Novel bio-based polymeric dispersants

for inkjet applications

Dr. Francisco Rodríguez

R&D Chemical Team Leader
UBE Corporation Europe, S. A. U.

Nuremberg, March 27th, 2023

Dispersants in the production of inks
Dispersant

Pigment

Wetting Dispersing Stabilization

Grinding

Steric repulsion Electrostatic repulsion

2
States of the suspension

Enough stabilization / Stable suspensions

4 4
𝑘𝑘𝑘𝑘 ≫ 𝜋𝜋 𝑅𝑅 3 Δ𝜌𝜌 𝑔𝑔 ℎ 𝑘𝑘𝑘𝑘 ≪ 𝜋𝜋 𝑅𝑅 3 Δ𝜌𝜌 𝑔𝑔 ℎ
3 3

Stable colloidal suspension Stable coarse suspension Stable coarse suspension

(uniform size) (size distribution)
3
States of the suspension

Low stabilization / Unstable suspensions

Coagulated suspension Coagulated suspension Coagulated suspension

(chain aggregates) (chain aggregates) (open structure)
4
States of the suspension

Flocculated suspensions

Weakly flocculated structure Bridging flocculation Depletion flocculation

5
Dispersant dosage

Why it is so important?

Defect of dispersant Correct formulation Excess of dispersant

Limited steric repulsion Maximum steric repulsion Collapsed stabilizing chains
Possibility of reagglomeration Minimum viscosity Dispersant in solution 6
UBEDISP® Dispersants portfolio

Aliphatic Water
E100 Series
AW Series

100 % Active content

PW
Series
Suitable for inorganic particles in organic systems Organic
particles

Non dangerous
Ester Alcohol

Bio-based USDA Certification from 95 % to 85 %

Inorganic particles

UV Curing

7
Types of dispersants

Dispersants Dispersants
of of
Low Molecular Weight High Molecular Weight

Fragment with high affinity

for the particle to disperse

E100 Series
Compatible fragment
with the dispersing vehicle

Limited performance Maximum performance

8
Design of UBEDISP® E100 Dispersants
Graft copolymers as dispersants

Anchoring groups
Anchoring polymer Density
Distribution
High affinity for the pigment Molecular weight
Type of polymer

O
O

O
C
OH HO

δ- -
δ+ Mx+δ δ+
δ+ O2- O2- δ+
H δ- Mx+ O2- Mx+ δ-
N
H δ+ O2- x+ O2- δ+
M
δ- + δ-
δ δ- δ+
O Cl
Cl C
O S OH Si l

9
Design of UBEDISP® E100 dispersants
Graft copolymers as dispersants

Polarity of polymer
Stabilizing polymer Length
Flexibility
High compatibility with the vehicle
Branching

Correct formulation
Minimum viscosity
Maximum steric repulsion
Maximum stability
Maximum performance

Incompatibility Compatibility Perfect match

Phase separation Good solubility Maximum steric repulsion
Lack of stabilization Acceptable stabilization Minimum viscosity 10
Design of UBEDISP® E100 dispersants
Graft copolymers as dispersants

Polarity of polymer
Stabilizing polymer Length
Flexibility
High compatibility with the vehicle
Branching

Dispersant/media Aliphatic Fatty acid Tripropylene glycol Methyl ethyl Dipropylene

Ethanol
compatibility hydrocarbon esters n-butyl ether ketone glycol diacrylate

UBEDISP® E101

UBEDISP® E102

UBEDISP® E103

UBEDISP® E1004D

11
Example of applications of UBEDISP®

Polyurethane coatings

Ceramic inkjet inks Conductive inkjet inks

LED inkjet inks

Acrylic coatings Alkyd coatings

Adhesives with inorganic fillers 12

Ceramic inkjet ink production

Pigment paste formulation Pigment dispersion Ceramic ink

+ Vehicle 1

+ Vehicle 2

Apolar vehicle (5-10 cPs) D90 < 0.6 μm D90 < 0.6 μm

Ceramic pigment (D90~5μm) Viscosity (10-100 cPs) Viscosity = 28 cPs

Dispersant

13
 UBEDISP ®

E101 E102 E103

Excellent Excellent
anti-settling properties viscosity reduction
Dispersing and milling procedure

Mill base formulation

Disperser with
cowless blade

2-Ethylhexyl laurate

60 % Praseodymium yellow pigment

0.5 to 4 % UBEDISP®

Dispersion procedure

1st Dispersant
2nd Vehicle + 20 min at 1500 rpm
3rd Pigment addition pigment
4th Dispersion at 1500 rpm x 20 min or until constant PSD
15
Milling performance
Optimal dispersant concentration (I)

3,0
3,5% E101
2,5% E101
2,5 1,5% E101
0,5% E101

2,0

d50 (μm)
1,5

1,0

0,5
Target:
d50=0.45 µm
Milling conditions
0,0
LabStar Netzsch
0 5 10 15 20 25 30 35 40 45 50 55 60 65
Zbeads 0.3 mm
3300 rpm time (min)
2 kg of pigment paste
Target d50 = 0.45 ± 0.02 µm
16
Milling performance
Optimal dispersant concentration (II)

100

90

80
E101

Mill base viscosity (cPs)

70

60
E102
50

40

30 E103
20

10
Milling conditions
0
LabStar Netzsch
0,0 0,5 1,0 1,5 2,0 2,5 3,0 3,5 4,0 4,5 5,0
Zbeads 0.3 mm
3300 rpm % Dispersant in mill base
2 kg of pigment paste
Target d50 = 0.45 ± 0.02 µm
17
Ink performance
Suspension stability with UBEDISP®

60
Initial After* E101 E102 E103
Viscosity at 5,6 s-1 (cPs, at 25 ºC)

50

40

30

20

10

0
4,0 3,0 2,0 1,0
% Dispersant

Yellow inks were adjusted at 45 % solid content and a viscosity of 28 ± 1 cPs at 25 ºC

18
*2 weeks at 50 ºC and ink recovery with disperser (20 min, 1400 rpm)
Characterization of mill base/ink
Filtration tests
Time that 15 mL of ink can pass through a microfiber filter (1µm)
Study in triplicate
T = 25 ºC and P = - 900 mbar

19
Ink performance
Filterability with UBEDISP®

900

800

700
Filtration time (t2, s)

E101
600

500

400 E102
300

200

100
E103
0
0,0 0,5 1,0 1,5 2,0 2,5 3,0 3,5 4,0 4,5 5,0
% Dispersant

20
*Yellow inks adjusted at 45 % solid content and a viscosity of 28 ± 1 cPs at 25 ºC
Characterization of mill base/ink
Sedimentation studies
Accelerated sedimentation studies by temperature
100 g of ink 14 days at 50 ºC

~ 1 % Soft sediment ~ 8 % Hard sediment

21
Ink performance
Sedimentation with UBEDISP® after 2 weeks at 50 ºC

18
Hard Medium Soft
16

14
E103
12 E102
% Sediment

10

8
E101
6

0
0,0 0,5 1,0 1,5 2,0 2,5 3,0 3,5 4,0 4,5 5,0
% Dispersant

22
Yellow inks adjusted at 45 % solid content and a viscosity of 28 ± 1 cPs at 25 ºC
Milling performance with different pigments

Apparent density Initial PSD Target PSD

Color Structure
(g/mL) d50 (µm) d50 (µm)
BLACK Co-Mg-Fe-Cr 5,4 2,01 0,45
BEIGE Zn-Fe-Cr 4,0 2,05 0,42
BLUE Co-Al-Zn 2,2 2,14 0,40
PINK Ca-Sn-Si-Cr 3,4 2,58 0,49
YELLOW Zr-Si-Pr 3,2 6,51 0,40

Milling conditions Formulation

LabStar Netzsch 38 %
Zbeads 0.3 mm
3300 rpm
2 kg of mill base 60 %
Duplicate
2%

23
Milling performance with different pigments

Apparent density Initial PSD Target PSD

Color Structure
(g/mL) d50 (µm) d50 (µm)
BLACK Co-Mg-Fe-Cr 5,4 2,01 0,45
BEIGE Zn-Fe-Cr 4,0 2,05 0,42
BLUE Co-Al-Zn 2,2 2,14 0,40
PINK Ca-Sn-Si-Cr 3,4 2,58 0,49
YELLOW Zr-Si-Pr 3,2 6,51 0,40

80
80
70
70

Mill Base Viscosity (cPs)

Milling time (min)

60 60
50 50
40 40
30 30
20 20
10 10
0 0
E101 E102 E103 E101 E102 E103
(6b63-N2) (1b69-N2) (1c55-N2s) (6b63-N2) (1b69-N2) (1c55-N2s) 24
 Ink performance with different pigments
Sedimentation with UBEDISP® after 2 weeks at 50 ºC

35
Hard Medium Soft
30

25
Sediment (%)

20

15

10

0
E101 E102 E103
(6b63-N2) (1b69-N2) (1c55-N2s)

Inks adjusted at 45 % solid content, 2 % of dispersant and a viscosity of 22 ± 1 cPs at 25 ºC.

25
UBEDISP® E100 Series

Milling efficiency
(time)
E101
Milling efficiency
Water compatibility
(consumption)

Ink durability
Low viscosity in
against thermal
E102 pigment dispersion
degradation

Filterability of
Sediment properties
pigment dispersion
E103 Final ink
Filterability of final
sedimentation
ink
stability
UBEDISP® E100 Series
Main features

- Non dangerous and bio-based (>90 %).

- 100 % active content hyperdispersants.

- Highly selective with a broad range of inorganic particles and long term stability.

- Compatible between them and with the different organic systems.

- High viscosity reduction and anti-setting properties.

- Fine tuning of final ink performance can be easy achieved using UBEDISP® E100.

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 Thank you for your attention!!!

Willing to improve the performance of your dispersions?

Wanting to learn more about UBEDISP® hyperdispersants?

✅ Come over our booth 1-124

✅ Visit our webpage www.ube.es
✅ Write me an e-mail to [email protected]