纸包装油墨中增塑剂向奶粉的迁移

纸包装油墨中含有有毒有害物质并可通过包装材料迁移进入内装食品从而危害人体健康。模拟实际印刷条件制作真实油墨迁移单元,研究纸张胶印油墨中4种主要增塑剂（3种邻苯二甲酸酯类增塑剂和近年流行的环保增塑剂乙酰基柠檬酸三丁酯）向奶粉的迁移,考察其在100、70、50、25 ℃的迁移行为,探讨增塑剂的性质及其在纸张中的分布等因素对迁移行为的影响。结果表明：4种增塑剂的最大迁移率在6.7%～67.8%之间。纸包装油墨中增塑剂的迁移防护性能还有待提高。     

Migration from plasticized films into foods. 3. Migration of phthalate, sebacate, citrate and phosphate esters from films used for retail food packaging

A UK survey of plasticizer levels in retail foods (73 samples) wrapped in plasticized films or materials with plasticized coatings has been carried out. A wide range of different food-types packaged in vinylidene chloride copolymers (PVDC), nitrocellulose-coated regenerated cellulose film (RCF) and cellulose acetate were purchased from retail and 'take-away' outlets. Plasticizers found in these films were dibutyl sebacate (DBS) and acetyl tributyl citrate (ATBC) in PVDC, dibutyl phthalate (DBP), dicyclohexyl phthalate (DCHP), butylbenzyl phthalate (BBP), and diphenyl 2-ethylhexyl phosphate (DPOP) in RCF coatings, and diethyl phthlate (DEP) in cellulose acetate. Foodstuffs analysed included cheese, pate, chocolate and confectionery products, meat pies, cake, quiches and sandwiches. Analysis was by stable isotope dilution GC/MS for DBP, DCHP and DEP, GC/MS (selected ion monitoring) for BBP and DPOP, and GC with flame ionization detection for DBS and ATBC, but with mass spectrometric confirmation. Levels of plasticizers found in foods were in the following ranges: ATBC in cheese, 2-8 mg/kg; DBS in processed cheese and cooked meats, 76-137 mg/kg; 76-137 mg/kg; DBP, DCHP, BBP, and DPOP found individually or in combination in confectionery, meat pies, cake and sandwiches, total levels from 0.5 to 53 mg/kg; and DEP in quiches, 2-4 mg/kg.     

微波条件下纸包装油墨中增塑剂向食品（模拟物）的迁移

研究纸张印刷油墨中4 种增塑剂（3 种邻苯二甲酸酯类增塑剂和近年流行的环保增塑剂乙酰基柠檬酸三丁酯）向食品模拟物Tenax和奶粉的迁移,考察其在110、250、440、600、900 W微波功率下的迁移行为,探讨迁移影响因素,并与常规条件下的迁移行为做比较。结果显示在一定条件下微波功率越高,迁移量越大;且迁移行为受增塑剂的分子质量、极性等性质的影响;常规条件下的迁移影响因素也适用于微波条件。     

应用气相色谱模拟分离软件快速检测火腿肠及肠衣中的塑化剂

利用气相色谱模拟分离软件,测定火腿肠及其肠衣中的塑化剂邻苯二甲酸二甲酯、邻苯二甲酸二乙酯、 邻苯二甲酸二丁酯、邻苯二甲酸二环己酯、邻苯二甲酸二（2-乙基）己酯和邻苯二甲酸二正辛酯的含量。对比超声 提取和索式提取2 种前处理方法对样品中塑化剂的提取效果,确定了程序升温条件,采用外标法定量。结果表明： 6 种标准物质的标准曲线R2为0.996 7～0.998 8,最小检出限为0.04 mg/kg,相对标准偏差为5.0%～9.3%;索式提取 法的提取效果更显著,某些火腿肠和火腿肠肠衣中含有高含量的生殖致癌物邻苯二甲酸酯类物质。     

2018年吉林省部分地区市售食用植物油产品中塑化剂含量的检测结果分析

目的 了解2018年吉林省部分地区食用植物油产品中塑化剂的污染情况。方法 检测并分析食用植物油产品155批次, 依据GB 5009.271-2016《食品安全国家标准 食品中邻苯二甲酸酯的测定》(第二法 气相色谱-质谱法 外标法), 对产品中的邻苯二甲酸二丁酯(dibutyl phthalate, DBP)和邻苯二甲酸二(2-乙基)己酯(di(2-ethylhexyl) phthalate, DEHP)2项塑化剂指标进行含量检测。结果 共有18批次食用植物油产品的塑化剂检测结果高于参考限值, 其中DBP超限率为11.61%, DEHP超限率为0.65%。结论 本次检测的食用植物油产品出现一定的塑化剂问题, DBP污染较为明显。污染来源可能来自塑料包装物、加工环节及环境污染, 塑化剂迁移途径和预防控制问题需要引起相关部门的重视。     

两种萃取溶剂对塑料食品包装材料上 有机污染物检测效果的影响

目的 检测两种萃取溶剂对塑料食品包装材料上有机污染物检测效果的影响。方法 分别以正己烷和无水乙醇为萃取溶剂对塑料食品包装材料上污染物进行超声提取, 提取后用旋转蒸发浓缩, 最后采用气相色谱-质谱联机(GC-MS)分析方法以离子化方式对浓缩的污染物进行表征。结果 正己烷作为萃取溶剂能萃取出抗氧化剂2, 6-二叔丁基对甲酚、增塑剂邻苯二甲酸二丁酯、油墨生产中所用的溶剂正十六烷; 乙醇作为萃取溶剂能萃取出抗氧化剂2, 6-二叔丁基对甲酚、油墨生产中所用的溶剂正十六烷和正二十烷。结论 正己烷作为萃取溶剂的提取效果要比乙醇作为萃取溶剂提取效果好。     

白酒中塑化剂GC-MS检测方法的研究

以邻苯二甲酸二丁酯（DBP）、邻苯二甲酸二（2-乙基）己酯（DEHP）、邻苯二甲酸二异壬酯（DINP）3种邻苯二甲酸酯类塑化剂为例,通过改进气相色谱-质谱法测定条件,研究得出适合白酒中塑化剂检测的方法。并采用不同包装的6个未知酒样进行方法应用测试,测试结果显示DBP含量高达2.03mg/kg,DEHP、DINP含量均在限量范围之内。     

Contents of plasticizers in cap-sealing for bottled food and their migration into food

Plasticizers in cap-sealing for bottled foods were analyzed. Twenty-three domestic samples and 80 imported samples, a total of 103 samples, were tested. Among them, 93 contained chloride, and 62 contained di(2-ethylhexyl) phthalate (DEHP), diisodecyl phthalate, O-acetyl tributyl citrate, diacetyllauroyl glycerol, di(2-ethylhexyl) adipate, diisononyl phthalate or dicyclohexyl phthalate. Twelve samples with DEHP-containing caps were further tested for plasticizer levels in the foods. Higher DEHP was detected in oily and fluid food specimens. However, the intake of plasticizers calculated based on usual food consumption did not exceed the tolerable daily intake level in any of the cases. A food sample containing the highest level of DEHP was stored under various conditions, and DEHP that migrated from the cap-sealing into the food was determined. Shaking the bottles increased migration of DEHP into foods.     

Estimated daily intake of plasticizers in 1-week duplicate diet samples following regulation of DEHP-containing PVC gloves in Japan

Duplicate hospital diet samples obtained over 1 week in 2001 were analysed to estimate the daily intake of plasticizers and the results were compared with those obtained in 1999. The plasticizers quantified in this study were: dibutyl phthalate, butylbenzyl phthalate (BBP), di(2-ethylhexyl) phthalate (DEHP), diisononyl phthalate (DINP), di(2-ethylhexyl) adipate (DEHA), diisononyl adipate (DINA) and O-acetyl tributyl citrate (ATBC). Dipropyl, dipentyl, dihexyl and dicyclohexyl phthalate were also analysed but not detected. The analytical procedure for this follow-up study was essentially the same as in the previous one. Detection limits were 0.1-15.6 ng g^-1 for each plasticizer. One-week duplicate diet samples provided by three hospitals in three remote prefectures of Japan were analysed as individual meals. DEHP was detected at 6-675 ng g^-1 in 62 of 63 meals, significantly lower levels compared with those detected in 1999. Levels of DEHA and DINP also decreased. The mean intake of plasticizers estimated from all samples was 160 μg DEHP day^-1, 12.5 μg DEHA day^-1, 4.7 μg DINP day^-1 and 3.4 μg BBP day^-1. Levels of DINA were relatively high in meals from one hospital: in those meals, the average daily intake was 1338 μg day^-1. Those of ATBC were also higher in meals from another hospital: the average daily intake was 1228 μg day^-1. The sources of DINA and ATBC can be cling-film or sausage packaging.     

Levels of phthalates and adipates in processed foods and migration of di-isononyl adipate from polyvinyl chloride film into foods

The levels of dibutyl phthalate (DBP), butylbenzyl phthalate (BBP), di-(2-ethylhexyl) phthalate (DEPHP), di-isononyl phthalate (DINP), di-(2-ethylhexyl) adipate (DEHA) and di-isononyl adipate (DINA) were determined in 50 processed foods (ham and sausage, fried dumpling and shao-mai, fish paste products, croquette and fried fish, bread, noodle, pickles, etc.). DBP, BBP, DEHP, DINP, DEHA, and DINA were contained at nd approximately 47.7, nd approximately 16.6, nd approximately 749, nd approximately 358, nd approximately 57.2 and nd approximately 20,200 ppb, respectively. High-level contamination of DINA was found in fish paste products, croquette and shao-mai, presumably because of migration from plasticized wrapping film using for food packaging. We studied the relationship between DINA migration from wrapped PVC film into fried croquette and its standing time after frying. When the croquette was wrapped immediately after frying, the migration from wrapping film into the croquette was highest (36,400 ng/g). On wrapping after standing for 5 min and 30 min, the migration level was reduced to 1/3.5 and 1/14 of the highest level, respectively.     

Migration of mineral oil,photoinitiators and plasticisers from recycled paperboard into dry foods: a study under controlled conditions

Migration from recycled paperboard was monitored after 2, 4 and 9 months of storage for six test foods industrially packed in five configurations, four with internal plastic films. After 9 months, the migration of mineral oil saturated hydrocarbons into foods directly packed in the paperboard amounted to 30–52 mg/kg, which corresponded to 65%–80% of those of a volatility up to that of the n-alkane C₂₄ in the paperboard. The concentration of the migrated aromatic hydrocarbons in the foods ranged from 5.5 to 9.4 mg/kg. More than half of this migration occurred in the first 2 months. Differences between the foods amounted to mostly less than a factor of 2 and seemed to be related to porosity or permeability more than fat content. Nine photoinitiators were detected in the paperboard, of which eight migrated into the packed food at up to 24%. Several plasticisers were present in the recycled paperboard, but only butyl phthalates showed significant migration. After 9 months, up to 40% of diisobutyl phthalate and 20% of dibutyl phthalate migrated into the food with direct contact. The internal polyethylene film hardly slowed migration, but the film and the tray absorbed approximately three times more mineral oil than the food, despite constituting merely 4% of the mass of the pack. Oriented polypropylene strongly slowed migration: The highest migration of saturated hydrocarbons measured after 9 months (2.3 mg/kg) corresponded to only 3% of the content in the paperboard and included migrated polyolefin oligomeric saturated hydrocarbons. Coating of polypropylene with an acrylate further slowed the migration, but the migration from the paperboard was still detectable in four of the six samples. Polyethylene terephthalate was a tight barrier.     

Development of anti-insect food packaging film containing a polyvinyl alcohol and cinnamon oil emulsion at a pilot plant scale

Anti-insect packaging films containing cinnamon oil (CO) encapsulated by polyvinyl alcohol (PVA) for repelling Plodia interpunctella (Hübner) larvae were manufactured using pilot plant scale instruments. The microcapsule emulsion of CO and PVA was printed onto polypropylene (PP) film as an ink mixture using the gravure printing method. The printed PP film was then laminated with a low-density polyethylene (LDPE) film to protect the printed side. Four types of multilayer films were produced: control film, 2% CO film, encapsulated 1% CO film, and encapsulated 2% CO film. When mechanical properties were assessed, tensile strength and elongation-at-break were not significantly different among films, whereas the Young's modulus values were different between the control film and the three types of CO-containing films. In a repellent test, 2% CO film repelled P. interpunctella larvae most effectively. For sensory evaluation, which was performed using milk chocolate, caramel soft candy, and cookies packaged with the produced films, the produced films did not affect the sensory characteristics. Therefore, the films printed with emulsions of CO and PVA could be applied in the food industry to help protect foods from infestation by P. interpunctella.     

Plasticizers in Brazilian food-packaging materials acquired on the retail market

Packaging materials intended for direct food contact were acquired on the Brazilian retail market and analysed for their plasticizer content. Analyses were carried out by gas chromatography with flame ionization detection. Di-2-ethyl-hexyl adipate (DEHA), di-2-ethyl-hexyl phthalate (DEHP) and di-iso-decyl phthalate (DIDP) plasticizers were identified in films and closure seals in concentrations ranging from 12 to 19% (w/w), 15 to 44% (w/w) and 10 to 11% (w/w), respectively. Brazilian regulations state that for use with foods with a fat content above 5%, the levels of DEHP and DIDP in the plastic material should be no greater than 3%. The results obtained demonstrate a lack of conformity. It would be advisable to include information on the labels of packaging materials about their restrictions of use in order to advise manufacturers and consumers about their proper usage.     

Migration analysis and health impact assessment of phthalates in takeaway food packaging materials

Plasticizers are commonly utilized as packaging additives in the food service industry. The takeaway food sector provides convenience to consumers, but also raises the risk of human exposure to plasticizers. The goal of this study is to determine the amount of phthalates in takeaway food packaging and compare the migration amounts under various situations. A comprehensive health impact assessment of phthalates was conducted to provide the evaluation of human's daily exposure to phthalates. The results revealed that five phthalates (di (2-ethylhexyl) phthalate (DEHP), butyl benzyl phthalate (BBP), diethyl phthalate (DEP), dimethyl phthalate (DMP), dibutyl phthalate (DBP)) could be detected in n-hexane extract of plastic food packaging materials at room temperature. High amount of phthalates was correlated with high temperature or in an oily food simulant solvent. Phthalate contents in dietary exposure did not surpass the concentration that could represent a risk to human health, based on the dietary exposure evaluation.     

PVC plasticizers/additives migrating from the gaskets of metal closures into oily food: Swiss market survey June 2005

Foods with at least a few percent of free oil packed in glass jars with metal closures were analyzed for migration of additives, primarily plasticizers, from the gasket of the lid. One hundred and fifty-eight samples were collected in June 2005, i.e., some 10 months after the problem of excessive migration into oily food was communicated to the industry. In a first step, the composition of the additives in the gaskets was determined. Then the compounds found in the lid were measured in the jar content. Sixty-four percent of the gaskets contained epoxidized soy bean oil (ESBO) as principal plasticizer, 22% a phthalate, and 6% substantial amounts of di(2-ethylhexyl) adipate (DEHA). Concentrations in the food reached 1,170 mg/kg for ESBO, 270 mg/kg for diisononyl phthalate (DINP), 740 mg/kg for diisodecyl phthalate (DIDP), 825 mg/kg for di(2-ethylhexyl) phthalate (DEHP), and 180 mg/kg for DEHA. Further, elevated concentrations of plasticizers not authorized by the EU were found: diisononyl-cyclohexane-1,2-dicarboxylate (DINCH), 2-ethylhexyl palmitate and stearate, as well as epoxidized linseed oil (ELO). The few samples complying with the European rules contained little or well emulsified oil; some others were probably of very recent production (beginning of shelf life). It is concluded that there was still no lid reliably complying with the European rules (EU and national legislation).     

Di(2-ethylhexyl) phthalate contamination of retail packed lunches caused by PVC gloves used in the preparation of foods

Plasticizer contamination of foods sold in retail packed lunches and set lunches in restaurants was determined by GC/MS. The phthalate esters were as follows: diethyl, dipropyl, dibutyl, dipentyl, dihexyl, butylbenzyl, dicyclohexyl, di(2-ethylhexyl), dioctyl, diisooctyl (mixture of isomers) and diisononyl (mixture). Di(2- ethylhexyl) adipate was also determined. Sixteen packed lunches and ten set lunches were analysed, and in all samples the concentration of di(2-ethylhexyl) phthalate (DEHP) was the highest, at 0.80-11.8 mg/ kg in packed lunches and 0.012-0.30 mg/kg in set lunches. The DEHP content of five packed lunches exceeded 1.85 mg, which is the EU tolerable daily intake (TDI) for a person of 50 kg body weight. Foodstuffs that were components of the packed lunches were taken from the factory at each step of preparation and phthalates were determined. For example, chicken contained 0.08 mg/kg DEHP when uncooked, 13.1 mg/ kg after frying and 16.9 mg/kg after packing. Disposable PVC gloves used in the preparation of foods were apparently the source of high DEHP concentrations. The gloves used during cooking or packaging were sprayed with 68% (w/w) ethanol to sterilize them. PVC gloves from the factory contained 22 or 41% by weight of DEHP. To confirm the link with the contamination problem, samples of boiled rice, croquette and boiled dry radish were handled in the laboratory with PVC gloves containing 30% (w/w) DEHP. DEHP migration levels of 0.05 mg/kg in rice or 0.33 mg/kg in croquette, and 11.1 mg/kg in radish were found. The alcohol sprayed onto the gloves increased the migration of DEHP to 2.03 mg/kg in rice, 2.45 mg/ kg in croquette, and 18.4 mg/kg in radish.     

可食性喷墨油墨性能对印刷品质量的影响

可食性喷墨油墨为水性油墨,绿色环保,其原料全部符合食品卫生标准,可以用喷墨印刷的方式直接在食品、药品或产品的包装表面印刷,具有色彩鲜艳、无毒、无污染的特点。采用在油墨中添加不同含量的染料、树脂及表面活性剂的方法,改变油墨的黏度和表面张力,探讨不同性能的可食性喷墨油墨对印刷品质量的影响。采用CCD图像检测分析系统,对印刷品的线条质量、实地填充质量及圆点质量进行评价和分析;用密度计测量印品的色密度并进行颜色评价。结果表明,可食性喷墨油墨的黏度和表面张力影响印刷品的质量,通过调整树脂及表面活性剂用量,可以获得适于喷墨印刷的可食性喷墨油墨。     

从SCI检索看国际绿色印刷包装研究发展态势

为了解国际上绿色印刷包装研究的现状与发展态势,选取科学引文索引(SCI)2008～2012年所收录的绿色印刷包装中有关印刷电子、环保油墨、按需喷墨、印后加工等4个研究方向的文献进行汇总、利用文献研究法进行综合分析,可以看出近5年来印刷电子文献高速增长,环保油墨文献量维持在相对较高的水平,而按需喷墨、印后加工的文献量明显下滑,印刷电子和环保油墨成为行业研究的热点。     

Effects of various plasticizers and nanoclays on the mechanical properties of red algae film

To manufacture red algae (RA) film, we used various plasticizers such as glycerol, sorbitol, sucrose, fructose, and polypropylene glycol (PPG), and then determined the mechanical properties of the RA films. The tensile strength (TS), elongation at break (E), and water vapor permeability (WVP) of the films containing various plasticizers ranged between 0.43 to 9.10 MPa, 10.93% to 47.17%, and 1.28 to 1.42 ng m/m2sPa, respectively. RA films containing fructose as a plasticizer had the best mechanical properties of all the films evaluated. Incorporation of nanoclay (Cloisite Na+ and 30B) improved the mechanical properties of the films. RA film with 3% Cloisite Na+ had a TS of 10.89, while RA film with 30B had a TS of 10.85 MPa; these films also had better E and WVP values than the other RA films evaluated. These results suggest that RA/nanoclay composite films are suitable for use as food packaging materials. PRACTICAL APPLICATION: Edible RE/nanoclay composite films prepared in the present investigation can be applied in food packaging.     

Phthalates in paper and board packaging and their migration into Tenax and sugar

Packaging samples for many kinds of foodstuffs were received from manufacturers together with basic information about the materials used in their production. Half of the 29 samples studied contained phthalates in amounts exceeding 5mg/kg. Two types of paper bag intended for sugar had exceptionally high phthalate contents although they were flexo printed. The maximum contents of di-isobutylphthalate (DIBP) and dibutylphthalate (DBP) were 450 and 200 mg/kg, respectively. The phthalates found originated from adhesives used in the joints of the packaging. In other packagings manufactured at the same time, DIBP concentrations varied from 92 to 193mg/kg. Phthalates were also determined in sugar before and after packaging. Migration of phthalates ranged from 57 to 74% of the original content in the packaging after 4 months storage. Packed sugar contained DIBP 2.2-2.6mg/kg and DBP 0.5-1mg/kg. The sugar packagings were also tested using Tenax as a food stimulant. The results indicated that 69-91% of the original content of the phthalates migrated into Tenex after 10 days at 40 C. The major drawback with migration testing using Tenax is its high cost; it is not practical to fill the whole 1kg packaging with Tenax, and smaller samples of packaging must be used instead. However, the distribution of substances in the packaging might be nonuniform. In the sugar packagings studied here, the difference between phthalate concentrations in two samples taken from the same packaging was nearly 100-fold.