CN112074390A - 塑料瓶用预塑形坯及其制造方法 - Google Patents

塑料瓶用预塑形坯及其制造方法 Download PDF

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CN112074390A
CN112074390A CN201980030288.8A CN201980030288A CN112074390A CN 112074390 A CN112074390 A CN 112074390A CN 201980030288 A CN201980030288 A CN 201980030288A CN 112074390 A CN112074390 A CN 112074390A
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preform
plastic bottle
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barrier layer
cylindrical body
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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

本发明提供一种可抑制脱层的聚酯瓶用预塑形坯及该预塑形坯的制造方法。具体而言，是在预塑形坯的外表面上形成包含聚酯类聚氨酯树脂的粘底层。

Description

塑料瓶用预塑形坯及其制造方法
技术领域
本发明涉及可抑制脱层的塑料瓶用预塑形坯及其制造方法。
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，使用有聚乙烯醇(以下简称为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，在可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。
然而，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。
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
本发明所要解决的技术问题是，提供一种可抑制脱层的聚酯瓶用预塑形坯及该预塑形坯的制造方法。
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，通过在预塑形坯的外表面和阻透膜之间，插入聚酯类聚氨酯树脂来作为粘底涂层剂，可显著抑制脱层的产生，从而完成了本发明。
即，本发明如下。
(1)一种塑料瓶用预塑形坯，由作为塑料瓶的开口的口部、圆筒状主体部、对该圆筒状主体部进行封闭的底部构成，其特征在于，在该预塑形坯的外表面上具有形成有包含聚酯类聚氨酯树脂的粘底层的涂膜。
(2)根据1所述的预塑形坯，其特征在于，在所述粘底层之上形成有包含聚乙烯醇(PVA)的阻透层。
(3)根据2所述的预塑形坯，其特征在于，在所述阻透层之上形成有包含聚乙烯醇缩丁醛(PVB)的保护层。
(4)根据1～3中任一所述的预塑形坯，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)。
(5)根据1～4中任一所述的预塑形坯，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)。
(6)一种塑料瓶，由作为塑料瓶的开口的口部、圆筒状主体部、对该圆筒状主体部进行封闭的底部构成，其特征在于，在该预塑形坯的外表面上具有形成有包含聚酯类聚氨酯树脂的粘底层的涂膜。
(7)根据6所述的塑料瓶，其特征在于，在所述粘底层之上形成有包含聚乙烯醇(PVA)的阻透层。
(8)根据7所述的塑料瓶，其特征在于，在所述阻透层之上形成有包含聚乙烯醇缩丁醛(PVB)的保护层。
(9)根据6～8中任一所述的塑料瓶，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)。
(10)根据6～9中任一所述的塑料瓶，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)。
(11)一种塑料瓶用预塑形坯的制造方法，其特征在于，包含：准备预塑形坯的工序，所述预塑形坯由作为塑料瓶的开口的口部、圆筒状主体部、对该圆筒状主体部进行封闭的底部构成；及形成粘底层的工序，在所述预塑形坯的外表面上涂布包含聚酯类聚氨酯树脂的粘底涂层剂，并使其干燥。
(12)根据11所述的方法，其特征在于，还包含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。
(13)根据12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。
(14)根据11～13中任一所述的方法，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)。
(15)根据11～14中任一所述的方法，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)。
(16)一种塑料瓶的制造方法，其特征在于，包含对通过11～15中任一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。
(17)一种塑料瓶用预塑形坯，其特征在于，通过11～15中任一所述的方法而制造。
(18)一种塑料瓶，其特征在于，通过16所述的方法而制造。
根据本发明，可提供一种可抑制脱层的产生的塑料瓶用预塑形坯及该预塑形坯的制造方法。
附图说明
图1是本发明的塑料瓶的制造方法的示意图
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。
在本发明的1个形态中，提供有一种塑料瓶用预塑形坯，由作为塑料瓶的开口的口部、圆筒状主体部、对该圆筒状主体部进行封闭的底部构成，其特征在于，该预塑形坯的外表面上具有形成有包含聚酯类聚氨酯树脂的粘底层的涂膜。
优选在本发明所涉及的预塑形坯上，在粘底层之上形成有包含聚乙烯醇(PVA)的阻透层，并且在阻透层之上形成有包含聚乙烯醇缩丁醛(PVB)的保护层。
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。本发明中使用的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)。本发明中使用的聚酯类聚氨酯树脂优选为水分散性。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)。
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。然而，仅由PVA构成的涂层的使用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 BDA0002760553470000051
(化学式2)
Figure BDA0002760553470000052
本发明的进一步的形态中，提供有一种塑料瓶用预塑形坯的制造方法，其特征在于，包含：准备预塑形坯的工序，所述预塑形坯由作为塑料瓶的开口的口部、圆筒状主体部、对该圆筒状主体部进行封闭的底部构成；及形成粘底层的工序，在所述预塑形坯的外表面上涂布包含聚酯类聚氨酯树脂的粘底涂层剂，并使其干燥。
优选本发明所涉及的方法还包含在粘底层之上涂布PVA溶液并使其干燥来形成阻透层的工序及在阻透层之上涂布PVB溶液并使其干燥来形成保护层的工序。
上述方法为本发明所涉及的预塑形坯的制法，并使用有上述的粘底涂层剂、PVA及PVB。
作为可用于PVA溶液的制备的溶剂，例如可列举水、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。
作为可用于PVB溶液的制备的溶剂，例如可列举甲醇、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。
优选溶液中的PVA的浓度为约1～约30重量％，且优选溶液中的PVB的浓度为约0.1～约50重量％。
对于上述各工序中的涂布，除浸渍(dipping)式、喷射式、喷雾式、涂布机式及转印式这样的本领域周知的涂布方法以外，例如可使用用有狭缝的点胶机涂布方法。
在专利文献5及6中详细公开有狭缝式的涂布方法，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，而后使涂布液从涂胶机(dispenser)的狭缝朝向旋转中的预塑形坯吐出成面状来实现。虽然通过使用这种方式的涂布方法，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，当在粘底层之上涂布PVA等阻透材料时，则无法均匀涂布。然而，通过在阻透材料中添加流平剂，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DYNOL-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。
在本发明所涉及的预塑形坯的制造方法中，优选在粘底涂层剂的涂布之前，对所述预塑形坯表面进行等离子体、电晕或电子射线处理。通过这样的前处理，可强化粘底层向基材的附着。但是，这样的前处理是任意附加的工序，在本发明中，在几乎所有的情况下，即使不进行前处理，也可制造出可被拉伸吹塑成形的具有机械性稳定的涂层的预塑形坯，且不会伴有裂纹、离层的产生。
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。
通过对本发明所涉及的预塑形坯进行拉伸吹塑成形，可制造塑料瓶。因而，本发明的进一步其他形态中，提供有一种通过对发明所涉及的塑料瓶用预塑形坯进行吹塑成形而得到的塑料瓶及其制造方法。
实施例
(实施例1：粘底涂层剂的脱层的抑制)
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，将预塑形坯在各品牌的粘底涂层剂中浸渍1次，在50℃的烤箱中干燥约30分钟，以便形成粘底层。干燥后，在保持在50℃的同时，将预塑形坯在10％的PVA溶液中浸渍1次，并使其在50℃的烤箱中干燥1小时。PVA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％，而后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。重复上述向PVA溶液的浸渍及干燥工序，以便形成阻透层。干燥后，在保持在50℃的同时，将预塑形坯在PVB溶液中浸渍1次，而后使其在50℃的烤箱中干燥30分钟，以便形成保护层。PVB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PVB粉末(株式会社Kuraray制，MOWITAL(注册商标)B-30HH，玻璃化温度63℃)，加入常温的乙醇(99.5％)使其成为浓度5重量％，而后在常温下进行搅拌，同时持续搅拌至PVB完全溶解为止。在常规条件下，用拉伸吹塑成形机对具有形成有各层的涂膜的预塑形坯进行拉伸吹塑成形，而制造了PET瓶。向PET瓶中添加柠檬酸和碳酸氢钠，并填充了4.2GV的碳酸水。将填充有碳酸水的PET瓶保管在23℃50％的恒温室内，并确认了有无产生脱层。
以下的表1中示出有使用各粘底涂层剂时的阻透材料(PVA)的涂布性及抗脱层天数。在此，作为粘底涂层剂，除上述的W5030、WS5000以外，使用有三井化学株式会社制的聚乙烯类聚氨酯树脂即W6010、W6020、W6061、WPB341、大阪印刷油墨制造株式会社制的苯乙烯类树脂的STYPOLI、Toyo-morton公司制的聚乙烯亚胺类树脂的AD373MW、大日精化工业公司制的聚丁二烯类树脂的SEIKADYNE、互应化学公司制的聚乙烯类树脂的Z-565、Z-730、Z-687、Z-880、RZ-105。
(表1)
Figure BDA0002760553470000081
已确认聚酯类聚氨酯树脂的且Tg为65℃～小于90℃的WS5000和W5030的抗脱层天数为1个月以上，可耐受实际使用。其中，已确认W5030的抗脱层天数为6个月，涂布剂可长时间不会发生剥离。

Claims (19)

1.一种塑料瓶用预塑形坯，由作为塑料瓶的开口的口部、圆筒状主体部、对该圆筒状主体部进行封闭的底部构成，其特征在于，在该预塑形坯的外表面上具有形成有包含聚酯类聚氨酯树脂的粘底层的涂膜。
2.根据权利要求1所述的预塑形坯，其特征在于，在所述粘底层之上形成有包含聚乙烯醇PVA的阻透层。
3.根据权利要求2所述的预塑形坯，其特征在于，在所述阻透层中还包含流平剂。
4.根据权利要求2或3所述的预塑形坯，其特征在于，在所述阻透层之上形成有包含聚乙烯醇缩丁醛PVB的保护层。
5.根据权利要求1～4中任意1项所述的预塑形坯，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。
6.根据权利要求1～5中任意1项所述的预塑形坯，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。
7.一种塑料瓶，由作为塑料瓶的开口的口部、圆筒状主体部、对该圆筒状主体部进行封闭的底部构成，其特征在于，在该预塑形坯的外表面上具有形成有包含聚酯类聚氨酯树脂的粘底层的涂膜。
8.根据权利要求7所述的塑料瓶，其特征在于，在所述粘底层之上形成有包含聚乙烯醇PVA的阻透层。
9.根据权利要求8所述的塑料瓶，其特征在于，在所述阻透层中还包含流平剂。
10.根据权利要求8或9所述的塑料瓶，其特征在于，在所述阻透层之上形成有包含聚乙烯醇缩丁醛PVB的保护层。
11.根据权利要求7～10中任意1项所述的塑料瓶，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。
12.根据权利要求7～11中任意1项所述的塑料瓶，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。
13.一种塑料瓶用预塑形坯的制造方法，其特征在于，包含：准备预塑形坯的工序，所述预塑形坯由作为塑料瓶的开口的口部、圆筒状主体部、对该圆筒状主体部进行封闭的底部构成；及形成粘底层的工序，在所述预塑形坯的外表面上涂布包含聚酯类聚氨酯树脂的粘底涂层剂，并使其干燥。
14.根据权利要求13所述的方法，其特征在于，还包含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。
15.根据权利要求14所述的方法，其特征在于，所述PVA溶液包含流平剂。
16.根据权利要求14或15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。
17.根据权利要求13～16中任意1项所述的方法，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。
18.根据权利要求13～17中任意1项所述的方法，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。
19.一种塑料瓶的制造方法，其特征在于，包含对通过权利要求13～18中任意1项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。
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