JP4989099B2 - ポリ(3−ヒドロキシアルカノエート)樹脂系発泡成形体、及びその製造方法 - Google Patents
ポリ(3−ヒドロキシアルカノエート)樹脂系発泡成形体、及びその製造方法 Download PDFInfo
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- JP4989099B2 JP4989099B2 JP2006117619A JP2006117619A JP4989099B2 JP 4989099 B2 JP4989099 B2 JP 4989099B2 JP 2006117619 A JP2006117619 A JP 2006117619A JP 2006117619 A JP2006117619 A JP 2006117619A JP 4989099 B2 JP4989099 B2 JP 4989099B2
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- 235000014593 oils and fats Nutrition 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
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- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
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Landscapes
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Description
[−O−CHR−CH2−CO−] (1)
(ここでRはCnH2n+1で表されるアルキル基で、nは1以上15以下の整数である。)で示される一種以上の単位からなる共重合体(以下、ポリ(3−ヒドロキシアルカノエート):略称はP3HA)からなる発泡粒子50体積%以上99体積%以下と、P3HAと異なる樹脂からなる発泡粒子1体積%以上50体積%以下とが略均一に混合され、互いに融着してなるP3HA樹脂系発泡成形体に関する。
(1)前記P3HAが、変性剤を含んでなる、
(2)P3HAと異なる樹脂が、ポリ乳酸系樹脂、又は、ポリメタクリル酸メチル系樹脂である、
(3)P3HAが、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)(以下、略称はPHBH)である、
(4)PHBHの共重合成分の組成中、ポリ(3−ヒドロキシヘキサノエート)が1mol%以上20mol%以下である、
前記記載のP3HA樹脂系発泡成形体に関する。
[−CHR−CH2−CO−O−]………式(1)
ここで、RはCnH2n+1で表されるアルキル基で、n=1〜15の整数である。
P3HA:ポリ(3−ヒドロキシアルカノエート)
PHBH:ポリ(3−ヒドロキシブチレート−コ−3−ヒドロキシヘキサノエート)
PLA:ポリ乳酸系樹脂
PMMA:ポリメタクリル酸メチル系樹脂
HH率:PHBH中のヒドロキシヘキサノエートのモル分率(mol%)
23℃のエタノールの入ったメスシリンダーを用意し、該メスシリンダーに相対湿度50%、23℃、1atmの条件にて7日間放置した500個以上のPHBH発泡粒子、PLA発泡粒子、PMMA発泡粒子(発泡粒子群の重量W(g))及び、適当な大きさに切り出した発泡成形体を金網などを使用して沈め、エタノール水位上昇分より読みとられる発泡粒子群及び、成形体の容積V(cm3)としたときに、樹脂密度ρ(g/cm3)から次式で与えられる。
発泡倍率=V/(W/ρ)
マルチピクノメーター(ベックマン・ジャパン(株)社製)を用い、ASTM D−2856に準じて測定した。
微生物として、Alcaligenes eutrophusにAeromonas caviae由来のPHA合成酵素遺伝子を導入したAlcaligenes eutrophus AC32(J.Bacteriol.,179,4821(1997))を用いて原料、培養条件を適宜調整して生産されたPHBH、HH率12mol%のPHBH(比重1.2g/ml)100重量部とポリイソシアネート化合物2重量部(日本ポリウレタン製、ミリオネートMR-200(イソシアネート基2.7〜2.8当量/モル))とをハンドブレンドした後、ニーダー付きφ35mm単軸押出成形機(笠松加工製ラボ万能押出機)でシリンダー温度145℃にて溶融混練し、押出機先端に取り付けられた3mmφの小孔ダイより押し出されたストランドを、ペレタイザーでカットして粒重量5mg、融点135℃のPHBH樹脂組成物を作製した。
D体比率10%、数平均分子量10万、重量平均分子量21万のPLA(比重1.2g/ml)100重量部と、上記同様のポリイソシアネート化合物2重量部とを溶融混練し、水中カッターを用いて約1mm径のビーズ状樹脂組成物を作製した。次いで、ビーズ状樹脂組成物を各々42℃の温水中で15時間熟成・二次架橋した後、脱水、乾燥し、発泡剤含浸を行った。発泡剤含浸は、各熟成ビーズを各々10L回転ドラム型密閉容器に4.3kg仕込み、メタノール215g、イソブタン1720gを添加して、85℃にて3時間含浸を行い、常温で通気風乾して、発泡剤含浸したビーズ状樹脂組成物を得た。それを発泡スチロール用予備発泡機(ダイセン工業(株)製DYHL−300)にて発泡し、発泡倍率が35倍、独立気泡率98%のPLA発泡粒子を得た。
攪拌機を具備した200Lオートクレーブに、イオン交換水111重量部、第三リン酸カルシウム1.8重量部、ドデシルベンゼンスルフォン酸ナトリウム0.036重量部を入れ攪拌し水懸濁液とした後、メタクリル酸メチル系樹脂粒子100重量部を加え、90℃まで昇温した。ブタン(i/n=60/40)9重量部、トルエン1重量部、シクロヘキサン1重量部を圧入した後、105℃まで昇温し5時間30分含浸して冷却した。得られた発泡性メタクリル酸メチル系樹脂粒子を予備発泡し発泡倍率50倍、独立気泡率98%のPMMA発泡粒子を得た。
PHBH発泡粒子75体積%とPLA発泡粒子25体積%とを予め混合し、混合した発泡粒子を300×400×30mmの金型に充填し、0.10〜0.32MPa(ゲージ)の水蒸気を金型に導入し、両者の発泡粒子を加熱、融着させ、発泡倍率23倍、独気率92%のP3HA系樹脂発泡成形体を得た。比較例1と比べると、発泡倍率の向上が得られ、軽量化した発泡成形体を得ることができた。結果を表1に示す。
PHBH発泡粒子60体積%とPLA発泡粒子40体積%と、混合割合が異なる以外は、実施例1と同様に行った。水蒸気導入後、発泡倍率26倍、独気率91%のP3HA系樹脂発泡成形体を得た。比較例1と比べると、発泡倍率の向上が得られ、軽量化した発泡成形体を得ることができた。結果を表1に示す。
PHBH発泡粒子75体積%とPMMA発泡粒子25体積%を用いた以外は、実施例1と同様に行った。水蒸気導入後、発泡倍率26倍、独気率93%のP3HA樹脂系発泡成形体を得た。比較例1と比べると、発泡倍率の向上が得られ、軽量化した発泡成形体を得ることができた。結果を表1に示す。
PHBH発泡粒子60体積%とPMMA発泡粒子40体積%と、混合割合が異なる以外は、実施例1と同様に行った。水蒸気導入後、発泡倍率33倍、独気率92%のP3HA樹脂系発泡成形体を得た。比較例1と比べると、発泡倍率の向上が得られ、軽量化した発泡成形体を得ることができた。結果を表1に示す。
PHBH樹脂発泡粒子のみを用いた以外は、実施例1と同様に行った。水蒸気導入後、発泡倍率18倍、独気率92%のP3HA樹脂系発泡成形体を得た。結果を表1に示す。
Claims (4)
- 式(1)
[−O−CHR−CH2−CO−] (1)
(ここでRはCnH2n+1で表されるアルキル基で、nは1以上15以下の整数である。)
で示される一種以上の単位からなる共重合体(以下、ポリ(3−ヒドロキシアルカノエート):略称はP3HA)と変性剤としてイソシアネート化合物とを含んでなる発泡粒子50体積%以上99体積%以下と、ポリ乳酸系樹脂又はポリメタクリル酸メチル系樹脂からなる発泡粒子1体積%以上50体積%以下とが略均一に混合され、互いに融着してなるP3HA樹脂系発泡成形体。 - P3HAが、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)(以下、略称はPHBH)である請求項1に記載のP3HA樹脂系発泡成形体。
- PHBHの共重合成分の組成中、ポリ(3−ヒドロキシヘキサノエート)が1mol%以上20mol%以下である請求項2に記載のP3HA樹脂系発泡成形体。
- P3HAと変性剤としてイソシアネート化合物とを含んでなる発泡粒子と、ポリ乳酸系樹脂又はポリメタクリル酸メチル系樹脂からなる発泡粒子とを金型に略均一に混合、充填し、次いで加熱成形してなる、請求項1〜3何れか一項に記載のP3HA樹脂系発泡成形体の製造方法。
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