DIRECT DYEING

LECTURE-3

By Robel L.

Department of Textile Technology

 Introduction
 Direct dyes are so called direct because they are applied to cellulosic
fiber directly with out the need for a mordant.

 Also known as substantive dyes

 Have excellent substantivity for cellulosic textile materials (cotton,

viscose rayon and others)

 Direct dyes are sodium salts of aromatic acids and most of them
contain azo group as the main chromophore.

 Can be denoted as DSO3Na

 Typical characteristics of Direct Dyes

Inherent substantivity to Do not require mordant, dyeing

cotton and other cellulosics procedure is quite simple.

Direct dyes are anionic in nature

Direct dyeing of cotton usually in the presence of an

electrolyte such as NaCl or Na2SO4.

Water soluble

Available in a full range of hues but

not known for their color brilliance.
Relatively inexpensive,
 Direct dyes usually have linear long coplanar molecular
structure Chromophore group

Solubilizing group

Sulphonated azo dyes constitute the predominant group of

direct dyes

Their major drawback is their poor to moderate fastness to

washing.

Various treatments to improve fastness After treatment

Dye Solubility depends on
Number of solubilizing groups,

Molecular weight and

Temperature of dyeing
 Nature of direct dyes

Molecules are large and conform to general formula

R1—N=N—X—N=N—R2. (disazo or polyazo types)

The chromophore in direct dyes includes the following

Azo (disazo, trisazo, polyazo)
Stilbene
Oxazine
phthalocynanine
Thiazole 6
 Application of direct dyes to cellulose

 By bringing dye bath to boil gradually and holding at boil whilst

the dye diffuses into the fiber.

 In absence of electrolyte some direct dyes will not dye cellulose at

all.

 Usually applied with the addition of electrolyte at or near the

boil.

 Dyeing with direct dyes is carried out in neutral solution

 Simple dyeing procedure

 Requirement of soft water for some direct dyes during application

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 CLASSIFICATION OF DIRECT DYES
CHEMICAL STRUCTURE OF CHROMOPHORE

DIRECT AZOIC DYES

DIRECT THIAZOLIC DYES

Contains both sulfur and nitrogen

Classification based on chemical structure is not significant for

the dyer because dyes with similar constitution can have quite
different application and fastness properties.
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 CI Direct Red 16 CI Direct Green 28

Very Good fastness to light

Good fastness to light

CI Direct Blue 106

CI Direct Blue 93
Pre-metallized azo copper complexes Tri-pheno-di-oxazine structure 9
 DYEING PROPERTIES [EQUALIZING]

The most common classification of direct dyes is that of the Society of

Dyers and Colorists (SDC), based on

 Their levelling ability and

 Their response to increase in the dyeing temperature and to added

salt during exhaust dyeing.

Class A: Self leveling

Class B: Average leveling

Class C: Poor leveling

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 Class A: Self leveling
 Low molecular weight => mono- Good migration, even in
and bis-azo dyes with several the presence of salt.
anionic sulphonate groups per
molecule.
Several sulphonated groups
per molecule
Good solubility and no aggregation
Low substantivity

Large amount of salt for exhaustion

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Dyeing is started at 50 °C in the presence of added salt, the bath
heated to the boil over 30–40 min, and dyeing continued at the boil
for up to an hour.

Several further salt additions, of increasing size, are required to

promote exhaustion, the total amount of salt (5–20% owf NaCl)
depending upon the depth of shade and the liquor ratio.

These dyes would give greater exhaustion by dyeing at lower

temperatures, dyeing at the boil allows good levelling and adequate
Penetration of the dyes into the fiber.
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 Class B: Salt Controllable
 Molecular weight higher than Class A

 Bis- and tris-azo dyes with lower sulphonated groups than

Class A dyes

 Medium solubility and degree of aggregation

 Low to moderate substanivity [Absence of salt]

 Salt sensitive (salt-controllable dyes) & exhaust well with salt

addition Give much increased exhaustion on addition
of small amounts of salt to the dyebath.

Similar dyeing method with Class A dyes but the initial salt is omitted.

Gradual addition of dissolved salt, at the boil, controls the exhaustion.

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 Class C: Temperature controllable

 High molecular weight

 polyazo dyes with few sulphonated groups per molecule

 Less solubility and high degree of aggregation

 High substantivity Dye aggregates are too large to

penetrate into the pores of
 Very sensitive to salt addition
cellulosic fibres.
 Leveling agents may be required
Lower the rate of
dyeing (diffusion)

Level dyeing depends on the gradual increase of the dyeing

temperature and subsequent additions of limited amounts of salt.

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 COMPARISON OF DIRECT DYES
TYPE MIGRATION LEVELING FASTNESS

Class A Good Self leveling Low

Class B Medium Medium leveling Moderate

Class C Poor Poor leveling High

Additional Classification Parameters:

Further treatment, continuous dyeing, high temperature dyeing

 DIRECT DYE SUBSTANTIVITY FOR CELLULOSE

 Long, coplanar dye molecules can sit on top of a cellulose

polymer chain with the aromatic rings parallel to the glucose

rings.

 Possibility of hydrogen bond formation

 Vander walls and other secondary forces of interaction

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Their long flat (coplanar) structure enables them to lie along a
cellulose chain in register with hydroxyl groups and results in
effective vander waals forces.

Cellulose has an abundance of hydroxyl groups

Direct cotton dyes often have hydroxyl, amino or amide groups

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 Dyeing methods

The selection of specific direct dyes for dyeing cellulosic fibres

depends on

Their dyeing properties,

The particular fastness requirements,

Any after treatments used to improve the

washing fastness, and

The particular finishing processes involved.

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A typical dyeing process for a Class B direct dye on cotton
EXHAUST DYEING

Dyeing with direct dyes is carried out in neutral solution.

Direct dyes usually have good water solubility but the

solubility is lower in the presence of salt.

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 Salient Features of Batch Dyeing

 Solution preparation starts with small dye paste to which is added

sufficient hot water for dissolution

 Wetting agent assist penetration and level dyeing

If the powder is difficult to wet.

 Depth enhancement by controlling salt addition & temperature

Levelling agents are useful when using
dyes that do not easily migrate.
 Hank and package dyeing for cotton yarns
EDTA
 Jigger for woven fabrics
Sodium hexa-meta-phosphate is the preferred
 Winch for knitted fabrics
sequestrant when using copper complex dyes.
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 FACTORS AFFECTING DIRECT DYEING
EFFECT OF SALT

 Cellulose immersed in water develops a negative surface potential

 Repulsion between negative charge of cellulose surface &

anionic dye molecule.

 The added salt provides sodium ions to counteract the negative

surface potential of the wet cotton

 Hence increase in exhaustion of direct dyes

 Commercial direct dyes already contain much electrolyte.

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 EFFECT OF TEMPERAURE

 Temperature increases dye migration and rate of dyeing.

 Equilibrium exhaustion decrease as dyeing temperature

increases (a)

 The actual dyeing temperature may often depend on machinery

limitations.

 Example, open jig dyeing machines cannot achieve dyeing

temperatures much above 85 °C.

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 EFFECT OF DYEING PH

 Acid baths specially strong acid not suitable

[Cellulose Damage]

 Dyeing of cotton with direct dyes at neural pH

If dyeing of cellulosic fibres is in acidic solution, only weak acids

are used.
The residual acid in the goods is thoroughly rinsed out before
drying.

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 EFFECT OF LIQUOR RATIO
Dye bath exhaustion should increase with decrease in the dyeing
liquor ratio in case of direct dye.
Lower liquor ratio enhances exhaustion for substantive dyes
Dyeing at low liquor ratio
 Decreases the amount of waste dye in the
effluent.
 Consumes less water and steam, and
 Allows a given salt concentration with less
added salt.
 EFFECT OF SURFACTANT

Inhibit the formation of larger aggregates and increase the

proportion of dye in the monomolecular form.

Hence solubilisation is increased.

TIME OF DYEING

The production of level and well-penetrated dyeings is usually

favored by an increased time of dyeing, although prolonged dyeing
at boil sometimes results in the decomposition of direct dyes.
 AFTERTREATMENT OF DYEINGS WITH DIRECT DYES

 Aftertreatment is carried out to improve washing fastness

 Basic principle involved is increasing the dye’s molecular weight

 Adsorbed dye becomes insolublized & has low diffusion

coefficient

 Impact on hue and light fastness, greatly impede shade correction

and color matching.

 Aftertreatments are difficult and costly to carry out

 Replacements of direct dyes today reduce use of aftertreatment

Reactive dye

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AFTERTREATMENTS IN DIRECT DYEING

Metal complex formation

Aftertreatment with formaldehyde

Use of cationic fixatives

Based on resin crosslinkks

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 METAL COMPLEX FORMATION
Treatment with acidic copper sulphate solution for the formation
of a complex between copper and adsorbed dye

Complexation usually increases

the light fastness.

 Most dye–copper complex dyes are pre-metallized by the dye manufacturers

due to environmental concern .

 Release in the effluent of the small amounts of copper in unexhausted pre-

metallized direct dyes is now reaching the point of exceeding allowable limits.
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 FORMALDEHYDE TREATMENT

Based on formation of methylene bridge between adsorbed

direct dye molecules

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 TREATMENT WITH CATIONIC FIXATIVES
Cationic agents of relatively high molecular weight form water-
insoluble salt like molecule with anionic direct dye.

Precipitation of anionic dyes in the cotton with a cationic surfactant

or polymer in warm water Reduce the light fastness
The change in hue is only slight
RESIN TREATMENT
Based on addition of crosslinking agents used for easy care
finishing Decrease the light fastness and give a hue change.

Direct dyed cellulose is crosslinked using crosslinking agents

Surface dyes have less tendency of movement Amino resins

Wash fastness is improved due to strong anchoring effect 32
END

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