JP2003049339A - Cord fabric - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a high-quality cord fabric which causes neither dislocation of meshes nor strain by heat shrinkage during or after weaving of cord fabric, forms neither fluff nor fibril-like material during twisting and weaving, has neither pill or powder on a cord fabric or a weaving machine and is useful for a material for rubber reinforcement, etc. SOLUTION: This cord fabric is characterized in that in a cord fabric constituted of warp and weft, >=50 mass % of fibers constituting the warp is a polyketone fiber and a coefficient (μs) of static friction between the fibers of the warp and weft is >=0.2.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a interwoven fabric using polyketone fiber as a warp. More specifically, the present invention relates to a warp yarn using a polyketone fiber and a weft yarn, which is uniform without slippage due to small slippage, and has excellent flatness due to small shrinkage during heating. The blind fabric of the present invention is used as a rubber-reinforcing material after applying an adhesive, and is extremely useful as a rubber-reinforcing fiber material for tires, belts, hoses and the like.

[0002]

2. Description of the Related Art In rubber products such as tires, belts and hoses, mainly metal fiber materials such as steel and organic fiber materials such as rayon, nylon 66 fiber and polyethylene terephthalate fiber are used as materials for bearing the strength of the product. Has been used. However, although a metal fiber material such as steel has excellent mechanical performance, it has a problem that it becomes heavy because of its large specific gravity. On the other hand, regarding conventional general-purpose organic fiber materials, rayon has a low mechanical strength and its physical properties deteriorate under water and high humidity. Nylon 66 fiber has a small elastic modulus and its dimensional stability under load is low, so that it cannot be heated. There were problems such as large heat shrinkage under heating, and there was a problem that polyethylene terephthalate fiber had large heat shrinkage under heating.

As a material that can replace these conventional organic fiber materials, carbon monoxide and olefins are polymerized by using palladium or nickel as a catalyst to polymerize carbon monoxide and olefins substantially completely in an alternating copolymerization. It was found that the obtained aliphatic polyketone was obtained (industrial materials, December issue, page 5, 1997).
), Research into fiberizing polyketones has been conducted. Polyketone fiber is known to have a higher melting point than conventional polyolefin fibers, and also to have high strength and high elastic modulus. Utilizing this excellent physical property, industrial material applications,
In particular, it is expected to be developed as a rubber reinforcing material for tires, belts, hoses, etc.

When a fiber material is used as a rubber reinforcing material, usually, after twisting the fiber, an adhesive is applied to form a cord, or it is embedded in the rubber material in the form of a blind cloth. Up to now, some techniques have been disclosed for polyketone fibers (see, for example, Japanese Patent Laid-Open No. 12461/1991).
Japanese Patent Laid-Open No. 7-112413, Japanese Patent Laid-Open No. 4-112413
505344, JP-A-4-228613,
Japanese Patent Publication No. 7-508317, Japanese Patent Publication No. 8-50732
No. 8, US Pat. No. 5,955,019, WO 99/18143 pamphlet, WO 00 /
No. 09611, etc.), these prior arts only describe a technique relating to a polyketone fiber having high strength and a high elastic modulus, and do not describe any use of the polyketone fiber in a blind fabric.
JP-A-1-124617 and JP-A-9-32437.
No. 7, Japanese Patent Laid-Open No. 9-329198, No. 11
-334313, JP-A-11-336957, JP-A-2000-14202, JP-A-2000
Japanese Unexamined Patent Publication No. 2000-190705.
Japanese Unexamined Patent Publication No. 2000-264012 and the like disclose techniques relating to polyketone cords and interwoven fabrics using polyketone cords as warp yarns.

However, according to the studies by the present inventors, it was found that the cord and the blind fabric disclosed in these prior arts have the following problems (a) to (c). However, the prior art is completely silent about the description of these problems, the means for solving these problems, and the technology for producing a high performance and high quality blind fabric. (A) Polyketone fibers and cords composed of polyketone fibers have a small coefficient of friction, and when used as warp yarns for a blind weave fabric, slippage occurs with the weft yarns, resulting in uneven warp yarn driving intervals. Is likely to occur. (B) Polyketone fiber having high strength and high elastic modulus and a cord made of polyketone fiber have a high heat shrinkage stress, and the heat shrinkage after weaving the blind fabric distorts the flat fabric and impairs the flatness. (C) Polyketone fibers with high strength and high elastic modulus, and cords made of polyketone fibers are prone to fluff and fibrils during twisting and weaving, and fluff and powder are generated on the blind fabric and loom, resulting in quality and process. Passability is reduced.

[0006]

SUMMARY OF THE INVENTION The present invention solves the above problems and provides (1) a uniform interlaced woven fabric in which slippage between warp and weft does not cause non-uniformity in warp intervals, resulting in non-uniform misalignment. (2) To provide a blind fabric that is excellent in dimensional stability and flatness without causing distortion due to heat shrinkage during weaving and after weaving, and (3)
No fluff or fibrils are generated during twisting or weaving,
It is to provide a high-quality blind fabric without pills or powder on the blind fabric or on a loom with good processability.

[0007]

[Means for Solving the Problems] The inventors of the present invention have conducted extensive studies to achieve the above object, and have completed the present invention. That is, according to the present invention, in the interwoven fabric composed of the warp and the weft, 50 of the fibers constituting the warp are used.
Mass% or more is polyketone fiber, and fiber-fiber static friction coefficient (μs) of warp and weft is 0.2 or more, and is a blind fabric.

The interwoven fabric of the present invention comprises 5 of the constituent fibers.
It is composed of a warp yarn in which 0 mass% or more is a polyketone fiber, and a weft yarn. The warp form of the interwoven fabric of the present invention is a cord or a strand. A cord is a yarn in which several yarns twisted in one direction are aligned and twisted in the opposite direction. Strand means a bundle of long fibers without twisting or 10
It is a yarn with a light twist of 0 T / m or less. In the present invention, the polyketone fiber has 95 to 100 repeating units.
Mass%, preferably 97 mass% or more, more preferably 1
The fiber is made of polyketone composed of 1-oxotrimethylene, of which 100% by mass is represented by the chemical formula (1).

[0009]

[Chemical 1]

The higher the proportion of 1-oxotrimethylene in the repeating unit, the more regular the molecular chain, and the more crystalline and highly oriented the fiber can be obtained. Therefore, by using this fiber, a warp yarn having high strength, high elastic modulus and high heat resistance can be obtained. The blind fabric of the present invention is excellent in strength, dimensional stability, heat resistance, and adhesiveness with rubber, but for that purpose, 50% by mass or more of the fibers constituting the warp must be polyketone fibers. Is.

The types of warp yarns used in the interwoven fabric of the present invention include, for example, (a) cords composed only of polyketone fibers, (b) strands composed only of polyketone fibers, (c) polyketone fibers and fibers other than polyketone fibers. A mixed or twisted cord, (d) a strand obtained by mixing polyketone fiber and a fiber other than polyketone fiber,
(E) Cords made of fibers other than polyketone fibers,
(F) Strands made of fibers other than polyketone fibers,
Etc. Thereafter, the above (a) is the “polyketone cord”, (b) is the “polyketone strand”, (a),
(C) is "cord made of polyketone fiber", (b),
(D) is called a "strand made of polyketone fiber".

In the cases of (c) and (d), 50% by mass of polyketone fiber is contained in one cord or strand.
It is preferable that the above is included. The warp is (a)
At least one selected from (d), or (a) ~
It may be composed of at least one selected from (d) and at least one selected from (e) and (f). In any case, the polyketone fiber is 50% by mass or more, preferably 7% by weight in all warp yarns in the interwoven fabric.
It is used in an amount of 5% by mass or more, more preferably 90% by mass or more, and most preferably 100% by mass. When the proportion of the polyketone fiber in the warp is less than 50% by mass, the performance of any of the strength, dimensional stability, heat resistance, and adhesiveness with rubber of the woven fabric becomes insufficient.

The fibers other than the polyketone fibers are not particularly limited as long as the proportion is less than 50% by mass, and known fibers such as polyamide fibers, polyester fibers, rayon fibers and aramid fibers can be used depending on the application and purpose. Used. When the content of fibers other than polyketone fibers exceeds 50% by mass, strength and dimensional stability are impaired in the case of warps made of polyester fibers or polyamide fibers, and strength is greatly impaired in the case of warps made of rayon fibers. In the case of a warp made of aramid fiber, the adhesiveness with rubber is greatly impaired.

The interwoven fabric of the present invention comprises 50% by weight of the warp.
It is preferable that the polyketone cord is at least 80% by mass, more preferably at least 100% by mass. When the proportion of polyketone cords in the warp is small, it is difficult to obtain a suede woven fabric excellent in strength, dimensional stability, heat resistance, adhesion to rubber, and fatigue resistance of a molded product. The interwoven fabric of the present invention is
Coefficient of static friction between fibers of warp and weft (hereinafter, μ
s, which may be abbreviated as s) is 0.2 or more, preferably 0.25 or more, and more preferably 0.3 or more. As described above, the warp yarn using the polyketone fiber is particularly slippery against the friction with the weft yarn as compared with the warp yarn using the other fibers. Therefore, μ of warp yarn using polyketone fiber
Setting s to 0.2 or more is extremely important in the present invention. When μs is less than 0.2, the warp and weft slip during storage as a warp after winding or due to fluctuations in tension applied to the warp, and the warp spacing becomes uneven, resulting in a poor quality drapery fabric. Not only that, but the warp density changes, and it becomes impossible to obtain a homogeneous product. On the other hand, the value of μs has no upper limit, but if it is too high, when it is used as a rubber reinforcing material, the weft cannot be removed smoothly after cutting the weft during molding, so that it is preferably 3 or less.

The fiber-fiber static friction coefficient (μs) between the warp yarn and the weft yarn forming the interwoven fabric is the single yarn fineness, the total fineness of the fibers forming the warp yarn, the type of oil agent and the oil agent application rate, and in the case of a cord. Since it varies depending on the combination of the number of twisted yarns, the twisted form, etc., these conditions are adjusted so that a desired μs can be obtained. A warp made of a fiber other than polyketone fiber usually has a μs of 0.2 or more with a weft, so that for a warp containing a polyketone fiber, μs is 0.2
It is necessary to be above. Of course, when the μs of the warp made of fibers other than the polyketone fiber is also less than 0.2, similarly, it is necessary to set the μs to 0.2 or more.

The warp yarn containing the polyketone fiber will be described below as an example. The same applies to warps made of fibers other than polyketone fibers. Setting the Single Yarn Fineness The smaller the single yarn fineness of the polyketone fiber used for the warp, the larger μs is, which is preferable from the viewpoint of preventing misalignment. However, if the single yarn fineness is too small, yarn breakage easily occurs, and the process passability such as drawability, twistability, and weavability is reduced,
Since fluff causes deterioration in quality, it is preferably 0.1.
-10 dtex, more preferably 0.5-5 dtex,
Most preferably, it is 0.8-2 dtex. The cross-sectional shape of the single yarn is not particularly limited, but a round cross section is preferable.

Selection of oil agent It is preferable that the oil agent is attached to the surface of the warp. From the viewpoint of drawability and twistability, it is preferable that an oil agent that enhances smoothness and lubricity be attached, but if the oil agent has too high smoothness, slippage between the warp and the weft occurs. Therefore,
The coefficient of dynamic friction between polyketone fibers-polyketone fibers (hereinafter sometimes abbreviated as μd) is preferably 0.0.
1 to 0.7, more preferably 0.05 to 0.6, and most preferably 0.1 to 0.5, and the oil composition is determined so that μs of the warp and the weft is 0.2 or more. It is preferable.

There is no particular limitation on the oil agent component that can be used for the polyketone fiber used in the warp of the blind fabric of the present invention. For example, the oil agent described in Japanese Patent Application No. 2000-19995 can be used. In order to impart smoothness and abrasion resistance, an oil agent containing an ester compound, a mineral oil, or a polyether compound is preferable. The oil agent preferably contains an emulsifier, an antistatic agent, a heat stabilizer and the like as its components. If the adhered amount of the oil agent is less than 0.1% by mass, the effect of reducing the frictional resistance is insufficient. 0.1 to 10% by mass is preferable, more preferably 0.3 to 5% by mass, and most preferably 0.5 to
It is 2% by mass.

The fineness of the warp yarn, the number of twisted yarns The total fineness of the cord made of polyketone fiber and the strand made of polyketone fiber is 300 to 30000 dte.
x is preferable, and more preferably 500 to 70.
It is 00 dtex. If it is less than 300 dtex, μs will be small when a strong twist cord is used. Also, 30000d
If it exceeds tex, the handlability of the woven fabric cloth deteriorates. The cords made of polyketone fibers used in the blind fabric of the present invention and warps other than the strands made of polyketone fibers also have a total fineness of 300 to 30,000 dt.
ex is preferably 500 to 7000 dtex
Is more preferable.

When a cord made of polyketone fiber is used as the warp, the number of twisted yarns is not particularly limited and is selected according to the application, and the twist coefficient K of the upper twist shown by the following formula is 10:
The range of 00 to 30,000 is preferable. K = Y × D ^0.5 where Y is the number of twists per meter of cord (T / m),
D is the total display fineness (dtex) of the cord. The total indicated fineness is the sum of the fineness of all the fibers used for the twisted yarn. For example, when three 1670 dtex polyketone fibers are twisted together, the total indicated fineness of the twisted yarn is 5010 dtex (1
670/3). When used as a strand, the number of twisted yarns is preferably 0 to 100 T / m, and more preferably 5 to 10 T / m from the viewpoint of the friction coefficient and the yarn converging property.

The interwoven fabric of the present invention is mainly subjected to a heat treatment process such as application of an adhesive or rubber vulcanization during the production of the interwoven fabric which is mainly used for rubber reinforcing materials. However, cords and strands composed of highly stretched polyketone fibers show a very strong heat shrinkage force, and tend to cause deformation of blinds and distortion of molded products. Therefore, the cord made of polyketone fiber and the strand made of polyketone fiber preferably have a small heat shrinkage stress, and the maximum heat shrinkage stress is preferably 0.01 to 0.6 cN / dtex, and more preferably 0.05. ~ 0.5 cN /
dtex, most preferably 0.1-0.4 cN / dte
x. If the maximum heat shrinkage stress exceeds 0.6 cN / dtex, the shrinkage force of the blind fabric may become so strong that the weft yarn may be deformed, the weave density may be uneven, or the molded product may be deformed. On the other hand, when the maximum heat shrinkage stress is less than 0.01 cN / dtex, the heat setting property may be deteriorated and slack may occur in the woven fabric or the molded product.

Kind and Fineness of Weft There are no particular restrictions on the kind and fineness of the weft used in the interwoven fabric of the present invention as long as μs is within the scope of the present invention, and it may be selected according to the application and purpose. it can. From the viewpoint of cost and handleability, polyester fibers, polyamide fibers and cellulose fibers are preferable, and from the viewpoint of friction characteristics with polyketone fibers and cutting properties during processing, cotton fibers, polynosic fibers, viscose rayon fibers, copper ammonia rayon fibers, etc. Cellulose fibers are particularly preferably used.

The shape retention ability of the blind and the cuttability during processing,
From the viewpoint of frictional characteristics with the warp and the weft, it is desirable to set the fineness of the weft within an appropriate range.
0 dtex, and in the case of short fibers, 10 ^s to 40 ^s is preferable. 50% by mass of polyketone fiber in the warp of the blind fabric of the present invention
The cords including the above are required to have high strength and high dimensional stability as their characteristics, and have a tensile strength of 7 cN /
dtex or more is preferable, and more preferably 10 cN / d
tex or more, most preferably 12 cN / dtex or more. Also, the elongation at 2.0 cN / dtex load is 5%
It is preferably at most 4%, more preferably at most 4%,
Most preferably, it is 3% or less. Tensile strength is 7cN
If it is less than / dtex, it is necessary to increase the total number of cords in order to exert sufficient strength as a reinforcing material.
If the elongation under a load of 2.0 cN / dtex exceeds 5%, the elongation of the cord when a load is applied becomes large, and the material is likely to undergo dimensional change.

In order to obtain the above-mentioned high performance warp, the polyketone fiber used for the warp must have high strength, high elastic modulus and high dimensional stability, and the polyketone fiber has a tensile strength of 10 cN / dtex or more. , The elastic modulus is 250
It is preferably cN / dtex or more, more preferably 5 cN / dtex or more in tensile strength and 3 in elastic modulus.
Polyketone fiber of 50 cN / dtex or more is used for the warp. Regarding the thermal characteristics of the polyketone fiber, the shrinkage rate by dry heat treatment at 150 ° C. for 30 minutes is 0 to 2%, and the maximum heat shrinkage stress is 0.
It is preferably from 01 to 0.6 cN / dtex, more preferably from 0 to 1% in dry heat shrinkage and 0.1 to 0.4 cN / dtex in maximum heat shrinkage stress.

In order for the warp to have a high quality with no fluff or yarn breakage, it is important that the polyketone fiber used in the warp has excellent drawability and twistability. The dynamic friction coefficient (μd) between the fibers and the polyketone fiber is preferably 0.01 to 0.7, and more preferably 0.05 to 0.3. The composition of the interwoven fabric of the present invention is not particularly limited, and the warp density, the weft density, the width and the length of the interlock, etc. can be arbitrarily selected.
The warp density may be any of high-ends, middle-ends and low-ends, but the warp density is 5 to 80 threads / 5 cm and the weft density is 1 to 10 threads / 5 cm from the viewpoint of the homogeneity and handleability of the blind fabric. It is preferable.

The interwoven fabric of the present invention is made of resin, adhesive, etc.
It may contain components other than fibers, and the components and amounts thereof are not particularly limited. As the resin, known resins such as thermosetting resins such as epoxy resin and phenol resin, thermoplastic resins such as polyester resin and polyamide resin can be used. When used as a rubber reinforcing material, in order to enhance the adhesiveness between the rubber and the blind fabric, a fabric to which an adhesive is attached is used. The kind of the adhesive is not particularly limited, and a known adhesive can be used as it is or by appropriately selecting the composition ratio. Among them, it is common to use an adhesive containing an RFL (resorcin-formalin-latex) solution as a main component, and in this case, the RFL solution may be used alone, and if necessary, an epoxy compound, an isocyanate compound, or a phenol. You may use it, mixing with a chemical | medical solution, such as a compound. There is no particular limitation on the amount of the adhesive to be attached to the suede woven fabric, and a desired amount may be given depending on the application and purpose, but in view of mechanical properties, processability, and adhesiveness with rubber, It is preferably 0.1 to 20% by mass, more preferably 1 to 10% by mass, and most preferably 2 to 8% by mass.

Next, the method for producing the interwoven fabric of the present invention will be described. The polyketone fiber used for the warp can be produced by a known wet spinning method (a method in which polyketone is dissolved in a solvent, made into a fibrous state in a coagulation bath, desolvated and dried, and then hot-drawn). 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 polyketone used for dissolution preferably has a repeating unit ratio of 1-oxotrimethylene of 95 to 100% by mass and an intrinsic viscosity of 2 to 20. This polyketone is a zinc halide, an alkali metal halide,
It is dissolved in a solution containing an alkaline earth metal halide or the like (eg, zinc chloride / calcium chloride aqueous solution). The dissolved solution is discharged from a spinneret into a liquid such as water to form a filament, and then the metal salt is washed off with an aqueous acid solution such as hydrochloric acid. Then, after drying, the temperature is 5 at 200 to 280 ° C.
Double heat stretching is performed. In the case of producing a high-strength polyketone fiber, it is preferable to set the total draw ratio to 10 times or more, more preferably 12 times or more, and perform multi-step drawing of two or more steps. At this time, an oil agent is applied before and / or after drawing to reduce μd during drawing and during twisting, and an oil agent is applied again after drawing and / or after twisting so that μs of the warp is 0.2 or more. It is important to. Furthermore, for the purpose of suppressing heat shrinkage of the blind fabric, 0.001-1 cN at 100-280 ° C. after completion of multi-stage drawing.
It is preferable to reduce the heat shrinkage stress of the polyketone fiber by performing a low tension heat treatment of / dtex.

The polyketone fiber thus obtained is twisted and processed into a cord, or it is aligned and used as a strand. When processing into a cord, there are no particular restrictions on the type of twisting yarn, the method, and the number of ply twisted yarns, and any method such as single-twisted yarn, wrought twisted yarn, picco fluffed twisted yarn, and strongly twisted yarn can be adopted. There is no particular limitation, such as two-ply twisting, and three or more twisted plies may be used.
The number of twisted yarns may be arbitrarily selected according to the application, use environment, etc. Generally, the twist coefficient K of the upper twist is 1000 to 30.
It is twisted in the range of 000. At this time, the twisting tension is preferably 0.01 to 0.2 cN / dtex for both the lower twist and the upper twist.

The cords and / or strands containing the polyketone fiber obtained in this way in at least a part thereof are arranged in 5 to 80 pieces / 5 cm, and 1 to 1 of weft yarns are woven with a weaving machine.
By driving at a rate of 10 pieces / 5 cm, the interwoven fabric of the present invention can be obtained. An RFL solution having a concentration of 10 to 30% by mass is attached to the obtained interwoven fabric, and at least 1
An RFL-treated woven fabric can be obtained by passing through a step of applying heat of 00 ° C. to fix the fabric (so-called Dip treatment). RF
The preferable composition of the L liquid is resorcin 0.1 to 10
Mass%, formalin 0.1 to 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. The drying temperature of the RFL liquid applied to the suede fabric is preferably 140 to 200.
Dry heat treatment at 0 ° C. for at least 10 seconds, preferably 20-120 seconds.

The dried interwoven fabric is heat-treated in the heat setting zone and the normalizing zone. At this time, it is important to set the heat treatment conditions (heat treatment temperature, tension during heat treatment, heat treatment time) within a specific range. The heat treatment temperature is preferably 150 to 250 ° C, more preferably 180 to 230 ° C. The heat treatment tension is preferably (maximum heat shrinkage stress ± 0.2) cN / dtex, more preferably the maximum heat shrinkage stress. The heat treatment time is preferably in the range of 10 to 300 seconds, more preferably 30 to 120 seconds. The heat treatment temperature and heat treatment time in the normalizing zone are preferably within the ranges of the heat setting temperature and heat treatment time described above. The tension during heat treatment in the normalizing zone is preferably about 10 to 80% of the tension during heat treatment in the heat setting zone.

[0032]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described by way of Examples, which do not limit the scope of the present invention. The measuring method of each measured value used in the present invention is as follows. (1) Intrinsic Viscosity [η] The 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 definition formula, t and T are hexafluoroisopropanol having a purity of 98% or more and polyketone dissolved in hexafluoroisopropanol. Flow-through time of the viscous tube at 25 ° C. for the diluted solution. C is the solute mass value in grams in 100 ml above.

[0033] (2) fineness, tensile strength, elongation fineness during modulus and 2.0 cN / dtex load, the sample 25 ° C., 48 hours after standing under 55% humidity, the mass W ₁ of the sample 100 m ( g) is weighed and W ₁ × 10
0 is defined as the fineness (dtex). This sample is sample length 25
The tensile strength, the elastic modulus, and the elongation under a load of 2.0 cN / dtex are measured under the conditions of 0 mm and a crosshead speed of 300 mm / min.

(3) The resin adhesion rate code of 5 m was heated at 105 ° C. for 5 hours and then the absolute dry weight W was obtained.
₂ Weigh (g). Next, the cord is chopped into 1 mm lengths and dissolved with 200 ml of hexafluoroisopropanol under stirring at 60 ° C. for 2 hours. After dissolution and filtration, the obtained residue is heat-treated at 105 ° C. for 5 hours, and then the mass W
₃ (g) is precisely weighed and the resin adhesion rate is calculated from the following formula. Resin adhesion rate _{= (W 3 × 10) /} (W 2) × 100
(%)

(4) Dry heat shrinkage ratio Dry heat treatment was carried out in an oven at 150 ° C. for 30 minutes, and the fiber length before and after the heat treatment was measured by applying a load of 1/30 (cN / dtex) according to the following formula. Ask. Dry heat shrinkage rate _{= (L b -L a) /} (L b) × 100
(%) In the formula, L _b is the fiber length before heat treatment, and L _a is the fiber length after heat treatment.

(5) Maximum heat shrinkage stress, maximum heat shrinkage temperature CORD-TESTER (trademark) (Goodrich)
Type) (manufactured by Toyo Seiki Seisakusho Co., Ltd.) 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 (g / dtex) Initial sample length: 250 mm Maximum shrinking force F _max from measured temperature-shrinking 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. F _ma maximum thermal shrinkage stress _x a is divided by the fineness of the sample (dtex) σ _MAX (c
N / dtex).

(6) Coefficient of static friction between warp and weft (μ
s) The measurement is performed using the apparatus shown in FIG. A weft yarn 1 having a length of about 690 m is wound around the cylinder 2 at a traverse angle of 15 ° to be about 0.2 cN /
Wrap with dtex tension applied. Furthermore, a length of 30.
A 5 cm warp 3 is hung on this cylinder. At this time, the warp 3 is on the cylinder 2 and is parallel to the winding direction of the cylinder.
A load of 0.1 cN is applied to one end of the warp thread 3 hung on the cylinder 2.
A weight 4 of / dtex (opposite warp) is tied, and a strain gauge 5 is connected to the other end. Next, set the cylinder 2 to 1 mm
The tension is measured by the strain gauge 5 while rotating at a peripheral speed of / min. From the tension thus measured, μs is obtained from the following formula. μs = (1 / π) × ln (T ₂ / T ₁ ) where T ₁ is the weight of the weight applied to the fiber, T ₂ is the tension measured by the strain gauge, ln is the natural logarithm, and π is a circle. Indicates the pi.

(7) Dynamic friction coefficient (μd) between polyketone fiber and polyketone fiber Measurement is carried out using the apparatus shown in FIG. A polyketone fiber (A) 6 having a length of about 690 m is wound around the cylinder 2 at a traverse angle of 15 °.
And apply a tension of about 0.2 cN / dtex to wind the polyketone, and further apply a polyketone fiber (B) 7 having a length of 30.5 cm, which is the same as the fiber wound on the cylinder 2, to the cylinder. At this time, the polyketone fiber (B) 7 is on the cylinder and is parallel to the winding direction of the cylinder. A weight 4 having a load of 0.1 cN / dtex (vs. polyketone fiber (B)) is connected to one end of the polyketone fiber (B) 7 hung on the cylinder 2, and a strain gauge 5 is connected to the other end. Next, the cylinder is 18m
The tension is measured by the strain gauge 5 while rotating at a peripheral speed of / min. From the tension thus measured, μd is obtained from the following formula. μd = (1 / π) × ln (T ₂ / T ₁ ) where T ₁ is the weight of the weight applied to the fiber, T ₂ is the tension when measured, ln is the natural logarithm, and π is the circular constant. Indicates.

[0039]

Example 1 A polyketone having an intrinsic viscosity of 6.0 in which ethylene and carbon monoxide were completely copolymerized by a conventional method,
It was dissolved in an aqueous solution containing 40% by mass of calcium chloride / 22% by mass of zinc chloride to obtain a dope having a polyketone concentration of 6.5% by mass. The obtained dope was heated to 80 ° C., passed through an air gap of 10 mm from a spinneret having a spinneret diameter of 0.15 mmφ, L / D = 1, and a number of holes of 250, and then 2% by mass.
Calcium chloride, 1.1% by weight zinc chloride and 0.
A filament was extruded at a discharge rate of 22.5 cc / min into a coagulation bath made of water at -2 ° C. containing 1% by mass of hydrochloric acid, and was drawn at a take-up speed of 5 m / min.

Subsequently, the yarn was washed with an aqueous solution of hydrochloric acid and then with water, and then IRGANOX (registered trademark) (Ciba
(Specialty Chemicals) 109
8. IRGANOX (registered trademark) (Ciba Spec)
ialty Chemicals Co., Ltd.) 1076 (0.05% by mass each) (combined with polyketone) was blended and then dried at 225 ° C. for a fixed length. 7 at 225 ° C
After double stretching, 6 polyketone fibers are combined to give an oil emulsion having a concentration of 1% by mass, and then 2
4-stage stretching was carried out at 40 ° C., 1.5 times, at 250 ° C., 1.3 times, and at 257 ° C., 1.2 times, a total of 16.4 times.
An oil emulsion having a concentration of 7.5% by mass was applied to this polyketone fiber, and it was heated at 220 ° C. for 15 seconds (tension = 0.1 cN
/ Dtex).

The oil having the following composition was used. Oleic acid lauryl ester / bisoxyethyl bisphenol A / polyether (propylene oxide / ethylene oxide = 35/65: molecular weight 20000) / polyethylene oxide 10 mol addition oleyl ether / polyethylene oxide 10 mol addition castor oil ether / sodium stearyl sulfonate / dioctyl phosphorus Sodium acidate =
30/30/10/5/23/1/1 (mass% ratio).

The stretchability was good, and there were no defects such as fluff or yarn breakage during stretching. The fineness of the obtained polyketone fiber is 1
510 dtex, tensile strength 17.0 cN / dte
x, the elastic modulus was 355 cN / dtex, and had excellent physical properties. The dry heat shrinkage rate was 0.4% and the maximum heat shrinkage stress was 0.25 cN / dtex, which was excellent in heat shrinkage characteristics. The μd of this fiber was 0.22. After ply twisting this polyketone fiber in the Z direction,
The main alignment was twisted and twisted in the S direction to obtain a polyketone cord. Twisting conditions are as follows: Twisted yarn number is 390
T / m, twisting tension is 0.8N (0.05cN / dte
x), ply twist: the number of twisted yarns is 390 T / m, and the twisted yarn tension is 1.
It was 8 N (0.05 cN / dtex) (twisting coefficient of top twist was 21432). The twistability was good, and no defects such as fluff and yarn breakage were observed during twisting.

The fineness of the obtained polyketone cord is 362.
At 0 dtex, tensile strength is 12.7 cN / dte
The elongation at x, 2.0 cN / dtex load was 3.1%, and had excellent mechanical properties. Also, the maximum heat shrinkage temperature is 218 ° C. and the maximum heat shrinkage stress is 0.20 cN / dte.
x, the dry heat shrinkage rate was 0.5%, and had stable heat shrinkage characteristics. Using this polyketone cord as a warp, a cotton spun yarn of 20 ^s was used as a weft, and a woven fabric having a warp density of 40/5 cm, a weft density of 4/5 cm, and a width of 1400 mm was woven. No fluff or fibrils were generated during weaving, and no lint or pills were observed on the loom, indicating good weavability. Μs of warp and weft is 0.3
It was 2. The resulting blind fabric was flat and free from misalignment, and was of excellent quality.

[0044]

Example 2 The blind fabric obtained in Example 1 was dipped in an RFL solution having the following liquid composition, then dried at 160 ° C. for 80 seconds, and heat-treated at 220 ° C. for 45 seconds at a fixed length.
Further, a normalizing treatment was performed at 220 ° C. for 45 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 Vinyl pyridine latex (41% by mass) 364.0 parts The RFL resin deposition rate of the thus obtained interwoven fabric was 5.5% by mass. The blind fabric was flat, no distortion due to heat shrinkage was observed at all, the warp cord density was uniform and there was no misalignment, and it was of high quality.

[0045]

[Comparative Example 1] In Example 1, except that the number of combined yarns after one-stage drawing was 3, the emulsion concentration of the finishing agent applied after the drawing was 30% by mass, and heat setting after the drawing was not performed was performed. In the same manner, spinning, drying and drawing were performed to produce a polyketone fiber having a fineness of 791 dtex. The tensile strength of the obtained polyketone fiber is 16.1 cN / dt.
ex, elastic modulus is 314 cN / dtex, dry heat shrinkage is 1.9%, maximum heat shrinkage stress is 0.72 cN / dte.
x and μd were 0.07.

This polyketone fiber was twisted in the same manner as in Example 1 (both twist / top twist 390 T / m: twist coefficient of top twist = 15512) to obtain a polyketone cord. The fineness of the cord made of this polyketone fiber is 180
1 dtex, tensile strength 13.1 cN / dtex,
The elongation under load of 2.0 cN / dtex is 3.0%, the maximum heat shrinkage temperature is 0.66 cN / dtex, and the dry heat shrinkage is 1.
It was 9%. A cord made of this polyketone fiber is used as a warp, and a cotton spun yarn of 10 ^s is used as a weft.
A weave fabric having 5 threads / 5 cm, weft density of 5 threads / 5 cm, and a width of 500 mm was woven. Μs of warp and weft is 0.08
Met. The length of the obtained bamboo blind fabric is 2 per 1 m.
There were 10 misalignments, and the quality was inferior to the suede woven fabric of Example 1.

[0047]

Comparative Example 2 The blind fabric obtained in Comparative Example 1 was treated with the RFL solution in the same formulation as in Example 2. The obtained fabric for RFL treatment had not only misalignment but also distortion due to heat shrinkage at 1 to 2 places per 1 m in length, and the flatness was poor and the quality was poor. The adhesion rate of the RFL resin of this blind fabric was 6.2% by mass.

[0048]

EFFECTS OF THE INVENTION The interwoven fabric of the present invention comprises a warp yarn made of polyketone fiber having excellent strength, dimensional stability and heat resistance, and a weft yarn, and has excellent mechanical and thermal properties. Furthermore, the interwoven fabric of the present invention has no misalignment due to slippage between the warp and the weft, does not cause distortion due to heat shrinkage, has excellent dimensional stability and flatness, and has no fluff or fibril-like material, pills, or powder. It is a graded woven fabric, such as twisted yarn and weaving,
It is also excellent in process passability such as RFL processing. The interwoven fabric of the present invention is preferably used as a rubber reinforcing material after applying an adhesive, specifically, a tire or a belt,
It is extremely useful as a fiber material for rubber reinforcement such as hoses.

[Brief description of drawings]

FIG. 1 is a schematic diagram of an apparatus for measuring a coefficient of static friction (μs) between a warp and a weft.

FIG. 2 is a schematic view of an apparatus for measuring a dynamic friction coefficient (μd) between polyketone fibers and polyketone fibers.

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Claims (9)

[Claims] 1. In a interwoven fabric composed of a warp and a weft, 50% by mass or more of fibers constituting the warp are polyketone fibers, and a fiber-fiber static friction coefficient (μs) between the warp and the weft is A blind fabric characterized by being 0.2 or more. 2. A cord containing a polyketone fiber in an amount of 50% by mass or more and having a maximum heat shrinkage stress of 0.01 to 0.
The interwoven fabric according to claim 1, which is 6 cN / dtex. 3. A cord containing a polyketone fiber in an amount of 50% by mass or more, the twisted yarn having a twist coefficient K of the upper twist of 1,000 to 30,000 and having a tensile strength of 7 cN / dtex or more, and , 2.0 cN / dt
The extruded fabric according to claim 1 or 2, which has an elongation of 5% or less under an ex load. K = Y × D ^0.5 (where Y is the number of twists per 1 m of cord (T / m),
D is the total display fineness (dtex) of the code) 4. The interwoven fabric according to claim 1, wherein the warp is a strand having a twist number of 0 to 100 T / m. 5. The polyketone fiber used for the warp has a tensile strength of 10 cN / dtex or more and an elastic modulus of 250 cN.
/ Dtex or more, shrinkage rate after dry heat treatment at 150 ° C for 30 minutes is 0 to 2%, and maximum heat shrinkage stress is 0.01 to 0.6c
N / dtex and fiber-fiber dynamic friction coefficient (μd)
Is 0.01 to 0.7.
4. The interwoven fabric according to any one of 4 above. 6. The total fineness of the warp is 300 to 30,000 dt.
Ex / this, the warp density is 5 to 80 threads / 5 cm, and the weft density is 1 to 10 threads / 5 cm, The blind fabric according to claim 1. 7. The blind fabric according to claim 1, wherein the resorcin-formalin-latex resin is provided in an amount of 0.1 to 10% by mass. 8. The interwoven fabric according to claim 1, wherein the weft is a cellulose fiber. 9. A rubber product, wherein the interwoven fabric according to any one of claims 1 to 8 is used at least in part.