Nanoparticles: The Basis of Ink-jet

Materials
Rita Hofmann
ILFORD Imaging Switzerland

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Lay-out
Company Profile ILFORD
Products
Technology
Advantages of nano particles
Risk assessment
Outlook

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Site Marly (FR)

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

Ca. 420 employees in Switzerland, ca 20 outside

Production

~ 200

Sales, Distribution, TS,

50

FO&E

70

Administration (Finance, IT, HR)

100

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125 Years of (international) History

1879

1879 H.A. Harmann, Britannia Plates founded in Ilford UK

1882 Lumire founded in Lyon France
1935 Telko founded in Fribourg CH
1882
1969 Consolidated by Ciba-Geigy
1935

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, of
ILFORD Imaging Switzerland)
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1879

Technological Transition: Photo to Ink-jet

100%
90%
80%
70%
60%

Traditional photo

50%

Ink-jet

40%
30%
20%
10%
0%
1998 1999 2000 2001 2002 2003 2004 2005 2006

Considerable market share in:

Colorants for
Photo-quality
IJ printers
IJ Proof papers
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IJ Photo papers

ILFORD Products
Sales of ILFORD in product categories
in 2006

Inks and dyes

Inkjet
21%

Photographic color products

6%

Desktop Inkjet
Papers
56%

Wide Format Inkjet

Papers
17%

All products are manufactured in Marly, Switzerland

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Technological Background

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Company BACKGROUND
Business

Photography

AgX
Core-shell
particles

Competence

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Ink-Jet

DyeSynthesis

Imaging

InkFormulation

Webcoating

From Tree to Photo: Manufacturing

processes
Manufacturing steps

forestry

Pulp
& Paper
making

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Base Paper
making

Raw
materials

Dispersion
making

Ink

Coating
Solution
making

Front and
backing
layer
coating

Photo Prinitng

Photo
performance

Layer technology of IJ Photo Media

Disperison making and

Ink-jet media production process resembles photographic coating

process,
Coating solutions are made of metal oxide nanoparticle instead of
silver halide dispersions

Coating solution making

Curtain Coating
Ink Jet

Thickness of layers
dry
1 50
wet
10 500

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Two types of Ink-Jet receiving layers

Dry

Polymer

time
Polymer technology

Nanoporous

SiO2
time

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Nanoporous technology

Wet

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

Glossy Photo paper

Receiving layer

12
Size of particles in dispersion
dv50 16nm
all particles < 43 nm

10
Vol %

Silica/Alumina
PE

6
4
2

Paper support

0
0

10

20
30
40
Diameter of particles [nm]

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50

Ink up-take volume

coalescence

ink overload
2.50

Cr
Mg
Yb
Rg
Rb
Gr
Gb

2.00

Ink up-take speed

1 00

Br
Bg
K
3K

1. 5 0

80

4K
W

60

1. 0 0

40

0.50

20

0
0.00
0

10

20

30

40

50

60

70

80

90

10 0

-80

-60

-4 0

-2 0

20

40

60

80

- 20

OD, gamut

Film transparency

Dye adsorption
characteristics

- 40

- 60

bronzing
feathering

Other
properties
ozone fastness
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Nano Pigment Ink

Surface
Tension
Dynes/cm

Primary size
(nm)

Mean
Particle
Sizes (nm)

Pigment Ink

Typ

Magenta1
Magenta2

PR122
PR122

60

32
36

130
108

Cyan 1
Cyan 2
Yellow 1
Yellow 4

PB15:3
PB15:3
PY155
PY74

85
90
65

32
36
36
35

129
86
160
111

120

120

100

100

80

80
G

G
R

60

-80

-60

-40

40

20

20

-20

L=90
20

60

40

0
-100

0
40

60

80

100

-100

-80

-60

-40

-20

L=20
L=90
20

60

80

100

-20
L=70

L=70

L=60

L=60
C

40
L=80

L=80
-20

-40

L=50

L=40
L=30
L=20

-60

-40

Inkset 2
M2,C2,Y4 - Gamut Total 33,452
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L=40
L=30
-60
B

B
-80

L=50

-80

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

BET
m2/g63
97
48
130
50
47

Success factors

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New competences through collaboration

EIF
ILFORD Nanoporous Ink-Jet Technology
Collaboration with Prof. H. Hofmann (EPFL)

Ink-Jet

Dispersion making + Gas-fading

Collaboration with Prof. G. Furrer (ETHZ)

Investigation of gas-fading mechanisms

Collaboration with Prof. Rossi (EPFL), J.-N. Aebischer (EIF)

Energy

Li-Ion Battery Project

Collaboration with Profs. M. Grtzel & H. Hofmann (EPFL)

Nanoporous polymer layers

Optics
&
Imaging

Collaboration with M. Liley (CSEM)

Thin film security labels

Collaboration with Dr. A. Stuck (CSEM)

Thin film optics and imaging

Collaboration with Prof. L. Zuppiroli (EPFL)

And many more....

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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)

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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.

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Form Polymer to nano particle layer technology

60%

45
40

Nano

35

Traditionel

50%
40%

30
25

30%

20
15

Part of Nano products

20%

10

10%

5
0

0%

2002

2003

2004

2005

2006

60%
50%

% Forschung
% Produktion

40%
30%
20%
10%
0%
1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006

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Research cost and Sales

Risk Management

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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

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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

NO

Full risk assessment required

NO

Different particles may need to be

assessed separately

YES
Are the particles of a substance
whose toxicology is known
YES
Are particles homogeneous
YES
Are particles soluble in aqueous media

YES

Further assessment may not be

needed +

NO
Are particles less than 0.1um

NO

Existing exposure data may be

sufficient +

YES

Existing exposure data may be

sufficient +

YES
Does rapid coalescence with other particles
occur
NO

Are other chemicals adsorbed onto the particle YES

NO
Is the reactivity much greater than for larger
particles ot the same substance
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High priority for ADME studies by

relevant routes of exposure

YES
NO

Existing exposure data may be sufficient

Industrial Nanochemistry

Beispiel :
Dry powder

Source: www.cabot-corp.com

Density (uncompressed):

40 kg/m3
1000 kg

25

m3 = 25000 l

Big-bag
1 m3

25 big-bags
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Risk Management
Risk management

No standards about toxicity and ecotoxicity 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

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Avoiding risk in manipulation

Further progress

Silo-Technology

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Outlook

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Technology Transition: Imaging

Maturity of technology

The future potential of the technology in other fields than hardcopy

imaging.

Photography
Ink-Jet
new technology

about 150
years
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products

ca.20
years

today

time

Ilford competences

Polymer

Sol-Gel

Aqueous coating of
flexible hybrid films
Design & Synthesis
of organic dyes and
functional hybrid
nanoparticles

Nanoparticle
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Formulation
of soluble
&
pigmented
inks

The future

New generation of products

2D-Pattern (Ink-Jet)
luminescent
conductive
low index n
barrier layer
transparent base
adhesive layer

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

Economical
large area
multilayer coatings
of functional materials
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Thank you

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