JP2015508848A - 低密度の再生可能ポリエステル繊維 - Google Patents
低密度の再生可能ポリエステル繊維 Download PDFInfo
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- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
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- 239000004753 textile Substances 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012549 training Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001862 ultra low molecular weight polyethylene Polymers 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 description 1
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Abstract
Description
本書で使用される場合、「繊維」という用語は、金型などの成形オリフィスを通してポリマーを通過させることによって形成される細長い押出成形物を指す。特に断りのない限り、「繊維」という用語は、明確な長さを持つ不連続繊維および実質的に連続するフィラメントの両方を含む。例えば、実質的にフィラメントは、長さと直径の比(「アスペクト比」)が約15,000対1よりも大きく、一部の場合は約50,000対1よりも大きいなど、直径よりもはるかに大きな長さを持ちうる。
A.再生可能ポリエステル
再生可能ポリエステルは、一般的に、熱可塑性組成物の約70重量%〜約99重量%、一部の実施形態では約75重量%〜約98重量%、および一部の実施形態では約80重量%〜約95重量%を占める。さまざまな再生可能ポリエステルの任意のものが、脂肪族ポリエステル、例えば、ポリカプロラクトン、ポリエステルアミド、ポリ乳酸(PLA)およびその共重合体、ポリグリコール酸、炭酸ポリアルキレン(例えば、炭酸ポリエチレン)、ポリ−3−ヒドロキシ酪酸(PHB)、ポリ−3−ヒドロキシ吉草酸(PHV)、ポリ−3−ヒドロキシ酪酸−コ−4−ヒドロキシ酪酸、ポリ−3−ヒドロキシ酪酸−コ−3−ヒドロキシ吉草酸共重合体(PHBV)、ポリ−3−ヒドロキシ酪酸−コ−3−ヒドロキシヘキサン酸、ポリ−3−ヒドロキシ酪酸−コ−3−ヒドロキシオクタン酸、ポリ−3−ヒドロキシ酪酸−コ−3−ヒドロキシデカン酸、ポリ−3−ヒドロキシ酪酸−コ−3−ヒドロキシオクタデカン酸、およびコハク酸ベース脂肪族ポリマー(例えば、ポリブチレンサクシネート、ポリ ブチレン サクシネート アジペート、ポリエチレンサクシネートなど)などや、脂肪族方向族コポリエステル(例えば、ポリブチレンアジペートテレフタレート、ポリエチレンアジペートテレフタレート、ポリエチレンアジペートイソフタレート、ポリブチレンアジペートイソフタレートなど)や、芳香族ポリエステル(例えば、ポリエチレンテレフタレート、ポリブチレンテレフタレートなど)などの熱可塑性組成物で一般的に用いられうる。
上記に示されるように、本発明の熱可塑性組成物は、高分子強化添加剤も含む。その重合体の性質のために、強化添加剤は比較的高い分子量を持ち、これは熱可塑性組成物の溶融強度および安定性の改善に役立ちうる。必須ではないが、高分子強化添加剤は、再生可能ポリエステルと一般的に混合しないことがある。このように、強化添加剤は、再生可能ポリエステルの連続相内に個別層領域として、よりよく分散しうる。個別領域は、外部力から生じるエネルギーを吸収することができ、結果として生じる材料の全体的靱性および強度を増加させる。領域は、楕円形、球形、円筒形などのさまざまな異なる形状を持ちうる。例えば、1つの実施形態では、領域は実質的に楕円の形状を持つ。個々の領域の物理的寸法は、一般的に、外部応力が加わった時、ポリマー材料を通した割れ目の伝播を最小化するために十分小さいが、微視的なプラスチックの変形を開始させ、粒子含有物およびその周りのせん断ゾーンを可能にするために十分大きい。
ここで、
Δ Hv = 蒸発熱
R = 理想気体定数
T = 温度
Vm = モル体積
相間改質剤も、強化添加剤と再生可能ポリエステルの間の摩擦および結合性の程度を減らし、従って剥離の程度および均一性を高めるために、熱可塑性組成物中に使用されうる。このように、空隙は、組成物全体に渡って実質的に均一な様式で分配することができる。改質剤は、比較的低い粘度を持ち、熱可塑性組成物に容易に組み込むことができ、ポリマー表面に簡単に移動できるよう、一般的に、室温(例えば、25℃)で液体または半固体の形態である。この点で、相間改質剤の動粘性率は、40℃で測定された時、一般的に約0.7〜約200センチストーク(「cs」)、一部の実施形態では、約1〜100cs、および一部の実施形態では約1.5〜約80csである。さらに、相間改質剤は、ポリマー強化添加剤に対する親和性を持ち、再生可能ポリエステルと強化添加剤との間の界面張力の変化を生じるように、一般的に疎水性でもある。ポリエステルと強化添加剤との間の界面での物理的力を減らすことによって、改質剤の低粘度、疎水性の性質がポリエステル基質からの剥離の促進を助けることができると考えられる。本書で使用されるとき、「疎水性」という用語は、一般的に、空気中の水の接触角が約40°以上、一部の場合は約60°以上の材料を指す。対照的に、「親水性」という用語は、一般的に、空気中の水の接触角が約40°未満の材料を指す。接触角の測定のための1つの適切な試験はASTM D5725−99(2008年)である。
上述のように、高分子強化添加剤は、概して、再生可能ポリエステルの溶解パラメータに比較的近い溶解パラメータを持つように選択される。とりわけ、これは相の適合性を高め、連続相内の個別領域の全体的分布を改善しうる。それでもなお、特定の実施形態では、再生可能ポリエステルと高分子強化添加剤との間の適合性をさらに高めるために、相溶化剤が随意に使用されうる。これは、高分子強化添加剤が、ポリウレタン、アクリル樹脂などの極性部分を持つ場合、特に望ましいことがある。使用される場合、相溶化剤は、一般的に、熱可塑性組成物の約0.5重量%〜約20重量%、一部の実施形態では約1重量%〜約15重量%、および一部の実施形態では約1.5重量%〜約10重量%を占める。適切な相溶化剤の一例は、官能性ポリオレフィンである。例えば、極性成分は1つ以上の官能基によって提供され、非極性成分はオレフィンによって提供されうる。相溶化剤のオレフィン成分は、概して、上述のようなオレフィンモノマーから由来する任意の直鎖または分岐α−オレフィンモノマー、オリゴマー、またはポリマー(共重合体を含む)から形成されうる。
本発明の1つの有益な側面は、発泡剤(例えば、クロロフルオロカーボン、ヒドロクロロフルオロカーボン、炭化水素、二酸化炭素など)および可塑剤(例えば、固体または半固体のポリエチレングリコール)など、さまざまな従来的添加剤を必要とすることなく、良好な機械的特性が提供されうることである。実際、熱可塑性組成物は、実質的に発泡剤および/または可塑剤を含まない場合がある。例えば、発泡剤および/または可塑剤は、熱可塑性組成物の約1重量%以下、一部の実施形態では約0.5重量%以下、および一部の実施形態では約0.001重量%〜約0.2重量%の量で存在しうる。さらに、以下で詳述されるその応力白化特性のために、結果として生じる組成物は、二酸化チタンなどの、従来的色素を必要とすることなく、不透明色(例えば、白色)を達成しうる。特定の実施形態では、例えば、色素は、熱可塑性組成物の約1重量%以下、一部の実施形態では約0.5重量%以下、および一部の実施形態では約0.001重量%〜約0.2重量%の量で存在しうる。当然、さまざまな異なる理由で、組成物には多種多様な原料を使用しうる。例えば、使用されうる材料には、触媒、抗酸化剤、安定剤、界面活性剤、ワックス、固体溶剤、充填剤、核形成剤(例えば、炭酸カルシウムなど)、微粒子、および熱可塑性組成物の処理可能性を高めるために追加されるその他の材料が含まれうるがこれに限定されない。
熱可塑性組成物は、さまざまな既知の技術のいずれかを使用して、混ぜ合わせうる。1つの実施形態では、例えば、組成物は別々に、または組み合わせて供給されうる。例えば、組成物は、まず乾燥混合されて基本的に均一な乾燥混合物を形成し、同様に、分散的に材料を混合する溶融処理装置に同時または順番に供給されうる。バッチおよび/または連続溶融処理技術を用いうる。例えば、ミキサー/混練機、バンバリーミキサー、ファレル連続ミキサー、単軸スクリュー押出機、二軸スクリュー押出機、ロールミルなどを使用して、材料を混合し溶融処理しうる。特に適切な溶融処理装置は、共回転式二軸スクリュー押出機(例えば、Werner & Pfleiderer Corporation(ニュージャージー州ラムジー)から入手可能なZSK−30押出機またはThermo Electron Corp.(イギリス、ストーン)から入手可能なThermo Prism(登録商標) USALAB 16押出機)でありうる。このような押出機は、供給ポートおよび換気ポートを含み、強力な分配・分散混合をもたらす。例えば、成分は二軸スクリュー押出機の同じまたは異なる供給ポートに供給され溶融混合されて、実質的に均一な溶融混合物を形成しうる。必要に応じて、その他の添加剤も、ポリマー溶解物に注入および/または押出機の長さに沿った異なる点で押出機に別々に供給されうる。
混合された熱可塑性組成物から形成された繊維は、一般的に、単一成分および多成分(例えば、シース・コア構成、横並び構成、セグメント化パイの構成、アイランド・イン・ザ・シーの構成など)を含む、任意の望ましい構成を持ちうる。一部の実施形態では、繊維は、強度およびその他の機械的特性を高めるために、成分(例えば、2成分)または構成成分(例えば、2構成成分)として1つ以上の追加的ポリマーを含みうる。例えば、熱可塑性組成物は、シース/コア複合繊維のシース成分を形成する一方、追加的ポリマーはコア成分を形成するか、またはその反対でありうる。追加的ポリマーは、ポリオレフィン(例えば、ポリエチレン、ポリプロピレン、ポリブチレンなど)、ポリテトラフルオロエチレン、ポリ酢酸ビニル、ポリ塩化ビニル‐酢酸ビニル、ポリビニルブチラール、アクリル樹脂(例えば、ポリアクリル酸塩、ポリアクリル酸メチル、ポリメタクリル酸メチルなど)、ポリアミド(例えば、ナイロン)、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリスチレン、ポリビニルアルコール、およびポリウレタンなど、一般的に再生可能と見なされない熱可塑性ポリマーでありうる。しかし、追加的ポリマーは再生可能であることがより望ましい。
Aは、溶融延伸後の繊維の線速度(例えば、ゴデット速度)であり直接測定され、
Bは、押出された繊維の線速度であり以下のように計算できる:
Cは、1つの穴を通したスループット(グラム/分)であり、
Dはポリマーの溶融密度(グラム/立方センチメートル)であり、
Eは、繊維がそれを通して押出される穴の直径(センチメートル)である。特定の実施形態では、ドローダウン比は約20:1〜約4000:1、一部の実施形態では、約25:1〜約2000:1、一部の辞し形態では約50:1〜約1000:1、および一部の実施形態では約75:1〜約800:1でありうる。
繊維および/またはそれから形成されたウェブは、幅広い用途に使用されうる。例えば、繊維は、ガウン、外科用ドレープ、フェースマスク、頭部カバー、手術帽、靴カバー、滅菌ラップ、毛布、加熱パッドなどの「医療製品」に組み込まれうる。当然、繊維はその他のさまざまな物品に使用されうる。例えば、繊維は、水またはその他の流体を吸収できる「吸収性物品」に組み込まれうる。一部の吸収性物品の例には、おむつ、トレーニングパンツ、吸収性下着、失禁物品、女性用衛生用品(例えば、生理用ナプキン)、水着、おしり拭き、ミットワイプなどのパーソナルケア吸収性物品、衣類、穿孔材料、アンダーパッド、ベッドパッド、包帯、吸収性ドレープ、および医療用ワイプなどの医療用吸収性物品、食品サービスタオル、衣料物品、パウチなどを含むがこれに限定されない。このような物品の形成に適した材料およびプロセスは、当業者にはよく知られている。例えば吸収性物品は、一般的に、実質的に液体透過性の層(例えば、外側カバー)、液体透過性層(例えば、体側のライナー、サージ層など)、および吸収性コアを含む。1つの実施形態では、例えば、本発明の繊維から形成される不織布ウェブは、吸収性物品の外側カバーを形成するために使用されうる。必要に応じて、不織布ウェブは、蒸気透過性または蒸気不透過性の液体不透過性フィルムへと積層されうる。
メルトフローレート:
メルトフローレート(「MFR」)は、一般的に190℃または230℃で、2160グラム/10分の負荷をかけた時、押出レオメーター口(直径0.0825インチ)を通して押出されるポリマーの重量(グラム)である。別段の指示がない限り、メルトフローレートは、Tinius Olsen Extrusion PlastometerでASTM試験方法D1239に従って測定される。
ガラス転移温度(Tg)は、ASTM E1640−09に従って、動的機械分析(DMA)で決定されうる。TA Instruments社のA Q800機器を使用しうる。実験は、張力/張力形状で、−120℃〜150℃の温度掃引モード、3℃/分の加熱率で実行されうる。歪振幅周波数は、試験中、一定(2 Hz)に保ちうる。3つの独立サンプルを試験して、平均ガラス転移温度を得るが、これはtan δ曲線の最大値によって定義され、ここでδは、貯蔵弾性率に対する損失弾性率の比(tan δ = E”/E’)として定義される。
引張特性は、ASTM 638−10に従って23℃で測定されうる。例えば、個別の繊維標本は、初めに38mmの長さまで短くされ、黒いベルベット布の上に別々に配置されうる。10〜15個の標本がこのようにして集められる。繊維標本は次に、51mm×51mmの外側寸法および25mm×25mmの内側寸法を持つ長方形の紙フレーム上に実質的に真っ直ぐな状態で取り付けられうる。各繊維標本の端部は、接着テープでフレームの側部に繊維端部を固定することにより、操作可能なようにフレームに取り付けられうる。各繊維標本は、適正に較正され倍率40Xに設定されうる従来的な実験用顕微鏡を使用して、その外部の比較的短い繊維断面寸法を測定しうる。この繊維断面寸法は、個々の繊維標本の直径として記録されうる。フレームは、繊維標本への過剰な損傷を避ける方法で、サンプル繊維標本の端部を、一定割合延長タイプ引張試験機の上部および下部グリップに取り付けるのに役立つ。
水分含量は、Arizona Instruments Computrac Vapor Pro水分分析器(モデル番号3100)を使用して、ASTM D 7191−05に実質的に従って決定することができ、これはすべての目的に対して参照によりその全体を本書に組み込む。試験温度(§X2.1.2)は130℃、サンプルサイズ(§X2.1.1)は2〜4グラム、およびバイアルパージ時間(§X2.1.4)は30秒としうる。さらに、終了基準(§X2.1.3)は、「予測」モードとして定義でき、これはプログラムされた内蔵基準(これは数学的に終了点水分含量を計算する)が満足された時に試験が終了することを意味する。
Claims (20)
- 熱可塑性組成物から形成される繊維であって、前記熱可塑性組成物が、
約0℃以上、好ましくは約50℃〜約75℃のガラス転移温度を持つ少なくとも1つの硬質再生可能ポリエステルと、
前記再生可能ポリエステルの重量に基づいて約1重量%〜約30重量%の少なくとも1つの高分子強化添加剤と、
前記再生可能ポリエステルの重量に基づいて約0.1重量%〜約20重量%の少なくとも1つの相間改質剤とを含み、
前記熱可塑性組成物が、複数の個別の主要領域および空隙が連続相内に分散された形態を持ち、前記領域が前記高分子強化添加剤を含み、前記連続相が前記再生可能ポリエステルを含み、
前記繊維が、約1.4グラム/立方センチメートル以下、好ましくは約0.5グラム/立方センチメートル〜約0.95グラム/立方センチメートルの密度を持ち、
前記空隙によって占められる前記組成物の平均体積パーセントが、約20%〜約80%/立方センチメートル、好ましくは約40%〜約60%/立方センチメートルである繊維。 - 前記空隙のアスペクト比が約0.1〜約1である、請求項1に記載の繊維。
- 前記空隙がマイクロ空隙およびナノ空隙の組合せを含む、請求項1または2に記載の繊維。
- 前記再生可能ポリエステルがポリ乳酸である、前述の請求項のいずれかの繊維。
- 前記高分子強化添加剤の溶解パラメータに対する前記再生可能ポリエステルの溶解パラメータの比が約0.5〜1.5であり、前記高分子強化添加剤のメルトフローレートに対する前記再生可能ポリエステルのメルトフローレートの比が約0.2〜8であり、前記高分子強化添加剤のヤングの弾性率に対する前記再生可能ポリエステルのヤングの弾性率の比が約2〜500である、前述の請求項のいずれかの繊維。
- 前記高分子強化添加剤が、ポリプロピレン・ホモポリマー、プロピレン/α−オレフィン共重合体、エチレン/α−オレフィン共重合体、またはその組合せなどのポリオレフィンを含む、前述の請求項のいずれかの繊維。
- 前記相間改質剤が、40℃の温度で測定された時、約0.7〜約200センチストークの動粘度を持つ、前述の請求項のいずれかの繊維。
- 前記再生可能ポリエステルの前記ガラス転移温度に対する前記熱可塑性組成物の前記ガラス転移温度の比が約0.7〜約1.3である、前述の請求項のいずれかの繊維。
- 前記相間改質剤が疎水性である、前述の請求項のいずれかの繊維。
- 前記相間改質剤がシリコン、シリコン・ポリエーテル共重合体、脂肪族ポリエステル、芳香族ポリエステル、アルキレングリコール、アルカンジオール、アミンオキシド、脂肪酸エステル、またはその組合せである、前述の請求項のいずれかの繊維。
- 前記組成物が、エポキシ官能性(メタ)アクリル単量体成分を含むポリエポキシド改質剤を含む、前述の請求項のいずれかの繊維。
- 前記再生可能ポリエステルが、前記熱可塑性組成物の約70重量%以上を占める、前述の請求項のいずれかの繊維。
- 前述の請求項のいずれかの繊維を含む不織布ウェブ。
- 液体透過性層と概して液体不透過性層との間に位置付けられた吸収性コアを含む吸収性物品であって、前記吸収性物品が請求項13の前記不織布ウェブを含む吸収性物品。
- 低密度繊維を形成する方法であって、前記方法が、
ポリ乳酸などの硬質再生可能ポリエステル、およびポリオレフィンなどの高分子強化添加剤を含む混合物を形成する手順であって、前記硬質再生可能ポリエステルが約0℃以上のガラス転移温度を持つ手順と、
金型を通して前記混合物を押出して前記繊維を形成する手順と、
前記再生可能ポリエステルの前記ガラス転移温度よりも低い温度、好ましくは前記再生可能ポリエステルの前記ガラス転移温度よりも少なくとも約10℃低い温度で前記繊維を延伸し、複数の空隙を含み、約1.4グラム/立方センチメートル以下、好ましくは約0.5グラム/立方センチメートル〜約0.95グラム/立方センチメートルの密度を持つ熱可塑性組成物を形成する手順とを含む方法。 - 前記再生可能ポリエステルの前記ガラス転移温度よりも高い温度で前記延伸繊維を焼きなます手順をさらに含む、請求項15に記載の方法。
- 前記空隙によって占められる前記繊維の平均体積パーセントが、立方センチメートルあたり約20%〜約80%である、請求項15に記載の方法。
- 前記混合物が、少なくとも1つの相間改質剤および/またはエポキシ官能性(メタ)アクリル単量体成分を含むポリエポキシド改質剤を含む、請求項15に記載の方法。
- 前記混合物が一般的に気体発泡剤を含まない、請求項15に記載の方法。
- 不織布ウェブを形成する方法であって、前記方法が、
硬質再生可能ポリエステルおよび高分子強化添加剤を含む混合物を形成する手順であって、前記硬質再生可能ポリエステルが約0℃以上のガラス転移温度を持つ手順と、
金型を通して前記混合物を押出して複数の繊維を形成する手順と、
前記延伸繊維を表面上に無作為に堆積させて不織布ウェブを形成する手順と、
前記不織布ウェブが形成される前および/または後に前記繊維を延伸する手順であって、前記再生可能ポリエステルの前記ガラス転移温度より低い温度で前記繊維が延伸されて、複数の空隙を含み、約1.4グラム/立方センチメートル以下の密度を持つ熱可塑性組成物を形成する手順とを含む方法。
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| US12139822B2 (en) | 2024-11-12 |
| EP2820175B1 (en) | 2019-11-27 |
| US20130210308A1 (en) | 2013-08-15 |
| US10858762B2 (en) | 2020-12-08 |
| BR112014019495A8 (pt) | 2017-07-11 |
| MX354160B (es) | 2018-02-14 |
| WO2013118019A2 (en) | 2013-08-15 |
| JP6168526B2 (ja) | 2017-07-26 |
| CN104093891A (zh) | 2014-10-08 |
| AU2013217362A1 (en) | 2014-07-24 |
| KR20140123061A (ko) | 2014-10-21 |
| EP2820175A4 (en) | 2015-11-04 |
| RU2620415C2 (ru) | 2017-05-25 |
| EP2820175A2 (en) | 2015-01-07 |
| US20210180216A1 (en) | 2021-06-17 |
| KR101964486B1 (ko) | 2019-07-31 |
| BR112014019495A2 (ja) | 2017-06-20 |
| RU2014135462A (ru) | 2016-04-10 |
| CN104093891B (zh) | 2017-04-12 |
| MX2014009542A (es) | 2014-11-10 |
| BR112014019495B1 (pt) | 2021-02-02 |
| AU2013217362B2 (en) | 2016-10-20 |
| WO2013118019A3 (en) | 2013-11-07 |
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