TEXTILE DYES: REACTIVE DYES

• Reactive dyes are available in a wide range of colours,

even in very bright tones.

• They form strong chemical bond (called covalent bond)

between their reactive groups and textile fibres, which
gives excellent colour fastness.

• They are especially suitable for cellulose fibres, but can

also be used to dye protein fibres and polyamide.
• Protein fibers require low pH level and higher dyeing
temperature than cellulose fibers – therefore cellulose
and protein fibers require different dyeing processes.
• Reactive dye doesn’t fix entirely to fabric (e.g. 70–98%)
and the rest is left in waste water.

Four dye batches with different types of cellulose fabrics, photo: Maija Fagerlund
BASIC PROCESS STEPS IN REACTIVE DYEING AND PRINTING

1. EXHAUSTION, where the dye is transferred from the dyebath to the fibre (dyeing)
or another method of applying the dye into fibre (screen or digital printing, hand-painting)

2. FIXATION, where the reaction takes place to fix the dye to the fibre

3. POST-DYE WASHING, where any excess dye is removed

DYEING CELLULOSE FIBERS WITH REACTIVE DYES

• Different reactive dyes have different degrees of reactivity, and this has an influence in the tempera-
ture of the exhaustion phase. In general, the higher the reactivity (= the speed at which the dye ex-
hausts onto the fibre), the lower its application temperature. See the suitable temperatures for dif-
ferent Remazol reactive dyes in Contemporary Colour Methods, p. 119-122

• Once the dye has exhausted onto the fibre with the addition of an electrolyte such as Glauber´s
salt, the reaction is promoted by the addition of an alkali such as calcinated soda.

• While the alkaline phase promotes the reaction of the dye with the fibre, it has the side effect of en-
couraging reaction of the dye with water (=hydrolysis). This is undesirable because:
• hydrolysed dye would be wasted and end up in waste water
• its presence on the fibre would reduce colour fastness

• There is always a degree of hydrolysis with reactive dyeing, and the dyer must minimize this by dye-
ing at as low a liquor-to-goods ratio as the machinery will allow. The liquor-to-goods ratio is the
ratio between the volume of the dyebath and the weight of goods. For example, a dyeing of 5 kg of
goods in 100 L of water has a liquor-to-goods ratio expressed as 20:1

• The final phase of the dyeing process is to remove any hydrolysed dye from the fibre by rinsing (first
in cold water, then in hot, and finally in cold again)
DYEING PROTEIN FIBERS WITH REACTIVE DYES

• Wool is dyed in mildly acidic liquor within the pH range of 4,5–5,5 and in high temperature. Acetic
acid is added to the dyeing liquor until the desired acidity value is reached. (approx. 3-5 g / l)

• The acidity of the liquor protects the wool from damage in high temperatures. However, the tem-
perature should be raised and reduced slowly.

• Dyeing wool requires less dye than cellulosic fibres, because:

• wool fiber has coarser structure
• acidic liquor does not create hydrolysis
• wool fibers have several dye-bonding groups

• Note: when dyeing wool the role of Glauber’s salt is different than when dyeing cellulosic fibres. It is
used as levelling agent, and it´s amount (conciderably smaller than when dyeing cellulosic fibres) is
calculated in percentage from the dry weight of material to be dyed.

• Silk is dyed in neutral liquor and only at 60 ºC, so its handle and lustre are not affected.

• Dyeing silk requires more dye than cellulosic fibres, because the structure of silk is fine, and the fi-
ber´s total surface is thus larger than that of cellulosic fibres.

The dyeing process of wool is explained in the book Contemporary Colour Methods by Maija Pellonpää-Forss, in pages 158-159, and
the dyeing process of silk is described in the page 159.
ENVIRONMENTAL ASPECTS

Waste water from dye houses using reactive dyes contain unfixed dye, alkali and considerable amounts
of salt. Some of the reactive dyes also contain metals. Hydrolysis should be minimised in the dyeing
process to avoid waste dye. Various end-of-pipe treatments such as decolorisation can be performed to
help to clean the waste water, however it is also important to minimise the use of chemicals. However,
especially considerable amounts of salt is always released in reactive dyeing process of cellulosic fibers.

On the other hand, modern reactive dyes are known for their bright colours and very good colour fast-
ness - textiles dyed with reactive dyes will last long without fading, and durability is also an important
factor when considering environmental aspects of different textile processes.

NOTE: The hydrolysis does not occur when dyeing wool, and also the amounts of salt are conciderably
smaller - this is not often mentioned when discussing reactive dyes, probably because wool´s market
share is much smaller than that of cellulosic fibers, and also because wool is often dyed with acid dyes.
 • The volume of dyeing liquor is calculated as the ratio of dry weight
of material to be dyed to the amount of liquor needed. The ratio
is often 1:20. Dyeing with a smaller liquor ratio results easily in an
uneven outcome, whereas when using a larger liquor ratio, the desired
depth of shade is not reached and the consumption of auxiliaries
increases.
• The amount of dye is calculated as the percentage of dry weight of
material to be dyed.
• The amounts of auxiliaries are calculated as grams per litre of dyeing
DYEING PROCESS OF REACTIVE DYES FOR CELLULOSE FIBERS liquor, unless otherwise announced in the instructions.

The outcome of insufficient amount of alkali appears as colour shade

In the page 129 of the book Contemporary Colour Methods by Maija Pellonpää-Forss,
än kirjan on hankkinut "Maija Fagerlund". Mikäli kirjaa jaellaan laittomasti, sen alkuperäiset ostotiedot voidaan selvittää.
lighter than desired .itHowever,
is explained how to incalculate
a slight difference the amountthe amount of
of salt
dyestuff and auxiliaries (glauber´s salt and calcined soda) needed in reactive dyeing process: hardly shows . According to the chart, the depth of shades of 0 .1–0 .5
Reactive dyes 129 % require 3–5 g/l of calcined soda . The subsequent depth of shades of
0 .5–1 .5 % need 5–10 g/l . When willing to dose the alkali precisely, the
chart on the next page provides assistance .
formula, except for the thickener and the oxidizer related to the formula .
This method is adapted to different sized material lots, such as sample
dyeing of swatches and machine dyeing of large lots . The amounts of auxiliaries according to dyeing temperature and the depth of shade in liquor
ratio 1:15–1:20
• The volume of dyeing liquor is calculated as the ratio of dry weight Dyeing depth of shade, % 0.1–0.5 0.5–1.5 1.5–3 >3
of material to be dyed to the amount of liquor needed. The ratio All colours* Electrolyte Cooking- or Glauber’s salt 20–30 30–50 50–70 80**
is often 1:20. Dyeing with a smaller liquor ratio results easily in an
Dyes with Alkali Calcined soda, g/l*** 3–5 5–10 10–15 15–20
uneven outcome, whereas when using a larger liquor ratio, the desired dyeing
or Calcined soda, g/l and 5 5 5 5
depth of shade is not reached and the consumption of auxiliaries temperature
NaOH, 32 %, ml/l**** 1 1–1.5 1.5–2 2–3
increases. of 40–60 ºC
• The amount of dye is calculated as the percentage of dry weight of Dyes with Alkali Calcined soda, g/l 2–3 3 3–5 5–10
material to be dyed. dyeing
or Calcined soda, g/l and 5 5 5 5
temperature
• The amounts of auxiliaries are calculated as grams per litre of dyeing NaOH, 32 %, ml/l – 0.5 0.5–1 1–1.5
of 60–80 ºC
liquor, unless otherwise announced in the instructions.
* Turquoise Blue G is always dyed with Glauber’s salt.
** For dyeing mercerized cotton and viscose, 60 g/l is sufficient at strengths of 3-5 %.
The outcome of insufficient amount of alkali appears as colour shade *** For dyeing mercerized cotton and viscose, approximately half the amount of
lighter than desired . However, a slight difference in the amount of salt calcined soda is sufficient, but not less than 3 g/l.
hardly shows . According to the chart, the depth of shades of 0 .1–0 .5 **** See appendix 1.
% require 3–5 g/l of calcined soda . The subsequent depth of shades of
0 .5–1 .5 % need 5–10 g/l . When willing to dose the alkali precisely, the
chart on the next page provides assistance .

Maija Pellonpää-Forss (2018) Contemporary Colour Methods, p.129

The amounts of auxiliaries according to dyeing temperature and the depth of shade in liquor
ratio 1:15–1:20
Dyeing depth of shade, % 0.1–0.5 0.5–1.5 1.5–3 >3
In the page 131, the stages of dyeing process of reactive dyes for cellulose fibres are explained:
Tämän kirjan on hankkinut "Maija Fagerlund". Mikäli kirjaa jaellaan laittomasti, sen alkuperäiset ostotiedot voidaan selvittää.
temperature, ºC
98
80
Dyeing process 60
diagram
40
25–30
10 20–30 60–90
A B C D
Stages of the dyeing process
A: Measure 25–30 ºC water, salt, dissolved dye and wetted material
and place into the dyeing pot. Thus, the dyeing liquor is measured
straight from the tap at 25–30 ºC. Add Glauber’s salt and stir to
aid the dissolving. Undissolved auxiliaries bind dye in a different
manner when coming into contact with the textile surface, which
produces an uneven dyeing result. Allow for the material to
absorb the dye and auxiliaries for 10 minutes. Agitate the material
diligently, especially during the first half of the dyeing time.
B: After 10 minutes of dyeing, remove the material with a ladle and
add half of the alkali that is dissolved in a small amount of liquor
taken from the pot. Use either calcined soda (= soda ash), or the
combination of calcined soda and lye (= NaOH) as the alkali. Salt
makes dye molecules migrate towards the fibres’ surface, close to
their bonding sites, whereas alkali causes the dye-fibre bond.
B–C: Raise the temperature according to the dyeing process diagram
to what is optimal for the colour in question (see list of colours
on p. 119–124). Different colours are most active in different
temperatures. For some colours, the dye-fibre affinity is strongest
at 40 ºC, while for others at 60 or 80 ºC. If the dyeing temperature
differs from the optimal, the dye fixation rate is not complete.
Some colours are applicable at more than one temperature. For
dyeing colour blends, the temperature is selected according to
what is suitable for both components. If the optimal temperature
is not known, all Remazol dyes can be dyed at 60 ºC.
Maija Pellonpää-Forss (2018) Contemporary Colour Methods, p.131
Reactive dyes 131
Tämän kirjan on hankkinut "Maija Fagerlund". Mikäli kirjaa jaellaan laittomasti, sen alkuperäiset ostotiedot voidaan selvittää.
Reactive dyes 132
C–E: The dyeing time at the highest temperature varies between
60–90 minutes, which depends on the depth of shade. For pale
shades, 60 minutes is a sufficient dyeing time, whereas deep
shades are dyed 90 minutes, in order to reach the highest possible
colour yield.
15 10 10 time, min D: Add the remaining alkali in the middle of the dyeing time. The
E F G H I
alkali is again dissolved to liquid taken from the dyeing liquor, and
not poured onto the material directly. During this stage, most of
the dye molecules have already reached their binding sites on the
fibres, and adding alkali accelerates the fixing process. Also, the
colour shade begins to level by diffusion, more specifically, dye
detaches from areas where the dye concentration is higher than
average and migrates to areas with a concentration lower than
average.
E–F: Cold rinsing removes the auxiliaries that are no longer needed,
and simultaneously some of the unbonded dye also. Cold water in
rinses saves energy.
F–G: Heat the water for the finishing wash.
G–H: Immerse the material into 98 ºC water and wash in boiling
water for approx. 10 min. The boil-wash removes the remaining
unbonded dye. Add detergent accordingly, especially if there
are significant colour differences on the textile surface, or if
colour turquoise is in question. The detergent binds unbonded
dye molecules to itself, thus preventing them from returning to
fibres. For reaching a good outcome, it is important to rinse off
thoroughly the alkali and salt before the hot wash. If auxiliaries still
remain in the material during the boil-wash, the affinity between
unbonded dye and fibres is activated, which complicates the
washing. This kind of poorly bonded dye detaches the material
during washes upon wear, thus weakening the wash fastness.
H–I: Final rinse: rinse off the unbonded dye residue and the possible
detergent, as in regular laundry.
NOTE

• Wear gloves during the whole process

• Wear a mask and use fume cabinet when handling the chemicals before they are solvent into water
• Dissolve dye and calsinated soda always in fume cabinet, and preferably also Glauber´s salt
PRINTING (AND HAND-PAINTING) PROCESSES OF REACTIVE DYES FOR CELLULOSE FIBERS

• Reactive dye printing requires an alkali as a fixing agent to establish the molecular bonds between
the dyes and the fibres
• Screen printing with reactive dyes also requires thickener
• Electrolyte such as Glauber´s salt is not needed, as colour is applied directly onto the desired areas
• In digital printing, the reactive dye is printed on a fabric pre-treated with the needeed auxiliaries
• Fixation process, which attaches reactive dyes to the fabrics, is generally made by steaming (or, in-
dustrially, in curing oven - note the difference in recipes)
• This is followed by washing to remove the excess dye and auxiliaries
 achieving a smooth paste requires the use of an electric mixer or a
handheld blender .
The auxiliaries of the printing paste are dissolved in water at room
In page 149 of Contemporary Colour Methods, the recipes and processtemperature,
of screen printing withalkali,
starting with reactive dyes on
and adding the cellulose are explained:
thickener last .
The stiffness of printing paste has an impact on dye penetration,
Tämän kirjan on hankkinut "Maija Fagerlund". Mikäli kirjaa jaellaan laittomasti, sen alkuperäiset ostotiedot voidaan selvittää.

and on the crispness of print outlines . Printing on thick base materials,

149
the amount of thickener may be decreased, and respectively, slightly
Reactive dye printed
increased on thin materials . When applying new base material
clothing fabric, viscose
velvet. Hanna-Maaria
qualities, the required number of pulls of the squeegee compared to dye
Sinkkonen and Sophie penetration and pattern/outline crispness are examined with tests before
Sälekari, TT
the actual printing . Also, the personal “printing power” of one’s hand is
taken into account .

Stages of reactive dye printing

• Prepare the printing paste and print colour.
• Attach the base fabric to a rubber- or plastic-covered table for printing.
• Print the fabric.
• Detach the printed fabric from the table and dry.
• Fix the dye with steam, or with dry heat (providing that the printing
Reactive dye’s direct application printing paste for cellulosic fibres
paste contains a sufficient amount of urea).
The function of Auxiliary/product Steam fixing, Dry heat fixing,
substance in the amount of amount of • Rinse with cold and then with lukewarm water to remove the thickener
printing paste auxiliary auxiliary
and auxiliaries.
Solvent Water, 20 ºC 335–345 ml 255–265 ml
Moisture binding agent Urea 100 g 200 g
• Remove unbonded dye in a boil-wash with or without detergent.
Sodium bicarbonate* 25 g 25 g A boil-wash is repeated if necessary.
Alkali
or calcined soda 15 g 15 g • Apply the final rinse to remove unbonded dye and detergent.
Dye’s protective agent, Rapidoprint XR 30 g 20 g
oxidizer
• Dry the material.
Alginate thickener, 500 g 500 g
CHT’s alginate NVS**,
8–10 %
(= 40–50 g CHT’s alginate
Thickener NVS + 460–450 g water)
or Lyoprint RD-HT, 7 % 500 g 500 g
(= 35 g Lyoprint +
465 g water)
Total, approximately 1000 g 1000 g

* Vinyl sulphone group reactive dyes fix also with milder alkali, such as sodium bicarbonate. Printing
paste and print colours prepared with it keep longer their bonding capacity than those prepared with
calcined soda, due to slower hydrolysis. Monochloretriazin group dyes require calcined soda for fixing.
** Other alginate thickener products are applicable also.
Maija Pellonpää-Forss (2018) Contemporary Colour Methods, p.149
 Tämän kirjan on hankkinut "Maija Fagerlund". Mikäli kirjaa jaellaan laittomasti, sen alkuperäiset ostotiedot voidaan selvittää.

Reactive dyes 146

145

In the page 145, the recipes and process of painting with reactive dyes on cellulose are explained:
A method, in which the painting
is done on a blank screen and
transferred to fabric by printing
with clear printing paste. The
first print is like the painting,
whereas the second is lighter in
shade. Susanna Junttila, MP-F

Preparing the painting colour

• Dissolve alkali, urea and oxidizer in approximately half the amount
of warm water. Add the remaining water, which is cold. Add alginate
Replace the powder gradually with an electric mixer. After the consistency is
amount of dye settled, the solution/paste is ready to use.
with water, • Add dye; granulates as such, powders dissolved in a small amount of
and add the hot water.
dye stuff later
similarly as to • Consider preparing generously the amount of clear painting liquor
printing paste Reactive dye painting colours from liquid to stiff (without dye), as it is used for diluting the dyes to create paler shades.
The function of Auxiliary/product Painting Painting Painting Painting Keeping the liquor’s pH value constant is important when diluting
substance in the colour I, colour II, colour III, colour IV, painting colours.
painting colour basic colour runny stiffer stiffest
Dye Remazol 20–40 g 20–40 g 20–40 g 20–40 g
Painting
Solvent Water, 20 ºC 875–885 ml 864–874 ml 857–867 ml 800–815 ml • The amount of alginate regulates, e.g. the dye’s ability to absorb into
Moisture-binding agent Urea 100 g* 100 g 100 g 100 g the material.
Dye’s protective agent, Rapidoprint XR – 1g 3g 5g • The fabric can be attached to a frame that is off the table top, to avoid
oxidizer dye from running onto the table. Alternatively, a backing cloth can be
Sodium bicarbonate 25 g 25 g 25 g 25 g placed underneath the fabric to absorb the excess dye that passes
Alkali
or calcined soda 15 g 15 g 15 g 15 g through the painted fabric.
Thickener Alginate thickener, – 10 g 25 g 35 g • When painting wet-on-wet, the first layer of dye cannot absorb new
powder, e.g. dye like when painting wet-on-dry. For the same reason, shades
CHT’s alginate NVS painted on wet fabric remain lighter.
Total, approximately 1000 g 1000 g 1000 g 1000 g

* With a double-dose of urea, the Drying, fixing the dye and finishing washes
painting can be dry heat fixed • Dry the painting and fix the dye by steaming. It can be also dry heat
A skilled execution of the reactive
also, just like a reactive dye print. fixed, but the painting colour must then contain a double-dose of urea.
dye painting method. A detail of
artwork Vanhankaupunginkoski • Apply the finishing washes as in other reactive dye methods for
(The old town’s rapid). Susanna
cellulosic fibres.
Junttila, SJ

Maija Pellonpää-Forss (2018) Contemporary Colour Methods, p.145

PRINTING (AND HAND-PAINTING) PROCESSES OF REACTIVE DYES FOR PROTEIN FIBERS

• The printing paste for protein fibres differs from the one for cellulosic fibres only by acidity - the pH
of printing paste is changed to mildly acidic with sodium acetate.
• When painting wool and silk, printing paste with reduced amount of thickener can be used.
• NOTE: if the dye does not absorb easily into the fabric when printing / painting, wetting agent can
be added.
• Finishing is done by steaming, similarly as for cellulosic fibers. This is followed by washing to remove
the excess dye and auxiliaries. Post-dye washing is done firstly with cold, then warm, and then again
cold tap water:
• for silk, raise the temperature from 50 ºC to 80 ºC
• for wool, raise the temperature from lukewarm to 60 ºC.
 The printing paste for protein fibres differs from the printing paste for
cellulosic fibres only by acidity .
and precise details, the printing paste should be prepared relatively
If the print outline on silk spreads during steaming, it is a sign
In pages 164-165 stiff . There are plenty
withofreactive
different dyes
qualityon
silks available, and a test prin
of tooof Contemporary
much urea and/or tooColour Methods,
long steaming time . the
This recipes
may happenand process of screen printing wool and silk
are explained:especially for light weight and sheer silk qualities . To print crisp outlines including steaming and finishing washes is always appropriate .
Printing deep shades onto wool requires smaller amounts of dye
than printing onto cellulosic fibres; the full depth of shade requires an
Dyed and printed organza.
average of 30 g/kg, for dark shades of blue and black 40 g/kg . Silk, in
Helmi Liikanen, TT turn, requires more dye, even 60 g/kg, because of the fibres’ large surfac
area .
Wool and silk are printed on a rubber- or plastic covered table, as
all dyes that require finishing washes . Since many silk qualities stretch
when wet, which makes colour registration difficult, the fabric is
attached to the table stretching it extra carefully . Light weight qualities
need also a backing cloth underneath to absorb the excess dye and
prevent the dye from spreading . The printed fabric is dried, and dye is
fixed by steaming .

Reactive dye printing paste for wool and silk

Steam fixing
The function of substance Auxiliary/product Wool, the amount Silk, the amount • Wool at 102 ºC for 10–20 min
in the printing paste of auxiliary of auxiliary
• Silk at 102 ºC for 10 min
Solvent Water, 20 ºC 170–160 ml 240–190 ml
Moisture binding agent Urea 100 g 50–10 g Finishing washes
Add only, if
needed after Acidity regulator Sodium acetate trihydrate 50 g 50 g • Rinse firstly with cold, then lukewarm running water to remove
test print: thickener and auxiliaries.
Dye’s protective agent, Rapidoprint XR 20 g 20 g
oxidizer • Wash by raising the temperature for silk from 50 ºC to 80 ºC,
Wetting agent Ecopon DG 1–2 g 1–2 g and for wool from lukewarm to 60 ºC.
Alginate thickener,
Thickener CHT’s alginate NVS, 8–10 % 650 g 650 g Wool- or silk printing paste can be used for printing polyamide . The
or Lyoprint RD-HT, 7% colours’ depth of shades differ from corresponding colours on wool and
Total, approximately 1000 g 1000 g silk . Therefore, colour testing is inevitable before the actual work .

Maija Pellonpää-Forss (2018) Contemporary Colour Methods, p.164-165

NOTE

• Printing/painting paste will only stay good for couple of weeks – make only the amount you need
• Wear gloves during the whole process
• Wear a mask and fume cabinet when handling the chemicals before they are solvent into water

Sources of the lecture:

Thomas Bechtold, Tung Pham: Textile Chemistry, 2019, Walter de Gruyter GmbH, Berlin/Boston

Maija Pellonpää-Forss (2018) Contemporary Colour Methods

Woodhead Publishing Series in Textiles: Number 126: Textiles and Fashion - Materials, Design and Technology, Edited by Rose Sinclair,
19.5.1.2 Reactive dyes
CALCULATIONS

Printing and painting

• Firstly, we mix the printing pastes and painting extenders in colour working groups - each team
mixes one paste, but the whole course can use them
• Group A: 2 kg of printing paste for cellulosic fibers
• Group B: 0,5 kg of stiffest painting extender for cellulosic fibers
• Group C: 0,5 kg of basic painting extender for cellulosic fibers
• Group D: 1 kg of printing paste for wool

• Then, each colour working group mixes the colours they want to use. Start with a 100 g batch of
one colour - later on afternoon and later on the course you can of course make more, in teams and also
individually. You may start by mixing the colour in printing paste or painting extender, for cellulose or
for wool - that is up to you.

• Make the calculations for paste and the first colour before going for lunch (except group C)

Dyeing

• Before Wed 1.11, decide the colour for your group´s exhaust dyeing and make calculations for it.
Note, that you need to weight the samples in advance to be able to make the calculations - you will get
your samples today, but you can also include (small amounts) of your own fabrics if you want.
CALCULATIONS - PRINTING AND PAINTING

Instructions: Eeva Heikkinen / colour swatch folders in dye kitchen

CALCULATIONS - EXHAUST DYEING

Instructions: Eeva Heikkinen / colour swatch folders in dye kitchen