Carrier dyeing: pros and cons

Miss Joshi Rashmi. M, Vignesh Dhanabalan and Prof Laga S.K

D.K.T.E.S Textile & Engineering Institute, Ichalkaranji-416115(M.H), India
xpress.joshi99@gmail.com, vigneshdhanabalan@hotmail.com & swapan.laga@gmail.com
Issue December, 2013

Volume 06, Issue 012

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Abstract:
Dyeing of fibers with disperse dyes takes place from a dilute solution of dye in the presence of
suspension of dye particle. As the dye molecule are absorbed by the fiber from solution, more
dye passes into solution from suspension in order to maintain the concentration of the solution,
which is in equilibrium with a definite concentration of dye on the surface of the fiber. As dyeing
proceeds these molecules are taken up from the solution by the fiber. The dye remaining in
suspension in the form of much larger particles dissolves slowly and is taken up by the fiber until
equilibrium is reached.
The attraction of the fiber from the dye is generally expressed in terms of standard affinity.
Dyeing in most cases is considered as a thermodynamically reversible process, that is desorption
is the reverse of adsorption. So it is advisable to use the thermodynamic function for the dyefiber system.
There are several proposed theories to explain the mode of action of carriers in disperse dyeing
of synthetics. According to most of the theory, it is proposed that carrier can increase in
plasticization of the fiber (reduction increasing) which felicitates dyeing at atmospheric
condition. In this paper the authors have tried to narrate the pros and cons of carrier dyeing along
with validity of various propped theory of carrier dyeing.
Keywords: Azo dyes, Anthraquinone dye, Carrier dyeing, Disperse dye, Plasticization, Polyester
dyeing.
Introduction
Carrier is an organic compound which accelerates dyeing by breaking up or dissolving dye
aggregates and bringing them to the fiber-water interface in size small quantities enough to be
absorbed by the material. Carriers allow dyeing of even deep shades at the boil within a
reasonable dyeing time. Carrier is a type of accelerant particulate used in the dyeing or printing
of hydrophobic fibers with disperses dyes. Disperse dyes are poorly soluble in hot water;
therefore, they are ground (dispersed) to a particle size of less than 2 microns. It could carry the
dye into the fibre, thus causing more rapid dyeing; it considerably increases the rate of dyeing
and has also altered the dispersing property of the dye. Terylene was first carrier put to use in
1960 which later paved way to use more than 300 products to use with carriers.

The difficulty in dyeing of polyester using disperse dyeing is, slow rate of dispersion of dye
molecules. The slow absorption rate is due to low aqueous solubility which intern gives
aggregate thereby decreasing their penetration into compact structure of fabric.
Robert and Solanki found that the concentration profiles of four carriers on PET were sigmoid in
shape and differed to those of disperse dye in the fiber. These workers considered that the initial
increase in the gradients of the profile curves was due to increase in plasticization of fiber as the
concentration of the fiber in the substrate increased, causing in the reduction in the glass
transition temperature (Tg) of the polymer and a consequent increase in rate of carrier diffusion,
the subsequent decrease rate of uptake of carriers may then be attributed to a reduction in the
carrier concentration gradient has equilibrium uptake is approached.
Disperse dyes
Disperse dyes are traditionally non-ionic chemicals with sparing solubility in water which,
consequently, are able to retain comparatively better substantivity for hydrophobic fibres, such as
polyester, nylon and acetate.Polyester exhibits a lower moisture regain (0.4% vs. 4% for nylon)
and does not possess a terminal functional group to which an ionic dye is attracted. However,
polyester can be dyed by disperse dyes, these are non-ionic dyes with finite.
Disperse dyes are often substituted azo, anthraquinone or diphenylamine compounds which are
non-ionic and contain no water solubilising groups. The dye particles are thus held in dispersion
by the surface-active agent and the dyes themselves are called disperse dyes.
Azo dyes
Azo dyes are defined as compounds containing at least one azo group attached to sp2-hybridized
carbon atoms. The azo group is an inherently intense chromophore in terms of the tinctorial
strength normally 2 or 3 times stronger in tinctorial strength.
Anthraquinone disperse dyes
Anthraquinone disperse dyes were among the early acetate dyes, Anthraquinone disperse dyes
were among the early acetate dyes. Anthraquinone disperse dyes containing alkylamino or
hydroxy groups (e.g. C.I. Disperse Violet 4, C.I. Disperse Red 15) can be used for the coloration
of cellulose acetate, although of limited color range and of moderate fastness. When more
hydrophobic substituents are introduced to enhance the affinity for polyester fibre, various
shades can be produced.
Other Disperse dyes used are

Nitroarylamino disperse dyes

Coumarin disperse dyes

Methine disperse dyes

Naphthostyryl disperse dyes

Quinophthalone disperse dyes

Formazan disperse dyes

Benzodifuranone disperse dyes

Sr.No

1
2
3
4
5
6

Solubility in water (mg dm-1)

Dye type

V
VI
VII
VIII
IX
X

25C
0.3
0.4
7.1
4.4
0.4
1.2

80C
7
18
240
43
11
35

Table 1: Solubility of disperse dye at respective temperatures

Necessity of Carriers Disperse dye

Lower hydrophilicity

The water affinity groups that are responsible for absorption of the water based dye molecule are
absent. It has only 0.4% moisture regain making it hydrophobic. Due to the absence the reactive
sites dyeing with regular dyes are difficult.

Reactive sites

There are no reactive sites in the polyester material that will lend hand to combine with dye
molecule.

Activation energy level

The obtaining and receiving material has to be activated for the reaction to be carried out. The
activation energy for polyester is around 30-35 kcal, so the dye particle is also expected to be
elevated to that level for the chemical to react.

Pore and particle size

The surface of the material have imperfection with pores that are very fine in the order of 1-10
microns, so the dye particle to be used in such cases should also have sizes at this range.
Disperse dye molecules are the only dye molecules having particle size nearer to this range.
Mechanism of Carrier Action
The fibres absorb the carrier and swell. This swelling can impede liquor flow in packages
causing unevenness. The overall effect is to lower the polymer glass transition temperature, thus
promoting polymer chain movements and creating free volume. This speeds up the diffusion of
the dye into the fibre.
A typical carrier dyeing procedure involves running the goods in the bath at 60C and adding
dilute dispersing agent, emulsified carrier and lastly the disperse dyes. The temperature is then
gradually raised to the boil and dyeing is continued at this temperature
Different theories have been put forward to explain the ability of the carrier to increase the rate
of dyeing.

Increased swelling of the fibre.

Increased water imbibitions by Vickerstaff

Transport theory by Summer et al

Increased solubility of Dye by Peter et al

Film formation by Vickerstaff

Liquid fibre theory.

Loosening of fibre structure by Water et al

Lubricity theory by Vickerstaff

Reduction in Tg / Plasticization theory by William Eenry and Laudel

a) Increased swelling of the fibre

Carrier causes swelling of fibre thus allowing larger dye molecules to diffuse rapidly into the
fibre. Although most of the carriers are swelling agents for PET fibre, a few such as
trichlorobenzene cause less swelling less than water.
b) Increased Water Imbibitions

Due to the presence of hydrophilic groups O,P-phenylphenol, the carrier increases the water of
imbibitions of fibre. The aromatic portion of such molecules is supposed to have
van der
vals force of attraction for the hydrophilic fiber, thereby enabling the dye molecule to move more
readily in the fibre. This theory cannot explain the action of hydrophobic carriers such as
trichlorobenzene and diphenyl.
c) Transport theory
In this theory, the dye forms a loose complex with the carrier which is more readily absorbed by
the fibre than the dye alone from its aqueous solution, making it difficult to accept the dye-carrier
complex, which has a larger size, can diffuse rapidly into the fibre.
d) Increased Solubility of Dye :
The carrier increases the solubility of the dye thereby bringing the dye in solution as single
molecules. However, several effective carriers have poor solublizing power for disperse dyes.
e) Film Formation :
That water insoluble carrier surrounds the fiber and forms a film. When the solubility of the dye
is higher the disperse dye then dissolves in the film and dyeing takes place more rapidly from the
film than from dilute aqueous solutions of the dye.
f) Liquid Fibre theory :
According to this theory, the carrier is first absorbed within the fibre. The combination of
absorbed carrier and fibre has more affinity for the dye, because of the solubility of the dye in the
carrier. This theory can not account for the fact that carrier of similar efficiency have vast
different solubilising power for disperse dyes.
g) Loosening of fibre structure :
It is suggested that carrier penetrates into the fiber structure and reduces the fiber-fiber inter
molecular force (van der wals force) and enables the rapid entry of dye into loose fibre structure.
h) Lubricity theory :
The carriers acting on the surface forming a lubrication on the surface of the fiber and breaks the
fiber-fiber inter molecular force.
i) Reduction in Tg / Plasticization Theory :
The carrier breaks the intermolecular bonds thereby reducing the Tg. and as Tg reduces the
dyeing is possible at lower temperature.
3. Effectiveness of carrier

Dyeing polyester with disperse dyes at 100C without special auxiliaries known as carriers only
light shades can be obtained, this is because of the low dye absorption rate. For efficient use of
dye no un-dissolved carrier should be present in the bath at the completion of dyeing. If separate
carrier phase is present dyeing will be weak, as a part of the dye present in the carrier; phase will
not be available to the fiber and this being insoluble may cause spot on the fabric. Therefore, it
should be carefully noted that the bath does not becomes saturated by the addition of too much
quantity of carriers. If it happens, the fiber also becomes saturated and greater carrier activity
cannot be achieved at a given temperature.
The effectiveness of the carrier decrease when its solubility in water increases, because in carrier
has high affinity for water and cannot form hydrogen bonds with fiber molecules but, in partlysoluble stage it is more effective in forming hydrogen bonding with fiber molecules. Example :
sodium based carrier (O and P phenyl phenol) have no effect as carriers but free phenols act as
great carrier agents, same way diphenyl ether has good effect for dyeing polyester. These carriers
should be finely distributed to avoid specky dyeing.

Fig 1: Penetration of dye molecule into polyester fiber

3.1 Common carrier agents in use

Phenolic substance: o & p phenylphenol

Primary amines

Hydrocarbons: Diphenyl

Esters: Di-methyl ester of terephthalic acid

Acids: Benzoic acid and salicylic acid

Amides: N-Alkyl phthalamide derivatives

Alcohols, ketones, Etheres

Nitriles

Carbamates: o-octyl carbamate

The dyeing of polyester fiber with disperse dye carrier is as follows.

Equilibrium of the surface of fiber with carrier, water and dye.

Diffusion of carrier and water into the fiber loosening the inter chain forces.

Diffusion of dye through somewhat more permeable fiber.

The concentration of the carrier is primary-boosts dye penetration. The ratio of the solubility is
the partition or distribution coefficient of the carrier between the fiber and the dye bath.
Distribution
coefficient
D
Carrier concentration in the dye bath

Carrier concentration in the fiber

3.2 Different phase with carrier dyeing

The rate of solution and equilibrium of the carrier and the fiber.

Rate of the collision and equilibrium between the dye and the fiber which has already
been treated with the carrier.

In short the effectiveness of the carrier depends on the concentration of the carrier in the fiber
and the bath.
Sr.

Effect on
Optimum
light
Odour
concentration
fastness

Chemical
Class

Trade
Name

Diphenyl

Tumescal
6 GPL
D [ICI]

Nil

Strong

Ease of
removal

Levelling
property

Moderate

Good [Tend
to cause
- Yellow in
staining in colour
more cases]

Insoluble in water
Non-toxic
Costly2O-dichloro benzeneDilatin DB [Sandoz]3-6 GPLNilModerate to strongReadily
removedGood- Water insoluble

Remark

 Volatile in nature
Toxic in nature
Costly
Treatment should be carried out in closed vessel3Benzoic acid10-20
GPLSlightNilModerateNon Good [cause staining]- Water soluble
Easily available
Cheap4Salicylic acid10-20 GPLSlightNilReadily removedIt can cause straining- Water
soluble5Trichlorobe-nzane [1:2:3, 1:2:4, 1:3:6]Dilatin ICI [Sandoz] Leva-gal TB [Bayer]5
GPLNilModerate to strongReadily removedGood- Water insoluble
Toxic
Volatile6Methyl ester of Salicylic acidLevagal PT [Bayer]1.5 to 8 GPLNoStrongDifficultGood
[cause staining]- Water insoluble
Non-toxic
Costly7O-Phenyl phenol [Sod. Salt]Tumescal OP [ICI]
Dawcibea Leva-gal OP [bayer]1 to 5 GPLLight fastness of most of dyes
reducesModerateDifficultGood- Non-toxic
Anionic
Water soluble
Cheaper8P-Phenyl PhenolTumescal pH [ICI]1-5 GPL- -Faint- -Good [cause staining]Anionic
Water insoluble
Non-toxic
Cheaper9Dimethyl ester of Phthalic acidLatyl carrier A [Dupont]5NoModerateReadily
removedGood- Water insoluble
Non-ionic in nature
costly
Table 2 : Performance characteristics of various carriers

4. Factors affecting the level of absorption

A. Adsorption of carriers
Hydrophobic carriers are more effective on PET fabrics than the hydrophilic carriers. Due to the
insolubility of dye the dye particles are transferred without causing higher shade variations.
Carriers get absorbed easily on to PET by virtue of the non-polar force operating between the
aromatic region in both carrier and fiber.
B. Particle size in dispersion of the dyes
The aqueous solubility of disperse dye particles in a dispersion increases with decreasing particle
size this is due to increase in the severity of milling that accompanies a reduction in the particle
size of the dye enhances the solubility and adsorption of disperse dye.
C. pH of dyebath
Generally, in the commercial dyeing of polyester fibres with disperse dyes, dyeing is carried out
within the pH range 5.5 to 6.5; Strongly alkaline or acidic conditions, such as higher than pH 9
and lower than pH 4, induce hydrolysis of the fibre as well as decomposition of azo disperse
dyes. In the case of high temperature dyeing, this degradation of polyester fibre and dye is
accelerated.
D. Crystal form of the disperse dyes
The possible different crystal forms (e.g. , , , and ) of disperse dyes have been suggested to
influence the saturation values achieved on polyester, due to differences in the vapour pressure
and solubility of the different forms of dye in both water and fibre.

Sr.No
1
2
3
4
5

Crystal
form

Saturation value
(g dye 100g-1
fiber)
077
1.0
2.13
3.07
5.5

Table 3: different crystal forms and their respective absorption rates

E. Temperature
The adsorption and diffusion of disperse dyes on polyester are greatly influenced by temperature
as an increase in temperature increases the mobility of the polymer chains in the amorphous
regions of the fibre. Polyester fibres dye very slowly at temperatures much below 100C. At

85C, the temperature normally used for the dyeing of secondary cellulose acetate, it was found
that polyester fibre dyed at rates between 700 and 1000 times slower than those measured for the
same dyes on secondary cellulose acetate and nylon.
5. Factors to be considered on selection of carriers:

Availability and cost

Effectiveness in increasing the rate of dyeing

Freedom from unpleasant odour

Absence of toxicity

Compatibility with dyes and other auxiliaries

Ease of removal after dyeing

Non volatility in steaming

Biodegradability

No adverse effect on fabric

No shrinking of material

Handle of dye and material

Irritation on skin

Uniformity of absorption by the fiber

Stability under dyeing condition

No degradation of discoloration

5.1 Desirable properties of a good Carrier:

It should increase the rate of dyeing.

It should be compatible with disperse dyes and auxiliaries used in dyeing and printing.

It should be non-volatile in nature.

It should be non-toxic.

It should not have adverse effect on fastness properties of the dyeing.

It should not cause undue shrinkage of material.

It should be uniformly absorbed by the material.

It should be odorless.

It should be biodegradable.

It should have good stability under dyeing and printing conditions.

It should be easily removed after dyeing and printing.

5.2 Merits / Advantages of Carriers:

Dyeing can be carried out at boil.

Dyeing cycle is reduced.

Penetration of the dye in the fibre is better thus it improves rubbing fastness.

It improves leveling property so uniform / leveled dyeing can be obtained.

5.3 Demerits / Disadvantages of Carriers:

It reduces the light fastness of dyed and printed material. Carriers based on O-phenyl
phenol and salicylic acid will affect adversary the light fastness of disperse dyed goods.
If it is blended fabric it affect light fastness of disperse and reactive dye average. [Vat,
Sulphur, no affect on light fastness].

Through washing is required to remove carrier otherwise due to retention of carrier on the
fabric material, treated material / fabric produces smell of carrier.

Most of carriers are toxic & unpleasant. They may be coloured. For such carrier it is
difficult to handle and change the tone of dyed material.

We have to take precise precaution for uniform application of carriers.

It can cause spotting / centre to selvedge shade variation.

It will increase the load an effluent plant. As carriers are oily / greasy in nature they
increase the oil content of waste water.

6. Conclusion:
The benefits of carriers were overwhelming in the early days of polyester dyeing because;
polyester fabrics could be dyed in unpressurized becks with no more dyeing problems than with
direct dyes. However, carrier dyeing has steadily declined since the development of suitable
machines for dyeing polyester under pressure at temperature around 130C. Carriers are still
used in some garment and small commission dye houses where high temperature pressurized
dyeing machines are not available.
7. Bibliography:
1. Radhakrishnan.T, Chemical Processing of Polyester/Cellulosic Blend, ATIRA, 1983.
2. Burkinshaw.S.M, Chemical properties of synthetic fiber dyeing, Blackie A.P, Chapman
and Hall, ISBN-0751400432, 1995.
3. Joonseok Koh (2011). Dyeing with Disperse Dyes, Textile Dyeing, Prof. Peter Hauser
(Ed.),
ISBN:
978-953-307-565-5,
InTech,
Available
from:
http://www.intechopen.com/books/textile-dyeing/dyeing-with-disperse-dyes.
4. S. M. Burkinshaw, Chemical Principles of Synthetic Fibre Dyeing, Springer, 1995.
5. Bradford, Colours Terms and Defenition, Society of colorist and dyers, 1988.
6. Koenhen.D.M and Smolders.C.A, Applied polymer science, pg 163, 1975.
7. Salvin.V.S, AATCC piedomont section, Amer,Dyest, rep48, 1959.
8. http://encyclopedia2.thefreedictionary.com/Dyeing
- See more at: http://www.textiletoday.com.bd/carrier-dyeing-pros-andcons/#sthash.k4sEYIkM.dpuf