 CC32 FF01 FF08 FF12 FF16 FF19 FF31 GG01 GG13 GG40 4L033 AA04 AC11 CA68 CA70 4L035 BB06 BB10 BB15 BB66 BB69 EE08 EE20 FF01 HH10 4L036 MA00 MA04 MA33 PA21 PA26 RA03 RA24 UA07 4L048 AA19 AA44 AA48 AA56 AB07 AB32 BB04 CA01 DA41 DA42 DA44

Claims (13)

[Claims] (1) 97 to 100% by mass of the repeating unit is 1
-A polyketone cord containing a polyketone fiber composed of a polyketone composed of oxotrimethylene in an amount of 80% by mass or more, and having characteristics satisfying the following (a) to (e): . (A) Tensile strength ≧ 8 cN / dtex (b) Toughness ≧ 20 + 14.6 × K / 10 ⁴ -14.1 × (K / 10 ⁴ ) ² + 2.7 × (K / 10 ⁴ ) ³ (cN ·% / Dtex) where K is the twist coefficient of the cord represented by the following equation 1. K = Y × D ^0.5 (Equation 1) where Y is the number of twists per meter of cord (T / m), D
Is the total indicated fineness (dtex) of the polyketone cord. (C) Intermediate elongation ≦ 1.5 × exp (5.5 × K / 10 ⁵ ) (%) (d) Dry heat shrinkage = 0 to 3% (e) Hot intermediate elongation ≦ 1.8 × exp (5.5 × K / 10 ⁵ ) (%) Here, the intermediate elongation is the elongation under a load of 2.0 cN / dtex, and the dry heat shrinkage is before and after heat treatment at 150 ° C. for 30 minutes. The shrinkage ratio, and the intermediate elongation under heat is the elongation under a load of 2.0 cN / dtex at 150 ° C. 2. The polyketone cord according to claim 1, wherein the dimensional stability parameter represented by the sum of the intermediate elongation and the dry heat shrinkage is 0 to 5%. 3. An intermediate elongation ≦ 1.2 × exp (5.5 × K
/ 10 ⁵ ), and the dry heat shrinkage = 0 to 2.5%,
Hot elongation ≦ 1.5 × exp (5.5 × K / 10 ⁵ )
The polyketone cord according to claim 1 or 2, wherein 4. Intermediate elongation ≦ 1.0 × exp (5.5 × K
/ 10^Five) And the dry heat shrinkage = 0-2% during hot
Elongation ≦ 1.0 × exp (5.5 × K / 10 ^Five)
The poly according to any one of claims 1 to 3,
Ketone cord. 5. The polyketone cord according to claim 1, wherein the cord has a tensile strength of 10 cN / dtex or more and a toughness in a range represented by the following formula. Toughness ≧ 30 + 14.6 × K / 10 ⁴ -14.1 ×
(K / 10 ⁴ ) ² + 2.7 × (K / 10 ⁴ ) ³ 6. The polyketone cord according to claim 1, wherein the polyketone cord contains at least 90 to 99.9% by mass of a polyketone fiber and 0.1 to 10% by mass of a resorcin-formalin-latex resin. The polyketone code according to any one of the above. 7. The polyketone cord having a total fineness of 2000 to 2000.
The polyketone cord according to any one of claims 1 to 6, wherein the cord has a 6000 dtex, a strength of 250 N / cord or more, and a rubber adhesive strength of 100 N / cord or more. 8. The polyketone cord according to claim 1, wherein the twist coefficient K is 1,000 to 30,000. 9. A rubber product comprising at least a part of the polyketone cord according to claim 1. 10. The rubber product according to claim 9, wherein the rubber product is a tire. 11. The rubber product according to claim 9, wherein the rubber product is a hose. 12. The rubber product according to claim 9, wherein the rubber product is a belt. 13. A polyketone fiber having the following properties (1) to (6) is produced by twisting a yarn with a twist tension of 0.01 to 0.2 cN /
After twisting with dtex, and then dipping in a resorcinol-formalin-latex solution, the maximum heat shrinkage temperature ± 50 ° C.
10-30 at maximum heat shrinkage stress ± 0.2 cN / dtex
A method for producing a polyketone cord, comprising a step of treating for 0 second. (1) Amount of 1-oxotrimethylene unit ≧ 97 mass% (2) Tensile strength ≧ 10 cN / dtex (3) Toughness ≧ 20 cN ·% / dtex (4) Intermediate elongation ≦ 1.5% (5) Dry heat shrinkage Rate = 0 to 2.5% (6) Intermediate elongation at heat ≦ 1.8%