General Part

1. Introduction

A printing process is an important method of decorating textile fabric and

it can be defined as the localized application of the colorant to the selected areas
of the substrate. This is usually achieved by applying printing pastes containing
dyes or pigments onto a fabric surface according to a given color design. [1]

Printing pastes are viscous liquids which containing dyes and other
essential ingredients and they are applied to the material by well-known methods,
such as screen and roller. Thickeners play paramount role in the formulation of
printing paste to modulate adequate rheological properties which ensure the
uniform flow of printing paste during the method of printing. A successful print
involves correct color, sharpness of mark, levelness, good hand and efficient use
of dye: all of these factors depend on the type of thickener used.[2]

Natural thickeners can be defined as products obtained from natural

sources such as plants, seeds, seaweeds and microorganisms. These products are
high molecular weight polymers composed of polysaccharides and are often
referred to as hydrocolloids. Production processes vary from simple collection of
tree exudates and milling in the case of gum arabic to more complex production
by fermentation as in the case of xanthan gum. [3, 4]

Printing paste’s main purpose is to catch, adhere, and move dye stuff to the
appropriate cloth. Thickeners have long been the main ingredient in textile

printing pastes. the role of thickening agents in the formulation of printing pastes

is of paramount importance since they impart adequate rheological properties to

the pastes in the different flow conditions encountered in the printing process.
During this process, the materials are moved by the sequence across the mask and
through the screen openings, to the substrate. [5]

The pastes are subjected to flows with shear, extensional, or both

components, at various strain rates. The paste will flow at very low shear rates
after being forced through the screen holes and deposited on the fabric, despite
the fact that high strain rate conditions exist during the first steps of the
application process. As a result, the thickening agents must provide both a
uniform distribution of the printing paste on the screen and a uniform flow of the
paste through the screen holes. [6]

The paste must have good screen ability and complete and uniform
penetrability into the cloth; additionally, the best definition sharpness must be
obtained, and flushing out must be avoided. As a result, low viscosity values at
high shear rates and high viscosities at low shear rates (or the existence of a yield
stress) are generally desirable properties for easy application and good printing
paste performance. [7]

In this study, we are going to use two natural thickeners extracted from
aloe vera and flaxseeds in the printing method for printing different fabrics
(cotton-wool-polyester) using different dyestuffs.

1.1. Thickeners

Thickeners are high molecular weight polymers used to impart viscosity

and plasticity to the printing paste. [8]

Thickeners play an essential role in any printing process. Their main

purpose is to hold dyestuffs, chemicals, and other printing auxiliaries to the
fabrics during the method of printing. The goodness of the resulting print depends
on the chemical and physical properties of the thickeners applied. The depth, the
brightness of the colors, and particularly the sharpness and smoothness of the
print are influenced or even determined by them. [9]

1.1.1. The essential properties of the Thickener

As printing paste should contain a thickener to improve their properties,

therefore thickeners should have characteristic properties such as:

1. Soluble in water and easily prepared with suitable rheological properties.

2. Suitable for mixing with other thickeners and compatible with other
ingredient in printing paste.
3. It should be cheap and easily available
4. Stability to storage, pressure and temperature during printing
5. It should not retain the color or keep away the color from the fabric
6. The thickener should have poor affinity for dyes and other chemicals
7. The thickener should produce a solid film that does not stick and that has
good mechanical and elastic properties and good adhesion.
8. Chemical stability in the drying process.
9. The thickener should produce good color intensity, brilliance, and
uniformity.
10. It should not retain the color or keep away the color from the fabric
11. Easily to be removed and after the washing process, the fabric should be soft
and feel must not be adversely affected. [10]

1.1.2. Classification of Thickeners

 Thickeners can be divided into three categories depending on their origin
(Table 1) [11]

a) Natural thickeners
b) Modified natural thickeners
c) Synthetic thickeners
d) Emulsion thickeners
Table 1: Classification of Thickeners
Thickeners
Natural Modified natural Synthetic Emulsions
A. Plant exudates A. Starch derivatives A. Vinyl polymers A. Water-in-Oil
1. Karaya gum 1. British gum 1. Polyvinyl Alcohol (W/O)
2. Tragacanth gum 2. Dextrin (PVA)
3. Arabic gum 3. Carboxymethyl 2.
Starch (CMS) Polyvinylpyrrolidone
(PVP)

B. Plant Seeds B. Cellulose B. Acrylic polymers B. Oil-in-Water

1. Locust bean gum derivatives 1. Polyacrylamide (O/W)
2. Tamarind seed 1. Carboxymethyl 2. Polyacrylic acid
gum Cellulose (CMC)
3. Guar gum 2. Methyl cellulose
3. Hydroxyethyl-
cellulose
C. Seaweed extracts
1. Alginates

D. Starch

[Link]. Natural Thickeners

Natural thickeners can be defined as products obtained from natural

sources such as plants, seeds, seaweeds and microorganisms. The natural thickening
agents used in printing process are mostly polysaccharides with plenty of hydroxyl groups

derived from plant exudates, sea weeds, seeds and roots. Some of them are
suitable for printing with certain class of dyes, but many times they have to be
modified to suit the requirements of printing. [12]

Polysaccharides are natural biopolymers isolated from renewable sources

such as animals, plants, fungi, bacteria and seaweeds. [13] the main characteristic
of polysaccharide is their ability to modify the properties of aqueous mediums
because of their capacity to thicken, chelate, emulsify, stabilize, flocculate, swell
and suspend, or to form gels, films and membranes. [14]

[Link].1. Plant exudates

Most plant families include types that exude gums in some extent.
Exudate gums are among the oldest natural gums being known. The three major
exudate gums Karaya gum, Tragacanth gum and Arabic gum have a unique range
of functionalities.

Gums are biopolymers which mainly consist of carbohydrates sometimes

with small amounts of proteins and minerals. [15]

a) Karaya gum

Karaya gum an acetylated polysaccharide exudate of Sterculia urens trees.

It is a branched anionic polysaccharide used as a thickener. Gum karaya is a
highly charged (ionic) hydrocolloid. It contains about 37% galacturonic acid. It is
partly acetylated (about 8% acetyl groups by weight). [16]

To be used as a thickener in printing process, Karaya gum is modified for

increasing its solubility because its Particles do not dissolve in water but swell
extensively. This is done by cooking a water suspension of gum karaya under
pressure or oxidizing it with some oxidizing agents such as persulfale or
persilicate.

Modified gum karaya is suitable for the direct printing of colors on cotton
fabrics. It produces smooth prints, and the printing film can be easily to be
removed from the fabric after fixation of the dye. [17]

b) Tragacanth gum

Tragacanth gum is an exudation from the stems and branches of Asiatic

species of Astragalus. It looks dull or milky white to brown depending on its
quality. It is so complex, extremely branched, hydrophilic, and heterogeneous
anionic polysaccharide. It is naturally found as a slightly acidic calcium,
magnesium, and potassium salt. [18]

In textile printing, Tragacanth gum is now less popular than other

thickening agents which can be processed more easily. It has 6- 7% solids
content. It can be used successfully for printing cotton with pigment. It is
combined with British gum for wool printing. It is also used in artificial silk
staple printing and in direct, acid, basic, and azoic color printing on cellulose.
[19]

c) Arabic gum

Arabic gum is a complex, branched, natural polysaccharide, extracted

from the stems and branches of Acacia trees manly Acacia Senegal and Acacia Seyal. It is a
highly neutral or slightly acidic in nature, and it contains calcium, magnesium,
and potassium salts. [20]
 Arabic gum as a Thickener is prepared with 50% solid content. Their
viscosity is very good. They have high ability of adhesion and pigment binding

capacity. Thickeners made from gum Arabic used in block printing on wool and
silk. Arabic gum is used in acid, direct, basic, and azoic color printing on
cellulose fabrics and disperses dyes on polyester fabrics. [19]

[Link].2. Plant Seeds

Plant seeds produce seed galactomannans commonly known as seed gums

located mainly in the endosperm particularly in Leguminosae. Seed
galactomannans are neutral, water-soluble, and heterogeneous polysaccharides. In
general, they are consisted of β-(1→4)‐linked D‐mannopyranose main chains to

which are attached α-(1→6)‐ linked D‐galactopyranosyl units (Figure 1). [21]

Figure 1: General Molecular structure of galactomannan

a) Locust bean gum

Locust bean gum (carob gum) is a white to yellowish white powder

obtained by crushing the endosperm of the seeds from the fruit pod of the carob
tree. It is mainly comprised of the high molecular weight polysaccharides
composed of galactomannans consisting of a linear chain of (1→4)-linked β-D
mannopyranosyl units with (1→6)-linked α-Dgalactopyranosyl residues as side
chains (Figure 2). Locust bean gum swells in cold water, but it does not
completely dissolve. It dissolves in high temperature and its viscosity increases
after cooling. [22]

Figure 2: Structure of locust bean gum

Locust bean gum Used as a Thickener can be used in alkali-resistant

printing pastes and is suitable for preparing printing pastes with all kinds of dyes.
It is removed easily after washing process and the printed fabric has soft tough.
[19, 23]

b) Tamarind seed gum

Tamarind seed gum is seed polysaccharide obtained from the endosperm

of the tamarind tree seeds. It is a high molecular weight, nonionic carbohydrate
polymer consisting of a main chain or β (1-4)-D- glucopyranosly units with a side
chain consisting of a single xylopyranosyl unit attached to every second, third
and fourth D-glucopyranosly unit through and an α-D-(1-6) linkage ( Figure 3).
[24]

Figure 3: Structure of Tamarind seed gum

Tamarind gum polysaccharide is a monomer of glucose, galactose and

xylose in molar ratio of 3:1:2. It is easily hydrating in cold water but required
viscosity is achieved by boiling. Its rheological properties are non-Newtonian
thixotropic solutions like most natural polysaccharides. [25]

c) Guar gum

Guar gum is extracted from the seed of the legume Cyamopsis

tetragonolobus. It is a non-ionic, hydrophilic polysaccharide composed of linear
chain of D-mannopyranose units joined by β-(1→4) linkage with a side-
branching unit of a single D-galactopyranosyl unit joined to every other mannose
unit by α-(1→6) linkages (Figure 4). [26]
 Figure 4: Chemical structure of guar gum

Guar gum contains higher galactose content than Locust bean gum. It is
insoluble in most organic solvents but it swells and disperses in cold and hot
water. Even at low concentrations, guar gum produces highly viscous and it is
influenced by temperature, pH, presence of salts and other solids. Gradually, by
increasing the concentration of Guar Gum in water the viscosity of Guar Gum
solution increases. Its rheological properties are non-Newtonian pseudoplastic
solutions related to its high molecular weight and the existence of hydrogen bonds.
[27]

[Link].3. Seaweed extracts

Seaweeds contain high molecular weight polysaccharides known as

phycocolloids. The principal extracts that could be obtained from seaweeds are
agars, alginates and carrageenan (Figure 5). Phycocolloids can be dissolved in
water to thicken solutions and form gels. Among the Phycocolloids, alginate is
widely used in textile industry as thickener, stabilizer, and gel and film former.
[28]

Figure 5: Molecular structures of agar, κ-carrageenan and alginate

polysaccharides

a) Alginates

Alginates are derived from brown seaweeds. They are salts of alginic acid
which consist of two monomers, D-mannuronic acid (M) and L-guluronic acid
(G). [29]

Alginates consist of 1, 4-β-D-mannuronic acid (M) and 1, 4 α-L-guluronic

acid (G) monomers, with a homogeneous (poly-G, poly-M) or heterogeneous
(MG) block composition (Figure 6). [30]
 Figure 6: Chemical structures of the various blocks in the alginates

Sodium alginate is produced by treating alginate with aqueous alkali

solutions, usually with NaOH. It is widely used in printing cellulose fabrics with
reactive dyes because there isn’t any interaction between sodium alginate and the
reactive dyes .It hasn’t primary hydroxyl groups so that there isn’t any
competition between with cotton for the dye. [31] Alginates have a unique
position in reactive printing because they give brilliant and soft prints with good
color intensity.[32]

b) Starch

The main stored carbohydrate in plants is starch. Starch is extracted from

seeds especially corn, wheat, and rice, and from tubers or roots especially potato,
sweet potato and tapioca. The different in appearance, properties and particle size
distribution of the starches depend on various plant sources and species. [33]
Starch is consisted of α-d-glucose repeated units attached together by α-(1, 4)-
glycosidic bonds and to some extent by α-(1, 6)-glycosidic bonds. It is a mixture
of linear and branched polysaccharides, amylose and amylopectin. [34] Amylose
consists of glucose units linked by α-glycosidic bonds α (1, 4), mainly forming a
linear chain. Amylopectin composes of glucose units attached in α (1, 4) and α
(1,6) links, fundamentally yielding a branched structure. (Figure 7) [35, 36]

Both of these ingredient’s starch is insoluble in water. When the starch is

boiled in water, these grains swell and explode forming a smooth and
homogeneous gelatin. [36] Starch as printing textile thickener is difficult to wash
out and imparts a harsh feeling and a stiff handle to a printed fabric with uneven
blotches. [37]

[Link]. Modified natural thickeners

These are obtained by the modification of cellulose, starch and gums by

chemical, physical and thermal means. Since they are more suitable when
compared to natural thickeners, their use in textile industry is increasing.
 Figure 7: Structure of starch amylose (A) and amylopectin (B)

[Link].1. Starch derivatives

a) British gum

British gum is formed by roasting unmodified starch. British gums are

prepared by heating starch at a high temperature without added acid but in some
cases some acids or alkalis are added.

b) Dextrin

Dextrin is produced by heating dry starch in the presence of an acid with

or without small amounts of moisture. There are categorized as white dextrin,
yellow (or canary) dextrin.
 British gum and dextrin are more water-soluble and form less viscous
solutions or dispersions than its main starch. [38]

c) Carboxymethyl Starch (CMS)

Carboxymethyl Starch (CMS) is acquired by etherification of native

starches. The properties of starch are significantly changed. Carboxymethylation
reaction was happened between starch and chloroacetic acid (MCA) in the
presence of alkali. [39, 40]

R-ONa + ClCH2COONa R-O-CH2COONa + NaCl

CMS has been evaluated as a thickener in polyester printing with

disperses dyes and it has also been used for reactive printing. This thickener gives
as good a color yield as sodium alginate. CMS gives very bright and soft prints.
CMS is suitable for use in alkaline or acidic printing pastes. In roller printing, a
higher color yield can be obtained using CMS. In the field of textile printing,
CMC is worse than CMS because it gives lower color yield. [2, 41]

[Link].2. Cellulose derivatives

Cellulose is the most numerous biopolymers found in the nature, and is

especially substantial polysaccharides because of its wide diversity of
applications in industry, (e.g., paper, textiles etc).

Cellulose is a linear and completely solid homopolymer containing D-

glucose repeating anhydroglucose units. These units are attached together by β-
(1→4) glycosidic bonds created between C-1 and C-4 of adjacent glucose unites
(Figure8). [42, 43]
 Figure 8: Chemical structure of cellulose

Cellulose derivatives were prepared and fine-tuned to get certain wanted

properties. Cellulosic ethers with good water solubility have been intensively
studied, to identify new thickening products for textile printing.

Figure 9: Chemical structure of Na salt of carboxymethyl cellulose

a) Methyl cellulose

Methylcellulose is one of cellulose derivatives. It can be made ready for

use from the reaction of alkali-cellulose with dimethyl sulfate (DMS) or methyl
chloride. Several products of great commercial prominence can be advanced from
methylcellulose. For instance, it may be used as thickener in the textile printing
industry. MC is the simplest cellulose derivative, where methyl groups (–CH 3)
replace the hydroxyls at C-2, C-3 and/or C-6 positions of anhydro-D-glucose units

(Figure 10). [44]

 Figure 10: Chemical structure of repeating unit of methylcellulose

b) Hydroxyethyl- cellulose
When soda cellulose (made by treating cellulose with concentrated
sodium hydroxide solution) is reacted with chlorohydrin , hydroxyethyl cellulose
is formed. The product is soluble in water and gives transluscent solutions which
on drying on textile materials give clear transparent films and find use in sizing,
dyeing, printing, and finishing. Solutions of hydroxyethyl cellulose on drying
give films which are stable to heat and light and are soluble in water but not in
organic solvents. The film does not become tacky, neither does it dust off. It does
not build static charges. In printing it performs better than gum tragacanth or gum
Arabic because it facilitates good penetration, promoting the production of
sharply outlined patterns. The printed fabrics acquire a soft hand. [45]
 Figure 11: Chemical structure of repeating unit of hydroxyethylcellulose

[Link]. Synthetic Thickeners

The use of polyacrylic acid in synthetic thickeners because of the

discovery of acrylic polymers .The aqueous-based synthetic thickeners are high
molecular weight polymers including an acidic monomer as fundamental
component (acrylic acid, methacrylic acid, maleic acid) .These monomers ionize
by adding a base to improve the desirable viscosity. [46]

[Link].1. Vinyl polymers

a) Polyvinyl alcohol (PVA)

Polyvinyl alcohol (PVA), which is basically made from polyvinyl acetate

through hydrolysis, is readily degradable by biological organisms and in water is
a solubilized crystalline structure polymer. Polyvinyl alcohol polymers are
uncommon crystalline water-soluble polymers and contain a hydrophilic group and

a hydrophobic group. There by showing a superior surface activity. [47] PVA as

thickener, PVA has extremely harmonized enough water solubility, thickening
characteristic and covering film strength, and having excellent storage stabilization
in terms of the viscosity in an aqueous solution. [48] Chemical structure of
polyvinyl alcohol was illustrated in Figure 12.

b) Polyvinyl pyrrolidone (PVP)

Polyvinylpyrrolidone (PVP) is a water-soluble, non-toxic and non-ionic

amorphous polymer with high solubility in polar solvents. It has been widely
used in textile field. PVP is also known as polyvidone or povidone. It is a
synthetic polymer including linear 1-vinyl-2-pyrrolidone groups. This polymer
has a carbon chain consisting of an amide group in the side substituent and
owning a poly-N-vinyl amide structure. [49] Chemical structure of
polyvinylpyrrolidone was illustrated in Figure 12.

Figure 12: Chemical structure of polyvinyl alcohol and polyvinylpyrrolidone

[Link].2. Acrylic polymers

a) Polyacrylamide

Polyacrylamides are high molecular weight water-soluble made from

acrylamide or the combination of acrylamide and acrylic acid. Polyacrylamide
has many applications because of its water solubility and versatile chemical and
physical properties. It is used as thickener in printing textiles. [50]

Polyacrylamides are generated by the polymerization of acrylamide

(C3H5NO), a component acquired by the hydration of acrylonitrile. The dissolved
monomers (single-unit molecules) are motivated to polymerize through the action
of free-radical initiators. In the consequent polymer, the acrylamide recurring unit
has the following structure: [51, 52] Chemical structure of Polyacrylamide was
illustrated in Figure 13.

b) Polyacrylic acid
 Acrylic polymers are generally known as acrylics. The monomers are esters

of acrylic and methacrylic acid. Acrylic acid polymers and copolymers cover a
very huge range of applications, such as

1. Hydrosoluble agents for dispersing agents

2. Thickeners
3. Flocculating and super-absorbent agents
4. Detergent auxiliaries
5. Organic synthesis
6. Copolymer emulsion for paints
7. Cosmetics, papers, varnishes and inks
8. In dispersions for leather, textiles, non-woven fabrics, glues and adhesives,
cleaning and waxing products. Besides, plastics, synthetic resins, synthetic
rubbers and lattices. [53]

Polyacrylic acid as thickener, it has been used successfully in many

aqueous systems for years. this thickener has been successfully used in the
printing of cotton fabrics with vat and reactive dyes and printing polyester with
disperse dye stuff. It is used for pigment printing. [54] Chemical structure of
polyacrylic acid was illustrated in Figure 13.

Figure 13: Chemical structure of polyacrylamide and polyacrylic acid

[Link]. Emulsion Thickeners

Emulsions are products of milky appearance resulting from the dispersion

of a liquid in another which is not miscible, using an emulsifier agent, whose role
is to facilitate and make stable the dispersion system obtained. Emulsifier
stabilizes the system by forming a thin film around the globules of dispersed
phase. [55, 56]

[Link].1. Types of emulsion

a) Water in oil emulsion (W/O)

Water in oil emulsions are colloidal systems having water droplets

dispersed throughout the oil. Therefore oil acts as the continuous phase of this
colloid while water is the dispersed phase (see Figure 14). Oil does not mix with
water under normal conditions. But with proper mixing and by using stabilizing
agents, we can obtain oil in water emulsion. The effectiveness of this system
enhances with a small size of dispersed oil droplets. To achieve the stability of
water in oil emulsions, it requires two or more emulsifiers. the common
emulsifiers useful in the formation of water in oil emulsions are Polysorbate,
sorbitan laurate, and Cetearyl alcohol. Water in oil emulsions is useful for the
production of oil-based products .Oil in water emulsions is useful in the
production of water-based products. [57]
 Figure 14: Water in oil emulsion (W/O)

b) Oil in Water emulsion (O/W)

Oil in water emulsions are colloidal systems that have oil droplets
dispersed throughout the water. Therefore water acts as the continuous phase of
this colloid while oil is the dispersed phase (see Figure 15). Oil does not mix with
water under normal conditions. But with proper mixing and using stabilizing
agents, we can obtain oil in water emulsion. The effectiveness of this system
enhances with a small size of dispersed oil droplets. to achieve the stability of oil
in water emulsions, it requires only one emulsifier. Sorbitan stearate, lecithin,
lanolin/lanolin alcohols, and glyceryl monooleate are the common emulsifiers
useful in the formation of oil in water emulsions. [58]
 Figure 15: Oil in Water emulsion (O/W)

For printing applications the emulsion thickening must be stable ( a ) to

the dye used and ( b ) t o the other constituents of the print paste (e.g. salt, acid,
alkali, and metal salts). The viscosity of the emulsion must be within a suitable
range for application by printing , and this is controlled by adjustment of the
phase volume relationship. Addition of water t o an oil-in-water emulsion reduces
the viscosity, while oil-phase additions cause the same change in water-in-oil
emulsions. For this reason oil-in-water emulsions are more easily washed off
from printing rollers than water- in-oil emulsions. [59]

Oil-in-water emulsions are usually less difficult, to prepare than water- in-
oil type and tend to be more stable towards electrolyte additions. Low-speed
stirrers are often sufficient to produce oil-in-water emulsions, whereas high-speed
stirring and homogenisation are usually required for the production of the water-
in-oil type.

Low-speed stirrers are often sufficient to produce oil-in-water emulsions,

whereas high-speed stirring and homogenisation are usually required for the
production of the water-in-oil type.[60, 61]

Both types of emulsion exhibit pseudo-plastic flow. [62]With the

introduction of emulsion thickening, pigment printing has been successfully
carried out for many years. Emulsion thickenings produce a better color yield and
brilliance than water-soluble thickenings and, because both phases of the
thickenings are volatile, they have no influence on the handle or fastness. [63]

Emulsions are metastable systems whose stability is influenced by the

degree of dispersion of the inner phase, by the type and quantity of the emulsifier
used, and by any substances that may be dissolved or dispersed in the inner or
outer phase. The origin and composition of the white spirit used can also affect
the stability. The quality normally employed has a boiling range of around 220 oC
and the aromatic content should be no higher than 15%. Since, in principle, all
the components of a print paste can affect the emulsion to a greater or lesser
extent, protective colloids are often added to improve the stability. In the W/O
system, the binders dissolved in the outer phase act as protective colloids and in
O/W systems, small amounts of water-soluble thickening agents are used. [64,
65]