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Dyeing & Printing

Classification of Dyes,
Application of Dyes on Textile Materials,
Introduction to Different types of Dyeing
Machineries
Dyeing & Printing 2

Title of Contents

1.0. Introduction to Textile Dyeing - 03

2.0. Classification of Dyes - 05

3.0. Dyeing Process - 07

3.1. Dyeing Methods - 07

3.2. Comparison of Dyeing in Various Stages - 09

3.3. Special Dyeing Effects - 10

3.4. Application of Dyes on Textile Materials - 11

3.5. Direct Dyes - 11

3.6. Azoic Colors - 12

3.7. Reactive Dyes - 15

3.8. Vat Dyes - 20

3.9. Acid Dyes - 25

3.10. Basic Dyes - 28

3.11. Sulphur Dyes - 29

3.12. Disperse Dyes - 30

4.0. Introduction to Different Dyeing Machineries - 31

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1.0. Introduction to Textile Dyeing

Dyeing is the process of imparting colours to a textile material in loose fibre,


yarn, cloth or garment form by treatment with a dye.
Dyeing is also the process of coloring textile materials by immersing them in an
aqueous solution of dye, called dye liquor. Normally the dye liquor consists of dye, water
and an auxiliary. To improve the effectiveness of dyeing, heat is usually applied to the
dye liquor.

1.1. Color – Definition

Color or colour is the visual perceptual property corresponding in humans to the


categories called red, green, blue and others. Color derives from the spectrum of light
(distribution of light energy versus wavelength) interacting in the eye with the spectral
sensitivities of the light receptors. Color categories and physical specifications of color
are also associated with objects, materials, light sources, etc., based on their physical
properties such as light absorption, reflection, or emission spectra. By defining a color
space, colors can be identified numerically by their coordinates.

Because perception of color stems from the varying sensitivity of different types
of cone cells in the retina to different parts of the spectrum, colors may be defined and
quantified by the degree to which they stimulate these cells. These physical or
physiological quantifications of color, however, do not fully explain the psychophysical
perception of color appearance.

The science of color is sometimes called chromatics. It includes the perception of


color by the human eye and brain, the origin of color in materials, color theory in art, and
the physics of electromagnetic radiation in the visible range (that is, what we commonly
refer to simply as light).

1.2. Definition – Dye

By definition Dyes can be said to be coloured, ionizing and aromatic organic


compounds which shows an affinity towards the substrate to which it is being applied. It
is generally applied in a solution that is aqueous. Dyes may also require a mordant to
better the fastness of the dye on the material on which it is applied.
The dyes were obtained from animal, vegetable or mineral origin with no or very little
processing. By far the greatest source of dyes has been from the plant kingdom, notably
roots, berries, bark, leaves and wood, but only a few have ever been used on a
commercial scale.

1.3. Definition – Pigment

Pigment is the substance or powder that makes up the color of paint. Pigments
are either organic (derived from plant or animal sources, e.g. ivory black, indigo) or
inorganic (derived from salts or metallic oxides e.g. ocher, cobalt blue).
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Pigment is a substance that can absorb light and reflect some lights to show color
but it is water insoluble substances. Normally it is used for printing (with the presence of
binder) or mass-coloration of the synthetic fibers.

1.4. Theory of Dyeing

The general theory of dyeing explains the interaction between dye, fiber, water
and dye auxiliary. More specifically, it explains:
i. Force of repulsion which are developed between the dye molecules and water and
ii. Force of attraction which are developed between the dye molecules and fibres.
These forces are responsible for the dye molecules leaving the aqueous dye liquor
entering and attaching themselves to the polymers of the fibres

1.4.1. Dye Molecule

Dye molecules are organic molecules, which can be classified as:

1. Anionic – in which the color is caused by the anionic part of the dye molecule;
2. Cationic – in which the color is caused by the cationic part of the dye molecule;
3. Disperse – in which the color is caused by the whole molecule.

The first two dye molecule types are applied from an aqueous solution. The third
is applied from an aqueous dispersion.

A dye stuff is a substance which is capable of coloring a textile material in such a


manner that it associate closely with the fiber, that it is not removable by simple physical
means (e.g.: rubbing or mild deterging). It must be soluble in water, are capable of going
into solution by chemical means, whereby a highly dispersed condition may be regarded
as a form of solution

An essential feature of the dyeing process is that the dye molecule must be
capable of entering the fiber structure, the path for the dye molecules is provided by the
intermolecular spaces in the fiber and once the dye has entered the fiber structure it
becomes firmly attached to the surface of the molecules either by purely physical forces
(Secondary Valences) or by chemical combination. The former mode of attachment is
believed to be prevalent in the dyeing of cellulosic fibres, the latter mode in the dyeing of
protein fibres.

Acetate rayon and synthetic fibres resist penetration by the dye molecules, but
certain dyes are capable of forming a solid solution with the fibrous molecule; for dyeing
with other dyes, the synthetic fibres may be swollen with suitable agents.

Swelling of the fibers appears to play a large part in dyeing of all fibres, and is
principally affected by water (or solvents in the case of synthetics) and by raising the
temperature of the dye bath.

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1.4.2. The Dyeing Process

The dyeing process can thus be considered as taking place in three phases
(i) Attachment of the dye molecule to the surface of the fiber
(ii) Penetration into the intermolecular spaces as well as diffusion through the fiber &
(iii) Orientation (and fixation) along the long chain molecules.
Dyeing is governed by three factors, the dye, the fiber and the dye liquor. All the
three lead an independent assistance which influences the technique of dyeing. A dye
must be water soluble in order to dye textile materials. It may be soluble by nature of its
chemical interference.

The solution of the dye from which it is applied is called the „dye bath‟. A dye
may have direct „affinity‟ for a fiber (or vice versa) i.e., it is held by the fibre either
physically (absorption) or chemically (combination) as soon as the fiber is immersed in
the dye bath.

Accumulation of the dye in the fiber is a gradual process, the rate of such building
up being referred to as the „rate of dyeing‟.
1. This rate of dyeing is governed by the condition of the dye bath, namely
concentration of dye, temperature, and presence of electrolytes; it is proportional
to all three factors.
2. The rate of dyeing is also influenced by the „Material to liquor‟ which is
expressed by a fraction, e.g. 1:20, which means one part (by weight) of the textile
material dyed in twenty times its weight of dye bath.
3. The rate of dyeing decreases with increasing ratio of goods to liquor.

Dyeing is carried out to produce a certain „Shade‟ by which is meant a certain


color, difference in shade being due to different ‟Hue‟. A blue shade may, for instance,
have a greenish or a reddish hue.

The amount of dye needed for the production of a certain depth of shade is
expressed as a percentage of the weight of the material. A 1% dyeing represents a shade
produced by the coloring of 100 lbs. of material with one lb. of (commercial) dye under
well defined dyeing conditions. It is necessary to define these conditions because of their
influence on the „exhaustion‟ of the dye bath. Exhaustion determines that amount of dye
which is taken up the fiber or in directly, that amount which remains in the dye bath after
„equilibrium‟ between dye and fiber is reached, i.e., at that point where no further dyeing
takes place.

2.0. Classification of Dyes

Dyestuffs can be classified by many methods as follows:

y their ionic e.g. Cationic, anionic and non-ionic)


y their fiber dye abilities e.g. On cellulosic, protein, polyester, polyamide etc.)
y their names e.g. Acid, direct, disperse, reactive, basic etc.)
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y their chemical structures e.g. azo, anthraquinone, stilbene etc.)


y their origins e.g. Natural, synthetic)
y their colors e.g. Red, green, black etc.)

2.1. Classification of Dyes by their Names

Though several classifications were available classification of dyes by their names is the
widely used one.

COLOURING MATTER

DYES PIGMENTS

Ready made dyes Ingrain dyes

Azoic Oxidation Mineral

Water-soluble Water insoluble

Vat Sulphur Disperse

Direct Acid Basic Reactive

So the Colouring matters can be classified as pigments and dyes. Dyes may be of
readymade dyes and ingrain dyes.

Ready made dyes are dyes which are readily available in powder form, liquid form.
These ready made are available in both water soluble and water in soluble form.

Ingrain dyes are those which will not be available in ready made form, two or more
compounds are combined together in the dyeing process to obtain the color in the final
finished product.

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3.0. Dyeing Process

Dyeing is the process of imparting colors to a textile material through a dye


(colour). Dyes are obtained from flowers, nuts, berries and other forms of vegetables and
plants as well as from animal and mineral sources. These are known as natural dyes.

The other classes of dyes are known as synthetic dyes. These are based on a
particular type of chemical composition. Some of these dyes are- Acid (Anionic) dyes,
Basic (Cationic) dyes, Neutral- Premetalized dyes, sulfur dyes, vat dyes, reactive dyes,
pigment dyes etc.

3.1. Dyeing Methods

Colour is applied to fabric by different methods of dyeing for different types of


fiber and at different stages of the textile production process. Dyeing can be done during
any stage in the textile manufacturing process. Textiles may be dyed as fibre, as yarn, as
fabric, as garments, depending upon the type of the fabric or garment being produced.
These methods include direct dyeing; Stock dyeing; top dyeing; Yarn dyeing;
Piece dyeing; Solution pigmenting or dope dyeing; Garment dyeing etc. Of these Direct
dyeing and Yarn Dyeing methods are the most popular ones.

3.1.1. Direct Dyeing

When a dye is applied directly to the fabric without the aid of an affixing agent, it
is called direct dyeing. In this method the dyestuff is either fermented (for natural dye) or
chemically reduced (for synthetic vat and sulfur dyes) before being applied. The direct
dyes, which are largely used for dyeing cotton, are water soluble and can be applied
directly to the fiber from an aqueous solution. Most other classes of synthetic dye, other
than vat and sulfur dyes, are also applied in this way.

3.1.2. Stock Dyeing

Stock dyeing refers to the dyeing of the fibers, or stock, before it is spun in to
yarn. It is done by putting loose, unspun fibres in to large vats containing the dye bath,
which is then heated to the appropriate temperature required for the dye application and
dyeing process.

Stock dyeing is usually suitable for woolen materials when heather like color
effects are desired. Wool fibre dyed black, for example, might be blended and spun with
un-dyed (white) wool fibre to produce soft heather like shade of grey yarn.

Tweed fabrics with heather like color effects such as Harris Tweed are examples
of stock dyed material. Other examples include heather like colours in covert and woolen
cheviot.

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3.1.3. Top Dyeing

Top dyeing is also the dyeing of the fibre before it is spun in to yarn and serves
the same purpose as stock dyeing – that is, to produce soft, heather like color effects. The
term top refers to the fibres of wool from which the short fibres have been removed. Top
is thus selecting long fibres that are used to spin worsted yarn. The top in the form of
sliver is dyed and then blended with other colors of dyed top to produce desired heather
shades.

3.1.4. Yarn Dyeing

Yarn dyeing is the dyeing of the yarns before they have been woven or knitted
into fabrics. Yarn dyeing is used to create interesting checks, stripes and plaids with
different-colored yarns in the weaving process. In yarn dyeing, dyestuff penetrates the
fibers in the core of the yarn. There are many forms of yarn dyeing- Skein (Hank)
Dyeing, Package Dyeing, Warp-beam Dyeing, and Space Dyeing.

3.1.4.1. Skein (Hank) Dyeing

Skein dyeing consists of immersing large, loosely wound hanks (skeins) of yarn
into dye vats that are especially designed for this purpose. Soft, lofty yarns, such as hand
knitted yarns are usually skein dyed. Skein dyeing is the most costly yarn-dye method.

3.1.4.2. Package Dyeing

In package dyeing the yarn is wound on a small perforated spool or tube called a
package. Many spools fit into the dyeing machine in which the flow of the dye bath
alternates from the center to the outside, and then from the outside to the center of the
package. Package dyed yarns do not retain the softness and loftiness that skein-dyed
yarns do. They are however satisfactory and very widely used for most types of yarns that
are found in knitted and woven fabrics.

3.1.4.3. Warp Beam Dyeing

Beam dyeing is the much larger version of package dyeing. An entire warp beam is
wound on to a perforated cylinder, which is then placed in the beam dyeing machine,
where the flow of the dye bath alternate as in the package dyeing. Beam dyeing is more
economical than skein or package dyeing, but it is only used in the manufacture of woven
fabrics where an entire warp beam is dyed. Knitted fabrics, which are mostly produced
from the cones of the yarn, are not adaptable to beam dyeing.

3.1.5. Piece Dyeing

The dyeing of cloth after it is being woven or knitted is known as piece dyeing. It
is the most common method of dyeing used. The various methods used for this type of
dyeing include jet dyeing. Jig dyeing, pad dyeing and beam dyeing.
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3.1.6. Garment Dyeing

Garment dyeing is the dyeing of the completed garments. The types of apparel
that can be dyed are mostly non-tailored and simpler forms, such as sweaters, sweatshirts,
T-shirts, hosiery, and pantyhose. The effect on sizing, thread, zippers, trims and snaps
must be considered. Tailored items, such as suits or dresses, cannot be dyed as garments
because the difference in shrinkage of the various components and linings disort and
misshape the article.

Garment dyeing is done by placing a suitable number of garments (usually about


24 sweaters or the equivalent, depending on the weight) into large nylon net bag. The
garments are loosely packed. From 10 to 50 of the bags are placed in large tubs
containing the dye bath and kept agitated by a motor – driven paddle in the dye tub. The
machine is appropriately called a paddle dryer.

3.2. Comparison of Dyeing in various stages.

Stage of Features and Advantages Limitations and Disadvantages Typical


Dyeing Dyed
Fabrics
Stock and Fabrics have soft, heather Most costly dyeing method. Chevoit
Top like coloration. Easiest Dyeing long before season covert
dye penetration. begins carries the risk of fashion molten
changing. High percentage of tweed.
fibre loss from dyeing and later
in yarn spinning
Yarn Used for fabrics with Second most costly method. Chambray
stripes, checks, plaids, Dyeing before season begins gingham
and other multi colored carries the risk of fashion brocade
patterns. changing, but less than for stock jacquard
dyeing knits
Piece Least costly stage for Limited to solid colors Batiste
dyeing of fabrics. broadcloth
Adaptable to all fabrics- challis
woven and knitted. corduroy
Dyeing is close to satin.
fashion seasons; minimal
color risk
Garment Choice of colors closest Limited to garments of simple Hosiery
to fashion season. construction panty hose
Elimination of material sweaters t-
(yarn and fabric) waste shirts.
from prior processing.

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3.3. Special Dyeing Effects

Piece dyeing, as described previously, primarily produces a solid color throughout the
goods being dyed. It is possible, however, to create effects such as multi-colours or multi-
shades by any yarn-dye or piece-dye method.

3.3.1. Cross Dyeing

Cross dyeing is a type of dyeing in which a yarn, a fabric, or even a garment made
with two or more genetic fibres types having different dye affinities is dyed in a single
bath containing two different class of dyes. Each class of dye colors only one type of the
fibre. Two different colors can be dyed in one bath or either type of fibre may be dyed,
leaving the other one white.

If different fibres are blended in the same yarn, a stock-dyed effect can be
obtained. If yarns of one kind of fibre and yarns of another kind of fibres are used in the
warp direction, vertical stripes can be produced after dyeing. A plaid effect can be
produced by weaving yarns of different kinds of fibre both in warp and filling directions
and then dyeing the fabric in single bath with a mixture of two kinds of dyes. Whereas
certain fibre combination allow for one bath process, other fibre combinations may
require a two –step dyeing process to produce two colours.

Cross dyeing is the more economical and quicker way to produce the same effects
obtained by other methods. The effects achieved by expensive stock dyeing method can
be replicated easily by this cross dyeing method.

3.3.2. Union Dyeing

Union dyeing is same as like cross dyeing, except that instead of multi color
effects, one solid color is produced. The dyer accomplishes this by using two or more
classes of dye, each of the same color. For example, a fabric composed of rayon and
acetate can be dyed by a solid green color by using a direct dye for rayon and disperse
dye for acetate.

3.3.3. Tone –on Tone Effects

Tone on tone effect is also possible by using one dye bath. They are light and dark
shades of the same color in a fabric containing only one generic fibre – for example, deep
red and light red colors on the same piece dyed polyester fabric. The effect can be
produced by combining two different types of polyester in the same fabric. Both types are
capable of combining with the same dye class, but one fibre has strong affinity for dye
than the other. The fibre with the stronger affinity combines with greater quantity of dye,
becoming deeper in shade, and second fibre remains a lighter shade of the same color.

Tone on tone effects can only be achieved with the specific varieties of nylon,
polyester and acrylic fibres. These special properties are imparted during the manufacture
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of the fibre, and the fibres are marketed to textile producers as deep –dye types. In
addition nylon is produced in both deep-dye and ultra-deep-dye varieties, thus providing
the possibility for three-tone effects of the same color. The tone on tone effects is widely
used in the carpet industry for producing tweed-effect designs on piece dyed carpeting.

3.4. Applications of Dyes on the textile materials

Let us discuss the application of following dyes in the textile materials


Direct Dyes
Azoic Dyes
Reactive Dyes
Vat Dye
Acid Dyes
Basic Dyes
Sulphur Dyes
Disperse Dyes

3.5. Direct Dyes

These colors are known as substantive dyes or Salt dyestuffs or even simply
cotton colors. The colors are well known for its use in dyeing cellulose fibres like cotton,
viscose rayon, animal fibres such as wool and silk. Selected substantive dyes can be used
to give solid shades on wool and cotton mixtures. Direct dyes are also called Substantive
dyes because of their excellent substantively for cellulose textile materials like cotton and
viscose rayon.

This class of dyes derives its name from its property of having direct affinity for
cellulosic fibres when applied from an aqueous solution.

3.5.1. Properties of Direct Dyes

1. Direct dyes are readily soluble in water.


2. Some of the dyes need a little amount of soda ash (Sodium Carbonate) for
complete dissolve them in water.
3. Direct dyes are used for dyeing cotton, viscose rayon, wool and silk fibres.
4. If common salt or Glauber‟s salt (Sodium sulphate) is added to the dye during
dyeing, more dye is taken up by the fiber i.e. the dye bath gets exhausted to a
greater extent. Hence these salts are exhausting agents for direct while dyeing or
cotton.
5. Direct dyes have poor washing fastness and poor light fastness. These fastness
properties can be improved by certain after-treatments. If a piece of cotton dyed
with a direct dye is boiled with soap and water which contains also a small piece
of un-dyed cotton, the latter generally becomes stained with the dye from former.
This is known as bleeding.

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6. All direct dyestuffs combine with basic dyes to give compounds which are less
soluble that the original direct dyes. The process of dyeing the direct dye on
cotton with basic color is known as topping.

3.5.2. Application of Direct Dyes to Cotton/Viscose

The dye bath is usually made up with twenty items as much water as the material.
Take for example, for 100 kilograms of cotton fabric 2,000 liters of water can be taken.
For dyeing only soft water should be used.

From 0.5 to 5% of the dyestuff according to the shade required to be taken. The
dyestuff is pasted with cold water and sufficient boiling water is then added, with
constant stirring to bring it into solution. It is then added to the dye liquor through a
strainer.

Some direct dyestuffs give better results in a slightly alkaline bath. In fact it is
advantageous in most cases, since it renders the dyestuff more completely soluble in the
dye bath. From 0.5 to 2% of Sodium carbonate may be used.

The cotton material is wetted out in water and entered into the dye bath at 41ºC to
50 ºC and the liquid is raised to the boil over a period of 30 to 40 minutes and then
common salt or Glauber‟s salt is added to the dye bath for the complete exhaustion of the
dye bath. These salts are exhausting agents for direct dyes while dyeing on cotton. The
dyeing is continued at the boil for ¾ to 1 hour. At the end of the dyeing the material is
rinsed in cold water and dried without soaping.

Direct dyes have poor washing fastness and poor light fastness. However, these
fastness properties can be improved by certain after treatments.

3.5.3. After Treatments

A dye fixing treatment may give in a fresh bath containing a cationic dye-fixing
agent before drying; this process improves the wet fastness of the dyed goods.

Fastness properties of Direct dyed goods - Both washing and light fastness of
most of the direct dyed goods are generally poor; to improve the fastness properties after
– treatments may be given improve the fastness

3.6. Azoic Dyes

Azoic dyes are so called because their molecules contain azo group. (N=N) Azoic
dyes are also called naphtha dyes or developed colors.
The fibres most readily colored with azoic dyes are the man-made and natural
cellulose fibres, e.g. Viscose, Cotton etc.

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3.6.1. Dyeing Cotton with Azoic Dyes

Coloring of textile materials with azoic dyes involved the reaction within the fibre
polymer system of the two components, which constitute the azoic dye. These two
components are the naphtha or coupling component, and the base or di-azo components.

The application of azoic colors involved two steps – naptholation (dyeing with
naphtha) and development (coupling of diazotized base with naphtha).

The Application of Azoic colors involves the following steps.


Preparation of Naphtha solution.
Dyeing of cotton yarn with Naphtha solution.
Preparation of Diazotized base solution.
After treatment of the dyed cotton material.

3.6.1.1. Preparation of Naphthol Solution

Naphtha‟s are insoluble in water. They can be dissolved in water by coveting


them into sodium compounds which are soluble in water. For this caustic soda i.e.
sodium hydroxide (NaoH) is used.

The Naphtha is pasted with its own weight of turkey – red oil and little hot water
avoiding any lump formation. The required amount of boiling water is then added to the
paste, followed by the required amount sodium hydroxide (NaoH) solution is added. The
mixture is boiled till a clear solution is obtained. Cool the solution to 50ºC by adding
about some quantity of cold water.

3.6.1.2. Dyeing of Cotton with Naphthol Solution

The well scoured wet yarn is entered in the cold Naphtha bath are kept turned for
several times. In some cases the addition of common salt or Glauber‟s salt increases the
absorption of the naphtha solution. The impregnated material must not be touched with
wet hand or exposed to direct sunlight or brought into contact with metals.

In most cases the amount of Naphtha which is absorbed decreases as temperature


raises and the operation is therefore carried out at 25º - 30ºC for 20 – 30 minutes. After
impregnation the goods should be hydro extracted or squeezed thoroughly, to avoid
carrying over retained liquor into the coupling bath where it would cause surface
deposition of the pigment cause the poor rubbing fastness.

The sodium salts of the coupling components are usually somewhat unstable
towards exposure to air, especially when in a wet state. If the impregnated goods lie
about for any period the decomposition will not occur uniformly and the final result will
be patchy. Therefore the naphthalene material should be developed without any delay.

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3.6.1.3. Preparation of Diazotized Base Solution

1) The base is insoluble in water. It should be converted into water soluble salt
(hydro chloride of the base) using concentrated hydrochloric acid.
2) The reaction of hydro chloride of the base with Nitrous acid usually at low
temperatures (Oº - 5ºc) for 20 – 30 minutes is called the Diazotization of the Base. This is
carried out by adding Sodium Nitrite to a solution of hydro chloride of the base in the
presence of excess of HCL.acid. Now the base is converted into diazonium chloride
(diazotized Base).

The base is pasted with a little amount of con. Hcl. Acid and a few drops of cold
water the mixture is then added cold water to dissolve the paste. The mixture is stirred till
a clear solution obtained. In some cases the mixture is to be heated or even boiled
complete conversion of Base into salt. The solution is cooled to 18º - 20 ºC by adding
Crushed ice directly into the solution when the required temperature is obtained the pre-
dissolved sodium Nitrite is added with constant stirring. Allow the solution for 20 – 30
minutes for the reaction to go to completion. Now the diazonium chloride which is
generally highly soluble in water is formed and a very clear solution is obtained. Now the
pH of the solution is too low. The reaction between diazonium chloride and Naphtha
(Coupling or developing) takes place quickly over the pH range of 5 to 6. The pH of the
solution is therefore raised by adding Sodium acetate. Sodium acetate converts the free
Hcl. Acid into acetic acid, after which the pH of the solution become in the range of 5 –
6. Coupling will also be retarded if the liquor becomes alkaline, too high a pH and this
can occur easily on account of sodium hydroxide (NaoH) which may be left in the cotton
after it has been impregnated with Naphtha solution. Excess of alkali can be neutralized
by adding acetic acid or sodium bicarbonate or Aluminum Sulphate. The developing both
should be maintained the pH of 5 – 6 and temperature should be kept below 20ºC in the
above manner. Now the base solution is ready for dyeing.

3.6.1.4. Dyeing of Naphthalene material with the Base Solution

The naphthalene material is entered the diazotized Base solution. It is turned


several times and kept for 20 – 30 minutes. This is called coupling (Or) developing
process. During coupling the Azoic color is formed on the cotton material. Through the
coupling process the pH should maintain 5-6 and temperature should below 20 ºC.

3.6.1.5. After treatment

After the dyeing the dyed material are rinsed in the cold water bath to which a
little Hcl acid is preferably added and are then treated in a soaping bath at boil for 30
minutes to remove the loosely combined dye stuffs.

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3.6.2. Dyeing of Viscose Rayon with Azoic Dyes

Azoic colors have a much greater affinity for Viscose rayon than for cotton. The
method of application is as follow,

Preparation of Naphtha solution


Dyeing of Viscose rayon with Naphtha solution.
Preparation of diazotized Base solution
Dyeing of Naphthalene mat. In the Base solution.
After treatment of Azoic Dyed Viscose Rayon mat.

Note: The procedure for dyeing viscose rayon with azoic dyes is the same as that of
cotton.

3.6.3. Properties of Azoic Dyes

1. It is insoluble in water.
2. It is not a readymade dye but is formed in the fibre substance by the dyer from
Components usually referred to as Naphtha and Base.
3. The dyed and printed azoic colors have very good to excellent light fastness.
4. The dyed azoic colors have good washing fastness.
5. Textile materials dyed with azoic dyes suffer from poor Rubbing – fastness. This
occurs because of the formation of the insoluble azoic dye on the surface of the
fibre which is not removed during the final stage of dyeing, which is not removed
during the final stage of dyeing. This rinsing stage is referred to as Soaping – off
and involves a through treatment of the dyed textile material with a detergent. If
all stages of azoic dyeing are carefully controlled and followed by thorough
soaping – off, poor rub-fastness is unlikely to occur.

3.7. Reactive Dyes

Reactive dyes are so called because their molecules react chemically with the fire
polymers of some fibres to form a covalent bond between the dye molecule and fibre
polymer.
The fibres most readily colored with reactive dyes are cellulose fibres, wool, silk
and nylon.
Reactive dyes are also called as Procion dyes

When direct dyestuff is applied to cotton and to viscose rayon the process is one
of Physical absorption there is no covalent union between dye and fibres.

DH + H O – cell DH……..HO –Cell


Direct dye cellulose dyed (not reactively) Cellulose

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Direct dye, DH, applied to cellulose, there is no chemical reaction and no covalent
union, there is, as indicated by the dotted bond, hydrogen bonding and attachment
thorough Vander walls forces. The nature of the union between bye and fibre, commonly
referred to absorption, may be difficult to analyze precisely; it may have been
mechanical, physical or chemical sorption, hydrogen bonding ands so no, but it was
certainly not covalent bond.

Drcl + HO - cell DH O cell + HCl

Reactive Dye Cellulose reactively (covalently) Dyed cellulose

With the old direct dye DH we obtained dyed rayon DH …..HO-cell. With the
reactive dye DRcl we have obtained reactively dyed rayon Dr – O cell. All that we have
gained is covalent union (i.e. Chemical combination) between dye and fibre. As a result
of this, fastness to washing and wet processing generally should be much better and so in
reactively dyed cellulose DR-O Cell, the dye is part of the fibre; it is impossible to wash
it out or to extract it even with such powerful agents as aqueous pyridine.

The porcine dyes, on account of the sulphonic acid groups in their molecules, are
readily soluble in water. In neutral solution, they have substantively towards cellulose
similar to that of very low affinity direct dyes, a wet-fastness of a low order, and they
exhaust better in the presence of an electrolyte (salt). In the neutral solution physical
adsorption and possibly some hydrogen bonding take place, but there is no formation of
covalent bonds until alkali has been added.

The application of reactive dyes to cotton materials involves two distinct steps

1) Dyeing with the dye in the presence of common salt to effect as much exhaustion
as possible and
2) Chemically reaching the dye with the fibre (fixation) in the presence of an alkali
like soda ash. In the first stage of dyeing, the reactive dye resembles like direct
dyes in that its exhaustion can be brought about by adding common salt or
Glauber‟s salt. However, it has much lower affinity to cotton than direct dyes.

During the second stage of application (fixation) the alkali is added to the dye
bath, when the dye reacts with the fibres, however the dye also reacts with water (only
after the addition of alkali) and when this rakes place, the dye gets deactivated
(hydrolyzed) and then it cannot react with the cotton fibre. In the dyeing and fixing of
reactive dyes, 5 to 30% of the dye used for dyeing and the remaining is deactivated and
hence this is a waste. The deactivated dye has some affinity for cotton and hence is
absorbed and retained by cotton. Because of the lower affinity of the deactivated dye
(compared to direct dyes on cotton) the washing fastness of this form of the dye present,
on cotton is very poor and hence it gets washed out progressively during the washing of
the garments made from such fabrics. Therefore, as part of the dyeing process the fabrics
Dyes, Theory of Dyeing, Classification of Dyes and its application
Dyeing & Printing 17

are boiled with a soap solution after the fixation step, when most of the deactivated dye is
removed from the dyed fabric. The other form of the dye present in the fibre in a
chemically reacted form is not removed during the soaping step, since it is firmly bound
to the fibre by a covalent bond.

3.7.1. Cold Brand & Hot Brand Reactive Dyes

The reactivity of these dyes is due to the chlorine atoms attached to the triazine
ring. When two chlorine atoms are present in the dye molecule are called Dichloride
Procions. Dichloride procions are referred to as M-type procions and their characteristic
is that they will combine with alkaline cellulose at room temperature (20ºC to 30ºC) and
hence they are called cold brand reactive dyes when only one chlorine atom is present in
the dyestuff molecule, the reactivity of the dye decreases considerably and the dyeing has
to be carried out at a higher temperature (65ºC to 80ºC). Hence these dyes are called hot
brand reactive dyes. Mono chloride procions are referred to as „H‟ type procions.
Normally „M‟ Brands are suitable for dyeing and H brands are suitable for printing.

The instability of the solutions of the cold-dyeing procion colors was a serious
disadvantage in their application to textile printing. The stock solution for printing must
be kept and used for several hours. The reactive dyes having only one chlorine atom in
their molecule are less reactive. Their aqueous, therefore, are more stable and very
suitable for printing.

3.7.2. Types of Reactive Dyes

1. Cold brand reactive dye - „M‟ brand


2. Hot brand reactive dye - „H‟ brand (or „X‟ brand)
3. High exhaust reactive dye - „HE‟ brand
4. High exhaust reactive dye - „ME‟ brand
5. Vinyl Sulphone reactive dye - for dyeing and printing
6. Low salt reactive dye - LS dyes

3.7.3. Properties of Reactive Dyes

1. The Procion dyes, on account of the sulphuric acid groups in their molecule, are
readily soluble in water.
2. These dyes, unlike any other class of dye stuffs, react and combine chemically
(covalently) with cellulose and this leading to excellent wash-fastness.
3. These dyes give very bright shades such as orange, pink, magenta etc, which were
not possible with other class of dyes.
4. They do not react with water nearly as readily as with cellulosic hydroxyl in
alkaline conditions, so that they can be applied from an aqueous solution.
5. Reactivity of the dyestuffs can be reduced when desirable by blocking one of the
reactive chlorine atoms giving H-type Procions.

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6. Procion dyes are dyes with small molecules; their molecules do not have to be
very long as those of direct dyes to match the distance between absorption sites on
the fibre. Short molecules bring two advantages (a) Clarity and brightness of hue
and (b) easy penetration and therefore good leveling.
7. Because there is some, even although not very much reaction between procion
dyestuffs and water it is very important to wash the dyes fibre thoroughly clean
and free from the reaction product with water.
8. Textile materials colored with reactive dyes have very good light fastness.
9. Textile materials colored with reactive dyed has very good wash-fastness.
10. Textile materials which are colored with reactive dyes have to be thoroughly
rinsed and scoured. Reactive dyes can react with the hydroxyl groups of the water
molecule to produce dye molecules to produce dye molecules with poor
substantively for the fiber. In fact it is these molecules which have to be removed
by a washing-off process, involving soaping and rinsing. If these molecules of dye
are not removed, poor rub-fastness may result.
11. The formation of the covalent bond between dye and fiber occurs under alkaline
conditions. The presence of acids may reverse this process. Perspiration and
atmospheric pollution which are both slightly acid may affect textile materials
colored with reactive dyes and result in some fading.

3.7.4. Application of Cold Brand Reactive Dyes on Cotton

(Dichlorotriazinyl Reactive dyes (or) Procion – M brand)

3.7.4.1. Preparation of Dye Solution

The dyestuff is dissolved by making them into paste with cold water, followed by
dilution with more water, the temperature of which must not exceed 50ºC, A stock
solution will not remain stable for more than about 4 hours, after which it will begin to
lose strength due to hydrolysis.

3.7.4.2. Dyeing

The goods are loaded into the machine and 30 and 60 parts per 1000 of common
salt are added, the quantity varying according to the depth of the shade. The liquor is then
raised to the required temperature either 40ºC or 60ºC and the pre dissolved dye is added
in the machine is then allowed to run for 20 to 30 minutes and the necessary amount of
Soda ash is added over a period of 10 to 30 minutes.

Dyeing is continued for further 20 to 40 minutes after which the goods are rinsed
to remove the salt and the alkali, and they are then washed off at the boil for 15 to 30
minutes to extract any of the products of hydrolyzed dye.

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Considerable importance must be attached to the final washing of goods dyed


with procion colors. The exhaustion is often not good and much dyestuff will be in
retained in the liquor, but of greater significance is the fact that cellulose has some
affinity for the hydrolyzed dye which is having lost its chlorine atoms, has not entered
into chemical combination. The load is first rinsed thoroughly in as great a volume of
cold water as the machine permits. The goods should then be rinsed in hot water nearly at
the boil, after which they are soured at the boil, for 15 to 30 minutes with a synthetic
detergent or soap and finally rinsed, first in hot and then in cold water.

3.7.5. APPLICATION OF HOT BRAND DYES ON COTTON

(MONOCHLOROTRIAZINYL, REACTIVE DYES (OR) PROCION + H brand)

The mono chlorotriazinyl dyes or hot brand reactive dyes are less reactive. Their
aqueous solutions are more stable but they do not react with cellulose so readily and the
temperature of dyeing must be increased to 60ºC to 70ºC and in some cases, as high as
90ºC to 95ºC.

The dyestuffs are dissolved by making them into a paste with cold water,
followed by dilution with more water.

The dye bath is made by dissolving sufficient common salt to give a concentration
of 40 to 80 parts per 1000 according to the depth of the shade, the goods already having
been entered. The temperature is brought up to 40ºC and the machine is run for five to ten
minutes in order that the fabric can be uniformly impregnated. The pre dissolved dye is
then added in two portions at five minute intervals followed by the alkali which should be
20 parts per 1000 of soda ash. The alkali should be added in two portions at five minute
intervals and the temperature then raised to between 60 to 90ºC according to that which is
recommended for the dye selected. Dyeing is continued for a period of 20 to 40 minutes
and then continued for 30 to 60 minutes when soda ash (alkali) is used. After dyeing, the
materials must be rinsed and soap boiled to remove hydrolyzed and unfixed dye.

3.7.5.1. After treatment

Treat the dyed material with 1 to 2 g/l of neutral soap at boil for 15
minutes and wash it.
Treat the soaped material with 2 to 3 g/l of cationic dye fixing agent at
40ºC for 20 to 30 minutes and dry it.

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3.8. Vat Dyes

The name Vat was derived from the large wooden vessel from which the Vat dyes
were first applied. Vat dyes provide textile materials with the best color fastness of all the
dyes in common use.

The fiber most readily colored with Vat dyes are the natural and man made
cellulose fibres of cotton, viscose rayon.

3.8.1. Properties of Vat Dyes

1. Vat dyes are insoluble in water and hence cannot be used directly for dyeing but
when treated with the reducing agent, they leuco compounds are soluble in
alkaline solutions in which cotton and other textile fibres have a considerable
affinity on them. When cotton containing these, is exposed to air, the leuco
compounds are oxidized and the insoluble coloring matters are produced on the
fibres.
2. Vat dyes fabrics have excellent light fastness.
3. Vat dyes fabrics have excellent washing fastness. This is attributed to the large vat
dye molecule as well as its aqueous insolubility. The large vat dye molecules is
trapped with the polymer system of the fibre, because of its size and aqueous
insolubility and is absorbed with in the fibre polymer system by Vander wail‟s
forces.
4. Vat dyes have always been very expensive compares with other dye classes.
5. Vat dyes are mainly used for coloring of cellulose fibres, but these dyes dyed at
low temperature and with small amount of alkali for dyeing wool and silk. Vat
dyes being insoluble in water cannot be directly applied to textile materials. They
have to be converted into water soluble form having affinity for textile fibres such
as cellulose fibres.

This conversion is usually brought about in two steps:

1. Reduction of the dye into the weakly acidic leuco vat form and
2. Salt formation by neutralizing these acidic leuco vat dyes by sodium hydroxide to
give a water-soluble product.

Since the second the step results in the formation of water-soluble sodium salt of
leuco vat dye, it may be called as the solubilizing step.

Reduction followed by solubilizing is called the vatting of the dye. For this
purpose sodium hydrosulphite, (Na2S2O4) (Usually called “hydrous”) is used as the
reducing agent and sodium hydroxide (NaOH) as the solubilizing (Neutralizing) agent.

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The different steps involve in the vatting of the dye are shown below:

Vat dye, Reduced Vat Sodium


Insoluble in Dye or Leuco salt of the
water and vat Dye. Also Leuco
soluble in called Vat dye.
caustic soda acid which is Soluble in
Reducing Solubilizing (NaoH)
solution insoluble in water
(Na2S2O4 Water, but
Soluble in
NAOH
solution

3.8.2. Classification of VAT dyes

Vat dyes are classified based on chemical constitution of the dyes or based on the
method of application.

Based on the chemical constitution, vat dyes are divided into two main classes

(1) Indigoid vat dye. & (2) Anthraquinone vat dye.

3.8.2.1. Indigoid Vat Dye

The indigoids are usually derivatives of indigo tin. The indigoids include natural
and synthetic Indigo and substituted Indigoes. These are characterized by forming pale
yellow leuco compounds which dissolve in week solutions of sodium hydroxide (NaoH).

The leuco compounds are oxidized readily when exposed to air. They are used in
neural or slightly alkaline bath and are suitable both for animal and vegetables fibres.
These Indigoid colors sublime when heated and are soluble in boiling pyridine.

3.8.2.2. Anthraquinone Vat Dyes

The Anthraquinone vat dyes are derived basically from Anthraquinone. The
Anthraquinone vat dyes give colored leuco compounds which are soluble only in Strong
alkaline solution and therefore not suitable for animal fibres or protein fibres. The
dyestuffs do not (with few exceptions) sublime when heated and are often insoluble in
boiling pyridine.

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3.8.3. Principles of application of Vat Dyes

Generally, the application of vat dyes to textile materials involves four distinct
steps.

a) Vatting in which the insoluble commercial dye is reduced and solidities


(vatted) by using Sodium hydrosulphite (hydrose) and sodium hydroxide
(NaoH).

b) Dyeing, in which the soluble sodium salt of the leuco vat dye is absorbed by
the textile material from an alkaline reducing medium in the presence of either
a retarding agent or an exhausting agent depending on the rate of dyeing.

c) Oxidation, in which the soluble form of the dye absorbed by the fibre, is
reconverted into the original insoluble dye by atmospheric oxygen (Airing) or
by the use of “chemical oxidation.” (i.e. involving the use of a chemical like
sodium per borate or potassium dichromate or Hydrogen per oxide).

d) After treatment, Soaping – off, in which the dyed material is subjected to a


treatment either boiling soap or other detergent solution in order to get the
proper tone by way of aggregation of smaller dye particles into bigger ones
and also to get the optimum fastness, especially rubbing fastness by removing
the surface deposited dye particles.

3.8.4. Application of Vat Dyes on Cotton

3.8.4.1. Preparation of leuco Vat dye solution

The Vat dyestuff powder is taken in a separate vessel and made into a paste with
Turkey red oil (the some weight of dyestuff to be taken) and add some hot water (50º -
60ºC). The caustic soda is first added and then sodium hydro sulphate is added, and
allows standing for 10-20 minutes with occasional stirring, the complete vatting taking
place. In above 10-20 minutes the dyestuff will be reduced completely and going to
solution. This can be seen by the clearness of the solution and characteristics of the vat
color. The vatting stage temporarily alters the original color of the dye (Reduced color).

3.8.4.2. Dyeing

The required water for dyeing is taken in the dye bath and it is maintain at proper
temperature (50º- 60 ºC) the reducing and dyeing temperatures vary from dyestuffs to
dyestuff. The vatted dye solution may than be added to the dye bath containing the
required amount of caustic soda sodium hydro sulphate, kept at recommended
temperature.

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The well scoured wet yarn is entered in the dye bath and turned several times, so
that the affinity of the color may be uniform. The yarn is then kept completely immersed
under the dye liquor and the dyeing is continued for one hour. The yarn is turned from
time to time… Care should be taken to keep the bath at required temperature and also to
keep the yarn thoroughly immersed under the liquor.

The exhaustion agents or retarding agents are added to the dye bath depending
upon the dyestuffs taken, during the entire dyeing period. Excess quantities of both
sodium hydroxide (NaoH) and sodium hydro sulphate (Na2s2O4) should be present in the
dye bath in order to keep the dye in the soluble form. At the end of the dyeing the partly
or completely exhausted dye bath must be kept in a distinctly reduced condition;
otherwise oxidation of the residual vatted dye takes place in the dye bath itself leading to
the appearance of turbidity. This is ensured by adding sufficient sodium hydro sulphate.
The dyed goods may then be removed from the dye bath and excess liquor which
contains the unexhausted vat dye, sodium hydroxide, sodium hydro sulphate is removed
as for as possible from the goods.

The dyed goods are rinsed with cold water and then subjected to an oxidation
treatment by exposure to atmospheric oxygen. This is called “air oxidation” or “airing”
but the oxidation may be accelerated by using stronger oxidizing agent such as sodium
per borate or hydrogen peroxide or sodium dichromate in the presence of acetic acid.
This process is usually referred to as chemical oxidation.

During the oxidation step the sodium salt of leuco vat dye absorbed by the fibre is
oxidized and converted into insoluble dye in the fibre. At the same time the vatted dye
contained in the residual liquor in the goods being dyed also gets converted into the
insoluble form which is loosely deposited on the fibre surface. This loosely deposited dye
on the surface of the fiber has to be removed for achieving optimum fastness properties
especially rubbing and washing fastness properties. This is achieved by soaping process.
The dyed material is treated in hot soap solution or a synthetic detergent solution for 15 –
30 minutes. After the soaping treatment the dyed goods should be rinsed thoroughly and
finally the dyed material is dried.

Important manufacturers of vat dyes in India are Indian Dyestuff Industries


(I.D.I) and ATIC Industries which market them under the trade names of NAVINON
and NOVATIC respectively.

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3.8.5. SOLUBILISED VAT DYES (INDIGOSOLS)

It is realized that the vatting process requires great care. To simplify the
application, solubilized vat dyes were developed.

Solubilized forms of Vat dyes are the leuco ester part of the dye molecule that is
responsible for the aqueous solubility of vat dyes. This has made vat dyes easier to handle
and results in more level dyeing.

3.8.5.1. Properties of Solubilized Vat Dyes:

1. Soluble in Water,
2. Vatting operation is not necessary and hence can be applied directly in the bath.
3. Solubilised vat dye have less affinity for the fibres and they exhausted by addition
of salt.
4. Suitable for light and medium depths.
5. Because of their low affinity, they are usually applied by padding process,
followed by a developing bath (an oxidizing treatment).
6. Indigo sols process a good coverage and leveling properties.

Soluble vat dyes are mainly applied to viscose rayon, cotton, wool, and silk
fabrics.
The solubilized leuco compounds are known as the Indigo sols. Another range
called the Solidness is prepared mainly from anothroquine vat dyes. Their application is
comparatively simple. Cellulosic fibres are dyed in neutral dye liquor and slightly acid
baths are used for protein fibres. They exhaust well at 20º to 40ºC although there are
some requiring temperatures ranging from 60º to 80ºC. Their affinity for cellulose is not
great and high percentages of electoral are often necessary and for this reason they have
only found favor in dyeing pale shades where color cost is not so important.

The general method of application is to dissolve the dye in hot but not boiling
water and added it to the dye liquor through a strainer, together with the required amount
of electrolyte. The goods are entered and the temperature is raised to that at which
maximum affinity is developed, which varies from one dye to another. The goods are
dyed at the appropriate for a period of 30 minutes.

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3.9. Acid Dyes

The Acid dye stuff is so called mainly due to two reasons. In the first place these
classes of dyestuff were applied in a bath containing mineral or organic acids like
sulphuric, acetic or formic acid and secondly most of them are sodium salts of organics
acids.

3.9.1. Properties of Acid Dyes:

1. Acid dyestuff is soluble in water.


2. These dyes are easily applied on wool, silk and nylon fibres,
3. These dyes are generally applied in the presence of acids like sulphuric, acetic or
formic acid.
4. They are in much case soluble in alcohol.
5. When acid dyestuffs are treated with a reducing agent they are generally
decolorized.
6. They are usually combined with basic dyes.
7. The dyed acid colors have good light fastness and moderate washing fastness.
And leveling characteristics:

3.9.2. Classification of Acid Dyes

Acid dyes are divided into three Groups according to the leveling characteristics

3.9.2.1. Acid dyes with Good leveling characteristics

This type of acid dye is responsible for their good leveling characteristics. As the
dye molecules have less attraction for the fibre they will migrate only slowly into the
polymer systems of wool or nylon fibres. However to obtain sufficient substantive and to
ensure, adequate exhausting agent (sulphuric acid) is added to the dye liquor, their lack of
substantive is evidence by their poor wash fastness. However the light fastness is very
good to excellent.

3.9.2.2. Acid dyes with average leveling characteristics

The moderate substantive of this type of acid dye is responsible for average
leveling characteristics. To obtain sufficient substantive and to and ensure it, adequate
exhausting agent, a week acid (Acetic acid or Formic acid) is added to the dye both. The
washing fastness of these dyes is fair, whilst their light – fastness is good to very good.

3.9.2.3. Acid dyes with poor leveling characteristics

These dyes are also known as fast acid dyes, and milling dyes or Natural dyeing
acid dyeing acid dyes. They have the best substantive of all the acid dyes, but have

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relatively poor leveling characteristics. Unless care is taken during, their relatively good
substantive for the fibre may result in too rapid uptake and consequently unleveled
dyeing

The excellent substantive of these dyes require neutral bath in order to obtain
slower exhaustion and more level dyeing. The wash fastnesses of these dyes are good to
very good, while their light fastness is fair to good. The better wash-fastness, compared
with the other two type of acid dyes, is due to the greater number of sodium sulphate
groups.

3.9.3. Application of acid dyes on wool:

The application of acid dyes to protein fibers results in an ionic or salt link
between the dye molecule and the fibre polymer. The point of the fibre polymer at which
the dye is attached is termed the dye site. In wool, the dye sites are of many amino group
of the fibre. Under dyeing conditions, the amino group becomes positively charged and
attracts the negatively charged dye anion.

There are a large number of amino groups are present in the wool fibre. As a
guide, there are approximately twenty times as many amino groups on wool as on nylon
and five times as many amino groups on wool as on silk. Dark shades can be readily be
obtained on wool because of the highly amorphous nature of the fibre, which results in
relatively easy penetration of the fibre polymer by the dye molecule and because of the
presence of minor groups.

3.9.3.1. Preparation of dye solution

The acid dyes are easy to dissolve, but care is necessary to avoid the
possibility of a dissolved particular becoming deposited on the goods. The requisite
amount of dyestuff is made into a smooth paste, preferably with a small amount of an
anionic or non ionic wetting agent, and sufficient boiling water is added to dissolve it
completely. It is advisable to strain the dye solution before adding it to the dye bath.

3.9.4. Method of dyeing with acid dyes on NYLON

The dyeing properties of acid dyes with regard to nylon and wool are
similar. The shades are very similar to the corresponding colors on wool, but the
saturation point is lower with nylon. When the pH of the dye solution is 2 or lower, nylon
has greatly increased affinity for acid dyes. In practice, dyeing cannot be carried out in
the pH region of 2 to 2.5 because the degradation of the nylon would be excessive.

Acid dyes requiring strong acid are applied from a dye liquor containing 3 to 5%
of formic acid. Sulphuric acid should not be used because it can cause degradation of the

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nylon, and the addition of Glauber‟s salt is omitted because it has no beneficial effect.
Non-ionic leveling agent, either alone or mixed with cationic products, are used. The
goods are entered cold and the dye bath is brought to the boil and dyeing continued at this
temperature for ¾ to 1 hour. With these acid dyes exhaustion takes place well with
weaker acid, 1 to 3% acetic acid (80%), may be substituted for the formic acid or,
alternatively, 1 to 3% of ammonium acetate may be used.

The application of acid dyes to nylon also results in ionic bonds or salt links
between the dye molecules and the polymer. The point at which the ionic is formed is the
terminal amino groups of nylon. The greater crystalline fibre structure of nylon compared
with wool as well as the relatively lower number of amino groups means that dark shades
on nylon cannot be obtained with acid dyes.

3.9.5. Stripping / leveling uneven Dyeing of Acid Dyes

a) With the molecularly – dispersed acid dyes, on account of their good


migrating properties, continued boiling in the same liquor is often effective. It
must, how ever be borne in mind that wool felts if it so boiled form too long.

b) Boiling in fresh liquor with 20% of Glauber‟s salt will strip some of the color,
and this can be exhausted again by cautious addition of acid or, preferably,
ammonium salt.

c) If treatment with Glauber‟s salt is not successful, more of the color can be
stripped by boiling with 0.5% ammonia, or in liquor containing 2% pyridine.

d) Another method is to boil the unevenly-dyed material with 3 to 5% of a


cationic, non-ionic mixture such as Tine gal W or Lyogen SMK. When
sufficient color has been removed by any of these compounds the wool is
rinsed and redeye.

3.9.6. Application of Acid dyes on silk

Although silk has an affinity for acid dyes the colors tend to be less fast than on
wool. Silk will exert its affinity for acid dyes at lower temperature than is the case with
wool, and dyeing is usually commenced at 40ºC and the temperature is not allowed to
rise above 85ºC. Glauber‟s salt is not suitable for use with silk as it diminishes its luster.
Sulfuric acid damages the silk. Acid used should be acetic acid. While using boiled off
liquor the bath must be neutral or only faintly acidic.

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3.10. Basic Dyes

Basic dyes are called so since they are salts of organic bases. Basic dyes are also
called cationic dyes because in solution the basic dye molecule ionizes, causing its
colored component to become an action of positively charged radical. Basic dyes are used
for dyeing wool, silk, and acrylic and mod-acrylic fibres.

3.10.1. Properties of Basic Dyes

1. The outstanding characteristics of the basic are brilliance and intensity of their
colors.
2. The bright colors achieved from basic dyes do not usually occur with other dye
classes.
3. Many of the basic dyes are sparingly soluble in water.
4. The addition of glacial acetic acid helps to dissolve the basic dye quickly in water.
5. Basic dyes are readily soluble in alcohol or mentholated spirit.
6. The basic dyes are poor fastness to light and vary with regard to washing fastness
from poor to moderate.
7. An important property of basic dyes is that they will combine with tannic acid to
form an insoluble compound provided mineral acid is absent.
8. The wet fastness of the basic dyes on protein fibres can also be improved by back
tanning. This consists of after treating the dyed material with tannic acid in order
to form the insoluble complex thereby reducing the tendency to migrate.
9. The basic dyestuff will combine with direct or sulphur or some acid dyestuffs. So
they cannot be used together in the same bath. But basic dyestuffs are used in
after treating cotton or other materials dyed with direct colors. Here the direct
dyestuff acts as mordant.
10. When treated with a reducing agent most of the basic dyes get converted into their
colors less leuco compounds, return to their original color by oxidizing agents or
even by exposure to air.
11. Basic dyes can be removed from the material by boiling it with dilute acetic acid
or hydrochloric acid.
12. Basic dyes are used for woolen goods when particularly bright shades are required
which cannot be obtained with an acid dyes.
13. Basic dyes do not have affinity for cellulosic fibres like cotton. The use of basic
dyes on cotton involves the troublesome process of mandating with tannic acid.
But, sometimes, bright shades are demanded on cotton which can only be
obtained with them.
14. Special cationic dyes are available for dyeing acrylic fibres.
15. Basic dyes are also used for making inks, typewriter ribbons and dyeing leather

3.10.2. Preparation of Dye Solution:

Owing to the relative insolubility special precautions are necessary when


dissolving basic dyes. The dyestuff is first made into a paste with about its own weight of
30% acetic acid. Sufficient boiling water is then added with constant stirring to dissolve
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Dyeing & Printing 29

the dye. The basic dyes have such a great affinity for wool fibres the presence of a
retarding agent is often desirable. The Acetic acid acts as a retarding agent.

The excess of hydrogen ions in the liquor counter acts the attracting of the electro
negative sites in the fibre and slows down the rate of absorption. When acid has been
used, the addition of a small amount alkali may be necessary towards the end of the
dyeing to complete exhaustion.

3.10.3. Dyeing:

The dye bath is made up containing 1 to 3 % of 40% acetic on the weight of the
wool, the dye solution, after being strained through a filter is added, and the goods, which
have previously been scoured, are entered. The dye bath temperature is slowly raised to
the boil and dyeing is continued for ½ to ¾ hour. After dyeing the goods are rinsed,
hydro-extracted and dried.

3.11. Sulphur Dyes

These dyes are so called because they contain sulphur atoms in their molecules.
The fibres most readily colored with sulphur dyes are the natural and man-made
cellulosic fibres. (Cotton, Viscose rayon)

The Characteristics feature of the dyes of this class is that they all contain sulphur
linkages within their molecules. They are usually insoluble in water but dissolve in a
solution of sodium sulphate to which sodium carbonate may or may not be added. The
sodium sulphate acts a reducing agent severing the sulphur linkage and breaking down
the molecules into simpler components which are soluble in water and substantive
towards cellulose.

3.11.1. General Properties of Sulphur Dyes

The sulphur dyes are cheap and easy to apply. Their wet fastness is good and the
light-fastness-satisfactory. They therefore provide a cheap method of dyeing cellulosic
fibres with a wet-fastness better than the direct dyes. The sulphur dyes have poor fastness
to chlorine and are no use for effect in merchandise which must be bleached with
hypochlorite, but they will withstand the conditions in an acid dye bath and can be
incorporated in woolen goods intended for subsequent dyeing, as will be referred to
latter, however, the after-treatments which improve the fastness of these dyes.

In their reduced state, their dyeing properties resemble in any respects those of the
direct dyes. They exhaust better in the presence of electrolytes and vary considerably
with regard to the temperature at which maximum exhaustion takes place. They are
decomposed with acids usually with the liberation of hydrogen sulphate and the
Dyes, Theory of Dyeing, Classification of Dyes and its application
Dyeing & Printing 30

precipitation of insoluble decomposition products. On exposure to air or when acted upon


by mild oxidizing agents, a part of the sulphur is oxidized to sulphuric acid.

The sulphur dyes resemble the vat dyes in that they are insoluble in water but
reduce to a soluble form, which readily converts to the accompanied by an alteration of
color. Sodium sulphate is the reducing agent commonly used but in some cases sodium
hydro sulphate may be substituted making it possible to dye selected vat and sulphur dyes
together.

3.12. Disperse Dyes

These dyes derive their name from the fact that they are insoluble in water and
are, for the purpose of dyeing, dispersed in the dye bath by means of dispersing agents.

The fibres most readily colored by disperse dyes are the acetate fibres, polyester,
acrylic and nylon.

3.12.1. General Properties of Disperse Dyes

1. Generally these dyes are insoluble in water.


2. However they are soluble in hot water to some extent, the solubility increasing
with temperature.
3. A feature of disperse dye molecules is their lack of polar groups, evidenced by the
insolubility of disperse dyes.
4. Textile materials which have been colored with disperse dyes have a fair to good
light-fastness.
5. Textile materials colored with disperse dyes have a moderate to good wash-
fastness.
6. Some of the disperse dyes are, however, sensitive to nitrogenous fumes, such as
may arise from gas, electric or other fibres, suffering serious discoloration,
referred to as gas-fading.
7. Disperse dyes have the ability to undergo sublimation: i.e. they can be vaporized
without a significant change in their color, i.e. light-fastness or wash-fastness.

3.12.2. Dyeing with Disperse Dyes

Disperse dyes are applied from an aqueous dispersion, not form solution, and
which, having a greater affinity for the organic fibre than for the water of the dye bath,
eventually migrate to the fibre and form a solid solution in it. The application of heat to
the dye liquor increase the energy of the dye molecules and accelerate the dyeing of the
textile fibre.

Heating the dye liquor swells the fibre to some extent and assists the dye to
penetrate the fibre polymer system resulting in the dye being located in the amorphous
Dyes, Theory of Dyeing, Classification of Dyes and its application
Dyeing & Printing 31

regions of the fibre. Once within the fibre polymer system, the dye molecules are held by
hydrogen bonds and Vander walls forces.

Polyester fibres are extremely crystalline and hydrophobic, lack of reactive


groups and much more closely packed polymer chains and there are no gaps which
molecule are very close to change their position to suitably accommodate they dyestuff
molecule, and further more the chain molecules are very reluctant to change their
positions i.e. to close their orientation. This result, the dyestuff particles do not penetrate
to the fibre easily and in fact the process is so slow that it takes a matter of days or even
weeks to dye a Terelene fibre at a dyeing temperate of 85ºC.

It is difficult to obtain medium or dark shades even by dyeing at the boil. In order
to obtain medium to dark shades, polyester fibre is dyed using carries or by using high
temperature dyeing techniques.

4.0. INTRODUCTION TO DIFFERENT DYEING MACHINES

There are several dyeing machines used for dyeing of fibre, yarn, fabric and garments.
Some of the important of them are

(1) Jigger Dyeing Machine

(2) Winch Dyeing Machine

(3) Jet Dyeing Machine

(4) Padding Mangle

(5) Package Dyeing Machine

(6) High Pressure High Temperature Dyeing Machine. (Beam Dyeing Machine)

4.1. Jigger Dyeing Machine

Jigger dyeing machine is the most commonly used for dyeing all kinds of cotton fabric.
There are mainly two types of jigger dyeing machine. One is open jigger dyeing machine
and other is closed jigger dyeing machine.

The open jigger dyeing machine is shown in the figure. This machine consists of V
shaped stainless steel vessel. Two rollers are fitted above the vessel called as cloth rollers.
These rollers are rotated by power.

Out of these two rollers one roller is driven by a motor which is called take up roller and
the other roller from which the cloth is delivered is called let off roller. When all the cloth
Dyes, Theory of Dyeing, Classification of Dyes and its application
Dyeing & Printing 32

is passed from the let off roller to the take up roller, it is called as one end or one turn.
The number of ends or turns depends upon the type of the fabric and also the percentage
of the shade.

Initially, a large length of (50 kg) cloth is wound on the let off roller and take up roller is
then driven by the power. After one end is taken, the take up becomes let off roller. These
backward and forward movements of cloth through the dye liquor absorb more and more
dye.

The capacity of the jigger is 100 to 150 gallons. In the modern jigger, automatic devices
are fitted along with the timing switch by using reversing will take place automatically.

When dyeing all the dye liquor should not be added at one time. The dye liquor should be
added in batch wise, in order to get even shade on the cloth. In the present scenario,
closed types of jiggers are used. The main advantage is to prevent heat loss and chemical
loses by evaporation. This type of jigger is very important for dyeing vat, Sulphur etc.

4.1.1. Advantages of Jigger Dyeing Machine

1. The cloth can be dyed in open width form of full width form.

2. Chemical and heat loses are less when compared to winch dyeing machine

3. The material to liquor ratio is 1:3 (or) 1:4 which saves considerable amount of
chemical cost and steam cost.

4.1.2. Disadvantages of Jigger Dyeing Machine

It exerts lot of tension in the warp direction and because of this normally woolen, knitted
fabrics, silk etc are not dyed in jigger dyeing machine.
Dyes, Theory of Dyeing, Classification of Dyes and its application
Dyeing & Printing 33

4.2. Winch Dyeing Machine

Winch dyeing machine is normally used for dyeing light weight fabrics like knitted
fabrics as well as woven, silk etc. The winch dyeing machine is different in construction
from the jigger. The machine consists of elliptical winch (or) circular winch which is
driven by hand or motor. Elliptical winches are most widely used.

It has a perforated portion dividing the machine in to two compartments. One is small and
the other one is bigger in size. Dye- liquor pipe, steam pipe, water inlet are provided in
small compartment. Dyeing is carried out in the larger compartment.

During working, one end of the fabric is passed over the guide rollers and winch and
under the dye liquor and passed in between the pegs. After the sufficient amount of cloth
is fed the ends are stitched and making a long continuous loop formation. Many such
loops run together separately by a series of pegs, to avoid entanglements. The loops are
drawn in and out of the bath by rotating the winch. After dyeing is over the pieces are
separated.

The winch is made up of stainless steel. Now-a-days closed type of winch is also used to
prevent the temperature loss and pressure loss.

4.2.1. Advantages

Thin and light weight fabrics like knitted fabrics, voile cloth etc, can be dyed successfully
in winch dyeing machine without exerting any tension.

Embroidery fabrics may be dyed in winch dyeing machine without affecting the
embroidery designs.
Dyes, Theory of Dyeing, Classification of Dyes and its application
Dyeing & Printing 34

4.2.2. Disadvantages

Fabrics are dyed in rope form, so there are more chances for uneven dyeing. Therefore,
we will get even dyeing only when retarding / leveling agent is added to the dye liquor.

The material to liquor ratio is very high i.e. 1:30 or 1:40. Therefore the heat and the
additional chemicals are provided more when compared to jigger.

Heat and chemical losses are more because of the wider open tank.

4.3. Padding Mangle

Continuous dyeing methods depend upon the impregnation with the padding mangles.
The padding mangles are equipped with two, three or even four mangles. The rollers are
arranged one above the other. Three bowl padding mangle are usually prepared for
dyeing of cloth.

The padding mangle consists of two ebonite rollers and one rubber covered roller. To
reduce the material to liquor ratio, low capacity troughs are generally used with the
different shapes.

Some of the machines are provided with jacket troughs for maintaining the temperature
of pad liquor. An over head tank is connected to the mangle for feeding the stock solution
through the perforated pipe. The supply of the dye-liquor is controlled automatically to
maintain a constant level. The pressure on the padding mangle is applied by hydraulic or
pneumatic system which enables heavier and uniform pressure.

The trough is fitted with dye-liquor and the cloth passes through the dye solution, which
is heated by steam. After that the cloth is passed between the ebonite and rubber covered
roller to give uniform pressure throughout the fabric.

The pressure can be altered depends upon the type of the fabric. The speed is 200
yards/minute. It is used for dyeing vat, Sulphur, Naphthol etc. The solution used in the
trough is divided in two equal portions to avoid uneven dyeing. The padding mangles
may also be used for desizing purposes.

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Dyeing & Printing 35

4.4. Jet Dyeing Machine

This is the most modern machine used for the dyeing of polyester using disperse dyes. In
this machine the cloth is dyed in rope form which is the main disadvantage of the
machine.

In this machine, the dye tank contains disperse dye, dispersing agent, leveling agent and
acetic acid. The solution is filled up in the dye tank and it reaches the heat exchanger
where the solution will be heated which then passed on to the centrifugal pump and then
to the filter chamber.

The solution will be filtered and reaches the tubular chamber. Here the material to be
dyed will be loaded and the winch is rotated, so that the material is also rotated. Again
the dye liquor reaches the heat exchanger and the operation is repeated for 20 to 30
minutes at 135o C. Then the dye bath is cooled down, after the material is taken out.

Metering wheel is also fixed on winch by external electronic unit. Its purpose is to record
the speed of the fabric. The thermometer, pressure gauge is also fixed in the side of the
machine to note the temperature and pressure under working. A simple device is also
fixed to note the shade under working.

4.4.1. Advantages

 Dyeing time is short compared to beam dyeing.


 Material to liquor ratio is 1:5 (or) 1:6
 Production is high compared to beam dyeing machine.
4.4.2. Disadvantages

 Cloth is dyed in rope form


 Risk of entanglement
 Chance for crease formation.
Dyes, Theory of Dyeing, Classification of Dyes and its application
Dyeing & Printing 36

4.5. Package Dyeing Machine

A series of technical developments in the recent


years has resulted into package dyeing being
developed into a highly sophisticated as well as an
economic process. Latest design Package Dyeing
machines are amenable to accurate control and
automation. These features would likely to lead to
increases in the application of package dyeing.

The term package dyeing usually denotes for dyeing


of yarn that has been wound on perforated cores.
This helps in forcing the dye liquor through the
package. With the start of dyeing cycle, the dye
liquor goes on circulating throughout the vessel and
tank. This happens till all the dye is used up or fully
exhausted. The dye flows through to the yarn package with the help of the deliberate
perforations in the tube package. Once full exhaustion is brought about, the carrier of
coloured yarn is consequently removed from the vessel. A large centrifuge removes
excess water from the packages. Finally the yarn is dried using an infra red drying oven.
The image shows the process working of a Package dyeing machine.

4.5.1. Advantages of Package Dyeing machine

Package dyeing methodologies have been subjected to intensive research and


development. As a result package dyeing machine has evolved into a very sophisticated
apparatus. It offers a number of advantages.

 Considerable reduction in yarn handling.


 Compatible to automatic control, in the process leading to reproducible dyeing‟s.
 Open to large batches.
 High temperature dyeing a possibility.
 Low liquor ratios, giving savings in water, effluent and energy.
 Uniform and High rates of liquor circulation, that leads to level application of
dyes.
 Machinery totally enclosed resulting in good working conditions at the dye-house.

4.6. Beam Dyeing Machine

The beam dyeing machine operates with the same principle as that of package dyeing
machine. It can be effectively used to dye yarn or fabric. The process works like this,
fabric or yarn in open width is rolled on to a perforated beam. The beam then
subsequently slid into a vessel that is closed and pressurized. The colour impregnates the
Dyes, Theory of Dyeing, Classification of Dyes and its application
Dyeing & Printing 37

fabric as the dye liquor is allowed to go on circulating through the perforations in the
beam. Usually the beam machines are designed in such a manner so as to hold a single
beam or multiple beams in a batch.

4.6.1. Features of Beam Dyeing Machine

 Able to adjust water level in accordance to fabric volume.


 Even dyeing and superior dyeing quality.
 Optimized circulation system along with high performance pumps.

4.6.2. Advantages of Beam Dyeing machine

 The fabric is put under controlled tension, and is wound on to a perforated beam.
This results in elimination of creases from the fabric. It also ensures total control
of dimensions of the roll of fabric.
 The fabric is not allowed to do any movement during the process of dyeing. This
actually means that there is no application of mechanical action on to the fabric.
As shown in the figure, there is no movement of the fabric as the hydrostatic
pressure of the pump forces the dye liquor through the fabric roll.

Dyes, Theory of Dyeing, Classification of Dyes and its application