PVC薄膜中邻苯二甲酸二乙基己酯对食品迁移的研究

邻苯二甲酸二乙基己酯(DEHP)作为增塑剂能改进聚合物的性能,特别是聚氯乙烯(PVC)一般添加该物质来生产薄膜。DEHP有害身体健康。当包装材料接触到食品时候,DEHP会通过迁移污染被包装物。研究了PVC塑料膜中增塑剂DEHP迁移到几种溶液。PVC塑料膜分别浸入100%正己烷、100%大豆色拉油、20%乙醇、10%食盐水、4%醋酸、蒸馏水中,在常温(25℃)下放2h、1d、2d、3d、4d、5d,溶液中DEHP浓度用高效液相检测。PVC薄膜分别浸入到100%正己烷、100%大豆在25、4、-18℃下放置1、2、3、4、5d。小包子蒸熟后马上用PVC塑料膜包装常温放置。猪肉用PVC塑料膜包装贮藏于4℃。西兰花和绿豆发芽后种植1周,通过覆盖地膜研究PVC塑料膜中DEHP迁移到植株中。研究结果显示:PVC塑料膜中DEHP最大迁移的溶液是100%正己烷,100%大豆色拉油、20%乙醇溶液中的迁移量也比较大,10%食盐水、4%醋酸、蒸馏水溶液中迁移量很少;DEHP对100%正己烷和100%大豆色拉油的迁移都是随温度上升而增加。PVC塑料膜中DEHP在30min内迁移到热的小包子已经很多。用PVC塑料膜包装猪肉在4℃下,...     

PVC as a food packaging material

Manufacture of polyvinyl chloride (PVC) in western Europe for all applications is now almost 4 m tonnes and the UK accounts for about 400 kt of this.The aim of this paper is to illustrate the relative importance of PVC as a packaging material where, in the UK for example, for food packaging it accounts for almost 40 kt (10%) of the PVC used.The different types of PVC packaging material—bottles, foil, cling film and cap sealing—and their method of manufacture are described, together with the range of food packaging applications in which they are used. The physical properties of PVC are described and, additionally, its cost and competitiveness with other materials are compared. The chemical nature of PVC compositions arising from the addition of heat stabilisers and plasticisers to achieve the desired properties is also described, with particular reference to heat stability.With the VCM toxicity issue now behind us, and PVC polymer with a maximum level of 1 ppm vinyl chloride monomer (VCM) being supplied for food packaging, PVC must be the most stringently controlled and thoroughly researched material for food packaging. Recent developments in polymerisation technology and polymer manufacture, which have enabled this level to be achieved, are briefly described.The current situation on the global migration issue, on which attention is currently focused, not only for plasticised PVC, but also other packaging materials as well, is briefly reviewed.     

EVALUATION OF PLASTICS PACKAGING MATERIALS FOR FOOD PACKAGING APPLICATIONS: FOOD SAFETY CONSIDERATIONS

In evaluating a packaging system for food packaging applications, consideration must be given to the physical properties, chemical composition and extractivity of the packaging material. The last point, extractivity, or migration from the packaging material to a food contact phase, is of major concern in the selection and use of plastics packaging materials for food packaging.
The present article deals specifically with migration of indirect food additives from plastics packaging materials and the scientific principles related to migrant transport or diffusion, as they apply to food safety. These principles and their experimental basis are discussed.     

Plastics packaging — perspectives and functions

The development of plastics materials is traced through their use as simple replacements for other packaging materials to their increasing sophistication in specialist applications. The development of improved barriers and conversion processes has increasing opened new areas of penetration for plastics in food packaging. The role of plastics in aseptics together with conversion processes commonly used is discussed, and it is considered that as filling technology develops, plastics materials will be available to package the products.     

食品塑料袋中DEHP气相色谱检测方法的建立

DEHP是塑料中常用的增塑剂之一,直接与内装高脂食品接触时,能够从塑料中迁移到内装食品中,造成内装食品的污染。DEHP对人体系统有不良影响,具有致畸、致癌的作用。本实验对各种材质(PVC、PE、PP、PS等)的食品塑料袋中DEHP的测定进行了较为系统的研究,采用气相色谱法,FID检测器,对DEHP进行测定。本方法检出限为3.38×10-3mg/kg,加标回收率为90.7%～105.1%,能够满足各种材质食品塑料袋中低浓度至高浓度DEHP含量测定的需要。     

The effect of microwave energy on specific migration from food contact plastics.

Experiments have been carried out with (a) microwave treatment of plastics followed by migration testing using the food simulant, olive oil, and (b) microwave treatment of plastics in direct contact with an organic extractant (iso-octane). In neither of these complementary approaches was there evidence of any difference in migration from plastics that had been microwave-treated compared with plastics that had received an equivalent thermal treatment. Five plastics commonly employed in microwave applications were tested and oligomers, plasticizer, antioxidant and volatile contaminants were monitored as representatives of typical migration species.     

邻苯二甲酸酯类综述

邻苯二甲酸酯类（Phthalic Acid Esters ,PAEs）是一种十分常见的增塑剂,广泛用于塑料、橡胶及乳化剂等工业中,用其增塑的聚氯乙烯（PVC）可用于制造包装材料、农用薄膜、电缆等。台湾塑化剂事件发生后,消费者对此类增塑剂产生恐慌。本文对PAEs类增塑剂毒性以及美国、欧盟、日本、我国法规进行小结,不同分子量PAEs类增塑剂的毒性强度不同,各国对PAEs的管理方式也不尽相同。本文还对近5年来食品,食品包装材料以及生物样品中PAEs的分析方法进行了回顾,检测结果提示食品、生物样品中均能检测出不同水平的PAEs。因此,需探索更为可靠的分析方法,加强人群暴露水平评估,制定PAEs更为合理的限制规定,以保障消费者饮食健康。     

Migration of 4-nonylphenol from polyvinyl chloride food packaging films into food simulants and foods.

Migration of 4-nonylphenol (NP) from polyvinyl chloride (PVC) films for food packaging into food simulants and foods has been studied in domestic applications such as wrapping of food and reheating in a microwave oven. The migration of NP from the PVC films was determined by high-performance liquid chromatography with electrochemical coulometric-array detection (LC/ED). Twelve PVC films intended for commercial use and ten for domestic applications (total: 22 samples) were analysed. Some of the PVC films (two home-use and ten retail-use) contained NP at concentrations of between 500 and 3300 microg/g. Migration of NP from the films was influenced by the test conditions (n-heptane at 25 degrees C for 60 min, distilled water at 60 degrees C for 30 min and 4% acetic acid at 60 degrees C for 30 min). The amount of NP migrating from the PVC films into n-heptane (0.33-1.6 microg/cm2) was higher than the amount migrating into distilled water or 4% acetic acid (up to 9.7 ng/cm2) for the 11 films in which NP was detected. Up to 0.23% of the NP migrated into distilled water and 4% acetic acid and up to 62.5% into n-heptane. In addition, we investigated NP migration into cooked rice samples wrapped in PVC film. Using spiked samples the method gave an average recovery of 83.7% (n = 5) with a standard deviation of 2.5%. Migration of NP ranged from not detectable (< 1.0 ng/g) to 410.0 ng/g by reheating samples in a microwave oven for 1 min and from not detectable to 76.5 ng/g by keeping samples at room temperature for 30 min.     

Compositional analysis of commercial PVC bottles and studies of aspects of specific and overall migration into foods and stimulants

Plastics additives and processing aids present severe difficulties for the legislator attempting to establish meaningful controls. In many cases information both on the substances added to the plastic and on the species migrating into food, which may well be different, are lacking. In the studies reported, information has been sought on the actual components employed in two typical commercial plastics. Analysis has been carried out of both the composition and trace constituents of the ingredients of commercial PVC formulations used for manufacturing bottles for orange squash and cooking oil applications. Assessment of maximum leachable material was made by solvent extraction of the individual additives, which was compared with overall migration from the PVC bottles into food stimulants using proposed EEC Statutory Methods. Additionally, specific migration measurements of epoxidized soyabean oil, tris(nonylphenyl) phosphite, nonylphenol, pentaerythritol, and BHT antioxidant were carried out in food stimulants and where possible also in foods.     

Effect of microwave heating on the migration of dioctyladipate and acetyltributylcitrate plasticizers from food-grade PVC and PVDC/PVC films into olive oil and water

Migration of dioctyladipate (DOA) and acetyltributylcitrate (ATBC) plasticizers from plasticized Polyvinylchloride (PVC) and polyvinylidene chloride (PVDC/PVC (Saran) films into both olive oil and distilled water during microwave heating has been studied. The plasticizer migrating into olive oil and water was determined using an indirect GC method after saponification of the ester-type plasticizer (DOA or ATBC) and subsequent collection of the alcohol component of the ester, namely: 2-ethyl-1-hexanol and 1-butanol, respectively. Migration was dependent on heating time, microwave power setting, the nature of the food simulant and the initial concentration of the plasticizer in the film. Migration of DOA into olive oil reached equilibrium after heating for 10 min at full power (604.6 mg DOA/1). Migration into distilled water was 74.1 mg/1 after 8 min of microwave cooking at full power. The amount of ATBC migrating into olive oil reached equilibrium after heating for 10 min at full power (73.9 mg ATBC/1). Migration into distilled water was 4.1 mg/1 after heating at full power for 8 min. Control samples containing olive oil gave DOA migration values which were significantly higher than the upper limit for global migration (60 mg/1) set by the European Community. It is proposed that PVC should not be used in direct contact with food in the microwave oven, while Saran may be used with caution in microwave heating and reheating applications, avoiding its direct contact with high fat foodstuffs.     

Chitosan application for active bio-based films production and potential in the food industry: Review

During the past decade, there was an increasing interest to develop and use bio-based active films which are characterized by antimicrobial and antifungal activities in order to improve food preservation and to reduce the use of chemical preservatives. Biologically active bio-molecules such as chitosan and its derivatives have a significant potential in the food industry in view of contaminations associated with food products and the increasing concerns in relation with the negative environmental impact of conventional packaging materials such as plastics. Chitosan offers real potential for applications in the food industry due to its particular physico-chemical properties, short time biodegradability, biocompatibility with human tissues, antimicrobial an antifungal activities, and non-toxicity. Thus, chitosan-based films have attracted serious attention in food preservation and packaging technology. This is mainly due to a fact that chitosan exhibits high antimicrobial activity against pathogenic and spoilage micro-organisms, including fungi, and both Gram-positive and Gram-negative bacteria. The aim of the present review was to summarize the most important information on chitosan from its bioactivity point of view and to highlight various preparative methods used for chitosan-based active bio-films and their potential for applications in the food preservation and packaging technology.     

食品和药品接触材料聚丙烯中添加剂及 物质迁移的液相色谱分析

聚丙烯(PP)塑料被广泛用在食品及药品的包装上,PP中有害物质的迁移现已成为食品及药品安全隐患的重要组成部分,当食品与包装材料直接接触时,残留在PP包装材料里的抗氧剂及分解产物可以迁移到食品中污染食品。由于食品的多样性,因此常用几种食品模拟液来代替食品在实验室各种控制条件下进行迁移试验,因为迁移到模拟液里的添加剂浓度非常小,其浓度的测定常使用灵敏度较高的高效液相色谱法。迁移受到很多因素的影响,比如:接触的时间温度、接触的方式、包装材料的类型、迁移物的性质等。本文综述了聚丙烯包装材料有害物质迁移的研究现状,为我国食品包装行业标准化体系的建立提供一定的理论依据。     

Migration from plasticized films into foods. 5. Identification of individual species in a polymeric plasticizer and their migration into foods.

To assess the significance of migration of polymeric plasticizers into foods, chemical characterization and quantification of individual oligomeric species is required. This paper reports the identification of seven individual oligomers isolated from a poly(butylene adipate) plasticizer. Based on mass spectrometry, NMR and chemical degradation, the oligomers were identified as a series of diol-terminated units ranging from a trimer up to an 11-monomer unit, along with a cyclic tetramer, all in the molecular weight range of 300-1100. A study of the migration of polymeric plasticizer from PVC film into olive oil indicated preferential migration of low molecular weight species. These oligomers which comprised 24% of the parent plasticizer contributed more than 90% of the plasticizer migration with the smallest oligomers migrating 90-fold more readily than the bulk of the plasticizer. From a knowledge of total polymeric plasticizer migration from PVC films under actual conditions of food-use, the abundance of individual oligomers in the foods has been estimated.     

2019年上海市微波食品包装中邻苯二甲酸酯类塑化剂迁移风险监测

目的 评估微波食品包装中的邻苯二甲酸酯类(phthalic acid esters, PAEs)塑化剂至食品中的迁移风险进行。方法 采集90批次微波加热食品, 依据GB 31604.30-2016《食品安全国家标准 食品接触材料及制品中邻苯二甲酸酯的测定和迁移量的测定》, 采用气相色谱-质谱法(gas chromatography-mass spectrometry, GC/MS)对样品中的PAEs含量进行检测, 并考察样品中PAEs的迁移风险。结果 90批次微波加热食品包装中, 共计有18批次样品中检出PAEs增塑剂, 检出率为20%。其中15批次样品检出含量在0~10 mg/kg范围内, 最高检出含量为29.86 mg/kg。迁移实验未检出有塑化剂的迁移。结论 2019年上海市微波食品包装引入塑化剂污染的风险较低, 正常使用过程中迁移风险较小。     

Overall migration from commercial coextruded food packaging multilayer films and plastics containers into official EU food simulants

The overall migration from a wide range of commercial five-layer coextruded packaging films into aqueous food simulants (distilled water, 3% aqueous acetic acid) and alternative fatty food simulant (iso-octane) was studied. The overall migration from commercial plastics cups (PS, HIPS, and PP) used for ice-cream or yogurt packaging into distilled water and 3% aqueous acetic acid was also studied. Test conditions for packaging material/food simulant contact and method of overall migration analysis were according to the EU directives and CEN-standards. The results showed that for all tested five-layer films and plastics (PS, HIPS, and PP) cups values of overall migration into aqueous simulants (0.11-0.79 mg/dm², 2.3-15.9 mg/l) and (<0.10-0.41 mg/dm², <0.80-3.1 mg/l) were significantly lower than the upper limit (10 mg/dm²) for overall migration from plastic packaging materials and articles into food and food simulants set by the EU Directive 90/128/EEC and their revisions. The overall migration values from five-layer materials into iso-octane were significantly higher (0.94-8.23 mg/dm², 18.8-164.7 mg/l) than the above values but are still lower than the upper limit for overall migration. Global migration values of five-layer films into aqueous food simulants seems to be independent of material thickness. In contrast, overall migration into iso-octane increases with film thickness.     

食品接触塑料中初级芳香胺检测方法研究进展

初级芳香胺是一类毒性较强的致癌物质,可通过皮肤、胃肠道和呼吸道进入人体,导致机体细胞的DNA功能和结构发生变化,严重者可引发人体输尿管癌、肾癌、膀胱癌等恶性疾病。塑料作为一种常见的食品接触材料,广泛用于食品包装、食品工具等。食品接触塑料中残留的初级芳香胺会在与食品接触的过程中向食品迁移,由此对食品安全和人身健康造成威胁。本文对国内外食品接触塑料中初级芳香胺的检测标准与相关的法规进行了对比,重点综述了近几年所报道的在食品接触塑料中初级芳香胺检测方法,包括高效液相色谱法、气相色谱.质谱法和液相色谱一质谱法等;对各种方法的前处理、仪器条件及优缺点等进行了分析;同时展望了食品接触塑料中初级芳香胺检测方法的发展趋势,以期为相关科技工作者提供参考。     

食品模拟体系中淀粉基膜材增塑剂的迁移

本文采用酯化淀粉以三乙酸甘油酯为增塑剂,经流延法制备了酯化淀粉薄膜,并利用傅里叶红外光谱衰减全反射技术(ATR-FTIR)和热重分析仪(TGA)分析了淀粉基膜材与不同食品模拟体系接触后其表层增塑剂和整体增塑剂的变化情况。结果表明,基于与淀粉基膜材、增塑剂之间的亲和性差异,食品模拟体系对淀粉基膜材产生不同的溶胀作用,导致不同程度的增塑剂迁移;与淀粉基膜材亲和性越高的食品模拟体系,对淀粉基膜材表层和内部的溶胀更迅速,并可溶解更多的增塑剂分子,从而导致淀粉基膜材中更大程度的增塑剂迁移;表层增塑剂和整体增塑剂的迁移情况差异表明,溶剂溶胀和增塑剂迁移由膜材表层向内部发生。基于以上结果可推断,在实际应用过程中,选择合适的应用领域、设计调整材料结构可主动抑制增塑剂迁移,实现这类新型包装材料的安全使用。     

食品包装PE材料中荧光增白剂迁移规律的分析

以PE塑料薄膜为研究对象,采用高效液相色谱法研究食品包装塑料材料中荧光增白剂在纯水、乙酸、乙醇、植物油4?种不同模拟物中的迁移规律,研究荧光增白剂溶出量与食品接触介质、乙酸质量浓度、乙醇体积分数、浸泡温度以及处理时间等因素的关系。结果表明：纯水基质食品模拟物对香豆素类荧光增白剂有一定溶解性,酸性食品模拟物相比于水模拟物有更强的溶解性,而含醇类食品模拟物和脂肪类食品模拟物对大部分荧光增白剂都具有较好的溶解效果;荧光增白剂的溶出量随着乙酸和乙醇含量的增加而增加;较高的温度对塑料包装材料中荧光增白剂的迁移溶出具有显著影响,并且随着接触时间的延长,塑料包装材料中的荧光增白剂向食品中迁移的可能性也不断增大。     

Global Status of the Production of Biobased Packaging Materials

Bioplastics from renewable origin are a new generation of plastics able to significantly reduce the environmental impact in terms of energy consumption and green‐house ef‐fect in specific applications. Bioplastics perform as traditional plastics when in use and are completely biodegradable within a composting cycle. Today bioplastics and partic‐ularly starch‐based plastics are used in specific industrial applications where bio‐degradability is required. Examples are composting bags and sacks, fast food service‐ware (cups, cutlery, plates, straws, etc.), packaging (soluble foams for industrial pack‐aging, film wrapping, laminated paper, food containers), agriculture (much films, nur‐sery pots, plant labels), hygiene (diaper back sheet, cotton swabs).Moreover new sec‐tors are growing outside biodegradability, driven by improved technical performances of bioplastics versus traditional materials, as in the case of biofillers for tires. The market of starch‐based bioplastics in 1999 has been estimated at about 20,000 t/a, with a strong incidence of soluble foams for packaging and films. Bioplas‐tics from renewable origin, either biodegradable or non‐biodegradable, still constitute a niche market which requires high efforts in the areas of material and application devel‐opment; the technical and economical breakthroughs achieved in the last three years, however, open new possibilities for such products in the mass markets and specifical‐ly in food packaging. This paper will review the recent industrial achievements of bioplastics in the sector of packaging, taking in consideration their in‐use performances, biodegradation behav‐iour and environmental impact.     

聚氯乙烯类食品包装材料中三甲基锡向食品模拟物的迁移规律

目的：建立聚氯乙烯类包装材料和食品模拟物中三甲基锡的超高效液相色谱-串联质谱（ultra performanceliquid chromatography-tandem mass spectrometry,UPLC-MS/MS）联用测定方法。用该方法研究聚氯乙烯中的三甲基锡向食品模拟物的迁移规律。方法：聚氯乙烯包装材料样品用乙酸乙酯提取。食品模拟物经阳离子固相萃取柱净化富集,洗脱液水浴条件下氮气吹干,残渣用流动相溶解,旋涡混匀,过0.22 μm微孔滤膜,经C18色谱柱完成分离,MS/MS仪上采用多反应监测正离子模式测定三甲基锡,外标法定量。在设定的不同温度条件下,将聚氯乙烯包装材料浸泡于食品模拟物中,于不同的时间点移取浸泡液,经前处理后测定三甲基锡迁移量。结果：三甲基锡在0.1～100.0 μg/L范围内线性关系良好（相关系数r=0.999 8）,检出限为0.02 μg/L。在1.0、10.0、50.0 μg/L 3 个添加水平范围内的平均回收率为90.6%～97.3%,相对标准偏差不高于6.9%。测定结果显示,三甲基锡迁移量在水模拟物中为0.19～1.65 μg/L、在体积分数10%乙醇模拟物中为0.19～9.89 μg/L、在3 g/100 mL乙酸模拟物中为0.11～9.96 μg/L、在正己烷模拟物中为0.15～3.54 μg/L。结论：建立的阳离子固相萃取-UPLC-MS/MS联用法测定食品模拟物中三甲基锡的方法快速简单、准确有效,三甲基锡在体积分数10%乙醇溶液和3 g/100 mL乙酸溶液迁移量较高,且随温度升高、时间延长,迁移量增加,一定时间后达到迁移平衡。