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BU AdditivesTechnical Marketing WaxesMay 2013

Innovative products -sole carrier with universal applicationsWAXES FOR MASTERBATCHES

BU Additives, Technical Marketing Waxes, May 2013

Table of contents

Public, Sole carrier with universal applictions2

1. Mega trends and innovation in the masterbatch industry

2. Optimizing dispersion

3. Possibilities for highly filled concentrates

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Mega trends and innovation in the masterbatch industry


Mega trends in the masterbatch industry and related challenges


• Increased demand for color

• Less masterbatch dosage

• Requirements changed to- more economical processing due to high

energy and material costs (especially in Europe)

- high quality and best cost- performance

• Increasing complexity of formulations

• Service-orientated customer structure

• Increase of sustainable resources

• “Downsizing versatility”:

- smaller and multiple useable machines

• Innovations

• Improvements in existing products and technologies

• Fully compatible products: Higher loadings of active substances

• Working in clusters instead of big companies: “flotillas of speedboats” instead of aircraft carriers

• Networking up- and downstream the plastics chain- shorter delivery times, just-in-time- “ad hoc-solution” providers (the

early bird catches the worm)

Demands of the plastics industry… …lead to a broad range of needs:


Innovation as a big lever to meet challenges for the masterbatch production process…

Components

Carriere.g. polymer

Active substancee.g. pigment

Dispersingagente.g. waxes

Cold mixing- Universal mixer- Container mixer- Vortex/Fluidizingmixer

- Ultrasonic mixer

Hot mixing- Frictioning mixer- Kneader- Continuous mixer

Premix-processmain-feedingSingle / twin / multiple-screw

Split feed-processside-feedingSingle / twin-screw

Special-process- co-kneader - standard kneader - compactator

Strand pelletization− hot cut process− cold cut process− underwater − special process

Premix Compounding Granulation


Simplified process scheme


…with waxes increasingly filling the gap between classical dispersing agents and classical polymers


• ....at 20°C kneadable, solid to brittle

• …crystalline, opaque or transparent

• …melting above 40°C without decomposition

• …slightly above the melting point of low viscosity

• …heavily depending in appearance and consistency on the temperature

• …polishable under slight pressure

Source: Deutsche Gesellschaft für Fettwissenschaft(DGF-Einheitsmethode M-I 1 (75)

Waxes are…

• Some metallocene catalyzed polymerisatesare no real waxes.

• They are filling the gap between classical waxes and classical polymers

Montan waxes Licowax® E, OP

Licolub® WE 4, WE 40, WM 31

Licomont® CAV 102, NAV 101

Amide waxes Licowax® C micro, C pwd

Licolub® FA 1 vegetable based

PE/PP waxes Licowax® H 4, PE 130, PE 190, PE 520

Metallocenecatalyzedpolymerisates

Licocene® PP 1302, PP 1502, PP 1602, PP 2602, PP 3602 PP 6102, PP 6502, PP 7502PE 4201, PE 5301 modified Licocene (Si-, MAH-grafted Licocene)

Wax Oxydates Licowax® PED 521

Licolub® H 12

Polymer Oxydates

Licowax® PED 191

Micronized Waxes

Ceridust® 6050 M, 3620,5551, 3910

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Optimizing dispersion


Three main influences on dispersion: Theoretical operating mode

EDispersion = ∑ (Eextruder , Epremix , Eformulation)Eformulation = ∑ (Ecarrier , Eactive substance , Edispersing agent)

Public, Sole carrier with universal applictions

– each dispersion needs an individual demand of dispersion energy

– every pigment is showing a self-reliant characteristic of dispersion

– the characteristic of dispersion within the main pigment classes is nearly similar (more than 20 different chemical classes)

8


Epremix: By fine tuning the hot mix, smaller particles and optimized energy input can be achieved


- bigger particles- energy input slightly too high- critical temperature „run over“

- smaller particles- optimized energy input- critical temperature reached


Epremix: Optimized mixing parameters by fine tuning of the premix (hot mix)



Eextruder: Optimized screw configuration is key

11 Public, Sole carrier with universal applictions


Eformulation: Optimized amorphous carrier offers higher loading

Drop/Softening point vs. melt viscosity

50

70

90

110

130

150

170

1 10 100 1000 10000 100000

[mPa.s] (Measuring temp. PE: 140°C, PP: 170°C)

[°C

]

PE 130

PE 520

A-C 6

PP 6102

PP 1302

PP 2602

PP 1502 PP 1602

PP 7502

PP 6502

PP 3602


crystalline

amorphous

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Possibilities for highly filled concentrates


Licocene: Unique, amorphous, low melting and high molecular weight Licocene grades

Advantages

– Full FDA and EU compliance of all Licocene PP grades

– Universal carrier assuring high compatibility with Polyolefin, TPOs, etc.

– Improved production quality at reduced costs

– Simplified inventory management

– Saving of energy due to low melting point and short mixing time = reduction of cycle time


Properties

The unique, amorphous, low melting and high molecular weight Licocene grades

- Licocene PP 3602, PP 2602, PP 1602 and Licocene PP 1502

can be used as a carrier for various masterbatch application

in combination with the crystalline Licocene PP 6102 as a dispersing agent


Licocene: Unlimited possibilities for highly filled concentrates

Carbon black with 50% loading

Inorganic pigment with 75% loading

Effect pigment with 80% loading

Organic pigments with 50% loading

Blowing agents with 70% loading

Antistatic agent with 85% loading

Light stabilizers with 70% loading


with Licocene PP 1502, Licocene PP 2602, Licocene PP 3602 as carrier

and Licocene PP 6102, Ceridust 6050 M as dispersing agent.

1

2

3

4

5

6

7

Examples:


Highly filled carbon black pigment masterbatcheswith 50 % loading


1

Masterbatch for Polypropylene (50% Carbon Black- various grades)

0.0

0.1

0.2

0.3

0.4

0.5

50% BP 800 +Licocene

PP6102 andLicocene PP 2602

50% L 46 +Licocene


50% BP 45 +Licocene



PP6102 andLicocene

PP 26



Filte

r pre

ssur

eva

lue

[bar

/g] D

IN E

N 1

3900

-5


Highly filled inorganic pigment masterbatcheswith 75% loading

– Recipe:

- 75 % Pigment Brown 29 (e.g. Sicopal Brown 2795)

- 25 % Licocene PP 2602 granules

– Processing on Ø 26 mm, 44 D twin screw extruder


3

300 rpm, 10 kg/h Main feeder (cold mix)1 2 3 4 5 6 7 8 9 10 11 12

45°C 90°C 230°C 250°C 200°C 170°C 130°C 130°C 110°C 110°C 110°C

17

2


Highly filled effect pigment masterbatches with 80% loading

– Lumilux® After-glowing pigments- average particle size 30 µm- shear sensitive

– Recipe- 80 % Lumilux® pigment- 20 % Licocene PP 1502

– Processing on 26 mm, 44 D twin screw extruder


1 2 3 4 5 6 7 8 9 10 11 12Main feeder (cold mix) 150 rpm, 8 kg/h

45°C 90°C 160°C 140°C 140°C 140°C 140°C 100°C 90°C 90°C 90°C

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3


Highly filled organic pigment masterbatches with 50% loading


4Fi

lter p

ress

ure

valu

e in

[b

ar/g

]

Rel

. col

or y

ield

in [%

]

9095100105110115120

0,00,51,01,52,02,53,0

Single Pigment Concentrate (SPC) of Graphtol® Yellow GR (50%)

Hot mix

LLDPE 35%

Licowax PE 520 15%

Licocene PP 6102 10%

Ceridust 6050 M 10%

Licocene PP 1502 40% 40%

filter value: DIN-EN 13900-5


Highly filled organic pigment masterbatch with 50% loading…


Picture: Leistritz, Masterbatch Workshop

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4

Colorbatch 50 % P.B. 15:1 and 50 % Licocene® (PP 1502 & PP 6102)


….with very low filter pressure and improved color yieldFilm note: 50% Pigment Blue 15:1 + 50% Licocene® (PP 1502; 2602; 6102)

FPV

in [b

ar/g

]

premix: hot mixing

rel.

colo

r yie

ld in

[%]

filter value: DIN-EN 13900-5filter: screen pack 2 color yield: DIN 55986

90

92

94

96

98

100

102

104

106

108

110

0,0

0,2

0,4

0,6

0,8

1,0

1,2

1,4

1,6

1,8

2,0

35% PP1502 + 15% PP6102 35% PP2602 + 15% PP6102


VN 102490-491

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0

0,5

1

1,5

2

2,5

0,0

0,2

0,4

0,6

0,8

1,0

1,2

1,4

1,6

1,8

2,0

35% PP1502 + 15% PP6102 35% PP2602 + 15% PP6102

FPV

in [b

ar/g

]

film

not

e

Relative color yield: 50% Pigment Blue 15:1 + 50% Licocene® (PP 1502; 2602; 6102)

filter value: DIN-EN 13900-5filter: screen pack 2 premix: hot mixing film note: Clariant norm

…excellent film note


VN 102490-491

22


…as well as outstanding strand elasticity

50 % organic pigment (P.B. 15:1) in Licocene® carrier resin



0

0,5

1

1,5

2

2,5

3

0,0

0,5

1,0

1,5

2,0

35% PP1502 +15% PP6102

35% PP1502 +15% PP6102

35% PP1502 +15% PP6102

(PR 122) PV-Echtrosa E (PY 155) PV-Echtgelb (PV 23) PV-Echtviolett

50% loading with different organic pigmentsFP

V in

[bar

/g]

film

not

e

FPV: DIN-EN 13900-5filter: screen pack 2 premix: hot mixing film note: Clariant norm

Quinacridone Diazo-condensation Dioxazine


VN 102089-095

24

4


Amorphous carrier allows low processing temperatures for reactive blowing agent

– Hydrocerol® (chemical foaming and nucleating agents)

– critical temperature: > 125°C

– Recipe

- 70 % Blowing agent

- 20 % Licocene PP 2602 granule

- 10 % Licocene PP 1502 fine grain


250 rpm, 7 kg/h

50°C 60°C 60°C 60°C 70°C 70°C 70°C 70°C 80°C 45°C

25

5


…and again outstanding strand elasticity

..70% blowing agent in Licocene® carrier resin



High loading with 85% GMS possible

– Recipe Processing on Ø 27 mm, 44 D twin screw extruder200 rpm & 8 kg/h (limitation through liquid pump)

- 85 % Hostastat FE 2 (GMS)



50 °C 50° 50 40 40 40 40 50 90 120 160 220 90 45 °C

Underwater-pelletizer

closedclosed

Degasing area

Dosing of the additive here

Licocene carrier

27

6


High loading with 70% light stabilizer

– Recipe Processing on Ø 27 mm, 44 D twin screw extruder 250 rpm & 8 kg/h (only processability test)

- 70 % Hostavin®* N 30 + Hostavin®* ARO 8 (2:1)



50 °C 50° 50 40 40 40 40 50 90 120 160 220 90 45 °C

Underwater-pelletizer

closedclosed

Degasing area

Dosing of the additive here

Licocene carrier

28

7


Summary: Innovative products - sole carrier with universal applications


• Higher molecular weight Licocene grades are suitable carrier materials for all kind of pigments, fillers and additives

• Due to the molecular structure, Licocene provides– outstanding capability of filler wetting – thermoplastic extrusion processing, – underwater pelletizing (recommended)– compatibility to polyethylene and polypropylene

• Applications can be:– carrier for highly loaded masterbatches – carrier for temperature sensitive active substances – carrier for effect pigments

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Back-Up

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Back-Up: Theory of manufacturing of masterbatches


PE/PP Waxes

– Raw material: Ethylene or Propylene

– Production: Low pressure Ziegler polymerization

Metallocene catalyzed polymerization

– Product characteristics: Non oxidized white substances based on PE or PP

- Drop/Softening point between: 120 °C to 130 °C (PE) and 90 °C to 165 °C (PP)

- Viscosity between: 60 mPa*s to ~ 9300 mPa*s (@ 140/170°C)

- Available in granules and powders



Theory - Improved pigment dispersion

Determinant propertiesProcessing step

Polarity Compatibility Viscosity

Stabilization

Drop point Viscosity Polarity

Pigment wetting(dispersing agent )

surplus of dispersing agent (e.g. wax) is beneficial

Viscosity Thermal and

Color Stability

Dispersion

prevention of flocculation



Theory - Improved pigment dispersionTheoretical operating mode

Fine dispersion of pigments is a function of :

- particle size distribution f (pigment, machinery, influx of energy, time)

- geometry and form of the f (pigment, method of processing, influx of particles / agglomerates energy, time)

- specific surface area f (pigment, method of processing)

- surface charge / polarity f (pigment, additives)

- rheology f (additive, pigment, polymer, parameter: pTv)

- compatibility f (pigment, polymer, additive, dispersing agent)



Pigment wetting


Wax / Polymer

Pigment(agglomerated)

+

• Capillary forces• Particle and

agglomerate size• Particle size distribution• Surface tension• Polarity

• Viscosity• Polarity

wetting

no wetting

completepenetration

only outsidewetting

› weakening of agglomerate cohesion

› stabilisation of primaryparts

» optimum dispersibility

› no weakening of agglomerate cohesion

› partly stabilisation ofprimary parts

» improved dispersibility

› no effect on agglomerate cohesion› no stabilisation»phase separation and chalking»no improvement of dispersibility

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100

102.5

105

107.5

110

112.5

115

117.5

120

0% 5% 10% 20% 30%

content of wax

colo

ur y

ield

in [%

]

0

0.5

1

1.5

2

2.5

3

3.5

4

filte

r pre

ssur

e va

lue

in (F

PV) i

n[b

ar/g

]

Influence of wax content on pigment dispersion - Theoretical scheme -


colour yield

filter pressure value

relation between color yield in [%] and filter pressure value in [bar/g] referring to the content of wax in [%]

36

BU Additives, Technical Marketing Waxes, May 2013Public, Sole carrier with universal applictions37

Examples of fine tuning possibilities via screw configuration


Licocene® as carrier – temperature profile Colorbatch 50 % P.B. 15:1 and 50 % Licocene®


VN

Feed zone T1 T2 T3 T4 T5 T6 T7 T8 T9

NozzleT 10

102490 90 140 150 120 100 100 120 120 120 130

102491 90 140 150 120 100 100 120 120 120 130

102495 90 140 150 120 100 100 120 120 120 130

102496 90 140 150 120 100 100 120 120 120 130

102779 120 145 145 160 160 165 165 170 170 170

102780 120 145 145 160 160 165 165 170 170 170

102782 120 145 145 160 160 165 165 170 170 170

Extruder temperature profile:

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Back-Up: Ceridust used as dispersing agents


Determination and comparison of pigment-dispersion-quality:- determination of the relative color yield (DIN 55986 ff)

- reduction in screen filter blockage / filter pressure value (DIN EN 13900-5)

- determination of specks, spots and surface irregularitiesat the final article (e.g. blown film) (internal standard)

Ceridust® and Licocene®

- New products - Meet your demands

the reduction of agglomerates of pigments within the master-batch is one key factor in order to get a fine dispersion


BU Additives, Technical Marketing Waxes, May 2013Public, Sole carrier with universal applictions

Influence of particle size and amount of wax30% Cu-Phthalocyanine in LLDPE

0

2

4

6

8

10

12

14

16

18

without wax 10% LicowaxPE 520

15% LicowaxPE 520

20% LicowaxPE 520

15% PE 520 +Ceridust 3620

(2:1)


(2:1)

filte

r pre

ssur

e va

lue

[bar

/g]

VN 86931 - 86941

filter value: DIN-EN 13900-5filter: 40 µm, 725 mesh premix: cold mixing

decrease of filter pressure value (FPV) due to finer particle size and higher amount of wax

30% Pigment Blue 15:1 + (50% + xwax) LLDPE (MFI 25) + xwax %

41


VN 86196- 86203

90

95

100

105

110

115

120

125

130

135

140

0

2

4

6

8

10

12

14

without wax 20% LicowaxPE 520

30% LicowaxPE 520


(2:1)


(2:1)

rel.

Col

or y

ield

in [%

]

Filte

r val

ue (F

PV) i

n [b

ar/g

]

40% P. Red 57:1 + 30% + xwax) LLDPE (MFR 25) + xwax %

filter value: DIN-EN 13900-5filter: 25 µm premix: cold mix color yield: DIN 55986

Influence of Ceridust® 3620 in LLDPE


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