Disperse dyes

Models for the dyeing of polyester fibers with disperse dyes have been developed [8], When the dye is applied from aqueous medium, it is adsorbed from the molecularly dispersed aqueous solution onto the fiber surface and then diffuses into the interior of the fiber. The following parameters determine the rate of dyeing and, to some extent, the leveling properties (1) the dissolution rate during the transition from the dispersed crystalline state of the dye into the molecularly dispersed phase, and (2) the diffusion rate at the fiber surface and, especially, in the interior of the fiber. The rates of both processes vary with temperature. 

Differences in geometry and polarity of the dye molecules can lead to wide variations in these finishing or dye-specific properties and can have a marked effect on the absorption characteristics of all dyes, irrespective of whether singlecomponent or combination dyeing processes are used. For instance, uneven dyeing may occur when an unequal distribution of particle size results in insufficient dispersion stability and hence crystal growth and precipitation at the substrate surface. 

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Antlblaze 19. Antiblaze 19 (Mobil), a flame retardant for polyester fibers (134), is a nontoxic mixture of cycHc phosphonate esters. Antiblaze 19 is 100% active, whereas Antiblaze 19T is a 93% active, low viscosity formulation for textile use. Both are miscible with water and are compatible with wetting agents, thickeners, buffers, and most disperse dye formulations. Antiblaze 19 or 19T can be diffused into 100% polyester fabrics by the Thermosol process for disperse dyeing and printing. This requires heating at 170—220°C for 30—60 s. 

Dyes. In contrast to benzotrifluorides and fluoropyrknidines, limited commercialization has developed for dyes containing a fluoroaromatic group. FluorophenyUiydrazines have been converted to (fluorophenyl)pyrazolones, which are disperse dyes for cellulose acetate and nylon (192). 

Macromolecular stmcture and supermolecular organization also affect dye affinity. Drawn (oriented) nylon-6 has more of a random open stmcture than nylon-6,6 (172). Nylon-6, therefore, dyes more rapidly than nylon-6,6, but is also more susceptible to color crocking, especially with disperse dyes. 

Phloroglucinol is Hsted in the Colourindex as Cl Developer 19. It is particularly valuable in the dyeing of acetate fiber but also has been used as a coupler for azoic colors in viscose, Odon, cotton (qv), rayon, or nylon fibers, or in union fabrics containing these fibers (157). For example, cellulose acetate fabric is treated with an aromatic amine such as (9-dianisidine or a disperse dye such as A-hydroxyphenylazo-2-naphthylamine and the amine diazotizes on the fiber the fabric is then rinsed, freed of excess nitrite, and the azo color is developed in a phloroglucinol bath at pH 5—7. Depending on the diazo precursor used, intense blue to jet-black shades can be obtained with excellent light-, bleach-, and mbfastness. 

Dyes, Dye Intermediates, and Naphthalene. Several thousand different synthetic dyes are known, having a total worldwide consumption of 298 million kg/yr (see Dyes AND dye intermediates). Many dyes contain some form of sulfonate as —SO H, —SO Na, or —SO2NH2. Acid dyes, solvent dyes, basic dyes, disperse dyes, fiber-reactive dyes, and vat dyes can have one or more sulfonic acid groups incorporated into their molecular stmcture. The raw materials used for the manufacture of dyes are mainly aromatic hydrocarbons (67—74) and include ben2ene, toluene, naphthalene, anthracene, pyrene, phenol (qv), pyridine, and carba2ole. Anthraquinone sulfonic acid is an important dye intermediate and is prepared by sulfonation of anthraquinone using sulfur trioxide and sulfuric acid. 

Sulfonic Acid-Based Dyestuffs. Sulfonic acid-derived dyes are utilized industrially in the areas of textiles (qv), paper, cosmetics (qv), foods, detergents, soaps, leather, and inks, both as reactive and disperse dyes. Of the principal classes of dyes, sulfonic acid derivatives find utiUty in the areas of acid, azoic, direct, disperse, and fiber-reactive dyes. In 1994, 120,930 t of synthetic dyes were manufactured in the United States, of which 5,600 t were acidic (74). The three largest manufacturers of sulfonic acid-based dyes for use in the United States are BASF, Bayer, and Ciba-Geigy. 

Blends of polyester with cotton (qv) or viscose are first dyed with disperse dyes, then with sulfur dyes (see Fibers, polyester Fibers, regenerated CELLULOSics). Disperse and sulfur dyes can also be appHed simultaneously in a pad—dry—thermofix/chemical reduction pad—steam sequence. In this case, the sulfur dyes cannot be used in thein reduced form because of the effect of the sodium sulfide on the disperse dye. Therefore, this method is confined to the solubilized sulfur dyes or sulfur dyes in the dispersed form. 

The sulfur dyes are widely used in piece dyeing of traditionally woven cotton goods such as drill and corduroy fabrics (see Textiles). The ceUulosic portion of polyester—cotton and polyester—viscose blends is dyed with sulfur dyes. Their fastness matches that of the disperse dyes on the polyester portion, especiaUy when it is taken into account that these fabrics are generaUy given a resin finish. 

Dyestuffs. The use of thiophene-based dyestuffs has been largely the result of the access of 2-amino-3-substituted thiophenes via new cycHzation chemistry techniques (61). Intermediates of type (8) are available from development of this work. Such intermediates act as the azo-component and, when coupled with pyrazolones, aminopyrazoles, phenols, 2,6-dihydropyridines, etc, have produced numerous monoazo disperse dyes. These dyes impart yeUow—green, red—green, or violet—green colorations to synthetic fibers, with exceUent fastness to light as weU as to wet- and dry-heat treatments (62-64). 

There are oxazine disperse dyes reported (4) and several reactive dyes containing the oxazine ring and a few containing thiazine (5) (see Dyes, reactive). 

Additional examples have been reported (5). Disperse dyes which contain an oxazine ring include the yeUow 1,3-dinitro-lOhd-phenoxazine... 

Table 12 compares disperse dye production and sales in the United States in 1980 and 1988 by color. ... 

Azo and anthraquinone compounds comprise the two principal stmctural types which are used as disperse dyes. Other compounds used to a much lesser extent include methines, cyanostyryls, hydroxyquinophthalones, and ifitrodiarylarnines. 

Commercial Disperse Azo Dyes. The first proposal to use insoluble dyes in suspension in an aqueous foam bath, ie, disperse dyes, to dye cellulose acetate was in 1921 (60). Commercialization of disperse dyes began in 1924 with the introduction of the Duranol dyes by British Dyestuffs Corporation (61) and the SRA dyes by British Celanese Company (62). In contrast to the acid monoazo dyes, derivatives of benzene rather than of naphthalene are of the greatest importance as coupling components. Among these components mono- and dialkylariifines (especially A/-P-hydroxyethyl-and A/-(3-acetoxyethylanifine derivatives) are widely used couplers. Nitrodiazobenzenes are widely used as diazo components. A typical example is CeUiton Scarlet B [2872-52-8] (91) (Cl Disperse Red 1 Cl 11110). 

Table 13. Yellow and Orange Shade Commercial Disperse Dyes...

The early yellow disperse dyes were based on phenolic coupling components, eg, Cl Disperse Yellow 3 (92) (diazotized 4-arninoacetanihde coupled to -cresol) which is still used today for the coloration of cellulose acetate and nylon fibers. 

Dispersion Technology. Substantial advancements in dispersion technology have been made since the initial introduction in 1923 of disperse dyes in paste form for cellulose acetate. Dyes were dissolved in sulfonated fatty acids such as sulforicinoleic acid [36634-48-7] (SRA),... 

Application Techniques, Structural Variations, and Fastness Properties. When appHed to polyester fiber, many of the disperse dyes originally developed for ceUulose acetate were found to be deficient in Hghtfastness, build-up properties, and especially fastness to the high temperatures employed in the newer dyeing and finishing, printing, and Thermosol (dry heat) processes. 

High energy dyes are requited in the Thermosol appHcation and in those instances in which the dyed fabric is subjected to a heat-setting treatment. Each energy type has a characteristic rate of exhaust and, as a consequence, only disperse dyes of the same energy class are used in mixes for shade matching purposes. 

Heterocyclic Disperse Dyes. Diazotizable aminoheterocychc compounds are also used in the production of disperse dyes. Examples of the important class of 2-aminobenzothiazole dyes foUow. Red shades include (121—123) ... 

A number of other heterocycHc diazo components such as thiazole, iadazole, thiophenes, and thiadiazole types (see Fig. 1), as well as heterocycHc couplers, ie, 6-hydroxy-2-pyridinone [626-06-2] barbituric acid [67-52-7] and tetrahydroquiaoline [25448-04-8] h.2L e been cited ia the Hterature (90,91). Reviews on disperse dyes have been pubUshed (92,93). 

Basic Orange 1 (130) (aniline coupled to 2,4-diamiaotoluene) and Basic Orange 2 (22) (aniline coupled to y -phenylenediamiae) are examples of amine salt type cationic azo dyes. The cation is formed by protonation under acidic conditions. Under neutral or alkaline conditions, these dyes behave more like disperse dyes. In 1988 the U.S. production of Cl Basic Orange 2 amounted to 132 tons. 

Deep shades and full fastness properties on polyester can be achieved using disperse dyes and carriers, or temperatures over 100°C with or without carriers. 

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