TWI418458B - 具有環狀構型之多層結構及其製造方法與裝置 - Google Patents
具有環狀構型之多層結構及其製造方法與裝置 Download PDFInfo
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Description
本發明係關於多層結構且更詳言之關於具有環狀構型之多層結構及其製造方法與裝置。
當前多層膜加工技術稱為鑄造膜及吹製膜。鑄造膜法使用平坦平面型製造法且適於製造平坦塑膠膜及塑膜板，其通常具有多達約15%邊緣下料。已知吹製膜法以相同生產線提供更具靈活性的膜寬或板寬變化，在需要頻繁轉變產品且體積專門性較低之應用中達成較佳經濟效益且通常避免與邊緣下料相關之產率損失。
多層膜係藉由已知分層法製造，通常使用單軸鑄造或平面板法或疊層。共擠鑄造膜或板結構通常具有3至5層；然而已知包括數百層之鑄造膜或板結構。舉例而言，早期多層製程及結構顯示於USP 3,565,985、USP 3,557,265及USP 3,884,606中。WO 2008/008875揭示形成具有許多(例如五十至數百)交替泡沫層及膜層之多層結構的相關技術方法。然而所示方法僅引起實質上單軸定向，亦即加工方向。此為不適宜的，因為所得結構可能由於極不平衡之定向而具有不平衡的機械性質。隨後可使用定向法(例如拉幅機法)達成雙軸定向。此等額外方法複雜而昂貴且所需定向度可能與所需不同，因為其存在尺寸限制且在低於多層膜中最高熔點聚合物熔點之相對較低聚合物溫度下產生。
具有層數有限之環狀構型之多層結構被用於許多應用中。此等環狀形狀管樣結構包括例如吹製膜法中之「氣泡」；電線或電纜上之塗層；吹塑物品及其製造中使用之型坯或預成型坯；及管道。該等物品通常含有2至10層且具有由各別歧管供應之環狀層。環狀構型及產品擠出中之定向製程步驟，諸如吹塑物品或吹製膜法中之「氣泡」之膨脹可極適宜用於提供雙軸定向(有時稱為多軸定向)，已知該定向提供具有極適宜物理性質組合之聚合物樹脂物品。
如此項技術中熟知，可藉由將聚合物熔融流饋入環狀模分配歧管中來製造吹製膜、吹塑及其他環狀形狀物品。獲得多層一般需要為各層設計及製作分配歧管或心軸，例如6層環狀結構將使用含有6個個別分配歧管(每層一個)之模來製造。設計及製作此等多個分配歧管以產生具有許多層之環狀結構極為困難且於一個結構中可製造之環狀層數有限。參見例如環狀模之連續歧管分層技術，如Dooley,J.及Tung,H.,Co-extrusion
,Encyclopedia of Polymer Science and Technology,John Wiley ＆ Sons,Inc.,New York(2002)中所教示。
製造具有環狀構型之多層結構的另一方法包括使用螺旋心軸模。在螺旋心軸/分配歧管模中，饋至模分配歧管中之聚合物熔融流流動通過自歧管入口至出口附近螺旋切割之歧管通道，如Extrusion Dies
,Design and Engineering Computations,Walter Michaeli,1984,第146-147頁中所述。流動通過螺旋模之分配歧管不適合在單分配歧管中加工單層以上熔融流，因為會引起多層熔融流不連續且喪失層完整性。
USP 3,308,508、5,762,971及6,413,595揭示於所謂的餅形模(亦稱為平面幾何形狀)中形成環狀多層結構。餅形模包括多個層疊之平面或平坦分配歧管。若干聚合物熔融流各饋入至分配歧管中。藉由在各熔融流離開其分配歧管後將若干同心熔融流接合而形成多層結構。若需要許多層，則需要許多層疊歧管。此可致使模中壓力降較大及滯留時間延長。USP 5,762,971及6,413,595揭示製造具有最多約27層之最終多層結構。
已知使用螺旋餅形模之具有多達11層之多層結構。然而，此等多層結構係類似地藉由將若干螺旋分配歧管彼此層疊形成一個環狀模且在熔融流離開整個環狀模時將其合併而製造。
製造具有環狀構型之多層結構的另一相關技術方法包括使用環狀模，諸如USP 6,685,872中描述之環狀模。如所揭示，於環狀模之一個單分配歧管中饋入3層。所揭示之歧管設計提供具有不均一圓周及經設計之重疊部分之環狀多層結構，其中層結構以重疊區至少維持不重疊區層結構之障壁性質的方式重疊。
US 2008/0157443描述製造型坯之方法及裝置。裝置具有心軸外殼，其具有側通道與心軸通道實質上成橫向。心軸在外表面中具有軸向定向凹口與環繞心軸不斷向下延伸，在凹口之心軸對側彼此相接之兩個流體通道流體連通。儘管其論述具有多達100層之複合流，但實例僅揭示具有多達17層之結構。
然而，一直需要製造具有更多層之環狀多層結構；於模中使用較少數目之分配歧管；製造具有改良之物理與機械性質組合之環狀多層結構；及/或減少加工步驟數且增加環狀結構製造設備之靈活性。
因此，本發明係關於實質上消除一或多個歸因於相關技術限制及缺陷之問題的具有環狀構型之多層結構及其製造方法與裝置。本發明之各種實施例可提供一或多個以下優勢。
本發明之一優勢為提供具有環狀構型且具有許多層之多層結構，該等結構可用以製造以一個步驟達成更均一雙軸定向的物品。
本發明之另一優勢為使用數目減少之分配歧管提供具有環狀構型且具有比先前環狀結構之層數目多及/或薄之層的多層結構。
本發明一項實施例之另一優勢為提供可用以製造吹製膜或吹塑物品之具有環狀構型之多層結構，其中該結構之圓周消除會不當或不利影響結構性質的習知焊接或重疊區。當然應認識到吹製膜產品通常不以環狀結構形式出售或使用，其已經由已知製程步驟由環狀結構轉化為平板產品。
本發明替代實施例之另一優勢為提供具有環狀構型之多層膜/泡沫結構，其具有含有泡沫層之橫截面且容許向下加重(down weighting)並同時維持可接受之其他物理性質平衡。
本發明替代實施例之另一優勢為提供具有環狀構型之多層膜結構，其具有含有控制量之無機填充層使得可調整物理性質之橫截面。
本發明一項實施例之另一優勢為提供具有環狀構型之多層結構，其中達成層數增加並同時一般維持大多數層之層完整性。
在另一替代實施例中，本發明之另一優勢為提供具有環狀構型之多層結構，其在各種應用中具成本效益且已用於或可用於提供具有以下至少一種特性之物品：降低之密度、改良之障壁性、改良之層均一性、改良之強度、改良之絕緣性、改良之韌性、改良之抗撕裂性、改良之抗穿刺性及改良之拉伸效能。
本發明之其他特徵及優勢於以下描述中闡明且自描述而部分顯而易見或可藉由實踐本發明而獲悉。本發明之優勢可藉由在書面描述及其申請專利範圍以及附圖中所特別指出之結構與方法來實現及達成。
為達成此等優勢且根據本發明目的，如本文中例示且廣泛描述，提供本發明之以下實施例及較佳態樣。本發明之一項實施例為製造環狀多層結構之方法，包含：提供具有至少四層熱塑性樹脂材料之多層流；將多層流饋入環狀模之分配歧管中形成環狀多層流；及將環狀多層流自環狀模移除形成環狀多層結構。
在另一實施例中，本發明方法包含提供具有至少兩層熱塑性樹脂材料之多層流；以至少一層封裝層封裝多層流形成經封裝之具有至少四層熱塑性樹脂材料之多層流；將該經封裝多層流饋至環狀模分配歧管中形成環狀多層流；及將該環狀多層流自環狀模移除形成環狀多層結構。在其他替代實施例中，分配歧管具有圓柱形主體、錐圓柱形主體或平面主體。
在替代實施例中，分配歧管具有十字頭型幾何形狀，其中多層流分成至少兩個物料流，其中兩個物料流以相反方向環繞分配歧管圓周移動，較佳為在一項實施例中，其中物料流重疊於變形十字頭分配歧管上之一區域中。在另一替代態樣中，將多層流經由具有弧形流動方向之圓形管流道饋入環狀模之單分配歧管中，其中弧之曲率半徑大於管直徑。
根據本發明之另一替代實施例，該方法進一步包含使用至少一個額外分配歧管提供至少一個額外流至環狀模內之多層流中且在該情況中，該額外流可視情況為多層流。本發明之其他可選方法進一步包含在提供多層流之前，添加發泡劑或無機填充劑至至少一種熱塑性樹脂材料中。
在另一替代實施例中，本發明方法包含將型坯形式之環狀多層結構置於吹塑模內且使環狀多層結構膨脹為模之形狀或拉伸熔融狀態之環狀多層結構以使該結構雙軸定向；及冷卻該結構且視情況包括再加熱冷卻之結構至低於結構中最高熔點聚合物熔點之溫度；單軸或雙軸拉伸結構以使結構定向；及隨後冷卻該結構。在其他可選態樣中，多層流包括多於約5層及或者多於約25層。
在另一替代態樣中，本發明為具有均一厚度、至少四層且包含重疊及不重疊圓周區之環狀多層物品；其中不重疊區之層結構在重疊區成雙倍；其中亦可選擇使物品在微層組件之任一側上包含兩個外皮層提供至少15層。在其他替代實施例中，多層吹製膜包含具有至少27層之微層組件。
在另一替代實施例中，本發明為包含以下之裝置：給料區段，具有視情況存在之層倍增器，提供具有至少四層之多層流至環狀模之歧管；及環狀模，具有至少一個分配歧管擠出多層流。視情況在本發明裝置中，環狀模歧管為在擠出多層流之前使物料流分開且提供物料流重疊區之變形十字頭設計，及/或具有圓柱形主體、錐圓柱形主體或平面主體。
在本發明裝置之另一替代實施例中，如上所述之裝置在給料區段(或視情況存在之層倍增器)與歧管之間進一步包含封裝模用以在物料流進入歧管中之前將其封裝，及/或在封裝模與歧管之間進一步包含弧形圓形管流道，且其中圓形管流道之物料流入口端定向為與圓形管流道之物料流出口端呈約90度角。
在本發明之較佳替代實施例中，本發明之吹製多層膜及方法因其環狀模製造、雙軸定向(相對於鑄造多層膜)及/或增加之層數而提供一般改良之性質。通常可獲得抗張、韌性、拉伸及/或障壁性質中一或多者之改良。儘管使用拉幅之鑄造膜亦可獲得雙軸定向，但此為昂貴、資本密集型單元操作。
應瞭解本發明之以上一般描述及以下詳細描述皆為例示性及解釋性的且意欲提供對所主張之本發明之進一步解釋。
為提供對本發明及本發明之可選實施例的進一步理解而包括附圖，將其併入本說明書中且構成本說明書之一部分，說明本發明實施例且與描述一起用以解釋本發明原理。
現詳細參考本發明實施例，其實例於說明書中揭示且於附圖中說明。熟習此項技術者顯而易見可在不偏離本發明精神或範疇之情況下在本發明中進行各種修改及變化。因此，本發明意欲涵蓋對本發明之修改及變化，只要其在隨附申請專利範圍及其相等物範疇以內。
本揭示案中之數值範圍包括自下限值至上限值且包括下限值及上限值，增量為一個單位之所有值，其限制條件為在任何下限值與任何上限值之間分開至少兩個單位。舉例而言，若組成、物理或其他性質(諸如厚度及密度降低等)大於10，則意欲明確列舉所有個別值，諸如10、11、12等及子範圍，諸如100至144，155至170，197至200等。對於含有小於1之值或含有大於1之分數(例如1.1，1.5等)之範圍而言，按需要將一個單位視為0.0001、0.001、0.01或0.1。對於含有小於10之單位數(例如1至5)之範圍而言，通常將一個單位視為0.1。此等僅為特別預期之實例，且所列舉之最低值與最高值之間數值之所有可能組合皆視為於本揭示案中明確闡述。
根據本發明及下文中所述製造環狀多層結構之方法包括獲得及利用多層流，其通常由多層共擠製程步驟提供且視情況可由其他層倍增製程步驟提供。所主張方法視情況包括封裝製程步驟。所主張方法包括在環狀模製程步驟中提供具有至少四層熱塑性樹脂材料之多層流至分配歧管中。視情況吹製膜製程步驟或吹塑製程步驟可在自環狀模出口接受多層流後進行。
多層流
如本文中關於熱塑性樹脂材料所使用之術語「物料流」或「熔融流」係指該材料(通常為如下文進一步描述之聚合物或聚合材料)經歷過熱塑化(加熱至處於或高於材料熔融溫度或玻璃轉移溫度之溫度，亦即材料變為充分液體狀以在此實施例中所提及之設備中流動的溫度)，在充分壓力條件下係可熱塑性加工及可流動。可藉由許多已知加工技術提供物料流。物料流較佳由為獲得流動均一性而視情況包括齒輪泵的擠壓機(亦即藉由擠出)提供，但其亦可提供為使用齒輪泵之其他熱塑化製程步驟之輸出物。具有熱塑性樹脂材料層之多層流可藉由已知分層技術(包括原先熟知之共擠法)及視情況亦藉由已知層倍增技術如下文進一步詳細論述由兩個或兩個以上物料流提供。
多個熱塑性樹脂材料流可經由使用已知分流技術共擠得到，其中安置兩個或兩個以上孔使得所得擠出物流熔合且焊接在一起成為多層流且繼續通過流道朝向環狀模。多層流可為例如一般平坦矩形層狀流，亦即厚度及寬度約相同之一般平坦平面層，如WO 2008/008875、USP 3,565,985、USP 3,557,265及USP 3,884,606中所教示，其皆以引用的方式併入本文中。或者，可藉由封裝技術，諸如USP 4,842,791中圖2及5所示使用層疊於核心周圍之一或多個一般圓形或矩形封裝層封裝或如USP 6,685,872中圖8所示使用一般圓形不均一封裝層封裝，來提供多層流之2層或2層以上。可設想封裝層具有在多層流提供至及離開環狀模時提供2個外層至物料流的作用。USP 4,842,791及USP 6,685,872以引用的方式併入本文中。
在本發明中，提供多層流之共擠法包括同時或相繼合併至少第一熱塑性樹脂材料熔融流與至少第二熱塑性樹脂材料熔融流及視情況額外物料流。在同時分層中，可在物料流之相同點添加或合併各層。若例如樹脂材料流變學類似，則可進行同時分層。在相繼分層給料區段中，在沿物料流之不同點添加額外層。舉例而言，可藉由分流法在同時合併物料流中提供多層流，如USP 3,565,985、USP 3,557,265及USP 3,884,606中所教示。如USP 3,557,265及USP 3,884,606中所教示，其多層流亦稱為「相互交叉(interdigitated)」或「交錯(interleaved)」的。
相繼物料流添加形式於USP 4,842,791及USP 6,685,872中顯示，其皆以引用的方式併入本文中，其中藉由封裝初始物料流來提供多層流。
在本發明之一項實施例中，如圖1中所示，將來自單螺桿擠壓機1
及5
之材料饋入具有至少兩個孔之兩層A/B給料區段模6
中。在本發明之另一實施例中，如圖2中所示，將來自單螺桿擠壓機1
及2
之材料饋入具有至少兩個孔之兩層A/B給料區段模4
中。
視情況選用之層倍增
視情況在分流共擠法或另外提供初始多層流後，接著可對多層流進行如此項技術中一般已知之進一步之層倍增製程步驟。參見例如USP 5,094,788及USP 5,094,793，其以引用的方式併入本文中，其教示多層流之形成，藉由將含有熱塑性樹脂材料之多層流分為第一子流、第二子流及視情況存在之其他子流且將多個子流以層疊方式合併且壓縮，藉此形成多層流。多個層疊子流在多層流中以彼此相鄰且一般平行的關係彼此融合。在多層流內，多個子流展現均一性、連續性及特別計算之厚度以提供具有所需性質之所需組態。層倍增法可產生含有許多層(諸如數百層)之多層流。
對於用於本發明中之多層流而言，視諸如所需性質、製造成本、最終用途等因素而定，物料流含有至少4層，較佳多於約4層，較佳多於約5層，較佳多於約8層，較佳多於約10層，較佳多於約11層，更佳多於約20層，更佳多於約25層，更佳多於約27層，更佳多於約30層或多於約40層或多於約50層或多於約60層或多於約70層或多於約75層或多於約80層或多於約90層。又，儘管物料流中層數可能基本上無限，但可使物料流最佳化而含有至多且包括約10000層，較佳至多且包括約1000層，更佳至多且包括約500層或至多且包括約400層或至多且包括約300層或至多且包括約250層或至多且包括約200層或至多且包括約175層或至多且包括約150層或至多且包括約125層或至多且包括約100層。如此項技術中已知，如一或多種上述方法中所提供之含有許多層之多層結構通常稱為「微層」結構。
在本發明之一項實施例中，如圖1中所示，將離開給料區段模6
之材料饋入至一系列視情況存在之層倍增器7
中。在本發明之另一實施例中，如圖2中所示，將離開給料區段模4
之材料饋入至一系列視情況存在之層倍增器5
中。
視情況選用之封裝
視情況，若尚未用以提供多層流中至少兩層，則接著可藉由如上所述之已知方法使用封裝來提供保護內層結構之表面層，諸如微層結構中提供之極薄層。參見例如USP 5,269,995，其以引用的方式併入本文中。舉例而言，在本發明中可使用如圖4所示及如參考USP 6,685,872(以引用的方式併入本文中)中所揭示之圖4、5、7及8所述之封裝模。使用相對均一封裝層之封裝亦可根據US 4,842,791之教示提供，其以引用的方式併入本文中。如USP 6,685,872中所述，可使用不均一封裝層，尤其若需要使用其中所示類型之變形十字頭環狀模來提供所需重疊區時。如其中所教示，不均一模間隙可提供封裝層之適當厚度變化。舉例而言，在本發明之一項實施例中，可封裝多層流之整個圓周或周邊。舉例而言，可完全封裝多層複合流之末端。例如，若多層流包括兩層且接著經封裝，則經封裝多層流之橫截面顯示四層。
封裝層可適宜地改良多層流流經封裝模、環狀模及任何後續操作時之流動穩定性，諸如USP 6,685,872中以封裝模所示。封裝層亦可具有功能性目的，例如用以改良風化情況、UV穩定性等。在本發明之替代實施例中，可替代地向多層流之不足整個圓周或周邊提供視情況存在之封裝層作用，包括藉由使用多於獲得基本所需環狀結構性質所需數目之保護性表面層或許多給料區段層。封裝層例如可為可隨後移除或損壞之犧牲層。如圖1中所示，於視情況存在之封裝模8
中使用視情況存在之擠壓機3
將至少一層封裝層併至多層複合流上。如圖2中所示，於視情況存在之封裝模6
中使用視情況存在之擠壓機3
將視情況存在之封裝層併至多層複合流上。
或者，可視需要僅封裝多層流圓周之一部分。舉例而言，物料流頂部及底部上可塗覆有塗層而同時暴露側邊。
視情況存在之流道
視情況在本發明之一些替代實施例中，在一般矩形或其他非圓形多層流形成後，物料流需行進相對長距離(例如大於流動直徑之約5倍至10倍)或需要改變流動方向(例如由水平擠出平面變為垂直吹製膜製程步驟)。在該等情況中，可提供圓形管流道供經封裝多層流進入。非圓形流之橫截面形狀平穩地轉變為圓形，在物料流中維持圓形橫截面時使由多層流中彈性力產生之次生流動所可能引起的層變形降至最低。若使用，則此圓形管流道可能形成為曲率半徑相對大於管直徑之弧以便改變多層流流動方向，例如由水平變為垂直。圓形管流道之排出端流動方向可定向為與進入圓形管流道之流動方向呈高達90度或大於90度之角。為使圓形管流道之流動方向變化約90度，圓形管流道曲率半徑(提供流動方向變化)與圓形管流道內徑之比率較佳大於1:1，較佳大於2:1，更佳大於3:1，且更佳大於5:1。圓形管橫截面中應維持多層流直至其到達環狀模之分配歧管通道，此時多層流可平穩地由圓形幾何形狀轉變為環狀模分配歧管通道之適當幾何形狀。
圖3顯示來自曲率半徑相對大於管直徑之圓形管流道之多層流樣品。圓形管流道曲率半徑為3.4，圓形管流道內徑為1.0且兩者比率為3.4。多層流包括著色黑色及白色以供比對之27層交替聚苯乙烯層。其係使用兩個在420℉下運作且速率為12 lb/hr之1.25吋擠壓機製造。方法細節及設備於下文程序中描述。停止擠壓機，且使多層流在圓形管流道中冷卻並硬化。接著移除圓形管流道，留下硬化之多層材料。流動方向朝向底部右側標記為4之位置。
4的橫截面區之像片如圖4所示(其為由圓形管流道之圓形幾何形狀轉變為正方形幾何形狀之後)。圖4顯示各層在其環繞彎曲流向標記4之位置時保持完整。
圖5顯示十字頭模100之一部分。在十字頭模中，流動方向必須由水平擠壓機平面變為垂直模平面。多層流流入管105中之模中。其經曲率半徑相對大於管直徑之圓形管流道110進入模100中。流動方向自進入時之水平轉動90°為垂直向上。物料流進入環繞模而導向對側重疊區之通道115中。材料自通道115向上流經通道120且流出模。熟習此項技術者應認識到在模中的流動可視特定模類型而定向上或向下。
圖6顯示具有小曲率半徑之十字頭模200之一部分。物料流自管205進入模中。圓形管流道210之曲率半徑相對小於管直徑，例如小於1:1。流動方向自水平轉動90°為垂直。物料流進入環繞模之通道215中，且自通道215向上通過通道220且離開模。
圓形管流道可在模內(如圖5中所示)或在模外。若其在模外，則管流道使物料流在進入模中之前由水平變為垂直，且模中物料流垂直於環繞模之通道。
因此，如上所述，多層流可由包括以下一或多者之各種不同來源或步驟提供：給料區段。視情況存在之層倍增器、視情況存在之封裝模或視情況存在之圓形管流道。
環狀模製程
藉由饋入或傳遞至環狀模之單分配歧管中來將多層流提供至環狀模中以在其離開環狀模時形成環狀多層流。分配歧管分配多層流形成環狀形狀並同時維持多層流之層連續性。單分配歧管可具有例如圓柱體形狀、錐圓柱體形狀或平面體形狀，均饋入及離開環狀模。
可向環狀模供應多於一個多層流，但各多層流具有其自身之分配歧管。舉例而言，在圖1中可用一或多個擠壓機、給料區段、層倍增器及封裝模之配置來替換擠壓機2(或擠壓機4或兩者)以獲得第二(或第三)多層原料流流入分配歧管11(或分配歧管9)中。
應注意在典型工業使用中，術語「心軸」通常指或包括「分配歧管」且在一定程度上可與彼術語互換使用。如本文中關於環狀模所使用，分配歧管為接受且轉移物料流橫越且環繞一般圓柱形、平面形或錐圓柱形心軸單元表面而產生環狀構型流離開環狀膜的流動空間或流道區。其通常藉由中心心軸單元及外或上殼或板單元產生且位於其之間。歧管分配聚合物熔融流環繞心軸且使物料流形成環狀形狀離開模。
若例如歧管具有平面主體，則其位於兩個水平定向之板型單元之間且導向垂直定向之環狀模。在此情形中，歧管將定向為一般與流動方向及多層流內的層界面平行且共平面的方向。平面歧管適宜地分配多層流且使其形成環狀形狀離開模。
在一項實施例中，單分配歧管可具有十字頭型幾何形狀。在具有十字頭型幾何形狀之分配歧管中，如例如USP 6,685,872之圖9中所示，進入之聚合物熔融流在歧管入口處或歧管入口處附近分成兩個物料流以一般相反之圓周方向環繞心軸行進，且亦提供極細物料流在軸向上沿心軸流向模出口。分開之聚合物熔融流接著以相反方向繼續環繞歧管，以在心軸對側或心軸對側附近使物料流相接或接合且形成一般環狀流朝向環狀模出口行進。在一些十字頭型環狀模中，視模構造及/或材料選擇而定，在兩個物料流相接之接頭或接縫處可能存在明顯焊接線。此在一些應用中可能不良而在其他應用中可能適宜。
在本發明之替代實施例中，單分配歧管具有變形十字頭型幾何形狀。分配歧管之變形十字頭型幾何形狀於以引用的方式併入本文中之USP 6,685,872之圖9、10、11及12中描述且顯示。此具有變形十字頭型幾何形狀之分配歧管包括一主體及一對自分配歧管入口以相反方向環繞心軸主體延伸之歧管通道。歧管通道之相對端彼此重疊且大幅減少焊接線之顯現及影響。
在較佳之變形十字頭環狀模實施例中，多層流可分為至少兩個分開之物料流，其中各分開之物料流以相反方向在環繞分配歧管主體圓周之歧管通道對中行進。在另一較佳實施例中，分開之物料流在分配歧管上歧管通道相對端彼此重疊之區域上彼此重疊，但保持分離。較佳地，重疊距離經最佳化以供多層結構於重疊區中提供所需物品性質。
如本文中所使用，術語「重疊區中所需物品性質」係指可藉由變形十字頭模提供之若干可能之作用。舉例而言，可設計重疊的歧管區以提供沿圓周環繞環狀結構，自不重疊區延伸至重疊區中且縱穿重疊區之一般一致性質。舉例而言，USP 6,685,872揭示使用此技術維持一致的障壁性質。或者，因為重疊區具有兩倍數量之厚度為平均層厚度一半之層，所以其可能企圖展現物理或光學性質之顯著轉變。具有該顯著轉變可能以許多方式適宜用於環狀結構。舉例而言，其可能用以實現環狀物品之一致定向或定位。其可能提供容易的方式來定位重疊區以在其不利於物品圓周平衡時將其移除。
關於平面模(「餅形」模)，可藉由彼此末端相疊置放使得兩個末端高度不同(而非如變形十字頭模之徑向距離不同)來形成重疊。
可以多種方式來形成重疊，包括(但不限於)如圖7A-B所示之階梯式變化或斜坡式變化。令人驚奇地發現無論藉由階梯式變化還是斜坡式變化形成，重疊區中之層均保持完整。此於圖8A-B及9A-B中證實。圖8A-B為吹製膜中微層之AFM影像。膜之核心中具有交替低密度聚乙烯與AffinityTM
聚烯烴塑性體之27層微層。膜係使用以50%/50%層比率運作之1.25吋及1.75吋擠壓機製造。核心速率為約60 lb/hr之總線速率中約12 lb/hr。方法細節及設備於下文程序中描述。圖8A顯示吹製膜中重疊區外存在完整微層。圖8B顯示圖8A膜之重疊區，其在相同總膜厚度下具有多達兩倍之層且各層保持完整。
圖9顯示吹製膜重疊區中微層之TEM影像。截面A及B之核心中各含有交替低密度聚乙烯與AffinityTM
聚烯烴塑性體之100層微層。膜係使用以50%/50%層比率運作之1.25吋及1.75吋擠壓機製造。核心速率為約60 lb/hr之總線速率中約12 lb/hr。方法細節及設備於下文程序中描述。各層完整。
應注意USP 6,685,872中所述之結構中之障壁層比本文中所述微層厚得多。與許多較薄層相比，操縱且維持少數較厚層完整較為容易。此外，操縱比典型吹製膜模小之吹塑模中之層較為容易。
如圖1中所示，將視情況經封裝之多層流饋入至環狀模之分配歧管10
中。視情況額外流可藉由兩個擠壓機2
及4
製造且可藉由環狀模內之額外分配歧管9
及11
施加於經封裝多層流。額外流可各自為單層或多層流，包括與最初的經封裝多層流相同或不同之多層流。分配歧管9
及11
各自可為習知歧管或可具有與分配歧管10
相同之變形十字頭型幾何形狀。
接著，環狀多層流離開環狀模，亦即自環狀模移除，形成環狀多層結構。
分開之物料流重疊形成物料流末端不暴露於所得結構之表面之物料流。在一項實施例中，藉由封裝及重疊多層流，可避免所得環狀多層結構之表面上出現分層之末端且消除習知焊接線。消除分層之末端及/或焊接線有益於改良所得環狀多層結構之機械及物理性質。在至少一項實施例中，消除分層之末端有益於藉由與環狀物品其餘圓周之性質相比，於重疊區中維持至少一致或改良之性質而改良環狀多層結構之性質。
吹製膜及/或吹塑製程
在自環狀模排出後，可在環狀多層結構於熔融狀態或半固體狀態時將其拉伸以使該結構單軸、雙軸或多軸定向。舉例而言，膨脹至模中產生徑向定向、軸向定向及不同厚度可稱為多軸定向。又，舉例而言單軸定向可用以形成電線及電纜塗層、管道、管等。在使用膨脹之熱塑性樹脂材料之實施例中，拉伸獲得膨脹之熱塑性樹脂材料內發泡單元之宏觀單元定向。發泡單元可具有不同的巨單元定向度。
拉伸之實例包括(但不限於)(i)在環狀模與拉伸捲筒之間單軸拉伸，(ii)三維膨脹，游離表面吹製膜起泡或型坯膨脹至模中(吹塑)，及(iii)拉伸構型縱穿校準器及/或淬滅槽。基於單軸拉伸法之典型拉伸比率在約2:1至約50:1，較佳約5:1至約30:1之範圍內。單軸「拉伸比」為拉伸速度與環狀結構離開模之速度之比率。雙軸拉伸法之吹脹比在約1.5:1至20:1，較佳約2:1至5:1之範圍內。吹脹比為最終環狀產品或物品之直徑與離開環狀模時物品直徑之比率。接著，藉由輔助(例如空氣冷卻、淬滅等)或無輔助(亦即平衡至周圍室溫)之冷卻使環狀多層結構穩定。
如圖1中所示，在一項實施例中，可形成吹製膜泡12
。
如圖2中所示，在吹塑物品形成中，環狀多層結構(型坯)可置於吹塑模中且膨脹為模之形狀形成環狀吹塑部件。例示性吹塑物品可使用典型吹塑頭7
及模腔8
形成。吹塑物品及吹塑製程之吹脹比在約2:1至10:1，較佳約3:1至5:1之範圍內。
視情況可在環狀多層結構上進行再加熱製程。將該結構再加熱至低於結構中最高熔點聚合物熔點之溫度。接著，將結構於半熔融狀態單軸或雙軸拉伸以使該結構定向且隨後使其冷卻。經冷卻之結構可用於例如收縮膜中。
所得環狀多層結構
本發明之環狀多層結構視諸如所需性質、製造成本、最終用途等之因素而定，可含有例如至少約4層，較佳多於約4層，較佳多於約5層，較佳多於約8層，較佳多於約10層，較佳多於約11層，更佳多於約20層，更佳多於約25層，更佳多於約27層，更佳多於約30層或多於約40層或多於約50層或多於約60層或多於約70層或多於約75層或多於約80層或多於約90層。應認識到在某些實施例中，結構上重疊區中之層數可能為結構上其他區域中層數之兩倍。又，儘管層數理論上接近無限，但可使物料流最佳化以含有至多且包括約10000層，較佳至多且包括約1000層，更佳至多且包括約500層或至多且包括約400層或至多且包括約300層或至多且包括約250層或至多且包括約200層或至多且包括約175層或至多且包括約150層或至多且包括約125層或至多且包括約100層。如此項技術中已知，如一或多種上述方法中所提供之含有許多薄層之多層結構通常稱為「微層」結構。
在本發明之一項實施例中，所得環狀多層物品具有一般均一厚度，且包含重疊及不重疊圓周區；其中不重疊區之層結構在重疊層中成雙倍。如上所提及，在變形十字頭模提供重疊區之某些實施例中，結構上重疊區中之層數可能為結構上其他區域中層數之兩倍。
如本文中關於環狀圓周使用之術語「一般均一厚度」主要係指在環狀多層物品具有重疊區之實施例中，重疊區厚度可為、通常預期為及典型地為與不重疊區實質上相同之厚度。此當然涵蓋較小、偶然及無意的厚度差異。因此一般厚度均一性意謂較佳地環繞環狀圓周，尤其任何重疊區與不重疊區之間之結構厚度變化(若存在)一般小於10%，較佳小於5%，更佳小於2%，最佳小於1%。在本發明之其他實施例中，模可能企圖在環狀結構之圓周中提供稍微不均一之厚度。
由此處及其他部分中對本發明之一般描述顯而易見，本發明提供環狀結構中多個環狀層及尤其環狀微層之益處，其中多個層之益處係環繞環狀物品圓周而提供且維持。如上所論述，在提供重疊區之情形下，可存在層自身不完全為環狀連續而是具有充分層重疊及/或冗餘以補償重疊區中層薄度及末端點的區域。舉例而言，可設計重疊區以提供沿圓周環繞環狀結構，自不重疊區延伸至重疊區中且縱穿重疊區之一般一致性質。
如多層化及微層化之實踐已知，平均層厚度隨結構中微層/多層結構或微層/多層組件之最終厚度及彼厚度中所獲層數而變且可由其計算。微層/多層結構或用作結構中組件之較佳厚度隨不同特定應用而變化且於下文中進一步論述。可根據本發明之各種態樣及實施例，藉由選擇且使用適當多層原料流及層倍增器技術，來形成具有各種重複層單元或重複模式(諸如重複A/A、A/B、A/B/A、A/B/C、A/B/C/B/A等)之分層構造的環狀多層結構。結構厚度可視各種因素而變化，諸如所使用之熱塑性樹脂材料，材料是否膨脹，所需結構性質等。又，應瞭解視其隨後是否與來自多層環狀模之額外層合併而定，多層/微層結構可形成膜結構之全部或一部分。在視情況存在之本發明替代實施例中，本發明之環狀多層結構實際上為主結構組件且與通過一或多個額外模歧管之額外層合併。
在多層環狀結構用作不膨脹膜應用(較佳為吹製環狀膜結構)之全部或一部分之本發明一項實施例中，該結構厚度為至少約7微米(0.3 mil)，較佳至少約10微米(0.4 mil)，更佳至少約15微米(0.6 mil)。對於膜應用而言，膜厚度通常小於約380微米(15 mil)，更佳小於約250微米(10 mil)且更佳小於約125微米(5 mil)。
將該等結構用於其他類型物品(諸如可吹塑型坯、擠出之環狀構型物品(例如管道)，尤其可使用膨脹層之物品)可能需要厚度為至少約1毫米(mm)，較佳至少約1.6 mm且對於管道而言厚度為至多約152毫米(6吋)，較佳至多且包括約90 mm(3.5吋)。對於吹塑物品自身而言，壁厚度在約1 mm至約13 mm範圍內。
視情況可存在外「皮」提供於環狀多層結構之表面(使用額外環狀模歧管)上或包括於如上所述之環狀多層結構中。其可為例如於環狀多層結構之一個或兩個相對側上所添加的一或多個共擠環狀頂蓋層或所包括的過多之多個外皮層。若存在則外皮層厚度可佔最終產品結構之大於0且至多約90%，或基於結構總厚度佔至多約80%厚度，或佔至多約70%厚度，或佔至多約60%厚度，或佔至多約50%厚度或佔至多約45%或至多約40%或至多約30%厚度。若使用則外皮一般佔至少約1%厚度，或至少約5%厚度或至少約10%或至少約20%或至少約30%，或至少約40%或至少約45%或至少約50%，或至少約60%或至少約70%或至少約75%或至少約80%厚度。
樹脂層(及視情況存在之膨脹層)材料
多層結構中之層可由相同材料或兩種或兩種以上不同材料製成。
可提供為熱塑性樹脂流且形成膜之任何熱塑性樹脂材料皆可用作本發明製程中之物料流及本發明物品中之層。對其之選擇係由物品所欲用途以及對其他層或物料流選擇之任何黏著及/或加工要求所決定。較佳熱塑性樹脂材料包括熱塑性聚合物。如本文中所使用之「聚合物」意謂藉由使單體(相同或不同類型)聚合而製備之聚合化合物。通用術語「聚合物」涵蓋術語「均聚物」、「共聚物」及「三元共聚物」以及「互聚物」。
「互聚物」意謂藉由使至少兩種不同類型之單體聚合所製備之聚合物。通用術語「互聚物」包括術語「共聚物」(其通常用以指由兩個不同單體製備之聚合物)以及術語「三元共聚物」(其通常用以指由三種不同類型單體製備之聚合物)。
舉例而言，可使用熱塑性聚烯烴聚合物(亦稱為聚烯烴)且適於實踐本發明。「聚烯烴聚合物」意謂由一或多種烯烴產生之熱塑性聚合物。聚烯烴聚合物可具有一或多個取代基，例如諸如羰基、硫醚基等之官能基。對於本發明之目的而言，「烯烴」包括具有一或多個雙鍵之脂族及脂環化合物。代表性烯烴包括乙烯、丙烯、1-丁烯、1-己烯、1-辛烯、4-甲基-1-戊烯、丁二烯、環己烯、二環戊二烯及其類似物。其包括(但不限於)聚乙烯(PE)、聚丙烯(PP)及聚丁烯(PB)及聚氯乙烯(PVC，硬質及可撓性)。
適用烯烴聚合物之特定實例包括超低密度聚乙烯(ULDPE，例如Dow Chemical Company(「Dow」)製造之ATTANETM
乙烯/1-辛烯聚乙烯，典型密度在約0.900至0.915之間且典型熔融指數(I2
)在約0.5至10之間)、線性低密度聚乙烯(LLDPE，例如由Dow製造之DOWLEXTM
乙烯/1-辛烯聚乙烯，典型密度在約0.915至0.940之間且典型I2
在約0.5至30之間)、均勻分支之線性乙烯/α烯烴共聚物(例如Mitsui Chemicals America公司之TAFMER聚合物及ExxonMobil Chemical(ExxonMobil)之EXACTTM
聚合物)、均勻分支之實質上線性乙烯/α烯烴聚合物(例如由Dow製造及USP 5,272,236、5,278,272及5,380,810中描述之AFFINITYTM
及ENGAGETM
聚合物)、催化線性統計烯烴共聚物(例如由Dow製造且於WO 2005/090425、2005/090426及2005/090427中描述之INFUSETM
聚乙烯/烯烴嵌段聚合物，尤其聚乙烯/α烯烴嵌段聚合物及尤其聚乙烯/1-辛烯嵌段聚合物)及高壓游離基聚合乙烯共聚物，諸如乙烯/乙酸乙烯酯(EVA)及乙烯/丙烯酸酯及乙烯/甲基丙烯酸酯聚合物(例如分別為E. I. Du Pont du Nemours ＆ Co.(Du Pont)之ELVAX及ELVALOY聚合物)及乙烯/丙烯酸及乙烯/甲基丙烯酸(例如Dow之PRIMACORTM
EAA聚合物及Du Pont之NUCREL EMAA聚合物)、各種聚丙烯樹脂(例如由Dow製造之INSPIRE及VERSIFY聚丙烯樹脂，由ExxonMobil製造之VISTAMAXX聚丙烯樹脂，及無規共聚物聚丙烯(「RCP」))及環烯或環狀烯烴聚合物及共聚物(分別為「COP's」及「COC's」，COC's包括例如來自Topas Advanced Polymers之Topas牌聚合物且COP's包括例如來自Zeon Chemicals之Zeonex牌聚合物)。COP's及COC's已知且描述於例如EP-A-0 407 870、EP-A-0 485 893、EP-A-0 503 422及DE-A-40 36 264中，其以引用的方式併入本文中。已知所使用之COP及COC樹脂由一或多種環烯(諸如降冰片烯)組成。
在本發明之替代實施例中，多層流及環狀多層結構中之一或多層為LLDPE。較佳LLDPE聚合物為乙烯與至少一種C3
-C20
α烯烴之乙烯互聚物。乙烯與C3
-C12
α烯烴之LLDPE共聚物尤佳。該等共聚單體之實例包括C3
-C20
α烯烴，諸如丙烯、異丁烯、1-丁烯、1-己烯、1-戊烯、4-甲基-1-戊烯、1-庚烯、1-辛烯、1-壬烯、1-癸烯及其類似物。較佳共聚單體包括丙烯、1-丁烯、1-戊烯、1-己烯、4-甲基-1-戊烯、1-庚烯及1-辛烯，且1-辛烯尤佳。
其他適合之熱塑性樹脂材料包括由一或多個單亞乙烯(monovinylidene)芳族單體製備之單亞乙烯芳族聚合物。代表性單亞乙烯芳族單體包括苯乙烯、甲苯、α甲基苯乙烯及其類似物。單亞乙烯芳族聚合物可具有一或多個取代基，例如諸如羰基、硫醚基等之官能基。適用作本發明多層流及環狀多層結構中之一或多層之單亞乙烯芳族聚合物實例包括聚苯乙烯、聚苯乙烯-丙烯腈(SAN)、橡膠改質之聚苯乙烯丙烯腈(ABS)及橡膠改質之聚苯乙烯(HIPS)。
適用作本發明多層流及環狀多層結構中一或多層之其他熱塑性樹脂材料包括聚酯，諸如聚對苯二甲酸伸乙酯及聚對苯二甲酸伸丁酯；聚碳酸酯樹脂；聚乳酸；聚醯胺，諸如耐綸樹脂(nylon resin)，包括耐綸6，耐綸66及耐綸MXD6；熱塑性聚胺基甲酸酯；乙基纖維素；聚(氯乙烯)-偏二氯乙烯(PVDC)；聚乙烯乙烯基醇(EVOH)；丙烯酸甲酯-偏二氯乙烯共聚物；聚甲基丙烯酸甲酯；及其類似物。
所選擇之用於此等層中之熱塑性樹脂材料較佳展現所得環狀多層結構用於指定應用之最佳性質。在較佳實施例中，基於最終所得結構中所需性質選擇材料。舉例而言，若需要收縮性質，則可選擇產生適當收縮性質之材料，諸如聚烯烴樹脂層。若需要障壁性質，則可選擇產生適當障壁性質之材料，諸如PVDC或EVOH。若需要黏著性質，則選擇在其他層之間產生適當黏著接合作用的材料，諸如EVA及EAA。舉例而言，可使用密度不同之聚乙烯樹脂使硬度及韌性最佳化。最終產品中所需性質可影響對用於多層結構之材料的選擇。可選擇材料使得所使用材料之流變學彼此互補且起作用。
此外，可視需要併入添加劑。通常併入聚合物組合物中獲得各種功能之典型添加劑包括催化劑或促進劑、界面活性劑、阻燃劑、孔隙率控制劑、抗氧化劑、著色劑、顏料、填充劑及其類似物。一般併入習知量之該等添加劑。
用於本發明方法之多層流之一或多個物料流層中的熱塑性樹脂材料可視情況含有能夠提供膨脹組合物之起泡劑。亦即多層流中多個熱塑性樹脂材料流可獨立提供膨脹或不膨脹組合物。在本發明替代實施例中，至少一個物料流包括起泡劑以提供膨脹組合物。如此項技術中一般熟知，膨脹組合物包括起泡劑、膨脹劑或發泡劑。此外，膨脹熱塑性樹脂組合物中可併入一或多種產生所需功能之組合物，諸如氣體障壁(例如氧氣、二氧化碳等)組合物(例如乙烯乙烯基醇共聚物或聚偏二氯乙烯之膜組合物)；實質上運作以防液體或濕氣自層之一側橫穿至層之另一側的液體或濕氣障壁組合物；實質上運作以防化學物質或氣體自層之一側橫穿至層之另一側的化學物質障壁組合物；氧清除劑調配物等。
包含膨脹或發泡層之多層環狀結構可為硬質或可撓性的且包括吹製膜及鑄造膜、管、電線塗層、纖維及其他具有環狀構型之形狀。
視需要多層結構可包括再循環材料。舉例而言，在吹塑應用中，吹塑操作中的下料可在總體結構中用作一層。此下料材料包括用於多層結構中之所有樹脂。對於複雜部件，再循環可總計達總結構的50%。再循環材料可用作微層結構中之一或多層，其可位於微層結構與任何皮層之間，或其可用作皮層。然而，再循環材料用作皮層可能不太理想，因為存在不同樹脂組合，該不同樹脂組合若在內部則可能干擾待填充之內容物或若在外部則可能干擾後印刷步驟(post printing step)。
包括膨脹樹脂層之替代實施例材料
在使用膨脹樹脂層之替代實施例中，可將填充有或未填充無機材料、可經吹製或發泡之任何熱塑性樹脂材料用於本發明層中。其包括且較佳為上文中關於不膨脹層所論述的熱塑性樹脂材料，包括其相對較佳選擇。在本發明之一項實施例中，各個目的可使用相同聚合材料，例如聚苯乙烯可在同一多層膜複合結構中同時用作可膨脹聚合物樹脂組合物與不可膨脹成膜樹脂組合物。
在共擠法之前可將實質上任何已知發泡劑、起泡劑或膨脹劑併入任一或多種熱塑性樹脂材料中。起泡劑或膨脹劑包括(但不限於)物理起泡劑，包括氣態材料及揮發性液體；及分解為氣體與其他副產物之化學劑。代表性起泡劑或膨脹劑包括(但不限於)氮氣、二氧化碳、空氣、氯甲烷、氯乙烷、戊烷、異戊烷、全氟甲烷、氯三氟甲烷、二氯二氟甲烷、三氯氟甲烷、全氟乙烷、1-氯-1,1-二氟乙烷、氯五氟乙烷、二氯四氟乙烷、三氯三氟乙烷、全氟丙烷、氯七氟丙烷、二氯六氟丙烷、全氟丁烷、氯九氟丁烷、全氟環丁烷、偶氮二甲醯胺、偶氮二異丁腈、苯磺醯肼、4,4-氧基苯磺醯基-半卡肼、對甲苯磺醯基半卡肼、偶氮二甲酸鋇、N,N'二甲基-N,N'-二亞硝基對苯二甲醯胺及三肼基三嗪。
化學起泡劑包括碳酸氫鈉、碳酸銨及碳酸氫銨、檸檬酸或檸檬酸鹽(諸如檸檬酸鈉)、麩胺酸鈉、鄰苯二甲酸酐、苯甲酸、苯甲酸鹽(諸如苯甲酸鋁)、偶氮二甲醯胺、偶氮異丁腈及二硝基環戊烷。較佳化學起泡劑包含碳酸氫鈉與檸檬酸之混合物，包括Foamazol 72牌CBA，其為可自Bergen International購得之顆粒形式之含有檸檬酸與碳酸氫鈉混合物的濃縮物。
起泡劑之一般使用量為可能於泡沫層及最終物品中提供所需密度降低量所需之量。術語「密度降低」及密度降低百分比意謂藉由使用化學及/或物理起泡劑，泡沫層及/或最終物品密度降低之百分比。舉例而言，自密度為1 g/cc之起始聚合物(固體板)，密度降低至0.9 g/cc為10%密度降低，降低至0.85 g/cc為15%密度降低等。為具有成本效益與物品效能之組合，發泡熱塑性聚合物層之理想密度降低為基於起始熱塑性聚合物密度至少約10重量%(「wt%」)，較佳至少約15 wt%，最佳至少約20 wt%。為維持最終產品效能性質，諸如熱成型性，發泡熱塑性聚合物層之理想密度降低為基於起始熱塑性聚合物密度不超過約90重量%(「wt%」)，較佳至多約80 wt%，更佳至多約70 wt%，最佳至多約60 wt%。在替代實施例中，此等密度降低範圍及程度可藉由按最終產品結構及所需密度降低之需要在膨脹層中達成適當但稍微更高程度之密度降低而提供於最終多層結構中。
併入可發泡組合物中提供所需密度降低程度之活性化學起泡劑的量(以重量計)視特定起泡劑之效率及有效性而定，但其添加量一般為以化學起泡劑活性成份之總重量計至少約0.016重量%，較佳至少約0.02重量%且更佳至少約0.16重量%，及以化學起泡劑活性成份與可發泡聚合物組合物之總重量計至多約0.8重量%，較佳0.4重量%且更佳0.36重量%。
在泡沫擠出製程中使用產生氣體之液體或其他物理起泡劑時，併入可發泡組合物中之物理起泡劑添加量視所需密度降低程度及特定起泡劑之效率及有效性而定，但已發現其適合之使用量為以物理起泡劑之總重量計至少約0.0001重量%，較佳至少約0.001重量%，更佳至少約0.01重量%且更佳至少約0.063重量%，及以物理起泡劑總重量計至多約0.7重量%，較佳至多約0.3重量%，更佳至多約0.2重量%且最佳至多約0.128重量%。
可藉由已知技術調節膨脹層之單元尺寸及單元定向以使其落在對於所需性質及密度降低及膨脹層厚度而言適當的所需或可接受範圍內。參見例如USP 5,215,691及WO 2008/008875，其揭示形成具有膨脹層之平坦多層結構且皆以引用的方式併入本文中。
起泡劑必須在足以抑制熔融流在擠壓通過共擠模之前發泡之壓力下併入膨脹熱塑性樹脂材料熔融流中。此壓力一般應為至少500 psig且較佳至少1000 psig。此外，選擇適當加工條件以確保起泡劑或膨脹劑充分混合且溶解於可膨脹熱塑性樹脂組合物中。舉例而言，不膨脹熱塑性材料之熔融溫度可低於可膨脹熱塑性材料之所需發泡溫度，如以引用的方式併入本文中之USP 5,215,691關於提供可膨脹及膨脹層所述。
所選擇之用於此等層中之熱塑性樹脂材料及起泡劑或發泡劑較佳展現所得多層結構用於指定應用之最佳性質。在較佳實施例中，如上所述基於最終所得結構中所需性質選擇熱塑性樹脂材料。
較佳在包含膨脹層之環狀多層結構之此等替代實施例中，層為膨脹層與不膨脹層之間交替。
包括膨脹熱塑性樹脂材料之此等泡沫層通常提供之厚度為至少約10微米，較佳至少約50微米且更佳至少約75微米。厚度可低於約1000微米，較佳低於約500微米且更佳低於約300微米。在較佳實施例中，如可藉由ASTM D 3575-93 W-B量測，各泡沫層之密度在約0.03至約0.8公克/立方公分(g/cc)之範圍內，較佳在約0.10至約0.5 g/cc之範圍內。在替代實施例中，已成為膨脹層之環狀多層結構之密度可在約0.05至約0.9 g/cc範圍內，較佳在約0.15至約0.6 g/cc範圍內。
本發明之多層環狀模產品及製程可適宜地應用於障壁包裝(諸如經加工肉包裝)領域中。目前使用之熱狗、午餐肉及其他加工肉之包裝材料通常具有7至11層。此類型之適合7層吹製膜結構(可隨後熱成型形成底部網)可製備為如下厚度約四密耳之結構：
*順丁烯二酸酐接枝聚乙烯。
如業界已知，EVOH樹脂之乙烯莫耳%含量減低通常增加障壁性質，但減低韌性及熱成型性。此等結構之形成網的厚度可在100-150微米(4至6 mil)範圍內。關於減薄(downgaging)此等現有之多層障壁結構的問題包括由於不良熱成型性及/或EVOH斷裂而損失障壁性，及障壁性質與韌性、光學性質及膜經濟效益之平衡。
本發明之微層吹製膜製程提供較高靈活性來獲得許多層(超過15層且較佳超過27層)使結構最佳化以改良至少一種關鍵效能性質或關鍵效能性質韌性、障壁性及熱成型性與總體較低膜成本或較佳膜經濟效益之較佳平衡。
舉例而言，減薄之多層障壁結構如下：
在上文及下文之結構中提及之微層係指本發明之複合多層結構，其中該結構包含具有多於10層，更佳多於15層且最佳多於27層之所揭示聚合物之交替層。此等結構亦可包括如本發明中所述之微層複合結構之封裝。
膜之一部分由耐綸6/EVOH/耐綸6微層或交替之耐綸6及EVOH微層構成。此結構提供障壁性、韌性、熱成型性及膜經濟效益之理想組合。
或者，原始4 mil膜結構之耐綸/EVOH/耐綸中心組件可用材料總體積百分比相同之微層中心組件置換，唯一變化為各組件之總層數增加，最終為應用提供增加之障壁性/存放期及韌性。
微層障壁結構之另一替代實例如下：
*VERSIFYTM
為可購自The Dow Chemical Company之丙烯-乙烯彈性體或塑性體樹脂。
順丁烯二酸酐(MAH)接枝乙烯共聚物亦可在結構中替代耐綸6用作EVOH之紮帶層。此結構可視所需韌性而製成3或4 mil膜以使成本效率平衡最佳化。聚丙烯(PP)及Versify之微層相對於直接PP改良成型性及韌性，使得可置換掉較昂貴的耐綸。
亦可適宜地應用本發明替代實施例之多層環狀結構產品及製程提供膜障壁性改良。已知耐綸MXD6障壁經由後製作定向步驟，諸如拉幅或雙泡法提供改良。此高障壁性在製備存放期長之蒸餾(retort)包裝(包裝中之食物在蒸餾製程期間暴露於高濕度)時較為理想。然而，經由拉幅之額外定向步驟顯著增加成本。本發明環狀微層法可提供極薄MXD6層自單歧管排出且隨後可於吹製膜製程中進一步定向。此提供具成本效益之障壁效能而無需將該膜拉幅(半固體定向)。耐綸6或PET與耐綸MXD6之摻合物亦可用於該等微層結構中，於最終膜中提供氧氣障壁功能。
在另一替代實施例中，本發明之多層環狀結構產品及環狀模製程可適宜地應用於供乾食物包裝用之膜結構領域中。乾食物包裝包括諸如穀類、脆點心、小甜餅及其他對濕氣敏感之產品之應用。此等結構中併入障壁材料來阻擋濕氣、氧氣及/或味道及香氣。用於對濕氣敏感之應用之典型多層包裝包含高密度聚乙烯(HDPE)層，其可與耐綸或EVOH障壁層(包括紮帶層及密封層)一起使用以提供用於指定應用之所需障壁性質。儘管可增加障壁層(例如EVOH或耐綸)厚度來改良障壁性，但由於障壁樹脂成本或因較厚結構產生之機械加工性問題，故一般不將其視為經濟的解決方案。
因此，在替代實施例中，本發明可極適宜地用以提供環狀多層結構(尤其吹製膜)中之微層障壁層以獲得較多較薄障壁層，尤其超過約15層且較佳超過約27層，以使得結構最佳化以改良至少一種關鍵效能性質或獲得關鍵效能性質(包括(但不限於)韌性、障壁性及光學性質)之較佳平衡，若選擇減薄(downgauge)則還可能使總體成本降低。
典型膜結構如下所述：
可根據本發明之替代實施例製造微層結構以使用具有單獨HDPE層之微層及密封層達成此平衡，密封層通常由許多已知聚合物製成，包括(但不限於)LLDPE、PB、EVA或丙烯塑性體及彈性體。儘管不受理論限制，但已假設改良障壁性質之獨特結晶形態係藉由微層化而產生於極薄層中。(Science
,223,
第725-726頁,(2009))。
所提出之結構類似於上述彼等：
或者，可藉由使用中等密度聚乙烯(MDPE)替代上述實例中之HDPE來增強韌性。又，為提供額外較佳障壁性及延長乾食物存放期之能力，鑒於吸水性可引起味道吸引力減低，故在上述微層結構中可用EVOH置換耐綸。
可引起韌性與障壁性組合改良之另一種結構在總膜結構內併入兩個微層複合結構。
另一替代實施例結構藉由去除紮帶層而獲得且提供改良之成本/效能平衡：
目前，當將併有障壁層(諸如EVOH、HDPE、耐綸MXD6或耐綸)之多層膜再循環時，所得聚合物摻合物只用作填充劑，因為其不進一步增強結構之障壁性。再循環之障壁膜可併入至具有極薄層之吹製微層結構中以進一步增強障壁性。此可產生較長存放期或經由使多層結構中障壁層減薄而使得改良經濟效益。
在另一替代實施例中，本發明之多層環狀模產品及製程可適宜地應用於奈米黏土障壁性改良領域中。研究者已試圖將奈米黏土或其他無機填充劑與聚合物一起使用來改良對氧氣及濕氣之障壁性。然而，此等技術尚不具有成本效益及一致性。使用奈米黏土或諸如滑石之其他無機填充劑與適合熱塑性聚合物組合之微層吹製膜使得能夠改良對氣體分子傳遞之障壁性且提供韌性與障壁性質之平衡。此使得能夠改良牧草膜(silage wrap)、重型裝貨紙袋(heavy duty shipping sack，HDSS)、發泡包裝及需要對氣體分子傳遞具有高抗性的其他應用。
在另一替代實施例中，本發明之多層環狀模產品及製程可適宜地應用於重型裝貸紙袋(HDSS)領域中。使用HDSS來包裝諸如寵物食物、水泥、覆蓋物、肥料及聚合物顆粒之物品。通常使用以線性低密度聚乙烯(LLDPE)或中等密度聚乙烯(MDPE)及聚丙烯為主之多層結構。典型結構包括厚度為3至5 mil之LLDPE/PP/LLDPE(40/20/40)三層結構。仍需要改良膜之硬度/韌性平衡。微層結構使得能夠實現所需硬度/韌性平衡之改良且可進一步使得能夠實現減薄。
包含微層核心層來提供所需硬度/韌性平衡改良之減薄微層障壁HDSS結構實例如下：
對照(collation)收縮膜通常由LDPE及LDPE/LLDPE摻合物及多層結構組成。效能目標包括良好光學性質(低濁度)、高收縮率及高收縮張力以獲得緻密包裝、良好抗穿刺性及高模數。舉例而言，使用約2.25 mil(62微米)厚之膜收縮包覆24包水或碳酸飲料。共擠結構之典型實例為LLDPE/LDPE/LLDPE(10/80/10體積%)。添加LLDPE皮改良韌性而LDPE提供收縮張力及光學性質。然而，使用單一樹脂或多層結構難以獲得上述性質平衡。
在本發明之替代實施例中，可提供含LDPE之微層核心(例如多於27層)以改良韌性而不損害光學性質或收縮張力。在另一實施例中，可使用微層LDPE/LLDPE核心(具有多於27層)。或者可使用微層(較佳多於27層)LDPE/LLDPE摻合物核心。
在本發明之替代實施例中，多層環狀結構及其製造方法可用於製造吹製拉伸膜。已知拉伸膜用於包覆大集裝架且經由機械或經由手動包覆來施用。集裝架包覆拉伸膜通常藉由裝備有拉伸捲筒之包覆機施用於重載上。此等拉伸膜通常在拉伸100-300%拉伸範圍後以螺旋式上下包覆法施用。手動包覆通常藉由手動施用且拉伸比不高於100%。所包覆之貨物一般為藉由集裝架運輸之任何工業產品，亦即化學品、塑膠、箱子、家用電器等。此等類型拉伸膜之關鍵效能性質為高斷裂伸長率、抗穿刺性及抗艾勉道夫撕裂性(elmendorf tear resistance)。儘管此等機械性質可用以衡量效能，但使用時之最終效能係使用實驗室標度拉伸包覆裝置(諸如由Highlight Industries供應)評估。此方法使得測定極限拉伸、拉伸力、退繞力及獲得抗滑性(cling)及抗穿刺性(puncture)之集裝架包覆。膜規格通常為約20微米(0.8 mil)。此外，膜通常具有賦予抗滑性之抗滑層。通常於抗滑層中使用極低密度聚乙烯(VLDPE)、EVA、LLDPE、LLDPE/LDPE摻合物、聚異丁烯(PIB)、聚烯烴塑性體與彈性體及其摻合物。此外，拉伸膜亦可具有脫模層，其具有典型脫模層材料，包括：MDPE、LLDPE/LDPE摻合物，以及以丙烯為主之聚合物，包括無規共聚物(RCP)，及其摻合物。
典型三層吹製拉伸膜結構(一側抗滑)為：
聚丙烯RCP(脫模層)-0.1 mil
LLDPE(核心層)-0.6 mil
VLDPE(抗滑層)-0.1 mil
根據本發明之替代實施例，其他用於拉伸包覆應用之類似環狀吹製一側抗滑膜結構具有含微層LLDPE或微層LLDPE A/LLDPE B之核心層，其中LLDPE A及LLDPE B為兩種不同的LLDPE樹脂。使用多於兩種LLDPE之微層核心層組件亦可用於以上結構中。以上微層複合膜結構與典型多層結構相比獲得韌性、拉伸性及固持力之理想組合且亦使得經由減薄改良膜之經濟效益。或者，可用LLDPE、LDPE、HDPE及以丙烯為主之聚合物及其摻合物之各種組合來置換LLDPE A/LLDPE B。
此外，在本發明之替代實施例中，可用微層LLDPE核心組件置換具有兩側抗滑膜性質之典型三層拉伸膜中的LLDPE核心層，提供如下結構：
LLDPE/VLDPE摻合物(抗滑層)-0.1 mil
微層LLDPE(核心層)-0.6 mil
LLDPE/VLDPE摻合物(抗滑層)-0.1 mil
以上微層複合膜結構與非微層多層結構相比獲得韌性、拉伸性及固持力之理想組合，使得經由減薄改良膜之經濟效益。
藉由以下實例進一步詳細說明本發明。該等實例僅用於說明之目的且不解釋為限制本發明範疇。
於吹製膜生產線上使用178 mm直徑之環狀模製造厚度為約50微米且含有31層低密度聚乙烯交替層的膜。此膜藉由製造27層層疊之多層流且用另一聚乙烯層封裝彼層疊且接著將彼結構饋入至多層層疊環狀模之中心分配歧管中來製造。該多層流結構例如一般根據如USP 3,557,265中所示之給料區段製程，藉由以51 mm擠壓機及19 mm擠壓機饋料之習知給料區段形成，接著藉由如USP 5,094,793中所示之倍增器步驟倍增。
接著一般根據如USP 6,685,872中所示之方法用另一聚乙烯層封裝此等層。經封裝之物料流具有一般矩形橫截面幾何形狀，使用圓形管流道轉移至圓形轉移流中且傳遞至具有變形十字頭幾何形狀之平面環狀模的歧管中提供具有重疊區之擠出多層環狀結構。如US 6,685,872中所示，多層結構流經分配歧管形成環狀多層結構且於擠出之環狀結構區中提供層重疊。亦如US 6,685,872中所示，於多層環狀模中使用單獨分配歧管施加兩個額外聚乙烯皮。環狀多層流以環狀多層結構形式離開環狀模且以2:1之吹脹比膨脹。氣泡破裂且分成兩個膜網。膜製造速率為14至32kg/hr。此製程於圖1中概述。
於吹製膜生產線上於178 mm直徑模上製造含有31層具有低密度聚乙烯泡沫與膜交替層之500微米環狀模/泡沫結構。如上文針對實例1所述，藉由製造27層(13層可膨脹層，14層不可膨脹膜層)層疊形式之多層流且用另一聚乙烯層封裝彼層疊來製造此膜。接著如上文關於實例1所述使經封裝之物料流傳遞通過轉移線至具有變形十字頭幾何形狀之環狀模中且如上文針對實例1所述進行擠出。多層結構流經中心分配歧管形成具有層重疊區之環狀微層結構且於多層環狀模中使用單獨分配歧管施加聚乙烯皮。環狀多層流離開環狀模且以2:1之吹脹比膨脹。氣泡破裂且分成兩個膜網。結構製造速率為14至32 kg/hr。該結構所得密度為約0.5 g/cc。
使用藉由共擠生產線提供的型坯製備多層聚乙烯吹塑結構，該共擠生產線具有兩個19 mm直徑單螺桿擠壓機將兩種組份通過齒輪泵饋入至一般根據US 3,557,265之給料區段中，及設計類似於US 5,202,074及5,094,783中所述彼等之一系列層倍增器。一般根據USP 6,685,872中所示之技術將多層聚乙烯樹脂供應流封裝以提供多層原料流且向前進入直徑為38 mm且在歧管背面合併分開之物料流的邊緣(亦即不在擠出之環狀結構中提供重疊區)之環狀十字頭模中。總擠出速率在約9 kg/h至18 kg/h之間變化。接著將環狀擠出物捕獲於350 ml圓柱形瓶模之腔中，膨脹且冷卻形成部件。此等結構形成於模唇間隙為1.52 mm之38 mm直徑模上。部件形成於膨脹壓力為0.4 MPa之350 ml圓柱形模中完成。
由根據實例3中所示之製程(其中一個擠壓機提供含有2重量%偶氮二甲醯胺化學發泡劑的聚乙烯組份)製備的型坯製備具有聚乙烯泡沫與膜之交替層且巨單元定向度不同的多層吹塑結構。總擠出速率在約9 kg/h至18 kg/h之間變化。接著將環狀擠出物捕獲於350 ml圓柱形瓶模之腔中，以0.4 MPa之膨脹壓力膨脹且冷卻形成部件。此等結構形成於模唇間隙為1.52 mm之38 mm直徑模上。瓶之總密度為約0.5 g/cc。
於吹製膜生產線上使用178 mm直徑環狀模製造厚度為約100微米且含有6個LLDPE皮及紮帶層單層及27個EVOH及紮帶層交替層的膜。此膜係藉由製造13個EVOH及14個紮帶層層疊之核心多層流、用另一紮帶層封裝彼層疊且接著將彼結構饋入至多層層疊環狀模之中心分配歧管中來製造。該多層流結構例如一般根據如USP 3,557,265中所示之給料區段製程，藉由以44.45 mm擠壓機及38.1 mm擠壓機饋料之習知給料區段形成，接著藉由如USP 5,094,793中所示之倍增器步驟倍增。
接著一般根據如USP 6,685,872中所示之方法用另一紮帶層封裝此等層。經封裝之物料流具有一般矩形橫截面幾何形狀，使用圓形管流道轉移至圓形轉移流中且傳遞至具有變形十字頭幾何形狀之平面環狀模的歧管中以提供具有重疊區之擠出多層環狀結構。如US 6,685,872中所示，多層結構流經分配歧管形成環狀多層結構且於擠出之環狀結構區中提供層重疊。亦如US 6,685,872中所示，於多層環狀模中使用單獨分配歧管施加兩個額外聚乙烯皮。環狀多層流以環狀多層結構形式離開環狀模且以約1.7:1之吹脹比膨脹。氣泡破裂且分成兩個膜網。膜製造速率為55 kg/hr。此製程於圖1中概述。
用於以下實例中之材料於表1中顯示。
使用習知7層模以吹脹比(BUR)為1.7，總線速率為120 lb/hr且擠出溫度列於表2中來製造以下比較結構。
此結構厚3.68 mil，23C及80% RH下之透氧率為0.238 cc/100 in2
/天/atm。此計算出滲透率為0.077 cc-mil/100 in2
/天/atm，與23c及80% RH下H171B之文獻值相當。
於如比較實例5中所述之設備上製造以下發明實例。其使用與比較實例相同之H171B，但H171B與紮帶層一起微層化製成27層之核心。擠出條件與對照組相當且列於表2中。結構如下：
此結構具有H171B及BYNEL/ADMER紮帶層以1:2之比率一起微層化形成佔結構15%之總核心厚度，其中膜結構中總共有5% H171B。此3.36 mil膜在23C及80% RH下之透氧率為0.19 cc/100 in2
/天/atm。此計算出滲透率為0.031 cc-mil/100 in2
/天/atm。此為透氧率自對照7層結構降低60%。
使用實例5中所述之設備及表2中之擠出條件製造另一發明實例。
使用10% H171B製造微層結構。此結構具有H171B及BYNEL/ADMER紮帶層以1:2之比率一起微層化形成佔結構20%之總核心厚度，其中膜結構中總共有10% H171B。
此微層膜厚度為3.59 mil，在23C及80% RH下之透氧率為0.29 cc/100 in2
/天/atm。此計算出滲透率為0.104 cc-mil/100 in2
/天/atm。
此等數據顯示實例5(僅具有5% H171B之3.36 mil膜)具有低於比較實例5或此10% H171B 27層核心之透氧率。此係歸因於H171B百分比分成薄層，使H171B結晶及晶體尺寸最佳化從而降低透氧率。
測試比較實例5中所製造之相同結構的膜性質。
此3.7 mil多層膜經量測落錘衝擊失敗(dart drop failure)為121公克或32.7 gm.mil(ASTM D1709)。此樣品之MD艾勉道夫撕裂為24 gm/mil且TD艾勉道夫撕裂為28 gm/mil(ASTM D1922)。
於如實例5中所述之設備上製造以下發明實例，其使用與比較實例相同之H171B且使其與紮帶層一起微層化製成27層核心。此樣品在表2中之條件下製造。結構如下：
此結構具有H171B及BYNEL紮帶層以1:2之比率一起微層化形成佔結構15%之總核心厚度，其中總共有5% H171B。此4.25 mil膜經量測落錘衝擊為259或60.9 gm/mil(ASTM D1709)。此樣品之MD艾勉道夫撕裂為44.5 gm/mil且TD艾勉道夫撕裂為50.4 gm/mil(ASTM D1922)。
於實例5中之設備上使用10% H171B微層含量製造另一發明微層結構。使用表2中之條件製造樣品。
此3.94 mil膜經量測落錘衝擊為189公克或48 gm/mil(ASTM D1709)。此樣品之MD艾勉道夫撕裂為19.8 gm/mil且TD艾勉道夫撕裂為16.8 gm/mil(ASTM D1922)。
在表2中之條件下於實例5中之設備上製造第三膜。
此3.23 mil膜經量測落錘衝擊為370公克或114.5 gm/mil(ASTM D1709)。此樣品之MD艾勉道夫撕裂為97 gm/mil且TD艾勉道夫撕裂為259 gm/mil(ASTM D1922)。
具有5% H171分成薄層之兩個微層結構顯示，可經由使個別層厚度最佳化以控制結晶來增加韌性。10% EVOH(個別層較厚)顯示比5%含量低之韌性。
1．．．擠壓機1
2．．．擠壓機2
3．．．擠壓機3
4．．．擠壓機4/給料區段/位置
5．．．擠壓機5/層倍增器
6．．．給料區段/封裝模
7．．．層倍增器/吹塑頭
8．．．封裝模/模腔
9．．．分配歧管
10．．．分配歧管
11．．．分配歧管
12．．．環狀膜泡
100．．．十字頭模
105．．．管
110．．．圓形管流道
115．．．通道
120．．．通道
200．．．十字頭模
205．．．管
210．．．圓形管流道
215．．．通道
220．．．通道
圖1為說明根據本發明實施例製造用於多層膜複合結構之多層吹製膜之方法的示意圖；
圖2為說明根據本發明實施例由多層膜複合結構製造多層吹塑物品之方法的示意圖；
圖3為來自大半徑圓形管流道之硬化多層流之像片；
圖4為圖3中區段橫截面之像片；
圖5為對具有大半徑圓形管流道之模之說明；
圖6為對具有小半徑圓形管流道之模之說明；
圖7A-B為對環狀多層結構重疊區不同實施例之說明；
圖8A-B為環狀多層結構重疊區及不重疊區中微層之原子力顯微(AFM)像片；及
圖9為環狀多層結構重疊區中微層之(TEM)像片。
1．．．擠壓機1
2．．．擠壓機2
3．．．擠壓機3
4．．．擠壓機4
5．．．擠壓機5
6．．．給料區段
7．．．層倍增器
8．．．封裝模
9．．．分配歧管
10．．．分配歧管
11．．．分配歧管
12．．．環狀膜泡
Claims (25)
- 一種製造環狀多層結構之方法，其包含：提供多層熱塑性樹脂材料流，該多層流包含具有至少30層之微層部分及在該微層部分之第一及第二側上的至少一額外層，該微層部分具有微層結構；將該多層流經由具有入口與出口的管流道饋入至環狀模之單分配歧管中，其中該管流道在該入口與出口之間具有弧區，該弧區具有圓形道直徑，其中該弧區具有大於圓形道直徑的曲率半徑；使該多層流分成至少兩個物料流，其中該至少兩個物料流以相反方向環繞該分配歧管之圓周移動形成環狀多層流，該等物料流中一物料流之一端與另一物料流之一端重疊於重疊區中，且其中在該重疊區中維持該微層結構；及自該環狀模移除該環狀多層流形成該環狀多層結構。
- 如請求項1之方法，其中提供該多層熱塑性樹脂材料流包含：提供該微層部分；及將該微層部分以至少一個封裝層封裝形成該多層流。
- 如請求項2之方法，其中提供該微層部分包含：提供具有至少兩層之第一流；將該第一流分成至少兩個子流；及使該至少兩個子流接合，使得該第一子流位於該第二子流上面形成該微層部分。
- 如請求項1至3中任一項之方法，其中該分配歧管具有變形十字頭型幾何形狀。
- 如請求項1至3中任一項之方法，其中該分配歧管具有平面幾何形狀。
- 如請求項1至3中任一項之方法，其中該分配歧管具有圓柱形主體、錐圓柱形主體或平面主體。
- 如請求項1至3中任一項之方法，其中該多層流經由具有弧形流動方向之圓形管流道饋入該環狀模之該單分配歧管中，其中該弧之曲率半徑大於該圓形管流道之直徑。
- 如請求項1至3中任一項之方法，進一步包含使用至少一個額外分配歧管提供至少一額外流至該環狀模內之該多層流中。
- 如請求項8之方法，其中該至少一額外流為多層流。
- 如請求項1至3中任一項之方法，進一步包含在提供該多層流之前，添加發泡劑或無機填充材料至該等熱塑性樹脂材料之至少一種中。
- 如請求項1至3中任一項之方法，進一步包含：將型坯形式之該環狀多層結構置於吹塑模內且使該環狀多層結構膨脹為該模之形狀。
- 如請求項1至3中任一項之方法，進一步包含：拉伸熔融狀態之該環狀多層結構以使該結構雙軸定向；及冷卻該結構。
- 如請求項12之方法，包含： 將該冷卻之結構再加熱至低於該結構中最高熔點聚合物熔點之溫度；單軸或雙軸拉伸該結構使該結構定向；及隨後冷卻該結構。
- 如請求項1至3中任一項之方法，其中該弧區的曲率半徑與圓形道直徑之比率係大於3：1。
- 一種藉由如請求項1至14中任一項之方法製造之物品。
- 一種環狀多層物品，其厚度均一且包含重疊及不重疊圓周區；該不重疊區具有微層部分，該微層部分之第一及第二側上具有至少一額外層，該微層部分具有至少30層，該微層部分具有微層結構；其中該不重疊區之層結構在該重疊區成雙倍且其中在該重疊區中維持該微層結構。
- 如請求項16之環狀多層物品，其中該環狀多層物品為多層吹製膜且其中該微層部分之該第一及第二側上的該至少一額外層封裝該微層部分。
- 一種裝置，包含：給料區段，其具有視情況存在之層倍增器，能夠向環狀模之分配歧管提供多層流，該多層流包含具有至少30層之微層部分及在該微層部分之第一及第二側上的至少一額外層；具有入口與出口的管流道，其中該管流道在該入口與出口之間具有弧區，該弧區具有圓形道直徑，且該弧區具有大於圓形道直徑的曲率半徑，該管流道改變該多層 流之方向並同時維持該微層部分之微層結構；及環狀模，其具有至少一個分配歧管擠出多層流，該分配歧管具有重疊區，該重疊區維持該微層結構。
- 如請求項18之裝置，其中該分配歧管具有變形十字頭型幾何形狀。
- 如請求項18或19之裝置，其中該分配歧管具有平面幾何形狀。
- 如請求項18或19之裝置，在該給料區段與該歧管之間進一步包含封裝模在該多層流進入該分配歧管之前將其封裝。
- 如請求項18或19之裝置，其中該管流道位於該封裝模與該分配歧管之間且其中該管流道之入口定向為與該管流道之出口呈約90度角。
- 如請求項18或19之裝置，其中該管流道位於該環狀模中。
- 如請求項18或19之裝置，其中該管流道位於該環狀模之前。
- 如請求項18或19之裝置，其中該分配歧管具有圓柱形主體、錐圓柱形主體或平面主體。
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- 2010-02-19 CA CA2753182A patent/CA2753182A1/en not_active Abandoned
- 2010-02-19 WO PCT/US2010/024653 patent/WO2010096608A2/en active Application Filing
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- 2010-02-19 MX MX2011008801A patent/MX2011008801A/es active IP Right Grant
- 2010-02-19 CN CN201080008555.0A patent/CN102325639B/zh active Active
- 2010-02-19 ES ES10737137.9T patent/ES2471461T3/es active Active
- 2010-02-19 KR KR1020117021986A patent/KR20110127231A/ko not_active Application Discontinuation
- 2010-02-19 JP JP2011551232A patent/JP5667091B2/ja not_active Expired - Fee Related
- 2010-02-22 TW TW099105112A patent/TWI418458B/zh not_active IP Right Cessation
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Also Published As
| Publication number | Publication date |
|---|---|
| EP2398632A2 (en) | 2011-12-28 |
| BRPI1005997A2 (pt) | 2016-02-16 |
| KR20110127231A (ko) | 2011-11-24 |
| EP2398632B1 (en) | 2014-03-26 |
| WO2010096608A3 (en) | 2011-02-17 |
| TW201043443A (en) | 2010-12-16 |
| US20100215879A1 (en) | 2010-08-26 |
| US9481143B2 (en) | 2016-11-01 |
| US20140044906A1 (en) | 2014-02-13 |
| CA2753182A1 (en) | 2010-08-26 |
| JP5667091B2 (ja) | 2015-02-12 |
| CN102325639B (zh) | 2014-04-09 |
| WO2010096608A2 (en) | 2010-08-26 |
| ES2471461T3 (es) | 2014-06-26 |
| MX2011008801A (es) | 2011-09-08 |
| RU2011138612A (ru) | 2013-03-27 |
| JP2012518557A (ja) | 2012-08-16 |
| US8562885B2 (en) | 2013-10-22 |
| CN102325639A (zh) | 2012-01-18 |
| RU2500540C2 (ru) | 2013-12-10 |
| BRPI1005997B1 (pt) | 2019-12-17 |
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