Radiation Curable Additives Enabling Excellent Paint …...The information contained herein...
Transcript of Radiation Curable Additives Enabling Excellent Paint …...The information contained herein...
RADTECH North America – April 2013
Paulo Roberto Vieira Jr, PhD
Radiation Curable Additives Enabling Excellent Paint Surfaces
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When and why do we need additives?
• Introduction
• Leveling and Flow
• Foam
• Rheology
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When and why do we need additives?
• Introduction
• Leveling and Flow
• Foam
• Rheology
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• Defects in the paint film are deviations in evenness and uniform smoothness of the paintsurface and are judged to be an indication of an imperfect coating process.
• Most defects are related to surface tension phenomena, which arise in a liquid because theforces in the air/liquid interface differ from those inside the liquid phase. To prevent orreduce such defects, flow and leveling additives are used.
• Examples of defects: orange peel, brush marks, peaks, craters, fish eyes, and pinholes.
When and why do we need additives?
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Surface tension effects drive two different mechanisms of flow:
1. To minimize the surface area of a liquid;
2. To minimize the surface tension differential (or surface tension gradient) to cover areas/liquids of high surface tension with lower ones.
Observation:Besides Surface Tension Differential, flow and leveling are influenced also by the following factors:
‐ Surface Roughness of the Substrate‐Wet Film Thickness‐ Rheological Behavior after Application‐ Drying Time/Flash Off Time and Speed of Solvent Evaporation
Surface Tension
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The concept of the surface energy can be more easily understood when looking to aliquid as an example. Atoms and molecules of the liquid may freely move in order to reachpositions with lower potential energy (thermodynamics law). In other words, a “place” where theforces (attractive and repulsive) acting in all directions are in equilibrium. On the other hand theparticles in the surface of the material experience only forces directed to the center of the liquid.
Due to this, the surfaces are always high energy regions. And precisely this difference between theenergies on the surface and on the interior is called SURFACE TENSION.
Surface Tension – Concept
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When and why do we need additives?
• Introduction
• Leveling and Flow
• Foam
• Rheology
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Coating
Substrate
Liquid attraction forces (surface tension of the fluid)
Repulsive forces of the solids towards flow (surface tension of the solid)
Ideal ‐ Substrate wetting: Substrate Surface Tension > Coating Surface TensionGood film establishment: Adhesion, Leveling, Flow, Gloss, D.O.I. (Image Definition).
Surface Tension – Substrate Wetting
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Surface Tension in Radiation Curing
A challenge in radiation curing formulations when dealing with SURFACE TENSIONcomes from a often polar profile of the regularly used components, which leads to higher liquidsurface tensions (or energies), impacting the leveling and mainly adhesion on some substrates.
This polarity is essentially determined by the type and number of functional groups.Polar groups, such as hydroxyl or carboxyl groups, increase the surface tension, while nonpolargroups, such as long alkyl chains, siloxanes, or (fluoro)alkyl groups, reduce it.
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Defects What happens in a non-ideal situation?
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Defects What happens in a non-ideal situation?
Example: Cratering
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(Meth-) Acrylic copolymers
Silicones
Fluoro surfactants
Fixing the Defects - Chemistries
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(Meth-) Acrylic Copolymers
No surface tension reduction
R1
C CH2
C O
O
R2 n
R1 = H ( Acrylate )CH3 ( Methacrylate )
R2 = AlkylPolyester/PolyetherSaltHO-functionalCOOH-functional
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Silicones
Modes of action depends on
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Silicones
Polydimethylsiloxanes
CH3
Si O
CH3
Si (CH3)3(CH3)3 Si O
X
2 – 27Levelling
45 - 230Slip
380 - 1500Defoaming
1800 - 2900Special Effects
X =
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Silicones
Modifications
Reduction of surface tension and/or slip improvement
Y Z
CH3
Si O
CH3
Si O Si (CH3)3(CH3)3 Si O
OrganicModific.
AlkylPolyesterPolyetherAlkylReactive:AcrylCOOHOH
mN/mCH3 21CH2CH3 26(CH2)9CH3 32
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Silicones
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Silicones and Interlayer Adhesion
Dosage
Cure Temperature
0,1%0,01% 0,2%
130°C/270°F
150°C/300°F
170°C/340°F
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Fluoro Surfactants
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Example
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ADDITOL® VXW 6503 N
Market standard
• Mobile polymer design for optimal dynamic surface tension reduction. Surface tension (< 22 mN/m)
• Low foam stabilization • Strong anti-crater efficiency • No influence on interlayer adhesion
• Comparable efficiency with Fluoro modified polymers.
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When and why do we need additives?
• Introduction
• Leveling and Flow
• Foam
• Rheology
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Incorporation of Air and Foam Generation
Production
Pumping and filtration
Manipulation
Application
During lacquer manufacturing
Application (airless/airmix)
Chemical reaction (e.g. NCO/H2O)
Porous substrates
!! Stabilised by the use of surface active substances - Surfactants !!
In some radiation curing formulations, foam can be a critical factor. The viscosity andrheological patterns, as well as the application conditions including the cure speed, can results in amore stabilized foam in the paint. Conventional actions such as viscosity lowering, addition of co‐solvents, and decreasing line speed, does not effectively collapse the foam. In this case, the use ofadditives are a very important part of the formulation.
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Foam Generation – Stabilizing effects
HydrophobicHydrophilic
Air
Liquid
Lamella
Air/Gas
Air/Gas
Gibbs elasticityMarangoni effectElectrostatic effectsHigh surface viscosity
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Foam Generation – Negative Impacts
Blisters Pinholes
Macro Foam MODAFLOW® , CYCAT®, ADDITOL®
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Foam Generation
Negative impacts
Poor pigment grinding
Increase of volume
Blisters
Pin holes
Poor gloss
Reduction in film quality
Foam prevention or destruction by using Defoamer and Air-release
Agents
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Formulation
DeaeratorDefoamerOrg. modified silicones
Silica
Waxes
Aliph. / arom. Mineral oils
Silicone oils
Special polymers
Fatty acid derivatives
Org. modified silicones
Aliph. / arom. Mineral oils
Silicone oils
Special polymers
Fatty acid derivatives
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Com
patib
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Effic
ient
StartMODAFLOW® , CYCAT®, ADDITOL®
ADDITOL® VXL 4951N “Best in class” for
Leveling/Defoaming on UV/EB formulations
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Defoaming and Air Release agents
Interface
Macrofoam
Microfoam
DEFOAMER
AIR-RELEASEAGENTS
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Defoaming mechanism
Air
DEFOAMERLamella
Deaerating mechanism
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Destabilising effect
Apolaric substance
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Deaerating mechanism
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Coalescence
Apolaric substance
V ~ r2
η
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When and why do we need additives?
• Introduction
• Leveling and Flow
• Foam
• Rheology
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Rheology
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Rheology is the study of the flow, or movement, of a substance in liquid formor solid under conditions where it exists a flow profile in stationary conditions undershear forces (e.g. agitation, roll application, spray gun pressure). The Rheological profile ofa fluid impacts directly on its applicability, drying, leveling, gloss and substrate wetting.
* OBS.: Radiation curing formulations are 100% solids fluids with a flow profile.
Thickeners
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Inorganic Organic
Associative Thickeners
Water-Phase
Starch derivatesCellulose derivates
Acrylic derivates
Associative cellulose ethersAssociative acrylic thickenersPUR - Thickener
Montmorillonite
Hectocrite
Silica
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Associative Thickeners – MechanismADDITOL® VXW 6360 / ADDITOL® VXW 6388
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Conclusions
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• Adjusting rheological profiles, leveling & flow parameters and breaking down the stabilized foam. Important characteristics in radiation curing coatings;
• Fixing defects and resolving deviations from the evenness and uniform smoothness of the paint surface, improving the final performance of the coating and optimizing the quality of the film leading to excellent finishes.
Additives play an important role on:
More info:
Latin America –Paulo Roberto Vieira Jr, PhDEmail: [email protected]
North America –Gary KlineEmail: [email protected]
Europe –Thomas SchoenbacherEmail: [email protected]
Asia –Yogesh DhamalEmail: [email protected]
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Thank you!
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