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Synthetic Papers based on

Biaxially Oriented Films


Brückner Maschinenbau GmbH, Siegsdorf, Germany
Dr. J. Breil, Dr. M. Wolf, J. Sänze

19. Leobener Kunststoff-


Kunststoff-Kolloquium, 16. & 17.11.2006
Überblick:
 1) Einleitung

 2) Definition Synthetisches Papier „Syn Pa“

 3) Verfahren zur Produktion biaxial orientierter Folien –


Vergleich simultanes/ sequentielles Verfahren

 4) Dichtereduktion durch den Verstreckungsprozess

 5) Beispiele experimenteller synthetischer Papiere


 Basis Polypropylen, dichtereduziert, mehrlagig
 Basis Blends, z. B. PET/ PP oder PA6/PP, dichtereduziert
 Geschäumte Systeme
 7-Lagen Barrierefolien

 6) Zusammenfassung und Ausblick

© Brückner
1) Introduction: Requirements to film packagings

Advertising
• Optics
• Printability
- brand name
- attractivity

Protection Environment-
friendly
• Mechanical
• Water vapour • Production
• Gas ( O2, CO2, …) Processing
• Light
• Minimization of
• Aroma,taste
material requirement
• Seal integrity
• Disposal

Econimcs
• Cost effective
production
• Suitability for fast
packaging machines

© Brückner
Improvement of properties by a stretching process
3500
CPP
BOPP 500 500 90

70

4 850
10
250 1500

560
160 160
1,5 5

60 200
50 100
30

MD TD MD TD H2O O2 CO2 N2
tensile - Elongation Haze Gloss
at break g 25µm cm³ 25µm
strength [%] [%]
[N/mm²] [%] m² d m² d bar

Mechanical properties Optical properties Barrier properties © Brückner


Share of thermoplastics for oriented films
Production capacity 2002 worldwide

PVC
PA Raw- 1000 %
Others
Others material t/a Share
PS

PP 4.970 66,0
PET
PET 1.780 23,6

PS 480 6,4

PVC 100 1,3


PA 120 1,6
PP
Others
Others 80 1,1
Sum 7.530 100,0

© Brückner
Classification of BOPP application areas

Market- Growth
share
Standard products:
Biscuit & cookies 31% 5%
Chips & Snacks 15% 7%
Candies 10% 6%
Noodles 8% 3%
Others 19%
Special products:
Labels 8% 8%
Ice cream 5% 10%
Others (new) 4%

Worldwide BOPP production capacity 2002: 4,97 Mio. t/a


Worldwide BOPP SYN PA production capacity 2002: ?????? t/a
© Brückner
2) A Definition of Synthetic Paper

 SYN PA is a film produced by extrusion:

 which contains high amounts of fillers/ pigments


 with a white opaque, paperlike appearance
 with high stiffness, good slip and antistatic properties
 with microscopic vacuoles and/or foam structures
 which is printable and writeable
 with three- or morelayered film structures possible
 offering all attributes of traditional cellulosic paper
 Restriction to biaxially stretched film, e.g. based on
Polypropylene as film forming polymer (Paper production
by using synthetic fibers shall not be discussed here)

There is not only one form of „SYN PA film“


© Brückner
Thickness Ranges and typical Applications

Thickness [µm] Recommended Applications

Pressure sensitive, cut and stack, and wrap-around labels; release


50-180 µm
liners, posters ink jet printing base

75-100 µm Pressure sensitive, wrap-around and in-mold labels

Cut and stack and wrap around labels, posters, maps, shopping bags,
75-200 µm
business cards, calendars, banners

75-250 µm Labels, books, posters, calendars

Maps, posters, tags, cards, charts, menus, phone cards, calendars,


75-400 µm
banners

130-700 µm Carriers, files, folders

250-1000 µm Cards, tags, book covers, folders, charts, maps

© Brückner
Synthetic Paper

© Brückner
Advantages of Synthetic Paper

Advantages

 Higher wet strength


 Higher dimension stability in wet condition
 Higher folding strength
 Low density
 Low anisotropy
 Higher tear resistance
 Heat-sealable, thermoformable
 Low surface roughness
 Flexible techniques for production
 Non-sensitivity against humidity, oil, fat, greases
 Good Barrier Properties against water vapour and gases
 Low waste water and air pollution in production
© Brückner
About the history of SYNPA-production:

 End of 60s and beginning of 70s the development of SYNPA started


 SYN PA production was thought to be less expensive
 especially in Japan and Great Britain because of rare timber existence

Between 1980 and 1995 the market share of SYNPA is <2%,


in the light of a constant fall in prices for conventional papers
Price for a coated, high grade cellulosic paper: ~1.600-1.700 €/ t
Price for a single side coated 75µm SYNPA : ~4.000 €/ t
Usually für SYNPA: Price in €/ m2
Today SYNPA is used for high price special applications

Basic patents are free  it is not to be expected, that anyone will


succeed in exclusively securing patent rights in the field of synthetic
paper (Basic patents between 1960 and 1970, until 2002 110 patents
in the field of SYN PA, mainly NANYA and Oji-Yuka)
© Brückner
© BRÜCKNER
Synthetic Paper Products and Players
Company Trade Name Resin Comments
American Profol Propaper PP 3-layer cast film
Arjobex Polyart HDPE Clay-coated on both sides, oriented
B&F Plastics Polyprint Polyester Talc (20%)
Cosmo Films Ltd. CMP III PP BOPP uncoated
ExxonMobil Films Label-Lyte PP BOPP clay-coated, corona treated
Flexcon AlphaMax Labels
Grafix Plastics GrafixPro Polyolefin
Granwell Polylith PP TiO2, CaCO3, monolayer
Harrier Paperfeel HDPE 3-layer coex
Hop Industries Hopsyn PP Calendered Film from Nan Ya

Mile High Eng Accuplot Outdoor posters, semi-gloss finish, needs pigment
Denver, CO inks to keep water proofing
NanYa Plastics Dura-Lite PP 3-layer with clay coating

Plastics Suppliers Duraflex BOPS Versatile Polyolefin


Polyflex BOPS
V-Max
Policrom SCO-PAT BOPP, Polyester
PPG Teslin PE Microporous film, silica-filled, single-layer (HiSil),
uncoated
A Schulmann Papermatch HDPE Fully compounded or in concentrates
Toyobo Crisper Opaque
Transilwrap Proprint PP Talc-filled
Van Leer Valeron Cross laminated
Yupo Corp Yupo BOPP Coated and Uncoated © Brückner
Synthetic Paper Market by Resin, 2000 – 2005

50
45
40 2000 2005
35
30
[tpa]

25
20
15
10
5
0
BOPP HDPE others

© Brückner
Production Capacity SynPa Worldwide

Country Company Line Capacity Production Domestic Export Comment


Rate
North Yupo U.S.A. 1 10000 9500 6000 3500 U.S.A. 60%, EU: 40%
America Arjobex 2 7000 6000 6000 HDPE
Mobil 4 Label
Europe Arjobex 2 7000 5000 5000
Mobil 3
Taiwan NanYa 2 50000 24500 5400 19100

Japan Yupo Co. 3 28000 19000 16000 3000


Chisso 1 2400

Others Shorko 1 Australia


Cosmo Film 1 India

© Brückner
Synthetic Paper Lines from Brückner

Customer Year of Country Capacity


Start-Up [ tpa ]
Arjobex 1988 UK 3000
Arjobex 1991 USA 3000

Nan Ya 1998 Taiwan 25000

Nan Ya 2001 Taiwan 25000

Nan Ya 2003 Taiwan 31500

Nan Ya 2003 Taiwan 31500

Nan Ya 2005 China 31500

Nan Ya 2005 China 31500

Nan Ya 2005 Vietnam 31500

© Brückner
Layer Structures of Synthetic Paper, examples

Single Layer Comprises:


60,0 % Polypropylene
25,0 % CaCO3
7,0 % TiO2
8,0 % PP-wax

Two / Three Layer Comprises: Core Layer:


77,5 % Polypropylene
15,0 % CaCO3
2,5 % TiO2
5,0 % MSA-PP wax MSA-PP wax:
 Better binding of the pigments
 Better bonding of the layers
Skin Layer (2-3 µm):
57,0 % Polypropylene
27,5 % CaCO3
7,5 % TiO2
0,5 % MSA-PP wax PP-wax:
7,5 % PP-wax  Viscosity reduction
 Surface coating
 Wetting and embedding of the
pigment particles

© Brückner
Film Sample: 80µm 5-layer white opaque film – pearlized - heatsealable
A: 1,0 µm Terpolymer / Slip + Antiblock MB
B: 1,0 µm Homopolymer + slip/antistatic MB
C: 74,0 µm Homopolymer + White MB + Pearlized MB
D: 2,0 µm Homopolymer + White + Antistatic MB
E: 2,0 µm Terpolymer / Slip + Antiblock MB

Film Test Results:


Applications:
No Description Unit Average Method • Name cards
1 Thickness -TD µm 80 DIN 53370 • Menus
-MD N/mm² 104 DIN 53455 • Biscuits
2 Tensile Strength
-TD N/mm² 171 DIN 53455 • Labels
-MD % 135 DIN 53455 • Leaflets
3 Elongation at Break
-TD % 34 DIN 53455 • Sheets for advertisement
Modulus of -MD N/mm² 1534 DIN 53457 • Calendars
4
Elasticity -TD N/mm² 2744 DIN 53457 • Lamination to aluminum
Coefficient of F/F- T/O - µs — 0,21 DIN 53375 • 2 Sheet lamination
5
Friction F/F- T/O - µk — 0,2 DIN 53375 • Labels for Bottles and Boxes
6 Haze % — ASTM 1003 Film Requirements:
• High Opacity
7 Gloss — 89 / 86 ASTM 2457 • High Yield due to low density
8 Opacity % 91 DIN 53146 • High surface treatment for good
-MD % 3,9 BMS TT 02 printability
9 Thermal Shrinkage • Reasonable slip properties
-TD % 2 BMS TT 02
• Reasonable antistatic properties
10 Density g/cm³ 0,68 ASTM 1501

11 Wetting Tension mN/m 42 ASTM 2587 © Brückner


Base Raw Materials for the Core and Intermediate Layers (Examples)

Homopolymer BOPP Grade or special grades, eg. high cryst.


Calcium Carbonate CaCO3 or other mineral fillers
Additives, e.g. Slip, Antistatics, compatibilizers, HC resins
PP in Mixture with other Polyolefins, e.g. PE or thermoplastics
like PA6, PBT, PET

Base Raw Materials for the Skin Layers (Examples)

Homopolymer BOPP Grade or


Copolymer BOPP Grade for sealing applications
TiO2, CaCO3 or other mineral fillers
PP in Mixture with other Polyolefins,
e.g. PE or thermoplastics like PA6
© Brückner
Example Formulations and purposes of the different layers

Formulation Purpose
 Increase in stiffness
1. PP with anorganic fillers
 Opacity
Core layer
 Density reduction of the
2. Chemically foamed PP-layer
stretched film

Intermediate 1. High crystallinity PP  Increase in stiffness


layer
2. PP / PA - blends  Increase in opacity
 Paperlike haptic
1. PP with anorganic fillers – high  Surface roughness
content  Printable
Skin layer
 Coatable
 Gloss
2. Pure homo- or copolymer
 Coatable

© Brückner
Increasing possibilities by using 5-layer Technology

 Excellent white film with high gloss: Film density and opacity are
functions of film thickness, orientation filler contents and type of
fillers. Five layer structures offer a broad spectrum in terms of film
density, gloss, opacity, whiteness and heatsealability.With three
layer strucure it is not possible to get:
 for non heatsealable film:
 High gloss, high opacity and low density
 for heatsealable film:
 High density, high opacity and high gloss
 Worst Combination: High gloss, high opacity and low density

 Cost savings due to lower additivation


 An increased percentage of recycled material can be processed
 Three- and five layer film with the same equipment

© Brückner
Concept of a Synthetic Paper Line

• Machine design for high output in thick film up to 200


µm
• Twin screw extrusion with direct additivation
technique
• All coextruders twin screw extruders
• 5-layer die design recommended

BR/BHP miami/!s_dtp/bhp/folien/Folien/SynPa Extrusion © BRÜCKNER


© Brückner
5-Layer Coextrusion System with Twin Screw

Output: 2400 kg/h+4 x 190kg/h

BR/BHP miami/!s_dtp/bhp/folien/Folien/5-Layer CoEx © BRÜCKNER


© Brückner
Extrusion
Main Extruder
• Co-rotating twin screw extruder
• Direct powder feeding (Brückner patent)
• Screw for optimum mixing of powder and PP in
agglomerate free quality
• Moisture and volatiles removal by vacuum (no
drying necessary)
• Controlled melt temperature

Coextruder
• Twin screw extruders for all coextruders
• Screw for excellent melt quality
• Improved optical properties by moisture and
volatiles vacuum removal
• No predrying of moisture sensitive additives
• Controlled melt temperature

VOB/ET miami/!s_dtp/bhp/folien/Folien/SynPa Extrusion © Brückner


© BRÜCKNER
3) Processes for the production of biaxially oriented films

Sequential Stretching Simultaneous Stretching


MDO - TDO Pentagraph, Spindle, LISIM Double-Bubble

© Brückner
LISIM® Principle
Linearmotor Simultaneous Stretching technology

Clips

Linear motors

Simultaneous stretched film

Cast-film
© Brückner
Comparison Sequential / Simultaneous Stretching Processes

Sequential Stretching Simultaneous Stretching


TD
10 10
9 9
8 8 MD
7 MD 7
TD
6 6
5 5 Useful area
4 4
3 3
Useful area
2 2
1 1

MDO TDO LISIM® Simultaneous stretch. technology


© Brückner
Comparison of mechanical film properties:
Sequential / Simultaneous

Sequential LISIM®

Stretching ratio
5x9 8x8 10 x 5
(MD x TD)

Tensile- MD 140 258 310


strength
[N/mm²] TD 290 252 208

MD 200 78 52
Elongation at
break [%]
TD 55 82 110

MD 2000 3060 4070


E-modulus
[N/mm²]
TD 3500 3130 2685
© Brückner
Selected current BOPP-trends:

 Low and very low sealing copolymers (SIT down to 80°C).


 More layer film structures, e.g. 7-Layer barrierfilms with
EVOH as barrier material.

 Development of copolymers for higher barrier values of metallized films

 Printable Cigarette film.

 Development of high speed resins.

 Material savings by thickness- and density reduction:

 Formation of vacuoles by adding matrix incompatible organic or


anorganic fillers (CaCO3, PBT).

 Use of chemical foaming agents and subsequent simultaneous


stretching.

© Brückner
4) Density reduction: Formation of vacuoles by incompatible additives
(Inorganic, organic e. g. PBT, -PP)

Y Vacuole
Z
Particle

Polymer matrix Side view


Top view

Sequential und simultaneous


© Brückner
Parameters influencing the Cavitation

Influence of CaCO3 Content


Influence of MDO Stretching Ratio

Influence of MDO Temperature Influence of TDO Stretching Ratio

© Brückner
BOPP SYN PA Density as a function of the filler´s nature

BOPP-SYN PA
Density [g/cm3]

0.79

0.69

0.57

Talcum CaCO3 TiO2 15% filler


© Brückner
© Brückner
Stearic Acid as a wetting agent for hydrophobisation of
CaCO3 during the extrusion process

70 °C ~ 245 °C

+ T °C

CaCO3 + Stearic Acid Ca-Stearate + H2O +


CO2
A wide range of CaCO3 types with and without surface treatment
was available for our work
© BRÜCKNER
© Brückner
Laboratory trials with precipitated CaCO3 fillers (Company Solvay):

PCC properties, controlled by the precipitation process

Particle form

Aragonit, Needles Calcit, Scalenoid Calcit Rhomboid

Primary particle diameter: 50 - 500 nm


© Brückner
5) Examples of synthetic papers

REM-photograph of a sequentially produced, density-


reduced 3- layer white film with a density of 0.68 g/ cm3.
© Brückner
Properties Unit SYN PA 3-layer SYN PA 3-layer Method
sequential simultaneous

Thickness µm 100 87 DIN 53370

Tensile - MD N/mm² 62 123 DIN 53455


strength TD N/mm² 122 110 DIN 53455

Elongation MD % 112 73 DIN 53455


at break TD % 37 57 DIN 53455

E- Modulus MD N/mm² 981 1775 DIN 53457


TD N/mm² 1690 2035 DIN 53457

Gloss T - 14 68 ASTM 2457


O - 12 15 ASTM 2457

Opacity % 94 79 DIN 53146

Density
Endfilm g/cm³ 0,68 0,91 DIN 53420

© Brückner
Properties Unit „Pearlized film“ „Pearlized film“ Method
sequential simultaneous

Thickness µm 19 34 DIN 53370

Tensile MD N/mm² 99 124 DIN 53455


strength TD N/mm² 174 128 DIN 53455

elongation MD % 117 53 DIN 53455


at break TD % 34 41 DIN 53455

E-Modulus MD N/mm² 1426 1800 DIN 53457


TD N/mm² 2618 1990 DIN 53457

Density
endfilm g/cm³ 0,75 0.73 DIN 53420
10 % CaCO3 20% CaCO3

Improvement of mechanical properties in machine direction possible.

Possibly improved behaviour on packaging machines (Project).


© Brückner
Other simultaneous stretched, density reduced systems:

PP/ PA6/ CaCO3-blend: Thickness (128 µm), highly opaque (98%)


white film with a density of 0.46 g/cm3, low water vapour
permeability, possible application as label or synthetic paper.

© Brückner
Other simultaneous stretched, density reduced systems:
PET/ PP/ CaCO3-blend: Thickness (120 µm), opaque (62%)
and stiff white film with a density of 0.97 g/cm3 (BOPET-film:
1.39 g/cm3), possible application as label or stiff synthetic paper.

© Brückner
Properties Unit „Pearlized film“ blend PP/ breathable Method
simultaneous PA6/ CaCO3 film

Thickness µm 34 128 83 DIN 53370

Tensile MD N/mm² 124 45 10 DIN 53455


strength TD N/mm² 128 56 10 DIN 53455

elongation MD % 53 69 24 DIN 53455


at break TD % 41 40 10 DIN 53455

E-Modulus MD N/mm² 1790 600 160 DIN 53457


TD N/mm² 1990 770 207 DIN 53457

Gloss T - 53 16 12 ASTM 2457


O - 57 16 13 ASTM 2457

Opacity % 58 98 95 DIN 53146

Density
endfilm g/cm³ 0,73 0,46 0,52 DIN 53420
20% CaCO3 22% CaCO3 60% CaCO3
© Brückner
Density reduction by foaming processes

Foaming process at the die exit, pressure increase towards die


© Brückner
Variation of endfilm properties by:
Use of the more layer technique: Foamed core with highly filled
rather smooth skin layers as foamed labels:

Skin layer with


Antiblock additive

Foamed
core

Skin layer

© Brückner
Variation of endfilm properties by:
• Use of different matrix polymers and raw material formulations:
As matrix polymers we used:

polypropylene-homopolymers,
polypropylene-block-copolymers,
high crystallinity polypropylene grades,
long chain branched polypropylene grades to increase the
melt strength,
blends thereof

Addition of different fillers like e.g. CaCO3 or TiO2 to influence


the surface properties, density reductions down to 0.30 g/ cm3,
wallpaper like structures, use of colour batches.
Use of other matrix polymers, e.g. PET or PA6.
High flexibility regarding machine settings (Stretching ratio MD
and TD, stretching temperatures, relaxation a.o.).
© Brückner
Structure of a density reduced, opaque, barrier BOPP film
Simultaneous biaxial orientation

Terpolymer 1,1 µm
Homopolymer, CaCo3 12,7 µm
Adhesive Layer 0,5 µm
EVOH 1,4 µm
Adhesive Layer 0,5 µm
Homopolymer, CaCo3 12,7 µm
Terpolymer 1,1 µm
Gauge: 30 µm

 Density: 0,78 g/ cm3


 OTR: 1,2 cm3/ m2 d bar 23°C/50% r.h.
 WVTR: 1,2 g/ m2 d 23°C/0 - 85% r.h.
© Brückner
Possible Applications: Research Project „Thin Films“

Project coordination

Database Simulation

End user

Film- Metallization Lamination Packaging Packaging


production SiOx Print properties
Adhesive e.g. haptics
simultaneous
sequential
© Brückner
Brückner Synthetic Paper R & D Activities
Year R & D Activity
1991 Development of biaxially oriented Synthetic Paper on
Brückner Sequential Pilot Line
1994 Introduction of Twin Screw Extrusion for
Synthetic Paper
1995 Printing Tests with Synthetic Paper
1996 Patent DE 19622082 Process for Synthetic Paper
1997 Patent WO 097/28948 Direct Additivation Process
1998 Transfer of Direct Additivation Process to
Production Scale
1998 Patent DE 19840991 Foamed Synthetic Paper
1999 Development of biaxially oriented Synthetic Paper on
Brückner Simultaneous Pilot Line
2001 Study on Coating Process for Synthetic Paper
2002 Experiments on Blend based Density Reduced Systems
2005 Development of White, Density Reduced 7-Layer Barrier Film
© Brückner
LISIM® Pilotline

© Brückner
LISIM® pilot line for simultaneous stretching
Film types PET PP PA
Thickness range [ µm ] 1 – 150 3 – 60 5 – 25
Stretching ratio MD 3–6 6 – 10 3–5
Stretching ratio TD 3–5 5 – 10 3–5
Speed (max.) [m/min] 150 150 50
Net output (max.) [kg/h] 250 200 70

Winder LISIM® IR- Chill-roll Extrusion


stretching preheating
oven

© Brückner
Laboratory Stretching Frame

 Low amounts of material needed


 Comparison of materials or mixtures
 Data for upscaling experiments

mode: simultan bei 155°C 7,5x7,5; 400%/s


35,00
E27_S
30,00
E32_S
25,00
E38_S
Force [N]

20,00
E44_S
15,00
E47_S
10,00
E44_N
5,00
E32_N
0,00
1 2 3 4 5 6 7 8
TD-Stretching Ratio [-] © Brückner
Upscaling Process
Method
Lab-Stretching Unit  Evaluation of Process Window
 Optimisation of Film Properties
 Measurement of Stretching Forces
 Simulation with FEM-Method
 Upscaling to production scale

Pilot-Line

Production-Line
Advantages
 Demonstration of the potentials of the
LISIM® - Technology
 Basic R & D for film stretching
 Development of new film types
 Development of new components
 Production of Sample Rolls for Pre-Marketing © Brückner
Path Forward and Conclusion

 There is no unambigious definition for a synthetic paper


 Even under the restriction to biaxially oriented films there is a wide
range regarding use of raw materials, processing conditions, film
structures and endfilm properties
 New driving forces could be 7-layer white barrier films or the use of
thermoplastics from renewable sources, e.g. PLA
 Additionally coating applications are possible

We do not think, that conventional cellulose papers could be


substituted in the near future

but…

SYN PA can be a high priced supplementation for special applications


© Brückner
Thank you very much for your attention!

© Brückner
© Brückner
© Brückner
© Brückner
One Main difference between simultaneous and sequential
stretching: Significantly higher stretching speeds
during the sequential MDO-stretching:

About 20% CaCO3 for a comparable density reduction.

Possible advantage by using a direct dosing equipment.


© Brückner
Advantages of 5-Layer Technology

Film Properties High Flexibility


 Enhanced transparency  Ready for new materials and future filmtypes
 Excellent white film with high gloss  3- and 5-layer film with the same equipment
 Special applications  Wide application range for white-opaque films

Raw Material Application


 An increased percentage of recycled  Self Adhesive Labels (Matt Or Glossy)
material can be processed  Wrap around labels
 Savings due to lower additivation  In-Mould Labels (Injection)
 In-Mould Labels (Thermo Forming)
 Film For Lamination To Paper, PE and other
Films
 Overwrapping
 Pressure Sensitive Labels

© Brückner
General Film Structure for Synthetic Paper

Film structure for synthetic paper with foamed core layer

PP filled with TiO2 or


other white pigments

Homo-PP filled with


CaCO3 drawn to a
defined foamed
structure
Remark:
For the skin layers either homo-PP or copo-PP can be
used.

© Brückner