WO2023074268A1 - Fibre de polypropylène à résistance élevée et à allongement élevé et son procédé de production - Google Patents

Fibre de polypropylène à résistance élevée et à allongement élevé et son procédé de production Download PDF

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WO2023074268A1
WO2023074268A1 PCT/JP2022/036940 JP2022036940W WO2023074268A1 WO 2023074268 A1 WO2023074268 A1 WO 2023074268A1 JP 2022036940 W JP2022036940 W JP 2022036940W WO 2023074268 A1 WO2023074268 A1 WO 2023074268A1
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polypropylene
temperature
molecular weight
sec
strength
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PCT/JP2022/036940
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Japanese (ja)
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緒臣 貝賀
輝之 谷中
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東洋紡株式会社
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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
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
    • D01F6/06—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins from polypropylene

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  • the present invention relates to polypropylene fibers with high strength, high elongation, and high crystallinity, preferably high strength, high elongation, high crystallinity, and excellent thermal stability at the same time. It also relates to polypropylene fibers.
  • Polypropylene fibers are excellent in chemical resistance, heat resistance, light weight, etc., and are widely used in various applications.
  • a method for producing polypropylene fibers for example, the production method of Patent Document 1 is known. It includes a special process of holding and forming fine crystal nuclei, and since it is manually stretched and heat-set by applying tension, it has poor productivity and cannot be applied as an industry. It was difficult.
  • the raw material used has a relatively low weight average molecular weight, a low stretching temperature, and a relatively low heat setting temperature of less than 150 ° C., it is difficult to obtain a high degree of crystallinity, and the strength is excellent. However, it has been difficult to obtain fibers with excellent thermal stability.
  • Patent Literature 1 no consideration is given to elongation.
  • Patent Document 2 a very high molecular weight raw material with an intrinsic viscosity of at least 5 dL/g is fiberized by employing a solution spinning method using a solvent.
  • melt spinning is difficult, and environmental impact due to the solvent used and a recovery step are required, which poses problems from the viewpoint of production cost and environmental impact.
  • the strength of the obtained fiber is as high as 0.832 to 1.376 GPa, but the elongation is as low as 8.3 to 10.4%, and polypropylene fibers having both strength and elongation could not be provided. .
  • melt-spun polypropylene fibers that have high strength, high elongation, high crystallinity, preferably high thermal stability, and can be produced inexpensively without using solvents.
  • the use of high-molecular-weight polymers is generally known as a method for increasing strength. Both elongation and elongation were not achieved.
  • an object of the present invention is to provide a melt-spun polypropylene fiber having high strength, high elongation, high crystallinity, and preferably also high thermal stability, and a method for producing the same.
  • the present inventor melt-spun using polypropylene having a weight-average molecular weight of 6.0 ⁇ 10 5 or more after fiberization, and stretched at a temperature and a deformation speed. By controlling the, it is possible to draw at a high magnification, and it is possible to produce a melt-spun polypropylene fiber having high crystallinity, high strength, high elongation, and high thermal stability. reached.
  • the present invention relates to a polypropylene fiber having high crystallinity, high strength, excellent elongation, and preferably excellent thermal stability.
  • the polypropylene fiber according to . [3] The polypropylene fiber according to [1] or [2] above, which has a dry heat shrinkage rate of 4% or less in a dry heat shrinkage measurement at a treatment temperature of 140° C.
  • the molecular chains of the present invention are highly oriented, it has a high degree of crystallinity, excellent strength and elongation, and also has thermal stability such as resistance to creep during heating and resistance to heat shrinkage. Excellent polypropylene fibers are obtained.
  • Polypropylene fiber The polypropylene fiber of the present invention has a breaking strength of 12.5 cN/dtex or more, a breaking elongation of 15% or more, a weight average molecular weight of 6.0 ⁇ 10 5 or more, and a crystallinity of 64% or more. characterized by
  • the weight average molecular weight (Mw) of the polypropylene fiber in the present invention is 6.0 ⁇ 10 5 or more.
  • the weight average molecular weight is preferably in the range of 6.0 ⁇ 10 5 to 9.0 ⁇ 10 6 , more preferably in the range of 7.0 ⁇ 10 5 to 4.0 ⁇ 10 6 . Most preferably, it ranges from 0.0 ⁇ 10 5 to 3.0 ⁇ 10 6 .
  • the number average molecular weight (Mn) of the polypropylene fiber in the present invention is preferably in the range of 1.0 ⁇ 10 4 to 5.0 ⁇ 10 5 , more preferably 2.0 ⁇ 10 4 to 4.0 ⁇ 10 5 . and most preferably 3.0 ⁇ 10 4 to 3.0 ⁇ 10 5 .
  • the weight-average molecular weight and number-average molecular weight are below this range, the number of molecular chain ends contained in the fiber increases, making it difficult to increase the strength and achieve high-temperature stretching.
  • the weight average molecular weight and number average molecular weight are above this range, the entanglement of the molecular chains increases, making it difficult to stretch and the molecular chains cannot be highly oriented, making it difficult to increase the strength.
  • the weight-average molecular weight and number-average molecular weight of polypropylene fibers are the molecular weight values after fiberization, unless otherwise specified.
  • a weight average molecular weight and a number average molecular weight can be determined by the GPC method.
  • the breaking strength of the polypropylene fiber in the present invention is 12.5 cN/dtex or more, preferably 14 cN/dtex or more, more preferably 15 cN/dtex or more.
  • the upper limit is not particularly limited, it is preferably 25 cN/dtex or less from the viewpoint of stretchability.
  • the breaking elongation of the polypropylene fiber in the present invention is 15% or more, preferably 18% or more, and more preferably 20% or more.
  • the upper limit is not particularly limited, the elongation at break is preferably 35% or less from the viewpoint of handling.
  • the polypropylene fiber of the present invention has a breaking strength of 12.5 cN/dtex or more and a breaking elongation of 15% or more.
  • the crystallinity of the polypropylene fiber in the present invention is 64% or more, preferably 66% or more, and more preferably 68% or more. Although the upper limit is not particularly limited, 95% or less is preferable. It is presumed that the increase in crystallinity leads to improved stability of the fiber structure and a reduction in defects, resulting in improved elongation as well as strength.
  • the creep rate of the polypropylene fiber in the present invention is preferably 1.0 ⁇ 10 ⁇ 6 sec ⁇ 1 or less at a measurement temperature of 70° C. and a load corresponding to 20% of the breaking strength, and 7.0 ⁇ 10 ⁇ 7 sec ⁇ 1 or less is more preferable, and 5.0 ⁇ 10 ⁇ 7 sec ⁇ 1 or less is even more preferable.
  • the lower limit is not particularly limited, it is preferably 1.0 ⁇ 10 ⁇ 9 sec ⁇ 1 or more.
  • the dry heat shrinkage rate of the polypropylene fiber in the present invention is preferably 4% or less, more preferably 3% or less, in dry heat shrinkage measurement at a treatment temperature of 140°C and a treatment time of 30 minutes.
  • the lower limit is not particularly limited, it is preferably 0.5% or more.
  • the elastic modulus of the polypropylene fiber in the present invention is preferably 130 cN/dtex or more, more preferably 140 cN/dtex or more, and 150 cN/dtex or more, from the viewpoint of achieving a high degree of molecular orientation in the fiber axis direction. is more preferable.
  • the upper limit is not particularly limited, it is preferably 200 cN/dtex or less from the viewpoint of not realizing excessive molecular orientation in the fiber axis direction.
  • the method for producing the polypropylene fiber of the present invention is not particularly limited, it is preferably produced by the following production method.
  • the method for producing polypropylene fiber according to the present invention comprises: (1) a step of melt spinning polypropylene having a weight average molecular weight of 6.0 ⁇ 10 5 or more after fiberization (melt spinning step); (2) a step of cooling the resulting melt-spun fibers to a temperature range from the glass transition temperature of the polypropylene used to the glass transition temperature +50°C (cooling step); (3) a step of drawing the cooled fiber at a drawing temperature of 150° C. or higher and 180° C. or lower at a deformation rate of 0.001 sec ⁇ 1 or more and less than 0.1 sec ⁇ 1 (drawing step); including.
  • melt spinning step melt spinning polypropylene having a weight average molecular weight of 6.0 ⁇ 10 5 or more after fiberization
  • cooling step cooling the resulting melt-spun fibers to a temperature range from the glass transition temperature of the polypropylene used to the glass transition temperature +50°C
  • drawing step a step of drawing the cooled fiber at a drawing temperature of 150° C.
  • ⁇ Raw material composition> In the method for producing a polypropylene fiber of the present invention, a raw material composition containing polypropylene is melt-spun, cooled, and drawn to form a polypropylene fiber.
  • the polypropylene in the raw material composition includes isotactic polypropylene, syndiotactic polypropylene, and atactic polypropylene. Moreover, it may be in a single form from among these, or in a mixed form of two or more thereof. More specifically, the polypropylene in the raw material composition preferably has a pentad (mmmm) fraction, which is an index of stereoregularity, of 0.8 or more (80% or more), and preferably 0.9 or more (90% or more). % or more), more preferably 0.95 or more (95% or more), and most preferably 0.97 or more (97% or more). The higher the pentad fraction, the higher the stereoregularity and the fewer defects when made into a fiber, which is preferable because it increases the strength.
  • mmmm pentad
  • the polypropylene in the raw material composition may be a homopolymer consisting only of propylene units, may be a copolymer with other monomers, or may be a homopolymer and/or copolymer of two or more may be a mixture of Copolymers can include block copolymers and random copolymers.
  • Monomers other than propylene that form the copolymer are not particularly limited, but include, for example, ethylene and 1-butene. In the present invention, a homopolymer consisting only of propylene units is preferred.
  • the weight average molecular weight (Mw) of polypropylene in the raw material composition is adjusted so that the weight average molecular weight after fiberization is 6.0 ⁇ 10 5 or more.
  • the weight average molecular weight of polypropylene as a raw material is not particularly limited, but is preferably 6.0 ⁇ 10 5 or more, more preferably 7.0 ⁇ 10 5 or more, and more preferably 8.0 ⁇ 10 It is more preferably 5 or more, and most preferably 8.5 ⁇ 10 5 or more.
  • the upper limit of the weight average molecular weight of polypropylene as a raw material is not particularly limited, but it is preferably 1.2 ⁇ 10 6 or less from the viewpoint of not impairing the melt-molding process.
  • melt flow rate can be mentioned as an indicator of molecular weight.
  • MFR test method values measured at a temperature of 230°C and a load of 2.16 kgf, which are general conditions applied to polypropylene resin in accordance with JIS K7210, are used.
  • the MFR of polypropylene as a raw material is preferably 2.4 g/10 min or less, more preferably 2.0 g/10 min or less, still more preferably 1.5 g/10 min or less, and most preferably 1.0 g/10 min or less.
  • the lower limit of MFR is not particularly limited, it is preferably 0.2 g/10 min or more.
  • the raw material composition used in the present invention contains polypropylene, and the content of polypropylene in the raw material composition is not particularly limited, but from the viewpoint of realizing a high degree of crystallinity after fiberization, 95% by mass or more, more preferably 98% by mass or more, even more preferably 99% by mass or more, and particularly preferably substantially only polypropylene (100%).
  • additives used in this field can be added to the raw material composition used in the present invention as long as the effects of the present invention are not impaired. Specifically, 5% by mass of the raw material composition or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less.
  • Additives include neutralizing agents, antioxidants, heat stabilizers, weathering agents, lubricants, UV absorbers, antistatic agents, antiblocking agents, antifogging agents, antifogging agents, dispersants, flame retardants, Additives such as antibacterial agents, fluorescent whitening agents, cross-linking agents and cross-linking aids, coloring agents such as dyes and pigments, and the like, among which antioxidants are preferred.
  • ⁇ Melt spinning process> In the method for producing a polypropylene fiber according to the present invention, first, a raw material composition containing polypropylene is melted, the melted product is extruded from a spinning nozzle having a predetermined hole diameter, and is wound by a roller set at a predetermined spinning speed to obtain an unspun fiber. It is preferable to include the step of obtaining a drawn yarn.
  • melt-extrusion of polypropylene a melt-extrusion technique for plastic fibers that is commonly used in the relevant technical field may be used.
  • Means for melt extrusion are not limited, but for example, an extruder that heats and melts a raw material plastic and then presses and extrudes the melt can be used.
  • the spinning temperature of polypropylene is preferably at least the melting point of the polypropylene used (melting point +50° C. or higher), that is, it is preferably at least 50° C. higher than the melting point temperature (melting point +70° C. to melting point +150° C.), That is, it is more preferable to be in the range of 70° C. higher than the melting point to 150° C. higher than the melting point.
  • melt flow it is necessary to suppress the decrease in molecular weight as much as possible during melt flow. From this point of view, if the temperature of the extruder is too high, the polypropylene will deteriorate and the molecular weight will decrease, which is not preferable. On the other hand, if the temperature is too low, the fluidity is lowered, which may cause damage to the apparatus and difficulty in molding due to melt fracture, which is not preferable.
  • the melting point of polypropylene is 150 to 180°C.
  • a method for suppressing the decrease in molecular weight during melt flow it is also preferable to adopt a method such as shortening the melt residence time or adding an antioxidant.
  • the upper limit of the single-hole discharge rate of the spinning nozzle is preferably 1.0 g/min or less, more preferably 0.5 g/min or less. If the single-hole discharge rate is higher than this range, melt fracture or the like may occur, resulting in unstable spinning.
  • the lower limit of the single-hole discharge rate of the spinning nozzle is not particularly limited, but from the viewpoint of productivity, it is preferably 0.05 g/min or more, more preferably 0.1 g/min or more.
  • the spinning speed is preferably 50-700 m/min, more preferably 100-500 m/min. By winding in this speed range, it is possible to control the degree of orientation, crystal structure, etc. in the undrawn yarn, and as a result, the strength of the obtained fiber is improved, which is preferable.
  • the production method of the present invention includes the step of cooling the obtained melt-spun fibers (undrawn fibers) to a temperature range of the glass transition temperature (Tg) of the polypropylene to be used to the glass transition temperature + 50 ° C. .
  • the undrawn yarn is rapidly cooled from the heating temperature in the melt extrusion means to a predetermined temperature A (the glass transition temperature (Tg) of polypropylene to the glass transition temperature + 50 ° C.), and is spun at this temperature A while being taken up.
  • the temperature A is the range of the glass transition temperature (Tg) to (Tg + 50 ° C.) of the polypropylene used, that is, the temperature range from the Tg temperature to 50 ° C. above Tg, and (Tg) to (Tg + 25 ° C.).
  • a temperature in the range is more preferable, and a temperature in the range of (Tg) to (Tg+10° C.) is even more preferable.
  • the Tg of polypropylene is -20°C to 5°C. Cooling can be performed using forced cooling means such as air cooling or refrigerants (eg, water, methanol, ethanol, mixed solvents thereof), or a combination of air cooling and refrigerants.
  • forced cooling means such as air cooling or refrigerants (eg, water, methanol, ethanol, mixed solvents thereof), or a combination of air cooling and refrigerants.
  • drawing process After cooling the undrawn yarn obtained by the melt spinning process, it is drawn by the drawing process to obtain the intended polypropylene fiber.
  • drawing of the undrawn yarn can be carried out using a drawing means commonly used in the technical field.
  • the fiber can be drawn continuously by a speed difference between the delivery roller and the take-up roller.
  • the draw ratio is defined by the speed difference between the delivery roller and the take-up roller.
  • the unstretched yarn pulled out from the delivery roller is heated to a predetermined temperature in an oven of a predetermined length and stretched. Further, the stretching may be performed in one stage or in multiple stages.
  • the draw ratio is preferably 2 times or more, more preferably 5 times or more.
  • the temperature for drawing the undrawn yarn is 150° C. or higher and 180° C. or lower, preferably 150° C. or higher and 175° C. or lower, more preferably 155° C. or higher and 173° C. or lower, and most preferably 160° C. or higher and 173° C. or lower. .
  • the melting point of the polypropylene fiber is increased, and stable drawing near the melting point becomes possible, and drawing at a relatively high temperature becomes possible. This makes it possible to obtain fibers with relatively high crystallinity and relatively low thermal shrinkage. If the drawing temperature is lower than 150° C., the crystallinity of the resulting fiber will be low, making it difficult to obtain a polypropylene fiber with high strength and high elongation.
  • the drawing temperature is in the temperature range from (glass transition temperature (Tg) + 150°C) to (Tg + 200°C), that is, the temperature range from 150°C above the Tg of the undrawn yarn to 200°C above the Tg. is preferred.
  • the undrawn yarn according to the present invention has a Tg of 0 to 20°C.
  • the delivery roller speed, take-up roller speed, and oven length are adjusted so that the deformation speed shown in the following formula is 0.001 sec ⁇ 1 or more and less than 0.1 sec ⁇ 1 , and 0.001 sec ⁇ 1 or more and 0.001 sec ⁇ 1 or more and less than 0.1 sec ⁇ 1 . 05 sec ⁇ 1 or less is preferable. If the deformation rate is higher than this range, the deformation rate of the high-molecular-weight polymer cannot catch up with the deformation rate of the drawing, resulting in a decrease in drawability. In addition, stretching at a deformation rate lower than this range lowers productivity. By adjusting the deformation speed within this range, uniform drawing becomes possible, so that the draw ratio is improved and the strength of the resulting fiber is improved.
  • Deformation speed (sec -1 ) [winding roller speed (m/sec) - delivery roller speed (m/sec)]/oven length (m)
  • Drawing is one of the challenges in obtaining high-strength fibers using high-molecular-weight polymers.
  • the use of a high-molecular-weight polymer tends to hinder stretching and make it difficult to stretch.
  • the reason for this is thought to be that the relaxation time becomes longer when the polymer has a higher molecular weight. Therefore, in the present invention, a drawing temperature of 150 to 180° C., which is a relatively high temperature near the melting point, is adopted, and the drawing is performed at a low deformation rate corresponding to the relaxation time of the polymer with a high molecular weight.
  • the method for producing polypropylene fibers of the present invention includes a melt spinning step, a cooling step, and a drawing step, but may include other steps within a range that does not impair the effects of the present invention.
  • the production method of the present invention employs a relatively high stretching temperature (150 to 180° C.), it does not require heat treatment after stretching, and does not include a heat treatment step after stretching.
  • the breaking strength, breaking elongation, weight average molecular weight, creep rate, dry heat shrinkage, and crystallinity of the polypropylene fiber obtained by the above production method are within the above ranges.
  • the molecular weight reduction from the raw material polypropylene resin to the finally obtained fiber is suppressed, and the molecular weight reduction rate ((weight average molecular weight of the raw material polypropylene resin - final The weight average molecular weight of the obtained fiber) / weight average molecular weight of the raw material polypropylene resin ⁇ 100) is preferably 35% or less, more preferably 25% or less, and 20% or less. More preferably, it is particularly preferably 15% or less.
  • Weight Average Molecular Weight The weight average molecular weight was measured using a high-temperature GPC analyzer HLC-8321GPC/HT manufactured by Tosoh Corporation as follows. Using o-dichlorobenzene as a solvent, the concentration of polypropylene was adjusted to 0.12% by mass. Further, 0.05% by mass of dibutylhydroxytoluene was added as an antioxidant to prepare a measurement sample. Waters Sytragel HT 3,4,6E was used for the column, and the measurement temperature was set to 140°C. 200 ⁇ L of the measurement sample was injected into the measuring device, and the measurement was performed at a flow rate of 0.3 mL/min. RI (polarity ( ⁇ )) was used as a detector.
  • HLC-8321GPC/HT manufactured by Tosoh Corporation as follows. Using o-dichlorobenzene as a solvent, the concentration of polypropylene was adjusted to 0.12% by mass. Further, 0.05% by mass of dibutylhydroxytolu
  • Fineness A sample was cut into 10 m lengths at five different positions, the mass was measured, and the average value was converted to 10000 m to obtain fineness (dtex).
  • one of the free ends of the sample 1 is fixed at the portion protruding from the metal plate 2 (fixed end 4 of the sample), and the other free end is the portion protruding from the metal plate 2.
  • the initial load was removed and a predetermined load 3 (20% of the breaking strength) was applied.
  • the cover 5 is closed from the upper side for heat retention so that the sample 1 on the metal plate 2 does not touch (the cover 5 and the sample 1 are not in contact), and creep measurement is started.
  • the lid 5 was opened and the measurement was performed.
  • the elongation L i (mm) of the sample at a certain time t is the distance L (t) between the marks attached to the sample 1 at that time t and the distance L 0 (50. 0 cm) and is expressed as follows.
  • ⁇ i (t) (%) (L (t) - L 0 ) x 100/L 0
  • the creep rate ⁇ (sec ⁇ 1 ) is defined as the change in length of the sample per second of time, and the creep rate ⁇ i for each measurement time is expressed as follows.
  • ⁇ i (sec ⁇ 1 ) [( ⁇ i ⁇ i ⁇ 1 )/(t i ⁇ t i ⁇ 1 )]/100
  • the distance between the marks was measured from the start of the measurement until 5 hours later, the creep rate ⁇ i for each measurement time was plotted on a logarithmic scale, and the minimum value was taken as the measured creep rate of the sample. After 1 hour, 2 hours, 3 hours, 4 hours, and 5 hours from the start of measurement, a total of 5 measurements were taken. If there is a minute change of less than 0.5 mm of the measurement range, the measurement is excluded. The average of the values obtained by measuring twice was used for the creep rate.
  • Crystallinity Measured using a differential scanning calorimeter DSC25 manufactured by TA Instruments. The degree of crystallinity was calculated by the following formula as the ratio of crystalline regions in the polymer.
  • the heat of fusion of a complete crystal is the heat of fusion when the degree of crystallinity is 100%, and polypropylene is 209 J/g.
  • Crystallinity (%) (measured heat of fusion/heat of fusion of complete crystal) x 100 Cut the sample to 3 to 5 mm or less, fill and seal about 2 mg in an aluminum pan, and use a similar empty aluminum pan as a reference, under a nitrogen gas atmosphere, from 30 ° C. to 250 ° C. at a rate of 10 ° C./min. The area of the obtained endothermic peak was taken as the measured heat of fusion. The average of the values obtained by measuring twice was used for the degree of crystallinity.
  • Melting point Measurement was performed using a differential scanning calorimeter DSC25 manufactured by TA Instruments. Cut the sample to 3 to 5 mm or less, fill and seal about 2 mg in an aluminum pan, and use a similar empty aluminum pan as a reference, under a nitrogen gas atmosphere, from 30 ° C. to 250 ° C. at a rate of 10 ° C./min. The temperature at the endothermic peak top obtained was taken as the melting point. As the melting point, the average of the values obtained by measuring twice was used.
  • the pentad (mmmm) fraction F (mmmm) is expressed as follows.
  • Example 1 Using a commercially available polypropylene resin (manufactured by SunAllomer Co., Ltd., VS200A, MFR: 0.45 g/10 min, weight average molecular weight: 9.5 ⁇ 10 5 ), spinning temperature: 295 ° C., single hole discharge rate: 0.26 g / It is melt extruded from a spinneret with a hole diameter of ⁇ 0.4 mm under the conditions of min, and cooled and solidified by blowing cooling air with a quenching temperature of 23° C. at 0.5 m / sec in the direction perpendicular to the yarn running direction. was taken up at a spinning speed of 250 m/min to obtain an undrawn yarn. This undrawn yarn was drawn 6.5 times under the conditions of drawing temperature: 171° C. and deformation speed: 0.02 sec ⁇ 1 to obtain polypropylene fiber 1 . Physical properties are shown in Table 1.
  • Example 2 Using a commercially available polypropylene resin (manufactured by SunAllomer Co., Ltd., VS200A, MFR: 0.45 g/10 min, weight average molecular weight: 9.5 ⁇ 10 5 ), spinning temperature: 295 ° C., single hole discharge rate: 0.20 g / It is melt extruded from a spinneret with a hole diameter of ⁇ 0.4 mm under the conditions of min, and cooled and solidified by blowing a cooling air with a quenching temperature of 20° C. at 0.5 m/sec in the direction perpendicular to the yarn running direction. was taken up at a spinning speed of 500 m/min to obtain an undrawn yarn. This undrawn yarn was drawn 6.0 times under the conditions of drawing temperature: 171° C. and deformation speed: 0.02 sec ⁇ 1 to obtain polypropylene fiber 2 . Physical properties are shown in Table 1.
  • Example 3 Using a commercially available polypropylene resin (manufactured by SunAllomer Co., Ltd., VS200A, MFR: 0.45 g/10 min, weight average molecular weight: 9.5 ⁇ 10 5 ), spinning temperature: 291 ° C., single hole discharge rate: 0.21 g / It is melt extruded from a spinneret with a hole diameter of ⁇ 0.4 mm under the condition of min, and cooled and solidified by blowing cooling air with a quenching temperature of 20 ° C. at 0.55 m / sec perpendicular to the yarn running direction. was taken up at a spinning speed of 250 m/min to obtain an undrawn yarn. This undrawn yarn was drawn 6.0 times under the conditions of drawing temperature: 172° C. and deformation rate: 0.01 sec ⁇ 1 to obtain polypropylene fiber 3 . Physical properties are shown in Table 1.
  • Example 4 Using a commercially available polypropylene resin (manufactured by SunAllomer Co., Ltd., VS200A, MFR: 0.45 g/10 min, weight average molecular weight: 9.5 ⁇ 10 5 ), spinning temperature: 291 ° C., single hole discharge rate: 0.21 g / It is melt extruded from a spinneret with a hole diameter of ⁇ 0.4 mm under the condition of min, and cooled and solidified by blowing cooling air with a quenching temperature of 20 ° C. at 0.6 m / sec in the direction perpendicular to the yarn running direction. was taken up at a spinning speed of 250 m/min to obtain an undrawn yarn. This undrawn yarn was drawn 6.0 times under the conditions of drawing temperature: 172° C. and deformation speed: 0.04 sec ⁇ 1 to obtain polypropylene fiber 4 . Physical properties are shown in Table 1.
  • Example 5 Using a commercially available polypropylene resin (manufactured by SunAllomer Co., Ltd., VS200A, MFR: 0.45 g/10 min, weight average molecular weight: 9.5 ⁇ 10 5 ), spinning temperature: 296 ° C., single hole discharge rate: 0.26 g / It is melt extruded from a spinneret with a hole diameter of ⁇ 0.3 mm under the condition of min, and cooled and solidified by blowing cooling air with a quenching temperature of 23 ° C. at 0.6 m / sec in the direction perpendicular to the yarn running direction. was taken up at a spinning speed of 250 m/min to obtain an undrawn yarn. This undrawn yarn was drawn 6.5 times under the conditions of drawing temperature: 151° C. and deformation speed: 0.02 sec ⁇ 1 to obtain polypropylene fiber 5 . Physical properties are shown in Table 1.
  • Example 6 Using a commercially available polypropylene resin (manufactured by Japan Polypropylene Corporation, EA9, MFR: 0.5 g/10 min, weight average molecular weight: 9.2 ⁇ 10 5 ), spinning temperature: 295 ° C., single hole discharge amount: 0.27 g /min, melt extruded from a spinneret with a hole diameter of ⁇ 0.6 mm, and cooled and solidified by blowing a cooling wind with a quenching temperature of 18 ° C. at 0.5 m / sec in the direction perpendicular to the yarn running direction, This was wound up at a spinning speed of 375 m/min to obtain an undrawn yarn. This undrawn yarn was drawn 5.5 times under the conditions of drawing temperature: 172° C. and deformation rate: 0.01 sec ⁇ 1 to obtain polypropylene fiber 6 . Physical properties are shown in Table 1.
  • Example 7 Sumilizer GA-80 (manufactured by Sumitomo Chemical Co., Ltd.) was added to a commercially available polypropylene resin (manufactured by Japan Polypropylene Corporation, EA9, MFR: 0.5 g/10 min, weight average molecular weight: 9.2 ⁇ 10 5 ) as an antioxidant. 0.1% by mass and 0.2% by mass of ADEKA STAB PEP-36 (manufactured by ADEKA Co., Ltd.). : Melt extruded from a spinneret with a hole diameter of ⁇ 0.6 mm under the condition of 0.23 g / min, and cooled and solidified by blowing cooling air with a quench temperature of 22 ° C.
  • Example 1 When the undrawn yarn obtained in Example 1 was drawn under the conditions of a drawing temperature of 171° C. and a deformation rate of 0.20 sec ⁇ 1 , it could only be drawn up to a maximum of 5.0 times.
  • Table 2 shows the physical properties of the polypropylene fiber 8 obtained by drawing 5.0 times.
  • Example 3 The undrawn yarn obtained in Example 4 was drawn 4.5 times under the conditions of drawing temperature: 172° C. and deformation speed: 0.12 sec ⁇ 1 to obtain polypropylene fiber 10 . Physical properties are shown in Table 2.
  • Example 4 The undrawn yarn obtained in Example 5 was drawn 5.0 times under the conditions of drawing temperature: 121° C. and deformation rate: 0.01 sec ⁇ 1 to obtain polypropylene fiber 11 . Physical properties are shown in Table 2.
  • Comparative Example 2 the raw material polypropylene had a low weight average molecular weight, and as a result, the obtained polypropylene fiber had a low weight average molecular weight, low crystallinity, and poor strength. In addition, the thermal stability was not sufficient. In Comparative Example 4, the temperature during drawing was low, and as a result, although the elongation of the obtained polypropylene fiber was excellent, the degree of crystallinity was low and the strength was inferior. In addition, the thermal stability was not sufficient.
  • the present invention makes it possible to produce polypropylene fibers with high strength, high elongation, and high crystallinity.
  • the polypropylene fiber of the present invention is suitable for reinforcing fibers for fiber-reinforced resins, ropes, fishing lines and the like.
  • Creep rate measuring device (with lid open) Creep rate measuring device (cover closed)

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Artificial Filaments (AREA)

Abstract

Le but de la présente invention est de fournir des fibres de polypropylène filées à l'état fondu qui ont une résistance élevée et un allongement élevé et qui ont un degré de cristallisation élevé, ainsi que des fibres de polypropylène filées à l'état fondu qui présentent une résistance élevée et un allongement élevé, qui ont un degré de cristallisation élevé, et qui ont une stabilité thermique élevée représentée par la vitesse de fluage et le taux de retrait thermique à sec. Il a été découvert qu'en filant à l'état fondu à l'aide de polypropylène ayant une masse moléculaire moyenne en poids après défibrage de 6,0 × 105 en tant que matière première et en régulant la température de la fibre et la vitesse de déformation pendant le laminage, il est possible de produire des fibres de polypropylène filées à l'état fondu qui peuvent être roulées avec les chaînes de molécules hautement orientées avec un grossissement élevé, qui ont un degré de cristallisation élevé, qui ont une résistance élevée et un allongement élevé, et qui ont une stabilité thermique élevée.
PCT/JP2022/036940 2021-10-28 2022-10-03 Fibre de polypropylène à résistance élevée et à allongement élevé et son procédé de production WO2023074268A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6241341A (ja) * 1985-08-08 1987-02-23 東洋紡績株式会社 ゲル繊維の高速延伸方法
JPS63323A (ja) * 1986-05-05 1988-01-05 ハ−キュルス　インコ−ポレ−テッド 放射抵抗性ポリプロピレン含有生成物の製造方法
JPH06217668A (ja) * 1993-01-29 1994-08-09 Mitsui Petrochem Ind Ltd 高強度ポリプロピレンフィラメント製釣糸
JPH11350283A (ja) * 1997-10-24 1999-12-21 Ube Nitto Kasei Co Ltd 延伸方法および延伸物
WO2013089175A1 (fr) * 2011-12-13 2013-06-20 ダイワボウホールディングス株式会社 Fibres pour le renforcement du ciment, son procédé de production et corps durci en ciment
JP2018500466A (ja) * 2014-12-17 2018-01-11 エテックス・サービシーズ・ナムローゼ・フエンノートシャップＥｔｅｘ Ｓｅｒｖｉｃｅｓ Ｎｖ 改良されたポリプロピレン繊維、その製造方法および繊維セメント製品の製造におけるその使用
JP2019099983A (ja) * 2017-12-01 2019-06-24 株式会社プライムポリマー ポリプロピレン延伸繊維

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6241341A (ja) * 1985-08-08 1987-02-23 東洋紡績株式会社 ゲル繊維の高速延伸方法
JPS63323A (ja) * 1986-05-05 1988-01-05 ハ−キュルス　インコ−ポレ−テッド 放射抵抗性ポリプロピレン含有生成物の製造方法
JPH06217668A (ja) * 1993-01-29 1994-08-09 Mitsui Petrochem Ind Ltd 高強度ポリプロピレンフィラメント製釣糸
JPH11350283A (ja) * 1997-10-24 1999-12-21 Ube Nitto Kasei Co Ltd 延伸方法および延伸物
WO2013089175A1 (fr) * 2011-12-13 2013-06-20 ダイワボウホールディングス株式会社 Fibres pour le renforcement du ciment, son procédé de production et corps durci en ciment
JP2018500466A (ja) * 2014-12-17 2018-01-11 エテックス・サービシーズ・ナムローゼ・フエンノートシャップＥｔｅｘ Ｓｅｒｖｉｃｅｓ Ｎｖ 改良されたポリプロピレン繊維、その製造方法および繊維セメント製品の製造におけるその使用
JP2019099983A (ja) * 2017-12-01 2019-06-24 株式会社プライムポリマー ポリプロピレン延伸繊維

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