JP2011202305A - Treating agent for polyphenylene sulfide fiber and polyphenylene sulfide fiber imparted therewith - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a treating agent for polyphenylene sulfide fiber which has sufficient electric insulation and exhibits excellent step passability in spinning and high-order processing, and a polyphenylene sulfide fiber imparted therewith.SOLUTION: A treating agent for polyphenylene sulfide fiber is an ester compound of a fatty acid and aliphatic alcohol, an oily type nonionic surfactant which is prepared by esterification of 85-95 wt.% of aliphatic polyvalent ester (A) having a molecular weight of 600-1,000 and the whole end hydroxyl group with the monovalent fatty acid, and is predominantly composed of a mixture formed of 5-15 wt.% of nonionic surfactant ingredient (B) having an HLB of 5-9 and a molecular weight of 2,000-3,000.

Description

  The present invention relates to a treatment agent for polyphenylene sulfide fibers and a polyphenylene sulfide fiber provided with the treatment agent. More specifically, the treatment agent has sufficient electrical insulation properties and good processability in yarn production and high-order processing. The present invention relates to a treatment agent for polyphenylene sulfide fiber and polyphenylene sulfide fiber provided with the treatment agent.

  Conventionally, methods for producing polyphenylene sulfide fibers include a method of producing by two-stage drawing (for example, see Patent Document 1), a method of applying an aqueous emulsion (for example, see Patent Document 2), and a special additive. There is known a method for imparting a dibasic acid ester or an aromatic ester excellent in heat resistance as a treating agent (for example, see Patent Document 3). The details are not mentioned, and nothing is said about the improvement of the electrical insulation of the fibers.

  On the other hand, as the electrical insulating oil agent for fibers, those relating to a novel electrical insulating oil agent (for example, see Patent Document 4), a method for applying known electrical insulating oil to special fibers (for example, see Patent Document 5), A method of using a specific nonionic surfactant in combination when using an electrical insulating oil as a lubricating oil in a treating agent for fibers (for example, see Patent Document 6) is known, and these are all polyphenylene sulfide. There is no mention of the use of electrical insulating oils in the fiber manufacturing process, and there is no known literature regarding the provision of polyphenylene sulfide fibers for applications with electrical insulation. It is.

JP-A-57-143518 Japanese Patent Laid-Open No. 04-100916 Japanese Patent Laid-Open No. 03-076812 Japanese Patent Application Laid-Open No. 61-016410 Japanese Patent Application Laid-Open No. 06-200489 JP 2000-319678 A

  An object of the present invention is to provide a treatment agent for polyphenylene sulfide fiber having sufficient electrical insulation and good process passability in the production and processing of polyphenylene sulfide fibers, and a polyphenylene sulfide fiber provided with the treatment agent. It is what.

  In order to solve the above-described problems, according to the present invention, an aliphatic polyhydric ester (A) having a molecular weight of 600 to 1000, which is an esterified product of a fatty acid and an aliphatic alcohol, and 85 to 95% by weight, and all terminal hydroxyl groups. A nonionic active agent of an oily type esterified with a monovalent fatty acid, the mixture comprising 5 to 15% by weight of a nonionic active agent (B) having an HLB of 5 to 9 and a molecular weight of 2000 to 3000 A treating agent for polyphenylene sulfide fibers is provided which is contained as a main component.

The polyphenylene sulfide fiber of the present invention is a polyphenylene sulfide fiber to which the fiber treatment agent of the present invention is applied, and has an insulation resistance value of 5 × 10 ¹² Ω or more. It is a preferable condition that the main component adhesion amount is 0.5 to 2.0% by weight based on the fiber weight.

  According to the present invention, a polyphenylene sulfide fiber having sufficient electrical insulation and good processability in yarn production and high-order processing is obtained, and the polyphenylene sulfide fiber has the characteristics of heat resistance and chemical resistance. It can be suitably used for various industrial material applications that make the most of the above, especially for motor bundling cords and motor sleeves of automobiles in which electrical insulation is an important required characteristic.

  The present invention is described in detail below.

  The treatment agent for polyphenylene sulfide fibers of the present invention needs to contain 85 to 95% by weight, preferably 87 to 93% by weight of the aliphatic polyvalent ester (A) in the main component. If the aliphatic polyvalent ester (A) is less than 85% by weight, the electric insulation which is the object of the present invention cannot be obtained, and if it exceeds 95% by weight, dilution with an organic solvent is required, which is not preferable in terms of cost.

  The aliphatic polyvalent ester (A) used in the treatment agent for polyphenylene sulfide fiber of the present invention is an esterified product of a fatty acid and an aliphatic alcohol and needs to be an aliphatic polyvalent ester having a molecular weight of 600 to 1,000. It is. If the molecular weight of the aliphatic polyvalent ester (A) is less than 600, the oil film and heat resistance of the treatment agent are insufficient, and yarn breakage and smoke generation tend to occur frequently. If the molecular weight exceeds 1,000, the smoothness of the treatment agent is increased. Unsatisfactory and frequent thread breakage and fluff are undesirable. In the case of monoesters, the oil film and heat resistance are also insufficient, which is also not preferable.

  Specific examples of the aliphatic polyvalent ester (A) used in the present invention include 1,6-hexanediol dilaurate, dioleyl adipate, diisostearyl adipate, dioleylthiodipropionate, trimethylolpropane trilaurate, Examples include coconut oil and rapeseed oil. Of these, diisostearyl adipate and trimethylolpropane trilaurate are preferable.

  The treatment agent for polyphenylene sulfide fiber of the present invention needs to contain 5 to 15% by weight, preferably 7 to 13% by weight of the nonionic active agent (B) in the main component. If the nonionic active agent (B) is less than 5% by weight, it is not preferable in terms of cost since water emulsification becomes impossible, and if it exceeds 15% by weight, the electrical insulation that is the object of the present invention cannot be obtained. Therefore, it is not preferable.

  The nonionic active agent (B) used in the polyphenylene sulfide fiber treatment agent of the present invention is an oily type nonionic active agent in which all terminal hydroxyl groups are esterified with monovalent fatty acids, and HLB is It is necessary to be a nonionic active agent having a molecular weight of 5 to 9 and a molecular weight of 2000 to 3000. HLB is an abbreviation for Hydrophile Lipophile Balance and is a value representing the affinity of a nonionic active agent for water and oil. When the HLB of the nonionic active agent (B) is less than 5, the uniform adhesion of the oil agent is insufficient, and yarn breakage and fluff tend to occur frequently. When the HLB exceeds 9, the smoothness of the treatment agent is insufficient. Further, it is not preferable because the electrical insulation is further lowered. When the molecular weight of the nonionic active agent (B) is less than 2000, the oil film of the treatment agent is insufficient, and when the molecular weight exceeds 3000, the friction increases, and in either case, yarn breakage and fluff tend to occur frequently. This is not preferable.

  Specific examples of the nonionic active agent (B) used in the present invention include polyoxyethylene lauryl ether monomethyl ether, polyoxyethylene diolate, polyoxypropylene diolate, polyoxyethylene sorbitan tetraoleate, and polyoxyethylene sorbitol. Examples include hexaoleate, polyoxyethylene sorbitol hexalaurate, polyoxyethylene glycerol trioleate, polyoxyethylene hydrogenated castor oil trilaurate, and polyoxyethylene hydrogenated castor oil trioleate. Of these, polyoxyethylene sorbitol hexalaurate and polyoxyethylene hydrogenated castor oil trilaurate are preferable.

  The treatment agent for polyphenylene sulfide fiber of the present invention includes, for example, an antioxidant, an antifoaming agent, an antiseptic, an anti-bacterial agent, in addition to the aliphatic polyvalent ester (A) and the nonionic active agent (B) as main components. Although a rusting agent etc. can be mixed and used as needed, the addition amount of these is preferably less than 2 weight% with respect to the whole oil agent.

The polyphenylene sulfide fiber to which the treatment agent for polyphenylene sulfide fiber of the present invention is applied preferably has an insulation resistance value of 5 × 10 ¹² Ω or more, more preferably 10 × 10 ¹² Ω or more, as measured by a superinsulator. is there.

  The polyphenylene sulfide fiber of the present invention is preferably attached with a treatment agent composed mainly of a mixture of the aliphatic polyvalent ester (A) and the nonionic active agent (B). The main component adhesion amount is preferably 0.5 to 2.0% by weight, more preferably 0.8 to 1.5% by weight, based on the fiber weight.

  The polyphenylene sulfide fiber treatment agent of the present invention may be used in any state of a non-aqueous oil agent diluted with a low-viscosity mineral oil, an emulsion oil agent emulsified with water, or a neat oil. Use in emulsion oils emulsified with water is preferred. What is necessary is just to give in a spinning process using well-known methods, such as roller oil supply and a guide oil supply apparatus, as a method provided to a raw yarn.

  Next, a typical method for producing the polyphenylene sulfide fiber of the present invention will be outlined.

  First, a known polyphenylene sulfide pellet having a melt flow rate (MFR) of 50 to 600 is dried at 140 to 180 ° C. for about 2 to 24 hours and melt-spun for removing low-boiling foreign substances. The melt flow rate (MFR) here is a parameter indicating the melt flowability of the polymer measured by the ASTM D1238-82 method when the set temperature is 316 ° C. and the load is 5 kgf. The polyphenylene sulfide used in the present invention is preferably substantially linear, may contain 0.1% by weight or less of trichlorobenzene (TCB), and may contain a small amount of other additives. .

In the present invention, an extruder type spinning machine is preferably used for melting the polymer pellets of polyphenylene sulfide. The spinning temperature is 300 to 320 ° C., and the mixture is filtered through a 5 to 20 μm filter in a spinning pack. The filtered polymer is spouted from the die pores using a die, passed through a slow cooling zone directly under the die, and then cooled and solidified by blowing cold air. In the die, the die pores are arranged in a normal zigzag arrangement or an annular arrangement, and the hole diameter and the hole length are 70 to 150 kg / cm ² at the die back pressure, and the ratio of the discharge linear velocity from the die hole to the take-off speed. What is necessary is just to design suitably so that the spinning draft defined by may be 20-50. When the spinning draft exceeds 50, fineness spots are deteriorated. A more preferable range of the pressure on the back surface of the die is 90 to 110 kg / cm ² . The slow cooling zone is attached with a heat-insulating cylinder having a length of 5 to 10 cm, and the temperature is controlled so that the ambient temperature at 10 cm directly below the base is 150 to 250 ° C. Cooling is performed by spraying cold air of 10 to 30 ° C. at a speed of 30 to 40 m / min, but it is preferable to spray at a speed of 35 m / min or more. Since it is necessary to enhance the cooling of single yarn thick fine yarn, it is better that the speed of the cold air to be blown is higher, but since the spinning tension is greatly reduced compared to the conventional single yarn fine yarn, the speed is 40 m / min or more. If cold air is blown on the yarn, it is not preferable because the yarn is likely to jump out of the spinning duct, or the fiber properties are lowered and fluff frequently occurs due to contact with the spinning duct. A horizontal chimney that blows cold air at right angles to the spun yarn may be used, or an annular cooling chimney may be used to spray from the outer periphery of the spun yarn bundle to the center or from the center to the outer periphery. It is preferable to use a side blowing cooling chimney.
Next, the fiber treating agent of the present invention is applied to the cooled and solidified yarn, and the yarn is wound around a take-up roll that rotates at a predetermined speed. The treatment agent can be applied using a known method such as roller lubrication or guide lubrication. As the take-up roll, a single-hanging type, a Nelson type or an S-roll type may be used, and any of them may be used. The temperature is usually normal temperature, but water is circulated inside the roll to 20 to 40 ° C. Control the temperature. The take-up speed is 400 to 1000 m / min, preferably 500 to 800 m / min. When the take-up speed, that is, the spinning speed is less than 400 m / min, the production amount per unit time is reduced, and it becomes impossible to obtain polyphenylene sulfide fibers with good productivity, and polyphenylene sulfide fibers satisfying the intended strength range are obtained. It becomes difficult to set an appropriate draw ratio for stable production. On the other hand, if it exceeds 1000 m / min, the amount of polymer discharged from the die becomes too large, and it becomes difficult to perform sufficient cooling with the current spinning technique, which is not preferable because it leads to deterioration of the spinning performance. It is necessary to once cool the polyphenylene sulfide yarn to below the glass transition point.

  Next, the take-up yarn is wound around a feed roll without winding once in order to stabilize the quality and yarn-making property, and after prestretching the yarn between the take-up roll and the feed roll, It can be wound using the same multi-stage stretching method, or can be wound using a unique multi-stage stretching method suitable for the production of polyphenylene sulfide fibers proposed in JP-A-2001-262436, The latter is preferably used when the spinning speed is low.

  In the same multistage drawing method as that for polyamide or the like, the polyphenylene sulfide fiber is drawn and heat treated by the following method. The pre-stretch is 2 to 10%, preferably 4 to 8%. It is preferable to control the temperature of a feed roll at 70-110 degreeC. Next, the first stage of stretching is performed between the feed roll and the first stretching roll. The first stretching roll is heated to 80 to 120 ° C. In order to obtain a high-strength polyphenylene sulfide fiber, it is preferable that the first stage draw ratio is 3.3 to 3.8 times as high as possible without causing single yarn breakage. The first-stage-stretched yarn is subjected to the second-stage stretching with the second stretching roll. A 2nd extending | stretching roll is set to the range of 180-250 degreeC. The second stage draw ratio is preferably set to 1.05 to 1.3 times. Further, if necessary, the third stage of stretching may be performed with the third stretching roll. In this case, the temperature of the third stretching roll is set to the same temperature range as that of the second stretching roll, and is usually set to a temperature higher than that of the second stretching roll. The third stage draw ratio is usually set by dividing the second stage draw ratio and setting the second stage draw ratio higher than the third stage draw ratio. The overall draw ratio is preferably 3.8 to 4.5 times, more preferably 3.9 to 4.4 times, and still more preferably 4.0 to 4.3 times. Without applying such a narrow range of overall draw ratios, it is impossible to obtain single-filament thick yarns made of polyphenylene sulfide with little fluff and yarn breakage. Fall into. In particular, when the temperature of the second stretching roll is a high temperature of 200 ° C. or higher, it is necessary to increase the orientation as much as possible and increase the strength before coming into contact with the high-temperature roll. The yarn stretched in two or three stages is then subjected to a relaxation heat treatment with a tension adjusting roll. The tension adjusting roll is not heated or set to 150 ° C. or lower. The relaxation rate is 2 to 10%, preferably 4 to 8%. Each roll from the first stretching roll to the tension adjusting roll is preferably a Nelson type roll.

  The polyphenylene sulfide of the present invention thus obtained has sufficient electrical insulation, and has good processability in yarn production and high-order processing, as well as its characteristics of heat resistance and chemical resistance. Therefore, it can be suitably used for various industrial material applications that make use of these characteristics, in particular, motor bundling cords and motor sleeve applications for automobiles in which electrical insulation is an important required characteristic.

  Next, the present invention will be described in detail by way of examples.

  In addition, the measuring methods, such as a physical property used for the main text and the Example, are as follows.

  (1) Total fineness: JIS L1013 (1999) 8.3.1 The positive fineness was measured at a predetermined load of 0.045 cN / dtex by the A method to obtain the total fineness.

  (2) Amount of attached oil: The diethyl ether extract was measured by the method of JIS L1013 (1999) 8.27 b) to obtain the amount of attached oil.

  (3) Strength / Elongation: Measured under constant speed elongation conditions shown in JIS L1013 (1999) 8.5.1 Standard Time Test. The sample was “TENSILON” UCT-100 manufactured by Orientec Co., Ltd., and the gripping interval was 25 cm and the pulling speed was 30 cm / min. In addition, elongation was calculated | required from elongation of the point which showed the maximum strength in a SS curve.

  (4) Yarn breakage: From the start of yarn making, the number of yarn breakage when a total of 1000 kg of yarn was made with the fiber package weight was evaluated.

  (5) Insulation resistance value: According to the method shown in JIS C2140 (2009), it was stored for 24 hours or more at a temperature of 25 ° C. and a humidity of 40% in a Super Megah Meter SM-5E manufactured by Toa Electronics Industry Co., Ltd. Using 30 g of the yarn sample, the insulation resistance value was measured when a voltage of 1000 kV was applied.

[Examples 1 to 3, Comparative Examples 1 to 5]
Toray polyphenylene sulfide polymer with MFR of 200 was melted with an extruder-type spinning machine under a vacuum of 1.33 kPa so that the polymer temperature was 315 ° C., and the melted polymer had 5 μm pores in the spinning pack. After filtering with a metal filter, spinning was performed using a spinneret with a staggered single row array having 19 discharge holes with a diameter of 0.50 mm. The discharge amount was calculated from the winding speed so that the obtained fiber was 440 dtex, and the metering pump was adjusted. A heating cylinder having a length of 100 mm is provided immediately below the base, and after slowly cooling the yarn, it is cooled and solidified with cold air at 25 ° C. at 25 ° C. using a side blowing cooling chimney. The treatment agent containing the ester (A) and the nonionic active agent (B) as main components was applied as a water emulsion liquid by an oiling roll rotating at 25 rpm. In addition, all the oil agent components shown in Table 1 are used by mixing single components made by Takemoto Yushi Co., Ltd., and each numerical value indicates the number of parts of the aliphatic polyvalent ester (A) and the nonionic active agent (B).

  The fed yarn is drawn to the take-up roll at a speed of 500 m / min, stretched by 6% between the take-up roll and the feed roll, and then stretched in the first stage between the feed roll and the first draw roll, The second stage stretching was performed between the first stretching roll and the second stretching roll. Subsequently, a relaxation heat treatment of 5% was performed between the second drawing roll and the relaxation roll, the yarn was entangled with an entanglement imparting device, and then wound with a winder. The surface temperature of each roll was set so that the take-up roll was at room temperature, the feed roll was 80 ° C., the first stretching roll was 110 ° C., the second stretching roll was 235 ° C., and the relaxation roll was 150 ° C. The rotation speeds of the first stretching roll and the second stretching roll were set so that the first stage stretching ratio was 3.70 times and the overall stretching ratio was 4.30 times.

  Table 2 shows the characteristic evaluation results of the polyphenylene sulfide fibers thus obtained.

  As is clear from the results in Table 2, Examples 1 to 3 showed results that all examples were excellent in electrical insulation, but Comparative Examples 1 and 5 were results that were poor in electrical insulation. Further, Examples 1 to 3 all showed no yarn breakage and good yarn-making properties, but Comparative Examples 2 to 5 had a result that the number of yarn breaks was large and the yarn-making properties were insufficient.

  The polyphenylene sulfide of the present invention has sufficient electrical insulation, and has good process passability in yarn production and high-order processing, as well as its characteristics of heat resistance and chemical resistance. It can be suitably used for various industrial material applications that make use of the above characteristics, and in particular, motor bundling cords and motor sleeves for automobiles that require electrical insulation as an important required characteristic.

Claims (3)

Fatty acid and aliphatic alcohol esterified product of 85 to 95% by weight of aliphatic polyvalent ester (A) having a molecular weight of 600 to 1000, and an oily type in which all terminal hydroxyl groups are esterified with monovalent fatty acid A polyionic sulfide containing a nonionic activator comprising 5 to 15% by weight of a nonionic activator (B) having an HLB of 5 to 9 and a molecular weight of 2000 to 3000 as a main component. Treatment agent for textiles. A polyphenylene sulfide fiber to which the fiber treating agent according to claim 1 is applied, wherein the insulation resistance value is 5 × 10 ¹² Ω or more. The polyphenylene sulfide fiber according to claim 2, wherein the main component adhesion amount of the fiber treatment agent is 0.5 to 2.0% by weight based on the fiber weight.