CN115380136A - Process for producing aliphatic polyester fiber, and multifilament - Google Patents
Process for producing aliphatic polyester fiber, and multifilament Download PDFInfo
- Publication number
- CN115380136A CN115380136A CN202180026855.XA CN202180026855A CN115380136A CN 115380136 A CN115380136 A CN 115380136A CN 202180026855 A CN202180026855 A CN 202180026855A CN 115380136 A CN115380136 A CN 115380136A
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- Prior art keywords
- resin composition
- aliphatic polyester
- hydroxybutyrate
- roll
- poly
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- 239000000835 fiber Substances 0.000 title claims abstract description 97
- 229920003232 aliphatic polyester Polymers 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title abstract description 21
- 239000011342 resin composition Substances 0.000 claims abstract description 73
- 229920005989 resin Polymers 0.000 claims abstract description 48
- 239000011347 resin Substances 0.000 claims abstract description 48
- 238000009987 spinning Methods 0.000 claims abstract description 48
- 229920000070 poly-3-hydroxybutyrate Polymers 0.000 claims abstract description 37
- 239000003484 crystal nucleating agent Substances 0.000 claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 claims abstract description 25
- 238000004804 winding Methods 0.000 claims abstract description 25
- 238000002844 melting Methods 0.000 claims abstract description 14
- 230000008018 melting Effects 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 238000005979 thermal decomposition reaction Methods 0.000 claims abstract description 10
- 238000007599 discharging Methods 0.000 claims abstract description 6
- 238000002425 crystallisation Methods 0.000 claims description 13
- 230000008025 crystallization Effects 0.000 claims description 13
- 229920001020 poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) Polymers 0.000 claims description 12
- 230000009477 glass transition Effects 0.000 claims description 8
- -1 3-hydroxyhexanoate ester Chemical class 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 6
- 238000007664 blowing Methods 0.000 claims description 2
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 description 9
- 229920000903 polyhydroxyalkanoate Polymers 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 238000001816 cooling Methods 0.000 description 6
- 238000002074 melt spinning Methods 0.000 description 6
- 238000010791 quenching Methods 0.000 description 6
- 230000000171 quenching effect Effects 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 239000004014 plasticizer Substances 0.000 description 5
- WHBMMWSBFZVSSR-UHFFFAOYSA-M 3-hydroxybutyrate Chemical compound CC(O)CC([O-])=O WHBMMWSBFZVSSR-UHFFFAOYSA-M 0.000 description 4
- HPMGFDVTYHWBAG-UHFFFAOYSA-N 3-hydroxyhexanoic acid Chemical compound CCCC(O)CC(O)=O HPMGFDVTYHWBAG-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- WHBMMWSBFZVSSR-UHFFFAOYSA-N R3HBA Natural products CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 description 4
- 229920000704 biodegradable plastic Polymers 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 239000000314 lubricant Substances 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229920006026 co-polymeric resin Polymers 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000000113 differential scanning calorimetry Methods 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 229920000520 poly(3-hydroxybutyrate-co-3-hydroxyvalerate) Polymers 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920002101 Chitin Polymers 0.000 description 2
- 229920001661 Chitosan Polymers 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- ORAWFNKFUWGRJG-UHFFFAOYSA-N Docosanamide Chemical compound CCCCCCCCCCCCCCCCCCCCCC(N)=O ORAWFNKFUWGRJG-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 2
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920001013 poly(3-hydroxybutyrate-co-4-hydroxybutyrate) Polymers 0.000 description 2
- 229920000747 poly(lactic acid) Polymers 0.000 description 2
- 239000004626 polylactic acid Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- FMZUHGYZWYNSOA-VVBFYGJXSA-N (1r)-1-[(4r,4ar,8as)-2,6-diphenyl-4,4a,8,8a-tetrahydro-[1,3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol Chemical compound C([C@@H]1OC(O[C@@H]([C@@H]1O1)[C@H](O)CO)C=2C=CC=CC=2)OC1C1=CC=CC=C1 FMZUHGYZWYNSOA-VVBFYGJXSA-N 0.000 description 1
- HDUNAIVOFOKALD-RLCYQCIGSA-N (1s,2s)-1-[(4r)-2-(4-methylphenyl)-1,3-dioxolan-4-yl]-2-[(4s)-2-(4-methylphenyl)-1,3-dioxolan-4-yl]ethane-1,2-diol Chemical compound C1=CC(C)=CC=C1C1O[C@@H]([C@@H](O)[C@H](O)[C@H]2OC(OC2)C=2C=CC(C)=CC=2)CO1 HDUNAIVOFOKALD-RLCYQCIGSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 1
- ALKCLFLTXBBMMP-UHFFFAOYSA-N 3,7-dimethylocta-1,6-dien-3-yl hexanoate Chemical compound CCCCCC(=O)OC(C)(C=C)CCC=C(C)C ALKCLFLTXBBMMP-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- HEBKCHPVOIAQTA-QWWZWVQMSA-N D-arabinitol Chemical compound OC[C@@H](O)C(O)[C@H](O)CO HEBKCHPVOIAQTA-QWWZWVQMSA-N 0.000 description 1
- XTJFFFGAUHQWII-UHFFFAOYSA-N Dibutyl adipate Chemical compound CCCCOC(=O)CCCCC(=O)OCCCC XTJFFFGAUHQWII-UHFFFAOYSA-N 0.000 description 1
- PYGXAGIECVVIOZ-UHFFFAOYSA-N Dibutyl decanedioate Chemical compound CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-UHFFFAOYSA-N 0.000 description 1
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 description 1
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 description 1
- 239000004386 Erythritol Substances 0.000 description 1
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 description 1
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940087101 dibenzylidene sorbitol Drugs 0.000 description 1
- 229940100539 dibutyl adipate Drugs 0.000 description 1
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920006240 drawn fiber Polymers 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 1
- 235000019414 erythritol Nutrition 0.000 description 1
- 229940009714 erythritol Drugs 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- FBPFZTCFMRRESA-GUCUJZIJSA-N galactitol Chemical compound OC[C@H](O)[C@@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-GUCUJZIJSA-N 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229940097275 indigo Drugs 0.000 description 1
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Chemical class 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000013502 plastic waste Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Images
Classifications
-
- 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
- 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
Abstract
The present invention relates to a method for producing an aliphatic polyester fiber containing a poly (3-hydroxybutyrate) resin and a crystal nucleating agent, the method comprising: (i) Heating a resin composition containing the poly (3-hydroxybutyrate) resin and the crystal nucleating agent to a temperature of not lower than the melting point of the resin composition and not higher than the thermal decomposition temperature, and discharging the resin composition from a spinning nozzle; (ii) A step of drawing the resin composition discharged from the spinning nozzle by using a drawing roll; and (iii) winding the stretched resin composition by using a winding roll, wherein the stretching roll is composed of two or more rolls including a first roll and a second roll, the total stretching ratio of the resin composition is 250 or more, and the speed of the winding roll is 500 to 1500m/min.
Description
Technical Field
The present invention relates to a method for producing an aliphatic polyester fiber, and a multifilament.
Background
In recent years, plastic waste has a problem of causing a large load on the global environment, such as an influence on the ecosystem, generation of harmful gas during combustion, global warming due to a large amount of combustion heat, and the like. Biodegradable plastics have been actively developed as a solution to this problem.
In such biodegradable plastics, carbon dioxide emitted during combustion of biodegradable plastics obtained using plant-derived raw materials is present in the air itself, and therefore, carbon dioxide in the atmosphere does not increase. This phenomenon is called carbon balance, and is emphasized in the background of the kyoto protocol focusing on the target value of carbon dioxide reduction, and is expected to be actively used.
Recently, from the viewpoint of biodegradability and carbon balance, aliphatic polyester-based resins have attracted attention as biodegradable plastics produced by microorganisms using plant-derived raw materials as carbon sources, and in particular, polyhydroxyalkanoic acid (hereinafter, sometimes referred to as PHA) based resins, and among PHA based resins, poly (3-hydroxybutyrate) homopolyresin, poly (3-hydroxybutyrate-co-3-hydroxyvalerate) copolymeric resin, poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) copolymeric resin (hereinafter, sometimes referred to as P3HB3 HH), poly (3-hydroxybutyrate-co-4-hydroxybutyrate) copolymeric resin, polylactic acid, and the like have attracted attention.
However, the PHA resin has a low crystallization rate and a glass transition temperature lower than room temperature (about 0 to 4 ℃ C.), and therefore, in molding, after heating and melting, the cooling time for solidification must be extended, resulting in poor productivity. In particular, when a PHA is used to produce fibers by a melt spinning method, the resin is slowly solidified, and therefore, adhesion between fibers and adhesion to a roll occur, and it is difficult to stably produce fibers, and the quality of the obtained fibers is low.
As a conventional example of a technique for melt-spinning a 3-hydroxyalkanoic acid polymer, patent document 1 describes a melt-spinning method in which a polyester resin containing poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) is spun at a take-off speed of 1500m/min to 7000 m/min. Further, it is described that the method can improve spinning property and productivity and improve tensile strength.
As another conventional example, patent document 2 describes a method for melt spinning biodegradable aliphatic polyester fibers containing a polyhydroxyalkanoate, a crystal nucleating agent, and a lubricant, as follows: in spinning, the melt is extruded from a spinning die at a temperature of 130 ℃ to 190 ℃ to obtain raw filaments, the raw filaments are extracted by a first extraction roller at an extraction speed of 300 m/min to 4000 m/min, and the raw filaments are continuously extracted by a second extraction roller at an extraction speed of 600 m/min to 7000 m/min, thereby carrying out stretch spinning. It is also described that the crystallization rate of polyhydroxyalkanoate is improved by this method, and that the suction (suction) property is improved, the spinning property and productivity of the fiber are improved, and the tensile strength is improved.
As another conventional example, patent document 3 describes that PHA is fiberized under specific spinning conditions, and further that the PHA is drawn in a temperature range in which energy used in production is not wasted in the drawing step, and further that the PHA is relaxed in the heat treatment step, thereby exhibiting excellent mechanical properties.
Documents of the prior art
Patent document
Patent document 1: international publication No. 2015/029316
Patent document 2: international publication No. 2017/122679
Patent document 3: international publication No. 2012/133231
Disclosure of Invention
Problems to be solved by the invention
However, the melt spinning methods disclosed in patent documents 1 and 2 cannot provide an aliphatic polyester fiber containing a poly (3-hydroxybutyrate) resin having sufficient tensile strength. In addition, the method disclosed in patent document 3 requires drawing after fiberization and further heat treatment, and requires a long time for producing fibers, resulting in poor productivity.
The purpose of the present invention is to improve the productivity and tensile strength of an aliphatic polyester fiber containing a poly (3-hydroxybutyrate) resin and a crystal nucleating agent.
Means for solving the problems
A first aspect of the present invention relates to a method for producing an aliphatic polyester fiber containing a poly (3-hydroxybutyrate) resin and a crystal nucleating agent, the method comprising: (i) Heating a resin composition containing the poly (3-hydroxybutyrate) resin and the crystal nucleating agent to a temperature not lower than the melting point of the resin composition and not higher than the thermal decomposition temperature, and discharging the resin composition from a spinning nozzle; (ii) A step of drawing the resin composition discharged from the spinning nozzle by using a drawing roll; and (iii) winding the stretched resin composition by using a winding roll, wherein the stretching roll is composed of two or more rolls including a first roll and a second roll, the total stretching ratio of the resin composition (the winding roll speed (m/min)/the spinning nozzle flow speed (m/min)) is 250 or more, and the winding roll speed is 500 to 1500m/min.
In the method for producing an aliphatic polyester fiber, the ratio of the winding roller speed (m/min) to the first roller speed (m/min) is preferably 1.5 or more.
In the method for producing an aliphatic polyester fiber, the ratio of the first roll speed (m/min) to the spinning nozzle flow speed (m/min) is preferably 55 or more.
In the method for producing an aliphatic polyester fiber, it is preferable that the resin composition is blown with a gas flow having a temperature of not lower than the glass transition temperature and not higher than the crystallization temperature of the resin composition before being discharged from the spinning nozzle and brought into contact with the drawing roll.
In the method for producing an aliphatic polyester fiber, it is preferable that in the step (ii) of drawing, the temperature of the resin composition is 40 to 100 ℃.
In the method for producing an aliphatic polyester fiber, the winding roller speed is preferably 2 to 15% lower than the maximum speed of 2 or more rollers constituting the stretching roller.
In the method for producing an aliphatic polyester fiber, it is preferable that the resin composition is conveyed from the spinning nozzle to the take-up roll within 1 minute.
In the method for producing an aliphatic polyester fiber, the spinning nozzle preferably has 15 or more discharge holes.
In the method for producing an aliphatic polyester fiber, the poly (3-hydroxybutyrate) resin preferably contains poly (3-hydroxybutyrate-co-3-hydroxyhexanoate), and the proportion of the 3-hydroxyhexanoate in all monomer units constituting the poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) is 3 to 15mol%.
A second aspect of the present invention relates to an aliphatic polyester fiber comprising a poly (3-hydroxybutyrate) resin and a crystal nucleating agent, wherein the fineness of a single fiber is 1 to 20dtex, and the tensile strength of the single fiber is 1.5cN/dtex or more.
In the aliphatic polyester fiber, the poly (3-hydroxybutyrate) resin preferably contains poly (3-hydroxybutyrate-co-3-hydroxyhexanoate), and the proportion of the 3-hydroxyhexanoate in all monomer units constituting the poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) is 3 to 15mol%.
A third aspect of the present invention relates to a multifilament comprising 15 or more of the above aliphatic polyester fibers.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, the productivity of an aliphatic polyester fiber containing a poly (3-hydroxybutyrate) resin and a crystal nucleating agent can be improved, and the tensile strength can be improved.
Drawings
Fig. 1 is a conceptual diagram showing an example of a production apparatus used in the method for producing an aliphatic polyester fiber of the present invention.
Description of the symbols
1. Spinning nozzle
2. First quenching field
3. Second quenching field
4. First roller
5. Second roll
6. Third roller
7. The fourth roller
8. The fifth roller
9. Winding roller
10. Aliphatic polyester fiber
Detailed Description
[ Process for producing aliphatic polyester fiber ]
The process for producing an aliphatic polyester fiber of the present invention is a process for producing an aliphatic polyester fiber containing a poly (3-hydroxybutyrate) resin and a crystal nucleating agent, the process comprising:
(i) Heating a resin composition containing the poly (3-hydroxybutyrate) resin and the crystal nucleating agent to a temperature not lower than the melting point of the resin composition and not higher than the thermal decomposition temperature, and discharging the resin composition from a spinning nozzle;
(ii) A step of drawing the resin composition discharged from the spinning nozzle by using a drawing roll; and
(iii) A step of winding the stretched resin composition by using a winding roll,
the stretching roll is composed of two or more rolls including a first roll and a second roll, the total stretching ratio of the resin composition (the winding roll speed (m/min)/the spinning nozzle flow velocity (m/min)) is 250 or more, and the winding roll speed is 500 to 1500m/min.
The step (i) of heating a resin composition containing a poly (3-hydroxybutyrate) resin and a crystal nucleating agent to a temperature not lower than the melting point of the resin composition and not higher than the thermal decomposition temperature and discharging the resin composition from a spinning nozzle will be described in detail below.
In the present invention, the poly (3-hydroxybutyrate) resin means an aliphatic polyester containing 3-hydroxybutyrate as a monomer unit constituting the resin.
Examples of the poly (3-hydroxybutyrate) resin include resins containing poly (3-hydroxybutyrate) such as poly (3-hydroxybutyrate); and a resin comprising a copolymer resin formed from 3-hydroxybutyrate and other hydroxyalkanoic acids.
Examples of the copolymer resin composed of 3-hydroxybutyrate and another hydroxyalkanoic acid include: p3HB3HH [ poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) ], PHBV [ poly (3-hydroxybutyrate-co-3-hydroxyvalerate) ], P3HB4HB [ poly (3-hydroxybutyrate-co-4-hydroxybutyrate) ], poly (3-hydroxybutyrate-co-3-hydroxyvalerate-co-3-hydroxyhexanoate, poly (3-hydroxybutyrate-co-3-hydroxyoctanoate), and poly (3-hydroxybutyrate-co-3-hydroxyoctadecanoate), and the like, among these, poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) is preferable because the obtained aliphatic polyester fiber is not only excellent in biodegradability, but also has practically sufficient forming processability, and is excellent in tensile strength and flexibility.
The resin constituting the copolymer resin comprising 3-hydroxybutyrate and another hydroxyalkanoic acid is preferably 0.5 to 15mol%, more preferably 1.5 to 15mol%, further preferably 3 to 15mol%, most preferably 3 to 8mol% of the 3-hydroxyhexanoate in all monomer units constituting the resin. This is because the obtained aliphatic polyester fiber is excellent in tensile strength and flexibility.
The weight average molecular weight Mw of the poly (3-hydroxybutyrate) resin is preferably 50000 to 3000000, more preferably 100000 to 1500000, and still more preferably 200000 to 1000000. This is because when the weight average molecular weight Mw is too low, the tensile strength of the obtained aliphatic polyester fiber tends to decrease, and when the weight average molecular weight Mw is too high, the processability may decrease and the molding may be difficult.
The weight average molecular weight Mw is measured by polystyrene-equivalent molecular weight distribution using Gel Permeation Chromatography (GPC) using chloroform eluent. As the column in GPC, a column suitable for measuring the molecular weight may be used.
In the present invention, the crystal nucleating agent is a compound having a melting point higher than that of the poly (3-hydroxybutyrate) resin and having an effect of promoting crystallization of the resin. The compound is not particularly limited. Examples of the crystal nucleating agent include: inorganic substances (boron nitride, titanium oxide, talc, layered silicate, calcium carbonate, sodium chloride, metal phosphate, and the like); sugar alcohol compounds derived from natural products (pentaerythritol, erythritol, galactitol, mannitol, arabitol, and the like); polyvinyl alcohol; chitin; chitosan; polyoxyethylene; an aliphatic carboxylic acid salt; an aliphatic alcohol; an aliphatic carboxylic acid ester; dicarboxylic acid derivatives (dimethyl adipate, dibutyl adipate, diisodecyl adipate, and dibutyl sebacate); cyclic compounds having C = O and a functional group selected from NH, S, and O in the molecule (indigo, quinacridone magenta, and the like); sorbitol derivatives (e.g., dibenzylidene sorbitol and bis (p-methylbenzylidene) sorbitol); compounds containing a nitrogen-containing heteroaromatic nucleus (pyridine ring, triazine ring, imidazole ring, and the like) (pyridine, triazine, imidazole, and the like); a phosphate ester compound; bisamides of higher fatty acids; metal salts of higher fatty acids; and branched polylactic acid. In addition, when the poly (3-hydroxybutyrate) resin is P3HB3HH, a poly (3-hydroxybutyrate) having a melting point higher than that of P3HB3HH may be used.
Among these, from the viewpoints of the effect of improving the crystallization rate of the poly (3-hydroxybutyrate) resin and the compatibility and affinity with the poly (3-hydroxybutyrate) resin, the sugar alcohol compound, polyvinyl alcohol, chitin, and chitosan are preferable, and pentaerythritol is more preferable. These compounds can be used alone, also can be combined with 2 or more.
The content of the crystal nucleating agent in the resin composition containing the poly (3-hydroxybutyrate) resin and the crystal nucleating agent is preferably 0.05 parts by weight or more, more preferably 0.1 parts by weight or more, and still more preferably 0.5 parts by weight or more, based on 100 parts by weight of the poly (3-hydroxybutyrate) resin. The content 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. When the content of the crystal nucleating agent is too small, the effect as the crystal nucleating agent may be insufficient, and when the content of the crystal nucleating agent is too large, the viscosity of the resin composition during heating may be lowered.
The resin composition may contain a known additive as needed, as an optional component other than the poly (3-hydroxybutyrate) resin and the crystal nucleating agent. Known additives include stabilizers such as antioxidants and ultraviolet absorbers; colorants such as dyes and pigments; a plasticizer; a lubricant; an inorganic filler; an organic filler; and antistatic agents, and the like. These additives may be used singly or in combination of two or more.
The plasticizer is not particularly limited, and examples thereof include adipate plasticizers, acetylated monoglyceride plasticizers, and polyglycerin fatty acid ester plasticizers. In addition, plasticization by a supercritical fluid such as carbon dioxide or nitrogen may be used.
The lubricant is not particularly limited, and examples thereof include: fatty acid amides such as behenamide, stearic amide, erucic amide, and oleic amide.
When the resin composition is heated to a temperature not lower than the melting point of the resin composition and not higher than the thermal decomposition temperature, the heating temperature may be appropriately adjusted depending on the kind of the resin composition, and is preferably not lower than the melting point of the resin composition +5 ℃, and more preferably not lower than the melting point +10 ℃. The heating temperature is preferably lower than the thermal decomposition temperature of the resin composition, and more preferably-5 ℃ or lower.
In the present invention, the melting point is measured by a Differential Scanning Calorimetry (DSC) method. Specifically, the temperature was measured at a temperature rise rate of 10 ℃ per minute using a differential scanning calorimeter, and the obtained endothermic peak was defined as the melting point.
In the present invention, the thermal decomposition temperature refers to a weight reduction initiation temperature measured by Thermogravimetry (TG). Specifically, the temperature was measured at a temperature increase rate of 10 ℃ per minute using a thermogravimetric instrument, and the temperature at the time of starting the weight reduction was defined as the thermal decomposition temperature.
The melt flow rate (hereinafter, sometimes referred to as MFR) of the resin composition containing the poly (3-hydroxybutyrate) resin and the crystal nucleating agent, measured at 165 ℃ and 5kgf, is preferably 0.1 to 100g/10min, more preferably 0.5 to 80g/10min, and still more preferably 1.0 to 60g/10min.
The melt flow rate was measured based on JIS K7210-2 at 165 ℃ under a 5kg load condition.
The spinning nozzle includes a discharge hole for discharging the resin composition, but the shape, size, and number of the discharge hole are not particularly limited. The size of the discharge hole is preferably set to be phi 0.1mm to 3.0mm, for example, when the discharge hole is circular. The number of the discharge holes also depends on the size of the discharge holes, and may be, for example, 15 or more, or 1000 or less.
The flow velocity of the spinning nozzle, i.e., the velocity at which the resin composition is discharged from the spinning nozzle, is preferably 0.05 to 6.0m/min, more preferably 0.1 to 6.0m/min, and still more preferably 0.5 to 6.0m/min.
The discharge amount from the spinning nozzle is preferably 0.10 g/min/hole or more, more preferably 0.15 g/min/hole or more. The discharge amount is preferably less than 1.0 g/min/hole, more preferably 0.90 g/min/hole or less.
Preferably, the resin composition is rapidly cooled by blowing a gas stream having a temperature of not lower than the glass transition temperature and not higher than the crystallization temperature of the resin composition before being discharged from the spinning nozzle and brought into contact with the stretching roll. By such rapid cooling, the cooling and solidification of the resin composition can be promoted, and the tensile strain imparted by the speed difference between the stretching rollers or the like can be reflected more effectively. As a result, the tensile strength of the obtained aliphatic polyester fiber can be further improved.
In the present invention, the glass transition temperature is measured by a Differential Scanning Calorimetry (DSC) method. Specifically, the temperature was measured at a temperature increase rate of 10 ℃ per minute using a differential scanning calorimeter, and the temperature at the inflection point of the obtained DSC curve was defined as the glass transition temperature.
The crystallization temperature was measured by Differential Scanning Calorimetry (DSC). Specifically, the temperature was measured at a cooling rate of 10 ℃ per minute using a differential scanning calorimeter, and the exothermic peak of the obtained DSC curve was defined as the crystallization temperature.
The temperature of the gas flow to be blown to the resin composition discharged from the spinning nozzle may be equal to or higher than the glass transition temperature of the resin composition and equal to or lower than the crystallization temperature, and may be appropriately adjusted according to the kind of the resin composition. The temperature of the gas flow is preferably lower than the crystallization temperature of the resin composition, more preferably-20 ℃ or lower, and still more preferably-40 ℃ or lower.
The velocity of the gas flow is not particularly limited, but is preferably 0.1m/s to 5m/s, more preferably 0.1m/s to 3 m/s. This is because when the velocity of the air flow is less than 0.1m/s, the obtained cooling effect becomes too small, and when it exceeds 5m/s, the resin composition discharged from the spinning nozzle oscillates by the air flow, and thereby fusion and/or yarn breakage of the discharged resin compositions occur, and the spinning stability may be lowered.
The type of the air flow is also not particularly limited, and is preferably air; inert gases such as nitrogen and argon.
The following details (ii) the step of stretching the resin composition discharged from the spinning nozzle by using a stretching roll; and (iii) winding up the stretched resin composition by using a winding roll.
The resin composition discharged from the spinning nozzle is first drawn by the first roll and then drawn by two or more rolls including the first roll and the second roll.
The stretching rolls include a first roll and a second roll, and the number of the stretching rolls is not particularly limited, and may be appropriately selected in consideration of the temperature control efficiency, the stretching magnification, and the like of the fiber. The number of the stretching rollers may be 3 or more, 4 or more, or 5 or more. The number of the stretching rolls is not particularly limited as long as it is within the range of the object of the present invention, and the upper limit is 10 or less from the viewpoint of not excessively increasing the facility cost and the manufacturing apparatus.
Further, each of the stretching rollers may be constituted not only by one roller but also by a set of two or more rollers at the same speed. The temperature of the drawn fiber can be made uniform, and a long fiber can be manufactured in a smaller space.
The ratio (hereinafter, may be referred to as NDR) of the first roll speed (m/min) to the spinning nozzle flow speed (m/min) is preferably 55 or more, more preferably 100 or more, further preferably 150 or more, and particularly preferably 200 or more. This is because increasing NDR promotes alignment of molecular chains of the resin composition, and further, because the diameter of the resin composition is reduced, cooling solidification is promoted. The NDR has no upper limit as long as fiber breakage does not occur, and may be 1000 or less.
The ratio of the take-up roller speed (m/min) to the first roller speed (m/min) is preferably 1.5 or more, more preferably 1.7 or more, and still more preferably 1.8 or more. This is because an aliphatic polyester fiber having more excellent tensile strength can be obtained. The ratio is not limited to an upper limit as long as the fibers are not broken, and may be 30 or less.
In the step (ii) of stretching the resin composition discharged from the spinning nozzle by using a stretching roll, the temperature of the resin composition is preferably 40 to 100 ℃, more preferably 50 to 80 ℃. This is because the crystallization rate of the resin composition can be increased, and the productivity and tensile strength of the aliphatic polyester fiber can be further improved. The temperature of the resin composition is adjusted by adjusting the temperature of the following object in contact with the resin composition: solids such as the surface of the draw rolls; liquids such as baths and droplets; and gases such as gas streams.
The stretched resin composition is wound up by a winding roll, and the total draw ratio of the resin composition is 250 or more. The total draw ratio is preferably 270 or more, more preferably 300 or more, still more preferably 330 or more, and still more preferably 340 or more. The total draw ratio is not limited as long as a fiber having a desired fineness can be stably obtained, and may be 2000 or less.
The total draw ratio is defined by the speed of the take-up roll (m/min)/the flow speed of the spinning nozzle (m/min).
The speed of the take-up roll is 500 to 1500m/min, and the speed of the spinning nozzle and the speed of other rolls may be appropriately adjusted within this range.
The winding roller speed is preferably 2 to 15% lower, more preferably 3 to 15% lower, and still more preferably 3 to 12% lower than the maximum speed of 2 or more rollers constituting the stretching roller. This is because the resulting aliphatic polyester fiber is less likely to have residual stress and to undergo dry heat shrinkage. The ratio indicated by "%", that is, (the maximum speed roller speed-the winding roller speed)/the winding roller speed × 100, may be referred to as "relaxation rate (%)".
The time for conveying the resin composition from the spinning nozzle to the take-up roll is preferably within 1 minute, preferably within 50 seconds, more preferably within 40 seconds, and still more preferably within 30 seconds. The time may be 1 second or more. According to the production method of the present invention, an aliphatic polyester fiber having high tensile strength can be produced in a short time with good productivity.
[ aliphatic polyester fiber ]
The aliphatic polyester fiber of the present invention comprises a poly (3-hydroxybutyrate) resin and a crystal nucleating agent, wherein the fineness of a single fiber is 1 to 20dtex, and the tensile strength of a single fiber is 1.5cN/dtex or more.
The content of the crystal nucleating agent in the aliphatic polyester fiber of the present invention is preferably 0.05 parts by weight or more, more preferably 0.1 parts by weight or more, and still more preferably 0.5 parts by weight or more, based on 100 parts by weight of the poly (3-hydroxybutyrate) resin. The content is preferably 12 parts by weight or less, more preferably 10 parts by weight or less, still more preferably 8 parts by weight or less, and most preferably 5 parts by weight or less, based on 100 parts by weight of the poly (3-hydroxybutyrate) resin.
The particle diameter of the crystal nucleating agent contained in the aliphatic polyester fiber is preferably one third or less with respect to the minimum diagonal length of the cross section of the fiber. This is because the tensile strength of the fiber is more excellent.
The particle diameter of the crystal nucleating agent was determined as D50 (median diameter) by a laser diffraction method.
The fineness of the single fiber of the aliphatic polyester fiber of the present invention may be 1.5dtex or more, or 2dtex or more. The fineness may be 15dtex or less, or 10dtex or less.
The fineness of a single fiber refers to the thickness of the fiber and is defined as the average mass per unit length. The average mass (g) per 10000m is expressed in units (dtex). Specifically, the measurement is carried out by an auto-vibrometer (auto-viscoscope) method.
The single fiber of the aliphatic polyester fiber of the present invention has a tensile strength of preferably 1.6cN/dtex or more, more preferably 1.7cN/dtex or more, still more preferably 1.8cN/dtex or more, and most preferably 1.9cN/dtex or more. The tensile strength is not particularly limited as long as the flexibility and toughness required for the application are not impaired, and may be 10cN/dtex or less. The aliphatic polyester fiber of the present invention is fine, but has excellent tensile strength.
The tensile strength of the single fibers was measured at an initial length of 20mm and a speed of 20mm/min in accordance with JIS L1015.
[ multifilament ]
The aliphatic polyester fiber of the present invention may constitute a multifilament. In the case of forming a multifilament, the number and fineness of the aliphatic polyester fibers forming the multifilament may be determined according to the required characteristics, and preferably 15 or more aliphatic polyester fibers are contained, more preferably 20 or more, and still more preferably 30 or more. The aliphatic polyester fiber may contain 1000 or less aliphatic polyester fibers. If the total fineness of the multifilament is the same, the greater the number of fibers constituting the multifilament, the higher the flexibility and softness, but the durability tends to be easily reduced.
Examples
The present invention will be described more specifically with reference to the following examples, but the technical scope of the present invention is not limited to these examples.
(example 1)
Dry blending was carried out in the following proportions: the resin was copolymerized with poly (3-hydroxybutyrate) resin (3-hydroxybutyrate-co-3-hydroxyhexanoate) (the ratio of 3-hydroxyhexanoate =6mol%, mw =55 ten thousand, MFR (165 ℃, 5 kg) =3g/10 min) 100 parts by weight, pentaerythritol "noiiraza (ノイライザー) P" (manufactured by japan synthetic chemical co., ltd.) 1 part by weight as a crystal nucleating agent, erucamide 0.5 part by weight as a lubricant, and behenamide 0.5 part by weight. The resin composition was obtained by melt-kneading the components at 150 ℃ using an extruder and pelletized.
The obtained pellets (resin composition) had a glass transition temperature of 2 ℃, a crystallization temperature of 80 ℃, a melting point of 142 ℃ and a thermal decomposition temperature of 180 ℃.
The process for producing an aliphatic polyester fiber using the obtained pellets will be described with reference to fig. 1. The following operations are sequentially carried out: the obtained pellets were melted by using a single screw extruder (not shown) having a cylinder diameter of 25mm, and the flow rate was adjusted by a gear pump, and the pellets were extruded from a spinning nozzle 1 (shape of discharge hole: circular) under the conditions described in table 1 at a melt spinning temperature of 170 ℃ to a first space (first quenching field) 2 through which air (quenching air) was blown at 14 ℃ and 1.0 m/s; sent to a second space (second quenching field) 3 where air (quenching air) at 13 ℃ and 1.0m/s is blown; the extraction was performed by using the first roll 4 under the conditions described in table 1; the aliphatic polyester fiber 10 was obtained by winding the fiber successively on a second roll 5 (896 m/min, 70 ℃), a third roll 6 (1050 m/min, 70 ℃), a fourth roll 7 (1050 m/min, 70 ℃), and a fifth roll 8 (1010 m/min, 34 ℃/36 ℃) by a winding roll 9 (1000 m/min). The time taken for the resin composition to be conveyed from the spinning nozzle to the take-up roll is 30 seconds or less.
In this case, the first roller 4, the second roller 5, the third roller 6, and the fourth roller 7 are each configured by a set of two rollers having the same speed and the same temperature. The fifth roller 8 is constituted by a set of two rollers having the same speed. NDR = first roll speed/spinning nozzle flow rate, relaxation rate (%) = (maximum speed roll speed-take-up roll speed)/take-up roll speed × 100, and total draw ratio = take-up roll speed/spinning nozzle flow rate. In the present invention, the normal temperature is a temperature included in the range of 5 to 35 ℃.
The individual fineness, fiber diameter and tensile strength of the obtained aliphatic polyester fiber were measured by the following methods. The results are shown in Table 1.
(Single degree)
The measurement was carried out using a specimen length of 50mm using a specimen length measuring machine Denier COMPUTER DC-11 of Search corporation.
(fiber diameter)
Since the discharge hole of the spinning nozzle had a circular shape and the cross-sectional shape of the obtained fiber was also circular, the fiber diameter was calculated from the cross-sectional area obtained from the single fineness and the specific gravity of the aliphatic polyester fiber measured in advance (the cross-sectional shape was calculated as a perfect circle).
(tensile Strength)
The tensile strength was measured under the following conditions using an Autograph AG-I, a tensile measuring apparatus manufactured by Shimadzu corporation. That is, the obtained aliphatic polyester fibers were used as samples, the initial length of each sample was set to 20mm, and the measurement was performed at a speed of 20mm/min using a load cell having a rated capacity of 5N. Further, the average tensile strength per fineness (cN/dtex) was calculated based on the single-fiber count measured in advance.
(examples 2 to 9 and comparative examples 1 to 4)
An aliphatic polyester fiber was obtained in the same manner as in example 1, except that the conditions were changed to those shown in table 1. The time taken for the resin composition to be conveyed from the spinning nozzle to the take-up roll is 30 seconds or less.
The results of measuring the physical properties of the obtained aliphatic polyester fibers are shown in table 1.
As shown in Table 1, the aliphatic polyester fibers of comparative examples 1 to 4, in which the total draw ratio was less than 250 or the take-up roll speed was less than 500m/min, all had low tensile strengths. In contrast, the aliphatic polyester fibers of the examples have excellent tensile strength, although they were produced using the same resin composition.
Claims (12)
1. A method for producing an aliphatic polyester fiber containing a poly (3-hydroxybutyrate) resin and a crystal nucleating agent, comprising:
(i) Heating a resin composition containing the poly (3-hydroxybutyrate) resin and the crystal nucleating agent to a temperature of not lower than the melting point of the resin composition and not higher than the thermal decomposition temperature, and discharging the resin composition from a spinning nozzle;
(ii) A step of drawing the resin composition discharged from the spinning nozzle by using a drawing roll; and
(iii) A step of winding the stretched resin composition by using a winding roll,
the stretching roll is composed of two or more rolls including a first roll and a second roll, the total stretching ratio (the speed of the take-up roll (m/min)/the flow rate of the spinning nozzle (m/min)) of the resin composition is 250 or more,
the speed of the coiling roller is 500-1500 m/min.
2. The method for producing aliphatic polyester fibers according to claim 1,
the ratio of the take-up roller speed (m/min) to the first roller speed (m/min) is 1.5 or more.
3. The method for producing an aliphatic polyester fiber according to claim 1 or 2,
the ratio of the first roller speed (m/min) to the spinning nozzle flow speed (m/min) is 55 or more.
4. The method for producing an aliphatic polyester fiber according to any one of claims 1 to 3,
blowing a gas flow having a temperature of not lower than the glass transition temperature and not higher than the crystallization temperature of the resin composition to the resin composition before being discharged from the spinning nozzle and being in contact with the drawing roll.
5. The method for producing an aliphatic polyester fiber according to any one of claims 1 to 4,
in the step of (ii) stretching, the temperature of the resin composition is set to 40 to 100 ℃.
6. The method for producing an aliphatic polyester fiber according to any one of claims 1 to 5,
the winding roller speed is 2-15% lower than the maximum speed of 2 or more rollers constituting the stretching roller.
7. The method for producing an aliphatic polyester fiber according to any one of claims 1 to 6,
transporting the resin composition from the spinning nozzle to the take-up roll within 1 minute.
8. The method for producing an aliphatic polyester fiber according to any one of claims 1 to 7,
the spinning nozzle has 15 or more discharge holes.
9. The method for producing an aliphatic polyester fiber according to any one of claims 1 to 8,
the poly (3-hydroxybutyrate) resin comprises poly (3-hydroxybutyrate-co-3-hydroxyhexanoate),
the proportion of the 3-hydroxyhexanoate ester in the total monomer units constituting the poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) is 3 to 15mol%.
10. An aliphatic polyester fiber comprising a poly (3-hydroxybutyrate) resin and a crystal nucleating agent,
the fineness of the single fiber is 1 to 20dtex, and the tensile strength of the single fiber is more than 1.5 cN/dtex.
11. The aliphatic polyester fiber according to claim 10,
the poly (3-hydroxybutyrate) resin comprises poly (3-hydroxybutyrate-co-3-hydroxyhexanoate),
the proportion of the 3-hydroxyhexanoate ester in the total monomer units constituting the poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) is 3 to 15mol%.
12. A multifilament comprising 15 or more of the aliphatic polyester fibers of claim 10 or 11.
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| PCT/JP2021/014957 WO2021206154A1 (en) | 2020-04-09 | 2021-04-08 | Method for producing aliphatic polyester fiber, aliphatic polyester fiber, and multifilament |
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| CN117795140A (en) * | 2021-08-18 | 2024-03-29 | 株式会社钟化 | Multifilament for stretching and method for producing the same, multifilament and method for producing the same, and staple fiber and method for producing the same |
| WO2023167245A1 (en) * | 2022-03-04 | 2023-09-07 | 株式会社カネカ | Multifilament and method for producing same |
| CN114851528B (en) * | 2022-07-06 | 2022-09-23 | 北京蓝晶微生物科技有限公司 | Polyhydroxyalkanoate forming body and preparation method thereof |
| CN115232455B (en) * | 2022-09-22 | 2023-01-17 | 北京蓝晶微生物科技有限公司 | Polyhydroxyalkanoate composition containing ester nucleating agent, polyhydroxyalkanoate molded body and preparation method thereof |
| CN115627559B (en) * | 2022-11-18 | 2023-05-16 | 北京微构工场生物技术有限公司 | Degradable filament and special material thereof |
| CN115637506B (en) * | 2022-11-18 | 2023-05-16 | 北京微构工场生物技术有限公司 | Filament, preparation method and application thereof |
| CN115613155B (en) * | 2022-11-18 | 2023-05-16 | 北京微构工场生物技术有限公司 | Filament or staple fiber and preparation method thereof |
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| US10760183B2 (en) * | 2016-01-12 | 2020-09-01 | Tokyo Institute Of Technology | Biodegradable aliphatic polyester fiber and method for producing the same |
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