Quinacridone Pigments Research Articles

Polypropylene Color Masterbatches Containing Layered Double Hydroxide Modified with Quinacridone and Phthalocyanine Pigments-Rheological, Thermal and Application Properties.

Polypropylene color masterbatches containing modified layered double hydroxides, LDHs, were created. The simple, industry-acceptable method of LDH surface modification with quinacridone and phthalocyanine pigments using the pulverization method in ball mills was applied. It was reported that the modification parameters such as time and rotational speed affected the tendency to create the aggregates for modified fillers. TGA analysis of the modified LDH showed that modification with phthalocyanine pigment shifted the temperature at which 5%, T5%, and 10% of mass loss, T10%, occurred compared with that for unmodified LDH. The viscoelastic properties of prepared masterbatches were investigated. The incorporation of the modified fillers instead of neat pigments led to an increase in the loss shear modulus, G″, indicating a stronger influence on the dissipation of energy by the melted masterbatch. The similar values of tan, δ, were determined for melted masterbatches containing phthalocyanine pigment and green modified LDH filler. The incorporation of both LDHs modified by phthalocyanine and quinacridone pigment fillers slightly increased the zero-shear viscosity, η0, compared with that of the masterbatches based on the neat pigments. The Cole-Cole plots and the analysis of the Maxwell and continuous relaxation models showed that modified colored LDH fillers facilitated the relaxation of the melted masterbatch, and shorter relaxation times were observed. The phthalocyanine-modified LDH filler improved the thermal stability of the masterbatches. Additionally, the impact of pigments and modified, colored LDH on the crystallization of polypropylene was investigated.

Influence of hemicellulose and lignin on intermolecular interaction between quinacridone and lignocellulosic fibers revealed by gel-state NMR and color measurements

Quinacridone, a π-conjugated planar molecule, and common red pigment in industrial and painting applications, easily aggregates to form large clusters of pigment particles, resulting in a reduction in color strength. Cotton-derived cellulose nanofiber (NF), which almost consists of cellulose without hemicellulose and lignin, has been found to adsorb quinacridone on the surface, which inhibits pigment aggregation. The aggregation inhibition property of cellulose NF was induced by the strong intermolecular interactions between cellulose and quinacridone. In this study, the properties of lignocellulosic fibers for suppressing the aggregation of quinacridone pigments were investigated to reveal the influence of hemicellulose and lignin on the intermolecular interactions between quinacridone and fibers. Two lignocellulosic fibers with different degrees of fibrillation were used as dispersants of the pigment. In the scanning electron microscopy (SEM) images of the quinacridone–lignocellulose mixture, quinacridone particles were observed along the lignocellulose fiber, indicating that the quinacridone particles were well-adsorbed on the fiber surface. Consequently, the color of the aqueous suspension of quinacridone–lignocellulose mixture became increasingly vivid as the weight ratio of the lignocellulose fibers increased and as the fiber was fibrillated. The nuclear Overhauser effect spectroscopy (NOESY)–nuclear magnetic resonance (NMR) spectrum for quinacridone–lignocellulose suspension in d-dimethyl sulfoxide showed several NOE cross-peaks between quinacridone and cellulose/hemicellulose, whereas no cross-peaks between quinacridone and lignin were observed. It can be concluded that cellulose and hemicellulose promote the adsorption of quinacridone on the fiber surface, whereas lignin does not interact with quinacridone, even though both are aromatic molecules. This suggests that the intermolecular interactions based on hydrogen bonding and CH–π attraction are more dominant than the π–π attraction between quinacridone and lignocellulosic fibers.

DCL ready for automotive color of the year

The most frequent colors for cars today are white, gray and black. Coatings company Axalta however recently announced their global automotive color for 2022 to be “Royal Magenta”, a very dark, purplish red, described by Axalta as luxurious and elegant, with a mysterious dark look at night and berry red in sunlight. DCL – a provider of pigments and dispersions for the coatings, plastics and ink industries – subsequently announced that their latest acquisition of perylene and quinacridone pigments from the Bushy Park manufacturing site will serve this magenta color trend.

Quinacridone pigments

Abstract This chapter surveys the structural and synthetic chemistry and the industrial applications of quinacridones, a small but extremely important group of high-performance carbonyl (or polycyclic) organic pigments. They are based on one of the most important new chromophoric systems developed specifically for pigment applications after the introduction of the phthalocyanines, and currently occupy a prominent position in the red to violet shade areas. A historical perspective on the discovery and commercial development of the quinacridones is presented initially. There then follows an illustrated discussion of the structural chemistry of the pigments, encompassing both molecular and crystal structures. Throughout the chapter, specific features of their molecular structures and the nature of the intermolecular association within the crystals are related to their influence on the color and technical performance in application, in which they exhibit some of the highest standards of heat stability, solvent resistance, and fastness to light and weather encountered in organic pigments. Finally, a survey of the principal current applications of the specific individual commercial quinacridone pigments is presented.

Diketopyrrolopyrrole (DPP) pigments

Abstract Since their industrial introduction in the 1980s, DPP pigments now constitute a highly important group of high-performance carbonyl pigments. The DPP system was first discovered by accident in 1974, and was subsequently re-investigated by Ciba Geigy who recognized its potential to provide commercial organic pigments. DPP pigments exhibit strong similarities compared with quinacridone pigments, in terms of their molecular and crystal structures and their properties, including low solubility and excellent fastness properties. X-ray crystal structural analysis has demonstrated that their technical performance is the result of intermolecular hydrogen bonding and π–π stacking interactions in the crystal lattice structure. Based on a simple retrosynthetic analysis, an efficient synthetic process was developed by Ciba Geigy for their large-scale manufacture. DPP pigments currently provide orange through to reddish violet shades and have become of special importance in providing brilliant saturated red shades with the outstanding durability required for applications such as automotive paints.

Carbonyl pigments: miscellaneous types

AbstractCarbonyl pigments are characterized by the presence of one or more carbonyl (C = O) groups in their structures, generally as a component of the chromophoric grouping and as part of an extended conjugated π-electron system. Structurally, they constitute a diverse group of pigments that offer a wide range of colors throughout the spectrum, and most of them provide high levels of technical performance. This paper provides a description of the historical development of thioindigoid, isoindoline, isoindolinone, and quinophthalone pigment types, and discusses their molecular and crystal structures in relation to their properties, the synthetic procedures used in their manufacture and their principal applications. They provide some of the most important high-performance yellow organic pigments for demanding applications in paints, inks, and plastics. Separate individual chapters in this series are devoted the anthraquinonoid, quinacridone, diketopyrrolopyrrole, perylene, and perinone carbonyl pigment subclasses.

Identification of Synthetic Organic Pigments in Contemporary Artists’ Paints by FT-IR and FT-Raman: An Advanced Analytical Experiment

The identification of coloring substances is a relevant task in the field of conservation and restoration, but it can be challenging as in real samples the target analytes are inserted in a very complex matrix made of binders and additives. Understanding this concept is fundamental for upper-division undergraduate students interested in conservation science; therefore, this laboratory experiment aims to make students aware of this problem and leads them to develop a simple protocol combining two spectroscopic techniques, FT-IR and FT-Raman, and basic chemical treatments to overcome this difficulty. The case of the two quinacridone pigments, PR122 and PV19, is presented and discussed, although the same approach can be extended to other commercially available organic pigments.

Highly Efficient and Stable Perovskite Solar Cells Enabled by Low‐Cost Industrial Organic Pigment Coating

AbstractSurface passivation of perovskite solar cells (PSCs) using a low‐cost industrial organic pigment quinacridone (QA) is presented. The procedure involves solution processing a soluble derivative of QA, N,N‐bis(tert‐butyloxycarbonyl)‐quinacridone (TBOC‐QA), followed by thermal annealing to convert TBOC‐QA into insoluble QA. With halide perovskite thin films coated by QA, PSCs based on methylammonium lead iodide (MAPbI3) showed significantly improved performance with remarkable stability. A PCE of 21.1 % was achieved, which is much higher than 18.9 % recorded for the unmodified devices. The QA coating with exceptional insolubility and hydrophobicity also led to greatly enhanced contact angle from 35.6° for the pristine MAPbI3 thin films to 77.2° for QA coated MAPbI3 thin films. The stability of QA passivated MAPbI3 perovskite thin films and PSCs were significantly enhanced, retaining about 90 % of the initial efficiencies after more than 1000 hours storage under ambient conditions.

Highly Efficient and Stable Perovskite Solar Cells Enabled by Low-Cost Industrial Organic Pigment Coating.

Surface passivation of perovskite solar cells (PSCs) using a low-cost industrial organic pigment quinacridone (QA) is presented. The procedure involves solution processing a soluble derivative of QA, N,N-bis(tert-butyloxycarbonyl)-quinacridone (TBOC-QA), followed by thermal annealing to convert TBOC-QA into insoluble QA. With halide perovskite thin films coated by QA, PSCs based on methylammonium lead iodide (MAPbI3 ) showed significantly improved performance with remarkable stability. A PCE of 21.1 % was achieved, which is much higher than 18.9 % recorded for the unmodified devices. The QA coating with exceptional insolubility and hydrophobicity also led to greatly enhanced contact angle from 35.6° for the pristine MAPbI3 thin films to 77.2° for QA coated MAPbI3 thin films. The stability of QA passivated MAPbI3 perovskite thin films and PSCs were significantly enhanced, retaining about 90 % of the initial efficiencies after more than 1000 hours storage under ambient conditions.

Suppressing aggregation of quinacridone pigment and improving its color strength by using chitosan nanofibers

Quinacridone, a red pigment, is prone to aggregation, which results in undesirable color changes. Cellulose nanofibers (NFs) have been reported to adsorb quinacridone and suppress its aggregation. In this study, we investigated the potential of chitin and chitosan NFs which possess acetoamide and amino groups, as a quinacridone dispersant. Chitosan NFs, obtained by fibrillation using high-pressure homogenizer, adsorbed more quinacridone than cellulose NFs. SEM observations showed that chitosan NFs inhibited the aggregation of quinacridone, but chitin NFs did not. NMR analysis suggested the hydrogen bonding between chitosan NFs and quinacridone induced by the amino groups. The results indicated that the amino groups more facilitated the intermolecular interactions between NFs and quinacridone than the hydroxyl groups whereas the acetamide groups hindered them. Color measurements showed that the redness of quinacridone improved when cellulose or chitosan NFs were added. Chitosan NFs were found to be a novel candidate for quinacridone dispersants.

Dispersion of quinacridone pigments using cellulose nanofibers promoted by CH–π interactions and hydrogen bonds

Organic pigments are prone to aggregate, resulting in decreasing of their properties. Therefore, pigment dispersants are demanded to have both high adsorption capacity and aggregation inhibiting property for pigment particles. In the present study, the suitability of cellulose nanofibers (CNFs) as a dispersant for quinacridone, a common red–violet organic pigment, was investigated. Quinacridone particles were well adsorbed on the CNFs. Scanning electron microscopy images of the quinacridone–CNF mixtures showed that the quinacridone primary particles were stacked along the cellulose fibers, and the aggregations were inhibited. In addition, the size of the quinacridone particles had an effect on their color. The interactions of quinacridone and cellulose were investigated by Fourier transform infrared (FTIR) and solution-state nuclear magnetic resonance (NMR) spectroscopies. FTIR spectra of the quinacridone–CNF mixtures indicated the intermolecular interactions between quinacridone and cellulose. Because quinacridone and CNFs were insoluble in the NMR solvents, gel-state NMR spectroscopy, which has been used for the whole plant cell wall analysis, was conducted on them. Consequently, whole signals arising from quinacridone and cellulose were enabled to be assigned, and the coupling constant of quinacridone has reported for the first time. The nuclear Overhauser effect spectroscopy (NOESY)-NMR spectrum of the quinacridone–CNF mixture revealed both NH group and aromatic moiety of quinacridone were interacted with glucose unit. The former was considered to be related to hydrogen bonding, and the latter to CH–π interactions. These specific interactions might contribute to achieve the high adsorption capacity of CNFs for quinacridone.

High temperature-stability of organic thin-film transistors based on quinacridone pigments

Abstract Robust organic thin-film transistors (OTFTs) with high temperature stability allow device integration with mass production methods like thermoforming and injection molding, and enable operation in extreme environment applications. Herein we elaborate a series of materials to make suitable gate dielectric and active semiconductor layers for high temperature stable OTFTs. We employ an anodized aluminum oxide layer passivated with cross-linked low-density polyethylene (LD-PE) to form a temperature-stable gate capacitor. As the semiconductor, we use quinacridone, an industrial organic colorant pigment produced on a mass scale. Evaporated MoOx/Ag source and drain electrodes complete the devices. Here we evaluate the performance of the OTFTs heating them in air from 100 °C in 25 °C increments up to 225 °C, holding each temperature for a period of 30 minutes. We find large differences in stability between quinacridone and its dimethylated derivative, with the former showing the best performance with only a factor of 2 decline in mobility after heating at 225 °C, and unaffected on/off ratio and threshold voltage. The approach presented here shows how industriallys calable fabrication of thermally robust OTFTs can be rationalized.

Cellular interfaces with hydrogen-bonded organic semiconductor hierarchical nanocrystals

Successful formation of electronic interfaces between living cells and semiconductors hinges on being able to obtain an extremely close and high surface-area contact, which preserves both cell viability and semiconductor performance. To accomplish this, we introduce organic semiconductor assemblies consisting of a hierarchical arrangement of nanocrystals. These are synthesised via a colloidal chemical route that transforms the nontoxic commercial pigment quinacridone into various biomimetic three-dimensional arrangements of nanocrystals. Through a tuning of parameters such as precursor concentration, ligands and additives, we obtain complex size and shape control at room temperature. We elaborate hedgehog-shaped crystals comprising nanoscale needles or daggers that form intimate interfaces with the cell membrane, minimising the cleft with single cells without apparent detriment to viability. Excitation of such interfaces with light leads to effective cellular photostimulation. We find reversible light-induced conductance changes in ion-selective or temperature-gated channels.

Effect of Quinacridone Pigments on Properties and Morphology of Injection Molded Isotactic Polypropylene

Two quinacridone pigments were added (0.01; 0.05; 0.1; 0.5; 1; 2 wt%) to isotactic polypropylene (iPP), and their influence on mechanical and thermomechanical properties were investigated. Complex mechanical and thermomechanical iPP properties analyses, including static tensile test, Dynstat impact resistance measurement, and hardness test, as well as dynamic mechanic thermal analysis (DMTA), were realized in reference to morphological changes of polymeric materials. In order to understand the differences in modification efficiency and changes in polymorphism of polypropylene matrix caused by incorporation of pigments, differential scanning calorimetry (DSC) and wide-angle X-ray scattering (WAXS) experiments were done. Both pigments acted as highly effective nucleating agents that influence morphology and mechanical properties of isotactic polypropylene injection molded samples. Differences between polypropylene samples nucleated by two pigments may be attributed to different heterogeneous nucleation behavior dependent on pigment type. As it was proved by WAXS investigations, the addition of γ-quinacridone (E5B) led to crystallization of polypropylene in hexagonal phase (β-iPP), while for β-quinacridone (ER 02) modified polypropylene no evidence of iPP β-phase was observed.

Growing low-dimensional supramolecular crystals directly from 3D particles

We show that one-dimensional (1D) nanostructures and two-dimensional (2D) supramolecular crystals of organic semiconductors can be grown on substrates under ambient conditions directly from three-dimensional (3D) organic crystals. The approach does not require dissolving, melting or evaporating of the source crystals and is based on organic solid–solid wetting deposition (OSWD). We exemplify our approach by using the pigment quinacridone (QAC). Scanning tunnelling microscopy (STM) investigations show that the structures of the resulting 2D crystals are similar to the chain arrangement of the alpha and beta QAC polymorphs and are independent of the 3D source crystal polymorph (gamma). Furthermore, distinct 1D chains can be produced systematically.

Terahertz Analysis of Quinacridone Pigments

We present terahertz spectroscopy and analysis of commercially available quinacridone pigments in the 0–5 THz range. Our results show clear distinction between the β and γ crystalline phases responsible for the deep violet (β) to red (γ) colour pigments. We reveal a large number of absorptions in the terahertz regime shown to depend on the constituent phase as well as temperature.

Spectroscopic characterization of charge carriers of the organic semiconductor quinacridone compared with pentacene during redox reactions

The molecular-scale changes of the pigment quinacridone, a hydrogen-bonded organic semiconductor, are evaluated during redox reactions.

Crystal structure of disordered nanocrystalline αII-quinacridone determined by electron diffraction

The nanocrystalline αII-phase of the industrially produced organic pigment quinacridone was studied by 3D electron diffraction. The average crystal structure was obtained directly from the data and validated by energy minimization. A model describing the experimentally observed diffuse scattering was proposed.

The Role of Heteroatoms Leading to Hydrogen Bonds in View of Extended Chemical Stability of Organic Semiconductors

The major challenge in organic electronics concerns the stability of organic semiconductor materials which affects the operational lifetime of devices. Recent reports have shown that hydrogen‐bonded pigments of the indigoid family are air‐ and moisture resistant. The magenta pigment quinacridone, a hydrogen‐bonded molecule in the solid state with a pentacene like frame, is a perfect example for extraordinary chemical stability. Here, studies using in situ spectroscopic methods comparing quinacridone and pentacene are presented. A different spectral response of their radical cations is observed upon chemical doping. While in pentacene the barrier between doping and irreversible overoxidation is small, this stability toward overoxidation is increased by the heteroatomic structure, leading to hydrogen‐bonded quinacridone. This work provides insight into molecular design principles that may lead to next‐generation organic semiconductors with enhanced stability and performance.

Pigment violet 19 - a test case to define a simple method to simulate the vibronic structure of absorption spectra of organic pigments and dyes in solution.

A typical quinacridone pigment, PV19, has been used to analyze the impact of several computational parameters on the UV/vis absorption band shape in solution, simulated using density functional theory and time-dependent density functional theory levels of approximation. These encompass, (i) the choice of exchange-correlation functional, (ii) the basis set, (iii) the method for non-equilibrium optimization of the excited state geometry, (iv) the approach for evaluating the vibronic band structure, (v) the peak broadening, and (vi) the scaling of the harmonic vibrational frequencies. Among these, the choice of exchange-correlation functional is certainly of the most importance because it can drastically modify the spectral shape. In the case of PV19, the M05-2X and to a lesser extent CAM-B3LYP XC functionals are the most efficient to reproduce the vibronic structure, confirming the important role of exact Hartree-Fock exchange. Still, these functionals are not the most reliable to predict the excitation energies and oscillator strengths, for which M05, a functional with less HF exchange, performs better. For evaluating the vibronic structure, the simple gradient method, where only one step of geometry optimization of the excited state is carried out and the gradients are used to evaluate the Huang-Rhys factors as well as to determine the excited state geometries produces a spectrum that is very similar to the ones obtained with the more involved Duschinsky and geometry methods, opening the way to a fast simulation of the UV/vis absorption spectra of pigments and dyes. Then, the effect of scaling the calculated vibrational frequencies to account for anharmonicity effects as well as for limitation of the method also impacts the shape of the vibronic spectrum and this effect depends on the method used to determine the Huang-Rhys factors. Indeed, scaling the vibrational frequencies by a factor which is typically smaller than 1.0 results in a relative decrease of the 0-1 peak intensity with respect to the 0-0 band when optimizing the geometry of the excited state whereas the effect is opposite and magnified if using the gradient method.