CN1089226A - 成型具有高结晶度的侧壁和低结晶度的底部的容器的方法 - Google Patents
成型具有高结晶度的侧壁和低结晶度的底部的容器的方法 Download PDFInfo
- Publication number
- CN1089226A CN1089226A CN93116495A CN93116495A CN1089226A CN 1089226 A CN1089226 A CN 1089226A CN 93116495 A CN93116495 A CN 93116495A CN 93116495 A CN93116495 A CN 93116495A CN 1089226 A CN1089226 A CN 1089226A
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- CN
- China
- Prior art keywords
- container
- sidewall
- crystallinity
- average crystallite
- thickening
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Abstract
一种制造具有高结晶度的侧壁和低结晶度的加
厚底部的聚酯容器的方法。该容器特别适于用作可
再填充的容器,它能耐受较高的碱洗温度并表现出在
香味滞留方面有所下降,或是用作热填充容器。根据
本方法,预成型物上的侧壁形成部分首先被膨胀,加
热后收缩并使其结晶,然后再膨胀;预成型物上的底
部形成部分在热处理时被屏蔽起来,并在热处理步骤
之前或之后膨胀。
Description
本发明是由W.Collette,S.Krishnakumar和C.Lina共同拥有的待批美国专利US-07/909,988号的后续申请,上述申请的申请日为1992年7月7日,题目为“可再填充的高性能压力容器及其成型方法”。
本发明涉及对容器的新的和有用的改进,更具体地说,涉及一种成型具有高的侧壁结晶度和低的底部结晶度的容器的方法。该容器尤其适于用作可再填充的碳酸饮料容器,它能耐受较高的碱洗温度,并表现出滞留较少的产品香味的能力,或用作热填充容器。
可再填充的PET碳酸软饮料(CSD)瓶的市场自从1987年由大陆PET技术公司介绍到市场上起,已在世界范围内明显扩大。这些瓶子已在欧洲大部的中、南美洲商业化,并正在进入远东市场。
可再填充的瓶子减少了常与可处理的塑料饮料瓶相伴的废渣填埋和回收问题。另外,这种可再填充的瓶子为目前由玻璃瓶主宰着的、法律上禁止使用非重复利用的包装的市场提供了一种较为安全、重量也较轻的塑料容器。其目的是生产一种具有能承受多次的再填充所需物理特性的可再填充的瓶子,而生产这种瓶子还要经济合算。
通常,一个可再填充的塑料瓶子在反复利用至少10个周期或循环后必须能保持其功能和美学特点,而且最好能使用20次以上,这样,从经济角度考虑它是实用的。一个循环包括(1)空瓶的热碱洗和紧接着的(2)污染物的检测和产品的填充/加盖,(3)入库储存,(4)分配给批发和零售点,(5)消费者购买、使用并储存空瓶,最终又送回到装瓶工手中。这一周期在图1中进行了说明。
为了实现商业上的使用寿命,可再填充的容器必须满足几个关键的性能标准,包括:
1.高透明度(透光度)以便能够在不停机的情况下进行目检。
2.超过容器寿命的形稳性;以及
3.对因碱洗引起的张力破裂和泄露的抵抗能力。
一种商业上很成功的PET可再填充的CSD容器目前正由可口可乐公司在欧洲推广(此后称之为“现有容器”)。这种容器是由单层的具有3-5%的共聚单体,如1,4-环己烷二甲醇(CHDM)或间苯二酸(IPA)的聚对苯二甲酸乙二醇酯(PET)共聚物制成的。用于拉伸吹塑模制这种瓶子的预先成型物,其侧壁厚度在5-7mm之间,或者说其厚度大约为用于制造易处理的一次性瓶子的预成型物的厚度2-2.5倍。这样就为瓶子提供了一个机械损伤和形稳性所需的较大的平均侧壁厚度(即,0.5-0.7mm),其平均拉伸比为10∶1。面板(标签以下的筒状侧壁部分)的平均结晶度约为15-20%。高共聚物含量能防止在注模过程中在预成型物中产生可见的结晶,即混浊。成型物混浊是不理想的,因为它会影响用再填充容器所需要的不停机目测检验。这种现有技术容器的各种特征在大陆PET技术公司的一系列美国专利中有记载,它们是US-4,725,464,4755404,5066528和5198248。
现有的容器被证实在高达60℃温度的碱洗条件下具有超过20次的野外装填寿命。尽管这种容器也很成功,商业上还是需要一种改进的容器,这样容器可把渺清洗温度提高到60℃以上,同时还能减少产品的香味滞留。香味滞留的发生是这样的,第一种产品(例如草根可口饮料)的香料渗入瓶壁中,当再填充第二种产品(例如,汽水)时香味又渗入到该产品中,这样就影响了第二种产品的风味。提高清洗度有助于提高清洗效率和/或减少碱洗时间,而且对于某些食品,如果汁或牛奶来说也是必要的。
因此,对于具有10次,最好是20次以上的再填充寿命的可回收瓶子来说,将碱洗温度提高到60℃以上是有利的,这样做还能减少香味的滞留。通过如下所述的本发明的方法可以实现这些和其它目的。
根据本发明,提供了一种成型具有较高结晶度的侧壁和较低结晶度的底部的容器的方法。该容器改善了其抗腐蚀性应力开裂的能力,同时还能保持其透明度(清晰度)和形稳性,因此,特别适于用作可再填充的饮料瓶。这种容器在碱洗温度超过60℃的条件下,具有至少10次再填充周期,最好是有至少20次再填充周期。这种容器与上述现有的可再填充的CSD容器相比,其香味滞留率降低了至少20%。
成型这种容器的方法,包括第一个膨胀步骤,在该步骤中,将基本上为非晶形的聚酯预成型至少部分地膨胀成一种中间制品,紧接着是热处理步骤,在该步骤中,中间制品至少被部分加热收缩并使其结晶,随后是第二个膨胀步骤,在该步骤中,收缩的中间制品被再次膨胀以制成最终的容器。
在本发明的第一方法实例中,预成型物上将形成底部的部分在第一个膨胀步骤中不被膨胀,在热处理步骤中不被加热,其结晶度基本上保持不变,在第二个膨胀步骤中被膨胀而结晶无明显变化。相反,预成型物上将形成侧壁的部分在第一个膨胀步骤中被膨胀到大体上等于或大于最终的容器侧壁的尺寸。在热处理步骤中加热结晶并收缩至小于最终的容器尺寸,在第二个膨胀步骤中再次膨胀到容器侧壁的最终尺寸。由此获得的相对较薄的侧壁,与较厚的底部相比具有较高百分比的结晶度,这样,提高了侧壁和底部的抗腐蚀性应力开裂的能力。
在第二个方法实施例中,预成型物上将形成底部的部分在第一个膨胀步骤中被膨胀,但在热处理步骤中不被加热,这样,与容器侧壁相比它能维持较低的结晶度。同样地,预成型物上将要形成侧壁的部分在第一个膨胀步骤中也被膨胀,以形成中间的、膨胀过的侧壁,其尺寸大体上等于或大于最终容器侧壁的尺寸。因此,较薄的容器侧壁与较厚的底部相比,具有较高百分比的结晶度,这样,可以提高侧壁的底部的抗腐蚀性应力开裂的能力。
预成型物将形成底部的部分通常略厚于形成侧壁的部分,因此,在热处理步骤中更能耐受加热(导致结晶)。此外,最好将热处理局限或限定在中间侧壁部分,而形成底部的部分(或底部)被屏蔽起来以免被加热。在一个优选的热处理步骤中,中间容器通过一排加热元件而被加热,同时屏蔽元件运动(或增大体积)以便当其随收缩的侧壁向上移动时保护形成底部的部分或底部。另外,将一个收缩定心杆放置在收缩的中间制品中,并且控制中间制品的内部压力,以促其均匀收缩。在另一个优选的热处理步骤中,有一个冷却机构,如一个水冷却的底部杯子与形成底部的部分(或底部)保持接触,以免其被加热。或者由一个冷却机构将冷却流体(如冷气)射向收缩的制品上将形成底部的部分(或底部),以免加热底部。此外,相对较厚的颈部和肩部也可放屏蔽起来,以免被加热。
所得到的容器具有高度定向、较薄和高度结晶的侧壁面板部分,其平均结晶度至少25%,最好为30-35%。容器的底部包括一个增厚的底部部分,它具有较低的定向和结晶度,即:其平均结晶度不超过10%。加厚的底部的壁厚通常至少为面板厚度的3倍,更常见的是3-4倍。面板上较高的结晶度使其可采用较高的清洗温度,例如65℃或75℃,但同时也要求较长的处理时间(以加热和冷却侧壁)。曾得到高达50%的很高的结晶度。所谓“平均结晶度”是指从容器上各相应部分,即面板或加厚的底部的整个面积上取的平均值。
在一个实例中,该容器是一个具有独立底部的整体式的可再填充的加压饮料容器。侧壁(特别是面板)的壁厚约为0.5-0.8mm,在第一个膨胀步骤中,预成型物上将形成侧壁的部分以10-16∶1的平面拉伸比被拉伸(即:被膨胀的侧壁与预成型侧壁的厚度减少比),在第二个膨胀步骤中,收缩的中间侧壁以7-15∶1,最好是9-11∶1的平面拉伸比被拉伸(即,最终侧壁与预成型侧壁相比的厚度减少比)。该容器有一个扁平的底部,该底部有一 个向上径向增大的弧形外壁,一个最低的凹边,和一个收缩的中央拱顶,凹边的平均百分比结晶度最好不超过10%,2-8%更好;中央顶的平均结晶度最好不超过8%,不超过2%更好。
另外,这种容器还可以有一个较薄的“带脚”的底部,包括半球形底板,和向下延伸至最低处的支脚的支腿。半球形的底板包括支腿之间的辐射肋。底部(包括肋、支腿和支脚)较薄的外部其平均结晶度最好至少为10%,15-20%更好。底部上较厚的中部(无支腿)的平均结晶度不超过8%,最好不超过2%。
在另一个实施例中,改善了在高温下抗应力裂变性能和抗尺寸改变性能使得本发明的容器特别适于用作热装容器。
下面将通过详细说明和几个特定实施例的附图对本发明的这些和其它特定做更具体的描述。
图1图示说明可再填充的容器必须经过的一个典型的周期或循环;
图2是本发明的一个1.5升的可再填充的PET碳酸饮料瓶的立体图,它有一个被部分切除的底部,示出了瓶上各处的壁厚的平均百分结晶度;
图3是本发明的一个1.5升的可再填充的PET碳酸饮料瓶的立体视图,它有一个被部分切除的带脚的底座,示出了瓶上各处的厚度和百分结晶度;
图4-7是本发明第一个方法实施例的图示说明,其中预成型物上将形成底部的部分在第一个膨胀步骤中未被膨胀,图4表示预成型物放在一个吹塑模具中,图5表示第一个膨胀步骤,图6表示由红外线加热元件进行的热处理,在形成底部的部分的周围有屏蔽元件,图7表示制成具有一个扁平底部的最终的容器的第二膨胀步骤;
图8-11是本发明第二个方法实施例的图示说明,其中,形成底部的部分在第一个膨胀步骤中被膨胀,图8表示预成型物放置在以塑模具中,图9表示第一个膨胀步骤,它包括底部的膨胀,图10表示热处理步骤,这里底部被屏蔽起来,图11表示第二个膨胀步骤,制成具有一个扁平底部的最终容器;
图12-13表示图14-11中的容器在连续的方法步骤中的图示外形,其中,图12表示图4-7(在第一个膨胀步骤中底部未被吹塑)中所示第一个方法实施例的顺序的外形,图13表示图8-11(在第一个膨胀步骤中底部被吹塑)中所示第二个方法实施例的顺序的外形;
图14-15表示按前述两个方法实施例所制造的另两种可行的带脚的容器的图示外形,其中,图14表示第一个方法实施例的顺序外形,这里,形成底部的部分在第一个膨胀步骤中未被膨胀,图15表示第二个方法实施例的顺序外形变化,这里,外层底座在第一个膨胀步骤中被部分膨胀;
图16是可用于热处理的另一种装置的放大示意图,在这里用由一对鼓风机送来的热空气对中间制品进行处理;所示容器有一个扁平的底部,是根据本发明的第一个方法实施例制成的;
图17是可用于热处理的另一种装置的放大示意图,除了热内机外,它还包括用于防止底部加热的水冷却底座,所示容器具有一个扁平的底部,是按照本发明的第二个方法实施例制造的。
图18是可用于热处理的另一种装置的放大示意图,除了对着侧壁的红外线加热元件和用于底部的移动式屏板外,它还包括一个把冷空气射向底部的管,以防止底部被加热;所示容器具有一个带脚的底部,是根据本发明的第二个方法实施例制成的;
图19是可用于热处理的另一种装置的放大示意图,其中,设置了各种长度的高频(RF)电极,用于有选择的加热根据本发明第一个方法实施例制成的、具有一个扁平底部的容器的侧壁。
参见附图,特别是图1,一个商用可再填充的容器必须能够承受多次的再填充循环,同时还能保持其美学和功能特性。模拟这样一种循环的试验方法如下所述。如在说明书和权利要求书中所用到的,耐受所设定的再填充周期数而无开裂缺陷和/或最大体积变化的能力,是按照下述试验方法确定的。
每个容器都要用商用碱性清洗液清洗,这种溶液是由重量百分比为3.5%氢氧化钠和自来水制备而成的。清洗液保持在设定的清洗温度,根据本发明为60℃或60℃以上。把瓶子不盖盖浸入清洗液15分钟,以模拟商用瓶子清洗系统的时间/温度条件。从清洗液中取出后用自来水漂洗,然后在4.0±0.2个大气压下填充酸水溶液(模拟碳酸饮料容器里的压力),加盖并放入38℃、相对湿度50%的热流炉中24小时。选择这种较高的炉温是为了模拟较低温度下的较长的商业储存期。容器从炉中取出后被倒空,并再次进行同样的再填充周期,直到损坏。
损坏是指瓶壁上产生的能导致泄漏和压力损失的任何裂口。体积的改变是通过比较每个再填充周期前后在室温下容器所盛液体的体积来确定的。
下面将要说明的图2所示的容器,在清洗温度高于60℃的条件下能经受20次以上的再填充循环而破损,而且在20个循环以后体积变化不超过1.5%。通过气相色谱质仪测量证实,这种容器对产品香味的滞留率也减少了20%(与现有的CSD瓶子相比)。
图3表示一个1.5升的PET可再填充的碳酸饮料瓶,它有一个较厚的扁平底部,是根据本发明制造的。瓶10是一个由整体软塑模制的、双轴取向的中空体,有一个开口的上端12,在颈部末端14上有外螺纹用于接纳瓶盖(未示出),以及下端封闭的底部16,在颈部末端与底部之间是垂直设置的侧壁18,它包括一个上锥形肩20,和一个大体上为筒状的面板部分22(由瓶子的竖轴或中心线CL界定)。扁平的底部16有一个中心向外凹陷的拱顶和一个中心突出部分24;一个向内凹边部分28,包括支撑瓶子的支撑环,以及直径渐增的弓形外底部分30,它平滑过渡到侧壁18。该凹边基本上是一个围绕着支撑环的环弓形区,它被加厚以抵抗应力开裂。拱顶和凹边构成加厚的底部,其厚度大约是侧板22厚度的3-4倍,且平均结晶度不超过10%。而且,突起部24的平均结晶度最好不超过2%,凹边的平均结晶度不超过8%。与较薄的侧壁板22相比,加厚的底部在热处理步骤中能抗加热(导致结晶)。凹边上部为较薄的外底部分,其厚度大约为加厚底部的50-70%,结晶度随着接近与侧壁的结合处而增加。较薄的外底壁改善了它的抗冲击性。
图2所示的1.5升的容器大约为13.2英寸(335mm)高,直径为3.6英寸(92mm)(最大处)。在图2中列出了瓶上从颈端到底部处的壁厚(以mm为单位),并给出了相应的平均百分结晶度。得处的结晶度与瓶壁各处的拉伸(张力纤的结晶)和加热(热致结晶)程度相关。为了保证其透明度,任何热致结晶都应当是低温热定形引起的,例如,对PET来说,与模温为110-140℃的模具接触。百分结晶度是根据ASTM1505计算的,公式如下:
%结晶度=[(ds-da)/(dc-da)]×100
其中,ds=样品密度(g/cm3),da=百分结晶度为零的非晶薄膜的密度(DET为1.333g/cm3),dc=由晶胞参数(PET为1.455g/cm3)计算出的晶体密度。
用于制造图2中容器的预成型物,其侧壁厚度约为0.24英寸(6.1mm),侧壁面板以约10∶1的平均平面拉伸比拉伸。平面拉伸比是预成型物上将形成面板部分的平均厚度与瓶子上面板平均厚度之比。对于体积为0.5-2.0升的聚酯再填充饮料瓶来说,优选的拉伸比为7-14∶1,拉伸比为8-13∶1更好。周向拉伸以3-3.6∶1为宜,轴向拉伸以2-3∶1为宜。这样,制成的容器具有理想的抗机械损伤性能,预成型的侧壁具有理想的目视透明度。侧壁厚度和拉伸比的选择,取决于特定瓶子的尺寸,内部压力(例如,啤酒2个大气压,软饮料4个大气压)以及特定材料的加工特性(例如由特性粘度决定)。
如图2所示,被吹塑主最大程度的面板部分22具有25-35%的最高平均百分结晶度。锥形肩部20的膨胀度比底部16高,其平均百分结晶度为20-30%。相反,较厚的、吹塑较少的底部16在中央突起部24的结晶度为0-2%,凹边28和突起与凹边之间的拱顶部分26的结晶度2-8%。外底30的结晶度在从凹边处的2-8%至外底与筒状面板22处的20-30%的范围内变化。颈端14未被膨胀,基本上仍保持结晶度为0-2%的非结晶形态。
不同的结晶度可以通过膨胀(张力引起)和热定形(热致)的联合作用而获得。通常,张力所致的结晶度在特定层次的厚度上趋于一致,而热致的结晶度在壁上呈梯度。本发明中,仅因侧壁内、外表面的高结晶度就是于改善其抗应力开裂性能。不过,通常在侧壁上有一个基本上恒定的平均结晶度。
根据上文限定的百分结晶度,吹塑的容器应当基本上是透明的。另一种透明度的量度是穿过壁板的透射光线的百分混浊度(HT),由下式算出:
HT=[Yd÷(Yd+Ys)]×100
其中,Yd是样品发出的散射光,Ys是样品发出的反射光。散射光和反射光的透射值是根据ASTM法D1003测定的,采用任何标准的色差仪,如由Hunterlab.Inc产生的D25D3P型。
本发明的容器应具有低于15%的百分混浊度(穿过壁板),低于10%较好,低于5%更好。
进行如下的实验,证明了图2中其面板部分平均结晶度为30-35%的1.5升的容器(容器Ⅰ)在香味滞留方面有所下降,上述具有相同大小、相同形状的现有瓶子其面板的平均结晶度为15-20%(容器Ⅱ)。
一种模拟的饮料类似物是由下列四种材料(对饮料制品来说是常见的)在去离子水中混合而成,深度与饮料制品的相同;
(a)材料A是环己烷;
(b)材料B是一种醛;
(c)材料C是一种乙基化合物,分子量在195-205的范围内;
(d)材料D是一种分子量在130-140范围内的单纯烃链。
将上述模拟饮料物注入样品瓶并在110°F下放置6周。
然后,倒空样品瓶,并模拟商业清洗,用2%的氢氧化钠溶液在60℃温度下洗涤15分钟。再用弱乙酸溶液填充样品瓶,并在110°放置6周。值得一提的是,该清洗方法是专用于滞留试验的,而不是为了改进上述再填充周期的模拟试验方法。
在第二个六周时间的放置期结束时,将溶液倒入密封良好的玻璃瓶中并冷藏测试。测试采用一台Hewlett-Packard气相色谱仪5890A进行。样品瓶中如下所示的材料A-D的平均残余物量(mg/l):
容器I 容器II
(图2) (现有技术)
材料A 92 155
材料B 560 962
材料C 0.13 0.25
材料D 0.57 1.2
本发明的容器(容器Ⅰ)一般表现出香味滞留量为现有商用瓶的一半。根据本发明制造的结晶度更高的容器表面出在香味滞留量方面下降更多。
进行了下述实验,并证实了在较高清洗温度下上述本发明容器(容器Ⅰ)与现有容器(容器Ⅱ)相比在形稳性方面的改进。这一特殊实验是为了说明用的。并不是为了改进上述再填充周期的模拟实验方法。
一般,一种商业上可用的可再填充的PET瓶,在5年内的20次再填充周期中其体积变化不应当超过1.5%。通过把瓶子在下面设定的清洗温度下浸没在2%的氢氧化钠溶液中5个小时来模拟在普通气候下的这种商业上的5年20个循环周期的收缩潜力。在三种中的每一个清洗温度下,本发明的容器(容器Ⅰ)与现有容器(容器Ⅱ)相比都表现出明显较小的体积变化。当提高清洗温度时收缩率增加,为了适应清洗温度的升高,可采用较高的结晶度的容器,即结晶度在30-35%以上。一般,较高的结晶度会增加生产费用,包括热处理时间,所以生产的瓶子也更昂贵。
清洗温度(℃) 容器I(图2) 容器II(现有技术)
60.0 0.6% 1.1%
62.5 0.9% 1.8%
65.0 1.7% 4.2%
根据本发明制造的另一种可再填充的1.5升装碳酸饮料示于图3,它具有较薄的、带脚的底部。瓶110是整体吹塑模制而成的,双轴取向的中空体,有一个可口的上端112,在颈部末端114上有用于接纳螺纹瓶盖(未示出)的外螺纹,一个封闭的下底116。在颈部末端与底部之间为基本上垂直设置的侧壁118,它包括上锥形肩部120,基本上为筒状的面板部分122(由瓶子的竖轴或中心线CL界定)。整合的底部116为一大体上呈半球形的底板129,具有向下突出的支脚125,每个支脚的最下部为支承容器的支脚128。辐射肋130在支脚125之间延伸并构成半球形底板129的一部分。半球形底板的中央拱顶部分124不包括任何支腿,它较厚,构成加厚的中央底部。较薄的外底部分131包括支腿125、支脚128的辐射肋130。支腿比半球形的底部做了更进一步的吹塑,因此,它要比辐射肋薄。支腿包括邻近拱顶的内支腿部分126和位于支脚与容器侧壁之间的外支腿部分127。
如图3所示,容器侧壁上各处的平均百分结晶度根据该处被吹塑和加热的程度而变化。面板部分122被吹塑的程度最大,它具有25-35%的最高平均结晶度。锥形肩部120其次,平均结晶度为20-30%。未被膨胀的颈部末端114基本上呈非晶态,平均结晶度为0-2%。底部116比侧壁118的吹塑程度小,在中央拱顶124处的平均结晶度为0-2%,支脚128的平均结晶度为15-18%,辐射肋130(支腿之间)的平均结晶度为10-15%,邻近与侧壁的接合部的平均结晶度20-30%。内支腿部分126的结晶度在拱顶124(0-2%)与支脚128(15-18%)之间变化。类似地,外支腿部分127的结晶度在支脚128(15-18%)与上底(20-30%)之间变化。
图2和3中具有较高侧壁面板结晶度和较低底部结晶度的容器,增强了其侧壁和底抗因碱洗引起的应力开裂性能。另外,在连续的再填充周期中填充不同的饮料时,香味滞留量也有所减少。通过以下两种生产容器的优选方法可以实现侧壁与底部的不同的结晶度。
本发明的第一个方法实施例示于图4-7中。在该实施例中,预成型物上形成底部的部分在第一个膨胀步骤未被膨胀,而直至第二个膨胀步骤形成底部的部分的尺寸都基本保持不变。尽管在说明对该方法是用于制造平底容器,不过同样可用于制造带脚的底部的容器(见图14)。
如图4所示,预成型物50由一个转动的套筒夹部件200悬挂并放置在第一个模具单元214中。套筒夹部包括一个夹持预成型物的颈端54的筒夹202和一个向预成型物内部提供流体的内孔204。套筒夹部件上还包括一个泄压阀206,用于在各个膨胀和收缩步骤中控制预成型物内的流体压力;一个移动式张力杆208用于提高预成型物的均匀膨胀和收缩。模具单元214包括颈板216用于咬合预成型物上、颈端54下部的凸缘;上模体218,它有一个用于成型中间容器侧壁的内表面219;下模体220,它有一个用于约束预成型物上形成底部部分的内表面221该部分在第1个膨胀步骤中未被膨胀)。由于下述原因,模具上各部分216、218、220保持不同的温度。预成型物50包括形成侧壁的部分58和形成底部的部分56。形成侧壁的部分包括形成上锥形肩部的部分60和形成筒状面板的部分62。形成底部分56可以包括加厚的上部64和较薄的下部66。专利权于1991年11月19日受予KrishnaKumar等人的5,066,528号美国专利中,公开了一种优选的、制造再填充饮料的预成型物,在这里用作参考。
如图5所示,在第一个膨胀步骤中,预成型物50被拉伸吹塑(通过杆208和高压流体)成初级中间制品70,它有一个膨胀的上肩部分72,膨胀的筒状面板部分74,和未膨胀的底部形成部分76,该部分在尺寸和结晶度方面基本上与预成型物上底部形成部分56基本上相同(部分56的直径可能较小于以便于插入下模220)。预成型物在进入模具时是热的,例如200°F(颈端除外)。预成型物在模具中膨胀时被冷却,而且各部分216、218和220保持不同的温度,以控制中间制品上不同部分的结晶度。颈板216(约束颈端)保持冷(例如40-70°F),上模体218(成型侧壁)保持热(例如180-210°F)。下模体(约束底部形成部分)保持温度(例如150-180°F)。这样,颈端保持非晶态,底部保持温热和极低(如果有的话)的结晶度。
如图6所示,初级中间制品70仍保持在转动的套筒夹202上以进行热处理步骤,制品70被插入热处理单元228中,热处理单元228包括一个外套230,它有一个上隔热板232,用于保护非晶态的颈端。外套230是一个长形的腔室,中间制品70从中通过,而且由一系列的红外线(IR)加热元件234加热(箭头235)肩部72和面板部分74,由此引起侧壁收缩和结晶,当其在腔室中运动时形成次级中间制品80的收缩的肩部82和收缩的面板部分84。热处理温度在400-500°F范围内。底部76由隔热元件236与热源235隔离,当收缩的制品通过该腔室时,隔热元件236一起向上运动。次级中间制品上的底部形成部分86在尺寸和结晶度方面基本上保持与初级中间制品上的底部形成部分76一致。为实现初级中间制品70的均匀收缩,定心杆通过内部的弹簧209缩短,制品70内的内压升高(由于收缩)由泄压阀206释放,这样制品70仍为同心的,并且以受控,一致的方式收缩。
如图7所示,在第二个膨胀步骤中,收缩的中间制品80被拉伸吹塑成最后的容器10(见图2)。制品80被保持在转动的套筒夹202上并被插入第二个模具单元240,它包括颈板242,上模体244和下模体246。高压空气通过套筒夹注入到制品80,以膨胀肩部82、面板84和底部86并制成容器10上相应的各个部分20、22和16。当中间制品80在模具中膨胀时被冷却,模具上的部分242,244和246具有不同的温度以控制最后容器上不同部分的结晶度。例如,颈板242保冷(例如40-70°F),上模体244保持温热,以释放侧壁上残余的张力(例如120-150°F),下模体246保持冷部),以保证底部的结晶度较低(例如40-70°F)。膨胀的肩部20和面板部分22因此具有高于底部16的较高的结晶度,它使得容器具有更好的抗因碱洗导致的应力裂变性能。
图12表示与图4-7中各个步骤相应的一系裂容器外形。轮廓1表示图4中具有底部形成部分56的预成形物50。轮廓2表示图5中所示第一个膨胀步骤之后的初级中间制品70,具有基本上未被膨胀的底部形成部分76。轮廓3表示图6中的所示热处理步骤之后的次级中间制品80,具有基本上未变的底部形成部分86。轮廓4表示图7中所示第二个膨胀步骤之后的最终容器10,它具有膨胀的、但结晶度低而且较厚的平底16。
图14中的轮廓线与图12中的相应,不过它表示的是具有带脚的底部的容器110的成型(见图3)。图14中的数字编号指示与图12中相类似的部件,但增加了编号“100”。因而,在图14中轮廓1表示成型带脚的容器的预成型物150,它具有底部形成部分156。轮廓2表示第一个膨胀步骤之后的初级中间制品170,具有基本上未变化的底部形成部分176。轮廓3表示热处理步骤之后的次级中间制品180,也具有基本上未变化的底部形成部分186。轮廓4表示第二个膨胀步骤之后的最终容器110,它有一个带脚的底部116。带脚的容器110可以用类似于图4-7的装置制造,只需做一些相应的调整以成型与平底相反的带脚的底部。
图8-11与图4-7相似,不过它说明的是本发明的第二个方法实施例,其中,预成型物上的底部形成部分在第一个膨胀步骤中被膨胀。图8-11表示的是平底容器的成型,不过,该方法也可用于成型具有带脚的底的容器的成型(见图15)。图8-11中的数字编号指示与图4-7中类似的部件,但增加了“撇”号。
因此,图8表示预成型物50′固定在转动的套筒夹部件200′上,并置于第一模具单元214′内。各部件基本上与图4中的相应,但模具单元214′的下部除外,这里在第一个膨胀步骤中由下模具单元220′成型膨胀的平底。
图9表示在第一个膨胀步骤中预成型物50′膨胀成为初级中间制品70′。同样,定心杆208′轴向拉伸预成型物50′,将流体射入被拉伸的预成型物中央,以将其径向膨胀到模具单元214′的内壁上。在第二个实施例中,侧壁部分72′和74′也被膨胀到等于或大于相应的最终容器侧壁部分(图2中的20和22)的尺寸。另外,底部形成部分56′也被膨胀到与最终容器底部(图2中的16)所需尺寸大致相同的尺寸。这样,在第一个膨胀步骤之后,预成型的底部形成部分56′被膨胀成型为平底76′,它有一个中央突起部分75′,凹陷77′,凹边78′和外底部分79′。与第一个实施例相似,颈板216′是冷的(例如40-70°F),上模体是热的(例如180-210°F)。不过,由于底部76′在第一个膨胀步骤中已被膨胀,下模220′是冷的(例如40-70°F),以防膨胀的底部结晶。
图10表示热处理步骤,在这里初级中间制品70′被收缩成次级中间制品80′。同样,制品70′也是固定在转动的套筒夹202′上并被插入热处理单元228′内部,该热处理单元包括外套230′,上隔热板232′和一系列的红外线加热元件234′,当它随着长形的热处理腔室运动时对制品70′加热235′(例如400-500°F)。同样,由移动式隔热板236′防护制品的底部。在热处理步骤之后,肩部72′和面板部分74′收缩成型为炊级中间制品80′的肩部82′和面板部分84′,膨胀的底部76′在尺寸和结晶度方面基本上保持不变,成为底部86′。
图11表示第二个膨胀步骤,在这里收缩的中间制品80′被膨胀成型为最终的容器10′(与图2中的容器10相似)。同样,通过套筒夹202′送入高压空气以膨胀肩部82′和面板部分84′,使其成型为最终容器10′上相应的肩部20和面板部分22。颈板242′也是冷的(例如40-70°F),所以颈端基本上保持其非晶态;上模体244′是热的(例如120-150°F)以释放容器肩部和面板部分的残留张力;下模体246′是冷的(例如40-70°F)以保持底部16较低的结晶度。在第二个膨胀步骤中,容器底部的尺寸和结晶度基本保持不变。
图13表示与制造平底容器的第二个方法实施例(图8-11)相关的容器外形。因此,轮廓1表示具有底部形成部分56′的预成型物50′。轮廓2表示第一个膨胀步骤之后的初级中间制品70′,它有一个未膨胀的底部76′。轮廓3表示热处理步骤之后的次级中间制品80′,底部86′基本保持不变。轮廓4表示最终的容器10′,它有收缩的侧壁和基本上未变的底部16′。
类似地,根据图8-11中的第二个方法实施例可以成型带脚的底部,如图15所示的容器外形所示。不过,在这种情况下底部中央增厚部分176在第一个膨胀步骤中保持不变,而上底部分177′在第一个膨胀步骤中被膨胀成型为上部半球形底部。轮廓1表示具有底部形成部分156′的预成型物150′。轮廓2表示第一个膨胀步骤之后的初级中间制品170′和底部173′,它具有膨胀的外底部分177′但仍维持较厚的、基本上未膨胀的中央底部形成部分176′。轮廓3表示热处理步骤之后的次级中间制品180′及其底部183′,其中中央加厚的底部形成部分186′基本不变(与176′部分相比),但膨胀的侧壁和膨胀的外底部分187′收缩了。轮廓4表示最终的容器110′及其底部116′,它具有结晶度很低(低于2%)的较厚中央半球形底壁部分124′(同图3中的124),以及较薄的膨胀的(尽管比例侧壁膨胀的少)部分131′(同图3中的131),包括支腿、支脚和肋,其结晶度相对较高(即:10-20%),但又低于侧壁的结晶度(即:25%或以上)。
图16-19表示另一种可用的热处理装置。图16表示了与图6相同的转动式套筒夹202、定心杆208和次级中间制品80,以及另一种热处理单元256,包括外套256鼓风机260,后者发送热气加热初级中间制品70以制成次级中间制品80。尽管也可采用图6所示的隔热元件,加厚的底部86本身能抗热致结晶。
图17中示出了图10所示的转动套筒夹202′、定心杆208′和次级中间制品80′。提供了处理单元256,包括热鼓风机260,用于加热侧壁,水冷底部杯272,用于约束底部76′,当其随收缩的侧壁向上运动时成为底部86′(尺寸结晶度大体相同)。水冷底部杯固定在可移动的活塞273上,以便在侧壁收缩并且底部向上运动时,保持与底部连续的接触。该杯包括约束加厚的底部的上表面274,板232′和感应加热杆234′,由它向中间制品170′的侧壁加热箭头(235′),以及保护底部176′用的移动式隔热板236′。初级中间制品170′适于成型带脚的容器,而且在第一个膨胀步骤之后加厚的中心部分176′仍保持不变,而外底部分177′被膨胀。初级中间制品170′收缩成型为次级中间制品180′,但中央的底部176′(及外底177′的邻近部分)由通过管282提供的冷气流(箭头283)冷却,以防中央底部的结晶和收缩。所得的次级中间制品180′有一个加厚的中央部分186′和较薄的上底部分187′。
图19中示出了类似图6的转动式套筒夹202,定心杆208和次级中间制品80,但它的热处理单元266包括外套267和一系列的射频(RF)电极268,当初级中间制品70沿腔室运动并收缩型为次级中间制品时,RF电极268随之变短,如图中箭头和虚线所示。RF电极268由RF能量输入端271和电感线圈270供能。当制品收缩并在热处理腔室中运动时,通过仅对侧壁局部加热的方式可以消除或大大减少对底部76(和86)的加热。
本发明中所用的热塑聚酯材料最好是基于聚亚烃的,具体来说,象聚对苯二甲酸乙二醇酯(PET)。PET聚合物是通过聚合对苯二酸或其酯形成衍生物和乙烯制备而成的。该聚合物包括重复的如下式所示的对苯二酸乙二醇单元:
本发明打算采用聚对苯二甲酸乙二醇酯的共聚物,其中,一小部分(例如:大约重量的10%)对苯二甲酸乙二醇单元被相容的单体单元所取代。因此,这里所用的“PET”是指适于制造容器的PET均聚物和PET共聚物,这在本领域是众所周知的。单体的乙二醇部分可以用脂族或脂环族乙二醇,象环己烷二甲醇(CHDM),三甲基乙二醇、聚四甲基乙二醇、六甲基乙二醇、十二甲基乙二醇、二甘醇、聚乙二醇、聚丙二醇,丙烷-1,3-二醇、丁烷-1,4-二醇和新戊二醇,以及其它芳族二醇,象氢醌和2,2-双(4′-B羟乙氧苯基)丙烷取代。可取代单体单元里的二羧酸部分的例子包括芳族二羧酸,象间苯二酸(IPA)、苯二甲酸、萘二羧酸、二苯基二羧酸,联苯氧乙烷二羧酸,联苯甲酸,以及脂族或脂环族二羧基酸,象己二酸,癸二酸、壬二酸、癸烷二羧酸和环己烷二羧酸。另外,还有多种多功能化合物,象三羟甲基丙烷、季戊四醇、1,2,4-苯三酸和1,3,5-苯三酸可以与聚对苯二甲酸乙二醇酯多聚体共聚合。
聚对苯二甲酸乙二醇酯多聚体还可以含有其它不会对容器的性能特征产生不利影响的、相容的添加剂和配料,这些不利影响是指对其所包装的产品的味道和其它性能的不良影响。这种配料的例子包括热稳定剂、光稳定剂、颜料、色素、增塑剂、填充剂、抗氧化剂、润滑剂、挤压助剂、残余单体净化剂等。
固有粘度(I.Vo)影响聚酯树脂的加工性能。固有粘度大约为0.8的聚对苯二甲酸乙二醇酯被广泛用于CSD行业。有多种用途的树脂其固有粘度可在0.55-1.04的范围内,更具体地说在0.65-0.85范围内。固有粘度的测量是根据ASTMD-2857方法进行的,在30℃下分别采用0.005±0.0002g/ml的多聚体溶于含有O-氯苯酚(熔点0℃)。固有粘度(I.Vo)通过下式给出:
I.Vo=(In(Vsoln./Vsol.))/C
其中Vsoln是溶液的任何单位的粘度;
Vsol是同样单位的溶剂的粘度;
C是每100ml溶液中多聚体克数的浓度。
用于制造本发明的高透明度再填充瓶子的预成型物应基本上是非晶态的,对PET来说意味着结晶度为10%,最好不超过5%,不超过2%更好。预成型物的非晶性透光性也可以用百分混浊度(HT)不超过20%来限定,最好不超过10%,不超过5%更好。基本上非晶形的预成型物可以是单层或多层(例如,具有抗O2和/或CO2滞留的阻挡层)根据已知注塑方法制造的预成型物,例如在1987年12月1日授予Kirshnakumar等人的美国专利4,710,118中所公开的,其全部在这里收作参考。
在预成型物的注模过程中,热注预成型物可冷却至室温,然后再在膨胀步骤之前将其再加热至定向温度范围内,即:再加热拉伸吹塑方法。另外,热注塑预成型物也可部分冷却,并在膨胀之前使其在定向温度范围内平衡。基本上为非晶态的预成型物随后被膨胀,在容器的侧壁上产生定向和结晶。拉伸的程度可以根据被吹塑容器所需形状和壁厚来决定,并通过固定原始预成型物和最终预成型物的尺寸来加以控制,膨胀步骤应当在所用聚酯材料的分子定向温度范围内进行。一般来说,可定向的热塑材料通常在该多聚体玻璃化转变温度以上(在该温度或较窄的温度范围以下,多聚体是玻璃态的),至熔化温度以下的温度范围内发生分子定向。实际上,成型分子定向的容器是在被称为分子定向温度范围的更窄的温度范围内完成的。这样做的理由是,温度愈接近玻璃化转变温度,材料愈坚硬,难于在常规加工设备上拉伸。随着温度的提高,材料的加工性能大大地改善。但是,当达到或接近被称做球晶的、大的晶粒聚集体开始形成的温度时,也就达到了其操作上限,因为球晶的生长会对定向过程产生不利影响。对非晶形聚酯材料来说,分子定向的温度范围通常在20-65°F(11-36℃)内,最好在30-40°F(17-22℃)内,这一范围在聚酯材料的玻璃化转变温度以上。玻璃化转变温度为168°F(76℃)的典型的非晶形PET多聚体,其定向温度一般在195°F(91℃)至205°F(96℃)范围内。
生产可再填充的聚酯饮料瓶的其它重要因素在下列美国专利中有记载:1982年6月15日授予Kirshnakumar等人专利权的US-4,334,627;1988年2月16日授予Collette专利权的US-4,725,464;以及1991年11月19日授予Krishnakumar等人的US-5,066,528号专利,以上所有专利这里收作参考。
作为一种选择,由发明人Collette等人于1992年7月7日申请的、题为“多层可再填充容器,预成型物及其成型方法”的普通转让的待批专利申请07/909,961号,以及与该申请的部分继续申请所公开的多层预成型物可以在本发明的方法中使用。除了可以采用在低共聚物(0-2%)内层与外层之间夹一层高共聚物(4-6%)芯层的形式外,其它多层容器可以包括阻挡层、高热稳定性、重复或二次使用PET,或其它面层。
如上所述,本发明的塑料容器最好由聚对苯二甲酸乙二醇酯(PET)制造。不过,其它热塑聚酯树脂也可使用。对于特定的终产品来说,可以改变材料、壁厚、预成型物和瓶子外形以及处理技术,同时结合本发明的内容。这种容器还可用来装其它的加压或不加压的饮料(如啤酒、果汁或牛奶),或用来装非饮料制品。本发明的优点,例如改善的在高温下的抗应力裂变性,尤其适于用作热装容器,如在于1989年9月5日授予Collette等人的美国专利US-4,863,046中公开的,该文献在这里用作参考。热塑容器通常必需能耐受180-185°F的高温(产品填充温度)、2-5磅的正内压(填充线压力)而无明显变形(即:体积变化不超过约1%)。
尽管这里特意说明和描述了本发明的几个优选实施例,不过应当知道,在不脱离由所附权利要求限定的本发明的精神和范围的情况下,可以对预成型物的结构、材料,容器的结构和成型容器的方法做一些改变。
Claims (45)
1、一种制造具有侧壁和底部的容器的方法,包括以下步骤:
提供一种基本上非晶形的聚酯预成型物,它有侧壁形成部分和底部形成部分,其中,侧壁形成部分是在该聚酯的定向温度范围内,
膨胀侧壁形成部分以形成一种中间制品,它具有尺寸大体上等于或大于最终容器侧壁尺寸的中间侧壁,而底部形成部分在大小方面基本保持不变;
加热膨胀的中间侧壁,以使其结晶并收缩至最终容器侧壁尺寸以下,而底部形成部分基本上保持非晶形态,尺寸也基本上保持不变;
在定向温度范围内,膨胀收缩了的中间侧壁和底部形成部分至容器侧壁和底部的最终尺寸。
2、如权利要求1所述的方法,其特征在于,在加热步骤中底部形成部分被保护起来,以防止底部形成部分结晶。
3、如权利要求1和2中任意一项所述的方法,其特征在于,在加热步骤中在预成型物里放置一个定心杆,它可随着收缩的中间容器收缩。
4、如权利要求3所述的方法,其特征在于,在加热步骤中对中间制品里的内压加以控制,以促进均匀收缩。
5、如权利要求1所述的方法,其特征在于,第一个膨胀步骤是在第一个外模具中吹塑模制,该模具的上部在第一温度下约束膨胀的中间侧壁,其下部在低于第二温度的条件下约束底部形成部分。
6、如权利要求5所述的方法,其特征在于,第二个膨胀步骤是在第二个外模具中吹塑模制,该模具的上部在第三温度下约束容器的侧壁,其下部在等于或低于第三温度的第四温度下约束底部,以阻止底部结晶。
7、如权利要求1所述的方法,其特征在于,形成的侧壁包括上锥形肩部和基本上为筒状的侧板,而且加热和膨胀在侧板上所产生的平均结晶度至少为25%。
8、如权利要求7所述的方法,其特征在于,形成的底部包括加厚的底部,它比侧板厚,而且平均结晶度不超过10%。
9、如权利要求8所述的方法,其特征在于,加热和膨胀提供了足够的壁厚、双轴取向和结晶度,以形成独立的可加压的容器。
10、如权利要求9所述的方法,其特征在于,加热和膨胀提供了足够的壁厚、双轴取向和结晶度,以形成可再填充的、独立的、可加压的容器。
11、如权利要求10所述的方法,其特征在于,加热和膨胀提供了足够的壁厚、双轴取向和结晶度,以形成可热填充的容器。
12、一种由权利要求1所述方法生产的容器。
13、如权利要求12所述的容器,其特征在于,形成的侧壁包括上锥形肩部和基本上为筒状的侧板,而且侧板的平均结晶度至少为25%。
14、如权利要求13所述的容器,其特征在于,容器底部13的至少一部分形成加厚的底部,其厚度至少比侧板的厚度大3倍,平均结晶度不超过10%。
15、如权利要求14所述的容器,其特征在于,容器被制成具有一个扁平的底,加厚的底部包括凹边和中央拱顶。
16、如权利要求12所述的容器,其特征在于,所用聚酯是聚对苯二甲酸乙二醇酯(PET)。
17、如权利要求16所述的容器,其特征在于,所用聚酯是PET的同聚物或共聚物。
18、如权利要求14所述的容器,其特征在于,形成的肩部其平均结晶度为20-30%,侧板的平均结晶度为25-35%,而加厚的底部其平均结晶度不超过10%。
19、如权利要求18所述的容器,其特征在于,所形成的侧板其平均结晶度为30-35%。
20、如权利要求19所述的容器,其特征在于,所形成的侧壁厚为0.5-0.8mm。
21、如权利要求12所述的容器,其特征在于,所生产的容器在碱洗温度超过60℃的情况下能承受至少10次再填充循环面无开裂缺陷。
22、如权利要求12所述的容器,其特征在于,所生产的容器在碱洗温度超过60℃的情况下能承受至少20次再填充循环而无开裂缺陷。
23、如权利要求21-22中任一项所述的容器,其特征在于,所生产的容器能够耐受设定的再填充循环而最大体积变化为±1.5%。
24、如权利要求12所述的容器,其特征在于,所生产的容器是独立的、双轴取向的耐压PET容器。
25、如权利要求13所述的容器,其特征在于,容器被制成具有大体上为半球形底板的带脚的底部,底板包括中央加厚的底部,其厚度至少为侧板厚度的3倍,平均结晶度不超过10%,还包括较薄的外底部分,其上有辐射肋和向下延伸至最低处的支脚的支腿。
26、如权利要求25所述的容器,其特征在于,较薄的外底部分其平均结晶度为10-20%。
27、一种制造具有侧壁和底部的容器的方法,包括以下步骤:
提供一种具有侧壁部分和底部形成部分的基本上非晶形的聚酯预成型物,其中,侧壁形成部分和底部形成部分在所用聚酯定向温度范围内;
膨胀侧壁形成部分以制成中间的、膨胀过的侧壁的中间制品,侧壁的尺寸基本上等于或大于最终容器侧壁的尺寸,并将底部形成部分膨胀至基本上与最终容器底部相同的尺寸;
加热膨胀的中间侧壁,以使其结晶并收缩至小于最终容器侧壁的尺寸,而底部仍保持其尺寸和百分结晶度;
在定向温度范围内,膨胀收缩过的中间制品侧壁至容器侧壁的最终尺寸,而底部仍保持其原有尺寸和百分结晶度。
28、如权利要求27所述的方法,其特征在于,在加热步骤中底部被保护起来以维持其尺寸和百分结晶度基本不变。
29、如权利要求27和28中任一项所述的方法,其特征在于,在加热步骤中底部被冷却以保持其尺寸和百分结晶度基本不变。
30、如权利要求29所述的方法,其特征在于,加热步骤包括加热底部,以便至少部分地释放在第一个膨胀步骤中底部上产生的张力。
31、一种由权利要求27所述方法生产的容器。
32、一种容器,包括基本上透明的、双轴取向的、独立的吹制聚酯腔体,该腔体有一个具有上锥形肩部和基本上为筒状侧板的侧壁,还有一个具有加厚的底部的底,其壁厚至少比侧板壁厚大3倍,侧板的平均结晶度至少为25%,而加厚的底部的平均结晶度不超过10%。
33、如权利要求32所述的容器,其特征在于,底是平底,加厚的底部包括中央拱顶和凹边。
34、如权利要求32所述的容器,其特征在于,底是带脚的底,它具有基本上为半球形的底板和向下延伸至最下方的支脚处的支腿,加厚的底部包括半球形底板(无腿)的中央部分。
35、如权利要求34所述的容器,其特征在于,底还包括与加厚的底部相比较薄的底部,包括支腿、支脚和底板上支腿之间的肋,较薄的底部其平均结晶度为10-20%。
36、如权利要求32所述的容器,其特征在于,侧板的平均结晶度为30-35%。
37、如权利要求32所述的容器,其特征在于,该容器在碱洗温度超过60℃的情况下能承受至少10次再填充循环而无开裂缺陷。
38、如权利要求32所述的容器,其特征在于,该容器在碱洗温度超过60℃的情况下能承受至少20次再填充循环而无开裂缺陷。
39、如权利要求37-38中任一项所述的容器,其特征于,该容器能承受设定的再填充循环而最大体积变化仅为±1.5%。
40、如权利要求32所述的容器,其特征在于,所用聚酯是聚对苯二甲酸乙二醇酯(PET)。
41、如权利要求40所述的容器,其特征在于,侧板的平均壁厚为0.50-0.80mm,平均结晶度为30-35%,加厚的底部的平均壁厚为2.0-4.0mm,平均结晶度不超过10%。
42、如权利要32所述的容器,其特征在于,该容器是独立的、双轴取向的加压PET容器。
43、如权利要求32所述的容器,其特征在于,该容器是热填充容器。
44、如权利要求12、31和32中任一项所述的容器,其特征在于,所用聚酯是制瓶级PET。
45、如权利要求44所述的容器,其特征在于,该容器有一个至少包括一层从阻挡层、高热稳定性、循环PET和再用PET中选择的一种材料的多层侧壁。
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US08/082,029 US5520877A (en) | 1992-07-07 | 1993-06-30 | Method of forming container with high-crystallinity sidewall and low-crystallinity base |
US08/082,029 | 1993-06-30 |
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JPH0643091B2 (ja) * | 1989-02-10 | 1994-06-08 | 東洋製罐株式会社 | 耐熱性ポリエステルボトルとその製造方法 |
EP0425360B1 (en) | 1989-10-23 | 1996-02-21 | Nissei Asb Machine Co., Ltd. | Method for manufacturing biaxially oriented blow containers and apparatus for manufacturing the same |
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US5066528A (en) † | 1990-03-05 | 1991-11-19 | Continental Pet Technologies, Inc. | Refillable polyester container and preform for forming the same |
JPH0735085B2 (ja) † | 1990-10-05 | 1995-04-19 | 日精エー・エス・ビー機械株式会社 | 2軸延伸結晶性樹脂容器およびその製造方法 |
JPH0688315B2 (ja) * | 1990-10-25 | 1994-11-09 | 日精エー・エス・ビー機械株式会社 | 耐熱性中空容器のための一次ブロー成形品 |
AU679186B2 (en) | 1992-07-07 | 1997-06-26 | Graham Packaging Pet Technologies Inc. | Method of forming container with high-crystallinity sidewalland low-clystallinity base |
US5281387A (en) * | 1992-07-07 | 1994-01-25 | Continental Pet Technologies, Inc. | Method of forming a container having a low crystallinity |
-
1993
- 1993-07-02 AU AU46637/93A patent/AU679186B2/en not_active Ceased
- 1993-07-02 SK SK15-95A patent/SK1595A3/sk unknown
- 1993-07-02 CA CA 2139741 patent/CA2139741C/en not_active Expired - Fee Related
- 1993-07-02 AT AT93916957T patent/ATE157927T1/de not_active IP Right Cessation
- 1993-07-02 EP EP93916957A patent/EP0653982B2/en not_active Expired - Lifetime
- 1993-07-02 DE DE69313862T patent/DE69313862T3/de not_active Expired - Fee Related
- 1993-07-02 WO PCT/US1993/006329 patent/WO1994001269A1/en active IP Right Grant
- 1993-07-07 CN CN93116495A patent/CN1089226A/zh active Pending
-
1996
- 1996-05-24 US US08/652,985 patent/US5829614A/en not_active Expired - Fee Related
-
1998
- 1998-10-30 US US09/183,702 patent/US6372318B1/en not_active Expired - Fee Related
-
2002
- 2002-04-16 US US10/122,297 patent/US6926859B2/en not_active Expired - Fee Related
-
2005
- 2005-08-08 US US11/199,422 patent/US7445826B2/en not_active Expired - Fee Related
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101027177B (zh) * | 2004-07-27 | 2010-09-29 | 东洋制罐株式会社 | 耐热性和耐冲击性优良的聚酯容器及其制造方法 |
CN101987505A (zh) * | 2009-07-31 | 2011-03-23 | 克朗斯股份有限公司 | 带有同步加热和拉伸的模塑塑料预制件的设备 |
US8517711B2 (en) | 2009-07-31 | 2013-08-27 | Krones Ag | Apparatus for moulding plastic preforms with synchronous heating and stretching |
CN101987505B (zh) * | 2009-07-31 | 2015-10-14 | 克朗斯股份有限公司 | 带有同步加热和拉伸的模塑塑料预制件的设备 |
CN104053604A (zh) * | 2012-02-16 | 2014-09-17 | 西德尔合作公司 | 包括具有方形底座的拱状底部的扁平容器 |
CN104053604B (zh) * | 2012-02-16 | 2016-08-31 | 西德尔合作公司 | 包括具有方形底座的拱状底部的扁平容器 |
CN105383868A (zh) * | 2014-08-29 | 2016-03-09 | 西得乐独资股份公司 | 容器处理机器和方法 |
CN105383869A (zh) * | 2014-08-29 | 2016-03-09 | 西得乐独资股份公司 | 容器处理机器和方法 |
CN105383869B (zh) * | 2014-08-29 | 2019-08-02 | 西得乐独资股份公司 | 容器处理机器和方法 |
CN107223110A (zh) * | 2014-12-04 | 2017-09-29 | 莱克斯诺弗莱托普欧洲有限公司 | 塑料瓶的输送 |
CN107223110B (zh) * | 2014-12-04 | 2019-10-18 | 莱克斯诺弗莱托普欧洲有限公司 | 塑料瓶的输送 |
Also Published As
Publication number | Publication date |
---|---|
US5829614A (en) | 1998-11-03 |
US6372318B1 (en) | 2002-04-16 |
DE69313862T2 (de) | 1998-01-22 |
US20020150703A1 (en) | 2002-10-17 |
US6926859B2 (en) | 2005-08-09 |
WO1994001269A1 (en) | 1994-01-20 |
EP0653982B2 (en) | 2001-01-03 |
CA2139741A1 (en) | 1994-01-20 |
EP0653982A1 (en) | 1995-05-24 |
AU679186B2 (en) | 1997-06-26 |
DE69313862D1 (de) | 1997-10-16 |
SK1595A3 (en) | 1995-09-13 |
EP0653982B1 (en) | 1997-09-10 |
AU4663793A (en) | 1994-01-31 |
CA2139741C (en) | 1998-08-25 |
DE69313862T3 (de) | 2001-04-26 |
US20050271843A1 (en) | 2005-12-08 |
US7445826B2 (en) | 2008-11-04 |
ATE157927T1 (de) | 1997-09-15 |
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