Reactive Phthalocyanine Dyes

They were introduced in the late 1940s for the textile printing of cellulosic fabrics under the trade names Alcian (ICI) and Phthalogen (BAY). Both types resulted in the insolubilisation of copper phthalocyanine or related pigments within the fibre, although the respective application techniques differed considerably. Reactive phthalocyanine dyes in the 1960s superseded these early approaches to the attainment of fast bright blues and turquoises on cellulosic fabrics [63]. 

The water-soluble reactive phthalocyanine dyes (see Section 2.8) yield brilliant turquoise and green shades not available from any other dye category. The most important reactive phthalocyanine dyes contain copper or nickel as their central atom they are substituted with sulfonic acid groups and also with reactive groups joined via sulfonamide bridges. An example is C.I. Reactive Blue 15, 74459 [12225-39-7] (23) ... 

Lever AB (1999) Palladium-catalyzed hydrogen reduction and decolorization of reactive phthalocyanine dyes. J Porphyr Phthal 3 488 99... 

Phthalocyanine Dyes. In addition to their use as pigments, the phthalocyanines have found widespread appHcation as dyestuffs, eg, direct and reactive dyes, water-soluble dyes with physical or chemical binding, solvent-soluble dyes with physical or chemical binding, a2o reactive dyes, a2o nonreactive dyes, sulfur dyes, and wet dyes. The first phthalocyanine dyes were used in the early 1930s to dye textiles like cotton (qv). The water-soluble forms Hke sodium salts of copper phthalocyanine disulfonic acid. Direct Blue 86 [1330-38-7] (Cl 74180), Direct Blue 87 [1330-39-8] (Cl 74200), Acid Blue 249 [36485-85-5] (Cl 74220), and their derivatives are used to dye natural and synthetic textiles (qv), paper, and leather (qv). The sodium salt of cobalt phthalocyanine, ie. Vat Blue 29 [1328-50-3] (Cl 74140) is mostly appHed to ceUulose fibers (qv). 

Dyes may be classified according to chemical stmcture or by thek usage or appHcation method. The former approach is adopted by practicing dye chemists who use terms such as a2o dyes, anthraquinone dyes, and phthalocyanine dyes. The latter approach is used predominantiy by the dye user, the dye technologist, who speaks of reactive dyes for cotton and disperse dyes for polyester. Very often, both terminologies are used, for example, an a2o disperse dye for polyester and a phthalocyanine reactive dye for cotton. 

Phthalocyanine Dyes. The phthalocyanine molecule is much too big to be used on hydrophobic fibers and therefore is only used in its sulfonated form as the basis for direct and reactive dyes (see Phthalocyanine compounds). Its forces of attraction are different from a small linear yeUow a2o dye with which it is used to form bright greens. CompatibiHty between the two is likely to be a problem in practice and to overcome this, green dyestuffs containing a phthalocyanine dye linked via a saturated chromophore blocker (—x—) have been made, eg,... 

In view of the immense commercial importance of phthalocyanines as pigments, it is perhaps surprising that only a few are of importance as textile dyes. This is primarily due to the size of the molecules they are too large to allow penetration into many fibres, especially the synthetic fibres polyester and polyacrylonitrile. An example of a phthalocyanine dye which may be used to dye cellulosic substrates such as cotton and paper is C. I. Direct Blue 86 (96), a disulfonated copper phthalocyanine. In addition, a few blue reactive dyes for cotton incorporate the copper phthalocyanine system as the chromophoric unit (Chapter 8). 

Water-soluble phthalocyanine dyes may contain only sulfonic acid groups but normally contain both sulfonic acid and sulfonamido groups. They are used as direct dyes for paper and as reactive dyes for cotton. Representative examples are Cl Direct Blue 199 (38) and Cl Reactive Blue 71 (39). These dyes are also used for the ink jet printing of textiles (see Section 9.12.6.2). 

An appropriate ion-specific electrode was found to provide a convenient, precise and relatively inexpensive method for potentiometry of copper(II) ion in copper-complex azo or formazan dyes. Copper(II) ion in copper phthalocyanine dyes can be quantified after anion exchange. Twelve commercial premetallised dyes evaluated using this technique contained copper(II) ion concentrations in the range 0.007 to 0.2%. Thus many copper-complex direct or reactive dyes are likely to contribute low but possibly significant amounts of ionic copper to textile dyeing effluents [52]. 

According to their chemical structures and the Cl system, dyes can be classified into 17 groups nitro dyes, triphenylmethane derivatives, xanthenes, acridine derivatives, quinoline derivatives, azines, ant-hraquinones, indigoid dyes, phthalocyanines dyes, oxydation bases, insoluble azo dye precursors, and azo dyes (classes XII-XVII). In practice, dyes are classified into different application classes disperse, acid, basic, direct, vat, fiber-reactive, sulfur, preme-tallic, solvent dyes, and naphthols. 

Tapley K N, Capillary electrophoretic analysis of the reactions of bifunctional reactive dyes under various conditions including a study of the analysis of the traditionally difficult to analyse phthalocyanine dyes , 7. Chromatography A, 1995, 706, 555. 

Approximately 90% of the phthalocyanines (predominantly copper phthalocyanine) are used as pigments (qv). In addition, they have found acceptance in many types of dyestuffs, eg, direct and reactive dyes, water-soluble and solvent-soluble dyes with physical and chemical binding, a2o-reactive dyes, a2o nonreactive dyes, sulfur dyes, and vat dyes (1) (see Dyes Dyes, reactive). 

Green dyes are obtained by bridging an anthraquinone blue chromogen with a yeUow chromogen, as in the following reactive green (28) [72090-52-9] (14) or from phthalocyanine (7). 

A detailed comparison [181] of three vinylsulphone dyes included a low-substantivity monoazo N-acetyl H acid derivative (Cl Reactive Red 35), a monoazo N-acetyl J acid type of higher substantivity (Cl Reactive Orange 82) and a phthalocyanine turquoise somewhat prone to aggregation (Cl Reactive Blue 21). Dyeings of these individual products were subjected to three wash-off procedures ... 

Baxter, A. G. W. Bostock, S. Greenwood, D. (ICI). Water-Soluble Phthalocyanine Black Dyes from Cellulose Reactive Groups and Suitable for Use in Inks. U.S. Patent 4,705,528, November 10,1987. 

Copper phthalocyanine derivatives are well established as turquoise blue direct and reactive dyes for cellulosic fibres. Chlorosulphonation at the 3-position, followed by hydrolysis, yields sulphonated direct dyes such as Cl Direct Blue 86 (5.32 X = H) and Blue 87 (5.32 X = S03Na). Solubility and dyeing properties can be varied by introducing four chlorosulphonyl groups, some of which are hydrolysed and some converted to sulphonamide by reaction with ammonia or alkylamines. This approach is also the main route to reactive dyes of the copper phthalocyanine type. The reactive system Z is linked to a 3-sulphonyl site... 

These dyes are invariably monoazo compounds with the reactive system attached to the diazo component, owing to the ready availability of monosulphonated phenylenediamine intermediates. Pyrazolone couplers are most commonly used, as in structure 7.82 (where Z is the reactive grouping), and this is particularly the case for greenish yellow vinylsulphone dyes. Catalytic wet fading by phthalocyanine or triphenodioxazine blues is a characteristic weakness of azopyrazolone yellows (section 3.3.4). Pyridones (7.83), barbituric acid (7.84) and acetoacetarylide (7.85 Ar = aryl) coupling components are also represented in this sector, with the same type of diazo component to carry the reactive function. 

At present, synthetic routes to more than 40 metal complexes other than the copper complex are known. Apart from a cobalt phthalocyanine pigment (P.B.75) which was introduced to the market just recently, none of the resulting products, however, has stimulated commercial interest as a pigment. Nickel complexes, however, are found in reactive dyes, while cobalt complexes of this basic structure are employed as developing dyes. 

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