Azomethine metal complex pigment

Azomethine metal complex pigments replace the metal with tin stabilizers, resulting in a change in shade. In the case of manganese-laked pigments trouble can also be expected in the presence of epoxy compounds. Pigment preparations based on epoxidized soya bean oil are normally used instead of diisodecyl phthalate pastes in the automotive sector e.g. for coloring PVC roofs etc. 

Yet another structural principle is represented by metal complex pigments based on isoindolinones. Condensation of amino-iminoisoindolinones (imino-phthalimide) with 2-aminobenzimidazole in a high boiling solvent affords an azomethine (36). This compound reacts with salts of divalent metals, such as Co, Cu, Ni, to yield yellow azomethine metal complex pigments [10] ... 

Commercially available azo and azomethine metal complex pigments cover the spectral range from considerably greenish to reddish yellow and yellowish orange. Compared to their parent structures (the corresponding azo and azomethine compounds), azomethine metal complexes frequently exhibit a distinctly duller shade. Formation of the metal complex often shifts the color of an originally yellow material in the greenish yellow direction. 

Table 25 Examples of azo and azomethine metal complex pigments.

It is only for reasons of simplified classification that the pigments which are described in this section, like azomethine metal complex pigments (Sec. 2.10.1.2), are listed in Chapter 2. Actually, rather than being azo pigments, these are azo methine and methine pigments, which in the classification system adopted in this book are formally located between azo pigments and polycyclic pigments. 

The commercially most interesting metal complex pigments within the azo series are those obtained from aromatic o,o -dihydroxyazo compounds, while important products within the azomethine series are nickel or copper complexes of aromatic o,o -dihydroxyazomethine compounds. 

Metal complex pigments are mainly used in paints. The products are fast enough to be applied especially in industrial finishes. Some representatives, particularly azomethine copper complex pigments, are very weatherfast, which makes them suitable candidates for automotive finishes. High transparency in combination with good weatherfastness is an asset for use in metallic finishes. It is not uncommon for metal complexes to lose much of their brilliance in white reductions. Some are also recommended for use in architectural paints, especially for emulsion paints. 

Further, stable 2 1 transition metal complex pigments 27 (C.I. Pigment Yellow 177) and 28 (C.I. Pigment Yellow 179), featuring six-ring chelates, have been prepared from methine and azomethine type isoindolinones l... 

The azo group (—N=N—) may be replaced by the analogous (—CH=N—) moiety to form an azomethine complex pigment, usually with copper as a chelating metal. The number of commercially available products in this group is also restricted. They typically afford yellow shades. Those species that provide the required lightfastness and weather resistance are used in automotive finishes and other industrial coatings. 

Metal complex formation considerably improves both lightfastness and weatherfastness in o,o -dihydroxyazo and o,o -dihydroxy azomethine pigments, usually compromised by distinctly dull color. 

Special consideration should be paid to metal complexes such as azomethine pigments (Sec. 2.10). At high temperatures, the yellow copper complex with the chemical constitution 10, incorporated in PVC, will exchange its chelated copper atoms with the metal atoms present in the application medium. Stabilizers containing barium/cadmium or lead produce yellow shades, while dibutyl tin thiogly-colate or other tin compounds produce a brilliant medium red. Color change is slow at low temperatures, but at 160°C the effect is rapid [108],... 

The aromatic moieties are possibly substituted benzene or napthaline rings. In azomethine pigments, only one form of metal complex is possible. This is in contrast to azo metal complexes, which may assume either structure 31 or 32 ... 

Recent developments in this class prefer azomethine complexes as chemical structures rather than azo metal complexes. The list of commercially available types includes Pigment Green 8 and 10, Pigment Yellow 117,129,150,153,177,179, and Pigment Orange 59,65, and 68, as well as P.R.257. 

In general, the stability of metal complexes of bidentate azomethines of the type (191) is comparable to that of metal complexes of the analogous bidentate azo compounds (14) and is inadequate for practical application in the dyestuffs field. Limited numbers of such complexes have, however, been claimed to be suitable for pigment applications. 

Metal complexes of tetradentate azomethines, e.g. (199), are reported136 to have very high light-fastness but to be tinctorially weak and dull in hue. Despite this they are of technical interest as very fast yellow to brown pigments. They find no application as dyestuffs, however, because of these deficiencies for example, the chromium complex of (200) gives dull, tinctorially weak dyeings on wool possessing poor wet-fastness properties. 

For example, meso-tetraaryltetrabenzoporphyrin zinc complex results from heat treatment of the corresponding 3-benzylidenisoindolinone with zinc benzoate l Appropriately substituted methine and azomethine isoindolinones featuring substructure 24 were also converted into stable metal chelate pigments of general structure 26 via a metal template reaction with aromatic and heterocyclic a-hydroxy aldehyde or ketone hydrazone derivatives incorporating the structural element 25 . ... 

Metal complexes of azo and azomethine dyes are an important class of industrially relevant pigments. Such pigments possess more advantageous properties compared to their parent chromophore including bathochromic shift of absorption, better weather- and lightfastness and enhanced solvent resistance [90]. 

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