Hydrophobing technology new defined Non-POP Alternative …Hydrophobing technology new defined-Non-POP Alternative to ... low critical surface energy high contact angles good repellency

Rudolf GmbH Geretsried HEAD of global R&D Rudolf Group Author: Dr. Duschekwww.rudolf-group.com Waterproofing at the crossroads 1 02.05.2013

Dr. Roland Weber for Rudolf Group @ COP6

HydrophobingHydrophobing technology new definedtechnology new defined-- NonNon--POP Alternative to POP Alternative to

PFOS and related substancesPFOS and related substances


Contents

1. Who is Rudolf Group

2. PFOS Stockholm Convention - Specific Exemptions

3. Why are/were fluorocarbons used for textile finishing?

4. FC-free water-repellent finish - BIONIC-FINISH ECO

5. Performance vs Environment – an overview

6. Conclusions and way forward


Who is Rudolf Group

German based speciality group with a focus on textile auxiliaries

The company has never used PFOS chemistry !

Global player with activities in all relevant markets

The Group has strong focus on R&D and supports variousproduction sites close to the customers

Rudolf Group is supported by more than 1´000 dedicated employees

Hydrophobicity (a key key expertise of the Rudolf Group) is an important effect for performance- and consumer textiles


Outdoor


(Alternatives needs phase-in)• Coatings

• Textiles • Upholstery• Carpets• Paper and packaging• Leather and apparel• Other coating additives

• Chemically driven oil production, • Insecticides for control of red imported fire

ants and termites, • Hard metal plating, Decorative metal plating• Photo masks in semiconductor and LCD

industries, • Electric/electronic parts for some color

printers/copy machines,

PFOS - Specific Exemptions (SC Annex B)

Rudolf GmbH Geretsried HEAD of global R&D Rudolf Group Author: Dr. Duschekwww.rudolf-group.com Waterproofing at the crossroads 6 02.05.2013Source: Risk and Policy Analysts (2004); Fricke & Lahl, UWSF 17, 36 – 49 (2005)

Fiber coating

PaperSurface

AFFFAviation

Plating

Photographic

Industrial application EU consumption(Tonnes/year

PFOS & PFOS-related chemical

6

Former PFOS Consumption in EU (2000)


Rudolf Group -Aware on the PFT Challenge


Part II

Why were/are fluorocarbons used for textile finishing?

State-of-the-art performance !


Why are fluorocarbons used for the impregnation of textiles?

Fluorocarbons reduce the critical surface energy of substrates, so that it is lower than the liquids in contact.

low critical surface energy

high contact angles

good repellency


PFOS/PFOA free products

• PFOS-free products due to the use of monomers from telomerisation.

• Free PFOA only in traces << 1 ppm contained in the product.

• FC-components are bonded to the polymer.

• Polymers are crosslinked on the substrate and are not bio-available.

But what about the future fate? –

Can these polymers break down to e.g. PFOA?


Examples:

Surface: γc [mN/m]

-CF3 6-CF2- 18-CH3 24-CH2- 31

Water 73

What is the effect of fluorocarbons based on?


The way to PFOA- / PFOS – free*

Finishes:

• Optimization of the FC-finishes

with building-block systems

(Booster & Dendrimers)

• Use of alternative Monomers (C6 chemistry)

•• FC-free products (for certain applications)


Part III

Fluorocarbon-free alternatives?


®®BIONICBIONIC--FINISH ECOFINISH ECO

is a water-repellent finish based on patented“dendrimer”-technology due to bionic principles


Textile

Selforganisation of a surface with hydrophobic modified hyperbranchedPólyurethane’s with wax-modified comb polymers

Surface with oriented CH3-groups

Fluorine-free, high-performance hydrophobing

*Source: Scientific Expertise“Characterization of Active Ingredientsin Water, Oil- and Soil-repellent TextileImpregnations”

Prof. Dr. Martin Moeller, Director of DWI at RWTH Aachen


*Source: Scientific Expertise“Characterization of Active Ingredientsin Water, Oil- and Soil-repellent TextileImpregnations”

Prof. Dr. Martin Moeller, Director of DWI at RWTH Aachen

SFM-Surface analysis


Conclusions from Scientific Expertise from the RWTH Aachen

BIONIC-FINISH ECO

•… does neither contain inorganic nanoparticles nor fluorinated or perfluorinated hydrocarbon polymers*

*Source: Scientific Expertise

“Characterization of Active Ingredients

in Water, Oil- and Soil-repellent Textile

Impregnations”

Prof. Dr. Martin Moeller,

Director of DWI at RWTH Aachen

•“Certain roughness of the waxy film is even expected to improve the repellency effect, as the super repellent wax-surfaces of plant leaves , e.g. those of Lotus, Lady’s mantle and others”*

•…is proved to have the ability of selforganisation of the two polymers on the surface…


Properties for textile applications:

• FC-free waterproofing agent• excellent water-repellent effects with

very good Bundesmann ratings• low curing temperatures• very good washfastness• better abrasion-resistance than

fluorocarbons

• no oil- or blood repellency


Part IV

Environment vs Performance –

an overview!


Performance: C8-chemistry C6-chemistry Bionic-Finish ECOWater repellency very good very good very good

Oil repellency good alike no OR

Washing Durability very high high high

Low temperature curing poor good excellent

Abrasion Resistance poor poor good

Handle moderate slightly softer very soft

Price “normal“ higher very competitive

Chemical base: fluorocarbon fluorocarbon PFC/POPs-free

Sustainability poor “accepted” very good!

Sustainability vs. Performance?


Sustainability profile

Conclusions from “Environment, Health and Safety Assessment”by Modern Testing Services Germany GmbH (MTS), MD Dr. Sedlak, Nov 2012

•“Safe regarding occupational health aspects…”

•“Safe for intended use regarding waste water emissions from the padding processes ….”

•“Safe regarding consumer health and safety aspects… “

•“Safe regarding air emissions aspects…”

•“Safe regarding all kind of disposals of the finished articles and products….”

®RUCO-DRY ECO


How “free” is free?

PFC-background-level in water, air and environment!

Cross-contamination of substrates running PFC- and PFC-free products on the same equipment.

The PFOS/PFC/fluorine-free*/POPs free finish is not based on fluorocarbon and cannot break-down to PFOS/PFC! – No active contribution to the PFC problem!

Limit of detection is down to ppb and ppt!

However the entire production cycle to be considered for “POPs-free”


• FC-polymers are still the state-of-the-art to achieve oil-, blood- and soil-repellency for certain applications. Rudolf new generation of C6-polymers is close to the performance of C8-chemistry and is no source for PFOS, PFOA and related chemicals (precursors).

• Bionic-Finish ECO (non-FC) confers optimal water-repellent effects on the textile, without using PFOS/POPs or Organofluorine/Organohalogen –components and also no nanoparticles.

• For some performance indicators (low temperature curing; abrasion resistance; handle) the Bionic-Finish ECO is superior to PFCs

• Risk/pollution assessment show that the entire life cycle of Bionic-Finish ECO (production, use phase in consumer articles and end-of-life phase) has no risk for health and is environmentally friendly (sustainable product).

Conclusion & Way Forward

At the end of the day the manufacturers of chemicals and the users (“Brands”! ) are both responsible what will be used for hydrophobing of textiles….

……and for the image!


Thank youvery much foryour attention!

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Hydrophobing technology new defined Non-POP Alternative …Hydrophobing technology new defined-Non-POP Alternative to ... low critical surface energy high contact angles good repellency