Wojciech Czajkowski,

Joanna Paluszkiewicz
Synthesis of Bifunctional
Institute of Polymers and Dyes Technology,
Monochlorotriazine Reactive Dyes
Technical University of Lodz.
ul. Żeromskiego 116, 90-543 Lodz, Poland Increasing UV-Protection Properties of
Cotton Fabrics
Fax (48)(42)6362596
E-mail:woczajk@p.lodz.pl,
joanna.paluszkiewicz@p.lodz.pl

Abstract
Several yellow and red bis-monochlorotriazine reactive dyes with built-in UV-absorber
residues were synthesised. Their application properties were determined during the col-
oration of cotton, and the UV-protection factor (UPF) of the dyed fabrics was measured.
The results of these measurements were compared with those obtained for coloration of the
same fabrics carried out with the use of dyebaths containing a composition of a model dye
and colourless fibre-reactive UV absorber.

Key words: chlorotriazine, UV-absorbers, ultraviolet protection factor (UPF).

Introduction ants or to prevent the photodegradation ate affinity to cellulose fibre, which lim-
of dyed fibres. ited their application in typical exhaust
In the last decade increasing attention methods [14].
has been paid to protective properties of In our previous work on the synthesis
textiles against UV radiation originat- of reactive dye derivatives of C.I. Re- The purpose of the present work is to ex-
ing from sunlight. In view of the practi- active Red 198 containing built-in UV- amine the synthesis of more substantive
cal and aesthetic points, in summer we absorber residue (2’-hydroxyphenyl- symmetric homobifunctional monochlo-
usually wear clothes which are made of benzotriazole) in their molecules, it was rotriazine yellow and red dyes of a gen-
cotton, but this natural fibre comprises found that cotton fabric dyed with new eral structure, as presented in Figure 2.
only a small barrier to ultraviolet radia- colorants exhibited approximately 10%
tion, especially when the textile garment higher UPF-factor values in comparison While preparing these dyes, three water-
is white or dyed with light colours. A with those of the same fabric coloured soluble aromatic diamines were used as
typical industrial practice used in order with model dye. A disadvantage of the diamine bridges: 4,4’-diaminostilbene-
to overcome this problem is the applica- dyes discussed above was their moder- 2,2’-disulphonic acid (D), 4.4’-diamino-
tion of a colourless water-soluble auxil-
iary which shows an affinity to cellulose
fibre and acts as a UV absorber [1-5]. SO3H
Especially interesting from a practical Cl N N Cl
point of view are fibre-reactive absorbers HN NH
N N N N
which, when fixed to the fabric, are able
HO3S
to maintain its protective properties for
NH NH
extended periods. Examples of such UV-
absorbers – derivatives of triazine [6] and
oxalic acid diarylide [7]- are presented in
Figure 1.
SO2CH2CH2OSO3H SO2CH2CH2OSO3H
In recent reviews of the possible devel-
opment of synthetic dyes for textile ap-
plications, it has been suggested that
NHCO-OCHN
a modern colorant could also perform
additional functions beside its specific
H3CO NH
colouristic and fastness properties , such N NH
as antibacterial action, increased UV- or SO3H SO3H
N N
IR- absorption, or water repellence [8, 9]. NH N Cl
These dual dye properties would allow Cl
N N
the number of chemicals used in the dye-
house to be reduced.
NH

A synthesis of a dyes with built-in UV- SO3H

absorber moiety was earlier reported in
groups of disperse [10-11], acid [12], di- HO3S
rect [12] and reactive dyes for cotton [13].
The aim of this work was to increase the Figure 1. Examples of fibre-reactive, water-soluble colourless UV-absorbers used for
lightfastness of newly-prepared color- increasing the protective properties of cotton fabrics.
Figure 1. Examples of fibre-reactive, water-soluble colourless UV-absorbers used for
122 increasing the protective
Czajkowski W., Paluszkiewicz properties
J.; Synthesis of Bifunctional of cotton
Monochlorotriazine fabrics
Reactive Dyes Increasing UV-Protection Properties of Cotton Fabrics.
FIBRES & TEXTILES in Eastern Europe January / December / A 2008, Vol. 16, No. 5 (70) pp. 122-126.
 Cl Cl
H3COCHN N N NHCOCH3
N N
SO3Na SO3Na

3,3’-disulpho-diphenylurea (D1) and 2- N N NH N NH-DIAMINE-NH N NH N N

Cl Cl
methoxy-1,3,5-triazynyl-4,6-bis-N1,N1’
H3COCHN NHCOCH3
-(1,4-diaminophenyl-3-sulphonic) acid SO3Na SO Na
N N N N
SO3Na SO3Na
3
(D2) (Figure 3). The use of 4,4’-diami- N N NH N NH-DIAMINE-NH N NH N N
nostilbene-2,2’-disulphonic acid in the Yellow dyes
preparation of UV-absorber derivatives of
SO3Na SO3Na
s-triazine was earlier reported [6, 7, 15]. Yellow dyes
The two latter diamines synthesised in our Yellow dyes
laboratory were used as intermediates in Cl Cl
the preparation of colourless bis-mono- N N
chlorotriazine cellulose-reactive UV ab- N NH-DIAMINE-NH N
SO3Na N N
sorbers of a similar type [16, 17]. OH NHCl NH OH
NaO3S
Cl
N N N N N N
Several UV-absorbers based on diamines N NH-DIAMINE-NH N
D1 and D2 prepared during our previous SO3Na
NaO3S SON Na
3 NaO
N
S NaO3S
SO3Na
OH NH 3
NH OH
work [16], such as A1 and A8 presented N N Red dyes
in Figure 4, were characterised by good N N

light stability, whose UV-protection prop- Figure 2. General

NaO3S structure of SO the homobifunctional
3Na Red dyes NaO3Smonochlorotriazine
SO3Na
reactive dyes
erties increased after their application in synthesised in present work.
cotton fabrics. These products may be
classified in the group of light stabilis-
ers without hydrogen bridges, which owe Red dyes
their properties to high molar absorption
Figure 2. General structure of the
H 2
N homobifunctional
CH CH monochlorotriazine
NH2 reactive dyes
in the 300-400 nm range [18]. synthesised
NaO3S in present work. SO3Na
D
It might be expected that introducing the Figure 2. General structure of the homobifunctional monochlorotriazine reactive dyes
same diamine bridges to the dye structure OMe
would increase its UV-absorption in the synthesised in present work.
N N
desired range. Due to the high level of
wash-fastness caused by the fact that a H2N NH C NH NH2 H2N NH N NH NH2
dye molecule is covalently bonded to the
NaO3S O SO3Na NaO3S SO3Na
fibre, it might also be expected that the
UV-protection properties of the dyed fab- D1 D2
ric should persist for an extended period.
Figure 3. Structure of diamine bridges used.
The application and protective properties of
the newly synthesised yellow and red dyes
were compared with a model yellow dye Figure 3. Structure of diamine bridges used
MeO N N OMe
Y1 and model red dye R1 (C.I. Reactive NH NH C NH NH
Red 120), in which, according to industrial N N N N
practice, simple derivatives of phenylen- NaO3S O SO3Na
ediamine were used as diamine bridges. Cl Cl
A1
In order to estimate the possibility of de-
creasing the number of chemicals used
MeO N N N OMe
in the dyehouse by using the newly syn- NH NH NH NH
thesised dyes, additional application tests N N N N N N
were carried out. In these tests, samples NaO3S SO3Na
OMe
of the same textile fabric were dyed with Cl Cl
14
a composition of a model reactive dye and A8
fibre-reactive UV-absorber auxiliary. For
this purpose, two colourless fibre-reac- Figure 4. Structure of colourless reactive UV-absorbers used in the present work.
tive UV-absorbers synthesised during our 14
earlier work [16], A1 and A8 (presented
the MALDI
in Figure 4), were used. A model reactive Figure (matrix assisted
4. Structure reactiveHPLC
laser desorp-
of colourless analysis was
UV-absorbers usedperformed using work.
in the present a
yellow (Y1) and reactive red (R1) were tion ionisation) technique. Spectropho- DAD 200 instrument with a Zorbex SB-
used as the reference dyes. tometric measurements were taken on a Phenyl column, eluent 50% phosphate
Perkin Elmer Lambda 40 spectrophotom- buffer pH = 6.9 (0.575g NH4H2PO4 +
Experimental eter in the UV-VIS range. The measure- 0.7 g Na2HPO4 in 900 ml water and 100
ments of UV transmittance through the ml methanol mixture) + 50% methanol.
Characterisation of products fabric samples were carried out with a
Mass spectra of the prepared dyes were Beckman DK-2A double-beam spectro- Synthesis of the reactive dyes
taken in a dihydroxybenzoic acid matrix photometer equipped with an Ulbricht Synthesis of the required intermedi-
with a Voyager Elite spectrometer using sphere and powered by a hydrogen lamp. ates was carried out as previously de-

FIBRES & TEXTILES in Eastern Europe January / December / A 2008, Vol. 16, No. 5 (70) 123

15
scribed: diamine D2 [17], diamine D1 filtered and buffered to a pH of 7.0 ± 0.2, the concentration of dye was measured
[19], absorbers A1 and A8 [16]. All the and finally dried. The main product area spectrophotometrically. The same proce-
other intermediates used, including 4,4’- determined (as in the above example) by dure was repeated with the sample which
diaminostilbene-2,2’-disulphonic acid water-pyridine
HPLC analysis was 90.3%.system. The percentage
The structure had not been degree
extractedof fixation was then calcul
with the water-
(D), were of technical grade, obtained by of this dye,water-pyridine
which was a mixture system.
of so-The pyridinepercentage system. degree of fixation
The percentage degreewas then cal
courtesy of Boruta S.A. Dyestuff Indus- dium andfollowing
potassiumformula: salts from the par- of fixation was then calculated from the
try Works, Zgierz (Poland). ent product,following
was also confirmed formula:by mass following formula:
spectroscopy in negative mode. Molecu-
C
The bi-functional reactive yellow dyes lar ions such as pentasodium, tripotas- F = 2 C×2100%
Y1-Y4 (Figure 2) were synthesised sium salt (M1) m/z = 1938 and trisodium F C=1 × 100%
by coupling diazotised 2-aminonaph- pentapotassium salt (M2) m/z 1974 and where: C1 – absorption C1 of the dissolved
thalene-4,8-disulphonic acid- (‘C-acid’) [M1-Na+H] m/z –
- = 1914,
where: C1[M1-2Na+2H]
– absorption
–
ofsample with pyridine-water
the- dissolved sample withazeotrope
pyridine-water aze
[M1-2K-2Na-2H](temperature
with 3-aminoacetanilide m/z=1812, m/z [M2-3Na+H]
= 1894,[M1-2K-2Na-2H] m/z=1902,
where: C m/z
– [M2-2K+2H]
= 1812,
absorption without
of the m/z=1894
extraction,
dissolved C were
– absorption
sample with of the
pyridine-water
witha
–
extraction,
1 C 2 – absorption of the dissolved
2 sample extracted
10-12 °C, pH = 3.5-4.0 from NaHCO3). [M2-3Na+H]– m/z = 1902, [M2-2K+2H]
extraction,
azeotrope. C -
2 – dissolved
absorption sample
of the extracted
dissolved with pyrid-
sample extracted wi
detected,theamong
After completing process,others.
the reaction m/z = 1894 were detected, among oth-
azeotrope. ine-water azeotrope.
mixture was alkalised to pH = 8.0-8.2 ers.
Results
with sodium and discussion
carbonate, and the monoazo
The total dyeing process efficiency was calculated
The total dyeing
fromefficiency
processfrom
the following
was
formula:
The total dyeing process efficiency was calculated the following formul
dye was separated by salting out with so- Results and discussion calculated from the following formula:
Application
dium chloride. tests the dye was
After filtration, E×F
Application tests T= E ×% F
dispersed in water and condensed with T =100 %
cyanuric chloride (3-5 °C, pH = 6.5-7.0), Application tests of the cotton
Application tests of the cotton fabrics were carried out on a Rotec (Roaches) laboratoryfabrics 100
and after that with appropriate amounts were carried out on a Rotec (Roaches) However, the above-described method
of diamine (30-40 °C, pH = 6.5-7.0). laboratory dyeing However,machinethe using a proc- was not
above-described applicable innotmeasurements of measureme
dyeing machine using a process typical for monochlorotriazine reactive dyes.method Bleached was cotton applicable in
Both condensation processes were con- ess typical for monochlorotriazine reac- the UV-absorber
However, the above-described methodfixation was not of theapplicable
fibre due in measure
trolled by TLC chromatography (Merck tive dyes. Bleached 2 cotton with a linen to to intense absorption
Kiesegelwith60 Fa254linen weave,
plates, ethyl with a weight
acetate, weave,
absorber
of with
104 g/m
a weight
fixation
(Fabric ofg/m
of 1041),
the
2 fibre
and bleached
(Fab-
due intense
cotton satin, withofa the
absorption of thedissolved
dissolved fabric
absorber fixation of the fibrefabricdue to samples
intense in the near UV-region.
absorption of the dissolved fabr
n-propanol, water in the ratio 2 of 1:6:2 ric 1), and bleached cotton satin, with a
weight
as the eluent; e.g.of for119 g/mTLC
dye Y4; (Fabric
data 2), wereofnear
weight used.
119 UV-region.
g/mDyeing
2
(Fabric was 2), werecarried
used. outStructuralfor 70 data minutesof the at a
prepared dyes, ac-
– dichlorotriazine dye Rf = 0.46, mono-
near UV-region.
Dyeing was carried out for 70 minutes at companied by their application proper-
3
chlorotriazine dye Rof
temperature f = 85˚C
0.05). (2g HPLC a temperature
fabric samples, 1:10of Structural
85 °C (2 gdata
fabric-bath of 50
fabric
ratio, theg/dm
sam- prepared
tiesoffor dyes, 2,
crystalline
Fabric accompanied
sodium
and UPF values byfortheir application
analysis of dye Y4 gave one single peak ples, 1:10 fabric-bath ratio, 50 g/dm3 of dyed fabricdyes,
Structural data of the prepared accompanied byboth
their applicati
samples are listed in Table 1.
with a retention
sulphatetime and of 20 6.55
g/dmmin,
3
of for
sodiumcrystalline sodium
Fabric
carbonate). 2, sulphate
Model and UPF and
yellow 20
Y1g/dm
values for3 both
and red R1 dyeddyesfabric used atare listed in Table 1.
weresamples
87.8% of the area. The structure of the of sodium carbonate). Fabric 2, and Model UPF values
yellow Y1 for Itboth can be noted that samples
dyed fabric col-in Table 1.
are listed
all the examined
final products was also confirmed by and
concentrations of 1% of the weight of fabric. red R1 dyes were
It can Thebe used at concentra-
noted that
amounts of theall the orants
R2-R4 exhaust
examined
and Y2-Y4 well in
colorantsdyestheexhaust
cotton fabric
well in the cotto
MALDI mass spectroscopy in negative tions of 1% of theItweight can be of noted
fabric. that
The allused, the examined colorantsofexhaust
and the substitution typical in-well in the co
mode. For the same Y4 dye, molecu- amounts of the R2-R4 and Y2-Y4 dyes termediates used in industrial practice,
used were calculated on the basis ofandtheirthespectrophotometric
used were calculated
substitution of typical measurements intermediates
in orderused to in industrial practice
lar ions [M-COCH3 + H]– m/z = 1644, and the onsubstitutionthe basis of their of typical p-phenylenediamine
such asintermediates used orin o-phe-
industrial pract
[M-2COCH3-Na + H] m/z = 1579, [M – C spectrophotometric measurements in or- nylenediamine, with diamines of a more
–

receive
acid residue + 2H] the
– same
m/z dyebath
= 1345 strengths
were de- phenylenediamine
der toasreceive
in thethecase same ofdyebath
the model o-phenylenediamine,
orstrengths
dyes. The percentage withdegrees
diamines of a more extended s
phenylenediamine extended structure
or o-phenylenediamine, withresults in practically
diamines of a more extended
tected, among others. as in the case of the model dyes. The per- no changes in the behaviour of dye ex-
of the dyes and UV- absorber centage in practically
exhaustion
degrees of the were no calculated
dyes changes
and UV- ab- in from
thehaustion.
behaviour of dye of
spectrophotometric
In the case
exhaustion.
yellow
In the case of
dyes, aIn the case o
in practically no changes
Reactive red dyes (R2-R4) and de- sorber exhaustion were calculated from slight increase in the exhaustion values in the behaviour of dye exhaustion.
rivativesmeasurements
of C.I. Reactiveaccording
Red 120 (R1) slight
spectrophotometric
to the following increase
formula: in the exhaustion
measurements ac- can values
even becanobserved.
even beAll observed.
the dyes Allgavethe dyes gav
were prepared by the usual methods, i.e. cording to the slight increase
following in the exhaustion
formula: values can even be observed.
very similar levels of fixation and dyeing
All the dyes
condensation of cyanuric chloride with levels ofDfixation and dyeing efficiency efficiencywhen when compared
compared withofthose of the
with those
1-amino-8-hydroxynaphtalene-3,6-di- E= (1 − of2 )fixation
levels × 100% and dyeing the efficiency
model dyes, when although compared
in the casewith of those of
sulphonic acid (‘H-acid’) in an aqueous D1
although in the case of red dyes red dyes
thesethese values
values arearesomewhat
somewhat low- lower than mi
medium at pH = 1.2-1.5 at a temperature where: D1 –although absorptioninof the the dyebath
case ofatred erdyes than these
might values
have been are expected.
somewhat Thelower than
of 0-5 °C followed
where: by coupling with dia- of λthe
D1 – absorption max before
dyebath dyeing,
at λmax D2 –before
absorption of theD2 –same
expected. The samedyeing, observations absorptionapply to theofcolour
observations theapply
dye to the
yield colour
of the dyeings, wher
zotised orthanilic acid (5-10bath°C, at λpH = 5-6 dye bath at λexpected.
max after dyeing max after dyeing The same observations yield apply
of the dyeings,
to the colourwhere yield
only aofslight
the dyeings, w
from trisodium phosphate). Dichloro- decrease in this parameter can be noted
triazine dye was then condensed with The dyedecrease fixation ofinthe thisfibre
parameter
was meas- can be noted in the case of the yellow dyes Y2 and Y
in be
the noted
case ofin thethe
yellow
decrease in this parameter can casedyes Y2 and
of the Y3. dyes Y2 an
yellow
an appropriate diamine at 30-40 °C and ured with the use of two samples of dyed Practically the same application results
The dye fixation of the fibre was measured with the use of two samples of dyed fabric of
pH = 6.5 ± 02 (10% NaOH). The process fabric ofthe thesamesame application
weight. One resultsof themwere obtained
were obtained while
whiledyeing Fabric
Fabric 1.1.
was controlled by TLC chromatography was subjected thetosame repeatedapplication results were
hot extraction obtained whiledyeing
dyeing Fabric 1.
the same weight. One of them was subjected
(Merck Kiesegel 60 F254 plates, ethyl ace- with pyridine-water azeotrope in orderto repeated hot extraction with pyridine-water
tate, n-propanol, water in the ratio of 1:6:2 to strip away any unfixed dye. After Measurements of the protective prop-
azeotrope
as the eluent; e.g. forin dyeorder
R3 TLC to data
strip– away anyinunfixed
rinsing water and dye. After
drying, sample in erties
therinsing waterofand the dyed
drying,fabrics
the
dichlorotriazine dye Rf = 0.32, monochlo- was dissembled into single threads and All the textiles used were examined for
o
rotriazinesample
dye Rf = was0.12). The dye was
dissembled dissolvedthreads
into single in cold and (0-5 °C)dissolved in coldtheir
concentrated (0-5protective properties by in vitro
C) concentrated
separated from the solution by salting out sulphuric acid. After pouring this solu- measurements of7 their UPF value, ac-
with the sulphuric
use of 7% acid.
sodium chloride
After and this
pouring tionsolution
on a water-ice mixture andmixture
on a water-ice diluting and cording to
it diluting it the
withmethod 7 laid down in the
distilled
9% potassium chloride (by volume), then with distilled water to a constant volume, appropriate European Standard [20]. The
water to a constant volume, the concentration of dye was measured spectrophotometrically.
124 FIBRES & TEXTILES in Eastern Europe January / December / A 2008, Vol. 16, No. 5 (70)

The same procedure was repeated with the sample which had not been extracted with the
 Table 1. Structure of synthesised dyes, their application properties for cotton and measured 120; this might be important when dye-
UPF values (1% dyeings owf). ing at lower colorant concentrations.
Fabric 2 UPF
Diamine
At present no data is available concern-
Dye Dyeing
Bridge Exhaustion, Fixation, efficiency, K/S3
Fabric 1 Fabric 2 ing how the protective properties of the
% % % dyed fabrics discussed above would
Y1 (R. Yellow ) o-PDA1 85.3 74.5 63.5 4.53 10.9 36.6 change after repeated laundering. It may
Y2 D 91.6 72.3 66.2 3.55 9.9 50.9 be expected that with the high level of
Y3 D2 91.1 74.5 67.8 3.81 14.7 69.6 wash-fastness specific to reactive dyes,
Y4 D1 93.7 76.0 71.2 4.90 12.3 96.6 the UV protection properties of dyed fab-
R1 (R. Red 120) p-PDA1 84.8 75.4 64.0 5.53 13.7 56.7 ric would persist for an extended period.
R2 D 89.7 76.5 68.6 5.10 11.9 70.9
The assumption is the good light-resist-
ance of UV-absorbers based on diamines
R3 D2 83.9 74.2 62.2 5.86 15.8 55.5
used in this research and determined in
R4 D1 86.0 78.0 67.1 5.80 11.5 70.7
the earlier work [16]. It would, however,
A1 D1 83.0 – – 81.6 2
12.8 41.8
require separate research, during which
nts of the protective A8
properties of
D2the dyed85.2
fabrics. – – 76.82 14.0 42.4 other factors such as the effect on UPF
1
o-PDA – o-phenylenediamine, p-PDA – p-phenylenediamine, measurements of fabric shrinkage, the in-
textiles used
2 were examined
whiteness, fora Gretag
measured on their protective by in vitro with illuminate
propertiesspectrophotometer
Macbeth SpectroEye fluence of detergents or optical brighten-
D65 and 10° additional normal observer, ers present in the washing medium would
s of their UPF
3
at value,
λmax of prepared dyes,
according to –the
yellow dyes 410
method laid nm, – red
down indyes
the 540 nm.
appropriate
also have to be considered.
ndard [20]. The UPF factor was calculated as follows:
UPF factor was calculated as follows: ecule usually results in an increase in the The protective properties of the new
measured UPF value. This phenomenon dyes were compared with results ob-
λ = 400
∑λ =290 E ( λ )ε ( λ ) ∆λ was especially noticeable in the case of tained using traditional methods, in
UPF = λ = 400 Fabric 2, which was less translucent to which samples of cotton fabrics were
∑λ =290 E (λ )Ti (λ )ε (λ )∆λ UV radiation. After dyeing with the yel- dyed with compositions of model dyes
where E(λ) is the solar spectral irradiance low dyes Y2-Y4, this fabric was charac- (Y1 and R1) and the colourless fibre-re-
[W/mirradiance
the solar spectral 2
nm], ε(λ) [W/m
the erythema
2
nm], ε(action erythematerised
λ) the spec- actionby UPF values
spectrum, Ti(λ) above 40, which active UV absorbers A1 and A8, shown
trum, Ti(λ) the spectral transmittance of according to Standard [20] ensure suffi- in Figure 4. As previously, 1% model
transmittancesample i at the
of sample i wavelength
at the wavelength λ, and Δλλ,isandthe ∆λcient UV-protection.
is the interval of theThe highest block- dye concentrations per weight of the fab-
interval of the wavelength in nm. A mean ing of ultraviolet radiation by the fabric ric were used, accompanied by 0.25%,
n nm. A meanvalue was was
value takentaken
fromfrom three three
measurements
measurements wasforobserved in the case of dyes Y3 and
UPF calculation. 0.5% and 1% wt concentrations of the
for UPF calculation. The results of these Y4. It is worth noting that despite the UV absorber applied. The UPF values of
measurements
f these measurements in Table
are given
are given 1. 1.
in Table lower colour yield of the resulting dye- dyed fabrics are graphically presented in
ing, dye Y3 gives a much higher UPF Figures 5 and 6.
It was already known [4] that the struc- value than the model dye Y1.
tural characteristics of a particular textile As expected, the simultaneous applica-
lready knowngarment
[4] that (thickness,
the structural characteristics
porosity etc) are theof a particular
Fabric 2,textile garment
coloured with all the examined tion of the dye and UV-absorber auxil-
main factors determining its UV-pro- red dyes, exhibited sufficient protective iary in the same dyeing bath increased
orosity etc) are the main
tecting factors determining
properties, can once again its UV-protecting
be properties properties,
(UPF > 40).canThis was probably the protective properties of the coloured
observed in the results presented. As ex- partially caused by the different chromo- textiles in comparison with the single use
be observed in the both
pected, results presented.
of the textiles used As expected,
exhibited both of the
phoric textiles
system used
of these dyes. However, the of the model dye. Nevertheless, for the
improved UV-protecting properties after use of new diamine bridges in the case of more UV-transparent Fabric 1, the UPF
proved UV-protecting
coloration,properties
compared after
withcoloration,
the blank compared
fab- dyes with
R2the
andblank fabric
R4 gave an increase of about values measured are still below the de-
ric samples. The introduction of special 20% in the UPF values, compared with sired level. While dyeing Fabric 2, it was
e introduction of special UV-absorbing residue to thethose dye molecule usually
of the model C.I. Reactive Red noted that the measured UPF values were
UV-absorbing residue to the dye mol-
ncrease in the measured UPF value. This phenomenon was especially noticeable
100 Dye Dye
100 Dye+0.25% absorber
Fabric 1 Dye+0.25% absorber
f Fabric 2, which was less translucent to UV radiation. After dyeing
Dye+0.5% with
absorber the Fabric 2 Dye+0.5% absorber
Dye+1% absorber
80 Dye+1% absorber 80

Y2-Y4, this fabric was characterised by UPF values above 40, which according
60 60
UPF

UPF

[20] ensure sufficient UV-protection. The highest blocking of ultraviolet

40 40
Blank fabric

the fabric was observed in the case of dyes Y3 and Y4. It is worth noting that
Blank fabric

20 20

wer colour yield of the resulting dyeing, dye Y3 gives a much higher UPF value
0 0
Y1+A8 Y1+A1 R1+A8 R1+A1 Y1+A8 Y1+A1 R1+A8 R1+A1
el dye Y1.
Figure 5. Protection properties of cotton (Fabric 1) coloured with Figure Figure 6. Protection
6. Protection propertiesproperties of cotton
of cotton (Fabric (Fabricwith
2) coloured 2) model
coloureddyes with
with the
Figure
model5. dyes
Protection
withproperties of cottonof
the addition (Fabric 1) coloured
colourless with model dyes(1%
UV-absorbers. with the model
dyes with the addition of colourless UV-absorbers. (1%
dyeings, UPF ofrating overUV-absorbers.
40 – adequate addition of colourless UV-absorbers. (1% dyeings, UPF rating:
dyeings, UPF rating: over 40 – adequate protection properties) over 40 – adequate
addition colourless (1%protection properties).
dyeings, UPF rating over 40 –
protection properties)
adequate protection properties).
FIBRES & TEXTILES in Eastern Europe January / December / A 2008, Vol. 16, No. 5 (70) 125

8
influenced by both the nature of the UV- of apparel textiles. Color. Technol., 118
absorber auxiliary used and the structure (2002) 52-58.
of the model dye. The competition be- 5. Riva A., Algaba I., Pepió M., Action of All Polish Scientific 6
tween dye and absorber during the sorp-
a finishing product in the improvement Conference:
of the ultraviolet protection provided by
tion process in the cellulose fibre might
be the cause of the different behaviour of
cotton fabrics. Modelisation of the effect.
Cellulose 13 (2006) 697-704.
‘Fashion and Ethics
the absorbers A1 and A8 when applied 6. Ciba, German Patent, Vervendung von tri- in the
with yellow and red model dyes. In the
case of the yellow dye Y1, the use of a
azinhaltigen verbindung als UV-absorber.
German patent DE 19720683 (1997). Textile-Clothing Tex
0.25-0.5% UV-absorber auxiliary per 7. Ciba, UV absorbers, their prepara- Industry’
tion and the use thereof. US patent
weight of the fabric was necessary to ob-
5,786,475 (1998). 17 March 2009, Łódź, Poland
tain a product characterised by adequate 8. Freeman H. S., Sokolowska J., Develop-
UV-protecting properties. ments in dyestuff chemistry. Rev. Progr. 5–7
Organisers:
Coloration, 29 (1999) 8-22.
 Faculty of Material Technologies
9. Iqbal A., Challenges in colour chemistry
Conclusions for the third millennium. 8th International
and Textile Design Organ
of the Technical University of Łódź,
Conference on Dyes and Pigments The
From the analysis of the results described  Polish Humanitary Action
COLORCHEM 2000. Spindleruv Mlyn of the
above, it may be concluded that introduc-
Czech Republic 2000.
ing appropriate residues to the molecule of 10. Freeman H. S., Posey J. C., Analogs of The Conference is sponsored
a reactive dye can increase its UV-protec- Disperse Red 167 containing a built-in by the European Union
tion properties. The coloration of cellulose photostabiliser moiety. Dyes & Pig- Confe
fabrics with the use of specially tailored ments, 20 (1992)147-169. Scientific Committee: Fields
dyes could eliminate the necessity of us- 11. Freeman H. S., Posey J. C., An ap- Chairperson:  Fibr
proach to the design of lightfast disperse  Prof. Zofia Wysokińska Ph. D., Dsc.,
ing additional UV-absorber auxiliaries, Technical University of Łódź (TUŁ),
- Te
dyes – analogs of Disperse Yellow 42.
and therefore decrease the number of Department of World Economy and Qua
Dyes & Pigments, 20 (1992)171-195.
chemicals used in the dyehouse. This fact 12. Rajagopal R., Seshadri S., Light stabi- Marketing of Textiles
 Sm
should be considered when designing new lised azo dyes containing a built-in ul- Members: &N
reactive dyes; although introducing UV- traviolet absorber residue. Dyes & Pig-  Prof. Iwona Frydrych, Ph.D., D.Sc.,
absorbing residues into dyes characterised ments, 9, (1988) 233-241. TUŁ Department of Clothing  Inno
by a different structure than that presented 13. Moura J. C. V. P., Oliveira-Campos A. Technology Dev
M. F., Griffiths J., The effect of additives  Prof. Janina Witkowska Ph.D., D.Sc.,
in Figure 1, would probably require more Mac
on the photostability of dyed polymers. University of Łódź, Department
pronounced efforts. In the case of current- of World Economy and European  Tex
Dyes & Pigments; 33, (1997)173-196.
ly manufactured dyes, the ‘colorant + UV- 14. Czajkowski W., Paluszkiewicz J., Stolar- Integration Col
absorber auxiliary’ method might still be ski R., Kaźmierska M., Reactive Dyes  Prof. Włodzimierz Cygan, TUŁ,
Institute of Textile Architecture  Fun
the most convenient way of improving the for Cellulose Fibres Including UV Ab-
 Prof. Maria Pawłowa Ph. D. D.Sc., Tex
UV-protection properties of dyed textiles. sorbers”; Fibres and Textiles in Eastern
Technical University of Radom,
Europe 13, (2), (2005) 76-80. Department of Footwear and  Nov
15. Wang S. Q., Kopf A. W., Marx J., Bogdan Clothing Material Science Adv
A., Polsky D., Bart R. S., Reduction of
ultraviolet transmission through cotton  App
Organising Committee:
T-shirt fabrics with low ultraviolet pro- Chairpersons or I
Acknowledgments tection by various laundering methods  Monika Malinowska-Olszowy Tex
and dyeing: clinical implications. J. Am. Ph. D. – TUŁ
This work was sponsored by the Polish Min- Acad. Dermatol., 44 (2001) 767-774.  Eco
 Anna Paluszek Msc. – Polish
istry of Education and Science; Department 16. Czajkowski W., Paluszkiewicz J., Stolarski and
Humanitary Action
of Scientific Research. Project No. 3 T09B R., Kaźmierska M., Grzesiak E., Synthe-
04826. The authors would like to thank Dr. The scope of the conference  Inno
sis of reactive UV absorbers derivatives
E. Grzesiak from the Institute of Dyes and of monochlorotriazine for improvement will include the following pre- Per
Organic Products, Zgierz (Poland) for the protecting properties of cellulose fabrics. sentations concerning the tex-  Tec
measurements of UPF factor values. Dyes & Pigments 71 (2006) 224-230. tile & clothin industry:
 Social responsibility of We
17. Czajkowski W., Paluszkiewicz J., Stolar-
ski R., Polish patent application P- business and corporations  App
 Globalisation
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126 FIBRES & TEXTILES in Eastern Europe January / December / A 2008, Vol. 16, No. 5 (70)
 Kaunas University of Technology
(KTU)
Kaunas, Lithuania
The roorts of the university go back to 1920 when the first centre of university-type higher courses was established.
In 1922 the Government of Lithuania accepted a resolution establishing Kaunas University, which was then given
the name of Vytautas the Magnus in 1930. In 1950 Kaunas University was reorganized into Kaunas Polytechnic
Institute (KPI) and Kaunas Medical Institute. In 1990 KPI changed its name to the present name of Kaunas
University of Technology (KTU). Now KTU is the largest technological University not only in Lithuania, but also
in all the Baltic States. Many Prime Ministers, Ministers, Members of the Lithuanian Parliament and even the
President of the Republic of Lithuania have graduated from KTU.

The University is the only one in Lithuania engaged in textile engineering. The Department of Textile Technology
dates back to 1929, when the decision to begin education in textile engineering at the University was accepted, and in
1932 the first lectures started. The Department of Textile Technologies, as an organisational unit, was established in
1940, due to the founding of a Laboratory of Fibre Technology in 1936. The creator and first Head of the Department
was Professor J. Indriunas. Up to now more than 2500 students have graduated in textile technology (including more
than 200 from Latvia and Estonia) and more than 80 postgraduate students have been awarded a Ph. D. degree.
The majority of textile engineers of the Lithuanian textile industry graduated from this department. Senior Professors
of the Department, such as A. Matukonis, V. Milašius, and A. Vitkauskas are well known not only in Lithuania, but
also in Poland and the whole of Europe.

Today the Department’s staff includes 7 professors, 4 associate professors, 7 lecturers and 12 doctoral students.
Up to now more than 2000 scientific articles have been published in Lithuanian and international journals as well as
in conference proceedings. The main fields of research activity carried out by the Department of Textile Technology
are as follows:
 the rheological properties of textiles,
 the flammability and heat transfer of textiles,
 the wettability of textiles,
 computerised structural design,
 the development of textile manufacturing technologies, and
 the manufacturing of nanofibres, among others.

The department is a member of the international Association of Universities for Textiles (AUTEX). The Professors
of the Department have given lectures at various European universities regarding the activities of AUTEX and
the European Masters Studies Programme in Textile Engineering (E-TEAM).

Kaunas University of Technology,

Studentų 56, LT-51424 Kaunas, Lithuania
http://www.textiles.ktu.lt/ E-mail: kat0504@ktu.lt

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FIBRES && TEXTILES
TEXTILES inin Eastern
Eastern Europe
Europe January / December2008,
July / September / A 2008, Vol.No.
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