NANOCONVENTION 2007

Nanoparticles: The Basis of Ink-jet Materials

Rita Hofmann

ILFORD Imaging Switzerland

NANOCONVENTION 2007

• Company Profile ILFORD

• Products

• Technology

• Advantages of nano particles

• Risk assessment

• Outlook

Lay-out

NANOCONVENTION 2007

Site Marly (FR)

Ca. 420 employees in Switzerland, ca 20 outside

Production ~ 200

Sales, Distribution, TS, 50

FO&E 70

Administration (Finance, IT, HR) 100

Production site in Marly (FR), since 2005 part of Oji Paper Group (Japan)

World-wide sales (Export >95%)

To key customers (>70%)

Own brand

Private label

NANOCONVENTION 2007

125 Years of (international) History

18791879

18821882

19351935

1879 H.A. Harmann, «Britannia Plates» founded in Ilford UK1882 «Lumière» founded in Lyon France1935 «Telko» founded in Fribourg CH1969 Consolidated by Ciba-Geigy

1989 Acquisition by International Paper USA

1997 Acquisition to Investment company Doughty Hanson (UK)

2005 Sale of the Swiss site to Oji Paper Group , Japan, ofILFORD Imaging Switzerland)

18791879

NANOCONVENTION 2007

Colorants for Photo-qualityIJ printers

IJ Photo papersIJ Proof papers

Considerable market share in:

Technological Transition: Photo to Ink-jet

0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

100%

1998 1999 2000 2001 2002 2003 2004 2005 2006

Traditional photoInk-jet

NANOCONVENTION 2007

Sales of ILFORD in product categoriesin 2006

ILFORD Products

Desktop InkjetPapers

56%

Wide Format InkjetPapers

17%

Inks and dyesInkjet21%

Photographic color products6%

All products are manufactured in Marly, Switzerland

NANOCONVENTION 2007

Technological Background

NANOCONVENTION 2007

Business Photography Ink-Jet Imaging

Competence

AgXCore-shellparticles

Dye-Synthesis

Web-coating

Ink-Formulation

Company BACKGROUND

NANOCONVENTION 2007

From Tree to Photo: Manufacturing processes

Pulp& Paper making

Base Paper making

Front and backinglayercoating

Dispersion making

Rawmaterials

forestry Photo Prinitng Photo performance

Manufacturing steps Ink

CoatingSolutionmaking

NANOCONVENTION 2007

Layer technology of IJ Photo Media

Thickness of layersdry 1 – 50 μwet 10 – 500 μ

Ink-jet media production process resembles photographic coatingprocess, Coating solutions are made of metal –oxide nanoparticle instead of silver halide dispersions

Curtain Coating

Ink Jet

Disperison making and

Coating solution making

NANOCONVENTION 2007

Polymer technology

Nanoporous technology

Dry Wet

time

Polymer

time

SiO2

Two types of Ink-Jet receiving layers

Nanoporous

NANOCONVENTION 2007

Advantages Nanoparticles

Receiving layerhν

hν

0

2

4

6

8

10

12

0 10 20 30 40 50

Vol

%

Diameter of particles [nm]

Size of particles in dispersiondv50 16nmall particles < 43 nm

Paper support

Glossy Photo paper

PE

Silica/Alumina

• Faster drying, faster printing• Water fast • Fine Pores=better transparency• better transparency =>• =>better Gloss• => better colour brilliance

NANOCONVENTION 2007

feathering

ozone fastness

coalescence

bronzing

ink overload

-60

-40

-20

0

20

40

60

80

100

0 -80 -60 -40 -20 0 20 40 60 800 . 0 0

0 . 5 0

1. 0 0

1. 5 0

2 . 0 0

2 . 5 0

0 10 2 0 3 0 4 0 5 0 6 0 7 0 8 0 9 0 10 0

C rM gY bR gR bG rG bB rB gK3K4KW

OD, gamut

Ink up-take volume

Ink up-take speed

Film transparency

Dye adsorptioncharacteristics

Otherproperties

NANOCONVENTION 2007

Nano Pigment Ink

Pigment Ink TypPrimary size(nm)

Surface TensionDynes/cm

Mean Particle Sizes (nm) BET

m2/gMagenta1Magenta2

PR122PR122

-60

3236

130108

6397

Cyan 1Cyan 2

PB15:3PB15:3

85-

3236

12986

48130

Yellow 1Yellow 4

PY155 PY74

9065

3635

160111

5047

L=90

L=80

L=70

L=60

L=50

L=40L=30

L=20

-80

-60

-40

-20

0

20

40

60

80

100

120

-100 -80 -60 -40 -20 0 20 40 60 80 100

R

G

Y

M

B

C

Inkset 2M2,C2,Y4 - Gamut Total 33,452

L=90

L=80

L=70

L=60

L=50

L=40L=30

L=20

-80

-60

-40

-20

0

20

40

60

80

100

120

-100 -80 -60 -40 -20 0 20 40 60 80 100

R

G

Y

M

B

C

Inkset 1M1,C1,Y1 - Gamut Total 22,329

NANOCONVENTION 2007

SuccessSuccess factorsfactors

NANOCONVENTION 2007

New competences through collaboration

EIF

ILFORD Nanoporous Ink-Jet TechnologyCollaboration with Prof. H. Hofmann (EPFL)

Dispersion making + Gas-fadingCollaboration with Prof. G. Furrer (ETHZ)

Investigation of gas-fading mechanismsCollaboration with Prof. Rossi (EPFL), J.-N. Aebischer (EIF)

Li-Ion Battery Project Collaboration with Profs. M. Grätzel & H. Hofmann (EPFL)

Nanoporous polymer layers Collaboration with M. Liley (CSEM)

Thin film security labels Collaboration with Dr. A. Stuck (CSEM)

Thin film optics and imagingCollaboration with Prof. L. Zuppiroli (EPFL)

And many more....

Ink-Jet

Energy

Optics&

Imaging

NANOCONVENTION 2007

Key factors

KMU have limited means (per year and cumulated ) for Investments. Important was :

• Motivation to change and take a risk• Evolutionary and not revolutionary technology

– Existing production machine could be used ( with modifications)– Traditional production could run in parallel – Additional investments were modest– Essential know how was available in the company, special know-how in

Switzerland (collaboration with universities)• Nano particle were only used in a closed production process, so that

the HS&E risk for could be estimated.• There was a need for the product in a world wide existing market.

– Assures fast sales – But also means that the competition will follow very soon. (other

companies, other technologies)

NANOCONVENTION 2007

Investments

New background technology is only slowly paid back in a traditional company, it must replace existing and proven technology

• Research effort had to be invested for more than 4 years (first patents) before the technology reached the development stage.

• Considerably more effort was necessary for the development stage (about 10x cumulated)

• Introduction into production took more than a year. Total time to large scale production was more than 8 years before first profits were made with the technology.

• Payback will be more than 4 years after introduction .

• Total time equals cycle times of technology today.

NANOCONVENTION 2007

Form Polymer to nano particle layer technology

Research cost and Sales

05

1015202530354045

2002 2003 2004 2005 2006

NanoTraditionel

0%

10%

20%

30%

40%

50%

60%

Part of Nano products

0%

10%

20%

30%

40%

50%

60%

1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006

% Forschung% Produktion

NANOCONVENTION 2007

RiskRisk ManagementManagement

NANOCONVENTION 2007

Scientific Research vs industrial Production

Scientific research• Small quantities for limited time• Aim is understanding and learning

Industrial Production • Large quantities over longer time , target are competitive products • Installation are often used for different processes.• Prevention of break down and events are high priority• Manufacturers are liable.

– much stricter selection of materials that are used.

Important: Risk assessment in production• Use of harmless raw materials or adapted manufacturing processes, work safety and strict

work practice• Responsible waste management• Prevention of accidents and events

NANOCONVENTION 2007

Exposure assessment algorithm (of the Scientific Committee on Emerging and newly identified Health risks SCENIHR)

Is human/environmental exposure likely NO Reassess if change in use/manufacture/disposal

YESAre the particles of a substance whose toxicology is known

YES

NO Full risk assessment required

Are particles homogeneous

Are particles soluble in aqueous media

YES

NO

NO Different particles may need to beassessed separately

YES Further assessment may not beneeded +

Are particles less than 0.1umYES

Does rapid coalescence with other particlesoccur

NO

Are other chemicals adsorbed onto the particle

NO

Is the reactivity much greater than for largerparticles ot the same substance

NO Existing exposure data may besufficient +

Existing exposure data may besufficient +

High priority for ADME studies by relevant routes of exposure

YES

NO Existing exposure data may be sufficient

YES

YES

NANOCONVENTION 2007

Industrial Nanochemistry

Dry powderBeispiel :

Source: www.cabot-corp.com

Density (uncompressed): 40 kg/m3

25 m3 = 25’000 l

1000 kg

Big-bag1 m3

25 big-bags

NANOCONVENTION 2007

Risk Management

Avoiding risk in manipulation

Risk management

• No standards about toxicity and eco-toxicity of Nano particles

• Open Dialogue with the public

Measures at ILFORD

• Final products have no nano particles Manipulation as much as possible in a closed process

• Eco-studies at intermediates were made and showed they are benign

• Support through SUVA in fine particle measurements

• Collaboration in the commission for standards

NANOCONVENTION 2007

Further progress

Silo-Technology

NANOCONVENTION 2007

OutlookOutlook

NANOCONVENTION 2007

The future potential of the technology in other fields than hardcopyimaging.

time

Mat

urity

of te

chno

logy

products

today

PhotographyInk-Jetnew technology

about 150 years

ca.20 years

Technology Transition: Imaging

NANOCONVENTION 2007

AqueousAqueous coatingcoating of of flexible hybrid flexible hybrid filmsfilms

PolymerSol-Gel

Nanoparticle

Ilford competences

Design & SynthesisDesign & Synthesisof of organicorganic dyesdyes andandfunctionalfunctional hybrid hybrid

nanoparticlesnanoparticles

FormulationFormulationof of solublesoluble

& & pigmentedpigmented

inksinks

NANOCONVENTION 2007

Building-block system to create a broad palette of new products

barrier layertransparent baseadhesive layer

luminescentconductivelow index n

Economical large area

multilayer coatingsof functional materials

2D-Pattern (Ink-Jet)

New generation of products

The future

NANOCONVENTION 2007

ThankThank youyou