JP2016186136A - Wet type spinneret for triangular cross-section acrylic fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an improved wet type spinneret so that it becomes possible to produce preferably fine-denier triangular cross-section acrylic fiber with excellent spinning stability and productivity.SOLUTION: Provided is a spinneret for wet spinning acrylonitrile-based polymer, more specifically a wet type spinneret for triangular cross-section acrylic fiber, where a length of a side of a nozzle hole is 0.060 to 0.080 mm and a length of a discharge hole is 0.04 to 0.15 mm. The wet type spinneret is used for wet-spinning a spinning dope having a polymer concentration of 18 to 26 mass%, the polymer being an acrylonitrile-based polymer containing acrylonitrile in an amount of 80 mass% or more.SELECTED DRAWING: None

Description

  The present invention relates to a wet spinneret that is improved so that acrylic fibers, preferably having a triangular cross-section, can be produced with excellent spinning draw stability and productivity.

  Acrylic fibers have a soft texture, heat retention, bulkiness and excellent dyeability that are most similar to wool compared to other synthetic fibers, and are widely used in the clothing and interior fields. However, in recent years, the demand for further soft texture and heat retention has been increasing for fiber products made of acrylic fibers, and improvement has been demanded by reducing the fineness of the irregular cross-section fibers.

  Conventionally, various proposals have been made for the fineness of an acrylic fiber having an irregular cross section. For example, a method has been proposed in which high-stretching at a draw ratio of 7 to 15 times is employed after solidification at a low spinning draft of 0.1 to 0.5 in a fiber production process to obtain a modified cross-section fineness acrylic fiber ( (See Patent Document 1). Also proposed is a method of spinning an acrylonitrile polymer into a dimethylacetamide aqueous bath to obtain a modified cross-section fine acrylic fiber so that the relationship between the spinning draft and the nozzle hole satisfies a specific numerical range. (See Patent Document 2).

  However, although these methods can obtain practically desirable modified cross-sectional fineness acrylic fibers, the spinning stability and productivity in the process of producing these modified cross-sectional fineness acrylic fibers are still unsatisfactory. It was enough.

JP 2003-301322 A Japanese Patent No. 4764378

  Accordingly, an object of the present invention is to provide an improved wet spinneret so that acrylic fibers having a fineness and a triangular cross section can be produced with excellent spinning stretch stability and productivity.

  The present invention is to solve the above-mentioned problems, and the spinneret for wet spinning of the acrylic fiber having a fineness and a triangular cross section according to the present invention has a length of one side of the nozzle hole of 0.00. It is a wet spinneret of a triangular cross-section acrylic fiber characterized by being a regular triangular hole having a length of 060 to 0.080 mm and a discharge hole length of 0.04 to 0.15 mm.

  According to a preferred aspect of the wet spinneret of the triangular cross-section acrylic fiber of the present invention, the spinneret comprises a spinning stock solution in which the polymer concentration of the acrylonitrile polymer containing 80% by mass or more of acrylonitrile is 18 to 26% by mass. A wet spinneret for wet spinning.

  According to the present invention, even when a wet spinneret having a plurality of discharge holes is formed on an acrylic fiber having a triangular cross-section, the close contact between the spun single fibers is preferably generated. In spite of insufficient solidification, it is possible to effectively suppress the occurrence of single fiber breakage, and at the time of high-speed take-up necessary to improve productivity, spinning without causing thread breakage on the base surface. A wet spinneret capable of achieving the above is obtained.

  In addition, the wet spinneret of the present invention can be stretched without causing yarn breakage even in the stretching process for obtaining the necessary tensile strength as a triangular cross-section acrylic fiber having a fineness. The cross-section of quality fineness enables stable production without substantially impairing the productivity of triangular acrylic fibers.

FIG. 1 is a front view of a nozzle hole for illustrating a hole of a spinneret for wet-spinning acrylic fibers having a triangular cross section according to the present invention. FIG. 2 is a cross-sectional view for illustrating the holes of a spinneret for wet-spinning acrylic fibers having a triangular cross section according to the present invention.

  The spinneret for wet-spinning acrylic fibers having a fineness and a triangular cross-section according to the present invention has a length of one side of the nozzle hole of 0.060 to 0.080 mm and a length of the discharge hole of 0.04 to 0.04 mm. It is a wet spinneret with a regular triangular hole of 0.15 mm.

  The wet spinneret of acrylic fiber having a triangular cross section according to the present invention is preferably for wet spinning a spinning stock solution having a polymer concentration of 18 to 26% by mass including an acrylonitrile polymer containing 80% by mass or more of acrylonitrile. The spinneret is a wet spinneret having a regular triangular hole in which the length of one side of the nozzle hole is 0.060 to 0.080 mm and the length of the discharge hole is 0.04 to 0.15 mm.

  The acrylonitrile polymer used in the present invention may be a homopolymer of acrylonitrile as long as it is a polymer containing acrylonitrile at 80% by mass or more, preferably 85% by mass or more, but within a range not exceeding 20% by mass. An acrylonitrile copolymer obtained by copolymerizing a vinyl monomer copolymerizable with acrylonitrile is preferable. When the amount of acrylonitrile in the acrylonitrile copolymer is less than 80% by mass, the fiber is inferior in physical properties and heat resistance.

  Examples of the ethylenic vinyl monomer copolymerizable with acrylonitrile include acrylic acid, methacrylic acid or esters thereof, acrylamide, methacrylamide, vinyl acetate, vinyl chloride, and vinylidene chloride, with methyl acrylate being particularly preferred. Used.

  Examples of the sulfonic acid-containing vinyl monomer include acidic monomers such as vinyl sulfonic acid, acrylic sulfonic acid, methallyl sulfonic acid and unsaturated sulfonic acid such as P-styrene sulfonic acid or salts thereof. Sodium sulfonate is preferably used.

  The polymer concentration of the acrylonitrile-based polymer used in the present invention is preferably 18 to 26% by mass, more preferably 20 to 24% by mass. If the polymer concentration is less than 18% by mass, an irregular cross-sectional shape cannot be obtained. If the polymer concentration exceeds 26% by mass, the spinning stock solution is not stable and adversely affects the spinnability and the like.

  Next, the wet spinneret of the present invention will be described with reference to the drawings. FIG. 1 is a front view of a nozzle hole for illustrating a spinneret hole for wet-spinning acrylic fibers having a triangular cross-section according to the present invention, and FIG. 2 is a cross-sectional view of a spinneret hole. .

  1 and 2, the wet spinneret of the present invention is a positive spinner having a length 1 of one side of the nozzle hole 3 of 0.060 to 0.080 mm and a length 4 of the discharge hole of 0.04 to 0.15 mm. It is a triangular hole. The acrylonitrile-based polymer is pushed through the introduction hole 2 and is pushed into the DMSO and water bath solution from the nozzle hole 3 to become a coagulated yarn of triangular cross-section acrylic fiber.

  The wet spinneret of the present invention is preferably a regular triangular hole, and the length of one side of the nozzle hole is 0.060 to 0.080 mm, preferably 0.065 to 0.075 mm. If the length of one side of the nozzle hole is less than 0.060 mm, it is difficult to manufacture the nozzle and the spinning stability is reduced due to nozzle clogging. On the other hand, if the length of one side of the nozzle hole exceeds 0.080 mm, thread breakage occurs at the die surface, making it difficult to obtain fine fiber having a single fiber fineness of 1.2 dtex or less.

The length of the discharge hole of the wet spinneret of the present invention is 0.04 to 0.15 mm, preferably 0.05 to 0.10 mm. If the length of the discharge hole is less than 0.04 mm, yarn breakage occurs on the die surface, which adversely affects the spinnability and the like, and if it exceeds 0.15 mm, it causes equipment damage such as an increase in nozzle pressure.

  Furthermore, the wet spinneret of the present invention is used to obtain a coagulated yarn of triangular cross-section acrylic fiber by immersing the acrylonitrile-based copolymer in a DMSO and water bath after discharge.

  Moreover, the single fiber fineness of the triangular cross-section acrylic fiber obtained by using the wet spinneret of the present invention is a single fiber fineness of 0.3 to 1.3 dtex, preferably 0.4 to 1.2 dtex. Regarding the single fiber fineness, it is possible to obtain a triangular cross-section acrylic fiber having a fineness of 0.3 to 1.3 dtex by changing the discharge amount of the acrylonitrile copolymer.

  The finely-decorated triangular cross-section acrylic fiber obtained by using the wet spinneret of the present invention is used for clothing such as sweaters, jerseys, underwear, socks and faux fur, or in the interior field such as blankets, carpets, bath mats and curtains. Can be used.

  Next, the wet spinneret of acrylic fiber having a triangular cross-section according to the present invention and the effects thereof will be specifically described by way of examples, but the present invention is not limited to these.

(1) Evaluation of spinnability and stretchability:
With respect to spinnability, “○” indicates that there is no yarn breakage on the die surface, and the spinnability was accepted. Further, “△” indicates that there is a slight thread breakage on the die surface, and “×” indicates that there is frequent breakage. Furthermore, about the drawability, the thing which does not wind the single fiber around a roller was set as "(circle)", and it was set as the pass as a drawability. Further, “△” indicates that the single fiber is slightly wound around the roller, and “X” indicates that the single fiber is frequently wound. [Table 1] shows the evaluation criteria for the spinnability and stretchability.

(2) Measuring method of single fiber fineness and tensile strength:
JIS L1015: (2010) Measured by chemical fiber staple test method.

[Example 1]
Acrylonitrile 87% by mass, methyl acrylate 12% by mass and sodium methallyl sulfonate 1% by mass were copolymerized in DMSO to obtain an acrylonitrile-based copolymer, and a spinning stock solution having a spinning stock solution concentration of 21% by weight was obtained. . The length of one side of the nozzle hole in the coagulation bath in which the spinning dope obtained as described above was adjusted to a temperature of 65 ° C. and a bath solution of DMSO 60 mass% and water 40 mass% was adjusted to 40 ° C. Is 0.075 mm, the length of the discharge hole is extruded from a hole of 0.060 mm, wet-spun, stretched 4.5 times in hot water at 98 ° C., and the post-stretching speed is 85 m / min. Washed with water, attached oil, dried and densified using a hot air drier, single fiber fineness of 1.0 dtex, tensile strength of 2.6 cN / dtex, fineness and triangular cross-section acrylic fiber Got. The spinnability in the process of obtaining acrylic fibers with a triangular cross-section of fineness is acceptable (◯) without yarn breakage on the die surface, and the stretchability is also acceptable without winding single fibers around the roller ( Yes). The results are shown in Table 2.

[Example 2]
Acrylonitrile 87% by mass, methyl acrylate 12% by mass and sodium methallyl sulfonate 1% by mass were copolymerized in DMSO to obtain an acrylonitrile-based copolymer, and a spinning stock solution having a spinning stock solution concentration of 21% by weight was obtained. . The length of one side of the nozzle hole in the coagulation bath in which the spinning dope obtained as described above was adjusted to a temperature of 65 ° C. and a bath solution of DMSO 60 mass% and water 40 mass% was adjusted to 40 ° C. Is 0.075 mm, and the length of the discharge hole is extruded from a hole of 0.060 mm, wet-spun, stretched 6.0 times in hot water at 98 ° C., and the speed after stretching is 85 m / min. Washed with water, attached oil, dried and densified with a hot air dryer, single fiber fineness of 1.0 dtex, tensile strength of 3.0 cN / dtex, fineness and triangular cross-section acrylic fiber Got. The spinnability in the process of obtaining acrylic fibers with a triangular cross-section of fineness is acceptable (◯) without yarn breakage on the die surface, and the stretchability is also acceptable without winding single fibers around the roller ( Yes). The results are shown in Table 2.

[Example 3]
Acrylonitrile (87% by mass), methyl acrylate (12% by mass) and methallyl sulfonic acid soda (1% by mass) were copolymerized in DMSO to obtain an acrylonitrile-based copolymer to obtain a spinning stock solution having a spinning stock solution concentration of 23% by weight. . The length of one side of the nozzle hole in the coagulation bath in which the spinning dope obtained as described above was adjusted to a temperature of 65 ° C. and a bath solution of DMSO 60 mass% and water 40 mass% was adjusted to 40 ° C. Is 0.075 mm, and the length of the discharge hole is extruded from a hole of 0.060 mm, wet-spun, stretched 6.0 times in hot water at 98 ° C., and the speed after stretching is 85 m / min. Washed with water, attached oil, dried and densified with a hot air dryer, single fiber fineness of 1.0 dtex, tensile strength of 3.0 cN / dtex, fineness and triangular cross-section acrylic fiber Got. The spinnability in the process of obtaining acrylic fibers with a triangular cross-section of fineness is acceptable (◯) without yarn breakage on the die surface, and the stretchability is also acceptable without winding single fibers around the roller ( Yes). The results are shown in Table 2.

[Example 4]
Acrylonitrile 87% by mass, methyl acrylate 12% by mass and sodium methallyl sulfonate 1% by mass were copolymerized in DMSO to obtain an acrylonitrile-based copolymer, and a spinning stock solution having a spinning stock solution concentration of 21% by weight was obtained. . The length of one side of the nozzle hole in the coagulation bath in which the spinning dope obtained as described above was adjusted to a temperature of 65 ° C. and a bath solution of DMSO 60 mass% and water 40 mass% was adjusted to 40 ° C. Is 0.067 mm, and the length of the discharge hole is extruded from a hole of 0.090 mm, wet-spun, stretched 4.5 times in hot water at 98 ° C., and the post-stretching speed is 85 m / min. Washed with water, attached oil, dried and densified using a hot air dryer, single fiber fineness of 0.7 dtex, tensile strength of 2.7 cN / dtex, fineness and triangular cross-section acrylic fiber Got. The spinnability in the process of obtaining acrylic fibers with a triangular cross-section of fineness is acceptable (◯) without yarn breakage on the die surface, and the stretchability is also acceptable without winding single fibers around the roller ( Yes). The results are shown in Table 2.

[Example 5]
92% by mass of acrylonitrile, 7% by mass of methyl acrylate and 1% by mass of sodium methallyl sulfonate were copolymerized in DMSO to obtain an acrylonitrile-based copolymer to obtain a spinning dope with a spinning dope concentration of 24% by mass. . The length of one side of the nozzle hole in the coagulation bath in which the spinning dope obtained as described above was adjusted to a temperature of 65 ° C. and a bath solution of DMSO 60 mass% and water 40 mass% was adjusted to 40 ° C. Is 0.067 mm, and the length of the discharge hole is extruded from a hole of 0.090 mm, wet-spun, stretched 4.5 times in hot water at 98 ° C., and the post-stretching speed is 85 m / min. Washed with water, attached oil, dried and densified using a hot air dryer, single fiber fineness of 0.7 dtex, tensile strength of 2.7 cN / dtex, fineness and triangular cross-section acrylic fiber Got. The spinnability in the process of obtaining acrylic fibers with a triangular cross-section of fineness is acceptable (◯) without yarn breakage on the die surface, and the stretchability is also acceptable without winding single fibers around the roller ( Yes). The results are shown in Table 2.

[Example 6]
92% by mass of acrylonitrile, 7% by mass of methyl acrylate and 1% by mass of sodium methallyl sulfonate were copolymerized in DMSO to obtain an acrylonitrile-based copolymer to obtain a spinning dope with a spinning dope concentration of 24% by mass. . The length of one side of the nozzle hole in the coagulation bath in which the spinning dope obtained as described above was adjusted to a temperature of 65 ° C. and a bath solution of DMSO 60 mass% and water 40 mass% was adjusted to 40 ° C. Is 0.075 mm, and the length of the discharge hole is extruded from a hole of 0.060 mm, wet-spun, stretched 6.0 times in hot water at 98 ° C., and the speed after stretching is 85 m / min. Washed with water, attached oil, dried and densified with a hot air dryer, single fiber fineness of 1.0 dtex, tensile strength of 3.0 cN / dtex, fineness and triangular cross-section acrylic fiber Got. The spinnability in the process of obtaining acrylic fibers with a triangular cross-section of fineness is acceptable (◯) without yarn breakage on the die surface, and the stretchability is also acceptable without winding single fibers around the roller ( Yes). The results are shown in Table 2.

[Comparative Example 1]
Acrylonitrile 87% by mass, methyl acrylate 12% by mass and sodium methallyl sulfonate 1% by mass were copolymerized in DMSO to obtain an acrylonitrile-based copolymer, and a spinning stock solution having a spinning stock solution concentration of 21% by weight was obtained. . The length of one side of the nozzle hole in the coagulation bath in which the spinning dope obtained as described above was adjusted to a temperature of 65 ° C. and a bath solution of DMSO 60 mass% and water 40 mass% was adjusted to 40 ° C. Is 0.082 mm, the length of the discharge hole is extruded from a hole of 0.020 mm, wet-spun, stretched 4.5 times in hot water at 98 ° C., and the speed after stretching was 60 m / min. The yarn breakage on the base is frequent and the spinnability is unacceptable (x). Also, the stretchability is often unacceptable (x), and the cross-section is triangular with a fineness. It was impossible to obtain an acrylic fiber. The results are shown in Table 3.

[Comparative Example 2]
Acrylonitrile 87% by mass, methyl acrylate 12% by mass and sodium methallyl sulfonate 1% by mass were copolymerized in DMSO to obtain an acrylonitrile-based copolymer, and a spinning stock solution having a spinning stock solution concentration of 21% by weight was obtained. . The length of one side of the nozzle hole in the coagulation bath in which the spinning dope obtained as described above was adjusted to a temperature of 65 ° C. and a bath solution of DMSO 60 mass% and water 40 mass% was adjusted to 40 ° C. Is 0.082 mm, the length of the discharge hole is extruded from a hole of 0.020 mm, wet-spun, stretched 6.0 times in hot water at 98 ° C., and the speed after stretching was 60 m / min. There is a slight breakage of the yarn on the base, the spinnability is (△), and the stretchability is often a single fiber wrapping around the roller and rejected (x), the fineness is fine and the cross section is triangular It was impossible to obtain fibers. The results are shown in Table 3.

[Comparative Example 3]
Acrylonitrile 87% by mass, methyl acrylate 12% by mass and sodium methallyl sulfonate 1% by mass were copolymerized in DMSO to obtain an acrylonitrile-based copolymer, and a spinning stock solution having a spinning stock solution concentration of 21% by weight was obtained. . The length of one side of the nozzle hole in the coagulation bath in which the spinning dope obtained as described above was adjusted to a temperature of 65 ° C. and a bath solution of DMSO 60 mass% and water 40 mass% was adjusted to 40 ° C. Is 0.075 mm, and the length of the discharge hole is extruded from a 0.020 mm hole and wet-spun, stretched 6.0 times in hot water at 98 ° C., and the speed after stretching was 85 m / min. The yarn breakage on the base is frequent and the spinnability is unacceptable (x). Also, the stretchability is often unacceptable (x), and the cross-section is triangular with a fineness. It was impossible to obtain an acrylic fiber. The results are shown in Table 3.

[Comparative Example 4]
Acrylonitrile 87% by mass, methyl acrylate 12% by mass and sodium methallyl sulfonate 1% by mass were copolymerized in DMSO to obtain an acrylonitrile-based copolymer, and a spinning stock solution having a spinning stock solution concentration of 21% by weight was obtained. . The length of one side of the nozzle hole in the coagulation bath in which the spinning dope obtained as described above was adjusted to a temperature of 65 ° C. and a bath solution of DMSO 60 mass% and water 40 mass% was adjusted to 40 ° C. Is 0.082 mm, the length of the discharge hole is extruded from a hole of 0.060 mm, wet-spun, stretched 6.0 times in hot water at 98 ° C., and the speed after stretching was 85 m / min. There is a slight breakage of the yarn on the base, the spinnability is (△), and the stretchability is often a single fiber wrapping around the roller and rejected (x), the fineness is fine and the cross section is triangular It was impossible to obtain fibers. The results are shown in Table 3.

[Comparative Example 5]
Acrylonitrile (87% by mass), methyl acrylate (12% by mass) and methallyl sulfonic acid soda (1% by mass) were copolymerized in DMSO to obtain an acrylonitrile copolymer to obtain a spinning dope with a spinning dope concentration of 24% by mass. . The length of one side of the nozzle hole in the coagulation bath in which the spinning dope obtained as described above was adjusted to a temperature of 65 ° C. and a bath solution of DMSO 60 mass% and water 40 mass% was adjusted to 40 ° C. Is 0.082 mm, the length of the discharge hole is extruded from a hole of 0.060 mm, wet-spun, stretched 6.0 times in hot water at 98 ° C., and the speed after stretching was 85 m / min. The yarn breakage on the base is frequent and the spinnability is unacceptable (x). Also, the stretchability is often unacceptable (x), and the cross-section is triangular with a fineness. It was impossible to obtain an acrylic fiber. The results are shown in Table 3.

[Comparative Example 6]
92% by mass of acrylonitrile, 7% by mass of methyl acrylate and 1% by mass of sodium methallyl sulfonate were copolymerized in DMSO to obtain an acrylonitrile-based copolymer to obtain a spinning dope with a spinning dope concentration of 24% by mass. . The length of one side of the nozzle hole in the coagulation bath in which the spinning dope obtained as described above was adjusted to a temperature of 65 ° C. and a bath solution of DMSO 60 mass% and water 40 mass% was adjusted to 40 ° C. Is 0.082 mm, the length of the discharge hole is extruded from a hole of 0.060 mm, wet-spun, stretched 6.0 times in hot water at 98 ° C., and the speed after stretching was 60 m / min. The yarn breakage on the base is frequent and the spinnability is unacceptable (x). Also, the stretchability is often unacceptable (x), and the cross-section is triangular with a fineness. It was impossible to obtain an acrylic fiber. The results are shown in Table 3.

  As is apparent from the results of Tables 2 to 3, according to the conditions satisfying the various process requirements related to the present invention, excellent spinning and drawing stability is obtained by wet spinning the acrylic fiber having a triangular cross section of such fineness. It can also be seen that it can be manufactured at a low cost in terms of productivity.

1: Length of one side of nozzle hole 2: Introduction hole 3: Nozzle hole 4: Length of discharge hole

Claims (2)

  A spinneret for wet-spinning an acrylonitrile-based polymer, a regular triangular hole having a nozzle hole with a side length of 0.060 to 0.080 mm and a discharge hole length of 0.04 to 0.15 mm A wet spinneret of triangular cross-section acrylic fiber, characterized in that   The wet spinneret of triangular cross-section acrylic fibers according to claim 1, for wet spinning a spinning dope having a polymer concentration of 18 to 26% by mass of an acrylonitrile polymer containing 80% by mass or more of acrylonitrile.

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