201016448 六、發明說明 【發明所屬之技術領域】 本發明係關於一種施加自動密封材料至可充氣物件之 內壁上的方法，且更特別地是當此自動密封材料層包含熱 塑性苯乙烯（TPS)彈性體作爲構成成分時。“可充氣物件” 一詞應了解是指：假定彼之可使用的形狀是在彼用空氣充 氣時的任何物件。 ❿ 【先前技術】 EP 1 090 069 B1文件揭示一種以熱塑性苯乙烯彈性 體爲底質之自動密封組成物，且建議在高溫下使用高壓擠 出或噴霧方法，將熔化態之該組成物施加至經硫化之可充 氣輪胎的內壁上。依以上文件，此種熔化態之直接施加， 使在輪胎硫化期間在輪胎表面上所沉積之多種非黏著劑的 移除之需得以避免。 φ 然而，此施加方法所需之裝置並非總是可獲得的。 【發明內容】 本發明之一目的是一種用於施加自動密封材料層至可 充氣物件之內壁上的施加方法，該自動密封材料層是一種 預先製造之預形成層，且包含至少一種熱塑性苯乙烯（TPS) 彈性體及用於使該彈性體增量之超過200 phe之增量劑油 (其中phe代表重量份/ 100份彈性體），其中： -將待塗覆之可充氣物件的內壁清潔； -5- 201016448 -將溶於溶劑中之液態聚合物組成物（或稱之爲“液 態組成物”）層施加至該自動密封材料層與該可充氣物件之 待接觸雙壁中的至少一者之上； 一將該層靜置乾燥；且 -將該自動密封材料層安置於該可充氣物件之內壁 上。 “可充氣物件內表面”的表示方式應了解是指與經加 壓之空氣接觸的物件表面。 此方法之第一步驟的目的是要移除在物件硫化期間沉 積在可充氣物件之內表面上的一些或所有非黏著劑。在此 清潔操作之後，施加液態二烯彈性體組成物，其促進可充 氣物件及自動密封層之二表面之間良好接觸。 申請人已發現：由於包含熱塑性苯乙烯彈性體及超過 2 00 phe含量之增量劑油的自動密封層的實質黏著性，這 些自動密封層不必熱施加來使彼等令人滿意地貼合至可充 氣物件之壁上。 可以使用抹布及/或刷子，用乙醇進行清潔。 較佳地，聚合物是一種二烯彈性體。 液體二烯彈性體組成物可以包括至少一種超快速硫化 加速劑。 液態組成物因此是自動硫化的，亦即彼能使用可充氣 物件中所存在之硫，將在二烯彈性體分子間待建立之橋交 聯。 依照一較佳具體實例，自動密封材料層包含至少30 -6 - 201016448 phe之飽和熱塑性苯乙烯彈性體及至多 70 phe之不飽和 TPS彈性體。 在自動密封層中不飽和TPS彈性體之存在使可充氣 物件之壁的二烯分子與自動密封層者之間能產生交聯橋。 這些化學鍵結導致二材料之間黏合性明顯的增加，特別是 在疲勞時及在高溫下。 依較佳具體實例，飽和TPS彈性體含量是至少50 Q phe，且不飽和TPS彈性體含量是至多50 phe。 飽和TPS彈性體可以選自由苯乙烯/乙烯/ 丁烯 (SEB)、苯乙烯/乙烯/丙烯（SEP)、苯乙烯/乙烯一乙 烯/丙烯（SEEP)、苯乙烯/乙烯一丁烯/苯乙烯 (SEBS)、苯乙烯/乙烯一丙烯/苯乙烯（SEPS)及苯乙烯 /乙烯一乙烯一丙烯/苯乙烯（SEEPS)共聚物及這些共聚 物之摻合物所組成之群組。 較佳地，飽和TPS彈性體係選自由SEBS共聚物、 Φ SEPS共聚物及這些共聚物之摻合物所組成之群組。 也可能自由以下所組成之群組選擇不飽和TP S彈性 體：苯乙烯/ 丁二烯（SB)、苯乙烯/異戊二烯（SI)、苯 乙烯/ 丁二烯/ 丁烯（SBB)、苯乙烯/ 丁二烯/異戊二 烯（SBI)、苯乙烯/ 丁二烯/苯乙烯（SBS)、苯乙烯/ 丁 二烯/ 丁烯/苯乙烯（SBBS)、苯乙烯/異戊二烯/苯乙 烯（SIS)及苯乙烯/ 丁二烯/異戊二烯/苯乙烯（SBIS)嵌段 共聚物及這些共聚物之摻合物。 若有以上所指明之推薦含量，在自動密封層中不飽和 201016448 TPS彈性體之存在使該層能更容易地貼合至至少部分不飽 和之聚合物基質，例如至二烯彈性體層上，例如至丁基橡 膠層上。 爲了在自動密封性及黏合性方面有最佳效能，較佳地 飽和TPS彈性體含量是至少等於60 phe，較佳地在70至 95 phe範圍，且不飽和TPS彈性體含量在至多等於40 phe，較佳地在5至30 phe範圍。 增量劑油可以選自由聚烯烴油類、石蠟油類、環烷油 @ 類、芳族油類、礦油類及這些油類之混合物所組成之群 組。 較佳地，此增量劑油係選自由聚丁烯類、石躐油類及 這些油類之混合物所組成之群組。 甚至更佳地，增量劑油是聚異丁烯油。 有利地，增量劑油含量是介於200至900 phe。 依本發明之方法也適用在自動密封層具有施加面及外 部面而該二面均受非黏性介層所保護的情況。在此情況 @ 中，置於施加面上的非黏性介層係在自動密封層置於可充 氣物件之內壁上之前被移除。 置於自動密封層之外部面上的第二介層可以由膜（諸 如聚丙烯膜）或可延伸之熱塑性膜（諸如聚乙烯、聚氯乙烯 或聚偏氯乙烯膜）所組成。此膜可以在彼已施加至可充氣 物件表面之後殘留在自動密封層表面上，且可以有助於裂 痕密合機制。 當需要在輪胎已硫化後施加抗裂保護層時，此種可應 -8- 201016448 用至任何形式之可充氣物件的方法是特別有利的。此方法 特別容易利用在力車空心輪胎（cycle tyre)的情況中。 本發明之另一目的是自動密封層及液態組成物容器用 於進行上述之施加方法的用途。依照所需之液態組成物的 量而定，此容器特別可以是一種管或罐。 特別有利的是使用藉由二非黏性介層之間所夾合之自 動密封層所形成的捲繞物以作爲自動密封層。 ❿ 【實施方式】 [本發明之具體實例的詳述] 依照ASTM D 2240標準獲得Shore 0硬度値。在施加 鋸齒器（indenter)lO秒後進行測量。 使用得自Alpha Technologies公司之RPA 2000流變 計，獲得彈性體材料之動力性質。樣品置於二個有條紋之 雙圓錐形的板之間的室中。在密合後，室之體積約4.5 參 cm3。一板被固定，另一板圍繞其中心正弦曲線地震盪。 加諸約20%之變形且進行介於〇.〇3 Hz至33 Hz之間的頻 率掃描。加諸於此室內部之溫度是60°C。所得之結果是 動力切變模數G*及損失因子tan 5 ’其中： G* = Vg,2+G"2 及 tanb% G* :動力切變模數，單位是MPa ; G’：真實切變模數，單位是MPa ; G”：損失模數，單位是MPa ;及 201016448 δ :所加諸之變形與所測量之應力之間的相變換。 材料之延伸模數應了解是指：對一特定之單軸延伸變 形ε而言，在第一伸長時（亦即無適應循環）’在23 °C下測 量所得之表觀橫切延伸模數；拉動速率是500 mm.mirT1 E = (ASTM D412標準）。此模數稱爲模數E。 5 ;其中 S〇是測試片之起初橫截面積。F是在所討論之變形下的延 伸應力，且σ =F/S〇是在所討論之變形下的延伸應力除以 測試片之起初橫截面積S。。 φ σΒ及εΒ二用語應了解是指：在材料測試片破裂點 所測量之應力及伸長度（使σ β標準化成測試片之起初橫截 面積S〇)。 在本描述中，除非另外明確地指明，否則所指明之所 有％係重量％。 再者，由“介於a及b之間”之表示方式所指明之任 何間隔或數値係代表由超過a至少於b之値的範圍（亦即 排除邊界値a及b);但是由“自a至b”之表示方式所指 ® 明之任何數値間隔是指自a至b之値的範圍（亦即包括嚴 格邊界a及b)。 圖1槪略地顯示供載客車輛用之合倂自動密封層的可 充氣輪胎或輪胎的徑向橫截面。 此輪胎1具有由胎冠強化物或帶6所強化之胎冠2， 二側壁3及二胎唇4 ’這些胎唇4均用輪胎鋼絲5來強 化。胎冠2之上安裝胎面（其未顯示於此槪略圖中）。骨架 強化物7纏繞在每一胎唇4中之二輪胎鋼絲5，此強化物 -10- 201016448 7之翻轉部分8係例如朝向輪胎1外側放置，在此顯示該 輪胎安裝在其輪緣9上。骨架強化物7，如本質已知的， 係由至少一個藉由繩索所強化之膠合板所構成，該繩索稱 爲“徑向”繩索，例如紡織繩索或金屬繩索，亦即這些繩 索實際上互相平行排列且從一胎唇延伸至另一胎唇，以與 輪胎之轉動軸形成介於80°及90°之角度。氣密層10相對 於骨架強化物7在內部徑向地由一胎唇延伸至另一胎唇。 φ 輪胎1是使其內壁包括自動密封層11。依一較佳具 體實例，自動密封層11覆蓋整個氣密層10且實質上構成 輪胎之整個內壁。自動密封層也可以從一側壁延伸至另一 側壁；當此輪胎係在配合位置上時，該層係至少從對應於 輪網溝槽端之徑向高度。依照其他可能的具體實例，自動 密封層1 1可以僅覆蓋氣密區（層10)之一部份，例如僅覆 蓋輪胎之胎冠區；或可以至少從胎冠區延伸至輪胎之側壁 中點（赤道）。 ❹ 氣密層（厚度0.7至0.8 mm)是以具有一般供內襯所用 之調和物的丁基橡膠爲底質，該氣密層經常以慣用方式來 限定輪胎之徑向內部面，意欲保護骨架強化物使之無空氣 從輪胎之內部空間擴散。此氣密層10因此使輪胎1能被 充氣且保持在壓力下。其密封性質能保證相對低比率之壓 力降，使輪胎能在正常操作狀態中保持足夠時間之充氣 態，正常是數星期或數月之充氣態。 圖2說明力車空心輪胎，其包括覆蓋自動密封層合物 或熱塑性膜之自動密封層。 -11 - 201016448 此輪胎20包含二個側壁21及一胎冠22。骨架強化 物（未顯示）在側壁及胎冠中從一胎唇延伸至另一胎唇。胎 面24置於胎冠處之骨架強化物上。此輪胎包括自動密封 層合物25。此層合物25係由自動密封層26所構成’而 該自動密封層26與覆蓋可延伸之熱塑性膜27的輪胎1者 類似。可延伸之熱塑性膜與輪胎內部空腔的空氣接觸。層 合物25實質僅延伸在輪胎20之胎冠22周圍。 圖3及4極槪略地說明：在穿刺用物體存在下及其移 除後，所述之自動密封層之密封機制。此二圖顯示輪胎1 之側壁3之S部件的放大部分。 在圖3中，穿刺用物體15已完全地穿過輪胎側壁 3，造成裂痕17a。穿刺用物體或釘子留在原位上，且箭 頭指明藉由在輪胎1之內部空腔12中的充氣壓力Pi所造 成之應力的方向。此充氣壓力Pi使自動密封層呈流體靜 力壓縮狀態，自動密封層之彈性延伸模數越低或其動力應 變模數越低，則其越完美。這些力將密封層材料施加向穿 刺用物體15且封住裂痕17a。 該圖3顯示：當側壁3之材料30及其他材料層中之 裂痕的二邊緣極接近時，在移除釘子15後之裂痕17b。 同樣地，該流體靜力壓縮力確保在自動密封層中裂痕17b 之邊緣的密合且因此封住此裂痕17b。 應注意：當釘子仍留在原位時，氣密層10使經過裂痕 17a之滲漏速率能受極大的限制。然而，當釘子移除時， 此氣密層絕對不能封住裂痕17b，且輪胎基本上常立即變 -12- 201016448 平。 圖4顯示：在穿刺用物體已移除後，在輪胎側壁3之 結構中所造成之裂痕邊緣實際上被移動分開且留下有限尺 寸的真實的孔的情況。此種孔普通可以具有數mm之直 徑。在此情況中，用於封住此種裂痕17b之驅動力再次地 是在自動密封層中藉由充氣壓力Pi所產生之流體靜力壓 力。這些力導致裂痕之置換，而塡充裂痕附近之密封層的 0 材料。這導致裂痕之優越的密封。 自動密封層材料之動力模數越低，則此置換越容易。 這些置換因此需要使自動密封層材料有在破裂點之高的伸 長度與在破裂點之高的應力的結合，以致能塡充裂痕且無 破裂。在破裂點之大於500%的伸長度及較佳地大於800% 的伸長度與在破裂點之大於0.2 MPa之應力的結合是令人 滿意的。 所述之自動密封層以極類似於彈性材料之方式機械地 # 作用。此作用令這些層’比一般之具有甚爲更黏稠機械作 用的自動密封層，有實際上的優點。當穿刺用物體被移除 時’特別是當此穿刺用物體已留在原位上數小時，或甚至 數曰，且甚至更久時’此優點被證明。在此種情況中，一 般自動密封層之材料大抵需要時間，以完全鬆弛穿刺用物 體周圍’且其黏度反對流體靜力壓縮力，此流體靜力壓縮 力使材料容易流入藉由該移除所產生之裂痕中。特別是若 材料對穿刺用物體之黏合已減低時，這可以導致相對長時 間之密封的缺乏。當穿物物體已移除時，此種密封之缺乏 -13- 201016448 可以極容易地聽到。 相反地，依本發明之自動密封層以實際純粹之彈性方 式作用，且在移除期間，經由流體靜力壓縮力之作用，反 映基本上是立即的。此密封缺陷不再被觀察到。 圖5及6極槪略地說明：在移除穿刺用物體後，依本 發明之密封層及密封層合物的密封機制。此二圖再次顯示 與圖1中所示者類似之輪胎側壁3之S部件的放大部分。 圖5說明：在沒有可延伸之熱塑性膜時，在穿刺用物 體移除後形成栓塞物34的機制。裂痕32之尺寸使自動密 封層11之材料被充氣壓力Pi所推動而直接經過側壁3, 且形成突出物或栓塞物在外側。此栓塞物經常令人滿意地 封住滲漏，但彼極暴於輪胎外側，且當彼撕裂時，輪胎可 能逐渐地或立即地變平。栓塞物形成的另一後果是輪胎內 側之密封層材料的量減少，因此破壞此層之效率》 圖6說明：可延伸之熱塑性膜27被放置於自動密封 層26之外表面上，以致形成依本發明之自動密封層合物 的情況。在此情況中，熱塑性膜27之存在機械性地強化 自動密封層且幫助限定自動密封材料於輪胎之S部分的壁 3之內。自動密封層26之材料沒有完全經過裂痕36，且 在外側沒有形成栓塞物。依照應用，可延伸之熱塑性膜之 形式，特別是其厚度，可以變化。應注意：熱塑性膜較佳 是可延伸的或是可拉伸而具有極小厚度，也因此有極低之 延伸硬度。正是由於此，使熱塑性膜明顯成功地用在所有 家庭應用中。此種極低之延伸硬度使該膜能包封穿刺用物 -14 - 201016448 件，且不降低自動密封層之有效性，且使該·膜能實質上地 延伸且不收縮。因此，當穿刺用物體排除時，可延伸之熱 塑性膜27易於伸展於裂痕36之內，且因此自動密封層 26之材料實質上被機械地強化。此種滲透槪略地顯示於 區38中。因此，觀察到依本發明之層合物的二成分之間 的真實的協乘作用。 熱塑性膜也具有使外部表面不蒙灰的優點。在力車空 0 心輪胎的情況中，此膜使輪胎能無任何問題地以一般方式 摺疊。 熱塑性苯乙烯（TPS)彈性體是以苯乙烯爲底質之嵌段 共聚物形式之熱塑性彈性體。 若在熱塑性聚合物與彈性體之間有中間結構，則如已 知的，彼係由聚苯乙烯硬嵌段所組成，該聚苯乙烯硬嵌段 係由彈性體軟嵌段’例如聚丁二烯、聚異戊二烯或聚（乙 稀- 丁烯）嵌段’所連接。彼常是具有由一個軟片段所連 β 接之二個硬片段的二嵌段彈性體。硬片段及軟片段可以用 直鏈形方式來排列’或用星狀或分枝構型來排列。這些 TPS彈性體也可以是具有連接至一個軟片段之單一硬片段 的二嵌段彈性體。典型地’這些片段或嵌段皆最少含有超 過5個基礎單元，通常超過10個基礎單元（在苯乙稀/異 戊一嫌/本乙燦欣段共聚物情況中是例如苯乙稀單元及異 戊二烯單元）。 較佳地’所用之自動密封層包含至少一種TPS彈性 體’其較佳選自由苯乙烯/ 丁二烯/苯乙烯（SBS)、苯乙 -15- 201016448 烯/異戊二烯/苯乙烯（SIS)、苯乙烯/異戊二烯/ 丁二 烯/苯乙烯（SIBS)、苯乙烯/乙烯一丁烯/苯乙烯 (SEBS)、苯乙烯/乙烯一丙烯/苯乙烯（SEPS)、苯乙 烯/乙烯-乙烯-丙烯/苯乙烯（SEEPS)嵌段共聚物及這 些共聚物之摻合物所組成之群組。 更佳地，自動密封層包含至少一種飽和TP S彈性體 及至少一種不飽和TPS彈性體。 依照一特佳之具體實例，自動密封層包含： —至少30 phe (亦即自30 phe至少於100 phe)，較佳 地至少50 phe (亦即自50 phe至少於100 phe)之飽和TPS 彈性體，其與以下者結合： 一至多70 phe (亦即自多於0 phe至70 phe)，較佳地 至多50 phe (亦即自多於〇 phe至50 phe)之不飽和TPS 彈性體。 換言之，飽和TPS彈性體含量在最少30 phe至少於 100 phe之範圍，且不飽和TPS彈性體含量在多於0 phe 至最多70 phe範圍。 在本發明中，適用以下習知的定義： -飽和TPS彈性體應了解是指不含烯式不飽和基團 (亦即無碳—碳雙鍵）的TPS彈性體；及 -不飽和TPS彈性體應了解是指具有烯式不飽和基 團之TPS彈性體，亦即彼包括碳-碳雙鍵（不管共軛與 否）。 較佳地，飽和TPS彈性體係選自由苯乙烯/乙烯/ 201016448 丁烯（SEB)、苯乙烯/乙烯/丙烯（SEP)、苯乙烯/乙烯 -乙烯/丙烯（SEEP)、苯乙烯/乙烯—丁烯/苯乙烯 (SEBS)、苯乙烯/乙烯一丙烯/苯乙烯（SEPS)及苯乙烯 /乙烯一乙烯一丙烯/苯乙烯（SEEPS)共聚物及這些共聚 物之摻合物所組成之群組。 更佳地，該彈性體係選自由SEBS共聚物、SEP S共 聚物及這些共聚物之摻合物所組成之群組。 φ 較佳地，不飽和TPS彈性體係選自由苯乙烯/ 丁二 烯（SB)、苯乙烯/異戊二烯（SI)、苯乙烯/ 丁二烯/ 丁 烯（SBB)、苯乙烯/ 丁二烯/異戊二烯（SBI)、苯乙烯 / 丁二烯/苯乙烯（SBS)、苯乙烯/ 丁二烯/ 丁烯/苯乙 烯（SBBS)、苯乙烯/異戊二烯/苯乙烯（SIS)及苯乙烯/ 丁二烯/異戊二烯/苯乙烯（SBIS)嵌段共聚物及這些共聚 物之摻合物所組成之群組。更佳地，此不飽和TPS彈性 體是一種選自由下列所組成之群組的三嵌段型共聚物：苯 φ 乙烯/ 丁二烯/苯乙烯（SBS)、苯乙烯/ 丁二烯/ 丁烯/ 苯乙烯（SBBS)、苯乙烯/異戊二烯/苯乙烯（SIS)及苯乙 烯/ 丁二烯/異戊二烯/苯乙烯（SBIS)嵌段共聚物及這些 共聚物之摻合物。 應強調：在自動密封組成物中，以上所指明之含量的 不飽和TPS彈性體的存在，使該自動密封組成物可能更 容易地貼合至至少部分不飽和的聚合物基質上，例如至二 烯彈性體（諸如丁烯橡膠）之層上。 爲要在自動密封性及黏合性方面有最佳效能，飽和 -17- 201016448 TPS彈性體的含量較佳是至少等於60 phe，更佳在70至 96 phe範圍；且不飽和TPS彈性體的含量較佳是至多等 於40 phe，較佳在5至30 phe範圍。 依本發明之另一較佳具體實例，在個別之飽和TPS 彈性體及不飽和TPS彈性體中苯乙烯的含量是介於5至 50%之間。在所指明之最小値以下，彈性體之熱塑性本質 會有實質減低的危險，但在所推薦之最大値以上，組成物 之彈性可能被不利地影響。因這些理由，苯乙烯含量更佳 介於10至40%之間，特別是介於15至35 %之間。 TPS彈性體之玻璃轉換溫度（Tg，依照ASTM D3418, 1 999藉由DSC(微分掃描量熱法）來測量）較佳是低於-2〇 °C，更佳是低於-40°C。 在這些最低溫度以上的Tg値，意即自動密封組成物 本身之更高的Tg，可以降低自動密封組成物之效能，當 在極低溫下使用時。對於此種用途而言，TPS彈性體之Tg 更佳甚至是低於-50°C。 TPS彈性體之數目平均分子量（由Mn所註明）較佳介 於50 000至500 000 g/mol之間，更佳介於75 000至450 000 g/mol之間。在所指明之最小値以下，因其之稀釋（增 量劑之量），在TPS彈性體鏈之間的內聚性有變差的危 險。再者，使用溫度之增加有不利地影響機械性（特別是 破裂點之性質）的危險，最終導致降低“熱”效能。再者， 太高的分子量Mn可能破壞在所推薦之增量劑油含量下組 成物之撓性。因此，已發現：在250 〇〇〇至400 000範圍 201016448 之Mn是特別適合的，特別是供充氣輪胎中自動密封組成 物之用。 TPS彈性體的數目平均分子量（Μη)用已知方式，藉 由SEC(空間排除層析法）來決定。樣品首先溶在四氫呋喃 中成爲約1 g/Ι之濃度，然後此溶液在注射前在0.45 μιη 孔隙度之濾器上過濾。所用之裝置是 WATERS Alliance 色層譜。洗提用溶劑是四氫呋喃；流速是0.7 ml/分鐘； ❹ 系統溫度是35 °C ;且分析時間是90分鐘。使用一組四個 串聯的 WATERS管柱，亦即一個 STYRAGEL HMW7管 柱、一個 STYRAGEL HMW6E 管柱、及二個 STYRAGEL HT6E管柱。聚合物樣品溶液之注射體積是ΙΟΟμΙ。偵測 器是WATERS 2410微分折射計，且其相關之用於處置層 析數據的軟體是WATERS MILLENIUM系統。所計算之平 均分子量是相對於使用聚苯乙烯標準物所得的校正曲線。 TPS彈性體或飽和及不飽和之二種TPS彈性體可以構 Φ 成全部的彈性體基質，或當基質包括一或多種其他彈性體 (不管是否爲熱塑性，例如二烯型之彈性體）時，彼可以構 成基質之主要的重量部分（較佳是超過50%，且更佳是超 過 70%)。 依照一較佳之具體實例，TPS彈性體或飽和及不飽和 之二種TPS彈性體是自動密封組成物中所僅存之的彈性 體及僅存的熱塑性彈性體。 爲獲得依本發明之動力模數，自動密封層較佳包括極 高使用含量（大於200 phe，亦即大於200重量份/100份 -19 - 201016448 彈性體）之增量劑油類（或塑化用油類）。 可以使用任何增量劑油類，較佳是具有弱極性特性而 能使彈性體，特別是熱塑性彈性體，增量或塑化者。 在室溫23 °C下，這些相對黏稠之油類是液體（亦即作 爲提醒，是具有最終能採取其容器形狀的物質），此與本 質爲固體之樹脂，特別是膠黏樹脂是相反的。 較佳地，增量劑油係選自由聚烯烴油類（亦即那些由 烯烴類、單烯烴類或二烯烴類之聚合所得者）、石蠟油 類、低或高黏度之環烷油類、芳族油類、礦油類、及這些 油類之混合物所組成之群組。 更佳地，使用聚異丁烯油，特別是使用聚異丁烯（PIB) 油、石蠟油或這些油類之混合物。 聚異丁烯油類之實例包括那些特別係由Univar所售 之商品名爲 “ Dynapak Poly” 者（例如 “ Dynapak Poly 190”，由 BASF所售之商品名爲“ Glissopal”者（例如 “ Glissopal 1 000”）或 “ Oppanol” 者（例如 “ Oppanol B12”）；石蠟油類是例如由 Exxon所售之商品名爲 “Telura 618”者或由 Repsol所售之商品名爲“Extensol 5 1”者。 增量劑油之數目平均分子量（Mu)較佳是介於200至 30 000 g/mol之間，更佳介於300至10 000 g/mol之間。 對於過低的Mn値而言，有油移至自動密封組成物外 側的危險；但過高之Mn値可以使此組成物變得太硬。介 於400至3 000之間的Mn値證明對於所要之應用，特別是 -20- 201016448 用於充氣輪胎，是一優越的折衷形式。 增量劑油之數目平均分子量（Mn)係由SEC來決定， 樣品首先溶在四氫呋喃中成爲約1 g/Ι之濃度，然後此溶 液在注射前在〇.45μιη孔隙度之濾器上過濾。裝置是 WATERS Alliance色層譜。洗提用溶劑是四氫呋喃；流 速是1 ml/分鐘；系統溫度是35°C ;且分析時間是30分 鐘。使用一組二個商品名爲“ STYRAGEL HT6E”之 φ “WATERS管柱。聚合物樣品溶液之注射體積是100μ1。 偵測器是WATERS 2410微分折射計，且其相關之用於處 置層析數據的軟體是WATERS MILLENIUM系統。所計算 之平均分子量是相對於使用聚苯乙烯標準物所得的校正曲 線。 鑒於以下之描述及具體實例，精於此技藝之人士將獲 知：如何依照自動密封組成物之特別使用狀況，特別是企 圖用於其中之輪胎的使用狀況，來調節增量劑油之量。 φ 增量劑油含量較佳介於500至900 phe之間。在所指 明之最小値以下，自動密封組成物對某些應用而言有硬度 太高的危險；但在所推薦之最大値以上，組成物有內聚性 不足的危險。 用多量之油類所增量之飽和TPS彈性體（諸如SEPS 或SEBS)是習知的且在商業上是可得的。作爲實例，可以 提及由 Vita Thermoplastic Elastomers 或 VTC(“VTC TPE group”）所售之商品名爲 “ Dryflex” （例如 “ Dryflex 967 1 00”）或 “Mediprene”（例如 “ Mediprene 5 00 000M，，）之 •21 - 201016448 產品，及那些由Multibase所售之商品名爲“ Multiflex” (例如 “ Multiflex G00”）者。 這些特別供醫療、醫藥或化妝品應用所發展的產品可 以藉由擠出或模製，一般可以在TPEs方面被處理，例如 從珠狀或顆粒狀之原料開始處理。當然，飽和TPS彈性 體也能以非增量形式被獲得。舉例而言，可以提及由 Kraton公司所售之商品名爲“ Kraton G”.（例如G1650、 G1651、G1654、G1730之產品）或由Kuraray公司所售之 商品名爲 “Septon” （例如 S2005 、 S2006、 S8004、 S8006) 的SEBS或SEPS彈性體。 不飽和TPS彈性體，例如SBS、SIS或SBBS，也是 習知的，且係在商業上可得自例如Kraton公司之商品名 爲“ Kraton D”者（例如在SIS及SBS彈性體之情況中爲 D1161、 D1118、 D1116、 D1163 之產品），得自 Dynasol 公司之商品名爲“ Calprene”者（例如在SBS例子中爲 C405、C41 1、C412之產品），或得自Asahi公司之商品名 爲“Tuftec”者（例如作爲SBBS之例子的P 1 500產品）。 施加依本發明之自動密封層在力車空心輪胎內壁上的 方法現在將連同圖7至15來描述。如同在所引證之美國 專利4,424,295中所強調的，在硫化後，極難沉積一層自 動密封產物在力車空心輪胎內側，因爲此型輪胎有極大的 撓性。所述方法使此種施加能容易地進行。 圖7說明依本發明之施加方法的第一步驟一用於施加 自動密封層至力車空心輪胎。此輪胎20特別包含二側壁 -22- 201016448 21及胎面24，且具有內壁28及外壁29。第一步驟係由 使輪胎內側外翻以致內壁28在輪胎外側且外壁29在內側 所組成。此外翻操作可以在圖7中所示之箭頭所指明的方 向上進行。 此內側外翻的操作在力車空心輪胎的情況中是極容易 的，因爲輪胎鋼絲有極大之撓性及彎曲而能容易地摺疊卻 不會永久變形。此種內側外翻之操作可以人工地進行。 φ 圖8顯示內部已外翻之輪胎。 其次，內側向外之輪胎20置於充氣筒50上（其在圖 9中槪略地說明），該充氣筒50具有被設計以容納輪胎之 胎唇23的二個凸緣51，52及意欲密封該筒、該凸緣及該 膜所形成之空腔54的膜53。 空腔54然後被充氣，同時使二個凸緣51及52更接 近在一起，如圖10所說明的。此空腔54之內部壓力Pc 將該膜53壓向輪胎之外壁29。圖10之二個箭頭顯示使 〇 該二個凸緣51、52更接近在一起的移動方向。 在圖11中，完成使該二個凸緣51及52更接近在一 起之移動，且空腔54中之內部壓力提升至Pf値。壓力Pf 是介於輪胎之表觀充氣壓力Pi的0.5至3倍之間。較佳 地，此壓力實質大於輪胎20之表觀充氣壓力，以使輪胎 20之骨架強化物呈現比一般在輪胎使用時所進行者更大 的延伸狀態。 此充氣壓力Pf也具有以下優點：使內側向外安裝之輪 胎20有相當充分之整體硬度，以致能施加自動密封層合 -23- 201016448 物25至內壁28。 在正要施加層合物25之前，輪胎被清潔。此清潔操 作較佳係使用抹布或刷子將醇施加至壁而進行。 在清潔之後，如圖12所說明的，自動硫化之液態組 成物被施加在二表面（亦即意圖互相接觸之輪胎之壁28及 自動密封層合物25之壁）之至少一者之上以作爲例如洗 劑。自動硫化液態組成物也可以在其組合之前沉積在此二 壁上。 液態組成物靜置乾燥，然後層合物25被沉積在內壁 28上，如圖13中所說明的。此層合物可以已藉由以下步 驟預先製造：擠出表層成爲所要之寬度及厚度，且沉積在 非黏性保護膜或介層（例如聚矽氧化或硫化之紙）上並纏繞 在捲筒中。在施加至輪胎期間，一層表層捲繞在輪胎周 圍，且在該表層施加及轉動輪胎期間剝除此聚矽氧化之保 護膜。然後施加熱塑性膜2 7。 較佳地，熱塑性膜27在捲繞之前被施加至表層之空 壁上，以使層合物之捲筒被捲繞而立即可施加至輪胎 2〇，此施加係以單一操作來進行。 自動密封層也可以藉由捲繞厚度及寬度小於所要尺寸 的條狀物而施加。 在層合物25已施加後，輪胎藉由第二次內側外翻操 作翻回成正確的圓，如圖14所說明的。然後獲得在圖15 中所說明之輪胎。 應注意：在充氣至Pf之內側向外的輪胎的內壁28上 -24- 201016448 無特別應力的情況下，被放置的層合物25之自動密封層 26，在內側外翻操作之後，係呈一種與輪胎20之正常形 狀之取得相關且與空腔54之抽氣相關的壓縮狀態。當輪 胎20被充氣至其表觀充氣壓力時，此種壓縮狀態必須被 保持，因爲是在空腔54中之壓力高於此表觀充氣壓力Pi 之情況中進行施加。此種壓縮狀態對於自動密封層26及 自動密封層合物25之效率是極有利的。當表觀充氣壓力 φ Pi是2巴時，所施加之壓力可以高達6巴或甚至8巴。 製造本發明之例示的具體實例以供52-559尺寸之力 車空心輪胎之用。由 SEBS彈性體（15%之Kraton G1654 產品）基質及1 000 Mn之聚異丁烯（PIB)油（85%之Dynapak 190)所組成之lmm厚之自動密封材料層沉積在這些輪胎 內壁上。也施加35 μπι厚之聚乙烯拉伸膜。層合物重量約 1〇〇克，此材料之Shore 0硬度是約8且其動力模數G*在 °C下是少於10 000 Pa。 Φ 這些輪胎用直徑1.8mm之釘子及用多種其他尖銳點 及造成破壞之物體（例如直徑2mm之穿刺用鑽床鑽頭）來 穿刺。壓力偵測5日。我們發現：使用1 .8 mm釘子的3 個釘孔是〇滲漏（亦即壓力降等於在穿刺前之輪胎的壓力 降）。使用其他物體所產生之滲漏是輕微的且對於力車空 心輪胎之使用是可容忍的。 在本申請案內，“液態組成物”一詞應了解是指溶於 溶劑中之液態聚合物組成物（在23 °C下）。 較佳地，聚合物是溶於溶劑（例如環己烷或脂族石腦 -25- 201016448 油或乙酸乙酯等）中的二烯彈性體，例如天然橡膠、 SBR、丁基橡膠或聚丁二烯。 自動硫化之液態組成物（或液態硫化流體）是習知的， 且數十年來已用來修復橡膠物件。讀者可以參考例如 1925年公告之FR 594224文件。彼經常含有能引起室溫 交聯之硫化劑，例如超快速加速劑，但排除硫以免於過早 交聯。彼也含有多種添加劑，例如抗氧化劑。交聯使用存 在於待組合或修復之零件中的硫。可以提及得自Schrader ^ 公司之液態組成物 Opale + Topaze 或得自 Tech International 公司之液態組成物 Tech Vulcanizing Fluid。 爲決定自動密封層之施加條件對輪胎壁貼合的影響， 製造且測試特定之剝離測試片。 在以下三步驟中製造測試片： 一製造由織物及厚度分別爲1.6 mm之非延伸SEBS 材料的二表層所組成的載體在180°C及低壓下組合5分 鐘； φ —將以上載體組合至厚度爲1 mm之自動密封層（約 10至20 Shore 00之極低Shore硬度的層）； 一將厚度爲1.5 mm之內部橡膠組合件製造成強化夾 層，將它們在8(TC下一同硫化10分鐘；及 一在周溫（23 °C )下藉由低壓組合以上二個半測試片而 製造完整的測試片，在有及沒有（對照組）液態組成物之情 況下製造此組件，以測試其有效性。 在此二個半測試片之間的介面的完整性係藉由對完整 -26- 201016448 測試片的180°剝離測試來分析。 下表顯示所測試之多種組合件： 成份 對照組 El E2 E3 E4 G1654(SEBS) 100 100 100 100 50 D1118(SBS) - 50 Dynapak 190 (聚異丁烯） 567 567 567 567 400 Topaze - 是 Tech 760 - 是 Opale+ - 是 是 表2 ‘·顯示所得之剝離結果： 成份 對照組 E1 E2 E3 E4 剝離力 100 1250 990 890 2260201016448 6. Technical Field of the Invention The present invention relates to a method of applying an automatic sealing material to an inner wall of an inflatable article, and more particularly when the layer of self-sealing material comprises thermoplastic styrene (TPS) When the elastomer is used as a constituent. The term "inflatable article" is understood to mean that it is assumed that the shape that can be used by him is any object that is inflated with air. ❿ [Prior Art] EP 1 090 069 B1 discloses an automatic sealing composition based on a thermoplastic styrene elastomer, and it is recommended to apply the composition in a molten state to a high temperature extrusion or spray method at a high temperature. The inner wall of the vulcanized inflatable tire. According to the above document, the direct application of such a molten state is required to avoid the removal of various non-adhesive agents deposited on the surface of the tire during vulcanization of the tire. φ However, the means required for this application method are not always available. SUMMARY OF THE INVENTION One object of the present invention is an application method for applying a layer of an automatic sealing material to an inner wall of an inflatable article, the layer of self-sealing material being a pre-formed preformed layer and comprising at least one thermoplastic benzene Ethylene (TPS) elastomer and extender oil for increasing the elastomer by more than 200 phe (where phe represents parts by weight per 100 parts of elastomer), wherein: - the inside of the inflatable article to be coated Wall cleaning; -5- 201016448 - applying a layer of liquid polymer composition (or "liquid composition") dissolved in a solvent to the layer of self-sealing material and the double wall of the inflatable article to be contacted Above at least one; one layer is allowed to dry; and - the layer of self-sealing material is placed on the inner wall of the inflatable article. The expression "inner surface of an inflatable article" should be understood to mean the surface of the article in contact with the pressurized air. The purpose of the first step of the method is to remove some or all of the non-adhesive agent deposited on the inner surface of the inflatable article during vulcanization of the article. After this cleaning operation, a liquid diene elastomer composition is applied which promotes good contact between the two surfaces of the inflatable article and the automatic sealing layer. Applicants have found that due to the substantial adhesion of the automatic sealing layer comprising thermoplastic styrene elastomer and extender oil in excess of 200 phe content, these automatic sealing layers do not have to be heat applied to allow them to be satisfactorily bonded to On the wall of the inflatable object. It can be cleaned with ethanol using a rag and/or brush. Preferably, the polymer is a diene elastomer. The liquid diene elastomer composition can include at least one ultra-fast vulcanization accelerator. The liquid composition is thus auto-vulcanized, i.e., it can use the sulfur present in the inflatable article to crosslink the bridge to be established between the diene elastomer molecules. According to a preferred embodiment, the layer of self-sealing material comprises at least 30 -6 - 201016448 phe of saturated thermoplastic styrene elastomer and up to 70 phe of unsaturated TPS elastomer. The presence of the unsaturated TPS elastomer in the elastomeric seal layer creates a cross-linking bridge between the diene molecules of the wall of the inflatable article and the elastomeric sealant. These chemical bonds result in a significant increase in adhesion between the two materials, especially during fatigue and at elevated temperatures. According to a preferred embodiment, the saturated TPS elastomer content is at least 50 Q phe and the unsaturated TPS elastomer content is at most 50 phe. The saturated TPS elastomer may be selected from the group consisting of styrene/ethylene/butylene (SEB), styrene/ethylene/propylene (SEP), styrene/ethylene-ethylene/propylene (SEEP), styrene/ethylene-butene/styrene. (SEBS), a group of styrene/ethylene-propylene/styrene (SEPS) and styrene/ethylene-ethylene-propylene/styrene (SEEPS) copolymers and blends of these copolymers. Preferably, the saturated TPS elastomeric system is selected from the group consisting of SEBS copolymers, Φ SEPS copolymers, and blends of these copolymers. It is also possible to choose unsaturated TP S elastomers from the group consisting of styrene/butadiene (SB), styrene/isoprene (SI), styrene/butadiene/butene (SBB) , styrene/butadiene/isoprene (SBI), styrene/butadiene/styrene (SBS), styrene/butadiene/butene/styrene (SBBS), styrene/isoprene Diene/styrene (SIS) and styrene/butadiene/isoprene/styrene (SBIS) block copolymers and blends of these copolymers. The presence of the unsaturated 201016448 TPS elastomer in the elastomeric seal layer allows the layer to more easily conform to at least partially unsaturated polymer matrix, such as to the diene elastomer layer, such as to the diene elastomer layer, if the recommended levels specified above are present. On the butyl rubber layer. For optimum performance in terms of auto-sealability and adhesion, preferably the saturated TPS elastomer content is at least equal to 60 phe, preferably in the range of 70 to 95 phe, and the unsaturated TPS elastomer content is at most equal to 40 phe. Preferably, it is in the range of 5 to 30 phe. The extender oil may be selected from the group consisting of polyolefin oils, paraffin oils, naphthenic oils @, aromatic oils, mineral oils, and mixtures of these oils. Preferably, the extender oil is selected from the group consisting of polybutenes, sarcophagus oils, and mixtures of these oils. Even more preferably, the extender oil is a polyisobutylene oil. Advantageously, the extender oil content is between 200 and 900 phe. The method according to the invention is also applicable where the automatic sealing layer has an application surface and an outer surface which are both protected by a non-adhesive layer. In this case @, the non-sticky layer placed on the application surface is removed before the automatic sealing layer is placed on the inner wall of the inflatable article. The second layer disposed on the outer face of the automatic sealing layer may be composed of a film such as a polypropylene film or an extensible thermoplastic film such as polyethylene, polyvinyl chloride or polyvinylidene chloride film. This film may remain on the surface of the automatic sealing layer after it has been applied to the surface of the inflatable article and may contribute to the crack adhesion mechanism. This method of using any form of inflatable article is particularly advantageous when it is desired to apply a crack resistant protective layer after the tire has been vulcanized. This method is particularly easy to use in the case of a cycle tire. Another object of the present invention is the use of an automatic sealing layer and a liquid composition container for carrying out the above-described application method. Depending on the amount of liquid composition required, the container may in particular be a tube or can. It is particularly advantageous to use a wound formed by an automatic sealing layer sandwiched between two non-adhesive layers as an automatic sealing layer.实施 [Embodiment] [Details of Specific Examples of the Invention] The Shore 0 hardness 获得 is obtained in accordance with the ASTM D 2240 standard. The measurement was performed 10 seconds after the application of the indenter. The kinetic properties of the elastomeric material were obtained using an RPA 2000 rheometer from Alpha Technologies. The sample is placed in a chamber between two striped double conical plates. After the close, the volume of the chamber is about 4. 5 Ref. cm3. One plate is fixed and the other plate oscillates around its center sinusoid. Add about 20% of the deformation and proceed between 〇. 频 Frequency sweep between 3 Hz and 33 Hz. The temperature applied to the interior of the chamber was 60 °C. The result is the dynamic shear modulus G* and the loss factor tan 5 ' where: G* = Vg, 2+G"2 and tanb% G*: dynamic shear modulus, in MPa; G': true cut Variable modulus, the unit is MPa; G": loss modulus, the unit is MPa; and 201016448 δ: phase transformation between the applied deformation and the measured stress. The extension modulus of the material should be understood as: For a particular uniaxially extended deformation ε, the apparent transverse transverse extension modulus measured at 23 ° C at the first elongation (ie no adaptation cycle); the pull rate is 500 mm. mirT1 E = (ASTM D412 standard). This modulus is called modulus E. 5; where S〇 is the initial cross-sectional area of the test piece. F is the extension stress under the deformation in question, and σ = F / S 〇 is the extension stress under the deformation in question divided by the initial cross-sectional area S of the test piece. . The terms φ σ Β and ε 应 should be understood to mean the stress and elongation measured at the fracture point of the material test piece (normalize σ β into the initial cross-sectional area S 测试 of the test piece). In the present description, all % indicated are % by weight unless otherwise explicitly indicated. Furthermore, any interval or number of lines indicated by the expression "between a and b" is represented by a range exceeding a between at least b (ie, excluding boundaries 値a and b); Any number of intervals from the meaning of a to b" refers to the range from a to b (that is, including strict boundaries a and b). BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing a radial cross section of an inflatable tire or tire for a self-sealing automatic sealing layer for a passenger vehicle. This tire 1 has a crown 2 reinforced by a crown reinforcement or belt 6, and both of the side walls 3 and the second bead 4' are reinforced with a tire wire 5. A tread is mounted over the crown 2 (which is not shown in this sketch). The skeleton reinforcement 7 is wound around two of the tire wires 5 in each of the bead 4, and the reversal portion 8 of the reinforcement-10-10, 16, 148, 448 is placed, for example, toward the outside of the tire 1, where it is shown that the tire is mounted on its rim 9 . The skeleton reinforcement 7, as is known per se, consists of at least one plywood reinforced by ropes, referred to as "radial" ropes, such as textile ropes or metal ropes, ie the ropes are actually parallel to each other Arrange and extend from one bead to the other to form an angle of 80° and 90° with the axis of rotation of the tire. The inner liner 10 extends radially from one bead to the other with respect to the skeleton reinforcement 7. The φ tire 1 is such that its inner wall includes an automatic sealing layer 11. According to a preferred embodiment, the automatic sealing layer 11 covers the entire inner liner 10 and substantially constitutes the entire inner wall of the tire. The automatic sealing layer may also extend from one side wall to the other side wall; when the tire is in the mating position, the layer is at least from a radial height corresponding to the groove end of the wheel mesh. According to other possible embodiments, the automatic sealing layer 11 may cover only a portion of the airtight region (layer 10), for example covering only the crown region of the tire; or may extend at least from the crown region to the midpoint of the sidewall of the tire (equatorial). ❹ Airtight layer (thickness 0. 7 to 0. 8 mm) is based on butyl rubber with a blend for general lining. The inner liner often defines the radially inner surface of the tire in a conventional manner, intended to protect the skeleton reinforcement from air. The internal space spreads. This inner liner 10 thus enables the tire 1 to be inflated and held under pressure. Its sealing properties ensure a relatively low ratio of pressure drop, allowing the tire to remain inflated for a sufficient period of time during normal operation, normally in an inflated state for weeks or months. Figure 2 illustrates a force car hollow tire comprising an automatic sealing layer covering an automatic sealing laminate or thermoplastic film. -11 - 201016448 This tire 20 comprises two side walls 21 and a crown 22 . Skeleton reinforcement (not shown) extends from one lip to the other in the sidewall and crown. The tread 24 is placed on the skeleton reinforcement at the crown. This tire includes an auto-sealing laminate 25. This laminate 25 is composed of an automatic sealing layer 26 which is similar to the tire 1 covering the stretchable thermoplastic film 27. The extendable thermoplastic film is in contact with the air of the interior cavity of the tire. The laminate 25 extends substantially only around the crown 22 of the tire 20. Figures 3 and 4 illustrate very briefly the sealing mechanism of the automatic sealing layer in the presence of the object for puncture and its removal. These two figures show an enlarged portion of the S-piece of the side wall 3 of the tire 1. In Fig. 3, the puncture object 15 has completely passed through the tire side wall 3, causing the crack 17a. The piercing object or nail remains in place, and the arrow indicates the direction of the stress caused by the inflation pressure Pi in the internal cavity 12 of the tire 1. This inflation pressure Pi causes the automatic sealing layer to be hydrostatically compressed, and the lower the elastic extension modulus of the automatic sealing layer or the lower the dynamic modulus, the more perfect it is. These forces apply the sealing layer material to the piercing object 15 and seal the crack 17a. Figure 3 shows the crack 17b after the nail 15 is removed when the material 30 of the side wall 3 and the two edges of the crack in the other material layers are in close proximity. As such, the hydrostatic compression force ensures adhesion of the edges of the cracks 17b in the automatic sealing layer and thus seals the cracks 17b. It should be noted that the leakage layer 10 allows the leakage rate through the crack 17a to be greatly limited when the nail remains in place. However, when the nail is removed, the inner liner is absolutely unable to seal the crack 17b, and the tire is almost always immediately -12-201016448 flat. Fig. 4 shows the case where the edge of the crack caused in the structure of the tire side wall 3 is actually moved apart and a true hole of a limited size is left after the object for piercing has been removed. Such a hole can generally have a diameter of a few mm. In this case, the driving force for sealing such cracks 17b is again the hydrostatic pressure generated by the inflation pressure Pi in the automatic sealing layer. These forces result in the replacement of cracks, while filling the 0 material of the seal layer near the crack. This leads to a superior seal of the crack. The lower the dynamic modulus of the automatic sealing layer material, the easier the replacement. These displacements therefore require the automatic sealing layer material to have a combination of a high elongation at the point of break and a high stress at the point of breakage so that the crack can be filled without cracking. The elongation at greater than 500% at the break point and preferably greater than 800% is greater than 0 at the break point. The combination of 2 MPa stress is satisfactory. The automatic sealing layer mechanically acts in a manner very similar to an elastomeric material. This effect gives these layers a more practical advantage than an automatic sealing layer which has a more viscous mechanical effect. This advantage is demonstrated when the puncture object is removed, especially when the puncture object has been left in place for hours, or even counts, and even longer. In this case, the material of the automatic sealing layer generally takes time to completely relax around the piercing object and its viscosity is against the hydrostatic compression force, which makes the material easy to flow through the removal site. Produced in the crack. In particular, if the adhesion of the material to the piercing object has been reduced, this can result in a lack of sealing for a relatively long period of time. When the object is removed, the lack of such a seal -13- 201016448 can be heard very easily. Conversely, the automatic sealing layer in accordance with the present invention acts in a substantially purely elastic manner and during the removal, the reflection is substantially immediate via the action of the hydrostatic compression force. This sealing defect is no longer observed. Figures 5 and 6 illustrate very briefly the sealing mechanism of the sealing layer and the sealing laminate according to the present invention after removal of the object for puncture. The two figures again show an enlarged portion of the S-piece of the tire sidewall 3 similar to that shown in FIG. Figure 5 illustrates the mechanism by which the embolic material 34 is formed after removal of the puncture object in the absence of an extensible thermoplastic film. The size of the crack 32 causes the material of the automatic sealing layer 11 to be pushed by the inflation pressure Pi directly through the side wall 3, and the protrusion or embolic material is formed on the outer side. This embolic material often satisfactorily seals the leak, but it is extremely violent on the outside of the tire, and when it tears, the tire may gradually or immediately flatten. Another consequence of the formation of the embolic material is that the amount of sealing layer material on the inside of the tire is reduced, thereby destroying the efficiency of the layer. Figure 6 illustrates that the stretchable thermoplastic film 27 is placed on the outer surface of the automatic sealing layer 26, so that The case of the automatic sealing laminate of the present invention. In this case, the presence of the thermoplastic film 27 mechanically strengthens the automatic sealing layer and helps define the automatic sealing material within the wall 3 of the S portion of the tire. The material of the automatic sealing layer 26 does not completely pass through the crack 36, and no embolic material is formed on the outer side. Depending on the application, the form of the stretchable thermoplastic film, particularly its thickness, can vary. It should be noted that the thermoplastic film is preferably extensible or stretchable to have a very small thickness and thus has an extremely low elongation hardness. Because of this, thermoplastic films have been used with significant success in all home applications. This extremely low elongation hardness allows the film to encapsulate the puncture material -14 - 201016448 without reducing the effectiveness of the automatic sealing layer and allowing the film to extend substantially without shrinking. Therefore, when the piercing object is removed, the extendable thermoplastic film 27 is easily stretched within the crack 36, and thus the material of the automatic sealing layer 26 is substantially mechanically strengthened. This permeation is shown schematically in zone 38. Therefore, a true synergistic effect between the two components of the laminate according to the present invention was observed. The thermoplastic film also has the advantage that the outer surface is not ashed. In the case of a pneumatic tire, the membrane allows the tire to be folded in a conventional manner without any problem. The thermoplastic styrene (TPS) elastomer is a thermoplastic elastomer in the form of a styrene-based block copolymer. If there is an intermediate structure between the thermoplastic polymer and the elastomer, as is known, it consists of a polystyrene hard block which is composed of an elastomeric soft block, such as a polybutylene. The diene, polyisoprene or poly(ethylene-butylene) block is attached. It is often a diblock elastomer having two hard segments joined by a soft segment. Hard and soft segments can be arranged in a linear fashion or arranged in a star or branch configuration. These TPS elastomers can also be diblock elastomers having a single hard segment attached to a soft segment. Typically, these fragments or blocks contain at least more than 5 base units, usually more than 10 base units (in the case of styrene/isoamyl/isobutylene copolymers, for example, styrene units and Isoprene unit). Preferably, the "automatic sealing layer used comprises at least one TPS elastomer" which is preferably selected from the group consisting of styrene/butadiene/styrene (SBS), phenethyl-15-201016448 ene/isoprene/styrene ( SIS), styrene/isoprene/butadiene/styrene (SIBS), styrene/ethylene-butene/styrene (SEBS), styrene/ethylene-propylene/styrene (SEPS), styrene /Group of ethylene-ethylene-propylene/styrene (SEEPS) block copolymers and blends of these copolymers. More preferably, the automatic sealing layer comprises at least one saturated TP S elastomer and at least one unsaturated TPS elastomer. According to a particularly preferred embodiment, the automatic sealing layer comprises: - a saturated TPS elastomer of at least 30 phe (i.e., at least 100 phe from 30 phe), preferably at least 50 phe (i.e., at least 50 phe from 50 phe). It is combined with: an unsaturated TPS elastomer of one to more 70 phe (i.e., from more than 0 phe to 70 phe), preferably up to 50 phe (i.e., from more than phephe to 50 phe). In other words, the saturated TPS elastomer content ranges from a minimum of 30 phe to at least 100 phe, and the unsaturated TPS elastomer content ranges from more than 0 phe to a maximum of 70 phe. In the present invention, the following conventional definitions apply: - saturated TPS elastomers are understood to mean TPS elastomers which do not contain ethylenically unsaturated groups (ie no carbon-carbon double bonds); and - unsaturated TPS elastomers It should be understood that TPS elastomers having ethylenically unsaturated groups, that is, they include carbon-carbon double bonds (whether conjugated or not). Preferably, the saturated TPS elastomer system is selected from the group consisting of styrene/ethylene/201016448 butene (SEB), styrene/ethylene/propylene (SEP), styrene/ethylene-ethylene/propylene (SEEP), styrene/ethylene-butyl Group of olefin/styrene (SEBS), styrene/ethylene-propylene/styrene (SEPS) and styrene/ethylene-ethylene-propylene/styrene (SEEPS) copolymers and blends of these copolymers . More preferably, the elastomeric system is selected from the group consisting of SEBS copolymers, SEP S copolymers, and blends of these copolymers. Preferably, the unsaturated TPS elastomer is selected from the group consisting of styrene/butadiene (SB), styrene/isoprene (SI), styrene/butadiene/butene (SBB), styrene/butyl Diene/isoprene (SBI), styrene/butadiene/styrene (SBS), styrene/butadiene/butene/styrene (SBBS), styrene/isoprene/styrene (SIS) and a group of styrene/butadiene/isoprene/styrene (SBIS) block copolymers and blends of these copolymers. More preferably, the unsaturated TPS elastomer is a triblock copolymer selected from the group consisting of benzene φ ethylene/butadiene/styrene (SBS), styrene/butadiene/butyl Alkene/styrene (SBBS), styrene/isoprene/styrene (SIS) and styrene/butadiene/isoprene/styrene (SBIS) block copolymers and blends of these copolymers Things. It should be emphasized that in the automatic sealing composition, the presence of the above-specified amount of unsaturated TPS elastomer allows the automatic sealing composition to be more easily applied to at least partially unsaturated polymer substrates, for example to two. On the layer of an olefin elastomer such as butylene rubber. In order to have the best performance in terms of automatic sealing and adhesion, the content of saturated -17-201016448 TPS elastomer is preferably at least equal to 60 phe, more preferably in the range of 70 to 96 phe; and the content of unsaturated TPS elastomer Preferably, it is at most equal to 40 phe, preferably in the range of 5 to 30 phe. According to another preferred embodiment of the invention, the styrene content is between 5 and 50% in the individual saturated TPS elastomer and the unsaturated TPS elastomer. Below the minimum specified enthalpy, the thermoplastic nature of the elastomer will be substantially reduced, but above the recommended maximum enthalpy, the elasticity of the composition may be adversely affected. For these reasons, the styrene content is better between 10 and 40%, especially between 15 and 35%. The glass transition temperature (Tg of the TPS elastomer, as measured by DSC (Differential Scanning Calorimetry) according to ASTM D3418, 1 999) is preferably less than -2 ° C, more preferably less than -40 ° C. Tg 在 above these minimum temperatures, meaning to automatically seal the higher Tg of the composition itself, can reduce the effectiveness of the auto-seal composition when used at very low temperatures. For such applications, the Tg of the TPS elastomer is preferably even below -50 °C. The number average molecular weight (indicated by Mn) of the TPS elastomer is preferably between 50 000 and 500 000 g/mol, more preferably between 75,000 and 450 000 g/mol. Below the specified minimum enthalpy, the cohesion between the TPS elastomer chains is at risk of dilution due to their dilution (the amount of extender). Moreover, the increase in the temperature of use adversely affects the risk of mechanical properties (especially the nature of the fracture point), ultimately resulting in reduced "hot" performance. Furthermore, too high molecular weight Mn may destroy the flexibility of the composition at the recommended extender oil levels. Therefore, it has been found that Mn in the range of 250 〇〇〇 to 400 000 201016448 is particularly suitable, especially for the automatic sealing of components in pneumatic tires. The number average molecular weight (??) of the TPS elastomer is determined by SEC (Spatial Exclusion Chromatography) in a known manner. The sample was first dissolved in tetrahydrofuran to a concentration of about 1 g/Ι, and then the solution was at 0 before injection. Filter on a 45 μιη porosity filter. The device used is the WATERS Alliance chromatogram. The solvent for elution is tetrahydrofuran; the flow rate is 0. 7 ml/min; ❹ The system temperature is 35 °C; and the analysis time is 90 minutes. A set of four series of WATERS columns, a STYRAGEL HMW7 column, a STYRAGEL HMW6E column, and two STYRAGEL HT6E columns were used. The injection volume of the polymer sample solution is ΙΟΟμΙ. The detector is a WATERS 2410 differential refractometer and the associated software for handling the analytical data is the WATERS MILLENIUM system. The calculated average molecular weight is a calibration curve obtained with respect to the use of polystyrene standards. The TPS elastomer or the saturated and unsaturated TPS elastomers may be configured to form the entire elastomeric matrix, or when the matrix comprises one or more other elastomers (whether thermoplastic or not, such as a diene type elastomer). It may constitute the major weight portion of the substrate (preferably more than 50%, and more preferably more than 70%). According to a preferred embodiment, the TPS elastomer or the two saturated and unsaturated TPS elastomers are the only elastomers remaining in the autoclave composition and the only thermoplastic elastomer present. In order to obtain the dynamic modulus according to the invention, the automatic sealing layer preferably comprises an extender oil (or plastic) having a very high use content (greater than 200 phe, i.e., greater than 200 deg/100 parts -19 - 201016448 elastomer) Chemical oil). Any extender oil may be used, preferably having a weakly polar character to enable the elastomer, particularly the thermoplastic elastomer, to be incremental or plasticized. At 23 ° C at room temperature, these relatively viscous oils are liquids (ie, as a reminder, they have the substance that can ultimately take the shape of their container), which is the opposite of solid-state resins, especially adhesive resins. . Preferably, the extender oil is selected from the group consisting of polyolefin oils (ie those obtained by polymerization of olefins, monoolefins or diolefins), paraffinic oils, low or high viscosity naphthenic oils, A group of aromatic oils, mineral oils, and mixtures of these oils. More preferably, polyisobutylene oil is used, in particular polyisobutylene (PIB) oil, paraffin oil or a mixture of these oils. Examples of polyisobutylene oils include those sold under the trade name "Dynapak Poly" by Univar (for example "Dynapak Poly 190", sold under the trade name "Glissopal" by BASF (eg "Glissopal 1 000") Or "Oppanol" (eg "Oppanol B12"); paraffinic oils such as those sold under the trade name "Telura 618" by Exxon or sold under the trade name "Extensol 5 1" by Repsol. The number average molecular weight (Mu) of the extender oil is preferably between 200 and 30 000 g/mol, more preferably between 300 and 10 000 g/mol. For too low Mn値, the oil is moved to Automatic sealing of the outside of the composition; however, too high Mn値 can make the composition too hard. Mn値 between 400 and 3,000 proves that for the desired application, especially -20- 201016448 for inflation The tire is a superior compromise. The number average molecular weight (Mn) of the extender oil is determined by SEC. The sample is first dissolved in tetrahydrofuran to a concentration of about 1 g/Ι, and then the solution is before the injection. Filter on a 45 μιη porosity filter. The device is the WATERS Alliance chromatogram. The solvent for elution was tetrahydrofuran; the flow rate was 1 ml/min; the system temperature was 35 ° C; and the analysis time was 30 minutes. Use a set of two φ "WATERS columns" under the trade name "STYRAGEL HT6E". The injection volume of the polymer sample solution is 100μ1. The detector is a WATERS 2410 differential refractometer and its associated for processing tomographic data. The software is the WATERS MILLENIUM system. The calculated average molecular weight is a calibration curve obtained with respect to the use of polystyrene standards. In view of the following description and specific examples, those skilled in the art will know how to follow the special composition of the automatic sealing composition. The amount of extender oil is adjusted by the condition of use, in particular the intended use of the tyres therein. φ The extender oil content is preferably between 500 and 900 phe. Automatically sealed below the specified minimum enthalpy The composition is dangerous to some applications for too high a hardness; however, above the recommended maximum enthalpy, the composition is at risk of insufficient cohesiveness. Saturated TPS elastomers (such as SEPS) in increments of a large amount of oil Or SEBS) is conventional and commercially available. As an example, it may be mentioned by Vita Thermoplastic Elastomers or VTC ("VTC TPE group") The product name is "Dryflex" (eg "Dryflex 967 1 00") or "Mediprene" (eg "Mediprene 5 00 000M,") • 21 - 201016448 products, and those sold under the trade name "Multiflex" by Multibase (eg "Multiflex G00"). These products, which are specially developed for medical, pharmaceutical or cosmetic applications, can be processed by extrusion or molding, generally in the form of TPEs, for example starting from beaded or granulated materials. Of course, saturated TPS elastomers can also be obtained in non-incremental form. For example, mention may be made of the trade name "Kraton G" sold by Kraton. (eg, products of G1650, G1651, G1654, G1730) or SEBS or SEPS elastomers sold by Kuraray under the trade name "Septon" (eg S2005, S2006, S8004, S8006). Unsaturated TPS elastomers, such as SBS, SIS or SBBS, are also conventional and are commercially available from, for example, Kraton Company under the tradename "Kraton D" (for example in the case of SIS and SBS elastomers). D1161, D1118, D1116, D1163 products), available from Dynasol Corporation under the trade name "Calprene" (for example, products of C405, C41 1, C412 in the SBS example), or from the trade name of Asahi Company. Tuftec" (for example, the P 1 500 product as an example of SBBS). The method of applying the automatic sealing layer according to the present invention to the inner wall of a hollow tire of a bicycle is now described in connection with Figures 7 to 15. As highlighted in the cited U.S. Patent 4,424,295, it is extremely difficult to deposit an automatic seal product on the inside of a hollow tire of a bicycle after vulcanization because of the great flexibility of this type of tire. The method allows such application to be carried out easily. Figure 7 illustrates a first step 1 of the application method according to the invention for applying an automatic sealing layer to a hollow tire. The tire 20 particularly includes two side walls -22-201016448 21 and a tread 24, and has an inner wall 28 and an outer wall 29. The first step consists of eversion of the inside of the tire so that the inner wall 28 is on the outside of the tire and the outer wall 29 is on the inside. Further, the flipping operation can be performed in the direction indicated by the arrow shown in Fig. 7. This operation of the inner valgus is extremely easy in the case of a hollow tire of a bicycle, because the tire wire is extremely flexible and curved and can be easily folded without permanent deformation. This operation of the medial valgus can be performed manually. φ Figure 8 shows the tires that have been turned inside. Secondly, the inner side outwardly facing tire 20 is placed on an inflating cylinder 50 (which is schematically illustrated in Figure 9) having two flanges 51, 52 designed to accommodate the bead 23 of the tire and intended The film, the flange and the film 53 of the cavity 54 formed by the film are sealed. The cavity 54 is then inflated while bringing the two flanges 51 and 52 closer together, as illustrated in FIG. The internal pressure Pc of this cavity 54 presses the membrane 53 against the outer wall 29 of the tire. The two arrows of Figure 10 show the direction of movement that brings the two flanges 51, 52 closer together. In Fig. 11, the movement of the two flanges 51 and 52 closer together is completed, and the internal pressure in the cavity 54 is raised to Pf. The pressure Pf is 0 between the apparent inflation pressure Pi of the tire. Between 5 and 3 times. Preferably, this pressure is substantially greater than the apparent inflation pressure of the tire 20 such that the skeletal reinforcement of the tire 20 exhibits a greater extended state than would normally be the case with the tire. This inflation pressure Pf also has the advantage that the inner side outwardly mounted tire 20 has a substantially sufficient overall hardness so that the automatic sealing lamination -23- 201016448 25 can be applied to the inner wall 28. The tire is cleaned before the laminate 25 is being applied. This cleaning operation is preferably carried out by applying an alcohol to the wall using a rag or a brush. After cleaning, as illustrated in Figure 12, the auto-vulcanized liquid composition is applied over at least one of the two surfaces (i.e., the walls of the tires that are intended to contact each other and the walls of the self-sealing laminate 25). As, for example, a lotion. The autocure liquid composition can also be deposited on the walls before it is combined. The liquid composition was allowed to stand to dry, and then the laminate 25 was deposited on the inner wall 28 as illustrated in FIG. The laminate may have been pre-manufactured by extruding the skin layer to a desired width and thickness and depositing it on a non-tacky protective film or interlayer (e.g., polyfluorinated or vulcanized paper) and wound in a roll. . During application to the tire, a layer of skin is wound around the tire and the protective film of the polyfluorene oxide is stripped during application and rotation of the tire. A thermoplastic film 27 is then applied. Preferably, the thermoplastic film 27 is applied to the void of the skin prior to winding so that the roll of the laminate is wound and immediately applied to the tire, the application being carried out in a single operation. The automatic sealing layer can also be applied by winding a strip having a thickness and width smaller than the desired size. After the laminate 25 has been applied, the tire is turned back into the correct circle by the second inside eversion operation, as illustrated in FIG. The tire illustrated in Figure 15 is then obtained. It should be noted that in the case of the inner wall 28 of the tire that is inflated to the inner side of the Pf, there is no special stress, the automatic sealing layer 26 of the placed laminate 25, after the inside eversion operation, It is in a compressed state associated with the acquisition of the normal shape of the tire 20 and associated with the pumping of the cavity 54. When the tire 20 is inflated to its apparent inflation pressure, this state of compression must be maintained because it is applied in the event that the pressure in the cavity 54 is above this apparent inflation pressure Pi. This state of compression is highly advantageous for the efficiency of the automatic sealing layer 26 and the automatic sealing laminate 25. When the apparent inflation pressure φ Pi is 2 bar, the applied pressure can be as high as 6 bar or even 8 bar. A specific example of the invention is made for use with a hollow tire of the size of 52-559. A layer of 1 mm thick automatic sealing material consisting of a SEBS elastomer (15% Kraton G1654 product) substrate and 1 000 Mn polyisobutylene (PIB) oil (85% Dynapak 190) was deposited on the inner walls of these tires. A 35 μm thick polyethylene stretch film was also applied. The laminate has a weight of about 1 gram, the Shore 0 hardness of this material is about 8 and its dynamic modulus G* is less than 10 000 Pa at °C. Φ These tires are used with a diameter of 1. 8mm nails and punctures with a variety of other sharp points and objects that cause damage, such as a drill bit with a diameter of 2 mm. Pressure detection for 5 days. We found that: use 1 . The 3 nail holes of the 8 mm nail are leaking (ie, the pressure drop is equal to the pressure drop of the tire before the puncture). Leakage caused by the use of other objects is slight and can be tolerated for the use of pneumatic tires. In the present application, the term "liquid composition" is understood to mean a liquid polymer composition (at 23 ° C) dissolved in a solvent. Preferably, the polymer is a diene elastomer dissolved in a solvent such as cyclohexane or aliphatic naphtha-25-201016448 oil or ethyl acetate, etc., such as natural rubber, SBR, butyl rubber or polybutylene. Diene. Autoclaved liquid compositions (or liquid vulcanizing fluids) are conventionally known and have been used to repair rubber articles for decades. The reader is referred to, for example, the FR 594224 document published in 1925. It often contains vulcanizing agents that cause room temperature cross-linking, such as ultra-fast accelerators, but excludes sulfur to avoid premature crosslinking. He also contains a variety of additives, such as antioxidants. Crosslinking uses sulfur that is present in the parts to be combined or repaired. Mention may be made of the liquid composition Opale + Topaze from Schrader ^ or the liquid composition Tech Vulcanizing Fluid from Tech International. To determine the effect of the application conditions of the automatic sealing layer on the fit of the tire wall, a specific peel test piece was fabricated and tested. The test piece was manufactured in the following three steps: a manufacturing fabric and a thickness of 1. The carrier consisting of two skin layers of 6 mm non-extended SEBS material was combined for 5 minutes at 180 ° C and low pressure; φ - the above carrier was combined to an automatic sealing layer with a thickness of 1 mm (approximately 10 to 20 Shore 00 is extremely low) Shore hardness layer); one will have a thickness of 1. The 5 mm inner rubber assembly is made into a reinforced sandwich, which is vulcanized at 8 (TC for 10 minutes); and at ambient temperature (23 °C), the two test pieces are combined at low pressure to make a complete test. Tablets were fabricated with and without (control) liquid compositions to test their effectiveness. The integrity of the interface between the two semi-test strips was tested by the complete -26- 201016448 The 180° peel test of the sheet was analyzed. The following table shows the various combinations tested: Ingredients Control El E2 E3 E4 G1654 (SEBS) 100 100 100 100 50 D1118 (SBS) - 50 Dynapak 190 (Polyisobutylene) 567 567 567 567 400 Topaze - Yes Tech 760 - Yes Opale+ - Yes Yes Table 2 '· Shows the peeling result: Ingredient control group E1 E2 E3 E4 Peeling force 100 1250 990 890 2260
自動硫化液態組成物之添加導致組合件之剝離強度之 極明顯的增加，因爲依照液態組成物之本質獲得高9至 φ 1 2倍的剝離強度。 藉由將不飽和熱塑性彈性體（在此是一種SBS(E4))併 入自動密封層之基質中而獲得最佳結果。 因此可以進行冷施加極高度延伸之以TPS爲底質之 自動密封層的方法，因爲此材料有極高之黏著性。雖然對 某些應用而言，此黏合性證實是足夠的，但藉由施加一較 佳之自動硫化液態組成物，則不管是否偶合至包含不飽和 TPS部分之自動密封層，其黏合性均可極大幅地增加。 本發明不限於所述及所示之實例，且可以對彼等進行 -27- 201016448 多種修正而不致偏離所附之申請專利範圍所定義之範圍。 【圖式簡單說明】 所有具體實例之細節在以下描述中給予，而該描述藉 由圖1至15補充，其中： 一圖1顯示倂有本發明自動密封層的輪胎的徑向截 面； 一圖2顯示倂有本發明自動密封層合物的力車空心輪 眙的部分徑向截面； 一圖3及4顯示在穿刺用物體存在下及在彼移除後， 本發明自動密封層合物的密封機制； 一圖5及6顯示在移除穿刺用物體或釘子之後，本發 明自動密封層合物的密封機制； 一圖7顯示施加自動密封層至力車空心輪胎的第一步 驟； -圖8說明在內側外翻之後的力車空心輪胎； @ 一圖9說明置於充氣筒上之內側外翻的力車空心輪 胎； 一圖10顯示將內側外翻之力車空心輪胎充氣的過 程； -圖1 1顯示經充氣之內側外翻的力車空心輪胎； 一圖1 2顯示液態組成物之施加； 一圖13顯示自動密封層之施加； 一圖14顯示回復成正確方式的圓形時之圖13的輪 -28- 201016448 胎；及 一圖15顯示回復成正確方式的圓形時之圖14之輪 胎。 【主要元件符號說明】 1 :輪胎 2 :胎冠 ❹ 3 :側壁 4 :胎唇 5 :輪胎鋼絲 6 :胎冠強化物或帶 7 :骨架強化物 8 ·翻轉部分 9 :輪緣 1 〇 :氣密層 _ 11 :自動密封層 12 :內部空腔 15 :穿刺用物體（釘子） 17a，b :裂痕 20 :輪胎 2 1 :側壁 2 2 ·胎冠 23 :胎唇 2 4 .胎面 29 - 201016448 25:自動密封層合物 26 :自動密封層 27 :可延伸之熱塑性膜 28 :內壁The addition of the autocured liquid composition results in a very significant increase in the peel strength of the assembly because a peel strength of 9 to 2 times higher than that of the liquid composition is obtained in accordance with the nature of the liquid composition. The best results are obtained by incorporating an unsaturated thermoplastic elastomer (here an SBS (E4)) into the matrix of the automatic sealing layer. Therefore, it is possible to carry out a cold-applied method of automatically opening a TPS-based automatic sealing layer because of the extremely high adhesion of the material. While this adhesion has proven to be sufficient for some applications, by applying a preferred auto-vulcanization liquid composition, the adhesion is extremely high, whether or not coupled to an automatic sealing layer containing an unsaturated TPS portion. Significantly increased. The invention is not limited to the examples described and illustrated, and various modifications may be made to them without departing from the scope of the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS The details of all specific examples are given in the following description, and the description is supplemented by FIGS. 1 to 15, wherein: FIG. 1 shows a radial section of a tire having the automatic sealing layer of the present invention; 2 shows a partial radial section of the wheel rim of the force car having the automatic sealing laminate of the present invention; FIGS. 3 and 4 show the automatic sealing laminate of the present invention in the presence of the object for piercing and after removal thereof Sealing mechanism; a Figures 5 and 6 show the sealing mechanism of the automatic sealing laminate of the present invention after removing the object or nail for puncture; Figure 7 shows the first step of applying the automatic sealing layer to the hollow tire of the force car; 8 illustrates the force car hollow tire after the inside outturn; @一图9 illustrates the inner car of the inner car that is placed on the inner side of the inflator; FIG. 10 shows the process of inflating the inner side of the inner car; - Figure 1 1 shows an inflated inner-overturned force car hollow tire; Figure 12 shows the application of the liquid composition; Figure 13 shows the application of the automatic sealing layer; Figure 14 shows the return to the correct way of the circle Figure 13 -28-201016448 tire; and Figure 15 shows a return to the tire 14 of a circular view of the correct way. [Main component symbol description] 1 : Tire 2 : Crown ❹ 3 : Side wall 4 : Nozzle 5 : Tire wire 6 : Crown reinforcement or belt 7 : Skeleton reinforcement 8 · Flip part 9 : Rib 1 〇: Gas Close layer _ 11 : automatic sealing layer 12 : internal cavity 15 : piercing object (nail) 17a, b : crack 20 : tire 2 1 : side wall 2 2 · crown 23 : bead 2 4 . tread 29 - 201016448 25: automatic sealing laminate 26: automatic sealing layer 27: extensible thermoplastic film 28: inner wall
29 :外壁 32 :裂痕 34 :栓塞物 3 6 :裂痕 5 0 :充氣筒 51，52 :凸緣 53 :膜 3 0 :側壁3的材料 54 :空腔29: outer wall 32: crack 34: embolic material 3 6 : crack 5 0 : inflatable cylinder 51, 52: flange 53 : membrane 3 0 : material of side wall 54 : cavity
S :側壁部件的放大部分 P i ·_充氣壓力 Pc :內部壓力 Pf:經提高的內部壓力 -30-S : enlarged part of the side wall part P i ·_ inflation pressure Pc : internal pressure Pf: increased internal pressure -30-