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Emerging/Future Applica6ons for UV Cure Technologies
Acknowledgements: Jo Ann Arceneaux, Marcus Hutchins, and Jonathan Shaw
1
Michael J. Dvorchak
2
Agenda
• Self Curing Resins
• High Func6onality Oligomers
• High Gloss UV Polyurethane Dispersions
• Acrylated Allophanate Oligomers
• Thick sec6on UV Cure Elastomers
• UV Cure Glass Coa6ngs
• 1K UV Dual Cure Conformal Coa6ngs • 1K UV-‐A Auto Refinish Clear Coats • UV-‐A Aerospace Coa6ngs • Direct to Metal Applica6ons
Raw Materials selec6on
Produc6on
Quality Control
Self Curing Resins -‐ Low Extractable / Low Odor versus Standard
Technical Performance
Cost
ISO 9001
Physico-‐Chemical
Technical Performance
Purity
Cost
ISO 9001
Longer Stripping
GMP
Physico-‐Chemical
ImpuriIes
GC-‐MS
Standard Self-‐Curing Resin
Mutagenicity NOT Evaluated NON Mutagenic
Self-‐Curing Resins -‐ Migra6on (extrac6on) Tes6ng for Low Extractable/Low Odor versus Standard Products
Formula6on:
6 µm film (on PP) Cure dose: ~800 mJ/cm² Direct contact: 10 days at 40°C Simulant: 95% Ethanol/5% water
50% Ethanol/50% water
Product %
TMPTA 70 Low extractable/low odor; Flexo/OPV or Litho self-‐curing resin
30
100
Product 95% Ethanol 5% water
50% Ethanol 50% water
Low extractable/ low odor ; Flexo/OPV self-‐curing resin
Not Detected DetecIon limit = 50 ppb
Not Detected DetecIon limit = 10 ppb
Low extractable/ low odor; Litho self-‐curing resin
Not Detected DetecIon limit = 50 ppb
Not Detected DetecIon limit = 10 ppb
Results (LC-‐MS):
Test condi6ons
Both self-‐curing resins are compliant with Nestlé guidance note & Swiss Ordinance B-‐list (leber)
Highly Func6onal (f = 9 & 10) Oligomer Proper6es
5
Characteris6c Bravo 1 Bravo 2
Appearance Clear liquid Clear liquid
Density (g/cm³) 1.19 1.19
Viscosity at 60°C (mPa.s) 3000 1700
80°C stability 10 days 10 days
Color, APHA Max 100 Max 100
FuncIonality 9 10
End applicaIon Hardcoat on Flexible/rigid
substrates
Hardcoat for rigid substrate or at low coat weight on filmic
substrates
Highly Func6onal (f=9 & 10) Low Coat Weight Applica6ons
3 to 5 g/m² (dry) 1100 mJ/cm² 6f ALUA Bravo 1 9f Bravo 2 10f
100 acetone double rubs OK OK OK
Cross hatch tape adhesion 100 % 100 % 100 % Visual inspecIon (µscope) aier 10 double rubs with 00 grade steel wool
Many scratches Some scratches Very few scratches
uncoated PMMA 6f ALUA Bravo 1 9f Bravo 2 10f
1 mm
UV Cure PUD -‐ High Gloss & Mirror Effect
7
Op6cal Proper6es (UV PUD Charlie) Substrate: Black ABS
Film thickness: 120µ wet Drying: 20 min, 40°C
Curing: 5m/min 80W Hg lamp
Gloss 20°, expressed in Gloss Unit (GU) 83.3 DOI (%) 98.8 LogHaze 1.6
Rspec (GU) 79.3
• DOI is the disInctness of Image = sharpness of a reflected image in a coaIng surface.
• RSpec is the Peak specular reflectance. RSpec is very sensiIve to any surface texture. When RSpec = Gloss , the surface is smooth.
• Haze describes the milky halo or bloom seen on the surface of high gloss surfaces. Haze is caused by microscopic surface texture which diffuses light adjacent to the main component of the reflected surface.
UV Cure PUDs -‐ Coa6ng Performance… Scratch Resistance
Picture of scratched high gloss coa6ngs 120µ wet -‐ dried 20 min at 40°C -‐ cured at 5m/min under a 80W Hg UV lamp
Linear Taber Abraser -‐ 500g load -‐ Steelwool 00 -‐ 10 DR -‐ 20 r/min
8 Scratched Zone
Acrylated Allophanate Oligomers
• Based on aliphaIc allophanate polyisocyanate (HDI-‐type)
• Low viscosity • High amount of urethane/allophanate structures
• Outdoor perfomance
March 14, 15 9
Idealized structure
Acrylated Allophanate Oligomers Applica6on on PC plas6c and outdoor stability
Formula6on Func6on %
by weight UV-‐curing allophanate resin 80
HDDA react. thinner 80 Irgacure® 184 UV-‐iniIator 4.9 BYK® 306 leveling agent 1.6 Hostavin® 3206 UV-‐absorber 3.8 Hoatavin® 3058 HALS-‐amine 1.7
Curing 1.800 mJ/cm² (Hg spectrum)
DFT ca. 25 µm Substrate Makrolon AL 2647
Weathering data Urethane Acrylate
ISO11341 Xenon Test CAM 180 UV -‐ B
Echo > 5000 h 5000 h 2500 h
Fox Trot 1 3750 h 3250 h 2500 h
Alpha 1 5000 h 5000 h 2500 h
Bravo 1 5000 h 5000 h 2500 h India 1 3000 h 3000 h 2500 h
Test parameters: Chalking, adhesion, cracks, blisters
Thick Sec6on UV Cure Elastomers
Ingredient A; Parts by weight
B; Parts by weight
C; Parts by weight
D; Parts by Weight
Oligomer LS 97.09 48.54 33.2 -‐
Oligomer LF -‐ 48.54 -‐ -‐
Oligomer EF -‐ -‐ 33.02 -‐
Oligomer MF -‐ -‐ -‐ 97.0
Monomer -‐ -‐ 28.3 -‐
PhotoiniIator 2.91 2.91 5.66 2.91
Tensile; PSI 10,395 9,615 7,314 1,677
% ElongaIon 3.7 5.9 8.3 124
Tear Strength 489 577 1,051 261
Cure; V-‐H bulbs Yes Yes Yes Yes
Line Speed; i./min
10 10 10 10
75 mils Yes Yes Yes yes
11
Glass Coa6ngs -‐ Glass Bokle Line Simula6on Test
Ingredient E; Parts by weight
F; Parts by weight
G; Parts by weight
J; Parts by Weight
Oligomer LS 255.12 228.36 201.58 187.94
Oligomer LF 13.43 40.30 67.19 80.55
PhotoiniIator 1 8.05 8.05 8.05 8.05
Flow AddiIve 1.68 1.68 1.68 1.68
PhotoiniIator 2 3.36 3.36 3.36 3.36
Pigment Paste 3.36 3.36 3.36 3.36
Butyl Acetate 115.07 115.07 115.07 115.07
ReacIve Dil. -‐ -‐ -‐ 115.07
RaIo:Hard/Soi 95/5 85/15 75/25 70/30
Mic.H; N/mm2 158 122 112 139
Scribe Adh. Pass Pass Pass Pass
Line SIM (min) 10 15 5 -‐
12
1K UV Cure -‐ Dual Cure Conformal Coa6ngs
• Conformal CoaIngs were developed to miIgate enviromental issues with the prinited circuit board
• Developments in this technology have led to a dual cure concept that uses the R-‐N=C=O and R-‐C=C as the funcIonal part of the system.
• Recent developments show extremely low VOC, 1K UV Cure systems with viscosiIes less then 800 mPa s
• This 1K UV Cure; Dual Cure system have proven themselves by passing the Delphi Delco Q1000-‐101, Test CondiIon D
13
Delphi Delco Q1000-‐101, Test CondiIon D = -‐ 40 F to 125 F, and 1,000 cycles This tesIng lasts 500 hours and dwell Ime was set at 12 min. for each temperature extreme
UV-‐A Auto Refinish -‐ Innova6on in the Market for Clear Coats
14
Resin °C
UA Resin A 10
UA Resin B 104
UA Blend 1 103
UA Blend 2 105
UA Blend 3 106
UA Blend 4 84
UA Blend 5 74
Commercial UV Refinish 101
Commercial 2K Refinish 62
Concept of matching the Tg’s of tradiIonal 2 K clear coat technology with a 1K UV-‐A cure clear coat 14
UV-‐A Auto Refinish -‐ Concept of matching the Tg’s of tradi6onal 2 K clear coat technology with a 1K UV A cure clear coat 14
15
Photo micrograph of a blend line for a commercially available 2K Clear Coat over a black base coat
Blend line Blend line
Photo micrograph of a blend line for a UV – A Cure Clear Coat Aier matching Tg of a
2K Clear Coat over a black base coat
UV-‐ A Aerospace Coa6ngs -‐ Gloss Reduc6on Techniques in UV
• Large parIcles • Increased viscosity • Produces a truly rough surface
• IncompaIble oligomers/monomers
• Curing with two high intensity lamps • Xenon lamp (172 nm) cures surface
• Mercury lamp provides through cure • Causes shrinkage and reduces gloss • Requires full spectrum lamps and inert environment (ozone formaIon)
UV-‐A Aerospace; Reducing Gloss and Oxygen Inhibi6on
• Gloss levels did not decrease with increasing flabener levels
• Decreased light intensity or resin content increases O2 inhibiIon
• Gloss proporIonal to degree of O2 inhibiIon
• Inhibited surface cures last
Light Type 60° Gloss
85° Gloss
Fusion Full Spectrum Light (Focused) 47 81
H & S UV-‐A Light (Flood) 3 26
Quantum UV-‐A Light (Flood)
4 27
AddiIonal 10% Monomer (H &S)
3 3 Focused Light
Flood Light
Direct to Metal (DTM) Coa6ngs -‐ Allophanate Modified Oligomers
18
XP 2666, PVK 17 ca. % FWO 5721- 2 C 120 h 240 h 120 h 240 h Stop 120 h 240 h Stop 120 h 240 h Stop
FWO 5721- 5 d FWO 5721- 4 C FWO 5721- 1 d FWO 5721- 2 c
Conclusion: Combined with UV inert extenders allophanate acrylates perform much beber than epoxy-‐ester acrylates
Salt spray results with Allophanate modified oligomers, pigmented
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For more informa6on, please visit us at www.allnex.com.
Contact Name: Michael J. Dvorchak Office Phone: 404-‐719-‐8912 E-‐mail: Michael.Dvorchak@allnex.com
Thank you
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