New Waterborne Radiation Curable Compositions for Digital Printing Applications

Transcription

1 26 October 2017 New Waterborne Radiation Curable Compositions for Digital Printing Applications M. Tielemans, K. Poelmans, L. Boutreau FINAL VERSION

2 PART 1 : FOOD CONTACT APPLICATIONS

3 [Towards food contact markets & applications] Up Estimated global market split between technologies in packaging coating and ink market (%) Down left Estimated global market split between inks and overprint varnishes for radiation curing (kmt) Down right Estimated global market split between packaging food and non-food applications for radiation curing (kmt) Others Packaging Non-Food; 22 Food; October

4 PART 2 : NEW POLYMER STRUCTURES

5 [Strategy for novel low migration UV-PUD s in food contact] 1 Eliminate chemicals of concern (Sn, BPA, APEO, solvent ) 2 Maximize acrylates with Mw >500 Daltons AND Fc 6 3 Control composition for specific requirements (ex: resolubility) 4 Validate low migration and [indirect] food contact compliance 26 October

6 [New prototypes composition: example of IRR 929] Mn 1,875 Mw 27,600 Mw/Mn Figure a: Molecular weight distribution (GPC) and relative cumulative values for 2 prototypes (standard PS; detection RI) Figure b: product contains ~99.5% (solids) Mw >500 Daltons and functionality =/> 6 26 October

7 [Value proposition of low migration UV-PUD s for food contact] versus conventional UV : versus conventional WB : High Mw / functionality Very low viscosity Low odor Tack-free before cure Flexibility vs hardness No emulsifier Low MFFT (no coalescent) Resolubility before cure Chemical resistance Gloss range 26 October

8 PART 3 : INKJET APPLICATIONS

9 [Main technical requirements for inkjet inks] 1 INK STABILITY Time evolution at elevated temperature (45-60 C) of viscosity, ph, particle size, coagulum 2 INK FILTERABILITY Capacity to be filtered efficiently for good nozzle flow in the print head 3 INK JETTABILITY Consistency of droplets formation at the nozzles as a function of rheology and surface tension 4 INK RESOLUBILITY Resolubility of the dry ink in water to reduce drying & clogging of the print head nozzles 5 INK REACTIVITY Curing speed and effectiveness to provide full ink performance with usual or LED cure 6 INK ADHESION Adhesion to substrates in relation with ink shrinkage upon cure 7 INK RESISTANCE Mechanical and chemical resistance of the printed material under intended usage 26 October

10 PART 4 : NEW LOW MIGRATION RANGE

11 [Water-based UV low migration range regulatory compliance] LOW MIGRATION RANGE (EXPERIMENTAL) Label-free BPA-free Tin-free APEO-free Swiss-list IRR 929 EXP A EXP B EXP C EXP C IS A LOW MIGRATION SELF-CURING BINDER PROTOTYPE Based on IRR 929 Proprietary acrylated polymeric type II photo-initiator for low migration Proprietary process for improved colloidal stability Not specifically recommended for LED cure Still at an early development stage Note: all regulatory information is provided to the best of allnex knowledge at the time of presentation and without any liability. Products indicated above are good candidates for inkjet application but can also be used for conventional inks and overprint varnishes. 26 October

12 [Water-based UV low migration range product characteristics] As a liquid IRR 929 EXP A EXP B EXP C Solids (%) ~35 ~35 ~35 ~35 Viscosity (mpa.s) ~100 ~100 <10 ~100 ph ~7.5 ~7.5 ~6.7 ~7.5 Particles (nm) ~80 ~15 ~60 ~100 Mw (Daltons) >10,000 >10,000 <5,000 >10,000 MFFT ( C) <10 <10 <5 <5 Grits 50µ (mg/l) <20 <20 <20 <20 Stability 60 C (days) >10 >10 >10 >10 As a coating before cure IRR929 EXP A EXP B EXP C Tack (Y/N) N N Y N Table: characteristics of new prototypes with low migration profile for indirect food contact application 26 October

13 [Water-based UV low migration range product appearance] IRR 929 EXP A EXP B EXP C Figure: comparative product appearance 26 October

14 [Application results I : water resolubility before cure] IRR 929 EXP A EXP C 4/5 EXP B 5/5 Figure: comparative water resolubility before cure (1 RT) [proprietary pigmented product formulation] 26 October

15 [Application results II : mechanical & chemical properties] IRR 929 EXP A EXP B EXP C Young s modulus (Mpa) (2890) Ultimate elongation (%) 0,6 9,5 0,7 (0,6) Ultimate tensile strength (Mpa) 15,6 44,7 13,4 (15,6) Tg ( C) (200) IRR 929 EXP A EXP B EXP C Acetone double rubs Tables: mechanical and chemical properties of new prototypes with low migration profile for indirect food contact application Mechanical properties from free films 2.0% ADDITOL BCPK and curing Hg 5 m/min 120/cm 2 Chemical properties from 15µ (wet) coating on Leneta or PMMA with drying 4 60 C 1.5% ADDITOL BCPK and curing Hg 10 m/min 120/cm 2 26 October

16 [Application results III : adhesion on plastics] IRR 929 EXP A EXP B EXP C Polycarbonate (0-5) (tape) 1H (cross-cut) 1H Polyethylene* (0-5) (tape) 1H (cross-cut) 1H Polypropylene* (0-5) (tape) 1H (cross-cut) 1H Table: adhesion of new prototypes with low migration profile for indirect food contact application Rating 0-5 with 5 = best (*) plastics have been corona-treated 26 October

17 PART 5 : EXTRACTION TESTS IRR 929

18 [Extraction results by combined GC-MS and LC-MS analysis] EXTRACTION CONDITIONS FOR DIRECT FOOD CONTACT Formulation ADDITOL VXW 6360 [0 0.75%] Coating thickness 30µ [wet] Substrate Aluminum sheet [no washing] Curing Electron Beam [250 kev; 5 MRad; 10 m/min] Extractant Ethanol 95% Extraction 24h 60 C [direct contact] Contact 100 ml per dm 2 Conditions Immersion in closed glass flask Repeats Single experiment with a blanco substrate Detection LC-MS + GC-MS Protocol Related to FDA conditions of use H Table: experimental extraction conditions used to simulate direct food contact 26 October

19 [Extraction results main conclusions] Extractables detected at suspected ppb level by Single Ion Monitoring [GC-MS/LC-MS] MS response areas used for a semiquantitative analysis at iso-response factors Extraction levels are categorized and normalized for easier interpretation Our low migration prototype (IRR 929) shows very favorable migration data! Figure: normalized extraction data based on combined GC-MS and LC-MS Single Ion Monitoring area Direct food contact protocol with EB curing selected for most stringent conditions 26 October

20 PART 6 : REACTIVITY & LED CURING [ IRR 929 ON THE SPOT ]

21 SURFACE CURE [Reactivity with high and low energy ultraviolet source] IRR 929 EXP C Reactivity (m/min) Hg #1 1x150 / Reactivity (m/min) LED #2 1x20 / Reactivity (m/min) Hg / 1x100 Reactivity (m/min) LED / 2x5 Formulation #1: Formulation #2: Hg 120W/cm 2 LED 8W/cm ,5% ADDITOL BCPK IRGACURE TPO-L Table: reactivity of new prototypes with low migration profile for indirect food contact application 15µ (wet) on Leneta with drying of 4 60 C (reactivity assessment by surface cure using carbon black method) 26 October

22 PART 7 : TEMPERATURE STABILITY [ EXP A ON THE SPOT ]

23 Solids (%) Solids (%) Solids (%) [Evolution of the dispersion characteristics at 60 C] EXP A EXP A 10% % 1,5 1,5 35% d60 C Ref. 35% d60 C Ref particle size (nm) Viscosity (mpa.s) EXP A 10% 35% 7,2 7,5 7,6 7,7 10d60 C Ref. Figures: there is a limited evolution of product characteristics after 10 days at 60 C especially at high dilution (10% vs 35%) 6 6,5 7 7,5 8 ph 26 October

24 EXP A [Turbiscan colloidal stability by Multiple Light Scattering] Turbiscan by Formulaction measures NIR light transmission and back scattering over the whole sample height fc time and temperature (Product E) sedimentation floculation clarification Destabilization kinetic of experimental products for 10 days at 60 C through backscattering measurement shows a limited tsi index evolution (EXP A) 26 October

25 PART 8 : SHEAR STABILITY [ EXP B ON THE SPOT ]

26 [Fluidicam rheology by microfluidics] Formulaction s Fluidicam measures viscosity by pushing 2 liquids through a microfluidic chip Fluidicam microfluidic chip with channel 2,2mm large x 50µm deep High flow rate and strong confinement provide a laminar flow : the sample and the reference fluids can t mix in these specific condition! Control of shear/flow rates Q/Q R, optical measurement of width W/W R and reference ƞ R, makes it possible to derive sample viscosity ƞ 26 October

27 [Fluidicam test results] Figure: product as such (35%) and diluted (10%) were measured at shear rates from 1,000 to 100,000 s -1 (5 points - 2 repeats) 26 October

28 [Conclusions on microfluidics investigations] Fluidicam by Formulaction accurately measures rheology of low viscous samples at high shear rates and at different temperatures it is thus particularly adapted to inkjet. Product presents a very low viscosity (<10 mpa.s) and a thixotropic character at 35% - becoming Newtonian after dilution at 10% - over the whole shear range (100,000 s -1 ) Because of the characteristics of the microfluidic chip (50 µm gap) and the high shear rates (100,000 s -1 ), the fluid behavior could be compared to the conditions in an inkjet nozzle for colloidal stability & processability (nozzle clogging). 26 October

29 PART 9 : CONCLUSIONS

30 [Conclusions] Allnex exports LEO core competences for the development of new WBUV products for indirect food contact applications A chemical concept was developed to reduce low Mw migrating species together with the highest regulatory compliance Four low-viscous & resoluble prototypes with high stability & performance are presented (incl. LED-curing and self-curing) These products are suitable as ink(jet) or OPV binder for high-end applications on corrugated sheets & plastics for food contact New technological steps and investigation methodologies were used to support growing market expectations Food contact WB polymers UV technology Graphic market 26 October

31 26 October 2017 Thank you Visit us at The Inkjet Conference! October 24-25, 2017 in Dusseldorf «LED Boosters and WBUV resins: solutions for next generation inkjet inks» by Kevin Poelmans UCECOAT Small particles for big success Disclaimer: Trademarks indicated with, TM or * as well as the allnex name and logo are registered, unregistered or pending trademarks of allnex IP s.à.r.l. or its directly or indirectly affiliated allnex Group companies. allnex Group companies ( allnex ) decline any liability with respect to the use made by anyone of the information contained herein. The information contained herein represents allnex's best knowledge thereon without constituting any express or implied guarantee or warranty of any kind (including, but not limited to, regarding the accuracy, the completeness or relevance of the data set out herein). Nothing contained herein shall be construed as conferring any license or right under any patent or other intellectual property rights of allnex or of any third party. The information relating to the products is given for information purposes only. No guarantee or warranty is provided that the product and/or information is adapted for any specific use, performance or result and that product and/or information do not infringe any allnex and/or third party intellectual property rights. The user should perform his/her own tests to determine the suitability for a particular purpose. The final choice of use of a product and/or information as well as the investigation of any possible violation of intellectual property rights of allnex and/or third parties remains the sole responsibility of the user allnex Belgium SA. All Rights Reserved