Colorant Pigment

The range of pigment colorants suitable for polyester roughly matches that for nylon.

From: Handbook of Textile and Industrial Dyeing, 2011

Related terms:

Solubility, Binders, Castor Oil, Colourants, Colouration, Polyolefin

View all Topics

Polymers for a Sustainable Environ-

ment and Green Energy
H. Lutz, ... W. Huster, in Polymer Science: A Comprehensive Reference, 2012

10.27.11.7.2 Water-based ink formulations and emulsion vehi-

cles – the workhorse in water-based printing inks
The main ingredients of flexographic/gravure printing inks are the colorant/pig-
ment, binder (emulsion vehicles), and solvent. Typical amounts of emulsion vehicles
in printing ink formulations vary between 25 and 35%. Emulsion polymers, especial-
ly water-soluble salts, are used up to 30% in pigment dispersions, too. The amount
of pigment dispersion is between 35 and 50% of the total ink formulation. The
colorant/pigment comprises 30–45% of the pigment dispersion. In water-based
systems, the solvent is mainly water ( 10%). The amount of other ingredients such as
neutralizer, surfactant, and defoamer can sum up to 10% of the total formulation.
The main function of the emulsion vehicle is to act as the pigment carrier and provide
excellent adhesion of pigments and additives onto the surface.285

The emulsion covers the pigment particles and supports dispersing of the pigments
– avoiding agglomerations and providing small particle size distributions. Without
the emulsion, the pigments would not adhere to the substrates after drying of the
printing ink. Depending on the emulsion vehicles used, the chemical and mechani-
cal resistance as well as the resistance against harsh environmental conditions, such
as water, radiation, and heat, of the print can be optimized.
The liquid printing ink industry differentiates between natural resins, such as guar
and xanthan gums, shellac, and proteins, and water-based resins. Water-based
resins can be differentiated into alkali-soluble resins, micro emulsions, and typical
latex emulsions. The emulsion vehicles support the following printing ink prop-
erties: pigment wetting, good film-formation properties, sufficient adhesion
to substrates, low viscosity, low odor, printability, hold-out on porous substrates,
re-solubility in water, and compatibility with other resins. Shellac-based flexographic
printing inks were first substituted by polyacrylic and polymethacrylic acid resins.
Over the last few decades, there has been excellent development of water-based inks,
and nowadays styrene acrylics and terpolymer acrylics are mainly used. The following
are some of the acrylic monomers used: methyl methacrylate, butyl acrylate, ethyl
acrylate, 2-ethylhexyl acrylate, acrylic and methacrylic acid, 2-hydroxyethyl acrylate,
and amino acrylate. Smaller volumes of styrene maleic anhydride (SMA) copolymers
are used too, especially in printing inks possessing high heat resistance. The required
water solubility can be achieved by transferring the resins by ammonia or sodium
hydroxide into their water-soluble salt forms. Such alkali-soluble resins are mainly
used in pigment dispersions. By varying the amount and Tg of the acrylic monomer
used, final printing ink properties such as flexibility, adhesion, film forming, and
hardness can be adjusted. Incorporation of functional groups into the polymer
chain can further increase the already quite good affinity of acrylic-based emulsion
vehicle for nonporous substrates. Styrene is used to adjust the strength and cohesion
properties.

Typical physical properties of styrene acrylic emulsions used for flexographic and
gravure printing can vary significantly depending on the final application, for
example, preprint corrugated, surface print (requiring softer polymers) up to folding
cartons, and flexo news (requiring harder polymers). The Tg range is from even
minus Tgs (< 0 °C) up to 100 °C. In general, the average particle size distribution of
emulsion vehicles is small and varies between 50 and 200 nm.

According to the polymerization technology used – emulsion polymerization – the

molecular weights are high, approximately >200 000 g mol−1, viscosity is low – as
required for the fluid ink process – and solids are between 40 and 50%.

> Read full chapter

Scales for communicating colours

A.K. Roy Choudhury, in Colour Measurement, 2010

Pope colour system

The rounded double cone with tilted central plane colour solid proposed by American
art educator Arthur Pope (1880–1974) is based on the subtractive mixing of pigment
colorants, primarily to assist the understanding of the relationships among colours
produced by the artists putting less importance on colour notations and more an
visual perception (Heila, 1988). The system has three attributes, namely: value, hue
and intensity. Twelve pure colours (of 100% intensity) are placed at equal distances
from the neutral axis. Scales of purity (i.e. the degree of blackness) and brilliance (i.e.
the degree of whiteness) lie on the two clearly placed and visually evident planes.
This is similar to the black or white content of the Ostwald system. Pope, however,
acknowledged that his system is based on approximations rather than scientific
measurement.

> Read full chapter

Colour printing techniques

C. Parraman, in Colour Design, 2012

18.4.1 Overview of differences between pigments and dyes

Pigments are finely ground coloured particles that are suspended in a carrier liquid.
In contrast to dyes, which colour by staining materials, pigment particles sit on top
of a material surface. However, in inkjet printing the objective is to maintain the dye
and pigment colourant on the paper surface by using a receptor layer (Mitsubishi,
2004). It is generally considered that permanent inks are made with pigments and
non-permanent inks are made with dyes.9 Furthermore, dyes are composed of
organic materials that are more susceptible to fading than pigments, which are made
from inorganic materials. Synthetic organic pigments tend to be more light-fast
than their natural organic counterparts. They are highly saturated and can be used
as an extender to replace larger proportions of inorganic pigments, thus reducing
manufacturing costs. Based on experience of inkjet dyes of the past, early inkjet
inks were dye-based inks and faded in a relatively short space of time. However, as
demand increases and with technological developments in high-performance dyes
and pigments, these definitions are beginning to be blurred. In very broad terms,
many materials exist with a range of solubility and permanence; pigments at the
low end and dyes at the higher end. Many definitions are not precise because of
highly sophisticated manufacturing methods; for example, pigments that have been
ground to such ultrafine particulates could be considered as a stain. Furthermore,
materials must be able to be resistant to light, moisture, air, alkalis, and acids and
also resistant to the heat and pressure generated by an inkjet printer head system.
These highly specialised materials required for high-performance applications are
very different to the traditional watercolours and paints as used by artists.

Some typical examples of organic and inorganic pigments (Hodges, 1989, 69–70)
are listed here:

• Organic: (i) vegetable source (indigo, madder); (ii) animal source (sepia,
cochineal); (iii) synthetic organic (phthalocyanine blue, alizarin crimson).
• Inorganic: (i) native earth (raw umber, raw sienna); (ii) calcined native earth
(burnt umber, burnt sienna); (iii) synthetic inorganic colour (titanium dioxide,
cerulean blue).

There is a huge range of pigments from which to choose, and for the inkjet chemist
the important factor is to choose a colorant for which the purity of colour is main-
tained when intermixed. A cyan, magenta, yellow and black inkset may comprise
a cyan ink that contains the chemical properties of a phthalocyanine pigment; the
magenta ink composition may contain the quinacridone pigment; and the black ink
is a carbon black, which is the most resistant to fading and which can withstand
visible and ultraviolet light, moisture and air.10

> Read full chapter

Chain Polymerization of Vinyl

Monomers
S. Slavin, ... D.M. Haddleton, in Polymer Science: A Comprehensive Reference, 2012

3.09.5.2 Direct Industrial Applications of CCTP

CCTP is used directly in a variety of applications, one of which is printing using
toner processes. Water-miscible CTA is used, along with initiator, to facilitate the
polymerization of monomers to form latex particles. Coalescence or fusion of these
latex particles with colorants, pigments, and/or dyes gives sediment-free toner
compositions used for electrographic imaging and printing processes.131,163

Polymerization of MMA to form thermoforming sheets is a process that utilizes

CCTP. Suitable compositions are placed between sheets of glass or two opposing
metal bands, providing a sheet of thermoformable PMMA. The sheet is heated and
then drawn into a mold under pressure or vacuum to manufacture items such as
baths, sinks, and shower trays.164

Emulsion polymerization is an important industrial process mainly used to create

high-molecular-weight lattices. The need to create lower-molecular-weight lattices
for certain applications became evident and CCTP was employed by the use of
specific CTAs to control the molecular weight of resulting polymers.19,165 CCTP in
emulsion polymerization facilitates the synthesis of macromonomers with a high
degree of terminal vinyl groups and can also be used in the synthesis of copolymers.
The stability of the boron fluoride-bridged cobaloxime catalysts toward hydroly-
sis enables the synthesis of methacrylic acid-containing polymers without catalyst
degradation.165 Due to the instability of cobalt CTAs toward peroxides, conventional
inexpensive peroxide initiators are avoided, with more expensive azo initiators being
used in their place. The evolution of nitrogen bubbles with initiator decomposition
can cause problems of coagulation. This problem can be overcome, however, by
conducting microemulsion polymerizations; the reduced particle size nucleation
occurs predominantly in the monomer droplets, as opposed to creating a new
particle phase, and so the CTA is separated from the primary initiator radicals.166

CCTP can be used for the removal of RAFT end groups to give vinyl-terminated
polymers. The presence of RAFT end groups can sometimes be detrimental to the
required application of the polymers as they can undergo aminolysis, hydrolysis, and
thermolysis, and may possibly cause cytotoxicity in biological applications; hence,
facile and complete removal of RAFT end groups is often desired. Once the RAFT
polymerization is complete, a cobalt CTA is added and the reaction continued for
several hours until the RAFT end groups are fully removed. Low concentrations
of CTA are used so that no further polymerization should occur that may have a
detrimental effect on the PDI of the synthesized polymer.150

The terminal vinyl groups of CCTP polymers have been of interest due to their
potential to be functionalized by click chemistry methodology. This would offer a
route to a wide range of functional polymers. Several click chemistry methods are
available for the functionalization of vinyl groups involving the attachment of a
functional thiol, termed thio-Michael addition. Haddleton et al. investigated the
validity of several of these methods for the functionalization of CCTP oligomers-
, including MMA dimer, HEMA, and ethylene glycol methyl ether methacrylate
oligomers, using the nucleophilic amine catalysts triethylamine (TEA), pentylamine,
and hexylamine, and phosphine catalysts dimethylphenylphosphine (DMPP) and
tris(2-carboxyethyl)phosphine hydrochloride (TCEP). A range of commercial func-
tional thiols were covalently attached by reaction with the terminal vinyl groups
of the CCTP oligomers using all catalysts, thus providing a facile route for the
formation of functionalized polymers.167 Various thermoresponsive oligomers of
ethylene glycol methyl ether methacrylate have also been synthesized by CCTP
and functionalized by thio-Michael addition in this manner, forming functional
thermoresponsive oligomers.73

> Read full chapter

Dyeing of synthetic fibres
A.K. Roy Choudhury, in Handbook of Textile and Industrial Dyeing, 2011

2.2.5 Mass coloration of polyolefins

Despite desirable properties, PP fibres traditionally have suffered from a major
drawback that has limited their adoption in textile apparel applications – in contrast
to other fibres, conventional PP fibres cannot be dyed. Instead, the colour has to
be imparted at the fibre extrusion step through mass coloration or solution dyeing.
The process involves adding a relatively thermally stable pigment colorant during the
melt spinning of the fibre. The pigments used are not usually miscible with PP. Thus,
the pigments are present as discrete particles in the fibre, and the colour imparted
becomes permanent in the fibre.

Because of lower melt temperature (165°C), a wider range of pigments including

chrome pigments, inexpensive azo pigments and toners are used. However, fine PP
filaments are extruded at temperature as high as 300°C and high thermal-stable
pigments, similar to those used for nylon and polyester, are to be selected for that
purpose.

Currently, some of the most widely used pigments for the mass coloration of PP
include C.I. Pigment Red 57:1, C.I. Pigment Blue 15:3, C.I. Pigment Yellow 62, C.I.
Pigment Green 7 and C.I. Pigment Red 48:2 (Lewis, 1988).

> Read full chapter

Additives for Plastics

J.A. Brydson, in Plastics Materials (Seventh Edition), 1999

7.7 COLORANTS
There are basically four methods used for colouring polymers. These are surface
coating (e.g. painting), surface dyeing, introduction of colour-forming groups into
the polymer molecules and mass colouration. Surface coating involves extra pro-
cessing and can substantially increase the cost of the product and is avoided where
possible except in the case of fibres. Surface dyeing can be of limited use with
some polar polymers such as the nylons where only a small quantity of material is
required to be coloured. Whilst academically interesting, the deliberate introduction
of chromophoric groups is an inflexible and expensive method. Therefore, for most
applications of rubbers and plastics the mass colouration approach is favoured.

Colorants are sometimes divided into two classes, insoluble colorants (pigments)
and soluble colorants (dyestuffs). It should, however, be noted that many colorants
have a low but finite solubility so that such a rigorous classification can be mislead-
ing. As explained previously, such a low solubility may in certain circumstances lead
to blooming. One way of reducing blooming tendencies is to use colorants of high
molecular weight. For a material to be a successful colorant it should meet all the
requirements listed on p. 120.

For example, to be efficient they should have a strong covering power although
in some circumstances a colorant of lower covering power than another might be
favoured if it was so much cheaper that more of the colorant could be incorporated
and still lead to a cheaper compound. Stability to processing covers not only the
obvious aspect of heat resistance but also resistance to shear. Particles of some
colorants break down under intensive shearing and as a result may change colour.
When colorants are added before polymerisation they should not interfere with the
polymerisation reaction nor should they be affected by the presence of some of
the polymerisation additives. Blooming and bleeding can both be problems. Some
colorants may also adversely affect polymer properties such as oxidation resistance
and electrical insulation behaviour. Anisotropic pigments may become oriented
during processing to give anomalous effects.

> Read full chapter

Compounding and Additives

Michael Niaounakis, in Biopolymers: Processing and Products, 2015

5.5.2.10 Colorants
Colorants, including pigments and dyes, are used to alter the color or improve the
aesthetics of a biopolymer. The choice of colorants depends on the ultimate color
desired by the designer for the polymer article. Like other additives, colorants must
not be toxic and harmful to the environment. Commercial sources for pigments
and dyes include multinational companies such as Polyone, Clariant, BASF, Bayer,
Danimer, Color-Chem International, Sun Chemical, Zhuhai Skyhigh Chemicals, and
others identified at Internet websites.
Table 5.8 lists eight commercially available pigment colorants in a variety of pri-
mary and secondary colors, five chromatics, two blacks, and one white as listed by
WO2011040905 A1 (2012, POLYONE CORP).

TABLE 5.8. Eight Commercial Pigment Colorants (2012, WO2011040905 A1, POLY-
ONE CORP)

Raw Material CI Name Family Color FDA1

Name
Tioxide R-FC6 Pigment White 6 Inorganic White Y
White
Regal 660R Black Pigment Black 7 Organic N
Powder
MPC Channel Pigment Black 7 Organic Y
Black
Heliogen Blue Pigment Blue 15:3 Organic Blue Y
K7090
Heliogen Blue Pigment Blue 15:1 Organic Blue Y
K6903
34L2000 Azure Pigment Blue 28 Inorganic Blue Y
Blue
Sicotan Yellow Pigment Brown 24 Inorganic Yellow Y
2001 FG
Sicotan Yellow K Pigment Yellow 53 Inorganic Yellow Y
1011

1 As published by the commercial producer or as tested by PolyOne or both.

Table 5.9 lists 14 commercially available dye colorants as listed by WO2011040905

A1 (2012, POLYONE CORP).

TABLE 5.9. Fourteen Commercial Dye Colorants (2012, WO2011040905 A1, POLY-
ONE CORP)

Raw Material CI Name Family Color FDA

Name
Lambdaplast Blue Solvent Blue 59 Anthraquinone Blue N
NL
Macrolex Blue RR Solvent Blue 97 Anthraquinone Blue N
Granular
Macrolex Green G Solvent Green 28 Anthraquinone Green N
Granular
Macrolex Green 5B Solvent Green 3 Anthraquinone Green N
Granular
Macrolex Orange Disperse Orange Polymethine Orange N
G Granular 47
Macrolex Orange Solvent Orange 60 Perinone Orange N
3G Granular
Macrolex Red EG Solvent Red 135 Perinone Red N
Granular
Macrolex Red E2G Solvent Red 179 Perinone Red N
Granular
Solvent Red 195 Anthraquinone Red N
Thermoplast Red
454
Violet R Granular Disperse Violet 26 Anthraquinone Violet N
Macrolex Violet B Solvent Violet 13 Anthraquinone Violet N
Granular
Macrolex Violet 3R Solvent Violet 36 Anthraquinone Violet N
Granular
Key Plast Yellow 3G Solvent Yellow 93 Pyrazolone Yellow N
Key Plast Yellow AG Solvent Yellow 114 Quinophthalone Yellow N

In addition to the traditional colorants, biobased colorants are now industrially

available [26,27]. Renol®-compostable product line of Clariant includes master-
batches based on over 80 different pigments, which can be incorporated in several
biopolymers (PLA, PHA, and starch based). Derived from natural resources, the
colors include red, orange, yellow, green, and blue. Orange is derived from the
root of the turmeric spice plant. Yellow comes from a tropical flower, green from
chlorophyll and other plant sources, and carmine red from the cochineal insect.
Some of them boast excellent clarity, but their lightfastness may be limited [28].

The OnColor™ BIO Colorants of Polyone range of masterbatches are based on

sustainable materials and can be used with commercially available biodegradable
polymers including starch, PLA, PHA, PHBHV, PBS, PBAT, and their blends. Teknor
Color Company has three series of color concentrates for use in PLA and its blends
that are suitable for injection, extrusion, and blow molding processes. The three
series of colorants differ in terms of their carrier resins, which are either PLA or
polyesters compatible with PLA and thus readily blended into it. Ampacet markets
a series of color masterbatches, including organic-based pigments from renewable
resources for a broad range of biopolymers. DaniMer offers also a wide range of
colorants compounded with PLA.

> Read full chapter

Additives in Polymers
V. Ambrogi, ... V. Marturano, in Modification of Polymer Properties, 2017

4.1 Introduction

4.1.1 Role of Polymer Additives

Pristine polymeric materials often show poor properties and would result in a
commercial failure. Additives play a very important role both in the processability of
plastic materials and in their applications (Gatcher and Muller, 1990). The incorpo-
ration of additives makes polymer materials suitable for multiple applications in the
plastic market: automotive, design, packaging, constructions, electronics, telecom-
munication (Pritchard, 1998). Additivation of molecules or particles to the virgin
polymer can improve its bulk and surface properties. For example, polypropylene
(PP) (and polyolefins in general) would not be one of the most widely employed
commodity polymer without additives. It would, in fact, degrade in weeks, because
of its poor thermal oxidative stability (Bockhorn et al., 1999). According to the
European Community an additive is “a substance which is incorporated into plastics
to achieve a technical effect in the finished product, and is intended to be an
essential part of the finished article.” This chapter aims to give an insight on the
most common additives used in plastic in the last few decades; in particular it
will be focused on the following additives: antioxidants, light stabilizers, ultraviolet
(UV) absorbers, flame retardants (FR), heat stabilizers, impact modifiers, plasticizers,
compatibilizers, coupling agents, colorants, pigments, whiteners. A brief description
of bio-based additives is also given.

4.1.2 Technological Aspects of Polymer Additives

Different effects can be achieved, such as protection from several external agents,
and improvement of the material performances in mechanical, processability, and
miscibility behavior. Additionally, the macroscopic appearance of material can be
changed by adding whiteners, dyes, or pigments to the standard formulations (Bart,
2006).

Depending on its nature, an additive is able to modify in a more or less strong

way the basic polymer characteristics, its performance, and durability. Traditionally
additives are added in powder form, although this may cause hygiene and handling
problems. On the other side, only a few additives are added in the liquid form
(e.g., Vitamin E). Additives in the ideal physical form have a spherical product shape
(500–1500 μm) ensuring at the same time the same performance as the original
powders, high homogeneity, dispersibility, and mechanical resistance. In recent
years the market has experienced an increase in additive masterbatches (concentrates
containing high level of additives already dispersed in the polymer), e.g., color
masterbatch (Kutz, 2011). Therefore, an effort is usually made in the compounding
techniques, because each complex material added to the pristine polymer could
result in different processability characteristics. For example, handling of solid
additives has been reviewed (Hubis, 2000).

A key parameter to take into account for the design of a compounding mecha-
nism is the surface energy involved in the polymer/filler interaction. High surface
energies create dispersion issues, adversely affecting mechanical properties in the
final product. Ideally, an additive needs to interact strongly with the polymer matrix,
minimizing the surface energy. Some of these dispersion problems can be overcome
by adding dispersing agents to the polymer/additive formulation, typically fatty
alcohols or phosphoric esters. For example, the addition of calcium carbonate, the
most used additive for plastics, rubbers, and paints, can be increased by up to 70%
without significant mechanical modifications.

Another concern is the aggregation of fillers, if added in particulate form. This is a

particularly dangerous effect because it can lead to processing problems, and can
even damage the mixing machinery. The basis of aggregation is to be found in
the attractive forces that can occur between similar particles, in particular adhesion
forces (hydrogen bonding, acid/base interactions, other specific interactions). A way
to hinder these processes is to increase shear forces, which instead lead to particle
separation (Nardin and Papirer, 2006).

As all areas in polymer technology, health standards must be applied to regulate

the use of additives. The most sensitive problems involve the use of halogen-con-
taining FR, heavy metals (as used in pigments and polyvinyl chloride (PVC) stabi-
lizer systems), and plasticizers. Nowadays the main concerns of society regarding
the polymer industry are focused on plastic recycling. So far, the most exploited
technology is incineration of plastics in order to produce energy. Additivation of
any particulate can affect the safety of the incineration process, releasing dangerous
combustion by-products into the atmosphere. Fortunately, toxicity and safety issues
have led research and development teams to study more sustainable alternatives
with applications in even wider areas than those originally envisaged. Therefore,
the last section of this chapter will be devoted to bio-based additives, which could
guarantee a valuable and more sustainable alternative to commercial additives.

> Read full chapter

Fabric Finishing
H. Ujiie, in Textiles and Fashion, 2015

20.2 Direct Printing

Direct printing is defined as a printing application in which colorants are applied to
the cloth in a single operation (with the appropriate fixation and washing processes).
All colorants prior to the mid-nineteenth century were derived from nature, and,
since some of these colorants were not substantive (i.e., they did not adhere directly
to the fibers) it was necessary to apply metal salts, in a process known as mordanting,
to color the cloth. Using such compounds carries pollution and occupational safety
risks. Direct printing does not involve mordanting, and most printed textiles today
are produced by direct printing.
The images or patterns are formed by what is also referred to as “localized dyeing,”
where the colorants are restricted to certain areas of the fabric. In order to achieve
this, it is necessary to formulate print pastes that will not bleed or wick through the
fabric. Thus, in conventional textile printing, the print pastes consist of:

• the colorants (pigment or dyes),

• a thickening agent, and

• the fixing agent.

No single colorant is substantive to all classes of fibers; therefore, the formulations

of print pastes are different and specific to each colorant and fiber type. Table 20.3
gives some of the formulations of major colorants.

Table 20.3. Textile colorants and substrates

Pigment All fibers including mixed fibers

Reactive dye Cellulose fibers (cotton, linen, and rayon), protein
fibers
(Silk and wool) and some nylon
It is mainly used for cellulose fiber
Disperse dye Polyester, some nylon, acrylics, triacetates, and
other synthetic fibers
It is mainly used for polyester
Vat dye Cellulose fibers and protein fibersIt is mainly used
for cellulose fibers
Acid dye Protein fibers and some nylon

20.2.1 Pigment Printing

Pigments are not substantive to any fiber, and are composed of colored substances
in a solid state that are completely insoluble to solvents (including water). Pigment
printing systems require a binder as a fixing agent, which helps the pigments to
bind with the textile substrates. In the fixation process, the printed fabrics are baked
in a curing oven. The heated dry air activates and allows the thermosetting binder
to adhere the pigments onto the surface of the cloth.

Pigment printing pastes also contain a thickening agent. Most thickeners are syn-
thetic compounds and can be categorized according their application system:

• emulsion, or

• aqueous.

The emulsion system is older and involves a solvent, whereas the aqueous system
does not.
Unlike dye applications, fabrics printed with pigments do not require washing after
fixations. Therefore, any thickening agents remain on the printed cloth and stiffen
the printed areas.

The emulsion thickening system does not stiffen the printed areas as much as the
aqueous system, and so it dominated the textile printing industry for many years.
However, the emulsion system is associated with hydrocarbon emissions and has
consequently been banned in many industrial countries due to environmental con-
cerns. As a result, the aqueous thickening system has been improved significantly,
and has now become the most popular method.

A disadvantage of pigment printing is that the polymer layers that enclose the
pigments on the cloth surface can break easily, and so its crock (rubbing) fastness
rating is poor. However, pigment printing dominates the textile printing industry,
with 45% of the total colorant consumption worldwide (see Table 20.4) (Stork, 2002),
mainly because pigment printing provides the following advantages:

Table 20.4. Colorants (pigment and dye)

Pigment 45%
Reactive dye 30%
Disperse dye 18%
Vat dye 4%
Acid dye 1%
Misc. 2%

Stork (2002).

• high fastness to light,

• vibrant colors,

• less expensive than dyestuffs, and

• it can be used on any fibers and blends.

20.2.2 Reactive Dye Printing

Reactive dyes have a wide color range and are mostly used for printing cellulosic
fibers such as cotton and linen. In reactive dye printing, dye molecules are diffused
into the fibers and establish chemical bonds with them after fixation occurs. Al-
though pigments are the most popular colorants in textile printing, reactive dyes
are the most frequently used out of all other dyes, accounting for 30% of the total
colorants used in the printing industry (see Table 20.4) (Stork, 2002).
Unlike pigments, most dyes are substantive to fibers if the chemistry used in the
coloration method is correct. Reactive dye printing chemistry requires an alkali, such
as sodium bicarbonate, as the fixing agent to establish the molecular bonds between
the dyes and the fibers. Printing with reactive dyes also requires a thickening agent.
Sodium alginate thickener, a derivative of seaweed, is the most common. Other
thickening agents, which are commonly used in other processes, are based on
carbohydrates and would react with the dyes, creating poor printing results.

Fixation processes, which cure reactive dyes to the fabrics, generally include steam-
ing the printed fabric with highly saturated steam followed by washing in hot water
to remove the thickening agent and excess dye particles.

20.2.3 Disperse Dye Printing

Disperse dyes are used for sublimation transfer printing, but can also be printed
directly to the cloth. Although disperse dyes are substantive to acrylics, triacetates,
and other synthetic fibers, polyesters are the largest fiber group for this printing
application.

Disperse dyes do not require any specific fixing agent because the dyes become
substantive to the fibers through phase changes initiated by temperature (solid to
vapor to solid). A wide range of thickening agents can be used, including crystal
gum, modified starch, locust-beans, etc. However, in choosing the thickener, it is
important to consider both proper adhesion of the thickener to the cloth and ease of
removal from the cloth in the washing process. Fixation is typically performed with
high temperature steaming and washing to remove excess dyes and thickeners.

20.2.4 Vat Dye Printing

Vat dyes have excellent wash and light fastness ratings and are used to print
textiles for high-end furnishing and military uniforms. They are substantive to both
cellulosic and protein fibers, but are mainly used for printing cellulosic fibers such
as cotton and linen.

Vat dye printing employs reduction-oxidation chemistry, where the reducing agent
becomes the fixing agent in the printing process. In the presence of a reducing
agent, an insoluble vat dye becomes soluble in the print paste. The most popular
reducing agent is sodium sulphoxylate-formaldehyde (commercial names are For-
mosul and Rongalite).

To fix the dyes after printing, the fabric is steamed, which initiates the chemical
reduction process and diffuses the dye further into the fibers. Afterward, washing
with an oxidation agent such as hydrogen peroxide converts the vat dye back to
an insoluble state. Lastly, the printed cloth is treated in a hot water bath with
detergent, which stabilizes the vat dye molecules and establishes maximum fastness
and optimum shades.

20.2.5 Acid Dye Printing

Acid dyes are substantive to protein and some polyamide fibers, including silk, wool,
and nylon 6.6. Acid dyes are characterized by clear and vivid colors and are used
for printing fabrics such as those used for swimwear, high-end fashion dresses, and
accessories. Depending on the selection of dye, the light fastness rating can become
problematic for certain applications.

In the printing process, acid dye molecules need to establish ionic bonds with
the fibers. Therefore, the print paste typically uses weak acid solutions, such as
ammonium sulfate, ammonium tartrate or acetic acid, as a fixing agent to create
the negatively charged dye site. The acid is mixed in the print paste together with a
thickening agent made from guar gum, locust-bean, crystal gum, etc. The fixation
processes are similar to those used for reactive dyes. After steaming with saturated
steam, the printed fabrics are washed to remove excess dyes and thickening paste.

20.2.6 Digital Inkjet Printing

Inkjet inks do not contain any thickening or fixing agents, unlike conventional print-
ing, which employs a paste with the colorant, thickener, and fixing agent. Instead,
they are applied to the textile substrate as a pre-treatment. Generally speaking,
inkjet inks consist of pure coloring matter and are formulated to achieve optimum
printability through ensuring that the print head nozzles eject perfect droplets at
the micro scale. These inks also have a longer shelf-life than conventional colorants,
which tend to separate and sediment. Four classes of inkjet inks are currently most
popular: reactive dye ink, acid dye ink, disperse dye ink, and pigment ink.

Prior to inkjet printing, the fabric needs to be treated with the appropriate thickening
and fixing agents. Pre-treatments are required to establish crisp and optimal print
qualities along with the proper chemical bonds for each coloration class. Fixation
after inkjet printing is similar to conventional fixation for each different class of
colorants. Cloth printed with reactive or acid dye inks is steamed with a saturated
steam and washed. Fabrics printed directly with disperse dye inks are steamed at
high temperature then washed, and fabrics printed with pigment inks are baked in
an oven with dry air.

> Read full chapter

Water- and Solvent-Based Coating
Technology
Edgar B. Gutoff, Edward D. Cohen, in Multilayer Flexible Packaging (Second Edi-
tion), 2016

14.3 Web-Coating Machine Hardware and Functions

The coating machine used to produce the coated product is complex and has
many separate elements that must function well while interacting with each other.
The machines are typically quite versatile. They can continuously produce different
product structures at high productivity and low cost. They can produce the more
common continuous coatings such as barrier layers, release layers, adhesives, or
antistatic layers. They may also produce intermittent coatings, such as in the printing
process and in coating anodes and cathodes for thin film batteries.

In general, there is an ideal coater arrangement for any given product. However,
most coating machines produce many different products with different coating
thicknesses, and therefore the machine usually is a compromise made for the several
applications. The coating machine has several process elements that are required to
continuously produce the coated product.

The first element, while essential, is not part of the coating machine itself. It is the
kettles and mixing equipment used to mix the fluids that are to be applied to the
substrate. The final coating solution contains solvents, binders, pigments, colorants,
cross-linkers, surfactants, etc., which need to be dissolved, dispersed, and mixed
and treated to prepare a uniform homogeneous solution or dispersion. Usually,
this is done in temperature-controlled kettles with high or low shear mixers. Scales
and filtration equipment are part of this system. High shear mixers are needed
to disperse particles and to obtain the desired particle size. After the solutions are
mixed, they are filtered to remove larger particles, and then either sent to storage
or transferred to the solution feed equipment, which is a part of the main coating
machine. The solution preparation equipment is not integrated into the coating
machine; it is a separate batch operation.

Coating itself is a continuous process and the individual elements must be inte-
grated and function at the same speed. While all coating machines have the same
common elements, the exact component design depends on the specific product
and productivity needs. Each unit is essentially a semi-custom unit. Coating machine
line speeds can range from about 0.01 m/s (2 fpm) for some medical test strips up
to 15 m/s (3000 fpm) or even faster for clay coatings on paper, depending on the
exact design. Coating widths can vary from about 10 cm (4 in) to 3.7 m (12 ft) or
even wider, depending on need. Fig. 14.1 shows the components of a typical coating
machine.

Figure 14.1. Coating machine with three unwinds and two laminating stations.-
Source: Polytype Converting SA.

The web transport system conveys the uncoated substrate from the unwind stand
through the coating station and the dryer to the rewind stand, while maintaining
the appropriate speed and tension control. It has several components. The unwind
stand holds the uncoated substrate roll and feeds it into the coating applicator and
then onto the dryer. Drive rolls, which may be pinch rolls or S-wrap rolls, or other
pull rolls with large wrap angles to avoid slippage, or vacuum rolls or tables, pull the
substrate through the coater at the desired speed and tension. At the rewind stand,
the coated product is wound into rolls. There are dancer rolls or force transducers
to measure and provide feedback to control the tension in the substrate, and edge
guide systems to keep the substrate running straight in the coating machine.

The feed system maintains the coating solution at the proper temperature and
pumps it at the desired rate to the coating applicator through filters to remove
unwanted solid particles and through a debubbling system.

The coating solution is applied to the moving web with a coating applicator. There are
many different applicators and configurations that can be used for this purpose, and
these details will be discussed later. The coating station holds the coating applicator
in a fixed position and permits the operator to precisely and accurately set the coating
parameters such as gaps, roll speeds, etc. These settings must be maintained during
the coating run. The coating station should not induce chatter in the coating.

The dryer dries the wet coating by supplying heat to evaporate the solvent and
circulating air to remove the solvent. Most web dryers are impingement devices that
blow hot air against the wet coating. In flotation dryers, hot air also blows against
the back, uncoated side. This not only supplies additional heat but also supports
the moving substrate. Additional heat may be supplied by infrared heaters. Infrared
heaters are frequently used to increase the dryer capacity without increasing the
dryer length.

The coating line may also contain a section between the unwind and the coating
applicator to surface treat the substrate before it is coated. Flame treatment, corona
treatment, and gas plasma treatment may used to improve the substrate wettability.
This improves the coating quality and increases adhesion to the substrate by increas-
ing the substrate surface energy and by removing or cross-linking a weak boundary
layer on the surface. Web cleaners and static control devices may also be included in
this section.

After the dryer and before the rewind, there may be a posttreatment section where
coatings may be cross-linked with ultraviolet light or an electron beam, moisture
may be added by passing the coated substrate through a steam chamber, or another
sheet may be laminated to the coated substrate.

In addition to production coating machines, laboratory pilot coater machines are

also available. These pilot coaters contain the same basic components as the manu-
facturing lines; however, they are narrower, often 15–60 cm (6–24 in) wide, and run
at relatively low speeds, 0.05–0.25 m/s (10–50 ft/min). They can produce commercial
quality coatings and can be used for research and development, scale-up, prod-
uct development, and small volume production. All of the components—unwind,
coater, web transport, dryer, rewind—and all of the control systems are contained
in a steel and glass enclosure as shown in Fig. 14.2.

Figure 14.2. Yasui Seiki CAD laboratory coater.Source: Reprinted with permission of
Yasui Seiki Co.

There are two laboratory coater designs that are used to develop product—batch
sheet coaters and continuous coaters. Sheet coaters are used to develop new prod-
ucts where many different solutions need to be coated and only small samples are
 available. These methods use devices such as draw-down blades, dies, or wire-wound
rods (Mayer rods) to spread a uniform solution layer across a substrate. Most
applicators can provide wet coating thicknesses from 5 to 1300 μm (0.2–50 mil).
Spray coaters may also be used to coat sheets. The coated substrates or sheets may
be dried by ambient air or in a lab oven.

Laboratory automated sheet coaters are available. In these coaters the sheet coating
is mechanically controlled. The coated sheets may be fed directly into a dryer, with
the temperature and residence time controlled. Compared to hand coaters, these
give better reproducibility with much higher productivity and lower overall costs. A
typical laboratory sheet coater is shown in Fig. 14.3.

Figure 14.3. Laboratory sheet coater.Source: Werner Mathis, USA.

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