JP2001123324A - Polyphenylene sulfide monofilament and sleeve for protecting cable - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a PPS monofilament which maintains the highly thermally stable quality, even when used at an extremely high temperature for a long time, scarcely has the irregularity of the diameter and can suitably be used for sleeves for protecting cables such as electric product cables and vehicle cables, and to provide a cable-protecting sleeve which comprises the PPS monofilaments and has excellent heat resistance, hydrolysis resistance, chemical resistance, flame retardancy and abrasion resistance. SOLUTION: This polyphenylene sulfide monofilament has a tensile strength retention of >=90% after a thermal treatment at 200 deg.C for 100 hr and that of >=80% after a thermal treatment at 200 deg.C for 400 hr, and the cable-protecting sleeve comprises the monofilaments.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention
Polyphenylene sulfide monofilament and polyphenylene sulfide monofilament that maintain extremely stable quality thermally even when used at high temperatures, have small unevenness in diameter, and can be suitably used for cable protection sleeve applications such as electric product cables and vehicle cables. And a cable protection sleeve comprising:

[0002]

2. Description of the Related Art Polyphenylene sulfide (hereinafter referred to as P
PS) is excellent in heat resistance, chemical resistance, flame retardancy, etc., and can be melt-molded. In addition to molded products that require these properties, it is used as a film or fiber. Widely used. Above all, PPS fibers make use of their excellent heat resistance, chemical resistance and flame retardancy, and are used for industrial fabrics such as papermaking and canvas, filters,
It is used in various applications, such as electrical insulation and brush bristles.

[0003] Regarding such a PPS fiber spinning technique, it can be easily formed into fibers by a melt spinning method similar to that of a general-purpose thermoplastic polymer.
No. 4617, and many proposals have been made with respect to a technique for producing PPS fibers and a technique for improving fibers.

For example, Japanese Patent Application Laid-Open No. 61-215715 discloses a high viscosity polyarylene thioether (PPS).
By carrying out melt spinning using, a tensile strength of 40 k
g / mm ² or more, tensile strength at 200 ° C. 20 kg /
A technique for obtaining a polyarylene thioether fiber having a characteristic of at least ² mm ² is disclosed in Japanese Patent Application Laid-Open No. 64-396.
No. 1 discloses that a PPS unstretched yarn is stretched in one step at a ratio of not less than a natural stretching ratio and then at 150 to 260 ° C.
Mechanical properties and heat resistance by performing constant length heat treatment at a temperature equal to or higher than the stretching temperature of the first stage, or by performing two-stage stretching in the same temperature range so that the total stretching ratio is 1-2 times the stretching ratio of the first stage. A technique for obtaining a PPS fiber having improved chemical resistance is disclosed.

[0005] Also, JP-A-1-229809 and JP-A-1-239109 disclose that PPS is melt-spun and subjected to one-step stretching using a heating element.
A technique is disclosed in which after heat setting using a heating element of up to 140 ° C., heat setting is further performed using a heating element having a surface temperature of 150 ° C. or higher and a melting point or lower to thereby obtain PPS fibers that are fuzzy and have extremely few single yarn breaks. Have been.

Further, Japanese Patent Application Laid-Open No. Hei 4-222217 discloses that unstretched yarn obtained by melt-spinning PPS is 80-26.
After stretching 2 to 7 times at 0 ° C, 0.1 to 30 at a take-up ratio of 0.8 to 1.35 times in a dry heat atmosphere of 285 to 385 ° C.
A technique is disclosed in which a PPS fiber having a tensile strength of 3.5 g / d or more and a knot strength of 2.5 g / d or more and having improved bending wear and bending fatigue characteristics is obtained by heat-treating for seconds.

[0007] The inventors of the present invention have also studied similar techniques. As a result, unstretched linear PPS having a melt flow rate of 200 g / 10 min or less was melt-spun and cooled in hot water at 60 ° C or higher. The monofilament is then subjected to primary stretching at a ratio of primary stretching ratio / total stretching ratio of 0.88 or less, and then to multiple stretching so that the total stretching ratio becomes 4 times or more, and then to a relaxation heat treatment in an air bath at 200 to 280 ° C. To produce an excellent PPS monofilament by balancing tensile strength and knot strength (JP-A-62-29951).
No. 3) and a melt flow rate of 20 to 120 g /
A PPS monofilament obtained by spin-drawing PPS for 10 minutes, the difference between the dry heat shrinkage at 200 ° C. (Sd200) measured in a free state and the dry heat shrinkage (Sd140) also measured at 140 ° C. Absolute value ΔSd is 3.0%
Hereinafter, Sd200 is 15 to 32%, and the strength is 3.5.
PPS monofilament having properties suitable for papermaking spiral canvas having characteristics of g / d or more, and a method for producing this PPS monofilament
No. 195318).

In addition to the above-described PPS fiber spinning technology and PPS fiber improvement technology, some proposals have already been made for industrial materials using PPS fibers, for example, Japanese Patent Application Laid-Open No. 61-6390. Gazette, JP-A-3-3
No. 2711, JP-A-2-71809, JP-A-6-22413, JP-A-2-126622, JP-A-10-273825, JP-A-11-6
Patent No. 1584 and Japanese Patent Application Laid-Open No. 11-93028 disclose PPS fiber in a bag filter, a nonwoven fabric for filtration,
It is disclosed to be applied to various uses such as a nonwoven fabric for papermaking, a cloth for a dryer, an electrical insulating material, a cord for reinforcing automobiles and a binding material for a motor.

[0009] Among these patents for use, a cable protective sleeve using PPS fiber (hereinafter sometimes simply referred to as a protective sleeve) and a technique similar thereto are disclosed in JP-A-10-273825 and JP-A-10-273825. Kaiping 1
Although these are described in Japanese Patent Application Laid-Open No. 1-61584, they all use PPS multifilaments, and from the viewpoint of appropriate flexibility required as a protective sleeve, none of these technologies exhibit excellent characteristics. However, this protective sleeve has poor durability against friction and abrasion due to abrasion due to the small diameter of the single yarn of the PPS fiber constituting the protective sleeve. Coating with a surface treating agent such as an agent or rubber has been required, leading to a significant cost increase.

On the other hand, monofilament materials which have been preferably used for protective sleeve applications include polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyamide resins such as nylon 6 and nylon 66; And vinylidene chloride and polyvinylidene fluoride.

However, among the above, when a protective sleeve using a polyester resin monofilament is used in an environment where the temperature is extremely high, such as in an engine room of an automobile, the influence of rainwater and the like also overlaps. This included the problem that the monofilament was liable to undergo hydrolysis degradation and was inferior in durability.

A protective sleeve using a monofilament made of a polyamide resin has a very good characteristic in terms of flexibility and has no problem such as hydrolysis.
Since it is inferior in chemical resistance and the like, it has a problem that its use is extremely limited.

Further, although a protective sleeve made of a monofilament made of polyvinylidene chloride or polyvinylidene fluoride is excellent in terms of chemical resistance, etc., when an electric product or an automobile using these is discarded and then incinerated, There is a problem in that it becomes a source of toxic gas such as dioxin and hydrogen fluoride, and may cause environmental pollution.

On the other hand, it is known that PPS is excellent in heat resistance and hydrolysis resistance, so that it does not cause a problem in use at high temperatures, and has a chemical resistance comparable to that of fluororesins. It has the feature of being excellent.

[0015] In addition, PPS may generate sulfurous acid gas during incineration.
Since the desulfurization technology using the desulfurization device has been established, it can be said that the environmental pollution is extremely superior to the above-mentioned polyvinylidene chloride or polyvinylidene fluoride.

[0016] However, despite having such excellent characteristics, PPS has a large unevenness in diameter when formed into a monofilament and has a large quality change under an extremely high temperature atmosphere. In fact, it has been hesitant to apply to the monofilament protective sleeve used.

[0017]

SUMMARY OF THE INVENTION The present invention has been accomplished in view of the above-mentioned situation, and has been accomplished as a result of an investigation for solving the problems in the prior art. A PPS monofilament and a PPS monofilament which maintain a very stable quality thermally even in a case and have a small unevenness in diameter and can be suitably used for a cable protection sleeve application such as an electric product cable and a vehicle cable.
An object of the present invention is to provide a cable protective sleeve made of S monofilament having excellent heat resistance, hydrolysis resistance, chemical resistance, flame retardancy and abrasion resistance.

[0018]

The inventors of the present invention have made various studies to achieve the above-mentioned object. As a result, even after performing a dry heat treatment at an extremely high temperature for a long period of time, the monofilament does not need to be dried before the heat treatment. PPS monofilament with very small variation in average diameter, and monofilament with very low tensile strength retention, that is, very low strength reduction before dry heat treatment of monofilament even after extremely high temperature and long time dry heat treatment, and both properties The present inventors have found that PPS monofilaments satisfying the above object satisfy the above-mentioned object, and that when these PPS monofilaments are used for a cable protection sleeve, an optimum effect is exhibited, and the present invention has been achieved.

That is, the PPS monofilament of the present invention has a tensile strength retention of 90% or more after a dry heat treatment at 200 ° C. for 100 hours.
The monofilament has a tensile strength retention of 80% or more after a dry heat treatment at 0 ° C. for 400 hours.

In the PPS monofilament of the present invention, the fluctuation rate of the average diameter of the monofilament after performing the dry heat treatment at 200 ° C. for 400 hours with respect to the monofilament before the dry heat treatment is 4% or less, and the drying rate at 250 ° C. for 400 hours. The variation rate of the average diameter of the monofilament after the heat treatment to the monofilament before the dry heat treatment is 7%.
It is characterized by the following.

Furthermore, the PPS monofilament of the present invention has a monofilament having a tensile strength retention of 90% or more after a dry heat treatment at 200 ° C. for 100 hours.
The monofilament has a tensile strength retention of 80% or more after the dry heat treatment at 400 ° C. for 400 hours, and
The monofilament after the dry heat treatment at 400 ° C. for 400 hours has an average diameter variation of 4% or less with respect to the monofilament before the dry heat treatment, and the monofilament after the dry heat treatment at 250 ° C. for 400 hours before the dry heat treatment The variation rate of the average diameter with respect to is not more than 7%.

In the PPS monofilament of the present invention, the diameter of the monofilament is 0.1 to 1.0 m.
m, less than 15% of unevenness in diameter relative to the average diameter of the monofilament measured in the fiber axis direction, and a tensile strength of 2.2 cN /
dtex or more, tensile elongation at break of fiber 20% or more, 1
It is more preferable that the dry heat shrinkage at 80 ° C. is 1.0 to 10.0%.

The cable protective sleeve of the present invention is made of a PPS monofilament, particularly the above-mentioned PPS monofilament, and more specifically, the above-mentioned PP
It is characterized in that a plurality of S monofilaments are aligned and tied, and can be preferably used particularly as a signal transmission protection sleeve or a vehicle protection sleeve.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail.

The PPS monofilament of the present invention has 20
The tensile strength retention after performing the dry heat treatment at 0 ° C. for 100 hours is 90% or more, and the tensile strength retention after performing the dry heat treatment at 200 ° C. for 400 hours is 80% or more. Even when used for a long time under high temperature, it is characterized by showing good strength retention,
The tensile strength retention after dry heat treatment at 200 ° C. for 100 hours is 95% or more, more preferably 97% or more;
When the strength retention after dry heat treatment at 400C for 400 hours is 85% or more, more preferably 90% or more, it leads to the manifestation of a more suitable effect.

That is, PP satisfying the above-mentioned strength retention rate
If it is an S monofilament, it will maintain good durability against heat even under the use environment in which it is used as an actual cable protection sleeve, and configure the sleeve after being tied even when used for an extremely long time. The monofilament does not break due to the bending of the sleeve or contact with other components, and the situation such as fraying of the sleeve does not occur.

In the PPS monofilament of the present invention, the variation rate of the average diameter of the monofilament after performing the dry heat treatment at 200 ° C. for 400 hours with respect to the monofilament before the dry heat treatment is 4% or less.
The variation rate of the average diameter of the monofilament after the dry heat treatment for 7 hours with respect to the monofilament before the dry heat treatment is 7%.
% Or less, that is, the diameter variation rate is small even when used for a long time at a high temperature, but the variation rate of the average diameter of the monofilament after dry heat treatment at 200 ° C. for 400 hours is 3%. % Or less and 25
More preferably, the variation rate of the average diameter of the monofilament after the dry heat treatment at 0 ° C. for 400 hours is 5% or less.

That is, PP that satisfies the above rate of change in diameter
If it is an S monofilament, even if it is used in an environment where the temperature is extremely high, important factors such as moderate elasticity and elasticity of the cable protection sleeve obtained by tying the cable due to the fluctuation of the diameter of the monofilament are important. Very stable quality can be maintained without loss of characteristics.

More specifically, the characteristics of these protective sleeves, which were maintained before receiving heat, include the fact that the diameter of the monofilament changes due to the heat, so that the rigidity changes and becomes harder. The problem that narrowing the gap between the monofilaments, which has a bad influence on the elasticity of the protective sleeve, is eliminated.

When the PPS monofilament of the present invention simultaneously satisfies the above-mentioned properties in both the strength retention and the diameter variation when exposed to high-temperature conditions, the PPS monofilament exhibits a more advantageous effect as a protective sleeve. I do.

Further, the PPS monofilament of the present invention has a diameter of 0.1 to 1.0 mm, a diameter variation of less than 15% based on the average diameter of the monofilament measured in the fiber axis direction, a tensile strength of 2.2 cN / dtex or more, Dry heat shrinkage at 180 ° C. at a tensile elongation of not less than 20% at break 1.
When having the characteristics of 0 to 10.0%, the most excellent effect for the protective sleeve can be expected.

That is, if the diameter of the PPS monofilament is in the range of 0.1 to 1.0 mm, the protective sleeve made of the PPS monofilament will not be too rigid and will have excellent flexibility. In addition, the handling and handling of the protective sleeve in the product becomes extremely good, and the protective sleeve has sufficient durability even when it is subjected to abrasion or the like.

Here, as the PPS monofilament of the present invention, one having a circular cross section perpendicular to the fiber axis direction of the monofilament (including a substantially circular shape) is usually preferably used. It is represented by the average value of the measured major axis and minor axis. Furthermore, the shape of the cross section perpendicular to the fiber axis direction of the PPS monofilament of the present invention can take a shape other than a circle depending on its use and characteristics. For example, any shape such as a rectangle, a polygon, and an ellipse can be used. The diameter in the case of adopting a shape other than these circles can be in the same range as the fineness when converted to a circular shape.

When the diameter variation of the PPS monofilament relative to the average diameter of the monofilament measured in the fiber axis direction is less than 15%, particularly 8% or less, the finish as a product of the protective sleeve obtained by stringing may be uneven. And unfavorable results such as a problem in the process passability at the time of stringing can be eliminated, and variations in the strength and elongation in the fiber axis direction can be eliminated.

Further, the tensile strength of the PPS monofilament is 2.2 cN / dtex or more, especially 2.6 to 3.5 c
When the N / dtex and the tensile elongation at break of the fiber are in the range of 20% or more, especially in the range of 30 to 45%, it is possible to form a protective sleeve having both appropriate flexibility and strength.

Further, the PPS monofilament 1
The dry heat shrinkage measured at 80 ° C. is 1.0 to 10.0
%, In particular, in the range of 2 to 8%, there is a problem that the protective sleeve using the same has a small shrinkage when receiving heat in its use environment, and the length of the sleeve product largely varies. Not only does this not occur, but even when a step of applying heat (for example, heat setting) is required in the step of forming a string on the protective sleeve, good process passability is exhibited.

The PPS monofilament of the present invention is substantially composed of PPS. The term “PSS” as used herein means a phenylene sulfide unit in which the repeating unit of the polymer is a p-phenylene sulfide unit or m-phenylene sulfide unit. Means the contained polymer.
Among these polymers, 90% or more of the repeating units are p
Polymers comprising phenylene sulfide units are preferably used.

A PPS polymer which can be particularly preferably used in the present invention can be produced by subjecting p-dichlorobenzene to a polycondensation reaction of sodium sulfide.
It may be produced by copolycondensation of p-dichlorobenzene with less than 10 mol% of trichlorobenzene as a branching component.

In the present invention, ASTM D1238
Based on -86, 316 ° C, orifice diameter 2.095m
m, the orifice length is 8.00 mm, and the melt flow rate (hereinafter referred to as MFR) represented by the amount (g) of effluent polymer per 10 minutes measured under the conditions of a load of 5 kg is 20 to 3.
Although PPS of about 00 g / 10 minutes can be used,
From the point of strength-elongation balance, unevenness of diameter, wear characteristics,
In particular, PPS having an MFR of about 70 to 200 g / 10 minutes,
It can be preferably used.

Here, examples of the PPS which can be used as a commercial product include, for example, E1880 and E2 of PPS manufactured by Toray Industries, Inc.
080, E2280, E2481, M2488 and M
2588 and the like.

PPS is usually obtained as a powder, but before being subjected to melt spinning, the powder PPS is extruded with an extruder or the like.
The PS is heated to a temperature equal to or higher than the melting point, and after melting and kneading, if necessary, foreign substances are removed by filtration with a filter, extruded in a gut shape, cooled, and then processed into pellets by a method such as cutting and used. be able to. And, the PPS powder or PPS pellet is approximately 100
It is preferable to dry under reduced pressure and vacuum at about 180 ° C. for about 5 to 24 hours before subjecting to spinning.

The method for producing the PPS monofilament of the present invention is not particularly limited, but usually the following method is preferably applied.

That is, using a spinning machine such as an extruder type, melt extrusion is performed at a temperature 20 to 80 ° C. higher than the melting point of PPS, and the extruded molten polymer is melted at 60 to 95 ° C.
Cool and solidify in warm water at ℃. Subsequently, the obtained undrawn yarn is guided to a drawing bath or drawing atmosphere adjusted to a temperature equal to or higher than the glass transition temperature of PPS, and subjected to single-stage drawing or multi-stage drawing of two or more stages. The total draw ratio is preferably in the range of about 3.5 to 5.5 times. Further, in order to adjust the dry heat shrinkage, the breaking elongation at break of the fiber, and the like, the drawing after passing through the drawing step is performed. 120-28 for yarn
It is desirable to perform a heat setting of about 0.8 to 1.0 times in a temperature atmosphere of about 0 ° C.

The PPS monofilament of the present invention obtained as described above can be made of various inorganic materials such as titanium oxide, silicon oxide, silicon nitride, clay, talc, kaolin and zirconate as long as the desired properties are not excluded. Particles and cross-linked polymer particles, conventionally known antioxidants, sequestering agents, ion exchangers, coloring inhibitors, light fastening agents, clathrate compounds, various coloring agents, waxes, silicone oil, various surfactants, various It can contain reinforcing fibers, fluororesins, polyesters, polyamides, polyolefins, polystyrenes, and the like.

The PPS monofilament of the present invention thus obtained has hydrolysis resistance, chemical resistance,
Equipped with flame retardancy and heat resistance etc., as well as conventional PPS
Since it has a thermally stable quality not found in a monofilament and has a small unevenness in diameter, it can be suitably used for a cable protection sleeve.

That is, the cable protection sleeve formed by arranging a plurality of PPS monofilaments of the present invention and braiding them has excellent heat resistance, hydrolysis resistance, chemical resistance, flame retardancy and abrasion resistance. In addition, it has excellent durability and stable quality, and exhibits extremely excellent effects particularly as a signal transmission cable protection sleeve and a vehicle cable protection sleeve.

[0047]

EXAMPLES Hereinafter, examples of the PPS monofilament of the present invention and a cable protection sleeve using the same will be described in more detail, but the present invention is not limited to the following examples unless it exceeds the gist. Absent.

It should be noted that the P of the present invention described above and below is
The physical properties of the PS monofilament are values measured by the following methods. (1) Tensile strength (N) and tensile strength (cN / dte)
x): Measured according to JIS L1013 7.5. That is, 50 m of the PPS monofilament was taken in a skein shape, and 10 were arbitrarily taken out of a sample cut (100) to a sample length of 50 cm, and this was taken at 20 ° C. and 65%
Made by Orientec Co., Ltd. in the RH temperature and humidity control room
Using Tensilon "UTM-4-100 type tensile tester,
An average value of tensile strength (N) was measured under the conditions of a test length: 250 mm, a tensile speed: 300 mm / min, and a tensile strength (cN
/ Dtex) was calculated. (2) Diameter (mm): Take 50 m of PPS monofilament in a skein shape and cut (100 pieces) into a sample length of 50 cm. From this, 10 samples are arbitrarily taken out, and MI
The major axis and the minor axis of each sample were measured one point at a time using a TUTYOYO digital micrometer, and the average value was shown. (3) Dry heat treatment: A 50 cm cut PPS monofilament sample whose diameter and tensile strength were measured in advance was bundled, and a gear oven GPHH- manufactured by Tabai Espec Co., Ltd. was used.
Dry heat treatment was performed in a hot air circulation at a specified temperature and for a specified time using the sample No. 101. (4) Tensile strength retention (%): PPS monofilament sample 1 subjected to dry heat treatment at a specified temperature for a specified time
For zero, the tensile strength was measured by the same method as the above tensile strength, and the strength retention of the monofilament before and after the dry heat treatment was calculated. The formula is the strength retention (%) = (strength of monofilament after dry heat treatment ÷ strength of monofilament before dry heat treatment) × 100.
This shows that the PPS monofilament has thermally stable quality. (5) Average diameter fluctuation rate (%): Dry heat treatment was performed on the 10 samples whose diameters were measured in advance by the above method at a specified temperature for a specified time, and the diameter fluctuation rate of the monofilament before and after the dry heat treatment was calculated. The formula is: diameter variation rate (%) = {(diameter of monofilament after dry heat treatment−diameter of monofilament before dry heat treatment) ÷ diameter of monofilament before dry heat treatment} × 100. This shows that the PPS monofilament has thermally stable quality. (6) Monofilament diameter unevenness (%): Anritsu Corporation
Laser outer diameter measuring machine KL15X series (Detector: KL
151A, display part: KL350A), the PPS monofilament is run at a speed of 50 m / min, the outer diameter is measured for 10 minutes, and the recorder LR42 manufactured by Yokogawa Electric Corporation is used.
At 20, a wire diameter chart (diameter unevenness) was recorded. The maximum value and the minimum value of the diameter of the measured monofilament sample are obtained from this wire diameter recording chart, and the difference A (maximum value-minimum value:
(Unit: mm) was calculated, and the variation with respect to the average diameter of the monofilament obtained by the above-mentioned diameter measurement was defined as a diameter irregularity.
In addition, the formula of the diameter irregularity is the diameter irregularity (%) = (A ÷ average diameter)
× 100, indicating that the smaller the unevenness in diameter, the more the PPS monofilament has a uniform wire diameter. (7) Dry heat shrinkage (%): JIS L1013 7.1
5 (2) Dry heat shrinkage rate Measured according to the method B (filament shrinkage rate). That is, PP cut to 50 cm
Using a gear oven GPHH-101 manufactured by Tabai Espec Co., Ltd. to bundle 10 S monofilaments, 180
C. for 30 minutes in hot air circulation, and the dry heat shrinkage was measured. The dry heat shrinkage (%) = {(length of monofilament before dry heat treatment (500 mm) -length of monofilament after dry heat treatment (unit: mm))} {length of monofilament before dry heat treatment} × 100. (8) Evaluation of Dry Heat Treatment of Protective Sleeve: A monofilament protective sleeve produced by pulling a pair of monofilaments together and forming a cord was cut into 25 cm, and this was cut using a gear oven GPHH-101 manufactured by Tabai Espec Co., Ltd. Dry heat treatment was performed in a hot air circulation at 200 ° C. for 200 hours.

The state of deterioration such as shrinkage, flexibility, elasticity, and elasticity of the monofilament protective sleeve after the treatment, and the visual quality of the sleeve before and after the treatment (misalignment, presence or absence of deformation or cut of the monofilament), etc. It was observed comprehensively and evaluated according to the following criteria.

○ (good): The monofilament constituting the sleeve is hardly deteriorated, and the flexibility, elasticity, elasticity, visual quality change and shrinkage of the sleeve itself required for the protective sleeve are small, and the protective sleeve is excellent. Can be used.

× (poor): As a protective sleeve, the deterioration of the monofilament constituting the sleeve, the flexibility, elasticity, elasticity, and visual quality changes required for the sleeve are recognized. Is inadequate for use.

[0052]

Example 1 As a PPS raw material, 150 ° C. for 15 hours
A PPS pellet E2080 (MFR = 90) manufactured by Toray Industries Co., Ltd., which was dried under vacuum conditions, was prepared. This PPS
The raw material is supplied to an extruder type spinning machine, and the spinning machine temperature 3
The mixture is melted and kneaded at 30 ° C., and the spinneret (hole diameter: 1.5 m
After extruding the molten polymer from mφ × 10 holes), an undrawn PPS yarn immediately cooled and solidified in hot water at 80 ° C. was obtained.

Subsequently, the unstretched PPS yarn was heated at 96 ° C.
The film is first stretched 3.6 times in hot water, and further stretched 1.19 times in a dry heat atmosphere at 170 ° C. to a total draw ratio of 4.3 times, and then dried in a 180 ° C. dry heat atmosphere. Heat set under constant tension conditions below, average diameter 0.3m
m PPS monofilaments were obtained.

The obtained PPS monofilament had a strength retention and a diameter variation rate after dry heat treatment, a tensile strength, a tensile elongation, a dry heat shrinkage, and a diameter irregularity (hereinafter simply referred to as an average diameter) of the monofilament measured in the fiber axis direction. Table 1 shows the evaluation results of the evaluation of the dry heat treatment of the protective sleeve.

[0055]

Examples 2 to 4 and Comparative Examples 1 to 4 Using the same spinning process as in Example 1, the spinning conditions, the MFR of the PPS polymer, and the addition of carbon black were changed as shown in Tables 1 and 2. The PPS monofilament having a diameter of 0.30 mm and the monofilament having a diameter of 0.30 mm obtained by changing the raw materials to polyethylene terephthalate (PET) and nylon 6 were subjected to diameter, tensile strength, tensile elongation at break, and drying at 180 ° C. Tables 1 and 2 show the results of the heat shrinkage, uneven diameter, tensile strength retention after dry heat treatment and average diameter change, and evaluation of dry heat treatment of the cable protective sleeve.

[0056]

[Table 1]

[0057]

[Table 2] As is evident from the results in Table 1, the PPS monofilament of the present invention had thermally stable quality and all had sufficient high elongation characteristics. And the protective sleeve obtained by tying using the PPS monofilament of the present invention sufficiently maintained the quality required for the protective sleeve even after performing the dry heat treatment.

On the other hand, as is clear from the results in Table 2, the PPs of Comparative Examples 1 and 2 which do not satisfy the conditions of the present invention are shown.
S monofilaments were tied to a protective sleeve and subjected to dry heat treatment, and as a result, all of them could only achieve insufficient quality. That is, a protective sleeve made of a PPS monofilament whose tensile strength retention rate after dry heat treatment, average diameter fluctuation rate or diameter unevenness does not satisfy the requirements of the present invention has a large misalignment of the sleeve due to diameter fluctuation of the monofilament due to dry heat treatment. In addition, the properties such as flexibility, elasticity and elasticity of the protective sleeve are not only insufficient, but also the protective sleeve itself is greatly deformed,
The quality was inferior.

In the case of Comparative Examples 3 and 4 in which the material was changed to PET or Nylon 6, the dry heat treatment was carried out for a long time, and as a result, the monofilament's strength retention was insufficient, and the diameter variation was also reduced. There is a problem such as an increase in size, and the protective sleeve obtained by using such a monofilament to form a cord not only has a large shrinkage but also has a large strength deterioration.

[0060]

As described above, the PPS monofilament of the present invention has very stable quality even when exposed to a high temperature for an extremely long time, has a small diameter unevenness, and is used for industrial materials. The PPS monofilament also has extremely good quality, and exhibits particularly excellent effects when it is applied to a cable protection sleeve.

Further, the cable protective sleeve made of the PPS monofilament of the present invention has excellent heat resistance, hydrolysis resistance, chemical resistance, flame retardancy and abrasion resistance, has excellent high temperature durability, and is stable. Especially, when used as a signal transmission cable protection sleeve or a vehicle cable protection sleeve, an extremely excellent effect is exhibited.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Akira Kinoshita 1 Kawara, Showa-cho, Okazaki-shi, Aichi F-Term in Toray Monofilament Co., Ltd. (Reference) 3B153 AA45 BB01 CC24 CC31 FF11 FF15 GG03 GG07 GG40 3H024 AA01 AB01 AC03 4L035 AA02 BB31 BB57 BB72 BB76 BB85 BB89 BB91 CC02 CC09 DD14 EE01 EE08 EE20 FF01 FF10 MF02

Claims (7)

[Claims] 1. A monofilament consisting essentially of polyphenylene sulfide, having a tensile strength retention of at least 90% after a dry heat treatment at 200 ° C. for 100 hours and a dry heat treatment at 200 ° C. for 400 hours. A polyphenylene sulfide monofilament, wherein the tensile strength retention of the monofilament after performing is 80% or more. 2. A monofilament consisting essentially of polyphenylene sulfide, wherein the monofilament subjected to a dry heat treatment at 200 ° C. for 400 hours has a variation rate of the average diameter of the monofilament before the dry heat treatment of 4%.
%, Wherein the variation rate of the average diameter of the monofilament after the dry heat treatment at 250 ° C. for 400 hours with respect to the monofilament before the dry heat treatment is 7% or less. 3. A monofilament consisting essentially of polyphenylene sulfide, having a tensile strength retention of at least 90% after a dry heat treatment at 200 ° C. for 100 hours and a dry heat treatment at 200 ° C. for 400 hours. The tensile strength retention of the monofilament after the heat treatment is 80% or more, and the variation rate of the average diameter of the monofilament after the dry heat treatment at 200 ° C. for 400 hours with respect to the monofilament before the dry heat treatment is 4% or less.
A polyphenylene sulfide monofilament, wherein a monofilament after a dry heat treatment at 50 ° C. for 400 hours has a variation rate of an average diameter of 7% or less with respect to the monofilament before the dry heat treatment. 4. The monofilament has a diameter of from 0.1 to 0.1.
1.0 mm, less than 15% of irregularity in diameter relative to the average diameter of the monofilament measured in the fiber axis direction, and tensile strength of 2.
2cN / dtex or more, tensile elongation at break of fiber is 20%
As described above, the dry heat shrinkage at 180 ° C. is 1.0 to 10.0.
% Of the polyphenylene sulfide monofilament according to claim 1. 5. A cable protective sleeve comprising a polyphenylene sulfide monofilament. 6. A cable protection sleeve comprising the polyphenylene sulfide monofilament according to claim 1. Description: 7. A cable protection sleeve comprising a plurality of polyphenylene sulfide monofilaments according to any one of claims 1 to 4, which are aligned and stringed.