JP5019554B2 - Biodegradable polyester resin composition - Google Patents
Biodegradable polyester resin composition Download PDFInfo
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- JP5019554B2 JP5019554B2 JP2005265121A JP2005265121A JP5019554B2 JP 5019554 B2 JP5019554 B2 JP 5019554B2 JP 2005265121 A JP2005265121 A JP 2005265121A JP 2005265121 A JP2005265121 A JP 2005265121A JP 5019554 B2 JP5019554 B2 JP 5019554B2
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- 239000011342 resin composition Substances 0.000 title claims description 29
- 229920000229 biodegradable polyester Polymers 0.000 title claims description 24
- 239000004622 biodegradable polyester Substances 0.000 title claims description 24
- 239000003484 crystal nucleating agent Substances 0.000 claims description 47
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 33
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 33
- 101710108497 p-hydroxybenzoate hydroxylase Proteins 0.000 claims description 25
- 229920002101 Chitin Polymers 0.000 claims description 20
- 229920001661 Chitosan Polymers 0.000 claims description 20
- HPMGFDVTYHWBAG-UHFFFAOYSA-N 3-hydroxyhexanoic acid Chemical compound CCCC(O)CC(O)=O HPMGFDVTYHWBAG-UHFFFAOYSA-N 0.000 claims description 15
- 238000000465 moulding Methods 0.000 claims description 12
- 229920003232 aliphatic polyester Polymers 0.000 claims description 11
- 244000005700 microbiome Species 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 9
- 229920000070 poly-3-hydroxybutyrate Polymers 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229920000739 poly(3-hydroxycarboxylic acid) polymer Polymers 0.000 claims description 2
- NYHNVHGFPZAZGA-UHFFFAOYSA-N 2-hydroxyhexanoic acid Chemical compound CCCCC(O)C(O)=O NYHNVHGFPZAZGA-UHFFFAOYSA-N 0.000 claims 1
- 238000002425 crystallisation Methods 0.000 description 29
- 230000008025 crystallization Effects 0.000 description 29
- 229920000331 Polyhydroxybutyrate Polymers 0.000 description 18
- 238000002844 melting Methods 0.000 description 11
- 230000008018 melting Effects 0.000 description 11
- 238000005187 foaming Methods 0.000 description 10
- 238000012545 processing Methods 0.000 description 9
- 238000005259 measurement Methods 0.000 description 8
- 238000001000 micrograph Methods 0.000 description 7
- 241000252867 Cupriavidus metallidurans Species 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000009987 spinning Methods 0.000 description 6
- 239000011324 bead Substances 0.000 description 5
- 238000000071 blow moulding Methods 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- REKYPYSUBKSCAT-UHFFFAOYSA-N 3-hydroxypentanoic acid Chemical compound CCC(O)CC(O)=O REKYPYSUBKSCAT-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- -1 SiO 2 Chemical class 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002667 nucleating agent Substances 0.000 description 3
- 229920000520 poly(3-hydroxybutyrate-co-3-hydroxyvalerate) Polymers 0.000 description 3
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 description 3
- 229920000903 polyhydroxyalkanoate Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- WHBMMWSBFZVSSR-UHFFFAOYSA-M 3-hydroxybutyrate Chemical compound CC(O)CC([O-])=O WHBMMWSBFZVSSR-UHFFFAOYSA-M 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- WHBMMWSBFZVSSR-UHFFFAOYSA-N R3HBA Natural products CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 239000012785 packaging film Substances 0.000 description 2
- 229920006280 packaging film Polymers 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 108010010718 poly(3-hydroxyalkanoic acid) synthase Proteins 0.000 description 2
- 229920001020 poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) Polymers 0.000 description 2
- 229920001013 poly(3-hydroxybutyrate-co-4-hydroxybutyrate) Polymers 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 239000002759 woven fabric Substances 0.000 description 2
- POMQYTSPMKEQNB-UHFFFAOYSA-N 3-hydroxyoctadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)CC(O)=O POMQYTSPMKEQNB-UHFFFAOYSA-N 0.000 description 1
- SJZRECIVHVDYJC-UHFFFAOYSA-M 4-hydroxybutyrate Chemical compound OCCCC([O-])=O SJZRECIVHVDYJC-UHFFFAOYSA-M 0.000 description 1
- 241000607534 Aeromonas Species 0.000 description 1
- 241000607516 Aeromonas caviae Species 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 241000588986 Alcaligenes Species 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241000193033 Azohydromonas lata Species 0.000 description 1
- 229910004762 CaSiO Inorganic materials 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 229920001222 biopolymer Polymers 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000004301 calcium benzoate Substances 0.000 description 1
- 235000010237 calcium benzoate Nutrition 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical compound [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 0.000 description 1
- GUPPESBEIQALOS-UHFFFAOYSA-L calcium tartrate Chemical compound [Ca+2].[O-]C(=O)C(O)C(O)C([O-])=O GUPPESBEIQALOS-UHFFFAOYSA-L 0.000 description 1
- 239000001427 calcium tartrate Substances 0.000 description 1
- 235000011035 calcium tartrate Nutrition 0.000 description 1
- HZQXCUSDXIKLGS-UHFFFAOYSA-L calcium;dibenzoate;trihydrate Chemical compound O.O.O.[Ca+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 HZQXCUSDXIKLGS-UHFFFAOYSA-L 0.000 description 1
- PYSZASIZWHHPHJ-UHFFFAOYSA-L calcium;phthalate Chemical compound [Ca+2].[O-]C(=O)C1=CC=CC=C1C([O-])=O PYSZASIZWHHPHJ-UHFFFAOYSA-L 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 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 1
- 239000000314 lubricant Substances 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- UQGPCEVQKLOLLM-UHFFFAOYSA-N pentaneperoxoic acid Chemical compound CCCCC(=O)OO UQGPCEVQKLOLLM-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 229940039790 sodium oxalate Drugs 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
Description
本発明は、生分解性ポリエステル系樹脂組成物、該樹脂組成物の成形体、ならびに新規な前記樹脂組成物用の結晶核剤に関する。 The present invention relates to a biodegradable polyester resin composition, a molded article of the resin composition, and a novel crystal nucleating agent for the resin composition.
近年廃棄プラスチックが引き起こす環境問題がクローズアップされ、地球規模での循環型社会の実現が切望される中で、使用後微生物の働きによって水と二酸化炭素に分解される生分解性プラスチックが注目を集めている。 In recent years, the environmental problems caused by waste plastics have been highlighted, and the realization of a recycling society on a global scale is eagerly desired. ing.
これらの生分解性プラスチックの大部分は脂肪族ポリエステルである。ポリエステルは一般に結晶化速度が遅いが、なかでも脂肪族ポリエステルは結晶化が遅く、さらにポリヒドロキシアルカノエート（略称ＰＨＡ）は結晶化が遅い（非特許文献１）。このため、成形加工時に溶融状態からの固化が遅くて加工が困難になり、加工できても、ラインスピードなどが遅くなり、成形加工の生産性が悪いという欠点がある。 Most of these biodegradable plastics are aliphatic polyesters. Polyesters generally have a slow crystallization rate, but aliphatic polyesters are slow to crystallize, and polyhydroxyalkanoates (abbreviated as PHA) are slow to crystallize (Non-patent Document 1). For this reason, the solidification from the molten state is slow at the time of molding and processing becomes difficult, and even if it can be processed, there is a disadvantage that the line speed is slowed and the productivity of molding processing is poor.
そこで、ポリエステルの結晶化速度を改善するために、種々の結晶核剤の添加が検討されている。従来知られている結晶核剤としては、例えば特許文献１に特定のポリエステルに対し、Ｚｎ粉末、Ａｌ粉末、グラファイト、カーボンブラックなどの無機単体；ＺｎＯ、ＭｇＯ、Ａｌ2Ｏ3、ＴｉＯ2、ＭｎＯ2、ＳｉＯ2、Ｆｅ3Ｏ4などの金属酸化物；窒化アルミ、窒化珪素、窒化チタン、窒化ホウ素などの窒化物；Ｎａ2ＣＯ3、ＣａＣＯ3、ＭｇＣＯ3、ＣａＳＯ4、ＣａＳｉＯ3、ＢａＳＯ4、Ｃａ3（ＰＯ4）3などの無機塩；タルク、カオリン、クレー、白土などの粘土類；シュウ酸カルシウム、シュウ酸ナトリウム、安息香酸カルシウム、フタル酸カルシウム、酒石酸カルシウム、ステアリン酸マグネシウム、ポリアクリル酸塩などの有機塩類；ポリエステル、ポリエチレン、ポリプロピレンなどの高分子化合物などを添加することが開示されている。 Therefore, in order to improve the crystallization speed of polyester, addition of various crystal nucleating agents has been studied. Examples of conventionally known crystal nucleating agents include inorganic simple substances such as Zn powder, Al powder, graphite, and carbon black, for example, specific polyester disclosed in Patent Document 1; ZnO, MgO, Al 2 O 3 , TiO 2 , and MnO. 2 , metal oxides such as SiO 2 , Fe 3 O 4 ; nitrides such as aluminum nitride, silicon nitride, titanium nitride, boron nitride; Na 2 CO 3 , CaCO 3 , MgCO 3 , CaSO 4 , CaSiO 3 , BaSO 4 Inorganic salts such as Ca 3 (PO 4 ) 3 ; clays such as talc, kaolin, clay, clay; calcium oxalate, sodium oxalate, calcium benzoate, calcium phthalate, calcium tartrate, magnesium stearate, polyacryl Organic salts such as acid salts; polymer compounds such as polyester, polyethylene, and polypropylene are added. Is disclosed.
また、特許文献２には、ＰＨＡの結晶核剤として、タルク、微粒化雲母、窒化ホウ素、炭酸カルシウムが挙げられ、より効果的なものとして、有機ホスホン酸もしくは有機ホスフィン酸、またはそれらのエステル、あるいはそれらの酸もしくはエステルの誘導体、及び周期律表の第I〜V族の金属の酸化物、水酸化物、及び飽和または不飽和カルボン酸塩
からなる群より選択される金属化合物が開示されている。
しかしながら、実質的に効果の高い結晶核剤は未だ見出されていないのが現状である。
However, the present situation is that a crystal nucleating agent having a substantially high effect has not yet been found.
本発明の課題は、使用後微生物の働きによって水と二酸化炭素に分解される生分解性ポリエステルの中でも特に結晶化の遅いＰ３ＨＡの欠点である結晶化の遅さを改善し、射出成形、フィルム成形、ブロー成形、繊維の紡糸、押出発泡、ビーズ発泡などの加工における加工性、加工速度を改善することである。 The object of the present invention is to improve the slow crystallization, which is a disadvantage of P3HA, which is slow to crystallize among biodegradable polyesters which are decomposed into water and carbon dioxide by the action of microorganisms after use, and injection molding, film molding It is to improve processability and processing speed in processes such as blow molding, fiber spinning, extrusion foaming and bead foaming.
本発明者らは、結晶化の遅いＰ３ＨＡに効果的な結晶核剤を見出すべく鋭意検討した結果、ポリビニルアルコール、キチンおよびキトサンから選ばれる１種以上の結晶核剤を混合することにより、結晶化速度を著しく改善できることを見出し、本発明を完成するに至った。
即ち本発明は、
〔１〕微生物から生産される式（１）：［−ＣＨＲ−ＣＨ2−ＣＯ−Ｏ−］（式中、ＲはＣnＨ2n+1で表されるアルキル基で、ｎ＝１以上１５以下の整数である。）で示される繰り返し単位からなる脂肪族ポリエステル系重合体（以下、ポリ（３−ヒドロキシアルカノエート）：略称Ｐ３ＨＡ）と、ポリビニルアルコール、キチンおよびキトサンから選ばれる１種以上からなる結晶核剤とを混合してなり、前記Ｐ３ＨＡが、式（１）において、ｎ＝１である繰り返し単位とｎ＝３である繰り返し単位とからなる、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：略称ＰＨＢＨ）である、生分解性ポリエステル系樹脂組成物、
〔２〕前記〔１〕記載の生分解性ポリエステル系樹脂組成物を成形加工してなる成形体、
に関する。
なお、本発明において、結晶核剤とは、脂肪族ポリエステル単独重合体または共重合体などの脂肪族ポリエステル系重合体を結晶化する際の核として作用する剤をいう。
As a result of diligent research to find an effective crystal nucleating agent for P3HA, which is slow to crystallize, the present inventors have mixed crystallization agent of at least one selected from polyvinyl alcohol, chitin, and chitosan, thereby crystallization. It has been found that the speed can be remarkably improved and the present invention has been completed.
That is, the present invention
[1] Formula (1) produced from a microorganism: [—CHR—CH 2 —CO—O—] (wherein R is an alkyl group represented by C n H 2n + 1 , and n = 1 to 15 An aliphatic polyester polymer (hereinafter referred to as poly (3-hydroxyalkanoate): abbreviated as P3HA), and at least one selected from polyvinyl alcohol, chitin, and chitosan. A poly (3-hydroxybutyrate-co-- compound, wherein the P3HA is composed of a repeating unit of n = 1 and a repeating unit of n = 3 in the formula (1). 3-hydroxyhexanoate: abbreviated as PHBH), a biodegradable polyester resin composition,
[2] A molded product obtained by molding the biodegradable polyester resin composition according to [1],
About.
In the present invention, the crystal nucleating agent refers to an agent that acts as a nucleus for crystallization of an aliphatic polyester polymer such as an aliphatic polyester homopolymer or copolymer.
本発明によれば、Ｐ３ＨＡの結晶化の速度が著しく改善され、射出成形、フィルム成形、ブロー成形、繊維の紡糸、押出発泡、ビーズ発泡などの加工における加工性、加工速度が改善されるという効果が奏される。また、結晶核剤がポリビニルアルコール、キチンおよびキトサンから選ばれる１種以上を含有しているため、基材の生分解性脂肪族ポリエステルの生分解性を損なうことがない。 According to the present invention, the crystallization speed of P3HA is remarkably improved, and the processability and processing speed in processes such as injection molding, film molding, blow molding, fiber spinning, extrusion foaming, and bead foaming are improved. Is played. Moreover, since the crystal nucleating agent contains one or more selected from polyvinyl alcohol, chitin and chitosan, the biodegradability of the biodegradable aliphatic polyester of the base material is not impaired.
本発明に用いられるＰ３ＨＡは、微生物から生産されるものであり、式（１）：
［−ＣＨＲ−ＣＨ2−ＣＯ−Ｏ−］
（式中、ＲはＣnＨ2n+1で表されるアルキル基で、ｎ＝１以上１５以下の整数である。）
で示される繰り返し単位を有する脂肪族ポリエステル系重合体である。
P3HA used in the present invention is produced from microorganisms and has the formula (1):
[—CHR—CH 2 —CO—O—]
(In the formula, R is an alkyl group represented by C n H 2n + 1 , and n is an integer of 1 to 15 inclusive.)
It is an aliphatic polyester-type polymer which has a repeating unit shown by these.
Ｐ３ＨＡを生産する微生物としては、Ｐ３ＨＡ類生産能を有する微生物であれば特に限定されない。
例えば、ＰＨＢ生産菌としては、アルカリゲネス・ユートロファス(Alcaligenes eutrophus、ラルストニア・ユートロファ(Ralstonia eutropha)ともいう)、アルカリゲネス・ラタス(Alcaligenes latus)などのアルカリゲネス属などの天然微生物が知られており、これらの微生物ではＰＨＢが菌体内に蓄積される。
また、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・キャビエ（Aeromonas caviae）、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）生産菌であるアルカリゲネス・ユートロファス(Alcaligenes eutrophus)などが知られている。
特に、ＰＨＢＨに関し、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)（J. Bateriol., 179, 4821-4830頁（1997））などがより好ましく、これらの微生物を適切な条件で培養して菌体内にＰＨＢＨを蓄積させた微生物菌体が用いられる。
The microorganism that produces P3HA is not particularly limited as long as it is a microorganism capable of producing P3HAs.
For example, as microorganisms producing PHB, natural microorganisms such as Alkigenes eutrophus (Alcaligenes eutrophus, also called Ralstonia eutropha) and Alkigenes latus (Alcaligenes latus) are known, and these microorganisms are known. Then, PHB accumulates in the microbial cells.
Examples of the copolymer-producing bacteria of hydroxybutyrate and other hydroxyalkanoates include PHBV and PHBH-producing bacteria such as Aeromonas caviae and poly (3-hydroxybutyrate-co-4-hydroxybutyrate). Alcaligenes eutrophus, which is a rate-producing bacterium, is known.
In particular, regarding PHBH, in order to increase the productivity of PHBH, Alcaligenes eutrophus AC32 strain (FERM BP-6038) into which genes of PHA synthase group have been introduced (J. Bateriol., 179, 4821-4830) (1997)) is more preferable, and microbial cells obtained by culturing these microorganisms under appropriate conditions and accumulating PHBH in the cells are used.
式（１）中、ｎ＝１（ＰＨＢホモポリマー）、ｎ＝１および２、３、５、７（Ｐ３ＨＡ共重合体）が好ましく、ｎ＝１および３がより好ましい。
Ｐ３ＨＡの重量平均分子量としては、５０,０００〜３０００、０００が好ましく、１００,０００〜１５００,０００がより好ましい。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、ポリスチレン換算分子量分布より測定されたものをいう。
In formula (1), n = 1 (PHB homopolymer), n = 1 and 2, 3, 5, 7 (P3HA copolymer) are preferable, and n = 1 and 3 are more preferable.
As a weight average molecular weight of P3HA, 50,000-3000,000 are preferable and 100,000-1500,000 are more preferable. The weight average molecular weight here refers to that measured from polystyrene-equivalent molecular weight distribution using gel permeation chromatography (GPC) using chloroform eluent.
本発明で使用するＰ３ＨＡとしては、例えば、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−ヒドロキシヘキサノエート）、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−４−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−ヒドロキシオクタノエート）、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）などが挙げられる。
なかでも、工業的に生産が可能であるものとして、ポリ（３−ヒドロキシブチレート）（略称ＰＨＢ）、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）（略称ＰＨＢＨ）、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）（略称ＰＨＢＶ）が挙げられる。
Examples of P3HA used in the present invention include poly (3-hydroxybutyrate), poly (3-hydroxybutyrate-co-3-hydroxyhexanoate), and poly (3-hydroxybutyrate-co-3-). Hydroxyvalerate), poly (3-hydroxybutyrate-co-4-hydroxybutyrate), poly (3-hydroxybutyrate-co-3-hydroxyoctanoate), poly (3-hydroxybutyrate-co-) 3-hydroxyoctadecanoate) and the like.
Among these, poly (3-hydroxybutyrate) (abbreviation PHB), poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) (abbreviation PHBH), poly (3-hydroxybutyrate) (abbreviation PHBH), poly (3-hydroxybutyrate) (abbreviation PHB), (3-hydroxybutyrate-co-3-hydroxyvalerate) (abbreviation PHBV).
Ｐ３ＨＡとしては、上記したように、工業的に生産が可能であり、物性的に有用なプラスチックであるという観点から、式（１）において、ｎ＝１である繰り返し単位からなる、ＰＨＢまたは、式（１）において、ｎ＝１である繰り返し単位とｎ＝３である繰り返し単位とからなる、ＰＨＢＨが好ましい。
ＰＨＢＨの繰り返し単位の組成比は、柔軟性と強度のバランスの観点から、ポリ（３−ヒドロキシブチレート）／ポリ（３−ヒドロキシヘキサノエート）が８０／２０以上９９／１以下（ｍｏｌ／ｍｏｌ）であることが好ましく、７５／１５以上９９／３以下（ｍｏｌ／ｍｏｌ）であることがより好ましい。前記組成比は、ＰＨＢと実質的に差がある点から、９９／１以下が好ましく、また樹脂が適度な硬度を有する点で８０／２０以上が好ましい。
As described above, as P3HA, from the viewpoint of being a plastic that can be industrially produced and is physically useful, in the formula (1), PHB or a formula consisting of a repeating unit where n = 1 is used. In (1), PHBH comprising a repeating unit with n = 1 and a repeating unit with n = 3 is preferred.
The composition ratio of PHBH repeating units is such that poly (3-hydroxybutyrate) / poly (3-hydroxyhexanoate) is 80/20 or more and 99/1 or less (mol / mol) from the viewpoint of balance between flexibility and strength. It is preferably 75/15 or more and 99/3 or less (mol / mol). The composition ratio is preferably 99/1 or less from the viewpoint of substantially different from PHB, and preferably 80/20 or more from the viewpoint that the resin has an appropriate hardness.
ＰＨＢＨは、繰り返し単位の組成比を変えることで、融点、結晶化度を変化させることができ、ヤング率、耐熱性などの物性を変化させることが可能であり、ポリプロピレンからポリエチレンの範囲の物性を持たせることが可能であり、より好ましい。 PHBH can change the melting point and crystallinity by changing the composition ratio of repeating units, and can change the physical properties such as Young's modulus and heat resistance. It is possible to have it, and it is more preferable.
ＰＨＢＶは、３−ヒドロキシブチレート（３ＨＢ）成分と３−ヒドロキシバレレート（３ＨＶ）成分の比率によって融点、ヤング率などが変化するが、３ＨＢ成分と３ＨＶ成分が共結晶化するため結晶化度は５０％以上と高く、ＰＨＢに比べれば柔軟にはなっているが、破壊伸びは５０％以下と低い傾向がある。 PHBV has different melting points, Young's modulus, etc. depending on the ratio of 3-hydroxybutyrate (3HB) component and 3-hydroxyvalerate (3HV) component. Although it is as high as 50% or more and is more flexible than PHB, the elongation at break tends to be as low as 50% or less.
本発明においては、前記Ｐ３ＨＡとポリビニルアルコール、キチン及びキトサンから選ばれる１種以上の結晶核剤とを混合することに一つの大きな特徴がある。
本発明は、ポリビニルアルコール、キチン、キトサンなどの生分解性ポリマーがＰ３ＨＡに対して、結晶核剤として従来公知のものに比べて優れた効果を発揮することを見出して完成されたものである。
従って、本発明は、ポリビニルアルコール、キチン又はキトサンを含有してなる脂肪族ポリエステル系重合体用結晶核剤（以下、単に結晶核剤ともいう）に関する。
In the present invention, one major characteristic is that the P3HA is mixed with at least one crystal nucleating agent selected from polyvinyl alcohol, chitin, and chitosan.
The present invention has been completed by finding that biodegradable polymers such as polyvinyl alcohol, chitin, and chitosan exhibit an excellent effect on P3HA as compared with conventionally known crystal nucleating agents.
Accordingly, the present invention relates to a crystal nucleating agent for aliphatic polyester-based polymer (hereinafter also simply referred to as a crystal nucleating agent) comprising polyvinyl alcohol, chitin or chitosan.
微生物が産生するＰ３ＨＡは、脂肪族ポリエステルの中でも特に結晶化速度が遅いため、本発明のような優れた結晶核剤を用いることがとりわけ有効である。また、Ｐ３ＨＡは、好気性、嫌気性何れの環境下での生分解性にも優れ、燃焼時には有毒ガスを発生しない。とりわけ、ＰＨＢＨは原料として石油由来のものを使用せず、植物原料を使用しており、地球上の二酸化炭素を増大させない、つまりカーボンニュートラルであるという優れた特徴を有している点でも好ましい。結晶核剤として混合するポリビニルアルコール、キチンおよびキトサンも生分解性を有しており、Ｐ３ＨＡの優れた分解性を損ねないという利点がある。 Since P3HA produced by microorganisms has a particularly low crystallization rate among aliphatic polyesters, it is particularly effective to use an excellent crystal nucleating agent as in the present invention. Moreover, P3HA is excellent in biodegradability in both aerobic and anaerobic environments, and does not generate toxic gas during combustion. In particular, PHBH is preferable in that it does not use petroleum-derived materials as raw materials, uses plant raw materials, and does not increase carbon dioxide on the earth, that is, has excellent characteristics of being carbon neutral. Polyvinyl alcohol, chitin, and chitosan mixed as a crystal nucleating agent also have biodegradability, and have an advantage that the excellent degradability of P3HA is not impaired.
本発明で使用するポリビニルアルコール、キチンおよびキトサンから選ばれる１種以上からなる結晶核剤は、Ｐ３ＨＡの結晶化を促進して加工を容易にする。これらの物質が結晶核剤として効果を発揮する理由は未だ明らかではないが、ポリマー分子中に存在する多くのヒドロキシル基と脂肪族ポリエステルのエステル基の水素結合などの相互作用により結晶化が促進されると考えられる。 The crystal nucleating agent comprising at least one selected from polyvinyl alcohol, chitin and chitosan used in the present invention facilitates processing by promoting crystallization of P3HA. The reason why these substances are effective as crystal nucleating agents is not yet clear, but crystallization is promoted by the interaction of many hydroxyl groups present in the polymer molecule and ester bonds of aliphatic polyester. It is thought.
中でも、結晶核剤の粒子径が小さいほど、同一添加量での結晶化促進効果が大きくなる傾向がある。これは、結晶核剤の粒径が小さいほど、結晶核の発生点が多くなるためと思われる。これらの結晶核剤の平均粒子径は、５０μｍ以下が好ましく、１０μｍ以下がさらに好ましく、５μｍ以下がより好ましい。粒子径を小さくするには、種々の粉砕機などを用いることができる。また、結晶核剤が分子分散しにくく、結晶核剤が有効に作用し、また、通常の粉砕機での粉砕して容易に得られる点から、平均粒子径は０.１μｍ以上が好ましい。 Among these, the smaller the particle size of the crystal nucleating agent, the greater the crystallization promoting effect with the same addition amount. This is probably because the smaller the particle size of the crystal nucleating agent, the more generation points of crystal nuclei. The average particle size of these crystal nucleating agents is preferably 50 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. Various pulverizers can be used to reduce the particle size. In addition, the average particle diameter is preferably 0.1 μm or more from the viewpoint that the crystal nucleating agent is difficult to disperse in the molecule, the crystal nucleating agent works effectively, and is easily obtained by pulverization with a normal pulverizer.
結晶核剤の添加量は、Ｐ３ＨＡ１００重量部に対して、０．１重量部以上１０重量部以下の範囲が好ましい。該添加量は、０．１重量部未満では結晶核数が不足して十分な結晶化促進効果が得られず、１０重量部を越えると添加効果が飽和に達してしまう他、混練して均一に分散するのが困難になる。更に好ましい添加量範囲は、０．３重量部以上７重量部以下である。 The addition amount of the crystal nucleating agent is preferably in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of P3HA. If the addition amount is less than 0.1 parts by weight, the number of crystal nuclei is insufficient and a sufficient crystallization promoting effect cannot be obtained. If the addition amount exceeds 10 parts by weight, the addition effect reaches saturation, and the addition is uniform. It becomes difficult to disperse in A more preferable addition amount range is 0.3 parts by weight or more and 7 parts by weight or less.
なお、本発明の生分解性ポリエステル系樹脂組成物は、上記成分の他に、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、無機充填剤、帯電防止剤などの他の成分を用いてもよい。これらの他の成分の添加量としては、前記Ｐ３ＨＡや結晶核剤の作用を損なわない程度であればよく、特に限定はない。 In addition to the above components, the biodegradable polyester resin composition of the present invention includes antioxidants, ultraviolet absorbers, colorants such as dyes and pigments, plasticizers, lubricants, inorganic fillers, antistatic agents, and the like. Other ingredients may be used. The amount of these other components added is not particularly limited as long as it does not impair the action of the P3HA and the crystal nucleating agent.
本発明の生分解性ポリエステル系樹脂組成物は、従来の樹脂組成物の調製方法として一般に用いられる公知の方法により容易に調製できる。例えば、Ｐ３ＡＨとポリビニルアルコール、キチンおよびキトサンから選ばれる１種以上からなる結晶核剤と、さらに必要であれば他の成分とを混合した後、押出機、ロールミル、バンバリーミキサーなどにより混練してペレットとし、成形に供する方法、ポリビニルアルコール、キチンおよびキトサンから選ばれる１種以上の結晶核剤の高濃度のマスターバッチを予め調製しておき、これを生分解性脂肪族ポリエステルに所望の割合で混合して成形に供する方法などが利用できる。 The biodegradable polyester resin composition of the present invention can be easily prepared by a known method generally used as a conventional method for preparing a resin composition. For example, P3AH is mixed with one or more crystal nucleating agents selected from polyvinyl alcohol, chitin and chitosan and, if necessary, other components, and then kneaded with an extruder, roll mill, Banbury mixer, etc. A high-concentration master batch of one or more crystal nucleating agents selected from polyvinyl alcohol, chitin and chitosan is prepared in advance and mixed with a biodegradable aliphatic polyester in a desired ratio. Then, a method for molding can be used.
以上のようにして得られる生分解性ポリエステル系樹脂組成物は、成形処理されて成形体が製造される。
成形処理方法としては、公知のものであればよく、例えば、射出成形、フィルム成形、ブロー成形、繊維の紡糸、押出発泡、ビーズ発泡などが挙げられる。加工条件としては、特に限定はない。
得られた成形体は、加工性に優れ、且つ加工時間も短時間で行え、例えば、食器類、包装用フィルム、各種液体ボトル、不織布、織物、緩衝包材用発泡成形体などの基材として好適に使用される。
The biodegradable polyester resin composition obtained as described above is molded to produce a molded body.
Any known molding method may be used, and examples thereof include injection molding, film molding, blow molding, fiber spinning, extrusion foaming, and bead foaming. There are no particular limitations on the processing conditions.
The obtained molded article is excellent in processability and can be processed in a short time, for example, as a base material for tableware, packaging films, various liquid bottles, nonwoven fabrics, woven fabrics, foam molded articles for cushioning packaging materials, etc. Preferably used.
次に本発明を実施例、比較例によりさらに具体的に説明するが、本発明はこれに限定されるものではない。なお、かぎ括弧内の用語は商品名を示す。 EXAMPLES Next, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to this. The term in the brackets indicates the product name.
（実施例１）
ポリビニルアルコール（ＰＶＡ、ＳＩＧＭＡ試薬「Ｐ１７６３」、重合度２０００）粒子を「Retsch MM200 ミキサーミル」を用いて２５Ｈｚの回転数で５分間粉砕して作製した。平均粒子径は、２〜５μｍであった。同じ粉砕機を用いて得られたポリ（３−ヒドロキシブチレート）粉末（ＰＨＢ、Aldrich Chemical社製、重量平均分子量Ｍｗ１９万）にＰＶＡ粒子２重量％を添加し、２５Ｈｚで２分間粉砕・混合した。
Example 1
Polyvinyl alcohol (PVA, SIGMA reagent “P1763”, degree of polymerization 2000) particles were prepared by pulverizing for 5 minutes at a rotational frequency of 25 Hz using a “Retsch MM200 mixer mill”. The average particle size was 2-5 μm. 2% by weight of PVA particles were added to poly (3-hydroxybutyrate) powder (PHB, manufactured by Aldrich Chemical, weight average molecular weight Mw 190,000) obtained using the same pulverizer, and pulverized and mixed at 25 Hz for 2 minutes. .
ブレンドしたパウダーをプレス(「Mini Test Press-10」, 東洋精機製)にて、１９０℃で３分間プレスしてシート（２ｍｍ×２ｍｍ×１００μｍ）を作製した。 The blended powder was pressed with a press (“Mini Test Press-10”, manufactured by Toyo Seiki) at 190 ° C. for 3 minutes to prepare a sheet (2 mm × 2 mm × 100 μm).
偏光顕微鏡写真は「Mettler FP82HTホットステージ付Olympus BX90偏光顕微鏡」を用いて撮影した（２００倍）。サンプルを１９０℃で２分間融解した後２０℃／分の速度で１１０℃まで冷却して偏光顕微鏡で等温結晶化挙動を観察した。 The polarizing microscope photograph was taken using an “Olympus BX90 polarizing microscope with a Mettler FP82HT hot stage” (200 ×). The sample was melted at 190 ° C. for 2 minutes, then cooled to 110 ° C. at a rate of 20 ° C./min, and the isothermal crystallization behavior was observed with a polarizing microscope.
等温と非等温ＤＳＣ測定は、「Perkin-Elmer(Pyris Diamond)示差走査熱量計」を用いて行った。等温結晶はサンプルを１９０℃で２分間融解した後１１０℃まで急冷し、 １１０℃にて３０分間にわたり測定した。非等温結晶はサンプルを１９０℃で２分間融解した後１０℃／分の速度で０℃まで冷却する過程で測定した。 Isothermal and non-isothermal DSC measurements were performed using a “Perkin-Elmer (Pyris Diamond) differential scanning calorimeter”. Isothermal crystals were measured by melting the sample at 190 ° C. for 2 minutes, quenching to 110 ° C., and measuring at 110 ° C. for 30 minutes. Non-isothermal crystals were measured in the process of melting the sample at 190 ° C. for 2 minutes and then cooling to 0 ° C. at a rate of 10 ° C./min.
結晶核剤を添加しない場合（図１）と、ＰＶＡを添加した場合（図２）の偏光顕微鏡写真を示す。結晶核剤を添加しない場合は、結晶化に時間がかかり、球晶径が大きいのに対し、ＰＶＡを添加した場合は、結晶化する時間が速く、球晶径が小さくなっているのが分かる。 Polarized micrographs of the case where no crystal nucleating agent is added (FIG. 1) and the case where PVA is added (FIG. 2) are shown. When no nucleating agent is added, crystallization takes time and the spherulite diameter is large, whereas when PVA is added, the crystallization time is fast and the spherulite diameter is small. .
図３に、結晶核剤を添加しない場合と、添加した場合の非等温ＤＳＣ測定の結果を示す。１９０℃からの１０℃／分の速度で冷却したとき、ＰＶＡを添加したものは、１１２℃にシャープな結晶化ピークを示すのに対し、結晶核剤を添加しない場合は、８６℃にブロードで小さい結晶化ピークしか示さない。このことは、ＰＶＡを添加した場合の結晶化が、添加しないものに比べて速いことを顕著に示している。 FIG. 3 shows the results of the non-isothermal DSC measurement when the crystal nucleating agent is not added and when it is added. When cooled at a rate of 10 ° C./min from 190 ° C., the one with PVA shows a sharp crystallization peak at 112 ° C., whereas when no nucleating agent is added, it is broad at 86 ° C. Only a small crystallization peak is shown. This remarkably indicates that the crystallization when PVA is added is faster than the case where PVA is not added.
図４に、結晶核剤を添加しない場合と、添加した場合の等温ＤＳＣ測定の結果を示す。１９０℃から１１０℃まで急冷し、１１０℃で等温保持したとき、ＰＶＡを添加したものは、短時間でシャープな結晶化ピークが現れるのに対し、結晶核剤を添加しない場合は、結晶化ピークの現れる時間が遅く、ブロードで小さいピークしか示さない。 FIG. 4 shows the results of isothermal DSC measurement when the crystal nucleating agent is not added and when it is added. When rapidly cooled from 190 ° C to 110 ° C and held isothermally at 110 ° C, the addition of PVA shows a sharp crystallization peak in a short time, whereas when no nucleating agent is added, the crystallization peak Appears slowly and shows only a small, broad peak.
前記の結晶核剤を添加しない場合のように、結晶化速度が遅いと、フィルム成形、ブロー成形、繊維紡糸、押出発泡、ビーズ発泡などの加工において、溶融した樹脂が相互融着して加工不能になったり、加工できても適正温度幅が狭くなるなどの加工条件が極めて厳しくなるという問題が生じ易い。具体的には、射出成形時に冷却時間を延長したり、フィルム成形時の引取線速や繊維紡糸時の引取線速の低下が起こり易くなる。
これに対して、結晶核剤を添加した場合のように結晶化速度が高いと前記問題が発生しにくくなるため、樹脂組成物のより優れた加工性を実現できることがわかる。
If the crystallization rate is slow, as in the case where the crystal nucleating agent is not added, the melted resin cannot be processed due to mutual fusion in processing such as film molding, blow molding, fiber spinning, extrusion foaming, and bead foaming. However, even if it can be processed, the problem that the processing conditions become extremely severe, such as the appropriate temperature range being narrow, is likely to occur. Specifically, the cooling time is extended at the time of injection molding, and the take-up line speed at the time of film forming and the take-up line speed at the time of fiber spinning tend to decrease.
On the other hand, when the crystallization rate is high as in the case of adding a crystal nucleating agent, the above-described problem is less likely to occur, so that it is understood that better processability of the resin composition can be realized.
（実施例２）
ポリビニルアルコールの替わりに、キチン（ＳＩＧＭＡ試薬「Ｃ７１７０」）、キトサン（ＳＩＧＭＡ試薬「Ｃ３６４６」）を用いた以外は、実施例１と同様にして、ＰＨＢにキチン、キトサンをブレンド後、熱プレスしてサンプルを作製し、偏光顕微鏡観察、ＤＳＣ測定を行った。
(Example 2)
Instead of polyvinyl alcohol, chitin (SIGMA reagent “C7170”) and chitosan (SIGMA reagent “C3646”) were used except that chitin and chitosan were blended into PHB and heat-pressed in the same manner as in Example 1. A sample was prepared, and observation with a polarizing microscope and DSC measurement were performed.
結晶核剤を添加しない場合（図１）とキチン粉末を２重量％添加した場合（図５）、キトサン粉末を２重量％添加した場合（図６）の偏光顕微鏡写真を示す。結晶核剤を添加しない場合は、結晶化に時間がかかり、球晶径が大きいのに対し、キチン、キトサンを添加した場合は、結晶化する時間が速く、球晶径が小さくなっている。 Polarized photomicrographs are shown when no crystal nucleating agent is added (FIG. 1), when 2% by weight of chitin powder is added (FIG. 5), and when 2% by weight of chitosan powder is added (FIG. 6). When the crystal nucleating agent is not added, crystallization takes time and the spherulite diameter is large, whereas when chitin and chitosan are added, the crystallization time is fast and the spherulite diameter is small.
図７に、結晶核剤を添加しない場合と、キチン、キトサンを添加した場合の等温ＤＳＣ測定の結果を示す。１９０℃から１１０℃まで急冷し、１１０℃で等温保持したとき、キチン、キトサンを添加したものは、短時間でシャープな結晶化ピークが現れるのに対し、結晶核剤を添加しない場合は、結晶化ピークの現れる時間が遅く、ブロードで小さいピークしか示さない。 FIG. 7 shows the results of isothermal DSC measurement when no crystal nucleating agent is added and when chitin and chitosan are added. When rapidly cooled from 190 ° C to 110 ° C and kept isothermally at 110 ° C, the addition of chitin and chitosan shows a sharp crystallization peak in a short time, whereas when no crystal nucleating agent is added, The time at which the crystallization peak appears is slow and shows only a broad and small peak.
（実施例３）
ＰＨＢの替わりに、３−ヒドロキシヘキサノエート成分が７．３ｍｏｌ％（Ｍｗ４３万）と１４．７ｍｏｌ％（Ｍｗ２７万）のＰＨＢＨを用いた以外は実施例１と同様にして、ＰＨＢＨにＰＶＡをブレンド後、熱プレスしてサンプルを作製し、偏光顕微鏡観察を行った。
(Example 3)
Instead of PHB, PVA was blended with PHBH in the same manner as in Example 1 except that PHBH with 7.3 mol% (Mw 430,000) and 14.7 mol% (Mw 270,000) of 3-hydroxyhexanoate component was used. Then, it hot-pressed and produced the sample and performed the polarization microscope observation.
ＰＨＢＨは、微生物として、アルカリゲネス・ユートロファス（Ａｌｃａｌｉｇｅｎｅｓ ｅｕｔｒｏｐｈｕｓ）にアエロモナス・キャビエ（Ａｅｒｏｍｏｎａｓ ｃａｖｉａｅ）由来のＰＨＡ合成酵素遺伝子を導入したアルカリゲネス・ユートロファス（Ａｌｃａｌｉｇｅｎｅｓ ｅｕｔｒｏｐｈｕｓ）ＡＣ３２（Ｊ．Ｂａｔｅｒｉｏｌ．，１７９，４８２１（１９９７））を用いて、原料、培養条件を適宜調整して生産されたものある。 PHBH is an alkaline genus eutrophus (Alcaligenes eutrohus), in which a PHA synthase gene derived from Aeromonas cavaeae is introduced into Alcaligenes eutrophus (Alcaligenes eutrophus) AC32 (J. ), And the raw materials and the culture conditions are appropriately adjusted.
３−ヒドロキシヘキサノエート成分が７．３ｍｏｌ％のＰＨＢＨを用いて、結晶核剤を添加しない場合と、ＰＶＡを添加した場合の、各々１９０℃で１分溶融させた状態と、１１０℃に急冷３０分後の偏光顕微鏡写真を示す。（図８（Ａ）〜（Ｄ）） 結晶核剤を添加しない場合は、１１０℃で３０分保持しても結晶数が少なく、球晶径が大きいのに対し（図８（Ａ）、（Ｂ）を参照）、ＰＶＡを２重量％添加した場合は、１０分でほぼ全面に結晶化しており、球晶径が小さくなっているのが分かる（図８（Ｃ）、（Ｄ）を参照）。 Using PHBH with a 3-hydroxyhexanoate component of 7.3 mol%, when no crystal nucleating agent is added and when PVA is added, each is melted at 190 ° C. for 1 minute, and rapidly cooled to 110 ° C. A polarizing micrograph after 30 minutes is shown. (FIGS. 8 (A) to (D)) When no crystal nucleating agent is added, the number of crystals is small and the spherulite diameter is large even when held at 110 ° C. for 30 minutes (FIG. 8 (A), ( B)), when 2% by weight of PVA is added, it can be seen that the crystallized surface almost in 10 minutes and the spherulite diameter is reduced (see FIGS. 8C and 8D). ).
３−ヒドロキシヘキサノエート成分が１４．７ｍｏｌ％のＰＨＢＨを用いて、結晶核剤を添加しない場合と、ＰＶＡを添加した場合の、１９０℃で溶融させた後、１１０℃に急冷したときの偏光顕微鏡写真を示す。（図９（Ａ）〜（Ｃ））結晶核剤を添加しない場合（Ａ）は、１１０℃で３０分保持しても結晶化は起こらないのに対し、ＰＶＡを２重量％添加した場合は、３０分で結晶化が起こり（図９（Ｂ））、１時間でほぼ全面に結晶化している（図９（Ｃ））。３−ヒドロキシヘキサノエート成分が多い場合は、少ない場合に比べて、結晶化が遅く、球晶径も大きい。 Polarized light when melted at 190 ° C. and rapidly cooled to 110 ° C., when PHBH having a 3-hydroxyhexanoate component of 14.7 mol% and no crystal nucleating agent was added and when PVA was added A micrograph is shown. (FIG. 9 (A) to (C)) In the case where the crystal nucleating agent is not added (A), crystallization does not occur even when held at 110 ° C. for 30 minutes, whereas in the case where 2% by weight of PVA is added. Crystallization occurred in 30 minutes (FIG. 9B), and crystallized almost on the entire surface in 1 hour (FIG. 9C). When there are many 3-hydroxyhexanoate components, crystallization is slow and a spherulite diameter is large compared with the case where there are few 3-hydroxyhexanoate components.
本発明の生分解性ポリエステル系樹脂組成物を射出成形、フィルム成形、ブロー成形、繊維の紡糸、押出発泡、ビーズ発泡などにより成形加工処理して得られる成形体は、食器類、包装用フィルム、各種液体ボトル、不織布、織物、緩衝包材用発泡成形体用部材として好適に使用することができる。 Molded products obtained by molding and processing the biodegradable polyester resin composition of the present invention by injection molding, film molding, blow molding, fiber spinning, extrusion foaming, bead foaming, etc. are tableware, packaging films, Various liquid bottles, non-woven fabrics, woven fabrics, and foam molded articles for cushioning materials can be suitably used.
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| JP5040236B2 (en) * | 2006-09-27 | 2012-10-03 | 凸版印刷株式会社 | Resin composition, molded article and flooring using the same |
| WO2009060554A1 (en) | 2007-11-08 | 2009-05-14 | Seed Company Ltd. | Elastomer composition, method for producing the same, and eraser using the composition |
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| TW201042103A (en) * | 2008-12-23 | 2010-12-01 | Metabolix Inc | Production of non-woven materials from polyhydroxyalkanoate |
| JP5577764B2 (en) | 2009-07-06 | 2014-08-27 | 株式会社リコー | Copolymer resin composition, molded article, and method for producing copolymer resin composition |
| WO2012153660A1 (en) * | 2011-05-09 | 2012-11-15 | 国立大学法人東京大学 | Nucleating agent, and crystalline polymer composition containing said nucleating agent |
| CN104662088B (en) | 2012-08-03 | 2018-11-02 | 株式会社钟化 | Polyester and resin composition and formed body containing the resin combination |
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