JP5587336B2 - 曇り度が低く防水性の高いアイオノマー組成物及びそれを含む物品 - Google Patents
曇り度が低く防水性の高いアイオノマー組成物及びそれを含む物品 Download PDFInfo
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Description
本願は、米国特許法第120条に基づき、2008年12月31日に出願された米国仮特許出願第61/141,940号への優先権を主張しており、これは、その全体が参照により本明細書に援用される。
下記実施例の各々において使用されるアイオノマーを、次のように調製した。先ず、アイオノマーの前駆体酸コポリマー(すなわち、エチレンとメタクリル酸とのコポリマー)を、断熱連続攪拌オートクレーブにおいて、以下を除き、米国特許第5,028,674号明細書の実施例1に記載される手順に実質的に従ってフリーラジカル重合により生成した:(1)エチレンとメタクリル酸の比率および開始剤の流量を制御することにより、反応器条件を、約200℃〜約260℃の温度、および170と240MPaの間の圧力で維持した;(2)(CE16以外において)プロパンテロゲンを反応器に供給しなかった;(3)反応器中のメタノールの総濃度を、エチレン、メタクリル酸、メタノールおよび開始剤溶液の総供給量に基づき(またはCE16においてはプロパンテロゲン、エチレン、メタクリル酸、メタノール、および開始剤溶液の総供給量に基づき)約2〜5mol%で維持した;(4)系を安定した状態で維持し、反応器を通って流れる材料の滞留時間を約5秒〜2分とした。また、合成されることになる個々の酸コポリマーに応じ、2つの異なるフリーラジカル開始剤、すなわちtert−ブチルペルアセテートまたはtert−ブチルペルオクトエート(peroctoate)のうちの一方を使用した。tert−ブチルペルアセテートが開始剤である場合(比較例CE1〜CE6、CE16およびCE18の場合)は、それを、50%濃度で無臭ミネラルスピリット中の溶液として利用した。tert−ブチルペルオクトエートが開始剤である場合(比較例CE7〜CE15、CE17、およびCE19の場合)は、それを、無臭ミネラルスピリット中90%濃度での混合物として利用した。アイオノマーを、溶融温度を200℃〜270℃に設定した高剪断溶融混練条件下の一軸スクリュー押出機において、または米国特許第6,518,365号明細書の実施例1に記載された一般的方法を用い、エチレンとメタクリル酸との前駆体コポリマーを水酸化ナトリウム溶液で部分的に中和することにより得た。
2 積層品中間シートを形成するアイオノマーを誘導するための前駆体酸コポリマーに含まれる、メタクリル酸の共重合単位の重量%。
3 前駆体酸コポリマーの溶融流量(MFR)は、アイオノマーのMFRに基づいて算出された。
4 「%中和 (ナトリウム)」は、中和された前駆体酸コポリマーに含まれるカルボン酸基の百分率である。
5 ASTM D1238に準拠して190℃および2.16 kgで測定される場合のアイオノマーの溶融流量(MFR)。
6 「n.d.」は、ASTM D3418-03に準拠して測定される場合に、凍結エンタルピーが検出不可能であることを意味する。
比較例CE20〜CE24において使用するアイオノマーを、CE22およびCE23において使用するアイオノマーの調製において水酸化ナトリウムの溶液の代わりに酢酸亜鉛または酸化亜鉛濃縮物の溶液を使用したということを除いて、比較例CE1〜CE19について上記したのと実質的に同様に調製した。実施例E1〜E3において使用するアイオノマーの調製においては、まず適切な量の水酸化ナトリウム溶液を注入し、次いで適切な量の酢酸亜鉛溶液を注入することにより前駆体酸コポリマーを中和したということを除いて、比較例CE1〜CE19において使用した方法と同様の方法に従った。実施例E4において使用するアイオノマーを、75重量%の比較例CE21において使用するアイオノマーおよび25重量%の比較例CE22において使用するアイオノマーを溶融ブレンドすることにより調製した。実施例E5において使用するアイオノマーを、50重量%の比較例CE21において使用するアイオノマーおよび50重量%の比較例CE22において使用するアイオノマーを溶融ブレンドすることにより調製した。実施例E6において使用するアイオノマーを、25重量%の比較例CE21において使用するアイオノマーおよび75重量%の比較例CE22において使用するアイオノマーを溶融ブレンドすることにより調製した。実施例E7において使用するアイオノマーを、50重量%の比較例CE22において使用するアイオノマーおよび50重量%の比較例CE24において使用するアイオノマーを溶融ブレンドすることにより調製した。
2 これらの例において使用されたガラス積層品は、2枚のガラスシートの間に挟まれた3層の0.84 mm厚のアイオノマーシートを有する。
3 これらの例において使用されたアイオノマーシートは、100×50×0.76 mmの大きさを有する。
次に、本発明の態様を示す。
1. ナトリウム/亜鉛混合アイオノマーを含む組成物であって、前記ナトリウム/亜鉛混合アイオノマーは前駆体酸コポリマーの中和生成物であり;さらに
(a)前記前駆体酸コポリマーは、2個〜10個の炭素原子を有するα−オレフィンの共重合単位、および前記前駆体酸コポリマーの総重量に基づき約20〜約30重量%の、3個〜8個の炭素原子を有するα,β−エチレン性不飽和カルボン酸の共重合単位を含み;前記前駆体酸コポリマーは、ASTM D1238に準拠して190℃および2.16kgで測定される場合に約10〜約4000g/10分のメルトフローレートを有し;かつ前記前駆体酸コポリマーは、前記前駆体酸コポリマー中に存在するカルボン酸基の総数に基づき約40%〜約90%のレベルまで中和されてカルボキシレート基とナトリウムイオンから実質的になる対イオンとを含む場合、ナトリウムアイオノマーを生成し、前記ナトリウムアイオノマーは、ASTM D3418に準拠して示差走査熱分析により測定される場合に検出不可能な、または約3.0j/g未満の凍結エンタルピーを有し;そして
(b)前記ナトリウム/亜鉛混合アイオノマーは、カルボキシレート基と対イオンの組み合わせとを含み;前記対イオンの組み合わせは、前記ナトリウム/亜鉛混合アイオノマー中のカルボキシレート基の総当量数に基づき約1〜約99当量%のナトリウムカチオン、および補完的に約99〜約1当量%の亜鉛カチオンから実質的になる
組成物。
2. 前記前駆体酸コポリマーの酸部分の約40%〜約70%が中和されているか;または前記ナトリウム/亜鉛混合アイオノマーが、190℃および2.16kgで約0.7〜約35g/10分以下のメルトフローレート(MFR)を有するか;または前記前駆体酸コポリマーが、前記α,β−エチレン性不飽和カルボン酸の共重合単位を約20〜約25重量%含むか;または前記対イオンの組み合わせが、約50〜約95当量%の前記ナトリウムカチオンおよび補完的に約5〜約50当量%の前記亜鉛カチオンから実質的になる、上記1に記載の組成物。
3. 上記1もしくは上記2に記載の組成物を含む、または上記1もしくは上記2に記載の組成物から製造された物品。
4. 前記物品が、浸漬被覆、溶液流延、積層、溶融押出、ブローンフィルム、押出被覆、およびタンデム押出被覆からなる群より選択される方法によって調製されたフィルムもしくはシートである;または前記物品が、圧縮成形、射出成形、押出成形、および吹込成形からなる群より選択される方法によって調製された成形品である、上記3に記載の物品。
5. 前記物品が、少なくとも約1mmの最小厚さを有する射出成形品である;または前記物品が、前記組成物から実質的になる層を少なくとも1層有する多層構造を有する射出成形品であり、前記少なくとも1層が少なくとも約1mmの最小厚さを有する、上記3または上記4に記載の物品。
6. 前記物品が、シート、容器、キャップもしくはストッパー、トレー、医療用デバイスもしくは器具、ハンドル、ノブ、押ボタン、装飾用品、パネル、コンソールボックス、または履物部材である、上記5に記載の物品。
7. 前記物品が、同時射出成形;オーバーモールド成形;射出吹込成形;射出延伸吹込成形、および押出吹込成形からなる群より選択される方法によって製造される、上記4に記載の物品。
8. 上記1に記載の組成物から実質的になり、約1〜約100mmの厚さを有する、射出成形により調製された物品。
Claims (3)
- ナトリウム/亜鉛混合アイオノマーを含む組成物であって、前記ナトリウム/亜鉛混合アイオノマーは前駆体酸コポリマーの中和生成物であり;さらに
(a)前記前駆体酸コポリマーは、2個〜10個の炭素原子を有するα−オレフィンの共重合単位、および前記前駆体酸コポリマーの総重量に基づき20〜30重量%の、3個〜8個の炭素原子を有するα,β−エチレン性不飽和カルボン酸の共重合単位を含み;前記前駆体酸コポリマーは、ASTM D1238に準拠して190℃および2.16kgで測定される場合に10〜4000g/10分のメルトフローレートを有し;かつ前記前駆体酸コポリマーは、前記前駆体酸コポリマー中に存在するカルボン酸基の総数に基づき40%〜90%のレベルまで中和されてカルボキシレート基とナトリウムイオンからなる対イオンとを含む場合、ナトリウムアイオノマーを生成し、前記ナトリウムアイオノマーは、ASTM D3418に準拠して示差走査熱分析により測定される場合に検出不可能な、または3.0j/g未満の凍結エンタルピーを有し;そして
(b)前記ナトリウム/亜鉛混合アイオノマーは、カルボキシレート基と対イオンの組み合わせとを含み;前記対イオンの組み合わせは、前記ナトリウム/亜鉛混合アイオノマー中のカルボキシレート基の総当量数に基づき1〜99当量%のナトリウムカチオン、および99〜1当量%の亜鉛カチオンを含有する
組成物。 - 前記前駆体酸コポリマーの酸部分の40%〜70%が中和されているか;または前記ナトリウム/亜鉛混合アイオノマーが、190℃および2.16kgで0.7〜35g/10分以下のメルトフローレート(MFR)を有するか;または前記前駆体酸コポリマーが、前記α,β−エチレン性不飽和カルボン酸の共重合単位を20〜25重量%含むか;または前記対イオンの組み合わせが、50〜95当量%の前記ナトリウムカチオンおよび5〜50当量%の前記亜鉛カチオンを含有する、請求項1に記載の組成物。
- 請求項1もしくは請求項2に記載の組成物を含む、または請求項1もしくは請求項2に記載の組成物から製造された物品。
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- 2009-11-02 JP JP2011544432A patent/JP5587336B2/ja active Active
- 2009-11-02 EP EP09836577.8A patent/EP2376548B1/en active Active
- 2009-11-02 US US12/610,881 patent/US8334033B2/en active Active
- 2009-11-02 CN CN201710206839.4A patent/CN107043486A/zh active Pending
- 2009-11-02 WO PCT/US2009/062932 patent/WO2010077428A1/en active Application Filing
- 2009-11-02 KR KR1020117017800A patent/KR101693902B1/ko active IP Right Grant
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KR20110119674A (ko) | 2011-11-02 |
CN107043486A (zh) | 2017-08-15 |
KR101693902B1 (ko) | 2017-01-06 |
WO2010077428A8 (en) | 2011-01-06 |
US20100166992A1 (en) | 2010-07-01 |
EP2376548A4 (en) | 2012-07-11 |
US8334033B2 (en) | 2012-12-18 |
CN102325812A (zh) | 2012-01-18 |
AU2009333797A1 (en) | 2011-06-30 |
WO2010077428A1 (en) | 2010-07-08 |
JP2012514100A (ja) | 2012-06-21 |
AU2009333797B2 (en) | 2015-05-14 |
EP2376548A1 (en) | 2011-10-19 |
EP2376548B1 (en) | 2020-04-01 |
BRPI0918690A2 (pt) | 2017-05-30 |
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