Passive and Active Barrier Systems for the best packaging Performance

Applications, developments and Legal Frame

IV Symposium Internacional Sobre tecnologia alimentariafood technology international symposium

26-27 October 09Murcia Spain

CTC Centro Tecnológico Nacional de la Conserva y AlimentaciónDidier Houssier

didier.houssier@eval.be

OutlookCompany IntroductionDefinitionsPassive Barriers

Analytical Methods, Barrier Properties and ProductsActive Barriers

Analytical Methods, Properties and ProductsDevelopmentsLegal FrameSummary

Company Introduction

Kuraray Co. Ltd.Established June 24, 1926Net Sales ¥385 Billion (€2.48 Billion) FY2007Total Assets ¥509 Billion (€3.28 Billion) FY2007Employees 6,812 (March 31, 2007)Head Office TokyoKuraray in Europe

Kuraray Europe GmbH (www.kuraray.eu)Kuraray Specialities GmbH (www.kuraray-kse.com )EVAL Europe (www.eval.eu )

Tokyo Antwerp Houston

Kuraray / EVAL Europe History1926 Kurashiki Kenshoku Co. founded1949 name changed to Kurashiki Rayon (Kuraray)1958 Poval sales begin1965 European representative office in Hamburg (Düsseldorf from 1968)1970 name changed to Kuraray Co. Ltd.1972 EVAL sales begin1983 EVAL America established, production starts in 19861995 Kuraray EVAL Europe GmbH sales company established1997 EVAL Europe nv established for plant construction1999 EVAL Europe nv and KEE unified in Antwerp1999 EVAL Europe nv production begins, total capacity 12,000T2004 EVAL Europe doubles capacity to 24,000T

Antwerp, Belgium• EVAL™ EVOH resins• EVAL™ Film• KURARISTER™

Frankfurt, Germany• POVAL™ MOVIOL™ PVOH resins• other Chemicals and Resins• High Performance Materials• Medical materials• Fibres and Textiles

Europe

Okayama Antwerp Houston10,000T 24,000T 35,000T

Europe’s Largest EVOH production site

24,000T annual production capacity

ISO9000:2000 since 2001

TS16949 since 2003

European Technical Centre Processing/Development Hall in 2005

European Technical Centre Analytical work/Development since 1999

Definitions

Active materials and articlesCOMMISSION REGULATION (EC) No 450/2009 of 29 May 2009 defines ‘active materials and articles’ asmaterials and articles that are intended to extend the shelf-life or to maintain or improve the condition of packaged food; they are designed to deliberately incorporate components that would release or absorb substances into or from the packaged food or the environment surrounding the food;

Barrier MaterialsA Barrier is a material which limits the transfer of a permeating substance.A barrier Polymer can be defined as a macromolecule having the ability to limit the passage of gases, vapors, and liquids (…)Unlike glass and metals, no polymer offers an infinite gas barrier. Combinations of different polymers in multilayer structures enable to provide barrier to various productsNo limited time efficiency and no specificity to a substance

Barrier DefinitionThe Barrier is defined by the Permeability Value:

Product of the Diffusion and the SolubilityP = D . S

To be consider as a Barrier, the Permeability Value must be low. Not Real Scientific Value but usually < 250cc per µm thicknessThe Units will depend on the Permeant

Active BarriersCan be defined as materials that can absorb substances when it is brought into contact with itIt actively react with a specific substance by chemical reactionIt has limited time efficiency (contact with the substance will consume the material)Trigger to initiate the reactionIt is usually specific to a substance: Oxygen, Ethylene, Water or OdoursRequires the use of a Passive Barrier type EVOH EVAL™

Passive Barriers Polymers

Analytical Methods and EquipmentsBarrier Properties and Polymers

Barrier to Oxygen

Standard Gas for testing is OxygenO2GTR

Determination of steady-state rate of Transmission of Oxygen gas through Ethylene/vinyl alcohol Copolymers in the form of film using Coulometric Sensor is standardised by the ISO 14663-2: 1999 (Annex C)Determination of steady-state rate of Transmission of Oxygen gas through films using Coulometric sensor is standardised by the ASTM D3985

The UnitsThe unit in Europe :

Officially (ISO) :Femtometre per Pascal SecondFm/Pa.s

1 fm/Pa.s = 8.752 cm³/m².24h.atm1 cc/m².day.atm = 0.1143 fm/Pa.s

Practically : cc/m².day.atmFor comparative data :

cc.µm/m².day.atm or cc.20µm/m².day.atm(cc of Oxygen at 0°C under standard atmospheric pressure)

The Unit in the US : cm³.mil/100 in².day.bar1 cm³.µm/m².day.atm = 394 cm³.mil/100 in².day.bar

Oxygen Barrier AnalysesAnalyses on film Analyses on packages

The Permeability Equipment at EVAL Europe

Ox-Tran 2/20 and 2/21 MH and SH Modules

Permatran C4/41MC moduleTo determine the Carbon Dioxide Transmision Ratetrough film, bottle, tray, ... samples at well definedconditions of temperature (10 40°C) and 0% RH.

The Polymers Permeability to Oxygen

OXYGEN TRANSMISSION RATE OF VARIOUS POLYMERS VERSUS RELATIVE HUMIDITY at 20°C

0.1

1

10

100

1000

10000

0 20 40 60 80 100

Relative Humidity, %

O2G

TR, c

c.20

µm/m

².day

.atm

EVAL Film (EF-XL)EVAL-F

EVAL-E

PVDC (Saranex)

PAN (Barex 210)OPA-6

OPET

UPVC

BOPP

LDPE

MXD-6

A bit of Marketing… EVAL is the best…

0.1

1.0

10.0

100.0

0 20 40 60 80 100

EVAL Resins

O2GTR, cc.20µm/m².day.atm

Relative humidity,%

G Grade

E Grade

H Grade J Grade

T GradeF Grade L Grade

EVAL - O2GTR vs RH

The permeating Gases

MAP : vacuum, CO2/N2 70/30, CO2/N2 30/70! Air : 21% Oxygen

Active Barriers

Analytical Methods and EquipmentsEfficiency and Products

Analytical methodOxygen scavenger, Ethylene Adsorber, Dessicant or Odour AbsorberVarious Technologies depending on the substance of interest: gas detectors, reactants, chromatographIn food packaging applications: Oxygen scavengers and Ethylene Adsorber are usedNo ISO norm

And Equipments Examples

Head Space Analyser for Dansensorwww.pbi-dansensor.comOxygen Analyser from

Oxtranwww.mocon.com

Non-Invasive Oxygen Sensors from presenshttp://www.presens.de/

• Evolution of the Oxygen in the head space in Oxygen Scavenger containing PP/EVOH/PP multilayer barrier containers

• Study conducted in cooperation with Ciba and RPC (www.rpc-group.com )

Oxygen in the headspace

O2 content measurement after 6 months

0.000.501.001.502.002.503.003.504.004.505.005.506.006.50

0 200

400600

800

1000

12001400

1600

1800

20002200

2400

2600

28003000

3200

3400

36003800

4000

4200

4400

hours

% O

2

0%1.9%3%4.5%3% Alu

1st month 2nd month 3rd month 5th month4th month 6th month

O2 content measurement after 6 months

0.000.501.001.502.002.503.003.504.004.505.005.506.006.50

0 200

400600

800

1000

12001400

1600

1800

20002200

2400

2600

28003000

3200

3400

36003800

4000

4200

4400

hours

% O

2

0%1.9%3%4.5%3% Alu

1st month 2nd month 3rd month 5th month4th month 6th month

Scavenging TechnologiesVarious Technologies to act on the head space composition during shelf lifeChoice will depend on the application and the requirements for the packaging: transparency, shelf life, temperature, Humidity, convenience,…costRequires a good know-how about the various constraints of the packaging and the packaged product (water activity for example)Oxygen scavenging systems are the most commonly used scavenging system today for food packaging applications

In practice Oxygen scavenging system

Segments Applications Requirements Commercial Systems in place

Bottles Beer, sauces, drinks Transparency, O2 and CO2 barrier

Inorganic in Caps or Closures; Organic in Bottle wall

Semi-rigid Packaging

Premium Chilled Meats (Sliced Ham, salami,…), Ham, sausage, chicken nuggets

High temperature and Humidity; low temperature storage 4°C

Inorganic as sachet or sticker in the head space

Semi-rigid Packaging

Pizza, pasta Packaging Room temperature storage

Inorganic as sachet or sticker in the head space

Rigid Packaging Wet Pet Food and Ready Meal

Retort resistant system Inorganic in Container Wall

Not presumed to be an exhaustive list but rather examples

Developments

DevelopmentsDevelopment of the Packaging system to improve food preservation has been conducted among the supply chain and still continuesProgress in

Food preservativesModified Atmosphere Packaging orPackaging technologies

Have been completed byOptimisation of passive barrier andDevelopment of Active barrier systems

More developments are to be expected in the future…

Legal Frame

Legal Frame (I)Thanks to the Regulation (EC) No 1935/2004 of the European Parliament and of the Council of 27 October 2004 on materials and articles intended to come into contact with foodrepealing Directives 80/590/EEC and 89/109/EEC (the mother directive)States thatPending the adoption of additional rules in a specific measure on active and intelligent materials and articles, substances deliberately incorporated into active materials and articles to be released into the food or the environment surrounding the food shall be authorised …

Legal Frame (II)COMMISSION REGULATION (EC) No 450/2009 on active and intelligent materials and articles intended to come into contact with food was adopted on 29 May 2009 It is a specific Directive as per 1935/2004/EC regulation.This Regulation establishes specific requirementsfor the marketing of active and intelligent materials and articles intended to come into contact with food.Only substances which are included in the ‘Community list’ of authorised substances may be used in components of active and intelligent materials and articles.

In Practice, what does it means forOxygen Scavenging systems

EVAL Europe Understanding

The Field of 450/2009/ECMany different types of active and intelligent materials and articles exist.

The substances responsible for the active and/or intelligent function can be contained in a separate container, for example, inclusion in a small paper sachet or, the substances can be directly incorporated into the packaging material, for example, incorporation in the plastic of a plastic bottle.

Those substances, responsible for creating the active and/or intelligent function of those materials and articles (the components) should be evaluated in accordance with this specific Regulation. The passive parts if all plastic is covered by 2002/72/EC Directive

O2 content measurement after 6 months

0.000.501.001.502.002.503.003.504.004.505.005.506.006.50

0 200

400

600

800

1000

1200

1400

1600

1800

2000

2200

2400

2600

2800

3000

3200

3400

3600

3800

4000

4200

4400

hours

% O

2

0%1.9%3%4.5%3% Alu

1st month 2nd month 3rd month 5th month4th month 6th month

O2 content measurement after 6 months

0.000.501.001.502.002.503.003.504.004.505.005.506.006.50

0 200

400

600

800

1000

1200

1400

1600

1800

2000

2200

2400

2600

2800

3000

3200

3400

3600

3800

4000

4200

4400

hours

% O

2

0%1.9%3%4.5%3% Alu

1st month 2nd month 3rd month 5th month4th month 6th month

Shelfplus 02

0.0000

0.0050

0.0100

0.0150

0.0200

0.0250

0.0300

0.0 5.0 10.0 15.0 20.0 25.0 30.0 35.0Time (days)

O2G

TR (c

c/tr

ay.d

ay)

4.5% SPO2 3% SPO2

1.9% SPO2 0% SPO2

Evolution of the Oxygen in the head space Oxygen Permeation after retort

Designed to Deliberately incorporate components that would absorb Oxygen from

the environment surrounding the food?

Oxygen Scavengers in Sachets

The free-oxygen absorbing agent, AGELESS™, absorbs oxygen in a sealed container and creates a deoxidized environment, where theconcentration of oxygen is 0.1% or lower.2002/72/EC listing: PM Ref. 81760: Powders, flakes and fibres of brass, bronze, copper, stainless steel, tin and alloys of copper, tin and iron SML = 48 mg/kg (expressed as iron)Designed to Deliberately incorporate components that would absorb Oxygen from the environment surrounding the food

Multilayer bottleO2 Scavenging layer

Tie layersPolyolefin layers

No

O2

envi

ronm

ent

O2

O2

O2

0 200 400

600

800 1000200

Oxygen Scavenger Polymeric Systems

NotNot Designed toDesigned to DeliberatelyDeliberatelyincorporate components that would incorporate components that would

absorb Oxygen absorb Oxygen from thefrom theenvironment surrounding environment surrounding the food.the food.

SUMMARY

SUMMARYKuraray / EVAL Europe is a major actor in the barrier packaging systemsOur presentation reviewed Active and Passive barrier systems from

The definition stands-pointThe Analytical MethodsThe Properties in terms of barrier or scavenging performanceThe Products applications and developments

A snap shot on the legal frame was madebefore getting to the end of our presentation

Thanks… visit us at www.eval.be