JP2003055855A - Polyketone intertwisted cord - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cord having high strength, excellent size stability, high toughness and homogeneous heat shrinking properties, and free from slackening and strain caused by an RFL treatment and vulcanization. SOLUTION: An intertwisted cord is obtained by intertwisting a polyketone fiber (A) having the following properties (a) to (c): (a) a tensile strength>=10 cN/dtex; (b) an elastic modulus>=200 cN/dtex; and (c) an elongation=3-9%, and a fiber (B) having a specific strength and elongation. The obtained intertwisted cord has a specific strength, elongation and elongation under 2.0 cN/dtex load.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a twisted cord containing polyketone fiber, which has excellent mechanical properties, dimensional stability and thermal characteristics of polyketone fiber and high elongation and high toughness. INDUSTRIAL APPLICABILITY The twisted cord of the present invention can be applied to a wide range of applications such as household materials, household materials, and industrial materials, and particularly industrial material applications exposed to high load, high impact and high temperature during processing or use, Specifically, it is extremely useful as a reinforcing fiber material for molded products such as tires, belts, hoses, FRPs, optical fibers and cement.

[0002]

2. Description of the Related Art In recent years, carbon monoxide and olefins such as ethylene and propene are polymerized with palladium and nickel as catalysts to obtain aliphatic polyketones in which carbon monoxide and olefins are copolymerized substantially completely. Was found. The polyketone fiber obtained by fibrating this polyketone has a higher melting point than conventional polyolefin fibers and has high strength and high elastic modulus, so that it is used for industrial materials, civil engineering materials, household materials, clothing applications, etc. It is expected to be applied to a wide range of purposes. In particular, it is expected to be developed as a rubber reinforcing material for tires, belts, hoses, etc., and as a reinforcing material for resins, cement, optical fibers, etc.

When polyketone fiber is used as a rubber reinforcing material, it is usually twisted and used as a cord. An interlaced cord containing a polyketone fiber has high strength and is excellent in dimensional stability under load and heating (for example, Japanese Patent Application No. 2001-146079). However, the twisted cord containing polyketone fiber has a low elongation,
Although it has high strength, its toughness is small, and there is a problem in impact resistance and fatigue resistance. To solve this problem, it is possible to increase the elongation by increasing the number of twisted yarns of the polyketone cord, but the strength of the cord decreases, and the elongation at 2.0 cN / dtex load increases and the polyketone cord increases. In addition to the poor dimensional stability, there was a large decrease in the tenacity factor due to the twisted yarn, and there was the problem that the toughness decreased.

The present inventors have found that a polyketone cord having a high twist yarn strength utilization ratio can be obtained by controlling the single yarn sticking of the polyketone fiber and the surface friction property of the fiber (Japanese Patent Application No. 2001-192739). ), Although this polyketone cord has high strength, it was still insufficient to obtain a cord having higher elongation and higher toughness. On the other hand, regarding a twisted cord obtained by combining a polyketone fiber and another fiber material, Japanese Patent Application Laid-Open No. HEI11-1999
-334313 and JP-A-11-336957.
Japanese Patent Publication discloses a technique of twisting polyketone fibers and polyethylene naphthalate fibers together. However, although this crossed cord has a high strength of 13 cN / dtex or more, it has an elongation of 6.5%, which is a completely insufficient level. Further, this prior art does not disclose any technique relating to a twisted cord containing a polyketone fiber having high elongation and toughness.

The inventors of the present invention have found that interlaced cords of polyketone fibers and other fiber materials are non-uniform during resorcin-formalin-latex (RFL) treatment or vulcanization because the heat shrinkage characteristics of both cords are different. Exhibits shrinkage behavior (for example, fibers with high heat shrinkage shrink more strongly, causing slack and strain in fibers with low heat shrinkage), which may reduce the mechanical properties of treated cords and rubber products, It was found that there is a problem that the quality of rubber products deteriorates. However, in the prior art so far, the problem of thermal dimensional stability of the twisted cord of the above polyketone fiber and other fiber materials, a means for solving this problem, and a high quality intersection showing uniform heat shrinkage. There is no disclosure of a technique for manufacturing a twisted cord.

As described above, a twisted cord containing polyketone fibers having high strength and high dimensional stability, but having high elongation and toughness, and further polyketone fibers having uniform heat-shrinking properties and good quality. Up to now, nothing has been known about the twisted and twisted cords and the manufacturing technology thereof.

[0007]

The problem to be solved by the present invention is to provide a cord having (1) high strength and high dimensional stability in a twisted cord using polyketone fiber, 2) Providing a cord having high elongation and high toughness, and (3) Providing a homogeneous cord having uniform heat-shrinking properties and having no slack or distortion due to RFL treatment or vulcanization. Is.

[0008]

Means for Solving the Problems The present inventors have completed the present invention as a result of intensive studies to solve the above problems. That is, the first invention relates to a polyketone fiber (A) having the following characteristics (a) to (c), in which 95 to 100% by mass of the repeating unit is composed of 1-oxotrimethylene, and the following (d) ) To (e), which are twisted cords obtained by twisting together fibers (B) having the characteristics, wherein the mass ratio (A / B) of A and B is 80/20 to 20 /.
The twisted cord is 80, and has the following characteristics (f) to (h). Fiber (A) (a) Tensile strength ≧ 10 cN / dtex (b) Elastic modulus ≧ 200 cN / dtex (c) Elongation = 3 to 9% Fiber (B) (d) Elastic modulus ≦ 200 cN / dtex (e) Elongation ≧ 10% Cord (f) Tensile strength ≧ 7 cN / dtex (g) Elongation ≧ 10% (h) 2.0 cN / dtex Elongation under load ≦ 6%

The second invention is the repeating unit of 95 to 10
0% by mass of 1-oxotrimethylene, polyketone fiber (A) having the following characteristics (a) to (c), and fiber (C) having the following characteristics (i) to (k): ) And a mass ratio (A / C) of A and C is 80/20 to 20/80, and has the following characteristics (l) to (n). It is a characteristic twisted cord. Fiber (A) (a) Tensile strength ≧ 10 cN / dtex (b) Elastic modulus ≧ 200 cN / dtex (c) Elongation = 3 to 9% Fiber (C) (i) Tensile strength ≧ 18 cN / dtex (j) Elastic modulus ≧ 450 cN / dtex (k) Elongation = 2 to 5% Cord (l) Tensile strength ≧ 12 cN / dtex (m) Elongation ≧ 6% (n) 2.0 cN / dtex Elongation ≦ 4%

A third invention is a molded product using the above cord, for example, a tire, a hose, a belt, an optical fiber,
Is.

The present invention will be described in detail below. The twisted cord in the present invention is a cord obtained by twisting the polyketone fiber (A) and the fiber (B) or the fiber (C). That is, the polyketone fiber and the fiber (B) twisted in one direction or the polyketone fiber and the fiber (C) twisted in one direction are aligned and then twisted in the opposite direction. The polyketone fiber used in the present invention is a polyketone in which 95 to 100% by mass, preferably 97% by mass or more, and more preferably 100% by mass of the repeating unit is composed of 1-oxotrimethylene represented by the chemical formula (1). .

[0012]

[Chemical 1]

The higher the proportion of 1-oxotrimethylene in the repeating unit is, the more regular the molecular chain is, and the fiber having high crystallinity and high orientation is obtained. As a result, a cord having high strength, high dimensional stability and high heat resistance can be obtained by using this fiber.

The polyketone intertwisted cord in the first invention is a polyketone fiber (A) and a fiber (B) having a higher elongation and a lower elastic modulus than the polyketone fiber (A) (hereinafter, abbreviated as "fiber (B)"). The weight ratio of polyketone fiber (A) and fiber (B) (A / B)
Is 80/20 to 20/80, preferably 70/3
0-30 / 70, more preferably 60 / 40-40 / 6
It is 0. If the proportion of polyketone fiber is less than 20% by mass, the strength of the cord will be low, and also 2.0 cN / dt
It becomes impossible to obtain a cord having a small elongation under ex load (a cord having excellent mechanical dimensional stability). On the other hand, when the proportion of the polyketone fiber exceeds 80% by mass, although the strength and the dimensional stability are excellent, a twisted cord having excellent fatigue resistance and impact resistance cannot be obtained.

It is extremely important that the polyketone fiber (A) and the fiber (B) constituting the twisted cord of the present invention have the following characteristics. Fiber (A) (a) Tensile strength ≧ 10 cN / dtex (b) Elastic modulus ≧ 200 cN / dtex (c) Elongation = 3 to 9% Fiber (B) (d) Elastic modulus ≦ 200 cN / dtex (e) Elongation ≧ 10% Tensile strength of polyketone fiber (A) is 10 cN / dt
If it is less than ex, a high-strength cord cannot be obtained, so the tensile strength must be 10 cN / dtex or more, preferably 12 cN / dtex or more,
It is more preferably 15 cN / dtex or more.

Polyketone fiber has an elastic modulus of 200 cN / d
If it is less than tex, a cord having excellent mechanical dimensional stability cannot be obtained. Therefore, the elastic modulus needs to be 200 cN / dtex or more, preferably 300 cN / d.
tex or more, more preferably 350 cN / dtex or more. If the elongation of the polyketone fiber is less than 3%, it is impossible to obtain a cord having a high elongation even when the twist is cross-twisted. On the other hand, when the elongation exceeds 9%, the polyketone fiber is mechanically
Due to poor thermal dimensional stability, the polyketone fiber has an elongation of 3
Is required to be 9%, preferably 4-8%,
It is more preferably 5 to 7%.

The elastic modulus of the fiber (B) is 200c.
It is necessary that N / dtex or less and elongation be 10% or more. If the elastic modulus exceeds 200 cN / dtex, the twisted cord becomes hard and the effect of increasing the elongation of the twisted cord cannot be sufficiently obtained. Elastic modulus is preferably 150c
N / dtex or less, more preferably 100 cN / dte
It is less than or equal to x. If the elongation is less than 10%, a twisted cord having sufficient elongation and toughness cannot be obtained even when twisted. The elongation is preferably 12% or more, more preferably 15% or more.

The type of the fiber (B) used in the present invention is not limited as long as its elastic modulus and elongation are within the range of the present invention.
From the viewpoints of strength, elongation, process passability and cost of the obtained twisted cord, nylon 66 fiber, nylon 6 fiber,
Rayon fiber, polyethylene terephthalate fiber, and polytrimethylene terephthalate fiber are preferable, and nylon 66 fiber is particularly preferable because a cord having high strength, high elongation and high toughness can be obtained and adhesion to rubber is easy. Further, the fiber (B) may be a polyketone fiber as long as the elongation and elastic modulus are within the above-mentioned ranges. For example, 7% by mass of the repeating unit is ethylene / l-oxo-3-methyltrimethylene. A polyketone fiber made of propylene / carbon monoxide copolymerized polyketone may be used.

Polyketone fiber (A) having the above characteristics
A twisted cord is obtained by twisting the fiber and the fiber (B) together. The twisted cord of the present invention has the following (f) to
It is extremely important to have the characteristics of (h). (F) Tensile strength ≧ 7 cN / dtex (g) Elongation ≧ 10% (h) 2.0 cN / dtex Elongation under load ≦ 6%

The twisted cord has a tensile strength of 7 cN / dt.
If it is less than ex, the function as an industrial material application such as a rubber reinforcing material is insufficient, and it becomes difficult to reduce the weight and cost. Therefore, the tensile strength of the cord is 7 cN
/ Dtex or more is required and 10 cN / d
tex or more, preferably 12 cN / dtex
The above is more preferable, and 15 cN / dtex or more is the most preferable. Elongation of twisted cord is 10% or more, preferably 1
When the content is 2% or more, the toughness of the twisted and twisted cord is increased, and fatigue resistance and impact resistance are remarkably improved. If the elongation of the polyketone intertwisted cord under a load of 2.0 cN / dtex exceeds 6%, the mechanical dimensional stability becomes poor, and the dimensional change of the product during use or processing tends to occur. Therefore, the elongation at 2.0 cN / dtex load needs to be 6% or less, preferably 5% or less, and more preferably 4% or less.

The twisted cord in the second invention has a polyketone fiber (A) and a higher strength than the polyketone fiber (A),
A cord made of a high-strength fiber (C), which is a twisted cord with a fiber (C) having a high elastic modulus and a low elongation, and has extremely high strength and high mechanical dimensional stability by the twisting. It is a twisted cord with higher elongation and higher toughness than that of.

That is, a polyketone fiber (A) having the following characteristics (a) to (c) as in the first invention, wherein 95 to 100% by mass of the repeating unit is composed of 1-oxotrimethylene. , A crossed cord formed by twisting together fibers (C) having the following characteristics (i) to (k), wherein the mass ratio of A / C is 80/20 to 20/80, and the following ( It is a twisted cord having characteristics 1) to (n). Fiber (A) (a) Tensile strength ≧ 10 cN / dtex (b) Elastic modulus ≧ 200 cN / dtex (c) Elongation = 3 to 9% Fiber (C) (i) Tensile strength ≧ 18 cN / dtex (j) Elastic modulus ≧ 450 cN / dtex (k) elongation = 2 to 5% Intertwisted cord (l) tensile strength ≧ 12 cN / dtex (m) elongation ≧ 6% (n) 2.0 cN / dtex elongation ≦ 4%

The twisted cord of the present invention comprises a polyketone fiber (A) and a fiber (C) having higher strength, higher elastic modulus and higher elongation than the polyketone fiber (A) (hereinafter referred to as "fiber (C)"). , Which may be abbreviated), and the mass ratio of the polyketone fiber (A) and the fiber (C) (A
/ B) is 80/20 to 20/80, preferably 7
0/30 to 30/70, more preferably 60/40 to 4
It is 0/60. If the proportion of the polyketone fiber (A) is less than 20% by mass, the elongation of the cord will be low and a cord having high toughness will not be obtained. On the other hand, when the proportion of the polyketone fiber (A) exceeds 80% by mass, the strength and the dimensional stability of the cord are the same as those of the cord composed of only the polyketone fiber.

It is extremely important that the polyketone fiber (A) and the fiber (C) constituting the twisted and twisted cord of the present invention have the following characteristics. Fiber (A) (a) Tensile strength ≧ 10 cN / dtex (b) Elastic modulus ≧ 200 cN / dtex (c) Elongation = 3 to 9% Fiber (C) (i) Tensile strength ≧ 18 cN / dtex (j) Elastic modulus ≧ 450 cN / dtex (k) Elongation = 2 to 5% The properties of the polyketone fiber (A) are the same as those of the first invention.

The fiber (C) has a tensile strength of 18 cN /
dtex or more is necessary, and preferably 20
It is at least cN / dtex. Tensile strength is 18 cN /
If it is less than dtex, it becomes difficult to obtain a twisted cord having extremely high tensile strength. The elastic modulus of the fiber (C) needs to be 450 cN / dtex or more,
It is preferably 500 cN / dtex or more. When the elastic modulus is less than 450 cN / dtex, the mechanical dimensional stability of the twisted cord is lowered. Furthermore, the elongation of the fiber (C) is 2
If it is less than 5%, it becomes difficult to obtain a crossed cord having a high elongation, and if the elongation exceeds 5%, the mechanical dimensional stability becomes insufficient. It is necessary to be 2 to 5%, preferably 2.5 to 4%.

The type of the fiber (C) used in the present invention is not limited as long as the tensile strength, elastic modulus and elongation are within the range of the present invention, but the strength, dimensional stability and elongation of the obtained twisted and twisted cord are not limited. From the viewpoint of the degree and processability, aramid fiber,
Polybenzazole fibers, polyvinyl alcohol fibers, polyethylene fibers, and polyvinyl alcohol fibers are preferable, and aramid fibers that can obtain a cord having high heat resistance at a relatively low cost are particularly preferable. Further, the fiber (C) may be a polyketone fiber as long as the tensile strength, the elongation and the elastic modulus are within the above-mentioned ranges, for example, Japanese Patent Application No. 2001-05.
The high-strength and high-modulus polyketone fibers described in Japanese Patent No. 2718 can be used.

Polyketone fiber (A) having the above characteristics
A twisted and twisted cord is obtained by twisting the fiber and the fiber (C) together. The twisted and twisted cord of the present invention has the following (l) to
It is extremely important to have the characteristics of (n). (L) Tensile strength ≧ 12 cN / dtex (m) Elongation ≧ 6% (n) 2.0 cN / dtex Elongation under load ≦ 4% Tensile strength of the twisted and twisted cord of the present invention is 12 cN / dte
By setting it to be x or more, preferably 15 cN / dtex or more, it is possible to significantly reduce the weight of the interlaced cord in the molded product.

It is particularly important that the twisted cord of the present invention has an elongation of 6% or more, preferably 8% or more, more preferably 10% or more. The twisted cord of the present invention has a higher toughness per the same elongation as compared with a cord composed of only polyketone fiber, and has practical toughness and fatigue resistance with a smaller elongation, but the elongation is still 6
If it is less than%, the toughness of the twisted cord is not sufficiently high, and the improvement in fatigue resistance and impact resistance is small.

Further, the twisted cord of the present invention is expected to make use of the feature of extremely high strength to reduce the amount of cord and reduce the weight of the molded product. Therefore, it is necessary that the mechanical dimensional stability is extremely excellent. In particular,
By setting the elongation at 2.0 cN / dtex load to 4% or less, preferably 3% or less, more preferably 2% or less, the mechanical dimensional stability is significantly improved.

As described above, the twisted cord of the present invention is formed by twisting the polyketone fiber and the fiber (B) or the fiber (C). It is desirable that the twisted cord of the present invention having such a structure has high toughness. Toughness is a property represented by the area (cN ·% / dtex) of the stress-elongation curve in the tensile test of the twisted and twisted cord, and the higher this value, the better the impact resistance and fatigue resistance of the twisted and twisted cord. Therefore, the toughness is preferably 30c.
N ·% / dtex or more, more preferably 40 cN ·% /
dtex or more, most preferably 50 cN ·% / dtex
That is all.

The fineness, the number of twisted yarns, and the twisted form of the twisted and twisted cord of the present invention are not limited, and can be appropriately selected according to the use and purpose. As a preferable range, the total fineness is usually 100 to 10000 dtex in the case of rubber reinforcement application,
It is preferably 1000 to 8000 dtex. The number of twisted yarns is preferably such that the twist coefficient K represented by the following equation is in the range of 100 to 30,000. K = Y × D ^0.5 (T / m · dtex ^0.5 ) In the formula, Y is the number of twists per 1 m of the twisted cord (T / m
m) and D are total display fineness (dtex) of the twisted and twisted cord.

The total fineness of the twisted and twisted cord is the sum of the finenesses of all the fiber materials used for producing the twisted and twisted cord. For example,
Two 1670dtex polyketone fibers and 1400d
When an intertwisted cord is formed using tex nylon 66 fiber, the total display fineness is 4740 dtex. The twisted yarn may have any form, and may be a cord formed by twisting two strands, three strands or four or more fibers.

Polyketone fiber (A), and fiber (B)
Alternatively, after twisting the fibers (C) with a twist,
When twisting together by twisting, twisting with different number of lower twists
You may combine. In this case, high strength and high elongation
To obtain a well-balanced twisted cord with
In one aspect of the invention, the number of lower twists of the polyketone fiber A is N _A
And the number of lower twists of fiber B N_BRatio of (N_A/ N_B), The second invention
In, the number of lower twists of polyketone fiber A is N_AAnd fiber C
The ratio of the number Nc of lower twists (N_A/ Nc), 0.5 to 2.0
Is preferable, and 0.8 to 1.25 is more preferable.
Yes.

Since the twisted and twisted cord of the present invention undergoes a heat treatment process such as resorcin-formalin-latex treatment or vulcanization during processing and is exposed to a high temperature environment during use, it is desired to have excellent thermal dimensional stability. . The present inventors set the difference in the maximum heat shrinkage temperature and the difference in the maximum heat shrinkage stress of the polyketone fiber (A) and the fiber (B) or the fiber (C) forming the twisted cord within a certain range. Due to
It has been found that a twisted cord having no thermal shrinkage and excellent thermal dimensional stability can be obtained. Here, the maximum heat shrinkage temperature and the maximum heat shrinkage stress are the temperature at which the fiber and the cord undergo the strongest heat shrinkage and the heat shrinkage force at that temperature, respectively, and are values measured by the method described later. As a preferable range, in the first invention,
A maximum thermal shrinkage stress sigma _B polyketone fiber maximum heat shrinkage temperature T _A and a maximum thermal shrinkage stress sigma _A and the fiber of the fiber maximum heat shrinkage temperature T _B and polyketone fibers (B) (A) of (A) (B) Is within the following range. Maximum thermal shrinkage temperature _{difference: | T A -T B | =} 0~30 ℃ maximum thermal shrinkage stress _{difference: | σ A -σ B | =} 0~0.2cN
/ Dtex Maximum heat shrinkage temperature difference is 0 ~ 10 ℃, Maximum heat shrinkage stress difference is 0
More preferably, it is 0.1 cN / dtex.

In the second invention, the maximum heat shrinkage temperature of the polyketone fiber (A) is T _A , the maximum heat shrinkage stress is σ _A ,
Assuming that the heat shrinkage stress of the fiber (C) at the temperature T _A is σ _{C (TA)} , the heat shrinkage stress difference: | σ _A −σ _{C (TA)} | = 0 to 0.2 cN
/ Dtex is preferable, and the heat shrinkage stress difference is 0 to 0.1 cN.
/ Dtex is more preferable. The maximum heat shrinkage stress is 0.01 cN / d.
If it is less than tex, the shape retention upon heating is reduced, and
If it exceeds 6 cN / dtex, a molded product obtained by heat shrinkage during heating is likely to be distorted or deformed. Therefore, the maximum heat shrinkage stress is preferably 0.01 to 0.6 cN / dtex, more preferably 0. .1 to 0.4 cN / dt
It is a range of ex. The twisted cord of the present invention has excellent performance as a reinforcing material such as a rubber reinforcing material, but when used as a rubber reinforcing material, the twisted cord is used as a reinforcing cord in order to enhance adhesion with rubber. Used with an adhesive attached.

The type of adhesive is not particularly limited, and known adhesives can be used. As the adhesive, it is common to use one having an RFL (resorcin-formalin-latex) solution as a main component, and in this case, the RFL solution alone, or an epoxy compound, an isocyanate compound, a phenol compound, etc. depending on the purpose, It may be a mixture with other chemicals. There is no limitation on the ratio of the adhesive attached to the twisted and twisted cord, and a desired amount may be given depending on the use and purpose. From the viewpoint of the mechanical properties of the cord, processability, adhesiveness with rubber, etc.
It is preferably in the range of 20 to 20% by mass, more preferably 1 to 10% by mass, and most preferably 2 to 7% by mass.

The interlaced cord with the adhesive thus obtained can be used as a reinforcing material in various molded products. Examples of molded products include not only textile products such as woven fabrics, knitted fabrics, nets and nets, but also rubber products such as tires, belts and hoses, resin products such as FRP, optical fibers and cement. In particular, it is very useful as a carcass material for tires, a belt material, a cap ply material, a belt core material, a canvas, a hose core wire, and an optical fiber tension member.

Next, a method for manufacturing the twisted cord of the present invention will be described. The polyketone fiber used for the twisted cord is
If the tensile strength, the elongation and the elastic modulus are in the above-mentioned ranges, the manufacturing method is not particularly limited, and a known manufacturing method can be applied. In order to industrially produce a polyketone fiber having high strength, high elastic modulus and high dimensional stability with high productivity, a wet spinning method using a metal salt as a solvent is preferably used.

The intrinsic viscosity of the polyketone is preferably 2-20. This polyketone is dissolved in a solution containing zinc halide, an alkali metal halide, an alkaline earth metal halide or the like (for example, zinc chloride / calcium chloride aqueous solution) to produce a dope. After the dope is discharged from the spinneret into a liquid such as water to form a yarn, the metal salt is washed off with an aqueous acid solution such as hydrochloric acid, and subsequently dried, and then hot drawing is performed at 200 to 280 ° C. five times or more. I do. When obtaining a high-strength polyketone fiber, the total draw ratio is preferably 10 times or more, more preferably 12 times or more, and in that case, it is preferable to perform multi-step drawing of two or more steps.

After completion of the multi-stage drawing, the temperature was 100 to 280 ° C.
Heat treatment under low tension of 001 to 1 cN / dtex,
It is preferable to control the heat shrinkage stress of the polyketone fiber. By making the maximum heat shrinkage stress of the polyketone fiber close to the maximum heat shrinkage stress of the fiber (B) or fiber (C) to be twisted, the twisted cord is uniform during RFL liquid treatment, vulcanization, and use. Shrinks to give a good quality twisted cord. When the polyketone fiber and the nylon 66 fiber are intertwisted, the tension is set to 0.2 after the multi-stage drawing is completed.
~ 0.5 cN / dtex, 180 ~ 240 ℃ 1 ~
It is preferable to perform heat treatment for 10 seconds to adjust the maximum heat shrinkage stress of the polyketone fiber to 0.2 to 0.6 cN / dtex, which is equivalent to the maximum heat shrinkage stress of the nylon 66 fiber. When the polyketone fiber and the aramid fiber are twisted together, the tension is 0.1 to 0.3 cN / dte.
x, and heat treatment at 180 to 240 ° C. for 1 to 20 seconds so that the maximum heat shrinkage stress of the polyketone fiber is 0.05 to 0.2.
It is preferable to adjust to cN / dtex.

The fineness of the polyketone fiber may be selected at any time depending on the use and purpose, but the single yarn fineness is 0.5 to 5d.
The tex having a total fineness of 300 to 3000 dtex is preferable. Polyketone fibers include oil agents, antioxidants, quenching agents, radical scavengers, gelation inhibitors, matting agents,
An ultraviolet absorber, an additive such as a pigment, and the like may be contained. The fiber (B) is not limited as long as the elongation and elastic modulus are within the range of the present invention, and known fibers can be used as they are. As the fineness, single yarn fineness 1 to 10 de
tx and total fineness of 300 to 3000 dtex are preferable. The fiber (C) is also not limited as long as the tensile strength, the elongation, and the elastic modulus are within the ranges of the present invention, and known fibers can be used. As the fineness, a single yarn fineness of 0.5 to 5
Fibers having a detx and a total fineness of 300 to 3000 dtex are preferably used. Since the fiber (C) has a high elastic modulus, when the single yarn fineness is large, the twisted cord becomes hard when twisted with the polyketone fiber, and it becomes difficult to obtain the high twisted twisted cord. Therefore, the single yarn fineness of the fiber (C) is preferably 2 dtex or less, and more preferably 1.5 dtex or less.

Polyketone fibers (A) and fibers (B) thus obtained, or polyketone fibers (A)
The fibers (C) and the fiber (C) are respectively twisted, then aligned and twisted. There are no restrictions on the type of twisted yarn, the method, and the number of twisted yarns, and any method such as a fragile twisted yarn, a picco mashed twisted yarn, and a strong twisted yarn can be adopted. There is no limitation on the number of twists to be twisted, and two twists or three or more twists may be used. When three or more twists are carried out within the scope of the present invention, nylon 66 fibers, polyethylene terephthalate fibers, and fibers (C) are used within the scope of the present invention (for example, in a twisted cord with fibers (B)). Aramid fiber and polyvinyl alcohol fiber) may be used at the same time in the interlaced cord with. The number of twisted yarns may be arbitrarily selected according to the application, usage environment and the like. Generally, the twist coefficient K is 1000 to 3
The yarn is twisted in the range of 0000. At this time, the twisting tension is preferably 0.01 to 0.2 cN / dtex for both the lower twist and the upper twist. In addition, the twisted cord of the present invention has a polyketone fiber (A) and a fiber (B) or a fiber (C) in an amount within the range of the present invention within the range of the present invention, and the content of the twisted cord is 30% by mass or less. Fibers having characteristics other than the above may be included in proportion. Examples of such fibers include polyethylene naphthalate fibers.

The interlaced cord thus obtained is then immersed in an RFL solution having a concentration of 10 to 30% by mass and passed through a step of applying heat of at least 100 ° C. to fix the RFL solution (so-called Dip treatment). The processing code is obtained. The preferred composition of the RFL solution is resorcin 0.1 to 0.1.
10 mass%, formalin 0.1-10 mass%, latex 1-28 mass%, more preferable composition is resorcin 0.5-3 mass%, formalin 0.5-3 mass%,
The latex content is 10 to 25% by mass. R as required
In addition to the FL treatment, a multi-step treatment of immersing in a liquid such as an epoxy compound or an isocyanate compound may be performed. In the case of the twisted cord with the fiber (B), a sufficient rubber adhesive force can be obtained by a one-bath treatment with only the RFL liquid (processability,
From the viewpoint of cost, a twisted cord of polyketone fiber and nylon 66 fiber and a twisted cord of polyketone fiber and viscose rayon fiber are preferable.

The drying of the RFL solution is preferably 140-2.
At 00 ° C for at least 10 seconds, preferably 20-120
Do it for a second. The dried cord is subsequently heat-treated in the heat setting zone and the normalizing zone. In order to obtain a uniform and high-performance treatment code without shrinkage unevenness, it is important to set the heat treatment conditions (heat treatment temperature, heat treatment tension, and heat treatment time) within a specific range. The heat setting is preferably the maximum heat shrinkage temperature of the twisted cord ± 20 ° C, more preferably the maximum heat shrinkage temperature ± 5 ° C.
And preferably the maximum heat shrinkage stress ± 0.2 cN / dte
x, more preferably maximum heat shrinkage stress ± 0.05 cN / d
Heat treatment is performed under the tension of tex. Also, the heat treatment time is
Preferably 10 to 300 seconds, more preferably 30 to 12
It is in the range of 0 seconds. The heat treatment temperature and heat treatment time of the normalizing zone are preferably within the above-mentioned heat set temperature and time range. The heat treatment tension is preferably 10% to 80% of the heat treatment tension in the heat setting zone.

[0045]

EXAMPLES The present invention will be described in more detail by way of examples, which should not be construed as limiting the scope of the present invention. The measuring method of each measured value used in the present invention is as follows. (1) Intrinsic viscosity Intrinsic viscosity [η] is a value obtained based on the following defining equation. [Η] = lim (T−t) / (t · C) [dl / g] C → 0 In the formula, t and T are hexafluoroisopropanol having a purity of 98% or more and a dilution of polyketone dissolved in hexafluoroisopropanol. Flow-through time of viscous tube at 25 ° C. of solution. C is the solute mass value in grams in 100 ml above.

(2) The amount ratio of 1-oxotrimethylene groups is determined by compositional NMR of polyketone. (3) Fineness, tensile strength, elastic modulus, elongation and 2.0
For the elongation under cN / dtex load and the toughness fineness, the sample is allowed to stand at 25 ° C. and 55% humidity for 48 hours, then the mass W _{1 of the} sample 100 m is weighed, and W ₁ × 100 is taken as the fineness (dtex). For this sample, sample length 25
The tensile strength, elastic modulus, elongation, elongation at 2.0 cN / dtex load and toughness are measured at 0 mm and a crosshead speed of 300 mm / min.

(4) Maximum heat shrinkage stress, maximum heat shrinkage temperature CORD-TESTER (G manufactured by Toyo Seiki Seisakusho Co., Ltd.
odrich Type) is used to measure the heat shrinkage force characteristics of the fiber and the cord under constant displacement under the following conditions. Temperature Program: EXP mode Θ _M : 250 ° C. T ₁ : 3 minutes Initial load: 1/80 (cN / dtex) Initial sample length: 250 mm Maximum shrinkage force F _max from measured temperature-shrinkage force curve
(CN) and the temperature T _max (° C.) showing the maximum shrinkage force are read, and T _max is taken as the maximum heat shrinkage temperature. Furthermore, F
_The maximum heat shrinkage stress σ _max (cN / dtex) is obtained by dividing _max by the fineness (dtex) of the sample.

(5) Resin adhesion rate About 5 m of a code sample cut into a length of 1 mm is heated at 105 ° C. for 5 hours, and then the absolute dry mass W ₂ (g) is measured. Then, the mixture is added to 300 ml of hexafluoroisopropanol, treated at 60 ° C. for 2 hours with stirring to dissolve the chopped cord, and then filtered with a glass filter. The sample residue after filtration is further dissolved according to the dissolution method corresponding to the twisted fibers described in JIS-L1017 (1995). This solution is filtered, the obtained residue is heat-treated at 105 ° C. for 5 hours, the mass W ₃ (g) is precisely weighed, and the resin adhesion rate is calculated from the following formula. Resin adhesion rate _{= [W 3 / (W 2} -W 3)] × 100 (%)

(6) Rubber Adhesion Strength Unvulcanized rubber containing 70% by mass of natural rubber, 15% by mass of SBR, and 15% by mass of carbon black was used, and a cord was embedded in this for 1 cm, 155 ° C., 3.5 MPa, 30 minutes. After vulcanization under the conditions, T pull-out strength (N) is measured at a crosshead speed of 300 mm / min.

[0050]

Reference Example 1 Production of Polyketone Fiber 1 A polyketone having an intrinsic viscosity of 5.9 in which 100% by mass of the repeating unit was 1-oxotrimethylene was produced by a conventional method. 40% by mass of calcium chloride /
It was added to an aqueous solution containing 22% by mass of zinc chloride to obtain a dope having a polymer concentration of 6.8% by mass. The obtained dope was discharged from a spinneret having a number of holes of 300 into a coagulation bath made of water at -2 ° C containing 2% by mass of calcium chloride, 1.1% by mass of zinc chloride and 0.1% by mass of hydrochloric acid. Then, after washing with hydrochloric acid and washing with water, IRGANOX
(Registered trademark) 1098 (manufactured by Ciba Specialty Chemicals Co., Ltd.) and IRGANOX (registered trademark) 1076 (manufactured by Ciba Specialty Chemicals Co., Ltd.) are impregnated with each 0.05 mass% (to polyketone), and then the temperature is set to 22.
After performing constant length drying at 5 ° C. for 1 minute, pressure treatment was performed. This fiber was drawn in the first stage (7 times) in a heating furnace at 225 ° C. Five of these 1-stage drawn yarns were drawn and aligned, and subsequently at 240 ° C / 253 ° C / 257 ° C, 1.5 / 1.
Multi-stage stretching of 3 / 1.25 times was performed. An oil agent was applied to the obtained drawn yarn, and heat treatment was performed at 210 ° C. for 3 seconds while applying a tension of 0.3 cN / dtex to obtain 1625 dtex.
/ 1500f polyketone fiber was produced.

The tensile strength of this polyketone fiber is 1
7.7 cN / dtex, elastic modulus 380 cN / dte
x, elongation is 5.5%, maximum heat shrink temperature is 218
C., the maximum heat shrinkage stress was 0.43 cN / dtex.

[0052]

[Reference Example 2] Production of polyketone fiber 2 In the production of polyketone fiber 1, a polyketone fiber was produced in the same manner except that the heat treatment after multi-stage drawing was performed at 225 ° C for 10 seconds while applying a tension of 0.1 cN / dtex. Manufactured. The tensile strength of this polyketone fiber is 1
7.8 cN / dtex, elastic modulus 388 cN / dte
x, elongation is 5.4%, maximum heat shrink temperature is 180
C., the maximum heat shrinkage stress was 0.12 cN / dtex.

[0053]

Example 1 The polyketone fiber 1 produced in Reference Example 1 and the nylon 66 fiber of 1400 dtex / (210) f (Leona 66 (registered trademark), manufactured by Asahi Kasei Corp.) were respectively twisted at 390 T / m (Z After twisting, 2
The books were aligned and further twisted (S twist) at 390 T / m to obtain an intertwisted cord. The obtained cord has a tensile strength of 10.1 cN / dtex and an elongation of 12.9.
%, The elongation under load of 2.0 cN / dtex was 4.5%, and the toughness was 40.1 cN ·% / dtex, which were extremely excellent. Table 1 shows the characteristics of the polyketone fiber 1, the nylon 66 fiber and the twisted cord, and the performance of the twisted cord.

[0054]

Example 2 A twisted yarn was prepared in the same manner as in Example 1 except that the number of lower twists and the number of upper twists were each 290 T / m. The tensile strength of the obtained twisted cord is 11.
The elongation under load of 5 cN / dtex and 2.0 cN / dtex was 3.7%, which was excellent in strength and dimensional stability. Furthermore, elongation is 10.8% and toughness is 42.2.
It was cN ·% / dtex and had excellent properties. This cord has a heat set tension of 0.45
RF in the same manner as in Example 1 except that cN / dtex is used.
L treatment was performed. The obtained treated cord was homogeneous, had no deformation or defects due to heat shrinkage, and had excellent characteristics of high strength and high elongation. Polyketone fiber 1, nylon 66
The properties of the fiber and the twisted cord, and the performance of the twisted cord are shown in Table 1.

[0055]

Example 3 Twisting was performed in the same manner as in Example 1 except that 1670 dtex / 384f polyethylene terephthalate fiber (SR3 (trademark), manufactured by Teijin Ltd.) was used in place of the nylon 66 fiber. The obtained twisted cord has a tensile strength of 9.5 cN / dtex and an elongation of 1
0.4%, elongation at load of 2.0 cN / dtex is 3.5
% And toughness were 35.5 cN ·% / dtex, which had excellent properties. Further, using this cord, RFL treatment was performed in the same manner as in Example 1 except that the heat setting tension was 0.36 cN / dtex and the heat setting temperature was 210 ° C. The obtained treated cord was homogeneous, had no deformation or defects due to heat shrinkage, and had excellent characteristics of high strength and high elongation. Characteristics of polyketone fiber 1, polyethylene terephthalate fiber and twisted cord,
Table 1 shows the performance of the twisted cord.

[0056]

Comparative Example 1 A polyketone cord was obtained in the same manner as in Example 1 except that the polyketone fiber 1 was used instead of the nylon 66 fiber. This code is 12.9
Although it had a very high tensile strength of cN / dtex, the elongation was low at 8.8%, which was outside the range of the present invention. Table 1 shows the characteristics of the polyketone fiber 1 and the twisted cord, and the performance of the twisted cord.

[0057]

Comparative Example 2 A nylon 66 cord was obtained by carrying out twisting in the same manner as in Example 1 except that nylon 66 fiber was used instead of polyketone fiber 1. The obtained cord has a tensile strength of 8.5 cN / dtex and an elongation of 24.7%.
However, the elongation at 2.0cN / dtex load is 1
It was 1.2%, which was outside the scope of the present invention. Table 1 shows the characteristics of the polyketone fiber 1, the nylon 66 fiber and the twisted cord, and the performance of the twisted cord.

[0058]

Comparative Example 3 A polyethylene terephthalate cord was obtained in the same manner as in Example 2 except that polyethylene terephthalate fiber was used instead of the polyketone fiber 1. The tensile strength of the obtained cord is 6.8 cN
/ Dtex, 2.0cN / dtex elongation at load 6.3
%, Which was outside the scope of the present invention. Table 1 shows the characteristics of the polyketone fiber 1, the polyethylene terephthalate fiber and the twisted cord, and the performance of the twisted cord.

[0059]

Example 4 The interlaced cord produced in Example 1 was dipped in an RFL liquid having the following liquid composition, and then dried (heat treatment at a tension of 0.3 cN / dtex at 160 ° C. for 120 seconds) and heat set zone. (Tension 0.4cN / dtex
At 225 ° C. for 60 seconds) and a normalizing zone (heat treatment at 220 ° C. for 60 seconds at a tension of 0.1 cN / dtex) to obtain a treated cord. (RFL liquid composition) Resorcin 22.0 parts Formalin (30% by mass) 30.0 parts Sodium hydroxide (10% by mass) 14.0 parts Water 570.0 parts Vinyl pyridine latex (41% by mass) 364.0 parts

The resin adhesion rate of the obtained treated cord was 5.5.
%, Tensile strength 9.5 cN / dtex, elongation 1
2.8%, elongation at load of 2.0 cN / dtex is 4.4
%, The toughness was 37.8 cN ·% / dtex, which had excellent mechanical properties. Rubber adhesion is 15
It was 5 N / cm / cord, and sufficient adhesion was exhibited by treatment with one bath of the RFL solution. This treated cord was homogeneous and had a high quality without sagging or distortion due to heat shrinkage.

[0061]

Example 5 Polyketone fiber 2 produced in Reference Example 2 and 1690 dtex / 1000f aramid fiber (KE
VLAR (registered trademark) K29, manufactured by DuPont)
After the lower twisting (Z twisting) was performed at 390 T / m, the two were aligned and the upper twisting (S twisting) was further added at 390 T / m to obtain an intertwisted cord. The obtained cord has a tensile strength of 13.5 cN / dtex and an elongation of 8.
The elongation at load of 3%, 2.0 cN / dtex is 2.4%, and the toughness is 33.9 cN ·% / dtex, which is high strength and low as compared with the cord made of only polyketone fiber.
It had an elongation under load of 0 cN / dtex and a high elongation and toughness. Polyketone fiber 2,
Table 2 shows the characteristics of the aramid fiber and the twisted cord, and the performance of the twisted cord.

[0062]

Example 6 A twisted yarn was prepared in the same manner as in Example 5, except that the number of lower twists and the number of upper twists were each 290 T / m. The tensile strength of the obtained twisted cord is 16.
The elongation under load of 4 cN / dtex and 2.0 cN / dtex was 1.9%, which was high in tensile strength and dimensional stability. Furthermore, the elongation is 7.2% and the toughness is 3
It was 4.5 cN ·% / dtex, and had excellent properties. Table 2 shows the properties of the polyketone fiber 2, the aramid fiber and the twisted cord, and the performance of the twisted cord.

[0063]

Example 7 A twisted yarn was prepared in the same manner as in Example 5, except that the number of lower twists and the number of upper twists were each 190 T / m. The tensile strength of the obtained twisted cord is 18.
The elongation under load of 1 cN / dtex and 2.0 cN / dtex was 1.4%, and the tensile strength and dimensional stability were high. Furthermore, the elongation is 6.1% and the toughness is 3
It was 6.0 cN ·% / dtex, and had excellent properties. Table 2 shows the properties of the polyketone fiber 2, the aramid fiber and the twisted cord, and the performance of the twisted cord.

[0064]

Comparative Example 4 A polyketone cord was obtained in the same manner as in Example 5, except that the polyketone fiber 2 was used instead of the aramid fiber. Although this cord had a higher elongation than the twisted cord, it had a low tensile strength and toughness and a large elongation at a load of 2.0 cN / dtex. Table 2 shows the properties of the polyketone fiber 2 and the twisted cord, and the performance of the twisted cord.

[0065]

Comparative Example 5 An aramid cord was obtained by performing twisting in the same manner as in Example 5 except that the aramid fiber was used instead of the polyketone fiber. The elongation of this cord is as low as 5.0%, which is outside the scope of the present invention. Table 2 shows the properties of the polyketone fiber 2, the aramid fiber and the twisted cord, and the performance of the twisted cord.

[0066]

[Embodiment 8] The interlaced cord produced in Embodiment 5 is dipped in an adhesive liquid 1 having the following composition, and then the tension is 0.9 cN / dt.
After heat treatment at 230 ° C. for 60 seconds with ex, it is subsequently immersed in an adhesive 2 having the following composition and a tension of 0.3 cN / dte.
Heat treatment was performed at 230 ° C. for 90 seconds at x to obtain a treatment code. (Composition of one liquid adhesive) Denacol (registered trademark) 614B (manufactured by Nagase & Co., Ltd.) 30.0 parts 2-pyrrolidone 100.0 parts sodium hydroxide 1.0 part Perex (registered trademark) OTP (Kao (stock) 20.0 parts Water 850.0 parts (Adhesive 2 liquid composition) Resorcin 14.0 parts Formalin 20.6 parts Sodium hydroxide 1.6 parts Water 106.7 parts Vinyl pyridine latex (49.8 mass) %) 857.1 parts

The resin adhesion ratio of the obtained treated cord was 6.1.
%, The tensile strength is 12.5 cN / dtex, the elongation is 8.1%, and the elongation under load of 2.0 cN / dtex is 2.
3%, toughness is 34.5 cN% / dtex,
It had excellent mechanical properties. The rubber adhesive strength is 150
The adhesive strength was as high as N / cm / cord. This treated cord was homogeneous and had a high quality without sagging or distortion due to heat shrinkage.

[0068]

[Table 1]

[0069]

[Table 2]

[0070]

INDUSTRIAL APPLICABILITY The interlaced cord of the present invention has excellent mechanical properties such as high strength and high dimensional stability close to those of cords made only of polyketone, and high elongation and toughness which cannot be obtained by cords made only of polyketone. It has the characteristics of. Furthermore, by controlling the heat shrinkage characteristics of the polyketone fiber used for twisting, it is possible to realize a high-performance and high-quality cord without sagging or distortion due to heat shrinkage and deterioration of physical properties. The twisted and twisted cord of the present invention makes use of the characteristics of high strength, high dimensional stability, high elongation, high toughness, and good adhesive strength with rubber, for industrial material applications under high load, particularly tires, belts, Hose, FRP,
It is extremely useful as a fiber material for reinforcing molded products such as optical fibers and cement.

Claims (14)

[Claims] 1. 95 to 100% by weight of the repeating unit is 1
The following (a) composed of -oxotrimethylene
A polyketone fiber (A) having the characteristics (c) and a fiber (B) having the following characteristics (d) to (e) are twisted together, and the mass of the fibers A and B is a twisted cord. Ratio (A
/ B) is 80/20 to 20/80, and the following (f) to
An interlaced cord having the characteristic (h). Fiber (A) (a) Tensile strength ≧ 10 cN / dtex (b) Elastic modulus ≧ 200 cN / dtex (c) Elongation = 3 to 9% Fiber (B) (d) Elastic modulus ≦ 200 cN / dtex (e) Elongation ≧ 10% Cord (f) Tensile strength ≧ 7 cN / dtex (g) Elongation ≧ 10% (h) 2.0 cN / dtex Elongation under load ≦ 6% 2. The twisted cord according to claim 1, wherein the toughness is 30 cN ·% / dtex or more. 3. A maximum heat polyketone fiber maximum heat shrinkage temperature T _A and the fiber maximum thermal shrinkage stress sigma _A and the fiber of the maximum thermal shrinkage temperature T _B and polyketone fibers (B) (A) of (A) (B) The twisted cord according to claim 1 or 2, wherein the contraction stress σ _B satisfies the following expression. _{| T A -T B | = 0~30} ℃ | σ A -σ B | = 0~0.2cN / dtex 4. The maximum heat shrinkage stress is 0.01 to 0.6 cN.
/ Dtex, The twisted cord according to any one of claims 1 to 3. 5. The fiber B is at least one fiber selected from the group consisting of nylon 66 fiber, nylon 6 fiber, rayon fiber, polyethylene terephthalate fiber and polytrimethylene terephthalate fiber. The twisted cord according to any one of 1 to 4. 6. The twisted cord according to any one of claims 1 to 5, wherein 1 to 10% by mass of resorcin-formalin-latex resin is attached to the twisted cord. A twisted cord with improved adhesion. 7. 95 to 100% by weight of the repeating unit is 1
The following (a) composed of -oxotrimethylene
A polyketone fiber (A) having the characteristics (c) and a fiber (C) having the following characteristics (i) to (k) are twisted together, and a mass of A and C. Ratio (A
/ C) is 80/20 to 20/80, and the following (l) to
A twisted cord having the characteristic (n). Fiber (A) (a) Tensile strength ≧ 10 cN / dtex (b) Elastic modulus ≧ 200 cN / dtex (c) Elongation = 3 to 9% Fiber (C) (i) Tensile strength ≧ 18 cN / dtex (j) Elastic modulus ≧ 450 cN / dtex (k) Elongation = 2 to 5% Cord (l) Tensile strength ≧ 12 cN / dtex (m) Elongation ≧ 6% (n) 2.0 cN / dtex Elongation ≦ 4% 8. The twisted cord according to claim 7, wherein the toughness is 30 cN ·% / dtex or more. 9. The maximum heat shrinkage stress is 0.01 to 0.6 cN.
/ Dtex, The twisted and twisted cord according to claim 7 or 8. 10. The fiber C is at least one fiber selected from the group consisting of aramid fiber, polyethylene fiber, polybenzazole fiber and polyvinyl alcohol fiber, according to any one of claims 7 to 9. The twisted cord according to item 1. 11. The twisted cord according to any one of claims 7 to 10, wherein the resorcin-formalin-latex resin is attached to the twisted cord in an amount of 1 to 10% by mass. A twisted cord with improved adhesion. 12. A molded product using the twisted cord according to any one of claims 1 to 11. 13. The molded product according to claim 12, wherein the molded product is one kind selected from tires, hoses, belts and optical fibers. 14. The method according to claim 1, 2, 3, 4, 5, 7, 8,
After immersing the interlaced cord according to any one of 9 and 10 in a resorcin-formalin-latex solution, the interlaced cord has a maximum heat shrinkage temperature of ± 20 ° C. and a maximum heat shrinkage stress of ± 20 ° C.
A method for producing a twisted and twisted cord having improved adhesiveness, which comprises a step of performing heat treatment for 10 to 300 seconds under a tension of 0.2 cN / dtex.