JP2015508341A - 多層フィルム - Google Patents
多層フィルム Download PDFInfo
- Publication number
- JP2015508341A JP2015508341A JP2014547625A JP2014547625A JP2015508341A JP 2015508341 A JP2015508341 A JP 2015508341A JP 2014547625 A JP2014547625 A JP 2014547625A JP 2014547625 A JP2014547625 A JP 2014547625A JP 2015508341 A JP2015508341 A JP 2015508341A
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- Prior art keywords
- multilayer film
- starch
- layer
- film according
- atm
- 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.)
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Abstract
Description
(a)加工デンプンを含む少なくとも1層のデンプン層;および
(b)38℃、相対湿度90%で測定される水蒸気透過係数が1g・mm/m2・24hr・atm未満である少なくとも1層の他の層
を含む多層フィルムであって、少なくとも1層のデンプン層の全体の厚さが多層フィルム全体の厚さの20%超であり、かつ加工デンプンが1.5未満の置換度を有する多層フィルムを提供する。
他の層は、作製される多層フィルムにある種の物理的および美的特性を付与するように選択され得る。これらの特性としては、例えば、防曇、強度、ヒートシール性、色、または透明性を挙げ得る。いくつかの実施形態では、特に好ましい他の層は、低水蒸気透過速度を有するものである。
多層フィルムは、置換度が1.5未満の加工デンプンを含む少なくとも1層のデンプン層を含む。置換度は、無水グルコース1単位当たりの平均置換数を定義する。したがって、定義によれば、デンプンの最大可能置換度は3.0である。
いくつかの実施形態では、少なくとも1層の他の層は、適切な接着剤を使用して、少なくとも1層のデンプン層に固定されていてもよい。これは滑りを最小限に抑え、したがって優れたバリア性能を維持する助けとなる。当業者であれば、数多くの適切な接着剤が容易にわかるであろう。接着剤は少なくとも1層のデンプン層に化学的に結合するように選択することが好ましい。好ましい接着剤は、1種または複数種のポリウレタンを含む。
多層フィルムは、各種の方法により作製することができる。多層フィルムは、共押出、コーティング、および他のラミネート法により作製することができる。フィルムはまた、キャスト法またはインフレーション法により作製することができる。
当業者であれば、3層または5層のフィルムが、デンプンおよび他の層を使用する多くの可能な実施形態のなかの1つにすぎないことを理解されたい。層の数およびそれらの相対的な厚さは、そのフィルムの機能または最終用途に応じて調節し得る。
適切なLLDPE、HDPEおよびポリプロピレンは、チーグラー(Ziegler)触媒、シングルサイト触媒、または他の任意のオレフィン重合触媒により製造することができる。チーグラー触媒および共触媒は、当該技術分野でよく知られている。メタロセンシングルサイト触媒は、シクロペンタジエニル(Cp)またはCp誘導配位子を含む遷移金属化合物である。例えば、米国特許第4,542,199号明細書には、メタロセン触媒の製造方法が記載されている。ヘテロ原子配位子を含む非メタロセンシングルサイト触媒、例えばボラアリール、ピロリル、アザボロリニルまたはキノリニルもまた、当該技術分野ではよく知られている。
好ましい加工デンプン成分は、ヒドロキシプロピル化アミロースデンプンである。他の置換基は、ヒドロキシエーテル置換基を生成するためのヒドロキシエチル基またはヒドロキシブチル基であってもよく、あるいはエステル誘導体を製造するために、マレイン酸、フタル酸またはオクテニルコハク酸無水物などの無水物を使用することができる。置換度(1単位中の置換されたヒドロキシル基の平均数)は0.05〜1.5であることが好ましい。好ましいデンプンは、高アミローストウモロコシデンプンである。他の好ましいデンプンは高アミロースタピオカデンプンである。好ましい加工デンプン成分はヒドロキシプロピル化高アミロースデンプン(例えば、NatIonal Starch and Chemical Companyから市販されているECOFILM(登録商標)、またはPenfordから市販されているGelose(登録商標))である。
デンプン層の水溶性ポリマー成分は、デンプンと相溶性があり、水溶性で、生分解性であることが好ましく、デンプンの加工温度と両立する低融点を有する。ポリビニルアルコールが好ましいポリマーであるが、エチレン・ビニルアルコール、エチレン・酢酸ビニルのポリマー、またはポリビニルアルコールとのブレンド物も使用し得る。濃度範囲は、好ましくは4〜12重量%、より好ましくは8%〜12%である。
加工の補助、ならびにバリア材料の機械的特性の制御および安定化のため、特に湿分含有量および相対湿度に対する依存性を低下させる点において、ある範囲の可塑剤および保湿剤は、デンプン層への有用な添加剤である。必要な可塑剤含有量は、主に、(共)押出加工時、およびその後のインフレーションまたは延伸加工時に要求される加工特性、ならびに最終製品に要求される機械的特性に主に依存する。
1.押出混練プロセスおよびラミネートプロセスに適切な流動性を付与し、
2.製品の機械的特性に良好な影響を与え、そして
3.劣化防止剤または結晶防止剤として機能し得る。
ポリエチレングリコール化合物は、乳化剤、可塑剤または保湿剤として使用し得る。ポリエチレンオキサイドおよびポリエチレングリコールの単独使用または併用はまた、耐水性を高め、多層構造体(MLS)の層剥離をもたらし得る膨潤を防止し得る。
潤滑剤として、脂肪酸および/または脂肪酸塩を使用し得る。デンプン層は0.1〜1.5重量%のC12〜22脂肪酸および/またはC12〜22脂肪酸塩を含むことが好ましい。脂肪酸および/または脂肪酸塩成分は、0.6〜1%の濃度で含まれることがより好ましい。ステアリン酸は特に好ましい成分である。ステアリン酸のナトリウム塩およびカリウム塩もまた使用し得る。コストはこの成分を選択する際の因子となり得るが、ラウリン酸、ミリスチン酸、パルミチン酸、リノール酸およびベヘン酸も全て適している。
他の層のデンプン層への固定には、ポリウレタンベースの接着剤が特に適している。ポリウレタン接着剤は、1種または複数種のイソシアネートをデンプン層と反応させることにより、その場で調製し得る。デンプン表面のヒドロキシル基とイソシアネートの反応により、ウレタン基が生成する。好ましいイソシアネートは、ジイソシアネートである。当業者であれば、ポリウレタン合成の技術分野で通常使用されている広い範囲から適切なイソシアネートを選択できるであろう。
88.5重量%の加工デンプン(ECOFILM(登録商標)、National Starch and Chemical Company)、9重量%のポリビニルアルコール(Elvanol(登録商標)71−30)、2重量%のCloisite 20A(Southern Clay Products)、および0.5%のステアリン酸の混合物を押出加工し、300μmのシートにキャスト成形してデンプンフィルムを製造した。次に、この両面に100μmのHDPEフィルムを、MOR Free PU接着剤(Rohm and Haas)を使用して接着し、ラミネートした。ラミネートは標準のラミネート加工機で行った。
88.5重量%の加工デンプン(ECOFILM(登録商標)、National Starch and Chemical Company)、9重量%のポリビニルアルコール(Elvanol(登録商標)71−30)、2重量%のCloisite 20A(Southern Clay Products)、および0.5%のステアリン酸の混合物を押出加工し、150μmのシートにキャスト成形してデンプンフィルムを製造した。次に、この両面に50μm(実施例2)または35μm(実施例3)のHDPEフィルムを、Specialty Adhesives and Coatingsのポリウレタン接着剤系を使用して接着し、ラミネートした。ラミネートは標準のラミネート加工機で行った。
90.5重量%の加工デンプン(ECOFILM(登録商標)、National Starch and Chemical Company)、9重量%のポリビニルアルコール(Elvanol(登録商標)71−30)、および0.5重量%のステアリン酸の混合物を押出加工し、350μmのシートにキャスト成形してデンプンフィルムを製造した。次に、この両面に50μmのHDPEフィルムを、Specialty Adhesives and Coatingsのポリウレタン接着剤系を使用して接着し、ラミネートした。ラミネートは標準のラミネート加工機で行った。
90.5重量%の加工デンプン(ECOFILM(登録商標)、National Starch and Chemical Company)、9重量%のポリビニルアルコール(Elvanol(登録商標)71−30)、および0.5重量%のステアリン酸の混合物を押出加工し、350μmのシートにキャスト成形してデンプンフィルムを製造した。次に、この一方の面に50μmのHDPEフィルムを、他方の面に80μmのポリプロピレンフィルムを、Specialty Adhesives and Coatingsのポリウレタン接着剤系を使用して接着し、ラミネートした。ラミネートは標準のラミネート加工機で行った。
88.5重量%の加工デンプン(ECOFILM(登録商標)、National Starch and Chemical Company)、9重量%のポリビニルアルコール(Elvanol(登録商標)71−30)、2重量%のCloisite 20A(Southern Clay Products)、および0.5%のステアリン酸の混合物を押出加工し、290μmのシートにキャスト成形してデンプンフィルムを製造した。
100重量%の加工デンプン(ECOFILM(登録商標)、National Starch and Chemical Company)を押出加工し、300μmのシートにキャスト成形してデンプンフィルムを製造した。
各実施例のOTRおよびOPV(酸素透過値)を表8にまとめる。OPVは、コアのデンプン層の厚さについてのみ、1mm厚さの試料として正規化してある。
Claims (24)
- (a)加工デンプンを含む少なくとも1層のデンプン層;および
(b)38℃、相対湿度90%で測定される水蒸気透過係数が1g・mm/m2・24hr・atm未満である少なくとも1層の他の層
を含む多層フィルムであって、
前記少なくとも1層のデンプン層の全体の厚さが前記多層フィルム全体の厚さの20%超であり、かつ前記加工デンプンが1.5未満の置換度を有する多層フィルム。 - 前記少なくとも1層の他の層の水蒸気透過係数が、0.5g・mm/m2・24hr・atm未満、好ましくは0.2g・mm/m2・24hr・atm未満である請求項1に記載の多層フィルム。
- 前記少なくとも1層のデンプン層の全体の厚さが、前記多層フィルム全体の厚さの30%超、好ましくは前記多層フィルム全体の厚さの40%超、より好ましくは前記多層フィルム全体の厚さの50%超である請求項1または2に記載の多層フィルム。
- 前記少なくとも1層の他の層が、ポリオレフィン、ポリエチレンテレフタレート、ナイロン、ポリ塩化ビニルおよびポリ二塩化ビニリデン、またはこれらの混合物を含む請求項1〜3のいずれか一項に記載の多層フィルム。
- 前記ポリオレフィンが、エチレンホモポリマー、プロピレンホモポリマー、エチレンとプロピレンの共重合体、およびエチレンまたはプロピレンと1種または複数種のC4−C10のα−オレフィンとの共重合体、環状オレフィンポリマーおよびコポリマー、2軸延伸ポリプロピレン、化学的に改質されたポリオレフィン、ならびにこれらの混合物からなる群から選択される請求項4に記載の多層フィルム。
- 前記ポリオレフィンが、高密度ポリエチレン、低密度ポリエチレン、直鎖状低密度ポリエチレン、ポリプロピレン、2軸延伸ポリプロピレン、およびこれらの混合物からなる群から選択される請求項4に記載の多層フィルム。
- デンプン内層と2層のポリオレフィン外層を含む請求項1〜6のいずれか一項に記載の多層フィルム。
- 前記少なくとも1層のデンプン層は、接着剤により前記少なくとも1層の他の層に固定されている請求項1〜7のいずれか一項に記載の多層フィルム。
- 前記接着剤が、ポリウレタンおよび/またはポリウレタン尿素を含む請求項8に記載の多層フィルム。
- 前記フィルムは、50%RHで0.6cm3mm/m2・24hr・atm未満、好ましくは50%RHで0.3cm3mm/m2・24hr・atm未満、より好ましくは50%RHで0.1cm3mm/m2・24hr・atm未満、最も好ましくは50%RHで0.05cm3mm/m2・24hr・atm未満の酸素透過係数(OPC)を有する請求項1〜9のいずれか一項に記載の多層フィルム。
- 前記多層フィルム全体の厚さが10〜1000ミクロンである請求項1〜10のいずれか一項に記載の多層フィルム。
- 前記少なくとも1層のデンプン層が100〜600ミクロンの全体厚さを有し、かつ前記少なくとも1層の他の層が10〜400ミクロンの全体厚さを有する請求項1〜11のいずれか一項に記載の多層フィルム。
- 前記少なくとも1層のデンプン層が10〜60ミクロンの全体厚さを有し、かつ前記少なくとも1層の他の層が5〜40ミクロンの全体厚さを有する請求項1〜11のいずれか一項に記載の多層フィルム。
- 前記加工デンプンが高アミロースデンプンを含む請求項1〜13のいずれか一項に記載の多層フィルム。
- 前記加工デンプンは、エーテルおよびエステル、ならびにそれらの混合物からなる群から選択される官能基でヒドロキシル官能基が置換されるように化学的に加工されている請求項1〜14のいずれか一項に記載の多層フィルム。
- 前記加工デンプンは、C2〜6のヒドロキシアルキル基を含むように化学的に加工されるか、またはカルボン酸無水物との反応により加工されている請求項1〜15のいずれか一項に記載の多層フィルム。
- 前記少なくとも1層のデンプン層は、少なくとも1種の水溶性ポリマーをさらに含む請求項1〜16のいずれか一項に記載の多層フィルム。
- 前記少なくとも1種の水溶性ポリマーは、ポリビニルアルコールおよびポリ酢酸ビニル、ならびにこれらの混合物からなる群から選択される請求項17に記載の多層フィルム。
- 前記少なくとも1層のデンプン層は、少なくとも1種の可塑剤をさらに含む請求項1〜18のいずれか一項に記載の多層フィルム。
- 前記少なくとも1種の可塑剤は、1種または複数種のポリオールを含む請求項19に記載の多層フィルム。
- 請求項1〜20のいずれか一項に記載の多層フィルムの製造方法であって、共押出、コーティング、キャストまたはフィルムインフレーションの工程の少なくとも1つを含む方法。
- 請求項1〜20のいずれか一項に記載の多層フィルムの包装、特に食品の包装における使用。
- 請求項1〜20のいずれか一項に記載の多層フィルムを含む製品。
- 前記製品が包装品である請求項23に記載の製品。
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WO2021048795A1 (ja) | 2019-09-13 | 2021-03-18 | プランティック・テクノロジーズ・リミテッド | 多層構造体、その製造方法および包装容器 |
DE112021002796T5 (de) | 2020-05-15 | 2023-04-13 | Plantic Technologies Ltd. | Laminat |
Also Published As
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BR112014015068A8 (pt) | 2017-07-04 |
CN104080715B (zh) | 2018-02-13 |
US20210094263A1 (en) | 2021-04-01 |
EP2794425A1 (en) | 2014-10-29 |
CN104080715A (zh) | 2014-10-01 |
AU2012318251B2 (en) | 2014-08-07 |
AR089443A1 (es) | 2014-08-20 |
EP2794425B1 (en) | 2023-06-07 |
US10894392B2 (en) | 2021-01-19 |
BR112014015068B1 (pt) | 2021-06-22 |
KR20140111300A (ko) | 2014-09-18 |
US11590738B2 (en) | 2023-02-28 |
BR112014015068A2 (pt) | 2017-06-13 |
US20140349047A1 (en) | 2014-11-27 |
AU2012318251C1 (en) | 2015-01-29 |
KR20190021476A (ko) | 2019-03-05 |
AU2012318251A8 (en) | 2014-08-21 |
EP2794425A4 (en) | 2015-08-26 |
JP6008980B2 (ja) | 2016-10-19 |
AU2012318251B8 (en) | 2014-08-21 |
AU2012318251A1 (en) | 2013-07-11 |
US20180229479A1 (en) | 2018-08-16 |
NZ625510A (en) | 2014-11-28 |
WO2013090973A1 (en) | 2013-06-27 |
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