JP2004292499A - Thermoplastic resin foam having fine cell and manufacturing method therefor - Google Patents
Thermoplastic resin foam having fine cell and manufacturing method therefor Download PDFInfo
- Publication number
- JP2004292499A JP2004292499A JP2003083550A JP2003083550A JP2004292499A JP 2004292499 A JP2004292499 A JP 2004292499A JP 2003083550 A JP2003083550 A JP 2003083550A JP 2003083550 A JP2003083550 A JP 2003083550A JP 2004292499 A JP2004292499 A JP 2004292499A
- Authority
- JP
- Japan
- Prior art keywords
- foam
- resin
- mass
- resin composition
- thermoplastic resin
- 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.)
- Granted
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- 239000006260 foam Substances 0.000 title claims abstract description 64
- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 239000011342 resin composition Substances 0.000 claims abstract description 46
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229920005989 resin Polymers 0.000 claims abstract description 37
- 239000011347 resin Substances 0.000 claims abstract description 37
- 239000004626 polylactic acid Substances 0.000 claims abstract description 21
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 18
- 150000004760 silicates Chemical class 0.000 claims abstract description 15
- 238000005187 foaming Methods 0.000 claims description 21
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 20
- 239000012530 fluid Substances 0.000 claims description 18
- 238000007872 degassing Methods 0.000 claims description 12
- 239000001569 carbon dioxide Substances 0.000 claims description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 230000009477 glass transition Effects 0.000 claims description 3
- 230000007613 environmental effect Effects 0.000 abstract description 9
- 210000004027 cell Anatomy 0.000 abstract 2
- 210000000497 foam cell Anatomy 0.000 abstract 1
- 239000006261 foam material Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 28
- 239000007789 gas Substances 0.000 description 18
- 239000000463 material Substances 0.000 description 13
- -1 polyethylene Polymers 0.000 description 12
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 9
- 229910052901 montmorillonite Inorganic materials 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 241000196324 Embryophyta Species 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000011229 interlayer Substances 0.000 description 7
- 239000010410 layer Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 229920006167 biodegradable resin Polymers 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 239000012760 heat stabilizer Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920000118 poly(D-lactic acid) Polymers 0.000 description 3
- 229920001432 poly(L-lactide) Polymers 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- PBLZLIFKVPJDCO-UHFFFAOYSA-N 12-aminododecanoic acid Chemical compound NCCCCCCCCCCCC(O)=O PBLZLIFKVPJDCO-UHFFFAOYSA-N 0.000 description 2
- WHBMMWSBFZVSSR-UHFFFAOYSA-N 3-hydroxybutyric acid Chemical compound CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 description 2
- REKYPYSUBKSCAT-UHFFFAOYSA-N 3-hydroxypentanoic acid Chemical compound CCC(O)CC(O)=O REKYPYSUBKSCAT-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 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
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 2
- 239000000805 composite resin Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 2
- 229910000271 hectorite Inorganic materials 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000002892 organic cations Chemical class 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910000275 saponite Inorganic materials 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- ZMKVBUOZONDYBW-UHFFFAOYSA-N 1,6-dioxecane-2,5-dione Chemical compound O=C1CCC(=O)OCCCCO1 ZMKVBUOZONDYBW-UHFFFAOYSA-N 0.000 description 1
- GUOSQNAUYHMCRU-UHFFFAOYSA-N 11-Aminoundecanoic acid Chemical compound NCCCCCCCCCCC(O)=O GUOSQNAUYHMCRU-UHFFFAOYSA-N 0.000 description 1
- SBAOEHHCKZJQAY-UHFFFAOYSA-N 2-[methyl(octadecyl)amino]ethane-1,1-diol Chemical compound CCCCCCCCCCCCCCCCCCN(C)CC(O)O SBAOEHHCKZJQAY-UHFFFAOYSA-N 0.000 description 1
- VQNQTIUCMJTZGX-UHFFFAOYSA-N 2-hydroxyethyl(triphenyl)phosphanium Chemical compound C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCO)C1=CC=CC=C1 VQNQTIUCMJTZGX-UHFFFAOYSA-N 0.000 description 1
- DJIHQRBJGCGSIR-UHFFFAOYSA-N 2-methylidene-1,3-dioxepane-4,7-dione Chemical compound C1(CCC(=O)OC(=C)O1)=O DJIHQRBJGCGSIR-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
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-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
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910000503 Na-aluminosilicate Inorganic materials 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
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- 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
- 229910021536 Zeolite Inorganic materials 0.000 description 1
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- 239000001361 adipic acid Substances 0.000 description 1
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- 150000001298 alcohols Chemical class 0.000 description 1
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- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
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- 235000012211 aluminium silicate Nutrition 0.000 description 1
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- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
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- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
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- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 1
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- UWHRNIXHZAWBMF-UHFFFAOYSA-N n-dodecyl-n-methyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)CCCCCCCCCCCC UWHRNIXHZAWBMF-UHFFFAOYSA-N 0.000 description 1
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- HKUFIYBZNQSHQS-UHFFFAOYSA-N n-octadecyloctadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCNCCCCCCCCCCCCCCCCCC HKUFIYBZNQSHQS-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、環境に対する負荷の小さいポリ乳酸と、層状珪酸塩を主成分とした熱可塑性樹脂の発泡体及びその製造方法に関する。特に、気泡径が非常に微細で、発泡による機械物性の低下が抑制された環境低負荷性発泡体及びその製造方法に関する。
【０００２】
【従来の技術】
従来から、熱可塑性樹脂にガスを含浸させた後脱ガスさせ、熱可塑性樹脂の発泡体を得る技術は幅広く用いられ、得られた発泡体は様々な用途に用いられてきた。しかし近年、大量に使用され、その後大量に廃棄される熱可塑性樹脂発泡体は、使用時や廃棄時に環境に大きな負荷を与え、地球温暖化問題、資源枯渇問題、廃棄物処理問題など、様々な社会問題の原因となっている。
【０００３】
発泡体の環境負荷を低減するための解決策の一つとして、ポリ乳酸などの、植物由来の原料から製造される生分解性樹脂を原料とする発泡体が種々提案されている（特許文献１〜７、非特許文献１、２）。しかし、これらの方法はいずれも、気泡径が大きく、発泡に伴い機械物性が低下するため、機械物性が要求される用途に使用することができなかった。
【０００４】
一方、熱可塑性樹脂発泡体において、気泡径を小さくする方法としては、特許文献８に、超臨界液体を材料に連続的に導入し、それを発泡させることにより得られる発泡材料が提案されている。また、特許文献９、１０には、それぞれ熱可塑性樹脂と層状珪酸塩からなる樹脂組成物に、超臨界流体等の発泡剤を浸透させた後、脱ガスさせて得られる発泡体が提案されている。しかし、これらの方法は、ポリ乳酸を主成分とした環境低負荷性樹脂に関して実際には検討されていなかった。また、特許文献１０に関しては、気泡が連続した構造の発泡体しか得ることができず、発泡による機械物性の低下を避けることができないものであった。
【０００５】
【特許文献１】
特開平４−３０４２４４号公報
【特許文献２】
特開平５−１４０３６１号公報
【特許文献３】
特開平６−２８７３４７号公報
【特許文献４】
特公平５−５０８６６９号公報
【特許文献５】
特開平９−２６３６５１号公報
【特許文献６】
特開平１１−１４７９４３号公報
【特許文献７】
特開平１０−３２４７６６号公報
【特許文献８】
特表平６−５０６７２４号公報
【特許文献９】
特開２００１−２８８２９３号公報
【特許文献１０】
特開２００２−３４８３９８号公報
【非特許文献１】
成形加工’００、Ｐ１４９〜１５０
【非特許文献２】
成形加工シンポジア’００、Ｐ２０７〜２０８
【０００６】
【発明が解決しようとする課題】
本発明は、上記の問題点を解決しようとするものであり、環境に対する負荷の小さい樹脂を原料とした、微細な気泡を有する発泡体と、その製造方法を提供することにある。
【０００７】
【課題を解決するための手段】
本発明者らは、上記課題を解決するために鋭意研究を重ねた結果、ポリ乳酸を主体とした樹脂と層状珪酸塩とを主成分とする樹脂組成物を、特定の方法で発泡させてなる発泡体が、微細な気泡を有し、発泡による機械物性の低下が少ないことを見いだし、本発明に到達した。
【０００８】
すなわち本発明の要旨は、次のとおりである。
（１）ポリ乳酸を５０質量部以上含有した熱可塑性樹脂１００質量部と、層状珪酸塩０．１〜５０質量部とを主成分とする樹脂組成物の発泡体であって、気泡径と層状珪酸塩の分散状態との関係が、下記式（１）、（２）を満たしていることを特徴とする熱可塑性樹脂発泡体。
ｄ／Ｌ≦５０ （１）
ｄ／ξ≦１００ （２）
式（１）、（２）において、ｄは平均気泡径（ｎｍ）、Ｌは層状珪酸塩の平均長径（ｎｍ）、ξは隣接する層状珪酸塩間の平均距離（ｎｍ）を表す。
（２）気泡密度が１．０×１０９（個／ｃｍ３）以上であることを特徴とする（１）記載の熱可塑性樹脂発泡体。
（３）上記樹脂組成物にガス及び／又は超臨界流体を含浸させる工程と、脱ガスさせて樹脂を発泡させる工程を有する熱可塑性樹脂発泡体の製造方法であって、樹脂を発泡させる工程における樹脂温度が、樹脂組成物のガラス転移温度（Ｔｇ）以上融点（Ｔｍ）以下であることを特徴とする（１）又は（２）記載の熱可塑性樹脂発泡体の製造方法。
（４）脱ガスさせて樹脂を発泡させる工程の開始時点における樹脂組成物の結晶化度が１０％以上であることを特徴とする（３）記載の熱可塑性樹脂発泡体の製造方法。
（５）ガス及び／又は超臨界流体の種類が二酸化炭素であることを特徴とする（３）又は（４）記載の熱可塑性樹脂発泡体の製造方法。
【０００９】
【発明の実施の形態】
以下、本発明を詳細に説明する。
本発明の発泡体は、ポリ乳酸を主成分とする樹脂と、層状珪酸塩とを主体とする樹脂組成物の発泡体である。本発明の発泡体を構成する樹脂組成物の、樹脂１００質量部中におけるポリ乳酸の含有量は、５０質量部以上であり、好ましくは７５質量部以上、より好ましくは９０質量部以上である。ポリ乳酸の含有量が少ないと、本発明の目的の一つである環境負荷低減が不十分となる。
【００１０】
本発明に使用されるポリ乳酸としては、ポリ（Ｌ−乳酸）、ポリ（Ｄ−乳酸）、およびこれらの混合物または共重合体もしくは共重合体と混合物の両方を用いることができる。好ましくは、異性体含有量が５％以下のポリ（Ｌ−乳酸）またはポリ（Ｄ−乳酸）、より好ましくは異性体含有量が２％以下のポリ（Ｌ−乳酸）またはポリ（Ｄ−乳酸）である。異性体の含有量が多いものは、結晶性が低下する傾向にある。
【００１１】
本発明においては、ポリ乳酸以外の他の重合体を、混合もしくは主成分であるポリ乳酸と共重合して使用してもよい。混合もしくは共重合される重合体としては特に制限がないが、融点もしくは軟化点が２８０℃以下の熱可塑性樹脂であることが好ましい。融点もしくは軟化点が２８０℃を超えると、加工温度が高くなりすぎてポリ乳酸が分解劣化する傾向が現れる。
【００１２】
混合もしくは共重合される重合体の具体例としては、生分解性の樹脂としては、ポリ（エチレンサクシネート）、ポリ（ブチレンサクシネート）、ポリ（ブチレンサクシネート−ｃｏ−ブチレンアジペート）等に代表されるジオールとジカルボン酸からなる脂肪族ポリエステル、ポリグリコール酸、ポリ（３−ヒドロキシ酪酸）、ポリ（３−ヒドロキシ吉草酸）、ポリ（３−ヒドロキシカプロン酸）等のポリヒドロキシカルボン酸、ポリ（ε−カプロラクトン）やポリ（δ−バレロラクトン）に代表されるポリ（ω−ヒドロキシアルカノエート）、さらに芳香族成分を含んでいても生分解性を示すポリ（ブチレンサクシネート−ｃｏ−ブチレンテレフタレート）やポリ（ブチレンアジペート−ｃｏ−ブチレンテレフタレート）の他、ポリエステルアミド、ポリエステルカーボネート、澱粉等の多糖類等が挙げられる。非生分解性の樹脂としては、ポリエチレン、ポリプロピレンなどのポリオレフィン類、ポリ塩化ビニル、ポリ酢酸ビニル、ポリスチレンなどのビニルポリマー類、ポリアミド、ポリエステル、ポリカーボネート、ポリブタジエン、ブタジエン／スチレン共重合体、アクリルゴム、エチレン／プロピレン共重合体、エチレン／プロピレン／ジエン共重合体、天然ゴム、塩素化ブチルゴム、塩素化ポリエチレン等のエラストマー又はこれらの無水マレイン酸等による酸変性物、スチレン／無水マレイン酸共重合体、スチレン／フェニルマレイミド共重合体、ブタジエン／アクリロニトリル共重合体、ポリアセタール、ポリフッ化ビニリデン、ポリスルホン、ポリフェニレンサルファイド、ポリエーテルスルホン、フェノキシ樹脂、ポリフェニレンエーテル、ポリメチルメタクリレート、ポリエーテルケトン、ポリカーボネート、ポリテトラフルオロエチレン、ポリアリレートなどが挙げられる。
【００１３】
樹脂組成物の生分解性という側面から、本発明の樹脂組成物は、樹脂１００質量部のうち、生分解性樹脂を７５質量部以上使用することが好ましく、９０質量部以上使用することがより好ましく、９９質量部以上使用することが最も好ましい。また、植物由来原料を使用することによる環境低負荷性という側面からは、本発明の樹脂組成物は、樹脂１００質量部のうち、植物由来原料からなる樹脂を７５質量部以上使用することが好ましく、９０質量部以上使用することがより好ましく、９９質量部以上使用することが最も好ましい。植物由来原料からなる樹脂としては、植物から直接得られる高分子量体、もしくはその誘導体でも良く、植物から得られた化合物をそのまま、もしくは変性させた後重合して製造したものでもよい。植物由来原料からなる樹脂の具体例としては、ポリ乳酸のほかに、セルロースおよびその誘導体、デンプンおよびその誘導体、ポリアミド１１、天然ゴムおよびその誘導体などが挙げられる。
【００１４】
本発明の発泡体を構成する樹脂組成物においては、樹脂１００質量部に対して層状珪酸塩が０．１〜５０質量部含まれている。好ましくは０．５〜２０質量部、より好ましくは１〜１０質量部である。層状珪酸塩が０．１質量部より少ないと、層状珪酸塩の発泡核材としての効果が小さくなり、気泡が微細になり難いので好ましくない。層状珪酸塩が５０質量部を超えると、樹脂組成物を製造する工程での操業性が悪化するだけでなく、樹脂の発泡が阻害されるため好ましくない。
【００１５】
本発明で用いられる層状珪酸塩とは、具体的には、スメクタイト、バーミキュライト、および膨潤性フッ素雲母等が挙げられる。スメクタイトの例としては、モンモリロナイト、バイデライト、ヘクトライト、サポナイト等が挙げられる。膨潤性フッ素雲母の例としては、Ｎａ型フッ素四ケイ素雲母、Ｎａ型テニオライト、Ｌｉ型テニオライト等が挙げられ、また上記の他に、カネマイト、マカタイト、マガディアイト、ケニアイト等のアルミニウムやマグネシウムを含まない層状珪酸塩を使用することもできる。天然品以外に合成品でもよく、合成方法としては、溶融法、インターカレーション法、水熱法等が挙げられるが、いずれの方法であってもよい。これらの層状珪酸塩は単独で使用してもよいが、鉱物の種類、産地、粒径等が異なるものを２種類以上組み合わせて使用してもよい。
上記層状珪酸塩の中では、モンモリロナイト、ヘクトライト、サポナイト、膨潤性フッ素雲母が好ましく使用される。特に好ましく使用されるのはモンモリロナイト又は膨潤性フッ素雲母である。
【００１６】
また、本発明で用いられる層状珪酸塩は、樹脂組成物中での層状珪酸塩の分散性を向上させる目的で、あらかじめ層間に有機化合物を挿入させておくことが好ましい。挿入の方法としては、（Ａ）層間に存在する交換性金属イオンを有機カチオンとイオン交換させる方法や、（Ｂ）単に層間に有機物を挿入し膨潤させる方法が挙げられる。また、両者の方法を併用してもよい。交換や挿入のための具体的な手段としては、通常公知の方法を使用することができる。
【００１７】
前記（Ａ）の方法で使用する有機カチオンとしては、１級ないし３級アミン、アミノカルボン酸などをプロトン化したカチオン、４級アンモニウムイオン、ホスホニウムイオン等が挙げられる。１級アミンとしては、オクチルアミン、ドデシルアミン、オクタデシルアミン等が挙げられる。２級アミンとしては、ジオクチルアミン、メチルオクタデシルアミン、ジオクタデシルアミン等が挙げられる。３級アミンとしては、トリオクチルアミン、ジメチルドデシルアミン、ジドデシルモノメチルアミン等が挙げられる。４級アンモニウムイオンとしては、テトラエチルアンモニウム、オクタデシルトリメチルアンモニウム、ジメチルジオクタデシルアンモニウム、ジヒドロキシエチルメチルオクタデシルアンモニウム、メチルドデシルビス（ポリエチレングリコール）アンモニウム、メチルジエチル（ポリプロピレングリコール）アンモニウム等が挙げられる。さらに、ホスホニウムイオンとしては、テトラエチルホスホニウム、テトラブチルホスホニウム、ヘキサデシルトリブチルホスホニウム、テトラキス（ヒドキシメチル）ホスホニウム、２−ヒドロキシエチルトリフェニルホスホニウム等が挙げられる。アミノカルボン酸の例としては、６−アミノカプロン酸、１１−アミノウンデカン酸、１２−アミノドデカン酸などが挙げられる。アミノカルボン酸は、対応するラクタムの形で混合し、層間において開環してアミノカルボン酸のカチオンとなって挿入される場合も含まれる。これらのうち、特に好ましいのは、１級ないし３級アミンのカチオン、４級アンモニウムイオン、ホスホニウムイオンである。また、これらの化合物は単独で使用しても、２種以上を組み合わせて使用してもよい。
【００１８】
また、（Ｂ）の方法で使用する化合物としては、メタノール、エタノール、プロパノール、ブタノールなどのアルコール類、エチレングリコール、プロピレングリコール、１，４−ブタンジオールなどのジオール類、酢酸、プロピオン酸、吉草酸、安息香酸、アジピン酸、セバシン酸、マレイン酸、テレフタル酸、イソフタル酸などのカルボン酸類、乳酸、ラクチド等のヒドロキシカルボン酸類等が挙げられる。
【００１９】
本発明の発泡体を構成する樹脂組成物中において、層状珪酸塩は、その層間に樹脂のポリマー分子が挿入され、層間距離が増大した状態で均一に分散していることが好ましい。具体的な層間距離としては、Ｘ線回折法によって測定された値を指標にした場合、２．６ｎｍ以上が好ましく、２．８ｎｍ以上がより好ましく、３．０ｎｍ以上がさらに好ましい。また、最も好ましくは層状珪酸塩が単層に近い状態まで剥離した状態であり、Ｘ線回折で層間距離に由来するピークが観測されない状態である。
【００２０】
本発明の発泡体を構成する樹脂組成物には、その特性を大きく損なわない限りにおいて、顔料、染料、熱安定剤、酸化防止剤、耐候剤、難燃剤、可塑剤、滑剤、離型剤、帯電防止剤、分散剤、充填材、結晶核材等を添加することも可能である。熱安定剤や酸化防止剤としては、たとえばヒンダードフェノール類、リン化合物、ヒンダードアミン、イオウ化合物、銅化合物、アルカリ金属のハロゲン化物あるいはこれらの混合物を使用することができる。無機充填材としては、タルク、炭酸カルシウム、炭酸亜鉛、ワラストナイト、シリカ、アルミナ、酸化マグネシウム、ケイ酸カルシウム、アルミン酸ナトリウム、アルミン酸カルシウム、アルミノ珪酸ナトリウム、珪酸マグネシウム、ガラスバルーン、カーボンブラック、酸化亜鉛、三酸化アンチモン、ゼオライト、ハイドロタルサイト、金属繊維、金属ウイスカー、セラミックウイスカー、チタン酸カリウム、窒化ホウ素、グラファイト、ガラス繊維、炭素繊維等が挙げられる。有機充填材としては、澱粉、セルロース微粒子、木粉、おから、モミ殻、フスマ等の天然に存在するポリマーやこれらの変性品が挙げられる。無機結晶核材としては、タルク、カオリン等が挙げられ、有機結晶核材としては、ソルビトール化合物、安息香酸およびその化合物の金属塩、燐酸エステル金属塩、ロジン化合物等が挙げられる。なかでも有機結晶核材は、少量添加することによって樹脂組成物の結晶が微細化し、透明性が向上するため好ましく使用することができる。
【００２１】
なお、本発明の樹脂組成物に上記の熱安定剤、酸化防止剤、可塑剤、充填材、結晶核材等を混合する方法は特に限定されるものではなく、原料樹脂の製造工程、あるいは原料樹脂と層状珪酸塩とを混合する工程、樹脂組成物にガス及び／又は超臨界流体を含浸させる工程、脱ガスさせて発泡させる工程のいずれの工程においても添加することができる。好ましくは、原料樹脂と層状珪酸塩とを混合する工程、もしくは原料樹脂を製造する工程において混合される。
【００２２】
本発明の発泡体は、上記樹脂複合体に、ガスもしくは超臨界流体を含浸させた後、脱ガスさせることによって製造される。超臨界流体とは、気体と液体の中間の性質をもったものであり、ガスの種類で定まった温度及び圧力（臨界点）以上になると超臨界流体となる。本発明においては、超臨界流体を含浸させる方法が好ましい。ガスの種類は、特に限定されず、ブタン、フロン、代替フロン、二酸化炭素、窒素等が挙げられるが、環境への負荷が低い二酸化炭素、窒素が好ましく、超臨界状態を得やすいため二酸化炭素が最も好ましい。
【００２３】
本発明の発泡体の製造方法としては、上記熱可塑性樹脂組成物にガス及び／又は超臨界流体を含浸させる工程と、脱ガスさせて樹脂を発泡させる工程とを有する方法が挙げられ、この２工程を備えていれば他の条件は特に限定されないが、好ましい例としては、密閉したオートクレーブ中にガス及び／又は超臨界流体を封入し、一定時間含浸させたのちオートクレーブの圧力を開放して発泡させる方法、熱可塑性樹脂組成物を溶融押出機に投入し、シリンダーの途中からガス及び／又は超臨界流体を注入し、シリンダー内の圧力を利用してガス及び／又は超臨界流体を含浸させ、押出機のダイ出口において発泡させる方法、射出成形機のシリンダー途中からガス及び／又は超臨界流体を注入し、金型内で発泡させる方法等が挙げられる。
【００２４】
樹脂組成物にガス及び／又は超臨界流体を含浸させる工程での温度は特に限定されないが、２８０℃以下であることが好ましい。２８０℃を超えると、樹脂組成物が分解劣化する傾向が現れる。
【００２５】
また、樹脂組成物にガス及び／又は超臨界流体を含浸させる際の圧力にも特に制限はない。好ましくは、ガスが超臨界状態になる温度、圧力であることが好ましい。二酸化炭素の場合、３５℃、７．５ＭＰａで超臨界状態となる。
【００２６】
脱ガスさせて樹脂を発泡させる工程での温度は、樹脂組成物のガラス転移温度（Ｔｇ）以上融点（Ｔｍ）以下であることが好ましい。この温度領域においては、樹脂組成物の結晶化が促進され、微細な気泡をもつ発泡体が得られやすくなる。より好ましくは、（Ｔｇ＋２０）℃〜（Ｔｍ−１０）℃である。Ｔｇに満たない場合には発泡が起こらず、Ｔｍを超えると樹脂の粘度が低下するため、気泡が大きくなりすぎて気泡密度が低下する、破泡するなどの現象が起こる。
【００２７】
また、脱ガスさせて樹脂を発泡させる工程の最初の段階において、樹脂組成物の結晶化度が高められていることが好ましく、具体的な結晶化度としては、ＤＳＣで測定した値で１０％以上であることが好ましく、２０％以上であることがより好ましく、４０％以上であることがさらに好ましい。樹脂組成物の結晶化度が上昇することで、気泡の過剰な成長が抑制され、気泡径の微細な発泡体が得られやすくなる。結晶化を促進させる時期としては、ガス及び／又は超臨界流体を含浸させる工程の前あるいはこの工程中でもよく、特に限定されない。
【００２８】
以上の方法で発泡させた発泡体は、気泡が非常に微細であることを特徴としている。具体的には、層状珪酸塩の分散状態と関連する、下記式（１）、（２）を満たしている。
ｄ／Ｌ≦５０ （１）
ｄ／ξ≦１００ （２）
ここで、ｄは平均気泡径（ｎｍ）、Ｌは層状珪酸塩の平均長径（ｎｍ）、ξは、隣接する層状珪酸塩間の平均距離（ｎｍ）を表す。
なお、式（１）の関係については、ｄ／Ｌ≦２０であることが好ましく、ｄ／Ｌ≦６がより好ましく、ｄ／Ｌ≦３が特に好ましい。また、式（２）に関しては、好ましくはｄ／ξ≦４０、より好ましくはｄ／ξ≦１２、特にに好ましくはｄ／ξ≦５、最も好ましくはｄ／ξ≦３である。
気泡径に関しては走査型電子顕微鏡観察で、層状珪酸塩の平均長径、隣接層状珪酸塩間距離に関しては透過型電子顕微鏡観察で好ましく測定される。
【００２９】
気泡密度は１０９（個／ｃｍ３）以上であることが好ましく、より好ましくは１０１１（個／ｃｍ３）以上、さらに好ましくは１０１４（個／ｃｍ３）以上である。１０９（個／ｃｍ３）未満の場合には、個々の気泡が過剰に成長し、気泡が大きくなる傾向がある。
【００３０】
発泡体の発泡倍率に関しては特に制限はないが、好ましくは１．１倍〜３倍、より好ましくは１．２〜２．５倍である。発泡倍率が低すぎると、発泡体の特徴の一つである軽量性が低くなる傾向にあり、発泡倍率が高すぎると、気泡径を微細に制御することが困難になる傾向にある。
【００３１】
本発明の発泡体は、軽量性に優れ、かつ非発泡体と比較して機械物性の低下も少ないことから、軽量性と機械物性の両方が要求される用途において特に好適に使用される。具体的には、容器、包装、生活雑貨の他、自動車部品、電器部品等にも好適に使用される。
【００３２】
【作用】
本発明において、微細な気泡を有する発泡体が得られる理由としては、以下の二つが挙げられる。一つは、樹脂中に分散した層状珪酸塩が発泡核材として作用していること、もう一つは、脱ガスさせて樹脂を発泡させる工程における温度条件、樹脂の結晶化度が最適化され、過剰な気泡成長が抑制されていることである。また、樹脂中に分散した層状珪酸塩は、樹脂の伸長粘度を増大させ、結晶化速度を増大させるといった好ましい効果も引き起こしている。
【００３３】
【実施例】
以下本発明を実施例によりさらに具体的に説明するが、本発明は実施例のみに限定されるものではない。なお、実施例および比較例の樹脂組成物および発泡体の評価に用いた測定法は次のとおりである。
（１）層状珪酸塩の平均長径Ｌ、隣接層状珪酸塩間距離ξ
透過型電子顕微鏡（日本電子製ＪＥＭ−２００ＣＸ）を用い、２万倍の倍率で、層状珪酸塩の粒子が２０以上観察される視野内で、各層状珪酸塩の長径および隣接する層状珪酸塩粒子間の距離を目視で測定して平均値を算出した。この作業を２０ヶ所の異なる視野で行い、平均値を算出して平均長径Ｌ、隣接層状珪酸塩距離ξとした。
（２）気泡径
走査型電子顕微鏡（日本電子製ＪＳＭ−５３１０ＬＶ）を用い、撮影された写真を画像処理し、気泡径の分布を求め、ガウス関数近似により平均気泡径を求めた。撮影倍率は、実施例１は３５００倍、実施例２は１０００倍、比較例１では７５倍とした。
（３）気泡密度
発泡体の密度と、発泡前の密度、及び気泡径から、下記式によって気泡密度を求めた。（ＮａｎｏＬｅｔｔｓ．２００１；１：５０３）
気泡密度（個／ｃｍ３）＝（１−ρｆ／ρｐ）／（１０−４×ｄ３）
上式において、ρｆは発泡体の密度、ρｐは発泡前の密度（いずれもｇ／ｃｍ３）、ｄは気泡径（ｍｍ）である。なお、ポリ乳酸の密度は１．２６６ｇ／ｃｍ３を用いた。
（４）結晶化度
示差走査熱量計（パーキンエルマー社製ＤＳＣ７）を用い、毎分５℃の速度で加熱し、このときに得られる結晶の融解ピーク面積と、樹脂組成物の結晶化ピーク面積とから、下記の式を用いて結晶化度を算出した。
結晶化度（％）＝（融解ピーク面積（Ｊ））−（結晶化ピーク面積（Ｊ））／（サンプル量（ｇ）×結晶融解エンタルピー（Ｊ／ｇ））
なお、ポリ乳酸の結晶融解エンタルピーは９３Ｊ／ｇである（Ｋｏｌｌｏｉｄ−Ｚ．Ｚ．Ｐｏｌｙｍｅｒ．１９７３；２５：９８０）。
【００３４】
実施例１
ポリ乳酸（ＰＬＡ）（カーギルダウ社製ＮａｔｕｒｅＷｏｒｋｓ、Ｔｇ＝５８℃、Ｔｍ＝１６８℃）１００質量部に対し、層間カチオンがトリメチルステアリルアンモニウムイオンで置換されたモンモリロナイト（ホージュン社製エスベンＥ）を５質量部混合し、スクリュー径４５ｍｍφの２軸押出機（池貝製ＰＣＭ−４５）を用いて１９０℃、スクリュー回転数２００ｒｐｍ、滞留時間２分の条件で溶融混練し、樹脂組成物を得た。この樹脂組成物中において、モンモリロナイトの層間距離は３．１ｎｍであった。
【００３５】
次に、得られた樹脂組成物を１１０℃で２時間熱処理し、結晶化させた後オートクレーブ中に投入し、４０℃、１０ＭＰａにおいて、超臨界状態の二酸化炭素を４時間含浸させた。オートクレーブに投入する直前の結晶化度は５６％であった。二酸化炭素を含浸させた樹脂組成物をオートクレーブから取り出し、１６０℃に保ったオイルバス中に投入し、３０秒間保持することで樹脂組成物の発泡体を得た。この発泡体について気泡径、層状珪酸塩の平均長径、隣接層状珪酸塩間距離を測定した。
【００３６】
実施例２
ＰＬＡ１００質量部に対し、層間カチオンがオクタデシルアンモニウムイオンで置換されたモンモリロナイト（ナノコール社製ＯＤＡ−ＣＷＣ）を５質量部混合し、スクリュー径４５ｍｍφの２軸押出機（池貝製ＰＣＭ−４５）を用いて１９０℃、スクリュー回転数２００ｒｐｍ、滞留時間２分の条件で溶融混練し、樹脂組成物を得た。この樹脂組成物中において、モンモリロナイトの層間距離は２．９ｎｍであった。
【００３７】
次に、得られた樹脂組成物を１１０℃で２時間熱処理し、結晶化させた後オートクレーブ中に投入し、４０℃、１０ＭＰａにおいて、超臨界状態の二酸化炭素を４時間含浸させた。オートクレーブに投入する直前の結晶化度は３９％であった。二酸化炭素を含浸させた樹脂組成物をオートクレーブから取り出し、１６０℃に保ったオイルバス中に投入し、３０秒間保持することで樹脂組成物の発泡体を得た。この発泡体について気泡径、層状珪酸塩の平均長径、隣接層状珪酸塩間距離を測定した。
【００３８】
比較例１
モンモリロナイトを使用せず、ポリ乳酸（ＰＬＡ）（カーギルダウ社製ＮａｔｕｒｅＷｏｒｋｓ）１００質量部のみに対し、実施例１と同様の方法で発泡体を作製し、気泡径、層状珪酸塩の平均長径、隣接層状珪酸塩間距離、また樹脂組成物の結晶化度を測定した。
【００３９】
比較例２
実施例１で使用したモンモリロナイトの使用量を、ポリ乳酸（ＰＬＡ）（カーギルダウ社製ＮａｔｕｒｅＷｏｒｋｓ）１００質量部に対し５５質量部とした他は実施例１と同様の方法で発泡体の作製を試みたが、良好な発泡体を得ることができなかった。
【００４０】
実施例１〜２および比較例１〜２の結果を表１に示す。
【００４１】
【表１】
実施例１、２では気泡が非常に微細な発泡体を得ることができた。特に、結晶化度を高めた実施例１では、気泡密度が高くなっていた。比較例１に関しては、層状珪酸塩を用いないで発泡体の作製を行ったため、気泡径が大きい発泡体が得られたに過ぎなかった。比較例２に関しては、層状珪酸塩の量が多すぎたため、良好な発泡体を得ることができなかった。
【００４３】
【発明の効果】
本発明によれば、非常に微細な気泡を有する環境低負荷性樹脂発泡体を得ることができ、容器、包装、生活雑貨の他、自動車部品、電器部品等のさまざまな分野に環境低負荷性の発泡材料を提供することができる。
【図面の簡単な説明】
【図１】実施例１で得られた発泡体の気泡径分布とガウス関数近似曲線を示すグラフである。
【図２】実施例２で得られた発泡体の気泡径分布とガウス関数近似曲線を示すグラフである。[0001]
TECHNICAL FIELD OF THE INVENTION
TECHNICAL FIELD The present invention relates to a thermoplastic resin foam mainly composed of polylactic acid and a layered silicate that have a small environmental load, and a method for producing the same. In particular, the present invention relates to an environmentally-friendly foam having a very small cell diameter and a decrease in mechanical properties due to foaming, and a method for producing the same.
[0002]
[Prior art]
2. Description of the Related Art Conventionally, a technique of obtaining a foam of a thermoplastic resin by impregnating a thermoplastic resin with a gas and then degassing the gas has been widely used, and the obtained foam has been used for various applications. However, in recent years, thermoplastic resin foams, which are used in large quantities and subsequently discarded in large quantities, have a great impact on the environment during use and disposal, and have various problems, such as global warming, resource depletion, and waste disposal. Causing social problems.
[0003]
As one of the solutions for reducing the environmental load of the foam, various foams using a biodegradable resin produced from a plant-derived material such as polylactic acid have been proposed (Patent Document 1). 7, Non-Patent
[0004]
On the other hand, as a method for reducing the cell diameter in a thermoplastic resin foam,
[0005]
[Patent Document 1]
Japanese Patent Application Laid-Open No. 4-304244 [Patent Document 2]
JP-A-5-140361 [Patent Document 3]
JP-A-6-287347 [Patent Document 4]
Japanese Patent Publication No. 5-508669 [Patent Document 5]
Japanese Patent Application Laid-Open No. 9-263652 [Patent Document 6]
JP-A-11-147943 [Patent Document 7]
JP 10-324766 A [Patent Document 8]
Japanese Patent Publication No. 6-506724 [Patent Document 9]
JP 2001-288293 A [Patent Document 10]
JP-A-2002-348398 [Non-Patent Document 1]
Forming process '00, P149-150
[Non-patent document 2]
Molding Symposia '00, P207-208
[0006]
[Problems to be solved by the invention]
An object of the present invention is to solve the above-mentioned problems, and an object of the present invention is to provide a foam having fine air bubbles, which is made of a resin having a small environmental load, and a method for producing the foam.
[0007]
[Means for Solving the Problems]
The present inventors have conducted intensive studies in order to solve the above-described problems, and as a result, a resin composition mainly containing a resin mainly composed of polylactic acid and a layered silicate is foamed by a specific method. The present inventors have found that the foam has fine cells and the mechanical properties due to the foaming are hardly reduced.
[0008]
That is, the gist of the present invention is as follows.
(1) A foam of a resin composition containing, as main components, 100 parts by mass of a thermoplastic resin containing 50 parts by mass or more of polylactic acid and 0.1 to 50 parts by mass of a layered silicate. A thermoplastic resin foam, wherein the relationship with the dispersion state of the silicate satisfies the following formulas (1) and (2).
d / L ≦ 50 (1)
d / ξ ≦ 100 (2)
In the formulas (1) and (2), d represents the average cell diameter (nm), L represents the average major axis diameter (nm) of the layered silicate, and ξ represents the average distance (nm) between adjacent layered silicates.
(2) The thermoplastic resin foam according to (1), wherein the bubble density is 1.0 × 10 9 (pieces / cm 3 ) or more.
(3) A method for producing a thermoplastic resin foam, comprising: a step of impregnating the resin composition with a gas and / or a supercritical fluid; and a step of degassing and foaming the resin. The method for producing a thermoplastic resin foam according to (1) or (2), wherein the resin temperature is not lower than the glass transition temperature (Tg) and not higher than the melting point (Tm) of the resin composition.
(4) The method for producing a thermoplastic resin foam according to (3), wherein the degree of crystallinity of the resin composition at the start of the step of degassing and foaming the resin is 10% or more.
(5) The method for producing a thermoplastic resin foam according to (3) or (4), wherein the type of gas and / or supercritical fluid is carbon dioxide.
[0009]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in detail.
The foam of the present invention is a foam of a resin composition mainly composed of a resin mainly composed of polylactic acid and a layered silicate. The content of the polylactic acid in 100 parts by mass of the resin of the resin composition constituting the foam of the present invention is 50 parts by mass or more, preferably 75 parts by mass or more, more preferably 90 parts by mass or more. When the content of polylactic acid is small, the reduction of the environmental load, which is one of the objects of the present invention, becomes insufficient.
[0010]
As the polylactic acid used in the present invention, poly (L-lactic acid), poly (D-lactic acid), a mixture thereof, or a copolymer or both a copolymer and a mixture thereof can be used. Preferably, poly (L-lactic acid) or poly (D-lactic acid) having an isomer content of 5% or less, more preferably poly (L-lactic acid) or poly (D-lactic acid) having an isomer content of 2% or less ). Those having a high isomer content tend to have reduced crystallinity.
[0011]
In the present invention, a polymer other than polylactic acid may be used by mixing or copolymerizing with polylactic acid as a main component. The polymer to be mixed or copolymerized is not particularly limited, but is preferably a thermoplastic resin having a melting point or softening point of 280 ° C. or less. If the melting point or softening point exceeds 280 ° C., the processing temperature becomes too high, and polylactic acid tends to decompose and deteriorate.
[0012]
Specific examples of the polymer to be mixed or copolymerized include, as biodegradable resins, poly (ethylene succinate), poly (butylene succinate), poly (butylene succinate-co-butylene adipate) and the like. Aliphatic polyester consisting of a diol and a dicarboxylic acid, polyglycolic acid, poly (3-hydroxybutyric acid), poly (3-hydroxyvaleric acid), poly (3-hydroxycaproic acid), etc .; Poly (ω-hydroxyalkanoate) represented by ε-caprolactone) and poly (δ-valerolactone), and poly (butylene succinate-co-butylene terephthalate) exhibiting biodegradability even if it contains an aromatic component And poly (butylene adipate-co-butylene terephthalate), polyester Amides, polyester carbonates, polysaccharides starch and the like. Non-biodegradable resins include polyolefins such as polyethylene and polypropylene, vinyl polymers such as polyvinyl chloride, polyvinyl acetate and polystyrene, polyamides, polyesters, polycarbonates, polybutadienes, butadiene / styrene copolymers, acrylic rubbers, Ethylene / propylene copolymer, ethylene / propylene / diene copolymer, natural rubber, chlorinated butyl rubber, chlorinated polyethylene and other elastomers or their acid-modified products such as maleic anhydride, styrene / maleic anhydride copolymer, Styrene / phenylmaleimide copolymer, butadiene / acrylonitrile copolymer, polyacetal, polyvinylidene fluoride, polysulfone, polyphenylene sulfide, polyether sulfone, phenoxy resin, polyphenylene Ether, polymethyl methacrylate, polyether ketone, polycarbonate, polytetrafluoroethylene, polyarylate, and the like.
[0013]
From the aspect of biodegradability of the resin composition, the resin composition of the present invention preferably uses 75 parts by mass or more of the biodegradable resin among 100 parts by mass of the resin, and more preferably uses 90 parts by mass or more. It is most preferable to use 99 parts by mass or more. In addition, from the aspect of low environmental load due to the use of plant-derived materials, the resin composition of the present invention preferably uses 75 parts by mass or more of a resin made of plant-derived materials among 100 parts by mass of the resin. , 90 parts by mass or more, and most preferably 99 parts by mass or more. The resin composed of a plant-derived raw material may be a high-molecular-weight product obtained directly from a plant or a derivative thereof, or a resin produced by polymerizing a compound obtained from a plant as it is or after modifying it. Specific examples of the resin composed of plant-derived raw materials include cellulose and derivatives thereof, starch and derivatives thereof, polyamide 11, natural rubber and derivatives thereof, in addition to polylactic acid.
[0014]
In the resin composition constituting the foam of the present invention, the layered silicate is contained in an amount of 0.1 to 50 parts by mass based on 100 parts by mass of the resin. Preferably it is 0.5 to 20 parts by mass, more preferably 1 to 10 parts by mass. If the amount of the layered silicate is less than 0.1 part by mass, the effect of the layered silicate as a foam nucleus material is reduced, and it is not preferable because bubbles are difficult to become fine. If the amount of the layered silicate exceeds 50 parts by mass, not only is the operability in the step of producing the resin composition deteriorated, but also the foaming of the resin is inhibited, which is not preferable.
[0015]
Specific examples of the layered silicate used in the present invention include smectite, vermiculite, and swellable fluoromica. Examples of smectites include montmorillonite, beidellite, hectorite, saponite and the like. Examples of swellable fluorine mica include Na-type tetrasilicon mica, Na-type teniolite, Li-type teniolite and the like, and in addition to the above, do not include aluminum and magnesium such as kanemite, macatite, magadiite, and kenyaite. Layered silicates can also be used. A synthetic product other than a natural product may be used, and examples of the synthesis method include a melting method, an intercalation method, and a hydrothermal method, and any method may be used. These layered silicates may be used alone, or two or more of them having different types, minerals, localities and particle sizes of minerals may be used in combination.
Among the above layered silicates, montmorillonite, hectorite, saponite, and swellable fluoromica are preferably used. Particularly preferred are montmorillonite or swellable fluoromica.
[0016]
Further, in the layered silicate used in the present invention, an organic compound is preferably inserted in advance between layers for the purpose of improving the dispersibility of the layered silicate in the resin composition. Examples of the method of insertion include (A) a method in which an exchangeable metal ion existing between layers is ion-exchanged with an organic cation, and (B) a method in which an organic substance is simply inserted between layers to swell. Further, both methods may be used in combination. As a specific means for replacement or insertion, a generally known method can be used.
[0017]
Examples of the organic cation used in the method (A) include cations obtained by protonating primary to tertiary amines, aminocarboxylic acids, and the like, quaternary ammonium ions, phosphonium ions, and the like. Examples of the primary amine include octylamine, dodecylamine, octadecylamine and the like. Examples of the secondary amine include dioctylamine, methyloctadecylamine, dioctadecylamine and the like. Examples of the tertiary amine include trioctylamine, dimethyldodecylamine, didodecylmonomethylamine and the like. Examples of the quaternary ammonium ion include tetraethylammonium, octadecyltrimethylammonium, dimethyldioctadecylammonium, dihydroxyethylmethyloctadecylammonium, methyldodecylbis (polyethylene glycol) ammonium, and methyldiethyl (polypropyleneglycol) ammonium. Further, examples of the phosphonium ion include tetraethylphosphonium, tetrabutylphosphonium, hexadecyltributylphosphonium, tetrakis (hydroxymethyl) phosphonium, and 2-hydroxyethyltriphenylphosphonium. Examples of aminocarboxylic acids include 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and the like. The aminocarboxylic acid may be mixed in the form of the corresponding lactam, and the ring may be opened between the layers to be inserted as a cation of the aminocarboxylic acid. Of these, cations of primary to tertiary amines, quaternary ammonium ions and phosphonium ions are particularly preferred. These compounds may be used alone or in combination of two or more.
[0018]
Compounds used in the method (B) include alcohols such as methanol, ethanol, propanol and butanol, diols such as ethylene glycol, propylene glycol and 1,4-butanediol, acetic acid, propionic acid and valeric acid. And carboxylic acids such as benzoic acid, adipic acid, sebacic acid, maleic acid, terephthalic acid and isophthalic acid, and hydroxycarboxylic acids such as lactic acid and lactide.
[0019]
In the resin composition constituting the foam of the present invention, it is preferable that the layered silicate is uniformly dispersed in a state where the polymer molecules of the resin are inserted between the layers and the interlayer distance is increased. When a value measured by an X-ray diffraction method is used as an index, a specific interlayer distance is preferably 2.6 nm or more, more preferably 2.8 nm or more, and still more preferably 3.0 nm or more. Also, most preferably, the layered silicate has been exfoliated to a state close to a single layer, and no peak derived from the interlayer distance is observed by X-ray diffraction.
[0020]
The resin composition constituting the foam of the present invention, as long as its properties are not significantly impaired, pigments, dyes, heat stabilizers, antioxidants, weathering agents, flame retardants, plasticizers, lubricants, release agents, It is also possible to add an antistatic agent, a dispersant, a filler, a crystal nucleus material, and the like. As the heat stabilizer and the antioxidant, for example, hindered phenols, phosphorus compounds, hindered amines, sulfur compounds, copper compounds, alkali metal halides, and mixtures thereof can be used. As the inorganic filler, talc, calcium carbonate, zinc carbonate, wollastonite, silica, alumina, magnesium oxide, calcium silicate, sodium aluminate, calcium aluminate, sodium aluminosilicate, magnesium silicate, glass balloon, carbon black, Examples include zinc oxide, antimony trioxide, zeolite, hydrotalcite, metal fibers, metal whiskers, ceramic whiskers, potassium titanate, boron nitride, graphite, glass fibers, and carbon fibers. Examples of the organic filler include naturally occurring polymers such as starch, cellulose fine particles, wood flour, okara, fir husk, and bran, and modified products thereof. Examples of the inorganic crystal nucleus material include talc and kaolin, and examples of the organic crystal nucleus material include a sorbitol compound, benzoic acid and a metal salt of the compound, a phosphate metal salt, and a rosin compound. Among them, the organic crystal nucleus material can be preferably used because the crystal of the resin composition becomes finer and the transparency is improved by adding a small amount thereof.
[0021]
The method of mixing the above-mentioned heat stabilizer, antioxidant, plasticizer, filler, crystal nucleus material and the like with the resin composition of the present invention is not particularly limited, and the production process of the raw material resin or the raw material It can be added in any of the steps of mixing the resin and the layered silicate, impregnating the resin composition with gas and / or supercritical fluid, and degassing and foaming. Preferably, they are mixed in the step of mixing the raw resin and the layered silicate or in the step of manufacturing the raw resin.
[0022]
The foam of the present invention is produced by impregnating the above resin composite with a gas or a supercritical fluid and then degassing the resin composite. A supercritical fluid has a property intermediate between that of a gas and a liquid, and becomes a supercritical fluid at a temperature and pressure (critical point) determined by the type of gas. In the present invention, a method of impregnating with a supercritical fluid is preferred. The type of gas is not particularly limited and includes butane, chlorofluorocarbon, alternative chlorofluorocarbon, carbon dioxide, and nitrogen.However, carbon dioxide and nitrogen having a low environmental load are preferable, and carbon dioxide is preferably used to easily obtain a supercritical state. Most preferred.
[0023]
Examples of the method for producing the foam of the present invention include a method having a step of impregnating the thermoplastic resin composition with a gas and / or a supercritical fluid, and a step of degassing and foaming the resin. Other conditions are not particularly limited as long as the process is provided, but as a preferable example, a gas and / or a supercritical fluid is sealed in a closed autoclave, impregnated for a certain period of time, and then the pressure of the autoclave is released to foam. A method for introducing the thermoplastic resin composition into a melt extruder, injecting gas and / or supercritical fluid from the middle of the cylinder, impregnating the gas and / or supercritical fluid using the pressure in the cylinder, A method of foaming at the die exit of the extruder, a method of injecting gas and / or supercritical fluid from the middle of the cylinder of the injection molding machine, and foaming in a mold are exemplified.
[0024]
The temperature in the step of impregnating the resin composition with a gas and / or a supercritical fluid is not particularly limited, but is preferably 280 ° C or lower. If it exceeds 280 ° C., the resin composition tends to decompose and deteriorate.
[0025]
Further, there is no particular limitation on the pressure at which the resin composition is impregnated with the gas and / or the supercritical fluid. Preferably, the temperature and pressure are such that the gas is in a supercritical state. In the case of carbon dioxide, it becomes a supercritical state at 35 ° C. and 7.5 MPa.
[0026]
The temperature in the step of degassing and foaming the resin is preferably not less than the glass transition temperature (Tg) and not more than the melting point (Tm) of the resin composition. In this temperature range, crystallization of the resin composition is promoted, and a foam having fine cells is easily obtained. More preferably, it is (Tg + 20) ° C to (Tm-10) ° C. If the temperature is less than Tg, foaming does not occur, and if the temperature exceeds Tm, the viscosity of the resin is reduced.
[0027]
Further, in the first stage of the process of degassing and foaming the resin, it is preferable that the crystallinity of the resin composition is increased, and the specific crystallinity is 10% as measured by DSC. It is preferably at least 20%, more preferably at least 20%, even more preferably at least 40%. By increasing the crystallinity of the resin composition, excessive growth of bubbles is suppressed, and a foam having a fine bubble diameter is easily obtained. The timing for promoting crystallization may be before or during the step of impregnating with gas and / or supercritical fluid, and is not particularly limited.
[0028]
The foam foamed by the above method is characterized in that the bubbles are very fine. Specifically, the following formulas (1) and (2) related to the dispersion state of the layered silicate are satisfied.
d / L ≦ 50 (1)
d / ξ ≦ 100 (2)
Here, d represents the average bubble diameter (nm), L represents the average major axis diameter (nm) of the layered silicate, and 表 す represents the average distance (nm) between adjacent layered silicates.
In addition, about the relationship of Formula (1), it is preferable that d / L ≦ 20, d / L ≦ 6 is more preferable, and d / L ≦ 3 is particularly preferable. Regarding the formula (2), preferably, d / ξ ≦ 40, more preferably d / ξ ≦ 12, particularly preferably d / ξ ≦ 5, and most preferably d / ξ ≦ 3.
The bubble diameter is preferably measured by observation with a scanning electron microscope, and the average major axis of the layered silicate and the distance between adjacent layered silicates are preferably measured with a transmission electron microscope.
[0029]
The bubble density is preferably 10 9 (pieces / cm 3 ) or more, more preferably 10 11 (pieces / cm 3 ) or more, and still more preferably 10 14 (pieces / cm 3 ) or more. If it is less than 10 9 (pieces / cm 3 ), individual bubbles tend to grow excessively and become larger.
[0030]
The expansion ratio of the foam is not particularly limited, but is preferably 1.1 to 3 times, and more preferably 1.2 to 2.5 times. If the expansion ratio is too low, the lightness, which is one of the characteristics of the foam, tends to be low. If the expansion ratio is too high, it is difficult to finely control the cell diameter.
[0031]
Since the foam of the present invention is excellent in lightness and has less decrease in mechanical properties as compared with a non-foamed body, it is particularly preferably used in applications where both lightweight and mechanical properties are required. Specifically, it is suitably used for containers, packaging, household goods, automobile parts, electric parts, and the like.
[0032]
[Action]
In the present invention, the following two reasons can be obtained as a foam having fine cells. One is that the layered silicate dispersed in the resin acts as a foam nucleating material, and the other is that the temperature conditions and the crystallinity of the resin in the process of degassing and foaming the resin are optimized. That is, excessive bubble growth is suppressed. Further, the layered silicate dispersed in the resin also has a favorable effect of increasing the elongational viscosity of the resin and increasing the crystallization rate.
[0033]
【Example】
Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to Examples. In addition, the measuring method used for evaluation of the resin composition of Example and a comparative example and a foam is as follows.
(1) Average major axis L of layered silicate, distance between adjacent layered silicates ξ
Using a transmission electron microscope (JEM-200CX manufactured by JEOL), at a magnification of 20,000 times, within the visual field in which 20 or more layered silicate particles are observed, the major axis of each layered silicate and the adjacent layered silicate particles The distance between them was visually measured to calculate an average value. This operation was performed in 20 different fields, and the average value was calculated to obtain the average major axis L and the distance between adjacent layered silicates ξ.
(2) Using a scanning electron microscope with a bubble diameter (JSM-5310LV manufactured by JEOL Ltd.), the photographed image was subjected to image processing, the distribution of the bubble diameter was determined, and the average bubble diameter was determined by Gaussian function approximation. The photographing magnification was 3500 times in Example 1, 1000 times in Example 2, and 75 times in Comparative Example 1.
(3) Cell density From the density of the foam, the density before foaming, and the cell diameter, the cell density was determined by the following formula. (NanoLets. 2001; 1: 503).
Bubble density (pieces / cm 3 ) = (1−ρf / ρp) / (10 −4 × d 3 )
In the above formula, ρf is the density of the foam, ρp is the density before foaming (all are g / cm 3 ), and d is the cell diameter (mm). The density of polylactic acid was 1.266 g / cm 3 .
(4) Crystallinity Using a differential scanning calorimeter (DSC7 manufactured by PerkinElmer), heating at a rate of 5 ° C. per minute, the melting peak area of the crystals obtained at this time and the crystallization peak area of the resin composition. Thus, the crystallinity was calculated using the following equation.
Crystallinity (%) = (melting peak area (J))-(crystallization peak area (J)) / (sample amount (g) x crystal melting enthalpy (J / g))
The enthalpy of fusion of polylactic acid is 93 J / g (Kolloid-ZZ Polymer. 1973; 25: 980).
[0034]
Example 1
For 100 parts by mass of polylactic acid (PLA) (NatureWorks, manufactured by Cargill Dow, Tg = 58 ° C., Tm = 168 ° C.), 5 parts by mass of montmorillonite (Esven E, manufactured by Hojun Co.) in which interlayer cations are substituted with trimethylstearyl ammonium ions. The mixture was mixed and melt-kneaded using a twin-screw extruder (PCM-45 manufactured by Ikegai) with a screw diameter of 45 mmφ under the conditions of 190 ° C., screw rotation speed of 200 rpm, and residence time of 2 minutes to obtain a resin composition. In this resin composition, the interlayer distance of montmorillonite was 3.1 nm.
[0035]
Next, the obtained resin composition was heat-treated at 110 ° C. for 2 hours, crystallized and then charged into an autoclave, and impregnated with supercritical carbon dioxide at 40 ° C. and 10 MPa for 4 hours. The crystallinity immediately before charging into the autoclave was 56%. The resin composition impregnated with carbon dioxide was taken out of the autoclave, placed in an oil bath kept at 160 ° C., and kept for 30 seconds to obtain a foam of the resin composition. About this foam, the cell diameter, the average major axis of the layered silicate, and the distance between adjacent layered silicates were measured.
[0036]
Example 2
To 100 parts by mass of PLA, 5 parts by mass of montmorillonite (ODA-CWC manufactured by Nanocor Co.) in which the interlayer cation was replaced by octadecyl ammonium ion was mixed, and a twin-screw extruder with a screw diameter of 45 mmφ (PCM-45 manufactured by Ikegai) was used. Melt kneading was performed at 190 ° C., a screw rotation speed of 200 rpm, and a residence time of 2 minutes to obtain a resin composition. In this resin composition, the interlayer distance of montmorillonite was 2.9 nm.
[0037]
Next, the obtained resin composition was heat-treated at 110 ° C. for 2 hours, crystallized and then put into an autoclave, and impregnated with supercritical carbon dioxide at 40 ° C. and 10 MPa for 4 hours. The crystallinity immediately before charging into the autoclave was 39%. The resin composition impregnated with carbon dioxide was taken out of the autoclave, placed in an oil bath maintained at 160 ° C., and held for 30 seconds to obtain a foam of the resin composition. About this foam, the cell diameter, the average major axis of the layered silicate, and the distance between adjacent layered silicates were measured.
[0038]
Comparative Example 1
Without using montmorillonite, for only 100 parts by mass of polylactic acid (PLA) (NatureWorks, manufactured by Cargill Dow), a foam was prepared in the same manner as in Example 1, and the cell diameter, the average major axis of the layered silicate, and the adjacent layer The distance between silicates and the crystallinity of the resin composition were measured.
[0039]
Comparative Example 2
An attempt was made to produce a foam in the same manner as in Example 1 except that the amount of montmorillonite used in Example 1 was 55 parts by mass with respect to 100 parts by mass of polylactic acid (PLA) (NatureWorks, manufactured by Cargill Dow). However, a good foam could not be obtained.
[0040]
Table 1 shows the results of Examples 1 and 2 and Comparative Examples 1 and 2.
[0041]
[Table 1]
In Examples 1 and 2, a foam having very fine air bubbles could be obtained. In particular, in Example 1 in which the degree of crystallinity was increased, the bubble density was high. As for Comparative Example 1, since a foam was produced without using a layered silicate, only a foam having a large cell diameter was obtained. In Comparative Example 2, a good foam could not be obtained because the amount of the layered silicate was too large.
[0043]
【The invention's effect】
According to the present invention, it is possible to obtain an environmentally-friendly resin foam having extremely fine air bubbles, and in addition to containers, packaging, household goods, automobile parts, electric parts, etc. Can be provided.
[Brief description of the drawings]
FIG. 1 is a graph showing a cell diameter distribution of a foam obtained in Example 1 and a Gaussian function approximation curve.
FIG. 2 is a graph showing a cell diameter distribution of a foam obtained in Example 2 and a Gaussian function approximate curve.
Claims (5)
ｄ／Ｌ≦５０ （１）
ｄ／ξ≦１００ （２）
式（１）、（２）において、ｄは平均気泡径（ｎｍ）、Ｌは層状珪酸塩の平均長径（ｎｍ）、ξは隣接する層状珪酸塩間の平均距離（ｎｍ）を表す。A foam of a resin composition containing, as main components, 100 parts by mass of a thermoplastic resin containing 50 parts by mass or more of polylactic acid and 0.1 to 50 parts by mass of a layered silicate. Characterized by satisfying the following formulas (1) and (2).
d / L ≦ 50 (1)
d / ξ ≦ 100 (2)
In the formulas (1) and (2), d represents the average cell diameter (nm), L represents the average major axis diameter (nm) of the layered silicate, and ξ represents the average distance (nm) between adjacent layered silicates.
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| JP2003083550A JP4473517B2 (en) | 2003-03-25 | 2003-03-25 | Thermoplastic resin foam having fine bubbles and method for producing the same |
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| JP2003083550A JP4473517B2 (en) | 2003-03-25 | 2003-03-25 | Thermoplastic resin foam having fine bubbles and method for producing the same |
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| WO2006103928A1 (en) * | 2005-03-28 | 2006-10-05 | Kaneka Corporation | Process for producing extruded foam of polyhydroxyalkanoate resin and extruded foam obtained by the process |
| WO2006103926A1 (en) * | 2005-03-28 | 2006-10-05 | Kaneka Corporation | Process for producing extruded polyhydroxyalkanoate resin foam |
| JP2007191553A (en) * | 2006-01-18 | 2007-08-02 | Teijin Chem Ltd | Foam molding |
| JP2009286812A (en) * | 2008-05-27 | 2009-12-10 | Kao Corp | Production method of polylactic acid resin injection molded article |
| JP2009286813A (en) * | 2008-05-27 | 2009-12-10 | Kao Corp | Production method of polylactic acid resin injection molded article |
| JP2010006040A (en) * | 2008-05-26 | 2010-01-14 | Kao Corp | Method for producing injection-molded article of polylactic acid resin |
| JP2010024689A (en) * | 2008-07-17 | 2010-02-04 | Panasonic Electric Works Co Ltd | Floor panel |
| WO2010029754A1 (en) * | 2008-09-10 | 2010-03-18 | Komatsu Michio | Molded article and method for production thereof |
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| JP2010077180A (en) * | 2008-09-24 | 2010-04-08 | Toray Ind Inc | Polylactic acid foamed article and method for manufacturing the same |
| JP2011001090A (en) * | 2009-06-18 | 2011-01-06 | Michio Komatsu | Thin-walled container and injection molding method for the same |
| JP5993108B1 (en) * | 2015-03-18 | 2016-09-14 | バンドー化学株式会社 | Foaming resin composition and foamed molded article |
| WO2016147883A1 (en) * | 2015-03-18 | 2016-09-22 | バンドー化学株式会社 | Foamable resin composition and molded foam |
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