CN1239311C - 以聚对苯二甲酸乙二醇酯树脂为主要材料的瓶的制造方法 - Google Patents

以聚对苯二甲酸乙二醇酯树脂为主要材料的瓶的制造方法 Download PDF

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Publication number
CN1239311C
CN1239311C CNB028025490A CN02802549A CN1239311C CN 1239311 C CN1239311 C CN 1239311C CN B028025490 A CNB028025490 A CN B028025490A CN 02802549 A CN02802549 A CN 02802549A CN 1239311 C CN1239311 C CN 1239311C
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article shaped
blow molding
time
pressure
high pressure
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CN1464833A (zh
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矢口弘实
石塚智彦
上杉大辅
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Yoshino Kogyosho Co Ltd
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Yoshino Kogyosho Co Ltd
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/18—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor using several blowing steps
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/08—Biaxial stretching during blow-moulding
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0012—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular thermal properties
    • B29K2995/0017—Heat stable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0065—Permeability to gases
    • B29K2995/0067—Permeability to gases non-permeable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/712—Containers; Packaging elements or accessories, Packages
    • B29L2031/7158—Bottles
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S264/00—Plastic and nonmetallic article shaping or treating: processes
    • Y10S264/90—Direct application of fluid pressure differential to shape, reshape, i.e. distort, or sustain an article or preform and heat-setting, i.e. crystallizing of stretched or molecularly oriented portion thereof
    • Y10S264/905—Direct application of fluid pressure differential to shape, reshape, i.e. distort, or sustain an article or preform and heat-setting, i.e. crystallizing of stretched or molecularly oriented portion thereof having plural, distinct differential fluid pressure shaping steps
    • Y10S264/906—And heat-shrinking outside of mold including subsequent re-expanding of shrunken article using differential fluid pressure

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  • Engineering & Computer Science (AREA)
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  • Thermal Sciences (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)

Abstract

本发明的目的是提供具有耐热性能且赋型性优良的容器或瓶的制造方法。本发明提供一种以聚对苯二甲酸乙二醇酯树脂为主要材料的瓶的制造方法，该方法包括下述工序：使用一次模子，将以聚对苯二甲酸乙二醇酯树脂为主要材料的预成型物进行一次双向拉伸吹塑成型，形成一次中间成型物，将该一次中间成型物加热，使一次中间成型物热收缩形成二次中间成型物，使用二次模子，将该二次中间成型物进行二次吹塑成型，在该二次吹塑成型中，将流体吹入二次中间成型物内使其膨胀之后，再将流体吹入成型物内并使流体循环从而使成型物冷却。

Description

以聚对苯二甲酸乙二醇酯树脂为 主要材料的瓶的制造方法
背景技术
本发明涉及以聚对苯二甲酸乙二醇酯树脂(以下称「PET」。)为主要材料的瓶的制造方法，更详细地说是涉及以具有优良的耐热性能及赋型性的PET为主要成分的瓶的制造方法。
PET由于具有优良的透明性，以及机械强度等，经双向拉伸吹塑成型后，广泛用于饮料用瓶等的容器。
在以PET为主要材料的饮料用瓶等容器的成型中，广泛使用向预先经注射成型的以PET为主要材料的预成型物吹入高压空气等压力流体的双向拉伸吹塑成型的方法。
然而在饮料用瓶等的情况下，要将填充的内容物进行加热杀菌等加热处理，该情况下对容器的耐热性能就有要求。为了提高成型容器或瓶的耐热性能，在如上述双向拉伸吹塑成型中，(金属)模子的温度为140～150℃的高温度，将成型的瓶进行热固化而制得的。
但是，如上述双向拉伸吹塑成型在赋型性方面出现问题，如果在玻璃化转变温度(Tg)以上的模子温度进行吹塑成型，随着模子的温度变高，成型瓶容易发生收缩，使成型瓶的容量大幅度减少，温度超过110℃则会出现外观明显受损的情况。因此，需要一种具有优良的耐热性能及赋型性优良的瓶的制造方法。
另外，以PET为主要材料的瓶为大量制造的物品，希望缩短制造时间。
发明的内容
本发明的目的是提供以尽可能短的时间制造具有耐热性且赋型性优良的容器或瓶的方法。
本发明提供一种以PET为主要材料的瓶的制造方法，该方法包括下述工序：使用一次模子，将以PET为主要材料的预成型物进行一次双向拉伸吹塑成型，形成一次中间成型物，将该一次中间成型物加热，使一次中间成型物热收缩形成二次中间成型物，使用二次模子，将该二次中间成型物进行二次吹塑成型，在该二次吹塑成型中，将流体吹入二次中间成型物内使其膨胀之后，再将流体吹入成型物内并使流体循环从而使成型物冷却。
在本发明中，较好的是，以维持进行二次吹塑成型所需的高压状态的高压吹塑时间，向二次中间成型物内吹入高压流体，减少了上述高压吹塑时间。
较好的是，上述一次双向拉伸吹塑成型是以维持高压状态的高压吹塑时间，向预成型物内吹入高压流体的方式进行的，减少了上述高压吹塑时间。
较好的是，上述高压吹塑时间为适合于得到良好赋型性的时间。
实施发明的最佳方式
本发明首先将以PET为主要材料的原料进行注射成型，形成预成型物。预成型物的形成可用公知的任何一种方法。
以PET为主要材料的原料是指可以是仅由PET组成的树脂，也可以是在聚对苯二甲酸乙二醇酯中共混入其他添加物的树脂。共混物有聚萘二甲酸乙二醇酯(PEN)、间苯二甲酰己二胺(MXD-6)、乙烯-醋酸乙烯共聚物(EVOH)等，但不仅限于此，可使用公知的物质。
另外，原料及瓶可以是单层结构，也可以是层压结构。例如，使用PET和共混物等2种以上的树脂或混合物制成3层结构或者5层结构，但不仅限于此。
然后，通过将上述预成型物进行一次双向拉伸吹塑成型，形成一次中间成型物(一次双向拉伸吹塑成型)。该一次吹塑成型为可使用公知的一次双向拉伸吹塑成型的方法，加热到可将预成型物进行吹塑成型的温度(90～130℃)，使用一次模子，向预成型物内吹入高压流体(空气等)。一次模子的温度以50～230℃为好。
该一次吹塑成型可使用公知的双向拉伸吹塑成型的方法，但如下述的通过在二次吹塑成型中进行空气循环，改善最终制品的赋型性，从而可不需长时间用高压流体进行吹塑即可完成一次促进成型物的成型。因此，可缩短一次吹塑成型中的高压吹塑时间(维持高压的时间)。
一次中间成型物比最终的瓶大，继续形成二次中间成型物。
通过一次吹塑得到的一次中间成型物从一次模子脱模，加热到110～255℃，强制使一次中间成型物热收缩，形成二次中间成型物。该加热温度较好的是比一次吹塑模子的模温高20～60℃，以这样的高温对一次中间成型物进行加热，则在一次吹塑成型中成型物内产生的内部应力减小，一次中间成型物发生热收缩，成为二次中间成型物。
二次中间成型物的大小与最终瓶大致相同或比最终瓶小。
用加热到60～120℃的二次模子将经热收缩得到的二次中间成型物进行二次吹塑成型，得到最终的瓶。
在本发明的该二次吹塑成型中，进行空气循环，使成型物内部的常温空气循环。吹塑成型是将用迄今为止的技术如通过拉伸用芯轴内供给的高压液体(空气等)，经穿设在芯轴上的孔吹入二次中间成型物内部，进行最终瓶的吹塑成型成最终瓶，吹塑成型需要吹入高压空气，膨胀、成型后还要继续吹入空气从而使成型物内部的流体循环，将成型物从内部冷却。
用于空气循环的空气压力为可使成型物内部的空气循环的压力即可。以低于吹塑成型的压力为好。另外，空气循环中的压力变化，可逐渐减少，也可阶段性地减少。阶段性地减少时，可为一个阶段，也可为多个阶段。
二次吹塑成型的吹塑时间以(1)上升到规定压力(高压例如约40MPa)的时间，(2)为了吹塑成型而维持高压的高压吹塑时间和(3)减少空气压力的同时吹入空气进行空气循环的空气循环时间进行掌握。阶段性(一阶段)地减少压力的情况下，以(1)上升到规定压力的时间，(2)为了吹塑成型而维持高压的高压吹塑时间和(3)将压力降至中压(例如约10～20MPa)维持中压状态进行空气循环的空气循环时间(从降压开始到维持中压结束为止)进行掌握。
本发明与不进行空气循环的方法比较虽然增加了(3)的空气循环时间，但因为可缩短(2)的高压吹塑时间，因此从二次吹塑成型工序的整体来看，可缩短二次吹塑成型的吹塑时间。且高压吹塑时间为可得到良好赋型性的合适的时间。
本发明的二次模子温度，可不需要在一阶段升至双向拉伸吹塑成型的上述迄今为止的方法中的如二次模子温度的高温(140～150℃)，而在105℃左右，即可制造具有耐热性能的瓶。
在上述点之外，二次吹塑成型可使用公知的吹塑成型的方法。
如上述，本发明与迄今为止的方法相比，可在更短时间内制造具有优良的耐热性能，且赋型性优良的以PET为主要材料的瓶，这可以有如下理由，由于在二次吹塑中进行空气循环，因此在二次模子内形成的成型物的内部发生空气的对流，成型物内面由于对流而冷却，成型物内面硬化，从而使成型物保持形状，得到赋型性优良的成型物。
由于进行空气循环而使赋型性优良，因此可缩短上述高压吹塑时间(维持高压的时间)，从整体来看可缩短吹塑时间，从而可提高生成效率。
另外，由于加热收缩工序中，在加热一次中间成型物提高结晶密度的同时，内部应力减小，从而可获得高的耐热性能。因此，在二次吹塑成型中使用的二次模子的温度可不需高温即可得到耐热性能优良的瓶。这样即可缩短二次模子升温所需要的时间，加之上述高压吹塑成型时间的缩短，具有优良的耐热性能及赋型性的瓶在短时间内即可制造。
本发明的方法不仅限于饮料用瓶的制造，还可适用于其它容器的制造。
实施例
如下述在实施例及比较例中，各制成10个瓶
比较例1
通过将PET进行注射成型，准备10个预成型物。
将该预成型物加热到110℃，用一次模子进行一次吹塑成型，得到一次中间成型物。一次模子的温度为160℃，空气吹塑的时间为如表1所示的2.95秒。
将该一次中间成型物从一次模子取出，加热到185℃，使其热收缩，得到二次中间成型物。
将该二次中间成型品加热到160℃，用二次模子进行二次吹塑成型，得到最终制品。二次模子的温度为105℃，空气温度为25℃，用高压(39MPa)进行空气吹塑的时间为如表1所示的2.85秒。在该比较例的二次吹塑成型中，没有进行空气循环。
分别测定得到的10个最终制品的总高度及容量，求得其平均值，同时求得总高度及容量的标准偏差。研究其赋型性。表1表示该结果。
另外，测试了得到的最终制品的耐热性能。耐热性能是通过在容器内装入93℃的热水，塞紧塞子，用75℃的热水进行3分钟喷淋后，通过目视确认变形情况。结果如表1所示。
实施例1
在二次吹塑成型中，除在减少高压吹塑时间的同时，进行空气循环之外，以与比较例1相同的方法制得10个最终制品。
空气循环是将压力从高压(39MPa)降至25.3MPa，维持该压力(从压力下降开始到维持压力结束的时间为0.2秒)，再将压力从25.3MPa降至16.6MPa，维持该压力(从压力下降开始到维持压力结束的时间为0.1秒)，之后进行排气。即，空气循环的时间合计为0.3秒。
二次吹塑成型中的高压吹塑时间及空气循环时间、赋型性、耐热性能的结果如表1所示。
实施例2～4
变化二次吹塑成型中的高压吹塑时间，另外，减少一次吹塑成型中的吹塑时间，除此之外，各实施例以与实施例1相同的方法制得10个最终制品。
一次吹塑成型中的吹塑时间、二次吹塑成型中的高压吹塑时间、二次吹塑成型中的空气循环时间、赋型性、耐热性能的结果如表1所示。
另外，实施例4的高压吹塑时间不能作为可得到良好的赋型性的合适时间，需加以注意。因此，仅在高压下的吹塑时间方面，将实施例4作为比较例掌握。
                                                表1
  一次吹塑吹塑时间        二次吹塑吹塑时间   赋型性(总高度)   赋型性(容量)   耐热性能
  高压吹塑时间   空气循环时间   合计   平均值   标准偏差   平均值   标准偏差
  比较例1   2.95秒   2.85秒   无   2.85秒   253.18mm   0.20   914.09ml   3.46   变形无
  实施例1   2.95秒   2.55秒   0.3秒   2.85秒   253.14mm   0.12   924.82ml   1.09   变形无
  实施例2   2.20秒(-0.75秒)   1.80秒   0.3秒   2.10秒(-0.75秒)   253.07mm   0.07   921.16ml   1.33   变形无
  实施例3   1.70秒(-1.25秒)   1.30秒   0.3秒   1.60秒(-1.25秒)   253.07mm   0.09   918.58ml   1.53   变形无
  实施例4   1.45秒(-1.50秒)   1.05秒   0.3秒   1.35秒(-1.50秒)   253.01mm   0.07   919.59ml   2.03   变形无
将比较例1与实施例1进行比较表明，在二次吹塑成型中虽然减少了高压吹塑时间，但通过进行空气循环，在二次吹塑成型中的总吹塑时间没有变化的状态下，总高度的标准偏差变小，容量的标准偏差显著改善，赋型性得到显著改善。另外，也充分确保了耐热性能。
实施例2～3的结果表明，减少二次吹塑成型中的高压吹塑时间，再减少一次吹塑成型中的高压吹塑时间，总高度的赋型性得到改善。结果还表明如果使用实施例3的条件，比较例1的一次吹塑时间可从2.95秒缩短到1.70秒，二次吹塑成型时间从2.85秒缩短到1.60秒，以整体来看循环上升了约43％。
实施例4表明总高度的赋型性得到的改善。
本发明通过在二次吹塑成型中进行空气循环，使成型瓶内部的空气流动，从内部使成型瓶冷却，从而抑制了结晶的过度成长，因此使赋型性得到改善。由于赋型性的改善，制品的尺寸大小的分散得到控制，从而可达到减少不良制品的目的，也可提高瓶制造的价格性能比。
另外，由于本发明缩短了高压吹塑时间，因此可缩短最终制得瓶的成型时间，提高循环率，从而可提高生产效率。

Claims (3)

1.一种以聚对苯二甲酸乙二醇酯树脂为主要材料的瓶的制造方法，该方法包括下述工序：
使用一次模子，通过以维持高压状态的高压吹塑时间，向以聚对苯二甲酸乙二醇酯树脂为主要材料的预成型物中吹入高压流体，进行一次双向拉伸吹塑成型，形成一次中间成型物，
将上述一次中间成型物加热，使其热收缩、形成二次中间成型物，
使用二次模子，将上述二次中间成型物进行二次吹塑成型，
在上述二次吹塑成型中，以维持高压状态的高压吹塑时间，将高压流体吹入二次中间成型物内使其膨胀之后，再将流体吹入成型物内并使流体循环从而使成型物冷却。
2.根据权利要求1所述的方法，其特征在于，所述高压吹塑时间为适合于得到良好赋型性的时间。
3.根据权利要求1所述的方法，其特征在于，吹入高压流体进行膨胀之后再吹入成型物内的流体的压力比所述高压流体的压力低。
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EP1424187B1 (en) 2012-06-13
WO2003011569A1 (fr) 2003-02-13
CA2455873C (en) 2010-09-21
EP1424187A1 (en) 2004-06-02
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US7485251B2 (en) 2009-02-03
KR20040020041A (ko) 2004-03-06

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