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530 VERNARDAKIS

Coatings Teehnology Handbook, D.Sotos, Ed., New York: Mareel Dekker, 1991. As a result of the physical and chemical characteristics of pigments, pigments and dyes
differ in lheir application: when a dye is applied, it penetrates the substrate in soluble form,
afler which il may or may not become insoluble. When a pigmenl is used to color or opacify
a substrate, the finely divided, insoluble so lid remains throughoUl the col'oration process.
Organic pigments are highly colored, inert synthelic compounds that are usually
brighler, purer, and richer in color than inorganic pigments. Generally, however, they are
less resistant to sunlighl (some fade badly on exposure to light), to chemicals (greater len-
61 dency to bleed in solvents), and to high processing temperatures (Iower heat stability); quite
often 100, lhey are more expensive than inorganic pigments. Pigmenls are c1assified by the
"Colour Index" according lo specific pigmenl name and conslilution number. For example,
Pigment Dispersion phthalocyanine blue is known by the C.I. name Pigment Blue 15 and, its el. number is
74160, while litanium dioxide is C.I. Pigment White 6, C.I. 77891. The greal number and
Theodore G. Vernardakis variely of organic ami inorganic pigments make it impossible to treat them al! in this chap-
Sun Chemjcal Corporation ter. References should be consulted for information on pigmenl types, chemical and physi-
Cjndnnati. Ohjo cal properties, melhods ofpreparation, grades, specifications, and applications. See, for ex-
am pie, References 8-11.

2.2 Pigment Particles


Pigments are normally produced in a wel presscake form, which upon drying and grinding
or spray drying assllmes the form of afine dry powder. Presscakes, either at their normal
pigment content (20-40%) or as "high solids"(50-60%), are used by the manufacturers of
aqueous pigment dispersions for paint, textile, and ink applications, as well as by those who
1.0 INTRODUCTION produce fIushed colors for oil ink or coatings applications. Dry pigment powders are used in
a host of other systems such as solvent inks,coatings, and plastics. Pigments in the presscake
The dispersion of pigments in fIuid media is of great technological importance to the coat- or dry powder form ar-e composed of fine particles, normally in the submicrometer size
ings manufacturers who deal with pigmented systems. The basic aim is to change the physi- range. Their color properties are generally influenced by particle size and partic1e size dis-
cal state of pigments to achieve desired effects in specific application systems. The disper- tribution; therefore, an assessment on the degree of dispersion must, above all, be consid-
sion process involves the breaking down and separation ofthe aggregated and agglomerated ered in terms of these critical measurements 12.In general, color properties, such as strength,
particles that are present in all pigmeñts in their normal form after their manufacture. Dis- transparency, gloss, rheology, and lightfastness of all pigmented systems, are affected to a
persion is not considered to be a process of pulverization, but rather a process of partic1e greater or lesser extent by the size and dislribution ofthe pigment partic1es in the dispersion,¡ .
separation, homogeneous distribution of the particles in a medium, and stabilization of the For example., phthalocyanine blue is first prepared commercially in a "crude" pigment form
resultant system to prevent reaggregation, reagglomeration, fIocculation, and settling. The having a large partic1e size, up to 25 11m.As such,it has little color value and must therefore
process of dispersion must be done efficiently and in the shortest time possible to draw out be reduced to smaller, finer particles to enhance its coloristic properties. After partic1e size
of the pigment its maximum color properties at the least cosI. reduction (down to 0.03--0.15 11m),an excellent pigment is obtained, which exhibits a high
The topic of pigment dispersion in fIuid media has been covered extensively in the litera- degree oftinctorial strength, transparency, and gloss. Typical electron micrographs of these
ture1~. The theoretical aspects of pigment dispersion apply equally well to inorganic and two materials, showing partic1e size, are reproduced in Figure 1. and associated crystals
organic pigments. In this chapter, the practical examples of surface treatments apply pri-
marily to organic pigments, but similar treatments can be carried out on inorganic pigments Pigment particles normally exist in the form of primary pa~ticles,laggregates, agglomer-
ates, and fIocculates. Primary particles are individual crystals as they are formed during the
as well. ' manufacturing process. (Fig. 2). They may vary in size depending on the c09ditions of pre-
cipitation and growth, which are controlled by the pigment manufacturero The scanning
2.0 A BRIEF INTRODUCTIONTO PIGMENTS electron photomicrograph ofFigure 2 for micronized sodium chloride (although this is not a
pigment), is used only to illustrate the individual and associated crystals that make up the
2.1 Pigment Definition primary particles of a compound.
Aggregates are collections of primary particles thal are attached to each other at their
Materials are colored by the use of pigments or dyes. Pigmenls are colored, black, while, or
surface~ or crystal faces and show a tightly packed structure. Agglomerates consist of pri-
tluorescent particulate organic or inorganic solids,'usually they are insoluble in, and essen-
mary particles and aggregates joined at the comers and edges in a ¡ooser type of arrange-
lially physically and chemically unaffected by, lhe vehic1e or substrale in which they are
menl. Aggregates are formed during the manufacturing process in the course of the ripening
incorporaled. They alter appearance by seleclive adsorption and/or by scattering of lighl?
period of the precipitates. Agglomerates, most often, are formed during the drying of the
Pigmenls usually are dispcrsed in vehicles or substrales for applicalion (e.g., in inks,
painls, plaslics,or olhcr polymeric material). Pigments rela in a cryslal or particulale struc-
tllre throllghoul the coloration process. be( ec(O I
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PIGMENT DISPERSION 531 532 VERNARDAKIS

Figure 2 Scanning electron photomicrograph showing primary parlicles: (a) individual cryslals
and (b) associatedcryslalsof micronizedNaCI.

."

0.5 ~m

Figure 1 Scannil1g eleetron photomierograph of copper phlhalocyanine blue crude (top) and
Iransmissiol1 electron pholomicrograph of copper phlhalocyanine blue pigment (bollom) showing
parlicle sizc differences; Pigment Blue 15.

Figure 3 Transmi~sion electron photomicrograph showing (a) aggregated and (b) agglomera\cd
pigment parlicles. D&C Red No. 30, Vat Red 1.

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PIGMENT DISPERSION 533 534 VERNARDAKIS

a minimum ofloose aggregates and agglomerates. In practice, reduction to the primary par-
ticle size is largely determined by the nature of the pigment (Le., its dispersibility), by the
dispersion systern and processing equipment, and by the end-use requirements of the prod-
uc!. .
Dispersion should not be confused with pulverization. The latter is simply a comminu-
tion process whereby large pigment lumps are broken down to smaller units, which consti-
tute the powder formo Pulverization does not break down the aggregated, agglomerated, and
flocculated particles into primary particles. Dispersion, however, accomplishes this effec-
tive[y.

3.1 Pigment Wetting


[t is generally recognized that the dispersion process consists of three distinct stages: wet-
ting, deaggregation-deagglomeration, and stabilization. The wetting st.1ge involves the re-
moval from the surface of the pigment particles of adsorbed molecules of gas, liquid, and
other materials and their replacement with molecules of the vehicle. [n other words, the
pigment-air interface in dry pigment powders or the pigment-water interface in
presscakes is replaced by the pigment-vehicle interface. This is accomplished through pref-
erential adsorption. The efficiency ofwetting depends primarily on the comparative surface
tension properties of the pigment and the vehicle, as well as the viscosity of the resultant
mix.

3.2 Particle Deaggregation and Deagglomeration


After the initial wetting stage, it is necessary to deaggregate and deagglomerate the pigment
particles. This is usually accomplished by mechanical action with devices such as ball milis,
Figure 4 Transrnission electron photornicrograph showing flocculated pigrnent particles.
bead milis, and two-roll milis. As the pigment powder is broken down to the individual
Dirnethylquinacridone rnagent.1,Pigrnent Red 122.
particles, higher surface areas becorne exposed to the vehicle and larger amounts of it are
required to wet out newly formed surfaces. During this stage of deaggregation, the amount
offree vehicle in the bulk diminishes; therefore, the viscosity ofthe dispersion increases. At
presscakes and the subsequent dry milling of the pigment lumps. Figure 3 shows typical higher viscosities, shear forces are greater and the breaking down and separation ofparticles
arrangements of aggregated and agglomerated pigment particles. become more efficien!. It is this process of mechanical breakdown of the aggregates and
Flocculates consist of primary particles, aggregates, and agglomerates, generally ar- agglomerates that demands a high energy input and can become quite costly. Some easily
ranged in a fairly open structure, as shown in Figure 4. Flocculates may be broken down dispersible pigments have been developed lately to aid in the reduction of energy require-
easily under shear, but they will form again when such shear forces are removed and the
mel,1ts.Such pigments are produced by surface treatment of the pigment during manufac-
dispersion is allowed to stand undisturbed.
ture, with the purpose of reducing or inhibiting agglomeration-aggregation formation. In
many cases, such treatments are highly specific to a single ink, paint, coating, or plastic
3.0 THE DISPERSION PROCESS medium. .

The primary purpose of dispersion is lo break down pigment aggregates and agglomerates 3.3 Dispersion Stabilization
to their optimum pigrnentary particulate size (down to individual single partic1es, if possi- The third stage of great importance in the dispersion process is the stabilization of the pig-
ble) and to distribute these pigment particles evenly throughout a medium (Le., the carrier).
ment dispersion. This ensures that complete wetting and separation of the partic1es has been
Usually the carrier is a liquid or a solid polymeric material that is deformable at high tem-
reached, and also that the pigment particles are homogeneously distributed in the medium.
peratures during processing. To achieve the optimum benefits of a pigment, bolh visual and
If the dispersion has not been stabilized, flocculation may occur as a result of clumping
econornic, it is necessary to obtain as full a reduction as possible to the primary particle size.
together of the pigment particles. Flocculation is generally a reversible process. Floccula-
After all, the color strength ofa pigrnent depends on its exposed surface area: the smaller the
tes typically break down when shear is applied and will form again when the shear is re-
particle size, the higher the surface area, and thus, the stronger the color. Furthermore, the
moved. Where a pigment dispersion is not stabilized by the action ofresin molecules in the
pigment is generally the l1Iostexpensive constituenl of any pigmented system; therefore the
vehicle, the use of surfactants or polymeric dispersants can be considered. Such additives
user normally wants to obtain optimum performance with the smallest possible amount of
pigmen!. [deally, a good pigment dispersion consists chiefly of primary particles, with only
PIGMENT DISPERSION 535 536 VERNARDAKIS

may be uSt:d dirt:ctly during pigment manufacture, or they may be incorporated in the vehi-
cJe.

4.0 THE ROLE OF SURFACE ENERGY

Jt is well known that mplecular forces at the surface of a liquid are in a state of imbalance.
The same is true of the surface of a sol id, where the molecules or ions on the surface are
subject to unbalanced forces of atlraction normal to the surface plane. Such atoms do not
have all their forces satisfied by union with other atoms. As a result, there is a net force,
which tends to pull the surface molecules into the bulk. The opposing force, which resists
Figure 5 Partial wetting of a salid surface by a liquid in aeeordance with the Young-Dupré
thisinwardlypullingforce,isknownasthesurfaceenergy or surface tension. To
equation.
satisfy these surface forct:s, liquids and solids tend to attract and retain on their surfaces
dissolved substances in the solution or gasses from the surrounding atmosphere. These
forces are short-ranged atlractive forces, known as van der Waals or London forces, and
they playa very important role in particJe aggregation, wetling, and dispersion stabilization. (high surface tension), such as water, will not entirely wet out a high energy surface. In this'
case, the wetling energy is equal to or less than thesumof theadsorption and interparticle
4.1 Surface Energy and Surface Area atlraction energies, and wetling may be either partial or nonexistent. The liquid will not
Pigments having a very small particJe size exhibit high surface arca and consequently high spread entirely over the surface, asshown in Figure 5. The relationship that describes such a
surfact: energies. A~ large pigment particles are broken down into several smaller particles, system is given by the Young-Dupré equation as follows:
new surfaces are constantly ereated, contributing to a higher surface arca and thus a higher
surface energy. Ysv= YSL+Yl.v. cosO
Let us assurne that a pigment powder has a surface area S of 60 m2/g and a density r>of
1.0 g/cm3. Its basic particle diameter D from
where ysv, YSL,and YLVare the interfacial energies at the solid-vapor, solid-liquid, and liq-
uid-vaporinterfaces,respectively,and e is the contactangle. For completewetting, the
D=~ contact angle is zero (cose becomes unity), and the liquid spreads entirely over the solid
pS
surface. For e > O, wetling either is incomplete or does not occur at al!.

4.3 Surface Energy and Destabilization of the Dispersion


will be 0.1 ¡.im. If these particles are cubic in structure, and if, for the sake of simplicity, we
assume that a 1 cm3 of pigment is broken down into particles 0.1 J.!min size, then 1 x 1015 Surface energies play an important role in the destabilization of the dispersion. ParticJes
particles will be produced. We assume also that the particles are in perfect cubic packing. To dispersed in liquid media are in constant motion (thermal or Brownian movement). As they
get an idea of the area created by the new surface, we need only compare the surface area of move through the medium, they collide with other pigmentparticJes.The frequency of these
6 cm2 for the 1 cm cubic particle to the surface area of 600,000 cm2 (60 m2) for the 1 x 1015 collisions depends on the size of the particJes and on the viscosity of the medium. During
cubic partic1es lhat are 0.1 11min size. The increase in surface area is 100,000-fold. The new such collisions, the particJes will attract and may join with other particles because of the
surfaces produced are tremendously large. The surface energies associated with these new powerful short-range London-van der Waals attractive forces, which in effect are surface
surfaces are also quite large. These van der Waals surface energies crea te the attraction energies. These forces are electrical and are due to the interaction of the dipoles that are
between the submicrometer particles that come together to form the aggregatesand agglom- present in the partic1es, as permanent dipoles (polar particles) or induced dipoles (nonpolar
era teso but polarized particJes).
Once the particles have come together, they may reaggregate or form flocculates if
4.2 Surface Energy and Pigment Wetting their surface is not protected, and they will settle to the bottom of the container. This is an
undesirable effect for the ink, paint, or coatings manufacturero Therefore, to prevent reag-
Surface energies p'layan important role in the wetling ami stabilization of pigment disper-
gregation or flocculation, such dispersions must be stabilized.
sions. Por wetting lo be efTeclive, the wetting energies nf the pigment-vehicJe interface
rnust be grealer than the surn nI' the adsorption energy (this is because 01'substanceson the 4.4 Surface Energy and the Acid-Base Concept
pigment surface)andthe attractive energy that holds the pigment partides together. Gener-
ally, lower energy (Iow surfact: tension) liquids, such as aliphatic and aromatic hydrocar- The idea of surface energy in pigments has been closely related
to the acid-base concept,
bons. will spread over. or wet. higher energy surfaces. Quite nften, it happens that a liquid advanced by Sorensen,13 who has used it to describe the interaction between pigments,
does not spread over a pigrnentsurfaee completely. This occurs when a high energyliquid hinders, and solvents, to oblain optil1lally stablc pigmcnt dispersions having the best appli-

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PIGMENT DISPERSION 537 538 VERNARDAKIS

, ------
~ation properties in fluid ink systems. Such interrelation between the surface energies 01'
these three components in a dispersion can be characterized by their acid-base properties. 1
// + "" E LECTRICAL
DOUBLE
Pigments can be classified as acidic (electron acceptors), basic (electron donors), am- I + +\ LAYER
photeric (electron acceptors ami donors), or neutral. Binders and solvents can be similarly /1 + + \/
I'+ +' \
characterized.
Acidic pigments should be used with basic resins (polyamide, melamine, alkyd), while I I
basic pigments should be used with acidic resins (vinyl, acrylic, maleic). Amphoterics can \ + + + I
be used with both resins. Neutral pigments should be surface treated to improve their disper- \ I
\ + I
sion characteristics. The solvent must have the same acid-base character as the pigment, \ + 1
whereby the interactinn between the solvent and the pigment surface is minimized and at the " + /
" + ,,"
same time the interaction between the resin binder and the pigment surface is maximized. In '-- - - - --- + -.,/./
nther wnrds, there shnuld he no cnmpetition between solvent and binder for the pigment
CHARGE STABILIZATION
surface; to obtain maximum dispersion amI stlhility, nnly the binder should adsnrb.

5.0 MECHANISMS FOR THE STABILlZATION OF DISPERSION

5.1 Charge Stabilization


Dispersions may become slable through two generally accepted mcchanisms: charge stabi-
lization and steric or entropic stabilizalion. Charge stabilization is due to electrical repul-
sion forces, which are the result of a charged electrical double layer surrounding the parti-
cles as shown in Figure 6. The charged electrical double layer developed around the parti-
cles extends well into the liquid medium, and since all the particles are surrounded by the
same charge (positive or negative), they repel each other when they come into close proxim-
ity.

5.2 Steric or Entropic Stabilízation STERIC OR ENTROPIC STABILIZATION

Steric stabilization is due to steric hindrance resuiting from the adsorbed dispersing agent, Figure 6 Charge and steric or entropic stabilizations.
the chains 01'which become solvated in the liquid medium, thus creating an effective steric
barrier that prevents the other particles from approaching too close. This phenomenon is
also called entropic stabilization because, as the coated particles approach each other, the
solvated chains 01'the adsorbed dispersant lose some 01'their degrees 01'freedom, resuiting their solubility in water or oil-solvent systems. High HLB values mean that the surfactant is
in a decrease in entropy. Such lowering in entropy gives rise to repulsive forces, which keep soluble in water (an abundance of hydrophilic groups).Low HLS values, on the other hand,
the particles away from each other. This type 01'steric or entropic stabilization is also repre- mean that the surfactant is soluble in oi! or solvents (an abundance of lipophilic groups).
sented in Figure 6. Surfactants attach themselves to the pigment partic1es via preferential adsorption, as
shown in Figure 7 for aqueous and nonaqueous systems. In aqueous systems, the lipophilic
(or hydrophobic) groups are adsorbed on the particle surface, and the hydrophilic (or
6.0 SURFACE TREATMENT lipophobic) groups extend into the bulk 01'the vehicle. In the case of non-aqueous solvent
6.1 Surfactants systems, the hydrophilic grollpsol' the surfactant are attached to the particle surface and the
lipophilic groups (lails) extend into and are solubilized by the solven!.
Surface active agents or, simply,surfactantsare substances that are used to lower the inter- Surface treatments are effective for pigments because their surfaces contain polar or po-
facial tension between a liquid and a solid. Such is the case for pigments in fluid media, with larized functional groups, which can serve as adsorption sites for the hydrophilic or
lhe expressed purpose 01'improving pigment dispersihility by improving pigment wetting lipophilic groups ofthe surfactants. Por instance, organic pigments typically contain groups
characleristics, (ueventing reaggregation, and increasing lhe stahilily 01'the dispcrsion. A I I
sllrfactant molecule typically contains two grollps 01'opposite polarity and solubility. The such as nilro (-N02), hydroxyl (--01-1), carbonyl (-C =0), amide(-NH - C =0),
hydrophilic group is the polar, water-Ioving part, while the lipophilic group is the nonpolar, methoxy (--O-CH3), chlorine (-Cl), hromine (-Sr), sulfonate (-SOj), carboxylate
oil-Inving part nI' the molecule. (-COO-), ami metal ions such as Ba+2, Ca+2, Mn+2, and Cu+2, which can function as the
Surfactanls are characterized by lheir IILB value (hydrophile-lipophile balance), which anchoring sites for the hydrophilic or lipophilic groups 01'the surfactants.
is a ratio 01'the hydrophilic to lipophilic groups on the molecule and gives an indication 01'
PIGMENT DISPERSION 539 540 VERNARDAKIS

poly(12-hydroxystearic acid)] with the carboxy group functioning as the anchor and the
polyester group as the solvated chain. Others with multiple anchor groups, are fatty
polyureas and polyurethanes, which may even contain polymeric solvatable groups instead
of the long fatty chains. .

6.3 Surface Modifying Agents

Surface modifying agents are another group of additives that can be used lo aid the disper-
sion of organic pigments in organic media. These agents are often pigment derivatives (e.g.,
large tlat dye molecules), which provide improved resistance to tlocculation and greater
AOUEOUS SYSTEM stability to the dispersion. The pigment derivative is adsorbed onto the pigment surface via
lhe van der Waals attraclive forces, which acl over a large area, because such large planar
dye molecules lif tlal on lhe pigmenl surface. They may be used either alone or in conjunc-
lion wilh a polymeric dispersan!. When used alone, lhey inlroduce or increase on the surface
"- of nonpolar or low polarily pigmenls, lhe number of polar sites, which are necessary to in-
LIPOPHILlC leract with lhe resin in the vehic1es, to slabilize lhe dispersion. When used logether with the
polymeric dispersanl, they provide anchoring siles on which the anchor groups of the dis-
¡ GROUPS persanl will become attached. In this contexl, they can be used synergistically with dispers-
ing agents, al which lime lhey are called colored synergists.

7.0 SURFACE TREATMENT DURING PIGMENT MANUFACTURE

NON-AOUEOUS SYSTEM Generally, surface-treated pigmenls are more easily dispersible, produce more stable dis-
persions in tluid media wilh improved tlow, and impar! higher slrenglh and gloss lo the
Figure 7 Surfac!:lnl altachmenl 011pigmenl particles in aqueous and nonaqueous dispersions. printed films, when compared wilh untreated pigments. Surface treatments can be carried
oul at different stages of pigmenl manufacture. Some pigments are prepared direclly as fin-
ished producls, while others are in the form ofa crude pigment that must be conditioned into
the pigmentary sta le.
Use of surfactants is typically made at the initial stage of pigment manufacture. During
It is well known, however, that classical surfactants do not always improve the disper- the precipitation of the intermediate (e.g., diazo in the preparation of azo pigments), surfac-
tants are used to wet out and control the fineness of the precipita te, and they may also act as
sion characteristics of pigmenls,especially when pigment surfaces are Iow in polarity or
promoters to accelerate the azo coupling teaction. At the second stage, during the precipita-
nonpolar and are dispersed in nonpolar vehic1es. With such pigments and vehicles, disper-
tion ofthe pigment (e.g., in the azo coupling reaction), surfactants may be used in the disper-
sants and surface modifying agents of other types must be used to improve wetting and dis-
persibility and to prevent flocculation of pigment particles. sion ofthe pigment particles as they are being formed-for example, in azo yellows, which
are precipitated in the pigmentary sta te, or in the dispersion of the precursor (dyestuff), as in
6.2 Polymeric Dispersants the case of metallized azo reds (which are first formed as sodium salts), to controllhe salt
formation (barium, calcium, etc.), and thus produce the final pigmento At the third stage,
Polymeric dispersants or "hyperdispersants" 14are claimed to be more effective dispersion during the conditioning of the pigment, surface treatments are used ter pigment particle dis-
stabilizers for nonaqueous systems. These substances have a two-part structure, one con- persion, for coating the pigmenl surface to prevent aggregation, and for controlling the
sisting of an anchoring functioning group (or groups), and the other consisting of a poly- growth of crystal parlic1es. If partic1es are too difficult to filler, use of a specific additive
meric solvatahle chain lo which the functional grnup is atlached. They are in effect poly- (tlocculant) somelimes induces controlled flocculation and facilitates filtration. Complex
meric surfactants or dispersanls but were developed for use in specific nonaqueous systems, formation with additives may also be carried out during this conditioning stage to stabilize
where classical surfaclanls have limitations. When they are used as dispersants for organic the partic1es and increase dispersibility, as is the case with diarylide yellows, which may be
pigments, il is prcferable thal they have mulliple anchoring groups on one polymeric chain, surface treated with fatty amines to produce Schiff base stabilization and result in easily
beca use organic particles are not as strongly polar as inorganic particles. Such dispersants dispersible pigmenls.
may be 01' a fally polyester type, containing a carboxy group at lhe end [e.g.,

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PIGMENT DlSPERSION 541 542 VERNARDAKIS

8;0 SURFACE TREATMENT OF PIGMENTS: APPLlCATION

8.1 Organic Pigments

The published literature dealing with surface treatments of organic pigments patented or
otherwise, is so extensive that no attempt is made to review it, although it may be referred to,
occasionally. Readers are urged however, to consult the review by Hayes,15 which covers
the role of classical surfactanls, polymeric dispersants, and pigment derivatives in surface
treatments. Othcr reviews of interest are those by Topham,16 Merkle and Schafer,17 and
Hampton and McMillan,14 the latter dealing specifically with polymeric dispersants. Fur-
ther examples will be presented here.
It is well known lo the pigment manufacturer that rosination is perhaps the oldest surface
treatment known, especially for azo pigments, where rosin (abietic acid) is precipitated onto
the pigment surface as the barium or calcium salt.1t can also be used to treat other pigments,
such as copper phthalocyanine blue, 18and for a host of similar applications, in a polymer-
ized formo Along lhe same lines, long chain carboxylic acids (fatty acids) have also been
used lo treat pigment surfacesl9. A likely arrangement of Ihese molecules adsorbed on the
surface is shown in Figure 8. The hydrophilic anchor groups are attached to the surface, with
the lipophilic groups projecting outward. The use ofrosin has been mentioned because ofits
historical significance and because it is still widely used today, since it is one of the least
expensive surface treating agents.
In the course of a study by the author for the development of a diarylide yellow AAOT
(Colour Index Pigment Yellow 14) for flexographic ink applications, it was found that a
desirable product was one prepared in the presence of an amine-type ethoxylated guanidine (/)
weakly cationic surfactant, in combination with a polar tetramethyl decynediol solvent.20 It W
..J
appears that these two surface active agents worked synergistically to produce a strong, ~ 16
DIAM -
transparent and nonflocculating pigment, as opposed to products in which the surfactant or 1- /' AVER-0.104 pm
el:
the solvent or both were absent from the preparation. Transmission electron micrographs <t
a.. 8
u.
o .
ci O
z
0.05 0.10 0.15 0.20

PAR TIC LE DIAMETER (pm)


BARIUM SALT OF ABIETlC ACID FATTY ACI D

Figure 9 Transmission electron photomicrograph and particle size distribution of an untreated


diarylide yellow AAOT, Pigment Yellow 14.

and particle size distributions for such pigments are shown in Figures 9 and 10. It is apparent
=
that the particlesize of the treated sample is smaller (average particle diameter 0.073 f.lm)
and much more uniform (narrow distribution) than that of the untreated sample (average
PIGMENT
particle diameter = 0.104 ¡.tm and wider distribution). To show pigment flocculation in
flexographic inks, optical photomicrographs were obtained. Figure 11, a micrograph of the
liquid ink on a glass slide with cover for the untreated pigment, exhibits flocculation. Figure
Figure 8 Trcatmcnt of pigmcnl surfaccs with rosins and rally acids.
PIGMENT DISPERSION 543

p.2 !-1m,

Figure 11 Oplical photomicrograph of liquid ink prepared with untreated diarylide yellow
CJ)
AAOT. Shows tlocculation of pigment particles. Same pigment as that of Figure 9.
24
-
u
~DIAMAVER = 0.073 pm
16
<t
c..
u. 8
o
¿
z o
0.05 0.10 0.15 ú.20

PA R TIC LE DIAMETER (p m)

Figure 10 Transmission electron photomicrograph and particle size distribution of a sur-


face-treated diarylide yellow AAOT, Pigment Yellow 14.

12, on the other hand, represents the liquid ink prepared with the surface-treated pigment
and shows that this is a non-
flocculating pigment.
Polymeric dispersants2l such as poly(12-hydroxystearic acid) are reportedly used both
as free acid and as a salt with a variety of organic toners; these agents show more effective-
ness when reacted with a primary amine (3--<1imethylaminopropylamine, 3-oc-
tadccylaminopropylamine, etc.). The latter types can be used with pigment derivatives to

Figure 12 OpliC:ll pholomicrograph of liquid ink prcparcd with surfac 'cd diarylidc ycl-
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low AAOT. Does not show (loccu]ation of pip,l11cnt particles. Samc pip,ll1c ,lal of Fip,ure 10.
(
PIGMENT DlSPERSION 545 546 VERNARDAKIS

POLY (12 - HYDROXYSTEARIC ACID)


SULFONATED PHTHALlMIDOMETHYL
COPPER PHTHALOCYANINE

CuPe-SO] H : COPPER PHTHALOCYANINE


SULFONIC ACID

3 - OCTADECYLAM INOPROPYLAMINE

Figure 14 Surface lrealmenl of copper phlhalocyanine blue, Pigment Blue 15. wilh a sulfonaled
copper phthalocyanine additive, sllrface modifying agent.

preceding cases, the planar sulfonated quinacridone molecules appear to lie flat on the
quinacridone pigment surface and thus improve considerably the dispersion properties of
COPPE R PHTHALOCYANINE BLUE the pigment, especially when used in coating applications. Figure 15 represents the arrange-
ment of sulfonated quinacridone derivative on the pigment surface.
Pigment derivatives of azo reds, 28 oranges, and yellows 29have also been used for sur-
Figure 13 Surface treatment of copper phlhalocyanine blue, Pigment Blue 15, showing Ihe syn-
face treating the corresponding pigments. With azo yellows, treatments can be carried out in
ergislic effcct belween slllfonalcd copper phlhalocyanine and a polymeric dispersanl on the pigment
surface. situ with fatty amines to produce easily dispersible products through a Schiffbase reaction
I
between the - e= o (carbonyl) groups ofthe pigmentand the -NH2 groups ofprimary
I
amines, to form - e = N- Schiffbases.29-32Derivatives of monoarylide and diarylide
produce a synergistic effect on the pigment surface for improved dispersion. An example is yellow pigments can also be prepared by reacting the pigment with a primary diamine and a
copper phthalocyanine sulfonic acid22.The mechanism of synergism is illustrated in Figure glycidyl ether33 to produce a Schiffbase. The structure of one of these derivatives is shown
13 for the surface treatment of copper phlhalocyanine blue. A great number of other in Figure 16 for Pigment Yellow 12, AAA yellow. Again, the planar pigment molecule ap-
phthalocyanine deriva tives have also been prepared and used as pigment stabilizers for pears to lie on the pigment surface, and the long chains project outward into the vehicle 10
produce stabilization of the dispersion.
phthalocyanine blue23.
Phthalocyanine pigments may be conditioned from the crude state to the pigmentary
8.2 Inorganic Pigments
form, for example, by milling the "crude" with a phthalocyanine derivative24 such as a sul-
fonated phthalim i domethyl phthalocyanine25 in the absence of any milling of grinding Titanium dioxide, in the two naturally occurring crystal forms, anatase and rutile, is the
aid26. These large planar molecules appear to lie flat on lhe copper phthaloeyanine surface, most important white pigment, which provides maximum opacifying power. Normally,
as shown in Figure 14, and they impart stability to the dispersions when used in printing Ti02 pigments are not useo in their pure form beca use of their poor oispersibility in a variety
inks, painL~, ano coalings, wilhout any aoditional conditioning of the mili ed product. of resins and solvents. Generally, they are surface coated with small amounts of alumina,
Pigmenl deriva tives are by no means limited to phthalocyanines. Quinacridone pigments silica, or bolh (up to 3% total, on Ti02) to increase the functionality of the surface (active
have been surt:lce lrealcd with sulfonateo quinacrioone oerivatives27 either as the slllfonic aosorption sites for the resin molecules) ano lo improve dispersibility ano impart stability lo
acio fonn or as lhe metal slllfonalc salt. wilh a wioe range of metals possible. As in the the oispersion, especially in alkyo resin paint systems. For alumina-i:oated titanium diox-
PIGMENT DISPERSION 547 548 VERNARDAKIS

ide, 34the highly basic sites on the alumina surface, which are much more basic than the sites
on the Ti02 surface, cause specific adsorption of the acidic functional groups of the alkyd
resin molecules. The remaining parts ofthe resin molecules (long chains) extend away from
the surface, creating a considerable amount of steric hindrance around each pigment parti-
cle, thus resulting in steric stabilization of the dispersion.
Alumina-coated titanium dioxide, iron oxide red, and other inorganic pigments and fill-
ers can be surface treated with alkanolamines (aminoalkanols), having the general formu-
SULFONATEO QUINACRIOONE RED las:

M = H,AI,Mg,Zn,Cu,Ni,Cd,Cr,Co,Mn R¡-CH-CI-I2-NH2. R2-CH-CH-R3, etc.


I I- I
01-1 01-1 NI-12

where R¡, R2, and R3 are alkyl groups containing from 1 to 22 carbon atoms in the chain. 35
The dispersibility of these pigments is increased considerably when used in paint formula-
tions containing air drying resin vehicles. The stability of the dispersion is similarly im-
proved because of the steric stabilization imparted to the pigment particles by the R¡, R2,
and R3 long chain alkyl groups.
Organic isocyanate adducts 36are uscd as effective dispersing agents for several classes
of inorganic pigments, including zinc oxide, iron oxides, Prussian Blue, cadmium sulfide,
I ultramarine, vermilion, and chrome pigments (zinc, barium, and calcium chromates). These
I Q U I N A C R I O O N E RED
agents improve the dispersion characleristics and the flocculation resistance of the above-
listed pigments when incorporated into conventional alkyd paint vehicles with organic sol-
Figure 15 Surfacc trcatmenl of quinacridone red, Pigment Violct 19, with a sulfonatcd vents, where these systems also contain a substantial amount of titanium dioxide.
quinacridone additive, surface modifying agent.

9.0 THE CHARACTERlZATION AND ASSESSMENT OF DISPERSION

The extent to which a pigment is dispersed in the medium or the degree of dispersion is
normally assessed in terms of color strength, gloss, brightness, and transparency, and it also
has an effect on the rheological properties of the system37-39.Since all these properties are
govemed by Ihe size and distribution of the pigment particles in the dispersion, one can,
H2N-R-NH2 : PRIMAR Y OIAMINE tOday, measure these properties using any of the latest particle size analyzers based on the
light scattering principIe of the dispersed particles 12.With theseinstruments,a verydilute
, /0\
ROCHrCH-CH2: GLYCIOYL ETHER
suspension is required, and it is necessary to know the refractive index and viscosity of the
suspending medium. The average particle diameters and the particle size distributions ob-
-' tained are those of individual particles, aggregates, agglomerates, and flocculates in the dis-
I
'-' , persion. The advantages of these inslruments are that they are quite easy to operate, they

H-N
Q N-H
give results rapidly, and they allow the dispersion process to be followed at different limes
and at different stages.
I CI CI I One such instrument is the Coulter model N4 Submicron Particle Analyzer. Figure 17
O=C C=O
I --, _o, I represents the particle size results for a green-shade phthalocyanine blue, CJ. Pigment Blue
H-C-N=N
I
,':
-@-d-
'..-'
: 1
'
N=N-C-H
I
15:3, in an aqueous dispersion. The distribution is quite narrow, and the mean particle di-
(R'oCH2CHCH~) ameter is 0.117 ¡.1m.These results are very similar to those obtained from inspection of the
I c:2 N-R-N=CI C=N-R-N(CH2CHCH20R')2
I I
transmission clectron micrographs of Figure 1 for the same phthalocyanine blue pigment in
OH CH3 CH:3 OH
the dry powder fonn, showing that very li!tle aggregalion exists in the dispersion.
Such particle size analyzers, based on light scattering, can be used very effectively 10
OIARYLlDE YELLOW AA A (PIGMENT YELLOW 12) OERIVATIVE study particle size changes that occur during the dispersion of pigments in fluid systems.
Furthermore, time studies may be carried out on the nocculation of pigments by determin-
Figure 16 Diarylidc ycllow AAA, Pigmenl Yellow 12, derivative; Schiffbase.

( ( (
( ( (
PIGMENT DISPERSION 549 550 VERNARDAKIS

quickly. And since this is an energy intensive process, in terms of the dispersion equipment
utilized, less energy is required, which results in greatcr economic benefits for the pigment
CUMULANT RESULTS SDP INTENSITY RESULTS user.
SAMPLE ID: CuPe AOUEOUS DISP. SAMPLE ID: CuPe AOUEOUS DISP.

MEANDIAMETER
= 118 NM _ MEANDIAMETER=117 NM - REFERENCES
95% LlMITS = 118 TO 118 NM S.D. = 30 NM C.V.= 26% 1. G. D. Parfitt, Ed., Dispersion o/ Powders in LU¡uids 2nd ed. New York: Wiley, 1973.
STANDARD = 37 NM SIZE S. D. AMOUNT 2. T. C. Patton, Painl F/ow and Pigmenl Dispersion, 2nd ed., New York: Wiley, 1979.
DEVIATION 1: 117 NM 30 NM 100 % 3. V. T. Crowl, J. Gil C%ur Chem. Assoc., 55, 388 (1972).
4. O. Hafner, J. Gi/ C%ur Chelll. Assoc., 57, 268 (1974).
20 5. W. Carr, J. Gi/ C%ur Chem. Assoc., 61, 397 (1978).
SDP DIFFERENTIAL INTENSITY 6. D. M. Varley and H. H. Bower, J. Gi/ C%ur Chelll, Assoc., 62, 401 (1979).
A
M 7. H. M. Smith, PolYIII. Pailll C%rl., 175,660 (1985).
15 SIZE (NM) AMOUNT(%> 8. P. A. Lewis, Ed., Pigmenl Handbook, Vol. 1, 2nd ed. New York: Wiley, 1988.
O
U 9. G. D. Parfitt and K. S. W. Sing, Eds., Characlerizalion o/ Powder Sur/aces. l..ondon: Aca-
31.6 O
N 10 demic Press, 1976.
T 46.4 O 10. H. P. Preuss, Pigmenls in Painl, Park Ridge, NJ: Noyes, 1974.
I 68.1 4 11. W. M. Morgans, Gutlineso/Painl Techn%gy, Vols. 1 and 2, 2nd ed.l..ondon: Charles Griffin
5 & ea., 1982.
N 100 53
147 41 12. T. G. Vernardakis, Am. lnk Maker, 62(2), 24 1984.
(%> O 13. P. Sorensen, J. Painl Techno/., 47, 31 (1975).
10 100 215 2
1000 14. J. S. Hamptom and J. F. MacMillan, Am. lnk Maker, 63(1), 16 (1985).
316 O 15. B. G. Hays, Am. lnk Maker, 62(6), 28 (1984).
PARTICLE DIAMETER (NM>
464 O 16. A Topham, Prog. Grg. Coalings, 5,237 (1977).
SDP DI FFERENTIAL INTENSITY
17. K. Merkle and H. Schafer, in Pigmenl Handbook, Vol. III, T.e. Patton, Ed., New York: Wiley
1973 pp. 157-167.
Figure 17 Parlicle sizc results of a copper phthalocyanine blue, Pigment Blue 15:3, aqueous 18. A. E. Ambler and R. W. Tomlinson, U.s. Patent 3,296,001 (Jan. 3, 1967); ICl.
19. T. C. Rees and R. J. Flores, U.S. Patent 4,032,357 (June 28,1977); Sherwin-Williams.
dispersion by the Coulter Model N4 Submicron Parlicle Size Analyzer, used 10assess the degree of
20. T. G. Vernardakis, Dyes Pigments, 2, 175 (1981).
dispersion (SDP = Size Dislribution Program).
21. J. F. St3nsfield and A. Topham, U.S. Patent 3,996,059 (Dec. 7,1976); ICl.
22. P. K. Davies, L. R Rogers, J. F. St3nsCield, and A. Topham, U.S. Patent 4,057,436 (Nov. 8,
1977; ICl.
23. Anon., British Patent 1,544,839 (Apr. 25, 1979); BASF.
24. W. H. McKellin, H. T. Lacey, and V. A. Giambalvo, U.S. Patent 2,855,403 (Gct. 7,1958);
ing partic1e size immediately after dispersion and then later, after the dispersions have been American Cyanamid.
allowed to stand for certain periods. This gives a measure of the stability of the dispersion. 25. V. A. Giambalvo and W. Berry, U.S. Patent 3,589,924; American Cyanamid(June 29.1971>-
26. S. L. Johnson, G. McLaren and G. H. Robertson, U.S. Patent4,448,607 (M ay 15, 198 4); Sun
Chemical.
10.0 CONCLUSION 27. E. E. Jaffe and W. J. Marshall, U.S. Patent 3,386,843 (June 4,1968); DuPont.
28. J. Mitchell and A. Topham, U.S. Patent 3,446,641 (May 27,1969); ICl.
There is no question as to the desirability and effectiveness of a fully dispersed and stabi-
29. J. Mitchell and A. Topham, British Patent 1,139,294 (Jan. 8, 1969); ICI.
lized pigmented system. Such a dispersion brings out the optimum color properties of the 30. Anon., British Patent 1,080,115 (Aug. 23, 1967): KVK.
pigment in terms of color strength, gloss, transparency, and rheology. When a pigment is 31. F. Dawson, J. Mitchell, L. R. Rogers, W. Todd, and A. Topham, British Patent 1,096,362
completely dispersed, it contains a larger number of primary partic1es; therefore, a smaller (Dec. 29, 1967); ICI.
amount is required to produce the necessary coverage and color strength than would be 32. G. H. Robertson, U.S. Patent 4,220, 473 (Sep. 2, 1980); Sun Chemical.
necessary for a pigment that was not as well dispersed and contained a larger number of 33. R. J. Schwartz and T. Sulzberg, U.S. Patent 4,468,255 (Aug. 28, 1984); Sun Chemical.
aggregates, agglomerates, and flocculates. 34. M. J. B. Franklin, K. Goldsbrough, G. D. ParCilt, and J. Peacock, J. Painl Technol., 42,740
The trend today is toward production of more and more easily dispersihle pigments, as (1970).
35. H. Linden, H. Rutzen, and B. Wegemund, U.S. Patent 4,167,421 (Sept. 11, 1979); Henkel.
counterparts to the easily dispersible azo yellows, which are already used widely in certain
36. F. Hauxwell, J. F. SL1nsfield, and A. Topham, U.S. Patent 4,042,413 (Aug. 16, 1977); ICl.
printing ink systems. Pigment manufactures are always improving pigment dispersibility, 37. W. Carr, J. Oil C%ur Chel/!. Assoc., 65, 373 (1982).
through the use of surfacc treatments, in terms of surfacL1nts, polymeric dispersants, and 3R. K. TsuL~ui and S. Ikcda, Prog. Org Coalillgs, 10,235 (19R2).
pigment derivatives. The end result is the achievement of complete dispersion easily and 39. R. Polke, Am. Ink Maker, 61(6), 15 (1983).