Acid Dyes:

The dye 2009 dyeing process, term, acidcarriedderives from, the which is out in an acidic aqueous solution (pH 2.6).The acid used in the dye bath is often vinegar (acetic acid) or citric acid Protein fibres contain amino and carboxyl groups, which are ionized mostly to NH3+ and C00~. In the acid dye bath the carboxylate ions are converted to undissociated carboxyl groups owing to the addition of acid HX (sulfuric or formic acid), which causes the positively charged wool to take up an equivalent amount of acid anions X. General Formula: Its general formula is D-S03-Na+ Fibre Application: These water-soluble anionic dyes are applied to Man Made Fibres o Nylon Natural Fibres o Wool, silk They are also used to some extent for paper, leather, ink-jet printing, food, and cosmetics. Classification: Acid dyes are divided into three groups based on their differences in affinity, which is primarily a function of the molecular size: Levelling dyes are relatively small molecules which form a salt linkage bond with the protein fibre. Milling dyes are large-volume dye molecules, for which salt formation with the fibre plays only a secondary role and the adsorption forces between the hydrophobic regions of the dye molecule and those of the protein fibre predominate. Dyes with intermediate molecular size not only form a salt linkage bond with the wool fibre but are also bonded to the fibre by intermolecular forces and have properties lying in an intermediate position between those of the levelling and the milling dyes. Acid dyes are thought to fix to fibres by Hydrogen bonding Van Der Waals forces Ionic bonding. They are normally sold as the Sodium salt therefore they are in solution

Assignment # 1 Acid, Basic, Disperse Dyes and their Application

PAKISTA N

anionic. Animal protein fibres and synthetic Nylon fibres contain many cationic sites therefore there is an attraction of anionic dye molecule to a cationic site on the fibre. The strength (fastness) of this bond is related to the desire/ chemistry of the dye to remain dissolved in water over fixation to the fibre.

Structures The chemistry of acid dyes is quite complex. Dyes are normally very large aromatic molecules consisting of many linked rings. Acid dyes usually have a sulphonyl or amino group on the molecule making them soluble in water. Water is the medium in which dyeing takes place. Most acid dyes are related in basic structure to the following: Anthraquinone Type: Many acid dyes are synthesised from chemical intermediates which form anthraquinone- like structures as their final state. Many blue dyes have this structure as their basic shape. The structure predominates in the levelling class of acid dye.

. Anthraauinon
Azo dyes:

The structure of azo dyes is based on azobenzene, Ph-N=N-Ph. Although Azo dyes are a separate class of dyesuff mainly used in the dyeing of cotton (cellulose) fibres many acid dyes have a similar structure, most are red in color. Triphenylmethane Related: Triphenylmethane Acid dyes having structures related to triphenylmethane predominate in the milling class of dye. There are many yellow and green dyes commercially applied to fibres that are related to triphenylmethane.

Triphenylmethane
Applica tion: These dyes are applied in the following way, 1. The dye is dissolved in the water and it dissociates as follows, D~S03Na + H20 ^ D-S03~ + Na+ 2. Wool-NH2 +H ^ Wool-NH3+ This H+ was liberated by the acid used for the acidic medium 3. Then the bond formation occurs as follows, D-S03- + WoolNH3+ ^ Wool-NH3-S03-D In case of the silk and nylon wool is replaced by them in the equation and the other reaction remains same. The temperature of dyeing is 60 DC and the migrating rate can be increased by increasing the temperature up to 70 C.

Exhausting Agent: Na2S04 is used as an exhausting agent. This causes the repelling of D~S03~ group more towards the fibres because of S03- group present in it. Retarding Agent: Usually NaCl is used as the retarding agent. It is used for the following purposes, For even distribution of the dye. For controlling the rate of reaction. For avoiding the shades in the fabrics. Fibre requirements: WOOL is usually dyed at 1% for a full shade except for blacks, navy blues, and maroons, which usually requires 3%. It may be boiled but should not be allowed to go to a rolling boil. Temperature change must be gradual to avoid felting. It should be processed at least 1 hour to 1.5 hour for good fastness. SILK is also dyed at 1% but will have richer concentration at this shade than wool. It must be dyed at lower temperature than wool not higher than 85 C. NYLON is dyed at 2% depth of shade for one hour or more and is brought to full boil. It does not absorb the dyes readily as wool and the silk do because of its molecular structure. Properties of Acid Dyes: Light Fastness: Light Fastness is the degree to which a dye resists fading due to light exposure. All dyes have some susceptibility to light damage, simply because their strong colours are indications that they absorb the wavelengths that they don't reflect back. Light Fastness is checked on BLUE SCALE. Acid dyes are resistant to sunlight and there light fastness rating is 4-5. Washing Fastness: Washing fastness of the acid dyes is also good. Its rating is from 4-5. This is checked on the GREY SCALE. Rubbing fastness: Acid dyes have also good rubbing fastness.

Basic Dyes:

These are also called as CATIONICDyes. Basic dyes are cationic, which means that the coloured part has a positive charge, when they are dissolved in water. They will bond to either carboxyl or sulfonic acid groups on a fibre, via the formation of salt links with these anionic groups in the fibre. The number of anionic sites in the fibre determine the saturation value SF, i.e. the maximum amount of dye which can be taken up by the fibre. Basic dyes can be used to dye wool or cotton, but they do not perform well, tending to fade in sunlight quite badly. So this dyeing stopped with the passage of time because these fibres were dyed much better with the other dyes. The first synthetic dye, Mauvein also known as aniline purple, discovered by William Henry Perkin in 1856, was a basic dye, almost a century before the development of acrylic fibre by DuPont, in 1944. General formu la:

Its general formula is D+. Fibre Application: Basic dyes are applied on Acrylic Fibres Modified Acrylic Fibres: These are the acrylic fibres that are produced by mixing another monomer to them. The reason for the mixing of the other monomer to it is that the Glass Transition Temperature (Tg) of the acrylic fibres is 104 UC that requires heating at high temperature. By this mixing the Glass Transition Temperature falls to 8085 C. The monomers that are usually added to them are Vinyl Chloride and Vinyl Pyridine. 15-20 % of these monomers are added. Application: When the dye is dissolved in the water this ionize and the dyeing portion of the dye is positively charged. While the fabric has the negative charged sited on it. Following reaction takes place in the dyeing process. Ac~S03~ +D+ ^ Ac-S03~~D+ If we dye the fabric below 80-85 C then the diffusion of the dye will be difficult also it will not be uniform and the rate of dyeing is slow. But as the temperature of the liquor is raised to 90 C the rate of dyeing becomes fast and the linkages will become fast. But as a result the levelling of the dye will not be uniform. Under such conditions the retarding agent is required that will level the dyeing process on the fabric. Usually NaCl is used for this function. The acidic pH condition is achieved by using the acid usually CH3C00H.

 Also a buffer solution is used to control the pH to a proper value. CH3C00Na is used for this purpose. Dyeing mechanism: The cationic chromophore is first absorbed by the negatively charged fibre surface and then diffuses, at elevated temperature, into the interior of the fibre; there it binds to active acid groups, the number of which is limited and the accessibility of which depends on temperature andfibre constitution. Therefore, the dyeing characteristics of a cationic dye are determined by affinity and diffusibility. The affinity of cationic dyes is enhanced by increasing the size of the molecule and especially by introducing aromatic residues. The phenyl substituted dye is absorbed onto polyacrylonitrile materials at a higher rate than the dye that is methine substituted as shown.
CHi CHj

Phenyl-substituted Basic dye

Methine Substituted Basic

Properties: Basic dyes have following properties/ Water Soluble Toxic in nature Produce Brilliant Shades Work under acidic conditions i. e. pH=4-5 Very Stable The light fastness of these dyes is excellent. The rating of there light fastness is 6-7. This means that these are very much stable in the light of sun. Wash fastness is also very good and the colour is not fade with the washing of the fabrics dyed with these dyes. The rating of wash fastness in about 56. The rubbing fastness of these dyes is also much better.

Oth er names for acrylic fibres: Acrylic is sold under names such as Orlon, Courtelle, Dralon, Leacryl, Acrilan, and Nitron. It is composed of poly(propenonitrile) (acrylonitrile) with small amounts of a comonomer. Modacrylic is sold under names such as BHS, Creslon, PAN, and Teklan, and also as Lycra. Modacrylic fibres are between 35% and 85% acrylonitrile, and are made from resins that are copolymers (combinations) of acrylonitrile and other materials such as vinyl chloride, vinylidene chloride or vinyl bromide. Modacrylic can probably be dyed just like acrylic.

Disperse Dyes.

These are substantially water-insoluble non ionic dyes for application to hydrophobic fibres from aqueous dispersion. They are used predominantly on polyester and to a lesser extent on nylon, cellulose, cellulose acetate, and acrylic fibres. Thermal transfer printing and dye diffusion thermal transfer processes for electronic photography represent niche markets for selected members of this class. Disperse dyes are colorants with low water solubility i.e. in the disperse colloidal form, are suitable for dyeing and printing hydrophobic fibres and fabrics. Since polyester fibres are hydrophobic, water-soluble dyes do not attach. In contrast, polyester fibres 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. Fibre Application: Disperse dyes are applied on Polyester Nylon Acetate Rayon Chemical Constitution: Industrially applied disperse dyes are based on numerous chromophore systems. Approximately 60 % of all products are azo dyes, and ca. 25 % are anthraquinone dyes, with the remainder distributed among quinophthalone, methine, naphthalimide, naphthoquinone, and nitro dyes. Azo dyes are currently employed to create almost the entire range of shades; Anthraquinone derivatives are used for red, violet, blue, and turquoise. The remaining dye classes are used mainly to produce yellow shades. Dyeing Methods: Disperse dyes are applied on the fibre in the following methods. 1) Carrier Dyeing Method 2) High Temperature Dyeing Method 3) Thermosol process

Carrier Dyeing Method: The difficulty with polyester dyeing is that it requires a lot of heat to get the dye into the fibre. Boiling water is not hot enough to do the job by itself, so a noxious-smelling carrier chemical must be added, for immersion dyeing, unless newer low-energy disperse dyes are used. The carrier often used is Phenol/Phenyl. It swells the chains in the fibre at 60-70 C so that the dye is penetrated in this state in the fibres. Following is the process for this way of dyeing. > Take the dye and disperse it into water > Add dispersing agent for the even distribution off the dye > Add acetic acid for attaining pH up to 5-6 > Add buffer solution i.e. CH3C00Na for stable pH > Add the carrier compound > Raise temperature gradually to 90-100 C > Dye for 30-35 minutes > Then drain the dye liquor and wash the fabric with detergent at 60-70 C. This washing will drain out all the carrier molecules. Reduction Clearing Treatment is then performed which removes all the dye molecules present in the surface of the fabric. Usually NaHS03+Na0H are used at 50-60 C. There are some limitations in the Carrier dyeing method because of following draw backs. Some Carriers are very expensive. Polyester and carrier are both organic in nature so it is difficult to remove completely from fabric. It uses the dispersing agent which also increases the cost and if not used then spotting may be caused. When drained into water causes pollution in it. Light fastness becomes poor with time by this dyeing process. High Temperature Dyeing Method: In this method no carrier is required and the polyester is dyed at an elevated temperature and high pressure. Temperature = 130 C Pressure = 30 lb/inch2 The other parameters and the reagents are same as used in the carrier dyeing method. Machines used in the High temperature dyeing process are High temperature Dyeing Jigger Here the fabric is dyed in the open width in the machine. JATDyeing Machine Here the fabric is dyed in the rope form and passed through a pipe for dyeing. Th ermosol Process: In dyeing polyester fibres, the dyeing time can be shortened significantly by increasing dyeing temperature. The rate of dyeing increases exponentially above the glass transition temperature; a temperature increase of 10

C doubles the rate. For this reason, at 200 C fast coloured fibres can be obtained with disperse dyes within seconds especially for polyester Cellulose mixtures. This property is used to dye polyester fibres continuously in a pad-fix process, which was introduced by Du Pont as the thermosol process. Application of the dye from an aqueous dispersion is followed by drying and fixing. Properties: Organic colouring substances Non ionic compounds Hydrophobic in nature Low water solubility that increases with the temperature Dispersed in the dye liquor Convert into fine particles in presence of the dispersing agent Forms H-Bonds when applied on the polyester Models for the dyeing of polyester fibres with disperse dyes have been developed. When the dye is applied from aqueous medium, it is adsorbed from the molecularly dispersed aqueous solution onto the fibre surface and then diffuses into the interior of the fibre. The following parameters determine the rate of dyeing and, to some extent, the levelling properties: The dissolution rate during the transition from the dispersed crystalline state of the dye into the molecularly dispersed phase. The diffusion rate at the fibre surface and, especially, in the interior of the fibre.