404

with Low Degrees of Substitution, Textile Res. J. 38, 10. Rollins, M. L., deGruy, I. V., Cannizzaro, A. M., and Carra,
842-854 (1968). J. H., Morphological Features of Chemically Modified
3. Bass,S. L., Barry, A. J., and Young, A. E., "Cellulose and Cotton Fibers, Norelco Reptr. 13, 119-125, 132 (1966).
Cellulose Derivatives," Ed. E. Ott, New York, Interscience, 11. Stanonis, D. J. and King, W. D., Preparation of Partially
1943, p. 800. Benzhydrylated Cotton Cellulose, Textile Res. J. 30,
4. Dlugosz, J., Fine Structure of Cotton Fiber as Revealed by 802-803 (1960).
Swelling During Methacrylate Embedding, J. A ppl. Polymer 12. Stanonis, D. J., King, W. D., and Harbrink, P., Certain Fine
6,
Sci.
427-436 (1965). Structural and Thermal Properties of Benzhydrylated
5. Heyn, A. N. J., "Fiber Microscopy," New York, Interscience, Cotton Cellulose, J. Appl. Polymer Sci. 11,
817-828 (1967).
1954, pp. 309-317. 13. Stanonis, D. J., Cellulose Ethers: Miscellaneous Cellulose
6. Klein, E., Stanonis, D. J., Harbrink, P., and Berni, R. J., Ethers, in "Encycl. Polymer Sci. Technol." Vol. 3, New
ThePreparation and Properties of Partially Benzylated York, Interscience, 1965, pp. 541-549.
Cotton, Textile Res. J. 28, 659-668 (1958). 14. Tripp, V. W. and Giuffria, R., Concentric Cellulose Layers in
7. McKelvey, J. B., Benerito, R. R., and Berni, R. J., Esterifica- Cotton Fiber Cellulose Wall, Textile Res. J. 24, 757-758
tion of Cotton with Certain Monofunctional Acid Chlorides (1954).
and Effect on Crease, Recovery, Textile Res. J. 35, 365-376 15. Tripp,
V. W., Giuffria, R., and deGruy, I. V., Microscopical
(1965). Observations of Partially Acetylated Cottons and Related
8. Preston, J. M., "Modern Textile Microscopy," Manchester, Fibers, Textile Res. J. 27, 14-24 (1957).
Emmott & Co. Ltd., 1933, p. 261. 16. Wade, R. H. and Welch, C. M., Iodide Ion Catalysis in the
9. Rollins, M. L., Moore, A. T., Goynes, W. R., and Carra, J. H., Benzylation of Cotton Cellulose, Textile Res. J. 37, 586-591
Electron Microscopy of Chemically Modified Cotton, Am (1967).
Dyestuff Reptr. 54, 512-524 (1965). .llaunscriJ rruitrd .1vJrrnbsr 8, IQ72.

Color Characteristics of Traditional Vegetable Dyeing

KENNETH M. KASHIWAGI
Department of Chemistry, School of Home Economics, Kyoritsu Womens University, Hitotsubashi, Chiyoda-ku, Tokyo, Japan

ABSTRACT
Kimonos and other decorational cloths dyed with vegetable extracts are still favored today in this country. Making
useof modern chemical knowledge, the author has attempted to show a few characteristic features of the traditional
vegetable dyeing.
Many plants contain more than one pigment, each exhibiting different color according to its chemical structure. Nat-
urally, occurring tannins have a very important role both in the dyeing and in the dyed color. Tannins have shown the
greying effect on the dyed color. Thus, the visible color is that of a complex nature. The reasonable color quality,
based on the measurements of tristimulus values, has shown that the tannins always decrease the chroma of dyed color,
while which do not contain tannin, like flower usually exhibit clear color of high chroma.

KEYWORDS
Vegetable extracts; tannins. Vegetable dyes; chemical structure; dyed color; complex nature. Tristimulus value
measurements; chroma.

Introduction clothes worn only occasionally, the fade of relatively

In view of its unique location in Asia and the E~eoples
enthusiasm for simulating foreign culture, japan was
using many natural dyeing materials, . including those
of foreign origin, as earlier than 1,(Xl() years ago [1~.
Our recent publication has revetied the beauties of
many typical Japanese colors, using vegetable dyes
only [13]. Those colors find their best fit for kimono
design because the inherent seasonat climatic conditions
are used with colors of vegetable origin; for formal
weak color does not become a serious problem. More-
over, distinct clear colors of high chroma have not been
favored among Japanese until recently, while moderate
colors representable by vegetable dyes have been more
favored. These are probably the main reasons why
kimonos and other decorational cloths dyed with
vegetable plants are still favored today.
Many studies of vegetable dyeing, mainly from an
artistic point of view, have been published, but few
cover from scientific point of view.

Apart from the dyeing technique, modern chemical
knowledge of botanic pigments and scientific color
analysis are etTectively applicable for vegetable dyeing.
The author has attempted to show few characteristic
features of vegetable dyeing in modern dye chemistry.
Emphasis has been placed upon the role of tannins
regarding its unique mordanting action and more
specifically its color characteristics.
Materials and Methods
Silk Cloth
Refined, white silk cloths with a 0.30-mm thickness
are the same Eas with] those used in previous reports
E6-8]. It shows 86.2% of average retlectance value
against green light with a Hitachi photoelectric reflect-
meter ERF-2..
Dyeing Plants
Most vegetable plants contain tannins as major
ingredients are purchased through a dye specialist
trading with overseas. The list of those tannin
producing from plants will be published later. But
Chinese gallotannins are extracted with hot water
from the lumps grown on the Rhus semiallata plant.
Myrica rubra is considered as one typical yellow dye
containing a flavonol type dye, myricetin, as well as
about 15% of condensed tannins M. Both plants
are grown in Shikkoku, Japan.
Exlraction
The [detailed] extractive processes are given else-
where ~12~. rhe conditions for typical extraction are
briefly described as follows : About 50 g of the barks of
Myrica rubra are placed in a 5(X)-ml flask into which
are added 200 ml water. The tlask is then heated with
stirring for30 min. This is sometimes called a Dye
Bath No. 1. After the first aqueous extract has been
obtained, the same procedure is repeated.
Dyeing Conditions
Usually, two or three aqueous extracts are added to
make up a dye bath. In most cases, a piece of cloth
is dyed at higher temperature for a certain time, then
it is immersed in mordant solution prepared with
chemical grade reagents. After mordanting, the cloth
is dyed again for a shorter time.
Although the dyeing conditions vary case by case,
the time for dyeing is usually 1 hr at 80C.
A nalysis and Spot Tests
The tannin content of various plants can be deter-
mined by the hide powder method J IS-K6S04(1964).
405
Since organic tannins are chemicallv classified into two
basic types [3J, namety, the hydrotysabte and the
condensed tannins, various spot tests [9] are performed
to determine the type of tannin.
In order to determine the structure of various
pigments and tannins in plants, paper chromatographic
techniques have been extensively used. For instanoe,
pigment compositions of three kinds of Rubiaceae and
of dyed silk fiber of 1300 years old have been successfully
determined, mainly from the paper chromatographic
analysis and color fade tests [6, 7].
For purified samples, ir spectrographic analyses are
applied.
Color Measurement and Quality of Dyed Color
The color of dyed cloth is measured by the multi-
purpose Hitachi Spectrophotometer EPR-2. From the
measured tristimulus values, the color of dyed cloth
can be expressed after the method J IS-Z8i21 (1964),
which is the combination of CIE color formula and
Munsel color system. Although the above instrument
can show the most accurate tristimulus values, a
simpler apparatus is used to obtain the conventional
values only for fresh flower and leaves (see Table III).
Results and Discussion
The Role of Tannins on Dyeing
Vegetable tannins, important constituents next to
dye, may be defined as polyphenolic compounds having
a molecular weight of 300 to 5000 [3~. Tannins at
the same time must be capable of converting hyde to
leather by reacting with protein at the peptide position
[3~. Tannins thus should react with silk protein.
The strong adsorption of tannin on cotton and silk
fibers is also experimentally demonstrated [11 J.
Some of the typical tannin from plants are listed in
Table I. These are still used as dye in this country.
TA13LE I. Examples of tannin from plants.
The color of dyed cloth may be expressed as a
combination of three attributes of color (Fig. 1), i.e., hue-
 406

value,~chroma (Fig. 2) which, in turn, are calculated x is wavelength. The color of cloths dyed with a
from measured tristimulus values. certain representative tannin may be illustrated in
Table II.

.
TABLE II. Colors of cloths dyed with Gohaishi tannin.

Somme mordant met als, except iron, can be used for

tannins (see Fig. 3), but iron gives a most distinctive
color reaction. It appears very interesting that the
presence of tannin atways gives the lowest chroma
shown in rable I I.
1~ ic. 1. Three attrihutcs of color. Theoretically,,
the position of hue is not very impor-
I tant if the value of chroma is very close to zero, since
the distance between two neighboring hues at near the
central axis is very small (see Fig. 1).
The presence of tannin may function to reduce the
chroma in vegetablc dyeing. Ihis darkening effect
of tannin may perhaps be demonstrated in a very
simpte way when colors of fresh tiowers and lcaves arc
shown in Table 111. All flowers exhibit cletr colors of

TABLE III. Colors of fresh flowers and leaves. ,

Tristimulus values may be expressed &dquo;as:

high chroma, since tannins arc not in there, while

leaves give a little darker color due to some tannin.
The cause of tannin biosynthesis might begin at the
leaves and, in fact, tannins arc found in leavesE2, 10].
where is the energy distribution of light source; X, fr, The author has not attempted to measure the color of
I, are tristimulus values at wave length x for the barks because of the very obvious reason. Barks
.
RCB system ; p is light reHectance in %; k is constant; usttally appears greying brown color.
 407

The effect of tannin is directly illustratcd in Iable IV, mental resemblanre except a few points. Synthetic
where comparison is made between cloths dyed onlv dyes are usually made water soluble by introducing

hydrophitic group into molecule, while vegetable dyes

arc often insoluble. In most cases, however, those
,rAliLE IV. Color companson between cloths dyed with Myricetin
and those with Myrica r~i6ru extract containing tannin. naturally occurrent dyes exist as aglycon, thus rendering
them soluble.
Among vegetable constituents, the dyes involved
are often more than one. For instance, one of the
oldest dyes, madder root (Rubia linclorum Linn.)
contains six derivatives of anthraquinone of which
alizarin is most well known E4]. Each dye exhibits
ditTcrent color according to its chemical structure.
rhus, the visible color is of a complex nature.
with a vegetable dye :Vlvricetin, which is extracted If the vegetable should contain onlv one pigment as in
from Myrica rubra barks and the others dyed with the case of Myrica rubra barks, tannins participate in
aqueous extracts of the same barks. The latter shows dyeing.
15% tannin based on dry material. ()nce again, the If either one of the three principal colors (1ellow,
presence of tannin is shown to reduce chroma. ld, and 131ue) is called as primary color, the secondary
The color characteristics of the silk cloths dyed with color may be detined as a combination of two primary
four other tannin from plants are schematicallv shown colors as shown in Figure 4.
in Figure 3. Ihe above mentioned rule that tannin
always decreases chroma is valid here. Relativelv
high chroma by aluminum mordanting is most likelv
due to the reaction of ilavonoid pi~;ment with aluminum
causing spectra shift [12].

lnc. 4. Three 1>rincipal colors and the secondary color.

Then,
1 + R ()range, R + B Viotet, 1 + B
= =

= Green. All other color, may be defined as the

third-order color. Then. 2R + I + B = R + (R + V
+B), where R + Y + B = black or white R + Y
+B actually shows intermediate color between
=

black and white, that is, gray.

Since the presence of tannin has proved to give this
graving effect, most colors of vegetable dyes are said
to be the third-order color. This is in a sense contra-
dictory of the color of synthetic dyes, because good
synthetic colors should give distinct colors of high
chroma. The average value for 100 representative
vegetables was found to be (_ 4.2. Onty those cloths
=

dyed with vegetable, without tannin and with insect

extracts, showed relatively high chroma.

Literature Cited
1. "Engishiki," One of the Oldest Governmental Documents in
Ivic. 3. Color characteristics of tannin-dyed cloths with
various mordant metals. Japan, Completed at the year of 927.
2. Freudenberg, K., "Chemistry of Flavonoid Compounds,"
Ed. Geissman, T. A., New York, MacMillan, 1962, pp.
I

of Vegetable Dyeing
Color Characteristie~s 211-213.
3. Haslam, E., "Chemistry of Vegetable Tannins," London,
Many contemporary synthetic dyes have been Academic Press, 1969, p. 10.
derived from naturally occurring pigments. The exam- 4. Hattori, S., "Vegetable Pigments," Tokyo, Iwanami Shoten,
ination of their chemical structures illustrates funda- 1942, pp. 422-425.
408

5. Jurd, L., Ibid in ref. [2]. pp. 107-130. Tokyo 26,

Of Tannin in Tea Leaves, J. Agr. Chem. )
( 373-377
6. Kashiwagi, K. M., Dyeing with the Extracts of Rubiaceae (1954).
Roots, J. Home Economics 22, 253-257 (1971). 11. Technical Report from the Central Handicrafts & Develop-
7. Kashiwagi, K. M. and Kondo, N., The Red Dyestuff in ment Center, Bangalore, Mysore State, India, Shown to the
Ancient Times, J. Home Economics 22, 258-262 (1971). author on his recent trip.
8. Kashiwagi, K. M. and Kondo, N., Dyeing with the Extracts 12. Yamazaki, S., "How to Dye with Vegetable Extracts,"
of Myrica rubra, J. Home Economics 23, 380-384 (1972). Tokyo, Art Pub. Co., 1969, pp. 26-50.
9. Miyamichi, E., "Modern Analytical Methods of Vegetable 13. Yamazaki, S., "Vegetable Dyeing-Colors of Japan," Tokyo,
Components," Tokyo, Hirokawa Shoten, 1965, p. 302. Art Pub. Co. 1972.
10. Oshima, Y. and Nakamura, T., Nepherometric Estimation .BIatluscr;p! rrcrivrd .1rpfrmbrr 11, 197...

Caustic Sorption in Cotton Fibers as Affected by Fabric Construction,

Pretreatment, and Tension Conditions During Crosslinking
EDITH HONOLD
Southern Regional Research Laboratory, New Orleans, Louisiana 70179, U. S. A.

ABSTRACT
The alkali centrifuge value (ACV) quantitatively measures caustic sorption in fibers and is related to the fibers swelling
capacity. The ACV decreases when fiber swelling is restrained by crosslinks. In fabrics treated with dimethylolethyl-
eneurea (DMEU), the magnitude of decrease in ACV depended upon fabric
construction and pretreatment. The basket-
weave fabrics had lower ACVs, i.e., more restraint to swelling, than the plain-weave fabrics; the mercerized fabrics had
lower ACVs than the scoured fabrics. Other data are presented to support the hypotheses deduced from the ACV
relationships.
. KEYWORDS
Fabric construction; basket-weave; plain-weave. Pretreatment; scouring; mercerization. Liquid sorption; swelling;
alkali. Crosslinked cotton; DMEU; MgCl
·6 H
2 O;
2 catalyst.

Introduction
Numerous reports in the literature have discussed
various factors in the preparation of chemicallv modi-
fied cottons and their effects on the degree of reaction
and the distribution of reagent residues throughout
the fibers. The authors considered such variables as
time of reaction, concentration of reagent solution,
catalyst, temperature and time of curing. Fre-
quently, the same fabric was used throughout a series
of tests.
The degree of compactness of a fabric may alter the
course of a chemical reaction since a looselv constructed
fabric should be more easily penetrated by a reagent
solution than a more compact fabric. Also, a pre-
treatment may change the fabric structure which, in
turn, could influence the chemical reaction.
The alkali centrifuge value (A(.V) is related to the
swelling capacity of cotton fibers and the A(V decreases
when fiber swelling is restrained by crosslinks. Our
1One of the facilities of the Agricultural Research Service,
U. S. Department of Agriculture.
earlier studies [5, 6] had shown that the alkali centri-
fuge test effectively distinguished among fabrics cross-
linked by different preparatory methods. Therefore,
similar distinctions, by means of ACVs, were antici-
pated if fabric construction and pretreatment affected
a crosslinking reaction. This report discusses ACVs
and related data for basket-weave and plainweave
fabrics which were prescoured or premercerized and
crosslinked both slack and under tension in 5% di-
methylolethyleneurea (DMEU) solutions.
Experimental
Sam ples
The fabrics were woven from a Deltapine cotton into
conventional 80 X 80 printcloth (coded P) and 3 X 3
basket-weave of printcloth weight (coded B) from
warp yarns of 19.7 tex with 9.2 turns/cm [30s; 4.25
T.M.] and filling yams of 14.8 tex and either 9.3
turns/cm (subscript 9) or 7.5 turns/cm (subscript 7)
[40s; 3.75 T.M. or 3.00 T.M.]. The fabrics were
desized and scoured, then rewetted and dried (scoured)