Reactive and Nylon Dyestuffs

One bath Dyeing of Nylon Cotton Combinations and Working on 360 Degree
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INTERLOOP LIMITED
Project Specific Training
Study on dye classes of reactive and Nylon Dyestuff
Submitted By : Abrar Ahmad Anjum

Designation : MTO Processing HD-2
Submitted To : Sir Zahid Hussain ( Sr. Manager Processing)
Date of Submission : 20, Feb 2017
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Abstract
This project report consists trails on one bath dyeing of Nylon/Cotton combinations and working
on 360 degree digital printing.. First part of the report shows the lab dips on one bath dyeing .
Then the second part of report shows working on 360 degree digital printing.
After this, the project report explains the complete working details of 360 degree digital printing.
Some suggestions and recommendations are also discussed at the end of the report for the
improvement. At the end of the report conclusion of the project report is also discussed.
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Acknowledgement
First of all, I offer my humblest and sincerest word of thanks to Almighty ALLAH for bestowing
upon me the sense of inquiring for successful accomplishment of this piece of work.
I owe my profound acknowledgment to my respected Sr. Manager Zahid Hussain for his kind co-
operation and support during the completion of this project. I am thankful to Deputy Manager
Kashif Naveed, Sr. Foreman Nouman Malik, Sr. Foreman Ijaz Hussain for their kind cooperation
during the whole period.
The services and tutelage provided by the staff of the Processing department are commendable.
A vital contribution has also been provided by some of the very established fellows. It would be
incomplete without thanking some of my friends whose sincere help made me succeed in this
way. I would like to thank all of my friends and beloved juniors for support.
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Table of Contents
1. Reactive Dyes ....................................................................................................................................... 6
1.1. Usages: .......................................................................................................................................... 6
1.2. Structure: ....................................................................................................................................... 6
1.3. Classification of Reactive dyes based on Reactive Group ............................................................ 7
1.3.1. Major Reactive Groups Commercially Available ................................................................. 9
1.4. Basic Principle of Dyeing with Reactive Dyes ........................................................................... 10
1.4.1. The three-step exhaust dyeing process................................................................................ 11
1.5. Bifunctional Reactive Dyes ........................................................................................................ 14
1.6. Reactive Dyes for Wool .............................................................................................................. 14
1.7. Classification of Reactive Dyes based on Application Method .................................................. 16
1.7.1. Reactive Dyes used at INTERLOOP ........................................................................................ 17
1.8. Factors Affecting the Reactive Dyeing ....................................................................................... 18
1.8.1. Alkali Controllable Reactive Dyes........................................................................................... 18
1.8.2. Salt Controllable Reactive Dyes ............................................................................................... 18
1.8.3. Temperature Controllable Reactive Dyes ................................................................................. 18
2. Dyes for Nylon .................................................................................................................................... 18
2.1. Acid Dyes.................................................................................................................................... 18
2.1.1. Classification of Acid Dyes ................................................................................................ 19
2.1.2. Acid Dyes used at INTERLOOP ........................................................................................ 20
2.1.3. Dyeing Nylon with Acid Dyes ............................................................................................ 21
2.1.4. Problems in Nylon Dyeing .................................................................................................. 26
2.1.5. Dyeing Nylon with Metal Complex Dyes ........................................................................... 28
2.1.6. Dyeing Nylon with Disperse Dyes ...................................................................................... 28
2.2. Dyeing Cotton/ Nylon Combinations ......................................................................................... 29
2.2.1. Different processes used for Dyeing of Nylon Cotton Combinations................................. 30
Project On 360 Degree Digital Printing ...................................................................................................... 36
3. References:.......................................................................................................................................... 48
List of Tables
Table 1: Commercial Reactive Dyes........................................................................................................ 17
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Table 2: List and Properties of Reactive Dyes used at INTERLOOP.................................................. 18

Table 3: Acid Dyes Types ......................................................................................................................... 20
Table 4: List and Properties of Acid Dyes used at INTERLOOP ........................................................ 21
List of Figures
Figure 1 : General Structure of Reactive Dye .......................................................................................... 7
Figure 2: Nucleophilic Substitution ........................................................................................................... 7
Figure 3 : Reaction of Triazine Dyes with Cellulose ................................................................................ 8
Figure 4: Reaction of Vinyl Sulphone Dyes with Cellulose ..................................................................... 8
Figure 5 : Dichlorotriazine (DCT) ............................................................................................................. 9
Figure 6 : Monochlorotriazine (MCT) ...................................................................................................... 9
Figure 7 : Monofluorotriazine (MFT) ....................................................................................................... 9
Figure 8 : Nicotinyltriazine (NT) ............................................................................................................... 9
Figure 9 : Trichloropyrimidine (TCP) .................................................................................................... 10
Figure 10 : Vinylsulphone (VS)................................................................................................................ 10
Figure 11 : Dichloroquinoxaline (DCQ).................................................................................................. 10
Figure 12 : Difluorochloropyrimidine (DFCP)....................................................................................... 10
Figure 13 : Structure of Bifunctional Reactive Dye ............................................................................... 14
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Chapter 1 One Bath Dyeing of Nylon/Cotton

Combinations
1.1. Reactive Dyes
Reactive dye is capable of reacting chemically with the substrate. It contains reactive group
which makes covalent bond with the fiber polymers. Covalent bond is formed between the dye
molecule and the terminal OH (Hydroxyl) group of cellulose, Terminal NH2 ( Amino )
groups of polyamide wool fibers.
1.1. Usages:
Cotton, Viscose Rayon and other cellulosic fibers.
Polyamide and wool fibers.
Silk and acetate fibers.
1.2. Structure:
General structure of reactive dyes is given below;
D-B-G-X
Here;
D = Dye part or chromogen (Color producing part of dye)
B = Bridging part (May be NH or NR group)
G = Reactive group bearing part.
X = Reactive group.
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Figure 1 : General Structure of Reactive Dye
1.3. Classification of Reactive dyes based on Reactive Group

Reactive Groups have two main types;
a. Those reacting with cellulose by nucleophilic substitution of a labile chlorine, fluorine,

methyl sulphone or nicotinyl leaving group activated by an adjacent nitrogen atom in a
heterocyclic ring.
Figure 2: Nucleophilic Substitution

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Figure 3 : Reaction of Triazine Dyes with Cellulose
b. Those reacting with cellulose by nucleophilic addition to a carboncarbon double bond,

usually activated by an adjacent electron-attracting sulphone group. This type of vinyl
sulphone group is usually generated in the dyebath by elimination of sulphate ion from a
2-sulphatoethylsulphone precursor group with alkali.
Figure 4: Reaction of Vinyl Sulphone Dyes with Cellulose

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Although many of the early reactive dyes had only one reactive group in the dyestuff molecule,
many of the newer reactive dyes are bifunctional with two or more identical or different reactive
groups.
1.3.1. Major Reactive Groups Commercially Available
Figure 5 : Dichlorotriazine (DCT)
Figure 6 : Monochlorotriazine (MCT)
Figure 7 : Monofluorotriazine (MFT)
Figure 8 : Nicotinyltriazine (NT)

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Figure 9 : Trichloropyrimidine (TCP)
Figure 10 : Vinylsulphone (VS)
Figure 11 : Dichloroquinoxaline (DCQ)
Figure 12 : Difluorochloropyrimidine (DFCP)
1.4. Basic Principle of Dyeing with Reactive Dyes

Dyeing is commenced in neutral solution, often in the presence of salt to promote exhaustion of
the dye onto the cotton. During this period, the dye does not react with the fibre and migration
from fibre to fibre is possible. Then, an appropriate alkali is added to the dyebath to increase its
pH. This initiates the desired dyefibre reaction. The hydroxyl groups in cellulose are weakly
acidic and absorption of hydroxide ions causes some dissociation, forming cellulosate ions.
It is these that react with the dye by nucleophilic addition or substitution. In general, the lower
the reactivity of the reactive group of the dye towards the alkaline cellulose, the higher the final
dyeing temperature and the higher the final pH of the dyebath. under the alkaline conditions
necessary for the dyefibre reaction, hydroxide ions also react with the reactive group of the dye
in much the same manner as the cellulosate ion.
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This produces the hydrolysed dye, which is incapable of reaction with the fibre. Hydrolysis of
the dye is slower than the reaction with the alkaline cotton but it is significant and reduces the
efficiency of the fixation process. After dyeing, any unreacted and hydrolysed dye present in the
cotton must be removed by thorough washing.
The higher the substantivity of the reactive dye for the cotton, the more difficult it is to wash out
unfixed dye from the material. Many of the first reactive dyes had quite simple molecular
structures and low substantivity for cotton, so that the removal of hydrolysed dye from the
material by washing was relatively easy. This is not necessarily true for reactive dyes of more
complicated molecular structure.
Good alkali boiling to remove wax is essential for goods to be dyed with cold-dyeing reactive
dyes because penetration of the dyes into the fibres is much more difficult at lower dyeing
temperatures. Reactive dyes often give such bright colours that bleaching may not be necessary.
1.4.1. The three-step exhaust dyeing process

a. The initial exhaustion phase. Dyeing is started in neutral solution so that there is little
likelihood of the dye reacting with the cellulose. During this stage of dyeing, some
reactive dye will be absorbed by the fibres, the amount depending upon its substantivity.
This dye is capable of migration to promote level dyeing. Sodium chloride or sulphate
will often be present initially or be added gradually to the dyebath during this phase to
promote exhaustion. The temperature of the dyebath may also be gradually increased to
aid penetration of dye into the fibres and to assist migration.
b. The fixation phase. After the initial exhaustion phase, the pH of the dyebath is increased
by complete or gradual addition of the appropriate type and amount of alkali. This causes
dissociation of some of the hydroxyl groups in the cellulose and the nucleophilic
cellulosate ions begin to react with the dye. The fixation process then results in additional
dye absorption, to re-establish the dyeing equilibrium. Dye absorption from solution and
reaction with the fibre then progress until no further dye is taken up.
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c. The post-dyeing washing. The rinsed dyeing contains dye bonded to the cellulose,
absorbed but unreacted dye, as well as hydrolysed dye. There will also be residual alkali
and salt. The latter are relatively easy to remove by successive rinsing in cold and then
warm water. As much unfixed dye as possible must be washed out of the dyeing. If this is
not done, desorption of this dye during washing by the consumer can cause staining of
other materials in the wash. Some unfixed dye is eliminated during the initial rinsing that
removes salt and alkali. Thorough washing of the dyeing using a boiling detergent
solution (soaping) eliminates the remainder. The dyeing is then finally rinsed in warm
water. Soaping must often be repeated for deep dyeing or the residual unfixed dye must
be complexed with a cationic agent.
The objective of dyeing with reactive dyes is to obtain the maximum degree of reaction between
the dye and fibre, with a minimum of dye lost through hydrolysis of the reactive group, and
under conditions where the colour of the dyed material is uniform. Dyes with different reactive
groups and molecular structures require different amounts of added salt to obtain economical
exhaustion. Some reactive dyes, including most of the oldest, have relatively simple molecular
structures and quite low substantivity for cellulosic fibres. They need high concentrations of salt,
up to 100 g l-1, particularly when dyeing deep shades or using long (high) liquor ratios.
At such high salt concentrations, there is always a risk of dye precipitation, particularly when
dyeing at low temperatures. Although Glaubers salt is more expensive than sodium chloride, it
is preferred for dyes prone to aggregation at low dyeing temperatures, such as the turquoise
copper phthalocyanine reactive dyes. The advantage of dyes with low substantivity is that they
diffuse easily in the fibres and are easy to wash out of the material after dyeing. The higher the
substantivity of the reactive dye for the cellulose, the higher the bath exhaustion and the greater
the chance of reaction with the fibre, but the greater the difficulty of removing unfixed dye
during the final washing.
For dyeings with vinyl sulphone dyes, it is advisable to ensure that the residual alkali has been
removed or neutralised prior to soaping since hydroxide ion can catalyse hydrolysis of the ether
type dye-fibre bond and result in additional colour bleeding from the goods. Dyeing with vinyl
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sulphone dyes have maximum dye-fiber bond stability at around pH 4.5, whereas the
corresponding value for dyes based on halogenated nitrogen heterocycles is 6-7. The latter type
have dye-fibre bonds that are more sensitive to acid-catalysed hydrolysis.
The dyeing temperature and the nature and concentration of the alkali required are determined by
the reactivity of the dye, its degree of sulphonation and its substantivity .For a higher fixation
temperature, reaction with the fibre occurs at lower pH, using a weaker alkali or a lower
concentration of the usual alkali. As is the case for salt addition, a deeper shade, or a higher
liquor ratio, will require more alkali. It is not usual to exceed a dyebath pH of 11, even with the
less reactive dyes since this invariably leads to lower colour yields because of dye hydrolysis.
For the polysulphonated dyes as the PH goes higher than 11, there is decrease in substantivity of
dye due to increase in anionic dissociated cellulose. The greater negative charge on cellulose
repels the dye anions. The substantivity of dye also decreases as dye fixation proceeds because
cotton contains more and more bounded anionic dye molecules which also repel the dye
molecules. This effect can be overcome by increasing the concentration of salt in the dyebath.
Dye hydrolysis is more and exhaustion is less at higher liquor ratios. Therefore in exhaust dyeing
reactive dyes of higher substantivity are preferred. The viscose fibers have higher rate of fixation
and exhaustion of reactive dyes than cotton. The washing fastness of reactive dyes on viscose is
also somewhat better than on cotton. Because of the ease of swelling of viscose, the dyeing pH
and temperature for a given dye may be different than for cotton, particularly if dye penetration
may be problematic.
One of the major problems in exhaust dyeing with many reactive dyes is the rather low level of
fixation, particularly when dyeing using a high liquor ratio. Often less than 70% of the original
There is always a risk of anionic reactive dyes being precipitated by calcium, magnesium or
heavy metal ions in the water supply, or of the formation of insoluble hydroxides of these metals
under the alkaline dyeing conditions.dye reacts with the fibre. This results in appreciable dye
concentrations in the dyehouse effluent.
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1.5. Bifunctional Reactive Dyes

Many of the new reactive dyes are bifunctional with identical or different reactive groupings in
the dye molecule. Adding more reactive groups to a given chromophore increases the molecular
weight but decreases the colour per unit weight of dye since the reactive groups are not part of
the chromophoric system.
This increase in molecular size usually results in an increase in substantivity that is of value for
exhaust dyeing with higher liquor ratios but which can impede washing-off of unfixed dye after
dyeing Bifunctional dyes with two reactive groups of different reactivity towards the cotton,
which have different optimal fixation conditions, give a more uniform degree of fixation over a
wider range of dyeing temperature and fixation pH than dyes containing two identical groups.
Therefore, process control does not need to be so stringent. These types of reactive dyes give
quite high fixation yields and thus less colour in the dyehouse effluent. Other important types of
bifunctional reactive dyes include the MFT-VS type (Cibacron C, Ciba) and the MCT-VS type
used in the Sumifix Supra dyes (Sumito). The Kayacelon React range of dyes (Nippon Kayaku)
are also bifunctional reactive dyes, having two NT reactive groups in each dye molecule.
Figure 13 : Structure of Bifunctional Reactive Dye
1.6. Reactive Dyes for Wool

The most important reactive groups in wool are all nucleophilic and are found mainly in the side-
chains of amino acid residues. They are, in order of decreasing reactivity, thiol (the SH of
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cysteine), amino (NH and NH2 of say histidine and lysine) and hydroxyl groups (OH of
serine or tyrosine). Difluorochloropyrimidines undergo aromatic nucleophilic substitution of one
or both fluorine atoms, the fluorine between the two nitrogen atoms being the most reactive.
Bromoacrylamido groups are stable in boiling water at pH 7 and react by both nucleophilic
addition to the double bond and nucleophilic substitution of the bromine atom.
Reactive dyes are usually applied to wool at pH 56 using ammonium salts, and acetic acid as
required. At higher pH values, exhaustion is too low, and at lower values rapid dye uptake gives
unlevel dyeings. Slightly higher pH values are used for dyeing paler shades (pH 5.56.0) and
lower values (pH 5.05.5) for deep shades. Reactive dyes often give quite good exhaustion at
temperatures below the boil but the dyeing temperature will eventually be raised to 100 C to
ensure that reaction with the wool is as complete as possible. Some procedures recommend a
holding stage at an intermediate temperature of 6570 C for 1520 min to allow the dye to
migrate before it reacts with the wool.
Because of their tendency to give unlevel, skittery dyeings, reactive dyes are usually applied to
wool in the presence of proprietary levelling agents. These are often amphoteric, having both
cationic and anionic groups in the molecule. In contrast to most levelling agents, which decrease
the dyeing rate, the auxiliary products for dyeing wool with reactive dyes accelerate dyeing. The
anionic dye complexes with the cationic site in the auxiliary product but the remaining anionic
site provide substantivity for the wool surface.
The bulky dyeauxiliary complex exhausts well onto the fibre surface at relatively low
temperature, better than the dye alone, but cannot penetrate into the fibres. The complex breaks
down as the dyeing temperature increases so that the smaller liberated dye molecules can then
absorb into the wool. The use of such products avoids unlevel, skittery dyeings and provides
better compatibility of dye mixtures.
After dyeing, the material can be washed at 80 C for about 15 min using a dilute ammonia
solution at pH 8.08.5, and then rinsed in water with a little acetic acid. To avoid any alkali
damage to the wool, washing can be done with hexamine (hexamethylenetetramine from
formaldehyde and ammonia) at pH 6.5, or with sodium bicarbonate.
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Shrink-proof wool, which has been treated with resins in the Hercosett process, remains cationic
on the surface and gives rapid uptake of reactive dyes. The usual auxiliary levelling agents may
be less effective in this case. The deposited resin protects the wool from damage and the best
fastness results for deep shades are obtained by dyeing at 110 C for 30 min.
Wool dyed in deep shades with reactive dyes is better protected from damage during dyeing. A
number of explanations for this have been proposed. These involve protein chain crosslinking,
reaction with thiol groups that interferes with the reformation of disulphide links, and reaction
with non-keratinous proteins in the cell membrane complex and endocuticle.
1.7. Classification of Reactive Dyes based on Application Method

2. Cold Brand Reactive Dyes
These dyes are applied at very low temperature i.e. 20- 40C0. These are highly reactive with
fibers at this temperature. Most reactive dyes such as DCT belong to this group and require
week alkali such as NaHCO3 or Na2CO3 for fixation
3. Hot brand Reactive Dyes
These dyes have reactive groups of least reactivity. So high temperature is required for their
reaction with the fibers i.e. 80-90C0. Most of MCT dyes belong to this group and require
stronger alkalis such as Na2CO3 plus NaOH for fixation.
Major Reactive groups used in Commercial dyes are;
Reactive Commercial Name Reactivity Dyeing Temperature

Groups
DCT Procion MX (BASF) High 25-40

Procion H (BASF)
MCT Basilen (BASF Low 80-85
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Cibacron (Ciba)
MFT Cibacron F (Ciba Moderate 40-60
DCQ Levafix E (DyStar) Low 50-70
Drimarene K (Clariant)
DFCP Levafix E-A (DyStar Moderate to high 30-50
VS Remazol (DyStar) moderate 4060
TCP Drimarene X (Clariant) Low 8095
NT Kayacelon React Moderate to high 100130
(Nippon Kayaku)
Table 1: Commercial Reactive Dyes
1.7.1. Reactive Dyes used at INTERLOOP
Comericial Usage Reactivity Fixation Reactive Group

Name Temperature
BEZAKTIV WO Wool Moderate 70 75 C Bi- Functional
Series
BEZAKTIV GO Cotton High 40-80C MonofluroTriazine
Series
BEZAKTIV S- Cotton Moderate 60-80C Multifunctional
MATRIX
DRIMARINE K Cotton, linen, Moderate to 30-50C Difluorochloropyrim
Series rayon (all High idine
cellulose fibers),
and silk
SUMIFIX SUPRA Cotton High 70-80 C Vnylsulfone
Series Monochlorotriazine
Bifunctional
SUMIFIX HF Cotton High 70-80 C Monocholoro
Series triazine
SUMIFIX Series Cotton Moderate to 40-60C Vinylsulfone
High
SYNOZOL K-HL Cotton Moderate 55-65C Monofluro Triazine
Series
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Table 2: List and Properties of Reactive Dyes used at INTERLOOP
1.8. Factors Affecting the Reactive Dyeing

2. PH: Reactive dyeing is done in Alkaline PH 10.5-11.
3. Electrolyte: Concentration of salt depends on the type of shade.
4. Time: Dyeing time varies between 60-90 minutes.
5. Liquor ratio: Higher the liquor ratio bettor the efficiency of dyeing.
1.8.1. Alkali Controllable Reactive Dyes

These dyes have optimum temperature of fixation between 40 and 60C0. They have low
exhaustion in neutral salt solution before alkali is added. They have very high reactivity, so care
is necessary to achieve the level dyeing. Typical examples of these have DCT, DFCP and VS
Reactive dyes.
1.8.2. Salt Controllable Reactive Dyes

These dyes show optimum fixation at a temperature between 80 C0 and the boil. Such dyes
exhibit high exhaustion at neutral PH, So care in necessary to achieve the level dyeing.
Electrolyte needs to be added at controlled rate. These dyes have low reactivity systems such as
TCP, MCT and MFT and have high substantively and called as salt controllable due to their high
reactivity at 60C0 or even lower temperature by exhaust applications.
1.8.3. Temperature Controllable Reactive Dyes

These dyes can react with cellulose at temperature above the boil in the absence of alkali,
although if desired can be applied under the same conditions as the salt controllable group with
alkaline fixation at a temperature between 80 C0 and the boil. Dyes in this group have self
levelling properties and need auxiliaries to facilitate the level dyeing. Only the NT dyes belong
to this group.
2. Dyes for Nylon
2.1. Acid Dyes

The name acid dye derives from the use of an acidic dyebath. Most pre-metallized and mordant
dyes are acid dyes. In the case of mordant dyes, the dyeing are after treated with a suitable metal
ion mordant, usually chromium. In fact, mordant dyes are often referred to as chrome dyes. The
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metal in pre-metallised dyes is incorporated into the dye molecule during the manufacturing
process.
The acids used in the dyebath range from sulphuric acid (dyebath pH < 2.0) to ammonium
acetate (dyebath pH > 6.5). Acid dyes are usually sodium salts of sulphonic acids, or less
frequently of carboxylic acids, and are therefore anionic in aqueous solution. They will dye
fibres with cationic sites. These are usually substituted ammonium ion groups in fibres such as
wool, silk and nylon. These fibres absorb acids. The acid protonates the fibres amino groups, so
they become cationic. Dyeing involves exchange of the anion associated with an ammonium ion
in thenfibre with a dye anion in the bath.
The dyes with larger molecules have higher substantivity for Nylon. They are more hydrophobic,
high molecular weight dyes therefore have better fastness to wet processes.
2.1.1. Classification of Acid Dyes
2.1.1.1. Classification According to Chemical Structure

Sulphonated azo dyes constitute the major group and are mainly mono- and bis-azo compounds
ranging in colour from yellow, through red to violet and brown. The substantivity of azo dyes for
polyamide and protein fibres is greater the higher their molecular weight and the lower the
number of sulphonate groups per dye molecule.
Acid dyes usually have low substantivity for cellulosic fibres and do not give appreciable
exhaustion onto them. Some of the higher molecular weight azo acid dyes, however, are difficult
to distinguish from direct dyes for cotton. The latter are often sulphonated bis-azo and polyazo
dyes.
There are therefore a number of acid and direct dyes with similar structural features that could
be classified in either group. These dyes will dye wool, nylon and cotton. One feature that
distinguishes acid dyes from direct cotton dyes, apart from their lower molecular weights, is that
molecular planarity is not essential for acid dyes, but is for direct cotton dyes.
Anthraquinone acid dyes complement the azo dyes, ranging in colour from violet through blue to
green. These dyes often have very good light fastness. Acid dyes with triphenylmethane (blues
and greens) and xanthene (reds and violets) chromophores are less important types noted for
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their brilliant colours. These dyes have poor light fastness properties. Sulphonated copper
phathalocyanine dyes are of good light fastness.
2.1.1.2. Classification According to dyeing Characteristics

Acid dyes are commonly classified according to their dyeing behaviour, especially in relation to
the dyeing pH, their migration ability during dyeing and their washing fastness. The molecular
weight and the degree of sulphonation of the dye molecule determine these dyeing
characteristics. The original classification of this type, based on their behaviour in wool dyeing,
is as follows:
Level Dyes or Equalized Acid Dyes
Milling Acid Dyes
Super Milling Acid Dyes
Fast Acid Dyes
Levelling Fast Acid Milling Acid Dyes Super Milling
Dyes dyes Acid Dyes
Acid Used Sulphuric Acetic Acetic NH+4
Dyebath PH 2-6 4-6 5-7 6-7
Migration Ability High Moderate Low Very Low
Washing fastness Poor- Fair Good Very Good Very Good
Molecular Weight Low Moderate Low Low
Dye Solubility High Moderate Low Low
State In Solution Molecular Aggregated Aggregated Aggregated
Substantivity Very Low Moderate High High
Table 3: Acid Dyes Types
2.1.2. Acid Dyes used at INTERLOOP

Commercial Usage Migration PH Fixation Properties
Name Temperature
BEMACID F Polyamide Good 4.0 5.5 70-100 Ideal For
Series Wool Printing
Used For Dark
Shades
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EVERACID N Polyamide Good Neutral 70-100 Milling Acid

Series Wool Dyes
Excellent
migration
Excellent
levelling
BEMACID E Polyamide Good 3-4 70-100 Good migration
Series Wool Good Control
of Barriness
EVERACID E Polyamide Good 4.4.5 70-100 No Metal
Series Wool Content
Excellent
Fastness
BEMAPLEX Polyamide Moderate to 4.5-5 30-50 Two Sulfo
D Series Wool High Groups
BEMAPLEX Polyamide Low 3-80-4 70-80 C No Sulfo Group
N Series Wool
BEMAPLEX Polyamide High fixation 3.5-4 70-80 C One Sulpho
M Series Wool Group
Table 4: List and Properties of Acid Dyes used at INTERLOOP
In the progression from levelling to super-milling dyes, the washing fastness improves gradually
as the dye molecular weight increases and the number of sulphonate groups per dye molecule
decreases. Larger molecules, with fewer sulphonate groups, have lower water solubility, migrate
least during dyeing, and give dyeings of better washing fastness. They exhaust well on wool
when dyeing in weakly acidic baths with a pH above 5.
On the other hand, small dye molecules with many sulphonate groups migrate very well during
dyeing and have poor wet fastness. For low molecular weight acid dyes the dyebath exhaustion
is low when dyeing at a pH greater than 4. Acid dyes therefore show the usual inverse
relationship of migration ability to wet fastness.
2.1.3. Dyeing Nylon with Acid Dyes

Nylon molecules have amino groups at the end of the polyamide chains. Nylon, like wool, can
therefore be dyed with all types of acid dyes by an ion exchange process. Nylon filaments are
sensitive to mechanical, thermal and chemical stresses during filament production as well as
during their assembly into fabric and its preparation for finishing.
These stresses modify both the chemical and physical structure of the nylon filaments and result
in changes in dyeing rate and dye uptake. If the modification of the nylon is not uniform along
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the length of the filament, the final colour will be uneven. Disperse dyes, which dye most
synthetic fibres, migrate readily when dyeing nylon and cover such chemical and physical
irregularities in the filaments (Section 15.6). Unfortunately, the washing fastness of disperse
dyes on nylon is only poor to moderate, particularly in heavy shades. They are used mainly for
ladies hosiery and lingerie.
The washing fastness of non metallized acid dyes on nylon is moderate to good and the light
fastness is usually good. Milling or metal-complex dyes give dyeings of superior washing
fastness on nylon. Their unlevel dyeing behavior, however, results in poor coverage of filament
irregularities. The 2:1 pre-metallised dyes, in particular, give dyeings of high light fastness, as
required for example for nylon automotive fabrics. Besides hosiery and apparel, carpets are a
major consumer of nylon, particularly in the USA, and are usually dyed with acid dyes.
2.1.3.1. Preparation of Nylon for Dyeing

Nylon filaments are relatively free from impurities. Scouring with a detergent and soda ash
(Na2CO3) at 70 C usually removes spin finishes and lubricants present on the filaments and any
polyvinyl alcohol.
2.1.3.2. Adsorption of dyes by Nylon

The dyeing of nylon with acid dyes differs in a number of respects from that of wool. A simple
ion exchange process, similar to that for dyeing wool, explains many practical dyeing
observations. The limited number of amino groups in nylon and its more hydrophobic nature,
however, have a profound influence on its dyeing behaviour.
In dyeing nylon at moderate acidity (pH 34), it is therefore relatively easy to saturate all the
available ammonium ion sites with acid dye anions.
The equilibrium molar adsorption of polysulphonated acid dyes is particularly low because of
this. A simple acid dye with three sulphonate groups per molecule will neutralise the positive
charge of all the available ammonium ion sites in the nylon at one third the molar quantity of a
dye with a single sulphonate group.
For a nylon with 45 mmol kg1 of amino groups, the maximum dye adsorption of a trisulphonate
dye is 15 mmol kg1. This corresponds to less than a 0.9 % owf dyeing for an acid dye with a
molecular weight less than 600. The equilibrium molar dye adsorption at saturation of a
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polysulphonated acid dye of known molecular weight and purity is, in fact, a good method of
determining the amino group content of the nylon.
The limited number of ammonium ion sites in nylon, when dyeing with acid dyes under weakly
acidic conditions, poses problems in dyeing deep shades. In particular, the production of blacks
and other deep shades is problematic, since the amount of dye that saturates all the ammonium
ion sites is insufficient to give the depth of colour required.
The non-polar environment inside nylon filaments, and the large separation between the amino
and carboxyl groups, may not favour a zwitterionic form in nylon, as in wool, and absorption of
acid probably involves protonation of free amino groups in a non-ionic polymer and the large
separation between the amino and carboxyl groups, may not favour a zwitter ionic form in nylon,
as in wool, and absorption of acid probably involves protonation of free amino groups in a non-
ionic polymer
Fiber- NH2 + H+ + HSO-4 Fiber- NH+3 HSO-4
Fiber- NH+3 HSO-4 + Dye- SO-3 Fiber- NH+3 Dye- SO-3+ HSO-4
Dye initially interacts with ammonium ion groups in the nylon until these are all occupied at
around pH 3. The amount of dye absorbed depends on acidity of dyebath, which determines the
number of ammonium ion sites. At low PH Nylon absorbs the dye beyond the saturation limit at
PH 3.
Under such acidic conditions, protonation of carboxylic group oxygen atom of amide groups
generates new cationic sites for dye absorption. It also prevents the amide group from hydrolysis
at elevated temperatures used in dyeing.
Once a dye anion with moderate substantivity adsorbs onto an ammonium ion site in the nylon, it
is quite resistant to displacement. A rapidly adsorbed dye anion can block a site and prevent
adsorption of other dyes in the dyebath.
Substantivity of milling and metal-complex acid dyes in neutral solution, under conditions where
the nylon only has very few ammonium ion groups. In the case of these types of acid dye, the
dyefibre interaction must involve forces other than the attraction of oppositely charged ions.
Dipoledipole and hydrophobic interactions between the dye and nylon molecules play an
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important role in determining the high substantivity and good washing fastness of these types of
dyes.
Many of the high substantivity acid dyes, particularly hydrophobic monosulphonated or non-
polar pre-metallised dyes, often dye nylon in amounts well over the amino group content, even at
pH values as high as 67. Build up of deep shades is not a problem with such dyes. This
phenomenon is called overdyeing.
Acid dyes are also classified according to their substantivity for nylon at a given dyeing pH.
a. Low molecular dyes of low substantivity for nylon at PH 6-7. Although these dyes have
good migration during dyeing, they require an acidic dyebath containing acetic and
formic acid for exhaustion.
b. Dyes that have moderate substantivity for nylon and good exhaustion when applied at PH
3-5 in the presence of acetic acid. These dyes have good fastness to washing on Nylon.
c. Higher molecular weight dyes of higher substantivity for nylon even in neutral solution.
Dyeing is usually carried out at PH 6.5-7 in the presence of ammonium acetate.
The substantivity of given acid dye is greater for Nylon than Woo. Even at boil, the extent of dye
migration when dyeing nylon will be less than for wool, but the dyed nylon will have better
washing fastness.
Monosulphonated acid dyes are preferred for Nylon since their fiber saturation concentration is
equal to amino group content of the Nylon and build up the deeper shades better than the
polysulphonated dyes.
Dyeing of nylon with acid dyes starts at 4050 C in the presence of an appropriate acid, such as
acetic acid or ammonium acetate depending on the substantivity. The temperature then gradually
increases to the boil. Dyeing with weak acids is essential to avoid acid-catalysed hydrolysis and
tendering of the nylon. The initial dyeing pH and the temperature gradient during the heating
phase control the rate of exhaustion. The paler the shade being dyed, the higher the initial pH
must be.
At low concentrations of dye in the dyebath, a greater percentage of the total amount of dye
present transfers to the fibre per unit time and the risk of unlevel dyeing is greater unless the bath
circulation is very efficient For deep shades, addition of acetic acid, to decrease the bath pH,
promotes better exhaustion as dyeing proceeds.
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Despite the uniform appearance of continuous nylon filaments, they are often difficult to dye
level. It is common to see paler filaments on a fabric surface where they have absorbed less dye
than their neighbours. This effect is called barr. It arises from physical and chemical differences
along the polymer filament, which influence both the dyeing rate and the total amount of
absorbed dye.
An anionic levelling agent present in the dyebath will block a number of ammonium ion sites in
the fibres This decreases the initial rate of dye adsorption and thus promotes level dyeing. goods
are run for some time in a heated bath with the required acid and anionic levelling agent before
dye addition. The levelling agent anions exhaust onto the nylon, the bath is cooled and the dyes
are then added to start the dyeing cycle.
Too much anionic levelling agent causes excessive blocking and lowers dyebath exhaustion.
Some levelling agents are cationic compounds, containing a non-ionic dispersant to prevent
precipitation of the dyeauxiliary anioncation complex. The formation of such a complex in
solution retards exhaustion at low temperatures. The complex gradually dissociates as the
temperature increases, liberating dye molecules that are then available for adsorption by the
nylon.
When dyeing nylon, acid dyes are often incompatible in mixtures. The dyes in a mixture must all
have similar solubility and fastness properties. They will usually have the same number of
sulphonate groups per dye molecule and give about the same rate of exhaustion. The dyeing will
then always be on tone and there will be no hue change on repeated washing or light fading. The
dyestuffs suppliers recommend suitable trichromatic combinations.
A number of direct cotton dyes are useful for dyeing nylon, particularly for deep shades. These
are applied as acid dyes. They do not cover yarn irregularities well in pale shades but give
reasonable fastness to light and washing. The addition of benzyl alcohol to the dyebath (Irga-
Solvent process, Ciba Geigy) improves the coverage of barr and the washing fastness of the
resulting dyeing.
Re-use of the exhausted dyebath minimises the cost of the benzyl alcohol. Better levelling during
nylon dyeing is also possible at temperatures above 100 C using pressurised dyeing machines.
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Under these conditions, mild reducing agents such as thiourea in the dyebath scavenge oxygen
that can oxidise amino groups in the nylon.
In most respects, the dyeing of nylon 6 with acid dyes resembles that of nylon 6.6. The washing
out of the unreacted caprolactam monomer after filament spinning gives a more porous fibre that
is easier to dye than nylon 6.6. Nylon 6 is more amorphous and has a lower melting point than
nylon 6.6. It can be heat set at lower temperatures. The more porous the fiber structure and high
the amino group content result in greater dye exhaustion, better dye build up and better migration
during dyeing with acid dyes.
Dyeing of nylon 6, however, have somewhat lower washing fastness than those on nylon 6.6
when compared at the same depth of shade. When dyeing nylon 6 fabric at the boil, using a
winch machine, permanent stretching of the fabric can occur. It may be necessary to use a lower
dyeing temperature so the goods are less plastic.
To correct unlevel dyeings on nylon, the goods are treated at pH 8.08.5 at the boil. At this pH,
there are few ammonium ion groups and some of the dye desorbs. The bath can then be acidified
and the desorbed dye re-exhausted onto the nylon. This is less successful with high substantivity
acid dyes. Chemical stripping requires the use of reducing agents such as sodium sulphoxylate-
formaldehyde (NaSO2.CH2OH) but complete stripping may be difficult.
2.1.4. Problems in Nylon Dyeing
2.1.4.1. Barre
Barr is the visual difference in colour depth, and possibly of hue, along the length of dyed nylon
filaments in a fabric caused by physical and chemical variations in the polymer. This gives a
continuous pattern of colour stripes seen in the course direction in circular knits. Chemical
irregularities in nylon filaments are mainly from a non-uniform distribution of the polymer
amino groups, which causes variations in the rate of dye up-take and particularly the equilibrium
dye content of the filaments.
Polyamide formation is reversible and the amino group content may change as additional
polycondensation or hydrolysis occur when the nylon is at high temperatures during processes
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such as heat setting or texturing. The number and distribution of amino groups may also vary
because of their oxidation during processing.
Similar differences in dyeing rate along filaments come from variations in the degree of polymer
orientation and crystallinity. These physical variations can arise from uneven treatment in
processes such as filament drawing and texturising, fabric heat setting, and from uneven filament
tensions during fabric construction and processing.
Barr from physical variations in filaments can be minimised by using levelling acid dyes, or by
promoting dye migration by dyeing above 100 C, using an anti oxidant such as thiourea to
protect the amino end groups.
Pretreatment of the nylon material in a blank dyebath at a temperature around 8590 C, above
the prevailing dyeing transition temperature, is also beneficial. Under these conditions, the
movement of polymer chain segments allows the relaxation of tensions. This gives filaments
with different chemical, thermal and mechanical histories time to equilibrate before dyeing takes
place.
A new dyeing process for nylon, developed by Du Pont and called the Infinity process, uses
this principle. The process involves running the goods in a blank bath containing the appropriate
weak acid, at a constant temperature above the prevailing dyeing transition temperature, usually
in the range 7590 C. The dye solution slowly runs into the bath over about 45 min using a
metering pump. The conditions are such that the dye strike is so rapid that the actual
concentration of dye in the bath is essentially zero during the entire dyeing operation.
The rapid strike and poor dye migration result in yarns whose filaments are unevenly ring dyed
on their exposed surfaces. This gives a higher colour yield than a well-penetrated dyeing. These
ring dyeings show no decrease in washing, light and abrasion fastness when compared with well
penetrated dyeings at the same depth. By allowing the filaments to equilibrate by dyeing in a hot
isothermal bath, barr is much less of a problem using this dyeing method.
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2.1.5. Dyeing Nylon with Metal Complex Dyes

The dyeing characteristics of pre-metallised dyes vary widely depending on the type of metal-
complex dye and on the molecular complexity and degree of sulphonation. Like all acid dyes,
their application to nylon involves the usual problems:
a. Competition for the available ammonium ion sites in the nylon and exclusion of the less
substantive dyes;
b. Difficulties in producing deep shades because of the limited number of available
ammonium ion sites in nylon;
c. Poor migration and levelling during dyeing, which accentuate barr
Many weakly polar 2:1 dyemetal complex dyes, particularly those without sulphonate groups in
the dye ligands, have good build-up properties on nylon, because of over-dyeing. In deep shades,
they absorb in amounts exceeding the amino group content of the nylon and therefore must
interact with the fibre by forces other than ionic forces.
Most 2:1 dyemetal complexes, however, accentuate physical irregularities in the nylon
filaments and cause barr. Dyeing with either a weakly dye-complexing (cationic) or site-
blocking (anionic) auxiliary levelling agent in the dyebath overcomes this problem.
The 2:1 pre-metallised dyes have poor migration during dyeing of nylon, and level dyeing
requires good control of the dyeing process. Dyeing is usually started at pH 7. The goods are
pretreated with a suitable levelling agent and ammonium sulphate. The dyes are added and the
temperature raised to the boil. Some dyes may have very rapid strike at 6070 C.
A decreased rate of heating in this temperature range lowers the risk of unlevel dyeing. The very
acidic dyebaths used in wool dyeing with 1:1 dyemetal complex dyes will cause hydrolysis of
the nylon. Some dyes of this type will dye nylon using acetic acid at pH 46 with a weakly
cationic levelling agent. They give dyeing of good washing and light fastness.
2.1.6. Dyeing Nylon with Disperse Dyes

Dyeing of Nylon with acid dyes produces the good washing fastness but involves the risk of
barre. This risk is almost absent with disperse dyes . It results the good migration during dyeing
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but have poor to moderate wet fastness in heavy shades. The dyeing of nylon with disperse dyes
is therefore limited mainly to pale shades for lingerie fabrics and sheer hose that do not require
repeated or severe washing.
Disperse dyes on nylon are much better in this respect than acid dyes. The disperse dye is pasted
in warm water and the dispersion slowly diluted. Hot water and concentrated dispersant favour
the formation of large dye particles. The concentrated dispersion is then strained into the dyebath
that usually also contains additional dispersing agent. The bath is gradually heated and dyeing
continued at the boil. The disperse dyes used for nylon are usually level dyeing. The exhaustion
rates of individual disperse dyes on nylon are not overly high. They do vary from dye to dye so
that selection of compatible dyes is necessary.
Dyes of higher fastness to sublimation are invariably of greater molecular size and therefore have
lower rates of dyeing. The usual temperature for rapid dyeing disperse dyes on nylon is 85100
C. If slow dyeing heat fast dyes are used, dyeing under pressure at up to 120 C may be useful.
The disperse dyes used for dyeing nylon will also colour spandex (segmented polyurethane)
filaments in stretch hose but the washing fastness is only fair. With rapid dyeing dyes, the dyeing
rate increases with increasing temperature but the equilibrium exhaustion decreases. The more
rapid dyeing dyes also migrate better and tend to be less temperature sensitive so that dyeings at
different temperatures are close in shade Nylon 6 is more amorphous and has a lower melting
point than nylon 6.6.
Disperse dyes dye nylon 6 using the same method as for nylon 6.6. Dyeing is usually faster than
for nylon 6.6 under the same conditions and the dyes will usually show better migration. This
usually means that the washing fastness is somewhat lower on nylon 6. One advantage of nylon
6 is that heat setting using hot air or steam is at lower temperatures than for nylon 6.6.
2.2. Dyeing Cotton/ Nylon Combinations

Cotton/nylon fabrics can be dyed using disperse or acid dyes for the nylon, and direct dyes for
the cotton. Some direct dyes will give a solid shade dyeing both cotton and nylon directly at pH
45. Alternatively, some direct dyes do not stain nylon in the presence of a syntan, or do not
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stain the nylon at 8090 C in a weakly alkaline bath. These can be used to correct the shade of
the cotton. Better washing fastness is obtained with a combination of fast acid dyes for the nylon,
and reactive dyes for the cotton.
Solid shades are more difficult to dye with 50/50 cotton/nylon blends as both fibres will be
visible For batch dyeing such fabrics, direct dyes of reasonable wet fastness are used for the
cotton in conjunction with a syntan to avoid their staining of the nylon and, in a second bath,
milling or metal-complex dyes are applied to the nylon. The milling and metal-complex dyes do
not cross-stain the cotton and have good light and wet fastness.
2.2.1. Different processes used for Dyeing of Nylon Cotton Combinations

There are three different processes are used for dyeing on nylon cotton combinations at
INTERLOOP..The choice of process depends on shade and class of dye and percentage nylon in
combination. The socks are first scoured or half bleached according to depth of shade. The socks
are usually half bleached for light shades and scoured for dark shades.
2.2.1.1. Double portion Dyeing (DP)
Double Portion Dyeing
Two Bath Dyeing
Half Bleach Hydrogen Peroxide 2g/l 95 C for 20 Minutes
Rucogen WPL 0.5 g/l
Contavan GAL O.5g/l
Caustic Soda Liquid 2g/l
Cool Down to 80C
Sample Checking
Drain Machine
Hot Wash 90 C for 5 minutes

Cool Down to 80C
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Drain Machine
Cold Wash 3 Minutes
Drain Machine
Neutral+ Enzyme + Leveller 50 C for 15 minutes
Nylon Color Feeding 15 minutes
Color Time 95C for 20 minutes
Cool Down to 80C
Sample Checking
Drain Machine
Cold Wash 3 minutes
Drain Machine
Salt Addition NaCl 20g/l
Fill Water with 1:6
Leveller Addition Sarabid LDR CHT 0.5g/l
Recyle Tank for 1 minutes 5 minutes
Cotton Color Feeding
Run for 5 minutes
Soda Ash Feeding 30 minutes
Color Time 60C for 20 minutes
Drain Machine
Cold Wash 3 minutes
Drain Machine
Hot Wash+ Neutral Citric Acid 1.5g/l 50C for 10 minutes

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Drain Machine
Run for 5 minutes
Fill water with 1:10
Finishing Citric Acid 1g/l
Tubingal RGH CHT 1.5g/l 40C for 20 minutes
Drain Machine
Hydro Extraction 15 Minutes
2.2.1.2. One bath dyeing
One Bath Process
HALF 0.5 g/l Rucogen WBL

BLEACH 0.5 g/l Contavan GAL
95 For 10 Min
2 g/l Hydrogen Per Oxide
50%
2 g/l Caustic Soda (Liq.)
HOT WASH Drain at 80C
NEUTRAL 1.5 g/l Citric Acid At 50C for 10 min.
WASHING One cold wash for 5 min.
Drain 5 Minutes
Machine
Neutral + 1g/l Citric Acid
Enzyme 0.50% Cellusoft L- 50 for 10 min
Novozymes
Drain 5 Minutes
Machine
Salt Addition 3 Minutes
Color Feeding
40 for 20 Minutes
Soda Soda Ash ICI 10g/l At 60C for 30 min

Feeding Pak
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Caustic Soda 2g/l

Liquid
Color Time At 60C for 20 min
Drain Machine 5 Minutes
Sample Checking
Neutral 1.5 g/l Citric Acid 50 for 10 min
FINISHING PH SET 5.3 ~ At 40 temperature for 20
5.5 min.
1.5 g/l Tubingal RGH
0.5g/l Jinsoft TWM
Hrdro Extraction

One Bath Process
HALF 0.5 g/l Rucogen WBL

BLEACH 0.5 g/l Contavan GAL
95 For 10 Min
2 g/l Hydrogen Per Oxide
50%
2 g/l Caustic Soda (Liq.)
HOT WASH Drain at 80C
NEUTRAL 1.5 g/l Citric Acid At 50C for 10 min.

Adjust PH to 4.5-5 and nylon color feeding 70 for 10 minutes
Cool Down To 60
Salt Addition+ Caustic Feeding 3 Minutes

Cotton Color Feeding 60 for 20 Minutes

Cold Wash 3 Minutes
Hot Wash 5 Minutes
Neutral Citric Acid 1.5 g/l 5 Minutes
FINISHING PH SET At 40 temperature for 20
5.3 ~ 5.5 min.
1.5 g/l Tubingal RGH
0.5g/l Jinsoft TWM
Hydro Extraction 15 Minutes
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2.2.1.3. One bath dyeing with Acid Dyes Only
3. Lab Dips (One Bathy Dyeing of Nylon/ Cotton Combinations

3.1. Half Bleaching
Rucogin WBL 0.5 g/l

Contavan GAL 0.5 g/l
Hydrogen Per Oxide 2 g/l 95C0 10 Minutes
50%
Caustic Soda (Liq.) 2
Hot Wash at 80C0 for 5 minutes
3.2. Neutral
Citric Acid 1.5 g/l 50C0 10 Minutes
3.3. Cationization
3.4. Dyeing
3.4.1. Recipe #1
Bemaplex 0.0220% 4 90C0 45 Minutes

Yellow NRN
Bemaplex Rubine 0.0625
DB
3.4.2. Recipe#2
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Bemacid Yellow 0.005% 4 90C0 45 Minutes

NTF
Bemaplex Rubine 0.02%
DB
3.4.3. Recipe#3
Bemacid Blue 0.04% 4 90C0 45 Minutes

NTF
Bemaplex Rubine 0.04%%
DB
3.4.4. Recipe#4
Bemacid Yellow 0.005% Neutral 60C0 45 Minutes

NTF
Bemacid Red FB 0.02%
Cold wash for 5 Minutes
Hot wash at 70C0 for 5 minutes
3.5. Finishing
Tubingal RGH 1.5g/l

Jinsoft TWM 0.5g/l 40C0 20 minutes
Hydrogen Per Oxide 2 g/l 95C0 10 Minutes
50%
Caustic Soda (Liq.) 2
3.6. Method
1. The Acro Sock which contains both nylon and cotton was taken.
2. The 5 g samples were taken from sock.
3. The sample was half bleached according to above mentioned recipe.
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4. Then sample was neutralized with citric acid.

5. The sample was cationized according to above mentioned recipe.
6. The sample was dyed according to above mentioned recipes at different PH and
temperatures.
7. Then the samples were washed and finished according to above method.
8. At last samples were dried.
3.7. Fastness Properties

Sr# Recipe# Wash Fastness Crocking Fastness
1 Recipe#1
2 Recipe#2
3 Recipe#3
4 Recipe#3
Chapter 2 360 Degree Digital

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2.2. Process of Reactive Digital Printing

Reactive printing can only be done on 100% cotton socks, as it reacts with cotton, resulting
excellent testing results, hand feel, color strength and sharpness.
Reactive printing is a comparatively lengthy process it includes following steps.
100% combed cotton bleached yarn with nylon plating.

Socks knitting according to required measurements with colored toe and welt.
Make chemical solution.
Dip the socks in the chemical solution, hydro and dry it completely.
Socks reactive printing.
Steaming
Washing and finishing
Drying
Boarding
In digital printing we are using active inks for reactive printing. The process route for reactive
printing is given below.
\
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Bleached Socks
Pretreatment with
Sodium Alginate
Hydroextraction
Drying
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Steaming
Drying
Washing &
Finishing
Drying
Boarding
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2.1.1. Pretreatment
For reactive digital printing socks must undergo following step
100% full bleached cotton yarn socks.

Toe should be dyed usually black (welt and heel dyed according to requirement).
Dip the socks in the reactive chemical solution as per given recipe below.
In production we are use Tupesa sampling machine for dipping.
It is found that for excellent results are achieved if minimum solution is taken 40 liters, in
which socks are completely dipped at 8 rpms for 50 mins. c
Hydro the socks in the dip dye hydro machine for 2 min at 250 RPMs.
Dry the sock completely on trivinta dryer at 130 c set temperature for 22 min (depending
on the socks construction, i.e. more dense construction more time is required, less dense
construction less time is required) at 22 rpms (depending on the socks quantity, i.e. large
quantity no. of RPMs increases short quantity no. of RPMs also decreases).
Check the socks it should be completely dry (color of socks will changed to pale yellow
from pure white).
Socks are ready to print.
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2.1.1.1. Reactive chemical solution recipe
Chemicals Quantity
Sodium Alginate 10 G/L
Soda Ash 20 G/L
Glauber Salt 30 G/L
Urea 150 G/L
2.1.2. Reactive Digital Printing

Sock are ready to be printed. But before printing check all the parameters according to the
requirement like.
Rip the design to be printed on ULTRA PRINT software by taking the size of the socks
after adjusting it on machine axial roller.
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Measure its width.

Measure its height (roundness).
Now adjust the two laser indicators (present on the top of axial roller) at the start (welt)
point and end (toe) point of the socks for continuous production of the next socks.
The next sock should be adjusted according to laser settings.
Now move the head forward to check the head height.
Head should not be so close to the socks surface that it touches any loses fiber or
contamination present on the sock surface, secondly it should not be at more height that
the image looks blurry, lower the head height more sharpness and excellent color depth is
observed.
Head is the most sensitive part of the machine so it should have to be protected from dust
and touching with the socks or any harsh surface.
Adjust the head at optimum height and check the head status, all nozzles should be
opened. Do not start printing unless the head status is found completely ok.
Check the bi-directional calibration the two horizontal lines should overlap completely
each other at 0 point.bi-direction calibration is the movement of head along x-axis, while
going from left to right and then coming back at start point in 1 pass.
Check off-set calibration. It is printed in three colors (Cyan, Magenta and Black) for best
results the two lines of each color should overlap each other on 0 point with variant of +-
2.
Always keep a close eye on the head status and check it after 20 to 30 pieces because if
the head nozzles are blocked during printing the shade becomes lighter and can cause
variation with in the lot.
Always check the elastic size of the socks. There are different sizes of rollers available
for printing of different socks size.
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Selection of roller should be optimum, that socks should be much stretched or much
loosen.
We have following rollers of different Width and height available.
Sr. Length (CM) Diameter (CM)
1. 105 9
2. 105 9
3. 105 9
4. 65 9
5. 65 9
6. 65 9
7. 50 6.5
8. 50 6.5
9. 50 6.5
10. 50 8
11. 50 8
12. 50 8
2.1.2.1. Roller Sizes

Always measure the height carefully by printing it on paper first rather than on socks.
Design should end at the same point from where it starts in height (roundness case).
Try to start printing from the same start point to every sock to ensure constant placement
of design i.e. it is taken from the center of the heal.
It is observed that room temperature and humidity has a great effect on the ink behavior it
should be optimized to 20 to 25 C temperatures and 50% to 60% relative humidity.
Temperature above 25 C causes a lot of problem to heads. It remains on the head surface
and block the nozzles to spray. Therefore the head status is not cleared, although a lot of
strong or normal cleaning is done.
To open swear blockage of nozzles normal or strong cleaning is not much efficient. So
manual cleaning is done.
For manual cleaning take out the heads carriage away from the axial roller and then clean
the head surface softly and gently with soft tissues or fabric piece (in case of strong
manual cleaning use distilled water).
Every part of the machine should remain always clean, specially the head surface, it
sides, the capping position and the sucker pumps should all remain very clean.
Start printing by checking all the parameters set according to the requirement.
Select the diameter (height) of the roller according to the elastic stretches of the socks.
Before placing the socks on the roller cover it completely with a piece of moisture
absorbing material, so that all the ink which penetrates the socks surface is absorbed by
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that material rather than making the roller surface dirty.(usually piece of newspaper is
used)
Start printing by ripping a design according to requirement (width and height).
For ripping, ULTRA PRINT software is used, which facilitate the user to adjust height,
width, resolutions and no. of passes.
As the resolutions are increased no.. of passes are also increased. More no. of passes
enhances the color depth and picture quality but it consumes more ink and more time.
Lower no. of passes lower the color depth and picture quality but time per socks and ink
consumed is also decreases.
In production no. of passes are optimized to 6 passes, having excellent results and
optimum speed and time.
No. Of pass means that how many time the head sprays the color on a particular point.
For reactive printing we are using 6 passes which means that head sprays the color 6
times while printing forward and backward on a same point.
In ultra print we have following options of passes and resolutions are present.
Sr.
No. Of Passes Resolution
1. 1-2 Passes 360x360
2. 3-6 Passes 360x1080
3. 6-12 Passes 720x1080
4. 4-8 Passes 720x720
5. 8-16 Passes 720x1440
For reactive printing 720x1080 resolutions with 6 passes is seems to be the optimum
no. of passes and resolution in which we are we are having excellent results with
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1:10 minute time consumption and 2.1ml total ink (Depending on the nature of
design) on one piece of sock.
The ink consumption and the time consumed can be checked accurately from the
machine software.
Start printing by checking the best possible height according to the design at which
neither the head touches the socks surface at any point nor the height is so high that
the color starts flushing and merging in each other.
After printing handle the socks carefully it should not touch with any part of the
machine while unmounting it from the axial roller.
Do not keep the socks for the long time in open air without steaming after printing.
Shade difference has been observed in the socks which are steamed after one or two
days.
It is suggested to add a mild oxidizing agent in the solution if socks have to be
stayed in air for long time.
After printing the socks are ready to be hanged on trolley for steaming purpose. For steaming, a
specially designed oven is made in which a trolley with socks can be adjusted.
2.1.3. Heating:
Thermal fixation and steaming are the two different processes to fix the printing color on any
fabric.
Disperse dyes are fixed at high thermal temperature; usually these dyes are fixed at 160C in case
of printing.
Behavior of reactive dyes used for printing is entirely different, instead of hot dry heat; steam is
used to fix the dyes. Moreover steaming enhances color brightness, sharpness, hand feel and
color strength. It helps the dye to penetrate it to the fiber by swelling the fiber with the help of
urea and helps the dye to react with cellulose of cotton.
2.1.4. Our practice:

In Interloop LTD. We are using a Chinese manufactured steam oven to steam the socks its a
dual purpose oven in which steam and hot air both can be used at one time. Steaming consist of
following two parts.
The trolley system

The steam oven
2.1.4.1. Trolley system:

A especially designed two parted trolley is used to steam the socks it consist of following
parameters
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Maximum 2.5 dozens of socks can be hanged on each part. Trolley consists of two parts
so 2.5x2= 5 dozens of socks can be hanged one trolley. We got 2 trollies so as total we
have a capacity to hang 10 dozens of socks at a time.
The trays of trolley are movable so we can enhance the capacity of trolley by adding
more trays in case small size socks or toe socks.
There should be a little bit difference between to adjacent and parallel socks.
Be careful in transporting the trolley to steamer the socks should not have tro and fro
motion while travelling, that the socks touch each other or with any trolley surface. It
can copy colors on each other because socks in such conditions are wet.
Always keep the trolley clean and rust free. .
2.1.4.2. Steam Oven:

We are working here with a Chinese manufactured steam oven with a capacity of 1 trolley at a
time. Its a dual purpose oven with both facilities of dry and wet heating at one time. We can
achieve the dry temperature at maximum 130C and direct steam application. To fix the reactive
inks we work on the following parameters.
At first put on the steam for sometime with the open door of oven to remove any
condensation present in the pipes.
Load the trolley and close the door.
Put on the steam for 4 mins with the exhaust fan off.
After steaming instantly put on the dry heat for 20 mins, it helps in drying the socks as
they got completely wet when direct steam is applied. Further more it also helps in
curing.
In case of dry heat we got an option to put on the exhaust in the same time with hot air
but we do not use that option for heating the exhaust is put off during heating.
In case of steam, we have direct insertion of pressurized steam therefore there could be an
issue of dropping on the socks hanged in the lower part of trolley so to avoid that
complete removal of condensation is required from the steam pipe.
After steaming the pieces become completely dry and ready for washing. Every reactive printing
needs to be washed to remove all the unfixed dye present on the surface of the substrate. In
interloop we use different parameters to wash the socks.
Digital Printing
2.1.5. Washing
Washing is the most critical step in the processing of reactive printing/dying. Reactive dyes react
with the cellulose of cotton fiber to be a part of it, resulting a much delegated feel and excellent
crocking values.
Reactive dyes are not all fix or react with the substrate some of its part (almost 40%) remains
unfix on the surface of the substrate. These dye particles has to be removed for this we have to
include the process of washing which make reactive printing process lengthy.
2.1.6. Our practice

In Interloop PVT LTD we do washing on Flainox machine with following parameters and
chemicals.
Cold wash with normal temperature (40C) for 5 mins.

Cold wash normal temperature (40C) and neutral with citric acid 2 G/L for 5 mins.
Hot wash with soaping (RUCOGEN WBL 2 G/L) at 80C for 5 mins. (For Dark Shades).
Hot wash at 70C for 5 mins.
Rinsing at normal temperature with plenty of water for 2 mins.
Centrifuge the socks with hydro at 350 RPMs for 15 Mins.
Dry the socks on TRIVINTA dryer till complete drying at 100C at 22 RPMs for 30 Mins.
3.8. Troubleshooting
We made trails on 0 g/l, 5 g/l, 10 g/l and 20 g/l of Sodium Alginate.
It was found that we can print without sodium alginate with good color strength and fastness
properties but migration is a potential problem. We can decide levelof sodium alginate addition
from design to design.
Digital Printing
Make pretreatment mixture by following method.

1. Sodium alginate 10 g/l
2. Soda ash 20 g/l
3. Glauber salt 30 g/l
4. Urea 150 g/l
Mix with stirrer for one hour. Make solution with very low viscosity.
Full hydroo at horizontal hydro. Pick up of flat knit socks was 131%, after drying a weight gain
of 26% was observed.
It was found that for designs with more solid areas, some color migration may occur in samples
done without sodium alginate. When same samples were repeated with alginate, no migration was
observed
Preferred curing cycle is 1 min steam and 10 minute dry. If we reverse it i.e., 10 minute dry and
1 min steam, migration increases
Alginate application makes the fabric stiff. It becomes difficult to mount it on the printing roller.
Pre stretching on the pipe is required otherwise printing roller alignment can be disturbed
40% ink limited option gives better color depth
PDF file is difficult to rip. Sometimes machine stops during printing
We found slight color difference between top and bottom racks mounting on production oven
We need to identify machine at bulk level pretreatment application
Dryer gets stained with alginate. Need to carefully clean and then neutralize the dryer by citric
acid soaked fabric
If Alginate solution is thick and not properly dissolved, it may arise to patchy look
If distance of head from the fabric is increased, color depth reduces, color spreads and a red tone
appears on white areas due to color spreading.
Dont allow printed socks to stay a longer time without curing as dye hydrolysis starts. Cure
socks with 2-3 hours after printing. Dont give longer stay time without curing.
We made trails with Lyoprint RG and without Lyoprint RG. We cured socks after 7 hours and
after 24 hours of printing. It was found that Lyoprint RG has not any prominent improvement in
results.
Distance of printing head from the fabric is crucial. Lesser the distance, more will be color depth
and design sharpness
Digital Printing
We found that after curing step, 20 g/l soda socks show darker color as compared to 50 g/l Soda
socks
After washing, 20 g/l socks gave depthy red color in Navy as compared to 50 g/l soda socks
Curing at five cycles give somewhat dark color as compared to curing at four cycles.
SOP TO CONTROL THE COLOR STAINING ON WELT:

In bulk production, we faced problem of color stains on welt portion of socks. Also
workers were trained to avoid stains due to handling problems.
SOP FOR AVOIDING STEAM SPOTS ON PRINTED AREA:
Steam spots were observed in initial bathes due to falling of condensed steam droplets on
printed area. To control color spots on rib area we took 2-steps.
1. The perforated pipe of steamer was covered with metal plates to avoid steam spots due
to condensed steam.
2. The steamer was left on for 2 minutes to allow the condensed steam disappears.
SOP FOR AVOIDING SPOTS DUE TO UNEVEN TREATMENT:
Uneven shade was observed due of uneven pretreatment of socks. To avoid this problem
we have trained our workers to properly mix the solution and do not hydro the socks with
hand.
SOP FOR AVOIDING BACK STAINING ON RIB AREA:
Back staining was observed on rib area of socks as compare to STD. In order to minimize
it, soaping profile was adjusted as mentioned below.
Rinsing done with 6 RPM at L:R 1:20 for 10 min
An-ionic fixer used at 80c * 10 min with pH 5.
4. References:
1. John Shore ,Cellulosics Dyeing, Society of Dyes and Colorist, 1992 Manchester UK.
2. D Broadbent , Basic Principles of Textile Coloration , Society of Dyes and Colorist,
2001 Sherbrooke, QC, J1K 2R1, Canada .
3. https://www.cht.com/cht/medien.nsf/gfx/med_ASAN-9QYLEK_55CC46/$file/Flyer-
BEMACID-BEMAPLEX-en.pdf
Digital Printing
4. https://www.cht.com/cht/web.nsf/id/pa_metal_complex_dyes_en.html
5. https://www.cht.com/cht/medien.nsf/gfx/med_ASAN9QYLEG_55CC00/$file/Flyer_
BEZAKTIV_en.pdf.

Reactive and Nylon Dyestuffs

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Reactive and Nylon Dyestuffs

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One bath Dyeing of Nylon Cotton Combinations and Working on 360 Degree

Submitted By : Abrar Ahmad Anjum

Table 2: List and Properties of Reactive Dyes used at INTERLOOP.................................................. 18

Chapter 1 One Bath Dyeing of Nylon/Cotton

D = Dye part or chromogen (Color producing part of dye)

B = Bridging part (May be NH or NR group)

G = Reactive group bearing part.

Figure 1 : General Structure of Reactive Dye

1.3. Classification of Reactive dyes based on Reactive Group

a. Those reacting with cellulose by nucleophilic substitution of a labile chlorine, fluorine,

Figure 2: Nucleophilic Substitution

Figure 3 : Reaction of Triazine Dyes with Cellulose

b. Those reacting with cellulose by nucleophilic addition to a carboncarbon double bond,

Figure 4: Reaction of Vinyl Sulphone Dyes with Cellulose

1.3.1. Major Reactive Groups Commercially Available

Figure 5 : Dichlorotriazine (DCT)

Figure 6 : Monochlorotriazine (MCT)

Figure 7 : Monofluorotriazine (MFT)

Figure 8 : Nicotinyltriazine (NT)

Figure 9 : Trichloropyrimidine (TCP)

Figure 10 : Vinylsulphone (VS)

Figure 11 : Dichloroquinoxaline (DCQ)

Figure 12 : Difluorochloropyrimidine (DFCP)

1.4. Basic Principle of Dyeing with Reactive Dyes

1.4.1. The three-step exhaust dyeing process

1.5. Bifunctional Reactive Dyes

Figure 13 : Structure of Bifunctional Reactive Dye

1.6. Reactive Dyes for Wool

1.7. Classification of Reactive Dyes based on Application Method

3. Hot brand Reactive Dyes

Major Reactive groups used in Commercial dyes are;

Reactive Commercial Name Reactivity Dyeing Temperature

DCT Procion MX (BASF) High 25-40

1.7.1. Reactive Dyes used at INTERLOOP

Comericial Usage Reactivity Fixation Reactive Group

Table 2: List and Properties of Reactive Dyes used at INTERLOOP

1.8. Factors Affecting the Reactive Dyeing

1.8.1. Alkali Controllable Reactive Dyes

1.8.2. Salt Controllable Reactive Dyes

1.8.3. Temperature Controllable Reactive Dyes

2. Dyes for Nylon

2.1. Acid Dyes

2.1.1. Classification of Acid Dyes

2.1.1.1. Classification According to Chemical Structure

2.1.1.2. Classification According to dyeing Characteristics

2.1.2. Acid Dyes used at INTERLOOP

EVERACID N Polyamide Good Neutral 70-100 Milling Acid

2.1.3. Dyeing Nylon with Acid Dyes

2.1.3.1. Preparation of Nylon for Dyeing

2.1.3.2. Adsorption of dyes by Nylon

2.1.4. Problems in Nylon Dyeing

2.1.5. Dyeing Nylon with Metal Complex Dyes

2.1.6. Dyeing Nylon with Disperse Dyes

2.2. Dyeing Cotton/ Nylon Combinations

2.2.1. Different processes used for Dyeing of Nylon Cotton Combinations

2.2.1.1. Double portion Dyeing (DP)

Double Portion Dyeing

Two Bath Dyeing

Half Bleach Hydrogen Peroxide 2g/l 95 C for 20 Minutes

Rucogen WPL 0.5 g/l

Contavan GAL O.5g/l

Caustic Soda Liquid 2g/l

Cool Down to 80C