452 SEN-IGAKKAISHI ( ) (102)

Transaction
(Received January 16, 1990)

THE CROSSLINKING STRUCTURES AND PHYSICAL PROPERTIES

OF THE COTTON FABRICS TREATED WITH TWO-STEP WET-CURE
OR POLY-SET PROCESS

By M. S. Yen and C. C. Chen

Department of Textile Engineering and Technology,

National Taiwan Institute of Technology, Taipei, R. 0. C.

ABSTRACT: The crosslinking structures and the physical properties of the fabrics treated with wet-cure
or poly-set process were studied. The lengths of crosslinks in the fabric treated with the wet-cure process
were longer than those with pad-dry-cure and poly-set processes. With the same crosslinking structure, the
fabric treated with the two-step wet-cure process showed better crease recovery under both dry and wet
conditions than the fabric treated with pad-dry-cure or two-step poly-set process. This effect was attri-
buted to the improved protection of hydrogen bonds and the enhanced swelling achieved by the first
method. The dry and wet crease recoveries and the degree of swelling of the wet-cured fabric were depend
ent on the moisture content of the fabric during the treatment.

and the TSR due to the penetration and condensation

1. INTRODUCTION
of crosslinking reagents into the microstructure of the
The effects of the finishing reagents, curing con- fiber, and the latter could improve the TSR due to the
ditions and predrying conditions on the physical prop- polymerization of crosslinking reagents. However,
erties and crosslinkingstructures of dimethylolethylene studies on the crosslinking structure and on its effect
urea (DMEU) -treated cotton fabrics for the pad- on the physical properties are still lacking.
dry-cure process have been widely studied.' -4) We In this study, we discuss the difference in the
found for the process that the shorter crosslinking structures of crosslinks between wet-cure and poly-
length resulted in a better dry crease recovery angle set processes and that between the one-step and two-
(DCRA) and a lower tensile strength retention (TSR) step treatments of both processes, and the effect of
at the same nitrogen content of the treated fabrics. the moisture content during wet-curing. The effects of
We also found, by changing curing and predrying the finishing process and the moisture content during
conditions3'4>,that the crease recovery angle was wet-curing on the relationship between the physical
largely affected by the crosslinking structures, the properties and the crosslinking structures are also re-
DCRA was affected by the hydrogen. bonding while ported.
the wet crease recovery angle (WCRA) was depend-
2. EXPERIMENTAL
ent on the swelling property of the treated fibers. It
was found difficult to improve both DCRA and 2.1 Material
WCRA together, and even more so to improve the The cotton fabric (unmercerized), 40s X 40s ends
TSR of the treated fabrics by the pad-dry-cure pro- (144) and picks (80), was desized, scoured, and
cess based on the results obtained for the effect of bleached.
crosslinking structures. 2.2 Finishing process
Wet-cure and poly-set processes for improving the 2.2.1 Pad-dry-cure
physical properties of the treated fabrics were re- Pieces of fabric were padded with 2 - 8% of DMEU
ported by many researchers.5-10~ According to the solutions containing Zn(N03)2 6H20 as catalyst (10
studies, the former process could improve the WCRA % of DMEU, wet pick-up was about 85 %), predried
 (103) Vol. 46, No. 10 (1990) 453

at 80 for 5 min, cured at 150 for 3 min, and then with DMEU solutions of various@ concentrations, con-

soaped and dried. taining AlC13.6H20 or 0.1 N H2S04 as catalyst (the

2.2.2 Wet-cure pH was adjusted to about 2.5 by changing the

(a) One-step wet-cure: Fabric samples were padded catalyst concentration, and wet pick-up was about 85

Table 1 Crosslinking Structures of DMEU-treated Fabrics bs Various Processes

The catalysts used were (*a), AICl3.6Hz0; (*b), H2S04; (*c), Zn(CH3C00)2-2H20; and (*d), Mg(CH3COO)2-4H2O.
 454 SEN-I GAKKAISHI( ) (104)

), predried at 80C to various moisture contents, and reformed as the second treatment proceeded.In a
and sealed in polyethylene bags at 25 for 24 h. The previous studyil>, we found that the crosslinks in
samples were neutralized with a Na2CO3 solution and DMEU-treated fabrics were decomposed and re-
then washed in cold running tap water for 30 min. formed as the curing conditions were changed.
(b) Two-step wet-cure: The one-step wet-cured For comparison between the crosslinking struc-
samples were further padded with a solution of Zn tures of the fabrics treated by wet-cure (two-step),
(N03)2.6H20 (10 % of DMEU used in the first step, poly-set (two-step) and pad-dry-cure processes, the
wet pick-up was 85 % ), predried at 80 for 5 min, crosslinking length (n) of the fabrics treated with
cured at 150 for 3 min, and then soaped and dried. each process is plotted against nitrogen content in
2.2.3 Poly-set Fig. 1 (a). The figure shows that the crosslinking
(a) One-step poly-set: Fabric samples were padded length of the fabric treated with the two-stepwet-cure
with DMEU solutions of various concentrations, con- process is longer than that by the two-step poly-set
taining Zn (CH3000)2.2H20 or Mg (CH3000)2.4H20 process, and n obtained with the pad-dry-cure pro-
as catalyst (25 % of DMEU, wet pick-up was about cess is the shortest for the same nitrogen content.The
85 % ), predried at 80 for 5min, cured at 150 for figure also shows that the crosslinking length is also
3 min, washed, and dried. affected by the catalyst used. This difference in the
(b) Two-step wet-cure: The one-step poly-set sam- crosslinking length may be attributed to the fact that
ples were further treated with the same method as de-

scribed in the two-step wet-cure process.

2.3 Test Method

Dry and wet crease recovery angles were measured

with a Monsanto tester. The tensile strength retention

was measured with an Instron tester, and the nitrogen

content was determined by the Kjeldahl method. The

amounts of combined CH2O in Fl (N-CH2OH), Fe

(N-CH2OCHz N), Fc (N-CH20-Cell) and Fm

(N-CHz N), the crosslinking length (n), the number

of crosslinks (r), the degree of crosslinking com-

pletion (a), and the strength loss caused only by the

crosslinks (SL') were determined by the method de-

scribed in the previous papers,2'3>

3. RESULTS AND DISCUSSION

3.1 The Crosslinking Structures of the Treated

Fabrics by Wet-cure or Poly-set Process

The crosslinking structures of the fabrics treated

with the wet-cure or poly-set process are listed in

Table 1 in comparison to those with the pad-dry-cure

process. Both for the wet-cure and poly-set processes,

Fig. 1. Plot of n against nitrogen content of fabrics
Fl (N-CHZOH) and Fe (N-CH2OCH2-N) are largely
treated (a) with various processes and (b) at different
decreased as the second step proceeds, while Fm
moisture contents in wet-cure process. Symbols: (...... )
(N-CH2-N) and Fc (N-CH2O-Cell) are obviously in-
one-step treatment; (-) two-step treatment; wet-cure
creased, the crosslinking length (n) is shortened, and
process catalyzed by (0, v) AlC13- 6H,20, ( C)
the number of crosslink (r) is increased, These re-
H2SO4; poly-set process catalyzed by () Zn

sults clearly show that the crosslinking structures (N03)2.2H20, () Mg (CH3C00)2-4H20; and (0) pad-

formed in the one-step treatment were decomposed dry-cure process.

 (165) Vol.46,
No.10(1990) 455
Table 2 Crosslinking Structures of Fabrics Treated with DMEU in Wet-cure Process at Different Moisture Content

The catalyst used was AICI3.6H2O

the condensation of crosslinking reagents is easier to creases obviously with the increase in moisture con-
occur in the wet-cure process than in poly-set and tent. The Fm, however, is almost constant. These re-
pad-dry-cure processes since the wet-curing is carried sults suggest that the decrease in n in the wet-cure
out at a higher moisture content, at a stronger acidity process was caused mostly by decomposition of N-
of catalyst, and for a longer period of treating time in CH2OCH2-N linkage as the second step proceeded.
the one-step treatment . Fig. 1 (b) shows the effect of moisture content in the
Table 2 shows the effect of moisture content in the wet-cure process on the crosslinking length. There is
wet-cure process on the crosslinking structures. It is no definite relation between the crosslinking length
found that the Fe is largely increased , and the Fm is and the moisture content, and the crosslinking lengths
obviously decreased with the increase in moisture for different moisture contents are in the order 10
content in the one-step wet-cure treatment. As the > 70 % > 20 %. The results may be due to the fact
second step proceeds , the Fe decreases and the Fc in- that the effect of the stronger acidity in the treatment
 456 SEN-I GAKKAISHI( ) (106)

at a lower moisture content on n is larger than the the relationship between the DCRA and the r 1f a
effect of the larger swelling property at a higher of the treated fabrics for various processes. Equation
moisture content by improving the condensation of 1 holds for all the processes with Kpl varying with
crosslinking reagents. Fig. I (b) also shows that the the process. The Ko1 for one-step or two-step wet-
longer the crosslinking lengths of one-step treated cure process is larger than that for one-step or two-
fabrics, the longer thecrosslinking lengths after the step poly-set process, respectively, and the Ko1 for
second step treatment. the two-step poly-set process is even smaller than
3.2 The Relationship between the Physical that for the pad-dry-cure process. The larger K01for
Properties and Crosslinking Structures wet-cure process may be caused by the higher degree
3.2.1 The dry crease recovery angle for the two-step of condensation of reagents due to the higher mois-
treatment ture content in the first step of the treatment result-
According to the previous papers3'4), the relation- ing in the protection of the hydrogen bonds. The
ship between the dry crease recovery angle (DCRA) smaller K01 for the poly-set process may be due to
and the crosslinking structure () of the fab- the fact that the condensation of reagents was not dis-
rics treated by the pad-dry-cure process can be writ- tributed uniformly to protect the hydrogen bonds be-
ten as; cause the condensation proceeded in a dry state. The
DCRA=Ko1r(1) fact that the hydrogen bonds affect the DCRAhas
In this equation, n is the crosslinking length, r is the been reported in our previous paper.3> Fig. 2 also
number of crosslinks and a is the degree of the cross- shows that the Ko1 for the two-step process is smaller
linking completion. The constants Koo and Ko1 are than that for the one-step process no matter what
affected by the hydrogen bond which is a function of type of wet-cure or poly-set process is adopted.The
the distribution of crosslinking reagents. Fig. 2 shows decrease in K01may be attributed to the fact that the
condensed reagents in the one-step treatment can be
decomposedand reformed to weaken the effect of pro-
tecting hydrogen bonds as the second step proceeds

Fig. 2. Relationship between DCRA and r f a of fab-

rics for various processes. Symbols: (------) one-step

treatment; (-) two-step treatment; wet-cure process

catalyzed by () A1C13.6H3O, () H2SO4; poly-

set process catalyzed by (.) Zn (CH3000)2'2H20, Fig. 3. RelationshipbetweenDCRAand r[a of fab-

()Mg (CH3000)2.41120, and (0) pad-dry-cure rics treated at different moisture contents in wet-cure
process. process (Symbolsare the same as shownin Fig. 1).
 (107) Vol.46, No.10 (1990)
(Table 1).
Fig. 3 shows the effect of moisture content in the
wet-cure process. Although the effect is not obvious
in the one-step treatment, the KDIfor the two-step in-
creases with the increase in moisture content. This
clearlyshows that a higher moisture content can cre-
ate the more effective protection of hydrogen bonds
becauseof the more uniform distribution of crosslink-
ing reagents.
3.2.2 The wet crease recovery angle for the
two-steptreatment
Fig. 4 shows the relationship between the WCRA
andthe rna of the fabrics treated with different pro-
cesses.The results show a relationship (equation 2)
equivalent to those reported in our previous
papers3,4);
WCRA=Kw1rna+Kwo (2)
whereKw1is affected by the swelling property of fi-
bers in the treated fabric.
The figure shows that (1) the Kwl for one-step
wet-cure or one-step poly-set process is obviously
higherthan that for two-step wet-cure or two-step
poly-setprocess, respectively; (2) the Kw1 for one-
step or two-step wet-cure process is higher than that
for one-step or two-step poly-set process, respective-
ly, while the Kw1for the two-step poly-set process is
similarto that for the pad-dry-cure process; and (3)
Fig.4. Relationship between WCRA and rna of.fabric
for various processes (Symbols are the same as shown in
Fig.2).
457
the lines are bent at rna = 100 - 200 for pad-dry-
cure, two-step wet-cure and two-step poly-set proces-
ses. The difference in the above results on WCRA at
the same rna is due to that in the swelling property
of fibers in the treated fabrics, which results from the
difference in the crosslinking structures and the dis-
tribution of reagents because the processes proceeded
at different moisture contents.
To examine the effect of the process on the swelling
property, the SEM photographs of the fiber cross-sec-
tions were taken (Fig. 5) after swelling treatment
according to Rollins et a1.12 The swelling of the fiber
after one-step treatments of poly-set and wet-cure (c
and e) was more remarkable than that after two-step
treatments (d and f), respectively; the swelling prop-
erty of fibers after resin finishing obviously de-
creased; and the fiber treated with wet-cure or poly-
set process showed greater swelling than that with
the pad-dry-cure process, and the one-step or two-
step wet-cure process effected greater swelling than
Fig. 5. Scanning electron micrographs of fiber cross-
sections of the treated fabrics: (a) untreated (4700X),
(b) pad-dry-cure (5100X), (c) one-step poly-set (5100
X), (d) two-step poly-set (4900X), (e) one-step wet-
cure (4700X), and (f) two-step wet-cure (4600X). The
nitrogen contents of the treated fabrics were about 600
pmol/g.
 458 SEN-I GAKKAISHI( ) (108)

Fig. 6. Scanning electron micrographs of the fiber

cross-sections(4600X) of the fabrics treated with two-
Fig. 7. Relationship between WCRA and rna of the
step poly-set process. The nitrogen contents of the tre-
fabrics treated at different moisture contents in wet-cure
ated fabrics were (a) 0; (b) 125; (c) 250; and (d) 350
process (Symbols are the same as shown in Fig. 1).
,amol/g,respectively.
affect the distribution of crosslinking reagents. The
the one-step or two-step poly-set process, respec- absence of the inflection in the case of the one-step
tively. Fig. 6 shows the cross-sections of the treated treatment may be due to the lower a (Table 1).
fibers with different Ma by the two-step poly-set The relationship between the WCRA and the ma
process. The swelling of the treated fibers decreases of the fabrics treated at different moisture contents in
obviously, especially in the case going from rna = 0 the wet-cure process is shown in Fig. 7. The Kwl in-
(untreated) to Ma=125. According to the above re- creases with the increase in the moisture content both
sults, it is clear that the Kw1 is largely affected by for one-step and two-step wet-cure treatments. This
the swelling property of fibers in the treated fabrics. result can also be attributed to the swelling property
From the results of the research on the crosslinking of the fibers.
structures described in section 3.1, it is found that
the one-step treatment results in a lower degree of
crosslinking completion (a) and a longer crosslinking
length (n), and the wet-cure treatment results in a
longer n and a more inner distribution than pad-dry-
cure and two-step poly-set treatments. The crosslink-
ing structure can certainly affect the swelling pro-
perty of fibers mentioned above, i. e., the one-step or
wet-cure treatmet will result in a better swelling
property. The inflections of the curves for pad-dry-
cure or two-step treatments shown in Fig. 4 may be
attributed to the change in the distribution of cross-
linking reagents. Baddi et at.13,14)pointed out that the
association of crosslinking reagents increased when Fig. 8. Relationship between SL' and ra of the fabrics
the concentration was higher than 4 %. This would for various processes (Symbols are the same as shownin
increase the length of crosslinking reagents, and Fig. 2).
 (109) Vol. 46, No. 10 (1990)
3.2.3 The strength retention for the two-step
treatment
Fig. 8 shows the relationship between the strength
loss caused by the crosslinks (SL') and the ra. The
SL'is closely related to the product of the number of
crosslinks and the degree of the crosslinking com-
pletion (ra) as shown in equation 3 which was re-
portedin our previous papers3'4);
SL'=Ks ra (3)
The strength loss caused by the crosslinks is near-
ly independentof the type of the process.
4. CONCLUSION
The crosslinking structures and the physical pro-
pertiesof the fabrics treated with DMEU by the two-
step treatment of wet-cure or poly-set process were
studiedand the followingresults were obtained.
(1) For both wet-cure and poly-set treatments, the
amountof combined CH20 in Fl and Fe were largely
decreasedas the second step proceeded, while those
in Fm and Fc obviously increased, the n decreased,
and Yincreased.The crosslinking length of the fabric
treated with the wet-cure process was longer than
that with pad-dry-cure and poly-set processes. The
crosslinkingstructures were clearly affected by the
moisturecontent during wet-cure treatment.
(2) The physical properties of treated fabrics were
affectedby the type of the process. With the same
crosslinkingstructure, the two-step wet-cure treat-
mentresulted in a better DCRAand WCRAthan pad-
dry-cureor two-step poly-set treatment. However, the
strengthloss caused by the crosslinks was nearly in-
dependentof the type of the process.
(3) The scanning electron micrographs of the
cross-sectionsof the fibers in the treated fabrics
, .
,
,
, . .
459
showed that the swelling property of fibers for the
wet-cure treatment was better than that for the pad-
dry-cure or poly-set treatment, and the WCRA of the
treated fabrics was obviously affected by the swelling
property of the fibers.
REFERENCES
1) M. S. Yen, Y. M. Chang, and C. C. Chen, Sen-i
Gakkaishi, 43, 300 (1987)
2) M.S. Yen, Sen-i Gakkaishi, 43, 305 (1987)
3) M. S. Yen and C. C. Chen, Sen-i Gakkaishi, 44,
421 (1989),
4) M. S. Yen and C. C. Chen, Sen-i Gakkaishi, 45,
473 (1989)
5) N.R. Bertoniere, L.F. Martin, F. A. Blouin,and S.
P. Rowland, Text. Res.J., 42, 734 (1972)
6) N.R. Bortoniere,L. A. Blouin, L.F. Martin, and S.
P. Rowland, Text. Res.J., 44, 140 (1974)
7) A. H. Lambert, R. A. Holser, and R. J. Happer, Jr.,
Text. Chemists Colorists,18, 39 (1986
8) W. A. Reeves, C. Hamalainen,H. H. St. Mard, and
A. S. Cooper,Jr., Text. Res.J., 37, 76 (1967)
9) H. Ohe, S. Matsuki, M. Terai, H. Kuroda, and S.
Matsukawa, Text. Res.J., 39, 1065 (1969)
10) S. P. Pandey and P. Nair, Text. Res. J., 51, 332
(1981)
11) M. S. Yen and H. Tonami, Sen-i Gakkaishi, 31,
420 (1975)
12) M. L. Rollins, J. H. Carra, E.tJ. Gonzales, and R. J.
Berni, Text. Res.J., 36, 185 (1966)
13) N. T. Baddi, S. B. Patel, and H. R. Chipalkatti,
Text. Res.J.. 41, 153 (1971)
14) G. L. Madan, S. B. Patal, N. T. Baddi, and P. C.
Mehta, Text. Res.J., 46, 329 (1976)