CN102947374A - 包含除氧剂的可生物降解聚合物制品 - Google Patents

包含除氧剂的可生物降解聚合物制品 Download PDF

Info

Publication number
CN102947374A
CN102947374A CN2011800238226A CN201180023822A CN102947374A CN 102947374 A CN102947374 A CN 102947374A CN 2011800238226 A CN2011800238226 A CN 2011800238226A CN 201180023822 A CN201180023822 A CN 201180023822A CN 102947374 A CN102947374 A CN 102947374A
Authority
CN
China
Prior art keywords
plastics
pla
film
iron particle
oxygen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN2011800238226A
Other languages
English (en)
Inventor
C·C·仇
T·H·鲍威尔斯
S·E·索洛夫约夫
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Multisorb Technologies Inc
Original Assignee
Multisorb Technologies Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Multisorb Technologies Inc filed Critical Multisorb Technologies Inc
Publication of CN102947374A publication Critical patent/CN102947374A/zh
Pending legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/02—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising animal or vegetable substances, e.g. cork, bamboo, starch
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B9/045—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/308—Heat stability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/716—Degradable
    • B32B2307/7163—Biodegradable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/02—Cellulose; Modified cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2303/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08J2303/02—Starch; Degradation products thereof, e.g. dextrin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0856—Iron
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y10T428/31681—Next to polyester, polyamide or polyimide [e.g., alkyd, glue, or nylon, etc.]
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31786—Of polyester [e.g., alkyd, etc.]
    • Y10T428/31797—Next to addition polymer from unsaturated monomers

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Laminated Bodies (AREA)
  • Wrappers (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Containers Having Bodies Formed In One Piece (AREA)
  • Gas Separation By Absorption (AREA)

Abstract

本发明提供一种可生物降解的氧吸收塑料制品，包括可生物降解的基体，足够浓度的还原铁粒子以吸附显著量的氧气，并且降低基体的变形温度至大大低于没有铁粒子存在时的变形温度。

Description

包含除氧剂的可生物降解聚合物制品
对于联邦政府资助的研究或开发的声明
无
″序列表″参考
无。
技术领域
本发明通常涉及除氧剂，尤其是包含除氧剂的可生物降解聚合物及其制备方法。
发明背景
对于由可再生资源制备的用于包装工业的聚合物的需求不断增加。由于消费者日益意识到聚合物对环境的影响，他们要求他们的产品包装在由可再生资源制成的容器里。
常见的可生物降解聚合物如聚乳酸(PLA)适用于许多包装应用中，但相比于聚烯烃其具有较高的气体渗透性，因此较不适用于包装在氧气、二氧化碳和水混同(weber among)其它气体存在下发生降解的产品。
需要能用于包装这种可降解产品的可生物降解聚合物。更具体地，需要PLA硬质包装，其对于例如饮料容器的应用提供对氧气有效的阻隔。
由PLA制得的软包装材料同样显示出相对于其它软质薄膜相对较高的透氧性，从而需要具有降低的透氧性的软质PLA薄膜。
已知PLA相对其它塑料制品具有相对低的热量(low heat)。如果将PLA制成的容器储存在温度可能超过PLA软化温度(约65℃)的仓库里，可能引发问题。
US6908652B1，Cryovac，6/21/2005，“Polylactic acid in oxygenscavenging article”，描述了由PLA和除氧剂构成的制品，该除氧剂选自可氧化化合物与过渡金属催化剂、烯属不饱和烃与过渡金属催化剂、抗坏血酸盐、异抗坏血酸盐、亚硫酸盐、抗坏血酸盐与过渡金属催化剂(该催化剂由过渡金属的金属单质或盐、化合物、配合物或螯合物，多聚羧酸、水杨酸或聚胺的过渡金属配合物或螯合物组成)、以及丹宁酸。该制品可以是薄膜、涂层、衬垫和其它版式的形式。
该专利没有包括不与其它材料联用的还原态的铁用作除氧剂。铁不是化合物，其不与如该现有技术所述的催化剂或化合物一起使用。
该专利同样说明加入无机粉末和/或盐导致壁透明度以及机械性能的下降。化合物可能导致加工困难，尤其是在制作薄膜或膜结构中的薄层时。与US6908652不同，本发明表明PLA薄膜通过使用铁基除氧剂制备。如下文实施例所示得到薄膜(3mil)，其具有良好的透明性和机械强度，无加工困难。关键之处在于从混配到薄膜挤出的步骤中适当地分散铁基除氧剂。通过在整个加工过程中保持化合物干燥使分散大为改善。通过用润滑剂或表面活性剂处理除氧剂来提高分散性，如4/1/09提交的美国专利申请#：12/416685中所述，其教导了制备除氧薄膜。薄膜由配比为17/3/80的铁、氯化钠和低密度聚乙烯混合物挤出。薄膜可以是独立的单层或多层结构，除氧剂位于该膜的任意层中。
US7615183，Plastics suppliers，11/10/2009，“PLA blown film andmethods of making”，描述了吹塑PLA薄膜的制备方法，没有提及除氧。
US7368160B2，Biax International，5/6/2008，“Packaging film”，表面修饰的PLA薄膜与还原COF(reduced COF)共挤出，没有提及除氧。
发明简述
本发明提供一种可生物降解的氧吸收塑料制品(oxygen absorbingplastic)，包括可生物降解的基体，足够浓度的还原铁粒子以吸附显著量(significant quantities)的氧气，并且降低基体的变形温度至大大低于(substantiallybelow)没有铁粒子存在时的变形温度。
附图简述
图1是用作封盖材料的本发明的一个实施方案的横截面图。
图2是用于形成热成型容器的本发明的一个实施方案的横截面图。
图3是显示根据本发明的袋子内的氧吸收率的曲线图。
发明概述
本发明的一个目的是提供一种可生物降解聚合物材料，其包含一种克服了现有技术中不利情况的除氧剂。
本发明更进一步的目的是提供一种聚乳酸(PLA)基除氧剂，其具有比至今已知的那些清除剂更高的透明度。
本发明的另一个目的是提供一种PLA基除氧剂，其具有与至今已知的PLA材料相比改进的热变形特性。
本发明更进一步的目的是提供一种制造PLA和铁基清除剂的挤出制品的方法。
本发明仍然更进一步的目的是提供以高透明度为特征的薄膜和薄片形式的除氧PLA挤出制品。
本发明的另一个目的是提供由箔层、粘合剂层、含有铁基氧吸收剂的PLA层、和密封剂层形成的多层层压结构，其可以转变为包装氧敏感材料的袋子。
本发明更进一步的目的是提供由常规聚苯乙烯泡沫薄片、粘合剂层、PLA+层、和密封剂层形成的多层层压结构。优选该层压物是可热成型的，以形成所需结构的容器。
发明详述
优选的原料、配方和产品结构如下：
除氧剂：
还原铁粉末优选具有1-25μm的平均粒径，更优选1-10μm的平均粒径以及最优选2-5μm的平均粒径。根据通过参考文献引入本文的US专利6,899,822、US专利申请2005/0205841和2007/020456的教导，选择涂覆到铁粒子上的活化和酸化组分的组合和相对分数。涂覆技术优选上述参考文献所述的干法涂覆。
可生物降解树脂：
本发明公开的主要聚合物为聚乳酸及其与各种丙交酯成分的共聚物或衍生物。所述衍生物为支化PLA或轻度交联PLA。PLA可以是无定形的或结晶态的。本发明声称的其它可生物降解聚合物包括聚羟基烷酸酯(PHA)脂肪族共聚酯，及其常见类型的聚合物聚羟基丁酸酯(PHB)，聚己内酯，热塑性淀粉(TPS)，纤维素及其它多糖。所有均可具有在宽范围内变化的的结晶度，从而导致各种物理性能。
以下实施例用来阐明本发明的一部分：
实施例1.含有铁作为除氧剂的PLA薄膜的挤出
NatureWorks PLA2002D树脂，聚乳酸，在干燥烘箱里60℃下干燥4小时。铁、NaCl和NaHSO4根据专利6,899,822、US专利申请2005/0205841和2007/020456所述的方法以Fe/NaCl/NaHSO4＝85/3/12的重量比混合形成FB。该混合物，FreshBlend(FB)，与PLA树脂以各种比例混合，并在平均挤出机和模具温度220℃下从双螺杆挤出机中挤出。通过使用缠绕器收集该挤出薄膜，制成5″宽以及约4mil厚的薄膜。该挤出薄膜用于除氧测试。将该薄膜保存在具有以湿毛毡纸包裹作为湿气来源的7″×7″塑料阻隔袋中。将袋子密封并注入350或150cc的O2/N2混合物以达到约1％的初始氧浓度。通过MOCON Pac CheckModel 450Head Space Analyzer在室温下测定随时间的袋中的氧浓度。
装载有3％和6％FreshBlend的PLA的除氧行为示于图3。可以看到袋内氧体积随时间快速减少。装载有6％的薄膜显示出比装载有3％的薄膜更高的除氧速率。两者均显示出在PLA基体中的一致的除氧性质。与等量纯PLA薄膜相比，两者均显示出高透明度。
实施例2.含有除氧剂的PLA层压物
图2显示根据本发明的层压物。实施例1制备的装载有6％FB的PLA薄膜用于对箔片的层压。Dow IntegralTM801薄膜用作粘结剂来制造箔/Integral801/(FB+PLA)结构的三层层压物，厚度分别为1/1/4mil。三个层在约180℃下在热密封层压机中热层压。形成各层之间良好粘合的层压物。将层压物密封在具有0.93水分活性湿度调节器(water activity moisture regulator)的阻隔袋中。在150cc O2/N2混合物以及1.04％或1.56cc的起始浓度下，除氧行为即对于FB/PLA膜和层压物氧浓度随时间的减少如图1所示。储存40小时后氧气耗尽。这表明了包含FB和PLA的层压结构的除氧能力。
实施例3.PLA薄膜的共挤出
通过利用薄膜共挤出系统，将同样的原料用于共挤出5层薄膜结构的PLA。5层结构按照A/B/C/B/A＝LDPE/粘结层/(PLA+FB)/粘结层/LDPE的顺序以约5/5/80/5/5的厚度比排列。仅分布在C层的FreshBlend净含量为5wt％。挤出在平均挤出机出口温度A＝500F、B＝500F和C＝390F下进行。LDPE树脂是Dow LDPE640I。粘结层树脂是Admer QF551A，马来酸酐改性的聚丙烯，以及PLA是NatureWorks 2002D树脂。通过适当调整挤出速率和模具温度，生产出由五层结构组成的3和3.5mil薄膜。包含FreshBlend的PLA层预计为2-3mil。这表明含铁基除氧剂的PLA形成多层结构薄膜的加工性能。

Claims (10)

1.可生物降解的氧吸收塑料制品，包括可生物降解的基体，足够浓度的还原铁粒子以吸附显著量的氧气，并且降低所述基体的变形温度至大大低于没有铁粒子存在时的变形温度。
2.权利要求1的塑料制品，其中还原铁粒子具有约1至约25μm的平均粒径。
3.权利要求2的塑料制品，其中还原铁粒子具有约1至约10μm的平均粒径。
4.权利要求3的塑料制品，其中还原铁粒子具有约2至约5μm的平均粒径。
5.权利要求1的塑料制品，其中所述可生物降解的基体选自支化PLA、交联PLA、无定形PLA、结晶态PLA、聚羟基烷酸酯(PHA)脂肪族共聚酯、聚羟基丁酸酯(PHB)、聚己内酯、热塑性淀粉(TPS)、纤维素及其它多糖。
6.权利要求5的塑料制品，其中铁粒子以约6％的量存在。
7.权利要求1的塑料制品，其中所述塑料制品为薄膜形式。
8.权利要求7的塑料制品，还包括层叠到薄膜的箔层。
9.权利要求7的塑料制品，包括层叠到薄膜的低密度聚乙烯层和粘结剂层。
10.权利要求9的塑料制品，其中这些层按照低密度聚乙烯-粘结剂-塑料层-粘结剂-低密度聚乙烯的顺序排列。
CN2011800238226A 2010-05-12 2011-02-25 包含除氧剂的可生物降解聚合物制品 Pending CN102947374A (zh)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US12/778,703 US20110281125A1 (en) 2010-05-12 2010-05-12 Biodegradable polymer articles containing oxygen scavenger
US12/778,703 2010-05-12
PCT/US2011/026148 WO2011142871A2 (en) 2010-05-12 2011-02-25 Biodegradable polymer articles containing oxygen scavenger

Publications (1)

Publication Number Publication Date
CN102947374A true CN102947374A (zh) 2013-02-27

Family

ID=44912050

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2011800238226A Pending CN102947374A (zh) 2010-05-12 2011-02-25 包含除氧剂的可生物降解聚合物制品

Country Status (15)

Country Link
US (1) US20110281125A1 (zh)
EP (1) EP2569355A4 (zh)
JP (1) JP2013533324A (zh)
KR (1) KR20130088029A (zh)
CN (1) CN102947374A (zh)
AR (1) AR081179A1 (zh)
AU (1) AU2011253437A1 (zh)
BR (1) BR112012028754A2 (zh)
CA (1) CA2799171A1 (zh)
CL (1) CL2012003170A1 (zh)
CO (1) CO6592018A2 (zh)
IL (1) IL222962A0 (zh)
MX (1) MX2012013132A (zh)
WO (1) WO2011142871A2 (zh)
ZA (1) ZA201209040B (zh)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130302620A1 (en) * 2012-05-09 2013-11-14 Ppg Industries Ohio, Inc. Basecoat with improved adhesion to bioplastic
WO2016190815A1 (en) * 2015-05-22 2016-12-01 Agency For Science, Technology And Research Nanostructured iron/carbon for scavenging oxygen
EP3784491A4 (en) 2018-04-27 2021-12-01 Amcor Rigid Packaging USA, LLC THERMOPLASTIC MULTI-LAYER ARTICLES WITH IMPROVED RECYCLABILITY
KR102152506B1 (ko) * 2018-11-08 2020-09-07 한국식품연구원 산소제거 기능성 마스터배치 및 이의 제조방법
CA3097347A1 (en) 2019-10-30 2021-04-30 Polyvalor, Limited Partnership Titanium dioxide catalyzed butadiene polymer based oxygen scavenging system

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000503339A (ja) * 1996-09-18 2000-03-21 クライオバツク・インコーポレイテツド 酸素捕捉用品中のポリ乳酸
JP2000248111A (ja) * 1999-02-26 2000-09-12 Toagosei Co Ltd 酸素吸収性樹脂用酸素吸収剤、酸素吸収性樹脂組成物、酸素吸収性フィルムまたはシートおよび脱酸素性容器
US20090110857A1 (en) * 2006-04-20 2009-04-30 Toyo Seikan Kaisha, Ltd. Oxygen absorber for blending in a resin and method of producing the same

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0367835B1 (en) * 1988-04-30 1996-07-31 Toyo Seikan Kaisha, Ltd. Multilayered plastic container
JP3969524B2 (ja) * 2002-04-09 2007-09-05 株式会社クレハ プラスチック多層構造体
US6899822B2 (en) * 2002-11-18 2005-05-31 Multisorb Technologies, Inc. Oxygen-absorbing composition
US20070218304A1 (en) * 2006-03-20 2007-09-20 Graham Packaging Company, Lp Active oxygen barrier compositions of poly(hydroxyalkanoates) and articles made thereof
US20110217430A1 (en) * 2010-03-08 2011-09-08 Chieh-Chun Chau Thermoplastic and biodegradable polymer foams containing oxygen scavenger
US8658714B2 (en) * 2009-04-06 2014-02-25 Biosphere Industries, Llc Ecologically friendly composition containing beneficial additives
US20110243483A1 (en) * 2010-03-31 2011-10-06 Multisorb Technologies, Inc. Oxygen and carbon dioxide absorption in a single use container

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000503339A (ja) * 1996-09-18 2000-03-21 クライオバツク・インコーポレイテツド 酸素捕捉用品中のポリ乳酸
JP2000248111A (ja) * 1999-02-26 2000-09-12 Toagosei Co Ltd 酸素吸収性樹脂用酸素吸収剤、酸素吸収性樹脂組成物、酸素吸収性フィルムまたはシートおよび脱酸素性容器
US20090110857A1 (en) * 2006-04-20 2009-04-30 Toyo Seikan Kaisha, Ltd. Oxygen absorber for blending in a resin and method of producing the same
CN101426858A (zh) * 2006-04-20 2009-05-06 东洋制罐株式会社 树脂配合用氧气吸收剂及其制备方法

Also Published As

Publication number Publication date
AU2011253437A1 (en) 2012-12-06
AR081179A1 (es) 2012-07-04
WO2011142871A2 (en) 2011-11-17
CO6592018A2 (es) 2013-01-02
ZA201209040B (en) 2014-02-26
EP2569355A4 (en) 2014-01-22
KR20130088029A (ko) 2013-08-07
WO2011142871A3 (en) 2012-01-05
US20110281125A1 (en) 2011-11-17
CA2799171A1 (en) 2011-11-17
BR112012028754A2 (pt) 2016-07-19
CL2012003170A1 (es) 2013-05-17
JP2013533324A (ja) 2013-08-22
MX2012013132A (es) 2013-04-03
IL222962A0 (en) 2013-02-03
EP2569355A2 (en) 2013-03-20

Similar Documents

Publication Publication Date Title
KR950013364B1 (ko) 폴리비닐 알코올 제품 및 이를 함유하는 다층 제품
EP2903909B1 (en) Food package
CN101868347B (zh) 具有阻隔性能的环保型多层柔性薄膜
EP2199077B1 (en) Packaging laminate, method for manufacturing of the packaging laminate and packaging container produced there from
CA2685260C (en) Biodegradable multilayer polymeric films and packages produced therefrom
CN103003065A (zh) 含有除氧剂的层压和热成型的物品
US20100282633A1 (en) Laminated and thermoformed articles containing oxygen scavenger
KR20080091396A (ko) 산소 및 습기 장벽 성질을 갖는 생분해성 종이-기재 라미네이트 및 생분해성 종이-기재 라미네이트의 제조 방법
KR20160067191A (ko) 산소 포집 필름
CN102947374A (zh) 包含除氧剂的可生物降解聚合物制品
CN101758959A (zh) 五层共挤高阻隔液体包装膜材及其制备方法
Farris et al. Emerging coating technologies for food and beverage packaging materials
US20110036059A1 (en) Container and Method for Making Container for Oxygen-Sensitive Products
JPH03109917A (ja) 乾燥剤成型品
EP2812262B1 (en) Film with oxygen absorbing regions
JP2669852B2 (ja) 制御した雰囲気下に物品を包装するための多層フイルム
CN103890058A (zh) 含有多孔结构和吸附剂的聚(乳酸)和聚烯烃膜
JP2003300292A (ja) プラスチック多層構造体
JPH0539379A (ja) 調湿性組成物及び調湿性成形品
JPH04191039A (ja) 包装体
JP2008119858A (ja) 包装積層材料
JP3277670B2 (ja) 多層射出成形物
CN113276526A (zh) 一种单向吸水复合膜及其制备方法和应用
JPH10235769A (ja) 脱酸素性多層体及びこれよりなる包装容器
CA2799173A1 (en) Laminated and thermoformed articles containing oxygen scavenger

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20130227