WO2022039033A1 - ポリアミドマルチフィラメントおよびその製造方法 - Google Patents

ポリアミドマルチフィラメントおよびその製造方法 Download PDF

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Publication number
WO2022039033A1
WO2022039033A1 PCT/JP2021/029073 JP2021029073W WO2022039033A1 WO 2022039033 A1 WO2022039033 A1 WO 2022039033A1 JP 2021029073 W JP2021029073 W JP 2021029073W WO 2022039033 A1 WO2022039033 A1 WO 2022039033A1
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Prior art keywords
polyamide
dtex
multifilament
polyamide multifilament
strength
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PCT/JP2021/029073
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English (en)
French (fr)
Japanese (ja)
Inventor
南井一志
重野久雄
潤間崇志
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Toray Industries Inc
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Toray Industries Inc
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Priority to JP2021551546A priority Critical patent/JP7797877B2/ja
Priority to US18/006,739 priority patent/US20230279586A1/en
Priority to CN202180049017.4A priority patent/CN115803484B/zh
Priority to EP21858180.9A priority patent/EP4202093A4/en
Publication of WO2022039033A1 publication Critical patent/WO2022039033A1/ja
Anticipated expiration legal-status Critical
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    • 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
    • D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
    • D01D10/02—Heat treatment
    • 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
    • D01D5/092—Cooling filaments, threads or the like, leaving the spinnerettes in shafts or chimneys
    • 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
    • D01D5/096—Humidity control, or oiling, of 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
    • D01D5/098—Melt spinning methods with simultaneous stretching
    • 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
    • D10B2401/061—Load-responsive characteristics elastic
    • 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

Definitions

  • the present invention relates to a polyamide multifilament.
  • Polyamide 6 also known as “polycaprolactum” and polyamide 66 (also known as “polyhexamethylene adipamide”) multifilaments have higher strength and elongation than general-purpose multifilaments such as polyester and polypropylene, and are excellent in fluff quality. Therefore, it is used in a wide variety of industrial applications such as airbags, sports racket guts, ropes, fishing nets, and bag belts.
  • airbags As an indispensable safety device to protect occupants in the event of a vehicle collision, airbags with rapidly increasing installation rates are used to protect the driver, passengers in the passenger seat, and knees, which have been introduced from the beginning.
  • the mounting area continues to expand, such as for chest protection built into the seat and for head protection installed in the ceiling above the window.
  • various studies have been made to reduce the weight and size of the base fabric used for airbags. I came.
  • the total fineness of the polyamide 66 yarn used for the airbag base fabric was generally 940 dtex, but in recent years, 470 dtex is mainly used, and further, low fineness of 235 dtex or less is also used. It is becoming more like.
  • Patent Document 1 and Patent Document 2 disclose a technique for obtaining fine-fine and high-strength polyamide fibers having excellent fluff quality, which can provide an airbag having excellent compactness. It is proposed that 100 to 250 dtex is set to 50 to 470 dtex in Patent Document 2. However, even if the section of the example is seen, only fibers having a fineness of up to 175 dtex are obtained, the total fineness is reduced to 150 dtex or less, and further to 100 dtex or less, and the fiber has high strength that can be used as an industrial fiber. No specific example of the raw yarn is given. The reason for this is that, as described in Patent Document 1 (paragraph [0021]), it is difficult to stably obtain high-strength fibers when the total fineness becomes thin.
  • the reason for this is that when a multifilament with a small total fineness is obtained, the influence of retention in the molten state until the polyamide chip is melted and spun, and the influence of defects such as bubbles remaining in the fiber during spinning become large. be. That is, in a general facility for producing fibers for high-strength industrial materials such as raw yarn for airbags, a spinning section that discharges a high total fineness of about 235 to 2000 dtex and a multi-stage heat for exhibiting high strength. Although it is composed of a direct stretching machine combined with a stretching machine, the problem that occurs when a multifilament having a fineness of 100 dtex or less is manufactured by using such a device is not considered.
  • Patent Document 3 paragraphs [0005] to [0008]
  • Patent Document 4 paragraph [paragraph [paragraph]]
  • fine foreign matter is generated by thickening, thermal deterioration, and gelation due to long-term retention of the polymer, and the foreign matter is mixed in the yarn to cause yarn-making failure, resulting in high strength and fluff quality.
  • Good polyamide fibers cannot be obtained.
  • Patent Document 5 In response to the demand for higher strength of polyamide fibers for clothing, in Patent Document 5, a hot plate obtained by heat-fixing or heat-stretching and once winding the yarn into a package is further heated to 170 to 205 ° C. A means of heat-stretching 1.15 times or more by contacting the yarn has been proposed. However, this means is a two-step method in which the spinning step and the drawing step are separated, and not only the steps become complicated, but also the winding speed is about 1000 m / min, the production speed is slow, and the cost is high. I am concerned.
  • Patent Document 6 as a product obtained in a process that can be commercialized, only a polyamide multifilament having a strength of up to 7.3 cN / dtex is obtained, and fibers and clothing for industrial materials such as airbags are obtained. The strength was insufficient to improve the durability of the fabric.
  • Japanese Unexamined Patent Publication No. 2017-22939 Japanese Patent Application Laid-Open No. 2003-20566 JP-A-2007-254945 Japanese Unexamined Patent Publication No. 2008-133566 Japanese Unexamined Patent Publication No. 11-247022 Japanese Unexamined Patent Publication No. 2002-88577
  • An object of the present invention is to solve the above problems, and to provide a polyamide multifilament having fineness, high strength, excellent toughness, and good fluff quality, and as described above, an airbag. It is an object of the present invention to provide a polyamide multifilament capable of reducing the weight of industrial materials such as the above and improving the durability of clothing fabrics. Further, according to the present invention, it is possible to obtain a polyamide multifilament having good production efficiency.
  • the raw materials used for the polyamide multifilament of the present invention include, for example, nylon 6, nylon 66, nylon 12, nylon 46, nylon 56, nylon 610, a copolymerized polyamide of nylon 6 and nylon 66, nylon 6 with polyalkylene glycol and dicarboxylic acid. , Copolymerized polyamide obtained by copolymerizing diamine or the like, and is known as a polymer in which repeating units are linked by an amide bond.
  • the polyamide is not particularly limited, but it is preferable to use the polyamide 66 having excellent impact resistance and heat resistance.
  • the polyamide multifilament of the present invention may contain a component other than the polyamide, if necessary, and such components include, for example, a terminal sequestering agent such as a monocarboxylic acid and a matting agent such as titanium oxide.
  • a terminal sequestering agent such as a monocarboxylic acid
  • a matting agent such as titanium oxide.
  • examples thereof include polymerization catalysts such as phosphorus compounds, heat resistant agents, antioxidants such as copper compounds and halides of alkali metals or alkaline earth metals, and heat stabilizers.
  • the content ratio of the polyamide contained in the polyamide multifilament is preferably 95% by weight or more, and more preferably 97% by weight or more. If the content of the polyamide is less than 95% by weight, the heat resistance may decrease.
  • the polyamide multifilament of the present invention has a total fineness of 30 to 150 dtex. More preferably, it is in the range of 50 to 120 dtex. When the total fineness is less than 30 dtex, it is difficult to secure a sufficient value as the total strength as a multifilament, and single yarn breakage occurs when stretching at a high magnification in order to obtain high strength. It is easy and the possibility of fluffing is high. If the total fineness exceeds 150 dtex, it does not lead to weight reduction of industrial materials and improvement of durability of garment fabrics.
  • the strength of the polyamide multifilament of the present invention is 7.5 to 10.0 cN / dtex, more preferably 8.0 to 9.7 cN / dtex.
  • the polyamide fiber is suitable for industrial materials such as airbags and woven fabrics with excellent durability. If the strength is less than 7.5 cN / dtex, it is insufficient to improve the durability of fibers for industrial materials such as airbags and fabrics for clothing.
  • the polyamide fiber has a strength exceeding 10.0 cN / dtex, mechanical stretching at a high magnification is required, single yarn breakage is likely to occur, and the fluff quality is deteriorated.
  • Such polyamide multifilament is not suitable for fibers for industrial materials such as airbags, which require high quality.
  • the elongation of the polyamide multifilament of the present invention is 15.0% to 35.0%, more preferably 17.0% to 30.0%.
  • the strong elongation product is preferably 38 cN / dtex ⁇ (% 1/2 ) or more, and more preferably 40 cN / dtex ⁇ (% 1/2 ) or more. ..
  • the strength (cN / dtex) and the elongation (%) refer to the values measured under the constant speed elongation conditions shown in the standard time test of JIS L1013 (1999) 8.5.1, and the strength product is [strength]. It is a value calculated by [ ⁇ ⁇ (elongation)].
  • the upper limit is not particularly limited, but it is practical to set it to 50.0 cN / dtex ⁇ (% 1/2 ) or less.
  • the polyamide multifilament of the present invention preferably has a thread spot (U%) of 1.2% or less. It is more preferably 1.0% or less, and particularly preferably 0.8% or less. By setting the U% to 1.2% or less, no stain spots or streaks are generated during dyeing as a woven fabric, and the appearance is good and the product quality is excellent.
  • the lower limit is not particularly limited, but it is practical to set it to 0.3% or more.
  • the polyamide multifilament of the present invention preferably has an elongation coefficient of variation of 1.00% or less when loaded with 3 cN / dtex. It is more preferably 0.80%, and particularly preferably 0.50% or less.
  • the coefficient of variation is 1.00% or less, the elongation of the multifilament is made uniform when a constant load is applied to an industrial fabric such as an airbag, which is advantageous in terms of suppressing misalignment.
  • the coefficient of variation is caused by the variation in the crystal structure, in the case of the woven fabric, it leads to the suppression of the dyeing spots.
  • the difference between the sulfuric acid relative viscosity of the polyamide chip used and the sulfuric acid relative viscosity of the obtained polyamide multifilament is controlled. Is simple. If this difference in viscosity is large, local thickening or hydrolysis may occur due to thermal cross-linking or the like from the raw material chip to the yarn. In the case of thickening, there are places where the crystal orientation locally increases in the longitudinal direction of the fiber, while in the case of hydrolysis, there are places where the crystal orientation locally decreases in the longitudinal direction of the fiber, and the elongation varies. Is easy to generate.
  • the coefficient of variation of elongation under 3cN / dtex load is obtained by the method described in the section of Examples.
  • the polyamide multifilament of the present invention preferably has a fluff number of 0 to 3 / 10,000 m or less, particularly preferably 0 to 2 / 10,000 m, and more preferably 0 to 1 / 10,000 m. Since the number of fluffs is small, it can be applied to applications that require excellent fluff quality such as airbags.
  • the number of fluffs is a value obtained by measuring the total number of fluffs with a filament length of 100,000 m or more while rewinding at a speed of 150 m / min and converting it into the number per 10,000 m.
  • the number of bubbles contained in the polyamide filament constituting the polyamide multifilament is preferably 50 cells / cm or less, that is, 0 to 50 cells / cm, and particularly 0 to 30 cells / cm. Further, it is preferably 0.2 to 20 pieces / cm.
  • the number of bubbles contained in the polyamide filament exceeds 50 cells / cm, the strength of the single fiber containing the bubbles decreases. This means that the bubbles in the single fiber inhibit the stretching.
  • the polymer being melted excessively takes in moisture in the air, which causes hydrolysis and a decrease in the viscosity of the polyamide, resulting in insufficient crystal orientation, resulting in a decrease in strength.
  • the fluff quality also deteriorates.
  • the number is 0.2 or more, the molten polymer takes in the moisture in the air to obtain a raw yarn having good fluff quality.
  • the pressure of the extruder when extruding the polyamide may be set to 20.0 to 80.0 kPa.
  • FIG. 1 is a schematic view of a direct spinning and drawing device preferably used in the present invention.
  • FIG. 1 the method for producing the polyamide multifilament of the present invention will be described by taking FIG. 1 as an example.
  • a polyamide raw material chip which is a raw material for the polyamide multifilament of the present invention, is prepared.
  • a method for polymerizing the polyamide a known polymerization method can be used.
  • the relative sulfuric acid viscosity (hereinafter, may be simply referred to as “viscosity”) of the polyamide raw material chip used in the polyamide multifilament of the present invention is preferably 2.8 to 3.9, more preferably 3.3 to 3.9. be.
  • viscosity of the chip is preferably 2.8 to 3.9, more preferably 3.3 to 3.9. be.
  • the viscosity of the chip is 4.0 or more, when the total fineness is within the specified range in the present invention, fine foreign matter is generated due to thickening, thermal deterioration, and gelation due to long-term retention of the polymer, resulting in fluff quality. Will get worse.
  • the viscosity of the chip is less than 2.8, it becomes difficult to obtain a polyamide multifilament having the strength specified in the present invention.
  • the relative sulfuric acid viscosity is a value measured at 25 ° C. using an Ostwald viscometer using a solution of 1 g of chips in 100 ml of 98% sulfuric acid and 98% sulfuric acid in which the chips are not dissolved. The details of the measurement are as described in the section of Examples.
  • the direct spinning and drawing method is used, and when the relative sulfuric acid viscosity of the polyamide chip used as a raw material is ⁇ a and the relative sulfuric acid viscosity of the produced polyamide multifilament is ⁇ b,
  • is less than 0.2.
  • ⁇ 0.3 has extremely good fluff quality, high strength elongation, and little variation in elongation at 3% elongation. Can be obtained as.
  • the above-mentioned polyamide chip having a relative sulfuric acid viscosity is prepared, dried, and then supplied to an extruder type spinning machine. It is placed on the spinneret by a measuring pump and melt-spun.
  • the pressure of the extruder supply unit is preferably 20.0 to 80.0 kPa instead of vacuum (pressure 0.0 kPa). More preferably, it is 40.0 to 60.0 kPa.
  • the pressure in the extruder supply section is less than 20.0 kPa, the fluff quality may deteriorate due to thickening, thermal deterioration, and gelation of the polymer, and high-strength yarn may not be obtained.
  • the pressure of the extruder supply unit is 80.0 kPa or more, the number of bubbles contained in the polyamide filament increases, and further, the hydrolysis reaction of the polymer becomes dominant, so that high-strength yarn cannot be obtained.
  • the polyamide discharged from the spinneret 1 passes through the heating cylinder 2 surrounding a range of 5 to 300 cm from directly below the spinneret.
  • the temperature inside the heating cylinder is preferably ⁇ 30 to + 30 ° C., more preferably ⁇ 15 to + 15 ° C. with respect to the melting point of the polymer polyamide.
  • the unstretched yarn 5 that has passed through the high temperature atmosphere is then cooled and solidified by blowing air at 10 to 80 ° C., preferably 10 to 50 ° C. by the cross-flow cooling device 3. Further, when the cooling air exceeds 80 ° C., the single fiber sway during spinning becomes large, so that the single fibers collide with each other and cause deterioration of the spinning property.
  • the obtained cooling yarn can be coated with an oil agent by a known refueling device 4, picked up by a take-up roll 6, stretched, and then wound up.
  • a known oil agent can be used as the oil agent, but in order to suppress the winding of the single thread on the take-up roll 6, the adhesion amount is preferably 0.3 to 1.5% by weight, more preferably 0.5 to 0.5% by weight. It is 1.0% by weight.
  • the spinning speed defined by the rotation speed of the take-up roll 6 is preferably 500 to 1200 m / min, more preferably 600 to 800 m / min.
  • the spinning speed is 500 m / min or more, the final production speed is sufficient, and the polyamide multifilament can be produced efficiently and inexpensively.
  • it is 1200 m / min or less, it is preferable because the occurrence of thread breakage and fluff can be suppressed.
  • the stretching speed represented by the maximum speed of the stretching roll is preferably 2800 m / min or more, more preferably 3000 m / min or more.
  • the spun yarn obtained by these above-mentioned methods can be drawn, relaxed heat-treated, wound, etc. by using a known method.
  • the spun yarn taken up by the take-up roller 6 (1FR) is referred to as a yarn feeding roller 7 (2FR), a first drawing roller 8 (1DR), and a second drawing roller.
  • the yarn is wound in the order of 9 (2DR) and the relaxation roller 10 (RR) to perform heat treatment and drawing treatment, and the yarn is wound on the winder 11.
  • Pre-stretch stretching is performed between 1FR and 2FR, and the first-stage stretching is performed between 2FR and 1DR, and the second-stage stretching is performed between 1DR and 2DR.
  • the temperature of 2FR is set to 30 to 50 ° C. and the temperature of 1DR is set to 100 to 225 ° C.
  • pre-stretch stretching and first-stage stretching are performed by thermal stretching at around the glass transition temperature.
  • the remaining stretching and heat setting temperature is usually preferably in the range of 180 to 240 ° C. More preferably, it is 200 to 220 ° C.
  • the total draw ratio (hereinafter, also simply referred to as “stretch ratio”), that is, the ratio when stretching is performed between the take-up roller 6 and the second draw roller 9, in order to obtain a high-strength polyamide multifilament, a high draw ratio is obtained.
  • the winding speed is usually preferably 2000 to 5000 m / min, more preferably 2500 to 4500 m / min. Further, it is preferable to wind the cheese on a cheese strip with a winding device under the condition that the winding tension is 20 to 250 gf.
  • the thickening, thermal deterioration, gelation, and hydrolysis of the polyamide polymer are suppressed, the influence of air bubbles on the mechanical properties is small, and the total fineness is as fine as 150 dtex or less. Further, it is possible to obtain a polyamide multifilament having high strength and high elongation, that is, high toughness and high quality.
  • Sulfuric acid relative viscosity ( ⁇ r): Using a polymer chip or raw yarn as a sample, 0.25 g of the sample was dissolved in 25 ml of 98% sulfuric acid, measured at 25 ° C. using an Ostwald viscometer, and calculated from the following formula. .. The measured value was obtained from the average value of 5 samples.
  • ⁇ r number of seconds for sample solution to flow down / number of seconds for sulfuric acid only to flow down.
  • Strength / strength / elongation Measured under constant speed elongation conditions shown in JIS L1013 (1999) 8.5.1 standard time test.
  • the multifilament sample was prepared by using "TENSILON" UCT-100 manufactured by Orientec, with a gripping interval of 25 cm and a tensile speed of 30 cm / min. The strength was determined from the elongation of the point showing the maximum strength on the SS curve, the elongation was determined from the elongation of the point showing the maximum strength on the SS curve, and the strength was determined by dividing the strength by the total fineness.
  • the multifilament sample was sampled every 1 m in the longitudinal direction, the measurement was performed at 5 points, and the average value was obtained from the measurement data.
  • Thread spot (U%) Using USTER TESTER IV manufactured by zellweger uster, the sample length was 500 m, the measurement thread speed was 25 m / min, and the measurement was performed at 1/2 Inert.
  • Number of fluffs The obtained fiber package is rewound at a speed of 150 m / min, and a laser fluff detector "Flytech V" manufactured by Heberline Co., Ltd. is installed at a position 2 m away from the thread being rewound and detected. The total number of fluff was evaluated. The evaluation was performed on a multifilament of 100,000 m or more, and the number was converted into the number per 10,000 m and displayed.
  • (9) Number of bubbles The number of bubbles observed was evaluated using a lens with a magnification of 1000 times with a microscope "VHX-5000" manufactured by KEYENCE. If bubbles are present in the fiber, a stretch-inhibited portion is generated starting from the bubbles. Therefore, after observing the bubbles with an optical lens having a magnification of 1000 times, the stretch-inhibited portion is confirmed with a polarizing lens. By doing so, it was confirmed that it was a bubble. Sampling was performed to cut out fibers of the same length from all the polyamide filaments constituting the polyamide multifilament. However, sampling was performed so that the total length of the cut fibers was 100 cm. Observation was performed on the cut-out sample, and the total number of bubbles was converted into the number per 1 cm and displayed. The sample to be cut out does not have to be exactly 100 cm as long as 100 cm is secured as the total length to be measured.
  • Example 1 A 5% by weight aqueous solution of copper acetate was added as an antioxidant to the nylon 66 chips obtained by liquid phase polymerization and mixed, and 68 ppm of copper was adsorbed with respect to the polymer weight. Next, a 50% by weight aqueous solution of potassium iodide and a 20% by weight aqueous solution of potassium bromide were added and adsorbed to 100 parts by weight of the polymer chip so as to be 0.1 part by weight of potassium, respectively, to form a batch type solid phase polymerization apparatus. Using solid phase polymerization, nylon 66 pellets having a relative sulfuric acid viscosity of 3.75 were obtained.
  • the obtained nylon 66 pellets were supplied to an extruder having a diameter of 110 mm and melted under an atmosphere of a melting temperature of 300 ° C. and a pressure of 50.0 kPa in the extruder supply section.
  • the molten polymer was dispensed by a metering pump so that a multifilament having a total fineness of 80 dtex could be obtained, and the molten polymer was placed in a spinning pack. Then, after filtering in a spinning pack with a metal non-woven fabric filter having a roughness of 40 ⁇ m, spinning was performed using a device having a configuration as shown in FIG. 1 through a base having circular holes and 24 holes.
  • a heating cylinder having a heating cylinder length of 20 cm was installed 3 cm below the base surface, and the temperature inside the cylinder was heated to 250 ° C.
  • the in-cylinder atmosphere temperature is the air temperature in the central portion of the length of the heating cylinder, which is 1 cm away from the inner wall.
  • a cross-flow type chimney that blows air from one direction was attached directly under the heating cylinder, and cold air at 18 ° C. was blown onto the yarn at a rate of 35 m / min to cool and solidify, and then an oil agent was applied to the yarn.
  • the undrawn yarn to which the oil was applied was wound around 1FR rotating at a surface speed of 800 m / min and taken up, and then drawn at a total draw ratio of 4.3 times.
  • the take-up thread is continuously stretched by 5% between the take-up roller and 2FR without being wound once, and then the first step is stretched at a rotation speed ratio of 2.80 times, and then the rotation speed.
  • the second step was stretched at a ratio of 1.46 times, and the film was wound at a speed of 3400 m / min.
  • the roller surface of 1FR and 2FR is mirror-finished, 1DR, 2DR and RR are satin-finished, and the roller temperature is 1FR unheated, 2FR 40 ° C., 1DR 150 ° C., 2DR 225 ° C., and RR.
  • the entanglement treatment was performed by injecting high-pressure air from the direction perpendicular to the traveling yarn in the entanglement applying device.
  • a guide for regulating the running thread was provided before and after the entanglement applying device, and the pressure of the injected air was kept constant at 0.2 MPa.
  • Example 2 The procedure was the same as in Example 1 except that the total fineness and the total draw ratio of the polyamide multifilament were changed as shown in Table 1.
  • Example 6 The procedure was the same as in Example 1 except that the number of single fibers of the polyamide multifilament was changed as shown in Table 1.
  • Example 9 The procedure was the same as in Example 1 except that the total draw ratio was changed as shown in Table 1.
  • Example 11 to 12 The procedure was the same as in Example 1 except that the pressure of the extruder supply section and the total draw ratio were changed as shown in Table 1.
  • Table 1 shows the results of evaluating the physical properties of the polyamide multifilaments obtained in Examples 1 to 12.
  • the polyamide multifilament of the present invention has good fluff quality while having fineness and high strength.
  • the polyamide multifilament of the present invention was produced with various total fineness. Compared with Examples 11 and 12 and Comparative Examples 1 to 5 described below, thickening can be suppressed by melting the polymer in an atmosphere of a pressure of 50.0 kPa in the extruder supply section, and the target polyamide multifilament can be suppressed. Has been obtained. Further, as the total fineness decreases and the single fiber fineness becomes finer, cooling becomes advantageous and the strong elongation product of the polyamide multifilament tends to improve. On the other hand, when the single fiber fineness was made too fine as in Example 8, the uniform cooling property in the chimney style was poor, and the effect on the thread spots (U%) appeared.
  • Examples 11 to 12 are examples in which the pressure of the extruder supply unit is 25.0 kPa and 75.0 kPa, respectively. There was a tendency for thickening or hydrolysis from the chip to the multifilament to occur, and an effect on the coefficient of variation of elongation under a 3cN / dtex load was observed.
  • Comparative Example 5 The procedure was the same as in Comparative Example 4 except that the pressure of the extruder supply section and the total draw ratio were changed as shown in Table 2.
  • Reference Example 2 The physical characteristics of a general polyamide multifilament for clothing manufactured according to the description of Example 1 of International Publication WO2016 / 076184 are shown as Reference Example 2.
  • Table 2 shows the results of evaluating the physical properties of the polyamide multifilaments obtained in Comparative Examples 1 to 5 and Reference Examples 1 and 2.
  • Reference Example 1 is a polyamide multifilament having a total fineness of 175 dtex, and the polymer is melted under vacuum (under an atmosphere of an extruder supply unit pressure of 0.0 kPa), so that the polymer thickens to some extent. With this total fineness, it can be seen that a polyamide multifilament having a level of strength required for industrial fibers is obtained. However, since the total fineness is large, it is not sufficient to achieve the object of the present invention, which aims to reduce the weight of industrial materials such as airbags and improve the durability of clothing fabrics with high production efficiency.
  • Comparative Example 1 a polyamide multifilament having a total fineness of 110 dtex was produced by the same method as in Reference Example 1, but in this case, silk reeling was impossible.
  • Comparative Example 2 when the same polyamide multifilament as in Comparative Example 1 was spun at a draw ratio of 3.6 times, the yarn could be spun. However, the obtained polyamide multifilament was thickened and thermally deteriorated due to long-term polymer retention, lost its strength, and fluffed frequently.
  • Comparative Example 3 a polyamide multifilament having a total fineness of 80 dtex was produced under the same silk-reeling conditions as in Comparative Example 2, but in this case, silk-reeling was impossible.
  • Comparative Example 4 when the draw ratio was reduced to 3.2 times in Comparative Example 3 and the yarn was produced, the yarn could be produced. However, the obtained polyamide multifilament thickened and deteriorated due to long-term polymer retention, lost its strength, and fluffed frequently. Compared with Comparative Examples 1 and 2, in Comparative Examples 3 and 4, the residence time of the polymer was increased due to the fineness, and the thickening of the polymer became more remarkable, so that the stretchability of the polymer was lost and the polymer was high. It can be seen that silk reeling at the draw ratio is impossible.
  • Comparative Example 5 the polymer was produced by the same method as in Example 1 except that the polymer was melted in an atmosphere of an extruder supply unit pressure of 101.3 kPa, but in this case, the hydrolysis reaction of the polymer became remarkable and the multifilament was obtained. The result was that the viscosity of the chip was much lower than the viscosity of the chip. Further, as the amount of air bubbles in the yarn increases, fluffing occurs frequently, and the strength specified in the present invention cannot be achieved.
  • Reference Example 2 is an example in which a polyamide multifilament is manufactured in a general facility for manufacturing clothing fibers based on the description of WO2016 / 076184. In this case, it can be seen that there is almost no polymer thickening due to the shorter residence time of the polymer as compared with the case of using general equipment for producing fibers for industrial materials. On the other hand, since the number of stretching steps is one and the drawing is at a low magnification, the strength is not sufficient, and the crystal structure tends to vary in the fiber longitudinal direction, and the elongation changes under a 3cN / dtex load. The effect on the coefficient was significant.
  • the polyamide multifilament of the present invention has fineness, high strength, and good fluff quality, it is suitable mainly for reducing the weight of industrial materials such as airbags and improving the durability of clothing fabrics.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Artificial Filaments (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
PCT/JP2021/029073 2020-08-21 2021-08-05 ポリアミドマルチフィラメントおよびその製造方法 Ceased WO2022039033A1 (ja)

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US18/006,739 US20230279586A1 (en) 2020-08-21 2021-08-05 Polyamide multifilament, and method of manufacturing same
CN202180049017.4A CN115803484B (zh) 2020-08-21 2021-08-05 聚酰胺复丝和其制造方法
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