JP2019119840A - Aliphatic polyester resin composition - Google Patents
Aliphatic polyester resin composition Download PDFInfo
- Publication number
- JP2019119840A JP2019119840A JP2018002736A JP2018002736A JP2019119840A JP 2019119840 A JP2019119840 A JP 2019119840A JP 2018002736 A JP2018002736 A JP 2018002736A JP 2018002736 A JP2018002736 A JP 2018002736A JP 2019119840 A JP2019119840 A JP 2019119840A
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- polyester resin
- poly
- acid
- polyhydroxyalkanoate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000000203 mixture Substances 0.000 title claims abstract description 43
- 239000004645 polyester resin Substances 0.000 title claims abstract description 32
- 229920003232 aliphatic polyester Polymers 0.000 title description 6
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 claims abstract description 33
- 229920000903 polyhydroxyalkanoate Polymers 0.000 claims abstract description 33
- 229920001225 polyester resin Polymers 0.000 claims abstract description 30
- 150000007523 nucleic acids Chemical class 0.000 claims abstract description 19
- 108020004707 nucleic acids Proteins 0.000 claims abstract description 19
- 102000039446 nucleic acids Human genes 0.000 claims abstract description 19
- PXQPEWDEAKTCGB-UHFFFAOYSA-N orotic acid Chemical compound OC(=O)C1=CC(=O)NC(=O)N1 PXQPEWDEAKTCGB-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920000739 poly(3-hydroxycarboxylic acid) polymer Polymers 0.000 claims abstract description 13
- 229960005010 orotic acid Drugs 0.000 claims abstract description 8
- ISAKRJDGNUQOIC-UHFFFAOYSA-N Uracil Chemical compound O=C1C=CNC(=O)N1 ISAKRJDGNUQOIC-UHFFFAOYSA-N 0.000 claims description 10
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 9
- 239000004626 polylactic acid Substances 0.000 claims description 9
- RWQNBRDOKXIBIV-UHFFFAOYSA-N thymine Chemical compound CC1=CNC(=O)NC1=O RWQNBRDOKXIBIV-UHFFFAOYSA-N 0.000 claims description 8
- 229920000520 poly(3-hydroxybutyrate-co-3-hydroxyvalerate) Polymers 0.000 claims description 6
- 229940035893 uracil Drugs 0.000 claims description 5
- 229920000070 poly-3-hydroxybutyrate Polymers 0.000 claims description 4
- 229940113082 thymine Drugs 0.000 claims description 4
- 229920001013 poly(3-hydroxybutyrate-co-4-hydroxybutyrate) Polymers 0.000 claims description 3
- 238000000465 moulding Methods 0.000 abstract description 21
- 239000011342 resin composition Substances 0.000 abstract description 15
- 238000007711 solidification Methods 0.000 abstract description 15
- 230000008023 solidification Effects 0.000 abstract description 15
- 238000000034 method Methods 0.000 description 15
- 101710108497 p-hydroxybenzoate hydroxylase Proteins 0.000 description 14
- 239000004014 plasticizer Substances 0.000 description 13
- -1 polybutylene adipate terephthalate copolymer Polymers 0.000 description 13
- 239000002253 acid Substances 0.000 description 11
- 229920001577 copolymer Polymers 0.000 description 11
- 235000014113 dietary fatty acids Nutrition 0.000 description 10
- 239000000194 fatty acid Substances 0.000 description 10
- 229930195729 fatty acid Natural products 0.000 description 10
- 150000004665 fatty acids Chemical class 0.000 description 10
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000002425 crystallisation Methods 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 7
- 244000005700 microbiome Species 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- WHBMMWSBFZVSSR-UHFFFAOYSA-N 3-hydroxybutyric acid Chemical compound CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 description 6
- 241000894006 Bacteria Species 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 238000001746 injection moulding Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229920000728 polyester Polymers 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 238000005187 foaming Methods 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 241000252867 Cupriavidus metallidurans Species 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000002667 nucleating agent Substances 0.000 description 4
- ORAWFNKFUWGRJG-UHFFFAOYSA-N Docosanamide Chemical compound CCCCCCCCCCCCCCCCCCCCCC(N)=O ORAWFNKFUWGRJG-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229920000331 Polyhydroxybutyrate Polymers 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 238000000071 blow moulding Methods 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000003484 crystal nucleating agent Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 108090000623 proteins and genes Proteins 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- RDYWHMBYTHVOKZ-UHFFFAOYSA-N 18-hydroxyoctadecanamide Chemical compound NC(=O)CCCCCCCCCCCCCCCCCO RDYWHMBYTHVOKZ-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- WHBMMWSBFZVSSR-UHFFFAOYSA-M 3-hydroxybutyrate Chemical group CC(O)CC([O-])=O WHBMMWSBFZVSSR-UHFFFAOYSA-M 0.000 description 2
- 241000607516 Aeromonas caviae Species 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910000410 antimony oxide Inorganic materials 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 229920000704 biodegradable plastic Polymers 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
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000012258 culturing Methods 0.000 description 2
- OPTASPLRGRRNAP-UHFFFAOYSA-N cytosine Chemical compound NC=1C=CNC(=O)N=1 OPTASPLRGRRNAP-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- UYTPUPDQBNUYGX-UHFFFAOYSA-N guanine Chemical compound O=C1NC(N)=NC2=C1N=CN2 UYTPUPDQBNUYGX-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920005615 natural polymer Polymers 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920001020 poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) Polymers 0.000 description 2
- 229920009537 polybutylene succinate adipate Polymers 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000004632 polycaprolactone Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- FYGFTTWEWBXNMP-UHFFFAOYSA-N 10-amino-10-oxodecanoic acid Chemical compound NC(=O)CCCCCCCCC(O)=O FYGFTTWEWBXNMP-UHFFFAOYSA-N 0.000 description 1
- DKNLMUCCEFHGNE-UHFFFAOYSA-N 2,2-dihydroxy-3-methylideneoctadecanamide Chemical compound CCCCCCCCCCCCCCCC(=C)C(O)(O)C(N)=O DKNLMUCCEFHGNE-UHFFFAOYSA-N 0.000 description 1
- YXUZGLGRBBHYFZ-UHFFFAOYSA-N 2,4-dioxo-1h-pyrimidine-6-carboxylic acid;hydrate Chemical compound O.OC(=O)C1=CC(=O)NC(=O)N1 YXUZGLGRBBHYFZ-UHFFFAOYSA-N 0.000 description 1
- NODRXLWVBKZXOO-UHFFFAOYSA-N 2-(hydroxymethyl)docosanamide Chemical compound CCCCCCCCCCCCCCCCCCCCC(CO)C(N)=O NODRXLWVBKZXOO-UHFFFAOYSA-N 0.000 description 1
- JRHWHSJDIILJAT-UHFFFAOYSA-N 2-hydroxypentanoic acid Chemical compound CCCC(O)C(O)=O JRHWHSJDIILJAT-UHFFFAOYSA-N 0.000 description 1
- HPMGFDVTYHWBAG-UHFFFAOYSA-N 3-hydroxyhexanoic acid Chemical compound CCCC(O)CC(O)=O HPMGFDVTYHWBAG-UHFFFAOYSA-N 0.000 description 1
- SJZRECIVHVDYJC-UHFFFAOYSA-N 4-hydroxybutyric acid Chemical compound OCCCC(O)=O SJZRECIVHVDYJC-UHFFFAOYSA-N 0.000 description 1
- 229940006015 4-hydroxybutyric acid Drugs 0.000 description 1
- IWHLYPDWHHPVAA-UHFFFAOYSA-N 6-hydroxyhexanoic acid Chemical compound OCCCCCC(O)=O IWHLYPDWHHPVAA-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 229930024421 Adenine Natural products 0.000 description 1
- GFFGJBXGBJISGV-UHFFFAOYSA-N Adenine Chemical compound NC1=NC=NC2=C1N=CN2 GFFGJBXGBJISGV-UHFFFAOYSA-N 0.000 description 1
- 241000607534 Aeromonas Species 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241000193033 Azohydromonas lata Species 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- 241000194107 Bacillus megaterium Species 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004605 External Lubricant Substances 0.000 description 1
- 239000004610 Internal Lubricant Substances 0.000 description 1
- 241000498271 Necator Species 0.000 description 1
- XZPKILNCJMTQRU-UHFFFAOYSA-N OC(=O)CCCCCCCCC.OC(=O)CCCCCCCCC.C=C Chemical compound OC(=O)CCCCCCCCC.OC(=O)CCCCCCCCC.C=C XZPKILNCJMTQRU-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 229920000954 Polyglycolide Polymers 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 229930003270 Vitamin B Natural products 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229960000643 adenine Drugs 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 229940104302 cytosine Drugs 0.000 description 1
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- GFQOFGWPGYRLAO-UHFFFAOYSA-N dodecanamide;ethene Chemical compound C=C.CCCCCCCCCCCC(N)=O.CCCCCCCCCCCC(N)=O GFQOFGWPGYRLAO-UHFFFAOYSA-N 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- SWSBIGKFUOXRNJ-CVBJKYQLSA-N ethene;(z)-octadec-9-enamide Chemical compound C=C.CCCCCCCC\C=C/CCCCCCCC(N)=O.CCCCCCCC\C=C/CCCCCCCC(N)=O SWSBIGKFUOXRNJ-CVBJKYQLSA-N 0.000 description 1
- ZJOLCKGSXLIVAA-UHFFFAOYSA-N ethene;octadecanamide Chemical compound C=C.CCCCCCCCCCCCCCCCCC(N)=O.CCCCCCCCCCCCCCCCCC(N)=O ZJOLCKGSXLIVAA-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- FEEPBTVZSYQUDP-UHFFFAOYSA-N heptatriacontanediamide Chemical compound NC(=O)CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(N)=O FEEPBTVZSYQUDP-UHFFFAOYSA-N 0.000 description 1
- HSEMFIZWXHQJAE-UHFFFAOYSA-N hexadecanamide Chemical compound CCCCCCCCCCCCCCCC(N)=O HSEMFIZWXHQJAE-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 238000003898 horticulture Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000004790 ingeo Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
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Landscapes
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Abstract
Description
本発明は、ポリヒドロキシアルカノエート(例えば、ポリ(3−ヒドロキシアルカノエート))を含む脂肪族ポリエステル樹脂組成物、及び、それを成形してなる成形体に関する。 The present invention relates to an aliphatic polyester resin composition containing polyhydroxyalkanoate (eg, poly (3-hydroxyalkanoate)), and a molded article obtained by molding the same.
従来、プラスチックは加工や使用の容易性、再利用の困難性、衛生上の問題などの観点から使い捨てされてきた。しかし、プラスチックが多量に使用、廃棄されるにつれ、その埋め立て処理や焼却処理に伴う問題がクローズアップされている。そのような問題としては、例えばゴミ埋め立て地の不足、非分解性のプラスチックが環境に残存することによる生態系への影響、燃焼時の有害ガス発生、大量の燃焼熱量による地球温暖化等、地球環境への大きな負荷などが挙げられる。 In the past, plastics have been disposable in view of ease of processing and use, difficulty of reuse, and hygiene problems. However, as plastics are used and disposed in large quantities, the problems associated with their landfill and incineration are being highlighted. Such problems include, for example, the shortage of landfills, the impact on ecosystems due to non-degradable plastics remaining in the environment, the generation of harmful gases during combustion, global warming due to large amounts of combustion heat, etc. There is a large burden on the environment.
近年、上述のプラスチック廃棄物の問題を解決できるものとして、生分解性プラスチックの開発が盛んになっている。一般的に生分解性プラスチックは、1)ポリヒドロキシアルカノエート等の微生物生産系脂肪族ポリエステル、2)ポリ乳酸やポリカプロラクトン等の化学合成系脂肪族ポリエステル、3)澱粉や酢酸セルロース等の天然高分子といった、3種類に大別される。化学合成系脂肪族ポリエステルの多くは嫌気性分解しないため廃棄時の分解条件に制約がある。また、澱粉は非熱可塑性で脆く、耐水性に劣るといった問題がある。 In recent years, development of biodegradable plastics has been promoted as a solution to the above-mentioned problems of plastic waste. Generally, biodegradable plastics are 1) microbial polyesters such as polyhydroxyalkanoates, 2) chemically synthesized aliphatic polyesters such as polylactic acid and polycaprolactone, and 3) natural highs such as starch and cellulose acetate It is roughly divided into three types such as molecules. Many of the chemically synthesized aliphatic polyesters do not undergo anaerobic decomposition, and therefore there are restrictions on decomposition conditions at the time of disposal. In addition, starch is non-thermoplastic and brittle, and has problems such as poor water resistance.
一方、ポリヒドロキシアルカノエートのなかでもポリ(3−ヒドロキシアルカノエート)(以下P3HAと略すことがある)は好気性、嫌気性何れの環境下での分解性にも優れ、燃焼時には有毒ガスを発生せず、植物原料を使用して微生物により生産され得るプラスチックであって高分子量化が可能であり、地球上の二酸化炭素を増大させずカーボンニュートラルである、といった優れた特徴を有している。該P3HAは脂肪族ポリエステルに分類されるが、先に述べた化学合成系脂肪族ポリエステルや天然高分子とはポリマーの性質が大きく異なり、嫌気性下で分解する性質や、耐湿性に優れる点、高分子量化が可能である点は特筆すべき性能である。 On the other hand, among polyhydroxyalkanoates, poly (3-hydroxyalkanoate) (hereinafter sometimes abbreviated as P3HA) is excellent in both aerobic and anaerobic decomposability and generates toxic gas at the time of combustion. It is a plastic that can be produced by microorganisms using plant materials, has high characteristics of high molecular weight, and is carbon neutral without increasing carbon dioxide on the earth. The P3HA is classified into aliphatic polyesters, but the properties of the polymer are significantly different from those of the chemically synthesized aliphatic polyesters and natural polymers described above, and they have the property of being degraded under anaerobic and excellent moisture resistance, The point that high molecular weight can be achieved is a remarkable performance.
一方、P3HAは加工性に関して依然改善の余地がある。主に改善が必要であるのは、結晶化速度が遅いことに由来する加工性の悪さである。このような結晶化速度を速くする方法として種々検討が行われている(例えば、特許文献1参照)。 On the other hand, P3HA still has room for improvement in terms of processability. The main need for improvement is the poor processability stemming from the slow crystallization rate. Various studies have been conducted as a method of increasing such crystallization rate (see, for example, Patent Document 1).
しかしながら、ポリヒドロキシアルカノエート(例えば、ポリ(3−ヒドロキシアルカノエート))の結晶核剤に関する従来技術は、結晶化速度向上、ひいては成形性改良の観点では、まだまだ改善の余地があるのが現状である。また、成形加工時の成形機の汚染等を防ぐ観点では、できるだけ昇華やブリードアウトしにくい結晶核剤の開発が望まれている。 However, the prior art concerning the nucleating agent of polyhydroxyalkanoate (for example, poly (3-hydroxyalkanoate)) is currently at present still a room for improvement in terms of improvement of crystallization rate and hence improvement of formability. is there. Further, from the viewpoint of preventing contamination of the molding machine at the time of molding processing, development of a crystal nucleating agent which is as difficult as possible to sublimation or bleed out is desired.
従って、本発明は、ポリヒドロキシアルカノエート(例えば、ポリ(3−ヒドロキシアルカノエート))を含む組成物であって、固化速度が改善された樹脂組成物、及びそれを成形してなる成形体を提供することを目的とする。 Accordingly, the present invention provides a composition comprising a polyhydroxyalkanoate (for example, poly (3-hydroxyalkanoate)), wherein the resin composition has an improved solidification rate, and a molded article obtained by molding the same. Intended to be provided.
本発明者らは、上記課題を解決するべく鋭意研究を重ねた結果、ポリヒドロキシアルカノエート(例えば、ポリ(3−ヒドロキシアルカノエート))に対し、特定の化合物を配合することで、従来よりも速い固化速度でポリヒドロキシアルカノエートを固化させることができ、また、核酸塩基類は昇華・ブリードアウトしにくいことを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that, by blending a specific compound with polyhydroxyalkanoate (for example, poly (3-hydroxyalkanoate)), It has been found that polyhydroxyalkanoate can be solidified at a high solidification rate, and nucleic acid bases are difficult to sublimate and bleed out, and the present invention has been completed.
すなわち本発明は、例えば下記の発明を提供する。 That is, the present invention provides, for example, the following inventions.
[1]ポリヒドロキシアルカノエートと核酸塩基類とを含む、ポリエステル樹脂組成物。 [1] A polyester resin composition containing polyhydroxyalkanoate and nucleic acid bases.
[2]核酸塩基類が、ウラシル、チミン及びこれらの誘導体からなる群より選択される少なくとも1種である、[1]に記載のポリエステル樹脂組成物。 [2] The polyester resin composition according to [1], wherein the nucleobases are at least one selected from the group consisting of uracil, thymine and derivatives thereof.
[3]核酸塩基類がオロチン酸である、[2]に記載のポリエステル樹脂組成物。 [3] The polyester resin composition according to [2], wherein the nucleic acid base is orotic acid.
[4]核酸塩基類の含有量が、ポリヒドロキシアルカノエート100重量部に対して0.01〜10重量部である、[1]〜[3]のいずれか1つに記載のポリエステル樹脂組成物。 [4] The polyester resin composition according to any one of [1] to [3], wherein the content of nucleic acid bases is 0.01 to 10 parts by weight with respect to 100 parts by weight of polyhydroxyalkanoate. .
[5]ポリヒドロキシアルカノエートが、ポリ(3−ヒドロキシアルカノエート)及びポリ乳酸からなる群より選択される少なくとも1種である、[1]〜[4]のいずれか1つに記載のポリエステル樹脂組成物。 [5] The polyester resin according to any one of [1] to [4], wherein polyhydroxyalkanoate is at least one selected from the group consisting of poly (3-hydroxyalkanoate) and polylactic acid Composition.
[6]ポリヒドロキシアルカノエートがポリ(3−ヒドロキシアルカノエート)である、[1]〜[4]のいずれか1つに記載のポリエステル樹脂組成物。 [6] The polyester resin composition according to any one of [1] to [4], wherein the polyhydroxyalkanoate is poly (3-hydroxyalkanoate).
[7]ポリ(3−ヒドロキシアルカノエート)が、ポリ(3−ヒドロキシブチレート)、ポリ(3−ヒドロキシブチレート−コ−3−ヒドロキシバレレート)、ポリ(3−ヒドロキシブチレート−コ−3−ヒドロキシヘキサノエート)及びポリ(3−ヒドロキシブチレート−コ−4−ヒドロキシブチレート)からなる群より選択される少なくとも一種である、[6]に記載のポリエステル樹脂組成物。 [7] Poly (3-hydroxyalkanoate) is poly (3-hydroxybutyrate), poly (3-hydroxybutyrate-co-3-hydroxyvalerate), poly (3-hydroxybutyrate-co-3) The polyester resin composition according to [6], which is at least one selected from the group consisting of -hydroxyhexanoate) and poly (3-hydroxybutyrate-co-4-hydroxybutyrate).
本発明のポリエステル樹脂組成物は上記構成を有するため、固化速度が速く、射出成形、フィルム成形、ブロー成形、繊維の紡糸、押出発泡、ビーズ発泡などの各種加工における加工性、加工速度が改善され、優れた生産性で成形体を製造することができる。また、核酸塩基類を結晶核剤として使用することで、組成物における昇華・ブリードアウトが抑制されるという効果も奏する。 Since the polyester resin composition of the present invention has the above constitution, the solidification speed is high, and the processability and processing speed in various processes such as injection molding, film forming, blow molding, fiber spinning, extrusion foaming, bead foaming are improved. The molded product can be produced with excellent productivity. Moreover, by using nucleic acid bases as a crystal nucleating agent, there is also an effect that sublimation and bleed out in the composition are suppressed.
本発明のポリエステル樹脂組成物は、ポリヒドロキシアルカノエートと、核酸塩基類とを必須成分として含む。 The polyester resin composition of the present invention contains polyhydroxyalkanoate and nucleic acid bases as essential components.
(ポリヒドロキシアルカノエート)
本発明で用いられるポリヒドロキシアルカノエートは、モノマー単位としてヒドロキシアルカン酸単位を含有するポリエステルである。ヒドロキシアルカン酸としては、例えば、グリコール酸、乳酸、6−ヒドロキシカプロン酸、後述の3−ヒドロキシアルカン酸、4−ヒドロキシアルカン酸等が挙げられる。ポリヒドロキシアルカノエートの具体例としては、例えば、ポリグリコール酸、ポリ乳酸、ポリカプロラクトン、ポリ(3−ヒドロキシアルカノエート)(以下、「P3HA」と称する場合がある)等が挙げられる。中でも、本発明による効果がより顕著に奏される点で、P3HA、ポリ乳酸が好ましく、より好ましくはP3HAである。
(Polyhydroxyalkanoate)
The polyhydroxyalkanoates used in the present invention are polyesters containing hydroxyalkanoic acid units as monomer units. Examples of the hydroxyalkanoic acid include glycolic acid, lactic acid, 6-hydroxycaproic acid, 3-hydroxyalkanoic acid described later, 4-hydroxyalkanoic acid and the like. Specific examples of polyhydroxyalkanoate include polyglycolic acid, polylactic acid, polycaprolactone, poly (3-hydroxyalkanoate) (hereinafter sometimes referred to as "P3HA"), and the like. Among them, P3HA and polylactic acid are preferable, and P3HA is more preferable, in that the effect of the present invention is more remarkably exhibited.
(P3HA)
本発明で用いられるP3HAとは、モノマー単位として3−ヒドロキシアルカン酸単位を含有するポリエステルであり、特に、式:[−CHR−CH2−CO−O−](式中、RはCnH2n+1で表される直鎖又は分岐鎖状のアルキル基を示し、nは1以上15以下の整数である。)で示される繰り返し単位を含むポリエステルが好ましい。該ポリエステルは単独重合体であってよいし、前記繰り返し単位を2種類以上含む共重合体であってもよい。このような共重合体は、単独重合体と比較して融点が低くなり得るために、溶融時の温度を低くすることができ、組成物の変質を抑制できるため好ましい。
(P3HA)
The P3HA used in the present invention is a polyester containing a 3-hydroxyalkanoic acid unit as a monomer unit, and in particular, the formula: [-CHR-CH 2 -CO-O-] (wherein R is C n H A linear or branched alkyl group represented by 2n + 1 is shown, and n is an integer of 1 or more and 15 or less. The polyester may be a homopolymer, or may be a copolymer containing two or more of the repeating units. Such a copolymer is preferable because the melting point can be lowered as compared with a homopolymer, so that the temperature at the time of melting can be lowered, and deterioration of the composition can be suppressed.
また、P3HAは、モノマー単位として3−ヒドロキシアルカン酸単位のみを含有するポリエステルであってもよいが、モノマー単位として3−ヒドロキシアルカン酸単位と共に、他のヒドロキシアルカン酸単位(例えば、4−ヒドロキシアルカン酸単位)を含有する共重合ポリエステルであってもよい。前記共重合ポリエステルでは、全ヒドロキシアルカン酸単位のうち3−ヒドロキシアルカン酸単位が占める含有割合は特に限定されないが、例えば50モル%以上が好ましく、60モル%以上がより好ましく、70モル%以上がさらに好ましく、80モル%以上が特に好ましく、90モル%以上が最も好ましい。 P3HA may be a polyester containing only 3-hydroxyalkanoic acid units as monomer units, but other hydroxyalkanoic acid units (for example, 4-hydroxyalkanes) may be used together with 3-hydroxyalkanoic acid units as monomer units. It may be a copolyester containing an acid unit). The content ratio of 3-hydroxyalkanoic acid units among all hydroxyalkanoic acid units in the above copolymerized polyester is not particularly limited, but for example, 50 mol% or more is preferable, 60 mol% or more is more preferable, and 70 mol% or more 80 mol% or more is especially preferable, 90 mol% or more is the most preferable.
本発明におけるP3HAの具体例としては、例えば、PHB〔ポリ(3−ヒドロキシブチレート)、又はポリ3−ヒドロキシ酪酸〕、PHBH〔ポリ(3−ヒドロキシブチレート−コ−3−ヒドロキシヘキサノエート)、又はポリ(3−ヒドロキシ酪酸−co−3−ヒドロキシヘキサン酸)〕、PHBV〔ポリ(3−ヒドロキシブチレート−コ−3−ヒドロキシバレレート)、又はポリ(3−ヒドロキシ酪酸−co−3−ヒドロキシ吉草酸)〕、P3HB4HB〔ポリ(3−ヒドロキシブチレート−コ−4−ヒドロキシブチレート)、又はポリ(3−ヒドロキシ酪酸−co−4−ヒドロキシ酪酸)〕、ポリ(3−ヒドロキシブチレート−コ−3−ヒドロキシオクタノエート)、又はポリ(3−ヒドロキシブチレート−コ−3−ヒドロキシオクタデカノエート)等が挙げられる。これらのなかでも、工業的に生産が容易であるものとして、PHB、PHBH、PHBV、P3HB4HBが好ましく、PHBHがより好ましい。 Specific examples of P3HA in the present invention include, for example, PHB [poly (3-hydroxybutyrate) or poly 3-hydroxybutyric acid], PHBH [poly (3-hydroxybutyrate-co-3-hydroxyhexanoate)] Or poly (3-hydroxybutyrate-co-3-hydroxyhexanoic acid) !, PHBV [poly (3-hydroxybutyrate-co-3-hydroxyvalerate), or poly (3-hydroxybutyrate-co-3-) Hydroxyvaleric acid]], P3HB4HB [poly (3-hydroxybutyrate-co-4-hydroxybutyrate), or poly (3-hydroxybutyric acid-co-4-hydroxybutyric acid)], poly (3-hydroxybutyrate-) Co-3-hydroxyoctanoate) or poly (3-hydroxybutyrate-co-3-hydroxyoc) Decanoate), and the like. Among these, PHB, PHBH, PHBV, and P3HB4HB are preferable as being industrially easy to produce, and PHBH is more preferable.
P3HAは、柔軟性と強度の観点から、3−ヒドロキシブチレート単位を含む単独重合体又は共重合体が好ましい。なかでも、柔軟性と強度のバランスの観点から、P3HAに含まれる3−ヒドロキシブチレート単位の平均組成比が80モル%〜99モル%を示すものがより好ましく、85モル%〜97モル%を示すものがさらに好ましい。3−ヒドロキシブチレート単位の平均組成比が80モル%未満であると剛性が不足する傾向があり、99モル%より多いと柔軟性が不足する傾向がある。 P3 HA is preferably a homopolymer or copolymer containing 3-hydroxybutyrate units from the viewpoint of flexibility and strength. Among them, from the viewpoint of balance between flexibility and strength, it is more preferable that the average composition ratio of 3-hydroxybutyrate units contained in P3HA is 80 mol% to 99 mol%, and 85 mol% to 97 mol%. Those shown are more preferred. If the average composition ratio of 3-hydroxybutyrate units is less than 80 mol%, the rigidity tends to be insufficient, and if it is more than 99 mol%, the flexibility tends to be insufficient.
本発明において、P3HAは1種類のみを単独で使用してもよいし、2種以上を混合して使用してもよい。また、P3HAとしてPHBH等の共重合体を使用する場合には、3−ヒドロキシブチレート単位等のモノマー単位の平均組成比が異なる2種類以上の共重合体を混合して使用することもできる。 In the present invention, P3HA may be used alone or in combination of two or more. Moreover, when using copolymers, such as PHBH, as P3HA, 2 or more types of copolymers from which the average composition ratios of monomer units, such as a 3-hydroxy butyrate unit, differ can also be mixed and used.
本発明で使用するP3HAの分子量は、最終物の成形体が目的とする用途で、実質的に十分な物性を示すものであればよく、特に限定されない。しかし、分子量が低いと成形体の強度が低下する傾向があり、逆に高いと加工性が低下し、加工が困難になる場合があるので、それらを勘案して分子量を決定すればよい。この観点から、本発明で使用するP3HAの重量平均分子量の範囲は、50,000〜3,000,000が好ましく、100,000〜1,500,000がより好ましい。なお、ここでの重量平均分子量は、クロロホルム溶離液を用いたゲルパーミエーションクロマトグラフィー(GPC)を用い、ポリスチレン換算の分子量として測定されたものをいう。当該GPCにおけるカラムとしては、前記分子量を測定するのに適切なカラムを使用すればよい。 The molecular weight of P3HA used in the present invention is not particularly limited as long as it exhibits substantially sufficient physical properties in the intended use of the final molded product. However, if the molecular weight is low, the strength of the molded article tends to decrease, and if it is high, the processability may decrease and processing may become difficult. Therefore, the molecular weight may be determined in consideration of them. From this viewpoint, the range of the weight average molecular weight of P3HA used in the present invention is preferably 50,000 to 3,000,000, and more preferably 100,000 to 1,500,000. In addition, the weight average molecular weight here refers to what was measured as a molecular weight of polystyrene conversion using the gel permeation chromatography (GPC) using a chloroform eluent. As a column in the said GPC, a column suitable for measuring the said molecular weight may be used.
本発明で使用するP3HAのガラス転移温度は特に限定されないが、−30〜10℃が好ましい。本発明において、ガラス転移温度は、示差走査熱量分析で10℃/minの昇温速度にて測定される。 Although the glass transition temperature of P3HA used by this invention is not specifically limited, -30-10 degreeC is preferable. In the present invention, the glass transition temperature is measured by differential scanning calorimetry at a heating rate of 10 ° C./min.
P3HAを製造する方法としては特に限定されないが、例えば、P3HA産生能を有する微生物によりP3HAを産生させる方法が挙げられる。そのような微生物としては特に限定されないが、例えば、PHB生産菌としては、1925年に発見されたBacillus megateriumの他、カプリアビダス・ネケイター(Cupriavidus necator)(旧分類:アルカリゲネス・ユートロファス(Alcaligenes eutrophus、ラルストニア・ユートロフア(Ralstonia eutropha))、アルカリゲネス・ラタス(Alcaligenes latus)等が挙げられる。また、3−ヒドロキシブチレートとその他のヒドロキシアルカノエートとの共重合体生産菌としては、PHBVおよびPHBH生産菌であるアエロモナス・キヤビエ(Aeromonas caviae)、P3HB4HB生産菌であるアルカリゲネス・ユートロファス(Alcaligenes eutrophus)等が挙げられる。特に、PHBH生産菌としては、PHBHの生産性を上げるためにPHA合成酵素群の遺伝子を導入したアルカリゲネス・ユートロファス AC32株(Alcaligenes eutrophus AC32, FERM BP−6038)(T.Fukui,Y.Doi,J.Bacteriol.,179,p4821−4830(1997))が挙げられる。 Although it does not specifically limit as a method to manufacture P3HA, For example, the method to which P3HA is produced by the microorganism which has P3HA production ability is mentioned. Such microorganisms are not particularly limited. For example, as PHB-producing bacteria, in addition to Bacillus megaterium discovered in 1925, Capriavidus necator (old classification: Alka And U.S. eutropha (Ralstonia eutropha), Alkaligenes latus (Alcaligenes latus), etc. Moreover, as a copolymer producing bacteria of 3-hydroxybutyrate and other hydroxyalkanoates, Aeromonas which is PHBV and PHBH producing bacteria.・ Cerpent (Aeromonas caviae), P3HB4HB producing bacteria Alkaline Genes Yu Alphagenes eutrophus AC32 strain (Alcaligenes eutrophus AC32, FERM BP-6038), in which a gene of PHA synthetic enzyme group was introduced to increase PHBH productivity, is particularly mentioned as PHHB producing bacteria. (T. Fukui, Y. Doi, J. Bacteriol., 179, p4821-4830 (1997)).
これらの微生物を適切な条件で培養して菌体内にP3HAを蓄積させ、そのP3HAを回収することでP3HAを製造することができる。用いる微生物にあわせて、基質の種類を含む培養条件を最適化することができる。また、上掲した微生物以外にも、生産したいP3HAに合わせて、各種P3HA合成関連遺伝子を導入した遺伝子組換え微生物を培養してP3HAを製造することもできる。 P3HA can be produced by culturing these microorganisms under appropriate conditions to accumulate P3HA in the cells and recovering the P3HA. Culture conditions including the type of substrate can be optimized according to the microorganism used. In addition to the above-mentioned microorganisms, P3HA can also be produced by culturing genetically modified microorganisms into which various P3HA synthesis-related genes have been introduced, in accordance with the P3HA to be produced.
本発明のポリエステル樹脂組成物におけるポリヒドロキシアルカノエート(例えばP3HA)の含有量は、特に限定されないが、10〜99重量%が好ましく、より好ましくは30〜96重量%、さらに好ましくは50〜96重量%である。ポリヒドロキシアルカノエート(例えばP3HA)の含有量を10重量%以上とすることにより、組成物全体としてのバイオベース度や生分解性がいっそう向上する傾向がある。一方、ポリヒドロキシアルカノエート(例えばP3HA)の含有量を99重量%以下とすることにより、相対的に核酸塩基類の量が確保され固化速度が向上したり、他の樹脂を増量することで組成物全体としての機械特性等がいっそう向上する傾向がある。 The content of polyhydroxyalkanoate (for example, P3HA) in the polyester resin composition of the present invention is not particularly limited, but 10 to 99% by weight is preferable, more preferably 30 to 96% by weight, still more preferably 50 to 96% %. By setting the content of polyhydroxyalkanoate (for example, P3HA) to 10% by weight or more, the degree of biobase and biodegradability as the whole composition tends to be further improved. On the other hand, by setting the content of polyhydroxyalkanoate (for example, P3HA) to 99% by weight or less, the amount of nucleic acid bases is relatively secured, the solidification rate is improved, and the composition is increased by increasing other resins. There is a tendency to further improve the mechanical properties as a whole of the object.
本発明のポリエステル樹脂組成物は、ポリヒドロキシアルカノエート以外の樹脂(高分子)を含んでいてもよい。ポリヒドロキシアルカノエート以外の樹脂としては、例えば、ポリブチレンアジペートテレフタレート共重合体(PBAT)、ポリプリブチレンサクシネート(PBS)、ポリブチレンサクシネートアジペート共重合体(PBSA)等の生分解性を有するポリエステル樹脂;デンプン、セルロースなどの天然高分子などを配合することもできる。また、上記以外の熱可塑性樹脂を必要に応じて配合することもできる。 The polyester resin composition of the present invention may contain a resin (polymer) other than polyhydroxyalkanoate. As resins other than polyhydroxyalkanoate, for example, those having biodegradability such as polybutylene adipate terephthalate copolymer (PBAT), polyprebutylene succinate (PBS), polybutylene succinate adipate copolymer (PBSA), etc. Polyester resin; natural polymers such as starch and cellulose can also be blended. Moreover, thermoplastic resins other than the above can also be blended as needed.
(核酸塩基類)
本発明のポリエステル樹脂組成物は、核酸塩基類を必須成分として含有する。当該核酸塩基類は、本発明のポリエステル樹脂組成物において効果的な結晶核剤として作用するものと推測される。核酸塩基類とは、アデニン、グアニン、チミン、シトシン、ウラシル及びこれらの誘導体を指す。中でも、結晶化促進効果及び固化速度の観点で、ウラシル、チミン、これらの誘導体が好ましく、ウラシルのC−6位がカルボキシル基で置換された誘導体であるオロチン酸(別名:オロット酸、ウラシル−6−カルボン酸、ビタミンB13)がより好ましい。
(Nucleic acid bases)
The polyester resin composition of the present invention contains nucleic acid bases as an essential component. The nucleic acid bases are presumed to act as an effective nucleating agent in the polyester resin composition of the present invention. Nucleobases refer to adenine, guanine, thymine, cytosine, uracil and derivatives thereof. Among them, uracil, thymine and derivatives thereof are preferable in view of the crystallization promoting effect and the solidification rate, and orotic acid (alias: olotic acid, uracil-6) which is a derivative in which C-6 position of uracil is substituted by a carboxyl group. -Carboxylic acid, vitamin B 13 ) is more preferred.
核酸塩基類は、予め粉砕等により平均粒径(d50)を小さくしてから添加することにより、結晶核剤としての効果をより高めることができる。平均粒径としては0.1〜500μmが好ましく、より好ましくは0.5〜50μmである。該平均粒径は、レーザー回折/散乱式粒子径分布測定装置により測定できる。 The effect as a nucleating agent can be further enhanced by adding nucleic acid bases after reducing the average particle size (d50) in advance by grinding or the like. The average particle size is preferably 0.1 to 500 μm, more preferably 0.5 to 50 μm. The average particle size can be measured by a laser diffraction / scattering type particle size distribution measuring apparatus.
核酸塩基類の粒径を小さくする方法としては、乳鉢による粉砕のほか、衝突板式または粉体衝突式のジェットミル、ビーズミル、ハンマーミル等従来公知の方法が使用できる。 As a method of reducing the particle size of nucleic acid bases, conventionally known methods such as collision plate type or powder collision type jet mill, bead mill, hammer mill, etc. can be used besides grinding with a mortar.
本発明のポリエステル樹脂組成物における核酸塩基類の含有量は、特に限定されないが、結晶化速度向上および得られる樹脂組成物の物理的性質のバランスの観点から、ポリヒドロキシアルカノエート(例えばP3HA)100重量部に対し、0.01〜10重量部が好ましく、より好ましくは0.3〜5重量部であり、さらに好ましくは0.5〜3重量部である。 The content of the nucleic acid bases in the polyester resin composition of the present invention is not particularly limited, but from the viewpoint of improving the crystallization rate and the balance of physical properties of the obtained resin composition, polyhydroxyalkanoate (for example, P3HA) 100 0.01 to 10 parts by weight is preferable, more preferably 0.3 to 5 parts by weight, and still more preferably 0.5 to 3 parts by weight with respect to the parts by weight.
本発明のポリエステル樹脂組成物は、上述した成分以外のその他の成分をさらに含んでいてもよい。その他の成分としては、各種添加剤、例えば酸化防止剤、紫外線吸収剤、染料・顔料などの着色剤、可塑剤、滑剤、離型剤、無機充填剤(例えば、カーボンブラック、炭酸カルシウム、酸化ケイ素、ケイ酸塩、亜鉛華、ハイサイトクレー、カオリン、塩基性炭酸マグネシウム、マイカ、タルク、石英粉、ケイ藻土、ドロマイト粉、酸化チタン、酸化亜鉛、酸化アンチモン、硫酸バリウム、硫酸カルシウム、アルミナ、ケイ酸カルシウム、窒化ホウ素、塩化アンモニウム、ガラス繊維、ウィスカー、炭素繊維等)、有機充填材(架橋高分子ポリスチレン、ロジン系金属塩等;人毛、羊毛、竹繊維、パルプ繊維の有機繊維等)、帯電防止剤、防カビ剤、撥水剤、抗菌剤、発泡剤、難燃剤、結晶核剤等が挙げられる。その他の成分の含有量は特に限定されず、適宜調整可能である。その他の成分は、1種を単独で使用することもできるし、2種以上を組み合わせて使用することもできる。 The polyester resin composition of the present invention may further contain other components in addition to the components described above. Other components include various additives such as antioxidants, UV absorbers, colorants such as dyes and pigments, plasticizers, lubricants, mold release agents, inorganic fillers (for example, carbon black, calcium carbonate, silicon oxide , Silicate, zinc flower, high site clay, kaolin, basic magnesium carbonate, mica, talc, quartz powder, kieselguhr, dolomite powder, titanium oxide, zinc oxide, antimony oxide, antimony oxide, barium sulfate, calcium sulfate, alumina, Calcium silicate, boron nitride, ammonium chloride, glass fiber, whisker, carbon fiber etc., organic filler (crosslinked polymer polystyrene, rosin metal salt etc .; human hair, wool, bamboo fiber, pulp fiber organic fiber etc) And antistatic agents, fungicides, water repellents, antibacterial agents, foaming agents, flame retardants, crystal nucleating agents and the like. The content of the other components is not particularly limited, and can be appropriately adjusted. The other components may be used alone or in combination of two or more.
本発明のポリエステル樹脂組成物は、可塑剤を含んでいてもよい。可塑剤としては特に限定されないが、例えば、エーテル系可塑剤、エステル系可塑剤、フタル酸系可塑剤、リン系可塑剤が好ましく、ポリヒドロキシアルカノエート、特にP3HAとの相溶性に優れる点から、エーテル系可塑剤、エステル系可塑剤がより好ましい。エーテル系可塑剤としては、例えば、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコールなどのポリオキシアルキレングリコール等を挙げることができる。エステル系可塑剤としては、例えば、脂肪族ジカルボン酸と脂肪族アルコールとのエステル類等を挙げることができ、脂肪族ジカルボン酸として、例えばシュウ酸、コハク酸、セバシン酸、アジピン酸等を挙げることができ、脂肪族アルコールとして、例えばメタノール、エタノール、n−プロパノール、イソプロパノール、n−ヘキサノール、n−オクタノール、2−エチルヘキサノール、n−ドデカノール、ステアリルアルコール等の一価アルコール;エチレングリコール、1、2−プロピレングリコール、1、3−プロピレングリコール、1、3−ブタンジオール、1、5−ペンタンジオール、1、6−ヘキサンジオール、ジエチレングリコール、ネオペンチルグリコール、ポリエチレングリコール等の2価アルコール;グリセリン、トリメチロールプロパン、ペンタエリストール等の多価アルコールを挙げることができる。また、上記脂肪族ジカルボン酸及び/又は脂肪族アルコールの2種以上の組み合わせを含む共重合体(ジ−コポリマー、トリ−コポリマー、テトラ−コポリマーなど)、または、これらのホモポリマーおよびコポリマーから選ばれる2種以上のブレンド物が挙げられる。更に、ヒドロキシカルボン酸のエステル化物も挙げられる。上記可塑剤は1種を単独で用いてもよいし、2種以上を組み合わせて用いてもよい。可塑剤の含有量は適宜選択可能である。 The polyester resin composition of the present invention may contain a plasticizer. The plasticizer is not particularly limited, but, for example, ether plasticizers, ester plasticizers, phthalic acid plasticizers and phosphorus plasticizers are preferable, and from the viewpoint of excellent compatibility with polyhydroxyalkanoate, particularly P3HA, Ether plasticizers and ester plasticizers are more preferable. Examples of ether plasticizers include polyoxyalkylene glycols such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol. Examples of ester plasticizers include esters of aliphatic dicarboxylic acids and aliphatic alcohols, and examples of aliphatic dicarboxylic acids include oxalic acid, succinic acid, sebacic acid, adipic acid, etc. As aliphatic alcohols, for example, monohydric alcohols such as methanol, ethanol, n-propanol, isopropanol, n-hexanol, n-octanol, 2-ethylhexanol, n-dodecanol, stearyl alcohol, etc .; ethylene glycol, 1, 2 -Propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, dihydric alcohols such as polyethylene glycol, etc. glycerin, Trimethylolpropane, it may be mentioned polyhydric alcohols pentaerythritol and the like. In addition, copolymers (di-copolymers, tri-copolymers, tetra-copolymers, etc.) containing combinations of two or more of the above aliphatic dicarboxylic acids and / or aliphatic alcohols, or homopolymers and copolymers thereof are selected. Two or more blends are mentioned. Furthermore, esters of hydroxycarboxylic acids are also mentioned. The above plasticizers may be used alone or in combination of two or more. The content of the plasticizer can be selected appropriately.
本発明の樹脂組成物には、本発明の効果を阻害しない範囲で、脂肪酸アミドを配合してもよい。本発明の樹脂組成物において脂肪酸アミドは、結晶核剤として、又は、内滑剤及び外滑剤として作用し得ると考えられる。 A fatty acid amide may be added to the resin composition of the present invention as long as the effects of the present invention are not inhibited. In the resin composition of the present invention, it is considered that the fatty acid amide can act as a nucleating agent or as an internal lubricant and an external lubricant.
脂肪酸アミドとしては、式:R1−C(=O)−NR2R3で表される化合物が挙げられる。ここで、R1、R2、R3は、それぞれ独立して、水素原子、又は炭素数1〜30の炭化水素基を表す。当該炭化水素基は、飽和であってもよいし、不飽和であってもよい。また、当該炭化水素基は、置換基を有していなくてもよいし、水酸基、アルコキシ基、ハロゲン基、カルボキシル基、アミノ基、アミド基等の置換基を有してもよい。さらに、R1とR2又はR3とが結合して環状構造を形成してもよい。 Examples of fatty acid amides include compounds represented by the formula: R 1 -C (= O) -NR 2 R 3 . Here, R 1 , R 2 and R 3 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. The hydrocarbon group may be saturated or unsaturated. The hydrocarbon group may have no substituent, or may have a substituent such as a hydroxyl group, an alkoxy group, a halogen group, a carboxyl group, an amino group, an amido group and the like. Furthermore, R 1 and R 2 or R 3 may combine to form a cyclic structure.
脂肪酸アミドの具体例としては、パルミチン酸アミド、ステアリン酸アミド、エルカ酸アミド(EA)、ベヘン酸アミド(BA)、リシノール酸アミド、ヒドロキシステアリン酸アミド、N−オレイルパルミチン酸アミド、N−ステアリルエルカ酸アミド、メチレンビスラウリン酸アミド、メチレンビスステアリン酸アミド、メチレンビスヒドロキシステアリン酸アミド、エチレンビスオレイン酸アミド、エチレンビスエルカ酸アミド、エチレンビスステアリン酸アミド、エチレンビスラウリン酸アミド、エチレンビスカプリン酸アミド、エチレンビスカプリル酸アミド、エチレンビスヒドロキシステアリン酸アミド、N,N’−ジステアリルセバシン酸アミド、ヘキサンメチレンビスステアリン酸アミド等が挙げられる。脂肪酸アミドは1種類を単独で使用してもよいし、2種以上を併用してもよい。 Specific examples of fatty acid amides include palmitic acid amide, stearic acid amide, erucic acid amide (EA), behenic acid amide (BA), ricinoleic acid amide, hydroxystearic acid amide, N-oleylpalmitic acid amide, N-stearyl eruka Acid amide, methylene bis lauric acid amide, methylene bis stearic acid amide, methylene bis hydroxy stearic acid amide, ethylene bis oleic acid amide, ethylene bis erucic acid amide, ethylene bis stearic acid amide, ethylene bis lauric acid amide, ethylene bis capric acid An amide, ethylenebiscaprylic acid amide, ethylenebishydroxystearic acid amide, N, N'-distearyl sebacic acid amide, hexane methylene bis stearic acid amide, etc. are mentioned. One type of fatty acid amide may be used alone, or two or more types may be used in combination.
脂肪酸アミドとしては、100〜150℃(特に100〜120℃)程度の融点を持つ化合物が好ましい。このような融点を示す脂肪酸アミドを、融点が90℃以上のP3HAに対して配合すると、当該P3HAの融点よりも10〜30℃高い温度での成形加工において結晶化速度が向上し、成形加工性を改善することができる。 As the fatty acid amide, a compound having a melting point of about 100 to 150 ° C. (particularly 100 to 120 ° C.) is preferable. When a fatty acid amide exhibiting such a melting point is blended to P3 HA having a melting point of 90 ° C. or higher, the crystallization speed is improved in molding processing at a temperature 10 to 30 ° C. higher than the melting point of the P3 HA, and molding processability Can be improved.
脂肪酸アミドのうち、前記式においてR1が炭素数1〜30(特に炭素数10〜20)の脂肪族炭化水素基を表し、R2及びR3が水素原子を表す1級アミドが好ましい。なかでも、ベヘン酸アミド(融点114℃)、ステアリン酸アミド(融点102℃)、エチレンビスステアリン酸アミド(融点147℃)、ヒドロキシステアリン酸アミド(107℃)、メチロールベヘン酸アミド(融点110℃)が好ましい。 Among fatty acid amides, preferred are primary amides in which R 1 represents an aliphatic hydrocarbon group having 1 to 30 carbon atoms (particularly 10 to 20 carbon atoms), and R 2 and R 3 each represent a hydrogen atom. Among them, behenic acid amide (melting point 114 ° C.), stearic acid amide (melting point 102 ° C.), ethylenebisstearic acid amide (melting point 147 ° C.), hydroxystearic acid amide (107 ° C.), methylol behenic acid amide (melting point 110 ° C.) Is preferred.
本発明の樹脂組成物における脂肪酸アミドの含有量は、特に限定されないが、ポリヒドロキシアルカノエート(例えばP3HA)100重量部に対して0.1〜10重量部が好ましく、より好ましくは0.2〜5重量部、さらに好ましくは0.5〜1重量部である。脂肪酸アミドの含有量を上記範囲に制御することにより、樹脂組成物の成形加工性がいっそう向上する傾向がある。 The content of fatty acid amide in the resin composition of the present invention is not particularly limited, but it is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 10 parts by weight with respect to 100 parts by weight of polyhydroxyalkanoate (eg P3HA) It is 5 parts by weight, more preferably 0.5 to 1 part by weight. By controlling the content of the fatty acid amide in the above range, the moldability of the resin composition tends to be further improved.
本発明の樹脂組成物は、上述のように溶融混練した後、それをストランド状に押し出してからカットして、円柱状、楕円柱状、球状、立方体状、直方体状などの粒子形状のペレットとすることができる。得られたペレットを、40〜80℃で十分に乾燥させて水分を除去した後、公知の成形加工方法で成形加工でき、任意の成形体を得ることができる。成形加工方法としては、例えば、フィルム成形、シート成形、射出成形、ブロー成形、ブロー成形、繊維の紡糸、押出発泡、ビーズ発泡等が挙げられる。 After melt-kneading as described above, the resin composition of the present invention is extruded into strands and then cut into pellets of particle shape such as columnar, elliptical columnar, spherical, cubic or rectangular solid. be able to. The obtained pellet can be sufficiently dried at 40 to 80 ° C. to remove moisture, and then molded and processed by a known molding method to obtain an arbitrary molded body. Examples of the molding method include film molding, sheet molding, injection molding, blow molding, blow molding, fiber spinning, extrusion foaming, bead foaming and the like.
フィルム成形体の製造方法としては、例えば、Tダイ押出し成形、カレンダー成形、ロール成形、インフレーション成形が挙げられる。ただし、フィルム成形法はこれらに限定されるものではない。また、本発明の樹脂組成物から得られたフィルムは、加熱による熱成形、真空成形、プレス成形が可能である。 Examples of the method for producing a film molded body include T-die extrusion molding, calendar molding, roll molding, and inflation molding. However, the film forming method is not limited to these. The film obtained from the resin composition of the present invention can be thermoformed by heating, vacuum formed, or press formed.
射出成形体の製造方法としては、例えば、熱可塑性樹脂を成形する場合に一般的に採用される射出成形法、ガスアシスト成形法、射出圧縮成形法等の射出成形法を採用することができる。また、その他の目的に合わせて、上記の方法以外でもインモールド成形法、ガスプレス成形法、2色成形法、サンドイッチ成形法、PUSH−PULL、SCORIM等を採用することもできる。ただし、射出成形法はこれらに限定されるものではない。 As a method for producing an injection-molded article, for example, injection molding such as injection molding, gas assist molding, injection compression molding and the like generally employed when molding thermoplastic resin can be adopted. In addition to the above methods, in-mold molding method, gas press molding method, two-color molding method, sandwich molding method, PUSH-PULL, SCORIM, etc. may be adopted according to other purposes. However, the injection molding method is not limited to these.
本発明の樹脂組成物は、押出成形機を用いてペレット、または、フィルム状、シート状、又は繊維状等の成形体に加工しても良いし、射出成形により所定形状の成形体に加工することも可能である。 The resin composition of the present invention may be processed into a pellet, or a film-like, sheet-like or fiber-like molded article using an extrusion molding machine, or may be processed into a molded article of a predetermined shape by injection molding. It is also possible.
また、本発明の樹脂組成物が発泡剤を含有する場合、本発明の成形体は発泡性の成形体であってもよいし、加工後に発泡させることで成形発泡体としてもよい。 When the resin composition of the present invention contains a foaming agent, the molded article of the present invention may be a foamable molded article or may be formed into a molded foam by foaming after processing.
本発明の樹脂組成物は各種形状の成形体に加工することができる。該成形体としては、例えば、紙、フィルム、シート、チューブ、板、棒、容器、袋、部品が挙げられる。また、本発明の成形体は、その物性を改善するために、本発明の樹脂組成物とは異なる材料から構成される成形体(例えば、繊維、糸、ロープ、織物、編物、不織布、紙、フィルム、シート、チューブ、板、棒、容器、袋、部品、発泡体等)と複合化することもできる。本発明の成形品の用途は特に限定されず、農業、漁業、林業、園芸、医学、衛生品、衣料、非衣料、包装、自動車、建材、その他の分野に好適に用いることができる。 The resin composition of the present invention can be processed into molded articles of various shapes. Examples of the molded body include paper, film, sheet, tube, plate, rod, container, bag, and part. Moreover, in order to improve the physical properties of the molded article of the present invention, a molded article composed of a material different from the resin composition of the present invention (for example, fiber, yarn, rope, woven fabric, knitted fabric, non-woven fabric, paper, Films, sheets, tubes, plates, rods, containers, bags, parts, foams, etc.) can also be combined. The application of the molded article of the present invention is not particularly limited, and can be suitably used in the fields of agriculture, fishery, forestry, horticulture, medicine, hygiene products, clothing, non-clothing, packaging, automobiles, building materials and the like.
次に実施例に基づいて本発明をさらに詳細に説明するが、本発明はかかる実施例のみに制限されるものではない。 Next, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.
<P3HA>
各実施例又は比較例では、P3HAとして、PHBH:ポリ(3−ヒドロキシブチレート−コ−3−ヒドロキシヘキサノエート)を使用した。このPHBHは、PHBH生産菌を培養した後、菌体から樹脂成分を回収して得たもので、HH率:PHBH中の3−ヒドロキシヘキサノエートのモル分率(mol%)は11mol%、Mwは67.2万である。なお、PHBH生産菌としては、Alcaligenes eutrophusに、Aeromonas caviae由来のPHA合成酵素遺伝子を導入したAlcaligenes eutrophus AC32(J.Bacteriol.,179,4821(1997))を使用した。
<P3HA>
In each example or comparative example, PHBH: poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) was used as P3HA. This PHBH is obtained by recovering PHBH-producing bacteria and then recovering the resin component from the cells, and the HH ratio: the molar fraction (mol%) of 3-hydroxyhexanoate in PHBH is 11 mol%, Mw is 67.2 thousand. In addition, Alcaligenes eutrophus AC32 (J. Bacteriol., 179, 4821 (1997)) which introduce | transduced the PHA synthetic enzyme gene derived from Aeromonas caviae into Alcaligenes eutrophus was used as PHBH production microbe.
<分子量測定>
PHBHの重量平均分子量Mwは、GPC測定により求めた。GPC装置はLC−10Aシステム(島津製作所製)を使用し、カラムはGPCK−806M(昭和電工製)を使用し、カラム温度は40℃とした。対象物質3mgをクロロホルム2mlに溶解したものを、10μl注入して、ポリスチレン換算によりMwを求めた。
<Molecular weight measurement>
The weight average molecular weight Mw of PHBH was determined by GPC measurement. The GPC apparatus used LC-10A system (made by Shimadzu Corp.), the column used GPCK-806M (made by Showa Denko), and column temperature was 40 degreeC. 10 μl of a solution of 3 mg of the target substance in 2 ml of chloroform was injected to determine Mw by polystyrene conversion.
<添加剤>
オロチン酸・一水和物(以降オロチン酸と称する)としては、和光純薬工業社品(特級試薬)を使用した。その他の試薬は、は各々和光純薬工業社品(特級試薬)を使用した。
<Additives>
A product from Wako Pure Chemical Industries, Ltd. (special grade reagent) was used as orotic acid monohydrate (hereinafter referred to as orotic acid). The other reagents used were products manufactured by Wako Pure Chemical Industries, Ltd. (special grade reagents).
<ポリ乳酸>
ポリ乳酸としては、結晶性ポリ乳酸(Ingeo3251D、ネイチャーワークス社品)を使用した。
<Poly lactic acid>
As polylactic acid, crystalline polylactic acid (Ingeo 3251D, manufactured by Nature Works Inc.) was used.
(実施例1)
ポリエステル樹脂組成物の製造は、DSM社製小型混練機XPloreシリーズMC5を用いて実施した。まず、表1に示すように、P3HA(PHBH)100重量部に対してオロチン酸1.5重量部をドライブレンドして、粉体の混合物を得た。この粉体混合物を、設定温度180℃、スクリュー回転数100rpm、混練時間3分の条件で溶融混練した後、混練機から吐出した直後の溶融物を約55℃の温浴に投入し、溶融物を固化させてポリエステル樹脂組成物を製造した。
Example 1
The polyester resin composition was manufactured using a small-sized kneader XPlore series MC5 manufactured by DSM. First, as shown in Table 1, 1.5 parts by weight of orotic acid was dry-blended with 100 parts by weight of P3HA (PHBH) to obtain a powder mixture. The powder mixture is melt-kneaded under conditions of a set temperature of 180 ° C., screw rotation speed of 100 rpm, and a kneading time of 3 minutes, and then the melt immediately after being discharged from the kneader is charged into a warm bath of about 55 ° C. It solidified and manufactured the polyester resin composition.
ポリエステル樹脂組成物を製造する際に、温浴に投入してから溶融物が固化するのに要した時間を「固化時間」として測定した。結晶化が速いほど固化時間が短くなり、固化時間が短いほど固化特性に優れていることを意味する。固化特性に優れていることは、成形加工の際に迅速に固化させることができ、成形体を優れた生産性で製造できる(即ち、成形加工性に優れる)ことを意味する。同じ手順で固化時間の測定を3回行い、その平均値を表に示す。 When manufacturing a polyester resin composition, the time which it took for a molten material to solidify after being injected | thrown-in to a warm water bath was measured as "solidification time." The faster the crystallization, the shorter the solidification time, and the shorter the solidification time, the better the solidification characteristics. Being excellent in solidification characteristics means that it can be solidified quickly during molding processing, and molded articles can be produced with excellent productivity (that is, excellent in moldability). The measurement of solidification time was performed three times in the same procedure and the average value is shown in the table.
<ブリードアウト有無の評価>
上記で得た粉体の混合物(PHBH100重量部に対してオロチン酸1.5重量部をドライブレンドして得られたもの)1kgを、東芝機械社製の二軸混錬押出機TEM−26SSにより150℃にて溶融加工を行い、樹脂ペレットを得た。このペレットを東洋精機社製ラボプラストミル モデル30C150を用いて140℃にて再度溶融加工を行い、厚さ約100μmのTダイシートを得た。このTダイシートを60℃のオーブン(ヤマト科学社製ドライオーブンDSV602)にて1日間放置した後、シート表面を目視観察することによりブリードアウトの有無を判定した。実施例1で得られたポリエステル樹脂組成物は、ブリードアウト無しとの結果であった。
<Evaluation of presence or absence of bleed-out>
1 kg of the powder mixture obtained above (obtained by dry blending 1.5 parts by weight of orotic acid with 100 parts by weight of PHBH) with a twin-screw kneading extruder TEM-26SS manufactured by Toshiba Machine Co., Ltd. Melt processing was performed at 150 ° C. to obtain resin pellets. The pellets were melt-processed again at 140 ° C. using a Labo Plastomill Model 30C150 manufactured by Toyo Seiki Co., Ltd. to obtain a T-die sheet having a thickness of about 100 μm. The T-die sheet was left in an oven at 60 ° C. (dry oven DSV602 manufactured by Yamato Scientific Co., Ltd.) for 1 day, and the surface of the sheet was visually observed to determine the presence or absence of bleed-out. The polyester resin composition obtained in Example 1 resulted in no bleed out.
(実施例2〜4、比較例1〜5)
添加剤の種類及び配合量を表1に示すように変更したこと以外は実施例1と同様にして、ポリエステル樹脂組成物の製造及び固化時間の測定を実施した。
(Examples 2-4, comparative examples 1-5)
The production of the polyester resin composition and the measurement of the setting time were carried out in the same manner as in Example 1 except that the types and amounts of additives were changed as shown in Table 1.
(比較例6)
結晶性ポリ乳酸100重量部に対して添加剤としてオロチン酸1.5重量部を用いて、固化させるための温浴の温度を80℃にして、実施例1と同様にして固化試験及び樹脂組成物の製造を実施した。
(Comparative example 6)
Solidification test and resin composition in the same manner as in Example 1 except that 1.5 parts by weight of orotic acid is used as an additive with respect to 100 parts by weight of crystalline polylactic acid, and the temperature of the bath for solidification is 80.degree. Production of
(比較例7)
添加剤の種類を表2に示したものに変更したこと以外は比較例6と同様にして、固化試験及び樹脂組成物の製造を実施した。
(Comparative example 7)
A solidification test and production of a resin composition were carried out in the same manner as in Comparative Example 6 except that the types of additives were changed to those shown in Table 2.
Claims (7)
Poly (3-hydroxyalkanoate) is poly (3-hydroxybutyrate), poly (3-hydroxybutyrate-co-3-hydroxyvalerate), poly (3-hydroxybutyrate-co-3-hydroxyhexa) The polyester resin composition according to claim 6, which is at least one selected from the group consisting of (noate) and poly (3-hydroxybutyrate-co-4-hydroxybutyrate).
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KR20230018416A (en) | 2020-06-02 | 2023-02-07 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | Method for producing a polymer molding involving pretreatment by heating |
CN113927987A (en) * | 2021-09-30 | 2022-01-14 | 彤程化学(中国)有限公司 | Full-biodegradable self-adhesive preservative film and preparation method thereof |
WO2024087609A1 (en) * | 2022-10-28 | 2024-05-02 | 北京蓝晶微生物科技有限公司 | Polybasic-acid-containing polyhydroxyalkanoate composition and polyhydroxyalkanoate molded body |
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