1.

1 TEXTILES:
The word textile encompasses anything that is associated with fibres, whether they be
of animal, vegetable or mineral origin, manufactured or natural. Fibres can be spun
together to form continuous filaments which can then be knotted, woven or felted.
When fibres are spun and then woven, the result may be, or can be, a length of fabric
(natural or synthetic). Fabrics can be further enhanced by controlled weaving to create
textured patterns within the woven form, colouring of different spun fibres to create
distinct pattern groupings and finally by adornment through such techniques as
creative stitchery, appliqué or beading. Textiles are historically an integral part of
many cultures. People have knotted woven, intertwined, felted, knitted, sewn for
many reasons. To create functional objects was always the primary aim, but personal
adornment and embellishment have grown into cultural traits over the years. People
have knotted and intertwined continuous filaments to create everyday usable objects
such as carry-bags. They have used the knotting technique to increase the strength of
fibres so that their function and life span may be extended and, of course, people have
woven fibres into continuous lengths of cloth for personal clothing and soft
furnishing. The urge to adorn and beautify has led people to embellish these
functional objects. Such embellishment has been handed down through generations so
that today we can see and identify pattern and colour combinations in one culture
uniquely different from those in another. Today, work with fibres encompasses not
only functional forms but also non-functional sculptural and/or pictorial forms. When
we look at the extensive range of textile products and techniques used to obtain these
products it may all seem quite daunting and you may wonder where to start. However,
by grouping according to technique it all begins to become a lot clearer.
1. Fibre to Fibre - spinning, weaving, tapestry, crochet, macramé, knitting, felting.
2. Colour to Fabric - tie dye, batik, gutta, dispersal dye, serigraphic printing
(silkscreen) relief printing - lino, card, string, hand painting.
3. Fabric to Fabric - patchwork, appliqué, quilting.
4. Fibre to Fabric - creative stitchery.
Each technique can be used by itself to create an end product, or they can be
combined to create further exciting products.

1.2 Dyes & Fibre Polymer System

1.2.1 Wool Fibres:

The wool fibre is composed of the protein keratin, which consists of long polypeptide
chains built from eighteen different amino acids. Most of these acids have the general
formula H2N.CHR.COOH, in which R is a side chain of varying character. The chain
structure is of the type:

And at intervals bridges derived from the amino acid cystine connect the chains.

1
Some of the side chains end in amino groups and others in carboxyl groups; internal
salts are therefore formed and the

Molecules are bound together by electrovalent linkages. The molecules of keratin are
very large, with and average molecular weight estimated at about 60,000. The wool
fibre is readily destroyed by alkali, but withstands acid conditions fairly well; some
hydrolysis of peplide linkages occurs on prolonged boiling with acids, however. The
carboxylic acid and amino groups in the keratin molecule confer affinity for basic and
acid dyes. Basic dyes are now little used on wool since their fugitive properties render
them unsuitable for such and expensive and durable fibre. Acid dyes, however, are
extensively used, and the general characteristics of this large class and the related
mordant and pre-metallised azo dyes are now described.

Since the bonds between dye anions and amino groups in the wool fibre are easily
broken and re-formed, dyes attached in this way are liable to migrate. This property is
advantageous, in that level dyeing is readily attained, but it leads to low fastness to
wet treatments, and any undyed wool present during washing becomes stained. These
characteristics are chiefly apparent in dyes of low molecular weight, and fastness to
washing is in general much better in more complex dyes. The larger dye molecules
are evidently attached the fibre by some means other than the ionic bonds mentioned
above, and it is believed that6 they are held by non-polar Van-der Waals forces
exerted between hydrophobic dye anions and hydrophobic regions of the wool fibre,
their strength being proportional to the area of contact. From an application point of
view acid dyes are classed as either Levelling or Milling types. The Levelling
(sometimes called Equalizing) dyes have fairly simple chemical structures, migrate
readily on wool, and are easily applied from strongly acid baths; their wet-fastness
properties are low. The Milling dyes are structurally more complex, have high affinity,
and must be applied form weakly acid baths for control of the rate of dyeing, but they
show high fastness to milling and other wet treatments. Milling is a felting process
applied to woolen cloth by squeezing or beating, usually in a soap solution. It
sometimes follows dyeing, and the dyes used must then have high wet-fastness
properties in order to withstand these severe conditions. The advantages of good
levelling and high milling fastness cannot be fully combined in a single dye, but there
are general purpose dyes with intermediate GTFVJ,./properties. The application
classes can becorrelated roughly with chemical types, as shown for monoazo and
disazo dyes in Table 4 – 1, which provides a few typical examples. As might be
expected from the foregoing generalizations, trisazo and other polyazo dyes are of the
milling class, but since shades are usually dull and uneven they are seldom of
technical value on wool.
1.2.2 Silk Fibres:
Cultivated silk is a natural fibre produced by larvae of the silkworm Bombyxmori,
and wild silk is produced similarly by silkdworms of various species. Raw silk
consists of the protein fibroin surrounded by silk gum (sericin), and the latter is
removed in the process of de-gumming or ‘boiling off’ which precedes dyeing.

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Fibroin consists of long parallel chain containing about 400 amino acid residues with
a structure of the general type

The residues are derived mainly from the amino acids glycine (R = H), alanine (R =
CH3), serine (R=CH2OH) and tyrosine (R= --CH2--- OH), but there are numerous
others in small quantities. Fibroin differs from keratin in that it contains no sulphur.
Its chemical properties are similar to those of keratin, but it is more sensitive to acids
than the latter and less sensitive to milk alkalis. Silk can be dyed with dyes of almost
every class, but some restrictions arise from the common practice of weighting the
fibre with tin salts, which is carried out in order to improve handling properties and
reduce cost. So far as azo dyes are concerned the main classes applied to silk are the
acid dyes and pre-metallised dyes already described as wool dyes, the direct dyes
described in Chapter and the reactive dyes described in Chapter. Mordant dyes
applied to silk are mainly of the anthraquinone type. It has never been necessary to
develop dyes especially for silk.

1.2.3 Cellulosic Fibres:

The earliest cellulosic fibres were lines and cotton, both of which have been used
since remote antiquity. Linen, or flax, is derived from ‘bast’ fibres of plants of the
Linum family, especially Linum usitatissimum. After removal of glutinous and
pectinous matter the fibre has cellulose content of 82 – 83%. Cotton, which is fine
hair attached to seeds of various species of plants of the Gossypium genus, has a
cellulose content which may reach 96%. Cellulose is a polymer of high molecular
weight consisting of long chains of D-glucose units connected by B-1, 4- glucosidic
bonds, and its structure may be represented as
follows:

Each glucose unit contains three alcoholic hydroxyl groups, of which two are
secondary and one is primary. The degree of polymerisation of cellulose varies from a
few hundred to 3500 or more.Regenerated cellulose fibres were introduced during the
last two decades of the 19th century. The first process was that Chardonnet (1884),
who produced a fibre by spinning a solution of nitrocellulose in a mixture of alcohol
and ether and subsequently removing nitro groups. The cuprammonium process
followed (1890), and in 1891 Cross and Bevan introduced the viscose process

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whereby wood pulp cellulose is treated with caustic soda and carbon disulphide to
form sodium cellulose xanthate, which, after a ‘ripening’ stage, is spun into an acid
coagulating bath. The nitrocellulose process is now obsolete, but the cuprammonium
process, which has the advantage of giving an exceptionally fine filament, is still
used. The viscose process is of much greater importance, but it is declining in
consequence of the development of the newer synthetic fibres. The dyeing properties
of the various cellulosic fibres are broadly similar, but application conditions are
affected by differences in physically properties. Thus lines, which has a harder
structure than cotton, is less readily penetrated by dyes. There are also differences in
dyeing properties between the several types of regenerated cellulose fibres;
cuprammonium rayon, for example, having fine filaments, is more easily dyed than
viscose. Dyes of many chemical classes are applied to cellulosic fibres. Azo dyes,
which predominate numerically, are described here, and others are dealt with in the
appropriate chapters. The first substantive or ‘direct’ dyes discovered in 1884 were
diazo dyes obtained from tetrazotised benzidine, but other structure have since been
found to confer affinity for cellulose. The azo group itself favours substantivity but
for adequate effect either a second azao group or another favourable group must also
be present in the dye molecule.The structures which are chiefly important in
substantive dyes are as follows

All of the other groupings listed find used in conjunction with the azo chromophore to
give a great variety of dyes for cellulosic fibres. Others of smaller importance, such as
the residues of pyrazol-5-one, resorcinol and m-phenylenedianine, also confer a
measure of cellulose affinity. Apart from the presence of one or more of the
favourable components there are other structure requirements for substantivity.
Typical substantive azo dyes of the various chemical classes are now described.

1.2.4 Monoazso Dyes:

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About 35 monoazo direct dyes are in use, most of them containing either a thiazole or
a J acid residue. Examples are CI Direct Yellow 8 (CI 13920), CI Direct Brown 30 (CI
17630) and CI Direct Red 118 (CI 17780) (diazotised and developed on the fibre with
B-naphtol or 3- methy-1-phenylpyrazol-5-one), with the structures shown:

1.2.5 Dyes with Mixed Chromophores:

Polyazo dyes normally contain a single chromophoric system, and a conjugated chain
runs through the whole molecule. It is possible, however, for a dye molecule to
contain two or more independent chromophoric systems electronically insulated from
each other. Such dyes were first introduced by CIBA, who utilized the triazinyl ring as
a chromophoric block. This ring serves as a convenient link since it can be introduced

5
by reaction of cyanuric chloride with two or three aminocontaining dyes in
succession. Substitution of the first chlorine atom takes place easily in presence of
alkali at atmospheric temperature. The second chlorine atom is less easily removed,
and reaction with an amino compound may require a temperature of 55o – 60oC, the
optimum conditions varying with the basicity of the amine. Replacement of the
clorine atom calls for still more vigorous conditions, and a temperature of 90o –
100oC may be suitable; much higher temperature are needed, however, in the case of
weakly basic compounds. The progressive loss of activity at each stage enables
condensation to be carried out with three different components to give a substantially
homogeneous product. The residues of three dyes (Dye 1)-NH2, (Dye 2)-NH2 and
(Dye 3)-NH2 may be linked by a series of reactions in alkaline medium, as shown:

In the resulting product each dye residue contributes its own absorption
characteristics; by combining yellow and blue components, green dyes can therefore
be obtained that are much brighter than normal polyazo greens. Dyes containing three
inde; pendent chromophoric system is of limited interest and the third condensation is
often carried out with a suitably reactive colourless compound such as aniline or
phenol.An example of a commercial dye containing two electronically insulated
chromophores is Chlorantine Fast Green BLL (CIBA) (CI Direct Green 26; CI
34045); it gives bluish green hue on cellulosic fibres. One of the aminoazo dye
residues. A commercial dye containing both azo and anthraquinone residues is
Chlorantine Fast 5 GLL (CIBA) (CI Direct Green 28; CI 14155), which has the
structure (2) and gives bright yellowish green shades on cellulosic fibres.

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1.2.6 Cellulose Acetate Fibres:

The D-glucose units in the cellulose polymer contain three hydroxyl groups, of which
one is primary and two are secondary. By acetylating all of the hydroxyl group in
cellulose a triacetate is obtained with a polymetric structure which may be represented
thus:

The triacetate is soluble in chloroform, and a fibre known as Lustron was spun from
chloroform solution in early small-scale American manufacture (1914-1924). If the
triacetate is partially hydrolysed to give a mixture with an average of 2 ½ acetyl
groups per glucose residue the product loses solubility in chloroform, but becomes
soluble in acetone. A different product, which is insoluble in acetone, is obtained by
direct introduction of 2 ½ acetyl groups; presumably the less accessible hydroxyl
groups are the last to be acetylated and the last to be re-formed on hydrolysis. During
the First World War incompletely acetylated cellulose was produced on a large scale
for use as a dope for aircraft fabric. After the war efforts to find a new use for it led to
the production of cellulose acetate fibre by British Celanese Corporation. The
commercial product contains an average of 2-3 acetyl groups per glucose residue, and

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is known as secondary acetate, or simply ‘acetate’. It is spun from acetone solution. In
spite of an inconveniently low melting-point acetate fibre attained great success and is
still extensively used, but in recent years it has been partly superseded by other
synthetic fibres. It was appreciated in the early days that the dyeing of acetae differs
from that of the natural fibres and viscose in that fibre serves as a solvent for the dye.
In 1923 work on dyes in the form of aqueous dispersions was carried out
independently by British Celanese Corporation and British Dyestuffs Corporation.
The SRA colours of British Celanese Corporation were dispersions of aminoazo or
hydroxyazo dyes obtained by means of the surface-active agent sulphated ricinoleic
acid. Other dispersing agents used included alkyl sulphates, alkaryl sulphonates and
fatty alcohol-ethylene oxide condensates (a long alkyl chain being usually present in
the molecule), and the dispersions obtained by applying them with various milling
techniques were often so fine as to be easily mistaken for true solutions. British
Dyestuffs Corporation marketed dispersed aminoazo and hydroxyazo dyes in their
Dispersol range, and this is still maintained by ICI (formed in 1926 by a union of
British dye stuffs Corporation with other firms). The Duranol range is a parallel range
of dispersed dyes of the anthraquinone series. Dyes of these types are now produced
by many manufactures. Whereas the dyes were formerly supplied only as aqueous
dispersionsthey are now usually marketed in the form of re-dispersible powders which
yield suitable dispersions on stirring with water. Hydroxyalkylamino groups impart a
small degree of watersolubility and assist dispersibility; coupling components such as
N-ethyl- N- B-hydroxyethylaniline or N, N-di (B-hydroxyethyl) aniline aretherefore
commonly used. Many of the earlier yellow and orange dyes proved to be
phototropic, but it was found that this groublesome characteristic can be largely
avoided by introducing nitro or other negative groups into the dye molecule; these
substituents restrain trans cis isomerizatrion. Since dye molecules must be fairly small
in order that they dissolve readily in the fibre monoazo dyes are commonly used, but a
few disazo dyes are included in commercial ranges. Blacks are obtained by
diazotising aminoazo dyes on the fibre and developing with a solution of 3-hydroxy-
2-naphthoic acid. In 1936 a range of water-soluble dyes for acetate was marketed by
ICI under the name Solacet. Their solubility was due to the presence of a sulphuric
ester group (-- OSO3Na), usually introduced by sulphation of a B-hydroxyethlamino
group, which did not seriously impair affinity for the fibre. The unsuitability of
conventional water-soluble dyes for acetate fibres is apparently due to the presence of
highly ionised – SO3-Na+ groups rather than their solubility in water. In consequence
of the of the development of dispersed dyes with improved dyeing and fastness
properties the Solacet range has now been superseded. Many dyes developed for
acetate have now been applied to the newer synthetic fibres, and the manufactured
ranges have been extended specially for these outlets. The term ‘Acetate dyes’ has
therefore, been discarded in favour of ‘Disperse dyes’ so that all applications may be
included. Disperse dyes for fibres other than acetate are described later. Examples of
azo disperse dyes applied to acetate are shown in Table 4.6; violet and blue dyes are
included, but disperse dyes of these shades are derived mainly from the anthraquinone
series.

1.2.7 Cellulose Triacetate Fibres:

Cellulose triacetate was manufactured in the United States during the period 1914-24,
but the process was unsatisfactory because the only suitable solvent then

8
commercially available was chloroform, and this was both toxic and expensive.
Methylene dichloride is a suitable solvent of low toxicity, and it became available
fairly cheaply about 1930, but by the eat time secondary acetate was fully established.
Later, however, when the hydrophobic fibres nylon and ‘Terylene’ had achieved great
success, the possibilities of triacetate as an inexpensive fibre sharing some of their
good properties became apparent, and it has now been introduced as a commercial
fibre under names such as Tricel (Courtaulds Ltd.), Armel (Celanese Corporation of
America) and Trilon (Canadian Celanese Ltd.). It has good shrink- and crease-
resistance, is quickdrying, shows good fastness to wet treatments and can be heat-set
without loss of lustre. As it has a higher melting point the hazards associated with the
ironing of fabrics of secondary acetate are largely avoided. Because of its
hydrophobic character triacetate is less easily dyed than acetate, but suitable dyes can
be selected from existing ranges of disperse dyes. Whereas acetate is dyed at 75o–
80oC, triacetate requires a temperature at or near the boil. If the fabric is to be heat-set
for pleats the dyes used must be stable at 200oC.

1.2.8 Poyamide Fibres:

Nylon 6,6 and Nylon 6 can be dyed by many disperse, acid and direct dyes. Since
many suitable dyes are available, commercial ranges are usually selected from
products already manufactured for other purposes, and (apart from the reactive dyes
discussed later) new structures have not been required. It has proved very difficult to
manufacture nylon with uniform dyeing properties, and for this reason dyes with good
leveling properties are necessary. In this respect disperse dyes have a great advantage
in that they conceal fibre irregularities. For high wet-fastness acid dyes are preferred,
but very careful application is necessary in order to secure level dying. These dyes
often show better wet-fastness properties on nylon than on wool because of the
hydrophobic character of the former. Fastness to light, however, is often slightly lower
on nylon than on wool. The affinity of acid dyes for Nylon 6 is higher than that for
other types because polycaprolactam fibres contain a higher proportion of free amino
groups Ranges of acid dyes for nylon are classified by the makiers so that users may
select dyes with good leveling or good wet-fastness properties according to their
requirements, there are also ranges with intermediate properties and others specially
designed for fabric printing.

1.2.9 Polyester Fibres:

In the course of the exploratory work that led to the development of nylon W.H.
Carothers examined aliphatic polyesters but abandoned them in favour of the more
promising polyamides. Subsequently, however, the late J.R. Whinfield and J.T.
Dickson of The Calico Printers’ Association re-examined polyesters for the purpose.
They extended the work to aromatic compounds and obtained a polymer with
excellent fibre-forming properties from terephthalic acid and ethyleneglycol. This has
the structure (3). The important fibre ‘Terylene’ was based on this

9
Work, and was first prepared in the laboratory in 1941. Development and production
of the fibre were carried out by ICI, and this fibre is now manufactured under various
names on a very large scale in many parts of the world. Dimethyl terephthalate is now
commonly used in place of the free acid so that the terminal carboxlic acid group is
esterified. Since n has a value of about 80 the properties of the fibre are not greatly
affected. The ester is preferred as starting material because it is more easily purified,
and purity is essential in the manufacture of high polymers. ‘Terylene’ fibre is highly
hydrophobic, withstands attack by bacteria, moulds, months, acid and alkali, has high
strength even in wet conditions, is superior to nylon in resistance to light, can be heat-
set and has glood di-electric properties. It is largely used for manufacture of net
curtains, in blends with wool for suitings and other outerwer,k and for many industrial
purposes. The hydrophobic nature of ‘Terylene’, its tightly packed molecular structure
and its lack of reactive groups all render it unreceptive to dye molecules. Certain
disperse dyes can be applied, but under normal conditions adsorption is slow and only
pale shades are obtained. Much better penetration is obtained by dyeing at about 12Oc
under pressure, and the special dyeing machinery required is now in general use.
Since diffusion is slow in conditions of normal use, dyeings obtained in this way have
good wet-fastness properties. Suitable dyes must be selected for this process since not
all will withstand the high temperature without change of shade. Disperse dyes can
also be applied at temperatures below 100oC by the aid of ‘carriers’ added to the
dyebath. These agents are supplied under various brand names, such as ‘Tumescal’
(ICI), and usually consist of compounds such as o- or phydroxydiphenyl. Their
presence greatly facilitates the dyeing process, but the mode of action is not fully
understood. This process enables dyeing to be carried out in standard machines, but it
is somewhat expensive and has disadvantages in that the carriers are often difficult to
remove completely; their presence may cause a noticeable odour and sometimes
impairment of light-fastness. Polyester fibres can be dyed by the Thermosol process
(DuPont), which consists in padding with disperse dye and a thickening agent, then
drying and heating at 175o – 200oC for about one minute. Under such conditions the
dye is absorbed rapidly; after scouring to remove loose colour the dyed material is
finished in the usual way.

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1.2.10 Polypropylene Fibres:

Polyethylene has many applications in the plastic industry, but its low melting-
pointrenders it unsuitable for fibre formation. Its homologure polypropylene exists in
various forms according to the disposition of the substituent methyl groups; the
isotactic polymers, in which these groups are all attached on the same side of the main
carbon chain, can be spun and drawn into fibres. Catalysts promoting formation of
isolactic polymers were discovered by Zeigler, and the process was further developed
by Natta and others Polyproplene fibres and hydrophobic and resist chemical attack,
but they are not readily dyed. Certain disperse dyes can be applied, but only pale and
medium shades are obtainable. Many methods have been described in the paten
literature whereby the fibre may be modified to confer affinity for acid or basic dyes.
Side chains carrying polar groups may be grafted to the main polymer chain, or basic
substances may be included in the melt from which the fibre is spun. Much attention
has been paid to a method whereby a compound of a polyvalent metal such as nickel,
zinc or aluminium is incorporated in the fibre, which can then be dyed with
metalisable dyes.

1.2.11 Polyurethane Fibres:

Several elastomeric fibres developed in America are based on polymeric structures
containing urethane (--NHCOO--) linkages. Full details of the processes used are not
available but complex cross-linked polymers with rubber-like properties are obtained
from polyesters or polyethers containing terminal hydroxyl groups by means of a
series of reactions involving di-isocyanantes and diamines. Typical examples of such
fibres are Lycra (Du Pont) and Vyrene (U.S. Rubber Co.), which are extensively used
for foundation garments and swimsuits. These fibres have advantages over rubber in
strength, resistance to oxidation, perspiration and cosmetic oils, also in whiteness and
affinity for dyes. They are readily dyed by acid, basic and disperse dyes, but fastness
properties are in general rather low.

1.2.12 Polyacrylonitrile Fibres:

The simplest, polyacrylonitrile fibres are straight polymers of

acrylonitrile with structure where n varies from

600 to 2000. The first commercial fibre of this type was Orlon, introduced by DuPont
in 1948. It can be dyed by basic dyes or by acid dyes in presence of copper sulphate.
Various modified acrylic fibres (often called ‘modacrylic’ fibres) are now obtained by
copolymerizing acfrylonitrile with other substances, and dyeing properties are thereby
improved; Orlon as now manufactured is a copolymer, but the identity of the second
component has not been disclosed. Acrilan (Chemstrand Corporation), Dynel (Union
Carbide Corporation) and courtelle (Courtaulds Ltd.) are other modified acrylic fibres.
In general acid, disperse, basic and vat dyes can be applied to these fibres, but acid
dyes are not recommended for Courtelle. The older basic dyes often show better light

11
fastness on acrylic fibres than on natural fibres, but new basic dyes have been
developed with fastness properties on polyacrylonitrile that are fully compatible with
modern standards.

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2.1 Dyestuff
Dyestuff is organic or inorganic substances which can absorb light and reflect some
lights to show color. Actually, the dyestuff is water soluble substances.

2.2 Pigment
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.
2.3 CRITERIEA FOR A SUITABLE DYESTUFF
1. Cheap
2. Non-toxic
3. Compatible to other dyes and chemicals
4. High color strength
5. Better brightness
6. Better fastness
7. Good levelness on the materials

2.4 Exhaustion of the dye stuff to the fibers is as follows:

1. Moving of dyestuff from dye bath to surface of the fiber
2. Adsorption of the dyestuff into the surface of the fiber
3. Diffusion of the dyestuff into the center of the fiber.

2.5 Classification of Dyestuffs

Dyestuffs can be classified according to two ways
1. According to common parent structure
2. According to application

2.5.1. Classification according to common parent structure or Chemical

classification of dyes:
The chemical constitution of dyes are varied that it is difficult to classify them
into distinct groups. The colour index classifies dyes as shown.

1. Nitro dyes.
2. Nitroso dyes.
3. Azo (Monazo) dyes.
4. Azoic dyes.

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 5. Stilbene dyes
6. Tgri0aryl methane dyes.
7. Xanthenei dyes.
8. Quinoline dyes.
9. Methine dyes.
10. Acridine dyes.
11. Nitro dyes.
12. Sulphur dyes.
13. Thiazole dyes.
14. Thizine dyes.
15. Indamine dyes.
16. Oxazine dyes.
17. Azine dyes.
18. Lectone dyes.
19. Anthra quinine dyes.
20. Indigoid dyes.
21. Phthalocyanin dyes.

2.5.2 CHEMISTRY OF SOME DYESTUFF

(1) Nitro Dyes:

Nitro dyes are polynitro derivatives of phenols containing at least one nitro group
ortho or para to the hydroxyl group. They are of relatively little importance
industrially, because the colours are not very fast. Examples of this class are picric
acid (2,4,6-trinitrophenol), Maritus yellow (2, 4-dinitro-1-naphthol), and Naphthol
yellow S (2,4-dinitro-1- naphthol-7-sulphonic acid). Naphthol yellow S can be used to
dye wool, and is one of thecolours permitted in foods. Naphthol yellow S can be used
to dye wool, and is one of the colours permitted in foods.
1. Naphthol yellow S can be used to dye wool, and is one of the colours
permitted in foods.

(2) Azo Dyes:

The azo dyes represent the largest and the most important group of dyes. They are
characterised by the presence of one or more azo groups (–N=N–), which form
bridges between two or more aromatic rings. Preparation of azo dyes involves the
following two steps.

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Step 1. Conversion of primary aromatic amines into diazonium compounds by
treatment with sodium nitrite in excess hydrochloric acid (Diazotisation)

Step2. Coupling of diazonium compounds with phenols, naphthols, or other aromatic

amines. Coupling with phenols and naphthols is carried out in basic solution; coupling
with amines is carried in acid solution.

The above reactions are carried out at low temperatures (0 – 5o) because diazonium
compounds are usually unstable. In the resulting dyes an aromatic system joined to
the azo group is the chromophore, and the hydroxyl group or amino group is an
auxchrome. To simplify the description of azo dyes, only the coupling step will be
shown. It will be assumed that the diazonium compound was obtained by
diazotisation of the corresponding amine.
(a) Aniline Yellow: Solvent Yellow 1. It is p-aminoazobenzene. Aniline yellow is the
simplest azo dye and is obtained by coupling benzenediazonium chloride with aniline
in acidic medium

Aniline yellow is used as a dye for oils and lacquers, and is also an intermediate for
other dyes.
(b) Chrysoidine: Basic Orange 2. It is 2, 4-diaminoazobenzene. Chrysoidine is
prepared by coupling benzenediazonium chloride with mphenylenediamine.

(3) Diphenlymethane Dyes:

Auramine O: It is one of the most valuable of the diphenylmethane dyes. It is

obtained by heating Michler’s ketone with ammonium chloride and zinc chloride at
160oC.

15
Auramine O is used to dye wool, silk, silk, nylon, rayon and paper.
(4) Triphenylmethane Dyes:
Triphenylmethane dyes can be identified by common structural cature shown below.
Notice that the central carbon atom is joined to two benzene rings and to p-quinoid
group.
Triphenylmethane dyes are not fast to light or
washing, however, except when applied to acrylic
fibres. They are used in large quantitiesfor colouring
paper, and typewriter ribbons where fastness to light
is not so important.

(a) Malachite Green: It is obtained by condensing

benzaldehyde (1 molecule) with N, N-
dimethylaniline (2 molecules) in the presence of concentrated sulphuric acid to give a
leuco base (Gr. Leuco, colourless). Oxidation of the leuco base with lead peroxide
followed by treatmen with hydrochloric acid yields the dye.

16
(b) Pararosaniline: It is the simplest triphenylmethane dye. Pararosaniline is
obtained by consdensinig p-toluidine (1 molecule) with aniline (2 molecules) in the
presence of nitrobenzene to give a colourless carbinol. Nitrobenzene serves both as a
solvent and an oxidising agent. Treatment of the carbinol with hydrochloric acid
yields the dye.
Pararosaniline has been used to dye cotton, wool and silk.

(5) Xanthene Dyes:

Xanthene dyes can be identified by a common
structural feature shown below. They are obtained
by condensing phenols with phthalic anhydride in
the presence of zinc chloride, sulphuric acid, or
anhydrous oxalic acid. Examples of this class are
fluorescein, eosin, and rhodamine B.

17
(a) Fluorescene. It is prepared by heating resorcinol (2 molecules) and phthalic
anhydridge (1 molecule) with zinc chloride at 190oC

Fluorescein is
of no value as a
dye. It is red
powder, which
is insoluble in
water. A dilute
solution of
fluorescein in
sodium
hydroxide gives
a strong yellow-
green
fluorescence
when exposed to light. It is used to trace pollution of water supplies by sewerage,
since if a small quantity of it is put in at the suspected source of pollution, the colour
will be detectable at some distance from the source, even after extensive dilution.
During World War II, fluorescein was used as a sea marker for airmen who had to bail
out from aeroplanes over water. It also aided searchers in locating them. Fluorescein
is also used as a mild purgative. The sodium salt of fluorescein is called Uranine. It is
used to dye wool and silk.
(6) Phthaeleins:
Phthaleins are related to xanthene dyes and are made in the same way.
Phenolphthalein: It is prepared by condensing phenol (2 molecules) with phthalic
anhydride (1
molecule) in
the presence
of zinc
chloride at
120oC

Phenollphthalein is not a dye. It is colourless solid, mp 261oC.Phenolphthalein is

insoluble in water, but dissolves in alkalis to form deep red solutions. This is due to
the formation of a disodium salt, the ion of which is coloured because of resonance.
When excess of strong alkali is added, the solution of phenolphthalein becomes
colourless. This is attributed to the formation of a trisodium salt, the ion of which is
colourless because of loss of resonance and quinoid structure.

18
Because of the colour changes shown above, phenolphthalein is used as an indicator
in acid-base titrations. Phenolphthalein is an extremely powerful laxative, and this
accounts for its widespread use as a denaturant for laboratory alchohol.
(7) Indigoid and Thioindigoid Dyes:
Indigoid. It is the parent compound of indigoid dyes and has been used in this country
from times immemorial. Egyptian mummy clothes, which are 5000 years old, were
dyed with it. Indigo was originally obtained from plants of indigofera group. The
leaves from these plants were covered with water and allowed to stand for several
hours. Enzymes present in the plants brought about fermentation, as a result of which
the β-glucoside of indoxyl (known as indican) in the leaves was converted into
indoxyl and glucose. Upon exposure to air the indoxy was oxidised to indigo.

19
Natural indigo contains an isomer of indigo known as indirubin(Indigo Red), and
other impurities in varying proportions. Most of the indigo used at the present time is
a synthetic product. It has replaced the natural stuff because of cheapness, purity, and
uniformity of the manufactured dye.
Preparation of Indigo. It may be obtained:
(1) By Heumann’s First Indigo Synthesis (1890). This involves the condensation of
aniline with chloroacetic acid to give Nphenylglycine. The phenylglycine is then
fused with sodium hydroxide and sodamide at 250oC to form indoxyl, which on
oxidation by air yields the dye.

N-Phenylglycine is now obtained in much higher yield by interaction of aniline and

the bisulphite compound of formaldehyde at 50-60oC, followed by treatment with
aqueous sodium cyanide, and hydrolysis of the resulting nitrile.

20
(2) By Heumann’s Second Indigo Synthesis (1896): This involves the condensation
of anthranilic acid with chloroacetic acid to form N-phenyl-o-carboxylic acid. This is
then fused with sodium hydroxide and sodamide to produce unstable indoxylic acid,
which decarboxyhlates to give indoxyl. Oxidation of indoxyl by air yields the dye.

21
Structure of Indigo: The structure of indigo has been deduced from consideration of
facts and conclusions such as the following.
1. Elemental analysis and molecular weight determinations show that the molecular
formula of indigo is C16H10O2N2.
2. Fusion of indigo with sodium hydroxide at low temperature produces anthranilic
acid. This indicates the presence of a benzene ring attached to one carbon atom and
one nitrogen atom in the ortho position.

3. Oxidation of indigo with nitric

acid yields only two molecules of
isatin. This indicates that the indigo
molecule contains two identical
units joined together, and that each
unit on oxidation produces a
molecule of isatin.
The following two possible
structures of indigo meet this
requirement.
4. Oxidation of indoxyl by air
yields indigo.
From above, it follows that (A)
represents the structure of
indigo. This has been confirmed
by the following synthesis by
Baeyer (1872).

22
X-Ray analysis shows that mostly indigo exist in the more stable transform. However,
derivatives of both are known.
(a) Tyrian Purple. It is 6, 6’-dibromoindigo. Its discovery was later than that of
indigo but it is believed to have been known in 1600 BC.

23
 Tyrian purple occures
naturally in the purple
snail, Murex Brandaris. It
takes about 12000 snails
to produce 1.4 g of the
dye. This explains its
rarity and why the colour
of mercial value.
(b) Thioindigo. It is
analogues to indigo in
which the two –NH–
groups are replaced by sulphur atoms. Thioindigo may be obtained by the reaction of
thiosalicylic acid, with chloroacetic acid, followed by fusion with sodium hydroxide
and oxidation by air. Thiosalicylic acid itself is made by diazotisation and reaction
with hydrogen sulphide.

Thioindigo is used to dye cotton, wool and polyesters.

(8) Anthraquinoid Dyes:
Anthraquinoid dyes can be identified by a common structural feature shown below.
Notice that a p-quinoid group is fused to
two other benzene rings.

Anthraqluinoid dyes are used for dyeing

wool, silk, nylon, cotton, leather and
paper. The most important dye in this
group is alizarin.
Alizarin. It is 1,2-
dihydroxyanthraquinone. Alizarin derives
its name from the fact that it was first
obtained from the roots of the madder plant (Fr. Alizari, madder). It is now prepared
from phthalic anhydride by the following six steps.
Step 1. Phthalic anhydride is treated with benzene in the presence of AlCl3 to give o-
benzoylbenzloic acid. (Friedel-Crafts Reaction)

24
 Step 2. O-
Benzoylbenzoic acid
is cyclized by
treatment with
concentrated
sulphuric acid to
form anthraquinone.

Step 3. Anthraquinone is heated with fuming sulphuric acid at 180oC to give

anthraquinone-2-sulphonic acid.

Step 4. Anthraquinone-2-sulphonic acid is converted into its sodium salt by treatment

with sodium hydroxide.

Step 5. Sodium salt of anthraquinone-2-sulphonic acid is fused with sodium

hydroxide in the presence of potassium chlorate at 200oC under pressure to give
sodium salt of 1, 2-dihydroxyanthraquinone. The purpose of potassium chlorate is to
provide oxygen for the oxidation of the carbon atom at C-1.

25
Step 6. Sodium salt of 1,2-dihydroxyanthraquinone is treated with sulphuric acid to
yield 1,2-dihydroxyanthraquinone (Alizarin).

Alizarin can also be made by condensing phathalic anhydride with catechol in the
presence of sulphuric acid at 180oC (See Below). Alizarin forms ruby red crystals, mp
290oC. It is insoluble in water and ethanol. It dissolves in alkalis to give purple
solutions. Alizarin is used to dye cotton and wool. It is also used for making printing
inks.
Structure of Alizarin:
The structure of Alizarin has been deduced as follows:
1. Elemental analysis and molecular weight determinations show that the molecular
formula of alizarin is CI4H3O4:
2. Reduction of alizarin with zinc dust at 400oC produces anthracene. This indicates
that it has the same carbon skeleton as that of anthracene.
3. Alizarin reacts with acetic anhydride to form a diacetate. This indicates the
presence of two hydroxyl groups in the molecule.
4. Alizarin can be prepared by condensing phthalic anhydride and catechol in the
presence of sulphuric acid at 180oC. This shows that alizarin is a dihydroxy derivative
of anthraquinone and both – OH groups are substituted in the same benzene ring.

The above facts limit our choice to two structural formula for alizarin.

26
5. Alizarin on nitration yields two isomeric mononitro derivatives, both of which on
oxidation give phthalic acid. This shows that in each of these derivatives, the – NO2
group is substituted on the hydroxylated benzene ring.
Let us now write down the possible mononitro derivatives from (A) and (B).
Mononitro derivatives from (A):

2.5.3 DYE CLASSES ACCORDING TO APPLICATION

1. BASIC DYES
The colours are very bright, but not very fast to light, washing, perspiration. Fastness
is improved if they are given an after-treatment or steaming, e.g. French Silk dyes are
basic dyes and should be steamed to fix.

2. ACID DYES
These are acidified basic dyes, intended for use on protein fibres but can be used on
nylon and acrylics. They have a fair light fastness but poor wash fastness

3. PREMETALLIZED DYES
These are an acid dyes with the addition of one or two molecules of chromium. The
dyesgive mutetonings, not unlike those of natural dyes. They are the synthetic dyes
mostly used by weavers who dye their own yarns.

27
4. DIRECT DYES
These substantive dyes colour cellulose fibres directly in a hot dyebath without a
mordant, to give bright colours. They are not very fast to light or to washing. Direct
dyes are generally any dyes which use salt as their only fixative, e.g. Dylon dyes (not
to be confused with reactive dyes, which use salt plus other chemicals).

5. AZOIC (NAPHTHOL) DYES

These are another sort of direct dye, but ones that are extremely fast to washing,
bleach and light. They are intended for cellulose fibres and can be used successfully
on protein fibres, although the colours are different. These dyes are widely used all
over Asia and Australia for batik and direct application. They can be used to give
interesting texture colour effects on fabric, thread or paper. Their use for straight silk
painting is minimal because of the difficulty in achieving evenness of painted colour.

6. DISPERSE DYES
Originally developed for acetate fibres, these are now the major dyes for synthetics.
They are not soluble in water, but in the actual fibres themselves. They require a
carrier to swell the fibres so that the finely ground particles can penetrate. They are
dyed hot, like direct dyes, but do not use salt. Disperse dyes are widely used for heat
transfer printing (Polysol). Dye is printed or painted onto paper and heat pressed onto
fabric. Prints have excellent light and wash fastness and strong bright colours. Their
major disadvantage is that only synthetic fabrics can be used.

7. VAT DYES
Vat dyes are the fastest for cellulose fibres. The dye is made soluble with alkali, put in
a 'vat' with a reducing agent, usually sodium hydrosulphite, which removes all oxygen
from the liquid, and the fabric is dyed, then oxidized in the air to achieve the true
colour. Synthetic indigo is a characteristic vat dye, but there are many colours
available

8. REACTIVE DYES
Reactive dyes are the most recent of dyes. These are the most popular in the world
among fibre and fabric artists, used at first only by surface designers, but recently by
weavers as well. There are now reactive dyes for a wide range of fibres, e.g. cotton
(PROCION), silk and wool (PROCILAN). The dye actually reacts with the fibre
molecules to form colour and is, as a result, extremely fast to both light and washing.
There are hot and cold water reactive dyes, in fact there is a dye for almost every
need. They can be most successfully used for silk painting, with a much better colour
fastness than the traditional basic dyes, and are already used by batik artists. we can
identify a reactive dye by the alkali used to set off the fixation process, which requires
time to take place (silk and wool reactives uses acetic acid). Assistants used are salt,
soda ash and resist salt, and sometimes bicarbonate of soda and urea. Reactive dyes
are equally suited to screen printing polychromatic printing, fabric painting yarn and
piece dyeing.

2.6 Dyestuff Selection

Fastness is always influencedby the type and constructionand the treatment (heat
setting of the fiber, and the typeand family of dyestuff.Dyes should show similar

28
diffusionand trichromatic behaviorand fixation rates. The combi-nation of fibers, dyes
and auxiliaries must be selected carefully

29
2.7 Dyes used for Textile Industry
Dyes for the textile dyeing can also be grouped according to the fibres to which they
can be applied. The strength of the dye-fibre attraction is called “Affinity”. Each class
of dye has a unique chemistry, structure and way of bonding to the fibre. Colour
consents are now being enforced and therefore dye fixation levels are becoming more
important. Selection of the right dyes helps to minimise effluent losses. Typical dye
fixation levels for most of the dye classes are shown in the table

30
3.1 Dyeing

Dyeing is the application of color to the whole body of a textile material with some
degree of color fastness. Textiles are dyed using continuous and batch processes and
dyeing may take place at any of several stages in the manufacturing process (i.e., prior
to fiber extrusion, fiber in staple form, yarn, fabric, garment). Most of textile dyeing is
done in finishing departments of basic textile manufacturing facilities, although there
are also several commission dye houses. From an environmental perspective, dyeing
has typically been viewed as a waste water issue due to large quantities of water,
chemicals, and auxiliaries (such as salt). Dyeing is essentially a mass transfer process
where the dye diffuses in solution, adsorbs onto the fiber surface, and finally, within
the fiber. Dyeing is complicated by the fact that there are many sources of color
variations, such as dyes, substrate, and preparation of substrate, dyeing auxiliaries
used, and water. Processing variables such as time, temperature, and dye liquor ratio
(pounds of dye bath to pounds of cloth) also affect dyeing results. There are hundreds
of dyes within several dye classes, each of which exhibits different results when
applied to different types of fabric. Various types of dyeing machines are used for
both continuous and batch processes. Every dye system has different characteristics in
terms of versatility, cost, tension of fabric, use of carriers, weight limitations, etc.
Dyeing systems can be aqueous, non-aqueous (in organic solvents), or use
sublimation (thermosal, heat transfer). Hydrophilic fibers such as cotton, rayon, wool,
and silk, are typically easier to dye as compared with hydrophobic fibers such as
acetate, polyesters, polyamides, and polyacrylonotriles. The four basic steps in the
dyeing process are: dissolving or dispersing dye; diffusing dye onto the fiber surface;
absorbing dye onto the fiber surface; and diffusing dye into the fiber. Batch dyeing
involves moving the dye liquor through the goods or moving the goods through the
dye liquor. The textile material is immersed in the dyebath during the entire period of
dyeing. In batch dyeing, a certain amount of textile substrate, usually 220 to 2200
pounds, is loaded onto a dyeing machine and is brought to equilibrium or near
equilibrium with a solution containing the dye. Once immersed in the dyebath,
because the dyes have an affinity for the fibers, the dye molecules leave the dye
solution and enter the auxiliary chemicals and controlled dye bath conditions (mainly
temperature) accelerate and optimize the action. The dye is fixed in the fiber using
heat and/or chemicals after which the substrate is washed to remove unfixed dyes and
chemicals. There is a trend to use of lower liquor ratios (pounds of dye bath to pounds
of cloth) in batch dyeing, which lends benefits such as faster heating/cooling and less
waste. Batch equipment can usually be purchased as atmospheric (operated below 212
°F) or pressurized (operated to about 280 °F) machines. Most batches dyeing are
being done using pressurized machines, although some facilities use atmospheric
machines, especially for fabric dyeing. Atmospheric dyeing might be required for
fleeces and stretch fabrics, such as Lycra®, which typically cannot be dyed using jet
equipment. Dyeing processes in pressurized machines release no HAP emissions to
the atmosphere since the process is totally enclosed and the pressure is released at the
end of the dyeing process by cooling the dye bath which is subsequently drained
before opening the dyeing machine. However, in some cases, the drying of the
pressure-dyed substrate releases HAP emissions. Continuous processes typically
consist of dye application, dye fixation with chemicals or heat, and washing. Almost
all continuous dyeing is done at atmospheric pressure. Continuous dyeing is usually
used for long runs of polyester/cotton fabrics and involves immersing fabrics in a
relatively concentrated dye bath for short periods. Textiles are fed continuously into a

31
dye range at speeds usually between 540 and 2690 feet per minute and a concentrated
solution of dyes and chemicals (held in pads) is moved evenly and uniformly to the
goods with thorough penetration. A pad mangle helps apply pressure to squeeze dye
solution into the fabric and the dye is usually diffused or fixed by heating in a steamer
or oven. Dye fixation on fiber occurs much more rapidly in continuous dyeing as
compared to batch dyeing. After fabrics are dyed, they are dried in ovens or tenter
frames after washing to remove un-reacted chemical or loose dye. Fabric that is
processed through atmospheric batch dyeing is not dried at the dye range; it is sent to
finishing and may be finished wet or dry. Various classes of dyes can be used, e.g.
disperse for synthetics and direct for cellulosics. Dyes used in the textile industry are
mostly synthetic and are derived from coal tar and petroleumbased derivatives. Dyes
are sold as powders, granules, pastes, liquid dispersions, and solutions.Not only are d
yes applied in different ways, and they also impart color using different mechanisms.
Dyes can be classified according to chemical constitution or method of application.
Dyestuffs can work on principles of electrostatic bonding, covalent bonding, or
physical entrapment. For example, acid dyes work through the mechanism of
electrostatic bonding, whereas disperse dyes work by physical entrapment. Different
dye classes exhibit different affinities depending on the type of fiber, although even
dyes within the same classes can show wide affinity variations. They also exhibit
different properties such as their fastness under end use conditions such as light,
laundering, or dry cleaning. Various combinations of chemical auxiliaries and process
conditions (temperature and pressure) may be used to better fix the dye on the fabric
or impart specific characteristics. For example, a dye bath may contain the dyestuffs
along with appropriate auxiliaries such as wetting agents and also specific chemicals
such as acetic acid or sodium hydroxide. The use of higher temperatures and
superatmospheric pressures have reduced the need for dye carriers (chemical
accelerants) that were required at lower temperatures for the use of disperse dyes on
synthetic substrates, such as polyester.

Staining:
Staining is an unpleasant of dyeing in the area that we do not want

3.2 A BRIEF HISTORY OF DYEING.

Ever since primitive people could create, they have been endeavoring to add
color to the world around them. They used natural matter to stain hides, decorate
shells and feathers, and paint their story on the walls of ancient caves. Scientists have
been able to date the black, white, yellow and reddish pigments made from ochre used
by primitive man in cave paintings to over 15,000 BCE. With the development of
fixed settlements and agriculture around 7,000-2,000 BCE man began to produce and
use textiles, and would therefore add color to them as well. Although scientists have
not yet been able to pinpoint an exact time where adding color to fibers first came into
practice, dye analysis on textile fragments excavated from archaeological sites in
Denmark have placed the use of the blue dye wood along with an as yet unidentified
red dye in the first century CE.

In order to understand the art and history of dyeing, we must first understand
the process of dyeing itself. According to Webster’s dictionary, dyeing is “the process
of coloring fibers, yarns or fabrics by using a liquid containing coloring matter for
imparting a particular hue to a substance.” There are three basic methods of

32
“imparting a particular hue to a substance.” The first is by staining an item, a without
the benefit of some sort of chemical fixative to preserve the color. The next is the use
of pigmentation, wherein the color is fixed to the surface of an object by another
adhesive medium. A true dye is when the color of a substance is deposited on another
substance in an insoluble form from a solution containing the colorant.

Natural dyes can be broken down into two categories: substantive and
adjective. Substantive, or direct dyes, become chemically fixed to the fiber without
the aid of any other chemicals or additives, such as indigo or certain lichens.
Adjective dyes, or mordant dyes, require some sort of substance, (usually a metal salt)
to prevent the color from washing or light-bleaching out. Most natural dyes are
adjective dyes, and do require the application of a mordant (the metal salt) solution to
the fibers at some point in the dyeing process. Aluminum and iron salts were the most
common traditional mordants, with copper, tin and chrome coming into use much
later. In rural areas where these metals were not widely available, plants were also
used as mordants, especially those that have a natural ability to extract such minerals
from the earth, such as club moss. Most ancient and medieval dyers mordanted their
yarns and fabrics before dyeing them. Alum and Iron were used as mordants in Egypt,
India and Assyria from early times, as there are many alum deposits in the
Mediterranean region. Medieval dyers used alum, copper and iron as mordants, and
cream of tartar and common salt were used as to assist in the dyeing process. </<
b>B>

Different fibers also have different tendencies to absorb natural and synthetic
dyes. Protein and cellulose fibers (the two main divisions for fibers used historically
in spinning and dyeing) need to be mordanted differently because of their structural
and chemical composition. Mordants to cellulose fibers such as cotton and linen
usually involve the use of washing soda or tannins to create an alkaline dye bath.
Tannins (plantstuffs, such as oak galls containing tannic acid) are widely used in
dyeing cellulose fibers as they attach well to the plant fibers, thus allowing the dyes to
attach thmselves to the tannins, wheras they might not be able to adhere to the fibers
themselves (Tannins are sometimes classified as mordants in and of themselves, but
are usually considered a chemical to assist in the dyeing process.) Mordants for
protein fibers, like wool and silk, are usually applied in acidic dye-baths. Alum with
the assistance of cream or tartar, is the most common mordant used to assist the dyes
inn taking to the fibers.

Since the difference in mordanting different fibers has been mentioned, it

would remiss not to spend a moment on the historic nature of the fibers themselves.
Wool, a protein-based fiber, has been found in Europe dating back to 2000 BCE. It
was a common medieval fabric in both dyed and natural colors, and was processed by
both professional manufacturers and housewives. Silk, another protein-based fiber,
was imported from China to Persia as early as 400-600 BCE. It became quite popular
in the Late Middle Ages, and major silk manufacturing centers were set up in France,
Spain and Italy. These silk production centers also became centers of dye technology,
as most silk was dyed and required the highest quality dyes available. Cotton was
considered a luxury fabric, as it was imported all the way from India and usually dyed
or painted before it was shipped. Cotton was also valued because of the brightness
and colorfastness of the dyes used to color it, and also for its use in making candle
wicks. Samples of cotton fabrics have been found in India and Pakistan dating to 300

33
BCE, but it did not appear in Europe until the 4th century. Cotton waving
establishments were formed in Italy in the 13th & 14th centuries ut they did not make a
significant economic impact on the industry as they produced a coarser quality of
fabric than the imported fabric, and therefore had difficulty in obtaining a good supply
of cotton fiber.

Scientists are almost certain that dyeing was practiced throughout the world,
but it is difficult to obtain proof on this for two reasons. First, not all cultures left
written records of their practices. Second, because of the wide variance of
environmental conditions and degree of geological disturbance, it is not easy to fine
well-preserved evidence of dyed textiles in many archaeological sites. A Chinese text
from 3,000 BCE lists dye recipes to obtain red, black and yellow on silks. Ancient
Indian texts describe several different yellow dyestuffs, how to obtain reds from the
wood and bark of certain trees, and also notes the use of indigo to create blues on
cotton. In central and South America they dyed bast fibers (plant fibers) in shades of
red and purple with the bodies of the cochineal insects.

A Greek artifact known as the Stockholm Papyrus details dyestuffs and

techniques in almost a recipe fashion as it was practiced Egypt in the third and fourth
centuries CE. The great detail in which the preparation of the fibers and the dyeing
materials and the dyeing process itself are recorded has led scholars to believe that it
had to have been practiced for thousands of ears previously in order to raise the
process to such a science and art. It discusses mordanting the fibers using alum,
copper and iron oxides to darken or “sadden” the red, blue, green and purple dyes, as
well as the occasional use of tin and zinc. It describes over ten different recipes for
using alkanet (Anchusa tinctoria) root as a dye employing camel and sheep urine,
lentils, vinegar, wild cucumber and barley malt among others as aids to producing
color. It also gave rcipes on obtaining purple hues by over dyeing the alkanet with
woad (Isatis tinctoria), madder (Rubia tinctrum), kermes (made from the dried bodies
of the female shield louse or scale insect (Kermers ilicis)) and the heliotrope plant
(Heliotropium arborescens). Excavated coptic textiles dating from the fourth to the
sixth century CE show use of weld (Reseda luteola) to produce yellow, madder and
woad for dark purple, and blue from indigo (Indigofera tinctoria). Scientists have been
able to date a red obtained from Egyptian madder root from the fourteenth century
BCE.

In the Mediterranean before the advent of Christianity, a whole dyeing

industry arose around Tyrian purple. Tyrian purple is produced from the mucous gland
adjacent to the respiratory cavity within some species of Purpura and Murex species
of shellfish (Schetky, 4). The shells were crushed to extract this fluid, which only
turns purple once it has been applied to the fiber and exposed to light and oxidation
with the air. The Phoenicians, skillful shipbuilders and sailors that they were, scoured
the coastlines for sight of these whelk shells, and established a dye works and trading
station wherever they found a plentiful population of these shellfish. Coastal Indians
of Mexico were also using shellfish, but their delicate method involved blowing and
tickling the shellfish to get them to spit out the dye precursor directly onto the cotton
fibers. Even Ireland can produce archaeological evidence of dyeing with the native
dog-whelk shells in the seventh century CE. Both Discorides, the Greek physician and
pliny the Elder, the Roman naturalist, mention in their first century works the
preparation and dyeing of wool with various shellfish to produce colors of red, blue,

34
purple and violet after first being mordanted with soapwort (Saponaria officinalis),
oxgall or alum. Both authors also mention the use of Indigo from the Orient to obtain
blues, and Herodotus describes its use in a 450 BCE text. Dioscorides also mentions
other dye palants of the ancient world, including madder, saffron (Crocus sativus) and
weld for yellow, and woad for blue. (Walnut shells (Juglans nigra), oak bark (Quercus
sp.), pomegranate flowers (Punica granatum) and broom (Genista tinctoria) were also
used in conjunction with various mordants; but galls formed on trees could mordant
themselves, being high in tannic acid.

In Europe the art of dyeing rose to new heights with the diversity of climate,
culture and migration/invasion waves. This further influenced by the direct impact of
trade instigated by the Crusades and furthered by the growing cultural awareness of
the Renaissance period-everyone in Europe wanted the exotic, colorful dyestuffs from
the Orient, and later rom the Americas. Caravans of camels would cross the Gobi
desert for centuries bringing goods from China to the Mediterranean. By the 12th
century the two main trade routes for imported dyestuffs headed through Damascus:
the first led rom Baghdad to Damascus to Jerusalem and Cairo, the other went to
Damascus to Mosul to the Black Sea to Byzantium (Istanbul).

Venice was one of the major early centers for imported dyestuffs, supplying
Brazilwood (Caesalpinia sappan) from the East, lac (another insect dye) and indigo
from India from the fifteenth century CE onward. Dyers of Italy soon became adept in
their use, in 1429 the Venetian dyer’s guild wrote a book for its members containing a
number of different dye recipes, including Brazilwood and lac. The Plictho de Larti de
Tentori by Venetian author Giovanni Ventur Rosetti (sp-also listed as Giovanventura
Rosetti) in the 1450s lists instructions for using both lac and indigo, as well as 217
other recipes for dyeing cloth, linen, cotton and silk with many varieties of dyestuffs.
It would remain the best source for dyeing instruction for the next 200 years.

From Venice the dyestuffs were traded by ship around the coast of France to
Flanders, Southampton and London; in the Mediterranean at Florence, Pisa and
genoa; and northward on the continent to the distribution centers of Basle and
Frankfurt. Basle was a noted center of trade for saffron, the expensive yellow
obtained from certain species of crocus. In later years crocus were grown in that area
directly, and the crop became such a vital part of the local economy that they crocus
was featured on the city’s coat of arms. Frankfurt housed trade fairs from the twelfth
to fourteenth centuries that dominated the trade of man dyestuffs, but mainly that of
locally grown woad, the only blue dyestuff available to European dyers before the
coming of indigo. Many regions in Germany specialized in growing and processing
the woad through its complex fermentation process, and strict legislation was placed
on every aspect of the trade.

The government of Spain controlled the trade of cochineal, the red dye from
the bodies of the Cochineal bugs of Central America. In 1587 approximately 65 tons
were shipped to Spain, and from there northward throughout Europe. Italian dyers
shunned cochineal in favor of the already established dye kermes, made from the
dried bodies of the female shield louse or scale insect. It’s use was first recorded in
1727 BCE and it was long the standard red dye for silk, wool and leather, but the
intense colorific value and relative cheapness of cochineal soon eliminated most of
the kermes use in England, so Spain hung on to control of their lucrative monopoly.

35
 European dyers reached their height of skill in the thirteenth century, mainly
use to the guild systems who vigilantly maintained a high standard of quality. In many
countries dyers were graded by the guild system, the master dyers being allowed to
use the major “fast” dyes while their lesser colleagues were restricted to the slower,
“fugitive” dyes. In some places it was forbidden to possess, let alone use, major
dyestuffs unless you were a member of a guild. In Germany, the dyers and wood
workers were regulated by the guilds, each grower having to present his crop to a
“sworn dyer” to determine its quality, weight and condition before it could be sold.
English producers of wood had fewer restrictions mainly that of a proclamation in
1587 to restrict growers to certain field size and ensure that no wood mills were sited
within three miles o a royal residence, market town or city because of the highly
offensive odor they emit. Even the local doctors in Venice in 1413, city fathers, to
prohibit dyeing with either wood or ox-blood after March first because of the
“unhealthy smell.”. France had developed an extensive and efficient textile industry
by the 13th century and also increased the dyers craft by developing varied techniques
to achieve additional colors from the basic dyestuffs. At the end of the 16th century,
there were over 220 master dyers listed in Paris alone.

While the powerful guild system had numerous dyestuffs with which to blend
their color palates of fiber for the bluebloods and wealthy merchants, dyeing in the
lower classes was a bit more restrictive. Without the money (or connections) to buy
indigo, cochineal and turmeric, clothing in the country tended to natural colours-
whites, blacks, browns, grays, and tans of the natural colors of the fibers themselves,
with the reds, greens and yellows of local plants used for both food, medicine and
dyes. In short, home dyers used any plants they could lay their hands on that world
give a good color. Some colors were even derived accidentally. Washing bee hives in
preparation for making mead could yield yellows and gold’s. Blackberries and
Bilberries that stained the fingers of pickers could also be used to achieve pale blues
and purples, although these were not often color or lightfast. In England, the
multitudinous variety o lichens and mosses produced greens, grays and browns.

By the seventeenth century a world-wide shipping and trading network was in

place, allowing dyestuffs from all parts of the world to be brought to Europe.
Legislation from earlier centuries to protect the growers and users of specific
dyestuffs was overturned in favor of new demands and standards set by the growing
consumer-focused society who wanted more colors and better quality. In the
eighteenth and nineteenth centuries the practice of colonialism insured that there
would always be a supply of foreign dyestuffs, and the Industrial Revolution met the
demands of large-scale productions while finding new ways to make he colors
brighter and longer-lasting to wear and washing.

As textile weaving technology advanced with the advent of machines to spin,

design and weave fabric, dyers were forced to be able to produce dyes with exact
shades, matching color lots and most importantly, ones that would stand “to the new
mechanical and chemical processing. In addition, exporters wanted colors that would
stand up to tropical sunlight and still be exotic enough for foreign tastes. Dyers in turn
demanded from their suppliers purer chemicals and dyestuffs of consistent quality.
Hand in hand, dyers, manufacturers, chemists, and dyestuff producers worked hand in
hand to keep up with the progress of technology. Chemists in many countries had

36
found a means of extracting highly concentrated powders or pastes from traditional
dyestuffs that made stronger colors, such as cochineal carmine and madder garancine.
Other procedures were used to extract indigo that gave us sulphonated indigo and
Saxon blue. A few novel dyes (precursors of future chemical dyes) such as the yellow
obtained from picric acid also made an appearance. With the tremendous rise in the
interest of Chemistry in the mid nineteenth century, several important innovations in
dyeing came about. W.H. Perkins, a student of celebrated European scientist Wilhelm
von Hoffman, accidentally discovered the first synthetic dye in an attempt to
synthesize quinine. The 18-year old student’s purple precipitate, later called
mauviene, was quickly put into industrial application, allowing the young Perkins to
start his own factory in London to commercially produce his dyestuff. Two years
letter a synthetic red dye called magenta or fuchsine was patented in France, and
hardly a year passed until the end of the century without a new synthetic dye being
patented.

Eventually, the old natural dyes lost popularity in favor of the newer synthetic
ones. By the end of the nineteenth century a few Scottish tweed producers were the
only ones still using natural dyes, and now the use of natural dyes on a commercial
scale barely exists, mainly in remote areas where people have either little access to
synthetic dyes or a vested interest in retaining their ancient dyeing customs. Use of
natural dyes is gaining popularity again with the renaissance in hand crafting, most
notable in the fields of spinning and weaving, basketry, papermaking and leather craft.
There is also renewed scientific and historic interest in natural dyeing, both to help
identify dyestuffs in recently discovered archaeological finds and to preserve the dyed
textiles housed in museums and private collections. As Su Grierson says in her book
Dyeing and Dyestuffs, “Whilst the dyeing industry of today keeps pace with modern
science, the future use of natural dyes will also follow a new path, but one firmly
rooted in tradition.”

3.3 MODERN CONCEPTS OF THE THEORY OF DYEING

It appears that the mechanism of dyeing depends on the nature of both the dye
and the fibre. Textile fall into two main groups : vegetable and animals vegetable fibre
is cellulose fibre, e.g. cotton, lined, flax, hemp and jute. Animal fibres are protein
fibre, e.g. wool, silk and leather.

There is also a third type of fibres, the artificial and synthetic fibres e.g.
rayon’s (cellulose-type) and nylons (protein-type).

Dyeing was already practiced inn ancient times and has undergo many
changes in its development. The first hypothesis of purely mechanical character
attempting to explain the processes underlying dyeing was advanced in 1740-41.
According to this hypothesis the fibre has pores which particles of dyes penetrate at
high temperature; when the dye bath cools, the pores of the fibre contract, thus fastly
retaining the dye. The problem of the different behavior of dyes in respect to various
kinds of the fibre was not referred to.

For about one and half a century, the dyeing process was considered was only
from the mechanical stand point without paying due regard to chemical essence o the

37
process, only at the end of the 19th century, when chemistry was developed, the
chemical nature of dyeing process was revealed.

New theories is come replace the old erroneous ones. thus, as a result of the
work carried out by two groups of English chemist-S Neale collaborators and J.
Belton, it was found that inn the process of dyeing, the was first absorbed by the
external surface of the fibrous materials and than started to diffuse inside in the
molecular-disperse state. this was the determining feature of the kinetics of the
process.

At organic fibres, cellulose,, protein and synthetic have one feature in

common; they are all macromolecules having a linear structure and more or less
oriented along the fibre axis. Macromolecules contain a great number of identical or
similar atoms linked by covalent bond. Most high polymers from which the fibres are
composed contain active functional groups, such as hydroxyl, carboxyl, nitrile and
amino groups. In cross longitudinal directions, macromolecules are interconnected by
the force of intermolecular attraction and in separated cases, by chemical bonds (wool
keratin). The super molecular structure of the fibrous polymer is characterized y chain
having in some portion a very regular arrangement crystalline region) and a maximum
density of packing and in other portions, regions with less regular arrangement
(amorphous region) and a maximum density of packing and in other portions, regions
with less regular arrangement (amorphous region) with loose structure.

3.3.1 Sticking of dyes to fibres:

This depends on the dye and the fibre to which the dye is attached. Protein-based
fibres such as wool and silk have free ionisable CO2H and NH2 groups on the protein
chains which can form an electrostatic attraction to parts of the dye molecule. For
example the sulphonate group, SO3 -, on a dye molecule can interact with a NH3 +
group on the protein chain.

Cotton is a polymer with a string

of glucose units joined together.
Indigo which is used to dye
denim jeans is a vat dye. Indigo
is insoluble in water. The reduced
form of indigo is soluble. Cotton
is soaked in a colourless solution
of the reduced form. This is then
oxidized to the blue form of
Indigo which precipitates in the
fibres. Direct dyes are applied to
the cotton in solution and are
held to the fibres by hydrogen
bonds and instantaneous dipole-
induced dipole forces. These are weak compared with covalent bonds hence these
dyes are only fast if the molecules are long and straight. Fibre reactive dyes actually
form covalent bonds with fibre molecules and are therefore extremely colour fast. A
dye molecule is reacted with the molecule trichlorotriazine:

38
 Trichlorotriazine can react with either
–OH groups (present in cotton) or –
NH groups (present in wool and
nylons), thus effectively bonding the
dye to the fabric.

3.2.2 DYE AND DYE SOLUTIONS

All water-soluble dyes use in the textile industry is electrolytes. In the aqueous
solution dissociate into ions with positive and negative charge :(a) into the dye
coloured ion and (b) into the usual colorless compensation ion with an opposite
charge.
The solution properties and the behavior or dyes in course of the dyeing
process are of great interest. It is established that the salt of the dyes in the solution
are electrolytically dissociated and their ions may from more or less large aggregates.
The possible types of dye ions association in aqueous solution, according to the data
presented by E. Valko, may be represented by the following three schemes (where A
and B are an anion and a cation respectively)

I II III
For the dye cation C+ (nC)n+ m(CA)nCn+
For the dye anion A- (nA)n- m(CA)nAn-

Scheme I represent the complete dissociation of the dye into ions, scheme II
association of the dye into ions and scheme II aggregate particles including
molecules.

39
Scheme I is typical of an electrolyte and scheme III of a colloidal particle. The
intermediate from (scheme-II) called the ionic micelle is characteristic of colloidal
electrolytes.
The size of dye particles in solution usually depends on the temperature as
well as on the concentration of the electrolytes contained in the solution.

3.2.3 SURFACE POTENTIAL OF FIBRES

When fibrous materials is immersed in water or in aqueous solution, important
electrochemical phenomena take place due to the absorption of certain ions from the
solution or to the dissociation of ionic groups contain in the fibres. Electrical change
formed on textile fibre at their immersion into water due to the electrostatic attractive
or repellent forces influence the distribution of coloured ions in the solution, thus
promoting the interaction with the fibre of ions having an opposite charge and on the
contrary, creating an energy barrier the approach to the fibre of ions with the same
charge, e.g. the protein fibre saturated with (positively charged)- NH3 groups is attract
by the negatively charged (acid) dye anions.
+ -
-NH3 + D –NH2D.

Conversely, the negatively charged ions of a direct dye will be repelled by the
surface potential of the cellulose fibre, this potential barrier will have to be overcome
before the ions enter the fibre. Whenever a dye anion will be energy-content of dye
anions can be raise by increasing the temperature of the dye solution. Hence, at higher
temperature, a greater portion of dye ions will e able to overcome the potential barrier
and penetrates into the fibre.

3.2.4 THE NATURE OF THE FORCE BETWEEN THE DYE AND THE
FIBRE MOLECULES
The fixation of dye depends on the physical and chemical properties of the dye
and on the kind and properties of the fibrous material. Evidently, the dye is retained
on the fibre by the physical and chemical forces of interaction. The attractive forces
between dye and the fibre molecules may be classified as follows:
1. Electrostatic attraction between charged sites exists in protein and polyamide
fibres.
2. Attraction by induction between ionic dyes and non-ionic dyes fibre. Induction
forces of second type above are very small and may be ignored.
3. Polar van der wall’s forces such as hydrogen bonds, e.g. such polar force are to
Hydrogen adjacent molecules of water as follows :

H H H H

H-O H-O H-O H- O

Non-polar van der wall’s dispersion force, e.g. in aqueous dye-bath, non-polar
bonding will occur between surface which are predominately hydrophobic.

4. Chemical forces, e.g. the sole example of a chemical bond between cellulose and
de molecules is in the case of reactive dyes where a covalent bond is performed

40
 between hydroxyl groups and reactive halogen containing groups in the dye
molecules.

3.3 Flow diagrammatic representation of dyeing process:

3.4 CLASSIFICATION OF DYEING PROCESS

1. Mass-coloration of the molten fibers This method is for dyeing the molten
fibers or plastic chips or textile polymers with pigment dyes. After that, the molten or
polymers will extrude from a spinneret to form fibers. Normally, the synthetic fibers
are added with white pigment in order to give a hiding power (non-see through
fabrics).

Advantage: give excellent

fastness

Disadvantage: very difficult to

clean

2. Fiber Dyeing is the method

of dyeing fibers before blending
with other colors to give fancy
yarns or fabrics.
Note: This is used for special purposes only.

41
3. Yarn Dyeing is the method of dyeing yarns in forms of hanks or packages dyeing.
This will give Scottish’s style fabrics, carpet with many colors and styles.
Note: This is used in hand loom weaving in the Northern and North-eastern parts of
Thailand.
4. Fabric Dyeing is the method after weaving, knitting, or non-woven to make fabrics.
This is very popular method of dyeing as the dyed fabrics will be processed further to

garment industries very easily. Dyeing forms of the fabric dyeing can be used in 2
ways:
1. Open width form using the fabrics to spread without any creases and dye them.
2. Rope form using the fabrics with the form like a rope (many creases and look like
“a rope”)

3.5 Some people classify into:

1. Exhaustion Process

This method is using lot of water as shown in “Liquor Ratio (ratio between water and
goods)” This should immerge the goods into dye solution for a long time in order to
let the dye penetrate into the goods. This will lead to produce more waste water than
the continuous process.
Advantage: inexpensive, no need to train the worker to look after and run them
properly.
Disadvantage: lots of water needed, very slow process (60-120 mm/batch.)
2. Continuous Process This method is designed by putting different machinery into a
sequence so that it can produce the dyed fabric in one pass.

Advantage: very fast process (10-100 m/min), small amount of water in the process.
Disadvantage: very expensive, need to train the worker to look after and run them
properly. Example of the open width form fabric dyeing

42
.

Examples of the rope form fabric dyeing loading and unloading reel heat exchange

5. Garment Dyeing: This method is the last process of the dyeing of goods.
However, the penetration of the dye solution may not be completely passed to the
fibers such as between the seams, buttons, zippers etc. Normally, it is used for

lingerie, socks, sweater dyeing etc.

43
44
4.1 DEFINATION:
a chemical or formulated chemical product which enables a processing operation in
preparation, dyeing, printing or finishing to be carried out more effectively, or which
is essential if a given effect is to be obtained’.

4.2 NECESSITY OF AUXILIARIES IN TEXTILE DYEING

(a) To prepare or improve the substrate in readiness for coloration by
– scouring, bleaching and desizing
– wetting
– enhancing the whiteness by a fluorescent brightening effect
(b) To modify the sorption characteristics of colorants by
– acceleration
– retardation
– creating a blocking or resist effect
– providing sites for sorption
– unifying otherwise divergent rates of sorption
– improving or resisting the migration of dyes
(c) To stabilize the application medium by
– improving dye solubility
– stabilizing a dispersion or solution
– thickening a print paste or pad liquor
– inhibiting or promoting foaming
– forming an emulsion
– scavenging or minimizing the effects of impurities
– preventing or promoting oxidation or reduction
(d) To protect or modify the substrate by
– creating or resisting dye ability
– lubricating the substrate
– protecting against the effects of temperature and other processing conditions
(e) To improve the fastness of dyeings, as in
– the after treatment of direct or reactive dyes
– the after treatment of acid dyes on nylon
– the chroming of mordant dyes on wool or nylon
– giving protection against atmospheric influences, as in UV absorbers or
inhibitors of gas-fume fading
– back-scouring or reduction clearing
(f) To enhance the properties of laundering formulations (fluorescent brightening
agents).

4.3 Some have more than one purpose

An auxiliary to improve dye solubility may also accelerate (or retard) a coloration
process, or an emulsifying agent may also act as a thickening agent; pH-control agents
may both stabilize a system and also affect the rate of dye sorption. Undesirable
effects during handling, through effluent discharge to surface waters, through
discharge to the atmosphere (e.g. via stenter gases), through consumer contact with
the finished product (e.g. skin sensitivity) or during the eventual disposal of solid
wastes (e.g. incineration or landfill)

45
4.4 CLASSIFICATION:
A) Non-surfactants
B) Surfactants,

Non-surfactants
Simple electrolytes, acids and bases, both inorganic and organic. E.g., sodium
chloride, sodium acetate, sulphuric acid, acetic acid and sodium carbonate, together
with complex salts (such as sodium dichromate, copper(II) sulphate, sodium
ethylenediaminetetra-acetate, sodium hexametaphosphate),
Oxidising agents(hydrogen peroxide, sodium chlorite)
Reducing agents (sodium dithionite, sodium sulphide).
Anionic polyelectrolytes such as sodium alginate or carboxymethylcellulose, used
mainly as thickening agents and migration inhibitors, also fall within the class of
nonsurfactants;
So too do sorption accelerants such as ophenylphenol, butanol and
methylnaphthalene, although they normally require an emulsifier to stabilise them in
aqueous media.
Fluorescent brightening agents (FBAs) form another large class of nonsurfactant
auxiliaries

Surfactants:
Organic in nature and more complex structures
DEFINITION:
‘An agent, soluble or dispersible in a liquid, which reduces the surface tension of the
liquid’ In coloration processes this reduction in surface tension usually takes place at a
liquid/liquid or liquid/solid interface, although liquid/gas interfaces are also
occasionally important

46
47
4.5 Classification of Dyeing Auxiliaries according to function

Dyeing Auxiliaries
1. Sequestrant.
2. Lubricants / Anticreasant.
3. Pretreatment Chemicals
4. Levelling and Dispersing Agent.
5. Sewuestering, Dispersing and Levelling Agentfor Reactive dyeing.
6. Antifoam.
7. pH Control and buffer system.
8. Desizing Agent
9. Yarn Lubricant
10. Mercerising agent
11. Dyefixing agent
12. Optical Brightener.
13. Soaping Agent / Washing off Agent.

4.5.1 Sequestrant:

The most undesirable impurities in Fibre, Common salt, Glauber salt, Caustic
Soda and Soda ash are the di- and tri-valent cations, e.g., Ca ++, Mg ++ Cu ++, Fe+++ etc.
These ions increase hardness of the process bath and generate iron oxides in the bath.
Calcium and Magnesium reacts with alkali and precipitates as a sticky substance on
the textile material, which creates patchy dyeing and discoloration of the fibre. The
ferric oxide with cellulose and creates small pinhole on the fibres also damages the
machinery by scale formation in the nozzles and base.

To overcome these deleterious effects in the scouring and bleaching bath

adequate amount of sequestrant must be used. Sequestrants prevent di-and tri-valent
metal ions, e.g., Cu++, Fe +++ , Mn ++, Ca++, Mg++ etc from interfering with the
chemical processing of the textile material. It prevents catalytic damage of cellulosic
fibres in bleaching hath during hydrogen peroxide bleaching.

48
 In Dye-bath Ca++, Mg ++, Fe +++ attack the dye molecules and forms aggregates
of molecules which deposits on the fabric as dye spots and also they prevent the
reaction process. Dye bath sequestrant should be of different strength than that of the
scouring and bleaching baths. Because some dyes have metal compounds and if
powerful chelating agents are used than it will attack the metal compound of dye.

4.5.2 Lubricating / Anticreasant.

Wet processing and dye-bath lubricants are used in any operation in which
rope marks, creases, crows feet buffing, abrasion can occur on textiles. In low liquor
ratios, full-loaded winches and jets when heavy materials re processed, fiber lubricant
is essential. The basic requirement is that is it should from a thin uniform protective
coating around the fiber to lower the surface friction and flexural rigidity, thus
minimizing the formation of durable creases during high temperature processing. The
most suitable lubricant should have the properties so that it helps to emulsify, it does
not undergo phase separation with extreme changes in pH and temperature, e.g. it is
stable in high temperature and over a wide range of pH; and it should have excellent
compatibility with all the chemicals in treatment bath, Suitable products are relatively
hydrophobic surfactants, many of which also contain a proportion of solubilized or
emulsified oil or wax.

4.5.3 Pretreatment Chemical :

a. Detergent & Wetting agent for cellulosic fibers.
b. Oil stain remover
c. Hydrogen peroxide Stabilizer.
d. Single0Bath Scouring & bleaching Agent.
e. Hydrogen Peroxide Killer;
f. Biopolish.

In both 1-bath and 2-bath process, a number of important auxiliaries with specific
properties are necessary along with 2-basic chemicals, as shown in the blocks below,
Pretreatment process Bleaching bath
2. Bath process 1. Bath process
Scouring/Boiling off
Bleaching Bath
Detergent & Wetting
Detergent & Wetting Agent
Agent Oil stain remove
Antifoaming Agent
Basic Chemical:
Sequestrant
Alkali
Lubricant/Antecreasant
Oil stain remove
Peroxide Stabilizer
Bleaching Bath Basic Chemical:
Alkali
Detergent & Wetting Agent Hydrogen Peroxide
Antifomking Agent
Sequestrant
Lubricant/Antecreasant
Peroxide Stabilizer
Basic Chemical:
Alkali
Hydrogen Peroxide
49
 Peroxide killer is used after both processes for eliminating residual hydrogen
peroxide.
Detergent & Wetting agent or Cellulosic fibres:

The purpose of scouring is to reduce the level of fats, waxes, oils, dirt and so
forth on the substrate. Apart from the aesthetic benefits of clean fabric, the major
technical reason for scouring is to improve the extent and uniform of absorbency for
subsequent processes, especially coloration.

In scouring 1, surface-active products function as primary, rather than

auxiliary agents as the basic requirements are for good wetting power and detergency,
the latter property generally including the ability to remove, emulsify and suspend the
extraneous matter in the liquor. Not all good detergents possess good wetting
properties; hence a combination of surface-active agents to provide both wetting and
detergency may be preferable. Detergency can be significantly improved with the use
of additional chemicals usually referred to as “builders” the chief of which
undoubtedly alkali in the form of sodium carbonate or hydroxide.

4.5.4 Levelling and Dispersing Agent:

Unleveled dyeing problems can be of two categories: Gross unlevelness

throughout the material or localized unlevelness e..g. barriness, skitteriness. There are
two fundamental mechanisms that can contribute to a dyeing.
a. Control of the exhaustion dye so that it is taken up evenly.
b. Migration of dye after initially unleveled absorption on the fibre.
c. Non-ionic agent usually from water soluble complexes with the dye, some degree
of solubilization being involved.
d. Ionic agent are primarily dye-of fibre-substantive ; in the former case they tend to
form complexes with the dye and there is competition between the leveling agent
and the fibre for the dye, while in the latter case the competition is between the
leveling agent and the dye for the fibre.

4.5.5 Sequestering, Dispersing and Levelling Agent for Reactive Dyeing :

It increases the solubility of dyes and controls the exhaustion of dyes so that
these are taken up evenly on the substrate. It effectively chelates Ca, Mg ions which
otherwise create while spots on the substrate. It also sequesters other di-and tri-valent
metal ions without impairing the metal complex dyes, and thus yiels uniformly dyed
fabric.

4.5.6 Antifoam:
Where the present and persistence of foam is a nuisance, defoaming agents or
antifoams are used. For maximum efficiency deform should be added to baths when
necessary.

There two groups of defoamers one that is water-soluble surfactants and other
is water insoluble emulsions of silicones of organic-based the most effective
defoamers are where the water-soluble compounds are used as vehicles for silicones
of organic emulsions.

50
4.5.7 pH Control and buffer system :

Many disperse dyes required controlled 4.5-5 and practically all disperse dyes
give good results in this pH range and are much more sensitive to minor changes in
pH. Thus there is greater awareness of the actors that not only determine pH but also
helps to stabilize it against interferences, in particular, from any acids or alkalies
carries over from previous process.

A buffered system is necessary for precise control of pH. By the use of that
tends to resist changes arising from contaminations entering y way of the substrate of
the water supply.

4.5.8 Desizing Agent:

Desizing is essentially a part of the scouring process, and rapid removal of size
is very important in the present trend towards continuous preparation processes.
Starch-based products and especially solubilised starches are still the sizes, most
commonly used on cellulosic goods. The are most frequently removed y enzymes
treatment, which since effect it affects only the starch product ensure that the
cellulosic fibre is undamaged; baterial amkulase id increasingly replacing malt and
pancreatic enzymes. The efficiency of desizing is often taken for granted, whereas
incomplete of uneven size removal is just likely to be the cause of uneven dyeing or
printing as inadequate scouring.

4.5.9 Yarn Lubricant:

In the textile industry, a smooth production process is essential for perfect

results and smooth production needs yarn and sewing thread lubricants. Yarn lubricant
are essential for dyed yarn used in modern knitting machine. They significantly
improve the slip properties of yarn and sewing thread, increased heat resistance, better
sewabilitym, reduced thread breakage and increase the lustre.

4.5.10 Mercerizing Agent:

The objective of mercerizing is to oil the cotton fibre, increase its lustre
strength and dyeability. Traditionally a cold solution of 25-26% by mass of sodium
hydroxide is used, although better penetration and more even treatment is obtained
with the more recent hot mercerizing technique. The addition of a wetting agent to the
mercerizing liquor give better penetration and more even treatment, the main
requirements being for a combination of stability and powerful wetting action.

4.5.11 Dye Fixing Agent:

Properties of a good fixing agent includes good capability with cross linking
agents without promoting yellowing effect; good leveling and migration properties,
does not affect the shade, has good affinity for the fiber, stable to steaming and dry
heat, and improved all round fastness properties of the fabric or yarn. Fixative is
generally used after completing the dyeing or in printing paste.

51
4.6.12 Optical Brightener:

An Optical Brightening Agent (OBA), also called Fluorescent Brightening

Agent (FBA) or Fluorescent whiteners (FW), are strongly fluorescent substance that
emits light in the blue-violet region of the visible spectrum. In the Color Index, OBA
or FBA’s are classified and are given C.I. number, i.e. they are treated as dyes. When
present on a substrate, OBA increase the apparent reflectance of the substrate and
makes it appear “whiter than white”. To evaluate an OBA it is necessary to apply the
product and measure the whiteness, preferably with a spectrophotometer.

4.5.13 Soaping Agent / Washing off Agent:

The important of proper washing after dyeing is painfully known to all dyers,
particularly the difficulty in washing off the unfixed dye in order to meet the required
fastness standard. The main functions of soaping agent are to:
a) Disperse the unfixed substanted hydrolyzed dyes, and solubilise and emulsify these
into the aqueous medium and keep these substances in suspension.
b) Prevent redeposition of hydrolyzed dyes and other particles of colloidal
substance into the textile material.
c) Removes the alkaline earth metal ions which have already deposited on the dyed
material.
d) Prevent the precipitation of insoluble calcium or magnesium salt.

4.5.14 Finishing Chemicals:

The Quality of softness is very difficult to define, although it is often confused with
only lubricity. Softness is more than lubricity, but these other attributes are difficult to
define scientifically. The various products used soften are divided into silicone,
anionic, non-ionic, amphoteric and reactive types, all of which falls under two basic
chemical classes: (a) Fatty acid derivatives and (b) silicon derivatives, by far the most
important softness today are the silicon derivatives and fatty acid cationic types;
however non-ionic softeners is used for textile materials because of its non-yellow
effect and compatibility with OBA. Relevant properties of softeners include aqueous
solubility, exhaustion, durability to washing, and compatibility with other additives to
the textile materials

4.6 Water in the Textile and Carpet Industry

Quality of process water is very critical and important for a successful dye and print
operation. Especially water hardness is of importance. Hard water will result in higher
usage of chemicals, thickeners and in bad results of dyeing and printing. A water
softener is recommended and in any way needed for the water used by the steam
generator. In case of high concentration of other minerals, elements and impurities it
is strongly recommended to use filters, chemicals and other methods to reduce or
remove them.

52
4.7 Thickeners (Gum)

As regards quality played by the flow behavior of the printing paste. This is
influenced by the thickener used. There is an extensive range of products available for
a wide variety of fibers, carpet qualities, dye classes and printing methods .Thickener
is a must in the printing process. It keeps the\dyestuff on top of the fiber to avoid
'frosting'. In addition it prevents the dye from migrating
between the piles.

4.7.1 Thickener for screen printing:

Most thickeners for screen printing are made of Guar,

Xanthan, seaweeds (= natural thickener).These type of
thickeners are relatively in expensive. The thickener is
normally mixed to a so called 'stock thickener'- thickener with a very high viscosity
which is then mixed in a certain portion (about 30-50%) with water, dye and other
additives. The result is there a dye made print paste with a certain viscosity. The
viscosity depends on the printing process and the quality of the carpet.

4.8 AUXILLIARIES USED WITH DIFFERENT DYES:

4.8.1 Dyes for Cellulosic Fibers:

Direct Dyes (Anionic): They can be dyed directly on cellulosic fibers.

Without the presence of salt, when the fibers are immerged in water, it will show

53
anionic charge which repels the dyes. Adding salt into the dye bath, it will reduce
anionic on the fibers so the dyes can get closer and adsorb into the fibers.
Advantage: cheap, easily dyed on fibers
Disadvantage: poor wet fastness and some dyes have poor light fastness.

Textile Auxiliaries:
1. Salt - reduce negative charges on the fibers
2. Water - dyeing media
3. Fixing Agent - enhance wet fastness but usually reduce light fastness

Dyeing Conditions:
(Exhaustion): dyeing lOOoC x 30-90 mm fixing 6OoC x 20 mm.
(Continuous) pad --> dry --> steam --> wash --> soap --> dry

Reactive Dyes (Anionic): They can be dyed on cellulosic fibers. The mechanism is
nearly the same as described in direct dyes.

Advantage: high wet fastness due to covalent bonding (Chemical Bonding) between
fibers and dyes, easily dyed on fibers.

Disadvantage: Expensive.

Dyeing Conditions:

1. Continuous Process:

1.1 Pad-dry-bake This is very easy method for cotton or cotton blends fibers.
1.2 Pad-dry-Pad (Chemical)-Steam This will give brighter and more intense color
than method 1.1.
1.3 Pad-batch This will put the goods into the dye solution and squeeze with 2 rubber
rollers to get rid of excess water and then batch at room temperature for 1-2 days.
2. Exhaustion Process: This method will be used in small factory. Dyeing conditions
will be 40-8OoC for 30-90 mm depending to the types and structures of the dyes.

Textile Auxiliaries:
1. Salt - reduce negative charges on the fibers
2. Water - dyeing media.
3. Soda Ash - excite the dye to link with the fibers with covalent bonding. Therefore,
it enhances wet fastness
4. Fixing Agent - enhances wet fastness for heavy shade but usually reduce light
fastness.

Vat Dye (Anionic when soluble):

The dye is named from the container (Vat) that used for rotting the dye with alkali
solution. This crucial process will reduce the dye from insoluble to soluble dye
(suitable for exhaustion in the cellulosic fibers). Now the manufacturer can synthesize
man-made vat dye.

Dyeing Process:

54
1. Dissolve dye into water (insoluble dye)
2. Vatting process by reducing the insoluble dye in alkali condition. (Soluble dye)
3. Absorb into fibers (soluble dye)
4. After dyeing, oxidize the dye with oxidizing agent (insoluble dye)
5. Wash and soap the goods

Dyeing Conditions:

1. Continuous Process:

1.1 Pad-dry-Pad (Chemical): The solution of the dye is prepared without adding
reducing agent to ensure leveling dyeing. After that, the goods are passed to chemical
bath to reduce the dye into soluble dye and fix within the goods. Oxidizing agent is
added to the goods and converted to insoluble dyes.
1.2 Pad-oxidize-pad-oxidize (many times): This will put the goods into the dye
solution and squeeze with 2 rubber rollers to get rid of excess water, oxidize with the
air and then immerse into the dye solution again and again to allow the dye penetrate
into the goods.

Textile Auxiliaries:
1. Salt - reduce the negative charges on the fibers
2. Sodium hydroxide - adjusts pH to the dyeing bath and makes the suitable
conditions for reducing agent.
3. Sodium hydrosulfite - reducing agent for the vat dyes.
4. Water - dyeing media
5. Oxidizing agents - (Hydrogen peroxide or Acetic acid or Air) oxidize the soluble to
insoluble dye

(Sulfur Dye Anionic when soluble) :

The dyeing process has the same process as described in the vat dye except that using
Sodium sulfide instead of Sodium hydrosulfide.

Dyes for Synthetic Fiber:

Disperse Dye (polyester, nylon, and acetate) (non-ionic): The dye is named from
less water soluble and normally appeared in dispersion in water. The dye shows no
charge due to the groups presented in the dye molecules.

Dyeing Conditions:
1. Insoluble dye in water
2. Less water soluble
3. Water insoluble in polyester fibers

1. Exhaustion Process:

55
1.1 At boil with carrier, this process is suitable for acetate fiber and pale shade
polyester fiber dyeing. Carrier is an auxiliary for swollen fiber in order to allow more
dyes absorbing in. Now the use of carrier is reduced because it may be a carcinogen.
1.2 At l3OoC without carrier with the high temperature, the dyes will be dissolved
into smaller molecules and the void in fiber structure will be opened. This will give
heavy shade.
2. Continuous Process Pad --> Pre-dry (100oC Thermo fixation (18OoC reduction
clearing (RC)

Printing with Disperse Dyes:

With the sublimation property, the dyes can be printed on paper, place the fabric with
a printed paper and then using an iron with high temperature pressed on the paper.
The dyes will transfer from paper to polyester fiber. This is called “Transfer Printing”.

Textile Auxiliaries:
1. Dispersing Agent - makes the dye solution stable and disperses in the dye bath.
2. Acid - adjust pH to the suitable condition for the dye bath.
3. Carrier - swell the fiber and dissolve the dye to make the dye getting into fiber.
4. Leveling agent - make more leveling dyeing (some will have adverse effect on
slower dyeing)
5. Water - dyeing media

Acid Dye (Anionic): The dye is called acid because it needs acidic dyeing condition.
It can be dyed on protein fibers (silk, wool, and other animal fibers) and on polyamide
fibers. Acidic condition will give the fibers showing positive charge. As the negative
charge will attach directly to positive charge, and penetrate into the fibers.
Dyeing conditions: l00oC x 30-60 mm

Textile Auxiliaries:
1. Leveling agent - for levelness dyeing.
2. Retarding agent - for inhibiting the dye not attach to fibers too fast.
3. Acid - adjust the dyeing condition and make the fibers to show positive charges.
4. Water - dyeing media.

Basic Dye (Cationic)

The dye shows positive charge. Normally, the dye can be applied on wool, silk and
poly-acrylonitrile (acrylic).
Dyeing Conditions:
l00oC x 30-60 mm Dyes Dyeing Condition (pH)
Acid (Wool) 2-4, 4-6, 6-8 (depends on types of dyes)
Acid (Nylon) 4.5-5.5, on types of dyes)
Basic 3.5-4
Direct 7.0
Disperse (Polyester) 5-6
Disperse (Acetate) 6.5-7.0
Disperse (Triacetate) 4.5-6.5
Reactive 7.0 (Exhaustion)
11.0 (Fixing)

56
Textile Auxiliaries:
1. Leveling agent - for levelness dyeing.
2. Retarding agent - for inhibiting the dye not attach to fibers too fast.
3. Acid - adjust the dyeing condition and make the fibers to show negative charges.
4. Water - dyeing media.

57
5.1 Synthesis of Reactive Auxiliaries for Dye Resist Treatment of
Wool

5.1.1 Abstract: Three reactive auxiliaries containing s-triazine-based reactive

groups were synthesized and the dye resist effects achieved on wool were evaluated.
The results obtained indicated that, the dye resist 2 effect achieved with the bi-
functional reactive Auxiliary (R ) was exhibited the highest value. The effect of the
dye bath pH, salt concentration, dyeing temperature, dyeing time, conc. of dye and
conc. Of auxiliaries were also studied. Good fastness properties of the dyed fabric
were achieved.

Keywords: Reactive auxiliaries, dyeing wool, dye resist, colour strength, fastness
properties

5.1.2 INTRODUCTION

Auxiliary products of various types are commonly used in the dye bath during the low
temperature dyeing of wool. Such [1] chemicals are used to promote dye bath
exhaustion and to achieve level dyeing[2]. A resist process may be defined [3] as one
which modifies a textile fiber in such away that when the resist treated fiber is
subsequently dyed, it absorbs dye to a lesser extent or at a slower rate than untreated
fiber. Various treatments have been proposed for imparting dye resist effects to wool,
for example, sulphonation,acetylation, glyoxylation, deposition of polymers, alkaline
chlorination and treatment with formaldehyde,sulphamic acid[4,5], tannic acid /metal
salts, synthetic tanning agents[6,7,8] and also colourless reactive compounds[9,10].
Among them reactive dye resist agents are preferred due to their easy handling and
application[10]. A viable dye resist agent must be completely cured and bound firmly
to the wool substrate in order to achieve satisfactory dye resist effects[11]. Increasing
the substantivity between the substrate and the dye resist agents is one of the most
important factors needed to improve dye resist effects.In order to increase this
substantivity one possible effective dye resist method would be to covalently bind the
dye resist agents to the wool substrate using suitable fiber reactive groups[11]. In this
work we synthesized three reactive auxiliaries containing s-triazine based reactive
groups which were used for treating wool. Three acid dyes containing different
number of sulphonic acid groups were used for dyeing treated wool.

5.1.3 MATERIALS AND METHODS

Material and Chemicals: Scoured and bleached wool fabric with the following
characteristics was purchased from Misr for Spinning and Weaving Company,
Mahalla El-Kobra, Egypt; weight 205 gm-2, 72 ends per inch, 64 picks per inch.
Before using, the fabric was treated with a solution containing 5g L-1 non-ionic
detergent (Hostapal CV, Clariant), at 50 oC for 30 min.Then, the fabric was
thoroughly washed with water and air dried at room temperature. Diamino benzene
sulphonic acid (95% assay), cyanuric chloride (99% assay) and sulphanilic acid (99%
assay) were supplied by Aldrich.All other chemicals employed were of analytical
grade. The codes, the chemical names and chemical structures of the synthesized
reactive auxiliaries are given in table (1).

58
Dyes: Three acid dyes which have different numbers of sulphonate groups were used
(fig.1). The commercial names and color Index names for these dyes are given in
table (2).

Reactive Dyes for Purification of Chemicals:

Cyanuric Chloride: Cyanuric chloride [1 2 ] was crystallized from petroleum ether

(b.p90-100 ºC), and dried under vacuum at room temperature.

Sulphanilic Acid: 100 gm of sulphanilic acid in about 500 ml sodium carbonate

solution was boiled then filtered and made strongly acid with hydrochloric acid. The
solution was then neutralized with 1N sodium carbonate. The hot solution was cooled
to 0 ºC with stirring and the precipitate of sodium sulphanilate was filtered off. The
crystals were dissolved in 500 ml distilled water and the solution was filtered and then
acidified with concentrated hydrochloric acid. The material was then re-crystallized
from hot distilled water and dried at 120 ºC overnight.

59
1-amino -8 naphthol -3, 6 disulphonic acid (H acid):

Sodium carbonate (20gm) was added to a solution of 100 gm of (H acid) in 750ml of

hot distilled water, followed by 5gm of activated charcoal. The suspension was stirred
for 20 min and filtered by suction. H acid was precipitated by adding 50 ml of conc.
HCL, then filtered by suction and washed with distilled water. The Mother H acid was
dried overnight.

Procedures:

Synthesis of 2,4 dichloro – s -triazine -6- yl- p- 1 amino phenyl sulphonic acid
sodium salt(R )[13]:

Sulphanilic acid (20 gm in 100 ml water) was added slowly to cyanuric chloride (22
gm in 200 ml acetone containing about 100 gm ice) whilst maintaining the pH of the
solution at 7 by the addition of 2 N sodium carbonate. the reaction mixture was stirred
for 1.5-2h the product was filtered off, washed thoroughly with acetone and then oven
dried.

Synthesis of 2, 5-Bis (2, 4 dichloro-s-triazine-6-yl) - 2 amino phenyl sulphonic

acid sodium salt (R):

Cyanuric chloride (20 gm) in acetone (100ml) and ice was added to a solution of 2,5-
diamino benzene sulphonic acid(10 gm) as a slurry, whilst maintaining the pH at 7 by
the addition of a solution of saturated sodium carbonate. The reaction mixture was
stirred for 3h and the product was filtered off, washed thoroughly with acetone and
then oven dried.

Synthesis of 2, 4- dichloro-s- triazine-6-yl-amino-8- 3 naphthol 3, 6 disulphonic

acid sodium salt (R) [14]:

20 gm (H-acid) was dissolved in 1N sodium bicarbonate solution, the solution diluted

to 250 ml and neutralized with acetic acid. this solution was dropped simultaneously
into a well stirred suspension of finely divided cyanuric chloride (10 gm)in acetone
and ice water (2:1)at 0ºC over 3h when pH was stable at 7 the reaction was complete,
the product was filtered off and dried at room temperature.

Characterization of Products: Melting points were measured by a Gallankamp

Melting Point Apparatus. IR Spectra were obtained (KBr discs) on Pue Unicam
Spectra 1000.1HNMR Spectra were measured on 3 2 avarian 400 MHz Spectrometer
for solutions in (CD) 4 SO using SiMe as internal standard.Mass Spectra were
performed on HP model MS-5988. Microanalyses for C, H and N were performed on
Avario Elementry (table 3). Analytical data were obtained from the service laboratory
center in NRC.

5.1.4 Application of Reactive Auxiliaries: The wool samples were treated with
each compound at various concentrations (1, 2, 4, 8 and 16% oww) by an exhaustion
process using liquor ratio of 20:1. Auxiliary were added and the process was started at

60
40 °C and run for 20 minutes, during which pH 4 was established, salt ammonium
sulphate (1% oww). Then the bath was raised to the boil over 30 minutes and held for
60 minutes at 100 ºC. Afterwards, samples were rinsed for 15 minutes and dried at
room temperature.

5.1.5 Determination of Mass Gain: Weight gain was determined on the basis of
oven dry weight, measured before and after the application of the reactive auxiliaries.

Fig. 2: The effect of pH on resist effectiveness of 1 2 3 auxiliaries (R , R , R ),

conditions: temperature100 0 C, time 40 min., dye conc. 3%,conc. of salt 1%and
conc. of auxiliaries 4%.

Fig. 3: the effect of the temperature on Resist 1 2 3 effectiveness of auxiliaries (R ,R

,R ), conditions : pH 4, time 40 min.dye conc. 3% ,conc. of salt 1% and conc. of
auxiliaries 4%.
5.1.6 Dyeing of Wool Fabric: The resist effectiveness of reactive auxiliaries on
wool was evaluated using the three dyes listed in table (2). Dyeing process was
carried out in a dye bath containing ammonium sulphate (0.5-2.5% oww), using a
liquor ratio of 20:1 at pH (3-8 ),the dye bath temperature (40- 100 ºC ) and dyeing

61
time(20- 90 minutes) and dye conc. (1- 4 %). Afterwards, samples were rinsed for 15
minutes and dried at room temperature.
5.1.7 Dye Resist Evaluation: To evaluate dye resist effectiveness, the treated wool
samples were dyed in a competition with untreated wool (differential dyeing
technique,DD), we quantified the dye resist effectiveness (RE) of the different
auxiliaries by calculating RE values from the reflectance values (K/S) of the dye
treated and untreated wool samples.K/S values were obtained at the wavelength of
maximum dye absorption:
untreated treated [(K/S ) - (K/S )]
%Resist = ------------------------------- x 100
Untreated (K/S)

5.1.8 RESULTS AND DISCUSSIONS

Dyeing:

Effect of Dye Bath pH: Figure 2 shows that the pH values of the dye bath have a
considerable effect on the dyeability of wool fabrics with dye resist technique, 1 2 3
DD process using the auxiliaries R , R and R and acid red 27. The effect of the dye
bath pH can be attributed to the correlation between auxiliary structure and wool
fabric. It can be seen from the results given 2 in fig (2) that the R treated wool
achieves a higher 3 1 dye resist at the same pH value than the R and R treated wool.
One might be attempted to deduce that 2 this differences arises because R reactive
resist contains two s- triazine reactive moieties which leads 2 to a higher degree of
fixation of R at pH 4 to the wool fiber. As clearly observed in figure (2) it was noticed
from the figure that higher dye ability at pH 4 and then the dye ability decreases as the
pH increases.

Effect of Temperature: The effect of temperature on the dye ability of wool fabrics
with dye resist technique, 1 DD process using the auxiliaries R , R and R and acid red
27 was conducted at different temperatures (40-100oC). As shown in figure (3), it is
clear that the dye resist increases with increasing dyeing temperature for the three
used auxiliaries R, R, R and reaches maximum value at 100oC.

62
Fig. 4: The effect of time on Resist effectiveness of 2 3 auxiliaries (R, R, R),
conditions: pH 4, temperature100 0 C, dye conc. 3 %, conc. Of salt 1% and conc. of
auxiliaries 4%.

Fig. 5: The effect of conc. of salt on Resist 2 3 effectiveness of auxiliaries (R , R , R ),

conditions: pH 4, temperature100 0 C, time 40 in, dye conc. 3 %and conc. of
auxiliaries 4%.

63
Fig. 6: the effect of the conc. of dye on Resist 2 3 effectiveness of auxiliaries (R, R,
R), conditions: pH 4 temperature100 0C, time 40min., conc. of salt1%and conc. of
auxiliaries4%.

Fig. 7: The effects of conc. of auxiliaries on Resist 2 3 effectiveness of auxiliaries (R,

R, and R), conditions: pH 4, time 40 min., temperature 100oConc. Of salt 1% and dye
conc.3% of acid red 27.

Effect of Dyeing Time: The effect of time on the dye ability of wool fabrics with dye
resist technique, 2 3 DD process using the auxiliaries R 1 R2and R3and cid red 27
was conducted at different temperatures 20-90 min.). As shown in fig. (4), it is clear
that the dye resist increased as the dyeing time increase up to40 min, and then it began
to decrease.

64
Effect of the Salt Conc.: The effect of conc. of salt on the dye ability of wool fabrics
with dye resist technique, DD process using the auxiliaries R, R and3 R and acid red
27 was conducted at different conc. (0.5-2.5% oww). As shown in figure (5), it is
clear that he dye resist increases with increasing conc. of salt and reaches maximum
value at 1% oww and then it began to decrease.

Effect of the Dye Bath Conc.: The effect of the dye bath conc. on the dye ability of
wool fabrics with dye resist technique, DD process 1 2 3 using the auxiliaries R , R
and R was conducted at different dye bath conc. (1-4% oww) of acid red 27. As
shown in figure (6), it is clear that the dye resists increase with the increasing of
dyeing concentration and reaches the maximum value at 3% of dye concentration.

Effect of the Conc. of Auxiliaries: The effect of the conc. of auxiliaries on the dye
ability of wool fabrics with dye resist technique, DD process using the 1 2 3
auxiliaries R, R and R was conducted at different conc. of auxiliaries (1, 2, 4,8
and16%oww). As shown in figure (7), it is clear that the dye resistant increases with
the increasing of the concentration of auxiliaries and reaches the maximum value at
(4% oww) of auxiliary concentration.

DD and DR techniques: After reaching the optimum 1 conditions for dyeing treated
wool using R, R2, R3, to obtain maximum dye resist effect, we investigated the
effectiveness of the auxiliaries using two different dyeing processes at the same
conditions. The treated wool was dyed separately (dye resist technique, DR) to
estimate the overall dye resist effect. On the other hand treated wool samples were
dyed in competition with untreated wool (differential dyeing technique, DD) to
estimate the differential dyeing behavior. The three acid dyes listed in table (2) were
used. The obtained results suggest that the dye resist 2 effect achieved with the bi-
functional reactive resist (R ) was superior to that achieved by the mono-functional 1
reactive resist (R ).The explanation for this difference might be that there are cross
links introduced by the

65
Auxiliaries Alt: alteration Sc: staining on cotton Sw: staining on wool 0: sample
without treatment of auxiliaries

Fig. 8 a,b: Resist effectiveness of R versus auxiliary uptake of the fibers

66
67
Fig. 9a,b: Resist effectiveness of R versus auxiliary uptake of the fibers.

68
Fig. 10a,b: Resist effectiveness of R versus auxiliary uptake of the fibres bi-
functional groups of (R ),increasing the substantivity between the substrate and the
dye resist agents which is one of the important factors needed to improve dye resist
effects. Figures (8, 9, 10) show the resist effectiveness of the three auxiliaries used,
depending on the amount of auxiliary fixed to the fibers. At low auxiliary uptake, the
three compounds differ greatly 2 from each other. At equal weight gain, R shows a 3,
3 better resist effect than R and R in turn have better 1 resist effect than R . Above an
uptake of 7.2%, the resist effectiveness of the auxiliaries tends toward a limiting resist
value for the three dyes used. It must be concluded that other factors such as
molecular configuration, in addition to ionic/ hydrophobic mechanism, could affect
the achieved weight gains, since the inductive effect of the electron withdrawing
nitrogen on the s- triazines activates the reactive centers on the carbon atoms of s-
triazines more than those of other hetero-cycles. Moreover, the electro negativity of
the leaving groups adjacent to the reactivity of the reactive centers. Also molecular
structures of the dyes used have an effect on the dye resist values obtained. Acid red
27 gives higher values of dye resist that is because this dye contains three sulphonic
acid groups, thus strong electrostatic forces are built up between treated fibers and
dye, which leads to an efficient electrostatic repulsion of the dye molecules. The dye
is not absorbed quite readily and is not able to penetrate into the fibers [17]. It can be
seen from the results given in 2 fig (8, 9, 10) that the R treated wool achieves a higher
1 weight gain than the R treated wool. One might be attempted to deduce that this
differences arises because2 R reactive resist contains two s- triazine reactive moieties
which leads to a higher degree of fixation of 2 R to the wool fiber.

Fastness Properties: Fastness properties of the dyed fabrics are shown in table 4.The
results indicated that 1ated wool with the three auxiliaries R ,R ,R using the three acid
dyes give good to very good results for 2 rubbing, perspiration, light and washing
fastness R 1 3 shows better fastness properties than R and R with the three acid dyes.

5.1.9 Conclusion:

69
Three reactive auxiliaries containing striazine- based reactive groups were
synthesized and the dye resist effects achieved on wool were evaluated using two
different techniques DR, DD. The obtained results suggested that the dye resist effect
achieved with the bifunctional reactive resist was superior to that achieved by the
monofunctional reactive resist and the DD technique gives better dye resist effect than
DR one. Good fastness properties of the dyed fabric were achieved.

5.2 The Effect of UV Absorbers on Ultra Violet Protection Properties

of Dyed Cellulosic Fibres.

5.2.1 Abstract

Several reactive dyes derivatives of C.I. Reactive Red 198 have been prepared. Three
of these dyes included additional UV-absorber systems based on 2’-hydroxy-
benzotriazole. The spectrophotometric properties of the dyes obtained were measured,
and their application properties on three different types of cotton fabric were
examined. It was found that newly-prepared dyes could be applied to the cotton fabric
by the pad dyeing method, which gives a higher dyeing efficiency than the exhaustion
method. the type of the fabric used has a significant influence on the measured UPF
value. It was found that the new products gave excellent UV protection properties to
dyed textiles, although only minor improvement was observed in comparison with the
reference dye.

5.2.2 Introduction

In practice, the UV protection properties of textiles are characterized by the UPF

value of a particular fabric. UPF is the abbreviation of the Ultraviolet Protection
Factor, The UPF of textiles depends on their chemical composition and physical
structure (thickness, porosity, method of manufacturing). The second important factor
which affects the UPF of textiles is the presence on the fabric of various chemicals
such as dyes and other auxiliaries. It was experimentally found that among natural
fibres the best protection against UV radiation is given by wool. On the other hand,
from the practical and aesthetic viewpoints, in summer we usually wear clothes which
are made from undyed cotton, a natural fibre which provides only little protection
from the ultraviolet radiation. The introduction of dyes and other auxiliaries which
possess their own significant absorption in the UV region can increase the protection
properties of this fibre. In practice, a series of special UV absorbers are used in order
to protect textiles and to improve the light-fastness of the coloured fabrics. These
compounds absorb the harmful UV radiation in the region of 250-400 nm and rapidly
convert it to harmless heat. Among various chemical structures, one of the most
important groups are 2’-hydroxyphenyl-benzotriazoles such as Tinuvin 326 (Figure
1), commercialised by Ciba-Geigy [4]. This product is widely used for polyester fi-
bres dyed by the exhaustion method. The specific nature of the hydrogen bridge for-
med in the molecule is responsible for its protective properties. In the excited state of
the molecule, after absorbing the part of radiation, the proton from the bridge is
transferred from the oxygen atom of the hydroxyl group to the nitrogen atom of the
benzotriazole ring. This leads to a new excited state with lower energy, from which
the molecule can easily return to the first basic state [5]. A similar absorber (Figure 2)
was designed to improve the photostability of the anionic dyes applied while dyeing

70
the wool. The sulphonic group in its molecule gives solubility in water and allows
fixation of t he absorber onto the fibre [6]. At present, other special compounds are
also used to increase the protective properties of coloured or undyed fabrics against
UV radiation. For example, for

Figure 1. Chemical structure of the UV absorber ‘Tinuvin 326’.

Figure 2. Water-soluble UV absorber of the benzotriazole-type.

cotton and cotton blends, studies recommend Cibatex UPF, a water-soluble oxalic
acid dianilide with two reactive groups (no structure details known). It is applied by
the exhaustion (1-4%) or pad batch methods (15-50 g/dm3) with reactive or direct
dyes [3].
One interesting experiment in this area was an attempt to incorporate the UV-ab-
sorbers system (of the benzophenone and benzotriazole type) to the molecule of
dispersed dye (Disperse Yellow 42) used in polyester fabric. One example of such a
prepared dye is presented in Figure 3. A slight improvement of light fastness in the
dyeing fabric was observed in some cases of these dyes [7].

Figure 3. Disperse Yellow 42 with built-up UV absorber.

71
Thus, the purpose of our research was the synthesis and examination of the
application properties of bifunctional reactive dyes for cellulose fibres which included
an additional UV absorber fragment in their molecule. The structure of these dyes is
presented in Figure 4.

Figure 4. The general structure of the prepared dyes

In this formula, A was a typical moderator used in the synthesis of reactive dyes such
as methanilic acid (A1) in the case of the standard reference dye (C.I. Reactive Red
198), or the amino group (A2). In the case of other dyes, we used as A specially
prepared water-soluble UV-absorbers, derivatives of the 2’-hydroxyphenyl-ben-
zotriazole presented by structures (A3, A4, and A5) in Table
In the present work, it was anticipated that cotton fabric coloured with some of the
synthesised dyes would also exhibit increasing protective properties in comparison
with fabric dyed with the standard dye.

5.2.3 Experimental
The UV absorbers were prepared by the methods usually used in the case of other
benzotriazole derivatives. Absorber A3 was prepared by a coupling reaction of
diazotized 3-amino-4-nitrobenzenesulphonic acid with 4-hydroxyacetanilide,
followed by the reduction of the nitro group of the monoazo dye to the triazole ring
with simultaneous hydrolysis of the acetylamino group (scheme shown in Figure 5):\

72
Figure 5. The synthesis route of the absorber A3.
A4 was prepared in a similar way to A3, but 4-methylphenol was used as a coupling
agent. The resultant 2’-hydroxy-4’-methylphenylbenzotriazole-6-sulphonic acid was
then coupled with diazotized methanilic acid, and the azo bond was reduced to the
amino group.
Absorber A5 was prepared by coupling diazotized 2-aminophenol-4-sulphonic acid
with 1,3-phenylenediamine, and the oxidation of the resultant o-aminoazo dye with
copper salts in a boiling aqueous-ammonia environment

73
Table 2. Spectrophotometric properties of Absorbers A3-A5
.

Reactive dyes P1-P5 were prepared by the condensation of 1,3,5-trichloro-s-triazine

(cyjanuric chloride) with 1-amine-8-hydroxy-3,6-naphtalenedisulphonic acid (H acid)
at the temperature of 0-5°C and pH=1.0±0.2. The completiong of this reaction was
confirmed by testing each sample on filter paper with an Ehrlich reagent. No colour
present means that all the aromatic amine had overreacted with the cyjanuric chloride.
Such prepared ‘triazinyl-H’ acid was then coupled with diazotized 4-(β-
sulphatoethyl)sulphonylaniline (‘paraester’) at the temperature of 0-5°C and
pH=7.0±0.2. The last step of the synthesis was the condensation of dichlorotriazinyl
dye with amine A at the temperature of 35-40°C and pH=7.0±0.2. The latter step was
monitored by paper chromatography (Whatman 3 paper, developing phase 1%
aqueous NaCl). The synthesis route of the reactive dyes is presented in the scheme in
Figure 6. Synthesised dyes P1-P5 were examined for their UV spectra in the UV-VIS
region. .

Figure 6. The synthesis route of prepared dyes, derivatives of C.I. Reactive Red 198

Table 4. The exhaustion degree, fixation degree and total dyeing efficiency of
prepared dyes.

74
All the prepared dyes were subjected to application examinations, during which the
following cellulose fabrics were used:
bleached cotton fabric with linen weave, weight 107 g/m2 (Fabric X);
bleached cotton with linen weave, weight 104 g/m2 (Fabric Y);
bleached cotton satin, weight 119 g/m2 (Fabric Z).
Dyeing was carried out by the exhaustion method (1% and 2% dyeings, dyebath ratio
1:20 in the presence of 50 g/dm3 sodium chloride and 20 g/dm3 sodium carbonate).
The percentage degree of exhaustion was calculated from spectrophotometric
measurements according to formula

B2
E=(1- )×100% (1)
B1
Where:
B1 – the absorption of the dyebath at λmax before dyeing;
B2 – the absorption of the dyebath at λmax after dyeing.
The results of these measurements are listed in Table 4.
Each fabrics was also coloured with the same dyes by the use of the pad dyeing
method. Each bath contained the following elements: 1 g dye, 10 g of urea, 1 g
NaHCO3 , 5 cm3 10% solution of 3-nitrobenzenesulphonic acid sodium salt (Nitrole
S), 5 cm3 5% solution of sodium alginate, and was completed to 50 cm3 with distilled
water). The fixation of the dyes was carried out at the temperature of 130°C over 5
minutes.
In order to more precisely characterise the prepared dyes, their fixation on the fabric
X was measured. Any unfixed dye was stripped from a sample of dyed fabric by
repeated hot extraction with pyridine-water azeotrope. After drying, the fabric sample
was then dissolved in concentrate sulphuric acid and poured onto a water-ice mixture.

75
The concentrations of dyes in these solutions were measured spectrophotometrically.
The same procedure was repeated with the samples of the dyed fibre which were not
extracted with the water-pyridine system. The percentage degree of fixation was then
calculated from formula (2):

(2)
where:
C1 – the absorption of the dissolved sample of the fabric without extraction with the
pyridine-water azeotrope,
C2 – the absorption of the dissolved sample of the fabric extracted by the pyridine-
water azeotrope.
The total efficiency of the dyeing process was calculated from formula (3):
The results of these measurements are listed in Table 4.
Finally, the dyeing textiles were examined for their protective properties according to
the European Standard. The measurements of UV transmittance were carried out with
the double beam Beckman DK-2A spectrophotometer equipped with an Ulbricht
sphere and powered by a hydrogen lamp. The UPF factor was calculated from
formula (4):

(3)
where:
E(λ) - the solar spectral irradiance, W/m2nm;
ε(λ) - the erythema action spectrum;
Ti(λ) - the spectral transmittance sample i at the wavelength λ;
Δλ - the interval of the wavelength, nm.
The results obtained are presented graphically in Figures 10 and 11.

5.2.4 Results and Conclusions

As can be seen from the results presented in Figure 7 and Table 2, all the examined
absorbers exhibit significant absorption in the near UV region as was expected. The
A4 absorber has the broadest absorption band, so one may expect the best increase in
UV protecting properties after building it up to the dye molecule. Similar properties
might also be expected in the case of absorber A3, which possesses the highest value
of the molar absorption coefficient.

76
 The analysis of the data presented in Figure 8 and in Table 3 shows that
introducing other moderators than metha-nilic acid to the dye molecule, such as am-
monia, results in only a small decrease in their molar absorption coefficients εmax, in
comparison with the standard dye P1. Some decrease in the absorption intensity in the
UV-B ultraviolet region absorption spectra (280-315 nm) is also visible, probably due
to the absence of the aromatic ring of the methanilic acid in P2.

The absorption curves of the dyes P3-P5 presented in Figure 9 show that
incorporating the 2’-hydroxybenzotriazole system into the dye molecule results in the
increase in absorption in the UV region, which is especially visible in the case of dye
P5, and also in the case of dye P4. On the other hand, due to the radical increase in the
molecular weight of these dyes, their molar absorption in the visible region is much
lower than in the case of the reference dye P1. The decrease in colour intensity of the
newly-prepared dyes is much greater than was expected. All the factors mentioned
above also influence the application properties of the prepared dyes. As can be seen
from the data presented in Table 4, in several cases (Dye P4), probably due to the
structural disturbance of the dye molecule, the degree of exhaustion on the coloured
fabric is visibly decreased. More comparable results were obtained during the pad
dyeing method with an average dyeing efficiency of 80–90%. For this reason,
prepared dyes could more readily be used in this method, or in the printing of
cellulose fibres. Figures 10 and 11 present the values of the UPF factor calculated
from the measurements of transmitted UV radiation through the cotton fabrics used.
As it mentioned earlier, the results again show that the physical properties of the
examined fabrics have a crucial influence on their UPF factor. The higher protection
properties of the uncoloured fabric are increased to a much greater extent after the
dyeing process. This is especially visible in the case of Fabric X and Fabric Z, where
an increase from ‘moderate’ and ‘good’ to ‘excellent’ protection can be observed for
several dyes.
Comparing the new dyes with the reference C.I. Reactive Red 198 (P1), one
may note that dye P3 gives the best UPF factor for the exhausting method, while in
the pad dyeing method the best results are obtained for the dye P4, although both
these values are practically very close to those of the reference dye. However, if one
considers the fixation degree on the fibre of the reference dye in comparison with the
new dyes, improvement of up to 10% of the UV-protecting properties may be
observed in the latter case. This result is however rather unimportant from the
practical point of view, so one may rather consider the use of new benzotriazoles as
the components of fibre-reactive, colourless UV absorbers, as we suggested in our
earlier work.

5.3 Influences of Non-ionic Auxiliaries on Absorption of Acid Milling

Dyes & on Colour Characteristics of Wool Fibre.

5.3.1 Abstract:

The influence of non-ionic auxiliaries on absorption of the acid milling CI Acid Blue
80 dye on wool fibre and on the colour changes of dyed fabric has been investigated.
The kinetics of dye absorption and the colour characteristics of dyed fabric, including
washing fastness, were determined. A non-ionic surfactant based on poly-ethoxylated

77
alkylphenol enables dyeing at low temperatures, colour characteristics and wash
fastness to be improved, whereas the alkylaminoethoxylated product enhances the
dyeing rate at higher temperatures. The variation of colour yield values in the dyed
fabric which occur due to the use of non-ionic auxiliaries or the difference in dyeing
temperatures is explained and discussed

5.3.2 Introduction:
Higher-affinity dyes, such as acid milling dyes with larger molecules, do not penetrate
into the wool fibre at lower temperatures, and dyeing unlevelness or ring dyeing
becomes a major problem. Ring dyeing can give problems such as reduced fastness,
shade change, or poor rubbing fastness. Localized unlevelness is primarily related to
the physical and/or chemical non-uniformity of the substrate; a typical example of this
is skitteriness in wool dyeing. One of the fundamental mechanisms that can contribute
to level dyeing is the migration of dye after initially unlevel sorption into the fibre
[1]. As a fibre, wool is heterogeneous, both chemically and physically. In the case of
wool without the damage in cuticle cells, it is assumed that the dye uptake in the early
stage of adsorption is subject to the dyeing behavior of the intercellular regions of the
cuticle-cuticle (surface) layer [2]. Dye most readily enters the fibres by diffusion
through the intercellular region between the scale cells of the wool fibre, penetrates
fairly rapidly into the non-keratinous endocuticle region of the surface layer, and soon
reaches equilibrium with the dye in the outer solution. Within the cuticle cells, the
endocuticle and then the exocuticle become coloured, as the dye travels through the
intercellular cement and penetrates into the cells from their undersides [2]. It has
been established that an increase in dye bath exhaustion and the improved levelness of
dyeing with selected milling acid dyes could be obtained when sparingly water-
soluble organic compounds are added to the dye bath, or wool fibres are pre-treated
before dyeing.

Riva et al have investigated the influence of pre-treating wool with a non-ionic

auxiliary on dye sorption, and assumed that the enhancement of the increase in dye
bath exhaustion and the faster rate of dyeing are due to the sorption of the auxiliary by
the wool [4]. The partial solubilisation of free fatty acids of a lipid layer of cellular
membrane complex (CMC) due to the treatment of the wool with non-ionic
polyglycol ethers and the modification of the hydrophobic domains of the CMC in
wool fibres were proved.

In the present work we examine the influence of how acid dye is taken up by wool
fabric on the changes in colour characteristics that occur thanks to applied non-ionic
auxiliary dyeing agents and temperature.

78
Figure 1. Chemical formula of C. I. Acid Blue 80 dye.

5.3.3 Experimental

Materials

The initial merino wool fabric corresponds to ISO 105/F: 1985 (E). The dye used in
this study was CI Acid Blue 80 (Sandolan Milling Blue N-BL 150), supplied by
Clariant and purified by recrystallisation three times: dissolving in hot
dimethylformamide, precipitation by acetone, and then filtered. The dyeing
auxiliaries non-ionic products, ethoxylated alkylnonylphenol and the dispersing agent
mixture Lanasan LT (NPE), are recommended for use in low-temperature wool dyeing
(Clariant); alkylaminoethoxylate and the glycolic ether mixture (AAE) Rucogal MSC
(Rudolf Chemie) are recommended for use in wool and polyamide levelling dyeing.
The other analytical-grade reagents were used without purification.

Dyeing

Before dyeing, the fabric samples were immersed for one hour in 0.1M acetic acid
buffer adjusted to a pH of 4.2±0.05. We measured the dyeing rates in a dye bath with
an initial concentration of dye of 1.7×10-4 mol/l or 2.3% owf. The dyeing took place
in a laboratory apparatus with a magnetic bar stirrer and cylinder to girdle the 10×20
cm fabric sample with dyeing liquor at a pH of 4.2±0.05. After dyeing, the dye bath’s
pH was unchanged. In all dyeing, we adopted the liquor-to-fibre ratio of 200:1 and a
temperature of 60 °C or 85 °C. Dyeing was carried out both in the absence and pres-
ence of auxiliaries (1.8% owf) up to the dye absorption equilibrium. At the end of the
dyeing process, the samples were rinsed thoroughly in water and dried in open air.
Conventional dyeing in the presence of electrolyte was carried out using 10% owf
sodium sulphate and 4% owf ammonium sulphate. Dye concentration in the dye bath
was measured at the start, after 5, 10, 15, 20, 30, 45, 60, 90 minutes, and up to the
dye’s exhaustion.
Dyeing characteristics

Dye absorption was calculated from the difference in dye concentration before and
after dyeing time t. Dye concentration in liquor was measured in a 10-mm cell using
the Spectronic Unicom Genesys TM spectrophotometer. On completion of dyeing, the

79
wool fabric samples were removed from the liquor, rinsed in water to remove any
loosely adsorbed dye, and dried in air.
The percentage dye bath exhaustion E was calculated according to Equation 1:

where Ao and Ad are the adsorbances at 590 λmax of Acid Blue 80 dye, initially in the
dye bath and of residual dye in the dye bath respectively.
For the dyed fabric samples, the light diffuse reflectance measurements were per-
formed with a Spectroflash SF 450 Plus spectrophotometer (Datacolour), and the
colour yield values were calculated according to the Kubelka-Munk function (K/S ) by
Equation 2 [10]:

(2)

where:
K - absorbance,
S - scattering,
R - reflectance.

Evaluating the colour parameters

Samples for colour measurements were prepared by folding the dyed wool fabric five
times to give samples measuring about 3×3cm. Five points on each trial sample were
measured using a spectrophotometer. The colour parameters were evaluated by means
of the Cielab system and the modified CIE L* C * h* (D65/10o) system. The
following colour parameters for the dyed samples were obtained by the digital Cielab
system: L* – lightness, a* – redness if positive coordinate, or greenness if negative
coordinate, b* – yellowness if positive coordinate, or blueness if negative coordinate,
C* – chromaticity, h – hue of the colour, X – coordinate x, Y – coordinate y, Z –
coordinate z [10].
The values of colour difference (ΔE) for the dyed samples after relative treatments
were calculated by Equation 3 [10]:

E  (L) 2  ( a) 2  (b) 2 (3)

ΔL*=L*trl-Lin,
Δa*=a*trl-a*in,
Δb*=b*trl-b*in Lin, a*in, and b*in are parameters of initial species before the
relevant treatments.

80
The ΔE deviation of all treated samples was no higher than 0.2. The coordinates of the
colours obtained and the results of the ΔE value determinations are summarised in
Tables 1-3.The yellowness index YI of the wool fabric samples in the blank dyeing
trials was calculated using equation 4 [10]:

1.28 X  1.06Z
YI  100 % (4)
Y

where: X, Y, and Z are the C/2 CIE tri-stimulus values of the specimen.

The level of wool fibre damage occurring during the blank dyeing of the wool fabric
was determined by means of tryptophan fluorescence intensity changes. The
fluorescence spectra were measured with an MPF-4 fluorescence spectrophotopmeter
(HITACHI). Samples of the blank dyed wool fabric signals (λex=295 nm, λex=346
nm) were measured and quantified by comparison with those of the initial untreated
fabric. The dyeing rate constants were calculated using a modified Cegarra-Puente
equation (5) suitable for exhaustion baths:

L*trl, a*trl, and b*trl are parameters of trials, i.e. after blank dyeing (treatment of
undyed fabric under dyeing conditions, but without using dye) or after washing the
dyed fabric samples.

Ct 2
ln[ ln(1  2 )]  a ln t  a ln k (5)
C

where a is a coefficient depending on exhaustion, Ct is the dye concentration in the

fibre at time t, C∞ is the dye concentration at the equilibrium, K is the absorption rate
constant, and t is the dyeing time.
Determining fastness

The samples were washed using an Isal AG 4006 Basel/Schweiz apparatus with
rotating stainless-steel hermetic autoclaves, according to standard ISO 105/C06 A1S
at 40 °C for 30 min. Colour difference (ΔE) and colour yield (K/S) data were obtained
with a Data colour SF450 Plus apparatus under illumination D65 using 10° standard
observation angle. Each sample was measured five times and the average values were
calculated.

5.3.4 Results and discussions

Dyeing rate
Figures 2 and 3 show the plots of the dyeing rate and relative dye uptake

Table 1. Effect of auxiliaries and temperature on dye exhaustion (E, % ), kinetic

constant (K)and on colour yield of wool fabric; Colorimetric measurements data of
fabric dyed using auxiliaries;Abbreviations given in Figure 1.

81
Ct/C∞ against the square root of dyeing time t1/2 for dyeing in solution without any
auxiliaries (A) and in the presence of dyeing organic auxiliaries (NPE or AAE) or
electrolyte (EL) respectively. The values for the kinetic constant K in the absence and
in the presence of auxiliaries are presented in Table 1. It is clear from these results that
the application of the non-ionic surface active agent NPE for dyeing at 60 °C leads to
a considerable increase in the apparent dye uptake, while in the presence of weakly
cationic alkylaminoethoxylate AAE, the rate of dye absorption was even lower
compared with that for dyeing without auxiliary. The application of the dyeing
auxiliary NPE as well as AAE makes the whole quantity of dye to penetrate the fibre
at 85 °C more readily as suggested by the dye exhaustion and dyeing rates.From
Figure 2 and Table 1, the NPE at 60 °C temperature can also be seen to cause the
higher increase in total dye absorption absorption and the rate of dyeing, compared
with the figures for AAE. As mentioned above, alkoxyethylated nonylphenol has a
significant effect on the cellular membrane complex (CMC) of wool fibre [5], while
the alkylaminoethoxylates, which combine non-ionic and cationic properties, are
capable of forming complexes with acid dyes, facilitate solubilisation, and provide
level dyeing of wool [3]. Non-ionic alkylphenolethoxylate-type surfactants, in
contrast to alkylaminoethoxylates, are not considered to have a structural effect on the
levelling agent, but are known to be adducts which form complexes with wool fibre
by means of hydrophobic interaction between hydrophobic sites [12]. Mieusset et al
have shown that when dyeing with a 1:2 metal complex dye, a quick initial surfactant
absorption by wool occurred regardless of the manner of surfactant application.
Surfactant absorption is followed by pronounced desorption, with an increase of
temperature and dye exhaustion [13].Mieusset et al have shown that when dyeing
with a 1:2 metal complex dye, a quick initial surfactant absorption by wool occurred
regardless of the manner of surfactant application. Surfactant absorption is followed
by pronounced desorption, with an increase of temperature and dye exhaustion.
Figure 3 shows that the intercept on the dye absorption axis, which proves the
existence of a barrier of diffusion, is significantly reduced in the case of NPE; with
AAE it did not reduce, compared with that during dyeing in the absence of an
auxiliary. The results presented in Figure 1 and Table 1 also show that when dyeing
was carried out at 85 °C, the AAE produced a higher increase in the total dye
absorption and dyeing rate, particularly in the early dyeing stage.

It is known from the relevant literature [1] that the gradual decomposition of
complexes between the levelling agent and the dye can occur when the dyeing
temperature increases. Therefore it is assumed that at a higher temperature, the
decomposition of AAE and anionic dye complexes could be a factor influencing the
renewal of acid milling dye’s affinity for wool fibre. The Blockage of electronegative
sites of wool, due to the interaction with AAE containing amino

82
groups could take place in this case, and an increase in the amount of the net positive
charge on the protein accessible to dye should therefore also be an important factor in
dye absorption.

Colour yield and colour characteristics:

In general, the colour yield for dyed wool should be related to the amount of dye in a
fibre, albeit only up to a certain dye concentration [10]. The K/S of dyed samples in
this study has been measured, and the results are presented in Table 1. The results
show that when the fabric samples were dyed at 60 °C, there was a significant
variation in the ratio of K/S values and dye exhaustion, which is proportional to the
amount of dye in the fibre. The variation of this ratio was small or disappeared
completely when dyeing occurred at 85 °C. A comparison of dye exhaustion and
colour yield data for the dyeings obtained at 60 °C and 85 °C temperature respectively
shows that at the same level of dye exhaustion, for example dyeings at 60 °C and 85
°C temperature respectively, higher K/S values are obtained for samples dyed at
higher temperature. This allows us to assume that when the dye absorption on the
fibre is faster and exhaustion tends to be completed, the dye is transferred from the
endocuticle to the sulphur-rich exocuticle rather than into the cortex, and therefore for
dyeings at 85°C, the colour yield was higher in all the cases studied. Our assumption
is in agreement with the conclusion made by Wolf et al [14]. Summarising the study
of the results by TEM of morphological changes within the fibre of wool during the
sorption and diffusion of 1:2 metal complex dyes, these authors have stated that the
sorption of dyes or surfactants is accelerated by morphological changes within the
cuticle-cellular membrane complex, which is the adsorption zone, or within the main
diffusion path endocuticula, and did not depend on the cortex penetration capacity
[14]. For the samples dyed at 60 °C, we have studied the effect of auxiliaries on the
rate of dyeing and on changes to colour yield (K/S) values. The ratio of K/S values
were compared with the ratio of kinetic constant values (K) for corresponding
dyeings. The result was surprising, because the ratio of kinetic constant values taken

83
from Table 1 KNPE/KA and the ratio of respective colour yield values
(K/S)NPE/(K/S)A were equal to 1.3 and 1.2 respectively. In other words, this compar-
ison shows that the colour yield of dyed wool fibre depends also on the rate of dye
absorption, and not only on the amount of dye in the fibre. The comparison of K and
K/S values for NPE with respect to the corresponding values for dyeing, in the
absence of auxiliary (KAAE ) and (K/S)AAE respectively, show that KNPE /KAAE
=1.5 and (K/S)NPE /(K/S)AAE =1.2. Thus, the results presented above allow us to
assume that the increase in the rate of dye uptake should be considered to be due to
the facility of increase on the amount of dye in the surface layer cuticle of wool fibre.
The approximate calculation of the amount of active sites represented by the basic
groups of cuticle proteins should be less than 8.3×10-5equiv/g. In the cellular-mem-
brane complex and endocuticle jointly, the amount of basic groups should be less than
3.8×10-5 equiv/g, while the amount of dye used in this study was 4.3×10-5 mol/g.
Thus, the dye absorbed in the wool fibres should correspond to to approximately half
the amount of the basic groups considered in the cuticle.

Our results as presented and discussed above are in agreement with the general
statement made by Rippon, that for non-reactive dyes, no thermodynamic equilibrium
with wool is established until the dye transfer into the keratinous regions is complete.
If the dye remains largely in the non-keratinous regions, rapid diffusion out of the
fibre can occur, and poor wet fastness properties are obtained [3].
The results presented in Table 1 show that dyeing at 60 °C both without the auxiliary
and in the presence of AAE results in lower values of both the Cielab coordinates and
the K/S values, compared with those for samples dyed in the presence of NPE. These
results are consistent with the values of dye exhaustion and dyeing rate constants for
the corresponding dyeings presented in Table 1. Increasing the dyeing temperature up
to 85 °C significantly enhanced the redness (a*) of samples dyed in the presence of
AAE, while for the samples dyed in the presence of NPE as well as in the absence of
the auxiliary, chroma (C*) values were reduced.

Colour difference

The colour differences of dyed wool samples could have been influenced by the
increase in wool yellowness or the reduction in the amount of melanin occurring due
to damage to the fibre during dyeing. The migrations of dye into or out of the fibre
during washing or thermal and hydrothermal treatment are also noted to be very
important factors in colour change [15]. We therefore attempted to determine whether
the colour difference of wool fabric dyed with milling Acid Blue 80 could depend on
the extent of fibre damage occurring during dyeing, on the change in the yellowness
index value, or on dye migration during dyeing or the washing of dyeings. In this
study, we introduced trials with benzyl alcohol, which is known as a very efficient
auxiliary for wool dyeing at low temperature, but which unfortunately damages fibres.
We expected that benzyl alcohol should be used to determine whether a relationship is
reliably predictable between the colour change or the yellowing of fabric and the level
of fibre damage occurring during blank dyeing.

84
Table 2. Colour difference and fibre damage by means of fluorescence emission
intensity changes in blank dyed wool fabric; Abbreviations given in Figure 2. • 3% v/v
of benzyl alcohol was added into the bath of blank dyeing.

Table 2 shows the colour difference and yellowness index values of the blank dyed
fabric samples, which have been prepared while maintaining all the other selected
conditions of dyeing, with the exception that the dye was not applied in these trials.
As could be seen, the extent of colour change was higher for dyeings obtained without
the auxiliary. The most significant colour change was when dyeing occurred in the
presence of benzyl alcohol, which was used in this study for comparison. The data of
fluorescence emission spectroscopy of the blank dyed wool fabric samples shows a
marked reduction in the fluorescence emission of tryptophan; that is, a significant
degree of the wool fibre damage was also caused in the sample which had been dyed
in the absence of the auxiliary, but longer exposed to dyeing conditions , than those
with NPE or AAE. The samples dyed in the presence of benzyl alcohol showed an
especially marked lowering in the fluorescence emission of tryptophan, an increase in
the yellowness index value and in colour difference. However, the colour difference
was not dependent upon the wool fibre damage occurring during blank dyeing in the
presence of the electrolyte. It can thus be concluded that neither the increase in
yellowness index value of wool fibre nor the fibre damage occurring during dyeing
was responsible for the general colour difference of the dyeings due to the auxiliaries
applied in this study.

In the light of the findings shown in Table 3, an attempt was made to explain
the beneficial effect of temperature and dyeing auxiliaries on colour wash fastness,
colour change and colour yield change during the treatment of dyed wool fabric. The
corresponding colorimetric data for the dyeings after wash fastness testing are
displayed in Table 3. The comparison of the changes in redness (Δa*), blueness (Δ(-
b*)), chroma (ΔC*) and colour difference ΔE values for dyed fabric samples show the
extent to which each of the different dyeings after washing was changed in terms of
colour loss from the original dyeings. Table 3 shows that the extent of changes for the
samples dyed while applying NPE at 60 °C were generally small, compared with
those for AAE or for dyeings without an auxiliary. The dyeing at 85 °C resulted in an
increase of the degree of colour change for AAE, but did not do so for the electrolyte,
or for dyeings prepared without an electrolyte.
Theoretically, the ability of a surface active levelling agent such as AAE to form

85
Table 3. Changes of colour characteristics after wash fastness testing of fabric dyed
using auxiliaries; Abbreviations given in Figure 2.

dye water-soluble complexes is an important factor within the fibre. The stability of
the AAE-dye complexes which are formed under selected dyeing conditions could be
responsible for AAE sorption into the inner layers of the fibre, either alone or together
with dye, and therefore a relatively greater colour change due to washing the dyed
fabric could occur. As seen from Table 3, the blueness (-b) of dyeings after washing
for AAE was significantly higher; that is to say, we could observe the result of dye
migration from the inner to the outer layers of the fibre. In the case of control dyeing
without auxiliary or dyeing in the presence of electrolyte at a temperature 85 °C, the
colour washing fastness by means of colour difference was higher due to the absence
of the auxiliary, which can modify the dye solubility and hence leads to a lower dye
affinity for wool fibre.

5.3.5 Conclusions

The dyeing behaviour of wool at low temperature using acid milling dyes and non-
ionic auxiliary agents have been investigated. Our work shows the effect of
temperature and auxiliaries on dyeing on acid milling dye equilibrium, rate of dye
uptake, colour yield and colour coordinates of dyed wool fabric. The use of a non-
ionic auxiliary based on alkylphenolethoxylate enhances both the rate of dyeing and
the colour yield of fabric at 60 °C, while the increase in dye substantivity, dyeing rate
and colour yield for alkylaminoethoxylate is most important at higher temperatures.
Increasing dyeing temperature from 60 °C to 85 °C, or using auxiliaries, leads to a
change in the colour yield of the wool fibre, which in general depends on dyeing rate
when dyeing is extended up to the equilibrium. From colour coordinate measurement
data, it is apparent that the colour changes of the dyed fabric sam samples which
occur due to the variation of dyeing temperature are most important, presumably due
to a variation of the dye-auxiliary complexes’ stability and the change of dye affinity
for wool, when alkylaminoethoxylate is used as a dyeing auxiliary.

5.4 Utilization of MLV Liposomes as a Carrier in Dyeing of

Wool/Polyester

86
5.4.1 Abstract

Liposomes are lipid-water systems that can carry hydrophobic and hydrophilic
materials because of their amphiphilic structures.Application of liposomes in dyeing
and finishing textiles is a new technology based on targeting and slow release which
can lead to dyeing at lower temperature along with energy savings and lower
environmental impacts. In this research work, a practical method for dyeing
wool/polyester blends with disperse dye using liposome-forming compounds is
proposed. Multi-lamellar liposomes (MLV) were prepare from Soya lecithin with
45% phosphatidylcholines and applied as an auxiliary in dyeing of wool/polyester
fabric with disperse dye under different experimental conditions of the temperatures,
time and liposome concentrations. The effect of liposomes in dye-bath on dye
exhaustion and dyed fabric properties was investigated to achieve optimum
conditions. The results were compared with those obtained with and without
conventional dyeing auxiliary which showed that the presence of liposomes in the
dye-bath helps to enhance the absorption of disperse dye on the wool/polyester fabric
which was evaluated by colour strength (K/S). An increase on K/S was observed more
significant for the samples dyed at 110ºC for 60 min using 2% owf (on weigh of
fabric) liposomes. Dyeing at higher temperature and longer time with higher liposome
concentrations doesn’t increase the final exhaustion remarkably. The tensile strength,
wash and light fastness of samples have not been changed significantly.

Keywords: MLV, Wool/polyester dyeing, Colour strength (K/S)

5.4.2 Introduction

Liposomes are defined as any structure composed of lipid vesicle bilayers that enclose
a volume, and liposomes containing a dye are generally large, irregular, and
unilamellar [1]. Liposomes have attracted a great deal of scientific interest because of
two reasons. First, liposomes can provide an excellent model for membranes. Second,
these phospholipic bilayers are being developed as a controlled delivery system for
therapeutic agents [2]. Although initially slow to exploit the technology of liposomes,
the textile industry has now produced a wide variety of innovations using the basic
principles of targeting slow release, and protection of sensitive chemicals, principally
in dyeing and finishing [3]. The schematic structure of liposomes is illustrated in
Figure 1.

Blending polyester with

wool is an attempt to
achieve a combination of the
most desirable features of
both fibers, providing
fabrics with good properties.
Dyeing wool is usually
carried out in a boiling bath,
but wool damage during
dyeing process is not severe
provided suitable dyeing
condition are chosen [4].
Polyester has a high glass

87
transition temperature, approximately 80°C, and so dyeing with disperse dyes is done
at high temperature. If a low dyeing temperature is selected in order to avoid
damaging the wool, the disperse dye uptake on the polyester will not be adequate to
achieve a good dyeing. On the other hand wool maybe damaged unacceptably if high
dyeing temperature or prolonged dyeing times are adopted in order to increase dye
uptake on polyester. Carriers are useful agents for wool/polyester blends and permit
dyeing at relatively low temperatures, although they have some disadvantages, e.g.
being toxic and harmful to the environment [5, 6]. In attempt to decrease high energy
costs, expensive machinery investment, and undesirable effects such as wool damage
during the conventional dyeing process and protect environment, alternative method
for dyeing wool/polyester blends with disperse dye is using liposome-forming
compounds. Although wool/polyester blends are industrially dyed simultaneously
with wool and polyester dyes and previous studies have already determined the effect
of liposomes on wool dyeing, this study focuses on the action of liposomes on
wool/polyester blend dyeing with disperse dyes. Therefore, we try to prepare and
produce multi-lamellar liposomes (MLV) from Soya lecithin with 45%
phosphatidylcholine and study the influence of liposomes in dye-bath at different
temperature, exhaustion time and concentration during in wool/polyester dyeing with
disperse dye. The dyeing temperature and time was optimized with optimum
concentration of liposomes. The tensile strength, wash and light fastness properties of
samples have also reported.

5.4.3 Experimental

Materials and Methods

The material to be dyed was woven wool/polyester fabric supplied by Iran Merinous
(Ghom, Iran). Soya lecithin (containing 45% phosphotydilcholin) with phase
transition temperature (Tc) of -18ºC was prepared by Lipoid (Germany). The disperse
dye Sumikaron Blue EF-BL (C.I.Disperse blue 56) was used; its chemical structure
indicated in Figure 2 [7]. Carrier used was
TANAVOL supplied by Tanatex Chemical Co.
(Netherlands), CATA PON 310N as a nonionic
detergent and CATA PERS 200 NDF as a dispersing
agent from Catan Chemical Co. (Iran).

Fig 2. Chemical structure of C.I.Disperse blue 56 dye. Dyeing was done in an Ahiba
Polymat Data Color dyeing machine and the reflectance spectras of the dyed samples
determined by ACS Spectra Sensor �� integrated with an IBM-PC. The wash-
fastness of the liposomes treated dyed fabric was measured according to ISO 150-C03
[8]. For light-fastness measurements, the samples were exposed to the daylight for 7
dyes according to the daylight ISO 105-B02 in Xenotest 150S\ machine [9] and
changes in the colour (fading) were assessed bye the blue scale. Also the tensile
strength of the samples evaluated according to ASTM 5035:1974 [10].

88
Preparation of MLV Liposomes:

Multilamellar Liposomes were prepared following the thin film hydration method
[11]. A lipid film was formed by removing the organic solvent under low vacuum
along with temperature by rotary evaporation (temperature bath being 35- 40ºC) from
Soya lecithin solution in chloroform. Aqueous phase containing distilled water was
added to the lipid film. The solution was then swirled to remove the lipid from the
walls of the flask and glass beads, also to disperse large lipid aggregates; glass beads
were added to facilitate dispersion. After preparation, the resulting milky liposome
suspension was left to equilibrate for 15 minutes and applied in wool/polyester dyeing
process.

Dyeing Procedure:

Before dyeing, the wool/polyester samples should be cleaned to become free from the
impurities. Therefore, samples were scoured using 1 gr/l nonionic detergent at a liquor
ratio of 40:1 for 30 min at 60ºC. The samples were then rinsed with warm water and
tap water and then dried at room temperature. Wool/polyester samples were treated
with liposomes, without liposomes or with conventional auxiliaries. The dye bath
were prepared with different concentrations of prepared MLV liposomes (0%, 1%,
2%, 3% o.w.f.), 2% o.w.f (on weight of fabric) disperse dye (Sumikaron Blue EF-BL)
and dispersing agent at a liquor ratio of 40:1; acetic acid was added to adjust the pH to
4.5-5.5. Dyeing in Polymat dyeing machine was initiated at room temperature and the
temperature raised by 2ºC/min until the maximum temperature (95ºC, 110ºC or
120ºC) was reached, remaining there for 45, 60 or 75 minutes. The samples were then
rinsed with tap water and dried at 60ºC for 10 minutes The reflectance values and the
corresponding CIE L*, a*, b*, C* and h0 of the dyed samples were measured using a
Datacolor Texflash spectrophotometer interfaced to a digital PC under illuminant
D65, using a 100 standard observer with UV component included and specular
component excluded. The distribution of disperse dye on the wool/polyester samples
were determined by the K/S values calculated according to the Kubelka-Munk
equation from the amount of reflectance (R) at the maximum wavelength (� max

5.4.4 Results and Discussions

Dyeing Profiles

The color strengths (K/S value) were calculated according to the equation1 from the
reflectance amount of samples at the maximum wavelength (which give maximum
dye absorption). All of the dyed samples indicated the minimum value of reflectance
at 460nm (_max). The K/S values of wool/polyester samples dyed with disperse dye,
applied liposome concentrations from 0% to 3% o.w.f at three different temperatures
(95ºC, 110ºC and 120ºC) and exhaustion times (45, 60 and 75 min) were obtained It
can be observed from figure 3, 4 and 5 that any increase in time of dyeing and
concentrations of liposome caused an increase in the values of K/S. Enhancement of

89
(K/S) values is more significant at 110ºC than 95ºC and 120ºC. Because of compact
crystalline structure of polyester dyeing at low temperature (95ºC) doesn.t lead to
achieve satisfactory dye absorption. Increasing of temperature to 120ºC, with different
exhaustion time and liposomes concentrations doesn.t raise the K/S values
significantly even in some samples, decrease in K/S values observed. This could be
related to the liposomes stability. The liposome above the 85ºC gradually converted to
the smaller particles of phospholipids. These changes of the particle size of
phospholipid lead to coating of wool/polyester surface with a layer of phospholipid at
120ºC which leads to decrease the value of K/S.

Fig 3. K/S values of the dyed samples with different liposomes concentration and
exhaustion time and at 95ºC.

Fig 4. K/S values of the dyed samples with different andliposomes

concentration and exhaustion time at 110ºC.

Fig 5. K/S values of the dyed samples with different liposome

concentration and exhaustion time at 120

90
The results also indicated that although the samples dyed without liposomes at 120ºC
have a higher value of K/S comparing with the samples dyed with liposomes at 110ºC
according to figure 4 and 5, but their differences were not significant along with
having preferences rather than synthetic auxiliaries e.g. not being toxic and harmful to
the environment. It can be concluded that in dyeing of wool/polyester with disperse
dyes, utilization of 2% o.w.f liposomes in dye-bath at 110ºC for 60 min, clearly
reduce the dyeing temperature about 10ºC compared with a conventional dyeing
process. These results are in accordance with the results obtained by Marti for the
dyeing of wool/polyester with disperse dye. 3.2 Fabric Properties in Liposome Dyeing
3.2.1 Wash & Light Fastness
In order to study the
effect of liposomes on the
dyed wool/polyester
samples, wash and light
fastness were tested and
the results listed in Tables
1 and 2. The results
showed that dyeing with
liposome doesn.t have
clear effect on wash and
light fastness of samples
compare with those dyed
with conventional dyeing
process

Tensile Strength

The results of tensile

strength test for dyed
wool/polyester samples
were shown in figure 6.
The influence of dyeing
temperature on the
strength of wool component was found to be very significant, even at short dyeing
times (45 min). The rate of decrease in tensile strength decreased with increasing
dyeing temperature. For this reason it is not recommendable to expose the wool
component to be dyed at above 110°C. Considering figure 6, comparing the tensile
strength obtained by dyed samples with 2 % liposome and conventional dyeing (with
carrier at 95°C and without auxiliaries at 120°C) for 60 min, reveals that increasing
temperature and time of dyeing decrease the tensile strength which is more rapidly
above 110°C and 60 minute. Also less decrease in tensile strength of dyed samples
with 2% liposome is observed compared with samples dyed conventionally

91
 Fig 6. Tensile strength of wool/polyester samples dyed with
disperse dye as a function of dyeing temperature for 60 min.

5.4.5 Conclusions

In this work, applications of liposomes as a carrier in dyeing of wool/polyester by

some of the synthetic dyes have already been reported. From our results, it concluded
that a new method of wool/polyester dyeing using disperse dye C.I. Disperse Blue 56
by means of large multilamellar liposomes could be considered appropriate for
improving dye exhaustion on samples and reduce the dyeing temperature
approximately 10ºC. The optimum dyeing condition of wool/polyester fabric with this
disperse dye is under 110°C for 60 minute with 2% liposomes concentration. Also
using liposomes could lead to decrease high energy costs, expensive machinery
investment, and undesirable effects such as wool damage during the dyeing process
and protect environment.

92
Conclusion:

The process of applying dye to a textile material or fibre is known as dyeing of textile
fibre. Auxiliaries are essential in the field of textile dying to achieve the desired goal
effectively and without facing difficulties. There are several hundreds of auxiliaries
and they perform very important role in the respected field of dyeing. New dyeing
auxiliaries in different types dye stuffs and dyeing process are constantly being
developed. Research is also going on to make the older ones more efficient. The
classification, function, necessity and different auxiliaries used with different dye stuff
have already been studied. The study of textile dyeing auxiliaries enables us to know
the influence of auxiliaries in fixing, absorption, exhaustion, sticking, improving the
substrate in readiness for colouration, stabilizing the application medium, improving
the fastness of dyeing etc. Here the synthesis of reactive auxiliaries for dye resist
treatment of wool, the effect of UV absorbers on ultra violet protection properties of
dyed cellulosic fibre, the influence of non ionic auxiliaries on absorption of acid
milling dye, the utilization of MLV liposome as a career in dye have been studied.

93
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