Lecture 000000

Cationic dyeing
(Basic dyes)

In this lecture We ''ll learn about

· Introduction of Disperse Dye
· Dyeing of Polyester With disperse dye
· Dyeing mechanism with and without carrier
· Thermosol dyeing of Polyester and its
mechanism
CATIONIC DYES
(Basic dyes)

2
 HISTORY
• Cationic dyes are one of the earliest synthetic dyes produced.
• The aniline violet synthesized by W.H. Perkin in the United States
in 1856 and the subsequent crystal violet and malachite green are
both cationic dyes.
• They have brilliant colors but are not light fast.

malachite green

crystal violet
3
H

4
 INTRODUCTION

• Basic dyes are also called cationic dyes because in solution the
basic dye molecule ionizes, causing its colored component
(chromophore) to become an action of positively charged radical.

• This is a class of synthetic dyes, that act as bases and when made
soluble in water, they form a colored cationic salt, which can react
with the anionic sites on the surface of the substrate. The basic dyes
produce bright shades with high tinctorial values, on textile materials.

5
 Classification of cationic dyes

The positively charged group in the cationic dye molecule is

connected to the conjugate system in a certain way, and then forms a
salt with the anionic group.
According to the position of the positively charged group in the
conjugate system, cationic dyes can be divided into two categories:

6
 (a) Isolated cationic dye
 The isolated cationic dye precursor and the positively charged group
are connected through the spacer, and the positive charge is
localized, similar to the introduction of a quaternary ammonium
group at the molecular end of a disperse dye.
 Because the positive charge is concentrated, it is easy to combine
with the fiber, and the dyeing percentage and the dyeing rate are
relatively high, but the leveling property is not good.
 Generally, the shade is dark, the molar absorbance is low, and the
shade is not strong enough, but it has excellent heat resistance and
light resistance and high fastness. It is often used for dyeing
medium and light colors. E.g. Basic red 18.

7
 (b) Conjugated cationic dyes
 The positively charged group of the conjugated cationic dye is
directly connected to the conjugated system of the dye, and the
positive charge is delocalized.
 The color of this kind of dye is very bright, the molar absorbance is
high, but some varieties have poor light resistance and heat
resistance.
 Among the types of use, the conjugate type accounts for more than
90%. There are many varieties of conjugated cationic dyes, mainly
including triarylmethane, oxazine, and polymethine structures.
 Example; Basic yellow 13

8
 Characteristics of Basic Dyes
• The outstanding characteristics of the basic are brilliance and intensity
of their colors.
• The bright colors achieved from basic dyestuffs do not usually occur
with other dye classes.
• Many of the basic dyestuffs are sparingly soluble in water.
• The addition of glacial acetic acid helps to dissolve the basic dye
quickly in water.
• Basic dye is readily soluble in alcohol or mentholated spirit.

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 Characteristics of Basic Dyes
 The basic dyestuffs are poor fastness to light and vary with
regard to washing fastness from poor to moderate.

 An important property of basic dye is that they will combine with

tannic acid to form an insoluble compound provided mineral
acid is absent.

 The wet fastness of the basic dye on protein fibers can also be
improved by back tanning. This consists of after treating the dyed
material with tannic acid in order to form the insoluble complex
thereby reducing the tendency to migrate.

10
 Characteristics of Basic Dyes
• The basic dyestuff will combine with direct dyes or sulphur dyes or
some acid dyestuffs.
• So they cannot be used together in the same bath. But basic
dyestuffs are used in after treating cotton or other materials dyed with
direct colors. Here the direct dyestuff acts as mordant.
• When treated with a reducing agent most of the basic dye get
converted into their colors less leuco compounds, return to their
original color by oxidizing agents or even by exposure to air.
• Special cationic dyes are available for dyeing acrylic fibers.

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 Characteristics of Basic Dyes
 Basic dye can be removed from the material by boiling it with
dilute acetic acid or hydrochloric acid.

 Basic dye are used for woolen goods when particularly bright shades
are required which cannot be obtained with an acid dyes.

 Basic dye do not have affinity for cellulosic fibers like cotton. The
use of basic dye on cotton involves the troublesome process of
mandating with tannic acid. But, sometimes, bright shades are
demanded on cotton which can only be obtained with them.
 Basic dyestuffs are also used for making inks, typewriter ribbons
and dyeing leather.

12
1. Solubility:
Nature of cationic dyes
 Salt-forming alkyl and anionic groups in the cationic dye molecule affect the
solubility of the dye.
 In addition, if there are anionic compounds in the dyeing medium, such as
anionic surfactants and anionic dyes, they will also combine with cationic dyes to
form a precipitate..
2. Sensitivity to pH:
 Generally, the stable pH range of cationic dyes is 2.5-5.5. When the pH value is
low, the amino group in the dye molecule is protonated, changing from an
electron donor to an electron withdrawing group, causing the color of the dye to
change; if the pH value is high, the cationic dye may form a quaternary amine
base, or the structure may be destroyed.
 Dyes precipitate, change color or fade. For example, oxazine dyes are transformed
into non-cationic dyes in alkaline medium and lose their affinity for acrylic fiber
and cannot be dyed.

13
 3. Compatibility:
 Cationic dyes have a relatively high affinity for acrylic fibers, and have poor
migration properties in the fibers, making it difficult to level dye.

 Different dyes have different affinities for the same fiber, and their diffusion rate inside
the fiber is also different.

 When dyes with a large difference in dyeing rate are mixed, the color change and
uneven dyeing are prone to occur during the dyeing process;

 When dyes with similar speeds are blended, their concentration ratio in the dyeing
bath is basically unchanged, so that the color of the product remains consistent and
the dyeing is more uniform. The performance of this type of dyeing is called the
compatibility of dyes.

14
 Basic/Cationic dyes are available in:
• Powders
• Pearls
• Liquids

15
 Advantages of Basic Dyes:
• High Tinctorial strength (depth of color achieved through pigmentation.)
• Moderate substantivity (the ability of a chemical or dye to stick to a target.)
• Relatively economical
• Wide shade range
• Includes some of the most brilliant synthetic dyes
• Shows good brightness.

16
 Limitations of Basic Dyes:
• Poor shade stability
• High acid content
• colored backwaters
• Very poor lightfastness
• Preferential dyeing

17
 Modified Basic Dyes:

 These dyes, generally based on the chemistry of basic dyes, have longer
molecular structures than traditional basic dye, and thus have significantly
improved properties.
 Though still cationic in nature, modified basic dyestuffs exhibit improved
fiber coverage and substantivity on many furnishes, making them ideal for
dyeing applications.
 Lightfastness is also improved considerably over traditional basic dye.

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Key Advantages of modified basic dyes Over
Conventional Basic Dyes:
• Excellent substantivity
• Better Lightfastness
• Covers all fibers
• Clear backwaters

19
 Application of the Basic Dyes:
• Basic dyestuffs are extensively used for dyeing of jute, cut flowers, dried flower,
coir, etc. For dyeing Acrylic fibers, basic dye are used widely.
• Modified basic dye is used for dyeing of Acrylic fiber, because these are perfect
for this material. If the reason behind the success of Basic dyes is analysed, it
would be seen that the positively charged cations of the Basic dyes gets attracted
towards the negatively charged anions in the acrylic fiber.
• Acrylic polymers have anionic groups attached to it. They are most commonly
the sulphonate group, –SO3−, followed closed by the carboxylate group, –CO2−.
• This reaction of the cation and anion results in salt linkages. Basic dye does not
show absolutely any migration in acrylic fibers under normal dyeing conditions.

20
 H

• Basic dyestuffs are also preferred to dye leather, because they can get
combined easily with vegetable-tanned leather thus doing away with
mordant.
• Basic dyes are also used in the coloring of papers. Basic dyestuffs for
paper widely used in textile industries. The dye is generally used to
produce bright and deep shades with superior light and wash fastness.
• Its application is similar to that of direct dyes but requires different and
more precise controls with auxiliaries and temperature.

21
a substance, typically an inorganic oxide, that combines with a dye or stain and thereby fixes it in a material.
 Cationic Dyes as Chromophores

• Cationic dyes carry a positive charge in their molecule. T

• he salt-forming counter ion is in most cases the colorless anion of
a low molecular mass inorganic or organic acid.
• Many of these dyes can be converted into water-insoluble dye
bases by addition of alkali.

• For this reason, they were formerly called basic dyes; although
still in use today, the term should be abandoned.

22
 H
• The positive charge of cationic dyes may be either localized or delocalized.
In 1, the positive charge is localized on an ammonium group

• In the diazahemicyanine dye 2, the positive charge is delocalized across the

dye cation.

As in these examples, the

charge-carrying atom is
usually nitrogen, but in
some dyes this function is
adopted by an oxygen,
sulfur, or phosphorus atom.

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 General Synthesis

Cationic functionality is found in various types of dyes, mainly in

cationic azo dyes and methine dyes, but also in anthraquinone di-
and triarylcarbenium , phthalocyanine dyes, and in various
polycarbocyclic and solvent dyes.

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 Chemical Structure and Classification
Dyes with Delocalized Charge
Cationic dyes with delocalized charge are classified with the methine dyes . They may
be viewed as vinylogous amidinium salts .

Dyes in which both charged terminal atoms are not part of a heterocyclic ring
are called streptocyanine dyes. An example is 4, which dyes paper in a
greenish yellow shade.

25
 H

• In the hemicyanine dyes, one of the charged terminal atoms is part of a

heterocyclic ring, and the other is a nitrogen atom directly linked to the
methine chain. An example of this type is the enamine dye 6, which
confers a yellow color to polyacrylonitrile fibers.

• Insertion of an aryl residue between the second nitrogen atom and the
methine chain leads to the styryl dyes, which dye polyacrylonitrile in red
and purple shades, e.g., 7

26
• Diphenylmethane and triphenylmethane dyes are monomethine
dyes with two or three terminal aryl groups, of which at least one,
but preferably two or three, are substituted by a donor group para
to the methine carbon atom. The most important donor is the amino
group. Important dyes belonging to this class include the well-
known malachite green (12) and crystal violet (13).

27
Dyes with Localized Charge
in contrast to dyes with delocalized charge, in
which the charge is an essential part of the
chromophore, in dyes with localized charge the
charged atom in most cases is isolated from the
chromophore by a non conjugated group.
Therefore, any chromophore can be used, and
this chromophore is not or only slightly
influenced by the charged atom.

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• Azo Dyes . The localized charge in cationic azo dyes may reside
either in the diazo moiety (e.g., 19) or in the coupling component (e.g.,
20

29
30
31
32
 Cationic Dyes for Synthetic Fibers
• The cationic chromophore is first absorbed by the negatively
charged fiber surface and then diffuses, at elevated
temperature, into the interior of the fiber; there it binds to
active acid groups, the number of which is limited and the
accessibility of which depends on temperature and fiber
constitution. Therefore, the dyeing characteristics of a cationic
dye are determined by affinity and diffusibility.
• The affinity of cationic dyes is enhanced by increasing the size
of the molecule and especially by introducing aromatic
residues. The phenyl-substituted dye 28 is absorbed onto
polyacrylonitrile materials.

33
• Residues which make the substance more hydrophilic, such as
carboxyl and hydroxyethyl groups, lower the affinity of
cationic dyes for polyacrylonitrile. Therefore, dye 29 is
absorbed onto polyacrylonitrile materials.

34
• High affinity may, however, lead to problems in leveling,
because these dyes are bound quickly and nearly
irreversibly to the acid groups of the fiber.
• Diffusibility increases with decreasing molecular mass.
Dyes with a cation mass of less than 275 migrate well
and are suitable for the production of level dyeings,
especially in the lighter shades.
• Cationic dyes are also used to dye polyacrylonitrile
fibers during the spinning process either from
dimethylformamide solution or in the gel stage
subsequent to aqueous spinning processes.
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Auxiliaries’ for basic Dyeing

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• Auxiliaries Associated With Basic/
Cationic Dyeing
• Wetting Agent
• Acetic Acid
• Sequestration or Chelation
• Leveling Agent/ Retarding Agent
• Electrolyte

37
Wetting agents are substances that reduce the surface
tension of water to allow it to spread drops onto a surface, increasing
the spreading abilities of a liquid. Lowering the surface tension lowers
the energy required to spread drops onto a film, thus weakening the of
the liquid and strengthening its adhesive properties. One principle of
how wetting agents work is in the formation of micelles.
• There are three main types of wetting agents
• Anionic
• Cationic
• Amphoteric wetting agents
• Nonionic wetting agents

38
Acetic acid used for maintain PH 4.5-5.5, because the basic
dye require acidic medium.
• Acetic acid (CH3COOH), also called ethanoic acid, the most
important of the carboxylic acids.
• Industrially, acetic acid is used in the preparation of metal
acetates, used in some printing processes; vinyl acetate, employed
in the production of plastics; cellulose acetate, used in making
photographic films and textiles; and volatile organic.
• Acetic acid has been prepared on an industrial scale by air
oxidation of acetaldehyde, by oxidation of ethanol (ethyl alcohol),
and by oxidation of butane and butane.

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Sequestrating or Chelating
 A sequestering or chelating agent is a complex forming
auxiliary chemical with metals such as Iron, Copper,
Nickel, Zinc and Magnesium that are present in water
and affects the textile processing in many way. It is a
dyeing auxiliaries which is used during dyeing for
removing hardness of water. They form molecules in
which the ions are held so securely (sequestered) that
they can no longer react.
 EXAMPLE
Aminopolycarboxylates(EDTA), phosphates and
phosphonates etc.

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EDTA :Good sequestering agent for
calcium and magnesium at alkaline pH but no
sequestering agents on Fe3+ at alkaline pH.
• Not stable with oxidizing agents and Low
solubility in acidic medium.
• Some ligands can bond to a metal atom using
more than two pairs of electrons.
• An example is ethylenediamminetetraacetate
ion (EDTA4-), the Lewis structure of which is
shown below

41
Retarding Agents
• To solve problem of dyeing on acrylic fibers various
approaches have been developed including the use of
temperature as well as cationic and anionic retarders.
• There are two types of retarding agents:-
a) those that form a complex with the dye and thus tend to
retain it in the dye bath.
b) those that compete with the dye for the ionic dye sites in
Retarding Agent.

42
• A cationic retarder based on a quaternary ammonium compound
competes with the cationic dye for the anionic dye sites in the
fiber. This competition reduces the initial strike rate of the dye, to
promote level dyeing, but may also reduce the final dye bath
exhaustion.
A useful general classification of cationic retarders according to their
properties has been given:
a) strongly cationic with a strong blocking effect
b) moderately cationic with a weak blocking effect
c) weakly cationic with no blocking effect
d) products with little or no retarding effect but giving some levellyng

43
44
Retarder has a compatibility value equal to or slightly lower than
that of the dyes, so that it will tend to be absorbed by the fiber
either at the same rate as the dyes or somewhat more quickly.

• Reatarders Containing long aliphatic chains. They act by

reducing the effective dye concentration in the bath at higher
temperatures, the dye cations replacing the retarder cations
due to their strong affinity. The multiple positive charges of
the polymeric film barrier, formed around the fiber surface,
greatly reduce the rate of dye adsorption. As the temperature
increases, this barrier film breaks down and dye molecule
diffuse in fibers.

45
Electrolytes such as sodium chloride and sodium
sulphate tend to retard dyeing through preferential
adsorption and subsequent displacement by the dye of the
more mobile sodium ions, although the effect is relatively
weak even compared with the weaker cationic retarders.
Nevertheless, the use of up to 10% o.w.f. sodium sulphate in
combination with a cationic retarder may enable the
amount of the Electrolytes.

46
• The limitations of electrolytes, apart from this
lower effectiveness, are that they reduce the final uptake
of dye, their effectiveness decreases with increase in
temperature and their effect is greatest with fibers fibers
containing weakly anionic groups such as carboxylate,
rather than stronger ones such as sulphonate. The
retarding effect of electrolytes in the application of basic
dyes to acrylic fibers increases with increasing
concentration of salt up to a to a certain level.

47
The Role of Electrolytes in the Cationic Dye-Acrylic Fiber System

48
Dyeing of Acrylic Fiber with
Basic Dyes

49
• Acrylic fiber has become the third
largest produced synthetic fiber in the
world. Regular acrylic fibers are
produced from polymers containing 85%
or more of acrylonitrile monomer, the
other co-monomers usually being
methacrylic acid, methylmethacrylate,
vinyl acetate or a similar vinyl
compound which are incorporated in
order to improve dyeability and
mechanical properties.

50
• Initially, acrylic fibers were very difficult to
dye and, until acidic groups were
incorporated as dye sites in the fiber, basic
dyestuffs were of little interest. Cationic
dyes are currently used in large quantities
to dye acrylics (Orlon, Acrilan, Creslan,
Zefran) and modified acrylics (Verel).
Subsequent developments led to the
introduction of acidic groups to polyester
and polyamide fibers, further increasing the
market for these dyes.
51
• To obtain fibers with satisfactory dyeing properties,
anionic comonomers are used. In this way, the glass
transition temperature Tg is lowered and anionic groups
are available that can act as dye sites for cationic dyes.
Thus, acrylic fibers are reliably and economically
dyeable with cationic dyes.
• Dyeing is performed mainly by exhaustion processes
(batchwise). Another dyeing method with increased
importance is the gel dyeing process. Dyeing in the gel
state takes place during production of the fiber, i.e., after
the fiber has been extruded and the solvent has been
washed out, but before the fiber is stretched and dried.
Continuous dyeing of stock, cable, and tops is also
possible according to the pad steam process

52
• Acrylic fibers can be dyed wih cationic dyes only
above the glass transition temperature Tg, which has
a characteristic value for each type of fiber and for
most fibers lies between 70 and 80 °C. Cationic dyes
form a heteropolar bond with anionic groups of the
fiber. The number of anionic sites in the fiber
determine the saturation value SF, i.e. the maximum
amount of dye which can be taken up by the fiber. Tg
and SF are indicated by the fiber producer.

53
• The dyeing process is governed by the affinity of the dyes to
the fiber and their diffusion in the fiber. Since cationic dyes
have a very high affinity to acrylic fibers, the equilibrium
distribution between dye liquor and fiber lies on the side of the
fiber and yields a normal bath exhaustion of 97-100 %. The
dye diffusion depends on the difference in dye concentration
between fiber and dye liquor according to Fick’s law.

54
• The speed of exhaustion based on dye diffusion is a fiber
characteristics and is strongly temperature dependent. Above
Tg it doubles with a temperature increase of 2.53 °C.
Therefore, it is very important for dyeing PAC with cationic
dyes to carefully control the temperature during dyeing.
Consequently, the optimum time temperature program for each
dyeing should be established before a production run.
• When the dyeing equilibrium is reached, the relative saturation
value Srel indicates the degree of levelness which can be
expected during dye absorpion; the higher Srel the better the
levelness. For similar Srel for different dyeings a similar
course of the dyeing process can be assumed

55
• High affinity for the fiber and rapid
diffusion mean short dye cycles, independence
from liquor ratio, no dyeing accelerants, and good
reproducibility. However it also means poor
migration properties of the dyes after they have
formed a heteropolar bond with the anionic sites on
the fiber, so that inequalities in the dyed material
are difficult to level out. Therefore, it is very
important to aim for homogeneous bath exhaustion.

56
Cationic dyes influence each other during
absorption. If several dyes exhaust tone-in-tone from
one bath (i.e., the depth of color, but not the shade,
changes in the course of absorption), the dyes are
referred to as compatible. In the case of cationic dyes
on PAC, the property of being compatible is dye
specific and also applies to dyeing under different
conditions and in different shades. It depends on the
product DA (D = diffusion coefficient, = dye affinity)
and can be described by the compatibility value K,
which ranges from 1 to 5.

57
 Exhaustion Process

• Normal PAC textile material is dyed as cable or stock in packages,

as yarn in hanks or packages (direction of liquor: inside to outside),
as pieces on beam, overflow, paddle machines (knitwear), or drums
(socks). High-bulk (HB) yarns are dyed as muffs.
• Strongly soiled textile material is prewashed, preferably in a
weakly alkaline bath.
• Because of the strong temperature dependence of exhaustion and
the poor migration properties, dye absorption must be as level as
possible from the start. Correspondingly, attention should be paid
to uniform packaging, package density, liquor flow or movement of
textile material, and controlled machine conditions.

58
Dyes with the same K value are selected; the largest choice
of dyes and most suitable retarders are available at K = 3. In
cases where sufficient levelness during absorption is critical,
dyes with a relatively low affinity (with high K) are
recommended . According to the dyes present in the actual
recipe the amount of retarder is adjusted to give a favorable
Srel. The dyes are dissolved in acetic acid, the dye bath is
made up with all auxiliaries at 60-70 °C, and the textile
material is added.
Dyeing is conducted by controlling the temperature. This is
followed by cooling (ca. 0.3 °C/min to 60 °C, i.e., well
below the glass transition temperature), rinsing, and after
treatment.
59
60
• Dyeing can be performed more economically and reliably by using
systematic methods for the optimization of formulations and dyeing
conditions.
• Dyes with the same K are selected and the following factors are determined
for each dyeing:
1. The amount of retarder that leads to the most favorable relative saturation
value Srel,
2. The temperatures at which exhaustion starts or ends (the critical temperature
range outside which rapid heating will not cause unlevelness),
3. The most favorable rate of heating in this temperature range, depending on
the dyeing machine and the textile material, and
4. The dwelling time at the maximum (final) dyeing temperature required for
penetration of the dyes used. It Leeds to level dyeing's in short dyeing times,
good reproducibility and savings in laboratory work.

61
 Dyeing of Special Fiber Types with
Cationic Dyes by the Exhaustion Process
• High-Bulk Material.
The bulking of high-bulk (HB) material proceeds either as a
pretreatment with steam continuously for yarn, batchwise for
yarn and knitwear, or in the dyebath before dye absorption at
ca. 80 °C for 5-10 min without liquor movement .
To avoid non levelness in this process, retarders are
employed to ensure that very little dye is absorbed during the
bulking time. With HB bicomponent fibers, a high Srel can
interfere with the reversible shrinkage. For this reason,
anionic retarders and dyes with a K value of 4 or more are
preferred.
62
• Pore Fibers.
As a result of their greater light scattering, pore fibers (light
fibers with high water absorption capacity) require up to
three times more dye than normal fibers
Navy and black shades are hard to dye; for dyeing other
deep hues, an ammonical reductive after cleaning step is
required. The diffusion of dyes proceeds mainly in the pores
of the fiber, changing the K values of the dyes. With the
exception of a higher softener requirement, the rules of
normal PAC dyeing apply.

63
• Microfibers.
PAC microfibers behave differently in some respects from
normal acrylic fibers. First, more dye is required for the
desired shade in each case because of the greater light
scattering of the fiber. This requirement increases more
than twofold with increasing depth of color (similar to
pore fibers). For this reason, the fiber saturation is usually
adjusted to a higher value by the fiber producer. The
characteristic dyeing rate of the fiber is also higher.
Corresponding to these increased values, more cationic
retarder is required and the starting temperatures are lower

64
• Modacrylic Fibers.
Modacrylic fibers containing more than 20 % of vinyl chloride
or vinylidene chloride as comonomer are used because of their
reduced flammability. Depending on the comonomers, various
types of modacrylic fibers exist that differ especially in the
range of dyeing temperatures. In all cases, the critical
temperature range is greater (25-50 °C) than with normal acrylic
fibers (15 °C), and absorption starts in most cases at lower
temperature. Modacrylic fibers generally exhibit increased
plasticity and a strong tendency to shrink at higher dyeing
temperature. The lightfastness on these fibers is considerably
poorer than on normal PAC fiber, making an appropriate dye
selection necessary. Dyeing is performed at pH 4.5 with acetic
acid, sodium acetate, and a nonionic dispersing agent.

65
Continuous Processes with Cationic Dyes

• Stock, cable, and top can be dyed on special machines

according to the pad steam process, preferably with
pressurized steam at temperatures above 100 °C to obtain
short fixing times. To avoid drying and condensed water
spots, the steam should be neither superheated nor wet. A
typical pad liquor contains acetic acid (pH 4.5) and dye
solvent in addition to steam-resistant, readily water
soluble cationic dyes (usually liquid brands).

66
• Space dyeing can be regarded as a variant
of this mode of dyeing. A new suggestion involves
simultaneous bulking and dyeing in a continuous
process . The pad steam process with fixing by
saturated steam at 100-102 °C is used for piece
goods, especially upholstery material (velour).
This requires longer fixing times (10ñ20 min).
Rapidly diffusing cationic dyes and dye solvents,
which also exhibit a carrier effect, are required

67
• If direct dyes are used simul4.14.6 Continuous
Processe with Cationic Dyes simultaneously (for
cotton backs), the dye solvent should also have a
good dispersing action. Dry heat fixing (thermosol
process,) is unimportant for PAC dyeing because
the fiber tends to yellow and harden in this process
and cationic dyes are fixed slowly and
incompletely .

68
• Gel dyeing, i.e. dyeing wet-spun PAC fibers during the production
process in the gel state is especially economical. It is estimated that ca.
25 % of PAC fiber production is dyed in the gel state by the fiber
producer.
• The gel state is defined as the state of production of the fiber after
extrusion, when the solvent has been washed out, either before or after
stretching, and before drying (sintering). Due to the high porosity of
the fiber in the gel state, cationic dyes are adsorbed very rapidly
(within seconds) on the fiber. Therefore, adsorption, which is
insensitive to temperature variations, is the rate-determining step of
dyeing . Fixation of the dye follows later during drying at 105-150 °C.
There is almost no difference from normal PAC dyeing with regard to
saturation, shade, and fastness. Liquid brands, which are miscible
without precipitation in the dye applicator, are preferably used. 69
• Mixtures, even diluted, must be stable on storage.
• Although acrylic fibers can also be printed with
disperse dyes, printing with cationic dyes is preferred
because of their high brilliance, spreading power and
good lightfastness. Preliminary tests should be carried
out, since acrylic fibers differ in their dye absorpion rates
for different groups of dyes. Best fixation results are
obtained with high-pressure steam at 0.12-0.14 MPa
(104- 110 °C) for 30min.

70
• Transfer printing is
not suitable without either
elaborate pretreatment or
special swelling agents or
solvents. Disperse dyes
produce only very light
shades

71
Mixtures of Acrylic with other Synthetic Fibers

• A frequently processed mixture (e.g., for outerwear or furnishing

fabrics), consists of PES and PAC fibers. No basic difficulties are
involved in dyeing, both union shades and bicolor dyeing being
possible. Selected disperse and cationic dyes are used. Although
disperse dyes color PAC more weakly than PES, the shade
produced is the same. In the case of bicolor dyeing, the PAC
component must always be kept darker. A dyeing temperature of
106 °C should not be exceeded because of the PAC component.
Thus, carriers must be used as a rule. In one-bath dyeing, attention
must be paid to the compatibility of the various dyebath additives
with each other. Cationic retarders are not used in one-bath dyeing
.
72
• Problems with the compatibility of the dyes can
also arise in dyeing mixtures of PA and PAC
fibers. Such blends are produced, e.g., for skiwear.
The cationic dyes used for the PAC component
do not dye normal PA fibers. Acid and metal
complex dyes leave PAC fibers practically white.
Sulfo group containing 1:1 metal-complex dyes
possess a zwitter ionic character and therefore can
be applied in low concentration in the same bath
with cationic dyes, without the occurrence of
precipitation. In this manner, one-bath dyeing can
be carried out.
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• The stability of Cationic Dyes on Acrylic Fibers the bath can
be improved by addition of a nonionic auxiliary. Cationic
retarders should be excluded in all cases. With 1:2 metal-
complex dyes dyeing is carried out in two steps: first with
cationic dyes, because they exhaust almost quantitatively, and
then with metal-complex dyes for the PA component.

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Cationic Dyes for Paper, Leather, and Other
Substrates

• Cationic dyes exhibit good affinity for negatively charged wood

pulp and unbleached pulp grades. Anionic fixing agents improve
their wetfastness.
• Cationic dyes are chosen because of their brilliance and intensity,
which makes them especially valuable for recycled paper grades.
Their poor lightfastness is not a maior problem because of the low
light stability of the substrate itself. They suffer from poor affinity
for bleached, lignin-free pulp grades, which are used, for instance,
in the manufacture of table cloths and napkins. Therefore, dyes
have been developed for this application that bear several cationic
charges linked by substantive moieties, such as urea or triazine
(e.g., 30). 75
H

76
 H

• Because of their coloring strength, cationic dyes are used

in the office supplies industry for the manufacture of ink,
typewriter ribbon, and copying paper.
• Colorless derivatives of the carbinol bases of cationic
dyes have recently found application for the manufacture
of carbonless copy paper and for special paper used for
thermal printers.
• Examples of such color formers are the crystal violet
derivative 31 , which develops a blue color, and the
black-developing fluorane lactone 32 and benzoxazine
33.
77
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78
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79
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 References

1. https://www.linkedin.com/pulse/what-cationic-dyes-jiang
-jiang
2. https://www.slideshare.net/pankajrajput33/basic-dyes-65
474700
3. https://www.slideshare.net/BerihunGashu/basic-dyes-248
325784
4. Book: Industrial dyes; Chemistry, Properties,
Applications edited by Klaus Hunger

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