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Introduction
Acid dyes are so called because they are usually applied in acidic condition This dyes are applicable for those fibres which have amino groups ( - NH2 -) List of fibres that could be coloured with acid dyes Wool Silk Nylon
Acid dyes produce a wide range of brilliant shades They do not have any affinity to cellulosic fibres They have a good affinity to protein and polyamide fibres Usually used for dyeing of wool, silk and nylon Fastness property of individual dyes varies Care should be taken while dyeing mixture shades
The rate of dyeing is a function of temperature Each member has a specific temperature at which the rate of dyeing and the exhaustion is maximum
Chemically acid dyes resembles the direct dye After dissolution they produce A coloured anion as DSO3 Colourless cation Na+
Classification by state of division i.e. size of dye molecule Molecularly split acid dyes Aggregated acid dyes Classification by the concentration of acid used in the dye bath and the fastness properties of the dye Levelling acid dyes Milling acid dyes Super milling acid dyes
These dyes, when dissolved in water, do not split into individual molecules
The dye molecules join together to from clusters or aggregates Owing to their limited solubility, their solutions become turbid Increase in ionization temperature, results increase in
Leveling acid dyes Dyes have high leveling properties They correspond to the molecularly split acid dyes These dyes are applied from a bath containing sulphuric acid or formic acid These dyes are also known as strongly acid dyes
Milling acid dyes Leveling property is low as compared to leveling acid dyes
Super milling acid dyes Dyes are used from neutral bath Also known as neutral acid dyes Do not give the true solution but produce colloidal solution, which breaks up on boiling The leveling is poor whereas, the wash & light fastness is good
pH of dye bath
Leveling property Fastness to wet treatments Molecular weight Solubility to water State of division in water Affinity to nylon, wool and silk
24
Good Poor Low High Molecularly split Low
46
Moderate Good High Low Colloidal High
67
Very Poor Very Good High Low Colloidal Very High
Mechanism of dyeing
Abbreviations used DSO3-Na+: The generalize formula of acid dye D: The colour component of the acid dye molecule DSO3-: The dye anion Na+: The sodium ion H+: Hydrogen ion
Wool can be represented as NH2 W COOH When dipped in water it becomes NH3+ W COO-
NH3+ W COO- +
Effect of electrolyte Salt functions as retarding agent for acid dyes i.e. for molecularly split acid dyes or leveling type acid dyes Salt functions as exhausting agent for milling and super milling acid dye
Effect of temperature No exhaustion takes place below 400 C Increase in temperature increases the rate of dyeing / exhaustion In each case of dye there is a specific temperature for which it shows the maximum rate of dyeing In case of milling and super milling the exhaustion starts at 600 C and reaches at maximum at 700 C
400 C
Time (minutes) Check pH and add pre-dissolved dyes Add 10% Glaubers salt 2 4% H2SO4 (pH = 2.5 to 3.5)
Dyeing of protein fibres with molecularly dispersed dye or levelling acid dyes
400 C
Time (minutes) Check pH and add pre-dissolved dyes Add 10% Glaubers salt 1 3% CH3COOH (pH = 4.5 to 5.5)
400 C
Time (minutes) Check pH and add pre-dissolved dyes Add ammonium acetate or sulphate 2 5 % based on depth of shade
Dyeing is continued at boil for 40 to 60 minutes Rinsed with cold water and dried
Dye bath temperature is raised gradually to the boil (at 10C /min)
** Note: 1) The dyeing time can be reduced if it is carried out at higher temperature 2) Excessive dyeing time, especially at temperatures above the boil, should be avoided to prevent the possibility of damage to the wool fibres
45 minutes
Drop Bath
10 minutes
40 450 C A
10 minutes
Nylon fibres are characterized by end amino group (NH2), end carboxylic acid (COOH) and interunit amide group along the chain ( - NHCO-) + H+
Hydrogen ion
Nylon NH2
Nylon polymer with terminal amino group
Nylon NH3+
Nylon polymer with positively charged terminal amino group
Nylon NH3+ + D-SO3Nylon polymer with positively charged terminal amino group Dye anion
The inability of the dye to migrate from a heavily dyed portion of the fibre material to a less heavily dyed one is the cause of uneven dyeing
Leveling agents are required to achieve better migration
Glauber salt is mainly used as leveling agent Other leveling agents (apart from Glaubers salt) is sometimes used particularly while dyeing with super milling acid dyes wherein electrolytes performs the function of exhausting agents because of dyeing at neutral pH
Pyridine can also be used as levelling agent which have the following functions Breaking down the dye aggregates and thus encouraging molecular dispersion (solvent action) Being alkali it combines with the dye anion and retards ionisation via complex formation
Anionic leveling agent Have sulphonic acid group and combine with amino groups in nylon; blocks the NH2 groups But affinity of dye to nylon fibres is higher than leveling agent With time and rise in temperature the dye replaces the leveling agents completely Therefore, though the initial rate of dyeing is slowed down, but the exhaustion is not affected significantly
Non anionic leveling agents These agents have no affinity for the fibres Dye aggregates molecules are broken down into single
For pH < 2 to 2.5, nylon has very high affinity towards acid dyes But dyeing could not be carried out at this pH since degradation of nylon is excessive Acid dyes requiring strong acid are applied from a dye liquor containing 3 to 5% formic acid Sulphuric acid is not used It can cause degradation to nylon Glauber salt is not used It has no beneficial effect Mainly non-ionic leveling agent is used
The material is entered cold and the dye bath is brought to the boil The dyeing is continued at boil for 45 min to 60 min This dye exhaust well in weaker acid and hence acetic acid could also be used The greater crystalline fibre structure of nylon compared with wool as well as relatively lower no. of amino groups means darker shades are not obtained with acid dyes
The light fastness rating of acid dyes is 4 5 The electron arrangement in the chromophores of the acid dye molecules is such that acid dye can resist the degrading effects of suns UV radiation for considerable time
The washing fastness is 2 3 for dyes with good leveling characteristics 3 -4 for dyes with average leveling characteristics 4 -5 for dyes with poor leveling characteristics
Note regarding wash fastness: Acid dye molecules attach itself by ionic and hydrogen bonds to nylon and wool fibre polymers. These bonds may be hydrolysed in water. Acid dye molecules which are held loosely or which are not penetrated the polymer sufficiently may be removed from the polymer system of wool and nylon during laundering.
Acid dyes are acidic in nature and so are resistant to acids. Being acidic they will combine with alkalis such as those present in the detergents used for washing. The result is that the excess or loosely attached dye molecules combine with the alkaline detergent and are removed from the textile material
Questions
Explain the mechanism of an anionic levelling agent in the acid dyeing of nylon
List the fastness properties of acid dyes