TWI290941B - Membranes with fluid barrier properties and articles containing such membranes - Google Patents
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Abstract
Description
1290941 案號·· 93123224 2006年8月28曰修正 九、發明說明: 【發明所屬之技術領域】 本發明關於具有符合阻障性及彎曲性需求之填料的 薄膜’特別是使用於準備用於充氣物品及缓衝裝置之膨脹 物。本發明進一步關於被充氣及具有充氣元件之物品。 【先前技術】 由此類薄膜形成之阻障薄膜及充氣膨脹物,已多樣化 使用於充氣物trcr及緩衝之物品,包含車輛之輪胎、球、使 用於重機械之蓄壓器以及鞋類,尤其是運動鞋。一般希望 使用熱塑性的聚合物材料製成薄膜,這是因為熱塑性的材 料可回收利用及重新製造成為新的物品,於製造過程中減 少廢棄物,且提升在物品的使用壽命後之再利用。然而熱 塑膠阻障薄膜很薄,可能收縮至一定範圍内,一般埶塑性 阻障薄膜僅具有阻障材料層,於許多應用中沒有足多句的彈 性,特別是應用在使用時承受高張力的充氣膨脹物。為了 解決這些問題,阻障材料使用已彎曲或多層的彈性材料。 彈性材料或彈性物本質上可在移除變形力後回復為原來 的形狀及大小,即便其部份已變形。彈性材料在許多充 的膨脹物麵上是重要的,包含鞋類、運動的球及式 蓄壓器的充氣膨脹物。 、 製造充氣膨脹物之薄膜的一項重要特性在於其「氣體 擴散速率(gas transmission rate)」。-種於製造步驟中 用於量測不同薄騎料之相關侵透(_eanee)、參透性 (permeability)的方法,係標明為 astmd—1434|^。 氣的膨脹物被期待為在其生命週期内能維持可用之 4HDP/04002TW/NIKE-替換頁 5 1290941 案號:93123224 2006年8月28曰修正 疋而無需週期性地重新引進充氣氣體,因此充氣的膨脹 ,可永久地密封,無須再次充氣。一種達到如此Γ永久地 密,」膨脹物所需的低氣體擴散速率的方法,為使膨脹物 之薄膜的阻障層厚度增加,然而由於增加硬度將會形成較 厚,的阻障材料,此並非吸引人的選擇。從維持薄膜彈性 的觀點,較佳為藉由一種不會本質上增加薄膜硬度的方 法,來降低氣體擴散速率。 在如鞋類或球類膨脹物的應用上,「款式」是膨脹物 ,另一個考量,款式吸引買方的眼光,並使物品有魅力, 最近,鞋類款式的一項改革是具有外觀表面的透明元件, y般期待此透明元件為輪廓鮮明、光潔的、「高科技」外 觀般清澈。包含在鞋中以提供緩衝的充氣膨脹物,也可具 有此透明元件的功能,然而,膨脹物必須維持彈性及氣體 =障特性,以完成其提供緩衝足部的主要功能。因此期待 藉由種方法,使付薄膜外觀非不透光(〇pa(jUe)或非朦朧 (hazy),且透過薄膜得以降低氣體擴散速率。 具有多層易彎曲材料層及多層流體阻障層的薄膜層 已被描述過,舉例來說,於2000年7月4日核准的美^ 專利號為6, 082, 025、於2000年1 $ n日核准的美國專 利號為6, 013, 340、於1999年9月14日核准的美國專利 號為5, 952, 065,以及於1998年2月3日核准的美國 號為5, 713,141合併於此作為參考。雖然這些參考 供具有易f曲、「永久地」密封、氣體填充_ 而仍期待能對其彈性有改善。 …、 4HDP/04002TW/NIKE-替換頁 1290941 案號:93 1 23224 2006年8月28日修正 雲母及其他具有大的外觀比值(aspect ratio)的板填 料已被使用,以降低充氣薄膜的氣體擴散速率。Tokoh et al·的美國專利5, 221,566,教導容器可以由具有50-95% 乙烯-乙烯醇共聚樹脂(EV0H)及5-50%無機填料的第一 層,以及具有如聚乙烯之濕潤阻抗熱塑性樹脂的第二層所 形成,無機填料之平均薄片厚度不大於50微米,外觀比 值至少3,以及潔白度(whiteness)至少80(由Kett分光 光度計(spectrophotometer)所量測)。Tokoh et al·的材 料不具有緩衝裝置以及其他充氣物品所需的彈性。 因此,一種對於充氣氣體具有高非滲透的流體阻障材 料的組成仍然是需要的。 【發明内容】 本發明提供一種至少具有一層之薄膜,此薄膜包含至 少一彈性材料及至少一聚合物流體阻障材料,其中此薄膜· 至乂有層疋一層狀奈米填料(laminar nano-fi 1 ler), 此層狀奈米填料具有達約10奈米之一平均薄層厚度,及 至少約200之一平均外觀比值。此薄膜較佳包含至少一具 ί二彈性材料之彈性層,以及至少一具有一聚合物流體阻 ρ早材料之巧體阻障層。此彈性材料提供本發明之薄膜之彈 =及尺寸穩定性,而流體阻障材料讓此薄膜防止流體由薄 移至另—侧。層狀奈米填料避免流體由薄膜之一 ’另二側,不會明顯造成薄膜之非透明及朦朧性增 加,且不會減少薄膜之彈性。 如此耐用、彈性之阻障薄膜可使用於充氣之膨脹物。 4HDP/04002TW/NIKE-替換頁 7 1290941 案號:93 1 23224 * , 2006年8月28日修正 「耐用」表示此薄膜具有絕佳能力阻抗彈性疲乏,尤其是 本發明之薄膜可承受重複收縮且/或重複製造以及重新恢 復,而不會延薄膜之層間介面剝離,較佳可承受廣泛之溫 度。 為了本發明之目的,「薄膜」此字義為表示獨立 (free-standing)薄層,用以將流體,尤其是氣體,較佳 在南於大氣壓,與另一流體(液體或氣體)或與低壓下之氣 體分隔。層化或壓印在另一物品非以分隔流體為目的之薄 膜’排除於本發明所定義之薄膜之外。 本發明之另一方面提供一種薄膜,包含一微層 (microlayer)聚合物複合層,此微層聚合物複合層具有含 至少一聚合物流體阻障材料之微層,及含至少一彈性體之 微層,任一層具有一或多種其他材料,所有不同各層規則 地排列於複合層中。聚合物流體阻障材料且/或彈性材料 層更包含一,狀奈米填料,此層狀奈米填料具有達約1〇 奈米之平均薄層厚度,及至少約200之平均外觀比值。 本發明進一步提供由本發明之薄膜形成之封體 (enclosure),包含但並未限定為永久地密封、充氣膨脹 物,包含士類封體及膨脹物之物品。膨脹物可能由如氮氣 之,體所密封,此膨脹物可用於充氣或緩衝,舉例來說為 充氣一運動球或提供鞋類之緩衝,此膨脹物可能結合其他 材料,如衣服或泡沫材料(f〇am)外層,以形成一緩衝裝置。 此阻障薄膜較佳具有相當低之氣體擴散速率,可供一 4HDP/04002TW/NIKE-替換頁 1290941 案號:93123224 2006年8月28曰修正 ,封知脹物維持「永久地(permanently)」密封,也就是 說,供包含此膨脹物之物品的可用壽命内,維持有用的内 部壓力。一種可接受用來測量不同薄膜材料的相關侵透、 ,透性及擴散的方法為ASTMD-1434-82-V。薄膜之氣體擴 散速率表示為單位面積及單位時間下氣體擴散通過薄膜 的量,氣體擴散速率可能於標準溫度及壓力下,表示的單 位為(cc)(mil/(m2)(24hour),本發明所提供之阻障薄膜較 佳為小於 1 (cc)(mil/(m2)(24hour)。 【實施方式】 下述之說明本質僅為一較佳實施例,非意欲限制本發 明及其應用及使用。 本發明提供一種至少具有一層之薄膜,此薄膜包含至 少一彈性材料及至少一聚合物流體阻障層,其中此薄膜· 至少有一層疋一層狀奈米填料,此層狀奈米填料具有達約 10奈米之一平均薄層厚度,及至少約2〇〇之一平均外觀比 值。此薄膜可能僅為一單層,此單層包含彈性材料、流體 阻IV層以及層狀奈米填料,但此薄膜較佳為具有至少兩 層。此薄膜較佳包含至少一層彈性材料,以及至少一声 合物阻障材料,其中此彈性材料層且/或聚合物阻^料 層包含層狀奈米填料,此層狀奈米填料具有達約太 之-平均薄層厚度,及至少約2GG之-平均外觀比值^ 層狀奈米填料較佳與流體阻障材料結合,例如 之流體阻障材料或於多層薄膜之流體阻障層。 曰職 此彈性材料可為-熱塑性彈性體或橡膠,熱塑性彈性 4HDP/04002TW/NIKE-替換頁 1290941 案號:93123224 2〇96年8月28曰修正 體一般具有一或多柔軟或易、脊曲區段(segment),以提供 译性性質’以及具有硬或剛性區段作為熱可逆物理交聯 (crosslink),可使聚合物以熱塑性材料處理,而於室溫 下保持彈性行為。舉例來說,一種熱塑性彈性體具有如聚 酯或聚醚區段般的柔軟或橡膠似的聚合物區段,以及如聚 氨酯區段般的硬或玻璃似的區段。如苯乙烯(styrene)/丁 二烯(butadiene)/苯乙烯的A-B-A嵌段共聚物(bl〇ck copolymer)具有相似的結構,此聚合鏈之中間總為軟或彈 性的區段(即橡膠似的聚丁二稀),而其尾端為玻璃似的區 段(即聚苯乙烯)。另一適當的熱塑性彈性體類別為動態的 硬橡膠(dynamic vulcanizate),在溶化熱塑性相下,橡 膠似的相(rubbery phase)被硫化。適於形成彈性層之彈 性體之實施例,包含並非限定於聚氨酯彈性體,具有基於 芳香族及脂肪族的彈性體、具有易彎曲聚乙烯及聚丙烯之 同元聚合物(homopolymer)和共聚物(cop〇iymer)的易彎 曲烯烴、具有苯乙烯(乙烯-丁二烯)苯乙烯之嵌段共聚物 的苯乙烯熱塑性彈性體、聚醯胺彈性體、聚醯胺—醚彈性 體、酯-醚及酯-酯彈性體、易彎曲的離子體、熱塑性硬橡 膠、易彎曲的聚氯乙烯的同元聚合物及共聚物、彈性的丙 烯酸聚合物,以及其混合物(blends)和合金,如聚氯乙稀 合金以及聚氯乙烯-聚氨酯合金。在交聯前可能被擠壓的 橡膠可被使用,伴隨著在此薄膜擠壓後進行交聯。橡膠包 含並非限定於腈橡膠(nitrile rubber)及丁基橡膠(butyl rubber)。不同的彈性材料可於同一層中結合為混合物, 或者是可能包含於薄膜中分開的各層。 特別適當的為熱塑性聚酯-聚氨酯、聚醚—聚氨酯以及 10 4HDP/〇4〇〇2Tvv/nikE-替換頁 1290941 案號:93 1 23224 • 2006年8月· 28曰修正 聚碳酸酯-聚氨酯,包含並非限定於將聚氨酯與當作二醇 試劑的聚四氫呋喃(0〇17七6仕81^(11'(^1^811)、聚醋、聚内 酯(polylactone)聚酯(尤其是聚己内酯 (polycaprolactone)二醇),或者是由具有羥基(hydroxy group)的單羧酸(monocarboxylic acid),與環氧乙烧 (ethylene oxide)及環氧丙烧(propylene oxide)之聚 醚、環氧乙烷及環氧丙烷之共聚物所製備之聚酯。這些聚 合物二醇性(diol-based)聚氨酯係由聚合物二醇(聚酯二 醇、聚醚二醇、聚己内酯二醇、聚四氬呋喃二醇或聚碳酸 酯二醇)、一或多種聚異氰酸酯(polyisocyanate),以及 選擇性地與一或鏈延伸化合物(chain extension compound)反應製備。在此所指的鏈延伸化合物為具有兩 個或多個官能基,較佳為兩個官能基,與聚異氰酸酯基易 反應,聚合物二醇性聚氨酯較佳為大致線性(意及大致上 所有反應物為雙重官能基(di-functional))。 本發明用於形成較佳的熱塑性聚氨酯之聚酯二醇,係 一般由多元酸(polyacid)(包含其無水物(anhydride)及 其酯類)及多元醇(polyol)縮聚(condensa t i on )而製備, 這些多元酸及多元醇化合物較佳具有雙重官能基,即二元 酸(diacid)化合物(包含二元酸化合物之無水物)與二元 醇(diol)用於製備實質上線性之聚酯二醇,雖然可能包含 有少量的單一官能基(mono-functional)、三官能基 (trifunctional)及更多官能基材料(可能高達5莫爾百分 比)。適當的二羧酸(dicarboxylic acid)包含並非限定為 戊二酸(glutaric acid)、丁二酸(succinic acid)、丙二 酸(malonic acid)、乙二酸(oxalic acid)、酞酸(phthalic 4HDP/04002TW/NIKE-替換頁 11 1290941 案號:93 1 23224 2006年8月28曰修正 acid)、六氫化鄰苯二甲酸(hexahydrophthalic acid)、 己二酸(adipic acid)、順-丁烯二酸(maleic acid)及其 無水物。適當的多元醇包含並非限定,其中延伸物係選自 乙二醇(ethylene glycol)、二乙二醇(diethylene glycol)、丙二醇(triethylene glycol)、丁二醇 (tetraethylene glycol)、戊二醇(propylene glycol)、 二丙二醇((^口1:€^716116忌17(:〇1)、三丙二醇(1:140]:(^7161^ glycol)、四丙二醇(tetrapropylene glycol)、環己烧二 曱醇(cyclohexanedimethanol)、2-乙基-1,6- 丙二醇 (2-ethyl-1,6-hexandiol) 、 1,4- 丁二醇 (1,4-butanediol)、1,5-丁二醇(1,5-pentanediol)、1,3-丙二醇(1,3-propanediol)、丁二醇(butylene glycol)、 新戊二醇(neopentyl glycol)及其混合物之群組。有時 會有少量的三元醇或更高官能基的多醇,如三甲醇丙烧 (trime仕lylolpropane)或季戊四醇(pentaerytrit〇l)。於 一較佳實施例中,二羧酸包含己二酸,而二醇包含丨,釭 丁二醇,一般用於酯化聚合的催化劑為多質子酸 (protonic acid)、路易士酸(Lewis acid)、鈦氧化物以 及二烧基錫氧化物。 羥基二羧酸化合物之聚合也會產生聚酯,這類 能包含或不包含一起始多元醇。 ' ~ 聚醚或聚内酯二醇可使用於製備較佳的熱塑性 酉曰,1醚或t内S曰一醇可藉由一起始二醇起始劑製, 乙二醇或丙二醇等二醇,與内醋或烯基氧化物或^他口 乙烷·(Oxirane)鏈延伸試劑。用於製備聚内酯之適當鏈= 4HDP/04002TW/NIKE-替換頁 12 1290941 案號:93123224 2006年8月28日修正 活化氫’之内酯。舉例來說,適當的 内,曰包,但非限定ε-己内醋个己内醋、万_丁;:1290941 Case No. · 93123224 August 28, 2006 Amendment IX. OBJECTS OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a film having a filler that meets the barrier and bendability requirements, particularly for use in preparation for inflation An expansion of the article and the cushioning device. The invention further relates to articles that are inflated and have an inflatable element. [Prior Art] The barrier film and the inflated product formed by such a film have been diversified for use in inflatable trcr and cushioning articles, including tires for vehicles, balls, accumulators for heavy machinery, and footwear. Especially sports shoes. It is generally desirable to use thermoplastic polymeric materials to form films because thermoplastic materials can be recycled and remanufactured into new articles, reducing waste during manufacturing and improving reuse after the life of the article. However, the thermal plastic barrier film is very thin and may shrink to a certain extent. Generally, the plastic barrier film only has a barrier material layer, and in many applications, there is not enough flexibility, especially when applied to withstand high tension. Inflatable expansion. In order to solve these problems, the barrier material uses an elastic material that has been bent or multi-layered. Elastomeric materials or elastomers can essentially return to their original shape and size after removal of the deforming force, even if part of it has been deformed. Elastomeric materials are important on many filled swell surfaces, including footwear, moving balls, and inflatable swells of accumulators. An important characteristic of the film for producing a gas-filled expander is its "gas transmission rate". - Method used in the manufacturing process to measure the relative penetration (_eanee) and permeability of different thin rides, marked as astmd-1434|^. The gas swell is expected to remain available during its life cycle. 4HDP/04002TW/NIKE-Replacement Page 5 1290941 Case No. 93132224 Modified on August 28, 2006 without periodically reintroducing the inflation gas, thus inflating The expansion is permanently sealed and does not require refilling. A method of achieving a low gas diffusion rate required for such a sturdy, permanent expansion, in order to increase the thickness of the barrier layer of the film of the swell, however, due to the increased hardness, a thicker barrier material is formed. Not an attractive choice. From the standpoint of maintaining film elasticity, it is preferred to reduce the gas diffusion rate by a method which does not substantially increase the hardness of the film. In applications such as footwear or ball swells, the "style" is an expansion, another consideration, the style attracts the buyer's vision, and makes the item attractive. Recently, a reform of the footwear style has a surface appearance. The transparent component, y expects the transparent component to be clear, smooth, and "high-tech". The inflatable expansion contained in the shoe to provide cushioning may also have the function of this transparent element, however, the expansion must maintain its elasticity and gas-barrier characteristics to accomplish its primary function of providing a cushioning foot. Therefore, it is expected that the appearance of the film is not opaque (〇pa (jUe) or non-hazy), and the gas diffusion rate is reduced by the film. The layer has a plurality of layers of flexible material and a multilayer fluid barrier layer. The film layer has been described, for example, the U.S. Patent No. 6,082,025 approved on July 4, 2000, and the U.S. Patent No. 6,013,340 approved on January 1, 2000. U.S. Patent No. 5, 952, 065, issued on Sep. 14, 1999, and U.S. Patent No. 5,713, issued to "Permanently" sealed, gas filled _ and still expected to improve its elasticity. ..., 4HDP/04002TW/NIKE-Replacement Page 1129941 Case No.: 93 1 23224 Modified August 28, 2006 Modified mica and other large appearance An aspect ratio of the plate filler has been used to reduce the gas diffusion rate of the aerated film. U.S. Patent No. 5,221,566 to the entire disclosure of the teachings of the present invention, which is incorporated herein by reference. EV0H) and the first layer of 5-50% inorganic filler, as well as A second layer of a wet-impedance thermoplastic resin of an alkene having an average sheet thickness of no greater than 50 microns, an apparent ratio of at least 3, and a whiteness of at least 80 (measured by a Kett spectrophotometer) The material of Tokoh et al. does not have the resilience required for cushioning devices and other inflated articles. Therefore, a composition of a fluid barrier material having a high impermeability to the inflation gas is still required. SUMMARY OF THE INVENTION The present invention provides a At least one film comprising at least one elastic material and at least one polymer fluid barrier material, wherein the film has a laminar nano-fi ler, and the layer is The nanofiller has an average sheet thickness of up to about 10 nanometers and an average aspect ratio of at least about 200. The film preferably comprises at least one elastic layer of elastic material and at least one polymer fluid. A barrier layer that resists the early material of the material. The elastic material provides the elastic and dimensional stability of the film of the present invention, and the fluid barrier material allows the thin The membrane prevents the fluid from moving from thin to the other side. The layered nanofiller avoids fluid from one of the other sides of the film, does not significantly increase the non-transparency and enthalpy of the film, and does not reduce the elasticity of the film. The flexible barrier film can be used to inflate the inflated material. 4HDP/04002TW/NIKE-Replacement Page 7 1290941 Case No.: 93 1 23224 * , August 28, 2006 Amendment "Durable" means that the film has excellent resistance The elasticity is fatigued, and in particular, the film of the present invention can withstand repeated shrinkage and/or repetitive manufacture and recovery without stretching the interlayer of the film, preferably to withstand a wide range of temperatures. For the purposes of the present invention, the term "film" is used to mean a free-standing layer for the exchange of fluids, especially gases, preferably at about atmospheric pressure, with another fluid (liquid or gas) or with low pressure. The gas is separated. A film that is layered or embossed on another article other than the purpose of separating the fluids' is excluded from the film defined by the present invention. Another aspect of the present invention provides a film comprising a microlayer polymer composite layer having a microlayer comprising at least one polymer fluid barrier material and comprising at least one elastomer A microlayer, any layer having one or more other materials, all of which are regularly arranged in the composite layer. The polymeric fluid barrier material and/or elastomeric layer further comprises a shaped nanofiller having an average sheet thickness of up to about 1 nanometer and an average appearance ratio of at least about 200. The invention further provides an enclosure formed from a film of the invention, including but not limited to a permanently sealed, inflated, inflated article comprising a gemstone closure and an intumescent article. The swell may be sealed by a body such as nitrogen, which may be used to inflate or cushion, for example, to inflate a sports ball or provide cushioning for footwear that may be combined with other materials such as clothing or foam ( F〇am) outer layer to form a buffer device. The barrier film preferably has a relatively low gas diffusion rate and can be used for a 4HDP/04002TW/NIKE-replacement page 1129941. Case number: 93132224 Modified on August 28, 2006, the bulge is maintained "permanently" Sealing, that is, maintaining a useful internal pressure for the useful life of the article containing the expansion. One acceptable method for measuring the relative penetration, permeability, and diffusion of different film materials is ASTM D-1434-82-V. The gas diffusion rate of the film is expressed as the amount of gas diffused through the film per unit area and unit time. The gas diffusion rate may be expressed under standard temperature and pressure in units of (cc) (mil/(m2) (24hour), the present invention. The barrier film is preferably less than 1 (cc) (mil/(m2) (24hour). [Embodiment] The following description is merely a preferred embodiment and is not intended to limit the invention and its application. The invention provides a film having at least one layer, the film comprising at least one elastic material and at least one polymer fluid barrier layer, wherein the film has at least one layer of a layer of nano filler, the layered nano filler Having an average thickness of one of up to about 10 nanometers, and an average appearance ratio of at least about one. The film may be a single layer comprising an elastomeric material, a fluid barrier IV layer, and a layered nanoparticle. a filler, but the film preferably has at least two layers. The film preferably comprises at least one layer of an elastomeric material, and at least one layer of a barrier material, wherein the layer of elastomeric material and/or the layer of polymer barrier comprises layered naphthalene Meter a filler having a layered nanofiller having an average thickness of at least about 2 GG and an average appearance ratio. The layered nanofiller is preferably combined with a fluid barrier material, such as a fluid barrier material or The fluid barrier layer of the multilayer film. The elastic material can be - thermoplastic elastomer or rubber, thermoplastic elastomer 4HDP / 04002TW / NIKE - replacement page 1129942 Case number: 93132224 2 〇 August 28, 曰 Correction generally has One or more soft or easy, segmental segments to provide translatability properties and having a hard or rigid segment as a thermoreversible physical crosslink, allowing the polymer to be treated as a thermoplastic material, while in the chamber The elastic behavior is maintained at a temperature. For example, a thermoplastic elastomer has a soft or rubbery polymer segment like a polyester or polyether segment, and a hard or glass-like segment like a polyurethane segment. An ABA block copolymer such as styrene/butadiene/styrene has a similar structure, and the middle of the polymer chain is always a soft or elastic segment (ie, rubber-like) Polybutylene ), and its tail end is a glass-like section (ie polystyrene). Another suitable class of thermoplastic elastomer is dynamic vulcanizate, rubbery phase in the melted thermoplastic phase (rubbery phase) An embodiment of an elastomer suitable for forming an elastic layer, comprising not limited to a polyurethane elastomer, having an aromatic- and aliphatic-based elastomer, a homopolymer having a flexible polyethylene and a polypropylene (homopolymer) And copolymers (cop〇iymer) flexible olefins, styrene thermoplastic elastomers with block copolymers of styrene (ethylene-butadiene) styrene, polyamine elastomers, polyamine-ether elasticity Body, ester-ether and ester-ester elastomers, flexible ionics, thermoplastic hard rubber, flexible polyvinyl chloride homopolymers and copolymers, elastomeric acrylic polymers, and blends thereof Alloys such as polyvinyl chloride and polyvinyl chloride-polyurethane alloys. Rubber which may be extruded prior to crosslinking may be used, with crosslinking after extrusion of the film. The rubber inclusion is not limited to nitrile rubber and butyl rubber. Different elastomeric materials may be combined into a mixture in the same layer, or may be included in separate layers of the film. Particularly suitable are thermoplastic polyester-polyurethane, polyether-polyurethane and 10 4HDP/〇4〇〇2Tvv/nikE-replacement page 1290941. Case number: 93 1 23224 • August 2006 · 28曰 Modified polycarbonate-polyurethane, Including polytetrahydrofuran which is not limited to polyurethane and diol reagent (0〇17七六仕81^(11'(^1^811), polyester, polylactone polyester (especially poly-self) a polycaprolactone diol, or a polycarboxylic acid having a hydroxy group, a polyether or a ring of ethylene oxide and propylene oxide. a polyester prepared from a copolymer of oxyethylene and propylene oxide. These polymer diol-based polyurethanes are composed of polymer diols (polyester diol, polyether diol, polycaprolactone II). Alcohol, polytetrahydrofuran diol or polycarbonate diol), one or more polyisocyanates, and optionally reacted with a chain extension compound. Chain extension as referred to herein The compound has two or more functional groups, preferably two The functional group is reactive with the polyisocyanate group, and the polymer glycol polyurethane is preferably substantially linear (meaning that substantially all of the reactants are di-functional). The present invention is used to form a preferred thermoplastic polyurethane. Polyester diols are generally prepared by polyacids (including their anhydrides and their esters) and polycondensates, which are more condensed and condensed. It is preferred to have a dual functional group, that is, a diacid compound (an anhydrate containing a dibasic acid compound) and a diol (diol) for preparing a substantially linear polyester diol, although it may contain a small amount of a single Mono-functional, trifunctional, and more functional based materials (possibly up to 5 mole percent). Suitable dicarboxylic acids include, but are not limited to, glutaric acid, Succinic acid, malonic acid, oxalic acid, citric acid (phthalic 4HDP/04002TW/NIKE-replacement page 11 1290941 Case number: 93 1 23224 August 28, 2006 Correction Acid), hexahydrophthalic acid, adipic acid, maleic acid, and anhydrate thereof. Suitable polyols are not limited, and the extensions are selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, and pentanediol. Glycol), dipropylene glycol ((^口1:€^716116忌17(:〇1), tripropylene glycol (1:140): (^7161^ glycol), tetrapropylene glycol, cyclohexanol (cyclohexanedimethanol), 2-ethyl-1,6-propanediol, 1,4-butanediol, 1,5-butanediol (1) , 5-pentanediol), 1,3-propanediol, butylene glycol, neopentyl glycol, and mixtures thereof. Sometimes there is a small amount of ternary An alcohol or a higher functional polyol such as trimethyl propyl alcohol or pentaerythritol. In a preferred embodiment, the dicarboxylic acid comprises adipic acid and the diol comprises hydrazine. Butylene glycol, a catalyst generally used for esterification polymerization is protonic acid, Lewis acid, titanium And dialkyltin oxides. Polymerization of hydroxydicarboxylic acid compounds also produces polyesters, which may or may not contain a starting polyol. ' ~ Polyether or polylactone diol can be used for preparation. The thermoplastic oxime, 1 ether or t-s-sterol can be made from a starting diol initiator, a glycol such as ethylene glycol or propylene glycol, and an internal vinegar or alkenyl oxide or (Oxirane) chain extension reagent. Suitable chain for the preparation of polylactone = 4HDP/04002TW/NIKE-Replacement page 12 1290941 Case number: 93132224 Modified activating hydrogenate lactone on August 28, 2006. For example, appropriate Inside, the bag, but not limited ε-hexa vinegar inside the vinegar, 10,000 _ ding;:
(butyrolactone) ^ Sl(propriolactone) ^ r-T(butyrolactone) ^ Sl(propriolactone) ^ r-T
Tl\a'J^~6'T^m ' ^ γ-Α 内自曰(valerolactone)、占-戊内酯、 穴 (decanolactone)、3 -葵内醋、^ —壬天:曰 lactone)、r-辛内酯(〇ctan〇ic lact〇ne)及其組 使用於本發明之環内酯可以下列化學式表之··Tl\a'J^~6'T^m ' ^ γ-Α 曰 valerolactone, valinolactone, decanolactone, 3 - vinegar, ^ —壬: lactone, R-octanolactone (及其ctan〇ic lact〇ne) and its group can be used in the following chemical formulas for the cyclic lactones of the present invention.
RR
Ο 〇 其中η為1-7的正數,R為一或多個氫原子或取 未取代的曱基® ’包含卜7個碳原子。可用的催化劑包 含上述可合成聚酯的催化劑,反應也可以開== 之鈉鹽於會產生内酯之環的分子上。 々取匕丞 f 施例中’二醇起始劑與包含環氧乙烷 ^ 聚⑽乙醇’以驗進行聚氨醋的聚合 反應,此包含裱氧乙烷的化合物較佳為伸烴基氧化物 (alkylene oxide)或環醚(cyciic ether),尤豆 氧乙爹、環氧丙烷、環氧丁烷、四氫呋喃其及;且合物。伸义 烴基氧化物之聚合物之區段包含但非限定於 ,丙烷、1:2-環氧己烷、1-環氧丁烷、2_環氧丁烷、“ 氧己烧、第二丁基環氧乙烧、笨聚縮水甘油_(油_ glycidyl ether)、1-環氧葵烷、環氧異丁烧Us〇b咖· 4HDP/04002TW/NIKE-替換頁 13 1290941 案號:93123224 2006年8月28曰修正 oxide)、氧化環戊烯(cyclipetene oxide)、1-環氧戊烷 及其組合物經聚合反應所得之產物,其中較佳為環氧乙 烧、環氧丙烧及其組合物,此伸烴基氧化物之聚合反應一 般為鹼性催化,此反應之進行,舉例來說,藉由加入羥基 起始劑、一催化量的苛性鈉(caustic),如氳氧化鈉、甲 醇鈉(potassium methoxide)或第三 丁醇鈉(p〇tassium tert-butoxide),以及以一足夠的速率下加入伸烴基氧化 物以保持反應時有足量的單體,二或多種不同的伸烴基氧 化物單體可能會任意地共聚合,這是因為併發加成 (coincidental addition)及依序加入造成塊狀聚合,較 佳為環氧乙烧、環氧丙烧的同元聚合物或共聚合物。 在已知條件下將四氫呋喃聚合以形成下列重複的單 元: —^CH2CH2CH2CH2〇J_ 四氳呋喃是使用如 SbFe-、AsF6-、PF6_、SbCl6-、BF4-、 CF3SO3、FS〇3、Cl〇4之相反離子(counterion)以進行陽離 子開%反應’開始時形成三級質子(tertiary oxonium ion)。製備此聚四氫呋喃以作為一活性聚合物(living polymer) ’且當加入前述之具有羥基之二醇時反應終止。 製備脂族(aliphatic)聚碳酸酯二醇可藉由二醇與二 烧基碳酸酯(dialkyl carbonate)(如二乙碳酸酯(diethyl carbonate))、二苯碳酸酯、二氧環内(diox〇lan〇ne)(如 具有五環及六環之環碳酸酯),於如鹼金屬之催化劑、錫 催化劑或鈦催化劑存在的環境下進行反應。可使用的二醇 4HDP/04002TW/NIKE-替換頁 14 1290941 案號:93123224 2006年8月28曰修正 包含但非限定於任何上述化合物。芳香族聚碳酸酯一般藉 由紛甲院〇^?1^11〇1),如2,2-酚曱烷八〇^0[^11〇1八), 與光氣(phosgene)或二苯碳酸酯製備而得。 較佳用於合成聚氨酯的聚二醇,如前述之聚酯二醇, 具有一平均分子量介於約300至約4000(樣品由ASTM D一4274所測定),較佳為約400至約30000,更佳者為約 500至約2000。此聚二醇一般形成彈性聚氨酯之r柔軟區 段」(soft segment)。 此彈性聚氨酯之合成可藉由一或多種上述之聚二 醇、一或多種具有至少兩個異氰酸酯基團之化合物,以及 選擇性地加入一或多種鏈延伸試劑。此彈性聚氨酯較佳為 線性的,因此異氰酸酯化合物較佳實質上具有雙官能基。 可用的異氰酸酯化合物,係用於製備本發明之熱塑性聚氨 醋’包含但非限定於二異氰酸異佛爾酮(isophorone diisocyanate(IPDI))、伸曱基雙-4-環己基異氛酸醋 (methylene bis-4-cyclohexyl isocynate)、環己烯二異 氰酸酯(cyclohexylene diisocyanate(CHDI))、m-四曱基 離氨酸二異氰酸酯(m-tetramethyl xylyene diisocyanate(m-TMXDI))、p-四甲基離氨酸二異氰酸酯 (P-TMXDI)、伸乙基二異氰酸酯、1,2-二異氰酸丙烷 (1,2-diisocyanatopropane)、1,3-二異氰酸丙烧、1,6-二異氰酸己烷(六甲基二異氰酸酯或HDI)、1,4-伸丁基二 異氰酸S旨、離氨酸二異氰酸醋、1,4-伸曱基雙環己基異氰 酸酯(1,4-methylene bis(cyclohexyl isocynate))、異 氰酸曱苯酯(toluene diisocyanate)之各種異構物、間離 15 4HDP/04002TW/NIKE-替換頁 1290941 案號:93123224 2006年8月28曰修正 氨酸二異氰酸酯及對離氨酸二異氰酸酯、4-氯-1,3-伸苯 基一異乱酸酯(4-chloro-1,3-phenylene diisocyanate) 、1,5-四氫萘二異氰酸酯 (l,5-tetranaphthalene diisocyanate)、4,4-二苯二異 氰酸酯及1,2, 4-三異氰酸苯酯、離氨酸二異氰酸酯(xdi) 及其組合物,特別適用者為二異氰酸二伸苯曱醋 (diphenylenemethane diisocyanate MDI)。 適當的活性氫(hydrogen-con t a i n i ng )鏈延伸試劑一 般包含兩個活性氫基團,如二醇、二硫醇、二胺,或如烧 醇胺(alkanolamine)、烷胺基硫醇(aminoaikyi mercaptan)、羥曱基硫醇等具有羥基、硫醇基及胺基的化 合物,此類鏈延伸試劑分子量從約60至約400,較佳為醇 及胺類。典型作為聚氨酯鏈延伸物之適當二醇包含但非限 定為1,6-己二醇、環己基二曱醇(Eastman化學公司銷售 之 CHDM)、2-乙基-1,6-己二醇、酯二醇 204(Esterdiol 204) (Eastman化學公司銷售)、1,4-丁二醇、乙二醇;以及乙 二醇之較低寡聚合物(oligomer),包含乙二醇、乙三醇、 乙四醇、乙五醇;以及丙二醇之較低寡聚合物,包含丙二 醇、丙三醇及丙四醇;1,3-丙二醇、1,4-丁二醇、新戊二 醇;二經曱基芳香族化合物,如對苯二盼(hydroquinone) 和間苯二酚(resorcin〇l)之二(2-羥乙基)乙謎 (bis(2-hydroxyethyl)ether);對離胺酸-α-α,-二 醇;對離胺酸-α-α’ -二醇之二(2-經乙基)乙_ ;間離 胺酸-α-α’ -二醇及其二(2-羥乙基)乙醚,及上述之組 合物。適當的二胺鏈延伸物包含但非限定於對伸苯基二 胺、間伸苯基二胺、聯苯胺(benzidine)、乙二胺及其組 16 4HDP/04002TW/NIKE-替換頁 •1290941 案號·· 93123224 2006年8月28曰修正 合物。其他典型的鏈延伸物為 二乙二 丙一醇、三丙二醇、四 ί醇:及ί組丁合,較佳的延伸物仏^、 私丙一知、丁二醇、戊二醇、 如二mn延伸物外’也可能會出現-少量 :一 6—己二醇及甘油之三官能基之 Ξ用且m丁醇或二甲胺之單官能基活性含氫化合物, ίϊ:1:ί之延伸物及單官能基之化合物,較佳為根據 反應產物及使用的.含氫化合物之總重量之5. ◦當量百 分比或更少。 一般藉由將化合物加熱,以實施聚異氰酸酯、聚二醇 及選擇性地鏈延伸試劑之反應,如藉由於雙螺桿擠壓機 (twin-screw extruder)中之溶解反應,而此類反應一般 之催化劑包含有機錫,如辛酸亞錫(stann〇us 〇ct〇ate)或 一月桂酸一丁基錫(dibutyl tin dilaurate)。一般如聚 酯二醇之聚二醇,其與延伸物之比例可以在相對寬的範圍 内變化,主要視最終聚氨酯彈性體所期待的硬度而定,舉 例來說聚酯二醇與延伸物之當量比可能在1 ·· 〇至1 : 12, 且較佳為1 ·· 1至1 : 8。較佳地使用的二異氰酸酯呈適當 比例,使得異氰酸酯之總當量比對活性含氫材料之比例在 0· 95 : 1 至 1· 10 : 1 之間,較佳為 〇· 98:1 至 1· 04 : 1。此 聚二醇區段一般由重量百分比約35%至約65%之聚氨酯聚 合物所形成,較佳為由重量百分比約35%至約50%之聚氨 酯聚合物所形成。 4HDP/04002TW/NIKE-替換頁 17 .1290941 案號:93 1 23224 2006 _ 8月28曰修正 於某些特定應用上,薄膜之彈性層或一些層具有聚氨 酯混合物是期待的,例如當對於水解敏感時,這是特別重 要。舉例來說,聚氨酯包含聚醚二醇或聚酯二醇之柔軟區 段,其中反應產物之重複單元具有大於八個碳原子,可與 具有八個或更少碳原子之聚酯二醇或二醇分枝之產物混 ^,較佳為不包含具有八個或更少碳原子,或氧原子接觸 三級f之重複單元之聚酯二醇的那些聚氨醇,於混合物中 具有高達30%重量百分比柔軟區段。(也就是說基於聚氨酯 中二基於·重量百分比之聚乙二醇己二酸g旨,與基於· · $量百分比液酞酸聚酯二醇)。聚酯二醇之範例為聚酯二 醇,其中反應產物具有大於八個碳原子,包含聚乙二醇駄 酸酯、聚1,4-丁二醇酞酸酯,以及聚—1,6—己二醇酜酸酯。 、可能使用具有多個柔軟區段的單一聚氨醋,而非多種 熱塑性聚氨酯之混合物,於一實施例中,柔軟區段可能包 含聚酯之柔軟區段;或是與聚酯之柔軟區段結合,且具有 總數八個或更少碳原子之重複單位的聚醚多元醇;或是具 f總數大於八個碳原子之重複單位的聚醚多元醇。較佳^ φ 是,具有總碳數大於八個之重複單位的柔軟區段總數,係 包含於聚氨酯中之柔軟區段總重約3〇%之重量百分比。於 另-較佳實施例中,包含至少約7隨量百分比之總數八 個或更少碳原子之重複單位的柔軟區段。 適用的商業化彈性材料的例子包含Elf At〇chem、商 心PEMAX®所銷售的聚酸胺—_,跡〇的、商標jjytrel®所 銷售的自曰-醚彈性體,DSM工程、商標y\RNITEL®所銷售的 4HDP/04002TW/NIKE-替換頁 18 .1290941 案號:93 1 23 224 , 2006年8月28 p修正 醋-醋及S旨-謎彈性體,Advanced Elastomeric System、 商標SANT0PRENE®所銷售的熱塑性硬塑膠,EMS-Chmie, Sumter, SC、商標GRILAMID®所銷售的彈性聚醯胺,Dow Chemical Company,Midland,Ml、商標 PELLETHANE®所銷 售的彈性聚氨酯、Bayer所銷售的商標TEX IN®及DESMOPAN 的聚氨酯’Huntsman所銷售的MORTHANE,Noveon所銷售 的ESTANE®聚氨酯。 此薄膜也可包含一聚合物阻障材料,此聚合物阻障材 料可能為彈性材料之混合物,舉例來說為單層薄膜,或作 為單層之多層薄膜。在此例中,較佳的是少量的聚合物阻 障材料與大量的彈性材料,使得彈性材料為一連續基質 (matrix)。 然而,此聚合物阻障材料較佳為與包含彈性材料之層 分隔為單獨一層,一般此聚合物阻障材料層較彈性材料層 薄,如此此薄膜將為易彎曲且耐用的。 適當的聚合物阻障材料包含但非限定於乙基乙浠醇 共1物,聚氣乙烯,聚偏二鹵乙烯聚合物及共聚物,包含 聚乙烯叉二氣;聚醯胺,包含非定型聚醢胺;丙浠腈,包 含丙烯腈—醯酸甲酯;聚氨酯工程塑膠;聚甲基戊稀樹脂; 乙烯―氧化碳共聚物;液晶聚合物;聚醋,如U酸乙 二醇;聚醯亞胺,包含聚醚醯亞胺及聚丙烯醯亞胺;以及 ,他已知具有低氣體擴散速率之聚合物材料。這些材料的 混合物及接枝(graft)也是適合的材料,舉 & 亞胺與如液晶聚合物之晶體聚合物之組合物 4HDP/〇4〇〇2TW/N|KE_ 替換頁 1290941 案號:93123224 2006年8月28曰修正 酞酸乙二醇,以及具有苯乙烯之聚醯胺之組合物。此薄膜 可能具有一層或不同流體阻障材料之組合物層,或不同流 體阻障材料也可能以分開之多層而包含在此薄膜中。 幸父佳為乙婦-乙稀醇共聚物’特別是那些具有乙稀共 聚早體之莫爾百分比為25至50的共聚物,最佳的是莫爾 百分比為25至50。乙浠-乙烯醇共聚物由已知之水解乙稀 -乙酸乙烯醋共聚物所製備。 適當的特定物品例子包含如BP Chemical Inc.,供應 的 BAREX® ;如 Dow Chemical Corp·,Midland,Ml 供應的Ο 〇 where η is a positive number from 1 to 7, and R is one or more hydrogen atoms or an unsubstituted fluorenyl group ’ contains 7 carbon atoms. The catalyst which can be used comprises a catalyst which synthesizes the above polyester, and the reaction can also be carried out on the molecule which will produce a ring of lactone. The diol starting agent and the epoxide containing poly(10) ethanol are used to carry out the polymerization of the polyurethane, and the compound containing oxirane is preferably a hydrocarbyl oxide. (alkylene oxide) or cyciic ether, especially styrene, propylene oxide, butylene oxide, tetrahydrofuran; The section of the polymer of the extended hydrocarbon-based oxide includes, but is not limited to, propane, 1:2-epoxyhexane, 1-butylene oxide, 2-epoxybutane, "oxygenated, second" Epoxy Ethylene Baked, Glycidyl Ether Glycerin_(Oil_Glycidyl Ether), 1-Epoxy Oxide, Epoxy Isobutyl Osmium, 4HDP/04002TW/NIKE-Replacement Page 13 1290941 Case No.: 93322324 A product obtained by polymerization of a modified oxide), cyclipetene oxide, 1-epoxypentane and a combination thereof, preferably Ethylene Ethylene, Epoxy-C-Athene, and In the composition, the polymerization of the hydrocarbyl oxide is generally basic catalysis, and the reaction is carried out, for example, by adding a hydroxyl initiator, a catalytic amount of caustic, such as sodium bismuth oxide, methanol. Sodium (meth) methoxide or sodium p-butoxide (t〇tassium tert-butoxide), and a sufficient rate of addition of a hydrocarbyl oxide to maintain a sufficient amount of monomer, two or more different hydrocarbyl groups Oxide monomers may be arbitrarily copolymerized because of the coincidental addition and The sequential addition results in a bulk polymerization, preferably a homopolymer or a copolymer of ethylene bromide or propylene oxide. The tetrahydrofuran is polymerized under known conditions to form the following repeating units: —^CH2CH2CH2CH2〇J_4 The terpene is a tertiary oxonium formed by using a counterion such as SbFe-, AsF6-, PF6_, SbCl6-, BF4-, CF3SO3, FS〇3, Cl〇4 for the cationic open % reaction. The polytetrahydrofuran is prepared as a living polymer' and the reaction is terminated when the aforementioned diol having a hydroxyl group is added. The preparation of an aliphatic polycarbonate diol can be carried out by using a diol and a diol. Dialkyl carbonate (such as diethyl carbonate), diphenyl carbonate, dioxane (diox〇lan〇ne) (such as a cyclic carbonate having a five-ring and a six-ring), The reaction is carried out in the presence of an alkali metal catalyst, a tin catalyst or a titanium catalyst. The diol 4HDP/04002TW/NIKE-replacement page 14 1290941 can be used. Case number: 93132224 August 28, 2006 Amendment includes but not limited to Any on Compounds. Aromatic polycarbonates are generally obtained by the genus 纷^?1^11〇1), such as 2,2-phenol decane 〇 0 ^0 [^11〇18), with phosgene or Diphenyl carbonate is prepared. Preferred are polyglycols for the synthesis of polyurethanes, such as the aforementioned polyester diols, having an average molecular weight of from about 300 to about 4,000 (samples as determined by ASTM D-4274), preferably from about 400 to about 30,000. More preferably, it is from about 500 to about 2,000. The polyglycol typically forms the soft segment of the elastomeric polyurethane. The elastomeric polyurethane can be synthesized by one or more of the above polyhydric alcohols, one or more compounds having at least two isocyanate groups, and optionally one or more chain extending agents. The elastic polyurethane is preferably linear, and therefore the isocyanate compound preferably has substantially a difunctional group. Useful isocyanate compounds for the preparation of the thermoplastic polyurethane of the present invention include, but are not limited to, isophorone diisocyanate (IPDI), diterpene bis-4-cyclohexyl enoic acid Methylene bis-4-cyclohexyl isocynate, cyclohexylene diisocyanate (CHDI), m-tetramethyl xylyene diisocyanate (m-TMXDI), p-four Methyl lysine diisocyanate (P-TMXDI), ethyl diisocyanate, 1,2-diisocyanatopropane, 1,3-diisocyanate, 1,6 - Hexane diisocyanate (hexamethyl diisocyanate or HDI), 1,4-butylene diisocyanate, isopropyl acetonate, 1,4-decyl biscyclohexyl isocyanate (1,4-methylene bis(cyclohexyl isocynate)), various isomers of toluene diisocyanate, separation 15 4HDP/04002TW/NIKE-Replacement Page 1129941 Case No.: 93322224 August 28, 2006曰 氨酸 二 二 diisocyanate and lysine diisocyanate, 4-chloro-1,3-phenylene monoisoester ( 4-chloro-1,3-phenylene diisocyanate), 1,5-tetranaphthalene diisocyanate, 4,4-diphenyldiisocyanate and 1,2,4-triisocyanate Esters, lysine diisocyanates (xdi) and combinations thereof, particularly suitable for diphenylenemethane diisocyanate MDI. Suitable active hydrogen (hydrogen-contained ng) chain extension reagents generally comprise two active hydrogen groups, such as diols, dithiols, diamines, or, for example, alkanolamines, alkylamine thiols (aminoaikyi) A compound having a hydroxyl group, a thiol group and an amine group, such as mercaptan), such as a hydroxymercaptothiol, has a molecular weight of from about 60 to about 400, preferably an alcohol and an amine. Suitable diols typically as extensions of the polyurethane chain include, but are not limited to, 1,6-hexanediol, cyclohexyldidecyl alcohol (CHDM sold by Eastman Chemical Company), 2-ethyl-1,6-hexanediol, Esterdiol 204 (sold by Eastman Chemical Company), 1,4-butanediol, ethylene glycol; and lower oligomer of ethylene glycol, including ethylene glycol, glycerol, Ethylene glycol, pentanediol; and lower oligomeric polymer of propylene glycol, including propylene glycol, glycerol and propylene glycol; 1,3-propanediol, 1,4-butanediol, neopentyl glycol; Aromatic compounds such as hydroquinone and resorcinol (bis(2-hydroxyethyl)ether); lysine-α -α,-diol; bis(2-ethyl)-ethyl phthalate-α-α'-diol; m-amino acid-α-α'-diol and its bis(2-hydroxyl) Ethyl)ether, and combinations thereof. Suitable diamine chain extensions include, but are not limited to, p-phenylenediamine, meta-phenylenediamine, benzidine, ethylenediamine, and their group 16 4HDP/04002TW/NIKE-Replacement Page • 1129094 No. · 93123224 August 28, 2006 correction compound. Other typical chain extensions are diethylenedipropanol, tripropylene glycol, tetrakiol: and butyl groups, preferred extensions 、^, isopropyl, butanediol, pentanediol, such as Mn extensions may also appear - small amounts: a 6-hexanediol and a trifunctional group of glycerol and a monofunctional active hydrogen-containing compound of m butanol or dimethylamine, ίϊ:1: The extender and the monofunctional group compound are preferably 5. The equivalent weight percentage or less based on the total weight of the reaction product and the hydrogen-containing compound used. The reaction is generally carried out by heating the compound to effect the reaction of a polyisocyanate, a polyglycol, and a selective chain extender, such as by a dissolution reaction in a twin-screw extruder. The catalyst comprises an organotin such as stannous 〇ct〇ate or dibutyl tin dilaurate. In general, such as polyglycols of polyester diols, the ratio of the diols to the extensions can vary over a relatively wide range, depending primarily on the hardness desired for the final polyurethane elastomer, for example, polyester diols and extensions. The equivalent ratio may be from 1 ··〇 to 1:12, and preferably from 1··1 to 1:8. Preferably, the diisocyanate is used in a suitable ratio such that the ratio of the total equivalent ratio of the isocyanate to the active hydrogen-containing material is between 0.95:1 and 1·10:1, preferably 〇·98:1 to 1. 04 : 1. The polyglycol segment is typically formed from about 35% to about 65% by weight of the polyurethane polymer, preferably from about 35% to about 50% by weight of the polyurethane polymer. 4HDP/04002TW/NIKE-Replacement Page 17.1290941 Case No.: 93 1 23224 2006 _ August 28曰 Revised in some specific applications, the elastic layer of the film or some layers with a polyurethane mixture is expected, for example when sensitive to hydrolysis This is especially important. For example, the polyurethane comprises a soft segment of a polyether diol or a polyester diol, wherein the repeating unit of the reaction product has more than eight carbon atoms, and can be combined with a polyester diol having eight or fewer carbon atoms or two Mixtures of alcoholic branches, preferably those which do not contain a polyester diol having eight or fewer carbon atoms, or an oxygen atom contacting a repeating unit of tertiary f, up to 30% in the mixture Weight percent soft section. (That is to say based on the polyurethane based on the weight percentage of polyethylene glycol adipate g, and based on the amount of liquid phthalic acid polyester diol). An example of a polyester diol is a polyester diol wherein the reaction product has more than eight carbon atoms, including polyethylene glycol phthalate, poly 1,4-butanediol phthalate, and poly-1,6- Hexanediol phthalate. It is possible to use a single polyurethane with multiple soft sections instead of a mixture of multiple thermoplastic polyurethanes. In one embodiment, the soft section may comprise a soft section of polyester; or a soft section with polyester a polyether polyol that is combined and has a repeating unit of a total of eight or fewer carbon atoms; or a polyether polyol having a repeating unit of f total of more than eight carbon atoms. Preferably, φ is the total number of soft segments having a repeating unit having a total carbon number of more than eight, and is a weight percent of the soft segment contained in the polyurethane of about 3% by weight. In another preferred embodiment, a soft segment comprising at least about 7 percent by number of repeating units of a total of eight or fewer carbon atoms. Examples of suitable commercial elastomers include Elf At〇chem, Polyamines sold by Shangxin PEMAX®, 曰, the self-twisting ether elastomer sold by the trademark jjytrel®, DSM Engineering, Trademark y\ 4HDP/04002TW/NIKE-Replacement Page for sale by RNITEL®18.1290941 Case No.: 93 1 23 224, August 28, 2006 p Modified vinegar-vinegar and S-mystery elastomer, Advanced Elastomeric System, trademark SANT0PRENE® Thermoplastic hard plastics sold, EMS-Chmie, Sumter, SC, elastomeric polyamines sold under the trademark GRILAMID®, flexible polyurethanes sold by Dow Chemical Company, Midland, Ml, trademark PELLETHANE®, and trademarks sold by Bayer TEX IN® And DESTHPAN's polyurethane 'Huntsman' sold by MORTHANE, Noveon sold by ESTANE® polyurethane. The film may also comprise a polymeric barrier material which may be a mixture of elastomeric materials, for example a single layer film, or a multilayer film as a single layer. In this case, a small amount of the polymer barrier material and a large amount of the elastic material are preferred, so that the elastic material is a continuous matrix. Preferably, however, the polymeric barrier material is separated from the layer comprising the elastomeric material as a separate layer. Typically, the polymeric barrier material layer is thinner than the elastomeric material layer such that the film will be pliable and durable. Suitable polymeric barrier materials include, but are not limited to, ethyl ethoxylate, polyglycol, polyvinylidene halide polymers and copolymers, including polyethylene fork gas; polyamine, including non-stereo Polyamide; acrylonitrile, including acrylonitrile-methyl decanoate; polyurethane engineering plastics; polymethyl pentylene resin; ethylene-oxygen oxyethylene copolymer; liquid crystal polymer; polyacetic acid, such as U acid glycol; A quinone imine comprising a polyether quinone imine and a polypropylene quinone imine; and, he is known to have a polymer material having a low gas diffusion rate. Mixtures and grafts of these materials are also suitable materials, and combinations of imines and crystalline polymers such as liquid crystal polymers 4HDP/〇4〇〇2TW/N|KE_ Replacement Page 1129941 Case No.: 93322324 Aug. 28, 2006 revised a composition of decanoic acid glycol and a polyamidamine having styrene. The film may have a layer of one or more fluid barrier materials, or different fluid barrier materials may be included in the film in separate layers. Fortunately, the father-in-law is a polyethylene-ethylene glycol copolymer, especially those having a molar percentage of 25 to 50 having a ethylene-accumulated precursor, and the most preferred molar percentage is 25 to 50. The acetamethylene-vinyl alcohol copolymer is prepared from a known hydrolyzed ethylene-vinyl acetate copolymer. Examples of suitable specific articles include BAREX® as supplied by BP Chemical Inc.; such as Dow Chemical Corp., Midland, Ml.
ISOPLAST®的聚氣S旨工程塑膠;如EVAL Company of America(EVALCA)所銷售、商標 EVAL®,Nippon Goshei Co., Ltd(USA) of New York, NY,的 Lisle Illinois, S0ARN0L®,Solvay 的 CLARENE®,DuPont 的 SEALR®0H 的乙 烯-乙烯醇共聚物;如Dow Chemical、商標SARAN®2K7, Solvay、商標 IXAN®偏二氯乙烯;如 Hoechst Celanese 的 VECTRA,如 Amoco Chemicals 的 XYDAR®的液晶聚合物; Mitsubishi Gas Chemical Co., Ltd, Solvay, and Toyobo 的 MXD6 尼龍;如 Mitsubishi 的 N0VAMID®X21,PA DuPont 的 SELAR® , General Electric Company 的 GEL0N A-100 的非定形尼龍;Rohm&Haas的KAMAX®聚丙烯醯亞胺共聚 物;General Electric所銷售、商標ULTEM®的聚乙醚醯 亞胺;Air Product供應的VINEX聚乙烯-乙烯醇;Phi 1 ips 66 Company 供應、商標 CRYSTALOR,來自 Mitsui Petrochemical Industries、商標 TPX®的聚甲基戊烯樹 脂。最佳的商業乙烯-乙烯醇共聚物,舉例來說為EVALCA 4HDP/04002TW/NIKE-替換頁 20 1290941 案號:93 1 23224 2006年8月28曰修正 =應的’具有約25莫爾百分比至48莫爾百分比的乙烯 ,膜之至少-層’或單層細之至少—聚合物材料包 二f狀奈米填料’層狀奈米填料具有達約10奈米之-二度及至少約之—平均外觀比值。於薄膜 ^ 一較j土實施例’包含一彈性層及一阻障材料層彈性 二阻障材料層或兩者具有一層狀奈米填料,具有約1〇 不米之一平均薄層厚度,及至少約200之一平均外觀比 ,^父佳的雜奈料料約為丨奈米至約1()奈米之厚度, 分別從G.1微米至丨.5微米。平均外觀比錄佳 石土最佳伽至約5— 於薄膜的-較佳實施例,單層包含佔 =橡二,性聚氨醋彈性體,佔少量的⑶ 胺’及佔全部組合物重量百分比約達⑽ 真料,於—較佳的實施例中,此彈性體於熱塑 ^材料中、於另-雜體’或於彈性體轉材料 橡膠及雜體轉材料,賴其他^塑^ 弹性體之間的共價鍵可用於促進介面的黏著。 ^狀奈米填料可與親水的共聚物一同使用而益 將之修飾,以增加聚合财層狀奈“ ιϋ'物的親合性(如有助於層狀奈米填料之剝離及 新堆疊。於一較佳的修飾為十八院基三甲 風她,斜八絲三甲顧'倾與紙層狀奈米埴料 4HDP/04002TW/NIKE-替換頁 21 1290941 案號:93 1 23224 2006年8月28曰修正 料,以及之後乾燥奈米材細g真制濕、加入處理材 -,ίΐΓΐίί料使祕_時具錢異的性質,第 1〇重“旦百:,善薄膜於負载(—g)a夺(約4至約 體阻障特性,這通f不會影㈣膜之 透月矛度:、、、、而,使用如滑石或雲母之傳统埴料,蔣佶尸ISOPLAST® is a engineering plastic; such as the EVAL Company of America (EVALCA), the trademark EVAL®, Nippon Goshei Co., Ltd (USA) of New York, NY, Lisle Illinois, S0ARN0L®, Solvay's CLARENE ®, DuPont's SEALR®0H ethylene-vinyl alcohol copolymer; such as Dow Chemical, trademark SARAN® 2K7, Solvay, trademark IXAN® vinylidene chloride; such as Hoechst Celanese's VECTRA, such as Amoco Chemicals' XYDAR® liquid crystal polymer Mitsubishi Gas Chemical Co., Ltd, Solvay, and Toyobo's MXD6 nylon; such as Mitsubishi's N0VAMID® X21, PA DuPont's SELAR®, General Electric Company's GEL0N A-100 amorphous nylon; Rohm & Haas' KAMAX® Propylene quinone copolymer; polyethyl phthalimide sold by General Electric under the trademark ULTEM®; VINEX polyethylene-vinyl alcohol supplied by Air Product; Phi 1 ips 66 Company supplied, trademark CRYSTALOR, from Mitsui Petrochemical Industries, trademark TPX ® Polymethylpentene Resin. The best commercial ethylene-vinyl alcohol copolymer, for example, EVALCA 4HDP/04002TW/NIKE-Replacement Page 20 1290941 Case No.: 93 1 23224 August 28, 2006 Correction = should have 'approximately 25 mole percentages to a percentage of 48 moles of ethylene, at least a layer of the film or at least a layer of fineness - a polymeric material comprising two f-type nanofillers' layered nanofillers having a di-nano-second degree and at least about - Average appearance ratio. The film comprises a layer of elastic layer and a layer of elastic barrier material of the barrier material layer or both of which have a layer of nano filler, having an average thickness of about 1 〇, and an average thickness of the layer. And an average appearance ratio of at least about 200, the father's hash material is about 丨 nanometer to about 1 () nanometer thickness, respectively, from G. 1 micron to 丨. 5 micron. The average appearance is better than that of the recorded stone soil to about 5 - in the case of the film - the preferred embodiment, the single layer comprises the rubber, the polyurethane polyurethane, the small amount of the (3) amine and the total weight of the composition The percentage is about (10). In the preferred embodiment, the elastomer is in the thermoplastic material, in the other-hybrid or in the elastomer-transferred rubber and the hybrid material. Covalent bonds between the elastomers can be used to promote adhesion of the interface. The n-type nanofiller can be used together with a hydrophilic copolymer to modify it to increase the affinity of the polymeric layered na[iota] (e.g., to facilitate stripping of the layered nanofiller and new stacking. In a better modification, it is the eighteen yards of the top three winds, she is inclined, eight silks, three nails, and the paper layered nano-materials 4HDP/04002TW/NIKE-replacement page 21 1290941 Case number: 93 1 23224 August 2006 28 曰 correction material, and after drying the nano material fine g really wet, adding processing material -, ΐΓΐ ί ί ί 使 秘 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ ) a capture (about 4 to about the body barrier properties, this pass f will not affect (four) the film through the moon::,,,,, using traditional materials such as talc or mica, Jiang Zang
St:透;,度增加至足以= 沾鱼j#、 相心於傳統填料,層狀奈米填料之較低 及勒产較小的薄片,將改善薄膜的模數(modulus) =。例子中’層狀奈米填料併入聚合物阻 增,物阻障材料之結晶度。層狀奈米 村提供層之氣_散速率,沒有層狀奈 未填科,财質上不㈣軸之鏡紐料有貢獻。 ϋ奈米填料可併入層材料,舉例來說,係藉由已知 j=(comp〇unding meth〇d)。併入層狀奈米填料也可 ΐΐΐί層狀奈米填料與—單體,或其他於聚合前用於形 的試劑。如所述,層狀奈米填料可由適當的試 處理,有助於其分散於層材料中。 了月b用於或夕層的額外材料包含修飾劑 巧他添加劑’少量為佳。此類修飾劑及添加劑舉例來說 =3^非限定於塑化劑、光穩定劑、水解穩定劑、熱穩定 ,、光澤劑、抗氧化劑、流變修飾劑、有機反阻斷 (anti-block)化合物、殺真菌劑、抗微生物劑(包含殺菌 4HDP/04002TW/NIKE-替換頁 22 1290941 案號:93123224 2006年8月28日修正 劑及類似者)、脫_、如Μ_η轉二 劑與及其組合物。著㈣__可由如射^透 之透明著色,形成。於透明薄膜中的特別 虹彩 (mdeSCene),可藉由特定效果的顏料達成。 石” f解,定劑,例來說包含兩種商業化之二亞醯胺化 =式(carbochmude based)水解穩定劑,如已知由St: Translucent;, the degree is increased enough = dimming fish j#, concentric with traditional fillers, lower layered nanofillers and lesser-produced flakes, will improve the modulus of the film =. In the example, the layered nanofiller is incorporated into the polymer to retard the crystallinity of the barrier material. The layered nano-village provides a layer of gas _ scatter rate, no layered nai is not filled, the financial quality does not (four) axis mirror material contribution. The nano-filler can be incorporated into the layer material, for example by knowing that j = (comp〇unding meth〇d). The incorporation of the layered nanofiller can also be used to form layered nanofillers and monomers, or other reagents used for the formation prior to polymerization. As noted, the layered nanofiller can be suitably treated to aid dispersion in the layer material. The extra material used for the month b or the layer of the layer contains a modifier. Such modifiers and additives are, for example, not limited to plasticizers, light stabilizers, hydrolysis stabilizers, heat stabilizers, gloss agents, antioxidants, rheology modifiers, organic anti-blocking (anti-block) Compounds, fungicides, antimicrobial agents (including bactericidal 4HDP/04002TW/NIKE-replacement page 22 1290941 case number: 93322224 August 28, 2006 amendments and the like), 脱,如Μ_η转二剂和Its composition. (4) __ can be formed by transparent coloring such as radiation. Special iridescent inks (mdeSCene) in transparent films can be achieved with pigments of specific effects. Stone"f solution, a formulation, for example, comprises two commercial diammonium-carbohydrate-based hydrolysis stabilizers, as known by
Ρ ΐΓ〇 ί J-611'011 f STABAX〇L P STABAX〇L 藉1 紹fc碳式或聚二競舰碳視之水解 豆油可能是有用的,-般使用水解 穩疋劑的總篁可能小於層總重之5 %。 塑化既可被包含在内,用於增加最終產物的彎曲性及 ,用性’以及增進材料從樹脂形式至薄膜或薄片,舉例來 說’但非用於限定’那些基於四苯基酞酯的塑化劑被證實 ,別有用。不論是塑化劑或塑化劑之混合物,塑化劑之總 里一般佔小於所有層之20%重量百分比,較佳為小於總層 重量之5%重量百分比。 ^發明之薄膜可能包含微層聚合物複合層,此微層聚 合物複合層至少具有如前所述之流體阻障材料之交替微 層’以及如前所述之彈性材料。也要考慮到微層聚合物複 合層包含不同流體阻障材料之微層,且/或包含不同彈性 材料之微層,這些不同層以一規律重複之排列。也可能包 含除了彈性層及流體阻障層之外的其他層,與彈性層及流 體阻障層以一規律重複之交替排列。此微層聚合物複合層 應至少具有約10微層,此微層聚合物複合層較佳至少具 23 4HDP/04002TW/NIKE-替換頁 ‘1290941 、 . 案號:93123224 , 2006年8月四日修正 有約20微層,此微層聚合物複合層更佳至少具有約3〇 層,此微層聚合物複合層尤佳至少具有約5〇微層,此微 層聚合物複合層可具有上千微層,熟此技藝者可了解的是 微層之數目視一些因子而定,如選定之特定材料、每一層 ^別的厚度、多層的製備條件,以及此微層聚合物複合^ 最終的應用。此被層^^合物衩合層較佳具有約至約1〇〇〇 微層,更佳具有約30至約1〇〇〇微層,尤佳具有約5〇至 約500微層。 於此微層聚合物複合層之流體阻障層之各層平均厚 度可能低至若干奈米(nm),高至若干密爾約1〇〇微 米(micron)),各層較佳具有達 〇.lmil(約 2.5 microns) 之平均厚度,各層尤佳具有達〇· 〇〇〇4mil(約〇. 〇i microns) 至約0· lmil(約2· 5 microns)之平均厚度,舉例來說,各 阻障材料可能具有平均約〇.〇5mil(約1.2 microns)之平 均厚度。具有較薄之流體阻障材料之微層能增加薄膜之耐 用度,此微層聚合物複合層具有約〇.25mil(約6. 35 microns)之平均厚度至約i〇2mil(約2600 microns)之平 均厚度’尤佳具有約3mil(約75 microns)至約200mil(約 0.5cm)之平均厚度’最佳具有約3mil(約75 microns)至 約40mil(約〇· lcm)之平均厚度。 結構聚合物及流體阻障聚合物之交替層具有其主要 表面’大致對準平行於複合物之主要表面,流體阻障聚合 物具有足夠數目的層,使得微層複合物具有期望的流體擴 散速率。 24 4HDP/04002TW/NIKE-替換頁 1290941 案號:93123224 2^)06年8月28曰修正 此微層聚合物複合層可藉由使用二層、三層或五層分 流器(feed block),導引層流(layered stream)成為靜態 的混合物或多層,此靜態的混合物具有多種混合元件,較 佳至少五種,以幾何的方式增加層的數目,一較佳形成微 層聚合物複合層之方法係於Schrenk,et al·,美國專利 號5, 094, 793,1992年3月10日核准,在此併入以作為 參考’保護邊界層可能根據Ramanathan,美國專利號 5, 269, 996,1993年12月14日核准之方法,而在此併入 以作為參考。此保護層保護此彈性體及流體阻障層,以免 於層形成及加乘(multiplication)時不穩定及解體,此保 護層由軟化的熱塑性材料所提供,以支撐複合物流之外部' 表面,以於共擠壓機構之壁形成一保護邊界層,此保護& 可將特定光或物理特性加至微層聚合物複合層,如特定^ 色,包含藉由具有金屬或其他薄片(flake)顏料於保= 界層中所獲得之金屬染料。 % 施认^然微層聚合物複合層並不—定要是完整層,盆係延 緣的平面中,但期待大部;的微Ρ ΐΓ〇ί J-611'011 f STABAX〇LP STABAX〇L l 1 may be useful for the fc carbon or poly-competition carbon hydrolyzed soybean oil, the total enthalpy of the hydrolytic stabilizer may be less than the layer The total weight is 5%. Plasticization can be included to increase the flexibility and usability of the final product, as well as to enhance the material from the resin form to the film or sheet, for example, but not to define those based on tetraphenyl decyl ester. The plasticizer was confirmed to be useful. Regardless of the mixture of plasticizer or plasticizer, the total amount of plasticizer will generally be less than 20% by weight of all layers, preferably less than 5% by weight of the total layer weight. The inventive film may comprise a microlayer polymer composite layer having at least alternating microlayers of fluid barrier materials as previously described and elastomeric materials as previously described. It is also contemplated that the microlayer polymer composite layer comprises microlayers of different fluid barrier materials and/or microlayers comprising different elastomeric materials, the different layers being arranged in a regular repeat. It is also possible to include layers other than the elastic layer and the fluid barrier layer, and the elastic layer and the fluid barrier layer are alternately arranged in a regular pattern. The microlayer polymer composite layer should have at least about 10 microlayers, and the microlayer polymer composite layer preferably has at least 23 4 HDP/04002 TW/NIKE-replacement page '1290941, . Case number 93122324, August 4, 2006 The modification has about 20 microlayers, and the microlayer polymer composite layer preferably has at least about 3 layers, and the microlayer polymer composite layer preferably has at least about 5 microlayers, and the microlayer polymer composite layer can have A thousand microlayers, as can be understood by those skilled in the art, the number of microlayers depends on a number of factors, such as the particular material selected, the thickness of each layer, the preparation conditions of the multilayer, and the composite of the microlayer polymer. application. The layered layer preferably has from about 1 to about 10 microlayers, more preferably from about 30 to about 1 microlayer, and more preferably from about 5 to about 500 microlayers. The average thickness of each layer of the fluid barrier layer of the microlayer polymer composite layer may be as low as several nanometers (nm), as high as several mils to about 1 micron (micron), and each layer preferably has a 〇.lmil (average thickness of about 2.5 microns), each layer preferably has an average thickness of about 4 mils (about ·i microns) to about 0·lmil (about 2.5 microns), for example, each resistance The barrier material may have an average thickness of about 5 mils (about 1.2 microns) on average. A microlayer having a thinner fluid barrier material can increase the durability of the film. The microlayer polymer composite layer has an average thickness of about 2525 mil (about 6.35 microns) to about i 〇 2 mil (about 2600 microns). The average thickness 'preferably has an average thickness of from about 3 mils (about 75 microns) to about 200 mils (about 0.5 cm), preferably having an average thickness of from about 3 mils (about 75 microns) to about 40 mils (about 〇·lcm). The alternating layers of the structural polymer and the fluid barrier polymer have a major surface 'substantially aligned parallel to the major surface of the composite, and the fluid barrier polymer has a sufficient number of layers such that the microlayer composite has a desired fluid diffusion rate. . 24 4HDP/04002TW/NIKE-Replacement Page 1290941 Case No.: 93322224 2^) August 28, 2006 Correction of this microlayer polymer composite layer can be achieved by using a two, three or five layer feed block. The layered stream becomes a static mixture or layers, the static mixture having a plurality of mixing elements, preferably at least five, geometrically increasing the number of layers, preferably forming a microlayer polymer composite layer The method is approved by Schrenk, et al., U.S. Patent No. 5,094, 793, issued Mar. 10, 1992, the disclosure of which is incorporated herein by reference in its entirety in The method approved on December 14, 1993, which is incorporated herein by reference. The protective layer protects the elastomer and fluid barrier from instability and disintegration during layer formation and multiplication, the protective layer being provided by a softened thermoplastic material to support the exterior 'surface of the composite stream to Forming a protective boundary layer on the wall of the co-extrusion mechanism, this protection & can add specific light or physical properties to the micro-layer polymer composite layer, such as a specific color, including by having a metal or other flake pigment The metal dye obtained in the boundary layer. % Appreciate that the microlayer polymer composite layer is not – it must be a complete layer, the basin is in the plane of the extension, but expects most of it;
曰貫貝上為元整層,及延伸至溥臈之所有邊緣。 可能未填料之薄膜, 膨脹物的合宜長歧^物。此相可為形成充氣 本發明之薄膜可能包含一或多 =數目的微層可用於薄膜,=層至=物= 層。此薄膜較佳包含至少另-層,為·^層^ 4HDP/04002TW/N|KE_ 替換頁 25 丄290941 案號:93123224 2〇〇6年8月28曰修正 佳為熱塑性聚氨g旨。本發 性聚氨醋A層,及至少膜包含至少-層彈 層或二 A = 氨醋彈性體及二料此3包含至少-熱塑性聚 聚物,此薄物輯斷 粗,=有ί、岐本㈣之層狀奈米填财-或多種材 程傾向於’軸微層之製 較平仃於薄縣蚊奈米麵 物人 般所期待醉行絲帅關之奈米频達到一 明之細的另—特徵為具有—增強的鍵結,其發 ^於,性材觸與_,獻微層聚合物複合層之流 體阻p早材料層之間,此增強的鍵結—般藉由使用材料相鄰 層適當的官能基團,可參與氫鍵,如祕中之氮原子 或疋虱原子接上聚截j旨之氮原子,可參與與不同受體基團 ,氫鍵,受體積團祕基中之氧原子、聚氨酯類中的絲 氧以及酯類,及如PVDC中之氯原子。舉例來說,相信氳 鍵是發生於當彈性材料包含基於聚酯二醇之聚氨酯,以及 流體阻障材料包含一聚合物,此聚合物選自乙烯及乙二醇 之共聚物、聚乙烯叉二氯、丙烯腈及醯胺甲酯之共聚物、 聚對酞酸乙二酸、脂肪族及芳香基聚醯胺、結晶聚合物及 聚氨酯工程熱塑性物。除了氳鍵,可能還有一定量之共價 4HDP/04002TW/NIKE-替換頁 26 1290941 案號·· 93123224 ’ 20.06年8月28日修,正 鍵於層之間,仍然有其他因素,如定向力及誘導力,其他 已知如凡得瓦力,相信其源自於存在於任兩分子之&敦 力,以及兩極性分子間之偶極-偶極力,提供相鄰層^之 鍵強度。相信除了這些物理作用力及化學作用力^化 鍵,界面結構也對鍵結強度有顯著的貢獻。 現在參考圖式,圖1揭示薄膜1()具有彈性材料層12、 14、18及20,以及聚合物流體阻障層16,層12及2〇較 厚,如12-14mil,具有聚合物彈性體所組成之彈性材 如熱塑性聚氨酯彈性體,但其可能包含微量之其他聚合物 鲁 材料,如聚合物流體阻障材料之層16。層14及18較^專, 如1-3 mi 1,作為外層12及20與内層,阻障層16之繫(衍幻 層。層14及層18之聚合物材料,舉例來說,必須由熱塑 性聚氨酯彈性體所組成。熱塑性聚氨酯彈性體可盥聚人物 流體,障材料之層16間有氫鍵,較佳為乙烯—乙^醇二聚 物。虱建發生於聚氣酯之胺基甲酸乙醋與乙烯—乙二醇共 聚物之醇基團之間。至少-層具有層狀奈米填料,較佳 層16 〇 十圖2說明一薄膜具有一作為核心、阻障層之微層聚合 物複合124,微層聚合物複合丨24可能為5—7mi丨厚,且且 有聚合物阻障層及彈性材料之交替層。層112及丨 ^ 如25-27mil,此彈性材料主要由聚合_性體所組成,如 熱塑性聚氨酯彈性體,但其可能具有少量之其他聚合材 料,如聚合物流體阻障材料。層114及118較薄,如 ,由熱塑性聚氨酯彈性體之聚合物材料所組成。此 薄膜 11〇 具有外層(outerskin layer)122& 126,卜2mil 4HDP/04002TW/NIKE-替換頁 27 1290941 案號·· 93 1 23224 2006年8月28曰修正 體之熱塑性聚氨酯彈 此層狀奈米填料較佳 厚,具有實質上同樣具有熱塑性彈性 性體。至少一層具有層狀奈米填料, 包含一或多之層112、124及120。 圖3揭示圖2之多層薄膜之侧視局部放大圖 14 圍住微層巧物複合層m之—㈣,微層聚合物複合層 揭示為具有3C替騎’包含聚合物流體卩蹲材料及彈性材 料之厚層,此聚合物流體阻障材料較佳為乙烯和乙二烯之 共聚物,如層140 ,此彈性材料之厚層較佳為熱塑性聚胺 酯彈性體,如層142。此層狀奈米填料可能兩種層,但較 佳此層狀奈米填料包含至少聚合物流體阻障材料層。 本發明進一步包含膨脹物,尤其是充氣的膨脹物,由 本發明之薄膜或者是包含膨脹物之其他物品所製備。本發 明之薄膜提供彎曲性且阻抗流體,如充氣氣體,的擴散。 這些薄膜可由如氮氣之氣體所充氣,較佳提供約1〇cc/m2· a^n· jay或更少值之氣體擴散速率。此充氣膨脹物之耐用、 彈性薄膜可用於許多應用中,尤其是充氣物或緩衝物之應 用。「耐用」意指此薄膜對於抵抗疲乏故障相當優異,也 就是說此薄膜忍受重覆曲張及/或變形及恢復,而無破裂 或其他故障,較佳可克服環境條件,如溫度及相度溼度。 為本發明之目的,這個字「薄膜(membrane)」用於表示將 一流體(不論是氣體或液體)與另一流體分開之獨立膜 (film)。層化或壓印在另一物品非以分隔流體為目的之薄 膜’排除於本發明定義之薄膜外。 此薄膜可能是薄或厚,此薄膜應足夠厚以提供足夠的 28 4HDP/04002TW/NIKE-替換頁 1290941 • 案號:93123224 , 2006年8月28曰修正 壁強度,足夠薄以提供足夠的彎曲性。薄膜之較佳厚度從 約20mil至約70mil,尤佳從約2〇mil至約4〇mii厚^於 一車父佳的五層結構,為了中間流體阻障材料層盘 障層相鄰於任-邊的彈性材料層,分別為期^至= 0· 4mil厚,較佳至少約〇· 5mil厚,尤佳至少約〇· 6mii厚, 以及更佳約至少lmil厚;以及達3mii厚,較佳達約& 5mil 厚、尤佳達約2mil厚,更佳約L 6mil厚。最外層較佳是 主要為彈性材料而具有少量流體阻障材料,此流^ 料較佳至少約7mil厚’尤佳至少約8mil厚,更佳至$ 9mil厚;以及較佳達約2〇mil厚,尤佳達約丨^丨丨厚。 _ —特別地’本發明提供一種充氣的膨脹物,用於如鞋類、 蓄電池,或如運動球之充器物,膨脹物具有一薄膜,此薄、 膜包含至少一彈性材料、至少一聚合物流體阻障材料,較 佳於一分開層,其中一層狀奈米填料具有達約10夺米之 一平均薄層厚度,及至少約200之一平均外觀比值存在於 至少一薄膜層中。本發明之薄膜具有彈性機制的特性,使 之可以被,覆地且確實地吸收使用預期間的高作用力,而 不會逐漸衰退或是疲乏故障。此薄膜在此類應用時特別重 鲁 要的是於循環的負載中具有絕佳的穩定性。此阻障材料且 ,一低氣體擴散速率,使其保持充氣,因此提供緩衝及& 氣,不需週期地再充氣及再加壓此膨脹體,物品實質地具 有期待的生命期,因此是永久地密封。 %脹物可以由RF(無線電頻率生產)焊接兩薄層科 層材料或包含微層之薄膜,尤其是當—層為二 極性材料。非極性材料如聚烯烴能使用超音波或熱封技術 4 H D P/04002TW/N | KE-替換頁 29 1290941 案號:93123224 2006年8月28曰修正 焊接。其他已知的焊接技術也可以被使用。 ⑽Ϊ膜可以藉由吹出成形製程形成膨脹物。—般說來, |二可以藉由首先於平坦的絲狀形狀的多層 L最二二壓辟之後吹出成形平坦的薄膜或管狀物為期i 糍胚、如,多層的溶化原料可能被共擠壓以作為 f胚。,、有大致上期待的膨脹物全形和結構的模且於The top of the shell is the entire layer and extends to all edges of the dragonfly. Possible unfilled film, suitable long-distance of the expansion. This phase may be a gas-forming formation. The film of the present invention may contain one or more = number of microlayers available for the film, = layer to = material = layer. Preferably, the film comprises at least another layer, which is a layer of 4HDP/04002TW/N|KE_. Replacement page 25 丄290941 Case No.: 93322224 2〇〇6年28月28曰 Correction is a thermoplastic polyurethane. The present polyurethane layer A, and at least the film comprises at least a layer of elastic layer or two A = ammonia vinegar elastomer and two materials. The third material comprises at least a thermoplastic polymer, and the thin material is broken, and has ί, 岐The layered nano-enrichment of this (4)- or a variety of materials tends to 'the axis of the micro-layer system is more flat than the thin county mosquitoes, and the nano-frequency is expected to be drunk. Another feature is that there is an enhanced bond, which is caused by the contact of the material with the _, and the fluid layer of the microlayer polymer composite layer is between the early material layers, and the enhanced bond is generally used by using the material. Appropriate functional groups in adjacent layers may participate in hydrogen bonding. For example, the nitrogen atom or the ruthenium atom in the secret chain is attached to the nitrogen atom of the poly-n-type, which can participate in different hydrogen-bonding groups. Oxygen atoms in the group, silk oxygen and esters in the polyurethane, and chlorine atoms such as PVDC. For example, it is believed that the 氲 bond occurs when the elastic material comprises a polyester diol-based polyurethane, and the fluid barrier material comprises a polymer selected from the group consisting of copolymers of ethylene and ethylene glycol, polyethylene forks Copolymers of chlorine, acrylonitrile and guanamine methyl ester, poly(p-citric acid oxalic acid), aliphatic and aromatic polyamines, crystalline polymers and polyurethane engineering thermoplastics. In addition to the 氲 key, there may be a certain amount of covalent 4HDP/04002TW/NIKE-replacement page 26 1290941 Case number··93123224 ' On August 28, 2006, the key is between the layers, there are still other factors, such as orientation And inducing forces, other known as van der Waals, are believed to originate from the presence of any two molecules of & Dun force, and the dipole-dipole force between the two polar molecules, providing the bond strength of the adjacent layer. It is believed that in addition to these physical forces and chemical forces, the interface structure also contributes significantly to bond strength. Referring now to the drawings, Figure 1 discloses that film 1 () has layers 12, 14, 18 and 20 of elastomeric material, and a polymeric fluid barrier layer 16, layers 12 and 2 are thicker, such as 12-14 mils, having polymer elasticity. The elastomeric material comprised of the body is a thermoplastic polyurethane elastomer, but it may contain traces of other polymeric Lu materials, such as layer 16 of polymeric fluid barrier material. Layers 14 and 18 are more specialized, such as 1-3 mi 1, as the outer layers 12 and 20 and the inner layer, the barrier layer 16 (the phantom layer. The polymer material of layer 14 and layer 18, for example, must be The thermoplastic polyurethane elastomer is composed of a thermoplastic polyurethane elastomer which can condense the human fluid, and the layer 16 of the barrier material has a hydrogen bond, preferably an ethylene-ethylene glycol dimer. The urethane which is formed by the polyglycol ester Between the alcohol group of the ethyl vinegar and the ethylene-ethylene glycol copolymer. At least the layer has a layered nanofiller, preferably the layer 16 〇10, FIG. 2 illustrates that the film has a microlayer polymerization as a core and a barrier layer. Composite 124, the microlayer polymer composite crucible 24 may be 5-7 mm thick, and has alternating layers of polymer barrier layer and elastic material. Layer 112 and 丨^ such as 25-27 mil, the elastic material is mainly polymerized. a composition of a plastid, such as a thermoplastic polyurethane elastomer, but which may have a small amount of other polymeric materials, such as polymeric fluid barrier materials. The layers 114 and 118 are relatively thin, such as a polymer material of a thermoplastic polyurethane elastomer. This film 11〇 has an outer layer (outerskin layer) 122 & 126, Bu 2mil 4HDP/04002TW/NIKE-Replacement page 27 1290941 Case No. · 93 1 23224 August 28, 2006 Revision of Thermoplastic Polyurethane This layered nanofiller is preferably thick and has substantially the same thermoplastic Elastomeric body. At least one layer has a layered nanofiller comprising one or more layers 112, 124 and 120. Figure 3 is a side elevational view of the multilayer film of Figure 2, partially enclosing the microlayer composite layer m - (d), the microlayer polymer composite layer is disclosed as having a thick layer comprising a polymer fluid enthalpy material and an elastomeric material. The polymer fluid barrier material is preferably a copolymer of ethylene and acetylene, such as The layer 140, the thick layer of the elastic material is preferably a thermoplastic polyurethane elastomer, such as layer 142. The layered nanofiller may have two layers, but preferably the layered nanofiller comprises at least a layer of polymer fluid barrier material. The invention further comprises an intumescent, in particular an aerated, inflated material, prepared from a film of the invention or other article comprising an intumescent material. The film of the invention provides for the diffusion of a flexible and resistive fluid, such as an inflation gas. These films may be inflated by a gas such as nitrogen, preferably providing a gas diffusion rate of about 1 〇 cc / m 2 · a ^ n · jay or less. The durable, elastic film of this aerated product can be used in many applications, especially It is an application of an inflator or a cushion. "Durable" means that the film is excellent for resisting fatigue failure, that is, the film is subjected to repeated varicose and/or deformation and recovery without cracking or other failure, and is preferably overcome. Environmental conditions, such as temperature and phase humidity. For the purposes of the present invention, the word "membrane" is used to mean a separate film that separates a fluid, whether a gas or a liquid, from another fluid. A film that is layered or embossed on another article other than the purpose of separating the fluids' is excluded from the film defined by the present invention. The film may be thin or thick, and the film should be thick enough to provide sufficient 28 4HDP/04002TW/NIKE- Replacement Page 1129941 • Case No.: 93322224, August 28, 2006 Correct wall strength, thin enough to provide adequate bending Sex. Preferably, the film has a thickness of from about 20 mils to about 70 mils, more preferably from about 2 mils to about 4 mils, and is a five-layer structure of a car-family, for the intermediate fluid barrier material layer. The edge of the elastic material layer, respectively, is from 0 to 4 mil thick, preferably at least about 〇 5 mil thick, particularly preferably at least about 6 mil thick, and more preferably at least about 1 mil thick; and up to 3 mii thick, preferably Dayo & 5mil thick, especially good for about 2mil thick, better about L 6mil thick. Preferably, the outermost layer is predominantly an elastomeric material having a small amount of fluid barrier material, preferably at least about 7 mils thicker, more preferably at least about 8 mils thick, more preferably up to $9 mils thick; and preferably up to about 2 mils. Thick, especially good for about 丨^丨丨 thick. In particular, the present invention provides an inflated article for use in a footwear, a battery, or a device such as a sports ball, the expansion having a film comprising at least one elastomeric material, at least one polymer stream The bulk barrier material is preferably a separate layer wherein the layered nanofiller has an average sheet thickness of up to about 10 minutes and an average aspect ratio of at least about 200 is present in at least one of the film layers. The film of the present invention has an elastic mechanism characteristic such that it can be overwhelmed and surely absorbed by the intended high force without gradual deterioration or fatigue failure. This film is particularly important in such applications with excellent stability in circulating loads. The barrier material also has a low gas diffusion rate that keeps it inflated, thus providing cushioning and & gas, without periodically refilling and repressurizing the expansion body, the article substantially has a desired life span, thus Permanently sealed. The % bulge can be welded by RF (radio frequency production) to two thin layers of material or a film containing microlayers, especially when the layer is a bipolar material. Non-polar materials such as polyolefins can be used with ultrasonic or heat sealing technology. 4 H D P/04002TW/N | KE-Replacement Page 29 1290941 Case No.: 9332224 Modified on August 28, 2006 Welding. Other known welding techniques can also be used. (10) The ruthenium film can be formed into an expansion by a blow molding process. In general, the second can be formed by first forming a flat film or tube after first pressing the second layer of the flat wire shape, and then, for example, the multi-layered molten material may be co-extruded. Take f as an embryo. , there is a general expectation of the full shape of the expansion and the structure of the
和包_關圍。模胚係於模具的邊緣模 麵位置。模型上方賴胚開口部份 Ϊ ΪΓ:人,通過之壓触氣或其他氣體,如氮 ί料/ΐ且t 空氣壓迫緊鄰模胚内表面的模具,此 物丄此吹_、成_薄财在從模財歸 = 胚中冷卻及硬化,約在30。F到I F,同時 ^And package _ Guanwei. The mold base is attached to the edge mold position of the mold. Above the model, the opening part of the embryo is Ϊ 人: person, through the pressure of gas or other gases, such as nitrogen / ΐ and t air pressing the mold next to the inner surface of the mold, this thing 吹 _, into _ thin Cooling and hardening in the embryo from the mold, about 30. F to I F, at the same time ^
被移到接絲自已被第-模具切除之模胚的下—部分L *往=====卜:形fr驟可能藉Moved to the lower part of the mold which has been cut by the first die - L* to =====Bu: The shape of fr may be borrowed
(accumulator-type)^^. ^Γΐ;Γα ' head),X^fBm^(intermittent)^ ; 吹膜管或勤。其他吹ii{絲財法包含^ 成形、真空成形、轉移成形、壓縮成㊉❹J镇t 熱熔鑄造、無線電頻焊接等等。辟 封、鉍以、 為期接的外彬壯,单抬瞄仏二〜.、’平土旦膜可以切割 t;irr〇 r ^ 為期待的外形狀,平坦膜的兩部分 : 膨脹物。此膜也可捲成-錄,邊緣’以形成 接,以形携脹物。 且在其雜以鱗電頻焊 4HDP/04002TW/NIKE-替換頁 30 1290941 案號:93 1 23224 2006年8月28日修正 ^ 此膨脹物可與流體密封,及永久地密封,流體較佳為 氣體。譬如,此膨脹的耐用、彈性薄膜可併入鞋類產品 的底部。「耐用」意指此薄膜對於抵抗疲乏故障相當優異, ^就是說此薄膜忍受重覆曲張及/或變形及恢復 ,而不會 沿混合阻障薄膜之層界面剝離,較佳可橫跨一寬區域的溫 度。鞋類(footwear),特別是鞋子(shoe),通常包括兩主 要主,:鞋的上部分(shoe upper)和底部。鞋的上部分的 目的是緊貼且舒適地包圍足部,鞋的上部分理想是由吸引 人的、非常耐用的、舒適的材料及材料的組合物所製造。 鞋的上^分可由料典型的材料製造,包含但非限定於皮 革’黑,、尼龍以及其他紡織材料。此底部由财用材料所 建構’设計為在使用時提供摩擦及保護腳,此底部典型也 =乍為運脑動雜供增加猶及魏肋,崎護腳、 踝和腿,以避免相當作用力產生的摩擦。在跑步活動產生 =力,穿戴時的體重的2或3倍, ,活動’物打籃球可以產生_力,為穿麟的體重 倍1 ° if供這些功能,底部典型地有有緩衝的底夾 ;On,e或内底部(inSQle),和具有摩擦表面的外底 。膨脹物較佳應用於鞋的内底部,即是一般 透明度’此膨脹物可以形成至少部分的鞋的外^ 此薄膜較佳是能夠於一相對長時間容納一束 鞋子之緩衝為習知之技術。_表面。個祕物供 Ϊ於ίί奈米填料之薄膜具有期待的低朦朧性和高 缚的氣 4HDP/04002TW/NIKE-替換頁 31 .1290941 案號:93 1 23224 , , ,2006年8月28日修正 體。於一較佳的實施例,譬如,薄膜在約2年期間將不會 損失大於最初的膨脹氣體壓力約20%。換言之,充氣的產 品最初在一穩定壓力狀態,在約20· 〇到22· 0 pSi ,在約 2年期間應至少會保持壓力在16· 〇到18· 〇 psi的範圍: 此膨脹物或是緩衝裝置可能以空氣,或如具有氮氣組 成之空氣或超氣體所充氣,當使用緩衝裝置於鞋類,如鞋 子,此膨脹物可能被充氣,較佳以氮氣充氣,至内壓達 3psi,較佳為至少大約5 psi到大約50 psi。較佳膨脹物 被充氣到内壓從大約5 psi到大約35 psi,更佳從大約5 psi到大約30 psi,特佳從大約1〇 psi到大約3〇,然而 最佳從大約10 psi到大約25 psi。熟此技藝者應知於其 他非鞋類之應用,期待且較佳的壓力可以變化很大,可^ 特定領域的熟此技藝者所決定。譬如,蓄電池壓力範圍可 到約1000 psi。蓄電池壓力較佳到大約500 psi,蓄電池 應用之一較佳範圍壓力是從大約200 psi到大約1〇〇〇 psi,但是壓力低到大約25 psi —樣是可能的。依蓄電池 的設計,此膨脹物使用於運動球類之典型壓力是從大約8 到大約40 psi。於充氣之後,此充氣部份可藉由無線電 頻焊接密封,以成為一永久密封且充氣的膨脹物。 為了膨脹物保持永久地充氣,氣體擴散速率必須適當 地低。於一較佳實施例中,膨脹物的薄膜具有膨脹傾向氣 體之氣體,較佳的是空氣或氮氣,應小於15cc/m2 · atln · day ’較佳小於約6 cc/m2·atm·day,特別是小於約4cc/m2 · atm · day ’更佳小於約2· 5 cc/m2 · atm · day,尤佳小於 約 1· 5 cc/m2 · atm · day,特佳小於約 1 cc/m2 · atm · day。 32 4HDP/04002TW/NIKE-替換頁 1290941 案號:93 1 23224 2006,年8月28曰修正 一種可用於測量不同層相關之侵透、滲透及擴散,稱為 ASTM D-143,係設置於製程之中。根據ASTM D-143,氮氣 為較佳的束缚氣體,用於許多實施例和作為分析氣體和擴 散速率的基準,薄膜能包含各種的不同的氣體及/或液體: 蓄電池’尤其是水壓式蓄電池係用於車輛懸吊系統、 車輛煞車系統、工業的水壓式蓄電池,或供其他具有應力 差於兩潛在相異的彎曲性媒介之應用。薄膜將水^式g電 池分開成兩腔體或隔間,其中之一個包含氣體,盆中 個包含液體。 〃 除了使用於鞋類及蓄電池之緩衝裝置,可了解的是本 發明之薄膜具有廣泛的應用範圍,包括但是不限定用於供 充氣物體的膨脹物,包含如美式足球、籃球、和足球之& 類;内管;彈性的漂浮設備諸如試管或筏;作為醫學的装 備的成分如導管氣球;作為傢倶物品之一部分,如椅子 座位,作為保護設備的一部分,包含攀登護具及鋼^; 為傢倶物品之支撐元件,且尤其是破舊傢俱的支撐物; 為車輛輪胎的一部分,尤其是輪胎外層;以及作為特定 製裝置之一部分,如用於同轴或輪式溜冰鞋之輪部分, 本發明更進一步以下列的例子所描述。這些例子僅 用於說明,並不以任何方式限定本發明之說明及範圍。 例子1 兩單層乙烯-乙烯醇共聚物的薄層[EV0H]包含5%重旦 百分比之的層狀奈米填料之製備,係藉由= 4HDP/04002TW/NIKE-替換頁 33 1290941 案號:93 1 23224 2006年8月28日修正(accumulator-type)^^. ^Γΐ;Γα 'head), X^fBm^(intermittent)^ ; Blowing tube or diligent. Other blowing ii{ silk money method includes ^ forming, vacuum forming, transfer forming, compression into ten ❹ J town t hot melt casting, radio frequency welding and so on. The seals, the seals, and the joints are strong, and the single lifts are aimed at 仏2~., the flattened film can cut t; irr〇 r ^ is the expected outer shape, the two parts of the flat film: the expansion. The film can also be rolled up, recorded, and edged to form a joint to shape the bulk. And in its miscellaneous electric welding 4HDP/04002TW/NIKE- replacement page 30 1290941 Case number: 93 1 23224 Modified on August 28, 2006 ^ This expansion can be sealed with fluid and permanently sealed, the fluid is preferably gas. For example, this expanded, durable, elastic film can be incorporated into the bottom of the footwear. "Durable" means that the film is excellent for resisting fatigue failure, that is, the film is subjected to repeated varicose and/or deformation and recovery without peeling off the interface of the mixed barrier film, preferably across a width. The temperature of the area. Footwear, especially shoes, typically consists of two main masters: the shoe upper and the bottom. The purpose of the upper portion of the shoe is to fit the foot snugly and comfortably, and the upper portion of the shoe is desirably made of a combination of attractive, very durable, comfortable materials and materials. The upper part of the shoe may be made of a typical material, including but not limited to leather black, nylon, and other textile materials. This bottom is constructed of financial materials' designed to provide friction and protect the feet during use. This bottom is also typical of 底部 运 运 运 犹 犹 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 崎 崎 崎 崎 崎 崎 崎 崎 崎 , , , , , , The friction generated by the force. In the running activity produces = force, 2 or 3 times the weight of the wearer, the activity 'playing basketball can produce _ force, for the wearer's weight 1 ° if for these functions, the bottom typically has a cushioned bottom clip ; On, e or inner bottom (inSQle), and an outsole with a friction surface. The swell is preferably applied to the inner bottom of the shoe, i.e., generally transparent. The swell may form at least a portion of the outer surface of the shoe. Preferably, the film is a conventional technique for accommodating a bundle of shoes for a relatively long period of time. _surface. The secret of the Ϊ ί 奈 填料 填料 具有 具有 具有 具有 具有 具有 具有 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 body. In a preferred embodiment, for example, the film will not lose more than about 20% of the initial inflation gas pressure over a period of about 2 years. In other words, the inflated product is initially in a steady state, at about 20 〇 to 22.0 pSi, and should remain at least for a period of about 2 〇 to 18 〇 psi for about 2 years: The cushioning device may be inflated with air, or air or supergas, such as nitrogen. When using a cushioning device in footwear, such as shoes, the inflated material may be inflated, preferably with nitrogen, to an internal pressure of 3 psi. Preferably at least about 5 psi to about 50 psi. Preferably, the expanded material is inflated to an internal pressure of from about 5 psi to about 35 psi, more preferably from about 5 psi to about 30 psi, particularly preferably from about 1 psi to about 3 Torr, but preferably from about 10 psi to about 25 psi. Those skilled in the art should be aware of other non-shoes applications, and the expected and preferred pressures can vary widely, as determined by those skilled in the art. For example, battery pressures can range from approximately 1000 psi. The battery pressure is preferably about 500 psi, and a preferred range of battery applications is from about 200 psi to about 1 psi, but the pressure is as low as about 25 psi. Depending on the design of the battery, the typical pressure of the expander used in sports balls is from about 8 to about 40 psi. After inflation, the inflated portion can be sealed by radio frequency welding to become a permanently sealed and inflated expansion. In order for the expansion to remain permanently inflated, the rate of gas diffusion must be suitably low. In a preferred embodiment, the film of the expanded material has a gas which expands the tendency gas, preferably air or nitrogen, and should be less than 15 cc/m2 · atln · day ' preferably less than about 6 cc/m2·atm·day, In particular, less than about 4 cc/m2 · atm · day 'more preferably less than about 2 · 5 cc / m 2 · atm · day, especially less than about 1.5 cc / m 2 · atm · day, particularly preferably less than about 1 cc / m 2 · atm · day. 32 4HDP/04002TW/NIKE-Replacement Page 1290941 Case No.: 93 1 23224 2006, August 28, 2008 A correction can be used to measure the penetration, penetration and diffusion associated with different layers, called ASTM D-143, which is set in the process. Among them. According to ASTM D-143, nitrogen is the preferred bound gas for many embodiments and as a reference for the analysis of gases and diffusion rates, the film can contain a variety of different gases and/or liquids: batteries 'especially hydraulic batteries It is used in vehicle suspension systems, vehicle brake systems, industrial hydraulic batteries, or other applications where the stress is poorer than the two potentially different bending media. The membrane separates the water cell into two chambers or compartments, one of which contains gas and one of which contains liquid. 〃 In addition to the cushioning devices used in footwear and batteries, it is understood that the films of the present invention have a wide range of applications, including but not limited to expansions for inflatable objects, including such as American football, basketball, and football. ; an inner tube; an elastic floating device such as a test tube or a sputum; as a component of medical equipment such as a catheter balloon; as part of a household item, such as a chair seat, as part of a protective device, including a climbing brace and steel; a support element for a household item, and in particular a support for worn furniture; a part of a vehicle tire, in particular an outer layer of the tire; and as part of a particular device, such as a wheel portion for coaxial or wheeled skates, The invention is further described by the following examples. These examples are for illustrative purposes only and are not intended to limit the scope and scope of the invention. Example 1 Preparation of a thin layer of two single-layer ethylene-vinyl alcohol copolymer [EV0H] comprising a layered nanofiller having a percentage of 5% by weight, replaced by = 4HDP/04002TW/NIKE-page 33 1290941 93 1 23224 Amendment of August 28, 2006
Kuraray/Evaica 之 ETC_ 133,以 A卜,•土與和二(硬化以和美C=e 處理)以及Cl〇isite 30 a(奈米 , 濃縮然後稀釋如以下程序|y備為糾。&些樣邱在 之高黏土藉由_/產t 含聚,樣品 合物再次擠壓以達到5%重量百5 士丨士工,、,立Γ 百分比黏土。從第二次擠壓製 成小丸子’处生缝聊133黏土奈倾合丸。齊 的mm的阻障性質係以下列方式決定。播壓 的ETC- 133黏土奈米複合丸被擠壓 (cast film),以供氣妒垆邱、去、玄,々、a=組W子的輪層 率,·二擴度 ϊ:ίτ^ΐ二:奈米複合層之氣體擴散速率與沒有填 iiZ 氣體擴散速率比較,由製造者記錄,結果 總結於表一。 樣品 —mi 1/m2-day-atm) 95 wt· ETC-133/5 wt% Cloisite 15A 5.16 95 wt· ETC-133/5 wt% Cloisite 30A 4.07 ETC-133 (如Kuraray所報告) 5. 76 ❿ 擠壓的ETC-133黏土奈米複合丸之後和熱塑性的聚亞 4HDP/04002TW/NIKE-替換頁 34 1290941 1290941 案號:93 1 23224 2006,8月28曰修正 ,這個薄膜被形成密 ,脹物,並以乳體充氣,如美國專利號5,952 祕物併入鞋子的底部,如同美國專利號5,952,所述。 例子2 以^ί^=ΐ^ΕΤ(Η33耻奈錢合丸擠壓, 微朴合物複合物,妖根#Bc)nket α J^8.2, 〇21^ 1 ? 1 ETC-133 # tsSii〜,專利例子中的LCF1G1材料。微層聚 、:ΐϊ”进封、充氣的膨脹物,然後被如同例子1所 述,被包含在鞋的底部。 』丁 叮 本發明已參照較佳實施例而描述。可瞭解的是,無論 何,其任何變化和修飾均落入本發明及以下專利申 圍之精神和範圍内。 卜寻扪甲明耗 【圖式簡單說明】 本發明可藉由以下詳細說明及其伴隨之圖式而 清楚明瞭。 圖1顯示本發明之一多層薄膜; 圖2顯 薄膜;以及 示本發明之含一微層聚合物複合層之一多層 圖3顯示圖2之多層薄膜之一局部放大圖。 【主要元件符號說明】 10薄膜 4HDP/04002TW/NIKE-替換頁 35 1290941 案號:9 3 1 2 3 2 2 4 2006年8月28日修正 12、14、18、20彈性材料層 16聚合物流體阻障層 110薄膜 112、114、118、120彈性材料層 122、126 外層 124微層聚合物複合 140、142聚合物流體阻障及彈性材料之厚層 4HDP/04002TW/NIKE-替換頁 36Kuraray/Evaica's ETC_133, with Ab, • soil and two (hardening to the United States C=e treatment) and Cl〇isite 30 a (nano, concentrated and then diluted as follows: y preparation for correction. & some In the high clay, the sample is re-extruded by _/ t, and the sample is re-extruded to reach 5% by weight, and the percentage of clay is reduced. From the second extrusion, the pellets are made. 'The stalking 133 clay naphtha pellets. The barrier properties of the mm are determined in the following manner. The weaved ETC-133 clay nanocomposite pellets are cast (cast film) for gas supply. , go, 玄, 々, a = group W sub-layer rate, · two expansion ϊ: ίτ^ ΐ 2: the gas diffusion rate of the nano-composite layer is compared with the diffusion rate of the iiZ gas, which is recorded by the manufacturer. The results are summarized in Table 1. Sample - mi 1/m2-day-atm) 95 wt· ETC-133/5 wt% Cloisite 15A 5.16 95 wt· ETC-133/5 wt% Cloisite 30A 4.07 ETC-133 (eg Kuraray Institute Report) 5. 76 挤压 Extrusion of ETC-133 Clay Nanocomposite Pills and Thermoplastic Poly 4HDP/04002TW/NIKE-Replacement Page 34 1290941 1290941 Case No.: 93 1 23224 200 6, August 28 曰 corrected, the film is formed into a dense, bulging, and inflated with a milk, such as U.S. Patent No. 5,952, which is incorporated into the bottom of the shoe, as described in U.S. Patent No. 5,952. Example 2 is ^ί^=ΐ^ΕΤ(Η33耻奈钱合丸压,微朴复合复合,妖根#Bc)nket α J^8.2, 〇21^ 1 ? 1 ETC-133 # tsSii~ , LCF1G1 material in the patent example. The micro-layered, "in", inflated, and inflated material is then included in the bottom of the shoe as described in Example 1. The present invention has been described with reference to the preferred embodiments. It will be understood that regardless of Any changes and modifications thereof fall within the spirit and scope of the present invention and the following patent claims. OBJECTIVES OF THE INVENTION The present invention can be illustrated by the following detailed description and the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 shows a multilayer film of the present invention; Figure 2 shows a film; and a multilayer of a microlayer polymer composite layer of the present invention. Figure 3 shows a partial enlarged view of the multilayer film of Figure 2. [Main component symbol description] 10 film 4HDP/04002TW/NIKE-replacement page 35 1290941 Case number: 9 3 1 2 3 2 2 4 August 28, 2006 Revision 12, 14, 18, 20 elastic material layer 16 polymer fluid Barrier layer 110 film 112, 114, 118, 120 elastic material layer 122, 126 outer layer 124 microlayer polymer composite 140, 142 polymer fluid barrier and thick layer of elastic material 4HDP/04002TW/NIKE-replacement page 36
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EP1651525A2 (en) | 2006-05-03 |
TW200505971A (en) | 2005-02-16 |
WO2005017024A2 (en) | 2005-02-24 |
EP1651525A4 (en) | 2010-11-10 |
KR20060076272A (en) | 2006-07-04 |
US20050031816A1 (en) | 2005-02-10 |
WO2005017024A3 (en) | 2005-06-23 |
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