CN117881820A - Composition for biodegradable fiber and biodegradable fiber manufactured using the same - Google Patents
Composition for biodegradable fiber and biodegradable fiber manufactured using the same Download PDFInfo
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- CN117881820A CN117881820A CN202280058438.8A CN202280058438A CN117881820A CN 117881820 A CN117881820 A CN 117881820A CN 202280058438 A CN202280058438 A CN 202280058438A CN 117881820 A CN117881820 A CN 117881820A
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- Prior art keywords
- biodegradable
- composition
- resin
- pha
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- 239000000835 fiber Substances 0.000 title claims abstract description 224
- 239000000203 mixture Substances 0.000 title claims abstract description 140
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 claims abstract description 222
- 229920005989 resin Polymers 0.000 claims abstract description 214
- 239000011347 resin Substances 0.000 claims abstract description 214
- 229920000903 polyhydroxyalkanoate Polymers 0.000 claims abstract description 209
- SJZRECIVHVDYJC-UHFFFAOYSA-M 4-hydroxybutyrate Chemical compound OCCCC([O-])=O SJZRECIVHVDYJC-UHFFFAOYSA-M 0.000 claims abstract description 100
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 19
- 230000004580 weight loss Effects 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- -1 polybutylene adipate terephthalate Polymers 0.000 claims description 88
- 239000002245 particle Substances 0.000 claims description 69
- 238000000034 method Methods 0.000 claims description 37
- 239000000155 melt Substances 0.000 claims description 33
- 239000004629 polybutylene adipate terephthalate Substances 0.000 claims description 28
- 239000004631 polybutylene succinate Substances 0.000 claims description 28
- 229920002961 polybutylene succinate Polymers 0.000 claims description 28
- 229920006167 biodegradable resin Polymers 0.000 claims description 27
- 239000004626 polylactic acid Substances 0.000 claims description 27
- 238000009987 spinning Methods 0.000 claims description 27
- 229920009537 polybutylene succinate adipate Polymers 0.000 claims description 20
- 239000004630 polybutylene succinate adipate Substances 0.000 claims description 20
- REKYPYSUBKSCAT-UHFFFAOYSA-N 3-hydroxypentanoic acid Chemical compound CCC(O)CC(O)=O REKYPYSUBKSCAT-UHFFFAOYSA-N 0.000 claims description 19
- 238000002844 melting Methods 0.000 claims description 18
- 230000008018 melting Effects 0.000 claims description 18
- 239000002131 composite material Substances 0.000 claims description 17
- 229920008262 Thermoplastic starch Polymers 0.000 claims description 16
- 230000009477 glass transition Effects 0.000 claims description 16
- 229920001610 polycaprolactone Polymers 0.000 claims description 16
- 239000004632 polycaprolactone Substances 0.000 claims description 16
- 239000004628 starch-based polymer Substances 0.000 claims description 16
- WHBMMWSBFZVSSR-UHFFFAOYSA-M 3-hydroxybutyrate Chemical compound CC(O)CC([O-])=O WHBMMWSBFZVSSR-UHFFFAOYSA-M 0.000 claims description 15
- 238000002074 melt spinning Methods 0.000 claims description 15
- WHBMMWSBFZVSSR-UHFFFAOYSA-N R3HBA Natural products CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 claims description 12
- 239000003963 antioxidant agent Substances 0.000 claims description 12
- 239000000654 additive Substances 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- ALRHLSYJTWAHJZ-UHFFFAOYSA-M 3-hydroxypropionate Chemical compound OCCC([O-])=O ALRHLSYJTWAHJZ-UHFFFAOYSA-M 0.000 claims description 10
- PHOJOSOUIAQEDH-UHFFFAOYSA-N 5-hydroxypentanoic acid Chemical compound OCCCCC(O)=O PHOJOSOUIAQEDH-UHFFFAOYSA-N 0.000 claims description 10
- 239000002667 nucleating agent Substances 0.000 claims description 10
- 230000000996 additive effect Effects 0.000 claims description 9
- 238000000113 differential scanning calorimetry Methods 0.000 claims description 8
- 229940070710 valerate Drugs 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000012748 slip agent Substances 0.000 claims description 7
- 239000006096 absorbing agent Substances 0.000 claims description 6
- 239000003623 enhancer Substances 0.000 claims description 6
- 239000000049 pigment Substances 0.000 claims description 5
- HPMGFDVTYHWBAG-UHFFFAOYSA-N 3-hydroxyhexanoic acid Chemical compound CCCC(O)CC(O)=O HPMGFDVTYHWBAG-UHFFFAOYSA-N 0.000 claims description 4
- FMHKPLXYWVCLME-UHFFFAOYSA-N 4-hydroxy-valeric acid Chemical compound CC(O)CCC(O)=O FMHKPLXYWVCLME-UHFFFAOYSA-N 0.000 claims description 4
- IWHLYPDWHHPVAA-UHFFFAOYSA-N 6-hydroxyhexanoic acid Chemical compound OCCCCCC(O)=O IWHLYPDWHHPVAA-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 229920000747 poly(lactic acid) Polymers 0.000 description 19
- 239000011118 polyvinyl acetate Substances 0.000 description 18
- 229920002689 polyvinyl acetate Polymers 0.000 description 18
- 230000000694 effects Effects 0.000 description 17
- 238000002425 crystallisation Methods 0.000 description 15
- 230000008025 crystallization Effects 0.000 description 15
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- 230000000704 physical effect Effects 0.000 description 14
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- 239000000047 product Substances 0.000 description 12
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- 238000005520 cutting process Methods 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 9
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- 230000001771 impaired effect Effects 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 6
- 241001550224 Apha Species 0.000 description 6
- 239000002028 Biomass Substances 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 230000003078 antioxidant effect Effects 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 239000003431 cross linking reagent Substances 0.000 description 5
- 150000002894 organic compounds Chemical class 0.000 description 5
- 238000004804 winding Methods 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
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- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 229920002988 biodegradable polymer Polymers 0.000 description 3
- 239000004621 biodegradable polymer Substances 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 150000007942 carboxylates Chemical group 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000001595 flow curve Methods 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 239000011147 inorganic material Substances 0.000 description 3
- 230000000813 microbial effect Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000005022 packaging material Substances 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical class C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000007791 dehumidification Methods 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000002296 dynamic light scattering Methods 0.000 description 2
- XMHIUKTWLZUKEX-UHFFFAOYSA-N hexacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O XMHIUKTWLZUKEX-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
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- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 2
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- 239000008117 stearic acid Substances 0.000 description 2
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
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- VHOCUJPBKOZGJD-UHFFFAOYSA-N triacontanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O VHOCUJPBKOZGJD-UHFFFAOYSA-N 0.000 description 2
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 235000014692 zinc oxide Nutrition 0.000 description 2
- XBUXARJOYUQNTC-UHFFFAOYSA-N ()-3-Hydroxynonanoic acid Chemical compound CCCCCCC(O)CC(O)=O XBUXARJOYUQNTC-UHFFFAOYSA-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
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- RGASRBUYZODJTG-UHFFFAOYSA-N 1,1-bis(2,4-ditert-butylphenyl)-2,2-bis(hydroxymethyl)propane-1,3-diol dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C RGASRBUYZODJTG-UHFFFAOYSA-N 0.000 description 1
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
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- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
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- MDWVSAYEQPLWMX-UHFFFAOYSA-N 4,4'-Methylenebis(2,6-di-tert-butylphenol) Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 MDWVSAYEQPLWMX-UHFFFAOYSA-N 0.000 description 1
- UNUVUYPEOAILGM-UHFFFAOYSA-N 4-ethenylbicyclo[2.2.1]heptane Chemical compound C1CC2CCC1(C=C)C2 UNUVUYPEOAILGM-UHFFFAOYSA-N 0.000 description 1
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Abstract
The present invention relates to a composition for biodegradable fibers and biodegradable fibers manufactured using the same. In detail, according to an embodiment of the present invention, a composition for biodegradable fiber includes a Polyhydroxyalkanoate (PHA) resin having a 4-hydroxybutyrate (4-HB) repeat unit and specifically includes a first PHA resin and/or a second PHA resin each having a 4-HB repeat unit and having a decomposition temperature (Td, 5% weight loss) of 220 ℃ or more measured by a thermogravimetric analyzer. Thus, the composition is environmentally friendly, has excellent biodegradability and biocompatibility, and can be used to easily manufacture biodegradable fibers having excellent properties.
Description
Technical Field
The present invention relates to a composition for biodegradable fibers and biodegradable fibers prepared therefrom.
Background
In recent years, with increasing attention to environmental problems, studies for treating and recycling various household garbage are actively being conducted. In particular, although polymer materials, which are inexpensive and have excellent processability, are widely used to manufacture various products (e.g., paper, film, fiber, packaging material, bottle, and container), when the life of these products is over, harmful substances may be discharged when they are burned, and depending on the types of harmful substances, it takes hundreds of years to be completely naturally decomposed.
Accordingly, research into biodegradable polymers that can be decomposed in a short time to improve environmental friendliness while improving mechanical properties (e.g., flexibility and strength), productivity and processability, and extending the life of the product itself, thereby reducing the amount of garbage or improving recyclability thereof, is still ongoing.
Polyhydroxyalkanoates (PHA) are biodegradable polymers composed of various types of hydroxycarboxylic acids produced by a large number of microorganisms and used as intracellular storage materials. Polyhydroxyalkanoates have physical properties similar to those of conventional petroleum-derived synthetic polymers such as polybutylene adipate terephthalate (PBAT), polybutylene succinate (PBS), polybutylene succinate terephthalate (PBST) and polybutylene succinate adipate (PBSA), exhibit complete biodegradability, and have excellent biocompatibility.
Meanwhile, biodegradable fibers made of biodegradable polymers are widely used for nonwoven fabrics, disposable tissues, packaging materials, masks, industrial materials (e.g., engineering plastics), or filters for air cleaners, etc. However, since these products are difficult to collect or recycle after use, they are abandoned in soil or the ocean, thereby severely polluting the environment. Therefore, although biodegradable fibers having improved biodegradability are being applied, it is difficult to apply various processes or expand the uses thereof in various ways due to the expensive raw materials, and there are limitations in improving physical properties (e.g., mechanical strength). Therefore, there is a need to develop biodegradable fibers capable of improving all characteristics such as flexibility, strength and processability while being environmentally friendly due to having excellent biodegradability and biocompatibility.
[ Prior Art literature ]
[ patent literature ]
(patent document 1) korean laid-open patent publication No. 2012-0103158
Disclosure of Invention
Technical problem
Accordingly, the present invention is directed to providing a biodegradable fiber composition capable of improving flexibility, strength and processability while being environmentally friendly due to excellent biodegradability and biocompatibility, and a biodegradable fiber prepared using the same.
Solution to the technical problem
The composition for biodegradable fibers according to the embodiment of the present invention comprises a polyhydroxyalkanoate resin comprising 4-hydroxybutyrate (4-HB) repeat units, wherein a decomposition temperature (Td, 5% weight loss) measured by a thermogravimetric analyzer (TGA) is 220 ℃ or higher.
According to an embodiment of the present invention, the polyhydroxyalkanoate resin may comprise 4-hydroxybutyrate (4-HB) repeat units in an amount of 0.1% to 60% by weight.
According to an embodiment of the present invention, the polyhydroxyalkanoate resin may further comprise at least one repeating unit selected from the group consisting of 3-hydroxybutyrate (3-HB), 3-hydroxypropionate (3-HP), 3-hydroxycaproate (3-HH), 3-hydroxyvalerate (3-HV), 4-hydroxyvalerate (4-HV), 5-hydroxyvalerate (5-HV), and 6-hydroxycaproate (6-HH).
According to embodiments of the present invention, the polyhydroxyalkanoate resin may comprise a first PHA resin.
According to embodiments of the present invention, the first PHA resin may comprise 4-hydroxybutyrate (4-HB) repeat units in an amount of 15 wt.% to 60 wt.% and have a Melt Flow Index (MFI) of 0.1g/10min to 20g/10min measured at 165℃and 5kg according to ASTM D1238.
According to embodiments of the invention, the polyhydroxyalkanoate resin may comprise a second PHA resin.
According to embodiments of the present invention, the second PHA resin can comprise 4-hydroxybutyrate (4-HB) repeat units in an amount of 0.1 wt.% to 30 wt.% and have a melt flow index of 0.1g/10min to 15g/10min measured at 165℃and 5kg according to ASTM D1238.
According to an embodiment of the present invention, the polyhydroxyalkanoate resin may include a first PHA resin and a second PHA resin, and the content of 4-HB repeating units of the first PHA resin and the content of 4-HB repeating units of the second PHA may be different from each other.
According to embodiments of the invention, the weight ratio of the first PHA resin to the second PHA resin may be 1:0.5 to 1:5.
According to an embodiment of the present invention, the polyhydroxyalkanoate resin may be used in an amount of 10 wt% to 100 wt% based on the total weight of the composition for biodegradable fibers.
According to an embodiment of the present invention, the composition for biodegradable fibers may comprise at least one biodegradable resin selected from the group consisting of polybutylene adipate terephthalate (PBAT), polylactic acid (PLA), polybutylene succinate (PBS), polybutylene adipate (PBA), polybutylene succinate-adipate (PBSA), polybutylene succinate-terephthalate (PBST), polyhydroxybutyrate-valerate (PHBV), polycaprolactone (PCL), polybutylene succinate adipate terephthalate (PBSAT), and thermoplastic starch (TPS).
According to an embodiment of the present invention, the biodegradable resin may be used in an amount of 30 wt% or more based on the total weight of the composition for biodegradable fibers, and the weight ratio of the polyhydroxyalkanoate resin to the biodegradable resin may be 1:0.2 to 1:4.5.
According to embodiments of the present invention, the composition for biodegradable fibers may comprise at least one additive selected from the group consisting of pigments, dye absorbers, light absorbers, antioxidants, compatibilizers, weighting agents, nucleating agents, melt enhancers, and slip agents.
According to an embodiment of the present invention, the composition for biodegradable fibers may have a melt flow index of 1g/10min to 30g/10min measured at 190 ℃ and 2.16kg, a melt flow index of 35g/10min to 130g/10min measured at 210 ℃ and 2.16kg, a glass transition temperature (Tg) of-35 ℃ to 15 ℃ measured by Differential Scanning Calorimetry (DSC), a melting temperature (Tm) of 105 ℃ to 200 ℃, and a decomposition temperature (Td, 5% weight loss) of 240 ℃ to 300 ℃ measured by thermogravimetric analyzer (TGA).
The biodegradable fiber according to another embodiment of the present invention comprises a polyhydroxyalkanoate resin comprising 4-hydroxybutyrate (4-HB) repeat units wherein the strength is 0.5g/D to 10g/D as measured according to ASTM D3822.
According to another embodiment of the present invention, the biodegradable fiber may have a diameter of 0.05mm to 10mm, a fineness of 100 denier to 10000 denier, and an elongation of 10% or more.
According to another embodiment of the present invention, the biodegradable fiber may be a composite fiber having a non-uniform cross section, or a composite fiber having two or more or three or more components.
According to another embodiment of the present invention, the biodegradable fiber may be of the sheath-core type comprising a core and a sheath, side-by-side type, islands-in-the-sea type or orange-peel type.
According to an embodiment of the present invention, the core may include a polyhydroxyalkanoate resin, the skin may include a biodegradable resin, and the biodegradable resin may be at least one selected from polybutylene adipate terephthalate (PBAT), polylactic acid (PLA), polybutylene succinate (PBS), polybutylene adipate (PBA), polybutylene succinate-adipate (PBSA), polybutylene succinate-terephthalate (PBST), polyhydroxybutyrate-valerate (PHBV), polycaprolactone (PCL), polybutylene succinate adipate terephthalate (PBSAT), polybutylene adipate succinate acetate (PBEAS), polybutylene succinate acetate (PBES), and thermoplastic starch (TPS).
A method for preparing a biodegradable fiber according to another embodiment of the present invention includes spinning and stretching a composition for a biodegradable fiber or particles prepared by melt extruding the composition, wherein the composition for a biodegradable fiber includes a polyhydroxyalkanoate resin including 4-hydroxybutyrate (4-HB) repeat units and a decomposition temperature (Td, 5% weight loss) measured by a thermogravimetric analyzer (TGA) is 220 ℃ or higher.
According to another embodiment of the present invention, the spinning speed may be 10mpm to 500mpm, the stretching may be performed by cold stretching or hot stretching at a stretching ratio of 1.1 times or more, the cold stretching may be performed at a chamber temperature of 25 ℃ to 35 ℃ and a roller temperature of 25 ℃ to 35 ℃, and the hot stretching may be performed at a chamber temperature of 150 ℃ to 200 ℃ and a roller temperature of 80 ℃ to 130 ℃.
According to another embodiment of the invention, the method may further comprise melt extruding a composition for biodegradable fibers at 150 ℃ to 200 ℃ to prepare particles.
According to another embodiment of the present invention, the step of spinning the particles may be melt spinning the particles at 140 to 190 ℃, and the method may further comprise drying the particles at 40 to 60 ℃ for 10 hours or more before the melt spinning step.
According to another embodiment of the present invention, the spinning step of the composition for biodegradable fibers may be performed using a sheath-core composite spinning apparatus.
According to another embodiment of the invention, the weight ratio of raw materials to be fed to the core and the skin may be 5:95 to 95:5.
According to another embodiment of the invention, the composition for biodegradable fibers may be fed to the core.
Advantageous effects of the invention
The composition for biodegradable fibers according to the embodiment of the present invention comprises a Polyhydroxyalkanoate (PHA) resin, which is a copolymerized polyhydroxyalkanoate resin comprising 4-hydroxybutyrate (4-HB) repeat units, specifically a first PHA resin and/or a second PHA resin each having 4-HB repeat units, wherein a decomposition temperature (Td, 5% weight loss) measured by a thermogravimetric analyzer (TGA) satisfies 220 ℃ or higher. Therefore, characteristics such as flexibility, strength, and workability can be improved while being friendly to the environment due to excellent biodegradability and biocompatibility.
In addition, the biodegradable fiber can be prepared not only directly from the composition for biodegradable fiber, but also using biodegradable particles obtained from the composition for biodegradable fiber, thereby conveniently selecting and applying a process as needed.
Further, since the composition for biodegradable fiber and the biodegradable fiber prepared therefrom are biodegradable in soil and sea and have excellent thermal and mechanical properties, it can be advantageously applied to a wider field to exhibit excellent characteristics.
Detailed Description
The present invention will be described in more detail below. The present invention is not limited to the disclosure given below, but may be modified into various forms as long as the gist of the present invention is not changed.
In this specification, when a component is referred to as being "comprising" an element, it is understood that the component may comprise other elements without excluding other elements unless the context clearly dictates otherwise.
Unless otherwise indicated, all numbers and expressions used herein relating to amounts of components, reaction conditions, and the like, are to be understood as modified by the term "about".
In this specification, the terms first, second, etc. are used to describe various components. The components should not be limited by these terms. These terms are only used to distinguish one component from another.
Composition for biodegradable fibers
Biodegradable fibers represent fibers that become inorganic substances by breaking the chains in the fibers by microorganisms. In recent years, with increasing attention to environmental problems, biodegradable fibers are widely used for the treatment and recovery of various household garbage.
For example, biodegradable fibers are widely used in hygiene and medical products (e.g., diapers, feminine products, sutures and gauzes), household products (e.g., disposable products and outdoor recreational products), industrial products (e.g., packaging materials), agricultural products (e.g., cladding materials), aquatic products (e.g., seaweed nets and fishing nets), and the like.
However, although the biodegradable fiber has advantages of being environmentally friendly and producing less waste, it is difficult to apply the biodegradable fiber to various fields due to limitations in mechanical properties and thermal properties (in particular, physical properties such as flexibility, durability, and strength).
The composition for biodegradable fibers according to an embodiment of the present invention comprises a polyhydroxyalkanoate resin comprising 4-hydroxybutyrate (4-HB) repeat units.
Specifically, the composition for biodegradable fibers according to the embodiment of the present invention comprises a Polyhydroxyalkanoate (PHA) resin, which is a copolymerized polyhydroxyalkanoate resin comprising a 4-hydroxybutyrate (4-HB) repeat unit, specifically a first PHA resin and/or a second PHA resin having a 4-HB repeat unit, wherein the composition for biodegradable fibers is environmentally friendly due to excellent biodegradability and biocompatibility, and can easily prepare biodegradable fibers having excellent characteristics.
Furthermore, conventional compositions for biodegradable fibers are not only expensive, but also do not have physical properties suitable for preparing particles, making it difficult to prepare particles; thus, the process is limited. In contrast, the composition for biodegradable fibers according to the embodiment of the present invention has excellent dispersibility and satisfies physical properties (e.g., glass transition temperature, melting temperature, and decomposition temperature) of an appropriate numerical range; thus, biodegradable particles can be easily prepared using the composition.
Thus, not only the biodegradable fiber can be directly prepared from the composition for biodegradable fiber, but also the biodegradable fiber can be prepared using the biodegradable particles obtained from the composition for biodegradable fiber, thereby providing advantages of conveniently selecting and applying a process according to need.
Further, since the composition for biodegradable fiber and the biodegradable fiber prepared therefrom are biodegradable in soil and sea and have excellent thermal and mechanical properties, it can be advantageously applied to a wider field to exhibit excellent characteristics.
The composition for biodegradable fibers according to an embodiment of the present invention comprises Polyhydroxyalkanoate (PHA) resin.
PHA is a thermoplastic natural polyester polymer that accumulates in microbial cells. Since it is a biodegradable material, it can be composted and eventually decomposed into carbon dioxide, water and organic waste without generating toxic waste. In particular, since PHA is biodegradable (even in soil and ocean), when the composition for biodegradable fiber and the biodegradable fiber prepared using the composition include PHA resin, it may have an environment-friendly characteristic. Thus, the composition for biodegradable fibers and the biodegradable fibers prepared using the composition are remarkably advantageous in that they can be used in various fields because they are biodegradable and environmentally friendly.
In particular, PHA is a thermoplastic natural polyester polymer that accumulates in microbial cells. When certain bacteria are disproportionately supplied with nutrients (nitrogen source, phosphorus, etc.), they are formed by accumulating PHA in the cells, thereby storing carbon and energy.
In addition, PHA has physical properties similar to those of conventional petroleum-derived synthetic polymers such as polybutylene adipate terephthalate (PBAT), polybutylene succinate (PBS), polybutylene succinate terephthalate (PBST) and polybutylene succinate adipate (PBSA), exhibits complete biodegradability, and has excellent biocompatibility.
In particular, unlike other environmentally friendly plastic materials (e.g., PBS, PLA, and PTT), PHA can be synthesized from more than 150 types of monomers, and thus hundreds of types of PHA can be prepared according to monomer types. Hundreds of different types of PHA, depending on the type of monomer, have quite different structures and properties.
PHA resins may be composed of single monomer repeat units in living cells and may be formed from the polymerization of one or more monomer repeat units. Specifically, the PHA resin may be a HOMO-polyhydroxyalkanoate resin (hereinafter referred to as HOMO PHA resin) or a co-polyhydroxyalkanoate resin (hereinafter referred to as co-PHA resin) (i.e. a copolymer in which different repeating units are randomly distributed in the polymer chain).
Examples of repeating units that may be included in the PHA resin include 2-hydroxybutyrate, lactic acid, glycolic acid, 3-hydroxybutyrate (hereinafter 3-HB), 3-hydroxypropionate (hereinafter 3-HP), 3-hydroxyvalerate (hereinafter 3-HV), 3-hydroxyhexanoate (hereinafter 3-HH), 3-hydroxyheptanoate (hereinafter 3-HHEP), 3-hydroxyoctanoate (hereinafter 3-HO), 3-hydroxynonanoate (hereinafter 3-HN), 3-hydroxydecanoate (hereinafter 3-HD), 3-hydroxydodecanoate (hereinafter 3-HDd), 4-hydroxybutyrate (hereinafter 4-HB), 4-hydroxyvalerate (hereinafter 4-HV), 5-hydroxyvalerate (hereinafter 5-HV), and 6-hydroxyhexanoate (hereinafter 6-HH). The PHA resin may comprise one or more repeat units selected from the above-mentioned repeat units.
In particular, the PHA resin may comprise one or more repeating units selected from the group consisting of 3-HB, 4-HB, 3-HP, 3-HH, 3-HV, 4-HV, 5-HV, and 6-HH.
More specifically, the PHA resin may comprise 4-HB repeat units in an amount of 0.1 wt.% to 100 wt.%. For example, the PHA resin may comprise 4-HB repeat units in an amount of 0.2 wt% to 100 wt%, 0.5 wt% to 100 wt%, 1 wt% to 100 wt%, 5 wt% to 100 wt%, 10 wt% to 100 wt%, 20 wt% to 100 wt%, 30 wt% to 100 wt%, 40 wt% to 100 wt%, 50 wt% to 100 wt%, 60 wt% to 100 wt%, 70 wt% to 100 wt%, 80 wt% to 100 wt%, or 90 wt% to 100 wt%.
That is, the PHA resin may be a HOMO PHA resin consisting of only 4-HB repeating units, or a copolymerized PHA resin comprising 4-HB repeating units.
Further, the PHA resin may be a copolymerized PHA resin comprising 4-HB repeating units, and further comprising one repeating unit other than 4-HB repeating units, or comprising two, three, four, five, six, or more repeating units other than one another. For example, the PHA resin may be poly-3-hydroxybutyrate-co-4-hydroxybutyrate (hereinafter 3 HB-co-4 HB).
In addition, the PHA resin may comprise isomers. For example, the PHA resin may comprise structural isomers, enantiomers or geometric isomers. In particular, PHA resins may comprise structural isomers.
Further, the PHA resin may be a copolymerized PHA resin having controlled crystallinity. For example, the PHA resin may comprise at least one or more 4-HB repeat units, and the content of 4-HB repeat units may be controlled to adjust the crystallinity of the PHA resin.
For example, the PHA resin may be a copolymerized PHA resin comprising at least one repeating unit selected from the group consisting of 3-hydroxybutyrate (3-HB), 4-hydroxybutyrate (4-HB), 3-hydroxypropionate (3-HP), 3-hydroxycaproate (3-HH), 3-hydroxyvalerate (3-HV), 4-hydroxyvalerate (4-HV), 5-hydroxyvalerate (5-HV), and 6-hydroxycaproate (6-HH).
Specifically, the copolymerized PHA resin may comprise 4-HB repeat units, and further comprise one or more repeat units selected from the group consisting of 3-HB repeat units, 3-HP repeat units, 3-HH repeat units, 3-HV repeat units, 4-HV repeat units, 5-HV repeat units, and 6-HH repeat units. More specifically, the PHA resin may comprise 4-HB repeat units and 3-HB repeat units.
More specifically, the PHA resin may be a copolymerized PHA resin comprising 4-HB repeating units and 3-HB repeating units, and may comprise 4-HB repeating units in an amount of 0.1 wt.% to 60 wt.%. For example, the PHA resin may comprise 4-HB repeat units in an amount of 0.1% to 55%, 0.5% to 50%, 1% to 49%, 3% to 48%, 5% to 48%, 6% to 35%, 7% to 30%, 15% to 50%, 10% to 40%, 10% to 30%, 10% to 20%, 20% to 30%, 20% to 40%, 35% to 49% or 6% to 28% by weight.
Further, the PHA resin may be a copolymerized PHA resin that includes 4-HB repeating units and 3-HB repeating units, and may include 3-HB repeating units in an amount of 20 wt.% or more. For example, the PHA resin may comprise 3-HB repeat units in an amount of 35% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more or 75% by weight or more and 99% by weight or less, 98% by weight or less, 97% by weight or less, 96% by weight or less, 95% by weight or less, 93% by weight or less, 91% by weight or less, 90% by weight or less, 80% by weight or less, 70% by weight or less, 60% by weight or less, or 55% by weight or less.
The PHA resin capable of adjusting crystallinity may be a PHA resin whose crystallinity and amorphous state are adjusted as irregularities in its molecular structure increase. Specifically, the type or proportion of the monomer or the type or content of the isomer may be adjusted.
According to embodiments of the present invention, the PHA resin may comprise two or more types of PHA resins having different degrees of crystallinity. Specifically, the PHA resin may be prepared by mixing two or more types of PHA resins having different crystallinity so that the content of 4-HB repeating units is within a specific range.
In particular, the PHA resin may comprise a first PHA that is an amorphous PHA resin having a controlled degree of crystallinity.
As an amorphous PHA resin (hereinafter referred to as an aapha resin) having a controlled crystallinity, the first PHA resin may include 4-HB repeating units in an amount of 15 to 60 wt%, 15 to 55 wt%, 20 to 55 wt%, 25 to 55 wt%, 30 to 55 wt%, 35 to 55 wt%, 20 to 50 wt%, 25 to 50 wt%, 30 to 50 wt%, 35 to 50 wt%, or 20 to 40 wt%.
The glass transition temperature (Tg) of the first PHA resin may be-45 ℃ to-10 ℃, 35 ℃ to-15 ℃, 35 ℃ to-20 ℃, or 30 ℃ to-20 ℃. In addition, the crystallization temperature (Tc) of the first PHA resin may not be measured or may be 60 ℃ to 120 ℃,60 ℃ to 110 ℃,70 ℃ to 120 ℃, or 75 ℃ to 115 ℃. The melting temperature (Tm) of the first PHA resin may not be measured or may be 100 ℃ to 170 ℃,100 ℃ to 160 ℃,110 ℃ to 160 ℃, or 120 ℃ to 150 ℃.
In this specification, the glass transition temperature (Tg), crystallization temperature (Tc), and melting temperature (Tm) can be measured using a Differential Scanning Calorimeter (DSC). Specifically, the glass transition temperature (Tg), crystallization temperature (Tc), and melting temperature (Tm) may be measured by performing a first scan or a second scan in a Differential Scanning Calorimetry (DSC) mode, and these temperatures may be determined from the heat flow curves obtained by these scans. More specifically, the glass transition temperature (Tg), crystallization temperature (Tc), and melting temperature (Tm) may be determined from a heat flow curve obtained by raising the temperature from 40 ℃ to 180 ℃ at a rate of 10 ℃/min and then cooling the temperature to-50 ℃ at a rate of 10 ℃/min.
The first PHA resin can have a Melt Flow Index (MFI) of 0.1g/10min to 20g/10min, measured at 165℃and 5kg according to ASTM D1238. For example, the first PHA resin may have a Melt Flow Index (MFI) of 0.1g/10min to 15g/10min,0.1g/10min to 12g/10min,0.1g/10min to 10g/10min,0.1g/10min to 8g/10min,0.1g/10min to 6g/10min,0.1g/10min to 5.5g/10min,0.5g/10min to 10g/10min,1g/10min to 10g/10min,2g/10min to 8g/10min,3g/10min to 6g/10min, or 3g/10min to 5.5g/10min, as measured according to ASTM D1238 at 165℃and 5 kg.
The first PHA resin can have a weight average molecular weight of 10000g/mol to 1200000g/mol,10000g/mol to 1000000g/mol,50000g/mol to 1000000g/mol,200000g/mol to 1200000g/mol,250000g/mol to 1000000g/mol,100000g/mol to 900000g/mol,500000g/mol to 900000g/mol,200000g/mol to 800000g/mol, or 200000g/mol to 500000g/mol.
Further, the PHA resin may comprise a second PHA resin, the second PHA resin being a semi-crystalline PHA resin.
As a semi-crystalline PHA resin having controlled crystallinity (hereinafter referred to as scPHA resin), the second PHA resin may comprise 4-HB repeating units in an amount of 0.1% to 30% by weight. For example, the second PHA resin may include 4-HB repeat units in an amount of 0.1% to 30% by weight, 0.5% to 30% by weight, 1% to 29% by weight, 3% to 29% by weight, 1% to 28% by weight, 1.5% to 25% by weight, 2% to 20% by weight, 2.5% to 15% by weight, 3% to 25% by weight, 5% to 21% by weight, 7% to 18% by weight, 10% to 30% by weight, 10% to 20% by weight, 15% to 23% by weight, or 20% to 30% by weight.
The glass transition temperature (Tg) of the second PHA resin may be-30 ℃ to 80 ℃, -30 ℃ to 10 ℃, -25 ℃ to 5 ℃, -25 ℃ to 0 ℃, -20 ℃ to 0 ℃ or-15 ℃ to 0 ℃. The crystallization temperature (Tc) of the second PHA resin may be 70 ℃ to 120 ℃,75 ℃ to 120 ℃, or 75 ℃ to 115 ℃. The second PHA resin may have a melting temperature (Tm) of 105 ℃ to 165 ℃,110 ℃ to 160 ℃,115 ℃ to 155 ℃, or 120 ℃ to 150 ℃.
Further, the second PHA resin can have a melt flow index of 0.1g/10min to 15g/10min, measured at 165℃and 5kg according to ASTM D1238. For example, the Melt Flow Index (MFI) of the second PHA resin, measured at 165℃and 5kg according to ASTM D1238, can be 0.1g/10min to 10g/10min,0.2g/10min to 7g/10min,0.5g/10min to 5.5g/10min,0.6g/10min to 5g/10min,0.8g/10min to 5g/10min,1g/10min to 5g/10min,0.1g/10min to 5g/10min,1g/10min to 6.5g/10min,1.5g/10min to 15g/10min,3g/10min to 10g/10min,3.5g/10min to 12g/10min, or 4.5g/10min to 10g/10min.
The second PHA resin can have a weight average molecular weight of 10000g/mol to 1200000g/mol,50000g/mol to 1100000g/mol,50000g/mol to 350000g/mol,100000g/mol to 1000000g/mol,100000g/mol to 900000g/mol,200000g/mol to 800000g/mol,200000g/mol to 600000g/mol,200000g/mol to 500000g/mol, or 500000g/mol to 1200000g/mol.
The first PHA resin and the second PHA resin may be distinguished according to the content of 4-HB repeating units, and may have at least one characteristic selected from the group consisting of glass transition temperature (Tg), crystallization temperature (Tc), melting temperature (Tm), and melt flow index. Specifically, the first PHA and the second PHA can be distinguished according to the content of 4-HB repeating units, glass transition temperature (Tg), crystallization temperature (Tg), melting temperature (Tm), melt flow index, and the like. For example, the content of 4-HB repeat units of the first PHA resin and the content of 4-HB repeat units of the second PHA can be different from each other.
According to embodiments of the invention, the PHA resin may comprise a first PHA resin or a second PHA resin, or it may comprise a first PHA resin and a second PHA resin.
Specifically, when the PHA resin comprises a first PHA resin (which is an amorphous PHA resin) or comprises a first PHA resin (which is an amorphous PHA resin) and a second PHA resin (which is a semi-crystalline PHA resin), more particularly, when the contents of the first and second PHA resins are adjusted, desired physical properties can be more effectively controlled.
According to embodiments of the present invention, the PHA resin may comprise a first PHA resin or a second PHA resin. In particular, the PHA resin may consist of only the first PHA resin or only the second PHA.
According to another embodiment of the present invention, the PHA resin may comprise a first PHA resin and a second PHA resin. In this case, the weight ratio of the first PHA resin to the second PHA resin may be 1:0.5 to 1:5. For example, the weight ratio of the first PHA resin to the second PHA resin may be 1:0.5 to 1:4.5, 1:0.6 to 1:4.2, or 1:0.7 to 1:3.5. When the weight ratio of the first PHA resin to the second PHA resin satisfies the above range, the desired physical properties can be more effectively controlled.
Furthermore, the glass transition temperature (Tg) of the PHA resin may be-45 ℃ to 80 ℃, 35 ℃ to 80 ℃, 30 ℃ to 80 ℃, 25 ℃ to 75 ℃, 20 ℃ to 70 ℃, 35 ℃ to 5 ℃, 25 ℃ to 5 ℃, 35 ℃ to 0 ℃, 25 ℃ to 0 ℃, 30 ℃ to 10 ℃, 35 ℃ to 15 ℃, 35 ℃ to 20 ℃, 20 ℃ to 0 ℃, 15 ℃ to 0 ℃, or 15 ℃ to 5 ℃.
In addition, the crystallization temperature (Tc) of the PHA resin may not be measured, or may be 60 ℃ to 120 ℃,60 ℃ to 110 ℃,70 ℃ to 120 ℃,75 ℃ to 115 ℃,75 ℃ to 110 ℃, or 90 ℃ to 110 ℃.
The melting temperature (Tm) of the PHA resin may not be measured or may be 100 ℃ to 170 ℃,105 ℃ to 165 ℃,110 ℃ to 160 ℃,115 ℃ to 155 ℃,110 ℃ to 150 ℃,120 ℃ to 150 ℃, or 120 ℃ to 140 ℃.
The decomposition temperature (Td, 5% weight loss) of the PHA resin as measured by thermogravimetric analysis (TGA) may be 220 ℃ to 280 ℃,245 ℃ to 275 ℃,255 ℃ to 270 ℃, or 260 ℃ to 270 ℃.
In this specification, the decomposition temperature (Td) may be measured using a thermogravimetric analyzer (TGA). Specifically, the decomposition temperature (Td) may be determined as a temperature at which the weight of the PHA resin is reduced by 5% on a weight change curve obtained by raising the temperature from room temperature to 600 ℃ at a rate of 10 ℃/min using a thermogravimetric analyzer (TGA).
In addition, the PHA resin may have a weight average molecular weight of 10000g/mol to 1200000g/mol. For example, the PHA resin can have a weight average molecular weight of 50000g/mol to 1200000g/mol,100000g/mol to 1000000g/mol,200000g/mol to 1200000g/mol,250000g/mol to 1150000g/mol,300000g/mol to 1100000g/mol,350000g/mol to 950000g/mol,100000g/mol to 900000g/mol,200000g/mol to 800000g/mol,250000g/mol to 650000g/mol,200000g/mol to 400000g/mol,300000g/mol to 600000g/mol,500000g/mol to 1200000g/mol,500000g/mol to 1000000g/mol,55000 g/mol to 1050000g/mol,55000 g/mol to 900000g/mol,600000g/mol to 900000g/mol, or 500000 g/to 900000g/mol.
The PHA resin may have a crystallinity of 90% or less as measured by a Differential Scanning Calorimeter (DSC). For example, the crystallinity of the PHA resin may be measured by differential scanning calorimetry, and may be 90% or less, 85% or less, 80% or less, 75% or less, or 70% or less.
In addition, the PHA resin may have an average particle size of 0.5 μm to 5 μm. For example, the PHA resin may have an average particle size of 0.7 μm to 4.6 μm,1.1 μm to 4.5 μm,1.5 μm to 4.3 μm,2.2 μm to 4.2 μm,2.6 μm to 4.0 μm,2.8 μm to 3.9 μm, or 3.1 μm to 3.8 μm.
The average particle size of the PHA resin can be measured using a nano-particle size analyzer (e.g., zetasizer Nano ZS). Specifically, PHA was measured for average particle size by Dynamic Light Scattering (DLS) using Zetasizer Nano ZS (manufacturer: marven) at a temperature of 25℃and a measurement angle of 175 ℃. In this case, the peak obtained by the polydispersity index (PDI) with a confidence interval of 0.5 was taken as the particle size.
The PHA resin may have a polydispersity index (PDI) of less than 2.5. For example, the polydispersity index of the PHA resin may be less than 2.5,2.3 or less, 2.1 or less or 2.0 or less.
In addition, PHA resins can be obtained by cell disruption using non-mechanical or chemical methods. In particular, since the PHA resin is a thermoplastic natural polyester polymer accumulated in microbial cells and has a relatively large average particle size, it can be obtained through a crushing method, thereby more effectively controlling the yield or physical properties of a desired material and improving process efficiency.
Meanwhile, according to another embodiment of the present invention, the composition for biodegradable fiber may include at least one biodegradable resin selected from the group consisting of polybutylene adipate terephthalate (PBAT), polylactic acid (PLA), polybutylene succinate (PBS), polybutylene adipate (PBA), polybutylene succinate-adipate (PBSA), polybutylene succinate-terephthalate (PBST), polyhydroxybutyrate-valerate (PHBV), polycaprolactone (PCL), polybutylene succinate adipate terephthalate (PBSAT), polybutylene adipate succinate (PBEAS), polybutylene succinate acetate (PBES), and thermoplastic starch (TPS).
Since the biodegradable resin is used together with the PHA resin, the composition for biodegradable fiber has excellent dispersibility, and properties such as melt flow index, glass transition temperature, melting temperature, and decomposition temperature can be further improved.
The composition for biodegradable fibers may comprise the polyhydroxyalkanoate resin in an amount of 10 wt% to 100 wt%, based on the total weight of the composition for biodegradable fibers. For example, the polyhydroxyalkanoate resin may be present in an amount of 10 wt% or more, 12 wt% or more, 15 wt% or more, 20 wt% or more, 25 wt% or more or 30 wt% or more and 100 wt% or less, 95 wt% or less, 90 wt% or less, 85 wt% or less, 80 wt% or less, 75 wt% or less or 70 wt% or less. Specifically, the content of the polyhydroxyalkanoate resin may be 10 wt% to 85 wt%, but is not limited thereto.
The composition for biodegradable fibers may contain the biodegradable resin in an amount of 30% by weight or more based on the total weight of the composition for biodegradable fibers. For example, the content of the biodegradable resin may be 32% by weight or more, 35% by weight or more, 50% by weight or more, 55% by weight or more, or 65% by weight or more. Further, the content of the biodegradable resin may be 95% by weight or less, 90% by weight or less, 85% by weight or less, 80% by weight or less, or 70% by weight or less.
In addition, the weight ratio of polyhydroxyalkanoate resin to biodegradable resin may be 1:0.2 to 1:4.5. For example, the weight ratio of polyhydroxyalkanoate resin to biodegradable resin may be 1:0.2 to 1:4.2,1:0.3 to 1:3.8,1:0.4 to 1:3,1:0.45 to 1:2.8,1:0.5 to 1:2.5,1:0.8 to 1:2.4, or 1:1 to 1:2.35.
In addition, the composition for biodegradable fibers may further comprise at least one additive selected from pigments, dye absorbers, light absorbers, antioxidants, compatibilizers, weighting agents, nucleating agents, melt enhancers, and slip agents.
The pigment may include at least one selected from carbon black and cobalt green. The pigment may further be used in an amount of 0.01 to 20 wt%, 0.01 to 15 wt%, 0.01 to 12 wt%, 0.01 to 10 wt%, 0.01 to 8 wt%, 0.01 to 5 wt%, 0.2 to 4.5 wt%, 0.2 to 4 wt%, or 0.5 to 3 wt%, based on the total weight of the composition for the biodegradable fiber.
An antioxidant is an additive for preventing decomposition by ozone or oxygen, oxidation during storage, or deterioration of physical properties. Conventional antioxidants may be used as long as the effects of the present invention are not impaired.
Specifically, the antioxidant may include at least one selected from hindered phenol-based antioxidants and phosphate-based (phosphorus-based) antioxidants.
The hindered phenol type antioxidant may include, for example, at least one selected from 4,4' -methylene-bis (2, 6-di-tert-butylphenol), octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythritol tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and 3, 9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) -propionyloxy ] -1, 1-dimethylethyl ] -2,4,8, 10-tetraoxaspiro [5.5] undecane.
The phosphate (phosphorus-based) antioxidant may include, for example, at least one selected from tris (2, 4-di-t-butylphenyl) phosphite, bis (2, 4-di-t-butylphenyl) pentaerythritol-diphosphite, bis (2, 6-di-t-butyl-4-methylphenyl) pentaerythritol-diphosphite, distearyl pentaerythritol diphosphite, [ bis (2, 4-di-t-butyl-5-methylphenoxy) phosphino ] biphenyl, and N, N-bis [2- [ [2,4,8, 10-tetrakis (1, 1-dimethylethyl) dibenzo [ d, f ] [1,3,2] dioxaphosphepin-6-yl ] oxy ] ethyl ] ethylamine.
The antioxidant may further be used in an amount of 0.01 to 20 wt%, 0.01 to 15 wt%, 0.01 to 12 wt%, 0.01 to 10 wt%, 0.01 to 8 wt%, 0.01 to 5 wt%, 0.2 to 4.5 wt%, 0.2 to 4 wt%, or 0.5 to 3 wt%, based on the total weight of the composition for biodegradable fibers. When the content of the antioxidant satisfies the above range, the physical properties of the fiber can be improved, and this may be more advantageous in obtaining the desired effect of the present invention.
A compatibilizer is an additive that imparts compatibility by removing the releasability of the biodegradable resin and/or PHA resin. Conventional compatibilizers may be used as long as the effects of the present invention are not impaired.
Specifically, the compatibilizer may include at least one selected from polyvinyl acetate (PVAc), isocyanate, polypropylene carbonate, glycidyl methacrylate, ethylene-vinyl alcohol, polyvinyl alcohol (PVA), ethylene vinyl acetate, and maleic anhydride.
The compatibilizer may further be used in an amount of 0.01 to 20 wt%, 0.01 to 15 wt%, 0.01 to 12 wt%, 0.01 to 10 wt%, 0.01 to 8 wt%, 0.01 to 5 wt%, 0.2 to 4.5 wt%, 0.2 to 4 wt%, or 0.5 to 3 wt%, based on the total weight of the composition for the biodegradable fiber. When the content of the compatibilizer satisfies the above range, the physical properties of the fiber can be improved by increasing the compatibility between the resins used, and this may be more advantageous in obtaining the desired effect of the present invention.
Weighting agents are an inorganic material and additives for improving formability by increasing crystallization rate during the forming process and for reducing the cost increase problems caused by the use of biodegradable resins. Conventional inorganic materials may be used as long as the effects of the present invention are not impaired.
The weighting agent may include at least one selected from inorganic materials (e.g., zinc and calcium, stearic acid, light or heavy calcium carbonate, silica, talc, kaolin, barium sulfate, clay, calcium oxide, magnesium hydroxide, titanium oxide, carbon black, and glass fibers).
The weighting agent may have an average particle size of 0.5 μm to 5 μm. For example, the average particle size of the weighting agent may be 0.5 μm to 4.8 μm,0.5 μm to 4.5 μm, or 0.7 μm to 4 μm. If the average particle size of the weighting agent is less than 0.5 μm, it is difficult to disperse the particles. If it exceeds 5 μm, the size of the particles becomes excessively large, which may impair the effect of the present invention.
The weighting agent may further be used in an amount of 0.01 wt% to 20 wt%, 0.01 wt% to 15 wt%, 0.01 wt% to 12 wt%, 0.01 wt% to 10 wt%, 0.01 wt% to 8 wt%, 0.01 wt% to 5 wt%, 0.2 wt% to 4.5 wt%, 0.2 wt% to 4 wt%, or 0.5 wt% to 3 wt%, based on the total weight of the composition for biodegradable fibers. When the content of weighting agent satisfies the above range, it may be more advantageous to obtain the desired effect of the present invention.
A nucleating agent is an additive that is used to supplement or alter the crystalline morphology of a polymer and to increase the rate of crystallization (solidification) as the polymer melt cools. In particular, because the PHA resin used in the present invention has a low crystallization rate, the process may be difficult to perform due to lack of crystallization during the process. If a nucleating agent is used to solve this problem, the crystallization rate can be increased to further improve processability, moldability and productivity, and desired physical properties can be effectively obtained.
Conventional nucleating agents may be used as long as the effects of the present invention are not impaired. Specifically, the nucleating agent may include, for example, a metal compound containing a single element substance (pure substance) or a complex oxide, a low molecular weight organic compound having a metal carboxylate group, a polymer organic compound, phosphoric acid or phosphorous acid or a metal salt thereof, a sorbitol derivative, mercaptoacetic anhydride, p-toluenesulfonic acid or a metal salt thereof, or the like. The nucleating agents may be used alone or in combination.
The metal compound containing a single element substance (pure substance) or a composite oxide may be, for example, at least one selected from carbon black, calcium carbonate, synthetic silicic acid and salts thereof, silica, zinc white, clay, kaolin, basic magnesium carbonate, mica, talc, quartz powder, diatomaceous earth, dolomite powder, titanium oxide, zinc oxide, antimony oxide, barium sulfate, calcium sulfate, aluminum oxide, calcium silicate, metal salts of organic phosphorus, and boron nitride.
The low molecular weight organic compound having a metal carboxylate group may be, for example, at least one metal salt selected from the group consisting of caprylic acid, toluic acid, heptanoic acid, nonanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, cerotic acid, montanic acid, melissic acid, benzoic acid, p-tert-butylbenzoic acid, terephthalic acid, monomethyl terephthalate, isophthalic acid, and monomethyl isophthalate.
The polymer organic compound having a metal carboxylate group may be, for example, at least one selected from the group consisting of a carboxyl group-containing polyethylene obtained by an oxidation reaction of polyethylene, a carboxyl group-containing polypropylene obtained by an oxidation reaction of polypropylene, a copolymer of acrylic acid or methacrylic acid with an olefin (e.g., ethylene, propylene, and 1-butene), a copolymer of acrylic acid or methacrylic acid with styrene, a copolymer of an olefin with maleic anhydride, and a metal salt of a copolymer of styrene with maleic anhydride.
The polymer organic compound may be, for example, at least one selected from α -olefins branched to carbon atoms at the position 3 and having 5 or more carbon atoms (e.g., 3-dimethyl-1-butene, 3-methyl-1-pentene, 3-methyl-1-hexene, and 3, 5-trimethyl-1-hexene), vinylcycloalkanes (e.g., vinylcyclopentane, vinylcyclohexane, and vinylnorbornane), polyolefin alcohols (e.g., polyethylene glycol and polypropylene glycol), poly (glycolic acid), cellulose esters, and cellulose ethers.
The phosphoric acid or phosphorous acid or a metal salt thereof may be, for example, at least one selected from the group consisting of diphenyl phosphate, diphenyl phosphite, bis (4-t-butylphenyl) phosphate and methylenebis (2, 4-t-butylphenyl) phosphate. The sorbitol derivative may be, for example, bis (p-methylbenzylidene) sorbitol or bis (p-ethylbenzylidene) sorbitol.
The nucleating agent may further be used in an amount of 0.01 to 20 wt%, 0.01 to 15 wt%, 0.01 to 12 wt%, 0.01 to 10 wt%, 0.01 to 8 wt%, 0.01 to 5 wt%, 0.2 to 4.5 wt%, 0.2 to 4 wt%, or 0.5 to 3 wt%, based on the total weight of the composition for biodegradable fibers. When the content of the nucleating agent satisfies the above range, the crystallization rate may be increased to improve the processability, and the productivity and the moldability may be further improved by, for example, increasing the crystallization rate during the cutting step for producing the pellets in the production method.
A melt enhancer is an additive that is used to increase the melt strength of a reactant. Conventional melt enhancers may be used as long as the effect of the present invention is not impaired.
In particular, the melt enhancer may include at least one selected from polyesters, styrenic polymers (e.g., acrylonitrile butadiene styrene and polystyrene), polysiloxanes, organically modified siloxane polymers, and maleic anhydride grafted ethylene propylene diene monomer (MAH-g-EPDM).
The melt reinforcement may further be used in an amount of 0.01 to 20 wt%, 0.01 to 15 wt%, 0.01 to 12 wt%, 0.01 to 10 wt%, 0.01 to 8 wt%, 0.01 to 5 wt%, 0.2 to 4.5 wt%, 0.2 to 4 wt%, or 0.5 to 3 wt%, based on the total weight of the composition for biodegradable fibers. When the content of the melt reinforcing agent satisfies the above range, it may be more advantageous to obtain the desired effect of the present invention.
A slip agent is an additive for improving the slip properties (slip properties) during extrusion and for preventing the fiber surfaces from adhering to each other. In particular, a conventional slipping agent may be used as long as the effect of the present invention is not impaired. For example, the slip agent may be at least one selected from erucamide, oleamide, and stearamide.
The slip agent may further be used in an amount of 0.01 to 20 wt%, 0.01 to 15 wt%, 0.01 to 12 wt%, 0.01 to 10 wt%, 0.01 to 8 wt%, 0.01 to 5 wt%, 0.2 to 4.5 wt%, 0.2 to 4 wt%, or 0.5 to 3 wt%, based on the total weight of the composition for biodegradable fibers. When the content of the slip agent satisfies the above range, the processability, productivity, and moldability can be further improved, and this may be more advantageous in obtaining the desired effect of the present invention.
The biodegradable resin composition may contain a crosslinking agent and/or a stabilizer as other additives.
The crosslinking agent is an additive that is used to alter the properties of the PHA resin and increase the molecular weight of the resin. Conventional crosslinking agents may be used as long as the effects of the present invention are not impaired.
For example, the crosslinking agent may be at least one selected from the group consisting of fatty acid esters, natural oils containing epoxy groups (epoxidised), diallyl phthalate, pentaerythritol tetraacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, diethylene glycol dimethacrylate and bis (2-methacryloyloxyethyl) phosphate.
The crosslinking agent may further be used in an amount of 0.01 to 20 wt%, 0.01 to 15 wt%, 0.01 to 12 wt%, 0.01 to 10 wt%, 0.01 to 8 wt%, 0.01 to 5 wt%, 0.2 to 4.5 wt%, 0.2 to 4 wt%, or 0.5 to 3 wt%, based on the total weight of the composition for biodegradable fibers.
The stabilizer may be at least one selected from trimethyl phosphate, triphenyl phosphate, trimethyl phosphine, phosphoric acid and phosphorous acid.
The stabilizing agent may further be used in an amount of 0.01 to 20 wt%, 0.01 to 15 wt%, 0.01 to 12 wt%, 0.01 to 10 wt%, 0.01 to 8 wt%, 0.01 to 5 wt%, 0.2 to 4.5 wt%, 0.2 to 4 wt%, or 0.5 to 3 wt%, based on the total weight of the composition for biodegradable fibers.
According to another embodiment of the present invention, the composition for biodegradable fibers may further comprise biomass.
When the composition for biodegradable fibers contains biomass, it is possible to improve biodegradability and improve soil. Namely, the biomass has excellent biodegradability, is easily destroyed when not decomposed, improves fertilizer and increases soil strength, thereby producing soil improvement effect.
The biomass may be used in an amount of 5 to 50 wt% based on the total weight of the composition for biodegradable fibers. Specifically, the biomass may be present in an amount of 10 to 48 wt%, 15 to 48 wt%, 20 to 45 wt%, 20 to 43 wt%, or 20 to 40 wt%, based on the total weight of the composition for biodegradable fibers. When the content of biomass satisfies the above range, biodegradability is further improved, soil improvement effect is produced, and crosslinking strength with PHA resin is improved, so that the desired effect of the present invention can be effectively obtained.
The composition for biodegradable fibers may have a melt flow index of 1g/10min to 30g/10min measured at 190 ℃ and 2.16kg according to ASTM D1238. For example, the composition for biodegradable fibers may have a melt flow index of 2.3g/10min to 28g/10min,2.3g/10min to 26g/10min,2.5g/10min to 22g/10min,3.3g/10min to 20g/10min,3.5g/10min to 19g/10min,4g/10min to 18.5g/10min,4.5g/10min to 18g/10min,1.5g/10min to 10g/10min,2.5g/10min to 8.5g/10min,3.2g/10min to 6.5g/10min,4.2g/10min to 6g/10min,11g/10min to 25g/10min,11.5g/10min to 21g/10min, or 12g/10min to 17.5g/10min measured according to ASTM D1238 at 190 ℃ and 2.16 kg.
In addition, the composition for biodegradable fibers may have a melt flow index of 35g/10min to 130g/10min measured at 210℃and 2.16kg according to ASTM D1238. For example, the melt flow index of the composition for biodegradable fibers may be 40g/10min to 120g/10min,42g/10min to 115g/10min,48g/10min to 112g/10min,50g/10min to 110g/10min, or 55g/10min to 108g/10min measured at 210 ℃ and 2.16kg according to ASTM D1238.
For particles prepared using the composition for biodegradable fibers, the melt flow index of the composition for biodegradable fibers, measured according to ASTM D1238, can be measured according to ASTM D1238.
Specifically, the melt flow index of biodegradable particles prepared by feeding the composition for biodegradable fibers to a twin screw extruder, mixing and melt extruding may be measured according to ASTM D1238. More specifically, the biodegradable particles may be prepared by: the screw rotation speed of the twin screw extruder was set to 200rpm, the composition for biodegradable fibers was mixed while the internal temperature was raised from 50 ℃ to 170 ℃, melt extrusion was performed at a pressure of 12 bar and a temperature of 177 ℃, and an underwater cutting system was used.
The composition for biodegradable fibers may have a glass transition temperature (Tg) of-35 ℃ to 15 ℃,25 ℃ to 5 ℃, 20 ℃ to 1 ℃ or 18 ℃ to 5 ℃ and a melting temperature (Tm) of 105 ℃ to 200 ℃,106 ℃ to 195 ℃,110 ℃ to 180 ℃, or 113 ℃ to 173 ℃ as measured by a Differential Scanning Calorimeter (DSC).
In addition, the composition for biodegradable fibers may have a decomposition temperature (Td, 5% weight loss) of 220 ℃ or more, 230 ℃ or more, 240 ℃ or more, 250 ℃ or more, or 260 ℃ or more, 220 ℃ to 275 ℃,235 ℃ to 273 ℃,240 ℃ to 300 ℃,245 ℃ to 285 ℃,255 ℃ to 280 ℃,260 ℃ to 275 ℃, or 263 ℃ to 270 ℃ as measured by thermogravimetric analyzer (TGA).
Biodegradable fibers
The biodegradable fiber according to another embodiment of the present invention comprises a polyhydroxyalkanoate resin comprising 4-hydroxybutyrate (4-HB) repeat units wherein the strength is 0.5g/D to 10g/D as measured according to ASTM D3822.
Biodegradable fibers can be prepared using a composition for biodegradable fibers. Details concerning the polyhydroxyalkanoate resin are as set forth above.
For example, the biodegradable fiber may have a strength of 0.5g/D or higher, 0.6g/D or lower, 0.75g/D or higher, 0.8g/D or higher, 0.9g/D or higher, 1g/D or higher, 1.1g/D or higher, 1.2g/D or higher, 1.5g/D or higher, 1.8g/D or higher, or 2g/D or higher, 10g/D or lower, 8.5g/D or lower, 7g/D or lower, 5.5g/D or lower, 5g/D or lower, 4.8g/D or lower, 4.5g/D or lower, 4.2 or lower, 3.9g/D or lower, 3.2g/D or lower, 2.9g/D or lower, 2.8g/D or lower, 8.5g/D to 3.1g/D, 3.5g/D to 3.1g/D, 2.5 g/D to 3.1g/D, 3.9g/D to 3.1g/D, 3.5g/D to 3.1.9 g/D, 2.1 g/D to 3.9g/D, 0.1 g/D to 2.9g/D or 3.1.9 g to 2g/D, 3.1.8 g/D to 2.8g/D or 3.1.9 g/2.2 g/2 g/D or lower, measured according to ASTM D3822.
Further, the biodegradable fiber may have a diameter of 0.05mm to 10mm and a fineness of 100 denier to 10000 denier. For example, the biodegradable fiber may be monofilament, wherein the biodegradable fiber may have a diameter of 0.06mm to 8mm,0.08mm to 6mm,0.1mm to 4mm,0.15mm to 2mm,0.2mm to 1mm, or 0.25mm to 0.6mm, and the biodegradable fiber may have a fineness of 120 denier to 8500 denier, 150 denier to 5500 denier, 200 denier to 4000 denier, 500 denier to 2500 denier, 650 denier to 2200 denier, 700 denier to 1950 denier, 800 denier to 1350 denier, 900 denier to 1800 denier, or 950 denier to 1600 denier.
Further, the biodegradable fiber may have an elongation of 10% or more, 12% or more, 15% or more, 20% or more, 25% or more, 32% or more, 35% or more, 40% or more, 45% or more, 50% or more, or 60% or more and 1000% or less, 850% or less, 650% or less, 500% or less, 350% or less, 200% or less, 130% or less, 90% or less, 80% or less, or 75% or less.
The weight average molecular weight of the biodegradable fiber may be 300000g/mol or more or 500000g/mol or more, 10000g/mol to 5000000g/mol,20000g/mol to 4000000g/mol or 50000g/mol to 3000000g/mol.
According to another embodiment of the present invention, the biodegradable fiber may be a composite fiber having a non-uniform cross section, or a composite fiber having two or more or three or more components.
The non-uniform cross-section fibers may have a circular, elliptical, or polygonal cross-section, but are not limited thereto.
Further, the biodegradable fiber may be of a sheath-core type including a core portion and a sheath portion, a side-by-side type, an island-in-sea type, or a orange-peel type.
In the sheath-core type, the cross section of the core and the cross section of the sheath may be different from each other. For example, the core may have a circular cross section, and the skin may have a circular ring-shaped cross section, but is not limited thereto.
Further, the biodegradable fiber may be a bicomponent composite fiber in which the sheath and core each comprise a different monocomponent resin. It may be a three-component composite fiber in which the sheath comprises a single component resin and the core comprises at least a two component resin, or the core comprises a single component resin and the sheath comprises at least a two component resin. Further, the biodegradable fiber may be a composite fiber in which the sheath and the core each contain at least a bicomponent resin.
For example, the core may comprise polyhydroxyalkanoate resin and the skin may comprise biodegradable resin. For example, the biodegradable resin may be at least one selected from the group consisting of polybutylene adipate terephthalate (PBAT), polylactic acid (PLA), polybutylene succinate (PBS), polybutylene adipate (PBA), polybutylene succinate-adipate (PBSA), polybutylene succinate-terephthalate (PBST), polyhydroxybutyrate-valerate (PHBV), polycaprolactone (PCL), polybutylene succinate adipate terephthalate (PBSAT), polybutylene adipate succinate acetate (PBEAS), polybutylene succinate acetate (PBES), and thermoplastic starch (TPS).
The weight ratio of the core to the skin may be 5:95 to 95:5. For example, the weight ratio of core to skin may be 5:95 to 85:15,7:93 to 80:20, 10:90 to 75:25, or 10:90 to 70:30.
Method for producing biodegradable fibers
A method for preparing a biodegradable fiber according to another embodiment of the present invention includes spinning and stretching a composition for a biodegradable fiber or particles prepared by melt extruding the composition, wherein the composition for a biodegradable fiber includes a polyhydroxyalkanoate resin including 4-hydroxybutyrate (4-HB) repeat units and a decomposition temperature (Td, 5% weight loss) measured by a thermogravimetric analyzer (TGA) is 220 ℃ or higher.
Details regarding the composition for biodegradable fibers are described above.
Specifically, in the method for preparing a biodegradable fiber according to another embodiment of the present invention, the composition for a biodegradable fiber may be directly fed into a device, spun, and then drawn, or the particles prepared by melt extrusion of the composition for a biodegradable fiber may be fed into a device, spun, and then drawn, thereby preparing a biodegradable fiber.
Since the spinning step is followed by the drawing step, the diameter or length of the biodegradable fiber can be more effectively controlled. In particular, if the length or diameter of the biodegradable fiber is controlled only through the spinning or melt spinning step, productivity and processability may be deteriorated.
According to another embodiment of the invention, the method may further comprise melt extruding a composition for biodegradable fibers at 150 ℃ to 200 ℃ to prepare particles.
In particular, melt extrusion may be performed at a pressure of 6 bar to 30 bar and a temperature of 150 ℃ to 200 ℃. For example, melt extrusion may be performed using a single screw extruder or a twin screw extruder at a pressure of 7 bar to 28 bar or 8 bar to 26 bar and a temperature of 155 ℃ to 190 ℃ or 165 ℃ to 185 ℃.
Furthermore, prior to the melt extrusion step, a single screw extruder or twin screw extruder may be used to further perform the mixing step at a temperature elevated from 50 ℃ to 170 ℃.
Further, after the melt extrusion step, the melt extrudate may be cooled to 15 ℃ or less, 10 ℃ or less, or 6 ℃ or less and then cut to prepare biodegradable particles, but is not limited thereto.
In addition, the spinning speed may be 10mpm to 500mpm. For example, the spinning speed may be 10mpm to 450mpm,10mpm to 400mpm, or 15mpm to 400mpm.
Further, the stretching may be performed by cold stretching or hot stretching at a stretching ratio of 1.1 times or more. For example, stretching may be performed at a stretch ratio of 1.1 times or more, 2.5 times or more, 3.5 times or more, 5 times or more, 5.5 times or more, 6 times or more, 6.5 times or more, or 7 times or more.
Cold stretching may be performed at a chamber temperature of 25 ℃ to 35 ℃ and a roll temperature of 25 ℃ to 35 ℃. The hot stretching may be performed at a chamber temperature of 150 to 200 ℃ and a roll temperature of 80 to 130 ℃.
According to another embodiment of the present invention, the step of spinning the particles may be a step of melt spinning the particles at 140 to 190 ℃. Specifically, biodegradable particles are extruded, melted and spun through a nozzle, cooled, and then wound using a roll to prepare biodegradable fibers.
For example, the particles may be melt spun at 150 ℃ to 190 ℃,155 ℃ to 190 ℃, or 160 ℃ to 185 ℃. In this case, a conventional melt spinning apparatus may be used without limitation. For example, melt spinning may be performed using a melt spinning apparatus based on a single screw extruder, but is not limited thereto.
Further, the melt spinning apparatus may include a melting portion, a nozzle portion including a filter, a drawing portion between the nozzle hole and the winding roller, and a winding portion. The melt temperature of the melt spinning apparatus, the diameter of the nozzle hole, the length of the nozzle hole, the ratio of the length of the nozzle hole to the diameter, the size of the filter in the nozzle, the discharge amount through the nozzle, the length of the drawing section, the spinning speed, the cooling temperature, the winding speed can be controlled to produce biodegradable fibers having desired physical properties.
According to another embodiment of the present invention, it may further comprise drying the pellets at 40 ℃ to 60 ℃ for 10 hours or more before the melt spinning step.
For example, before the melt spinning step, a step of drying the pellets at 40 ℃ to 58 ℃ or 42 ℃ to 60 ℃ for 11 hours or more or 12 hours or more may be further performed.
In addition, the drying step may be performed until the resin moisture content of the particles is 2000ppm or less, 1500ppm or less, 1100ppm or less, 500ppm or less, 300ppm or less, 150ppm or less, 100ppm or less, 60ppm or less or 50ppm or less, and the drying step may be performed by hot air drying or dehumidification drying, but is not limited thereto.
According to another embodiment of the invention, the spinning step of the composition for biodegradable fibers may be performed using a composite spinning apparatus. For example, the composite spinning apparatus may be a sheath-core composite spinning apparatus.
In particular, the composition for biodegradable fibers can be fed directly to the core or sheath of a sheath-core composite spinning apparatus to produce biodegradable fibers.
More specifically, a composition for biodegradable fibers may be fed to the core or the sheath, and a biodegradable resin may be fed to the core or the sheath, the biodegradable resin including at least one selected from the group consisting of polybutylene adipate terephthalate (PBAT), polylactic acid (PLA), polybutylene succinate (PBS), polybutylene adipate (PBA), polybutylene succinate-adipate (PBSA), polybutylene succinate-terephthalate (PBST), polyhydroxybutyrate-valerate (PHBV), polycaprolactone (PCL), polybutylene succinate adipate terephthalate (PBSAT), polybutylene acetate succinate adipate (PBEAS), polybutylene acetate succinate (PBES), and thermoplastic starch (TPS).
For example, a composition for a biodegradable resin may be fed to the core, and a biodegradable resin may be fed to the skin, the biodegradable resin including at least one selected from the group consisting of polybutylene adipate terephthalate (PBAT), polylactic acid (PLA), polybutylene succinate (PBS), polybutylene adipate (PBA), polybutylene succinate-adipate (PBSA), polybutylene succinate-terephthalate (PBST), polyhydroxybutyrate-valerate (PHBV), polycaprolactone (PCL), polybutylene succinate adipate terephthalate (PBSAT), polybutylene adipate succinate adipate (PBEAS), polybutylene succinate acetate (PBES), and thermoplastic starch (TPS).
Furthermore, the weight ratio of raw materials fed to the core to skin may be 5:95 to 95:5,5:95 to 85:15,7:93 to 80:20, 10:90 to 75:25, or 10:90 to 70:30.
Modes of the invention
The present invention will be described in more detail hereinafter with reference to the following examples. However, the following examples are intended to illustrate the invention, and the scope of the examples is not limited thereto.
Examples (example)
Preparation of biodegradable particles
Example 1-1
30% by weight of Polyhydroxyalkanoate (PHA) resin (3-HB-co-4-HB, manufacturer: CJ) comprising 100% by weight of the second PHA resin (scPHA (a), 4-hydroxybutyrate (4-HB) content: 8% by weight, weight average molecular weight (Mw): 600000g/mol, melt flow index at 165 ℃ and 5 kg: 1.1g/10 min) was mixed with 70% by weight of polylactic acid (PLA, manufacturer: total Corbion), followed by adding thereto 1phr of polyvinyl acetate (PVAc, manufacturer: wacker) to prepare a composition for biodegradable fibers.
Thereafter, the composition is fed to a twin screw extruder, mixed and melt extruded to prepare biodegradable particles. Specifically, the biodegradable particles are prepared by: the screw rotation speed of the twin screw extruder was set to 190rpm, the composition was mixed while raising the internal temperature from 50 ℃ to 170 ℃, melt extrusion was performed at a pressure of 14 bar and a temperature of 176 ℃, and a strand cutting method was used.
Examples 1 to 2
30% by weight of a Polyhydroxyalkanoate (PHA) resin (3-HB-co-4-HB, manufacturer: CJ) comprising 100% by weight of a second PHA resin (scPHA (b), a 4-hydroxybutyrate (4-HB) content of 17% by weight, a weight average molecular weight (Mw) of 600000g/mol, a melt flow index at 165 ℃ and 5kg of 4.86g/10min, a melt flow index at 190 ℃ of 19.72g/10 min) was mixed with 70% by weight of polylactic acid (PLA, manufacturer: total Corbion) followed by the addition thereto of 1phr of polyvinyl acetate (PVAc, manufacturer: wacker) to prepare a composition for biodegradable fibers.
Thereafter, the composition is fed to a twin screw extruder, mixed and melt extruded to prepare biodegradable particles. Specifically, the biodegradable particles are prepared by: the screw rotation speed of the twin screw extruder was set at 200rpm, the composition was mixed while raising the internal temperature from 50 ℃ to 170 ℃, melt extrusion was performed at a pressure of 17 bar and a temperature of 180 ℃, and a strand cutting method was used.
Examples 1 to 3
Biodegradable particles were prepared in the same manner as in example 1-1 except that polybutylene adipate terephthalate (PBAT) was used instead of polylactic acid.
Examples 1 to 4
Biodegradable particles were prepared in the same manner as in examples 1-2, except that polybutylene adipate terephthalate (PBAT) was used instead of polylactic acid.
Examples 1 to 5
30% by weight of Polyhydroxyalkanoate (PHA) resin (3-HB-co-4-HB, manufacturer: CJ) comprising 100% by weight of second PHA resin (scPHA (a), 4-hydroxybutyrate (4-HB) content: 8% by weight, weight average molecular weight (Mw): 600000g/mol, melt flow index at 165 ℃ and 5 kg: 1.1g/10 min) was mixed with 70% by weight of polybutylene succinate (PBS), followed by adding thereto 1phr of polyvinyl acetate (PVAc, manufacturer: wacker) to prepare a composition for biodegradable fibers.
Thereafter, the composition is fed to a twin screw extruder, mixed and melt extruded to prepare biodegradable particles. Specifically, the biodegradable particles are prepared by: the screw rotation speed of the twin screw extruder was set at 200rpm, the composition was mixed while raising the internal temperature from 50 ℃ to 170 ℃, melt extrusion was performed at a pressure of 12 bar and a temperature of 177 ℃, and a strand cutting method was used.
Examples 1 to 6
30% by weight of Polyhydroxyalkanoate (PHA) resin (3-HB-co-4-HB, manufacturer: CJ) comprising 100% by weight of a second PHA resin (scPHA (b), 4-hydroxybutyrate (4-HB) content: 17% by weight, weight average molecular weight (Mw): 600000g/mol, melt flow index at 165 ℃ and 5 kg: 19.72g/10min, melt flow index at 190 ℃:19.72g/10 min) was mixed with 70% by weight of polybutylene succinate (PBS), followed by the addition thereto of 1phr of polyvinyl acetate (PVAc, manufacturer: wacker) to prepare a composition for biodegradable fibers.
Thereafter, the composition is fed to a twin screw extruder, mixed and melt extruded to prepare biodegradable particles. Specifically, the biodegradable particles are prepared by: the screw rotation speed of the twin screw extruder was set at 200rpm, the composition was mixed while raising the internal temperature from 50 ℃ to 170 ℃, melt extrusion was performed at a pressure of 12 bar and a temperature of 177 ℃, and a strand cutting method was used.
Examples 1 to 7
30% by weight of a Polyhydroxyalkanoate (PHA) resin (3-HB-co-4-HB, manufacturer: CJ) comprising 25% by weight of a first PHA resin (aPHA, 4-hydroxybutyrate (4-HB) content of 33% by weight, a weight average molecular weight (Mw) of 600000g/mol, a melt flow index at 165 ℃ and 5kg of 5.5g/10 min) and 75% by weight of a second PHA resin (scPHA (a), 4-hydroxybutyrate (4-HB) content of 8% by weight, a weight average molecular weight (Mw) of 300000g/mol, a melt flow index at 165 ℃ and 5kg of 1.1g/10 min) were mixed with 70% by weight of polylactic acid (PLA, manufacturer: total Corbion) followed by adding thereto 1phr of polyvinyl acetate (PVAc, manufacturer: wacker) to prepare a composition for biodegradable fibers.
Thereafter, the composition is fed to a twin screw extruder, mixed and melt extruded to prepare biodegradable particles. Specifically, the biodegradable particles are prepared by: the screw rotation speed of the twin screw extruder was set at 200rpm, the composition was mixed while raising the internal temperature from 50 ℃ to 170 ℃, melt extrusion was performed at a pressure of 21 bar and a temperature of 178 ℃, and a strand cutting method was used.
Examples 1 to 8
30% by weight of a Polyhydroxyalkanoate (PHA) resin (3-HB-co-4-HB, manufacturer: CJ) comprising 50% by weight of a first PHA resin (aPHA, 4-hydroxybutyrate (4-HB) content of 33% by weight, a weight average molecular weight (Mw) of 600000g/mol, a melt flow index at 165 ℃ and 5kg of 5.5g/10 min) and 50% by weight of a second PHA resin (scPHA (a), a 4-hydroxybutyrate (4-HB) content of 8% by weight, a weight average molecular weight (Mw) of 600000g/mol, a melt flow index at 165 ℃ and 5kg of 1.1g/10 min) were mixed with 70% by weight of polylactic acid (PLA, manufacturer: total Corbion) followed by adding thereto 1phr of polyvinyl acetate (PVAc, manufacturer: wacker) to prepare a composition for biodegradable fibers.
Thereafter, the composition is fed to a twin screw extruder, mixed and melt extruded to prepare biodegradable particles. Specifically, the biodegradable particles are prepared by: the screw rotation speed of the twin screw extruder was set at 200rpm, the composition was mixed while the internal temperature was raised from 50 ℃ to 170 ℃, melt extrusion was performed at a pressure of 14 bar and a temperature of 175 ℃, and a strand cutting method was used.
Examples 1 to 9
Biodegradable particles were prepared in the same manner as in examples 1 to 7 except that polybutylene adipate terephthalate (PBAT) was used instead of polylactic acid.
Examples 1 to 10
Biodegradable particles were prepared in the same manner as in examples 1 to 8 except that polybutylene adipate terephthalate (PBAT) was used instead of polylactic acid.
Examples 1 to 11
Biodegradable particles were prepared in the same manner as in examples 1-5, except that Polyhydroxyalkanoate (PHA) resin (3-HB-co-4-HB, manufacturer: CJ) comprising 25% by weight of the first PHA resin (aPHA, 4-hydroxybutyrate (4-HB) content of 33% by weight, weight average molecular weight (Mw) of 600000g/mol, melt flow index at 165℃and 5kg of 5.5g/10 min) and 75% by weight of the second PHA resin (scPHA (a), 4-hydroxybutyrate (4-HB) content of 8% by weight, weight average molecular weight (Mw) of 600000g/mol, melt flow index at 165℃and 5kg of 1.1g/10 min) was used.
Examples 1 to 12
Biodegradable particles were prepared in the same manner as in examples 1-5, except that Polyhydroxyalkanoate (PHA) resin (3-HB-co-4-HB, manufacturer: CJ) comprising 50% by weight of the first PHA resin (aPHA, 4-hydroxybutyrate (4-HB) content: 33% by weight, weight average molecular weight (Mw) of 600000g/mol, melt flow index at 165 ℃ and 5 kg: 5.5g/10 min) and 50% by weight of the second PHA resin (scPHA (a), 4-hydroxybutyrate (4-HB) content: 8% by weight, weight average molecular weight (Mw) of 600000g/mol, melt flow index at 165 ℃ and 5 kg: 1.1g/10 min) was used.
Examples 1 to 13
30% by weight of a first PHA resin (aPHA, 4-hydroxybutyrate (4-HB) content: 33% by weight, weight average molecular weight (Mw): 600000g/mol, melt flow index at 165 ℃ and 5 kg: 5.5g/10 min) was mixed with 70% by weight of polylactic acid (PLA, manufacturer: total Corbion), followed by the addition of 1phr of polyvinyl acetate (PVAc, manufacturer: wacker) thereto to prepare a composition for biodegradable fibers.
Thereafter, the composition is fed to a twin screw extruder, mixed and melt extruded to prepare biodegradable particles. Specifically, the biodegradable particles are prepared by: the screw rotation speed of the twin screw extruder was set at 200rpm, the composition was mixed while raising the internal temperature from 50 ℃ to 170 ℃, melt extrusion was performed at a pressure of 21 bar and a temperature of 178 ℃, and a strand cutting method was used.
Examples 1 to 14
Biodegradable particles were prepared in the same manner as in examples 1 to 13 except that 40% by weight of the first PHA resin and 60% by weight of polylactic acid were used.
Examples 1 to 15
Biodegradable particles were prepared in the same manner as in examples 1-13, except that 50 wt% of the first PHA resin and 50 wt% of polylactic acid were used.
Comparative example 1-1
1phr of polyvinyl acetate (PVAc, manufacturer: wacker) was added to 100% by weight of polylactic acid (PLA, manufacturer: total Corbion) to prepare a composition for biodegradable fibers.
Thereafter, the composition is fed to a twin screw extruder, mixed and melt extruded to prepare biodegradable particles. Specifically, the biodegradable particles are prepared by: the screw rotation speed of the twin screw extruder was set at 200rpm, the composition was mixed while raising the internal temperature from 50 ℃ to 170 ℃, melt extrusion was performed at a pressure of 21 bar and a temperature of 178 ℃, and a strand cutting method was used.
TABLE 1
Test example 1-1: melt flow index
Melt flow indices (g/10 min) of the compositions for biodegradable fibers prepared in examples 1-1, 1-2, 1-5 to 1-8 and 1-11 to 1-15 were measured according to ASTM D1238 at 190℃and 2.16kg, respectively.
Specifically, melt flow indexes of biodegradable particles of examples 1-1, 1-2, 1-5 to 1-8, and 1-11 to 1-15, which were prepared by feeding a composition for biodegradable fibers to a twin screw extruder, mixing, and melt extruding, respectively, were measured according to ASTM D1238.
Test examples 1-2: tg and Tm
The glass transition temperature (Tg) and melting temperature (Tm) of the compositions for biodegradable fibers prepared in examples 1-1, 1-2, 1-5 to 1-8 and 1-11 to 1-15 were measured using Differential Scanning Calorimetry (DSC), respectively.
Specifically, 5mg to 20mg of each composition for biodegradable fibers was placed in an aluminum pan, and the temperature was raised from 40 ℃ to 180 ℃ at a rate of 10 ℃/min using a differential scanning calorimeter, followed by cooling to-50 ℃ at a rate of 10 ℃/min to obtain a heat flow curve from which the glass transition temperature (Tg) and the melting temperature (Tm) were measured.
Test examples 1-3: td (Td)
The decomposition temperatures (Td) of the compositions for biodegradable fibers prepared in examples 1-1, 1-2, 1-5 to 1-8 and 1-11 to 1-15 were measured using a thermogravimetric analyzer (TGA), respectively.
Specifically, the decomposition temperature (Td) was measured as a temperature at which the weight of each composition for biodegradable fibers was reduced by 5% on a weight change curve obtained by raising the temperature from room temperature to 600 ℃ at a rate of 10 ℃/min using a thermogravimetric analyzer (TGA).
TABLE 2
As can be seen from table 2 above, the compositions for biodegradable fibers of examples 1-1, 1-2, 1-5 to 1-8 and 1-11 to 1-15 each have excellent dispersibility and satisfy the glass transition temperature, melting temperature and decomposition temperature of the appropriate numerical ranges; thus, biodegradable particles can be easily prepared using the composition. In addition, the biodegradable fiber can be prepared not only directly from the composition for biodegradable fiber, but also using biodegradable particles obtained from the composition for biodegradable fiber, thereby conveniently selecting and applying a process as needed.
Preparation of biodegradable fibers
Example 2-1
The biodegradable particles prepared in example 1-1 were dried at about 40 to 60 ℃ using hot air or dehumidification for at least 12 hours until the moisture content thereof was 100ppm or less. Then, it was melted and spun using a single screw extruder-based melt spinning apparatus to prepare biodegradable fibers.
Specifically, the pellets are extruded, melted and spun through a nozzle, cooled, and then wound using a roll to prepare biodegradable fibers (monofilaments).
In this case, the process conditions of the melt spinning apparatus are as follows.
Melting and spinning temperatures: about 140 ℃ to 190 DEG C
Diameter of nozzle hole: 0.1mm to 5.0mm (ψ0.2to 5.0)
Ratio of nozzle length to nozzle hole diameter (length/diameter (L/D)): 1.0 or more
Size of filter in nozzle: 10 μm to 250 μm
Discharge rate: 5 g/min/hole to 20 g/min/hole
Distance between nozzle hole and winding roller (traction portion): 1m or longer
Spinning speed: 10mpm to 500mpm
-cooling air temperature: 10 ℃ to 30 DEG C
Winding speed: 10mpm to 500mpm
Stretch ratio: 5.0 times to 7.0 times
Stretching temperature
: cold stretching (Chamber temperature: 25 ℃ to 35 ℃, roller temperature: 25 ℃ to 35 ℃)
: hot stretching (room temperature: 150 ℃ to 200 ℃, roll temperature: 80 ℃ to 130 ℃)
Examples 2-2 to 2-15 and comparative example 2-1
Biodegradable fibers were prepared in the same manner as in example 2-1, respectively, except that the biodegradable particles prepared in examples 1-2 to 1-15 and comparative example 1-1 were used, respectively.
Test example 2-1: denier of fiber
The titers (denier, D) of the biodegradable fibers prepared in examples 2-1, 2-2, 2-5, 2-6, 2-8 and 2-12 to 2-15 and comparative example 2-1 were measured according to the skein method of KS K ISO 2060, respectively.
In this case, denier (D) is a unit representing the fineness of a fiber or yarn, and represents the gram weight of 9000m of the fiber or yarn.
Test example 2-2: strength and elongation of fibers
The strength (g/D) and elongation (%) of the biodegradable fibers prepared in examples 2-1, 2-2, 2-5, 2-6, 2-8 and 2-12 to 2-15 and comparative example 2-1 were measured according to ASTM D3822, respectively.
Specifically, when the fiber is drawn with a constant force until it breaks, a value (g/d) obtained by dividing the applied load by denier is the strength, and a value (%) of the initial length to the drawn length in percent is the elongation.
TABLE 3
As can be seen from Table 3, the biodegradable fibers prepared in examples 2-1, 2-2, 2-5, 2-6, 2-8 and 2-12 to 2-15 each have the desired range of diameter, fineness, strength and elongation characteristics. Specifically, the biodegradable fibers prepared in examples 2-1, 2-2, 2-5, 2-6, 2-8 and 2-12 to 2-15 have excellent flexibility, strength, elongation, productivity and processability because they were prepared using the biodegradable particles having excellent spinning properties of examples 1-1, 1-2, 1-5, 1-6, 1-8 and 1-12 to 1-15, respectively.
Preparation of biodegradable fibers
Example 3-1
A composition for biodegradable fibers comprising a Polyhydroxyalkanoate (PHA) resin (3-HB-co-4-HB, manufacturer: CJ) containing 100 wt% of the second PHA resin (scPHA (c), 4-hydroxybutyrate (4-HB) content: 6 wt%, weight average molecular weight (Mw): 410000g/mol, melt flow index at 165 ℃ and 5 kg: 2.88g/10 min) was prepared as a core, and polybutylene succinate (PBS) was prepared as a sheath.
Thereafter, 10 wt% of the core composition and 90 wt% of PBS were spun at a spinning speed of 100mpm to 150mpm using a sheath-core composite spinning apparatus and drawn at a draw ratio of 6.0 times to prepare biodegradable fibers. In this case, the stretching temperature is as follows.
Stretching temperature
: cold stretching (Chamber temperature: 25 ℃ to 35 ℃, roller temperature: 25 ℃ to 35 ℃)
: hot stretching (room temperature: 150 ℃ to 200 ℃, roll temperature: 80 ℃ to 130 ℃)
Examples 3-2 to 3-22
Biodegradable fibers were prepared in the same manner as in example 3-1, except that the components and process conditions were changed as shown in tables 4 to 6 below. Here, in examples 3-17 to 3-22, the first PHA resin (aPHA, 4-hydroxybutyrate (4-HB) content was used in an amount of 33% by weight, weight average molecular weight (Mw) of 600000g/mol, melt flow index at 165℃and 5kg of 5.5g/10 min.
Test example 3-1: denier of fiber
The titer (denier, D) of the biodegradable fibers prepared in examples 3-1 to 3-22 were measured according to the skein method of KS K ISO 2060, respectively.
In this case, denier (D) is a unit representing the fineness of a fiber or yarn, and represents the gram weight of 9000m of the fiber or yarn.
Test example 3-2: strength and elongation of fibers
The strength (g/D) and elongation (%) of the biodegradable fibers prepared in examples 3-1 to 3-22 were measured according to ASTM D3822, respectively.
Specifically, when the fiber is drawn with a constant force until it breaks, a value (g/d) obtained by dividing the applied load by denier is the strength, and a value (%) of the initial length to the drawn length in percent is the elongation.
TABLE 4
TABLE 5
TABLE 6
As can be seen from tables 4 to 6, the biodegradable fibers prepared in examples 3-1 to 3-22 each have desired ranges of diameter, fineness, strength and elongation characteristics. Specifically, the biodegradable fibers of examples 3-1 to 3-22 were each prepared in a sheath-core type including a sheath portion and a core portion, and more specifically, the sheath portion contained a composition for the biodegradable fiber. In secondary processes (e.g., secondary processes such as dyeing and braiding) for manufacturing products (e.g., garments and fishing nets), the workability can be further improved.
Claims (24)
1. A composition for biodegradable fibers comprising a polyhydroxyalkanoate resin comprising 4-hydroxybutyrate (4-HB) repeat units, wherein a decomposition temperature (Td, 5% weight loss) as measured by a thermogravimetric analyzer (TGA) is 220 ℃ or higher.
2. The composition for biodegradable fibers according to claim 1, wherein the polyhydroxyalkanoate resin comprises 4-hydroxybutyrate (4-HB) repeat unit in an amount of 0.1 wt% to 60 wt%.
3. The composition for biodegradable fibers according to claim 1, wherein the polyhydroxyalkanoate resin further comprises at least one repeating unit selected from the group consisting of 3-hydroxybutyrate (3-HB), 3-hydroxypropionate (3-HP), 3-hydroxycaproate (3-HH), 3-hydroxyvalerate (3-HV), 4-hydroxyvalerate (4-HV), 5-hydroxyvalerate (5-HV) and 6-hydroxycaproate (6-HH).
4. The composition for biodegradable fibers of claim 1, wherein the polyhydroxyalkanoate resin comprises a first PHA resin and the first PHA resin comprises 4-hydroxybutyrate (4-HB) repeat unit in an amount of 15% to 60% by weight and has a Melt Flow Index (MFI) of 0.1g/10min to 20g/10min measured at 165 ℃ and 5kg according to ASTM D1238.
5. The composition for biodegradable fibers of claim 1, wherein the polyhydroxyalkanoate resin comprises a second PHA resin and the second PHA resin comprises 4-hydroxybutyrate (4-HB) repeat units in an amount of 0.1% to 30% by weight and has a melt flow index of 0.1g/10min to 15g/10min measured at 165 ℃ and 5kg according to ASTM D1238.
6. The composition for biodegradable fibers of claim 1, wherein the polyhydroxyalkanoate resin comprises a first PHA resin and a second PHA resin, and the content of 4-HB repeat units of the first PHA resin and the content of 4-HB repeat units of the second PHA are different from each other.
7. The composition for biodegradable fibers of claim 6, wherein the weight ratio of the first PHA resin to the second PHA resin is 1:0.5 to 1:5.
8. The composition for biodegradable fibers according to claim 1, comprising polyhydroxyalkanoate resin in an amount of 10 to 100 wt%, based on the total weight of the composition for biodegradable fibers.
9. The composition for biodegradable fibers according to claim 1, wherein the composition for biodegradable fibers comprises at least one biodegradable resin selected from the group consisting of polybutylene adipate terephthalate (PBAT), polylactic acid (PLA), polybutylene succinate (PBS), polybutylene adipate (PBA), polybutylene succinate-adipate (PBSA), polybutylene succinate-terephthalate (PBST), polyhydroxybutyrate-valerate (PHBV), polycaprolactone (PCL), polybutylene succinate adipate terephthalate (PBSAT), and thermoplastic starch (TPS).
10. The composition for biodegradable fibers according to claim 9, wherein the biodegradable resin is used in an amount of 30 wt% or more based on the total weight of the composition for biodegradable fibers, and the weight ratio of polyhydroxyalkanoate resin to biodegradable resin is 1:0.2 to 1:4.5.
11. The composition for biodegradable fibers according to claim 1, wherein the composition for biodegradable fibers comprises at least one additive selected from the group consisting of pigments, dye absorbers, light absorbers, antioxidants, compatibilizers, weighting agents, nucleating agents, melt enhancers, and slip agents.
12. The composition for biodegradable fibers according to claim 1, wherein the composition for biodegradable fibers has a melt flow index of 1g/10min to 30g/10min measured at 190 ℃ and 2.16kg and a melt flow index of 35g/10min to 130g/10min measured at 210 ℃ and 2.16kg according to ASTM D1238, a glass transition temperature (Tg) of-35 ℃ to 15 ℃ and a melting temperature (Tm) of 105 ℃ to 200 ℃ measured by Differential Scanning Calorimetry (DSC), and a decomposition temperature (Td, 5% weight loss) of 240 ℃ to 300 ℃ measured by thermogravimetric analyzer (TGA).
13. A biodegradable fiber comprising a polyhydroxyalkanoate resin comprising 4-hydroxybutyrate (4-HB) repeat units, wherein the strength measured according to ASTM D3822 is 0.5g/D to 10g/D.
14. The biodegradable fiber according to claim 13, wherein the biodegradable fiber has a diameter of 0.05mm to 10mm, a denier of 100 denier to 10000 denier, and an elongation of 25% or more.
15. The biodegradable fiber according to claim 13, wherein the biodegradable fiber is a composite fiber having a non-uniform cross section, or a composite fiber having two or more or three or more components.
16. The biodegradable fiber of claim 15, wherein the biodegradable fiber is of a sheath-core type, side-by-side type, islands-in-the-sea type, or orange-peel type comprising a core portion and a sheath portion.
17. The biodegradable fiber of claim 16, wherein the core comprises a polyhydroxyalkanoate resin, the sheath comprises a biodegradable resin, and the biodegradable resin is at least one selected from the group consisting of polybutylene adipate terephthalate (PBAT), polylactic acid (PLA), polybutylene succinate (PBS), polybutylene adipate (PBA), polybutylene succinate-adipate (PBSA), polybutylene succinate-terephthalate (PBST), polyhydroxybutyrate-valerate (PHBV), polycaprolactone (PCL), polybutylene succinate adipate terephthalate (PBSAT), polybutylene adipate succinate glycolate (PBEAS), polybutylene succinate acetate succinate (PBES), and thermoplastic starch (TPS).
18. A method for preparing a biodegradable fiber, the method for preparing a biodegradable fiber comprising spinning and stretching a composition for a biodegradable fiber or particles prepared by melt extruding the composition for a biodegradable fiber, wherein the composition for a biodegradable fiber comprises a polyhydroxyalkanoate resin comprising 4-hydroxybutyrate (4-HB) repeat units and a decomposition temperature (Td, 5% weight loss) measured by a thermogravimetric analyzer (TGA) is 220 ℃ or higher.
19. The method for producing biodegradable fiber according to claim 18, wherein the spinning speed is 10mpm to 500mpm, the stretching is performed by cold stretching or hot stretching at a stretching ratio of 1.1 times or more, the cold stretching is performed at a room temperature of 25 ℃ to 35 ℃ and a roll temperature of 25 ℃ to 35 ℃, and the hot stretching is performed at a room temperature of 150 ℃ to 200 ℃ and a roll temperature of 80 ℃ to 130 ℃.
20. The method for preparing a biodegradable fiber according to claim 18, wherein the method for preparing a biodegradable fiber further comprises melt extruding a composition for a biodegradable fiber at 150 ℃ to 200 ℃ to prepare particles.
21. The method for producing biodegradable fibers of claim 20, wherein the step of spinning the particles is melt spinning the particles at 140 ℃ to 190 ℃, and the method further comprises drying the particles at 40 ℃ to 60 ℃ for 10 hours or more before the melt spinning step.
22. The method for preparing a biodegradable fiber according to claim 18, wherein the spinning step of the composition for a biodegradable fiber is performed using a sheath-core composite spinning apparatus.
23. The method for producing biodegradable fibers according to claim 22, wherein the weight ratio of the raw materials to be supplied to the core and the sheath is 5:95 to 95:5.
24. The method for producing biodegradable fibers according to claim 22, wherein the composition for biodegradable fibers is supplied to the core.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2021-0115993 | 2021-08-31 | ||
| KR10-2022-0067166 | 2022-05-31 | ||
| KR1020220067166A KR20230032861A (en) | 2021-08-31 | 2022-05-31 | Composition for biodegradable fiber and biodegradable fiber using the same |
| PCT/KR2022/012960 WO2023033518A1 (en) | 2021-08-31 | 2022-08-30 | Composition for biodegradable fiber and biodegradable fiber manufactured using same |
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| Publication Number | Publication Date |
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| CN117881820A true CN117881820A (en) | 2024-04-12 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN202280058438.8A Pending CN117881820A (en) | 2021-08-31 | 2022-08-30 | Composition for biodegradable fiber and biodegradable fiber manufactured using the same |
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| Country | Link |
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| CN (1) | CN117881820A (en) |
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- 2022-08-30 CN CN202280058438.8A patent/CN117881820A/en active Pending
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