Coatings and Inks

Dr Ian Maxwell
HYPERDISPERSANTS IN
NANOTECHNOLOGY APPLICATIONS
NanoMaterials 07
1st May 2007
Ian Maxwell - Noveon
© The Lubrizol Corporation 2006, all rights reserved

OUTLINE
• Nano particles / properties / stabilisation needs
• Overview of Hyperdispersants technology
• Solsperse product range – how to choose
• How to use dispersants – milling or surface treatment
• Noveon TS and Development Capability

WHAT IS NANOTECHNOLOGY
• Working with particles with sizes between say 5 nm and 100nm
• Working with giant molecules that have some defined shape

– Buckminster fullerene (“Fullerene”)
– Carbon nanotubes
• Molecular Electronics/Molecular computing.

– Processes happening within a single molecule
• Microengineering
– Tiny machines (actually micron, not nanometre sizes)
– “Nanobots”
Only the first named area probably has

any interest for Noveon Hyperdispersants
Some “nanoparticle” products
Transparent pigments
Iron oxides, TiO2 based UV absorbers
Conventional tinting
pigments
5 nm 50 nm 100nm
Ceramics
Sol gel processing conventional/grinding processing
“Quantum Dots”

TYPES OF NANOPARTICLES
MATERIAL PROPERTY
CARBON BLACK COLOR / MECHANICAL STR

SILICA HARDNESS
ALUMINA HARDNESS
ZIRCONIA HARDNESS
CLAY MECHANICAL STR
DIAMOND HARDNESS
SILICONE CARBIDE HARDNESS
CERIUM OXIDE UV ABSORPTION / HARDNESS
ZINC OXIDE UV ABSORPTION / ANTIMICROBIAL
TITANIUM DIOXIDE UV ABSORPTION / ANTIMICROBIAL
COPPER OXIDE ANTIMICROBIAL
SILVER OXIDE ANTIMICROBIAL
METALS (SILVER) ANTIMICROBIAL
INDIUM TIN OXIDE CONDUCTIVITY / IR ABSORBANCE
ANTIMONY TIN OXIDE CONDUCTIVITY / IR ABSORBANCE
CARBON NANOTUBES CONSUCTIVITY / MECHANICAL STR
IRON OXIDE MAGNETISM
WHAT’S NEEDED TO STABILISE
NANOPARTICLES?
• The smaller the particle, the shorter the range of the interactive
forces between them
– The steric stabilisation barrier doesn’t need to be so thick
BUT
• The surface area per gram of particles gets bigger and bigger,
so the amount of dispersant required increases
Thus, on theoretical grounds, smaller particles require

larger amounts of dispersants

STERIC STABILISATION OF PARTICLES
Localised high concentration of polymer

through compression or interpenetration gives
• When two particles with entropic repulsion and/or increased osmotic
absorbed polymeric or pressure
oligomeric chains come
together, the chains are forced
to intermingle or to compress
• Generally this intermingling or

compression is energetically is a
LESS favourable state. The
particles are therefore kept
apart
• Polymeric dispersants used to

generate the steric stabilisation
layer

DISPERSANT DESIGN
• Pigment dispersants contain anchoring and stabilising segments
Random Single point anchor AB block
BAB block Linear comb Branched / crosslinked

comb - brush
• For solvent based dispersants anchor groups tend to be polar / ionic.

• The stabilising segments need to be soluble in the continuous medium

CRITERIA FOR THE STERIC STABILISING
POLYMER CHAINS
Solubility/Polymer Chain Chemistry
• The stabilisation chain must be soluble in the liquid phase.

Must be a “better than theta” solvency system.
• End Use Compatibility – the chain must be compatible with
resin/binder after solvent has evaporated. Otherwise film properties
such as haze, durability and adhesion may be degraded.
Polymer chain length
• The chain must be long enough to form a barrier of the required

thickness
• Too long a chain tends to aid desorption
Ability to control composition and molecular weight of the steric chain

segment is critical in dispersant design

WHAT MAKES A GOOD DISPERSANT?
• Segmented architecture vs random.

• Intuitively expect controlled architecture to be best with
anchoring and soluble portions of dispersant well segregated.
• Limited ability of random structures to provide effective steric
stabilisation.
Random vs segmented structures

Random AB block copolymer Linear comb polymer
Anchoring and
soluble segments all
mixed together.

MOL WT CONTROL
Schematic illustration of block colplymers with broad mol Schematic illustration of linear
wt distribution comb with broad mol wt
distribution of steric chains
• Polymers have a distribution of molecular weights.

• Therefore even if the average mol wt of stabilisation chain is correct there
will be lot of material where the stabilisation chain is too small or too big
• The concept is the same for block or comb structures

SOLVENT HYPERDISPERSANTS
INFLUENCE OF
FIRST RECOMMENDATION SOLVENT SOLUBILITY
NOT RECOMMENDED
(HIGHLY SOLUBLE)
RECOMMENDED (SOLUBLE) INSOLUBLE

ADDITIVES FOR THERMOPLASTICS AND THERMOSETS
Unsaturated Polyesters Thermoplastics
And GelCoats
Masterbatch and Compound
Thermosets/ 28000 R700 DP310

Composites Liquid Colours
For Plastics
D510 21000
Acrylics D550
D540 DP310
D520 3000 Wire and Cable

11000 And Compounds
D520
D530 2155
C800 SOLSPERSE
D510
Epoxies D510 C825 IRCOSPERSE
SOLPLUS
organic pigment inorganic and fillers 2153
3000
2155
Polyester - 32000 20000 K500
Polyol 3000 K210
Phthalate
13650 Based
20000 K500
K200
Polyols R700 Plasticiser
Dispersions
Polyether -
Polyol Non-Phthalate
based
SOLVENT-FREE COATINGS
OVERVIEW OF 100% ACTIVE SOLSPERSE PRODUCTS
PRODUCT PHYSICAL FORM ANCHOR GROUP TYPE SOLUBILISING

CHAIN
POLARITY
20000 Liquid Basic High
32000 Solid (MPT 30 0C) Basic Medium
28000 Liquid Basic Medium - Low
8000 Liquid Basic Medium - Low
41000 Liquid Anionic High
36000 Solid (MPT 30 0C) Anionic Medium

DOSAGE
SOLSPERSE Hyperdispersants
Theoretical Amount 2mg Polymeric SOLSPERSE / m2 Pigment Surface Area
This dosage can be more easily understood as % agent on weight of pigment (% AOWP)
To convert 2mg/m2 TO % AOWP use PIGMENT SURFACE AREA (BET)

= % AOWP
5
200 X
PIGMENT
SURFACE
AREA 100 X
(m2/g)
20% 40%
% POLYMERIC SOLSPERSE REQUIRED BASED ON WEIGHT

OF PIGMENT IN MILLBASE (% AOWP)

WHICH ANCHOR GROUP IS BEST?
ACID v AMINE
on TiO2

TYPICAL SURFACE TREATMENT ADDITIVES
PRESENT ON RUTILE TITANIUM DIOXIDE
INORGANIC ORGANIC
ALUMINA TRIETHANOLAMINE
SILICA POLYDIMETHYLSILOXANE
ZIRCONIA TRIMETHYLOLPROPANE
SURFACTANTS

WHAT CONTRIBUTION DOES THE SURFACE
TREATMENT MAKE TO THE PROPERTIES OF TiO2?
SURFACE TREATMENT KEY PROPERTY
ALUMINA Improves pigment wetting

in the dispersion
SILICA Promotes coating durability
ZIRCONIA Improves pigment durability
ORGANIC Dispersability + compatibility

in the final application

DO PAINT PRODUCERS NEED POLYMERIC
DISPERSANTS TO DISPERSE TiO2?
Surface treatments do contribute significantly to the
dispersibility and stability of the titanium dioxide, but……………
In many cases this treatment is not enough to fulfill all

the coating requirements.
Coating properties can be enhanced further using polymeric

dispersants (gloss, haze, opacity and the ‘blueness’ of the white).
Pigment concentration in the dispersion can be increased, thus

increasing the potential for better hiding power and improved
productivity.
CAN THE TYPE OF POLYMERIC DISPERSANT
AFFECT THE DISPERSION PROPERTIES OF TiO2 ?
The anchor group on the polymeric dispersant can influence

the extent of dispersion stability and pigment loading with
tio2
This anchor group can be acidic, neutral or basic in nature
More effective dispersants will give better deflocculation

of the tio2 resulting in higher dispersion pigment concentration,
increased gloss and reduced haze.

POLYMERIC DISPERSANT CHOICE FOR
DISPERSING TiO2
SOLSPERSE 32600 - amine anchored, multiple chain,

multiple anchor type polymeric
dispersant (basic)
SOLSPERSE 36600 - acid anchored, multiple chain,

multiple anchor type polymeric
dispersant (acidic)

GRADES OF TiO2 AND THEIR
SURFACE TREATMENTS
GRADE INORGANIC ORGANIC NATURE
TIOXIDE TR92 Zirconia / Alumina Yes Basic
TIPURE R700 Alumina Yes Basic
TIOXIDE TR81 Zirconia / alumina Yes Basic
TIOXIDE TR85 Zirconia / Alumina Yes Basic
TIOXIDE RTC30 Silica / Alumina Yes Neutral / Basic
TIOXIDE RXL Silica / Alumina No Acidic
TIPURE R931 Silica / Alumina No Acidic

TiO2 GRADE v PIGMENT CONCENTRATION :
AMINE AND ACID ANCHORED DISPERSANTS
Dispersion System : MS Polyester
Solsperse Dosage : 2% AOWP
Dispersion Viscosity : Approx. 1 pas (1000 cps) @ low shear (37.6s-1)
TiO2
Conc(%)
85
80
75 32600
70
36600
65
60
55
50
TR92 R700 TR81 TR85 RTC30 RXL R931

TiO2 GRADE v GLOSS : AMINE AND ACID
ANCHORED DISPERSANTS
System : MS Polyester / Melamine

Gloss (600)
100
95
90
32600
85
80 36600
75
70
65
60
55
TR92 R700 TR81 TR85 RTC30 RXL R931

TiO2 GRADE AND DISPERSANT CHOICE
Choice of optimum anchor group

can make a significant difference
- To rheology and
- Application performance

ROUTES TO NANO PARTICLES
• Top Down - Milling
• Bottom Up- Particle formation/surface treatment

MILLING ROUTE
• Conventional bead mills - Bead size (0.3mm +)
- Difficult to achieve <100nm
• Nano Mills - Bead size (0.05 – 0.1mm)
- Can achieve <100nm
• General rule : Particle size = Bead Size

achieved 1000

MILLING ROUTE
MAGENTA UV INK JET FORMULATION
Ink Jet Magenta E02 VP2621 8 12.5
Solsperse 35000 - 15.0
Sartomer SR 306 92.0 72.5
100.0

MILLING CONDITIONS
• Bead mill with 0.3mm beads – 4 hours
- Particle size reduces from 185 ! 135nm
JN4824 Form 4Milling time vs Particle Size
Particle size- initial (nm) Particle size- 1 day (nm)
200
Particle size (nm)
180
160
140
120
100
0 50 100 150 200 250
Milling time (mins)

MILLING CONDITIONS
• Bead mill with 0.1mm beads – 50 mins
- Particle size reduces from 185 ! 82nm
Ink Jet Magenta E 02 VP 2621

With
Solsperse 35000
200
180
160 Particle Size - Diameter (nm)
140
120
Particle Size (nm)
100
80
60
40
20
0
0
20
30
50
Milling Time

MILLING CONDITIONS - SUMMARY
• Nano mills - Are critical for <100nm
- Particularly small beads
• As particle size reduces, surface area increases
• Dosage should be optimised for each specific PS produced

PARTICLE FORMATION – BOTTOM UP PROCESS
- Flame Pyrolysis
- Sol Gel
- Organic Pigmentation Processes
- Variety of Other Routes

HOW CAN DISPERSANTS HELP?
• Dispersants may control the growth of particles, giving

smaller particles
• Dispersants may increase the solids loading achievable

before gelation. This should then give reduced shrinkage
on drying / firing, and better final product properties

SURFACE TREATMENT
WITH ADDITIVES

SOLSPERSE! HYPERDISPERSANTS
Applications in Pigment/Particle Treatment
Solsperse hyperdispersants can be utilised in the manufacture of pigments

to provide a surface treatment which can improve the pigment
Process Stage
Anchor Group
Polymeric Chain
The anchor group of the hyperdispersant strongly adsorbs on to the pigment

surface, whilst the polymeric chain provides a high degree of steric stabilisation

SOLSPERSE! FOR PIGMENT / PARTICLE
Treatment - Benefits
QUALITY PRODUCTIVITY
Flow Throughput/Cycle Time
Strength Decreased mechanical wear
Dispersibility Increased solids (slurry, paste)
Product Stability Improved dry pigment for milling

SOLSPERSE! FOR PIGMENT
Treatment - Quality
Solsperse!
Quality
treated pigment
+
(strength or Untreated Solsperse! in
brightness or Pigment the formulation
dispersibility, +
etc) Solsperse! in Pigment
the formulation treated with
Solsperse!
Untreated
Pigment

SOLSPERSE! GRADES FOR
Surface Treatment
• Choice by solvent / medium
• By particle surface
• Dosage by surface area

POSSIBLE PIGMENT TREATMENT OPTIONS
WITH SOLSPERSE! ADDITIVES
STEPS TO CONSIDER WHEN INVESTIGATING USE OF

SOLSPERSE! IN PIGMENT TREATMENT
• WHICH PIGMENT AND WHICH SYNTHETIC ROUTE?

• Organic or inorganic?
• WHICH APPLICATION IS THE PIGMENT DESIGNED FOR?
• Ink or paint?
• CHOOSE THE BEST SOLSPERSE! AGENT FOR PIGMENT SURFACE AND DESIRED
APPLICATION
•CONSIDER BEST APPROACH TO GETTING AGENT ONTO PIGMENT SURFACE,
ie WHERE TO ADD SOLSPERSE!?
• Add during particle formation e.g. azo precipitation after coupling
• To an aqueous phase/as an emulsion prior to drying or milling (ensure homogeneous)

APPLICATIONS IN PIGMENT TREATMENT
DOSAGE
Generally much less agent is utilised compared

with conventional solsperse applications
But for NANO:-
For inorganic pigments around 5-10% active SOLSPERSE!

agent should be used
For organic pigments around 20-40% active SOLSPERSE!

agent should be used
(THESE LEVELS ARE BASED ON NON DRYING PROCESSES)

Pigment Type Potential Points of Addition Benefits Seen

(very dependent on pigment producer) (where known)
Mono Azo Reds

Inks:
Rubines (Red 57.1) • Add as an emulsion with rosin solution Better gloss, intensity
• Can be added after laking stage, but ... Higher transparency
• Best results obtained if Solsperse/rosin Better strength development
solution added to coupling stage Reduced cycle times of production
Improved dispersibility and reduced

viscosity
Improved performance in packaging

gravure inks
Red Lake C (Red 53.1) • Best results seen when added as an emulsion Transparent, easy to disperse
Lithol Reds (Red 49.1) after coupling but prior to laking pigments for offset paste inks or
Permanent Red 2B (Red 48s) gravure liquid inks
Diarylide Yellows
Yellow 12, Yellow 13 • Added as a solution (in acetic acid) during the Stronger, brighter pigments
coupling stage
• Can be used also as an alternative to post- Improved dispersibility in inks
treatment with rosins or fatty amines
• Can be added as an emulsion prior to drying Improved dispersibility
Control opacity/transparency

Potential Points of Addition Benefits Seen

Pigment Type (very dependent on pigment producer)
(where known)
Phthalocyanine Blues • Added during or after milling processes Improved rheology in solventborne
• Or added during solvent crystallisation paint and ink systems
Blue 15.4, 15.3 • Or added as an emulsion prior to drying Increased colour strength

Pigment Type Potential Points of Benefits Seen (Where

Addition (Very known)
dependent on pigment
producer)
Inorganics
Synthetic iron- • Post treatments after • Improved dispersibility in
oxides high temperature solvent paint system
- Yellow 42 processing • Higher strength pigment in
- Red 101 solvent borne paint
formulation
Titanium • Added as an emulsion • Increased solids loading

Dioxide prior to drying in the slurry
• Improved performance in
• plastics final application
• Improved performance in
solvent systems
Zinc Oxide • Dependent on pigment • Improved application

manufacturer performance

Pigment Potential Points of Benefits Seen (Where

Type Addition (Very known)
dependent on pigment
producer)
Iron blue or • Added to presscake • Improved dry pigments

Milori blue prior to drying for publication gravure
- Blue 27 applications - improved
• As above dispersibility
• Decreased mechanical
abrasion
Fillers • Added to an aqueous • Improved application

(ATH, talc, slurry as emulsion performance in plastics
kaolin, prior to drying
CaCO3 etc)

SOLSPERSE! HYPERDISPERSANTS
EMULSION/SOLUTION PREPARATION
SOLSPERSE! 3000 EMULSIONS
NON-IONIC EMULSION
1. MELT & MIX TOGETHER 20 PARTS SOLSPERSE! 3000 AND 5 PARTS SYNPERONIC A14
SYNPERONIC A14: C13-C15 MIXED ALCOHOL + 14 ETHYLENE OXIDE UNITS
2. WITH HIGH SHEAR STIRRING POUR MIXTURE INTO 75 PARTS OF WATER WHICH IS AT 50°C
ANIONIC EMULSION
1. MELT 25 PARTS SOLSPERSE! 3000 AND POUR INTO A SOLUTION OF 2.5 PARTS
TRIETHANOLAMINE/72.5 PARTS WATER WHICH IS AT 50°C AND BEING STIRRED RAPIDLY
USING A HIGH SHEAR MIXER
THESE EMULSIONS ARE STABLE FOR SEVERAL MONTHS AT AMBIENT TEMP. & IN pH2-pH10
SOLSPERSE! 3000 SOLUTION

SOLSPERSE! 3000 12.5
BUTYL CELLOSOLVE 12.5
1N KOH SOLUTION 75.0
SLURRY THE SOLSPERSE! P850 IN THE KOH SOLUTION AND CLARIFY THE SLURRY BY THE ADDITION OF THE BUTYL CELLOSOLVE
FINAL SOLUTION IS SLIGHTLY HAZY AND AFTER STANDING 4 DAYS A SMALL AMOUNT OF PRECIPITATE
SETTLES WHICH IS READILY RE-DISPERSED ON STIRRING
TECHNICAL SERVICE / DEVELOPMENT
CAPABILITY
• Bead Mills - Conventional Range (x3)

- Nano Mill Shortly
• Standard Additive recommendation based on enquiry
• Development capability for Polyester, Acrylics, PU,

Dispersants

DISPERSANT RECOMMENDATIONS FOR
NANOPARTICLE APPLICATIONS
Alcohol / water based Low polarity Medium polarity

Sol-gel process solvents Solvents
e.g. aliphatics e.g. esters, ketones,
Aromatics, glycol,
esters, terpineol
Smaller SOLSPERSE 21000 SOLPLUS D520
Nanoparticles SOLPLUS D540 or or
or SOLSPERSE 8000 SOLPLUS D510
SOLSPERSE 20000
Larger SOLSPERSE 3000 SOLSPERSE 36000
Nanoparicles or or
[SOLSPERSE 27000/54000 SOLSPERSE SOLSPERSE 39000
if very hydrophobic] 11000/11200
Note: A few products contain phosphorus, and this may cause

problems in some advanced electronic applications

PLEASE CONTACT US FOR YOUR
DISPERSANT NEEDS
QUESTIONS ?

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Dr Ian Maxwell

© The Lubrizol Corporation 2006, all rights reserved

• Nano particles / properties / stabilisation needs

• Overview of Hyperdispersants technology

• Solsperse product range – how to choose

• How to use dispersants – milling or surface treatment

• Noveon TS and Development Capability

© The Lubrizol Corporation 2006, all rights reserved

• Working with particles with sizes between say 5 nm and 100nm

• Working with giant molecules that have some defined shape

• Molecular Electronics/Molecular computing.

Only the first named area probably has

Sol gel processing conventional/grinding processing

© The Lubrizol Corporation 2006, all rights reserved

CARBON BLACK COLOR / MECHANICAL STR

Thus, on theoretical grounds, smaller particles require

© The Lubrizol Corporation 2006, all rights reserved

Localised high concentration of polymer

• Generally this intermingling or

• Polymeric dispersants used to

© The Lubrizol Corporation 2006, all rights reserved

• Pigment dispersants contain anchoring and stabilising segments

Random Single point anchor AB block

BAB block Linear comb Branched / crosslinked

• For solvent based dispersants anchor groups tend to be polar / ionic.

© The Lubrizol Corporation 2006, all rights reserved

• The stabilisation chain must be soluble in the liquid phase.

Polymer chain length

• The chain must be long enough to form a barrier of the required

Ability to control composition and molecular weight of the steric chain

© The Lubrizol Corporation 2006, all rights reserved

• Segmented architecture vs random.

Random vs segmented structures

© The Lubrizol Corporation 2006, all rights reserved

• Polymers have a distribution of molecular weights.

© The Lubrizol Corporation 2006, all rights reserved

RECOMMENDED (SOLUBLE) INSOLUBLE

© The Lubrizol Corporation 2006, all rights reserved

Thermosets/ 28000 R700 DP310

D520 3000 Wire and Cable

PRODUCT PHYSICAL FORM ANCHOR GROUP TYPE SOLUBILISING

20000 Liquid Basic High

32000 Solid (MPT 30 0C) Basic Medium

28000 Liquid Basic Medium - Low

8000 Liquid Basic Medium - Low

41000 Liquid Anionic High

36000 Solid (MPT 30 0C) Anionic Medium

© The Lubrizol Corporation 2006, all rights reserved

Theoretical Amount 2mg Polymeric SOLSPERSE / m2 Pigment Surface Area

To convert 2mg/m2 TO % AOWP use PIGMENT SURFACE AREA (BET)

% POLYMERIC SOLSPERSE REQUIRED BASED ON WEIGHT

© The Lubrizol Corporation 2006, all rights reserved

© The Lubrizol Corporation 2006, all rights reserved

© The Lubrizol Corporation 2006, all rights reserved

SURFACE TREATMENT KEY PROPERTY

ALUMINA Improves pigment wetting

SILICA Promotes coating durability

ZIRCONIA Improves pigment durability

ORGANIC Dispersability + compatibility

© The Lubrizol Corporation 2006, all rights reserved

In many cases this treatment is not enough to fulfill all

Coating properties can be enhanced further using polymeric

Pigment concentration in the dispersion can be increased, thus