JP2022142016A - 海洋生分解促進添加剤及びこれを含む海洋生分解性樹脂組成物 - Google Patents
海洋生分解促進添加剤及びこれを含む海洋生分解性樹脂組成物 Download PDFInfo
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- JP2022142016A JP2022142016A JP2021041970A JP2021041970A JP2022142016A JP 2022142016 A JP2022142016 A JP 2022142016A JP 2021041970 A JP2021041970 A JP 2021041970A JP 2021041970 A JP2021041970 A JP 2021041970A JP 2022142016 A JP2022142016 A JP 2022142016A
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Abstract
Description
JIS K0102には、工場排水などのBOD(生物化学的酸素要求量)を測定する場合、微生物の植種として市街地の廃水等を10%程添加するとともに、微生物の増殖に必要な一般的な栄養源として、0.025%塩化鉄溶液、2.75%塩化カルシウム、2.25%硫酸マグネシウム、0.85%リン酸二水素一カリウム溶液、3.34%リン酸一水素二カリウム溶液、2.17%リン酸一水素二カリウム、0.17%塩化アンモニウム等を含む栄養塩液を加えることが記載されている。
竹本修明らは、陸上からの汚濁物質の海域における生分解性を評価するため、海水を用いて種々の有機物のBODを測定している。この場合もJIS K0102に従って、微生物の植種として大阪府の大津川の河川水を添加するとともに、微生物の一般的な栄養源を添加している。しかし、海水を用いたBOD測定の場合の栄養源の添加効果については記載が見当たらない。
国立研究開発法人産業技術総合研究所(産総研)の中山らは、大和川河口の大阪南港海域の海水を用いたBOD試験(27℃、28日間)により、PHB、PCLおよびPBSAは生分解が認められたが、PCLとPBSAについては海水の採取時期により分解率が大きく変動したことを報告している。
一方、株式会社カネカと産総研は、大阪南港海域の海水を用いたBOD試験(27℃、28日間)により、3-ヒドロキシ酪酸89モル%と3-ヒドロキシヘキサン酸11モル%からなる微生物由来の共重合体(PHBHH)が31%分解されたが、PBS、PBSAおよびPLAについては生分解に基づく酸素吸収が認められなかったことを報告している。
すなわち、本発明は有効成分として窒素化合物およびリン化合物を含有することを特徴とする海洋生分解促進添加剤、海洋生分解促進添加剤を含む海洋生分解性樹脂組成物および海洋生分解促進添加剤を用いた生分解性素材の海水中の分解方法に関する。
さらに、ポリウレタン、脂肪族ポリカーボネート、脂肪族ポリエステルと芳香族ポリエステルあるいはポリアミドとの共重合体、ビニル結合を含む脂肪族ポリエステル、ポリエーテルやエーテル結合を含むポリエステルなどがあげられる。
その他、2種以上の高分子を化学的に結合した共重合高分子や2種以上の高分子を物理的に混合した高分子ブレント体もあげられる。
生分解性を有する親水性高分子素材の用途としては、衛生用品、紙コーティング剤、農業・園芸資材、土木・建築資材などの他に、塗工紙(ポスター、カレンダー、雑誌のグラビア、折り込み広告等)や塗料などに添加される防汚剤や顔料の分散剤としても期待される。また、海洋生分解性素材の利用が期待できる分野として、船底や漁網、養殖基材、浮標、海水構造物などに海洋生物が付着するのを防止するための海洋生物付着防止塗料がある。
従来、防汚剤や顔料の分散剤として非生分解性の高分子量ポリアクリル酸系ポリマーが広く使用されてきたが、環境への影響が懸念されている。今後は生分解性を有する低・中分子量領域のポリアクリル酸(Na塩)系の素材や、ポリアクリルアミド、ポリビニルピロリドン、ポリプロピレングリコール、ポリブチレングリコールなどの代替品の開発が注目される。
例えば、無機系の窒素化合物としては硫酸アンモニウム、塩化アンモニウム、硝酸アンモニウム等の各種アンモニウム塩、有機系の窒素化合物としては各種アミノ酸およびそれらの誘導体、各種アミノ酸の重合体、ペプチド類、タンパク質、尿素などがあげられるが、これらに限定するものではない。
無機系のリン化合物としてはリン酸二水素ナトリウム、リン酸水素二ナトリウム、リン酸水素二カリウム等の各種リン酸塩及びポリリン酸など各種重合体、有機系のリン化合物としては各種のアルキルおよびアルケニルリン酸エステル、フィチン酸などの糖リン酸エステル、酵母エキス、ペプトン、核酸、などがあげられるがこれらに限定するものではない。
窒素とリンの両方を含む化合物としては、リン酸二水素アンモニウムやリン酸水素二アンモニウムなどの無機系化合物の他に、リボ核酸、デオキシリボ核酸などの核酸類、酵母エキス、肉エキス、海藻エキスやペプトン、トリプトン、など微生物や動植物の抽出液などがあげられるがこれらに限定するものではない。
海洋生分解促進添加剤は、粉末やペレット状の固体の他に、親水性あるいは親油性の液体・ゾル・ゲルに溶かした状態や分散させた状態で使用することも想定される。また、海洋生分解促進添加剤を天然や化学合成した低分子・高分子素材や樹脂などと混合して粉末・粒状・ペレット状・繊維状・棒状・フィルム状・板状に加工して各種のプラスチック製品等に溶融混合して使用することもできる。
本発明の海洋生分解性樹脂組成物は、海洋生分解促進添加剤と生分解性高分子素材を加熱溶融混合することによっても調整することができる。
図1は、BOD測定装置の構成を示した概要図である。500ml容量の褐色瓶の上部には圧力の変化により酸素消費量を検知してppmで表示する圧力センサーがセットされている。瓶の口部分には瓶と圧力センサーの間のパッキングも兼ねたゴム製のホルダーがセットしてある。ホルダーの中には被試験試料の生分解にともなって発生する二酸化炭素を吸収するソーダ石灰が入っている。被試験試料の分解率は、炭素C、水素H、窒素NおよびイオウSが、それぞれ二酸化炭素CO2、水H2O、硝酸HNO3、酸化イオウSO3に変換されるとして求めた理論的酸素要求量(ThOD)を100%として求めた値である。
海洋生分解促進添加剤NPを添加しなかった場合は、いずれも被試験物質も酸素消費は認められなかったが、海洋生分解促進添加剤NPを添加した場合は、PHB粉末、PCL粉末、ポリ-L-乳酸、L-乳酸とD-3-ヒドロキシ酪酸(D-3HB)の共重合体(モル比95:5と90:10)およびD-乳酸とD-3HBの共重合体(モル比95:5)の分解率は、それぞれ77.2%、51.9%、38.5%、53.4%、57.6%、74.6%であった。
なお、BAK2195とBAK1095の分解率については、ポリアミドとポリエステルの割合が不明なために、分解にともなう酸素消費量であるBOD値をppmで表した。PHBV(8%)については、共重合割合が分かっているのでBOD値とともに、PHBV(8%)の理論的酸素要求量(ThOD)を100%として求めた分解率も示した。その結果を表6に示した。海洋生分解促進添加剤を添加した場合、PHBV、BAK2195およびBAK1095の分解が認められた。
また、メノウ鉢で細かく粉砕したリン酸アンモニウムを新たな海洋生分解促進添加剤としてPHB粉末の重量に対して0.5%と5.0%になるように添加して、同様に海洋生分解促進添加剤を含むPHB樹脂組成物のフィルムを調製した。PHBが40mg含まれるそれぞれのフィルムをBOD瓶に入れて、27℃で7日間撹拌しながら海水による生分解性試験を行った。
さらに、海洋生分解促進添加剤NPを加えないで、セルロースとしてろ紙(アドバンテック5A)40mgのみをBOD瓶にいれて、同様に海水による生分解試験を行った。
窒素源およびリン源としては、それぞれ硫酸アンモニウム20ppmとリン酸一カリウム4ppmの濃度で使用した。また、海水の代わりに湖水、河川水、地下水(湧き水)、水道水、無機塩類培地なども使用できる。
2 BODボトル
3 CO2吸収剤を入れるホルダー
4 CO2吸収剤
5 海水
6 被試験試料
7 攪拌子
Claims (5)
- 窒素化合物およびリン化合物を有効成分として含有することを特徴とする海洋生分解促進添加剤。
- 窒素化合物中の窒素の重量が、リン化合物中のリンの重量の、2~15倍であることを特徴とする請求項1に記載の海洋生分解促進添加剤。
- 請求項1または2に記載の海洋生分解促進添加剤を含むことを特徴とする海洋生分解性樹脂組成物。
- 窒素及びリンの含量が、炭素重量に対して、それぞれ3~30%、0.3~10%であることを特徴とする海洋生分解性樹脂組成物。
- 被処理水中の窒素及びリンの濃度が、それぞれ1~2000ppm、0.1~400ppmになるように、被処理水に窒素及びリンを添加することを特徴とする海洋生分解性樹脂組成物の分解処理方法。
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JP2005334727A (ja) * | 2004-05-25 | 2005-12-08 | Tosoh Corp | 油汚染土壌の浄化法 |
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