JP6210985B2 - 断熱容器用のポリマー材料 - Google Patents
断熱容器用のポリマー材料 Download PDFInfo
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- JP6210985B2 JP6210985B2 JP2014528384A JP2014528384A JP6210985B2 JP 6210985 B2 JP6210985 B2 JP 6210985B2 JP 2014528384 A JP2014528384 A JP 2014528384A JP 2014528384 A JP2014528384 A JP 2014528384A JP 6210985 B2 JP6210985 B2 JP 6210985B2
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- JP
- Japan
- Prior art keywords
- formulation
- cup
- aromatic polymer
- agent
- blowing agent
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B29B7/00—Mixing; Kneading
- B29B7/80—Component parts, details or accessories; Auxiliary operations
- B29B7/88—Adding charges, i.e. additives
- B29B7/94—Liquid charges
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Description
本出願は、参照により本明細書に明示的に援用される、2011年8月31日に出願された米国仮特許出願第61/529,632号、および2012年3月30日に出願された米国仮特許出願第61/618,604号の優先権を米国特許法第119条(e)の下で主張するものである。
DAPLOY(商標)WB140ポリプロピレンホモポリマー(Borealis A/Sから入手可能)を、ポリプロピレン系樹脂として使用した。Braskemから入手可能なF020HC、ポリプロピレンホモポリマー樹脂を、二次的な樹脂として使用した。2つの樹脂を、主要な核形成剤としてのHydrocerol(商標)CF−40E(商標)、二次的な核形成剤としてのタルク、発泡剤としてのCO2、スリップ剤、および着色剤としての二酸化チタンと混合した。パーセンテージは以下のとおりであった。
79.9%の主要な樹脂:高溶融強度ポリプロピレンBorealis WB140
HMS15%の二次的な樹脂:F020HC(Braskem)
0.1%の主要な成核剤:Clariant Hyrocerol CF−40E(商標)
2%の二次的な成核剤:タルク
1%の着色剤:TiO2 PE(あるいは、PPが使用され得る)
2%のスリップ剤:Ampacet Corporationから入手可能なAmpacet(商標)102823 LLDPE(直鎖状低密度ポリエチレン)。
1.1ポンド/時のCO2
0.7ポンド/時のR134a。
実施例1にしたがって形成された材料の試験結果は、材料が、約0.1902g/cm3の密度および約0.089インチ(2.2606mm)の公称シートゲージを有していたことを示した。
12オンスの室温水が充填された、この材料を用いて製造された容器を、FISO Microwave Station(1200ワット)電子レンジ中で、2.5分間にわたって加熱したところ、カップに燃焼または焼け焦げまたは他の目に見える影響はなかった。比較すると、同じ電子レンジ中で加熱された紙コップは、90秒未満で焼け焦げ、燃焼された。
試験方法
試料は、73°F(22.8℃)および50%の相対湿度であった。以下の試験条件にかけられたときのカップの抵抗力を測定するために、ロードセルを含む水平力ゲージを用いて、カップの硬さ/剛性試験を行った。(a)カップにおける試験箇所は、カップの縁から1/3下であり;(b)試験移動距離は0.25インチ(6.35mm)であり;(c)試験移動時間は10秒間であった。
約0.064インチ(1.6256mm)の平均壁厚、約0.1776g/cm3の平均密度、および約9.86gの平均カップ重量で、材料の剛性が、以下の表2〜5に示される。
・(カップ外部)表面温度熱電対をカップに接着剤で取り付ける。
・熱電対が継ぎ目の反対側のカップの中央にあるように、取り付けられた熱電対をセロハンテープでカップに貼る。
・水または他の水性液体を、マイクロ波などで、沸点近くまで加熱する。
・液体温度を観察しながら、球温度計で温水を連続的に撹拌する。
・熱電対温度を記録する。
・液体が200°Fになったら、カップにほぼ満杯になるまで注ぐ。
・カップに蓋をする。
・最低でも5分間にわたって表面温度を記録する。
約0.190g/cm3の密度および約0.089インチの壁厚を有する、上記の配合物から形成されるカップを使用した。200°F(93.3℃)の温水をカップに入れた。
カップの外壁において測定された温度は、約140.5°F(60.3℃)であり、約59.5°F(33℃)低下した。5分間の間の最高温度は、約140.5°F(60.3℃)でピークに達することが観察された。温度が低くなるほど、材料が液体からカップ材料外部への熱伝達を減少させるため、カップ材料の断熱特性がより良好になる。
粉砕性は、破砕を引き起こす引裂または突刺に対する抵抗として定義され得る。
ASTM D1922−93に記載されるエルメンドルフ試験方法を使用した。引裂の半径は、1.7インチ(43.18mm)であった。
試験結果が、以下の表6〜7に示される。本開示の例示的一実施形態で形成される材料は、EPSと比較した際に、引裂力に対するより優れた抵抗を提供する。
試験方法
カップの側壁および底部を突刺すのに必要な力および移動を測定する。Instron機器を、10インチ(254mm)/分の移動速度に設定された圧縮モードで使用する。Instronに基づくカップ突刺試験装置(fixture)を使用する。この装置により、Instron試験装置の移動に対して垂直な上面を有するカップに合致する形状にカップを合わせることができる。装置の直径1インチの孔は、上向きに配置されるべきである。移動するInstronの位置に、直径0.300インチ(7.62mm)のパンチが装着されるべきである。孔とパンチは、試験装置において位置合わせされる。カップを、装置上に配置し、カップ側壁を突刺すのに必要とされる力および移動を記録する。側壁突刺試験を、3つの等間隔の箇所で繰り返す一方、カップの継ぎ目における突刺試験は行わない。カップの底部を試験する。これは、装置を使用しないことを除いて側壁試験と同じ方法で行うべきである。カップを、Instronに基づいてちょうど上下逆に配置する一方、パンチをカップ底部の中央に下ろす。
典型的な側壁突刺および底部突刺の結果が、以下の表8に示される。
試験方法
本開示の例示的一実施形態で形成される材料は、ASTM D−3763−86に記載される低速突刺抵抗試験方法(Slow Puncture Resistance Test Method)を用いて、発泡ポリスチレンと比較した際に突刺に対するより優れた抵抗を提供する。試験結果が、以下の表9〜12に示される。
試験結果
以下の配合物を使用した。
81.70%のBorealis WB140HMS主要なポリプロピレン
0.25%のAmco A18035 PPROタルク充填濃縮物
2%のAmpacet 102823 Process Aid PE MB直鎖状低密度ポリエチレンスリップ剤
0.05%のHydrocerol CF−40E化学的発泡剤
1%のColortech 11933−19着色剤
15%のBraskem F020HC high結晶化度ホモポリマーポリプロピレン
3.4ポンド/時のCO2を、溶融樹脂中に導入した。
例示的実施形態において、押し出された断熱発泡非芳香族ポリマー材料のチューブは、材料が押し出されるときに、異なる冷却条件下で形成された2つの表面を有する。押出チューブの外面としてさらに言及される1つの表面は、空気と接触しており、発泡を制限する物理的障壁を有さない。押出チューブ表面の外面は、12°F/秒以上の冷却速度で吹き込む圧縮空気によって冷却される。反対側の表面は、押出チューブの内側として言及される。押出チューブ表面の内側は、押出チューブの内側を物理的に制限し、かつ10°F/秒未満の冷却速度で水と圧縮空気との組合せによって冷却されるトーピードマンドレル(torpedo mandrel)の金属冷却表面において、押出チューブが、ウェブまたは縦方向に延伸されるときに形成される。例示的実施形態において、冷却水温度は約135°F(57.22℃)である。例示的実施形態において、冷却空気温度は約85°F(29.44℃)である。異なる冷却機構の結果として、押出チューブの外面および押出チューブ表面の内側は、異なる表面特性を有する。冷却速度および方法が、ポリプロピレンの結晶化プロセスに影響を与えて、そのモルホロジー(結晶ドメインのサイズ)およびトポグラフィー(表面形状および平滑度)を変更することが知られている。
試験方法
試験方法は、実施例1の剛性試験について記載されるものと同じである。
剛性試験の結果が、以下の表14に示される。
試験方法−−壁の温度
約0.18g/cm3の密度および約0.074インチ(1.8796mm)の壁厚を有する、上記の配合物から形成される断熱カップを使用した。200°F(93.3℃)の温水をカップに入れた。
カップの外壁で測定された温度は、約49.0°F(27.2℃)低下して、約151°F(66.1℃)であった。5分間の間の最高温度は、約151°F(66.1℃)でピークに達することが観察された。
この試験は、周囲温度および93℃(199.4°F)で測定されるバルク熱伝導性(W/m−K)を測定する。ISO/DIS 22007−2.2の試験方法を用いて、かつ低密度/高断熱(Low Density/High Insulating)オプションを用いて、ThermTest TPS 2500 S Thermal Constants Analyzer機器を使用した。Kapton(登録商標)断熱材とともに0.2521インチの半径(6.403mmの半径)のTPSセンサー番号5501を、全ての測定に使用した。0.02ワットの電力を用いて、20秒間の試験を行った。ポイント100〜200を用いたデータを報告した。
以下の表15に示される試験結果。
Claims (21)
- 密度が0.05〜0.19g/cm3の断熱発泡非芳香族ポリマー構造を形成するための配合物であって、
長鎖分枝を有する少なくとも1つの高溶融強度ポリプロピレンを含む第1のポリマー材料と、
高結晶性ポリプロピレンホモポリマーからなる第2のポリマー材料と、
少なくとも1つの成核剤と、
少なくとも1つのスリップ剤と
を含む配合物。 - (i)前記第1の材料がホモポリマーであるか、
(ii)前記第1のポリマー材料が、ISO16790にしたがって、少なくとも36cNの溶融強度を有するか、
(iii)前記第1のポリマー材料が、少なくとも163℃の溶融温度を有する請求項1に記載の配合物。 - (i)前記成核剤が、化学的成核剤、物理的成核剤、ならびにそれらの混合物および組合せからなる群から選択される少なくとも1つの材料であるか、
(ii)前記成核剤が、クエン酸またはクエン酸ベースの材料であるか、
(iii)前記成核剤が、タルク、CaCO3、マイカ、および上記のものの少なくとも2つの混合物からなる群から選択される少なくとも1つの材料であるか、又は、
(iv)前記発泡剤が、化学的発泡剤、物理的発泡剤、およびそれらの組合せからなる群から選択される少なくとも1つの材料である、請求項1に記載の配合物。 - 少なくとも1つの発泡剤をさらに含むことを特徴とする請求項1に記載の配合物。
- 前記少なくとも1つの発泡剤が、前記配合物が溶融される前に前記配合物中に導入され、混合されることを特徴とする請求項4に記載の配合物。
- 前記発泡剤が、加圧液体として導入される少なくとも1つのガスであることを特徴とする請求項5に記載の混合物。
- 前記発泡剤が、二酸化炭素、窒素、ヘリウム、アルゴン、空気、ペンタン、ブタンまたは他のアルカン、およびそれらの混合物からなる群から選択される少なくとも1つのガスであることを特徴とする請求項6に記載の配合物。
- 前記発泡剤が、反応または分解して、ガスを放出する化学的発泡剤であることを特徴とする請求項4に記載の配合物。
- 前記化学的発泡剤がCaCO3であることを特徴とする請求項8に記載の配合物。
- 前記成核剤が、触媒をさらに含むことを特徴とする請求項8に記載の配合物。
- 前記構造が、0.41mmの長さおよび0.08mmの幅の縦方向における平均気泡サイズならびに0.43mmの長さおよび0.08mmの幅の横断方向における平均気泡サイズを有する、請求項10に記載の配合物。
- (i)前記発泡剤が、アゾジカーボンアミド;アゾジイソブチロ−ニトリル;ベンゼンスルホンヒドラジド;4,4−オキシベンゼンスルホニルセミカルバジド;p−トルエンスルホニルセミ−カルバジド;アゾジカルボン酸バリウム;N,N’−ジメチル−N,N’−ジニトロソテレフタルアミド;トリヒドラジノトリアジン;メタン;エタン;プロパン;n−ブタン;イソブタン;n−ペンタン;イソペンタン;ネオペンタン;フッ化メチル;パーフルオロメタン;フッ化エチル;1,1−ジフルオロエタン;1,1,1−トリフルオロエタン;1,1,1,2−テトラフルオロ−エタン;ペンタフルオロエタン;パーフルオロエタン;2,2−ジフルオロプロパン;1,1,1−トリフルオロプロパン;パーフルオロプロパン;パーフルオロブタン;パーフルオロシクロブタン;塩化メチル;塩化メチレン;塩化エチル;1,1,1−トリクロロエタン;1,1−ジクロロ−1−フルオロエタン;1−クロロ−1,1−ジフルオロエタン;1,1−ジクロロ−2,2,2−トリフルオロエタン;1−クロロ−1,2,2,2−テトラフルオロエタン;トリクロロモノフルオロメタン;ジクロロジフルオロメタン;トリクロロトリフルオロエタン;ジクロロテトラフルオロエタン;クロロヘプタフルオロプロパン;ジクロロヘキサフルオロプロパン;メタノール;エタノール;n−プロパノール;イソプロパノール;炭酸水素ナトリウム;炭酸ナトリウム;重炭酸アンモニウム;炭酸アンモニウム;亜硝酸アンモニウム;N,N’−ジメチル−N,N’−ジニトロソテレフタルアミド;N,N’−ジニトロソペンタメチレンテトラミン;アゾビスイソブチロニトリル;アゾシクロヘキシルニトリル;アゾジアミノベンゼン;ベンゼンスルホニルヒドラジド;トルエンスルホニルヒドラジド;p,p’−オキシビス(ベンゼンスルホニルヒドラジド);ジフェニルスルホン−3,3’−ジスルホニルヒドラジド;カルシウムアジド;4,4’−ジフェニルジスルホニルアジド;およびp−トルエンスルホニルアジドからなる群から選択される少なくとも1つの材料であるか、
(ii)前記スリップ剤が、少なくとも1つの脂肪酸または脂肪酸ベースの材料であるか、又は、
(iii)前記スリップ剤が、エルカ酸アミド、オレイン酸アミド、およびそれらの混合物からなる群から選択される少なくとも1つの材料である、請求項1に記載の配合物。 - (i)耐衝撃性改質剤、着色剤、発泡剤、化合物リグラインド、および上記のものの少なくとも2つの混合物からなる群から選択される少なくとも1つの材料をさらに含むか、
又は、
(ii)着色剤をさらに含む、請求項1に記載の配合物。 - (i)前記構造が、0.41mmの長さおよび0.08mmの幅の縦方向における平均気泡サイズ、ならびに0.43mmの長さおよび0.08mmの幅の横断方向における平均気泡サイズを有するか、
(ii)前記構造が、1.0〜3.0の範囲の少なくとも1つの方向における平均気泡アスペクト比を有する気泡を有するか、又は、
(iii)前記構造が、1.0〜2.0の範囲の少なくとも1つの方向における平均気泡アスペクト比を有する気泡を有する、請求項1に記載の配合物。 - (i)前記構造が、10度/分の加熱および冷却速度で、160℃〜172℃の溶融温度、108℃〜135℃の結晶化温度、および42%〜62%の結晶化度パーセントを有するか、又は、
(ii)前記構造が、10度/分の加熱および冷却速度で、162℃の溶融温度、131℃の結晶化温度、および46%の結晶化度を有する、請求項1に記載の配合物。 - 前記断熱発泡非芳香族ポリマー構造が、0.1g/cm3〜0.185g/cm3の範囲の密度を有する、請求項1に記載の配合物。
- (i)前記構造が、目に見える燃焼または焼け焦げを伴わずに、最大で2.5分間にわたって1,200ワットのマイクロ波エネルギーに曝され得るか、
(ii)前記断熱発泡非芳香族ポリマー構造から形成された、平均壁厚が1.6256mm、平均密度が0.1776g/cm 3 、平均重量が9.86gのカップにおいて、前記カップに蓋をしない状態で、かつ、前記カップに93.3℃の液体を充填した条件で、0.238重量キログラム(kg−F)〜0.324重量キログラム(kg−F)の範囲の剛性を有するか、又は、
(iii)前記断熱発泡非芳香族ポリマー構造が厚さ2.3mm、密度0.1902g/cm3であって、前記断熱発泡非芳香族ポリマー構造から形成されたカップにおいて、ASTM D3763−86に記載される低速突刺抵抗試験方法にしたがって測定した前記断熱発泡非芳香族ポリマー構造の突刺抵抗の平均値が、15,210重量グラムであることを特徴とする請求項1に記載の配合物。 - (i)前記構造が、ASTM D1922−93にしたがって、少なくとも282重量グラムの縦方向における引裂抵抗を有するか、
(ii)前記構造が、エルメンドルフ試験方法ASTM D1922−93にしたがって、前記構造を縦方向に引き裂くのに少なくとも282重量グラムを必要とするか、又は、
(iii)前記構造が、ASTM D1922−93に記載されるエルメンドルフ試験方法にしたがって、前記構造を横断方向に引き裂くのに少なくとも212重量グラムを必要とする、請求項1に記載の配合物。 - (i)前記構造が、エルメンドルフ試験方法ASTM D1922−93にしたがって、前記構造を縦方向に引き裂くのに213重量グラム〜351重量グラムの範囲の力を必要とするか、
(ii)前記構造が、エルメンドルフ試験方法ASTM D1922−93にしたがっ
て、前記構造を横断方向に引き裂くのに143重量グラム〜281重量グラムの範囲の力
を必要とするか、
(iii)前記構造が、カップへと形成される場合、前記カップに93.3℃の液体が充填され、前記カップに蓋がされたとき、60.28℃の最高外部表面温度を有するか、
(iv)前記構造が、ストリップへと形成される場合、21℃で0.00005W/m−Kの標準偏差で、21℃で0.05792W/m−Kの平均熱伝導性を有するか、
(v)前記構造が、ストリップへと形成される場合、93℃で0.00025W/m−Kの標準偏差で、93℃で0.06680W/m−Kの平均熱伝導性を有するか、
(vi)前記構造がリサイクル可能であるか、又は、
(vii)前記構造が、その少なくとも1つの表面上にグラフィックスの印刷を受け入れることができる、請求項1に記載の配合物。 - 断熱発泡非芳香族ポリマー構造を形成するための配合物であって、
少なくとも36cNの溶融強度および少なくとも163℃の溶融温度を有する少なくとも1つの高溶融強度ポリプロピレンを含む第1のポリマー材料と、
高結晶性ポリプロピレンホモポリマーからなる第2のポリマー材料と、
化学的成核剤、物理的成核剤、ならびにそれらの組合せおよび混合物からなる群から選択される少なくとも1つの成核剤と、
少なくとも1つの発泡剤と、
脂肪酸または脂肪酸ベースの組成物を含む少なくとも1つのスリップ剤と
を含む請求項1に記載の配合物。 - 密度が0.05〜0.19g/cm3の断熱発泡非芳香族ポリマー材料の構造を形成するための方法であって、
a.少なくとも1つの高溶融強度ポリプロピレンポリマーを含む第1の材料を提供する工程と、
b.高結晶性ポリプロピレンホモポリマーからなる第2の材料を提供する工程と、
c.化学的成核剤、物理的成核剤、およびそれらの組合せからなる群から選択される少なくとも1つの成核剤を提供する工程と、
d.スリップ剤を加える工程と、
e.工程a〜dで提供される前記材料を混合して、樹脂混合物を形成する工程と、
f.前記樹脂混合物を加熱して、溶融樹脂混合物を形成する工程と、
g.前記溶融樹脂混合物に発泡剤を加えて、押出樹脂混合物を生成する工程と、
h.前記押出樹脂混合物を押し出して、気泡が中に形成された構造を形成する工程と
を含む方法。
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