Ozone-Gas Treatment of Cationic Dyeable Polyester

and Poly(butylene terephthalate) Fibers

Myung Sun Lee,1 Muncheul Lee,1 Tomiji Wakida,2 Masumi Saito,2 Takumi Yamashiro,3
Kenji Nishi,4 Goichi Inoue,5 Shinzo Ishida5
1
Department of Textile Engineering, Pusan National University, Pusan 609-735, South Korea
2
Department of Home Economics, Gifu Women’s University, Taromaru, Gifu 501-2592, Japan
3
Kyoto Municipal Industrial Research Institute, Kamikyo-ku, Kyoto 602-0898, Japan
4
Meisei Chemical Works, Sakyo-ku, Kyoto 615-8666, Japan
5
Iwatani International Corporation, Ltd., Moriyama, Shiga 524-0041, Japan

Received 9 August 2006; accepted 29 November 2006

DOI 10.1002/app.25978
Published online in Wiley InterScience (www.interscience.wiley.com).

ABSTRACT: Cationic dyeable polyester and poly(buty- not only on the fiber surface but also in the internal struc-
lene terephthalate) fabrics were treated with ozone gas ture of both fibers. Then, it seemed that the treatment
under atmospheric pressure and at a pressure of 0.1 MPa. brought about an effect on the dyeing properties. The
The effect of the ozone-gas treatment was investigated on apparent dyeing rate with the cationic dye increased
the basis of electron spectroscopy for chemical analysis, remarkably with the ozone-gas treatment, whereas that
Fourier transform infrared spectrum, X-ray diffraction, with the disperse dye increased slightly. Therefore, it was
moisture regain, water absorption, and dyeing properties. clear that the ozone-gas treatment caused a change not
The ozone-gas treatment caused an increase in the oxygen only in the fine structure but also in the dyeing behavior.
content of each fiber. From the wave separation of C1s, the These phenomena were the same as those of poly(ethylene
oxygen was incorporated in the form of

CO

and terephthalate) fibers. Ó 2007 Wiley Periodicals, Inc. J Appl


COO

on the fiber surface, and also, despite an increase Polym Sci 104: 2423–2429, 2007
in the water absorption, the fiber density as an index of
crystallinity increased a little with the treatment. As the Key words: dyes/pigments; ESCA/XPS; FTIR; modifica-
result, we concluded that the treatment caused a change tion; polyesters

INTRODUCTION vious articles, we reported the ammonia-gas treatment

of silk fiber9 and ozone gas treatments of wool,10 nylon
Polyester fiber has been used widely in the textile
6, and polyester fabrics.11 The treatment took in oxygen
industry, but it is not always possible to obtain bright
in the form of

CO

and

COO

on the fiber sur-
and vivid shades because of its high refractive index. It
face. As the result, the wettability, apparent dyeing
is difficult to dye deeply due to its high crystallinity
rate, and equilibrium dye uptake increased appa-
and high hydrophobicity. It is well known that cationic
rently. Therefore, it seems that ozone-gas treatment
dyeable polyester (CDP) fibers have overcome the
causes a change not only on the surface but also in
problem of dull color compared to regular polyester
the internal structure, such as in the crystallite
fibers. Furthermore, these fibers can be dyed under
and amorphous regions of the fiber.
atmospheric pressure (AP). They are also available for
Furthermore, in this study, CDP and PBT fabrics
energy conservation.1,2 On the other hand, poly(buty-
were treated with ozone gas under various condi-
lene terephthalate) (PBT) has wide engineering appli-
tions. The results were evaluated on the basis of the
cations because of the higher crystallization rate than
X-ray diffraction, electron spectroscopy for chemical
that of poly(ethylene terephthalate) (PET), and also,
analysis (ESCA), and dyeing properties.
PBT is more suitable for injection molding.3 PBT has a
relatively lower glass-transition temperature, lower
melting point, higher crystallization rate, and lower
maximum attainable crystallinity than PET fibers.4,5 EXPERIMENTAL
Ozone-gas treatment has had interest in gas-phase tex- Materials
tile finishing.6–8 Recently, we have studied ammonia-
gas and ozone-gas treatments of textile fabrics. In pre- CDP (182 g/m2), which contained 5-sulfoisophthalic
acid as a cationic dyeing site, and PBT (218 g/m2)
knitted fabrics were used as materials. Ozone-gas
Correspondence to: M. Lee (leemc@pusan.ac.kr).
treatment was carried out with the same equipment
Journal of Applied Polymer Science, Vol. 104, 2423–2429 (2007) that was used in a previous study12 for 10 min at
V
C 2007 Wiley Periodicals, Inc. AP and at 0.1 MPa.
2424 LEE ET AL.

Physical properties and then centrifuged for 20 min at 3000 rpm (W1). Sub-
sequently, the fabric was kept for 48 h at 65% RH (W2)
ESCA of the treated CDP and PBT fabrics was carried
and then dried for 3 h at 1058C (W0). Moisture regain
out with a VG Scientific ESCALAB 250 spectrometer
and water absorption were calculated with the follow-
(West Sussex, England). From the wide-scanning
ing equations:12
ESCA spectra, the relative intensities of the C1s and O1s
were determined. Furthermore, to elucidate the details Moisture regain ð%Þ ¼ ððW2
W0 Þ=W0 Þ  100
of the chemical composition, curve fitting of the C1s
spectra was performed, and relative components of Water absorption ð%Þ ¼ ððW1
W0 Þ=W0 Þ  100


CH,

CO

, and

COO

were determined. Fou-
rier transform infrared (FTIR) spectroscopic measure- where W1 is the weight of the centrifuged sample,
ment was performed with a Nicolet Impact 400D FTIR W2 is the weight of the water absorbed sample, and
spectrometer (Madison, WI) by the KBr pellet method. W0 is the absolute dry weight of the sample.
The X-ray refraction curve was obtained with a Rigaku
Denki III D-Max (Tokyo, Japan). Also, as a measure of
the internal compactness in relation to crystallinity,
Dyeing and color measurement
density was measured by means of the density gradi-
ent column method. Moisture regain and water The treated CDP knitted fabrics were dyed with a
absorption were measured according to the following cationic dye, C. I. Basic Red 46, and a disperse dye,
procedure: the fabric was immersed in water for 24 h C. I. Disperse Blue 56:

The dyebath was adjusted to pH 4.0 for the cationic dye fiber increases O1s intensity by the ozone-gas treat-
and pH 5.0 for the disperse dye with acetic acid and so- ment. Treatment is expected to cause oxidation of
dium acetate buffers (1 : 1). The initial dye concentration the fiber surface and lead to the chemical modifica-
in dyeing rate and equilibrium dye uptake was prepared tion of the fiber, especially the hydrophobic fiber.
to 4  10
4 mol/L for the two dyes. Dyeing was carried Table I shows the ESCA wide-scan relative intensity
out at 1008C at a liquor ratio of 500 : 1, and the equilib- of C1s and O1s of ozone-gas-treated CDP and PBT
rium dye uptake was obtained with dyeing for 24 h. The fabrics, respectively. The O1s intensity corresponds
fabrics were extracted with 100% dimethylformamide, to the relative functional oxygen component on the
and the dye uptake was determined photometrically. fiber surface. To elucidate the details of oxygen on
Color measurement of the dyed fabric was done
with a MacBeth Color Eye 3100, and K/S value in TABLE I
Kubelka-Munk equation (K: absorption coefficient; S: Relative Intensities of C1s and O1s in the Wide-Scanning
scattering coefficient) and lightness (L*) were obtained. ESCA Analysis of CDP and PBT Fabrics
Treated with Ozone Gas
Surface chemical
Lightfastness test
composition (%)
The lightfastness test was carried out in accordance Treatment C1s O1s
with ISO 105-B02. The samples dyed with cationic CDP
and disperse dyes for 60 min at 1008C were exposed Untreated 74.1 25.9
to a xenon arc lamp for 120 h. Ozone-gas-treated
AP, 208C/10 min 73.4 26.6
0.1 MPa, 208C/10 min 71.4 28.6
RESULTS AND DISCUSSION PBT
Untreated 78.3 21.7
ESCA Ozone-gas-treated
AP, 208C/10 min 74.8 25.2
Ozone gas is effective method for oxidizing organic 0.1 MPa, 208C/10 min 74.9 25.1
materials. As reported in a previous article,11 PET

Journal of Applied Polymer Science DOI 10.1002/app

OZONE TREATMENT OF POLYESTER AND PBT 2425

TABLE II
Wave Separation of the C1s Spectra of CDP and PBT
Fabrics Treated with Ozone Gas
Relative peak area (%)


CH

CO



COO


Treatment (285.0 eV) (286.5 eV) (289.0 eV)
CDP
Untreated 67.4 22.9 9.7
Ozone-gas-treated
AP, 208C/10 min 55.9 31.4 12.7
0.1 MPa, 208C/10 min 47.2 40.2 12.6
PBT
Untreated 72.9 15.2 11.9
Ozone-gas-treated
AP, 208C/10 min 66.4 20.3 13.3
0.1 MPa, 208C/10 min 62.3 25.6 12.1

Figure 2 FTIR spectra of untreated and ozone-gas-treated

the fiber surface, curve fitting of the C1s spectra for PBT fiber.
the fabrics was done, and

CH,

CO

and


COO

peaks corresponding to 285.0, 286.5, and
289.0 eV are summarized in Table II. The

CO


and

COO

contents were increased by the treat-
ment. From the results, it is clear that polymer sur-
face of the CDP and PBT fibers were oxidized by the
ozone-gas treatment. So, from the C1s wave separa-
tion, it was obvious that an increase in the O1s inten-
sity contributed to an increase in the

CO

and


COO

functional groups. As a result, it seems that
a change in the fine structure influenced the dyeing,
adhesion, and mechanical properties.

Figure 1 FTIR spectra of untreated and ozone-gas-treated Figure 3 X-ray diffraction profiles of ozone-gas-treated
CDP fiber. CDP and PBT fibers.

Journal of Applied Polymer Science DOI 10.1002/app

2426 LEE ET AL.

FTIR spectra These peaks turned sharply with ozone-gas treat-

ment. The C

C stretching in the benzene ring
Figure 1 shows the FTIR spectra of CDP fabrics
appeared at 1025 cm
1 (p6). Particularly, p2 and p6
treated with ozone gas. Generally, carboxylic acid
denoted a-form crystals,14,15 and the increase in the
salts have a band in the region 1440–1335 cm
1 due
intensity of these peaks meant that the a-form rate
to symmetric stretching vibration of

COO
, which
was increased by the ozone-gas treatment.
is of medium intensity and broad, and generally has
two or three peaks;13 the c3 and c4 peaks correspond
to these peaks. So, it seems that ozone-gas treatment
X-ray diffraction and density
introduced oxygen in the form of

COO
onto the
CDP fiber surface. Figures 3 and 4 show wide-angle X-ray diffraction
As shown in Figure 2, for PBT fiber, p1 included equatorial scans for ozone-gas-treated CDP and PBT
the C¼ ¼O stretching vibrations in carboxylic acid at fibers, respectively. CDP fiber had crystalline reflec-
1720 cm
1 and became sharp with the ozone-gas tions at 2y ¼ 17.8, 23.1, and 26.48, which were equiv-
treatment. p2 and p3 were assigned to a C

H bend- alent to (010), (110), and (100), respectively. The crys-
ing vibration and wagging at 1465 and 1403 cm
1, tallite form was not changed by the ozone-gas treat-
respectively. Two peaks, p4 and p5, appeared due to ment. On the other hand, PBT fiber had crystalline
symmetric stretching vibrations of ester

COO

. reflections at 2y ¼ 9.2, 15.8, 17.2, 20.5, and 23.58,

Figure 4 Dyeing rates of disperse and cationic dyes for ozone-gas-treated CDP and PBT fabrics.

Journal of Applied Polymer Science DOI 10.1002/app

OZONE TREATMENT OF POLYESTER AND PBT 2427

TABLE III TABLE V

Density of CDP and PBT Fibers Treated with Ozone Gas Effect of Ozone-Gas Pretreatment on the Color Depth
of CDP and PBT Fabrics Dyed with Basic Blue 3
Density (g/cm3)
Treatment L* K/S
Treatment CDP PBT
CDP
Untreated 1.319 1.322
Untreated 75.61 1.13
Ozone-gas-treated
Ozone-gas-treated 65.20 3.91
AP, 208C/10 min 1.320 1.325
PBT
0.1 MPa, 208C/10 min 1.323 1.325
Untreated 82.79 0.12
Ozone-gas-treated 69.54 2.23

which were equivalent to (001), (010), (111), (100), Dyeing was carried out at 508C for 5 min at a liquid
and (111) of the a-form crystallite. It is well known ratio of 100 : 1. After dyeing, the fabric was soaped with
that there are a- and b-form crystallites in PBT anionic detergent.
fibers.16 However, it is difficult to calculate the crys-
tallinity by means of the density method because the are shown in Figure 4. The apparent dyeing rate of
crystallite densities of the a and b types are not the fabric with cationic dye was accelerated consid-
known. Table III shows the densities of the CDP and erably by the ozone-gas treatment, despite an in-
PBT fibers treated with ozone gas. As a measure of crease in the fiber density.11 On the other hand, the
the compactness of the fiber, density increased with dyeing rate with disperse dye was only slightly
ozone-gas treatment. These results correspond well changed. In PBT fabric, the apparent dyeing rates of
to the intensity increases of p2 and p6 in the FTIR both the cationic and disperse dyes increased consid-
spectra with ozone-gas treatment. erably with the treatment. From these results, it is
clear that oxygen was taken as a result of the
Moisture regain and water absorption treatment and was in the form of

COO

in the
fiber, and the group changed to

COO
in the dye-
Table IV shows the moisture regain and water ab-
bath, which could be bound with the cationic ion of
sorption of the CDP and PBT fabrics treated with
the cationic dye.
the ozone gas. The moisture regain of CDP increased
The apparent dyeing rate of CDP and PBT in-
only a little with the treatment. The water absorption
creased apparently with the ozone-gas treatment in-
of CDP fabric showed almost no change with the
dependently in the cationic and disperse dyes. CDP
treatment, whereas for PBT, moisture regain and
fiber has a sulfonic acid group itself as a dyeing site
water absorption clearly increased with the treat-
for cationic dye. The ozone-gas treatment of PBT
ment. This result corresponded well to oxygen quan-
fiber increased the dye uptake; nevertheless, PBT
tities measured by ESCA. Therefore, it seemed that
fiber has no cationic dyeing site itself. Therefore, it
changes in the amorphous structure caused by the
was clear that carboxlylate group (

COO
) contrib-
treatment played a great role not only in the water
uted to the dye uptake of PBT. Table V shows the
absorption but also in the dyeing properties.
color measurement L* and K/S of CDP and PBT
dyed with Basic Blue 3 at 508C for 5 min. The
Dyeing properties untreated CDP fabric was dyed a little, whereas
The apparent dyeing rates of the cationic and dis-
perse dyes in the ozone-gas-treated CDP and fabrics TABLE VI
Equilibrium Dye Uptake of Cationic and Disperse Dyes
TABLE IV for Ozone-Gas-Treated CDP and PBT Fabrics
Effect of Ozone-Gas Treatment on the Moisture Regain Equilibrium dye uptake
and Water Absorption of CDP and PBT Fabrics (mol/g  105)
Moisture Water Basic Disperse
Treatment regain (%) absorption (%) Treatment Red 46 Blue 56
CDP CDP
Untreated 0.89 1.65 Untreated 16.91 2.95
Ozone-gas-treated Ozone-gas-treated
AP, 208C/10 min 0.94 1.64 AP, 208C/10 min 16.85 2.97
0.1 MPa, 208C/10 min 0.90 1.65 0.1 MPa, 208C/10 min 16.76 2.95
PBT PBT
Untreated 0.20 0.63 Untreated 0.89 2.27
Ozone-gas-treated Ozone-gas-treated
AP, 208C/10 min 0.42 2.62 AP, 208C/10 min 1.97 3.21
0.1 MPa, 208C/10 min 0.38 2.47 0.1 MPa, 208C/10 min 1.80 3.16

Journal of Applied Polymer Science DOI 10.1002/app

2428 LEE ET AL.

Figure 5 Relationship between dye uptake and dyeing temperature of Basic Red 46 for ozone-gas-treated CDP and PBT
fabrics.

untreated PBT was dyed almost negligibly. Never- temperature is shown in Figure 5. Dyeing was done
theless, the color depth of the ozone-gas-treated CDP for 10 min at each temperature. The dyeing tran-
and PBT fabrics increased not only for cationic but sition temperature decreased with the ozone-gas
also for disperse dyeings. Therefore, it was clear that treatment. Therefore, it was clear that ozone-gas
the dyeing acceleration of CDP and PBT by the treatment of the CDP and PBT fabrics induced the
ozone-gas treatment was caused by the incorporation relaxation of the fiber structure, and the effect con-
of the

COO

group. tributed to an increase in the dyeing rate.
The equilibrium dye uptake of the treated fabrics The effect of ozone-gas treatment on the light-
is shown in Table VI. It is well known that equilib- fastness of the samples dyed with Basic Red 46
rium dye uptake reflects the amorphous internal and Disperse Blue 56 is shown in Table VII. It
volume in relation to dyeing with cationic and is well known that lightfastness of cationic dye is in-
disperse dyes. Although the ozone-gas treatment did ferior to that of disperse dye. It seemed that the
not change the equilibrium dye uptake for both dyes lightfastness was not influenced by the ozone-gas
in the CDP fabric, in the PBT fabric, it increased treatment.
apparently for cationic and disperse dyes.
As an illustration of the dyeing transition behav-
CONCLUSIONS
iors of the CDP and PBT fabrics, the relationship
between the dye uptake of Basic Red 46 and dyeing CDP and PBT knitted fabric were treated with ozone
gas under AP and 0.1 MPa, and the effect was inves-
tigated by ESCA analysis, X-ray refraction, FTIR
TABLE VII
measurement, and dyeing properties with ozone-gas
Lightfastness of Cationic and Disperse Dyes
for Ozone-Gas-Treated CDP and PBT Fabrics treatment. The ozone-gas treatment induced an
increase in O1s intensity. Oxygen was incorporated
Change of shade
(gray scale)
in the form of

OH,

COOH, which led to an in-
crease in moisture regain and water absorption. The
Basic Disperse
treatment caused an acceleration in the dyeing rate
Treatment Red 46 Blue 56
for the cationic and disperse dyes, especially for
CDP the cationic dye. Despite an increase in the fiber
Untreated 2 4
Ozone-gas-treated density with the treatment, the equilibrium dye
AP, 208C/10 min 4 4 uptake with cationic and disperse dyes increased for
0.1 MPa, 208C/10 min 3 4 PBT, but it did not increase for CDP fibers.
PBT
Untreated — 4
Ozone-gas-treated References
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Journal of Applied Polymer Science DOI 10.1002/app

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Journal of Applied Polymer Science DOI 10.1002/app