JP5722629B2 - 二峰性アイオノマー組成物を含有する物品 - Google Patents
二峰性アイオノマー組成物を含有する物品 Download PDFInfo
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- JP5722629B2 JP5722629B2 JP2010534255A JP2010534255A JP5722629B2 JP 5722629 B2 JP5722629 B2 JP 5722629B2 JP 2010534255 A JP2010534255 A JP 2010534255A JP 2010534255 A JP2010534255 A JP 2010534255A JP 5722629 B2 JP5722629 B2 JP 5722629B2
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Description
本出願は、その全体が参照により本明細書に援用される、2007年11月16日出願の米国仮特許出願第61/003,432号明細書の優先権を米国特許法第120条のもとで主張するものである。
(i)1種以上のE/X/Yコポリマー(ここで、Eはエチレンの共重合単位を表し、XはC3〜C8のα,β−エチレン系不飽和カルボン酸の共重合単位を表し、Yは、酢酸ビニル、アルキル基が1〜8個の炭素原子を有するアルキルアクリレートおよびアルキルメタクリレートからなる群から選択される軟化コモノマーの共重合単位を表し、Xの量はE/X/Yコポリマーの約2〜約30重量%であり、Yの量はE/X/Yコポリマーの0〜約45重量%であり、E/X/Yコポリマーは80,000〜500,000Daの範囲の重量平均分子量(Mw)を有する)を含むハイコポリマーと;
(ii)1種以上のE/Zコポリマー(ここで、Eはエチレンの共重合単位を表し、Zはアクリル酸またはメタクリル酸の共重合単位を表し、Zの量はE/Zコポリマーの約3〜約25重量%であり、E/Zコポリマーは2,000〜30,000Daの範囲のMwを有する)を含むローコポリマーと
を含む二峰性アイオノマー組成物を含む、それから本質的になる、それから製造される少なくとも1つの表面層を有し、
ここで、E/X/YコポリマーおよびE/Zコポリマー中の合わせた酸性基の少なくとも35%が名目上中和されてカルボン酸塩を形成する物品が記載される。
(2)二峰性アイオノマー組成物に高周波電磁放射線、および任意選択的に圧力、熱、またはそれらの組み合わせを適用し、それによって二峰性アイオノマー組成物を軟化させるかまたは溶融させる工程と;
(3)軟化または溶融した二峰性アイオノマー組成物をそのまま固め、それによって二峰性アイオノマー組成物の第1表面を第1基材に接合させ、および二峰性アイオノマー組成物の第2表面を、存在する場合、第2基材に接合させる工程と
を含む多層物品の製造方法であって、
二峰性アイオノマー組成物が上記のように特徴付けられ、第1基材および任意の第2基材が、熱可塑性フィルムおよびシート、気泡質発泡体、織布、編布および不織布、紙、パルプおよび板紙製品、木材および木材製品、金属、ガラス、石、セラミック、および皮革および皮革様製品、熱可塑性樹脂、熱硬化性樹脂、ならびに上記のように特徴付けられる第2二峰性アイオノマー組成物からなる群から独立して選択される方法もまた提供される。
二峰性アイオノマーのハイコポリマー成分は好ましくは、約80,000〜約500,000DaのMwを有する「直接」酸コポリマー(グラフト化コポリマーとは対照的に)である。同様に好ましくは、それは、約1〜約15、より好ましくは約1〜約10の多分散性(Mw/Mn)を有する。
ローコポリマーは好ましくは、約2,000〜約30,000Daの分子量(Mw)を有する「直接」酸コポリマーである。好ましくはそれらは、約1〜約10、より好ましくは約1〜約6の多分散性(Mw/Mn)を有する。それらは好ましくは、α−オレフィン、特にエチレン、C3~8のα,β−エチレン系不飽和カルボン酸、特にアクリル酸およびメタクリル酸、コポリマーである。好ましくは、これらのコポリマー中の酸部分は、コポリマーの約3〜約30(または5〜20、または3〜15、最も好ましくは5〜10)重量%である。
アイオノマーは、コポリマー中のカルボン酸基の少なくとも幾らかが中和されて相当するカルボン酸塩を形成する酸コポリマーである。存在するカルボン酸基が塩基性化合物によって少なくとも部分的に中和されてアルカリ金属イオン、遷移金属イオン、アルカリ土類金属イオンまたはカチオンの組み合わせを含む塩を形成する、アイオノマーは、上記のハイおよびローコポリマーから製造されてもよい。アイオノマーの製造方法は、例えば、米国特許第3,264,272号明細書に開示されている。
任意選択的に、二峰性アイオノマー組成物は、ハイコポリマーとローコポリマーとのブレンドの100重量部を基準にして、200重量部以下の1種以上の他の熱可塑性ポリマーおよび/または170重量部以下の1種以上のフィラーを含有してもよい。例えば、組成物は、(a)二峰性アイオノマー組成物と(b)(a)+(b)を基準にして約1〜約60重量%の少なくとも1種の他の熱可塑性ポリマーとから本質的になってもよい。
式中、Gは、約400〜6,000の分子量および約2.0〜4.3の炭素対酸素比を有するポリ(アルキレンオキシド)グリコールからの末端ヒドロキシル基の除去後に残る二価ラジカルであり;Rは、約300未満の分子量を有するジカルボン酸からのカルボキシル基の除去後に残る二価ラジカルであり;Dは、約250未満の分子量を有するジオールからのヒドロキシル基の除去後に残る二価ラジカルであり;ただし、前記短鎖エステル単位は合計して前記コポリエーテルエステルの約15〜95重量パーセントになる。好ましいコポリエーテルエステルポリマーは、ポリエーテルセグメントがテトラヒドロフランの重合によって得られ、ポリエステルセグメントがテトラメチレングリコールとフタル酸との重合によって得られるものである。コポリエーテルエステル中へ組み込まれたポリエーテル単位が多ければ多いほど、ポリマーはよりソフトになる。エーテル:エステルモル比は、90:10〜10:90、好ましくは80:20〜60:40と変わってもよく;ショアD硬度は70未満、好ましくは約40未満であってもよい。
式中、PAは、4〜14個の炭素原子を含有する炭化水素鎖を有するラクタムもしくはアミノ酸から、または4〜20個の炭素原子を有する鎖長制限脂肪族ジカルボン酸の存在下に、脂肪族C6〜C9のジアミンから形成される直鎖状飽和の脂肪族ポリアミド配列であり;前記ポリアミドは300〜15,000の平均分子量を有し;PEは、直鎖状もしくは分岐の脂肪族ポリオキシアルキレングリコール、それらの混合物またはそれらに由来するコポリエーテルから形成されるポリオキシアルキレン配列であり、前記ポリオキシアルキレングリコールが6,000以下の分子量を有し、nは、前記ポリエーテルアミドコポリマーが約0.8〜約2.05の固有粘度を有するほどに十分な繰り返し単位の数を示す。これらのポリエーテルアミドの製造は、そのCOOH基が鎖端にあるジカルボン酸ポリアミドを、一般式Ti(OR)4(式中、Rは、1〜24個の炭素原子を有する直鎖状、分岐の脂肪族炭化水素ラジカルである)を有するテトラアルキルオルトチタネートなどの触媒の存在下に、鎖端でヒドロキシル化されたポリオキシアルキレングリコールと反応させる工程を含む。再び、コポリエーテルアミド中へ組み込まれたポリエーテル単位が多ければ多いほど、ポリマーはよりソフトになる。エーテル:アミド比は、エーテル:エステル比について上に記載された通りであり、ショアD硬度も同様である。
1種以上のフィラーが、フィラーと関連する利益のいずれかを提供するために二峰性組成物中に含められてもよい。例えば、任意のフィラー成分が、二峰性アイオノマー組成物にまたは他の材料とのそれらのブレンドに追加の密度を付与するために選択されてもよい。好ましい密度は用途に依存する。フィラーは、約4gm/ccより大きい、好ましくは5gm/chより大きい密度を有する無機物であってもよく、組成物の総重量を基準にして0〜約60重量%の量で存在してもよい。有用なフィラーには、TiO2、酸化亜鉛、硫酸バリウム、ケイ酸鉛および炭化タングステン、酸化スズ、ならびにそれらの他の周知の相当する塩および酸化物が含まれる。フィラーは好ましくは、それらが完全によりも少なく中和されるときに上記のアイオノマーと反応しないかまたはほとんど反応しない。フィラーは、二峰性アイオノマー組成物の透明性が望まれるときには好適ではない可能性がある。
組成物は、ポリマー技術分野で一般に使用され、よく知られている少量の任意の材料をさらに含んでもよい。かかる材料には、可塑剤、粘度安定剤および加水分解安定剤を含む安定剤、例えばIRGANOX 1010などの一次および二次酸化防止剤、紫外線吸収剤および安定剤、帯電防止剤、染料、顔料または他の着色剤、難燃剤、滑剤、加工助剤、スリップ添加剤、シリカまたはタルクなどのブロッキング防止剤、剥離剤、および/またはそれらの混合物が含まれる。他の任意の添加剤には、上記のような無機フィラー;顔料としてかまたは増白剤として使用される、TiO2;蛍光増白剤;界面活性剤;およびポリマー技術分野で公知の他の成分が含まれる。多くのかかる添加剤は、Kirk Othmer Encyclopedia of Chemical Technology(カーク−オスマー化学技術事典)、第5版、John Wiley & Sons(Hoboken、2005年)に記載されている。
フィルムは、フィルムの少なくとも1つの表面が本二峰性アイオノマー組成物を含むという条件で、単層もしくは多層フィルムとして製造されてもよい。フィルムは、周知の手順に従ってキャストまたはブローンフィルムを製造するために(共)押出によって製造されてもよい。シートはフィルムに似ているが、フィルムより厚いと考えられる。便宜上下記の説明はフィルムに関するが、この説明はまたシートにも適用されることが理解されるべきである。
ハイコポリマーについてこれらの実施例で用いられる省略形を上の表Aに、ローコポリマーについてのそれらを表Bに、アイオノマーについてのそれらを表Cに特定する。
NA−1:ZnOと酢酸亜鉛とのブレンド
NA−2:HC−3中の50重量%のMg(OH)2
が含まれる。
90:10のブレンド比でのHC−3とLC−2とのブレンドを、単軸スクリュー押出機を用いてNA−1で70%まで中和して1.35のMIを有する二峰性アイオノマー(BMI−1)を調製した。80:20のブレンド比でのHC−3とLC−2とのブレンドを、単軸スクリュー押出機を用いてNA−2で中和して4.5のMIを有する二峰性アイオノマー(BMI−2)を調製した。BMI−1を、下の表1にまとめられるようにI−3、I−4および/またはBMI−2と混合した。これらの組成物を、実施例1〜8に示される2〜50ミル厚さのフィルムもしくはシートへ押出ブローンまたはキャストした。これらのフィルムを、下記のようにRF溶接性および耐引っ掻き性について試験した。
無線周波(RF)溶接研究は、10kWの最大出力を有し、27MHzで動作するSolidyne Industrial RF Generator(発生器)を用いることによって行った。2つの別個のプラスチックフィルムシートを2つの電極間に置いた。これらの電極を2インチ直径ラムで60psiの圧縮空気を使って押し付けた。電界強度を、電極間の電圧を上げるかまたは下げることによって2.0kV〜9.5kVに調節した。これらの実施例では、0の電極ギャップ(フラット)、90のカウンター設定および85ミルKapton緩衝剤を使用して、RFエネルギーを6.4kVで6または8秒の溶接時間フィルムサンプルに適用し、次に溶接サンプルを4秒の滞留時間圧力下に一緒に保持し、溶融ポリマーを固めた。HFシールされたフィルムの2つの層を、T−剥離試験を用いて剥離してシール強度を評価し、次の通り格付けした:
良好:2つのフィルムは、シールの破壊またはフィルム引裂なしに引き離すことはできない。
不十分:2つのフィルムは容易に引き離すことができる。
なし:2つのフィルムはHF処理下にシールしなかった。
RFシール研究の結果を表1に報告する。
試験フィルムまたはプラークを、ASTM D7187に従ってCSM Instruments(Switzerland)によって製造されたナノ−引っ掻き試験機を用いて耐引っ掻き性について試験した。10および50マイクロニュートンの力を、プラークの表面上を引っ張られる20μm直径の圧子先端を持った圧子に適用した。この装置は、引っ掻きマークが表面上に目に見えるニュートン単位の力を測定する。残存深さを、初期マイクロ引っ掻き試験から2分の緩和後に測定した。旗材料からのTPU−コーティング布(C1)およびレインコート材料からのTPU単層フィルム(C2)の市販サンプルを比較サンプルとして使用した。各材料の2つの試験についての結果を表2および3に報告する。
90:10のブレンド比での(実施例9)および80:20のブレンド比での(実施例10)HC−1とLC−3とのブレンドを単軸スクリュー押出機で、NA−2で中和して下に示される中和のレベルの二峰性アイオノマーを調製した。
90重量%のアイオノマーI−1と10重量%のLC−3とのペレットブレンドを、二軸スクリュー押出機で溶融ブレンドし、NA−2で70%の名目中和レベルまで中和して二峰性アイオノマーBMI−3を調製した。90重量%のアイオノマーI−2と10重量%のLC−4とのペレットブレンドを、二軸スクリュー押出機で溶融ブレンドし、Na2CO3コンセントレートで60%の名目中和レベルまで中和して二峰性アイオノマーBMI−4を調製した。ブレンドを次に、二峰性アイオノマー、すなわちBMI−3、BMI−4ならびに従来型アイオノマー、すなわちアイオノマーI−1およびアイオノマーI−2の50:50比で、二軸スクリュー押出機で溶融ブレンドすることによって調製した。
90:10比での11%MAAを含有するNaおよびZnアイオノマー、すなわち、それぞれアイオノマーI−5およびアイオノマーI−6と、LC−3とをベースにする二峰性アイオノマーを、Na2CO3コンセントレートまたはNA−1を使用して上の実施例と類似のブレンディング/中和条件下に二軸スクリュー押出機で調製した。
90:10重量比でのHC−2とLC−3とのブレンドを、単軸スクリュー押出機で、NA−2で中和して2g/10分のMIおよび63%の名目中和レベルの二峰性アイオノマーを調製した。
90:10重量比でのアイオノマーI−7とLC−4とのブレンドを、単軸スクリュー押出機で、NA−1で中和してBMI−7を得た。
90:10重量比でのアイオノマーI−8とLC−4とのブレンドを、単軸スクリュー押出機で、Na2CO3コンセントレートで中和してBMI−8を得た。
HC−1を単軸スクリュー押出機で、Mg(OH)2コンセントレートNA−2で部分中和し(約51%)、その後90:10(実施例21)および85:15(実施例22)比でLC−1とブレンドし、およそ51%中和を維持するためにNA−2でさらに中和した。
実施例8の組成物を、26インチの型枠開口部、2.25インチのプラグ、1.5インチのブレード、−0.5インチのリード、およびエアギャップ6インチで、CLOEREN EBR 40−インチスロットダイを用いてコロナ処理紙上へ押出コートした。マット仕上げチルロールを、60psiのニップロール圧力でのEDLON−TEFLON圧力ロールで、70°Fに設定した。次の異なる設定条件を用いた:
4.0kWコロナ処理付きで300フィート/分のライン速度での450°F樹脂溶融温度で1.0および0.5および0.25ミル厚さ。
5.3kWコロナ処理付きで150フィート/分のライン速度での550°F樹脂溶融温度で1.0ミル厚さ。
実施例1および3の組成物を、26インチの型枠開口部、2.25インチのプラグ、1.5インチのブレード、−0.5インチのリード、およびエアギャップ6インチで、530°FのCLOEREN EBR 40−インチスロットダイを用いてコロナ処理(0.9kW/平方フィート)布上へ押出コートした。マット仕上げチルロールを、60psiのニップロール圧力でのEDLON−TEFLON圧力ロールで、70°Fに設定した。ライン速度は70フィート/分であった。組成物を5.0ミル厚さでコートした。
(2a)20重量%の、9重量%のマレイン酸水素エチルとのエチレンコポリマー(8g/10分のMI)と80重量%の、20重量%のメチルアクリレートとのエチレンコポリマーとの組成物(ここで、この組成物は1.8重量%の共重合マレイン酸水素エチルを有する)の8.0ミル(0.203mm)層;
または(2b)ブレンドが15.4g/10分のMIを有する、60重量%の、27重量%のn−ブチルアクリレートとのエチレンコポリマー(MI=4g/10分)と、20重量%の、35重量%のn−ブチルアクリレートとのエチレンコポリマー(MI=40g/10分)と、20重量%の、9重量%のマレイン酸水素エチルとのエチレンコポリマー(8g/10分のMI)との組成物の8.0ミル(0.203mm)層
のどちらかとの
布上への共押出によって調製して二峰性アイオノマー組成物のスキン層および(2a)または(2b)のどちらかの中間バルク層が布構造体に接着した3層構造体を得た。
次に、本発明の好ましい態様を示す。
1 物品の形状が球形ではないという条件で、単層フィルム、シートもしくはチューブ、多層フィルム、シートもしくはチューブ、または別の多層構造体である物品であって、前記物品が二峰性アイオノマー組成物を含む少なくとも1つの表面層を有し、前記二峰性アイオノマー組成物が、
(i)1種以上のE/X/Yコポリマー(ここで、Eはエチレンの共重合単位を表し、XはC 3 〜C 8 のα,β−エチレン系不飽和カルボン酸の共重合単位を表し、Yは、酢酸ビニル、アルキル基が1〜8個の炭素原子を有するアルキルアクリレートおよびアルキルメタクリレートからなる群から選択される軟化コモノマーの共重合単位を表し、Xの量はE/X/Yコポリマーの約2〜約30重量%であり、Yの量はE/X/Yコポリマーの0〜約45重量%であり、E/X/Yコポリマーは80,000〜500,000Daの範囲の重量平均分子量(Mw)を有する)を含むハイコポリマーと;
(ii)1種以上のE/Zコポリマー(ここで、Eはエチレンの共重合単位を表し、Zはアクリル酸またはメタクリル酸の共重合単位を表し、Zの量はE/Zコポリマーの約3〜約25重量%であり、E/Zコポリマーは2,000〜30,000Daの範囲のMwを有する)を含むローコポリマーと
を含み、
ここで、E/X/YコポリマーおよびE/Zコポリマー中の合わせた酸性基の少なくとも35%が名目上中和されてカルボン酸塩を形成する物品。
2 前記ハイコポリマーと前記ローコポリマーとを合わせた総重量を基準にして、ハイコポリマーの重量%が約40〜約95重量%であり、ローコポリマーの重量%が約5〜約60重量%であり、かつ、前記酸基の約40〜100%が名目上中和されて1種以上のアルカリ金属、アルカリ土類金属または遷移金属カチオンを含むカルボン酸塩を形成する上記1に記載の物品。
3 前記組成物中の前記金属カチオンの少なくとも20当量%が亜鉛カチオンである上記1に記載の物品。
4 前記1種以上のE/X/Yコポリマーの少なくとも1種が、少なくとも1種のE/X/Yコポリマーの総重量を基準にして、約2〜約25重量%のXと約45重量%以下の有限量のYとを含む上記1に記載の物品。
5 前記Xの量がE/X/Yコポリマーの約5〜約25重量%であり、前記Yの量がE/X/Yコポリマーの約10〜約45重量%である上記4に記載の物品。
6 前記Yの量が前記ハイコポリマーの0%である上記1に記載の物品。
7 前記E/Zコポリマー含有率が、前記ハイコポリマーと前記ローコポリマーとを合わせた総重量を基準にして約5〜約40重量%の範囲である上記1に記載の物品。
8 (a)前記二峰性アイオノマー組成物と(b)他のアイオノマー、他のエチレンコポリマー、無水マレイン酸および/または無水マレイン酸モノエステル含有ポリマー、ポリアミド、ポリエステル、コポリエーテルエステル、コポリエーテルアミド、弾性ポリオレフィン、スチレンジエンブロックコポリマ−、ポリ塩化ビニルおよび熱可塑性ポリウレタンからなる群から選択される少なくとも1種の熱可塑性樹脂とから本質的になる熱可塑性組成物を含む上記1に記載の物品であって;前記少なくとも1種の熱可塑性樹脂の量が前記熱可塑性組成物の総重量を基準にして約1〜約60重量%である物品。
9 前記熱可塑性樹脂が前記他のアイオノマーを含み、前記他のアイオノマーがエチレン(メタ)アクリル酸コポリマーであり、前記(メタ)アクリル酸が前記ポリマーの2〜30重量%であり、かつ、酸部分の約40〜100%が中和されて1種以上のアルカリ金属、アルカリ土類金属または遷移金属カチオンを含むカルボン酸塩を形成する上記8に記載の物品。
10 前記二峰性アイオノマー組成物を含む表面層を含む多層フィルムを含む上記1に記載の物品であって、(i)または(ii)と同じものまたはそれらとは異なるものである1種以上のポリマー樹脂を含む少なくとも1つの追加の層をさらに含み、前記ポリマー樹脂が、ポリ塩化ビニル、熱可塑性ウレタン、ポリエステル、ポリアミド、ポリエチレンホモポリマー、ポリエチレンコポリマー、ポリプロピレンホモポリマー、ポリプロピレンコポリマー、エチレン酢酸ビニルコポリマー、エチレンアルキルアクリレートコポリマー、エチレンアルキルメタクリレートコポリマー、エチレン酸コポリマー、エチレン酸アイオノマー、酸無水物グラフト変性ポリマー、およびエチレンと、少なくとも2個のカルボン酸基を有するC 4 〜C 8 の不飽和酸、ならびに環状酸無水物、少なくとも2個のカルボン酸基を有するC 4 〜C 8 の不飽和酸のモノエステルおよびジエステルからなる群から選択されるコモノマーとの共重合単位を含むコポリマーからなる群から選択される、物品。
11 前記二峰性アイオノマー組成物を含むまたはそれから製造された少なくとも1つの表面層と、基材の形状が球形ではないという条件で、熱可塑性フィルムおよびシート、気泡質発泡体、織布、編布および不織布、紙、パルプおよび板紙製品、木材および木材製品、金属、ガラス、石、セラミック、および皮革および皮革様製品;ならびに熱可塑性または熱硬化性プラスチックからなる群から選択される基材を含む少なくとも1つの追加の層とを含む上記1に記載の多層構造体。
12 (1)上記1に記載の二峰性アイオノマー組成物の第1表面を第1基材の表面の少なくとも一部と接触させ、および任意選択的に前記二峰性アイオノマー組成物の第2表面を第2基材の表面の少なくとも一部と接触させる工程と;
(2)前記二峰性アイオノマー組成物に高周波電磁放射線、および任意選択的に圧力、熱、またはそれらの組み合わせを適用し、それによって前記二峰性アイオノマー組成物を軟化させるかまたは溶融させる工程と;
(3)前記軟化したまたは溶融した二峰性アイオノマー組成物をそのまま固め、それによって前記二峰性アイオノマー組成物の第1表面を前記第1基材に接合し、および前記二峰性アイオノマー組成物の第2表面を、存在する場合、前記第2基材に接合する工程と
を含む多層物品の製造方法であって、
前記第1基材および前記任意の第2基材が、熱可塑性フィルムおよびシート、気泡質発泡体、織布、編布および不織布、紙、パルプおよび板紙製品、木材および木材製品、金属、ガラス、石、セラミック、および皮革および皮革様製品、熱可塑性樹脂、熱硬化性樹脂、ならびに上記1に記載の二峰性アイオノマー組成物からなる群から独立して選択される方法。
13 上記12に記載の方法であって、前記二峰性アイオノマー組成物の第2表面を、工程(1)の前に、直接または介在層を介して、第3基材の表面の少なくとも一部に接着させる工程を含み、ここで、第2基材が存在せず、前記第3基材が、熱可塑性フィルムおよびシート、気泡質発泡体、織布、編布および不織布、紙、パルプおよび板紙製品、木材および木材製品、金属、ガラス、石、セラミック、および皮革および皮革様製品;熱可塑性樹脂、熱硬化性樹脂、ならびに前記二峰性アイオノマー組成物と同じものまたはそれとは異なるものであってもよい第2二峰性アイオノマー組成物からなる群から独立して選択され、前記第2二峰性アイオノマー組成物が、
(i)1種以上のE/X/Yコポリマー(ここで、Eはエチレンの共重合単位を表し、XはC 3 〜C 8 のα,β−エチレン系不飽和カルボン酸の共重合単位を表し、Yは、酢酸ビニル、アルキル基が1〜8個の炭素原子を有するアルキルアクリレートおよびアルキルメタクリレートからなる群から選択される軟化コモノマーの共重合単位を表し、Xの量はE/X/Yコポリマーの約2〜約30重量%であり、Yの量はE/X/Yコポリマーの0〜約45重量%であり、E/X/Yコポリマーは80,000〜500,000Daの範囲の重量平均分子量(Mw)を有する)を含むハイコポリマーと;
(ii)1種以上のE/Zコポリマー(ここで、Eはエチレンの共重合単位を表し、Zはアクリル酸またはメタクリル酸の共重合単位を表し、Zの量はE/Zコポリマーの約3〜約25重量%であり、E/Zコポリマーは2,000〜30,000Daの範囲のMwを有する)を含むローコポリマーと
を含み;
ここで、E/X/YコポリマーおよびE/Zコポリマー中の合わせた酸性基の少なくとも35%が名目上中和されてカルボン酸塩を形成する方法。
14 前記接着工程が、押出積層、押出コーティング、共押出積層、共押出コーティング、積層、カレンダー加工積層、接着剤支援積層、熱積層、シーリング、ホットロール積層を用いる熱溶接、フレーム積層、ヒートシーリング、無線周波または高周波溶接、水性分散系コーティング、粉末散乱、粉末ドットおよびペーストドットプロセスからなる群から選択される1つ以上のプロセスを含む上記13に記載の方法。
15 前記二峰性アイオノマー組成物が単層または多層のフィルムもしくはシートの形態にある上記12に記載の方法。
16 二峰性アイオノマーフィルムが前記第1基材であり;二峰性アイオノマーフィルムの2つのシートを層状にする工程か、または同一の二峰性アイオノマーフィルムをそれ自体上に折り重ねる工程と;高周波電磁放射線を適用することによってシートの周辺を密封してバッグまたはパウチを形成する工程とを含む上記12に記載の方法。
17 前記二峰性アイオノマー組成物が粉末または顆粒の形態にある上記12に記載の方法。
18 前記第2基材が存在する上記12に記載の方法。
19 前記ハイコポリマーと前記ローコポリマーとを合わせた総重量を基準にして、ハイコポリマーの重量%が約40〜約95重量%であり、ローコポリマーの重量%が約5〜約60重量%であり、かつ、前記酸基の約40〜100%が名目上中和されて1種以上のアルカリ金属、アルカリ土類金属または遷移金属カチオンを含むカルボン酸塩を形成する上記12に記載の方法。
20 前記組成物中の前記金属カチオンの少なくとも20当量%が亜鉛カチオンである上記12に記載の方法。
21 前記1種以上のE/X/Yコポリマーの少なくとも1種が、少なくとも1種のE/X/Yコポリマーの総重量を基準にして、約2〜約25重量%のXと約45重量%以下の有限量のYとを含む上記12に記載の方法。
22 Xが前記E/X/Yコポリマーの約5〜約25重量%であり、Yが前記E/X/Yコポリマーの約10〜約45重量%である上記21に記載の方法。
23 Yが前記ハイコポリマーの0%である上記12に記載の方法。
24 前記E/Zコポリマー含有率が(i)+(ii)を基準にして約5〜約40重量%の範囲である上記12に記載の方法。
25 製品の表面の少なくとも一部が、
(i)1種以上のE/X/Yコポリマー(ここで、Eはエチレンの共重合単位を表し、XはC 3 〜C 8 のα,β−エチレン系不飽和カルボン酸の共重合単位を表し、Yは、酢酸ビニル、アルキル基が1〜8個の炭素原子を有するアルキルアクリレートおよびアルキルメタクリレートからなる群から選択される軟化コモノマーの共重合単位を表し、XはE/X/Yコポリマーの約2〜約30重量%であり、YはE/X/Yコポリマーの約45重量%までの有限量であり、E/X/Yコポリマーは80,000〜500,000Daの範囲の重量平均分子量(Mw)を有する)を含むハイコポリマーと;
(ii)1種以上のE/Zコポリマー(ここで、Eはエチレンの共重合単位を表し、Zはアクリル酸またはメタクリル酸の共重合単位を表し、ZはE/Zコポリマーの約3〜約25重量%であり、E/Zコポリマーは2,000〜30,000Daの範囲のMwを有する)を含むローコポリマーと
を含むまたはそれらから製造される二峰性アイオノマー組成物を含み、
ここで、E/X/YコポリマーおよびE/Zコポリマー中の合わせた酸性基の少なくとも35%が、相当する塩へ金属イオンで名目上中和されている製品であって、
防水布、旗、標識、室内装飾品、履物、衣類、防水衣、レインコート、保護掛布、保護カバー、壁紙、ブラインドまたはカーテン、キーボード保護カバー、自動車内装内張、映写膜、皮革商品、アップリケ、装飾フィルム、履物用の装飾パッチ、装飾ラップ、サッカーボールスキンを含む運動競技用器材用のカバーまたは保護表面、装飾箱、本の表紙、バインダー、管材料、フレキシブルパッケージング、硬質パッケージング、バッグ、医療液含有用パウチ、熱成形品、およびワイヤからなる群から選択される製品。
Claims (5)
- 物品の形状が球形ではないという条件で、多層フィルム、シートもしくはチューブ、または別の多層構造体である物品であって、前記物品が(a)二峰性アイオノマー組成物と(b)他のアイオノマーを含む少なくとも1つの表面層を有し、前記二峰性アイオノマー組成物が、
(i)1種以上のE/X/Yコポリマー(ここで、Eはエチレンの共重合単位を表し、XはC3〜C8のα,β−エチレン系不飽和カルボン酸の共重合単位を表し、Yは、酢酸ビニル、アルキル基が1〜8個の炭素原子を有するアルキルアクリレートおよびアルキルメタクリレートからなる群から選択される軟化コモノマーの共重合単位を表し、Xの量はE/X/Yコポリマーの2〜30重量%であり、Yの量はE/X/Yコポリマーの0〜45重量%であり、E/X/Yコポリマーは80,000〜500,000Daの範囲の重量平均分子量(Mw)を有する)を含むコポリマーと;
(ii)1種以上のE/Zコポリマー(ここで、Eはエチレンの共重合単位を表し、Zはアクリル酸またはメタクリル酸の共重合単位を表し、Zの量はE/Zコポリマーの3〜25重量%であり、E/Zコポリマーは2,000〜30,000Daの範囲のMwを有する)を含むコポリマーと
を含み、
ここで、前記コポリマー(i)と前記コポリマー(ii)とを合わせた総重量を基準にして、コポリマー(i)の重量%が40〜95重量%であり、コポリマー(ii)の重量%が5〜60重量%であり、かつ、E/X/YコポリマーおよびE/Zコポリマー中の合わせた酸基の40〜100%が名目上中和されて1種以上のアルカリ金属、アルカリ土類金属または遷移金属カチオンを含むカルボン酸塩を形成し、
前記表面層における前記他のアイオノマーの量が、前記二峰性アイオノマー組成物と前記他のアイオノマーの合計重量を基準にして、1〜30重量%であり、
防水布、旗、標識、室内装飾品、履物、衣類、防水衣、レインコート、保護掛布、保護カバー、壁紙、ブラインドまたはカーテン、キーボード保護カバー、自動車内装内張、映写膜、皮革商品、アップリケ、装飾フィルム、履物用の装飾パッチ、装飾ラップ、サッカーボールスキンを含む運動競技用器材用のカバーまたは保護表面、装飾箱、本の表紙、バインダー、管材料、フレキシブルパッケージング、硬質パッケージング、バッグ、医療液含有用パウチ、熱成形品、およびワイヤからなる群から選択される製品用の物品。 - 前記組成物中の前記金属カチオンの少なくとも20当量%が亜鉛カチオンである請求項1に記載の物品。
- 前記Xの量がE/X/Yコポリマーの5〜25重量%であり、前記Yの量がE/X/Yコポリマーの10〜45重量%である請求項2に記載の物品。
- (a)前記二峰性アイオノマー組成物と(b)他のアイオノマーとから本質的になる熱可塑性組成物を含む請求項1に記載の物品であって;前記他のアイオノマーがエチレン(メタ)アクリル酸コポリマーであり、(メタ)アクリル酸単位がコポリマーの2〜30重量%であり、かつ、酸部分の40〜100%が中和されて1種以上のアルカリ金属、アルカリ土類金属または遷移金属カチオンを含むカルボン酸塩を形成する物品。
- 前記二峰性アイオノマー組成物を含む表面層を含む多層フィルムを含む請求項1に記載の物品であって、(i)または(ii)と同じものまたはそれらとは異なるものである1種以上のポリマー樹脂を含む少なくとも1つの追加の層をさらに含み、前記ポリマー樹脂が、ポリ塩化ビニル、熱可塑性ウレタン、ポリエステル、ポリアミド、ポリエチレンホモポリマー、ポリエチレンコポリマー、ポリプロピレンホモポリマー、ポリプロピレンコポリマー、エチレン酢酸ビニルコポリマー、エチレンアルキルアクリレートコポリマー、エチレンアルキルメタクリレートコポリマー、エチレン酸コポリマー、エチレン酸アイオノマー、酸無水物グラフト変性ポリマー、およびエチレンと、少なくとも2個のカルボン酸基を有するC4〜C8の不飽和酸、ならびに環状酸無水物、少なくとも2個のカルボン酸基を有するC4〜C8の不飽和酸のモノエステルおよびジエステルからなる群から選択されるコモノマーとの共重合単位を含むコポリマーからなる群から選択され、または、前記少なくとも1つの追加の層が、基材の形状が球形ではないという条件で、熱可塑性フィルムおよびシート、気泡質発泡体、織布、編布および不織布、紙、パルプおよび板紙製品、木材および木材製品、金属、ガラス、石、セラミック、および皮革および皮革様製品;ならびに熱可塑性または熱硬化性プラスチックからなる群から選択される基材を含む物品。
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PCT/US2008/083727 WO2009065100A1 (en) | 2007-11-16 | 2008-11-17 | Articles containing bimodal ionomer compositions |
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