Novel, Cross-linkable Polymers and Applications in …€¦ · · 2018-04-04Ashland Specialty Ingredients Novel, Cross-linkable Polymers and Applications in Reactive Coatings May

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

2


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


• 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

4


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

5


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

6


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

7


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…

8


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

9


VCL/DMAPMA/HEMA – Cross-linking

Cross-linking

with aziridine

Reference: D.K. Hood et. al., JIST, 49, 6, 646-651 (2005).

10


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).

11


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).

12



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.

13


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


14


Typical industrial coating machine

Source: http://www.polytype.com/en/converting/03_technology_centre/index.php?navid=13

15



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


16


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

17


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

18


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

19


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

20


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

21


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

22


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

23


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

24


Michael Addition of AAEM in “Oligomer”

25


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

26


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.

27


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

28


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

29


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.

Novel, Cross-linkable Polymers and Applications in …€¦ · · 2018-04-04Ashland Specialty Ingredients Novel, Cross-linkable Polymers and Applications in Reactive Coatings May

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