JP4374409B2 - Cable protection sleeve - Google Patents

Description

【００５７】
【表２】

表１の結果から明らかなように、本発明のＰＰＳモノフィラメントは、熱的に安定した品質を有するものであり、かついずれも十分な強伸度特性を兼ね備えるものであった。そして、本発明のＰＰＳモノフィラメントを用い製紐して得た保護スリーブは、乾熱処理を行なった後も、十分に保護スリーブとして求められる品質を維持するものであった。
【００５８】
一方、表２の結果から明らかなように、本発明の条件を満たさない比較例１および比較例２のＰＰＳモノフィラメントは、保護スリーブに製紐し乾熱処理を行なった結果、いずれも不十分な品質しか達成し得ないものであった。すなわち、乾熱処理後の引張強力保持率、平均直径変動率や直径斑が本発明の規定を満たさないＰＰＳモノフィラメントからなる保護スリーブは、乾熱処理によるモノフィラメントの直径変動によりスリーブの目合いのずれが大きくなり、保護スリーブとしての柔軟性、弾力性、伸縮性などの特性が不十分となるばかりか、保護スリーブそのものが大きく変形してしまい、品位の劣るものであった。
【００５９】
また、素材をＰＥＴやナイロン６に変更した比較例３および４の場合は、長時間にわたる乾熱処理を行なった結果、モノフィラメントの強力保持率が不十分であり、さらに直径の変動率も大きくなるなどの問題があり、これらモノフィラメントを用い製紐して得た保護スリーブも収縮が大きいばかりか、強力劣化が大きいものであった。
【００６０】
【発明の効果】
以上説明したように、本発明のケーブル保護スリーブに使用するＰＰＳモノフィラメントは、極めて長い時間高温下に晒された場合でも非常に安定した品質を有すると共に、直径斑も少なく、産業資材用途に利用されるＰＰＳモノフィラメントとしても極めて良好な品質を兼ね備えている。
【００６１】
また、本発明のケーブル保護スリーブは、優れた耐熱性、耐加水分解性、耐薬品性、難燃性および耐摩耗性を具備すると共に、高温耐久性に優れ、安定した品質を兼ね備えており、特に信号伝達ケーブル保護スリーブや車両ケーブル保護スリーブとして用いた場合に、極めて優れた効果を発揮する。[0001]
BACKGROUND OF THE INVENTION
The present invention has few diameter spots and maintains a thermally extremely stable quality even when used at a high temperature, and has a small diameter spot, and is suitably used for cable protection sleeve applications such as electrical appliance cables and vehicle cables. The present invention relates to a polyphenylene sulfide monofilament to be obtained and a cable protection sleeve made of the polyphenylene sulfide monofilament.
[0002]
[Prior art]
Polyphenylene sulfide (hereinafter referred to as PPS) is excellent in heat resistance, chemical resistance and flame retardancy, and can be melt-molded. Widely used as film and fiber. Among these, PPS fibers are used in various applications such as industrial fabrics such as papermaking and canvas, filters, electrical insulation materials and brush hairs, taking advantage of their excellent heat resistance, chemical resistance and flame resistance. ing.
[0003]
With regard to such a PPS fiber spinning technique, it is known from, for example, Japanese Patent Application Laid-Open No. 49-54617 that it can be easily made into a fiber by the same melt spinning method as that of a general general-purpose thermoplastic polymer. Many proposals have also been made for techniques related to the improvement of fibers and fibers.
[0004]
For example, in Japanese Patent Application Laid-Open No. Sho 61-215715, a tensile strength of 40 kg / mm is obtained by performing melt spinning using high viscosity poly (arylene thioether) (PPS).²Above, tensile strength at 200 ° C. 20 kg / mm²A technique for obtaining a polyarylene thioether fiber having the above characteristics is disclosed. Japanese Patent Application Laid-Open No. 64-3961 discloses that a PPS undrawn yarn is drawn in one step at a ratio higher than the natural draw ratio, and thereafter 150- Heat treatment at 260 ° C or higher and above the first stage stretching temperature, or by two-stage stretching in the same temperature range so that the total stretching ratio is 1 to 2 times the first stage stretching ratio. A technique for obtaining PPS fibers with improved mechanical properties, heat resistance, and chemical resistance is disclosed.
[0005]
In JP-A-1-229809 and JP-A-1-239109, PPS is melt-spun, subjected to one-stage stretching using a heating body, and then heat-set using a heating body at 100 to 140 ° C. After that, a technique for obtaining PPS fibers with extremely little fuzz and single yarn breakage by further performing heat setting using a heating body having a surface temperature of 150 ° C. or higher and a melting point or lower is disclosed.
[0006]
Further, JP-A-4-222217 discloses that an undrawn yarn obtained by melt spinning PPS is drawn 2 to 7 times at 80 to 260 ° C and then drawn in a dry heat atmosphere at 285 to 385 ° C. Heat treatment at 0.8 to 1.35 times for 0.1 to 30 seconds results in a tensile strength of 3.5 g / d or more and a knot strength of 2.5 g / d or more. Techniques for obtaining PPS fibers with improved s are disclosed.
[0007]
In addition, as a result of studying the same technique by the present inventors, an unstretched monofilament obtained by melt spinning a linear PPS having a melt flow rate of 200 g / 10 min or less and cooling in warm water of 60 ° C. or higher, Subsequently, after the primary stretch ratio of the primary stretch ratio / total stretch ratio is 0.88 or less, multistage stretching is performed so that the total stretch ratio is 4 times or more, and then relaxation heat treatment is performed in an air bath at 200 to 280 ° C. , A method for producing an excellent PPS monofilament with balanced tensile strength and knot strength (Japanese Patent Laid-Open No. Sho 62-299513), or a PPS monofilament obtained by spinning and stretching PPS with a melt flow rate of 20 to 120 g / 10 min The difference between the 200 ° C. dry heat shrinkage (Sd200) measured in the free state and the dry heat shrinkage (Sd140) measured at 140 ° C. Producing a PPS monofilament having a characteristic suitable for a spiral canvas for papermaking having a characteristic of a value ΔSd of 3.0% or less, Sd200 of 15 to 32%, and a strength of 3.5 g / d or more, and the PPS monofilament Have already been proposed (Japanese Patent Laid-Open No. 5-195318).
[0008]
In addition to the above-described PPS fiber spinning technology and PPS fiber improvement technology, several proposals have already been made regarding industrial materials using PPS fibers. For example, Japanese Patent Laid-Open No. 61-6390, JP-A-3-32711, JP-A-2-71809, JP-A-6-22413, JP-A-2-126622, JP-A-10-273825, JP-A-11-61584 and JP-A-11 -93028 discloses that PPS fibers are applied to various uses such as bag filters, filtration nonwoven fabrics, papermaking nonwoven fabrics, dryer fabrics, electrical insulation materials, automobile reinforcement cords, and motor binding materials. Has been.
[0009]
Among these application patents, Japanese Patent Application Laid-Open No. 10-273825 and Japanese Patent Application Laid-Open No. 11-1990 disclose a cable protection sleeve using PPS fibers (hereinafter, sometimes simply referred to as a protection sleeve) and similar techniques. Although these are described in Japanese Patent No. 61588, all of these use PPS multifilaments, and from the viewpoint of appropriate flexibility required as a protective sleeve, all of them are technologies that exhibit excellent characteristics. This protective sleeve has poor durability against abrasion and abrasion due to scratching due to the thin single yarn diameter of the PPS fibers constituting the protective sleeve, and in order to compensate for such drawbacks, Since coating with a surface treatment agent such as rubber is required, it has a problem that it leads to a significant cost increase.
[0010]
On the other hand, as monofilament materials that have been preferably used for protective sleeve applications, polyester resins such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate, polyamide resins represented by nylon 6 and nylon 66, polyvinylidene chloride, and the like Examples thereof include polyvinylidene fluoride.
[0011]
However, among the above, when the protective sleeve using the 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 overlaps, so It included the problems of being prone to degradation and inferior in durability.
[0012]
Protective sleeves using polyamide resin monofilaments have very good characteristics in terms of flexibility and have no problems such as hydrolysis, but are inferior in heat resistance and chemical resistance. It included the problem of limited use.
[0013]
Furthermore, although protective sleeves made of polyvinylidene chloride or polyvinylidene fluoride monofilaments are superior in terms of chemical resistance, etc., if the electrical products or automobiles using them are discarded and then incinerated, they are treated with dioxin or fluoride. There is a problem that it becomes a source of toxic gases such as hydrogen fluoride, which may cause environmental pollution.
[0014]
On the other hand, PPS is known to cause almost no problems when used at high temperatures because of its excellent heat resistance and hydrolysis resistance, and its chemical resistance is as good as that of fluororesin. have.
[0015]
In addition, although PPS may generate sulfurous acid gas when incinerated, since desulfurization technology using a desulfurization apparatus has been established for this, in terms of environmental pollution, the above-mentioned polyvinylidene chloride and polyvinylidene fluoride are used. It can be said that it is very excellent compared to.
[0016]
However, despite having such excellent characteristics, PPS has a large diameter spot when used as a monofilament, and has a large change in quality in an extremely high temperature atmosphere, so it is used particularly at high temperatures. The actual situation is that application to a monofilament protective sleeve has been hesitant.
[0017]
[Problems to be solved by the invention]
The present invention has been achieved as a result of investigations to solve the problems in the prior art in view of the above situation, and is extremely thermally effective even when used at a very high temperature for a long time. PPS monofilament that has a small diameter variation and can be suitably used for cable protection sleeve applications such as electrical cable and vehicle cable, and excellent heat resistance, hydrolysis resistance, The main purpose is to provide a cable protection sleeve having chemical resistance, flame resistance and abrasion resistance.
[0018]
[Means for Solving the Problems]
As a result of various studies to achieve the above-mentioned object, the present inventors have found that the PPS monofilament has a very small variation in average diameter with respect to the monofilament before the dry heat treatment even after the high temperature and long time dry heat treatment. In addition, a monofilament having an extremely low tensile strength retention ratio, that is, a very low decrease in strength even after a dry heat treatment at a very high temperature for a long time, and a PPS monofilament satisfying both of these characteristics are provided for the above purpose. The present inventors have found that an optimum effect is exhibited when these PPS monofilaments are used in a cable protection sleeve, and the present invention has been achieved.
[0019]
  That is, the present inventionCable protection sleeveIsIt consists of a PPS monofilament. The cable protection sleeve of the present invention is a PPS monofilament.After performing dry heat treatment at 200 ° C for 100 hoursPullingAfter performing a dry heat treatment with a tensile strength retention of 90% or more at 200 ° C. for 400 hoursPullingThe tensile strength retention is 80% or more.
[0020]
  In addition, the present inventionCable protection sleeveIsOf PPS monofilamentAfter performing dry heat treatment at 200 ° C for 400 hoursFlatThe variation rate of the uniform diameter isBefore dry heat treatmentAfter performing dry heat treatment for 4 hours or less at 250 ° C. for 400 hoursFlatThe variation rate of the uniform diameter isBefore dry heat treatmentIt is characterized by being 7% or less.
[0021]
  Furthermore, the present inventionCable protection sleeveIsOf PPS monofilamentAfter performing dry heat treatment at 200 ° C for 100 hoursPullingAfter performing a dry heat treatment with a tensile strength retention of 90% or more at 200 ° C. for 400 hoursPullingAfter a tensile strength retention of 80% or more and after performing a dry heat treatment at 200 ° C. for 400 hoursFlatThe variation rate of the uniform diameter isBefore dry heat treatmentAfter performing dry heat treatment for 4 hours or less at 250 ° C. for 400 hoursFlatThe variation rate of the uniform diameter isBefore dry heat treatmentIt is characterized by being 7% or less.
[0022]
  These of the present inventionCable protection sleeve is PPSThe monofilament diameter was 0.1 to 1.0 mm, measured in the fiber axis direction.PPSThe diameter variation with respect to the average diameter of the monofilament is less than 15%, the tensile strength is 2.2 cN / dtex or more, the tensile elongation at the time of fiber breakage is 20% or more, and the dry heat shrinkage at 180 ° C. is 1.0 to 10.0%. It is a more preferable condition.
[0023]
  And the cable protection sleeve of this invention is,UpA plurality of the PPS monofilaments described above are arranged and made into a string, and can be preferably used particularly as a signal transmission protective sleeve or a vehicle protective sleeve.
[0024]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in more detail.
[0025]
  Of the present inventionCable protection sleeveIsIt is necessary to be composed of PPS monofilament,Tensile strength retention after 90 hours of dry heat treatment at 200 ° C. is 90% or more, and tensile strength retention after 200 hours of 400 ° C. dry heat treatment is 80% or more. Even when used at a high temperature for a long time, it exhibits good strength retention, but the tensile strength retention after dry heat treatment at 200 ° C. for 100 hours is 95% or more, more preferably 97% or more. In the case where the strength retention after the dry heat treatment at 200 ° C. for 400 hours is 85% or more, more preferably 90% or more, it leads to the expression of a more suitable effect.
[0026]
That is, if it is a PPS monofilament satisfying the above-mentioned strong retention rate, even if it is used as an actual cable protection sleeve, the durability against heat is well maintained and even when used for an extremely long time. The monofilament constituting the sleeve after stringing does not cause a situation such as the sleeve being bent or coming into contact with other parts, or the sleeve fraying.
[0027]
  In addition, the present inventionCable protection sleeveIsOf PPS monofilamentMonofilament after 400 hours of dry heat treatment at 200 ° CFlatThe variation rate of the uniform diameter isBefore dry heat treatmentMonofilament that is 4% or less and is subjected to dry heat treatment at 250 ° C. for 400 hoursFlatThe variation rate of the uniform diameter isBefore dry heat treatment7% or less, that is, even when used at a high temperature for a long time, the diameter variation rate is small, but the variation rate of the average diameter of monofilaments after dry heat treatment at 200 ° C. for 400 hours is More preferably, the variation rate of the average diameter of the monofilament after the dry heat treatment at 250 ° C. for 400 hours is 5% or less.
[0028]
That is, if the PPS monofilament satisfying the above-mentioned diameter variation rate, even when used in an extremely high temperature environment, the cable protection sleeve obtained by stringing due to the monofilament diameter variation is suitable. Important characteristics such as elasticity and stretchability are not lost, and extremely stable quality can be maintained.
[0029]
More specifically, the characteristics of these protective sleeves that were maintained before receiving heat are that the diameter of the monofilament fluctuates due to heat and the rigidity changes and becomes harder, By narrowing the gap between the monofilaments, the problem of adversely affecting the expansion / contraction performance of the protective sleeve is eliminated.
[0030]
The PPS monofilament of the present invention exhibits a more suitable effect as a protective sleeve application when both the strength retention rate and the diameter variation rate when exposed to high temperature conditions simultaneously satisfy the above-described characteristics.
[0031]
  Furthermore, the present inventionCable protection sleeveIsOf PPS monofilamentDiameter is 0.1 to 1.0 mm, diameter variation with respect to average diameter of monofilament measured in fiber axis direction is less than 15%, tensile strength is 2.2 cN / dtex or more, tensile elongation at break of fiber is 20% or more, 180 ° C. In the case of having a dry heat shrinkage ratio of 1.0 to 10.0% at the same time, it can be expected to exhibit the most excellent effect as a protective sleeve.
[0032]
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 does not become too rigid and has excellent flexibility. In this case, the protective sleeve can be handled and handled in a very good manner, and it has sufficient durability even when it is rubbed.
[0033]
  Here, the present inventionCable protection sleeveIs thatPPSA monofilament having a circular cross section perpendicular to the fiber axis direction (generally including a circular shape) is usually preferably used, but the diameter is represented by an average value obtained by measuring the major axis and minor axis of the circle. . 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 according to its use and characteristics. For example, any shape such as a rectangle, a polygon, and an ellipse can be used. In addition, the diameter in the case of adopting a shape other than these circular shapes can take a range equal to the fineness when converted into a circular shape.
[0034]
Further, if the diameter unevenness with respect to the average diameter of the monofilament measured in the fiber axis direction of the PPS monofilament is less than 15%, particularly 8% or less, unevenness may occur in the finished product of the protective sleeve that can be formed into a string. Unfavorable results such as causing problems in process passability during stringing can be eliminated, and variations in the strength and elongation in the fiber axis direction can be eliminated.
[0035]
Furthermore, if the tensile strength of the PPS monofilament is 2.2 cN / dtex or more, particularly 2.6 to 3.5 cN / dtex, and the tensile elongation at break of the fiber is 20% or more, particularly 30 to 45%, it is appropriate. It is possible to form a protective sleeve having both flexibility and strength.
[0036]
Furthermore, if the dry heat shrinkage rate of the PPS monofilament measured at 180 ° C. is in the range of 1.0 to 10.0%, particularly 2 to 8%, the protective sleeve using the PSL monofilament can be used under the usage environment. There is little shrinkage when exposed to heat, and there is no problem such as large fluctuations in the product length of the sleeve, as well as a process of applying heat in the process of stringing the protective sleeve (for example, heat setting) ) Is required, it will show good processability.
[0037]
  Of the present inventionCable protection sleeveIs substantially PPSMonofilamentHowever, PPS here means a polymer in which the repeating unit of the polymer contains a phenylene sulfide unit composed of a p-phenylene sulfide unit or an m-phenylene sulfide unit. Among these polymers, a polymer in which 90% or more of repeating units are composed of p-phenylene sulfide units is preferably used.
[0038]
A PPS polymer that can be used particularly preferably in the present invention can be produced by polycondensation reaction of sodium sulfide with p-dichlorobenzene, but the p-dichlorobenzene has less than 10 mol% of trichlorobenzene as a branching component. It may be produced by polycondensation.
[0039]
In the present invention, in accordance with ASTM D1238-86, the melt indicated by the amount (g) of spilled polymer per 10 minutes measured under the conditions of 316 ° C., orifice diameter 2.095 mm, orifice length 8.00 mm, and load 5 kg. PPS having a flow rate (hereinafter referred to as MFR) of about 20 to 300 g / 10 min can be used, but in particular, MFR is 70 to 200 g / 10 from the standpoints of balance of strength and elongation, diameter unevenness, wear characteristics, and yarn production. PPS of about a minute can be preferably used.
[0040]
Here, as PPS which can be used as a commercial item, E1880, E2080, E2280, E2481, M2488, M2588, etc. of Toray Industries, Inc. can be mentioned, for example.
[0041]
PPS is usually obtained as a powder, but before being melt-spun, the powder PPS is heated to a temperature above its melting point with an extruder or the like, melted and kneaded, and then filtered to remove foreign substances as necessary. It can be extruded into a gut shape, cooled, and then processed into a pellet shape by a method such as cutting. The PPS powder or PPS pellets are preferably subjected to spinning after being dried at about 100 to 180 ° C. for about 5 to 24 hours under a vacuum.
[0042]
  Of the present inventionUsed for cable protection sleeveAlthough there is no restriction | limiting in particular in the manufacturing method of a PPS monofilament, Usually, the method described below is applied preferably.
[0043]
That is, using an extruder type spinning machine or the like, melt extrusion is performed at a temperature 20 to 80 ° C. higher than the melting point of PPS, and the extruded molten polymer is cooled and solidified in warm water at 60 to 95 ° C. Subsequently, the obtained undrawn yarn is led 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 one-stage drawing or two-stage or more multi-stage drawing. In addition, as a total draw ratio, the range of about 3.5 to 5.5 times is preferable. Furthermore, in order to adjust a dry heat shrinkage rate, a breaking elongation at the time of fiber breakage, etc. It is desirable to heat set the yarn about 0.8 to 1.0 times in a temperature atmosphere of about 120 to 280 ° C.
[0044]
The PPS monofilament of the present invention thus obtained has various inorganic particles such as titanium oxide, silicon oxide, silicon nitride, clay, talc, kaolin, zirconic acid, and cross-linking as long as the desired characteristics are not excluded. Polymer particles, conventionally known antioxidants, sequestering agents, ion exchange agents, anti-coloring agents, light resistance agents, inclusion compounds, various coloring agents, waxes, silicone oils, various surfactants, various reinforcing fibers , Fluororesins, polyesters, polyamides, polyolefins, polystyrenes, and the like.
[0045]
  AnywayRu PPS monofilament has hydrolysis resistance, chemical resistance, flame resistance and heat resistance, etc., which are the characteristics of PPS, and also has thermally stable quality not found in conventional PPS monofilaments, Since there are few diameter spots, it can be used suitably for a cable protection sleeve use.
[0046]
  Ie, PThe cable protection sleeve made by arranging and stringing multiple PS monofilaments has excellent heat resistance, hydrolysis resistance, chemical resistance, flame resistance and abrasion resistance, and excellent durability. Combined with stable quality, it is extremely effective as a signal transmission cable protection sleeve and a vehicle cable protection sleeve.
[0047]
【Example】
  Hereinafter, the present inventionNoAlthough the embodiment of the cable protection sleeve will be described in more detail, the present invention is not limited to the following embodiment unless it exceeds the gist.
[0048]
The physical properties of the PPS monofilament of the present invention described above and below are values measured by the following method.
(1) Tensile strength (N) and tensile strength (cN / dtex):
Measured according to JIS L1013 7.5. In other words, PPS monofilament 50m was taken in a bowl shape, and 10 pieces were arbitrarily taken out from the sample cut to 100 cm in length (100 pieces), and this was taken in a temperature / humidity adjustment chamber at 20 ° C. and 65% RH in the Orientec Co., Ltd. Using an “Tensilon” UTM-4-100 type tensile tester manufactured by the same company, the average value of tensile strength (N) was measured under the conditions of test length: 250 mm, tensile speed: 300 mm / min, and tensile strength (cN / dtex). ) Was calculated.
(2) Diameter (mm):
PPS monofilament 50m is taken in a bowl shape and cut into a sample length of 50 cm (100 pieces). Ten samples were arbitrarily taken from here, the major axis and minor axis of each sample were measured one by one with a digital micrometer made by MITUTOYO, 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 dry heat treatment was performed in a hot air circulation at a specified temperature for a specified time using a gear oven GPHH-101 manufactured by Tabay Espec.
(4) Tensile strength retention (%):
Ten PPS monofilament samples subjected to dry heat treatment at a specified temperature for a specified time were measured by the same method as the tensile strength described above, and the monofilament strength retention before and after the dry heat treatment was calculated. The formula is: strength retention (%) = (strength of monofilament after dry heat treatment ÷ monofilament strength before dry heat treatment) × 100, and the higher the strength retention, the more thermally stable PPS monofilament Indicates that
(5) Average diameter fluctuation rate (%):
Ten samples whose diameters were measured in advance by the above method were subjected to dry heat treatment at a specified temperature for a specified time, and the diameter variation rate of the monofilament before and after the dry heat treatment was calculated. In addition, a formula is a diameter fluctuation rate (%) = {(the diameter of the monofilament after the dry heat treatment−the diameter of the monofilament before the dry heat treatment) ÷ the diameter of the monofilament before the dry heat treatment} × 100, and the lower the diameter fluctuation rate, It shows a PPS monofilament with thermally stable quality.
(6) Monofilament diameter spot (%):
Using an Anritsu Corporation laser outer diameter measuring machine KL15X series (detection part: KL151A, display part: KL350A), PPS monofilament was run at a speed of 50 m / min and the outer diameter was measured for 10 minutes. ) A wire diameter chart (diameter spot) was recorded with a recorder LR4220. The maximum and minimum diameters of the measured monofilament samples are obtained from this wire diameter recording chart, and the difference A (maximum value-minimum value: unit mm) is calculated. Were used as diameter spots. In addition, the formula of a diameter spot is diameter spot (%) = (A ÷ average diameter) × 100, and the smaller the diameter spot, the more the PPS monofilament has a uniform wire diameter.
(7) Dry heat shrinkage (%):
Measured according to JIS L1013 7.15 (2) Dry heat shrinkage ratio B method (filament shrinkage ratio). That is, 10 PPS monofilaments cut to 50 cm were bundled and treated with hot air circulation at 180 ° C. for 30 minutes using a gear oven GPHH-101 manufactured by Tabai Espec Co., Ltd., and the dry heat shrinkage was measured. The formula is dry heat shrinkage (%) = {(monofilament length before dry heat treatment (500 mm) −monofilament length after dry heat treatment (unit: mm)) ÷ monofilament length before dry heat treatment} X100.
(8) Protection sleeve dry heat treatment evaluation:
A monofilament protective sleeve made by stringing together a pair of two monofilaments was cut out to 25 cm, and this was circulated in hot air at 200 ° C. for 200 hours using a gear oven GPHH-101 manufactured by Tabai Espec Co., Ltd. A dry heat treatment was performed.
[0049]
Comprehensive state of deterioration such as shrinkage, flexibility, elasticity, stretchability of the monofilament protective sleeve after treatment, and visual quality of the sleeve before and after treatment (out-of-scale deviation, presence or absence of deformation or cutting of the monofilament) Observed and evaluated according to the following criteria.
[0050]
○ (Good): Deterioration of monofilaments constituting the sleeve is small, flexibility, elasticity, stretchability, change in quality by visual inspection and shrinkage of the sleeve itself are small,
And can be used well.
[0051]
× (defect): Deterioration of monofilaments constituting the sleeve, flexibility, elasticity, elasticity, and changes in visual quality required for the sleeve, and large shrinkage of the sleeve itself.
It is insufficient as a probe and cannot be used.
[0052]
[Example 1]
A PPS pellet E2080 (MFR = 90) manufactured by Toray Industries, Inc., which was dried under vacuum conditions at 150 ° C. for 15 hours, was prepared as a PPS raw material. This PPS raw material is supplied to an extruder type spinning machine, melted and kneaded at a spinning machine temperature of 330 ° C., extruded from a spinneret (hole diameter: 1.5 mmφ × 10 holes), and immediately heated at 80 ° C. in warm water. The PPS undrawn yarn obtained by cooling and solidifying with was obtained.
[0053]
Subsequently, the unstretched PPS yarn was first stretched 3.6 times in 96 ° C. warm water, and further subjected to secondary stretching 1.19 times in a dry heat atmosphere at 170 ° C. to give a total draw ratio of 4. Then, heat setting was performed under a constant tension condition at 180 ° C. in a dry heat atmosphere to obtain a PPS monofilament having an average diameter of 0.3 mm.
[0054]
The obtained PPS monofilament has a strength retention ratio and a diameter fluctuation ratio after dry heat treatment, a tensile strength, a tensile elongation, a dry heat shrinkage rate, and a diameter spot (hereinafter simply referred to as a diameter spot) relative to the average diameter of the monofilament measured in the fiber axis direction. Table 1 shows the evaluation results of the protective sleeve dry heat treatment evaluation.
[0055]
Examples 2 to 4 and Comparative Examples 1 to 4
A PPS monofilament having a diameter of 0.30 mm obtained by using the same spinning process as in Example 1 and changing conditions such as the spinning conditions, the MFR of PPS polymer, and the addition of carbon black as shown in Tables 1 and 2. And 0.30 mm monofilament obtained by changing the raw material to polyethylene terephthalate (PET) and nylon 6, diameter, tensile strength, tensile elongation at break, 180 ° C. dry heat shrinkage, diameter irregularity, tensile strength after dry heat treatment Tables 1 and 2 show the retention rate, the average diameter variation rate, and the evaluation results of the cable protection sleeve dry heat treatment evaluation.
[0056]
[Table 1]

[0057]
[Table 2]

As is apparent from the results in Table 1, the PPS monofilament of the present invention has a thermally stable quality, and both have sufficient strength and elongation characteristics. The protective sleeve obtained by stringing using the PPS monofilament of the present invention sufficiently maintains the quality required as a protective sleeve even after dry heat treatment.
[0058]
On the other hand, as is clear from the results of Table 2, the PPS monofilaments of Comparative Example 1 and Comparative Example 2 that do not satisfy the conditions of the present invention were both formed with a protective sleeve and subjected to dry heat treatment. However, it could only be achieved. That is, a protective sleeve made of a PPS monofilament whose tensile strength retention rate, average diameter variation rate and diameter unevenness after dry heat treatment do not satisfy the provisions of the present invention has a large deviation in the size of the sleeve due to monofilament diameter variation due to dry heat treatment. Thus, not only the properties such as flexibility, elasticity and stretchability of the protective sleeve become insufficient, but also the protective sleeve itself is greatly deformed, resulting in poor quality.
[0059]
Further, in the case of Comparative Examples 3 and 4 in which the material is changed to PET or nylon 6, as a result of performing the dry heat treatment for a long time, the strength retention of monofilament is insufficient and the variation rate of the diameter is also increased. The protective sleeve obtained by stringing using these monofilaments was not only greatly shrunk but also greatly deteriorated in strength.
[0060]
【The invention's effect】
  As explained above, the present inventionUsed for cable protection sleevePPS monofilaments have extremely stable quality even when exposed to high temperatures for an extremely long time, have few diameter spots, and have extremely good quality as PPS monofilaments used for industrial materials.The
[0061]
  In addition, the present inventionNoThe cable protection sleeve has excellent heat resistance, hydrolysis resistance, chemical resistance, flame resistance and wear resistance, as well as high temperature durability and stable quality, especially for signal transmission cable protection When used as a sleeve or a vehicle cable protection sleeve, it exhibits an extremely excellent effect.

Claims (6)

A cable protection sleeve made of polyphenylene sulfide monofilament . The cable protection sleeve according to claim 1, wherein a plurality of the polyphenylene sulfide monofilaments are aligned and made into a string . The polyphenylene sulfide 100 hours tensile strength retention after performing a dry heat treatment at 200 ° C. for the monofilament 90% or more, 200 ° C. at 400 hours tensile strength retention after performing a dry heat treatment of not less than 80% The cable protection sleeve according to claim 1 or 2, wherein The variation rate of the average diameter of the polyphenylene sulfide monofilament after the dry heat treatment at 200 ° C. for 400 hours is 4% or less of that before the dry heat treatment, and the average diameter after the dry heat treatment at 250 ° C. for 400 hours is The cable protection sleeve according to claim 1 or 2, wherein the variation rate is 7% or less with respect to that before the dry heat treatment. The polyphenylene sulfide monofilament has a tensile strength retention of 90% or more after being subjected to a dry heat treatment at 200 ° C. for 100 hours, and a tensile strength retention rate of 80% or more after being subjected to a dry heat treatment at 200 ° C. for 400 hours. And, the variation rate of the average diameter after performing the dry heat treatment at 200 ° C. for 400 hours is 4% or less than that before the dry heat treatment, and the variation rate of the average diameter after performing the dry heat treatment at 250 ° C. for 400 hours is The cable protection sleeve according to claim 1 or 2, wherein the content is 7% or less of that before the dry heat treatment . The polyphenylene sulfide diameter of the monofilament is 0.1 to 1.0 mm, diameter plaque to the average diameter of the polyphenylene sulfide monofilaments, measured in the fiber axis direction is less than 15%, the tensile strength is 2.2 cN / dtex or more, a tensile at fiber breakage The cable protection sleeve according to any one of claims 1 to 5, wherein the elongation is 20% or more and the dry heat shrinkage at 180 ° C is 1.0 to 10.0%.