CN101389460A - 熔融树脂供给方法以及熔融树脂供给装置 - Google Patents
熔融树脂供给方法以及熔融树脂供给装置 Download PDFInfo
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Abstract
本发明提供一种熔融树脂供给方法以及熔融树脂供给装置,目的在于熔融树脂的挥发成分不附着于输送部件的表面上,且使熔融树脂供给装置可长时间稳定地运行。压缩成形机的熔融树脂供给装置的挤压机的挤压单元(4)从挤压喷嘴(30)的挤压开口(35c)将熔融树脂(11)排出。在挤压喷嘴(30)的外周部设置有喷出冷却用气体的喷气喷嘴(35),使该喷气喷嘴(35)朝向自挤压开口(35c)挤压出的熔融树脂(11)的表面,借助冷却用气体使熔融树脂(11)的表面冷却。
Description
技术领域
本发明涉及一种利用切断部件将自挤压喷嘴的挤压开口挤压出的熔融状态树脂切断、由保持部件将所切断的熔融树脂保持而供给到成形装置的熔融树脂供给方法以及熔融树脂供给装置。
背景技术
作为饮料等使用的容器,由聚酯等合成树脂形成的合成树脂制容器被广泛使用。近年来,通过吹塑成形而制成合成树脂制容器的预成形体(preform,预成形件)可在压缩成形装置中通过压缩成形来进行一体成形。
完成这样的压缩成形时,如下所示那样将自挤压喷嘴的挤压开口挤压出的熔融状态的合成树脂向压缩成形装置供给(输送)。
在挤压机中将被加熟、熔融的熔融树脂自设置于挤压机上的挤压喷嘴的挤压开口挤压出。使用切断部件将挤压出的熔融树脂切断,从挤压开口处将其切断。将所切断的熔融树脂(被切断熔融树脂)供给到配置在移送机构上的熔融树脂输送部件。
将输送部件选择性地设定为保持熔融树脂的闭合状态、或将所保持的熔融树脂向下方排出的打开状态,并且使其绕旋转轴移动。收纳于闭合状态的保持部件中的熔融树脂被移动到设置于压缩成形装置中的阴模的上方位置后,通过将保持部件形成打开状态而使其向下方排出(落下),并被移送到阴模中。
通过与设置于压缩成形装置中的阳模一起动作将移送至阴模处的熔融树脂压缩成形,用于以所需要形状的聚酯等饮料瓶用预成形件为首的各种产品的成形上。
作为将挤压出的熔融树脂定量、切断而供给到压缩成形用模具的装置,提出了日本专利第3674337号公报中所述的合成树脂供给装置等,但是,特别在树脂为聚酯树脂的情况下,极微量的挥发成分会从所挤压出的熔融树脂表面挥发。经过长时间运行后,挥发成分附着于切断工具、输送部件、模具的各表面上,随着该表面附着物堆积于所述部件的表面上,还使低分子量的树脂成分发生附着。附着树脂成分时,存在容易使熔融树脂粘着于输送部件上,改变熔融树脂供给到模具的时机的问题。因此,在以往的熔融树脂供给装置中,无法长时闻稳定地将熔融树脂供给到模具,为了进行连续生产需要每隔一定时间对工具和模具进行清洗。
发明内容
本发明是鉴于这样的问题而做成的,因此,目的在于提供一种熔融树脂供给方法以及熔融树脂供给装置,挥发成分不附着到输送部件的表面上,能长时闻稳定地运行。
本发明在使用溶剂清洗熔融树脂供给装置后,连续供给熔融树脂,之后中断供给,分析附着于熔融树脂的夹持部等上的附着物总量,每一次对熔融树脂进行切断、输送时都会产生低聚体成分为0.1~0.15μg、高分子PET成分为0.15μg左右的附着物。对此,本发明得到了如下的结果:在空气供给压力为0.1MPa而吹到熔融树脂上的情况下,每一次对熔融树脂进行切断、输送时,着眼于将低聚体成分减少至0.04~0.05μg,高分子PET减少至0.003μg。
为了达到上述目的,本发明的熔融树脂供给方法将熔融树脂从挤压喷嘴的挤压开口挤压出,在将冷却用流体对相对于熔融树脂的挤压方向与该挤压开口隔开一定间隔的熔融树脂的表面部位进行喷射之后或进行喷射的同时,使用切断工具将熔融树脂切断,将所切断的熔融树脂保持并输送到压缩成形用模具的阴模,在该阴模的正上方位置使熔融树脂落下到该阴模内。
而且,为了达到上述目的,本发明的熔融树脂供给装置包括:挤压喷嘴,其将熔融树脂从挤压开口排出;切断工具,其将自该挤压喷嘴的挤压开口排出的熔融树脂切断;保持构件,其具有对自该挤压开口排出的熔融树脂进行保持以及解除保持的机构;输送部件,其在支承着该切断工具和该保持构件的同时,将切断熔融树脂后保持着熔融树脂的该保持构件输送到压缩成形用模具的阴模;在该阴模的上方位置由该保持构件释放出熔融树脂而使熔融树脂供给到该阴模内,其中,在该挤压喷嘴的周围设置喷出流体的喷出部件,该喷出部件的喷出口朝向从该挤压喷嘴的该挤压开口向该挤压喷嘴的挤压方向隔开一定间隔的熔融树脂的表面,使该保持构件保持表面被流体冷却后的熔融树脂。
上述熔融树脂供给装置可在该挤压喷嘴的周围将该喷出部件设置为环状,且在该流体供给部件与该挤压喷嘴之间呈环状地形成绝热用间隙。
而且,上述熔融树脂供给装置在该熔融树脂为聚酯的熔融树脂时更有效。
附图说明
图1是本发明的实施方式的熔融树脂供给装置的概略俯视图。
图2是图1的熔融树脂供给装置的挤压成形机的挤压单元的剖视图。
图3是图1的熔融树脂供给装置的输送部件的夹持构件处于闭合状态时的剖视图。
图4是图1的熔融树脂供给装置的输送部件的俯视图。
图5是图1的熔融树脂供给装置的输送部件的夹持构件处于打开状态时的剖视图。
图6是图2的挤压成形机的挤压单元的挤压喷嘴的放大剖视图。
具体实施方式
以下,参照附图对本发明的实施方式熔融树脂供给装置进行说明。
图1表示本发明的熔融树脂供给装置1和压缩成形装置6;图2是合成树脂供给装置1的挤压机2的挤压单元4的放大图,图3是挤压单元4与输送单元20之间的熔融树脂交接部位置剖视图,图4是输送单元20和压缩成形装置6的俯视图,图5是输送单元20与压缩成形装置6之间的熔融树脂交接位置的剖视图。
首先,对利用挤压机2生成的熔融树脂11(参照图2)的流程进行简单的说明。
以合成树脂作为材料的熔融树脂供给装置1设置有圆筒(cylinder)状的挤压机2。挤压机2对聚对苯二甲酸乙二醇酯(PET)等合成树脂材料进行加热熔融和混炼,并将熔融树脂11输送往齿轮泵3。在齿轮泵3中,为了使熔融树脂11稳定地供给,通过齿轮的啮合来进行熔融树脂11的喷出。齿轮泵3借助导管2a与图2所示的朝下的挤压单元4相连接,在挤压单元4的下端部形成有挤压开口35c。挤压开口35c具有圆形截面,熔融树脂11从挤压开口35c形成大致圆柱形状而连续地向下方被挤压出。
如图3所示,使用刀具12切断挤压出的熔融树脂11(滴状物,drop),从挤压开口35c将其切开。将所切开的熔融树脂11供给到配置于移送机构上的熔融树脂的输送单元20。
输送单元20通过开闭用于保持熔融树脂11的保持单元21,来以闭合状态保持熔融树脂11,在打开状态下使保持的熔融树脂11向下方排出,并且可使保持单元21绕旋转轴移动。并且,将保持于闭合状态的保持单元21中的熔融树脂11移动到设置于压缩成形装置6上的阴模7的上方位置后,使保持单元21变为打开状态而使熔融树脂11在重力作用下向下方落下,再移送到图4和图5所示的阴模7中。利用设置于压缩成形装置6上的未图示的阳模和阴模7,形成作为容器预成形体的预成形件(preform)。
另外,图1所示的附图标记8表示将成形后的预成形件取出的取出机构。
图2是挤压机2的挤压单元4的放大剖视图。
挤压单元4在筒状构件29的下部安装有挤压喷嘴30。将熔融树脂导入挤压单元4的内部,形成有轴线沿上下方向延伸而横截面为圆形的流通孔29a。在挤压喷嘴30的外周围配置有用于防止通过流通孔29a的熔融树脂11冷却的加热器31。在加热器31的外周部设置有安装于筒状构件29的下部的支承架33。支承架33的半截面形状呈大致コ字形状,使呈コ字形的开口侧朝向外侧且形成环状的形状,将与供给未图示的常温空气的泵等空气供给部件23相连接的喷气喷嘴35支承于下表面上。
挤压喷嘴30的比对应于加热器31的位置更靠下的下侧由前端喷嘴30a(图6所示的是其放大图)形成,位于前端喷嘴30a下端的前端边缘30b形成为锐角的刀刃状。也可根据情况在该部分将微型加热器等卷起来,或安装浇铸加热器。
喷气喷嘴35由上下配置的环状的上板35a和下板35b构成,在一端部设置有与空气供给部件23相连接的空气供给口36。在空气供给口36处,在挤压喷嘴30的周围形成有环状通道37。如图6所示,环状通道37朝着环状的喷气喷嘴35的径向内侧的斜下侧延伸,与在上板35a与下板35b之间形成的喷气通道37a相连通。在喷气通道37a的下端形成有环状的喷气口37b。喷气口37b的位置处于比挤压喷嘴30的顶端边缘30b的位置高的位置,换言之,挤压喷嘴30的顶端边缘30b从喷气口37b向下方突出地配置。
需要将该喷气通道37a的倾斜角设定为在比挤压喷嘴30的顶端边缘30b低的位置自喷气喷嘴35喷出的空气吹不到顶端边缘30b,优选需要设定为使空气能吹到熔融树脂11与下述的保持熔融树脂11的保持单元21相连接的部分的整个周围那样的角度。
在挤压喷嘴30的顶端喷嘴30a与喷气喷嘴35的内周面之间形成有环状的间隙38。
如图1所示,挤压机2的挤压单元4构成为,利用未图示的驱动源,该推压单元4可在位于输送单元20的保持单元21的旋转轨迹的垂直上方的作用位置(虚线)、与从该旋转轨迹向水平方向退避的非作用位置(实线)之间移动。
如图3~图5所示,熔融树脂供给装置1的输送单元20具有旋转台9。旋转台9被具有垂直轴线的转轴9a支承,利用电动机等未图示的驱动源可沿图4中的顺时针方向进行旋转驱动。输送单元20对熔融树脂11进行输送,使其通过与挤压喷嘴30相对置的接收位置P1、以及与压缩成形装置6的阴模7相对置的排出位置P2。在输送单元20上包含刀具12和保持单元21,该刀具12用于切断熔融树脂,该保持单元21对所切断的熔融树脂进行保持。
刀具12安装于处于输送单元20的旋转台9的下表面侧的安装部15上。在刀具12安装在旋转台9上的状态下,将刀具12的刃尖缘13定位成从旋转台9的周缘向旋转台9的径向外侧水平地突出。
因此,将熔融树脂11从挤压喷嘴30的挤压开口35c挤压出,使旋转台9旋转时,刀具12的刃尖缘13在挤压开口35c的铅直下方隔开规定间隙地沿水平方向进行横切,可将自挤压开口35c向铅直下方挤压出的熔融树脂11切断。
如图2所示,在空气供给部件23与空气供给口36之间安装有截止阀24,利用控制部25来控制截止阀24的开闭。而且,通过控制部25检测各刀具12的旋转角度,在刀具12的刃尖缘13切断熔融树脂11的旋转角的规定角度之前,打开截止阀24,使空气喷出到熔融树脂11的表面上。可由控制部25任意调整该截止阀24的开闭度、开闭时间、形成打开状态的时机(timing)。
保持单元21包含第一夹持构件21和第二夹持构件21b。这些夹持构件21a、21b可开闭地构成,在与挤压喷嘴30相对置的熔融树脂的接收位置P1上,夹持构件21a、21b处于关闭状态,图3表示处于夹持着熔融树脂11的状态下的夹持构件21a、21b。另外,在图5所示的熔融树脂的排出位置P2,夹持构件21a、21b处于打开状态,使熔融树脂11向阴模7落下。
压缩成形装置6具有包括旋转支承体6a以及配置于旋转支承体6a上的多个阴模7的成形模,如图4所示那样沿着逆时针旋转。
接着,对本实施方式的作用进行说明。
供给成形作业初期的熔融树脂11时,将图1所示的挤压机2的挤压单元4定位于图3以及图4所示的接收位置P1上。通过齿轮泵3的动作,使熔融树脂11连续地从挤压开口35c挤压出。并且,当熔融树脂的供给状态稳定时,将熔融树脂11供给到输送部件上。
如图2所示,当将熔融树脂11从挤压开口35c挤压出、且刀具12来到规定位置时,控制部25发出指令使截止阀24成为打开状态,打开截止阀24。由此,将来自空气供给部件23的空气加压输送到空气供给口36,空气通过环状通道37,送到喷气通道37a、喷气口37b。空气从该空气喷气口37b在恒定时间内喷出到熔融树脂的表面上,如图6的箭头A所示,空气喷射到熔融树脂11的外周面上。该喷出空气吹飞了自熔融树脂11产生的挥发成分,可防止挥发成分附着到切断工具之后的单元、特别是保持单元21的夹持构件21a、21b的表面上。
关于吹喷出空气所造成的恶劣影响,由于喷气通道37a的朝向是朝着比挤压喷嘴30的顶端边缘30b高度低的位置,因此顶端边缘30b不被喷出空气冷却。喷出空气只将熔融树脂11的表面冷却,防止因顶端边缘30b冷却而造成杂质附着到顶端边缘30b上。另外,使顶端喷嘴30a的顶端边缘30b逐渐变细,因此,可进一步防止杂质附着到顶端边缘30b上。
在挤压单元4中,将喷气喷嘴35配置于挤压喷嘴30的顶端喷嘴30a的周围,但在顶端喷嘴30a与喷气喷嘴35之间形成间隙38。以该间隙中的空气作为绝热材料,可防止顶端喷嘴30a因空气流通而被冷却。同样也可防止或减轻自喷气喷嘴35喷出的空气因熔融树脂11的热量而温度上升。这样,可防止因空气喷出到自挤压喷嘴30挤压出的熔融树脂11上所产生的恶劣影响。
当刀具12利用输送单元20的旋转将熔融树脂11切断时,保持单元21的夹持构件21a、21b对熔融树脂11进行夹持(参照图3)。使输送单元20的旋转台9进行旋转,利用各个驱动源将旋转台9与压缩成形装置6的旋转支承体6a以相互同步的转速进行旋转。
参照图4或图5,这些旋转台9与旋转支承体6a的旋转方向是相互反向的,因此,在两者的旋转轨道的切点上为相同方向。因此,夹持构件21a、21b与阴模7同步,在作为这些旋转轨道的切点的排出位置P2成为相对静止的状态。因此,熔融树脂11位于阴模7的正上方时,通过解除夹持构件21a、21b的夹持状态而落下,并供给到阴模7内。此时,在熔融树脂11的表面形成有温度比内侧低的冷却薄膜,因此熔融树脂11的粘性变小,减小了与夹持构件21a、21b的表面的摩擦系数,可顺利地将熔融树脂供给到阴模7内。
如上所述,减轻了低聚体、高分子PET等附着物粘着到夹持构件21a、21b上,因此,即使熔融树脂供给装置1连续运行,也可减少通过打开夹持构件21a、21b而使熔融树脂11落下到阴模7的时机变化变慢。这样,通过减少附着物,可使熔融树脂11长时间稳定地供给到阴模7,可连续制作预成形件,也可减少保持单元21等的清理次数,提高熔融树脂供给装置1的工作效率。
在图1所示的压缩成形装置6中,利用旋转支承体6a的旋转使接收了熔融树脂11的阴模7到达规定位置时,配置于阴模7的垂直上方的未图示的阳模开始下降,开始进行压缩成形,在下游侧的规定位置完成压缩成形。这样,按顺序重复进行上述的熔融树脂供给装置1的运行。
根据本实施方式,将熔融树脂供给装置的运行设为如下条件,试着测量熔融树脂的表面温度和熔融树脂的连续供给次数。
材料:PET
挤压量:300kg/小时
树脂挤压口直径:20mm
空气喷射部的间隙:0.6mm
空气喷出部直径:23mm
空气供给压力:0.1MPa
挤压熔融树脂量(1滴):25g
作为测量结果,使用放射温度计测出自挤压机的挤压开口挤压出的熔融树脂的表面温度在250℃~240℃的范围内。
而且,熔融树脂供给装置进行清理、连续运行后,测出刀具12和保持部件21到需要进行下一次清理时的每个循环(set)的连续供给次数。该装置可进行10000~15000次左右的熔融树脂(1滴)的连续供给。
比较例
作为比较例,其材料、挤压量、树脂挤压口直径以及挤压熔融树脂量与上述实施例相同,不将空气吹到熔融树脂的表面上,试着测量熔融树脂的表面温度和熔融树脂的连续供给次数。
作为测定结果,使用放射温度计测出熔融树脂的表面温度在288℃~282℃的范围内。
另外,对熔融树脂供给装置的熔融树脂的连续供给次数进行了测定。可以进行2000~3000次左右的熔融树脂的连续供给。
与比较例相比,实施例通过使熔融树脂的表面温度下降大约42℃~38℃的温度,可获得能使熔融树脂的连续供给次数达到比较例大约5倍的连续供给次数这样好的结果。
以上,对本发明的实施方式进行了说明,当然,在基于本发明的技术构思,本发明可进行各种变形或变更。
例如,在上述实施方式中,在挤压喷嘴30的顶端喷嘴30a与喷气喷嘴35的内周面之间形成环状空间的间隙38作为绝热材料。也可以配置具有绝热性的单个材料作为绝热材料,来变为该间隙38中的空气。而且,本发明也可以适用于不是恒定半径的圆周运动的、连续旋转的供给装置,在运行中连续喷射空气。
而且,上述实施方式中,使用了空气作为冷却用流体,作为冷却用流体,除了空气以外,也可以是含有惰性气体、液体蒸气的压缩空气,以及惰性气体。
本发明的熔融树脂供给方法从挤压喷嘴的挤压开口挤压出熔融树脂,在将冷却用流体对相对于熔融树脂的挤压方向而与该挤压开口隔开一定间隔的熔融树脂的表面部位进行喷射后或进行喷射的同时,使用切断工具将熔融树脂切断。这样,通过流体吹飞熔融树脂表面上的低聚体成分、高分子PET,或者通过冷却熔融树脂表面,可抑制低聚体成分、高分子PET本身的发生。由于低聚体成分,高分子PET难以附着、转移到熔融树脂切断工具之后的工序所使用的工具上,因此能够保持被切断的熔融树脂而输送到压缩成形用模具的阴模。当熔融树脂从阴模的正上方位置落入到该阴模内时,在熔融树脂的输送中不会附着阻碍熔融树脂块滑动的成分,因此可保持其滑动性。其结果,能延长熔融树脂可顺利从保持构件落下的连续运行时间,并提高装置的工作效率。
本发明的熔融树脂供给装置包含:挤压喷嘴,其将熔融树脂从挤压开口排出;切断工具,其将自该挤压喷嘴的挤压开口排出的熔融树脂切断;保持构件,其具有对自该挤压开口排出的熔融树脂进行保持以及解除保持的释放机构;输送部件,其在支承该切断工具和该保持构件的同时,将切断熔融树脂后保持着熔融树脂的该保持构件输送到压缩成形用模具的阴模;在该阴模的上方位置该保持构件释放出熔融树脂而将熔融树脂供给到该阴模内,其中,在该挤压喷嘴的周围设置有喷出流体的喷出部件,该喷出部件的喷出口朝向从该挤压喷嘴的该挤压开口向该挤压喷嘴的挤压方向隔开一定间隔的熔融树脂的表面,该保持构件保持表面被流体冷却的熔融树脂。这样,通过在熔融树脂的表面形成与内部温度不同的冷却薄膜,使附着物难以附着到输送部件的熔融树脂的保持构件上。由于附着物难以附着到输送部件上,因此当熔融树脂下落到压缩成形装置的阴模时,可长时间顺利地供给熔融树脂。其结果,可提高熔融树脂供给装置的工作效率。
上述熔融树脂供给装置在该挤压喷嘴的周围将该喷出部件设置为环状,且在该流体供给部件与该挤压喷嘴之间呈环状形成绝热用间隙,因此喷出部件的流体难以吸收熔融树脂的热量。而且,不使用流体使挤压喷嘴前端进行极端冷却,因此,可一边稳定地进行熔融树脂的喷出,一边将挤出后的熔融树脂表面上的挥发成分吹飞或对挤压树脂表面进行冷却。
而且,由于该熔融树脂是聚酯的熔融树脂,附着物更容易附着于保持构件上,因此上述熔融树脂供给装置更能有效地减轻附着物附着到保持部上。
Claims (4)
1.一种熔融树脂供给方法,其将熔融树脂从挤压喷嘴的挤压开口挤压出,在将冷却用流体对相对于熔融树脂的挤压方向与该挤压开口隔开一定间隔的熔融树脂的表面部位进行喷射后或进行喷射的同时,使用切断工具将熔融树脂切断,将所切断的熔融树脂保持并输送到压缩成形用模具的阴模,在该阴模的正上方位置使熔融树脂落下到该阴模内。
2.一种熔融树脂供给装置,其包括:
挤压喷嘴,其将熔融树脂从挤压开口排出;
切断工具,其将自该挤压喷嘴的挤压开口排出的熔融树脂切断;
保持构件,其具有对自该挤压开口排出的熔融树脂进行保持以及解除保持的机构;
输送部件,其在支承着该切断工具和该保持构件的同时,将切断熔融树脂后保持熔融树脂的该保持构件输送到压缩成形用模具的阴模,
该保持构件在该阴模的上方位置释放出熔融树脂而将熔融树脂供给到该阴模内,其特征在于,
在该挤压喷嘴的周围设置有喷出流体的喷出部件,
该喷出部件的喷出口朝向自该挤压喷嘴的该挤压开口向该挤压喷嘴的挤压方向隔开一定间隔的熔融树脂的表面,使该保持构件保持表面被流体冷却后的熔融树脂。
3.根据权利要求2所述的熔融树脂供给装置,其特征在于,在该挤压喷嘴的周围将该喷出部件设置为环状,且在该流体供给部件与该挤压喷嘴之间呈环状形成绝热用间隙。
4.根据权利要求2或3所述的熔融树脂供给装置,其特征在于,该熔融树脂为聚酯的熔融树脂。
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JP2006051659A JP4725362B2 (ja) | 2006-02-28 | 2006-02-28 | 溶融樹脂供給方法及び溶融樹脂供給装置 |
JP051659/2006 | 2006-02-28 | ||
PCT/JP2007/053460 WO2007105464A1 (ja) | 2006-02-28 | 2007-02-20 | 溶融樹脂供給方法及び溶融樹脂供給装置 |
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EP2206592B1 (en) | 2007-10-24 | 2016-05-18 | Toyo Seikan Group Holdings, Ltd. | Compression-molding apparatus |
JP5151566B2 (ja) * | 2008-03-07 | 2013-02-27 | 東洋製罐株式会社 | 圧縮成形に用いる溶融樹脂を切断するカッターを備えた圧縮成形装置。 |
JP5967076B2 (ja) | 2011-03-10 | 2016-08-10 | 東洋製罐株式会社 | 溶融樹脂供給システムと溶融樹脂供給方法 |
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DE2836941A1 (de) * | 1978-08-24 | 1980-03-13 | Walter Goern | Verfahren und vorrichtung zum kuehlen von extrudierten hohlprofilstraengen |
DE3804464C1 (zh) | 1988-02-12 | 1989-06-08 | Aisa Automation Industrielle S.A., Vouvry, Ch | |
JPH05293799A (ja) | 1992-04-20 | 1993-11-09 | Japan Steel Works Ltd:The | 噴流カット方法及び装置 |
JP2595867B2 (ja) * | 1992-12-28 | 1997-04-02 | 株式会社新潟鉄工所 | 注入圧縮成形機における樹脂の注入装置 |
JP3674337B2 (ja) | 1998-10-02 | 2005-07-20 | 東洋製罐株式会社 | 合成樹脂供給装置 |
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ITRE20030012A1 (it) * | 2003-01-31 | 2004-08-01 | Sacmi | "dispositivo di separazione e trasporto della dose |
JP4042596B2 (ja) * | 2003-03-14 | 2008-02-06 | 東洋製罐株式会社 | 合成樹脂供給装置 |
JP4340853B2 (ja) * | 2003-04-11 | 2009-10-07 | 東洋製罐株式会社 | 中空状多層樹脂成形物の圧縮成形方法 |
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WO2007105464A1 (ja) | 2007-09-20 |
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JP4725362B2 (ja) | 2011-07-13 |
US7776245B2 (en) | 2010-08-17 |
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