TWI630087B - 用以製造多層吹鑄中空物件之方法 - Google Patents

用以製造多層吹鑄中空物件之方法 Download PDF

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TWI630087B
TWI630087B TW100112971A TW100112971A TWI630087B TW I630087 B TWI630087 B TW I630087B TW 100112971 A TW100112971 A TW 100112971A TW 100112971 A TW100112971 A TW 100112971A TW I630087 B TWI630087 B TW I630087B
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blow
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TW201210792A (en
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馬里吉歐 托其歐
克勞迪歐 米諾帝
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科萊恩色母粒(義大利)股份有限公司
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    • B65D1/0207Bottles or similar containers with necks or like restricted apertures, designed for pouring contents characterised by material, e.g. composition, physical features
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    • B29K2023/00Use of polyalkenes or derivatives thereof as moulding material
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    • B29K2023/04Polymers of ethylene
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    • B29K2023/10Polymers of propylene
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
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Abstract

本發明關於吹鑄成形多層中空物件及用於該等由熱塑性聚合物製成之多層中空物件之製造的共擠出吹鑄成形法,且該中空物件之特徵為特定視覺效應。更特別的是,本發明關於多層中空物件及用於該等多層中空物件之製造的共擠出吹鑄成形法,其中至少一層為帶有均勻厚度之連續層及至少一層為帶有變化厚度之不連續或不均勻連續層,其造成特定表面圖案及/或視覺色彩效應。

Description

用以製造多層吹鑄中空物件之方法
本發明關於吹鑄成形多層中空物件及用於該等由熱塑性聚合物製成之多層中空物件之製造的共擠出吹鑄成形法,且該中空物件之特徵為特定視覺效應。更特別的是,本發明關於多層中空物件及用於該等多層中空物件之製造的共擠出吹鑄成形法,其中至少一層為帶有均勻厚度之連續層及至少一層為帶有變化厚度之不連續或不均勻連續層,其造成特定表面圖案及/或視覺色彩效應。
為了達成本發明的目的,吹鑄成形中空物件較佳為容器,例如瓶子。
熱塑性中空物件之吹鑄成形習慣上係藉由擠出熱塑性聚合性型坯之吹鑄成形或藉由熱塑性聚合性預塑坯之吹鑄成形進行,後者通常係由熱塑性聚合物射出成形。將該熱的熱塑性聚合性型坯或被加熱之預塑坯納入模穴,於是加壓氣體將該中空物件吹鑄成形為該模穴形狀。
熟於熱塑性聚合物工程工藝之士周知擠出技術。塑化之熱塑性聚合物(也就是說,被加熱至能流至模子之點的聚合物)通常於塑化擠出機中形成,其中將該等聚合物丸劑熔融同時藉由螺桿輸送及急轉向通過長螺缸。
商業上可購得之熱塑性樹脂係於該特定樹脂特有的溫度擠出。為了保持該樹脂之性質,擠出時之流動溫度必須在該樹脂的預定熔融流動溫度範圍內。當該樹脂被明顯加熱至高於其熔融流動溫度時該樹脂之性質可能會降低。特別是,共擠出吹鑄成形法為習用二步驟方法,其在於藉由至少兩台擠出機連續共擠出至少兩種塑化聚合物而初步形成多層管式型坯。各層通常使用獨立擠出機。這些擠出機利用各層之同心通道把該等塑化聚合物擠入模頭。該模頭中之各通道具有其自己的入口、其自己的型坯頭及其自己的出料口(outlet orifice),以致於該模頭中將多個同心聚合性管合併並自該多通道模頭之最終出料口或最終擠出模擠出具有多個同心聚合性層的最終管式型坯。
US 5 840 232於第2圖中揭示用於共擠出三層型坯之共擠出吹鑄成形的多層模頭實例。形成於內部圓形通道中之第一管式層,接著進一步於下游形成及自其出料口擠出於中間圓形通道中之第二管式層並藉以連合或對齊該第一管式層,接著又更下游,形成及自其出料口擠出於外部圓形通道中之第三管式層並藉以呈第三層連合或對齊由該第一和第二層構成之通過的管式層。最終,此管式三層型坯係透過短軸(pin)和軸襯建立之最終擠出孔口,即該模頭之最終模隙,擠出。US 5 840 232之第2圖中顯示乾氣隙的收斂型。
相對於US 5 840 232,其中該等個別同心通道之出料口依照流動方向相互之間保持一定距離依序一個接著一個放置,US 2003/0077347 A1揭示用於製造三層管式型坯之多層模頭,其中該三個通道之三個出料口在空間上彼此非常靠近,藉以將該三層中只有兩層已經連合擠出,及該三層之一層仍然保持分離之距離最小化。
在多層模頭中,供各自樹脂流動用之各通道於其開端,即於其入口,放置個別型坯頭,將來自該擠出機之聚合物流供入該型坯頭。型坯頭可藉由自實心熔融束條形成管之方式加以區分。已知的有三種型坯頭之主要設計:支臂頭(spider head)、頂心頭(mandrel head)和螺旋頭。
在該支臂頭(也叫做中心供料頭)中,芯部(所謂之篩濾網)藉由小臂(支臂)固定於定位。
在頂心頭(或魚雷頭,“心形曲線頭”,或心形頭)中,將該實心芯部(魚雷)整合於該頭的基本構造中。這些頭也被叫做側供料頭。將該實心熔融條移成兩半,二者繞著該魚雷走於相反側碰頭。同時一定量之熔融物向下流過狹窄縫隙。
螺旋頭為帶有數螺旋溝槽特徵之側供料頭。這些流動通道之深度縮小,以致於越來越多材料越過這些帶狀物流動。
將該等型坯頭建構成能確保管中流入之聚合物能被轉移成個別通道中之垂直流並形成帶有同樣圓周壁厚度分佈之呈圓形完全封閉管。為了改善此功能,文獻中已經知道這三種基本型式之多種不同變化例。於多層型坯中之各層因此為呈圓形完全封閉管或層;藉以也確保於吹鑄成形之中空物件中,各層也呈圓形完全封閉。這是中空物件吹鑄成形時之必備條件。
擠出之後,將該型坯置於展開模的兩半之間。藉由關閉該模,將該型坯夾緊於該模的兩半之間。接著藉由將氣體(即空氣)注入該夾緊型坯內部引伸該型坯,藉以當該型坯靠在該模穴之壁時使該型坯膨脹成該模內部形狀,形成該多層容器。一旦該型坯變成該容器模之形狀,該吹鑄成形步驟便完成,展開該模子並自該模移除該容器以供進一步加工。
共擠出提供將多於一種聚合物之所欲性質加入單一加工操作中之單一結構中的方法。然而,可被製造之結構類型卻有若干限制。這些限制一般係由於該等共擠出模頭內發生之流動現象引起,其可能影響產品之功能性、外觀或品質。界面不安定及欠佳之層分佈是共擠出時遇到的最嚴重問題。這些現象發生之實際成因或理由一般歸因於黏度差異造成之二材料界面處的大應力。
照慣例,為了將相鄰聚合物層之間的界面不安定性最小化及降低層厚度變化,將加工條件設定成使該等聚合物熔融物之黏度儘可能匹配。此外儘可能互相調整個別層之擠出速率以確保均勻及連續層。而且將該模頭中之各自個別通道設計成能確保同心完全密封及均勻層之形成。採取所有這些步驟是為了確保各自個別通道形成帶同樣圓周壁厚度分佈之呈圓形完全密封管。
於連續共擠出時需要調整之另一個參數是可產生該型坯之速度。型坯滴下時間(drop time)為自該頭部開始形成該型坯之時間測量完全形成該型坯所花的時間。關於由帶低熔融強度之聚合物製成的大多層輕質容器型坯,若該滴下時間太長,形成時該熔融型坯之重量將高於該熔融物強度及該型坯將在該型坯可完全形成之前掉落於地板。
現在製造中空物件不僅想要特定形狀及充分機械安定性,而且還顯示特定視覺外觀。因此本發明之目的在於提供具有顯著表面圖案及/或視覺色彩效應之吹鑄成形中空物件,尤其是容器,例如瓶子。
本發明之目的係一種用於製造含至少二層之多層吹鑄成形中空物件之方法,藉以至少一層為帶均勻厚度之連續層及至少一層為帶變動圓周及/或縱長厚度之不連續或不均勻連續層,其藉由彩色漩渦、波、條紋及/或變化之半透明性,藉由於二接連步驟中共擠出吹鑄成型產生圖案及/或視覺效應,其中於第一步驟中藉由至少兩種不同熱塑性聚合物之共擠出由多層共擠出模頭形成至少兩層管式型坯,藉以(i)形成帶有均勻厚度之連續層的聚合物通過該共擠出模頭時具有比形成不連續或不均連續層之聚合物低的動態黏度;及(ii)形成帶有均勻厚度之連續層的聚合物係於比形成不連續或不均連續層之聚合物高的擠出速率擠出,及在該第二步驟中,將該型坯吹鑄成形以形成該多層吹鑄成形中空物件。
較佳地,該至少一個不連續或不均連續層之聚合物具有不連變化之圓周及/或縱長厚度。
當通過該模頭時該等聚合物之黏度宜指該模頭中之指定溫度的動態黏度(以Pa.s為單位)。擠出速率(以kg/h為單位)指透過該模頭於指定時段中擠出之材料量,而該擠出機宜在穩定條件,例如不變之速度和溫度,下運轉。
較佳地,當通過該模頭時形成不連續或不均連續層之聚合物的動態黏度對形成帶有均勻厚度之連續層的聚合物之動態黏度的比率為9.0至4.0,較佳8.6至4.2,更佳8.0至4.4,尤其是7.7至4.6。較佳地,形成帶有均勻厚度之連續層的聚合物之擠出速率對形成不連續或不均連續層之聚合物的擠出速率之比率為30.0至2.5,較佳25.0至3.0,更佳20.0至4.0,尤其是18.9至4.2。
較佳地,該共擠出吹鑄成形方法係藉由使用擠出吹鑄成形機以形成多層中空容器,其中該吹鑄成形機包含至少兩個獨立擠出機,其中把該至少兩種熱塑性聚合物熔融及供入模頭中,其中使該等熔融之熱塑性聚合物呈獨立聚合性流合在一起及透過塑造成圓狀之狹縫擠出以形成呈同心設置之層製成的單管式型坯。
較佳地,該多層擠出模頭中之各自通道的型坯頭為頂心頭或螺旋頭,更佳地,其係頂心頭。
接著將該呈同心設置之層製成的管式型坯封圍於模子兩半之間,該型坯可於該模子內吹氣以便當該塑料接觸該模穴時變成該模子形狀,形成該多層中空物件。
為了達到本發明的目的,多層結構由至少兩個熱塑性聚合物製成之接連層,換言之外和內層,及位於該外和內層之間的任意一或多個其他及接連中間層構成。
為了達到本發明的目的,“外”層意指透過多層共擠出模頭同時共擠出之多個呈同心設置的層之最外層;該模頭中之外層可能是該擠出管式型坯中之外層,在多層中空吹鑄成形物件之案例中,該外層可能是形成中空物件之外表面的層。“內”層意指透過多層共擠出模頭同時共擠出之多個呈同心設置的層之最內層;該模頭中之內層可能是該擠出管式型坯中之內層,在多層中空吹鑄成形物件之案例中,該內層可能是形成吹鑄成形中空物件之內表面的層。“中間側”層意指介於多層結構之外和內層之間的任何層。
因此該外和內層二者之兩個主要表面只有一個表面直接黏於該結構之另一層,而任何中間層之兩個主要表面均直接黏於該多層結構之另一層。
為了達到本發明的目的,含該聚合物A之層A為該外層;含該聚合物C之層C為該內層;及任何該聚合物B之層B為多層結構之中間層。
該多層型坯和容器之任何外、中間和內層可沿著圓周方向或沿著縱長方向(擠出方向)帶均勻或不均勻壁厚度而依圓周閉合。為了達到本發明的目的,不均勻層厚度意指該層厚度可沿著圓周及/或沿著該多層型坯和容器之縱長方向變化。不均勻也可意指該層可變得不連續,也就是說該圓周及/或縱長層厚度於該型坯或該容器之一或多個部分變成0及被該型坯或該容器之其他層的任何者中斷。
在本發明之較佳具體實施例中,由輸送兩種熱塑性聚合物A和C之二獨立擠出機供料的雙層共擠出模頭形成雙層型坯。有一個具體實施例中,聚合物A具有比聚合物C低之黏度及係於比聚合物C高之速度擠出,造成具有均勻連續外層A和不均勻內層C之容器。在另一個具體實施例中,聚合物C具有比聚合物A低之黏度及係於比聚合物A高之速度擠出,造成具有均勻連續內層C和不均勻外層A之容器。
在本發明之另一個較佳具體實施例中,由輸送三種熱塑性聚合物A、B和C之三獨立擠出機供料的三層擠出模頭形成三層型坯。有一個具體實施例中,聚合物A具有比聚合物B和聚合物C低之黏度及係於比聚合物B和C高之速度擠出,造成具有均勻連續外層A和不均勻內層C和不均勻中間層B之容器。在另一個具體實施例中,聚合物B具有比聚合物A和聚合物C低之黏度及係於比聚合物A和聚合物C高之速度擠出,造成具有均勻連續中間層和不均勻內層C和不均勻外層A之容器。
上述具體實施例各個中形成之型坯接著被吹鑄成形以形成雙-或三-層聚合性中空物件,例如容器(例如瓶子)。
大體上,該等熱塑性聚合物之黏度可藉由該聚合物本身之本性,藉由該模頭中之溫度,及藉由其他成分如溶劑或聚合物添加物如被稱作“物質F”之添加予以控制。
本發明另外關於一種多層吹鑄成形中空物件,其係由熱塑性聚合物製成且其特徵為由彩色漩渦、波、條紋及/或變化半透明性所給予之圖案及/或視覺效應,藉以至少一層為帶有均勻厚度之連續層,及至少一層為帶有變化圓周及/或縱長厚度之不連續或不均勻連續層。
本發明之目的亦為一種多層吹鑄成形中空物件,其係根據文中所述之方法製造。
多層物件意指一種至少雙層之物件,較佳地,一種二、三、四或五層之物件。該不均勻層可為不連續層或連續層,二者均具有變化之圓周及/或縱長厚度。該圓周及/或縱長厚度較佳為呈不連續變化。
在本發明之一較佳具體實施例中,該物件為具有外層A和內層C之兩層容器。在其一個具體實施例中,該容器具有均勻連續外層A和不均勻內層C。在其另一個具體實施例中,該容器具有均勻連續內層C和不均勻外層A。
在本發明之另一個具體實施例中,該物件為具有外層A、中間層B和內層C之三層容器。在其一個具體實施例中,該容器具有均勻連續外層A和不均勻內層C和不均勻中間層B。在其另一個具體實施例中,該容器具有均勻連續中間層B和不均勻內層C和不均勻外層A。
在文中所述之所有具體實施例中,具有均勻圓周和縱長壁厚度之層適於作為為了該中空吹鑄成形物件之形狀和物理強度而提供之結構建造和結構支撐層。該均勻層之壁厚度較佳為0.1至5 mm,更佳0.5至3 mm。形成該圖案及/或該等視覺效應之不均勻層的壁厚度可為0至5 mm,更佳0至3 mm。由本發明之方法所形成的圖案實例為帶液滴狀正視圖、彈坑狀窟窿、凹槽、脊、條紋或漩渦之區域。視覺效應之實例可為該等圖案以及藉由變化色彩及/或變化半透明性造成之條紋、波及/或漩渦。該吹鑄成形中空物件,例如容器(例如瓶子),可具有任何可藉由吹鑄成形法製作之尺寸和形狀。
該等熱塑性聚合物A、B和C可為相同或不同及較佳為選自由聚烯烴類、聚烯烴共聚物和聚苯乙烯類組成的群組,更佳為- 聚乙烯(PE),較佳選自由高密度聚乙烯(HDPE)、中密度聚乙烯(MDPE)、低密度聚乙烯(LDPE)、線性低密度聚乙烯(LLDPE)、二茂金屬低密度聚乙烯(mLDPE)和二茂金屬線性低密度聚乙烯(mLLDPE)組成的群組,- 聚丙烯(PP),較佳選自由聚丙烯均聚物(PPH)、聚丙烯無規共聚物(PP-R)和聚丙烯嵌段共聚物(PP-嵌段-COPO)組成的群組,- 聚烯烴硬質塑料,較佳1-辛烯與乙烯之聚合物,- PE共聚物,較佳選自由乙烯-醋酸乙烯酯共聚物(EVA)、乙烯和丙烯酸甲酯(EMA)之共聚物、乙烯和醋酸丁酯(EBA)之共聚物、乙烯和丙烯酸乙酯(EEA)之共聚物和環烯烴共聚物(COC)組成的群組,- 泛用聚苯乙烯(GPPS)和高衝擊性聚乙烯(HIPS);又更佳- 高密度聚乙烯(HDPE)、低密度聚乙烯(LDPE)、線性低密度聚乙烯(LLDPE),- 聚丙烯均聚物(PPH)、聚丙烯無規共聚物(PP-R)和聚丙烯嵌段共聚物(PP-嵌段-COPO),- 乙烯-醋酸乙烯酯共聚物(EVA)、乙烯和丙烯酸甲酯(EMA)之共聚物,- 泛用聚苯乙烯(GPPS);特佳為- 高密度聚乙烯(HDPE)、中密度聚乙烯(MDPE)、線性低密度聚乙烯(LLDPE),- 聚丙烯均聚物(PPH)和聚丙烯無規共聚物(PP-R)。
任何內、外及/或中間層可能含有一或多種著色劑如顏料或染料。熟於此藝之士周知將著色劑併入該層聚合物之方法。
較佳地,至少一層包含著色劑P。為了達成本發明之目的,著色劑P為顏料或染料,其給予色彩效應如顏色、亮度、透明度、半透明或不透明。為了達成本發明之目的,將半透明界定為部分不透明或完全透明和完全不透明之間的狀態。
該著色劑P可由多於一種顏料及/或染料構成,較佳地,該著色劑P由一、二、三、四或五種顏料及/或染料構成。若多於一層含有著色劑P,該等個別層中之著色劑P可為相同或不同。該著色劑P較佳為選自由天然著色劑組成的群組,較佳衍生自植物或動物、合成著色劑,較佳合成著色劑為合成之有機和無機的染料和顏料,- 較佳之合成有機顏料係選自由偶氮顏料、雙偶氮顏料、已溶偶氮顏料(laked azo pigment)、已溶雙偶氮顏料、多環性顏料組成的群組,特佳多環性顏料為酞花青、二酮基吡咯並吡咯、喹吖酮、苝、二噁嗪、蒽醌、硫靛或喹啉黃;- 較佳之合成無機顏料係選自由碳黑、金屬氧化物、混合氧化物、矽酸鹽類、金屬硫酸鹽類、鉻酸鹽類、金屬粉末、珍珠光顏料、發光顏料組成的群組,更佳碳黑、氧化鈦、鎘顏料、鉛顏料、氧化鐵、鈦酸鎳、硫酸鋁、硫酸鋇、鈷為底質之顏料、雲母為底質之珍珠光顏料和氧化鉻。
本發明之一較佳具體實施例為一種雙層吹鑄成形中空物件,其具有由透明或半透明聚合物製成之均勻連續外層A,並具有不均勻內層C,該二層無一包含著色劑P。
本發明之另一個較佳具體實施例為一種雙層吹鑄成形中空物件,其具有由透明或半透明聚合物製成之均勻連續外層A,並具有不均勻內層C,且該內層包含著色劑P。
本發明之另一個較佳具體實施例為一種雙層吹鑄成形中空物件,其具有由透明或半透明聚合物製成之均勻連續外層A,並具有不均勻內層C,且該內層和該外層各自包含著色劑P,該著色劑P可為相同或不同。
本發明之另一個較佳具體實施例為一種三層吹鑄成形中空物件,其具有由透明或半透明聚合物製成之均勻連續外層A,並具有不均勻中間層B和不均勻內層C,且只有該中間層和內層各自包含著色劑P,該著色劑P可為相同或不同。該外、中間和內層之聚合物可為相同或不同,較佳該等聚合物為不同。
本發明之另一個較佳具體實施例為一種三層吹鑄成形中空物件,其具有由透明或半透明聚合物製成之均勻連續中間層B,並具有不均勻外層A和不均勻內層C,且只有該外層和內層各自包含著色劑P,該著色劑P可為相同或不同。該外、中間和內層之聚合物可為相同或不同,較佳該等聚合物為不同。
該吹鑄成形多層中空物件之任何層任意含有一或多種其他物質F,該物質F係選自下列組成的群組- 填料,較佳氧化矽、沸石、矽酸鹽類,特佳矽酸鋁、矽酸鈉、矽酸鈣;白堊或滑石;金屬水合物;該等填料可為奈米化填料;- 助劑,較佳酸捕集劑、加工助劑、偶合劑、潤滑劑、硬酸鹽類、發泡劑、多羥醇類、成核劑、過氧化物或抗氧化劑(例如硬脂酸鹽)或氧化物(如氧化鎂);- 抗氧化劑,較佳一級或二級抗氧化劑;- 防靜電劑,較佳硬酯酸甘油酯類、單硬脂酸甘油酯類、烷基胺類、脂肪酸混合物、胺類、乙氧基化胺類、烷基磺酸酯類、甘油酯類或其混合物(摻混物);UV吸收劑、滑劑、防霧劑、防凝結劑及/或懸浮安定劑、火焰延遲劑、生物殺菌劑、防滑和防結塊劑、起泡劑、成核劑、蠟類;及其混合物。
在含著色劑P及/或物質F之上述所有具體實施例中,宜在開始本發明之共擠出吹鑄成形法之前將著色劑P及/或物質F呈母料形態引進分別層之聚合物中。該母料引進該聚合物可藉由任何慣用之混合方法如捏合或擠出進行。
母料(MB)係含一或多種聚合性載劑和一或多種其他物質之組成物,這些其他物質為一或多種添加物及/或一或多種著色劑如顏料或染料,其中這些其他物質係以比於最終用途或最終物件中高之濃度存於該母料中,及其中該載劑或該等載劑不一定必須為該最終用途或最終物件之有機聚合物。母料中之添加物的較佳濃度較佳介於0.5至90重量%,更佳1至80重量%,在各案例中該重量%以該母料之總重量為基準。母料中之著色劑的較佳濃度較佳介於0.5至80重量%,更佳1至60重量%,在各案例中該重量%以該母料之總重量為基準。
令人驚訝的是,與一般嚴謹觀測到之程序參數如同等擠出速率及同等或類似黏度之偏差,能製造帶有該多層結構至少一層中之彩色漩渦及條紋所給予的迷人視覺效應及/或圖案之吹鑄成形中空物件。
測試方法:除非另行指明,否則該等產物性質係藉由下列方法測定:密度或比重(g/cm3)之值係根據製造廠商之規範並依據ASTM D1505、ISO1183或ASTM D792測定。
熔融流速(MFR)(於指定溫度和重量之g/10 min)之值係根據製造廠商之規範並依據ASTM D1238或ISO 1133測定。
黏度(η)之測量方法(帕斯卡.秒;Pa.s):動態黏度數據能於對應擠出機之分別溫度分佈的溫度(細節參見表2)使用毛細管流變儀及依據標準ASTM D3835測量。
該擠出速率(kg/h)之測量方法由稱取於指定時間中擠出的材料量組成,而該擠出機係於穩定條件下運轉;將稱重重複進行5次並將結果平均。
實施例:
重量%係以該混合物、組成物或物件之總重量為基準;份數為重量份;LDR意指“下降率”並表示成品中之母料稀釋度;其係以該混合物總重量為基準以母料重量%為單位表示;“ex”意指實施例;MB意指母料;L/D描述該擠出機螺桿相對長度,以該供料開口前緣至該螺桿螺紋前端之螺桿長度除以該螺桿直徑表示;該比率係將其分母換算成1表示;例如,24/1螺桿具有等於其直徑24倍之螺桿長度。
使用之物質:組分A0:低密度聚乙烯(LDPE),其具有0.919 g/cm3之密度(ISO 1183)及8.0 g/10 min之MFR(ISO 1133;於190℃/2.16 kg測量)。
組分A1或B1或C1:低密度聚乙烯(LDPE),其具有0.924 g/cm3之密度(ASTM D1505)及2.2 g/10 min之MFR(ASTM D1238;於190℃/2.16 kg測量)。
組分A2或B2或C2:高密度聚乙烯(HDPE),其具有0.960 g/cm3之密度(ISO 1183)及0.3 g/10 min之MFR(ISO 1133;於190℃/2.16 kg測量)。
組分A3或B3或C3:高光澤之高密度聚乙烯(HDPE),其具有0.957 g/cm3之密度(ISO 1183)及1.1 g/10 min之MFR(ISO 1133;於190℃/2.16 kg測量)。
組分A4或B4或C4:高密度聚乙烯(HDPE),其具有0.960 g/cm3之密度(ISO 1183)及8.0 g/10 min之MFR(ISO 1133;於190℃/2.16 kg測量)。
組分A5或B5或C5:聚丙烯均聚物(PPH),其具有0.903 g/cm3之比重(ASTM D792)及11 g/10 min之MFR(ASTM D1238;於230℃/2.16 kg測量)。
組分A6或B6或C6:聚丙烯無規共聚物(PP-R),其具有0.900 g/cm3之密度(ISO 1183)及1.8 g/10 min之MFR(ISO 1133;於230℃/2.16 kg測量)。
組分A7或B7或C7:高透明性聚丙烯無規共聚物(PP-R),其具有0.905 g/cm3之密度(ISO 1183)及8 g/10 min之MFR(ISO 1133;於230℃/2.16 kg測量)。
組分P1:C.I. Pigment Blue 15:3(C.I. No. 74160)。
組分P2:C.I. Pigment Brown 24(C.I. No. 77310)。
組分P3:C.I. Pigment Red 101(C.I. No. 77491)。
母料MB1至MB3
藉由於160至220℃之雙螺桿擠出機將該等組分一起均質化並獲得有色濃縮物MB1至MB3;表1列出細節。
實例1至實例22
藉由多層吹鑄成形機Magic MP IB500/ND製備雙層及三層瓶子,該多層吹鑄成形機係配備各自具有24之相對螺桿長度L/D的三個獨立擠出機1、2和3及帶有進料塊且帶有43 mm之最大環直徑的共擠出多層模頭。擠出機1搭配形成外層之聚合物A運轉,擠出機2搭配形成任意中間層之聚合物B運轉及擠出機3搭配形成該多層中空物件的內層之聚合物C運轉,且聚合物A、B或C任意與有色濃縮物MB1至MB3混合以給予該多層中空物件之一或多於一層顏色。表2列出該等擠出機之溫度分佈細節;表3列出該模頭之溫度分佈細節。
將聚合物A、B和C均質化並最終依表4記載之比率與有色濃縮物MB1至MB3混合。表4也列出各層之動態黏度和擠出速率的測值及特定實施例之相對比率。依據挑選出來之程序參數,獲得於該多層結構之至少一層中的多種不同視覺效應及/或圖案。根據下列標度估計此等視覺效應及/或圖案。
(+++) 非常顯著
(++) 顯著
(+) 淺
根據此等進行試驗為,顯而易見該等漩渦和條紋效應係於本發明範圍內之各式各樣條件下產生。
在表4中,實例1至實例22,該外層A為均勻連續層及該內層C為不連續或不均連續層。

Claims (12)

  1. 一種多層吹鑄成形中空物件,其係由熱塑性聚合物製成且其特徵為由彩色漩渦、波、條紋及/或變化半透明性所給予之圖案及/或視覺效應,其中至少一層為帶有均勻厚度之連續層,及至少一層為帶有變化圓周及/或縱長厚度之不連續或不均勻連續層,其中該物件為兩層容器,該兩層容器具有均勻連續外層A及不連續或不均勻連續內層C:或其中該物件為三層容器,該三層容器具有均勻連續外層A及不連續或不均勻連續內層C及不連續或不均勻連續中間層B。
  2. 如申請專利範圍第1項之物件,其中該不均勻連續層具有不連續變化圓周及/或縱長厚度。
  3. 如申請專利範圍第1或2項之物件,其中該均勻連續層具有介於0.1與5mm之間的厚度。
  4. 如申請專利範圍第1或2項之物件,其中該等熱塑性聚合物係選自由聚烯烴、聚烯烴共聚物及聚苯乙烯類所群組成的群組。
  5. 如申請專利範圍第1或2項之物件,其中該等熱塑性聚合物係選自由高密度聚乙烯、中密度聚乙烯、線性低密度聚乙烯、聚丙烯均聚物及聚丙烯無規共聚物所群組成的群組。
  6. 如申請專利範圍第1或2項之物件,其中任何層均含有一或多種著色劑。
  7. 一種用於製造如申請專利範圍第1至6項中任一項之多層吹鑄成形中空物件之方法,其係於二接連步驟中藉由共擠出吹鑄成形達成,其中於第一步驟中藉由多層共擠出模頭而以至少兩種不同熱塑性聚合物之共擠出來形成至少兩層管式型坯,藉以(i)形成帶有均勻厚度之連續層的聚合物通過該共擠出模頭時具有比形成不連續或不均連續層之聚合物低的動態黏度;及(ii)形成帶有均勻厚度之連續層的聚合物係於比形成不連續或不均連續層之聚合物高的擠出速率擠出,及在該第二步驟中,將該型坯吹鑄成形以形成該多層聚合性中空物件。
  8. 如申請專利範圍第7項之方法,其中形成該不連續或不均勻連續層的聚合物之動態黏度對帶有均勻厚度之連續層的聚合物之動態黏度的比率,當通過該模頭時,為9.0至4.0。
  9. 如申請專利範圍第8項之方法,其中該動態黏度比率為7.7至4.6。
  10. 如申請專利範圍第7至9項中任一項之方法,其中形成帶有均勻厚度之連續層的聚合物之擠出速率對形成不連續或不均連續層的聚合物之擠出速率的比率為30.0至2.5。
  11. 如申請專利範圍第10項之方法,其中該擠出速率比率為18.9至4.2。
  12. 如申請專利範圍第7至9項中任一項之方法,其中該共擠出吹鑄成形法係藉由使用擠出吹鑄成形機以形成多層中空物件而進行,其中該吹鑄成形機包含至少兩個獨立擠出機,其中將該至少兩種熱塑性聚合物熔融並供入模頭,其中該等呈獨立聚合性流合在一起並透過似圓形之狹縫擠出以形成由配置成同心圓之層製成的單管式型坯。
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