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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, appliqu 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, macram, 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, appliqu, 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.
And at intervals bridges derived from the amino acid cystine connect the chains.
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.
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
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:
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.
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 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 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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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 creaseresistance, 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
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 heatset 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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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.
Nitro dyes.
Nitroso dyes.
Azo (Monazo) dyes.
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.
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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.
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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, Ndimethylaniline (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.
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(2) By Heumanns 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.
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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).
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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.
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Step
2.
OBenzoylbenzoic acid
is
cyclized
by
treatment
with
concentrated
sulphuric acid to
form anthraquinone.
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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.
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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.
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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
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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
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BCE, but it did not appear in Europe until the 4th century. Cotton waving
establishments were formed in Italy in the 13 th & 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 12 th
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 dyers 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 citys 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. Its 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 16 th 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 colourswhites, 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 golds. 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
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.
38
I
C+
A-
II
(nC)n+
(nA)n-
III
m(CA)nCn+
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
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 walls forces such as hydrogen bonds, e.g. such polar force are to
Hydrogen adjacent molecules of water as follows :
H
H-O
H
H-O
H-O H- O
Non-polar van der walls 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.
give
excellent
41
3. Yarn Dyeing is the method of dyeing yarns in forms of hanks or packages dyeing.
This will give Scottishs 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)
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
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.
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
4.5.1 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.
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
Detergent & Wetting
Agent Oil stain remove
Basic Chemical:
Alkali
Bleaching Bath
Detergent & Wetting Agent
Antifomking Agent
Sequestrant
Lubricant/Antecreasant
Peroxide Stabilizer
Basic Chemical:
Alkali
Hydrogen Peroxide
Bleaching Bath
Detergent & Wetting Agent
Antifoaming Agent
Sequestrant
Lubricant/Antecreasant
Oil stain remove
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.
4.5.6 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
51
52
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
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)
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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.
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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.
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).
59
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
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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 C. 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.
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)
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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%.
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 bifunctional 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
66
67
68
Fig. 10a,b: Resist effectiveness of R versus auxiliary uptake of the fibres bifunctional 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 striazines 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
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 fibres dyed by the exhaustion method. The specific nature of the hydrogen bridge formed 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
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.
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
73
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
)100% (1)
B1
Where:
B1 the absorption of the dyebath at max before dyeing;
B2 the absorption of the dyebath at max after dyeing.
The results of these measurements are listed in Table 4.
E=(1-
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 130C 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
(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 pyridinewater 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() - the solar spectral irradiance, W/m2nm;
() - the erythema action spectrum;
Ti() - the spectral transmittance sample i at the wavelength ;
- the interval of the wavelength, nm.
The results obtained are presented graphically in Figures 10 and 11.
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 ammonia, results in only a small decrease in their molar absorption coefficients max, 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 8090%. 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.
77
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 watersoluble 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
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 max 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 performed 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.
(3)
L*=L*trl-Lin,
a*=a*trl-a*in,
b*=b*trl-b*in Lin, a*in, and b*in are parameters of initial species before the
relevant treatments.
80
The E deviation of all treated samples was no higher than 0.2. The coordinates of the
colours obtained and the results of the E 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]:
YI 100
1.28 X 1.06Z
%
Y
(4)
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 (ex=295 nm, ex=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
C
(5)
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 dyes 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.
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 comparison 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 8.310-5equiv/g. In the cellular-membrane
complex and endocuticle jointly, the amount of basic groups should be less than
3.810-5 equiv/g, while the amount of dye used in this study was 4.310-5 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 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 (a*), blueness ((b*)), chroma (C*) and colour difference E 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 nonionic 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 nonionic 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.
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 110C for 60 min using 2% owf (on weigh of
fabric) liposomes. Dyeing at higher temperature and longer time with higher liposome
concentrations doesnt 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 80C, 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 -18C 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 washfastness 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
89
(K/S) values is more significant at 110C than 95C and 120C. Because of compact
crystalline structure of polyester dyeing at low temperature (95C) doesn.t lead to
achieve satisfactory dye absorption. Increasing of temperature to 120C, 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 85C 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
120C 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 95C.
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The results also indicated that although the samples dyed without liposomes at 120C
have a higher value of K/S comparing with the samples dyed with liposomes at 110C
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 110C for 60 min, clearly
reduce the dyeing temperature about 10C 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 110C. Considering figure 6, comparing the tensile
strength obtained by dyed samples with 2 % liposome and conventional dyeing (with
carrier at 95C and without auxiliaries at 120C) for 60 min, reveals that increasing
temperature and time of dyeing decrease the tensile strength which is more rapidly
above 110C and 60 minute. Also less decrease in tensile strength of dyed samples
with 2% liposome is observed compared with samples dyed conventionally
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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 10C. The optimum dyeing condition of wool/polyester fabric with this
disperse dye is under 110C 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.
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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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