WO2023171699A1 - Composition contenant un polymère, procédé de production d'une composition contenant un polymère, et procédé de production de fibres polymères - Google Patents

Composition contenant un polymère, procédé de production d'une composition contenant un polymère, et procédé de production de fibres polymères Download PDF

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WO2023171699A1
WO2023171699A1 PCT/JP2023/008752 JP2023008752W WO2023171699A1 WO 2023171699 A1 WO2023171699 A1 WO 2023171699A1 JP 2023008752 W JP2023008752 W JP 2023008752W WO 2023171699 A1 WO2023171699 A1 WO 2023171699A1
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Prior art keywords
polymer
containing composition
organic solvent
liquid
polymer fiber
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PCT/JP2023/008752
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English (en)
Japanese (ja)
Inventor
伸一 八木
淮中 徐
秀樹 山根
毅紘 永濱
直人 山本
雅士 清水
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国立大学法人京都工芸繊維大学
株式会社Rinnovation
Ｃｕｒｅｌａｂｏ株式会社
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Publication of WO2023171699A1 publication Critical patent/WO2023171699A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/19—Quaternary ammonium compounds
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3445—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/16—Compositions of unspecified macromolecular compounds the macromolecular compounds being biodegradable
    • 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
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

  • the present invention relates to a polymer-containing composition, a method for producing a polymer-containing composition, and a method for producing a polymer fiber.
  • a method for producing cellulose fibers has been proposed in which purified cellulose fibers are spun by a known spinning method such as dry spinning or wet spinning using a cellulose solution obtained by dissolving a cellulose raw material in an organic solvent containing an ionic liquid. (For example, see Patent Document 1).
  • the present invention has been made in view of the above reasons, and aims to provide a polymer-containing composition, a method for producing a polymer-containing composition, and a method for producing a polymer fiber that can spin polymer fibers at high speed.
  • the polymer-containing composition according to the present invention includes: It is gel-like and contains a biodegradable polymer, a sulfoxide-based organic solvent or a nitrogen-containing organic solvent, and an ionic liquid,
  • the weight ratio of the ionic liquid to the polymer is 8 or more and 10 or less
  • the weight ratio of the ionic liquid to the organic solvent is 0.4 or more and 0.5 or less.
  • the method for producing a polymer-containing composition according to the present invention from another perspective is as follows: a dipping step of immersing the biodegradable polymer in a sulfoxide-based organic solvent or a nitrogen-containing organic solvent; a polymer solution preparation step of mixing the polymer, the organic solvent, and the ionic liquid to prepare a polymer solution; The method includes a crosslinking treatment step of crosslinking a part of the polymer contained in the polymer solution by adding a liquid containing water to the polymer solution.
  • the polymer fiber manufacturing method according to the present invention from another perspective is as follows: heating a gel-like polymer-containing composition containing a biodegradable polymer, a sulfoxide-based organic solvent or a nitrogen-containing organic solvent, and an ionic liquid to form a viscous liquid; The viscous liquid polymer-containing composition is removed by removing the organic solvent from the polymer-containing composition using a nozzle that discharges the viscous liquid polymer-containing composition.
  • the method includes an ionic liquid removal step of removing an ionic liquid contained in the polymer fiber precursor by immersing the polymer fiber precursor in a liquid containing water.
  • the polymer-containing composition according to the present invention is in the form of a gel, and by heating the polymer-containing composition, it can be turned into a viscous liquid and discharged from a nozzle into a coagulation tank. As a result, the time required to recover the polymer-containing composition discharged into the coagulation tank as a polymer fiber precursor can be shortened, so that polymer fibers can be spun at a correspondingly high speed.
  • 1 is a schematic diagram of a polymer fiber manufacturing apparatus according to an embodiment of the present invention.
  • 3 is a SEM photograph of the surface of a polymer fiber according to Comparative Example 3.
  • 3 is a SEM photograph of a cross section of a polymer fiber according to Comparative Example 3.
  • 3 is a SEM photograph of the surface of a polymer fiber according to Comparative Example 4.
  • 3 is a SEM photograph of a cross section of a polymer fiber according to Comparative Example 4.
  • 3 is a SEM photograph of the surface of a polymer fiber according to Comparative Example 5.
  • 3 is a SEM photograph of a cross section of a polymer fiber according to Comparative Example 5.
  • 1 is a SEM photograph of the surface of a polymer fiber according to Example 1.
  • FIG. 1 is a SEM photograph of a cross section of a polymer fiber according to Example 1.
  • FIG. 7 is a diagram showing a diffraction pattern of wide-angle X-ray diffraction measurement of a polymer fiber according to Comparative Example 6.
  • 3 is a diagram showing a diffraction pattern of wide-angle X-ray diffraction measurement of the polymer fiber according to Example 1.
  • FIG. FIG. 7 is a diagram showing the temperature dependence of loss modulus and loss coefficient of polymer fibers according to Comparative Example 7 and Example 1.
  • 3 is a photograph of the appearance of a polymer fiber according to Comparative Example 8.
  • 3 is a photograph of the appearance of a polymer fiber according to Comparative Example 9.
  • 3 is a SEM photograph of a cross section of a polymer fiber according to Comparative Example 9.
  • 3 is a SEM photograph of a cross section of a polymer fiber according to Comparative Example 10.
  • 3 is a SEM photograph of a cross section of a polymer fiber according to Comparative Example 11.
  • 3 is a SEM photograph of the surface of a polymer fiber according to Comparative Example 9.
  • 3 is a SEM photograph of a cross section of a polymer fiber according to Comparative Example 9.
  • 3 is a SEM photograph of the surface of a polymer fiber according to Comparative Example 9.
  • 3 is a SEM photograph of a cross section of a polymer fiber according to Comparative Example 9.
  • 3 is a SEM photograph of the surface of a polymer fiber according to Example 3.
  • 3 is a SEM photograph of a cross section of a polymer fiber according to Example 3.
  • polymer fibers are spun using a gel-like polymer-containing composition.
  • the polymer-containing composition according to this embodiment is in the form of a gel and includes a biodegradable polymer, a sulfoxide-based organic solvent or a nitrogen-containing organic solvent, and an ionic liquid.
  • biodegradable polymers include cellulose, collagen, fibrin, chitin, chitosan, alginate, oxidized alginate, starch, hyaluronic acid, laminin, agarose, gelatin, glucan, or multiple polymers selected from these polymer groups. Examples include combinations of polymers.
  • examples of the biodegradable polymer include a derivative of one polymer selected from these polymer groups, or a derivative of a combination of a plurality of polymers selected from these polymer groups.
  • Examples of the above-mentioned cellulose include those made from bagasse, which is the residue after squeezing sugarcane.
  • the raw material for cellulose is not particularly limited as long as it contains cellulose, and may be other plant-derived raw materials, animal-derived raw materials, microbial-derived raw materials, or recycled raw materials.
  • Other plant-based cellulose materials include unprocessed natural plant-based materials such as wood, cotton, hemp, and other herbs, and pre-processed plant-based materials such as pulp, wood flour, and paper products. Examples include processed raw materials.
  • examples of animal-derived raw materials include cellulose raw materials derived from ascidians.
  • Examples of recycled raw materials include raw materials derived from plants, animals, microorganisms, etc., which are regenerated by known methods such as the viscose method.
  • biodegradable polymers include polyphosphazene, polyacrylic acid, polymethacrylic acid, polylactic acid (PLA), polyglycolic acid (PGA), poly-(lactide-coglycolide acid) (PLGA), polyorthoester ( POE), polycaprolactone (PCL), polyhydroxylate (PHB), polylysine, degradable polyurethane, or a combination of multiple polymers selected from these polymer groups.
  • examples of the biodegradable polymer include a copolymer of one polymer selected from these polymer groups, or a copolymer of a combination of multiple polymers selected from these polymer groups.
  • Examples of sulfoxide-based organic solvents include dimethyl sulfoxide and hexamethylene sulfoxide.
  • Examples of organic solvents include amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, 1-methyl-2-pyrrolidone, and 1-vinyl-2-pyrrolidone, acetonitrile, propionitrile, and benzonitrile. or cyclic ether solvents such as 1,3-dioxolane, tetrahydrofuran, tetrahydropyran, 1,3-dioxane, 1,4-dioxane, and 1,3,5-trioxane, or aromatic solvents such as pyridine.
  • a group amine solvent may also be used.
  • nitrogen-containing organic solvents examples include N,N-dimethylacetamide, N,N-dimethylformamide, and 1-methyl-2-pyrrolidone.
  • the ionic liquid one containing an imidazolium cation or an N-butylammonium cation can be employed.
  • the ionic liquid containing the imidazolium cation an ionic liquid containing the 1-butyl-3-methylimidazolium cation can be adopted, and as the ionic liquid containing the 1-butyl-3-methylimidazolium cation, for example, 1-Butyl-3-methylimidazolium chloride (BMIMCl) is mentioned.
  • BMIMCl 1-Butyl-3-methylimidazolium chloride
  • an ionic liquid containing tetrabutylammonium cation can be employed, and as the ionic liquid containing tetrabutylammonium cation, tetrabutylammonium acetate (TBAA) can be mentioned.
  • TBAA tetrabutylammonium acetate
  • ionic liquids those containing other imidazolium cations, or pyridinium cations, pyridazinium cations, pyrimidinium cations, pyrazinium cations, pyrazonium cations, oxazolium cations, 1,2, It may contain nitrogen-containing aromatic cations such as 3-triazolium cations, 1,2,4-triazolium cations, thiazolium cations, piperidinium cations, and pyrrolidinium cations. Alternatively, the ionic liquid may contain other tetrabutylammonium cations.
  • the cellulose-containing composition according to the present embodiment is in the form of a gel, and the weight ratio of the ionic liquid to the cellulose is 8 or more and 10 or less, and the weight ratio of the ionic liquid to the organic solvent is 0.4 or more and 0.4 or more. 5 or less.
  • the biodegradable polymer is cellulose
  • impurities are removed by immersing the cellulose raw material in hot water at a temperature of 50°C or higher and 100°C or lower to create a polymer base raw material that has cellulose as its main component.
  • impurities include hemicellulose and lignin.
  • the temperature of the hot water is particularly preferably 80°C or higher and 100°C or lower.
  • a polymer purification step is performed to purify cellulose from the produced raw material whose main component is cellulose. Note that if the biodegradable polymer is a polymer other than cellulose, these steps can be omitted as appropriate.
  • a polymer solution preparation step is performed in which a polymer solution is prepared by mixing the polymer, the aforementioned organic solvent, and ionic liquid at 140° C. and stirring the mixture.
  • the amount of the ionic liquid is such that the weight ratio to the polymer is 8 or more and 10 or less, and the weight ratio to the organic solvent is 0.4 or more and 0.5 or less.
  • calcium chloride may be further added.
  • the amount of calcium chloride added is preferably such that the weight ratio to the polymer is 5% or more and 20% or less.
  • a crosslinking treatment step is performed in which a portion of the polymer contained in the polymer solution is crosslinked by adding a liquid containing water to the polymer solution.
  • Liquids containing water include water, alcohol, and the like.
  • the water-containing liquid is added so that the proportion of water in the polymer solution to which the water-containing liquid is added is 1% by weight or more and 30% by weight or less.
  • the proportion of water in this polymer solution is particularly preferably 2% by weight or more and 6% by weight or less.
  • the polymer-containing composition prepared in this way has a three-dimensional network structure formed by hydrogen bonding between polymers, and is a gel-like composition that contains an ionic liquid and is insoluble in organic solvents. . Note that in an environment at a temperature equal to or higher than the melting point of the ionic liquid included in the polymer-containing composition, the gel-like polymer-containing composition becomes liquid.
  • the polymer fiber manufacturing apparatus 1 includes a head 11 that discharges a polymer-containing composition, a coagulation tank 12, a stretching tank 13, a heater 14 that heats the stretching tank 13, and an ionic liquid removal tank 15.
  • the polymer fiber manufacturing apparatus 1 also includes a conveying device 21 that collects thread-like polymer fiber precursors from the coagulation tank 12 and transports the collected polymer fiber precursors to a drawing tank 13, and a transport device 21 that collects the polymer fiber precursors from the drawing tank 13.
  • the present invention includes a transport device 22 that transports the polymer fibers to the ionic liquid removal tank 15, and a winder 23 that winds up and collects the polymer fibers from the ionic liquid removal tank 15.
  • the head 11 includes a cylinder 111 having a cylindrical shape, both ends of which are closed in the axial direction, and an opening 111a formed through the bottom wall and an opening 111b formed through the top wall. and a piston 112 arranged therein.
  • the space between the bottom wall and the piston 112 in the cylinder 111 is filled with the aforementioned polymer-containing composition G1.
  • the head 11 is also connected to the cylinder 111 via a nozzle 115 attached to the bottom wall of the cylinder 111, a heater 113 that heats the cylinder 111, and a pipe TU that communicates with the inside of the cylinder 111 through an opening 111b. and a gas supply source 114 that supplies gas into the interior of the air conditioner 111 .
  • the gas supply source 114 supplies nitrogen gas into the cylinder 111, for example.
  • the gas supplied into the cylinder 111 by the gas supply source 114 may be other inert gas.
  • the heater 113 heats the cylinder 111 with the aforementioned polymer-containing composition G1 filled between the bottom wall and the piston 112 in the cylinder 111
  • the gel-like polymer-containing composition G1 is heated. It dissolves into a viscous liquid.
  • the temperature of the liquid polymer-containing composition G1 inside the cylinder 111 is set to 80°C or more and 150°C or less, preferably 140°C or more and 150°C or less.
  • the gas supply source 114 is connected to the top wall and the piston 112 in the cylinder 111. Supply gas to the area between the Then, the piston 112 is pushed out toward the bottom wall of the cylinder 111 by the pressure of the supplied gas, and the viscous liquid polymer-containing composition G1 filled between the bottom wall and the piston 112 in the cylinder 111 is , is discharged from the nozzle 115 to the coagulation tank 12.
  • the coagulation tank 12 is filled with a coagulation liquid ME that coagulates the polymer-containing composition G1 by removing the organic solvent from the polymer-containing composition G1.
  • a coagulation liquid ME that coagulates the polymer-containing composition G1 by removing the organic solvent from the polymer-containing composition G1.
  • the coagulating liquid ME to be filled in the coagulating tank 12 for example, alcohol such as methanol or ethanol, a ketone such as acetone, a mixed liquid of alcohol and ketone, or water can be used.
  • rollers 31 are disposed within the coagulation tank 12 to guide the polymer fiber precursor M1 produced from the polymer-containing composition G1.
  • the stretching tank 13 is also filled with the coagulation liquid ME.
  • alcohol such as methanol or ethanol can be used, for example.
  • rollers 32 and 33 are provided in the drawing tank 13 for guiding the polymer fiber precursor M1 transported from the coagulation tank 12 by the transport device 21.
  • the ionic liquid removal tank 15 is filled with highly pure water W. Note that the liquid filled in the ionic liquid removal tank 15 is not limited to water W, and may be a ketone such as acetone, or an alcohol such as methanol or ethanol. Further, in the ionic liquid removal tank 15, rollers 34 are provided for guiding the polymer fiber precursor M1 transported from the stretching tank 13 by the transport device 22.
  • a heating step is performed in the head 11 to heat the aforementioned gel-like polymer-containing composition G1 to make it into a viscous liquid state.
  • the viscous liquid polymer-containing composition G1 is discharged into the coagulation tank 12 filled with the coagulation liquid ME, and the polymer-containing composition G1 is coagulated.
  • a polymer fiber precursor production step is performed in which the filamentous polymer fiber precursor M1 flowing out of the tank 12 is recovered by the conveying device 21.
  • a stretching step is performed in which the coagulating liquid ME and the polymer fiber precursor M1 are stretched while being heated by heating the stretching tank 13 with the heater 14.
  • alcohol, ketone, water, etc. are employed as the coagulating liquid ME.
  • the polymer fiber precursor M1 can be stretched so that the stretching ratio is 1.5 times or more and 4 times or less.
  • an ionic liquid removal step is performed in which the ionic liquid contained in the polymer fiber precursor M1 is removed by immersing the polymer fiber precursor M1 in water, alcohol, ketone, etc. filled in the ionic liquid removal tank 15.
  • the polymer-containing composition G1 is in the form of a gel, and by heating this polymer-containing composition G1, it is turned into a viscous liquid and used in the above-mentioned polymer fiber manufacturing apparatus 1. It can be discharged from the nozzle 115 of the head 11 to the coagulation tank 12 . As a result, the time required to recover the polymer-containing composition G1 discharged into the coagulation tank 12 as the polymer fiber precursor M1 can be shortened, so that the polymer fiber can be spun at a correspondingly high speed.
  • the polymer fiber manufacturing apparatus 1 including the coagulation tank 12 and the drawing tank 13 is used.
  • the polymer fiber precursor can be stretched so that the stretching ratio is 1.5 times or more and 4 times or less.
  • the method for producing polymer fibers according to the present invention will be explained based on Examples.
  • the polymer-containing compositions serving as the basis for the polymer fibers of Comparative Examples 1 to 3 and Examples 1 to 3 all used Thai sugarcane bagasse as the raw material for cellulose, and dimethyl sulfoxide (Nacalai Tesque Co., Ltd.) as the organic solvent. (manufactured by) was adopted. Then, the cellulose contained in the bagasse was extracted by removing impurities contained in the bagasse by immersing the shredded bagasse in hot water. In the production of the polymer-containing composition according to Example 1, first, 2 g of cellulose was immersed in 33 g of 0.42 mol dimethyl sulfoxide and left for 30 minutes.
  • a cellulose solution was prepared by adding and stirring BMIMCl to a mixed solution of cellulose and dimethyl sulfoxide in the same manner as in Example 1, and then a cellulose solution was prepared. After adding 2 g of polylactic acid to the cellulose solution, the mixture was stirred until the polylactic acid was completely dissolved. Here, the weight ratio of polylactic acid and dimethyl sulfoxide in the solution was 1:18. Subsequently, water is added to the cellulose solution containing polylactic acid to perform a crosslinking treatment to gel the cellulose solution, and then the polymer-containing composition is dried in an oven at a temperature of 50°C. A polymer-containing composition according to Example 2 was prepared by removing water from the sample.
  • BMIMCI and dimethyl sulfoxide were added at a weight ratio of 7:3 and stirred at 140°C for 30 minutes.
  • cellulose was added to a mixed solvent of BMIMCl and dimethyl sulfoxide, and stirred while maintaining the temperature at 140° C. until the cellulose was completely dissolved, thereby preparing a cellulose solution having a cellulose concentration of 6% by weight.
  • the cellulose solution is cross-linked by adding water to gel it, and then dried in an oven at a temperature of 50°C to remove water in the polymer-containing composition. In this way, a polymer-containing composition according to Example 3 was prepared.
  • the states of the polymer-containing compositions, types of ionic liquids, and spinning methods of Comparative Examples 1 to 4 and Examples 1 to 3 are as shown in Table 1 below.
  • the concentration of cellulose was 4% by weight.
  • the cellulose concentration was 6% by weight.
  • the speed at which the polymer fiber precursor flowing out from the drawing tank 13 described in the embodiment is recovered was set to 1.98 m/min.
  • polymer-containing compositions were produced by the same manufacturing method as Comparative Example 2, and the speed at which the polymer fiber precursor flowing out from the coagulation tank was recovered was adjusted. , 0.94 m/min, 1.98 m/min, and 2.92 m/min.
  • the time for immersing the polymer fiber precursor in the ionic liquid removal tank 15 was set to 30 min, and the water temperature was set to 25°C.
  • the polymer fiber manufacturing method according to Comparative Example 6 uses water as the coagulating liquid in the wet spinning method
  • the polymer fiber manufacturing method according to Comparative Example 7 uses 50% by weight each of acetone and methanol as the coagulating liquid in the wet spinning method.
  • a mixed solution was used.
  • the temperature of the coagulation liquid in Comparative Examples 6 and 7 was set at 25°C, and the speed at which the polymer fiber precursor flowing out from the coagulation tank in the wet spinning method was collected was set at 1.98 m/min. .
  • the speed at which the polymer fiber precursor flowing out from the drawing tank 13 was collected was set to 10 m/min. Further, the temperature of the coagulating liquid filled in the stretching tank 13 was set to 100°C. The ionic liquid removal tank 15 was filled with water at 90°C.
  • the polymer fiber according to Example 1 had a higher tensile strength than the polymer fibers according to Comparative Examples 1 and 2, especially in terms of tensile strength. Furthermore, it was found that the elongation rate of the polymer fiber according to Example 2 was more than twice as high as that of the polymer fibers according to Comparative Examples 1 and 2 and Example 1. This shows that the elongation rate of the polymer fibers is significantly improved by adding polylactic acid.
  • FIG. 5A is a SEM photograph of the surface of the polymer fiber according to Example 1
  • FIG. 5B is a SEM photograph of the cross section of the polymer fiber according to Example 1. From the photographs shown in FIGS. 2A to 5B, it can be seen that the polymer fibers according to Comparative Examples 3 to 5 are all porous fibers having a cavity inside, whereas the polymer fiber according to Example 1 has a cavity inside. It can be seen that the fibers are dense with almost no cavities.
  • Example 6 a polymer-containing composition was produced by the same production method as in Example 1, and the coagulation tank 12 and drawing tank 13 were filled with water in the polymer fiber production method described in the embodiment.
  • the results of comparing the stretchability of the polymer fiber and the polymer fiber according to Example 1 are shown below.
  • the coagulation tank 12 and the stretching tank 13 were filled with methanol.
  • the speed at which the polymer fiber precursor flowing out from the drawing tank 13 described in the embodiment is recovered was set to 1.98 m/min.
  • 6(A) shows a diffraction pattern obtained by wide-angle X-ray diffraction measurement of the polymer fiber according to Comparative Example 6, and FIG.
  • FIG. 6(B) shows a diffraction pattern obtained by wide-angle X-ray diffraction measurement of the polymer fiber according to Example 1.
  • the obtained diffraction pattern is shown. From the results shown in FIG. 6, in the polymer fiber according to Comparative Example 6, a pattern reflecting the collapse of crystallinity caused by being stretched was measured, whereas in Example 1, the crystallinity was maintained. A pattern was measured that reflected the From this, by filling the coagulation tank 12 and drawing tank 13 with alcohol as in the polymer fiber manufacturing method according to Example 1, the ionic liquid can remain in the polymer fiber precursor, and the polymer It is believed that the drawability of the fiber precursor can be increased.
  • Comparative Example 7 in which a polymer-containing composition was produced using the same production method as in Example 1, and immersion in water in the ionic liquid removal tank 15 was omitted in the polymer fiber production method described in the embodiment.
  • the results of comparing the heat resistance of the polymer fiber according to Example 1 and the cellulose fiber according to Example 1 are shown below.
  • the heat resistance was evaluated by measuring the dynamic viscoelastic coefficient while changing the temperature using a dynamic viscoelasticity device Rheogel-E4000 (manufactured by UBM).
  • the temperature range is -25°C to 300°C
  • the measurement mode is tensile measurement mode
  • the distance between the chucks when chucking the polymer fiber is 15 mm
  • the temperature range is set to 15 mm when changing the temperature.
  • the temperature rate was set at 3°C/min
  • the measurement temperature was set at 1°C/min
  • the measurement frequency was set at 16Hz.
  • the measurements were performed under a nitride atmosphere.
  • FIG. 7 shows the results of comparing the loss modulus and loss coefficient between the polymer fiber according to Example 1 and the polymer fiber according to Comparative Example 7. Note that in FIG. 7, circles surrounded by broken lines indicate the results of Example 1.
  • FIG. 10A shows an SEM photograph of the surface of the polymer fiber when it was coagulated with the above-mentioned coagulating liquid and then washed with water for 30 minutes, and an SEM photograph of the cross section is shown in FIG. Shown at 10B.
  • FIG. 11B an SEM photograph of the surface of the polymer fiber is shown in FIG. 11B. In both cases, it can be seen that the polymer fibers are porous fibers with cavities inside, and grooves are formed on the fiber surface along the fiber direction.
  • the polymer fiber according to Example 3 was found to have higher tensile strength and elongation than the polymer fiber according to Comparative Example 9, especially in terms of tensile strength and elongation. Furthermore, it was found that the polymer fiber according to Example 3 had higher tensile strength and tensile resistance than the polymer fibers according to Examples 1 and 2.
  • the present invention is suitable for manufacturing yarns that utilize plant fibers such as bagasse.

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Abstract

Une composition contenant un polymère (G1) selon la présente invention contient : un polymère biodégradable qui est dans un état de gel ; un solvant organique à base de sulfoxyde ou un solvant organique contenant de l'azote ; et un liquide ionique. Le rapport en poids du liquide ionique au polymère est de 8 à 10 ; et le rapport en poids du liquide ionique au solvant organique est de 0,4 à 0,5.
PCT/JP2023/008752 2022-03-08 2023-03-08 Composition contenant un polymère, procédé de production d'une composition contenant un polymère, et procédé de production de fibres polymères WO2023171699A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101328626A (zh) * 2007-06-21 2008-12-24 中国科学院化学研究所 一种连续制备再生纤维素纤维的方法
JP2012021048A (ja) * 2010-07-12 2012-02-02 Bridgestone Corp 精製セルロース繊維の製造方法
JP2016176158A (ja) * 2015-03-20 2016-10-06 国立大学法人信州大学 セルロース多孔質糸状成形体の製造方法

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CN101328626A (zh) * 2007-06-21 2008-12-24 中国科学院化学研究所 一种连续制备再生纤维素纤维的方法
JP2012021048A (ja) * 2010-07-12 2012-02-02 Bridgestone Corp 精製セルロース繊維の製造方法
JP2016176158A (ja) * 2015-03-20 2016-10-06 国立大学法人信州大学 セルロース多孔質糸状成形体の製造方法

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