WO2009087901A1

WO2009087901A1 - Polyphenylene sulfide fiber and process for producing the same

Info

Publication number: WO2009087901A1
Application number: PCT/JP2008/073521
Authority: WO
Inventors: Hirotaka Horiguchi; Hiroaki Ozawa
Original assignee: Toray Industries, Inc.
Priority date: 2008-01-09
Filing date: 2008-12-25
Publication date: 2009-07-16
Also published as: JP2009185438A; CN101960058B; EP2246463A4; US20100285315A1; EP2246463A1; JP2012246599A; CN101960058A; JP5251490B2; EP2246463B1

Abstract

Polyphenylene sulfide fibers having a large value of single-fiber fineness and especially suitable for use as an industrial material required to have rigidity are provided without the need of using a special apparatus. Also provided is a technique for producing the polyphenylene sulfide fibers inexpensively while attaining satisfactory spinnability. The polyphenylene sulfide fibers are characterized by having a single-fiber fineness of 10-50 dtex and a strength of 4.5-6 cN/dtex. The technique is a process for polyphenylene sulfide fiber production which is characterized by adhering an aqueous lubricant in an amount of 0.1-1 wt.% and then adhering a nonaqueous lubricant in such an amount as to result in a total adherent-lubricant amount of 0.5-2 wt.%.

Description

Polyphenylene sulfide fiber and method for producing the same

The present invention relates to polyphenylene sulfide fiber and a method for producing the same. More specifically, the present invention relates to a polyphenylene sulfide fiber having a large single yarn fineness particularly suitable for industrial materials and a method for producing the same, and more specifically, it can be obtained with high production efficiency with less fuzz and yarn breakage during yarn production. The present invention relates to polyphenylene sulfide fiber and a method for producing the same.

Polyphenylene sulfide has excellent properties such as heat resistance, chemical resistance, flame retardancy, and electrical insulation, and is known as a high-performance engineering plastic used in harsh environments. In the field of fibers, the characteristics of materials have been used to expand their applications, but the types of fibers that are currently in practical use are multifilaments with a single yarn fineness of several dtex and monofilaments with a diameter of several hundred μm. Broadly divided, the final product is manufactured by using them alone or in combination, and multifilaments of intermediate thickness are not manufactured. This is because it was extremely difficult to produce polyphenylene sulfide fibers having a large single yarn fineness, and almost no technology for producing such a multifilament made of polyphenylene sulfide fibers having a large single yarn fineness was disclosed. Not.

Patent Document 1 discloses basic matters relating to fiber formation of polyphenylene sulfide, and describes that polyphenylene sulfide fibers can be produced by a melt spinning technique similar to polyamide and polyester. However, the method proposed in Patent Document 1 cannot obtain a polyphenylene sulfide fiber having high strength and high toughness, which has been required in recent years. Also, although proposals have been made to use a liquid refrigerant for cooling enhancement when the yarn is thick, an actual production example is not disclosed, and special equipment is used for the use of the refrigerant. Therefore, there is a problem that the direct spinning drawing method is difficult to apply.

Further, Patent Document 2 discloses that polyphenylene having a single yarn fineness of 50 deniers or less having high strength, high toughness, suitable shrinkage properties, and less fluff suitable for textile use by controlling fiber structure parameters within a specific range. A sulfide fiber and a method for producing the same are disclosed. However, the technique described in Patent Document 2 is inferior in dimensional stability because the atmosphere during stretching or the maximum temperature of the roller surface is set to a relatively low temperature of 120 to 180 ° C. in order to reduce the crystal size. In addition, even if the technique described in Patent Document 2 is actually used, polyphenylene sulfide having a single yarn fineness of 10 dtex or more cannot be stably obtained.
JP-A-57-143518 (Claims) Japanese Patent Laid-Open No. 4-100916 (Claims)

The present invention has been achieved as a result of studying the solution of the above-described problems in the prior art as a subject, and is manufactured at low cost by using a conventional direct spinning drawing method with less fuzz and yarn breakage during yarn production. An object of the present invention is to provide a polyphenylene sulfide fiber having a large single yarn fineness.

In order to achieve the above object, according to the present invention, there is provided a polyphenylene sulfide fiber having a single yarn fineness of 10 to 50 dtex and a strength of 4.5 to 6 cN / dtex.

In the polyphenylene sulfide fiber of the present invention,
That at least a surfactant component and an antioxidant component are attached to the fiber surface;
The total amount of adhered oil relative to the fiber weight is 0.5 to 2% by weight, of which the surfactant component amount is 0.01 to 1% by weight and the antioxidant component amount is 0.002 to 0.1% by weight. Being
The total fineness is 100 to 1000 dtex, the number of single yarns is 2 to 50, and no twisting;
Elongation is 15-25%, 150 ° C. dry heat shrinkage is 2-10%,
It is preferable that the fineness unevenness is 0.5 to 1%, and more excellent effects can be expected by applying these conditions.

The polyphenylene sulfide resin is melt-spun, and the yarn is treated with a water-based emulsion oil agent so that the amount of adhered oil becomes 0.1 to 1% by weight. A method for producing a polyphenylene sulfide fiber having a single yarn fineness of 10 to 100 dtex, characterized by drawing at 4.5 times is provided.

Furthermore, in the method for producing the polyphenylene sulfide fiber of the present invention,
Adhering a non-aqueous oil agent to the taken yarn so that the total amount of oil adhering is 0.5 to 2% by weight;
The concentration of the water-based emulsion oil is 15 to 40% by weight;
Are preferable conditions, and by applying these conditions, further excellent effects can be expected.

According to the present invention, as will be described below, polyphenylene sulfide fibers suitable for industrial material applications with thick single yarn, high strength, and high toughness can be produced with high quality and high production efficiency at a low cost. Even if it is used as an application, it is no different from conventional thin fibers of single yarn.

It is an example of the schematic diagram of the manufacturing method of this invention.

Explanation of symbols

1: Spinneret 2: Insulating tube 3: Side blowing cooling chimney 4: Cooling air 5: Yarn 6: Spinning duct 7: First oil supply roller 8: Take-up roller 9: Second oil supply roller 10: Feed roller 11: First Stretching roller 12: Converging air nozzle 13: Second stretching roller 14: Third stretching roller 15: Relaxing roller 16: Entangling device 17: Winder 18: Textile package

Hereinafter, the present invention will be described in detail with reference to an example of a schematic diagram of the manufacturing method of FIG.

In the polyphenylene sulfide fiber of the present invention, the single yarn fineness is required to be 10 to 100 dtex, preferably 10 to 50 dtex, more preferably 15 to 45 dtex, and still more preferably 20 to 40 dtex. When the single yarn fineness is less than 10 dtex, there is no great difference in characteristics from the product using the conventional polyphenylene sulfide multifilament. On the other hand, although fibers exceeding 100 dtex can be produced, in this case, since the cooling is insufficient, the spinning property and the physical properties of the fiber are deteriorated, or in order to avoid this, the spinning speed must be extremely low. Anyway, it is not preferable because productivity deteriorates. Further, the polyphenylene sulfide fiber of the present invention is required to have a strength of 4.5 to 6 cN / dtex, and a more preferable range is 4.8 to 5.5 cN / dtex. This range is not a characteristic required for a product, but to obtain a good yarn-forming property equivalent to that of manufacturing a conventional polyphenylene sulfide fiber (hereinafter referred to as a single yarn fine yarn) having a single yarn fineness of several dtex. It has been clarified that it is an indispensable range. When the strength is less than 4.5 cN / dtex, the fluff is severely generated and the yarn breakage occurs frequently, so that the fiber product can hardly be wound up, and the fiber is used after being unwound from the obtained fiber package. I can't even do it. This is a very unique phenomenon that is not recognized in the conventional single-fine fine yarn. In the conventional single-fine fine yarn, for example, the yarn can be stably produced even at a strength around 4.0 cN / dtex. Further, when polyamide or polyester is produced, the above-described low-strength side does not deteriorate the yarn-making property, and when the same raw material is used, the low-strength side has better yarn-making property. That is, in the conventional melt spinning, when there are many fuzz and yarn breakage, it is preferable to reduce the strength by a method such as lowering the draw ratio, whereas the polyphenylene sulfide fiber (hereinafter referred to as the single yarn fineness) having a large single yarn fineness of the present invention. In the case of single yarn thick yarn), it has been found that there is an effect of increasing the draw ratio and improving the yarn forming property on the higher strength side. When the strength exceeds 6 cN / dtex, there is a phenomenon in which the fiber breaks without being able to withstand stretching, as is known in ordinary melt spinning. That is, in the production of single-filament thick yarn made of polyphenylene sulfide, there is an appropriate range within a narrow range on the high strength side. In order to obtain a single yarn thick fine yarn having such a strength range, it is preferable to draw at a total draw ratio of 3.8 to 4.5 times by a direct spinning drawing method.

In addition, in order to obtain the polyphenylene sulfide fiber of the present invention, it is preferable to treat the yarn with an aqueous emulsion oil so that the amount of attached oil is 0.1 to 1% by weight as a solid content. In general, in order to effectively suppress fluff and yarn breakage during stretching heat treatment, it is preferable that the amount of oil attached to the fiber is relatively large. For example, according to Japanese Patent Application Laid-Open No. 2001-262436, an aqueous oil agent is used for polyphenylene sulfide. In addition, it is said that the amount of oil adhered is preferably 1.0 to 3.0% by weight as a solid content, and 1.5 to 2.5% by weight of polyphenylene sulfide having a single fiber fineness of 4.5 dtex. It is disclosed that fibers can be obtained with a good amount of yarn-making property, while fluff and yarn breakage are deteriorated when the attached amount is 0.6% by weight. Even in the case of the polyphenylene sulfide fiber having a single yarn thickness according to the present invention, when the amount of attached oil is low, the yarn forming property is deteriorated as in the case of polyamide. However, when an amount exceeding 1% by weight as a solid content is adhered using a water-based emulsion oil agent, the yarn-making property is extremely deteriorated, the fuzz is severely generated, and the yarn breakage occurs frequently. Not only can the fibers be unwound from the resulting fiber package 18 but even used. This tendency becomes more prominent as the fineness of the single yarn increases. Surprisingly, when the single yarn is thickened, the fiber can be obtained with better yarn production by reducing the amount of aqueous oil used. Even more surprisingly, when a non-aqueous oil agent is attached to an undrawn yarn of a thick single polyphenylene sulfide without using a water-based oil agent, the fiber strength and elongation are improved. The tendency increases as the single yarn becomes thicker and the amount of non-aqueous oil attached increases. In order to obtain a polyphenylene sulfide fiber having a large single yarn fineness and a high strength without impairing the spinning property, it has been found that it is preferable to attach 0.1 to 1% by weight of an aqueous emulsion oil as a solid content as described above. It was.

In addition, it is preferable to feed the non-aqueous oil agent in the second stage so that the total amount of adhered oil is 0.5 to 2% by weight. In particular, it is effective when producing polyphenylene sulfide fibers having a single yarn fineness so large that the solid adhesion amount of the water-based oil must be adjusted to less than 0.5% by weight. The total amount of adhered oil may be determined by taking into consideration the manufacturing conditions as appropriate. However, if the yarn adhering property and the fluff quality are good, it is more economical to reduce the total amount of adhered oil. No problem at about 5 to 1% by weight. This is particularly effective when the single yarn fineness is 50 dtex or less.

It is not clear what effect water has on the physical properties and yarn-forming properties of such polyphenylene sulfide fibers, but the polyhydrate sulfide fibers have a very low saturated moisture content, and undrawn yarns with aqueous emulsion oils attached. There is almost no difference in strength and elongation between the undrawn yarn and the non-drawn yarn with non-aqueous oil adhered, and the properties of polyphenylene sulfide fibers change greatly with the treatment temperature. It is presumed that the amount of heat exchanged by the moisture adhering to the yarn surface being vaporized during the drawing heat treatment is greatly related. That is, even when only a non-aqueous oil agent is supplied without using an aqueous emulsion oil agent, there is a possibility that the polyphenylene sulfide fiber of the present invention can be obtained by supplying water in a mist-like or steam-like manner before oil supply. However, it is more economical to use as an aqueous emulsion oil. The solid content of the aqueous emulsion oil adhered to the polyphenylene sulfide fiber having a single yarn fineness of 50 dtex or less, preferably 40 dtex or less, more preferably 25 dtex or less is preferably 0.5 to 1% by weight, more preferably 0. .6 to 0.9% by weight, more preferably 0.7 to 0.8% by weight. Within this range, high-strength fibers can be easily obtained without impairing the spinning performance. However, in consideration of cost, the total adhesion amount of a non-aqueous oil agent having a known composition is 2% by weight or less, more preferably 1. There may be no additional oil supply so as to be 5% by weight or less, more preferably 1% by weight or less. If the single yarn fineness is less than 25 dtex, an aqueous emulsion alone is sufficient. On the other hand, when the single yarn fineness exceeds 50 dtex, the solid content of the aqueous emulsion oil is preferably 0.1 to 0.5% by weight, more preferably 0.1 to 0.3%, and still more preferably. Is 0.1 to 0.2%. In this case, a non-aqueous oil agent is further added so that the total adhesion amount exceeds 0.5% by weight, preferably 2% by weight or less, more preferably 1.5% by weight or less, and further preferably 1% by weight or less. Refueling is effective. Further, the concentration of the water-based emulsion oil is preferably 15 to 40% by weight, more preferably 15 to 30% by weight, and still more preferably 18 to 22% by weight. By adjusting the concentration within this range, an inexpensive and highly stable water-based emulsion oil agent can be obtained, and it is preferable because appropriate moisture can be adhered even in oil supply to the polyphenylene sulfide fiber. Further, it is preferable to add a surfactant and an antioxidant component to the oil agent so that these components adhere to the fiber surface, and the amount of the surfactant component is 0.01 to 1 wt. %, And the antioxidant component is more preferably 0.002 to 0.1% by weight. More preferably, the surfactant component is 0.1 to 0.5% by weight and the antioxidant component is 0.003 to 0.05% by weight. By adjusting and adhering both components within this range, the damage received during the stretching heat treatment is reduced, the variation in the strength and elongation is small, and high toughness is easily maintained.

The polyphenylene sulfide fiber of the present invention preferably has a total fineness of 100 to 1000 dtex, more preferably 200 to 900 dtex, still more preferably 400 to 700 dtex. It can be manufactured even if it is less than 100 dtex, but in that case, it often fails to satisfy the desired fiber strength, and may be combined or may be processed into the target product by combining and twisting. If the fineness is thin, the efficiency is low and this is not preferable. On the other hand, polyphenylene sulfide fibers having a total fineness exceeding 1000 dtex can also be obtained. However, in that case, they may be appropriately combined and used, and it is not necessary to dare to produce a large fine yarn using a large-scale yarn making facility.

Further, the number of single yarns is preferably 2 to 50, and more preferably 10 to 40. When the number of single yarns is 1, that is, in the state of monofilament, there are almost no applications that can be developed at present within the range of single yarn fineness of the present invention, and it is more productive to produce and split multifilaments of multiple yarn There are many. On the other hand, when the number of single yarns exceeds 50, although it depends on the size of the spinning equipment, it is difficult to provide the preferred level of cooling for the production of single yarn thick fine yarns with the current direct spinning drawing technology. Furthermore, the polyphenylene sulfide fiber of the present invention is preferably untwisted. A single yarn thick fine yarn can also be used as a multifilament. In this case, it is sufficient to apply a desired twist in a higher order process, but it can also be used after splitting. Since it cannot be done, it is not preferable. If a known winder used in a normal direct spinning drawing method is used, the fiber package 18 can be obtained without twisting.

The elongation is preferably 15 to 25%, more preferably 17 to 23%. If it is less than 15%, not only fuzz and yarn breakage occur frequently during yarn production, but the toughness is lowered, so that the high-order workability is also deteriorated. If it exceeds 25%, it is not preferable because the strength hardly satisfies the requirements of the present invention. However, if the relaxation rate after stretching is as large as possible, it is possible to obtain polyphenylene sulfide exceeding 25%.

The dry heat shrinkage at 150 ° C. is preferably 2 to 10%, more preferably 2 to 6%, and further preferably 2 to 4%. Since the single-filament thick polyphenylene sulfide of the present invention has a relatively high strength, it is difficult to obtain a 150 ° C. dry heat shrinkage of less than 2%. On the other hand, when it is desired to improve the rigidity of the product by using a high-temperature heat set at the time of high-order processing, it is preferable that the shrinkage rate is high. This is not preferable because the necessity of the stretching tension increases and the yarn-making property tends to deteriorate and the toughness decreases, and the fibers are freely shrunk and handling becomes complicated.

The fineness unevenness is preferably 0.5 to 1%, more preferably 0.6 to 0.8%. Fineness spots of 0.5% or less are difficult to obtain with current technology. On the other hand, if it exceeds 1%, the spinnability and stretchability deteriorate, which is not preferable.

The polyphenylene sulfide fiber of the present invention can be produced by the following method.

・ Polyphenylene sulfide pellets having a melt flow rate (MFR) of 50 to 600 are dried at 140 to 180 ° C. for about 2 to 24 hours to remove low-boiling foreign matters and melt-spun. 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, but may contain 0.1% by weight or less of trichlorobenzene (TCB) and may contain a small amount of other additives. Good.

An extruder type spinning machine is preferably used for melting the polymer pellets of the polyphenylene sulfide of the present invention. 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 spun from the spinneret pores using the spinneret 1, passed through a slow cooling zone directly under the die, and then cooled and solidified by blowing cold air. In the die, the orifices of the die 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 pressure on the back surface of the die. The spinning draft defined in (1) may be appropriately designed so as to 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 2 having a length of 5 to 10 cm, and the temperature is controlled so that the ambient temperature under the base 10 cm is 150 to 250 ° C. Cooling is performed by blowing cooling air 4 at 10 to 30 ° C. at a speed of 30 to 40 m / min, preferably at a speed of 35 m / min or more. Since it is necessary to enhance the cooling of the single yarn thick fine yarn of the present invention, the speed of the cold air to be blown is better. However, since the spinning tension is greatly reduced as compared with the conventional single yarn fine yarn, 40 m / min. If cold air is blown at the above speed, the yarn 5 is likely to jump out of the spinning duct 6 or comes into contact with the spinning duct, resulting in a decrease in fiber properties and frequent occurrence of fluff. A side blowing cooling chimney 3 that blows cold air at right angles to the spun yarn may be used, or an annular cooling chimney may be used to blow from the outer periphery to the center of the spun yarn bundle, or from the center to the outer periphery. However, it is preferable to use a side blowing cooling chimney.

Next, an oil agent is applied to the cooled and solidified yarn, and the yarn is wound and taken up by a take-up roller 8 that rotates at a predetermined speed. Oil supply can be carried out using a known method such as roller lubrication or guide lubrication. The oil agent used here may be either an aqueous emulsion oil agent or a non-aqueous oil agent mainly composed of a smoothing agent, an activator, an emulsifier, etc., but the first oil supply roller 7 is used for the first stage oil supply. It is preferable that the water-based emulsion oil is supplied and the second-stage oil supply is supplied with the non-aqueous oil using the second oil supply roller 9. The oil agent composition is, for example, an ester compound formed from polytetramethylene glycol having an average molecular weight of 600 to 6000, a dibasic acid, and a monovalent fatty acid, and includes a polyether ester having an average molecular weight of 2000 to 15000. However, the present invention is not limited to this, and other additives such as pH adjusters such as alkylene oxide adducts of alkylamines, antioxidants, ultraviolet absorbers, and fluorine compounds may be added as necessary. .

Specific examples of the smoothing agent component include esters of dihydric alcohols and higher fatty acids such as neopentyl glycol dilaurate and diethylene glycol diolate, esters of trihydric alcohols and higher fatty acids such as glycerol triolate and trinetyl roll propane triolate, penta Higher fatty acid esters such as erythritol tetraoleate and higher fatty acid esters, dioctyl sebacate, dioleyl adipate, esters of higher alcohols and dibasic acids such as diisostearyl thiodipropionate, dioleyl phthalate, trioctyl trimellitate , Esters of higher alcohols and aromatic carboxylic acids, such as tetraoctyl pyromellitate, and bityl stearate, isostearyl palmitate, oleyl larate, oleyl oleate Such as esters of higher alcohols and higher fatty acids.

Specific examples of the surfactant component include ester compounds of polyhydric alcohol alkylene oxide adducts, which are a reaction product of a compound having an alkylene oxide addition mole number of 10 to 40 mol and a monocarboxylic acid and / or dicarboxylic acid. Is mentioned. Examples of the ester compound include hardened castor oil EO (25), stearic acid of hardened castor oil ethylene oxide EO (25), maleic acid ester, and ethylene oxide EO (20) distearate.

Specific examples of the antioxidant include a single component or a mixture of two or more of a phenolic antioxidant, a phosphoric acid antioxidant, an amine antioxidant, a hindered antioxidant, and a sulfur antioxidant. The thing which was done is mentioned. The antioxidant is included in the surfactant.

The take-up roller 8 may be a single-hanging type, a Nelson type or a separate roller type, and any of them may be used, and the temperature is usually normal temperature, but water is circulated inside the roller to 20 to 40 ° C. To 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 polyphenylene sulfide fibers cannot be obtained with good productivity, and the polyphenylene sulfide fibers satisfy the strength range of the present invention. It is difficult to set an appropriate draw ratio for stably producing the film. 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 undesirable because it leads to deterioration of the spinning performance. It is necessary to once cool the polyphenylene sulfide yarn below the glass transition point.

Next, the take-up yarn is wound around the feed roller 10 without being wound once in order to stabilize the quality and yarn-making property, and after prestretching the yarn between the take-up roller and the feed roller, It can be wound using a multistage drawing method similar to that of polyester, or can be wound using a unique multistage drawing method suitable for the production of polyphenylene sulfide fibers proposed in JP-A-2001-262436. However, when the spinning speed is low, the latter is preferably used.

In a multi-stage drawing method similar to polyamide, etc., the polyphenylene sulfide fiber is drawn and heat-treated by the following method. The pre-stretch is 2 to 10%, preferably 4 to 8%. The temperature of the feed roller 10 is preferably controlled to 70 to 110 ° C. Next, the first stage of stretching is performed between the feed roller and the first stretching roller 11. The first stretching roller is heated to 80 to 120 ° C. In order to obtain the polyphenylene sulfide fiber of the present invention, the first stage draw ratio is preferably 3.3 to 3.8 times as high as possible without causing single yarn breakage. The first-stage-stretched yarn performs second-stage stretching with the second stretching roller 13. The second stretching roller is set in the range of 180 to 250 ° C. The second stage draw ratio is preferably set to 1.05 to 1.3 times. At this time, it is preferable to use the converging air nozzle 12 to condense the yarn between the first drawing roller and the second drawing roller, because yarn breakage is reduced. Further, if necessary, the third stage of stretching may be performed with the third stretching roller 14. In this case, the temperature of the third stretching roller is 180 to 250 ° C., and is usually set higher than that of the second stretching roller. 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 ratio, it is not possible to obtain a single yarn thick fine yarn made of polyphenylene sulfide with less fluff and yarn breakage according to the present invention, and only by selecting a magnification outside this range. It falls into a state where it cannot be made. In particular, when the temperature of the second stretching roller 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 contacting the high temperature roller. The yarn stretched in two or three stages is then subjected to a relaxation heat treatment with the relaxation roller 15. The relaxation roller is not heated or set to 150 ° C. or lower. The relaxation rate is 2 to 10%, preferably 4 to 8%. Each roller from the first stretching roller to the relaxation roller is preferably a Nelson type roller.

If the spinning speed is low and spinning is not possible even under the above-mentioned conditions, the polyphenylene sulfide fiber is drawn and heat-treated by the following method. The pre-stretch is set to 1.2 to 1.6 times, the first stage draw ratio is set to 2.5 to 3.5 times, and all other conditions may be set as the above conditions. The first stage draw ratio is 1.2 to 1.6, the second stage draw ratio is 2.5 to 3.5 times, and the third stage draw ratio is 3.8. It is also possible to use a method of setting to be 4.5 times. In this case, it is preferable that the temperature of the first stretching roller is 70 to 110 ° C., the temperature of the second stretching roller is 80 to 120 ° C., and the temperature of the third stretching roller is 180 to 250 ° C.

Further, when the obtained polyphenylene sulfide yarn is used without being split, it is preferable to provide entanglement by fluid treatment before winding the yarn. In order to impart entanglement, the entanglement imparting device 16 for fluid treatment, the flow rate of the fluid during treatment, the winding tension, etc. may be set as appropriate, so that the number of entanglement is 5 to 20 / m. It is preferable to carry out.

The polyphenylene sulfide fiber of the present invention can be obtained by the above method. The polyphenylene sulfide fiber of the present invention can be simultaneously drawn by multiple yarns at a spinning speed of 2000 m / min or more by the direct spinning drawing method, and has very good drawability in the yarn making process. And there is almost no catching by fluff when the fiber is unwound. That is, it is possible to obtain high-order process passability at a level comparable to that of conventional single-fine fine yarns made of polyphenylene sulfide. The polyphenylene sulfide fiber of the present invention is suitably used for applications where the characteristics and rigidity of polyphenylene sulfide are required, particularly for industrial materials.

Hereinafter, the present invention will be described in detail by way of examples. The definition of each characteristic and the measuring method in the present invention are as follows.

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

(2) Number of single yarns: Calculated by the method of JIS L1013 (1999) 8.4.

(3) Single yarn fineness: Calculated by dividing the total fineness by the number of single yarns.

(4) Amount of adhered oil: The diethyl ether extract was measured by the method of JIS L1013 (1999) 8.27 b) and used as the amount of adhered oil. The amount of water-based oil was measured by collecting the undrawn yarn subjected to the first-stage oiling and measuring the amount of oil attached. The total amount of attached oil was measured from the wound drawn yarn. The adhesion amount of the surfactant and the antioxidant was determined from the oil composition and the adhesion amount in the first and second stages.

(5) Strength / Elongation: Measured under the constant speed extension condition shown in JIS L1013 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. The elongation was obtained from the elongation at the point showing the maximum strength in the SS curve.

(6) 150 ° C. dry heat shrinkage: Measured by a method of JIS L1013 (1999) 8.18.2 b) using a dryer heated to 150 ° C.

(7) Number of entanglements: The number of entangled portions having a length of 1 mm or more was measured by a water immersion method and converted to the number per 1 m. Ten raw yarns were measured and indicated by the average value.

As the water immersion bath, a bath having a length of 70 cm, a width of 15 cm, and a depth of 5 cm and provided with a partition plate at a position 10 cm from both ends in the longitudinal direction was used. The bath was filled with pure water, the raw yarn sample was immersed in water, and the number of entangled portions was measured. In addition, in order to exclude the influence of impurities, such as an oil agent, the pure water was replaced | exchanged for every measurement.

(8) Fineness spots: Half value was measured using Wooster Tester Monitor C (USTER TESTER MONITOR C) manufactured by Zellweger Wooster. Using the INEAT mode, a measurement of 125 m was performed at a yarn speed of 25 m / min.

(9) Yarn breakage: This is the number of yarn breakage when yarn can be produced until the total weight of the fiber package reaches 300 kg.

(10) Yarn fluff: A laser type fluff detector is installed at a location 5 mm away from the roller installed between the stretching and relaxation heat treatment roller and the winder, and the number of fluff detected until the total weight of the fiber package reaches 300 kg. Displayed in terms of the number per 10,000 km.

(11) Unwinding property: Six obtained fiber packages (30 kg) were wound back at a speed of 300 m / min, and the number of times that they could not be unwound due to being caught by fluff during the rewinding was counted.

(12) Fluffing of twisted yarn: Three fibers obtained were aligned and twisted with a twisting machine so that the number of turns was 5 turn / 10 cm, and the presence or absence of fluffing of the obtained twisted yarn was confirmed.

[Example 1]
Toray polyphenylene sulfide polymer with MFR of 200 is melted by an extruder type spinning machine under a vacuum of 1.33 kPa so that the polymer temperature is 315 ° C., and the melted polymer has 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 solidified by cooling with cold air at 25 ° C. and 38 m / min using a side blowing cooling chimney, and then an aqueous system having a smoothing agent, etc. The emulsion oil (water system 20) was applied by an oil supply roller rotating at 10 rpm, wound around a spinning take-up roller rotated at a speed of 558 m / min, and the spun yarn was taken up. The water-based emulsion oil (water-based 20) is mainly composed of polyether ester, which is a smoothing agent composed of polytetramethylene glycol, adipic acid and oleic acid made by Takemoto Yushi. Of IRGANOX 245, lauryl (EO) 2 phosphate K salt, an extreme pressure agent made of lauryl alcohol PO / EO adduct, and a surfactant such as hydrogenated castor oil EO25, and 80% by weight of pure water are emulsified. The ratio of the components in the oil is 42.3% by weight of the surfactant and 0.96% by weight of the antioxidant.

Subsequently, a non-aqueous oil agent comprising 43.4% by weight of a surfactant and 1.42% by weight of an antioxidant diluted with 14% by weight of mineral oil continuously at 8 rpm. Both sides were lubricated with a rotating oiling roller and fed to a stretching / heat treatment zone to produce polyphenylene sulfide fibers by a direct spinning stretching method.

First, a stretch of 6% is applied between the take-up roller and the feed roller, then the first stage of stretching between the feed roller and the first stretching roller, and the second stage between the first stretching roller and the second stretching roller. The eye was stretched. Subsequently, 5% relaxation heat treatment was performed between the second stretching roller and the relaxation roller, the yarn was entangled with the entanglement imparting device, and then wound with a winder. The surface temperature of each roller was set so that the take-up roller was normal temperature, the feed roller was 80 ° C., the first stretching roller was 110 ° C., the second stretching roller was 235 ° C., and the relaxation roller was 150 ° C. The rotation speeds of the first stretching roller and the second stretching roller were set so that the first stage stretching ratio was 3.70 times and the overall stretching ratio was 4.30 times.

Table 1 shows the properties and evaluation results of the obtained polyphenylene sulfide fibers. High strength at high draw ratio, proper oiling method and amount of attached oil, there are few yarn breaks and yarn fluffs, and there are no catches due to fluffing during unwinding. A fiber package could be obtained. Moreover, the twisted yarn without fluff could be obtained.

[Examples 2 and 3]
Example 2 uses a spinneret in a staggered single-row arrangement having eight discharge holes with a diameter of 0.70 mm, changes the rotation speed of each roller with a take-up speed of 512 m / min, and Except that the rotational speed was set to 12 rpm, Example 3 used a spinneret of a staggered single row arrangement having five discharge holes having a diameter of 0.75 mm, and a take-up speed of 512 m / min. Polyphenylene sulfide fibers were obtained in the same manner as in Example 1 except that the rotation speed of each roller was changed and the rotation speed of the second-stage oil supply roller was changed to 15 rpm. Table 1 shows the properties and evaluation results of the obtained polyphenylene sulfide fibers. As compared with Example 1, the results were slightly inferior in yarn making, yarn fluff and unwinding, and the strength and elongation decreased as the single yarn fineness increased, but a satisfactory evaluation result could be obtained. .

[Example 4]
A polyphenylene sulfide fiber was obtained in the same manner as in Example 1 except that the take-up speed was 628 m / min and the rotation speed of each roller was changed. Table 1 shows the properties and evaluation results of the obtained polyphenylene sulfide fibers. As compared with Example 1, the results were slightly inferior in yarn cutting and yarn fluff, but a satisfactory evaluation result could be obtained.

[Example 5]
The metering pump is adjusted so that the total fineness becomes 220 dtex, a spinneret with a staggered single row arrangement having 10 discharge holes with a diameter of 0.50 mm is used, the rotation speed of the first-stage oil supply roller is 15 rpm, A polyphenylene sulfide fiber was obtained in the same manner as in Example 1 except that the rotation speed of the oil supply roller at the stage was set to 5 rpm. Table 1 shows the properties and evaluation results of the obtained polyphenylene sulfide fibers. As compared with Example 1, the results were slightly inferior in yarn cutting and yarn fluff, but a satisfactory evaluation result could be obtained.

[Example 6]
Polyphenylene sulfide fibers were obtained in the same manner as in Example 1 except that the rotation speed of the first-stage oil supply roller was 25 rpm and the second-stage oil supply was not performed. Table 1 shows the properties and evaluation results of the obtained polyphenylene sulfide fibers. Although the result was slightly inferior to that of Example 1, the satisfactory evaluation result could be obtained.

[Examples 7 and 8]
A polyphenylene sulfide fiber was obtained in the same manner as in Example 6 except that the overall draw ratio was changed and the production conditions such as the spinning speed were as shown in Table 2. Table 2 shows the properties and evaluation results of the obtained polyphenylene sulfide fibers. As compared with Example 6, yarn cutting breakage, yarn fluffing, and unwinding properties were slightly inferior, but satisfactory evaluation results could be obtained.

[Example 9]
Using a zigzag two-row array spinneret with 30 discharge holes with a diameter of 0.35 mm, the spinning speed was 690 m / min, the first stage draw ratio was 3.50 times, and the overall draw ratio was 4.20 times. The polyphenylene sulfide fibers were obtained in the same manner as in Example 6 except that the production conditions were as shown in Table 2 and the rotation speed of the first stage oiling roller was changed to 35 rpm. Table 2 shows the properties and evaluation results of the obtained polyphenylene sulfide fibers. Although the number of yarns was increased, satisfactory results were obtained.

[Example 10]
In the same manner as in Example 1, except that the antioxidant component of the aqueous emulsion oil used for the first-stage oil supply was halved and the antioxidant component was removed from the non-aqueous oil oil used for the second-stage oil supply, polyphenylene was obtained. Sulfide fiber was obtained. Table 2 shows the properties and evaluation results of the obtained polyphenylene sulfide fibers. Compared to Example 1, since the antioxidant component was reduced, the strength and elongation decreased, resulting in inferior yarn cutting, yarn fluff, and unraveling properties, but obtaining a generally satisfactory evaluation result. I was able to.

[Example 11]
A polyphenylene sulfide fiber was obtained in the same manner as in Example 6 except that the rotation speed of the first-stage oil supply roller was 15 rpm. Table 2 shows the properties and evaluation results of the obtained polyphenylene sulfide fibers. The strength and elongation, yarn breakage, yarn fluff, and unwinding property were inferior to Example 6, but generally satisfactory evaluation results could be obtained.

[Comparative Examples 1 and 2]
The polyphenylene sulfide fiber was changed in the same manner as in Example 6 except that the overall draw ratio was changed and the production conditions such as the spinning speed were as shown in Table 2 and the rotation speed of the first stage oiling roller was 30 rpm. Table 3 shows the results of yarn production. Since Comparative Example 1 was low in strength, yarn breakage occurred frequently, and polyphenylene sulfide fibers could be collected only in an amount sufficient to measure fiber characteristics. Yarn fluff was always detected with a laser fluff detector. In Comparative Example 2, the overall draw ratio was too high, and even a fiber sample could not be collected.

[Comparative Examples 3 and 4]
Table 3 shows the results of spinning polyphenylene sulfide fibers in the same manner as in Example 6, except that the rotation speed of the first-stage oiling roller was changed to 35 rpm in Comparative Example 3 and 50 rpm in Comparative Example 4, respectively.

In Comparative Example 3, the amount of attached oil was large, so that the yarn breakage, the yarn fluff, and the unwinding property were extremely deteriorated, and the generated fluff was quite large, and many fuzzes of the twisted yarn were observed.
In Comparative Example 4, the amount of attached oil is the same as that of a conventional polyphenylene sulfide fiber having a single yarn fineness, but since the amount of attached oil is too much in the single yarn thick yarn of the present invention, yarn breakage occurs frequently, and the fiber Even samples could not be collected.

[Comparative Example 5]
A polyphenylene sulfide fiber was used in the same manner as in Example 6 except that the spinning nozzle of a staggered arrangement having 24 discharge holes with a diameter of 0.40 mm was used and the rotation speed of the first stage oiling roller was changed to 45 rpm. Table 3 shows the results of yarn production.
Although the yarn cutting and the yarn fluff were clearly inferior, the results were not as high as those in Comparative Example 4, the unraveling property was not a problem, and the fuzz of the twisted yarn was not observed.

[Comparative Example 6]
Table 3 shows the results of spinning polyphenylene sulfide fibers in the same manner as in Example 1 except that a water-based emulsion oil used for first-stage oiling was emulsified with 90% by weight of pure water (aqueous 10). Show. Since the amount of water-based oil attached was small and the amount of moisture applied was large, yarn breakage occurred frequently, and polyphenylene sulfide fibers could only be collected to measure fiber characteristics.

[Comparative Example 7]
The composition is the same as that of the oil agent of Example 1, and the component ratio in the oil agent when the mineral oil component is removed is 31% by weight of the surfactant, 0.4% by weight of the antioxidant, and 75% by weight. A non-aqueous oil diluted with mineral oil was used as the first-stage oil supply, the number of rotations of the oil supply roller was 25 rpm, and the second-stage oil supply was not performed. Table 4 shows the results of spinning polyphenylene sulfide fibers. Yarn breakage, yarn fluff, and unwinding were good, but the strength and elongation were greatly reduced.

[Comparative Example 8]
A comparative example, except that a spinneret in a staggered array with 12 discharge holes with a diameter of 0.60 mm was used, the take-up speed was 512 m / min, and the production conditions such as the roller speed were as shown in Table 2. Table 4 shows the results of spinning polyphenylene sulfide fibers in the same manner as in Table 7. The yarn breakage, yarn fluff, and unwinding property were good, but the strength and elongation were further reduced.

[Comparative Example 9]
Except for using a spinneret in a staggered array with four discharge holes with a diameter of 0.80 mm, the rotational speed of the first stage oiling roller was 15 rpm, and the rotational speed of the second stage oiling roller was 20 rpm, Table 4 shows the results of spinning polyphenylene sulfide fibers in the same manner as in Example 2. As a result, the strength and elongation decreased, and the yarn cutting, yarn fluff and unwinding properties were poor.

[Reference Examples 1 to 3]
It is an example which shows the polyphenylene sulfide fiber of the conventional single yarn fineness finely threaded on the manufacturing conditions shown in Table 4. In Reference Example 1, the first-stage oil supply aqueous emulsion oil of Example 1 was applied at a roller rotation speed of 25 rpm, and in Reference Examples 2 and 3, the first-stage oil supply non-aqueous oil agent of Comparative Example 7 was rotated at a roller rotation speed. Adjustments were made to be 17 rpm and 25 rpm, respectively. Although Reference Example 1 does not belong to the scope of the present invention in terms of strength and amount of attached oil, it has a good yarn production record. Reference Examples 2 and 3 were also the same as Reference Example 1, and no deterioration in physical properties was observed even when a large amount of non-aqueous oil was used.

According to the present invention, a polyphenylene sulfide fiber having a large single yarn fineness can be obtained with a good yarn forming property equivalent to a single fine yarn by a conventional direct spinning drawing method without using special equipment.

Therefore, the technology of the present invention greatly contributes to the field of industrial materials that require rigidity more than conventional polyphenylene sulfide fiber products.

Claims

A polyphenylene sulfide fiber having a single yarn fineness of 10 to 100 dtex and a strength of 4.5 to 6 cN / dtex.
2. The polyphenylene sulfide fiber according to claim 1, wherein at least a surfactant component and an antioxidant component are adhered to the fiber surface.
The total amount of adhered oil relative to the fiber weight is 0.5 to 2% by weight, of which the surfactant component amount is 0.01 to 1% by weight and the antioxidant component amount is 0.002 to 0.1% by weight. The polyphenylene sulfide fiber according to claim 1, wherein the polyphenylene sulfide fiber is.
The polyphenylene sulfide fiber according to any one of claims 1 to 3, wherein the total fineness is 100 to 1000 dtex, the number of single yarns is 2 to 50, and the yarn is untwisted.
The polyphenylene sulfide fiber according to any one of claims 1 to 4, having an elongation of 15 to 25% and a dry heat shrinkage of 150 ° C of 2 to 10%.
The polyphenylene sulfide fiber according to any one of claims 1 to 5, wherein fineness spots are 0.5 to 1%.
A polyphenylene sulfide resin is melt-spun, the yarn is treated with a water-based emulsion oil so that the amount of adhered oil is 0.1 to 1% by weight, and then taken up, and then the total draw ratio is 3.8 to 4 without winding. A method for producing a polyphenylene sulfide fiber having a single yarn fineness of 10 to 100 dtex, characterized by stretching at a magnification of 5 times.
The method for producing a polyphenylene sulfide fiber according to claim 7, wherein a non-aqueous oil agent is adhered to the taken yarn so that the total amount of adhered oil is 0.5 to 2% by weight.
The method for producing polyphenylene sulfide fiber according to claim 7 or 8, wherein the concentration of the aqueous emulsion oil is 15 to 40% by weight.