CN1251805A - 聚酯树脂的发泡片 - Google Patents
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Abstract
用于制造饮料和食品用容器的聚酯树脂发泡片,其密度小于700千克/米3,当材料于120℃加热5分钟时结晶度不大于15%。用于制备发泡片的芳族聚酯树脂可与脂族聚酯树脂混合,以便赋予片以生物降解性和/或堆肥处理性。
Description
本发明涉及聚酯树脂的发泡片,这种片可热封,适用于制成饮料和食品的容器,在这种片上,借压力将设计图形压贴在片上,通过折叠得到容器的形状,制成饮料和食品容器。
本发明包括由这些片获得的容器。特别是具有气体屏障性,适合制造用于饮料(如果汁、适中储存期的牛奶、茶等)的容器的片。
目前,仍使用的制造饮料和食品容器(如用于果汁、牛奶或其它)的材料基本上包括功能层的卡纸板,它提供了容器机械性能,特别是刚性;一些情况下,在与饮料或食物接触的一面,有一层粘合在卡纸板上的涂铝的聚乙烯薄膜或类似的聚合物材料的薄片。
用这样的多层材料制得的容器,由于各层的化学性质不同而很难循环再生。
无论从循环再生可以达到的节省金额还是从生态方面考虑,制造食品或饮料容器的材料的循环再生都是极为重要的必需条件。
材料的循环再生可能性是这方面的非常重要的课题。
有使用聚合物材料制造的用于饮料和液体的容器,但是这类聚合物材料不能提供与卡纸板相比的刚性,由于这一原因,它们不适合制造有刚性的容器。用这类材料制得的容器限于小的袋类。
目前试图用聚合物材料制得所需刚性容器的努力仍未能获得成功。
容器的刚性随壁厚变化,更精确地说是随壁厚的立方变化。
使用诸如聚烯烃的聚合物材料制造具有足够刚性的容器意味着容器的壁厚将是不经济的,而且不能加工,因为在容器闭合时会遇到折叠和密封上的困难。
另一种诸如发泡聚苯乙烯的材料不能使用,因为当使其成为薄层时易碎。
由专利文献(US 5,000,991)可知刚性层叠物可制造用于食品的热成形容器,这类层叠物可由发泡的聚酯材料片和发泡聚酯材料的薄膜、或其它聚合物材料制成。由EB-A-836937可知,0.5-1.5毫米厚的半刚性层叠物包括一层密度为0.7-1克/厘米3的聚酯发泡树脂,其上粘合了一层具备气体屏障性能的层,是由不同于聚酯发泡层的聚合物材料制成。
这种层叠物可制造用于包装的热成形制品。
包含聚酯发泡层并能根据压在该材料上的设计图形折叠成容器形状的材料,专利文献中还未见报道。
单层或多层聚合物发泡材料,按设计图样式折痕,通过折叠得到容器形状的能力以及材料可依据这样图形的折叠性构成了采用折痕和折叠技术制造饮料和食品容器的必不可少的要求。
如果压制在材料上的图形在一定时间保持稳定,并且压贴这样的图形时不会发生断裂,即不会损害材料的可折叠性,这类材料适合于折痕。
而且这类材料必须是可热封,能够闭合容器。
目前已意外地发现一种聚酯树脂泡沫的聚合物材料,它适合于制造饮料和食品的容器,满足上述对折痕的要求,并能为组成的卡纸板提供足够的刚性。
本发明的发泡材料包括一种聚酯树脂获得的基本上无定形(含有小于5%的结晶度)发泡片或由其构成的发泡片,其结晶速率使120℃加热5分钟的结晶度不大于15%,较好的不大于10%。
用于制备发泡片的较好的聚酯树脂是共聚对苯二甲酸乙二醇酯,其中约2-20%(摩尔)的对苯二甲酸酯单元被源自间苯二酸和/或萘-二羧酸的单元取代。
较好的聚对苯二甲酸乙二醇酯包含4-10%间苯二酸衍生的单元。
要达到改善发泡片的气体屏障性能的目的,发泡片上可涂布聚酯树脂薄膜或其它具有气体屏障性的材料。
在片覆盖了聚酯薄膜的情况下,通过使薄膜经表面处理提供气体屏障性或通过施用具有气体屏障性的材料如铝和氧化铝以及氧化硅(Al2O3和SiOx),赋予薄膜气体屏障性。
代表性的表面处理是在表面上喷涂一层聚硅酸锂或聚硅酸钾。这种处理可使氧渗透速率非常缓慢,为0.3毫升/米2/24小时/大气压或更小。
根据现有技术施用一层铝和氧化铝和/或氧化硅。
可选择表面处理和沉积屏障材料,并按照能赋予聚酯薄膜一般小于70毫升/米2/24小时/大气压(ASTM 1434)氧渗透性机械薄膜材料和屏障材料的沉积法。在用铝金属化或涂布氧化铝和/或氧化硅的情况下,氧渗透度可降至小于0.3毫升/米2/24小时/大气压。优选小于10毫升/米2/24小时/大气压。用铝金属化的聚酯薄膜可以商品名Nu Roll of Nurol S.p.A.购得(Nu Roll是Nurol S.p.A.的注册商标)。
将具有屏障性能的薄膜粘合在片上时,薄膜未经处理的一面是将与饮料或食品接触的容器内面。
随各种要求,如印刷油墨或其它材料而变,可以使用符合上述要求的薄膜作外层,该外层粘合在作为内层的发泡片上。
具有屏障性能的薄膜或其它薄膜在发泡片上的粘合,可通过胶粘或热叠合或通过共挤出的现有方法来进行。
本发明的发泡片厚度为0.2-3毫米,最好为0.2-1.5毫米。片的密度小于700千克/米3,较好的是10-500千克/米3,最好是100-200千克/米3。
还可以用一层不同于聚酯树脂的可热封的聚合物层覆盖发泡聚酯片。
可根据已有的挤出发泡法制备发泡片。
在USP 5,362,763中揭示了一种较好的方法,该专利的说明在此引用作为参考。
在USP 5,362,763中还揭示了其它的方法,这些专利的说明在此引用作为参考。
发泡片刚性是片厚度的函数:它随厚度增加(不成比例)。使用无机填料(可达约20%(重量))可以提高片的刚性。填料的例子有硅石、氧化铝、二氧化钛、碳酸钙等。
可根据已有的方法,即通过折叠由压制在片上的图形折痕,形成容器的形状,来制造容器。
容器依其最终用途有不同的形状和体积。可以使用立方形、长方形或锥形。用于饮料和果汁容器的体积一般在0.2-2升之间。
制备发泡片的聚酯可通过芳族二羧酸(较好是对苯二甲酸)与2-12个碳原子的二醇(如乙二醇、1,4-丁二醇和1,4-二羟甲基-环己醇)的缩聚获得,较好的聚酯选自聚对苯二甲酸乙二醇酯共聚物,其中有达20%(摩尔)的源自对苯二甲酸酯的单元被源自间苯二酸和/或萘-二羧酸的单元取代。
要使发泡片具有生物降解性和/或堆肥处理性,制备发泡片的聚酯树脂可与10-35%(重量)的可生物降解的脂族聚酯树脂混合,使该混合物在四羧酸二酐(以芳族的为宜)存在下,于固态进行加聚反应。
1,2,4,5-苯四酸酐是较好的二酐,其用量为树脂总重量的0.05-2%。
固态的加聚反应在约150-220℃下进行一定的时间,二酐浓度要大到足以获得特性粘度大于0.7dl/g(于25℃,60/40重量比值的酚和四氯乙烷中测得的粘度)且熔体强度要大到足可使树脂发泡的数值。
特性粘度一般为0.8-1.2dl/g。
合适的熔体粘度大于8厘牛顿(centinewton),较好的大于20厘牛顿。
根据US 5,442,381披露的方法,使用Geottfert毛细管流变仪测定熔体强度,该专利的说明书在此引用作为参考。
脂族聚酯树脂可通过2-22个碳原子的羟基-酸或其内酯或交酯的缩聚,或通过2-22个碳原子的脂族二羧酸与2-22个碳原子的脂族或芳族二醇的缩聚制得。聚己内酯是较好的聚酯。所述聚酯的特点是可生物降解。
由下面的实施例说明本发明,但不构成对本发明的限制。
实施例1
将从筒管取出的0.7毫米厚,密度为180千克/米3,如果于120℃加热时结晶度不大于15%的发泡COPET(共聚对苯二甲酸乙二醇酯,含4%(重量)的间苯二酸)片按设计折痕,折叠后制得平行六面体形状的容器。
用已折痕的片制造用于中等储存期限的牛奶和果汁的容器。
该容器通过热封闭合。封闭是不透气地闭住的,并能够通过撕开或割开或其它方法容易地打开闭合处。
实施例2
用能适应容器循环再生的胶水将具有实施例1所述的特点的PET发泡片粘合到Nurol S.p.A.的Nu Roll金属化薄膜上,薄膜厚度为15微米。
该片可用于制造用于液体的容器。
实施例3
含4%间苯二酸单元的共聚对苯二甲酸乙二醇酯与10%(重量)Union Carbide的聚己内酯UC PCL 787混合,然后在180℃固态进行加聚反应,直到达到0.85dl/g粘度,制得0.7毫米厚,密度为180千克/米3的发泡片,其结晶率为在120℃加热时不大于15%,根据要求的设计压制该片,以折痕出平行六面体形状的容器。
折痕后的片可制造中等储存期限的牛奶和果汁用的容器。
通过热封闭合容器。该闭合能保持不透气的闭合,能够通过撕开或割开或其它方法容易地打开闭合处。容器在正常的堆肥处理条件下堆肥,结果是可以堆肥处理的。
实施例4
用能适应容器循环再生的胶水将具有实施例3所述特点的PET发泡片粘合到Nurol S.p.A.的Nu Roll金属化薄膜上,薄膜厚度为15微米。
该片可用于制造用于液体的容器。
Claims (17)
1.一种适合制造饮料和食品容器的材料,它包括基本为无定形的发泡片,可由密度小于700千克/米3,在120℃加热5分钟时结晶度不大于15%的结晶速率的聚酯树脂制得。
2.如权利要求1所述的材料,其特征在于所述发泡片由含2-20%摩尔的源自间苯二酸和/或萘-二羧酸单元的共聚对苯二甲酸乙二醇酯制得。
3.如权利要求1或2所述的材料,其特征在于所述发泡片的结晶速率为在120℃加热5分钟时结晶度小于10%。
4.如权利要求1-3中任一权利要求所述的材料,其特征在于将所述发泡片粘合到具有气体屏障性能的薄膜上。
5.如权利要求4所述的多层材料,其特征在于所述粘合的聚酯薄膜的氧渗透率小于70毫升/米2/24小时/大气压(根据ASTM 1434测定)。
6.如权利要求5所述的材料,其特征在于所述聚酯薄膜是用铝金属化,或涂有一层氧化铝或氧化硅,或聚硅酸钾或聚硅酸锂。
7.如权利要求3-6中任一权利要求所述的材料,其特征在于所述具有气体屏障性的膜通过使用胶粘或热叠合被粘合到发泡片上。
8.如权利要求1-7中任一权利要求所述的材料,其特征在于所述发泡片的密度为10-500千克/米3。
9.如权利要求1-8中任一权利要求所述的材料,其特征在于所述发泡片的密度为100-200千克/米3。
10.如权利要求1-9中任一权利要求所述的材料,其特征在于所述材料厚度为0.2-3毫米。
11.如权利要求10所述的材料,其特征在于所述材料厚度为0.2-1.5毫米。
12.如权利要求1-10中任一权利要求所述的材料,其特征在于所述发泡片中包含一种无机填料。
13.如权利要求1-12中任一权利要求所述的材料,其特征在于所述发泡片是由混合了10-30%重量的脂族聚酯树脂的芳族聚酯树脂制得。
14.一种饮料或食品容器,它由权利要求1-13中任一权利要求所述的材料制成。
15.如权利要求14所述的容器,其特征在于可以通过热封进行闭合。
16.一种用于果汁或消毒牛奶的容器,可使用权利要求1-13中任一权利要求所述的材料制造,发泡片可粘合到具有相应小于70毫升/米2/24小时/大气压渗透速率的隔氧性的薄膜上。
17.如权利要求16所述的容器,其特征在于粘合到片上的薄膜具有小于10毫升/米2/24小时/大气压的氧渗透速率。
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
IT98MI002078 IT1302278B1 (it) | 1998-09-25 | 1998-09-25 | Materiali multistrato reciclabili in resina poliestere |
ITMI98A002078 | 1998-09-25 | ||
ITMI982081 IT1302281B1 (it) | 1998-09-29 | 1998-09-29 | Foglia espansa in resina poliestere |
ITMI98A002081 | 1998-09-29 | ||
ITMI98A002208 | 1998-10-14 | ||
IT98MI002208 IT1302669B1 (it) | 1998-10-14 | 1998-10-14 | Foglia poliestere espansa compostabile |
Publications (1)
Publication Number | Publication Date |
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CN1251805A true CN1251805A (zh) | 2000-05-03 |
Family
ID=27274103
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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CN99120732A Pending CN1251805A (zh) | 1998-09-25 | 1999-09-24 | 聚酯树脂的发泡片 |
Country Status (17)
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US (1) | US6365249B1 (zh) |
EP (1) | EP0989148B1 (zh) |
JP (1) | JP3549781B2 (zh) |
KR (1) | KR100589081B1 (zh) |
CN (1) | CN1251805A (zh) |
AR (1) | AR023053A1 (zh) |
AT (1) | ATE290563T1 (zh) |
AU (1) | AU764281B2 (zh) |
BR (1) | BR9904333A (zh) |
CA (1) | CA2283039C (zh) |
DE (1) | DE69924063T2 (zh) |
ES (1) | ES2238801T3 (zh) |
HU (1) | HU224201B1 (zh) |
NO (1) | NO319966B1 (zh) |
PL (1) | PL195935B1 (zh) |
RU (1) | RU2183557C2 (zh) |
TW (1) | TWI239969B (zh) |
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CN111559101A (zh) * | 2020-05-15 | 2020-08-21 | 东莞中和生物材料科技有限公司 | 一种由可生物降解材料制成的饮用容器的生产工艺 |
CN112203835A (zh) * | 2018-06-28 | 2021-01-08 | 株式会社Huvis | 包括气体阻隔层的成型体、包括其的包装容器及成型体的制备方法 |
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JP4877906B2 (ja) * | 2005-08-05 | 2012-02-15 | 麒麟麦酒株式会社 | 飲料用又は食品用の密封容器の製造方法 |
EP1790468A1 (en) | 2005-11-24 | 2007-05-30 | Sudnif S. A. | Package, blank and method of producing package |
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US7807260B2 (en) | 2007-01-17 | 2010-10-05 | Microgreen Polymers, Inc. | Multi-layered foamed polymeric objects and related methods |
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CA2795961A1 (en) | 2010-04-19 | 2011-10-27 | Krishna Nadella | A method for joining thermoplastic polymer material |
US9914247B2 (en) | 2012-02-29 | 2018-03-13 | Dart Container Corporation | Method for infusing a gas into a thermoplastic material, and related systems |
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KR101888820B1 (ko) * | 2016-08-11 | 2018-08-16 | 주식회사 휴비스 | 비결정성 폴리에스테르 발포 조성물 및 이를 포함하는 발포체 |
EP3438020B1 (en) * | 2016-09-30 | 2021-10-06 | Huvis Corporation | Food container with reduced elution of hazardous substances |
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KR102319817B1 (ko) * | 2017-12-18 | 2021-11-02 | 주식회사 휴비스 | 내열성 및 가공성이 우수한 식품용기용 복합시트 및 이의 제조방법 |
KR102091526B1 (ko) | 2018-03-14 | 2020-03-24 | 김형호 | 공기 집진기 |
KR20190119861A (ko) | 2018-04-13 | 2019-10-23 | 조이운 | 고온 및 저온 냉각방식을 이용한 공기 정화장치 |
JP6986075B2 (ja) * | 2018-12-18 | 2021-12-22 | ヒューヴィス コーポレーションHuvis Corporation | 熱成形性が優秀な発泡シートおよびその製造方法 |
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-
1999
- 1999-09-14 ES ES99117928T patent/ES2238801T3/es not_active Expired - Lifetime
- 1999-09-14 AT AT99117928T patent/ATE290563T1/de not_active IP Right Cessation
- 1999-09-14 EP EP19990117928 patent/EP0989148B1/en not_active Expired - Lifetime
- 1999-09-14 DE DE1999624063 patent/DE69924063T2/de not_active Expired - Lifetime
- 1999-09-20 KR KR19990040362A patent/KR100589081B1/ko not_active IP Right Cessation
- 1999-09-21 NO NO19994587A patent/NO319966B1/no not_active IP Right Cessation
- 1999-09-21 US US09/400,918 patent/US6365249B1/en not_active Expired - Fee Related
- 1999-09-22 PL PL335534A patent/PL195935B1/pl not_active IP Right Cessation
- 1999-09-22 JP JP26829299A patent/JP3549781B2/ja not_active Expired - Fee Related
- 1999-09-23 AR ARP990104795 patent/AR023053A1/es unknown
- 1999-09-23 CA CA 2283039 patent/CA2283039C/en not_active Expired - Fee Related
- 1999-09-23 BR BR9904333A patent/BR9904333A/pt not_active IP Right Cessation
- 1999-09-24 HU HU9903239A patent/HU224201B1/hu not_active IP Right Cessation
- 1999-09-24 CN CN99120732A patent/CN1251805A/zh active Pending
- 1999-09-24 RU RU99120388A patent/RU2183557C2/ru not_active IP Right Cessation
- 1999-09-24 AU AU50138/99A patent/AU764281B2/en not_active Ceased
- 1999-10-01 TW TW88116940A patent/TWI239969B/zh not_active IP Right Cessation
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112203835A (zh) * | 2018-06-28 | 2021-01-08 | 株式会社Huvis | 包括气体阻隔层的成型体、包括其的包装容器及成型体的制备方法 |
CN112203835B (zh) * | 2018-06-28 | 2022-08-30 | 株式会社Huvis | 包括气体阻隔层的成型体及其制备方法、以及包装容器 |
CN111559101A (zh) * | 2020-05-15 | 2020-08-21 | 东莞中和生物材料科技有限公司 | 一种由可生物降解材料制成的饮用容器的生产工艺 |
Also Published As
Publication number | Publication date |
---|---|
RU2183557C2 (ru) | 2002-06-20 |
KR20000023302A (ko) | 2000-04-25 |
EP0989148A3 (en) | 2002-03-20 |
PL335534A1 (en) | 2000-03-27 |
HU9903239D0 (en) | 1999-11-29 |
NO994587L (no) | 2000-03-27 |
KR100589081B1 (ko) | 2006-06-13 |
ATE290563T1 (de) | 2005-03-15 |
JP2000109042A (ja) | 2000-04-18 |
CA2283039A1 (en) | 2000-03-25 |
HUP9903239A3 (en) | 2003-02-28 |
AU5013899A (en) | 2000-03-30 |
BR9904333A (pt) | 2000-09-12 |
AU764281B2 (en) | 2003-08-14 |
JP3549781B2 (ja) | 2004-08-04 |
US6365249B1 (en) | 2002-04-02 |
CA2283039C (en) | 2010-03-02 |
HU224201B1 (hu) | 2005-06-28 |
HUP9903239A2 (hu) | 2000-06-28 |
NO319966B1 (no) | 2005-10-03 |
DE69924063D1 (de) | 2005-04-14 |
AR023053A1 (es) | 2002-09-04 |
EP0989148A2 (en) | 2000-03-29 |
TWI239969B (en) | 2005-09-21 |
NO994587D0 (no) | 1999-09-21 |
PL195935B1 (pl) | 2007-11-30 |
EP0989148B1 (en) | 2005-03-09 |
ES2238801T3 (es) | 2005-09-01 |
DE69924063T2 (de) | 2006-04-13 |
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