WO2016052295A1 - ポリフェニレンスルフィド繊維 - Google Patents
ポリフェニレンスルフィド繊維 Download PDFInfo
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- WO2016052295A1 WO2016052295A1 PCT/JP2015/076911 JP2015076911W WO2016052295A1 WO 2016052295 A1 WO2016052295 A1 WO 2016052295A1 JP 2015076911 W JP2015076911 W JP 2015076911W WO 2016052295 A1 WO2016052295 A1 WO 2016052295A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/14—Polysulfides
- C08G75/16—Polysulfides by polycondensation of organic compounds with inorganic polysulfides
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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
- D01F6/76—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from other polycondensation products
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/08—Filter cloth, i.e. woven, knitted or interlaced material
- B01D39/083—Filter cloth, i.e. woven, knitted or interlaced material of organic material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/375—Thiols containing six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L23/32—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with compounds containing phosphorus or sulfur
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- 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
-
- 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
- D01F6/76—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from other polycondensation products
- D01F6/765—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from other polycondensation products from polyarylene sulfides
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- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
- D02J1/00—Modifying the structure or properties resulting from a particular structure; Modifying, retaining, or restoring the physical form or cross-sectional shape, e.g. by use of dies or squeeze rollers
- D02J1/22—Stretching or tensioning, shrinking or relaxing, e.g. by use of overfeed and underfeed apparatus, or preventing stretch
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- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
- D02J13/00—Heating or cooling the yarn, thread, cord, rope, or the like, not specific to any one of the processes provided for in this subclass
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- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
- D02J13/00—Heating or cooling the yarn, thread, cord, rope, or the like, not specific to any one of the processes provided for in this subclass
- D02J13/005—Heating or cooling the yarn, thread, cord, rope, or the like, not specific to any one of the processes provided for in this subclass by contact with at least one rotating roll
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/06—Filter cloth, e.g. knitted, woven non-woven; self-supported material
- B01D2239/0604—Arrangement of the fibres in the filtering material
- B01D2239/0618—Non-woven
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- 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
- D10B2505/00—Industrial
- D10B2505/04—Filters
Definitions
- the present invention relates to a polyphenylene sulfide fiber having a small change in fiber structure and excellent long-term heat resistance.
- Polyphenylene sulfide (hereinafter abbreviated as PPS) fiber has high heat resistance, chemical resistance, electrical insulation, and flame retardancy, so it can be used in industrial materials such as various filters, electrical insulation, and papermaking canvas.
- PPS Polyphenylene sulfide
- it is widely used for filter cloths used in various industrial filters such as bag filters for collecting waste gas dust.
- a composite fiber is obtained by blend spinning of PPS and another thermoplastic resin, and then subjected to stretching and heat treatment, and then the other thermoplastic resin is eluted and removed.
- a method for obtaining nanofibers Patent Document 4.
- the degree of crystallinity may be high, but it is difficult to reduce the movable amorphous material that bears the molecular motion, and the structural stability of the obtained fiber becomes insufficient.
- the fiber is a nanofiber, the use application is limited, and a process of eluting other thermoplastic resins is required.
- Patent Document 5 a PPS fiber (Patent Document 5) excellent in yarn-making property and yarn physical properties is disclosed.
- Patent Document 5 a technique for increasing the stability of the fiber structure at high temperature and suppressing the strength reduction when the PPS fiber is used.
- the present invention it is an object to provide a PPS fiber that has excellent long-term heat resistance and is suitably used as a bag filter because the change in fiber structure such as crystallinity is small and the decrease in strength is small when used at high temperatures.
- the present inventors have found that the crystallinity is 45.0% or more and the movable amorphous amount is 15.0% or less, and the weight average It has been found that PPS fibers characterized by a molecular weight of 300,000 or less have a small change in fiber structure and a small decrease in strength.
- the present invention it is possible to obtain a PPS fiber that is excellent in long-term heat resistance and suitably used as a bag filter because the change in fiber structure at high temperature is small and the strength decrease is small.
- the PPS in the present invention is a polymer composed of a phenylene sulfide unit such as a p-phenylene sulfide unit represented by the structural formula (1) or an m-phenylene sulfide unit as a main repeating unit. From the viewpoint of heat resistance, a polymer containing 70 mol% or more, further 90 mol% or more of the repeating unit represented by the structural formula (1) is preferable.
- the PPS fiber of the present invention is preferably higher in purity than conventional ones, and the content of alkali metal as an impurity is 50 ppm or less, more preferably 30 ppm or less, and still more preferably 10 ppm or less.
- the alkali metal content of PPS in the present invention is, for example, a value calculated from the amount of alkali metal in the ash that is a residue obtained by baking PPS using an electric furnace or the like. It can be quantified by analyzing by an atomic absorption method.
- the alkali metal refers to lithium, sodium, potassium, rubidium, cesium, and francium in Group IA of the periodic table.
- alkali metals tend to have a strong influence on the thermal characteristics of PPS compared to metal species other than alkali metals, such as alkaline earth metals and transition metals. Therefore, it is speculated that among the various metal species, the increase in the weight average molecular weight of the PPS fiber at a high temperature can be reduced by controlling the alkali metal content within the above range.
- alkali metal sulfides typified by sodium sulfide are most commonly used.
- the heat resistance of the PPS fiber is improved by setting the sodium content within the above range. I guess you can.
- the alkali metal content of PPS in the present invention is, for example, a value calculated from the amount of alkali metal in ash, which is a residue obtained by baking PPS using an electric furnace or the like. Or by atomic absorption spectrometry.
- the PPS fiber of the present invention preferably contains substantially no halogen other than chlorine, that is, fluorine, bromine, iodine, or astatine.
- halogen other than chlorine that is, fluorine, bromine, iodine, or astatine.
- the preferable amount is 1% by weight or less, more preferably 0.5% by weight or less, and further preferably 0.2% by weight or less. And the retention stability tends to be better.
- the fiber diameter of the PPS fiber of the present invention is preferably 1.0 ⁇ m or more, more preferably 5.0 ⁇ m or more, and further preferably 10.0 ⁇ m or more.
- the upper limit of the fiber diameter is preferably 50.0 ⁇ m or less, more preferably 20.0 ⁇ m or less, and further preferably 16.0 ⁇ m or less.
- the single fiber fineness of the PPS fiber of the present invention is preferably 27.0 or less, more preferably 20.0 dtex or less, further preferably 5.0 dtex or less, and particularly preferably 3.0 dtex or less.
- the lower limit of the single fiber fineness is preferably 0.2 dtex or more, and more preferably 0.5 dtex or more.
- the elongation of the PPS fiber of the present invention is preferably less than 50.0%, more preferably 40.0% or less.
- the lower limit of the elongation is preferably 5.0% or more in order to ensure good handleability and process passability.
- the strength of the PPS fiber of the present invention is preferably 1.0 cN / dtex or more, and more preferably 2.0 cN / dtex or more. As the strength is higher, yarn breakage due to external force during use is less likely to occur, and for example, it can be used under high tension.
- the upper limit of the strength is not particularly limited, but the upper limit that can be reached in the present invention is about 20.0 cN / dtex.
- the elastic modulus of the PPS fiber of the present invention is preferably 20.0 to 90.0 cN / dtex. By setting the elastic modulus within this range, the fiber is suitable for high-order workability and durability during actual use.
- the boiling water shrinkage at 98 ° C. of the PPS fiber of the present invention is preferably 1.0% or less, more preferably 0.5% or less, and further preferably 0.3% or less.
- the lower limit of the boiling water shrinkage at 98 ° C. is not particularly limited, but the lower limit that can be achieved in the present invention is about 0.0%.
- the molecular weight of the PPS fiber of the present invention is 300,000 or less in weight average molecular weight, preferably 150,000 or less, more preferably 100,000 or less, and further preferably 70,000 or less.
- the weight average molecular weight is 300,000 or less, the decrease in strength is small because the increase in molecular weight is small even in long-term use at high temperatures.
- the upper limit of the weight average molecular weight of the non-crosslinked linear PPS was about 100,000. Therefore, when the weight average molecular weight of PPS is larger than 300,000, it is considered that the high molecular weight component is not generated as a linear polymer but is generated due to a side reaction such as crosslinking.
- the weight average molecular weight in this invention points out the value calculated
- the PPS fiber in the present invention has a crystallinity of 45.0% or more, preferably 48.0% or more.
- the degree of crystallinity is 45.0% or more, an increase in the degree of crystallinity at a high temperature can be reduced, and a decrease in strength can be suppressed.
- the present inventors performed heat treatment for a long time on the PPS fiber and analyzed the fiber structure. It was found that crystallization progresses continuously until the crystallinity reaches 45.0%, whereas the increase in crystallinity almost converges at 45.0% or more. That is, when the crystallinity is 45.0% or more, the change in crystallinity at high temperatures can be reduced, and a stable fiber structure can be obtained.
- the upper limit at which the crystallinity can be reached is about 60.0% in the present invention.
- the crystallinity in this invention points out the value calculated
- the melting point of the PPS fiber of the present invention is preferably 270.0 to 295.0 ° C, more preferably 275.0 to 285.0 ° C.
- the melting point is 270.0 to 295.0 ° C.
- the crystal size is not excessively large and the structure is uniform, so that high strength can be obtained.
- the melting point exceeds 295.0 ° C. In this case, the fiber structure is not uniform.
- the movable amorphous amount of the PPS fiber of the present invention is 15.0% or less, preferably 10.0% or less, more preferably 9.5% or less.
- the amount of movable amorphous is 15.0% or less, an increase in crystallinity at a high temperature can be reduced, and a decrease in strength can be suppressed.
- the present inventors performed heat treatment for PPS fibers for a much longer time than before and analyzed the fiber structure. And when the amount of movable amorphous is more than 15.0%, the amount of movable amorphous decreases continuously, and the degree of crystallinity increases. I found out.
- the movable amorphous amount in the present invention refers to a value obtained by the method described in the examples.
- the important point of the present invention is that the crystallinity is increased to 45.0% or more and the movable amorphous amount is reduced to 15.0% or less, and at the same time, the weight average molecular weight is controlled to 300,000 or less. It is.
- a means for obtaining such a fiber for example, a method of performing heat treatment for a long time in a temperature range in which crystallization proceeds but side reaction does not proceed is adopted. Can be obtained.
- the PPS fiber of the present invention has a stable fiber structure and excellent long-term heat resistance, it has chemical resistance, mechanical properties, electrical insulation, and flame retardancy.
- Filter applications such as bug filters, chemical filters, food filters, chemical filters, oil filters, engine oil filters, air purification filters, paper applications such as electrical insulation paper, heat resistant work clothes applications such as fire clothes, safety Clothes, experimental work clothes, warm clothing, flame retardant clothing, felt for papermaking, sewing thread, heat-resistant felt, release material, paper dryer dryer, battery separator, electrode separator, heart patch, artificial blood vessel, artificial skin, printed circuit board
- Base material, copy rolling cleaner, ion exchange base material, oil retaining material, heat insulating material, cushion material, brush, net Nbea, motor annoyed yarn can be suitably used in various applications such as motor binder tape, in particular can be preferably used as a bag filter, is not limited to these applications.
- Examples of the method for producing a PPS polymer in the present invention include a method for obtaining a PPS polymer by melting and heating a cyclic PPS compound, as described in JP-A-2008-202164.
- a PPS polymer By using such a PPS polymer, the alkali metal content is low, so that side reactions such as crosslinking can be suppressed during heat treatment.
- the PPS polymer in the present invention is dried before being subjected to melt spinning in order to suppress foaming due to water mixing and to improve the yarn production. Moreover, since the low boiling point monomer remaining in the PPS polymer can be removed by performing vacuum drying, it is possible to further improve the yarn-making property, and it is more preferable. As drying conditions, vacuum drying at 100 to 200 ° C. for 8 to 24 hours is usually used.
- melt spinning a known melt spinning technique using a spinning machine such as a pressure melter type, a single-screw / double-screw extruder type, or the like can be applied.
- the extruded polymer is measured by a known measuring device such as a gear pump through a pipe, and after passing through a filter for removing foreign matter, is guided to a base.
- the temperature from the polymer pipe to the die is preferably not less than the melting point of PPS, and more preferably not less than the melting point of PPS + 10 ° C. in order to improve fluidity.
- the temperature is preferably 400 ° C. or less, and more preferably 380 ° C. or less. It is also possible to independently adjust the temperature from the polymer pipe to the base. In this case, the discharge is stabilized by making the temperature of the part close to the base higher than the temperature on the upstream side.
- the base used in discharge preferably has a base hole diameter D of 0.10 mm to 0.40 mm, and the land length L of the base hole (the length of the straight pipe portion equal to the diameter of the base hole).
- the L / D defined by the quotient divided by the pore diameter is preferably 1.0 or more and 4.0 or less. Further, the number of holes per cap is preferably 20 holes or more from the viewpoint of production efficiency.
- the yarn discharged from the cap hole is cooled and solidified with gas or liquid.
- gas any gas such as air or a mixed gas such as nitrogen, oxygen, and water vapor can be used, but air is preferable from the viewpoint of handleability.
- the temperature of the cooling gas may be determined by the balance with the cooling air speed from the viewpoint of cooling efficiency, but is preferably 50 ° C. or less from the viewpoint of fineness uniformity.
- the cooling gas is allowed to cool the yarn by flowing in a direction substantially perpendicular to the yarn. In that case, the speed of the cooling air is preferably 5 m / min or more from the viewpoint of cooling efficiency and fineness uniformity, and is preferably 50 m / min or less from the viewpoint of yarn production stability.
- any liquid such as water, alcohol, or an organic solvent can be used, but water is preferable from the viewpoint of handleability.
- the yarn discharged from the base hole is converged within 500 mm to 7,000 mm from the cooling start position.
- the distance from the cooling start position to the convergence position is less than 500 mm, the yarn may converge before solidification, and there is a decrease in physical properties due to the occurrence of fusion between single yarns and fiber diameter variation due to destabilization of the solidification point. It leads to increase. If it does not converge within 7,000 mm, yarn breakage is likely to occur due to an increase in spinning tension, and spinning stability is reduced.
- the cooled and solidified yarn is taken up by a roller (godet roller) that rotates at a constant speed.
- the take-up speed is preferably 300 m / min or more, and more preferably 500 m / min or more in order to improve linear uniformity and productivity.
- the upper limit is preferably 4000 m / min or less in order to suppress crystal formation during high speed spinning.
- the unstretched yarn obtained in this way is stretched between the first roller and the second roller after being taken up once or continuously after being taken up. That is, the undrawn yarn is heated to a predetermined temperature by a heated first roller or a heating device provided between the first roller and the second roller, and according to the ratio of the peripheral speeds of the first roller and the second roller. The conditions are set so that the film is stretched near the heating source.
- the first roller When the first roller is used as the heating source, a separate roller may be attached to these rollers, and the fiber may be heated and fixed at a speed while the rollers are circulated.
- the number of times of fiber circulation to each roller is 6 times or more. From the viewpoint of equipment productivity, the upper limit is about 10 times.
- the heating device When using a heating device provided between the first roller and the second roller as a heating source, the heating device may be a contact type or a non-contact type.
- a hot pin, a hot plate, a liquid bath, laser, infrared rays, heated steam and the like can be used, and it is preferable to use a liquid bath from the viewpoints of handleability and thermal efficiency.
- any liquid such as water, alcohol, or an organic solvent can be used as the liquid, but water is preferable from the viewpoint of handleability.
- the temperature of the heating source in the stretching step is preferably 70 ° C or higher and 130 ° C or lower.
- the temperature of the heating source in the stretching step is preferably 70 ° C or higher and 130 ° C or lower.
- process passability is improved and stable stretching is possible.
- temperature is set to 130 ° C. or lower, fluff and yarn breakage can be suppressed, and excellent quality fibers can be obtained.
- the presence or absence of heating of the second roller is arbitrary, but when the second roller is heated, it is preferable to set it to 130 ° C. or less from the viewpoint of process passability.
- the temperature of a 2nd roller exceeds 130 degreeC, possibility that it will be extended
- a third roller group having a plurality of rollers, or a heating device provided between the rollers is used. It is preferable to heat and set the strip.
- the heating device may be a contact type or a non-contact type, and specific means such as a hot pin, a hot plate, a liquid bath, a laser, infrared rays, and heated steam can be used.
- the heating temperature of the heating roller as a means for performing the heat treatment is preferably 160 ° C. or higher, and more preferably 180 ° C. or higher. Moreover, since it fuses when the temperature of a heating roller becomes near melting
- the heating time is preferably 0.1 seconds or more, and more preferably 0.3 seconds or more because crystallization does not proceed sufficiently if the heating time is extremely short.
- the upper limit of the heating time is not particularly limited, but is preferably 1,000 seconds or less from the viewpoint of productivity.
- the draw ratio between the second roller and the third roller can be arbitrarily adjusted within a range where the fibers are not broken, but can be set within a range of 0.9 to 1.1 times, and 0.9 to 1.0. A range of double is more preferable.
- the total draw ratio represented by the ratio of the peripheral speed of the third roller to the peripheral speed of the first roller is 2.0 times or more, and more preferably 2.5 times or more. By setting the total draw ratio to 2.0 times or more, it is possible to produce fibers having mechanical properties that can withstand practical use.
- the upper limit of the total draw ratio is not particularly limited, but the upper limit that can be reached in the present invention is about 6.0 times.
- the total draw ratio in the present invention is defined by the ratio of the feed speed of undrawn fibers used for drawing, that is, the ratio of the peripheral speed of the last roller to the peripheral speed of the first roller used for drawing.
- the last roller is a final roller that regulates the speed of the yarn in the drawing and heat treatment processes, and generally the drawing and heat treatment are continuously performed, and thus represents the final roller after the heat treatment. That is, when winding as a long fiber, it is a roller immediately before the winder, and when crimping for short fiber, it becomes a roller after heat treatment and before crimping.
- the PPS fibers obtained in this way are subjected to heat treatment for a long time to stabilize the structure.
- the temperature is preferably 85 to 240 ° C, more preferably 130 to 230 ° C, and still more preferably 180 to 220 ° C.
- the heat treatment time depends on the heat treatment temperature, but at any temperature of 85 to 240 ° C., at least 500 hours or more is necessary to achieve a crystallinity of 45.0% or more. For example, at a temperature of 220 ° C., a crystallinity of 45.0% or more can be reached by performing a heat treatment for 500 hours (21 days). Since it does not depend on the form and method of the heat treatment, it is possible to carry out the heat treatment with the actual use environment as a product of the bag filter in which the heat of about 150 to 210 ° C. continues.
- A. Weight average molecular weight The weight average molecular weight of the PPS polymer and the PPS fiber was calculated in terms of polystyrene using gel permeation chromatography (GPC) which is a kind of size exclusion chromatography (SEC). The measurement conditions for GPC are shown below. Apparatus: SSC-7100 manufactured by Senshu Scientific Co., Ltd. Column name: GPC3506 manufactured by Senshu Kagaku Co., Ltd.
- the observed exothermic peak temperature was defined as the crystallization temperature (Tc), and Tc
- the amount of heat of crystallization was ⁇ Hc (J / g).
- the temperature of the endothermic peak observed at a temperature of 200 ° C. or higher was defined as the melting point (Tm), and the heat of fusion at Tm was defined as ⁇ Hm (J / g).
- the difference between ⁇ Hm and ⁇ Hc was divided by the heat of fusion of complete crystal PPS (146.2 J / g) to determine crystallinity Xc (%).
- Xc ⁇ ( ⁇ Hm ⁇ Hc) /146.2 ⁇ ⁇ 100 D.
- Movable amorphous amount (Xma), thermal characteristics (Tg, ⁇ Cp) Differential scanning calorimetry was performed under the conditions of a temperature modulation DSC of the same equipment as C above under a temperature rise rate of 2 ° C./min, a temperature amplitude of 1 ° C., and a temperature modulation period of 60 seconds under nitrogen, and the glass transition temperature ( Tg)
- Tg glass transition temperature
- An auxiliary line is drawn on the front and back baselines, and the difference is defined as the specific heat difference ⁇ Cp (J / g ° C.), divided by the specific heat difference (0.2699 J / g ° C.) before and after the Tg of the completely amorphous PPS.
- the crystal amount Xma (%) was determined.
- Xma ( ⁇ Cp / 0.2699) ⁇ 100 E.
- the fiber diameter was measured by observing the side of the fiber using a fiber diameter microscope.
- the total fineness and the single fiber fineness measuring machine were used to remove 100 m of fiber, the weight (g) was multiplied by 100, the measurement was performed three times per level, and the average value was defined as the total fineness (dtex). The quotient obtained by dividing this by the number of filaments was defined as the single fiber fineness (dtex).
- Boiling water shrinkage rate In accordance with the method described in JIS L 1013, the measurement was performed by the following method. The sample was allowed to stand in an atmosphere of 20 ° C. and 65% RH, and then the thread length before the treatment was measured by applying a load of 1/30 g / dtex to the crushed yarn. The yarn was heat treated in hot water at 98 ° C. for 30 minutes, the yarn length after treatment was measured under the same load as before treatment, and the average value of 5 times calculated by the following equation was used as the boiling water shrinkage rate. did.
- reaction vessel After gradually heating over 3 hours and distilling 14.8 kg of water and 280 g of NMP through a rectifying column, the reaction vessel was cooled to 160 ° C. In addition, 0.02 mol of hydrogen sulfide per 1 mol of the sulfur component charged during this liquid removal operation was scattered out of the system.
- the weight average molecular weight of this white powder is 900, and the ash content, which is a residue baked in an electric furnace or the like, is analyzed by ion chromatography. As a result, the Na content is 4 ppm and the chlorine content is 2.2% by weight. Alkali metals other than Na and halogens other than chlorine were below the detection limit.
- the absorption spectrum in the infrared spectroscopic analysis of this white powder revealed that the white powder was PPS.
- a differential scanning calorimeter temperature increase rate 40 ° C./min
- it shows a broad endotherm at about 200 to 260 ° C., and the peak temperature is about 215 ° C. I found out.
- this white powder is a linear PPS having 4 to 11 repeating units and a linear chain having 2 to 11 repeating units. It was found that the weight ratio of cyclic PPS to linear PPS was about 9: 1. The white powder thus obtained was found to be a PPS oligomer containing about 90% by weight of cyclic PPS and about 10% by weight of linear PPS.
- the resin was supplied to In the spin pack, the polymer was filtered using a metal nonwoven fabric filter, and the polymer was discharged under the condition of 18 g / min from a die having 36 die holes having a hole diameter D of 0.23 mm and a land length L of 0.30 mm. .
- the introduction hole located immediately above the die hole was a straight hole, and the connection portion between the introduction hole and the die hole was tapered.
- the discharged polymer was passed through a 40 mm heat-retaining region, then cooled from the outside of the yarn by air flow at 25 ° C., solidified, and then a spinning oil mainly composed of a fatty acid ester compound was applied to make all filaments 600 m. It was taken up by the first godet roll at a spinning speed of / min. This was passed through a second godet roll having the same speed, and then wound with a winder to obtain an undrawn yarn.
- the undrawn yarn is taken up by a feed roller attached with a nip roller, and tension is applied to the undrawn yarn between the first roller and the first and second rollers heated to 100 ° C. and 110 ° C., respectively. Stretched 6 times and stretched at a stretch ratio of 3.8 times.
- the third roller heated to 230 ° C. was rotated six times and subjected to heat setting.
- the peripheral speed of the third roller was 400 m / min, and the peripheral speed ratio with respect to the second roller was 0.95.
- the fiber coming out of the third roller was taken up by a non-heated roller having the same speed as that of the third roller and wound up by a winder.
- the obtained fiber was made into 1.125 m / lap ⁇ 15 lap, folded and placed in a beaker, kept at 220 ° C. in an inspec thermostat (PHH-201), and heat-treated for 21 days.
- Example 1 The fiber properties of the obtained fiber are shown in Table 1. Since the weight average molecular weight is 300,000 or less, the crystallinity is 45.0% or more, and the movable amorphous amount is 15% or less, it is presumed that the structural change at high temperature is small and the strength reduction is small. [Example 2] In Example 1, spinning, stretching, and heat treatment were performed in the same manner as in Example 1 except that the heat treatment time was 42 days.
- Example 1 The fiber properties of the obtained fiber are shown in Table 1. Although the treatment is longer than that in Example 1, the weight average molecular weight is not increased. Since the weight average molecular weight is 300,000 or less, the crystallinity is 45.0% or more, and the movable amorphous amount is 15% or less, it is presumed that the structural change at high temperature is small and the strength reduction is small. [Comparative Example 1] In Example 1, spinning and stretching were performed in the same manner as in Example 1 except that the heat treatment was not performed.
- Example 1 The fiber properties of the obtained fiber are shown in Table 1. Since no heat treatment is performed, the crystallinity is less than 45.0%, the amount of movable amorphous material exceeds 15%, and the increase in crystallinity is large and the strength is greatly reduced in long-term use at high temperatures. Guessed. [Comparative Example 2] In Example 1, spinning, stretching, and heat treatment were performed in the same manner as in Example 1 except that the heat treatment time was 1 day.
- the fiber properties of the obtained fiber are shown in Table 1. Since the heat treatment time is not enough, the degree of crystallinity is less than 45.0%, the amount of movable amorphous material exceeds 15%, and it is estimated that the increase in crystallinity is large and the strength is greatly reduced in long-term use at high temperatures. Is done.
- the fiber properties of the obtained fiber are shown in Table 1. Since heat treatment has not been performed, the degree of crystallinity is less than 45.0%, the amount of movable amorphous material exceeds 15%, and it is assumed that the increase in crystallinity is large and the strength is greatly reduced in long-term use at high temperatures. Is done.
- the fiber properties of the obtained fiber are shown in Table 1. Since the heat treatment time is not enough, the degree of crystallinity is less than 45.0%, the amount of movable amorphous material exceeds 15%, and it is estimated that the increase in crystallinity is large and the strength is greatly reduced in long-term use at high temperatures. Is done. [Comparative Example 5] Spinning, stretching, and heat treatment were performed in the same manner as in Example 1 except that the PPS resin (B) obtained in Reference Example 3 was used.
- Table 1 shows the fiber properties of the obtained fibers. It can be seen that the heat treatment resulted in a crystallinity of 45.0% or more and a mobile amorphous amount of 15% or less, but the weight average molecular weight was greater than 300,000. It is estimated that the strength reduction is large due to the influence of the crosslinking component.
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Abstract
Description
PPSポリマーおよびPPS繊維の重量平均分子量はサイズ排除クロマトグラフィー(SEC)の一種であるゲルパーミエーションクロマトグラフィー(GPC)を用いて、ポリスチレン換算で算出した。GPCの測定条件を以下に示す。
装置:(株)センシュー科学製 SSC-7100
カラム名:(株)センシュー科学製 GPC3506
溶離液:1-クロロナフタレン
検出器:示差屈折率検出器
カラム温度:210℃
プレ恒温槽温度:250℃
ポンプ恒温槽温度:50℃
検出器温度:210℃
流量:1.0mL/min
試料注入量:300μL(スラリー状:約0.2重量%)
B.アルカリ金属含有量
PPS樹脂およびPPS繊維中のアルカリ金属含有量の定量は下記により行った。
(a) 試料を石英るつぼに秤とり、電気炉を用いて灰化した。
(b) 灰化物を濃硝酸で溶解した後、希硝酸で定容とした。
(c) 得られた定容液をICP重量分析法(装置;Agilent製4500)及びICP発光分光分析法(装置;PerkinElmer社製Optima4300DV)に処した。
示差走査熱量計(TA Instruments社製DSCQ1000)で窒素下、昇温速度10℃/分の条件で示差走査熱量測定を行い、観測される発熱ピークの温度を結晶化温度(Tc)とし、Tcでの結晶化熱量をΔHc(J/g)とした。また、200℃以上の温度にて観測される吸熱ピークの温度を融点(Tm)とし、Tmでの融解熱量をΔHm(J/g)とした。ΔHmとΔHcの差を完全結晶PPSの融解熱量(146.2J/g)で割り、結晶化度Xc(%)を求めた。
D.可動非晶量(Xma)、熱特性(Tg、ΔCp)
上記Cと同一機器の温度変調DSCで窒素下、昇温速度2℃/分、温度振幅1℃、温度変調周期60秒の条件で示差走査熱量測定を行い、得られたチャートのガラス転移温度(Tg)前後のベースラインに補助線を引き、その差を比熱差ΔCp(J/g℃)とし、完全非晶PPSのTg前後での比熱差(0.2699J/g℃)で割り、可動非晶量Xma(%)を求めた。
E.繊維直径
顕微鏡を用い、繊維の側面を観察することで繊維直径を測定した。
検尺機にて繊維を100mカセ取りし、その重量(g)を100倍し、1水準当たり3回の測定を行い、平均値を総繊度(dtex)とした。これをフィラメント数で除した商を単繊維繊度(dtex)とした。
JIS L1013:2010記載の方法に準じて、試料長200mm、引張速度200mm/分の条件で、(株)オリエンテック社製テンシロンUCT-100を用い1水準当たり10回の測定を行い、平均値を強力(cN)、強度(cN/dtex)、伸度(%)、弾性率(cN/dtex)とした。
JIS L 1013記載の方法に準じて、以下の方法で測定を行った。試料を20℃、65%RHの雰囲気下で放置後、カセ取りした糸条に1/30g/dtexの荷重をかけて処理前の糸長を測長した。その糸条を98℃の熱水中にて30分間熱処理後、処理前と同じ荷重下で処理後の糸長を測長し、下式により算出した5回の平均値を沸騰水収縮率とした。
[参考例1]
<PPSオリゴマーの作製>
撹拌機付きの70リットルオートクレーブに、47.5%水硫化ナトリウム8.27kg(70.0モル)、96%水酸化ナトリウム2.96kg(71.0モル)、N‐メチル‐2‐ピロリドン(以下、NMPと略すことがある)を11.44kg(116モル)、酢酸ナトリウム1.72kg(21.0モル)、及びイオン交換水10.5kgを仕込み、常圧で窒素を通じながら約240℃まで約3時間かけて徐々に加熱し、精留塔を介して水14.8kgおよびNMP280gを留出した後、反応容器を160℃に冷却した。なお、この脱液操作の間に仕込んだイオウ成分1モル当たり0.02モルの硫化水素が系外に飛散した。
[参考例2]
<PPS樹脂(A)の作製>
参考例1で得られた環式PPSを含むPPSオリゴマーを攪拌機を取り付けたオートクレーブ中に仕込み、窒素で雰囲気を置換し、オートクレーブを1時間かけ340℃に昇温した。昇温途中でPPSオリゴマーが溶融したら、攪拌機の回転を開始し、回転数10rpmで攪拌しながら180分間溶融加熱した。その後、窒素圧により樹脂を吐出孔よりガット状で取り出し、ガットをペレタイズした。このようにして得られた固形物を130℃で熱風乾燥し、乾燥されたPPS樹脂(A)を得た。
[参考例3]
<PPSポリマー(B)の作製>
参考例1で得られた粗PPS樹脂20kgにNMP約50リットルを加えて85℃で30分間洗浄し、ふるい(80mesh、目開き0.175mm)で濾別した。得られた固形物を50リットルのイオン交換水で希釈して、70℃で30分攪拌後、80meshふるいで濾過固形物を回収する操作を合計5回繰り返した。このようにして得られた固形物を130℃で熱風乾燥し、乾燥されたPPS樹脂(B)を得た。
[実施例1]
参考例2で得られたPPS樹脂(A)を用い、150℃にて10時間の真空乾燥を行った後、テクノベル社製KZW二軸押出し機にて溶融押出しし、ギアーポンプで計量しつつ紡糸パックに樹脂を供給した。紡糸パック内では金属不織布フィルターを用いてポリマーを濾過し、孔径Dが0.23mm、ランド長Lが0.30mmの口金孔を36孔有する口金より、18g/minの条件にてポリマーを吐出した。なお、口金孔の直上に位置する導入孔はストレート孔とし、導入孔と口金孔の接続部分はテーパーとしたものを用いた。吐出したポリマーは40mmの保温領域を通過させた後、25℃、空気流により糸条の外側から冷却し固化させ、その後、脂肪酸エステル化合物を主成分とする紡糸油剤を付与し、全フィラメントを600m/minの紡糸速度で第1ゴデットロールに引き取った。これを同じ速度である第2ゴデットロールを介した後、ワインダーにて巻き取り未延伸糸を得た。
[実施例2]
実施例1において、熱処理時間を42日間にしたこと以外は、実施例1と同様にして、紡糸・延伸・熱処理を行った。
[比較例1]
実施例1において、熱処理を実施しなかったこと以外は、実施例1と同様にして、紡糸・延伸を行った。
[比較例2]
実施例1において、熱処理時間を1日間にしたこと以外は、実施例1と同様にして、紡糸・延伸・熱処理を行った。
[比較例3]
参考例3で得られたPPS樹脂(B)を用い、熱処理を実施しなかったこと以外は、実施例1と同様の方法で紡糸・延伸を行った。
[比較例4]
参考例3で得られたPPS樹脂(B)を用い、熱処理時間を1日とした以外は実施例1と同様の方法で紡糸・延伸・熱処理を行った。
[比較例5]
参考例3で得られたPPS樹脂(B)を用いた以外は実施例1と同様の方法で紡糸・延伸・熱処理を行った。
Claims (3)
- 結晶化度が45.0%以上および可動非晶量が15.0%以下であって、重量平均分子量が300,000以下であることを特徴とするポリフェニレンスルフィド繊維。
- 繊維直径が5.0μm以上であることを特徴とする、請求項1記載のポリフェニレンスルフィド繊維。
- 98℃での沸騰水収縮率が1.0%以下であることを特徴とする、請求項1または2記載のポリフェニレンスルフィド繊維。
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US15/515,519 US10106655B2 (en) | 2014-09-30 | 2015-09-24 | Polyphenylene sulfide fiber |
EP15847414.8A EP3202961A4 (en) | 2014-09-30 | 2015-09-24 | Polyphenylene sulfide fiber |
AU2015325717A AU2015325717B2 (en) | 2014-09-30 | 2015-09-24 | Polyphenylene sulfide fiber |
JP2015556328A JP6642004B2 (ja) | 2014-09-30 | 2015-09-24 | ポリフェニレンスルフィド繊維 |
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CN107447288A (zh) * | 2017-03-06 | 2017-12-08 | 东华大学 | 一种抗热氧老化PPS/大内腔HNTs杂化纤维及其制备方法 |
JP2018127739A (ja) * | 2017-02-09 | 2018-08-16 | 帝人フロンティア株式会社 | 食品フィルター用ポリフェニレンサルファイド繊維およびその製造方法 |
CN110983460A (zh) * | 2019-12-26 | 2020-04-10 | 重庆普力晟新材料有限公司 | 一种一步牵伸制备高性能聚苯硫醚纤维的生产方法 |
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US10829595B2 (en) * | 2018-02-06 | 2020-11-10 | Solvay Specialty Polymers Usa, Llc | Polyphenylene sulfide polymers having improved melt-stability |
KR102692412B1 (ko) * | 2018-09-27 | 2024-08-05 | 도레이 카부시키가이샤 | 공중합 폴리페닐렌술피드 섬유 |
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US20170226292A1 (en) | 2017-08-10 |
US10106655B2 (en) | 2018-10-23 |
EP3202961A1 (en) | 2017-08-09 |
KR102259621B1 (ko) | 2021-06-02 |
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EP3202961A4 (en) | 2018-05-02 |
TW201619462A (zh) | 2016-06-01 |
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