CN102869712A - 包含除氧剂的热塑性和生物可降解聚合物泡沫 - Google Patents

包含除氧剂的热塑性和生物可降解聚合物泡沫 Download PDF

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CN102869712A
CN102869712A CN2011800229867A CN201180022986A CN102869712A CN 102869712 A CN102869712 A CN 102869712A CN 2011800229867 A CN2011800229867 A CN 2011800229867A CN 201180022986 A CN201180022986 A CN 201180022986A CN 102869712 A CN102869712 A CN 102869712A
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foam
oxygen scavenger
oxygen
building enclosure
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C-C.仇
S.A.因科维亚
D.S.佩恩
T.H.鲍威尔斯
S.E.索洛夫约夫
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Multisorb Technologies Inc
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Abstract

本发明涉及包含在低密度泡沫中分配的除氧剂的除氧材料，其中除氧剂具有小于25μm的粒径。在另一个实施方案中，本发明涉及一种产品包装，所述产品包装包含泡沫盘、在泡沫盘中的产品和包围肉和盘的聚合物包裹材料，其中泡沫盘包含除氧材料，其中除氧材料包含在泡沫中分配的除氧剂，其中除氧剂具有小于25μm的粒径。

Description

包含除氧剂的热塑性和生物可降解聚合物泡沫
相关申请交叉引用
本申请为要求2010年3月8日提交的美国专利申请12/719,160的优先权的国际申请，其全部公开内容明确通过引用结合到本文中。
关于联邦资助的研究或开发的声明
不适用
序列表引用
不适用。
发明背景
发明领域，
本发明涉及在低密度泡沫中分配的除氧剂材料。具体地讲，本发明涉及用于包装食品的泡沫盘形式的除氧剂材料。
相关技术描述
刚性食品容器，如肉盘和一次性杯，广泛用于食品包装和服务。用于肉或食品包装的常规盘和容器通常为泡沫，以减小重量，为了包装和运输仍提供刚性。材料一般为聚苯乙烯和其它聚烯烃。
容器的合乎需要性质是保持食品的鲜度。改善肉包装鲜度的一般方法是用浸垫去除过量液体。更有效的方法是减小包装内的氧含量。有效性已由利用除氧剂包装的盒装分割肉显示。
盒装分割肉在中央屠宰加工厂包装，然后在包含多个肉包装的袋中运输到使用的食品杂货店或饭店。包装的肉通常在聚苯乙烯泡沫盘中，并用以小孔穿孔以便允许气体循环的聚合物包装材料包裹。袋一般由耐氧聚合物片形成，并且含有包含除氧剂材料的片或囊袋形式的除氧剂。已发现，泡沫盘和肉放出氧，并且难以包括成本有效和快速吸收所有氧的足够除氧剂。
吸收食品包装中氧的已知方法是通过在聚合物基质中包埋或挤压除氧剂。本领域的现有技术主要集中在固体聚合物薄膜或片，虽然已知在多孔结构挤压除氧剂。
以下专利涉及包装中的氧控制：
美国专利6,194,042 B1(Tri-Seal Holdings, Inc, 2001)描述在层中具有泡沫芯的多层衬垫。
美国专利4,188,457(Metal Box Limited, 1980)描述用于酒瓶的软木塞封口。
美国专利4,781,295(Mobil Oil Co, 1988)描述通过掺合聚苯乙烯与聚乙烯改善的泡沫肉盘。
美国专利6,908,652 B1(Cryovac, 2005)描述不包括起泡的多层制品中利用聚乳酸的除氧剂。
美国专利6,213,294 B1(Tres Fresh LLC, 2001)描述使用泡沫盘的改进气调包装。
美国专利 6,071,580(Dow Chemical, 2000)描述制造用于流体吸收应用的开孔泡沫和盘的方法。
因此，仍需要制备用于肉和其它产品的包装的改进方法。仍需要在远离销售点的场所包装的肉包装的较佳氧控制。
发明概述
本发明涉及包含在低密度泡沫中分配的除氧剂的除氧材料，其中除氧剂具有小于25μm的粒径。
在另一个实施方案中，本发明涉及一种产品包装，所述产品包装包含泡沫盘，所述泡沫盘包含除氧材料；在泡沫盘中的产品；和包围产品和盘的聚合物包裹材料，其中除氧材料包含在泡沫中分配的除氧剂，并且其中除氧剂具有小于25μm的粒径。
附图简述
图1为本发明的泡沫材料的横截面图。
图2为本发明的产品包装的横截面示意图。
图3为在围护结构中具有产品包装的主产品围护结构的横截面示意图。
图4表示除氧剂聚苯乙烯泡沫的氧吸收性质。
图5显示除氧剂PLA泡沫与纯泡沫在92% RH长期储存的比较。
发明详述
本发明具有超过现有产品包装材料和运输由于存在氧易于变质的产品的主围护结构的方法的多个优点。本发明减少对包装中松散除氧剂单元的需要。本发明的优选产品允许由被包装的产品中的水活化除氧剂。泡沫产物盘中的水活化氧吸收材料减少主围护结构中单独的除氧剂并允许在没有过早氧吸收过多保护下运输空泡沫容器的需要。
在泡沫容器中加入活性除氧剂的优点包括增加肉/食品包装的鲜度，为盒装分割肉提供另外的鲜度，用从肉/食品渗出的液体活化清除剂，并且不需要或很少需要清除囊袋。
本发明的泡沫制品的属性进一步包括下列：(a)均匀分散得到良好的外观；(b)通过孔眼大小、开孔水平和密度控制可调节的氧吸收速率；(c)改进的膨胀比或减少的起泡剂，以减少挥发性有机化合物(VOC)；(d)保留的机械性质；和(e)可印刷和可装饰。
通过以下详细说明和附图，这些和其它优势将变得显而易见。
图1为除氧材料10的横截面。除氧剂材料提供有表层12和14和泡沫芯层16。表层12和14和泡沫芯层16包含除氧剂22。泡沫芯层16包含孔18和除氧剂材料22。应注意，一些除氧剂材料22与孔18接界，并帮助孔18成核。在帮助孔形成时，清除剂材料允许使用较少起泡剂。
图2显示用除氧材料10(如图1所示)形成的产品包装30。除氧剂材料10已通过熟悉的方法形成盘32，例如热成型，未显示。盘32含有包含一些水分的产品(例如牛肉36)和优选的吸收垫38。盘32已用聚合物片包裹，并在底部42密封。聚合物包裹材料可以为隔氧材料，或者在一些实施方案中，可有微孔，以允许从包装排出气体。对于主产品围护结构运输，包裹材料应有微孔。对于当地和店内使用，包裹材料应不是有孔的。吸收垫38为在肉的盘包装使用的常规吸收垫，以吸收肉液。
在图3中显示主产品围护结构50。主产品围护结构50显示有四个产品包装30，这些包装堆叠在由隔氧聚合物片形成的袋56内。将气体从袋56抽出，并由封口58将袋56密封。在密封前为袋56提供除氧剂单元52和54。产品包装30提供有微孔包裹材料34，以允许通过盘32中的除氧剂材料和除氧剂单元52和54二者清除氧。袋56中的氧源为未去除的残余空气、从肉脱出氧和从泡沫盘32脱出氧。如果盘32具有足够除氧能力，可能不必使用除氧单元52和54。
在本发明中公开一种制造包含除氧剂的多孔泡沫片的方法。该方法通过在起泡树脂中直接挤出基于铁的除氧剂，以允许活性成分均匀分散于泡沫基质。通过使用常规热成型方法，可使泡沫片热成型形成容器。优选的起泡剂为不包含或产生水分的物理起泡剂，例如轻质烃或惰性气体。
在优选的实施方案中提供包含充分分散于结构的基于铁的除氧剂的热塑性聚合物泡沫，所述泡沫具有从纯聚合物>50%的密度减小和<31 lb/ft3的密度。由于成本低，优选的聚合物为聚苯乙烯。优选的基于铁的除氧剂为用活化和氧化反应促进剂预涂覆或与其混合的具有1-25μm平均粒径的细粉末形式。在熔融前，基于铁的除氧剂作为母料混合并送料或者与固态起泡树脂预混。然后将起泡剂注入聚合物熔体。除氧剂可作为泡沫孔眼的成核剂。起泡树脂和基于铁的清除剂任选包含其它添加剂作为成核剂，以形成细孔眼。
本发明的另一个实施方案提供包含充分分散于结构的基于铁的除氧剂的生物可降解聚合物泡沫。泡沫具有30%或更高的密度减小和43 lb/ft3或更低的密度。优选的生物可降解聚合物为聚乳酸。
在另一个实施方案中，本发明提供热塑性聚合物泡沫，所述泡沫可用减小量的起泡剂和加入基于铁的除氧剂达到低泡沫密度，因此减少放出的挥发性有机化合物。热塑性泡沫的特征是在泡沫片离开模时通过形成表层形成的闪光反射外观。
可在本发明中利用任何适用的除氧剂。除氧剂一般为二氧化硫、水杨酸或水杨酸盐的螯合物。适用的除氧剂材料为金属(例如，锌、铜、铝和锡)的盐或螯合物。由于有效且成本低，铁除氧剂是优选的。
最优选的除氧剂为用活化和酸化材料涂覆的经还原铁粉。为了快速清除和良好地形成孔，它优选具有1-25μm平均粒径，更优选1-10μm平均粒径，最优选2-5μm平均粒径。涂覆于铁颗粒上的活化和酸化组分的组合和相对分数根据美国专利6,899,822、美国专利申请2005/0205841和2007/0020456的教授选择，所述专利通过引用结合到本文中。涂覆技术优选为干燥涂覆，如以上参考文献中所述。本发明特别集中在具有1-25μm平均粒径的基于铁的粉末，其中铁颗粒用活化和氧化反应促进剂颗粒预涂覆，以形成均匀粉末。用精细分散的除氧颗粒制造的起泡片或制品有利地具有与氧的高反应性。除氧颗粒充分地遍布泡沫结构分散。
由于可形成的泡沫制品的低成本和强度，用于泡沫除氧材料的优选聚合物为聚苯乙烯和苯乙烯-丁二烯共聚物。其它适合的聚合物包括苯乙烯-乙烯共聚物、聚丙烯、聚乙烯、聚氨酯及其共聚物或衍生物。也可利用生物可降解聚合物和以上聚合物的组合。
用于本发明中公开的任选生物可降解树脂的优选聚合物为聚乳酸(PLA)及其共聚物或衍生物。由于通过在PLA中支化或交联诱导的较高熔体强度促进树脂的发泡性并且得到较低密度泡沫，优选的衍生物为支化PLA或轻度交联的PLA。其它适合的生物可降解聚合物包括聚羟基链烷酸酯(PHA)、脂族共聚酯、聚羟基丁酸酯(PHB)的一般类型聚合物、聚己内酯、热塑性淀粉(TPS)、纤维素和其它多糖。它们均可具有在宽范围变化的结晶度，以得到不同的物理性质。
无机或有机添加剂，例如滑石粉、CaCO3、硬脂酸锌和0.1-5%低浓度的市售抗氧化剂，可加到树脂作为泡沫孔眼的成核剂。起泡剂包括轻质烃，例如异丁烷、异戊烷、HCFC-142B、141B。它也包括惰性气体，例如CO2、N2、Ar或这些组分的混合物。
起泡条件应遵循已知制造低密度片泡沫的条件。一般利用在树脂熔融态注射的起泡剂通过串列式挤出机挤出泡沫。应适当保持挤出机和模温度和压力，以达到有利于低密度泡沫的条件。聚苯乙烯的泡沫密度优选<31.5 lb/ft3，更优选<10 lb/ft3，最优选2-5 lb/ft3。聚乳酸的泡沫密度优选<43 lb/ft3，更优选<20 lb/ft3，最优选2-10 lb/ft3。由于成本较低，较低密度是优选的。
除氧材料挤成泡沫片，泡沫片在通过挤出模形成的表面上具有表层，其中模使泡沫表面破裂形成表层；和泡沫芯。片为热塑性，并且可通过热成型形成容器。用于本发明的优选容器为盘，例如，用于肉包装。然而也可形成其它形状，例如杯、碗和碟。杯和碗也可提供有热成型除氧泡沫材料的盖。
可通过控制泡沫挤出过程形成接近泡沫材料表面具有更多开孔的泡沫材料。泡沫材料的开孔区域比封闭孔更快地吸收氧。封闭孔区域提供较佳的强度，并使泡沫材料增强。开孔形成与封闭孔形成的平衡通过在挤出期间控制起泡温度、添加剂和树脂配料进行。
利用水活化的除氧剂有特别的益处。在使用水活化的除氧剂时，很少在使用前需要成型泡沫盘的高代价无氧储存，虽然优选在使用前将它们保持在隔氧和水蒸气的袋中，以免减小它们的氧吸收能力。
主产品围护结构作为隔氧和水蒸气聚合物袋显示于图3中。如果具有阻隔氧和水蒸气通过的性质，可利用任何适合的聚合物袋。袋可利用金属层作为隔离层或者由具有隔离性质的聚合物形成。已发现，优选材料为聚偏二氯乙烯袋，因为它具有良好的隔离性质，强且成本低。作为袋的替代，可利用可热封并且以隔离材料(例如，金属薄膜和/或聚合物材料)为衬里的刚性容器。
在封闭前，从主产品围护结构抽出空气。这使氧吸收最大限度地减小。然而，氧也由产品发出，例如肉和蔬菜。另外，泡沫盘将包含排入袋的一些氧。虽然已知在抽空之前将氧吸收单元以片或囊袋形式放入袋，但如果泡沫盘具有氧吸收性质，很少或不需要另外的氧吸收单元。如果盘的氧吸收性质由来自盘中储存的肉的水分活化，则特别有效，因为肉放出的氧由盘更快速地吸收，而不必费力到主产品围护结构中的囊袋。在品质显著变坏可检测之前，使用在泡沫盘中加到除氧剂已显示对牛肉和猪肉得到较长的储存时间。
已显示氧吸收材料保护不变质的产品为肉，因为这是利用牛肉和猪肉的较佳用途。然而，本发明的氧吸收材料也可用于包装制备的食品、蔬菜产品、鱼和鸡肉。在其它情况下，可在本发明的包装和主产品围护结构中销售或运输这些物料，例如烟草、医药、水果和实验室样品。
实施例：除非另外指明，份数和百分比以重量计。
实施例1：包含除氧剂的挤出的聚苯乙烯混合物。
通过用硫酸氢钠和氯化钠涂覆4-5μm平均粒径的铁颗粒，以形成具有80%铁、10%硫酸氢钠和10%氯化钠的组成的均匀涂覆复合粉末，制备除氧剂包装。将经涂覆的复合粉末除氧剂用于与聚苯乙烯树脂(Dow Chemical Styron 666)挤出。将双螺杆挤压机混合设备用于混合除氧剂与树脂。在与除氧剂混合之前，将树脂粒料与0.2%重量矿物油(零售药学级)混合。然后在挤出机中加入混合物。将挤出机对于所有加热区域设定在200℃，对于模温度设定在190℃。挤出除氧剂/树脂混合物，得到20重量份除氧剂和80重量份聚合物的混合物和40/60重量比除氧剂和聚合物的混合物。在制粒前，使挤出股经空气冷却。
实施例2：挤出除氧聚苯乙烯泡沫
将1.5"和2.5"单螺杆串列式挤出机系统用于挤出聚苯乙烯片泡沫。将来自实施例1的除氧剂和树脂混合物、聚苯乙烯(Dow Styron 685)和滑石粉母料按批混合，并送入对所有挤出机区域设定到180℃的1.5"挤出机。滑石粉母料包含40/60比的滑石粉和聚苯乙烯。除氧剂混合物、聚苯乙烯和滑石粉母料的量在表1中给出。异丁烷接近连接到2.5"挤出机的1.5"挤出机的出口注入。将3.5"平片模连接到2.5"挤出机的出口，并设定到150℃，以挤出片泡沫。
将包含除氧剂混合物的3-5mm厚泡沫片挤出，并作为板收集。泡沫为银白色，并且为反射性，没有可见的附聚。纯除氧剂树脂混合物为2至8%重量。泡沫的密度通过水浸渍试验测定。表1列出除氧聚苯乙烯泡沫的配料、工艺条件和性质。如表所示，除氧剂泡沫的密度为2.8-3.1 lb/ft3，可与没有除氧剂的纯聚苯乙烯泡沫相比，并且与市售泡沫盘的密度一致。这表明形成可用于制造容器或盘的低密度除氧泡沫。
表-1：挤出除氧剂聚苯乙烯泡沫
树脂 SR 滑石粉 起泡剂   模T 模P 膨胀比 密度
  纯% % 类型 pph C psi   pcf
Styron 685 0 0.5 异丁烯 7 135 350 20 3.12
Styron 685 2 0.5 异丁烯 8 125 350 20 3.12
Styron 685 4 1 异丁烯 6.5 140 210 21 2.97
Styron 685 8 1 异丁烯 5.2 135 170 22 2.84
* 模T =模温度℃　　　　　　模P =模压力psi
* pph =百分份数　　　　　　　SR =除氧剂树脂混合物
已观察到，制造相同低密度泡沫需要的起泡剂的量一般随除氧剂量的增加而减少。这表明使用基于铁的除氧剂潜在减少起泡剂，而不牺牲泡沫密度。
除氧性能用囊袋试验检测。切割新的泡沫板，称重，并放入贴箔的囊袋。提供92%相对湿度的增湿剂也储存在囊袋中，以通过除氧剂激活氧吸收能力。然后将囊袋密封，随后用来自O2/N2=20/80的混合物的300cc气体注入囊袋。通过MOCON Pac Check 450型顶部空间分析仪测定氧浓度。对于2-8%重量除氧树脂混合物填充量，每单位泡沫重量的氧吸收显示于图4中。应注意到，由于泡沫孔眼包含异丁烷，并且在开始有很少或没有空气和水分，氧吸收性质可只主要归因于表面除氧剂。多孔结构内的除氧剂的功能性可能未活化。然而，除氧剂泡沫显示超过纯泡沫的增强吸收性质。如果有更多水分存在，则由于更快地清除氧，结果会较好。
实施例3：挤出除氧PLA泡沫
将NatureWork PLA 2002D挤出机用于挤出除氧剂泡沫。将树脂与具有2-4%填充量的与实施例1中相同的除氧剂树脂混合物、作为成核剂滑石粉和作为起泡剂的异丁烷混合。配料、工艺条件和性质列于表3中。泡沫片具有与纯树脂比较约50%或更大的密度减小。尽管由于线型聚合物具有相对较弱可成型性，但PLA泡沫具有适用于制造容器和盘所用泡沫片的性质。这表明形成用基于铁的除氧剂制造的活性多孔PLA。
表3：挤出除氧剂PLA泡沫
树脂 SR 滑石粉 起泡剂   模T 模P 膨胀比 密度
  纯% % 类型 pph C psi   pcf
PLA2002 0 1 异丁烯 5 120 750 2.5 24.96
PLA2002 2 1 异丁烯 7 130 300 2 31.20
PLA2002 4 .05 异丁烯 9 130 385 2.9 21.30
SR =除氧剂树脂混合物
除氧剂PLA泡沫样品的氧吸收性质用与上述相同的方法检测。图5显示除氧剂PLA泡沫与纯泡沫在92% RH长期储存的比较。新制的泡沫在多孔结构中包含异丁烷，因此，由于氧跨过泡沫孔眼流入和异丁烷跨过泡沫孔眼流出，纯泡沫也显示氧吸收。除氧剂PLA泡沫显示与纯泡沫比较增强的氧吸收。

Claims (29)

1. 一种包含在低密度泡沫中分配的除氧剂的除氧材料，其中除氧剂具有小于25μm的粒径。
2. 权利要求1的除氧材料，其中泡沫具有小于31.5磅/立方英尺的密度。
3. 权利要求1的除氧材料，其中除氧剂包含铁。
4. 权利要求1的除氧材料，其中泡沫包含聚苯乙烯聚合物。
5. 权利要求1的除氧材料，其中材料包含表层。
6. 权利要求5的除氧材料，其中材料包括肉盘。
7. 权利要求1的除氧材料，其中除氧剂具有2和5μm之间的粒径。
8. 权利要求1的除氧材料，其中低密度泡沫包含生物可降解聚合物。
9. 权利要求1的除氧材料，其中生物可降解低密度泡沫包括包含聚乳酸聚合物或其衍生物的生物可降解聚合物。
10. 权利要求1的除氧材料，其中泡沫具有15和25磅/立方英尺之间的密度。
11. 权利要求1的除氧材料，其中泡沫具有2至15磅/立方英尺之间的密度。
12. 一种产品包装，所述产品包装包含泡沫盘、在盘中的产品和包围产品和盘的聚合物包裹材料，其中泡沫盘包含除氧材料，除氧材料包含在泡沫中分配的氧清除剂，其中氧清除剂具有小于25μm的粒径。
13. 权利要求12的产品包装，其中产品为肉。
14. 权利要求12的产品包装，其中除氧剂包含铁。
15. 权利要求12的产品，其中除氧剂包含铁颗粒、氯化钠和硫酸氢钠。
16. 权利要求15的产品，其中泡沫包含聚苯乙烯聚合物。
17. 权利要求13的产品包装，其中肉液使除氧剂活化。
18. 一种主产品围护结构，所述主产品围护结构包含由隔氧材料形成的容器；多个产品包装，所述多个产品包装包含泡沫盘、在盘中的产品和包围各产品和盘的聚合物包裹材料，以形成肉包装，其中泡沫盘包含在泡沫中分配的除氧材料，其中除氧剂具有小于25μm的粒径。
19. 权利要求18的主产品围护结构，其中容器包括袋。
20. 权利要求18的主产品围护结构，其中容器包括包含聚偏二氯乙烯的袋。
21. 权利要求18的主产品围护结构，其中聚合物包裹材料是多孔的。
22. 权利要求18的主产品围护结构，其中产品为肉，来自肉的液体用于使泡沫中的除氧剂材料活化。
23. 权利要求18的主产品围护结构，其中至少一个除氧剂单元在围护结构中。
24. 一种减少用于多个产品包装的主产品围护结构中氧浓度的方法，所述方法包括，提供多个产品包装，各产品包装包含惰性除氧剂材料和与惰性除氧剂材料接触的产品，以促进除氧；提供主围护结构；并将产品包装放入主围护结构；从主围护结构清除氧；并且密封主围护结构，其中主围护结构包含不透氧层。
25. 权利要求24的方法，其中惰性除氧剂由来自产品的液体活化。
26. 权利要求24的方法，其中除氧剂包含用吸水材料涂覆的铁颗粒。
27. 权利要求26的方法，其中吸水材料为无机盐。
28. 权利要求20的方法，其中主产品围护结构包含隔氧材料。
29. 权利要求25的方法，其中产品为肉。
CN2011800229867A 2010-03-08 2011-02-11 包含除氧剂的热塑性和生物可降解聚合物泡沫 Pending CN102869712A (zh)

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