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wool blends
Accepted Manuscript Title: Smart Options For Simultaneous Functionalization and Pigment Coloration of Cellulosic/Wool Blends Author: N.A. Ibrahim H.M. Khalil E.M.R. El-Zairy W.A. Abdalla PII: DOI: Reference:
S0144-8617(13)00334-2 http://dx.doi.org/doi:10.1016/j.carbpol.2013.03.084 CARP 7606
To appear in: Received date: Revised date: Accepted date:
4-3-2013 18-3-2013 26-3-2013
Please cite this article as: Ibrahim, N. A., Khalil, H. M., El-Zairy, E. M. R., & Abdalla, W. A., Smart Options For Simultaneous Functionalization and Pigment Coloration of Cellulosic/Wool Blends, Carbohydrate Polymers (2013), http://dx.doi.org/10.1016/j.carbpol.2013.03.084 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
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Smart Options For Simultaneous Functionalization and Pigment Coloration of
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Cellulosic/Wool Blends
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N. A. Ibrahim a*, H. M. Khalilb, E. M. R. El-Zairyb, W. A. Abdallab a
Textile Research Division, National Research Centre, Dokki, Cairo, Egypt.
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b
Faculty of Applied Arts, Printing, Dyeing and Finishing Department, Helwan University, Cairo, Egypt.
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ABSTRACT
The present innovative research work deals with the individual use of chitosan (2.5g/Kg),
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Aloe vera (10g/Kg), triclosan (10g/Kg), TiO2-nanoparticles (TiO2-NP's ,10g/Kg), silicon micro-
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emulsion (20g/Kg) or a water/oil-repellent agent (40g/Kg) for modifying the pigment print paste
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to produce functionalized cotton/wool and viscose/wool pigment prints in one step process. The
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imparted functional properties such as antibacterial, antibacterial/UV-protection, soft-handle or
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water/oil-repellency together with the change in the printing properties were evaluated. Some of
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the obtained pigment prints were characterized by Scanning Electron Microscope (SEM), and
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Energy Dispersive X-rays (EDX) to confirm deposition of certain functional additives on printed
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fabrics. The wide-range of imparted functional properties together with the depth of the obtained
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pigment prints were maintained over 80% even after 15 consecutive laundering cycles. The
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extent of retention in functional and pigment printing properties is influenced by the type of
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functional additive as well as the kind of substrate.
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Keywords
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Cellulosic/Wool blends, Functional finishes, Pigment Printing, one step process, Chitosan, Aloe
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vera, Triclosan, Silicon softener, Water/oil repellent, TiO2-NP's.
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Corresponding author, Fax: +202 333 70931 E-mail address: [email protected] (N. A. Ibrahim).
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1. Introduction It is well known that, the most important natural fibers are cellulosic and protein fibers.
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They have been extensively utilized, alone and in admixtures, as textile materials. Blending of
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cellulosic and protein fibers results in improving the performance and quality properties,
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developing new textile products, minimizing the production cost as well as enhancing the
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possibility of imparting new functional properties. The abundant hydroxyl groups on the hydro-
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glucose units of cellulose are responsible for its chemicals reactivity. On the other hand, wool is
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made up of different amino acids, and its main functional groups include carboxyl (-COOH),
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amino (-NH2) and hydroxyl (-OH) groups; thus, the wool is chemically extremely active
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(Ibrahim, 2011; Hsieh 2007 & Lewis 2011).
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The use of pigment for textile printing has dramatically increased over the last 50 years,
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about 50% share, due to ease of application on various substrates, meet the demands of fastness
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properties, versatility as well as no need for after washing steps, i.e. energy and water
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conservation as well as a reduction in environmental impact. The main components of a pigment
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printing paste are pigment dispersion, binding agent, thickening agent, fixing agent and some
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auxiliaries, e.g. emulsifier, softener, defoamer..etc. taking in consideration the ecological concern
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(Giesen & Eisenlohr 1994; Ibrahim, et.al. 2005; Yaman et.al. 2012; Uddin & Lomas, 2005).
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In recent years, textile products with multi-functionality have gained interest to comply
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with the demands for high quality, comfort and healthy life styles. Functional properties, such as
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antibacterial, UV-protection, self-cleaning, water and oil-repellency, softness, anti-crease, and
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flame proofing, all have potential industrial applications (Gowri, et.al. 2010; Simoncic &
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Tomsic, 2010; Holme, 2007, Ibrahim et.al., 2010a; Bajaj, 2002; Hebeish & Ibrahim, 2007;
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Ibrahim et.al., 2010b; Ibrahim et.al., 2012a; Ibrahim et.al., 2008; Schindler & Hauser, 2004).
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In our present study, we develop a novel one-step process for producing cellulosic/wool
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pigment prints with desirable and durable functional and printing properties via incorporation of
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certain functional finishing agents, at proper concentration, into the pigment printing pastes
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followed by screen printing and microwave curing. All modified pigment prints were monitored
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for printability, fastness properties, functionality, and durability to wash. In addition, mode of
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interactions as well as surface modification of some printed fabric samples were also confirmed
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by SEM and EDX analysis.
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2. Experimental
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2.1. Materials
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Mill-scoured and semi-bleached cotton/wool (50/50, 450g/m2) and viscose/wool (50/50, 340g/m2) blended fabrics were used.
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Chitosan (degree of deacetylation > 82.9%, Sigma), Ciba® Oleophobol® Co. (oil, water and
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stain repellent agent based on dispersion of fluoropolymers containing extender, Ciba), Knittex®
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FEL cross-linking agent (reactant cross-linking agent based on a modified dimethylol dihydroxy
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ethyleneurea, Huntsman), Ultratex® MHT conc. (softening agent based on micro emulsion
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concentrate of a quaternary polydimethyl siloxane, Huntsman), Invasan® (antibacterial agent
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based on triclosan derivative, Huntsman), DAICO® Thick. 160 (synthetic thickener based on
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polyacrylate, Daico, Egypt), Pigment Red 146, Pigment Blue 153 and Pigment Orange 13
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(Daico, Egypt), as well as Printofix® Binder MTB-01 liquid (binding agent based on acrylate
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copolymer, Clariant) were of commercial grade. Aloe gel was extracted from Aloe vera plant, available in Egypt using methanol as a
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solvent (Jothi, 2009). All other chemicals used in this study such as ammonium persulphate
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[(NH4)2S2O8], and acetic acid were of laboratory reagent grade.
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TiO2-nanoparticles (TiO2-NP's) were prepared as previously reported (Bozzi et.al., 2005) using
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titanium tetraisoproproxide precursor (Sigma) with 2-propanol and nitric acid.
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2.2. Methods
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2.2.1. Functional finishing and pigment printing
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Simultaneous functionalization and pigment printing of the nominated cellulosic/wool
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blends were carried out using the flat screen technique and the following print paste
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formulations:
Pigment
g/Kg paste
20 100
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Binder
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Thickener
20
Functional additives: Silicon-softener
10-30
Chitosan
2.5-10
Water & oil repellent
20-60
TiO2-NP's
5-20
Invasan®
5-20
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or Aloe vera
5-20
H2O
X
Total
1000
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Printed fabric samples were then simultaneously dried and fixed in a commercial microwave oven at output of 1300W/4 min.
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2.2.2. Measurements
The depth of the obtained prints, expressed as K/S values, were determined from the
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reflectance measurements using the Kubelka Munk equation (Judd & Wyszeck, 1975): K/S = (1-
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R)2 / 2R, where K/S is the ratio of absorption and scattering coefficient, R is the reflectance at
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the wave length of maximum absorbance of the used pigment colorants.
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Fastness properties to washing, rubbing and light were assessed according to AATCC Test Methods: (61-1972), (8-1972), and (16A-1972) respectively.
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Antibacterial activity assessment against G+ve bacteria (S. aureus) and G-ve bacteria (E.
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coli) was evaluated qualitatively according to AATCC test method (147-1988) and expressed as
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zone of growth inhibition (ZI, mm).
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UV-protection factor (UPF) was evaluated according to AS/NZS 4399-1996 standard.
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According to the Australian classification scheme, fabrics can be rated as providing good, very
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good, or excellent protection if their UPF values range from 15 to 24, 25 to 39, or above 40
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respectively.
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Stiffness of the treated and untreated samples was evaluated according to AATCC Test Method (D 1388-96). Surface roughness of the treated and untreated samples was evaluated according to JIS 94 Standard, using surface roughness measuring instrument, SE 1700α (Japan).
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Water and oil repellency were evaluated according to AATCC Test Method 22-1989.
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Scanning electron microscope (SEM) images of some selected samples were obtained with
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a JEOL, JXA-840A electron probe micro-analyzer, equipped with energy disperse X-ray
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spectroscopy (EDX) for the composition analysis.
Standard Method (D 737-96).
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3. Results and Discussion
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Durability to washing was evaluated for some selected samples according to ASTM
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Factors affecting the imparted functional properties and pigment printing properties of
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cotton/wool and viscose/wool blended fabrics brought about by individual incorporation of
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certain functional finishing agents, namely chitosan, Aloe vera, triclosan derivative, TiO2-NP's,
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silicon softener and water-oil repellent into the pigment paste formulation, using different
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pigment colorants, followed by screen printing and microwave curing were thoroughly
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investigated. Discussion of the obtained results follows.
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3.1. Type and concentration of functional finishing agent Fig 1 (a) shows the influence of chitosan concentration on the extent of pigment coloration,
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expressed as K/S value. For a given set of printing paste formulation and curing conditions, it is
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clear that increasing chitosan concentration up to 2.5g/Kg paste results in a remarkable
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improvement in the depth of obtained pigment prints, regardless of the used substrate. This
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improvement in K/S values is a direct consequence of enhancing the extent of encapsulation,
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fixation and adhesion of the dispersed pigment particles, which have no affinity for any fibre,
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onto the substrate via enhancing the film forming properties and providing an extra active sites,
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i.e.
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et.al. 2005; Ibrahim et.al.2010c; Yaman et.al. 2012; Giesen & Eisenlohr 1994). Further increase
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in the chitosan concentration, beyond 2.5 g/Kg, is accompanied by a gradual decrease in the
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depth of the obtained prints most probably due to the gradual increase in the pigment print paste
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viscosity as well as a reduction in paste uptake/binder film formation and subsequent pigment
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entrapment during the microwave curing step. On the other hand, the extent of pigment fixation
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follows the decreasing order cotton/wool > viscose/wool reflects the differences between them in
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fabric structure, weight, porosity, thickeners, morphology, amount and availability of the
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chemical groups of the substrate components, which influence the extent of fixation and
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adhesion strength of the binder-to-fibre, as well as extent of undue penetration of dispersed
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pigment particles (Ibrahim et.al., 2013a & 2013b).
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–NH2 and –OH groups, for cross-linking and pigment particles accommodation (Ibrahim
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Fig. 1 (b) shows that increasing Aloe vera gel, a naturally occurring biopolymer,
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concentration up to 10g/Kg pigment paste is accompanied by a noticeable increase in the K/S
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values of the obtained pigment prints irrespective of the used substrate. The enhancement in the
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K/S value is determined by type of substrate: cotton/wool (K/S= 22.0) > viscose/wool (K/S=
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16.63). This remarkable increase in the K/S values most probably reflects the positive impacts of
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potentially active chemical constituents of Aloe vera gel such as carbohydrates, anthraquinones,
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organic compounds and lipids, proteins, enzymes and amino acids along with their active groups,
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e.g. – OH, -COOH, -NH2 groups (Hamman 2008; Moghaddasi & Verma, 2011), on enhancing
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the extent of formation of flexible three dimension binder film that encapsulates and entraps
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pigment particles and adheres them to fabric surfaces during microwave fixation step with a
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consequent darker depth of shades. Further increase in Aloe vera gel concentration up to 20 g/Kg
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is followed by a slight decrease in the fixation of the pigment particles, regardless of the used
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cellulosic/wool blended substrate.
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Fig. 1 (c) illustrates the effect of incorporating triclosan derivative, at different
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concentration (0-20 g/kg pigment paste) in the printing paste on the K/S values of the obtained
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pigment prints. Within the range examined the so-obtained results indicate that increasing
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triclosan concentration up to 10g/Kg results in increasing the K/S value of the cotton/wool prints
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from 17.48 up to 20.52 and viscose/wool prints from 14.02 up to 15.52. This can be discussed in
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terms of better encapsulation, binding and fixation of pigment particles onto the fabrics surface
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via the cross-linked binder film. Further increase in triclosan derivative concentration results in a
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slight decrease in the depth of the obtained prints; i.e. less extent of pigment fixation.
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As far as the changes in the K/S values of the obtained pigment prints as a function of the
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TiO2-NP's concentration, Fig. 1 (d) shows that the maximum values of K/S (20.92 and 19.00) for
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cotton/wool and viscose/wool respectively, attained at a TiO2-NP's concentration 10g/Kg
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pigment paste. It may be due to the positive role of TiO2-NP's, as a co-catalyst, in enhancing the
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extent of cross-linking of the binder film thereby improving the performance of capturing and
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entrapping pigment particles with subsequent adhesion to and fixation onto the fabrics surface
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(Ibrahim et.al., 2010a; Wang et.al., 2005; Nazariet et.al., 2009). Further increase in TiO2-NP's,
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beyond 10g/Kg, has a slight negative impact on the depth of the obtained prints as manifested by
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a decrease in the K/S values irrespective of the used substrate.
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On the other hand, Fig. 1(e) shows that inclusion of the quaternary polydimethyl siloxane
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softener Ultratex® HMT up to 20g/Kg, into the pigment printing paste along with other
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ingredients is accompanied by a significant increase in K/S value of the printed cellulosic/wool
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substrates, most probably due to the better accommodation and fixation of the pigment particles
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within the binder and/or the softener film onto the printed fabrics surface (Schindler & Hauser,
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2004 & Ibrahim et.al., 2005). Further increase in the softener film has practically no significant
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effect.
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Moreover, Fig. 1 (f) shows the effect of the used water/oil repellent agent, Ciba®
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Oleophobol, concentration on the K/S values of the obtained pigment prints. It is clear that depth
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of the printed fabric samples is gradually increased as the water/oil repellent concentration
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increase up to 40g/Kg then decreases slightly. This enhancement in K/S values could be
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discussed in terms of the formation of water/oil repellent polymer film alone or in combination
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with other components, i.e. binder and cross-linker, during the microwave curing step, thereby
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increasing the extent of fixation of pigment particles onto the coated fabric surface (Schindler &
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Hauser, 2004, Ibrahim et.al. 2010d). Further increase in the water/oil repellent agent results in a
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marginal decrease in the depth of the obtained prints.
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Based on the aforementioned studies, incorporation of chitosan (2.5g/Kg), Aloe vera gel
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(10g/Kg), triclosan derivative (10g/Kg), TiO2-NP's (10g/Kg), silicone softener (20g/Kg), or the
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water-oil repellent agent (40g/Kg) into the pigment printing paste formulation followed by
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screen printing and microwave fixation at 1300w/4 min seems to be a proper concentration for
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obtaining the higher depth of the obtained pigment prints, keeping other parameters constant.
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3.2. Combined functional finishing and pigment printing in one step Results of the foregoing section made it possible to obtain pigment prints with darker depth
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of shade along with expected functional properties by including the nominated functional
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additives, at the proper concentrations, into the print paste. With this in mind, systematic study
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was carried out to investigate the impact of using the nominated additives along with different
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pigment colorants on the functional and printing properties of the simultaneously finished and
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printed cellulosic/wool fabrics.
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3.2.1. Antimicrobial finishing/pigment printing
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The antimicrobial and pigment properties of printed cotton/wool and viscose/wool blended
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fabrics in the absence and presence of chitosan (2.5g/Kg), Aloe vera (10g/Kg) or triclosan
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derivatives (10g/Kg) were assessed and presented in Table 1. For a given set of printing
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conditions, the data in Table 1 signify that: i) incorporation of any of the nominated active
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ingredients into the printing paste results in a remarkable improvement in the antibacterial
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activity, expressed as ZI value, against the G+ve (S. aureus) and G-ve (E. coli) bacteria, ii) the
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extent of improvement in the imparted antimicrobial properties is governed by the type of
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functional additive: chitosan > Aloe vera > triclosan >> none, kind of substrate: cotton/wool >
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viscose/wool, as well as pigment colorant: Pigment Orange 13 > Pigment Red 146 > Pigment
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Blue 153, keeping other parameters fixed, iii) the variation in the antibacterial activity of the
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obtained pigment prints using chitosan, Aloe vera or triclosan could discussed in terms of the
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differences among them in: chemical structure, active ingredients, i.e. amino groups in chitosan,
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antiseptic agent (lupeol, salicylic acid, urea nitrogen, cinnamonic acid, phenols and sulfur) in
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Aloe vera or a chlorinated bis-phenols as in case of triclosan (Ibrahim et.al., 2010c, Zemljic
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et.al., 2009, Moghaddasi & Verma, 2011; Orhan et.al., 2007), compatibility with other
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ingredients in the printing paste, extent of fixation and loading onto the printed fabric surface as
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well as, iv) the difference in mode of antibacterial action, i.e. by interfering with bacterial
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metabolism and/or binding with DNA to inhibit mRNA synthesis due to the polycationic nature
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of chitosan especially in acidic medium (Zitao et.al., 2003; Kong et.al., 2010), via an
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electrochemical mode of action of penetrate and disrupt the cell walls of bacterial as in case of
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using Aloe vera thereby preventing the bacteria from functioning or reproducing (Jothi, 2009;
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Sarkar et.al., 2003), or by inhibiting fatty acid biosynthesis through the blocking of lipid bio-
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synthesis as in case of using triclosan derivative (Orhan et.al., 2009; Ibrahim et.al., 2013;
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Ibrahim et.al., 2010e).
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On the other hand, incorporation of chitosan, Aloe vera or triclosan derivative into the
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pigment printing paste is accompanied by an improvement in both the depth of the obtained
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prints along with their fastness properties, regardless of the used pigment colorant. This
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improvement in printing properties, i.e. K/S and fastness properties reflects the positive role of
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the aforementioned functional additives in enhancing the extent of fixation and accommodation
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of extra pigment particles within the cross-linked network formed onto the fabric surface during
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the microwave fixation step. Moreover, the variation in the printing properties upon using the
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aforementioned additives may be attributed to their differences in chemical structure, functional
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groups, extent of fixation and interaction among other ingredients during the fixation step as well
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as the differences among the used pigments in particle size, chemical composition, location and
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extant of distribution, color, hue as well as subsequent immobilization onto the fabric surface
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(Ibrahim et.al., 2005; Uddin & Lomas, 2005; Yaman et.al., 2012).
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Furthermore, the imparted antibacterial properties as well as the extant of pigment printing,
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in general, depend on the fabric structure, its functional groups, availability and accessibility of
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its active sites, mode of interaction and extent of modification, as well as location and extent of
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distribution of the formed film incorporating different ingredients, especially the antibacterial
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pendant groups and the pigment particles.
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Table 1 also clearly indicates that the effectiveness against the most common causes of
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bacterial infection, i.e. E. coli and S. aureus bacteria, follows the decreasing order G+ve > G-ve,
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irrespective of the used functional additive. This reflects the differences between the nominated
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bacteria in cell wall structure, sensitivity to disruption and/or in response to inactivation (Gupta
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et.al., 2008; Gouda & Ibrahim, 2008).
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3.2.2. Antibacterial/ anti-UV/ pigment printing To evaluate the dual role of TiO2-NP's as antibacterial and anti-UV agent, TiO2-NP's
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(10g/Kg) were included into the pigment printing paste followed by screen printing and
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microwave fixation. The data in Table 2 indicate that incorporate of TiO2-NP's into the printing
262
paste results in: i) a remarkable improvement in the antibacterial activity, expressed as ZI values,
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as well as in the UV-protecting properties, expressed as UPF values, of the printed fabric
264
samples, ii) an improvement in both the depth of the obtained pigment prints along with their
265
fastness properties, regardless of the used pigment colorant, iii) the enhancement in the imparted
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antibacterial functional property as well as the printing properties is determined by the type of
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substrate and follows the decreasing order: cotton/wool > viscose/wool, keeping other
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parameters constant and iv) the change in the pigment printing properties is governed by the type
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of pigment colorant as mentioned before.
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The imparted multifunctional properties, anti-bacterial/ anti-UV, reflects the dual role of
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loaded TiO2-NP's in i) generation of extremely reactive species, e.g. superoxide ions, hydroxyl
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radicals...etc, thereby enhancing the extent of attacking the bacterial cell membrane, losing of its
274
essential functions and destroying it (Ibrahim et.al., 2010a; Ibrahim et.al., 2012b; Chen & Wang,
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2006), as well as ii) scattering and absorbing the harmful UV-B radiation (Ibrahim et.al., 2012b;
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Ibrahim et.al., 2010a; Ibrahim et.al., 2013a; Abidi et.al., 2007).
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It is also clear from the Table 2 that: i) the nominated G+ve bacteria are more susceptible to
279
the action of the loaded TiO2-NP's than the G-ve bacteria, regardless of the used substrate, ii) the
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darker the depth of the shade, the greater is the UV-protection, irrespective of the used pigment
281
colorant, iii) the UPF-values of the functionalized pigment prints is governed by the extent of
282
loading TiO2-NP's onto the substrate: viscose/wool > cotton/wool , as well as the kind of
283
pigment colorant, iv) the enhancement in the pigment printing properties upon inclusion of TiO2-
284
NP's into the printing paste could be ascribed to the positive role of the TiO2-NP's as a co-
285
catalyst for cross-linking and intensifying the extent of polymerization and fixation of the binder
286
film onto fabrics surface and subsequent fixation and entrapment of extra pigment particles
287
(Chen & Wang, 2006; Nazari et.al., 2009; Dastjerdi & Motazer, 2010), and v) the slight
288
improvement in the light fastness properties of the obtained pigment prints could be attributed to
289
the UV light- absorption capacity of the loaded TiO2-NP's.
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3.2.3. Soft-handle finishing and pigment printing in one step For given set of soft-finishing and pigment printing of the nominated substrates using
293
different pigment colorants, the data in Table 3 demonstrate that: i) inclusion of the silicone
294
softener in the printing paste, 20 g/Kg, results in a significant improvement in the smoothness
295
along with a remarkable reduction in the stiffness of the produced pigment prints, ii) the positive
296
variation in the aforementioned surface properties reflects the positive role of silicone film as a
297
lubricating agent between the fibers in the yarn and between the yarns of the fabric, thereby
298
imparting softness and minimizing stiffness (Wahle & Falkowski, 2002; Harbered & Bereck,
299
2002; Hashem & Ibrahim, 2002; Ibrahim et.al., 2009), ii) the extent of reduction in fibre friction
300
which results in soft yarn and improved fabric handle, in the presence and absence of silicone
301
softener, is governed by the type of substrate and its components and follows the decreasing
302
order: viscose/wool > cotton/wool, iii) the enhancement in the printing properties, i.e. K/S and
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fastness properties, reflects the positive role of the silicone micro emulsion in leading to better
304
extent of binding film orientation, formation and/or distribution on the fabric surface thus
305
creating a proper conditions for accommodation and anchoring of pigment particles as well as
306
their fixation during the microwave curing step (Ibrahim et.al., 2005).
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3.2.4. Concurrent water/oil repellent and pigment printing
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Table 4 shows that printing of the nominated substrates in the presence of the water/oil
310
repellent additive (40g/Kg) followed by screen printing and microwave fixation is accompanied
311
by a remarkable increase in water/oil repellent ratings 70/6, and 50/5 for cotton/wool and
312
viscose/wool fabric respectively. The type of pigment colorant has practically no effect on the
313
imparted repellent properties. The imparted functional properties are governed by type of
314
substrate and follow the decreasing order: cotton/wool > viscose/wool fabric. The improvement
315
in the repellent properties is attributed to the formation of a hydrophobic/oleophobic polymer
316
film on the printed fabric surface thereby lowering the fabric surface energy and hence repellent
317
properties (Abo-Shosha et.al., 2009; Ibrahim et.al., 2010d). Incorporation of the nominated
318
water/oil repellent in the printing paste has a positive impact on the depth of the obtained prints
319
along with a slight enhancement in the fastness properties ratings as a direct consequence of
320
increasing the extent of entrapment and entanglement of the pigment particles within the cross-
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linked polymer film onto the fabric surface.
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309
323
On the other hand, the data so obtained signify that inclusion of the used water/oil-repellent
324
results in a remarkable reduction in the roughness, i.e. promoting surface smoothening, of the
325
obtained pigment prints as a direct consequence of the deposition of a hydrophobic smooth film
15
Page 15 of 32
326
on the fibre and fabric surface. The extent of improvement in surface smoothening is governed
327
by type of substrate i.e. viscose/wool > cotton/wool, keeping other parameters constant.
328
3.2.5. SEM images and EDX spectra
ip t
329
The SEM was used to observe the cotton/wool and viscose/wool blended fabrics before
331
(Fig. 2a & c) and after printing (Fig. 2b & d) respectively in the presence of certain functional
332
additives namely Aloe vera, TiO2-NP's (Fig. 3a & c) and the water/oil repellent (Fig. 3e & g)
333
respectively. According to the given SEM images, the pigment printed fabric surfaces were
334
clearly covered with deposited printing paste and loaded with the pigment particles along with
335
the nominated active ingredients; endow the fabric functionalization and coloration.
an
us
cr
330
On the other hand, EDX spectra of pigment printed cotton/wool and viscose/wool fabric
337
samples and loaded with TiO2-NP's (Fig. 3b & d) or the water/oil repellent (Fig. 3f & h)
338
confirmed the existence of titanium element or silicon and fluorine elements respectively on the
339
obtained pigment prints. The results were reported based on both the weight percentages (%).
340
Once again, the distribution of the deposited printing paste onto the fabric surface is influenced
341
by type and morphology of untreated substrate.
343
ed
pt
Ac ce
342
M
336
3.2.6. Durability to wash
344
The durability of the imparted functional properties as well as the retained depth of shade,
345
expressed as K/S values, of some pigment prints until 15 laundering cycles were determined
346
according to ASTM Standard Test (D737-96) and demonstrated in Table 5. For a give set of
347
printing condition, the data in Table 5 signify that: i) inclusion of the nominated functional
348
additives in the printing paste results in a significant improvement in the imparted functional
16
Page 16 of 32
properties along with an enhancement in the depth of the obtained pigment prints, ii) the
350
durability to wash, after 15 washing cycles, was slightly decreased, which can be discussed in
351
terms of desorption and/or removal of physically absorbed or unfixed active ingredients and
352
pigment particles, iii) the extent of retention of the imparted properties as well as the pigment
353
particles onto the printed substrate are governed by type of functional additive, kind of substrate,
354
along with the ability to form a durable three-dimensional cross-linked sheath or film containing
355
both the active species and the pigment particles on the fabric surface and iv) the obtained
356
functionalized pigment prints exhibited very sufficient: antibacterial and/or UV-blocking
357
properties, soft-handle, or water/oil repellency in addition to high depth of shades even after 15
358
washing cycles.
an
us
cr
ip t
349
361
4. Conclusions
Functionalized cotton/wool and viscose/wool pigment prints were achieved by individual
ed
360
M
359
including of chitosan (2.5g/Kg), Aloe vera (10g/Kg), triclosan (10g/Kg), TiO2-NP's
363
(10g/Kg), silicone softener (20g/Kg) or the water/oil repellent agent (40g/Kg) in the print
364
paste, followed by screen printing and microwave fixation at 1300W/4 min.
Ac ce
365
pt
362
The enhancement in the imparted functional properties such as antibacterial,
366
antibacterial/UV-protection, soft-handle or water-repellency with the improve in the
367
printing properties are governed by both the type of the functional additive and the kind
368
of substrate.
369 370
The functionalized pigment prints were found to have good functionality and printability even 15 consecutive laundering cycles.
17
Page 17 of 32
371
Finally, the obtained results have important practical implications for the establishment of
372
simultaneous functional finishing and pigment printing in one step process talking both
373
the environmental and economical aspects in concern. References
375
Abidi, N., Hequete, E., Tarimala, S. & Dai, I. I. (2007), Cotton fabric surface modification for
376
improved UV-radiation protection using sol- gel process", Journal of Applied Polymer Science,
377
104, 111-117.
378
Abo-Shosha, M. H., El-Hilw, Z. H., Aly, A. A. & Amr, A. (2009), New textile water repellent
379
based on reaction of toluene 2, 4-diisocyanate with stearyl alcohol, AATCC Review, 9 (7), 38-
380
42.
381
Bajaj, P. (2002), Finishing of textile materials, Journal of Applied Polymer Science, 83, 631-659.
382
Bozzi, A, Yuranova, T. & Kiwi, J. (2005), Self cleaning of wool-polyamide and polyester
383
textiles by TiO2-rutile modification under daylight irradiation at ambient temperature, Journal of
384
Photochemistry and Photobiology A: Chemistry, 172, 27-34.
385
Chen, C. C. & Wang, C. C. (2006), Crosslinking of cotton cellulose with succinic acid in the
386
presence of titanium dioxide nano-catalyst under UV-irradiation, Journal of Sol-Gel Science and
387
Technology, 40, 31-38.
388
Dastjerdi, R. & Montazer, M. (2010), A review on the application of inorganic nano-structured
389
materials in the modification of textiles: Focus on anti-microbial properties, Colloids and
390
Surfaces B: Biointerfaces, 79, 5-18.
391
Giesen, V. & Eisenlohr, R. (1994), Pigment printing, Review progress coloration, 24, 26-30.
392
Gouda, M., Ibrahim, N. A. (2008), New approach for improving antibacterial function to cotton
393
fabric, Journal of Industrial Textiles 37, 327-339.
Ac ce
pt
ed
M
an
us
cr
ip t
374
18
Page 18 of 32
Growri, S., Almeida, L., Amorim, T., Carneiro, N., Souto, A. P., & Esteves, M. F. (2010),
395
Polymer nonaparticles for multifunctional finishing of textiles-A review, Textile Research
396
Journal, 80, 1290-1306.
397
Gupta, P., Bajpai, M. & Bajpai, S. K. (2008), Investigation of antibacterial properties of silver
398
nanoparticles-loaded poly (acrylamide-co-itaconic acid)-grafted cotton fabric, Journal of Cotton
399
Science, 12, 280-286.
400
Habered, P. & Bereck, A. (2002), part 2: Silicone softeners, Review Progress Coloration, 32,
401
125-136.
402
Hamman, J. H. (2008), Composition and application of Aloe vera leaf gel, Molecules, 13, 1599-
403
1616.
404
Hashem, M. & Ibrahim, N. A. (2002), Response of linen fabric to finishing treatments, Journal
405
Textile Association, 63, 189-194.
406
Hebeish, A & Ibrahim, N. A. (2007), The impact of frontier sciences on textile industry,
407
Colourage Annual, 54, 41-55.
408
Holme, I. (2007), Innovative technologies for high performance textiles, Coloration Technology,
409
123, 59-73.
410
Hsieh, Y. L. (2007), Chemical structure and properties of cotton. In Cotton: Science and
411
Technology, Gordan, S. and Hsieh, Y. L. (Eds.), Woodhead, Cambridge.
412
Ibrahim, N. A., El-zairy, M. R., Zaky, S. & Borham, H. A. (2005), Environmental sound
413
synthetic pigment printing using synthetic thickening agents, Polymer-Plastics Technology and
414
Engineering, 44, 111-132.
415
Ibrahim, N. A., Gouda. M. & Zairy, W. M. (2008), Enhancing easy care and antibacterial
416
functions of cellulose/wool blends, Journal of Natural Fibers, 5, 347-365.
Ac ce
pt
ed
M
an
us
cr
ip t
394
19
Page 19 of 32
Ibrahim, N. A., Gouda, M., Husseiny, Sh. M., El-Gammal, R. M. & Mahrous, F. (2009), UV-
418
protecting and antibacterial finishing of cotton knits, Journal of Applied Polymer Science, 112,
419
3589-3596.
420
Ibrahim, N. A., Refai, R., & Ahmed, A. F. (2010a), Novel approach for attaining cotton fabric
421
with multifunctional properties, Journal of Industrial Textiles, 40, 65-83.
422
Ibrahim, N. A., Mahrous, F., El-Gamal, A. R., Gouda. M. & Husseiny, Sh. M. (2010b),
423
Multifunctional anionic cotton dyeing, Journal of Applied Polymer Science, 115, 3249-3255.
424
Ibrahim, N. A., El-Zairy, E. M. R., El-Zairy, M. R. and Khalil, H. M. (2010c), Improving
425
transfer printing and UV-blocking properties of polyester-based textiles using MCT-βCD,
426
chitosan and ethylenediamine, Coloration Technology 126, 330 -336.
427
Ibrahim, N. A., Amr, A., Eid, B. M. and El Sayed, Z. M. (2010d), Innovative multifunctional
428
treatments of ligno-cellulosic jute fabric, Carbohydrate Polymers, 82, 1198-1204.
429
Ibrahim, N. A., Hashem, M., El-Sayed, W. A., El-Husseiny, Sh., Elanany, E. M. (2010e),
430
Enhancing antimicrobial properties of dyed and finished cotton/polyester fabrics, AATCC
431
Review, 10, 55-63.
432
Ibrahim, N. A. (2011), Dyeing of textile fibre blends, In M.Clark (Ed.), Handbook of textile and
433
industrial dyeing, vol. 2: Application of dyes (pp.147-172), Oxford: Woodhead publishers,
434
Chapter 4.
435
Ibrahim, N. A., Eid, B. M. & El-Batal, H. (2012a), A novel approach for adding smart
436
functionalities to cellulosic fabrics, Carbohydrate Polymers, 87, 744-751.
437
Ibrahim, N. A., Amr, A., Eid, B. M., Mohammed, Z. E. and Fahmy, H. M. (2012b), Poly (acrylic
438
acid)/poly (ethylene glycol) adduct for attaining multifunctional cellulosic fabrics, Carbohydrate
439
Polymers 89, 648-660.
440
Ibrahim, N. A., El-Zairy, E. M. R., Abdalla, W. A. and Khalil, H. M. (2013a), Combined UV-
441
protecting and reactive printing of cellulosic/wool blends, Carbohydrate Polymers, 92, 1386-
442
1394.
Ac ce
pt
ed
M
an
us
cr
ip t
417
20
Page 20 of 32
Ibrahim, N. A., Abdalla, W. A., El-Zairy, E. M. R. and Khalil, H. M. (2013b), Utilization of
444
monochloro-triazine β-Cyclodexrtin for enhancing printability and functionality of wool,
445
Carbohydrate Polymers 92, 1520-1529.
446
Jothi, D. (2009), Experimental study on antimicrobial activity of cotton fabric treated with aloe
447
gel extract from aloe vera plant for controlling the Staphylococcus aureus (bacterium), African
448
Journal of Microbiology Research, 3, 228-232.
449
Judd, D. & Wyszeck, G. (1975), Color in business science and industry, 3rd ed., New York: John
450
Wiley & Sons.
451
Kong, M., Chen, X. G., Xing, K. & Park, H. J. (2010), Antimicrobial properties of chitosan and
452
mode of action: A state of the art review, International Journal of Food Microbiology, 144, 51-
453
63.
454
Lewis, D. M. (2011), Coloration of wool, in M. Clark (Ed.), Handbook of textiles and industrial
455
dyeing, vol. 2: Applications of dyes, pp. (6-7), Oxford: Woodhead publisher, Chapter 1.
456
Moghaddasi, M. S. & Verma, S. K. (2011), Aloe vera their chemicals composition and
457
applications: A review, International Journal of Biological & Material Research, 2, 466-471.
458
Nazari, A., Montazer, M. & Rahimi, M. K. (2009), Concurrent antimicrobial and crosslinking of
459
bleached and cationic cotton using nano- TiO2 and BTCA, Iranian Polymer Science and
460
Technology Journal, 22, 41-51.
461
Nazari, A., Montazer, M., Rashidi, A., Yazdanshenas, M. & Abbasinejad, M. A. (2009), Nano-
462
TiO2 photo-catalyst and sodium hypophosphite for crosslinking cotton with polycarboxylic acids
463
under UV and high temperature, Applied Catalysis A: General, 371, 10-16.
464
Orhan, M., Kut, D., & Gunesoglu, C. (2007), Use of triclosan as antibacterial agent in textiles,
465
Indian Journal of Fibre & Textile Research, 32, 114-118.
466
Orhan, M., Kut, D. & Gunesoglu, C. (2009), Improving the antibacterial activity of cotton fabrics
467
finished with triclosan by the use of 1, 2, 3, 4- butanetetracarboxylic acid and citric acid, Journal
468
of Applied Polymer Science, 111, 1344-1352.
Ac ce
pt
ed
M
an
us
cr
ip t
443
21
Page 21 of 32
Sarkar, R. K., Purushottam, D. E. & Chanuhan, P. D. (2003), Bacteria-resist finish on cotton
470
fabrics using natural herbal extracts, Indian Journal of Fibers & Textile Research, 28, 322-331.
471
Schindler, W. D & Hauser, P. I. (2004), Chemical finishing of textiles, Woodhead Publisher,
472
Cambridge, England.
473
Simoncic, B., & Tomsic, B. (2010), Structure of novel antimicrobial agents for textiles-A review,
474
Textile Research Journal, 80, 1721-1737.
475
Uddin, F. & Lomas, M. (2005), Combined crease recovery finishing and pigment printing,
476
Coloration Technology, 121, 158-163.
477
Wahle, B. & Falkowski, J. (2002), Softeners in textile processing, part 1: An overview, Review
478
Progress Coloration, 32, 118-124.
479
Wang, C. C. & Chen, C. C. (2005), Physical properties of crosslinked cellulose catalyzed with
480
nano-titanium dioxide, Journal of Applied Polymer Science, 97, 2450-2456.
481
Yaman, N., Ozdogan, E. & Seventekin, N., (2012), Improvement in fastnesses and color strength
482
of pigment printed textile fabric, Journal of Engineered Fibers & Fabrics, 7, 40-46.
483
Zemljic, L. F., Strand, S., Sauperl, O. X. & Kleinschek, K. S. (2009), Characterization of amino
484
groups for cotton fabrics coated with chitosan, Textile Research Journal, 79, 219-226.
485
Zitao, Z., Chen, L., Jinmin, J., Yanliu, H. & Donghui, C. (2003), Antibacterial properties of
486
cotton fabrics treated with chitosan, Textile Research Journal, 73, 1103-1106.
488
cr
us
an
M
ed
pt
Ac ce
487
ip t
469
489 490 491
22
Page 22 of 32
492
List of Figures
493 494 495 496 497 498 499 500 501 502 503 504 505 506
Fig.1. Effect of Chitosan (a), Aloe vera (b), Triclosan (c), TiO2-NP's (d), Silicone Softener (e), and Oleophobol® (f) concentration on the depth of the obtained prints.
ip t
Printing paste components: Pigment Red 146(20g/Kg); synthetic thickener(20g/Kg); Printofix®Binder - MTB(100g/Kg); cross-linker(10g/Kg); and (NH4)2S2O8(2g/Kg). Microwave fixation: 1300W/4min.
cr
Fig.2. SEM of untreated Cotton/Wool fabric (a), SEM of treated Cotton/Wool fabric with Aloe vera (b), SEM of untreated Viscose/Wool fabric (c), SEM of treated Viscose/Wool fabric with Aloe vera (d).
us
Fig.3. EDX image and element content of TiO2-NP’s loaded Cotton/Wool blend (a, b) and Viscose/Wool blend (c, d), EDX image and element content of water/oil repellent loaded Cotton/Wool blend (e, f) and Viscose/Wool blend (g, h).
an
507 508
M
509 510
Ac ce
pt
ed
511
23
Page 23 of 32
Highlights
512
-
Functionalized Cellulosic/Wool pigment prints
513
-
Inclusion of certain functional additives
514
-
Functional finishing and pigment printing in one step
515
-
Innovative pigment prints with durable functionalities
cr
516
ip t
511
us
517
Ac ce
pt
ed
M
an
518
24
Page 24 of 32
Table 1
Table1. Antibacterial/printing properties of printed cellulosic/wool blended fabrics using different pigment colorants along with antimicrobial additives in the printing paste a
Pigment Blue 153
Cotton/ Wool
Viscose/ Wool
Wet
4-5 (4)
4-5 (4)
4-5 (4)
4 (3-4)
4-5 (3-4)
22.00
4-5
4-5
4-5
4-5
4-5
13.0
20.52
4-5
4-5
5
4-5
4-5
19.0 (00.0)
18.0 (00.0)
19.43 (14.02)
4 (3-4)
4 (3-4)
4 (3-4)
4 (3)
4 (3)
Aloe vera
16.0
14.5
16.63
4-5
4-5
4-5
4
4
Triclosan
13.5
11.5
15.52
Chitosan
21.0 (00.0)
18.0 (00.0)
13.22 (11.60)
Aloe vera
18.0
16.0
Triclosan
14.0
12.0
Chitosan
18.0 (00.0)
16.0 (00.0)
Aloe vera
14.0
13.0
22.0 (00.0)
20.0 (00.0)
21.61 (17.48)
Aloe vera
19.5
17.0
Triclosan
15.5
Chitosan
Triclosan
4-5
4
4
4-5 (4)
4-5 (3-4)
4-5 (3)
4 (3)
4-5 (4)
16.39
5
4-5
4-5
4
4-5
14.78
4-5
4-5
3-4
3-4
4-5
12.52 (11.25)
4-5 (4)
4-5 (3-4)
4-5 (3)
4 (3)
4-5 (4)
15.55
4-5
4-5
4-5
4
4-5
13.34
4-5
4-5
4
4
4-5
24.0 (00.0)
22.0 (00.0)
8.61 (6.75)
5 (4)
4-5 (4)
4-5 (4)
4 (3-4)
5 (4)
20.5
19.0
10.35
4-5
4-5
4-5
4-5
5
Triclosan
18.0
16.0
9.93
4-5
4-5
4-5
4-5
5
Chitosan
20.5 (00.0)
18.5 (00.0)
8.31 (6.24)
4-5 (3)
4 (3)
4 (3)
4 (3)
4 (3-4)
Aloe vera
16.5
15.0
10.03
4
3-4
4
4
4
Triclosan
14.5
12.5
9.52
4
4
4-5
4-5
4
Aloe vera
Ac a
4-5
10.0
ce pt
Pigment Orange 13
-
Viscose/ Wool
4-5
12.0
Chitosan Cotton/ Wool
cr
Chitosan
ip t
Dry
G −ve
us
Viscose/ Wool
LF f
St.
Alt
G +ve
an
Pigment Red 146
Cotton/ Wool
K/S
Additive
RF e
c
M
Substrate
WF d
ed
Pigment
ZI b (mm)
Printing paste components : pigment colorant (20 g/Kg); synthetic thickener (20g/Kg); binder
(100g/Kg); cross-linker (10g/Kg); catalyst (2g/Kg) in the absence and presence of Chitosan (2.5g/Kg), Aloe vera (10g/Kg) or Triclosan (10g/Kg). Microwave fixation at 1300W/4min.
-
b
ZI: zone of inhibition; c K/S: color strength; d WF: wash fastness; Alt: alteration; St. staining on
cotton; e RF: rubbing fastness; f LF: light fastness. -
Values in parenthesis are the values of the pigment prints in the absence of the aforementioned functional additives.
24 Page 25 of 32
Table 2
Table 2. Antibacterial/UV-protecting and printing properties of printed cellulosic/wool blended fabrics using different pigment colorants along with TiO2-NP's in the printing paste a .
Pigment Red 146
Substrate
WF e UPF
TiO2-NP's (10g/Kg)
G +ve
G −ve
Without
00.0
00.0
63
With
16.0
15.0
Without
00.0
With
c
K/S
St.
Dry
Wet
17.48
4
4
4
3-4
80
20.91
4-5
00.0
74
14.02
13.0
11.5
99
19.03
Without
00.0
00.0
60
11.60
With
23.0
20.0
76
Without
00.0
00.0
85
With
18.0
17.0
Without
00.0
00.0
With
21.0
Without
00.0
a
4
cr
3
3
4-5
4-5
4
4
4
4
3-4
3
3
4
13.89
4-5
4-5
4-5
4
4-5
11.25
4
3-4
3
3
4
118
13.40
5
4-5
4-5
4
4-5
81
6.75
4
4
4
3-4
4
us
an
ed 18.0
95
9.87
5
4-5
4-5
4
4-5
00.0
98
6.24
3
3
3
3
3-4
137
8.98
4
3-4
4
4
4
ce pt 15.0
With
4
3-4
M
Pigment Blue 153 Pigment Orange 13
Cotton/ Wool
4-5
3-4
Cotton/ Wool
Viscose/ Wool
4-5
3-4
3-4
Viscose/ Wool
-
LF g
Alt
Cotton/ Wool
Viscose/ Wool
RF f
d
ip t
Pigment
ZI b (mm)
13.0
Printing paste components : pigment colorant (20 g/Kg); synthetic thickener (20g/Kg); binder (100g/Kg); cross-
Ac
linker (10g/Kg); catalyst (2g/Kg) in the absence and presence of TiO2-NP's (10g/Kg). Microwave fixation at 1300W/4min. -
b
ZI: zone of inhibition;
c
UPF: ultraviolet protection factor;
d
K/S: color strength;
e
WF: wash fastness; Alt:
alteration; St. staining on cotton; f RF: rubbing fastness; g LF: light fastness.
25 Page 26 of 32
Table 3
Table3. Softness and printing properties of printed cellulosic/wool blended fabrics using different
Pigment Red 146
Substrate
WF c
Surface roughness (mm)
Stiffness
Without
29.05
3833
17.48
4
With
15.96
1340
25.02
4-5
Without
22.54
2519
14.02
3-4
3-4
With
13.41
1114
16.90
4
26.95
4100
11.60
With
14.98
1768
Without
23.11
1866
With
14.03
Without
25.49
With
14.10
Without
21.68
Silicon softener (20g/Kg)
K/S
Alt
-
a
13.25
4
4
3-4
4-5
4-5
3-4
3
3
4
4
4
4-5
cr
5
3-4
3
3
4
17.64
4-5
4
4-5
4
5
11.25
4
3-4
3
3
4
1458
15.81
4-5
4-5
4
4
4-5
2880
6.75
4
4
4
3-4
4
2099
9.47
4-5
4-5
4-5
4-5
4-5
2548
6.24
3
3
3
3
3-4
1865
9.06
3-4
3-4
4
4
4
ed
ce pt With
Wet
3-4
an
M
Pigment Blue 153 Pigment Orange 13
Viscose/ Wool
Dry
4
Cotton/ Wool
Cotton/ Wool
St.
4-5
Viscose/ Wool
Viscose/ Wool
LF e
us
Cotton/ Wool
Without
RF d
b
ip t
Pigment
pigment colorants along with Silicone softener in the printing paste a .
Printing paste components : pigment colorant (20g/Kg); synthetic thickener (20g/Kg); binder (100g/Kg); cross-
Ac
linker (10g/Kg); catalyst (2g/Kg) in the absence and presence of Silicon softener (20/Kg). Microwave fixation at 1300W/4min. -
b
K/S: color strength; c WF: wash fastness; Alt: alteration; St. staining on cotton; d RF: rubbing fastness; e LF: light
fastness.
26 Page 27 of 32
Table 4
Table 4. Water/Oil repellency and printing properties of printed cellulosic/wool blended fabrics
Repellency rating
Surface roughness (mm)
WF c K/S
Alt
St.
17.48
4
4
20.19
22.38
4-5
4-5
0
22.54
14.02
3-4
3-4
70
5
16.85
20.03
4-5
4-5
Without
0
0
26.95
11.60
With
80
7
20.58
Without
0
0
23.11
With
70
5
Without
0
0
With
80
7
Without
0
0
Water
Oil
Without
0
0
29.05
With
80
7
Without
0
With
Cotton/ Wool
Viscose/ Wool
With
a
70
5
Wet
4
3-4
4-5
us
3-4
4-5
4
3-4
3
3
4
4
3-4
3
3
4
13.75
4-5
4-5
4
3-4
4-5
11.25
4
3-4
3
3
4
18.54
13.44
4-5
4-5
3-4
3-4
4-5
25.49
6.75
4
4
4
3-4
4
18.34
9.69
4-5
4-5
5
4-5
4-5
21.68
6.24
3
3
3
3
3-4
16.30
9.40
3-4
3-4
4
3-4
4
an
ed
ce pt
Pigment Orange 13
Cotton/ Wool
Dry
3-4
Cotton/ Wool
Viscose/ Wool
LF e
4
M
Pigment Blue 153
Viscose/ Wool
-
RF d
b
ip t
Substrate
Water/Oil repellent (40g/Kg)
cr
Pigment Red 146
Pigment
using different pigment colorants along with the water/oil repellent agent in the printing paste a .
Printing paste components : pigment colorant (20 g/Kg); synthetic thickener (20g/Kg); binder (100g/Kg); cross-
Ac
linker (10g/Kg); catalyst (2g/Kg) in the absence and presence of the Water/oil repellent agent (40/Kg). Microwave fixation at 1300W/4min. -
b
K/S: color strength; c WF: wash fastness; Alt: alteration; St. staining on cotton; d RF: rubbing fastness; e LF:
light fastness.
27 Page 28 of 32
Table 5
Table 5. Durability of the imparted functional and coloration properties to wash using different printing pastea
ZI b (mm)
00
00
V/W
00
00
22.0 (19.5) 19.0 (17.0) 19.5 (17.5) 16.0 (14.0) 19.0 (17.0) 13.5 (11.5) 16.0 (14.5) 13.0 (11.0)
20.0 (17.5) 18.0 (16.0) 17.0 (15.0) 14.5 (13.0) 18.0 (16.5) 11.5 (10.0) 15.0 (13.5) 11.5 (10.0)
Aloe vera (10 g/Kg)
Triclosan (10 g/Kg)
Antibacterial & Anti-UV
TiO2-NP's (10 g/Kg)
Soft-handle
Softener (20 g/Kg)
C/W
-
-
V/W
-
Water/Oil repellent (40 g/Kg)
C/W
-
V/W
-
V/W C/W V/W C/W V/W C/W V/W
29.05 (25.52) 22.54 (20.08)
-
-
-
-
-
-
-
-
80 (68) 99 (87) -
-
-
-
-
-
-
ed
Water/Oil repellent
C/W
63 (50) 74 (60)
K/S d Water
Oil
00
00
00
00
-
-
-
-
ip t
C/W
M
Antibacterial
a
G −ve
None
Chitosan (2.5 g/Kg)
-
G +ve
Roughness (mm)
cr
None
UPF
Substrate
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
80 (70) 70 (50)
7 (5) 5 (4)
us
Additive
Repellency rate c
an
Functional finish
15.96 (17.65) 13.41 (11.23) 20.91 (23.30) 16.85 (18.20)
17.48 (13.15) 14.02 (10.62) 21.61 (17.75) 19.43 (16.22) 22.00 (18.92) 16.63 (13.32) 20.52 (16.85) 15.52 (12.48) 20.91 (17.38) 19.03 (16.00) 25.02 (22.01) 16.90 (13.87) 22.38 (19.22) 20.03 (16.88)
Printing paste components : Pigment Red 146 (20 g/Kg); synthetic thickener (20g/Kg); Printofix® Binder MTB
-
C/W: cotton/wool blend; V/W: viscose/wool blend; color strength.
b
ZI: zone of inhibition; c UPF: UV-protection factor; d K/S:
Values in parenthesis are the values of some pigment prints properties after 15 washing cycles.
Ac
-
ce pt
(100g/Kg); cross-linker (10g/Kg); catalyst (2g/Kg). Microwave fixation at 1300W/4min.
28 Page 29 of 32
Figure 1
22
24
20
22 20
K/S
K/S
18
16
18 16
14
12
■
▲
12
Cotton/Wool Viscose/Wool
■
10 0
5
10
0
10
20
cr
(a) Chitosan Conc. (g/Kg) 22
22
20
20
an
us
(b) Aloe Vera Conc. (g/Kg)
18
K/S
18
16
14
16
M
K/S
Cotton/Wool Viscose/Wool
▲
10
14
12
0
12
10
■
10
20
0
(c) Triclosan Conc. (g/Kg)
24
18 16
22 20
K/S
20
18 16 14
14
■
12
20
24
Ac
22
10
(d) TiO2-NP's Conc. (g/Kg)
ce pt
26
Cotton/Wool Viscose/Wool
▲
ed
■ Cotton/Wool ▲ Viscose/Wool
10
K/S
ip t
14
▲
■
12
Cotton/Wool Viscose/Wool
▲
10
Cotton/Wool Viscose/Wool
10
0
10
20
30
0
20
40
60
®
(f) Oleophobol Conc. (g/Kg)
(e) Silicone Softener Conc. (g/Kg)
Fig.1. Effect of Chitosan (a), Aloe vera (b), Triclosan (c), TiO 2-NP's (d), Silicone Softener (e), and Oleophobol® (f) concentration on the depth of the obtained prints. Printing paste components: Pigment Red 146(20g/Kg); synthetic thickener (20g/Kg); Printofix®Binder MTB (100g/Kg); crosslinker(10g/Kg); and (NH 4)2S2O8(2g/Kg). Microwave fixation: 1300W/4min. Page 30 of 32
29
Figure 2
(b)
an
us
cr
ip t
(a)
(d)
Ac ce p
te
d
M
(c)
Fig.2. SEM of untreated Cotton/Wool fabric (a), SEM of treated Cotton/Wool fabric with Aloe vera (b), SEM of untreated Viscose/Wool fabric (c), SEM of treated Viscose/Wool fabric with Aloe vera (d).
30
Page 31 of 32
(b)
(c)
(d)
M
an
us
cr
(a)
ip t
Figure 3
(e)
Ac
(g)
ce pt
ed
(f)
(h)
Fig.3. EDX image and element content of TiO2-NP’s loaded Cotton/Wool blend (a, b) and Viscose/Wool blend (c, d), EDX image and element content of water/oil repellent loaded Cotton/Wool blend (e, f) and Viscose/Wool blend (g, h). Page 32 of 32
S0144-8617(13)00334-2 http://dx.doi.org/doi:10.1016/j.carbpol.2013.03.084 CARP 7606
To appear in: Received date: Revised date: Accepted date:
4-3-2013 18-3-2013 26-3-2013
Please cite this article as: Ibrahim, N. A., Khalil, H. M., El-Zairy, E. M. R., & Abdalla, W. A., Smart Options For Simultaneous Functionalization and Pigment Coloration of Cellulosic/Wool Blends, Carbohydrate Polymers (2013), http://dx.doi.org/10.1016/j.carbpol.2013.03.084 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
1
Smart Options For Simultaneous Functionalization and Pigment Coloration of
2
Cellulosic/Wool Blends
3
N. A. Ibrahim a*, H. M. Khalilb, E. M. R. El-Zairyb, W. A. Abdallab a
Textile Research Division, National Research Centre, Dokki, Cairo, Egypt.
5
b
Faculty of Applied Arts, Printing, Dyeing and Finishing Department, Helwan University, Cairo, Egypt.
6
ip t
4
ABSTRACT
The present innovative research work deals with the individual use of chitosan (2.5g/Kg),
8
Aloe vera (10g/Kg), triclosan (10g/Kg), TiO2-nanoparticles (TiO2-NP's ,10g/Kg), silicon micro-
9
emulsion (20g/Kg) or a water/oil-repellent agent (40g/Kg) for modifying the pigment print paste
10
to produce functionalized cotton/wool and viscose/wool pigment prints in one step process. The
11
imparted functional properties such as antibacterial, antibacterial/UV-protection, soft-handle or
12
water/oil-repellency together with the change in the printing properties were evaluated. Some of
13
the obtained pigment prints were characterized by Scanning Electron Microscope (SEM), and
14
Energy Dispersive X-rays (EDX) to confirm deposition of certain functional additives on printed
15
fabrics. The wide-range of imparted functional properties together with the depth of the obtained
16
pigment prints were maintained over 80% even after 15 consecutive laundering cycles. The
17
extent of retention in functional and pigment printing properties is influenced by the type of
18
functional additive as well as the kind of substrate.
Ac ce
pt
ed
M
an
us
cr
7
19 20
Keywords
21
Cellulosic/Wool blends, Functional finishes, Pigment Printing, one step process, Chitosan, Aloe
22
vera, Triclosan, Silicon softener, Water/oil repellent, TiO2-NP's.
23 *
Corresponding author, Fax: +202 333 70931 E-mail address: [email protected] (N. A. Ibrahim).
1
Page 1 of 32
24
1. Introduction It is well known that, the most important natural fibers are cellulosic and protein fibers.
26
They have been extensively utilized, alone and in admixtures, as textile materials. Blending of
27
cellulosic and protein fibers results in improving the performance and quality properties,
28
developing new textile products, minimizing the production cost as well as enhancing the
29
possibility of imparting new functional properties. The abundant hydroxyl groups on the hydro-
30
glucose units of cellulose are responsible for its chemicals reactivity. On the other hand, wool is
31
made up of different amino acids, and its main functional groups include carboxyl (-COOH),
32
amino (-NH2) and hydroxyl (-OH) groups; thus, the wool is chemically extremely active
33
(Ibrahim, 2011; Hsieh 2007 & Lewis 2011).
an
us
cr
ip t
25
The use of pigment for textile printing has dramatically increased over the last 50 years,
35
about 50% share, due to ease of application on various substrates, meet the demands of fastness
36
properties, versatility as well as no need for after washing steps, i.e. energy and water
37
conservation as well as a reduction in environmental impact. The main components of a pigment
38
printing paste are pigment dispersion, binding agent, thickening agent, fixing agent and some
39
auxiliaries, e.g. emulsifier, softener, defoamer..etc. taking in consideration the ecological concern
40
(Giesen & Eisenlohr 1994; Ibrahim, et.al. 2005; Yaman et.al. 2012; Uddin & Lomas, 2005).
ed
pt
Ac ce
41
M
34
42
In recent years, textile products with multi-functionality have gained interest to comply
43
with the demands for high quality, comfort and healthy life styles. Functional properties, such as
44
antibacterial, UV-protection, self-cleaning, water and oil-repellency, softness, anti-crease, and
45
flame proofing, all have potential industrial applications (Gowri, et.al. 2010; Simoncic &
2
Page 2 of 32
46
Tomsic, 2010; Holme, 2007, Ibrahim et.al., 2010a; Bajaj, 2002; Hebeish & Ibrahim, 2007;
47
Ibrahim et.al., 2010b; Ibrahim et.al., 2012a; Ibrahim et.al., 2008; Schindler & Hauser, 2004).
48
In our present study, we develop a novel one-step process for producing cellulosic/wool
50
pigment prints with desirable and durable functional and printing properties via incorporation of
51
certain functional finishing agents, at proper concentration, into the pigment printing pastes
52
followed by screen printing and microwave curing. All modified pigment prints were monitored
53
for printability, fastness properties, functionality, and durability to wash. In addition, mode of
54
interactions as well as surface modification of some printed fabric samples were also confirmed
55
by SEM and EDX analysis.
an
us
cr
ip t
49
2. Experimental
58
2.1. Materials
60
Mill-scoured and semi-bleached cotton/wool (50/50, 450g/m2) and viscose/wool (50/50, 340g/m2) blended fabrics were used.
pt
59
ed
57
M
56
Chitosan (degree of deacetylation > 82.9%, Sigma), Ciba® Oleophobol® Co. (oil, water and
62
stain repellent agent based on dispersion of fluoropolymers containing extender, Ciba), Knittex®
63
FEL cross-linking agent (reactant cross-linking agent based on a modified dimethylol dihydroxy
64
ethyleneurea, Huntsman), Ultratex® MHT conc. (softening agent based on micro emulsion
65
concentrate of a quaternary polydimethyl siloxane, Huntsman), Invasan® (antibacterial agent
66
based on triclosan derivative, Huntsman), DAICO® Thick. 160 (synthetic thickener based on
67
polyacrylate, Daico, Egypt), Pigment Red 146, Pigment Blue 153 and Pigment Orange 13
Ac ce
61
3
Page 3 of 32
68
(Daico, Egypt), as well as Printofix® Binder MTB-01 liquid (binding agent based on acrylate
69
copolymer, Clariant) were of commercial grade. Aloe gel was extracted from Aloe vera plant, available in Egypt using methanol as a
71
solvent (Jothi, 2009). All other chemicals used in this study such as ammonium persulphate
72
[(NH4)2S2O8], and acetic acid were of laboratory reagent grade.
73
TiO2-nanoparticles (TiO2-NP's) were prepared as previously reported (Bozzi et.al., 2005) using
74
titanium tetraisoproproxide precursor (Sigma) with 2-propanol and nitric acid.
us
cr
ip t
70
76
2.2. Methods
77
2.2.1. Functional finishing and pigment printing
an
75
Simultaneous functionalization and pigment printing of the nominated cellulosic/wool
79
blends were carried out using the flat screen technique and the following print paste
80
formulations:
Pigment
g/Kg paste
20 100
Ac ce
Binder
pt
Content
ed
M
78
Thickener
20
Functional additives: Silicon-softener
10-30
Chitosan
2.5-10
Water & oil repellent
20-60
TiO2-NP's
5-20
Invasan®
5-20
4
Page 4 of 32
or Aloe vera
5-20
H2O
X
Total
1000
83
Printed fabric samples were then simultaneously dried and fixed in a commercial microwave oven at output of 1300W/4 min.
cr
82
ip t
81
85
us
84
2.2.2. Measurements
The depth of the obtained prints, expressed as K/S values, were determined from the
87
reflectance measurements using the Kubelka Munk equation (Judd & Wyszeck, 1975): K/S = (1-
88
R)2 / 2R, where K/S is the ratio of absorption and scattering coefficient, R is the reflectance at
89
the wave length of maximum absorbance of the used pigment colorants.
M
ed
91
Fastness properties to washing, rubbing and light were assessed according to AATCC Test Methods: (61-1972), (8-1972), and (16A-1972) respectively.
pt
90
an
86
Antibacterial activity assessment against G+ve bacteria (S. aureus) and G-ve bacteria (E.
93
coli) was evaluated qualitatively according to AATCC test method (147-1988) and expressed as
94
zone of growth inhibition (ZI, mm).
Ac ce
92
95
UV-protection factor (UPF) was evaluated according to AS/NZS 4399-1996 standard.
96
According to the Australian classification scheme, fabrics can be rated as providing good, very
97
good, or excellent protection if their UPF values range from 15 to 24, 25 to 39, or above 40
98
respectively.
5
Page 5 of 32
100 101 102
Stiffness of the treated and untreated samples was evaluated according to AATCC Test Method (D 1388-96). Surface roughness of the treated and untreated samples was evaluated according to JIS 94 Standard, using surface roughness measuring instrument, SE 1700α (Japan).
ip t
99
Water and oil repellency were evaluated according to AATCC Test Method 22-1989.
104
Scanning electron microscope (SEM) images of some selected samples were obtained with
105
a JEOL, JXA-840A electron probe micro-analyzer, equipped with energy disperse X-ray
106
spectroscopy (EDX) for the composition analysis.
Standard Method (D 737-96).
109
3. Results and Discussion
us
an
pt
110
M
108
Durability to washing was evaluated for some selected samples according to ASTM
ed
107
cr
103
Factors affecting the imparted functional properties and pigment printing properties of
112
cotton/wool and viscose/wool blended fabrics brought about by individual incorporation of
113
certain functional finishing agents, namely chitosan, Aloe vera, triclosan derivative, TiO2-NP's,
114
silicon softener and water-oil repellent into the pigment paste formulation, using different
115
pigment colorants, followed by screen printing and microwave curing were thoroughly
116
investigated. Discussion of the obtained results follows.
Ac ce
111
117 118 119 6
Page 6 of 32
120
3.1. Type and concentration of functional finishing agent Fig 1 (a) shows the influence of chitosan concentration on the extent of pigment coloration,
122
expressed as K/S value. For a given set of printing paste formulation and curing conditions, it is
123
clear that increasing chitosan concentration up to 2.5g/Kg paste results in a remarkable
124
improvement in the depth of obtained pigment prints, regardless of the used substrate. This
125
improvement in K/S values is a direct consequence of enhancing the extent of encapsulation,
126
fixation and adhesion of the dispersed pigment particles, which have no affinity for any fibre,
127
onto the substrate via enhancing the film forming properties and providing an extra active sites,
128
i.e.
129
et.al. 2005; Ibrahim et.al.2010c; Yaman et.al. 2012; Giesen & Eisenlohr 1994). Further increase
130
in the chitosan concentration, beyond 2.5 g/Kg, is accompanied by a gradual decrease in the
131
depth of the obtained prints most probably due to the gradual increase in the pigment print paste
132
viscosity as well as a reduction in paste uptake/binder film formation and subsequent pigment
133
entrapment during the microwave curing step. On the other hand, the extent of pigment fixation
134
follows the decreasing order cotton/wool > viscose/wool reflects the differences between them in
135
fabric structure, weight, porosity, thickeners, morphology, amount and availability of the
136
chemical groups of the substrate components, which influence the extent of fixation and
137
adhesion strength of the binder-to-fibre, as well as extent of undue penetration of dispersed
138
pigment particles (Ibrahim et.al., 2013a & 2013b).
cr
us
pt
ed
M
an
–NH2 and –OH groups, for cross-linking and pigment particles accommodation (Ibrahim
Ac ce
139
ip t
121
140
Fig. 1 (b) shows that increasing Aloe vera gel, a naturally occurring biopolymer,
141
concentration up to 10g/Kg pigment paste is accompanied by a noticeable increase in the K/S
142
values of the obtained pigment prints irrespective of the used substrate. The enhancement in the
7
Page 7 of 32
K/S value is determined by type of substrate: cotton/wool (K/S= 22.0) > viscose/wool (K/S=
144
16.63). This remarkable increase in the K/S values most probably reflects the positive impacts of
145
potentially active chemical constituents of Aloe vera gel such as carbohydrates, anthraquinones,
146
organic compounds and lipids, proteins, enzymes and amino acids along with their active groups,
147
e.g. – OH, -COOH, -NH2 groups (Hamman 2008; Moghaddasi & Verma, 2011), on enhancing
148
the extent of formation of flexible three dimension binder film that encapsulates and entraps
149
pigment particles and adheres them to fabric surfaces during microwave fixation step with a
150
consequent darker depth of shades. Further increase in Aloe vera gel concentration up to 20 g/Kg
151
is followed by a slight decrease in the fixation of the pigment particles, regardless of the used
152
cellulosic/wool blended substrate.
an
us
cr
ip t
143
M
153
Fig. 1 (c) illustrates the effect of incorporating triclosan derivative, at different
155
concentration (0-20 g/kg pigment paste) in the printing paste on the K/S values of the obtained
156
pigment prints. Within the range examined the so-obtained results indicate that increasing
157
triclosan concentration up to 10g/Kg results in increasing the K/S value of the cotton/wool prints
158
from 17.48 up to 20.52 and viscose/wool prints from 14.02 up to 15.52. This can be discussed in
159
terms of better encapsulation, binding and fixation of pigment particles onto the fabrics surface
160
via the cross-linked binder film. Further increase in triclosan derivative concentration results in a
161
slight decrease in the depth of the obtained prints; i.e. less extent of pigment fixation.
pt
Ac ce
162
ed
154
163
As far as the changes in the K/S values of the obtained pigment prints as a function of the
164
TiO2-NP's concentration, Fig. 1 (d) shows that the maximum values of K/S (20.92 and 19.00) for
165
cotton/wool and viscose/wool respectively, attained at a TiO2-NP's concentration 10g/Kg
8
Page 8 of 32
pigment paste. It may be due to the positive role of TiO2-NP's, as a co-catalyst, in enhancing the
167
extent of cross-linking of the binder film thereby improving the performance of capturing and
168
entrapping pigment particles with subsequent adhesion to and fixation onto the fabrics surface
169
(Ibrahim et.al., 2010a; Wang et.al., 2005; Nazariet et.al., 2009). Further increase in TiO2-NP's,
170
beyond 10g/Kg, has a slight negative impact on the depth of the obtained prints as manifested by
171
a decrease in the K/S values irrespective of the used substrate.
cr
us
172
ip t
166
On the other hand, Fig. 1(e) shows that inclusion of the quaternary polydimethyl siloxane
174
softener Ultratex® HMT up to 20g/Kg, into the pigment printing paste along with other
175
ingredients is accompanied by a significant increase in K/S value of the printed cellulosic/wool
176
substrates, most probably due to the better accommodation and fixation of the pigment particles
177
within the binder and/or the softener film onto the printed fabrics surface (Schindler & Hauser,
178
2004 & Ibrahim et.al., 2005). Further increase in the softener film has practically no significant
179
effect.
M
ed
pt
180
an
173
Moreover, Fig. 1 (f) shows the effect of the used water/oil repellent agent, Ciba®
182
Oleophobol, concentration on the K/S values of the obtained pigment prints. It is clear that depth
183
of the printed fabric samples is gradually increased as the water/oil repellent concentration
184
increase up to 40g/Kg then decreases slightly. This enhancement in K/S values could be
185
discussed in terms of the formation of water/oil repellent polymer film alone or in combination
186
with other components, i.e. binder and cross-linker, during the microwave curing step, thereby
187
increasing the extent of fixation of pigment particles onto the coated fabric surface (Schindler &
Ac ce
181
9
Page 9 of 32
188
Hauser, 2004, Ibrahim et.al. 2010d). Further increase in the water/oil repellent agent results in a
189
marginal decrease in the depth of the obtained prints.
190
Based on the aforementioned studies, incorporation of chitosan (2.5g/Kg), Aloe vera gel
192
(10g/Kg), triclosan derivative (10g/Kg), TiO2-NP's (10g/Kg), silicone softener (20g/Kg), or the
193
water-oil repellent agent (40g/Kg) into the pigment printing paste formulation followed by
194
screen printing and microwave fixation at 1300w/4 min seems to be a proper concentration for
195
obtaining the higher depth of the obtained pigment prints, keeping other parameters constant.
us
cr
ip t
191
197
an
196
3.2. Combined functional finishing and pigment printing in one step Results of the foregoing section made it possible to obtain pigment prints with darker depth
199
of shade along with expected functional properties by including the nominated functional
200
additives, at the proper concentrations, into the print paste. With this in mind, systematic study
201
was carried out to investigate the impact of using the nominated additives along with different
202
pigment colorants on the functional and printing properties of the simultaneously finished and
203
printed cellulosic/wool fabrics.
205
ed
pt
Ac ce
204
M
198
3.2.1. Antimicrobial finishing/pigment printing
206
The antimicrobial and pigment properties of printed cotton/wool and viscose/wool blended
207
fabrics in the absence and presence of chitosan (2.5g/Kg), Aloe vera (10g/Kg) or triclosan
208
derivatives (10g/Kg) were assessed and presented in Table 1. For a given set of printing
209
conditions, the data in Table 1 signify that: i) incorporation of any of the nominated active
210
ingredients into the printing paste results in a remarkable improvement in the antibacterial
10
Page 10 of 32
activity, expressed as ZI value, against the G+ve (S. aureus) and G-ve (E. coli) bacteria, ii) the
212
extent of improvement in the imparted antimicrobial properties is governed by the type of
213
functional additive: chitosan > Aloe vera > triclosan >> none, kind of substrate: cotton/wool >
214
viscose/wool, as well as pigment colorant: Pigment Orange 13 > Pigment Red 146 > Pigment
215
Blue 153, keeping other parameters fixed, iii) the variation in the antibacterial activity of the
216
obtained pigment prints using chitosan, Aloe vera or triclosan could discussed in terms of the
217
differences among them in: chemical structure, active ingredients, i.e. amino groups in chitosan,
218
antiseptic agent (lupeol, salicylic acid, urea nitrogen, cinnamonic acid, phenols and sulfur) in
219
Aloe vera or a chlorinated bis-phenols as in case of triclosan (Ibrahim et.al., 2010c, Zemljic
220
et.al., 2009, Moghaddasi & Verma, 2011; Orhan et.al., 2007), compatibility with other
221
ingredients in the printing paste, extent of fixation and loading onto the printed fabric surface as
222
well as, iv) the difference in mode of antibacterial action, i.e. by interfering with bacterial
223
metabolism and/or binding with DNA to inhibit mRNA synthesis due to the polycationic nature
224
of chitosan especially in acidic medium (Zitao et.al., 2003; Kong et.al., 2010), via an
225
electrochemical mode of action of penetrate and disrupt the cell walls of bacterial as in case of
226
using Aloe vera thereby preventing the bacteria from functioning or reproducing (Jothi, 2009;
227
Sarkar et.al., 2003), or by inhibiting fatty acid biosynthesis through the blocking of lipid bio-
228
synthesis as in case of using triclosan derivative (Orhan et.al., 2009; Ibrahim et.al., 2013;
229
Ibrahim et.al., 2010e).
cr
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230
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211
231
On the other hand, incorporation of chitosan, Aloe vera or triclosan derivative into the
232
pigment printing paste is accompanied by an improvement in both the depth of the obtained
233
prints along with their fastness properties, regardless of the used pigment colorant. This
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Page 11 of 32
improvement in printing properties, i.e. K/S and fastness properties reflects the positive role of
235
the aforementioned functional additives in enhancing the extent of fixation and accommodation
236
of extra pigment particles within the cross-linked network formed onto the fabric surface during
237
the microwave fixation step. Moreover, the variation in the printing properties upon using the
238
aforementioned additives may be attributed to their differences in chemical structure, functional
239
groups, extent of fixation and interaction among other ingredients during the fixation step as well
240
as the differences among the used pigments in particle size, chemical composition, location and
241
extant of distribution, color, hue as well as subsequent immobilization onto the fabric surface
242
(Ibrahim et.al., 2005; Uddin & Lomas, 2005; Yaman et.al., 2012).
an
us
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234
243
Furthermore, the imparted antibacterial properties as well as the extant of pigment printing,
245
in general, depend on the fabric structure, its functional groups, availability and accessibility of
246
its active sites, mode of interaction and extent of modification, as well as location and extent of
247
distribution of the formed film incorporating different ingredients, especially the antibacterial
248
pendant groups and the pigment particles.
ed
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249
M
244
250
Table 1 also clearly indicates that the effectiveness against the most common causes of
251
bacterial infection, i.e. E. coli and S. aureus bacteria, follows the decreasing order G+ve > G-ve,
252
irrespective of the used functional additive. This reflects the differences between the nominated
253
bacteria in cell wall structure, sensitivity to disruption and/or in response to inactivation (Gupta
254
et.al., 2008; Gouda & Ibrahim, 2008).
255 256
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Page 12 of 32
257 258
3.2.2. Antibacterial/ anti-UV/ pigment printing To evaluate the dual role of TiO2-NP's as antibacterial and anti-UV agent, TiO2-NP's
260
(10g/Kg) were included into the pigment printing paste followed by screen printing and
261
microwave fixation. The data in Table 2 indicate that incorporate of TiO2-NP's into the printing
262
paste results in: i) a remarkable improvement in the antibacterial activity, expressed as ZI values,
263
as well as in the UV-protecting properties, expressed as UPF values, of the printed fabric
264
samples, ii) an improvement in both the depth of the obtained pigment prints along with their
265
fastness properties, regardless of the used pigment colorant, iii) the enhancement in the imparted
266
antibacterial functional property as well as the printing properties is determined by the type of
267
substrate and follows the decreasing order: cotton/wool > viscose/wool, keeping other
268
parameters constant and iv) the change in the pigment printing properties is governed by the type
269
of pigment colorant as mentioned before.
cr
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270
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259
The imparted multifunctional properties, anti-bacterial/ anti-UV, reflects the dual role of
272
loaded TiO2-NP's in i) generation of extremely reactive species, e.g. superoxide ions, hydroxyl
273
radicals...etc, thereby enhancing the extent of attacking the bacterial cell membrane, losing of its
274
essential functions and destroying it (Ibrahim et.al., 2010a; Ibrahim et.al., 2012b; Chen & Wang,
275
2006), as well as ii) scattering and absorbing the harmful UV-B radiation (Ibrahim et.al., 2012b;
276
Ibrahim et.al., 2010a; Ibrahim et.al., 2013a; Abidi et.al., 2007).
Ac ce
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271
277 278
It is also clear from the Table 2 that: i) the nominated G+ve bacteria are more susceptible to
279
the action of the loaded TiO2-NP's than the G-ve bacteria, regardless of the used substrate, ii) the
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Page 13 of 32
darker the depth of the shade, the greater is the UV-protection, irrespective of the used pigment
281
colorant, iii) the UPF-values of the functionalized pigment prints is governed by the extent of
282
loading TiO2-NP's onto the substrate: viscose/wool > cotton/wool , as well as the kind of
283
pigment colorant, iv) the enhancement in the pigment printing properties upon inclusion of TiO2-
284
NP's into the printing paste could be ascribed to the positive role of the TiO2-NP's as a co-
285
catalyst for cross-linking and intensifying the extent of polymerization and fixation of the binder
286
film onto fabrics surface and subsequent fixation and entrapment of extra pigment particles
287
(Chen & Wang, 2006; Nazari et.al., 2009; Dastjerdi & Motazer, 2010), and v) the slight
288
improvement in the light fastness properties of the obtained pigment prints could be attributed to
289
the UV light- absorption capacity of the loaded TiO2-NP's.
an
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280
291
M
290
3.2.3. Soft-handle finishing and pigment printing in one step For given set of soft-finishing and pigment printing of the nominated substrates using
293
different pigment colorants, the data in Table 3 demonstrate that: i) inclusion of the silicone
294
softener in the printing paste, 20 g/Kg, results in a significant improvement in the smoothness
295
along with a remarkable reduction in the stiffness of the produced pigment prints, ii) the positive
296
variation in the aforementioned surface properties reflects the positive role of silicone film as a
297
lubricating agent between the fibers in the yarn and between the yarns of the fabric, thereby
298
imparting softness and minimizing stiffness (Wahle & Falkowski, 2002; Harbered & Bereck,
299
2002; Hashem & Ibrahim, 2002; Ibrahim et.al., 2009), ii) the extent of reduction in fibre friction
300
which results in soft yarn and improved fabric handle, in the presence and absence of silicone
301
softener, is governed by the type of substrate and its components and follows the decreasing
302
order: viscose/wool > cotton/wool, iii) the enhancement in the printing properties, i.e. K/S and
Ac ce
pt
ed
292
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Page 14 of 32
fastness properties, reflects the positive role of the silicone micro emulsion in leading to better
304
extent of binding film orientation, formation and/or distribution on the fabric surface thus
305
creating a proper conditions for accommodation and anchoring of pigment particles as well as
306
their fixation during the microwave curing step (Ibrahim et.al., 2005).
308
3.2.4. Concurrent water/oil repellent and pigment printing
cr
307
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303
Table 4 shows that printing of the nominated substrates in the presence of the water/oil
310
repellent additive (40g/Kg) followed by screen printing and microwave fixation is accompanied
311
by a remarkable increase in water/oil repellent ratings 70/6, and 50/5 for cotton/wool and
312
viscose/wool fabric respectively. The type of pigment colorant has practically no effect on the
313
imparted repellent properties. The imparted functional properties are governed by type of
314
substrate and follow the decreasing order: cotton/wool > viscose/wool fabric. The improvement
315
in the repellent properties is attributed to the formation of a hydrophobic/oleophobic polymer
316
film on the printed fabric surface thereby lowering the fabric surface energy and hence repellent
317
properties (Abo-Shosha et.al., 2009; Ibrahim et.al., 2010d). Incorporation of the nominated
318
water/oil repellent in the printing paste has a positive impact on the depth of the obtained prints
319
along with a slight enhancement in the fastness properties ratings as a direct consequence of
320
increasing the extent of entrapment and entanglement of the pigment particles within the cross-
321
linked polymer film onto the fabric surface.
an
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322
us
309
323
On the other hand, the data so obtained signify that inclusion of the used water/oil-repellent
324
results in a remarkable reduction in the roughness, i.e. promoting surface smoothening, of the
325
obtained pigment prints as a direct consequence of the deposition of a hydrophobic smooth film
15
Page 15 of 32
326
on the fibre and fabric surface. The extent of improvement in surface smoothening is governed
327
by type of substrate i.e. viscose/wool > cotton/wool, keeping other parameters constant.
328
3.2.5. SEM images and EDX spectra
ip t
329
The SEM was used to observe the cotton/wool and viscose/wool blended fabrics before
331
(Fig. 2a & c) and after printing (Fig. 2b & d) respectively in the presence of certain functional
332
additives namely Aloe vera, TiO2-NP's (Fig. 3a & c) and the water/oil repellent (Fig. 3e & g)
333
respectively. According to the given SEM images, the pigment printed fabric surfaces were
334
clearly covered with deposited printing paste and loaded with the pigment particles along with
335
the nominated active ingredients; endow the fabric functionalization and coloration.
an
us
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330
On the other hand, EDX spectra of pigment printed cotton/wool and viscose/wool fabric
337
samples and loaded with TiO2-NP's (Fig. 3b & d) or the water/oil repellent (Fig. 3f & h)
338
confirmed the existence of titanium element or silicon and fluorine elements respectively on the
339
obtained pigment prints. The results were reported based on both the weight percentages (%).
340
Once again, the distribution of the deposited printing paste onto the fabric surface is influenced
341
by type and morphology of untreated substrate.
343
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342
M
336
3.2.6. Durability to wash
344
The durability of the imparted functional properties as well as the retained depth of shade,
345
expressed as K/S values, of some pigment prints until 15 laundering cycles were determined
346
according to ASTM Standard Test (D737-96) and demonstrated in Table 5. For a give set of
347
printing condition, the data in Table 5 signify that: i) inclusion of the nominated functional
348
additives in the printing paste results in a significant improvement in the imparted functional
16
Page 16 of 32
properties along with an enhancement in the depth of the obtained pigment prints, ii) the
350
durability to wash, after 15 washing cycles, was slightly decreased, which can be discussed in
351
terms of desorption and/or removal of physically absorbed or unfixed active ingredients and
352
pigment particles, iii) the extent of retention of the imparted properties as well as the pigment
353
particles onto the printed substrate are governed by type of functional additive, kind of substrate,
354
along with the ability to form a durable three-dimensional cross-linked sheath or film containing
355
both the active species and the pigment particles on the fabric surface and iv) the obtained
356
functionalized pigment prints exhibited very sufficient: antibacterial and/or UV-blocking
357
properties, soft-handle, or water/oil repellency in addition to high depth of shades even after 15
358
washing cycles.
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349
361
4. Conclusions
Functionalized cotton/wool and viscose/wool pigment prints were achieved by individual
ed
360
M
359
including of chitosan (2.5g/Kg), Aloe vera (10g/Kg), triclosan (10g/Kg), TiO2-NP's
363
(10g/Kg), silicone softener (20g/Kg) or the water/oil repellent agent (40g/Kg) in the print
364
paste, followed by screen printing and microwave fixation at 1300W/4 min.
Ac ce
365
pt
362
The enhancement in the imparted functional properties such as antibacterial,
366
antibacterial/UV-protection, soft-handle or water-repellency with the improve in the
367
printing properties are governed by both the type of the functional additive and the kind
368
of substrate.
369 370
The functionalized pigment prints were found to have good functionality and printability even 15 consecutive laundering cycles.
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Page 17 of 32
371
Finally, the obtained results have important practical implications for the establishment of
372
simultaneous functional finishing and pigment printing in one step process talking both
373
the environmental and economical aspects in concern. References
375
Abidi, N., Hequete, E., Tarimala, S. & Dai, I. I. (2007), Cotton fabric surface modification for
376
improved UV-radiation protection using sol- gel process", Journal of Applied Polymer Science,
377
104, 111-117.
378
Abo-Shosha, M. H., El-Hilw, Z. H., Aly, A. A. & Amr, A. (2009), New textile water repellent
379
based on reaction of toluene 2, 4-diisocyanate with stearyl alcohol, AATCC Review, 9 (7), 38-
380
42.
381
Bajaj, P. (2002), Finishing of textile materials, Journal of Applied Polymer Science, 83, 631-659.
382
Bozzi, A, Yuranova, T. & Kiwi, J. (2005), Self cleaning of wool-polyamide and polyester
383
textiles by TiO2-rutile modification under daylight irradiation at ambient temperature, Journal of
384
Photochemistry and Photobiology A: Chemistry, 172, 27-34.
385
Chen, C. C. & Wang, C. C. (2006), Crosslinking of cotton cellulose with succinic acid in the
386
presence of titanium dioxide nano-catalyst under UV-irradiation, Journal of Sol-Gel Science and
387
Technology, 40, 31-38.
388
Dastjerdi, R. & Montazer, M. (2010), A review on the application of inorganic nano-structured
389
materials in the modification of textiles: Focus on anti-microbial properties, Colloids and
390
Surfaces B: Biointerfaces, 79, 5-18.
391
Giesen, V. & Eisenlohr, R. (1994), Pigment printing, Review progress coloration, 24, 26-30.
392
Gouda, M., Ibrahim, N. A. (2008), New approach for improving antibacterial function to cotton
393
fabric, Journal of Industrial Textiles 37, 327-339.
Ac ce
pt
ed
M
an
us
cr
ip t
374
18
Page 18 of 32
Growri, S., Almeida, L., Amorim, T., Carneiro, N., Souto, A. P., & Esteves, M. F. (2010),
395
Polymer nonaparticles for multifunctional finishing of textiles-A review, Textile Research
396
Journal, 80, 1290-1306.
397
Gupta, P., Bajpai, M. & Bajpai, S. K. (2008), Investigation of antibacterial properties of silver
398
nanoparticles-loaded poly (acrylamide-co-itaconic acid)-grafted cotton fabric, Journal of Cotton
399
Science, 12, 280-286.
400
Habered, P. & Bereck, A. (2002), part 2: Silicone softeners, Review Progress Coloration, 32,
401
125-136.
402
Hamman, J. H. (2008), Composition and application of Aloe vera leaf gel, Molecules, 13, 1599-
403
1616.
404
Hashem, M. & Ibrahim, N. A. (2002), Response of linen fabric to finishing treatments, Journal
405
Textile Association, 63, 189-194.
406
Hebeish, A & Ibrahim, N. A. (2007), The impact of frontier sciences on textile industry,
407
Colourage Annual, 54, 41-55.
408
Holme, I. (2007), Innovative technologies for high performance textiles, Coloration Technology,
409
123, 59-73.
410
Hsieh, Y. L. (2007), Chemical structure and properties of cotton. In Cotton: Science and
411
Technology, Gordan, S. and Hsieh, Y. L. (Eds.), Woodhead, Cambridge.
412
Ibrahim, N. A., El-zairy, M. R., Zaky, S. & Borham, H. A. (2005), Environmental sound
413
synthetic pigment printing using synthetic thickening agents, Polymer-Plastics Technology and
414
Engineering, 44, 111-132.
415
Ibrahim, N. A., Gouda. M. & Zairy, W. M. (2008), Enhancing easy care and antibacterial
416
functions of cellulose/wool blends, Journal of Natural Fibers, 5, 347-365.
Ac ce
pt
ed
M
an
us
cr
ip t
394
19
Page 19 of 32
Ibrahim, N. A., Gouda, M., Husseiny, Sh. M., El-Gammal, R. M. & Mahrous, F. (2009), UV-
418
protecting and antibacterial finishing of cotton knits, Journal of Applied Polymer Science, 112,
419
3589-3596.
420
Ibrahim, N. A., Refai, R., & Ahmed, A. F. (2010a), Novel approach for attaining cotton fabric
421
with multifunctional properties, Journal of Industrial Textiles, 40, 65-83.
422
Ibrahim, N. A., Mahrous, F., El-Gamal, A. R., Gouda. M. & Husseiny, Sh. M. (2010b),
423
Multifunctional anionic cotton dyeing, Journal of Applied Polymer Science, 115, 3249-3255.
424
Ibrahim, N. A., El-Zairy, E. M. R., El-Zairy, M. R. and Khalil, H. M. (2010c), Improving
425
transfer printing and UV-blocking properties of polyester-based textiles using MCT-βCD,
426
chitosan and ethylenediamine, Coloration Technology 126, 330 -336.
427
Ibrahim, N. A., Amr, A., Eid, B. M. and El Sayed, Z. M. (2010d), Innovative multifunctional
428
treatments of ligno-cellulosic jute fabric, Carbohydrate Polymers, 82, 1198-1204.
429
Ibrahim, N. A., Hashem, M., El-Sayed, W. A., El-Husseiny, Sh., Elanany, E. M. (2010e),
430
Enhancing antimicrobial properties of dyed and finished cotton/polyester fabrics, AATCC
431
Review, 10, 55-63.
432
Ibrahim, N. A. (2011), Dyeing of textile fibre blends, In M.Clark (Ed.), Handbook of textile and
433
industrial dyeing, vol. 2: Application of dyes (pp.147-172), Oxford: Woodhead publishers,
434
Chapter 4.
435
Ibrahim, N. A., Eid, B. M. & El-Batal, H. (2012a), A novel approach for adding smart
436
functionalities to cellulosic fabrics, Carbohydrate Polymers, 87, 744-751.
437
Ibrahim, N. A., Amr, A., Eid, B. M., Mohammed, Z. E. and Fahmy, H. M. (2012b), Poly (acrylic
438
acid)/poly (ethylene glycol) adduct for attaining multifunctional cellulosic fabrics, Carbohydrate
439
Polymers 89, 648-660.
440
Ibrahim, N. A., El-Zairy, E. M. R., Abdalla, W. A. and Khalil, H. M. (2013a), Combined UV-
441
protecting and reactive printing of cellulosic/wool blends, Carbohydrate Polymers, 92, 1386-
442
1394.
Ac ce
pt
ed
M
an
us
cr
ip t
417
20
Page 20 of 32
Ibrahim, N. A., Abdalla, W. A., El-Zairy, E. M. R. and Khalil, H. M. (2013b), Utilization of
444
monochloro-triazine β-Cyclodexrtin for enhancing printability and functionality of wool,
445
Carbohydrate Polymers 92, 1520-1529.
446
Jothi, D. (2009), Experimental study on antimicrobial activity of cotton fabric treated with aloe
447
gel extract from aloe vera plant for controlling the Staphylococcus aureus (bacterium), African
448
Journal of Microbiology Research, 3, 228-232.
449
Judd, D. & Wyszeck, G. (1975), Color in business science and industry, 3rd ed., New York: John
450
Wiley & Sons.
451
Kong, M., Chen, X. G., Xing, K. & Park, H. J. (2010), Antimicrobial properties of chitosan and
452
mode of action: A state of the art review, International Journal of Food Microbiology, 144, 51-
453
63.
454
Lewis, D. M. (2011), Coloration of wool, in M. Clark (Ed.), Handbook of textiles and industrial
455
dyeing, vol. 2: Applications of dyes, pp. (6-7), Oxford: Woodhead publisher, Chapter 1.
456
Moghaddasi, M. S. & Verma, S. K. (2011), Aloe vera their chemicals composition and
457
applications: A review, International Journal of Biological & Material Research, 2, 466-471.
458
Nazari, A., Montazer, M. & Rahimi, M. K. (2009), Concurrent antimicrobial and crosslinking of
459
bleached and cationic cotton using nano- TiO2 and BTCA, Iranian Polymer Science and
460
Technology Journal, 22, 41-51.
461
Nazari, A., Montazer, M., Rashidi, A., Yazdanshenas, M. & Abbasinejad, M. A. (2009), Nano-
462
TiO2 photo-catalyst and sodium hypophosphite for crosslinking cotton with polycarboxylic acids
463
under UV and high temperature, Applied Catalysis A: General, 371, 10-16.
464
Orhan, M., Kut, D., & Gunesoglu, C. (2007), Use of triclosan as antibacterial agent in textiles,
465
Indian Journal of Fibre & Textile Research, 32, 114-118.
466
Orhan, M., Kut, D. & Gunesoglu, C. (2009), Improving the antibacterial activity of cotton fabrics
467
finished with triclosan by the use of 1, 2, 3, 4- butanetetracarboxylic acid and citric acid, Journal
468
of Applied Polymer Science, 111, 1344-1352.
Ac ce
pt
ed
M
an
us
cr
ip t
443
21
Page 21 of 32
Sarkar, R. K., Purushottam, D. E. & Chanuhan, P. D. (2003), Bacteria-resist finish on cotton
470
fabrics using natural herbal extracts, Indian Journal of Fibers & Textile Research, 28, 322-331.
471
Schindler, W. D & Hauser, P. I. (2004), Chemical finishing of textiles, Woodhead Publisher,
472
Cambridge, England.
473
Simoncic, B., & Tomsic, B. (2010), Structure of novel antimicrobial agents for textiles-A review,
474
Textile Research Journal, 80, 1721-1737.
475
Uddin, F. & Lomas, M. (2005), Combined crease recovery finishing and pigment printing,
476
Coloration Technology, 121, 158-163.
477
Wahle, B. & Falkowski, J. (2002), Softeners in textile processing, part 1: An overview, Review
478
Progress Coloration, 32, 118-124.
479
Wang, C. C. & Chen, C. C. (2005), Physical properties of crosslinked cellulose catalyzed with
480
nano-titanium dioxide, Journal of Applied Polymer Science, 97, 2450-2456.
481
Yaman, N., Ozdogan, E. & Seventekin, N., (2012), Improvement in fastnesses and color strength
482
of pigment printed textile fabric, Journal of Engineered Fibers & Fabrics, 7, 40-46.
483
Zemljic, L. F., Strand, S., Sauperl, O. X. & Kleinschek, K. S. (2009), Characterization of amino
484
groups for cotton fabrics coated with chitosan, Textile Research Journal, 79, 219-226.
485
Zitao, Z., Chen, L., Jinmin, J., Yanliu, H. & Donghui, C. (2003), Antibacterial properties of
486
cotton fabrics treated with chitosan, Textile Research Journal, 73, 1103-1106.
488
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489 490 491
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492
List of Figures
493 494 495 496 497 498 499 500 501 502 503 504 505 506
Fig.1. Effect of Chitosan (a), Aloe vera (b), Triclosan (c), TiO2-NP's (d), Silicone Softener (e), and Oleophobol® (f) concentration on the depth of the obtained prints.
ip t
Printing paste components: Pigment Red 146(20g/Kg); synthetic thickener(20g/Kg); Printofix®Binder - MTB(100g/Kg); cross-linker(10g/Kg); and (NH4)2S2O8(2g/Kg). Microwave fixation: 1300W/4min.
cr
Fig.2. SEM of untreated Cotton/Wool fabric (a), SEM of treated Cotton/Wool fabric with Aloe vera (b), SEM of untreated Viscose/Wool fabric (c), SEM of treated Viscose/Wool fabric with Aloe vera (d).
us
Fig.3. EDX image and element content of TiO2-NP’s loaded Cotton/Wool blend (a, b) and Viscose/Wool blend (c, d), EDX image and element content of water/oil repellent loaded Cotton/Wool blend (e, f) and Viscose/Wool blend (g, h).
an
507 508
M
509 510
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Page 23 of 32
Highlights
512
-
Functionalized Cellulosic/Wool pigment prints
513
-
Inclusion of certain functional additives
514
-
Functional finishing and pigment printing in one step
515
-
Innovative pigment prints with durable functionalities
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516
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511
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517
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Page 24 of 32
Table 1
Table1. Antibacterial/printing properties of printed cellulosic/wool blended fabrics using different pigment colorants along with antimicrobial additives in the printing paste a
Pigment Blue 153
Cotton/ Wool
Viscose/ Wool
Wet
4-5 (4)
4-5 (4)
4-5 (4)
4 (3-4)
4-5 (3-4)
22.00
4-5
4-5
4-5
4-5
4-5
13.0
20.52
4-5
4-5
5
4-5
4-5
19.0 (00.0)
18.0 (00.0)
19.43 (14.02)
4 (3-4)
4 (3-4)
4 (3-4)
4 (3)
4 (3)
Aloe vera
16.0
14.5
16.63
4-5
4-5
4-5
4
4
Triclosan
13.5
11.5
15.52
Chitosan
21.0 (00.0)
18.0 (00.0)
13.22 (11.60)
Aloe vera
18.0
16.0
Triclosan
14.0
12.0
Chitosan
18.0 (00.0)
16.0 (00.0)
Aloe vera
14.0
13.0
22.0 (00.0)
20.0 (00.0)
21.61 (17.48)
Aloe vera
19.5
17.0
Triclosan
15.5
Chitosan
Triclosan
4-5
4
4
4-5 (4)
4-5 (3-4)
4-5 (3)
4 (3)
4-5 (4)
16.39
5
4-5
4-5
4
4-5
14.78
4-5
4-5
3-4
3-4
4-5
12.52 (11.25)
4-5 (4)
4-5 (3-4)
4-5 (3)
4 (3)
4-5 (4)
15.55
4-5
4-5
4-5
4
4-5
13.34
4-5
4-5
4
4
4-5
24.0 (00.0)
22.0 (00.0)
8.61 (6.75)
5 (4)
4-5 (4)
4-5 (4)
4 (3-4)
5 (4)
20.5
19.0
10.35
4-5
4-5
4-5
4-5
5
Triclosan
18.0
16.0
9.93
4-5
4-5
4-5
4-5
5
Chitosan
20.5 (00.0)
18.5 (00.0)
8.31 (6.24)
4-5 (3)
4 (3)
4 (3)
4 (3)
4 (3-4)
Aloe vera
16.5
15.0
10.03
4
3-4
4
4
4
Triclosan
14.5
12.5
9.52
4
4
4-5
4-5
4
Aloe vera
Ac a
4-5
10.0
ce pt
Pigment Orange 13
-
Viscose/ Wool
4-5
12.0
Chitosan Cotton/ Wool
cr
Chitosan
ip t
Dry
G −ve
us
Viscose/ Wool
LF f
St.
Alt
G +ve
an
Pigment Red 146
Cotton/ Wool
K/S
Additive
RF e
c
M
Substrate
WF d
ed
Pigment
ZI b (mm)
Printing paste components : pigment colorant (20 g/Kg); synthetic thickener (20g/Kg); binder
(100g/Kg); cross-linker (10g/Kg); catalyst (2g/Kg) in the absence and presence of Chitosan (2.5g/Kg), Aloe vera (10g/Kg) or Triclosan (10g/Kg). Microwave fixation at 1300W/4min.
-
b
ZI: zone of inhibition; c K/S: color strength; d WF: wash fastness; Alt: alteration; St. staining on
cotton; e RF: rubbing fastness; f LF: light fastness. -
Values in parenthesis are the values of the pigment prints in the absence of the aforementioned functional additives.
24 Page 25 of 32
Table 2
Table 2. Antibacterial/UV-protecting and printing properties of printed cellulosic/wool blended fabrics using different pigment colorants along with TiO2-NP's in the printing paste a .
Pigment Red 146
Substrate
WF e UPF
TiO2-NP's (10g/Kg)
G +ve
G −ve
Without
00.0
00.0
63
With
16.0
15.0
Without
00.0
With
c
K/S
St.
Dry
Wet
17.48
4
4
4
3-4
80
20.91
4-5
00.0
74
14.02
13.0
11.5
99
19.03
Without
00.0
00.0
60
11.60
With
23.0
20.0
76
Without
00.0
00.0
85
With
18.0
17.0
Without
00.0
00.0
With
21.0
Without
00.0
a
4
cr
3
3
4-5
4-5
4
4
4
4
3-4
3
3
4
13.89
4-5
4-5
4-5
4
4-5
11.25
4
3-4
3
3
4
118
13.40
5
4-5
4-5
4
4-5
81
6.75
4
4
4
3-4
4
us
an
ed 18.0
95
9.87
5
4-5
4-5
4
4-5
00.0
98
6.24
3
3
3
3
3-4
137
8.98
4
3-4
4
4
4
ce pt 15.0
With
4
3-4
M
Pigment Blue 153 Pigment Orange 13
Cotton/ Wool
4-5
3-4
Cotton/ Wool
Viscose/ Wool
4-5
3-4
3-4
Viscose/ Wool
-
LF g
Alt
Cotton/ Wool
Viscose/ Wool
RF f
d
ip t
Pigment
ZI b (mm)
13.0
Printing paste components : pigment colorant (20 g/Kg); synthetic thickener (20g/Kg); binder (100g/Kg); cross-
Ac
linker (10g/Kg); catalyst (2g/Kg) in the absence and presence of TiO2-NP's (10g/Kg). Microwave fixation at 1300W/4min. -
b
ZI: zone of inhibition;
c
UPF: ultraviolet protection factor;
d
K/S: color strength;
e
WF: wash fastness; Alt:
alteration; St. staining on cotton; f RF: rubbing fastness; g LF: light fastness.
25 Page 26 of 32
Table 3
Table3. Softness and printing properties of printed cellulosic/wool blended fabrics using different
Pigment Red 146
Substrate
WF c
Surface roughness (mm)
Stiffness
Without
29.05
3833
17.48
4
With
15.96
1340
25.02
4-5
Without
22.54
2519
14.02
3-4
3-4
With
13.41
1114
16.90
4
26.95
4100
11.60
With
14.98
1768
Without
23.11
1866
With
14.03
Without
25.49
With
14.10
Without
21.68
Silicon softener (20g/Kg)
K/S
Alt
-
a
13.25
4
4
3-4
4-5
4-5
3-4
3
3
4
4
4
4-5
cr
5
3-4
3
3
4
17.64
4-5
4
4-5
4
5
11.25
4
3-4
3
3
4
1458
15.81
4-5
4-5
4
4
4-5
2880
6.75
4
4
4
3-4
4
2099
9.47
4-5
4-5
4-5
4-5
4-5
2548
6.24
3
3
3
3
3-4
1865
9.06
3-4
3-4
4
4
4
ed
ce pt With
Wet
3-4
an
M
Pigment Blue 153 Pigment Orange 13
Viscose/ Wool
Dry
4
Cotton/ Wool
Cotton/ Wool
St.
4-5
Viscose/ Wool
Viscose/ Wool
LF e
us
Cotton/ Wool
Without
RF d
b
ip t
Pigment
pigment colorants along with Silicone softener in the printing paste a .
Printing paste components : pigment colorant (20g/Kg); synthetic thickener (20g/Kg); binder (100g/Kg); cross-
Ac
linker (10g/Kg); catalyst (2g/Kg) in the absence and presence of Silicon softener (20/Kg). Microwave fixation at 1300W/4min. -
b
K/S: color strength; c WF: wash fastness; Alt: alteration; St. staining on cotton; d RF: rubbing fastness; e LF: light
fastness.
26 Page 27 of 32
Table 4
Table 4. Water/Oil repellency and printing properties of printed cellulosic/wool blended fabrics
Repellency rating
Surface roughness (mm)
WF c K/S
Alt
St.
17.48
4
4
20.19
22.38
4-5
4-5
0
22.54
14.02
3-4
3-4
70
5
16.85
20.03
4-5
4-5
Without
0
0
26.95
11.60
With
80
7
20.58
Without
0
0
23.11
With
70
5
Without
0
0
With
80
7
Without
0
0
Water
Oil
Without
0
0
29.05
With
80
7
Without
0
With
Cotton/ Wool
Viscose/ Wool
With
a
70
5
Wet
4
3-4
4-5
us
3-4
4-5
4
3-4
3
3
4
4
3-4
3
3
4
13.75
4-5
4-5
4
3-4
4-5
11.25
4
3-4
3
3
4
18.54
13.44
4-5
4-5
3-4
3-4
4-5
25.49
6.75
4
4
4
3-4
4
18.34
9.69
4-5
4-5
5
4-5
4-5
21.68
6.24
3
3
3
3
3-4
16.30
9.40
3-4
3-4
4
3-4
4
an
ed
ce pt
Pigment Orange 13
Cotton/ Wool
Dry
3-4
Cotton/ Wool
Viscose/ Wool
LF e
4
M
Pigment Blue 153
Viscose/ Wool
-
RF d
b
ip t
Substrate
Water/Oil repellent (40g/Kg)
cr
Pigment Red 146
Pigment
using different pigment colorants along with the water/oil repellent agent in the printing paste a .
Printing paste components : pigment colorant (20 g/Kg); synthetic thickener (20g/Kg); binder (100g/Kg); cross-
Ac
linker (10g/Kg); catalyst (2g/Kg) in the absence and presence of the Water/oil repellent agent (40/Kg). Microwave fixation at 1300W/4min. -
b
K/S: color strength; c WF: wash fastness; Alt: alteration; St. staining on cotton; d RF: rubbing fastness; e LF:
light fastness.
27 Page 28 of 32
Table 5
Table 5. Durability of the imparted functional and coloration properties to wash using different printing pastea
ZI b (mm)
00
00
V/W
00
00
22.0 (19.5) 19.0 (17.0) 19.5 (17.5) 16.0 (14.0) 19.0 (17.0) 13.5 (11.5) 16.0 (14.5) 13.0 (11.0)
20.0 (17.5) 18.0 (16.0) 17.0 (15.0) 14.5 (13.0) 18.0 (16.5) 11.5 (10.0) 15.0 (13.5) 11.5 (10.0)
Aloe vera (10 g/Kg)
Triclosan (10 g/Kg)
Antibacterial & Anti-UV
TiO2-NP's (10 g/Kg)
Soft-handle
Softener (20 g/Kg)
C/W
-
-
V/W
-
Water/Oil repellent (40 g/Kg)
C/W
-
V/W
-
V/W C/W V/W C/W V/W C/W V/W
29.05 (25.52) 22.54 (20.08)
-
-
-
-
-
-
-
-
80 (68) 99 (87) -
-
-
-
-
-
-
ed
Water/Oil repellent
C/W
63 (50) 74 (60)
K/S d Water
Oil
00
00
00
00
-
-
-
-
ip t
C/W
M
Antibacterial
a
G −ve
None
Chitosan (2.5 g/Kg)
-
G +ve
Roughness (mm)
cr
None
UPF
Substrate
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
80 (70) 70 (50)
7 (5) 5 (4)
us
Additive
Repellency rate c
an
Functional finish
15.96 (17.65) 13.41 (11.23) 20.91 (23.30) 16.85 (18.20)
17.48 (13.15) 14.02 (10.62) 21.61 (17.75) 19.43 (16.22) 22.00 (18.92) 16.63 (13.32) 20.52 (16.85) 15.52 (12.48) 20.91 (17.38) 19.03 (16.00) 25.02 (22.01) 16.90 (13.87) 22.38 (19.22) 20.03 (16.88)
Printing paste components : Pigment Red 146 (20 g/Kg); synthetic thickener (20g/Kg); Printofix® Binder MTB
-
C/W: cotton/wool blend; V/W: viscose/wool blend; color strength.
b
ZI: zone of inhibition; c UPF: UV-protection factor; d K/S:
Values in parenthesis are the values of some pigment prints properties after 15 washing cycles.
Ac
-
ce pt
(100g/Kg); cross-linker (10g/Kg); catalyst (2g/Kg). Microwave fixation at 1300W/4min.
28 Page 29 of 32
Figure 1
22
24
20
22 20
K/S
K/S
18
16
18 16
14
12
■
▲
12
Cotton/Wool Viscose/Wool
■
10 0
5
10
0
10
20
cr
(a) Chitosan Conc. (g/Kg) 22
22
20
20
an
us
(b) Aloe Vera Conc. (g/Kg)
18
K/S
18
16
14
16
M
K/S
Cotton/Wool Viscose/Wool
▲
10
14
12
0
12
10
■
10
20
0
(c) Triclosan Conc. (g/Kg)
24
18 16
22 20
K/S
20
18 16 14
14
■
12
20
24
Ac
22
10
(d) TiO2-NP's Conc. (g/Kg)
ce pt
26
Cotton/Wool Viscose/Wool
▲
ed
■ Cotton/Wool ▲ Viscose/Wool
10
K/S
ip t
14
▲
■
12
Cotton/Wool Viscose/Wool
▲
10
Cotton/Wool Viscose/Wool
10
0
10
20
30
0
20
40
60
®
(f) Oleophobol Conc. (g/Kg)
(e) Silicone Softener Conc. (g/Kg)
Fig.1. Effect of Chitosan (a), Aloe vera (b), Triclosan (c), TiO 2-NP's (d), Silicone Softener (e), and Oleophobol® (f) concentration on the depth of the obtained prints. Printing paste components: Pigment Red 146(20g/Kg); synthetic thickener (20g/Kg); Printofix®Binder MTB (100g/Kg); crosslinker(10g/Kg); and (NH 4)2S2O8(2g/Kg). Microwave fixation: 1300W/4min. Page 30 of 32
29
Figure 2
(b)
an
us
cr
ip t
(a)
(d)
Ac ce p
te
d
M
(c)
Fig.2. SEM of untreated Cotton/Wool fabric (a), SEM of treated Cotton/Wool fabric with Aloe vera (b), SEM of untreated Viscose/Wool fabric (c), SEM of treated Viscose/Wool fabric with Aloe vera (d).
30
Page 31 of 32
(b)
(c)
(d)
M
an
us
cr
(a)
ip t
Figure 3
(e)
Ac
(g)
ce pt
ed
(f)
(h)
Fig.3. EDX image and element content of TiO2-NP’s loaded Cotton/Wool blend (a, b) and Viscose/Wool blend (c, d), EDX image and element content of water/oil repellent loaded Cotton/Wool blend (e, f) and Viscose/Wool blend (g, h). Page 32 of 32