DYEING OF POLYAMIDE FIBRES WOOL, SILK AND NYLON

DYEING MECHANISM POLYAMIDE STRUCTURE NH2---XCOOH NH2 COOH X END AMINO GROUP END CARBOXYL GROUP POLYAMIDE CHAIN (CONH)

EFFECT OF pH
END GROUP ISONIZATION IS pH DEPENDENT
H20 NH2----X----COOH ------ +NH3 ---X---COOH+ +NH3---X---COO- ---------- +NH3 ---X---COOH (IN WATER)

(IN ACIDIC SOLUTION)

OH +NH3---X---COOH ------- NH2---X---COO- (IN ALKALINE SOLUTION)

DYEING MECHANISM WITH ANIONIC DYES

UNDER NEUTRAL OR ACID CONDITIONS
H+ DIFFUSE RAPIDLY AND GET ADSORBED ON WOOL FIBRE

BECOME ASSOCIATED WITH END NH2 GROUP OF FIBRE TO GIVE CATIONIC NH3+ GROUP DYE IONISES TO DSO3- Na+ ELECTROSTATIC ATTRACTION BETWEEN DSO3 AND NH3+
H20/H NH2XCOOH ---- +NH3 X COO- (Fibre in water)) H2O DSO3Na ---- DSO3- + Na+ (Dye in water) NH2XCOOH + DSO3Na - DSO3- +NH3---X---COO- +Na (Dyed fibre)

DYEING MECHANISM
THE HYPOTHESIS THAT ANIONIC DYE IS ATTRACTED TO CATIONIC DYE SITE IS OVER SIPLIFICATION WATER SOLUBLE DYES HAVE HYDROPHILIC WATER SOLUBILIZING GROUP HYDROPHOBIC REGIONS IN THE FORM OF BENZENE RING WITH GROUPS LIKE OH, NH2 ETC CAPABLE FORMING H BONDS AND VANDER WAALS INTERACTION WITH FIBRE NATURE OF INTERACTION WILL VERY FROM DYE TO DYE

SCHEMATIC DYE-FIBRE INTERACTION

SUITABLE DYE CLASSES

1. Acid dyes: are cheaper and produce bright shades, generally show low wash fastness Chrome mordant dyes: expensive. Produce dull shades of good all round fastness Metal-complex dyes: Are pre-metallized dyes . easy to apply and produce dyeings of reasonably good fastness

2.

3.

4.

Reactive dyes: comparatively new entrants. Give bright dyeings with good fastness properties.

DYE UNIFORMITY AND WASH FASTNESS

MIGRATION AND FASTNESS

MIGRATION DECREASESS WITH mol.wt OF DYE (rmm) AFFINITY AND WET FASTNESS INCREASES WITH mol. Wt LEVELLING OR MIGRATION CAN BE IMPROVED USING SUITABLE DYEING AUXILIARY PRODUCTS

ACID DYES
produce wide shade range.

Acid dyes are so called because the original members of the dye class were applied in a bath containing mineral or organic acid
most of the acid dyes are sulphonic acid salts but there are few containing carboxylic acid groups.

Acid dyes have direct affinity to wool silk and nylon but no affinity to cellulosic fibres.

CLASSIFICATION
APPLICATION POINT VIEW LEVEL DYEING OR EQUALIZING ACID DYES MILLING ACID DYES SUPER MILLING ACID DYES

LEVEL DYEING ACID DYES

TWO SUB DIVISIONS MONOSULPHONATED DYES (r.m.m 300-500) DISULPHONATED DYES (r.m.m 400-600) POSSESS VERY GOOD LEVELING / MIGRATION PROPERTIES AT BOIL WET FASTNESS IS NOT SATISFACTORY. THE LIGHT FASTNESS IS GENERALLY GOOD.

DYEING METHOD
These are applied at low pH value (2.5-4) using sulphuric acid(5% owm) there is danger of fibre damage at such a low pH. Glaubers salt (10-20% owm) must be added to assist leveling by competition between sulphate ions and dye anions for the positive sites. The goods are entered at 600C, raised to boil in 30 min. and boiled for 45 min, cool, wash and dry. Level dyeing acid dyes are most appropriate when uniform dyeing is critically important with moderate wet fastness. used for dyeing of bright shades in pale and medium depth with high light fastness on woolen fabrics for ladies wear, upholstery and furnishings.

DYEING CYCLE
acid is essential to achieve the optimum pH (2.5-4) sulphate ions are necessary to assist migration and levelness sulphate and dye anions compete for cationic sites on wool fibre.
W-SO4 + D2- W-D + SO4 2-

W represents a cationic site in the fibre D is the dye anion having 2 SO3- groups. Protonated amine groups in fibre are considered to be the primary sites of absorption but other groups such as amides may be involved at these low pH value.

DYEING CYCLE

DYEING PRECAUTIONS
To achieve good levelness it is essential to give sufficient time at the boil to permit the dyes to migrate this is the main mechanism by which levelness is achieved. Procedure of dye additions for shade adjustment Turn off the steam supply Add the previously dissolved dyes Run for 5 min. Return to boil and boil for 30 min.

ACID MILLING DYES

These dyes are so named because they have some degree of fastness to milling process, which indicates a higher level of wet fastness than other acid dyes. Two main subdivisions. A. Monosulphonted dyes (mol.Wt 500-600), these have been described as half acid milling dyes since they migrate and cover well but are little inferior to traditional acid milling dyes in terms of wet fastness. B. Disulphonated dyes of high mol. Wt (r.m.m) 600-900. These dyes diffuse much more slowly than typical leveling acid dyes and exhibit correspondingly higher wet fastness. However, migration and coverage properties are inferior and the addition of leveling agent is necessary. Non-polar Vander Waals forces are involved between these dyes and wool. Resulting in relatively poor migration properties. Hydrophobic interactions lead to reduced migration but increased wet fastness

DYEING BEHAVIOUR
These dyes also tend to be more tippy- dyeing than leveling dyes i.e. the affinity of the dyes for weathered tip of the wool fibre is different from that for the bulk of the fibre. For this reason and to obtain a slower and more uniform rate of absorption, dye leveling agents are normally used These products form complexes with dyes and allow solid, nonskittery dyeing with improved levelness Control of recommended temp and pH is essential Milling dyes are not easily combinable; they are therefore most suitable for self-shades. Typical dyeing recipe for milling dyes is Leveling agent 1-2% Sodium acetate 2 g/l Acetic acid to pH 5-6.5

DYEING BEHAVIOUR
There is no significant migration at boil, therefore uniform dye uptake right from beginning must be ensured. The effect of sodium sulphate on level dyeing performance of milling dyes is negligible The dyeing pH will depend on depth of shade . pH 5-6.5 may be used

APPLICATION AREAS
Milling dyes are used where good wet fastness properties are necessary. Loose fibre or slubbing for multicolour yarns or yarns for coloured woven fabrics. or for fabrics which are subjected to wet finishing particularly milling, machine washable fabrics. Milling dyes are employed primarily for bright shades. Milling dyes have also been used for black and navy shades in piece dyeing since levelness is less critical in this shade areas and fastness of leveling dyes is not adequate.

SUPER MILLING ACID DYES

Super milling acid dyes are similar to disulphonated milling acid dyes but contain higher alkyl substituents (e.g. butyl, octyl, dodecyl) to impart more hydrophobic character to the dye molecule. These dyes show exceptionally good wet fastness. They are used for bright colours on loose wool or slubbing where any batch to batch variations can be eliminated by blending These dyes are applied with a leveling agent and dyeing method is carefully designed to ensure uniform uptake since the dyes do not migrate readily. . This group comprises the dyes of high anion affinity which require minimum of acid. These are sometimes called neural dyeing acid dyes. The dyeing procedure is The material is entered at 600C into dyebath containing 2-5% of ammonium acetate The temp. is raised to boil in 45 min. It may be necessary to add 1-2% of acetic acid (30%) after boiling for 30 min. in order to exhaust the dye bath.

CHROME MORDANT DYES

Chemically chrome mordant dyes are closely related to acid dyes but their molecules contain additional groups in O,O position ( such as OH OH, OH NH2, COOH COOH etc) which enables the dye to form stable co-ordination complex with chromium within the fibre.

CHROME MORDANT DYES

Mordant dyes show good wet fastness property. The salts of Al, Cr, Cu, Fe and Sn are suitable as mordants. Of these the salts of Cr are of importance to wool dyeing. Hence mordant dyes for wool are usually referred to as chrome dyes. Methods of application Chrome mordant method Metachrome method Afterchrome method

1. 2. 3.

CHROME MORDANT METHOD

Wool is first treated with Cr compound like Sod. Or Potassium dichromate and then dyed. This is the oldest method but now not very popular because it involves two bath process, lengthy and expensive in terms of time and energy Mordanting The material is entered at 600C into a bath containing dichromate (1.5% owm) and formic acid (2% owm). The temperature is raised to boil in 45 min. and boiling continued for 60-75 min. The fabric is then washed with hot and cold water. Dyeing The well-rinsed material is entered into the dye bath containing 1-5% acetic acid (30%) at 500C, the temperature is raised to boil and boiling continued for 60-90 min. The fabric is then washed with hot and cold water.

METACHROME METHOD
With many chrome dyes it is possible to combine mordanting and dyeing in the same bath. The necessary requirement being the dye must exhaust well from the bath of pH 6-7. This obviously restricted the method to those dyes which had reasonable neutral affinity for wool Disadvantage Chances of metal complex formation in the dye bath The limited number of suitable dyes. The inability to achieve very heavy shades because of limited exhaustion at neutral pH values. Not suitable for dyeing Blacks and navy blues. High residual levels of chromium because of limited exhaustion of chromium at neutral pH

AFTER CHROME METHOD

Most widely adopted method. The dyeing and chroming processes although separate steps are often carried out in the same bath, thereby reducing dyeing times, water and energy requirements. Additionally there is no restriction on shades as there is with the metachrome process. After chroming, dyeing gives better fastness properties than either of the other two chrome-dyeing techniques. The main disadvantage of after chrome dyeing is the difficulty in shade matching, since the final colour is not developed until the chroming stage. For this reason, shading additions are often made with milling or 1:2 metal complex dyes. Shading dyes must be suitably resistant to chromate or dichromate anions in the bath.

DYEING CYCLE

DYENG METHOD
The dyeing is carried out as follows. The goods are entered at 45 0C into a bath containing dye, 2% acetic acid (30%) and 10% Glaubers salt, the temp. is raised to boil in 45 min. kept at boil for 30 min. the dyebath is then exhausted. If necessary by adding more acetic acid or 0.5-1% or formic acid and boiling for a further 30 min.. When the dyebath has been exhausted completely it is cooled slightly, Add dichromate Continue dyeing for a further 30-60 min. Boiling must be continued sufficiently long to ensure complete reduction of the chromate on the fibre. This method provides best fastness properties.

METAL COMPLEX DYES

These dyes are also referred to as premetallized dyes.

Earlier members of this class of dyes were produced from the premetallisable acid dyes.
Therefore these dyes are also classified as acid dyes in the Colour Index. Though most of the transition metals can form complex with the dye, commercially, chromium complex dyes are mostly synthesized and marketed.

1:1 METAL COMPLEX DYES

the 1:1 metal complex dyes are prepared from dyes possessing chelating groups e.g O O dihydroxy azo dyes containing one or two sulphonic groups to render them water solubility

1:1 METAL COMPLEX DYES

Besides o odihydroxyazo compounds, the 1:1 metal complex dyes include o-amino-o-hydroxy azo compounds and derivatives of salicylic acid. (COOH COOH groups). These dyes are mostly monosulphonates of mol.Wt. 400-500. This gives them dyeing properties somewhat similar to those of monosulphonated leveling acid dyes. In spite of the decline in recent years in the use of 1:1 metal complex dyes, the dyes continue to be used in the dyeing of loose stock and yarn for floor coverings, hand knitting yarns and piece goods. They exhibit excellent level dyeing and penetration characteristics. The dyes have good light fastness and moderate wet fastness.

DYEING METHOD
1:1 metal complex dyes are usually applied to wool from a strongly acidic (pH 2) dye bath ( hence dyes some times are referred to as acid dyeing metal complex dyes). Under these conditions the dyes possess excellent migrating and leveling properties. Since wool absorbs approximately 4% owf of sulphuric acid (96%), an excess of acid is required in order to maintain a suitably acidic dyebath. Chelating agents for water softening should not be used owing to demetallization of some dyes. Because prolonged boiling under such low pH conditions can cause fibre damage, either reduced amounts of sulphuric acid or other acids such as formic acid (810%) owf) or proprietory leveling agent can be used. The dyes can also be applied at 80 0C so as to reduce fibre damage. BASF suggest the use of sulphamic acid in place of sulphuric acid. The pH of the dye bath at the beginning is 1.8, but as the temp. rises to boil the pH increases between 3 3.5 owing to hydrolysis of sulphamic acid leading to less fibre damage compared to sulphuric acid. NH2SO3H + H2O NH4HSO4

DYEING CYCLE

1:2 METAL COMPLEX DYES

The wet fastness properties of 1:1 metal complex dyes are lower than those of mordant dyes their excellent migrating and penetration character, ease of application, good light fastness and comparatively bright shades made them popular till the introduction of 1:2 metal complex dyes in 1951. Owing to the weakly acid or neutral pH conditions used for application of 1:2 metal complex dyes they are sometimes referred as neutral dyeing metal complex dyes. These dyes are classified into two groups
1. unsulphonated 1:2 metal complex dyes 2. sulphonated 1:2 metal complex dyes

UN-SULPHONATED 1:2 METAL COMPLEX DYES

UN-SULPHONATED 1:2 METAL COMPLEX DYES

These dyes are free of strongly polar ionic water solubilizing group like SO3Na. Water solubility is conferred by the inherent anionicity of the 1:2 structure (arising from the loss of four protons from the two dye ligands) and the presence of non-ionic, hydrophilic substituents such as methyl sulphone (SO2CH3), sulphonamide (SO2NH2), methyl sulphonamide ( SO2NHCH3). these dyes are salts of strong acid dissociate completely in dilute solutions to give a Vely charged dye molecule. They show high neutral dyeing affinity and very good fastness to light and wet treatments. Their high affinity can cause rapid initial strike have slow diffusion and migration properties.

SULPHONATED 1:2 METAL COMPLEX DYES

Introduction of sulphonic solubilizing group leads to dyes having poor leveling properties and lower fastness to wet treatments. Over the last 30 years great advances have been made in developing auxiliary products which improve the level dyeing properties of sulphonated 1:2 metal complex dyes Sulphonated 1:2 metal complex dyes are divided into two sub-classes Unsymemetrical monosulphonated dyes: The two dye molecules in the complex may be different Disulphonated dyes: Many of these dyes are symmetrical in structure and are cheaper than unsymmetrical monosulphonated dyes. They are slow in dyeing and do not cover irregularities well. They can be applied on wool using amphoteric or weakly cationic leveling agent with control of pH and temperture, but their intrinsic migration properties are poor.

DYE STRUCTURE

DYEING METHOD
Dyeing is carried out at pH 5-6 using ammonium acetate.

The usual method of application typically is as follows. The yarn or cloth is treated at 40 0C for 10 min. in a bath set with 2-4% ammonium acetate. Dissolved dye is then added the temperature is raised to boil in 45 min. After 30-60 min at boil the bath should have exhausted to the extent of 90% After dyeing rinse with hot and cold water

DYEING pH FOR DYE CLASSES FOR WOOL

Typical dyeing pH for different dye classes for wool Dye bath pH for 80-85% exhaustion dye class pH Leveling acid dyes 2.5-4 Milling acid dyes 4.5-5.5 Super-milling acid dyes 5-6 1:1 metal complex dyes 2- 4 1:2 metal complex dyes 5-6

REACTIVE DYES
Following ranges of reactive dyes available for dyeing of wool

CHARACTERISTICS
High degree of dye-fibre covalent bonding at the end of dyeing operation, minimizing the washing treatment required to give maximum wet fastness. The rates of adsorption is higher than rate of reaction to avoid uneven dyeing. A highly reactive dye will react rapidly with the fibre during exhaust dyeing reducing its chances of migration to get uniform dyeing. Whereas a low reactive dye will require extended dyeing time for the reaction to complete

CHEMISTRY OF REACTIVE DYES

In theory dyes are capable of reacting with sites in the fibre such as OH in cellulose and NH2, SH (Thiol), OH in wool or silk. The dye fibre reaction can take place either by nucleophilic substitution or nucleophilic addition.

LANASOL DYES
These have been introduced as compatible trichromatic system based on Lanasol Yellow 4 G, Lanasol Blue 3 G, and Red 6 G. Lanasol dyes based on -bromo acrylamido reactive group were introduced in 1966 are known for their brightness of shade, high reactivity and good all round fastness properties. These dyes are capable of reacting with polypeptides through both nucleophilicsubstitution and nucleophilic addition reactions. The rate of fixation of these dyes on merino wool is 3 times higher than that of boiled silk.

LANASOL DYES

DRIMALAN F DYES
These dyes were specially synthesized for wool and are among the most important reactive dyes for machine washable wool. They are distinguished by brilliance of shade, high efficiency of reaction with the fibre and good wet and light fastness. The reactive group in these dyes is 2,4, difluoro- 5chloropydimidine. The reasons for the success of these dyes is the resistance to hydrolysis and high degree of reaction with fibre. The fluorine atom in position 4 reacts first because of its high reactivity but the reactivity of fluorine atom in position 2 is also high enough to further react with wool. Their excellent wet fastness is due to their high fixation ratio of the order of 95% and above.

DRIMALAN F DYES
The high fixation ratio has been attributed to the high reactivity of partially hydrolyzed dye, since the reactivity of second fluorine -carbon is only slightly decreased after the first fluorine has reacted with wool. These findings indicate that the dye molecule has two reactive centers, which can react independently with the nucleophiles in protein fibres. There is also evidence that these dyes form cross-links both with wool and silk. In silk tyrosine OH group also takes part in the reaction. Levelling agents Drimagen F (S) and Avolan RE (BAY) are recommended to get uniform dyeing.

DRIMALAN F DYES

HOSTALAN AND PROCILAN E DYES

The novelty of this class of dyes lies in the controlled nature of the reaction with fibre. The actual reactive group is formed only gradually during the exhaustion dyeing, so that in the early stages of dyeing these dyes behave more like an acid level dyes, offering a real chance of sufficient dye migration to obtain level dyeings. These dyes are blocked vinyl sulphone derivatives which gradually activate to the reactive vinyl sulphone at elevated temperature.even under slightly acidic conditions. The main advantage of such system is an improvement in dye levelness, due to suppression of dye-fibre covalent bonding at temp. below boil. It is believed that Hostalan E brands are the most level dyeing Nmethyltaurine adducts, other Hostalans are -sulphatoethyl sulphone specially selected for their ready formation of the reactive vinyl sulphone form under the weakly acidic boiling conditions required for wool dyeing.

HOSTALAN OR PROCILAN E DYES

DSO2CH2CH2OS03- Na+ PEPTIDE Beta Sulphatoethyl sulphone DSO2CH=CH2 + NH2

Vinyl Sulphone

- DSO2CH2CH2NH--PEPTIDE

CHEMISTRY OF HOSTALAN DYES

CONVENTIONAL REACTIVE DYES

Wool can be dyed with conventional rective dyes namely Procion M, H and vinyl sulphone (Remazol). These dyes produce shades with good wet fastness and brilliance when dyed at pH 8-9.

REACTIVE DYE REACTION WITH SILK

Reactive dyes also form covalent bond with silk giving good wet fastness just as with wool or cellulose. Their preferred applications are in the yarn sector for coloured wovens in prints on washable goods and shirtings for dyeing discharge grounds on woven fabrics due to their good dischargeability for dyeing knit goods especially washable articles. REACTION WITH SILK The reaction partners are mainly the terminal amino groups of the lysine, especially when dyeing is carried out in the neutral to weakly acidic region. In the alkaline region the phenol group of the tyrosine side chain may also react with the dye.

REACTION WITH SILK