WOOL, Silk and Nylon

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

Properties of acid dyes

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

Properties of acid dyes

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 of Acid Dye

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

Molecularly split acid dyes

The dye gives a clear aqueous solution

The individual molecule is ionized when dissolved in water D SO3Na D SO3- + Na+ Dyes are applied from baths containing sulphuric acid and formic acid

In absence of the acid they show a poor affinity to protein fibres

Aggregated 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

Dyes are applied from a bath containing acetic acid

Also known as weakly 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

Comparison of different acid dyes

Characteristic Chemical added to dye bath Leveling Acid Dye Sulphuric acid Milling Acid Dye Acetic acid Super Milling Acid Dye Ammonium acetate

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

Nylon: Nylon polymer

W: wool polymer

Mechanism of acid dyeing

Wool can be represented as NH2 W COOH When dipped in water it becomes NH3+ W COO-

In presence of acid (say HCl) it becomes HCl = H+ + Cl

H+ + ClCl- +H3N- W COOH

NH3+ W COO- +

Therefore, the dye will react as below DSO3Na DSO3- + Na+

DSO3- +H3N- W COOH

Factors affecting the Acid Dyeing

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

Factors affecting the Acid Dyeing

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

Principle of application of Acid dye on Wool

Boil Temperature (0C)
Rate of rise in temp at 10 C / min

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

Principle of application of Acid dye on Wool

Boil Temperature (0C) Rate of rise in temp at 10 C / min Cool at 800 C and add 0.5 1 % HCOOH

400 C

Time (minutes) Check pH and add pre-dissolved dyes Add 10% Glaubers salt 1 3% CH3COOH (pH = 4.5 to 5.5)

Dyeing of protein fibres with milling acid dyes

Principle of application of Acid dye on Wool

Boil Temperature (0C) Cool

400 C

Rate of rise in temp at 10 C / min

Time (minutes) Check pH and add pre-dissolved dyes Add ammonium acetate or sulphate 2 5 % based on depth of shade

Dyeing of protein fibres with super milling acid dyes

Procedure for dyeing wool

Bath prepared at 400 C Acid (sulphuric acid 2%) is added to obtain the right dyeing pH Retarding agent is added (glauber salt )

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)

Dye bath is circulated for 5 to 10 minutes

** 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

Principles of Application of Acid Dye on Silk

980 C 30 90 minutes

45 minutes

Drop Bath

10 minutes
40 450 C A

10 minutes

A Acetic acid + Glauber salt (pH = 4 5) B Dye solution is added

The dyeing cycle for acid dyes on silk

Application of acid dyes to Silk

Acid (Acetic acid 2%) and glauber salt are added to obtain the right dyeing pH ( 4 to 5) Dyeing is continued at higher temperature for 30 to 90 minutes Rinsed with cold water and dried Dye solution is added Dye bath is circulated for 5 to 10 minutes

Dye bath temperature is raised gradually to the boil in 45 minutes**

** It is advisable to control the dyeing at 80 to 850 C to preserve the lustre of silk

Application of Acid Dyes to Nylon

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

Nylon NH3+ SO3- -D

Ionic bond formed between positively charged terminal amino group in nylon polymer and dye anion

Points to note Nylon fibre is susceptible to uneven dyeing

Variation in molecular structure due to variation in the manufacturing process parameters

Therefore, leveling agent is required pH of the dye bath plays a prominent role Uptake is low to moderate at pH 6 10 Uptake is moderate and constant at pH 2.5 6 Uptake is high for pH < 2.5

Leveling agent in nylon dyeing

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

Leveling agents function by

Lowering initial retarding agent) rate of dyeing (acting as

Improve migration property of the dye

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

Types of leveling agents

Anionic leveling agent

Cationic leveling agent

Non ionic leveling agent

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

Cationic leveling agent

They have no affinity towards nylon fibres

Forms a salt with the dye ions and does not allow it to react readily with the ionic sites (end amino group) Hence, the initial rate slows down As the temperature is raised the salts dissociates into ions The released dye anions are taken up by the fibre

Non anionic leveling agents These agents have no affinity for the fibres Dye aggregates molecules are broken down into single

Therefore the rate of dyeing is retarded and the migration improves

Method of Dyeing Nylon with Acid Dyes

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

Fastness properties of 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

Why are acid dyes called so?

Questions

State any four of their properties

How acid dyes are classified? Explain the mechanism of dyeing wool with acid dye What do you mean by molecularly split acid dye? Discuss the factors that affect the acid dyeing of protein fibres

Explain the mechanism of an anionic levelling agent in the acid dyeing of nylon
List the fastness properties of acid dyes