WO2024171745A1 - マルチフィラメントの製造方法 - Google Patents

マルチフィラメントの製造方法 Download PDF

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Publication number
WO2024171745A1
WO2024171745A1 PCT/JP2024/002110 JP2024002110W WO2024171745A1 WO 2024171745 A1 WO2024171745 A1 WO 2024171745A1 JP 2024002110 W JP2024002110 W JP 2024002110W WO 2024171745 A1 WO2024171745 A1 WO 2024171745A1
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WO
WIPO (PCT)
Prior art keywords
multifilament
poly
outer edge
hydroxyalkanoate
peripheral region
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2024/002110
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English (en)
French (fr)
Japanese (ja)
Inventor
貴志 荻野
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kaneka Corp
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Kaneka Corp
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Filing date
Publication date
Application filed by Kaneka Corp filed Critical Kaneka Corp
Priority to EP24756596.3A priority Critical patent/EP4667629A1/en
Priority to JP2025500999A priority patent/JPWO2024171745A1/ja
Publication of WO2024171745A1 publication Critical patent/WO2024171745A1/ja
Priority to US19/291,157 priority patent/US20250361652A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D4/00—Spinnerette packs; Cleaning thereof
    • D01D4/02—Spinnerettes
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D01D5/088—Cooling filaments, threads or the like, leaving the spinnerettes
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D01D5/088—Cooling filaments, threads or the like, leaving the spinnerettes
    • D01D5/092—Cooling filaments, threads or the like, leaving the spinnerettes in shafts or chimneys
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/24—Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
    • 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
    • D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
    • D01D5/30—Conjugate filaments; Spinnerette packs therefor
    • D01D5/36—Matrix structure; Spinnerette packs therefor
    • 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
    • D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
    • 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
    • D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
    • D01F6/625—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters derived from hydroxy-carboxylic acids, e.g. lactones
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/04—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyesters, e.g. polyethylene terephthalate [PET]
    • D10B2331/041—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyesters, e.g. polyethylene terephthalate [PET] derived from hydroxy-carboxylic acids, e.g. lactones

Definitions

  • the present invention relates to a method for manufacturing multifilaments.
  • the carbon dioxide released when these biodegradable plastics made from plant-derived raw materials are burned is the same carbon dioxide that was originally in the air, so there is no increase in the amount of carbon dioxide in the atmosphere. This is called carbon neutral, and is considered important under the Kyoto Protocol, which set targets for reducing carbon dioxide emissions, and active use of these plastics is desired.
  • aliphatic polyester resins and in particular polyhydroxyalkanoate resins, have been attracting attention as biodegradable plastics that are produced by microorganisms using plant-derived raw materials as a carbon source.
  • Patent Document 1 discloses a method for producing a multifilament containing a poly(3-hydroxybutyrate) resin.
  • the manufacturing method described in Patent Document 1 includes a step of heating a resin composition containing a poly(3-hydroxybutyrate)-based resin to a temperature equal to or higher than the melting point and equal to or lower than the thermal decomposition temperature of the resin composition and discharging the resin composition from a spinning nozzle, a step of applying an air flow having a temperature equal to or higher than the glass transition temperature and equal to or lower than the crystallization temperature of the resin composition to the resin composition discharged from the spinning nozzle having 80 holes, and a step of stretching the resin composition to which the air flow has been applied with a roll to obtain a multifilament.
  • Patent Document 1 describes that if the speed of the airflow is less than 0.1 m/s, the cooling effect obtained will be too small.
  • the present invention relates to a method for producing a multifilament having 50 or more single yarns by a melt spinning method, A step (A) of discharging a composition containing a poly(3-hydroxyalkanoate)-based resin from a spinning nozzle to obtain 50 or more molten yarns; and (B) cooling the molten yarn by blowing gas onto the molten yarn,
  • the spinning nozzle has a nozzle surface having 50 or more discharge holes, The nozzle surface is divided into a central region and a peripheral region surrounding the central region, an outer edge of the central region and an outer edge of the peripheral region have similar shapes that share an area center of gravity; a homothetic ratio between an outer edge of the central region and an outer edge of the peripheral region is 1:2; the number of ejection holes present in the peripheral region exceeds 75% of the number of ejection holes present in the nozzle surface, the temperature of the gas is (Tc-45) to (Tc-20) ° C.
  • the present invention relates to a method for producing a multifilament, wherein the average fineness of the single yarn is 3.0 dtex or more and 15.0 dtex or less.
  • FIG. 1 is a schematic diagram of an apparatus used in a method for producing a multifilament according to an embodiment of the present invention.
  • Schematic diagram of the nozzle surface side of the spinning nozzle of the present embodiment Schematic diagram of the nozzle surface side of the spinning nozzle of the present embodiment.
  • Schematic diagram of the nozzle surface side of the spinning nozzle of the present embodiment Schematic diagram of the nozzle surface side of the spinning nozzle of the present embodiment.
  • the method for producing a multifilament according to the present embodiment is a method for producing a multifilament having 50 or more single yarns by a melt spinning method.
  • the method for producing a multifilament according to this embodiment includes a step (A) of discharging a composition containing a poly(3-hydroxyalkanoate)-based resin (hereinafter also referred to as a "raw material composition") from a spinning nozzle to obtain 50 or more molten raw yarns, and a step (B) of cooling the molten raw yarns by blowing gas onto the raw yarns.
  • the spinning nozzle has a nozzle surface having 50 or more discharge holes.
  • the nozzle face is divided into a central region and a peripheral region surrounding the central region.
  • the outer edge of the central region and the outer edge of the peripheral region are similar in shape and share an area center of gravity.
  • the homothetic ratio between the outer edge of the central region and the outer edge of the peripheral region is 1:2.
  • the number of ejection holes present in the peripheral region exceeds 75% of the number of ejection holes present in the nozzle surface.
  • the temperature of the gas is (Tc-45) to (Tc-20)° C. (Tc: crystallization temperature of the composition containing the poly(3-hydroxyalkanoate) resin).
  • the gas has a wind speed of 0.01 m/s or more and less than 0.10 m/s.
  • the average fineness of the single yarn is 3.0 dtex or more and 15.0 dtex or less.
  • the method for producing the multifilament according to this embodiment further includes a step (C) of obtaining the multifilament by taking up the raw yarn cooled in the step (B) with a take-up roll.
  • Patent Document 1 International Publication No. 2021/206154 describes that "if the speed of the airflow applied to the resin composition discharged from the spinning nozzle is less than 0.1 m/s, the cooling effect obtained is too small, so that the airflow speed is preferably 0.1 m/s or more. " In contrast, in this embodiment, the wind speed of the gas in the step (B) is set to 0.01 m/s or more and less than 0.10 m/s.
  • the similarity ratio is 1:2 and the ejection holes are evenly distributed on the nozzle surface
  • the ratio of the number of ejection holes present in the peripheral region to the number of ejection holes present on the nozzle surface is 75%.
  • the abundance ratio exceeds 75%, so that the ejection holes are unevenly distributed more in the peripheral region than in the central region.
  • the productivity of multifilament containing a poly(3-hydroxybutyrate)-based resin and having a small average single yarn fineness (3.0 dtex or more and 15.0 dtex or less) can be improved.
  • the reasons for this are thought to be as follows: That is, since the discharge holes are unevenly distributed in the peripheral region, the inner yarns in the bundle of yarns, which are harder to cool than the outer yarns, can be cooled sufficiently in the step (B). As a result, even if the gas speed is less than 0.10 m/s, the time during which the yarns are in a molten state can be shortened, making the yarns less likely to break.
  • the raw yarn becomes in a state of excellent flexibility (a state in which the shape is easily deformed), and the raw yarn is less likely to break when it is taken up by the take-up roll. Furthermore, since the raw yarn is less likely to break, the spinning speed (the speed of the take-up roll) can be increased, thereby improving the productivity of the multifilament.
  • the raw material composition contains a polymer component and an additive.
  • the polymer component includes a poly(3-hydroxyalkanoate)-based resin.
  • the polymer component may contain other polymers in addition to the poly(3-hydroxyalkanoate) resin.
  • the poly(3-hydroxyalkanoate) resin is a polyester having 3-hydroxyalkanoic acid as a monomer. That is, the poly(3-hydroxyalkanoate) resin is a resin containing 3-hydroxyalkanoic acid as a constituent unit.
  • the poly(3-hydroxyalkanoate) resin is a biodegradable polymer.
  • biodegradability refers to the property of being decomposed into low molecular weight compounds by microorganisms in nature.
  • the presence or absence of biodegradability can be determined based on tests suitable for each environment, such as ISO 14855 (compost) and ISO 14851 (activated sludge) under aerobic conditions, and ISO 14853 (aqueous phase) and ISO 15985 (solid phase) under anaerobic conditions.
  • the decomposition ability of microorganisms in seawater can be evaluated by measuring the biochemical oxygen demand.
  • the poly(3-hydroxyalkanoate) resin includes a homopolymer and/or a copolymer.
  • the poly(3-hydroxyalkanoate) resin preferably contains a structural unit represented by the following formula (1).
  • [-CHR-CH 2 -CO-O-] (1) (In the formula (1), R represents an alkyl group represented by C p H 2p+1 , and p represents an integer of 1 to 15.)
  • the poly(3-hydroxyalkanoate) resin is preferably a resin containing 3-hydroxybutyrate as a constituent unit (poly(3-hydroxybutyrate) resin).
  • the poly(3-hydroxybutyrate) resin includes a homopolymer and/or a copolymer.
  • poly(3-hydroxyalkanoate) resins containing 3-hydroxybutyrate as a constituent unit examples include P3HB, P3HB3HH, P3HB3HV, P3HB4HB, poly(3-hydroxybutyrate-co-3-hydroxyoctanoate), poly(3-hydroxybutyrate-co-3-hydroxyoctadecanoate), and the like.
  • P3HB means poly(3-hydroxybutyrate) which is a homopolymer.
  • P3HB3HH means poly(3-hydroxybutyrate-co-3-hydroxyhexanoate).
  • P3HB3HV means poly(3-hydroxybutyrate-co-3-hydroxyvalerate).
  • P3HB4HB means poly(3-hydroxybutyrate-co-4-hydroxybutyrate).
  • P3HB has the function of promoting the crystallization of P3HB itself and poly(3-hydroxyalkanoate)-based resins other than P3HB, it is preferable that the poly(3-hydroxyalkanoate)-based resin contains P3HB.
  • poly(3-hydroxyalkanoate) resin from the viewpoint of achieving both excellent biodegradability and moldability, P3HB, P3HB3HH, P3HB3HV, P3HB4HB, and the like are preferred, but there are no particular limitations.
  • P3HB3HH is preferable from the viewpoint of increasing the strength of the multifilament according to this embodiment and improving the moldability.
  • the poly(3-hydroxyalkanoate) resin contains 3-hydroxybutyrate as a constituent unit in an amount of preferably 80 mol % or more, more preferably 85.0 mol % to 99.5 mol %, and even more preferably 85.0 mol % to 97.0 mol %.
  • the poly(3-hydroxyalkanoate) resin contains 80 mol % or more of 3-hydroxybutyrate as a constituent unit, the rigidity of the multifilament is increased.
  • the poly(3-hydroxyalkanoate) resin contains 99.5 mol % or less of 3-hydroxybutyrate as a constituent unit, the multifilament has excellent flexibility.
  • the content of 3-hydroxybutyrate units in poly(3-hydroxyalkanoate) resins can be determined by the method described in the examples below.
  • the polymer component may contain only one type of the poly(3-hydroxyalkanoate) resin, or may contain two or more types of the poly(3-hydroxyalkanoate) resin.
  • the poly(3-hydroxyalkanoate) resin contains a copolymer (such as P3HB3HH), it may contain two or more types of copolymers having different average composition ratios of structural units.
  • the weight average molecular weight of the poly(3-hydroxyalkanoate) resin in the raw material composition is preferably 3.0 ⁇ 10 5 to 7.0 ⁇ 10 5 , more preferably 3.5 ⁇ 10 5 to 7.0 ⁇ 10 5 , even more preferably 4.0 ⁇ 10 5 to 7.0 ⁇ 10 5 , and most preferably 4.5 ⁇ 10 5 to 6.5 ⁇ 10 5 .
  • the weight average molecular weight of the poly(3-hydroxyalkanoate) resin in the raw material composition is 3.0 ⁇ 10 or more, the weight average molecular weight of the poly(3-hydroxyalkanoate) resin in the single yarn can be easily increased, and as a result, the strength of the multifilament can be easily increased.
  • the weight average molecular weight of the poly(3-hydroxyalkanoate) resin in the raw material composition is 7.0 ⁇ 10 5 or less, it becomes easy to mold the multifilament.
  • the weight average molecular weight of the poly(3-hydroxyalkanoate) resin in the raw material composition means the weight average molecular weight of the poly(3-hydroxyalkanoate) resin in the raw material composition before it is melted by heating.
  • the weight average molecular weight is measured from the polystyrene equivalent molecular weight distribution by gel permeation chromatography (GPC) using chloroform as an eluent.
  • GPC gel permeation chromatography
  • the column for the GPC a column suitable for measuring the molecular weight may be used.
  • Mw weight average molecular weight
  • the weight average molecular weight (Mw) can be determined by setting the column temperature at 40° C., injecting 10 ⁇ l of a solution of 3 mg of the target substance in 2 ml of chloroform, and setting the flow rate of the chloroform eluent (mobile phase) to 1.0 ml/min.
  • Shimadzu 20A manufactured by Shimadzu Corporation
  • Shodex K-806M manufactured by Showa Denko
  • the other polymers are preferably biodegradable.
  • biodegradable polymers examples include polycaprolactone, polylactic acid, polybutylene succinate, polybutylene succinate adipate, polybutylene adipate terephthalate, polyethylene succinate, polyvinyl alcohol, polyglycolic acid, unmodified starch, modified starch, cellulose acetate, chitosan, and poly(4-hydroxyalkanoate)-based resins.
  • the polycaprolactone is a polymer obtained by ring-opening polymerization of ⁇ -caprolactone.
  • the polymer component may contain one type of other polymer, or may contain two or more types of other polymers.
  • the polymer component preferably contains 50% by weight or more, more preferably 80% by weight or more, and even more preferably 90% by weight or more of poly(3-hydroxyalkanoate) resin.
  • the raw material composition contains a biodegradable polymer, so even if the multifilament is discarded in the environment, it is easily decomposed in the environment, thereby reducing the burden on the environment.
  • the additives include, for example, crystal nucleating agents, lubricants, plasticizers, spinning oils, stabilizers (antioxidants, UV absorbers, etc.), colorants (dyes, pigments, etc.), inorganic fillers, organic fillers, antistatic agents, etc.
  • the raw material composition preferably contains a crystal nucleating agent.
  • the crystal nucleating agent is a compound that has the effect of promoting the crystallization of the poly(3-hydroxyalkanoate) resin, and has a melting point higher than that of the poly(3-hydroxyalkanoate) resin.
  • crystal nucleating agent examples include inorganic substances (boron nitride, titanium oxide, talc, layered silicate, calcium carbonate, sodium chloride, metal phosphate, etc.); sugar alcohol compounds derived from natural products (pentaerythritol, erythritol, galactitol, mannitol, arabitol, etc.); polyvinyl alcohol; chitin; chitosan; polyethylene oxide; aliphatic carboxylates; aliphatic alcohols; aliphatic carboxylate esters; dicarboxylic acid derivatives (dimethyl adipate, dibutyl adipate, diisodecyl adipate, dibutyl selenite, etc.); Examples of such compounds include cyclic compounds having, in the molecule, C ⁇ O and a functional group selected from NH, S, and O (such as indigo, quinacridone, and quinacridone magenta); sorbitol derivatives,
  • sugar alcohol compounds from the viewpoint of the effect of improving the crystallization rate of the poly(3-hydroxyalkanoate) resin and from the viewpoint of compatibility and affinity with the poly(3-hydroxyalkanoate) resin.
  • sugar alcohol compounds polyvinyl alcohol, chitin, and chitosan are preferred.
  • pentaerythritol is preferred.
  • the crystal nucleating agent preferably has a crystal structure at room temperature (25° C.).
  • the crystal nucleating agent has a crystalline structure at room temperature (25° C.), which has the advantage of further promoting the crystallization of the poly(3-hydroxyalkanoate) resin.
  • the crystal nucleating agent having a crystal structure at room temperature (25° C.) is preferably in a powder form at room temperature (25° C.).
  • the average particle size of the crystal nucleating agent in powder form at room temperature (25° C.) is preferably 10 ⁇ m or less.
  • the content of the crystal nucleating agent in the raw material composition is preferably 0.05 parts by weight or more, more preferably 0.1 parts by weight or more, and even more preferably 0.5 parts by weight or more, relative to 100 parts by weight of the poly(3-hydroxyalkanoate)-based resin.
  • the content of the crystal nucleating agent in the raw material composition be 0.05 parts by weight or more relative to 100 parts by weight of the poly(3-hydroxyalkanoate)-based resin, there is an advantage in that the crystallization of the poly(3-hydroxyalkanoate)-based resin can be further promoted.
  • the content of the crystal nucleating agent in the raw material composition is preferably 10 parts by weight or less, more preferably 8 parts by weight or less, and even more preferably 5 parts by weight or less, relative to 100 parts by weight of the poly(3-hydroxyalkanoate)-based resin.
  • the content of the crystal nucleating agent in the raw material composition be 10 parts by weight or less relative to 100 parts by weight of the poly(3-hydroxyalkanoate)-based resin, when producing a multifilament from the melt, the viscosity of the melt can be reduced, which has the advantage of facilitating the production of the multifilament.
  • P3HB is a poly(3-hydroxyalkanoate) resin and can also function as a crystal nucleating agent. Therefore, when the raw material composition contains P3HB, the amount of P3HB is included in both the amount of the poly(3-hydroxyalkanoate) resin and the amount of the crystal nucleating agent.
  • the raw material composition may contain a lubricant.
  • the lubricant may, for example, be a fatty acid amide.
  • the fatty acid amide preferably includes at least one selected from lauric acid amide, myristic acid amide, stearic acid amide, behenic acid amide, and erucic acid amide.
  • the content of the lubricant in the raw material composition is preferably 0.05 parts by weight or more, more preferably 0.1 parts by weight or more, and even more preferably 0.5 parts by weight or more, relative to 100 parts by weight of the poly(3-hydroxyalkanoate)-based resin.
  • the content of the lubricant in the raw material composition be 0.05 parts by weight or more relative to 100 parts by weight of the poly(3-hydroxyalkanoate)-based resin, there is an advantage in that the lubricity of the single yarn is excellent.
  • the content of the lubricant in the raw material composition is preferably 12 parts by weight or less, more preferably 10 parts by weight or less, further preferably 8 parts by weight or less, and most preferably 5 parts by weight or less, relative to 100 parts by weight of the poly(3-hydroxyalkanoate)-based resin.
  • the content of the lubricant in the raw material composition be 12 parts by weight or less relative to 100 parts by weight of the poly(3-hydroxyalkanoate)-based resin, there is an advantage in that the lubricant can be inhibited from bleeding out onto the surface of the multifilament.
  • Step (A) In the step (A), first, the materials are dry-blended and then melt-kneaded in an extruder to obtain pellets as a raw material composition. Then, the pellets are fed into a feeder 10 as shown in FIG. Next, the pellets fed from the feeder 10 are heated and melted in an extruder 20 to obtain a molten material that is a molten raw material composition.
  • a screw extruder can be used as the extruder 20.
  • the extruder 20 may be a single screw extruder or a twin screw extruder.
  • the molten material composition is then discharged from the spinning nozzle 40 to obtain 50 or more molten yarns A.
  • the flow rate of the molten material discharged from the spinning nozzle 40 is adjusted by the gear pump 30 .
  • the spinning nozzle 40 has a nozzle surface 41 having 50 or more discharge holes 42. In addition, if the spinning nozzle 40 has an outermost edge region 43 in which no discharge holes 42 are formed, the outermost edge region 43 is not included in the nozzle surface 41.
  • the spinning nozzle 40 may have a hole (e.g., a hole for fixing the spinning nozzle 40) formed therein in addition to the discharge hole 42.
  • the spinning nozzle 40 may have the configuration shown in FIGS.
  • the nozzle surface 41 is divided into a central region 41a and a peripheral region 41b surrounding the central region 41a.
  • the outer edge 41a1 of the central region and the outer edge 41b1 of the peripheral region are similar in shape and share a common area center of gravity.
  • the area center of gravity refers to the center of gravity of a thin plate having an outer edge of the same shape as the outer edge of the region and having a uniform weight per unit area.
  • the outer edge 41b1 of the peripheral region is a line drawn so as to connect the group of ejection holes 42 on the nozzle surface 41 on the outside.
  • a line drawn so as to surround the group of ejection holes 42 on the nozzle surface 41 is the outer edge 41b1 of the peripheral region.
  • a line that shares the area center of gravity with the outer edge 41b1 of the peripheral region is similar to the outer edge 41b1 of the peripheral region, and is half the length of the outer edge 41b1 of the peripheral region, becomes the outer edge 41a1 of the central region.
  • the ejection holes 42 are formed in the peripheral region 41b at a higher density than in the central region 41a.
  • the number of ejection holes 42 present in the peripheral region 41b exceeds 75% of the number of ejection holes 42 present in the nozzle surface 41, and is preferably 80 to 100% of the number of ejection holes 42 present in the nozzle surface 41, more preferably 85 to 100% of the number of ejection holes 42 present in the nozzle surface 41, even more preferably 90 to 100% of the number of ejection holes 42 present in the nozzle surface 41, and particularly preferably 95 to 100% of the number of ejection holes 42 present in the nozzle surface 41.
  • the inner yarns in the bundle of yarns are also more likely to be cooled sufficiently, and uneven cooling between the outer yarns and the inner yarns in the bundle of yarns can be suppressed.
  • the raw yarn is less likely to break even if the take-up roll speed is increased, and the productivity of the multifilament can be improved.
  • the variation in the fineness of the raw yarn A can be suppressed, and as a result, the variation in the fineness of the single yarns of the obtained multifilament can also be suppressed.
  • the area of the specific ejection hole in the central region 41a is compared with the area of the specific ejection hole in the peripheral region 41b, and the specific ejection hole is deemed to be located in the region with the larger area, and the number of ejection holes 42 in each region is counted.
  • the discharge holes 42 are arranged in a circumferential row on the nozzle surface 41 .
  • the nozzle surface 41 may have one row of ejection holes 42 arranged circumferentially ( FIG. 3 ).
  • the nozzle surface 41 preferably has two or more rows of ejection holes 42 arranged circumferentially, and more preferably has four or more rows of ejection holes 42 arranged circumferentially (five rows in FIG. 2 and eight rows in FIG. 4 ).
  • the number of rows is 20 or less, more specifically, 15 or less.
  • the peripheral region 41b may have a region where no ejection holes 42 exist on the central region 41a side.
  • the ejection holes 42 may be arranged approximately evenly over the entire peripheral region 41b. 2 to 4, from the viewpoint of further improving the productivity of the multifilament, it is preferable that the central region 41a does not have an outlet hole 42. However, the central region 41a may have an outlet hole 42.
  • the distances between adjacent discharge holes 42 are approximately the same as each other. From the viewpoint of facilitating relatively uniform cooling of the raw yarn, it is preferable that the discharge holes 42 are arranged approximately evenly in the region of the nozzle surface 41 where the discharge holes 42 are present.
  • the outer edge 41a1 of the central region and the outer edge 41b1 of the peripheral region are each circular, elliptical, regular polygonal, or star-shaped regular polygonal, more preferably circular, elliptical, or regular polygonal, and even more preferably circular.
  • the spinning nozzle 40 has 50 or more, preferably 50 to 10,000, more preferably 50 to 5,000, even more preferably 50 to 3,000, still more preferably 50 to 2,000, and particularly preferably 50 to 1,000 discharge holes .
  • the spinning nozzle 40 has 50 or more discharge holes 42, but in this embodiment, the number of discharge holes 42 present in the peripheral region 41b exceeds 75% of the number of discharge holes 42 present in the nozzle surface 41, making it easier for the inner yarn A in the bundle of yarns to be sufficiently cooled.
  • the spinning nozzle 40 has 10,000 or less discharge holes 42, the inner yarn A in the yarn bundle can also be cooled sufficiently.
  • each discharge hole 42 are selected according to the characteristics required of the multifilament (for example, appearance, fineness, strength, cross-sectional shape, etc.). It is preferable that the shapes of the ejection holes 42 are substantially the same. It is also preferable that the cross-sectional areas of the ejection holes 42 are substantially the same. Examples of the shape of the discharge hole 42 include a circle, an ellipse, a regular polygon, and a star-shaped regular polygon. The area (cross-sectional area) of each discharge hole 42 is preferably 1.0 ⁇ 10 ⁇ 3 to 20 mm 2 , and more preferably 5.0 ⁇ 10 ⁇ 3 to 10 mm 2 .
  • the flow rate of the composition (molten material) discharged from the spinning nozzle 40 is preferably 1.0 to 20 kg/h, more preferably 2.0 to 15 kg/h.
  • the temperature of the composition (raw material composition) immediately after being discharged from the spinning nozzle 40 is preferably 150 to 168°C, more preferably 151 to 167°C.
  • the temperature is 150° C. or higher, the composition is sufficiently melted, and the composition can be easily discharged from the discharge hole 42 .
  • Step (B) In the step (B), 50 or more molten yarns A are cooled by blowing gas onto the yarns A.
  • the gas include air, inert gases (nitrogen gas, argon gas, etc.), and water vapor.
  • gas is blown onto 50 or more molten raw yarns A in a cooling section 50.
  • the cooling section 50 has a cooling box 51.
  • gas is blown onto the raw yarn A in the cooling box 51.
  • the spraying method include the circular method and the backside method.
  • the back surface method is a method in which the gas is blown from one direction onto 50 or more strands of the raw yarn A in a cooling box 51 when viewed in the longitudinal direction of the raw yarn A (a cross-sectional view of the raw yarn A perpendicular to the longitudinal direction of the raw yarn A).
  • the circular method uses a cooling box 51 having a cylindrical side wall, and blows gas into the cylindrical box 51 in a spiral shape along the inner circumferential surface of the cylindrical side wall, thereby blowing the gas onto 50 or more of the raw yarns A.
  • the flow direction of the raw yarns A is approximately parallel to the imaginary axis of the cylindrical side wall.
  • the cooling box 51 has a cylindrical punched metal on the inside of the cylindrical side wall, and may further have a cylindrical mesh (e.g., 80 mesh) on the inside of the cylindrical punched metal.
  • the outer diameter of the cylindrical punched metal is smaller than the inner diameter of the cylindrical side wall.
  • the outer diameter of the cylindrical mesh is smaller than the inner diameter of the cylindrical punched metal.
  • 50 or more of the raw yarns A pass through the inside of a cylindrical net.
  • the blowing method is preferably the circular method, which can blow gas relatively uniformly onto 50 or more raw yarns A, thereby making it possible to cool the raw yarns A more uniformly and suppressing the variation in fineness of the raw yarns A.
  • step (B) it is preferable to discharge the gas that has come into contact with the raw yarn A to the outside of the cooling box 51 along the flow direction of the raw yarn A.
  • a straightening plate, a straightening fin, an ejector, a Venturi tube, a transvector manufactured by Kogi Co., Ltd., etc. can be used.
  • the temperature of the gas is (Tc-45) to (Tc-20) °C (Tc: crystallization temperature of the composition (raw material composition) containing the poly(3-hydroxyalkanoate) resin), and preferably (Tc-40) to (Tc-25) °C.
  • the temperature of the gas means the temperature of the gas immediately before the gas hits the raw yarn A.
  • the temperature of the gas By setting the temperature of the gas to (Tc-20)°C or lower, breakage of the raw yarn A is suppressed, and as a result, productivity of the multifilament is easily improved. This is believed to be because the temperature of the gas is (Tc-20)°C or lower, and thus the yarn A is sufficiently cooled, shortening the time during which the yarn A is in a molten state, and as a result, the yarn A is less likely to break.
  • the productivity of the multifilament can be easily improved. This is believed to be because, since the temperature of the gas is (Tc-45)°C or higher, the composition constituting the raw yarn is more easily crystallized after the raw yarn is taken up by the take-up roll, thereby suppressing fusion between the single yarns.
  • the crystallization temperature (Tc) of the raw material composition can be measured in accordance with JIS K7121-1987 "Method for measuring transition temperature of plastics.” Specifically, a differential scanning calorimeter (e.g., DSC25 differential scanning calorimeter manufactured by TA Instruments) is used, about 6.0 mg of the raw material composition as a sample is filled into a measurement container, and the temperature is increased and decreased between ⁇ 30° C. and 180° C. at a heating and cooling rate of 10° C./min under a nitrogen gas flow rate of 50 ml/min, and the peak top temperature of the exothermic peak during the second cooling is taken as the crystallization temperature. When there are two or more exothermic peaks, the peak top temperature of the exothermic peak having the largest peak area is taken as the crystallization temperature.
  • a differential scanning calorimeter e.g., DSC25 differential scanning calorimeter manufactured by TA Instruments
  • the gas has a wind speed of 0.01 m/s or more and less than 0.10 m/s, and preferably 0.01 m/s or more and 0.09 m/s or less.
  • the gas velocity means the gas velocity immediately before the gas hits the raw yarn A.
  • the raw yarn A is less likely to break when taken up by the take-up roll even if the take-up roll speed is increased, and as a result, the productivity of the multifilament is easily improved. This is believed to be because, by setting the gas velocity to less than 0.10 m/s, the raw yarn A can be prevented from being cooled to a temperature at which the composition is likely to crystallize before being taken up by the take-up roll, making it easier for the raw yarn A to be taken up by the take-up roll in a flexible state.
  • the molten yarn A can be sufficiently cooled by the gas. As a result, the molten yarn A is less likely to break, making it easier to improve the productivity of multifilament.
  • the distance between the discharge hole of the spinning nozzle 40 and the position where the gas comes into contact with the raw yarn A obtained by being discharged from the discharge hole in the step (B) is determined by the required characteristics of the multifilament, but generally the shorter the distance the better.
  • Step (C) In the step (C), the raw yarn A cooled in the step (B) is taken up by a take-up roll 62 of a take-up machine 60 to obtain the multifilament B.
  • the take-up speed at the take-up roll 62 is, for example, 150 to 2000 m/min, preferably 200 to 1000 m/min, and more preferably 250 to 750 m/min. By setting the take-up speed at the take-up roll 62 within the preferred range, it becomes easier to further increase the productivity of the multifilament.
  • a spinning oil may be applied to the surface of each of the cooled raw yarns A by the oiling roll 61 of the take-up machine 60 before the raw yarns A are taken up by the take-up roll 62.
  • the spinning oil include cationic surfactants, anionic surfactants, nonionic surfactants, refined esterified oils, mineral oils, poly(oxyethylene) alkyl ethers, silicone oils, paraffin waxes, etc. These may be used alone or in combination of two or more. From the viewpoint of further suppressing fusion between adjacent filaments, the spinning oil is preferably silicone oil.
  • the spinning oil is preferably an anionic surfactant or a nonionic surfactant.
  • a spinning oil containing silicone oil and an anionic surfactant for example, "Polymax FKY” manufactured by Marubishi Chemical Co., Ltd.
  • an anionic surfactant for example, "Polymax FKY” manufactured by Marubishi Chemical Co., Ltd.
  • the multifilament B can be wound around a winding roll 71 of a winding machine 70.
  • the multifilament B is wound around a winding roll 71.
  • the multifilament B may be stored in a storage container without being wound around the winding roll 71.
  • the multifilament B as a multifilament to be drawn may be drawn to obtain a multifilament (drawn multifilament).
  • the drawing method include a sequential drawing method (also called a "post-drawing method") and a spin-draw method (also called an "SDY method” or a "direct spinning drawing method”).
  • the sequential drawing method the multifilament for drawing wound around the winding roll 71 is drawn to obtain a drawn multifilament.
  • the spin-draw method the multifilament to be drawn taken up by the take-up roll 62 is drawn to obtain a drawn multifilament, and the drawn multifilament is wound up by the take-up roll 71.
  • the steps from the step of obtaining a plurality of molten raw yarns by discharging a molten material from a plurality of discharge holes to the step of drawing the multifilament to be drawn are carried out in one step.
  • the multifilament has 50 or more single yarns, preferably 50 to 10,000, more preferably 50 to 5,000, and even more preferably 50 to 3,000.
  • the multifilament may be used in the form of a thread.
  • the multifilament may be cut to obtain a staple having a length of 20 cm or less.
  • the staple may be used in the form of a thread.
  • a textile product (fibrous body) may be produced using the multifilament and/or staple.
  • the textile product can be in various forms (eg, in the form of a nonwoven fabric, etc.).
  • the multifilaments, staples, and fiber products can be suitably used for conventionally known applications.
  • the multifilaments, staples, and textile products can be suitably used in fields such as agriculture (e.g., horticulture), fishing, forestry, the medical industry, and the food industry. Examples of the textile products include clothing, curtains, carpets, bags, shoes, wiping materials, sanitary products, automobile parts, building materials, and filtering materials (filters).
  • a method for producing a multifilament having 50 or more single yarns by a melt spinning method comprising the steps of: A step (A) of discharging a composition containing a poly(3-hydroxyalkanoate)-based resin from a spinning nozzle to obtain 50 or more molten yarns; and (B) cooling the molten yarn by blowing gas onto the molten yarn,
  • the spinning nozzle has a nozzle surface having 50 or more discharge holes, The nozzle surface is divided into a central region and a peripheral region surrounding the central region, an outer edge of the central region and an outer edge of the peripheral region have similar shapes that share an area center of gravity; a homothetic ratio between an outer edge of the central region and an outer edge of the peripheral region is 1:2; the number of ejection holes present in the peripheral region exceeds 75% of the number of ejection holes present in the nozzle surface, the temperature of the gas is (Tc-45) to (Tc-20) ° C.
  • Tc crystallization temperature of the composition containing the poly(3-hydroxyalkanoate)-based resin
  • the gas velocity is 0.01 m/s or more and less than 0.10 m/s
  • the method for producing a multifilament, wherein the average fineness of the single yarn is 3.0 dtex or more and 15.0 dtex or less.
  • Item 4 The method for producing a multifilament according to item 3, wherein an outer edge of the central region and an outer edge of the peripheral region are each circular.
  • the present invention is not limited to the above-described embodiment.
  • the present invention is also not limited to the above-described effects.
  • the present invention can be modified in various ways without departing from the spirit of the present invention.
  • Example 1 (Step (A) First, the following materials were dry-blended in the following ratio, and the mixture was melt-kneaded at 150° C. in an extruder to obtain a raw material composition in the form of pellets.
  • Poly(3-hydroxyalkanoate) resin (P3HA) was poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (3-hydroxybutyrate unit content: 94.0 mol%, 3-hydroxyhexanoate content: 6 mol%, weight average molecular weight (Mw): 582,936)
  • P3HB3HH 100 parts by mass Erucic acid amide (EA) as lubricant: 0.5 parts by mass Behenic acid amide (BA) as lubricant: 0.5 parts by mass Pentaerythritol (PETL) as crystal nucleating agent (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., Neu-Rizer P): 1.0 part by mass
  • the weight average molecular weight of P3HA was measured by the method described above.
  • the first reaction liquid was then cooled, and 1.5 g of sodium bicarbonate was gradually added to the cooled first reaction liquid to neutralize it, and the mixture was left to stand until the evolution of carbon dioxide gas ceased, thereby obtaining a second reaction liquid. Furthermore, the second reaction solution and 4 mL of diisopropyl ether were thoroughly mixed to obtain a mixture. The mixture was then centrifuged to obtain a supernatant. The monomer unit composition of the decomposition product in the supernatant was analyzed by capillary gas chromatography under the conditions described below to determine the content of 3-hydroxybutyrate units and the content of 3-hydroxyhexanoate (3HH) units in P3HA.
  • the crystallization temperature of the composition (raw material composition) was measured using the method described above.
  • the crystallization temperature of the composition (raw material composition) was 50°C.
  • the pellets were melted at an extrusion temperature of 170.0° C. using an extruder 20 (single-screw extruder, screw diameter: 25 mm) to obtain a melt.
  • the molten material was then extruded from the nozzle surface 41 of the spinning nozzle 40 in Figure 2 (total number of ejection holes 42: 400, number of ejection holes 42 in the peripheral region 41b: 400, number of ejection holes 42 in the central region 41a: 0, shape of the ejection holes 42: circular, diameter of the ejection holes 42: 0.5 mm) to obtain 400 raw yarns A.
  • the ratio (presence ratio) of the "number of ejection holes 42 present in the peripheral region 41b" to the "number of ejection holes 42 present in the nozzle surface 41" is 100%.
  • the temperature of the composition (molten material) immediately after being discharged from the spinning nozzle 40 (also simply referred to as the "temperature of the composition") was 161°C.
  • the flow rate of the composition (melt) discharged from the spinning nozzle 40 was adjusted to 7.0 kg/h by the gear pump 30.
  • Step (B) In the cooling section 50, 400 raw yarns A in a molten state were cooled by blowing gas (air) at 20° C. at a wind speed of 0.08 m/s by a circular blowing method.
  • the value (Tc-T) obtained by subtracting the gas temperature (T) from the crystallization temperature (Tc) of the composition is shown in Table 1 below.
  • Step (C) 400 strands of raw yarn A were taken up by the take-up roll 62 to obtain a multifilament B.
  • the raw yarn A was taken up at a high take-up speed by the take-up roll 62 (650 m/min).
  • the average value of the single yarn fineness of the multifilament B was measured by the above-mentioned method.
  • the average value of the single yarn fineness was 5.0 dtex.
  • Example 2 Comparative Examples 1 to 7
  • a multifilament was produced in the same manner as in Example 1, except that the production conditions for the multifilament were as shown in Table 1 below.
  • the average fineness of the single yarns was adjusted by adjusting the flow rate of the composition (melt) discharged from the spinning nozzle 40, adjusting the total cross-sectional area of the discharge holes, and adjusting the take-up speed at the take-up roll 62.
  • the spinning nozzle shown in FIG. 3 was used, and in Example 3, the spinning nozzle shown in FIG.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
PCT/JP2024/002110 2023-02-15 2024-01-24 マルチフィラメントの製造方法 Ceased WO2024171745A1 (ja)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07310230A (ja) * 1994-05-11 1995-11-28 Unitika Ltd ポリエステル繊維の製造法
JPH10226920A (ja) * 1997-02-12 1998-08-25 Nippon Ester Co Ltd ポリエステル極細マルチフィラメントの溶融紡糸方法
WO2021206154A1 (ja) 2020-04-09 2021-10-14 株式会社カネカ 脂肪族ポリエステル繊維の製造方法、脂肪族ポリエステル繊維及びマルチフィラメント
WO2022202397A1 (ja) * 2021-03-26 2022-09-29 株式会社カネカ マルチフィラメント及びその製造方法、並びに、ステープル及びその製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07310230A (ja) * 1994-05-11 1995-11-28 Unitika Ltd ポリエステル繊維の製造法
JPH10226920A (ja) * 1997-02-12 1998-08-25 Nippon Ester Co Ltd ポリエステル極細マルチフィラメントの溶融紡糸方法
WO2021206154A1 (ja) 2020-04-09 2021-10-14 株式会社カネカ 脂肪族ポリエステル繊維の製造方法、脂肪族ポリエステル繊維及びマルチフィラメント
WO2022202397A1 (ja) * 2021-03-26 2022-09-29 株式会社カネカ マルチフィラメント及びその製造方法、並びに、ステープル及びその製造方法

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