143
J. Cosmet. Sci., 74.3, 143–157 (May/June 2023)
*Address all correspondence to Masato Yoshida, myoshida@milbon.com
Repairing Bleach-Damaged Hair by Treating With Polyphenol
in the Presence of Cu (II) Ions
MASATO YOSHIDA, RYO MARUYAMA AND ASAO YAMAUCHI
Development Headquarters, Milbon Co., Ltd., Zengenji-cho, Miyakojima-ku, Osaka, Japan (M.Y.)
Manufacturing Technology Development Production Headquarters, Milbon Co., Ltd., Yumegaoka, Iga, Mie,
Japan (R.M.)
Biomaterials Research Division, Osaka Research Institute of Industrial Science and Technology, Morinomiya,
Joto-ku, Osaka, Japan (A.Y.)
Accepted for publication July 10, 2023.
Synopsis
This study first examined a quinone-crosslinking reaction by treating the model protein (lysozyme and water-
soluble keratin) with various polyphenols (hydroquinone, catechol, chicoric acid, and others) in the presence of
copper (II) chlorophyllin in an aqueous phase. The amino acid analysis, the SDS-PAGE, and the quantification
of the SH group for the treated proteins suggested that the lysine, histidine, and cysteine residues of the
proteins underwent cross-linking reaction with the polyphenols. Based on these findings, the bleached hair
fibers were treated with the polyphenol in the presence of the copper salt (4 ppm). The resulting polyphenol-
treated hair fibers were examined by means of optical microscopes (fluorescence and light-transmission modes)
and an automatic tensile tester. It was found that the treatment of the bleached hair with chicoric acid in
the presence of the copper salt was especially effective in repairing the hair damage, with respect to the
cuticle scale-lifting, the swelling degree, and the mechanical properties (the breaking stress and initial elastic
modulus). The present treatment was conducted under mild conditions and its potential application to hair-
care technology for repairing bleached hair damage was briefly discussed.
INTRODUCTION
Many people today color their scalp hair using various dyes at home or in a beauty salon.
The purpose of hair dyeing is mainly to modify the color of hair for one’s liking or to
make gray hair look inconspicuous.1,2 However, the aesthetic effects deteriorate with time,
since hair grows from the root immediately after the treatment and the dyeing effect fades
gradually due to hair washing. Because of this it is necessary to re-dye regularly. The
repeated dyeing, as expected, gradually damages the physical properties of hair including
tensile strength and texture.
Hair damage from dyeing and bleaching treatments is mainly caused by alkaline and
oxidizing reagents, where the alkaline component assists the swelling and dyeing of the
144 JOURNAL OF COSMETIC SCIENCE
hair fibers and the oxidizing component mainly functions to decompose the melanin
molecules—the coloring ingredient of natural hair. Through the treatments, a small
portion of the keratin protein of the hair is changed to water-soluble products to escape
from the fibers.3-5
Various repair methods have been proposed by cosmetic scientists to cope with these types
of hair damage.6 Many of the methods aim to restore the physical properties of hair through
by mending the damaged part of the hair using hair-care products.7,8 Some repair methods
are similar to the processing technologies employed in the textile and food industries,9
such as a formation of complexes between proteins and phenols and tyrosine derivatives10,11
and a copper ion-catalyzed crosslinking reaction of gelatin with a quinone compound in
an aqueous phase.12 This study aims to explore a new hair treatment using a copper (II)
ion-catalyzed cross-linking reaction with various polyphenols (Figure 1). The treated hair is
evaluated mainly by the amino acid analysis, microscopic observations, and the mechanical
characteristics.
EXPERIMENTAL
HAIR SAMPLES AND REAGENTS
Straight reddish black hairs (natural hair color) were kindly donated by Japanese women
aged in their 20s and 30s. The hair fibers were neither bleached nor colored previously. The
lysozyme from hen egg white (Sigma-Aldrich, Tokyo, Japan) and the water-soluble keratin
(Keratec® IFP-HMW, Croda Japan KK, Shiga, Japan) were commercially available.
Catechol, hydroquinone, and resorcinol were all reagent-grade (Sigma-Aldrich, Tokyo,
Japan). Chicoric acid (Tokyo Kasei, Tokyo, Japan), copper (II) chlorophyllin (Croron®
Figure 1. The polyphenols and the copper (II) chlorophyllin catalyst, which were used in this study.
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