CN112074391A - 塑料瓶用预塑形坯的涂布方法 - Google Patents

塑料瓶用预塑形坯的涂布方法 Download PDF

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CN112074391A
CN112074391A CN201980030306.2A CN201980030306A CN112074391A CN 112074391 A CN112074391 A CN 112074391A CN 201980030306 A CN201980030306 A CN 201980030306A CN 112074391 A CN112074391 A CN 112074391A
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preform
coating
solution
pva
plastic bottle
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西山优范
泊一朗
山根亮
铃木秀幸
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Suntory Holdings Ltd
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Abstract

本发明可在狭缝式涂布中，在形成于塑料瓶用预塑形坯的外表面上的粘底层之上涂布PVA溶液后进行加热时，抑制PVA膜的收缩。具体而言，在PVA溶液中添加有硅氧烷等流平剂。

Description

塑料瓶用预塑形坯的涂布方法
技术领域
本发明涉及塑料瓶用预塑形坯的涂布方法，即使在形成于塑料瓶用预塑形坯的外表面上的粘底层之上涂布聚乙烯醇(以下简称为PVA)溶液后进行加热，也可抑制PVA膜的收缩。
背景技术
现今，饮料、食品(以下也称为饮料等)用的聚对苯二甲酸乙二醇酯制的塑料容器(以下也称为PET瓶)已被广泛使用，该PET瓶是在预塑形坯的形态下被供给到制瓶机，并通过吹塑成形而制造。
公知有下述情况，即，在这样的PET瓶的表面上应用有阻透涂层，可减少气体尤其是氧气、二氧化碳的向容器内外的透过，由此可改善填充在瓶内部的饮料等的保存寿命。
例如，在以下的专利文献1中公开有下述内容，即，使用有PVA来作为PET瓶上的阻气层，并使用有包含聚乙烯醇缩丁醛(以下简称为PVB)的追加的顶涂层来改善阻透涂层的耐水性。这样的多层涂层显示有良好的对氧气及二氧化碳的阻透性能、耐划伤性，且由于该阻透涂层为水溶性，因此可在对该顶涂层进行机械破坏后回收利用。
用于软饮料的PET瓶通常是由所谓的预塑形坯通过注塑拉伸吹塑成形而制造。通常，在这样的吹塑法中，预塑形坯膨胀成比原来的体积更大10倍，其结果，在预塑形坯的表面上层状化的涂层显著变薄。因而，最终得到的阻透涂层的机械及化学稳定性很重要。
因而，在阻透涂层应用前，对预塑形坯的表面进行化学或物理的前处理也很重要，已知有在阻透涂布前通过等离子体、电晕或电子射线、火炎、氯、氟、化学蚀刻等对基材进行前处理的情况。
此外，消费者及制造业者是希望在不改变PET瓶的厚度、组成的情况下延长填充于PET瓶的饮料等的贮藏寿命。
在这样的现有技术的状况下，在以下的专利文献2中提出有下述内容，即，通过在PET及聚丙烯(以下称为PP)容器的表面上依次涂布PVB、PVA及PVB，可在预塑形坯表面上形成耐吹塑成形的机械及化学上稳定的阻透涂层。
并且，在以下的专利文献3中提出有下述内容，即，在使预塑形坯的筒状主体部水平旋转的同时，在该筒状主体部上形成PVA涂层，并接下来在其上形成PVB涂层，且在以下的专利文献4中提出有下述内容，即，在PET瓶上层叠有阻气涂层树脂层叠体，所述阻气涂层树脂层叠体层叠有由规定的聚乙烯醇缩醛类树脂构成的层。
此外，在以下的专利文献5及6中提出有下述涂布方法(狭缝式)，即，为了在降低形成在预塑形坯上的涂层的膜厚的不均的同时，抑制在涂布于预塑形坯的涂布液中产生气泡，而在水平方向上保持预塑形坯，并使该预塑形坯绕轴线旋转，而后使涂布液从点胶机的狭缝朝向旋转中的预塑形坯吐出成面状的涂布方法。
专利文献
专利文献1：国际公开第03/037969号公报
专利文献2：日本国特开2012-250771号公报
专利文献3：日本国特开2014-151632号公报
专利文献4：日本国特开2014-151631号公报
专利文献5：日本国特开2017-65149号公报
专利文献6：日本国特开2017-64640号公报
发明内容
在预塑形坯涂布技术中，在内容物为碳酸时，由于作用有因经时变化而导致的内容液中的碳酸气向外逸出的力，因此仍然存在有瓶外面的涂布膜(阻透/顶涂层)发生剥离(脱层)这样的问题。
对此，本发明者近来发现，通过在预塑形坯的外表面和阻透层之间形成粘底层，可显著抑制脱层的产生。另一方面，本发明者发现，虽然通过利用狭缝式来涂布预塑形坯，可在降低形成在预塑形坯上的涂层的膜厚的不均的同时，抑制在涂布于预塑形坯的涂布液中产生气泡，但通过这样的方式，产生有下述这样的现象，即，当在粘底层之上涂布PVA后进行加热时，则PVA膜向中央收缩。
因而，本发明所要解决的技术问题是，在狭缝式涂布中，在形成于塑料瓶用预塑形坯的外表面上的粘底层之上涂布PVA溶液后进行加热时，抑制PVA膜的收缩。
本发明者们为了解决这样的课题而进行了深入研究并重复进行了实验，结果发现，通过向PVA溶液添加硅氧烷等流平剂，即使在形成于塑料瓶用预塑形坯的外表面上的粘底层之上涂布PVA溶液后进行加热，也可抑制PVA膜的收缩，从而完成了本发明。
本发明如下。
(1)一种塑料瓶用预塑形坯的涂布方法，包含：在所述预塑形坯的外表面上涂布粘底涂层剂并使其干燥来形成粘底层的工序；及在所述粘底层之上涂布聚乙烯醇(PVA)溶液并使其干燥来形成阻透层的工序，其特征在于，所述涂布PVA溶液的工序还包含：在水平方向上保持所述预塑形坯且使所述预塑形坯绕所述预塑形坯的轴线旋转的工序；及使所述溶液从点胶机的狭缝朝向旋转中的预塑形坯吐出成面状的工序，所述PVA溶液的吐出方向为所述预塑形坯的外周面的法线方向，而且所述PVA溶液包含流平剂。
(2)根据1所述的方法，其特征在于，所述粘底涂层剂包含聚酯类聚氨酯树脂。
(3)根据2所述的方法，其特征在于，所述聚酯类聚氨酯树脂具有约65℃～小于约90℃的玻璃化温度(Tg)。
(4)根据2或3所述的方法，其特征在于，所述聚酯类聚氨酯树脂具有约80℃～约85℃的玻璃化温度(Tg)。
(5)根据1～4中任一所述的方法，其特征在于，所述流平剂为硅氧烷。
(6)根据1～5中任一所述的方法，其特征在于，还包含在所述阻透层之上涂布聚乙烯醇缩丁醛(PVB)溶液并使其干燥来形成保护层的工序。
(7)一种塑料瓶用预塑形坯的制造方法，其特征在于，包含通过1～6中任一所述的方法对塑料瓶用预塑形坯进行涂布的工序。
(8)一种塑料瓶的制造方法，其特征在于，包含对通过7所述的方法而制造的塑料瓶用预塑形坯进行吹塑成形的工序。
通过本发明，即使在使用狭缝式涂布的情况下，即使在粘底层之上涂布PVA溶液后进行加热，也可抑制PVA膜的收缩。
附图说明
图1是本发明的塑料瓶的制造方法的示意图。
图2是本发明的实施方式所涉及的预塑形坯涂布装置的主要部分的示意主视图。
图3是对涂布液进行涂布时的预塑形坯涂布装置的示意局部侧视图。
具体实施方式
本说明书中，术语“塑料瓶”是指，包含聚对苯二甲酸乙二醇酯(PET)、聚丙烯(PP)及聚乙烯(PE)制的瓶，而不局限于PET瓶。
在本发明所涉及的塑料瓶用预塑形坯的涂布方法中，通过在预塑形坯的外表面上涂布粘底涂层剂并使其干燥，可在该预塑形坯的外表面上形成包含粘底涂层剂的粘底层。
虽然上述粘底涂层剂不受特别限制，但优选为聚酯类聚氨酯树脂。聚酯类聚氨酯树脂可由聚酯多元醇与聚异氰酸酯根据需要在低分子的二醇、二胺等的存在下进行反应来制造。所述聚酯类聚氨酯树脂典型而言具有约65℃～小于约90℃的玻璃化温度(Tg)，优选具有约80℃～约85℃的玻璃化温度(Tg)，且优选为水分散性。作为这样的聚酯类聚氨酯树脂，例如可列举TAKELAC(注册商标)W-5030(三井化学株式会社)、WS-5000(三井化学株式会社)、WS-5984(三井化学株式会社)。
对于粘底涂层剂的涂布，除浸渍(dipping)式、喷射式、涂布机式及转印式这样的本领域周知的涂布方法以外，例如可使用以下说明的狭缝式。
在本发明所涉及的塑料瓶用预塑形坯的涂布方法中，通过在所述粘底层之上涂布PVA溶液并使其干燥，可形成阻透层。
在PVA溶液的制备中，作为溶剂，例如可使用水、甲醇、乙醇、IPA、MEK、丙酮、乙二醇、三乙二醇、甘油、乙酰胺、二甲胺、二甲基乙酰胺、二甲基亚砜、环己酮、四氢呋喃、DMSO、吡啶及/或它们的组合。溶液中的PVA的浓度优选为约1～约30重量％。
阻透层(即PVA涂膜的膜厚)例如依赖于PET瓶所要求的阻气性能，例如可通过以吹塑成形后的PET瓶上的膜厚0.01～5μm为基准，由对PET瓶的延伸倍率5倍～15倍进行反算来算出。例如，如果延伸倍率为15倍，则预塑形坯上的膜厚计算为0.15～75μm。
在本发明所涉及的塑料瓶用预塑形坯的涂布方法中，是通过狭缝式涂布来进行PVA溶液的涂布。在专利文献5及6中详细公开有狭缝式涂布，是通过在水平方向上保持预塑形坯，使该预塑形坯绕轴线旋转，而后使涂布液从点胶机的狭缝朝向旋转中的预塑形坯吐出成面状来实现。具体而言，使用了图2及3所示的预塑形坯涂布装置5来进行狭缝式涂布。
具体而言，预塑形坯涂布装置5构成为，通过在外表面上形成有粘底层的预塑形坯1之上涂布PVA溶液并使其干燥，而在粘底层之上形成阻透层。因此，预塑形坯涂布装置5具备将PVA溶液涂布在预塑形坯1上的点胶机6、使涂布的PVA溶液干燥的干燥机7。干燥机7被配置成距点胶机6离开。优选将干燥机7配置成在水平方向上距点胶机6离开。
预塑形坯涂布装置5还具备运送预塑形坯1的运送部8。运送部8使预塑形坯1从点胶机6的位置朝向干燥机7的位置移动。例如，运送部8可为传送带。运送部8具有2个带轮81a、81b、挂在带轮81a、81b上的带82。带轮81a、81b被可旋转地固定于在水平方向上延伸存在的带轮支撑板20上。带轮支撑板20被在铅垂方向上延伸存在的两个支柱21a、21b支撑。带轮81a、81b的任意一方被马达(未图示)驱动。通过使带轮81a、81b的任意一方向图2中的顺时针旋转，可向图2中的顺时针驱动带82。由此，运送部8可运送预塑形坯1。另外，带轮的数量也可为3个以上。此外，只要可运送预塑形坯1，则运送部8也可为传送链等其他机构。
预塑形坯涂布装置5还具备，在水平方向上保持预塑形坯1的同时使预塑形坯1绕预塑形坯1的轴线A旋转的旋转保持部9。旋转保持部9具有把持预塑形坯1的口部1a的卡盘91、与卡盘91连结的旋转轴92。
通过用卡盘91把持预塑形坯1的口部1a，旋转保持部9可将预塑形坯1保持在水平方向上。因而，预塑形坯1被旋转保持部9单侧支撑。卡盘91例如为用空气来吸附预塑形坯1的真空吸盘或者机械性把持预塑形坯1的机械卡盘。例如，卡盘91把持预塑形坯1的口部1a的内侧，但卡盘91也可以把持预塑形坯1的口部1a的外侧。
旋转轴92被马达(未图示)驱动而与卡盘91一起旋转。旋转轴92的轴线与预塑形坯1的轴线A同轴。因而，通过使旋转保持部9旋转，可以使预塑形坯1绕预塑形坯1的轴线A旋转。此外，旋转保持部9可通过控制马达的转速来控制预塑形坯1的转速。预塑形坯1的转速例如为30rpm～240rpm。如图2所示，旋转保持部9与带82连结。因此，通过使旋转保持部9移动，运送部8可运送预塑形坯1。此外，预塑形坯涂布装置5还可以具备对供给到点胶机6的涂布液进行脱气的脱气组件。
虽然通过使用这样的装置来进行涂布，可在降低形成在预塑形坯上的涂层的膜厚的不均的同时，抑制在涂布于预塑形坯的涂布液中产生气泡，但产生有下述这样的问题，即，由于当在粘底层之上涂布PVA后进行加热时，则PVA膜向中央收缩，因此无法均匀地涂布。然而，通过在PVA溶液中添加流平剂可避免这样的涂布不良。
可用于本发明的流平剂不受特别限制，只要可赋予PVA溶液以均匀的涂布性即可，但优选硅氧烷、聚硅氧烷类树脂、氟类树脂。作为这样的流平剂，例如可列举DYNOLTM 980(Air Products公司)、KP-104及KP-110(信越硅胶公司)、MEGAFACE F-477及RS-72-K(DIC株式会社)等。
PVA溶液中的流平剂的浓度典型而言为约0.0001～约0.1重量％，优选为约0.001～约0.01重量％，最优选为约0.004～约0.006重量％。
虽然PVA可使基材的透气性(尤其是O2及CO2)显著降低，并由此可改善包装的食品、软饮料或啤酒等饮料等的保存寿命，但仅由PVA构成的涂层的使用则因其吸湿性而受到限制。因此，已发现有聚乙烯醇缩醛例如PVB适于用作PVA层(阻透层)的顶涂层(保护层)。如以下的化学式所示，PVA聚合物和PVB聚合物具有相似的聚合物主链，且在广泛的混合物中具有相容性。
(化学式1)
Figure BDA0002760592240000071
(化学式2)
Figure BDA0002760592240000072
因而，在本发明所涉及的方法中，优选在阻透层之上涂布PVB溶液并使其干燥来形成保护层。
在PVB溶液的制备中，作为溶剂，例如可使用甲醇、乙醇、n-丙醇、IPA、n-丁醇、辛醇、甲基溶纤剂、乙基溶纤剂、丁基溶纤剂、丙酮、MEK、MIBK，环己酮、异佛尔酮、N，N-二甲基乙酰胺、N，N-二甲基甲酰胺、N-甲基-2-吡咯烷酮、乙酸甲酯、乙酸乙酯、乙酸异丙酯、乙酸-n-丁酯、乙醚、二恶烷、四氢呋喃、甲苯、二甲苯、吡啶、二甲基亚砜、乙酸、松油醇、丁基卡必醇、丁基卡必醇乙酸酯及/或它们的组合。溶液中的PVB的浓度优选为约0.1～约50重量％。
保护层(即PVB涂膜的膜厚)的膜厚可通过以吹塑成形后的PET瓶上的膜厚0.01～5μm为基准，由对PET瓶的延伸倍率5倍～15倍进行反算来算出。例如，如果延伸倍率为15倍，则预塑形坯上的膜厚计算为0.15～75μm。
对于PVB溶液的涂布，除浸渍(dipping)式、喷射式、涂布机式及转印式这样的本领域周知的涂布方法以外，例如可使用上述的狭缝式。
只要可形成各层，则上述各工序中的干燥单元不受特别限制，但优选通过加热器及通风(常温或热风)来实施。通过选择具有适于溶剂即水及羟基的吸收波长的加热波长的热源，进行从膜的内部的加热，可有效缩短涂布溶液的加热干燥时间。根据这一点，优选使用可产生近红外线～中红外线的碳加热器。此外，为了高效去除蒸发的水且不使膜冷却，也可在使用产生近红外线～中红外线的碳加热器的同时，并用远红外线加热器、通风(常温)或吹热风。
上述各工序中的干燥温度优选为常温～80℃。在100℃以上时，可能会导致溶液沸腾，此外，当超过80℃时，则可能会导致基材因过度加热而白化或是变形。
在本发明的其他形态中，提供有使用了本发明所涉及的预塑形坯的涂布方法的塑料瓶用预塑形坯的制造方法。
通过对所得到的预塑形坯进行拉伸吹塑成形，可制造塑料瓶。因而，在本发明的进一步其他形态中，提供有一种塑料瓶的制造方法，其包含对通过本发明所涉及的方法而制造的塑料瓶用预塑形坯进行吹塑成形的工序。
通过这样的方法，可实现塑料瓶的制造，所述塑料瓶在瓶外表面上具有均匀地形成有粘底层、阻透层及/或保护层的涂膜，且不会伴有白化部分。
实施例
(实施例1：PVA狭缝式涂布不良的评价)
在用大气等离子体照射表面改性装置(Wedge株式会社制，PS-1200AW)对500ml用PET瓶用预塑形坯(24g)的外表面进行约3秒钟等离子体照射后，在烤箱中加热至50℃。其后，将预塑形坯浸渍在TAKELAC(注册商标)W-5030(三井化学株式会社)等各品牌的粘底涂层剂中1次，在50℃的烤箱中干燥约30分钟，而形成粘底层。干燥后，将预塑形坯暂时冷却至常温的状态。将预塑形坯安装在涂布实验装置的卡盘上，使其以60rpm旋转。向狭缝式涂布装置的料箱中加入约500ml的含流平剂的PVA水溶液，将兵神点胶机(Heishin Dispenser)的涂布量设定成300mg，将涂布宽度设定成40mm，对旋转中的预塑形坯进行1次涂布。含流平材料的PVA水溶液是通过下述内容而制备，即，向具备加热装置及搅拌机的烧杯中加入PVA粉末(株式会社Kuraray制，EXCEVAL(注册商标)HR-3010)，加入常温的水使其成为浓度10重量％，在搅拌的同时加热至溶液温度95℃，并持续搅拌至PVA完全溶解为止，其后，作为流平剂而添加DYNOLTM980(Air Products公司)并使其成为0.005重量％，在常温下搅拌30分钟。涂布结束后，将预塑形坯运送到设定温度设定成300℃的加热器中，使其干燥1分钟。干燥后，以目视确认PVA溶液是否涂匀涂布。
对于用浸渍式代替狭缝式来进行涂布的情况、不添加流平剂且用浸渍式进行涂布的情况、添加IPA来代替流平剂且用狭缝式进行涂布的情况、添加流平剂和IPA且用狭缝式进行涂布的情况，也进行了与上述相同的试验。
以下的表1示出结果。
(表1)
涂布方式 IPA(％) 流平剂(ppm) PF涂布性(收缩)
浸渍 ○
浸渍 5 ○
狭缝 ×
狭缝 5 ○
狭缝 5 5 ○
狭缝 5 ○
如表1所示，在用狭缝式形成粘底层后，在不添加流平剂而涂布PVA时，产生有PVA的收缩，但在添加了流平剂且用狭缝式进行涂布时、添加了流平剂和IPA且用狭缝式进行涂布时，未产生PVA的收缩。
另外，在对用狭缝式涂布的预塑形坯进行吹塑而形成的PET瓶的外观进行确认时，虽然在添加了IPA时均见有白化，但在仅添加了流平剂时未见白化。

Claims (8)

1.一种塑料瓶用预塑形坯的涂布方法，包含：在所述预塑形坯的外表面上涂布粘底涂层剂并使其干燥来形成粘底层的工序；及在所述粘底层之上涂布聚乙烯醇PVA溶液并使其干燥来形成阻透层的工序，其特征在于，
所述涂布PVA溶液的工序还包含：在水平方向上保持所述预塑形坯且使所述预塑形坯绕所述预塑形坯的轴线旋转的工序；及使所述溶液从点胶机的狭缝朝向旋转中的预塑形坯吐出成面状的工序，
所述PVA溶液的吐出方向为所述预塑形坯的外周面的法线方向，而且所述PVA溶液包含流平剂。
2.根据权利要求1所述的方法，其特征在于，所述粘底涂层剂包含聚酯类聚氨酯树脂。
3.根据权利要求2所述的方法，其特征在于，所述聚酯类聚氨酯树脂具有约65℃～小于约90℃的玻璃化温度Tg。
4.根据权利要求2或3所述的方法，其特征在于，所述聚酯类聚氨酯树脂具有约80℃～约85℃的玻璃化温度Tg。
5.根据权利要求1～4中任意1项所述的方法，其特征在于，所述流平剂为硅氧烷。
6.根据权利要求1～5中任意1项所述的方法，其特征在于，还包含在所述阻透层之上涂布聚乙烯醇缩丁醛PVB溶液并使其干燥来形成保护层的工序。
7.一种塑料瓶用预塑形坯的制造方法，其特征在于，包含通过权利要求1～6中任意1项所述的方法对塑料瓶用预塑形坯进行涂布的工序。
8.一种塑料瓶的制造方法，其特征在于，包含对通过权利要求7所述的方法而制造的塑料瓶用预塑形坯进行吹塑成形的工序。
CN201980030306.2A 2018-05-10 2019-05-10 塑料瓶用预塑形坯的涂布方法 Pending CN112074391A (zh)

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