201236849 六、發明說明： 【發明所屬之技術領域】 本發明標的物係關於在呈預先成形狀態時、且尤其在吹 氣模製物件之前標示各種物件。在標示後，然後藉由（例 如）吹氣模製使物件膨脹並形成。本發明標的物亦係關於 標§己施加、用於該等施加中之油墨及相關方法。 本申請案主張2010年10月20日提出申請之美國臨時申請 案第61/394,882號之優先權。 【先則技術】 通常藉由一或多個模製作業形成具有中空内部之塑膠容 器或其他物件。儘管可使用一系列廣泛的模製作業及技 術，但吹氣模製已眾所周知。大多數吹氣模製作業包括以 下步驟：形成熔融熱塑性材料之中空管，通常稱作「型 坯」；將該型坯放置於吹氣模製腔内部；藉由將加壓氣體 注射入該型坯中或藉由在該型坯周圍產生真空使該型坯膨 脹以形成目標物品；冷卻所得形成物品；且隨後自模具移 出該物品。 如將瞭解，通常以某一方式標示容器及物件，標記可包 括關於谷器之内容物及/或供應商的資訊文字、關於容器 内容物之使用的說明書、或諸如此類。另外，標記亦可含 有用以吸引對容器及/或供應商之注意的設計及彩色資 訊。 傳統上，大多數標記係在形成容器後對容器施加。然 而’已知在容器形成（亦即，藉由模製）期間對容器施加一 159650.doc 201236849 或多種標S己的各種技術。已知模内標示技術，其中沿模製 腔内之暴露面定位標記。在模製腔内之聚合物物件期間， 該標記接觸聚合物材料並保留在所形成物件之外壁或表面 内。儘管在很多方面令人滿意，但業内仍需要沿模製容 器、且尤其吹氣模製容器之外表面納入一或多個標記的改 良方法。 【發明内容】 在與經標示物件、標記及油墨之方法及材料相關的本發 明標的物中解決與先前已知之標示方法相關的困難及缺 點。 在一個態樣令，本發明標的物提供形成經標示物件之方 法。該方法包含提供標記亦及提供預先成形件。該方法亦 包含對預先成形件施加標記，藉此形成經標示預先成形 件。該方法進一步包含使經標示預先成形件膨脹，藉此形 成標示物件。 在另一態樣中，本發明標的物提供形成經標示物件之方 法°亥方法包含提供聚合物標記。該方法亦包含提供聚合 物預先成形件。該方法亦包含提供黏著劑組合物。該方法 另外包含對私§己及預先成形件中之至少一者施加有效量之 黏著劑組合物。該方法進—步包含將該標記黏附至預先成 形件’藉此形成經標示預先成料。並且，财法包含使 經標示預先成形件膨脹，藉此形成經標示物件。 在又一態樣t，本發明標的物提供用於形成經標示預先 成形件之系統。該系統包含至少—種標記及將該至少一種 159650.doc 201236849 才不。己以黏著方式施加至預先成形件的設施，藉此形成經標 示預先成形件。 在又態樣中’本發明標的物提供用於形成經標示容器 ，系統。該系統包含用於吹氣模製預先成形件之設施。該 系統亦包3至J/ 一種包括黏著劑之標記。且該系統包含用 於‘不預先成形件之設施，丨中對預先成形件施加至少一 種心。己。藉由使用標示設施對預先成形件施加至少一種標 §己來使用該系、統。在形成經標示預先成形件後，自經標示 預先成形件使用吹氣模製之設施形成經標示容器。 應瞭解，本發明標的物能夠具有其他及不同之實施例且 其數個細節能夠在各個方面進行修改，而所有此等皆不脫 離該標的物。相應地，應將各附圖及說明視為闡釋性而非 限定性。 【實施方式】 在最後形成物件之間，為標示物件或物件中間體提供各 種較佳貫施例方法。未完全成形之物件在本文中稱作「預 先成形件」。根據較佳實施例方法，標示預先成形件且隨 後對其進行吹氣模製作業，其後產生標示之完全形成容 器。較佳地，在自經標示預先成形件形成物件期間，與預 先成形件相聯之標記膨脹。本發明標的物亦提供與標記一 起使用之各種油墨及相關組合物’該等標記亦經歷膨脹而 不會有害地使標記破裂或以其他方式扭曲。此外，闡述可 視情況用於將標記黏附至預先成形件且亦經歷膨脹之較佳 黏著劑。另外，亦基於本發明標的物提供各種較佳替代性 159650.doc 201236849 貫施例。下文更為詳細地闡述所有該等熊樣。 預先成形件 預先成形件較佳係藉由傳統注射模製方法或藉由擠吹模 製製造。對於擠吹模製而言，通常擠出聚合物之圓柱形中 空部件’在兩端切斷，且隨後在中空部件仍熱時立刻吹服 成瓶或另一室。擠吹模製係形成大多數聚烯烴容器（例如 牛奶壺及洗髮精瓶）之較佳方法。由於擠吹模製通常涉及 炼體強度較低之較熱聚合物溫度，故需注意確保預先成形 件足夠熱且柔物，否則預先成形件將不能適當地膨服或拉 伸幸運的疋，較熱溫度往往更快速地軟化預先成形件。 本文所用術5吾「吹氣模製」包括拉伸吹氣模製方法及擠吹 模製方法。本發明標的物包括所有各種形式之拉伸吹氣模 製，例如單階段吹氣模製及2階段吹氣模製、及各種形式 之擠吹模製，例如輪型擠吹模製及儲料缸式機頭型方法。 本發明標的物+所用之預先成形件較佳包括習用熱塑性 模製聚合物，例如聚酯、聚烯烴、聚碳酸酯、及其組合。 預先成形件可為各種聚合物之單層或多層組合。可使用其 他聚合物形成多層容器之某些層。該等聚合物已為業内所 熟知且包括再循環聚合物（例如聚酯）、性能聚合物（例如乙 烯與乙烯基醇之共聚物（例如乙基乙烯基醇聚合物或 EVOH)、聚醯胺、全芳香族聚酯、聚醚、其摻合物及共聚 物）。 -曰係在本發明;的物中用作預先成形件之聚合物的較 佳類別。適宜聚酯包含二羧酸組份（其較佳包含對苯二曱 159650.doc 201236849 酸或間苯二f酸，較佳至少約5〇莫耳％對苯二甲酸，且在 某些實施财，較佳至少約7 5莫耳％對苯二f酸）及二醇組 份(其包含至少-種選自以下之二醇：乙二醇、環己烷二 甲醇一乙一醇、丁二醇及其混合物聚酯可進—步包 3以1〇0莫耳％二羧酸及100莫耳％二醇計高達約50莫耳％ 之一或多種不同二羧酸及/或高達約5〇莫耳％之一或多種二 醇之量的共單體殘基。在某些實施例中，二缓酸組份、二 醇組份或每—者個別地具有高達約25莫耳％或高達約15莫 耳％之共單體改質可較佳。適宜二㈣共單體包含芳香族 一羧酸、二羧酸之酯、二羧酸酯之酐及其混合物。更具體 而5，適宜二羧酸共單體包括較佳具有8至14個碳原子之 芳香族二羧酸、較佳具有4至12個碳原子之脂肪族二鲮 酸、或較佳具有8至丨2個碳原子之環脂族二羧酸。二綾酸 共單體之實例包括但不限於鄰苯二曱酸、間苯二曱酸、 ‘ 2’6-—甲酸、環己烧二甲酸、環己院二乙酸、二苯基_ 4’4 -一甲酸、二苯基_3,4’_二甲酸、琥珀酸、戊二酸、己二 酉欠、壬二酸、癸二酸、其混合物及諸如此類。 若需要，用於預先成形件令之聚合物及較佳聚酯亦可包 3通$用於聚酯中之添加劑。該等添加劑包括但不限於著 色劑、調色劑、顏料、碳黑、玻璃纖維、填充劑、衝擊改 良劑、抗氡化劑、穩定劑、阻燃劑、再熱助劑、乙醛還原 化合物、氧清除劑、障壁增強助劑、UV抑制劑及其組 合〇 經由業内熟知之方法、例如藉由注射模製或較不通常地 159650.doc 201236849 藉由管材擠出及旋鍛形成預先成形件。首先使用例如 SIDELtm型機器上之一組紅外燈將預先成形件再加熱至期 望吹氣溫度（對於聚（對苯二甲酸乙二酯）（pET)預先成形件 而言通常在約l〇(TC附近）。在紅外加熱後，隨後直接將熱 的預先成形件輸送至吹氣輪，該等預先成形件於其中吹脹 至模具中。應瞭解’本發明標的物可採用以幾乎任一方式 製造之預先成形件。 標記 標記膜材料包括在吹氣模製製程期間可在必需拉伸條件 下存在的聚合物。通常，此需要聚合物具有小於所選吹氣 溫度之玻璃化轉變溫度（rTg」）（用於許多蘇打瓶之ρΕτ具 有77°C之Tg)或在即將吹氣模製之前適宜地加熱標記。在 本發明軚的物之較佳實施例中，可在約23。匚至約〖1 之 溫度下顯著變形而未撕裂之任—聚合物可能可用作標記材 料。多種該等聚合物已為熟習此項技術者所知。較佳地， 標記包括熱塑性聚合物。適宜聚合物包括但不限於聚酯、 共聚酯、聚烯烴、聚醯胺、乙基乙烯基醇（ev〇h)聚合 物、彈性體聚合物摻合物、彈性體摻合物之共聚物及其混 合物。聚醋、共聚醋及聚烯烴（例如聚乙烯及聚丙烯')較 佳。具有類似於容器之定向性質的聚醋（例如聚（對苯二甲 酸乙二酯）（PET))及共聚酯較佳’以使標記之拉伸特性與 吹脹預先成形件匹配更緊密。聚丙烯作為標記材料較佳:、 此乃因因其低成本其係玉業中目前選擇之標記材料。聚丙 稀亦較佳’此乃因其.容易地在再循環流中經由漂浮分離， 159650.doc 201236849 此分離係由於聚丙烯之密度小於水之密度。 標5己可呈單一膜材料形式或多個膜或層之總成形式。對 於夕層軚§己總成而言，每一層之材料可不同或相同。然 而，較佳地，對於使用多種材料之多層總成而言，各種材 料之拉伸特性類似或至少彼此相容。在提及彼此相容之標 記材料時係指在預先成形件膨脹期間其相對於彼此之行 為，以使層不會有害地破裂、撕裂或以其他方式分離。 較佳使用熟習此項技術者已知之方法利用期望標記設計 印刷較佳實施例中所用之標記膜。較佳地，使用變形印刷 方法，該方法補償在吹氣模製製程期間標記將經歷之膨 脹。由於膨脹將逐點變化，例如，容器頸之膨脹將小於側 壁，故變形印刷圖案將相應地變化。通常在平的標記膜上 貫施印刷’該標記膜中之邊緣隨後結合在一起以製得標記 官特疋應用之最合意的標記印刷方法取決於期望圖案及 用於製造容器之設備的類型。 另外且如本文中更詳細闡述，經吹氣膜適於不需印刷但 功能添加劑合意的應用。舉例而言，可向聚合物中添加著 色劑或顏料以產生彩色標記。類似地，如本文中更詳細闊 述’可向所用聚合物中納入uv阻斷濃縮物、障壁層或其 他功能添加劑以產生標記及/或功能膜。類似地，可在預 先成形件周圍安裝染色管以改變容器之整體顏色且隨後將 以黏著方式施加之傳統標記施加至染色管頂部。 端視特定應用而定，可形成標記及/或可選擇其材料， 以使在經標示預先成形件膨脹期間，標記在所有方向上、 159650.doc 201236849 在僅特定方向上、及/或在所有方向但不同程度上拉伸或 膨脹。在形成標記駐留於複合曲率上之經標示物件時，本 發明標的物之後一型式可較佳。 預先成形件及黏著劑之標示 儘管可使用各種技術將一或多個標記緊固及/或附接至 預先成形件，但通常使用黏著劑將標記施加至預先成形 件。可使用一系列廣泛的黏著劑，.例如但不限於非反應性 黏著劑，例如壓感性黏著劑、熱黏著劑及乾燥黏著劑。各 種反應性黏著劑可為有用的，例如多部分黏著劑及單部分 黏著劑。 較佳地，黏著劑係壓感性黏著劑且呈現適宜性質以使黏 著劑以與預先成形件及標記相容之方式膨脹。可接受之代 表性壓感性黏著劑包括彼等闡述於以下專利文件中者：美 國專利5,558,913、美國專利6，187,432、美國專利5,622,783、 美國專利5，183,841、美國專利5,593,759、美國專利 5，100,963、美國專利 5,262,216及美國專利5，180,635。 在某些貫施例中，使用一或多種可活化黏著劑將如本文 更詳細闡述之一或多個標記或拉伸套管緊固及/或附接至 預先成形件。可活化點著劑最初呈非黏性狀態且在使用或 施加之前將其活化以使得黏著劑具有黏性或發黏。 較佳地，可活化黏著劑系統採用本文所述之特定黏著劑 基質聚合物。黏著劑系統通常包含⑴黏著劑基質聚合物、 (11)增塑劑及（iii)增黏劑。該等組份中之每一者之典型且較 佳重量百分比濃度係如下表1中所述。應瞭解，所提及重 159650.doc 10 201236849 量百分比濃度係基於組份（i)-(iii)之總重量。因此，預計且 期望黏著劑系統除下表1中所述組份（ί)_(Π1)外亦可包括其 他組份及添加劑。 表1 -較佳黏著劑系統中之組份的典型及較佳濃度 組份 典型濃度 較佳濃度 黏著劑聚合物基質 20% - 35% 24% - 30% 增塑劑 50% - 75% 56% - 68% 增黏劑 5% - 20% 8% -16% 本文所述之較佳可活化黏著劑系統通常包含黏著劑基質 聚合物（本文中更詳細闡述）、較佳在施加溫度下呈固體結 晶狀態之增塑劑、及較佳在施加溫度下亦呈固體狀態之固 體增黏劑。黏著劑材料之物理狀態可藉由改變溫度在固體 與非固體之間轉換。可藉由調節各組份（亦即黏著劑聚合 物基質、增塑劑及增黏劑）之比率控制黏著劑之間斷時間 (open time)。較佳活化溫度較佳在約5〇。〇至約120〇C範圍 内。然而’應理解’標的物並不限於呈現此範圍内之活化 溫度的黏著劑系統。 在黏著劑之轉換溫度下，黏著力及黏度之性質顯著改 變。因此，可藉由使用本文所述該等策略使壓感性黏著劑 系統自「關閉」熱轉換為「開放」。若隨後於低於指定轉 換溫度之溫度下將該黏著劑系統塗覆至片料上，則材料呈 其非黏性固體狀態。因此’標記構造可捲繞成卷形式。在 施加過程期間’將溫度增大至轉換溫度以使材料變為非固 態且隨後呈現其壓感性黏著劑性質，其使標記由於增大之 159650.doc 11 201236849 黏著性質而黏附至期望基板。若基板呈現多孔表面，則由 於聯鎖效應，即使在溫度降低至低於黏著劑之轉換溫度 時，較佳實施例黏著劑系統亦將流入孔中並充分「黏 結」。 表2中所示調配物闡釋一種例示性黏著劑調配物，其中 使用鄰苯二曱酸二環己基酯作為增塑劑及能量吸收劑二 者。較佳增塑劑之另一實例係甘油三苯甲酸g旨。較佳增塑 劑之其他實例包括鄰苯二曱酸二苯基酯及1，4-環己烷二曱 醇二苯曱酸酯。 表2-例示性黏著劑調配物 黏著劑聚合物基質 濃度重量％ 丙烯酸丁酯（「BA」） 37.2% 苯乙烯 29.3% 甲基丙烯酸曱酯（「MMA」） 29.3% 曱基丙烯酸（「MAA」） 1.7% 丙烯酸（「AA」） 2.5% 熱可活化黏著劑： 黏著劑聚合物基質 28.6% 苯二甲酸二環己基酯（增塑 劑） 57.1% TACOLYN 3400(增黏劑） 14.3% 如本文中更詳細解釋，在形成黏著劑聚合物基質中，較 佳採用有效量之一或多種多官能團單體及一或多種鏈轉移 劑。代表性較佳多官能團單體係乙二醇二曱基丙烯酸酯 (EGDMA)。較佳鏈轉移劑係正十二烷基硫醇（n-DDM)。 本發明標的物亦提供各種較佳實施例黏著劑聚合物基 159650.doc •12- 201236849 質，其包含（1) 一或多種丙烯酸低碳數烷基酯、（ii)苯乙 烯、（iii)甲基丙賴甲酿（MMA)、（iv)甲基丙烯酸（MAA)、 (V)丙烯酸（AA)、一或多種多官能團單體及一或多種鏈轉 移劑。在一個實施例中，該等組份令之每一者的典型且較 佳濃度闡述於如下下表3中。表3中列舉之重量百分比濃度 係基於黏著劑聚合物基質之總重量。應理解，本文所述之 各種黏著劑基質聚合物僅實質上具有代表性。儘管標的物 通常構成本發明標的物之較佳實施例，但絕不限於本文所 述特定黏著劑基質聚合物之使用。 表3 -黏著劑聚合物基質中之組份的典型及較佳濃度 組份 典型濃度 較佳濃度 丙烯酸低碳數烷基酯 苯乙烯 5% - 50% 12% - 48% 20% - 85% 23% - 78% MMA 1% - 35% 3% - 30% MAA 0.5% - 5% 1% - 2% AA 0.5% - 5% 1% - 3% 多官能團單體 0% - 5% 0.5% - 2.5% 鏈轉移劑 0% - 5% 1.0% - 4.0% 在較佳實施例黏著劑聚合物基質中，一系列廣泛的丙稀 酸低碳數烷基酯可單獨或組合用於組份（i)。舉例而言，可 使用丙烯酸曱酯、丙烯酸丁酯、丙烯酸乙酯及丙烯酸2_乙 基己基酯。然而，丁基酯丙烯酸酯及丙烯酸乙酯通常較 佳，丙稀酸丁酯最佳。 一系列廣泛的苯乙烯及基於苯乙烯之材料可用於組份 (ii)。 159650.doc •13· 201236849 類似地，對於組份（iii)而言，通常較佳使用曱基丙烯酸 甲酉旨（MMA)。然而，應瞭解，其他類似物及功能等效單體 可與MMA結合或代替MMa。 組份（iv)之較佳單體係甲基丙烯酸（MAA)。然而，應瞭 解，標的物包括其他等效單體與MAA結合使用或代替 MAA使用。 並且，儘管標注丙烯酸（AA)用作組份卜），但應理解， 本發明標的物包括其他等效單體之使用。 一系列廣泛的多官能團單體或多官能團單體試劑可用於 本發明標的物中。多官能團單體可用於達成基質聚合物之 父聯該等夕g旎團單體之代表性實例包括但不限於二官 此團單體、三官能團單體、及具有三個以上活性功能位點 之多官能團單體。二官能團單體之較佳實例包括但不限於 1，4丁二醇二丙烯酸酯、聚乙二醇（2〇〇)二丙烯酸酯、及其 組合。另-較佳二官能團單體係乙二醇二子基丙烯酸酯 (EGDMA)。三官能圏單體之較佳實例包括但不限於乙氧基 化（15)二經f基丙烧三丙婦酸醋、丙氧基化⑺甘油三丙烯 、及其組合。具有三個以上活性功能位點之多官能團 單體的較佳實例包括但不限於乙氧基化異戊四醇四丙稀酸 H戊四醇五丙稀酸醋、及其組合。該等及多種其他 適且多g月匕團單體可自各種供應商購得，例如如仙，之 。多官能團單體之典型濃度在约〇至約邊範圍 内’約〇·5%至約2.5%較佳，且約1.5%至約2爲最佳。 在形成㈣财所用之鏈轉移劑it常係以約〇至約 I59650.doc 201236849 5.0%、且較佳約！·〇%至約4 〇%之濃度使用（百分比係基於 單體之總重量）。適宜鏈轉移劑之代表性實例包括但不限 於正十二烷基硫醇（n-DDM)、第三壬基硫醇、3-巯基丙酸 異辛基酿、及其組合。應理解’本發明標的物絕不限於該 等鏈轉移劑。相反，可使用一系列廣泛的鏈轉移劑。適宜 鏈轉移劑可自（例如）St. Louis，M0之Sigma Aldrich購得。 最佳地，黏著劑聚合物基質包括⑴一或多種多官能團單體 試劑及（ii)一或多種鏈轉移劑二者。 在一個實施例中，尤佳之黏著劑聚合物基質組合物闡述 於下表3 A中。 表3 A-黏著劑聚合物基質中之組份的較佳及最佳濃度 組份 較佳濃度 最佳濃度 丙烯酸丁酯 9% -14% 12.8% 笨乙烯 ------- 68% - 80% 77.6% MMA 2% - 6% 3.2% MAA 1% - 2% 1.2% AA 1% - 2% 1.7% EGDMA — —----- 0.5% - 2.5% 1.5% n-DDM — ---- 1.0% - 4.0% 1.9% 本發明標的物提供一系列廣泛的具有獨特特性之黏著 劑，該等特性可使黏著劑用於多種應用中。黏著劑之一個 特徵係關於活化黏著劑(亦即’將黏著劑自非黏性狀態選 擇性變為黏性狀態）需要相對較短時間段。快速活化時間 使得黏著劑可用於高速標示作業中。較佳地，本發明標的 物之黏著劑可在約〇3秒之時間段内活化且通常在小於丄 159650.doc •15- 201236849 秒、且更通常小於0.5秒之時間段内活化。此時間段在本 文中稱作黏著劑之「活化時間」。 如本文中先前所述，黏著劑在活化後保留其活化狀態長 達在黏著劑失去其黏性之前至少使具有黏著劑之標記施加 至物或接收基板。此特性在本文中闡述為黏著劑之「間 斷時間」。標的物之黏著劑較佳呈現至少約〇.丨秒至丨〇分 鐘或更長時間之間斷時間。對於某些應用而言，黏著劑可 適於呈現相對較長間斷時間，例如高達72小時或更長時 間。通常，標的物之黏著劑呈現10秒至60秒之間斷時間。 本發明標的物之輪著劑活化後，亦即在呈其「間斷」及 黏性狀態時，黏著劑呈現相對較高黏性。舉例而言，黏著 劑對基板（例如卡板或鋼）呈現至少約10牛頓、且較佳至少 約1.25牛頓之初始峰值黏性。如結合本文所提供實例所 述，較佳實施例黏著劑通常呈現丨.0牛頓至2 〇牛頓範圍内 之初始峰值黏性·值。使用SPAT量測該等黏性值，本文中 加以詳細闡述。較佳地，該等黏性值係關於本文所述基 板。然而，應瞭解，本發明標的物並不限於呈現與本文所 述基板相關之該等黏性值的黏著劑。亦即，預計標的物包 括呈現與本文未明確闌述之其他基板及基板材料相關之該 等黏性值的黏著劑。此外，通常較佳地，在黏著劑活化 時’增黏劑軟化且呈可流動狀態。 SPAT測試係由 Avery Dennison Research Center研發。通 常，此測試程序係如下：藉由將可自Avery Dennis〇n購得 之雙面塗覆帶FT530施加至】/36英吋鋁板上製備試樣。利 159650.doc 201236849 用14.5碎輥將該帶軋製兩次。隨後移除雙面帶之襯墊。隨 後將試樣向下面向暴露雙重塗覆帶定位。使用丨4.5磅輥將 試樣及帶片軋製兩次。隨後使軋製試樣在測試之前經受2〇 分鐘停歇時段。隨後在測試之前移除剩餘釋放襯墊。如下 實施機器設定》使用來自New York，ΝΥ之Texture Technologies的質構分析儀ΤΑ.XT2i。使用具有1英吋直徑 不銹鋼探針之SPAT測試器以0.04 mm/sec之測試速度、4.5 牛頓之壓縮力、及0.01 sec之接觸時間實施分析。關於 SPAT測試程序之其他詳細内容闡述於chuang hk ; Chiu C. . Paniagua R. Avery Adhesive Test yields more performance data than traditional probe, Adhesives Age (10) 1997, 18_ 23中。 應瞭解’本發明標的物絕不限於任一特定黏著劑之使 用。反之，本發明標的物包括幾乎任一黏著劑之使用該 黏著劑令人滿意地將目標標記黏附至預先成形件及容器或 自預先成形件形成之產物，且其呈現適宜性質以便與預先 成形件及標記之膨脹相容。此實踐可有利於標記之拉伸並 減少沿標記及預先成形件界面干擾之潛能。 可根據一或多種圖案將黏著劑施加至預先成形件及/或 標記。在某些應用中，圖案化黏著劑層之使用可為有益 的。舉例而言，可使用黏著劑將標記邊緣區域之部分或全 部黏附至·成形件1於標記之内部區域而言，黏著劑 可不為必需的。 如先前所提及，通常較佳藉由使用黏著劑至少最初將一 159650.doc 17 201236849 或多個標記附接或緊固至預先成形件。然而，可使用一系 列廣泛的其他策略將標記聯合、保留或以其他方式附接至 預先成形件。舉例而言，可使用一或多種焊接作業。可藉 由雷射焊接、熱焊接、RF焊接、或藉由業内已知之任一^ 他焊接技術實料接。替代或除焊接及/或使用黏著劑 外，可使用標記與預先成形件之間之摩擦嚙合。本發明標 的物包括在使用或不使用黏著劑情況下該等策略中之任一 者之使用。若使用黏著劑，則在某些實施例中，黏著劑係 可活化黏著劑，且具體而言係熱活化黏著劑、紅外活 化黏著劑、紫外（uv)活化黏著劑、或諸如此類。 可在預先成形件即將進入模製腔或輪之前之任一時間點 對預先成形件施加標記。根據期望在最後物件上有多少輪 廓標記覆蓋，較佳將標記切成適當長度。此可在將標記放 置於預先成形件上方或其上時於原位進行或可將標記預先 切割成離散單元。使用任—技術，適當絲網/膜操作系統 較佳快速將標記放置於預先成形件上方。常用於工業中之 規則模内標示的系統可經修飾以對標記進行操作。 在吹氣模製製程中，預先成形件及標記將進入吹氣模具 且吹脹成容器形狀。較佳地，預先成形件之殘餘熱用於加 熱標記以使其足夠柔韌來膨脹。或者，可跨越各組份吹/ 施加熱空氣或輻射熱。由於標記及預先成形件在較高溫度 下具有黏性，故在翻轉預先成形件時標記滑落之潛能（正 如一些吹氣模製機器之情形）可忽略。若需要，可使用索 引及註冊設備將標記相對於預先成形件固持在適當位置。 159650.doc •18- 201236849 隨著預先成形件膨脹，標記亦膨服。最終，隨著標記將拉 伸直至其接觸模具壁’標記將採用物件之最後形狀。因 此’產生緊密裝配之輪廓標記而無需雙軸定向膜或收縮隧 道。 在-個實施例中’在重新加熱之前將標記放置於預先成 形件上方對於預先成形件之紅外加熱而言，若標記及用 於印刷標記之油墨不會過度吸收紅外輻射，則此較佳進 行。舉例而言，若油墨阻斷IR輻射，則標記可在油墨定位 處具有熱斑點且預先成形件可在標記下具有冷斑點。此可 產生預先成形件及標記二者之不均勻拉伸。 油墨 較佳地，施加至本文所述預先成形件之標記包括一或多 個裝飾性印刷及/或含有標誌之層。藉由對一或多個標記 層施加油墨或其他彩色調配物形成該等裝飾性印刷或標 4。較佳地，與本文所述標記及策略結合使用之油墨組合 物可膨脹以使在經標示預先成形件膨脹成完全成形之經標 示容器時，油墨組合物亦膨脹。膨脹程度係使得在標記及 預先成形件膨張期間及之後（例如在吹氣模製作業之後）， 油墨組合物未破裂、碎裂及/或自下伏標記基板剝離。因 此，油墨調配物較佳呈現適宜性質以使油墨以與預先成形 件及標記相容之方式膨脹。 儘嘗不希望受限於任何特定態樣或組合物，但油墨調配 物之較佳種類包括經改質之環氧丙烯酸酯預聚物組合物， 其較佳經聚酯或胺基曱酸酯寡聚物改質以增強其撓性及對 I59650.doc •19· 201236849 難黏基板（difficult substrate)之黏著力。用於增強撓性及對 難黏基板之黏著力之該等寡聚物包括二聚體、三聚體、四 聚體或其他共聚子單元《另外，可藉由添加單體及寡聚物 組份（例如丙烯酸酯及曱基丙烯酸酯）進一步改質該組合物 以提供增強黏度。 可適於與本文所述之可膨脹或可拉伸標記及/或預先成 形件一起使用之油墨及油墨調配物之代表性實例提供於 WO 03/106143 中。 在某些較佳態樣中，用於本文所述標記及方法中之油墨 可藉由除藉由暴露於UV輻射來固化外之方法固化。 儘管預期一系列廣泛的油墨（或油墨調配物）可用於本發 明標的物中，但已令人驚奇地發現，包含約10重量％至約 20重量％聚胺基曱酸酯之油墨呈現以下性質：在印刷於標 圯上及標示預先成形件後，油墨可在與吹氣模製預先成形 件相關之典型高溫下耐受膨脹。較佳地，油墨可經歷高達 150%、更佳高達2〇〇%、更佳高達300%、且最佳高達4〇〇% 之膨脹，而不會呈現任何有害效應。如先前所解釋，有害 效應包括油墨自標記破裂、破碎及/或剝離。舉例而言， 在預先成形件在1 00°C下在雙軸拉伸機器上膨脹期間，含 有10%至20%聚胺基甲酸酯且印刷於施加至預先成形件之 才示δ己上的黑色及紅色油墨在雙軸及圓周上分別呈現古達 200%及400%之拉伸大小，而不會呈現有害效應。應瞭 解，可容易地調節聚胺基甲酸酯在油墨調配物中之比例以 適應更高溫度、不同拉伸大小、不同預先成形件及容器幾 159650.doc •20- 201236849 何形狀、及該等因素之組合。預計包含約〗0〇/❶至約2〇%聚 胺基甲酸Sa之油墨通常適於在約1 至約13 〇。〇範圍内之 溫度下雙軸拉伸，且在一個方向上4X大小且在另一方向上 2x大小。该等油墨之代表性實例包括但不限於彼等自201236849 VI. OBJECTS OF THE INVENTION: FIELD OF THE INVENTION The subject matter of the present invention relates to the marking of various articles when in a pre-formed state, and particularly prior to blowing a molded article. After labeling, the article is then expanded and formed by, for example, blow molding. The subject matter of the present invention is also directed to inks and related methods that have been applied, used in such applications. The present application claims priority to US Provisional Application No. 61/394,882, filed on October 20, 2010. [Technology] Plastic containers or other articles having a hollow interior are usually formed by one or more molding operations. Blow molding is well known, although a wide range of molding operations and techniques can be used. Most blow molding operations include the steps of forming a hollow tube of molten thermoplastic material, commonly referred to as a "parison"; placing the parison inside a blow molding cavity; by injecting pressurized gas into the chamber The parison is expanded in the parison or by creating a vacuum around the parison to form the target article; the resulting article is cooled; and the article is subsequently removed from the mold. As will be appreciated, the containers and articles are typically labeled in a manner that may include informational text about the contents of the cereal and/or supplier, instructions for use of the contents of the container, or the like. In addition, the mark may also contain design and color information to attract attention to the container and/or supplier. Traditionally, most markings are applied to the container after it has been formed into a container. However, it is known to apply a variety of techniques to the container during the formation of the container (i.e., by molding) a 159650.doc 201236849 or a plurality of standards. In-mold marking techniques are known in which the indicia are positioned along the exposed faces within the molding cavity. The mark contacts the polymeric material and remains within the outer wall or surface of the formed article during molding of the polymeric article within the cavity. While satisfactory in many respects, there is still a need in the art for improved methods of incorporating one or more indicia along the outer surface of the molded container, and particularly the blow molded container. SUMMARY OF THE INVENTION The difficulties and disadvantages associated with previously known labeling methods are addressed in the present subject matter associated with methods and materials for labeling articles, indicia, and inks. In one aspect, the subject matter of the present invention provides a means of forming a labeled article. The method includes providing a mark and providing a preform. The method also includes applying a marking to the preform to thereby form the marked preform. The method further includes expanding the marked preform to thereby form the marking article. In another aspect, the subject matter of the present invention provides a method of forming a labeled article comprising providing a polymeric label. The method also includes providing a polymeric preform. The method also includes providing an adhesive composition. The method additionally includes applying an effective amount of the adhesive composition to at least one of the private and preformed parts. The method further includes adhering the indicia to the preforms' thereby forming the preformed preform. Also, the financial method includes expanding the marked preform to thereby form the marked article. In yet another aspect, the subject matter of the present invention provides a system for forming a preformed preform. The system contains at least one type of mark and the at least one of 159650.doc 201236849 is not. The means of applying the preform to the preform has been applied in an adhesive manner, thereby forming a preformed preform. In still another aspect, the subject matter of the present invention provides for the formation of a labeled container, system. The system includes a facility for blow molding a preform. The system also includes 3 to J/ a mark including an adhesive. And the system includes a facility for 'unpreformed parts in which at least one core is applied to the preform. already. The system is used by applying at least one standard to the preform by using a marking facility. After forming the preformed preform, the marked container is formed from the preformed preform using a blow molded device. It is to be understood that the subject matter of the invention may be Accordingly, the drawings and description are to be regarded as illustrative and not limiting. [Embodiment] Various preferred embodiments of the method are provided for the object or the intermediate of the object between the finally formed articles. An article that is not fully formed is referred to herein as a "preformed piece." According to the preferred embodiment method, the preform is marked and subsequently subjected to a blow molding operation, after which a fully formed container is produced. Preferably, the indicia associated with the pre-formed member expands during formation of the article from the preformed preform. The subject matter of the present invention also provides various inks and related compositions for use with the indicia' which also undergo expansion without damaging or otherwise distort the indicia. In addition, a preferred adhesive that can be used to adhere the indicia to the preform and also undergo expansion is illustrated. In addition, various preferred alternatives are also provided based on the subject matter of the present invention 159650.doc 201236849. All such bears are described in more detail below. The preformed preform is preferably manufactured by a conventional injection molding method or by extrusion blow molding. For extrusion blow molding, the cylindrical hollow member 'of the extruded polymer is usually cut at both ends, and then immediately blown into a bottle or another chamber while the hollow member is still hot. Extrusion blow molding is the preferred method of forming most polyolefin containers, such as milk jugs and shampoo bottles. Since extrusion blow molding usually involves the temperature of the hot polymer with lower strength of the refining body, care must be taken to ensure that the preform is sufficiently hot and soft, otherwise the preform will not properly expand or stretch the lucky crucible. The hot temperature tends to soften the preforms more quickly. As used herein, "blowing molding" includes a stretch blow molding method and an extrusion blow molding method. The subject matter of the present invention includes all forms of stretch blow molding, such as single-stage blow molding and 2-stage blow molding, and various forms of extrusion blow molding, such as wheel extrusion blow molding and storage. Cylinder head type method. The preforms used in the subject matter of the present invention preferably comprise conventional thermoplastic molding polymers such as polyesters, polyolefins, polycarbonates, and combinations thereof. The preform can be a single layer or a combination of layers of various polymers. Other polymers can be used to form certain layers of the multilayer container. Such polymers are well known in the art and include recycled polymers (e.g., polyesters), performance polymers (e.g., copolymers of ethylene and vinyl alcohol (e.g., ethyl vinyl alcohol polymer or EVOH), polyfluorene. Amines, wholly aromatic polyesters, polyethers, blends and copolymers thereof). - The lanthanide is used in the present invention as a preferred class of polymers for preforms. Suitable polyesters comprise a dicarboxylic acid component (which preferably comprises p-benzoquinone 159650.doc 201236849 acid or isophthalic acid, preferably at least about 5 mole % terephthalic acid, and in some implementations Preferably, at least about 75 mole percent p-phenylene acid and a diol component comprising at least one glycol selected from the group consisting of ethylene glycol, cyclohexane dimethanol monoethanol, butanediol And the mixture of polyesters thereof can be as high as about 50 mole % of one or more different dicarboxylic acids and/or up to about 5 Å based on 1 〇 0 mol % dicarboxylic acid and 100 mol % diol. a molar amount of one or more conjugated amounts of a comonomer residue. In certain embodiments, the bis-acidic component, the diol component, or each individually has up to about 25 mole percent or up to Preferably, about 15 mole % of the comonomer is modified. Suitable di(tetra) co-monomers include aromatic monocarboxylic acids, esters of dicarboxylic acids, anhydrides of dicarboxylic acid esters, and mixtures thereof. More specifically, 5 is suitable. The dicarboxylic acid co-monomer comprises an aromatic dicarboxylic acid preferably having 8 to 14 carbon atoms, preferably an aliphatic dicarboxylic acid having 4 to 12 carbon atoms, or preferably having 8 to 2 carbons. Examples of cycloaliphatic dicarboxylic acids. Examples of dinonanoic acid co-monomers include, but are not limited to, phthalic acid, isophthalic acid, '2'6-carboxylic acid, cyclohexanedicarboxylic acid, cyclohexyl Diacetic acid, diphenyl-4'4-monocarboxylic acid, diphenyl-3,4'-dicarboxylic acid, succinic acid, glutaric acid, hexamethylene dioxime, sebacic acid, sebacic acid, mixtures thereof and the like If desired, the polymer used for the pre-formed parts and the preferred polyester may also be included in the additive for the polyester. These additives include, but are not limited to, colorants, toners, pigments, carbon black. , glass fiber, filler, impact modifier, anti-cracking agent, stabilizer, flame retardant, reheating auxiliary, acetaldehyde reducing compound, oxygen scavenger, barrier reinforcing agent, UV inhibitor and combination thereof Forms well known in the art, such as by injection molding or less commonly 159650.doc 201236849, are formed by pipe extrusion and swaging. The preforms are first formed using a set of infrared lamps, such as on a SIDELtm type machine. Reheat to the desired blowing temperature (for poly(ethylene terephthalate) (pET) The preform is typically about 1 Torr (near TC). After infrared heating, the hot preform is then directly transferred to the blow wheel, where the preforms are inflated into the mold. The subject matter of the present invention may employ a preform formed in almost any manner. The marking film material includes a polymer which may be present under the necessary stretching conditions during the blow molding process. Typically, this requires the polymer to be less than The glass transition temperature (rTg) of the selected blowing temperature (the ρ τ for many soda bottles has a Tg of 77 ° C) or the heating of the mark appropriately just prior to blow molding. In a preferred embodiment, the polymer may be significantly deformed without tearing at a temperature of from about 23 Torr to about 1:1, and the polymer may be used as a marking material. A variety of such polymers are known to those skilled in the art. Preferably, the indicia comprises a thermoplastic polymer. Suitable polymers include, but are not limited to, polyesters, copolyesters, polyolefins, polyamines, ethyl vinyl alcohol (ev〇h) polymers, elastomeric polymer blends, copolymers of elastomer blends And mixtures thereof. Polyacetal, copolymerized vinegar and polyolefins such as polyethylene and polypropylene ') are preferred. Polyketone having a directional property similar to that of the container (e.g., poly(ethylene terephthalate) (PET)) and copolyester is preferred to make the tensile properties of the mark more closely match the inflated preform. Polypropylene is preferred as a marking material: this is due to its low cost and its currently selected marking material in the jade industry. Polypropylene is also preferred 'this is because it is easily separated by floatation in the recycle stream, 159650.doc 201236849 This separation is due to the fact that the density of polypropylene is less than the density of water. The label 5 can be in the form of a single membrane material or a plurality of membranes or layers. For the 軚 軚 軚 己 总 assembly, the material of each layer may be different or the same. Preferably, however, for multilayer assemblies using a plurality of materials, the tensile properties of the various materials are similar or at least compatible with one another. Reference to mutually compatible marking materials refers to their behavior relative to each other during expansion of the preform so that the layers do not deleteriously crack, tear or otherwise separate. The marking film used in the preferred embodiment is preferably printed using the desired marking design using methods known to those skilled in the art. Preferably, a anamorphic printing method is used which compensates for the expansion that the marking will experience during the blow molding process. Since the expansion will vary point by point, for example, the expansion of the container neck will be less than the side walls, the deformed printed pattern will vary accordingly. The printing method which is generally applied to the flat marking film and the edges of the marking film are then bonded together to produce the most desirable marking printing application depends on the desired pattern and the type of equipment used to manufacture the container. Additionally and as explained in more detail herein, the blown film is suitable for applications where printing is not required but functional additives are desirable. For example, a coloring agent or pigment can be added to the polymer to produce a colored marking. Similarly, uv blocking concentrates, barrier layers or other functional additives may be incorporated into the polymers used to produce labeled and/or functional films, as described in more detail herein. Similarly, a dye tube can be placed around the preform to change the overall color of the container and then conventionally applied in an adhesive manner to the top of the stain tube. Depending on the particular application, the markings may be formed and/or materials may be selected such that during expansion of the marked preforms, the markings are in all directions, 159650.doc 201236849 in only certain directions, and/or at all Oriented but stretched or expanded to varying degrees. A preferred form of the subject matter of the present invention may be preferred when forming a labeled article that resides on a composite curvature. Labeling of Preforms and Adhesives While one or more indicia can be secured and/or attached to the preforms using a variety of techniques, the indicia is typically applied to the preforms using an adhesive. A wide variety of adhesives can be used, such as, but not limited to, non-reactive adhesives such as pressure sensitive adhesives, thermal adhesives, and dry adhesives. Various reactive adhesives can be useful, such as multi-part adhesives and single-part adhesives. Preferably, the adhesive is a pressure sensitive adhesive and exhibits suitable properties to allow the adhesive to expand in a manner compatible with the preform and the marking. Acceptable representative pressure sensitive adhesives include those described in the following patent documents: U.S. Patent 5,558,913, U.S. Patent 6,187,432, U.S. Patent 5,622,783, U.S. Patent 5,183,841, U.S. Patent 5,593,759, U.S. Patent 5,100,963, U.S. Patent 5,262,216 and U.S. Patent 5,180,635. In some embodiments, one or more indicia or stretch sleeves as described in more detail herein are secured and/or attached to the preform using one or more activatable adhesives. The activatable dispensing agent is initially in a non-adhesive state and is activated prior to use or application to render the adhesive viscous or tacky. Preferably, the activatable adhesive system utilizes the particular adhesive matrix polymer described herein. Adhesive systems typically comprise (1) an adhesive matrix polymer, (11) a plasticizer, and (iii) a tackifier. Typical and preferred weight percent concentrations for each of these components are as described in Table 1 below. It should be understood that the weight percent concentration referred to is based on the total weight of components (i)-(iii). Therefore, it is expected and desirable that the adhesive system include other components and additives in addition to the components (ί)_(Π1) described in Table 1 below. Table 1 - Typical and preferred concentrations of components in a preferred adhesive system Typical concentration Preferred concentration Adhesive polymer matrix 20% - 35% 24% - 30% Plasticizer 50% - 75% 56% - 68% tackifier 5% - 20% 8% -16% The preferred activatable adhesive system described herein typically comprises an adhesive matrix polymer (described in more detail herein), preferably solid at application temperature A plasticizer in a crystalline state, and a solid tackifier which is preferably in a solid state at the application temperature. The physical state of the adhesive material can be converted between solid and non-solid by varying the temperature. The adhesive can be controlled by adjusting the ratio of the components (i.e., the adhesive polymer matrix, the plasticizer, and the tackifier) to control the open time of the adhesive. Preferably, the activation temperature is about 5 Torr. 〇 to about 120〇C. However, it is understood that the subject matter is not limited to an adhesive system that exhibits an activation temperature within this range. At the conversion temperature of the adhesive, the properties of adhesion and viscosity change significantly. Thus, the pressure sensitive adhesive system can be converted from "off" heat to "open" by using the strategies described herein. If the adhesive system is subsequently applied to the sheet at a temperature below the specified switching temperature, the material is in a non-stick solid state. Thus the 'marker construction can be wound into a roll form. During the application process, the temperature is increased to the transition temperature to render the material non-solid and then exhibit its pressure-sensitive adhesive properties which cause the marking to adhere to the desired substrate due to the increased adhesive properties of 159650.doc 11 201236849. If the substrate exhibits a porous surface, the preferred embodiment of the adhesive system will flow into the pores and sufficiently "bond" due to the interlocking effect even when the temperature is lowered below the transition temperature of the adhesive. The formulations shown in Table 2 illustrate an exemplary adhesive formulation in which dicyclohexyl phthalate is used as both a plasticizer and an energy absorber. Another example of a preferred plasticizer is glycerol tribenzoate. Other examples of preferred plasticizers include diphenyl phthalate and 1,4-cyclohexanedonol dibenzoate. Table 2 - Exemplary Adhesive Formulation Adhesive Polymer Matrix Concentration Weight % Butyl Acrylate ("BA") 37.2% Styrene 29.3% Ethyl Methacrylate ("MMA") 29.3% Mercapto Acrylic Acid ("MAA") ) 1.7% Acrylic ("AA") 2.5% Heat-activatable adhesive: Adhesive polymer matrix 28.6% Dicyclohexyl phthalate (plasticizer) 57.1% TACOLYN 3400 (tackifier) 14.3% In more detail, it is preferred to employ an effective amount of one or more polyfunctional monomers and one or more chain transfer agents in forming the adhesive polymer matrix. Representative polyfunctional monosystem ethylene glycol dimercapto acrylate (EGDMA) is representative. A preferred chain transfer agent is n-dodecyl mercaptan (n-DDM). The subject matter of the present invention also provides various preferred embodiments of the adhesive polymer base 159650.doc • 12-201236849 comprising (1) one or more lower alkyl acrylates, (ii) styrene, (iii) Methyl propylene (MAA), (iv) methacrylic acid (MAA), (V) acrylic acid (AA), one or more polyfunctional monomers, and one or more chain transfer agents. In one embodiment, the typical and preferred concentrations of each of the components are set forth in Table 3 below. The weight percent concentrations listed in Table 3 are based on the total weight of the adhesive polymer matrix. It should be understood that the various adhesive matrix polymers described herein are only representative in nature. Although the subject matter typically constitutes a preferred embodiment of the subject matter of the invention, it is in no way limited to the use of the particular adhesive matrix polymer described herein. Table 3 - Typical and preferred concentrations of components in the adhesive polymer matrix Typical concentration Preferred concentration Acrylic lower alkyl styrene 5% - 50% 12% - 48% 20% - 85% 23 % - 78% MMA 1% - 35% 3% - 30% MAA 0.5% - 5% 1% - 2% AA 0.5% - 5% 1% - 3% Polyfunctional monomer 0% - 5% 0.5% - 2.5 % chain transfer agent 0% - 5% 1.0% - 4.0% In the preferred embodiment of the adhesive polymer matrix, a wide range of low alkyl acrylates can be used alone or in combination for the component (i) . For example, decyl acrylate, butyl acrylate, ethyl acrylate, and 2-ethylhexyl acrylate can be used. However, butyl acrylate and ethyl acrylate are generally preferred, and butyl acrylate is preferred. A wide range of styrene and styrene-based materials are available for component (ii). 159650.doc •13· 201236849 Similarly, for component (iii), it is generally preferred to use methacrylic acid methyl hydrazine (MMA). However, it should be understood that other analogs and functionally equivalent monomers may be combined with or substituted for MMA. The preferred single system of component (iv) is methacrylic acid (MAA). However, it should be understood that the subject matter includes other equivalent monomers used in conjunction with or in place of MAA. Also, although the labeling of acrylic acid (AA) is used as the component, it is to be understood that the subject matter of the invention includes the use of other equivalent monomers. A wide variety of polyfunctional monomeric or polyfunctional monomeric reagents can be used in the subject matter of the present invention. Representative examples of polyfunctional monomers that can be used to achieve the parental association of the matrix polymer include, but are not limited to, the dilute monomer, the trifunctional monomer, and having more than three active functional sites. Multifunctional monomer. Preferred examples of the difunctional monomer include, but are not limited to, 1,4 butanediol diacrylate, polyethylene glycol (2〇〇) diacrylate, and combinations thereof. Further - a preferred difunctional monosystem ethylene glycol diarytacrylate (EGDMA). Preferred examples of the trifunctional fluorene monomer include, but are not limited to, ethoxylated (15) di-f-propylpropanol acetoacetate, propoxylated (7) glycerol tripropylene, and combinations thereof. Preferred examples of polyfunctional monomers having three or more active functional sites include, but are not limited to, ethoxylated pentaerythritol tetraacrylic acid H pentaerythritol pentaacetic acid vinegar, and combinations thereof. These and a variety of other suitable and multi-glycol monomers can be purchased from various suppliers, such as, for example, Xian. Typical concentrations of the polyfunctional monomer range from about 〇 to about 约 约 5% to about 2.5%, and from about 1.5% to about 2 are preferred. In the formation of (4) financial chain transfer agent it is usually from about I to about I59650.doc 201236849 5.0%, and preferably about! • 〇% to a concentration of about 4% (the percentage is based on the total weight of the monomers). Representative examples of suitable chain transfer agents include, but are not limited to, n-dodecyl mercaptan (n-DDM), third mercapto mercaptan, 3-mercaptopropionic acid isooctyl, and combinations thereof. It is to be understood that the subject matter of the present invention is by no means limited to such chain transfer agents. Instead, a wide range of chain transfer agents can be used. Suitable chain transfer agents are commercially available, for example, from Sigma Aldrich of St. Louis, M0. Most preferably, the adhesive polymer matrix comprises (1) one or more multifunctional monomeric agents and (ii) one or more chain transfer agents. In one embodiment, a preferred adhesive polymer matrix composition is set forth in Table 3A below. Table 3 Preferred and optimal concentration of components in A-adhesive polymer matrix. Preferred concentration Best concentration butyl acrylate 9% -14% 12.8% Stupid ethylene ------- 68% - 80% 77.6% MMA 2% - 6% 3.2% MAA 1% - 2% 1.2% AA 1% - 2% 1.7% EGDMA — —----- 0.5% - 2.5% 1.5% n-DDM — --- - 1.0% - 4.0% 1.9% The subject matter of the present invention provides a wide range of adhesives with unique characteristics that allow adhesives to be used in a variety of applications. One characteristic of the adhesive is that it takes a relatively short period of time to activate the adhesive (i.e., 'selectively change the adhesive from a non-adhesive state to a viscous state). The fast activation time allows the adhesive to be used in high speed marking operations. Preferably, the adhesive of the subject matter of the invention is activated over a period of about 3 seconds and is typically activated over a period of time less than 159 159650.doc • 15 - 201236849 seconds, and more typically less than 0.5 seconds. This period of time is referred to herein as the "activation time" of the adhesive. As previously described herein, the adhesive retains its activated state upon activation until at least the marking with the adhesive is applied to the receiving or receiving substrate before the adhesive loses its viscosity. This property is described herein as the "interruption time" of the adhesive. Preferably, the adherent of the subject exhibits a break time of at least about 〇.丨 seconds to 丨〇 minutes or longer. For some applications, the adhesive can be adapted to exhibit a relatively long interruption time, such as up to 72 hours or longer. Typically, the adherent of the subject exhibits a break time of between 10 seconds and 60 seconds. The adhesive exhibits a relatively high viscosity after activation of the wheel of the present invention, i.e., in its "intermittent" and viscous state. For example, the adhesive exhibits an initial peak viscosity to the substrate (e.g., a card or steel) of at least about 10 Newtons, and preferably at least about 1.25 Newtons. As described in connection with the examples provided herein, the preferred embodiment adhesives typically exhibit an initial peak viscosity value in the range of 牛.0 Newtons to 2 Newtons. These viscosity values are measured using SPAT and are described in detail herein. Preferably, the viscosities are for the substrates described herein. However, it should be understood that the subject matter of the present invention is not limited to adhesives that exhibit such viscosities associated with the substrates described herein. That is, it is contemplated that the subject matter includes adhesives that exhibit such viscosities associated with other substrates and substrate materials not specifically described herein. Further, it is generally preferred that the tackifier softens and is flowable when the adhesive is activated. The SPAT test was developed by the Avery Dennison Research Center. Typically, this test procedure is as follows: Samples were prepared by applying a double coated tape FT530 available from Avery Dennis(R) to a /36 inch aluminum plate. Lee 159650.doc 201236849 The belt was rolled twice with a 14.5 crushing roll. The liner of the double-sided tape is then removed. The sample is then positioned downward facing the exposed double coated strip. The sample and the strip were rolled twice using a 磅4.5 lb. roller. The rolled samples were then subjected to a 2 minute rest period prior to testing. The remaining release liner was then removed prior to testing. The following is the implementation of the machine settings. Using the texture analyzer ΤΑ.XT2i from Texture Technologies of New York, ΝΥ. The analysis was performed using a SPAT tester with a 1 inch diameter stainless steel probe at a test speed of 0.04 mm/sec, a compression force of 4.5 Newtons, and a contact time of 0.01 sec. Further details on the SPAT test procedure are set forth in chuang hk; Chiu C. . Paniagua R. Avery Adhesive Test yields more performance data than traditional probe, Adhesives Age (10) 1997, 18_23. It should be understood that the subject matter of the present invention is in no way limited to the use of any particular adhesive. Conversely, the subject matter of the present invention includes the use of the adhesive to satisfactorily adhere the target indicia to the preform and the container or the product formed from the preform, and which exhibits suitable properties for use with the preform. And the expansion of the mark is compatible. This practice can facilitate the stretching of the mark and reduce the potential for interference along the mark and preform interface. The adhesive can be applied to the preform and/or indicia according to one or more patterns. In some applications, the use of a patterned adhesive layer can be beneficial. For example, an adhesive may be used to adhere part or all of the marked edge region to the inner region of the indicia 1 and the adhesive may not be necessary. As mentioned previously, it is generally preferred to initially attach or fasten a 159650.doc 17 201236849 or plurality of indicia to the preform by using an adhesive. However, a wide range of other strategies can be used to join, retain, or otherwise attach the indicia to the preform. For example, one or more welding operations can be used. It can be connected by laser welding, heat welding, RF welding, or by any welding technique known in the art. Instead of or in addition to welding and/or the use of an adhesive, frictional engagement between the marking and the preform can be used. The subject matter of the present invention includes the use of any of these strategies with or without the use of an adhesive. If an adhesive is used, in some embodiments, the adhesive can activate the adhesive, and in particular is a heat activated adhesive, an infrared active adhesive, an ultraviolet (uv) activated adhesive, or the like. The preform can be marked at any point prior to the preform being advanced into the molding cavity or wheel. Depending on how many contour marks are desired on the final object, it is preferred to cut the marks to the appropriate length. This may be done in situ when the indicia is placed over or over the preform or the indicia may be pre-cut into discrete units. Using any technology, a suitable screen/membrane operating system preferably places the indicia over the preform. Systems that are commonly used in the industry for regular in-mold marking can be modified to operate on the indicia. In the blow molding process, the preforms and indicia will enter the blow mold and be inflated into a container shape. Preferably, the residual heat of the preform is used to heat the indicia to make it flexible enough to expand. Alternatively, air or radiant heat can be blown/applied across the components. Since the markings and preforms are tacky at higher temperatures, the potential for marking slippage when flipping the preforms (as in the case of some blow molding machines) is negligible. If desired, the index can be held in place relative to the preform using the indexing and registration equipment. 159650.doc •18- 201236849 As the preforms expand, the markings are also swollen. Eventually, the final shape of the article will be used as the indicia will stretch until it contacts the mold wall. Therefore, a tightly assembled contour mark is produced without the need for a biaxially oriented film or a shrink tunnel. In one embodiment, 'putting the indicia over the preform prior to reheating is preferred for infrared heating of the preform, if the indicia and the ink used to print the indicia do not overly absorb infrared radiation. . For example, if the ink blocks IR radiation, the indicia can have hot spots at the ink location and the preform can have cold spots under the indicia. This can result in uneven stretching of both the preform and the indicia. Ink Preferably, the indicia applied to the preforms described herein include one or more layers of decorative printing and/or marking. The decorative prints or labels are formed by applying ink or other color formulation to one or more of the marking layers. Preferably, the ink composition used in conjunction with the markings and strategies described herein is expandable to expand the ink composition as the preformed preform is expanded into a fully formed marked container. The degree of expansion is such that the ink composition is not broken, chipped, and/or peeled from the underlying marking substrate during and after expansion of the marking and preform formation (e.g., after a blow molding operation). Accordingly, the ink formulation preferably exhibits suitable properties to allow the ink to expand in a manner compatible with the preform and the indicia. It is not intended to be limited to any particular aspect or composition, but a preferred class of ink formulations includes a modified epoxy acrylate prepolymer composition, preferably a polyester or amine phthalate. The oligomer was modified to enhance its flexibility and adhesion to the I59650.doc •19·201236849 difficult substrate. Such oligomers for enhancing flexibility and adhesion to difficult-to-adhere substrates include dimers, trimers, tetramers, or other copolymerized subunits. Additionally, by adding monomers and oligomer groups Parts such as acrylates and methacrylates further modify the composition to provide enhanced viscosity. Representative examples of inks and ink formulations that may be suitable for use with the swellable or stretchable markings and/or preforms described herein are provided in WO 03/106143. In certain preferred embodiments, the inks used in the markings and methods described herein can be cured by methods other than curing by exposure to UV radiation. While a wide variety of inks (or ink formulations) are contemplated for use in the subject matter of the present invention, it has been surprisingly discovered that inks comprising from about 10% to about 20% by weight of polyaminophthalic acid ester exhibit the following properties : After printing on the label and marking the preform, the ink can withstand expansion at typical elevated temperatures associated with blow molded preforms. Preferably, the ink can experience an expansion of up to 150%, more preferably up to 2%, more preferably up to 300%, and optimally up to 4%, without exhibiting any deleterious effects. As explained previously, deleterious effects include ink rupture, breakage and/or peeling from the mark. For example, during the expansion of the preform on the biaxial stretching machine at 100 ° C, it contains 10% to 20% polyurethane and is printed on the pre-formed part. The black and red inks exhibit a 200% and 400% stretch on the biaxial and circumferential sides, respectively, without exhibiting deleterious effects. It will be appreciated that the ratio of polyurethane in the ink formulation can be readily adjusted to accommodate higher temperatures, different stretch sizes, different preforms and containers, and the shape and A combination of factors. It is contemplated that an ink comprising from about 0 Torr/hr to about 2% polycarbamic acid Sa is generally suitable for from about 1 to about 13 Torr. The biaxial stretching at a temperature within the range of 〇 is 4X in one direction and 2x in the other direction. Representative examples of such inks include, but are not limited to,
Addison，IL 之 Toyo Ink America，LLC 以 LIOVALUE 或 AQUALIONA或自 Amherst, NY之IIMAK以 FK002e購得者。 方法 通常，本發明標的物之方法包含提供標記或標記總成、 k供預先成形件 '對預先成形件施加標記、及自預先成形 件形成最終或完全成形之經標示物件。本文提供與提供標 記及預先成形件、對預先成形件提供標記及自其形成最終 物件相關之詳細内容及較佳態樣。 可使用多種不同技術對預先成形件施加標記。可使用標 記施加技術，例如在預先成形件與標記之間使用壓感性黏 著劑。或者’可藉由模内標示技術對預先成形件施加標 記。舉例而言’可沿模具壁佈置具有^拉伸特性之一或 多個標記’在該模具壁内形成預先成形件。在（例如）藉由 注射模製來模製預先成形件時，將一或多個標記緊心固 定至預先成形件之外周邊。 在形成涇標示預先成形件後，隨後使經標示預先成力 經受一或多個作業以視需要形成具有標記之期望物件< 佳地’吹氣模製經標示預先成形件以形成經標示物件( 此技術中，將經標示預先成形件加熱至大於預先成形卡 標記二者之玻璃化轉變溫度的溫度。纟已充分加熱㈣ 159650.doc • 21· 201236849 預先成形件後’隨後視需要拉伸經標示預先成形件、使其 膨脹及/或對其進行吹氣以形成目標物件。在實施此作業 時，標記亦經歷廢j脹以使標記與預先成形件一起拉伸、變 形並改變形狀。最佳地，標記之玻璃化轉變溫度小於或等 於預先成形件之玻璃化轉變溫度。 本發明標的物方法之較佳且顯著態樣係在對預先成形件 施加標記後，標記與預先成形件同時經歷膨脹。因此，在 預先成形件吹脹或以其他方式經歷膨脹以形成期望目標物 件時，與預先成形件相聯之標記亦經歷膨脹。最佳地，預 先成形件及標記之膨脹程度相同或實質上相同。 管代貫施例及應用 在又一態樣中，本發明標的物提供含有一或多種試劑$ 膜或相對較薄層’其佈置在預先成形件之外周邊周圍以崔 在預先成形件膨脹時，完全成形之物件含有具有一或多卷 °式劑之外層’該等試劑納人所形成物件之外周邊周圍。摩 里 或夕種试劑可為著色劑、調色劑、顏料、碳 ·:抗氧化劑、穩定劑、阻燃劑、氧清除劑、障壁添加 劑、uv抑制劑及其組合。該等適宜可以此方式容易地納 外周邊周圍。可藉由已知擠出技術或其他方法形 ff等試劑及/或其他添加劑之臈或聚合物層。 J::乎任一方式將含有試劑之膜(在本文中通常稱作 藉由Γ二）附接至預先成形件。在某些較佳態樣中，可 然而’或黏著劑將含有試劑之膜附接至預先成形件。 …、在昨多應用巾，可較佳避免使用黏著劑。不含點著 159650.doc •22· 201236849 劑之構造可節省成本。棗你丨二a 舉例而言，呈管形式之標記可適當 定位㈣先絲件周圍1管可為具有接縫之閉合管^ 接縫係以化學或機械方式形式，例如溶合、焊接等 者’拉伸管可自適當標記材料形成並定位於預先成形件^ 外周邊周目。在某些實施例中，較佳自作為㈣成形件之 相同聚合物材料形成管及/或標記。此舉措將有利於自瘦 標不預先成形件產生之標示物件的再循環努力。此外，預 計使用生物可降解添加劑或部分水溶性聚合物在用於本文 所达標記中時可在再循環期間更易於自剩餘容器分 標記。 通常’對於使用-或多個功能膜之應用而言，較佳在任 何標記之前（亦即在1下古、& h #, &、λ I隹/、下方）施加該（等）膜，然而，標的物 包括在經標示預先成形件上方施加—或多個功能膜之實施 例。亦預計可在兩個或更多個功能膜之間佈置一或多個標 記0 在某些H樣巾’較佳提衫位㈣先成形件之外周邊周 圍之拉伸管或「拉伸套管」。可藉由有效量之一或多種黏 著劑將拉伸㈣緊W預先成料。在其他實施例中，藉 由雷射焊接將拉伸套管較或以其他方式聯合至預先成形 件。涵蓋其他類型之焊接。在又一些實施例卜拉伸套管 可相對於預先成形件適當地定位而不使用黏著劑。拉伸套 管與預先成形件之間之接觸及/或摩擦嚙合可足以維持拉 伸套管之期望位置或定向。涵蓋不使用黏著劑之其他實施 例，然而，以適宜定向及/或位置保留拉伸套管。然而， 159650.doc •23- 201236849 對於許多實施例而言，較佳採用黏著劑以至少最初將拉伸 套管緊固至預先成形件。如本文所提及，可使用一系列廣 泛的黏著劑。在某些實施例中，黏著劑係可活化黏著劑且 具體而言熱活化黏著劑、紅外（IR)活化黏著劑、紫外（uv) 活化黏著劑、或諸如此類。 圖1係根據本發明標的物之較佳實施例製程1的流程圖。 在此較佳製程1中，提供預先成形件，通常表示為1〇。預 先成形件可自存貨提供或可自業内已知之技術形成。預先 成形件較佳係如本文所述。亦在作業20中提供標記或標記 總成。同樣，標記可自存貨提供或可視需要形成或以其他 方式成形。標記較佳係如本文所述，可以任一方式實施作 業10及20，且在某些情況性，可同時實施。如本文中先前 所述，預計對於大多數應用而言，將對標記施加一或多種 設計、文字、標誌、標識及/或顏色。此作業表示為作業 3 〇。可藉由幾乎任一方式（例如藉由包括（例如）凹版印刷、 膠版印刷、柔性版印刷、凸版印刷、絲網印刷及數位印刷 之印刷技術）對標記施加各種設計及/或文字。 車乂佳地，使用數位印刷技術印刷標記。通常，電子控制 之印刷機將一或多種適宜油墨組合物沈積於標記表面上。 較佳使用具有資料存儲設施之電子控制器以使印刷機作 業，從而在標記上形成期望圖案、文字或標誌。在標記上 形成期望圖案或諸如此類可在製程令之任一點處實施。然 而’較佳在即將對預先成形件施加標記之前且最佳通常在 對預先成形件施加標記之相同處理線内實施印刷。數位印 159650.doc -24- 201236849 刷設施非常適用於連續標示作業且在生產線自一個容器或 產物變為另一者時可容易地重新組態。 在作業40中，對預先成形件施加經裝飾標記以形成經標 示預先成形件。此作業可以多種不同方式來實施。較佳 地，使用黏著劑將標記黏附至預先成形件。黏著劑較佳係 如本文所述。黏著劑可沿預先成形件及標記之一者或二者 之外表面施加或以其他方式存在。亦預計不使用黏著劑。 相反，根據構成預先成形件及標記之材料及各自表面之溫 度，黏著劑可充分黏附至預先成形件。儘管通常較不佳， 但亦預計可使用模内標示技術。 在適宜地標示預先成形件時，經標示預先成形件在作業 50中膨脹形成目標產物或標的。如本文中所解釋，較佳藉 由吹氣模製實施膨脹。同時，作業50通常包括一或多個加 熱作業以使預先成形件及施加於其上之標記足夠柔勒用於 膨脹及/或拉伸。可在經標示預先成形件膨脹之前及/或期 間實施加熱。 圖2繪示根據本發明標的物之另一較佳實施例製程丨。 在製程100中，通常提供預先成形件，表示為作業11〇。此 可對應於圖1之製程1中先前所述之作業1〇。在作業12〇中 提供標記或標記總成。作業120對應於圖丨中先前所述之作 業20。作業110及120可以任一方式實施且在某些情況下可 同時實施。 在作業130中，將如本文所述一或多種油墨沈積於標記 上。油墨較佳呈現如本文所述之特性，該等特性使得其可 159650.doc -25- 201236849 用於拉伸或膨膜應用較佳地，使用數位印刷技術在標 記上印刷油墨或其他調配物。 在作業140争’對標記、預先成形件或二者施加有效量 之黏著劑’且將標記適當定位並施加於預先成形件以形成 經標示預先成形件4佳地，黏著劑係㈣性黏著劑。 隨後在作業150中加熱經標示預先成形件。加熱可在（例 如)自環境溫度至小於預先成形件發生膨脹之溫度之中間 溫度、或自+ @溫度至膨服溫度的任一溫度範圍内。 在作業160中’所加熱經標示預先成形件膨脹。較佳 地，藉由吹氣模製技術實施膨脹。此外，膨服可僅偏愛形 成中間產物。 在作業I7G中’形成最終產物。通常，可對完全成形之 產物實施-或多種最終作業。作業m亦可包括中間產物 之進-步膨脹。最終作業可(例如)包括在完全成形之物件 之外表面上施加一或多個外塗層、頂塗層或保護層。可對 物件貫施機械或化學作業。 圖3繪示根據本發明標的物之另—較佳實施例製程2〇〇。 車乂佳製程2GG通常對應於先前所述之製程i及⑽且包括形 或多個功能膜及/或將其施加至預先成形件。具體而 吕’參照圖3，在作業加及細中提供預先成形件及標記 (或標記總成）。該等作業係如^之先前所述作㈣、汕及 圖2之作業11〇、120 ’且可以任一順序實施。 在作業21G中提供—或多個减成形件後，實施可選作 業230，《中對預先成形件施加—或多個功能膜。功能膜 159650.doc -26- 201236849 係如本文所述且可以如本文先前所述之幾乎任一方式施 加0 在作業240中，在標記上形成一或多種設計、文字、標 誌或諸如此類。此作業可如針對圖1中之作業3 0或圖2中之 作業130先前所述來實施。亦可如本文所提及來闡述該等 設計、文字、標誌或諸如此類的形成。 在作業250中對預先成形件施加經裝飾（例如印刷）標 記°對預先成形件施加標記會產生經標示預先成形件。同 樣’此可如圖1之作業4〇、圖2之作業140中先前所述及/或 如本文通常所述來實施。 隨後視情況在作業260中加熱經標示預先成形件◎該可 選加熱可如聯合圖2之作業150先前所述或如本文通常所述 來實施。 在作業270中實施經標示預先成形件之膨脹。此可如結 合圖1之作業50、圖2之作業160所述及/或如本文通常所述 來實施。 隨後可對產物實施一或多個最終作業，如參照圖3中之 作業280，例如如本文先前所述。 儘官已主要在標示單一預先成形件且隨後使預先成形件 膨脹形成目標標的或物件方面闡述本發明標的物及其各種 實施例，但應瞭解，本發明標的物包括標示複數個預先成 形件且隨後使其膨脹形成複數個標的之作業。亦即，標的 物包括同時或實質上同時標示多個預先成形件、且隨後使 其經受-或多個諸如吹氣模製等作#以形成目標產物的製 159650.doc •27· 201236849 程。因此，本文所述製程可在高體積及/或高速商業製造 製程中執行。 系統 本發明標的物亦提供與形成經標示預先成形件及標示容 器相關之各種系統。用於形成經標示預先成形件之系統通 常包含用於標示之設施及用於施加至預先成形件之一或多 種標記材料。該等系統亦可包含印刷設施或用於將油墨或 著色劑施加至標記之其他構件。用於形成經標示容器之系 統通常包含用於使預先成形件膨脹之設施。如本文所述， 該等設施較佳呈吹氣模製設備形式，其通常用於吹氣模製 預先成形件或型坯。用於形成經標示容器之系統進一步包 含如本文所述經標示預先成形件及/或用於形成經標示預 先成形件之所提及系統。 實例 以下實例闡釋利用拉伸套管裝飾容器。 在此貫例中，產生聚乙烯膜，印刷，形成套管，將其施 加至PET預先成形件且隨後利用標準拉伸吹氣瓶製程處理 成16 〇Z Boston圓底瓶。結果係為容器提供顏色及透明度 之預先裝飾之PET瓶。Addison, IL's Toyo Ink America, LLC is available as LIOVALUE or AQUALIONA or as IMAK from Amherst, NY as FK002e. Methods In general, the method of the subject matter of the present invention comprises providing a marking or marking assembly, k for the preforming member to apply a marking to the preform, and forming a final or fully formed marked article from the preform. The details and preferred aspects associated with providing the indicia and preforms, providing indicia to the preforms, and forming the final articles therefrom are provided herein. The preform can be marked with a number of different techniques. Marking application techniques can be used, such as the use of a pressure sensitive adhesive between the preform and the indicia. Alternatively, the preform can be marked by in-mold marking techniques. For example, one of the tensile properties or a plurality of indicia can be disposed along the mold wall to form a preform in the mold wall. When the preform is molded, for example, by injection molding, one or more indicia are tightly secured to the periphery of the preform. After forming the 泾 mark preform, the marked pre-force is then subjected to one or more operations to form the desired article with the mark as needed. < Preferably, the blow molded molded preform is formed to form the marked article (In this technique, the marked preform is heated to a temperature greater than the glass transition temperature of both pre-formed card marks. The crucible has been heated sufficiently (4) 159650.doc • 21· 201236849 After the preform is formed, 'then stretched as needed The preform is marked, expanded, and/or blown to form the target article. In doing so, the indicia also undergoes augmentation to cause the indicia to stretch, deform, and change shape with the preform. Most preferably, the glass transition temperature of the mark is less than or equal to the glass transition temperature of the preform. A preferred and significant aspect of the subject method of the present invention is that after marking the preform, the mark is simultaneously with the preform. Experiencing expansion. Thus, when the preform is inflated or otherwise undergoes expansion to form the desired target article, it is associated with the preform. The indentation also undergoes expansion. Optimally, the degree of expansion of the preform and the indicia is the same or substantially the same. Tube Embodiments and Applications In yet another aspect, the subject matter of the present invention provides one or more reagents or membranes or a relatively thin layer 'which is disposed around the periphery of the pre-formed part with the crest being expanded in the preform, the fully formed article containing the outer layer of one or more rolls of the agent' Surroundings. Mori or eve reagents can be colorants, toners, pigments, carbons: antioxidants, stabilizers, flame retardants, oxygen scavengers, barrier additives, uv inhibitors, and combinations thereof. The periphery of the outer periphery can be easily obtained in this manner. The ruthenium or polymer layer of the reagent and/or other additives can be formed by known extrusion techniques or other methods. J: The film containing the reagent is used in any manner ( It is generally referred to herein as attaching to a preform by means of a second embodiment. In some preferred aspects, the adhesive-containing film can be attached to the pre-formed part. Application towel, can be better avoided No adhesives are used. It does not contain the point 159650.doc •22· 201236849 The construction of the agent can save costs. Jujube 2a For example, the mark in the form of tube can be properly positioned (4) 1 tube around the first wire can have The closure tube of the seam is in a chemical or mechanical form, such as fused, welded, etc. The 'stretch tube can be formed from the appropriate marking material and positioned in the outer perimeter of the preform. In some embodiments Preferably, the tubes and/or indicia are formed from the same polymeric material as the (iv) shaped part. This move will facilitate the recycling of the labeled items from the thin preforms that are not preformed. In addition, biodegradable additives are expected to be used. Or a portion of the water soluble polymer may be more readily labeled from the remaining container during recycling as used in the markings herein. Generally, for applications using - or multiple functional films, preferably prior to any marking ( That is, applying the film (under 1), & h #, &, λ I隹/, below), however, the target includes application over the marked preforms - or the implementation of a plurality of functional films exampleIt is also envisaged that one or more markings 0 may be placed between two or more functional membranes. In some H-skins, it is preferred to have a stretched tube or "stretching sleeve" around the periphery of the first forming member. tube". The stretching (four) can be pre-formed by one or more effective amounts of one or more adhesives. In other embodiments, the stretch sleeve is more or otherwise joined to the preform by laser welding. Covers other types of welding. In still other embodiments, the stretch sleeve can be properly positioned relative to the preform without the use of an adhesive. Contact and/or frictional engagement between the stretch sleeve and the preform may be sufficient to maintain the desired position or orientation of the draw sleeve. Other embodiments that do not use an adhesive are contemplated, however, the stretch sleeve is retained in a suitable orientation and/or position. However, 159650.doc • 23- 201236849 For many embodiments, an adhesive is preferably employed to at least initially secure the stretch sleeve to the preform. As mentioned herein, a wide range of adhesives can be used. In certain embodiments, the adhesive is an activatable adhesive and in particular a heat activated adhesive, an infrared (IR) activated adhesive, an ultraviolet (uv) activated adhesive, or the like. 1 is a flow diagram of a process 1 in accordance with a preferred embodiment of the subject matter of the present invention. In this preferred process 1, a preform is provided, generally designated 1 inch. The preforms can be provided from stock or can be formed from techniques known in the art. The preforms are preferably as described herein. A marker or marker assembly is also provided in assignment 20. Likewise, the indicia can be provided from stock or formed or otherwise shaped as desired. Preferably, the markings are as described herein, and operations 10 and 20 can be performed in any manner, and in some cases, can be performed simultaneously. As previously described herein, it is contemplated that for most applications, one or more designs, words, logos, logos, and/or colors will be applied to the indicia. This job is represented as job 3 〇. Various designs and/or words can be applied to the indicia by any of a variety of means, such as by printing techniques including, for example, gravure, offset, flexographic, letterpress, screen, and digital printing. The car is well-placed and printed with digital printing technology. Typically, electronically controlled printers deposit one or more suitable ink compositions onto the marking surface. It is preferred to use an electronic controller with a data storage facility to operate the printer to form a desired pattern, text or logo on the indicia. Forming a desired pattern on the mark or the like can be performed at any point of the process order. However, it is preferred to perform printing in the same processing line that is to be applied to the preform beforehand and which is preferably best applied to the preform. Digital printing 159650.doc -24- 201236849 The brushing facility is ideal for continuous marking operations and can be easily reconfigured when the production line changes from one container or product to another. In operation 40, a decorative indicia is applied to the preform to form a marked preform. This job can be implemented in a number of different ways. Preferably, the adhesive is used to adhere the indicia to the preform. The adhesive is preferably as described herein. The adhesive may be applied or otherwise present along the outer surface of one or both of the preform and the indicia. Adhesives are also not expected to be used. On the contrary, depending on the materials constituting the preform and the mark and the temperature of the respective surfaces, the adhesive can be sufficiently adhered to the preform. Although generally less preferred, it is also expected to use in-mold marking techniques. When the preform is suitably labeled, the preformed preform is expanded in operation 50 to form the target product or target. As explained herein, expansion is preferably performed by blow molding. At the same time, operation 50 typically includes one or more heating operations to cause the preform and the marking applied thereto to be sufficiently flexible for expansion and/or stretching. Heating may be performed before and/or during expansion of the marked preform. 2 illustrates a process 丨 according to another preferred embodiment of the subject matter of the present invention. In the process 100, a preform is typically provided, indicated as work 11". This may correspond to the previously described job 1 in Process 1 of Figure 1. Provide a marker or marker assembly in job 12〇. Job 120 corresponds to job 20 previously described in the figure. Jobs 110 and 120 can be implemented in any manner and in some cases can be implemented simultaneously. In operation 130, one or more inks as described herein are deposited on the indicia. The ink preferably exhibits characteristics as described herein which render it 159650.doc -25 - 201236849 for stretching or swell application. Preferably, the printing ink or other formulation is printed on the mark using digital printing techniques. At work 140, an effective amount of adhesive is applied to the indicia, the preform, or both and the indicia is properly positioned and applied to the preform to form the indicia 4, the adhesive (four) adhesive. . The marked preform is then heated in job 150. The heating may be in any temperature range from, for example, ambient temperature to an intermediate temperature less than the temperature at which the preform is expanded, or from + @temperature to the expansion temperature. The heated preformed article is expanded in operation 160. Preferably, the expansion is carried out by a blow molding technique. In addition, the expansion may only favor the formation of intermediate products. The final product was formed in operation I7G. Typically, the finished product can be subjected to - or a variety of final operations. Work m may also include advance-step expansion of the intermediate product. The final work can, for example, include applying one or more overcoats, topcoats, or protective layers on the outer surface of the fully formed article. Mechanical or chemical work can be applied to the object. 3 illustrates a further preferred embodiment of the subject matter in accordance with the present invention. The Tractor Process 2GG generally corresponds to the previously described processes i and (10) and includes a shape or plurality of functional films and/or applies to the preforms. Specifically, referring to Fig. 3, a preform and a mark (or mark assembly) are provided in the work addition and fineness. These operations are performed as previously described (4), 汕, and operations 11〇, 120' of Figure 2 and may be performed in any order. Optional job 230, "applied to the preform" - or multiple functional films, is provided after the job 21G is provided in the operation 21G. Functional film 159650.doc -26- 201236849 is as described herein and can be applied in almost any manner as previously described herein. In job 240, one or more designs, words, logos, or the like are formed on the indicia. This job can be implemented as previously described for job 30 in Figure 1 or job 130 in Figure 2. The formation of such designs, words, logos or the like may also be set forth as referred to herein. Applying a decorative (e.g., printed) mark to the preform in job 250. Applying a mark to the preform creates a marked preform. The same can be implemented as previously described in FIG. 1 of FIG. 1, operation 140 of FIG. 2, and/or as generally described herein. The marked preforms are then heated in operation 260 as appropriate. The optional heating can be performed as previously described in connection with operation 150 of Figure 2 or as generally described herein. The expansion of the marked preform is performed in operation 270. This can be accomplished as described in connection with operation 50 of Figure 1, operation 160 of Figure 2, and/or as generally described herein. The product may then be subjected to one or more final operations, such as operation 280 in Figure 3, for example as previously described herein. The subject matter of the present invention and its various embodiments have been described primarily in the context of labeling a single preform and subsequently expanding the preform to form the target or article, but it should be understood that the subject matter of the present invention includes indicating a plurality of preforms and It is then expanded to form a plurality of targets. That is, the subject matter includes the simultaneous or substantially simultaneous labeling of a plurality of preforms and subsequent subjecting it to - or a plurality of processes such as blow molding to form the target product 159650.doc • 27· 201236849. Thus, the processes described herein can be performed in high volume and/or high speed commercial manufacturing processes. System The subject matter of the present invention also provides various systems associated with forming the preformed preformed and labeled containers. The system for forming the marked preforms typically includes a facility for marking and one or more marking materials for application to the preform. The systems may also include printing facilities or other means for applying ink or colorant to the indicia. The system used to form the labeled container typically includes a means for expanding the preform. As described herein, the devices are preferably in the form of a blow molding apparatus that is typically used for blow molding a preform or parison. The system for forming the labeled container further comprises the indicated preforms as described herein and/or the mentioned system for forming the labeled preforms. EXAMPLES The following examples illustrate the use of a stretch sleeve to decorate a container. In this example, a polyethylene film was produced, printed, formed into a sleeve, applied to a PET preform and then processed into a 16 〇Z Boston round bottom bottle using a standard stretch blow bottle process. The result is a pre-decorated PET bottle that provides color and transparency to the container.
具體而言’膜係自線性低密度聚乙烯樹脂D〇wLEX 2247G(密度為〇·9ΐ7 g/cc，於19〇。(：下熔體流動指數為2.3 g/ΙΟ分鐘）製得’該樹脂係針對其能夠在9〇<>c之標準PET瓶 吹氣模製溫度下拉伸來選擇。利用單層澆鑄膜製程以最小 定向產生厚度為4密耳（mil)之膜。除LLDpE樹脂外，亦向 159650.doc •28· 201236849 調配物中添加4%標準防結塊濃縮添加劑。在室溫下測試 時，膜具有表4十所提及之以下性質。 表4-膜性質 MD CD 單位 卡尺 4.0 4.0 密耳 抗拉強廑 5,200 4,300 psi 拉伸伸長率 980 1,700 % 2%正割模數 20,000 22,000 psi 另外，於90°C下在機器及橫向方向上成功地將上述膜拉 伸至其初始長度之五倍，從而確認膜在pET瓶吹氣模製條 件下拉伸之能力。 在吹氣模製試驗之前’將該膜電暈處理至約45達因 (dyne)且隨後用可熱成形之不透明白色uv絲網印刷油墨印 刷。油墨係Polymeric Imagin公司之產品且使用其等級 「Thermoform TF-3 11 Opaque White」UV Screen 〇 利用平板式絲網裝置將油墨以5微米厚度施加至膜且在 UV燈系統下固化。作為對適宜性之進一步檢查，亦於 9〇°C下在任一方向上成功地將印刷膜拉伸至其初始長度之 五倍。 根據欲測試之預先成形件的尺寸自印刷測試膜切割套管 且利用熱密封器使膜本身結合而形成側接縫。在吹氣模製 之前對預先成形件施加套管。將預先套管之預先成形件放 置於作業瓶吹氣模製製程中’藉此經由IR燈將其預加熱至 約90°C至1〇〇。(： ’轉移至瓶模具中且隨後拉伸吹氣成觀並 159650.doc -29· 201236849 冷卻。預先裝飾之套管提供PET瓶之完全覆蓋且為容器提 供顏色及透明度。 根據此技術之未來應用及發展將毫無疑問地明瞭許多其 他益處。 本文所提及之所有專利、公開申請案及文章之全文皆以 引用方式併入本文中。 應瞭解，本文所述一個實施例之任一或多個特徵或組件 可與另一實施例之一或多個其他特徵或組件組合。因此， 本發明標的物包括本文所述實施例之組件或特徵之任一及 所有組合" 如上文所述，本發明標的物解決與先前已知方法及產物 相關之許多問題。然而，應瞭解，彼等熟習此項技術者可 對為解釋本發明標的物之性f本文所闡述及闡釋的詳細内 容、材料及作業及組件佈置做出各種改變而不背離本發明 私的物如隨附申請專利範圍中所表述之原理及範圍。 【圖式簡單說明】 圖1係根據本發明標的物之較佳實施例方法的流程圖。 圖2係根據本發明標的物之另一較佳實施例方法的流程 圖。 圖3係根據本發明標的物之又—較佳實施例方法的流程 圖。 159650.doc 30-Specifically, the film was obtained from a linear low-density polyethylene resin D〇wLEX 2247G (density: 〇·9ΐ7 g/cc at 19〇. (: lower melt flow index: 2.3 g/ΙΟ minute). It is selected for its ability to be stretched at a standard PET bottle blow molding temperature of 9 Å. The single layer cast film process produces a film having a thickness of 4 mils with minimal orientation. In addition to LLDpE In addition to the resin, 4% standard anti-caking concentrate additive was also added to the formulation of 159650.doc •28· 201236849. When tested at room temperature, the film has the following properties mentioned in Table 40. Table 4 - Film Properties MD CD unit caliper 4.0 4.0 mil tensile strength 廑 5,200 4,300 psi tensile elongation 980 1,700 % 2% secant modulus 20,000 22,000 psi In addition, the film was stretched successfully at 90 ° C in the machine and transverse directions Up to five times its original length to confirm the ability of the film to stretch under pET bottle blow molding conditions. 'The film was corona treated to about 45 dyne and subsequently used before the blow molding test. Thermoformable opaque white uv screen printing ink printing. Ink is Polymeric Imag In the company's products and using its grade "Thermoform TF-3 11 Opaque White" UV Screen 〇 using a flat screen device to apply ink to the film at a thickness of 5 microns and curing under the UV lamp system. Further inspection of suitability The film is also successfully stretched to any of its original length in any direction at 9 ° C. The sleeve is cut from the test film according to the size of the preform to be tested and the film itself is made using a heat sealer. Combining to form a side seam. A sleeve is applied to the preform prior to blow molding. The pre-formed preform is placed in the operating bottle blow molding process 'by preheating it via an IR lamp to Approximately 90 ° C to 1 〇〇. (: 'Transfer to the bottle mold and then stretch blow air into the view and 159650.doc -29· 201236849 cooling. Pre-decorated casing provides complete coverage of the PET bottle and provides the container Color and Transparency. There are no doubts that many other benefits will be apparent from the future application and development of this technology. All patents, published applications and articles referred to herein are hereby incorporated by reference. It should be understood that any one or more of the features or components of one embodiment described herein may be combined with one or more other features or components of another embodiment. Accordingly, the subject matter of the present invention includes the embodiments described herein. Any and all combinations of components or features " As described above, the subject matter of the present invention addresses many of the problems associated with previously known methods and products. However, it should be understood that those skilled in the art can interpret this The present invention is to be construed as being limited to the details and details of the details of the invention, and the scope of the invention. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a flow diagram of a method in accordance with a preferred embodiment of the subject matter of the present invention. Figure 2 is a flow diagram of a method in accordance with another preferred embodiment of the subject matter of the present invention. Figure 3 is a flow diagram of a further preferred embodiment of the subject matter in accordance with the present invention. 159650.doc 30-