单体对UV油墨颜色特性影响的研究

为了研究UV油墨的主要成分——单体的种类对油墨颜色特性的影响,使用制备UV油墨常用的11种丙烯酸酯系列单体,配制UV四色油墨,通过测试油墨的色度值,并比较各种油墨的色相和饱和度,以及不同种类油墨的色差,从而研究丙烯酸酯单体对UV油墨颜色特性的影响。研究结果表明,不同种类单体对油墨的明度值影响较小,而对a^＊、b^＊值有一定的影响,但对不同颜色油墨影响不同,采用PETA配制的黑油墨的颜色性能较其他种类单体好;单体种类对UV油墨的饱和度影响较小,主要影响了UV油墨的色相;单体结构对油墨的颜色特性是有影响的,双官能团单体所配油墨与三官能团所配油墨的颜色差别很大,而三官能团所配油墨的颜色相互差别较小。     

UV油墨固化速率的影响因素研究

UV油墨固化速率不仅受到油墨中各组分的影响,而且与墨膜厚度有密切关系.本研究分别使用不同种类的预聚物、单体、光引发剂配制油墨,研究油墨各组分对UV油墨固化速率的影响;进而固定油墨其他组分,改变光引发剂种类及其含量配制油墨,并制备不同墨层厚度的样品,测试不同墨层厚度下的油墨预聚物双键转化率,分析光引发剂种类及其含量与不同厚度墨膜固化速率的关系.测试不同UV光源功率下的双键转化率,研究含不同光引发剂的油墨在不同功率下的固化速率.研究结果表明,油墨各组分对UV油墨固化速率有一定影响,此外,随着墨层厚度的增大,油墨双键转化率降低;当光引发剂含量小于10％时,UV油墨的固化速率随着光引发剂含量的增加而增大;UV油墨的双键转化率随着UV光源功率的增大而增大.     

颜料型UV喷墨油墨的配方研究

UV喷墨油墨是一种绿色环保型油墨,但是目前来看UV喷墨油墨的价格昂贵,且在生产过程中提高油墨的分散性和稳定性是较大的技术难题。本研究针对如何减小油墨粒径,提高油墨稳定性等性能问题,用UV-2700紫外光分光光度计测定颜料和光引发剂的紫外透射光谱图,找出颜料的透光窗口和光引发剂的吸收峰值,匹配出不干扰紫外光吸收的颜料和光引发剂,再在后期的性能测定试验中确定颜料和光引发剂的种类和比重,运用均匀设计法,以达到D95粒径最小为指标,确定单体、分散树脂和分散剂的最优配方;配制出色浆基墨后,运用正交试验设计方法,以黏度、表面张力、固化速度和色密度为指标,确定色浆、成膜树脂、光引发剂、助剂的配方,最终优选出各方面都达到指标要求的UV喷墨油墨的最佳配方。     

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。     

Rapid multi-analyte quantification of benzophenone, 4-methylbenzophenone and related derivatives from paperboard food packaging

Photo-initiators are used in printing inks hardened with UV light and one of the most commonly used photo-initiators is benzophenone (BP). Recent notifications under the Rapid Alert System for Food and Feed have shown migration of 4-methylbenzophenone (4-MBP) from packaging into cereals. A specific migration limit exists for BP of 0.6 mg kg^?1 for its use as an additive in plastics. There is no specific European legislation covering cardboard boxes and/or printing inks for food contact use. However, due to the high levels detected, the European Food Safety Authority (EFSA) published recommendations and the Standing Committee for the Food Chain and Animal Health endorsed a limit of 0.6 mg kg^?1 for the sum of BP and 4-MBP. While studies have been published on photo-initiators in the past, there is a fundamental lack of data on 4-MBP especially for its combined analysis with others. We present an HPLC method with diode array detector to simultaneously determine the levels of BP, 4-MBP as well as 7 other possible derivatives from secondary packaging for food applications. The method was tested and applied to 46 samples of paperboard for secondary packaging collected both from supermarkets and directly from a paperboard supplier. In addition, a survey was conducted on recycled paperboard (n = 19) collected from a supplier, to evaluate the background quantity of BP and other derivatives in recycled board. The most abundant photo-initiator found in the survey was BP, in 61% of samples, and 4-MBP was found in 30% of the samples. It seems that these compounds are used to replace one another. Other derivatives were found in minor quantities. Traces of BP were also found in 42% of the samples of recycled, unprinted board.     

Survey on the occurrence of photo-initiators and amine synergists in cartonboard packaging on the German market and their migration into the packaged foodstuffs

In a surveillance study from 2008 to 2011, in total 310 food products, predominately packed in cartonboard, were collected from the German market. First, the packaging materials were analysed for their content of six photo-initiators and five amine synergists by high-performance liquid chromatography with diode array detection (HPLC-DAD). If high amounts of these substances were detected, subsequently the foodstuffs were analysed by means of HPLC-MS or tandem MS, respectively. Benzophenone (BP) was detected in 49% of the packaging materials and was thus the most often determined compound, followed by 4-methylbenzophenone (MBP, 8%), 1-hydroxy-cyclohexylphenylketone (HCHPK, 7%) and methyl-o-benzoylbenzoate (MOBB, 5%). In total, 99 foodstuffs were analysed and in 20 cases one or more photo-initiators and/or amine synergists were detected in quantities above the legally acceptable limits in food. This resulted in several notifications in the European Rapid Alert System for Food and Feed (RASFF); the best known is MBP in breakfast cereals. Contamination of the foodstuff by the photo-initiators and/or amine synergists also occurred when it was in indirect contact with the printed packaging material and no adequate barrier material was used to prevent migration. The data also clearly demonstrate that polyethylene films are not suitable to inhibit migration. Storage of samples until the best before date showed that HCHPK, BP and MBP migrate very easily via the gas phase. In contrast, 4-phenylbenzophenone and 4,4′-bis(diethylamino)benzophenone migrated only very slowly or, respectively, not in quantifiable amounts into the foodstuffs. Differences in transfer rates for HCHPK, BP and MBP from several packagings into food and Tenax^®, respectively, lead to the assumption that both the food matrix as well as the extent of cross-linking of the printing ink during curing may have an influence on the level of migration.     

Performance testing and evaluation of reactive dye inks for silk digital printing北大核心CSCD

In order to explore suitable reactive inks for silk digital printing, reactive dye inks of eight brands were selected from the domestic market to evaluate their pH, Conductivity, absorption spectrum, color gamut range and their application performance including color yield, dry and wet rubbing fastness. The results showed that pH values of ink of different brands ranged from neutral and weakly acidic property, which would be helpful to reduce hydrolysis of the reactive dye and improve their stability. Reactive inks with lower conductivity could avoid salt crystallization which would cause nozzle blocking and corrosion problem. The hue of three primary colors (CMY) was stable, while that of spot color (BRO) had some differences, and the overall gamut range of these ink sets were different at different brightness levels. The application performance of the printed silk demonstrated that the increase in the stability of reactive ink would improve the color yield and color fastness of the printed fabric. © 2018 China Silk Association. All rights reserved.     

Utility of nonwovens in the production of integrated electrical circuits via printing conductive inks

This study reports on the printing of conductive inks directly onto nonwovens to produce circuits and embedded systems. The approach adopted applies polymer thick film (PTF) processing technologies directly onto compliant, flexible, nonwoven substrates. The paper reports on the characterization of various PTF conductive inks and printed transmission lines. The performance metrics related to the circuits are impacted by the ink viscosity and by the contact angle of the ink on the surface of the nonwoven structure. These parameters dictate the manner in which the ink is distributed onto and into the substrate. The manner in which ink droplets interact with the surface of the substrate determines the mechanisms responsible for both in-plane flow and through-the-plane flow of the ink.     

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。     

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。     

Radikalische Photoinitiatoren - Verfahren für Migrationsanalysen und Ihre Anwendung

Radical Photoinitiators: Detection Methods for Migration Analyses and their Application The idea for this dissertation was triggered by a RASFF notification in 2005 on the contamination of baby milk packaged in beverage cartons with isopropylthioxanthone (ITX), which was used as photoinitiator (PI) in the UV ink applied to print the packaging material. UV printing inks have a broad range of applications in food packaging and cover all types of materials such as paper and board, rigid and flexible plastics and multilayer materials. In the framework of this thesis, a surveillance study was carried out on predominately cartonboard packaged foodstuffs. 310 samples were collected on the German market and analysed for a total of eleven PIs and amine synergists (ASs). For 290 samples, either none of these PIs and/or ASs were detected in the packaging material or their calculated or analysed amount that might migrate or had migrated into the packaged food was below the migration limits specified in the Swiss “Printing Ink Ordinance” or, for not evaluated PIs and ASs, below 10 μg kg¹ food. In 20 foodstuffs, however, these limits were exceeded. Most notable was a sample of instant noodles in which the PI 1-hydroxycyclohexylphenylketone had migrated at a level more than 400-fold above the tolerable amount of 10 μg kg^-1 food for toxicologically not assessed substances. Contamination of the food occurred even during frozen storage and both in direct and indirect contact when no adequate barrier material was used to prevent migration. Here polyethylene was proven not to provide an adequate migration barrier. The analysis of samples stored until their best before date indicated that the degree of migration depends on the vapour pressures of the PIs and ASs, the food matrix and the extent of polymerisation and cross-linking of the printing ink monomers/oligomers. Transfer rates up to 52% were observed for PIs with high vapour pressures. These result from the contribution of all three possible mass transfer ways: set-off, permeation and gas phase transfer. Migration is also enhanced due to the porous structure of cartonboard and the usually very long shelf life and thus storage time of foodstuffs packaged in such food contact materials (FCMs). The results of this study contributed to the draft of a national regulation on printing inks for FCMs in Germany, which was adopted in December 2021. For stacked FCMs such as yoghurt cups, it was not clear which of the three mass transfer ways determines or contributes to the contamination of the packaged food. The study conducted here on this issue showed that under the selected contact conditions the contamination of yoghurt with ITX and an AS occurred via set-off. Transfer rates of up to 2.8% were determined. The degree of ITX migration increased with both the UV lamp age and the storage time of the printed, unfilled cups. Migration of another PI present in the ink was not detectable (< 4 μg kg^-1 yoghurt), although its amount on the printed cups was up to twice that of the AS. In addition, it could be demonstrated for the three examined substances that 50% ethanol is suitable as a simulant for yoghurt. Furthermore, five frequently used PIs were examined for their decomposition products (DPs). Both in UV irradiated isopropanol solutions and in extracts of cured model inks, a multitude of DPs was detected for each PI and for a total of 34 DPs structure proposals could be made. Among these were twelve that, to my best knowledge, were previously not described as (possible) DPs of the studied PIs. Yoghurt cups printed with inks containing all five PIs were subjected to migration tests with 50% ethanol. Transfer rates of up to 1.5% were observed for the PIs, which are comparable to those of the study on mass transfer ways for yoghurt cups. The same migrates were also analysed for eight of the identified DPs for which reference standards were available. Only the migration of 4-morpholinobenz-aldehyde was detected. Its transfer rate was considerably more, at 14%, due to its higher polarity and the much lower molecular weight compared to the PIs. Except for two DPs that were reaction products with isopropanol, a preliminary risk assessment using the TTC concept was performed for all DPs identified in the isopropanol solutions and/or ink extracts. Structural alerts of genotoxic carcinogenicity were found for five of the DPs, including 4-morpholinobenzaldehyde. Thus, these were prioritised for a toxicological evaluation by the TTC approach and their exposure should not exceed the threshold of 0.0025 μg kg bw^-1 day^-1 without further toxicological data. The maximum concentration of 4-morpholinobenzaldehyde determined in the migration tests was equivalent to 0.3 μg per 150 g yoghurt, i.e. the content of one cup. In consequence, for a European adult, the TTC threshold would already be exceeded by the daily consumption of the yoghurt contained in one cup. For a toddler, this would result in a tenfold exceedance. Further data on both toxicology and exposure are needed to assess whether the transfer of 4-morpholinobenzaldehyde into food could pose a risk to consumer health. This example illustrates the importance of conducting risk assess-ments not only for the substances used in FCMs, here the PIs, but also for their DPs and reaction products, the so- called “non-intentionally added substances” (NIAS). Two multi-analyte methods for the detection of a total of 63 PIs and ASs were also developed within the scope of this thesis. First, a HPLC-DAD method was designed primarily for screening FCMs. With this method, 50 mainly monomeric PIs and ASs, respectively, can be analysed simultaneously. Selectivity was enhanced by preparing a database containing all spectra and retention times of these substances, also relative to two internal standards. Together with the described extraction procedure, it is simple and easy performable without high technical effort and can thus be conducted by many laboratories. For the analysis of a total of 13 polymeric PIs and ASs, a hydrolysis method was used that reduces their multitude of UV detectable substance peaks to only one of each. This allows easier identification and, due to low conversion rates and high variation coefficients, preliminary semiquantification of these by standard addition. Furthermore, an UHPLC-DAD-MS/MS method was developed which allows the identification and quantification of a total of 53 PIs and ASs in extracts of FCMs and foodstuffs in only 11.5 min, enabling a high sample throughput. The analysis of a spiked muesli mix showed that this method can be used to control the migration limits in food for the majority of the analytes. Both presented multi-analyte methods allow, to the best of my knowledge, the identification and determination of almost twice as many PIs and ASs than other methods published before.     

Migration kinetics of four photo-initiators from paper food packaging to solid food simulants

ABSTRACT

The migration behaviour of four photo-initiators (BP, EHA, MBP and Irgacure 907) was studied by ‘printing’ onto four different food-packaging materials (Kraft paper, white cardboard, Polyethylene (PE)-coated paper and composite paper) and tracking movement into the food simulant: Tenax-TA (porous polymer 2,6-diphenyl furan resin). The results indicated that the migration of the photo-initiators was related to the molecular weight and log K_o/w of each photo-initiator. At different temperatures, the migration rates of the photo-initiators were different in papers with different thicknesses. The amount of each photo-initiator found in the food was closely related to the food matrix. The Weibull model was used to predict the migration load into the food simulants by calculating the parameters τ and β and determining the relationship of the two parameters with temperature and paper thickness. The established Weibull model was then used to predict the migration of each photo-initiator with respect to different foods. A two-parameter Weibull model fitted the actual situation, with some deviation from the actual migration amount.     

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。     

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.     

两亲复鞣加脂剂的合成

以疏水性单体(顺酐十二醇单酯或丙烯酸高级醇酯)和丙烯酸、丙烯晴等多种有效单体进行乳液共聚,制得两亲共聚物皮革复鞣加脂剂。探讨了各种单体成分及各种反应条件对产品性能的影响。     

不同类型烟用接装纸表面性能及其对卷接效果的影响

采用接触角测试比较了水溶性和溶剂型油墨印刷后接装纸表面润湿性能的差异,通过卷烟卷接实验,考察了不同类型接装纸的卷接适应性和卷接的卷烟质量,并运用飞行时间二次离子质谱仪(TOFSIMS)分析了影响卷烟质量和卷接效果的原因,结果表明:①水溶性油墨印刷的接装纸表面润湿性能优于溶剂型油墨印刷的接装纸;②溶剂型油墨印刷的接装纸接装适应性优于水溶性油墨印刷的接装纸,且在卷接成卷烟后,出现外观缺陷的卷烟比例明显低于水溶性油墨印刷的接装纸;③为提高水溶性油墨印刷的接装纸的卷接适应性,需增大印刷后接装纸表面的接触角或改善胶水性能,从而保证接装时接装纸表面有足够的胶水来满足粘接需求.     

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     

Printing newspaper free of mineral oil: report on a test run

The Swiss retailer Coop printed part of his weekly newspaper with inks formulated without mineral oil. The experiment explored this approach to reduce the migration of mineral oil into food when newspaper is recycled to paperboard for food packaging. The mineral oil was replaced by plant oils as well as poly alpha olefins (PAO) with the lowest mass above the n-alkane C₂₄, i.e. of a volatility low enough to prevent transfer through the gas phase into food. With this composition, no major adjustments of the printing machine were necessary. The printing quality was judged excellent by the International Newspaper Color Quality Club (INCQC). As the carryover in the installations was known to be a serious problem, 30 t of inks were used, initially printing daily newspapers and other printed material. Measurement of the residual mineral oil in the inks as delivered to the printing plant and monitored at the top of a printing tower confirmed that no rapid exchange of inks is possible.     

Safety by design of printed multilayer materials intended for food packaging

ABSTRACT

Printing inks are commonly used in multilayer plastics materials used for food packaging, and compounds present in inks can migrate to the food either by diffusion through the multilayers or because of set-off phenomena. To avoid this problem, the right design of the packaging is crucial. This paper studies the safety by design of multilayer materials. First, the migration from four different multilayers manufactured using polyethylene terephthalate (PET), aluminium (Al) and polyethylene (PE) was determined. The structural differences among materials such as the presence of inks or lacquer coatings as well as the differences in layers position allowed the study of a safety-by-design approach. Sixty-nine different compounds were detected and identified; 49 of them were not included in the positive list of Regulation EU/10/2011 or in Swiss legislation and 15 belong to Cramer class III, which means that they have a theoretical high toxicity. Some of the compounds related to ink composition were pyrene, a compound commercially used to make dyes and dye precursors and the antioxidant Irganox 1300. The application of external lacquers decreased the concentration of some migrants but also brought the potential for new migrants coming from its composition. A final risk assessment of the material allowed evaluating food safety for different food simulants and confirm it.     

胶印气相转移印花油墨及其应用

研究胶印气相转移印花油墨的组成及转移条件对油墨转移性能的影响。所研制的胶版印刷油墨对纸张有较好的适应性，印制的转移纸可对织物转印多次。