JP2022553314A - 多層水分散性物品 - Google Patents
多層水分散性物品 Download PDFInfo
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- JP2022553314A JP2022553314A JP2022523458A JP2022523458A JP2022553314A JP 2022553314 A JP2022553314 A JP 2022553314A JP 2022523458 A JP2022523458 A JP 2022523458A JP 2022523458 A JP2022523458 A JP 2022523458A JP 2022553314 A JP2022553314 A JP 2022553314A
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- water
- wax
- phr
- article
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Abstract
Description
本出願は、米国特許法第119条(e)に基づき、2019年10月25日に出願された米国仮特許出願第62/926,293号の恩典を主張し、その開示全体は参照により本明細書に組み込まれる。
本開示は、一般に、多層水分散性物品などの水分散性物品に関する。特に、本開示は、水溶性ポリマーと蝋を含む水分散性物品に関する。より具体的には、本開示は、水溶性ポリマーを含む水分散性基材層または材料と、前記基材層または材料の表面上に配置または配列された水分散性コーティング層または材料とを有する多層水分散性物品に関する。本開示は、水分散性物品であって、前記物品は、約20gH2O/m2/日またはそれ未満、例えば10gH2O/m2/日またはそれ未満の水蒸気透過率(MVTR)を有する、水分散性物品に関する。
水溶性および水分散性物品は、送達されるべき組成物の分散、注入、溶解および投与を単純化するための包装として一般的に使用されている。消費者は、バケツ、シンクまたは水を保持するのに適した任意の容器などの混合容器に包装された組成物を直接添加することができる。有利には、これにより、消費者が組成物を測定する必要性を除去しながら、正確な投与が提供される。包装された組成物は、材料を注ぐまたはすくい取るなど、製品容器からの組成物の分配に伴う混乱も低減し得る。要するに、可溶性および分散性の予め測定された包装または物品は、様々な用途における消費者使用の利便性を提供する。
本開示の一態様は、水溶性ポリマーと蝋とを含む多層水分散性物品、必要に応じてフィルムであって、前記蝋は、前記水溶性ポリマーの100重量部に基づいて、約5PHR~約30PHRの範囲の量で存在し、前記水分散性物品は、約20gH2O/m2/日またはそれ未満の水蒸気透過率(MVTR)を有する、多層水分散性物品を提供する。
複数の実施形態において、本開示は、水溶性ポリマーと蝋とを含む多層水分散性物品を提供する。複数の実施形態において、本開示は、ポリマー層(例えば、水溶性ポリマーを含む)と蝋層(例えば、蝋を含む)とを含む多層水分散性物品を提供する。本明細書に記載されているように、物品は多層水分散性物品である。本明細書で使用される「多層水分散性物品」という用語は、別個の自己支持性基材層をコーティング層でコーティングして多層物品を提供することを含むプロセスによって調製された物品を指すことができる。このプロセスにもかかわらず、このようにして調製された物品は、分離した(discrete)またはその他別個の(distinct)層を有していなくてもよい、すなわち、コーティング層は、基材層の表面にもつれ合い、融合し、絡み合い、一体化され、またはその他結び付けられ、基材層自体と共に物品の水蒸気透過率に寄与することができる相互作用性のバリアを基材層上に提供することができることを当業者は理解すべきである。これに代えてまたはこれに加えて、「多層水分散性物品」という用語は、単一の組成物中で成分(例えば、基材および/またはコーティング層を構成する成分)を一緒に混合し、その後、前記単一の組成物から物品を注型、押出成形またはその他形成(例えば、成形)することを含む過程によって調製された物品を指すことができる。この過程によって形成された物品は、いくつかの構成要素が物品を通って物品の表面に移動して、物品の表面上に多層の「擬似コーティング」を付与する「ブルーミング効果(blooming effect)」を受けることができる。有利には、本開示の物品、例えば水分散性フィルムは、コーティング材料を含まない水分散性フィルムと比較して、成形性および密封特性(例えば、パウチの形成および密封)、ならびに引張特性を含むがこれらに限定されない、実質的に維持または改善された機能的特性を示すことができる。さらに有利には、物品のMVTRは、長期間(例えば、貯蔵寿命)維持することができるが、使用時に容易に分散することができる。
基材層およびコーティング層を含む多層水分散性物品
基材層
コーティング層
水溶性ポリマーと蝋を含む多層水分散性物品
多層水分散性物品の作製方法
方法A
方法B
パケット/パウチ
多層水分散性フィルムの垂直型充填封止
多層水分散性フィルムの成形、封止および熱成形
多層水分散性物品の含有物
水蒸気透過率(MVTR)試験
透明度/黄色度
摩擦係数(COF)試験
1. Instron(登録商標)Coefficient of Friction Testing Fixture Model 2810-005上の下あごからUリンクピンを取り外して、取り除く。
2. 上あごからUリンクピンを取り外して、取り除く。
3. Instron(登録商標)Testing Machine Model #5543のベースアダプタ上に摩擦フィクスチャ下方継手を配置する。
4. Uリンクピンで下方継手を取り付ける。
5. プルコードの一端のループを上方Uリンクピンの上に滑り込ませ、ロッククリップを取り替える。
6. Testing Machine Model#5543を較正する
7. プルコードの他端のループを摩擦スレッドフック上に滑り込ませる。
8. 滑車が自由に回転できることを確認する
9. プルコードに弛みがなく、滑車の周りの溝の中に配置されるまで、スレッドを移動させる。
10. スレッドを滑車の中に走行させることなく試験の全長50mmに沿って摩擦スレッドを引っ張るのに十分な移動空間が存在するように、Instron(登録商標)Coefficient of Friction Testing Fixture Model 2810-005の可動クロスヘッド(上方ヘッド(heard))を位置決めする。
11. クロスヘッドが動いている間、コードをピンと張った状態に保つ。
12. Instron#5543制御パネル上のJOG制御を使用して、摩擦スレッドの遠端が摩擦フィクスチャの背面(運動の軸に対して垂直であり、滑車から最も遠い平面)を超えないように伸長限度を設定する。GLボタンを押して走行限度を設定する。これにより、試験中に摩擦スレッドが滑車と衝突することが防止され、関心対象のサンプルの摩擦係数が適切に測定されることが保証される。
13. これで、試験フィクスチャは、試験の準備が整った。
1. アルミニウム摩擦フィクスチャの上に、表面サンプルを適切な方向で配置する。
2. アルミニウム表面の端部の上に表面サンプルをきつく引っ張り、摩擦フィクスチャの底部側にサンプルをテープで留める。
3. 表面上でのスレッドの結合を避けるために、継手から最も遠い摩擦フィクスチャの端部に沿ってテープを貼り付けることが重要である。
4. 材料がピンと張っているが伸張していないことを確認する。
5. 5×5インチのサンプルで摩擦スレッドを包む
6. スレッドの上に最先端の重なりをテープで貼り付け、表面サンプル上に結合する過剰な材料が存在しないようにする。
7. 摩擦スレッド上のサンプルの他方の縁部をテープで固定して、測定されている接触面上でサンプルがピンと張るようにする。
8. スレッド上の対象表面と摩擦フィクスチャ上の対象表面との間にテープが入らないようにする。
9. 摩擦面上および摩擦スレッド上のサンプルは、しわまたは膨らみがなくピンと張った状態でなければならない;しわまたは膨らみは、COFを測定する際に誤差の原因となる。
10. スレッドを検査して、試験されている表面に触れている異物が存在しないことを確認する。
11. 2つの検体の間に不自然な結合が生じるのを防ぐために、スレッドをプルコードに取り付け、摩擦テーブル上にスレッドを極めてそっと静かに置き、直ちに試験を開始する。
12. 完全に伸長したときに、スレッドが摩擦フィクスチャ上に置かれたサンプルの上に完全に位置し、テープに接触したり、または摩擦フィクスチャの端部から突出しないようにする。
1. 要求される向き(例えば、コーティング層側または基材層側)ごとに3つまたはそれを超える検体を試験する。
2. フィルムのコーティング層側の向きは、アルミニウム試験表面上に配置されたフィルムサンプルであるべきであり、試験をするための基材層側は、スレッドの周りに巻き付けられた材料を含むべきである。
3. フィルム検体を取り扱う際には、粉末が存在しない防湿手袋を必ず着用すること;粉末または水分が、試験の精度を損ない得る。
4. 例えばテンプレートを使用して、上記のようにサンプルを切断する。
5. 第1の検体に包まれた摩擦スレッドを、滑車から最も遠い摩擦フィクスチャの末端に配置する。
6. プルコードがピンと張った状態で引っ張られていることを確認する。
7. 試験画面から「COF.im ptf」と題する摩擦係数試験を開く。
8. 画面上の開始ボタンをクリックすると試験が開始される。
9. 検体の試験実行が完了したら、OKをクリックし、摩擦スレッドを開始位置に戻し、摩擦スレッドおよびフィクスチャ上のフィルム検体を交換する。試験を繰り返す。
剥離強度測定
引張強度試験および伸度試験(ASTM D 882)
化学的安定性試験
溶解および崩壊試験(改変MSTM 205)
1. 500mLビーカー
2. マグネチックスターラー(Labline Model No.1250または同等品)
3. マグネチックスターラーバー(5cm)
4. 温度計(0~100℃±1℃)
5. テンプレート、ステンレス鋼(3.8cm×3.2cm)
6. タイマー(0~300秒、秒単位で正確)
7. ポラロイド(登録商標)35mmスライドマウント(または同等品)
8. MonoSol 35mmスライドマウントホルダー(または同等品)
9. 蒸留水
1. 各検体を別個の35mmスライドマウントに固定する。
2. ビーカーに500mLの蒸留水を充填する。温度計で水温を測定し、必要であれば、水を加熱または冷却して温度を20℃(68°F)に維持する。
3. 水中の高さに印をつける。マグネチックスターラーをホルダーの基台部に置く。ビーカーをマグネチックスターラーの上に置き、マグネチックスターラーバーをビーカーに加え、スターラーを作動し、水柱の高さの約1/5の渦が発生するまで撹拌速度を調整する。渦の深さに印をつける。
4. スライドマウントの長端が水面と平行になるように、35mmスライドマウントホルダーのワニ口クランプに35mmスライドマウントを固定する。ホルダーの深さ調節装置は、下ろされたときにクランプの端部が水面下0.6cmになるように設定されるべきである。スライドマウントの短辺の一方はビーカーの側面に隣接し、短辺の他方は、物品表面が水の流れに対して垂直になるようにスターラーバーの中心の真上に配置されるべきである。
5. 1つの動作で、固定されたスライドおよびクランプを水の中に下ろし、タイマーを始動させる。崩壊は、物品がばらばらになったときに起こる。300秒後、溶解していない物品断片について溶液をモニターし続けながら、スライドを水から持ち上げる。すべての物品断片がもはや見えなくなり、溶液が透明になったときに、溶解が起こる。フィルムがスライドから完全に溶解していない場合、スライド中に無傷で残っているフィルムのおよそのパーセント(%)表面積:0~25%、25~50%、50~75%または75~100%に注目されたい。これはパーセント残留(%)と呼ばれる。
I補正=I測定×(基準厚さ/測定厚さ)1.93 [1]
S補正=S測定x(基準厚さ/測定厚さ)1.83 [2]
一次組成物を提供するために、水溶性ポリマーと蝋エマルジョンを混合することと、
前記多層水分散性物品を提供するために前記一次組成物を注型または押出成形することと、
を含み、前記水分散性物品は、約60gH2O/m2/日~約300gH2O/m2/日の水蒸気透過率(MVTR)を有する、方法。
(A)PVOH/マレイン酸モノメチル(MMM)コポリマー、または(B)PVOHホモポリマーを含む水分散性基材層を、溶液流延および乾燥を通じて調製した。PVOHホモポリマーをベースとする基材層は、約50PHR(層の約30重量%)の総量での可塑剤としてのグリセリン、プロピレングリコール、ソルビトールおよびキシリトールと、セルロースと、ならびに他の様々な添加剤をさらに含んだ。PVOH/MMMコポリマーをベースとする基材層は、約7.5PHR(層の約6.6重量%)の総量での可塑剤としてのグリセリン、ソルビトールおよびジグリセロールと、デンプンと、ならびに他の様々な添加剤とをさらに含んだ。基材層は、表1および表2に示されている厚さを有した。
実施例2:実施例1の物品の剥離強度データ
実施例3:フィルムMVTRの評価
実施例4:フィルムのジオキサン含有量の評価
Claims (53)
- 多層水分散性物品、必要に応じてフィルムであって、水溶性ポリマーを含むポリマー層と、蝋を含む蝋層とを備え、前記蝋が、前記水溶性ポリマーの100重量部に基づいて、約5PHR~約200PHRの範囲の量で存在し、前記水分散性物品が、約60gH2O/m2/日~約300gH2O/m2/日の水蒸気透過率(MVTR)を有する、多層水分散性物品。
- 前記蝋が、パラフィン蝋、微結晶蝋、天然石油蝋、合成石油蝋、カルナバ蝋、カンデリラ蝋、蜜蝋および前述のいずれかの任意の混合物からなる群から選択される、請求項1に記載の多層水分散性物品。
- 前記ポリマー層または蝋層が、酸化ポリエチレン、鉱油、ウッドロジン、シェラック、トリグリセリド、亜麻仁油、トウモロコシ油、キャノーラ油、麻油、ヤシ油、未修飾ポリビニルアルコール、アニオン性基で修飾されたポリビニルアルコール、ポリアクリルアミド、ポリ(アクリル酸)、ポリ(メタクリル酸)、ポリビニルピロリドン、第四級アンモニウムポリマー、ポリ酢酸ビニル、エチレンビニルアルコール、アルギネート、多糖類、タンパク質、pH調整されたタンパク質、木材パルプ、非木材パルプ、不織繊維、天然発泡体、合成発泡体および前述のいずれかの誘導体の1またはそれより多くをさらに含む、請求項1または2に記載の多層水分散性物品。
- 前記水溶性ポリマーが、ポリビニルアルコール、ポリアクリルアミド、ポリ(アクリル酸)、ポリ(メタクリル酸)、ポリビニルピロリドン、第四級アンモニウムポリマー、セルロースエーテルまたは前述のいずれかの任意の混合物を含む、請求項1~3のいずれか一項に記載の多層水分散性物品。
- 前記水溶性ポリマーが未修飾ポリビニルアルコールを含む、請求項4に記載の多層水分散性物品。
- 前記水溶性ポリマーが、イタコン酸、マレイン酸モノメチル、スルホン酸アミノプロピル、マレイン酸、無水マレイン酸、n-ビニルピロリドン、n-ビニルカプロラクタム、および前述のいずれかの誘導体の群中の1またはそれより多くで修飾された、アニオン性基で修飾されたポリビニルアルコール樹脂を含む、請求項4または5に記載の多層水分散性物品。
- 前記アニオン性基で修飾されたポリビニルアルコールが、マレイン酸モノメチルで修飾されたポリビニルアルコールを含む、請求項6に記載の多層水分散性物品。
- 前記アニオン性基で修飾されたポリビニルアルコールが少なくとも0.5mol%のアニオン性基修飾を含む、請求項6または7に記載の多層水分散性物品。
- 前記アニオン性基で修飾されたポリビニルアルコールが約1.0~約4.0mol%のアニオン性基修飾を含む、請求項6~8のいずれか一項に記載の多層水分散性物品。
- 前記アニオン性基で修飾されたポリビニルアルコールが約1.0~約3.5mol%のアニオン性基修飾を含む、請求項6~9のいずれか一項に記載の多層水分散性物品。
- 前記ポリビニルアルコールが、少なくとも88mol%の加水分解度を有する、請求項4~10のいずれか一項に記載の多層水分散性物品。
- 前記ポリビニルアルコールが、90mol%~99mol%未満の範囲の加水分解度を有する、請求項4~11のいずれか一項に記載の多層水分散性物品。
- 前記ポリビニルアルコールが、20℃で少なくとも約6cPの4%水溶液粘度を有する、請求項4~12のいずれか一項に記載の多層水分散性物品。
- 前記水溶性ポリマーがセルロースエーテルを含む、請求項4~13のいずれか一項に記載の多層水分散性物品。
- 前記セルロースエーテルがカルボキシメチルセルロースを含む、請求項14に記載の多層水分散性物品。
- 前記物品が、第1の面と、前記第1の面の反対側に位置する第2の面とを備え、前記第1の面が前記ポリマー層を備え、前記第2の面が前記蝋層を備える、請求項1~15のいずれか一項に記載の多層水分散性物品。
- 前記水分散性物品が、内部パウチ容積に面する内面と前記内面の反対側に位置する外面とを有する、前記内部パウチ容積を規定するパウチの形態であり、前記蝋層が、前記パウチの前記外面の少なくとも一部を形成する、請求項1~16のいずれか一項に記載の多層水分散性物品。
- 前記水分散性物品が、内部パウチ容積に面する内面と前記内面の反対側に位置する外面とを有する、前記内部パウチ容積を規定するパウチの形態であり、前記蝋層が、前記パウチの前記内面の少なくとも一部を形成する、請求項1~16のいずれか一項に記載の多層水分散性物品。
- 前記ポリマー層と前記蝋層の間に配置された中間領域を備え、前記中間領域は、前記水溶性ポリマーと前記蝋の混合物を含む、請求項1~18のいずれか一項に記載の多層水分散性物品。
- 前記ポリマー層または前記蝋層が可塑剤をさらに含む、請求項1~19のいずれか一項に記載の多層水分散性物品。
- 前記可塑剤が、グリセロール、ジグリセロール、プロピレングリコール、ジプロピレングリコール、エチレングリコール、ジエチレングリコール、トリエチレングリコール、最大MW400のポリエチレングリコール、ソルビトール、2-メチル-1,3-プロパンジオール、エタノールアミン、トリメチロールプロパン(TMP)、ポリエーテルポリオール、イソマルト、マルチトール、キシリトール、エリスリトール、アドニトール、ズルシトール、ペンタエリスリトール、マンニトール、または前述のいずれかの組合せを含む、請求項20に記載の多層水分散性物品。
- 前記ポリマー層または前記蝋層が、充填剤、界面活性剤、ブロッキング防止剤、酸化防止剤、スリップ剤、分散剤、または前述のいずれかの組合せをさらに含む、請求項1~21のいずれか一項に記載の多層水分散性物品。
- 前記可塑剤、前記充填剤、前記界面活性剤、前記ブロッキング防止剤、前記酸化防止剤、前記スリップ剤、前記分散剤、または前記のいずれかの組合せが、前記水溶性ポリマーと混合される、請求項21または22に記載の多層水分散性物品。
- 前記蝋が、約5重量%~約30重量%の蝋を含む蝋エマルジョンを含む、請求項1~23のいずれか一項に記載の多層水分散性物品。
- 前記蝋が、パラフィン蝋、蜜蝋、またはこれらの組合せを含む、請求項1~24のいずれか一項に記載の多層水分散性物品。
- 前記蝋が、2またはそれを超える異なる蝋の混合物を含む、請求項1~25のいずれか一項に記載の多層水分散性物品。
- 前記蝋が、前記蝋の総重量に基づいて、約10重量%~約90重量%のパラフィン蝋および約10重量%~約90重量%の蜜蝋を含む、請求項25または26に記載の多層水分散性物品。
- 前記蝋が、約40℃~約100℃の範囲の融点を有する、請求項1~27のいずれか一項に記載の多層水分散性物品。
- 前記物品が、約60gH2O/m2/日~約250gH2O/m2/日の範囲の水蒸気透過率(MVTR)を有する、請求項1~28のいずれか一項に記載の多層水分散性物品。
- 前記物品が、約60gH2O/m2/日~約205gH2O/m2/日の範囲の水蒸気透過率(MVTR)を有する、請求項1~29のいずれか一項に記載の多層水分散性物品。
- 前記物品が、約60gH2O/m2/日~約150gH2O/m2/日の範囲の水蒸気透過率(MVTR)を有する、請求項1~30のいずれか一項に記載の多層水分散性物品。
- 前記物品が、約60gH2O/m2/日~約100gH2O/m2/日の範囲の水蒸気透過率(MVTR)を有する、請求項1~31のいずれか一項に記載の多層水分散性物品。
- 前記水溶性ポリマーが、未修飾ポリビニルアルコール樹脂とカルボキシメチルセルロースの混合物を含み、前記蝋が、蜜蝋と、ポリソルベート80と、水とを含む蝋エマルジョンを含む、請求項1~32のいずれか一項に記載の多層水分散性物品。
- 多層水分散性物品を作製する方法であって、
一次組成物を提供するために、水溶性ポリマーと蝋エマルジョンを混合することと、
前記多層水分散性物品を提供するために前記一次組成物を注型または押出成形することと、
を含み、前記水分散性物品は、約60gH2O/m2/日~約300gH2O/m2/日の水蒸気透過率(MVTR)を有する、方法。 - 前記水溶性ポリマーが、ポリビニルアルコール、ポリアクリルアミド、ポリ(アクリル酸)、ポリ(メタクリル酸)、ポリビニルピロリドン、四級アンモニウムポリマーおよびセルロースエーテルの群中の1またはそれより多くから選択される、請求項34に記載の方法。
- 前記水溶性ポリマーが未修飾ポリビニルアルコールを含む、請求項35に記載の方法。
- 前記水溶性ポリマーが、イタコン酸、マレイン酸モノメチル、スルホン酸アミノプロピル、マレイン酸、無水マレイン酸、n-ビニルピロリドン、n-ビニルカプロラクタム、および前述のいずれかの誘導体の群中の1またはそれより多くで修飾された、アニオン性基で修飾されたポリビニルアルコール樹脂を含む、請求項35または36に記載の方法。
- 前記アニオン性基で修飾されたポリビニルアルコールが少なくとも0.5mol%のアニオン性基修飾を含む、請求項37に記載の方法。
- 前記アニオン性基で修飾されたポリビニルアルコールが約1.0~約4.0mol%のアニオン性基修飾を含む、請求項37または38に記載の方法。
- 前記アニオン性基で修飾されたポリビニルアルコールが約1.0~約3.5mol%のアニオン性基修飾を含む、請求項37~39のいずれか一項に記載の方法。
- 前記ポリビニルアルコールが、少なくとも88mol%の加水分解度を有する、請求項35~40のいずれか一項に記載の方法。
- 前記ポリビニルアルコールが、90mol%~99mol%未満の範囲の加水分解度を有する、請求項35~41のいずれか一項に記載の方法。
- 前記ポリビニルアルコールが、20℃で少なくとも約6cPの4%水溶液粘度を有する、請求項35~42のいずれか一項に記載の方法。
- 前記水溶性ポリマーがセルロースエーテルを含む、請求項35~43のいずれか一項に記載の方法。
- 前記セルロースエーテルがカルボキシメチルセルロースを含む、請求項44に記載の方法。
- 前記蝋エマルジョンが、パラフィン蝋、蜜蝋、またはこれらの組合せを含む、請求項34~45のいずれか一項に記載の方法。
- 前記蝋エマルジョンが、前記蝋エマルジョンの総重量に基づいて、約5重量%~約30重量%の範囲の量で前記パラフィン蝋、前記蜜蝋、またはこれらの組合せを含む、請求項46に記載の方法。
- 前記一次組成物を提供するために、前記水溶性ポリマーおよび前記蝋エマルジョンを、可塑剤、充填剤、界面活性剤、ブロッキング防止剤、酸化防止剤、スリップ剤および分散剤の群中の1またはそれを超える追加成分と混合することをさらに含む、請求項34~47のいずれか一項に記載の方法。
- 前記可塑剤が、グリセロール、ジグリセロール、プロピレングリコール、ジプロピレングリコール、エチレングリコール、ジエチレングリコール、トリエチレングリコール、最大MW400のポリエチレングリコール、ソルビトール、2-メチル-1,3-プロパンジオール、エタノールアミン、トリメチロールプロパン(TMP)、ポリエーテルポリオール、イソマルト、マルチトール、キシリトール、エリスリトール、アドニトール、ズルシトール、ペンタエリスリトール、マンニトール、または前述のいずれかの組合せを含む、請求項48に記載の方法。
- 前記可塑剤が、ソルビトール、キシリトール、またはこれらの組合せを含む、請求項48または49に記載の方法。
- 前記可塑剤が、前記水溶性ポリマーの100重量部に基づいて、約10PHR~約25PHRの範囲の量で前記一次組成物中に存在する、請求項48~50のいずれか一項に記載の方法。
- 前記蝋エマルジョンが、前記水溶性ポリマーの100重量部に基づいて、約70PHR~約200PHRの範囲の量で前記一次組成物中に存在する、請求項34~51のいずれか一項に記載の方法。
- 前記蝋エマルジョンが、前記水溶性ポリマーの100重量部に基づいて、約90PHR~約120PHRの範囲の量で前記一次組成物中に存在する、請求項52に記載の方法。
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AU2020371791B2 (en) | 2024-03-14 |
BR112022007571A2 (pt) | 2022-07-05 |
KR20220095198A (ko) | 2022-07-06 |
JP7428794B2 (ja) | 2024-02-06 |
WO2021081475A1 (en) | 2021-04-29 |
CN114901736A (zh) | 2022-08-12 |
EP4048724A1 (en) | 2022-08-31 |
AU2020371791A1 (en) | 2022-04-28 |
US20220410543A1 (en) | 2022-12-29 |
MX2022004428A (es) | 2022-08-04 |
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