Migrating vs non migrating in polymer

Additives, Compounds & Color Masterbatches for the plastics industry
Dr. Evgeni Zelikman / Irina Shtein Rozenman
R&D Division, Tosaf
Israel
Migrating Additives vs. Non
Migrating Additives
in Polymer Films
5th Specialty Films & Flexible Packaging Global Summit 2016, 21st - 22nd September 2016 at Grand Hyatt, Mumbai, India

Outline
Outline
• Tosaf at a Glance
• Introduction
• Slip
• Antifog
• Summary

Tosaf at a glance
 Sales Turnover - $400m
 Sales Offices - 50 countries
 Production Capacity -100K tons
 Number of Employees - 1000
 Production Sites -11 plants in 7
countries

TOSAF is a leading manufacturer
Tosaf at a glance

Introduction
Migration mechanism of migrating additives
Film
Time

Introduction
Structure of migrating molecules
Polar - Non compatible with polyolefin
Non Polar (Alkyl) - compatible with polyolefin
antifog
antistatic / antifog slip

Introduction
Migrating
Non Migrating
Time

Introduction
• Factors which control migration of additives:
• Polymer/Additive compatibility (Solubility Parameter,
Polarity), Polymer crystallinity
• Temperature
• Concentration of additive in the bulk
• Concentration of additive on the surface
• Other migrating additives
• External conditions

Introduction
Requirements from migrating additives:
 Create optimal surface coverage for additive activity
 Avoid excessive surface concentration (blooming)
 Minimal effect on optical properties
 Minimal effect on printing
 Minimal effect on lamination
 Minimal effect on sealing

Introduction
Migrating
Additives
Non Migrating
Additives
Negative Effect
on Printing,
Sealing,...
Might Be No
Concentration Low High
Effect on
Optical
Properties
Lower Higher
Permanent No Yes

Slip
COF
Time
Film
Mechanism

Slip
0
0.5
1
1.5
2
20 30 40 50 60
COF
Temperature [oC]
Erucamide
Temperature Dependence

Slip
• Standard, Erucamide type, slip migrates to the surface at
room temperature and creates the slip effect.
• At 60oC the solubility of Erucamide inside the polymer
matrix increases, it migrates inside and the slip effect
disappears.
(C. A. Shuler, A.V. Janorkar, D.E. Hirt, Polymer Engineering and Science, 2004, 44, 2247)
25 oC 60 oC
Film

Slip
• Hot slip (SB5851PE) contains Erucamide and another special
slip additives, which active primarily at elevated
temperatures.
• At 60oC the solubility of Erucamide inside the polymer matrix
increases, it migrates inside while the other slip agents
migrate outside maintaining the slip effect.
25 oC 60 oC
Film

Slip
0
0.5
1
1.5
2
20 30 40 50 60
COF
Temperature [oC]
Hot Slip
Erucamide
(SB5851PE)
Migrating Hot Slip Temperature Dependence

Slip
Non migrating slip usually consists of solid, filler
type, additive (PMMA beads, silicone beads).
The use of non migrating slip ensures permanent,
temperature independent slip properties.
Permanent slip additive is usually expensive, used in
relatively high dosing and may compromise optical
properties.

Slip
Permanent Slip
To overcome price issue Tosaf developed new cost effective
permanent slip masterbatch, SB6484PE.
Antiblock
Special
Slip
Extruder
Film Production

Antifog
Film
Time
Water droplet
on neat PE film
Water layer
on PE film with antifog
Wetting (contact) angle
Neat PE

Antifog
ICI’s Cold fog test parameters,40C
A C E
Neat PE film PE film with antifog
Fog (dripping) - condensation of water vapor

Antifog
Corona treatment - Surface modification
-OH Hydroxyl group
>O=H Carbonyl group
-COOH Carboxyl group
PE with ADDITIVES
PE
3 - Ozone
3
2
H2O

Corona treatment for printing /coating /lamination
PE with ADDITIVES
PE
PA
PA Tie
PE
PE Tie
EVOH
9 layer barrier film
 Corona treatment
 Polar polymers – EVOH, PA
 Tie layers
 Lamination glue
Antifog
Factors which influence direction of migration

food contact side
Antifog
Our Goal – to direct the migration to the desired surface

Antifog
Corona treatment for printing /coating /lamination
AF (Antifog)
Tosaf’s novel additive for PE – BR7483PE MB

General experimental design
Antifog
 3-layer blown & cast film
 Corona treated PE skin on the opposite skin of AF4953PE
 Barrier additive BR7483PE in PE core
 Cold fog test
PE skin with corona
PE core with BR7483PE
PE skin with AF additive
General structure - A/B/C – 15/10/15 µm
B
A
C

Antifog
Cast 3-layer films
 3, 4, 5 % of AF4953LL, 700 ppm antiblock.
 17, 33% of BR7483PE with LDPE.
 Thickness of the BR7483PE core layer – 3, 5, 10 µm.
5% AF
with corona
10 µm
5% AF+ 33%
BR7483PE
with corona
10 µm
5% AF+ 17%
BR7483PE
with corona
10 µm
5% AF
no corona
10 µm
5% AF+ 33%
BR7483PE
with corona
5 µm
5% AF+ 33%
BR7483PE
with corona
3 µm
A A
E
E
E E

Blown 3-layer films
Antifog
 3, 4, 5, 7 % of AF4953LL
 5, 11, 17, 25, 33% of BR7483PE
 Thickness of the BR7483PE core layer – 5, 10, 15 µm
3% AF + 11% BR7483PE with corona
3% AF + 11% BR7483PE no corona
3% AF no corona
3% AF with corona
E
E
B
B

Antifog
* taken from en.wikipedia.org
XPS: X-ray photoelectron spectroscopy – surface sensitive
quantitative spectroscopic technique to analyze the surface chemistry of
a material.

XPS results for cast films 1
Antifog
4
6
8
10
12
14
16
18
0 10 20 30 40
No corona side
Corona side
AF 5% opposite to corona + barrier additive in middle
4
6
8
10
12
14
16
18
0 10 20 30 40
No corona side
Corona side
PE without additives + corona one side
 Layers containing AF have different %O level
vs. corona treated sides.
 Barrier keeps the difference in %O stable by
preventing AF migration to the corona side.
Δ=4
4
6
8
10
12
14
16
18
0 10 20 30 40
No corona side
Corona side
AF 5% opposite to corona side

Summary
 There are many advantages for both
migrating and non migrating additives.
 Altering migration of the migrating
additives opens a lot of new possibilities
for packaging films.
 Various mechanisms are available for
migration control.

Studies presented were partially supported supported by the Magnet Program of
the Israeli Ministry of Economy and the Israeli P^3 Consortium with Technion
Research group: Y. Cohen, L. Vaikhanski, R. Khalfin
Acknowledgment

Migrating vs non migrating in polymer

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