Classifications

• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
  • D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
  • D01D5/00—Formation of filaments, threads, or the like
  • D01D5/08—Melt spinning methods
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
  • D01D5/00—Formation of filaments, threads, or the like
  • D01D5/08—Melt spinning methods
  • D01D5/088—Cooling filaments, threads or the like, leaving the spinnerettes
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
  • D01D5/00—Formation of filaments, threads, or the like
  • D01D5/08—Melt spinning methods
  • D01D5/088—Cooling filaments, threads or the like, leaving the spinnerettes
  • D01D5/0885—Cooling filaments, threads or the like, leaving the spinnerettes by means of a liquid
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
  • D01D5/00—Formation of filaments, threads, or the like
  • D01D5/08—Melt spinning methods
  • D01D5/098—Melt spinning methods with simultaneous stretching
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
  • D01D5/00—Formation of filaments, threads, or the like
  • D01D5/12—Stretch-spinning methods
  • D01D5/16—Stretch-spinning methods using rollers, or like mechanical devices, e.g. snubbing pins
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
  • D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
  • D01D4/00—Spinnerette packs; Cleaning thereof
  • D01D4/02—Spinnerettes
• • D—TEXTILES; PAPER
  • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
  • D10B2331/02—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides
• • D—TEXTILES; PAPER
  • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B2401/00—Physical properties
  • D10B2401/06—Load-responsive characteristics
  • D10B2401/063—Load-responsive characteristics high strength
• • D—TEXTILES; PAPER
  • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B2507/00—Sport; Military

Definitions

• the present invention relates to a monofilament of polyamide 4 and a method for producing the same.
• PA4 polyamide 4
• linear strength, knot strength, and transparency are important required properties.
• an undrawn monofilament formed in an extrusion process in melt spinning is required to be in an amorphous state, that is, to have a low density.
• PA4 may undergo thermolysis during melt spinning
• a spinning temperature needs to be set around a melting temperature.
• the amount of residual crystal nuclei tends to be large, and a crystallization rate in a cooling process after the extrusion becomes faster. Therefore, it is difficult to produce a monofilament in an amorphous state.
• An object of an aspect of the present invention is to provide a monofilament of PA4, which has a low density.
• a monofilament according to an aspect of the present invention is a monofilament of polyamide 4, and the density thereof is 1.230 g/cm 3 or less.
• a method for producing a monofilament according to an aspect of the present invention includes: melt-extruding polyamide 4; and cooling a melted and extruded fibrous matter of the polyamide 4 obtained by the melt-extruding process, at ⁇ 10° C. or lower by using a nonpolar solvent.
• a PA4 monofilament having a low density can be provided.
• the monofilament of an embodiment of the present invention is substantially made of polyamide 4 (PA4).
• PA4 is a polymer compound containing a structural unit represented by Formula (1) below. In the formula, x is 4.
• a polymer compound constituting a structure of a monofilament may be PA4 alone.
• an additional component besides the PA4 may be further contained in a range where the effects of the present embodiment can be provided.
• the additional component may be one or more kinds, examples of which include a reinforcing agent, a plasticizer, a lubricant, and a stabilizer.
• the additional component may contain a polymer compound other than the PA4.
• the additional component is appropriately used in an amount that further exhibits the effects of the additional component.
• the monofilament of an embodiment of the present invention is a monofilament of the PA4.
• the monofilament of an embodiment of the present invention has a density of 1.230 g/cm 3 or less.
• the density of the monofilament correlates with the degree of crystallization of the monofilament, and a lower density tends to result in a lower degree of crystallization.
• the density of the monofilament of 1.230 g/cm 3 corresponds to a degree of crystallization of the monofilament of approximately 10%.
• the density of the monofilament is high, the tensile strength and elongation when the monofilament is knotted may be insufficient.
• the density of the monofilament is preferably 1.225 g/cm 3 or less, and more preferably 1.223 g/cm 3 or less.
• the density of the monofilament is only required to be in a range that can be achieved for the monofilament of the PA4 and, for example, may be 1.215 g/cm 3 or greater.
• the density of the monofilament can be determined by a method that is also called “density gradient method”. Furthermore, the density of the monofilament can be adjusted by the cooling conditions in the production of an undrawn monofilament and, for example, the density can be reduced by cooling in the cooling process in the production method described below.
• the monofilament of an embodiment of the present invention is only required to have the physical properties described above and may further has other physical properties besides those described above as long as the effect of the present embodiment described above is achieved.
• the filament diameter of the monofilament of an embodiment of the present invention may be appropriately selected based on the use of the monofilament; however, from the viewpoint of adequately reducing the density of the monofilament, the filament diameter is preferably 1 mm or less. Note that, herein, the filament diameter of the monofilament is a filament diameter of an undrawn monofilament.
• the filament diameter of the monofilament is preferably 0.8 mm or less, and more preferably 0.5 mm or less. Meanwhile, the filament diameter of the monofilament is only required to be in a range that can be achieved for the monofilament of the PA4 based on the use of the monofilament; however, from the viewpoint of adequately performing cooling described above, the filament diameter may be 0.1 mm or greater.
• the filament diameter of the monofilament can be adjusted by a pore diameter of the die.
• the filament diameter of the monofilament can be measured by a known technique for measuring a filament diameter, and for example, the measurement can be performed by a known method for measuring the filament diameter of a monofilament by sandwiching the monofilament.
• the filament diameter of the monofilament tends to be smaller when the drawing ratio in the production method described below is higher.
• the filament diameter of the monofilament is more preferably 0.4 mm or less, and even more preferably 0.25 mm or less, from the viewpoint of adequately reducing the density of the monofilament before drawn.
• the filament diameter of the monofilament as a drawn monofilament may be, for example, 0.05 mm or greater from the viewpoint of practical usability as a monofilament based on the use.
• the filament diameter of the monofilament as a drawn monofilament can be adjusted by the drawing ratio.
• the tensile strength when the drawn monofilament of an embodiment of the present invention is knotted is preferably 460 MPa or greater from the viewpoint of achieving adequate tensile strength for use where the monofilament may be used in a knotted state.
• An example of use where the monofilament may be used in a knotted state is a fishing line.
• the tensile strength of the monofilament when knotted can be appropriately selected depending on the use of the monofilament. From the viewpoint of preventing cutting of the monofilament at a knotted position when the monofilament is pulled, the tensile strength of the monofilament when knotted is preferably high and, for example, more preferably 470 MPa or greater, and even more preferably 480 MPa or greater.
• the tensile strength of the monofilament when knotted is only required to be in a range that can be achieved for the monofilament of the PA4, and from such a viewpoint, the tensile strength of the monofilament when knotted may be 800 MPa or less.
• the tensile strength of the monofilament when knotted can be measured by using a known instrument that can perform a tensile test for a monofilament.
• the tensile strength of the monofilament when knotted can be adequately increased by setting the density of the monofilament to the range described above. Furthermore, the tensile strength of the monofilament when knotted can be enhanced by drawing in the production of the monofilament.
• the elongation at break when the drawn monofilament of an embodiment of the present invention is knotted is preferably 10% or greater from the viewpoint of suppressing breakage when the monofilament is used in a knotted state.
• the elongation at break of the monofilament when knotted can be appropriately selected depending on the use of the monofilament. From the viewpoints described above, the elongation at break is more preferably 12% or greater, and even more preferably 14% or greater.
• the elongation at break of the monofilament when knotted is only required to be in a range that can be achieved for the monofilament of the PA4, and from such a viewpoint, the elongation at break of the monofilament when knotted may be 30% or less.
• the elongation at break of the monofilament when knotted can be measured by using a known instrument that can perform a tensile test for a monofilament.
• the elongation at break of the monofilament when knotted can be adequately increased by setting the density of the monofilament to the range described above.
• the elongation at break of the monofilament when knotted can be enhanced by drawing in the production of the monofilament.
• the PA4 having a specific orientation is preferred from the viewpoint of enhancing tensile characteristics of the monofilament.
• the monofilament has a birefringence of preferably 50 ⁇ 10 ⁇ 3 or greater.
• the birefringence of the monofilament material is a scale of degree of orientation with respect to a filament axial direction of a polymer chain of a polymer compound constituting the monofilament. A larger absolute value of the birefringence indicates a larger degree of orientation in the monofilament of the polymer compound.
• the birefringence of the monofilament is more preferably 55 ⁇ 10 ⁇ 3 or greater, and even more preferably 60 ⁇ 10 ⁇ 3 or greater.
• the birefringence of the monofilament in an embodiment of the present invention is only required to be in a range that can be achieved for the monofilament of the PA4 and, from such a viewpoint, the birefringence may be 90 ⁇ 10 ⁇ 3 or less.
• the birefringence of the monofilament can be determined by retardation measurement using a polarizing microscope equipped with a Berek compensator and a sodium lamp as a light source. Furthermore, the birefringence of the monofilament can be adjusted by the degree of orientation of the PA4 in the monofilament, and can be further increased when a drawing ratio in the production method described below is increased.
• the method for producing a monofilament according to an embodiment of the present invention includes melt-extruding polyamide 4, and cooling a melted and extruded fibrous matter of the polyamide 4 obtained by the melt-extruding process, at ⁇ 10° C. or lower by using a nonpolar solvent.
• melt-extruding polyamide 4 and cooling a melted and extruded fibrous matter of the polyamide 4 obtained by the melt-extruding process, at ⁇ 10° C. or lower by using a nonpolar solvent.
• a melted and extruded fibrous matter of the PA4 is produced by extruding a melted and kneaded matter of the PA4 through extrusion molding.
• the spinning temperature in the melt-extruding process described above is preferably high from the viewpoint of reducing the amount of crystal nuclei of the PA4 in the melted and extruded matter. From such viewpoints, the spinning temperature is preferably 255° C. or higher, more preferably 260° C. or higher, and even more preferably 262° C. or higher, in terms of the resin temperature. Meanwhile, the spinning temperature is preferably low from the viewpoint of suppressing thermolysis of the PA4. From such viewpoints, the spinning temperature is preferably 275° C. or lower, more preferably 270° C. or lower, and even more preferably 267° C. or lower, in terms of the resin temperature.
• the cooling temperature of the melted and extruded matter in the cooling process by the nonpolar solvent is ⁇ 10° C. or lower.
• the cooling temperature is preferably ⁇ 15° C. or lower, and more preferably ⁇ 20° C. or lower.
• the cooling temperature can be appropriately selected based on the type of the coolant and production cost in a range in which the effects of the present embodiment can be achieved, and in the present embodiment in which the coolant is a nonpolar solvent, for example, from the viewpoint of cost, the cooling temperature may be ⁇ 60° C. or higher.
• the cooling time is preferably long and, more specifically, preferably 0.1 seconds or longer, more preferably 0.2 seconds or longer, and even more preferably 0.3 seconds or longer. From the viewpoint of productivity, the cooling time is preferably short. From such a viewpoint, the cooling time is preferably 5 seconds or less, more preferably 3 seconds or less, and even more preferably 2 seconds or less.
• the nonpolar solvent is substantially inert to the melted and extruded matter of the PA4.
• “Substantially inert” means that substantially no action is applied to the melted and extruded matter, and more specifically indicates being dissolved sparingly or insoluble in PA4 and having no permeability into the melted and extruded matter of the PA4.
• the melting point (Tm) of the nonpolar solvent is preferably ⁇ 20° C. or lower, and the boiling point (Tb) of the nonpolar solvent is preferably 100° C. or higher.
• One or more nonpolar solvents may be used.
• the nonpolar solvent include silicone oil, hexane, nonane, decane, ethylcyclohexane, isopropylcyclohexane, toluene, and p-cymene. Examples of the nonpolar solvent and their melting points and boiling points are listed in Table 1.
• the method for producing the monofilament of an embodiment of the present invention may further include another process besides the melt-extruding and cooling processes described above as long as the effects of an embodiment of the present invention can be achieved.
• the production method may further include drawing the monofilament cooled in the cooling process (drawing process). The drawing process is more effective from the viewpoint of enhancing tensile characteristics of the monofilament.
• the drawing process may be dry heat drawing or wet heat drawing. Furthermore, the drawing process may be performed once or for multiple times.
• the drawing temperature in the drawing process can be appropriately set to a range of 40 to 240° C. based on an aspect of the drawing process.
• the final drawing ratio in the drawing process can be appropriately set to a range of 3.5 to 6 times based on an aspect of the drawing process. Note that, in the present specification, the wording “from A to B” represents a range including numerical values on both ends, which is a range of A or greater and B or less.
• the drawing temperature may be from 150 to 240° C. (e.g., 200° C.), and the drawing ratio may be from 3.5 to 5 times (e.g., 4 times).
• the drawing temperature in the first round of dry heat drawing may be from 40 to 80° C. (e.g., 60° C.), and the drawing ratio may be from 2.5 to 3.5 times (e.g., 3 times).
• the drawing temperature in the second round of dry heat drawing may be from 150 to 240° C. (e.g., 200° C.), and the drawing ratio may be from 1.05 to 2.0 times (e.g., 1.33 times).
• the melted and extruded fibrous matter is cooled while being pulled at a rate greater than a discharging rate of the melted and extruded matter and then supplied to a drawing device.
• from the melt-extruding process to the cooling process and the pulling of the melted and extruded matter to supply the melted and extruded matter to the following drawing process are not included in the drawing process and may be set appropriately in a range in which the effects of the present embodiment can be achieved.
• the monofilament in an embodiment of the present invention is substantially made of the PA4 described above, and is a monofilament having a density of 1.230 g/cm 3 or less.
• the monofilament having a low density has higher tensile characteristics when the monofilament is knotted as compared to a monofilament having a high density.
• a monofilament having improved tensile characteristics when the monofilament is knotted can be provided and, more specifically, a monofilament having high tensile strength and high elongation at break when the monofilament is knotted can be provided.
• the method for producing a monofilament according to an embodiment of the present invention includes melt-extruding a monofilament, and cooling a melted and extruded monofilament, at ⁇ 10° C. or lower by using a nonpolar solvent. According to this configuration, a monofilament having a density of 1.230 g/cm 3 or less can be produced.
• the diameter of the monofilament is advantageously 1 mm or less.
• the nonpolar solvent of an embodiment of the present invention can be selected from the group consisting of silicone oil, hexane, nonane, decane, ethylcyclohexane, isopropylcyclohexane, toluene, and p-cymene. These nonpolar solvents are preferred from the viewpoint of stability as a coolant in the cooling process described above.
• the method for producing a monofilament of an embodiment of the present invention further includes drawing the monofilament cooled in the cooling process, adequate tensile characteristics that are applicable to use in a fishing line, a fishing net, or the like can be exhibited.
• a monofilament according to an embodiment of the present invention is a monofilament of polyamide 4, and the density thereof is 1.230 g/cm 3 or less.
• a method for producing a monofilament according to an embodiment of the present invention includes melt-extruding polyamide 4, and cooling a melted and extruded fibrous matter of the polyamide 4 obtained by the melt-extruding process, at ⁇ 10° C. or lower by using a nonpolar solvent.
• the monofilament may have a diameter of 1 mm or less. This configuration is even more effective from the viewpoint of enhancing tensile characteristics of the monofilament.
• the nonpolar solvent may be at least one solvent selected from the group consisting of silicone oil, hexane, nonane, decane, ethylcyclohexane, isopropylcyclohexane, toluene, and p-cymene.
• the method for producing a monofilament of an embodiment of the present invention may further include drawing the monofilament cooled in the cooling process. This configuration is even more effective from the viewpoint of producing a monofilament having excellent tensile characteristics.
• the Mw of the PA4 was measured using the following procedure, analysis device and conditions.
• HFIP hexafluoroisopropanol
• GPC apparatus HLC-8420 GPC, available from TOSOH CORPORATION
• the PA4 was molded in a fibrous form by melt-extrusion at a temperature of 265° C., and immediately after the molding, the resulting melted and extruded fibrous matter was passed through a volatile silicone oil (“KF-995”, available from Shin-Etsu Chemical Co., Ltd.) bath at ⁇ 20° C. for 0.3 seconds, and cooled and solidified.
• KF-995 available from Shin-Etsu Chemical Co., Ltd.
• the density of the undrawn monofilament was measured by the measurement method described below. The density of the undrawn monofilament was 1.220 g/cm 3 .
• the density of the undrawn monofilament was determined by a density gradient method.
• As the solvent 6 mixed solvents, in which the densities were adjusted to a range of 1.20 to 1.30 g/cm 3 and varied in 0.02 increments by changing the mixing ratio of heptane and carbon tetrachloride, were used.
• the produced undrawn monofilament was drawn by dry heat drawing at a drawing temperature of 60° C. and a drawing ratio of 3.0 times.
• drawing was performed by dry heat drawing at a drawing temperature of 200° C. and a drawing ratio of 1.33 times (4.0 times in terms of total drawing ratio).
• a humidity of an atmosphere during dry heat drawing was 10% RH or less.
• a monofilament was produced in the same manner as in Example 1 except for changing the filament diameter of the undrawn monofilament to 480 ⁇ m.
• the density of the undrawn monofilament was 1.220 g/cm 3 .
• a monofilament was produced in the same manner as in Example 1 except for changing the coolant to hexane and changing the temperature of the coolant to ⁇ 55° C.
• the density of the undrawn monofilament was 1.219 g/cm 3 .
• a monofilament was produced in the same manner as in Example 1 except for changing the coolant to toluene and changing the temperature of the coolant to ⁇ 50° C.
• the density of the undrawn monofilament was 1.219 g/cm 3 .
• a monofilament was produced in the same manner as in Example 1 except for changing the coolant to water and changing the temperature of the coolant to 4° C. Due to surface roughness of the undrawn monofilament, measurement of the density of the undrawn monofilament was not possible.
• a monofilament was produced in the same manner as in Example 1 except for changing the coolant to tetradecane and changing the temperature of the coolant to 40° C.
• the density of the undrawn monofilament was 1.240 g/cm 3 .
• a monofilament was produced in the same manner as in Example 1 except for changing the temperature of the coolant to 40° C.
• the density of the undrawn monofilament was 1.240 g/cm 3 .
• the filament diameter of the drawn monofilament of each of Examples 1 to 4 and Comparative Examples 1 to 3 was determined in the same manner as for the filament diameter of the undrawn monofilament, and the filament diameter was from 170 to 240 ⁇ m.
• the density of the drawn monofilament of each of Examples 1 to 4 and Comparative Examples 1 to 3 was determined in the same manner as for the density of the undrawn monofilament, and the density was from 1.246 to 1.250 g/cm 3 .
• the birefringence of the drawn monofilament of each of Examples 1 to 4 and Comparative Examples 1 to 3 was determined, and the birefringence was from 58 ⁇ 10 ⁇ 3 to 67 ⁇ 10 ⁇ 3 .
• the birefringence of the PA4 in the drawn monofilament was determined by retardation measurement using a polarizing microscope equipped with a Berek compensator and a sodium lamp as a light source.
• Tensilon RTF-1210 As a tester, tensile measurement was performed by setting a distance between chucks to 150 mm and a tensile test speed to 150 mm/min at 23° C. and a humidity of 50% RH. When the monofilament was knotted, the knotted part was placed at a center of the chucks.
• the densities of the monofilaments of Examples were all 1.230 g/cm 3 or less.
• the tensile strength and knot elongation of the drawn monofilament obtained by drawing the undrawn monofilament when knotted were higher than those of the drawn monofilaments of Comparative Examples.
• Comparative Example 1 surface roughness occurred in the undrawn monofilament. It is conceived that this is because water was used as the coolant, the PA4 of the undrawn monofilament was dissolved in water or moistened during the cooling. Furthermore, in Comparative Example 1, drawing of the undrawn monofilament could not be performed. It is conceived that this is because the strength of the undrawn monofilament deteriorated due to the surface roughness and dissolution or moisture absorption of the undrawn monofilament described above.
• the monofilament of the PA4 of an embodiment of the present invention can be used as a synthetic monofilament having excellent tensile characteristics. According to an embodiment of the present invention, environmental damage upon use of the synthetic monofilament is expected to be further reduced.

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