JP2018172674A - Tpuキャップ層を有する、共押出された架橋ポリオレフィン発泡体 - Google Patents
Tpuキャップ層を有する、共押出された架橋ポリオレフィン発泡体 Download PDFInfo
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- JP2018172674A JP2018172674A JP2018067293A JP2018067293A JP2018172674A JP 2018172674 A JP2018172674 A JP 2018172674A JP 2018067293 A JP2018067293 A JP 2018067293A JP 2018067293 A JP2018067293 A JP 2018067293A JP 2018172674 A JP2018172674 A JP 2018172674A
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- foam
- layer
- polypropylene
- polyethylene
- multilayer
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Abstract
Description
本明細書におけるある値又はパラメータの「約」を言う場合、その値又はパラメータ自体を対象とするばらつきを含む(及びばらつきを記載する)。例えば、「約X」と言及している記載は、「X」の記載を含む。更に、言い回し「未満」、「超」、「多くとも」、「少なくとも」、「以下」、「以上」、又は他の類似の言い回しとその後の一連の値若しくはパラメータを言う場合、その一連の値又はパラメータにおける各値若しくはパラメータへの言い回しが該当することが意図される。例えば、層が約20質量%未満、約15質量%未満又は約10質量%未満の化学発泡剤を有するという記載は、この層中の化学発泡剤の質量百分率が、約20質量%未満、約15質量%未満又は約10質量%未満となり得ることを意味することが意図されている。
さらなる利点が、以下の詳細説明から当業者に容易に明らかになろう。本明細書における例及び説明は、本質的に例示として見なされるべきであり、限定ではない。
例示的な実施形態は、添付の図面を参照して記載する。
TPUキャップ層を有する、架橋独立気泡共押出成形ポリオレフィン発泡体を生成する方法は、(a)共押出成形、(b)照射及び(c)発泡からなる工程を含んでもよい。
多層シート全体の厚さは、総合的なダイギャップによって制御することができる。しかし、多層シート全体の厚さは、例えば、溶融した多層押出物を伸縮(すなわち、「引っ張り」)、及び/又はニップにより溶融多層押出物を平坦化することによって、更に調節することができる。
押出成形機に供給される発泡可能な組成物は、少なくとも1つのポリプロピレン、少なくとも1つのポリエチレン又はそれらの組合せを含むことができる。一部の実施形態では、発泡体組成物は、多層構造体のポリオレフィン発泡体層(A)を形成することができる。一部の実施形態では、発泡体組成物は、多層構造体のTPUキャップ層(B)を形成することができる。
押出成形機に供給される発泡体組成物はまた、少なくとも1つのTPUを含むことができる。TPUは、以下に限定されないが、ポリエステルベースの熱可塑性ポリウレタン、ポリエーテル、ポリカプロラクトン、並びにポリカプロラクトンコポリエステルなどのTPUコポリマーを含む。TPUは、芳香族又は脂肪族の種類のものとすることができる。
一部の実施形態では、発泡体組成物中のTPUの量は、該組成物の、約30PPHR以下、約25PPHR以下、約20PPHR又は約15PPHR以下とすることができる。一部の実施形態では、発泡体層中のTPUは、発泡体層の多くとも約25質量%、約20質量%又は約15質量%となり得る。一部の実施形態では、発泡体層中のTPUは、発泡体層の約0〜25質量%、約1〜22質量%、約5〜20質量%、約10〜20又は約10〜15質量とすることができる。
押出成形機に供給されるキャップ組成物は、少なくとも1つのTPU及び少なくとも1つのポリプロピレン及び/又は少なくとも1つのポリエチレン、すなわち上記のTPU、ポリプロピレン及びポリエチレンを含むことができる。一部の実施形態では、キャップ組成物は、多層構造体のTPUキャップ層(B)を形成することができる。
幅広い範囲の多層構造体及び発泡体物品は、本開示組成物を用いて生成することができるので、幅広い範囲のポリプロピレン、ポリエチレン及びTPUが、本組成物に使用されて、様々な製造過程中の製造要件及び商業的な最終使用要件を満たすことができる。
市販の「熱可塑性ポリウレタン」(TPU)の非限定例は、以下に限定されないが、CovestroからのTEXIN(登録商標)シリーズ、BASFからのELASTOLLAN(登録商標)シリーズ、LubrizolからのESTANE(登録商標)シリーズ及びHuntsmanからのIROGRAN(登録商標)シリーズを含む。
「ポリプロピレン」の非限定例は、アイソタクチックホモポリプロピレンである。市販の例には、以下に限定されないが、BraskemからのFF018F、Total Petrochemicalsからの3271及びConocoからのCOPYLENE(商標)CH020を含む。
「衝撃改質ポリプロピレン−エチレンコポリマー」は、ランダムエチレン単位及びエチレン−プロピレン(EP)コポリマーゴムを有するポリプロピレンである。ゴムは、アモルファスはまた半結晶とすることができるが、材料にいかなるプラストマー特性又はエラストマー特性も付与するのに十分な量ではない。市販の衝撃改質ポリプロピレン−エチレンコポリマーの非限定例は、BraskemからのPRISMA(登録商標)6910である。
「メタロセンポリプロピレン−エチレンコポリマー」は、ランダムエチレン単位を有する、メタロセンシンジオタクチック、メタロセンアタクチック、及びメタロセンイソタクチックポリプロピレンである。市販の例には、以下に限定されないが、Total PetrochemicalsからのLumicene(登録商標)MR10MX0及びLumicene(登録商標)MR60MC2、並びにLyondellBasellからのPurell(登録商標)SM170Gを含む。
「メタロセンポリプロピレンオレフィンブロックコポリマー」は、結晶性硬質「ブロック」とランダム分布していないアモルファス性軟質「ブロック」が交互のポリプロピレン(すなわち、ブロック配列が制御されている)である。「メタロセンポリプロピレンオレフィンブロックコポリマー」の一例は、以下に限定されないが、Dow Chemical CompanyからのINTUNE(商標)製品ラインを含む。
「ポリプロピレンベースのポリオレフィンエラストマー」(POE)は、エラストマー特性を有する、メタロセンプロピレンベースコポリマーと非メタロセンプロピレンベースコポリマーの両方である。プロピレンベースのポリオレフィンエラストマーの非限定例は、Dow Chemical CompanyからのVERSIFY(商標)(メタロセン)、及びExxonMobilからのVISTAMAXX(商標)(メタロセン)という商標名で市販されているそのようなポリマーである。
「メタロセンポリエチレン」は、非エラストマーからエラストマーまでの範囲の特性を有する、メタロセンベースのポリエチレンである。メタロセンポリエチレンの非限定例は、Dow Chemical CompanyからのENGAGE(商標)、並びにExxonMobilからのENABLE(商標)及びEXCEED(商標)、並びにBorealisからのQUEO(商標)という商標名で市販されている。
「メタロセンポリエチレンオレフィンブロックコポリマー」は、結晶性硬質「ブロック」とランダム分布していないアモルファス性軟質「ブロック」が交互のポリエチレン(すなわち、ブロック配列が制御されている)である。「メタロセンポリエチレンオレフィンブロックコポリマー」の一例は、以下に限定されないが、Dow Chemical CompanyからのINFUSE(商標)製品ラインを含む。
ポリエーテルアミン修飾ポリプロピレン及びポリエチレンは、官能基化されているポリプロピレン及びポリエチレン上のポリエーテルアミンをグラフトすることにより生成される。官能基化ポリプロピレン及びポリエチレンは、モノマーが、通常、遊離ラジカル反応によってグラフトされているところである。官能基化ポリプロピレン及びポリエチレンを調製するのに好適なモノマーは、例えば、オレフィン性不飽和モノカルボン酸、例えばアクリル酸又はメタクリル酸、並びに対応するtert−ブチルエステル、例えば(メタ)アクリル酸tert−ブチル、オレフィン性不飽和ジカルボン酸、例えばフマル酸、マレイン酸及びイタコン酸、並びに対応するモノ及び/又はジ−tert−ブチルエステル、例えば、フマル酸モノ又はジ−tert−ブチル及びマレイン酸モノ又はジ−tert−ブチル、オレフィン性不飽和ジカルボン酸無水物、例えば無水マレイン酸、スルホ又はスルホニル含有オレフィン性不飽和モノマー、例えば、p−スチレンスルホン酸、2−(メタ)アクリルアミド−2−メチルプロペンスルホン酸又は2−スルホニル−(メタ)アクリレート、オキサゾリニル含有オレフィン性不飽和モノマー、例えばビニルオキサゾリン及びビニルオキサゾリン誘導体、並びにエポキシ含有オレフィン性不飽和モノマー、例えば(メタ)アクリル酸グリシジル又はアリルグリシジルエーテルである。
他のグラフト化モノマーにより官能基化されているポリエチレンもまた、市販されている。非限定例は、DuPontからのBYNEL(登録商標)1100、2200及び3100シリーズ、並びにArkemaからのLOTADER(登録商標)AXシリーズである。
無水マレイン酸により官能基化されているポリプロピレン及びポリエチレン以外のポリマーも市販されていることに留意されたい。例えば、AddivantからのROYALTUF(登録商標)シリーズは、無水マレイン酸により官能基化されている一連のEPDMゴムである。別の例において、KratonからのKRATON(商標)FGシリーズは、無水マレイン酸により官能基化されている一連のSEBSポリマーである。
ポリマーに加えて、押出成形機に供給する組成物はまた、開示されている多層構造体の生成と適合性のある添加剤も含有してもよい。一般的な添加剤は、以下に限定されないが、有機物過酸化物、酸化防止剤、潤滑剤、熱安定剤、着色剤、難燃剤、帯電防止剤、核化剤、可塑剤、抗微生物剤、殺真菌剤、光安定剤、UV吸収剤、ブロッキング防止剤、フィラー、脱臭剤、臭気吸着剤、増粘剤、気泡サイズ安定剤、金属不活性化剤及びそれらの組合せを含む。
成分をどのように押出成形機に供給するかにかかわらず、押出成形機内のせん断力及び混合は、均質な層を製造するのに十分となり得る。同方向回転(co-rotating)及び異方向回転(counter-rotating)二軸押出成形機は、均一な特性を有する層を押出成形するための押出成形機のバレルにより十分なせん断力及び混合を実現することができる。
発泡体組成物は、様々な異なる化学発泡剤を含むことができる。化学発泡剤の例には、以下に限定されないが、アゾ化合物、ヒドラジン化合物、カルバジド、テトラゾール、ニトロソ化合物及びカーボネートが含まれる。更に、化学発泡剤は、単独で、又は任意の組合せで使用することができる。一部の実施形態において使用することができる化学発泡剤の1つは、アゾジカルボンアミド(ADCA)である。ADCAの熱分解は、通常、約190℃と230℃との間の温度で起こる。ADCAが押出成形機中で熱により分解するのを防ぐために、押出成形温度は、190℃以下に維持することができる。
化学発泡剤の上記の列挙されている量は、ADCAのみに特異的ではないことに留意されたい。他の発泡剤が、CFAの質量あたり様々な体積量のガスを生成することができ、それにより、考慮することができる。例えば、ADCAを化学発泡剤であるp−トルエンスルホニルセミカルバジド(TSS)と比較する場合:発泡可能な層が40PPHRのADCAを含有する場合、約63PPHRのTSSは、発泡工程中にほぼ同じ量のガスを生成することが必要になると思われる。
押出成形発泡物品のより粗い表面は、一般に、より大きなサイズの気泡(本開示により生成する発泡体と比べた場合)により引き起こされ得る。表面粗さが気泡サイズの関数となるので、気泡サイズ及びサイズ分布は、大部分の商業的用途において重要とはなり得ないが、より大きな気泡を有する発泡体は、滑らかな発泡体表面を必要とする用途にとって、より小さな気泡を有する発泡体ほど望ましいものとはなり得ない。
共押出成形非発泡多層シートは、最大、個別で4回、好ましくは1回以下、好ましくは1回だけ照射され得る。照射の頻度が、約4回超となる場合、ポリマー構成成分は分解を受けることがあり、その結果、発泡時に、例えば、得られる発泡体層中に、均一な気泡が生成しない。押出成形構造体の厚さが、約4mm超の場合、電離放射線を用いる多層プロファイルの各一次表面への照射は、一次表面及び内部層の架橋度を一層均一にするのが好ましいものとなり得る。
架橋は、様々な異なる技法を使用して行うことができ、分子間の両方、異なるポリマー分子間、及び分子内、単一ポリマー分子の一部の間に形成することができる。そのような技法は、以下に限定されないが、架橋を形成することができるか、又は活性化されて架橋を形成することができる官能基を含有する架橋剤を組み込むポリマー鎖から分離される、及びこのようなポリマー鎖をもたらす、架橋剤を供給することを含む。
共押出成形シートを照射した後、発泡は、架橋多層シートを熱的に分解可能な発泡剤の分解温度より高い温度まで加熱することにより行うことができる。発泡は、連続法で、約200〜260℃又は約220〜240℃で行うことができる。連続発泡法は、連続発泡体シートを生成するため、バッチ法よりも好ましいものとなり得る。
多層発泡体シートは、約250kg/m3の断面密度に限定されない。約350kg/m3、約450kg/m3又は約550kg/m3の断面密度をおよそ有する発泡体も生成することができる。しかし、より大きな密度は、所与の用途において使用され得る他の材料と比べた場合、一般に、法外な費用がかかる恐れがあるので、発泡体シートは、約250kg/m3未満の密度を有するのが好ましいものとなり得る。
多層ポリオレフィン発泡体/TPUキャップシートの全体厚さは、約0.2mm〜約50mm、約0.4mm〜約40mm、約0.6mm〜約30mm又は約0.8mm〜約20mmとすることができる。厚さが約0.2mm未満である場合、発泡は、一次表面からかなりのガスを喪失するために、効率的にならないことがある。厚さが、約50mmを超える場合、発泡工程中の膨張により、制御が徐々に困難になる恐れがある。したがって、一定の断面密度及び厚さを有する多層ポリオレフィン発泡体/TPUキャップシートを生成することが徐々に一層困難になり得る。一部の実施形態では、発泡共押出成形多層構造体のキャップ層は、約0.1〜100μm、約1〜100μm、約5〜75μm、約10〜60μm、約15〜50μm、約15〜25μm、約20〜50μm、約20〜35μm又は約25〜30μmの厚さを有することができる。一部の実施形態では、発泡共押出成形多層構造体の発泡体層は、約0.1〜5mm、約0.5〜5mm、約1〜5mm、約2〜5mm又は約2〜4mmの厚さを有することができる。
一部の実施形態では、所望の厚さは、スライス、剥離又は接合などの二次処理によって得ることができる。スライス、剥離又は接合は、約0.1mm〜約100mmの範囲の厚さを生成することができる。
開示されている多層ポリオレフィン発泡体/TPUキャップシートは、ウレタンベースの接着剤への接着が必要な用途に使用することができる。ウレタンベースの接着剤は、例えば、発泡体テープ及びガスケット;床の下葺き用発泡体;フィルム、ファブリック、繊維層及び皮革に積層される発泡体;及び基材に接着する発泡体に使用される。
別の実施形態では、開示されている多層発泡体は、発泡体表面(キャップ表面よりむしろ)及び/又はパネル表面の少なくとも一部の上に配置され得る、感圧接着剤層を介して、床パネル、特に、中実堅木張り床パネル、工学設計木造床パネル及び積層体床パネルに取り付けることができる。この実施形態では、キャップ層が露出される。一成分ウレタン接着剤及び二成分ウレタン接着剤を使用する最終使用者(床の設置者)は、TPUキャップ層のない発泡体に比べて、下張り床への改善された接着を得ることができる。
以下の表1に、以下の例において使用される、様々な構成成分及びそのような構成成分の説明の一覧表示を示す。
以下の表2に、例1〜3の配合物を示す。
Claims (21)
- ポリプロピレン、ポリエチレン、又はポリプロピレンとポリエチレンとの組合せを含む共押出された発泡体層、並びに
発泡体層の側面上の共押出されたキャップ層であって、
少なくとも40質量%の熱可塑性ポリウレタン(TPU)、及び
ポリプロピレン、ポリエチレン、又はポリプロピレンとポリエチレンとの組合せ
を含むキャップ層
を含むことを特徴とする多層発泡構造体。 - 共押出発泡体層が、5〜20質量%のTPUを含む、請求項1に記載の多層発泡構造体。
- 共押出発泡体層が、少なくとも70質量%のポリプロピレン、ポリエチレン又はポリプロピレンとポリエチレンとの組合せを含む、請求項1に記載の多層発泡構造体。
- 発泡体層が、添加剤を1〜15質量%の量で含む、請求項1に記載の多層発泡構造体。
- キャップ層が、添加剤を1〜8質量%の量で含む、請求項1に記載の多層発泡構造体。
- ポリプロピレンが、230℃において、10分あたり0.1〜25gのメルトフローインデックスを有する、請求項1に記載の多層発泡構造体。
- ポリエチレンが、190℃において、10分あたり0.1〜25gのメルトフローインデックスを有する、請求項1に記載の多層発泡構造体。
- 多層発泡構造体の密度が、20〜250kg/m3である、請求項1に記載の多層発泡構造体。
- 20〜75%の架橋度を有する、請求項1に記載の多層発泡構造体。
- 0.05〜1.0mmの平均独立気泡サイズを有する、請求項1に記載の多層発泡構造体。
- 0.2〜50mmの厚さを有する、請求項1に記載の多層発泡構造体。
- 多層発泡構造体であって、
ポリプロピレン、ポリエチレン、又はポリプロピレンとポリエチレンとの組合せを含む共押出発泡体層、並びに
発泡体層側面上の共押出されたキャップ層であって、
少なくとも40質量%の熱可塑性ポリウレタン(TPU)、及び
ポリプロピレン、ポリエチレン、又はポリプロピレンとポリエチレンとの組合せを含む、キャップ層
を含む多層発泡構造体と、
発泡体層の反対側のキャップ層側面上の積層と、
を含むことを特徴とする積層体。 - 積層が、フィルム、ファブリック、繊維層及び皮革からなる群から選択される、請求項12に記載の積層体。
- 積層が、感圧接着剤層である、請求項12に記載の積層体。
- 積層が、ウレタンベースの接着剤、ポリウレタン発泡体又は反応性ウレタン発泡体を含む、請求項12に記載の積層体。
- 共押出発泡体層が、5〜20質量%のTPUを含む、請求項12に記載の積層体。
- 共押出発泡体層が、少なくとも70質量%のポリプロピレン、ポリエチレン、又はポリプロピレンとポリエチレンとの組合せを含む、請求項12に記載の積層体。
- 発泡体層が、添加剤を1〜15質量%の量で含む、請求項12に記載の積層体。
- ポリプロピレンが、230℃において、10分あたり0.1〜25gのメルトフローインデックスを有する、請求項12に記載の積層体。
- ポリエチレンが、190℃において、10分あたり0.1〜25gのメルトフローインデックスを有する、請求項12に記載の積層体。
- 床面システムであって、
上部床層、
下張り床層、並びに
下張り床層と上部床層との間に配置されている、少なくとも1つの下葺き層、
を含む床面システムであって、前記少なくとも1つの下葺き層が、
ポリプロピレン、ポリエチレン、又はポリプロピレンとポリエチレンとの組合せを含む共押出された発泡体層、並びに
発泡体層側面上の共押出されたキャップ層であって、
少なくとも40質量%の熱可塑性ポリウレタン(TPU)、及び
ポリプロピレン、ポリエチレン、又はポリプロピレンとポリエチレンとの組合せを含む、キャップ層、
を含む多層発泡構造体を含むことを特徴とする床面システム。
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Also Published As
Publication number | Publication date |
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KR102493850B1 (ko) | 2023-01-30 |
EP3385073A1 (en) | 2018-10-10 |
CN108688281A (zh) | 2018-10-23 |
MX2018003201A (es) | 2018-11-09 |
KR20180111603A (ko) | 2018-10-11 |
JP7066483B2 (ja) | 2022-05-13 |
US20180281358A1 (en) | 2018-10-04 |
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