CATIONIC PIGMENT DISPERSIONS

CATIONIC PIGMENT DISPERSIONS

Vishal Y. Gehlot
On: 17/09/08

What are cationic pigment dispersions?

Cationic pigment dispersion is a system which includes at least one pigment, dispersion
medium (e.g., water) & at least one quaternary salt (e.g., quaternary salt of styrene maleimide
imide resin) in an amount effective to disperse the pigment in dispersion medium.

These cationic pigment dispersions can be prepared by [1]:

1) mixing, at 500 to 10000 rpm, at least one pigment, water & a quaternary salt of styrene
maleimide imide resin, thereby forming a dispersion premix;
2) milling the dispersion premix in a mixer filled with ceramic, metal or glass beads for a period
of time sufficient to reduce pigment agglomerates to primary particles, thereby forming a non-
standardized dispersion;
3) standardizing the dispersion against a color standard by adding water.

Applications of cationic pigment dispersions:

1) Coloring of cellulose [1], [2]:

Papermaking is a well known process in which a cellulosic material, typically obtained

from wood, is mechanically or chemically pulped, dispersed in water, formed into a planar sheet,
dried & wound onto a roller for later use.

Colorants such as dyes & pigments may also be added during papermaking process,
either by coloring the paper pulp, or applying the colorant to the paper surface by dip coating,
spraying or pad printing. Pulp coloration is the most widely used type of paper coloration.

The anionic character of cellulosic materials in water affects the substantivity & affinity of
dyes & pigments for paper. Pigments do not contain solubilizing functional groups & have little
affinity for or substantivity to cellulose. Thus, the addition of a fixing agent, such as cationic
starch, aluminium sulfate & cationic polymers, is typically required to fix pigments to cellulosic
materials.

An advantage of using cationic aqueous pigment dispersion for dyeing cellulose is that it
permits consistent coloring of cellulosic materials over time, which is important in continuous &
semi-continuous papermaking operations. Another advantage is that it exhibits essentially
100%, rapid exhaustion of pigment particles into cellulosic materials, thereby generating clear
backwaters. This is vitally important both from an economical & environmental viewpoint.

Both inorganic as well as organic pigments can be used to produce cationic pigment
dispersion for dyeing cellulosic material. Inorganic pigments include red oxide, black iron oxide,

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cobalt blue, carbon black, & bismuth vanadate. Organic pigments include azo pigments such as
azo lake pigments, condensed azo pigments, & polycyclic pigments such as phthalocyanine
pigments, perylene pigments, perinone, anthraquinone, quinacridone, dioxazine, thioindigo,
isoindoline, quinophthalone, arylide, diarylide, & naphthol red pigments.

Synthesis of quaternary salt of styrene maleimide imide resin:

H3C
N CH3

H3C
O
O O
N CH3 N
O O
0
H2 C 150-180 C,
m +
H2 C
30-40 mins. m

NH2
n
dimethylamino
styrene maleimide resin n
propylamine styrene maleimide imide resin

where, n = 1-3, m = 6-8

These styrene maleimide imide resins are insoluble in water. However, they can be converted to
their corresponding quaternary ammonium salts, which are water soluble, by reaction with a
weak acid such as acetic acid, citric acid, hydrofluoric acid, oxalic acid & nitrous acid. The pH of
resulting quaternary salt is preferably set to 4-6.

The cationic pigment dispersion employed for dyeing cellulosic material consists of 10
wt% pigment, 3-8 wt.% dispersing agent. A slight excess of weak acid is used to ensure that the
quaternary salt of the styrene maleimide imide resin remains solubilized. Suitable additives such
as viscosity control agents, surfactants & biocides can also be added.

The amount of viscosity control agent will depend on relative amounts of dispersing
agent, pigment & water forming the dispersion & may range from 0.5% to 2% by weight of
dispersion. Surfactants are added to the dispersion to reduce foaming during mixing of the
dispersion. A surfactant concentration of 0.1 wt% is normally sufficient. A biocide concentration
of about 0.1 wt% is normally sufficient to ensure that no harmful or objectionable bacteria
colonize the dispersion.

Example of a cationic pigment dispersion for dyeing cellulose:

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Materials Weight percent

Styrene maleimide imide 5.50
Phthalocyanine blue pigment 43.00
Acetic acid 1.00
Defoamer 0.10
Biocide 0.10
Water 50.30

Example of coloring of paper pulp using above cationic aqueous pigment dispersion:

4 gms of 50/50 blend of hard & soft wood fibres are added to a beaker containing 100
gms of water & mixed using a flat mixing blade operating at a speed of at least 100 rpm to
produce an aqueous suspension of cellulosic fibres.

Separately, 1 gm of cationic dispersion is diluted with 250 gms of water. 25 ml of diluted

dispersion is pipetted into the aqueous suspension, which is mixed for another 5 minutes using
the same mixing conditions, thus resulting in an aqueous suspension of colored cellulosic fibres.
This aqueous colored suspension is then used to form sheets of colored paper. The cationic
dispersion completely exhausted its pigment into the paper pulp, & gave crystal clear
backwater. The colored paper is blotted & dried on small paper dryer.

This completely dried color paper when evaluated for color continuity, two sidedness,
color matching to a standard, & color strength, had passed all the tests.

The styrene maleimide imide resin quaternary salt is only soluble in acidic solution &
becomes insoluble in alkaline environment. Thus, it is necessary to maintain the pH below 7
during papermaking to ensure optimum performance of the cationic pigment dispersion.

2) Coloring building materials [3], [4]:

It is desirable to color exposed concrete surfaces for both aesthetic & functional reasons.
Colored concrete buildings do not present an environment as sterile & cold as white concrete. In
addition, light colors can be used in sunny climates to help reduce glare while darker colors may
be used to increase a building’s heat storage capacity in cooler climates.

Coloring the exposed surface by painting or by coating the surface with some other
decorative layer is known. However, painting or application of a coating layer is an additional
step in construction which adds cost & complexity to a construction project. Moreover, an
exterior painted surface may require repainting in a relatively short period of time.
Cationic pigment dispersions which are used to dye cellulosic materials can also be
used for coloring building materials such as concrete, asphalt, plaster, mortar, & cement mortar.
The only requirement here is that the pigment selected must exhibit good alkali resistance &
light resistance.

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Suitable organic pigments include azo pigments such as azo lake pigments, condensed
azo pigments, & polycyclic pigments such as phthalocyanine pigments, perylene pigments,
perinone, anthraquinone, quinacridone, dioxazine, thioindigo, isoindoline, & quinophthalone
pigments.

An advantage of cationic pigment dispersion is its ability to color building materials with
bright organic pigments that do not suffer from poor alkali resistance & poor light fastness.
Another advantage is that it permits ready removal of graffiti or other surface defacement from a
concrete surface without impairing its surface appearance.

Example of a cationic aqueous pigment dispersion for coloring concrete:

Materials Weight percent

Styrene maleimide imide 5.10
Pigment Yellow 97 40.00
Acetic acid 1.00
Defoamer 0.10
Bioacid 0.10
Water 53.70

This cationic dispersion is used to integrally color concrete by mixing an appropriate

amount (1%) of the dispersion with concrete in a mixer for 15 minutes. The cationic dispersion
readily becomes a part of the concrete matrix.

The styrene maleimide imide quaternary salt is only soluble in acidic medium & becomes
insoluble in alkaline medium. Thus, when the dispersion is mixed with concrete, the coated
pigment particles are rapidly dispersed throughout the wet concrete, which has a high pH,
typically above 10. The styrene maleimide imide quaternary salt is converted into its
corresponding styrene maleimide imide resin by deprotonation due to alkalinity of the cement,
thus becoming water insoluble & immobilising the coated pigment particles within the concrete
matrix.

3) Ink-jet printing inks [5]:

An ink-jet printer is capable of printing with colored ink, such as magenta, cyan & yellow
as well as black ink. When two colors are printed side by side, particularly when black ink is
printed next to any other colored ink, the colors can bleed into one-another. “Bleed” is defined
as the migration of one ink color into the region of other ink color, particularly when black ink
moves into a region of any other color. It is desirable to have clean & sharp border between
areas of two different colors. Common methods used to control bleed between different colors
of ink include surface tension control, chelation control, & neutralization control. A new method
to control bleed is described below by using a cationic dispersion based pigmented ink along
with an anionic dispersion based ink.

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A cationic pigmented ink consists of at least one cationic dye as a dispersant & a
pigment. Advantages of using cationic dye as a dispersant as compared to conventional
polymeric dispersants to disperse a pigment are:

• Cationic dyes have strong interaction with pigments due to their aromatic structure.
• As cationic dyes are soluble in water they are capable of stabilizing pigments in acidic
solutions.
• Specific cationic dyes can also change the shade of the pigment.
• The combination of cationic dye with a pigment produces an ink-jet ink with improved
light fastness.

Here, the flocculation characteristics or, in other words, the charge neutralization
interaction, between the cationic dispersion based pigmented ink & anionic dispersion based ink
is utilized. When the cationic dispersion based pigmented ink comes into contact with the
anionic dispersion based ink, flocculation occurs at the interface, thus reducing or eliminating
bleed between different colored inks.

The cationic dye to be used as dispersant must satisfy the following criteria:

• The dye must have a net positive charge.

• The dye must be able to disperse the pigment & must consist of a hydrophobic region as
well as a hydrophilic region.
• The dye must exhibit sufficient solubility in water to be used in ink-jet ink applications.

Examples of cationic dyes which can be used are:

CH3 CH3 C 2 H5 CH3 CH3 C2 H 5

+ +
N N N N
H3C CH3 H5 C 2 C 2 H5
- -
Cl Cl

Cl Cl

C. I. Basic Blue 1 C. I. Basic Blue 5

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CH2CH2Cl
N
S
+
N
N +
- N
Cl

C.I. Basic Yellow 1 C.I. Basic Red 13

Other examples of cationic dyes include C.I. Basic Red 12, , 14, 15, etc., C.I. Basic Violet 10, 7,
3, 1, 2, etc., C.I. Basic Black 8, C.I. Basic Yellow 2, 4, 11, 13, etc.

Pigments which can be used to get cationic dispersion based pigmented ink include dye
lakes, azo pigments, condensed azo pigments, polycyclic pigments such as phthalocyanine,
anthraquinone, quinacridone, dioxazine, thioindigo, isoindoline, & quinophthalone pigments.
Other pigments include titanium dioxide, iron oxide, aniline black & carbon black.

Example of a cationic dispersion based pigmented ink:

First a dye solution is prepared. 10 gms of cationic dye is added to 100 ml deionized
water in a beaker. While stirring this mixture, acetic acid is added to maintain the pH of the
solution between 4-5. It may be necessary to add additional water to dissolve dye completely.
The final dye solution strength should be between 4-5 % with pH of dye solution being 4-5. The
dye solution is then filtered.

A dispersion is made at a pigment : cationic dye (P : D) ratio of 4:1 by adding 28.8 gms
of Monarch 880 carbon black pigment into an attritor cup, followed by the addition of dye
solution prepared above. The mixture is stirred carefully with a spatula till pigment gets wetted
thoroughly. The attritor cup is placed onto the attritor assembly. Next, a grinding media is added
into the attritor cup. The attritor is set on high & allowed to grind the mixture at 300C until a
suitable particle size is reached. Once the suitable particle size is reached, the dispersion is
separated from the grinding media using a sieve.

Ink-jet ink formulation using cationic pigment dispersion prepared above:

Ingredients Amount (wt%)

Pigment (P:D::4:1) 4
Polyethylene glycol (molecular weight 1000) 5
2-pyrrolidone 5
2,2-thiodiethanol 5
1,2-hexanediol 0.2
Deionized water 80.8

This cationic dispersion based pigmented ink (INK 1) can be first applied onto the first
area of a substrate & then the anionic dispersion based ink (INK 2) can be applied onto the

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second area of the substrate, wherein said first area is in communication with the said second
area. The steps of applying INK1 & INK 2 can be in any order or they can be applied
simultaneously.

4) Dyeing anionic materials [6]:

Pigment dyeing of cellulosic material is well known. Conventional method for dyeing
cellulosic textile materials comprises padding these materials with a bath containing anionic or
neutral pigment dispersions, an anionic binder, an acid-liberating catalyst, a cross-linking agent,
an anti-migrating agent, & other additives. The textile materials are then dried at about 1000C &
then further heated at about 1500C for about 5 minutes to cure the pigment colours & film-
forming binders on the textiles.

Problems associated with conventional method of pigment dyeing are:

• Since cellulosic surface has a uniform negative charge & the pigment dispersions
commercially available are also anionic in nature, there is repulsion between the pigment
particles & the cellulosic surface during padding operation ultimately leading to light
shades along with poor leveling on the cellulosic materials even when these materials
are padded from a bath containing a high concentration of pigment dispersions.
• The colors often thermomigrate to one side of the textile thereby producing poor leveling
of the shade.
• The dry & wet rubbing as well as washing fastness of the pigment dyed cellulosic
material is generally poor.

Therefore, there is a need in the art to provide a method of pigment dyeing cellulosic
materials & other anionic textile materials that overcome these problems.

A novel method for dyeing anionic cellulosic materials with cationic pigment dispersion
has been developed. The method comprises padding the textile material with a cationic pigment
dispersion comprising a pigment & a cationic dispersant & consequently padding the textile
material with a film-forming polymer (binder). The padding steps can occur simultaneously with
both the cationic pigment dispersion & the film-forming polymer in the same bath or in
consecutive padding steps with the cationic pigment dispersion applied before the film-forming
polymer or vice-versa. The padded materials are dried & cured to produce the pigment-dyed
materials.

This method produces pigment colors of light to deep shades on anionic cellulosic
textiles having excellent fastness & leveling of shade with little or no thermomigration of the
pigments. Various types of binders can also be used. The cationic pigment dispersion has a net
positive charge & the film-forming polymer has a net positive, negative or neutral charge. Pad-
Dry-Cure or Pad-Dry-Pad-Dry-Cure techniques can be used to obtain excellent pigment-dyed
cellulosic material.

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Suitable pigments include Permanent Yellow DHG, Permanent Yellow GR, Permanent
Yellow PG, Permanent Orange G, Permanent Red FGR, Permanent Red F4R 1747, Permanent
Bordeaux FRR, Hostaperm Blue CBR, Hostaperm Violet RLSPL, Hostaperm Green GNX-D,
titanium dioxide & carbon black.

Examples of pigments used:

OH
Cl
N NH
N OH N
O Cl N
O N
N N N
N N N HO
NH N
Cl Cl
HO

Permanent Yellow DHG Permanent Orange G

Cl

O O
HO NH HO NH
O2N N N
N N
O 2N

Permanent Bordeaux FRR Permanent Red F4R

Cellulosic materials used can be cotton, rayon, & solvent spun cellulose fibres, & blends
thereof. It can also be a blend of these cellulosic fibres & non-cellulosic fibres.

Additives such as wetting agents, cationic or nonionic surfactants, defoamers, solvents,

biocides, & fungicides, can be applied to the surface of the textile material typically by adding
the additives to the bath comprising the cationic pigment dispersion or the bath comprising the
film-forming polymer.

The cationic dispersant used is either a monomeric or polymeric compound which

consists at least one cationic group such as tertiary amine, quaternary amine, sulfonium or
phosphonium. This cationic dispersant should have good adsorption to the pigment surface so
that the dispersion remains stable & positively charged even when diluted.

Example of a cationic pigment dispersion for dyeing cellulosic material:

Phase Ingredients Quantity (gms)

A Cationic resin 4.00
Defoamer 1.50
Biocide 0.10
Water 47.00
Ethylene oxide of nonylphenol 1.50

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50% aq. ethylene oxide of nonylphenol 8.00

Dilauryl polyethylene glycol (mol. wt. 1500) 2.00
B Pigment 15.00
C Cationic resin 1.00
Water 19.90
Total 237.50

Pigment dispersion is prepared by using the formulation shown in above table by

grinding them for two hours in an atritor pigment mill with 2-3 mm glass beads until a finish of
Hegman gauge of minimum 7 is achieved. Phase A is mixed with the cationic resin & additives
forming the cationic dispersion. Phase A is stirred at low speed while adding phase B. The
stirrer speed is increased & after 1.5 hours, phase C is added & the mixture is stirred for another
30 minutes. The pigment dispersion is then filtered & used further.

Example of dyeing cellulosic material using cationic pigment dispersion:

10 gms of cationic pigment dispersion prepared above & 90 gms of water are combined
to prepare 10% solution & a knitted cotton fabric having good absorbency is padded using this
dye bath at 80% wet pick-up. The padded fabric is completely dried at 1000C. The second dye
bath is prepared using the following ingredients:

Ingredient Quantity (gms)

Binder 15
Urea 2
Melamine resin 1
30% amino silicone 1
Ammonium chloride 1
Water 80

The fabric padded with the cationic pigment dispersion is padded using this prepared
binder bath at 80% wet pick up. The padded fabric is completely dried at 1000C & cured at
1500C for 5 minutes.

References:

1. US2005025972.
2. WO02095130.
3. US2005014868.
4. WO02094733.
5. US2004118320.
6. WO0055420.

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