Print quality and resistance for water-based flexography on polymer-coated boards: Dependence on ink formulation and substrate pretreatment

The performance of water-based acrylic flexographic inks laboratory printed on three different polymer-coated boards, namely coated with LDPE, OPP and PP, have been analysed and interpreted. The print quality and resistance properties obtained were related to varying ink formulation, in particular choice of emulsion polymer and presence of silicone additive in the vehicle, as well as varying levels of corona pretreatment. Print mottle and adhesion were worst on PP, while wet (water) rub and scratch resistance were worst on OPP and PE, respectively. However, these properties could be greatly influenced by the ink formulation, more so than corona level. In general addition of silicone improved scratch resistance, due to reduction in polar energy component of the print surface, but at the expense of worsened wet rub resistance. The emulsion polymer giving best resistance performance was generally found to give poorest optical properties, presumably due to more limited resolubility on press.     

Surface graft copolymerization of 2‐hydroxyethyl methacrylate onto low‐density polyethylene film through corona discharge in air

The corona discharge technique was explored as a means of forming chemically active sites on a low‐density polyethylene (LDPE) film surface. The active species thus prepared at atmospheric pressure in air was exploited to subsequently induce copolymerization of 2‐hydroxyethyl methacrylate (HEMA) onto LDPE film in aqueous solution. The results showed that with the corona discharge voltage, reaction temperature, and inhibitor concentration in the reaction solution the grafting degree increased to a maximum and then decreased. As the corona discharge time, reaction time, and HEMA concentration in the reaction solution increased, the grafting degree increased. With reaction conditions of a 5 vol % HEMA concentration, 50°C copolymerization temperature, and a 2.0‐h reaction time, the degree of grafting of the LDPE film reached a high value of 158.0 μg/cm² after treatment for 72 s with a 15‐kV voltage at 50 Hz. Some characteristic peaks of the grafted LDPE came into view at 1719 cm^?1 on attenuated total reflectance IR spectra (C?O in ester groups) and at 531 eV on electron spectroscopy for chemical analysis (ESCA) spectra (O_1s). The C_1s core level ESCA spectrum of HEMA‐grafted LDPE showed two strong peaks at ～286.6 eV (? C ? O? from hydroxyl groups and ester groups) and ～289.1 eV (O?C ? O? from ester groups), and the C atom ratio in the ? C? O? groups and O?C? O groups was 2:1. The hydrophilicity of the grafted LDPE film was remarkably improved compared to that of the ungrafted LDPE film. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2881–2887, 2001     

Ozone‐induced grafting of a sulfoammonium zwitterionic polymer onto low‐density polyethylene film for improving hemocompatibility

Ozone‐induced grafting was developed to improve the hemocompatibility of biomaterials based on low‐density polyethylene (LDPE). An LDPE film was activated with ozone and graft‐polymerized with N,N′‐dimethyl(methacryloylethyl)ammonium propane sulfonate (DMAPS). The existence of sulfobetaine structures on the grafted film was confirmed by X‐ray photoelectron spectroscopy and attenuated total reflection/Fourier transform infrared (ATR–FTIR). More DMAPS was grafted onto the LDPE film as the DMAPS concentration increased, as determined by ATR–FTIR. Static contact‐angle measurements indicated that the DMAPS‐grafted LDPE film had a significant increase in hydrophilicity. The blood compatibility of the grafted film was preliminarily evaluated with a platelet‐rich‐plasma (PRP) adhesion study. No platelet adhesion was observed on the grafted film incubated with PRP at 37°C for 180 min. This new sulfoammonium zwitterionic‐structure‐grafted biomaterial might have potential for biomedical applications. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3697–3703, 2006     

Surface structure and adhesive properties of biaxially oriented polypropylene film grafted with poly(acrylic amide) using corona discharge

Corona discharge was explored as a means of forming chemically active sites on the surface of biaxially oriented polypropylene (BOPP) film. The active species formed in air was used to induce graft copolymerization of acrylic amide (AAM) in aqueous solution. The surface structure, hydrophilicity and adhesion of the grafted BOPP film were characterized by the extent of grafting, electron spectroscopy for chemical analysis (ESCA), scanning electron microscopy (SEM), peel strength and contact angle measurements. Surface graft‐copolymerization of AAM onto BOPP film by corona discharge in air can be carried out with high efficiency. With increasing copolymerization time, the degree of grafting of AAM onto BOPP increases. The degree of grafting achieved a relatively high value of 2.13 wt% for the conditions of 1 min corona discharge and a copolymerization reaction time of 2.5 hr in 20% AAM aqueous solution at 70°C. After corona discharge grafting, the contact angle of water on the BOPP film decreased and the peel strength increased compared with those for ungrafted BOPP film. The hydrophilicity and adhesion of BOPP were improved by surface graft copolymerization with AAM induced by corona discharge.     

Artificial ageing of low density polyethylene film containing chemically bound UV - stabilizer

This paper deals with photostabilization of low density polyethylene films (LDPE) grafted with the UV-stabilizer 2-hydroxy-4-(3-methacryloxy-2-hydroxy-propoxy) benzophenone (HMB). The influence of grafting yield and the other grafting conditions upon photostabilization efficiency of LDPE films were then studied. The chemically bound monomer (HMB) was localized mainly near the surface of an LDPE film. The grafted LDPE film was exposed to an ultraviolet radiation source, and the degree of oxidation and other photooxidative changes were determined by transmission IR and ATR IR spectroscopy. Experimental results show that radiation grafting of a UV-stabilizer upon LDPE films is an efficient photostabilization method.     

Preparation and properties of alcohol-resistant thermal transfer printing inks for multifunctional label printing via physical blending of resins

Due to the rise of the logistics industry and the widespread use of ink labels, problems such as the narrow operating temperature range of ink, poor alcohol resistance, and insufficient scratch resistance need to be solved urgently. In this work, creates alcohol-resistant thermal transfer inks by mixing polypropylene chloride (VP-365) and epoxidized hydrogenated bisphenol A (P) resin and incorporating them into the ink formulation. The synthetic ink has a lower glass transition temperature (118.2°C), allowing the ink to print at lower temperatures. It has small wetting angles (68°, 63°, 58°, 46°, and 40°) and a large adhesion force (10.44 – 14.4 N) for different labels. Further, to evaluate the printing performance of the ink, the ink was scratched under 1000 g pressure and in the environment of isopropyl alcohol to evaluate its printing performance. The produced ink has high scratch resistance (300 times) and good alcohol resistance (140 times). Moreover, the developed ink showed good printability, printing media versatility, high adhesion, and excellent alcohol resistance. The synthesis method is facile and cost-effective, which paves a novel way towards high-performance ink printing and thermal transfer technology industries.     

Chemical modification of LDPE film

Low‐density polyethylene (LDPE) film was chemically modified by chromic acid treatment to generate polar groups on the surface. The film samples were etched by chromic acid with variation of temperature at a constant time (30 min) and variation of time at a constant temperature (room temperature = 26°C). The variation of weight and thickness of the film samples before and after etching was measured. The surface morphology of the etched films was studied by Scanning Electron Microscopy (SEM). IR and XPS analysis revealed the introduction of polar groups like  COOH, 〉CO,  SO₃H on the etched LDPE film surface, which exhibited improved printability. Etching also enhanced adhesion with epoxy resin. The mechanical properties of the laminates of the two specimens of the same film sample with epoxy resin were also measured. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1041–1048, 1999     

Etching of a low-density polyethylene film by fuming nitric acid

Low-density polyethylene (LDPE) films were treated with fuming nitric acid (FNA). The surface characteristics and also the insertion of polar groups like on the etched LDPE film surface were measured by SEM, IR and XPS analyses, respectively. The mechanical performance of a laminate of the etched film with epoxy resin and also the printability of the etched film surface were tested and compared with the unetched sample. The surface roughening and the presence of polar groups enhance the mechanical strength of the laminate of FNA-treated film due to mechanical interlocking and chemical interaction. The printability of the treated film surface is also superior to that of the untreated LDPE film surface.     

Surface modification of LDPE film by chemical processes with Ni2+ and ammonium persulfate

Chemical modification of the surface of low-density polyethylene (LDPE) film was performed with an aqueous solution of ammoniacal ammonium persulfate in the presence of Ni²⁺ ions, where the polar groups were generated on the surface of the LDPE film. The surface of the LDPE film was modified chemically with an ammoniacal solution of ammonium persulfate (1.1M) and Ni(SO₄)₂ (0.02M) heated at about 70°C for 3 h. The morphologies of the surfaces were studied with scanning electron microscopy and infrared spectroscopy; electron spectroscopy for chemical analysis revealed the introduction of polar groups on the surface, which improved printability and adhesion properties. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 406–415, 2001     

Maleic acid grafted low density polyethylene for thermally sprayable anticorrosive coatings

Low density polyethylene (LDPE) coatings are being used in an ever growing range of applications. However, non-polar characteristics of LDPE make its adhesion poor to metal substrate and so become less suitable for anticorrosive coating application. An anticorrosive coating can therefore be developed if LDPE is modified with requisite polar groups. In the present work, a polar group has been introduced in polyethylene matrix by grafting maleic acid. Grafted LDPE was characterized by chemical method, Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), thermo-gravimetric analysis (TGA), melt flow index (MFI), particle size analysis and hot stage optical microscopy. The presence of carbonyl peak of high intensity, high acid value and low melt flow index value confirmed grafting of maleic acid on LDPE. Change in crystallization behaviour of LDPE has been noticed after grafting. Grafted LDPE was applied on grit blasted mild steel surface by flame spray technique and adhesion study showed improved adhesion of grafted LDPE than LDPE. The coated panels were evaluated for resistance to corrosion in salt spray, humidity cabinet and seawater. The corrosion resistance of modified LDPE was also studied by AC Impedance technique. Grafted LDPE showed satisfactory corrosion resistance. Grafted LDPE was pigmented with red iron oxide and pigmented composition has shown improved resistance to corrosion in laboratory tests.     

Surface modification of low‐density polyethylene (LDPE) film and improvement of adhesion between evaporated copper metal film and LDPE

To improve the interfacial adhesion between evaporated copper film and low‐density polyethylene (LDPE) film, the surface of LDPE films was modified by treating with chromic acid [K₂Cr₂O₇/H₂O/H₂SO₄ (4.4/7.1/88.5)]/oxygen plasma. Chromic‐acid‐etched LDPE was exposed to oxygen plasma to achieve a higher content of polar groups on the LDPE surface. We investigated the effect of the treatment time of chromic acid in the range of 1–60 min at 70°C and oxygen plasma in the range of 30–90 sec on the extent of polar groups created on the LDPE. We also investigated the surface topography of and water contact angle on the LDPE film surface, mechanical properties of the LDPE film, and adhesion strength of the evaporated copper metal film to the LDPE film surface. IR and electron spectroscopy for chemical analysis revealed the introduction of polar groups on the modified LDPE film surface, which exhibited an improved contact angle and copper/LDPE adhesion. The number of polar groups and the surface roughness increased with increasing treatment time of chromic acid/plasma. Water contact angle significantly decreased with increasing treatment time of chromic acid/plasma. Combination treatment of oxygen plasma with chromic acid drastically decreased the contact angle. When the treatment times of chromic acid and oxygen plasma were greater than 10 min and 30 sec, respectively, the contact angle was below 20°. With an increasing treatment time of chromic acid, the tensile strength of the LDPE film decreased, and the film color changed after about 10 min and then became blackened after 30 min. With the scratch test, the adhesion between copper and LDPE was found to increase with an increasing treatment time of chromic acid/oxygen plasma. From these results, we found that the optimum treatment times with chromic acid and oxygen plasma were near 30 min and 30 sec, respectively. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1677–1690, 2001     

Coating based on the modified chlorinated polypropylene emulsion for promoting printability of biaxially oriented polypropylene film

In this paper, a polymeric coating based on the modified chlorinated polypropylene (CPP) emulsion was synthesized, methyl methacrylate (MMA), butyl acrylate (BA) and acrylic acid (AA) were grafted onto CPP backbone and phase inversion was conducted to obtain waterborne emulsion. Results showed that the concentration of initiator (BPO) had the greatest effect on graft copolymerization. The concentration of emulsifier and temperature influenced the results of phase inversion. Besides, the thermal performances of modified CPP were better than untreated one. In addition, the coating obtained in optimum condition had excellent adhesion to BOPP film, and apparently improved the printing quality of the film. The printability promotion should be attributed to the different movement trend of coating’s polar and un-polar chains during the baking step, as well as the subsequent formations of new coating/substrate and coating/ink interface layer.     

Corona-induced graft polymerization of ethyl acrylate onto cellulose film

Ethyl acrylate was readily grafted from an aqueous solution onto cellophane film previously treated in a corona discharge at atmospheric pressure. The effect was found when the corona treatment was carried out not only in air but also in pure nitrogen. The observed grafting was not promoted but depressed by the presence of ferrous ion, which indicated that peroxide radicals were not initiating the graft. A high grafting efficiency was obtained, and the grafted surface was covered with a smooth uniform layer of polymer.     

Synthesis of waterborne acrylic copolymer resin as a binding agent for the development of water-based inks in the printing application

In this study, a new waterborne acrylic copolymer resin (acrylic-co-resin) was synthesized to develop water-based printing inks on polyester (PET) film. The synthesized acrylic resin showed good water solubility, high acid value (120 mg KOH/g), about 57% solid content. The developed water-based inks (cyan, magenta, and yellow) exhibited small particle size (<1 μm) and optimum surface energy within required values (31.5, 32, and 30 mN/m) for good adhesion of ink upon PET films. The developed inks also showed good storage stability for 30 days. Further, to evaluate the application performance, the inks were printed on corona-treated PET films at room temperature, and the ink drying time was measured. Further, the inks were printed on the corona-treated PET film to evaluate the application performance. The developed inks showed a short drying time (7–9 s), which indicates their fast drying nature. Moreover, the developed inks showed good printability, color strength, high adhesion, and excellent rub-resistant properties. Thus, the overall results demonstrated the potential of water-based inks in printing applications.     

High oxygen barrier multilayer EVOH/LDPE film/foam

High oxygen barrier film/foam system had been developed using multilayer coextrusion technology. The film/foams contained alternating ethylene–vinyl alcohol (EVOH) copolymer film layers and low‐density polyethylene (LDPE) foam layers. To ensure good adhesion and layer integrity, the LDPE was preblended with LDPE grafted maleic anhydride. The layered structure of film/foam was characterized by scanning electron microscopy. The film/foams showed adjustable density, oxygen permeability, and mechanical properties by changing the film and foam composition. Film/foam with 10% EVOH film layer was successfully thermoformed at room temperature. The cells in the foam layer were observed to deform during the mechanical forming process. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46425.     

等离子体引发丙烯酸在LDPE薄膜表面接枝聚合的研究（Ⅱ）

利用等离子体引发的接枝反应对低密度聚乙烯（LDPE）薄膜进行表面改性处理,通过对接枝单体后LDPE薄膜表面单体接枝率的计算和表面接触角以及表面自由能的测量,系统地研究了单体浓度、反应温度、处理时间等对等离子体引发接枝反应的影响,并利用红外光谱、扫描电镜对接枝单体后薄膜表面的化学组成及表面结构进行了表征分析。     

Suture Fiber Reinforcement of a 3D Printed Gelatin Scaffold for Its Potential Application in Soft Tissue Engineering

Gelatin has excellent biological properties, but its poor physical properties are a major obstacle to its use as a biomaterial ink. These disadvantages not only worsen the printability of gelatin biomaterial ink, but also reduce the dimensional stability of its 3D scaffolds and limit its application in the tissue engineering field. Herein, biodegradable suture fibers were added into a gelatin biomaterial ink to improve the printability, mechanical strength, and dimensional stability of the 3D printed scaffolds. The suture fiber reinforced gelatin 3D scaffolds were fabricated using the thermo-responsive properties of gelatin under optimized 3D printing conditions (−10 °C cryogenic plate, 40–80 kPa pneumatic pressure, and 9 mm/s printing speed), and were crosslinked using EDC/NHS to maintain their 3D structures. Scanning electron microscopy images revealed that the morphologies of the 3D printed scaffolds maintained their 3D structure after crosslinking. The addition of 0.5% (w/v) of suture fibers increased the printing accuracy of the 3D printed scaffolds to 97%. The suture fibers also increased the mechanical strength of the 3D printed scaffolds by up to 6-fold, and the degradation rate could be controlled by the suture fiber content. In in vitro cell studies, DNA assay results showed that human dermal fibroblasts’ proliferation rate of a 3D printed scaffold containing 0.5% suture fiber was 10% higher than that of a 3D printed scaffold without suture fibers after 14 days of culture. Interestingly, the supplement of suture fibers into gelatin biomaterial ink was able to minimize the cell-mediated contraction of the cell cultured 3D scaffolds over the cell culture period. These results show that advanced biomaterial inks can be developed by supplementing biodegradable fibers to improve the poor physical properties of natural polymer-based biomaterial inks.     

Surface modification of polypropylene film by grafting with vinyl monomers for the attachment of chitosan

Polypropylene (PP) film activated by corona discharge treatment was grafted with methyl methacrylate (MMA) and acrylic acid (AA). The grafted PP was characterized by spectral, thermal analysis and swelling behavior which confirmed the occurrence of the grafting. The water vapor and oxygen permeability (OTR and WVTR) as well as the mechanical properties have been enhanced by grafting with both AA and MMA. The grafted PP was further immobilized with chitosan (CS) using ceric ammonium nitrate (CAN) as an initiator under ultraviolet radiation. The chitosan immobilized grafted film was characterized by FTIR, mechanical properties, thermal properties and swelling measurements. Scanning electron microscope (SEM) confirmed that the CS is bonded to the grafted PP film. The CS modified PP film has acquired enhanced antibacterial and antifungal properties.     

Graft copolymerization of polyethylene glycol methacrylate onto polyethylene film and its blood compatibility

In an attempt to produce surfaces that show low levels of adsorption of protein and adhesion of platelets, different molecular weights of polyethylene glycol methacrylate (PEG‐MA) were grafted onto polyethylene film by a preirradiation grafting process. The extent of grafting was found to be dependent on the storage condition of the irradiated polyethylene film, the preirradiated dose, reaction time and temperature, molecular weight of PEG‐MA, and the type of solvent. The grafting yield was found to decrease rapidly with storage time for irradiated polyethylene film stored at room temperature. On the other hand, the grafting yield in the irradiated polyethylene stored at −130°C remained nearly constant up to 20 days after irradiation. The grafting yield decreased with an increased PEG‐MA molecular weight. Human plasma protein was adsorbed onto control and PEG‐MA‐grafted polyethylene film surfaces, and the relative adsorbed amount of proteins on the surfaces was evaluated by electron spectroscopy for chemical analysis. The adsorbed protein and platelet adhesion on the polyethylene film surface decreased rapidly with the grafting yield. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 631–641, 1999     

Surface structure of low density polyethylene films grafted with acrylic acid using corona discharge

Chemical composition, morphology, and crystalline structure of low density polyethylene (LDPE) films surface grafted with acrylic acid (AA) using corona discharge were studied by attenuated total reflection infrared (ATR-IR), electron spectroscopy for chemical analysis (ESCA), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and wide angle X-ray diffraction (WAXD) techniques. The grafted film surface is covered with grafted chains. After grafting for 3.0 h in 20% aqueous solution of AA, the depth of the grafted layer is more than 10 nm. A grain structure was observed on the grafted surfaces which was probably caused by the isolated dispersion of active sites generated by corona discharge, and these active sites initiated the graft copolymerization. However, surfaces of grafted films were smoother than that of ungrafted ones. DSC curves of grafted films show a small peak at about 100°C due to vaporization of adsorbed water. The longer the graft copolymerization time, i.e. the higher the graft degree of AA on LDPE, the higher the amount of adsorbed water. The position of each peak in WAXD patterns, crystal axial length, crystal plane distance and crystal grain size remain almost unchanged during the graft copolymerization time of 2.0 h. However, when the graft copolymerization time reaches 3.0 h, twin peaks at about 21.4° and 22.0° are observed, indicating that a different crystal form is formed at longer copolymerization time, i.e. at a higher graft degree.