Rheology Modifiers Advanced sheen Paint Training Part 5

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Rheology Basics

TYPES OF RHEOLOGICAL BEHAVIOUR

NEWTONIAN FLOW PSEUDOPLASTICITY SHEAR THINNING FLOW (case with Yield Value) THIXOTROPY

Yield Value

Viscosity

Viscosity

Viscosity

Shearing at constant shear

Viscosity recovery at rest

. Shear Rate
Increased shear does not impact viscosity.

. Shear Rate
Flow starts at a given shear (yield) Increased shear rate induces lower viscosity Multiple viscosity measurements required to have rheology profile

Time
At constant shear, viscosity drops When shear is stopped, viscosity recovers

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Water borne Rheological additives: Thickener Types

SYNTHETIC CONVENTIONAL ASSOCIATIVE Polyvinyl alcohol Polyacrylamide Alkali Soluble Emulsion -Acrylic Polyacrylic acids

NATURAL DERIVATIVES Cellulose ethers - CMC - MC, HEC, EHEC, etc.. Other polysaccharides

HASE HEUR

HM-HEC

THIXOTROPY:

Clays (Bentonite, Laponite) Titanium chelates Attapigalite Clays (Min-u-gel)

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Water borne Rheological additives: Conventional Thickeners

CELLULOSIC THICKENERS (Cellulose Ether)

ACRYLIC THICKENERS (ASE) (Alkali Soluble Emulsion)

CH 2OH O O OH OH

OR" O OH O CH 2OR'

CH 2OH O O OH OH

C O O H

a m m o n i a a m i n e h a r d b a s e

O O C

O O C O O C C O O C O O -

p H ~ 3 . 0

p H ~ 8 . 0

EFFICIENT VISCOSITY BUILDERS FLOCCULATE MANY LATEX BINDERS AND PIGMENTS RESTRICTING GLOSS DEVELOPMENT AND LEVELLING MICROBIAL DEGRADATION

EASY TO FORMULATE WITH RESTRICTING GLOSS DEVELOPMENT AND LEVELLING

LIQUID PHASE THICKENING

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Water borne Rheological additives: Conventional Thickeners

THICKENING MECHANISM

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Water borne Rheological additives: Conventional Thickeners

THICKENING MECHANISM
H H O H H H O H H H O H O H O

H
O

Large hydrodynamic volume due to hydrogen bonding of the water molecules to the polymer Viscosity strongly dependent upon the polymer Molecular Weight Polymer chain entanglement and cross-linking (ASE)

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Water borne Rheological additives: Conventional Thickeners

VOLUME RESTRICTION FLOCCULATION

Water

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Water borne Rheological additives: Conventional Thickeners

VOLUME RESTRICTION FLOCCULATION

Water

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Water borne Rheological additives: Associative Thickeners

HEUR HASE

: Hydrophobically modified Ethylene oxide URethane : Hydrophobically modified Alkali Soluble Emulsion

Nonflocculating - excellent gloss and levelling

Easy to manipulate high and low shear rheology Good roller spatter resistance Very formulation dependent - complex interactions

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Water borne Rheological additives: Associative Thickeners

ASSOCIATIVE THICKENER CONCEPT

hydrophilic tail hydrophobe

Non-ionic Surfactant

hydrophilic Polymer

hydrophobes

Associative Thickener

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Water borne Rheological additives: Associative Thickeners

THICKENING MECHANISM
latex particle flower micelle

in water

in a latex polymer
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Water borne Rheological additives

CONVENTIONAL versus ASSOCIATIVE THICKENER IN A LATEX

Conventional thickener

Associative thickener
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Rheology of paints

RHEOLOGY PROFILE

1000

100

10

Viscosity

0.1

0.01 0.001

0.01

0.1

10

100

1000

10 000

Shear rate
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Rheology of paints

APPLICATION versus RHEOLOGY PROFILE

1000

100

10

Viscosity

0.1

0.01 0.001

0.01

0.1

10

100

1000

10 000

Shear rate
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Rheology of paints

APPLICATION versus RHEOLOGY PROFILE

1000

100

10

Viscosity

0.1

Settling
0.01 0.001 0.01 0.1

Sagging, Levelling
1

Brush, Loading Spreading, Spattering

10 100

Brush drag, Rolling

1000 10 000

Shear rate
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Rheology of paints

Rheology Modifiers can control: Package stability Application Feel / Drag Sag Brush marks Levelling Flow Spattering Pattern Spreading Water sensitivity

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ROHM and HAAS Rheology Modifiers

Technologies

Conventional thickeners ASE : Alkali Soluble Emulsion

Associative thickeners
HEUR : Hydrophobically modified Ethylene oxide URethane

HASE : Hydrophobically modified Alkali Soluble Emulsion

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ROHM and HAAS Rheology Modifiers

ACRYSOLTM Product Line

ASE
Purely Alkali soluble

ASE 60 ER

HASE
Alkali soluble/associative Economic

RM-5

TT-935 ER TT-615

RM-935

DR
Technology similar to HASE Reduced colorant viscosity drop HEC replacement DR-72 DR-73 ER DR-300

HEUR
Non ionic Highly associative Sensitive to colorants

RM 2020 RM-5000 RM-6000 RM-8W RM-12W SCT-275

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ROHM and HAAS Rheology Modifiers

ACRYSOLTM Product Line

1000

100

10

Viscosity

0.1

Settling
0.01 0.001 0.01 0.1

Sagging, Levelling
1

Brush, Loading Spreading, Spattering

10 100

Brush drag, Rolling

1000 10 000

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ROHM and HAAS Rheology Modifiers

ACRYSOLTM Product Line

1000

100

10

Viscosity

0.1

Settling
0.01 0.001 0.01 0.1

Sagging, Levelling
1

Brush, Loading Spreading, Spattering

10 100

Brush drag, Rolling

1000 10 000

TT-615 ASE-60 ER

DR-72

TT-935 ER RM-935 DR-300

RM-5

DR-73 ER
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ROHM and HAAS Rheology Modifiers

ACRYSOLTM Product Line

1000

100

10

Viscosity

0.1

Settling
0.01 0.001 0.01 0.1

Sagging, Levelling
1

Brush, Loading Spreading, Spattering

10 100

Brush drag, Rolling

1000 10 000

RM-12W

SCT-275

RM-6000 RM-2020 RM-5000

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ROHM and HAAS Rheology Modifiers

Conventional Thickeners

ACRYSOLTM ASE-60 ER

ASE-60 ER

(Log) Viscosity, Pa

Acrylic thickener (30% solids) Specifically designed to develop a high level of structure (high molecular weight, crosslinked) Generally used as a co-thickener
250 MBR

Recommended for: - structured paints - settling & sag resistance (Log) Shear Rate, s-1

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ROHM and HAAS Rheology Modifiers

HEUR Thickeners (Hydrophobically modified Ethylene oxide URethane)

poly (EO)

Linear
Telechelic
urethane linkage Hydrophobe

Branched
Random

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ROHM and HAAS Rheology Modifiers

AcrysolTM HEUR Family
High shear Medium Shear Low shear

Linear Polymers
RM-8
35% Water/PG

RM-2020
20% Water

RM-5000
18,5% Water

RM-6000
17,5% Water

RM-8W
21.5% Water

RM-12 W
19 % Water

Branched Polymers
SCT-275
17.5% Water/Butyl Carbitol
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ROHM and HAAS Rheology Modifiers

AcrysolTM HEUR Family

Acrysol RM-2020 RM-5000 RM-6000 RM-8/825/8W SCT-275 RM-12W

Hydrophobe RM-2020 RM-8/825/8W small medium medium large

(Log) Viscosity Rate of Shear

SCT-275 RM-12W

New technology RM-5000 RM-6000 small medium

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ROHM and HAAS Rheology Modifiers

HASE Thickeners

(Hydrophobically modified Alkali Soluble Emulsion)

poly (EO) spacer

COO

Acid copolymer backbone

COO
ester or urethane linkage

Hydrophobe

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ROHM and HAAS Rheology Modifiers

AcrysolTM HASE and DR Family

Newtonian High Shear RM 5 Flow,levelling

Medium Shear shear Medium TT 935 ER KU Efficient Low spatter

Low shear Low shear TT 615 Structure, sag resistance

Low Mw HEC DR-73 ER Natrosol Plus like rheology Low formulated cost All liquid productivity gains Less viscosity drop than HASE

High Mw HEC DR-72 Rheology like high Mw HEC Low formulated cost All liquid productivity gains Less viscosity drop than HASE

DR-300 Improved water resistance

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ROHM and HAAS Rheology Modifiers

AcrysolTM HASE and DR Family

TT-615 DR-73 ER DR-72 TT-615 DR-300 TT-935 ER DR-72/DR-300

Molecular weight

(Log) Viscosity

DR-73 ER RM-55

RM-55

TT-935 ER

Hydrophobe size

Rate of Shear

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ROHM and HAAS Rheology Modifiers

AcrysolTM HASE and DR Family
Acrysol DR : Technology to replace dry thickeners
powders cause long preparation time and low plant productivity Difficult to adjust viscosity after production High formulated cost Poor flow and roller spatter Sensitive to microbial attack

High Mw HEC Acrysol DR-72

Low Shear Viscosity

Medium Mw HEC
Acrysol DR-72 + Acrysol DR-73

Low Mw HEC HMHEC Acrysol DR-73

High Shear Viscosity

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ROHM and HAAS Rheology Modifiers

AcrysolTM HASE and DR Family
Acrysol DR : Technology to replace dry thickeners

MASONRY WHITE PAINT 48% PVC / 30% VS ACRYLIC BINDER

0.72% MHEC (high Mw) VISCOSITIES AFTER EQUILIBRIUM ICI Cone & plate (Poise) KU Brook field Sp. 4/6 rpm (cPs) VISCOSITIES AFTER COLORANT ADDITION ICI Cone & plate (Poise) KU Brook field Sp. 4/6 rpm (cPs) VISCOSITIES AFTER HEAT AGEING 5 DAYS AT 60C ICI Cone & plate (Poise) KU Brook field Sp. 4/6 rpm (cPs) 1.5% Acrysol DR-72 (30%solids) 2.9% Acrysol-DR300 (20%solids)

0.9 110 29 300

0.7 113 25 000

0.7 110 29 800

0.9 116 29 700

0.8 130 39 000

0.9 126 38 200

0.8 108 23 000

0.7 120 30 000

0.7 108 25 000

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ROHM and HAAS Rheology Modifiers

AcrysolTM HASE and DR Family
Acrysol DR : Technology to replace dry thickeners

2000 1900 1800

Wet-scrub cycles

1700 1600 1500 1400 1300 1200 1100 1000 MHEC, high Mw Acrys ol DR-72 Acrys ol DR-300

Acrysol DR-300 with superior water resistance

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ROHM and HAAS Rheology Modifiers

AcrysolTM HASE and DR Family
Acrysol DR : Technology to replace dry thickeners

SPATTER RESISTANCE *
5 4 3 2 1 0
MHEC, high Mw Acrysol DR-72 Acrysol DR-300

*Spatter resist. during roller application. Rated from 1-5; 5=excellent

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ROHM and HAAS Rheology Modifiers

ACRYSOLTM Product Line Rheology profile at constant mid shear viscosity

HASE ASE

Low Shear Viscosity

RM-12W TT-615 DR-72 ASE-60 ER

DR-300 RM-6000
TT-935 ER SCT-275 RM-8W/825 RM-55 DR-73 ER RM-5000

RM-2020

High Shear Viscosity

HEUR New
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KEY INTERACTIONS OF ASSOCIATIVE THICKENERS WITH PAINT INGREDIENTS

Effect of latex particle size

Effect of latex stabilization Interaction with pigments Interaction with dispersants Interaction with surfactants

Interaction with solvents

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Handling and Formulating Guidelines

Mixing conditions
Ensure sufficient agitation at the moment of RM addition

Addition order
Both HASE and HEUR can be added in the grind or the letdown For HASE thickeners : - grind : adjust pH before addition - letdown : adjust pH and pre-diluted RM with 50% water HASE are easily incorporated when diluted and preneutralized (pH= 8 to 9)

Dispersant choice
Look at the interactions between dispersant type and RM

RM efficiency depends on
- Concentration, molecular weight and associativity of the RM - PVC and VS of the formulation - Binder hydrophobicity - Viscosity suppressants (surfactants, cosolvents)
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