Band 6, Heft 10

Natural and synthetic iron oxide pigments are by far the most important colored pigments. Their high importance is based on the variety of stable colors ranging from yellow via orange, red and brown to black. Iron oxide yellow (α-FeOOH), iron oxide red (α-Fe 2 O 3 ) and iron oxide black (Fe 3 O 4 ) are the most important representatives of the iron oxide pigments. Synthetic iron oxide pigments are produced industrially on a large scale by solid-state processes, precipitation processes and by the Laux process. Main advantages of synthetic iron oxide pigments compared with natural types are their pure hue, the consistent, reproducible quality and their tinting strength. Iron oxide pigments are mainly used in construction materials, paints, coatings, and plastics, but also in cosmetics, pharmaceuticals and special applications such as ceramics, magnetic coatings and toners.

Transparent pigments are characterized by very small particles with sizes in the range below 100 nm and large specific surface areas. Most of the technically relevant pigments consist of inorganic compounds. Transparent pigments are classified as nanomaterials. Nanosized primary particles do not or only slightly scatter visible light, which is the reason for their transparency. Pigmentation with these pigments leads to a transparent appearance of the application systems. There are colored and colorless transparent pigments. If colored pigments such as α-FeOOH, α-Fe2O3, and CoAl 2 O 4 are used, the application medium takes on color while remaining transparent. Colorless transparent pigments are nearly invisible in the application system. Only in combination with effect pigments or conventional colored pigments, effects with a special appearance are possible, e.g., frost effects. There are two industrially relevant colorless transparent pigments, TiO 2 and ZnO. Both pigments find their main applications as functional powders. They are characterized by strong UV absorption and are therefore applied as UV absorbers. As such, they are used for the protection of organic materials such as plastics and coatings. They are used in addition in a broad diversity of sun screen products where they protect human skin. The manufacture of transparent pigments takes place mostly using wet-chemical or gas-phase reactions.

Cationic (or basic) dye complex pigments are classical organic pigments obtained from water-soluble cationic dyes for textiles, mainly of triarylmethine (arylcarbonium ion) types, which are precipitated using large inorganic counterions, especially those derived from heteropolyacids such as phosphotungstomolybdic acid or, to a certain extent, using the counteranion derived from copper ferrocyanide. This range of pigments includes red, violet, blue and green products, offering brilliant shades, high color strength and good transparency. They are well suited to printing ink applications, although they provide only moderate levels of fastness properties. The pigments are synthesized by treating aqueous solutions of the dyes under highly controlled conditions with solutions of the heteropolyacids, prepared in situ. The copper ferrocyanide salts are obtained by treatment of potassium ferrocyanide with sodium sulfite in water, and subsequently with solutions of the cationic dye and copper (II) sulfate. The pigments are primarily used in inks for packaging and advertising materials. However, they have little use outside printing inks. Reflex or alkali blue pigments are structurally related cationic dye derivatives which are inner salts of the dye structures and are also used in printing inks.

Perylenes and perinones are separate groups of pigments categorized within the carbonyl chemical class. The two pigment groups show similarities, for example, in their chemical structural features and, to an extent, in their technical and application properties as high-performance organic pigments. Perylenes constitute a series of firmly established high-performance pigments, offering red and violet colors, and also extending to black. Synthetically, they are derived from perylene-1,4,5,8-tetracarboxylic acid. The perylenes tend to be quite expensive pigments, but their high levels of fastness properties mean that they are suitable for highly demanding applications. In particular, they offer very high heat stability. Two perinone pigments are used commercially. In their synthesis from naphthalene-1,4,5,8-tetracarboxylic acid, they are formed as mixtures of the two isomers, which can be separated. The trans isomer, CI Pigment Orange 43, is a highly important commercial pigment, especially for plastics, while the cis isomer, CI Pigment Red 194, is bordeaux in color and is of much lesser importance. The perinone, CI Pigment Orange 43, provides a brilliant orange color and has very good fastness properties. Its commercial manufacture involves a challenging multistage procedure and consequently it is one of the most expensive organic pigments on the market.

This chapter describes the range of industrial monoazo pigments based on the 2-naphthol (β-naphthol) ring system. This group includes some of the earliest organic pigments introduced commercially and is also numerically the largest group of products currently described in the Colour Index. Most of the pigments within this group are red (with a few oranges), thus complementing the azoacetoacetanilides, which are mostly yellows. Three groups of monoazonaphthol-based pigments may be identified categorized according to the chemical structure of the coupling components used in their synthesis. The first group contains products based on 2-naphthol itself, a second is based on amide derivatives of 3-hydroxy-2-naphthoic acid (naphtharylamides), and the third is a series of metal salt azo pigments. The historical development of these pigments, outlined in an early section of this chapter, originated in the late 19th century with pigments described as ‘lakes’, derived from water-soluble anionic dyes absorbed on to inert colorless substrates, which were the forerunners of products now referred to as metal salt pigments. The non-ionic 2-naphthol-based pigments were introduced soon after. In the early to mid-20th century, a series of monoazonaphtharylamide (Naphthol AS) pigments were developed and introduced commercially. The pigments of this type that are currently manufactured can be sub-divided into products containing a single amide group (group 1) and higher performance products containing more than one amide or sulfonamide groups. Several group 1 pigments have diminished in importance over the years, while some higher performing group 2 pigments have grown in importance. The molecular and crystal structures of the range of pigments are presented and discussed in relation to their performance characteristics. The manufacture of the pigments involves the reaction of a diazotized aromatic amine with the appropriate 2-naphthol-based coupling component, using synthesis conditions typical of phenolic coupling components, followed by conditioning aftertreatments that are typical for azo pigments in general. Finally, there is an extensive discussion of the wide-ranging applications in which the individual pigments are used. While the pigments are especially well-suited to printing ink applications, many products also find use in paints and a few in plastics.

Our color perception is characterized by subjective influences. Color measurement enables an objective description of colors. In this process, white light is sent onto a color sample and the reflected rays are measured as a percentage compared to a white standard. The physiological standard color values are first calculated from the physical measured values by standardized conversions. From these, the L*a*b* values can be determined as they are given by the CIE (Commission Internationale de l’Éclairage). While one geometry is sufficient for color pigments to describe them, several defined geometries are required for aluminum and interference pigments. These geometries (illumination and observation angles) are specified for the different measuring instruments.