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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)
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
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Reactive dyes: comparatively new entrants. Give bright dyeings with good fastness properties.
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
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.
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.
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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
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.
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.
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
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
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
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
Vinyl Sulphone
- DSO2CH2CH2NH--PEPTIDE
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.