JP6638134B2 - Highly processed polyetheretherketone yarn, method for producing the same, and woven / knitted fabric using the same - Google Patents

Description

The present invention is a polyetheretherketone bulky processed yarn which has not only excellent heat resistance and chemical resistance but also a good expansion and contraction rate, expansion elasticity and expansion recovery rate and an excellent appearance, and is less likely to generate fluff and dust. And a non-contact dry heat treatment.
In addition, the present invention relates to a woven or knitted fabric having a bulkiness and a stretch property using at least a part of a polyetheretherketone bulky processed yarn.

General-purpose thermoplastic synthetic fibers such as nylon and polyester fibers dissolve or hydrolyze in an acidic solution or an alkaline solution, whereas polyetheretherketone fibers have high resistance not only to an acidic solution or an alkaline solution but also to an organic solvent. Further, while the general-purpose thermoplastic synthetic fiber is melted at 300 ° C., the melting point is 340 ° C., the shape can be maintained even at 300 ° C., and the continuous usable temperature is 250 ° C. to 260 ° C., so that the heat resistance is excellent. Furthermore, since it has excellent radiation resistance and steam resistance, it is suitable for use in the medical field. Since no other outgassing occurs, it is a safe material to be used in extreme environments.
Therefore, for example, it is used in various shapes as an industrial part requiring heat resistance, chemical resistance, and abrasion resistance, as a molded part in a power plant, medical equipment, an automobile engine room, and the like.

Polyetheretherketone fiber, which is such an excellent material, is not only used as a single yarn, but is further processed into a textile shape such as a woven or knitted fabric or a braid, for example, heat resistance and abrasion resistance are required. It is used as a filter, a power station, a medical device, a harness covering material in an automobile engine room, and various reinforcing materials requiring high strength, abrasion resistance and heat resistance.
However, when used as these polyetheretherketone fibers, most of them are monofilaments (Patent Document 1) and multifilaments (Non-Patent Document 1), and these fibers and textiles such as woven and knitted fabrics using the same are used. It is not suitable for fields requiring stretch properties, such as insufficient stretch properties and poor recoverability even with stretchability.

As bulky processed yarns having excellent heat resistance, many methods for imparting bulky processing to heat-resistant and high-performance fibers have been researched and developed (Patent Document 2). However, a bulky yarn having excellent heat resistance and chemical resistance and excellent stretchability has not been put to practical use.

For example, as one of the cases that require stretch characteristics, if the woven or knitted fabric or braid is used for protective clothing with excellent heat and chemical resistance, conventional products have low shape fit when worn, making it difficult to perform activities. Alternatively, there is a problem that wearing discomfort occurs.
In addition, when used as a protective material for heat and chemicals, the elastic properties of the yarns that make up the textile are indispensable, especially for coating materials for industrial robots and other machinery that require the ability to follow deformation such as elongation and bending. However, since a yarn composed of polyetheretherketone fiber and having excellent stretch characteristics has not been put to practical use, it has not been realized.
In addition, polyetheretherketone is also used in various applications as a biomaterial, but as described above, a yarn made of polyetheretherketone fibers with excellent elasticity has not been put to practical use, Has not been developed for applications that require

  In order to solve these problems, the present inventors have improved the yarn processing equipment and developed a processing method capable of giving bulky processing to polyetheretherketone multifilament fibers, and if only heat resistance and chemical resistance are used, The development of polyetheretherketone bulky yarn with good stretchability, stretch elasticity, and elastic recovery is now under development.

JP 2008-240225 A JP 2005-307429 A

"Molten spinning of polyetheretherketone (PEEK)-cooling, thinning, and structure formation on spinning line", Journal of the Textile Society of Japan 49 (5), pp. 211-219, 1993

The present invention has been made in view of the above-described problems of the related art, and has as its object to provide a bulky yarn having good stretchability while maintaining the original properties of the material.
Another object of the present invention is to provide a production method that is practical in terms of productivity.
Further, another object of the present invention is to provide a woven or knitted fabric having excellent stretch characteristics.

  The present inventors have conducted intensive studies to achieve the above object,

In particular,
The bulky polyetheretherketone yarn according to the present invention is composed of a polyetheretherketone multifilament fiber having a single-fiber fineness of 0.05 tex or more and 1 tex or less, and has a stretchable elongation of 30% or more and 200% or less, and a stretchable elasticity of 30% or more and 200% or less. It is characterized in that it is 80% or more and 100% or less, and the expansion / contraction restoration rate is 30% or more and 55% or less.
The tensile strength is 0.2 N / tex or more and 0.5 N / tex or less, and the strain at the time of tensile strength is 20% or more and 60% or less.
The tensile strength, the maximum strain, and the expansion / contraction restoration rate in a tensile test after a dry heat treatment at 200 ° C. or more and 250 ° C. or less for 60 minutes are 90% or more as compared with those before the dry heat treatment.

The woven fabric according to the present invention is a woven fabric using at least a part of a polyetheretherketone bulky textured yarn, in which the stretchability of the polyetheretherketone bulky textured yarn constituting the textile is expressed as the stretchability of the textile. An elongation rate is 3% or more, and an elongation modulus (JIS L 1096) is 80% or more and 100% or less, and a residual strain is 10% or less after 10 times of repeated elongation tests for 10% elongation. .
The knitted fabric according to the present invention is a knitted fabric using at least a part of a polyetheretherketone bulky textured yarn, and the stretchability of the textile has an elongation modulus (JIS L 1018) of 10% or more and 100% or less. Features.

The method for producing a bulky polyetheretherketone yarn according to the present invention uses a polyetheretherketone multifilament fiber at a processing yarn speed of 50 m / min to 100 m / min and a spinner method of 2800 t / m to 3600 t. / M or less, and heat treatment is performed at a heating temperature of 280 ° C. or more and 330 ° C. or less using a non-contact type heater, and then the same number of twists is added in the direction opposite to the twisting.

The present invention is composed of a polyetheretherketone multifilament fiber having a single-fiber fineness of 0.05 tex or more and 1 tex or less. The tensile strength, the maximum strain, and the elasticity of the tensile test after a dry heat treatment at a rate of 30% or more and 55% or less and a dry heat treatment at 200 ° C. or more and 250 ° C. or less for 60 minutes are 90% or more as compared with those before the dry heat treatment. It has excellent stretch characteristics such as a good stretch ratio, stretch elastic modulus and stretch recovery ratio, and also has heat resistant stretch characteristics that can maintain stretch characteristics even in a high temperature environment.

  Hereinafter, embodiments according to the present invention will be described in detail. The embodiment described below is a preferred specific example for practicing the present invention, and thus various technical limitations are made. However, the present invention is particularly limited in the following description. It is not limited to these forms unless otherwise specified.

The polyetheretherketone multifilament fiber used for the polyetheretherketone bulky-processed yarn of the present invention has a plurality of filaments of 2 or more, preferably 20 to 100. Suitable for yarn flexibility and ease of manufacture.
Further, the single fiber fineness of the polyetheretherketone multifilament fiber is about 0.08 tex or more and 1.5 tex or less, preferably 0.08 tex or more and 0.6 tex or less. Suitable for ease of manufacture.
The fineness is represented by tex defined in JIS L 0101. For example, 1 tex indicates that a fiber having a length of 1000 m has a mass of 1 g. The measurement was performed in accordance with JIS L1013 8.3.1 A method.

The polyetheretherketone multifilament fiber used in the bulky polyetheretherketone yarn of the present invention has a tensile strength of 0.05 N / tex or more, more preferably 0.1 N / tex or more. If the tensile strength is less than 0.05 N / tex, filament breakage or yarn breakage in false twisting for imparting bulkiness occurs, and processing becomes impossible or productivity and quality are significantly reduced.
The tensile strength and the maximum strain are based on the tensile test (JIS L1013 8.5. 1) of the chemical fiber filament yarn, the maximum strength during the tensile test is defined as the tensile strength (N / tex), and the elongation at that time is defined as the maximum strain. (%).

Also, due to the false twisting processability for imparting the same bulkiness, the maximum strain of the polyetheretherketone multifilament fiber used for the polyetheretherketone bulky yarn needs to be 30% or more. In order to obtain a bulky textured yarn having more excellent stretchability, a polyetheretherketone filament fiber having a large maximum strain is suitable, and preferably has a maximum strain of 100% or more, more preferably 150% or more. . However, in the case of a polyetheretherketone multifilament fiber having a large maximum strain, it is difficult to perform uniform processing in the drawing step in false twisting. Therefore, the maximum strain of the polyetheretherketone multifilament fiber used for the polyetheretherketone bulky yarn is 30% or more and 200% or less, preferably 100% or more and 180% or less, more preferably 150% or more. 180% or less is good.

The single yarn fineness of the polyetheretherketone bulky processed yarn according to the present invention is 0.05 tex or more and 1 tex or less, preferably 0.05 tex or more and 0.3 tex or less. Suitable for use as a product and subsequent processing into textiles.

The tensile strength, which is one of the physical properties of the polyetheretherketone bulky yarn according to the present invention, is preferably from 0.1 N / tex to 0.5 N / tex, and more preferably from 0.25 N / tex to 0.5 N / tex. It is. If the tensile strength is less than 0.1 N / tex, filament breakage or yarn breakage occurs in the subsequent yarn processing such as twisting and weaving and knitting, resulting in a significant decrease in productivity and quality. . In addition, when performing false twisting to achieve physical properties such that the tensile strength exceeds 0.5 N / tex, the stretchability of the bulky polyetheretherketone yarn is not exhibited, which is not suitable. In particular, in order to obtain a polyetheretherketone bulky textured yarn having more excellent stretch characteristics, a polyetheretherketone multifilament fiber having a large maximum strain that can be drawn is suitable. When comparing the tensile strength of the ether ketone multifilament fiber and the polyether ether ketone bulky processed yarn according to the present invention, it is preferable that the tensile strength is equal (100%) or higher. Was compared with the tensile strength of the polyetheretherketone multifilament fiber before false twisting (tensile strength of polyetheretherketone bulky processed yarn / tensile strength of polyetheretherketone multifilament fiber before false twisting × 100). ), The range is 100% or less. 300% or less.
Due to similar workability to various textile processes and handleability as a single yarn, the polyetheretherketone bulky yarn according to the present invention also requires a maximum strain of 20% or more. In the case of a polyetheretherketone bulky processed yarn having a maximum strain of more than 60%, since the drawing is not uniformly applied, the quality of the bulked processed yarn greatly varies and is not suitable for practical use. The maximum strain is preferably 60% or less, more preferably 50% or less, from the viewpoint of the quality stability of the yarn physical properties. Also, in order to obtain a polyetheretherketone bulky textured yarn having more excellent stretch characteristics, a polyetheretherketone multifilament fiber having a large maximum strain is suitable, and to obtain a polyetheretherketone bulky textured yarn having excellent quality. Since it is preferable that the maximum strain is small, in order to obtain a high quality polyetheretherketone bulky processed yarn such as excellent stretch characteristics and small variations in physical properties, the maximum strain of the polyetheretherketone bulky processed yarn must be reduced. Maximum strain ratio compared to polyetheretherketone multifilament fiber before false twisting (maximum strain of polyetheretherketone bulky yarn / maximum strain of polyetheretherketone multifilament fiber before false twisting x 100) In this case, the range is preferably 10% or more and 70% or less.

As the expansion and contraction properties of the bulky processed yarn according to the present invention, "stretching elongation rate", "stretching elastic modulus" and "stretching recovery rate" which are generally used for evaluating the expansion and contraction properties of the bulked processing yarn are used. Specific measuring methods of each physical property were based on the following methods.
-Elasticity JIS L1013 8.11 A method
Calculate the “stretch elongation rate” and “stretch elastic modulus” as the stretchability. • Stretch recovery rate JIS L1013 8.12

The stretch rate of the polyetheretherketone bulky yarn according to the present invention is preferably 30% or more and 200% or less, more preferably 40% or more and 200% or less. If the stretch ratio is less than 30%, the texture created with the bulky yarn is reduced, and the stretchability cannot be obtained. On the other hand, if the expansion / contraction rate exceeds 200%, the strain becomes large even under a constant tension, so that quality control in the textile manufacturing process becomes difficult, which is not practical. The elastic modulus of elasticity is preferably 80% or more and 100% or less, more preferably 90% or more and 100 or less. If the elastic modulus is less than 80%, the yarn is hardly recovered after elongation, and the yarn is elongated.

The bulky processed polyetheretherketone yarn according to the present invention preferably has an elasticity recovery ratio of 30% or more and 5550% or less, and more preferably 40% or more and 55% or less. If the elasticity restoration ratio is less than 30%, the shape restorability when a load is applied and elongation is reduced, so that the physical properties of a woven or knitted fabric made of a bulky polyetheretherketone yarn and a product using the same are reduced. On the other hand, if the expansion / contraction restoration rate exceeds 55%, the crimp becomes large and quality control in the textile manufacturing process becomes difficult, which is not practical.

The polyetheretherketone bulky yarn according to the present invention has excellent heat resistance.
When left standing at 200 ° C. or more and 250 ° C. or less for 60 minutes, the physical properties of the tensile strength, maximum strain and elastic modulus of the polyetheretherketone bulky yarn before and after the dry heat treatment ((Polyetheretherketone bulky work after dry heat treatment) Tensile strength, maximum strain and elastic modulus of the yarn) / (tensile strength, maximum strain and elastic modulus of the polyetheretherketone bulky processed yarn before dry heat treatment) × 100) are 90% or more and 100% or less, preferably It is approximately equal to or higher than 95% and equal to or lower than 100%. When the elastic modulus of elasticity cannot be maintained at 90% or more even in an environment of 200 ° C. or more, it is difficult to use them together in a general environment in a room temperature region and a heat-resistant environment.
For example, operating area covering materials such as automatic transfer devices and robot arms that transfer between room temperature and high temperature environments in industrial machines and factories, etc., may have the same strength and elasticity in different temperature ranges as in room temperature environments. It is necessary.

The stretchability of a woven fabric using the polyetheretherketone bulky yarn according to the present invention for at least a part of the stretchable fabric is generally referred to as “elongation rate”, “elongation modulus”, or “elongation recovery” used for evaluation of stretchable fabrics. The "ratio", "residual strain", and "residual strain" after repeated elongation were used.
-Elongation rate JIS L1096 8.14.1 A method-Elongation modulus JIS L1096 8.13.1 A method-Elongation recovery rate JIS L1096 8.14.2 A method-Residual strain (after repeated elongation)
A repetitive elongation test at a constant strain (for example, 10%) with respect to the sample length is performed at a rate of 100% strain / min, and the strain at the initial load is repeated from the result of the nth elongation test as in the elongation modulus measurement. Measured as residual strain during elongation.

The stretch characteristics of a knitted fabric using at least a part of the polyetheretherketone bulky processed yarn according to the present invention include "stretch elastic modulus" generally used for evaluation of stretchable knitted fabric, and "hysteresis at the time of a repeated stretch test. Loss "was used.
-Elongation modulus JIS L1018 8.15.1. Method A ・ Hysteresis loss (during repeated elongation)
A repeated elongation test at a constant strain (for example, 20%) with respect to the sample length is performed at a rate of 100% strain / min, and the amount of energy (energy increase) required at the n-th elongation and the amount of energy (energy restored at the time of recovery) Hysteresis loss is calculated from the following equation:

As a stretching property of the woven fabric using the polyetheretherketone bulky processed yarn according to the present invention, the elongation rate in the yarn direction using the polyetheretherketone bulky processed yarn is 3% or more, preferably 5% or more. Similarly, it is preferable that the elastic modulus in the yarn direction using the polyetheretherketone bulky yarn is 80% or more and the residual elongation is 1% or less. Furthermore, it is preferable that the residual strain after 10 times of 10% repetitive elongation is 5% or less.
The elongation rate of 3% or more as the stretch property of the woven fabric is a set value assuming outer clothing such as work clothes, etc. If it is not at least 3% or more, the movement at the time of wearing is restricted and it is very comfortable to work This is because it is preferably at least 5%. For the same reason, it is necessary that the elongation modulus, which is a measure of recovery after elongation, is 80% or more and the residual elongation is 1% or less. In addition, since it is not practical if the stretching property is reduced by the frequency of use, it is required that the residual strain after 10 times 10% strain repeated elongation is 5% or less.

In the present invention, a dry heat type false twisting method can be used as a method for producing the bulky polyetheretherketone yarn.
Specifically, the polyetheretherketone multifilament fiber is drawn between two rollers at a constant feed rate, and is heat-set with a dry heat heater. A twisting mechanism for twisting the polyetheretherketone multifilament fiber after the dry heat heater imparts a reverse twist to the polyetheretherketone multifilament fiber before and after the twisting mechanism. By being fixed by heat and being untwisted at the rear, a crimping property is imparted to the yarn, and a bulky polyetheretherketone processed yarn having excellent elasticity can be obtained.

As the twisting method of the false twisting method in the present invention, any method such as a spinner method, a friction method, and a belt nip method may be used, and is not particularly limited as long as bulking can be performed. However, since the polyetheretherketone multifilament fiber has good slidability, it is preferable to twist the fiber by a spinner method.

Any type of heater for the heat treatment may be used as long as heat treatment in a high-temperature region of 280 ° C. or higher is possible, but a non-contact type in which the traveling path of the yarn to be processed does not contact the heater. Heater is good. When processing is performed by a contact-type heater, the effect of heat is different between polyetheretherketone multifilament fibers running on a contact surface and polyetheretherketone multifilament fibers running on a non-contact surface. In particular, when heat treatment is performed in a high-temperature region of 280 ° C. or more as in the present invention, the difference is remarkable, and regions having different physical properties are mixed in the same polyetheretherketone bulky processed yarn. appear. On the other hand, by using a non-contact type heater, it is possible to prevent deterioration in physical properties or quality after processing.

The heating temperature for the heat treatment is from 280 ° C to 330 ° C, preferably from 300 ° C to 325 ° C. If the temperature exceeds 330 ° C., filament breakage occurs, and the quality of the bulky processed yarn after processing deteriorates. On the other hand, when the temperature is 280 ° C. or lower, the quality of the bulky processed yarn after processing is deteriorated, for example, the stretchability and the elastic modulus are reduced.

The twist direction of the processing conditions may be either the s direction or the z direction.
The number of twists is preferably 2800 t / m or more and 3600 t / m or less. If the processing is performed with a twist number lower than 2800 t / m, sufficient stretch characteristics of the polyether ether ketone bulky processed yarn cannot be obtained, and if the processing is performed with a twist number higher than 3600 t / m, filament breakage or yarn breakage occurs during processing. And a stable processing state cannot be obtained.
The feed rate of the processing conditions is preferably 35% or more and 55% or less. If the processing is performed at a feed rate lower than 35%, sufficient stretch characteristics of the polyetheretherketone bulky processed yarn cannot be obtained, and if the processing is performed at a feed rate higher than 55%, filament breakage or yarn breakage occurs during processing. Frequent occurrence and stable processing state cannot be obtained. Here, the feed rate F% is F = (V1 / V2), where V1 is the yarn speed by the positive roller before the heater, and V2 is the yarn speed by the roller after the twisting section in the spinner. It is a value represented by × 100.
The processing yarn speed under the processing conditions is preferably from 50 m / min to 100 m / min. When processing at a yarn speed lower than 50 m / min, the rotation of the feed roller for setting a constant feed rate and the fluctuation of the de-spreading tension of the yarn become large. Can not be obtained. Furthermore, it is not realistic due to low productivity. If processing is performed at a processing speed higher than 100 m / min, the filaments and yarns of the polyetheretherketone bulky processed yarn frequently occur during processing, so that a stable processing state cannot be obtained.

The woven or knitted fabric using the polyetheretherketone bulky yarn of the present invention has excellent heat resistance because the continuous usable temperature of the polyetheretherketone is from 250 ° C to 260 ° C. It has excellent chemical resistance, such as high resistance to organic solvents, and has the characteristics of a material that does not generate outgas and is safe even when used in an extreme environment. It is expected to be developed in various industrial fields. In particular, demand is expected for members that require elasticity, heat resistance, and environmental resistance, such as members that protect the moving parts of industrial machines. It can be used for textile products other than woven and knitted fabrics, for example, it can be used for braids.
Furthermore, because of its excellent radiation resistance and steam resistance, polyetheretherketone bulky processed yarn is also expected to be used in the medical field, where molded products have been mainly used.

Next, the present invention will be specifically described with reference to examples.

[Example 1]
As Example 1, a polyetheretherketone multifilament fiber composed of 48 polyetheretherketone fibers having a single yarn average diameter of 26.8 μm (16.7 tex / 48f, Kuraray Co., Ltd., tensile strength 0.17 N / tex, False twisting was performed using the maximum strain of 160%) to obtain a polyetheretherketone bulky processed yarn according to the present invention.

The polyether ether ketone bulk processing was performed by a spinner method using a false twisting machine (TH-312 MK type manufactured by Aiki Seisakusho). The first heater for fixing the twist was processed using a non-contact type ceramic heater capable of heating up to 500 ° C. Processing was performed at a yarn speed of 70 m / min, a feed rate of 50%, a number of false twists of 3500 t / m, and a heater temperature of 320 ° C. The spinner used was a single spinner and was wound once.
The physical properties of the false twisted polyetheretherketone bulky yarn (Example 1) were measured. As comparative examples, polyetheretherketone multifilament fibers (Comparative Example 1) and monofilament fibers (Comparative Example 2) before false twisting were used. The physical properties of the fibers of Comparative Examples 1 and 2 were measured in the same manner as in Example 1. Table 1 shows the results.

The fineness of the polyetheretherketone bulky processed yarn of Example 1 is 8.65 tex, the tensile strength is 0.3 N / tex, the maximum strain is 28.8%, the elongation is 76.4%, the elastic modulus is 96.1%, and the elasticity is 96.5%. The restoration rate was 47.8%, indicating that the yarn had high tensile strength and excellent stretchability. Conversely, in the case of the polyetheretherketone fibers of Comparative Examples 1 and 2, the tensile strength is low and the strain is large, but the stretch rate is 5% or less, and the stretch recovery rate is 10% or less. Is not suitable.

As a result of using the plying machine (manufactured by Ishikawa Seisakusho Co., Ltd.) to twist the polyetheretherketone bulky processed yarn of Example 1, the workability in the twisting process and the yarn after the twisting were processed. No problems were found in the visual inspection.
A weaving test was performed using only the polyetheretherketone bulky processed yarn of Example 1 as the weft of a rapier loom (ER Rapier manufactured by Tsuda Koma Kogyo Co., Ltd.). As a result, there was a problem in weaving properties and appearance inspection of the woven fabric after weaving. Was not seen.
In addition, as a result of a knitting test using a circular knitting machine (manufactured by Eiko Sangyo Co., Ltd.) using only the polyetheretherketone bulky processed yarn of Example 1, problems were found in knitting properties and appearance inspection of the knitted fabric after knitting. I couldn't.
Furthermore, as a result of performing braid processing using a braid machine (manufactured by Kokubun Tekko Co., Ltd.) using only the polyetheretherketone bulky processed yarn of Example 1, the workability in the braid processing step and the appearance inspection after braid processing were performed. No problem was seen.
From the above results, it is found that the polyetheretherketone bulky processed yarn of the present invention can be processed without any problem in the textile production process.

[Example 2]
As a heat resistance evaluation sample, a sample subjected to dry heat treatment in which the polyetheretherketone bulky processed yarn of Example 1 was allowed to stand at 230 ° C. for 60 minutes was used as Example 2. As a comparative sample, a polyester false twisted yarn (8.4 tex / 36f, manufactured by Toray Industries, Inc.) was used as Comparative Example 3 of a general-purpose yarn having excellent stretch characteristics, and a dry heat treatment was performed in the same manner to obtain Comparative Example 4.
The heat resistance was evaluated by measuring the tensile strength, the maximum strain, and the expansion / contraction restoration rate as physical properties before and after the dry heat treatment test, and assuming the rate of change as “ratio”, the following formula: ratio = (physical property value after dry heat treatment) / (Physical properties before dry heat treatment) and evaluate.
Table 2 shows the test results.

The dry-heat-treated polyetheretherketone bulky textured yarn of Example 2 has almost no decrease in the fineness, tensile strength, maximum strain, and expansion / recovery ratio as compared with before the dry heat treatment, and can maintain the physical properties, and is excellent in heat resistance. ing. On the other hand, in the case of the polyester false twisted yarn after the dry heat treatment in Comparative Example 4, the fineness and the maximum strain are the same, but the tensile strength is reduced by about 40% and the elasticity recovery rate is reduced by 17% from Comparative Example 3. Therefore, physical properties cannot be maintained until after the dry heat treatment, and heat resistance is poor.

[Example 3]
In Example 3, a polyester multifilament fiber (8.4 tex / 36f manufactured by Toray Industries Co., Ltd.) was used by using an ER rapier loom manufactured by Tsuda Koma Kogyo Co., Ltd., using a polyetheretherketone bulky processed yarn (Example 1) as a weft. ) Was used as the warp yarn, and weaving was performed at a warp yarn density of 68 yarns / cm and a weft yarn density of 28 yarns / cm using a warp double structure (both sides satin weave). As a comparative example, the same weaving process was performed using a polyetheretherketone multifilament fiber and a monofilament fiber having no stretch characteristics (Comparative Examples 1 and 2) and a polyester false twisted yarn having a stretch characteristic (Comparative Example 3). Then, Comparative Examples 5 to 7 were performed.

The elastic properties of this woven fabric sample were evaluated by observing the appearance at 5% and 10% elongation, and by elongation modulus, residual elongation, elongation, and residual strain of the woven fabric after ten repeated elongation tests.
The appearance of the sample at 5% and 10% elongation was observed using an Autograph AG manufactured by Shimadzu Corporation, and the shape of the sample obtained by applying 5% and 10% strain to a 30 mm wide sample at a rate of 100% strain / min. Was visually observed to evaluate the retention of the woven fabric shape. In the evaluation, “○” indicates no misalignment, “×” indicates misalignment, and “△” indicates partial misalignment. The results are shown in Table 3. Note that “misalignment” is a phenomenon in which a gap occurs between warp yarns of a woven fabric. If misalignment is observed in all three measured samples, it is determined that there is a misalignment of “x” and three misalignments are detected. When misalignment was observed in one or all of the samples, it was determined that some misalignment occurred with “Δ”.

In the appearance inspection at the time of elongation, in the case of Comparative Example 6, misalignment was observed at 5% elongation, and at 10% elongation, misalignment was completely generated. Therefore, the polyetheretherketone monofilament of Comparative Example 2 was observed. The woven fabric of Comparative Example 6 using fibers has no stretch property. Therefore, the subsequent evaluation was performed in Example 2 and Comparative Examples 5 and 7.

The elongation modulus and residual strain of the woven fabric were measured at a sample width of 30 mm and an initial load of 0.5 N according to JIS L1096 8.13.1A method.
The elongation modulus of the woven fabric was measured according to JIS L1096 8.14.1A method, with a sample width of 30 mm and an initial load of 0.5N.
The evaluation of the repetitive stretching characteristics of the woven fabric was performed by repeating a 10% repetition elongation test with respect to the sample length 10 times at a rate of 100% strain / min. The strain at (0.5N) was measured as the residual strain during repeated elongation.
Table 4 shows the results.

Comparing the elongation percentages, which are the stretch characteristics of the woven fabric, it is found that Example 3 and Comparative Example 7 are 3% or more, whereas Comparative Example 5 is very small at 1.2%, indicating almost no stretchability. In addition, Example 3 shows an elongation ratio of 14% and 5% or more, which indicates that the woven fabric has very good stretch characteristics.
When the elongation elastic modulus and the residual strain, which are the elastic properties of the woven fabric, are compared, Example 3 and Comparative Examples 5 and 7 show that the residual elongation is within 1%, the elongation elastic modulus is 80% or more, and the elastic properties are good. Understand. In particular, in the case of Example 3 and Comparative Example 7, the residual strain is within 0.75%, the elongation modulus is 85% or more, and it can be seen that the stretch characteristics are excellent.
Further, in the cyclic elongation test, Example 3 and Comparative Example 7 had excellent residual elasticity after repeated elongation of 5% or less, whereas Comparative Example 5 had residual elongation after repeated elongation of 6%. It is 53% and has poor durability and stretchability, and is not practical as a material requiring stretchability.

[Example 4]
In Example 4, a knitting process was performed using a circular knitting machine (NCR-B, 24G, manufactured by Eiko Sangyo Co., Ltd.) using a polyetheretherketone bulky processed yarn (Example 1). As a comparative example, the same knitting process was performed using a polyetheretherketone multifilament fiber having no stretch characteristics (Comparative Example 1), and Comparative Example 8 was obtained.
JIS L1018 8.15.1. The elongation modulus was measured in accordance with Method A. As the sample, the knitted sample from the circular knitting machine is used in the same width, and the elongation modulus at 20% elongation is 100 mm, the initial load is 0.1 N, and the elongation elasticity measurement load is the same as the initial load. The measurement was carried out at 1N, 1 and 5 repetition times. Further, the hysteresis loss was determined from the difference between the amount of energy required during elongation (increased energy) and the amount of energy restored during recovery (decreased energy). Table 5 shows the results.

Comparing the elongation elastic modulus, which is the elastic characteristic of the knitted material, it can be seen that in Example 4, both the first and fifth repeated elongation had an elongation elastic modulus of 10% or more, and the elastic characteristic was good. On the other hand, the elongation modulus of Comparative Example 8 was -16.7% at the first time, -35.9% at the fifth time, and the elongation modulus at the time of 20% elongation was shown by a negative value of the elongation modulus. The shape of the knitted fabric has not been restored, which is not preferable as a material requiring stretch characteristics.
In addition, the hysteresis loss of Example 4 was 71.7% at the first time and 61.9% at the fifth time, both of which were 80% or less. It can be seen that the elongation recovery characteristics are inferior at 88.8% for the first time and 93.2% for the fifth time.

[Example 5]
Example 5 is a sample when the same apparatus as in Example 1 is used and the number of twists under the processing conditions is 3000 t / m. Further, as Comparative Examples 9 to 12, samples having twist numbers of 500, 1000, 2000, and 4000 t / m under processing conditions were processed. Tables 6 and 7 show the results of evaluating the processability and the physical properties of the yarn. The evaluation of the workability was "good" for good workability, "x" for no workability, and "△" for workability but not practical.

When processing is performed at 4000 t / m with a twist number higher than 3600 t / m as in Comparative Example 12, filament breakage and yarn breakage occur frequently during processing, and a stable processing state cannot be obtained.
Therefore, the number of twists of the polyetheretherketone bulky yarn under false twisting conditions is preferably 3600 t / m or less.

Table 7 shows the evaluation results of various physical properties of Examples 1 and 5 and Comparative Examples 9 to 11.

In the case of Examples 1 and 5, the stretch ratio is in the range of 30% to 200%, the stretch modulus is in the range of 80% to 100%, and the stretch restoration ratio is in the range of 30% to 55%. Have been. However, when processing is performed with a twist number lower than 2800 t / m as in Comparative Examples 9 to 11, the bulkiness of the processed polyetheretherketone bulky processed yarn is reduced, and the expansion and contraction rate is reduced in Comparative Example 9 and Comparative Example 10, the elasticity of elasticity is 80% or less in Comparative Examples 9 to 11, and the elasticity of elasticity is 30% or less in Comparative Examples 9 to 11, and the elasticity cannot be obtained.

[Examples 6 and 7]
Examples 6 and 7 are samples obtained by using the same apparatus as in Example 1 and setting the heater temperature to 280 ° C. (Example 6) and 300 ° C. (Example 7) as the processing temperature conditions. Further, as Comparative Examples 13 and 14, samples having heater temperatures of 260 ° C. (Comparative Example 13) and 340 ° C. (Comparative Example 14) were processed.

Table 8 shows the results of evaluating the workability.

  In Examples 1, 6, 7 and Comparative Example 13, there was no problem in workability, but in Comparative Example 14, filament breakage and thread breakage occurred frequently during processing, and a stable processing state could not be obtained. This is because if the processing temperature at the time of twisting is high, the strength of the polyetheretherketone fiber is reduced by approaching the melting point of the polyetheretherketone fiber, and filament breakage occurs during false twisting. It has been found that a processing temperature of 320 ° C. or less is suitable.

Table 9 shows the results of evaluating the physical properties of Examples 1, 6, 7 and Comparative Example 13 in which the heater temperature was changed.

In the case of Examples 1, 6, and 7 processed at a heater temperature of 280 ° C. or more and 320 ° C. or less, the stretching elongation is 30% or more and 200% or less, the stretching elasticity is 80% or more and 100% or less, and the stretching recovery rate is It is in the range of 30% or more and 55% or less, and stretch characteristics are obtained. On the other hand, when processing is performed at a temperature lower than 280 ° C., the stretch ratio becomes 30% or less, and sufficient stretch characteristics are not obtained. This is because if the processing temperature at the time of twisting is low, the bulky shape by the false twisting cannot be sufficiently fixed, so that the elastic property when a load is applied decreases.

Example 8
Example 8 is a sample using the same apparatus as in Example 1 and having a feed rate of 40% as a processing condition. Further, as Comparative Examples 15 and 16, the feed rates were processed at 30% and 60%. Table 10 shows their workability.

From the evaluation results of the workability in Table 10, it is understood that the feed rates of the processing conditions of 40% and 50% are suitable. When processing is performed at a feed rate higher than 60%, the feed rate is too large to exceed the elongation limit of the polyetheretherketone multifilament fiber, and filament breakage occurs and a stable processed state cannot be obtained. On the other hand, when the feed rate is as low as 30%, the draw ratio is low, so that the drawing unevenness of the polyetheretherketone multifilament fiber becomes large, so that the tension fluctuation during processing becomes large, and the filament breakage or yarn breakage resulting from the breakage occurs. And a stable processing state cannot be obtained.

Table 11 shows the measurement results of the physical properties of Example 8 in the same manner as in Example 1.

The physical properties of the bulky polyetheretherketone processed yarn at feed rates of 40% and 50% show values within the preferred range of the present invention.

[Example 9]
Example 9 is a bulky polyetheretherketone processed yarn using the same apparatus as in Example 1 and changing the processed yarn speed to 100 m / min as processing conditions. Further, as Comparative Examples 17 and 18, using the same apparatus as in Example 1, processing was performed at a processing yarn speed of 40 m / min and 150 m / min. Table 12 shows their workability.

When processing is performed at a low yarn speed of 40 m / min or less, the processing is performed at a low speed, so that the processing tension is reduced and the fluctuation of the processing tension is increased. Filament breakage occurs due to sliding, etc., and a stable processing state cannot be obtained. Conversely, when processing is performed at a high processing speed of 150 m / min or more, a high processing tension causes filament breakage and thread breakage in the heating heater portion, and a stable processing state cannot be obtained.

Table 13 shows the measurement results of physical properties of the polyetheretherketone bulky processed yarn of Example 9 which could be processed stably in the same manner as in Example 1.

When processed at a processing yarn speed of 50 m / min or more and 100 m / min or less, the physical properties of the polyetheretherketone bulky processed yarn show values within the preferred range of the present invention.

Claims (6)

It is made of polyetheretherketone multifilament fiber having a single-fiber fineness of 0.05 tex or more and 1 tex or less, and has a stretch elongation of 30% or more and 200% or less, an elastic modulus of 80% or more and 100% or less, and an elastic recovery of 30% A polyether ether ketone bulky textured yarn having a content of not less than 55% or less. The polyetherether according to claim 1, wherein a tensile strength measured by a tensile test (JIS L 1013) is 0.2 N / tex or more and 0.5 N / tex or less, and a maximum strain is 20% or more and 60% or less. Ketone bulky yarn.   A tensile test (JIS L 1013) after a dry heat treatment at 200 ° C. or more and 250 ° C. or less for 60 minutes has a tensile strength, a maximum strain, and an elastic recovery ratio of 90% or more as compared with those before the dry heat treatment. The bulky textured polyetheretherketone yarn according to claim 1 or 2. A woven fabric using the polyetheretherketone bulky textured yarn according to claim 1, 2 or 3 as at least a part thereof, wherein the stretchability of the polyetheretherketone bulky textured yarn constituting the textile is exhibited as the textile stretchability. The elongation rate in the direction of the elongation is 3% or more, and the elongation modulus (JIS L 1096) is 80% or more and 100% or less, and the residual strain after 10 times of repeated elongation tests of 10% elongation is 5% or less. Characteristic woven fabric. A knitted fabric using the polyetheretherketone bulky processed yarn according to claim 1, 2 or 3 for at least a part thereof, wherein the textile has a stretch elasticity (JIS L 1018) of 10% or more and 100% or less. A knitted fabric characterized by being. Using a filament fiber of polyetheretherketone, a twisting number of 2800 t / m or more and 3600 t / m or less using a spinner method at a processing yarn speed of 50 m / min or more and 100 m / min or less, and a non-contact type heater A method for producing a bulky processed polyetheretherketone yarn in which a heat treatment is performed at a heating temperature of 280 ° C. or more and 330 ° C. or less, and then the same number of twists is applied in the opposite direction to the twisting.