旧报纸脱墨的研究进展

介绍了新闻纸的主要印刷方式、不同印刷方式所用油墨的组成及其脱墨性能。针对目前回收废纸中柔版印刷(水基油墨)废纸比例的增大对旧报纸(ONP)脱墨带来的影响,重点介绍了水基油墨印刷废纸的脱墨化学品研究、脱墨工艺、脱墨废水的处理技术以及脱墨效果评价方法,对旧报纸的脱墨过程提出了一些建议。     

Analysis of food packaging UV inks for chemicals with potential to migrate into food simulants

Ultraviolet (UV) inks are an alternative formulation system to the more usual paste or liquid inks (oils or solvents based) that dry mainly by evaporation or penetration into the printed substrate. Based on acrylic acid chemistry, UV inks dry (the exact term is 'curing') by the chemical process of photopolymerization. Their composition (acrylate monomers and oligomers together with photo-initiators) exposed to UV emission lamps on the printing press units enable the transformation of the freshly printed ink layer into a tack-free film. For UV inks intended for primary food packaging, special care has to be paid to potential migrating species like small photo-initiator molecules and acrylate monomers not cross-linked in the formed network. The paper presents chromatographic methods to ascertain the level of ink ingredients potentially available to migrate into food simulants (migration tests). GC/MS was employed to quantify the levels of photo-initiators or acrylic esters (acrylates).     

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。     

Factors affecting 3D printing and post-processing capacity of cookie dough

This study aimed to investigate the factors affecting the printability and post-processing capacity of cookie dough in extrusion-based three-dimensional (3D) printing by modifying the recipe without the addition of gums or stabilizers. Cookie dough formulations with different types of fat (butter and shortening), flour (wheat, rice, and tapioca), the amount of non-fat milk (32.5 or 65 g/100 g flour), and the sugar level (37.5 or 55 g/100 g flour) were investigated for their printability and post-processing capacity. Rheological properties, microstructure, and printability of printing inks were monitored while the moisture loss and dimensional stability after baking were analyzed in printed and baked structures, respectively. Results indicated that cookie dough formulations with reduced sugar content were more printable. The best sample to build a shape that could withstand the baking process was the recipe of 37.5 g sugar, 62.5 g shortening, 100 g tapioca flour, and 32.5 g milk, which yielded printed cookie samples with the ease of printing, better visual printing outcomes, and no structural deformation after baking.Industrial relevance3D food printing is an emerging technology with many potential applications in the food industry. It is important to understand the effects of key components of food materials on the printing, which enable a wider range of structures just using a single nozzle, and provide tailored nutrition and personalization in extrusion-based 3D printing. Understanding the effects of food processing on 3D printed food items is critical to broadening its applications. This study selected cookie dough as a model system to investigate the 3D food printing since it is mainly composed of fat, sugar, flour, and milk that are the most common ingredients in many food products. Establishing knowledge of the interactions between different food components and contribution of each individual ingredient may help develop a guideline for extrusion-based 3D food printing. In addition, the results acquired from this study can fill knowledge gaps regarding the role of cookie dough component in 3D printing and their effects on post-processing of 3D printed foods.     

Is recycled newspaper suitable for food contact materials? Technical grade mineral oils from printing inks

Recycled paper and board used in food packaging materials (boxes, paper bags) often cause migration of mineral oil into food at levels which are unacceptable according to present toxicological assessments. When foods in recycled board are densely packed into larger boxes or onto pallets, most of the hydrocarbons up to n-C₂₀ may migrate into the packed food within a few weeks, those up to n-C₂₈ at a decreasing rate. Unprinted recycled board contained 300–1,000 mg/kg mineral oil <n-C₂₈. The main sources are the inks used for printing newspapers: newspapers contained roughly 3,000 mg/kg mineral oil <n-C₂₈. These mineral oils fall into classes for which JECFA established a tolerable daily intake of 0.01 mg/kg body weight. Using standard assumptions for calculating specific migration limits, a maximum tolerable concentration in food of 0.6 mg/kg is derived. This evaluation assumes highly refined white oils, whereas the oils found in recycled board are of technical quality and contain 15–25% aromatic compounds, predominantly with 1–3 aromatic rings, as shown by comprehensive GC × GC. This finding precipitates authorities into a dilemma: recycling is supported for the sustainable use of materials, but on the basis of present toxicological assessments the migration is often far beyond acceptable.     

Saturated and aromatic mineral oil hydrocarbons from paperboard food packaging: estimation of long-term migration from contents in the paperboard and data on boxes from the market

In the absence of a functional barrier, mineral oil hydrocarbons from printing inks and recycled fibres tend to migrate from paper-based food-packaging materials through the gas phase into dry food. Concentrations easily far exceed the limit derived from the acceptable daily intake (ADI) of the Joint FAO/WHO Expert Committee on Food Additives (JECFA). Since the estimation of long-term migration into the food by testing at 40°C for 10 days is difficult, it seems preferable (and easier) to use the mineral oil content in the paperboard. Evaporation experiments showed that hydrocarbons eluted up to about n-C₂₄ are sufficiently volatile for relevant migration into dry food: in worst-case situations, about 80% migrate into the packed food. The extraction of the paperboard was optimised to give good recovery of the relevant hydrocarbons, but to discriminate against those of high molecular mass which tend to disturb gas chromatographic analysis in on-line coupled normal phase HPLC-GC-FID. Even though some of the relevant hydrocarbons had already evaporated, the average concentration of?<?C₂₄ mineral oil saturated hydrocarbons (MOSH) in the paperboard boxes of 102 products from the Swiss and Italian market was 626?mg?kg^?1. Nearly 15% of investigated boxes still contained more than 1000?mg?kg^?1?<?C₂₄ MOSH up to over 3000?mg?kg^?1 (maximum?=?3500?mg?kg^?1). This amount of MOSH in the board have the potential of contaminating the packed food at a level exceeding the limit, derived from the JECFA ADI, hundreds of times.     

Determination of food contamination by mineral oil material from printed cardboard using on-line coupled LC-GC-FID

 Inks used for printing paper and cardboard are dispersions of synthetic organic pigments in a bonding agent system built up essentially of resins, vegetable oils and high-boiling-point mineral oil products (b.p. >250°C). The proportion of mineral oil material in the ink ranges between 20 and 30%. The more volatile mineral oil components slowly evaporate from the printed cardboard box and may migrate into the food product. They contaminated cereals and dry baby-food products at concentrations between 10 and 150 mg/kg. Received: 27 January 1997     

Comparing the rheological and 3D printing behavior of pea and soy protein isolate pastes

In this study the viscoelastic properties of pea and soy protein pastes with concentrations ranging from 10 to 21%w/w were correlated with their ‘printability’ following extrusion 3D printing. The rheological parameters G´, tanδ and σ_y were affected by the protein concentration, and a different viscoelastic behavior was observed for PPI and SPI pastes. At low protein concentrations (10–16%w/w) SPI presents a more elastic behavior than PPI, whereas at higher protein concentrations (>17%w/w) their rheological behavior was similar. No self-supporting structures could be printed for pastes with protein concentrations <15%w/w. In the protein range of 15–17%w/w, SPI formed more stable 3D printed objects compared to PPI. SPI shows a more elastic structure that increases stability against collapse during 3D printing. At higher protein concentrations for PPI, the increase of G´, σ_y and K counteracted the importance of n and tanδ, resulting in self-supporting 3D printed products comparable to SPI.Industrial relevanceThis work provides a better understanding of the importance of rheology of plant-protein food inks to printability by attempting to establish printing predictors, which is important for the development of new inks for 3D printed foods.     

旧报纸和旧杂志油墨的老化对可脱墨性的影响

本文介绍了矿物油基黑色油墨印刷的报纸和植物油基彩色油墨印刷的报纸,分别与杂志纸按比例一起在自然地和人为地老化（陈化）后的可脱墨性,从而提高了老化对旧报纸和旧杂志可脱墨性影响的认识。     

Saturated and aromatic mineral oil hydrocarbons from paperboard food packaging: estimation of long-term migration from contents in the paperboard and data on boxes from the market

In the absence of a functional barrier, mineral oil hydrocarbons from printing inks and recycled fibres tend to migrate from paper-based food-packaging materials through the gas phase into dry food. Concentrations easily far exceed the limit derived from the acceptable daily intake (ADI) of the Joint FAO/WHO Expert Committee on Food Additives (JECFA). Since the estimation of long-term migration into the food by testing at 40°C for 10 days is difficult, it seems preferable (and easier) to use the mineral oil content in the paperboard. Evaporation experiments showed that hydrocarbons eluted up to about n-C?? are sufficiently volatile for relevant migration into dry food: in worst-case situations, about 80% migrate into the packed food. The extraction of the paperboard was optimised to give good recovery of the relevant hydrocarbons, but to discriminate against those of high molecular mass which tend to disturb gas chromatographic analysis in on-line coupled normal phase HPLC-GC-FID. Even though some of the relevant hydrocarbons had already evaporated, the average concentration of < C?? mineral oil saturated hydrocarbons (MOSH) in the paperboard boxes of 102 products from the Swiss and Italian market was 626 mg kg?1. Nearly 15% of investigated boxes still contained more than 1000 mg kg?1 < C?? MOSH up to over 3000 mg kg?1 (maximum = 3500 mg kg?1). This amount of MOSH in the board have the potential of contaminating the packed food at a level exceeding the limit, derived from the JECFA ADI, hundreds of times.     

低黏度油墨和橡皮布对无水胶印印刷导电层的影响研究

近年来,随着全球市场对电子器件需求量的不断增长,许多科研院所及部分企业都在尝试利用传统印刷(柔印、凹印、网印等)和数码印刷(喷墨印刷等)技术来制作电子器件。为了实现电子器件的高沉积精度,对印刷技术提出了以下几点要求:线条无缺陷,有锐边且分辨率高;图层无针孔,均匀且表面光滑;墨层厚度较薄。     

不同类型油墨碱法脱墨性能的研究

对采用不同类型油墨印刷的新闻纸、胶版纸和铜版纸的脱墨性能进行了初步研究,同时评价了不同类型脱墨剂对新闻纸脱墨效果的影响。实验结果表明,在常规的碱法浮选脱墨工艺中,油基油墨的脱墨效果最好,水性光固化油墨次之,水性柔性版油墨脱除率最低;3种不同类型的脱墨剂中,BH脱墨剂的脱墨效果最好。     

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。     

适应不同承印物的UV喷墨油墨印刷适性

为了探讨在不同承印物上UV喷墨油墨印刷适性的差异,提高UV喷墨油墨在不同承印物上的印刷质量,选用铜版纸、玻璃卡标签纸、PVC塑料薄膜3种承印材料,分别用相同的UV喷墨油墨进行喷墨印刷,测试样张中线条的密度、模糊度、粗糙度、线宽、对比度等印刷质量指标;测量喷墨油墨在各承印材料上的接触角,结合其润湿情况,分析UV喷墨油墨在不同承印材料上的印刷质量。实验共制备10种不同表面张力与黏度的油墨进行喷墨印刷并测试印刷质量,采用综合分析评价方法评价其印刷质量。结果表明：在不同承印物上印刷时,UV喷墨油墨的印刷质量存在较大差异,实际生产中应根据所采用的承印物匹配相应印刷适性的UV喷墨油墨,以得到最佳印刷效果。     

Development of an analytical method for the determination of photoinitiators used for food packaging materials with potential to migrate into milk

Photoinitiators are used in the curing process during UV printing of food carton labels. The alarm concerning the detection of a photoinitiator, 2-isopropyl thioxanthone (ITX), in food samples packed with cartons printed with UV-cured inks has focused the attention of legislative authorities on the potential migrants from packaging inks into foods. For this reason it is very important to carry out analytical methods for the detection of those compounds in food as potential migrants from packaging. The aim of the present work was to develop a multimethod for the analysis of 6 photoinitiators in milk. The selected photoinitiators were Irgacure 184, benzophenone, Irgacure 651, Irgacure 907, Quantacure ITX, and Quantacure EHA (2-ethylhexyl-4-dimethylaminobenzoate). Milk (10 mL) extraction was carried out by using ammoniac and hexane. The supernatant was evaporated and the residue was redissolved with acetonitrile. Then, the extract was analyzed by HPLC-UV. Calibration lines were carried out over the concentration range of 0.1 to 10 mg/L. The calibration data presented high correlation coefficients (>0.9999). Mean recoveries (n = 6) of the 6 photoinitiators were 83.4% (residual standard deviation = 2.3%) at 0.5 mg/kg and 81.0% (residual standard deviation = 4.6%) at 1 mg/kg. Several milk samples and their respective packaging cartons were analyzed. Results were confirmed by HPLC-mass spectrometry.     

蓖麻油基紫外光固化水性涂料墨水制备及其印花性能

为解决传统涂料印花存在的手感和牢度难以兼顾的问题,以蓖麻油、异佛尔酮二异氰酸酯、2,2-二羟甲基丁酸缩聚,再以季戊四醇三丙烯酸酯为封端剂,制得具有优异分散性、耐水性、黏结牢度的水性聚氨酯乳液,并在加入纳米颜料后制得蓖麻油基紫外光固化水性涂料墨水。研究并分析了蓖麻油含量对乳液粒径、固化胶膜性能、耐水性等的影响及原因。随后以涤纶平纹织物为代表,对比表征了蓖麻油基紫外光固化水性涂料墨水喷墨印花织物表面形貌和硬挺度、耐干湿摩擦色牢度等性能,结果表明,在最佳蓖麻油质量分数为42.1%时,喷墨印花织物具有良好的柔性和色牢度。     

聚乙烯亚胺/氮掺杂纳米TiO2喷墨打印墨水的制备及性能研究

由于纳米二氧化钛（TiO₂）具有无毒、折射率高、化学稳定性高的特点,特别是因存在光生空穴而具有强氧化性,已广泛应用于光催化剂、光电池、电池组、光致/电致变色装置、气敏传感器、薄膜晶体管等光化学产品中。然而,未改性的TiO₂只能吸收波长小于387nm的紫外光,在一定程度上限制了其应用范围。采用氮掺杂技术可以缩小锐钛型TiO₂的带宽,从而提高TiO₂在可见光区的光吸收性和光催化性。如将N-TiO₂分散后用于光催化和光伏研究方面,时间稳定性高的N-TiO₂溶液可用于喷墨打印。     

Potential for short-term migration of mineral oil hydrocarbons from coated and uncoated food contact paper and board into a fatty food simulant

ABSTRACT

Mineral oil hydrocarbons (MOH) are widely used in the food industry for applications such as printing inks, additives, adhesives, and processing aids for food additives. Recently, the migration of MOH from food contact paper and board into foods has raised public health concerns. In this study, a total of 110 food contact paper and board samples, including baking and cooking paper (23), baking cups (28), food packaging bags (22), lunch boxes (8), party plates (26), and straws (3) were evaluated to quantify the content and short-term migration levels of MOH. The MOH were separated into mineral oil saturated hydrocarbons (MOSH)/polyolefin oligomeric saturated hydrocarbons (POSH) and mineral oil aromatic hydrocarbons (MOAH) via a validated on-line liquid chromatography?gas chromatography?flame ionisation detection (LC–GC–FID) technique. The coating materials of the sample products comprised polyethylene, polypropylene, polyethylene terephthalate, and silicone. The effects of the coating materials on the content and migration of MOH/POSH were evaluated. Quantitative analysis of the MOH in the samples showed that the MOSH/POSH and MOAH content varied widely, ranging from 16 to 5626 mg kg^?1 for MOH, regardless of the coating materials. Short-term migration of MOSH/POSH was observed only in samples with polyolefinic coatings, such as polyethylene and polypropylene, in experiments conducted at 25 °C for 10 min, although the extent of MOAH migration for all samples was at the trace level. The migration of MOSH/POSH was detected within the range of 0.93 to 62.3 μg L^?1 in 22 samples, and the migration of MOAH was detected within the range of 0.80 to 2.6 μg L^?1 in only 4 samples. These results demonstrate that although the short-term migration potential of MOH is generally negligible, the migration of MOSH/POSH into wet fatty foods can be accelerated by polyolefinic coatings, even within a very short time.     

Activated carbon added to recycled paperboard to prevent migration into food: approach for determining efficacy,and first results

Catcherboard MB12® from Smurfit Kappa is a recycled paperboard incorporating activated carbon to reduce the release of contaminants into food. An approach is proposed to determine the efficacy of the activated carbon. Sorption into activated carbon increases the concentration ratio paperboard/food (distribution coefficient) and reduces the migration rate, i.e. prolongs the time for equilibration. Using silicone paper as food simulant, the concentration ratio was increased by a factor of at least 1000 compared to recycled paperboard without activated carbon, which is sufficient to meet the 1% criterion proposed for barriers. Sorbents have limited capacity. A load with in total 4000 mg surrogate substances/kg paperboard (in addition to the material from the paperboard) exceeded the capacity: concentration ratios were reduced and the release of paperboard constituents increased. Capacity is consumed by constituents from the printing inks and the packed food. Total amounts of substances in dry foods of sufficient volatility to potentially migrate into the paperboard through the gas phase at ambient temperature were determined by GC-FID. For the large majority of the dry foods, these amounts were clearly below the capacity limit even under the exaggerated assumption of total transfer. Migration of mineral oil hydrocarbons into cat food over up to 1 year was not detectable at 1 mg/kg. It is concluded that recycled paperboard with activated carbon is promising for respecting the 1% criterion stipulated for functional barriers to avoid food contamination from recycled paperboard.     

快餐包装纸中矿物油向固体食品模拟物的迁移

研究从市场上收集到的24 种快餐包装纸中的矿物油向固体食品模拟物Tenax的迁移规律。在多个不同的迁移条件（40 ℃/0.5、1、2、3 h,40 ℃/10 d和70 ℃/2 h）,探究矿物油的迁移行为及其影响因素,以评价其安全性。选择正己烷-乙醇（1∶1,V/V）混合溶液对Tenax进行过夜萃取,采用质量分数0.3%硝酸银固相萃取柱对饱和烃矿物油（mineral oil saturated hydrocarbons,MOSH）和芳香烃矿物油（mineral oil aromatic hydrocarbons,MOAH）进行分离纯化,最后用气相色谱-氢火焰离子化检测法和气相色谱-质谱法分别进行定量和定性分析。结果表明：随着温度的升高,多种快餐包装纸中矿物油向Tenax的迁移量也随之增加。涂蜡纸中MOSH迁移量均有所检出,其数值为110.49～615.40 mg/kg,而MOAH部分均未检出,这可能是因为涂蜡纸表面涂覆的石蜡层属于MOSH类,导致其MOSH部分的迁移量较高。网购餐盘纸和常规餐盘纸中MOSH迁移量约为其特定限量值（0.6 mg/kg）的10～400 倍,MOAH的迁移量约为其特定限量值（0.5 mg/kg）的10～70 倍,而使用优质胶印油墨的原生纤维餐盘纸均未超过其限量值。最后,通过对印有胶印油墨的原生纤维餐盘纸中矿物油进行溯源分析,发现经过迁移的矿物油一部分可能来源于其所用油墨,其他来源可能来自于回收纤维、黏合剂、添加剂和加工助剂等。