Ashland Specialty Ingredients
Novel, Cross-linkable Polymers and Applications
in Reactive Coatings
May 15, 2012
David K. Hood*, Surya Kamin, and Karyn B. Visscher
Ashland Specialty Ingredients (ASI), 500 Hercules Rd., Wilmington, Del. 19080
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Ashland Specialty Ingredients
Technical capability of novel PVP “oligomer”
• PVP functionality, such as high-quality print receptivity, with built in cross-
linking capability
• Potential to transform oligomer into a free-radical generator
• Solvent coating performance, such as good solution-wetting properties
• No-VOC, 100%-solids coating potential
• Potential for indefinite, cross-linkable coating formulation stability
• Potential for expanded array of difficult-to-adhere-to substrates:
polyolefins, polyvinylidene chloride (PVDC) and polyvinyl chloride (PVC)
• Potential for savings on energy
NOO
O
O
O
O
O
O
O
x y z
3
Ashland Specialty Ingredients
• Background to use of water-soluble polymers in inkjet receptive coatings
• Functional examples for PVP
• Problem statement for traditional coating approaches
• The UV potential
• Review of “PVP” oligomer chemistry
• Radiation and thermal prototype formulations and properties
• Conclusions
Outline
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Ashland Specialty Ingredients
Background
Benefits of water-soluble polymers in inkjet
• Printability
• Image resolution and stability
• Optical density
• Cross-linkable
Additional benefits of polymers in this study
• Film formation
• Gloss
• Fluid management of ink
• Transparency
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Ashland Specialty Ingredients
Background
Common water-soluble polymers in inkjet
Other materials common to inkjet coatings
• Polyvinylpyrrolidone
• Polyvinyl alcohol
• Cellulosics
• Starches
• Gelatin
• Acrylic latexes
• Modified styrenic latexes
• Polyurethanes
• Acrylates, modified acrylates
• Silicates, alumina
• Calcium carbonates
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Ashland Specialty Ingredients
Historical example of water-soluble polymer utility
Coating 1
• Type A pigskin
gelatin
• PVP K-60
Coating 2
• Polyvinyl alcohol
(Vinol 325)
• PVP K-60
In the absence of PVP, coating materials
produced inferior images.
Reference: US 4,503,111 assigned to Tektronix
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Ashland Specialty Ingredients
Historical aspects to use of water soluble polymers
• Good film formation
• Excellent absorption of dye-based inks
• Excellent optical density
• High gloss
• Compatible with solvent and aqueous systems
• Compatible with many typical formulation components
• Low water-resistance
Especially for PVP, the benefits are:
The inherent challenge is…
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Ashland Specialty Ingredients
VCL/DMAPMA/HEMA Terpolymer
Physical Properties • Slightly viscous aqueous liquid
• 29.0 – 31.0% solids
• 3,000 – 15,000 cps – as supplied
• pH = 6.5 – 7.8
• Specific Gravity = 1.054
• MW = 1.0-1.5MM (GPC/MALLS)
• Tg = 139C (freeze-dried)
• Cross-linkable with aziridine, epoxy and MF resins
NO
HN
N
O
OH
CH3H3C
O On
H+Cl
-
CH3 CH3
A cross-linkable
“PVP-like” material
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Ashland Specialty Ingredients
VCL/DMAPMA/HEMA – Cross-linking
Cross-linking
with aziridine
Reference: D.K. Hood et. al., JIST, 49, 6, 646-651 (2005).
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Ashland Specialty Ingredients
VCL/DMAPMA/HEMA – Cross-linking
CX-100 cross-linking of VCL/DMAPMA/HEMA
Reference: D.K. Hood et. al., JIST, 49, 6, 646-651 (2005).
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Ashland Specialty Ingredients
Prototype matte vinyl inkjet media
• Vinyl softening via VCL/DMAPMA/HEMA to improve
coating penetration into vinyl
• Use acrylic latex and Aquazol™ polymers to boost
adhesion of film
• Acrylic latex, Aquazol polymers, ViviPrint™ polymers
and PDADMAC polymers to form essential elements of
film
• Add silica gel to matte coating
• Silica gel yields nearly instantaneous drying of the print
• Cross-linking to boost water resistance of film
Strategy
Reference: D.K. Hood et. al., ECJ, 4, 150-154 (2007).
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Ashland Specialty Ingredients
Prototype matte vinyl inkjet media
Ingredient Product,
Supplier
Mass (g) % Solids Solid % Composition
Water 675.0
Colloidal Silica (~50 nm) 30.0 30.0 9.0 3.0
Silica Gel Silcron* G-100,
PQ Corp
144.0 100.0 144.0 48.6
Polyvinylpolypyrrolidone ViviPrintTM PS-10,
ASI
6.0 100.0 6.0 2.0
Acrylic latex NeoCar* 820,
Dow
50.0 45.0 22.5 7.6
Cationic vinyl pyrrolidone copolymer ViviPrint 131,
ASI
50.0 11.0 5.5 1.9
Poly(2-ethyl-2-oxazoline) AquazolTM 200,
ASI
50.0 20.0 10.0 3.4
Acrylate copolymer of HEMA/DMAPMA ViviPrintTM 300,
ASI
50.9 30.0 15.3 5.2
VCL/DMAPMA/HEMA ASI 160.5 30.0 48.2 16.3
pDADMAC Aldrich 45.0 35.0 15.8 5.3
Ethoxylated 2,4,7,9-tetramethyl 5 decyn-
4,7-diol
Surfynol* 440,
Air Products
3.0 100.0 3.0 1.0
Waterborne epoxy resin Ancarez* AR 550,
Air Products
31.0 55.0 17.1 5.8
TOTAL 1295.4 296.2 100.0
Reference: D.K. Hood et. al., ECJ, 4, 150-154 (2007). * Trademark owned by a third party.
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Ashland Specialty Ingredients
Prototype matte vinyl ink-jet media
Property
Solids 23%
Viscosity 260 cPs
pH ~7
Coating Weight (gsm) 36
Coating Bar #50 wire rod
Machine Web Speed 1.5 meters per minute
Gloss ~2
Drying Conditions 3 Infrared Lamps
Oven #1: 165oC
Oven #2: 165oC
Oven #3: 165oC
Solution Appearance Milky, white
Reference: D.K. Hood et. al., ECJ, 4, 150-154 (2007).
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Ashland Specialty Ingredients
Typical industrial coating machine
Source: http://www.polytype.com/en/converting/03_technology_centre/index.php?navid=13
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Ashland Specialty Ingredients
Prototype matte vinyl inkjet media
Water misting and Submersion data
OEM matte vinyl printed
with Epson R220
Prototype matte vinyl
printed with Epson R220
OEM matte vinyl printed
with HP 6840
Prototype matte vinyl
printed with HP 6840
Prototype matte OEM matte vinyl
vinyl with HP 6840 with HP 6840
Reference: D.K. Hood et. al., ECJ, 4, 150-154 (2007).
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Ashland Specialty Ingredients
Some challenges to traditional coatings
• Fluid viscosity/rheology and its relation to commercial coating
technique
• Solid content of coating solutions
• “Pot life” of coating solution
• Degree of cross-linking, batch-to-batch, process-to-process can
require study
• High energy costs to operate ovens
• Thermal and dimensional stability of substrates
• Safety and handling of coating components, particularly cross-linkers
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Ashland Specialty Ingredients
The next-generation PVP technology potential
• 100%-solids content of coating solutions are possible
• “Pot life” of coating solutions can be significantly improved
• Potentially more control of degree of cross-linking
• Cross-linking via thermal and/or UV treatments
• Wider variety of substrates are possible
• Potential big savings on energy and VOC/emissions
• Potential for lower total process costs
A more-sustainable and “greener” process
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Ashland Specialty Ingredients
VCL/DMAPMA/HEMA/GMA“UV Oligomer”
N
O
HN
N
O
OR
OO
OH
O
O
HN
NH
O
R= H or possibly
x yz a
OH
O
O
ClCl
Property Data
Viscosity (cPs) ~100 at 15% solids in water
Molecular Weight (g/mol) 115,000
Tg (oC) 159
Reference: Hood, D.K.; Kamin, S.; Musa, O.M.; Tallon, M.A., 24th International Conference on Digital Printing
Technologies and Digital Fabrication 2008, Pittsburgh, Pennsylvania; September 8, 2008; p. 367-369 (2008).
Free-radical
curing
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Ashland Specialty Ingredients
PVP/VA Vinyl Pyrrolidone/Vinyl Acetate Copolymer
Physical Properties
Functionality
• Linear, random copolymers, thermoplastic
• Aqueous or alcoholic solutions (50%) or powder (S-630)
• Soluble in water, alcohols, esters and ketones
• Available in range of VP / VA ratios
• Soluble in water when VP > 50%
• Soluble in ethers and aliphatic hydrocarbons
Increasing water solubility,
Film Hardness, Adhesive
strength, Glass transition
temperature &
Propane/Butane solubility
Increasing Humidity
resistance, Flexibility,
Cohesive strength
Polymer %VP
Series 100
E-735
I-735 70
W-735
W-635
S-630 60
E-535
I-535 50
E-335
I-335 30
NO
xO
z
O
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Ashland Specialty Ingredients
PVCap/VA/GMA and PVP/VA/GMA“Oligomers”
Property PVCap/VA/GMA PVP/VA/GMA
K-Value 19.3 (1% in MEK) 38.2 (1% in M-Pyrol)
Tg (oC) (1st Heating) 76 80
N
O
O
O
O
O
x y z
O
N
O
O
OO O
x y z
O
Thermal- and
cationic-curing
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Ashland Specialty Ingredients
O
O
O
O
O
NO
OOO
O
O
O
O
O
NO
O
OO
O
O
O
O
O
O
NO
HO
OO
OH
wy
x
wy
x
wy
x
NH4NH4
Novel PVP “PVP/MAN/AAEM”
• Thermal
• Inorganic (Al2O3)
• “Dual” thermal
• “Dual” UV-thermal
Curing Possibilities
Property PVP/MAN/AAEM Data
Viscosity (cPs) (50% in HEA) (DV-III, 100 RPM, #4 Spindle) 1,580
Tg (oC) ~95 (1st Heating)
K-Value range ~10
Presented at the American Coatings Congress
May 7th, 2012 Indianapolis, Indiana
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Ashland Specialty Ingredients
Coating
Composition
Mix
Ratio
pH Brookfield Viscosity (DVIII+)
(cPs, 100 RPM, RT))
Observation
PVP K-30 + HEC 1:1 6 260 Minor water resistance
PVP/MAN/AAEM +
HEC 1:1 3 176
Excellent water
resistance
PVP K-30 + PVOH 1:1 7 17 No water resistance
PVP/MAN/AAEM +
PVOH 1:1 3 20
Excellent water
resistance
PVP K-30 1 6 17 No water resistance
PVP/MAN/AAEM 1 2 8 No water resistance
HEC 1 6 2000 No water resistance
PVOH 1 7 42 No water resistance
PVP/MAN/AAEM – Thermal Cure w/ MAN
O
O
O
O
O
NO
HO
OO
wy
x
O
n
Proposed Structures
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Ashland Specialty Ingredients
NOO
O
O
O
O
O
O
O
x y z
O
HO
O
a
PVCap“Oligomers”
Property o(VPA) oligomer Data
o(VPHA) oligomer Data
Relative Viscosity (1% in MEK) 1.035 1.045
Viscosity in PEA (10% Solids) (cPs) ~30 ~20
Molecular Weight (g/mol) ~3,000 ~3,300
K-Value range ~8-10 ~10-12
Tg (oC) ~38 ~8oC
“o(VPHA)”
NOO
O
O
O
O
O
O
O
x y z
“o(VPA)”
Free-radical
curing
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Ashland Specialty Ingredients
Michael Addition of AAEM in “Oligomer”
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Ashland Specialty Ingredients
Experimental materials and equipment
• DuPont-Teijin Melanex* polyester film
• Fusion UV LC-6B bench top conveyor equipped with a
F300S/SQ lamp (200 to 350 nm)
• Belt speed set for 15 ft/min.
* Trademark owned by a third party
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Ashland Specialty Ingredients
Prototype Non-Aqueous-Based UV Curable Coating
Material Supplier Formulation #1
(g)
Formulation #2
(g)
Formulation #3
(g)
Formulation #4
(g)
Dipropylene glycol
diacrylate Aldrich 5.1 5.1 5.0 5.0
Hexanediol diacrylate Aldrich 2.0 2.0 2.0 2.0
urethane monoacrylate Ebecryl®*
1039, Cytec 2.0 - - -
o(VPA),
VCap/PEA/AcAc - 2.0 2.0 2.0
Isocyanatoethyl
methacrylate Aldrich - - 0.1 -
difunctional amine
coinitiator (amine
acrylate)
CN384,
Sartomer - - - 0.1
2-hydroxy-2-methyl-1-
phenyl-1-propanone
Darocur®*
1173, BASF 0.9 0.9 0.9 0.9
Total 10 10 10 10
* Trademark owned by a third party.
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Ashland Specialty Ingredients
Properties of Non-Aqueous Prototype UV Curable Coating
Property Formulation #1 Formulation #2 Formulation #3 Formulation #4
Adhesion 100% 100% 100% 100%
Hardness HB HB 2B 2B
MEK rubs @ 200
rubs No discoloration
Slight
discoloration
Slight
discoloration
Slight
discoloration
Crumple Good Good Good Good
Gloss High High High High
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Ashland Specialty Ingredients
Potentially less coating equipment required
Source: http://www.polytype.com/en/converting/03_technology_centre/index.php?navid=13
Roll Unwind Coating
Applicator UV Light Rewind
A simplified coating machine configuration
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Ashland Specialty Ingredients
Conclusions
• A novel, nonionic, inkjet-receptive polymer, suitable for free-
radical UV curing, has been designed and demonstrated.
• Functional prototype coatings have been designed.
• PVP functionality with built in cross-linking capability has
been demonstrated.
• Solvent coating performance.
• No-VOC, 100%-solids coating.
• Potential for indefinite, cross-linkable coating formulation
stability.
• Inkjet-receptive coatings produced by UV processes
comprising “PVP” like polymer materials is viable.
PVP “oligomer,” with built-in cross-linking functionality, can be incorporated into a variety of formulations, employing a
variety of industrial curing methods.
