Leveling agents: chemistry and performance

Prof. S.K. Laga (1), Miss Rashmi Joshi M. (2), Mr. Vignesh Dhanabalan (3),

D.K.T.E.S Textile & Engineering Institute, Ichalkaranji-416115 (M.H), India,

swapan.laga@gmail.com (1), xpress.joshi99@gmail.com (2), vigneshdhanabalan@hotmail.com (3)

February 1, 2014

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Abstract

The appeal (comfort) of the fabric material is a main parameter that decides the market flow of the product. To bring
in complicated design and trendy material, shade variations have always been a hurdle. It remains so as, the dye
uptake and fixation and of the dye material is random. Leveling agent are chemical agents that work on the dye
molecule and help in fixing the dye particles uniformly. In this paper we have made efforts to share the knowledge
on what leveling agents and dispersing agents are, the necessity of leveling agent, different classes of leveling agent,
their testing methods and some means of synthesizing leveling agents for industry and laboratory use.

Keywords: Colloidal particle, color tone, dispersing agent, dye uptake, leveling agents.

Introduction

Dyeing and printing are processes of imparting color onto the substrate. This imparting of color is done by use of wet
and dry processing techniques. In wet processing, substrate comes in contact with the dye solution and coloring
takes place. Due to various reasons like surface tension, unevenness, capillary action, polar component and other
parameters, the uniform dyeing gets affected. To yield color in wet processing in a better manner, chemical
Auxiliaries are used. One such kind is leveling agent and the other is dispersing agent. Dispersing agents are
substances that promote the more or less uniform and stable suspension of relatively small particle in a given matrix.
The function of dispersing agent is to prevent agglomeration of individual dye particle during dyeing. They play a
subsidiary role in dispersion involving in textile coloration. Dispersing agents are much preferred for Vat dyeing,
Disperse dye and pigment padding. The anionic product ionizes water and form an electrical double layer. The
mutual repulsion between these groups keep dye particle apart and prevent agglomeration

Many fabrics during dyeing have high initial dye uptake causing unevenness or shade variation. Leveling agents are
added to the dye bath to regulate the process of dyeing to obtain uniform shade throughout the substrate. Leveling
agents are soluble in water but, the solubility reduces with increase in temperature and finally becomes insoluble
after a temperature called as the cloud point. On selection of leveling agent the cloud point temperature of the
leveling agent is an important parameter.

Level dyeing can be broadly classified into two categories

 Gross unlevelness throughout the material : The substrate is uniform throughout both physically and
chemically

 Localized unlevelness: Non uniformity of substrate (either wise).

Unlevelness, bareness or patchy dyeing occurs during dyeing due to

 deformity in fibre/yarn, fabric structure,

 Improper dyeing process or condition,

 Improper selection of dyestuffs for dyeing.

Difference between leveling and dispersing agent:

Dispersing agents are known to improve the migration and leveling of disperse dye on polyester during HT dyeing.

Leveling agent tend to slow down the dye uptake of the fibers helping to produce more uniform color in the textile
fiber. They are also termed as retarding agents or retarders. The use of retarders is essential in situation in which dye
tends to rush on to the fiber and results in unevenly colored textile material. Leveling agents are surface active
agents and are chemically related to soaps, synthetic detergents and wetting agents. They may be anionic, cationic
or non-ionic organic compounds.

Effect of leveling agents:

Specific leveling agents, that can be either no-ionic or anionic surfactants or compounds, increase the solubility of
the dye, thereby lowering the initial strike and overall rate of the dye uptake which can also cause a restraining
effect resulting in a loss of color yield. The solubility of the leveling agent decreases with increasing temperature, and
if, the temperature of the bath increases above the cloud point of the agent then the dye dispersion takes place
resulting in dye aggregation and attendant of unlevel dyeing.

Herlinger et al proposed that at concentration above CMC, non-ionic agents lower the dye uptake owing to a
corresponding increase in solubility of the dye, this reduction increases with increase in solubility of the dye. Anionic
agents increase the cloud point of the non-ionic leveling agents. Careful consideration must be given to the amount
of non-ionic leveling agent used owing to the often marked restraining effect exerted by the compound on dye
uptake. [1-3]

Table 1: Commercially available leveling agents

Trade Name Nature Manufacturer

Supersol VL Super Chem. Non-ionic (for PET, vat dyes)

Dispersol K paste Anionic ICI, India

Deterzol D Paste Anionic fatty alcohol sulphate Associated Enterprise

Dispersol VLH Non-ionic ICI, India

Lyogen DK Wool, Silk and Nylon Sandoz (I)

Lyogen SMK For wool, silk, nylon Sandoz (I)

Tenegal CVN (liquid) Anionic Suhred Geigy Co.

Polylevel SG Non-ionic (for wool) Suhred Geigy Co.

Tenegal CVN (liquid) Anionic (for nylon) Suhred Geigy Co.

Lyogen DFT Non-ionic for PET & blends Sandoz (I)

Types (or) classification of leveling agents:

Leveling agents are classified into two main groups based on ionization and structure wise

1. According to the ionic nature

 Anionic
  Cationic

 Non-ionic [used for PET dyes]

Anionic agent:

The molecules of these compounds consist of largely negative charged or anionic organic radical. When anionic
agents are added to the dye liquor, the anionic agents will be attracted to any positive sites of the fiber. The anionic
agents try to repel similarly charged anionic dye molecules. As the bath is heated the molecules develop sufficient
energy to overcome the repulsive forces between the retarder and the dye. These anionic agents tend to give more
uniform dye uptake of the fiber.

Cationic agents:

The molecules of these compounds consist of largely positively charged or cationic organic radical. When cationic
agents are added to the dye liquor, their captions are attracted to the anionic dye molecule. This neutralizes the
electrical charge of the dye molecule and minimizes the substantively of the fibers. The energy provided by heating
cause the cationic radicals of the leveling agent to gradually dissociate of the cationic agent from the anionic dye
molecule slowly releases the dye and ensures a more uniform absorption of the polymer system of the fiber.

Anionic Leveling agents   ->       silk, wool, nylon, Bast.

Cationic leveling agents   ->       wool, silk, acrylic, nylon, cellulosic
Non-ionic                        ->       synthetics & blends

2. According to the chemical structure

 Fatty Acid (Ethylene Urea)

 Fatty alcohol (Sulphates)

 Sulphated (Fatty amine)

 Alkyl aryl (Sulphonates)

 Fatty alcohol ethylene (oxide condensate)

Mechanism of functioning of leveling agents:

The two fundamental mechanisms that contribute to level dyeing are

 Control of exhaustion of dye so that it is taken up evenly

 Migration of dye after initial unlevel sorption on the fiber.

The attractive force between agent and dye create a counter balancing mechanism against fiber-dye attractive
forces, restraining the uptake of the dye by the fiber. As the temperature increases the complex gradually breaks
down, progressively releasing the dye for more gradual sorption by the fiber, this clearly shows leveling agent
working by this mechanism that rely on the attractive force between the fiber and the dye particle but, similarly
strong force of attraction may result in a complex that is difficult to break down.

Leveling agent (a) allows the dye to get in to the fiber regardless of initial Unevenness.  During the course of further
dyeing levelness is achieved through migration.  For this selection of dyes for dyeing is of utmost importance or (b) it
controls/retards the rate of dyeing throughout the dyeing cycle.  Sometimes the leveling agent acts in both the ways.

Some mechanisms are stated below:

 Non-ionic leveling agents are used in direct dyeing. They promote leveling by breaking the dye aggregates
that migrate slowly.
  The action of a non-ionic surfactant in reducing the uptake of dye by wool and silk is based on the formation
of a complex between the dye and the surfactant; it reduces the effective concentration of dye, i.e. the
complex acts as a reservoir from which dye is gradually released on heating owing to decomposition of the
complex.

 Leveling agent selected for vat dyeing must give the required initial retardation without a significant loss in
color yield.  Leuco vat dyes have greater affinity to absorption, which causes unlevel dyeing.  The two most
widely used types of Leveling agents for Vat dyes are cationic active surfactants and non-ionic ethylene oxide
condensate.  The cation active products compete with the leuco vat dye for available sites in the fibre and thus
retard the dyeing process. The retarder-dye complex acts as a reservoir for the leuco vat dye preventing from
dye rushing to the fibre in the initial stages.  The complex breaks so that, the dye is slowly released during the
later stage of dyeing.

 In case of dyeing nylon with 1:2 metal complex dye, due to poor migration of dyes unlevel dyeing is
obtained.  Non-ionic Leveling agents have affinity for these dyes hence; they retard the exhaustion and
produce level dyeing.

 If a mixture of mono-sulphonic and trisulphonic acid is used in dyeing of nylon to produce compound shades,
the mono sulphonic acid dye will be first taken by the fibre and will turn black for the polysulphonic dye.  Here,
anionic Leveling agents will complete with monosulphonic acid dyes for available sites in the fiber and thus it
will minimize the blocking effect and produce level dyeing.

Table 2: Use of leveling agents based on ion type

Ion type Fiber type Dye

Cotton, Wool, Nylon, Azoic, Vat, Direct milling, Metal
Non-Ionic/Anionic
Polyester Complex, Disperse
Direct milling, Metal Complex,
Nonionic/Cationic Wool, Nylon, Polyester
Disperse
Acid, Mordant, Metal Complex,
Anionic Wool
Reactant
Cotton, Wool, Nylon,
Weakly Anionic Acid, Direct, Disperse
Polyester
Anionic/Cationic Polyester Acid, Metal-Complex
Cationic Wool, Nylon, Basic, Acid, Metal-Complex, Reactive
Weakly cationic Acrylic, Wool, Nylon, Acid, Mordant, Metal-Complex
Cationic/Polymeric Cotton Vat, Sulphur
Acid, Mordrant, Metal-Complex,
Amphoteric Wool
Reactive

Testing method for evaluation of efficiency of leveling agent:

(a) By Performance Test

Carry out separate dyeing with and without pressure of leveling agent with blue dyes (which would be easier to plot
the blot marks).  Then, compare the levelness of both the samples.  Choose any class of blue dye having poor
Leveling properties.

Concentration of Leveling agent = Max. 5 gpl.

Fig 1: optimum concentration to exhaustion rate

Higher the concentration higher will be leveling effect but after certain level the attraction force becomes very high
that it is difficult to break down. By incorporating certain chemicals in the dyeing liquor we can overcome one or
more causes of non-uniformity.

(b) By determining active content

To determine the active content of the material prepare a solution of 20 ml Leveling agent sample in 100 ml
graduated measuring cylinder and add 20 ml 2 N sulfuric acid to it. Place the measuring cylinder in water bath at 60
0C for 2 hrs and then cool it. Observe the height of the oil layer after cooling.
The active content can be calculated using the following relationship

                                   V2
Active Content  =  ————   x  100 %
                                    V1
Where,  V1 = Volume of Sample taken.
V2 = Volume of Oil Layer.

(c) By determining the strike percentage

The Strike (S) is defined as the color on 1 min sample expressed as % of the color on the one hour sample.

To determine the strike percentagePrepare a small fabric sample measuring 2 x 2 cm and another large fabric sample
measuring 10 cm x 10 cm and a solution of (0.1 %) Foron Blue SE2RI 200%.

Prepare the dye-bath using the above dye solution keeping material to liquor ratio 1: 50 and add 2 gm/liter leveling
agent to this dye-bath. Dip the sample in the dye bath and increase the temperature to 80 0C. Remove small sample
after one minute and the large sample after an hour. Measure the reflectance for both the using spectrophotometer.

 To calculate the strike % using the following relationship

( R0 – R1 )
S   =  —————–  x  100
( R0 – R60 )

Where,  R0 = Total reflectance on undyed sample, R1 = Total reflectance on 1 min sample.

R60 = Total reflectance on 60 min sample.

Efficiency of leveling agent:

Table 3: Test results conducted by ATIRA on different grades of dye with varying concentrations of leveling agent

Trials were conducted by ATIRA to determine the effect of dye absorption by leveling agent. Various dyes were used
at concentrations between 0.5 to 2.0 g/l of water and concentrations of leveling agents at 0.25, 0.5, 1.0, 1.5, 2.0 g/l.
Dyed material without use of leveling agent were kept as 100% and the test was conducted, it was found that
leveling agents gave good distribution results up to 0.5 g/l followed by depreciation in the color yield. This loss in
effect may be due to more energy required to break the attraction force between the fiber-dye solutions.

Root causes for uneven / unlevel dyeing:

 Improper dye dissolution.

 Too much affinity of dye towards substrate.

Role of leveling agent in dyeing:

The leveling agent will compete with the dyes having affinity towards substrate.  HLB value of leveling agent is higher
than that of dispersing agent. For Synthetic and its blends, generally non-ionic leveling agents are used that can
withstand higher temp of dyeing, Say 1300C.  These are the condensates of ethylene oxide and higher fatty alcohol,
fatty amines.

General Preparation of Leveling Agents

The category of chemical used for preparation of leveling agent has been shown below with an example is illustrated
below

Example
Fatty alcohol Sulphates :

Lauryl alcohol and oleum on sulphation at 1.5 atm. pressure.  The Sulphated product is further alkali fused. The
product is chemically identical to commercial product (Gardinal WA). It can be used as leveling agent for dyeing
nylon with acid dyes.

Sulphated  fatty amines:

The final product has same chemical composition as the commercial product EMCOL. It can be used for dyeing of
wool, silk with acid colors.
Fatty acid ethylene Urea Product :
General prepration

Example

The final product has same chemical composition as the commercial product Lyogen SMK. It is used for dyeing of
wool with neutral acid dyes.

Alkyl naphthalene Sulphonate :

The final product is a non-ionic alkyl naphthalene sulphonate which has chemical components similar to Lyogen DFT
used as leveling agent in disperses dyeing.

Commercial Method for preparation of Alkyl naphthalene Sulphonate

In industry first sulphonation is carried out.  Then, methylation is done and lastly alkali fusion.

First step (1600C / 1-2 hrs.) with

Naphthalene      =          190 – 200 kg.

98% H2SO4        =          1900 – 2000 liters.

2nd Step: Methylation (80 – 85°C temp. for a period of 18 – 24 hrs.) with

37 – 41% formaldehyde soln. / formalin.

990 kg of formalin
1000 – 1100 lts of water

3rd Step: Alkali fusion [NaOH / Na2CO3] with

NaOH = 0.7 kg [48%] i.e. Caustic lye.

NaCO3 = 1.5 to 1.6 kg.
And then final product is achieved.

In the preparation of Alkyl naphthalene Sulphonate solution 2:1 mole ratio of naphthalene and HCOH is taken and
methylation is carried around 80-85ºC, followed by sulphonation in the presence of 98% H2SO4 at around 160-170ºC
which is followed by alkali fusion.
Impact of leveling agent on physical properties of the substrate

Leveling agents have no effect on physical properties of the substrate as they do not interact with the textile fiber.
They have profound effect on the dye molecule only.

Method of removing leveling agent

Generally leveling agents are removed simply by boating with 2-3 gpl NaOH and 2-5 gpl of sodium hydrosulphate at
80-85ºC for 30 min followed by hot wash and cold wash.

Limitation of leveling agent:

Depth of the shade is reduced by 10 to 15%.  Therefore, in case of Leveling agent add 10 to 15% more dye from the
recipe.