Acid mordant dyes

Purpurin [81-54-9] (179) is a usefiil iatemiediate for preparing acid-mordant dyes, and is prepared by oxidation of alizarin with manganese dioxide and sulfuric acid (145). 

Acid—mordant dyes have characteristics similar to those of acid dyes which have a relatively low molecular weight, anionic substituents, and an affinity to polyamide fibers and mordant dyes. In general, brilliant shades caimot be obtained by acid—mordant dyes because they are used as their chromium mordant by treatment with dichromate in the course of the dyeing procedure. However, because of their excellent fastness for light and wet treatment, they are predominandy used to dye wool in heavy shades (navy blue, brown, and black). In terms of chemical constitution, most of the acid—mordant dyes are azo dyes some are triphenyhnethane dyes and very few anthraquinone dyes are used in this area. Cl Mordant Black 13 [1324-21 -6] (183) (Cl 63615) is one of the few examples of currentiy produced anthraquinone acid—mordant dyes. It is prepared by condensation of purpurin with aniline in the presence of boric acid, followed by sulfonation and finally by conversion to the sodium salt (146,147). 

Aminosalicylic acid is used in preparing azo dyes, conferring on them, as does salicylic acid, mordant dyeing properties. 

The group includes many natural and synthetic dyes, the latter usually being obtained from anthracene. They have no natural affinity for textiles but are applied to cellulosic or protein fibres which have been mordanted previously with a metallic oxide. The acid mordant dyes are a special class of dyes applied to wool or polyamide fibres as if the were acid dyes, and then given very high wet-fastness by subsequent mordanting. 

A naturally-occurring mordant dye, used extensively until a few years ago, and now probably the only one still in use, is logwood. It yields a navy blue or a black, with what is called a good bloom, when dyed on chrome mordanted wool. Until the advent of acid mordant dyes, which will be described later, it was the only dyestuff with which wool could be dj ed black with any measure of fastness. 

The shades can be brightened by the addition of acid dyes at the commencement of the dyeing, but their presence will diminish the wet-fastness. The dyes must be unaffected by dichromate and such that can be dyed satisfactorily at the pH necessary to exhaust the acid mordant dye. Some recommended dyes are given below. 

If a correction to the shade is necessary and the standard of fastness is to be maintained, the most convenient procedure is to cool the liquor to 60°C (140°F) and add sufficient sodium acetate to convert any free sulphuric to acetic acid, and then correct with an acid mordant or a premetallized dye. If the amount of dye required is not great the wool will already contain sufficient Cr Os to combine with the acid mordant dye. A few dyes suitable for shading are shown below. 

An exhaustive investigation of the acid mordant dyes was made by Stevens, Rowe, and Speakman J.S.D.C., 1943, 59, 165) with a view to ascertaining why some responded to the metachrome-mordant method and others did not. In the first place they examined the behaviour of wool towards the mordant in the absence of the dye. It was found that, after boiling or 6 hours, 99-7 per cent of the chromium in the dyebath had been adsorbed by tlie wool and about 42 per cent of the total ammonia had been wolved, leaving the liquor with a p of 5 02. They suggested that the first... 

The acid mordant dyes are applied, in the first stage, in the manner already described for acid dyes. Because the exhaustion is not so good as with wool it is advisable to run the dye liquor off when the dyeing cycle is complete and refill with fresh water for chroming. The chroming is carried out with 3 to 4 per cent of formic acid (85 per cent) and the following quantities of dichromate ... 

Better resistance to laundering and non-staining of cellulose is obtained with virtually all the premetallized dyes. The 1 1 chromium complex dyes should not be used under conditions when very high sulphuric acid concentrations are necessary because of the risk of degrading the cellulose. Many of the acid mordant dyes can be used with success. 

Most xanthene dyes are classified as basic dyes by their method of appHcation acid dyes can be produced by introduction of sulfonic acid groups. The fluoresceins, which contain carboxy and hydroxy substituents, are also acid dyes for coloration of silk. Some of the fluoresceins in which the carboxy group has been esterified, are soluble in alcohol or other organic solvents and can be classified as solvent dyes. Mordant dyes can be produced by introducing o-dihydroxy or sahcyhc acid groups (2), which when metallised can have very good lightfastness. 

PurpurogaHin (5), a red-brown to black mordant dye, forms from electrolytic and other mild oxidations of pyrogaHol (1). The reaction is beHeved to proceed through 3-hydroxy-(9-benzoquinone (2) and 3-hydroxy-6-(3,4,5-trihydroxyphenyl)-(9-benzoquinone (3). The last, in the form of its tautomeric triketonic stmcture, represents the vinylogue of a P-diketone. Acid hydrolysis leads to the formation of (4), foHowed by cyclization and loss of formic acid... 

Amino-4,6-dinitropheno1 is an important intermediate in the manufacture of colorants, especially mordant dyes. It has also been used as an indicator dye in titrations (yellow with acid, red with alkali) and as a reagent for albumin deterrnination. 

Dihydroxynaphthalene [83-56-7] behaves similarly to 1-naphthol coupling takes place mainly in the 4-position by simple diazonium compounds, and in the 2-position with diazophenols. Diazotized 2-arninophenol-4-sulfonic acid [98-37-3] couples with 1,5-dihydroxynaphthalene to produce the important mordant dye Diamond Black PV [2052-25-7] (see stmcture 53) (Cl Mordant Black 9 Cl 16500). 

There are three general classifications of acid dyes depending on their method of apphcation acid dyes that dye direcdy from the dyebath, mordant dyes that are capable of forming metallic lakes on the fiber when aftertreated with metallic salts, and premetallized dyes. 

Mordant Dyes. MetaUizable azo dyes are appHed to wool by the method used for acid dyes and then treated with metal salts such as sodium chromate [7775-11-5] sodium dichromate [10588-01-9] and chromium fluoride [1488-42-5] to form the metal complex in situ. This treatment usually produces a bathochromic shift ia shade, decreases the solubUity of the coloring matter, and yields dyeiags with improved fastness properties. The chromium salts can be appHed to the substrate before dyeiag (chrome-mordant or chrome-bottom method), together with the dye ia a single bath procedure (metachrome process), or as a treatment after dyeiag (afterchrome process). 

Most mordant dyes are monoazo stmctures. The most important feature of this class of dyes is excellent fastness to light and washing. Mordant dyes are available ia aU shades of the spectmm with the exceptioa of bright violets, blues, and greens. To be useful, the metal complexes must be stable, ie, must not demetallize when subjected to dyebath conditions and aU aftertreatment processes, especially repeated washings. Chromium forms stable chelate rings with mordant dyes which are not affected by treatment with either weak acid or alkaU (see Coordination compounds). 

In mordant dyes, phenols, naphthols, and enolizable carbonyl compounds, such as pyrazolones, are generally the couplers. As a rule, 2 1 metal complexes are formed ia the afterchroming process. A typical example of a mordant dye is Eriochrome Black T (18b) which is made from the important dyestuff iatermediate nitro-l,2,4-acid, 4-amiQO-3-hydroxy-7-nitro-l-naphthalenesulfonic acid [6259-63-8]. Eriochrome Red B [3618-63-1] (49) (Cl Mordant Red 7 Cl 18760) (1, 2,4-acid — l-phenyl-3-methyl-5-pyrazolone) is another example. The equiUbrium of the two tautomeric forms depends on the nature of the solvent. 

Subsequendy, H. Caro and W. H. Perkin independendy developed the commercial manufacturing process of alizarin from anthraquinone (qv) through anthraquinone-2-sulfonic acid. Taking advantage of these inventions, many manufacturers came to produce various kinds of hydroxyanthraquinones, which were used as mordant dyes for dyeing cotton and wool. 

Meta.1 Complex Dyes. Metals such as chromium and cobalt can be iatroduced iato dye molecules to give larger molecules. They can be regarded as being a special form of mordant dye. The complexes can be formed by chelating one or two molecules of dye with metal. They are appHed ia a similar manner to acid dyes. 

Mordant dyes generally have the characteristics of acid dyes but with the ability in addition to form a stable complex with chromium. Most commonly, this takes the form of two hydroxy groups on either side of (ortho to) the azo group of a monoazo dye, as illustrated for the case of C. I. Mordant Black 1 (151). The dye is generally applied to the fibre as an acid dye and then treated with a source of chromium, commonly sodium or potassium dichromate. As a result of the process, the chromium(vi) is reduced by functional groups on the wool fibre, for example the cysteine thiol groups, and a chromium(m) complex of the dye is formed within the... 

Elder leaves combined with alum or chrome as a mordant dyes fabric green. When the leaves are mixed with alum and salt, a lilac color emerges. Adding elder leaves to copper and acetic acid yields a... 

Many dyes that have no chemical affinity to fibrous substrates can be attached to such substrates by intermediary (go-between) substances known as mordants. These are either inorganic or organic substances that react chemically with the fibers as well as with the dyes and thus link the dyes to the fibers. Mordants are traditionally classified into two main classes, acid and metallic mordants. The acid mordants are organic substances that contain tannins (see Textbox 64) as for example, gall nuts and sumac. The metallic mordants are inorganic substances, mostly mineral oxides and salts that include metal atoms in their composition. Table 94 lists mordants of both these types, which have been used since antiquity. 

Only the products associated with acid and premetallised dyes are dealt with in this section. The auxiliaries used with mordant dyes are covered in section 5.8. Anionic acid dyes, applied principally to wool and nylon, vary widely in their fastness and level-dyeing properties (section 3.2.2) in general, the higher the wet fastness of a dye the more difficult it is to apply evenly. Hence it is not surprising that the use of auxiliaries with acid dyes is related mainly to level-dyeing properties. There are two basic aspects ... 

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