Disperse Dyeing Cellulose 2.5 Acetate

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). 

In 1923, the first disperse dye was developed for dyeing cellulose acetate fibers. However, in recent years the most important appHcation of disperse dyes has been to dye polyester fibers. Accompanied by the rapid growth of polyester fibers after World War II, disperse dyes have currendy achieved the largest production among all dye classes in terms of quantity (106). 

Much of the available published data on the aqueous solubility of disperse dyes was accumulated during the 1960s in the course of studies of the mechanism of dyeing cellulose acetate with disperse dyes. Most of the dyes examined were low-energy types for dyeing acetate (Table 3.5). Particular attention was given to monoazo dyes derived from aniline or... 

Nitro Dyes. 2-Nitrodiphenylamines are readily obtained by condensation of derivatives of 2-nitrochlorobenzene 88-73-3] with suitable aromatic amines. Because of their accessibility and good lightfastness, these dyes became very important for dyeing cellulose acetate and, more recently, have gained a solid position as disperse dyes for polyester fibers. This is especially true for the reaction product of 1 mol of 3-nitro-4-chlorobenzenesulfonyl chloride [97-08-5] and 2 mol of aniline. An exhaustive review of the constitution and color of nitro dyes is given by Merian [40], The yellow nitroacridones may also be classified in this group. 

Since PES fibers are hydrophobic, water-soluble dyes do not attach. In contrast, PES fibers can be dyed easily with water-insoluble, small molecular dyes originally developed for dyeing cellulose acetate. Since the preferred dyeing medium is an aqueous liquor, the poorly water-soluble dyes must be dispersed before application (Section 3.2). 

I he simplest is the partition of a solute between two immiscible solvents. In this case [0] /[Z)], = K, where K is the partition coefficient. This equilibrium is often referred to as the Nernst distribution. When [Z)], is plotted against [Z)], at constant temperature the curve is a straight line which terminates at the point when both the fibre and the dyebath are saturated. There are slight deviations from the linearity of the curve, particularly as the solutions become more concentrated. This system is probably exhibited in its ideal form when dyeing cellulose acetate rayon from an alcoholic dye solution, but it is also essentially true in the case of the application of disperse dyes in aqueous suspension to cellulose acetate, because the dyes are all soluble in water to a very limited extent and the undissolved particles act as a reservoir to maintain the concentration of the solution. The curve for this isotherm is shown in Fig. 12.14. 

DISPERSE DYES AND DYEING CELLULOSE ACETATES Table 21.3... 

When the disperse dyes were in their early state of development it was observed that compounds containing an external sulphate group, having the general formula R NH.C2H4.0.S03Na, would dye cellulose acetate from an aqueous solution (B.D.C., Perkin and Bate, Brit. Pat. 237739). Little attention was paid to this at the time because it appeared that the disperse dyes would fulfil all requirements. In 1936 interest was revived and these dyes were placed on the market as the Solacet range by I.C.I. An example is Solacet Fast Scarlet B, formula (9), C.I. acid red 53. 

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). 

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. 

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. 

Monoazo dyes such as Disperse Blue 11 (102) and Disperse Black 1 (103) are appHed to cellulose acetate as a dispersion and dyed in the usual way, then diazotized in situ and coupled in this instance, to 3-hydroxy-2-naphthoic acid forming the blue and black shades, respectively. 

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),... 

The appearance of synthetic fibers in the 1920s accelerated the further development of anthraquinone dyes. Soon after British Celanese succeeded in commerciali2ing cellulose acetate fiber in 1921, anthraquinone disperse dyes for this fiber were invented by Stepherdson (British Dyestuffs Corp.) and Celatenes (Scottish Dyes) independendy. Anthraquinone disperse dyes for polyester fiber were developed after the introduction of this fiber by ICI and Du Pont in 1952. These dyes were improved products of the disperse dyes that had been developed for cellulose acetate fiber 30 years before. 

With simple partition the situation is comparable to the partition of a solute between two solvents. The bonding forces involved between uncharged dye and uncharged fiber, and uncharged dye and uncharged solvent are considered to be the same. The dye is sometimes referred to as in soHd solution in the fiber. This type of isotherm is found in practice with disperse dyes on cellulose acetate and polyester. It represents the dyeing situation with the minimum restrictions for the dye to enter the fiber the only restriction is when the fiber solution becomes saturated. 

Acetate fibers are dyed usually with disperse dyes specially synthesized for these fibers. They tend to have lower molecular size (low and medium energy dyes) and contain polar groups presumably to enhance the forces of attraction by hydrogen bonding with the numerous potential sites in the cellulose acetate polymer (see Fibers cellulose esters). Other dyes can be appHed to acetates such as acid dyes with selected solvents, and azoic or ingrain dyes can be apphed especially for black colorants. However thek use is very limited. 

The compound exists normally as the trans or ( )-isomer 21a. This molecule is essentially planar both in the solid state and in solution, although in the gas phase there is evidence that it deviates from planarity. When irradiated with UY light, the ( )-isomer undergoes conversion substantially into the cis or (Z)-isomer 21b which may be isolated as a pure compound. In darkness, the (Z)-isomer reverts thermally to the (F)-isomer which is thermodynamically more stable because of reduced steric congestion. Some early disperse dyes, which were relatively simple azobenzene derivatives introduced commercially initially for application to cellulose acetate fibres, were found to be prone to photochromism (formerly referred to as phototropy), a reversible light-induced colour change. C. I. Disperse Red 1 (22) is an example of a dye which has been observed, under certain circumstances, to give rise to this phenomenon. 

The three most important types of synthetic fibres used commonly as textiles are polyester, polyamides (nylon) and acrylic fibres. Polyester and the semi-synthetic fibre cellulose acetate are dyed almost exclusively with the use of disperse dyes. Polyamide fibres may be coloured using either acid dyes, the principles of which have been discussed in the section on protein fibres, or with disperse dyes. Acrylic fibres are dyed mainly using basic (cationic) dyes. 

These dyes have affinity for one or, usually, more types of hydrophobic fibre and they are normally applied by exhaustion from fine aqueous dispersion. Although pure disperse dyes have extremely low solubility in cold water, such dyes nevertheless do dissolve to a limited extent in aqueous surfactant solutions at typical dyeing temperatures. The fibre is believed to sorb dye from this dilute aqueous solution phase, which is continuously replenished by rapid dissolution of particles from suspension. Alternatively, hydrophobic fibres can absorb disperse dyes from the vapour phase. This mechanism is the basis of many continuous dyeing and printing methods of application of these dyes. The requirements and limitations of disperse dyes on cellulose acetate, triacetate, polyester, nylon and other synthetic fibres will be discussed more fully in Chapter 3. Similar products have been employed in the surface coloration of certain thermoplastics, including cellulose acetate, poly(methyl methacrylate) and polystyrene. 

An aqueous dispersion of a disperse dye contains an equilibrium distribution of solid dye particles of various sizes. Dyeing takes place from a saturated solution, which is maintained in this state by the presence of undissolved particles of dye. As dyeing proceeds, the smallest insoluble particles dissolve at a rate appropriate to maintain this saturated solution. Only the smallest moieties present, single molecules and dimers, are capable of becoming absorbed by cellulose acetate or polyester fibres. A recent study of three representative Cl Disperse dyes, namely the nitrodiphenylamine Yellow 42 (3.49), the monoazo Red 118 (3.50) and the anthraquinone Violet 26 (3.51), demonstrated that aggregation of dye molecules dissolved in aqueous surfactant solutions does not proceed beyond dimerisation. The proportion present as dimers reached a maximum at a surfactant dye molar ratio of 2 5 for all three dyes, implying the formation of mixed dye-surfactant micelles [52]. 

Numerous disperse dyes are marketed in a metastable crystalline form that gives significantly higher uptake than the corresponding more stable modification. The molar free enthalpy difference can be used as a criterion of the relative thermodynamic stabilities of two different modifications [53]. Certain dyes can be isolated in several different morphological forms. For example, an azopyrazole yellow disperse dye (3.52) was prepared in five different crystal forms and applied to cellulose acetate fibres. Each form exhibited a different saturation limit, the less stable modifications giving the higher values [54]. 

Table 3.11 Partition coefficient and saturation value of disperse dyes on secondary cellulose acetate [85]...

Measurements of aqueous solubility and partition coefficient between cellulose acetate and water were compared for thirty disperse dyes and an approximate inverse relationship was postulated [60]. This can only be valid to a limited extent, however, because the partition ratio also depends on the saturation solubility of the dye in cellulose acetate. This property varies from dye to dye and is not directly related to aqueous solubility. The solubilities of four dyes in a range of solvents were compared with their saturation values on cellulose acetate. Solubilities in benzene showed no significant correlation. With the other solvents the degree of correlation increased in the order ethanol < ethyl acetate < 20% aqueous diethylene glycol diacetate (CH3COOCH2CH2OCH2CH2OCOCH3). The last-named compound was suggested as a model with polar groups similar to those in cellulose acetate [86]. 

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