1009

Wash-and-Wear Finishing of Silk Fabrics

with a Water-Soluble Polyurethane
CHENG HU
College of Chemistry & Chemical Engineering, Dong Hua University,
Shanghai 200051, People’s Republic of China.

YEJUAN JIN
Department of Textiles, Merchandising, and Interiors, University of Georgia, Athens, Georgia 30605, U.S.A.

ABSTRACT
A water-soluble bifunctional polyurethane WPU200 is prepared and used for wash-and-
wear finishing of silk fabrics. The wet resiliency of the finished silks
greatly improves, and
dry resiliency drops a little. Anionic and nonionic softeners, which can improve the dry
crease recovery angle and handle of finished silk fabrics, can be used in a
single bath with
WPU200. Factors that have a great influence on the resiliency of the finished fabrics include
WPU200 concentration, curing temperature and time, and pH of the finishing bath. All these
factors have been optimized. Changes in the physical properties of the finished silk fabrics
are reported, such as breaking strength, elongation, moisture regain, whiteness, and
stiffness. Finished silk fabrics have good laundry durability after twenty washing cycles.

Silk is a top quality textile material because of its erties on them. We report on optimized finishing condi-
excellent wear comfort and elegant appearance. Un- tions, mechanical, and other important properties of the
fortunately. it has a fatal weakness: its very low wet finished silk.
resiliency means it is inconvenient to care for. and
there has been a decline in worldwide consumption .

[6-7. 16]. This poor wet resiliency is due to silk’s lack Experimental
of intermolecular chemical crosslinkages. When the
HDI ( 1,6-hexamethylene diisocyanate). obtained from
fibers absorb water and swell, the salt linkages be-
tween polymers, which give the fibers high dry crease
Shanghai No. I Chemicals Factory, was freshly distilled
just prior to use. PEG’00 (polyethylene glycol, molecular
recovery, are broken [ 18]. Thus, silk fabrics have no
wash-and-wear properties.
weight of 200), manufactured by Tianjin Tiantai Fine
Chemicals Corp., was heated to 100-110°C under re-
Effective chemical finishing methods that can im-
duced pressure (below 5 mmHg) for more than three
prove the resiliency of silk fibers include graft-copo- hours. Butanone was used as a solvent after immersion of
lymerization, reaction with epoxides, and dibasic an- 4-A molecular sieves for more than a week with occa-
hydrides [2-3, 6-17]. Amino formaldehyde resins sional shaking. The nonionic silicone
have also been used for crease-resistant finishing of softener.
EPIOIO,
was provided by Henkel (Shanghai) Co.. Ltd. Silk habu-
silk, but they have one major disadvantage: formalde- tae (plain woven, 36.5 g/m‘) fabrics were used through-
hyde release 18, 20]. The curing temperature required out this study.
to finish silk fabrics with polycarboxylic acids, mainly A prepolymer of wPu2oo was prepared from the reac-
citric acid and 1,2,3,4-butanetetra carboxylic acid, is tion of 1 mol PEG2oo and 2.1 mol HDI at 60°C in butanone
so high (up to 170°C) that it .may affect the intrinsic in a stirred reactor. The reactor was constantly purged
physicochemical and mechanical properties of the fi- with dry N, gas. The conversion of the reagents was
bers [ 18-19]. Finishing with polycarboxylic acids has followed by determining the amount of NCO groups
not been industrialized even on cotton fabrics till
according to ASTM D-2572. After the remaining NCO
recently. content reached the ideal percentage, a calculated
In this study, we explore the possibility of using a amount of isopropanol was added to the prepolymer with
reactive water-soluble polyurethane to improve the wet stirring at room temperature, and without delay an aque-
resiliency of silk fibers and confer wash-and-wear prop- ous solution containing sodium bisulfite (two times the
 1010

mole of the remaining NCO) was added. After half an

hour, the solution of wPU?c~ was acidified by dilute
hydrochloric acid to pH 5-6. The final concentration of
WPU200 was 25%. The expected structure of WPV200 is
shown below [ 1, 4-5]:

Silk fabric was padded twice through a finishing bath

containing WPU200 with a pick-up of 90%. The, padded
fabric was dried at 40°C for 5 minutes, then cured at
100’C for 3 minutes.
The crease recovery angle (CRA. warp plus fill) was
measured on a YG541 A crease recovery apparatus,
which is similar to that used in AATCC Test Method
66-1990. For the wet CRA (wcRA ) measurement, the test FICI’RE l. lnfluence of WPl’2tN) concentration on the C~R.B of fabric
cured at I(>D‘C for 3 minute, at pH =
ti.
fabric was immersed in distilled water containing 2 gll
nonionic wetting agent Peregal 0. and the excess liquid
was removed between sheets of blotting paper before
CURING TEMPERATLTRE AND TI,BIE
testing.
Breaking strength and elongation were determined by
ASTM D5305-95. Laundering durability was evaluated Curing temperature and curing time also are important
by AATCC Test Method 124- I 984. Fabric stiffness was factors affecting the CRA of finished silk fabrics (Figures
tested by ASTM D 1388-6.~. Fabric whiteness was mea- 2 and 3). The optimum curing temperature is 100°C. The
sured on a ZBD whiteness meter. According to ASTM lowest unblocking temperature of the bifunctional poly-
D4920-98, fabric moisture regain was determined by the urethane WPL!200 is 50°C. The higher the curing temper-
weight difference between the standard conditions (65 ature, the faster the reaction rate, so the more crosslink-
RH, 25°C) and bone-dry fabric samples. ages produced. When the curing temperature exceeds
IOOOC, the BN’CRA of the finished silk fabrics has a ten-
dency to decline, and DCRA further decreases. A high
.
Results and Discussion curing temperature also gives a harsh handle to the
finished silk fabrics.
INFLUENCE OF WPU200 CONCENTRATION

WPU200 concentration has a direct impact on the CRA of

the finished silk fabrics, as shown in Figure I. With
increasing WPU200 concentration up to 4~c, wCRA in-
creases to the maximum value, but DCRA drops about 20

degrees. Further increases in WPU200 concentration do not

improve wcRA anymore.
wPU?oo has twoblocked isocyanate groups.
-NHCOSO~Na, which unblock and release the re-
can
active isocyanate group -NCO under temperatures
higher than 50°C [4-5]. During the curing process.
wPU2oo can react with functional groups of amino acid
residues of silk fibroin and form crosslinkages between
protein molecular chains of silk fibers. Thus, the wet
resiliency of silk fibers improves. The slight decrease in
dry resiliency of the finished silk fibers is probably
caused by the destruction of the original salt linkages
between protein molecular chains during the finishing FtGLRh 2, Curing temperature Bersus CRA of fabric treated with .l~’~
process. wpL 200and cured at various temperatures for 3 minutes at pH 8. =
 1011

This bisulfite released during curing acidihes the reaction

system, which increases with subsequent aerial oxidation
of the bisulfite. This acidification retards the unblocking
of WPL’200 [5]. Thus, increasing the pH of the finishing
bath is beneficial to the reaction of WPL’200 and silk
fibroin.
In Figure 4, WCRA rises rapidly from pH 7 to 9.5, but
silk fibers degrade easily under a high pH. The suitable
pH range of the finishing bath is from 9 to 9.5.
SOFTENER EFFECT
WPU200 is an anionic compound, which can be used in ;.’
the same bath with anionic and nonionic softeners. Silk
fabric is padded through a finishing bath containing 4%
WPL’200 and 30 g/1 EP 10 10 softener (pH = 9 ), dried at 40°C
for 5 minutes, then cured at 100°C for 3 minutes. The
CRA of the finished silk fabric is shown in Table I.

FIGI’RE 3. Effect of curing time on the CRA of fabric treated Bkith 4%

wpL 2’x’ and cured at 100&dquo;C for different times at pH
=
8. TABLE 1. Softener effect on CRA ( ~ 3.5 degrees..

A curing time of 3 minutes is enough for a satisfactory

WCRA. Prolonging the curing time will have negative effects
on the handle and other properties of the finished silks.

1~INISHING BATH PH The softener EPioio has little effect on the BVCRA. but it
does improve the DCRA by about 10 degrees. The handle
The an important role in the reaction of
pH plays of the finished fabrics is also ameliorated by the softener.
wPU?oo and silk fibroin (Figure 4). The main reason is
that curing of WPL200 releases an inorganic salt NaHSO.,. HOME LAUNDERING
DL RABtUTY TO

Table II shows that the finished silk fabric has very

good laundering durability. After twenty cycles of stan-
dard home laundering, the wet resiliency of the finished
fabric only drops by 2.9~. This durability is due to
WPl’200’S two functional groups, which can form covalent

linkages between molecular chains of silk fibroins.

TABLE I1. CRA (~32 degrees) of the finished silk fabric

after cashing

CHANGES IN PHYSICAL PROPERTIES

Both breaking strength and elongation of the finished

silk fabric drop slightly (Table III ). Whiteness and mois-
ture regain (65% RH. 25°C) of the finished fabric are a
FIGL’RE 4. pH of finishing bath versus CRA of fabric treated with 4%
and cured at 100-’C for 3 minutes. Na~CO, was used to adjust
,A,PL2(x)
little lower than those of control samples. and stiffness is
the pH of the finishing bath. a bit higher.
1012

TABLE III. Physical properties of the silk fabric finished with 4% wpu2(x) and 30 gll EPIOIO softener (pH =
9). dried at 40&dquo;C for 5 minutes.
then cured at 100°C for 3 minutes.

Conclusions Fabrics with a Novel Multifunctional Epoxide, Part 2, J.

Soc. Dyers Colour, 116, 204-207 (2000).
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